Carbon and Coal Gasification

Transcription

1 Carbon and Coal Gasification

2 NATO ASI Series Advanced Science Institutes Series A Series presenting the results of activities sponsored by the NATO Science Committee, which aims at the dissemination of advanced scientific and technological knowledge, with a view to strengthening links between scientific communities. The Series is published by an international board of publishers in conjunction with the NATO Scientific Affairs Division A Life Sciences Plenum Publishing Corporation B Physics London and New York C Mathematical and D. Reidel Publishing Company Physical Sciences Dordrecht and Boston D Behavioural and Martinus Nijhoff Publishers Social Sciences DordrechtiBoston/Lancaster E Applied Sciences F Computer and Springer-Verlag Systems Sciences Berlin/Heidelberg/New York G Ecological Sciences Series E: Applied Sciences - No. 105

3 Carbon and Coal Gasification Science and Technology edited by Jose L. Figueiredo Faculty of Engineering University of Porto 4099 Porto Codex Portugal Jacob A. Moulijn Institute for Chemical Technology University of Amsterdam Nieuwe Achtergracht WV Amsterdam The Netherlands 1986 Martinus Nijhoff Publishers Dordrecht / Boston / Lancaster Published in cooperation with NATO Scientific Affairs Division

4 Proceedings of the NATO Advanced Study Institute on Carbon and Coal Gasification - Science and Technology, Alvor, Portugal, May 20-31, 1985 Library of Congress Cataloging in Publication Data NATO Advanced Study Institute on Carbon and Coal Gasification--Science and Technology (1985 : Alvor, Portugal) Carbon and coal gasification. (NATO ASI series. Series E, Applied sciences v. 105) "Proceedings of the NATO Advanced Study Institute on Carbon and Coal Gasification--Science and Technology, Alvor, Portugal, May 20-31, 1985"--T.p. verso. "Published in cooperation with NATO Scientific Affairs Division." Includes index. 1. Coal gasification--congresses. 2. Carbon- Congresses. I. Fiegueiredo, Jose Luis. II. Moulijn, Jacob A. III. North Atlantic Treaty Organization. Scientific Affairs Division. IV. Title. V. Series. TP759.N ' ISBN-J3: ISBN-I3: : e-isbn-i3: Distributors for the United States and Canada: Kluwer Academic Publishers, 190 Old Derby Street, Hingham, MA 02043, USA Distributors for the UK and Ireland: Kluwer Academic Publishers, MTP Press Ltd, Falcon House, Queen Square, Lancaster LA1 1 RN, UK Distributors for all other countries: Kluwer Academic Publishers Group, Distribution Center, P.O. Box 322, 3300 AH Dordrecht, The Netherlands All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, mechanical, photocopying, recording, or otherwise, without the prior written permission of the publishers, Martinus Nijhoff Publishers, P.O. Box 163, 3300 AD Dordrecht, The Netherlands Copyright 1986 by Martinus Nijhoff Publishers, Dordrecht Softcover reprint ofthe hardcover 1st edition 1986

5 PREFACE Carbon gasification reactions form the basis of many important industrial processes, such as the combustion of coal and the production of synthesis gas, fuel gases and activated carbons. They are also involved in metallurgical processes and in the regeneration of coked catalysts. Thus, understanding the fundamentals of carbon gasification is of vital importance for further technological development. Moreover, the subject is of interdisciplinary nature, involving chemistry, materials science and chemical engineering. Therefore, it was thought that an Advanced Study Institute would be fruitful in establishing the state of the art, in bringing together experts from the various sectors involved and in identifying areas of required research and industrial development. Such a meeting was held at Alvor, Portugal, from the 20th to the 31st May 1985, and the lectures presented thereof are collected in this volume. The present volume is organized in seven chapters. The Introduction presents the carbon gasification reactions an~ their relevance for particular processes and industrial uses. In the second chapter, the structures of carbon and coal are reviewed, together with methods of structural, chemical and textural characterization. Catalysis of carbon gasification is addressed next, and the mechanisms of catalysis by alkali, alkaline-earth and transition metals are discussed in the context of C-C02, C-H20 and C-H2 reactions. In the fourth chapter, chemical engineering aspects relevant for gasification technology are covered. The remaining chapters are concerned with the major industrial applications involving gas-carbon reactions: - Coal gasification to produce fuel gases or synthesis gas;

6 - The production of cokes for metallurgy and the removal of coke from catalysts; - The production of activated carbons. In addition to the main lectures published here, a number of shorter communications were presented during the Institute, which could not be included in this volume for lack of space. Their titles are listed separately. All lecturers are to be thanked for their excellent contributions and for their cooperation in setting up the scientific programme of this Institute. In particular, we are indebted to Professor Philip L. Walker,Jr., for his support in the early stages of the organization of the meeting. Unfortunately, health problems prevented him from attending. He was nevertheless able to send one of his lectures, which constitutes the introductory chapter of this book. The collaboration of Dr. C.A.Bernardo in all stages of the organization is acknowledged with gratitude. Thanks are also due to J.J.Orfao, J.I.Martins, S.Alves, Alcina Bernardo, Helena Silva and Maria Idalina, who made an important contribution to the smooth running of the meeting, and to Mr. L.Santana and his staff at the Torralta complex, who made our stay a very pleasant one. The support of the Scientific Affairs Division of NATO, through the Advanced Study Institutes Programme, is gratefully acknowledged. Jose L. Figueiredo Jacob A. Moulijn

7 NATO ADVANCED STUDY INSTITUTE "CARBON AND COAL GASIFICATION - SCIENCE AND TECHNOLOGY" Organizing Committee Director: J.L. Figueiredo Associate Director: C.A. Bernardo Scientific Advisors: H. Marsh, J.A. Moulijn, K.H. van Heek Lecturers R.T.K. Baker, Exxon, NJ, USA J.L. Figueiredo, Univ. Porto, Portugal K.H. van Heek, Bergbau-Forschung, F.R. Germany K.J. Hlittinger, Univ. Karlsruhe, F.R. Germany A. Linares, Univ. Alicante, Spain A. Marchand, Univ. Bordeaux I, France H. Marsh, Univ. Newcastle upon Tyne, England J.A. Moulijn, Univ. Amsterdam, The Netherlands A.E. Rodrigues, Univ. Porto, Portugal F. Rodriguez Reinoso, Univ. Alicante, Spain K.M. Thomas, British Gas, England D.L. Trimm, Univ. New South Wales, Australia T. Wigmans, Norit, The Netherlands

8 LIST OF CONTRIBUTED PAPERS PRESENTED DURING THE A.S.I. BUT NOT INCLUDED IN THIS VOLUME: Characterization of carbons using the TPR technique, J.G.McCarty - Kinetics of the alkali carbonate catalysed C02 gasification of activated carbon, F.Kapteijn, M.B.Cerfontain, O.Peer, J.A.Moulijn - Reactivities and active surface areas of steam-gasified coal chars, P.D.Causton, B.McEnaney - Influence of temperature, pressure and gasifying agent on the KzC03 catalysed and uncatalysed gasification of char, H.J.MUhlen, W.Schumacher, K.H. van Heek Coal gasification processes in Turkey, S. UlkU - The status of coal classification, M.J.Lemos de Sousa - The potential impact of catalysts in coal gasification, R.Shinnar, C.A.Feng, A.Avidan - Catalytic COz activation of almond shells, M.Almela-Alarcon, A. Linares-Solano, F.Rodriguez-Reinoso, C.Salinas-Martinez de Lecea, A.Sepulveda-Escribano - Possible use of C02 adsorption as a "theoretical pre-adsorbate", M.Almela-Alarcon, A.Linares-Solano, F.Rodriguez-Reinoso, C.Salinas Martinez de Lecea, A.Sepulveda-Escribano - Recirculating fluidized bed gasifier, J.B.Escudero, J.J.Pis - Structural variations and kinetics of coal gasification with carbon dioxide, S.Balci - Experiences with catalan lignites gasification in a fluidized bed reactor, A.Lucas,J.Arnaldos, J.Casal, L.Puigjaner - The characterization of the plastic properties of a medium volatile bituminous coal by means of hot-stage microscopy, P.J.J.Tromp, J.A.Moulijn Interaction between potassium and calcium catalysts and mineral matter during coal gasification, R.E.Quartermaine

9 TABLE OF CONTENTS Part I. Introduction P.L. Walker, Jr. Carbon gasification - A ubiquitous reaction of great importance to mankind 3 Part II. Structure and characterization H. Marsh Structure in carbons K.M. Thomas Coal structure A. Marchand Physico-chemical and structural characterization of carbons 93 A. Linares-Solano Textural characterization of porous carbons by physical adsorption of gases 137 Part III. Catalytic gasification J.A. Moulijn, F. Kapteijn Catalytic gasification K.J. HUttinger, R. Minges Alkali metal catalyzed water vapour gasification of carbon using mineral catalyst raw materials K.J. HUttinger, J. Adler, G. Hermann Iron catalyzed water vapour gasification of carbon R.T.K. Baker Metal catalyzed gasification of graphite 231 J.L. Figueiredo, C.A. Bernardo, J.J.M. 6rfao Gasification of carbon deposited on metallic catalysts 269

10 Part IV. Chemical Engineering principles F. Kapteijn, J.A. Moulijn Kinetics of catalysed and uncatalysed coal gasification 291 A.E. Rodrigues Single particle models for fluid-solid reactions 361 Part V. Coal gasification K.H. van Heek General aspects and engineering principles for technical application of coal gasification 383 K.H. van Heek Technical status and new developments of coal gasification processes K.M. Thomas Characterisation of coal for gasification processes K.M. Thomas Some scientific aspects of the development of the slagging gasifier 439 J.A. Moulijn, P.J.J. Tromp Coal pyrolysis 455 K.J. HUttinger, A. Michenfelder Hydrogasification of brown coal - Chemism, kinetics and technical aspects 485 Part VI. Coke production and removal H. Marsh The making of coke in the delayed coker and in the slot coking oven 511 D.L. Trimm Coke formation and gasification in refineries 523 D.L. Trimm The regeneration of coked catalysts 543 Part VII. Activated carbons T. Wigmans Fundamentals and practical implications of activated carbon production by partial gasification of carbonaceous materials 559

11 F. Rodriguez-Reinoso Preparation and characterization of activated carbons 601 List of participants 643 Subject index 645