Crude Oil Chemistry. Vastly Simanzhenkov University Duisburg-Essen Duisburg, Germany. Raphael Idem University of Regina Regina, Saskatchewan, Canada

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1 Crude Oil Chemistry Vastly Simanzhenkov University Duisburg-Essen Duisburg, Germany Raphael Idem University of Regina Regina, Saskatchewan, Canada

2 Although great care has been taken to provide accurate and current information, neither the author(s) nor the publisher, nor anyone else associated with this publication, shall be liable for any loss, damage, or liability directly or indirectly caused or alleged to be caused by this book. The material contained herein is not intended to provide specific advice or recommendations for any specific situation. Trademark notice: Product or corporate names may be trademarks or registered trademarks and are used only for identification and explanation without intent to infringe. Library of Congress Cataloging-in-Publication Data A catalog record for this book is available from the Library of Congress. ISBN: X This book is printed on acid-free paper. Headquarters Marcel Dekker, Inc., 270 Madison Avenue, New York, NY 10016, U.S.A. tel: ; fax: Distribution and Customer Service Marcel Dekker, Inc., Cimarron Road, Monticello, New York 12701, U.S.A. tel: ; fax: Eastern Hemisphere Distribution Marcel Dekker AG, Hutgasse 4, Postfach 812, CH-4001 Basel, Switzerland tel: ; fax: World Wide Web The publisher offers discounts on this book when ordered in bulk quantities. For more information, write to Special Sales/Professional Marketing at the headquarters address above. Neither this book nor any part may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, microfilming, and recording, or by any information storage and retrieval system, without permission in writing from the publisher. Current printing (last digit): PRINTED IN THE UNITED STATES OF AMERICA

3 Preface This book is devoted to students as well as scientists and process engineers involved in petroleum science, refining and engineering. Part I of the book gives a historical overview of the origin of petroleum. The first chapter shows how crude oil is linked with human civilization. In this chapter it is also shown that the energy used to run most of today's machinery derives from petroleum. It also provokes our imagination on how the various moving parts of machinery would operate without mineral oil or lubricating oil, both of which are also produced from crude oil. The first chapter also provides insight into the problems that have arisen as a result of applying different standards by different countries to similar crude oil products and how these problems are tackled. The second chapter of Part I deals with modern analytical methods used in crude oil chemistry. Modern and classical methods of petroleum and petroleum product characterization are explained. This chapter is an essential chapter for present and potential crude oil chemists since analytical chemistry constitutes an important part of crude oil chemistry. Besides, crude oil products have so many special properties that are important for the industry. The need to determine these properties gives rise to the use of very many analytical methods in the petroleum industry. Part II (i.e. chapters 3 and 4) shows the geopolitical and economic nature of petroleum chemistry. In this chapter, the initial stages of development of various petroleum companies are shown. It gives a historical run-down on how small companies of the past have blossomed into giant multinational companies of worldwide repute. For readers, it is especially interesting to learn the history of the development of the Eastern Bloc companies, especially the Russian companies. In this chapter, it is shown how the political situation in this country has had a great influence on the economic development of all Russian industries in general and the petroleum industry in particular. It is also shown how it has been possible for the big Russian petroleum concerns to be formed in less than twenty years during the difficult times of political and economic reforms. Chapters 5 and 6 of Part III of the book introduce the reader to the science of crude oil refining. An illustration of the complete process scheme that starts from crude oil all the way to final products is given. In particular, the process route of crude oil from the well to the gas station and indeed the car tank is provided. These chapters also present the techniques and technologies involved in most of the important processes used in modern petroleum refineries for processing light and heavy distillate fractions. Chapter 7 in Part III looks at ecological problems that

4 arise in the crude oil industry. The chapter also shows that, in order to develop an appropriate technology for crude oil treatment, not only are economically rational decisions required, but also, ecologically acceptably decisions are needed. This chapter looks at our environment as a very sensitive system that must be protected with respect to the many processes that take place in the petroleum refining industry. Good quality crude oil is often defined in terms of high API gravity and low sulfur content. However, reserves of this type of oil are disappearing, giving rise to increasing contributions from oil of lower API gravity and higher sulfur content. Is the chemistry of processing of the two types of oil different? This question is answered in Part IV of this book. The chapter also introduces the presence of asphaltenes in crude oil. A list of problems that occur during oil production, transportation, and processing that could be attributed to asphaltene presence in crude oil is presented. New concepts and approaches that aid in the processing of crude oils with significant amounts of asphaltenes are introduced. Part IV also looks at future processes that may be introduced in the petroleum refinery. These are hybrid fuel production processes that involve combining the well-known modern cracking process with the recycling of waste plastics or bio-fuels. The advantages than can be derived from co-processing of asphaltene-containing crude oils with plastics or biomass materials are given. Part IV also presents some analytical techniques that could be used by petroleum engineers and chemists to better understand the nature of heavy crude oil and residues, and possible ways to positively influence their processing. In all, Part IV presents critical material that can contribute towards further development of the petroleum industry. This is especially true for the nonconventional petroleum industry, and it can be particularly important for North America, since Canada has the largest reserves of non-conventional petroleum in the world. Both authors have worked extensively in the areas of petroleum science and engineering. We hope that this book will go a long way in introducing the reader to the fascinating world and concepts of the black gold of our planet. Vasily Simanzhenkov Raphael Idem

5 Contents Preface Part I Classification and Characterization of Crude Oil 1 Nature and Classification of Crude Oil 1. History and nature of petroleum 1..1 Origin of petroleum 1..2 Oil formation in the world's oceans 1..3 Modern concept of formation of petroleum 1..4 Consequences of intensive extraction and processing of oil Dangerous fogs Black oceans 1.2 General properties and classification of petroleum: comparison of petroleum from different countries Fractions and chemical composition of petroleum Chemical classification of petroleum Classification by density Characterization by viscosity-gravity constant (vgc) Technological classification of petroleum 1.3 Products from crude oil Gasoline Jet fuel (kerosene) Diesel.3.4 Residual fuel.3.5 International standards for fuels.4 Lubricating oils and lubricants.4. International standards for lubricating oils Industrial oils.4..2 Motor oils.4..3 Transmission oils.4..4 Hydraulic oils 2 Modern Characterization and Analysis Techniques for Crude Oil 2.1 Chromatographic methods Gas chromatography High performance liquid chromatography Thin layer chromatography 2.2 Spectroscopic methods Infrared spectroscopy

6 2.2.2 Raman spectroscopy Colorimetry and photometry Fluorescence and phosphorescence spectroscopy Atomic absorption spectroscopy and atomic emission spectroscopy X-ray fluorescence spectroscopy 2.3 Other methods for elucidating the structure of crude oil Separation methods Chemical analysis methods of crude oil products: determination of unsaturated compounds Structural bulk analysis of heavy crude oil fractions: n-d-m method 2.4 Methods of characterization of colloidal properties of crude oil and its products Direct methods Indirect methods 2.5 Determination of the physical properties of crude oil Density determination Viscosity determination Refractive index determination Bibliography Part II Regional Petroleum Industry 3 Petroleum Producing Countries: OPEC and Non-OPEC 3.1 Introduction Short background on OPEC 3.2 North America United States Canada 3.3 Russia The role of the petroleum industry for Russia Reforms in the Russian oil industry Russian petroleum and gas in the world market Structure of the petroleum sector in Russia 3.4 Arabian East Oman Iraq Iran Qatar Kuwait United Arab Emirates Saudi Arabia

7 4 International Petroleum Companies 4.1 British Petroleum 4.2 Castrol 4.3 ExxonMobil 4.4 Neste/Fortum 4.5 Shell 4.6 Total /Fina/ Elf 4.7 LUKOil 4.8 Yukos 4.9 TNK Bibliography Part III Main Processes in the Petroleum Refining Industry 5 Crude Oil Distillation 5.1 Petroleum and gas preparation Formation of petroleum emulsions and their basic properties Separation of water-oil emulsions Mechanical petroleum drying Thermal petroleum drying Chemical methods of petroleum drying Thermal chemical petroleum drying Stabilization of petroleum Technological schemes for petroleum preparation Pressure extraction system 5.2 Desalting 5.3 Atmospheric rectification 5.4 Vacuum rectification 5.5 Heat exchangers and separators 6 Processing of Light and Heavy Distillates 6.1 Thermal cracking 6.2 Catalytic cracking 6.3 Visbreaking 6.4 Coking 6.5 Hydroprocessing 6.6 Reforming 6.7 Isomerization 6.8 Alkylation 6.9 Blending 7 Environmental Issues Facing the Refining Industry 7.1 Introduction 7.2 Methods of cleaning crude oil contaminated water and soil

8 7.3 Methods of air and gas cleaning used in the crude oil industry 7.4 Conclusion to Part III Bibliography Part IV Heavy Oil Processing - Chemistry of Asphaltenes 8 Chemistry of Crude Oil Asphaltenes 8.1 Introduction 8.2 Problems of crude oil residue treatment with respect to asphaltenes Coke formation and reduction of heavy metals Treatment possibilities for crude oil residues Physical treatment - deasphalting Chemical treatments Visbreaking Coking Coke forming reactions during residue treatment Catalytic treatment Thermal treatment 8.3 Methods of analysis of crude oil residue Methods and main definitions for the determination of coke formation tendency Analytical characterization of heavy oil residues and asphaltenes Solution analysis Coagulation analysis Distillation method Chromatography B C-NMR analysis Ultimate analysis Molecular weight determination Temperature influence on molecular weight determination 9 Processing of Heavy Crude Oils and Crude Oil Residues 9.1 Introduction 9.2 Chemistry and reaction of asphaltenes during co-processing of crude oil residue and plastics Change of asphaltene structure during thermal processing Evaluation of possibilities of various asphaltene reactions based on thermodynamics Hydrogen transfer 9.3 Co-processing with cracked products Co-processing with cracked products from aromatics containing plastics (e.g. polystyrene) Co-processing with cracked products from plastics containing

9 paraffin groups Possibilities that exist for carrying out co-processing of heavy crude oils and various co-feeds Behavior of heavy metals during co-processing Conclusions of co-processing of crude oil residue and co-feed 9.4 Industrial methods of crude oil residue treatment Fluid catalytic cracking Hydrocracking Coking Bibliography Appendix A: Conversion Factors Important for Crude Oil Chemists Appendix B: Glossary