the chemistry and technology of petroleum,3rd edition

THE
CHEMISTRY
flND
TECHNOLOGY
OF
PETROLEUM
Third
Edition,
Revised
and
Expanded
James
G.
Speight
Consultant,
CDW
Inc.
Laramie,
Wyoming
MARCEL
MARCEL
DEKKER,
INC.
NEW
YORK
•
BASEL
D £
K K
E R

Library of Congress Cataloging-in-Publication Data
Speight, J. G.
The chemistry and technology of petroleum / James G. Speight.—3rd ed.,
rev. and expanded.
p. cm.—(Chemical industries : v. 76)
Includes bibliographical references and index.
ISBN 0-8247-0217-4 (acid-free paper)
1. Petroleum. 2. Petroleum—Refining. I. Title. II. Series.
TP690.S74 1998
665.5—dc21 98-50966
CIP
This book is printed on acid-free paper.
Headquarters
Marcel Dekker, Inc.
270 Madison Avenue, New York, NY 10016
tel: 212-696-9000; fax: 212-685-4540
Eastern Hemisphere Distribution
Marcel Dekker AG
Hutgasse 4, Postfach 812, CH-4001 Basel, Switzerland
tel: 44-61-261-8482; fax: 44-61-261-8896
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.
Copyright  1999 by Marcel Dekker, Inc. All Rights Reserved.
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):
10987654321

PRINTED IN THE UNITED STATES OF AMERICA
CHEMICAL INDUSTRIES
A Series of Reference Books and Textbooks
Founding Editor
HEINZ HEINEMANN
1. Fluid Catalytic Cracking with Zeolite Catalysts, Paul B. Venuto and E. Thomas
Habib, Jr.
2. Ethylene: Keystone to the Petrochemical Industry, Ludwig Kniel, Olaf Winter, and
Karl Stork
3. The Chemistry and Technology of Petroleum, James G. Speight
4. The Desulfurization of Heavy Oils and Residua, James G. Speight
5. Catalysis of Organic Reactions, edited by William R. Moser
6. Acetylene-Based Chemicals from Coal and Other Natural Resources, Robert J.
Tedeschi
7. Chemically Resistant Masonry, Walter Lee Sheppard, Jr.
8. Compressors and Expanders: Selection and Application for the Process Industry,
Heinz P. Bloch, Joseph A. Cameron, Frank M. Danowski, Jr., Ralph James, Jr.,
Judson S. Swearingen, and Marilyn E. Weightman
9. Metering Pumps: Selection and Application, James P. Poynton
10. Hydrocarbons from Methanol, Clarence D. Chang
11. Form Flotation: Theory and Applications, Ann N. Clarke and David J. Wilson
12. The Chemistry and Technology of Coal, James G. Speight
13. Pneumatic and Hydraulic Conveying of Solids, O. A. Williams
14. Catalyst Manufacture: Laboratory and Commercial Preparations, Alvin B. Stiles
15. Characterization of Heterogeneous Catalysts, edited by Francis Delannay
16. BASIC Programs for Chemical Engineering Design, James H. Weber
17. Catalyst Poisoning, L. Louis Hegedus and Robert W. McCabe
18. Catalysis of Organic Reactions, edited by John R. Kosak
19. Adsorption Technology: A Step-by-Step Approach to Process Evaluation and
Application, edited by Frank L. Slejko

20. Deactivation and Poisoning of Catalysts, edited by Jacques Oudar and Henry
Wise
21. Catalysis and Surface Science: Developments in Chemicals from Methanol,
Hydrotreating of Hydrocarbons, Catalyst Preparation, Monomers and Polymers,
Photocatalysis and Photovoltaics, edited by Heinz Heinemann and Gabor A.
Somorjai
22. Catalysis of Organic Reactions, edited by Robert L. Augustine
23. Modern Control Techniques for the Processing Industries, T. H. Tsai, J. W. Lane,
and C. S. Lin
24. Temperature-Programmed Reduction for Solid Materials Characterization, Alan
Jones and Brian McNichol
25. Catalytic Cracking: Catalysts, Chemistry, and Kinetics, Bohdan W. Wojciechowski
and Avelino Corma
26. Chemical Reaction and Reactor Engineering, edited by J. J. Carberry and A.
Varma
27. Filtration: Principles and Practices: Second Edition, edited by Michael J. Matteson
and Clyde Orr
28. Corrosion Mechanisms, edited by Florian Mansfeld
29. Catalysis and Surface Properties of Liquid Metals and Alloys, Yoshisada Ogino
30. Catalyst Deactivation, edited by Eugene E. Petersen and Alexis T. Bell
31. Hydrogen Effects in Catalysis: Fundamentals and Practical Applications, edited by
Zoltán Paál and P. G. Menon
32. Flow Management for Engineers and Scientists, Nicholas P. Cheremisinoff and
Paul N. Cheremisinoff
33. Catalysis of Organic Reactions, edited by Paul N. Rylander, Harold Greenfield,
and Robert L. Augustine
34. Powder and Bulk Solids Handling Processes: Instrumentation and Control, Koichi
Iinoya, Hiroaki Masuda, and Kinnosuke Watanabe
35. Reverse Osmosis Technology: Applications for High-Purity-Water Production, edited
by Bipin S. Parekh

36. Shape Selective Catalysis in Industrial Applications, N. Y. Chen, William E.
Garwood, and Frank G. Dwyer
37. Alpha Olefins Applications Handbook, edited by George R. Lappin and Joseph L.
Sauer
38. Process Modeling and Control in Chemical Industries, edited by Kaddour Najim
39. Clathrate Hydrates of Natural Gases, E. Dendy Sloan, Jr.
40. Catalysis of Organic Reactions, edited by Dale W. Blackburn
41. Fuel Science and Technology Handbook, edited by James G. Speight
42. Octane-Enhancing Zeolitic FCC Catalysts, Julius Scherzer
43. Oxygen in Catalysis, Adam Bielanski and Jerzy Haber
44. The Chemistry and Technology of Petroleum: Second Edition, Revised and
Expanded, James G. Speight
45. Industrial Drying Equipment: Selection and Application, C. M. van't Land
46. Novel Production Methods for Ethylene, Light Hydrocarbons, and Aromatics,
edited by Lyle F. Albright, Billy L. Crynes, and Siegfried Nowak
47. Catalysis of Organic Reactions, edited by William E. Pascoe
48. Synthetic Lubricants and High-Performance Functional Fluids, edited by Ronald L.
Shubkin
49. Acetic Acid and Its Derivatives, edited by Victor H. Agreda and Joseph R. Zoeller
50. Properties and Applications of Perovskite-Type Oxides, edited by L. G. Tejuca
and J. L. G. Fierro
51. Computer-Aided Design of Catalysts, edited by E. Robert Becker and Carmo J.
Pereira
52. Models for Thermodynamic and Phase Equilibria Calculations, edited by Stanley I.
Sandler
53. Catalysis of Organic Reactions, edited by John R. Kosak and Thomas A. Johnson
54. Composition and Analysis of Heavy Petroleum Fractions, Klaus H. Altgelt and
Mieczyslaw M. Boduszynski
55. NMR Techniques in Catalysis, edited by Alexis T. Bell and Alexander Pines
56. Upgrading Petroleum Residues and Heavy Oils, Murray R. Gray

57. Methanol Production and Use, edited by Wu-Hsun Cheng and Harold H. Kung
58. Catalytic Hydroprocessing of Petroleum and Distillates, edited by Michael C.
Oballah and Stuart S. Shih
59. The Chemistry and Technology of Coal: Second Edition, Revised and Expanded,
James G. Speight
60. Lubricant Base Oil and Wax Processing, Avilino Sequeira, Jr.
61. Catalytic Naphtha Reforming: Science and Technology, edited by George J.
Antos, Abdullah M. Aitani, and José M. Parera
62. Catalysis of Organic Reactions, edited by Mike G. Scaros and Michael L. Prunier
63. Catalyst Manufacture, Alvin B. Stiles and Theodore A. Koch
64. Handbook of Grignard Reagents, edited by Gary S. Silverman and Philip E. Rakita
65. Shape Selective Catalysis in Industrial Applications: Second Edition, Revised and
Expanded, N. Y. Chen, William E. Garwood, and Francis G. Dwyer
66. Hydrocracking Science and Technology, Julius Scherzer and A. J. Gruia
67. Hydrotreating Technology for Pollution Control: Catalysts, Catalysis, and
Processes, edited by Mario L. Occelli and Russell Chianelli
68. Catalysis of Organic Reactions, edited by Russell E. Malz, Jr.
69. Synthesis of Porous Materials: Zeolites, Clays, and Nanostructures, edited by
Mario L. Occelli and Henri Kessler
70. Methane and Its Derivatives, Sunggyu Lee
71. Structured Catalysts and Reactors, edited by Andrzej Cybulski and Jacob A.
Moulijn
72. Industrial Gases in Petrochemical Processing, Harold Gunardson
73. Clathrate Hydrates of Natural Gases: Second Edition, Revised and Expanded, E.
Dendy Sloan, Jr.
74. Fluid Cracking Catalysts, edited by Mario L. Occelli and Paul O’Connor
75. Catalysis of Organic Reactions, edited by Frank E. Herkes
76. The Chemistry and Technology of Petroleum: Third Edition, Revised and Ex-
panded, James G. Speight
77. Synthetic Lubricants and High-Performance Functional Fluids: Second Edition,

Revised and Expanded, Leslie R. Rudnick and Ronald L. Shubkin
78. The Desulfurization of Heavy Oils and Residua, Second Edition, Revised and
Expanded, James G. Speight
79. Reaction Kinetics and Reactor Design: Second Edition, Revised and Expanded,
John B. Butt
80. Regulatory Chemicals Handbook, Jennifer M. Spero, Bella Devito, and Louis
Theodore
81. Applied Parameter Estimation for Chemical Engineers, Peter Englezos and
Nicolas Kalogerakis
82. Catalysis of Organic Reactions, edited by Michael E. Ford
83. The Chemical Process Industries Infrastructure: Function and Economics,
James R. Couper, O. Thomas Beasley, and W. Roy Penney
84. Transport Phenomena Fundamentals, Joel L. Plawsky
85. Petroleum Refining Processes, James G. Speight and Baki Özüm
86. Health, Safety, and Accident Management in the Chemical Process Industries,
Ann Marie Flynn and Louis Theodore
87. Plantwide Dynamic Simulators in Chemical Processing and Control, William L.
Luyben
88. Chemicial Reactor Design, Peter Harriott
89. Catalysis of Organic Reactions, edited by Dennis Morrell
90. Lubricant Additives: Chemistry and Applications, edited by Leslie R. Rudnick
91. Handbook of Fluidization and Fluid-Particle Systems, edited by Wen-Ching
Yang
92. Conservation Equations and Modeling of Chemical and Biochemical Processes,
Said S. E. H. Elnashaie and Parag Garhyan
93. Batch Fermentation: Modeling, Monitoring, and Control, Ali Cinar, Satish J.
Parulekar, Cenk Ündey, and Gülnur Birol
94. Industrial Solvents Handbook, Second Edition, Nicholas P. Cheremisinoff
ADDITIONAL VOLUMES IN PREPARATION
Chemical Process Engineering: Design and Economics, Harry Silla

Process Engineering Economics, James R. Couper
Petroleum and Gas Field Processing, H. K. Abdel-Aal, Mohamed Aggour, and
M.A. Fahim
Thermodynamic Cycles: Computer-Aided Design and Optimization, Chih Wu
Re-Engineering the Chemical Processing Plant: Process Intensification,
Andrzej Stankiewicz and Jacob A. Moulijn
Preface to the Third Edition
Since the publication of the second edition, the refining industry has continued to evolve and
there is an increasing need to develop options to upgrade the abundant supply of known heavy
oil reserves into more value-added products. In addition, there has been an increased emphasis
on the need to understand the structure of petroleum and how this structure affects conversion
processes and the nature of the products. Indeed, the incompatibility of different feedstocks and
their respective products has also received considerable attention. This book follows that evolu-
tion with the inclusion of chapters on the structure of petroleum and the development of new
technologies for refining the heavier feedstocks.
The success of the first and second editions of this text has been the primary factor in the
decision to publish a third edition. Petroleum is perhaps the most important substance consumed
in modern society. It provides not only raw materials for the ubiquitous plastics and other prod-
ucts, but also fuel for energy, industry, heating, and transportation. From a chemical standpoint
petroleum is an extremely complex mixture of hydrocarbon compounds, usually with minor
amounts of nitrogen-, oxygen-, and sulfur-containing compounds as well as trace amounts of
metal-containing compounds.
Petroleum remains the main source of liquid fuels. The fuels that are derived from petro-
leum supply more than half of the world’s total supply of energy. Gasoline, kerosene, and diesel
oil provide fuel for automobiles, tractors, trucks, aircraft, and ships. Fuel oil and natural gas
are used to heat homes and commercial buildings, as well as to generate electricity. Petroleum
products are the basic materials used for the manufacture of synthetic fibers for clothing and
in plastics, paints, fertilizers, insecticides, soaps, and synthetic rubber. The uses of petroleum
as a source of raw material in manufacturing are central to the functioning of modern industry.
Petroleum refining is now in a significant transition period as the industry moves into the

21st century and the demand for petroleum products has shown a sharp growth in recent years.
The demand for light fuel oils for transport purposes is forecast to show steady growth in the
future, surely contributing to petroleum product demand patterns toward lighter oils. The sim-
plest means to cover the demand growth in light-oil products is to increase the imports of light
crude oils and light petroleum products, but these steps may be limited in the future.
Ultimately the essential step required of refineries is to upgrade heavy feedstocks, particu-
larly residua. In fact, the increased supply of heavy crude oils is a matter of serious concern
iii
iv Preface to the Third Edition
for the petroleum industry. In order to satisfy the changing pattern of product demand, significant
investments in refining conversion processes will be necessary to profitably utilize these heavy
crude oils. The most efficient and economical solution to this problem will depend to a large
extent on individual country and company situations. However, the most promising technologies
will likely involve the conversion of vacuum bottom residual oils, asphalt from deasphalting
processes, and super-heavy crude oils into useful light and middle distillate products.
The more efficient use of petroleum is of paramount importance. Petroleum technology,
in one form or another, is with us until suitable alternative forms of energy are readily available.
Therefore, a thorough understanding of the benefits and limitations of petroleum recovery and
processing is necessary and is introduced within the pages of this book.
Finally, I am indebted to my colleagues in many different countries who have continued
to engage me in lively discussions and who have offered many thought-provoking comments.
Thanks are also owed to those who have made constructive comments on the first edition, which
were of great assistance in the writing of the second edition and have been helpful in formulating
the contents and expanded sections of this third edition. For such discussions and commentary,
I continue to be grateful.
James G. Speight
Preface to the Second Edition
The success of the first edition of this text has been the primary factor in the decision to publish
a second edition. This second edition has been greatly expanded and rewritten to be more in
keeping with the technological aspects of the petroleum industry. For example, the original

section on petroleum recovery has been expanded to such an extent that it is now worthy of a
separate chapter. The origin of petroleum has been the subject of much discussion oflate; accord-
ingly, this section has also been expanded to such an extent that it was thought necessary to
include a chapter on kerogen. There are also expanded updates on the nature of the asphaltic
constituents of petroleum and how such constituents might be related to kerogen.
Since the first edition, there have been many changes in the refining industry. The overall
character of the feedstocks entering refineries has changed to such an extent that the difference
can be measured by a decrease of several points on the API gravity scale. Hence, in this edition,
frequent reference is made to refining of the heavier feedstocks, such as the heavy oils and
bitumens. There is also a more detailed section on the nature of the porphyrinic constituents of
petroleum as well as a section on how these particular constituents behave during refinery opera-
tions. There are also additions to the original chapter on refining chemistry so that the reader
can obtain a better understanding of the chemistry involved in the processing of the heavier
feedstocks. In addition, environmental issues have become of such importance that a vastly
expanded section on the cleanup of refinery gases and of natural gas (as it occurs with petroleum)
is now also a separate chapter. Finally, there are also further updates on the nature of petroleum
products as well as petrochemicals.
In addition, this edition has references cited throughout the text, in contrast to the first
edition, which contained general references provided in the form of bibliographies at the end
of each chapter. The decision to cite the references in the text will guide the reader to the original
article for more detail. I would also like to mention that there are many thousands of references
contained in my personal files. No attempt has been made to include all these references. I have
included those references that might give the reader the most information.
There are many people who should be thanked for their assistance in the preparation of
this text. My sincere appreciation is expressed to Professors Gordon Harris and Jack Evers,
Department of Petroleum Engineering, University of Wyoming, for the loan of the drill bits
(Figure 5, Chapter 5).
v
vi Preface to the Second Edition
The following oil companies, which contributed photographs of refinery operations, are

also gratefully acknowledged: Phillips Petroleum Company (Figure 11, Chapter 5), Sinclair
Refinery (Figure 12, Chapter 13; and Figure 12, Chapter 15), Shell Oil Company (Figure 13,
Chapter 13; and Figure 11, Chapter 15), Sun Oil Company (Figure 14, Chapter 13; and Figure
1, Chapter 19), and Chevron Oil Company (Figure 18, Chapter 16; and Figure 5, Chapter 19).
Finally, the author is indebted to his colleagues in many different countries who have
engaged him in lively discussions and have been responsible for many thought-provoking com-
ments. Thanks are also owed to those colleagues who have made constructive comments on the
first edition, which have been of great assistance in the writing of the second edition. Such is
the nature of scientists, and I am grateful.
James G. Speight
Preface to the First Edition
For many years petroleum has been regarded as the cheapest source of liquid fuels by many
countries, especially the United States and Canada. However, with recent ‘‘energy crises’’ and
concern over future supplies of gaseous and liquid fuels in many parts of the world, particularly
western Europe and North America, we have seen a gradual acceptance by the petroleum indus-
try and the general public of the inevitability that petroleum and natural gas will, at some time
within the foreseeable future, be in very short supply.
As a result, petroleum technology is being expanded to such an extent that wells that
were previously regarded as nonproductive because of their inability to produce oil without
considerable external stimulation are now being reexamined with the object of, literally, recov-
ering every last possible ‘‘drop’’ of petroleum.
Serious attempts are also underway to produce liquid fuels from unconventional sources,
such as coal, oil shale, and oil sands (also variously referred to as tar sands or bituminous sands).
Oil sands, in fact, have already been developed to such an extent that commercial production
of a synthetic crude oil from the oils sands located in northeastern Alberta (Canada) has been
underway for some ten years, with a second plant on-stream since 1978 and serious negotiations
underway for other oil sands plants.
This expansion of liquid fuels technology has resulted in a vacuum in the labor output
insofar as the universities have been unable to produce sufficient people with any form of training
in petroleum technology and petroleum chemistry. However, it now appears that various univer-

sities, which have initiated research into the various aspects of petroleum science, are now
considering some form of formal training in this area.
Thus it happened that during the winter of 1976–1977 the author organized a course
entitled ‘‘An Introduction to the Chemistry of Petroleum’’ through the Faculty of Extension at
the University of Alberta. In the early stages of preparation, it became apparent that, although
several older books were available, there was no individual book that could serve as a teaching
text for teachers and engineers as well as chemists. Therefore, this book is the outcome of the
copious notes collected as a result of that course. The text introduces the reader to the science
of petroleum, beginning with its formation in the ground, and eventually leads to analyses of
the production of a wide variety of petrochemical intermediates as well as the more conventional
fuel products. This book has also been written for those people already engaged in the petroleum
vii
viii Preface to the First Edition
industry (engineers and chemists) who wish to gain a general overview of the science of petro-
leum.
Although any text on petroleum must of necessity include some chemistry, attempts have
been made, for the benefit of those readers without any formal college training in chemistry,
to keep the chemical sections as simple as possible. In fact, there are, within the text, several
pages of explanatory elementary organic chemistry for the benefit of such people.
At a time when the anglicized nations of the world are undergoing a transferral to the
metric system of measurement, there are still those disciplines that are based upon such scales
as the Fahrenheit temperature scale as well as the foot measure instead of the meter. Accordingly,
the text contains both the metric and nonmetric measures, but it should be noted that exact
conversion is not often feasible, and thus conversion data are often taken to the nearest whole
number. Indeed, conversions involving the two temperature scales—Fahrenheit and Celsius—
are, at the high temperatures quoted in the text, often ‘‘rounded off’’ to the nearest 5°, especially
when serious error would not arise from such a conversion.
For the sake of simplicity, illustrations contained in the text, especially in the chapter
relating to petroleum refining, are line drawings, and no attempt has been made to draw to scale
the various reactors, distillation towers, or other equipment.

The majority of the work on this text was carried out while the author was a staff member
of the Alberta Research Council. Thus, the author wishes to acknowledge the assistance given
by the many members of the Alberta Research Council. The author is particularly indebted to
his colleagues Mr. J. F. Fryer and Dr. S. E. Moschopedis for their comments on the manuscript,
as well as to Mrs. P. Williams, Mrs. M. A. Harris, and Mrs. H. Radvanyi for typing the manu-
script.
James G. Speight
Contents
Preface to the Third Edition iii
Preface to the Second Edition v
Preface to the First Edition vii
Part I. History, Occurrence, and Recovery
1. History and Terminology 1
1. Historical Perspectives 1
2. Modern Perspectives 7
3. Definitions and Terminology 10
4. Native Materials 11
5. Manufactured Materials 20
6. Derived Materials 31
References 33
2. Classification 35
1. Introduction 35
2. Classification Systems 37
3. Miscellaneous Systems 48
4. Reservoir Classification 50
References 53
3. Origin and Occurrence 55
1. Introduction 55
2. Origin 58
3. Occurrence 106

References 118
ix
x Contents
4. Kerogen 121
1. Introduction 121
2. Composition 123
3. Classification 123
4. Isolation 126
5. Methods for Probing Kerogen Structure 128
6. Structural Models 134
7. Kerogen Maturation 139
References 146
5. Exploration, Recovery, and Transportation 149
1. Introduction 149
2. Exploration 150
3. Drilling 158
4. Well Completion 163
5. Recovery 164
6. Well Products and Product Quality 203
7. Transportation 207
References 213
Part II. Composition and Properties
6. Chemical Composition 215
1. Introduction 215
2. Ultimate (Elemental) Composition 216
3. Chemical Composition 221
References 241
7. Fractional Composition 244
1. Introduction 244
2. Distillation 249

3. Solvent Treatment 255
4. Adsorption 268
5. Chemical Methods 278
6. Use of the Data 286
References 298
8. Properties and Evaluation 300
1. Introduction 300
2. Physical Properties 304
3. Thermal Properties 322
4. Electrical Properties 342
5. Optical Properties 345
6. Spectroscopic Methods 347
7. Chromatographic Techniques 349
8. Molecular Weight 350
Contents xi
9. Use of the Data 351
References 355
9. Identification and Structural Group Analysis 358
1. Introduction 358
2. Chromatographic Methods 360
3. Structural Group Analysis 372
4. Miscellaneous Methods 405
References 405
10. Asphaltenes 412
1. Introduction 412
2. Separation 413
3. Composition 419
4. Molecular Weight 436
5. Reactions 442
6. Solubility Parameters 452

7. Structural Aspects 453
References 464
11. The Structure of Petroleum 468
1. Introduction 468
2. Molecular Species in Petroleum 469
3. The Structure of Petroleum 475
4. The Stability/Instability of the Crude Oil System 483
References 495
Part III. Refining
12. Refining Chemistry 499
1. Introduction 499
2. Cracking 503
3. Hydrogenation 508
4. Isomerization 509
5. Alkylation 512
6. Polymerization 514
7. Process Chemistry 514
8. Chemistry in the Refinery 527
References 533
13. Refinery Distillation 536
1. Introduction 536
2. Pretreatment 544
3. Early Processes 545
4. Modern Processes 548
xii Contents
5. Other Processes 557
References 563
14. Thermal Cracking 565
1. Introduction 565
2. Early Processes 571

3. Commercial Processes 573
References 584
15. Catalytic Cracking 585
1. Introduction 585
2. Early Processes 589
3. Commercial Processes 590
4. Catalysts 598
References 602
16. Hydroprocessing 604
1. Introduction 604
2. Commercial Processes 615
3. Catalysts 626
4. Hydrogen Production 633
References 638
17. Refining Heavy Feedstocks 641
1. Introduction 641
2. Thermal Processes 646
3. Catalytic Cracking Processes 651
4. Hydroconversion Processes 657
5. Solvent Processes 672
References 678
18. Product Improvement 680
1. Introduction 680
2. Thermal Reforming 681
3. Catalytic Reforming 684
4. Isomerization 693
5. Alkylation 698
6. Polymerization 699
7. Catalysts 704
8. Heteroatom Removal 706

References 708
19. Treatment Processes 709
1. Introduction 709
2. Commercial Processes 714
References 746
Contents xiii
20. Gas Cleaning 747
1. Introduction 747
2. Gas Cleaning 752
References 776
21. Products 777
1. Introduction 777
2. Gaseous Fuels 781
3. Gasoline 783
4. Solvents (Naphthas) 792
5. Kerosene 797
6. Fuel Oil 798
7. Lubricating Oil 799
8. Other Oil Products 803
9. Greases 805
10. Waxes 808
11. Asphalt 809
12. Coke 812
13. Sulfonic Acids 815
14. Acid Sludge 816
References 816
22. Instability and Incompatibility 818
1. Introduction 818
2. Instability and Incompatibility 822
3. Factors Influencing Instability and Incompatibility 823

4. Methods for Determining Instability and Incompatibility 828
5. Instability and Incompatibility in Petroleum Products 831
References 832
23. Petrochemicals 835
1. Introduction 835
2. Chemicals from Paraffins 840
3. Chemicals from Olefins 843
4. Chemicals from Aromatics 847
5. Chemicals from Natural Gas 848
6. Inorganic Petrochemicals 850
7. Synthesis Gas 851
References 853
Part IV. Environmental Issues
24. Environmental Aspects of Refining 854
1. Introduction 854
2. Definitions 857
3. Environmental Regulations 859
xiv Contents
4. Process Analysis 862
5. Epilog 871
References 872
Conversion Factors and Tables 875
Glossary 879
Index 909
1
History and Terminology
1. HISTORICAL PERSPECTIVES
Petroleum is perhaps the most important substance consumed in modern society. It provides
not only raw materials for the ubiquitous plastics and other products, but also fuel for energy,
industry, heating, and transportation. The word petroleum, derived from the Latin petra and

oleum, means literally rock oil and refers to hydrocarbons that occur widely in the sedimentary
rocks in the form of gases, liquids, semisolids, or solids.
From a chemical standpoint petroleum is an extremely complex mixture of hydrocarbon
compounds, usually with minor amounts of nitrogen-, oxygen-, and sulfur-containing com-
pounds as well as trace amounts of metal-containing compounds (Chapter 6).
The fuels that are derived from petroleum supply more than half of the world’s total
supply of energy. Gasoline, kerosene, and diesel oil provide fuel for automobiles, tractors, trucks,
aircraft, and ships. Fuel oil and natural gas are used to heat homes and commercial buildings,
as well as to generate electricity. Petroleum products are the basic materials used for the manu-
facture of synthetic fibers for clothing and in plastics, paints, fertilizers, insecticides, soaps, and
synthetic rubber. The uses of petroleum as a source of raw material in manufacturing are central
to the functioning of modern industry.
Petroleum is a carbon-based resource. Therefore, the geochemical carbon cycle is also of
interest to fossil fuel usage in terms of petroleum formation, use, and the buildup of atmospheric
carbon dioxide (Chapter 24). Thus, the more efficient use of petroleum is of paramount impor-
tance. Petroleum technology, in one form or another, is with us until suitable alternative forms
of energy are readily available (Boyle, 1996; Ramage, 1997). Therefore, a thorough understand-
ing of the benefits and limitations of petroleum recovery and processing is necessary and, hope-
fully, can be introduced within the pages of this book.
The history of any subject is the means by which the subject is studied in the hopes that
much can be learned from the events of the past. In the current context, the occurrence and use
of petroleum, petroleum derivatives (naphtha), heavy oil, and bitumen is not new. The use of
petroleum and its derivatives was practiced in pre-Christian times and is known largely through
historical use in many of the older civilizations (Henry, 1873; Abraham, 1945; Forbes, 1958a,b;
James and Thorpe, 1994). Thus, the use of petroleum and the development of related technology
1
2 Chapter One
is not such a modern subject as we are inclined to believe. However, the petroleum industry is
essentially a twentieth-century industry but to understand the evolution of the industry, it is
essential to have a brief understanding of the first uses of petroleum.

Although it is possible to differentiate between the words bitumen and asphalt in modern
use, the occurrence of these words in older texts offers no such possibility. It is significant that
the early use of bitumen was in the nature of a cement for securing or joining together various
objects, and thus it seems likely that the name itself was expressive of this application.
The word asphalt is claimed to be derived from the Accadian term asphaltu or sphallo,
meaning to split. It was later adopted by the Homeric Greeks in the form of the adjective
α σφαλη ς, ⑀ς, signifying firm, stable, secure, and the corresponding verb α σφαλι
´
ζω, ι
´
σω,
meaning to make firm or stable, to secure. It is a significant fact that the first use of asphalt by
the ancients was in the nature of a cement for securing or joining together various objects, such
as the bricks used for building and it thus seems likely that the name itself was expressive of
this application. From the Greek, the word passed into late Latin (asphaltum, aspaltum), and
thence into French (asphalte) and English (aspaltoun).
The origin of the word bitumen is more difficult to trace and subject to considerable
speculation. The word was proposed to have originated in the Sanskrit, where we find the words
jatu, meaning pitch, and jatukrit, meaning pitch creating. From the Sanskrit, the word jatu was
incorporated into the Latin language as gwitu and is reputed to have eventually become gwitumen
(pertaining to pitch). Another word, pixtumen (exuding or bubbling pitch) is also reputed to
have been in the Latin language, although the construction of this Latin word from which the
word bitumen was reputedly derived, is certainly suspect. There is the suggestion that subsequent
derivation of the word led to a shortened version (which eventually became the modern version)
bitu
ˆ
men thence passing via French into English. From the same root is derived the Anglo Saxon
word cwidu (mastic, adhesive), the German work kitt (cement or mastic) and the equivalent
word kvada which is found in the old Norse language as being descriptive of the material used
to waterproof the long ships and other sea-going vessels. It is just as (perhaps even more than)

likely that the word is derived from the Celtic bethe or beithe or bedw which was the birch tree
that was used as a source of resin (tar). The word appears in Middle English as bithumen.In
summary, a variety of terms exist in ancient language from which, from their described use in
texts, they can be proposed as having the meaning bitumen or asphalt (Table 1-1) (Abraham,
1945).
Using these ancient words as a guide, it is possible to trace the use of petroleum and its
derivatives as described in ancient texts. And, preparing derivatives of petroleum was well within
the area of expertise of the early scientists (perhaps refiners would be a better term) since al-
chemy (early chemistry) was known to consist of four sub-routines: dissolving, melting, combin-
ing, and distilling (Cobb and Goldwhite, 1995).
Early references to petroleum and its derivatives occur in the Bible, although by the time
the various books of the Bible were written, the use of petroleum and bitumen was established.
Nevertheless, these writings do offer documented examples of the use of petroleum and related
materials.
The caulking of a vessel with pitch is noted (Genesis 6:14):
Make thee an ark of gopher wood; rooms shalt thou make in the ark, and shalt pitch it within
and without with pitch.
and the occurrence of slime (bitumen) pits in the Valley of Siddim (Genesis, 14:10), a valley
at the southern end of the Dead Sea, is reported. There is also reference to the use of tar as a
mortar when the Tower of Babel was under construction (Genesis 11:3):
And they said one to another, Go to, let us make brick, and burn them throughly. And they
had brick for stone, and slime had they for mortar.
History and Terminology 3
Table 1-1 Linguistic Origins of Words Related to the Various Aspects of
Petroleum Technology
Language Word Possible meaning
Sumerian esir petroleum
bitumen
esir-lah hard/glossy asphalt
esir-harsag rock asphalt

esir-e
´
-a mastic asphalt
esir-ud-du-a pitch
Sanskrit jatu bitumen
pitch
s
´
ila
¯
-jatu rock asphalt
as
´
maja
¯
tam-jatu rock asphalt
Assyrian/Accadian idd
¯
, ittu
ˆ
, it-tu
ˆ
-u bitumen
amaru bitumen
sippatu pitch
Hebrew zephet bitumen
kopher or kofer pitch
he
ˆ
ma

ˆ
r pitch
Arabic and Turkish seyali bitumen
zift or zipht bitumen or pitch
chemal rock asphalt
humar (houmar) rock asphalt
gasat (qasat) rock asphalt
ghir or gir asphalt mastic
kir or kafr asphalt mastic or pitch
neftgil mineral wax
Greek maltha soft asphalt
asphaltos bitumen
pissasphaltos rock asphalt
pittasphaltos rock asphalt
pittolium rock asphalt
pissa or pitta pitch
ampelitis mineral wax and asphaltites
Latin maltha soft asphalt
bitumen liquidum soft asphalt
pix pitch
In the Septuagint, or Greek version of the Bible, this word is translated as asphaltos, and in
the Vulgate or Latin version, as bitumen. In the Bishop’s Bible of 1568 and in subsequent
translations into English, the word is given as slime. In the Douay translation of 1600, it is
bitume, while in Luther’s German version, it appears as thon, the German word for clay.
Another example of the use of pitch (and slime) is given in the story of Moses (Exodus
2:3):
And when she could not longer hide him, she took for him an ark of bulrushes, and daubed
it with slime and with pitch, and put the child therein; and she laid it in the flags by the
river’s brink.
Perhaps the slime was a lower melting bitumen whereas the pitch was a higher melting material;

the one (slime) acting as a flux for the other (pitch). The lack of precise use of the words for
bitumen and asphalt as well as for tar and pitch even now makes it unlikely that the true nature
4 Chapter One
of the biblical tar, pitch, and slime will ever be known, but one can imagine their nature! In
fact, even modern Latin dictionaries give the word bitumen as the Latin word for asphalt!
It is most probable that, in both these cases, the pitch and the slime were obtained from the
seepage of oil to the surface, which was a fairly common occurrence in the area. And during biblical
times,bitumenwasexportedfromCanaantovariousparts of thecountriesthatsurroundtheMediter-
ranean (Armstrong, 1997). Hence the use of such material in Egypt to caulk Moses’ vessel.
In terms of liquid products, there is an interesting reference (Deuteronomy, 32:13) to
bringing oil out of flinty rock. The exact nature of the oil is not described nor is the nature of
the rock. The use of oil for lamps is also referenced (Matthew, 23:3) but whether is was mineral
oil (a petroleum derivative such as naphtha) or whether is was vegetable oil is not known.
Excavations conducted at Mohenjo-Daro, Harappa, and Nal in the Indus Valley indicated
that an advanced form of civilization existed there. An asphalt mastic composed of a mixture
of asphalt, clay, gypsum, and organic matter was found between two brick walls in a layer about
25 mm thick, probably a waterproofing material. Also unearthed was a bathing pool that con-
tained a layer of mastic on the outside of its walls and beneath its floor.
In the Bronze Age, dwellings were constructed on piles in lakes close to the shore to
better protect the inhabitants from the ravages of wild animals and attacks from marauders.
Excavations have shown that the wooden piles were preserved from decay by coating with
asphalt, and posts preserved in this manner have been found in Switzerland. There are also
references to deposits of bitumen at Hit (the ancient town of Tuttul in Mesopotamia) and the
bitumen from these deposits was transported to Babylon for use in construction (Herodotus,
The Histories , Book I). There is also reference (Herodotus, The Histories, Book IV) to a Cartha-
ginian story in which birds’ feathers smeared with pitch are used to recover gold dust from the
waters of a lake.
One of the earliest recorded uses of asphalt was by the pre-Babylonian inhabitants of the
Euphrates Valley in southeastern Mesopotamia, present-day Iraq, formerly called Sumer and
Akkad and, later, Babylonia. In this region there are various asphalt deposits, and uses of the

material have become evident. For example, King Sargon as an infant was reputed to have been
placed by his mother in a reed basket coated with asphalt and set adrift on the waters of the
Euphrates River during one of its frequent overflows. On the other hand, the bust of Manishtusu,
King of Kish, an early Sumerian ruler (about 2270 BC), was found in the course of excavations
at Susa in Persia, and the eyes, composed of white limestone, are held in their sockets with the
aid of bitumen. Fragments of a ring composed of asphalt have been unearthed above the flood
layer of the Euphrates at the site of the prehistoric city of Ur in southern Babylonia, ascribed
to the Sumerians of about 3500 BC.
An ornament excavated from the grave of a Sumerian king at Ur consists of a statue of
a ram with the head and legs carved out of wood over which gold foil was cemented by means
of asphalt. The back and flanks of the ram are coated with asphalt in which hair was embedded.
Another art of decoration consisted in beating thin strips of gold or copper, which were then
fastened to a core of asphalt mastic. An alternative method was to fill a cast metal object with
a core of asphalt mastic, and such specimens have been unearthed at Lagash and Nineveh.
Excavations at Tell-Asmar, 50 miles northeast of Baghdad, revealed the use of asphalt by the
Sumerians for building purposes.
Mortar composed of asphalt has also been found in excavations at Ur, Uruk, and Lagash,
and excavations at Khafaje have uncovered floors composed of a layer of asphalt that has been
identified as asphalt, mineral filler (loam, limestone, and marl), and vegetable fibers (straw).
Excavations at the city of Kish (Persia) in the palace of King Ur-Nina showed that the founda-
tions consist of bricks cemented together with an asphalt mortar. Similarly, in the ancient city
of Nippur (about 60 miles south of Baghdad), excavations show Sumerian structures composed
History and Terminology 5
of natural stones joined together with asphalt mortar. Excavation has uncovered an ancient
Sumerian temple in which the floors are composed of burnt bricks embedded in an asphalt
mastic that still shows impressions of reeds with which it must originally have been mixed.
The Epic of of Gilgamesh (written before 2500 BC) and transcribd on to clay tablets
during the time of Assurbanipal, king of Assyria (668–626 BC), make reference to the use of
asphalt for building purposes. In the eleventh tablet, Ut-Napishtim relates the well-known story
of the Babylonian flood, stating that he smeared

. . . . the inside of a boat with six sar of kupru and the outside with three sar . . . .
There are indications from these texts that asphalt mastic was sold by volume (by the gur). On
the other hand, bitumen was sold by weight (by the mina or shekel).
Use of asphalt by the Babylonians (1500 to 538 BC) is also documented. The Babylonians
were well versed in the art of building, and each monarch commemorated his reign and perpetu-
ated his name by the construction of a building or other monuments. For example, the use of
bitumen mastic in cities such as Babylon, Nineveh, Calah, and Ur has been observed (Speight,
1978) and the bitumen lines are still evident.
Bitumen was used as mortar from very early times, and sand, gravel, or clay was employed
in preparing these mastics. Asphalt-coated tree trunks were often used to reinforce wall corners
and joints, for instance in the temple tower of Ninmach in Babylon. In vaults or arches, a mastic-
loam composite was used as mortar for the bricks, and the keystone was usually dipped in
asphalt before being set in place. The use of bituminous mortar was said to have been introduced
in the city of Babylon by King Khammurabi, but the use of bituminous mortar was abandoned
toward the end of Nebuchadnezzar’s reign in favor of lime mortar to which varying amounts
of asphalt were added. The Assyrians recommended the use of asphalt for medicinal purposes,
as well as for building purposes, and perhaps there is some merit in the fact that the Assyrian
moral code recommended that asphalt, in the molten state, be poured onto the heads of delin-
quents. Pliny, the Roman author, also notes that bitumen could be used to stop bleeding, heal
wounds, drive away snakes, treat cataracts as well as a wide variety of other diseases, and
straighten out eyelashes which inconvenience the eyes. One can appreciate the use of bitumen
to stop bleeding but its use to cure other ailments is questionable and one has to consider what
other agents were being used concurrently with bitumen.
The Egyptians were the first to adopt the practice of embalming their dead rulers and
wrapping the bodies in cloth.
Before 1000 BC, asphalt was rarely used in mummification, except to coat the cloth wrap-
pings and thereby protect the body from the elements. After the viscera had been removed, the
cavities were filled with a mixture of resins and spices, the corpse immersed in a bath of potash
or soda, dried, and finally wrapped. From 500 to about 40 BC, asphalt was generally used both
to fill the corpse cavities, as well as to coat the cloth wrappings. The word mu

ˆ
mu
ˆ
ia first made
its appearance in Arabian and Byzantine literature about 1000 AD, signifying bitumen.
In Persian, the term bitumen is believed to have acquired the meaning equivalent to paraf-
fin wax which might be symptomatic of the nature of some of the crude oils in the area. Alterna-
tively, it is also possible that the destructive distillation of bitumen to produce pitch produced
paraffins which crystallized from the mixture over time. In Syriac, the term alluded to substances
used for mummification. In Egypt, resins were used extensively for purposes of embalming up
until the Ptolemaic period, when asphalts gradually came into use.
The product mu
ˆ
mu
ˆ
ia was used in prescriptions, as early as the 12th century, by the Arabian
physician Al Magor, for the treatment of contusions and wounds. Its production soon became
a special industry in the Alexandria. The scientist Al-Kazwı
ˆ
nı
ˆ
alludes to the healing properties
of mu
ˆ
mu
ˆ
ia, and Ibn Al-Baita
ˆ
r gives an account of its source and composition. Engelbert Ka
¨

mpfer
6 Chapter One
(1651–1716) in his treatise Amoenitates Exoticae gives a detailed account of the gathering of
mu
ˆ
mu
ˆ
ia, the different grades and types, and its curative properties in medicine. As the supply
of mummies was of course limited, other expedients came into vogue. The corpses of slaves
or criminals were filled with asphalt, swathed and artificially aged in the sun. This deception
continued for several centuries until in 1564 AD, it was exposed after a journey into Egypt by
the French physician, Guy de la Fontaine, and as a result, this trade became extinct in the 17th
century.
Many other references to bitumen occur throughout the Greek and Roman empires, and
from then to the Middle Ages early scientists (alchemists) frequently alluded to the use of bitu-
men. In later times, both Christopher Columbus and Sir Walter Raleigh (depending upon the
country of origin of the biographer) have been credited with the discovery of the asphalt deposit
on the island of Trinidad and apparently used the material to caulk their ships.
The use of petroleum has also been documented in China: as early as 600 BC (Owen,
1975), petroleum was encountered when drilling for salt and mention of petroleum as an impurity
in the salt is also noted in documents of the third century AD. It is presumed that the petroleum
that contaminated the salt might be similar to that found in Pennsylvania and was, therefore, a
more conventional type rather than the heavier type.
There was also an interest in the thermal product of petroleum (nafta; naphtha) when it
was discovered that this material could be used as an illuminant and as a supplement to asphalt
incendiaries in warfare. For example, there are records of the use of mixtures of pitch and/or
naphtha with sulfur as a weapon of war during the Battle of Palatea, Greece, in the year 429
BC (Forbes, 1959). There are references to the use of a liquid material, naft (presumably the
volatile fraction of petroleum which we now call naphtha and which is used as a solvent or as
a precursor to gasoline), as an incendiary material during various battles of the pre-Christian

era (James and Thorpe, 1994). This is the so-called Greek fire, a precursor and chemical cousin
to napalm.
This probably represents the first documented use of the volatile derivatives of petroleum
which led to a continued interest in petroleum.
Greek fire was a viscous liquid that ignited on contact with water and was sprayed from
a pump-like device on to the enemy. One can imagine the early users of the fire attempting to
ignite the liquid before hurling it towards the enemy
However, the hazards that can be imagined from such tactics could become very real, and
perhaps often fatal, to the users of the Greek fire if any spillage occurred before ejecting the
fire towards the enemy. The later technology for the use of Greek fire probably incorporated a
heat-generating chemical such as quicklime (CaO) (Cobb and Goldwhite, 1995) which was
suspended in the liquid and which, when coming into contact with water (to produce [Ca(OH)
2
]),
released heat that was sufficient to cause the liquid to ignite. One assumes that the users of the
fire were extremely cautious during periods of rain or, if at sea, during periods of turbulent
weather.
The combustion properties of bitumen (and its fractions) were known in Biblical times.
There is reference to these properties (Isaiah, 34:9) when it is stated that:
And the stream thereof shall be turned into pitch, and the dust thereof into brimstone, and
the land thereof shall become burning pitch.
It shall not be quenched night nor day ; the smoke thereof shall go up forever: from
generation to generation it shall lie waste; none shall pass through it for ever and for ever.
One might surmise that the effects of the burning bitumen and sulfur (brimstone) were long
lasting and quite devastating.
Approximately two thousand years ago, Arabian scientists developed methods for the