148,99 €
Mehr erfahren.
- Herausgeber: John Wiley & Sons
- Kategorie: Fachliteratur
- Sprache: Englisch
Handbook of Heavy Oil Properties and Analysis Understand the future of oil production with this comprehensive guide Heavy oil, also known as viscous oil, is oil too viscous to flow normally from wells and reservoirs. In recent decades it has become increasingly important as a source of liquid oil for use in industrial processes. This places all the greater importance on proper analysis of heavy oil and its properties, so that it can be more effectively refined and deployed to meet ever-growing energy needs. Handbook of Heavy Oil Properties and Analysis provides a comprehensive introduction to the analysis of viscous oil and its properties. It discusses the full range of tests and analytical procedures by which the behavior and refinability of viscous oil samples can be predicted and connects theoretical knowledge to refinery practice throughout. Additionally, its incorporation of the latest environmental regulations makes it an invaluable resource. Readers will also find: * Detailed coverage of both physical properties and chemical composition of heavy oil * An author more than fifty years of experience in the process industries * Discussion of new methods for determining instability and incompatibility This book is a useful reference for scientists and engineers in the oil refining industries, chemists and researchers in heavy oil and adjacent industries, and government officials and regulators.
Sie lesen das E-Book in den Legimi-Apps auf:
Seitenzahl: 978
Veröffentlichungsjahr: 2023
Ähnliche
Table of Contents
Cover
Title Page
Copyright Page
About the Author
Preface
1 History and Terminology
1.1 Introduction
1.2 Historical Perspectives
1.3 Definitions and Terminology
1.4 Classification
1.5 Feedstock Evaluation
1.6 Modern Analytical Perspectives
References
2 Sampling and Measurement
2.1 Introduction
2.2 Sampling
2.3 Measurement
2.4 Method Validation
2.5 Quality Control and Quality Assurance
2.6 Assay and Specifications
2.7 Environmental Issues
References
3 Chemical Composition
3.1 Introduction
3.2 Elemental Composition
3.3 Chemical Composition
3.4 Chemical Composition by Distillation
3.5 Chemical Composition by Spectroscopy
References
4 Fractional Composition
4.1 Introduction
4.2 Distillation
4.3 Solvent Treatment
4.4 Adsorption
4.5 Chemical Methods
4.6 The Asphaltene Fraction
4.7 Carbenes and Carboids
4.8 Use of the Data
References
5 Chemical Properties
5.1 Introduction
5.2 Acid Number
5.3 Elemental Analysis and Metals
5.4 Emulsion Formation
5.5 Evaporation
5.6 Flash Point and Fire Point
5.7 Functional Group Analysis
5.8 Halogenation
5.9 Hydrogenation
5.10 Oxidation
5.11 Thermal Methods
5.12 Miscellaneous Methods
References
6 Physical Properties, Electrical Properties, and Optical Properties
6.1 Introduction
6.2 Physical Properties
6.3 Electrical Properties
6.4 Optical Properties
References
7 Thermal Properties
7.1 Introduction
7.2 Ash Production
7.3 Carbon Residue
7.4 Critical Properties
7.5 Enthalpy
7.6 Heat of Combustion
7.7 Latent Heat
7.8 Liquefaction and Solidification
7.9 Pour Point
7.10 Pressure–Volume–Temperature Relationships
7.11 Softening Point
7.12 Specific Heat
7.13 Thermal Conductivity
7.14 Volatility
References
8 Chromatographic Properties
8.1 Introduction
8.2 Adsorption Chromatography
8.3 Gas Chromatography
8.4 Gel Permeation Chromatography
8.5 High‐Performance Liquid Chromatography
8.6 Ion Exchange Chromatography
8.7 Simulated Distillation
8.8 Supercritical Fluid Chromatography
8.9 Thin Layer Chromatography
References
9 Structural Group Analysis
9.1 Introduction
9.2 Physical Property Methods
9.3 Spectroscopic Methods
9.4 Heteroatom Systems
9.5 Miscellaneous Methods
References
10 Molecular Weight Determination
10.1 Introduction
10.2 Methods for Molecular Weight Measurement
10.3 Molecular Weights of Volatile Fractions
10.4 Molecular Weights of Nonvolatile Fractions
References
11 Instability and Incompatibility
11.1 Introduction
11.2 Occurrence of Instability and Incompatibility
11.3 Factors Influencing Instability and Incompatibility
11.4 Determination of Instability and Incompatibility
References
12 Use of the Data
12.1 Introduction
12.2 Use of the Data
12.3 Process Analysis and Feedstock Mapping
12.4 Environmental Aspects of Processing
12.5 Analytical Methods for Environmental Regulations
References
Glossary
Conversion Factors
Index
End User License Agreement
List of Tables
Chapter 1
Table 1.1 Examples of the Origins of Words Related to Crude Oil and Bitumen...
Table 1.2 Boiling Fractions of Conventional Crude Oil
Table 1.3 Hydrocarbon and Heteroatom Types in Crude Oil, Heavy Oil, and Tar...
Table 1.4 Examples of the Variation in the Properties of Crude Oil
Table 1.5 Feedstock Properties and Their Respective Impacts on Refining
Table 1.6 Example of the Properties of Vacuum Gas Oil
Table 1.7 Example of the Properties of Heavy Crude Oil
Table 1.8 Simplified Differentiation Between Conventional Crude Oil, Tight ...
Table 1.9 Use of Pour Point and Reservoir/Deposit Temperature to Differenti...
Table 1.10 Examples of the Properties of Tar Sand Bitumen
Table 1.11 Comparison of the Properties of Conventional Crude Oil and Tar S...
Table 1.12 Properties of Residua Showing the Differences Between Atmospheri...
Table 1.13 Properties of Tia Juana Crude Oil and the Different Residua
Table 1.14 Examples of ASTM Standard Test Methods for Asphalt and Pitch
Table 1.15 Recommended Inspection Data Required for Crude Oil and the Visco...
Chapter 2
Table 2.1 Example of the Content and Makeup of a Sampling Log
Table 2.2 Recommended Analytical Inspections
a
for Crude Oil and the Viscous...
Chapter 3
Table 3.1 Hydrocarbon Derivatives and Heteroatom Derivatives that Occur in ...
Table 3.2 Standard Test Methods Designated for Elemental Analysis
Table 3.3 Hydrocarbon Derivatives Present in Feedstocks
Chapter 4
Table 4.1 Definition of the Parameters for the Separation of the Asphaltene...
Table 4.2 Separation of Asphaltene Constituents Based on Functionality (Pol...
Table 4.3 Operative Parameters in the Separation of the Asphaltene Fraction...
Table 4.4 Representation of the Multi‐Reaction Sequence for the Thermal Dec...
Chapter 9
Table 9.1 The Various Compound Classes and Compound Types in Petroleum
Table 9.2 Infrared Absorption Frequencies
Chapter 11
Table 11.1 Examples of Properties Related to Instability in Feedstocks
Table 11.2 Standard Methods for Asphaltene Precipitation
Table 11.3 Simplified representation of the concentration of the feedstock ...
List of Illustrations
Chapter 1
Figure 1.1 Thiophene (the numbers, 2–5, indicate the positions of the substi...
Figure 1.2 Examples of organic sulfur derivative that occur in crude oil and...
Figure 1.3 Benzene (showing the various alternate structures; in terms of re...
Figure 1.4 Pyridine (the numbers, 2–6, indicate the positions of the substit...
Figure 1.5 Examples of organic nitrogen derivatives that occur in crude oil ...
Figure 1.6 Examples of organic oxygen derivatives that occur in crude oil an...
Figure 1.7 Examples of (a) peri‐condensed and (b) kata‐condensed aromatic sy...
Figure 1.8 Schematic of the separation of oil into various bulk fractions.
Chapter 3
Figure 3.1 Nomenclature and types of thiophene compounds.
Figure 3.2 Nomenclature and types of organic nitrogen compounds.
Figure 3.3 Examples of the common organic‐containing functional groups.
Figure 3.4 The structure of porphine.
Figure 3.5 The nickel chelate of porphine.
Figure 3.6 (a) Examples of peri‐condensed aromatic systems. (b) Examples of ...
Chapter 4
Figure 4.1 General fractionation scheme for crude oil and the viscous feedst...
Chapter 5
Figure 5.1 Examples of oxygen‐containing functional groups.
Chapter 10
Figure 10.1 Representation of the difference between the number average mole...
Chapter 11
Figure 11.1 General fractionation scheme and nomenclature of petroleum fract...
Guide
Cover Page
Title Page
Copyright Page
Preface
Table of Contents
Begin Reading
Glossary
Conversion Factors
Index
Wiley End User License Agreement
About the Author
Pages
iii
iv
xiii
xiv
xv
xvi
xvii
xviii
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
143
144
145
146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
180
181
182
183
184
185
186
187
188
189
191
192
193
194
195
196
197
198
199
200
201
202
203
204
205
206
207
208
209
210
211
212
213
214
215
216
217
218
219
220
221
222
223
224
225
226
227
229
230
231
232
233
234
235
236
237
238
239
240
241
242
243
244
245
246
247
248
249
250
251
252
253
255
256
257
258
259
260
261
262
263
264
265
266
267
268
269
270
271
272
273
274
275
276
277
278
279
280
281
282
283
284
285
286
287
288
289
290
291
292
293
294
295
296
297
298
299
300
301
302
303
304
305
306
307
308
309
310
311
312
313
314
315
316
317
318
319
320
321
322
323
324
325
326
327
328
329
330
331
332
333
334
335
336
337
338
339
340
341
342
343
344
345
346
347
348
349
350
351
352
353
354
355
357
358
359
360
361
362
363
364
365
366
367
368
369
370
371
372
373
374
375
376
377
378
379
380
381
383
384
385
386
387
388
389
390
391
392
393
394
395
396
397
398
399
400
401
402
403
404
405
406
407
408
409
410
411
412
413
414
415
416
417
418
419
420
421
422
423
424
425
426
427
428
429
430
431
432
433
434
435
436
437
438
439
441
442
443
444
445
446
447
448
449
450
451
452
453
454
455
456
457
458
459
460
461
462
463
464
465
466
467
468
469
470
471
472
473
474
Handbook of Heavy Oil Properties and Analysis
James G. Speight
CD & W Inc.Laramie, WY, USA
Copyright © 2023 by John Wiley & Sons Inc. All rights reserved.
Published by John Wiley & Sons, Inc., Hoboken, New Jersey.Published simultaneously in Canada.
No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning, or otherwise, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per‐copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, (978) 750‐8400, fax (978) 750‐4470, or on the web at www.copyright.com. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, (201) 748‐6011, fax (201) 748‐6008, or online at http://www.wiley.com/go/permission.
Trademarks: Wiley and the Wiley logo are trademarks or registered trademarks of John Wiley & Sons, Inc. and/or its affiliates in the United States and other countries and may not be used without written permission. All other trademarks are the property of their respective owners. John Wiley & Sons, Inc. is not associated with any product or vendor mentioned in this book.
Limit of Liability/Disclaimer of Warranty: While the publisher and author have used their best efforts in preparing this book, they make no representations or warranties with respect to the accuracy or completeness of the contents of this book and specifically disclaim any implied warranties of merchantability or fitness for a particular purpose. No warranty may be created or extended by sales representatives or written sales materials. The advice and strategies contained herein may not be suitable for your situation. You should consult with a professional where appropriate. Further, readers should be aware that websites listed in this work may have changed or disappeared between when this work was written and when it is read. Neither the publisher nor authors shall be liable for any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential, or other damages.
For general information on our other products and services or for technical support, please contact our Customer Care Department within the United States at (800) 762‐2974, outside the United States at (317) 572‐3993 or fax (317) 572‐4002.
Wiley also publishes its books in a variety of electronic formats. Some content that appears in print may not be available in electronic formats. For more information about Wiley products, visit our web site at www.wiley.com.
Library of Congress Cataloging‐in‐Publication Data:
Names: Speight, James G., author.Title: Handbook of heavy oil properties and analysis / James G. Speight, CD & W Inc., Laramie, WY, USA.Description: Hoboken, NJ, USA : John Wiley & Sons, Inc, 2023. | Includes bibliographical references and index.Identifiers: LCCN 2023001790 (print) | LCCN 2023001791 (ebook) | ISBN 9781119577157 (hardback) | ISBN 9781119577126 (adobe pdf) | ISBN 9781119577102 (epub)Subjects: LCSH: Heavy oil–Testing. | Analytical chemistry. Classification: LCC TP691 .S6869 2023 (print) | LCC TP691 (ebook) | DDC 553.2/82–dc23/eng/20230213LC record available at https://lccn.loc.gov/2023001790LC ebook record available at https://lccn.loc.gov/2023001791
Cover Design: WileyCover Images: © Adrienne Bresnahan/Getty Images
About the Author
Dr. James G. Speight has a BSc and PhD in Chemistry; he also holds a DSc in Geological Sciences and a PhD in Petroleum Engineering. He has more than 50 years of experience in areas associated with (1) the properties, recovery, and refining of reservoir fluids, conventional petroleum, heavy oil, and tar sand bitumen; (2) the properties and refining of natural gas, gaseous fuels; (3) the properties and refining of biomass, biofuels, biogas; and (4) the generation of bioenergy. His work has also focused on environmental effects, environmental remediation, and safety issues associated with the production and use of fuels and biofuels. He is the author (and coauthor) of more than 100 books in petroleum science and engineering, biomass, biofuels, and environmental sciences.
Although he has always worked in private industry which focused on contract‐based work, Dr. Speight has served as Adjunct Professor in the Department of Chemical and Fuels Engineering at the University of Utah and in the Departments of Chemistry and Chemical and Petroleum Engineering at the University of Wyoming. In addition, he was a Visiting Professor in the College of Science, University of Mosul (Iraq) and has also been a Visiting Professor in Chemical Engineering at the following universities: University of Akron (Ohio), University of Missouri‐Columbia, Technical University of Denmark, and University of Trinidad and Tobago. He has served as a thesis examiner for more than 30 theses and has been an advisor/mentor to MSc and PhD students.
Dr. Speight has been honored as the recipient of the following awards:
Diploma of Honor, United States National Petroleum Engineering Society.
For Outstanding Contributions to the Petroleum Industry,
1995.
Gold Medal of the Russian Academy of Sciences.
For Outstanding Work in Petroleum Science
. 1996.
Einstein Medal of the Russian Academy of Sciences.
In recognition of Outstanding Contributions and Service in the field of Geologic Sciences
. 2001.
Gold Medal—Scientists without Frontiers, Russian Academy of Sciences.
In recognition of His Continuous Encouragement of Scientists to Work Together across International Borders
. 2005.
Methanex Distinguished Professor, University of Trinidad and Tobago.
In Recognition of Excellence in Research
. 2006.
Gold Medal—Giants of Science and Engineering, Russian Academy of Sciences.
In recognition of Continued Excellence in Science and Engineering
. 2006.
Preface
The need for, and the acceptance of, the use of the viscous feedstocks as refinery feedstocks oil has increased substantially during the second half of the 20th century. Thus, attempts to understand and manipulate refinery processes have persisted over centuries, with an explosion of technological innovation and research occurring in the last 100 years. The majority of these efforts have focused on using the knowledge gained to produce a useful product and achieve a perceived improvement in the performance of that product.
The laws of science will ultimately dictate what can or cannot be done with feedstocks to provide the needed products. The science of analytical chemistry is at the core of understanding of both the problems of processing various feedstocks. This book will examine through a presentation discussion of the way that the analytical science has been applied to defining the properties and behavior of the different feedstocks that are used in the heavy crude oil, extra heavy crude oil, and tar sand bitumen (known collectively in this text as viscous feedstocks) refining industry.
In the 20th century and at the beginnings of the 21th century, scientists and engineers have become increasingly well‐versed in utilizing chemical knowledge to better understand the nature of the feedstocks that arbitrarily fall under the term “heavy oil” but are more correctly known as viscous feedstocks (which include heavy crude oil, extra heavy crude oil, and tar sand bitumen) and the influence of each feedstock on refining scenarios and on product slate. Definitions of processing do's and don'ts abound in the scientific and engineering literature but the essence of these rules depends on analytical chemical measurements.
Heavy crude oil, extra heavy crude oil, and tar sand bitumen exhibit a wide range of physical properties and a wide range of tests have been (and continue to be) developed to provide an indication of the means by which a particular feedstock should be processed. Initial inspection of the nature of the viscous feedstocks will provide deductions about the most logical means of refining or correlation of various properties to structural types present and hence attempted classification of the viscous feedstocks. Proper interpretation of the data resulting from the inspection of crude oil requires an understanding of their significance.
Evaluation of heavy crude oil, extra heavy crude oil, and tar sand bitumen for use as refinery feedstocks usually involves an examination of one or more of the physical properties of the material. By this means, a set of basic characteristics can be obtained that can be correlated with utility. Consequently, various standards organizations, such as the American Society for Testing and Materials in North America have devoted considerable time and effort to the correlation and standardization of methods for the inspection and evaluation of the products from the viscous feedstocks.
The acceptance of the viscous feedstocks by refineries has meant that the analytical techniques used for the lighter feedstocks have had to evolve to produce meaningful data that can be employed to assist in defining refinery scenarios for processing the feedstocks. In addition, selection of the most appropriate analytical procedures will aid in the predictability of feedstock behavior during refining. This same rationale can also be applied to feedstocks behavior during recovery operations.
Because of the wide range of chemical and physical properties, a wide range of tests have been (and continue to be) developed to provide an indication of the means by which a particular feedstock should be processed. Initial inspection of the nature of the heavy crude oil, extra heavy crude oil, and tar sand bitumen will provide deductions about the most logical means of refining or correlation of various properties to structural types present and hence attempted classification of the viscous feedstocks. Proper interpretation of the data resulting from the inspection of crude oil requires careful consideration and an understanding of the significance of the data.
It is for these reasons that understanding the composition of the viscous feedstocks, as well as the chemical and physical properties of these feedstocks, is extremely important. Thus, an efficient evaluation of a feedstock requires the application of tests than specifications. These are then used to provide adequate control of product quality without being over restrictive with the minimum of testing effort.
Product quality is judged by the performance during service. The performance of any product in particular service applications is therefore the ultimate criterion of quality. It is therefore necessary to find properties that allow assessment of the service performance, especially those tests that correlate closely with the service conditions. Sometimes the inspection tests attempt to measure these properties, for example, the research octane number test that was devised to measure the antiknock performance of motor fuel or, in many cases, the significant property is obtained indirectly from the inspection test results.
However, where the specified property is not measured directly, it is important to ensure that a suitable combination of inspection tests is selected to give a high degree of correlation with the specified property.
Although the focus on this book is on the relevant ASTM test methods with the numbers given, where possible the corresponding IP test method number is also presented. As an aside, the ASTM or the IP may have withdrawn some of the tests noted herein. Nevertheless, the method is still included because of its continued use, for whatever reason, by analysts and also for historical (not hysterical) reference purposes!
Thus, this book will deal with the various aspects of the analysis (and properties) of the viscous feedstocks and will provide a detailed explanation of the necessary standard tests and procedures that are applicable to feedstocks in order to help define predictability of behavior. In addition, the application of test methods for determining instability and incompatibility as well as test methods related to environmental regulations will be described.
More important, the book will provide details of the meaning of the various test results and how they might be applied to predict feedstock behavior. In fact, analytical techniques for chemical analysis of crude oil and the viscous feedstocks as well as the transformation products formed by photochemical processes and biological processes is a necessary next step after a spill. In addition to the standard test method present elsewhere in this text, the spilled material can be investigated by advanced gas chromatography (GC) techniques such as comprehensive two‐dimensional GC (GC‐GC), pyrolysis GC with mass spectrometry (MS), and GC with tandem mass spectrometry (GC‐MS/MS) which will provide a greater understanding at the molecular level of composition and complexity of the spilled material and any chemical changes that occur to the spilled material.
Analytical chemists represent a rich resource for the various aspects of feedstock refining and recognize that while the recent decades of experience have enhanced analytical knowledge, they have also revealed large gaps in the kind of data needed to thoroughly understand the nature of heavy crude oil, extra heavy crude oil, and tar sand bitumen as feedstocks for refineries.
The significance of a particular test is not always apparent by reading the procedure, and sometimes can only be gained through a working (i.e., a hands‐on) familiarity with the test. The following tests are commonly used to characterize asphalts but these are not the only tests used for determining the property and behavior of an asphaltic binder. As in the petroleum industry, a variety of tests are employed having evolved through local, or company, use.
The development of laboratory instrumentation over the last 50 years has been one of the forces shaping analytical standards and improved instrumentation is already changing approaches to the analysis of viscous feedstocks. Like the twin strands of the famous DNA double helix, technology and analytical science and regulation will continue their closely linked relationship.
The prime focus of the book is the emphasis of the analytical methods applied to heavy crude oil, extra heavy crude oil, and tar sand bitumen with lesser emphasis on product analysis. Although product analysis is an extremely important aspect of the science and technology of the viscous feedstocks, it is felt that the move to these feedstocks for refinery operations requires that more emphasis be placed on the analysis and properties of refinery feedstocks.
Furthermore, while the focus of this chapter is on the sampling and preparation of the viscous feedstocks for refining, it is worthwhile (because of the similarity of the methods) to consider the application of the sampling and measurement methods to situations where the feedstock has been spilled into the environment. In fact, the spills of crude oil and viscous feedstocks can occur anywhere that the material is being stored, transported, transferred from one tank to another, or refined. Thus, methods that are applicable to both refining and environmental issues are cited in this chapter. This will save unnecessary repetition of the methods at other parts of the book.
This book will assist the reader to gain an understanding of the criteria for determining the quality and processability of heavy crude oil, extra heavy crude oil, and tar sand bitumen and the production of products from these viscous feedstocks as well as the appropriate test methods when one of these feedstocks is spilled into the environment.
Dr. James G. Speight,Laramie, WyomingDecember 2022
1History and Terminology
1.1 Introduction
Crude oil (also commonly referred to as “petroleum”) is typically a mixture of hydrocarbon derivatives that occurs widely in the sedimentary rocks in the form of gases, liquids, semisolids, or solids. Crude oil provides not only raw materials for the ubiquitous plastics and other products but also fuel for energy, industry, heating, and transportation. Chemically, crude oil is an extremely complex mixture of organic compounds many of which (in conventional crude oil) are hydrocarbon derivatives along with minor amounts of nitrogen‐containing compounds, oxygen‐containing compounds, and sulfur‐containing compounds as well as trace amounts of metal‐containing compounds (Chapter 2) (Parkash, 2003; Gary et al., 2007; Speight, 2014a; Hsu and Robinson, 2017; Speight, 2017).
However, over the past several decades, the feedstocks available to refineries have generally decreased in API gravity and a major focus in refineries is to develop processing options for the viscous feedstocks (Khan and Patmore, 1997; Gary et al., 2007; Rana et al., 2007; Rispoli et al., 2009; Stratiev and Petkov, 2009; Stratiev et al., 2009; Motaghi et al., 2010a, 2010b; Speight, 2011a; Hsu and Robinson, 2017; Speight, 2017). Simultaneously, the changing crude oil properties are reflected in changes such as an increase in asphaltene constituents, and an increase in sulfur, metal, and nitrogen contents. Pretreatment processes for removing such constituents or at least negating their effect in thermal process would also play an important role.
The limitations of processing these heavy feedstocks depend to a large extent on the amount of higher molecular weight constituents (i.e., asphaltene constituents and resin constituents) that contain the majority of the heteroatom‐containing compounds, which are responsible for high yields of thermal and catalytic coke. Be that as it may, the essential step required of a modern refinery is the upgrading of heavy feedstocks, particularly the complex atmospheric residua and vacuum residua.
Upgrading feedstocks such as heavy oils and residua began with the introduction of hydrodesulfurization processes (Speight, 2000). In the early days, the goal was desulfurization but, in later years, the processes were adapted to a 10–30% partial conversion operation, as intended to achieve desulfurization and obtain low‐boiling fractions simultaneously, by increasing severity in operating conditions. However, as refineries have evolved and feedstocks have changed, refining viscous feedstocks has become a major part of modern refinery practice and there has also been the evolution and the necessity of the development of process configurations to accommodate the viscous feedstocks (Khan and Patmore, 1997; Parkash, 2003; Gary et al., 2007; Speight, 2011a; Hsu and Robinson, 2017; Speight, 2017).
For example, hydrodesulfurization of the light (low‐boiling) distillate (naphtha or kerosene) is one of the more common catalytic hydrodesulfurization processes since it is usually used as a pretreatment of such feedstocks prior to deep hydrodesulfurization or prior to catalytic reforming. A similar concept of pretreating residua prior to hydrocracking to improve the quality of the products is also practiced (Speight, 2011a). Hydrodesulfurization of such feedstocks is required because sulfur compounds poisoning the precious‐metal catalysts used in the hydrocracking process can be achieved under relatively mild conditions. If the feedstock arises from a cracking operation (such as cracked residua), hydro‐pretreatment will be accompanied by some degree of saturation resulting in increased hydrogen consumption.
In fact, since the so‐called oil shocks of the 1970s, the refining industry been the subject of the forces which have hastened the development of refineries such as (1) the demand for products such as gasoline, diesel, fuel oil, and jet fuel; (2) feedstock supply, specifically the changing quality of crude oil and geopolitics between different countries; (3) the emergence of alternate feed supplies such as heavy crude oil, extra heavy crude oil, and tar sand—collectively known as viscous feedstocks; (4) technology development such as new catalysts and processes, especially processes involving the use of hydrogen; and (5) environmental regulations that include more stringent regulations in relation to sulfur in gasoline and diesel (Parkash, 2003; Gary et al., 2007; Speight, 2011a; Hsu and Robinson, 2017; Speight, 2017).
The viscous feedstocks by virtue of the generation and maturation process that contribute to the formation of these feedstocks have lesser amounts of hydrocarbon derivatives and have properties characteristics that affect their flowability in the processes of recovery, pipeline transportation, and in the refinery. Moreover, the key to feedstock refining is, as in any industrial process, knowledge of the character of the feedstock. Chemical composition is the starting point for the oil characterization and it has a major impact on other properties, including key properties for their dynamics, such as density and viscosity (Chapter 2).
The particular characteristics of the viscous oils are mainly attributed to a biodegradation process in which microorganisms on a geological time scale degrade light and medium hydrocarbons, making the reserves rich in polynuclear aromatic derivatives, resin constituents, and asphaltene constituents (Parkash, 2003; Gary et al., 2007; Speight, 2014a; Hsu and Robinson, 2017; Speight, 2017). Microbial degradation reaches optimal temperatures below 80 °C (715 °F), promoting oil oxidation, reduction of the gas/oil ratio (GOR), and increasing density, acidity, and viscosity as well as the relative proportion of sulfur and heavy metals. In addition to bio‐processes, the formation of heavy crude oil (as well as extra heavy crude oil and tar sand bitumen) occurs through mechanisms such as water washing and phase fractionation, which are based on the loss of a significant fraction of the original source mass as well as removal of lower boiling constituents (and fractions) by physical rather than bio‐processes.
The viscous feedstocks display a high content of high molecular weight constituents that contain elevated levels of heteroatom constituents including sulfur, nitrogen, oxygen, and metals that require modification of the refinery processing options (Speight, 2011a, 2017). Typically, the molecules present in the viscous oils have more than 15 carbon atoms in the chain which can lead to the generation of products (in the refinery) such as a low yield of content of high‐octane naphtha and kerosene. Although the amount of compounds containing heteroatom constituents is relatively small, the effect of these compounds on the refining processes and the properties of the products are usually significant.
Chemical species containing sulfur atoms are often regarded as harmful for their effects on the refining process. The most common types are thiol derivatives (RSH), sulfide derivatives (R1SR2, where R1 and R2 are the same or different organic moieties), and thiophene and derivatives.
By way of definition, thiophene (C4H4S) is a heterocyclic compound (the sulfur is in a ring structure) that is a colorless liquid with a benzene‐like odor that is only one of several sulfur‐containing derivatives that occur in crude oil and the viscous oils (Figure 1.1).
These derivatives consist of thiol mercaptan derivatives (RSH, where R is an alkyl moiety or an aromatic moiety), sulfide derivatives (R1SR2, where R1 and R2 are the same or different moieties), disulfide derivatives (R1SSR2, where R1 and R2 are the same or different moieties), and cyclic sulfide derivatives where the sulfur atom occurs in a six‐membered saturated ring system consisting of five carbon atoms and one sulfur atom. There are also examples where the sulfur atom occurs in a five‐membered saturated ring system consisting of four carbon atoms and one sulfur atom. The remaining derivatives may be (arbitrarily or simple) considered to be derivatives of thiophene (Figure 1.2).
Figure 1.1 Thiophene (the numbers, 2–5, indicate the positions of the substitutable hydrogen atoms).
Figure 1.2 Examples of organic sulfur derivative that occur in crude oil and the viscous oils.
Figure 1.3 Benzene (showing the various alternate structures; in terms of reactivity, the structures are equivalent).
Figure 1.4 Pyridine (the numbers, 2–6, indicate the positions of the substitutable hydrogen atoms).
Thiophene is a planar five‐membered ring and reacts very much in the manner of benzene derivatives.
Benzene is an organic hydrocarbon (C6H6), that is, the benzene molecule is composed of six carbon atoms joined in a planar ring with one hydrogen atom attached to each carbon (Figure 1.3).
The nitrogen compounds are generally basic, formed by pyridine and its homologs (Figure 1.4). Pyridine is a basic heterocyclic organic compound (C5H5N) which is structurally related to benzene, with one methine (─C─H) group replaced by a nitrogen atom. It is a weakly alkaline, water‐miscible liquid.
However, nitrogen compounds can also occur in nonbasic forms, formed by species including pyrrole derivatives, indole derivatives, and carbazole derivatives (Figure 1.5) (Speight, 2014a, 2017). Significant amounts of porphyrin derivatives (which contain nickel, Ni, and vanadium, V) may occur in the nonbasic fraction of the nitrogen compounds. Other metal‐containing derivatives are generally present in the form of organic salts (R−M+) where R is an organic moiety and M is a metal dissolved in oil‐emulsified water. Heavy crude oils often contain a large portion of nickel and vanadium, which form chelates with porphyrins that are responsible for catalyst contamination and corrosion problems (Speight, 2014c).
Figure 1.5 Examples of organic nitrogen derivatives that occur in crude oil and the viscous oils.
Oxygenated compounds appear as carboxylic derivatives (RCO2H, where R is an aliphatic group or aromatic group) and phenol derivatives (ArCO2H, where Ar is an aromatic group), although the presence of ketone derivatives (R1COR2, where R1 and R2 are either aliphatic or aromatic hydrocarbon groups) and ether derivatives (R1OR2, where R1 and R2 are either aliphatic or aromatic hydrocarbon groups) have also been identified in some feedstocks (Figure 1.6) (Speight, 2014a, 2017). The content of the oxygen‐containing compounds (especially the carboxylic acid derivatives) and the phenol derivatives determines the acidity of the feedstock and, hence, the corrosivity (Speight, 2014c), which is particularly important in the refining processes. These features can occur on the same molecular structure, further increasing the complexity and difficulty of the characterization of the compounds present in the crude oil.
Due to the impossibility of an elemental characterization of crude oils and viscous oils because of their complex nature, a complete characterization has been satisfactorily obtained by fractionation, based on fraction polarity and solubility (Chapter 3). The saturates, aromatics, resins, asphaltene (SARA) analysis is the most widely used method to subdivide refinery feedstocks (and many higher boiling refinery products) into four subfractions, namely (1) a saturates fraction, (2) an aromatics fraction, (3) a resins fraction, and (4) an asphaltene fraction. The method produces the fractions based on molecular weight (by solvent treatment of the feedstock) and polarity through a chromatographic technique. Thus, by using different solvents (such as n‐pentane or n‐heptane), the asphaltene fraction can be separated from the whole feedstock (or a topped feedstock—the feedstock from which the more volatile constituents boiling up to, say, 200 °C, 390 °F have been removed)—while an adsorbent is (or different adsorbents are) employed to separate the saturates, aromatics, and resin fractions (Chapter 3) (Speight, 2014a, 2015a). The method is reproducible and applicable to a wide variety of heavy crude oil, extra heavy crude oil, tar sand bitumen, and crude oil residua.
Figure 1.6 Examples of organic oxygen derivatives that occur in crude oil and the viscous oils.
Finally, there is not one single heavy feedstock upgrading solution that will fit all refineries. Market conditions, existing refinery configuration, and available crude prices all can have a significant effect on the final configuration. Furthermore, a proper evaluation, however, is not a simple undertaking for an existing refinery. The evaluation starts with an accurate understanding of the market for the various products along with corresponding product values at various levels of supply. The next step is to select a set of crude oils that adequately cover the range of crude oils that may be expected to be processed. It is also important to consider new unit capital costs as well as incremental capital costs for revamp opportunities along with the incremental utility, support, and infrastructure costs. The costs, although estimated at the start, can be better assessed once the options have been defined leading to the development of the optimal configuration for refining the incoming feedstocks.
In fact, the limitations of processing these heavy feedstocks depend to a large extent on the amount of higher molecular weight constituents (i.e., asphaltene constituents and resin constituents) that contain the majority of the heteroatom‐containing compounds, which are responsible for high yields of thermal and catalytic coke (Parkash, 2003; Gary et al., 2007; Speight, 2014a; Hsu and Robinson, 2017; Speight, 2017). Be that as it may, the essential step required of a modern refinery is the knowledgeable upgrading of the heavy feedstocks through the data acquisition programs (analytical test methods) that provide indication of the behavior of the feedstocks during refining.
Furthermore, there is not one single upgrading option that will accommodate all of the viscous feedstocks and that will fit all refineries and feedstock composition can have a significant effect on the necessary processing configuration. Thus, a proper evaluation that starts with an analytical program that will identify the characteristics of the feedstocks accepted by the refinery as well as afford the luxury of predictability of the behavior of the feedstock constituents during refining.
Thus, the focus of this text is on the test methods that will assist the refiner to identify the appropriate options for the various viscous refinery feedstocks that are currently accepted as feedstocks for refineries. This chapter begins with a presentation of the terminology of the feedstocks.
1.2 Historical Perspectives
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 crude oil, crude oil derivatives (naphtha), and the viscous feedstocks (such as heavy crude oil, extra heavy crude oil, and tar sand bitumen) are not new. The use of crude oil and the viscous materials that seeped from outcrops was practiced in pre‐Christian times and is known largely through historical use in many of the older civilizations, particularly the civilization of the Middle Eastern countries where seepages from outcrops were widely recognized (Henry, 1873; Abraham, 1945; Forbes, 1958a, 1958b; James and Thorpe, 1994; Speight, 2014a).
As a brief introduction to the historical aspects of the subject, crude oil (also known as petroleum) was originally referred to as “rock oil” which was derived from the Latin “petra” which, in turn, was derived from the Greek word “πέτρα” (meaning “rock” or “stone”) and “oleum” which originally meant “olive oil” and, in turn, was derived from the ancient Greek word “ἔλαιον” (élaion also meaning “olive oil”). However, the development of a system of terminology is more complex and has evolved from pre‐Christian times (years typically designated by the term “BC”) to the present time and, with the incursion of the viscous feedstocks into refining processing, is continuing to evolve.
1.2.1 Pre‐Christian Era Use of Heavy Oil and Bitumen
The word asphalt is derived from the Akkadian term “asphaltu” or “sphallo,” meaning to split, which is indicative of the early use of an asphalt as a mastic between stones.
As an explanatory note, the Akkadian Empire was the first ancient empire of Mesopotamia that existed after the long‐lived southern Mesopotamian civilization of Sumer. The empire was centered in the city of Akkad and the immediately surrounding region, and the empire united the Sumerian and Akkadian speakers under one rule and language. Sargon of Akkad (also known as Sargon the Great and sometimes identified as the first person in recorded history to rule over an empire rather than a city‐state) was the first ruler of the Akkadian Empire, known for his conquests of the Sumerian city‐states in the 24th to 23rd centuries BC.
The term “asphaltu” was later adopted by the Homeric Greeks in the form of the signifying firm, stable, secure, and the corresponding verb ασϕαλίζω ίσω meaning to make firm or stable, to secure. On the other hand, the origin of the word bitumen is more difficult to trace and subject to considerable speculation. The word has been proposed to have originated in the Sanskrit, in which language the words “jatu”, meaning pitch, and “jatukrit” occur and have been proposed to mean “pitch creating” (Speight, 2011b, 2014a, 2016).
From the Sanskrit, the word “jatu” was incorporated into the Latin language as “gwitu” and is reputed to have eventually morphed into the word “gwitumen” (supposedly meaning “pertaining to pitch”). Another word, “pixtumen” (which has been proposed and assumed to mean “exuding pitch” 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 formed and derived, is certainly suspect (Speight, 2014a, 2016). However, there is the possibility that subsequent derivation of the word led to a shortened version (which eventually became the modern version) “bitûmen” from which the word has passed into the English language by way of the French language.
In this text for convenience and to avoid confusion that can exist from the use of different names, the word “bitumen” is used to indicate the naturally occurring viscous organic material that occurs in various deposits and outcrops. In the modern world, the word “asphalt” is used to indicate the manufactured organic material and does not include the inorganic aggregate that is mixed with the paving as a lay‐down for road paving systems (Speight, 2014a, 2016).
More generally, bitumen (often incorrectly referred to as natural asphalt since the word “asphalt” is used to describe a refinery product) was used as mortar from very early times, and sand, gravel, or clay was employed in preparing these mastics. Bitumen‐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 bitumen before being set in place. The use of bituminous mortar was introduced into the city of Babylon by King Hammurabi, but the use of bituminous mortar was abandoned toward the end of the reign of King Nebuchadnezzar in favor of lime mortar to which varying amounts of bitumen were added. The Assyrians recommended the use of bitumen 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 bitumen, in the molten state, be poured onto the heads of criminals as a form of punishment.
One of the earliest recorded uses of bitumen 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 bitumen deposits, and uses of the material have become evident. For example, King Sargon Akkad (Agade) (at about 2550 BC) was (for reasons that are lost in the annals of time) set adrift by his mother in a basket of bulrushes on the waters of the Euphrates and he was discovered by Akki the husbandman (the irrigator), whom he brought up to serve as gardener in the palace of Kish. Sargon eventually ascended to throne.
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 bitumen 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.
The Tigris‐Euphrates valley, in what is now Iraq, was inhabited as early as 4000 BC by the people known as the Sumerians who established one of the first great cultures of the civilized world. The Sumerians devised the cuneiform script, built the temple‐towers known as ziggurats, and had an impressive law, literature, and mythology. As the culture developed, bitumen was used as a sealant (sometimes incorrectly referred to as natural occurring bitumen). In fact, there is evidence that bitumen was used as a sealant for water channels to, and within, several of the ancient cities in the region (Speight, 1978).
Nevertheless, these writings do offer documented examples of the use of crude oil and related materials. For example, in the Epic of Gilgamesh written more than 2,500 years ago, in anticipation of a forthcoming deluge, the principal of the story builds an ark (a very large boat) to accommodate and save his family as well as a host of animals. The wooden boat is caulked with bitumen and pitch (see for example, Kovacs, 1990) and in a related story, also set in Mesopotamia just prior to the deluge (the Biblical Flood), (it is not the intent here to discuss the similarities or relationship or origin of the two stories), a man (Noah) is commanded to build a boat that also includes instructions for caulking the vessel with pitch (Genesis 6:14).
Make yourself an ark of cypress wood; rooms shalt thou make in the ark, and shalt coat it with pitch inside and out.
The occurrence of slime (bitumen) pits in the Valley of Siddim, a valley at the southern end of the Dead Sea, is also noted (Genesis 14:10). 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 thoroughly. And they had brick for stone, and slime had they for mortar.
In the Septuagint, or Greek version of the Bible, this work 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 the German version of the Bible (assigned to Martin Luther), it appears as the word “thon”—the word is of linguistically questionable origin and has been suggested to mean “clay.” Another example of the use of pitch (and slime) is given in the story of Moses (Exodus 2:3):
And when she could no 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.
It is convenient (if not very reasonable) to assume that the word “slime” referred to a lower melting bitumen (such as extra heavy crude oil) whereas the word “pitch” referred to a higher melting material—the slime acting as a flux for the pitch.
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, bitumen was exported from Canaan to various parts of the countries that surround the Mediterranean (Armstrong, 1997).
In terms of liquid products, there is a noteworthy reference that relates to bringing oil out of flinty rock (Deuteronomy 32:13). 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 it was mineral oil (a crude oil derivative such as naphtha or kerosene) or whether it was vegetable oil is not known.
Excavations conducted at Mohenjo‐Daro and Harappa (founded and occupied in approximately 2500 BC) in the Indus Valley indicated that a bitumen‐type mastic composed of a mixture of bitumen, 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 contained a layer of mastic on the outside of its walls and beneath its floor.
Also in the Bronze Age (approximately 3300 to 1200 BC), 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. The wooden piles were preserved from decay by coating with bitumen and there are also references to deposits of bitumen at Hit (the ancient town of Tuttul on the Euphrates River 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 Carthaginian story in which birds' feathers smeared with pitch are used to recover gold dust from the waters of a lake.
Use of bitumen by the Babylonians (1500 to 538 BC) is also documented and each monarch commemorated their reign and perpetuated their name by construction of building or other monuments. This includes references to deposits of bitumen at Hit (the ancient town of Tuttul on the Euphrates River) 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 Carthaginian story in which birds' feathers smeared with pitch are used to recover gold dust from the waters of a lake. Also, the use of bitumen mastic as a sealant for water pipes, water cisterns, and in outflow pipes leading from flush toilets in ancient cities such as Babylon, Nineveh, Calah, and Ur has been observed and the bitumen lines are still evident in uncovered systems (Speight, 1978).
Early references to crude oil and its derivatives occur in the Bible, although by the time the various books of the Bible were written, the use of crude oil and bitumen was established. For example, the combustion properties of bitumen (and its fractions) were known in Biblical times. There is the 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. And the streams thereof shall be turned into 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.
It can be concluded (based on current knowledge) that the effects of the burning bitumen and sulfur (brimstone) were long lasting and quite devastating.
The Egyptians were the first to adopt the practice of embalming their dead rulers and wrapping the bodies in cloth. Before 1000 BC, bitumen was rarely used in mummification, except to coat the cloth wrappings and thereby protect the body from the elements. From 500 to about 40 BC, bitumen was generally used both to fill the corpse cavities (after the viscera had been removed) as well as to coat the cloth wrappings. The word mûmûia first made its appearance in Arabian and Byzantine literature about 1000 AD, signifying bitumen. In fact, it was through the spread of the Islamic Empire that, it is believed, brought Arabic science and the use of bitumen to Western Europe.
In the Roman world, bitumen was also an important commodity and could also be used for medicinal purposes such as to stop bleeding, heal wounds, drive away snakes, treat cataracts, and straighten out eyelashes which inconvenience the eyes as well as a wide variety of other diseases.
From the same roots as used by the pre‐Christian builders, the Anglo Saxon word “cwidu” (mastic, adhesive) was derived. Also, the German word “kitt” (translated as filler, cement, or mastic) which is also 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” that was the birch tree that was used as a source of resin (tar). From this, the word appears in Middle English as bithumen (Speight, 2014a, 2016).
In fact, a variety of words exist in ancient languages which, from the use of the words in the relevant contexts, can be proposed as referring to bitumen (Table 1.1) (Abraham, 1945). From the Greek language, the word passed into (early medieval) Latin as “asphaltum” or “aspaltum” and from there into French (“asphalte”) and Old English (“aspaltoun”).
Table 1.1 Examples of the Origins of Words Related to Crude Oil and Bitumen
Language
Word
Possible meaning
Sumerian
esir
Petroleum, bitumen
esir‐harsag
Rock asphalt
esir‐ud‐du‐a
Pitch
kupru
Slime
kupru
Pitch
Sanskrit
jatu
Bitumen
Jatu
Pitch
śilā‐jatu
Rock asphalt
Assyrian/Akkadian
idd
Bitumen
Ittû
Bitumen
it‐tû‐u
Bitumen
amaru
Bitumen
sippatu
Pitch
Greek
maltha
Soft asphalt
asphaltos
Bitumen
pittasphaltos
Rock asphalt
pittolium
Rock oil
pittolium
Rock asphalt
pissa
Pitch
pitta
Pitch
Latin
maltha
Soft asphalt
bitumen liquidum
Soft asphalt
pix
Pitch
In addition to bitumen, there was also an interest in the distillation product derived from crude oil (nafta, which is presumably the product now referred to as naphtha) which was also derived from the thermal treatment of bitumen. 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).
1.2.2 Post‐Christian Era Use of Heavy Oil and Bitumen
Approximately two thousand years ago, Arabian scientists developed methods for the distillation of crude oil, which were introduced into Europe by way of Spain. This represents another documented use of the volatile derivatives of crude oil which led to a continued interest in crude oil and its derivatives as medicinal materials and materials for warfare, in addition to the usual construction materials.
There are references to the use of naft as an incendiary material (Greek fire, a precursor and chemical cousin to napalm) during various battles (James and Thorpe, 1994). Greek fire is also recorded as being used in the period 674–678 AD when the city of Constantinople was saved by the use of the fire against the by an Arab fleet (Davies, 1996). In 717–718 AD, Greek fire was again used to save the city of Constantinople from attack by another Arab fleet; again with deadly effect (Dahmus, 1995).
Many other references to bitumen occur throughout the empires of Greece and Rome and from then to the Middle Ages, early scientists (alchemists) frequently alluded to the use of bitumen for a variety of purposes of which bitumen use as a mastic appears to have been popular. 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 bitumen deposit on the island of Trinidad and apparently used the material to caulk the ships.
Bitumen (or a bitumen‐type material, i.e., a viscous naturally occurring material) was used in prescriptions, as early as the 12th Century, by the Arabian physician Al Magor, for the treatment of contusions and wounds. The 13th Century scientist Al‐Kazwînî alluded to the healing properties of mûmûia, and Ibn Al‐Baitâr gives an account of its source and composition. The region around Baku (currently, the capital and largest city of Azerbaijan, as well as the largest city on the Caspian Sea and of the Caucasus region) was also reported (by Marco Polo in 1271–1273) as having an established commercial crude oil industry. It is believed that the prime interest was in the kerosene fraction that was then known for its use as an illuminant. By inference, it has to be concluded that the distillation, and perhaps the thermal decomposition, of crude oil were established technologies. If not, Polo's diaries might well have contained a description of the stills or the reactors.
In addition, bitumen was investigated in Europe during the Middle Ages (Bauer, 1546, 1556), and the separation and properties of bituminous products were thoroughly described. Other investigations continued, leading to a good understanding of the sources and use of this material even before the birth of the modern crude oil industry (Forbes, 1958a, 1958b). Also, in Europe, Engelbert Kämpfer (1651–1716) gave a detailed account of the collection of bitumen in his treatise Amoenitates Exoticae (Exotic Pleasantries) as well as the different grades and types and the use of the material as a curative in medicine.
There are also records of the use of crude oil spirit, probably a higher boiling fraction of or than naphtha that closely resembled the modern‐day liquid paraffin, for medicinal purposes. In fact, the so‐called liquid paraffin has continued to be prescribed up to modern times. The naphtha of that time was obtained from shallow wells or by the destructive distillation of asphalt.
Parenthetically, the destructive distillation operation may be likened to modern thermal cracking or coking operations (Parkash, 2003; Gary et al., 2007; Speight, 2014a; Hsu and Robinson, 2017; Speight, 2017) in which the overall objective is to convert the feedstock into distillates for use as fuels. This particular interest in crude oil and its derivatives continued with an increasing interest in nafta (naphtha) because of its aforementioned used as an illuminant and as a supplement to asphaltic incendiaries for use in warfare.
In summary, the use of crude oil and bitumen has been observed for almost 6000 years (Mallowan and Rose, 1935; Nellensteyn and Brand, 1936; Mallowan, 1954; Marschner et al., 1978
