Coal Science. Volume 2 PDF
Preview Coal Science. Volume 2
CONTRIBUTORS Richard J. Baltisberger Zeinab Baset Bradley C. Bockrath John P. de Neufville Howard Freund Martin L. Gorbaty Stephen C. Mraw Kundan M. Patal Janet R. Pullen Krishna Raman Virgil I. Stenberg Neil F. Woolsey Franklin J. Wright Coal Science V O L U ME 2 Edited by MARTIN L. GORBATY Corporate Research-Science Laboratories Exxon Research and Engineering Company Linden, New Jersey JOHN W. LARSEN Department of Chemistry The University of Tennessee Knoxville, Tennessee IRVING WENDER Chemical and Petroleum Engineering Department The University of Pittsburgh Pittsburgh, Pennsylvania 1983 ACADEMIC PRESS A Subsidiary of Harcourt Brace Jovanovich, Publishers New York London Paris San Diego San Francisco Sao Paulo Sydney Tokyo Toronto COPYRIGHT © 1983, BY ACADEMIC PRESS, INC. ALL RIGHTS RESERVED. NO PART OF THIS PUBLICATION MAY BE REPRODUCED OR TRANSMITTED IN ANY FORM OR BY ANY MEANS, ELECTRONIC OR MECHANICAL, INCLUDING PHOTOCOPY, RECORDING, OR ANY INFORMATION STORAGE AND RETRIEVAL SYSTEM, WITHOUT PERMISSION IN WRITING FROM THE PUBLISHER. ACADEMIC PRESS, INC. 111 Fifth Avenue, New York, New York 10003 United Kingdom Edition published by ACADEMIC PRESS, INC. (LONDON) LTD. 24/28 Oval Road, London NW1 7DX ISBN 0-12-150702-5 ISSN 0730-5397 This publication is not a periodical and is not subject to copying under CONTU guidelines. PRINTED IN THE UNITED STATES OF AMERICA 83 84 85 86 9 8 7 6 5 4 3 2 1 Contributors Numbers in parentheses indicate the pages on which the authors' contributions begin. Richard J. Baltisberger (125), Department of Chemistry, University of North Dakota, Grand Forks, North Dakota 58202 Zeinab Baset1 (1), Exxon Research and Engineering Company, Linden, New Jersey 07036 Bradley C. Bockrath (65), U.S. Department of Energy, Pittsburgh Energy Technology Center, Pittsburgh, Pennsylvania 15236 John P. de Neufville2 (1), Exxon Research and Engineering Company, Linden, New Jersey 07036 Howard Freund (1), Exxon Research and Engineering Company, Linden, New Jersey 07036 Martin L. Gorbaty (1), Corporate Research-Science Laboratories, Exxon Research and Engineering Company, Linden, New Jersey 07036 Stephen C. Mraw (1), Exxon Research and Engineering Company, Linden, New Jersey 07036 Kundan M. Patal (125), Department of Chemistry, University of North Dakota, Grand Forks, North Dakota 58202 Janet R. Pullen (173), IEA Coal Research, London SW1W 0EX, England Krishna Raman (125), Department of Chemistry, University of North Dakota, Grand Forks, North Dakota 58202 'Present address: Exxon Research and Engineering Co., Baytown, Texas 77520. 2Present address: Energy Conversion Devices, Inc., North Branch, New Jersey 08876. vii viii Contributors Virgil I. Stenberg (125), Department of Chemistry, University of North Dakota, Grand Forks, North Dakota 58202 Neil F. Woolsey (125), Department of Chemistry, University of North Dakota, Grand Forks, North Dakota 58202 Franklin J. Wright (1), Exxon Research and Engineering Company, Linden, New Jersey 07036 Preface The ultimate need to replace liquid and gaseous fuels now derived from petroleum and natural gas resources with synthetic fuels from coal is gen- erally recognized. Although technological bases already exist for utilizing coal directly in combustion and for converting it to liquid and gaseous fuels, we feel that considerable improvements in these technologies (such as greater overall thermal efficiency, hydrogen utilization, and selectivity to specific products) are needed. These improvements, along with new, more efficient routes to coal utilization, will only come about if we are able to gain more fundamental knowledge of coal in terms of its structure and reactivity. Because coal is such a heterogeneous material, coal science in its broadest sense embraces many scientific disciplines—including chemistry (organic, inorganic, and physical), physics, and engineering (chemical and me- chanical). Consequently, the literature of coal science is vast and complex, containing a great deal of information—but only rarely in such a form that this information is logically assembled, reviewed, and evaluated. Because of the current interest in coal, we felt that critical reviews written by experts and aimed at the professional chemist or engineer now working (or contemplating working) in coal science would be both timely and useful. These reviews would not only pull together what has been reported in the past into a coherent picture, they would also point out the original reports' significance as well as areas where more research is needed. Ul- timately, coal science should furnish data and clues for solving or bypassing many of the problems now associated with coal conversion technologies. This is the second in a series devoted to presenting and evaluating se- lected fundamental scientific areas involved with our understanding of coal structure, reactivity, and utilization. Reviews describing current state- of-the-art knowledge of coal's inorganic structure and reactivity and the role ionic bonding plays in coal's chemical and physical structure and reactivity are included, as well as contributions on hydrogen donor chem- ix X Preface istry and solvent extraction, both relating to coal conversion and utili- zation. It is our hope that this and subsequent volumes will not only be a valuable source of information and a guide to the coal literature, but will also stimulate research and serve as a basis for further advances in science and technology. The editors would like to thank the contributing authors for their time and diligence in helping to make this volume a reality. We may have acted as catalysts, but the major share of the credit belongs to them. Contents of Volume 1 Coal Plasticity Mechanism: Inferences from Liquefaction Studies Richard C. Neavel The Physical Structure of Coal Warren R. Grimes Magnetic Resonance Studies of Coal H. L. Retcofsky Molecular Structure of Coal Robert M. Davidson The Reductive Alkylation Reaction Leon M. Stock Index xi The Science of Mineral Matter in Coal STEPHEN C. MRAW, JOHN P. DE NEUFVILLE,* HOWARD FREUND, ZEINAB BASET,| MARTIN L. GORBATY, and FRANKLIN J. WRIGHT Exxon Research and Engineering Company Linden, New Jersey I. Introduction 2 II. Mineral Matter in Coal: Origin, Characterization, and Implications for Coal-Processing Technologies 3 A. Introduction 3 B. Origin of Mineral Matter in Coal and Resulting Mineralogical and Chemical Variations 4 C. Identification and Characterization of Mineral Matter in Coal. 10 D. Role of Chemical Bonding of Inorganic Matter in Coal Conversion or Combustion 24 III. Combustion 26 A. Introduction 26 B. Pulverized Coal Combustion Overview 27 C. Particulate Formation 29 D. Slagging 32 E. Fouling 36 F. Attempts to Combat Slagging and Fouling 37 G. Reduction of S0 Emissions via Ca-S Reactions 40 2 IV. Gasification and Liquefaction 42 A. Introduction 42 B. Sintered Deposits Formed in Gasification of Coal Liquefaction Residues 42 C. Inorganic Components of Gaseous Streams 45 D. Catalytic Effects of Mineral Matter in Gasification 46 E. Catalytic Effects of Mineral Matter in Liquefaction 47 * Present address: Energy Conversion Devices, Inc., North Branch, New Jersey 08876. t Present address: Exxon Research and Engineering Co., Baytown, Texas 77520. 1 COAL SCIENCE Copyright © 1983 by Academic Press, Inc. Volume 2 All rights of reproduction in any form reserved. ISBN 0-12-150702-5 2 Stephen C. Mraw et al. V. Silicate Chemistry at Elevated Temperature and Its Relevance to Ash Fusion Phenomena 49 A. Introduction 49 B. Sintering Phenomena—Combustion or Gasification of Coal in a Bedded Unit: Relevance of ASTM Ash Fusion Test (Initial Deformation Temperature) 50 C. Slagging Phenomena—Conventional Combustion of Pulverized Coal in a Nonslagging Boiler: Relevance of ASTM Ash Fusion Test to Actual Slagging Behavior 52 D. Summary Comparison of ASTM Test versus Sintering and Slagging 57 References 59 I. INTRODUCTION In this article we give a general overview of the area of mineral matter in coal and a critical review of many specific aspects which are most in- triguing scientifically. We consider the term mineral matter in its widest sense, that is, all of the inorganic material found in coal as mineral phases and the elements in coal that are considered inorganic (Gluskoter et al., 1977). Such a broad area as mineral matter in coal would be extremely difficult to review totally in all of its complex scientific and technological aspects. It is our intent in this article to concentrate in detail on specific portions of the total picture which are particularly intriguing to us on a scientific basis, because complex and poorly understood chemical and physicochemical mechanisms appear to be operating to produce the ob- served results. Throughout the article, we shall often go beyond merely reviewing the literature, in that we shall attempt to analyze the reported results further and even speculate upon their significance, as a means of indicating where further research is needed and would be most fruitful. Our discussion of these questions will include mineral matter in what can be thought of as "before, during, and after" processing, that is, (1) The modes of introduction of mineral matter into coal and the chemical and physical nature of the mineral matter in a present-day coal (2) The effect of coal combustion or conversion on the mineral matter and, conversely, the effect of the mineral matter on these high-temperature processes (3) The final chemical and physical state of the mineral matter or ash after processing, and whether it is potentially hazardous or potentially useful In this vein we present, in Section II, a critical review of the modes of occur- rence of inorganic elements in coal, both as mineral phases and as organ- ically bonded elements, and we examine the effects that highly dispersed
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