Composition, Geochemistry and Conversion of Oil Shales NATO ASI Series Advanced Science Institutes Series

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Series C: Mathematical and Physical Sciences - Vol. 455 Composition, Geochemistry and Conversion of Oil Shales

edited by

Colin Snape Department of Pure and Applied Chemistry, University of Stratchclyde, Glasgow, Scotland, U.K.

Springer-Science+Business Media, B.V. Proceedings of the NATO Advanced Study Institute on Composition, Geochemistry and Conversion of Oil Shales Akcay, Turkey 18-31 July 1993

Library of Congress Cataloging-in-Publication Data

ISBN 978-94-010-4140-9 ISBN 978-94-011-0317-6 (eBook) DOI 10.1007/978-94-011-0317-6

Printed on acid-free paper

All Rights Reserved © 1995 Springer Science+Business Media Dordrecht Originally published by Kluwer Academic Publishers in 1995 Softcover reprint of the hardcover 1 st edition 1995 No part of the material protected by this copyright notice may be reproduced or utilized in any form or by any means, electronic or mechanical, including photo• copying, recording or by any information storage and retrieval system, without written permission from the copyright owner. Preface

Oil shales are broadly dermed as petroleum source rocks containing sufficiently high contents of organic matter (above ca 10-15 wt.%) to make utilisation a possibility. Like coal, the world's reserves of oil shales are vast being many times larger than those proven for crude oil. Indeed, some of the largest deposits occur in the USA and Europe where Estonia and Turkey have large reserves. The first recorded interest in oil shale retorting was an English patent in 1694 (Eele, Hancock and Porter, No. 330) which refers to distilling noyle from some kind of stone". The oil shale retorting industry dates back to the middle of the last century, notably Scotland, Estonia, France and Sweden in Europe. Indeed, my own Department at the University of Strathclyde has a historical link with James "Paraffin" Young, the founder of the Scottish oil shale industry who endowed a chair in Applied Chemistry. The growth of the oil industry saw the demise of the oil shale industry in most countries with the notable exception of Estonia, where kukersite has continued to be used for power generation and retorting. However, oil shale utilisation has attracted renewed attention since the early 1970s as a source of transport fuels and chemical feedstocks due to the the long term uncertainties over crude oil supplies. Indeed, the last 15 years has seen the development of a number of innovative process concepts, such as fluid-bed pyrolysis and hydroretorting which have enabled considerably higher oil yields to be obtained than by the classic retorting procedures.

The yield of shale oil obtained from retorting is governed by the organic matter content and maturity of the shale (crudely classified into Types I, II and III on the basis of atomic HlC and OIC ratios), the retorting regime and interactions between the organic material and the minerals present To understand these phenomena, detailed structural information is clearly required on the organic matter present Although microscopy and reflectance measurements enable the visibly distinct organic classes - macerals and the overall thermal maturity to be assessed no information is provided on the chemical structure. The facts that most of the organic matter is insoluble in common organic solvents (kerogen is the generic term used to describe this insoluble matter) and the organic matter occurs in a mineral matrix pose considerable problems for detailed characterisation. Indeed, the problems are more acute than for coals where the mineral concentrations are much lower. Nonetheless, the organic geochemistry and analytical chemistry communities have made considerable strides in the application of gas chromatography, mass spectrometry, nuclear magnetic resonance and a number of other advanced analytical methods to assess the structure and biological origins of kerogens. Therefore, it was considered timely to bring together leading scientists from the analytical/geochemistry and chemical engineering communities involved in fossil fuel research for this NATO ASI.

The aim of the ASI was to provide a comprehensive coverage of oil shale chemistry and conversion technology emphasing the key role oil shale could have in the future for helping to meet the increasing world's demand for transport fuels and chemical feedstocks. The major themes of the ASI were the (i) composition and geochemistry encompassing microscopy, advanced specroscopic and pyrolysis techniques, biomarkers and mineral matter and (ii) conversion including static and fluid-bed retorting, hydropyrolysis, co-processing, gasification. beneficiation. upgrading strategies and environmental considerations. The reviews in first two sections of the book reflect these major themes. In addition to the review lectures, over 25 research contributions were presented as posters at the ASI which contributed greatly to the success of the scientific programme. A number of these have been included the third section of the book.

Special thanks are due to Ekrem Ekinci of Istanbul Technical University for his invaluable assistance in helping me organise the NATO ASI. Further, I wish to acknowledge the contributions from E. Putun, F. Yardim, H. Atakul and D. Ercikan - the local organising committee in Turkey - and that from my wife, Anne who acted as secretary, in helping to make the ASI a success. Colin E. Snape 9.10.94 v TABLE OF CONTENTS Preface v

Part I Reviews: Geochemista & Characterisation

1. Organic petrography: principles and techniques. 1 A. Hutton, University ofWollongong, Australia

2. Organic petrography of oil shales. 17 A. Hutton, University ofWollongong, Australia

3. Demineralisation and kerogen maceral separation and chemistry. 35 T.L. Robl and D.N. Taulbee, University of Kentucky, Centre for Applied Energy Research, USA

4. Alkane biomarkers. Geochemical significance and application in oil shale geochemistry. . 51 P.J. Gonzalez-Vila, Instituto de Recursos Naturales, Spain

5 . Solid state 13C NMR in oil shale research: an introduction with selected applications. 69 F.P. Miknis, Western Research Institute, USA

6. Introduction to mass spectrometric techniques for fossil fuel analysis. 93 G.A. Veloski and C.M. White, Pittsburgh Energy Technology Centre, USA

7. An introduction to open-tubular gas chromatography - analysis of fossil 107 and synthetic fuels. C.M. White, Pittsburgh Energy Technology Centre, USA

8. Speciation of organic sulphur forms in solid fuels and heavy oils. 125 C.E. Snape, K. Ismail, S. Mitchell, University of Strathclyde, UK and K.D. Bartle, University of Leeds, UK

9. Detailed structural characterization of the organic material in Rundle Ramsay Crossing and Green River oil shales. 143 M. Siskin, C.G. Scouten, K.D. Rose, T. Aczel, S.G. Colgrove and R.E. Pabst, Jr., Exxon Research & Eng. Co., USA Part II Reviews: Conversion: Processinr. Mechanisms and Products 1. Economic considerations of the oil shale and related conversion processes. 159 E. Ekinci, Istanbul Technical University, Turkey

2. Oil shale beneficiation for processing. 175 J.G. Groppo, University of Kentucky, Centre for Applied Energy Research, USA viii

3. Methods of oil shale analysis. 191 F.P. Miknis, Western Research Institute, USA

4. Relationship between hydrous and ordinary pyrolysis. 211 AK. Burnham, Lawrence Livennore National Laboratory, USA

5. Fluidized bed retorting of oil shale. 229 S.D. Carter, U.M. Graham, AM. Rubel and T.L. Robl, University of Kentucky, Centre for Applied Energy Research, USA

6. Steam and co-processing of oil shales. 247 E. Ekinci,lstanbul Technical University, Turkey and Y. Yurum, Hacettepe University, Turkey

7. Chemical kinetics and oil shale process design. 263 AK. Burnham, Lawrence Livennore National Laboratory, USA

8. Hydropyrolysis: fundamentals, two-stage processing and PDU operation. 277 M.J. Roberts, Gas Research Institute, USA, C.E. Snape and S.C. Mitchell, University of Strathclyde, UK

9. The bitumen intennediate in isothennal and non-isothennal decomposition of oil shales. 295 F.P. Miknis, Western Research Institute, USA

10. Aqueous organic chemistry: geochemical aspects. 313 M. Siskin and AR. Katritzky, Exxon Res. and Eng. Co., USA

11. Asphaltites composition and conversion. 329 E. Ekinci, Istanbul Technical University, Turkey and Y. Yurum, Hacettepe University, Turkey

12. Oil shale residues as a feedstock for carbon materials. 347 F.Derbyshire, U. Graham, Y.Q. Fei and M. Jagtoyen, University of Kentucky, Centre for Applied Energy Research, USA

13. Combustion reactivity of chars. 365 B.Z. Uysal, Gazi University, Turkey Part 111 Research contributions

1. A probe for the rapid analysis of Vanadium: An Electron Paramagnetic Resonance and theoretical perspective. 379 S.M. Mattar and R. Sammynaiken and I Unger, University of New Brunswick, Canada ix

2. Characterization of Jurassic black shales from Asturias (Northern Spain): evolution and petroleum potential. 387 I Suarez Ruiz and lG. Prado, Instituto Nacional del CarbOn, Oviedo, Spain 3. n-Alkanoic compounds in sulphur-rich macromolecular substances: a detailed investigation of sulphur incorporation and cross-linking. 395 J. Hefter, H.H. Richnow, R. Seifert and W. Michaelis, University of Hamburg, Germany

4. Biodegradation of hydrocarbons by sulphate reducing-bacteria in the Cretaceous Bahloul Formation (Tunisia). 407 M. Pervaz and W. Puttman, Lehrstuhl fiir Geologie, Geochemie und Lagerstiitten des ErdtHs und der Kohle, Aachen, Germany

5. Origin, evolution and petroleum potential of a Cambrian source rock: implications ofpyrolysate and bitumen composition. 419 S. Bharati, Geolab Nor, Trondheim, Norway and S. Larter, University of Newcastle upon Tyne, UK

6. Carbon isotopic compositions of individual alkaneslalkenes in leaf fossils and sediments from the P-33 site of the Miocene Clarkia deposit 439 Y. Huang, M.J. Lockheart, J.W. Collister and G. Eglinton, Organic Geochemistry Unit, School of Chemistry, University of Bristol, Bristol, UK

7. Atmospheric pressure temperature programmed reduction (AP-TPR) as a tool to investigate the changes in sulphur functionalities in solid fuels. 449 J. Yperman, D. Franco, J. Mullens, G. Reggers, M. d'Olieslaeger, L.c. Van Poucke, Limburgs Universitair Centrum, Diepenbeek, Belgium and S.P. Marinov, Bulgarian Academy of Sciences, Sofia, Bulgaria

8. Organic geochemical characterization of some carboniferous coal seams of the Zonguldak basin (N.W. Turkey). 461 M.N. Yal~in, TUBITAK, Marmara Research Centre, Turkey

9. X-ray studies of the structure of coals and cokes. 477 P. Wilk and S. Jasie6ko, Institute of Chemistry and Technology of Petroleum and Coal, Technical University ofWroclaw, Poland

10. The aspects of microscopic studies as exemplified by the macroporous structure of cokes from bituminous coal range. 485 P. Wilk and K. Bratek, Institute of Chemistry and Technology of Petroleum and Coal, Technical University ofWroc1aw, Poland x

11. Determination of organic sulphur forms in Type IIll kerogens by high pressure temperature programmed reduction. 493 S.C. Mitchell and K. Ismail, University of Strathclyde, Dept. of Pure & Applied Chemistry, Glasgow, UK, R. Garcia and S.R. Moinelo, Instituto Nacional del CarbOn, Oviedo, Spain.

Index 501