Coal Desulfurization: Chemical and Physical Methods

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.fw001

Coal Desulfurization Chemical and Physical Methods

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.fw001

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Coal Desulfurization Chemical and Physical Methods Thomas D . Wheelock, EDITOR

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.fw001

Iowa State University

Based on a symposium sponsored by the Division of Fuel Chemistry at the 173rd Meeting of the American Chemical Society, New Orleans, La., March 23,

1977

64

ACS SYMPOSIUM SERIES

AMERICAN CHEMICAL SOCIETY WASHINGTON, D. C.

1977

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.fw001

Library of Congress

Data

Coal desulfurization. (ACS symposium series; 64 ISSN 0097-6156) Includes bibliographic references and index. 1. Coal—Desulphurization—Congresses. I. Wheelock, Thomas D . , 1925II. American Chemical Society. Division of Fuel Chemistry. III. Series: American Chemical Society. ACS symposium series; 64. TP325.C516 662'.623 77-17216 ISBN 0-8412-0400-4 ACSMC8 64 1-332 1977

Copyright © 1977 American Chemical Society All Rights Reserved. N o part of this book may be reproduced or transmitted in any form or by any means—graphic, electronic, including photocopying, recording, taping, or information storage and retrieval systems—without written permission from the American Chemical Society. The citation of trade names and/or names of manufacturers in this publication is not to be construed as an endorsement or as approval by ACS of the commercial products or services referenced herein; nor should the mere reference herein to any drawing, specification, chemical process, or other data be regarded as a license or as a conveyance of any right or permission, to the holder, reader, or any other person or corporation, to manufacture, reproduce, use, or sell any patented invention or copyrighted work that may in any way be related thereto. PRINTED IN T H E UNITED STATES O F AMERICA

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

ACS Symposium Series

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.fw001

Robert F. G o u l d , Editor

Advisory Board Donald G . Crosby Jeremiah P. Freeman E. Desmond Goddard Robert A . Hofstader John L. Margrave Nina I. McClelland John B. Pfeiffer Joseph V . Rodricks Alan C. Sartorelli Raymond B. Seymour Roy L. Whistler Aaron Wold

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.fw001

FOREWORD The ACS SYMPOSIUM SERIES was founded in 1974 to provide

a medium for publishing symposia quickly in book form. The format of the SERIES parallels that of the continuing ADVANCES IN CHEMISTRY SERIES except that in order to save time the papers are not typeset but are reproduced as they are submitted by the authors in camera-ready form. As a further means of saving time, the papers are not edited or reviewed except by the symposium chairman, who becomes editor of the book. Papers published in the ACS SYMPOSIUM SERIES are original contributions not published elsewhere in whole or major part and include reports of research as well as reviews since symposia may embrace both types of presentation.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

PREFACE mong the various impurities in coal, sulfur is one of the most prevalent and pervasive, and it has long been a serious problem since it interferes in one way or another with most major uses of coal. In metallurgical coal, sulfur adds to the difficulty and cost of making steel because it must be kept out of the final product. In steam coal, sulfur compounds contribute significantly to the wear of pulverizing mills and conveying equipment and, furthermore, upon combustion produce sulfur oxides which corrode boilers and create an environmental problem. Since the rate of coal use for heat and power generation is projected to increase greatly during the next few years, the problems caused by the sulfur are also projected to increase. Among various methods which have been proposed to solve these problems, precombustion desulfurization of steam coal offers several potential advantages over flue gas desulfurization, fluidized bed combustion, and conversion of coal into liquid and gaseous fuels. Precombustion desulfurization involves physical or chemical operations which span an entire range of complexity and sophistication. The simpler physical methods are the most cost effective, and even some of the proposed chemical desulfurization methods are likely to be more cost effective than processes which convert coal into liquid and gaseous fuels. Also precombustion desulfurization addresses not only the problem of environmental pollution but also the other problems of equipment wear and corrosion. In addition, desulfurized coal can be utilized in existing plants without extensive modification or retrofitting, and for non-base load power plants, the use of desulfurized coal can avoid tieing up investment capital in flue gas desulfurization systems which are not fully utilized. Furthermore in comparison with gaseous fuels, desulfurized coal is stored readily for future use. In spite of these foreseen advantages and years of research and development, only a few desulfurization methods are highly perfected and used commercially. These methods in commercial use generally depend on making a simple physical separation of coarse sulfur-bearing mineral particles from coal. Unfortunately many coal deposits contain finely disseminated minerals and organically combined sulfur which cannot be removed by these methods. However, because of the impetus of government pollution control regulations, increasing demand for coal,

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In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

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and greater influx of both government and private sector research funds, the development of new and more effective methods for desulfurizing coal is accelerating. The new methods include a wide gamut of physical and chemical processes with many different workers and organizations involved in their development. As a result of this effort and an attractive cost-benefit ratio, it is anticipated that coal desulfurization will be increasingly important in the future, not only in preparing coal for direct combustion but also for coking and for conversion into liquid and gaseous fuels. Because of the rising interest in coal desulfurization processes, a symposium on this subject was held which attracted a series of papers describing the results of recent research on a number of promising proc­ esses. These papers form the nucleus of the present volume. However, since not all areas of the field were equally well represented, additional material was added to produce a volume which provides a broad coverage of recent research. Included are reports of basic and applied research and development on physical separation methods ( such as froth flotation, selective oil agglomeration, high-gradient magnetic separation, and dynamic segregation ) and on chemical processes ( such as leaching, chlorinolysis, pyrolysis, hydrodesulfurization, and gas-phase oxidation). There is also a review of both current and developing industrial coal preparation practices. Although these methods may alter the physical and/or chemical properties of coal and may produce liquid or gaseous by-products, the principal product is still a solid carbonaceous material. Hence, methods designed primarily to produce desulfurized liquid or gaesous fuels are not included. Since progress in the field of desulfurization depends on knowing and understanding the nature and amount of sulfur in coal, several reports of work on characterizing the size distribution and physical form of the principal sulfur-bearing minerals (iron pyrite and marcasite) in coal and on developing new methods for determining the various chemi­ cal forms of sulfur in coal are also included. This related work is impor­ tant because the total amount of sulfur in coal and its distribution be­ tween various physical and chemical forms vary greatly. Among the new developments discussed is a method for the direct determination of organically bound sulfur. Because of its broad coverage and in-depth review of much of the current research on coal desulfurization, this volume provides both an introduction to the subject as well as a fairly comprehensive treatment and status report. Thus it should be of value to both the neophyte and the experienced worker not only because it describes possible solutions to the problem of sulfur in coal but also because it indicates where science χ

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

and technology stand in achieving these solutions and where there is need for more research and development. Many individuals contributed to the preparation of this volume. A number of researchers contributed the results of their efforts, the officers of the Fuel Chemistry Division of the American Chemical Society provided encouragement, and the editor and staff of the Symposium Series produced the volume. All of these individuals deserve our appreciation. THOMAS D. WHEELOCK

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Iowa State University Ames, Iowa October 3, 1977

xi

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

1 Coal Microstructure and Pyrite Distribution

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RAYMOND T. GREER Department of Engineering Science and Mechanics, Engineering Research Institute, Ames Laboratory, U.S. ERDA, Iowa State University, Ames, IA 50011

The microstructure of coal is of interest in understanding coal properties. Microstructural features may affect the selection of coal beneficiation methods for removing impurities. For example, in planning sulfur removal schemes it is useful to understand the proportionment of inorganic sulfur compared with that of organic sulfur. Details of size, shape, orientation, and distribution factors for pyrite, certain pyrite and maceral groupings or fields, or other coal constituents(maceralsand other inorganic components) are of importance in supporting rational designs of sulfur removal processes. Recent scanning electron microscope (SEM) investigations help to show the interrelations between macerals and inorganic phases such as pyrite (FeS , the primary inorganic source of sulfur in coal) (1,2,3,4). This form of characterization complements optical microscope studies (5,6,7,8) and conventional transmission electron microscope (TEM) studies (9-15) which have been used to classify and to study coal constituents. SEM offers a way to visualize features hundreds and thousands of Angstroms in diameter by direct observation in three dimensions which is not available by any other technique. Many significant coal features (such as cellular components) and impurity crystals occur in this size range. Important features of coal constitution discovered by SEM are discussed below. 2

Experimental

Investigation

A p p a r a t u s . A JSM-U3 SEM w i t h a n EDAX e n e r g y d i s p e r s i v e x - r a y a n a l y s i s system i s used f o r t h e m i c r o s c a l e s t r u c t u r a l and c h e m i c a l studies. The r e s o l u t i o n c a p a b i l i t i e s o f t h e i n s t r u m e n t o n a d a y t o - d a y b a s i s a r e somewhat b e t t e r t h a n 200 Â f o r m i c r o s t r u c t u r a l i n f o r m a t i o n and s u b m i c r o m e t e r i n a c h e m i c a l a n a l y s i s mode f o r l o c a l i z e d c r y s t a l d e s c r i p t i o n . The s y s t e m p r o v i d e s s i z e , s h a p e , o r i e n t a t i o n , and d i s t r i b u t i o n i n f o r m a t i o n f o r i n o r g a n i c phases and coal constituents.

3

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COAL DESULFURIZATION

Procedure. Samples f o r SEM s t u d i e s a r e mounted i n an o r i e n t a t i o n where t h e f a c e and v e r t i c a l p o s i t i o n i n t h e c o a l seam a r e maintained. The e l e c t r o n beam a c c e l e r a t i n g p o t e n t i a l u s u a l l y u s e d i n v i e w i n g t h e s p e c i m e n s i s 25 kV. S a m p l e s r e c e i v e a vacuumd e p o s i t e d c o a t i n g o f a p p r o x i m a t e l y 200 Â g o l d ( f o r m i c r o s t r u c t u r a l s t u d i e s ; to m i n i m i z e c h a r g i n g problems) or a vacuum-deposited g r a p h i t e c o a t i n g of 20-100 Â ( f o r m i c r o c h e m i c a l s t u d i e s ; to a v o i d p o s s i b l e i n t e r p r e t a t i o n d i f f i c u l t i e s o f t h e s u l f u r and t h e g o l d x-ray fluorescence l i n e s ) . A d d i t i o n a l i n f o r m a t i o n about e x p e r i m e n t a l t e c h n i q u e a p p e a r s i n R e f . 4_.

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Materials. Samples o f h i g h - v o l a t i l e C b i t u m i n o u s c o a l f r o m b o t h s t r i p and s h a f t m i n e s i n Iowa f o r m t h e p r i m a r y m a t e r i a l s o f i n t e r e s t i n t h i s work. Results

and

Discussion

Microstructural Features. To see t h e i n t e r r e l a t i o n o f i n o r g a n i c p h a s e s s u c h as p y r i t e t o t h e c o a l c o n s t i t u e n t s (macérais), m i c r o g r a p h s have been chosen f i r s t to p r e s e n t the r e l a t i v e o r g a n i z a t i o n o f t h e m i c r o s t r u c t u r a l components. T h e s e w i l l be f o l l o w e d by a d d i t i o n a l m i c r o g r a p h s r e p r e s e n t a t i v e o f t h e common ways w h i c h p y r i t e c r y s t a l s occur i n c o a l . F i g u r e 1 p r o v i d e s d e t a i l s of c e l l u l a r compression. The c o a l s p e c i m e n f r o m t h e L o v i l i a ( s h a f t ) m i n e i s e x a m i n e d i n two o r i e n t a t i o n s : t h e top o f a f r e s h f r a c t u r e s u r f a c e c o r r e s p o n d i n g t o v a r i o u s m a g n i f i c a t i o n v i e w s o f the top o f t h e c o a l seam ( F i g u r e s l a - c ) ; and t h e s i d e , end-on v i e w o f t h e s t r a t i f i e d material (Figures l d - f ) . F r a g m e n t a t i o n and c o m p r e s s i o n f e a t u r e s of c e l l u l a r m a t e r i a l are seen f o r other c o a l s i n F i g u r e s 2, 3 , and 4 and i n R e f s . 1^ and 4_. I n F i g u r e s l a - c , the c o a l i f i e d p l a n t f i b e r s run from l e f t to r i g h t i n t h e i m a g e s . M o s t o f t h e f i b e r s a r e a p p r o x i m a t e l y 25 ym t h i c k , as s e e n f o r e x a m p l e i n a h i g h m a g n i f i c a t i o n v i e w i n F i g u r e le. M i c r o s t r u c t u r a l d e t a i l o f p i t s and o t h e r i n d i v i d u a l c e l l u l a r f i b e r d e t a i l s can be d i s c r i m i n a t e d i n t h i s v i e w as w e l l . The o p e n i n g s and r e g i o n s f o r m i n g p a t h w a y s o f i n t e r c o m m u n i c a t i o n f o r f l u i d s and gas b e t w e e n and w i t h i n c e l l s can be s e e n i n s i d e v i e w s ( F i g u r e s l d - f ) of the stacked f i b e r s . As t h e r e s o l u t i o n o f t h e s c a n n i n g e l e c t r o n m i c r o s c o p e i s o f t h e o r d e r o f 150 t o 200 A n g s t r o m s , m i c r o p o r e s o c c u r r i n g b e l o w t h i s s i z e w i l l n o t be o b s e r v e d , even a t the h i g h e s t m a g n i f i c a t i o n s . F i g u r e I f shows t h e c o a l o p e n i n g s i n t h i s c a s e t o be o f t h e o r d e r o f 20 ym o r l e s s , as i n f l u e n c e d by t h e d e g r e e o f c o m p r e s s i o n o f t h e f i b e r s s e e n i n t h e p a r t i c u l a r f i e l d o f view.* C o n s i d e r a b l e c o m p r e s s i o n o f t h e p l a n t s o u r c e m a t e r i a l i n t h e c o a l can o c c u r , and i n c e r t a i n e x a m p l e s t h e c e l l u l a r d e t a i l may be c o m p l e t e l y a b s e n t down t o t h e r e s o l u t i o n l i m i t of t h i s e l e c t r o n m i c r o s c o p y t e c h n i q u e . The c e l l w a l l s a r e o f t h e o r d e r o f 2 ym t h i c k i n t h e s e s i d e v i e w s ( F i g u r e I f , f o r e x ample) . F i g u r e 2 r e p r e s e n t s an e x a m p l e o f b o t h c o m p r e s s i o n and d i s -

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

GRÉER

Coal Microstructure and Pyrite Distribution

5

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1.

Figure 1. Coal from the Lovilia mine (Iowa) showing detailed cellular features of the coalified plant material (a) (top left) Top view; scale bar, 200 \xm. (b) (top right) Top view; scale bar, 100 pm. (c) (middle left) Top view; scale bar, 20 ^m. (d) (middle right) Side view; scale bar, 200 fxm. (e) (bottom left) Side view; scale bar, 100 \xm. (f) (bottom right) Side view; scale bar, 20 pm.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

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COAL DESULFURIZATION

t o r t i o n of the c o a l i f i e d p l a n t c e l l u l a r f e a t u r e s . The s p e c i m e n was t i l t e d so t h a t b o t h t h e t o p and s i d e o f t h e s p e c i m e n c o u l d be seen i n t h i s v i e w . Across the c e n t r a l r e g i o n of the micrograph this i s particularly clear. An a n a l o g y w o u l d be t o t a k e a s t a c k of s o l i d r e c t a n g u l a r b o x e s ( e a c h open a t t h e e n d s ) , e a c h a p p r o x i ­ m a t e l y 25 ym χ 25 ym on t h e end by s e v e r a l h u n d r e d ym i n l e n g t h , to r e p r e s e n t a f i b e r , and c r u s h and bend t h e s t a c k by c o m p r e s s i o n p e r p e n d i c u l a r to the long dimension of the boxes. A r e s u l t some­ what s i m i l a r i n a p p e a r a n c e t o F i g u r e 2 c o u l d be o b t a i n e d . V a r i a t i o n s o f c e l l u l a r f o r m s and f r a g m e n t s a r e s e e n i n F i g ­ u r e s 3 and 4. These r e p r e s e n t f r e s h f r a c t u r e s u r f a c e s of the c o a l t h a t r e v e a l t h e m a t e r i a l was a l r e a d y f r a g m e n t e d and c r u s h e d p r i o r to t h e s c a n n i n g m i c r o s c o p e i n v e s t i g a t i o n . T h i s i s a way t h e c o a l c o n s t i t u e n t s c a n o c c u r and s t a c k w i t h i n t h e seam i t s e l f , e x c l u s i v e of s a m p l i n g and p r e p a r a t i o n f o r e x a m i n a t i o n on a m i c r o s c a l e . T h u s , a w i d e r a n g e o f d e t a i l may be p r e s e n t , f r o m e x a c t s u b c e l l u l a r f e a t u r e s w h e r e l i t t l e o r no p e r t u r b a t i o n c a n be d e t e c t e d by m i c r o s t r u c t u r a l e x a m i n a t i o n , t o t h a t where t h e r e i s a complete absence of d e t a i l o f t h e s o u r c e m a t e r i a l . T h e s e c e l l u l a r o p e n i n g s c a n be f i l l e d w i t h p y r i t e , gypsum, c a l c i t e o r o t h e r m i n e r a l i n c l u s i o n s which were d e p o s i t e d e i t h e r a t t h e t i m e o f e a r l y s t a g e s o f c o a l i f i c a t i o n o r a f t e r t h e c o a l had formed. I n c e r t a i n p r o c e s s i n g schemes t o remove c r y s t a l l i n e p y ­ r i t e , t h e p r e s e n c e o f t h i s t y p e o f open m i c r o m e t e r s i z e n e t w o r k m i g h t be u s e d t o a d v a n t a g e d e p e n d i n g i n p a r t on t h e o c c u r r e n c e , d i s t r i b u t i o n and s u r f a c e c h a r a c t e r i s t i c s o f t h e t y p e o f c o a l c o n ­ stituent. M i c r o c h e m i c a l F e a t u r e s . M i n e r a l i n c l u s i o n s s u c h as p y r i t e a r e r e v e a l e d o v e r a v a r i e t y o f s c a l e s o f m i c r o s c o p i c and m a c r o ­ scopic investigations. The s u l f u r - b e a r i n g p h a s e s a r e o f p a r t i c u ­ l a r i n t e r e s t i n v i e w o f a t t e m p t s t o remove s u l f u r p r i o r t o combus­ tion. The p r i m a r y f o r m s o f s u l f u r i n c o a l i n c l u d e : (1) P y r i t i c s u l f u r : FeS (2) Sulfate sulfur: CaSOi *2H 0 (3) O r g a n i c s u l f u r : a. m e r c a p t a n o r t h i o l RSH (R and R b e i n g a l k y l b. s u l f i d e or thio-ether RSR or a r y l groups) c. disulfide RSSR d. a r o m a t i c s y s t e m s c o n t a i n i n g HC — CH the thiophene r i n g || || HC CH 2

+

2

f

1

1

V A s i g n i f i c a n t p o r t i o n o f t h e s u l f u r i n c o a l may o c c u r as p y ­ r i t e i n t h e f o r m o f i n d i v i d u a l c r y s t a l s , o r as a s s e m b l i e s o f c r y s ­ t a l s f o r m i n g f r a m b o i d s (a w o r d c o i n e d by R u s t (16) i n 1935 m e a n i n g b e r r y - l i k e ) , o r a s a s s e m b l i e s o f f r a m b o i d s i n t e r c o n n e c t e d by a d d i ­ t i o n a l p y r i t e o c c u r r i n g o v e r a l a r g e - s i z e r a n g e up t o c e n t i m e t e r s i n w i d t h o r g r e a t e r . P y r i t e ( F e S , c u b i c ) and m a r c a s i t e ( F e S , 2

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

2

1.

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Coal Microstructure and Pyrite Distribution

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Figure 2. Compressed coalified plant cellular material showing both the top and the side of the fibers. Number 6, Midland, III. coal. Scale bar, 15 μm.

Figure 3. Phnt debris. Mich mine (Iowa). Scale bar, 10 μm.

Figure 4. Plant debris. Both fragmenta­ tion and distortion are seen. Horton, KY. Scale bar, 10 μm.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

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orthorhombic) are observed i n c o a l samples, the c u b i c form b e i n g t h e most a b u n d a n t o f t h e s u l f i d e m i n e r a l s . O t h e r i n o r g a n i c f o r m s o f s u l f u r s u c h a s gypsum a r e r e l a t i v e l y l o w i n abundance (<0.5 wt %) o r r a p i d l y a p p e a r a s w e a t h e r i n g p r o d u c t s f r o m t h e p y r i t e ( 1 7 ) . There i s l i t t l e e x a c t knowledge of the forms i n which s u l f u r exi s t s i n organic combination. Organic s u l f u r i s present i n a l l c o a l ; i t i s determined as a n u m e r i c a l d i f f e r e n c e between t o t a l s u l f u r and t h e sum o f c h e m i c a l l y d e t e r m i n e d s u l f a t e s u l f u r ( g e n e r a l l y a t t r i b u t e d t o gypsum) and c h e m i c a l l y d e t e r m i n e d p y r i t i c s u l f u r (18). R e p r e s e n t a t i v e f o r m s o f p y r i t e a r e shown i n F i g u r e s 5a-k. In t h e s e s a m p l e s , m i c r o m e t e r - s i z e d p y r i t e i s an i m p o r t a n t c o n s t i t u e n t of p a r t i c l e s , n o d u l e s , c o n c r e t i o n s , and o t h e r p y r i t e a s s e m b l i e s . The a s s o c i a t i o n o f t h e p y r i t e w i t h m i c r o s t r u c t u r a l f e a t u r e s o f t h e c o a l c o n s t i t u e n t s c a n be o b s e r v e d i n s e v e r a l o f t h e s e m i c r o g r a p h s . F o r a d d i t i o n a l e x a m p l e s , s e e R e f s . 1, 2, _3, and 4_. D e t a i l e d p y r i t e s i z e d i s t r i b u t i o n d a t a and d i s t r i b u t i o n d a t a f o r t h e f o r m s of p y r i t e w i t h d e p t h i n a seam a r e p r e s e n t e d i n R e f s . JL, 4_, 19, and 20. The s i n g l e c r y s t a l f o r m o f p y r i t e p r e d o m i n a t e s a t a p p r o x i m a t e l y 1-ym p a r t i c l e d i a m e t e r s , b u t i t i s an i m p o r t a n t f o r m o v e r a wide range of s i z e s . Commonly, m i c r o m e t e r d i a m e t e r c r y s t a l s w i l l be m a j o r c o n s t i t u e n t s o f l a r g e p y r i t e m a s s e s . I n F i g u r e s 5a and b, t h e o c c u r r e n c e o f s m a l l i n d i v i d u a l p y r i t e c r y s t a l s w i t h i n s e t s of c o a l i f i e d p l a n t f i b e r s ( t e l e n i t e ) i s p r e s e n t e d a t two d i f f e r e n t m a g n i f i c a t i o n s . The e x a m i n a t i o n i s made i n a n o r i e n t a t i o n p e r p e n d i c u l a r t o t h e t o p o f t h e seam o f c o a l f o r t h i s s p e c i m e n f r o m t h e seam ( i . e . , t h e t o p o f a p o r t i o n of a seam o f c o a l i s s e e n ) . M o s t o f t h e s m a l l b r i g h t s p e c s s e e n i n F i g u r e 5a a r e p y r i t e c r y s t a l s . The c e n t r a l r e g i o n o f F i g u r e 5a c a n be e x a m i n e d a t much h i g h e r m a g n i f i c a t i o n i n F i g u r e 5b. Here the pocket of p y r i t e c r y s t a l s i n r e l a t i o n to the c o a l i f i e d p l a n t f i b e r i s presented. The p y r i t e c r y s t a l s o c c u r i n o t h e r ways as w e l l w i t h i n t h e coalified material. A h o r i z o n t a l opening i n the c o a l ( a p p r o x i m a t e l y 9 ym i n h e i g h t ) f o r m s t h e p r i m a r y f i e l d o f v i e w i n F i g u r e 5c. The u p p e r s u r f a c e i s c o v e r e d w i t h a l a y e r o f i n d i v i d u a l p y rite crystals. I n F i g u r e 5d, b o t h i n d i v i d u a l s e p a r a t e p y r i t e c r y s t a l s and r o u g h l y s p h e r i c a l a g g l o m e r a t i o n s ( " f r a m b o i d s ... b e r r y - l i k e ) o f s i n g l e c r y s t a l s o f p y r i t e f i l l an o p e n i n g i n t h e c o a l ( p o r t i o n s o f t h e c o a l a r e s e e n i n t h e u p p e r l e f t c o r n e r and lower r i g h t corner of the photograph). I n t h i s example, n o t i c e t h a t t h e r e i s s p a c e b e t w e e n t h e i n d i v i d u a l c r y s t a l s and t h e f r a m b o i d ( t h e f r a m b o i d i s a p p r o x i m a t e l y 10 ym i n d i a m e t e r and i s l o c a t e d i n the l e f t c e n t e r of the f i e l d of view; each of the c r y s t a l s w h i c h c o m p r i s e t h e f r a m b o i d a r e a p p r o x i m a t e l y 1 ym i n d i a m e t e r ) . By c o m p a r i s o n , F i g u r e s 5 j and 5k r e p r e s e n t a f i e l d o f many f r a m b o i d s where a d d i t i o n a l p y r i t e has f i l l e d i n b e t w e e n t h e f r a m b o i d s and cemented them t o g e t h e r t o f o r m a n o d u l e o r c o n c r e t i o n ( t h e s p e c i m e n f r o m t h e m i n e was a b o u t a c e n t i m e t e r i n d i a m e t e r ) . A n o t h e r e x a m p l e o f f r a m b o i d s h a v i n g f o r m e d w i t h i n an o p e n i n g i n 11

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

GRÉER

Coal Microstructure and Pyrite Distribution

9

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1.

Figure 5. Forms of pyrite found in Iowa coal (a) (top left) Deposit of micrometersized pyrite crystals within cellular features. Refer to Figure 5b also. Star mine. Scale bar, 20 μπι. (b) (top right) Higher magnification view of central region of Figure 5a. Scale bar, 2.5 μm. (c) (bottom left) Pyrite crystals attached to upper surface of a hori­ zontal opening in the coal ICO mine. Scale bar, 1 μm. (d) (bottom right) Pyrite crys­ tals occurring as a cavity filling. Both individual crystals and a spherical crystal assembly (a framboid) are seen. In this case, there is no infilling of material between the individual crystals and the framboid. Otley mine. Scale bar, 5 μm.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

COAL DESULFURIZATION

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch001

10

Figure 5. Forms of pyrite found in Iowa coal, (e) (top left) In the center of the field of view,a cluster of four spherical assemblies of pyrite crystals (four framboids) are seen. Star mine. Scale bar, 30 μm. (f) (top right) Infrequently observed polycrystalline sulfide. Otley mine. Scale bar, 3 μm. (g) (bottom left) Fresh fracture surface showing pyrite crys­ tals within a coalified plant cell network. The arrow indicates a broken cell wall reveal­ ing a single pyrite crystal within this particular cellular feature. Compare this with Figure 5h. Mich mine. Scale bar, 2 μm. (h) (bottom right) Polished smooth surface of fusinite indicating coalified plant cell features (similar to a honeycomb appearance) with the roughly circular interiors filled with pyrite (or occasionally calcite, CaC0 ). Jude mine. Scale bar, 30 μm. 3

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

GRÉER

Coal Microstructure and Pyrite Distribution

11

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch001

1.

Figure 5. Forms of pyrite found in Iowa coal (i) (top left) Gypsum crystals in fusinite. Jude mine. Scale bar, 4 μm. (j) (top right) Etched surface of a large (centimeter diame­ ter) pyrite inclusion. Note spherical forms (framboids) and surrounding material (addi­ tional pyrite). Refer to Figure 5k aho. Etching is necessary to reveal this. Mich mine. Scale bar, 50 μm. (k) (bottom) Higher magnification view of Figure 5/ showing that each framboid is comprised of similarly sized individual cry stab within a framboid. Mich mine. Scale bar, 10 μm.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

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12

COAL DESULFURIZATION

c o a l i s shown i n F i g u r e 5e. F i g u r e 5f r e p r e s e n t s a p y r i t e i n t e r growth f e a t u r e . I n c e r t a i n c a s e s ( F i g u r e s 5g and 5h, f o r e x a m p l e ) , i n d i v i d u a l c r y s t a l s may be s u f f i c i e n t l y l a r g e t o c o m p l e t e l y f i l l c o a l i f i e d p l a n t f i b e r openings. To s t u d y t h i s , f l a t p o l i s h e d s e c t i o n s a r e of v a l u e . U s i n g an e l e c t r o n m i c r o p r o b e x - r a y a n a l y z e r w i t h wave­ length d i s p e r s i v e a n a l y s i s , two-dimensional surface d i s t r i b u t i o n a n a l y s e s f o r e l e m e n t s s u c h as c a r b o n , s u l f u r , i r o n , and c a l c i u m can be d e t e r m i n e d . The c a r b o n d i s p l a y s can be a s s o c i a t e d w i t h t h e l o c a t i o n o f t h e c o a l , f o r e x a m p l e . The c a l c i u m d i s p l a y s ( s h o w i n g the p r e s e n c e or absence of c a l c i u m ) can h e l p i n l o c a t i n g c a l c i t e (CaCU3) c r y s t a l s . The c o m b i n e d o c c u r r e n c e o f b o t h i r o n and s u l f u r i s o f v a l u e i n i d e n t i f y i n g t h e p r e s e n c e and l o c a t i o n o f t h e py­ r i t e c r y s t a l s i n r e l a t i o n to c e l l w a l l s . Subsequently, scanning e l e c t r o n m i c r o s c o p e p h o t o g r a p h s o f t h e r e g i o n s e x a m i n e d by the m i c r o p r o b e a n a l y s e s can be o b t a i n e d ( F i g u r e 5h, f o r e x a m p l e ) . Gypsum c r y s t a l s o f v e r y s m a l l s i z e ( a p p r o x i m a t e l y 4 μπι i n d i a m e t e r by 8 t o 20 urn i n l e n g t h ) a r e shown i n F i g u r e 5 i . Many t e x t u r a l f o r m s o c c u r i n c o a l ; h o w e v e r , t h e amount o f gypsum u s u ­ a l l y p r e s e n t i s v e r y low. L a r g e m a s s e s o f p y r i t e may be c o m p r i s e d o f p y r i t e c r y s t a l s where t h e c o n s t i t u e n t p y r i t e c r y s t a l s i z e may a v e r a g e l e s s t h a n a micrometer i n diameter. An e x a m p l e of t h i s i s p r e s e n t e d i n F i g u r e s 5 j and 5k. The e n t i r e f i e l d o f v i e w i n t h e s e f i g u r e s i s p y r i t e ( t h e s u r f a c e has b e e n e t c h e d t o r e v e a l m i c r o s t r u c t u r a l fea­ t u r e s ) . Here f r a m b o i d s comprised of i n d i v i d u a l c r y s t a l s of the o r d e r o f a m i c r o m e t e r o r l e s s i n d i a m e t e r a r e p r e s e n t , and are i n t e r c o n n e c t e d by a d d i t i o n a l p y r i t e . T h i s i s the r e s u l t of a m u l t i s t a g e c o l l o i d a l assembly p r o c e s s w h i c h formed the s o l i d . W i t h i n e a c h f r a m b o i d ( F i g u r e 5k, f o r e x a m p l e ) t h e d i s t r i b u t i o n o f s i z e s of the c o n s t i t u e n t i n d i v i d u a l p y r i t e c r y s t a l s i s s m a l l . A v e r a g e s i z e s o f c r y s t a l s among f r a m b o i d s a r e q u i t e v a r i a b l e as s e e n i n F i g u r e 5k. F i g u r e s 5 j and 5k a r e c r o s s - s e c t i o n a l v i e w s ; however, i n F i g u r e 5 j , f o r example, t h e r e i s a s u f f i c i e n t depth of f i e l d so t h a t t h e s p h e r i c a l f o r m s o f some o f t h e f r a m b o i d s can be seen even i n such a c r o s s - s e c t i o n a l e x a m i n a t i o n ( r e f e r to the up­ p e r r i g h t c e n t r a l p o r t i o n o f t h e m i c r o g r a p h t o see a few o f t h e s e clearly). Pyrite Distribution. C o m p l e t e c o a l seam m i c r o s c a l e c h e m i c a l and s t r u c t u r a l a n a l y s e s h a v e b e e n p e r f o r m e d f o r s e v e r a l c h a n n e l s a m p l e s f r o m Iowa s t r i p and s h a f t m i n e s ( 1 , 1 9 ) . U s i n g an e n e r g y d i s p e r s i v e x - r a y a n a l y s i s s y s t e m f o r p o i n t by p o i n t s u l f u r and i r o n analyses together w i t h a scanning electron microscope f o r m i c r o s t r u c t u r a l i n f o r m a t i o n ( f o r s t u d y i n g c r y s t a l f o r m s and coal m a c e r a l - i n o r g a n i c p h a s e i n t e r r e l a t i o n s h i p s ) the d i s t r i b u t i o n w i t h d e p t h o f p y r i t e c r y s t a l s i n c h a n n e l s a m p l e s f r o m s e v e r a l m i n e s has been c h a r a c t e r i z e d . A l s o , f o r t h e s e mine samples the d i s t r i b u t i o n o f p y r i t e among v a r i o u s f o r m s o f i n t e r e s t f o r p l a n n i n g p y r i t e s r e ­ m o v a l schemes has b e e n o b t a i n e d as w e l l as t h e p r o p o r t i o n n a n t o f

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

1.

GRÉER

TABLE I .

D i s t r i b u t i o n o f P y r i t e Among V a r i o u s

Forms

D i s t r i b u t i o n , wt.!

Form o f P y r i t e Mich Single crystal Framboids Other l a r g e r , massive forms

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13

Coal Microstructure and Pyrite Distribution

S t a r mine

mine

Lovilia

69.7 12.3

21.1 10.9

7.5 6.1

18.0 100.0

68.0 100.0

86.4 100.0

b mine

F i e l d s o f i n d i v i d u a l c r y s t a l s a r e taken as s i z e u n i t s ; note, s i n g l e c r y s t a l s w i t h i n these f i e l d s as w e l l as i s o l a t e d s i n g l e c r y s t a l s are included i n the s i n g l e c r y s t a l category. 'From Réf. 1.

p y r i t e i n c e r t a i n s i z e ranges of p r a c t i c a l i n t e r e s t . A summary o f some o f t h i s i n f o r m a t i o n a p p e a r s i n T a b l e s I a n d I I . I n T a b l e I , t h e d a t a a r e p r e s e n t e d i n a c o n v e n i e n t way w h e r e t h e p y r i t e i s d i s t r i b u t e d among t h r e e f o r m s i n t h e seams ( 1 , 1 9 ) : s i n g l e c r y s t a l s , f r a m b o i d s , and o t h e r l a r g e r , m a s s i v e f o r m s . The d i f f i c u l t y o f s e p a r a t i o n o f t h e p y r i t e f r o m t h e c o a l by c o n v e n t i o n a l w a s h i n g and f l o t a t i o n methods i s r e f l e c t e d i n a h i g h a b u n dance o f v e r y s m a l l c r y s t a l s and f r a m b o i d s , f o r example, such as s e e n i n F i g u r e 5.

Table

Mich

II.

P r o p o r t i o n of P y r i t e

3

mine 50% < 12 ym 75% < 76 ym ( i . e . ,

200 mesh)

5

M i c h mine* 50% < 96% < c S t a r mine 50% < 57% <

2 ym 76 ym ( i . e . ,

200 mesh)

45 ym 76 ym ( i . e . , 200 mesh) c L o v i l i a mine 50% < 300 ym 30% < 76 ym ( i . e . , 200 mesh)

^ i t h e x t e n s i v e f i e l d s of s i n g l e c r y s t a l s considered as s i z e .units. S i n g l e c r y s t a l s c o n s i d e r e d on a c o n s t i t u e n t c r y s t a l b a s i s . From R e f . 1.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

14

COAL DESULFURIZATION

An i n s i g h t i n t o t h e d i f f i c u l t y o f p y r i t e r e m o v a l by c o n v e n ­ t i o n a l s e p a r a t i o n t e c h n i q u e s c a n b e g a i n e d by e x a m i n i n g p r o p o r ­ t i o n n a n t d a t a f o r t h e p y r i t e where t h e i n f o r m a t i o n i s e x p r e s s e d a s a w e i g h t ( o r volume) p e r c e n t o f p y r i t e l e s s than a p a r t i c u l a r s i z e (compared t o t h e t o t a l p y r i t e d e t e r m i n e d f o r a c h a n n e l s a m p l e ) . A b r i e f summary i s i n c l u d e d i n T a b l e I I . The 76 ym s i z e i s o f p o ­ t e n t i a l i n t e r e s t s i n c e most o f t h e c o a l b u r n e d f o r s t e a m - r a i s i n g i s c r u s h e d t o a p p r o x i m a t e l y 200 mesh.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch001

Conclusions The p y r i t e i n c o a l o c c u r s i n s e v e r a l ways. The d i s t r i b u t i o n of t h e forms o f p y r i t e c a n be s t u d i e d o v e r an extended s i z e r a n g e , t o s u b m i c r o m e t e r s i z e s where n e c e s s a r y , o n a b a s i s o f m i c r o s t r u c t u r e as w e l l as element i d e n t i f i c a t i o n . This i s of value i n current investigations to assess the c a p a b i l i t i e s of coal d e s u l f u r i z a t i o n and r e c o v e r y t e c h n o l o g y . Acknowledgement T h i s w o r k i s s u p p o r t e d a t Iowa S t a t e U n i v e r s i t y by t h e E n g i ­ n e e r i n g R e s e a r c h I n s t i t u t e a n d t h e Ames L a b o r a t o r y u n d e r c o n t r a c t t o t h e U.S. E n e r g y R e s e a r c h and D e v e l o p m e n t A d m i n i s t r a t i o n u n d e r c o n t r a c t number W-7405-ENG-82.

Literature Cited

1. Greer, R. T., "Scanning Electron Microscopy/1977," I: 79-93, IIT Research Institute, Chicago, 1977. 2. Greer, R. T., "Recent Advances in Colloid and Interface Sci­ ence," Vol. 5: p. 411-423, Academic, New York, 1976. 3. Greer, R. T., "Proc. Electron Microscopy Society of America," p. 620-621, Claitor's Press, Baton Rouge, 1976. 4. Greer, R. T., "Microstructural Characterization of Iowa Coal," IS-ICP-13, 1-76, June 30, 1975; IS-ICP-12, 1-14, May 31, 1975; IS-ICP-11, 1-20, Feb. 28, 1975; IS-ICP-10, 1-20, Oct. 3, 1974; available from Ames Laboratory, U.S. ERDA. Pub. Office, 201 Spedding Hall, Ames, IA 50011. 5. Augustyn, D., Iley, Μ., Marsh, H., Fuel (1976) 55: 25-38. 6. Boateng, D. A. D., Phillips, C. R., Fuel (1976) 55: 318-322. 7. Stach, E., "Stach's Textbook of Coal Petrology," 3-17, Gebruder Borntraeger, Berlin, 1975. 8. Spackman, W., Trans. N.Y. Acad. Sci., (1958) 20: 411-423. 9. Harris, L. Α., Yust, C. S., Fuel (1976) 55: 233-236. 10. Leonard, J. W., Mitchell, D. R., "Coal Preparation," 1-44, 153, American Institute Mining, Metallurgical, and Pet. Engr., N.Y., 1968. 11. McCartney, J. T., O'Donnell, H. J., Ergun, S., "Coal Sci­ ence," Adv. Chem. Ser. (1966) 55: 261-273.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

1. GREER Coal Microstructure and Pyrite Distribution

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12. Spackman, W., Barghoorn, E. S., "Coal Science," Adv. Chem. Ser. (1966) 55: 695-707. 13. Taylor, G. H., "Coal Science," Adv. Chem. Ser. (1966) 55: 274-283. 14. Brown, H. R., Taylor G. H., Nature (1962) 193: 1146-1148. 15. McCartney, J. T., Econ. Geol. (1949) 44: 617-620. 16. Rust, G. W., J. Geol. (1935) 43: 398-426. 17. Gluskoter, H., Energy Sources (1977) 3: 125-131. 18. Shimp, N. F., Kuhn, J. K., Helfinstine, J. Κ., Energy Sources (1977) 3: 93-109. 19. Greer, R. T., Proc. Int. Conf. X-ray Opt. Microanal. 8th (1977) in press. 20. Greer, R. T., "Proc. Electron Microscopy Society of America," Claitor's Press, Baton Rouge, 1977, p. 150-151.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

2 The Determination of Forms of Sulfur in Coal and Related Materials

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch002

JOHN K. KUHN Illinois State Geological Survey, Urbana, IL 61801 Standard methods of analysis for forms of sulfur in coal are adequate for geological mapping and present commercial usage. But because these procedures were intended for coal only, they will not give consistently correct values for coal-related materials. Additionally, as energy needs grow, the increasing use of coals of lower rank or of higher ash or sulfur content may present new unique problems in analysis. Direct determination of sulfides (other than as pyrite), organic sulfur, and elemental sulfur, is not a part of routine analysis for forms of sulfur in coal. Kinetic and mass balances for processing systems require not only these determinations but also a degree of accuracy heretofore unnecessary. A recent review of the methods for determining sulfur and forms of sulfur in coal by Shimp et al. (1) considered thoroughly the existing procedures but did not discuss in detail the problems associated with unusual coals or coal-related materials. The following discussion of these problems as well as of current efforts to develop new methods may help the coal conversion industry to meet the demands likely to be placed on it in the future. Standard ASTM Methods Standard ASTM procedures (2) c a l l f o r r e f l u x i n g a c o a l sample f o r 30 min with d i l u t e HC1, u s i n g a c o l d f i n g e r condenser, and then determining the s u l f a t e s u l f u r by weighing the barium s u l f a t e p r e c i p i t a t e d when barium c h l o r i d e i s added to the e x t r a c t . The p y r i t e i s e x t r a c t e d from the i n s o l u b l e m a t e r i a l remaining a f t e r the HC1 leach with d i l u t e H N O 3 , and the p y r i t i c i r o n i s determined by t i t r a t i o n with potassium dichromate or potassium permanganate. A recent r e v i s i o n i n the method allows determina t i o n o f the p y r i t i c i r o n by atomic a d s o r p t i o n spectrometry, which may be the more accurate technique (3). A l t e r n a t i v e l y the H C l - s o l u b l e i r o n and the HNO3-soluble i r o n may be determined on separate samples; the d i f f e r e n c e i n the two values then

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r e p r e s e n t s the p y r i t i c i r o n . The organic s u l f u r i s then determined by the d i f f e r e n c e between the inorganic s u l f u r (sulfate + p y r i t i c s u l f u r ) and the t o t a l s u l f u r i n the o r i g i n a l m a t e r i a l , determined by the Eschka method (2), or by Eschka determination of the s u l f u r i n the i n s o l u b l e m a t e r i a l from the HNO3 e x t r a c t i o n . I f the organic s u l f u r obtained by d i f f e r e n c e exceeds the value determined on the r e s i d u e , the former value i s to be the accepted one. The major o b j e c t i o n to t h i s standard method i s the f a c t t h a t an e r r o r i n any one step o f the procedure can a f f e c t the values determined i n other p o r t i o n s o f t h e method.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch002

Unusual Problems The standard ASTM a c i d d i g e s t i o n procedure, f o r example, poses a p o t e n t i a l problem. I t has long been known that a number of c o a l s c o n t a i n f i n e l y d i s p e r s e d p y r i t e , both c r y s t a l l i t e s and framboidal p y r i t e (4), that may be as much as 80 % o f the t o t a l p y r i t e i n the sample. T h i s f i n e l y d i v i d e d p y r i t e has caused l i t t l e problem i n analyses f o r d i f f e r e n t forms o f s u l f u r because most o f i t can u s u a l l y be d i s s o l v e d e a s i l y , and e r r o r s o f 0.1 0.2 % (absolute) are c o n s i d e r a b l y l e s s than the v a r i a t i o n s i n sampling a c o a l seam or p i l e . However, some o f the p y r i t e p a r t i c l e s are small enough t o be occluded i n c o a l p a r t i c l e s or to be encased i n a k a o l i n l a t t i c e which can r e t a r d or prevent t h e i r d i s s o l u t i o n i n the standard ASTM a c i d d i g e s t i o n procedure, thus g i v i n g r i s e t o small e r r o r s i n the p y r i t e c o n c e n t r a t i o n obtained. Undissolved p y r i t e w i l l cause e r r o r s i n both the p y r i t i c s u l f u r value and the organic s u l f u r value, which, even a t the 0.1 % (absolute) l e v e l , w i l l cause s i g n i f i c a n t problems with k i n e t i c or mass balance e v a l u a t i o n . The problem i s not u s u a l l y solved by g r i n d i n g the sample more f i n e l y because these p a r t i c l e s may be a few microns or l e s s i n s i z e , and i t i s d i f f i c u l t to g r i n d the samples s u f f i c i e n t l y t o i n s u r e t o t a l p y r i t e exposure. Another source o f e r r o r i s the occurrence o f s u l f i d e s ( s p h a l e r i t e , c h a l c o p y r i t e , galena, e t c . ) , other than p y r i t e , i n many c o a l s . While t h i s occurrence i s i n f r e q u e n t , i n v e s t i g a t i o n s a t the I l l i n o i s State G e o l o g i c a l Survey have d i s c l o s e d c o a l s c o n t a i n i n g as much as 1.0 % s p h a l e r i t e (ZnS) on a d r y whole c o a l b a s i s (_5) . When c o a l s are processed o r the mineral matter conc e n t r a t e d i n some way, the c o n c e n t r a t i o n o f these s u l f i d e s can exceed 10 % i n the r e s u l t i n g samples. The a c i d d i g e s t i o n f o r s u l f a t e s u l f u r i n the ASTM procedure converts many o f these s u l f i d e s to H 2 S , which i s evolved from the d i g e s t i o n f l a s k and not r e t a i n e d f o r subsequent determination, t h e r e f o r e causing an e r r o r i n the value o f the organic s u l f u r content o f the m a t e r i a l . In a d d i t i o n , the c o n c e n t r a t i o n o f v a r i o u s i o n i c s p e c i e s , which can be excessive i n r e s i d u e s e t c . , may i n t e r f e r e i n the t i t r a t i o n f o r p y r i t i c s u l f u r , but t h i s problem i s u s u a l l y solved i f atomic a d s o r p t i o n spectrometry i s used to determine p y r i t i c i r o n .

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

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Another s e r i o u s source o f d i f f i c u l t y i n the a n a l y s i s o f c o a l r e l a t e d m a t e r i a l s i s the occurrence o f minerals not found normally i n c o a l s i n the r e s i d u e s and products o f l i q u e f a c t i o n and g a s i f i c a t i o n processes. In the reducing systems o f t e n used t o convert c o a l t o gas o r l i q u i d f u e l , p y r i t e can be converted to p y r r h o t i t e (FeS). S u l f u r i s again l o s t as H 2 S from p y r r h o t i t e i n a sample d i s s o l v e d i n HC1 f o r determination o f s u l f a t e s u l f u r , with a resulting error i n analysis. Other systems may change some o f the s u l f u r t o the elemental form which i s not s e p a r a t e l y accounted f o r i n the ASTM procedures. Extreme o x i d i z i n g c o n d i t i o n s i n some systems, on the other hand, may y i e l d l a r g e amounts o f s u l f a t e s , some o f which are not very s o l u b l e i n d i l u t e HC1, and may give r i s e t o erroneous r e s u l t s . Two other f a c t o r s r e l a t e d t o the analyses are important i n o b t a i n i n g c o r r e c t determinations o f forms o f s u l f u r . F i r s t , the need f o r a r e p r e s e n t a t i v e and homogeneous sample i s obvious, but i t can be very d i f f i c u l t to o b t a i n because c o a l - r e l a t e d m a t e r i a l s can occur as l i q u i d s , s o l i d s , s l u r r i e s , or h i g h l y v i s c o u s t a r s , some with ash o r mineral content ranging from near 0 t o 100 %. Often, extraneous m a t e r i a l s such as f i l t e r a i d s , c a t a l y s t s , etc., occur i n the m a t e r i a l s and are extremely d i f f i c u l t t o remove or to p r o p e r l y account f o r . Second, the c a l c u l a t i o n s necessary to compare the products and r e s i d u e s from g a s i f i c a t i o n and l i q u e f a c t i o n processes t o the feed m a t e r i a l s are a f f e c t e d by the mineral changes which have taken p l a c e . For example, values are normally reported on an ash-free b a s i s , which works reasonably w e l l f o r c o a l s . Residues from reducing l i q u e f a c t i o n processes, however, can produce values i n excess o f 100 % upon ashing. The reduced minerals can gain weight i n an o x i d i z i n g ashing system, and s u l f u r can be r e t a i n e d i n the ash i n a d d i t i o n t o being r e p o r t e d s e p a r a t e l y . Large e r r o r s w i l l be caused i n the c a l c u l a t e d values unless the r e s u l t s are r e p o r t e d on the m i n e r a l - f r e e b a s i s (6). New Methods These problems have l e d a number o f l a b o r a t o r i e s and concerned groups, such as ERDA, EPA, and ASTM, to i n v e s t i g a t e d i f f e r e n t approaches t o determining forms o f s u l f u r i n c o a l and, p a r t i c u l a r l y , i n r e l a t e d m a t e r i a l s . The need f o r a standardized method o f a n a l y s i s f o r comparing data between l a b o r a t o r i e s and processes i s e v i d e n t . While such a method would not be necessary f o r r o u t i n e c o a l a n a l y s i s , the present ASTM methods being s u f f i c i e n t , i t could serve as a special-purpose procedure. Among the methods i n v e s t i g a t e d i s one adapted to c o a l (7) from a technique f o r determining forms o f s u l f u r i n o i l shale (8). A strong reducing agent, l i t h i u m aluminum hydride, i s added to the c o a l i n a c l o s e d system. A f t e r the p y r i t e i s reduced t o FeS, the H 2 S l i b e r a t e d on r e a c t i o n with HC1 i s trapped i n a cadmium sulfate solution. T h i s method can prevent the l o s s o f s u l f i d e

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

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s u l f u r , s i n c e the s u l f a t e s u l f u r can be removed a f t e r the p y r i t i c s u l f u r i s determined. T h i s procedure has s e v e r a l drawbacks, however. Organic s u l f u r i s e i t h e r c a l c u l a t e d by d i f f e r e n c e o f the t o t a l s u l f u r and the i n o r g a n i c s u l f u r values or determined on the r e s i d u e l e f t a f t e r removal o f the other forms of s u l f u r and i s , t h e r e f o r e , s u b j e c t t o the same e r r o r s as i n the standard method. The sample must be very f i n e l y ground to l e s s than -400 mesh i n order to o b t a i n the same l e v e l of p r e c i s i o n as obtained with the standard procedure. The method uses p o t e n t i a l l y hazardous chemicals and i s not s u i t a b l e f o r use by an inexperienced a n a l y s t . F i n a l l y , the p y r i t i c s u l f u r value determined by t h i s procedure i n c l u d e s H S evolved from other s u l f i d e s . Despite these d i s advantages, the method can, when used i n c o n j u n c t i o n with the ASTM procedure, y i e l d i n f o r m a t i o n about the amount o f s u l f i d e s other than p y r i t e present and about the c o n c e n t r a t i o n o f elemental s u l f u r i f i t s l e v e l exceeds approximately 0.1 %. Another approach t o the problems i s being used by the I n s t i t u t e o f Gas Technology (9). T h e i r method c l o s e l y f o l l o w s the ASTM scheme except t h a t r e f l u x i n g with HC1 i s done i n a c l o s e d system with the evolved H 2 S c o l l e c t e d i n a s o l u t i o n o f cadmium s u l f a t e and determined i o d o m e t r i c a l l y . S u l f a t e s u l f u r i s determined as i n the standard ASTM procedure. The p y r i t i c i r o n i s e x t r a c t e d from the i n s o l u b l e r e s i d u e by r e f l u x i n g with d i l u t e H N O 3 , and s u l f a t e s u l f u r i s subsequently determined by atomic a b s o r p t i o n spectrometry. The n i t r i c - a c i d s o l u b l e s u l f u r i s p r e c i p i t a t e d as barium s u l f a t e ; the d i f f e r e n c e between t h i s value and p y r i t i c s u l f u r c o n c e n t r a t i o n i s considered to be s o l u b l e organic s u l f u r . T h i s value f o r s o l u b l e s u l f u r i s then added t o the value obtained f o r the s u l f u r i n the r e s i d u e by the standard Eschka method. The sum o f these two values represents the t o t a l organic s u l f u r . While these procedures do provide u s e f u l i n f o r m a t i o n , the most i n t e r e s t i n g approaches attempt a more d i r e c t determination of o r g a n i c s u l f u r . Recent i n v e s t i g a t i o n s a t TRW (10), f o r example, i n d i c a t e t h a t a low-temperature ashing technique can be of s i g n i f i c a n t value i n determining forms of s u l f u r i n c o a l r e l a t e d m a t e r i a l s . The method assumes t h a t a radio-frequency generated plasma a t t a c k s s e l e c t i v e l y the organic c o n s t i t u e n t s o f c o a l and r e l a t e d m a t e r i a l s . Previous i n v e s t i g a t i o n s by Gluskoter e t a l . (11) have i n d i c a t e d t h a t most minerals remain unchanged i n t h i s process. In the TRW procedure, c o a l s or r e l a t e d products are lowtemperature plasma ashed t o remove the organic s u l f u r as S 0 . T o t a l i n o r g a n i c s u l f u r i s then determined by x-ray f l u o r e s c e n c e a n a l y s i s , the Eschka method, HNO3 e x t r a c t i o n , or another method f o r the o r i g i n a l m a t e r i a l . T h i s g i v e s an organic s u l f u r value r e p o r t e d to be, based on TRW s i n v e s t i g a t i o n s , more p r e c i s e than that obtained by the standard method. Organic s u l f u r i s s t i l l determined by d i f f e r e n c e , but TRW i s attempting t o t r a p the SO evolved and t o determine i t d i r e c t l y . A r e p o r t on the p r e c i s i o n

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch002

2

X

1

x

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

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and accuracy o f t h i s approach i s expected soon. The use o f plasma ashing f o r the d i r e c t determination o f organic s u l f u r i s a l s o being i n v e s t i g a t e d a t B a t t e l l e ' s Columbus l a b o r a t o r i e s (12). T h i s method i s designed s p e c i f i c a l l y f o r determining organic s u l f u r without i n t e r f e r e n c e from the other forms o f s u l f u r present. The c o a l sample i s plasma-ashed, and the r e s u l t i n g products ( S O 2 + S O 3 ) are trapped i n a cryogenic condenser and subsequently measured by i o n chromatography. Results thus f a r show an i n c r e a s e d r e p e a t a b i l i t y over the r e s u l t s obtained by the ASTM procedure, and experiments with p y r i t e "spiked" samples have shown no i n t e r f e r e n c e from large amounts o f p y r i t e upon the determination o f organic s u l f u r . T h i s procedure works w e l l with c o a l ; however, the e f f e c t o f minerals such as p y r r h o t i t e i s s t i l l being s t u d i e d and may cause d i f f i c u l t i e s i n the a n a l y s i s o f c o a l - r e l a t e d m a t e r i a l s . A method f o r the d i r e c t determination o f elemental s u l f u r i s being developed a t Iowa State U n i v e r s i t y (13). A 1 g sample of c o a l i s r e f l u x e d with cyclohexane and the s o l u b l e s u l f u r determined by gas chromatography. P r e l i m i n a r y r e s u l t s r e p o r t e d l y i n d i c a t e t h a t 200 - 2000 ppm elemental s u l f u r may be present i n v a r i o u s c o a l s . While v e r i f i c a t i o n o f these values i s s t i l l necessary, they do not d i s a g r e e s i g n i f i c a n t l y with i n f o r m a t i o n reported by Y u r o v s k i i {14). Conclusion Although these methods and others are s t i l l i n the experimental stage, enough progress has been made t h a t development o f a standard method may soon be considered. T h i s method should, i f p o s s i b l e , i n c l u d e a d i r e c t determination o f s u l f i d e s u l f u r (other than p y r i t i c s u l f u r ) , organic s u l f u r , and elemental s u l f u r . A working committee formed by EPA i s c o n s i d e r i n g the procedures with the i n t e n t i o n o f proposing and t e s t i n g a method t o serve the needs o f developing process technology. These needs are a l s o under c o n s i d e r a t i o n by ASTM; when a method o f s u f f i c i e n t m e r i t i s presented, s t a n d a r d i z a t i o n of a procedure may be expected. Literature Cited

1. 2. 3. 4. 5. 6.

Shimp, Neil F., Kuhn, John K, Helfinstine, Roy J., Energy Sources (1977) 3, (2), 93-109. Book of A.S.T.M. Standards, (1976), Pt. 26, 269-283. To be published in Book of A.S.T.M. Standards, (1978) Pt. 26, Revision approved by ASTM June 24, 1977. Thiessen, R., Coal Age (1919) 16, (17), 668-673. Ruch, Rodney R., Gluskoter, Harold J., Shimp, Neil F., Ill. State Geol. Surv., Environ. Geol. Note (1973), 61. Givens, Peter H., Fuel (1976), 55, 256.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

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7. 8. 9. 10. 11. 12. 13. Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch002

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Kuhn, John Κ., Kohlenberger, Larry, Shimp, Neil F., Ill. State Geol. Surv. Environ. Geol. Note (1973), 66. Lawlor, D. L., Fester, J. T., Robinson, W. Ε., Fuel (1963), 42, (3), 239-244. Stotz, Robert, Institute of Gas Technology, personal communication (1977). Kraft, Morton L., Hamersma, Warren W., T.R.W., personal communication (1977). Gluskoter, Harold J., Fuel (1965), 44, 185-291. Paris, Bernard, Battelle Columbus laboratories, personal communication (1977). (See also this volume.) Richard, John, Vick, Ray, Junk, Gregor, Iowa State University, personal communication (1977). Yurovskii, Α. Ζ., "Sulfur in Coals", p. 80, translated from Russian 1974. Published for the U.S. Dept. of Interior, Bureau of Mines, and the National Science Foundation, Washington, D.C. by the Indian National Scientific Documentation Center, New Delhi. Available from: U.S. Dept. of Commerce, NTIS, Springfield, VA 22161.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

3 Direct Determination of Organic Sulfur in Raw Coals

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch003

B. PARIS Battelle, Columbus Laboratories, 505 King Ave., Columbus, OH 43201

The sulfur content among coals varies to some degree in total quantity and in the forms present. Generally, the forms of sulfur in coals are the inorganic (pyrite and sulfate) and the organic (a complex mixture of organo types). The sulfate content is usually present in low amounts except in some instances where weathering has converted some of the pyrite to sulfate. The pyrite form can occur in a rough size range from 0.25 to 200 μm. The organic sulfur in coals is intimately bound to the coal molecule and is difficult to determine directly when other forms are present. The organic sulfur content in most American coals ranges from about 0.5 to 3%. A total sulfur analysis will determine whether present SO2 emission standards will be met upon combustion of the candidate coal. If the total sulfur is too high and stack gas cleaning is not available, some form of desulfurization is required before this energy source can be used. Cleaning processes can remove varying amounts of the inorganic forms, and some organic sulfur may also be extracted, but for all intents, the content of this latter form may be regarded as the lower level to which coal can be physically beneficiated. Therefore, the baseline level of organic sulfur must be known so that economic and time effective inorganic sulfur extractions can be applied which in turn can comply with combustion standards. C u r r e n t ASTM methods p r o v i d e f o r t h e d i r e c t a n a l y s e s o f t h e t o t a l , s u l f a t e , and p y r i t i c s u l f u r s . The a c c e p t e d t e c h n i q u e s f o r d e t e r m i n i n g t h e s u l f u r f o r m s i n c o a l s a r e t h e ASTM CO s t a n d a r d wet methods. The t o t a l s u l f u r i s d e t e r m i n e d b y t h e E s c h k a method (D3177-75) and t h e s u l f a t e and p y r i t e b y s e l e c t i v e a c i d l e a c h e s (D2492-68). The o r g a n i c s u l f u r i s t h e n o b t a i n e d f r o m t h e d i f f e r e n c e o f t h e t o t a l and t h e two i n o r g a n i c forms s i n c e no r e l i a b l e d i r e c t method i s a v a i l a b l e . The p o s s i b l e a c c u m u l a t i o n o f e r r o r s a n d t h e t i m e r e q u i r e d (^1 1/2 d a y s ) t o o b t a i n t h e o r g a n i c s u l f u r b y d i f f e r e n c e h a s made t h i s a p p r o a c h undesirable but necessary.

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In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch003

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The p r e c i s i o n o f t h e o r g a n i c s u l f u r v a l u e o b t a i n a b l e f r o m t h i s a p p r o a c h was c a l c u l a t e d f r o m numerous a n a l y s e s a t B a t t e l l e Columbus L a b o r a t o r i e s (BCL) i n c o n j u n c t i o n w i t h p r e c i s i o n e s t i m a t e s o f t h e r e s p e c t i v e ASTM methods. A t two s t a n d a r d d e v i a t i o n s ( 9 5 % c o n f i d e n c e l e v e l ) t h e p r e c i s i o n was f o u n d t o be ±25%. I n s t r u m e n t a l methods a l s o c a n be u s e d t o d e t e r m i n e t h e i n o r g a n i c f o r m s and t o t a l s u l f u r f o r a n e s t i m a t i o n o f t h e o r g a n i c s u l f u r content. The two methods u s e X - r a y a n a l y s e s o n p r e s s e d pellets of pulverized coal. I n o n e , H u r l e y and W h i t e ( 2 ) , u s e d X-ray f l u o r e s c e n c e t o c h a r a c t e r i z e a l l o f t h e s u l f u r forms by w a v e l e n g t h s h i f t o f t h e SK^ peak c a u s e d b y v a r i a t i o n i n t h e s u l f u r bonding. The s e c o n d method (3) i s d i s c u s s e d i n an u n p u b l i s h e d r e p o r t on s u l f u r d e t e r m i n a t i o n i n c o a l s and u t i l i z e s X - r a y f l u o r e s c e n c e f o r c o a l and s u l f a t e s u l f u r s and X - r a y d i f f r a c t i o n for p y r i t i c sulfide sulfur. O r g a n i c s u l f u r i s o b t a i n e d by t h e d i f f e r e n c e i n the l a t t e r technique. B o t h o f t h e X - r a y methods a g r e e w i t h c o r r e s p o n d i n g wet c h e m i c a l d a t a on t h e same s a m p l e s . The p r e c i s i o n o f t h e s e i n s t r u m e n t a l methods t h e r e f o r e i s a t l e a s t a s good a s t h e ASTM procedure, but the time o f analyses i s reduced t o s e v e r a l hours. A d i r e c t method f o r d e t e r m i n i n g o r g a n i c s u l f u r i n c o a l s was r e p o r t e d by S u t h e r l a n d ( 4 ) u s i n g t h e e l e c t r o n m i c r o p r o b e o n pressed p e l l e t s of coal. A BCL s u p p o r t e d p r o g r a m , t h e r e f o r e , was i n i t i a t e d t o d e v e l o p a d i r e c t and s p e c i f i c method t o d e t e r m i n e t h e o r g a n i c s u l f u r c o n t e n t i n c o a l s and i n t h e p r e s e n c e o f t h e o t h e r s u l f u r forms. The a p p r o a c h t a k e n e n t a i l e d t h e l o w - t e m p e r a t u r e reaction o f i o n i z e d o x y g e n s p e c i e s w i t h raw c o a l s t o y i e l d v o l a t i l e S 0 components w h i c h a r e t h e r e a c t i o n p r o d u c t s o f t h e o r g a n i c s u l f u r content of the coals. The S 0 p r o d u c t s c a n be c o l l e c t e d i n a s u i t a b l e t r a p m a i n t a i n e d a t l o w t e m p e r a t u r e s and s u b s e q u e n t l y analyzed. X

X

Experimental

Conditions

Equipment. F o r t h i s purpose, t h e i n s t r u m e n t used f o r t h e o x i d a t i o n o f c o a l s d u r i n g t h i s p r o g r a m was t h e L F E LTA 600L l o w temperature asher. The g e n e r a t o r o p e r a t e s a t a c r y s t a l c o n t r o l l e d f r e q u e n c y o f 13.56 MHz and h a s a n o u t p u t c a p a b l e o f d e l i v e r i n g 300 W o f c o n t i n u o u s l y v a r i a b l e power d i s t r i b u t e d among f i v e s e p a r a t e r e a c t i o n c h a m b e r s . N o r m a l a s h i n g i s c a r r i e d o u t u n d e r c o n t i n u o u s r o u g h pumping (300 L/min c a p a c i t y ) so a s t o m a i n t a i n a p r e s s u r e o f 1 t o r r a t an oxygen i n p u t f l o w o f about 50 c c / m i n . The l o w t e m p e r a t u r e o x i d a t i o n t e c h n i q u e h a s b e e n used t o study the m i n e r a l matter content o f c o a l s . As i n d i c a t e d p r e v i o u s l y , the technique u t i l i z e s the o x i d a t i v e p r o p e r t i e s o f t h e r e a c t i v e i o n i c and a t o m i c s p e c i e s o f o x y g e n w h i c h a r e p r o d u c e d when m o l e c u l a r o x y g e n i s p a s s e d t h r o u g h a h i g h f r e q u e n c y field. The i o n i z e d o x y g e n s p e c i e s a r e d i r e c t e d t o t h e s u r f a c e

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24

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o f t h e raw c o a l where s e l e c t i v e o x i d a t i o n o f t h e o r g a n i c c o n t e n t l e a v e s the m i n e r a l matter r e l a t i v e l y u n a l t e r e d f o r study. The r e a c t i o n produces v o l a t i l e o x i d e s of the t o t a l o r g a n i c content. T h e s e p r o d u c t s a r e CO, CO2, H2O, S0 , and N0 , and t h e y a r e a l l o w e d n o r m a l l y t o be d i s c h a r g e d t h r o u g h the vacuum pump. The t e m p e r a t u r e o f the c o a l s u r f a c e r e a c t i o n under t h e s e c o n d i t i o n s c a n v a r y f r o m 50° t o 300° C d e p e n d i n g p r i m a r i l y upon t h e power a p p l i e d t o t h e RF c o i l s . F r a z e r e t a l . (5) and M i t c h e l l e t a l . (6) used low temperature a s h i n g o f c o a l s to s t u d y m i n e r a l s t a b i l i t y under a v a r i e t y o f c o n d i t i o n s . Although better s t a b i l i t y of m i n e r a l s was o b s e r v e d t h a n t h a t shown by t h e a i r o x i d a t i o n method a t 400°C, i t was n o t e d t h a t p u r e p y r i t e c o u l d be o x i d i z e d a t t e m p e r a t u r e s o f 200 t o 300°C. To p r o v i d e f o r t h e c o l l e c t i o n o f t h e d e s i r e d v a p o r s p e c i e s , t h e e x i t o f one o f t h e r e a c t i o n chambers was r e r o u t e d t o accommodate a g l a s s t r a p p i n g s y s t e m . T h i s m o d i f i c a t i o n i s shown s c h e m a t i c a l l y i n F i g u r e 1. The a l l g l a s s a s s e m b l y , w i t h b a l l j o i n t c o n n e c t o r s i n c l u d e s a s t o p c o c k (D), a low t e m p e r a t u r e t r a p (C) t o c o l l e c t t h e o x i d i z e d s p e c i e s , and a c o n n e c t o r a t (E) t o e i t h e r e v a c u a t e d u r i n g a r u n o r t o a t t a c h a gas b u b b l i n g t r a p f o r c o l l e c t i n g t h e SO2 a t t h e end o f a r u n . The r e m a i n i n g chambers were l e f t i n t a c t so as n o t t o i n t e r f e r e w i t h t h e o p e r a t i o n of the instrument. F i g u r e 2 shows t h e s a m p l e h o l d e r u s e d f o r l o a d i n g t h e s a m p l e f o r the o x i d a t i o n run. Sample p l a t e (A) i s p l a c e d i n t h e h o l d e r as shown a f t e r l o a d i n g w i t h c o a l . The s a m p l e h o l d e r c o n t a i n i n g t h e s a m p l e i s i n s e r t e d i n t h e m o d i f i e d sample chamber. This o v e r a l l arrangement p r o v i d e s ease of h a n d l i n g of the sample.

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X

X

R e a c t i o n and C o l l e c t i o n P r o c e d u r e . A w e i g h e d sample i s l o a d e d i n t o t h e s a m p l e h o l d e r o n t o a g l a s s p l a t e . The s a m p l e h o l d e r i s i n s e r t e d i n t o t h e r e a c t i o n chamber (A) t h r o u g h p o r t (B). The s y s t e m i s c a r e f u l l y e v a c u a t e d t o a b o u t 0.2 t o r r . As t h e o x i d a t i o n o f t h e c o a l s p r o g r e s s , t h e t e m p e r a t u r e (-196°C) and p r e s s u r e (1 t o r r ) c o n d i t i o n s p e r m i t t r a p p i n g o f t h e SO2 and SO3 g a s e s as s o l i d s . The g e n e r a t o r i s t u r n e d o f f a f t e r , upon v i s u a l e x a m i n a t i o n , t h e s a m p l e s a p p e a r t o be c o m p l e t e l y o x i d i z e d . The o x i d a t i o n time can v a r y from 1 to 3 h o u r s . Helium i s slowly admitted t h r o u g h s t o p c o c k (D) u n t i l t h e s y s t e m c a n be opened t o t h e a i r . A g l a s s i m p i n g e r b o t t l e c o n t a i n i n g a b o u t 50 c c o f 3% H2O2 s o l u t i o n i s a t t a c h e d t o ( E ) . W i t h a s l o w p u r g e o f He t h r o u g h t h e t r a p and i m p i n g e r , t h e Dewar i s removed t o p e r m i t t h e t r a n s f e r o f t h e c o n d e n s e d SO2 i n t o t h e p e r o x i d e s c r u b b e r . The t r a p i s then r i n s e d w i t h a p e r o x i d e s o l u t i o n to c o l l e c t the SO3 component o f t h e p r o d u c t . The two s o l u t i o n s a r e c o m b i n e d f o r s u l f a t e a n a l y s e s u s i n g t h e D i o n e x M o d e l 10 i o n c h r o m a t o g r a p h . Samples. The c o a l s w h i c h w e r e s e l e c t e d f o r t h i s p r o g r a m w e r e u s e d as r e c e i v e d e x c e p t t h a t t h e y w e r e g r o u n d t o p a s s

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

PARIS

Organic Sulfur in Coals

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch003

3.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

25

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26

COAL DESULFURIZATION

-200 mesh s i e v e (74 ym). Wet c h e m i c a l s u l f u r a n a l y s e s were o b t a i n e d on t h e s e c o a l s . I n a d d i t i o n to a r e p r o d u c i b i l i t y study on one c o a l , s e v e r a l o t h e r c o a l s o f v a r y i n g s u l f u r and a s h c o n t e n t s w e r e r u n t o e s t a b l i s h t h e s u i t a b i l i t y o f t h i s method t o c o a l s p o s s e s s i n g v a r y i n g c h e m i c a l c o n t e n t s . The c a n d i d a t e c o a l s a r e l i s t e d i n T a b l e I a l o n g w i t h t h e i r p e r t i n e n t makeup. The s u l f u r v a l u e s w e r e d e t e r m i n e d by ASTM methods. The amount o f c o a l s a m p l e s t a k e n f o r t h e s e r u n s was i n t h e 20-30 mg r a n g e . The r e s u l t i n g s u l f u r c o l l e c t i o n s w e r e e x p e c t e d t o be o f s u f f i c i e n t q u a n t i t y t o be d e t e r m i n e d by t h e a n a l y t i c a l method t o be u s e d . S m a l l c h a r g e s w e r e u s e d i n an e f f o r t t o reduce the o x i d a t i o n time to s e v e r a l hours. A f t e r the i n i t i a l s u r f a c e o f c o a l i s removed, t h e p e n e t r a t i o n o f the i o n i z e d oxygen t o the c o a l u n d e r l y i n g the ash i s time dependent. The p o s s i b l e e r r o r s introduced i n the o v e r a l l d e t e r m i n a t i o n of o r g a n i c s u l f u r f r o m m a c r o s c o p i c i n h o m o g e n i e t i e s a c c e n t u a t e d by the s m a l l s a m p l e c h a r g e s c o u l d be e v a l u a t e d i n t h e p r e c i s i o n series.

Table I .

Samples U s e d i n Low

Sample 719-2 ( O h i o ) 719-3 ( O h i o H a z a r d #4 ( K e n t u c k y ) C o l s t r i p #2 ( W e s t e r n ) Beach B o t t o m #1 (W.Va.)

Total

Temperature

Oxidation Studies

S u l f u r (%) Sulfate Pyritic

Organic

Ash(%) 14.2 17.1 12.8 9.0 25.1

1.58 3.6 0.66 0.18 1.35

2.74 0.07 0.04 0.14 0.03

17.7

0

0

17.7

0

24.7

0

0

24.7

0

6.3 5.2 1.52 0.68 1.97

1.9 1.4 0.82 0.36 0.59

O r g a n i c Compounds Dithiopropionic acid 2-Thiophene Carboxylic Acid

The p u r e o r g a n o s u l f u r compounds shown were a l s o r u n s i n c e the r e s u l t s w o u l d r e p r e s e n t i d e a l r e c o v e r y e x p e r i m e n t s i n t h e absence o f i n t e r f e r i n g m i n e r a l forms. The s a m p l e c h a r g e s u s e d f o r t h e s e r u n s w e r e i n t h e 5-10 mg r a n g e . A s t u d y was a l s o made o f t h e s t a b i l i t y o f FeS2 under t h e ashing conditions f o r coal. O x i d a t i o n o f t h i s compound y i e l d s v o l a t i l e SO2 w h i c h w o u l d be i n d i s t i n g u i s h a b l e f r o m t h a t d e r i v e d from the o r g a n i c s u l f u r i n c o a l . I n a d d i t i o n , t h e p u r e FeS2 was a l s o m i x e d w i t h o t h e r components t o a s s e s s t h e i r e f f e c t upon i t s c o n v e r s i o n . T h e s e m a t e r i a l s i n c l u d e d p u r e S i 0 graphite, a s h , and c o a l . 2

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

3.

PARIS

27

Organic Sulfur in Coals

Experimental

Results

O x i d a t i o n S t u d y o f FeS2I t was f i r s t n e c e s s a r y t o e s t a b l i s h c o n d i t i o n s which prevented or reduced c o n s i d e r a b l y the oxidation of p y r i t e to y i e l d S0 . The e x p e r i m e n t a l c o n d i t i o n s w h i c h w e r e v a r i e d f o r t h e FeS2 s t u d y i n c l u d e d a p p l i e d power t o the p l a s m a , o x y g e n f l o w , p o s i t i o n o f s a m p l e s i n r e l a t i o n t o t h e p l a s m a , p a r t i c l e s i z e o f F e S 2 , and m i x t u r e s o f v a r i o u s m a t e r i a l s w i t h p u r e FeS2» F o r the runs w i t h o n l y FeS2, i t appears t h a t the c o n v e r s i o n t o Fe203 and v o l a t i l e SO2 o c c u r s u n d e r any c o n dition. However, t h e s e v e r i t y o f c o n v e r s i o n i n c r e a s e s d i r e c t l y w i t h t h e a p p l i e d power and i n v e r s e l y w i t h p a r t i c l e s i z e . The p o s i t i o n o f t h e sample i n t h e chamber and t h e r a t e o f o x y g e n f l o w u s e d h a v e m i n i m a l , i f a n y , e f f e c t upon t h e o x i d a t i o n o f FeS . The r u n s made u s i n g m i x t u r e s o f FeS2 w i t h t h e l i s t e d a d d i t i v e s produced v a r i e d r e s u l t s . I t was f o u n d t h a t a d d i n g g r a p h i t e , S1O2, o r an o r g a n i c s u l f u r compound t o p u r e FeS2 d i d n o t p r e v e n t t h e FeS2 r e a c t i o n w i t h o x y g e n . However, a d m i x t u r e s w i t h c o a l o r f l y a s h a p p e a r t o p r e v e n t FeS2 o x i d a t i o n . The r e a s o n f o r t h e a p p a r e n t i n h i b i t i o n o f t h e r e a c t i o n i s n o t known b u t seems t o be a s s o c i a t e d w i t h c h a r a c t e r i s t i c s o f t h e a s h o t h e r t h a n S1O2. The p r e s e n c e o f t h e n a t u r a l a s h i n c o a l s a c c e l e r a t e s the r e a c t i o n o f the o r g a n i c phase w i t h the plasma. I n s a m p l e s c o n t a i n i n g no a s h , s u c h a s g r a p h i t e o r an o r g a n o s u l f u r compound, t h e r e a c t i o n w i t h i o n i z e d o x y g e n i s s l o w e r .

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X

2

Coal Studies. C o a l s w e r e o x i d i z e d u s i n g t h e optimum i n s t r u m e n t a l c o n d i t i o n s a s d e t e r m i n e d t o be s u i t a b l e by t h e pyrite studies. T h e s e w e r e f o u n d t o be (a) a p p l i e d power o f 150 W o v e r a l l (20 W/chamber), (b) o x y g e n f l o w a t 30 c c / m i n * and ( c ) a p r e s s u r e o f 1 t o r r . A sample c h a r g e o f a b o u t 25 mg was u s e d . The c o l l e c t e d s u l f a t e s w e r e d e t e r m i n e d on a D i o n e x M o d e l 10 i o n c h r o m a t o g r a p h . B o t h c h e m i c a l and s y s t e m b l a n k s w e r e d e t e r m i n e d t h r o u g h o u t the sample r u n s . The c h e m i c a l b l a n k s w e r e o b t a i n e d on e q u i v a l e n t volumes o f p e r o x i d e - w a t e r s o l u t i o n s as used i n the S 0 r e coveries. The s y s t e m b l a n k s w e r e d e t e r m i n e d f r o m a c t u a l o x i d a t i o n - t r a n s f e r techniques w i t h o u t samples. Both blank l e v e l s w e r e f o u n d t o v a r y f r o m 15 t o 25 y g o f s u l f u r . A t t e m p t s were made t o measure t h e t e m p e r a t u r e o f c o a l s u r f a c e s u n d e r o x i d i z i n g c o n d i t i o n s a t 3 d i f f e r e n t RF power s e t t i n g s u s i n g a r a d i a t i o n thermometer. The s u r f a c e t e m p e r a t u r e s c o r r e s p o n d i n g t o a p p l i e d powers o f 20 W, 30 W, and 40 W w e r e 130°C, 210°C, and 230°C, r e s p e c t i v e l y . T h e r e may be some doubt a b o u t the a b s o l u t e a c c u r a c y o f t h e s e v a l u e s , b u t t h e r e l a t i v e d i f f e r e n c e s s h o u l d be s a t i s f a c t o r y . U s i n g t h e above c o n d i t i o n s f o r c o a l 719-2, a s e r i e s o f 10 r u n s s u p p l i e d a measure o f t h e r e p e a t a b i l i t y o f t h i s t e c h n i q u e f o r t h e o r g a n i c s u l f u r r e c o v e r y i n one c o a l . These r e c o v e r y X

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d a t a and p r e c i s i o n a r e shown i n T a b l e I I . The r a t i o o f t h e obtained/expected values allows f o r the c a l c u l a t i o n of the r e l a t i v e s t a n d a r d d e v i a t i o n o f 19% a t t h e 95% c o n f i d e n c e l e v e l . This i s s l i g h t l y b e t t e r t h a n t h a t a c h i e v a b l e b y t h e i n d i r e c t ASTM method. The r e p e a t a b i l i t y d a t a shown i n T a b l e I I i n c l u d e a w i d e range o f v a r i a b l e s . These i n c l u d e : p o s s i b l e inhomogeneity of s m a l l c o a l c h a r g e s , a b i l i t y t o d u p l i c a t e r e a c t i o n and c o l l e c t i o n t e c h n i q u e s , a n a l y s e s o f s u l f a t e s o l u t i o n s , and r u n s e x t e n d e d over a p e r i o d o f s e v e r a l weeks.

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Table

II.

Net O r g a n i c Expected 440 405 420 420 380 430 440 415 430

R e p e a t a b i l i t y Runs o f t h e A n a l y s e s o f O r g a n i c S u l f u r From O x i d a t i o n o f 719-2 C o a l S u l f u r (yg) Obtained

Ratio

450 410 475 360 360 450 440 380 350

Obtained/Expected 1.023 1.012 1.131 0.861 0.949 1.047 1.00 0.916 0.814

Mean % SD ( 9 5 % c o n f i d e n c e l e v e l )

0.971 19.0

I t i s noteworthy to p o i n t out t h e low r e c o v e r y runs which a r e r e p r e s e n t e d i n T a b l e I I by t h e r a t i o v a l u e s 0.861 and 0.814. Although the inhomogeniety o f the s u l f u r d i s t r i b u t i o n i n the c o a l could e x p l a i n the o v e r a l l v a r i a t i o n of the r e s u l t s , another p o s s i b i l i t y f o r t h e l o w r e c o v e r i e s c o u l d be t h e l o s s o f SO2 during transfer. More s p e c i f i c a l l y , t h e l o s s c o u l d have o c c u r r e d d u r i n g the h e l i u m purge i n t o the evacuated system. An i n i t i a l h i g h f l o w o f h e l i u m c o u l d warm t h e d e p o s i t e d S 0 s u f f i c i e n t l y t o cause a s l i g h t v a p o r i z a t i o n l o s s to the system. At a temperature o f -196°C and a p r e s s u r e o f 1 t o r r , t h e c a l c u l a t e d l o s s o f SO2 t h r o u g h v a p o r i z a t i o n c o u l d be 6 n g / h r . However, w i t h t h e same p r e s s u r e c o n d i t i o n s b u t a t t h e h i g h e r t e m p e r a t u r e o f -160°C, t h e v a p o r i z a t i o n l o s s c o u l d be 30 mg/hr. P a s t e x p e r i e n c e h a s shown t h a t SO2 c a n n o t be c o n d e n s e d q u a n t i t a t i v e l y a t t h i s p r e s s u r e and the h i g h e r temperature. Therefore, i t i s p o s s i b l e that f o r the two l o w r e c o v e r y v a l u e s , t h e t e c h n i q u e s o f sample t r a n s f e r w e r e inadequate. 2

6

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

3.

PARIS

29

Organic Sulfur in Coals

The s e c o n d s t u d y i n v o l v i n g c o a l 719-2 was t o o x i d i z e f o r S 0 r e c o v e r y a f t e r s p i k i n g w i t h q u a n t i t i e s o f FeS2 h a v i n g a p a r t i c l e s i z e r a n g e o f <37 ym. The p y r i t e was p r e m i x e d w i t h c o a l a t a b o u t t h e 12% l e v e l so t h a t t h e c h a r g e t o be o x i d i z e d was a b o u t 25 mg o f c o a l and 3 mg o f p u r e p y r i t e . The o v e r a l l p r o c e d u r e f o r t h e m i x r u n s was s i m i l a r t o t h a t f o r t h e c o a l - o n l y runs. R e s u l t s o f t h e c o a l - F e S 2 r u n s a r e shown i n T a b l e I I I . The r e l a t i v e s t a n d a r d d e v i a t i o n a t t h e 95% c o n f i d e n c e l e v e l i s 17%. X

Table I I I .

Analyses of Organic S u l f u r from O x i d a t i o n of 719-2 C o a l S p i k e d W i t h P u r e F e S

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch003

2

O r g a n i c S u l f u r (yg) Expected Obtained 350 345 370 300

330 350 440 320

Mean % SD ( 9 5 % c o n f i d e n c e l e v e l )

Ratio

Obtained/Expected 0.943 1.014 1.190 1.07 1.054 17.0

The t h i r d m a j o r e x p e r i m e n t i n v o l v e d t h e r e p e a t a b i l i t y o f the d e s c r i b e d t e c h n i q u e when a p p l i e d t o a w i d e r a n g e o f c o a l s . The b a s i s f o r s e l e c t i o n i n c l u d e d a v a r i a t i o n i n t o t a l , p y r i t i c , and o r g a n i c s u l f u r s a s w e l l as t h e a s h c o n t e n t . The c o a l s u s e d for these runs are l i s t e d i n Table I . The f o u r c o a l s w e r e r u n i n t r i p l i c a t e u s i n g s i m i l a r p r o c e d u r e c o n d i t i o n s as f o r t h e two p r e v i o u s s t u d i e s w i t h c o a l 719-2. The r e s u l t s f o r t h e f o u r c o a l s a r e shown i n T a b l e I V . One r u n ( C o l s t r i p ) a p p e a r s t o be o u t o f l i n e , b u t t h e o t h e r r a t i o d a t a seem t o be w e l l w i t h i n t h e e r r o r s a s s o c i a t e d w i t h e i t h e r t h e ASTM o r t h e p r e s e n t d i r e c t method. The r e s u l t s show t h a t t h e d i r e c t ( o x i d a t i o n ) method does p r o v i d e a r e a s o n a b l e e s t i m a t e of the o r g a n i c s u l f u r content i n a v a r i e t y of c o a l s . T h e o r e t i c a l r e c o v e r i e s o f s u l f u r i n p u r e o r g a n i c compounds w e r e i n t h e 90-95% r a n g e . The m e l t i n g p o i n t s o f t h e two o r g a n o s u l f u r components a r e n e a r t h e t e m p e r a t u r e s a c h i e v e d d u r i n g t h e oxidations. I t i s u n c e r t a i n w h a t , i f any, e f f e c t t h i s h a s on f u l l recoveries. Observations. Other o x i d i z e d p r o d u c t s o f c o a l s were cond e n s e d a t t h e l i q u i d n i t r o g e n t e m p e r a t u r e s . A l t h o u g h no a t t e m p t s w e r e made t o a n a l y z e t h e f u l l c o n t e n t s o f t h e c o n d e n s e d m a t e r i a l , s m a l l amounts o f o z o n e w e r e p r e s e n t i n r u n s w h i c h

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

COAL DESULFURIZATION

30

contained organic carbon. T h e r e was no e v i d e n c e o f c o n d e n s e d o z o n e when o n l y FeS2 o r c o a l a s h w e r e e x p o s e d t o t h e p l a s m a .

Table

A p p l i c a t i o n o f the O x i d a t i o n Technique to V a r i o u s C o a l s Organic

S u l f u r (yg)

Expected

Obtained

Ratio

77 75 70

123 85 80

1.6 1.1 1.1

220 185 200

173 173 190

0.79 0.94 0.95

C o s h o c t o n 719-3

330 330 325

300 313 340

0.91 0.95 1.05

B e a c h B o t t o m #1

180 185 170

195 210 190

1.1 1.1 1.1

Colstrip

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch003

IV.

Hazard

#2

#4

A c c i d e n t a l l e a k s i n t h e system d u r i n g a r u n appear t o d e p l e t e n o t o n l y t h e o z o n e , b u t a l s o t h e c o n d e n s e d SO2. The r e s u l t i n g N0 a p p a r e n t l y r e a c t s w i t h SO2 t o f o r m a NO-SO comp l e x w h i c h makes i t u n a v a i l a b l e f o r t h e a n a l y t i c a l method u s e d . P r e d e p o s i t i o n o f SO3 ( p r o b a b l y a s H2SO3 o r R^SO^) o n t h e w a l l s o f the g l a s s system can occur a t h i g h S0 c o n c e n t r a t i o n s . The d e p o s i t i o n o n t h e g l a s s s u r f a c e s was v e r y much i n e v i d e n c e i n t h e i n v e s t i g a t i o n s w i t h p u r e FeS2» B l a n k l e v e l s were found a f t e r c o a l runs. O t h e r S 0 c o l l e c t i o n t e c h n i q u e s were t r i e d i n e f f o r t s t o s i m p l i f y i t s recovery f o ranalysis. One a t t e m p t i n c l u d e d t h e p o s s i b l e c a t a l y t i c c o n v e r s i o n o f S 0 t o SO3 f o r i t s h i g h e r temperature c o l l e c t i o n . Poisoning of the platinum surface o c c u r r e d about halfway t h r o u g h t h e r u n t o make t h i s a p p r o a c h unsuccessful. A n o t h e r a t t e m p t i n v o l v e d p l a c i n g a NaOH-laden q u a r t z w o o l p l u g and a l s o a s c a r i t e i n t h e r e a r o f t h e h o l d e r insert. B o t h a p p e a r t o be v e r y e f f e c t i v e i n c a p t u r i n g t h e S 0 vapor. However, t o be e f f e c t i v e t h e NaOH q u a r t z p l u g s h o u l d be s l i g h t l y moist. X

X

X

2

X

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

3.

PARIS

Organic Sulfur in Coals

31

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch003

Conclusions B a s e d on t h e e x p e r i m e n t a l work c a r r i e d o u t f o r t h i s p r o g r a m , a d i r e c t method f o r d e t e r m i n i n g t h e o r g a n i c s u l f u r c o n t e n t o f c o a l has been d e v e l o p e d . The p r o c e d u r e makes u s e o f t h e r e l a ­ t i v e e a s e o f o x i d a t i o n o f t h e o r g a n i c a l l y bound component o f c o a l s w i t h i o n i z e d plasma o f oxygen t o y i e l d v o l a t i l e o x i d i z e d s p e c i e s p e c u l i a r t o t h e t o t a l o r g a n i c makeup. The d e s i r e d p r o ­ d u c t s a r e condensed a t a low temperature f o r subsequent a n a l y s i s . The work r e p o r t e d h e r e i n h a s d e m o n s t r a t e d t h a t t h i s t e c h ­ nique i s s p e c i f i c f o r the organic s u l f u r content of coals w i t h i n the e r r o r o f the o v e r a l l procedure. R e p e a t a b i l i t y r u n s on one c o a l (719-2) h a s p r o d u c e d r e l a t i v e s t a n d a r d d e v i a t i o n s b e t t e r than those o b t a i n e d f o r o r g a n i c s u l f u r using the d i f f e r e n t methods o f ASTM. S i m i l a r p r e c i s i o n was o b t a i n e d f r o m t h e same c o a l e v e n when s p i k e d w i t h c o m p a r a t i v e l y l a r g e q u a n t i t i e s o f p u r e FeS2 h a v i n g a p a r t i c l e s i z e o f <37 ym. No s a c r i f i c e i n t h e amount o f o r g a n i c s u l f u r r e c o v e r e d was i n d i c a t e d i n t h e s e spiked runs. I t h a s a l s o b e e n shown t h a t t h i s t e c h n i q u e i s s u i t a b l e f o r c o a l s o f v a r y i n g makeup. I n a d d i t i o n , r e c e n t s u c c e s s i n d e t e r ­ m i n i n g o r g a n i c s u l f u r i n s o l v e n t and c h e m i c a l l y r e f i n e d c o a l p r o d u c t s p r o v i d e s a w i d e r b a s e o f a p p l i c a b i l i t y o f t h e method. The r e p e a t a b i l i t y r u n s i n d i c a t e t h a t t h e u s e o f t h e 25 mg sample charge i s j u s t i f i e d . Any e r r o r f r o m t h e inhomogeneous d i s t r i b u t i o n o f o r g a n i c s u l f u r i n the use of s m a l l charges a p p e a r s t o be m i n i m a l o r w i t h i n t h e e x p e c t e d l i m i t s o f p r e c i s i o n o f t h e method.

Literature Cited

1. "Book of ASTM Standard Methods Part 26", D3177-75, D2492-68 (1976). 2. Hurley, R. G., White, E. W., "New Soft X-ray Method for Determining Chemical Forms of Sulfur in Coal", Anal. Chem. (1974), 46, 2243. 3. Paris, B., Schumacher, P. W., "An XRF-XRD Method for Deter­ mining the Total and Inorganic Sulfur Quantities in Coal", Proceedings of the Symposium on Electron Microscopy and X-ray Applications to Environmental and Occupational Health Analyses (April 25-27, 1976), Denver, Colo. (To be published). 4. Sutherland, D. C ., "Determination of Organic Sulfur in Coal by Microprobe", Fuel (1975), 54, 41. 5. Frazer, F. W., Belcher, C. Β., "Quantitative Determination of the Mineral--Matter Content of Coal by a Radio Frequency Oxidation Technique", Fuel (1973), 52, 41. 6. Mitchell, R. S., Gluskoter, H. J., "Mineralogy of Ash of Some American Coals: Variation with Temperature and Source", Fuel (1976), 55, 90.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

4 A n Overview of Coal Preparation

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch004

J. A. CAVALLARO and A. W. DEURBROUCK Coal Preparation and Analysis Laboratory, Bureau of Mines, U.S. Department of the Interior, Pittsburgh, PA 15213

Current Coal Preparation Practices 01) In the United States today coal preparation practices are directed toward maximizing Btu recovery, 3-shift-per-day operation of preparation plants, fine-size coal washing, closed water circuits, and reducing sulfur in the final product. In 1976, about 665 million tons of coal were produced, an increase of 24 million tons from 1975. Table I compares clean coal tonnage produced by mechanical cleaning and thermal drying equipment in 1975. Dense-medium processes produced 32.6% of all the clean coal, an increase of 1.6%, while the percentage of coal cleaned by jigs dropped 2.2% to 46.6%. Although only 2.5% of the coal was produced by dry cleaning, interest is growing in the application of dry separation techniques to remove impurities from western coal deposits where water is limited. The tonnage of thermally dried coal continues to decrease as increasingly stringent particulate emission regulations escalate the cost of thermal drying. Since 1970 the proportion of thermally dried bituminous coal has decreased 50%. However, the use of thermal drying will increase in the future as more of the low-sulfur western coals with high inherent moisture of about 25% are used to meet the increased demand for low-sulfur coal. Fluidized­ -bed dryers now dry 72.5% of all the thermally dried coal. In the United States t h e average c o a l p r e p a r a t i o n p l a n t i s o p e r a t e d o n l y a b o u t 13 h r . p e r day, 5 d a y s p e r week. A o n e - a n d two-shift-per-day operation i s being questioned as the cost of c o a l p r e p a r a t i o n i n c r e a s e s o w i n g t o i n f l a t i o n a n d a s t h e new p l a n t c i r c u i t s b e i n g d e v e l o p e d become more c o m p l e x t o meet e x a c t i n g a s h and s u l f u r l e v e l s w i t h minimum l o s s o f B t u s . Consequently, a number o f t h e new p l a n t s a r e b e i n g d e s i g n e d t o wash c o a l 24 h r . p e r day. Where e q u i p m e n t must be o u t o f s e r v i c e f o r p e r i o d i c m a i n t e n a n c e , s u c h a s pumps t h a t move a b r a s i v e m a t e r i a l , b a c k u p u n i t s are being i n s t a l l e d . T h e s e new p l a n t s n o r m a l l y w i l l h a v e c a p a c i t i e s o f 1000-1500 t o n s p e r h r . and w i l l h a v e two o r more p a r a l l e l c o a l washing c i r c u i t s . I n t h i s way, one c i r c u i t c a n b e f

35

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

COAL DESULFURIZATION

Table I .

M e c h a n i c a l C l e a n i n g and T h e r m a l D r y i n g o f B i t u m i n o u s C o a l and L i g n i t e , by Type o f E q u i p m e n t , 1975

Type o f

(thousand

equipment

short

tons)

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch004

Cleaners Wet methods Jigs Concentrating Classifiers Launders

124,317 28,682 6,176 2,664

tables

Dense-medium p r o c e s s e s Magnetite Sand Calcium c h l o r i d e

72,448 13,533 951

Total Flotation

86,932 11,518

T o t a l , wet methods P n e u m a t i c methods Grand

260,289 6,704

total

266,993 Dryers

Fluidized-bed Multilouver Rotary Screen Suspension or f l a s h V e r t i c a l t r a y and c a s c a d e Total a

25,866 1,969 794 2,798 4,184 70 35,681

D a t a may n o t add t o t o t a l s shown b e c a u s e o f i n d e pendent r o u n d i n g .

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

4.

CAVALLARO AND DEURBROUCK

Coal Preparation

37

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch004

down f o r m a i n t e n a n c e w h i l e t h e o t h e r i s p r o c e s s i n g c o a l , t h u s a v o i d i n g a c o m p l e t e shutdown of the c o a l w a s h i n g f a c i l i t y . In t h i s way, p l a n t o p e r a t i n g c o s t s c a n be c o n s i d e r a b l y r e d u c e d . S u l f u r and I t s R e m o v a l . Sulfur i n coal occurs i n three f o r m s — o r g a n i c , s u l f a t e , and p y r i t i c . Organic s u l f u r , which i s an i n t e g r a l p a r t o f t h e c o a l m a t r i x and w h i c h g e n e r a l l y c a n n o t be removed by d i r e c t p h y s i c a l s e p a r a t i o n , c o m p r i s e s 30-70% o f t h e t o t a l s u l f u r o f most c o a l s . G e n e r a l l y , the o r g a n i c s u l f u r - t o t a l s u l f u r r a t i o i s h i g h e s t f o r l o w - s u l f u r c o a l s and d e c r e a s e s as t h e t o t a l s u l f u r content increases. The s u l f a t e i s n o r m a l l y an o x i d a t i o n p r o d u c t w h i c h i s w a t e r s o l u b l e and t h e r e f o r e r e a d i l y removed d u r i n g c o a l c l e a n i n g . Sulf a t e s u l f u r c o n t e n t i s u s u a l l y l e s s t h a n 0.05%. P y r i t i c s u l f u r i n the form of m i n e r a l p y r i t e o c c u r s i n c o a l as d i s c r e t e and s o m e t i m e s m i c r o s c o p i c p a r t i c l e s . I t i s a h e a v y m i n e r a l w i t h a s p e c i f i c g r a v i t y o f a b o u t 5.0 w h e r e a s c o a l has a maximum s p e c i f i c g r a v i t y o f o n l y 1.8. The p y r i t i c s u l f u r c o n t e n t o f a c o a l g e n e r a l l y c a n be r e d u c e d s i g n i f i c a n t l y by s i z e r e d u c t i o n and s u b s e q u e n t s p e c i f i c g r a v i t y s e p a r a t i o n . F i g u r e 1 shows t h e r e s u l t s o f s t a g e c r u s h i n g f r o m 1 1 / 2 - i n c h t o p s i z e t o 200 mesh t o p s i z e and g r a v i m e t r i c a l l y s e p a r a t i n g a s a m p l e o f Lower F r e e p o r t bed c o a l f r o m O h i o and a s a m p l e o f P i t t s b u r g h bed c o a l f r o m West V i r g i n i a . F o r t h e Lower F r e e p o r t bed c o a l s a m p l e , c r u s h i n g f r o m 3/8 i n c h t o 14 mesh p r o v i d e d t h e m a x i mum change i n p y r i t i c s u l f u r r e d u c t i o n f o r t h e f l o a t - 1 . 3 0 - s p e c i f i c g r a v i t y m a t e r i a l and a l s o f o r t h e f l o a t - 1 . 6 0 - s p e c i f i c - g r a v i t y material. F o r t h e P i t t s b u r g h bed c o a l s a m p l e , maximum c h a n g e i n s u l f u r r e d u c t i o n o f a b o u t 0.8 p e r c e n t a g e p o i n t was o b t a i n e d a t e i t h e r s p e c i f i c g r a v i t y by c r u s h i n g f r o m 14 t o 48 mesh. Interesti n g l y , f u r t h e r c r u s h i n g o f t h e P i t t s b u r g h bed c o a l sample f r o m 48 t o 200 mesh showed a n a d d i t i o n a l p y r i t i c s u l f u r r e d u c t i o n o f a b o u t 0.5 p e r c e n t a g e p o i n t f o r t h e f l o a t - 1 . 6 0 - s p e c i f i c - g r a v i t y m a t e r i a l . R e g a r d l e s s o f how d i f f i c u l t and e x p e n s i v e t h e p r o c e s s i n g o f c o a l c r u s h e d t o 48 o r 200 mesh t o p s i z e i s , t h e p o t e n t i a l b e n e f i t s o f o b t a i n i n g l o w - s u l f u r p r o d u c t s may w e l l j u s t i f y t h e a d d i t i o n a l c o s t s and p r o b l e m s e n c o u n t e r e d . C o n t r o l l i n g S u l f u r Oxide Emissions. A v a i l a b l e methods f o r c o n t r o l l i n g s u l f u r oxide emissions from s t a t i o n a r y combustion sources f a l l i n t o the f o l l o w i n g major c a t e g o r i e s : (1) The p h y s i c a l r e m o v a l o f p y r i t i c s u l f u r by c o a l c l e a n i n g p r i o r to combustion. (2) The r e m o v a l o f s u l f u r o x i d e s f r o m t h e c o m b u s t i o n f l u e gas. (3) C o n v e r s i o n o f c o a l t o a c l e a n f u e l by s u c h p r o c e s s e s a s g a s i f i c a t i o n , l i q u e f a c t i o n , and chemical extraction. Of t h e s e m e t h o d s , p h y s i c a l r e m o v a l o f p y r i t i c s u l f u r i s t h e l e a s t e x p e n s i v e and most h i g h l y d e v e l o p e d . The d e g r e e o f s u l f u r

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

38

COAL DESULFURIZATION

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch004

r e d u c t i o n p o s s i b l e depends on t h e w a s h a b i l i t y c h a r a c t e r i s t i c s o f t h e raw c o a l and i t s a m e n a b i l i t y t o s u l f u r r e l e a s e upon c r u s h i n g ; t h e s e c h a r a c t e r i s t i c s a r e u n i q u e and v a r y f r o m c o a l t o c o a l . S u l f u r R e d u c t i o n P o t e n t i a l S t u d i e s . I n 1965, NAPCA (EPA) f u n d e d a s t u d y t o d e t e r m i n e w a s h a b i l i t y c h a r a c t e r i s t i c s o f U.S. coals. The p u r p o s e o f t h i s c o n t i n u i n g s t u d y i s t o d e t e r m i n e t h e f o r m s o f s u l f u r i n t h e m a j o r s o u r c e s o f u t i l i t y s t e a m c o a l s and the s u l f u r r e d u c t i o n p o t e n t i a l of these c o a l s . The i n f o r m a t i o n g e n e r a t e d by t h i s s t u d y i s n e c e s s a r y t o a s s e s s t h e i m p a c t p h y s i c a l d e s u l f u r i z a t i o n o f c o a l m i g h t h a v e on t h e l e v e l o f s u l f u r o x i d e emissions from s t a t i o n a r y combustion sources. A Bureau of Mines r e p o r t e n t i t l e d " S u l f u r Reduction P o t e n t i a l o f t h e C o a l s o f t h e U n i t e d S t a t e s " (2) s u m m a r i z e s t h e w o r k p e r f o r m e d f r o m 1965 t o m i d - 1 9 7 4 . T h i s r e p o r t p r e s e n t s t h e r e s u l t s of a w a s h a b i l i t y s t u d y o f 455 raw c o a l c h a n n e l s a m p l e s w i t h s p e c i a l e m p h a s i s on s u l f u r r e d u c t i o n . The 455 U.S. c o a l s a m p l e s e v a l u a t e d c o n t a i n e d on t h e a v e r a g e 1.91% p y r i t i c s u l f u r and 3.02% t o t a l s u l f u r . Of t h e 455 s a m p l e s t e s t e d , 174 e i t h e r r e q u i r e d no b e n e f i c i a t i o n o r c o u l d be u p g r a d e d t o meet t h e EPA new s o u r c e e m i s s i o n s t a n d a r d o f 1.2 l b SO2/MM B t u . The B t u r e c o v e r y o f t h e s e s a m p l e s a v e r a g e d 88.7% and r a n g e d f r o m 5.6 t o 100%. I f o n l y t h o s e c o a l s w i t h a minimum B t u r e c o v e r y o f 50% a r e c o n s i d e r e d , t h e n 36% o f t h e 455 s a m p l e s t e s t e d w o u l d meet t h e new s t a n d a r d w i t h an a v e r a g e B t u r e c o v e r y o f 9 1 % . E f f e c t s o f B e n e f i c i a t i o n on C o a l R e s e r v e s ( 3 ) . The c o a l r e s o u r c e s i n the S t a t e s east of the M i s s i s s i p p i R i v e r c o n t a i n i n g 1.0% s u l f u r o r l e s s a r e e s t i m a t e d a t 95.3 b i l l i o n t o n s ( F i g u r e 2 ) . A l t h o u g h t h i s i s o n l y 20% o f t h e t o t a l r e m a i n i n g r e s o u r c e , i t i s s t i l l a s i g n i f i c a n t amount. A v a i l a b l e w a s h a b i l i t y d a t a i n d i c a t e t h a t much o f t h e m e d i u m - s u l f u r - c o n t e n t c o a l c a n be u p g r a d e d t o 1.0% s u l f u r o r l e s s u s i n g s t a t e - o f - t h e - a r t c o a l c l e a n i n g techniques. An e f f o r t i s now underway t o d e t e r m i n e how t h e p r e s e n t r e s e r v e s o f c o a l s e a s t o f t h e M i s s i s s i p p i R i v e r w o u l d be c a t e g o r i z e d i n terms of s u l f u r c o n t e n t i f they were s u b j e c t e d t o d i f f e r e n t l e v e l s of c o a l b e n e f i c i a t i o n . T h i s i n v o l v e s an o v e r l a y o f t h e s u l f u r r e d u c t i o n p o t e n t i a l d a t a and t h e r e s e r v e b a s e d a t a g e n e r a t e d by t h e B u r e a u o f M i n e s E a s t e r n F i e l d O p e r a t i o n s C e n t e r . This s t u d y has b e e n c o m p l e t e d f o r t h e N o r t h e r n A p p a l a c h i a n R e g i o n , where a dramatic i n c r e a s e occurs i n the p r o j e c t e d reserves of l o w - s u l f u r coal. The t o n n a g e s , by s u l f u r c a t e g o r y and e x t e n t o f p r e p a r a t i o n , for the e n t i r e Northern Appalachian Region are given i n Table I I . The p r e s e n t r e s e r v e s w i t h s u l f u r c o n t e n t l e s s t h a n 0.85% amount t o 1,727.45 m i l l i o n t o n s . C r u s h i n g t o 1 1/2 i n . t o p s i z e and w a s h i n g a t 1.60 s p e c i f i c g r a v i t y y i e l d s 4,172.32 m i l l i o n t o n s o f l o w - s u l f u r c o a l , w h i c h i s 2.4 t i m e s t h e e x i s t i n g r e s e r v e s .

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

CAVALLARO AND DEURBROUCK

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch004

Float

Coal Preparation

I 6 0 sp gr

TOP SIZE TO WHICH F E E D WAS C R U S H E D , inches ond mesh

Figure 1. Pyritic sulfur reduction potential for two Appafochian region coals as a result of stage crushing

Figure 2. Estimated remaining coal resources of all ranks, by sulfur content, in states east of the Mississippi River, Jan. 1,1965

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

40

COAL DESULFURIZATION

C r u s h i n g t o 14-mesh t o p s i z e and c l e a n i n g a t 1.60 s p e c i f i c g r a v i t y w o u l d r e s u l t i n a t o t a l o f 8,546.31 m i l l i o n t o n s o f l o w - s u l f u r c o a l , w h i c h i s 4.9 t i m e s t h e p r e s e n t r e s e r v e s . Four percent of the Northern Appalachian Region r e s e r v e s w i t h a s u l f u r content g r e a t e r t h a n 0.85% c a n be u p g r a d e d t o l o w - s u l f u r c o a l by c r u s h i n g t o 1 1 / 2 - i n . t o p s i z e and w a s h i n g a t 1.60 s p e c i f i c g r a v i t y ; t h e p e r c e n t a g e i n c r e a s e s t o 10 when c r u s h i n g t o 14-mesh t o p s i z e and w a s h i n g a t 1.60 s p e c i f i c g r a v i t y .

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch004

Table I I .

C o a l P r e p a r a t i o n Wins L o w - S u l f u r C o a l f o r Energy Market i n Northern Appalachian Region, M i l l i o n s o f Tons

<0.85% Sulfur

Product

Raw

coal

1,727.45 Crushed t o 1

C l e a n e d a t 1.30 C l e a n e d a t 1.60

0.85-3.00% Sulfur

38,995.41

>3.0% Sulfur

27,535.04

1/2- i n c h t o p s i z e

4,237.93 4,172.32

20,398.17 43,396.58

637.26 14,164.45

C r u s h e d t o 3/8-i n c h t o p s i z e C l e a n e d a t 1.30 C l e a n e d a t 1.60

6,485.79 6,224.53

22,350.99 44,595.82

651.68 9,918.26

C r u s h e d t o 14-mesh t o p s i z e C l e a n e d a t 1.30 C l e a n e d a t 1.60

7,136.62 8,546.31

21,691.77 45,873.05

395.59 5,956.40

F i g u r e s 3 and 4 show g r a p h i c a l l y t h e e f f e c t o f c r u s h i n g t o v a r i o u s t o p s i z e s on t h e t o n n a g e s o f l o w - s u l f u r c o a l p o t e n t i a l l y a v a i l a b l e i n the Northern Appalachian Region. I n examining these f i g u r e s to e s t a b l i s h the b e n e f i t s of c o a l preparation, i t i s n e c e s s a r y t o keep s e v e r a l t h i n g s i n m i n d . F i r s t o f a l l , e v e n t h o u g h t h e t o n n a g e s o f l o w - s u l f u r c o a l ( l e s s t h a n 0.85% s u l f u r ) r e s u l t i n g from c o a l p r e p a r a t i o n a r e a r e l a t i v e l y s m a l l f r a c t i o n of the t o t a l r e s e r v e base, they represent s i z a b l e q u a n t i t i e s of c o a l , e q u i v a l e n t t o many y e a r s o f p r o d u c t i o n a t c u r r e n t and f o r e s e e n r a t e s . M o r e o v e r , many p o w e r p l a n t s c o n s t r u c t e d p r i o r t o 1975 c a n be b r o u g h t i n t o c o m p l i a n c e w i t h l o c a l e m i s s i o n s t a n d a r d s by using c o a l cleaned to the appropriate s u l f u r l e v e l . I n summary, c o a l p r e p a r a t i o n has t h e p o t e n t i a l o f p r o v i d i n g s i z a b l e t o n n a g e s o f c o a l t h a t w i l l meet t h e EPA n e w - s o u r c e

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

CAVALLARO AND DEURBROUCK

Coal Preparation

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch004

10,000

TOP SIZE A F T E R CRUSHING

Figure 3. Effect of crusing and cleaning at 1.60 specific gravity on the availability of < 0.85% sulfur coal

Figure 4. Effect of crushing and cleaning at 1.30 specific gravity on the availability of < 0.85% sulfur coal

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

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emission standards. I n a d d i t i o n , f o r powerplants b u i l t p r i o r to 1975, f a r g r e a t e r q u a n t i t i e s o f c o a l c a n b e b u r n e d a f t e r u p g r a d i n g by c o a l p r e p a r a t i o n .

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch004

New D e v e l o p m e n t s i n C o a l P r e p a r a t i o n

(4 )

Coal p r e p a r a t i o n s t a t e - o f - t h e - a r t i s changing r a p i d l y i n the United States today. The s c o p e o f t h e s e c h a n g e s and some o f t h e new c i r c u i t and e q u i p m e n t i n n o v a t i o n s w h i c h h a v e b e e n r e c e n t l y i n t r o d u c e d a r e d i s c u s s e d below. The m a j o r e m p h a s i s i s o n r e d u c i n g s u l f u r a n d m a x i m i z i n g B t u recovery. The n e e d f o r s u l f u r r e d u c t i o n stems f r o m t h e e n f o r c e ment o f SO2 e m i s s i o n s t a n d a r d s , w h i l e h i g h B t u r e c o v e r y becomes e s s e n t i a l as a r e s u l t o f t h e i n c r e a s e d v a l u e o f c o a l as an energy source. The r e s u l t i n g i r o n y s p e l l s o u t t h e c h a l l e n g e f a c i n g c o a l p r e p a r a t i o n today: How t o e c o n o m i c a l l y p r o d u c e i n c r e a s i n g amounts of c o a l that s a t i s f y t h e s t r i c t p o l l u t i o n standards. Homer C i t y P r e p a r a t i o n P l a n t . A p o s s i b l e s o l u t i o n t o t h e d u a l p r o b l e m s o f e n v i r o n m e n t a l r e s t r i c t i o n s a n d maximum r e c o v e r y i s t h e h i g h l y p u b l i c i z e d Homer C i t y m u l t i s t r e a m c o a l c l e a n i n g p l a n t ( F i g u r e 5 ) . The p l a n t i s b e i n g b u i l t f o r j o i n t o w n e r s , New Y o r k S t a t e E l e c t r i c and Gas C o r p . a n d P e n n s y l v a n i a E l e c t r i c Co., b y H e y l & P a t t e r s o n , I n c . The p l a n t w i l l p r o d u c e two streams of c l e a n c o a l . The f i r s t s t r e a m w i l l be a n e x t r e m e l y h i g h q u a l i t y p r o d u c t w h i c h w i l l meet t h e e n v i r o n m e n t a l standards f o r f i r i n g i n t h e new U n i t 3 g e n e r a t i n g s t a t i o n ( 6 5 0 MW) w i t h o u t subsequent s t a c k gas s c r u b b i n g . The s e c o n d c l e a n c o a l s t r e a m i s o f i n t e r m e d i a t e q u a l i t y and w i l l meet t h e e x i s t i n g s o u r c e r e q u i r e m e n t s f o r U n i t s 1 and 2, w h i c h a r e 600 MW e a c h . The e x p e c t e d p r e p a r a t i o n p l a n t p e r f o r m a n c e , g i v e n i n T a b l e I I I , shows t h a t t h e s u l f u r c o n t e n t i s r e d u c e d a b o u t 70% f r o m 2.8% t o 0.88% i n t h e U n i t 3 c l e a n c o a l w h i l e t h e o v e r a l l B t u r e c o v e r y i s 94.5%. Table I I I .

Homer C i t y P r e p a r a t i o n P l a n t E x p e c t e d P e r f o r m a n c e '

Recovery (weight percent) Recovery (Btu percent)* P r o d u c t Btu/pound (dry b a s i s ) Ash, percent S u l f u r , percent Pounds s u l f u r / M M B t u 5

Units 1 & 2

Unit 3

Refuse

56.2 61.6 °12,549 17.8 2.84 1.79

24.7 32.9 15,200 2.8 0.88 0.58

19.1 5.5 3,367 69.7

a

(Loss)

R e f e r e n c e : J . F. M c C o n n e l l , Homer C i t y C o a l C l e a n i n g D e m o n s t r a t i o n , 4 t h N a t i o n a l C o n f e r e n c e on E n e r g y and E n v i r o n m e n t ( E P A ) . ^ G r o s s r e c o v e r y , 94.5%; n e t r e c o v e r y i s 9 3 . 5 % w i t h l o s s e s f o r thermal dryer included. B l e n d o f m i d d l i n g and c l e a n c o a l . c

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch004

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch004

44

COAL DESULFURIZATION

The p l a n t i n c l u d e s s e v e r a l i n n o v a t i v e a p p l i c a t i o n s o f e x i s t i n g t e c h n o l o g y w h i c h we a t t h e B u r e a u o f M i n e s h a v e b e e n r e s e a r c h i n g a t a p i l o t p l a n t l e v e l i n c o o p e r a t i o n w i t h t h e owners and designers. I n p r o d u c i n g t h e c l e a n c o a l f o r U n i t 3, dense-medium c y c l o n e s c l e a n a t a s p e c i f i c g r a v i t y o f s e p a r a t i o n o f 1.3; a s p e c i f i c g r a v i t y o f 1.8 i s u s e d t o r e c l e a n t h e u n d e r f l o w m a t e r i a l f o r U n i t s 1 and 2. These s e p a r a t i n g s p e c i f i c g r a v i t i e s a r e s i g n i f i c a n t l y b e y o n d t h e n o r m a l o p e r a t i n g r a n g e o f a b o u t 1.4-1.6 f o r dense-medium c y c l o n e s w a s h i n g b i t u m i n o u s c o a l . A l s o , t h e u s u a l 28-mesh b o t t o m s i z e o f t h e c o a l c l e a n e d i n t h e c y c l o n e w i l l be e x t e n d e d t o 100 mesh, o r t o a b o u t o n e - f o u r t h the u s u a l s i z e . The f e e d i s s i z e d a t 1 / 4 - i n . by 9-mesh and 9- by 100-mesh f r a c t i o n s and c l e a n e d i n two s e p a r a t e c y c l o n e c i r c u i t s , i n s t e a d o f t h e w h o l e f e e d b e i n g washed i n one c y c l o n e c i r c u i t . Because of the s m a l l p a r t i c l e s i z e of c o a l cleaned i n the 9- by 100-mesh c y c l o n e c i r c u i t , c o n v e n t i o n a l d r a i n and r i n s e s c r e e n s f o r s u b s e q u e n t m a g n e t i t e r e c o v e r y a r e r e p l a c e d by twostage magnetic s e p a r a t o r s which handle the f u l l streams of overf l o w and u n d e r f l o w p r o d u c t s f r o m t h e c y c l o n e . The c l e a n i n g o f f i n e r s i z e c o a l i n c y c l o n e s f o l l o w e d by t h e a b o v e a p p l i c a t i o n o f m a g n e t i c s e p a r a t o r s i s a l s o b e i n g c o n s i d e r e d f o r i n s t a l l a t i o n s by o t h e r companies. Another i n t e r e s t i n g f e a t u r e i s a novel c o n t r o l c i r c u i t f o r c l o s e s p e c i f i c g r a v i t y c o n t r o l of the feed s l u r r y to the densemedium c y c l o n e s . When o p e r a t i n g a t s p e c i f i c g r a v i t i e s o f s e p a r a t i o n a r o u n d 1.3, t h e ±0.10 n e a r - g r a v i t y m a t e r i a l i n t h e f e e d i s a b o u t 60%. T h e r e f o r e , t h e e n t e r i n g s l u r r y must be r i g i d l y m a i n t a i n e d a t t h e p r o p e r s p e c i f i c g r a v i t y o r m a t e r i a l w i l l be m i s placed. T h i s w i l l r e s u l t i n e i t h e r a c l e a n c o a l t h a t does not meet s p e c i f i c a t i o n s o r a d e c r e a s e i n h i g h - q u a l i t y c l e a n c o a l tonnage. F i g u r e 6 shows t h e p i l o t p l a n t c o n t r o l s y s t e m t h a t i s now b e i n g t e s t e d a t t h e B u r e a u o f M i n e s . Three s t r e a m s — f r e s h w a t e r , c o a l s l u r r y , and m a g n e t i t e s l u r r y — a r e c o m b i n e d i n t h e m i x i n g sump and r e p r e s e n t t h e f e e d t o a dense-medium c y c l o n e . Ins t r u m e n t s m e a s u r e t h e d e n s i t y and f l o w r a t e o f e a c h s t r e a m and s e n d t h e measurement s i g n a l s t o an a n a l o g c o m p u t e r . The c o m p u t e r c a l c u l a t e s t h e s e s i g n a l s , compares t h e a c t u a l d e n s i t y and f l o w f o r t h e f e e d s l u r r y w i t h t h e p r e s e t v a l u e s , and t h e n c o n t r o l s t h e w a t e r and m a g n e t i t e s l u r r y f l o w r a t e s a c c o r d i n g l y t o p r o d u c e t h e preset values. The s y s t e m n o t o n l y m a i n t a i n s s t r i c t q u a l i t y c o n t r o l a t a h i g h e f f i c i e n c y , but p r o v i d e s the f l e x i b i l i t y needed to make q u i c k c h a n g e s i n t h e s p e c i f i c g r a v i t y o f s e p a r a t i o n , s h o u l d t h e w a s h a b i l i t y c h a r a c t e r i s t i c s o f t h e raw c o a l change. B a t a c J i g . The t r e n d t o w a r d f i n e - s i z e c o a l c l e a n i n g t o remove more s u l f u r and r e c o v e r more B t u s has s p u r r e d t h e d e v e l o p ment o f c l o s e d w a t e r c i r c u i t s and many new t e c h n i q u e s and c i r c u i t s i n w a s h i n g , d e w a t e r i n g , and s i z i n g . Baum j i g s w a s h i n g c o a r s e c o a l s t i l l p r o d u c e t h e most c l e a n c o a l ; h o w e v e r , t h e B a t a c j i g , d e v e l o p e d i n Germany t o c l e a n f i n e c o a l , has b e e n i n s t a l l e d i n a t 1

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Figure 6.

Dense-medium specific gravity control circuit

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch004

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COAL DESULFURIZATION

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch004

l e a s t t h r e e U.S. p l a n t s t o p r o c e s s 1 / 2 - i n . by 0 raw c o a l . It is g e n e r a l l y i n s t a l l e d a f t e r a Baum j i g w h i c h c l e a n s t h e p l u s 1/2i n c h raw c o a l . In the Batac j i g , a i r p u l s a t i o n s are produced i n m u l t i p l e chambers d i r e c t l y b e n e a t h t h e bed s c r e e n , a s shown i n F i g u r e 7. The p u l s e s i n e a c h chamber a r e c o n t r o l l e d i n d e p e n d e n t l y and p r e c i s e l y . The j i g p r o v i d e s s i g n i f i c a n t l y h i g h e r t h r o u g h p u t i n t h e same s p a c e a s a c o n v e n t i o n a l Baum j i g b e c a u s e o f i t s i m p r o v e d e f f i c i e n c y and e l i m i n a t i o n o f t h e a d j a c e n t a i r chamber. The B a t a c j i g c l e a n s w i t h a s h a r p n e s s s i m i l a r t o t h a t o f c o n c e n t r a t i n g t a b l e s f o r t h e same s i z e r a n g e . Novel F i n e - S i z e Cleaning C i r c u i t . An i n t e r e s t i n g new f i n e s i z e c o a l c l e a n i n g c i r c u i t has b e e n i n s t a l l e d i n a P e n n s y l v a n i a p r e p a r a t i o n p l a n t by R o b e r t s & S c h a e f e r Co. The p l a n t was o r i g i n a l l y s t r i c t l y an a i r t a b l e p l a n t , b u t a dense-medium c y c l o n e has b e e n i n c o r p o r a t e d t o r e c l e a n t h e s e c o n d and t h i r d r e f u s e d r a w s from the a i r t a b l e . The f i r s t d r a w i s e s s e n t i a l l y p u r e r e f u s e w i t h no m i s p l a c e d f l o a t m a t e r i a l . W i t h t h e s e c o n d and t h i r d d r a w s w i d e o p e n , t h e amount o f s i n k m a t e r i a l r e p o r t i n g t o t h e c l e a n c o a l i s reduced. A t t h e s e t a b l e s e t t i n g s , a b o u t 20% o f t h e f e e d i s sent to the cyclone to maximize Btu recovery w h i l e upgrading the f i n a l product. The c y c l o n e p r o d u c e s a 5.6%-ash c l e a n c o a l , w h i c h i s combined w i t h t h e c l e a n c o a l from the a i r t a b l e . The n e t r e s u l t s a r e a 5% i n c r e a s e i n y i e l d and a 20% d e c r e a s e i n a s h c o n tent. The a i r t a b l e i s r e c e i v i n g a t t e n t i o n f r o m w e s t e r n c o a l p r o d u c e r s who a r e l o o k i n g f o r a d r y method o f c l e a n i n g c o a l i n the water-scarce Western S t a t e s . D e w a t e r i n g and S i z i n g . One o f t h e b i g g e s t p r o b l e m s i n p r o c e s s i n g f i n e - s i z e c o a l i s d e w a t e r i n g and s i z i n g . The s e v e r e b l i n d i n g t e n d e n c y o f m i n u s 28-mesh c o a l s l u r r i e s on c o n v e n t i o n a l s c r e e n s makes f o r e x t r e m e l y i n e f f i c i e n t and u n r e l i a b l e s e p a r a tions. A new s c r e e n i n g d e v i c e has b e e n d e v e l o p e d by D e r r i c k M a n u f a c t u r i n g Corp. w h i c h p u r p o r t s t o have s o l v e d t h e b l i n d i n g problem. I t c o n s i s t s of a "sandwich s c r e e n " concept, which binds two f i n e s c r e e n s u r f a c e s one on t o p o f t h e o t h e r . The a c t i o n o f t h e two s c r e e n s a g a i n s t e a c h o t h e r , f r o m a s p e c i a l h i g h f r e q u e n c y low a m p l i t u d e v i b r a t i n g motor, p r e v e n t s n e a r - s i z e p a r t i c l e s from becoming lodged i n the top s c r e e n . The o p e n i n g s i n t h e b o t t o m screen are s l i g h t l y l a r g e r than those i n the top to ensure t h a t p a r t i c l e s a r e not t r a p p e d between s c r e e n s . D e r r i c k claims these s c r e e n s c a n make s h a r p s e p a r a t i o n s down t o 400 mesh. The f i n a l s e c t i o n o f t h e s c r e e n may be a s l o t t e d n a t u r a l r u b b e r s u r f a c e f i t t e d w i t h a p a t e n t e d vacuum a r r a n g e m e n t t o h e l p remove a d d i t i o n a l surface moisture. C l o s e d Water C i r c u i t s . I n a d d i t i o n to the enforcement of a i r e m i s s i o n s t a n d a r d s , s t r e a m p o l l u t i o n and r e f u s e d i s p o s a l l a w s h a v e become more s t r i n g e n t r e c e n t l y . T h u s , new p r e p a r a t i o n p l a n t s u s e some t y p e o f c l o s e d w a t e r c i r c u i t w i t h a g r a v i t a t i o n a l

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Coal Preparation

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch004

CAVALLARO AND DEURBROUCK

Library American Chemical Society T.; In Coal Desulfurization; Wheelock, ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

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COAL DESULFURIZATION

c l a r i f i e r as t h e p r i m a r y p i e c e o f e q u i p m e n t i n t h e s y s t e m . Two new t h i c k e n e r d e s i g n s — t h e L a m e l l a and t h e E n v i r o - C l e a r — a r e o f i n t e r e s t f o r p o s s i b l e a p p l i c a t i o n a t p l a n t s i t e s where l a n d a r e a i s a t a premium. T h e s e u n i t s h a v e b e e n i n s t a l l e d a t o l d e r p l a n t s w h i c h had s p a c e l i m i t a t i o n s and w e r e e x p a n d i n g t h e i r p l a n t c a p a c i t y o r e l i m i n a t i n g waste ponds. B o t h compact t h i c k e n e r s may r e q u i r e as l i t t l e as o n e - t e n t h o f t h e s p a c e o c c u p i e d by a c o n v e n t i o n a l c i r c u l a r t a n k t h i c k e n e r . The c l a r i t y of t h e i r o v e r f l o w i s c o m p e t i t i v e w i t h t h a t of c o n v e n t i o n a l t h i c k e n e r s w i t h o v e r f l o w c o n c e n t r a t i o n s o f 500 t o 100 ppm o r l e s s of s o l i d s , while underflow concentrations are s l i g h t l y higher at 30-40% s o l i d s . E a c h t h i c k e n e r o p e r a t e s on a d i f f e r e n t d e s i g n p r i n c i p l e . The L a m e l l a ( F i g u r e 8) has t h e same s e t t l i n g a r e a f o r a g i v e n f l o w r a t e as a c o n v e n t i o n a l t h i c k e n e r by v i r t u e o f a s e r i e s o f p l a t e s . The s e t t l i n g o u t o f s o l i d s on t h e s e p l a t e s i s much l i k e t h a t i n a s t a c k of c o n v e n t i o n a l t h i c k e n e r s , but the p l a t e s a r e i n c l i n e d to a l l o w continuous removal of the s o l i d s . L a m e l l a s have f e e d l o a d i n g r a t e s o f 0.5 t o 0.6 g p m / f t ^ , and u s e f l o c c u l a n t d o s a g e s o f a b o u t 2 ppm. These v a l u e s a r e i n l i n e w i t h those of the l a r g e c i r c u l a r tank t h i c k e n e r s . At present, the l a r g e s t Lamella w i l l h a n d l e 1,500 gpm. The E n v i r o - C l e a r ( F i g u r e 9) has a much h i g h e r f e e d l o a d i n g r a t e , 3 t o 4 gpm/ft^, because i t does not have the s e t t l i n g a r e a of the L a m e l l a t h i c k e n e r . I t i s a bottom-fed u n i t which a c t u a l l y u s e s t h e s e t t l e d s o l i d s a s a f i l t e r i n g medium f o r t h e w a t e r as i t f l o w s upward t o t h e o v e r f l o w . T h e r e a r e o n l y two z o n e s i n t h i s t h i c k e n e r , c l a r i f i e d l i q u i d and c o m p r e s s e d s o l i d s . Feed f l u c u a t i o n s c a n be a b s o r b e d by a l l o w i n g t h e s l u d g e bed l e v e l t o r i s e o r f a l l w i t h no d e t r i m e n t t o t h e o v e r f l o w c l a r i t y . Both u n i t s a r e more s e n s i t i v e t o f e e d v a r i a t i o n s , and t h e y l a c k t h e huge advantage of a l a r g e storage c a p a c i t y which c o n v e n t i o n a l t h i c k eners have. The e x a m p l e s d i s c u s s e d show t h a t t h e r e a r e i n n o v a t i o n s i n a l l areas of c o a l p r e p a r a t i o n . The new e q u i p m e n t , n o v e l techniques, c o m p l e x c i r c u i t r y , and h i g h e r l e v e l s o f c o n t r o l a r e a l l needed i n o r d e r t o i n s u r e t h a t c o a l m a r k e t demands c a n be met economically. Summary o f U.S.

Bureau of Mines C o a l P r e p a r a t i o n Program

(5)

P r i o r t o 1965, t h e m a i n t h r u s t o f t h e B u r e a u o f M i n e s c o a l p r e p a r a t i o n r e s e a r c h e f f o r t was d i r e c t e d t o w a r d a s h r e d u c t i o n w i t h l i t t l e e f f o r t aimed a t the e n v i r o n m e n t a l a s p e c t s of c o a l u t i l i z a tion. The r e s e a r c h i m p e t u s c l e a r l y mandated by t h e C l e a n A i r A c t o f 1970 i s t h a t S 0 e m i s s i o n s must be c o n t r o l l e d , t r a c e e l e m e n t s p r e s e n t i n t h e raw c o a l must be i d e n t i f i e d and t r a c k e d t o f i n a l d i s p o s a l , and t h e e n v i r o n m e n t a l e f f e c t s o f t h e c o a l p r e p a r a t i o n p r o c e s s i t s e l f must meet s t r i n g e n t r e q u i r e m e n t s . W i t h t h i s l e g i s l a t e d mandate, an e n t i r e l y new d i m e n s i o n o f c o a l p r e p a r a t i o n r e s e a r c h has emerged. The B u r e a u o f M i n e s has X

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

CAVALLARO AND DEURBROUCK

Coal Preparation

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4.

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Figure 8. Lamelfo thickener

Figure 9.

Enviro-Clear thickener

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

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i n i t i a t e d a c o a l p r e p a r a t i o n p r o g r a m commensurate w i t h t h e v i t a l e n e r g y demands o f t h i s N a t i o n . The f o r m e r s p e c t r u m o f c o a l p r e p a r a t i o n r e s e a r c h has n o t b e e n e l i m i n a t e d b u t r a t h e r b r o a d e n e d t o meet t h e s e new demands. The p r i m a r y o b j e c t i v e o f t h e B u r e a u o f M i n e s C o a l P r e p a r a t i o n Program i s to i n c r e a s e the a v a i l a b i l i t y of e n v i r o n m e n t a l l y a c c e p t a b l e f u e l s f o r combustion use through the removal of p o l l u t i n g constituents. T h i s i s t o be a c c o m p l i s h e d by a d v a n c i n g t h e s t a t e o f - t h e - a r t o f c o a l c l e a n i n g t o a l e v e l where l o w - p o l l u t a n t f u e l s c a n be p r o d u c e d i n a c o s t - e f f e c t i v e manner i n c o m m e r c i a l - s c a l e q u a n t i t i e s w i t h o u t a l t e r i n g t h e b a s i c f o r m of t h e p r o c e s s e d f u e l . Two-Stage C o a l - P y r i t e F l o t a t i o n . F r o t h f l o t a t i o n of c o a l s u f f e r s as a d e s u l f u r i z a t i o n method b e c a u s e of t h e t e n d e n c y f o r the f i n e - s i z e p y r i t e p a r t i c l e s to f l o a t w i t h the c o a l . As a c o n s e q u e n c e , t h e B u r e a u o f M i n e s has b e e n c o n d u c t i n g r e s e a r c h t o i m p r o v e f l o t a t i o n p r o c e d u r e s so t h a t b e t t e r p y r i t e r e j e c t i o n i s possible. E a r l y l a b o r a t o r y f l o t a t i o n w o r k showed t h a t t h e q u a n t i t y of p y r i t e r e p o r t i n g w i t h the c l e a n c o a l f r o t h product i n c r e a s e d w i t h i n c r e a s i n g a d d i t i o n s o f t h e f r o t h i n g a g e n t and w i t h lengthy f r o t h c o l l e c t i o n times. T h e r e f o r e , some d e s u l f u r i z a t i o n was made p o s s i b l e by u s i n g s t a r v a t i o n amounts o f r e a g e n t and v e r y b r i e f s l u r r y residence times. S u b s t a n t i a l s u l f u r r e d u c t i o n s w e r e a l s o a c h i e v e d w i t h some c o a l s by t w o - s t a g e r o u g h e r - c l e a n e r f l o t a t i o n i n w h i c h t h e c l e a n c o a l f r o t h c o n c e n t r a t e f r o m t h e f i r s t s t a g e was r e f l o a t e d . I n a l l o f t h i s e a r l i e r w o r k , i t was r e c o g n i z e d t h a t a p o r t i o n o f t h e p y r i t e r e p o r t e d t o t h e c l e a n c o a l f r o t h p r o d u c t b e c a u s e i t was a t t a c h e d t o f l o a t a b l e c o a l o r b e c a u s e i t was t o o f i n e and became m e c h a n i c a l l y entrapped i n the f r o t h . To combat t h i s p r o b l e m , a u n i q u e t w o - s t a g e f l o t a t i o n p r o c e s s was d e v e l o p e d and p a t e n t e d (6) by t h e B u r e a u . The p r o c e s s c o n s i s t s o f a f i r s t - s t a g e c o a l f l o t a t i o n s t e p i n w h i c h h i g h - a s h r e f u s e and t h e c o a r s e o r s h a l e a s s o c i a t e d p y r i t e a r e removed as t a i l i n g s . The f i r s t - s t a g e c o a l f r o t h c o n c e n t r a t e i s t h e n r e p u l p e d i n f r e s h w a t e r , and a c o a l d e p r e s s a n t , a p y r i t e c o l l e c t o r , and a f r o t h e r a r e added. A h i g h s u l f u r - c o n t e n t p r o d u c t i s t h e n f l o a t e d , and t h e s e c o n d - s t a g e u n d e r f l o w i s c o l l e c t e d as t h e f i n a l c l e a n c o a l . I n l a b o r a t o r y and p i l o t p l a n t f l o t a t i o n t e s t s w i t h c o a l s from v a r i o u s coalbeds throughout the E a s t e r n U n i t e d S t a t e s , p y r i t i c s u l f u r r e d u c t i o n s o f up t o 90% w e r e a c h i e v e d u s i n g t h i s t e c h n i q u e ( 7 ) . The f i r s t c o m m e r c i a l i n s t a l l a t i o n o f t h e c o a l - p y r i t e f l o t a t i o n p r o c e s s w i l l go on l i n e a t t h e L a n c a s h i r e No. 25 p r e p a r a t i o n p l a n t o f t h e B a r n e s and T u c k e r Co. i n A u g u s t 1977. This i s a c o o p e r a t i v e e f f o r t w i t h the Bureau of Mines. I f i t works succ e s s f u l l y , i t w i l l mean t h e r e c o v e r y o f an a d d i t i o n a l 8 t o n s p e r h o u r o f f i n e - s i z e c o a l t h a t i s now b e i n g d i s c a r d e d as w a s t e because of i t s h i g h s u l f u r content. R e s e a r c h i s b e i n g c o n d u c t e d as t h e U n i v e r s i t y o f U t a h t o i n v e s t i g a t e t h e d e p r e s s a n t and c o l l e c t o r a d s o r p t i o n r e a c t i o n s

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4.

CAVALLARO

A N D DEURBROUCK

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i n v o l v e d i n the C o a l - P y r i t e F l o t a t i o n Process. The o b j e c t i v e s o f t h i s p r o g r a m w i l l be t o — (1) I d e n t i f y and c h a r a c t e r i z e the h y d r o p h i l i c polymeric coal depressants. (2) Determine the important o p e r a t i n g v a r i a b l e s which c o n t r o l the a d s o r p t i o n - d e s o r p t i o n r e a c t i o n s and r e l a t e these r e s u l t s t o the f l o t a t i o n response o f t h e mineral constituents. (3) E s t a b l i s h procedures, i f necessary, t o allow f o r subsequent c o a l f l o t a t i o n and p l a n t water r e c y c l e without d e l e t e r i o u s e f f e c t s from r e s i d u a l reagent concentrations. High-Gradient Magnetic Separation. High-gradient magnetic s e p a r a t i o n (HGMS) u s e s l a r g e - c a p a c i t y d e v i c e s a s a p r a c t i c a l means t o s e p a r a t e s m a l l , w e a k l y m a g n e t i c p a r t i c l e s o n a l a r g e scale. This technology, which i s being u t i l i z e d commercially to p u r i f y k a o l i n c l a y , i s being i n v e s t i g a t e d through s e v e r a l Bureau o f Mines c o n t r a c t s t o determine i t s p o t e n t i a l f o r a p p l i c a t i o n i n the c o a l p r e p a r a t i o n i n d u s t r y . G e n e r a l E l e c t r i c Co., i n c o n j u n c t i o n w i t h t h e M a s s a c h u s e t t s I n s t i t u t e o f Technology and E a s t e r n A s s o c i a t e d C o a l Corp., i s a t t e m p t i n g t o e s t a b l i s h the t e c h n i c a l f e a s i b i l i t y o f removing a s u b s t a n t i a l f r a c t i o n o f t h e i n o r g a n i c s u l f u r f r o m d r y c o a l powders by HGMS. In a d d i t i o n t o sponsoring these c o n t r a c t s , the Bureau w i l l e s t a b l i s h i n h o u s e c a p a b i l i t y f o r HGMS i n t h e n e a r f u t u r e . A highg r a d i e n t m a g n e t i c s e p a r a t o r o f t h e c a n i s t e r t y p e h a s been o r d e r e d , and a r e s e a r c h p r o g r a m i n v o l v i n g a w i d e v a r i e t y o f c o a l s w i l l b e i n i t i a t e d w i t h i n s e v e r a l months. C o a l Prep/FGD C o m b i n a t i o n S t u d y . I n a s t u d y j u s t c o m p l e t e d f o r the Bureau o f Mines by the Hoffman-Muntner Corp. ( 8 ) , t h e e c o n o m i c p o t e n t i a l o f c o a l p r e p a r a t i o n combined w i t h s t a c k g a s s c r u b b i n g was e v a l u a t e d . The c o n c e p t o f p h y s i c a l c o a l c l e a n i n g combined w i t h f l u e gas d e s u l f u r i z a t i o n i s n o t new. I n t h e H o f f m a n - M u n t n e r s t u d y , a c t u a l c o a l u s e a r e a s , c o a l s o u r c e a r e a s , a n d t h e most p r o b a b l e c o a l b e d s o u r c e a r e d e f i n e d a n d u s e d t o make a n e c o n o m i c e v a l u a tion of physical coal cleaning. Then t h e c o s t o f a new u t i l i t y p l a n t r e m o v i n g SO2 ( e x c l u s i v e l y ) b y s t a c k g a s s c r u b b i n g t o meet t h e new s o u r c e e m i s s i o n s t a n d a r d was e v a l u a t e d . T h i s was f o l l o w e d b y a s i m i l a r e v a l u a t i o n o f t h e combined u s e o f p h y s i c a l c o a l c l e a n i n g p l u s s t a c k g a s s c r u b b i n g t o a t t a i n t h e same SO2 emission l e v e l . T h e s e c a s e s t u d i e s i n d i c a t e t h a t f o r many s i t u a t i o n s t h e e c o n o m i c a d v a n t a g e o f a combined a p p r o a c h i s q u i t e s i g n i f i c a n t . T h i s a d v a n t a g e depends o n :

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(1) The a v a i l a b i l i t y o f c o a l s c a p a b l e o f s i g n i f i c a n t r e d u c t i o n s i n a s h a n d s u l f u r by p h y s i c a l u p g r a d i n g w i t h minimal Btu l o s s . (2) A c l e a n c o a l s u l f u r l e v e l t h a t i s c o m p a t i b l e w i t h s i g n i f i c a n t l y l e s s than f u l l - s c a l e scrubbing requirements. Even so, t h e range o f v a r i a b l e s i s such t h a t each c o a l s o u r c e - u s e r c o m b i n a t i o n must b e i n d i v i d u a l l y a s s e s s e d . Chemical D e s u l f u r i z a t i o n . P r e s e n t methods o f p h y s i c a l c o a l preparation i n r e l a t i o n t o s u l f u r reduction apply only to the p a r t i a l removal o f p y r i t i c s u l f u r . A s t h e s e p h y s i c a l methods do n o t remove o r g a n i c a l l y bound s u l f u r , t h e y c a n be a p p l i e d e f f e c t i v e l y only to selected coals. T h e r e f o r e , t h e Bureau of Mines p r o g r a m h a s b e e n expanded t o i n c l u d e r e s e a r c h o n e x p e r i m e n t a l and developmental techniques using chemical, i n a d d i t i o n t o p h y s i c a l , methods f o r c o a l d e s u l f u r i z a t i o n s o t h a t more c o a l s w i l l be made a v a i l a b l e w i t h i n t h e framework o f e n v i r o n m e n t a l r e s t r a i n t s . P r e s e n t l y , t h e B u r e a u i s engaged i n a n i n h o u s e r e s e a r c h program t o develop i n n o v a t i v e c h e m i c a l treatments s p e c i f i c a l l y aimed a t o r g a n i c s u l f u r r e m o v a l . The c h e m i c a l o x i d a t i o n o f t h e o r g a n i c s u l f u r t o a f o r m w h i c h c o u l d b e removed more r e a d i l y a p p e a r s t o have p o t e n t i a l and i s b e i n g i n v e s t i g a t e d a c t i v e l y . We e n v i s i o n t h a t t h e optimum d e s u l f u r i z a t i o n o f c o a l w i l l i n c l u d e b o t h p h y s i c a l and c h e m i c a l t r e a t m e n t . The r a w c o a l w i l l be c r u s h e d f i n e enough t o m a x i m i z e p y r i t e r e l e a s e . I t w i l l t h e n be p h y s i c a l l y t r e a t e d u s i n g wet p r o c e s s e s t o remove t h e l i b e r a t e d pyrite. The f i n e - s i z e wet c o a l p r o d u c t w i l l t h e n b e t r e a t e d b y a c h e m i c a l p r o c e s s t h a t w i l l remove s u f f i c i e n t o r g a n i c and r e maining p y r i t i c s u l f u r t o p r o v i d e an e n v i r o n m e n t a l l y a c c e p t a b l e f i n a l product. Dewatering. Hot S u r f a c t a n t S o l u t i o n A s D e w a t e r i n g A i d ( 9 ) . A p r i n c i p a l area of c o a l preparation research i n v o l v e s dewatering. M o i s t u r e r e m o v a l c a n b e a c c o m p l i s h e d by m e c h a n i c a l m e t h o d s , c h e m i c a l t r e a t m e n t , o r t h e r m a l d r y i n g . C o a l f i n e r t h a n 28 mesh i s t h e most d i f f i c u l t s i z e t o d e w a t e r a n d i s n o r m a l l y f i l t e r e d and t h e n , when n e c e s s a r y , t h e r m a l l y d r i e d . Some e a r l y r e s e a r c h w o r k i n o u r l a b o r a t o r y h a s s u g g e s t e d t h a t t h e u s e o f s u r f a c t a n t s d u r i n g t h e vacuum f i l t r a t i o n c y c l e w i l l i n c r e a s e t h e amount o f w a t e r removed. The t e c h n i q u e c o n s i s t s o f p o u r i n g a c o a l s l u r r y o n t o a m o d i f i e d f i l t e r l e a f a p p a r a t u s and washing t h e f i l t e r cake w i t h a s u r f a c t a n t s o l u t i o n d u r i n g t h e a i r drying cycle. The e f f i c i e n c y o f t h e p r o c e s s depends o n t h e amount of s u r f a c t a n t i n t h e wash w a t e r and o n t h e t e m p e r a t u r e o f t h e wash water. I t i s p o s s i b l e t o i m p r o v e on t h e r e s u l t s b y h e a t i n g t h e washed f i l t e r c a k e s w i t h s t e a m . U s i n g t h i s t e c h n i q u e , t h e m o i s t u r e c o n t e n t o f s l u r r i e s made w i t h m i n u s 35-mesh c o a l c o n t a i n i n g a b o u t 2 5 % minus 325-mesh m a t e r i a l was r e d u c e d t o a b o u t 1 0 % . I n c o n t r a s t , u n t r e a t e d f i l t e r cakes c o n t a i n e d about 19% m o i s t u r e .

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S u r f a c e Phenomena i n C o a l D e w a t e r i n g . An i n v e s t i g a t i o n t o i m p r o v e m e c h a n i c a l methods f o r d e w a t e r i n g f i n e c o a l t o m i n i m i z e t h e need f o r t h e r m a l d r y i n g i s b e i n g c a r r i e d o u t u n d e r a g r a n t w i t h Syracuse U n i v e r s i t y . B l a c k Water S t u d i e s . Treatment of b l a c k waters from c o a l p r e p a r a t i o n p l a n t s i s c o m p l i c a t e d by t h e h e t e r o g e n e o u s n a t u r e o f t h e w a t e r s and by t h e l a c k o f i n f o r m a t i o n on t h e b e h a v i o r o f r e l a t i v e l y s i m p l e systems. T h i s water c o n s i s t s of m i x t u r e s of f i n e c o a l , c l a y m i n e r a l s , q u a r t z , c a l c i t e , p y r i t e , and o t h e r m i n e r a l p a r t i c l e s d i s p e r s e d i n water. E f f e c t i v e treatment of the e f f l u e n t s must be c a r r i e d o u t r e g a r d l e s s o f w h e t h e r t h e w a t e r i s t o be r e u s e d o r d i s c h a r g e d . Under a g r a n t , t h e P e n n s y l v a n i a S t a t e U n i v e r s i t y i s i n v e s t i g a t i n g the treatment of b l a c k water from c o a l p r e p a r a t i o n p l a n t s by a f l o c c u l a t i o n p r o c e s s . R e f u s e Pond S u r v e y . In coal preparation plants u t i l i z i n g wet c l e a n i n g m e t h o d s , t h e f i n e c o a l r e f u s e m a t e r i a l c o n s t i t u t e s a b o u t 10% o f t h e t o t a l r e f u s e m a t e r i a l and i s d i s c h a r g e d i n s u s p e n s i o n e i t h e r as t a i l i n g s from the f r o t h f l o t a t i o n p r o c e s s or a s wet f i n e s t a k e n d i r e c t l y f r o m t h e c o a r s e c o a l w a s h e r y c i r c u i t s . The U n i v e r s i t y o f A l a b a m a c u r r e n t l y has a g r a n t f r o m t h e B u r e a u t o s u r v e y e x i s t i n g c o a l w a s t e ponds i n A l a b a m a t o d e t e r m i n e the l o c a t i o n of t h e wastes, the approximate q u a n t i t y of c o a l i n e a c h w a s t e p o n d , and t h e p o t e n t i a l r e c o v e r y o f t h e c o a l b a s e d on w a s h a b i l i t y t e s t s of r e p r e s e n t a t i v e samples of the waste. R e f u s e Pond S t a b i l i z a t i o n S t u d y . A l t h o u g h r e f u s e ponds c o n t i n u e t o be u s e d f o r t a i l i n g s d i s p o s a l , o t h e r c o n s i d e r a t i o n s s u c h as g r o u n d and s u r f a c e w a t e r p o l l u t i o n , l a c k o f s u i t a b l e t e r r a i n , and e n v i r o n m e n t a l r e s t r i c t i o n s may r e n d e r t h e p o n d i n g method t o t a l l y u n a c c e p t a b l e o r p r o h i b i t i v e l y e x p e n s i v e i n t h e future. Under a c o n t r a c t j u s t s i g n e d w i t h t h e Dravo L i m e Co., t h e c r i t i c a l p a r a m e t e r s f o r l a n d f i l l - t y p e d i s p o s a l w i l l be e s t a b l i s h e d by d e t e r m i n i n g t h e e n g i n e e r i n g p r o p e r t i e s and t h e p h y s i c a l and chemical c h a r a c t e r i s t i c s a f f e c t i n g s t a b i l i z a t i o n f o r t y p i c a l samples o f p r e p a r a t i o n p l a n t wastes from t h e t r e a t m e n t of e a s t e r n bituminous coals. C a l c i l o x a d d i t i v e , a Dravo-developed product, w i l l be one o f t h e p r i n c i p a l s t a b i l i z i n g a g e n t s u s e d i n t h i s study. L i g n i t e Upgrading. L i g n i t e d e p o s i t s i n the North DakotaM o n t a n a r e g i o n r e p r e s e n t one o f t h e l a r g e s t f o s s i l f u e l r e s e r v e s i n the United States. However, t h e u t i l i z a t i o n o f t h i s f u e l has b e e n l i m i t e d by i t s h i g h i n h e r e n t m o i s t u r e and i t s o f t e n h i g h s o d i u m c o n t e n t . L i g n i t e c o n t a i n s a b o u t 38% m o i s t u r e , and b e c a u s e of t h i s h i g h m o i s t u r e c o n t e n t , the market a r e a f o r l i g n i t e i s l i m i t e d t o a b o u t a 3 0 0 - m i l e r a n g e . Beyond t h i s d i s t a n c e , t h e c o s t of d e l i v e r e d B t u s exceeds t h a t of h i g h e r rank c o a l s . 1

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R e d u c i n g m o i s t u r e c o n t e n t t o 10% o r l e s s a t r e a s o n a b l e c o s t s w o u l d make t h i s l o w - s u l f u r c o a l c o m p e t i t i v e o v e r a much w i d e r market a r e a . Other problems a s s o c i a t e d w i t h t h e h i g h m o i s t u r e content of l i g n i t e a r e f r e e z i n g i n r a i l r o a d c a r s d u r i n g c o l d w e a t h e r and s l a c k i n g upon e x p o s u r e t o a i r , w h i c h c a u s e s d u s t p o l l u t i o n p r o b lems. L i g n i t e i s a l s o e x t r e m e l y r e a c t i v e t o w a r d o x y g e n and i s thus s u s c e p t i b l e t o spontaneous combustion. The s o d i u m c o n t e n t o f l i g n i t e v a r i e s w i d e l y and may be a s h i g h a s 1.2%. L i g n i t e c o n t a i n i n g l e s s t h a n 0.3% s o d i u m c a n be f i r e d w i t h o u t d i f f i c u l t y w h i l e h i g h e r percentages o f sodium c a u s e b o i l e r t u b e f o u l i n g , r e d u c e d e f f i c i e n c i e s , and e x c e s s i v e downtime t o remove a s h d e p o s i t s . The s o d i u m c o n t e n t o f l i g n i t e c a n be r e d u c e d b y i o n e x c h a n g e u s i n g m e t a l s a l t s w h i c h s u p p l y c a t i o n s t h a t a r e exchangeable w i t h sodium; t h e i r e f f e c t i v e n e s s depends upon t h e s i z e o f t h e l i g n i t e p a r t i c l e and t h e c o n tact time. The g o a l o f o u r l i g n i t e - u p g r a d i n g p r o g r a m i s t o p r o d u c e a f i n a l p r o d u c t c o n t a i n i n g l e s s t h a n 1 0 % m o i s t u r e and 0.3% s o d i u m . C r u s h e d r a w l i g n i t e w i l l be p r o c e s s e d i n a n i o n - e x c h a n g e v e s s e l where t h e s o d i u m c o n t e n t w i l l be r e d u c e d t o a n a c c e p t a b l e l e v e l . The i o n - e x c h a n g e p r o d u c t w i l l be d e w a t e r e d , p e l l e t i z e d , and h e a t d r i e d t o the d e s i r e d moisture content. This f i n a l product w i l l be a w e l l compacted w a t e r - r e s i s t a n t p e l l e t w h i c h w i l l n o t combust s p o n t a n e o u s l y and w i l l h a v e s u f f i c i e n t m e c h a n i c a l s t r e n g t h t o r e s i s t b r e a k a g e d u r i n g h a n d l i n g and s t o r a g e . Equipment Performance S t u d i e s . A s i g n i f i c a n t p a r t o f t h e B u r e a u ' s p r o g r a m f o r many y e a r s h a s b e e n equipment p e r f o r m a n c e evaluations. These s t u d i e s p r o v i d e t h e n e c e s s a r y i n f o r m a t i o n f o r c o a l p r e p a r a t i o n p l a n t o p e r a t o r s and equipment d e s i g n e r s t o s e l e c t and recommend e x i s t i n g c o a l w a s h e r s . I n t h i s study, o n l y two t y p e s o f c o a l - w a s h i n g e q u i p m e n t r e m a i n t o be e v a l u a t e d : j i g w a s h e r s , t o be c o m p l e t e d by t h e end o f 1978, and f r o t h f l o t a t i o n c e l l s , t o be c o n c l u d e d i n 1981. At t h i s time, an e v a l u a t i o n o f t h e performance of a Batac j i g i s underway. E a r l y i n 1978, a s t u d y w i l l b e g i n c o v e r i n g t h e p r i n c i p a l p i e c e s o f c o a l d e w a t e r i n g and d r y i n g e q u i p m e n t . A l l o f t h e s e s t u d i e s w i l l b e done by c o n t r a c t . Each i s s c h e d u l e d t o t a k e a p p r o x i m a t e l y 3 y e a r s . S c r e e n s , c o n t r i f u g e s , vacuum and p r e s s u r e f i l t e r s , and f i n a l l y t h e r m a l d r y e r s w i l l be e v a l u a t e d . Trace Elements. There i s an a c u t e awareness t h a t t r a c e elements i n c o a l might c o n t r i b u t e s u b s t a n t i a l q u a n t i t i e s o f p o t e n t i a l l y hazardous m a t e r i a l s t o t h e environment. Since c e r t a i n t r a c e elements c o n c e n t r a t e s e l e c t i v e l y i n p a r t i c u l a r s p e c i f i c g r a v i t y f r a c t i o n s o f raw c o a l , r e d u c t i o n o f t h e m i n e r a l m a t t e r may c a r r y t h e c o n c u r r e n t b e n e f i t o f r e d u c i n g t h e t r a c e e l e m e n t concentration i n the clean coal.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

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The B u r e a u o f M i n e s r e c e n t l y c o m p l e t e d a w a s h a b i l i t y s t u d y (10) s h o w i n g t h e t r a c e e l e m e n t c o n t e n t s o f v a r i o u s s p e c i f i c g r a v i t y f r a c t i o n s f o r 10 c o a l s a m p l e s c o l l e c t e d f r o m v a r i o u s U.S. c o a l producing regions. R e l i a b l e a n a l y t i c a l methods w e r e d e v e l o p e d t o d e t e r m i n e cadmium, chromium, c o p p e r , f l u o r i n e , m e r c u r y , manganese, n i c k e l , and l e a d i n t h e w h o l e c o a l s and t h e v a r i o u s s p e c i f i c g r a v i t y f r a c t i o n s of the c o a l s . Most o f t h e t r a c e e l e m e n t s of i n t e r e s t c o n c e n t r a t e d i n t h e h e a v i e r s p e c i f i c g r a v i t y f r a c t i o n s of the c o a l , i n d i c a t i n g t h a t they are a s s o c i a t e d w i t h m i n e r a l matter; removal of t h i s m a t e r i a l w o u l d s i g n i f i c a n t l y r e d u c e t r a c e e l e m e n t s up t o 88%. I n a r e l a t e d , but g r e a t l y expanded, e f f o r t , the Bureau, t h r o u g h EPA, i s a b o u t t o f u n d a p r o g r a m w i t h B i t u m i n o u s C o a l R e s e a r c h . The o b j e c t i v e s o f t h i s p r o j e c t a r e — (1) To p r e p a r e a c o m p r e h e n s i v e s t a t e - o f - t h e - a r t assessment of the f a t e of t r a c e elements i n c o a l m i n i n g , p r e p a r a t i o n , t r a n s p o r t a t i o n , and u t i l i z a t i o n ; and (2) To d e t e r m i n e t h e e f f e c t o f c o a l c l e a n i n g on t r a c e elements. Computer S i m u l a t i o n . To a s s i s t i n t h e p r e d i c t i o n o f f u l l s c a l e p r e p a r a t i o n p l a n t o p e r a t i o n , a computer s i m u l a t i o n program i s b e i n g developed under c o n t r a c t w i t h the U n i v e r s i t y of P i t t s burgh (11). The s t a n d a r d p r e d i c t i o n o f p r o d u c t q u a l i t y ( s u c h as a s h , s u l f u r , B t u , and y i e l d ) i s c a l c u l a t e d b a s e d on t h e e x t e n s i v e equipment performance d i s t r i b u t i o n d a t a o b t a i n e d from p r e v i o u s U.S. B u r e a u o f M i n e s i n v e s t i g a t i o n s . S e v e r a l o t h e r f e a t u r e s , t h o u g h , a r e more n o v e l and i n c l u d e t h e m a t h e m a t i c a l m o d e l i n g o f t h e r o t a r y b r e a k e r , o t h e r c r u s h e r s , and b o t h wet and d r y s c r e e n s . The o v e r a l l c a p a b i l i t y o f t h e computer p r o g r a m i s s u c h t h a t a b u i l d - y o u r - o w n p r e p a r a t i o n p l a n t c a n be s i m u l a t e d . A l l i e d t o t h i s work i s a study b e i n g conducted f o r the Bureau by t h e H o f f m a n - M u n t n e r C o r p o r a t i o n . The i n f o r m a t i o n g e n e r a t e d under t h i s c o n t r a c t w i l l c o n s t i t u t e the economic s u b r o u t i n e f o r the t o t a l computer s i m u l a t i o n program. M

n

New F a c i l i t y . I n t h e U n i t e d S t a t e s t h e r e i s no a v a i l a b l e f u l l y i n t e g r a t e d d e m o n s t r a t i o n - t y p e f a c i l i t y f o r t e s t i n g a new c o a l washing t e c h n i q u e , flowscheme, or p i e c e of equipment. Cons e q u e n t l y , a s i g n i f i c a n t t i m e l a p s e e x i s t s between development of new e q u i p m e n t and t e c h n i q u e s and t h e i r a c c e p t a n c e by t h e c o a l industry. To a l l e v i a t e many o f t h e p a s t p r o b l e m s o f i n t r o d u c i n g new technology to the i n d u s t r y , a c e n t r a l c o a l p r e p a r a t i o n process d e v e l o p m e n t f a c i l i t y has b e e n d e s i g n e d . T h i s w i l l p e r m i t u n b i a s e d e n g i n e e r i n g d a t a t o be s c a l e d up r e a d i l y t o f u l l - s i z e c o m m e r c i a l coal preparation plant operation. Moreover, the expense of e v a l u a t i n g p r o c e s s e s t h a t p r o v e t o be o f l i m i t e d v a l u e t o t h e i n d u s t r y w i l l be r e d u c e d g r e a t l y .

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The p l a n t w i l l have a n o m i n a l c a p a c i t y o f 10-25 t o n s p e r h o u r o f r a w c o a l , d e p e n d i n g on t h e f l o w s c h e m e u s e d . P r o c e s s f l e x i ­ b i l i t y i s a prime design r e q u i s i t e . New c r u s h i n g , s c r e e n i n g , d e w a t e r i n g , and c l e a n i n g e q u i p m e n t and c o a l w a s h i n g c i r c u i t s w i l l be e v a l u a t e d . T h i s p l a n t w i l l be used t o p r o c e s s c o a l s from d i f f e r e n t a r e a s a n d w i l l p r o v i d e optimum o p e r a t i n g c o n d i t i o n s needed t o p r o d u c e a c o a l o f a c c e p t a b l e s u l f u r , a s h , and t r a c e element c o n t e n t . An a d d i t i o n a l f u n c t i o n o f t h e d e m o n s t r a t i o n p l a n t w i l l b e t o p r o d u c e t o n l o t s o f s p e c i f i c a t i o n c o a l f o r com­ b u s t i o n t e s t i n g , s t a c k gas s c r u b b i n g work, o r f e e d s t o c k t o c o a l conversion processes. This b r i e f overview of c o a l preparation research a t the F e d e r a l B u r e a u o f M i n e s shows a w i d e s p e c t r u m o f i n t e r e s t i n p h y s i c a l , a s w e l l a s c h e m i c a l , c o a l p r e p a r a t i o n . As t h e N a t i o n g i v e s i n c r e a s i n g a t t e n t i o n t o e n e r g y - r e l a t e d problems, t h e pace of these c o a l p r e p a r a t i o n r e s e a r c h e f f o r t s i s l i k e l y t o accelerate.

Literature Cited

1. Deurbrouck, A. W., Jacobsen, P. S., "Coal Cleaning--State-of the-Art," Coal and Environmental Technical Conference and Equipment Exposition, Louisville, Ky., Oct. 22-24, 1974. 2. Cavallaro, J. Α., Johnston, M. T., Deurbrouck, A. W., "Sulfur Reduction Potential of the Coals of the United States," BuMines RI 8118, 1976, 323 pages. 3. Hucko, R. E., Cavallaro, J. Α., "Effect of Coal Preparation on Northern Appalachian Reserves," 4th National Conference on Energy and the Environment, American Institute of Chemical Engineers, Cincinnati, Ohio, Oct. 3-7, 1976, pp. 307-316. 4. Killmeyer, R. P., Jr., "State-of-the-Art of Coal Cleaning and Recent Developments in Equipment and Circuits," Third Kentucky Coal Refuse Disposal and Utilization Seminar, Pineville, Ky., May 11-12, 1977. 5. Hucko, R. E., Deurbrouck, A. W., "Overview of the U.S. Bureau of Mines Coal Cleaning Program," Coal Contaminant/Removal Technology Conference, Research Triangle Park, N.C., Apr. 27-28, 1977. 6. Miller, K. J., "Flotation of Pyrite From Coal," U.S. Patent No. 3807557, Apr. 30, 1974. 7. Baker, A. F., Miller, K. J., Deurbrouck, A. W., "Desulfuriza­ tion of Coal by Froth Flotation," Int. Coal Prep. Cong., Paris, France, March 1973, Paper 27E, 13 pp.; Available for consultation at the Bureau of Mines Coal Preparation and Analysis Laboratory, Bruceton, Pa. 8. Hoffman, L., Aresco, S. J., Holt, E. C., Jr., "Engineering/ Economic Analyses of Coal Preparation WithSO Cleanup Processes for Keeping Higher Sulfur Coals in the Energy Market," NCA/BCR Coal Conference and Expo III, Louisville, Ky., Oct. 19-21, 1976. 2

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

4.

CAVALLARO

AND

DEURBROUCK

Coal

Preparation

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9. Baker, A. F., Deurbrouck, A. W., "Hot Surfactant Solution as Dewatering Aid During Filtration," 7th Int. Coal Prep. Cong., Sydney, Australia, May 23-28, 1976. 10. Cavallaro, J. Α., Gibbon, G. Α., Hattman, Ε. Α., Schultz, H., Deurbrouck, A. W., "A Washability and Analytical Evaluation of Potential Pollution From Trace Elements in Coal," Joint EPA/Bureau report, not yet published. 11. Gottfried, B. S., Jacobsen, P. S., "A General Distribution Curve for Characterizing the Performance of Coal Cleaning Equipment," BuMines RI 8238, to be published in 1977.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

5 Chemical Comminution: A Process for Liberating the Mineral Matter from Coal

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch005

PHILIP H. HOWARD and RABINDER S. DATTA Syracuse Research Corp., Syracuse, NY 13210 Conventional coal preparation consists of mechanical size reduction, which liberates the pyritic sulfur and other mineral matter, followed by a separation step, the cost of which depends upon the size consist of the crushed coal. In general, as the coal size consist decreases, the amount of mineral matter liberated and the cost of separation increase. Physical coal cleaning processes are not able to liberate organic sulfur, and, therefore, the organic sulfur concentration places an upper limit on the amount of sulfur that can be removed. Chemical comminution provides a unique way of crushing coal for mineral matter liberation. Instead of mechanical size reduction, the coal is treated with a chemical (usually ammonia gas or a concentrated aqueous ammonia solution), resulting in selective breakage which appears to occur along the bedding planes and along the mineral matter (e.g., pyrite) and maceral boundaries. Washability comparisons of mechanically crushed and chemically comminuted coal samples have indicated that, at a given size consist, more liberation of pyritic sulfur and comparable liberation of ash are possible with chemical comminution. Figures 1, 2, and 3 provide a comparison of typical mechanical and chemical breakage and liberation. The recoveries noted in Figures 2 and 3 only apply to +100 mesh product, and, therefore, the -100 mesh material should be considered when calculating recoveries based upon feed. Intermsof decreasing size consist (Figure 1), the following order is found: 1 1/2" top size ROM > c h e m i c a l l y f r a c t u r e d > 3/8" t o p s i z e m e c h a n i c a l l y c r u s h e d > 14 mesh t o p s i z e m e c h a n i c a l l y c r u s h e d . The same o r d e r i s f o u n d f o r t h e a s h v s . r e c o v e r y c u r v e s i n F i g u r e 2. I n c o n t r a s t , t h e t o t a l s u l f u r v s . r e c o v e r y c u r v e s ( F i g u r e 3) d e m o n s t r a t e t h a t c h e m i c a l f r a c t u r e ( o n l y 4.53% i s < 100 mesh) l i b e r a t e s c o n s i d e r a b l y more p y r i t i c s u l f u r t h a n m e c h a n i c a l c r u s h i n g e v e n t o -14 mesh ( 2 1 . 9 % i s < 100 mesh). S i m i l a r r e s u l t s have been f o u n d w i t h R e d s t o n e , P i t t s b u r g h , and Upper F r e e p o r t seam c o a l s (1,2,3) a n d w i t h some Iowa c o a l s ( 4 ) . K e l l e r and S m i t h (_5) h a v e r e p o r t e d t h a t g r e a t e r s u l f u r l i b e r a t i o n does n o t o c c u r

58

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch005

Figure 1.

Size consist of Illinois No. 6 coal samples (Franklin County, IL)

Figure 2. Ash vs. recovery curves comparing the 3-hr chemical comminution to the mechanical crushing of the Illinois No. 6 seam coal sample (Franklin County, IL)

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

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w i t h c h e m i c a l f r a c t u r i n g but they d i d not c o n s i d e r y i e l d s i n t h e i r comparisons ( 6 ) . The f a c t t h a t c h e m i c a l c o m m i n u t i o n c a n l i b e r a t e more o f t h e p y r i t i c s u l f u r w i t h o u t g r i n d i n g t o s m a l l s i z e s has c o n s i d e r a b l e economic b e n e f i t s . Although, a t t h i s stage i n the development, i t i s d i f f i c u l t to estimate the exact c o s t s of a c o a l p r e p a r a t i o n f l o w s h e e t u s i n g c h e m i c a l c o m m u n i t i o n as t h e s i z e r e d u c t i o n m e t h o d , some p r e l i m i n a r y e s t i m a t e s h a v e b e e n d e v e l o p e d ( 3 ) . The t o t a l c a p i t a l and o p e r a t i n g c o s t s f o r t h e c h e m i c a l t r e a t m e n t a l o n e u s i n g ammonia v a p o r , u n d e r c o n d i t i o n s shown t o be t e c h n i c a l l y f e a s i b l e i n t h e l a b o r a t o r y , v a r y f r o m $1.00 t o $1.50 per ton of c o a l product. Using r e l a t i v e l y inexpensive density s e p a r a t i o n t e c h n i q u e s , f e a s i b l e b e c a u s e o f t h e s m a l l amount o f f i n e s produced i n the c h e m i c a l f r a g m e n t a t i o n s t e p , would b r i n g t h e t o t a l c o s t f o r p r o d u c i n g c l e a n c o a l t o b e t w e e n $2.50 - $3.00 per ton of product. This i s very competitive with other processes c u r r e n t l y being considered f o r producing clean c o a l . I t i s e n v i s a g e d t h a t t h e c h e m i c a l l y comminuted p r o d u c t a f t e r c l e a n i n g w i l l c o n t a i n 80-90% l e s s p y r i t i c s u l f u r and 50-60% l e s s a s h , a n d , i n a p p r o x i m a t e l y 30-40% o f t h e N o r t h e r n A p p a l a c h i a n seam c o a l s , w i l l meet EPA new s o u r c e e m i s s i o n s t a n d a r d s . Because of the commercial s i g n i f i c a n c e of c h e m i c a l comminution, the e f f e c t s of d i f f e r e n t r e a c t i o n c o n d i t i o n s have b e e n s t u d i e d p r e l i m i n a r i l y t o p r o v i d e some i n s i g h t i n t o t h e mechanism o f t h e phenomena. The a v a i l a b l e i n f o r m a t i o n i s p r e s e n t e d i n t h e f o l l o w i n g s e c t i o n s , and f u r t h e r i n f o r m a t i o n i s being developed. E q u i p m e n t and

Procedures

The p r o c e d u r e s u s e d t o c h e m i c a l l y comminute 100 l b s . s a m p l e s ( F i g u r e s 1, 2, and 3) a r e d e s c r i b e d e l s e w h e r e ( 3 ) . S m a l l e r s a m p l e s were comminuted i n t h e a p p a r a t u s d e p i c t e d i n F i g u r e 4. U n l e s s i n d i c a t e d , t h e s m a l l e r c o a l s a m p l e s were f l o a t e d a t 1.6 s p e c i f i c g r a v i t y t o remove l a r g e p i e c e s o f m i n e r a l m a t t e r and t h e n c l o s e l y s i z e d ( e . g . , 3/4" χ 1/4") so t h a t t h e f r a g m e n t a t i o n r a t e s c o u l d be compared. The o p e r a t i o n of s m a l l bomb a p p a r a t u s i s o u t l i n e d i n P r o c e d u r e A. The f r a g m e n t a t i o n r a t e s u n d e r d i f f e r e n t c o n d i t i o n s o r w i t h d i f f e r e n t c o a l s w e r e compared i n two ways. One way was t o compare t h e w e i g h t p e r c e n t o f t h e v a r i o u s c o a l s a m p l e s t h a t p a s s e d 5 mesh. The o t h e r method c o n s i s t e d o f p l o t t i n g t h e s c r e e n a n a l y s i s o f t h e c o a l s a m p l e s on a R o s i n Rammler g r a p h and c o m p a r i n g t h e a b s o l u t e s i z e c o n s t a n t ( x j . The a b s o l u t e s i z e c o n s t a n t i s t h e s i z e where 36.79% o f t h e c o a l p a r t i c l e s a r e r e t a i n e d on t h e s c r e e n . U s i n g t h e a b s o l u t e s i z e c o n s t a n t f o r comparison r e q u i r e s t h a t the s l o p e of the s i z e d i s t r i b u t i o n r e m a i n a p p r o x i m a t e l y c o n s t a n t . W i t h c h e m i c a l l y comminuted s a m p l e s , a c o n s t a n t s l o p e has b e e n o b s e r v e d .

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

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Liberation

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M i c r o s c o p i c e x a m i n a t i o n o f c h e m i c a l l y comminuted c o a l has b e e n c o n d u c t e d by G r e e r (7) o f Iowa S t a t e U n i v e r s i t y u s i n g a s c a n n i n g e l e c t r o n m i c r o s c o p e . The r e s u l t s d e m o n s t r a t e d t h a t f r a g m e n t a t i o n f r o m c h e m i c a l t r e a t m e n t was s t r o n g l y c o n t r o l l e d by m a c e r a l b o u n d a r i e s and o t h e r d e p o s i t s w i t h i n t h e m a t e r i a l s u c h as p y r i t e b a n d s . The a b o v e r e s u l t d e m o n s t r a t e s t h e s e l e c t i v e b r e a k a g e t h a t o c c u r s w i t h c h e m i c a l c o m m i n u t i o n and e x p l a i n s why p y r i t e i s l i b e r a t e d d u r i n g chemical treatment without excessive s i z e r e d u c t i o n . However, t h e d i f f e r e n c e b e t w e e n s u l f u r and a s h l i b e r a t i o n ( F i g u r e s 2 and 3) has n o t b e e n d e t e r m i n e d . Further pétrographie s t u d i e s o f t h i s e f f e c t a r e a n t i c i p a t e d . Effective

Chemicals

A l t h o u g h a number o f c h e m i c a l s h a v e some c o m m i n u t i o n a b i l i t y ( 8 ) , the c h e m i c a l s t h a t appear to have the g r e a t e s t e f f e c t a r e ammonia (gas and a n h y d r o u s and h y d r o u s l i q u i d ) and methanol. T h e s e compounds f a l l i n a c l a s s o f c h e m i c a l s c o n t a i n i n g a n o n b o n d i n g p a i r o f e l e c t r o n s ( o x y g e n and n i t r o g e n compounds) w h i c h s w e l l (9,10) and d i s s o l v e (10) c o a l a t a m b i e n t t e m p e r a t u r e s . A l t h o u g h s w e l l i n g s t u d i e s have not been conducted by u s , v e r y l i t t l e c o a l (< 0.1%) was d i s s o l v e d by e i t h e r m e t h a n o l o r l i q u i d a n h y d r o u s ammonia. The s w e l l i n g e f f e c t , w h i c h has b e e n o b s e r v e d w i t h m e t h a n o l - t r e a t e d c o a l by Bangham and Maggs ( 9 ) , may c a u s e t h e f r a g m e n t a t i o n w h i c h o c c u r s d u r i n g chemical treatment. K e l l e r and S m i t h (5) h a v e s u g g e s t e d t h a t s o l v e n t s w e l l i n g i s t h e mechanism c a u s i n g t h e b r e a k a g e . However, t h e i r o n l y s u p p o r t o f t h i s c o n t e n t i o n was a t h e o r e t i c a l discussion. The f a c t t h a t c o a l does comminute w i t h g a s e o u s ammonia i s n o t e x p l a i n e d by t h i s t h e o r y ( 6 ) . A n o t h e r a n a l o g y b e t w e e n c o a l s o l v e n t s and c o a l c o m m i n u t a n t s i s a r e d u c t i o n i n e f f e c t as the s o l v e n t i s d i l u t e d w i t h water. Other s p e c i f i c s o l v e n t s m e n t i o n e d as good c o a l s o l v e n t s ( 1 0 ) , s u c h as n - p r o p y l a m i n e and p y r i d i n e , h a v e b e e n b r i e f l y e x a m i n e d . These c h e m i c a l s do c a u s e f r a g m e n t a t i o n b u t a r e n o t a s e f f e c t i v e as ammonia. S i n c e t h e s e c h e m i c a l s a r e l a r g e r i n m o l e c u l a r s i z e , i t i s p o s s i b l e t h a t m o l e c u l a r s i z e i s an i m p o r t a n t p a r a m e t e r f o r chemical comminution, e s p e c i a l l y i f p e n e t r a t i o n of the c o a l i s a rate-determining factor. E f f e c t of R e a c t i o n C o n d i t i o n s The f r a g m e n t a t i o n c a u s e d by c h e m i c a l t r e a t m e n t i s a f f e c t e d by s u c h p a r a m e t e r s as m o i s t u r e , p r e s s u r e , w a t e r c o n c e n t r a t i o n i n t h e c h e m i c a l , s t a r t i n g s i z e o f t h e c o a l , and p r e c o n d i t i o n i n g o f the c o a l before treatment. T h e s e e f f e c t s , u s i n g I l l i n o i s No. 6 seam c o a l a s an e x a m p l e , a r e i l l u s t r a t e d i n F i g u r e s 5, 6, 7, and

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch005

COAL

DESULFURIZATION

Igure 3. Sulfur vs. recovery curves comparing the 3-hr chemical comminution to the mechanical crushing of the Illinois No. 6 coal sample (Franklin County, IL)

Figure 4.

Small bomb apparatus.

Procedure given on

following page.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

5.

HOWARD

AND DATTA

Chemical Comminution Procedure A

P r o c e d u r e f o l l o w e d when p e r f o r m i n g t e s t s i n s m a l l p r e s s u r e v e s s e l s d e p i c t e d i n F i g u r e 4. At S t a r t :

C o v e r s removed f r o m Bombs © a n d © . P i p i n g on c o v e r s i n p l a c e up t o u n i o n s © a n d © .

D i p tube(Din p l a c e .

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch005

S t e p No. 1 2 3 4 5 6 7

W e i g h 300 gms. c o a l i n t o ® . C l o s e © w i t h c o v e r and a t t a c h p i p i n g t o © . E v a c u a t e (A) v i a c o n n e c t i o n a t © . Close valve© . C o o l down © w i t h d r y i c e a r o u n d i t . Add h y d r o u s o r a n h y d r o u s NH3 t o n e a r 1/2 f u l l . Close cover w i t h attached p i p i n g , v a l v e © o p e n , and t i g h t e n n u t s . Close valve© . I n s t a l l c o n n e c t i n g t u b i n g between © a n d © . Evacuate tubing through v a l v e © . Remove d r y i c e f r o m r o u n d © a n d add warm w a t e r t o c o n t a i n e r s © s o a s t o m a i n t a i n t e m p e r a t u r e a t 75°F. A l l o w p r e s s u r e t o b u i l d up i n © t o a c o n s t a n t amount, m a i n t a i n i n g w a t e r j a c k e t t e m p e r a t u r e a t 75°F. Open v a l v e s © a n d © , f o r c i n g c o n t e n t s f r o m ® t o © u n t i l p r e s s u r e i n © and © e q u i l i z e s . S t a r t t i m e r ( r e c o r d i n g t e m p e r a t u r e and p r e s s u r e ) , m a i n t a i n t e m p e r a t u r e o f w a t e r j a c k e t a t 75°F. Close valveffi). Disconnect © f r o m tubing a t © . 60 s e c . b e f o r e t h e d u r a t i o n o f t h e e x p e r i m e n t , remove w a t e r j a c k e t f r o m r o u n d © a n d c o o l © d o w n with dry ice. Vent © t o 0 p . s . i . g . through v a l v e s © a n d © . Remove c o v e r and s e p a r a t e l i q u i d f r o m s o l i d . Remove t h e r e s i d u a l NH i n c o a l by e l l u t r i a t i n g t h e sample w i t h b o i l i n g water i n an e l l u t r i a t i n g column. C o l l e c t s a m p l e , d r y , and p e r f o r m a p p r o p r i a t e analyses.

8 9 10 11 12

13 14

15 16

17 18 19

20 Note:

1. 2.

I n c a s e o f NH^ g a s t r e a t m e n t , t h e d i p t u b e © h a s t o be removed. F o r making hydrous known v o l u m e o f a n h y d r o u s NH^ i s added t o a known w e i g h t o f i c e . a

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch005

64

COAL

DESULFURIZATION

8. I l l i n o i s No. 6 seam c o a l i s v e r y s u s c e p t i b l e t o c h e m i c a l comminution, and, t h e r e f o r e , the r e s u l t s w i t h t h i s c o a l a r e not necessarily representative of other coals. F i g u r e 5 demonstrates the importance of evacuating the r e a c t o r before chemical treatment. The c o n t r a s t i n t h e e f f e c t o f e v a c u a t i o n b e t w e e n l i q u i d and g a s e o u s c o n d i t i o n s i s q u i t e a p p a r e n t . This effect has a l s o b e e n n o t i c e d w i t h o t h e r c o a l s , a l t h o u g h t h e y h a v e n o t been as d e m o n s t r a t i v e . F o r example, a l l t h e c o n d i t i o n s used i n F i g u r e 5 w o u l d h a v e no f r a c t u r i n g e f f e c t o n a P i t t s b u r g h seam c o a l t h a t was e x a m i n e d . F i g u r e 6 i l l u s t r a t e s t h e e f f e c t o f p r e s s u r e and w a t e r c o n t e n t and d e m o n s t r a t e s t h a t m e t h a n o l i s n o t a s e f f e c t i v e a c o m m i n u t i n g a g e n t a s even a d i l u t e ammonia-water s o l u t i o n . With gas t r e a t m e n t , i t a p p e a r s t h a t a l i t t l e m o i s t u r e i n t h e c o a l aids fracture. A l s o , when u s i n g g a s , a change o f p r e s s u r e f r o m 90 p s i g t o 120 p s i g h a s c o n s i d e r a b l e i m p a c t o n t h e amount o f breakage. D e t e r m i n a t i o n o f any t r e n d s w i t h t h e l i q u i d systems i s d i f f i c u l t b e c a u s e t h e p r e s s u r e was n o t h e l d c o n s t a n t . As m i g h t be e x p e c t e d , t h e i n i t i a l s i z e o f t h e c o a l b e f o r e t r e a t m e n t can e f f e c t t h e s i z e o f t h e t r e a t e d p r o d u c t . This effect i s i l l u s t r a t e d i n F i g u r e 7. As n o t e d p r e v i o u s l y ( F i g u r e 5 ) , e v a c u a t i o n b e f o r e t r e a t m e n t appears t o have a c o n s i d e r a b l e e f f e c t , e s p e c i a l l y w i t h gaseous treatment. E v a c u a t i o n a f t e r t r e a t m e n t a l s o appears t o have an e f f e c t ( F i g u r e 8) w h i c h may be c a u s e d by j u s t a d i f f e r e n c e i n r e a c t i o n t i m e , s i n c e r e a c t i o n i n t h e evacuated sample s h o u l d s t o p r a p i d l y w h i l e t h e u n e v a c u a t e d s a m p l e may c o n t i n u e t o r e a c t e v e n a f t e r t h e p r e s s u r e i s removed. E f f e c t o f C o a l Type The r e a c t i o n c o n d i t i o n s h a v e a c o n s i d e r a b l e i m p a c t on t h e amount o f b r e a k a g e t h a t o c c u r s w i t h d i f f e r e n t c o a l r a n k s ( F i g u r e 9 ) . G a s e o u s ammonia i s l e a s t a f f e c t e d by r a n k w h i l e l i q u i d ammonia e i t h e r a t e l e v a t e d o r a t a t m o s p h e r i c p r e s s u r e is strongly affected. The l i q u i d ammonia c o r r e l a t i o n b e t w e e n r a n k and c o m m i n u t i o n may be f o r t u i t o u s and c a u s e d i n s t e a d by d i f f e r e n c e s i n m i c r o o r macro p o r o s i t y , m a c e r a l c o n t e n t , c l e a t system, s w e l l i n g a b i l i t y ( 1 1 ) , m i n e r a l matter d i s t r i b u t i o n , o r perhaps other f a c t o r s . Chemical

Reactions

C h e m i c a l r e a c t i o n s b e t w e e n t h e ammonia and c o a l c o u l d h a v e an a d v e r s e e f f e c t on t h e r e c o v e r y o f t h e ammonia and o n t h e amount o f n i t r o g e n o x i d e s e m i t t e d when t h e c o a l i s c o m b u s t e d . T h e r e f o r e , t h e n i t r o g e n c o n t e n t o f c o a l b e f o r e and a f t e r ammonia t r e a t m e n t was d e t e r m i n e d f o r a v a r i e t y o f c o a l seams. The r e s u l t s presented i n Table I vary s l i g h t l y f o r d i f f e r e n t c o a l s , and t h e i n c r e a s e i n n i t r o g e n a p p e a r s t o be i n c o r r e l a t i o n w i t h a

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

5.

HOWARD

65

Chemical Comminution

AND DATTA

Comminution Conditions / \

30% N H O H . 3 Hours. 7 5 ° F . Atmospheric Pressure. Without Evacuation

A

30% N H O H . 3 Hours. 75° F. Atmospheric Pressure . With Evacuation

4

4

Original Sample Chemically Comminuted in Gaseous N H . 3 Hours. 7 5 ° F . Atmospheric Pressure. With Evacuation

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch005

3

Chemically Comminuted in Gaseous N H . 3 Hours. 7 5 ° F . Atmospheric Pressure. Without Evacuation 3

1000

10000 Size (Microns)

Figure 5.

Effect of preevacuation on chemical comminution of Illinois No. 6 coal

Ο

Coal Contained 5% Moisture. Treated with NH3 Gas. 120 psig. Alter Evacuation

φ

Coal Contained 5% Moisture. Treated with NH3 Gas. 90 psig. After Evacuation

X

Coal Oven (100°C) Dried.

A

50% N H and 50% H 0 Solution. 55 psig. 75° F

^

75% N H and 25% H 0 Solution. 105 ps.g. 75° F

Q

Methanol. Atmospheric Pressure. 75° F

Treated with NH3 Gas. 120 psig. After Evacuation 3

3

2

2

T i m e (Minutes)

Figure 6. Effect of reaction pressure and water content in the coal or comminuting agent on fragmentation of A in. X V4 in. samples of Illinois No. 6 coal. 3

Illinois Number 6, Liquid N H , - 3 0 ° C . Atmospheric Pressure 3

Ο 3/4" χ 1/4" X

T i m e (Minutes)

1 1/2" χ

3/4"

Figure 7. Effect of start­ ing size on chemical com­ minution of Illinois No. 6 seam coal

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

C O A L DESULFURIZATION

Ο

N H Gas. 120 ps.g. 7 5 ° F, No Evacuation After Treatment 3

X

-)

N H Gas. 120 ps.g. 7 5 ° F. Evacuation After Treatment 3

T i m e (Minutes)

Effect of evacuation after chemical treatment of Illinois No. 6 seam coal

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch005

Figure 8.

Δ

N H Liquid, 120 psig. 75° F

ο

N H Gas, 120 psig. 75° F

•

100% Liquid N H , - 3 3 ° F

3

3

3

Exposure Time 3hrs. Starting Size 1/2" χ 0

ANTH S. ANTH

LV

MV

H VA

HVB

SubC

RANK

Figure 9.

Effect of coal rank on the amount of breakage at various reaction conditions

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Numbers i n percent t o t a l

3

1.94 1.74

1.74

1,58

1.62

1.80

1.72

e l u t r i a t e d w i t h water at 100°C f o r 2 1/2 hr

1.71

1.69

1.96

1.75

1.94

1.58

e l u t r i a t e d w i t h water at 100°C f o r 1/2 h r

dried

air

1.39

1.21

0.98

1.25

e l u t r i a t e d w i t h water 100°C f o r 2 1/2 hr

1.37

1.15

1.21

0.97

1.44

20xl00M

1.20

8x20M

1,08

+8M

1.43

1.70

1.68

1.91

1.64 1.59

1.24

1.24

1.21

A i r Dried a t 100°C f o r 4 hr

1.16

1.22

1,21

-100M

A i r D r i e d a t 60°C and S i z e d

e l u t r i a t e d w i t h water 100°C f o r 1/2 h r

nitrogen.

240 min, 100% NH l i q u i d , atm. p r e s s . , -30°F

111inois No. 6, Franklin County, I L

1.12

1.21

air

dried

1.50

e l u t r i a t e d w i t h water a t 100°C, a i r d r i e d

240 min, 100% NH3 l i q u i d , atm. p r e s s . , -30°F

1.53

1.51

r i n s e d with d i l u t e HCl at 20°C, a i r d r i e d

1.43

30 rain, 100% NH liquid, 120 p s i g , 75°F

d r i e d , 60°C

Original ROM Sample

air

Treatment t o Remove Ammonia

Air Dried at 60°C Overnight

Nitrogen Content of Chemically Comminuted Coal

180 min, NH3 g a s , 120 p s i g , 75°F

Ammonia Treatment

Upper F r e e p o r t , Westmoreland County, PA

Pittsburgh, Green County, PA

Coal

Table I.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch005

1.69

1.69

1.94

1.26

1.37

1.20

A i r Dried a t 200°C f o r 2 hr

1.96

1.82

2.00

1.11

1.38

1.24

A i r Dried at 300°C f o r 1 hr

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch005

68

C O A L DESULFURIZATION

d e c r e a s e i n r a n k . No i n c r e a s e a p p e a r s t o t a k e p l a c e w i t h Upper F r e e p o r t seam c o a l , a s l i g h t i n c r e a s e ( 6 % ) w i t h P i t t s b u r g h seam c o a l , and a p p r o x i m a t e l y a 20% i n c r e a s e w i t h I l l i n o i s No. 6 seam c o a l when t h e s a m p l e i s a i r d r i e d . However, some o f t h e n i t r o g e n c a n be removed b y h o t w a t e r w a s h i n g . I n g e n e r a l , t h e +8 mesh p a r t i c l e s show a l o w e r i n c r e a s e i n n i t r o g e n t h a n t h e o t h e r sizes. The n a t u r e o f t h e c h e m i c a l r e a c t i o n t h a t may be t a k i n g p l a c e i s unknown, b u t t h e r e a r e f u n c t i o n a l g r o u p s ( e . g . , e s t e r s ) i n c o a l t h a t c o u l d f o r m n i t r o g e n compounds. W i t h I l l i n o i s No. 6 seam c o a l , t h e l o s s o f ammonia w o u l d s t i l l be s m a l l (4.4 l b s . ammonia p e r t o n o f t r e a t e d c o a l when a h o t w a t e r wash i s u s e d ) , and i t i s unknown w h e t h e r n i t r o g e n o x i d e s e m i s s i o n s w o u l d change. From t h e a b o v e r e s u l t s , i t c a n be s e e n t h a t c o n s i d e r a b l y more i n f o r m a t i o n i s n e c e s s a r y b e f o r e t h e mechanism o f c h e m i c a l comminution i s understood. Studies directed at a better u n d e r s t a n d i n g o f t h e phenomena and t h e e f f e c t i t h a s o n t h e c h e m i c a l l y t r e a t e d c o a l a r e p r e s e n t l y underway. Acknowledgements T h i s w o r k was p a r t i a l l y s u p p o r t e d 14-32-0001-1777.

by ERDA

Contract

Literature Cited

1. Datta, R.S., Howard, P.H., Hanchett, A., "Pre-Combustion Coal Cleaning Using Chemical Comminution," NCA/BCR Coal Conference and Expo III. Coal: Energy for Independence, Louisville, October 19-21, 1976. 2. Howard, P.H., Hanchett, Α., Aldrich, R.G., "Chemical Comminution for Cleaning Bituminous Coal," Clean Fuels from Coal Symposium II Papers, Institute of Gas Technology, Chicago, Ill., June 23-27, 1975. 3. Datta, R.S., Howard, P.H., Hanchett, Α., "Feasibility Study of Pre-combustion Coal Cleaning Using Chemical Comminution," FE-1777-4, Final Report ERDA Contract 14-32-0001-1777, Syracuse Research Corp., November 1976. 4. Min, S., Wheelock, T.D., "Cleaning High Sulfur Coal," NCA/BCR Coal Conference and Expo III. Coal: Energy for Independence, Louisville, October 19-21, 1976. 5. Keller, D.V., Jr., Smith, C.D., "Spontaneous Fracture of Coal," Fuel (1976), 55, 273-280. 6. Howard, P.H., Datta, R.S., Hanchett, Α., "Chemical Fracture of Coal for Sulfur Liberation," Fuel (1977), 56, 346. 7. Greer, R.T., "Coal Microstructure and the Significance of Pyrite Inclusions," Scanning Electr. Microscopy, Vol. I, Proceedings of the Workshop on Materials and Component Characterization/Quality Control with the SEM/STEM, IIT Research Institute, Chicago, Ill., March 1977.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

5. HOWARD AND DATTA

Chemical Comminution

69

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch005

8. Aldrich, R.G., Keller, D.V., Jr., Sawyer, R.G., "Chemical Comminution and Mining of Coal," U.S. Patent 3,815,826 (June 11, 1974) and 3,850,477 (November 26, 1974). 9. Francis, W., "Physical Considerations," Chapter XI in "Coal, Its Formation and Composition," 2nd ed., Edward Arnold, London, 1961. 10. Dryden, I.G.C., "Solvent Power for Coals at Room Temperature," Chem. Ind. (June 2, 1952), 502. 11. van Krevelen, D.W., "Chemical Structure and Properties of Coal. XVIII-Coal Constitution and Solvent Extraction," Fuel (1965), 44, 229.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

6 Use of the Flotation Process for Desulfurization of Coal

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch006

F. F. APLAN Mineral Processing Section, Pennsylvania State University, University Park, PA 16802

The flotation process is a method for desulfurizing fine coal whose time has come. The process has proven to be a great success in the beneficiation of a wide variety of metalliferous ores and industrial minerals, and currently, the United States has an installed capacity to treat about 1.7 million tons of ore per day. Unfortunately, coal processing has not participated in this growth in any major way. In the U.S. in 1973 only 14 million tons of clean coal were produced by the flotation process (1) . By comparison, in the same year approximately 400 million tons of coal were treated in preparation plants to produce 300 million tons of clean coal. This amount of coal produced by washing techniques was about half of the 600 million tons of the marketable coal produced in the U.S. that year. There are many reasons why coal flotation has not made a greater impact on the coal industry, but chief among them are the effectiveness of coarse cleaning processes (which treat particles of 1-5 in. top size), the low value of a ton of coal until recent years, the lack of an adequate research and development program to evaluate the process thoroughly, and, to some extent, inertia. To these reasons should be added the following shortcomings of the coal flotation process enumerated by Mitchell (2) in 1948: (1) (2) (3) (4) (5)

M a r k e t i n g problems w i t h t h e f i n e s , Cost of dewatering, I n d i f f e r e n t t e s t r e s u l t s i n removing s u l f u r , I n a b i l i t y t o make c l e a n s e p a r a t i o n s w i t h t h e f i n e r s i z e s , I n a b i l i t y t o clean s l u r r i e s containing a high percentage of c l a y . Two new f a c t o r s , w h i c h have come t o t h e f o r e w i t h i n t h e p a s t d e c a d e , have c a u s e d a s e r i o u s r e - e v a l u a t i o n o f t h e p r o c e s s i n c o a l preparation: t h e s h a r p l y i n c r e a s e d market value o f a t o n o f c o a l and e n v i r o n m e n t a l c o n s i d e r a t i o n s . The i n c r e a s e d c o a l p r i c e h a s l e d t o a g r e a t l y i n c r e a s e d e m p h a s i s on f i n e c o a l c l e a n i n g i n o r d e r to achieve a g r e a t e r y i e l d of combustible m a t e r i a l from a t o n o f raw c o a l . On t h e e n v i r o n m e n t a l f r o n t c o a l f l o t a t i o n h e l p s t o c l a r i f y t h e l a r g e q u a n t i t i e s o f w a t e r u s e d and r e c y c l e d i n t h e

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p r e p a r a t i o n p r o c e s s and i n t h e r e m o v a l o f p y r i t i c s u l f u r f r o m t h e coal. While f o r coarse c o a l , g r a v i t y concentration processes are very e f f i c i e n t , t h e i r f i n e c l e a n i n g counterparts are not n e a r l y as e f f e c t i v e i n e i t h e r c o a l r e c o v e r y o r i n p y r i t e r e m o v a l . The c o a l f l o t a t i o n process o f f e r s the p o t e n t i a l of overcoming both of t h e s e d e f e c t s f o r t h e t r e a t m e n t o f t h e f i n e , -28 mesh c o a l . In t h i s r e s p e c t i t c a n r e d u c e t h e s u l f u r c o n t e n t o f some c o a l s t o EPAa c c e p t a b l e l e v e l s o r , f o r h i g h e r s u l f u r c o a l s , can reduce the o v e r a l l s u l f u r c o n t e n t o f t h e c o a l s u c h t h a t t h e n e e d f o r f l u e gas d e s u l f u r i z a t i o n a t t h e power p l a n t c a n be m i n i m i z e d . Where a p p l i c a b l e , c o a l p r e p a r a t i o n t e c h n i q u e s c a n remove p y r i t i c s u l f u r f o r a f r a c t i o n o f t h e c o s t o f s u l f u r r e m o v a l by a f l u e gas s c r u b b i n g system. I n a r e c e n t a r t i c l e H o f f m a n e t a l . C3), have shown t h e e c o n o m i c p o t e n t i a l o f s u c h c o m b i n a t i o n c o a l p r e p a r a t i o n and f l u e gas d e s u l f u r i z a t i o n t e c h n i q u e s . The c o a l f l o t a t i o n p r o c e s s has b e e n d e t a i l e d i n t h e l i t e r a t u r e i n r e v i e w a r t i c l e s by A p l a n ( 4 ) , Brown ( 5 ) , and Zimmerman ( 6 ) . U n f o r t u n a t e l y , s i n c e the h i s t o r i c a l purpose of c o a l p r e p a r a t i o n has b e e n t o remove t h e h i g h - a s h c o n s t i t u e n t s , t h e l i t e r a t u r e does n o t c o n t a i n a g r e a t d e a l o f i n f o r m a t i o n on s u l f u r r e d u c t i o n by flotation. F o r t h i s r e a s o n , t h e M i n e r a l P r o c e s s i n g S e c t i o n a t The P e n n s y l v a n i a S t a t e U n i v e r s i t y s e v e r a l y e a r s ago embarked on a c o m p r e h e n s i v e p r o g r a m aimed a t u n d e r s t a n d i n g t h e f u n d a m e n t a l s o f the process, d e l i n e a t i n g the best c o n d i t i o n s f o r r e j e c t i n g p y r i t i c s u l f u r d u r i n g c o a l f l o t a t i o n , and e s t a b l i s h i n g a d a t a b a s e . T h i s c h a p t e r w i l l e m p h a s i z e t h a t work. G e n e r a l Methods of P y r i t e Removal T h e r e a r e t h r e e g e n e r a l methods t h a t may be u s e d t o r e j e c t p y r i t i c s u l f u r during coal f l o t a t i o n : (1) m u l t i p l e c l e a n i n g , (2) p y r i t e d e p r e s s i o n , and (3) c o a l d e p r e s s i o n w i t h c o n c u r r e n t f l o t a t i o n of the p y r i t e . The f i r s t p r o c e s s i s b a s e d on t h e a s s u m p t i o n t h a t c o a l i s e a s i l y f l o a t a b l e whereas p y r i t e i s not. I n t h i s c a s e any p y r i t e w h i c h f l o a t s w o u l d be c a u s e d by m e c h a n i c a l e n t r a p m e n t w i t h t h e floating coal. I t c o u l d t h u s be removed by r e p u l p i n g t h e f l o a t e d c o a l and r e p e a t i n g t h e f r o t h f l o t a t i o n p r o c e s s s e v e r a l t i m e s ; e a c h t i m e r e j e c t i n g some of t h e m e c h a n i c a l l y e n t r a p p e d p y r i t e p a r t i c l e s . The a s s u m p t i o n t h a t p y r i t e i s n o t f l o a t a b l e i s t r u e o n l y as a gross g e n e r a l i z a t i o n , s i n c e , i n p r a c t i c e , f i n e p y r i t i c s u l f u r o f t e n f l o a t s w i t h the c o a l . The f l o t a t i o n o f p y r i t e o c c u r s n o t o n l y by i t s e l f , b u t i t s f l o t a t i o n i s o f t e n e n c o u r a g e d by t h e e x i s t a n c e o f l o c k e d p y r i t e - c o a l p a r t i c l e s o r by t h e u s e o f an o i l y c o l l e c t o r f o r the f l o t a t i o n of the c o a l . Early-day ore f l o t a t i o n p r o c e s s e s , c i r c a 1905, u s e d f u e l o i l i n t h e f l o t a t i o n o f s u l f i d e minerals including pyrite. S t u d i e s by M i l l e r e t a l . (7) and more r e c e n t l y by Im (8) show t h a t t h e m u l t i p l e c l e a n i n g method i s n o t o n l y l a b o r i o u s but o f t e n not p a r t i c u l a r l y e f f e c t i v e . The f r o t h s p r i n k l i n g method, a l s o e v a l u a t e d by M i l l e r (9) i s a m u t a t i o n o f

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the m u l t i p l e c l e a n i n g p r o c e s s . P y r i t e d e p r e s s i o n d u r i n g c o a l f l o t a t i o n w o u l d a p p e a r t o be t h e most l o g i c a l a p p r o a c h t o t h e p r o b l e m e s p e c i a l l y i n v i e w o f t h e f a c t t h a t p y r i t e d e p r e s s i o n t e c h n i q u e s d u r i n g the f l o t a t i o n of c o p p e r , l e a d , n i c k e l , and z i n c s u l f i d e s a r e w e l l known ( 1 0 ) . In c o a l f l o t a t i o n use has been made of pH c o n t r o l , l i m e , s o d i u m c y a n i d e , s o d i u m s u l f i d e , h y d r o s u l f i d e and s u l f i t e , p o t a s s i u m d i c h r o m a t e , p o t a s s i u m p e r m a n g a n a t e , and f e r r o u s and f e r r i c s u l f a t e t o r e j e c t p y r i t e ( 4 ) . The c l a s s i c w o r k i n t h i s a r e a i s t h a t o f Y a n c e y and T a y l o r ( 1 1 ) , and more r e c e n t w o r k has b e e n done by M i l l e r (12). Zimmerman (13) d e m o n s t r a t e d t h a t t h e s u l f u r c o n t e n t o f c l e a n c o a l p r o d u c e d by f l o t a t i o n o f P i t t s b u r g h Seam c o a l d e c r e a s e s as t h e pH i s r a i s e d f r o m 4 t o 11. U n f o r t u n a t e l y , the r e c o v e r y o f c l e a n c o a l d e c r e a s e s as t h e pH i s i n c r e a s e d above pH 7. The p r a c t i c a l i t y o f t h e s i t u a t i o n i s t h a t none o f t h e s e t e c h n i q u e s a r e u s e d i n d u s t r i a l l y , and l a b o r a t o r y t e s t i n g o f t e n shows m e d i o c r e r e s u l t s a t b e s t . T r u l y , t h i s i s an a r e a where an expanded r e s e a r c h and d e v e l o p m e n t e f f o r t i s c l e a r l y n e e d e d . The t h i r d method o f p y r i t e r e j e c t i o n i s t h a t o f c o a l d e p r e s s i o n and has r e c e n t l y been t e s t e d by t h e U.S. B u r e a u o f M i n e s (14) i n a process c a l l e d the two-stage or reverse f l o t a t i o n process. I t i n v o l v e s a f i r s t - s t a g e (rougher) f l o t a t i o n of the c o a l to r e j e c t t h e b u l k o f t h e a s h - c o n t a i n i n g c o n s t i t u e n t s i n c l u d i n g much o f t h e pyrite. The r o u g h e r f r o t h i s t h e n s e n t t o a c l e a n e r c i r c u i t where a p r o p r i e t a r y d e p r e s s a n t ( A m e r i c a n Cyanamid R e a g e n t 633) i s added t o d e p r e s s t h e c o a l w h i l e a x a n t h a t e c o l l e c t o r and a f r o t h e r a r e added t o f l o a t p y r i t e f r o m t h e c o a l . The p r o c e s s has r a t h e r s t r i k i n g l y reduced the s u l f u r l e v e l of the c l e a n c o a l a l t h o u g h the p r o b l e m s o f e x c e s s i v e r e a g e n t u s e and c o s t and i n a d e q u a t e r e c o v e r y of c l e a n c o a l w i l l r e q u i r e a d d i t i o n a l study. T h e r e i s a need t o e v a l u a t e c o a l d e p r e s s i n g a g e n t s , and t h e s e s t u d i e s a r e p r e s e n t l y in progress (8). Response of P y r i t e i n C o a l F l o t a t i o n Systems Because of the d e a r t h of d a t a c o n c e r n i n g the response of p y r i t e i n a c o a l f l o t a t i o n c i r c u i t , t h e c u r r e n t p r o g r a m a t Penn S t a t e has f o c u s e d on e s t a b l i s h i n g a p r o p e r d a t a b a s e . F a c t o r s t o be c o n s i d e r e d i n a d d i t i o n t o t h e n a t u r e o f t h e c o a l a r e t h e amount and k i n d o f f r o t h e r , q u a n t i t y and t y p e o f c o l l e c t o r ( i f a n y ) , t y p e o f f l o t a t i o n c e l l , and o p e r a t i n g c o n d i t i o n s . The f o l l o w i n g r e p o r t on t h e e x p e r i m e n t a l p r o g r a m i n p r o g r e s s e v a l u a t e s many o f t h e s e factors. E x p e r i m e n t a l Methods. A l l of the work r e p o r t e d h e r e , e x c e p t t h a t i n t h e f i r s t f i g u r e , has b e e n done w i t h c l e a n c o a l f r o m t h e Lower K i t t a n n i n g o r P i t t s b u r g h Seam t o w h i c h 5% p u r i f i e d p y r i t e has b e e n added. R e c e n t w o r k has shown (15) t h a t p y r i t e s a m p l e s from d i f f e r e n t c o a l sources possess d i f f e r e n t f l o a t a b i l i t i e s (which, i n t u r n , are d i f f e r e n t from the f l o a t a b i l i t y of ore p y r i t e ) .

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T h e r e f o r e , t h e p y r i t e u s e d i n e a c h t e s t came f r o m t h e same seam as d i d t h e c o a l . T h i s p r o c e d u r e e l i m i n a t e s l o c k e d p a r t i c l e s so t h a t t h e p a t h o f t h e p y r i t e d u r i n g f l o t a t i o n c a n be a c c u r a t e l y t r a c e d , u n c o m p l i c a t e d by t h e i n t e r m e d i a t e r e s p o n s e o f p a r t i c l e s t h a t a r e p a r t c o a l and p a r t p y r i t e . O t h e r s t u d i e s a r e underway t o e v a l u a t e the response of l o c k e d p a r t i c l e s i n c o a l f l o t a t i o n systems. C o a l f r o m t h e Lower K i t t a n n i n g seam ( C a m b r i a C o u n t y , PA.) o r t h e P i t t s b u r g h seam ( F a y e t t e C o u n t y , PA.) was p u l v e r i z e d t o 100% -14 mesh, 90% -28 mesh, t o w h i c h -28 mesh p u r i f i e d p y r i t e f r o m e a c h r e s p e c t i v e seam was added. C o a r s e r p y r i t e was n o t added s i n c e R a s t o g i and A p l a n (16) have d e m o n s t r a t e d t h a t +28 mesh p y r i t e w i l l not f l o a t under the c o n d i t i o n s n o r m a l l y encountered i n f r o t h flotation. To i n s u r e t h a t s u r f a c e o x i d a t i o n d i d n o t i n f l u e n c e t h e r e s u l t s , t h e c o a l and p y r i t e s a m p l e s w e r e g r o u n d s h o r t l y b e f o r e flotation. The o l d e r s t y l e F a g e r g r e n l a b o r a t o r y f l o t a t i o n c e l l was u s e d , and t h e p u l p c o n c e n t r a t i o n was a b o u t 17% s o l i d s . The s p e c i f i c d a t a g i v e n i n t h i s r e p o r t w e r e drawn f r o m s t u d i e s on two d i f f e r e n t c o a l seams and t h u s a r e i n t e n d e d t o i l l u s t r a t e g e n e r a l p r i n c i p l e s r a t h e r t h a n t o s e r v e as a b a s i s f o r a f l o t a t i o n scheme f o r a g i v e n c o a l sample. I n u s i n g t h e d a t a , one c a u t i o n s h o u l d be n o t e d : s i n c e 95% c l e a n c o a l and 5% p y r i t e were u s e d , t h e maximum y i e l d o f c o m b u s t i b l e m a t e r i a l i s 95%. Y i e l d s a p p r o a c h i n g and e x c e e d i n g t h i s v a l u e a r e most c e r t a i n l y a c c o m p a n i e d by t h e f l o t a t i o n o f much l i b e r a t e d p y r i t i c s u l f u r (SLP). Coal F l o t a t i o n K i n e t i c s . H i s t o r i c a l l y , the r e s u l t s of s o f t c o a l p r e p a r a t i o n h a v e been most o f t e n a n a l y z e d i n t e r m s o f y i e l d and o f p r o d u c t a s h and, more r e c e n t l y , s u l f u r . As a r e s u l t o f o u r e x t e n s i v e s t u d i e s on t h e n a t u r e o f c o a l f l o t a t i o n , h o w e v e r , we b e l i e v e t h a t t h e r a t e o f c o a l f l o t a t i o n s h o u l d be added t o t h e l i s t of e v a l u a t i o n c r i t e r i a used f o r l a b o r a t o r y s t u d i e s . I t has b e e n amply d e m o n s t r a t e d (16) t h a t d i f f e r e n t f r a c t i o n s i n t h e raw c o a l f l o a t a t d i f f e r e n t r a t e s , and t h u s t h e c o a l f l o t a t i o n r a t e i s a v a r i a b l e t h a t c a n be u s e d t o a c h i e v e b e t t e r s e p a r a t i o n s , most p a r t i c u l a r l y b e t w e e n c o a l and p y r i t e . Coal f l o t a t i o n f o l l o w s a f i r s t - o r d e r r a t e equation (16): - £ = k C at

(1)

where C = c o n c e n t r a t i o n o f f l o a t a b l e m a t e r i a l ; t = t i m e , s e c ; k = r a t e constant, sec""l. This agrees w i t h the f i n d i n g s of B u s h e l l f o r the f l o t a t i o n of q u a r t z w i t h an amine (17) and t h e f i n d i n g s o f numerous o t h e r i n v e s t i g a t i o n s f o r ores (18). The e x p e r i m e n t a l a p p r o a c h was t o use a b a t c h f l o t a t i o n method and t o a p p l y t h e a n a l y s i s p r o p o s e d by B u s h e l l (17). F i g u r e 1 f o r t h e f l o t a t i o n o f P i t t s b u r g h Seam c o a l w i t h MIBC, shows t h a t c o a l f l o t a t i o n f o l l o w s t h e c u r v e AB3C3, and t h i s c u r v e i s a s t r a i g h t l i n e , and h e n c e f o l l o w s E q u a t i o n 1, o v e r t h e segment A-B3. T h i s c o r r e s p o n d s t o t h e f l o t a t i o n o f 80% o f t h e

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

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TIME, MINUTES American Institute of Mining, Metallurgical and Petroleum Engineers

Figure 1. The rate of flotation of Pittsburgh seam coal using 0.84 lb/ton pine oil. Percentage remaining in the flotation cell as a function of time (16).

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c o a l , and, i n f a c t , there i s o n l y s l i g h t d e v i a t i o n from l i n e a r i t y f o r t h e f l o t a t i o n o f 90% o f t h e c o a l . The f i r s t - o r d e r r a t e c o n s t a n t , i n s e c ~ l , may be d e t e r m i n e d g r a p h i c a l l y f r o m p l o t s s u c h a s t h o s e g i v e n i n F i g u r e 1 o r may be c a l c u l a t e d o v e r t h e s t r a i g h t l i n e p o r t i o n o f t h e c u r v e by t h e f o l l o w i n g equation: log k = 2.303

C

- log C Ν — ~

(2)

where = concentration of material at t ^ ; C = concentration of material at t . From F i g u r e 1 i t may be s e e n t h a t t h e f l o t a t i o n o f t h e a s h b e a r i n g c o n s t i t u e n t s and t h e l i b e r a t e d p y r i t i c s u l f u r (SLP) a l s o f o l l o w s the f i r s t - o r d e r r a t e law over the f i r s t minute t o minute and o n e - h a l f o f f l o t a t i o n . This period corresponds to the f l o t a ­ t i o n o f n e a r l y a l l o f t h e c o a l p r e s e n t . Numerous o t h e r f l o t a t i o n t e s t s w i t h a v a r i e t y of c o a l samples, f r o t h e r s , c o l l e c t o r s , p a r t i c l e s i z e s , and o p e r a t i n g c o n d i t i o n s c o n f i r m t h e a c c u r a c y o f t h i s i n t e r p r e t a t i o n ( 1 5 , 1 6 , 1 9 , 2 0 ) . The s l o w f l o a t i n g f r a c t i o n t h a t f l o a t i n g a f t e r ^ 90 s e c - i s composed o f c o a r s e r p a r t i c l e s , t h o s e whose s u r f a c e i s s l i g h t l y o x i d i z e d , l o w e r r a n k and h i g h a s h f r a c t i o n s s u c h a s f u s i n i t e , a n d , i n raw c o a l s y s t e m s , l o c k e d particles. As w i l l be d e m o n s t r a t e d l a t e r , k i n e t i c a n a l y s i s i s a v a l u a b l e a i d i n e v a l u a t i n g t h e c o m p l i c a t e d i n t e r a c t i o n s between c o a l t y p e , f r o t h e r s y s t e m , and f l o t a t i o n o p e r a t i n g c o n d i t i o n s . 2

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2

E f f e c t o f F r o t h e r Systems. A comparison o f f r o t h e r s i s g i v e n i n T a b l e I (15) s h o w i n g t h e y i e l d ( a f t e r 7.75 m i n o f f l o t a t i o n t i m e ) , p e r c e n t a g e o f l i b e r a t e d p y r i t i c s u l f u r (% S L P ) , and t h e amount o f c o a r s e , 14 χ 28 mesh, c o a l f l o a t e d . An e q u i m o l a r c o n ­ c e n t r a t i o n o f e a c h f r o t h e r was c h o s e n a s t h e b a s i s o f c o m p a r i s o n . TABLE I .

F r o t h e r C o m p a r i s o n f o r t h e F l o t a t i o n o f Lower K i t t a n n i n g and P i t t s b u r g h Seam C o a l s ( 1 5 ) .

C o a l Type

Lower Kittanning Pittsburgh Seam

Frother

MIBC^ Pine O i l Cresol C

MIBC Pine O i l Cresol

Concentration mol lb. L. ton

Floated mat'l. Yield, %

h

SLP

+28 mesh

-4 2.4x10" 2.4x10"-4 2.4x10"-4

0.28 0.44 0.29

94 96 69

—

92 91 24

-4 2.4x10" 2.4x10"-4 2.4x10"-4

0.28 0.44 0.29

84 89 19

16 21 2

29 48 2

20 33

C o a l y i e l d a f t e r 7.75 m i n o f f l o t a t i o n . b SLP = L i b e r a t e d p y r i t i c s u l f u r . ° MIBC = M e t h y l i s o b u t y l c a r b i n o l , 4 - m e t h y l - 2 - p e n t a n o l .

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

%

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76

C O A L DESULFURIZATION

From t h i s t a b l e s e v e r a l c o n c l u s i o n s emerge: (1) MIBC and p i n e o i l a r e r o u g h l y e q u i v a l e n t f r o t h e r s on an e q u i m o l a r b a s i s , b u t MIBC i s s u p e r i o r on a pounds p e r t o n b a s i s (2) C r e s o l i s a much i n f e r i o r f r o t h e r t o e i t h e r MIBC o r p i n e oil (3) P i n e o i l t e n d s t o f l o a t s l i g h t l y more p y r i t e t h a n does MIBC (4) P i n e o i l i s a s u p e r i o r f r o t h e r f o r the f l o t a t i o n of c o a r s e r c o a l p a r t i c l e s , e s p e c i a l l y f o r an i n t e r m e d i a t e f l o a t i n g c o a l s u c h as t h e P i t t s b u r g h seam (5) The Lower K i t t a n n i n g c o a l i s a f a s t e r f l o a t i n g c o a l t h a n i s t h a t f r o m t h e P i t t s b u r g h seam T h e s e a r e o n l y g e n e r a l c o n c l u s i o n s , and t h e n a t u r e o f t h e c o a l and t h e n a t u r e and c o n c e n t r a t i o n o f t h e f r o t h e r may w e l l change t h e o r d e r o f t h i n g s . Most c r i t i c a l i s the problem of i m p u r i t i e s w h i c h t e n d t o f l o a t p y r i t e . The p r o b l e m o f i m p u r e c r e s o l s i s p a r t i c u l a r l y c r i t i c a l ; t h e o i l y i m p u r i t i e s a c t as c o l l e c t o r s and, h e n c e , f a v o r t h e f l o t a t i o n o f c o a r s e and o t h e r d i f f i c u l t - t o - f l o a t p a r t i c l e s — b u t a t the expense of encouraging the f l o t a t i o n of u n d e s i r a b l e p y r i t e . O i l has l o n g b e e n u s e d t o enhance t h e f l o t a t i o n o f c o a l p a r t i c l e s otherwise d i f f i c u l t to f l o a t w i t h a f r o t h e r only. The i n t r o d u c t i o n o f an o i l y c o l l e c t o r i s , h o w e v e r , a c c o m p a n i e d by t h e f l o t a t i o n o f much u n d e s i r a b l e p y r i t e . T h i s i s c l e a r l y i l l u s t r a t e d i n T a b l e I I (21) w h e r e t h e i n t r o d u c t i o n o f 0.46 l b . / t o n o f f u e l TABLE I I .

E f f e c t o f F u e l O i l on I n c r e a s i n g t h e F l o t a t i o n o f P y r i t i c S u l f u r D u r i n g t h e F l o t a t i o n o f Lower K i t t a n n i n g Coal (21). 3 Flotation

MIBC lb./ton 0.17 0.17

Fuel O i l lb./ton 0 0.46

r a t e χ 10

,sec

-1 Yield,

k

C

37.5 55

k

SLP 2.3 12.4

a

SLP

floated,

%

kc/^SLP

90 97

16 4

% 13 56

C o a l y i e l d a f t e r 7.75 min o f f l o t a t i o n . k£ = F l o t a t i o n r a t e c o n s t a n t f o r c o a l . o i l t o a c o a l f l o t a t i o n s y s t e m u s i n g MIBC as f r o t h e r i n c r e a s e d the amount o f t h e l i b e r a t e d p y r i t i c s u l f u r (SLP) w h i c h f l o a t e d f r o m 13 t o 5 6 % ! ! ! I n t h i s c a s e t h e k i n e t i c a n a l y s i s i s h e l p f u l . Numerous o t h e r d a t a (15,16,19) have e s t a b l i s h e d t h a t c o a l g e n e r a l l y f l o a t s a b o u t 10-30 t i m e s f a s t e r t h a n d o e s p y r i t e ; t h e e x a c t v a l u e o f t h e r a t i o depends on t h e s p e c i f i c c o a l and p y r i t e and on t h e f r o t h e r s y s t e m and f l o t a t i o n o p e r a t i n g c o n d i t i o n s . An i m p o r t a n t e v a l u a t i o n c r i t e r i o n i s thus to l o o k at the r a t i o of the f l o t a t i o n r a t e c o n s t a n t of c o a l to t h a t of p y r i t e , k / k . As t h e v a l u e o f p

q T p

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

6.

Flotation Process for Coal Desulfurization

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77

t h i s r a t i o d i f f e r s f r o m an a v e r a g e v a l u e o f , s a y , 16, t h o s e f l o t a t i o n c o n d i t i o n s e i t h e r f a v o r a b l e or unfavorable f o r p y r i t e r e j e c t i o n may be r e a d i l y d i s c e r n e d . I t c a n be s e e n f r o m T a b l e I I t h a t w i t h the a d d i t i o n of f u e l o i l , the c o a l f l o t a t i o n r a t e i n c r e a s e d somewhat b u t t h a t t h e p y r i t e f l o t a t i o n r a t e i n c r e a s e d f i v e - f o l d ; t h e k ç / k s p r a t i o d r o p p e d t o 4. O i l encourages the f l o t a t i o n o f p y r i t e much more t h a n i t d o e s t h a t o f c o a l i n t h i s instance.

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L

E f f e c t of F r o t h e r Concentration. F i g u r e s 2 and 3 show t h e e f f e c t o f an i n c r e a s i n g amount o f t h e f r o t h e r , p i n e o i l , on c o a l y i e l d and t h e amount of l i b e r a t e d p y r i t i c s u l f u r (SLP) f l o a t e d as a f u n c t i o n of f l o t a t i o n time (22). With respect to y i e l d (Figure 2 ) , t h e r e i s a t h r e s h o l d amount o f f r o t h e r needed t o o b t a i n good coal yields. Beyond t h i s i n c i p i e n t amount o f f r o t h e r , h o w e v e r , a d d i t i o n a l f r o t h e r does n o t f u r t h e r i n c r e a s e y i e l d w i t h t h i s c o a l . The same p a t t e r n h o l d s f o r a f l o t a t i o n t i m e o f 0.25 o r o f 7.75 min. A 1-min f l o t a t i o n t i m e i s s u f f i c i e n t t o a c h i e v e n e a r l y c o m p l e t e y i e l d f o r f r o t h e r c o n c e n t r a t i o n s o f 0.5 l b . / t o n o r more. However, w i t h the f l o t a t i o n of p y r i t e (Figure 3 ) , a d i f f e r e n t p a t t e r n emerges: b o t h an e x c e s s f r o t h e r d o s a g e and e x t e n d e d f l o t a t i o n t i m e s l e a d t o t h e f l o t a t i o n o f an e v e r - i n c r e a s i n g amount o f p y r i t e . The a d v a n t a g e o f u s i n g s h o r t f l o t a t i o n t i m e s and a low f r o t h e r concentration i s obvious.

three

E f f e c t of F l o t a t i o n Operating Conditions. T a b l e I I I compares l e v e l s o f a i r r a t e and f l o t a t i o n c e l l i m p e l l e r s p e e d ( 1 6 ) .

TABLE I I I .

E f f e c t o f A i r F l o w R a t e and I m p e l l e r Speed on F l o t a t i o n o f P i t t s b u r g h Seam C o a l ( 1 6 ) .

C e l l Operating Conditions air rate speed (cfm) (rpm)

3 -1 F l o t . r a t e χ 10 , sec

Flotation

the

Data^

a

0.535 0.233 0.136

2540 1660 1380

.

h k

73 25.5 15.3

SLP

4.5

15.9

0.2

76

Yield

% SLP floated

92.4 79.1 67.8

27.9 17.7 1.4

C

% + 28M floated 70.3 29.8 15.0

MIBC 0.57 l b . / t o n . b kç = F l o t a t i o n r a t e c o n s t a n t f o r c o a l . ° SLP = L i b e r a t e d p y r i t i c s u l f u r ^ One m i n u t e f l o t a t i o n t i m e . I n t e n s e f l o t a t i o n c o n d i t i o n s ( h i g h a e r a t i o n r a t e s and h i g h i m p e l l e r speed) f a v o r t h e f a s t f l o t a t i o n o f c o a l , t h e f l o t a t i o n o f c o a r s e p a r t i c l e s , and t h e f l o t a t i o n o f p y r i t e . A g a i n , u s i n g t h e r a t i o o f t h e f l o t a t i o n r a t e c o n s t a n t s f o r c o a l and p y r i t e , k ç / k g L p , t h e maximum r e j e c t i o n o f p y r i t e o c c u r s u n d e r g e n t l e o p e r a t i n g

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

DESULFURIZATION

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COAL

American Institute of Mining, Metallurgical and Petroleum Engineers

Figure 2. (top) Flotation yield of Lower Kittanning coal as a function of pine oil concentration and time (22) American Institute of Mining, Metallurgical and Petroleum Engineers

Figure 3. (bottom) Effect of pine oil dosage on the amount of liberated pyritic sulfur floated. Lower Kittanning coal (22).

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

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conditions. Long f l o t a t i o n r e s i d e n c e t i m e s f a v o r t h e f l o t a t i o n o f b o t h c o a r s e p a r t i c l e s and p y r i t e . R a s t o g i and A p l a n (4,16) have d e m o n s t r a t e d t h a t t h e a i r r a t e alone i s r e s p o n s i b l e f o r the bulk of the increase i n c o a l f l o t a tion. The c o n t r i b u t i o n o f i m p e l l e r speed i s modest. T e s t E v a l u a t i o n . A s t u d y o f numerous f l o t a t i o n t e s t s shows t h a t t h e r e i s a r e l a t i o n s h i p b e t w e e n y i e l d and t h e amount o f p y r i t e w h i c h f l o a t s ( F i g u r e 4) ( 4 , 2 3 ) . This curve i s s i m i l a r to t h e g r a d e - r e c o v e r y c u r v e s o f t e n u s e d i n o r e d r e s s i n g s t u d i e s (24) and t o c o a l - s u l f u r d a t a r e p o r t e d by M i l l e r ( 1 2 ) . E a c h p a r t i c u l a r f l o t a t i o n s y s t e m shows a s i m i l a r f a m i l y o f c u r v e s . A s h , t o t a l s u l f u r , o r f l o t a t i o n r a t e may a l s o be u s e d as t h e a b s c i s s a and s i m i l a r l y shaped c u r v e s r e s u l t ( 4 , 2 3 ) . T h i s method may be u s e d to save c o n s i d e r a b l e time i n f l o t a t i o n t e s t i n g s i n c e s u l f u r v a l u e s a t i n t e r m e d i a t e y i e l d s may be r e a d i l y e s t i m a t e d w i t h o u t t h e need t o r e s o r t to s t i l l another t e s t . The b u l k o f t h e f r e e p y r i t e t h a t f l o a t s a c c o m p a n i e s t h e l a s t 20% o r so o f y i e l d . T h i s f a c t has b e e n u s e d t o d e v e l o p a c o a l f l o t a t i o n p r o c e d u r e c a l l e d t h e " g r a b and run" technique. The "Grab and Run" P r o c e s s . I n t h i s method a p p r o x i m a t e l y one-half to t w o - t h i r d s of the u l t i m a t e c o a l y i e l d i s f l o a t e d i n the rougher c e l l under g e n t l e o p e r a t i n g c o n d i t i o n s ( s t a r v a t i o n q u a n t i t i e s o f a g e n t l e f r o t h e r s u c h as MIBC, l o w a i r r a t e , l o w i m p e l l e r s p e e d , s h o r t f l o t a t i o n r e s i d e n c e t i m e , e t c . ) t o remove a f r a c t i o n low i n p y r i t e . U n d e r most c o n d i t i o n s s t u d i e d so f a r , t h i s f a s t - f l o a t i n g f r a c t i o n c a n go d i r e c t l y t o t h e c l e a n c o a l p r o d u c t ; hence t h e name " g r a b and r u n . " The b a l a n c e o f t h e r e c o v e r a b l e c o a l i s removed i n a s c a v e n g e r c i r c u i t u n d e r more i n t e n s e o p e r a t i n g c o n d i t i o n s . As t h e u l t i m a t e y i e l d i s a p p r o a c h e d , t h e amount o f p y r i t i c s u l f u r t h a t f l o a t s i n c r e a s e s g r e a t l y . The scavenger c o n c e n t r a t e , which i s h i g h e r i n p y r i t i c s u l f u r than the rougher c o n c e n t r a t e , i s sent to c l e a n e r f l o t a t i o n . H e r e two options are a v a i l a b l e : d e p r e s s p y r i t e and f l o a t c o a l o r v i c e versa. In the l a t t e r o p t i o n the scavenger c l e a n e r c i r c u i t r e s e m b l e s t h e U.S. B u r e a u o f M i n e s r e v e r s e f l o t a t i o n p r o c e s s e x c e p t t h a t o n l y a f r a c t i o n o f t h e t o t a l t o n n a g e n e e d be t r e a t e d . D e t a i l s o f t h i s p r o c e s s w i l l be r e p o r t e d s o o n ( 2 5 ) . Summary. P y r i t e i s b e s t r e j e c t e d u n d e r g e n t l e f r o t h i n g and o p e r a t i n g c o n d i t i o n s u s i n g short residence times i n the f l o t a t i o n cell. The u s e o f e x c e s s f r o t h e r and, e s p e c i a l l y an o i l y f r o t h e r and/or c o l l e c t o r , i s p a r t i c u l a r l y c o u n t e r - p r o d u c t i v e t o p y r i t i c sulfur rejection. The l a s t i n c r e m e n t f o r t h e r e c o v e r y o f c o a r s e o r o t h e r h a r d - t o - f l o a t p a r t i c l e s i s i n v a r i a b l y a c c o m p a n i e d by t h e f l o t a t i o n o f much p y r i t i c s u l f u r .

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

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C O A L DESULFURIZATION

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100

70h ι

0

•

10

20

30

ι

I

40

50

PERCENT SLP FLOATED American Institute of Mining, Metallurgical and Petroleum Engineers

Figure 4. Coal yield vs. liberated pyritic sul­ fur (SLP) recovery for Lower Kittanning coal

(4, 23j

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

6.

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Acknowledgements The a u t h o r w i s h e s t o t h a n k t h e A m e r i c a n I r o n a n d S t e e l I n s t i t u t e , The P e n n s y l v a n i a S c i e n c e and E n g i n e e r i n g F o u n d a t i o n , and t h e A p p a l a c h i a n R e g i o n a l C o m m i s s i o n f o r f i n a n c i a l s u p p o r t i n conducting these s t u d i e s . Acknowledgement i s made t o t h e f o l l o w i n g f o r m e r a n d p r e s e n t g r a d u a t e s t u d e n t s i n The M i n e r a l P r o c e s s i n g S e c t i o n , The P e n n s y l v a n i a S t a t e U n i v e r s i t y , who have c o n t r i b u t e d d a t a f r o m w h i c h t h i s r e p o r t was drawn: C. M. B o n n e r , V. C h o u d h r y , W. C. H i r t , C. J . Im, T. J . O l s o n and R. C. R a s t o g i .

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch006

Literature Cited

1. Miner. Yearbk., 1973 (1975). 2. Mitchell, D. R., Trans. AIME (1948), 177, 315. 3. Hoffman, L., Aresco, S. J., Holt, E. C , Deurbrouck, A. W., "Engineering/Economic Analysis of Coal Preparation with SO2 Clean-up Process for Keeping Higher Sulfur Coals in the Energy Market," in Second Symposium on Coal Preparation, J. F. Boyer, Jr., Ed., Bituminous Coal Research Inc., Monroeville, Pa. (1976). 4. Aplan, F. F., "Coal Flotation," in A. M. Gaudin Memorial International Flotation Symposium, M. C. Fuerstenau, Ed., AIME, New York (1976). 5. Brown, D. J., "Coal Flotation," in Froth Flotation - 50th Anniversary Volume, D. W. Fuerstenau, Ed., AIME, New York (1962). 6. Zimmerman, R. E., "Flotation," in Coal Preparation, J. W. Leonard and D. R. Mitchell, Eds., 3rd ed., AIME, New York (1968). 7. Miller, F. G., Podgursky, J. M., Aikman, R. P., "Study of the Mechanism of Coal Flotation and its Role in a System for Processing Fine Coal," Trans. AIME (1967), 238, 276. 8. Im, Chang J., unpublished data (1977). 9. Miller, F. G., "The Effect of Froth Sprinkling on Coal Flota­ tion Efficiency," Trans. AIME (1969), 244, 158. 10. Gaudin, Α. Μ., Flotation, 2nd ed., McGraw-Hill, New York (1957) 11. Yancey, H. F., Taylor, J. Α., "Froth Flotation of Coal; Sulfur and Ash Reduction," U.S. Bur. Mines Rep. Invest. (1935), 3263. 12. Miller, F. G., "Reduction of Sulfur in Minus 28 Mesh Bitumin­ ous Coal," Trans. AIME (1964), 228, 7. 13. Zimmerman, R. Ε., "Flotation of Bituminous Coal," Trans. AIME (1948), 117, 338. 14. Miller, K. J., "Coal - Pyrite Flotation," Trans. AIME (1975), 258, 30. 15. Hirt, W. C., Aplan, F. F., unpublished data (1977). 16. Rastogi, R. C., Aplan, F. F., "Coal Flotation as a Rate Process," accepted for publication in Trans. AIME.

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17. Bushell, C. H. G., "Kinetics of Flotation," Trans. AIME (1962), 223, 266-278. 18. Arbiter, Ν., Harris, C. C., "Flotation Kinetics," in Froth Flotation - 50th Anniversary Volume, D. W. Fuerstenau, Ed., AIME, New York (1962). 19. Rastogi, R. C., Hirt, W. C., Aplan, F. F., "An Evaluation of Several Variables Influencing the Rate of Coal Flotation," submitted to Trans. AIME. 20. Rastogi, R. C., Hirt, W. C., Aplan, F. F., unpublished data (1977). 21. Bonner, C. Μ., Im, C. J., Choudhry, V., Aplan, F. F., "The Influence of Oil on Pyritic Sulfur Rejection During Coal Flotation," submitted to Trans. AIME. 22. Bonner, C. Μ., Aplan, F. F., "Frother Comparisons in the Flotation of Coal," accepted for publication in Trans. AIME. 23. Bonner, C. Μ., Hirt, W. C., Aplan, F. F., unpublished data (1977). 24. Aplan, F. F., "Mineral Processing - Evaluation to Indicate Processing Approach," Section 27.3 in SME Mining Engineering Handbook, A. B. Cummins and I. A. Given, Eds., pp. 27, 15-28, 86-88, New York (1973). 25. Bonner, C. Μ., Hirt, W. C., Im, C. J., Aplan, F. F., unpublished data (1977).

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

7 A Comparison of Coal Beneficiation Methods 1

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch007

SEONGWOO MIN and T. D. WHEELOCK Iowa State University, Department of Chemical Engineering and Nuclear Engineering, Energy and Mineral Resources Research Institute, Ames, IA 50011

Although iron pyrites and other minerals are removed from coal on an industrial scale almost exclusively by gravity separation methods at the present time, other beneficiation methods are coming into use. Among the developing methods, froth flotation (1,2,3) is the foremost, although the oil agglomeration method (4,5,6) is also promising. Both of these methods take advantage of the difference in surface properties of coal and inorganic mineral particles suspended in water to effect a separation. In the first method the hydrophobic coal particles are removed from the hydrophilic mineral particles by selective attachment to a mass of air bubbles, while in the second method the coal particles are selectively coated and agglomerated by fuel oil and then recovered by screening. While gravity separation methods are well suited for removing coarse mineral particles from coal, they are generally ineffective for removing microscopic particles. On the other hand, both the froth flotation and oil agglomeration methods offer the potential for recovering and separating coal fines from microscopic impurit i e s , t h u s c o m p l e m e n t i n g t h e gravity separation methods. However, none o f t h e s e p h y s i c a l s e p a r a t i o n methods a r e e f f e c t i v e u n l e s s the m i n e r a l i m p u r i t i e s a r e f i r s t l i b e r a t e d o r f r e e d f r o m t h e c o a l . A l t h o u g h m e c h a n i c a l c r u s h i n g a n d / o r g r i n d i n g have a l w a y s been used i n d u s t r i a l l y t o u n l o c k i m p u r i t i e s , t h e r e s u l t s have n o t a l w a y s been s a t i s f a c t o r y . C h e m i c a l c o m m i n u t i o n h a s been p r o p o s e d a s a means t o u n l o c k t h e i m p u r i t i e s (7,8,9) and t o s o l v e t h i s p r o b l e m . T h i s method o f c o m m i n u t i o n u s e s s p e c i f i c c h e m i c a l a g e n t s s u c h a s a n h y d r o u s ammonia t o f r a g m e n t c o a l . Since fragmentation occurs a l o n g b e d d i n g p l a n e s a n d b o u n d a r i e s between c o a l and m i n e r a l m a t t e r , t h e m i n e r a l i m p u r i t i e s t e n d t o be f r e e d more c o m p l e t e l y f o r a g i v e n s i z e r e d u c t i o n than would r e s u l t from m e c h a n i c a l comminution ( 7 ) .

P r e s e n t a d d r e s s : B a t t e l l e Columbus L a b o r a t o r i e s , Ohio 43201

Columbus,

83

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In the work d e s c r i b e d h e r e , h i g h - s u l f u r b i t u m i n o u s c o a l s f r o m two Iowa s t r i p m i n e s were s u b j e c t e d t o a s e r i e s o f 16 d i f f e r e n t t r e a t m e n t s t o compare t h e e f f e c t i v e n e s s o f v a r i o u s b e n e f i c i a t i o n methods. These t r e a t m e n t s i n v o l v e d d i f f e r e n t com­ b i n a t i o n s o f s i z e r e d u c t i o n methods ( c r u s h i n g , p u l v e r i z i n g , g r i n d ­ i n g , and c h e m i c a l c o m m i n u t i o n ) and o f p h y s i c a l s e p a r a t i o n methods ( g r a v i t y s e p a r a t i o n , f r o t h f l o t a t i o n , and o i l a g g l o m e r a t i o n ) . The r e s u l t s a r e compared b e l o w on t h e b a s i s o f p r o d u c t y i e l d and on t h e p e r c e n t a g e r e d u c t i o n i n s u l f u r and a s h b r o u g h t a b o u t by t h e treatments.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch007

Experimental The f o l l o w i n g m e t h o d s , e q u i p m e n t , and m a t e r i a l s were u s e d the e x p e r i m e n t a l i n v e s t i g a t i o n : R o l l C r u s h i n g . Lump c o a l (4 cm χ 0) was c r u s h e d t o 6 mm t o p s i z e by p a s s i n g i t t h r o u g h a b e n c h - s c a l e d o u b l e r o l l c r u s h e r m a n u f a c t u r e d by S m i t h E n g i n e e r i n g W o r k s , M i l w a u k e e , WI. Pulverizing. P r e v i o u s l y c r u s h e d c o a l was p u l v e r i z e d t o -35 mesh by a M i k r o - S a m p l m i l l m a n u f a c t u r e d by P u l v e r i z i n g M a c h i n e r y D i v i s i o n , A m e r i c a n - M a r i e t t a Co., Summit, N J . Ball Milling. P r e v i o u s l y p u l v e r i z e d c o a l was ground t o -400 mesh s i z e i n a c e r a m i c j a r m i l l . F o r t h i s o p e r a t i o n 200 g c o a l , 1000 g w a t e r , and 1900 g f l i n t p e b b l e s were p l a c e d i n a 5.7-L j a r m i l l , and t h e m i l l was t h e n r u n f o r 20 h r . C h e m i c a l C o m m i n u t i o n . F o r t h i s o p e r a t i o n 500 g lump c o a l (4 cm χ 0) were p l a c e d i n a 2000-ml E r l e n m e y e r f l a s k w h i c h was t h e n p l a c e d i n a c o l d b a t h o f d r y i c e and m e t h a n o l and c o o l e d t o -70°C. L i q u i d a n h y d r o u s ammonia was t h e n added t o t h e f l a s k u n t i l t h e c o a l was immersed i n t h e l i q u i d . A f t e r t h e c o a l had s o a k e d f o r 1.0 h r , t h e f l a s k was removed f r o m t h e c o l d b a t h and was p l a c e d i n a w e l l v e n t i l a t e d hood where t h e ammonia e v a p o r a t e d . When t h e o d o r o f ammonia c o u l d no l o n g e r be d e t e c t e d , t h e comminu­ t i o n s t e p was c o m p l e t e d . G r a v i t y S e p a r a t i o n . To e f f e c t t h e g r a v i t y s e p a r a t i o n o f c o a l and m i n e r a l m a t t e r , 500 g c r u s h e d c o a l (6 mm χ 0) were added t o 2000 ml t e t r a c h l o r o e t h y l e n e ( s p e c i f i c g r a v i t y = 1.613) i n a l a r g e b e a k e r p l a c e d i n a w e l l v e n t i l a t e d hood. The m i x t u r e was s t i r r e d by hand t o i n s u r e w e t t i n g o f a l l p a r t i c l e s , and t h e n i t was a l l o w ­ ed t o s t a n d f o r 30 m i n . The f l o a t p r o d u c t was s u b s e q u e n t l y skimmed o f f and p l a c e d on a 100-mesh s i e v e t o a l l o w any a d h e r i n g l i q u i d t o d r a i n away. The f l o a t p r o d u c t was t h e n p l a c e d i n a d r y i n g o v e n a t 100°C f o r 4 h r . Froth Flotation. To c o n d u c t a f r o t h f l o t a t i o n t e s t , 200 g p u l v e r i z e d c o a l (-35 mesh) were added t o 2000 ml t a p w a t e r i n a b o w l o f a l a b o r a t o r y model Wemco F a g e r g r e n f l o t a t i o n c e l l . With t h e a g i t a t o r r u n n i n g , t h e pH o f t h e s l u r r y was l o w e r e d b e l o w 5 by a d d i n g 10 ml a c i d s o l u t i o n c o n t a i n i n g 10 v o l % c o n c e n t r a t e d hydrochloric acid. B o t h k e r o s e n e (1.0 ml) and m e t h y l i s o b u t y l c a r b i n o l (0.5 ml) were added t o t h e a g i t a t e d s l u r r y , and t h e a i r for

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch007

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MIN

AND

WHEELOCK

Coal Bénéficiât ion Methods

85

f l o w t o t h e c e l l was s e t a t 9.3 L/min. The r e s u l t i n g f r o t h was c o l l e c t e d u n t i l i t a p p e a r e d t h a t no more c o a l was b e i n g r e c o v e r e d . The m a t e r i a l r e m a i n i n g i n t h e b o w l was p o u r e d o u t , t h e f r o t h p r o d u c t was p u t b a c k i n t h e b o w l , and f r e s h t a p w a t e r was added t o b r i n g t h e s l u r r y volume t o 2000 m l . W i t h t h e a g i t a t o r r u n n i n g , t h e pH o f t h e s l u r r y was r a i s e d above 9 by a d d i n g 40 ml b a s e c o n t a i n i n g 5 wt % p o t a s s i u m h y d r o x i d e . The c o a l was t h e n r e f l o a t ed w i t h o u t a d d i n g f u r t h e r r e a g e n t s and u s i n g t h e same a i r f l o w r a t e a s b e f o r e . A t w o - s t a g e s e p a r a t i o n was made b e c a u s e a l o w pH seemed t o f a v o r t h e r e m o v a l o f a s h w h e r e a s a h i g h pH seemd t o f a v o r the removal of p y r i t e . O i l Agglomeration. O i l a g g l o m e r a t i o n t e s t s were c a r r i e d o u t w i t h a 1 4 - s p e e d k i t c h e n b l e n d e r ( S e a r s I n s t a - B l e n d M o d e l 400) w h i c h h e l d up t o 1200 ml f l u i d . F o r an a g g l o m e r a t i o n t e s t , 200 ml o f an aqueous s l u r r y c o n t a i n i n g 10 wt % c o a l was p l a c e d i n t h e b l e n d e r t o g e t h e r w i t h 10 ml o f s o l u t i o n c o n t a i n i n g 0.2 wt % s o d i u m c a r b o n a t e . The s o d i u m c a r b o n a t e n o t o n l y i n c r e a s e d t h e pH o f t h e s l u r r y but a l s o s e r v e d as a d i s p e r s i n g agent f o r the c l a y p a r t i cles. The s l u r r y was a g i t a t e d f o r 5 min a t t h e l o w e s t s p e e d . An e m u l s i o n o f f u e l o i l and w a t e r was t h e n added t o t h e c o a l s l u r r y , and t h e a g i t a t i o n c o n t i n u e d f o r a n o t h e r 5 min a t t h e same speed to form agglomerates. The e m u l s i o n was p r e p a r e d by c o m b i n i n g 2.0 ml o f a m i x t u r e o f No. 1 f u e l o i l (86 v o l %) and No. 5 f u e l o i l (14 v o l % ) , t h e m i x t u r e h a v i n g a s p e c i f i c g r a v i t y o f 0.83, w i t h 200 ml t a p w a t e r and e m u l s i f y i n g t h e m i x t u r e w i t h an u l t r a sonic vibrator. The a g g l o m e r a t e d c o a l s l u r r y was p o u r e d i n t o a 1000-ml s e p a r a t o r y f u n n e l whereupon t h e c o a l f l o a t e d t o t h e s u r f a c e , and t h e r e f u s e p a r t i c l e s s e t t l e d t o t h e b o t t o m . The w a t e r and r e f u s e were d r a i n e d o u t t h r o u g h t h e b o t t o m o p e n i n g , and t h e a g g l o m e r a t e d c o a l was p u t b a c k i n t h e b l e n d e r and m i x e d w i t h 200 ml f r e s h t a p w a t e r . A f t e r a g i t a t i n g t h e m i x t u r e f o r 2 min a t t h e l o w e s t s p e e d , t h e c o a l s l u r r y was p o u r e d b a c k i n t o t h e s e p a r a t o r y f u n n e l where t h e a g g l o m e r a t e d c o a l was r e c o v e r e d a g a i n . T h i s w a s h i n g o p e r a t i n g was r e p e a t e d once more t o r e d u c e e n t r a p p e d impurities. C h e m i c a l A n a l y s i s M e t h o d s . C o a l s a m p l e s were a n a l y z e d f o r s u l f u r and a s h by t h e s t a n d a r d ASTM p r o c e d u r e s ( 1 0 ) . Materials. C o a l f r o m two Iowa s t r i p m i n e s was u s e d f o r t h i s investigation. A c h a n n e l sample f r o m t h e ICO mine and a r u n - o f mine sample f r o m t h e J u d e mine were t h e s o u r c e o f t h e m a t e r i a l s used. The p r o x i m a t e a n a l y s i s and s u l f u r d i s t r i b u t i o n o f e a c h o f t h e s e s a m p l e s a r e shown i n T a b l e I . A l t h o u g h t h e s u l f u r and a s h c o n t e n t s o f t h e s e s a m p l e s were w i d e l y d i f f e r e n t , t h e s a m p l e s r e p r e s e n t e d c o a l o f t h e same r a n k ( h i g h v o l a t i l e C ) . Investigation of the c o a l m i c r o s t r u c t u r e w i t h a s c a n n i n g e l e c t r o n microscope r e v e a l e d s u b s t a n t i a l amounts o f f i n e l y d i s s e m i n a t e d m i c r o c r y s t a l s of i r o n p y r i t e s (11,12). E a c h c o a l sample was c r u s h e d t o 4 cm t o p s i z e and t h e n was d i v i d e d i n t o t h r e e s i z e f r a c t i o n s (4 cm χ 1 cm, 1 cm χ 48 mesh, and 48 mesh χ 0 ) . E a c h s i z e f r a c t i o n was t h e n f l o a t - s i n k t e s t e d

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Table I.

Composition

o f C o a l f r o m ICO and

Jude S t r i p M i n e s

P e r c e n t by Type o f A n a l y s i s Proximate

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch007

ICO

Jude

44.0 43.2 4.5 8.3

39.4 37.6 8.8 14.2

100.0

100.0

analysis

v o l a t i l e matter f i x e d carbon moisture ash total Sulfur

Weight

distribution

pyritic sulfate organic

2.41 0.05 0.99

2.97 0.44 3.53

total

3.45

6.94

a t v a r i o u s s p e c i f i c g r a v i t i e s u s i n g o r g a n i c l i q u i d s o f known specific gravity. The s t a n d a r d B u r e a u o f M i n e s p r o c e d u r e was used f o r t h i s t e s t ( 1 3 ) . The d a t a f o r t h e d i f f e r e n t s i z e f r a c ­ t i o n s were combined t o p r o v i d e t h e c o m p o s i t e w a s h a b i l i t y a n a l y s i s f o r 4 cm χ 0 c o a l shown i n T a b l e I I . Treatment R e s u l t s The s e q u e n c e o f s t e p s i n v o l v e d i n e a c h o f t h e 16 t r e a t m e n t s w h i c h were a p p l i e d t o e a c h o f t h e two c o a l s a m p l e s i s shown i n F i g u r e 1. The f i r s t t r e a t m e n t was t h e s i m p l e s t and i n v o l v e d c r u s h i n g w i t h the r o l l c r u s h e r , p u l v e r i z i n g w i t h the M i k r o S a m p l m i l l , and o i l a g g l o m e r a t i o n . The s e c o n d t r e a t m e n t i n c l u d e d a b a l l m i l l i n g s t e p i n a d d i t i o n t o the o t h e r s t e p s . The t h i r d and f o u r t h t r e a t m e n t s i n c l u d e d a f r o t h f l o t a t i o n s t e p . I n t h e f i f t h t h r o u g h e i g h t h t r e a t m e n t s the c r u s h e d c o a l was s u b j e c t e d to g r a v i t y s e p a r a t i o n b e f o r e b e i n g p u l v e r i z e d and o t h e r w i s e t r e a t e d as i n t h e f i r s t f o u r t r e a t m e n t s . I n the l a s t e i g h t t r e a t ­ ments t h e c o a l was c h e m i c a l l y comminuted b e f o r e b e i n g c o n d u c t e d through the r o l l c r u s h e r . F o l l o w i n g the c h e m i c a l comminution s t e p , the p a t t e r n o f t r e a t m e n t s was t h e same as f o r t h e f i r s t eight treatments. The f i n a l s t e p o f e a c h t r e a t m e n t was an o i l agglomeration step. A f t e r e a c h s e p a r a t i o n s t e p w i t h i n any g i v e n t r e a t m e n t , t h e w e i g h t o f c o a l r e c o v e r e d was measured a f t e r d r y i n g t h e m a t e r i a l

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch007

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COAL

Table

II.

Composite W a s h a b i l i t y A n a l y s i s o f Coal ICO and J u d e S t r i p M i n e s

D i r e c t D a t a (%) Product Fraction

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch007

ICO

Weight

DESULFURIZATION

(4 cm χ 0) f r o m

Cumulative

Data

(%)

Sulfur Total

Weight

Ash

5.36 11.98 15.63 16.84 20.47 22.50 25.39 42.05

1. 80 2. 74 3. 66 4. 18 4. 83 4. 01 6. 46 17. 57

78 .7 85 .0 87 .8 90 .7 92 .7 94 .2 94 .7 100 .0

5 .36 5 .85 6 .16 6 .50 6 .80 7 .05 7 .15 9 .00

1.80 1.87 1.93 2.00 2.06 2.09 2.11 2.93

5.67 12.03 15.84 19.94 23.80 28.30 31.51 48.92

5. 07 4. 83 5. 24 6. 41 7. 91 7. 53 6. 79 12. 84

46.5 65.5 73.1 80.2 84.1 87.1 88.8 100.0

5.67 7.51 8.38 9.40 10.07 10.70 11.10 15.33

5 .07 5 .00 5 .03 5 .15 5 .28 5 .36 5 .38 6 .22

Ash

Sulfur Total

Coal

F l o a t 1.30 1.30 - 1.35 1.35 - 1.40 1.40 - 1.45 1.45 - 1.50 1.50 - 1.55 1.55 - 1.60 S i n k 1.60

78.7 6.3 2.8 2.9 2.0 1.5 0.5 5.3

Jude C o a l F l o a t 1.30 1.30 - 1.35 1.35 - 1.40 1.40 - 1.45 1.45 - 1.50 1.50 - 1.55 1.55 - 1.60 S i n k 1.60

46.5 19.0 7.6 7.1 3.9 3.0 1.7 11.2

o v e r n i g h t i n an oven a t 80°-100°C. A s m a l l sample o f t h e d r i e d c o a l was s u b s e q u e n t l y a n a l y z e d f o r a s h and p y r i t i c s u l f u r . The p e r c e n t a g e r e d u c t i o n i n e i t h e r a s h o r s u l f u r c o n t e n t was f o u n d f o r e a c h s e p a r a t i o n s t e p and f o r t h e o v e r a l l t r e a t m e n t by u s i n g the r e l a t i o n : π j . . Reduction

/ α , χ content of feed - content of product , (/ ) = —— ^ χ 100 content of feed The y i e l d o f c o a l f o r e a c h s e p a r a t i o n s t e p and t h e t o t a l y i e l d f o r t h e o v e r a l l t r e a t m e n t were d e t e r m i n e d a s f o l l o w s : Yield

n r k

0

(%) = d r y w e i g h t o f p r o d u c t dry weight of feed

In the case of o i l - a g g l o m e r a t e d c o a l ,

the y i e l d determined

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

i n this

7.

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Coal Beneficiation

Methods

89

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manner i n c l u d e d t h e s m a l l amount o f o i l w h i c h was n o t v a p o r i z e d d u r i n g oven d r y i n g . T h e r e f o r e , t o e x p r e s s t h e y i e l d on an o i l f r e e as w e l l as on a m o i s t u r e - f r e e b a s i s , the c a l c u l a t e d y i e l d was r e d u c e d b y 2%. I t was assumed t h a t l o s s e s o f m a t e r i a l s i n t h e c r u s h i n g and p u l v e r i z i n g s t e p s was n e g l i g i b l e . F i g u r e s 2, 3, a n d 4 show t h e c u m u l a t i v e e f f e c t s o f t h e d i f f e r e n t s e p a r a t i o n s t e p s w i t h i n each treatment as w e l l as the o v e r a l l r e s u l t s o f e a c h t r e a t m e n t . I n g e n e r a l t h e r e s u l t s were q u i t e v a r i e d between t r e a t m e n t s a n d b e t w e e n c o a l s . Thus i n t h e c a s e o f ICO c o a l , t h e o v e r a l l y i e l d v a r i e d among t h e d i f f e r e n t t r e a t m e n t s between 74 a n d 96%, t h e o v e r a l l r e d u c t i o n i n p y r i t i c s u l f u r c o n t e n t b e t w e e n 12 and 87%, a n d t h e o v e r a l l r e d u c t i o n i n a s h c o n t e n t between 22 and 72%. S i m i l a r l y i n the case o f Jude c o a l , t h e o v e r a l l y i e l d v a r i e d among t h e d i f f e r e n t t r e a t m e n t s b e t w e e n 75 and 92%, t h e o v e r a l l r e d u c t i o n i n p y r i t i c s u l f u r c o n t e n t b e t w e e n 31 and 88%, a n d o v e r a l l r e d u c t i o n i n a s h c o n t e n t b e t w e e n 34 and 8 4 % . Although the f i r s t s e p a r a t i o n step o f a m u l t i s t e p treatment produced t h e g r e a t e s t r e d u c t i o n i n l e v e l o f i m p u r i t i e s , subs e q u e n t s e p a r a t i o n s t e p s a l s o removed s i g n i f i c a n t amounts o f s u l f u r and a s h ( F i g u r e s 3 a n d 4 ) . Hence, t h e s e p a r a t i o n methods a p p e a r e d t o be c o m p l e m e n t a r y , p a r t i c u l a r l y when u s e d i n c o n j u n c tion with particle size reduction. Among t h e v a r i o u s t r e a t m e n t s , t r e a t m e n t 1 6 , w h i c h i n c l u d e d a l l o f t h e c o m m i n u t i o n and s e p a r a t i o n s t e p s , p r o d u c e d t h e c l e a n e s t p r o d u c t f r o m ICO c o a l . T h i s p r o d u c t , r e c o v e r e d w i t h an o v e r a l l y i e l d o f 7 8 % , c o n t a i n e d o n l y 2.3% a s h and 0.3% p y r i t i c s u l f u r w h i c h r e p r e s e n t e d a n o v e r a l l r e d u c t i o n o f 7 2 % i n a s h c o n t e n t and 8 7 % i n p y r i t i c s u l f u r c o n t e n t . T r e a t m e n t s 8, 1 2 , and 14 were n e a r l y a s e f f e c t i v e i n r e m o v i n g s u l f u r a n d a s h f r o m ICO c o a l a n d p r o v i d ed h i g h e r y i e l d s t h a n t r e a t m e n t 16. T r e a t m e n t s 8, 1 4 , a n d 16 were a b o u t e q u a l l y e f f e c t i v e i n r e m o v i n g s u l f u r a n d a s h f r o m Jude c o a l . The p r o d u c t o f t h e s e t r e a t m e n t s c o n t a i n e d a b o u t 0.4% p y r i t i c s u l f u r a n d 2.2-2.7% a s h w h i c h r e p r e s e n t e d a n o v e r a l l r e d u c t i o n o f 86-88% i n p y r i t i c s u l f u r c o n t e n t and 81-84% i n a s h c o n t e n t . However, t r e a t m e n t s 14 and 16 p r o v i d e d a l a r g e r o v e r a l l y i e l d (84%) t h a n t r e a t m e n t 8 (75%). The r e l a t i v e e f f i c i e n c y o f t h e v a r i o u s t r e a t m e n t s i s i l l u s t r a t e d by F i g u r e s 5 and 6 i n w h i c h t h e o v e r a l l y i e l d o f p r o d u c t i s p l o t t e d a g a i n s t the c o r r e s p o n d i n g p y r i t i c s u l f u r o r a s h c o n t e n t . The upper c u r v e i n e a c h d i a g r a m i s drawn t h r o u g h t h e p o i n t s r e p r e s e n t i n g t h e treatments which p r o v i d e d the h i g h e s t y i e l d s f o r t h e corresponding l e v e l s of impurities. Thus f o r ICO c o a l t r e a t m e n t s 2, 1 0 , 1 2 , 1 4 , and 16 were t h e most e f f i c i e n t f r o m t h e s t a n d p o i n t o f s u l f u r r e m o v a l and t r e a t m e n t s 2, 6, 8, 1 4 , and 16 f r o m t h e standpoint o f ash removal. S i m i l a r l y f o r Jude c o a l t r e a t m e n t s 10, 1 1 , 1 2 , and 14 were t h e most e f f i c i e n t f r o m t h e s t a n d p o i n t o f s u l f u l r r e m o v a l a n d t r e a t m e n t s 1 0 , 1 2 , 1 4 , a n d 16 f r o m t h e s t a n d p o i n t of ash removal. F o r t h e most p a r t , t h e s e t r e a t m e n t s had two t h i n g s i n common. Thus, e x c e p t f o r t r e a t m e n t 11 a p p l i e d t o Jude

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

COAL

TREATMENT 3 8 10 12

DESULFURIZATION

14 16

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MM

• OIL AGGLOM. E) FROTH FLOT. • GRAVITY SEP. ICO COAL

100"

2

4

TREATMENT 6 8 10

m

12

14 16

95 90 Q _J

80 75

i

Figure 2.

JUDE COAL

Weight yield of product from the different treatments

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch007

7.

M I N AND WHEELOCK

Coal Beneficiation Methods

6

8 10 TREATMENT

100

• OIL AGGLOM. Θ FROTH FLOT. : 80U Ξ GRAVITY SEP.

60

JUDE COAL

m pi

40

:

1

2 0

ο 6

8 10 TREATMENT

12

14

16

Figure 3. Reduction in pyritic sulfur content provided by the different treatments

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

91

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92

COAL

DESULFURIZATION

TREATMENT

100 80

OIL AGGLOM. FROTH FLOT. GRAVITY SEP.

JUDE COAL

il

§60 Ο

m

Ω 40 LU

3 20 0 6

Figure 4.

8 Ί0 TREATMENT

12

14

16

Reduction in ash content provided by the different treatments

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

M I N AND

WHEELOCK

Coal Beneficiation Methods

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch007

7.

Figure 5.

Overall yield vs. final pyritic sulfur content of the product from the different treatments

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

93

DESULFURIZATION

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch007

COAL

\ure 6.

Overall yield vs. the ash content of the final product from the different treatments

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch007

7.

MIN

AND

WHEELOCK

Coal Beneficiation Methods

95

c o a l , a l l of the treatments i n v o l v e d f i n e g r i n d i n g b e f o r e the o i l a g g l o m e r a t i o n s t e p . I n a d d i t i o n , e x c e p t f o r t r e a t m e n t s 2 and 6 a p p l i e d t o ICO c o a l , a l l o f the t r e a t m e n t s i n v o l v e d c h e m i c a l comminution. The u p p e r c u r v e i n e a c h d i a g r a m o f F i g u r e s 5 and 6 i l l u s ­ t r a t e s t h e t r a d e o f f b e t w e e n o v e r a l l y i e l d and l e v e l o f i m p u r i t i e s i n the p r o d u c t . The y i e l d f e l l o f f as t h e l e v e l o f i m p u r i t i e s was r e d u c e d t h r o u g h a p p l i c a t i o n o f t r e a t m e n t s o f g r e a t e r and g r e a t e r c o m p l e x i t y . W i t h ICO c o a l t h e d r o p i n y i e l d was q u i t e p r e c i p i t o u s when t h e p y r i t i c s u l f u r c o n t e n t was r e d u c e d b e l o w 0.5% o r t h e a s h c o n t e n t b e l o w 2.5% ( F i g u r e s 5 and 6 ) . Therefore f o r t h i s c o a l , t r e a t m e n t s 14 and 16, w h i c h p r o v i d e d t h e c l e a n e s t c o a l b u t a t c o n s i d e r a b l e s a c r i f i c e i n y i e l d , w o u l d be e s p e c i a l l y hard to j u s t i f y . N e a r l y a l l o f t h e t r e a t m e n t s d e s c r i b e d by F i g u r e 1 were more e f f i c i e n t t h a n s i n g l e - s t a g e g r a v i t y s e p a r a t i o n o f 4 cm χ 0 c o a l . The y i e l d and c o r r e s p o n d i n g a s h c o n t e n t p r o v i d e d by g r a v i t y s e p a r a t i o n of the coarse m a t e r i a l s i n l i q u i d s of d i f f e r e n t s p e c i f ­ i c g r a v i t y a r e r e p r e s e n t e d by the w a s h a b i l i t y c u r v e s i n F i g u r e 6. F o r e i t h e r k i n d o f c o a l t h e y i e l d f e l l o f f s h a r p l y as t h e a s h c o n t e n t was r e d u c e d t o l o w e r l e v e l s by s e p a r a t i o n i n l i g h t e r liquids. A comparison o f the r e s u l t s o f the f i r s t s e p a r a t i o n s t e p o f e a c h o f the v a r i o u s t r e a t m e n t s i n d i c a t e s t h e r e l a t i v e e f f i c i e n c y o f t h e d i f f e r e n t s e p a r a t i o n methods w h i c h were u s e d . Thus i n t h e c a s e o f ICO c o a l , the f r o t h f l o t a t i o n s t e p o f t r e a t m e n t s 11 o r 12 r e d u c e d t h e p y r i t i c s u l f u r c o n t e n t more t h a n t h e f i r s t s e p a r a t i o n s t e p o f any o t h e r t r e a t m e n t , and t h e f r o t h f l o t a t i o n s t e p o f t r e a t m e n t s 3 o r 4 r e d u c e d the a s h c o n t e n t more t h a n t h e f i r s t s e p a r a t i o n s t e p o f any o t h e r t r e a t m e n t . A l s o the r e s p e c t i v e f r o t h f l o t a t i o n s t e p s p r o v i d e d the h i g h e s t y i e l d s f o r the l e v e l o f i m p u r i t i e s a t t a i n e d . The g r a v i t y s e p a r a t i o n s t e p o f t r e a t m e n t s 5-8 was n e a r l y as e f f i c i e n t i n r e d u c i n g t h e a s h c o n t e n t o f ICO c o a l as t h e f r o t h f l o t a t i o n s t e p o f t r e a t m e n t s 3 o r 4, b u t i t was n o t as e f f i c i e n t i n r e d u c i n g t h e s u l f u r c o n t e n t . However, g r a v i t y s e p a r a t i o n was a p p l i e d t o c o a r s e r m a t e r i a l t h a n f r o t h f l o t a t i o n . In the case of Jude c o a l , the g r a v i t y s e p a r a t i o n s t e p o f t r e a t ­ ments 13-16 p r o v i d e d t h e g r e a t e s t r e d u c t i o n i n p y r i t i c s u l f u r and a s h c o n t e n t s o f any o f t h e f i r s t - s t e p s e p a r a t i o n s as w e l l as t h e h i g h e s t y i e l d f o r t h e l e v e l o f i m p u r i t i e s a t t a i n e d . The n e x t most e f f e c t i v e f i r s t - s t e p s e p a r a t i o n was t h a t p r o v i d e d by o i l a g g l o m e r a t i o n o f b a l l - m i l l e d Jude c o a l i n t r e a t m e n t 10. This s t e p r e d u c e d t h e a s h c o n t e n t o f J u d e c o a l a l m o s t as much as t h e g r a v i t y s e p a r a t i o n s t e p and a l s o p r o d u c e d a h i g h e r y i e l d . On t h e o t h e r h a n d , i t was n o t n e a r l y as e f f e c t i v e i n r e d u c i n g t h e p y r i t i c s u l f u r c o n t e n t as t h e g r a v i t y s e p a r a t i o n s t e p o f t r e a t ­ ments 13-16. I t has a l r e a d y been n o t e d t h a t g e n e r a l l y t h e most e f f i c i e n t t r e a t m e n t s i n v o l v e d f i n e g r i n d i n g and c h e m i c a l c o m m i n u t i o n . To e x a m i n e t h e e f f e c t o f f i n e g r i n d i n g f u r t h e r , the o v e r a l l r e s u l t s

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

96

C O A L DESULFURIZATION

T a b l e I I I . E f f e c t o f G r i n d i n g on O v e r a l l R e s u l t s

Excluded (Odd T r t . )

Included (Even T r t . )

ICO c o a l ash r e d u c t i o n pyritic sulfur reduction yield

47 58 83

55 67 87

65 61 82

71 71 84

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Jude c o a l ash r e d u c t i o n pyritic sulfur reduction yield

o f t h e even-numbered t r e a t m e n t s w h i c h i n c l u d e d f i n e g r i n d i n g and the o v e r a l l r e s u l t s o f t h e odd-numbered t r e a t m e n t s w h i c h e x c l u d e d t h i s s t e p were a v e r a g e d s e p a r a t e l y . The two s e t s o f v a l u e s w h i c h a r e p r e s e n t e d i n T a b l e I I I i n d i c a t e t h a t on t h e a v e r a g e t h e t r e a t ments w h i c h i n c l u d e d f i n e g r i n d i n g p r o d u c e d a c l e a n e r p r o d u c t i n g r e a t e r y i e l d than the treatments which d i d n o t i n c l u d e i t . T h e r e f o r e i t a p p e a r s t h a t f i n e g r i n d i n g i s a v e r y e f f e c t i v e means f o r i m p r o v i n g t h e s e p a r a t i o n o f p y r i t e and o t h e r a s h - f o r m i n g m i n e r a l s f r o m b o t h ICO and J u d e c o a l s . S i m i l a r l y t o study the e f f e c t o f chemical comminution f u r t h e r , the o v e r a l l r e s u l t s o f the l a s t e i g h t treatments which i n c l u d e d t h i s s t e p and t h e r e s u l t s o f t h e f i r s t e i g h t t r e a t m e n t s w h i c h e x c l u d e d t h i s s t e p were a v e r a g e d s e p a r a t e l y . The two s e t s o f v a l u e s ( T a b l e I V ) i n d i c a t e t h a t on t h e a v e r a g e t h e t r e a t m e n t s wich i n c l u d e d c h e m i c a l comminution p r o v i d e d a c l e a n e r product than t h e t r e a t m e n t s which d i d n o t . A l s o w i t h Jude c o a l , b u t n o t w i t h ICO c o a l , a l a r g e r y i e l d was p r o v i d e d on t h e a v e r a g e by t h e t r e a t m e n t s which i n c l u d e d t h i s s t e p . T h e r e f o r e , a t l e a s t f o r Jude c o a l , c h e m i c a l c o m m i n u t i o n i s an e f f e c t i v e method o f i m p r o v i n g the s e p a r a t i o n o f m i n e r a l i m p u r i t i e s . The e f f e c t i v e n e s s o f t h e g r a v i t y s e p a r a t i o n s t e p was a l s o e v a l u a t e d f u r t h e r by a v e r a g i n g t h e o v e r a l l r e s u l t s o f t h e t r e a t ments w h i c h i n c l u d e d i t and t h e r e s u l t s o f t h e t r e a t m e n t s w h i c h e x c l u d e d i t s e p a r a t e l y . The a v e r a e e r e d u c t i o n i n b o t h D v r i t i c s u l f u r and a s h was much g r e a t e r f o r t h o s e t r e a t m e n t s w h i c h i n c l u d e d t h i s step than f o r those which excluded i t (Table V ) . A l t h o u g h t h e a v e r a g e p r o d u c t y i e l d was l o w e r f o r t h e t r e a t m e n t s w h i c h i n c l u d e d g r a v i t y s e p a r a t i o n , t h e p e n a l t y i n y i e l d was r a t h e r modest f o r t h e l a r g e r e d u c t i o n i n l e v e l o f i m p u r i t i e s w h i c h was a c h i e v e d .

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

7.

MIN

AND

WHEELOCK

Table IV.

97

Coal Beneficiation Methods

E f f e c t o f C h e m i c a l C o m m i n u t i o n on O v e r a l l R e s u l t s

Excluded ( T r t . 1-8)

Included ( T r t . 9-16)

ICO c o a l ash r e d u c t i o n p y r i t i c sulfur reduction yield

50 55 88

52 70 82

63 63 80

73 68 86

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Jude c o a l ash r e d u c t i o n p y r i t i c sulfur reduction yield

T a b l e V.

E f f e c t o f G r a v i t y S e p a r a t i o n on O v e r a l l R e s u l t s

Excluded ( T r t . 1-4,9-12)

Included ( T r t . 5-8,13-16)

ICO c o a l ash r e d u c t i o n pyritic sulfur reduction yield

41% 51% 88%

62% 74% 82%

60% 54% 86%

76% 77% 80%

Jude c o a l ash r e d u c t i o n p y r i t i c sulfur reduction yield

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

COAL

98

Table V I .

DESULFURIZATION

E f f e c t o f F r o t h F l o t a t i o n on O v e r a l l R e s u l t s

Excluded ( T r t . 1,2,5,6, 9,10,13,14)

Included ( T r t . 3,4,7, 8,11,12,15,16)

ICO c o a l ash r e d u c t i o n pyritic sulfur yield

reduction

40% 50% 87%

62% 75% 83%

reduction

61% 56% 84%

74% 75% 82%

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Jude c o a l ash r e d u c t i o n pyritic sulfur yield

The e f f e c t i v e n e s s o f t h e f r o t h f l o t a t i o n s t e p was a l s o e v a l u a t e d by c o m p a r i n g t h e a v e r a g e o v e r a l l r e s u l t s o f t h e t r e a t ments w h i c h i n c l u d e d t h i s s t e p w i t h t h e a v e r a g e r e s u l t s o f t h e o t h e r t r e a t m e n t s T a b l e V I ) . Here a g a i n t h e t r e a t m e n t s w h i c h i n c l u d e d t h i s method o f s e p a r a t i o n p r o v i d e d a much c l e a n e r p r o d u c t than those which d i d not i n c l u d e i t w h i l e e x p e r i e n c i n g o n l y a modest r e d u c t i o n i n y i e l d . The e f f e c t i v e n e s s o f f r o t h f l o t a t i o n was v e r y s i m i l a r t o t h a t o f g r a v i t y s e p a r a t i o n , a l t h o u g h t h e two methods were a p p l i e d t o d i f f e r e n t s i z e s o f c o a l . The r e s u l t s o f t h e i n d i v i d u a l s t e p s o f o i l a g g l o m e r a t i o n and f r o t h f l o t a t i o n were a v e r a g e d t o compare t h e e f f e c t i v e n e s s o f one method a g a i n s t t h e o t h e r . A l s o i n the case o f o i l agglomeration, the r e s u l t s o f a g g l o m e r a t i n g -35 mesh c o a l were a v e r a g e d s e p a r a t e l y f r o m t h e r e s u l t s o f a g g l o m e r a t i n g -400 mesh c o a l t o d e t e r m i n e t h e e f f e c t o f p a r t i c l e s i z e on t h i s method o f s e p a r a t i o n . From the d a t a p r e s e n t e d i n T a b l e V I I i t c a n be s e e n t h a t t h e o i l a g g l o m e r a t i o n s t e p was much more e f f e c t i v e when i t was a p p l i e d t o -400 mesh c o a l t h a n when i t was a p p l i e d t o -35 mesh c o a l ; n o t o n l y d i d a c l e a n e r p r o d u c t r e s u l t , i t was r e c o v e r e d i n a l a r g e r yield. I n a d d i t i o n t h e o i l a g g l o m e r a t i o n s t e p a p p l i e d t o -400 mesh Jude c o a l was more e f f e c t i v e on t h e a v e r a g e t h a n t h e f r o t h f l o t a t i o n s t e p a p p l i e d t o -35 mesh m a t e r i a l . However, i n t h e c a s e o f ICO c o a l t h e r e s u l t s were m i x e d w i t h f r o t h f l o t a t i o n a p p e a r i n g t o have t h e edge w i t h r e g a r d t o s u l f u r r e m o v a l b u t n o t w i t h regard to ash removal. Conclusions The l a b o r a t o r y a p p l i c a t i o n o f 16 d i f f e r e n t

treatments i n -

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

7.

MIN

AND WHEELOCK

Table V I I .

Coal Beneficiation Methods

99

O i l A g g l o m e r a t i o n Step v s . F r o t h F l o t a t i o n

O i l Aggl. -35 mesh ( T r t . 1,5, 9,13)

O i l Aggl. -400 mesh ( T r t . 2,6, 10,14)

Step

Froth Flot. -35 mesh ( T r t . 3,7, 11,15)

ICO c o a l

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ash r e d u c t i o n pyritic sulfur yield

reduction

20 16 89

34 40 95

30 51 93

reduction

36 23 88

47 44 93

31 35 94

Jude c o a l ash r e d u c t i o n pyritic sulfur yield

v o l v i n g s i z e r e d u c t i o n and p h y s i c a l s e p a r a t i o n t o h i g h - s u l f u r c o a l c o n t a i n i n g s u b s t a n t i a l amounts o f f i n e l y d i s s e m i n a t e d microc r y s t a l s o f i r o n p y r i t e s p r o v i d e d s e v e r a l i n t e r e s t i n g and i m ­ portant r e s u l t s . Comparison o f these r e s u l t s w i t h a standard w a s h a b i l i t y a n a l y s i s showed t h a t most o f t h e t r e a t m e n t s p r o d u c e d a c l e a n e r c o a l f o r a g i v e n y i e l d t h a n c o u l d be o b t a i n e d by g r a v i t y s e p a r a t i o n a l o n e o f 4 cm χ 0 s i z e c o a l . In t h i s regard the t r e a t m e n t s w h i c h f a i l e d t o p r o d u c e c o a l w i t h a l o w e r s u l f u r c o n t e n t were g e n e r a l l y t h o s e w h i c h i n v o l v e d o n l y s i z e r e d u c t i o n and o i l a g g l o m e r a t i o n . T r e a t m e n t s i n v o l v i n g two and sometimes t h r e e methods o f s e p a r a t i o n i n sequence proved p a r t i c u l a r l y e f f e c t i v e . Thus t h e p y r i t i c s u l f u r c o n t e n t o f two Iowa c o a l s was r e d u c e d 85-86% w i t h an o v e r a l l y i e l d o f 82-84% by t r e a t m e n t 14 w h i c h i n c l u d e d c h e m i c a l comminution, r o l l c r u s h i n g , g r a v i t y s e p a r a t i o n , f i n e g r i n d i n g , and o i l a g g l o m e r a t i o n . T h i s s u l f u r r e d u c t i o n was c o n s i d e r a b l y h i g h e r t h a n t h a t p r o v i d e d by s i n g l e - s t a g e s e p a r a t i o n . Thus a maximum r e d u c t i o n o f 6 6 % i n t h e p y r i t i c s u l f u r c o n t e n t o f ICO c o a l was r e a l i z e d d u r i n g t h e f r o t h f l o t a t i o n s t e p o f t r e a t m e n t s 11-12 and o f 64% i n t h e p y r i t i c s u l f u r c o n t e n t o f J u d e c o a l d u r i n g the g r a v i t y s e p a r a t i o n s t e p o f t r e a t m e n t s 13-16. E a c h o f t h e s e p a r a t i o n methods u s e d i n t h e s e treatments proved e f f e c t i v e i n i t s e l f . M o r e o v e r t h e methods seemed t o com­ p l e m e n t e a c h o t h e r , p a r t i c u l a r l y when used i n c o n j u n c t i o n w i t h particle size reduction. Chemical comminution g e n e r a l l y improved the s e p a r a t i o n e f f i c i e n c y o f t h e v a r i o u s t r e a t m e n t s and f i n e g r i n d i n g t h e s e p a r a t i o n e f f i c i e n c y o f t h e o i l a g g l o m e r a t i o n method o f sépara-

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COAL

DESULFURIZATION

tion i n particular. Acknowledgement T h i s r e p o r t i s b a s e d on a p a p e r w h i c h was p r e s e n t e d a t t h e NCA/BCR CoaJ C o n f e r e n c e and Expo I I I , L o u i s v i l l e , KY, O c t . 1 9 - 2 1 , 1976. The work was s p o n s o r e d by t h e Iowa C o a l P r o j e c t and c o n ­ d u c t e d i n t h e E n e r g y and M i n e r a l R e s o u r c e s R e s e a r c h I n s t i t u t e a t Iowa S t a t e U n i v e r s i t y .

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Literature Cited

1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13.

Aplan, F. F., this volume, in press. Cavallaro, J. Α., Deurbrouck, A. W., this volume, in press. Zimmerman, R. Ε., Min. Cong. J. (1964) 50 (5), 26. Capes, C. E., Smith, A. E., Puddington, I. Ε., CIM Bull. (1974) 67, 115. Capes, C. E.,McIlhinney,A. E., Coleman, R. D., Trans. Soc. Min. Eng., AIME (1970) 247, 233. Brisse, A. H., McMorris, W. L., Jr., Trans. Soc. Min. Eng., AIME (1958) 211, 258. Howard, P. Η., Datta, R. S., this volume, in press. Datta, R. S., Howard, P. Η., Hanchett, Α., NCA/BCR Coal Conference and Expo III (Oct. 19-21, 1976), Louisville, KY. Howard P. Η., Hanchett, Α., Aldrich, R. G., Symposium II Clean Fuels from Coal, (June 23-27, 1975), Institute of Gas Technology, Chicago, IL. Book ASTM Stan., (1976) Part 26, "Gaseous Fuels; Coal and Coke; Atmospheric Analysis," Methods D2015-66, D2492-68, D3174-73, D3177-75. Greer, R. T., this volume, in press. Greer, R. T., "Nature and Distribution of Pyrite in Iowa Coal," Joint Meeting of the Electron Microscopy Society of America and Microbeam Analysis Society, (August 9-13, 1976), Miami, FL. Methods of Analyzing and Testing Coal and Coke, U.S. Bur. Min. Bull. (1967) 638.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

8 Dry Table—Pyrite Removal from Coal D. C. WILSON

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FMC Corp., Santa Clara, CA 95052

Particle segregation within a flowing granular bed during passage through material handling equipment or during transfer from one piece of equipment to another is commonplace. The most readily observable of these is size segregation. Usually such segregations are undesirable in a system because of the potential of unstable processing and an interruption of product continuity. Three factors determine the extent of particle segregation in a moving particle bed: the physical configuration of the material handling equipment, the forces which convey the particles through that equipment, and the differences between the particles in one or more of their physical properties (size, shape, bulk density, resiliency and surface roughness). The equipment described below, specifically designed as a separator for dry particulates, combines these factors to exploit the inherent segregation within moving particle beds. The equipment can be used to remove pyrite and other ash-forming minerals from coal; experimental results of cleaning bituminous and subbituminous coals with it are reported. Equipment D e s c r i p t i o n Figure 1 contains a p e r s p e c t i v e drawing o f the d r y t a b l e , being developed by FMC Corporation, and a c r o s s s e c t i o n through the u n i t i l l u s t r a t i n g the p a r t i c l e bed. The d r i v e u n i t f o r the t a b l e shown i s an electromechanical e x c i t e r o f the type used f o r v i b r a t i n g feeders. In f a c t , t h i s r e c e n t l y developed c o a l c l e a n ing u n i t i s a feeder, but with the f o l l o w i n g design d i f f e r e n c e s : (1) The deck surface i s short but very wide. (2) The c o a l i s i n s e r t e d a t one side o f the feeder's deck. (3) The conveying f o r c e i s reversed; i t feeds the m a t e r i a l i n t o the t a b l e ' s backwall. (4) The p a r t i c l e bed's net flow i s from one side o f the feeder t o the other s i d e . (5) The deck i s nonsymmetrical about the v e r t i c a l plane passing through i t s center o f g r a v i t y and the e x c i t e r ' s l i n e o f 101

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102

DESULFURIZATION

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COAL

Figure 1.

Dry table principle; schematic view

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

8.

WILSON

Dry Table—Pyrite Removal from Coal

drive. C o a l i s f e d o n t o t h e l o n g e s t s i d e o f t h e u n i t , and t h e c o n v e y i n g f o r c e f r o m t h e d r i v e moves t h e p a r t i c l e s t o w a r d s t h e backwall. A l a r g e p i l e of p a r t i c l e s forms a g a i n s t the b a c k w a l l , f i l l i n g the e n t i r e trough. G r a v i t y moves t h e p a r t i c l e s on t h e p i l e s s u r f a c e down t h e open s l o p e as t h e c o n v e y i n g f o r c e c o n ­ t i n u e s to d r i v e the u n d e r l y i n g m a t e r i a l a g a i n s t the b a c k w a l l . The r e s u l t i s t h e c o n t i n u o u s o v e r t u r n i n g o f t h e bed. The p r e s s u r e o f t h e i n c o m i n g f e e d f o r c e s t h e o v e r t u r n i n g bed t o f l o w a c r o s s t h e d e c k away f r o m t h e f e e d s i d e i n a h e l i c a l m o t i o n , and b e c a u s e t h e deck's l e n g t h d i m i n i s h e s (tapers) i n t h i s d i r e c t i o n , the toe of the p i l e i s being c o n t i n u o u s l y d i s c h a r g e d . S i m u l t a n e o u s l y , s i z e and b u l k d e n s i t y s e p a r a t i o n s a r e o c c u r ­ r i n g i n t h e o v e r t u r n i n g bed. The l a r g e o r l o w - d e n s i t y p a r t i c l e s move i n t o a s p i r a l l i n g p a t h t h a t m i g r a t e s t o w a r d t h e t o e o f t h e p i l e ( S e c t i o n Α-A, F i g u r e 1) w h e r e a s t h e s m a l l o r h i g h - d e n s i t y p a r t i c l e s move i n t o a s m a l l e r s p i r a l and c o n c e n t r a t e t o w a r d s t h e backwall. Those p a r t i c l e s t h a t a r e b o t h l a r g e and o f low d e n s i t y ( c o a l ) a d v a n c e p a s t t h e l a r g e and h i g h - d e n s i t y p a r t i c l e s ( r o c k and p y r i t e ) and p r e v a i l i n o b t a i n i n g p o s i t i o n s a t t h e t o e o f t h e pile. A l s o s m a l l p a r t i c l e s of p y r i t e w i l l c o n c e n t r a t e a t the b a c k w a l l i n preference to s m a l l p a r t i c l e s of c o a l . The o v e r a l l r e s u l t i n g d i s c h a r g e f r o m t h e h o r i z o n t a l d e c k p o r ­ t i o n of the u n i t i s a s e r i e s of staggered p a r t i c l e s i z e g r a d a t i o n s o f d i f f e r e n t d e n s i t i e s (when b u l k d e n s i t i e s a r e d i r e c t l y r e l a t e d to apparent d e n s i t i e s ) . To a v o i d t h i s o v e r l a p p i n g o f t h e s i z e g r a d a t i o n s o f t h e r o c k and p y r i t e w i t h t h e c o a l , t h e f e e d t o t h e u n i t i s p r e s i z e d t o d e f i n i t e s i z e r a n g e s . F o r t h e c o a l , r o c k , and p y r i t e s e p a r a t i o n , the g e n e r a l i z e d top s i z e t o bottom s i z e of the f e e d p a r t i c l e s i n any one p a s s i s a 4 - t o - l r a t i o (8 χ 2 i n . , 2 χ 1/2 i n . , e t c . ) . The optimum ratio» however, i s a f u n c t i o n o f b u l k d e n s i t y , s h a p e , r e s i l i e n c y , and s u r f a c e r o u g h n e s s d i f f e r e n c e s b e t w e e n t h e c o a l and r o c k - p y r i t e f o r a p a r t i c u l a r c o a l seam and mining c o n d i t i o n s . The p a r t i c l e s d i s c h a r g e f r o m t h e n e a r l y h o r i z o n t a l d e c k o n t o an a t t a c h e d downward s l o p i n g s u r f a c e r e f e r r e d t o as t h e " d i s c h a r g e lip". T h i s l i p c a n make f u r t h e r s e p a r a t i o n s b a s e d on p a r t i c l e s h a p e , r e s i l i e n c y , and s u r f a c e r o u g h n e s s i f d e s i r e d . The shape s e p a r a t i o n i s b a s e d on t h e c u b i c a l c o a l p a r t i c l e s b e i n g u n s t a b l e on t h e d i s c h a r g e l i p and t h e n e a r t a b u l a r r o c k and p y r i t e p a r t i ­ c l e s b e i n g s t a b l e when t h e u n i t i s v i b r a t i n g . The u n s t a b l e c o a l w i l l t h u s be d i s c h a r g e d by r o l l i n g o f f t h e l i p w h i l e t h e t a b u l a r r o c k and p y r i t e a r e c o n v e y e d b a c k up t h e l i p i n t o t h e p i l e . The s u r f a c e roughness of the h i g h l y m i n e r a l i z e d p a r t i c l e s i s g r e a t e r than that f o r the c l e a n c o a l p a r t i c l e s . T h i s a d d i t i o n a l roughness h e l p s t o c o n v e y t h e r o c k and p y r i t e b a c k i n t o t h e deep p a r t i c l e bed w h e r e a s t h e s l i c k c o a l t e n d s t o s l i p o f f t h e l i p . Generally, the r e s i l i e n c y of the c o a l i s g r e a t e r than t h a t of the r o c k particles. The c o n v e y i n g v i b r a t i o n s c a u s e s t h e more r e s i l i e n t c o a l p a r t i c l e s t o bounce and a s s u r e t h e i r u n s t a b i l i t y on t h e 1

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discharge l i p . The above d e s c r i b e s t h e m a j o r s e p a r a t i o n s o c c u r r i n g a t s p e c i f i e d l o c a t i o n s on t h e d r y t a b l e . Even t h o u g h p a r t i c l e s h a p e , r e s i l i e n c y , and s u r f a c e r o u g h n e s s d i f f e r e n c e s a r e n o t i n c l u d e d i n t h e d e s c r i p t i o n o f t h e o v e r t u r n i n g p a r t i c l e p i l e , t h e y do c o n t r i bute t o minor s e p a r a t i o n s w i t h i n the p i l e . Likewise, particle b u l k d e n s i t y and s i z e d i f f e r e n c e s a r e i n v o l v e d i n t h e s e p a r a t i o n on t h e l i p , b u t t h e s e a r e o f m i n o r i m p o r t a n c e when compared t o t h e d i f f e r e n c e s i n p a r t i c l e s h a p e , r e s i l i e n c y and s u r f a c e - r o u g h n e s s . W i t h t h e s e p a r a t i o n d r i v i n g f o r c e s o f t h e f i v e known p h y s i c a l property differences operating simultaneously, i t i s highly u n l i k e l y that a l l f i v e are working together to a r r i v e a t the d e s i r e d c o a l c l e a n i n g . T h e r e f o r e , most c o a l c l e a n i n g s e p a r a t i o n s a r e a compromise i n w h i c h t h e d r y t a b l e ' s o p e r a t i n g p a r a m e t e r s a r e a d j u s t e d t o enhance t h e d e s i r e d p h y s i c a l p r o p e r t y s e p a r a t i o n s and depress the undesirable separations. The f o l l o w i n g p h y s i c a l p r o p e r t y d i f f e r e n c e s l i s t d e s c r i b e s how t h e d r y t a b l e p a r a m e t e r c o n t r o l s i n f l u e n c e t h e d e g r e e o f t h e individual separations. Size. For c o a l c l e a n i n g , the feed t o the d r y t a b l e i s pre-screened i n t o s i z e ranges t o minimize the n a t u r a l l y strong s i z e s e g r e g a t i o n e f f e c t s i n a m o v i n g p a r t i c l e b e d . The n a r r o w e r t h e s i z e r a n g e , t h e l e s s s i z e s e g r e g a t i o n e f f e c t on t h e o v e r a l l separation. Systems c a n be d e v i s e d f o r p o s t - s c r e e n i n g b u t a t a s a c r i f i c e of the d r y t a b l e ' s throughput r a t e . Bulk Density. F o r c o a l c l e a n i n g a m o d e r a t e l y deep p i l e i s b e s t , as d e s c r i b e d below. I f t h e f r e q u e n c y and/or a m p l i t u d e i s i n c r e a s e d above a n o r m a l l e v e l , t h e n t h e p a r t i c l e bed becomes q u i t e p o r o u s and a l l p a r t i c l e s w i l l e x h i b i t a l i g h t e r b u l k d e n s i t y , thus reducing the e f f e c t i v e bulk d e n s i t y d i f f e r e n c e s . Shape. F o r w a r d o r b a c k w a r d t i l t i n g o f t h e d r y t a b l e c a u s e s t h e d i s c h a r g e l i p t o be a t d i f f e r e n t a n g l e s r e l a t i v e t o t h e h o r i z o n t a l w h i c h d e t e r m i n e s what s h a p e s a r e r e j e c t e d o r r e t a i n e d o n the t a b l e . A d i s c h a r g e l i p a n g l e o f -12° i s g e n e r a l l y u s e d f o r the s e p a r a t i o n o f c u b i c c o a l from t a b u l a r r o c k - p y r i t e . I f t h e r o c k - p y r i t e i s present as round p a r t i c l e s , then a l e s s steep d i s charge l i p i s used. Resiliency. By i n c r e a s i n g t h e u n i t ' s f r e q u e n c y a n d / o r s t r o k e above t h e n o r m a l l e v e l , t h e more r e s i l i e n t p a r t i c l e s i n t h e bed w i l l e x h i b i t a l o w e r b u l k d e n s i t y i n t h e p i l e s e c t i o n and s i m u l t a n e o u s l y become more u n s t a b l e on t h e l i p s e c t i o n . S u r f a c e R o u g h n e s s . The t y p e o f s u r f a c e f i n i s h on t h e d i s c h a r g e l i p combined w i t h t h e p a r t i c l e ' s own s u r f a c e r o u g h n e s s w i l l d e t e r m i n e i f i t i s d i s c h a r g e d o r r e t a i n e d on t h e t a b l e . A very hard s l i c k s u r f a c e w i l l discharge n e a r l y a l l p a r t i c l e types w h i l e

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

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105

a very hard rough s u r f a c e w i l l r e t a i n n e a r l y a l l p a r t i c l e types. The t h r o u g h p u t r a t e and bed r e t e n s i o n t i m e a r e c o n t r o l l e d by a l t e r i n g the c r o s s - s l o p e ( s i d e t o s i d e of u n i t ) . I n c r e a s i n g the c r o s s - s l o p e , by l o w e r i n g t h e f e e d s i d e o f t h e u n i t w i t h r e s p e c t t o i t s o p p o s i t e s i d e , w i l l c a u s e l o w e r t h r o u g h p u t r a t e s and l a r g e bed r e t e n s i o n times. There i s a c l o s e r e l a t i o n s h i p between the d r y t a b l e ' s v e r t i c a l s t r o k e component and f r e q u e n c y , w i t h some l i m i t a t i o n s d i c t a t e d by t h e p a r t i c l e s i z e s b e i n g s e p a r a t e d and t h e o p t i m i z a t i o n o f throughput r a t e s . Of o b v i o u s i m p o r t a n c e i s t h e h o r i z o n t a l c o n v e y ance of p a r t i c l e s t o form the o v e r t u r n i n g p i l e . The d e p t h o f t h a t p i l e i s t h e n , t o a l a r g e e x t e n t , d e t e r m i n e d by t h e v e r t i c a l c o n v e y a n c e . And t h e p i l e d e p t h i s i m p o r t a n t b e c a u s e v e r y deep p i l e s favor s i z e s e g r e g a t i o n w h i l e p i l e s of moderate depth favor b u l k density segregations. For c o a l c l e a n i n g , t h e r e f o r e , a f i x e d d r i v e a n g l e o f 30° was s e l e c t e d as t h e b e s t c o m b i n a t i o n o f h o r i z o n t a l and v e r t i c a l c o n v e y a n c e s i n f o r m i n g t h e d e s i r e d p i l e s o f m o d e r a t e d e p t h . The f r e q u e n c y i s r e l a t e d t o t h e s t r o k e ; w i t h i n c r e a s i n g s t r o k e l e n g t h , t h e f r e q u e n c y must be r e d u c e d t o m a i n t a i n t h e d e s i r e d t a b l i n g a c t i v i t y a t the s e l e c t e d d r i v e angle: 2 Stroke

(Frequency)

= Constant

The s t r o k e s h o u l d n o t be l a r g e r t h a n t h e s m a l l e s t p a r t i c l e d i a m e t e r t o be s e p a r a t e d o r p a r t i c l e m i x i n g becomes a f a c t o r i n t h e separation. However, u s i n g t h e l a r g e s t s i z e s t r o k e p o s s i b l e i s d e s i r a b l e because the throughput r a t e i n c r e a s e s w i t h i n c r e a s i n g stroke: 2 Stroke

<x ( T h r o u g h p u t R a t e )

S i n c e most o f t h e bed p a r t i c l e s a r e i n c o n t a c t w i t h e a c h o t h e r r a t h e r than w i t h the dry t a b l e s u r f a c e s , the c h a r a c t e r of the p a r t i c l e d i s c h a r g e i s a f u n c t i o n o f t h e bed c o m p o s i t i o n i t s e l f as w e l l as t h e a b o v e d e s c r i b e d p a r a m e t e r s . I f the r o c k - p y r i t e cont e n t of the feed i n c r e a s e s , a p r o p o r t i o n a l i n c r e a s e i n r o c k - p y r i t e w o u l d be e x p e c t e d t h r o u g h o u t a l l t h e d i s c h a r g e p r o d u c t s , i n c l u d i n g the c l e a n e s t c o a l product. T h i s phenomenon has been d e m o n s t r a t e d many t i m e s f o r a w i d e c o m p o s i t i o n o f f e e d w h i c h i n d i c a t e s t h a t t h e d r y t a b l e ' s s e p a r a t i o n p r i n c i p l e i s b a s e d on a p r o b a b i l i t y function. The d r y t a b l e has a d i s c h a r g e s i m i l a r i n c h a r a c t e r t o t h a t o f a wet c o n c e n t r a t i o n t a b l e i n t h a t i t i s a g r a d a t i o n f r o m a c l e a n c o a l product through m i n e r a l i z e d p a r t i c l e s to p y r i t e along the d i s c h a r g e edge. T h i s d r y method o f s e p a r a t i o n i s f u n c t i o n a l o v e r a b r o a d s p a n o f p a r t i c l e s i z e s . The l i m i t i n g f a c t o r f o r t h e minimum s i z e p a r t i c l e i s t h e f o r m a t i o n o f p a r t i c l e a g g l o m e r a t i o n s because of e l e c t r o s t a t i c charges or s u r f a c e moisture. No l i m i t i n g f a c t o r has b e e n e n c o u n t e r e d f o r t h e maximum s i z e p a r t i c l e s . The p r e s e n t p r a c t i c a l r a n g e i n c o a l p r e p a r a t i o n i s 1/8 - 8 i n . , t h e

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

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l o w e r l i m i t b e i n g d i c t a t e d b y s c r e e n i n g p r a c t i c e s and t h e u p p e r l i m i t b y t h e s i z e o f t h e p r e s e n t 15 f t p r o t o t y p e d r y t a b l e . A small 12 i n . l a b u n i t c a n p r e d i c t t h e p e r f o r m a n c e o f t h e l a r g e r 8- and 1 5 - f t u n i t s o n a p a r t i c u l a r r a w c o a l w i t h a f e e d o f p r o p o r t i o n a l l y s i z e d p a r t i c l e s because o f t h e p r o b a b i l i t y base o f the d r y t a b l e ' s s e p a r a t i o n p r i n c i p l e . Therefore, small-scale coal c l e a n i n g t e s t s a r e made f i r s t w i t h t h e l a b u n i t t o d e t e r m i n e t h e p a r a m e t e r s e t t i n g s and t o r e d u c e f i e l d t e s t t i m e r e q u i r e m e n t s . S t a n d a r d w a s h a b i l i t y d a t a o f raw c o a l i s o f l i t t l e v a l u e i n p r e ­ d i c t i n g what t h e p e r f o r m a n c e o f t h e d r y t a b l e w o u l d be b e c a u s e t h i s d a t a i s based on apparent d e n s i t i e s a l o n e . Most o f t h e d r y t a b l e e x p e r i e n c e i s i n t h e r e d u c t i o n o f t h e ash c o n t e n t o f c o a l s . However, t h e r e h a s b e e n a r e c e n t i n c r e a s e of i n t e r e s t i n t h e u s e o f t h e d r y t a b l e a s a method f o r s u l f u r reduction. Experimental Runs w e r e made w i t h t h e f o l l o w i n g - d e s c r i b e d s a m p l e s by p a s s ­ i n g them t h r o u g h one o f t h e d r y t a b l e u n i t s i n one p a s s and c o l l e c t i n g the discharge as m u l t i p l e products. I n F i g u r e 1, a n 1 1 - p r o d u c t d i s c h a r g e i s shown, A t h r o u g h K, where t h e d i s c h a r g e s a r e o f e q u a l increments spaced a l o n g t h e d i s c h a r g e l i p . Each d i s c h a r g e p r o d u c t was a n a l y z e d f o r a s h , p y r i t i c s u l f u r , and BTU c o n t e n t , f o l l o w i n g t h e a c c e p t e d ASTM methods D-271 and D-2492. The two c o a l s a m p l e s u s e d a r e d e s c r i b e d i n T a b l e I . Table I .

Sample D e s c r i p t i o n s and T e s t P a r a m e t e r s Bituminous Subbituminous

Source location condition mine Analysis BTU/lb Ash (%) P y r i t i c s u l f e r (%) Sample r u n p a r t i c l e s i z e (range) surface moisture Dry t a b l e p a r a m e t e r s location unit size throughput r a t e d r i v e type f r e q u e n c y (Hz) stroke (in.) d r i v e angle

R a t o n , NM wet p r o c e s s e d (heavy m e d i a ) underground

F r u i t l a n d , NM raw ( d i r e c t f r o m p i t )

13,460 10.1 0.44

8,060 25.8 0.19

1/4 i n . χ 8 mesh ~ 0 % , as r e c e i v e d S a n t a C l a r a , CA (FMC) 12-in (labunit) 0.01 t o n s / h r . electromagnetic 60 0.03 30°

surface

2 χ 1/2 i n . ~ 0 % , as r e c e i v e d Navajo Mine 8-ft ( p i l o t only) 3 tons/hr. electromechanical 18 0.25 30°

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Results The a n a l y t i c a l r e s u l t s o f t h e r u n s w i t h t h e b i t u m i n o u s and subbituminous samples were used t o c o n s t r u c t t h e d i s t r i b u t i o n c u r v e s shown i n F i g u r e 2. The h o r i z o n t a l a x i s f o r b o t h t h e u p p e r and l o w e r p o r t i o n o f t h e g r a p h r e p r e s e n t s t h e d i s c h a r g e f r o m t h e dry t a b l e as the 11-discharge products. I n t h e upper p o r t i o n , t h e v e r t i c a l a x i s g i v e s the r e c o v e r y as a percentage of the o r i g i n a l f e e d f o r h e a t i n g c o n t e n t (BTU), a s h , and p y r i t e . The c l e a n c o a l product i s the accumulation of discharge products s t a r t i n g at the f a r l e f t ( p e r c e n t a g e on l e f t v e r t i c a l a x i s ) , and t h e r e j e c t s t a r t s on t h e f a r r i g h t ( r i g h t v e r t i c a l a x i s ) . The d a t a p o i n t s p l o t t e d on t h e g r a p h a r e f o r r u n s w h i c h had a n e i g h t - p r o d u c t discharge. In t h e lower p o r t i o n of the graph, separate curves a r e p l o t t e d f o r p r o d u c t and r e j e c t w h i c h show t h e d i s t r i b u t i o n o f t h e p y r i t i c s u l f u r a s l b p e r m i l l i o n BTUs. Discussion As w i t h a l l c o a l c l e a n i n g e q u i p m e n t , t h e p e r f o r m a n c e i s a f u n c t i o n of the c o a l being cleaned. The d r y t a b l e i s no e x c e p t i o n t o t h i s and c a n be c o n s i d e r e d more s e n s i t i v e b e c a u s e i t u s e s a s many a s f i v e o f t h e p a r t i c l e s ' p h y s i c a l p r o p e r t y d i f f e r e n c e s f o r separation r a t h e r than j u s t the d e n s i t y d i f f e r e n c e alone. Also a f f e c t i n g t h e s e p a r a t i o n i s the degree t o which t h e major cons t i t u e n t s o f t h e r a w c o a l ( c l e a n c o a l , r o c k , and p y r i t e ) a r e l i b e r a t e d from each other. Therefore, a gradation of property differences f o r a l l the p a r t i c l e s p r o p e r t i e s , as w e l l as f o r s i z e , c a n e x i s t i n t h e g r a n u l a r f e e d t o be s e g r e g a t e d . Then t o t h i s add t h e d r y t a b l e ' s p r o b a b i l i t y b a s e f o r p a r t i c l e s e g r e g a t i o n , and t h e c o m p l e x i t y o f i n d e p t h i n t e r p r e t a t i o n o f t h e d r y t a b l e ' s r e s u l t s c a n be i n v i s i o n e d . The p y r i t e i n t h e two e x a m p l e s s e l e c t e d f o r t h i s d i s c u s s i o n i s u n l i b e r a t e d and o f r e l a t i v e l y l o w c o n c e n t r a t i o n . The l e t t e r e d discharge products A through D are d i v i s i o n s of the d r y t a b l e ' s d i s c h a r g e a r b i t r a r i l y s e l e c t e d f o r a n a l y t i c a l and d i s c u s s i o n p u r p o s e s , and t h e l a r g e number o f p r o d u c t d i v i s i o n s o r t h e i r s p e c i f i c b o u n d a r i e s , need n o t be u s e d i n a c t u a l c o a l c l e a n i n g applications. Subbituminous Coal. The o n l y p r e p a r a t i o n t h i s c o a l r e c e i v e d p r i o r t o b e i n g f e d t o t h e d r y t a b l e was p r e s i z i n g i n t o 4:1 s i z e r a n g e s . The s e q u e n c e o f t h e d i s t r i b u t i o n c u r v e s , ( F i g u r e 2, t o p ) show t h a t i n t h i s t h r e e component s y s t e m , c l e a n c o a l (BTU) r o c k (ash) - p y r i t e , t h e major s e p a r a t i o n i s between t h e c l e a n c o a l and t h e r o c k . The p y r i t e - a s h s e p a r a t i o n i s r e v e r s e d t o what w o u l d be e x p e c t e d f o r t h e more d e n s e p y r i t e , w h i c h f u r t h e r demons t r a t e s that t h e p y r i t e i s not l i b e r a t e d . There a r e three z o n a l types o f d i s c h a r g e from t h e d r y t a b l e w i t h t h i s c o a l . In the f i r s t z o n e , p r o d u c t d i s c h a r g e s A and B, t h e c o a l c o n t a i n s l o w a s h and h a s t h e p y r i t e m a i n l y a s s o c i a t e d w i t h t h e c o a l . I n t h e second 1

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COAL

Figure 2.

Dry table discharge distribution

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

8.

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109

Dry Table—Pyrite Removal from Coal

z o n e , p r o d u c t d i s c h a r g e s C t h r o u g h G, t h e c o a l c o n t a i n s l o w p y r i t e and a s h , b u t t h e p y r i t e i s a s s o c i a t e d w i t h t h e a s h . In the t h i r d z o n e , p r o d u c t d i s c h a r g e s H t h r o u g h K, t h e d i s c h a r g e c o n t a i n s a c o a l and r o c k m i x t u r e where t h e p y r i t e i s a s s o c i a t e d w i t h b o t h c o a l and r o c k a t h i g h e r c o n c e n t r a t i o n s . S e l e c t i n g d i s c h a r g e s A t h r o u g h I as a c l e a n c o a l p r o d u c t and J and Κ as r e j e c t g i v e s a 90% r e c o v e r y o f t h e c o a l ' s p o t e n t i a l h e a t i n g c o n t e n t and r e m o v a l s o f 75% o f t h e a s h and 50% o f t h e pyrite. The c o m p o s i t i o n s o f t h e p r o d u c t and r e j e c t a r e g i v e n i n Table I I .

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch008

Table I I .

S e l e c t e d Subbituminous Product

Yield (%) BTU/lb Ash (%) Pyritic sulfur

(%)

Coal

72 10,360 10.8 0.13

Product Rej e c t 28 2,160 64.1 0.32

W i t h t h e d i s c h a r g e s p l i t i n t o j u s t a c l e a n c o a l p r o d u c t and r e j e c t , t h e w e l l known compromise must be made b e t w e e n r e c o v e r i n g as much c l e a n c o a l as p o s s i b l e w h i l e r e j e c t i n g most o f t h e r o c k and p y r i t e . W i t h the d r y t a b l e , however, i t i s p o s s i b l e t o have a s many p r o d u c t s a s a r e r e a s o n a b l e . T h e r e f o r e , one c o u l d s e l e c t t h e zone o f l o w a s h c o n t e n t A t h r o u g h G as t h e c l e a n c o a l p r o d u c t and H t h r o u g h J f o r r e t r e a t m e n t , where t h e r e i s a m i x t u r e o f b o t h r o c k and c o a l , and Κ as t h e r e j e c t w h i c h e s s e n t i a l l y c o n t a i n s no usuable heat (Table I I I ) . Table I I I .

S e l e c t e d Subbituminous Product

Y i e l d (%) BTU/lb A s h (%) Pyritic sulfer

(%)

47 11,260 4. 7 0. 08

C o a l P r o d u c t and R e c y c l e Retreatment Reject 37 7,390 30.0 0.27

16 0 78 0.29

B o t h t h e c l e a n c o a l p r o d u c t and t h e r e j e c t a r e d e s i r a b l e : t h i s a r r a n g e m e n t , and i t s s u c c e s s depends upon t h e c h a r a c t e r o f the retreatment d i s c h a r g e . In t h i s p a r t i c u l a r case, the r e t r e a t ­ ment i s a m i x t u r e o f c l e a n c o a l and l i b e r a t e d r o c k w i t h a s m a l l amount o f m i d d l i n g s ( t h i s w o u l d be e x p e c t e d b e c a u s e t h e d r y t a b l e ' s p a r t i c l e s e g r e g a t i o n has a p r o b a b i l i t y b a s e ) . The r e t r e a t m e n t c a n be r e c y c l e d t h r o u g h t h e same u n i t o r s e n t t o a n o t h e r u n i t f o r a second p a s s . Bituminous C o a l . T h i s c o a l i s the product from a p r e p a r a t i o n p l a n t , and t h e r e f o r e t h e r e i s e s s e n t i a l l y no l i b e r a t e d p y r i t e o r r o c k p r e s e n t . The s e q u e n c e o f t h e c u r v e s shows t h a t t h e u n l i b e r a t e d p y r i t e i s u n e v e n l y d i s t r i b u t e d among t h e c o a l p a r t i c l e s and t h a t t h e m a j o r s e p a r a t i o n i s b e t w e e n t h e c l e a n c o a l and p y r i t e . The a s h and BTU c u r v e s a r e v e r y s i m i l a r , e x c e p t f o r a s l i g h t

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch008

110

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d i f f e r e n c e i n s l o p e s , showing t h a t t h e r e i s a n e a r - c o n s t a n t i n h e r e n t a s h i n t h e c o a l f o r t h e d i s c h a r g e p r o d u c t s A t h r o u g h H. The p y r i t e c u r v e i s q u i t e d i f f e r e n t i n shape and shows s m a l l amounts o f p y r i t e i n d i s c h a r g e p r o d u c t s A t h r o u g h D, i n c r e a s i n g amounts i n Ε t o J , and s u b s t a n t i a l q u a n t i t i e s i n K. There are f o u r z o n a l types of d i s c h a r g e f o r t h i s p a r t i c u l a r s e p a r a t i o n . In t h e f i r s t z o n e , d i s c h a r g e p r o d u c t s A t h r o u g h D, t h e c o a l has a minimum a s h and p y r i t e c o n t e n t . In the second zone, d i s c h a r g e p r o d u c t s D t o H, t h e c o a l c o n t a i n s a minimum o f a s h b u t has an increasing p y r i t e content. In the t h i r d zone, d i s c h a r g e p r o d u c t s I t h r o u g h J , t h e ash, and p y r i t e c o n t e n t p r o g r e s s i v e l y i n c r e a s e i n the c o a l . I n t h e f o u r t h z o n e , d i s c h a r g e p r o d u c t K, t h e c o a l i s h i g h e s t i n b o t h a s h and p y r i t e and c o n t a i n s a l l t h e m i s p l a c e d s i n k m a t e r i a l f r o m t h e wet w a s h i n g p r o c e s s . The s p e c i f i c g r a v i t y d i f f e r e n c e b e t w e e n t h e f i r s t and s e c o n d z o n e s i s q u i t e s m a l l , so t h e s e p a r a t i o n i s most l i k e l y c a u s e d by the o t h e r p h y s i c a l p r o p e r t i e s of the p a r t i c l e s . S i n c e the ash d i f f e r e n c e i s a l s o s m a l l , i t i s assumed t h a t t h e p r e s e n c e o f t h e p y r i t e i s r e l a t e d to the p h y s i c a l p r o p e r t y d i f f e r e n c e s which the d r y t a b l e c a n d i s t i n g u i s h f o r s e p a r a t i o n p u r p o s e s . The s u g g e s t e d method o f p r o c e s s i n g i s t o c o l l e c t t h e d i s c h a r g e f r o m d i s c h a r g e p r o d u c t s A t o H as a c l e a n c o a l p r o d u c t and I t o Κ f o r r e t r e a t m e n t (Table I V ) . T a b l e IV.

Selected

Yield (%) BTU/lb Ash (%) Pyritic sulfur

(%)

B i t u m i n o u s C o a l P r o d u c t and R e c y c l e Product Retreatment 75 13,750 7.5 0.22

25 12,600 17. ,5 1. ,08

F o r t h i s c o a l s a m p l e t h e r e t r e a t m e n t d i s c h a r g e s h o u l d not be p r o ­ c e s s e d as a s e c o n d p a s s on t h e d r y t a b l e b e c a u s e l i t t l e b e n e f i t w o u l d be r e a l i z e d i n a s h and p y r i t e r e d u c t i o n . The b e s t a p p r o a c h w o u l d be t o r e c y c l e t h i s m a t e r i a l t o t h e wet p r e p a r a t i o n p l a n t after crushing. Conclusion The d r y t a b l e c a n r e d u c e t h e s u l f u r c o n t e n t o f a c o a l t h r o u g h p y r i t e r e m o v a l . The e x t e n t o f t h e c o a l - p y r i t e s e p a r a t i o n w i l l be a f u n c t i o n o f p y r i t e l i b e r a t i o n and t h e p h y s i c a l p r o p e r t y d i f f e r ­ e n c e s b e t w e e n t h e f r e e f l o w i n g c o a l and p y r i t e p a r t i c l e s . How­ e v e r , t h e r e a r e c a s e s where e v e n c o a l c o n t a i n i n g u n l i b e r a t e d p y r i t e c a n be s e p a r a t e d i n t o c o a l p r o d u c t s o f l o w and h i g h p y r i t i c s u l f u r contents. The d r y t a b l e i s b e s t u s e d a s a r o u g h e r , s i n c e i t has a s e p a ­ r a t i o n s i m i l a r t o t h a t o f a Baum J i g . I t c a n be u s e d a l o n e o r i n c o n j u n c t i o n w i t h e x i s t i n g c o a l c l e a n i n g e q u i p m e n t . And i t i s

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

8.

WILSON

Dry Table—Pyrite Removal from Coal

111

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch008

e s p e c i a l l y a p p l i c a b l e where t h e u s e o f w a t e r i s r e s t r i c t e d b e c a u s e of l i m i t e d s u p p l y , f r e e z i n g , o r c o s t l y treatment p r i o r t o d i s charge or reuse.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

9 Magnetic Desulfurization of Some Illinois Basin Coals H A Y D N H. M U R R A Y

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch009

Dept. of Geology, Indiana Univ., Bloomington, I N 47401

High extraction magnetic filtration (HEMF) is used successfully to process kaolin (1). This is the first successful commercial application of a new level of magnetic separation equipment and processing technology which resulted from the joining of four major concepts (2). 1. Discovery of the importance of retention time in mineral separation. 2. Development of very high gradient matrix collectors. 3. High intensity fields in wet magnetic separator (up to 20 kG). 4. Modern design of large high field magnets. Use of longer retention time permits finely divided particles to migrate and be captured by a magnetized collection surface. The canister in the magnet is filled with a matrix of steel wool, screens made of sharp thin ribbons, or other filamentary material which provides very high gradients. Modern electronic and magnet technology led to the design of a magnet with a high field throughout a large cavity. A diagrammatic sketch of a large high intensity magnet is shown on Figure 1. The diameter of the canister can be up to 84 in. with a height of 20 in. Up to 120 tons of kaolin per hour can be processed through the 84-in. unit. Fabrication of equipment larger than 84 in. is feasible, but the problems involved in shipping and for on site fabrication are such that it is probably more efficient to consider multiple installations of 84-in. machines. High e x t r a c t i o n magnetic f i l t r a t i o n i s very s u c c e s s f u l i n r e m o v i n g i r o n and t i t a n i u m i m p u r i t i e s f r o m k a o l i n . Potential a p p l i c a t i o n s f o r i t s use f o r b e n e f i c i a t i o n o f o t h e r i n d u s t r i a l m i n e r a l s and c o a l have been demonstrated by Murray ( 3 , 4 , 5 ) . P r e s e n t HEMF e q u i p m e n t u s e s e l e c t r o m a g n e t s t o g e n e r a t e f i e l d s

112

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

9.

MURRAY

Magnetic Desulfurization of Illinois Coals

113

o f 20 kG. Power c o n s u m p t i o n o f t h i s e q u i p m e n t i s i n t h e r a n g e o f 400-500 kW. The p r e s e n t HEMF e q u i p m e n t i s o p t i m i z e d f o r s e p a r a t i o n o f s l u r r y c o n t a i n i n g f i n e s b e l o w 200 mesh and p r e f e r a b l y b e l o w 20 microns. O t h e r m a t r i x t y p e s can be s u b s t i t u t e d f o r s t a i n l e s s s t e e l w o o l t o a c c o m o d a t e c o a r s e r f e e d m a t e r i a l s (up t o 20 mesh) i n c l u d i n g F r a n t z s c r e e n s , l o o s e l y packed coarse s t e e l w o o l , s t e e l s h o t , s t e e l f i l i n g s , and o t h e r f i l a m e n t a r y m a t e r i a l . New d e v e l ­ opments a r e underway i n m a t r i x d e s i g n and c o m p o s i t i o n w h i c h can g r e a t l y enhance HEMF t e c h n o l o g y .

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch009

Magnetic D e s u l f u r i z a t i o n of

Coal

The e a r l i e s t w o r k c o n c e r n i n g t h e r e d u c t i o n o f s u l f u r i n c o a l by m a g n e t i c s e p a r a t i o n was d e s c r i b e d i n a German p a t e n t by S i d d i q u i i n 1957 ( 6 ) . Y u r o v s k y and R e m e s n i k o v (7) p u b l i s h e d a p a p e r i n 1958 r e p o r t i n g t h a t c o a l p u l v e r i z e d f i n e r t h a n 16-mesh s i z e s u b j e c t e d t o a t h e r m a l s t e a m - a i r t r e a t m e n t made t h e p y r i t e more m a g n e t i c , w h i c h e n h a n c e d b e n e f i c i a t i o n when p r o c e s s e d i n a s p e c i a l l y b u i l t magnetic separator. S u l f u r r e d u c t i o n s o f 85, 74.9, and 70% w e r e r e p o r t e d . P e r r y (8) r e p o r t e d t h a t f i n e p y r i t e (65 - 70 mesh) t r e a t e d i n s t e a m - a i r a t m o s p h e r e a t t e m p e r a t u r e s o f 570° - 750°F f o r v a r y i n g t i m e s up t o 10 m i n . i n c r e a s e d t h e q u a n t i t y o f p y r i t e amenable t o m a g n e t i c s e p a r a t i o n w i t h i n c r e a s ­ ing i n t e n s i t y of treatment. K e s t e r ( 9 , 10,) d e m o n s t r a t e d t h a t s u l f u r c o u l d be r e d u c e d t o a g r e a t e r e x t e n t by m a k i n g a h i g h i n t e n s i t y m a g n e t i c s e p a r a t i o n d i r e c t l y on raw u n t r e a t e d c o a l without u s i n g the thermal pretreatment s t e p . T h u s , by p u l v e r i z ­ i n g t h e c o a l t o a t y p i c a l power p l a n t s i z e and by m a g n e t i c a l l y s e p a r a t i n g t h e c o a r s e 48 by 200-mesh s i z e f r a c t i o n , s i g n i f i c a n t s u l f u r r e d u c t i o n was achieved. K e s t e r r e p o r t e d t h a t p y r i t i c s u l f u r a c c o u n t s f o r 40 t o as much as 80% o f t h e s u l f u r c o n t e n t o f most c o a l s ( 9 ) . Gluskoter and Simon (11) r e p o r t e d t h a t t h e mean t o t a l s u l f u r c o n t e n t i n 474 a n a l y s e s was 3.57% i n c o a l s f r o m I l l i n o i s , and t h e mean v a l u e o f p y r i t i c s u l f u r i n t h e s e same c o a l s was 2.06%. They f o u n d t h a t t h e r e i s on an a v e r a g e a p p r o x i m a t e l y 150% more p y r i t i c s u l f u r i n a s a m p l e as t h e r e i s o r g a n i c s u l f u r . Macroscopic p y r i t e occurs i n c o a l i n : v e i n s , u s u a l l y t h i c k and f i l m l i k e a l o n g v e r t i c a l j o i n t s ; i n l e n s e s t h a t a r e e x t r e m e l y v a r i a b l e i n shape and s i z e ; i n n o d u l e s o r b a l l s ; and i n d i s s e m i ­ n a t e d c r y s t a l s and i r r e g u l a r a g g r e g a t e s . Microscopic pyrite o c c u r s as s m a l l g l o b u l e s and b l e b s , f i n e v e i n l e t s , d e n d r i t e s , s m a l l e u h e d r a l c r y s t a l s , c e l l f i l l i n g s , and r e p l a c e m e n t p l a n t material. K e s t e r , L e o n a r d , and W i l s o n (12) r e p o r t e d t h a t t h e mass s u s c e p t i b i l i t y o f powdered p y r i t e was 4.53 χ 10^ cgs u n i t s . A n o t h e r v a l u e commonly u s e d f o r t h e m a g n e t i c s u s c e p t i b i l i t y o f p y r i t e i s 25 χ ΙΟ ** e l e c t r o m a g n e t i c u n i t s p e r cm. The s t r e n g t h o f m a g n e t i s m , w h i c h c a n be i n d u c e d i n t o a m i n e r a l depends upon -

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

114

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DESULFURIZATION

the p e r m e a b i l i t y o f the m i n e r a l a c c o r d i n g t o the e q u a t i o n : Β = uH W h e r e — = m a g n e t i c i n d u c t i o n i n g a u s s i n t h e m i n e r a l , _u = perme­ a b i l i t y o f t h e m i n e r a l , and Η = m a g n e t i c f i e l d i n t e n s i t y i n g a u s s . Therefore the s u s c e p t i b i l i t y i s :

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch009

B/H = 1 + 4 πΚ Where—Κ = magnetic s u s c e p t i b i l i t y expressed i n e l e c t r o m a g n e t i c u n i t s cm/gm/sec. I f t h e v a l u e o f Κ i s p o s i t i v e , t h e m i n e r a l i s termed p a r a m a g n e t i c and e x p e r i e n c e s a f o r c e w h i c h t e n d s t o a t t r a c t i t i n the d i r e c t i o n o f i n c r e a s i n g magnetic g r a d i e n t . I f Κ i s n e g a t i v e , t h e m i n e r a l i s d i a m a g n e t i c and e x p e r i e n c e s a repulsive force. Ferromagnetic m i n e r a l s , such as i r o n , e x p e r i ­ ence s t r o n g m a g n e t i c f o r c e s i n t h e d i r e c t i o n o f i n c r e a s i n g mag­ n e t i c g r a d i e n t and t h u s have v e r y l a r g e p o s i t i v e v a l u e s o f K. C o a l i s d i a m a g n e t i c ( 1 3 ) , and p y r i t e i s p a r a m a g n e t i c . Thus, i f t h e c o a l i s c r u s h e d and p u l v e r i z e d f i n e enough t o l i b e r a t e t h e p y r i t e , a good m a g n e t i c s e p a r a t i o n i s p o s s i b l e . A r e c e n t s t u d y by K i n d i g and T u r n e r ( 1 4 ) r e p o r t e d on a new p r o c e s s f o r r e m o v i n g p y r i t i c s u l f u r and a s h f r o m c o a l . The p u l v e r i z e d c o a l i s t r e a t e d w i t h i r o n c a r b o n y l vapor which puts a t h i n s k i n o f m a g n e t i c m a t e r i a l on t h e p y r i t e and a s h b u t does not a f f e c t the c o a l . Thus m a g n e t i c s e p a r a t o r s y i e l d a n o n ­ m a g n e t i c c o a l l o w i n s u l f u r and a s h and a m a g n e t i c f r a c t i o n h i g h i n s u l f u r and a s h . Experimental The c o a l s a m p l e s used f o r t h i s r e p o r t were p u l v e r i z e d so t h a t 90% p a s s e d t h r o u g h a 200-mesh s i e v e . The s a m p l e s were s l u r r i e d a t 30% s o l i d s f o r t h e wet m a g n e t i c t e s t s . F r a n t z s c r e e n s made f r o m t h i n s h a r p r i b b o n s o f 430 m a g n e t i c s t a i n l e s s s t e e l were u s e d a s the m a t r i x i n t h e c a n i s t e r . F o r the wet magnetic t e s t s r e t e n t i o n t i m e s o f 30, 6 0 , and 120 sec. were u s e d f o r one s e r i e s , and m u l ­ t i p l e p a s s e s w i t h a r e t e n t i o n t i m e o f 30 sec. e a c h were used f o r a second s e r i e s . F o r t h e d r y t e s t s t h e s e r i e s were r u n u s i n g g r a v i t y feed w i t h m u l t i p l e passes. The m a g n e t i c s e p a r a t o r used i n t h i s s t u d y was a p i l o t p l a n t model m a n u f a c t u r e d by P a c i f i c E l e c t r i c M o t o r Co. o f O a k l a n d , California. The HEMF e q u i p m e n t i n c l u d e s a f i l t e r c a n i s t e r w h i c h can be p a c k e d w i t h a f i l a m e n t a r y m a g n e t i c m a t e r i a l . The m a t r i x m a t e r i a l c a n e a s i l y be changed d e p e n d i n g o n t h e p a r t i c l e s i z e o f the feed s l u r r y . The c a n i s t e r i s s u r r o u n d e d by h o l l o w c o n d u c t o r c o p p e r c o i l s w h i c h e n e r g i z e t h e e n t i r e c a n i s t e r volume t o a f i e l d up t o 20 kG. The c o p p e r c o i l s a r e s u r r o u n d e d by a b o x - l i k e enclosure of s t e e l p l a t e which completes the magnetic c i r c u i t . The u n i t e o p e r a t e s a t power l e v e l s o f 200 kW.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

9.

MURRAY

Magnetic Desulfurization of Illinois Coals

The c o a l s a m p l e s were p u l v e r i z e d i n a l a b o r a t o r y hammer m i l l and a s m a l l r i n g m i l l . A f t e r t h e p u l v e r i z e d c o a l was s l u r r i e d w i t h t h e a i d o f a d i s p e r s a n t ( s o d i u m h e x a m e t a p h o s p h a t e ) , i t was a g i t a t e d w i t h a L i g h t n i n m i x e r and pumped up t h r o u g h t h e c a n i s t e r w i t h a p e r i s t a l t i c pump a t c o n t r o l l e d r a t e s . A p p r o x i m a t e l y 1 l b o f c o a l was r u n t h r o u g h t h e c a n i s t e r f o r e a c h t e s t . Samples o f -100 mesh were r u n and compared w i t h t h e -200 mesh s a m p l e s and much b e t t e r r e s u l t s were o b t a i n e d w i t h t h e f i n e r s a m p l e s . The c o a l s used f o r t h i s r e p o r t were c o m m e r c i a l l y mined c o a l s from the I l l i n o i s B a s i n . These a r e C o a l s V and V I f r o m I l l i n o i s and I n d i a n a . T a b l e I shows t h e s u l f u r c o n t e n t o f t h e v a r i o u s samples.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch009

Table I . S u l f u r Content

Coal

(%)

Total Sulfur

Inorganic Sulfur

4.63 4.17 3.59 1.98

2.44 2.20 2.39 1.02

I n d i a n a V ( W a r r i c k Co.) I n d i a n a V I ( W a r r i c k Co.) I l l i n o i s V (Wabash Co.) I l l i n o i s V I ( W i l l i a m s o n Co.)

Organic Sulfur

% Ash 12.8 11.4 10.3 7.1

2.19 1.97 1.20 0.96

F i g u r e s 2 and 3 i n d i c a t e t h e s u l f u r r e d u c t i o n o b t a i n e d w i t h i n c r e a s i n g r e t e n t i o n t i m e and up t o t h r e e p a s s e s t h r o u g h t h e magnet u s i n g wet s e p a r a t i o n methods. F i g u r e 4 shows t h e s u l f u r reduction obtained using a dry separation technique. The d a t a show t h a t t h e b e s t r e s u l t s a s f a r a s s u l f u r r e d u c t i o n i s c o n ­ c e r n e d were a t t a i n e d u s i n g a s l u r r y and t h r e e p a s s e s t h r o u g h t h e magnet, e a c h w i t h a r e t e n t i o n t i m e o f 30 s e c . T a b l e I I i s a summary o f t h e s u l f u r r e d u c t i o n o b t a i n e d u s i n g b o t h wet and d r y s e p a r a t i o n methods w i t h -200 mesh s a m p l e s . Table I I . S u l f u r Reduction

Coal Indiana Indiana Indiana Indiana Indiana Indiana Illinois Illinois Illinois Illinois Illinois Illinois a

Total S i n Product

Total S V V V VI VI VI V V V VI VI VI

3.00 3.30 3.78 2.30 2.45 3.31 1.96 2.18 2.87 1.15 1.29 1.57

4.63 4.63 4.63 4.17 4.17 4.17 3.59 3.59 3.59 1.98 1.98 1.98

Wet-three passes ;

a

b

c

a

b

e

D

a

b

e

a

b

e

(%)

Inorganic S i n Product 0.81 1.11 1.59 0.10 0.25 1.01 0.83 0.99 1.67 0.21 0.32 0.61

120-sec r e t e n t i o n ;

e

/'ζ I n o r g a n i c S Removed

dry- - t h r e e

)I A s h 6.4 7.9 9.2 6.2 7.1 8.8 5.8 6.3 8.6 4.1 4.9 5.6

67 55 25 85 78 39 65 59 30 79 69 40 passes

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

116

COAL DESULFURIZATION

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T O P VIEW

SLURRY OUT MAGNET

STEEL

ΙI

v

~

" *

ELECTRIC POWER

SLURRY

IN

SIDE V I E W SECTION THRU MAGNET

Figure 1.

Diagrammatic side and top view of HEMF

5.0

unit

I-

4.0

Figure 2. Sulfur content after I, 2, and 3 passes at 30 sec retention each (wet)

Control

ι 2 Number of Passes

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

9.

MURRAY

Magnetic Desulfurization of Illinois Coals

EXPLANATION • Coal V , Warrick C o . , Ind. A Coal V I , Warrick C o . , Ind. Ο

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch009

Coal V , Wabash C o . , III.

Δ Control

30

60

90

120

Coal V I , Williamson C o . , III.

Retention T i m e (seconds)

Figure 3.

Sulfur content wtih increasing retention time (wet)

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

117

118

C O A L DESULFURIZATION

One sample o f C o a l V f r o m I n d i a n a was p u l v e r i z e d so t h a t 90% o f i t s p a r t i c l e s p a s s e d 325 mesh and u s i n g 3 p a s s e s w i t h 3 0 - s e c r e t e n t i o n e a c h , 93% o f t h e p y r i t i c s u l f u r was removed. Further t e s t s on f i n e g r i n d i n g and o p t i m i z a t i o n o f the t e s t c o n d i t i o n s a r e now b e i n g c a r r i e d o u t i n t h e a u t h o r ' s l a b o r a t o r i e s . I n a d d i t i o n to the s u l f u r r e d u c t i o n , ash r e d u c t i o n i s b e i n g measured. The l o s s o f c o a l i n t h e m a g n e t i c f r a c t i o n s v a r i e d f r o m 6 t o 14% and i s r e l a t e d t o t h e s i z e and d i s t r i b u t i o n o f t h e p y r i t e i n t h e coal.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch009

Economics Q u i n l a n and V e n k a t e s a n (15) r e c e n t l y d i s c u s s e d t h e e c o n o m i c s of c o a l p r e p a r a t i o n c o a l c l e a n i n g processes comparing j i g versus heavy media p l a n t c i r c u i t s . The o p e r a t i n g c o s t o f the j i g p l a n t was $0.85 p e r c l e a n t o n and f o r t h e h e a v y m e d i a c i r c u i t $1.25 per c l e a n ton. The c a p a c i t y o f e a c h was 500 TPH, and t h e c a p i t a l c o s t o f t h e j i g c i r c u i t was $6,000,000 and f o r t h e h e a v y m e d i a c i r c u i t $8,500,000. To d e s i g n a c l e a n i n g c i r c u i t t o p r o d u c t 500 TPH o f c o a l w o u l d r e q u i r e f i v e 8 4 - i n . magnets. The c a p i t a l c o s t ( i n s t a l l e d ) w o u l d be a p p r o x i m a t e l y $8,000,000. Table I I I . Operating

Costs

o f HEMF F o r 500 C o s t p e r Hour

A m o r t i z a t i o n of i n s t a l l e d s e p a r a t o r s o v e r 10 y e a r s , 80,000 h r . Magnet power (2000 kW @2c kW-h) Pumping and f l u s h i n g power (1000 kW @2ç kW-h) Labor Maintenance Total

Tons/hr.

Capacity

Cost per

$100. .00

$0. 20

40. ,00

0. 08

20. .00

0. 04

15. .00 10. .00

0. 03 0. 02

185, .00

0. 37

Ton

The c o s t p e r t o n o f m a g n e t i c c l e a n i n g i s r e l a t i v e l y l o w compared w i t h t h e o t h e r two methods c i t e d . In a d d i t i o n to the p o t e n t i a l r e m o v a l o f 70 - 90% o f the i n o r g a n i c s u l f u r , t h e a s h c o n t e n t o f t h e c o a l w o u l d be s u b s t a n t i a l l y r e d u c e d . A h i g h p e r c e n t a g e of the f o l l o w i n g i m p u r i t i e s , i f p r e s e n t , i n a d d i t i o n t o p y r i t e , w o u l d be removed m a g n e t i c a l l y b e c a u s e a l l o f t h e s e m i n e r a l s and r o c k s have a mass s u s c e p t i b i l i t y h i g h e r t h a n p y r i t e except f o r limestone: s i d e r i t e , l i m o n i t e , f e r r o u s and f e r r i c s u l f a t e , l i m e s t o n e , c l a y and s h a l e , and s a n d . Much a d d i t i o n a l r e s e a r c h and d e v e l o p m e n t work must be done to s u b s t a n t i a t e the p r e l i m i n a r y r e s u l t s r e p o r t e d i n t h i s paper. S e v e r a l s t u d i e s a r e underway i n t h e a u t h o r ' s l a b o r a t o r i e s a t

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

9.

MURRAY

Magnetic Desulfurization of Illinois Coals

119

Indiana University. S i n c e c o a l i s t o become t h e m a j o r e n e r g y s o u r c e i n t h e U.S. i n t h e f o r e s e e a b l e f u t u r e , m a g n e t i c c l e a n i n g o f c o a l l o o k s a s i f i t w i l l be a v i a b l e method o f p r o c e s s i n g which can provide a l o w - s u l f u r , low-ash c o a l .

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch009

Conclusions H i g h e x t r a c t i o n m a g n e t i c f i l t r a t i o n (HEMF) i s a p r o v e n comm e r c i a l p r o c e s s used e x t e n s i v e l y i n t h e p r o c e s s i n g o f k a o l i n . F i n e p u l v e r i z a t i o n t o -200 mesh o r p r e f e r a b l y t o -325 mesh t o l i b e r a t e t h e p y r i t e f r o m t h e c o a l i s n e c e s s a r y t o a c h i e v e optimum separation. From 65 - 9 0 % o f t h e i n o r g a n i c s u l f u r c a n b e s e p a r a t e d from a c o a l s l u r r y b y HEMF p r o c e s s i n g . The e s t i m a t e d c o s t p e r t o n i s l o w and compares f a v o r a b l y w i t h o t h e r methods o f p y r i t e removal. The r e s u l t a n t c o a l p r o d u c t f r o m t h e HEMF p r o c e s s i s r e l a t i v e l y c l e a n o f i n o r g a n i c s u l f u r and a s h c o n t e n t .

Abstract High extraction magnetic filtration (HEMF) has potential application to remove a high percentage of inorganic pyritic sulfur from coal. Newly developed high intensity separators with high intensity (20 kG) and high gradient collectors can remove up to 90% of the pyritic sulfur under optimum conditions. A canister filled with a filamentary matrix of sharp stainless steel screens provides high gradients and pyrite in pulverized coal (-200 mesh) will be attracted and held. Coal is diamagnetic, and pyrite is paramagnetic, and if the pyrite can be liberated from the coal, it can be magnetically filtered out in commercial practice. Coals V and VI from Indiana and Illinois were used for this study. These coals have a total sulfur content of between 1.98 and 4.63% of which approximately 60% is pyritic sulfur. Both dry and wet magnetic separation methods were used. Wet methods were more successful in that up to 90% of the pyrite was removed whereas the best results from the dry separation was 40% removal. The cost per ton of a 500 ton/hr installation would be of the order of $0.50 per ton and would produce a relatively low-sulfur, low-ash product. Literature Cited 1. 2. 3.

Iannicelli, J., "High Extraction Magnetic Filtration of Kaolin Clay," Clays Clay Miner., (1976) 24, 64-68. Iannicelli, J., "Assessment of High Extraction Magnetic Filtration," Special Report-RANN-National Science Foundation (1974). Murray, H.H., "Beneficiation of Selected Industrial Minerals and Coal by High Intensity Magnetic Separation," IEEE Trans. Magn., (1976) MAG-12, 498-502.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

120 4. 5. 6. 7.

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8. 9. 10. 11. 12. 13. 14. 15.

COAL DESULFURIZATION Murray, H.H., "High Intensity Magnetic Beneficiation of Industrial Minerals-Α Survey," Preprint 76-H-93 Amer. Inst. Min. Engrs. (1976). Murray, H.H., "High Intensity Magnetic Cleaning of Bituminous Coal," Proc. National Coal Research Symposium - Louisville, Ky., pp 74-81, Oct. 1976. Siddiqui, S., "Desulfurization and Concentration of Coal," German Patent 1,005,012, 1957. Yurovsky, A.Z., Remesnikov, I.D., "Thermomagnetic Method of Concentrating and Desulfurizing Coal," Coke Chem. (1958) 12, 8-13. Perry, Η., "Potential for Reduction of Sulfur in Coal by Other Than Conventional Cleaning Methods," SymposiumEconomics of Air Pollution Control, AICHE 59th Nat. Meeting 1966. Kester, W.M., Jr., "Magnetic Demineralization of Pulverized Coal," Mining Eng. (1965) 17. Kester, W.M., Jr., "The Effect of High Intensity Magnetic Cleaning on Pulverized High Sulfur, Bituminous Coals," Thesis, School of Mines, West Virginia Univ., 1966. Gluskoter, H.J., Simon, J.A., "Sulfur in Illinois Coals," Ill. State Geol. Surv., Circ. (1968) 432. Kester, W.M., Jr., Leonard, J.W., Wilson, E.B., "Reduction of Sulfur from Steam Coal by Magnetic Methods," Tech. Report 31, Coal Research Bureau, West Virginia Univ. (1967). Wooster, W.A., Wooster, Ν., "The Magnetic Properties of Coal," Bull. British Coal Utilization Research Assoc. (1944). Kindig, J.K., Turner, R.L., "Dry Chemical Process to Magnetize Pyrite and Ash for Removal from Coal," AIME Preprint 76-F-306 (1976). Quinlan, R.M., Venkatesan, S., "Economics of Coal Prepara­ tion" AIME Preprint 76-F-108 (1976).

This study was supported by a grant from the Electric Power Research Institute. The chemical analyses were done by Nily Sofer in the chemistry lab, Geology Department at Indiana University.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

10 Desulfurization of Coals by High-Intensity High-Gradient Magnetic Separation: Conceptual Process Design and Cost

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch010

Estimation

C. J. LIN and Y. A. LIU Magnetochemical Engineering Laboratory, Department of Chemical Engineering, Auburn University, Auburn, AL 36830 It is well known that the main difficulty in increasing the utilization of coal in the United States lies in the pollution problem, and emission levels of sulfur oxides and ash particles from coal burning facilities must be reduced to meet stringent environmental standards. Although the particulate emission standards can generally be met by using electrostatic precipitators, there apparently exists no accepted technology for controlling sulfur oxide emissions in flue gases (1). Thus, there has been a growing effort recently to develop effective and economical alternatives to flue gas desulfurization. One of the most attractive alternatives is the precombustion cleaning of coal. Several new physical and chemical methods for removing sulfur and ash from coal prior to its combustion have already been proposed and are currently under intensive further development (2). An important physical method for cleaning coal that appears to hold much promise is the well established magnetic separation technique. Previous experimental investigations have indicated clearly that most of the mineral impurities in coal which contribute to the pyritic sulfur, the sulfate sulfur, and the ash content are paramagnetic. These sulfur-bearing and ash-forming minerals, if sufficiently liberated as discrete particles, can be separated from the pulverized diamagnetic coal by magnetic means (3-8). Indeed, the technical feasibility of the magnetic cleaning of coal has been demonstrated in a number of previous studies, with substantial amounts of sulfur and ash removal reported (9,10). D u r i n g t h e past few y e a r s , the magnetic c l e a n i n g o f c o a l has b e e n g i v e n new i m p e t u s w i t h t h e i n t r o d u c t i o n o f a new l e v e l o f magnetic separation technology, t h e h i g h - i n t e n s i t y h i g h - g r a d i e n t m a g n e t i c s e p a r a t i o n (HGMS). The HGMS t e c h n o l o g y was d e v e l o p e d a r o u n d 1969 f o r t h e wet s e p a r a t i o n o f f e e b l y m a g n e t i c c o n t a m i n a n t s f r o m k a o l i n c l a y ( 1 1 - 1 7 ) . A t y p i c a l HGMS u n i t f o r t h i s wet a p p l i c a t i o n i s shown s c h e m a t i c a l l y a s F i g u r e l a . The e l e c t r o m a g n e t s t r u c t u r e c o n s i s t s o f e n e r g i z i n g c o i l s and a s u r r o u n d i n g i r o n enclosure. The c o i l s i n t u r n e n c l o s e a c y l i n d r i c a l , h i g h l y magn e t i z a b l e w o r k i n g volume p a c k e d w i t h f i n e s t r a n d s o f s t r o n g l y

121

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

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122

COAL

DESULFURIZATION

f e r r o m a g n e t i c p a c k i n g m a t e r i a l such a s f e r r i t i c s t a i n l e s s s t e e l wool. W i t h t h i s d e s i g n , a s t r o n g f i e l d i n t e n s i t y o f 20 kOe c a n be g e n e r a t e d and d i s t r i b u t e d u n i f o r m l y t h r o u g h o u t t h e w o r k i n g v o l u m e . F u r t h e r m o r e , by p l a c i n g i n t h e u n i f o r m m a g n e t i c f i e l d t h e f e r r o m a g n e t i c p a c k i n g m a t e r i a l s w h i c h i n c r e a s e and d i s tort the f i e l d i nt h e i r v i c i n i t y , large f i e l d gradients of the o r d e r o f 1-10 kOe/pmcan be p r o d u c e d . I n t h e wet b e n e f i c i a t i o n o f k a o l i n c l a y , t h e HGMS u n i t i s u s e d i n a b a t c h o r c y c l i c a l l y o p e r a ted p r o c e s s l i k e a f i l t e r . The k a o l i n f e e d c o n t a i n i n g t h e f e e b l y m a g n e t i c c o n t a m i n a n t s i n l o w c o n c e n t r a t i o n s i s pumped t h r o u g h t h e s t a i n l e s s s t e e l wool p a c k i n g o r m a t r i x o f t h e s e p a r a t o r from t h e b o t t o m w h i l e t h e magnet i s on. The m a g n e t i c m a t e r i a l s (mags) a r e c a p t u r e d and r e t a i n e d i n s i d e t h e s e p a r a t o r m a t r i x , and t h e n o n m a g n e t i c components ( t a i l s ) p a s s t h r o u g h t h e s e p a r a t o r m a t r i x and a r e c o l l e c t e d a s t h e b e n e f i c i a t e d p r o d u c t s f r o m t h e t o p o f t h e magnet. A f t e r some t i m e o f o p e r a t i o n , t h e s e p a r a t o r m a t r i x i s f i l l e d t o i t s l o a d i n g c a p a c i t y . The f e e d i s t h e n s t o p p e d , and the s e p a r a t o r m a t r i x i s r i n s e d w i t h water. F i n a l l y , t h e magnet i s t u r n e d o f f , and t h e mags r e t a i n e d i n s i d e t h e s e p a r a t o r m a t r i x a r e backwashed w i t h w a t e r and c o l l e c t e d . The w h o l e p r o c e d u r e i s repeated i n a c y c l i c f a s h i o n . I n general, i f t h i s batch process i s u s e d i n o t h e r wet a p p l i c a t i o n s where t h e m a g n e t i c m a t e r i a l s o c c u p y a l a r g e f r a c t i o n o f t h e f e e d s t r e a m , t h e down t i m e f o r b a c k w a s h i n g w i l l be c o n s i d e r a b l e , p o s s i b l y n e c e s s i t a t i n g t h e u s e o f one o r more b a c k - u p s e p a r a t o r s . To overcome t h i s p r o b l e m w h i c h i s inherent i n batch operations, a continuous process using a m o v i n g m a t r i x HGMS u n i t , c a l l e d t h e C a r o u s e l s e p a r a t o r , h a s been p r o p o s e d ( 1 2 , 15-17) a s shown s c h e m a t i c a l l y i n F i g u r e l b . A numb e r o f p i l o t - s c a l e s t u d i e s o f t h e wet b e n e f i c i a t i o n o f k a o l i n c l a y and i r o n o r e s u s i n g t h e C a r o u s e l s e p a r a t o r have b e e n r e p o r t e d (17). B e c a u s e o f t h e v e r y l o w c o s t s and t h e o u t s t a n d i n g t e c h n i c a l p e r f o r m a n c e o f HGMS d e m o n s t r a t e d i n t h e k a o l i n a p p l i c a t i o n , HGMS was r e c e n t l y a d a p t e d i n a b e n c h - s c a l e e x p l o r a t o r y s t u d y (8) t o remove s u l f u r and a s h f r o m a f i n e l y p u l v e r i z e d B r a z i l i a n c o a l suspended i n w a t e r . S i n c e t h e n , o t h e r i n v e s t i g a t o r s have u t i l i zed p i l o t - s c a l e HGMS u n i t s t o d e s u l f u r i z e and d e a s h w a t e r s l u r r i e s o f some E a s t e r n U.S. c o a l s . F o r i n s t a n c e , r e s u l t s o f p i l o t - s c a l e s t u d i e s that demonstrated t h e t e c h n i c a l f e a s i b i l i t y o f t h e m a g n e t i c s e p a r a t i o n o f s u l f u r and a s h f r o m w a t e r s l u r r i e s o f p u l v e r i z e d I l l i n o i s No. 6, I n d i a n a No. 5 and No. 6, K e n t u c k y No. 9/14, P e n n s y l v a n i a Upper F r e e p o r t and Lower K i t t a n n i n g c o a l s h a v e been r e p o r t e d ( 4 - 7 , 1 8 , 1 9 ) . I n p a r t i c u l a r , the q u a n t i t a t i v e e f f e c t s o f major s e p a r a t i o n v a r i a b l e s such as f i e l d i n t e n s i t y , r e s i d e n c e t i m e , e t c . , o n t h e g r a d e , r e c o v e r y and c o n c e n t r a t i o n breakthrough f o r the magnetic s e p a r a t i o n o f s u l f u r and a s h f r o m a w a t e r s l u r r y o f p u l v e r i z e d I l l i n o i s No. 6 c o a l have been e s t a b l i s h e d e x p e r i m e n t a l l y , and c a n be p r e d i c t e d s a t i s f a c t o r i l y by a n e w l y d e v e l o p e d m a t h e m a t i c a l m o d e l f o r HGMS ( 4 , 5 , 7 , 1 3 , 1 8 ) . D e p e n d i n g upon t h e t y p e s o f c o a l and t h e s e p a r a t i o n

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

L I N A N D Liu

High-Intensity and -Gradient Magnetic Separation

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch010

CLEANED

TAILINGS OUT

Figure 1.

(a) (above) Cyclic high-gradient magnetic separator; (b) (below) carousel high-gradient magnetic separator

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

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124

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c o n d i t i o n s u s e d , t h e e x i s t i n g b e n c h - a n d p i l o t - s c a l e r e s u l t s have shown t h a t t h e u s e o f s i n g l e - p a s s HGMS was e f f e c t i v e i n r e d u c i n g t h e t o t a l s u l f u r by 4 0 - 5 5 % , t h e a s h by 35-45%, and t h e p y r i t i c s u l f u r b y 80-90%, w h i l e a c h i e v i n g a maximum r e c o v e r y o f a b o u t 95% ( 1 0 , 1 8 ) . These a v a i l a b l e r e s u l t s have i n d i c a t e d a l s o t h a t b o t h t h e g r a d e and r e c o v e r y o f t h e s e p a r a t i o n c a n be enhanced g e n e r a l l y w i t h the u s e o f a l a r g e r s e p a r a t o r m a t r i x o r by t h e recycle of thet a i l products. Further detailed review of the r e p o r t e d r e s u l t s on t h e m a g n e t i c c l e a n i n g o f p u l v e r i z e d c o a l s i n w a t e r s l u r r i e s c a n be found i n t h e l i t e r a t u r e ( 9 , 1 0 , 1 8 ) . These p u b l i s h e d d a t a and o t h e r r e c e n t a n a l y s e s (2,10,18,20^24) have i n d i c a t e d t h a t a s i g n i f i c a n t p o r t i o n o f t h e U.S. c o a l r e s e r v e s , l o w enough i n o r g a n i c s u l f u r , c a n be m a g n e t i c a l l y c l e a n e d f o r u s e as a n e n v i r o n m e n t a l l y a c c e p t a b l e , l o w s u l f u r f u e l . i t has been e s t i m a t e d t h a t 100 m i l l i o n s h o r t t o n s o f U.S. c o a l s p e r y e a r may be m a g n e t i c a l l y c l e a n e d . T h i s amounts t o o v e r 1 7 % o f t h e t o t a l U.S. p r o d u c t i o n p e r y e a r ( 1 0 ) . A l t h o u g h t h e e x i s t i n g d a t a have n o t y e t e s t a b l i s h e d t o t a l d e a s h i n g b y m a g n e t i c means, t h e r e i s some i n d i c a t i o n t h a t b y o p t i m i z i n g t h e s e p a r a t i o n c o n d i t i o n s , and e n h a n c i n g t h e m a g n e t i s m o f a s h - f o r m i n g m i n e r a l s , e t c . , t h e e f f e c t i v e n e s s o f m a g n e t i c s e p a r a t i o n o f a s h f r o m c o a l c a n be i m p r o v e d (10) . R e c e n t s t u d i e s (4,5,9,10,25-27) have a l s o s u g g e s t e d t h a t c o a l c l e a n i n g b y HGMS c o u l d s e r v e a s a s i g n i f i c a n t a d j u n c t t o coal l i q u e f a c t i o n processes. In particular, thetechnical feasib i l i t y o f a d a p t i n g HGMS a s a n e f f e c t i v e a l t e r n a t i v e t o convent i o n a l p r e c o a t f i l t r a t i o n i n t h e s o l v e n t r e f i n e d c o a l (SRC) p r o c e s s h a s a l r e a d y b e e n d e m o n s t r a t e d by a b e n c h - s c a l e , e x p l o r a t o r y s t u d y done a t H y d r o c a r b o n R e s e a r c h , I n c . ( H R I ) . HGMS e f f e c t i v e l y removed up t o 9 0 % o f t h e i n o r g a n i c s u l f u r f r o m t h e l i q u e f i e d SRC f i l t e r f e e d s l u r r y o f I l l i n o i s No. 6 c o a l , and a b o u t h a l f o f t h e e x p e r i m e n t a l r u n s c o n d u c t e d by HRI i n d i c a t e d o v e r 8 7 % i n o r g a n i c s u l f u r removal (6,15,26). I n g e n e r a l , t h e work done by HRI showed t h a t HGMS was l e s s e f f e c t i v e i n a s h r e m o v a l b u t d i d remove 25-35% o f t h e a s h . Q u i t e r e c e n t l y , a p i l o t - s c a l e HGMS s y s t e m t o remove m i n e r a l r e s i d u e f r o m l i q u e f i e d c o a l h a s b e e n d e s i g n e d and c o n s t r u c t e d by t h e a u t h o r s ( 5 , 2 5 ) . Typical results f r o m e x p e r i m e n t s c o n d u c t e d w i t h t h e l i q u e f i e d SRC f i l t e r f e e d s l u r r y o f K e n t u c k y No. 9/14 and I l l i n o i s M o n t e r e y c o a l s have been q u i t e e n c o u r a g i n g , i n d i c a t i n g t h a t HGMS c o u l d r e d u c e t h e t o t a l s u l f u r , a s h and p y r i t i c s u l f u r c o n t e n t s by a s much a s 7 0 , 76, and 95%, r e s p e c t i v e l y . A v a i l a b l e d a t a from the above benchand p i l o t - s c a l e i n v e s t i g a t i o n have showed a l s o t h a t a n even g r e a t e r d e a s h i n g o f t h e l i q u e f i e d SRC f i l t e r f e e d c a n be a c h i e ved b y i m p r o v e d s e p a r a t i o n c o n d i t i o n s . A d e t a i l e d d i s c u s s i o n o f t h e s e r e s u l t s a l o n g w i t h t h e i r t e c h n i c a l i m p l i c a t i o n s c a n be found i n the l i t e r a t u r e (10,25,27). Furthermore, c l o s e examinat i o n o f t h e i n h e r e n t p h y s i c a l and c h e m i c a l c h a r a c t e r i s t i c s o f the hydrogenated products p r i o r t o t h e f i l t r a t i o n step i n the SRC and o t h e r r e l a t e d l i q u e f a c t i o n p r o c e s s e s i n d i c a t e s t h a t HGMS

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch010

10.

L I N A N D Liu

High-Intensity and -Gradient Magnetic Separation

may be d e v e l o p e d a s a p r a c t i c a l m i n e r a l r e s i d u e s e p a r a t i o n method. Hydrogénation w i l l g e n e r a l l y r e d u c e a m a j o r p o r t i o n o f t h e p y r i t i c s u l f u r t o t h e h i g h l y m a g n e t i c p y r r h o t i t e ; and t h e s u l f u r b e a r i n g and a s h - f o r m i n g m i n e r a l s t e n d t o be l i b e r a t e d more e a s i l y f r o m t h e d i s s o l v e d o r g a n i c components i n t h e f i l t e r f e e d s l u r r y t h a n f r o m p u l v e r i z e d c o a l suspended i n w a t e r . A l s o , t h e t y p i c a l mean p a r t i c l e s i z e o f t h e f i l t e r f e e d sample i s o f t e n l e s s t h a n 5 m i c r o n s , w h i c h d i c t a t e s t h e u s e o f s e p a r a t i o n methods l i k e HGMS c a p a b l e o f h a n d l i n g m i c r o n - s i z e m a t e r i a l s . A l l o f these f a c t o r s seem t o s u g g e s t a v e r y s i g n i f i c a n t p o t e n t i a l f o r u t i l i z i n g HGMS t o remove m i n e r a l r e s i d u e s f r o m l i q u e f i e d c o a l . F o r c e r t a i n t y p e s o f c o a l , e v e n w i t h o u t f u r t h e r improvement i n t h e m a g n e t i c r e m o v a l o f a s h , m a g n e t i c a l l y c l e a n e d SRC w o u l d be a c c e p t a b l e f o r u s e a s a f e e d t o b o i l e r s w h i c h a l r e a d y have e l e c t r o s t a t i c p r e c i p i t a t o r s (28). T h i s f o l l o w s because t h e c o s t o f s o l i d - l i q u i d s e p a r a t i o n i n c o a l l i q u e f a c t i o n i s g e n e r a l l y subs t a n t i a l , and m o d e r a t e l y l o w - a s h SRC s h o u l d be l e s s e x p e n s i v e (27-29). Indeed, a p r e l i m i n a r y c o s t e s t i m a t e f o r the magnetic d e s u l f u r i z a t i o n o f l i q u e f i e d c o a l b a s e d on t h e l a b o r a t o r y d a t a o b t a i n e d by HRI seems t o s u p p o r t t h i s o b s e r v a t i o n ( 2 7 ) . The p r e c e d i n g d i s c u s s i o n h a s i n d i c a t e d t h a t t h e s c i e n t i f i c and t e c h n i c a l f e a s i b i l i t y o f m a g n e t i c d e s u l f u r i z a t i o n o f b o t h c o a l / w a t e r s l u r r y and l i q u e f i e d c o a l h a s b e e n w e l l established. R e c e n t l y , s e v e r a l e s t i m a t e s o f the c o s t o f m a g n e t i c d e s u l f u r i z a t i o n have b e e n r e p o r t e d i n t h e l i t e r a t u r e ( 8 , 1 4 , 1 9 , 2 2 , 2 7 ) . B e c a u s e o f t h e s i m p l i f y i n g a s s u m p t i o n s i n v o l v e d , as w e l l a s t h e t e c h n i c a l p e r f o r m a n c e s p e c i f i e d and t h e e s t i m a t i o n methods u s e d , t h e r e s u l t s seem t o be somewhat a p p r o x i m a t e i n n a t u r e . In this p a p e r , t h e l a t e s t d a t a f r o m p i l o t - s c a l e s t u d i e s o f s u l f u r and a s h r e m o v a l f r o m b o t h l i q u e f i e d c o a l and c o a l / w a t e r s l u r r y by HGMS a r e used t o d e s i g n c o n c e p t u a l p r o c e s s e s f o r m a g n e t i c d e s u l furization of coal. Estimates o f magnetic d e s u l f u r i z a t i o n chara c t e r i s t i c s and c o n c e p t u a l p r o c e s s r e q u i r e m e n t s a s w e l l a s i n s t a l l a t i o n and p r o c e s s i n g c o s t s a r e p r e s e n t e d . In particular, t h e e x t e n t t o w h i c h t h e p r o c e s s i n g c o n d i t i o n s c a n a f f e c t magnet i c d e s u l f u r i z a t i o n c o s t s i s examined. F i n a l l y , t h e r e s u l t s a r e compared w i t h o t h e r a p p r o a c h e s f o r the d e s u l f u r i z a t i o n o f coal. Magnetic D e s u l f u r i z a t i o n

o f Coal/Water S l u r r y :

P r o c e s s and C o s t s

A c o n c e p t u a l p r o c e s s f o r the magnetic d e s u l f u r i z a t i o n o f p u l v e r i z e d c o a l suspended i n w a t e r by HGMS i s shown s c h e m a t i c a l l y i n F i g u r e 2. A c o a l s l u r r y o f a f i x e d c o n c e n t r a t i o n i s p r e p a r e d f i r s t by m i x i n g known amounts o f p u l v e r i z e d c o a l , w a t e r , and a dispersant (wetting agent) l i k e Alconox. The HGMS u n i t used h e r e i s t h e l a r g e s t c o m m e r c i a l u n i t now i n u s e f o r p r o d u c i n g h i g h q u a l i t y paper c o a t i n g c l a y s . I t i s operated at a f i x e d f i e l d i n t e n s i t y o f 20 kOe g e n e r a t e d i n a n open volume 7 f t i n d i a m e t e r and 20 i n . l o n g . A s t a i n l e s s s t e e l w o o l s e p a r a t o r m a t r i x h a v i n g

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

125

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch010

126

COAL DESULFURIZATION

94% v o i d s i s p l a c e d i n t h e open v o l u m e . The c o a l s l u r r y i s pumped t h r o u g h t h e e n e r g i z e d s e p a r a t o r m a t r i x a t a f i x e d r e s i ­ dence time ( f l o w v e l o c i t y ) u n t i l the m a t r i x reaches i t s l o a d i n g capacity. A f t e r r i n s i n g w i t h w a t e r , t h e mags a r e s e n t t o a s e t t l i n g pond o r a c l a r i f i e r t o r e c o v e r w a t e r f o r r e - u s e . The t a i l s a r e c o l l e c t e d , d e w a t e r e d , and d r i e d . The s p e c i f i c a t i o n s o f p r o c e s s s t r e a m s f o r a t y p i c a l c a s e (Case Β i n T a b l e I ) a r e a l s o i n c l u d e d i n F i g u r e 2, and t h e d e t a i l e d o p e r a t i n g c o n d i t i o n s for such a case are g i v e n i n the Appendix. By r e m o v i n g 80-90% o f t h e p y r i t i c s u l f u r m a g n e t i c a l l y and a c h i e v i n g 85-90% r e c o v e r y as was d e m o n s t r a t e d by t h e r e s u l t s o f r e p o r t e d s t u d i e s of magnetic d e s u l f u r i z a t i o n of p u l v e r i z e d c o a l s i n w a t e r s l u r r i e s ( 4 - 1 0 , 1 3 , 1 8 , 1 9 ) , t h e p r o c e s s c a n be u s e d to c l e a n a b o u t o n e - f i f t h o f t h e r e c o v e r a b l e U.S, c o a l s w i t h a low o r g a n i c s u l f u r c o n t e n t o f 0.7-0.9 wt % t o p r o d u c e a n e n v i r o n ­ mentally acceptable f u e l . A d e t a i l e d documentation of the r e ­ s e r v e s and p r o d u c t i o n o f U.S. c o a l s w h i c h may be m a g n e t i c a l l y c l e a n a b l e t o 1 wt% t o t a l s u l f u r a c c o r d i n g t o t h e seam, d i s t r i c t and c o u n t y i n e a c h s t a t e , a l o n g w i t h t h e t o t a l and o r g a n i c s u l f u r c o n t e n t s c a n be f o u n d i n t h e l i t e r a t u r e ( 2 1 ) . H e r e , a r e a s o n a b l e r a n g e o f add-on c o s t s ( e x c l u d i n g t h o s e f o r g r i n d i n g , d e w a t e r i n g and d r y i n g and r e f u s e d i s p o s a l ) i s e s t i ­ mated f o r t h e wet m a g n e t i c c l e a n i n g o f c o a l s l u r r i e s w h i c h have d e s u l f u r i z a t i o n c h a r a c t e r i s t i c s s i m i l a r to those r e p o r t e d i n the r e c e n t s t u d i e s ( 4 - 1 0 , 1 3 , 1 8 , 1 9 ) . The method used t o e s t i m a t e t h e c o s t s o f m a g n e t i c d e s u l f u r i z a t i o n i s b a s e d on t h e t e c h n i q u e u s e d by t h e F e d e r a l Power C o m m i s s i o n S y n t h e t i c G a s - C o a l F o r c e t o e s t i m a t e t h e c o s t o f s y n t h e s i s gas (29, 3 4 ) . The i n v e s t o r c a p i ­ t a l i z a t i o n method u s e d i n t h i s a p p r o a c h i s t h e d i s c o u n t c a s h f l o w (DCF) f i n a n c i n g method w i t h assumed DCF r a t e s o f r e t u r n s u c h as 15% a f t e r t a x e s . T h i s method e s s e n t i a l l y d e t e r m i n e s t h e a n n u a l r e v e n u e d u r i n g t h e p l a n t l i f e w h i c h w i l l g e n e r a t e a DCF equal t o the t o t a l c a p i t a l i n v e s t m e n t f o r the p l a n t . Several m a j o r a s s u m p t i o n s a r e i n c l u d e d i n t h e method ( 2 9 , 3 4 ) : (1) The p l a n t l i f e i s assumed t o be 20 y e a r s w i t h no c a s h v a l u e a t t h e end o f l i f e . (2) A s t r a i g h t - l i n e method i s u s e d t o c a l c u l a t e t h e a n n u a l d e p r e ­ ciation. (3) O p e r a t i n g c o s t s and w o r k i n g c a p i t a l r e q u i r e m e n t s a r e assumed to be c o n s t a n t d u r i n g t h e c o n s t r u c t i o n p e r i o d , and 100% e q u i t y c a p i t a l i s assumed. (4) T o t a l p l a n t i n v e s t m e n t , r e t u r n on i n v e s t m e n t d u r i n g t h e p l a n t l i f e , and w o r k i n g c a p i t a l a r e t r e a t e d as c a p i t a l c o s t s i n year zero (the year ending w i t h the c o m p l e t i o n of s t a r t - u p operations). (5) S t a r t - u p c o s t s a r e t r e a t e d as an e x p e n s e i n y e a r z e r o . (6) 48% f e d e r a l income t a x i s assumed. Based on t h e s e a s s u m p t i o n s , e q u a t i o n s f o r c a l c u l a t i n g t h e u n i t c o s t s ($ p e r t o n o f c o a l p r o c e s s e d ) a r e s u g g e s t e d by t h e p u b l i s h e d documents ( 2 9 , 3 4 ) . They a r e summarized i n t h e A p p e n d i x , i n w h i c h

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch010

10.

L I N A N D Liu

High-Intensity and -Gradient Magnetic Separation

t h e d e t a i l e d o p e r a t i n g c o n d i t i o n s and e s t i m a t e d c o s t s f o r a t y p i c a l example shown i n F i g u r e 2 a r e a l s o g i v e n . The c o s t s o f m a j o r i n s t a l l e d equipment and t h e u n i t c o s t s l i s t e d i n t h e A p p e n d i x a r e based o n v a l u e s a s o f June 1976. For instance, the costs of pump and t a n k u s e d were e s t i m a t e d f i r s t a c c o r d i n g t o R e f . 3^5 and t h e n b r o u g h t up t o d a t e by m u l t i p l y i n g by t h e CE p l a n t c o s t index r a t i o o f (205/113.6), w h i l e the c o s t o f t h e i n s t a l l e d HGMS u n i t w i t h a s e p a r a t o r m a t r i x 7 f t i n d i a m e t e r and 20 i n . l o n g was e s t i m a t e d t o be $1.936 m i l l i o n ( 2 6 ) . The e s t i m a t e d c a p i t a l i n v e s t m e n t and u n i t c o s t s f o r f o u r t y p i c a l c a s e s , d e s i g n a t e d a s A-D, a r e summarized i n T a b l e I . S l u r r y v e l o c i t i e s o f 2.61 and 4.0 cm/sec, s l u r r y c o n c e n t r a t i o n s o f 15,25 and 35 wt%, a s w e l l a s s e p a r a t i o n d u t y c y c l e s o f 59,077.9% a r e c o n s i d e r e d . These s e p a r a t i o n c o n d i t i o n s i l l u s t r a t e c l e a r l y t h e e f f e c t s o f s l u r r y v e l o c i t y and c o n c e n t r a t i o n a s w e l l as s e p a r a t i o n d u t y c y c l e . F o r i n s t a n c e , c o m p a r i s o n o f c a s e s A t o C shows t h a t a t t h e same s l u r r y v e l o c i t y and s i m i l a r magnet i c d e s u l f u r i z a t i o n c h a r a c t e r i s t i c s the h i g h e r t h e s l u r r y conc e n t r a t i o n , t h e c h e a p e r w i l l be t h e i n v e s t m e n t and u n i t c o s t s . W h i l e t h i s o b s e r v a t i o n i s t o be e x p e c t e d , t h e r e h a v e been p i l o t s c a l e t e s t s which i n d i c a t e that i n c r e a s i n g the s l u r r y concent r a t i o n o f p u l v e r i z e d I l l i n o i s No. 6 c o a l f r o m 2.57 t o 28.4 w t % d i d n o t a p p r e c i a b l y change t h e g r a d e and r e c o v e r y o f t h e s e p a r a tion. F u r t h e r e f f e c t s o f p r o c e s s i n g c o n d i t i o n s , and o t h e r c o s t f a c t o r s on the u n i t c o s t s a r e i l l u s t r a t e d i n T a b l e I I . I t i s s e e n f r o m t h e t a b l e t h a t b y d o u b l i n g t h e amount o f c o a l p r o c e s s e d p e r c y c l e r e l a t i v e t o a f i x e d amount o f s t a i n l e s s s t e e l w o o l p a c k e d i n t h e s e p a r a t o r m a t r i x , t h e u n i t c o s t c a n be r e d u c e d by a b o u t 15%. T h i s r e s u l t shows t h e i m p o r t a n c e o f t h e s e p a r a t o r m a t r i x l o a d i n g c h a r a c t e r i s t i c s on t h e c o s t s o f m a g n e t i c d e s u l furization. Another f a c t o r w h i c h a f f e c t s the u n i t c o s t s cons i d e r a b l y i s the washing time r e q u i r e d i n a complete s e p a r a t i o n cycle. T h i s i s s e e n by c o m p a r i n g i t e m s 4 and 6 i n T a b l e I I . I n p a r t i c u l a r , t h e computed r e s u l t s i n d i c a t e t h a t d o u b l i n g t h e amount o f wash w a t e r r e q u i r e d o n l y l e a d s t o n e g l i g i b l e i n c r e a s e ( 0 . 2 7 0.60%) i n u n i t c o s t s . However, i f b o t h t h e amount o f wash w a t e r and t h e w a s h i n g t i m e a r e d o u b l e d , t h e u n i t c o s t s a r e i n c r e a s e d by a b o u t 15%. The above o b s e r v a t i o n s c l e a r l y s u g g e s t a n i m p o r t a n t economic i n c e n t i v e f o r f u r t h e r p i l o t - s c a l e i n v e s t i g a t i o n o f t h e s e p a r a t o r m a t r i x l o a d i n g and w a s h i n g c h a r a c t e r i s t i c s i n the magnetic d e s u l f u r i z a t i o n o f coal/water s l u r r y . F i n a l l y , item 7 o f T a b l e I I shows t h a t l a b o r c o s t seems t o be a s i g n i f i c a n t f r a c t i o n o f the u n i t c o s t . F o r t u n a t e l y , i t i s not expected that t h e l a b o r r e q u i r e m e n t w i l l be d o u b l e d i n a c t u a l c o m m e r c i a l p r a c t i c e from the nominal case i n Table I . T h i s f o l l o w s because e x i s t i n g experience i n the commercial c l e a n i n g o f k a o l i n c l a y s by HGMS i n d i c a t e s t h a t t h e l a b o r r e q u i r e m e n t s f o r b o t h o p e r a t i o n and m a i n t e n a n c e a r e m i n i m a l ( 1 1 , 2 2 ) . In Table I I I , the r e p o r t e d c o s t s o f magnetic d e s u l f u r i z a t i o n e x p r e s s e d i n t e r m s o f t h e c a p i t a l and u n i t c o s t s ($ p e r t o n o f

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

127

128

COAL

Table

1. 2. 3. 4. 5. 6.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch010

7.

I.

Cost o f D e s u l f u r i z a t i o n o f Coal/Water S l u r r y by HGMS U s i n g S e p a r a t o r M a t r i x o f 7 - F t D i a m e t e r and 2 0 - I n L e n g t h

S l u r r y v e l o c i t y (cm/sec) S l u r r y c o n c e n t r a t i o n (wt %) Coal feed rate (ton/hr) C y c l e t i m e (min) D u t y c y c l e (%) Tons o f c o a l p r o c e s s e d per c y c l e U n i t c o s t s ($ p e r t o n coal processed) U

8.

Hi 5 C a p i t a l investment per ton c o a l p r o c e s s e d p e r y e a r ($)

Table I I .

DESULFURIZATION

Case A

Case Β

Case C

Case D

2.61 15 44.77 9.00 77.9

2.61 25 66.13 6.10 67.4

2.61 35 83.07 4.85 59.0

4.0 25 89.61 4.50 59.6

6.7

6.7

6.7

6.7

2.083

2.369

1.109

1.067

1.802

1.063

0.858

0.829

3.676

2.412

1.967

1.880

6.93

4.69

3.73

3.53

S e n s i t i v i t y A n a l y s i s o f U n i t C o s t s ($ P e r Ton C o a l P r o ­ c e s s e d ) o f D e s u l f u r i z a t i o n o f C o a l / W a t e r S l u r r y by HGMS U $

1. B a s i s : 2.61 cm/sec, 25 wt % s l u r r y , and o t h e r c o n d i t i o n s i n t h e A p p e n d i x and T a b l e I 2. Amount o f c o a l p r o c e s s e d p e r c y c l e doubled 3. 25% r e d u c t i o n i n c a p i t a l investment 4. Amount o f wash w a t e r r e q u i r e d doubled (washing time un­ changed) 5. C o s t o f w a t e r i n c r e a s e d 5/3 t i m e s (5C/1000 g a l ) 6. B o t h amounts o f wash w a t e r and w a s h i n g t i m e d o u b l e d 7. L a b o r r e q u i r e m e n t d o u b l e d

—ο

% Change

$

% Change

1. 0628

0.00

2.4117

0.00

0. 9004

-15.28

2.0341

-15.66

0. 9389

-11.66

1.9506

-19.12

1. 0691

+0.60

2.4181

+0.27

1. 0835

+1.95

2.4324

+0.86

1. 2256 1. 3587

+15.32 +27.82

2.7883 2.7077

+15.62 +19.12

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch010

10.

L I N A N D Liu

High-Intensity

and -Gradient

Magnetic

Separation

129

c o a l p r o c e s s e d ) a r e compared w i t h t h e r e s u l t s o f t h i s s t u d y . The c o s t s g i v e n by M u r r a y (19) were b a s e d o n t h e e x i s t i n g c o s t e s t i mate f o r k a o l i n b e n e f i c i a t i o n by HGMS g i v e n i n R e f . 1 1 . F o r a r e s i d e n c e t i m e o f 0.5 m i n , t h e c o a l f e e d r a t e t o a c o m m e r c i a l HGMS u n i t w i t h a s e p a r a t o r m a t r i x 7 f t i n d i a m e t e r and 20 i n . l o n g was s e t a t 100 t o n s p e r h r by M u r r a y . T h i s r a t e a p p e a r s t o be h i g h e r t h a n t h a t e x p e c t e d i n c o m m e r c i a l p r a c t i c e . I n a d d i t i o n , t h e c o s t s o f l a b o r and m a i n t e n a n c e p e r HGMS u n i t were e s t i m a t e d by M u r r a y t o be $1 and $2 p e r h r , r e s p e c t i v e l y . These c o s t s a l s o a p p e a r t o be l o w e r t h a n t h o s e r e p o r t e d i n R e f . _11. C o n s e q u e n t l y , t h e c o s t s e s t i m a t e d by M u r r a y shown i n T a b l e I I I e s p e c i a l l y t h e u n i t c o s t U^, ($0.37 p e r t o n p r o c e s s e d ) , a r e b e l i e v e d t o be l o w e r t h a n t h e a c t u a l c o s t s . N e x t , w h i l e t h e c o s t s e s t i m a t e d by Oder (22) seem t o be r e l a t i v e l y c o m p a r a b l e to those obtained i n t h i s study, i t i s d i f f i c u l t t o i d e n t i f y c l e a r l y t h e d i f f e r e n c e s between the two e s t i m a t e s . T h i s f o l l o w s because s p e c i f i c d e t a i l s r e g a r d i n g the c o s t s o f major i n s t a l l e d e q u i p m e n t , c y c l e t i m e , a n d w a s h i n g t i m e , e t c . , were n o t r e p o r t e d i n R e f . _22. F i n a l l y , t h e c o s t s e s t i m a t e d by T r i n d a d e (8) a r e a l s o b e l i e v e d t o be l o w e r t h a n t h e a c t u a l c o s t s . I n t h e c o s t e s t i m a t e b y T r i n d a d e , a C a r o u s e l s e p a r a t o r was u s e d a s a b a s i s f o r t h e e s t i m a t i o n , a l t h o u g h t h e r e h a v e n o t y e t been a n y t e s t data r e p o r t e d on the magnetic d e s u l f u r i z a t i o n o f c o a l / w a t e r s l u r r y u s i n g a C a r o u s e l s e p a r a t o r . O n l y t h e s e p a r a t o r c o s t was i n c l u d e d i n t h e c a p i t a l c o s t i n t h e a n a l y s i s b y T r i n d a d e , and i t was a b o u t o n e - h a l f o f t h e c o s t o f i n s t a l l i n g a n e q u i v a l e n t c y c l i c HGMS u n i t . This l e d t o the r e l a t i v e l y low c a p i t a l investment p e r t o n o f c o a l p r o c e s s e d ( $ 0 . 8 2 - $ l . 6 4 ) e s t i m a t e d by T r i n d a d e as shown i n T a b l e I I I . The c o s t e s t i m a t i o n method u s e d by T r i n dade g e n e r a l l y l e a d s t o l o w e r u n i t c o s t s . F o r i n s t a n c e , b y u s i n g T r i n d a d e s method, t h e u n i t c o s t Up o b t a i n e d i n t h i s work f o r a s l u r r y v e l o c i t y o f 2.61 cm/sec shown i n T a b l e I I I w i l l be r e d u c e d f r o m $1.06 t o $0.85 p e r t o n o f c o a l p r o c e s s e d . 1

A c o m p a r i s o n o f a p p r o x i m a t e e s t i m a t e d c a p i t a l and u n i t c o s t s of d i f f e r e n t p y r i t i c s u l f u r removal p r o c e s s e s c u r r e n t l y under a c t i v e d e v e l o p m e n t (2,30,31,33) i s g i v e n i n T a b l e IV. With t h e e x c e p t i o n o f t h e MAGNEX p r o c e s s ( 3 1 ) , a l l t h e methods l i s t e d i n T a b l e I V a r e wet p r o c e s s e s and r e q u i r e g r i n d i n g o f f e e d c o a l , thus r e q u i r i n g r e l a t i v e l y comparable g r i n d i n g , dewatering, and d r y i n g c o s t s . T h i s t a b l e i n d i c a t e s t h a t t h e c o s t s o f wet m a g n e t i c d e s u l f u r i z a t i o n by HGMS a r e a t t r a c t i v e when compared w i t h those o f o t h e r approaches, even a f t e r adding the n e c e s s a r y c o s t s o f g r i n d i n g , d e w a t e r i n g and d r y i n g . However, t h e above c o m p a r i s o n i s o n l y a n a p p r o x i m a t e one, b e c a u s e o f t h e d i f f e r e n c e i n t h e methods u s e d t o e s t i m a t e t h e c o s t s and i n t h e d e s u l f u r i z a t i o n c h a r a c t e r i s t i c s r e p o r t e d , e t c . Based on t h e a v a i l a b l e c o s t i n f o r m a t i o n f o r these p y r i t i c s u l f u r removal p r o c e s s e s (3,30,31, 33), i t i s n o t y e t p o s s i b l e t o c a r r y out a r i g o r o u s comparison. Magnetic

Desulfurization of Liquefied Coal:

P r o c e s s and C o s t s

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

130

COAL

Table I I I .

Comparison

of Estimated Costs of D e s u l f u r i z a t i o n of Coal/Water

Murray(l_9)

1. 2. 3.

Slurry velocity (cm/sec) Slurry concentration (wt %) U n i t c o s t s , $ per ton c o a l processed

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch010

4.

C a p i t a l investment per ton c o a l processed per year ($)

T a b l e IV.

Oder(_22)

Trindade(8)

]1.7-3.4

2

2. .02

2. 3. A.

5.

25

1 .06 .

0..83

2..47-0.93

2,.41

1..88

4,.69

3..53

5..95-2.28

Comparison of U n i t Costs of

MAGNEX-Hazen Research, Inc.(31) Froth f l o t a t i o n Bureau of Mines(31) Meyers-TRW Systems and Energy Ledgeraont oxygen leaching-Kennecott Copper Corp.(30) HGMS-This work, see T a b l e I

4..0

2,.61

0..70-0.25. 0.39-0.84 0.22-0.45

1.64

0.82

E s t i m a t e d Approximate C a p i t a l and D i f f e r e n t P y r i t e Removal P r o c e s s e s

Process

1.

4

S l u r r y by HGMS

T h i s Work

30

0..37

i!o

DESULFURIZATION

hi

Capital

Investment^

5.83

7.05

4.17

2.77

4.47

5.71 13.80 (leaching 11.30 (leaching

6.0-14.0 comparable to Meyers 0.83-1.06

only)

3.53-A.69

1.88-2.41

U n i t c o s t s expressed i n $ per ton c o a l p r o c e s s e d . C a p i t a l investment expressed i n $ per ton c o a l p r o c e s s e d

only)

per

year.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch010

10.

L I N A N D Liu

High-Intensity

and -Gradient

Magnetic

Separation

131

A f l o w d i a g r a m o f t h e c o n c e p t u a l p r o c e s s t o remove t h e m i n e r a l r e s i d u e f r o m l i q u e f i e d SRC by HGMS i s shown i n F i g u r e 3. The HGMS u n i t u s e d h e r e i s t h e same c o m m e r c i a l s e p a r a t o r used t o d e s u l f u r i z e the coal/water s l u r r y . The m a g n e t i c d e s u l f u r i z a t i o n o f l i q u e f i e d SRC i s t o be c o n d u c t e d a t e l e v a t e d t e m p e r a t u r e t o reduce the v i s c o s i t y o f the c o a l s l u r r y . Furthermore, the packed s t a i n l e s s s t e e l w o o l m a t r i x i s a l s o t o be h e a t e d t o t h e d e s i r e d s e p a r a t i o n t e m p e r a t u r e d u r i n g o p e r a t i o n . The e l e v a t e d t e m p e r a t u r e o f the m a t r i x w i l l prevent the c o a l s l u r r y from c o n g e a l i n g and p l u g g i n g t h e m a t r i x . I t i s a l s o necessary t o i n s u l a t e the h e a t e d p o r t i o n o f t h e m a t r i x f r o m t h e magnet w i n d i n g s . The i n s u l a t e d m a t r i x i s f u r t h e r s u r r o u n d e d by a w a t e r j a c k e t . These p r o v i s i o n s f o r h e a t i n g , i n s u l a t i n g , and c o o l i n g t h e s e p a r a t o r m a t r i x s l i g h t l y reduce the a c t u a l working volume o f t h e s e p a r a t o r m a t r i x and i t s d i a m e t e r f r o m 7.0 t o 6.83 f t . I n a c t u a l s e p a r a t i o n r u n s , t h e u n f i l t e r e d l i q u e f i e d SRC i s pumped t h r o u g h t h e energized separator a t a constant flow rate u n t i l the separator matrix reaches i t s l o a d i n g l i m i t . A f t e r r i n s i n g w i t h a process g e n e r a t e d s o l v e n t , t h e m a t r i x i s backwashed w i t h t h e same s o l v e n t w i t h t h e magnet d e - e n e r g i z e d . The mags a r e s e n t t o a h y d r o c l o n e separator. The o v e r f l o w f r o m t h e h y d r o c l o n e i s r e c y c l e d b a c k t o t h e wash s o l v e n t t a n k f o r r e - u s e ; w h i l e the u n d e r f l o w i s s e n t t o an e v a p o r a t o r t o r e c o v e r t h e s o l v e n t , and t h e r e s i d u a l s o l i d s a r e packed f o r o t h e r u s e s . The t a i l s f r o m t h e s e p a r a t o r a r e s e n t t o a vacuum c o l u m n t o r e c o v e r t h e s o l v e n t f o r p r o c e s s r e c y c l e and t h e vacuum b o t t o m i s s e n t t o a p r o d u c t c o o l e r t o p r o d u c e t h e s o l i d i f i e d SRC. The c o n c e p t u a l p r o c e s s i s d e s i g n e d t o a c h i e v e t h e same e x t e n t o f i n o r g a n i c s u l f u r r e m o v a l and m a t r i x l o a d i n g o b s e r v e d by HRI f o r s l u r r y v e l o c i t i e s o f 0.25-14.0 cm/sec ( 2 6 ) . The s p e c i f i c magnetic d e s u l f u r i z a t i o n c h a r a c t e r i s t i c s Corresponding t o t h e s e s l u r r y v e l o c i t i e s a r e summarized a s t h e f i r s t t h r e e rows o f T a b l e V. A c c o r d i n g t o a s u r v e y o f 455 U.S. c o a l s a m p l e s c o n d u c t e d by t h e B u r e a u o f M i n e s , t h e a v e r a g e t o t a l and i n o r g a n i c s u l f u r c o n t e n t s o f t h e s e s a m p l e s were 3.02 and 1.91 wt%, r e s p e c t i v e l y ( 2 0 ) . T h u s , i f t h e hydrogénation s t e p i n t h e SRC a n d o t h e r r e l a t e d l i q u e f a c t i o n p r o c e s s e s c a n remove 7 0 % o f t h e o r g a n i c s u l f u r , a r e d u c t i o n i n t h e i n o r g a n i c s u l f u r c o n t e n t by a b o u t 6 7 % a f t e r hydrogénation w i l l be s u f f i c i e n t t o p r o d u c e SRC w i t h a n e m i s s i o n l e v e l s m a l l e r t h a n 1.20 l b S 0 2 / m i l l i o n B t u , a s s u m i n g t h a t t h e SRC h a s a h e a t i n g v a l u e o f 16,000 B t u / l b . The same method o f c o s t e s t i m a t i o n summarized i n t h e Append i x e x c e p t f o r r e p l a c i n g t h e d i s p e r s a n t by steam w i t h a n o m i n a l c o s t o f $2/1000 l b was u s e d t o e s t i m a t e c a p i t a l i n v e s t m e n t and u n i t c o s t s o f the c o n c e p t u a l p r o c e s s . The r e s u l t s a r e p r e s e n t e d i n T a b l e V. H e r e , t h e c o s t o f m a j o r i n s t a l l e d equipment s u c h a s t h e HGMS u n i t , wash s o l v e n t t a n k , f e e d s u r g e t a n k , f e e d pump, f l u s h pump and e v a p o r a t o r , e t c . , h a s b e e n i n c l u d e d . I n T a b l e V I , t h e e f f e c t o f steam p r i c e on t h e u n i t c o s t U o f m a g n e t i c desulfurization of liquefied coal i s i l l u s t r a t e d . Doubling the Q

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

132

C O A L DESULFURIZATION

Water Supply 1.653 million gal/day Dispersant 5.3 Lb/Hr

Feed Ball Coal — 66.13 TPH Mill

Rinse Water 720 gal/cycle

794 6PM 25 Mixing Wt%j Tank Slurry 10,000 gal

Wash Water 1440 gal/cycle

HGMS 7'D, 20" L. 1480 2.61 cm/sec Velocity 6PM 480 gal. Canister Pump Volume 096 Tons S S. Wool 94% Void Volume 3846 GPM/Ft

Water Tails Vacuum Filter

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch010

2

Cycle Time 6.1 min. Duty Cycle 674%

Mags

Refute 9.92 TPH -

Figure 2.

Thermal Dryer

Clarifier or Settling Pond

Clean Dry Coal 56.21 TPH

Desulfurization of coal/water slurry by HGMS

Wash Oil Wash Oil Tank 2300 Gallons Rinse Oil 686 gal/cycle

Wash Oil 1372 gal/cycle Recycle Solvent

HGMS 7'D, 20" L. 2928 5.42 cm/sec Velocity GPM 457.23 gal. Canister Volume Pump 0.915 Tons S.S. Wool 94% Void Volume

Surge SRC Tank Filter Fee
Cycle Time 4.32 min. Duty Cycle 59.8%

Tails

Vacuum Column

Mags Product Cooler

Hydroclone

Solvent Refined Coal Evaporator W Condenser Mineral Residue Figure 3.

Desulfurization of liquefied coal by HGMS

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

LIN AND Liu

T a b l e V.

Costs of D e s u l f u r i z a t i o n of

1. 2. 3. 4. 5.

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6.

7.

High-Intensity and -Gradient Magnetic Separation

Slurry velocity (cm/sec) Apparent % p y r i t i c s u l f u r removal C y c l e time (min) Duty c y c l e (%) Tons o f SRC f e e d c o a l processed per c y c l e F i l t r a t i o n rate based o n a c t u a l f i l t e r i n g time (GPM/ft2)

0.,25

1..60

90

2.71 78

87

45. ,86

Separator

Matrix

Length

5.84

9..15

2.71 74 11.33

5..42 67..7 4..32

14. ,0 66. ,4 2.,39

85. .8

74.,9

66.3

82.6

59..8

33.,5

22.,52

24..71

23.63

57.21

31..48

25..25

3.,74

23..56

39.91

39.91

79..82

6..58 15.,65 8..64 30..5

1..45 3,.31 1,.87 6..26

206. .2

Unit costs, $ per t o n c o a l processed Uo

8.

o f SRC Feed C o a l by HGMS U s i n g

6.83-Ft D i a m e t e r and 20-In

Ë15 u C a p i t a l investment per t o n c o a l processed p e r year

Table VI.

1.10 2.53 1.42 4.79

0,.67 1,.54 0..87 2..89

0..61 1..37 0..79 2..53

Effect of Steam Price on the Unit Cost f o r Des u l f u r i z a t i o n of SRC Feed Coal by HGMS

Slurry Velocity (cm/sec)

Case A

Case Β

0.254 2.71^ 2.71 5.42 14.00

6.580 1.100 0.763 0.670 0.614

6.600 1.311 0.850 0.836 0.811

e

0.76 1.80 1.00 3.49

Unit

Cost

a

% Increase from Case A to Case Β

0.3 19.2 11.4 24.8 32.1

a Unit cost expressed i n $ per ton SRC feed coal processed Case A: steam p r i c e = 2 $/1000 l b ; Case B: steam p r i c e = 4 $/1000 l b . b Amount of l i q u e f i e d coal processed per cycle = 23.62 tons = 25.83 times weight of s t a i n l e s s s t e e l wool. ο Amount of l i q u e f i e d coal processed per cycle = 57.21 tons = 62.53 times weight of s t a i n l e s s s t e e l wool.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

133

C O A L DESULFURIZATION

Table V I I .

Approximate Comparison of C a p i t a l and U n i t C o s t s o f D i f f e r e n t S o l i d - L i q u i d S e p a r a t i o n Methods (29)

Method

1.

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2.

3,

4. 5.

So"

R o t a r y drum filtration (SRC) Pressure leaf filtration (SRC) Two-stage c e n trifugation^ (H-Coal) Solvent p r e c i p a t i o n (H-Coal) HGMS 5.4 cm/sec 2.7 cm/sec

£15*

Capital

Investment^

2.77

8.10

17.89

7.03

9.87

9.52

2.57

7.57

15.38

1.82

3.98

6.70

0.68 1.10

1.54 2.53

2.89 4.79

C

a U n i t c o s t s e x p r e s s e d i n ? per t o n SRC f e e d c o a l p r o c e s s e d . b C a p i t a l i n v e s t m e n t e x p r e s s e d i n $ per t o n SRC f e e d c o a l p r o c e s s e d per y e a r . ο The ash c o n t e n t o f s e p a r a t e d p r o d u c t may not s a t i s f y EPA s p e c i f i c a t i o n , and t h e use of e l e c t r o s t a t i c p r e c i p i t a t o r s may be needed.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch010

10.

LIN AND Liu

High-Intensity and -Gradient Magnetic Separation

135

s t e a m p r i c e w i l l i n c r e a s e t h e u n i t c o s t U q b y 0.3-32% i n t h e r a n g e o f s l u r r y v e l o c i t y c o n s i d e r e d . A s steam i s m a i n l y u s e d i n t h e e v a p o r a t o r t o r e c o v e r t h e wash s o l v e n t , t h i s c o m p a r i s o n a l s o i m p l i e s t h a t t h e h i g h e r t h e p r o c e s s t h r o u g h p u t , t h e more e x p e n s i v e w i l l be t h e o p e r a t i n g c o s t f o r s o l v e n t r e c o v e r y . F i n a l l y , a c o m p a r i s o n o f t h e a p p r o x i m a t e c a p i t a l i n v e s t m e n t and u n i t c o s t s o f s e v e r a l s o l i d - l i q u i d s e p a r a t i o n methods, i n c l u d i n g p r e c o a t f i l t r a t i o n , c e n t r i f u g a t i o n , s o l v e n t p r e c i p i t a t i o n and HGMS, i s g i v e n i n T a b l e V I I ( 2 9 ) , T h i s t a b l e shows t h a t a l t h o u g h the p r e c o a t f i l t r a t i o n and s o l v e n t p r e c i p a t i o n c a n g e n e r a l l y meet t h e s t r i n g e n t e n v i r o n m e n t a l s t a n d a r d s f o r b o t h s u l f u r a n d a s h , t h e c o s t s o f t h e s e methods a r e h i g h e r t h a n t h o s e f o r HGMS, T h u s , t h e r e seems t o b e some e c o n o m i c i n c e n t i v e f o r u s i n g mag­ n e t i c a l l y c l e a n e d SRC a s a f e e d t o b o i l e r s w h i c h a l r e a d y h a v e electrostatic precipitators. O b v i o u s l y , a d d i t i o n a l development w o r k i s needed t o s u p p o r t t h i s o b s e r v a t i o n f i r m l y . Acknowledgement The f i n a n c i a l s u p p o r t p r o v i d e d by the Auburn U n i v e r s i t y B o a r d o f T r u s t e e s 1975-1976 R e s e a r c h A w a r d , t h e N a t i o n a l S c i e n c e F o u n d a t i o n ( G r a n t Nos. G I - 3 8 7 0 1 and AER 7 6 - 0 9 3 0 0 ) , t h e G u l f O i l F o u n d a t i o n , and t h e E n g i n e e r i n g Experiment S t a t i o n o f Auburn U n i v e r s i t y are g r a t e f u l l y acknowledged.

Abstract The latest experimental data from pilot-scale studies of sulfur and ash removal from both pulverized coal suspended in a water slurry and from liquefied solvent refined coal by high gradient magnetic separation are used to design conceptual processes for desulfurization. Estimates of magnetic desulfuri­ zation characteristics and conceptual process requirements as well as installation and processing costs are presented. The results indicate that the magnetic processes appears to be attrac­ tive in terms of costs and performance when compared with other approaches to desulfurization. Appendix B a s i s f o r E s t i m a t i n g the U n i t Costs o f Magnetic D e s u l f u r i ­ z a t i o n o f Coal/Water S l u r r y . The d e t a i l e d o p e r a t i n g c o n d i t i o n s and e s t i m a t e d u n i t c o s t s f o r a t y p i c a l c o n c e p t u a l p r o c e s s f o r the magnetic d e s u l f u r i z a t i o n o f coal/water s l u r r y (case Β i n Table I ) a r e i l l u s t r a t e d as f o l l o w s . Operating

Conditions

(1) C o n c e n t r a t i o n o f c o a l / w a t e r s l u r r y = 25 w t % (2) S u p e r f i c i a l f l o w v e l o c i t y = 2.61 cm/sec

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

136

COAL

DESULFURIZATION

(3) S t a i n l e s s s t e e l w o o l p a c k i n g d e n s i t y = 6 w t % (4) Amount o f c o a l p r o c e s s e d p e r c y c l e = 7 t i m e s w e i g h t o f s t a i n l e s s s t e e l wool (5) Amount o f r i n s e w a t e r r e q u i r e d p e r c y c l e = 1,5 t i m e s v o l u m e of separator matrix (6) Amount o f wash w a t e r r e q u i r e d p e r c y c l e = 3 t i m e s volume of separator matrix (7) F l o w v e l o c i t y o f r i n s e w a t e r = f l o w v e l o c i t y o f c o a l s l u r r y (8) W a s h i n g t i m e p e r c y c l e = 1 m i n (9) Time f o r e n e r g i z i n g t h e magnet p e r c y c l e = 0.5 m i n (10) L a b o r r e q u i r e d = 2 men p e r s h i f t (11) Amount o f d i s p e r s a n t r e q u i r e d = 10 ppm

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch010

Investment Costs (1) C o s t s o f m a j o r i n s t a l l e d e q u i p m e n t ($) one HGMS u n i t pump tank (2) Add 2 0 % C o n t i n g e n c y

$1,936,000 38,480 24,370 1,998,850 399,770 $2,398,670

T o t a l I n v e s t m e n t ( I $) O p e r a t i n g C o s t s ($ p e r y e a r ) (1) D i s p e r s a n t

24,120 102,960 16,440

(57ç/lb)

(2) E l e c t r i c power (2Ç/KWH, 650 KW) (3) W a t e r (3C/1000 g a l ) (4) O p e r a t i n g l a b o r (2 m e n / s h i f t X 8304 h r / y r X 6.5$/man-hr) (5) M a i n t e n a n c e l a b o r ( 1 . 5 % o f i n v e s t m e n t c o s t ) (6) S u p e r v i s i o n ( 1 5 % o f o p e r a t i n g and m a i n t e n a n c e labor costs) (7) O p e r a t i n g s u p p l i e s ( 3 0 % o f o p e r a t i n g l a b o r c o s t ) (8) M a i n t e n a n c e s u p p l i e s ( 1 . 5 % o f i n v e s t m e n t c o s t ) (9) L o c a l t a x e s and i n s u r a n c e ( 2 . 7 % o f i n v e s t m e n t c o s t ) A n n u a l Net O p e r a t i n g Cost Ν $ Coal Processed Annually G tons

107,960 35,980

$

21,590 32,390 35,980 64,760 442,180 528,900

U n i t C o s t s ($ p e r t o n c o a l p r o c e s s e d ) See R e f . _29 and 34 f o r t h e c o s t e q u a t i o n s u s e d b e l o w . (1) B a s e d o n 0% DCF r a t e o f r e t u r n : Up = (N + 0.05 I ) /G = 1.063 $ / t o n (2) B a s e d on 1 5 % DCF r a t e o f r e t u r n : £l5 = (N + 0.34749 I ) / G = 2.412 $ / t o n (3) B a s e d on c a p i t a l a m o r t i z a t i o n o v e r 20 y e a r s a t 1 0 % i n t e r e s t rate: U = (Ν + 0.11746 I)/G = 1.369 $ / t o n

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

10. LIN AND LIU High-Intensity and -Gradient Magnetic Separation 137

Literature Cited 1. 2. 3.

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4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15.

Slack, Α.V., "Flue Gas Desulfurization An Overview," Chem. Eng. Progr., (1976), 72 (8), 94-97, Davis, J.C., "Coal Cleaning Readies for Wider Sulfur-Removal Role", Chem. Eng. (March 1, 1976) 83, 70-74. Kester, W.M., "The Effect of High-Intensity Magnetic Clean­ ing on Pulverized High Sulfur, Bituminous Coals", Master Thesis, School of Mines, West Virginia University, Morgantown, W. Va., 1966. Lin, C.J., Liu, Y.A., Vives, D.L., Oak, M.J., Crow, G.E., "Sulfur and Ash Removal from Coals by High Gradient Magnetic Separation", ACS Div. Fuel Chem. Preprints (1976), 21 (7), 124 (Papers presented at 172nd National Meeting.) Lin, C.J., Liu, Y.A., Vives. D.L., Oak, M.J., Crow, G.E., Huffman, E.L., "Pilot-Scale Studies of Sulfur and Ash Remo­ val from Coals by High Gradient Magnetic Separation", IEEE Trans. Magn., (1976), MAG-12, 513-521. Luborsky, F.E., "High Gradient Magnetic Separation for Re­ moval of Sulfur from Coal", Final report, issued by the General Electric Corporate Research and Development to the Bureau of Mines under contract no. H0366008, February, 1977, Oak, M.J., "Modeling and Experimental Study of High Gradient Magnetic Separation with Application to Coal Beneficiation", M.S. Thesis, Department of Chemical Engineering, Auburn University, Auburn, AL, 1977. Trindade, S.C. , "Studies on the MagneticDemineralizationof Coal", Ph.D. Thesis, Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA, 1973. Liu, Y.A., Editor, "Proceedings of Magnetic Desulfurization of Coal Symposium: A Symposium on the Theory and Applica­ tions of Magnetic Separation", IEEE Trans. Magn. (1976), MAG-12 (5), 423-551. Liu, Y.A., Lin, C.J., "Assessment of Sulfur and Ash Removal from Coals by Magnetic Separation", IEEE Trans. Magn. (1976), MAG-12, 538-550. Iannicelli, J., "Assessment of High Extraction Magnetic Fil­ tration", Special Report to the National Science Foundation, available as document No. Pb240-880/5 from the National Tech­ nical Information Service, Springfield, VA, 1974. Iannicelli, J., "New Developments in Magnetic Separation", IEEE Trans Magn. (1976), MAG-12, 436-443. Liu, Y.A., Lin, C.J., Vives, D.L., Oak, M.J., Crow, G.E., "Theory and Applications of High Gradient Magnetic Separa­ tion: A Review", invited paper, International Magnetics Conference, Los Angeles, CA, 1977, Luborsky, F.E., "High-Field High-Gradient Magnetic Separa­ tion: A Review", 21st National Conference on Magnetism and Magnetic Materials, Philadelphia, PA, December, 1975. Oberteuffer, J.A., "Magnetic Separation: A Review of Prin­

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Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch010

19. 20. 21.

GOAL DESULFURIZATION ciples, Devices and Applications", IEEE Trans. Magn. (1974), MAG-10, 223-238. Oberteuffer, J.A., "Engineering Development of High Gradient Magnetic Separation", IEEE Trans.Magn.,(1976), MAG-12, 444-449. Oder, R.R., "High Gradient Magnetic Separation: Theory and Applications", IEEE Trans. Magn. (1976), MAG-12, 428-435, Liu, Υ.Α., Lin, C.,J., "Status and Problems in the Develop­ ment of High Gradient Magnetic Separation Processes Applied to Coal Beneficiation", in "Proceedings of Engineering Foundation Conference on Clean Combustion of Coal", Rindge, N.H., July 31-August 5, 1977; to be published by the National Technical Information Service, Springfield, VA, 1977. Murray, H.H., "High Intensity Magnetic Cleaning of Bitumi­ nous Coals", National Coal Association and Bituminous Coal Research, Inc. Coal Conference and Expo III, Lexington, KY, 1976. Cavallaro, J.A., Johnston, M.T., and Deurbrouck, A,W., "Sulfur Reduction Potential of the Coals of the United States", U.S. Bur. Mines, Rep. Invest. (1976), 8118. Hoffman, L., "The Physical Desulfurization of Coal: Major Consideration of SO Emission Control", Special Report, Mitre Corp., MeLean, VA, November, 1970. Oder, R.R., "Pyritic Sulfur Removal from Coals by High Gradient Magnetic Separation", The 2nd National Conference on Water Re-Use, Chicago, IL, May, 1975. Thompson, R.D., York, H.F., "The Reserve Base of U.S. Coals by Sulfur and Ash Content, Part I. The Eastern States", U.S. Bur. Mines, Inf. Circ. (1975), 8680. Thompson, R.D., and York, H.F., "The Reserve Base of U.S. Coals by Sulfur and Ash Content, Part II. The Western States", U.S. Bur. Mines, Inf. Circ. (1975), 8693. Crow, G.E., "A Pilot-Scale Study of High Gradient Magnetic Desulfurization of Solvent Refined Coal", M.S. Thesis, Department of Chemical Engineering, Auburn University, Auburn, AL 1977. Hydrocarbon Research, Inc., Trenton, NJ, ReportNos.L-12-61501, issued to Electric Power Research Institute of Palo Alto, under Contract RP-340, 1975. Oder, R.R., "Magnetic Desulfurization of Liquefied Coals: Conceptual Process Design and Cost Estimation", IEEE Trans. Magn. (1976), MAG-12, 532-537. Wolk, R., Stewart, N., Alpert, S., "Solvent Refining for Clean Coal Combustion", EPRI J., (May 1976), 12-16. Batchelor, J.D., Shih, C., "Solid-Liquid Separation in Coal Liquefaction Processes", AIChE National Meeting, Los Angeles, CA, November, 1975. Agarwal, J.C., Gilberti, R.A., Irminger, P.F., Sareen, S.S., Chemical Desulfurization of Coal", Min. Congr. J. (1975), 70 (3), 40-43. 2

22. 23. 24. 25. 26. 27. 28. 29. 30.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch010

10.

LIN

AND

LIU

High-Intensity

and

-Gradient

Magnetic

Separation

139

31. Kindig, J.K., Turner, R.L., "Dry Chemical Process to Magnetize Pyrite and Ash Removal from Coal", Preprint No. 76-F366, SME-AIME Fall Meeting, Denver, September, 1976. 32. Ouinlan, R.M., Venkatesan, S., "Economics of Coal Preparation", Preprint No. 76-F-108, AIME Annual Meeting, Las Vegas, NV, February, 1976. 33. Van Nice, L.J., Santy, M.J., Meyers, R.A., "Meyers Process; Plant Design, Economics and Energy Balance", National Coal Association and Bituminuous Coal Research, Inc. Coal Conference and Expo, III, Lexington, KY, October, 1976. 34. Federal Power Commission, "Final Report: The Supply-Technical Advisory Task Force on Synthetic Gas-Coal", April, 1973. 35. Guthrie, D.M., "Capital Cost Estimating", Chem. Eng. (March 24, 1969), 76, 114-142. 36. Iannicelli, J., personal communication, Aquafine Corp., Brunswick, GA, October, 1976.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

11 Applicability of the Meyers Process for Desulfurization of U.S. Coal (A Survey of 35 Coals) J. W. HAMERSMA, M. L. KRAFT, and R. A. MEYERS

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch011

TRW

Systems and Energy, Redondo Beach, CA 90278

The Meyers process (1,2) is a new chemical leaching process which allows many coal-fired power plants and industrial sources to meet federal and state sulfur oxide emission standards without the use of flue gas cleaning. This process uses a regenerable aqueous ferric sulfate leaching unit to chemically convert and remove the pyritic sulfur content of the coal as elemental sulfur and iron sulfate. Although only pyritic sulfur is removed (organic sulfur remains), the Meyers process has wide applicability for converting U.S. coal reserves to a sulfur level consistent with present and proposed governmental sulfur oxide emission standards. Thirty-five mines from the major coal basins were investigated in this study. Because of the relatively high pyritic sulfur and low organic sulfur contents and because of high production of Appalachian coals (70% of current U.S. output), the Meyers process appears to have major impact in this area. In the Meyers process, aqueous ferric sulfate is used at 90°130°C t o oxidize selectively the pyritic sulfur c o n t e n t o f coal t o y i e l d i r o n s u l f a t e and f r e e e l e m e n t a l s u l f u r a s shown i n E q u a t i o n 1. The i r o n s u l f a t e d i s s o l v e s i n s o l u t i o n w h i l e t h e f r e e s u l f u r i s removed f r o m t h e c o a l m a t r i x e i t h e r b y v a p o r i z a t i o n o r s o l v e n t extraction. The l e a c h i n g ( o x i d i z i n g ) a g e n t i s t h e n r e g e n e r a t e d a t a s i m i l a r t e m p e r a t u r e u s i n g o x y g e n o r a i r and i s r e c y c l e d w h i l e p r o d u c t i r o n s u l f a t e s a r e removed b y l i m i n g a n d / o r c r y s t a l l i z a t i o n . 4.6 F e ( S 0 ) 2

4

3

+ 4.8 H 0 + F e S 2

2

10.2 FeSO^ + 4.8 H S 0 2

4

+ 0.8 S ( 1 )

The d e t a i l e d c h e m i s t r y , l e a c h i n g c o n d i t i o n s , r e a c t i o n k i n e t i c s , p r o c e s s e n g i n e e r i n g , and c o s t e s t i m a t e s h a v e b e e n p u b l i s h e d (3,4,5,6,7), and a r e a c t o r t e s t i n g u n i t has been b u i l t . T h i s c h a p t e r p r e s e n t s e x p e r i m e n t a l r e s u l t s and d i s c u s s i o n for: p y r i t i c s u l f u r removal from c o a l , p y r i t i c s u l f u r p a r t i t i o n by f l o a t - s i n k s e p a r a t i o n f r o m t h e same c o a l s , t h e e f f e c t o f t h e Meyers p r o c e s s on t h e t r a c e element c o n t e n t o f t h e t r e a t e d c o a l s , and a p p l i c a b i l i t y o f t h e M e y e r s p r o c e s s f o r m e e t i n g a i r p o l l u t i o n

143

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

144

C O A L DESULFURIZATION

c o n t r o l standards. T h i s w o r k was p e r f o r m e d u n d e r c o n t r a c t t o E n v i r o n m e n t a l P r o t e c t i o n Agency ( 8 , 9 ) .

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch011

Sulfur

the

Reduction

A summary o f t h e s u l f u r a n a l y s e s o f t h e r u n - o f - m i n e c o a l u t i l i z e d i n t h i s s t u d y i s shown i n F i g u r e 1. The o r g a n i c and p y r i t i c s u l f u r c o n t e n t s a r e p l o t t e d a l o n g t h e x-and y - a x i s r e s p e c t i v e l y w h i l e t h e sum o f t h e s e v a l u e s f o r a g i v e n c o a l c a n be reaù f r o m t h e diagonal lines. The a v e r a g e c o a l f o r t h i s s u r v e y c o n t a i n e d 2.02% p y r i t i c s u l f u r and 3.05% t o t a l s u l f u r . This corresponds to the U.S. B u r e a u o f M i n e s a v e r a g e f o r 325 raw c o a l s ( 1 0 ) , i n d i c a t i n g that the survey c o a l s r e p r e s e n t r e a s o n a b l y the s u l f u r d i s t r i b u t i o n i n U.S. coal. The r e s u l t s t o d a t e f o r c h e m i c a l r e m o v a l o f p y r i t i c s u l f u r (100-150 μ t o p - s i z e c o a l ) and t h e o p t i m a l r e s u l t s f o r c o n v e n t i o n a l c o a l w a s h i n g ( b a s e d on t h e 1.4 mm, 1.90 f l o a t f r a c t i o n o f a f l o a t s i n k a n a l y s i s ) a r e shown i n T a b l e I , i n t e r m s o f t o t a l s u l f u r c h a n g e s , and i n g r a p h i c a l f o r m i n F i g u r e 2. The t a b l e d e s c r i b e s t h e r e s u l t s o b t a i n e d on c o a l s w h i c h c o n t a i n e d s u f f i c i e n t p y r i t i c s u l f u r f o r a c c u r a t e s u l f u r r e m o v a l d e t e r m i n a t i o n ( i . e . , >0.25% w/w). Three of the mines sampled were below t h i s l i m i t and, t h e r e f o r e , do n o t a p p e a r i n t h e t a b l e . A c t u a l t o t a l s u l f u r v a l u e s b e f o r e and a f t e r c h e m i c a l r e m o v a l a r e shown i n columnsΟ and 4. These may be compared w i t h c o l u m n 5, w h i c h shows s u l f u r v a l u e s w h i c h c a n be o b t a i n e d w i t h f u l l p r o c e s s o p t i m i z a t i o n . T h i s l a t t e r v a l u e was c a l c u l a t e d by a d d i n g t h e a c t u a l r e s i d u a l p y r i t i c s u l f u r and s u l f a t e c o n t e n t s of the c o a l to the i n i t i a l o r g a n i c s u l f u r v a l u e a f t e r c o r r e c t i o n f o r any c o n c e n t r a t i o n e f f e c t s r e s u l t i n g f r o m a s h r e ­ moval. I n the survey program, complete removal of r e s i d u a l e l e ­ m e n t a l s u l f u r and s u l f a t e was n o t a l w a y s o b t a i n e d s i n c e c o n d i t i o n s were s t a n d a r d i z e d but not o p t i m i z e d f o r each i n d i v i d u a l c o a l . T h u s , f o r e x a m p l e , a l t h o u g h 96% p y r i t e c o n v e r s i o n was o b t a i n e d f o r t h e B i r d No. 3 c o a l , t h e t o t a l s u l f u r was r e d u c e d t o 0.80%, n o t t h e t h e o r e t i c a l 0.45% c a u s e d by t h e s e e f f e c t s . These p r o c e s s i n g p r o b l e m s h a v e now b e e n r e s o l v e d as p a r t o f o t h e r p r o j e c t s ( 3 , 9 ) , and t h e v a l u e s shown i n c o l u m n 5 can be c o n s i d e r e d t o r e p r e s e n t the t r u e p o t e n t i a l of the p r o c e s s . Because of the widespread a p p l i c a t i o n of p h y s i c a l c l e a n i n g t e c h n i q u e s f o r removal of nonc o m b u s t i b l e r o c k ( w h i c h i n c l u d e s v a r y i n g amounts o f p y r i t e a l o n g w i t h some c a r b o n ) f r o m c o a l , f l o a t - s i n k f r a c t i o n a t i o n was p e r ­ f o r m e d i n o r d e r t o d e f i n e t h e r e l a t i v e u t i l i t y o f w a s h i n g and chemical d e s u l f u r i z a t i o n f o r each c o a l . The r e s u l t s a r e shown i n c o l u m n 8 and a l s o i n F i g u r e 2. The s u l f u r r e d u c t i o n p o t e n t i a l o f t h e M e y e r s p r o c e s s i s h i g h l y a t t r a c t i v e and i n p a r t i c u l a r i t was found t h a t : (1) The M e y e r s p r o c e s s , a t i t s c u r r e n t s t a t e o f d e v e l o p m e n t , removed 83-99% o f t h e p y r i t i c s u l f u r c o n t e n t o f t h e 32 coals s t u d i e d , r e s u l t i n g i n t o t a l s u l f u r content r e ­ d u c t i o n s o f 25-80%

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

11.

HAMERSMA

Meyers Process for Desulfurization

E T A L .

APPALACHIAN INTERIOR BASINS WESTERN

Ο Δ •

Ν 24 Ν- 7 Ν -• 4

TOTAL SULPHUR,

% w/w \

\

\ \

Δ

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch011

ο

\

Ρ

\

Ο

Δ

\ \

\

\

N

v

ο

° n

Ο Ο

\

v

\ ό

Ο

V , \

^o

OOO

\

S

\ \

co\ L_2 l l _ 0.5

1.0

\

\

_J 1.5

\

\

M . 2.0

2.5

ORGANIC SULPHUR, % W/W

ι

5

6

7

8

Figure 1.

Sulfur forms of sampled U.S. coals

Figure 2. Sulfur content of survey run-ofmine coals (curve a), the same coals physically cleaned (curve c), and chemically de­ sulfurized (curve b)

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Navajo Kopperston No. 2 H a r r i s Nos. 1 & 2 Colstrip Warwick Marion Mathies Isabella Orient No. 6 Lucas Jane Martinka North River Humphrey No. 7 No. 1 Bird No. 3 Williams Shoemaker Meigs Fox Dean Powhattan No. 4 Eagle No. 2 Star Robinson Run

Mine 0..8 0.,9 1.,0 1.,0 1.,4 1.,4 1.,5 1.,6 1.,7 1.,8 1.,8 2.,0 2. ,1 2,,6 3..1 3.,1 3..5 3..5 3,.7 3,.8 4,.1 4..1 4,.3 4,.3 4,.4 0,.6 0,.6 0..8 0,.6 0,,6 0,,7 0,,9 0,,1 0..9 0..6 0,,7 0,.6 0..9 1..5 1..6 0,.8 1..7 1,.7 1,.9 1,.6 2,.1 1,.9 2,.0 2..5 2,.2

0.,5 0..5 0.,6 0.,7 0.,4 0.,6 0.,5 0.,5 0.,8 0.,5 0.,6 0.,8 0.,8 1.,2 1.,4 0.,4 1.,4 1.,5 1,.7 1..2 1,.6 1,.9 1,.9 1,.8 1,.6

% T o t a l S u l f u r w/w i n Coal2 A f t e r Meyers Process Current Revised Initial Results Processing^ 90 92 94 83 92 96 95 96 96 94 91 92 91 91 90 96 96 96 93 89 94 85 94 91 97

25 33 23 30 54 50 36 54 44 64 63 70 55 42 48 75 50 51 48 57 49 53 54 43 50

Meyers P r o c e s s " Pyrite Total S Conv. Decrease (% w/w) (% w/w)

Summary of P y r i t i c S u l f u r Removal Results^(100-150 u t o p - s i z e coal)

Nos. 6,7,8 Campbell Creek Eagle & No. 2 Gas Rosebud Sewickley Upper Freeport Pittsburgh Pittsburgh H e r r i n No. 6 Middle K i t t a n n i n g Lower Freeport Lower K i t t a n n i n g Corona Pittsburgh Mason Lower K i t t a n n i n g Pittsburgh Pittsburgh C l a r i o n 4A Lower K i t t a n n i n g Dean P i t t s b u r g h No. 8 I l l i n o i s No. 5 No. 9 Pittsburgh

Seam

Table I.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch011

1.0 1.2 1.7 1.5 1.4 0.7 0.8 0.8 2.2 1.9 2.3 1.5 2.3 3.6 2.8 2.0 3.0 3.3 2.9 3.0 3.0

0.8 0.9

% Sulfur i n Coal^ After FloatSink

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

No. 11 No. 9 (W. Ky.) No. 9 Upper F r e e p o r t Meigs Creek Des M o i n e s No. 1 P i t t s b u r g h No. 8

Seam 4.5 4.5 4.8 4.9 6.1 6.4 6.6

Initial

% Total

1.7 2.0 2.8 0.8 3.2 2.2 2.7

1..6 2. ,1 2. ,2 0..5 2. ,7 1. ,7 2. ,1

S u l f u r w/w i n C o a l 2 ~ A f t e r Meyers Process Current Revised Results Processing^ 93 89 91 965 94 92 89

47 55 42 80 47 65 59

Meyers P r o c e s s " Pyrite Total S Conv. Decrease (% w/w) (% w/w) 3,.2 2,.9 3..5 2,.1 4,Λ 3.,9 4.,6

% Sulfur i n Coal^ After FloatSink

moisture-free

Run

using

a t 200 m χ 0.

Calculated

l a t e s t process

improvement.

14 mesh χ 0, i s d e f i n e d

basis.

1.90 f l o a t m a t e r i a l ,

Dry,

here as the l i m i t o f c o n v e n t i o n a l

coal

cleaning.

A 100 g s a m p l e o f c o a l was r e f l u x e d w i t h 2 L o f I N F e 2 ( S 0 4 ) 3 s o l u t i o n . A f t e r 4-6 h r s , t h e r e d u c e d s o l u t i o n was f i l t e r e d f r o m t h e c o a l a n d t h e c o a l was r e f l u x e d w i t h 2 L o f f r e s h I N F e 2 ( S 0 4 ) 3 . A f t e r a t o t a l e x t r a c t i o n t i m e o f 10-24 h r , t h e s l u r r y was f i l t e r e d and t h e c o a l c a k e was washed w i t h 0.2N H2SO4, t h e n w i t h w a t e r t o remove r e s i d u a l s u l f a t e . T o l u e n e (400 m l ) e x t r a c t i o n o f t h e c o a l removed e l e m e n t a l s u l f u r . The c o a l c a k e was t h e n d r i e d i n a vacuum oven a t 100-120°C.

Homestead Camp Nos. 1 & 2 Ken Delmont Muskingum Weldon No. 11 Egypt V a l l e y No. 21

Mine

Table I continued.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch011

148

C O A L DESULFURIZATION

(2)

T w e l v e (38%) o f t h e c o a l s w e r e r e d u c e d i n s u l f u r c o n t e n t to t h e 0.6-0.8% s u l f u r l e v e l s g e n e r a l l y c o n s i s t e n t w i t h t h e F e d e r a l New S o u r c e P e r f o r m a n c e S t a n d a r d s ar»H many s t a t e standards I n a l l c a s e s , t h e M e y e r s p r o c e s s removed s i g n i f i c a n t - t o v e r y l a r g e i n c r e m e n t s o f s u l f u r o v e r t h a t s e p a r a b l e by physical cleaning I n two c a s e s , t h e C o r o n a and M a t h i e s m i n e s , c o a l c l e a n ­ ing a c t u a l l y r e s u l t e d i n a s u l f u r content i n c r e a s e i n the f l o a t product.

(3)

(4)

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch011

Rate of P y r i t i c

S u l f u r Removal

The r e m o v a l o f p y r i t i c s u l f u r was measured as a f u n c t i o n o f t i m e a t 100°C f o r 18 A p p a l a c h i a n and 3 e a s t e r n i n t e r i o r r e g i o n coals. The r e s u l t s a r e d i s p l a y e d i n T a b l e I I , w h i c h shows t h e range of r a t e s observed. I t was assumed t h a t t h e e m p i r i c a l k i n ­ e t i c r a t e e x p r e s s i o n (3) w h i c h was d e v e l o p e d p r e v i o u s l y f o r t h i s process i s a p p l i c a b l e to a l l c o a l s i n the survey. The k i n e t i c e q u a t i o n c a n be s i m p l i f i e d by h o l d i n g t h e r e a g e n t c o n c e n t r a t i o n r e l a t i v e l y c o n s t a n t , as was t h e c a s e i n t h i s s t u d y , t o y i e l d E q u a t i o n 2: -d[W ] p

, °τ» 2 _ . = k W = r a t e of p y r i t e D

removal

(2)

dt w h e r e : W = w e i g h t p e r c e n t p y r i t e i n t h e c o a l , and k° = f u n c t i o n of tempeTâture, c o a l t y p e and p a r t i c a l s i z e . By i n t e g r a t i n g E q u a t i o n 2, t h e f r a c t i o n o f p y r i t e removed as a f u n c t i o n o f t i m e i s shown i n E q u a t i o n 3: p

1-F where: F centration, The i n i t i a l f o r WWp ° and n

Ρ

_

(3)

F

f r a c t i o n o f p y r i t e removed, W = i n i t i a l p y r i t e con­ and t p = t i m e t o r e m o v a l a t T r a c t i o n F. w e i g h t p e r c e n t o f p y r i t i c s u l f u r Sp° may be s u b s t i t u e d E q u a t i o n 3 be r e a r r a n g e d t o E q u a t i o n 4 p

ο k = a c t u a l r a t e constant

(A)

T h u s , a s s u m i n g 80% r e m o v a l as a p o i n t o f c o m p a r i s o n , t h e v a l u e s o f 1/Sp_°_t80% shown i n c o l u m n 6 o f T a b l e I I i n d i c a t e t h e r e a c t i v i t i e s of t h e p y r i t e c o n t a i n e d i n t h e c o a l s t h a t w e r e s t u d i e d . A l a r g e amount o f e x p e r i m e n t a t i o n and e n g i n e e r i n g has b e e n p e r f o r m e d u s i n g r a t e d a t a o b t a i n e d f o r M a r t i n k a (3) c o a l ; t h e r e f o r e , t h e M a r t i n k a c o a l Sp°tftQ% has b e e n s e t e q u a l t o 1 as a b a s i s o f c o m p a r i s o n (as shown i n c o l u m n 7 ) .

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Campbell Creek E a g l e & No. 2 Gas Upper F r e e p o r t Middle Kittanning Pittsburgh Pittsburgh No. 9 Corona No. 9 Pittsburgh P i t t s b u r g h No. 8 No. 11 Lower K i t t a n n i n g Pittsburgh Lower K i t t a n n i n g C l a r i o n 4A Lower K i t t a n n i n g Dean M e i g s C r e e k No. 9

Seam 149 149 149 100 149 100 149 149 100 100 75 149 75 149 149 149 100 100 149 0.47 0.49 0.90 1.42 2.19 2.23 2.85 1.42 2.66 1.05 2.75 3.11 3.09 1.07 1.42 2.19 2.87 2.62 3.65

Sp°

forPyritic

Top Size (Microns)

R e l a t i v e Rate Constants

2.0 2.3 3.0 3.25 2.9 3.0 2.5 5.0 3.0 9.0 4.0 3.5 4.5 13.0 10.0 8.5 8.0 10.2 8.0

80% (hrs)

u

Sulfur

1.1 0.89 0.37 0.22 0.16 0.15 0.14 0.14 0.13 0.11 0.091 0.092 0.072 0.072 0.070 0.054 0.044 0.037 0.034

^ % 0 %

1

R e a l t i v e Rate

Removal

16 13 5.3 3.1 2.3 2.1 2.0 2.0 1.9 1.6 1.3 1.3 1.0 1.0 1.0 0.77 0.62 0.53 0.49

Relative Rate

2

Constants

l/S>p_tgQ0£ r e l a t i v e t o v a l u e f o r M a r t i n k a m i n e .

o

As i n f o o t n o t e 1 o f T a b l e I , e x c e p t t o l u e n e e x t r a c t i o n was o m i t t e d . P y r i t e removal r a t e data was o b t a i n e d by p y r i t e a n a l y s i s o f c o a l s a m p l e s o b t a i n e d f r o m s l u r r y a l i q u o t s by c e n t r i f u g a t i o n .

K o p p e r s t o n No. 2 H a r r i s Nos. 1 & 2 Marion Lucas Shoemaker Williams Ken North River Star Mathies P o w h a t t a n No. 4 Homestead Fox Isabella Martinka Meigs B i r d No. 3 Dean Muskingum

Coal Mine

Table I I .

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch011

150

DESULFURIZATION

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch011

COAL

FLOAT - SINK SEPARATION (FLOAT FRACTION) MEYERS PROCESS

Figure 3.

Trace element removal data

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

11.

HAMERSMA

E T

AL.

Meyers Process for Desulfurization

151

I t c a n be e a s i l y s e e n f r o m T a b l e I I t h a t t h e r e i s a w i d e band o f r a t e c o n s t a n t s r a t h e r e v e n l y s p r e a d o v e r a f a c t o r o f a p p r o x i m a t e l y 30. The K o p p e r s t o n No. 2 a n d H a r r i s N o s . 1 and 2 c o a l s r e a c t more r a p i d l y t h a n t h e s l o w e s t c o a l s (Dean a n d Muskingum) b y a f a c t o r o f a b o u t 30. T h u s , i t i s a p p a r e n t t h a t r e a l a n d s i g n i f i c a n t r a t e d i f f e r e n c e s do e x i s t b e t w e e n p y r i t e i n various coals. C h a r a c t e r i s t i c s o f c o a l such as pore s t r u c t u r e , s i z e a n d s h a p e d i s t r i b u t i o n o f p y r i t e , e t c . may be t h e p r i m a r y f a c t o r s a f f e c t i n g t h e r a t e c o n s t a n t as r e f l e c t e d i n t h e observed band o f v a l u e s f o u n d f o r t h e r a t e s g i v e n i n T a b l e I I .

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch011

T r a c e Element Removals B e c a u s e b o t h c h e m i c a l l e a c h i n g and p h y s i c a l c l e a n i n g p r o c e s s e s c a n remove p o t e n t i a l l y h a r m f u l t r a c e e l e m e n t s f r o m c o a l e i t h e r by l e a c h i n g o r by p h y s i c a l p a r t i t i o n i n g , 50 c o a l s a m p l e s have been a n a l y z e d i n d u p l i c a t e o r t r i p l i c a t e t o determine t h e e x t e n t o f t h e r e m o v a l , i f a n y , o f 18 e l e m e n t s o f i n t e r e s t t o t h e E n v i r o n m e n t a l P r o t e c t i o n A g e n c y . The s a m p l e s i n c l u d e d 20 a s r e c e i v e d , 20 c h e m i c a l l y l e a c h e d , and 10 f l o a t - s i n k t r e a t e d c o a l s a m p l e s . The r e s u l t s a r e shown f o r 12 e l e m e n t s i n F i g u r e 3 i n cumulative fashion. The e x t r a c t i o n p r o c e d u r e was a s i n T a b l e I . S i x e l e m e n t s , B, B e , Hg, Sb, Se, and Sn y i e l d e d n e g a t i v e o r i n c o n c l u s i v e r e s u l t s because of low l e v e l s o r a n a l y s i s d i f f i c u l t i e s and t h u s a r e n o t p l o t t e d . A l t h o u g h t h e r e s u l t s v a r i e d g r e a t l y f r o m c o a l t o c o a l w i t h r e s p e c t t o t h e e l e m e n t s e x t r a c t e d and t h e d e g r e e o f e x t r a c t i o n , some g e n e r a l c o n c l u s i o n s c a n be r e a c h e d . (1) A s , C d , Mn, N i , P b , and Zn a r e removed t o a s i g n i f i c a n t l y g r e a t e r e x t e n t by t h e Meyers p r o c e s s (2) F and L i a r e p a r t i t i o n e d t o a g r e a t e r e x t e n t by p h y s i c a l separation procedures. (3) Ag a n d Cu a r e removed w i t h a s l i g h t p r e f e r e n c e f o r f l o a t - s i n k separation (4) C r a n d V a r e removed by b o t h p r o c e s s e s w i t h e q u a l success. The e f f e c t i v e r e m o v a l o f A s , C d , C r , N i , P b , and Zn f r o m t h e c o a l b y t h e M e y e r s p r o c e s s i s e s p e c i a l l y n o t e w o r t h y a s t h e s e compounds a r e c o n c e n t r a t e d ( a l o n g w i t h Se) i n t h e f i n e p a r t i c u l a t e s e m i t t e d f r o m c o a l - f i r e d power p l a n t s . This f i n e p a r t i c u l a t e matter passes through conventional f l y - a s h c o n t r o l devices.

Literature Cited

1. Meyers, R.A., Hamersma, J.W., Land, J.S., Kraft, M.L., Science, (1972),177,1187. 2. Meyers, R.A., "Removal of Pyritic Sulfur from Coal Using Solutions Containing Ferric Ions," U.S. Patent 3768988, 1973. 3. Koutsoukos, E.P., Kraft, M.L., Orsini, R.A., Meyers, R.A., Santy, M.J., Van Nice, L.J., "Final Report Program for BenchScale Development of Processes for the Chemical Extraction of

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

152 4. 5. 6.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch011

7. 8.

9. 10.

COAL DESULFURIZATION

Sulfur from Coal," Environ. Prot. Technol. Ser., (May 1976), EPA-600/2-76-143a. Hamersma, J.W., Koutsoukos, E.P., Kraft, M.L., Meyers, R.A., Ogle, G.J., Van Nice, L.J., "Chemical Desulfurization of Coal: Report of Bench-Scale Developments, Volumes 1 and 2," Environ. Prot. Technol. Ser., (February 1973),EPA-R2-173a. Magee, E.M., "Evaluation of Pollution Control in Fossil Fuel Conversion Processes, Coal Treatment: Section 1. Meyers Process," Environ. Prot. Technol. Ser., (September 1975), EPA-650/2-74-009k. Nekervis, W.F., Hensley, E.F., "Conceptual Design of a Commercial Scale Plant for Chemical Desulfurization of Coal," Environ. Prot. Technol. Ser. (September 1975), EPA-600/2-75-051. Tek, M. Rasin, "Coal Beneficiation," in Evaluation of Coal Conversion Processes, (1974) PB-234202. U.S. Environmental Protection Agency, Office of Research and Development, Washington, DC, "Applicability of the Meyers Process for Chemical Desulfurization of Coal: Initial Survey of Fifteen Coals," by J.W. Hamersma et al, Systems Group of TRW, Inc., Redondo Beach, CA. (April 1974), EPA-650/2-74-025, Contract No. 68-02-0647. Hamersma, J.W., Kraft, M.L., "Applicability of the Meyers Process for Chemical Desulfurization of Coal: Survey of Thirty-Five Coals," Environ. Prot. Technol. Ser., (September 1975), EPA-650/2-74-025a. Deurbrouck, A.W., "Sulfur Reduction Potential of Coals of the United States," U.S. Bur. Mines Rep. Invest. (1972), 7633.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

12 Coal Desulfurization Test Plant Status—July 1977 L. J. VAN NICE, M. J. SANTY, E. P. KOUTSOUKOS, R. A. ORSINI, and R. A. MEYERS

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch012

TRW

Systems and Energy, Redondo Beach, CA 90278

An 8-metric ton/day process test plant for chemical desulfurization of coal utilizing ferric sulfate leach solution, has just been built atTRW'sCapistrano Test Site in California. The plant, shown in Figures 1 and 2, was constructed under an Environmental Protection Agency sponsored project for the development of the Meyers process. Current plans call for plant shakedown followed by processing of 100-200 tons of American Electric Power Service Corporation's Martinka mine coal. The Meyers process and its applicability for directly desulfurizing raw run-of-mine coal were presented in the previous chapter and the process is described in connection with the broad field of chemical desulfurization in a newly issued book (1). We have very recently verified that the ferric sulfate leach solution, which has a specific gravity of 1.2-1.4, can be used to gravity separate coal into float and sink fractions in a manner very advantageous to the Meyers process. This float-sink approach was tested many years ago by A. Z. Yurovskii in the U.S.S.R but only published in the open literature very recently (2). Yurovskii subsequently treated the sink coal with a mixture of nitric acid and ferric sulfate to remove pyritic sulfur, not realizing, that the separation medium itself was sufficiently active to accomplish near total pyritic sulfur removal. I n f a c t , a p r a c t i c a l method f o r a c t u a l f l o a t - s i n k c l e a n i n g of c o a l i n a dense l i q u i d has l o n g been sought as an a l t e r n a t i v e to mechanical c l e a n i n g . Heavy l i q u i d s , s u c h a s z i n c c h l o r i d e water, o r c h l o r i n a t e d , brominated, o r f l u o r i n a t e d hydrocarbons a r e u s e f u l f o r p r e d i c t i o n o f y i e l d s w h i c h c a n t h e o r e t i c a l l y be obtained i n mechanical washing p l a n t s , but a r e i m p r a c t i c a l f o r a c t u a l p r o d u c t i o n b e c a u s e t h e y a r e e x p e n s i v e and a d d p o l l u t a n t s t o t h e c o a l , a t m o s p h e r e o r w a t e r t a b l e . We f i n d t h a t t h e d e n s i t y o f aqueous f e r r i c s u l f a t e l e a c h s o l u t i o n , a s u t i l i z e d i n t h e M e y e r s process, i s i d e a l for accomplishing a p r a c t i c a l gravity separation o f c o a l f o r s p e c i f i c g r a v i t i e s b e t w e e n 1.2 a n d 1.4. F o r a b o u t 4 0 % o f A p p a l a c h i a n c o a l , t h e f l o a t c o a l ( w h i c h i s o f t e n 40-60% b y w e i g h t o f t h e t o t a l ) a v e r a g e s 0.8-1.2 l b s S O / 1 0 b t u a n d n e e d s 6

2

153

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

DESULFURIZATION

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch012

COAL

a.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977. Figure 2.

Test plant—view through tank farm

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch012

αχ

CO

3

«5

ο

Η

ο w

2

156

C O A L DESULFURIZATION

no f u r t h e r p r o c e s s i n g t o meet s t a n d a r d s , w h i l e t h e s i n k c o a l s l u r r y c o n t a i n s most o f t h e c o a l p y r i t e . T h i s c o a l s l u r r y can be p r o c e s s e d t h r o u g h t h e M e y e r s p r o c e s s t o g i v e c o a l c o n t a i n i n g 1.21.5 l b s b t u . This approach a l l o w s p r o d u c t i o n o f c o a l which w i l l meet a i r p o l l u t i o n c o n t r o l s t a n d a r d s f o r b o t h New a n d E x i s t ing S t a t i o n a r y S o u r c e s , and reduces t h e c o s t o f t h e Meyers p r o c e s s t h r o u g h a l l o w i n g 40-60% o f t h e c o a l t o b y p a s s r e a c t o r , e l e m e n t a l s u l f u r e x t r a c t i o n and d r y e r u n i t s . We t e r m t h i s a p p r o a c h , G r a v i c h e m C l e a n i n g . Where e s t i m a t e d processing costs using u t i l i t y financed depreciation of c a p i t a l and i n c l u d i n g c o a l g r i n d i n g a n d c o m p a c t i o n w e r e f o r e c a s t s f o r t h e new G r a v i c h e m C l e a n i n g a p p r o a c h a r e $8.50/ton

SO2/IO6

$10-12/ton (1),

6

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch012

($0.35/10 b t u ) . Process

Chemistry,

K i n e t i c s a n d Scheme

The p r o c e s s i s b a s e d o n t h e o x i d a t i o n o f c o a l p y r i t e w i t h f e r r i c s u l f a t e ( E q u a t i o n 1). The l e a c h i n g r e a c t i o n i s h i g h l y s e l e c t i v e t o p y r i t e w i t h 60% o f the p y r i t i c s u l f u r converted t o s u l f a t e s u l f u r and 40% t o e l e m e n t a l s u l f u r . The r e d u c e d f e r r i c i o n i s r e g e n e r a t e d b y o x y g e n o r a i r a c c o r d i n g t o E q u a t i o n s 2 o r 3. FeS

2

+

4.6 Fe (S0 ) + 4.8 H 0 -* 10.2 FeS0 + 4.8 H S0 + 0.8 S (1) 2

4

3

4

2

2

4

2.4 0 + 9.6 FeS0 + 4.8 H S0 + 4.8 Fe (S0 ) + 4.8 H 0

(2)

2.3 0 + 9.2 FeS0 +4.6 H S0 +4.6 Fe (S0 ) + 4.6 H 0

(3)

2

4

2

2

4

4

2

2

4

4

2

3

4

2

3

2

R e g e n e r a t i o n c a n be p e r f o r m e d e i t h e r c o n c u r r e n t l y w i t h c o a l p y r i t e l e a c h i n g i n a s i n g l e o p e r a t i o n o r s e p a r a t e l y . The n e t e f f e c t o f t h e p r o c e s s i s t h e o x i d a t i o n o f p y r i t e w i t h oxygen to y i e l d r e c o v e r a b l e i r o n , s u l f a t e s u l f u r , a n d e l e m e n t a l s u l f u r . The f o r m o f p r o c e s s p r o d u c t s v a r i e s t o some e x t e n t w i t h t h e d e g r e e of r e g e n e r a t i o n . Thus, E q u a t i o n s 1 and 2 l e a d t o t h e o v e r a l l p r o cess c h e m i s t r y i n d i c a t e d by E q u a t i o n 4 p r o d u c i n g a m i x t u r e o f i r o n s u l f a t e s and e l e m e n t a l s u l f u r . E q u a t i o n s 1 and 3 y i e l d f e r r o u s s u l f a t e , s u l f u r i c a c i d , and e l e m e n t a l s u l f u r as i n d i c a t e d by E q u a t i o n 5. FeS

2

+

2.4

0 + 0.6 FeS0 + 0.2 Fe (S0 ) + 0.8 S

(4)

FeS

2

+

2.3

0 + 0.2 H 0 -> FeS0 + 0.2 H S0 + 0.8 S

(5)

2

2

4

2

2

4

4

3

2

4

Several options e x i s t i n product recovery. I r o n s u l f a t e s may be r e c o v e r e d a s p u r e s o l i d s b y s t e p w i s e e v a p o r a t i o n o f a s p e n t r e agent s l i p s t r e a m w i t h f e r r o u s s u l f a t e b e i n g recovered f i r s t b e cause o f i t s lower s o l u b i l i t y . A l t e r n a t e l y , f e r r o u s s u l f a t e may be r e c o v e r e d b y c r y s t a l l i z a t i o n a n d f e r r i c s u l f a t e o r s u l f u r i c

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch012

12.

V A N NICE

E T A L .

Desulfurization

Test Phnt

Status

157

a c i d removed b y l i m i n g s p e n t r e a g e n t o r s p e n t wash w a t e r s l i p streams. I r o n s u l f a t e s may b e s t o r e d a s s o l i d s f o r s a l e o r may be c o n v e r t e d e a s i l y t o h i g h l y i n s o l u b l e b a s i c i r o n s u l f a t e s (by a i r o x i d a t i o n ) o r c a l c i u m s u l f a t e (by low-temperature s o l i d phase r e a c t i o n ) f o r d i s p o s a l . E l e m e n t a l s u l f u r may b e r e c o v e r e d f r o m c o a l b y v a p o r i z a t i o n w i t h s t e a m o r b y vacuum, o r i t c a n b e l e a c h e d out w i t h o r g a n i c s o l v e n t s such as acetone depending on product m a r k e t a b i l i t y and p r o d u c t r e c o v e r y economics. Recovery economics may b e i n f l u e n c e d b y q u a n t i t y a n d c o n c e n t r a t i o n o f p r o d u c t i n t h e process e f f l u e n t streams which i n t u r n a r e i n f l u e n c e d by t h e p y r i t e c o n c e n t r a t i o n i n t h e c o a l and t h e d e s i r e d e x t e n t o f d e s u l f u r i z a tion. The p r o c e s s h a s b e e n e x t e n s i v e l y s t u d i e d a t b e n c h - s c a l e . Parameters i n v e s t i g a t e d include c o a l t o p - s i z e , reagent composition, s l u r r y c o n c e n t r a t i o n , r e a c t i o n t e m p e r a t u r e and p r e s s u r e , and r e a c t i o n time. A d d i t i o n a l i n v e s t i g a t i o n s c o m p l e t e d o r underway i n c l u d e c o n current coal leaching-reagent regeneration, product recovery, product s t a b i l i t y , and t h e e f f e c t o f c o a l p h y s i c a l c l e a n i n g on p r o c e s s p e r f o r m a n c e a n d e c o n o m i c s . The p r o c e s s scheme d e p i c t e d i n F i g u r e 3 i s based on t h e b e n c h - s c a l e t e s t i n g . Coal i s (1) Crushed t o t h e d e s i r e d s i z e f o r p r o c e s s i n g (2) Contacted w i t h h o t r e c y c l e d reagent i n the mixer (90°-100°C) (3) Leached o f p y r i t e i n t h e r e a c t o r ( s ) w i t h simultaneous or separate reagent regeneration (4) Washed w i t h h o t w a t e r (5) S t r i p p e d o f e l e m e n t a l s u l f u r , d r i e d and f i n a l l y cooled. The i r o n a n d s u l f a t e s u l f u r a r e r e c o v e r e d f r o m s p e n t r e a g e n t s l i p s t r e a m s p r i o r t o r e a g e n t r e c y c l e . F i g u r e 4 shows t y p i c a l d a t a o n p y r i t e r e m o v a l r a t e s f r o m A p p a l a c h i a n c o a l a s a f u n c t i o n o f temperature. D u r i n g s l u r r y m i x i n g a n d h e a t - u p , 10-20% o f t h e p y r i t e i s removed. Bench-scale data i n d i c a t e d that t h e p y r i t e l e a c h i n g r a t e from c o a l c a n be a d e q u a t e l y r e p r e s e n t e d by t h e e m p i r i c a l r a t e e x p r e s s i o n (Equation 6 ) . r. = -

=h

W

2

Y

2

(6)

where: = A^ exp (-E^/RT), W = w t % p y r i t e i n c o a l , Y = f e r r i c i o n - t o - t o t a l i r o n r a t i o i n t h e r e a c t o r r e a g e n t , a n d A^ and E^ a r e c o n s t a n t s f o r e a c h c o a l a n d p a r t i c l e s i z e a t l e a s t o v e r most o f the r e a c t i o n range. The l e a c h r a t e i s a f u n c t i o n o f c o a l t y p e . Pyrite extraction r a t e s vary c o n s i d e r a b l y , as d e t a i l e d i n a study o f the Meyers p r o c e s s a s a p p l i e d t o U.S. c o a l ( 3 ) , e.g., t h e r e was more t h a n one o r d e r o f magnitude d i f f e r e n c e between t h e f a s t e s t and s l o w e s t r e a c t i n g c o a l . The r e a g e n t r e g e n e r a t i o n r a t e i s g o v e r n e d b y t h e rate expression (Equation 7 ) .

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch012

COAL DESULFURIZATION

Figure 3.

Process flow schematic

REACTION TIME, HOURS

Figure 4.

Temperature effect on processing of 14 mesh top-size Lower Kittanning coal (33% w/w slurries)

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

12.

VAN

NICE

ET

Desulfurization

AL.

£

R

= "

= Κ* Pô Qt

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch012

Test Phnt

Status

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+ 2

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2

159

7

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+2 where: = exp (-E^/RT), = o x y g e n p a r t i a l p r e s s u r e , Fe = f e r r o u s i o n c o n c e n t r a t i o n i n t h e r e a g e n t s o l u t i o n , and and are constants. E n g i n e e r i n g e v a l u a t i o n o f a v a i l a b l e d a t a shows t h a t i t i s p r e f e r a b l e t o p r o c e s s f i n e c o a l (<2 mm t o p - s i z e ) u n d e r s i m u l t a n ­ eous l e a c h i n g - r e g e n e r a t i o n c o n d i t i o n s a t 110°-130°C u n t i l most o f the p y r i t e i s leached out. Ambient p r e s s u r e p r o c e s s i n g ( a p p r o x i ­ m a t e l y 100°C) i s i n d i c a t e d t o remove t h e l a s t few t e n t h s p e r c e n t o f p y r i t e s i n c e t h e l o w Wp v a l u e s u b s t a n t i a l l y r e d u c e s t h e r a t e o f f e r r i c i o n c o n s u m p t i o n and, t h e r e f o r e , t h e need f o r s i m u l t a n e o u s r e a g e n t r e g e n e r a t i o n . A m b i e n t p r e s s u r e p r o c e s s i n g a p p e a r s t o be i n d i c a t e d a l s o f o r c o a r s e c o a l ( e . g . , 10 mm t o p - s i z e ) f o r s e v e r a l reasons. I t i s d i f f i c u l t to feed continuously a non-slurryable c o a l i n t o and remove i t f r o m a p r e s s u r e v e s s e l . I t i s much e a s i e r and l e s s c o s t l y t o d r a i n l e a c h s o l u t i o n f r o m t h e c o a l and pump i t i n t o a s m a l l pressure v e s s e l f o r r e g e n e r a t i o n . A l s o the slower r e a c t i o n r a t e w i t h c o a r s e c o a l w o u l d r e q u i r e much l o n g e r r e s i d e n c e t i m e s and u n r e a s o n a b l y l a r g e t o t a l v o l u m e f o r p r e s s u r e v e s s e l s . These e n g i n e e r i n g e v a l u a t i o n s w e r e p a r t o f t h e d a t a u s e d t o d e s i g n the t e s t p l a n t . T e s t P l a n t D e s i g n and

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A t e s t p l a n t s i z e d t o p r o c e s s up t o 8 m e t r i c t o n s p e r day o f c o a l has b e e n b u i l t u n d e r t h e s p o n s o r s h i p o f t h e E n v i r o n m e n t a l P r o t e c t i o n A g e n c y a t TRW s C a p i s t r a n o t e s t s i t e . A p l a n t f l o w d i a g r a m i s shown i n F i g u r e 5. The f a c i l i t y c a n e v a l u a t e t h e following c r i t i c a l on-line operations : (1) P r e s s u r e l e a c h i n g o f p y r i t i c s u l f u r f r o m 150 μ t o 2 mm t o p - s i z e c o a l a t p r e s s u r e s up t o 100 p s i g (2) R e g e n e r a t i o n o f f e r r i c s u l f a t e b o t h s e p a r a t e l y , f o r p r o ­ c e s s i n g l a r g e r t o p - s i z e c o a l o r l o w p y r i t e c o a l , and i n a s i n g l e v e s s e l w i t h the l e a c h i n g step f o r p r o c e s s i n g of suspendable c o a l (3) F i l t r a t i o n o f l e a c h s o l u t i o n f r o m r e a c t e d c o a l (4) W a s h i n g o f r e s i d u a l i r o n s u l f a t e f r o m t h e c o a l 1

I r o n s u l f a t e c r y s t a l l i z a t i o n , e l e m e n t a l s u l f u r r e c o v e r y , and c o a l - d r y i n g u n i t o p e r a t i o n s w i l l be e v a l u a t e d i n an o f f - l i n e mode i n equipment vendor p i l o t u n i t s . L e a c h i n g o f 10 mm t o p - s i z e c o a l c a n be e v a l u a t e d i n an o f f - l i n e mode i n an a t m o s p h e r i c pressure v e s s e l i n t h e t e s t p l a n t . C o a r s e c o a l p r o c e s s i n g (5-10 mm t o p - s i z e ) has b e e n v e r y p r o m i s i n g i n l a b o r a t o r y t e s t s ( 4 ) . I f t h i s a p p r o a c h p r o v e s o u t i n b e n c h - s c a l e e v a l u a t i o n s , more e x t e n s i v e and o n - l i n e c o a l l e a c h i n g u n i t s c a n be added r e a d i l y t o t h e p r e s e n t t e s t p l a n t . P r o c e s s i n g f i n e c o a l a l l o w s the h i g h e s t r a t e of p y r i t i c s u l f u r

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

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In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch012

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removal w h i l e p r o c e s s i n g coarse c o a l , although slower, a l l o w s l o w e r c o s t c o a l d e w a t e r i n g u n i t s and t h e d i r e c t s h i p p i n g o f des u l f u r i z e d c o a l p r o d u c t w i t h o u t need f o r p e l l e t i z i n g . The t e s t p l a n t c o n s t r u c t e d a t t h e C a p i s t r a n o t e s t s i t e i s a h i g h l y f l e x i b l e f a c i l i t y c a p a b l e o f t e s t i n g t h e numerous a l t e r n a t e p r o c e s s i n g modes o f p o t e n t i a l i n t e r e s t i n t h e M e y e r s p r o c e s s . The f l o w d i a g r a m shown i n F i g u r e 5 p r e s e n t s an e q u i p m e n t t r a i n f o r c o n tinuous process t e s t i n g of s l u r r i e d c o a l . F i n e c o a l ground to the d e s i r e d s i z e i s s t o r e d u n d e r n i t r o g e n gas i n 1.8 m e t r i c t o n s e a l e d bins. As r e q u i r e d , b i n s a r e e m p t i e d i n t o t h e f e e d t a n k ( T - l ) . Dry c o a l i s f e d c o n t i n u o u s l y by a l i v e b o t t o m f e e d e r t o a w e i g h b e l t which d i s c h a r g e s through a r o t a r y v a l v e to the three stage m i x e r ( s t r e a m 1 ) . The aqueous i r o n s u l f a t e l e a c h s o l u t i o n ( s t r e a m 2) e n t e r s t h e m i x e r a f t e r f i r s t p a s s i n g t h r o u g h a foam b r e a k e r (T-2). Steam i s added ( s t r e a m 3) t o r a i s e t h e s l u r r y t o i t s b o i l i n g p o i n t . Foaming o c c u r s i n t h e e a r l y s t a g e s o f m i x i n g , b u t c e a s e s when p a r t i c l e w e t t i n g i s c o m p l e t e . I t i s b e l i e v e d t h a t the m i x i n g t i m e and c o n d i t i o n s n e c e s s a r y t o c o m p l e t e t h e w e t t i n g and d e f o a m i n g o f t h e s l u r r y depend on t h e c o a l t y p e and s i z e and on the r e s i d u a l m o i s t u r e i n the feed c o a l . To a l l o w s t u d y o f t h e m i x i n g parameters, the m i x e r s t a g e s have v a r i a b l e volume w i t h v a r i a b l e s p e e d a g i t a t o r s , and t h e f e e d f l o w r a t e s f o r c o a l , l e a c h s o l u t i o n and s t e a m c a n be v a r i e d o v e r w i d e r a n g e s . The defoamed s l u r r y ( s t r e a m 4) i s pumped t o a f i v e - s t a g e p r e s s u r e v e s s e l ( r e a c t o r 1) i n w h i c h most o f t h e p y r i t e i s removed. Some o f t h e p y r i t e r e a c t i o n o c c u r s d u r i n g m i x i n g , b u t i n t h e m i x e r the r e a c t i o n r a t e slows r a p i d l y because the remaining p y r i t e (Wp) d e c r e a s e s and b e c a u s e t h e f e r r i c i r o n i s r a p i d l y b e i n g c o n v e r t e d t o f e r r o u s i r o n (Y d e c r e a s e s ) . The p r e s s u r e r e a c t o r o v e r c o m e s t h e d e c r e a s e d r a t e i n two ways. F i r s t , i t i n c r e a s e s t h e t e m p e r a t u r e (and p r e s s u r e ) t o i n c r e a s e t h e r e a c t i o n r a t e c o n s t a n t . Second, o x y g e n i s i n t r o d u c e d u n d e r p r e s s u r e t o r e g e n e r a t e f e r r i c i r o n and t o m a i n t a i n a h i g h s o l u t i o n Y. The f l o w d i a g r a m shows t h a t s t e a m and o x y g e n c a n be added t o any o r a l l o f t h e f i v e s t a g e s and t h a t c o o l i n g c a n be p r o v i d e d f o r any s t a g e i f n e c e s s a r y t o remove t h e excess heat of r e a c t i o n . The u n u s e d o x y g e n s a t u r a t e d w i t h s t e a m ( s t r e a m 7) i s c o n t a c t e d i n a s m a l l p r e s s u r e v e s s e l (T-3) w i t h t h e f e e d l e a c h s o l u t i o n ( s t r e a m 5) t o p r o v i d e h e a t e d l e a c h s o l u t i o n f o r t h e m i x e r ( s t r e a m 2) and c o o l e d v e n t g a s . The v e n t gas f r o m b o t h T-2 and T-3 a r e s c r u b b e d i n T-4 t o remove any t r a c e s o f a c i d mist. The i m p o r t a n t r e a c t i o n p a r a m e t e r s h a v e a l r e a d y b e e n w e l l s t u d i e d a t l a b o r a t o r y and b e n c h - s c a l e i n b a t c h mode. The t e s t p l a n t r e a c t o r w i l l accommodate t h e n e c e s s a r y s t u d i e s o f k e y p a r a m e t e r s i n a c o n t i n u o u s r e a c t o r a t c o a l t h r o u g h p u t s b e t w e e n 2 and 8 m e t r i c t o n s p e r day. P a r a m e t e r s w h i c h w i l l be s t u d i e d i n c l u d e temperature, p r e s s u r e , oxygen p u r i t y , s l u r r y c o n c e n t r a t i o n , i r o n s u l f a t e concentration, f e r r i c - t o - t o t a l i r o n r a t i o , acid concentrat i o n , r e s i d e n c e t i m e p e r s t a g e , number o f s t a g e s , m i x i n g e n e r g y , t y p e o f m i x i n g , c o a l s i z e , and t y p e . The r e a c t o r c a n a l s o be u s e d to study l e a c h s o l u t i o n r e g e n e r a t i o n i n the absence of c o a l .

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R e a c t e d c o a l s l u r r y ( s t r e a m 8) a t e l e v a t e d t e m p e r a t u r e and pressure i s f l a s h e d i n t o a g a s - l i q u i d separator v e s s e l (T-5). The s t e a m g e n e r a t e d ( s t r e a m 9) i s c o n d e n s e d i n T-4, and t h e c o n d e n s a t e p l u s any e n t r a i n e d a c i d m i s t i s removed w i t h t h e w a t e r . The r e s i d u a l s l u r r y ( s t r e a m 10) i s f e d t o a b e l t f i l t e r . The f i l t r a t e , w h i c h i s r e g e n e r a t e d l e a c h s o l u t i o n , i s removed f r o m t h e c o a l s l u r r y t h r o u g h a vacuum r e c e i v e r (T-9) and pumped ( s t r e a m 12) t o a l a r g e l e a c h s o l u t i o n s t o r a g e t a n k ( T - 6 ) . The c o a l on t h e f i l t e r b e l t i s washed w i t h w a t e r ( s t r e a m 11) and d i s c h a r g e d f r o m the f i l t e r b e l t . The wash w a t e r i s removed t h r o u g h a vacuum r e c e i v e r (T-10) and s e n t t o a l a r g e l i q u i d w a s t e h o l d i n g t a n k (T-8) f o r subsequent d i s p o s a l . The f i l t e r i s a h i g h l y v e r s a t i l e u n i t w h i c h s h o u l d p r o v i d e t h e d a t a n e c e s s a r y f o r s c a l e - u p . I t has v a r i a b l e b e l t speed, v a r i a b l e b e l t areas assigned to washing, v a r i a b l e c a k e w a s h i n g r a t e s , b e l t s p r a y s i f needed t o c o n t r o l b l i n d i n g o f t h e p o r e s i n t h e b e l t , and s t e a m n o z z l e s t o p r o v i d e f o r p a r t i a l cake d r y i n g . As an a l t e r n a t e p r o c e s s s e e p , t h e s l u r r y f r o m t h e f l a s h t a n k (T-5) c a n be p a s s e d i n t o a s e c o n d a r y r e a c t i o n v e s s e l ( r e a c t o r 2 ) . A t t y p i c a l c o a l f e e d r a t e s , t h i s v e s s e l can be f i l l e d i n a b o u t 2 h r and t h e n c l o s e d o f f , s t i r r e d and h e a t e d f o r any d e s i r e d t i m e b e f o r e b e i n g pumped t o t h e f i l t e r . R e s i d e n c e t i m e s up t o a b o u t 10 h r a r e a v a i l a b l e i n t h e p r i m a r y r e a c t o r ( r e a c t o r 1 ) . This s e c o n d a r y r e a c t o r c a n be u s e d t o e x t e n d r e s i d e n c e t i m e s t o much l o n g e r times f o r examining the removal of f i n a l t r a c e s of p y r i t e o r e x a m i n i n g any o t h e r l o n g - t e r m b e h a v i o r . The s t i r r e d v e s s e l a l s o can r e p u l p the f i l t e r cake f o r a d d i t i o n a l c o a l washing studies. The f i n a l i t e m o f m a j o r e q u i p m e n t i n t h e t e s t p l a n t i s t h e c o a r s e c o a l c o n t a c t v e s s e l ( r e a c t o r 3 ) . T h i s i n s u l a t e d and h e a t e d t a n k w i l l h o l d a f u l l b i n ( a b o u t 1.8 m e t r i c t o n s ) o f c o a r s e c o a l (5-10 mm t o p - s i z e ) . T h i s v e s s e l i s used p r i n c i p a l l y to c o n v e r t t h e r e g e n e r a t e d l e a c h s o l u t i o n i n s t o r a g e t a n k T-6 t o a more dep l e t e d s o l u t i o n i n t h e p r o c e s s f e e d t a n k , T-7. In g e n e r a l , the i r o n s u l f a t e l e a c h s o l u t i o n i n t h e f i l t r a t e g o i n g t o t a n k T-6 w i l l h a v e a h i g h Y b e c a u s e no s e c o n d a r y r e a c t o r was i n u s e . F o r some t e s t c o n d i t i o n s , t h e f e e d t o t h e p r o c e s s must be a t a l o w e r Y t o s i m u l a t e r e c y c l e l e a c h s o l u t i o n from a secondary r e a c t o r . P a s s i n g a l l o r some p o r t i o n o f t h e s o l u t i o n t h r o u g h c o a l w i l l l o w e r t h e Y of t h e s o l u t i o n t o t h e d e s i r e d v a l u e . T h i s v e s s e l i s b a s i c a l l y a c o a r s e c o a l r e a c t o r , and i f a p p r o p r i a t e s a m p l i n g p o r t s and p o s s i b l y some f l o w d i s t r i b u t i o n i n t e r n a l s were a d d e d , i t c o u l d be used to o b t a i n d e s i g n data f o r coarse c o a l p r o c e s s i n g . S o l u t i o n t a n k s a r e s i z e d a t a b o u t 50,000 L t o p r o v i d e f o r a b o u t a week o f c o n t i n u o u s o p e r a t i o n on t h e same f e e d w i t h o u t r e c y c l e o r change. I t a l s o p r o v i d e s f o r u n i f o r m l e a c h s o l u t i o n and c o a l s a m p l e s o f a l a r g e enough s i z e f o r p r o d u c t r e c o v e r y s t u d i e s p e r f o r m e d by e q u i p m e n t v e n d o r s . Operation at the s c a l e of the t e s t p l a n t w i l l p r o v i d e a d e q u a t e e x p e r i e n c e and d a t a f o r t h e d e s i g n of a d e m o n s t r a t i o n - s i z e c o m m e r c i a l p l a n t .

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

12.

V A N NICE E T A L .

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163

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Literature Cited

1. Meyers, R.A., "Coal Desulfurization," Marcel Dekker, Inc., New York (1977). 2. Yurovskii, A.Z., "Sulfur in Coals," U.S. Department of Commerce, National Technical Information Service, Springield, Va. 22161 (1974). 3. Kraft, M.L., Hamersma, J.W., "Applicability of the Meyers Process for Chemical Desulfurization of Coal: Survey of 35 Coal Mines," Environ. Prot. Technol. Ser., (September 1975), EPA-650/2-74-025-a. 4. Koutsoukos, E.P., Kraft, M.L., Orsini, R.A., Meyers, R.A., Santy, M.J., Van Nice, L.J., "Final Report Program for BenchScale Delevopment of Processes for the Chemical Extraction of Sulfur from Coal," Environ. Prot. Technol. Ser., (May 1976), EPA-600/2-76-143a.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

13 Oxidative Desulfurization of Coal SIDNEY FRIEDMAN, ROBERT B. LACOUNT, and ROBERT P. WARZINSKI

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch013

Pittsburgh Energy Research Center, U.S. Energy Research and Development Administration, 4800 Forbes Ave., Pittsburgh, PA 15213

It is becoming increasingly apparent that the solution to our national energy problems will require a variety of approaches and that these must be compatible with environmental restrictions. Coal, only recently considered destined for obscurity, has been rescued by a combination of international political events and increasing difficulties in developing a nuclear power industry. Although coal as an energy source presents problems, at least it is available and can be utilized. The Federal Government, as part of the program administered by the Energy Research and Development Administration, is carrying out research on many phases of coal utilization to overcome the environmental problems involved in the combustion of coal. One research project, which has been in progress at the Pittsburgh Energy Research Center since 1970, is concerned with chemical beneficiation of coal and most specifically with removal of sulfur from coal prior to combustion. Experimental Batch Experiments. Thirty-five grams of -200 mesh coal and 100 ml water were placed in a liner (glass or teflon) in a 1-L, magnetically stirred, stainless steel autoclave. The autoclave was p r e s s u r i z e d w i t h c y l i n d e r a i r t o t h e r e q u i r e d gauge p r e s s u r e (800 p s i i n t h e e x p e r i m e n t s i n T a b l e s I , I I , a n d I I I ) and t h e n was h e a t e d w i t h s t i r r i n g a t 800-1000 rpm u n t i l t h e s p e c i f i e d t e m p e r a t u r e was r e a c h e d ( a p p r o x i m a t e l y 1 h r h e a t - u p t i m e ) . O p e r a t i n g p r e s s u r e f o r 800 p s i i n i t i a l e x p e r i m e n t s was 1000-1200 p s i , d e p e n d i n g o n t e m p e r a t u r e and e x t e n t o f r e a c t i o n . After a s p e c i f i e d time a t r e a c t i o n temperature, r a n g i n g from 5 min t o 2 h r , t h e a u t o c l a v e was c o o l e d b y a n i n t e r n a l c o o l i n g c o i l . Final p r e s s u r e a t room t e m p e r a t u r e was b e t w e e n 650 a n d 750 p s i . The c o n t e n t s w e r e removed, f i l t e r e d , washed u n t i l t h e pH o f t h e f i l t r a t e was n e u t r a l , and t h e n e x t r a c t e d i n a S o x h l e t t h i m b l e w i t h w a t e r u n t i l s u l f a t e ( p r e s e n t a s CaSO,) was no l o n g e r p r e s e n t i n the fresh extract. The c o a l was t h e n d r i e d t h o r o u g h l y i n a

164

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

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165

the Coal A n a l y s i s S e c t i o n ,

Semicontinuous Experiments. Using a s i m i l a r autoclave f i t t e d w i t h p r e s s u r e r e g u l a t i n g v a l v e s , the a u t o c l a v e c o n t a i n i n g t h e c o a l and w a t e r was h e a t e d t o t h e s p e c i f i e d t e m p e r a t u r e u n d e r 1 atra ( i n i t i a l p r e s s u r e ) N . At temperature, or s h o r t l y b e f o r e r e a c h i n g i t , a i r was a d m i t t e d t o t h e d e s i r e d p r e s s u r e , w h i c h was 1000 p s i e x c e p t f o r e x p e r i m e n t s d e s i g n e d t o i n v e s t i g a t e t h e e f f e c t of p r e s s u r e . T e m p e r a t u r e was k e p t a t t h e r e q u i r e d v a l u e by h e a t i n g and cooling ( c o o l i n g c o i l ) while a i r (approximately 2 c u f t / h r ) flowed through the a u t o c l a v e . A f t e r t h e r e q u i r e d t i m e a t temp e r a t u r e , t h e a u t o c l a v e was c o o l e d , and t h e p r o d u c t s were w o r k e d up a s i n t h e p r e v i o u s example.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch013

?

R e s u l t s and

Discussion

A l t h o u g h t h e p r o j e c t was i n i t i a l l y d i v i d e d i n t o r e m o v a l o f o r g a n i c and o f i n o r g a n i c s u l f u r (1), i t was s o o n e v i d e n t t h a t , t h o u g h one c o u l d remove p y r i t i c s u l f u r w i t h o u t r e m o v i n g o r g a n i c s u l f u r , t h e r e v e r s e was n o t t r u e . Any p r o c e s s w h i c h removed o r g a n i c s u l f u r w o u l d a l s o remove p y r i t i c s u l f u r . So t h e a p p r o a c h t o t h e p r o b l e m became one o f f i n d i n g c h e m i c a l r e a c t i o n s s u i t a b l e f o r removing o r g a n i c s u l f u r from c o a l . The c h e m i s t r y w h i c h we c h o s e t o e x p l o r e was b a s e d on two premises: t h e m a j o r p o r t i o n o f t h e o r g a n i c s u l f u r i n c o a l was of the dibenzothiophene (DBT) t y p e , and, t h e r e a g e n t s had t o be inexpensive. W h i l e we now b e l i e v e t h a t a t l e a s t a s i z a b l e f r a c t i o n o f t h e o r g a n i c s u l f u r i n c o a l i s n o t d i b e n z o t h i o p h e n i c , we have no r e a s o n t o d o u b t t h a t o v e r 50% o f i t may be. T h e s e p r e m i s e s l e d us t o t h e f o l l o w i n g h y p o t h e t i c a l twostep removal of o r g a n i c s u l f u r from c o a l . (1). O x i d a t i o n of o r g a n i c (or d i b e n z o t h i o p h e n i c ) s u l f u r to sulfone.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

166

COAL

DESULFURIZATION

B o t h o f t h e s e r e a c t i o n s a r e i n t h e l i t e r a t u r e , so we had to m o d i f y and i m p r o v e them so t h a t t h e y c o u l d be a p p l i e d t o d e s u l f u r i z a t i o n of c o a l . The s e c o n d s t e p — t h e r e m o v a l o f SO^ f r o m DBT s u l f o n e by b a s e — was e s s e n t i a l l y q u a n t i t a t i v e when t h e s u l f o n e was h e a t e d t o 300°C i n the p r e s e n c e o f aqueous NaOH and n e a r l y as e f f i c i e n t w i t h Na CO~. T h i s was an improvement on t h e nonaqueous treatment The f i r s t s t e p i n t h e r e a c t i o n — o x i d a t i o n t o s u l f o n e — a l t h o u g h e x t e n s i v e l y documented i n t h e l i t e r a t u r e , p r e s e n t e d more o f a c h a l l e n g e . T h e r e a r e numerous o x i d a n t s r e p o r t e d w h i c h c a n e f f e c t t h e c o n v e r s i o n o f o r g a n o s u l f u r compounds t o s u l f o n e s , i n c l u d i n g KMnO^, HNC> , CrO^, H ^ / H O A c , and h y d r o p e r o x i d e s ( 3 ) . T h e s e o b v i o u s l y do n o t f i t t h e s e c o n d p r e m i s e t h a t t h e r e a g e n t s must be i n e x p e n s i v e . I t was a g r e e d t h a t t h e o n l y r e a g e n t w h i c h c o u l d be used as an o x i d a n t was t h e o x y g e n i n a i r . But DBT, and presumably the o r g a n i c s u l f u r i n c o a l , i s i n e r t to a i r at r e l a t i v e l y h i g h p r e s s u r e and t e m p e r a t u r e . T r a n s f e r o f o x y g e n t o a c a r r i e r t o f o r m a h y d r o p e r o x i d e , f o l l o w e d by r e a c t i o n o f t h e h y d r o p e r o x i d e w i t h DBT, d i d g i v e s u l f o n e . We f o u n d t h a t w i t h many h y d r o c a r b o n s , s u c h as t e t r a l i n , d e c a l i n , and c y c l o h e x a n e , m e r e l y h e a t i n g DBT w i t h a i r u n d e r p r e s s u r e i n t h e p r e s e n c e o f the hydrocarbon r e s u l t e d i n f o r m a t i o n of s u l f o n e ( 4 ) , presumably as a r e s u l t o f i n s i t u f o r m a t i o n o f h y d r o p e r o x i d e s . Benzene, w h i c h does n o t f o r m a h y d r o p e r o x i d e , a f f o r d s no s u l f o n e f o r m a t i o n under comparable c o n d i t i o n s . A p p l y i n g o u r t w o - s t e p r e a c t i o n — a i r o x i d a t i o n f o l l o w e d by t r e a t m e n t w i t h aqueous b a s e — t o c o a l , we removed up t o 50% o f o r g a n i c s u l f u r , and a l m o s t c o m p l e t e l y e l i m i n a t e d p y r i t i c s u l f u r as a b o n u s . A l t h o u g h t h i s scheme a p p e a r e d p r o m i s i n g , i t d i d r e q u i r e a s u i t a b l e o r g a n i c l i q u i d and a l s o NaOH. We a l s o e x p l o r e d a n o t h e r o x i d a t i o n s y s t e m w h i c h u s e s a i r as t h e u l t i m a t e s o u r c e o f o x y g e n . N i t r o g e n d i o x i d e ( N 0 ) i s a good r e a g e n t f o r c o n v e r t i n g s u l f i d e s t o s u l f o n e s , and i t can be u s e d i n an e a s i l y r e g e n e r a b l e s y s t e m . 9

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch013

3

2

2N0 2N0

2

+

-S-

">

2N0

+

0

->

2NX>

2

+

-S0 2

2

(3) (4)

We f o u n d t h a t we c o u l d i n d e e d o x i d i z e DBT t o i t s s u l f o n e u s i n g NO^ and a i r . When t h e r e a c t i o n was e x t e n d e d t o c o a l , h o w e v e r , a s i g n i f i c a n t amount o f c o n c u r r e n t r e a c t i o n t o o k p l a c e , i n c l u d i n g n i t r a t i o n o f t h e c o a l , w h i c h consumed t h e n i t r o g e n o x i d e s and t h u s w o u l d have n e c e s s i t a t e d a c o n t i n u o u s a d d i t i o n o f NO^ r a t h e r t h a n t h e r e c y c l i n g shown i n E q u a t i o n s 3 and 4. I n t h e meantime, o u r e x p e r i m e n t s on a i r o x i d a t i o n o f o r g a n o s u l f u r u s i n g h y d r o p e r o x i d e p r e c u r s o r s l e d us t o t h e u l t i m a t e e x p e r i m e n t , t h e one i n w h i c h H«0 was u s e d i n p l a c e o f an o r g a n i c l i q u i d p h a s e . T h i s r e a c t i o n o f c o a l w i t h w a t e r and c o m p r e s s e d a i r almost q u a n t i t a t i v e l y c o n v e r t e d the p y r i t i c s u l f u r i n c o a l

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch013

13.

FRIEDMAN

E T

AL.

Oxidative

Desulfurization

of

167

Coal

t o H^SO^. I n a d d i t i o n , we a l s o removed 2 5 % o f t h e o r g a n i c sulfur. H e r e was e v i d e n c e t h a t t h e r e was some o r g a n o s u l f u r i n c o a l w h i c h was n o t D B T - l i k e , s i n c e DBT f a i l e d t o r e a c t w i t h a i r and w a t e r u n d e r t h e s e c o n d i t i o n s . I n i t i a l experiments on t h e a i r - w a t e r o x y d e s u l f u r i z a t i o n o f c o a l were c a r r i e d o u t u s i n g a b a t c h , s t i r r e d a u t o c l a v e s y s t e m . In t h i s a p p a r a t u s , i n o r d e r t o r e p l a c e o x y g e n a s i t was u s e d , i t was n e c e s s a r y t o c o o l t h e a u t o c l a v e t o n e a r room t e m p e r a t u r e , v e n t t h e s p e n t a i r , r e p r e s s u r e , a n d r e h e a t . A l t h o u g h t h i s gave s a t i s f a c t o r y d e s u l f u r i z a t i o n , i t was a n i m p r a c t i c a l a p p r o a c h f o r s t u d y i n g r e a c t i o n parameters. The r e s u l t s c i t e d i n T a b l e s I , I I , and I I I a r e f r o m 1-hr b a t c h s t u d i e s w i t h o u t r e p r e s s u r i z a t i o n a n d t h u s r e p r e s e n t l e s s t h a n maximum d e s u l f u r i z a t i o n i n some c a s e s . A l l c o a l s , except those noted, a r e bituminous. The a p p a r a t u s h a s b e e n m o d i f i e d t o a l l o w a i r t o f l o w through t h e s t i r r e d r e a c t o r w h i l e the coal-water s l u r r y remains as a b a t c h r e a c t a n t . T h i s i s o u r c u r r e n t s y s t e m . I n t h i s way, we a r e s t u d y i n g many o f t h e v a r i a b l e s a s t h e y w i l l a f f e c t t h e r e a c t i o n i n a continuous system. Our newest a p p a r a t u s , now b e g i n n i n g o p e r a t i o n , i s a f u l l y c o n t i n u o u s u n i t , f e e d i n g b o t h a i r and c o a l - w a t e r s l u r r y i n t o a r e a c t o r tube. T h i s sytera i s d e s i g n e d t o o b t a i n d a t a on r e a c t i o n r a t e s , d e v e l o p i n f o r m a t i o n f o r e c o n o m i c e v a l u a t i o n , a n d answer those q u e s t i o n s which a r i s e concerning e n g i n e e r i n g aspects o f the p r o c e s s . H e a t i n g h i g h - p y r i t e c o a l s i n aqueous s l u r r y w i t h c o m p r e s s e d a i r a t 1000-1200 p s i and a t 150°-160°C d e c r e a s e s p y r i t i c s u l f u r to n e a r t h e l o w e r l i m i t o f d e t e c t i o n b y s t a n d a r d a n a l y t i c a l procedure. Some r e s u l t s o f 1 h r b a t c h e x p e r i m e n t s a r e shown i n T a b l e I . The s u l f u r w h i c h i s removed i s c o n v e r t e d p r i m a r i l y t o aqueous s u l f u r i c a c i d , w i t h s m a l l amounts o f f e r r i c a n d f e r r o u s sulfates i nsolution. A t i n i t i a l p r e s s u r e s o f 800 p s i a n d above and a t t e m p e r a t u r e s above 160°C, 8 0 % o r more o f t h e p y r i t i c s u l f u r i n t h e M i n s h a l l Seam ( I n d i a n a ) c o a l i s removed i n 5 m i n at temperature. S i m i l a r p y r i t i c s u l f u r r e m o v a l was o b s e r v e d i n a s e r i e s o f 10 m i n e x p e r i m e n t s a t 1000 p s i i n t h e c o n t i n u o u s unit. TABLE I . P y r i t e Removal f r o m R e p r e s e n t a t i v e C o a l s by Oxydesulfurization

Seam

State

Temp (°C)

I l l i n o i s No. 5 Minshall L o v i l i a No. 4 Pittsburgh Lower F r e e p o r t Brookville

Illinois Indiana Iowa Ohio Pennsylvania Pennsylvania

150 150 150 160 160 180

P y r i t i c S u l f u r (wt %) Treated Untreated 0.9 4.2 4.0 2.8 2.4 3.1

0.1 0.2 0.3 0.2 0.1 0.1

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch013

168

C O A L DESULFURIZATION

A t 200 p s i , t h e r e a c t i o n i s much s l o w e r , r e q u i r i n g s e v e r a l h o u r s t o a c h i e v e even 6 0 % p y r i t i c s u l f u r r e m o v a l . F o r some c o a l s , a t l e a s t , t h e d e s u l f u r i z a t i o n i s a l m o s t a s r a p i d a t 500 p s i a s a t 1000 p s i . The o x i d a t i o n o f p y r i t i c s u l f u r i s temp e r a t u r e dependent, but a t the c o n d i t i o n s of our experiments, r e a c t i o n i s s u f f i c i e n t l y f a s t t h a t above 150°C l i t t l e i m p r o v e ment i s n o t e d . I n a few c a s e s , where a c o a l a p p e a r s t o h a v e some r e s i d u a l p y r i t e w h i c h i s n o t o x i d i z e d r e a d i l y a t 150°C, i t may be removed a t 180°C. As t h e t e m p e r a t u r e a t w h i c h t h e o x i d a t i o n i s c o n d u c t e d i s i n c r e a s e d a b o v e 150°C, a n i n c r e a s i n g amount o f o r g a n i c s u l f u r i s removed f r o m t h e c o a l . A l t h o u g h t h e p e r c e n t a g e o f o r g a n i c s u l f u r removed p a r a l l e l s t h e t e m p e r a t u r e r i s e , so does t h e amount o f c o a l w h i c h i s o x i d i z e d . To p r e v e n t e x c e s s i v e l o s s o f c o a l , a p r a c t i c a l l i m i t o f 200°C h a s been c h o s e n f o r c a r r y i n g o u t t h e r e a c t i o n on most c o a l s . Removal o f o r g a n i c s u l f u r f r o m a s e r i e s o f c o a l s , shown i n T a b l e I I , v a r i e s f r o m 20 t o o v e r 40%. Further reduction of organic s u l f u r content i s probably p o s s i b l e w i t h some o f t h e s e c o a l s w i t h o u t s a c r i f i c i n g c o a l recoverability. An upper l i m i t on o r g a n i c s u l f u r r e m o v a l a p p e a r s t o be b e t w e e n 40 and 5 0 % , and v a r i e s f r o m c o a l t o c o a l . We b e l i e v e t h i s i s c a u s e d by t h e f u n c t i o n a l i t y o f t h e o r g a n i c s u l f u r , and g i v e s some r o u g h measure o f o x i d a t i o n r e s i s t a n t o r DBT t y p e o f sulfur. O b v i o u s l y , t h a t s u l f u r w h i c h i s removed by o x y d e s u l f u r i z a t i o n must be i n some o t h e r s t r u c t u r e w h i c h i s r e a d i l y o x i d i z e d , such as t h i o l , s u l f i d e , and/or d i s u l f i d e . A s i m i l a r amount o f o r g a n i c s u l f u r i s removed f r o m c o a l when i t i s h e a t e d a t 300°C w i t h aqueous a l k a l i , a r e a g e n t w h i c h does n o t a t t a c k DBT (_5,6) . TABLE I I .

O r g a n i c S u l f u r Removal f r o m R e p r e s e n t a t i v e C o a l s by O x y d e s u l f u r i z a t i o n

Seam

State

Temp (°C)

Bevier Mammoth Wyoming No. 9 Pittsburgh Lower F r e e p o r t I l l i n o i s No. 6 Minshall

Kansas Montana Wyoming Ohio Pennsylvania Illinois Indiana

150 150 150 180 180 200 200

O r g a n i c S u l f u r (wt %) Untreated Treated 2.0 0.5 1.1 1.5 1.0 2.3 1.5

1.6 0.4 0.8 0.8 0.8 1.3 1.2

Subbituminous. Even a t 150°-160°C many c o a l s , i n c l u d i n g some w i t h r a t h e r h i g h s u l f u r c o n t e n t s , c a n be d r a m a t i c a l l y d e s u l f u r i z e d a s shown i n Table I I I .

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Indiana Illinois Iowa Montana Pennsylvania Wyoming Ohio Pennsylvania

Minshall I l l i n o i s No. 5 L o v i l i a No. 4 Mammoth Pittsburgh Wyoming No. 9 Pittsburgh Upper F r e e p o r t

Subbituminous.

State 150 150 150 150 150 150 160 160

Temp (°C) 5.7 3.3 5.9 1.1 1.3 1.8 3.0 2.1

2.0 2.0 1.4 0.6 0.8 0.9 1.4 0.9

T o t a l S u l f u r (wt %) Untreated Treated

Oxydesulfurization of Representative

Seam

TABLE I I I . 6

4.99 2.64 5.38 0.91 0.92 1.41 2.34 1.89

1.81 1.75 1.42 0.52 0.60 0.78 1.15 0.80

Sulfur ( l b / 1 0 Btu) Treated Untreated

Coals

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch013

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch013

170

COAL

DESULFURIZATION

The r e a c t i o n c o n d i t i o n s w h i c h we have f o u n d t o be s u i t a b l e for o x y d e s u l f u r i z a t i o nare: t e m p e r a t u r e b e t w e e n 150° and 220°C, o p e r a t i n g p r e s s u r e b e t w e e n 220 and 1500 p s i , and r e s i d e n c e t i m e of 1 h r or l e s s . Most o f o u r e x p e r i m e n t s h a v e b e e n c a r r i e d o u t b e l o w 220°C a n d a t a p p r o x i m a t e l y 1000 p s i . R e c o v e r i e s o f f u e l v a l u e s a r e e x c e l l e n t , g e n e r a l l y 9 0 % o r b e t t e r . The o n l y b y p r o d u c t o f t h e r e a c t i o n i s d i l u t e H«S0^ c o n t a i n i n g i r o n sulfates. T h i s c a n be r e c y c l e d w i t h no o b s e r v a b l e e f f e c t on desulfurization for at least five cycles. When t h e H^SO^ becomes t o o c o n c e n t r a t e d f o r f u r t h e r u s e , i t c a n be c o n v e r t e d to a commercial grade o f s u l f u r i c a c i d i f a s u i t a b l e , economic m a r k e t e x i s t s , o r i t c a n be d i s p o s e d o f by l i m e s t o n e n e u t r a l i z a t i o n a s a r e a d i l y f i l t e r a b l e CaSO,. The p r o c e s s , o u t l i n e d i n F i g u r e 1, n e e d s no n o v e l technology t o produce c o a l having over 95% o f i t s p y r i t i c s u l f u r and a s much a s 4 0 % o f i t s o r g a n i c s u l f u r removed. O t h e r t h a n t h e c o a l , a i r , and w a t e r , t h e o n l y o t h e r m a t e r i a l needed f o r t h e p r o c e s s i s t h e l i m e s t o n e u s e d t o n e u t r a l i z e t h e H^SO^. No s l u d g e i s f o r m e d , much o f t h e w a t e r c a n be r e c y c l e d , and t h e o n l y w a s t e p r o d u c t i s s o l i d CaSO^. S i m i l a r o x i d a t i v e d e s u l f u r i z a t i o n s u s i n g a i r and w a t e r (7) and o x y g e n and w a t e r (8) have been r e p o r t e d . A p r e l i m i n a r y estimate f o r t h i s process i n d i c a t e s a cost o f $8.00-$10.00 p e r t o n . A t t h i s p r i c e , t h e p r o c e s s w o u l d s t i l l be c o n s i d e r a b l y l e s s e x p e n s i v e t h a n c o a l c o n v e r s i o n t o gas o r l i q u i d f u e l . A s s u m i n g r e m o v a l o f 9 5 % p y r i t i c s u l f u r and 40% o r g a n i c s u l f u r , an e s t i m a t e d 4 0 % o f t h e c o a l mined i n t h e e a s t e r n U.S. c o u l d be made e n v i r o n m e n t a l l y a c c e p t a b l e a s b o i l e r f u e l a c c o r d i n g t o EPA s t a n d a r d s f o r new i n s t a l l a t i o n s . And t h e s u l f u r c o n t e n t o f t h e r e m a i n d e r o f t h e e a s t e r n c o a l c o u l d be d r a s t i c a l l y r e d u c e d , m a k i n g i t e n v i r o n m e n t a l l y acceptable f o r e x i s t i n g b o i l e r s . Conclusions T r e a t m e n t w i t h c o m p r e s s e d a i r a n d w a t e r a t 150°-200°C r e p r e s e n t s a p r a c t i c a l method t o d e s u l f u r i z e t o a c c e p t a b l e l e v e l s a s i z a b l e percentage of the a v a i l a b l e c o a l i n the e a s t e r n U n i t e d S t a t e s a t a c o s t i n money and f u e l v a l u e w h i c h i s l e s s t h a n c o a l c o n v e r s i o n and t o an e x t e n t w h i c h i s g r e a t e r t h a n c a n be a c h i e v e d b y p h y s i c a l d e p y r i t i n g methods. Abstract

Both pyritic and organic sulfur in coal can be removed by a variety of oxidation techniques, including treatment with NO , peroxygen compounds, air in the presence of specific organic media, or air and water at elevated temperature and pressure. The most promising method involves contacting an aqueous slurry of coal with air at pressures up to 1000 psi x

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

FRIEDMAN

Oxidative Desulfurization of Coal

E T A L .

COMPRESSOR

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch013

AIR

-CPGRINDING DESULFURIZED COAL FOR POWER PLANTS AND INDUSTRIAL BOILERS

HIGH-SULFUR COAL

MIXING TANK

DRYER

γ

HEAVY MINERALS WAT^R]

FILTER

+ LIMESTONE

CtS0

Figure 1.

4

Air-water oxydesulfurization process

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch013

172

COAL

DESULFURIZATION

and temperatures of 140°-200°C. Coals from different geo­ graphic areas of the U.S. have been treated with air and water in this way, resulting in removal of more than 90% of pyritic sulfur and up to 40% of organic sulfur as sulfuric acid, which is separated from the desulfurized coal by filtration. Fuel value losses are usually less than 10%. Costs for processing coal by this procedure will be somewhere between the less efficient, less thorough and less costly physical coal cleaning methods and the more thorough but much more costly coal conversion techniques. Oxidative desulfurization potentially can upgrade up to 40% of the bituminous coal in the U.S. to environmentally acceptable boiler fuel and can bring most of the rest of the bituminous coals at least close to acceptability with relatively little loss in total fuel value. Literature Cited 1. Reggel, L., Raymond, R., Wender, I., Blaustein, B. D., Am. Chem. Soc., Div. Fuel Chem. Preprints, (1972) 17 (2), 44. 2. Wallace, T. J., Heimlich, Β. Ν., Tetrahedron (1968), 24, 1311. 3. Reed, Ε., "Organic Chemistry of Bivalent Sulfur," Vol. II, p. 64, Chemical Publishing Co., Inc., New York, 1968. 4. LaCount, R. Β., Friedman, Sidney, J. Org. Chem (1977), 42, 2751. 5. Worthy, W., Chem. Eng. News, (July 7, 1975), pp. 24-25. 6. Friedman, Sidney, Warzinski, R. P., Trans. ASME, J. Eng. Power, (1977) 99A, 361. 7. Thomas, J., Warshaw, Α., U.S. Pat. 3,824,084 (Assigned to Chemical Construction Corp.) July 16, 1974. 8. Agarwal, J. C., Giberti, R. Α., Irminger, P. F., Petrovic, L. F., Sareen, S. S., Min. Congr. J., (1975) 61 (3), 40.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

14 Sulfur Removal from Coals: Ammonia/Oxygen System S. S.

SAREEN

1

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch014

Ledgemont Laboratory, Kennecott Copper Corp., 128 Spring Street, Lexington, MA 02172

The emergence of chemical desulfurization of coal as a viable alternative to stack gas scrubbing (1) has prompted researchers in this field to consider a variety of chemical systems which remove pyritic sulfur or both the pyritic and part of the organic sulfur (2,3,4,5,6). A review of the more prominent chemical desulfurization schemes is presented in a recent article (6). Because chemical desulfurization is cost competitive with stack gas scrubbing (1), utilities are beginning to show an interest in the development of this technology which could provide them with a source of clean fuel to meet the rigorous EPA standards for sulfur emissions. This chapter discusses the sulfur removal from coals using an ammonia/oxygen/water system which removes almost all of the pyritic sulfur and up to 25% of the organic sulfur in about 2 hr. Because organic sulfur removal necessarily implies coal carbon losses, a balance must be struck between the amount of organic sulfur removed and the thermal losses that can be economically tolerated from the coals being cleaned. A l t h o u g h no e f f o r t h a s b e e n made t o o p t i m i z e t h e s y s t e m r e p o r t e d h e r e , t h e r e s u l t s o f B t u l o s s , oxygen consumption, r e t e n t i o n t i m e , e t c . , a r e f a i r l y c o n s i s t e n t w i t h t h e oxygen/water s y s tem f o r p y r i t e r e m o v a l f r o m c o a l s ( 2 ) . The c a r b o n l o s s e s , a s m i g h t b e e x p e c t e d , a r e somewhat h i g h e r . Furthermore, the data p r e s e n t e d h e r e c a n b e u s e d t o c o n s t r u c t a n o p t i m i z a t i o n scheme f o r f u t u r e d e v e l o p m e n t work. Process Description I n t h i s d e s u l f u r i z a t i o n scheme, r u n - o f - m i n e c o a l i s t r e a t e d i n a c o n v e n t i o n a l p r e p a r a t i o n p l a n t , where t h e c o a l i s c r u s h e d and washed t o remove r o c k a n d c l a y m a t e r i a l . The c o a r s e l y c r u s h e d c o a l i s t h e n f e d i n t o c l o s e d - c i r c u i t w e t b a l l m i l l s where i t i s f u r t h e r g r o u n d t o -100 mesh. The g r o u n d s l u r r y i s pumped i n t o TRW E n e r g y S y s t e m s , 7600 C o l s h i r e D r i v e , M c L e a n , V a . 22101 173

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

174

C O A L DESULFURIZATION

o x y g e n - s p a r g e d l e a c h r e a c t o r s w h i c h o p e r a t e a t a b o u t 130°C a n d 300 p s i o x y g e n p r e s s u r e . A l l o f t h e p y r i t i c s u l f u r and up t o 2 5 % o f t h e o r g a n i c s u l f u r i s removed i n a b o u t 2 h r . The d e s u l f u r i z e d s l u r r y now goes t h r o u g h a s o l i d / l i q u i d s e p a r a t i o n o p e r a t i o n where t h e c o a l and l i q u i d a r e s e p a r a t e d . Because o f t h e f o r m a t i o n o f s u l f a t e s a n d t h e a b s o r p t i o n o f some o f t h e CO2 ( f r o m c o a l o x i d a t i o n ) i n t o t h e ammonia s o l u t i o n , t h i s m i x e d s u l f a t e / c a r b o n a t e s t r e a m must be r e g e n e r a t e d t o r e c y c l e t h e ammonia b a c k i n t o t h e process. The ammonia r e g e n e r a t i o n may be a c c o m p l i s h e d b y c a l c i n i n g and/or steam s t r i p p i n g . S u l f u r removal from c o a l s as a f u n c t i o n o f ammonia c o n c e n t r a t i o n and r e t e n t i o n t i m e i s d i s c u s s e d below.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch014

Experimental

Conditions

A l l o f t h e e x p e r i m e n t s r e p o r t e d h e r e were c a r r i e d o u t i n a b a t c h mode i n h i g h - p r e s s u r e s t i r r e d a u t o c l a v e s . The a u t o c l a v e s w e r e e q u i p p e d w i t h b a f f l e s , a n d t h e s p e e d o f a g i t a t i o n was c o n t r o l l e d w i t h t h e h e l p o f a t a c h o m e t e r and was v e r i f i e d a t f r e quent i n t e r v a l s w i t h a s t r o b o s c o p e . The s y s t e m was h e a t e d w i t h a j a c k e t e d e l e c t r i c h e a t e r e x t e r i o r t o t h e chamber, a n d t h e t e m p e r a t u r e was c o n t r o l l e d t o w i t h i n a c o u p l e o f d e g r e e s w i t h a t e m p e r ature c o n t r o l l e r . The r e a c t i o n m i x t u r e was c o o l e d r a p i d l y a t t h e end o f t h e e x p e r i m e n t w i t h a c o o l i n g s y s t e m f i t t e d i n s i d e t h e h i g h - p r e s s u r e r e a c t o r s . The mode o f o p e r a t i o n was a s f o l l o w s : 120 gms ( d r y b a s i s ) o f I l l i n o i s No. 6 c o a l was s l u r r i e d i n ammon i a c a l s o l u t i o n s t o g i v e a s o l i d s p u l p d e n s i t y o f 20 w/o. The a u t o c l a v e s w e r e s e a l e d and t h e a i r p u r g e d w i t h i n e r t g a s . This i n s u r e d no r e a c t i o n w i t h t h e c o a l s u l f u r d u r i n g t h e h e a t u p p e r i o d . The h e a t e r a n d s t i r r e r s w e r e t u r n e d o n , and t h e t e m p e r a t u r e was a l l o w e d t o s t a b i l i z e a t 130°C. The s y s t e m was t h e n p r e s s u r i z e d t o y i e l d a n o x y g e n p a r t i a l p r e s s u r e o f 300 p s i , and t h e r e a c t i o n was p e r m i t t e d t o p r o c e e d . The o x y g e n was a s p i r a t e d f r o m t h e v a por space o f t h e a u t o c l a v e , through t h e h o l l o w a g i t a t o r s h a f t , t o t h e i m p e l l e r . The r o t a t i n g i m p e l l e r a c t i o n r e s u l t e d i n t h e g a s being f i n e l y dispersed i n t o the s l u r r y . The v a p o r s p a c e o f t h e r e a c t o r was c o n n e c t e d t o a g a s c h r o m a t o g r a p h f o r measurement o f the gas phase f o r p r o d u c t s o f r e a c t i o n . Except f o r s m a l l q u a n t i t i e s o f g a s removed f o r a n a l y t i c a l p u r p o s e s , t h e r e was no g a s b l e d f r o m t h e s y s t e m o r any o x y g e n s u p p l i e d d u r i n g a n e x p e r i m e n t a l run. M i n u s 100 mesh c o a l was u s e d , a n d t h e d e g r e e o f a g i t a t i o n was f i x e d t o m a i n t a i n t h e system i n a k i n e t i c a l l y c o n t r o l l e d r e gime ( 2 ) . Ammonia c o n c e n t r a t i o n s b e t w e e n 0.5M a n d 5M were s t u d ied. An a n a l y s i s o f t h e s t a r t i n g I l l i n o i s No. 6 c o a l i s l i s t e d i n Table I .

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

14.

175

Ammonia/Oxygen System for Sulfur Removal

SAREEN

Table I.

Starting Coal

Analysis

ash 19.27% v o l . matter 35.6% f i x e d carbon 45.13% ΒTU (maf) 13477

Total sulfur 4.99% Pyritic sulfur 2.06% Sulfate sulfur 0.65% Organic s u l f u r 2.28% Experimental Results

The c h e m i c a l r e a c t i o n f o r t h e o x i d a t i o n n i a c a l s y s t e m i s g i v e n by E q u a t i o n 1 :

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch014

FeS

2

+

4NH + 7/2 H 0 3

2

+

15/4

o f p y r i t e i n an ammo­

0 + 4NH* + 2S0^ 2

+

Fe(0H>

3

where a l l of the s u l f i d e s u l f u r i s o x i d i z e d to s o l u b l e s u l f a t e s . C a r e was t a k e n t o i n s u r e t h a t t h e molar r a t i o f o r the e x p e r i m e n t a l s t u d y was a l w a y s i n e x c e s s o f t h e 4 r e q u i r e d s t o i c h iometrically: a r a n g e b e t w e e n 6.5 and 65 was c o n s i d e r e d . The e f f e c t o f r e t e n t i o n t i m e and ammonia c o n c e n t r a t i o n on s u l f u r r e m o v a l f r o m I l l i n o i s No. 6 c o a l s i s g r a p h i c a l l y d i s p l a y e d i n F i g u r e 1. A p p r o x i m a t e l y 90% o f t h e p y r i t i c s u l f u r can be r e ­ moved, and t h e r e a p p e a r s t o be no a p p a r e n t e f f e c t o f NH3 concen­ t r a t i o n on p y r i t e r e m o v a l . T h e r e seems t o be a d e f i n i t e t r e n d , h o w e v e r , i n t h e o r g a n i c s u l f u r r e m o v a l as a f u n c t i o n o f NH3 con­ centration. Measurements o f t o t a l change i n s u l f u r c o n t e n t o f t h e c o a l , e x p r e s s e d as l b s . SU2/MMBtu, shows a 50% change b e ­ tween t h e s t a r t i n g c o a l and t h e d e s u l f u r i z e d c o a l . T h i s compares a g a i n s t a 25% change a f t e r d e s u l f u r i z a t i o n o f I l l i n o i s No. 6 c o a l s when u s i n g t h e system where o n l y p y r i t i c s u l f u r i s removed. The d e s u l f u r i z e d c o a l s , a f t e r an treatment, a l s o show no r e s i d u a l s u l f a t e s u l f u r . An i m p o r t a n t c o n s i d e r a t i o n i n any c h e m i c a l d e s u l f u r i z a t i o n p r o c e s s i n which the c o a l s u l f u r i s o x i d i x e d i s the o x i d a n t con­ sumption. For t h i s p r o c e s s the oxygen consumption to o x i d i z e the c o a l s u l f u r s p e c i e s and t h e c o a l i t s e l f may be l i s t e d as f o l l o w s :

NH3/FeS2

O2/H2O

(2)

(1)

Reaction with

(2)

O x i d a t i o n of o r g a n i c

sulfur

(3)

Oxygen u p t a k e by

coal

(4)

O x i d a t i o n o f c o a l t o f o r m CO phase

(5)

Formation of carbonates i n

NH3/O2

pyrite

the

and

CO2

i n the

gaseous

solution

The s t o i c h i o m e t r i c o x y g e n c o n s u m p t i o n f o r t h e p y r i t e r e ­ a c t i o n , g i v e n by E q u a t i o n c a l c u l a t e s t o be l b . 02/lb.

FeS2.

1,

1.0

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

(1)

COAL

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch014

176

DESULFURIZATION

REACTION TIME, MINS.

Figure 1.

Sulfur removal as a function of ammonia concentration and time

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch014

14.

SAREEN

Ammonia/Oxygen System for Sulfur Removal

177

In the o x i d a t i o n of p y r i t e w i t h oxygen, i t i s inescapable t h a t oxygen w i l l a l s o r e a c t w i t h the c o a l c a r b o n . T h i s o x i d a t i o n o f t h e c o a l u s u a l l y r e s u l t s i n t h e f o r m a t i o n o f CO and CO2, together with soluble coal a c i d s . There i s a g r e a t e r p r o p e n s i t y f o r the f o r m a t i o n of c o a l a c i d s i n b a s i c systems than i n a c i d systems. F u r t h e r m o r e , t h e r e i s some p i c k u p o f o x y g e n by t h e c o a l t o f o r m an i n t e r m e d i a t e oxygen-coal complex. The g a s e s , as a n a l y z e d i n t h e v a p o r s p a c e o f t h e a u t o c l a v e s , u s i n g a gas c h r o m a t o g r a p h , show t h a t CO f o r m a t i o n i s n e g l i g i b l e and t h a t CO2 i s t h e m a j o r p r o d u c t o f r e a c t i o n . Some o f t h e CO2 formed from carbon o x i d a t i o n tends t o d i s s o l v e i n the ammoniacal l i q u o r and r e p o r t as c a r b o n a t e s i n s o l u t i o n . To d e t e r m i n e a c c u r a t e l y the e x a c t oxygen consumption f o r c o a l o x i d a t i o n , s o l u t i o n a n a l y s e s w e r e c o n d u c t e d t o measure t h i s amount o f c a r b o n a t e f o r m e d . T h e s e a n a l y s e s showed t h a t t h e amount o f c a r b o n a t e m e a s u r e d i n s o l u t i o n i n c r e a s e d w i t h i n c r e a s i n g ammonia c o n c e n t r a t i o n . The t o t a l o x y g e n consumed by c o a l o x i d a t i o n t o f o r m b o t h CO2 i n t h e v a p o r s p a c e and c a r b o n a t e i n s o l u t i o n , as a f u n c t i o n o f r e t e n t i o n t i m e and ammonia c o n c e n t r a t i o n , i s shown i n F i g u r e 2. These r e s u l t s show t h a t c o a l o x i d a t i o n i s f a i r l y i n s e n s i t i v e t o t h e ammonia concentration. B e c a u s e o f t h e f o r m a t i o n o f an o x y g e n - c o a l c o m p l e x , t h e r e i s some o x y g e n t i e d up w i t h t h e c o a l . T h i s c o n s u m p t i o n i s g r a p h i c a l l y d i s p l a y e d i n F i g u r e 3, w h i c h a g a i n shows no dependence on ammonia c o n c e n t r a t i o n . These oxygen v a l u e s r e f l e c t the t o t a l oxygen c o n t e n t o f t h e c o a l , f o r b o t h t h e s t a r t i n g c o a l s and a f t e r dep y r i t i z a t i o n , as m e a s u r e d by n e u t r o n a c t i v a t i o n t e c h n i q u e s . A minimum o x y g e n c o n s u m p t i o n f o r t h i s p r o c e s s i s t a b u l a t e d i n T a b l e II. Table I I .

Minimum Oxygen C o n s u m p t i o n LBS.

0 / L B . COAL 2

O2

for pyrite reaction

0.0375

a

O2

u p t a k e by

coal

0.0340

b

O2

f o r C0

C0 =

0.0350

b

2

+

3

0.1065 a

B a s e d on 2% p y r i t i c s u l f u r c o a l . A f t e r 2 hr. of s u l f u r removal.

T h i s t a b l e does n o t t a k e i n t o a c c o u n t any o x y g e n c o n s u m p t i o n f o r o r g a n i c s u l f u r o x i d a t i o n , w h i c h i s d i f f i c u l t t o measure. For a p l a n t p r o c e s s i n g 8000 t o n s / d a y o f 2% p y r i t i c s u l f u r c o a l ( w i t h a p y r i t i c s u l f u r / o r g a n i c s u l f u r r a t i o o f 1 ) , t h e o x y g e n demand b a s e d on T a b l e I I c a l c u l a t e s t o be 850 t o n s / d a y . W i t h a 20% c o n t i n g e n c y

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

178

COAL

•

0.5MNH

Ô

1.04MNH

Ο

1.94MNH-,

3

3

Ο

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch014

DESULFURIZATION

Ο Δ

•· t ? 20

J 40

-L

L

60

80

100

120 140

160 180

REACTION TIME, MINS. Figure 2.

Oxygen consumption for coal oxidation

Figure 3.

Oxygen uptake by coal

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

14.

Ammonia/Oxygen

SAREEN

System for

Sulfur

179

Removal

f a c t o r t o a l l o w f o r o r g a n i c s u l f u r o x i d a t i o n , a 1000 t o n s / d a y o x y gen p l a n t w o u l d be n e e d e d . T h i s t o t a l o x y g e n d u t y i s t h e same as that required f o r coal d e s u l f u r i z a t i o n using the system (2). An i m p o r t a n t c o n s i d e r a t i o n f o r t h e v i a b i l i t y o f any d e s u l f u r i z a t i o n process i s the o v e r a l l thermal e f f i c i e n c y o f the system. The B t u l o s s , on a m o i s t u r e - a s h - f r e e b a s i s , as a f u n c t i o n o f r e a c t i o n t i m e and ammonia c o n c e n t r a t i o n i s p r e s e n t e d i n F i g u r e 4. T h i s g r a p h shows t h a t b e t w e e n 8% and 1 3 % l o s s may be e x p e c t e d a f t e r 2 h r . o f s u l f u r r e m o v a l . The p a i r i n g o f t h e B t u l o s s a s a f u n c t i o n o f ammonia c o n c e n t r a t i o n shown i n F i g u r e 4 i s n o t immed i a t e l y o b v i o u s . The l o s s o f c a r b o n d u r i n g t h e d e s u l f u r i z a t i o n p r o c e s s i s g r a p h i c a l l y d i s p l a y e d i n F i g u r e 5. I n a l l c a s e s t h e c a r b o n l o s s i s much g r e a t e r t h a n c a n be a c c o u n t e d f o r by CO2 and carbonate formation. This suggests that the d i f f e r e n c e reports i n s o l u t i o n as c o a l a c i d s . The f o r m a t i o n o f t h e s e a c i d s i s n o t s u r p r i s i n g s i n c e t h e r e a c t i o n o f a l k a l i s w i t h c o a l t o form humic a c i d s i s w e l l known. A c o m p a r i s o n between t h e k e y parameters o f t h e systems ( o n l y p y r i t i c s u l f u r r e m o v a l ) and t h e system ( p y r i t i c s u l f u r and some o r g a n i c s u l f u r r e m o v a l ) i s p r e s e n t e d i n T a b l e I I I .

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch014

O2/H0O

H2O/O2

NH3/O2

Table I I I .

Comparison between H 0 / 0 ?

9

and mj0

Systems

o

H 0/0 2

2

N H

3

/ 0

3

2

S u l f u r removal pyritic

+

90 %

+

90 %

organic

0 %

25

%

Oxygen c o n s u m p t i o n (lbs. 0 / l b . coal) 2

Btu

0

2

f o rpyrite reaction

0.035

0.0375

0

2

uptake by c o a l

0.054

0.0340

0

2

t o form C 0

0.032

0.0350

loss

2

(MAF)

Carbon l o s s

(MAF)

8 %

13

%

10%

6.5%

I l l i n o i s No. 6 c o a l s , 20% s l u r r y d e n s i t y , 2% p y r i t i c s u l f u r . The h i g h e r B t u and c a r b o n l o s s e s f o r t h e N H / 0 s y s t e m a r e t o be e x p e c t e d b e c a u s e o r g a n i c s u l f u r r e m o v a l n e c e s s a r i l y i m p l i e s some c o a l (and t h e r e f o r e B t u ) l o s s e s . 3

2

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch014

180

COAL

DESULFURIZATION

2h 0

20

40

60

80

100 120 140

160 180 200

REACTION TIME, MINS. Figure 4.

Figure 5.

Btu loss from coals

Carbon loss from coals

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

14.

Ammonia/Oxygen System for Sulfur Removal

SAREEN

181

Summary and C o n c l u s i o n s 1. I n c r e a s i n g r e a c t i o n t i m e a n d ammonia c o n c e n t r a t i o n i m ­ proved t h e extent o f o r g a n i c s u l f u r removal. F o r example, a f t e r 2 h r . u s i n g a 5M NH^ s o l u t i o n , 2 5 % o f t h e o r g a n i c s u l f u r c a n be removed. 2. C h a n g i n g t h e NH^ c o n c e n t r a t i o n h a d no a p p a r e n t a f f e c t on p y r i t i c s u l f u r removal. 3. The o x y g e n consumed t o o x i d i z e t h e c o a l c a r b o n ( r e p o r t ­ i n g a s C 0 i n t h e gas p h a s e and c a r b o n a t e i n s o l u t i o n ) i s f a i r l y i n s e n s i t i v e t o t h e NH^ c o n c e n t r a t i o n . Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch014

2

4. Ammonia c o n c e n t r a t i o n h a s no a p p a r e n t a f f e c t on o x y g e n uptake by t h e c o a l . 5. B o t h t h e ammonia c o n c e n t r a t i o n and r e a c t i o n t i m e h a v e a n e f f e c t on t h e B t u a n d c a r b o n v a l u e s o f c o a l . Increasing either one d e c r e a s e s t h e B t u and c a r b o n v a l u e . A s much a s a 1 3 % B t u a n d 10% c a r b o n l o s s may be r e a l i z e d w i t h u s i n g a 3M NH^ s o l u t i o n and r e a c t i n g t h e c o a l f o r 2 h r . The l a r g e c a r b o n l o s s e s a r e f r o m t h e formation of coal acids.

Literature Cited

1. Agarwal, J. C., Giberti, R. Α., Irminger, P. F., Petrovic, L. J., Sareen, S. S., Min. Congr. J., (1975), 61 (3), 40-43. 2. Sareen, S. S., Giberti, R. Α., Irminger, P. F., Petrovic, L. J., AIChE Symp. Ser., (1977), 73 (165), 183-189. 3. Lorenzi, L. Jr., Land, J. S., VanNice, L. J., Koutsoukas, E. P., Meyers, R. Α., Coal Age, (Nov. 1972), 77 (11), 70-76. 4. Diaz, A. F., Guth, E. D., U.S. Patent No. 3,909,211 (1975). 5. Smith, E. G., Am. Chem. Soc., Div. of Fuel Chemistry, 169th National Meeting, Philadelphia, Pa., April 6-11, 1975. 6. "Coal Cleaning Readies for Wider Sulfur-Removal Role," Chem. Eng., (March 1, 1976), 83 (6), 70-74.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

15 Desulfurizing Coal with Alkaline Solutions Containing Dissolved Oxygen

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch015

C. Y. TAI,* G. V. GRAVES, and T. D. WHEELOCK Iowa State University, Department of Chemical Engineering and Nuclear Engineering, Energy and Mineral Resources Research Institute, Ames, IA 50011 The extraction of pyritic sulfur from coal by leaching the comminuted material with hot aqueous solutions containing dissolved oxygen has been demonstrated in numerous laboratory experiments (1-6). Although acidic solutions have generally been used for such experiments, basic solutions appear to offer several important advantages. Thus Majima and Peters (7) showed that the rate of extraction of sulfur from relatively pure pyrite is much greater in basic solutions containing dissolved oxygen than in neutral solutions. Moreover it has been shown recently that basic solutions containing ammonium hydroxide and oxygen can extract a significant portion of the organic sulfur as well as most of the inorganic sulfur from coal at relatively moderate temperatures (e.g., 130°C) (4,5) whereas higher temperatures (150°-200°C) seem to be required with acidic solutions to remove organic sulfur (6). Furthermore some types of basic solutions are much less corrosive towards the common materials of construction than acidic solutions. A l t h o u g h the chemical kinetics and mechanism o f pyrite r e a c tion with an o x y g e n - b e a r i n g caustic solution have been studied, t h e y a r e n o t c o m p l e t e l y d e f i n e d . S t e n h o u s e and A r m s t r o n g ( 8 ) f o u n d s u l f a t e i o n s and i r o n o x i d e s t o be t h e f i n a l p r o d u c t s o f reaction. B o t h Fe2Û3 and Fe3Û4 were i d e n t i f i e d i n t h e r e s i d u e . I t a p p e a r e d t o t h e s e i n v e s t i g a t o r s t h a t t h e i r o n o x i d e s formed a s t a b l e l a y e r around t h e u n r e a c t e d p y r i t e . As a r e s u l t o f a l a t e r i n v e s t i g a t i o n , B u r k i n and Edward ( 9 ) c o n c l u d e d t h a t t h e f i n a l o x i d a t i o n p r o d u c t o f i r o n i s maghemite (yFe203) w h i c h i s formed t h r o u g h a s e r i e s o f t o p o t a c t i c t r a n s f o r m a t i o n s . These i n v e s t i g a t o r s o b s e r v e d t h a t t h e r a t e o f a t t a c k was more r a p i d a l o n g g r a i n b o u n d a r i e s and c r a c k s i n impure and i m p e r f e c t p y r i t e c r y s t a l s , w i t h t h e r e s u l t t h a t t h e s e p a r t i c l e s were l e a c h e d more r a p i d l y t h a n p a r t i c l e s c o n t a i n i n g few i m p e r f e c t i o n s and i m p u r i t i e s ,

*Present address: T a i w a n , R.O.C.

Chung-Shen I n s t i t u t e o f S c i e n c e and T e c h n o l o g y ,

182

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch015

15.

TAi E T A L .

Alkaline

Solutions

with Dissolved

Oxygen

183

even though t h e i n s o l u b l e o x i d a t i o n p r o d u c t adhered t o t h e imper­ f e c t c r y s t a l s b u t n o t t o t h e p e r f e c t o n e s . As a r e s u l t o f t h e i n t e r g r a n u l a r a t t a c k by t h e l e a c h s o l u t i o n , t h e s m a l l e r c r y s t a l s w i t h i n p a r t i c l e s composed o f d i f f e r e n t - s i z e d c r y s t a l s were d e s u l ­ f u r i z e d b e f o r e t h e l a r g e r c r y s t a l s . The r e a c t i o n r a t e i n c r e a s e d w i t h temperature a c c o r d i n g t o the A r r h e n i u s e q u a t i o n w i t h an a c t i v a t i o n energy o f 9 k c a l / m o l . A l s o t h e r e a c t i o n r a t e was c o n t o l l e d by t h e o x y g e n c o n c e n t r a t i o n a t t h e m i n e r a l - s o l u t i o n i n t e r ­ face so t h e r a t e i n c r e a s e d w i t h the oxygen p a r t i a l p r e s s u r e . In a d d i t i o n , the r a t e increased with i n c r e a s i n g concentration o f s o d i u m h y d r o x i d e up t o 2 wt %. H i g h e r c o n c e n t r a t i o n s r e d u c e d t h e rate s l i g h t l y . I n a s o l u t i o n o f some b a s e s u c h a s s o d i u m h y d r o x i d e , t h e s t o i c h i o m e t r y o f t h e r e a c t i o n o f p y r i t e w i t h o x y g e n and t h e s u b ­ s e q u e n t n e u t r a l i z a t i o n o f t h e a c i d p r o d u c e d c a n p r o b a b l y be r e ­ p r e s e n t e d by t h e f o l l o w i n g e q u a t i o n s : FeS

2

+ ^| 0

2

+ 2 H 0 = y F e ^ + 2 H SC> 2

2

4

2 H S 0 . + 4 NaOH = 2 N a S 0 , + 4 H 0 2 4 2 4 2 o

o

o

(1) (2)

A l t h o u g h these e q u a t i o n s s u g g e s t t h a t the main purpose o f t h e a l k a l i i s t o n e u t r a l i z e t h e a c i d and t o d r i v e t h e f i r s t r e a c t i o n t o c o m p l e t i o n , t h e a c t u a l r e a c t i o n mechanism i s p r o b a b l y more c o m p l e x w i t h t h e a l k a l i p l a y i n g a more s u b t l e r o l e a s w e l l a s t h e o b v i o u s one. An i n v e s t i g a t i o n by McKay a n d H a l p e r n ( 1 0 ) o f t h e r e a c t i o n o f p y r i t e w i t h o x y g e n i n a c i d i c s o l u t i o n s showed t h a t t h e p r o d u c t d i s t r i b u t i o n , and t h e r e f o r e t h e r e a c t i o n mechanism, i s q u i t e d i f ­ f e r e n t f r o m t h a t n o t e d above f o r b a s i c s o l u t i o n s . Thus p y r i t e was c o n v e r t e d t o s o l u b l e f e r r o u s and f e r r i c s u l f a t e , s u l f u r i c a c i d , and e l e m e n t a l s u l f u r when l e a c h e d w i t h o x y g e n - b e a r i n g a c i d i c s o l u t i o n s a t 100°-130°C. The p r o d u c t d i s t r i b u t i o n depended on t e m p e r a t u r e a n d a c i d i t y , w i t h a l o w e r t e m p e r a t u r e and h i g h e r a c i d ­ i t y f a v o r i n g t h e p r o d u c t i o n o f e l e m e n t a l s u l f u r a n d a h i g h e r tem­ p e r a t u r e and l o w e r a c i d i t y f a v o r i n g t h e p r o d u c t i o n o f s u l f u r i c a c i d and s o l u b l e s u l f a t e s . A l s o a t m o d e r a t e pH ( b u t n o t a t l o w ρΗ), t h e f e r r i c h y d r o x i d e h y d r o l y z e d , and f e r r i c o x i d e p r e c i p i ­ tated. The A r r h e n i u s a c t i v a t i o n e n e r g y was d e t e r m i n e d t o be 13 k c a l / m o l , w h i c h , b e i n g s i g n i f i c a n t l y l a r g e r t h a n t h a t n o t e d above for the reaction of p y r i t e i na caustic s o l u t i o n , indicates a g r e a t e r e n e r g y b a r r i e r f o r t h e r e a c t i o n i n a n a c i d i c medium. The p r e s e n t i n v e s t i g a t i o n was u n d e r t a k e n t o e v a l u a t e t h e t e c h n i c a l f e a s i b i l i t y o f e x t r a c t i n g s u l f u r from c o a l w i t h h o t oxygen-bearing s o l u t i o n s . S i n c e i t was s o o n c o n f i r m e d t h a t a l k a ­ l i n e o r b a s i c s o l u t i o n s r e s u l t e d i n a much g r e a t e r r a t e o f e x ­ t r a c t i o n t h a n a c i d i c s o l u t i o n s , c o n s i d e r a b l e e m p h a s i s was p l a c e d on d e t e r m i n i n g t h e e f f e c t i v e n e s s o f d i f f e r e n t a l k a l i s a n d a l k a l i concentrations. Several h i g h - s u l f u r bituminous c o a l s , as w e l l as

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

184

COAL

DESULFURIZATION

p y r i t e w h i c h had been i s o l a t e d f r o m one o f t h e s e c o a l s , were l e a c h e d i n a s m a l l s t i r r e d r e a c t o r under a v a r i e t y of e x p e r i mental c o n d i t i o n s . In a d d i t i o n the o v e r - a l l e f f e c t i v e n e s s of c h e m i c a l l e a c h i n g i n c o m b i n a t i o n w i t h p h y s i c a l b e n e f i c i a t i o n was investigated.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch015

Experimental L e a c h i n g e x p e r i m e n t s were c a r r i e d o u t i n a 1-L, s t a i n l e s s s t e e l a u t o c l a v e e q u i p p e d w i t h a r e m o v a b l e n i c k e l l i n e r and an a g i t a t o r c o n s i s t i n g o f two p i t c h e d b l a d e t u r b i n e i m p e l l e r s (7.3 cm d i a m e t e r ) mounted on a s h a f t d r i v e n by a c o m p r e s s e d a i r m o t o r . The a u t o c l a v e was a l s o e q u i p p e d w i t h a p r e s s u r e gauge, t e m p e r a t u r e i n d i c a t o r , and e l e c t r i c h e a t i n g j a c k e t . A s u s p e n s i o n o f c o a l o r p y r i t e p a r t i c l e s i n an a l k a l i n e s o l u t i o n o f a s p e c i f i c c o n c e n t r a t i o n was p l a c e d i n t h e r e a c t o r w h i c h was t h e n s e a l e d and h e a t e d t o a s p e c i f i c o p e r a t i n g t e m p e r a ture. A f t e r t h e s y s t e m a t t a i n e d t h i s t e m p e r a t u r e , o x y g e n was introduced f r o m a h i g h - p r e s s u r e c y l i n d e r e q u i p p e d w i t h a comb i n a t i o n p r e s s u r e - r e d u c i n g v a l v e and r e g u l a t o r . D u r i n g t h e s u c c e e d i n g o p e r a t i o n , t h e s y s t e m p r e s s u r e was k e p t c o n s t a n t by s u p p l y i n g o x y g e n on demand. A l s o a s m a l l amount o f gas was b l e d c o n t i n u o u s l y f r o m t h e r e a c t o r t o a v o i d any b u i l d - u p o f g a s e o u s r e a c t i o n p r o d u c t s i n the s y s t e m . R e a c t i o n c o n d i t i o n s were k e p t c o n s t a n t f o r a s p e c i f i c t i m e w h i l e t h e m a t e r i a l was l e a c h e d . At t h e end o f t h e r e a c t i o n p e r i o d , the f l o w o f o x y g e n i n t o t h e s y s t e m was s t o p p e d , and t h e s y s t e m was c o o l e d . Throughout the o p e r a t i o n t h e a g i t a t o r was k e p t r u n n i n g a t a c o n s t a n t speed w h i c h was u s u a l l y i n the r a n g e o f 250-350 rpm. A f t e r a run the l e a c h e d s o l i d s were r e c o v e r e d , d r i e d , and w e i g h e d . C o a l s a m p l e s w e r e a n a l y z e d by t h e s t a n d a r d ASTM methods o f a n a l y s i s ( 1 1 ) . When p y r i t e a l o n e was l e a c h e d , t h e amount o f s u l f u r e x t r a c t e d was d e t e r m i n e d by m e a s u r i n g t h e s u l f a t e c o n t e n t o f t h e s p e n t l e a c h a n t u s i n g t h e s u l f a t e t i t r a t i o n method o f F r i t z and Yamaraura ( 1 2 ) . C o a l s a m p l e s f r o m t h e B i g Ben, ICO, and ISU Demonstration M i n e No. 1, a l l l o c a t e d i n S o u t h e a s t e r n Iowa, were l e a c h e d . The rank of the c o a l from these mines i s h i g h v o l a t i l e C b i t u m i n o u s c o a l ; t y p i c a l c o m p o s i t i o n s a r e shown i n T a b l e I . S i n c e t h e c o a l from these mines i s v e r y heterogeneous, v a r i o u s batches used f o r s p e c i f i c s e t s o f e x p e r i m e n t s were r e - a n a l y z e d and the c o m p o s i t i o n reported along with other experimental r e s u l t s . A h a n d p i c k e d sample o f i r o n p y r i t e s was o b t a i n e d f r o m t h e c o a l d e p o s i t a t ISU D e m o n s t r a t i o n M i n e No. 1. T h i s m a t e r i a l was v e r y i m p u r e and seemed t o c o n t a i n a b o u t 74% FeS2» Nevertheless, i t was g r o u n d and s c r e e n e d i n t o v a r i o u s s i z e d f r a c t i o n s w h i c h were u s e d s u b s e q u e n t l y f o r v a r i o u s l e a c h i n g e x p e r i m e n t s . The s u l f u r c o n t e n t o f t h e d i f f e r e n t s i z e f r a c t i o n s i s shown i n T a b l e II. I n a d d i t i o n t o p y r i t i c s u l f u r , t h e m a t e r i a l c o n t a i n e d some s u l f u r i n t h e f o r m o f s u l f a t e s and some i n a f o r m w h i c h was n e i t h e r p y r i t i c nor s u l f a t e .

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

15.

TAi E T A L .

Alkaline

Solutions

with Dissolved

185

Oxygen

T a b l e I . P r o x i m a t e A n a l y s i s o f Iowa C o a l s

Proximate A n a l y s i s

Source o f C o a l

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch015

Big

Ben mine

Volatile Matter

Fixed Carbon

(wt %)

Ash

Moisture

37.5

48.8

1.2

12.5

ICO mine

44.0

42.0

4.5

9.5

ISU mine

38.1

44.2

2.2

15.5

Table I I .

Composition of Iron

Pyrites

Composition Size Fraction (U.S. S e r i e s Mesh)

Iron

Pyritic Sulfur

Sulfate Sulfur

(wt %) Total Sulfur

41.7

-60/+80 39.,2

0.,5

40.9

-200/+230

36.,4

0.,7

40.3

-230/+270

36.,3

0..7

39.4

-120/+140

Other

42.5

16.6

P y r i t e Leaching Experiments A s e r i e s o f l e a c h i n g e x p e r i m e n t s was c a r r i e d o u t t o d e t e r mine t h e e f f e c t o f v a r i o u s s y s t e m p a r a m e t e r s on t h e e x t r a c t i o n o f s u l f u r f r o m impure p y r i t e . F o r each experiment a s u s p e n s i o n cons i s t i n g o f 2.0 g o f p y r i t e p a r t i c l e s and 500 m l o f a n aqueous s o l u t i o n was t r e a t e d i n t h e s t i r r e d a u t o c l a v e a t 150°C w i t h o x y g e n d i s s o l v e d under a p a r t i a l p r e s s u r e o f 3.27 atm. S i n c e t h e v a p o r p r e s s u r e o f w a t e r a t t h i s t e m p e r a t u r e i s 4.56 atm, t h e t o t a l s y s t e m p r e s s u r e was 7.8 atm. U n l e s s i n d i c a t e d o t h e r w i s e , t h e l e a c h i n g o p e r a t i o n under o x y g e n p r e s s u r e a t t h e s p e c i f i e d t e m p e r a t u r e was c o n d u c t e d f o r 1 h r . The c o n v e r s i o n o f a l l forms o f s u l f u r i n t h e p a r t i c l e s t o s o l u b l e s u l f a t e was d e t e r m i n e d by a n a l y z ing the spent l e a c h a n t . The r e s u l t s p r e s e n t e d i n F i g u r e 1 i n d i c a t e t h a t among t h e v a r i o u s a l k a l i s t e s t e d , s o d i u m c a r b o n a t e was t h e most e f f e c t i v e . E s s e n t i a l l y a l l o f t h e s u l f u r was e x t r a c t e d f r o m -200/+230 mesh

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch015

186

C O A L DESULFURIZATION

p y r i t e p a r t i c l e s i n 1.0 h r by an o x y g e n a t e d s o l u t i o n c o n t a i n i n g 1.5 wt % s o d i u m c a r b o n a t e . The b e s t r e s u l t s o b t a i n e d w i t h e i t h e r s o d i u m h y d r o x i d e o r s o d i u m p h o s p h a t e were s l i g h t l y l e s s f a v o r a b l e and w i t h ammonium c a r b o n a t e much l e s s f a v o r a b l e . The ammonium c a r b o n a t e s o l u t i o n s were n o t i c e a b l y l e s s b a s i c t h a n t h e o t h e r s o l u t i o n s and t h i s f a c t o r p r o b a b l y a c c o u n t e d f o r t h e p o o r e r r e s u l t s o b t a i n e d w i t h them. However, t h e ammonium c a r b o n a t e s o l u t i o n s , as w e l l as t h e o t h e r a l k a l i n e s o l u t i o n s , a l l gave b e t t e r r e s u l t s t h a n w a t e r and o x y g e n a l o n e . Thus o n l y 27% o f the s u l f u r was e x t r a c t e d f r o m t h e p y r i t e d u r i n g a r u n made w i t h o u t any alkali. The e f f e c t i v e n e s s o f a l l o f the a l k a l i s i n c r e a s e d w i t h i n i t i a l c o n c e n t r a t i o n up t o some optimum v a l u e and t h e n d e c r e a s e d . F o r s o d i u m h y d r o x i d e t h e optimum i n i t i a l c o n c e n t r a t i o n was a b o u t 1 wt %, f o r s o d i u m c a r b o n a t e 1.5 wt %, f o r s o d i u m p h o s p h a t e 3 wt %, and f o r ammonium c a r b o n a t e 4 wt %. The s h a r p i n c r e a s e i n c o n v e r s i o n f o r i n i t i a l c o n c e n t r a t i o n s a t the low end o f the c o n c e n t r a t i o n s c a l e seems t o be r e l a t e d t o t h e amount o f a l k a l i r e q u i r e d to n e u t r a l i z e a l l of the a c i d produced i n o x i d i z i n g the pyrite. Thus i f i t i s assumed t h a t a l l o f the s u l f u r i n t h e s o l i d s was c o n v e r t e d i n t o s u l f u r i c a c i d d u r i n g t h e l e a c h i n g o p e r a t i o n , i t w o u l d have r e q u i r e d an i n i t i a l s o d i u m h y d r o x i d e c o n c e n t r a t i o n o f 0.40 wt % t o n e u t r a l i z e a l l o f t h e a c i d p r o duced. I n t e r e s t i n g l y enough, t h e d a t a p r e s e n t e d i n F i g u r e 1 show t h a t t h e c o n v e r s i o n f e l l o f f s h a r p l y when l e s s t h a n 0.40 wt % c a u s t i c was u s e d . The amount o f s o d i u m c a r b o n a t e r e q u i r e d t o n e u t r a l i z e t h e a c i d depends on t h e f i n a l p r o d u c t s o f n e u t r a l i z a t i o n . Two p o s s i b i l i t i e s a r e shown b e l o w . H S0. + N a C 0 2 4 2 3 o

o

o

= Na S0. + C0 + H 0 2 4 2 2 o

o

(3)

o

H S 0 . + 2 N a C 0 = N a S 0 . + 2 NaHC0 2 4 2 3 2 4 3 o

o

o

o

o

(4)

The f i r s t r e a c t i o n w o u l d have r e q u i r e d an i n i t i a l s o d i u m c a r b o n a t e c o n c e n t r a t i o n o f 0.53 wt % t o n e u t r a l i z e a l l o f t h e s u l f u r i c a c i d w h e r e a s t h e s e c o n d r e a c t i o n w o u l d have r e q u i r e d an i n i t i a l c o n c e n t r a t i o n o f 1.1 wt %. The e x p e r i m e n t a l r e s u l t s ( F i g u r e 1) i n d i c a t e t h a t t h e c o n v e r s i o n f e l l o f f s h a r p l y when l e s s t h a n a b o u t 1 wt % s o d i u m c a r b o n a t e was u s e d . I n t h e c a s e o f s o d i u m p h o s p h a t e an i n i t i a l c o n c e n t r a t i o n o f 1.65 wt % w o u l d have been r e q u i r e d t o n e u t r a l i z e a l l o f the p o s s i b l e s u l f u r i c a c i d a c c o r d i n g to the f o l l o w i n g r e a c t i o n : H S 0 . + 2 N a P 0 . = N a S 0 . + 2 Na HP0. 2 4 3 4 2 4 2 4 o

o

o

o

(5)

A l t h o u g h the e x p e r i m e n t a l r e s u l t s shown i n F i g u r e 1 i n d i c a t e t h a t the c o n v e r s i o n f e l l o f f s h a r p l y between 2 and 3 wt %, the s p a r s i t y o f t h e d a t a l e a v e c o n s i d e r a b l e d o u b t as t o the e x a c t c r i t i c a l

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch015

15.

TAI E T A L .

Alkaline

Solutions

with Dissolved

Oxygen

187

concentration. Why t h e c o n v e r s i o n d e c l i n e d a t h i g h e r a l k a l i c o n c e n t r a t i o n s w h i c h e x c e e d e d t h e optimum l e v e l s c a n n o t be e x p l a i n e d w i t h c e r tainty. A s i m i l a r d e c l i n e was o b s e r v e d by B u r k i n and Edwards ( 9 ) when p y r i t e was l e a c h e d w i t h c a u s t i c s o l u t i o n s , a n d t h e y a t t r i b u t ed t h e d e c l i n e t o the r e d u c e d s o l u b i l i t y o f o x y g e n i n t h e s e s o l u tions. A l s o s i m i l a r b e h a v i o r was o b s e r v e d i n l e a c h i n g b o t h g a l e n a and m o l y b d e n i t e w i t h c a u s t i c s o l u t i o n s c o n t a i n i n g d i s s o l v e d o x y g e n (13,14). I n the case o f both m i n e r a l s , a d e c l i n e i n r e a c t i o n r a t e w i t h i n c r e a s i n g a l k a l i c o n c e n t r a t i o n was a t t r i b u t e d t o t h e d e c r e a s i n g s o l u b i l i t y o f oxygen. The r e s u l t s o f l e a c h i n g d i f f e r e n t s i z e d f r a c t i o n s o f p y r i t e w i t h sodium carbonate s o l u t i o n s o f d i f f e r e n t c o n c e n t r a t i o n s a r e p r e s e n t e d i n F i g u r e 2. C l e a r l y t h e e f f e c t o f p a r t i c l e s i z e o n c o n v e r s i o n was v e r y p r o n o u n c e d w i t h t h e c o n v e r s i o n i n c r e a s i n g i n an a l m o s t e x p o n e n t i a l manner a s t h e s i z e was r e d u c e d ( F i g u r e 2 ) . P a r t i c l e s s m a l l e r t h a n 60 ym i n d i a m e t e r were c o m p l e t e l y d e s u l f u r i z e d i n 1.0 h r by s o l u t i o n s c o n t a i n i n g 2-5 wt % s o d i u m c a r b o n a t e f o r t h e c o n d i t i o n s shown i n F i g u r e 2. On t h e o t h e r h a n d , p a r t i c l e s l a r g e r t h a n 210 ym i n d i a m e t e r were o n l y a b o u t h a l f d e s u l f u r i z e d u n d e r t h e s e c o n d i t i o n s . F i g u r e 2 a l s o shows t h e advantage o f u s i n g an a l k a l i n e s o l u t i o n . The l o w e r c u r v e i n t h i s d i a g r a m r e p r e s e n t e d t h e c o n v e r s i o n o b t a i n e d when no a l k a l i was added t o t h e s y s t e m . Even w i t h t h e s m a l l e s t p a r t i c l e s o f p y r i t e , o n l y 3 5 % o f t h e s u l f u r was e x t r a c t e d i n the a b s e n c e o f a n a l k a l i . S e v e r a l r u n s were made u s i n g l o n g e r r e a c t i o n t i m e s t o s e e how the c o n v e r s i o n w o u l d change w i t h t i m e ( F i g u r e 3 ) . The r e s u l t s i n d i c a t e t h a t t h e r e a c t i o n r a t e d e c r e a s e d a s the b a t c h l e a c h i n g o p e r a t i o n p r o c e e d e d . The d e c l i n i n g r a t e c o u l d have been c a u s e d by t h e d e c r e a s i n g a v a i l a b i l i t y o f u n r e a c t e d p y r i t e , i n c r e a s i n g resistance to diffusion of reactants within p a r t i c l e s , increasing c o n c e n t r a t i o n o f some r a t e - i n h i b i t i n g r e a c t i o n p r o d u c t i n t h e l e a c h s o l u t i o n , o r a combination o f these f a c t o r s . Coal Leaching

Experiments

A s e r i e s o f l e a c h i n g e x p e r i m e n t s was c a r r i e d o u t t o d e t e r mine t h e e f f e c t s o f v a r i o u s a l k a l i s and a l k a l i c o n c e n t r a t i o n s on t h e d e s u l f u r i z a t i o n o f c o a l f r o m t h e I S U D e m o n s t r a t i o n M i n e No. 1. The raw c o a l was p u l v e r i z e d s o t h a t 9 0 % was f i n e r t h a n 200 mesh. F o r e a c h e x p e r i m e n t 50 g o f c o a l and 500 ml o f w a t e r o r a l k a l i n e s o l u t i o n were p l a c e d i n t h e s t i r r e d a u t o c l a v e . The c h e m i c a l t r e a t m e n t was c a r r i e d o u t f o r 2 h r a t 150°C w i t h o x y g e n d i s s o l v e d u n d e r a p a r t i a l p r e s s u r e o f 3.27 atm and u s i n g a t o t a l s y s t e m p r e s s u r e o f 7.8 atm. The t r e a t e d c o a l was r e c o v e r e d , d r i e d , w e i g h e d , and a n a l y z e d t o d e t e r m i n e t h e e f f e c t i v e n e s s o f t h e t r e a t ment . The b e s t o v e r a l l r e s u l t s were o b t a i n e d w i t h s o d i u m c a r b o n a t e among t h e f o l l o w i n g a l k a l i s w h i c h were t e s t e d i n v a r i o u s c o n c e n trations: sodium carbonate, sodium h y d r o x i d e , sodium phosphate,

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch015

188

COAL DESULFURIZATION

PYRITE -200/+23O MESH 7.8 atm. TOTAL PRESS. 150 °C 1.0 h r .

Figure 1. The effect of different alkalis and alkali concentrations on the extraction of sulfur from pyrite

Figure 2. The effect of particle size on the extraction of sulfur from pyrite

J 2

4

L

6

8

10

INITIAL CONCENTRATION, wt. %

100

150

200

PYRITE PARTICLE SIZE, microns

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

250

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch015

15.

TAI E T A L .

Alkaline

Solutions

with Dissolved

Oxygen

189

c a l c i u m c a r b o n a t e , c a l c i u m h y d r o x i d e , and ammonium c a r b o n a t e . The o n l y a l k a l i w h i c h a p p r o a c h e d s o d i u m c a r b o n a t e i n e f f e c t i v e n e s s was s o d i u m p h o s p h a t e . However, i t r e q u i r e d a 7 wt % i n i t i a l c o n c e n t r a t i o n o f sodium phosphate t o produce c o a l w i t h a s u l f u r c o n t e n t c o m p a r a b l e t o t h a t o b t a i n e d w i t h a 1.4 wt % i n i t i a l c o n c e n t r a t i o n of sodium carbonate. M o r e o v e r , t h e B t u r e c o v e r y was l o w e r and t h e a s h c o n t e n t o f t h e p r o d u c t h i g h e r when s o d i u m p h o s p h a t e was used to o b t a i n c o m p a r a b l e d e s u l f u r i z a t i o n . The i n i t i a l c o n c e n t r a t i o n o f s o d i u m c a r b o n a t e had a v e r y p r o nounced e f f e c t on t h e e x t e n t o f d e s u l f u r i z a t i o n and t h e r e s u l t i n g s u l f u r c o n t e n t o f t h e t r e a t e d c o a l ( T a b l e I I I , F i g u r e 4 ) . The b e s t r e s u l t s were o b t a i n e d w i t h an i n i t i a l c o n c e n t r a t i o n o f 1.4 wt % and u s i n g e i t h e r l o w e r o r h i g h e r c o n c e n t r a t i o n s r e s u l t e d i n l e s s desulfurization. The t r e a t m e n t w i t h t h e optimum c o n c e n t r a t i o n r e duced t h e p y r i t i c s u l f u r c o n t e n t o f t h e c o a l by t w o - t h i r d s . A s i m i l a r e f f e c t o f c o n c e n t r a t i o n was o b s e r v e d when s o d i u m h y d r o x i d e was u s e d w i t h the optimum i n i t i a l c o n c e n t r a t i o n b e i n g a b o u t 1 wt %. Hence, t h e e f f e c t o f a l k a l i c o n c e n t r a t i o n was l i k e t h a t e x p e r i e n c e d in leaching pyrite (Figure 1 ) . Under t h e m i l d l e a c h i n g c o n d i t i o n s used i n t h i s w o r k , m a i n l y i n o r g a n i c s u l f u r was e x t r a c t e d f r o m t h e c o a l . Essentially a l l o f t h e s u l f a t e f o r m o f s u l f u r was e x t r a c t e d a n d a good s h a r e o f the p y r i t i c s u l f u r . Unfortunately the r e s u l t s reported i n Table I I I f o r o r g a n i c s u l f u r a r e so e r r a t i c t h a t i t i s n o t p o s s i b l e t o d i s c e r n w h e t h e r o r g a n i c s u l f u r was removed o r n o t . For the e x p e r i m e n t s i n v o l v i n g sodium c a r b o n a t e , the y i e l d o f d r y c o a l was 93-94%, and t h e B t u r e c o v e r y was 88-92%. These v a l u e s c o u l d have been h i g h e r w i t h t h e e x e r c i s e o f g r e a t e r c a r e in conducting the experiments. Since the heating value o f the t r e a t e d c o a l on a m o i s t u r e and a s h f r e e (maf) b a s i s was n e a r l y t h e same as t h a t o f t h e u n t r e a t e d c o a l , i t does n o t a p p e a r t h a t t h e c o a l was s i g n i f i c a n t l y d e g r a d e d by t h e t r e a t m e n t . A l s o the oxygen c o n t e n t o f t h e c o a l , a s d e t e r m i n e d by u l t i m a t e c h e m i c a l a n a l y s i s , d i d n o t a p p e a r t o be s i g n i f i c a n t l y d i f f e r e n t f r o m t h a t o f t h e untreated coal. These r e s u l t s c o n t r a s t m a r k e d l y w i t h t h o s e r e p o r t e d b y S a r e e n e t a l . ( 3 , 4 ) f o r t r e a t m e n t s u s i n g much h i g h e r oxygen p a r t i a l p r e s s u r e s which r e s u l t e d i n n o t i c e a b l e oxygen upt a k e by I l l i n o i s No. 6 c o a l . As a r e s u l t o f t h e a l k a l i t r e a t m e n t , t h e s o d i u m and a s h c o n t e n t o f t h e c o a l i n c r e a s e d m e a s u r a b l y ( T a b l e I I I , F i g u r e 5 ) . The i n c r e a s e i n a s h c o n t e n t was d i r e c t l y p r o p o r t i o n a l t o t h e i n c r e a s e i n s o d i u m c o n t e n t and seemed c a u s e d a l m o s t e n t i r e l y by t h e a d s o r p t i o n o f s o d i u m . Most o f t h e i n c r e a s e i n s o d i u m o r a s h c o n t e n t t o o k p l a c e a t l o w e r a l k a l i c o n c e n t r a t i o n s , and more t h a n 2 wt % sodium carbonate i n t h e l e a c h a n t g e n e r a l l y produced l i t t l e a d d i tional increase. I n o t h e r w o r d s , t h e c o a l seemed t o become s a t u r a t e d when t h e l e a c h s o l u t i o n c o n t a i n e d 2 wt % s o d i u m c a r b o n a t e o r more. On t h e o t h e r hand, t h e c o a l r e t a i n e d v e r y l i t t l e s o d i u m when t h e l e a c h s o l u t i o n i n i t i a l l y c o n t a i n e d 0.8 wt % s o d ium c a r b o n a t e o r l e s s b e c a u s e t h e s o l u t i o n became a c i d i c b y t h e

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

92

91

93

93

94

94

94

2.0

5.0

8.0

10.0

15.0

chemical

chemical

chemical

chemical

89

90

88

11,010

10,940

10,950

10,590

10,880

10,580

10,780

18.5 19.4 19.7 18.2

— — —

17.8

17.7

13,800

13,520

13,520

16.4

chemical

91

89

—

93

1.4

93

1.0

chemical

10,740

16.3

chemical

90

—

94

0.8

16.2

13,430

chemical

10,950

94

0.8

chemical

92

17.5

—

10,440

88

0

chemical

95

15.3

15.5

13,970

13,660

maf

1.52

1.90

—

1.29

1.14

0.80

0.33

0.10

0.10

—

0.03

0.05

Ash Na ( w t . % ) (wt %)

11,577

as r e e v d .

Heat Value ( B t u / l b )

wash

Btu Recov. (%) 11,240

Wt Yield (%)

none

Treatment

Na2CC>3 Cone. (wt %)

0.17

3.,21

2.,34

1.,63

1.,76

1.,75

1.,23

1.,11

1.,46

1.,89

1.,62

0.18

0.11

0.09

0.11

0.07

0.06

0.05

0.03

0.05

0.11

0.60

2.,28

(lb/10

6

Btu)

3.66 1.80

2.65

2.28

5.17

4.02

4.24

3.15

1.85

2.39

2.99

3.90 1.81

2.39

4.23

3.47

1.80 2.32

5.29

5.63

5.63

2.89

2.25

1.81

S u l f a t e Organic Total

3.,22

Pyritic

Sulfur Distrib.

T a b l e I I I . R e s u l t s o f L e a c h i n g ISU C o a l w i t h D i f f e r e n t C o n c e n t r a t i o n s o f A l k a l i

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch015

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch015

AL.

Alkaline Solutions tvith Dissolved Oxygen

191

PYRITE -120/+Ί40

7.8

MESH

atm.

150 °C

2

3

Figure 3. The effect of reaction time on the extraction of sulfur from pyrite

REACTION T I M E , h r .

-200 7.8

4 INITIAL

Figure 4.

6

8

SODIUM CARBONATE

10

MESH I S U COAL a t m . TOTAL P R E S S .

150° C 2.0 h r . I 12

CONCENTRATION,

I

WT. %

Sulfur content of IS U coal after leaching

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch015

192

COAL

DESULFURIZATION

end o f a r u n . W a s h i n g w i t h w a t e r d i d n o t remove s o d i u m f r o m the t r e a t e d c o a l , b u t w a s h i n g w i t h d i l u t e a c i d (0.1N hydrochloric a c i d ) d i d remove i t . A n o t h e r s e r i e s o f e x p e r i m e n t s was c o n d u c t e d t o see what e f f e c t r e d u c i n g the s i z e o f t h e c o a l w o u l d have on d e s u l f u r i z a t i o n by c h e m i c a l l e a c h i n g . ISU c o a l was f i r s t p u l v e r i z e d to -35 mesh ( a b o u t 50% b e l o w 200 mesh) w i t h a M i k r o - S a m p l m i l l ( P u l v e r i z i n g Machinery D i v i s i o n , A m e r i c a n - M a r i e t t a Co.). The c o a l was t h e n wet-ground i n a ceramic j a r m i l l f o r d i f f e r e n t time p e r i o d s . The p a r t i c l e s i z e d i s t r i b u t i o n o f the c o a l a f t e r g r i n d i n g f o r 2, 4, 8, and 20 h r i s shown i n F i g u r e 6. A f t e r g r i n d i n g f o r 2 h r , 97% o f t h e c o a l was f i n e r t h a n 400 mesh (38 ym) s i z e . The p u l v e r i z e d o r g r o u n d c o a l was t h e n l e a c h e d i n t h e s t i r r e d a u t o c l a v e f o r 2 h r a t 140°C w i t h a 2.0 wt % s o l u t i o n o f s o d i u m c a r b o n a t e c o n t a i n ­ i n g o x y g e n d i s s o l v e d u n d e r a p a r t i a l p r e s s u r e o f 2.4 atm and w i t h a t o t a l s y s t e m p r e s s u r e o f 5.8 atm. F o r e a c h l e a c h i n g r u n 25 g o f c o a l was m i x e d w i t h 500 ml o f s o l u t i o n . The r e s u l t s p r e s e n t e d i n T a b l e IV show t h a t more s u l f u r was e x t r a c t e d f r o m c o a l w h i c h had been ground i n t h e b a l l m i l l t h a n f r o m c o a l w h i c h had o n l y been p u l v e r i z e d w i t h the M i k r o - S a m p l m i l l . Thus t h e p y r i t i c s u l ­ f u r c o n t e n t o f t h e b a l l - m i l l e d c o a l was r e d u c e d 87% w h e r e a s t h e p y r i t i c s u l f u r c o n t e n t o f t h e p u l v e r i z e d c o a l was r e d u c e d o n l y 71%. However, g r i n d i n g t h e c o a l f o r more t h a n 2 h r d i d n o t p r o ­ duce any a d d i t i o n a l b e n e f i t . Combined P h y s i c a l and

Chemical

Cleaning

A f i n a l s e t o f e x p e r i m e n t s i n v o l v e d combined p h y s i c a l and c h e m i c a l c l e a n i n g o f s e v e r a l Iowa c o a l s . Each c o a l was c r u s h e d t o 6 mm χ 0 s i z e w i t h a d o u b l e r o l l c r u s h e r and t h e n c l e a n e d by g r a v i t y s e p a r a t i o n i n an o r g a n i c l i q u i d h a v i n g a s p e c i f i c g r a v i t y o f 1.60. The c l e a n e d f l o a t f r a c t i o n was r e c o v e r e d , d r i e d , and p u l v e r i z e d w i t h the M i k r o - S a m p l m i l l . The p u l v e r i z e d c o a l was wetg r o u n d n e x t i n t h e c e r a m i c j a r m i l l f o r 20 h r and f i n a l l y l e a c h e d i n the s t i r r e d a u t o c l a v e f o r 2.0 h r w i t h a 2.0 wt % s o d i u m c a r ­ b o n a t e s o l u t i o n . The e f f e c t s o f d i f f e r e n t l e a c h i n g t e m p e r a t u r e s and o x y g e n p a r t i a l p r e s s u r e s were s t u d i e d . The r e s u l t s p r e s e n t e d i n T a b l e V show t h a t g r a v i t y s e p a r a t i o n removed a s u b s t a n t i a l p a r t o f the p y r i t i c s u l f u r f r o m e a c h c o a l and t h a t c h e m i c a l l e a c h i n g removed most o f the r e m a i n i n g i n o r g a n i c s u l f u r , b o t h p y r i t i c and s u l f a t e . Thus t h r o u g h t h e combined t r e a t m e n t , the i n o r g a n i c s u l f u r c o n t e n t of each of the t h r e e c o a l s was r e d u c e d 93-95%. The t r e a t e d ICO c o a l came c l o s e to m e e t i n g the f e d e r a l new s o u r c e p e r f o r m a n c e s t a n d a r d o f 0.6 l b S/10 Btu. F o r the p h y s i c a l l y c l e a n e d and f i n e l y g r o u n d c o a l , i t d i d n o t seem to make any d i f f e r e n c e what l e a c h i n g t e m p e r a t u r e i n t h e r a n g e o f 120°-150°C o r what o x y g e n p a r t i a l p r e s s u r e i n t h e r a n g e o f 2.4-5.2 atm was u s e d b e c a u s e e s s e n t i a l l y a l l o f the i n o r g a n i c s u l f u r was removed even u n d e r the m i l d e s t t r e a t m e n t c o n d i t i o n s . 6

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

ET

AL.

Alkaline Solutions with Dissolved Oxygen

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch015

TAI

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

193

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

chemical

3-•108-8 b.mill (8hr) 11,237

11,070

b.mill

chemical

3-•108-6

(4 h r )

11,500

b.mill (2hr)

chemical

3-•108-7

11,360

11,040

H.V. (Btu/lb)

pulverized

pulverized

Grind

chemical

none

Treatment

16.2

16.6

14.7

15.8

12.0

Ash (wt %)

0.34

0.30

0.29

0.67

2.31

Pyritic

0.05

0.05

0.04

2.06

2.17

2.10

2.32

2.19

0.54 0.05

Organic

Sulfate

Sulfur Distribution (lb/10

R e s u l t s o f T r e a t i n g D i f f e r e n t G r i n d s o f ISU C o a l

3-•108-5

Run No.

Table IV.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch015

b

2.46

2.51

2.43

3.05

5.04

Total

Btu

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

B i g Ben B i g Ben B i g Ben B i g Ben

ICO ICO ICO ICO ICO ICO ICO

ISU ISU ISU ISU ISU

Source

25 25

—

40 40 40 25 25

—

40 40 20

—

Amt.(g)

Coal

none float/sink chemical chemical

none float/sink chemical chemical chemical chemical chemical

none float/sink chemical chemical chemical

Treatment

T a b l e V.

— 2.9 3.2

132 150

2.7 3.7 5.2 3.2 3.2

120 120 120 150 150

—

—

5.8 7.8

—

4.7 5.8 7.3 7.8 7.8

—

4.4 5.8 6.9

2.4 2.7 2.4

Total

—

2

(atm.)

—

0

Pressure

—

120 135 150

—

iemp. (°C)

11,800 12,790 10,950 11,680

12,040 12,690 11,630 11,480 11,640 11,220 11,740

10,990 12,390 11,650 11,490 10,770

η. ν . (Btu/lb)

10.6 10.0

— —

11.6 11.6 10.8 14.1 13.2

— —

Ι­.37 Ο,.42 0,.09 0.16

0.,37 0.,28 0..03 0.,04

0.,25 0.,20 0.,02 0.,02 0.,02 0.,03 0.,04

0.,33 0.,23 0.,06 0.,07 0.,04

3.,96 1,,38 0,,13 0.,18 0..21 1,,66 0.,70 0,.10 0,.15 0,.09 0,.14 0.11

Sulfate

%) P y r i t i c

12.2 12.1 24.0

—

(wt

Sulfur Distrib.

R e s u l t s o f Combined P h y s i c a l and C h e m i c a l T r e a t m e n t

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch015

,53 ,41 ,34 ,32 ,04

0..61 0,.81 0,.89 0.81

0.,62 0.,64 0.,58 0.,64 0.,60 0.,56

0. ,61

2. 2. 2. 2. 2.

2.36 1.47 1.00 1.01

2.52 1.53 0.76 0.75 0.74 0.77 0.71

6.81 4.02 2.53 2.57 2.29

Organic Total

(lb/10° B t u )

196

COAL DESULFURIZATION

T h e r e f o r e , i t s h o u l d have b e e n p o s s i b l e t o o b t a i n a s good r e s u l t s even w i t h m i l d e r treatment c o n d i t i o n s o r a s h o r t e r r e a c t i o n time.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch015

Conclusions D i l u t e a l k a l i n e s o l u t i o n s c o n t a i n i n g oxygen d i s s o l v e d u n d e r p r e s s u r e were v e r y e f f e c t i v e a t e l e v a t e d t e m p e r a t u r e s f o r e x ­ t r a c t i n g t h e i n o r g a n i c s u l f u r f r o m c o a l . Of v a r i o u s a l k a l i s t e s t e d , s o d i u m c a r b o n a t e gave t h e b e s t r e s u l t s . T h i s m a t e r i a l a l s o has the advantages o f b e i n g r e a d i l y a v a i l a b l e , low i n c o s t , and r e l a t i v e l y n o n c o r r o s i v e i n aqueous s o l u t i o n t o w a r d s s t e e l and o t h e r common m a t e r i a l s o f c o n s t r u c t i o n . Although s u f f i c i e n t a l k a l i s h o u l d be u s e d t o n e u t r a l i z e a l l o f t h e a c i d w h i c h i s p r o d u c e d t h r o u g h o x i d a t i o n o f t h e c o a l s u l f u r , an e x c e s s i v e c o n ­ c e n t r a t i o n o f a l k a l i seems t o s l o w t h e r a t e o f d e s u l f u r i z a t i o n . On t h e o t h e r h e a d , t h e r a t e o f d e s u l f u r i z a t i o n c a n be i n c r e a s e d by r e d u c i n g t h e s i z e o f t h e c o a l a n d / o r p y r i t e p a r t i c l e s . Leach­ i n g c o a l f i n e s w i t h d i l u t e sodium carbonate s o l u t i o n s a t tempera­ t u r e s up t o 150°C and w i t h o x y g e n p a r t i a l p r e s s u r e s up t o 5 atm f o r up t o 2 h r does n o t seem t o d e g r a d e h i g h v o l a t i l e b i t u m i n o u s coal. However, t h e c o a l does a d s o r b s o d i u m f r o m t h e l e a c h s o l u ­ t i o n w h i c h c a n be removed s u b s e q u e n t l y by w a s h i n g w i t h d i l u t e acid. C h e m i c a l l e a c h i n g c a n be combined a d v a n t a g e o u s l y w i t h p h y s i c a l c l e a n i n g s i n c e t h e l a t t e r i s more a d e p t a t r e m o v i n g c o a r s e r p a r t i c l e s o f p y r i t e w h i l e t h e f o r m e r i s more a d e p t a t removing the microscopic p a r t i c l e s . Ac k n o w l e d gemen t T h i s work was s p o n s o r e d by t h e Iowa C o a l P r o j e c t and c o n ­ d u c t e d i n t h e E n e r g y and M i n e r a l R e s o u r c e s R e s e a r c h I n s t i t u t e a t Iowa S t a t e U n i v e r s i t y .

Literature Cited

1. Nelson, H. W., Snow, R. D., Keyes, D. B., Ind. Eng. Chem. (1933) 25, 1355. 2. Agarwal, J. C., Giberti, R. Α., Irminger, P. F., Petrovic, L. J., Sareen, S. S., Min. Congr. J. (1975) 61 (3), 40. 3. Sareen, S. S., Giberti, R. Α., Irminger, P. F., Petrovic, L. J., Preprint 50c, 80th National Meeting AIChE, (Sep. 7-10, 1975), Boston. 4. Agarwal, J. C., Giberti, R. Α., Petrovic, L. J., U.S. Patent No. 3,960,513, 1976. 5. Sareen, S. S., This volume, in press. 6. Friedman, S., LaCount, R. B., Warzinski, R. P., This volume, in press. 7. Majima, Η., Peters, Ε., Trans. Metall. Soc. AIME (1966) 1409. 8. Stenhouse, J. E., Armstrong, W. M., Can. Min. Metall. Bull. (1952) 45, 49.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

15.

TAI

ET

AL.

Alkaline

Solutions

with

Dissolved

Oxygen

197

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch015

9. Burkin, A. R., Edwards, Α. Μ., in "Mineral Processing," (A. Roberts, Ed.), pp. 159-169, Pergamon, Oxford, 1965. (Procedding of the Sixth International Congress held at Cannes, May 26-June 2, 1963.) 10. McKay, D. R., Halpern, J., Trans. Metall. Soc. AIME (1958) 301. 11. Book ASTM Stand., Part 26, "Gaseous Fuels; Coal and Coke; Atmospheric Analysis," Methods D2015-66, D2492-68, D3174-73, D3177-75, 1976. 12. Fritz, J. S., Yamamura, S. S., Anal. Chem. (1955) 27, 1461. 13. Anderson, J. E., Halpern, J., Samis, C. S., J. Met. (1953) 5, 554. 14. Dresher, W. H., Wadsworth, M. E., Fassell, W., Jr., J. Met. (1956) 8, 794.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

16 Hydrothermal Coal Process E D G E L P. S T A M B A U G H

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch016

Battelle, Columbus Laboratories, 505 King Avenue, Columbus, O H 43201

Coal is the major source of energy for the U.S. and will continue to be so for many years. However, coal is dirty, containing high concentrations of contaminants such as sulfur, nitrogen, and mineral matter. These contaminants, if not removed from the coal before or during combustion, will find their way into the environment and thus constitute a serious health hazard. An alternative to insure a healthier environment, as the consumption of coal as the major source of energy increases, is to remove these contaminants by chemical coal cleaning before combustion. One such method based on hydrothermal technology is the hydrothermal coal process in which certain coals can be chemically cleaned to produce solid fuels which meet Federal sulfur emission standards for new sources. Process Description The basic process, as shown schematically in Figure 1, comprises five major processing operations: coal preparation, hydrothermal (desulfurization) treatment, liquid/solid separation, fuel drying, and leachant regeneration. Coal preparation may entail a simple grinding operation to reduce the raw coal to the desired particle size of 70% -200 mesh or 100% -28 mesh. On the other hand, this operation may involve two operations—grinding of the coal to the desired particle size followed by physical beneficiation to remove a portion of the mineral matter including a portion of the pyritic sulfur. Hydrothermal treatment e n t a i l s b a s i c a l l y three p r o c e s s i n g steps : (1) The g r o u n d c o a l i s m i x e d w i t h a n aqueous a l k a l i n e l e a c h a n t , f o r e x a m p l e , an aqueous s o l u t i o n / s l u r r y o f s o d i u m h y d r o x i d e and l i m e , t o produce a raw c o a l s l u r r y . (2) T h i s r a w s l u r r y i s h e a t e d i n an a u t o c l a v e a t a b o u t 250°-350°C ( s t e a m p r e s s u r e o f 600-2500 p s i g ) t o e x t r a c t a s i g n i f i c a n t p o r t i o n o f t h e s u l f u r and t h e m i n e r a l m a t t e r , d e p e n d i n g on t h e l e a c h a n t and p r o c e s s i n g c o n d i t i o n s .

198

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch016

16.

STAMBAUGH

Hydrothermal

Coal

Process

199

(3) The c o a l p r o d u c t s l u r r y i s c o o l e d and pumped i n t o a r e c e i v i n g tank. The d e s u l f u r i z e d c o a l i s t h e n s e p a r a t e d f r o m t h e s p e n t l e a c h a n t and washed w i t h w a t e r . The f i n a l p r o d u c t i s a s o l i d f u e l c o n t a i n i n g r e d u c e d c o n c e n t r a t i o n s o f s u l f u r a n d , d e p e n d i n g on t h e leaching c o n d i t i o n s , mineral matter. D r y i n g t h e f u e l t o remove t h e r e s i d u a l m o i s t u r e i s o p t i o n a l . F o r some u s e s , i t may be d e s i r a b l e t o b u r n t h e f u e l wet; i n o t h e r s , r e m o v a l o f a p a r t o r a l l o f t h e r e s i d u a l m o i s t u r e may be desirable. I n a n y e v e n t , t h e c o a l c a n be d r i e d i n c o m m e r c i a l l y available dryers. The s p e n t l e a c h a n t c o n t a i n i n g t h e e x t r a c t e d s u l f u r a s s o d i u m s u l f i d e (Na2S) c a n be r e g e n e r a t e d f o r r e c y c l e i n s e v e r a l ways; one a p p r o a c h i n v o l v e s t r e a t m e n t o f t h e s p e n t l e a c h a n t w i t h c a r b o n d i o x i d e t o remove t h e s u l f u r a s H2S w h i c h i s s u b s e q u e n t l y c o n v e r t e d t o e l e m e n t a l s u l f u r by t h e C l a u s o r S t r e t f o r d p r o c e s s . The r e s u l t i n g l i q u o r c o n t a i n i n g s o d i u m c a r b o n a t e s i s t r e a t e d w i t h l i m e t o c o n v e r t t h e c a r b o n a t e s back t o sodium h y d r o x i d e which i s r e c y c l e d t o t h e d e s u l f u r i z a t i o n segment a f t e r a d j u s t i n g t h e concentration. The c a l c i u m c a r b o n a t e i s t h e r m a l l y decomposed t o l i m e and c a r b o n d i o x i d e f o r r e c y c l e t o t h e l e a c h a n t r e g e n e r a t i o n segment. C a p a b i l i t y o f Process Sulfur Extraction. The p r o c e s s i s c a p a b l e o f c o n v e r t i n g , on a l a b o r a t o r y ( b a t c h ) and m i n i p l a n t (1/4 t o n p e r day) s c a l e , a v a r i e t y o f m a j o r seam c o a l s o f d i f f e r e n t r a n k s and l i g n i t e t o clean s o l i d f u e l s having a t o t a l s u l f u r content equivalent t o o r l e s s t h a n 1.2 l b S0 /10° B t u a s shown i n T a b l e I . T h i s i s a c h i e v e d by e x t r a c t i n g g r e a t e r t h a n 90% o f t h e p y r i t i c s u l f u r f r o m a l a r g e number o f c o a l s and e x t r a c t i n g up t o 50% o f t h e o r g a n i c s u l f u r from c e r t a i n c o a l s . Btu recovery as s o l i d c l e a n f u e l i s i n t h e r a n g e o f 90-95%, d e p e n d i n g on t h e c o a l and p r o c e s s i n g c o n d i t i o n s . The r e m a i n d e r , s o l u b i l i z e d b y t h e l e a c h a n t i s recovered during leachant regeneration. This m a t e r i a l could be u s e d a s p r o c e s s h e a t . T h u s , a w i d e v a r i e t y o f m a j o r seam, h i g h - s u l f u r b i t u m i n o u s c o a l s and s u b b i t u m i n o u s c o a l s i n a d d i t i o n t o l i g n i t e c a n be c o n v e r t e d t o e n v i r o n m e n t a l l y a c c e p t a b l e s o l i d fuels. These c o a l s c a n be u s e d d i r e c t l y a s a s o u r c e o f e n e r g y w i t h o u t f u r t h e r c l e a n i n g d u r i n g t h e combustion p r o c e s s , assuming a l l o f t h e s u l f u r i s e m i t t e d t o t h e atmosphere. With a l k a l i hydrothermally t r e a t e d c o a l s , a l l o f the s u l f u r i s n o t e m i t t e d t o the atmosphere. D u r i n g the d e s u l f u r i z a t i o n o p e r a t i o n , t h e c o a l s t r u c t u r e i s opened up t o g i v e a p r o d u c t h a v i n g a s p o n g e - l i k e m o r p h o l o g y ( s e e F i g u r e 2 ) . The p o r o u s s t r u c t u r e a l l o w s t h e a l k a l i t o p e n e t r a t e t h e c o a l p a r t i c l e s and subsequently t o r e a c t w i t h t h e f u n c t i o n a l groups, f o r example, c a r b o x y l i c a c i d groups, o f t h e c o a l molecules. A l s o , the a l k a l i 2

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

9

200

COAL

HEAT

DESULFURIZATION

EXCHANGER

GRINDING MIXING H I G H - SSUULLFFUURR COAL

^

^

j

REGENERATED LEACHANT

TANK

FILTER

S U L F U R REMOVAL AUTOCLAVE

HZ

J]H** DRYER

CLEAN

SPENT LEACHANT

SULFUR

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch016

SULFUR RECOVERY PLANT

Figure 1.

COAL

FOR POWER P L A N T S AND INDUSTRIAL BOILERS

LEACHANT REGENERATION

Schematic of hydrothermal coal process

Figure 2. Comparison of morphology of untreated (top) and HTT coal (bottom)

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

16.

STAMBAUGH

Hydrothermal Coal Process

Table I .

S u l f u r Emissions of Low-Sulfur Coals from Hydrothermal Coal Process

C o a l Source Seam

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch016

201

S0 Raw

o

Equivalent (lb/10 HTT Coal

6

Btu) Coal

Laboratory scale Lower K i t t a n n i n g Upper F r e e p o r t Ohio 6 Pittsburgh 8 . Pittsburgh Lignite Western

2.2 2.4 3.9 4.6 3.4 1.5 1.0

0.9 0.9 1.2 0.9 0.7 1.2 0.3

Prepilot plant Lower K i t t a n n i n g Upper F r e e p o r t

4.0 2.4

1.1 0.8

i s p h y s i c a l l y d e p o s i t e d w i t h i n and on t h e c o a l p a r t i c l e s . Conseq u e n t l y , i n a d d i t i o n to h a v i n g a reduced s u l f u r c o n t e n t , the h y d r o t h e r m a l l y t r e a t e d c o a l i s impregnated w i t h a l k a l i which a c t s as a s u l f u r s c a v e n g e r d u r i n g t h e c o m b u s t i o n p r o c e s s . I n some r e c e n t c o m b u s t i o n s t u d i e s s u p p o r t e d by EPA ( 1 ) , 41.4-75.7% o f t h e s u l f u r r e m a i n i n g i n t h e t r e a t e d c o a l was c a p t u r e d by t h e a l k a l i i n t h e t r e a t e d c o a l s , as shown i n T a b l e I I . ( T h i s c o m b u s t i o n s t u d y was c o n d u c t e d i n a 1 - l b / h r l a b o r a t o r y c o m b u s t i o n f a c i l i t y . ) S t a c k g a s e s c o n t a i n e d 120-290 ppm SO2 e q u i v a l e n t t o a b o u t 0.3-0.6 l b S 0 / 1 0 6 B t u . T h e o r e t i c a l l y , a s s u m i n g no s u l f u r c a p t u r e , t h e s t a c k g a s e s w o u l d have c o n t a i n e d 490-650 ppm SO2, e q u i v a l e n t t o a b o u t 1.0-1.5 l b S 0 / 1 0 B t u . T h i s added f e a t u r e o f t h e h y d r o t h e r m a l p r o c e s s g r e a t l y i n c r e a s e s t h e number o f c o a l s w h i c h can be u s e d as a s o u r c e o f c l e a n e n e r g y , e s p e c i a l l y t h o s e c o a l s c o n t a i n i n g r e l a t i v e l y h i g h c o n c e n t r a t i o n s of o r g a n i c s u l f u r not s u b j e c t t o r e m o v a l by m e c h a n i c a l c l e a n i n g . 2

6

2

Metal Extraction. Hydrothermal treatment r e s u l t s i n the e x t r a c t i o n o f a number o f t h e t r a c e m e t a l s . Examples of these a r e shown i n T a b l e I I I . T h e r e f o r e , t r a c e m e t a l e m i s s i o n s f r o m t h e c o m b u s t i o n o f h y d r o t h e r m a l l y t r e a t e d c o a l s h o u l d be l o w e r t h a n t h o s e f r o m t h e c o m b u s t i o n o f t h e c o r r e s p o n d i n g raw c o a l s . F u r t h e r m e t a l e x t r a c t i o n i s a c h i e v e d by c h e m i c a l l y d e a s h i n g the h y d r o t h e r m a l l y t r e a t e d c o a l w i t h d i l u t e a c i d , f o r example, sulfuric acid. As an i l l u s t r a t i o n , t h e a s h c o n t e n t o f u n t r e a t e d c o a l s f r o m O h i o , K e n t u c k y , West V i r g i n i a , and P e n n s y l v a n i a r a n g e d f r o m 4.6-13.2%; a s h c o n t e n t o f c h e m i c a l l y d e a s h e d h y d r o t h e r m a l l y t r e a t e d c o a l s r a n g e d f r o m 0.7-5.3%. Improved C o m b u s t i o n B e h a v i o r . C e r t a i n general combustion c h a r a c t e r i s t i c s o f b o t h t h e raw and t r e a t e d c o a l s , s u c h as

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

S0

2

(ppm)

(%)

30.7

41.4

120 75.7

1910 —

1115

290

493

1610

Westland Raw C o a l

1877

495

Martinka Coal Mixed Leachant

Coals

220

250

66.2

651

580

56.9

Westland Coal Mixed Leachant

Westland Coal Caustic

M a r t i n k a c o a l r e p r e s e n t s t h e Lower K i t t a n i n g Seam; W e s t l a n d c o a l r e p r e s e n t s t h e P i t t s b u r g h Seam.

Sulfur capture

SO^ i n s t a c k gas (ppm)

Theoretical

Martinka Coal Caustic

S u l f u r C a p t u r e by A l k a l i i n HTT

Martinka Raw C o a l

Table I I .

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch016

16.

STAMBAUGH

Hydrothermal Coal Process

Table I I I .

203

T o x i c M e t a l s E x t r a c t e d by H y d r o t h e r m a l Treatment o f C o a l

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch016

Concentration Metal

Raw C o a l

Arsenic Beryllium Boron Lead Thorium Vanadium

25 10 75 20 3 40

Average v a l u e s from 3 Ohio

a

(ppm)

Treated

Coai

a

2 3 4 5 0.5 2 coals.

i g n i t i o n t e m p e r a t u r e and r e a c t i v i t y , were d e t e r m i n e d q u a n t i t a t i v e l y f r o m t h e d e r i v a t i v e t h e r m o g r a v i m e t r i c (dTGA) and t h e d i f f e r e n t i a l t h e r m a l (DTA) f u e l a n a l y s e s . The r e s u l t s o f t h e dTGA a n d DTA a r e summarized i n T a b l e s I V and V, r e s p e c t i v e l y . From t h e s e a n a l y s e s , t h e c o m b u s t i o n c h a r a c t e r i s t i c s o f t h e s e c o a l s i n terms o f i g n i t i o n , r e a c t i v i t y , and p o s s i b l y f l a m m a b i l i t y may have b e e n i m p r o v e d by t h e h y d r o t h e r m a l t r e a t m e n t . F o r e x a m p l e , t h e i g n i t i o n t e m p e r a t u r e o f W e s t l a n d c o a l was r e d u c e d f r o m 426°-344°C ( T a b l e I V ) , a r e d u c t i o n o f 82°C, by t r e a t i n g t h e c o a l w i t h s o d i u m h y d r o x i d e and t h e m i x e d l e a c h a n t s y s t e m s . A s i m i l a r e f f e c t was n o t e d by h y d r o t h e r m a l t r e a t m e n t o f t h e M a r t i n k a c o a l w i t h these leachant systems. T h i s was e x p e c t e d i n v i e w o f o t h e r h y d r o t h e r m a l work w h i c h has been c o n d u c t e d a t B a t t e l l e - C o l u m b u s . I n t h i s w o r k , h y d r o t h e r m a l t r e a t m e n t o f c o a l s r e s u l t e d i n a l t e r a t i o n and m o d i f i c a t i o n o f t h e c o a l s t r u c t u r e t o a more s i m p l i f i e d s t r u c t u r e . This i s e v i d e n c e d by t h e f a c t t h a t t h e l i q u i d p r o d u c t s f r o m t h e p y r o l y s i s o f HTT c o a l s c o n t a i n e d l e s s a s p h a l t e n e s t h a n t h e l i q u i d p r o d u c t s f r o m t h e c o r r e s p o n d i n g r a w c o a l s ( 2 ) . The l o w e r m o l e c u l a r w e i g h t o r g a n i c l i q u i d s f r o m t h e HTT c o a l s s h o u l d have a l o w e r i g n i t i o n t e m p e r a t u r e and a h i g h e r d e g r e e o f f l a m m a b i l i t y t h a n t h e h i g h e r m o l e c u l a r w e i g h t l i q u i d s from t h e raw c o a l s . The i n c r e a s e d r e a c t i v i t y i s r e f l e c t e d i n T a b l e V. F o r e x a m p l e , t r e a t m e n t o f t h e M a r t i n k a and W e s t l a n d c o a l s w i t h t h e m i x e d l e a c h a n t s y s t e m r e s u l t e d i n HTT c o a l s w h i c h b u r n e d o u t a t a maximum o f a b o u t 470°C w h e r e a s t h e r a w c o a l s b u r n e d o u t a t a b o u t 585°-600°C. A s i m i l a r e f f e c t , b u t n o t t o t h i s d e g r e e , was observed w i t h t h e sodium h y d r o x i d e - t r e a t e d c o a l s . W h i l e t h e r e may n o t be a d i r e c t c o r r e l a t i o n between c o m b u s t i o n and g a s i f i c a t i o n , h y d r o t h e r m a l t r e a t m e n t o f c o a l w i t h t h e m i x e d l e a c h a n t s y s t e m i n c r e a s e s s t e a m g a s i f i c a t i o n and h y d r o g a s i f i c a t i o n r a t e s by a s much as 40-50 f o l d ( 3 ) . T h i s h a s been a t t r i b u t e d t o a l t e r a t i o n and m o d i f i c a t i o n o f t h e c o a l s t r u c t u r e and t o i m p r e g n a t i o n o f t h e c o a l p a r t i c l e w i t h a c a t a l y s t , i n t h i s case c a l c i u m and/or sodium. T h i s work h a s a l s o

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

range^

622

-

243 432

615

233 426

252 344 488 564 263 360 508 578

Martinka Coal Sodium Treated

275

19.0

250-600

Martinka Raw C o a l

305

21.5

230-570

275

27.5

240-510

Martinka Coal NaOH Leachant

285

23.0

240-465

310

27.0

270-470

Martinka Coal Mixed Leachant

252 376 493 553

Martinka Coal Mixed Leachant

Westland Coal Mixed Leachant

Coals

268 344 494 555

Westland Coal Mixed Leachant

TGA p e r f o r m e d w i t h Cahn E l e c t r o b a l a n c e a t 15°C/min and a i r f l o w o f 800 m l / m i n . T e m p e r a t u r e r a n g e o v e r w h i c h most o f t h e sample i s l o s t .

320

17.5

220-585

Westland Raw C o a l

Westland Coal NaOH Leachant

T h e r m o g r a v i m e t i c A n a l y s e s o f Raw and HTT

T e m p e r a t u r e a t maximum r a t e o f w e i g h t l o s s (°C)

Maximum r a t e o f w e i g h t l o s s (mg/min)

Temperature

TABLE V.

S t a r t i n g e x o t h e r m (°C) I g n i t i o n p o i n t (°C) S e c o n d a r y e x o t h e r m (°C) End o f e x o t h e r m (°C)

Martinka Raw C o a l

Westland Coal Sodium Treated

D i f f e r e n t i a l Thermal A n a l y s e s o f C o a l Samples i n an A t m o s p h e r e o f A i r

We s t l a n d Raw C o a l Low A s h

Table IV.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch016

>

16.

STAMBAUGH

Hydrothermal Coal Process

shown t h a t t h e m i x e d l e a c h a n t - t r e a t e d c o a l i s more r e a c t i v e the sodium h y d r o x i d e - t r e a t e d c o a l .

205 than

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch016

Summary Hydrothermal p r o c e s s i n g i s a p o t e n t i a l technology f o r c o n v e r t i n g a v a r i e t y o f m a j o r seam, h i g h - s u l f u r c o a l s and l i g n i t e to c l e a n s o l i d f u e l s having a t o t a l s u l f u r content e q u i v a l e n t t o o r l e s s t h a n 1.2 l b SO2/IO" B t u . D u r i n g t h e t r e a t m e n t , t h e c o a l s are impregnated w i t h a l k a l i which a c t s as a s u l f u r scavenger, thereby reducing s u l f u r emissions s t i l l f u r t h e r d u r i n g combustion. The p r o c e s s i s a l s o e f f e c t i v e i n r e m o v i n g t r a c e m e t a l s s u c h a s b e r y l l i u m , b o r o n , v a n a d i u m , and a r s e n i c ; t h e r e f o r e , t h e g a s e o u s e m i s s i o n s f r o m c o m b u s t i o n o f HTT c o a l s s h o u l d be l e s s p o l l u t i n g i n terms o f s u l f u r and t r a c e m e t a l e m i s s i o n s t h a n f r o m r a w c o a l s . Hydrothermal treatment a l s o appears t o improve t h e combustion c h a r a c t e r i s t i c s o f c o a l i n terms o f i g n i t i o n , r e a c t i v i t y , and possibly flammability. Thus, h y d r o t h e r m a l treatment c o n v e r t s a t l e a s t c e r t a i n h i g h sulfur coals to environmentally acceptable s o l i d fuels with p o t e n t i a l l y improved combustion c h a r a c t e r i s t i c s . These c o a l s a r e p o t e n t i a l s o u r c e s o f e n e r g y f o r p u l v e r i z e d , s t o k e r , and c o a l s l u r r y combustion. Acknowledgement R e s u l t s a s r e p o r t e d were s u p p o r t e d i n p a r t by t h e B a t t e l l e E n e r g y P r o g r a m and i n p a r t by t h e U.S. E n v i r o n m e n t a l P r o t e c t i o n A g e n c y , R e s e a r c h - T r i a n g l e P a r k , NC, u n d e r C o n t r a c t No. 68-02-2119.

Literature Cited

1. Stambaugh, E. P., Levy, Α., Giammar, R. D., Sekhar, K. C., "Hydrothermal Coal Desulfurization with Combustion Results," Proceedings of the Fourth National Conference (October 3-7, 1976) 386-394. 2. Stambaugh, E. P., Feldmann, H. F. , Liu, K. T., Sekhar, K. C., "Novel Concept for Improved Pyrolysis Feedstock Production," 173rd National Meeting American Chemical Society, New Orleans, Louisiana (March 21-25, 1977). 3. Stambaugh E. P., Miller, J. F., Tam, S. S., Chauhan, S. P., Feldmann, H. F., Carlton, H. E., Nack, H., Oxley, J. H., "Battelle Hydrothermal Coal Process," 12th Air Pollution and Industrial Hygiene Conference on Air Quality Management in EPI, University of Austin, Austin, Texas (January 1976).

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

17 Coal Desulfurization by Low-Temperature Chlorinolysis

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch017

GEORGE C. HSU, JOHN J. KALVINSKAS, PARTHA S. GANGULI, and GEORGE R. GAVALAS* Jet Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Drive, Pasadena, CA 91103 Since most of the coals in this country, particularly the eastern and mid-western coals, have a high sulfur content (>2%), there is a need for an economical process of converting high-sulfur coals to clean fuel (<1.2 lbs of SO emission per million Btu by EPA standards) so that coal can be used as a source of energy without causing serious air pollution. Among the three principal methods for precombustion desulfurization of coal - physical depyriting, chemical desulfurization (1,2,3,4), and coal conversion to low-sulfur liquid and gaseous fuels, the potential of chemical methods looks promising in terms of both total sulfur removal and processing cost. The principal chemical methods for coal desulfurization involve treatment with either oxidizing agents (1,2,3) or basic media (4)at elevated temperature and pressure. For example, the method of oxidation (1) by contacting an aqueous slurry of coal with air at pressures up to 1000 psi and temperatures of 140° - 200°C can remove more than 90% of the pyritic sulfur and up to 40% of the organic sulfur as sulfuric acid. Fuel value losses are usually less than 10%. 2

Most o f t h e e a r l i e r s t u d i e s (5,6,7,8,9) o n c h l o r i n o l y s i s o f c o a l were conducted t o understand t h e c h e m i s t r y o f t h e p r o c e s s , t o p r o d u c e a n o n - c a k i n g f u e l s u i t a b l e f o r b u r n i n g , and t o i n v e s t i g a t e the p o s s i b l e p r o d u c t i o n o f c h l o r o h y d r o c a r b o n s from c o a l . However, t h e r e was a l i m i t e d amount o f w o r k (10,11) on d e s u l f u r i z a t i o n by c h l o r i n a t i o n o f c o a l i n t h e g a s p h a s e a t h i g h t e m p e r a t u r e (400°C) and e l e v a t e d p r e s s u r e . These s t u d i e s showed t h a t b o t h o r g a n i c and i n o r g a n i c s u l f u r c o u l d be removed t o a c e r t a i n e x t e n t , b u t t h e l o s s o f c o a l was more t h a n 2 0 % and b e c a u s e o f h i g h - t e m p e r a t u r e c h l o r i n a t i o n , s a t i s f a c t o r y d e c h l o r i n a t i o n a f t e r w a r d s was n o t a c h i e v e d . A few s t u d i e s ( 1 2 ) on t h e c h l o r i n a t i o n o f c o a l i n a n aqueous m e d i a a t 25°C r e s u l t e d i n p o o r r e m o v a l o f s u l f u r .

P r o f e s s o r , Chemical E n g i n e e r i n g Department, C a l i f o r n i a I n s t i t u t e o f T e c h n o l o g y , P a s a d e n a , C a l i f o r n i a 91125

206

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

17.

Hsu E T A L .

207

Low-Temperature Chlorinolysis

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch017

T h i s c h a p t e r i s an u p d a t e d v e r s i o n o f the p r e s e n t a t i o n (13) g i v e n i n 1976 a t the ACS C e n t e n n i a l M e e t i n g a t San F r a n c i s c o . It i n c l u d e s some r e c e n t e x p e r i m e n t a l r e s u l t s s h o w i n g the f e a s i b i l i t y of removing s u l f u r , p a r t i c u l a r l y o r g a n i c s u l f u r , from h i g h - s u l f u r c o a l s by a s i m p l e method o f l o w - t e m p e r a t u r e c h l o r i n o l y s i s f o l l o w e d by h y d r o l y s i s and d e c h l o r i n a t i o n . The c h e m i c a l f e a s i b i l i t y o f s u l f u r r e m o v a l by c h l o r i n o l y s i s r a t h e r t h a n t h e d e t a i l e d e n g i n e e r i n g p r o c e s s i s e m p h a s i z e d . The c o n c e p t o f t h i s c h l o r i n a t i o n method i s d e s c r i b e d , and e x p e r i m e n t a l r e s u l t s and d i s c u s s i o n o f t h i s method of d e s u l f u r i z a t i o n a r e p r e s e n t e d f o r two b i t u m i n o u s c o a l s . On the b a s i s o f e x p e r i m e n t a l d a t a , t h e l o w - t e m p e r a t u r e c h l o r i n o l y s i s d e s u l f u r i z a t i o n method p r o v i d e s a number o f b a s i c a d v a n tages that include: (1)

A h i g h degree of s u l f u r removal;

s u l f u r removal, p a r t i c u l a r l y organic

(2)

A d d i t i o n a l removal of t r a c e m e t a l c o n c e n t r a t i o n s cont a i n e d i n the o r i g i n a l c o a l t h a t r e d u c e s p o t e n t i a l l y h a z a r d o u s e m i s s i o n s t o the a t m o s p h e r e ;

(3)

A r e l a t i v e l y simple coal-processing operation mostly at low t e m p e r a t u r e s and a t m o s p h e r i c p r e s s u r e w h i c h t r a n s lates into a low-cost process;

(4)

A beneficiation b u s t i o n as w e l l

(5)

Improved c o a l f e e d s t o c k s f o r c o m b u s t i o n and g a s i f i c a t i o n o p e r a t i o n s s i n c e t r e a t e d c o a l i s n o n - c a k i n g and nonswelling.

o f t h e c o a l f o r use i n d i r e c t - f i r e d comas i n g a s i f i c a t i o n p r o c e s s e s ;

Concept of C o a l D e s u l f u r i z a t i o n

by

Low-Temperature

Chlorinolysis

Chlorination. The e s s e n t i a l , a l t h o u g h c o n s i d e r a b l y s i m p l i f i e d , d e s u l f u r i z a t i o n r e a c t i o n s i n v o l v e d d u r i n g c h l o r i n o l y s i s of c o a l , as i d e n t i f i e d i n s u l f u r and p o l y m e r c h e m i s t r y l i t e r a t u r e and s u p p o r t e d by J e t P r o p u l s i o n L a b o r a t o r y e x p e r i m e n t a l r e s u l t s , may be i l l u s t r a t e d as f o l l o w s : Because o f h i g h s t e r i c a c c e s s i b i l i t y o f b i c o v a l e n t s u l f u r and the e l e c t r o n - r e l e a s i n g and e l e c t r o n - d e m a n d i n g n a t u r e o f the s u l f u r atom, the c a r b o n - s u l f u r ( s u l f i d e ) and s u l f u r - s u l f u r ( d i s u l f i d e ) bonds i n c o a l w i l l be h i g h l y r e a c t i v e . The s c i s s i o n o f c a r b o n s u l f u r and s u l f u r - s u l f u r bonds i n o r g a n i c compounds has been exp e r i m e n t a l l y d e m o n s t r a t e d i n p o l y m e r and s u l f u r c h e m i s t r y , (14)

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

COAL

208

OS

DESULFURIZATION

Bond C l e a v a g e :

+ R-S-R' + C l where R and R sulfur.

f

H

- Cl

f

^

^ . RSC1 + R C l

(1)

r e p r e s e n t h y d r o c a r b o n g r o u p s , and S s t a n d s f o r

S-S Bond ( e l e c t r o p h i l i c RS-SR

1

cleavage):

+ Cl

- Cl

^

^

RSC1 + R ' S C l

(2)

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch017

Conversion to Sulfates: Sulfenyl chloride i s oxidized the f o l l o w i n g r e a c t i o n s : CI

, HO * - RS0 C1

HO

f L

RSC1

R S 0 H + HC1

2

RSC1 + 2 C 1

C 1

RSC1

H

2'

RSO^

+ 3H 0

2

2

2°

RS0 C1

Δ

—

+ 4H 0

0

+ 5HC1

—^-S0

(3b)

+ RC1

4

(4a)

RC1 + H S 0 , + 6HC1

o

2

(3a)

3

2

RSC1 + 3 C 1

Pyritic

t o s u l f o n a t e or s u l f a t e a c c o r d i n g t o

(4b)

o

2

2

4

Sulfur:

R e a c t i o n s (15) a r e summarized a s f o l l o w s : FeS

+ 2C1

2

2FeS + 7 C 1 2FeS

S

2

C 1

2

+

8 H

+

2° S

5 C 1

RH + 2 FeS

2

+ 7C1

2

C 1

*-2FeCl

2

+ 10SC1

2

*-FeCl

2

2

+ S C1

3

+ 4SC1

2

2FeCl

2

^

2

2

2

H

2

S

0

+

4

(5)

2

(6)

+ 7S C1

3

1

2

2

2

H

C

1

(

(7)

2

f a s t

)

* - R S C l + HC1 ( s l o w ) 2

+ 8H 0 2

FeCl

2

+ 2H S0 2

4

+ 12HC1.

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

W (9) (10)

17.

Hsu E T A L .

Low-Temperature

Chlorinolysis

209

These r e a c t i o n s a r e e x o t h e r m i c i n n a t u r e and o c c u r f a v o r a b l y a t m o d e r a t e t e m p e r a t u r e . The o v e r a l l c h l o r i n e r e q u i r e m e n t t o c o n v e r t o r g a n i c s u l f u r t o s u l f o n a t e s u l f u r and s u l f a t e s u l f u r i s a p p r o x i m a t e l y 3 m o l e s o f C l and 4 m o l e s o f C I 2 , r e s p e c t i v e l y , p e r m o l e o f o r g a n i c s u l f u r and 3.5 m o l e s o f C l p e r m o l e o f i n o r g a n i c s u l f u r . I n t h e p r e s e n c e o f w a t e r and a t a t e m p e r a t u r e ( i . e . , >50°C) h i g h e r t h a n room t e m p e r a t u r e , t h e S2CI2 formed f r o m FeS2 c h l o r i n a t i o n i s r e a d i l y c o n v e r t e d t o HC1 a n d H2SO4. However a t room temp e r a t u r e and w i t h o u t adequate m o i s t u r e , t h i s r e a c t i o n i s slow, and S2CI2 may r e a c t w i t h o r g a n i c compounds t o f o r m o r g a n o - s u l f u r compounds. On t h e o t h e r h a n d , i n a n o r g a n i c s o l v e n t a t a s l i g h t l y elevated temperature, the r a t e of c h l o r i n a t i o n of c o a l i s slower t h a n i n aqueous m e d i a a t room t e m p e r a t u r e . A l s o o r g a n i c s o l v e n t media g i v e a g r e a t e r d e g r e e o f s t r u c t u r a l l o o s e n i n g o f c o a l and c o n s e q u e n t l y more o r g a n i c s u l f u r may be removed w i t h a l e s s e r d e g r e e o f c h l o r i n a t i o n . S t r u c t u r a l l o o s e n i n g o f c o a l by t h e a c t i o n of t h e o r g a n i c s o l v e n t w i l l make c h l o r i n e more a c c e s s i b l e t o s u l f u r compounds. H i g h c h l o r i n e s o l u b i l i t y i n a n o r g a n i c s o l v e n t may a l s o be a d v a n t a g e o u s f o r d e s u l f u r i z a t i o n . M o r e o v e r , a n o r g a n i c s o l v e n t may d i s s o l v e some o f t h e o r g a n o - s u l f u r compounds. C h l o r i n a t i o n o f the c o a l m a t r i x i s m a i n l y a s u b s t i t u t i o n r e a c t i o n , and hydrogen c h l o r i d e i s evolved as a product. Chlorine i ncoal chlorinated u n d e r m i l d c o n d i t i o n s c a n be removed c o m p l e t e l y a s h y d r o g e n c h l o r i d e by h e a t i n g a t 300°-550°C. C h l o r i n a t i o n a t h i g h t e m p e r a t u r e and p r e s s u r e r e s u l t s i n c o a l w h i c h i s d i f f i c u l t t o d e c h l o r i n a t e . A f t e r c h l o r i n o l y s i s c o a l becomes n o n - v o l a t i l e , a s i n d i c a t e d by no t a r f o r m a t i o n on h e a t i n g up t o 550°C. O n l y HC1 gas i s e v o l v e d on h e a t i n g o f c h l o r i n a t e d c o a l . A l s o c h l o r i n a t e d c o a l becomes n o n - c a k i n g and n o n - s w e l l i n g upon h e a t i n g . I t appears reasonable t o i n f e r that the carbon present i n s t r u c t u r e s normally g i v i n g r i s e t o t h e f o r m a t i o n o f t a r , w h i c h may be assumed t o be hydroaroraatic o r other r e a d i l y dehydrogenated s t r u c t u r e s , i s r e t a i n e d i n t h e s o l i d r e s i d u e by a r o m a t i z a t i o n , c r o s s l i n k i n g , o r o t h e r forms o f c o n d e n s a t i o n r e a c t i o n s . 2

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch017

2

Hydrolysis. C h l o r i n a t e d c o a l i s hydrolyzed t o produce hydroc h l o r i c acid according t o the following reaction: RC1

+ H 0 2

ROH + HC1

(11)

where R r e p r e s e n t s a h y d r o c a r b o n g r o u p i n c o a l . The s u l f u r c o n v e r t e d t o s u l f a t e s o r s u l f o n a t e i s w a t e r s o l u b l e and i s l e a c h a b l e by w a t e r w a s h i n g a t 60°C f o r r e t e n t i o n t i m e s up to 2 h r i n a s t i r r e d r e a c t o r . Dechlorination. After hydrolysis, thecoal i s dechlorinated by h e a t i n g i n s t e a m o r a n i n e r t g a s a t m o s p h e r e . T h i s c a n be accomplished e a s i l y because o f c h l o r i n a t i o n a t low temperature. The p o s s i b l e r e a c t i o n s d u r i n g d e c h l o r i n a t i o n a r e :

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

210

C O A L DESULFURIZATION

1)

i n an i n e r t gas

atmosphere: f

RH + R C l

^-RR

1

+ HC1

(12)

and 2)

i n steam a t m o s p h e r e : RCl(s) + H 0(g)

*-R0H(s) + HCl(g)

2

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch017

T h i s r e a c t i o n i s e n d o t h e r m i c and p r o c e e d s f a v o r a b l y m o d e r a t e l y h i g h t e m p e r a t u r e (300°-500°C).

(13) at

a

A c c o r d i n g t o t h e l i t e r a t u r e (16) s t e a m w i l l a s s i s t p y r i t i c s u l f u r r e m o v a l . D e c h l o r i n a t i o n i n a s t e a m a t m o s p h e r e p r o c e e d s by s u b s t i t u t i o n o f - C I i n c h l o r i n a t e d c o a l by -OH and p o s s i b l y -H g r o u p s f r o m H2O. No l o s s o f h e a t i n g v a l u e i s e x p e r i e n c e d by t h e p r o c e s s e d c o a l when d e c h l o r i n a t e d i n a s t e a m a t m o s p h e r e . Laboratory

Processing

The l a b o r a t o r y p r o c e s s i n g o f c o a l f o r d e s u l f u r i z a t i o n by c h l o r i n o l y s i s i s d e p i c t e d i n F i g u r e 1. C h l o r i n e gas i s b u b b l e d t h r o u g h a s u s p e n s i o n o f powdered (100-200 mesh) m o i s t h i g h s u l f u r c o a l i n m e t h y l c h l o r o f o r m a t 74°C and a t m o s p h e r i c p r e s s u r e f o r 1 - 4 h r . The c o a l s l u r r y i s d i s t i l l e d f o r s o l v e n t r e c o v e r y . The c h l o r i n a t e d c o a l i s h y d r o l y z e d w i t h w a t e r a t 50°-70°C f o r 2 h r and t h e n f i l tered. The c o a l f i l t e r c a k e i s d r i e d and d e c h l o r i n a t e d by h e a t i n g a t 300°-500°C i n a steam o r vacuum a t m o s p h e r e f o r a p p r o x i m a t e l y 1 hr. A n a l y s i s of t h e o r i g i n a l and p r o c e s s e d c o a l was made f o r o r g a n i c , p y r i t i c , and s u l f a t e s u l f u r as w e l l as an u l t i m a t e a n a l y s i s o f t h e c o a l i n c l u d i n g an a n a l y s i s f o r t r a c e m e t a l r e m o v a l by the d e s u l f u r i z a t i o n p r o c e s s . Coal. Two h i g h - s u l f u r c o a l s were used f o r e x p e r i m e n t a l studies. The I l l i n o i s No. 5 h i g h - v o l a t i l e b i t u m i n o u s c o a l f r o m t h e H i l l s b o r o m i n e had 4.77% t o t a l s u l f u r c o n t e n t . The o t h e r h i g h v o l a t i l e b i t u m i n o u s c o a l was a K e n t u c k y No. 9 c o a l f r o m H a m i l t o n , K e n t u c k y . P r o x i m a t e a n a l y s e s of t h e s e two c o a l s a r e g i v e n i n Table I. TABLE I .

Proximate A n a l y s i s

D a t a o f Two

Tested Coals

Fixed Carbon

Volatile Matter

Moisture

Illinois No. 5

42.74%

36.35%

9.88%

11.03%

Kentucky No. 9

52.45%

35.0%

4.49%

8.06%

Coal

Ash

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch017

17.

HSU

ET

AL.

Low-Temperature Chlorinolysis

211

Apparatus. The c h l o r i n a t i o n u n i t c o n s i s t s o f a 1000-ml g l a s s k e t t l e h e a t e d by a c o n s t a n t t e m p e r a t u r e b a t h and e q u i p p e d w i t h a s t i r r e r , a c h l o r i n e b u b b l e r made up o f f r i t t e d g l a s s d i s c s , a s l u r r y sampling l i n e , a r e f l u x condenser s u i t a b l e f o r complete t o t a l r e f l u x o f t h e s o l v e n t , and a gas h o l d e r . The hydrolyzer c o n s i s t s o f a 2000-ml g l a s s k e t t l e e q u i p p e d w i t h a h e a t i n g m a n t l e , a temperature c o n t r o l l e r , a s t i r r e r , a t o t a l r e f l u x condenser, a s l u r r y s a m p l i n g l i n e , and a gas h o l d e r . The d e c h l o r i n a t i o n u n i t c o n s i s t s o f a r o t a r y d r y e r (1/2 i n . i . d . χ 24 i n . l o n g ) e q u i p p e d w i t h a h e a t e r and a t e m p e r a t u r e c o n t r o l l e r . The d r y e r i s made up o f a s t e e l s h e l l w i t h a p r o t e c t i v e l i n i n g t h a t i n c l u d e s a c i d r e s i s t a n t b r i c k s u i t a b l e f o r o p e r a t i o n s up t o 600°C and a t e l e v a t e d p r e s s u r e . The d r y e r has p r o v i s i o n f o r vacuum, s t e a m , o r i n e r t gas o p e r a t i o n . The c o a l s a m p l e i s h e a t e d i n s i d e t h e r o t a r y d r y e r i n vacuum, s t e a m , o r i n e r t gas a t m o s p h e r e . The o u t g o i n g g a s e s p a s s t h r o u g h c o l d t r a p s t o a gas h o l d e r . For e x a m p l e , steam f r o m a steam g e n e r a t o r f l o w s o v e r t h e h o t c o a l a t 300°-450°C i n s i d e t h e d r y e r f o r l e s s t h a n 1 h r . Results

and

Discussion

E x p e r i m e n t a l d a t a o b t a i n e d w i t h a h i g h - s u l f u r (4.77%) b i t u m i n ­ ous c o a l f r o m H i l l s b o r o , I l l i n o i s a r e p r e s e n t e d i n T a b l e I I . C h l o r i n a t i o n was c a r r i e d o u t i n a s t i r r e d r e a c t o r o p e r a t i n g a t a t m o s p h e r i c p r e s s u r e and 74°C. C h l o r i n e was b u b b l e d i n t o t h e r e a c ­ tor f o r 1 hr. Powdered c o a l b e t w e e n 100 and 150 mesh was used w i t h 50% w a t e r and a m e t h y l c h l o r o f o r m - t o - c o a l r a t i o o f 2/1. The o r i g i ­ n a l s u l f u r c o n t e n t o f t h e c o a l c o n s i s t e d o f 1.89% p y r i t i c , 2.38% o r g a n i c , and 0.5% s u l f a t e s u l f u r . A f t e r h y d r o l y s i s and w a t e r wash­ i n g o f t h e c h l o r i n a t e d c o a l a t 60°C f o r 2 h r i n a s t i r r e d r e a c t o r w i t h e x c e s s w a t e r , t h e p y r i t i c s u l f u r was 0.43%, o r g a n i c s u l f u r was 0.72%, and s u l f a t e s u l f u r was 0.35%. I t i s assumed t h a t a d d i ­ t i o n a l w a t e r w a s h i n g w o u l d remove t h e s u l f a t e s u l f u r c o m p l e t e l y . The h y d r o l y s i s s o l u t i o n c o n t a i n e d m a i n l y and o t h e r s o l ­ u b l e s u l f a t e and c h l o r i d e compounds. The e x p e c t e d o v e r a l l s u l f u r r e m o v a l was 76% w i t h a r e d u c t i o n o f c o a l s u l f u r f r o m 4.77% t o 1.153. R e s u l t s of a l l the experiments w i t h t h i s c o a l i n d i c a t e that removal of up t o 70% o r g a n i c s u l f u r , up t o 90% p y r i t i c s u l f u r , and 76% t o ­ t a l s u l f u r h a v e been a c h i e v e d by c u r r e n t c h l o r i n o l y s i s p r o c e d u r e s . A l t h o u g h t h e EPA s t a n d a r d s f o r r e s i d u a l s u l f u r (~0.7%) have n o t been met f o r t h i s h i g h - s u l f u r c o a l , t h e g u i d e l i n e s s h o u l d be met by f u r t h e r i m p r o v e m e n t s i n t h e p r o c e s s . C h l o r i n a t e d c o a l had an a v e r a g e o f 22% c h l o r i n e b e f o r e and 11% a f t e r the h y d r o l y s i s s t e p . D e c h l o r i n a t i o n o f t h e washed c o a l was c a r r i e d o u t ( T a b l e I I I ) a t 500° and 550°C under vacuum f o r 1 h r . The r e s i d u a l e l e m e n t a l c h l o r i n e c o n t e n t was 0.06 wt % a t 550°C and 0.15-0.3 wt % a t 500°C. F u r t h e r m o r e , h e a t i n g t h e powdered c o a l t o 450°C f o r 1 h r u n d e r a s t e a m a t m o s p h e r e gave a r e s i d u a l e l e m e n t a l c h l o r i n e c o n t e n t o f 0.064 wt %. These a r e compared w i t h t h e o r i g i ­ n a l e l e m e n t a l c h l o r i n e c o n t e n t o f 0.14%. T h e r e f o r e , d e c h l o r i n a t i o n of t h e c o a l i s n o t e x p e c t e d t o be a p r o b l e m .

HC1, H2SO4,

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

212

COAL

TABLE I I .

Sulfur

P r e l i m i n a r y C h l o r i n o l y s i s Data f o r Bituminous Coal ( H i l l s b o r o , 111.) D e s u l f u r i z a t i o n

Form

Pyritic Organic Sulfate Total

Raw C o a l (% S u l f u r )

a

1.89 2.38 0.50 4.77

'Up t o 90% p y r i t i c conditions.

S u l f u r Removal

Treated Coal (% S u l f u r ) a

Achieved

(%)

Expected b

77 70 30 69

0.43 0.72 0.35 1.50

A n a l y s e s by G a l b r a i t h L a b o r a t o r i e s , Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch017

DESULFURIZATION

77 70 100° 76

I n c . , K n o x v i l l e , Tenn.

s u l f u r r e m o v a l has been a c h i e v e d i n o t h e r

A d d i t i o n a l w a t e r w a s h i n g s h o u l d remove 100% o f s u l f a t e . *For a 3% s u l f u r b i t u m i n o u s c o a l w i t h same s u l f u r d i s t r i b u t i o n as t h i s c o a l , t h e 76% r e m o v a l l e v e l may meet t h e EPA s t a n d a r d o f 0.7% s u l f u r .

TABLE I I I .

Preliminary Dechlorination Bituminous Coal)

D a t a ( H i l l s b o r o , 111.

Dechlorination Temp (°C)

Coal Raw

coal

Chlorinated coal (after hydrolysis)

Time (hr)

Atmosphere

-

-

-

-

-

-

Elemental (wt

Chlorine %)

0.14 11.0

Dechlorinated

coal

450

1

steam

0.064

Dechlorinated

coal

500

1

vacuum

0.15-0.30

Dechlorinated

coal

550

1

vacuum

0.06

In Coal Desulfurization; Wheelock, T.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0064.ch017

17.

Hsu E T A L .

Low-Temperature Chlorinolysis

213

The k i n e t i c d a t a f o r c h l o r i n a t i o n and d e s u l f u r i z a t i o n o f I l l i n o i s b i t u m i n o u s c o a l (-100 mesh) a r e p r e s e n t e d i n F i g u r e 2. The i n i t i a l r a t e o f c h l o r i n a t i o n i s v e r y f a s t . The c h l o r i n e c o n ­ t e n t o f c o a l i s 2 3 % i n 1/2 h r and t h e n s l o w l y i n c r e a s e s t o 26% w i t h i n t h e n e x t lh h r . W i t h i n t h e 1/2-hr p e r i o d most o f t h e p y r i t i c s u l f u r and a p o r t i o n o f t h e o r g a n i c s u l f u r a r e c o n v e r t e d t o sulfate sulfur. I n t h e n e x t 1^-hr p e r i o d p y r i t i c and o r g a n i c s u l ­ fur are slowly converted to s u l f a t e s u l f u r . Based o n t h e s u l f u r b a l a n c e , t h e g a i n i n s u l f a t e s u l f u r i s e q u a l t o t h e combined r e d u c ­ t i o n o f p y r i t i c and o r g a n i c s u l f u r . The above r e a c t i o n s e x t e n d t o t h e h y d r o l y s i s p e r i o d . The o v e r a l l s u l f a t e compounds, c o n v e r t e d f r o m o r g a n i c s u l f u r , p y r i t i c s u l f u r and o r i g i n a l s u l f a t e s u l f u r , produced e i t h e r d i r e c t l y o r i n d i r e c t l y through s u l f o n a t e a r e removed f r o m c o a l i n t h e h y d r o l y s i s s t e p a s i n d i c a t e d by a n a n a l y ­ s i s of the h y d r o l y s i s s o l u t i o n . H e a t i n g v a l u e s o f t h e o r i g i n a l c o a l and o f t h e f i n a l t r e a t e d c o a l were 11052 B t u / l b and 11,340 B t u / l b , r e s p e c t i v e l y , on a n a s r e c e i v e d b a s i s . The f i n a l v a l u e r e p r e s e n t s a s l i g h t i n c r e a s e o v e r the o r i g i n a l v a l u e . The i n c r e a s e i s a t t r i b u t e d t o a d i f f e r e n c e i n moisture content, e t c . Trace element c o n c e n t r a t i o n s found i n the o r i g i n a l H i l l s b o r o , 111., b i t u m i n o u s c o a l a r e p r e s e n t e d i n T a b l e IV a l o n g w i t h t h e t r a c e e l e m e n t c o n c e n t r a t i o n s a f t e r c h l o r i n a t i o n and h y d r o l y s i s . P r e l i m i n a r y d a t a i n d i c a t e d a p p r e c i a b l e r e d u c t i o n s o f Pb, V a , Ρ, L i , Be, and A s . A number o f t h e s e t r a c e e l e m e n t s c a n p o s e s e r i o u s environmental p o l l u t i o n problems u n l e s s t h e i r c o n c e n t r a t i o n s a r e r e d u c e d by t h e c o a l p r e t r e a t m e n t . R e s u l t s o f a c h l o r i n o l y s i s experiment w i t h the a d d i t i o n of 0.5% A I C I 3 i n d i c a t e d t h a t A I C I 3 d i d n o t have any a d d i t i o n a l e f f e c t on t h e r e m o v a l o f o r g a n i c s u l f u r f r o m c o a l . Coal contains s u f f i ­ c i e n t i r o n t o form about 1 - 2 % FeCl3 d u r i n g c h l o r i n o l y s i s . This q u a n t i t y o f i r o n i n t h e f o r m o f F e C l 3 may be a d e q u a t e t o c a t a l y z e ionic chlorination reactions. R e s u l t s o f c h l o r i n o l y s i s e x p e r i