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The Science and Technology of Coal and Coal Utilization EDITED BY
BERNARD R. COOPER West Virginia University Morgantown, West Virginia
AND
WILLIAM A. ELLINGSON Argonne National Laboratory Argonne, Illinois
PLENUM PRESS • NEW YORK AND LONDON
Library of Congress Cataloging in Publication Data
Main entry under title:
The Science and technology of coal and coal utilization.
Includes bibliographical references and index. Contents: Introduction to the science and technology of coal and coal utiliza
tion/Bernard R. Cooper and William A. Ellingson-Coal characterization/Heinz
H. Damberger ... et al. -Coal preparation and cleaning/T.D. Wheelock and R. Markuszewski- etc.
1. Coal-Addresses, essays, lectures. I. Cooper, Bernard R. II. Ellingson, W. A. TP325.S36 1984 83-26189
ISBN-13: 978-1-4684-4582-4
DOl: 10.1007/978- I -4684-4580-0
e-ISBN-13: 978-1-4684-4580-0
© 1984 Plenum Press, New York
Softcover reprint of the hardcover 15t edition 1984
A Division of Plenum Publishing Corporation 233 Spring Street, New York, N.Y. 10013
All rights reserved
No part of this book may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher
Preface
Filling the need for new and improved energy sources is an area where societal effects of science and technology will surely increase. The editors and authors have attempted in this volume to present the most current work on the science and technology of coal and coal utilization.
Serious disagreement exists on several key issues such as carbon dioxide release and acid rain. At the same time, however, coal is the world's most abundant fossil fuel and will have to be used to supply the world's energy needs for the next several decades. The 1979 National Research Council Report, "Energy in Transition: 1985-2010," has estimated that the United States alone may go from a 1979 coal consumption of 14 QUADS per annum (approximately 750 million tons per year) to approximately 40-50 QUADS per annum (approximately 2 billion tons per year) by the year 2010. If this scale of coal utilization is to become a reality, a significant level of research and development will be necessary to establish advanced process technologies and to improve related areas such as materials and instrumentation.
The editors hope that this volume will allow a technically educated person to become aware of the several aspects of coal utilization, from characterization of coal itself to the processes of coal utilization.
B. R. Cooper and W. A. Ellingson March, 1983
vii
Contents
1. THE SCIENCE AND TECHNOLOGY OF COAL AND COAL UTILIZATION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Bernard R. Cooper and William A. Ellingson
2. COAL CHARACTERIZATION. . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Heinz H. Damberger, Richard D. Harvey, Rodney R. Ruch, and Josephus Thomas, Jr.
1. 2. 3.
Introduction ......................................... . Samples and Their Analyses ........................... . Megascopic and Microscopic Characterization of Coal ...... . 3.1. Megascopic Characterization ...................... . 3.2. Microscopic Characterization ...................... .
4. Mineral Matter in Coals ............................... .
7 10 11 12 13 21
5.
6. 7. 8.
Standard Chemical Analyses and Some Special Evaluation Tests ............................................... 25 Analyses of Major, Minor, and Trace Ash-Forming Elements Isotopic Studies ...................................... . Physical Properties of Coal ............................ . 8.1. Porosity and Internal Surface Area ................. . 8.2. Permeability ................................... . 8.3. Structure and Density ............................ . 8.4. Spontaneous Combustion ......................... . 8.5. Electrical Conductivity ........................... .
26 30 31 31 36 36 37 38
8.6. Optical Properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 39 8.7. Grindability, Hardness, Strength . . . . . . . . . . . . . . . . . . .. 39
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 39
ix
x CONTENTS
3. COAL PREPARATION AND CLEANING .................. 47
T. D. Wheelock and R. Markuszewski
1. Introduction.......................................... 47 2. Present Coal-Cleaning Practice .......................... 52
2.1. Basic Cleaning Process. . . . . . . . . . . . . . . . . . . . . . . . . . .. 52 2.2. Washability Tests. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 54 2.3. Beneficiation Methods ............................ 57 2.4. Separation Efficiency. . . . . . . . . . . . . . . . . . . . . . . . . . . .. 60 2.5. Industrial Plant Performance ....................... 65
3. Experimental Coal-Cleaning Plants. . . . . . . . . . . . . . . . . . . . . .. 68 4. New Developments in Physical Cleaning. . . . . . . . . . . . . . . . .. 74
4.1. Chemical Comminution ... . . . . . . . . . . . . . . . . . . . . . . .. 75 4.2. Screening....................................... 77 4.3. Hydraulic Separation ............................. 78 4.4. Heavy Media Separation .......................... 79 4.5. Separations Based on Surface Properties. . . . . . . . . . . . .. 81 4.6. Magnetic Cleaning .. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 87 4.7. Electrostatic Separation ........................... 92
5. Development of Chemical Cleaning Methods. . . . . . . . . . . . . .. 94 5.1. Oxidative Desulfurization . . . . . . . . . . . . . . . . . . . . . . . . .. 96 5.2. Caustic Treatments. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 101 5.3. Reductive Desulfurization ......................... 105 5.4. Miscellaneous Methods ........................... 106 5.5. Economics of Chemical Coal Cleaning. . . . . . . . . . . . . .. 107
6. Research on Bacterial Desulfurization . . . . . . . . . . . . . . . . . . . .. 108 7. Summary and Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 109
Conversion Factors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 113 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 113
4. ROLE OF IMPURITIES .................................. 125
P. A. Montano, B. Granoff, and T. D. Padrick
1. Impurities in Coal: Introduction. . . . . . . . . . . . . . . . . . . . . . . . .. 125 1.1. Physical and Chemical Properties of the Major Minerals 126 1.2. Trace Elements. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 128 1. 3. Identification and Characterization of Minerals and Trace
Elements in Coal. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 129 2. Role of Impurities in Coal Mining ....................... 133 3. Coal Combustion ..................................... 133 4. Coke ............................................... 134
CONTENTS xi
5. Coal Liquefaction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 135 5.1. Kinetics of Pyrite Decomposition ................... 137 5.2. Pyrrhotites ...................................... 140 5.3. Active Catalytic Sites. . . . . . . . . . . . . . . . . . . . . . . . . . . .. 143 5.4. Slurry Phase Catalysts ............................ 147
6. Coal Gasification. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 150 6.1. Introduction..................................... 150 6.2. Rapid Devolatilization ............................ 150 6.3. Char Gasification ................................ 153
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 159
5. GASIFICATION AND INDIRECT LIQUEFACTION. . . . . . . .. 163
James C. W. Kuo
1. Introduction.......................................... 163 2. Coal Gasification. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 165
2.1. Introduction ..................................... 165 2.2. Chemistry of Coal Gasification. . . . . . . . . . . . . . . . . . . .. 166 2.3. Classification of Coal Gasifiers ...... . . . . . . . . . . . . . .. 170 2.4. Commercial Gasifiers. . . . . . . . . . . . . . . . . . . . . . . . . . . .. 178 2.5. Gasifiers under Development ....................... 181
3. Synthesis Gas Purification and Water-Gas Shift Processes. . .. 190 3. 1. Introduction..................................... 190 3.2. Commercial Synthesis Gas Purification Processes ...... 191 3.3. Water-Gas Shift Processes ......................... 197
4. Indirect Liquefaction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 199 4.1. Introduction..................................... 199 4.2. Methanol Synthesis ............................... 200 4.3. Methanol-to-Gasoline Conversion ................... 205 4.4. Fischer-Tropsch Synthesis ......................... 210 4.5. Fischer-Tropsch Product Upgrading ................. 221
5. Summary and Conclusion ............................... 224 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 226
6. DIRECT LIQUEFACTION ............................... 231
Michael G. Thomas
1. Introduction.......................................... 231 1.1. Historical Perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 231
xii CONTENTS
1.2. Definition of Processes. . . . . . . . . . . . . . . . . . . . . . . . . . .. 232 1.3. Types of Coals .................................. 233 1.4. Objectives ...................................... 234
2. Thermal Chemistry .................................... 234 2. 1. Concepts ....................................... 234 2.2. Stoichiometry ................................... 236 2.3. Mechanisms ..................................... 238 2.4. Effects of Independent Variables .................... 240 2.5. Current Concepts on Rates and Activation Energies .... 241
3. Catalytic Chemistry ................................... 248 3.1. Objectives ...................................... 248 3.2. Effects on Coal Dissolution ........................ 249 3.3. Effects on Preasphaltene Decomposition .............. 250 3.4. Synergistic Effects with Catalysts . . . . . . . . . . . . . . . . . .. 251 3.5. Catalytic Mechanisms ............................. 254
4. Direct Liquefaction Technology .......................... 255 4.1. Current Status ................................... 255 4.2. Advanced Concepts .............................. 257
5. Summary ............................................ 259 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260
7. FLUIDIZED-BED COMBUSTION . ........................ 263
Walter F. Podolski
1. Introduction.......................................... 263 2. Fluidization Background ................................ 265 3. FBC System Description ............................... 267
3.1. Atmospheric Fluidized Bed Combustors . . . . . . . . . . . . .. 267 3.2. Pressurized Fluidized Bed Combustors ............... 268 3.3. Comparison to Conventional Combustors ............. 269
4. FBC Design .......................................... 271 4.1. Mechanical Design Consideration ................... 274 4.2. Environmental Considerations ...................... 285
5. Analytical System Performance Modeling ................. 295 5.1. Hydrodynamics .................................. 296 5.2. Combustion Process .............................. 297
6. Concluding Remarks. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 300 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
CONTENTS xiii
8. COAL-FIRED OPEN-CYCLE MHD PLANTS ............... 307
George R. Seikel
1. Introduction.......................................... 307 1.1. Plant Concept . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 308 1.2. Historical Perspective. . . . . . . . . . . . . . . . . . . . . . . . . . . .. 310 1.3. MHD Generator ................................. 311
2. MHD Plants ......................................... 315 2.1. Types of MHD Plants. . . . . . . . . . . . . . . . . . . . . . . . . . . .. 315 2.2. MHD Plant Efficiency ............................ 317 2.3. Summary of MHD Plant Performance ................ 320 2.4. Early Commercial MHD Plant Designs ............... 322 2.5. Alternative Disk Generator Plants ................... 326 2.6. Nonutility MHD Plants. . . . . . . . . . . . . . . . . . . . . . . . . . .. 326
3. Status and Cost of MHD Plant Systems ................... 327 4. Concluding Remarks. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 333
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 333
9. FUEL CELL POWER PLANT SySTEMS .................. 339
Marvin Warshay
1. Summary............................................ 339 2. Introduction .......................................... 340
2.1. Brief History .................................... 341 2.2. Fuel Cell Basic Concepts .......................... 342 2.3. Fuel Cell Power Plant System Characteristics ......... 345
3. Predicted Performance and Cost of Fuel Cell Systems Operating on Coal-Derived Fuels ........................ 354 3.1. Low-Temperature Fuel Cells . . . . . . . . . . . . . . . . . . . . . .. 354 3.2. High-Temperature Fuel Cells ....................... 360
4. Discussion ........................................... 365 4.1. Study Assumptions and Sensitivity .................. 365 4.2. Fuel Cell Problems, Solution Prospects, and
Commercialization ............................... 371 5. Concluding Remarks ................................... 375
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 377
10. CATALYSIS AND CATALYTIC DEACTIVATION .......... 381
Leon M. Polinski, V. Udaya S. Rao, and John M. Stencel
1. Preface.............................................. 381 2. Instrumental Analysis of Liquefaction Catalysts. . . . . . . . . . . .. 382
xiv CONTENTS
2.1. Introduction ..................................... 382 2.2. Analytical Techniques for Catalyst Characterization .... 383 2.3. Indirect Liquefaction .............................. 391 2.4. Direct Liquefaction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 401
3. Catalysts for the Indirect Liquefaction of Coal .............. 408 3.1. Possible Routes for Indirect Liquefaction of Coal ...... 408 3.2. Aspects of Hydrocarbon Synthesis (Polymerization
Kinetics) ....................................... 410 3.3. Catalysts for Alcohol Synthesis ..................... 415 3.4. Zeolite Catalysts for Methanol to Gasoline Process ..... 417 3.5. Fischer-Tropsch Catalysts ......................... 442
4. Catalysts for the Direct Liquefaction of Coal. . . . . . . . . . . . . .. 455 4.1. Overview of Direct Coal Liquefaction ............... 455 4.2. General Problems of Catalytic Systems for Coal
Liquefaction Processes . . . . . . . . . . . . . . . . . . . . . . . . . . .. 458 4.3. Conversion Measurement .......................... 458 4.4. History of Supported Catalyst Coal Conversion Process
Investigations ................................... 460 4.5. Variations in Test Procedures for Catalyst Evaluation by
Investigations ................................... 461 4.6. Catalytically Active (Co/MoIAI20 3 , Ni/MoiAlz03 and
SnClz)Ingredients and Some Experimental Results Indicating the Importance of Metal-to-Metal and Metal-Support Interactions .............................. 464
4.7. Catalyst Preparation ................... . . . . . . . . . .. 466 4.8. Pore Size Distribution-Selectivity and Activity Effects 472 4.9. H-Coal Catalyst Process Behavior ................... 473
4.10. Analysis of the Types of Catalyst Aging and of Aging Dynamics ....................................... 475
4.11. Catalyst Diameter Effect .......................... 477 4.12. Coal-Liquids-Upgrading Catalysis-Recent Work ...... 479 4.13. Heteroatom Removal Characteristics of Catalysts ...... 480 4.14. Slurry Phase Catalysts ............................ 481
5. Concluding Remarks. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 482 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 482
11. MATERIALS OF CONSTRUCTION ....................... 489
W. A. Ellingson, K. Natesan, and T. Vojnovich
1. Introduction.......................................... 489 2. Low-Temperature Corrosion ............................ 489
2.1. Aqueous Corrosion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 490 2.2. Stress Corrosion Cracking ......................... 492 2.3. Steam Corrosion ................................. 493
CONTENTS xv
2.4. Hydrogen Attack ................................. 496 3. High-Temperature Corrosion ............................ 497
:3 .1. Gaseous Corrosion .. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 497 3.2. Corrosion of Refractories by Coal Slag ............... 515 3.3. Molten Salt Corrosion ............................ 528 3.4. Deposit-Induced Corrosion ......................... 532
4. Erosive Wear. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 537 4.1. Erosion by Solid Particles Entrained in Gas Streams. . .. 538 4.2. Consideration of Fluid Mechanics on Erosive Wear
Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 550 4.3. Erosive Wear by Solid Particles Entrained in Liquid
Streams (Slurry Erosion) .......................... 550 4.4. Cavitation Erosion ............................... 552
5. Mechanical Properties .................................. 553 5.1. Tensile Properties ................................ 553 5.2. Creep and Creep-Rupture Properties ................. 557 5.3. Impact Properties ................................ 562 5.4. Low-Cycle Fatigue Properties ...................... 563 5.5. Susceptibility to Stress-Corrosion Cracking ........... 563
6. Materials-Design Interface. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 564 6.1. Pressure Vessels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 564 6.2. Refractory Linings ............................... 570 6.3. Heat Exchangers ................................. 572 6.4. Turbines ........................................ 579
7. Nondestructive Evaluation .............................. 585 7.1. Pressure Vessel Inspection. . . . . . . . . . . . . . . . . . . . . . . .. 587 7.2. Refractory Lining Inspection ....................... 588 7.3. Steam Boiler and Heat Exchanger Inspection . . . . . . . . .. 591 7.4. Monitoring Methods. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 595
8. Summary ............................................ 600 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 601
12. INSTRUMENTATION AND MONITORING •...••.....•.••• 611
Nancy M. O'Fallon
1. Introduction.......................................... 611 1.1. Types of Instrumentation . . . . . . . . . . . . . . . . . . . . . . . . .. 611 1.2. Difficulties in Instrumenting Coal Utilization Systems ... 614
2. Multiphase Flow Measurement .......................... 615 2.1. Description of Available Multiphase Flow Instruments .. 616 2.2. Multiphase Flowmeters under Development ........... 621
3. Temperature Measurement .............................. 632 3.1. Description of Available Temperature Instruments. . . . .. 632 3.2. Temoerature Instrumentation under Development ...... 633
xvi CONTENTS
4. Gas Stream Analysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 636 4.1. Description of Available Gas Stream Analyzers ........ 636 4.2. Gas Stream Analyzers under Development ............ 637
5. Particulate Monitors ................................... 640 5.1. Description of Available Particulate Monitors ......... 640 5.2. Particulate Monitoring Systems under Development .... 642
6. Solid and Slurry Stream Analysis ..... . . . . . . . . . . . . . . . . . .. 644 6.1. Description of Available Solid and Slurry Stream
Analyzers ....................................... 644 6.2. Solid and Slurry Stream Analyzers under Development 644
7. Level Detection. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 647 7. 1. Description of Available Level Detection Instruments . .. 648 7.2. Level Detection Instruments under Development . . . . . .. 649
8. Nondestructive Evaluation Instruments .................... 651
INDEX . ................................................ 659
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