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Catalytic Naphtha
Reforming Process
Catalytic Naphtha
Reforming Process
Soni O. Oyekan
CRC Press
Taylor & Francis Group
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Contents
Preface.......................................................................................................................xi
Acknowledgments..................................................................................................... xv
Author.....................................................................................................................xvii
Chapter 1 Introduction to Catalytic Reforming and the Oil Business................... 1

1.0 Introduction................................................................................1
1.1 Early History of Crude Oil Business.......................................... 2
1.2 Post-1900 History of Crude Oil Business...................................3
1.3 Source of Crude Oil.................................................................... 4
1.4 Crude Oil Reserves.....................................................................5
1.5 Introduction to Opportunity Oils and Unconventional Oils....... 7
1.6 Global Oil Production................................................................8
1.7 Oil Consumption...................................................................... 12
1.8 Crude Oil and Other Hydrocarbon Liquid Qualities................ 13
References........................................................................................... 17
Chapter 2 Basics of Crude Oil Refining.............................................................. 19

2.0 Introduction to Basics of Oil Refining..................................... 19
2.1 Crude Oil Composition............................................................ 19
2.1.1 Paraffins...................................................................... 21
2.1.2 Naphthenes.................................................................. 22
2.1.3 Aromatics.................................................................... 23
2.1.4 Olefins......................................................................... 23
2.1.5 Heteroatom Compounds in Oils..................................24
2.1.6 Sulfur Compounds in Oils..........................................25
2.1.7 Nitrogen Compounds in Oils....................................... 27
2.1.8 Asphaltenes.................................................................28
2.1.9 Porphyrins................................................................... 30
2.2 Oil refining Economics............................................................ 31
2.2.1 Oil Refining Profitability............................................. 31
2.3 Refinery Configurations...........................................................34
2.3.1 Topping Refineries...................................................... 38
2.3.2 Hydroskimming Refineries.........................................40
2.3.3 Cracking Refineries..................................................... 42
2.3.4 Coking Refineries........................................................ 43
2.4 Oil Refineries, Fuels, and Global Warming............................. 51
2.4.1 Overview of Global Transportation Fuels................... 54
2.4.2 Diesel Fuels................................................................. 55
2.4.3 Gasoline Fuels............................................................. 56
References...........................................................................................60
v
vi Contents
Chapter 3 Overview of Oil Refining Process Units............................................. 63

3.0 Introduction.............................................................................. 63
3.1 Crude Distillation Unit............................................................. 63
3.2 Vacuum Distillation Unit.......................................................... 67
3.3 Butane Isomerization Unit........................................................ 70
3.4 Light Naphtha Isomerization Unit............................................ 72
3.5 Hydrotreating Units.................................................................. 75
3.5.1 Hydrotreating Reactions.............................................. 76
3.5.2 Hydrotreating Process Feedstocks and
Catalysts...................................................................... 76
3.5.3 A Generalized Hydrotreating Process Unit................80
3.5.4 Light Naphtha Hydrotreating...................................... 81
3.5.5 Heavy Naphtha Hydrotreating.................................... 82
3.5.6 Gasoline Desulfurization............................................ 86
3.5.7 Distillate Hydrotreating............................................... 87
3.5.8 Vacuum Gas Oil Hydrotreating...................................90
3.5.9 Residual Oil Hydrotreating.........................................94
3.6 Fluid Catalytic Cracking Units................................................. 95
3.7 Coking Process Units............................................................... 98
3.8 Hydrocracking Processes....................................................... 100
3.9 Alkylation Processes.............................................................. 102
3.10 Other Processes and Auxiliary Systems................................ 104
3.10.1 Increased Hydrogen Demand.................................... 104
3.10.2 Sulfur Recovery Processes........................................ 105
References......................................................................................... 107
Chapter 4 Basic Principles of Catalytic Reforming Processes.......................... 111

4.0 Introduction to Basic Principles............................................. 111
4.1 A Brief History of Pre-1950 Catalytic
Reforming Processes�� 112
4.2 Reforming Process Fundamentals.......................................... 113
4.2.1 Octane Numbers........................................................ 114
4.2.2 Process Objectives and Naphtha Feedstocks............ 117
4.2.2.1 Naphtha Composition................................ 117
4.2.2.2 Heavy Naphtha Boiling Range.................. 121
4.3 Key Catalytic Reforming Reactions....................................... 123
4.3.1 Naphthene Dehydrogenation..................................... 123
4.3.2 Isomerization of Naphthenes and Paraffins.............. 124
4.3.3 Paraffin Dehydrocyclization...................................... 125
4.3.4 Paraffin Hydrocracking............................................. 127
4.3.5 Hydrodealkylation of Alkyl Aromatics..................... 127
4.4 Process Variables of Catalytic Reformers.............................. 129
4.4.1 Reactor Temperature................................................. 130
4.4.2 Reactor Pressure........................................................ 131
Contents vii
4.4.3 Recycle Gas Hydrogen to Hydrocarbon Molar

Ratio.......................................................................... 133
4.4.4 Reformate Octane...................................................... 133
4.5 General Catalytic Reforming Operations............................... 134
4.6 Catalytic Reforming Process Equipment............................... 135
4.6.1 Reactors..................................................................... 136
4.6.1.1 Downflow Reactor..................................... 136
4.6.1.2 Spherical Reactor....................................... 137
4.6.1.3 Radial Downflow Reactor.......................... 138
4.6.1.4 Advances in Continuous Catalyst
Regeneration Radial Reactor Design�� 138
4.6.2 Process Heaters......................................................... 141
4.6.3 Heat Exchangers........................................................ 145
4.6.3.1 Shell and Tube Heat Exchangers............... 145
4.6.3.2 Plate Heat Exchangers............................... 148
4.6.4 Process Gas Compressors......................................... 149
References......................................................................................... 152
Chapter 5 Catalytic Reforming Catalysts.......................................................... 155

5.0 Introduction to Catalytic Reforming Catalysts...................... 155
5.1 Reforming Catalyst Nomenclatures....................................... 156
5.2 Dehydrogenation/Hydrogenation Functionality of
Reforming Catalysts�� 157
5.3 Acidic Isomerization Functionality........................................ 157
5.4 Platinum Catalytic Reforming Catalysts................................ 159
5.5 Multimetallic Catalytic Reforming Catalysts........................ 160
5.6 Catalyst Manufacturing Process............................................. 161
5.7 Catalyst Properties.................................................................. 162
5.7.1 Physical Properties.................................................... 163
5.7.1.1 Bulk Density.............................................. 163
5.7.1.2 Crush Strength........................................... 164
5.7.1.3 Catalyst Porosity........................................ 164
5.7.1.4 Surface Area.............................................. 165
5.7.1.5 Attrition Resistance................................... 168
5.7.2 Chemical Properties.................................................. 170
5.7.2.1 Catalytic Reforming Catalyst Metals........ 170
5.7.2.2 Catalyst Chloride....................................... 171
5.8 Catalyst Evaluation Program.................................................. 172
5.8.1 Catalyst Testing......................................................... 173
5.8.1.1 Model Feed Test Program.......................... 173
5.8.1.2 Naphtha Feed Test Program...................... 174
5.8.1.3 Catalyst Activation..................................... 175
5.8.1.4 Yield/Octane Test...................................... 176
5.8.1.5 Constant Octane Stability Test.................. 177
viii Contents
5.9 Alumina Hydrothermal Stability Test.................................... 184

References......................................................................................... 187
Chapter 6 Catalytic Reforming Technologies.................................................... 191

6.0 Introduction to Reforming Technologies................................ 191
6.1 Semiregenerative Catalytic Reforming.................................. 192
6.1.1 Reformer Naphtha Feed............................................ 196
6.1.1.1 Heavy Naphtha Contaminants................... 198
6.1.1.2 Sulfur in Naphtha Feeds............................ 198
6.1.1.3 Nitrogen in Naphtha...................................200
6.1.1.4 Naphtha Metal Contaminants.................... 201
6.1.2 Process Variables......................................................205
6.1.3 Water/Chloride Management....................................206
6.1.4 Catalyst Regeneration................................................208
6.1.4.1 Catalyst Coke Burn Principles................... 210
6.1.4.2 Catalyst Rejuvenation................................ 212
6.1.4.3 Catalyst Metal Oxide Reduction................ 213
6.1.4.4 Catalyst Sulfiding...................................... 215
6.1.4.5 Sulfate Removal Procedure....................... 216
6.2 Cyclic Catalyst Regenerative Reformers................................ 218
6.2.1 Special Features of Cyclic Reforming Catalysts
and Regenerations�� 221
6.2.2 Reliability Enhancement Programs.......................... 222
6.3 Continuous Catalyst Regenerative Reformers........................ 222
6.3.1 Catalyst Circulation Systems..................................... 228
6.3.2 Catalyst Regeneration in Continuous Catalyst
Regenerative Process Units�� 230
6.3.2.1 Primary and Secondary Coke Burns......... 232
6.3.2.2 Oxy-Chlorination Process......................... 234
6.3.2.3 Drying and Cooling................................... 235
6.3.2.4 Catalyst Reduction..................................... 236
6.4 Hybrid Catalyst Regenerative Reformers............................... 237
References.........................................................................................240
Chapter 7 Catalyst and Process Management Challenges................................. 245

7.0 Introduction to Catalyst and Process Challenges................... 245
7.1 Physical and Chemical Characteristics of Catalysts.............. 245
7.2 Catalyst Handling and Management...................................... 249
7.2.1 Catalyst Unloading Principles................................... 249
7.2.2 Catalyst Loading Principles...................................... 251
7.3 Catalyst Management in Catalytic Reforming Operations.... 252
7.3.1 Key Performance Indicators and Unit Monitoring... 254
7.4 Troubleshooting for Process Profitability............................... 257
Contents ix
7.4.1 High Pressure Drop in Continuous Catalyst

Regenerative Reformer Reactors�� 258
7.4.2 Managing Low Coke Naphtha Reforming in
Continuous Catalyst Regenerative Process Units......260
7.4.3 Catalyst Regeneration Challenges.............................264
7.4.3.1 Flow Distribution Challenges in a
Fixed-Bed Regenerative Reformer............ 265
7.4.3.2 Eliminate Delays after the Catalyst
Oxy-Chlorination.......................................266
7.4.3.3 Transition Smoothly between Black
and White Burns in Continuous
Catalyst Regenerative Regenerators..........266
References......................................................................................... 270
Chapter 8 Special Catalytic Reforming Topics.................................................. 273

8.0 Introduction to Special Catalytic Reforming Topics.............. 273
8.1 Brief Review of Opportunity Oils and Reforming
Operations�� 274
8.1.1 Initial Experiences with the Processing of
Shale Oil.................................................................... 274
8.1.2 Challenges in the Processing of Opportunity
Bitumen..................................................................... 276
8.1.3 Guidelines for Refining Opportunity Oils Can
Minimize Losses....................................................... 279
8.2 Strategies for Meeting Gasoline Benzene Regulations.......... 282
8.2.1 Process Technologies for Meeting Gasoline
Benzene Regulations................................................. 291
8.3 Chloride Management and Refinery Reliability..................... 296
8.3.1 Management of Total Chlorides in Crude Unit
Operations................................................................. 296
8.3.2 Management of Chlorides in Oil Refining
Processes...................................................................300
8.3.2.1 Chloride Management for Optimizing
Reforming Operations...............................302
8.3.2.2 Mitigating HCl-Induced Fouling in
Catalytic Reformers................................... 303
8.3.2.3 Eliminating HCl in Net Hydrogen Gas
from Catalytic Reformers..........................306
8.4 Catalytic Reformer Operations and Reliability
Challenges with Refinery Maximum Achievable Control
Technology II��309
8.5 Summary................................................................................ 314
References......................................................................................... 315
x Contents
Chapter 9 Special Topics—Turnaround and Platinum Management................. 319

9.0 Introduction to Turnaround and Platinum Management........ 319
9.1 Turnaround Planning and Maintenance................................. 319
9.1.1 Turnaround Planning for Catalytic Reforming
Units.......................................................................... 321
9.2 Overview of Platinum Supply and Management.................... 326
9.2.1 Platinum Acquisition Cost......................................... 327
9.2.2 Fresh Catalyst Purchase............................................ 329
9.2.3 Catalyst Platinum Agreements.................................. 330
9.2.4 Catalyst Selection and Platinum Management.......... 331
9.2.5 Overview of Platinum Management and
Recovery.................................................................... 332
9.2.6 Platinum Recovery Processes................................... 334
9.2.7 Catalyst Sampling and Settlement............................ 335
References......................................................................................... 337
Glossary................................................................................................................. 339
Index....................................................................................................................... 353
Preface
It is with great pleasure that I offer this book as a product of my goal of conveying
relevant information on key concepts, operations, and practices of catalytic naphtha
reforming technologies and associated oil refining processes. This book will most
likely be of use to those in academia and oil refining, petrochemicals, and allied
businesses. I was motivated by several factors to write a book on the catalytic naphtha
reforming process and technologies. Foremost is the need to review the collective
technical and operational advancements with respect to efficient use of catalysts and
catalytic reformers in oil refining.
The book on catalytic reforming by Donald Little published in 1985 and useful
chapters in several other books provide fundamental and some practical aspects of
catalytic reforming and light naphtha isomerization processes. Some of the chapters
in separate books by James Gary and Glenn Handwerk; James Speight; and Bruce
Gates, James Katzer, and G. C. A. Schuit provide relevant sections on catalytic
reforming technologies. Books on catalytic naphtha reforming by George Antos,
Abdullah Aitani, and Jose Parera provide comprehensive works with key basic and
practical concepts of the catalytic reforming process and related sciences. The listed
books were foundational for writing this book.
A second factor has been the need to incorporate key advancements from recent
developments in catalytic reforming technologies and processes. Most of the recent
innovations have been in continuous catalyst regenerative processes, and some of
the enhancements are covered in this book. Some of the advancements in catalytic
reforming have been driven by the need to provide high-octane reformate gasoline
blendstock in current markets for unleaded and regulated environmentally friendly
gasoline products. It is expected that this trend will continue as US and relevant
global markets position to meet the projected Tier 3 Corporate Average Fuel Economy
(CAFÉ) standard of 54.5 miles per gallon of gasoline for automobiles by 2025. In
addition, as important as reformate production is, the higher demand for hydrogen
production from catalytic reformers has re-emphasized interests in achieving reliable
and efficient operations of the process units. Higher hydrogen demand is due to the
increased requirements of oil refiners to produce ultralow-sulfur gasoline and diesel
products. Furthermore, high-severity processing operations of catalytic reformers
have led to increased organic chloride usage. Higher usage of organic chloride has
exacerbated reliability challenges and heightened the need to establish cost-effective
maintenance programs for piping and equipment, and for the other process units in
oil refineries. Higher production of net hydrogen gas in catalytic reforming operations
leads to increased use of chloride management strategies to protect oil refining
equipment and process units from fouling and corrosion. The US Environmental
Protection Agency (EPA) established stringent environmental regulations for the
reduction of hydrogen chloride and toxic organic compounds (TOCs) in catalyst
regeneration vent gases. Three major technologies are used for meeting the lower
levels of hydrogen chloride and TOCs in regeneration vent gases. The caustic wash
vent gas tower system, adsorbents, and Honeywell UOP’s Chlorsorb are the available
xi
xii Preface
technologies for reducing hydrogen chloride and volatile organic compounds in

regenerator vent gas. The challenges associated with use of these technologies are
discussed.
Third, with the shift to more abundant, high-contaminant conventional crude
oils and unconventional bitumen and shale oils, catalytic reforming process units
have now developed another critical role in conjunction with crude distillation
units as “gatekeepers” in the optimization of the crude slates that are processed in
oil refineries. The highly sensitive platinum-containing catalysts used in catalytic
reforming units are very susceptible to metal contaminant poisoning in naphtha
feeds at fractional parts per million levels. Oil refiners with good analytical and
continuous monitoring programs can use their assets beneficially by applying them
for monitoring the quality of the naphtha feed to catalytic reformers. These resources
could enable oil refiners to detect changes in naphtha feed qualities, especially with
respect to catalyst contaminants. Oil refiners can then develop timely responses to
naphtha feed quality changes in catalytic reformers. These contaminants could be due
to contaminant contributions from one of the oils that is being processed in the crude
slate. Appropriate adjustments can then be made to optimize the percentages of oil
constituents in the crude slates in order to minimize or eliminate catalytic reformer
and refinery reliability and productivity challenges associated with the constituent
oils in the crude slate. Meticulous and continuous monitoring of key performance
indicators of the crude distillation and catalytic reforming process units are required,
and the benefits of timely, effective unit monitoring are covered in this book.
The factors listed motivated me to write this book to incorporate many of the
current key challenges, process developments, effective operations, and monitoring of
catalytic reformers in order to achieve optimized oil refining operations and desired
refinery reliability and profitability. In addition, since I could have benefited from a
brief introduction to the history of the oil and oil refining business at the start of my
career in oil refining about four decades ago, I devoted the first chapter of this book to
a brief history of the oil business and emphasized the pioneering business leadership
of John D. Rockefeller in growing Standard Oil at the turn of the twentieth century.
Standard Oil became the dominant global oil production, refining, and marketing
company at the beginning of the twentieth century. The history of oil production
can enhance our understanding of current geopolitical developments that have led to
changes in crude oil production and supply, crude oil quality, crude oil prices, and
their impacts on oil refinery operations, profitability, and the fiscal health of national
and global economies. The basics of oil refining are covered in the second chapter,
and several oil refinery processes and transportation fuel specifications are covered
in the third chapter. Brief reviews of oil refining process units are also provided in
the third chapter. The reviews help to emphasize the pivotal position of the catalytic
reforming process unit in oil refineries for the processing of straight run naphtha
and unsaturated naphthas from other downstream thermal and catalytic conversion
units in oil refineries. Catalytic reforming technologies, catalysts, and processes are
covered in detail in the six chapters that follow. The eighth chapter is devoted to
coverage of key specially selected topics of vital interest to enable successful, reliable,
and optimal operations of catalytic reforming process units and oil refineries. Due
to several challenges that can arise due to inadequate turnaround planning, subpar
Preface xiii
execution of turnarounds, and safety problems during catalytic reformer startups,

some best-practice concepts for turnaround maintenance are offered in Chapter 9. An
overview of cost-effective management programs for precious metals is provided with
great emphasis on platinum management. Platinum management principles discussed
can also be extended to managing other platinum group metals, as well as silver,
rhenium, and palladium.
One of the goals of writing this book is to encourage a more proactive approach
in the planning, operations and maintenance of catalytic reforming units and oil
refineries. A number of recommendations are provided in this book for enhancing
the operations, reliability, and productivity of catalytic reformers and oil refineries.
These recommendations can lead to cost-effective, safer, and optimal process unit
operations and maximization of the profitability of oil refiners.
Acknowledgments
The contents, technical knowledge, and practical experiences covered in a book of
this nature are developed via grounding in the principles of chemical engineering,
catalysis, and oil refining processes. As a result, it is appropriate for me to start by
acknowledging the training that I received from Professor Anthony Dent during my
doctoral studies on reactor engineering and catalysis at Carnegie Mellon University.
I am also grateful to Professors Csaba Horvath and Harding Bliss for the positive
influences they had on me in my studies of reaction kinetics and thermodynamics,
respectively, when I was at Yale University.
In the writing of a book of this scope, I have had to draw from course notes,
technical presentations, and relevant data from my patents on the catalytic naphtha
reforming process and other sources. The information that I share comes from about
40 years of technology development and training course notes that I shared with
oil refining engineers and operators. Some of the older introductory information
comes from the Petroleum Refining course that I taught at the New Jersey Institute
of Technology, Newark, in 1983. Over the past 25 years, I taught courses on catalytic
reforming, naphtha hydrotreating, paraffin isomerization, fluid catalytic cracking,
aromatics isomerization, and sulfur guard bed systems to oil refining process
technology personnel who worked with me at Sunoco, Amoco, and Marathon
Petroleum Corporation.
My lecture notes were updated and used as part of a course that was offered in
collaboration with Peter Kokayeff of Unocal and Dr. Stuart S. Shih of Mobil Oil for the
American Institute of Chemical Engineers (AIChE) Continuing Education program
between 1992 and 1998. The title of the course was Catalytic Processes in Petroleum
Refining. Dr. Shih taught the hydrotreating processes section, the hydrocracking
processing was taught by Kokayeff, and I taught the sections on catalytic reforming
and fluid catalytic cracking processes.
A number of companies contributed to my development and experiences in
research and development of oil refining technologies and operations of oil refining,
and I gratefully acknowledge them. The companies are Exxon (now ExxonMobil),
Engelhard (now BASF), DuPont, Sunoco, Amoco, and Marathon Petroleum
Corporation.
For the continuous catalyst regenerative (CCR) process units and technologies,
I acknowledge with special gratitude Axens and Honeywell UOP, for the
opportunities to collaborate on several technical, revamp, and grassroots catalytic
reforming projects with many of their personnel on CCR process-related challenges.
In a number of sections, figures of process units from technical papers by Axens
and Honeywell UOP have been used to enhance the quality of the description of the
CCR processes. I thank the companies for granting me copyright permissions to
use relevant images.
Lastly and foremost, I thank my wife, Priscilla Ann, for her love, support, and
encouragement always, and especially during the time that I spent in writing this
book. In addition, I am indebted to her for encouraging me to write with greater
xv
xvi Acknowledgments
clarity and make the content of the book of higher value for a wide spectrum of
persons such as business executives, financial analysts and planners, environmental
engineers, oil refining technical personnel and operators, chemical plant operators,
and persons in academic communities. I thank my wife also for the many useful
suggestions that she offered with respect to the chapters in the book.
Author
Soni O. Oyekan, PhD, is president and CEO of Prafis Energy Solutions. He is a
globally renowned expert in oil, gas, and oil refining. Dr. Oyekan was the corporate
process technologist for Marathon Petroleum Corporation, BP/Amoco, and Sunoco
separately, with responsibilities for naphtha processing, oil refining processes, and
technology support over a span of 20 years. Prior to 1993, Dr. Oyekan conducted
R&D studies at Exxon, Engelhard, and DuPont for 16 years, which resulted in his
inventions for catalytic naphtha reforming. His key inventions are used globally to
enhance the production of transportation fuels. Dr. Oyekan is the 2008 recipient of
the AIChE William M. Grimes award for excellence in chemical engineering. He was
awarded the NOBCChE Percy Julian award in 2009 for his outstanding contributions
in oil refining.
The author, a resident of Richmond, Texas, is a Fellow of the American Institute
of Chemical Engineers and a member of the AIChE Foundation Board of Trustees
and of NOBCChE. He is a member of the Nigerian Society of Chemical Engineers,
Sigma Xi, and Phi Kappa Phi societies.
Dr. Oyekan earned his BS degree (1970) in Engineering and Applied Sciences
from Yale University, New Haven, Connecticut, and his MS (1972) and PhD (1977)
degrees in Chemical Engineering from Carnegie Mellon University, Pittsburgh,
Pennsylvania.
xvii
1 Introduction to
Catalytic Reforming
and the Oil Business
1.0 INTRODUCTION
Catalytic reforming is the process used in oil refineries for converting the low-value
heavy naphtha fraction of crude oil to premium reformate, benzene, toluene and
xylene (BTX), and hydrogen. As will be reviewed in detail, reformate constitutes
about 30% of the gasoline that is produced. Hydrogen from catalytic reformers
is used as coreactant in several hydroprocessing units in oil refineries. In some
oil refineries, the catalytic reformer is the sole provider of a refinery’s hydrogen.
Additionally, benzene, toluene, and xylenes are used in the petrochemical industry
in the production of other chemicals and solvents. Numerous technological advances
have been made to improve catalytic reforming processes so as to provide increased
productivity over much longer times between turnaround maintenance periods.
Starting with a thermal naphtha cracking process, reforming technologies have
evolved through fixed-bed semiregenerative catalytic reforming and fixed-bed
cyclic regenerative reformers to the current high-performance, high-productivity
continuous catalytic regenerative technologies. In the catalytic reforming process, as
is the case for other catalytic processes, the catalyst during hydrocarbon processing
loses activity with time and has to be regenerated. With the exception of continuous
catalyst regenerative reforming processes, a reformer or a reactor shutdown is
required to effect necessary catalyst regeneration and catalytic activity recovery for
fixed-bed regenerative catalytic reformers.
In this book, some of the regulated gasoline quality requirements such as lower
benzene concentrations and oxygenate blending that have some impact on catalytic
reforming process operations are reviewed in appropriate chapters. Some of the
expected regulated reductions of aromatics may further impact catalytic reforming
units’ utilization. The demand for BTX in the petrochemical industry and hydrogen
for increased upgrading of heavy sour crude oil and unconventional bitumen-derived
oils in oil refineries will continue to drive the need for more efficient and smart
operations of catalytic reformers. Additionally, I have dubbed catalytic reformers
“gate keepers” of oil refineries, as they are the first major catalytic conversion units
after the crude distillation units. Catalytic reformers, with their highly sensitive
platinum-containing catalysts, exhibit catalytic performance declines with the
introduction of low concentrations of contaminants from the crude unit that are
present in hydrotreated naphtha feeds. In the current era of the processing of a
variety of crude oils and unconventional oils with highly variable qualities, changes
1
2 Catalytic Naphtha Reforming Process
in catalytic reforming operations are often relatable to changes in either one of the
crude oils or crude slate that the oil refiner is processing.
1.1 EARLY HISTORY OF CRUDE OIL BUSINESS

There is a long history of the use of oil by people. Historians suggest that crude oil
was used over 5000 years ago and that Noah applied heavy crude oil or tar to his ark
to maintain the ark and protect it from water damage. Noah, the ark, and the flood
are discussed in the book of Genesis of the Bible. It has also been reported that China
used oil in laboratories as early as 200 BCE. There are some historical reports of the
use of crude oil in China and Japan in the seventh century. Historians indicate that
by 1100 CE, Christian crusaders were “setting petroleum alight” and frightening and
overcoming their enemies in battles. We are also informed that early immigrants in
North America gathered the “black goo” or oil and used it for medicinal purposes.
The “black goo” was used as ointment and medicine for toothache, fever, burns, open
sores, and rheumatism and for caulking canoes by the Seneca Indians.(1)
The vast global oil and gas businesses that we now participate in and enjoy owe
some of their origins to a little-known Persian physician and chemist, Muhammad
Ibn Zakariya Razi, who in the ninth century demonstrated that kerosene could be
produced via distillation of oil to generate a clean product for lamps.(2) In the middle
of the nineteenth century, a Polish chemist, Filip Neriusz Walter, and a Scottish
chemist, James Young, were later credited as key contributors in improving the
process for the production of kerosene from crude oil via distillation. By 1848,
James Young had an operating oil refining company producing kerosene.(3) Ignacy
Lukasiewics is credited by some with building the world’s first oil refinery in 1856.
His legendary achievements included the discovery of how to distill kerosene from
crude oil, the invention of the modern kerosene lamp, the introduction of the first
street lamp in Europe in 1853, and the construction of the world’s first modern
oil well in 1854.(4) About this time, there was significant oil production in Baku,
and Meerzoeff is reported to have built the first modern Russian refinery at Baku
by 1861.(5)
Abraham Pineo Gesner is recognized as one of the founders of the oil business in
North America and Canada based on his three initial US patents on the production
of kerosene from crude oils, which spurred extensive exploration and production of
oil within the United States and Canada.(6) Kerosene was found to burn cleaner and
cheaper than whale oil, and interest in the production of kerosene for lighting led to
the beginnings of businesses based on oil. Oil and gas businesses have now grown
exponentially into the global oil and gas business that we know.
After the startup of a plant by Abraham Pineo Gesner in 1854 for the production
of kerosene for lamps, kerosene production reached 5000 gallons per day in the
United States. The lure of instant wealth from the production of kerosene from crude
oil led to increased exploration and production of oil. George Bissell, Edmund L.
Drake, and William Smith were early innovators in developing technologies for the
exploration and production of oil. By 1859, there were 34 startup companies, and they
were producing a staggering 5 million gallons of kerosene annually. At the famous
Pithole City, Pennsylvania, oil production reached 6000 barrels per day by 1865, and
Introduction to Catalytic Reforming and the Oil Business 3
unfortunately, this was followed soon by diminishing oil production rates, which
finally led to a deserted Pithole City by 1869.(1,7,8)
Major investors made their play for oil, and that group included the great
entrepreneur, business genius, and oil magnate, John Davidson Rockefeller, who
transformed the oil business through ownership of Standard Oil. By 1879, Standard
Oil owned 90% of the oil refining capacity in the United States, and by 1891, it owned
an overwhelming 25% of oil production, 90% of the oil refining capacity, and an
extensive transportation system for moving oil and refined products in the United
States and in the world. The most productive oil find known at that time occurred
in 1901 in Spindletop, just outside of Beaumont, Texas, in the United States. The
Spindletop oil production rate was estimated at 72,000 barrels per day, and money
from Spindletop later fueled the growth of the Gulf Oil Company.(7)
1.2 POST-1900 HISTORY OF CRUDE OIL BUSINESS

As a result of the oil business boom in the United States, a number of companies
such as Gulf Oil, Phillips, and Texaco Fuels Oil began to operate and compete with
Standard Oil at the start of the twentieth century. With the invention of electricity by
Thomas Edison, the kerosene business for lighting was severely challenged, and rescue
came from Ford and the automobile industry. The automobile’s internal combustion
engine had to be powered with gasoline or petrol. New demand for gasoline led to
the installation of more oil refining capacities, which led to an increased need for
oil exploration and production. This was followed by expansion of infrastructure for
storage, capital for pipelines, and railroads for movement of crude oil and distribution
and marketing of finished products.(8–10)
John D. Rockefeller continued to lead and grow Standard Oil and the United States
economy by his exceptional business acumen and practices. However, some of his
business practices were unacceptable for his competitors. Essentially, Rockefeller’s
business strategies eliminated inefficient businesses as Rockefeller focused on
acquisition of smaller competing companies. Rockefeller understood the benefits
of vertical and horizontal integration and the economy of scale, as his leadership
strategies for Standard Oil positioned his company as the leader in oil exploration and
production, oil refining, petrochemicals, transportation and distribution, and retail
marketing in the United States and worldwide.(11)
To compete effectively with Standard Oil, Royal Dutch Oil and Shell Transportation
and Trading Company (Shell) amalgamated to form the Royal Dutch Shell Company
in 1907. As the application of mechanization increased in the early 1900s, the demand
for gasoline increased, as gasoline was used as fuel by automobiles and airplanes.
Increased demand for gasoline was met with greater expansion of every aspect of the
oil business from exploration and production to distribution and marketing of refined
transportation fuels. Standard Oil continued to encounter increased distrust of its
business practices, which in part had its origin in Standard Oil’s business relationships
with the railroad companies and its effort to eliminate competition in the business
segments that Standard Oil was engaged in. Due to the highly aggressive business
practices of Standard Oil and concerns about a possible oil business monopoly,
the United States Supreme Court ruled in 1911 that Standard Trust or Standard
Oil Company had operated to monopolize and restrain trade and ordered that the
company be dissolved into 34 smaller competing companies, significantly degrading
the size and business clout of Standard Oil.(11,12)
A major global oil and energy–impacting event occurred in September 1960 in
Baghdad, Iraq, with the formation of the Organization of the Petroleum Exporting
Countries (OPEC) by five countries, namely Iran, Iraq, Kuwait, Saudi Arabia, and
Venezuela. The OPEC group was later expanded to include Qatar (1961), Indonesia
(1962), Libya (1962), the United Arab Emirates (1967), Algeria (1969), Nigeria
(1971), Ecuador (1973), Gabon (1975), and Angola (2007). Gabon and Ecuador later
terminated their memberships, while Indonesia suspended its membership in 2009
and reactivated it in 2016. The OPEC countries currently produce about 40% of global
oil and have about 75% of the proved oil reserves.(11,12)
The 1973 oil embargo and subsequent events in the oil and gas industry continue to
show the clout of OPEC in crude oil pricing and the politico-economic decisions of non-
OPEC countries. Impacts of a number of OPEC decisions and drastic cyclical economic
downturns for the oil and gas industry led to consolidations of oil and gas companies
through mergers and acquisitions after 1995. Merger and acquisition activities led to the
formation of super major oil companies such as ExxonMobil, British Petroleum, Royal
Dutch Shell, Total S.A., and Chevron. Other major global companies based on assets and
revenues include Saudi Aramco of Saudi Arabia, Sinopec, Chinese National Petroleum
Corporation (CNPC) and PetroChina of China, Kuwait Petroleum Corporation of Kuwait,
ENI of Italy, and Lukoil of Russia. There are other national oil-exporting companies
that also feature prominently with respect to crude oil source and oil qualities and in
disruption of crude oil supplies and pricing. National oil-exporting companies such as
National Iranian Oil Company (NIOC), Petroleos de Venezuela, (PDVSA), Nigerian
National Petroleum Corporation (NNPC), and Petroleos Mexicanos (PEMEX) are
expected to continue to impact crude oil supply and pricing for a variety of factors. Some
of the factors include the size of proved oil reserves for Iran and Venezuela and periodic
oil production challenges in some of the countries such as Nigeria and Venezuela.
1.3 SOURCE OF CRUDE OIL

Crude or petroleum oil is a complex mixture of thousands of hydrocarbon
compounds with broad ranges of molecular weights and boiling points. In addition
to compounds that contain only carbon and hydrogen, there are also a variety of
organic compounds containing separately sulfur, nitrogen, nickel, and vanadium,
as well as other contaminant metals. Inorganic contaminant metals such as
sulfur, nitrogen, nickel, vanadium, calcium, magnesium, and copper are referred
to as heteroatoms, as they are different from the carbon and hydrogen atoms in
hydrocarbons. The wide variety of thousands of hydrocarbon compounds provides
the bases for the use of various fractions, components, and compounds of oil in energy
generation and in the manufacture of products for transportation, heating, lubrication,
chemicals, pharmaceuticals, plastics, automotive industries, agriculture, clothing, and
packaging. As a result of the use of oil and oil products as feedstocks in so many
chemically based manufacturing industries, oil is most essential for sustaining our
manufacturing plants and driving national economies.
Oils are usually found in various reservoirs where they have accumulated over the
past millions of years. During that time, conversion of dead organisms, zooplanktons
and algae, have occurred to form complex hydrocarbon mixtures through intense
compression and heating in geologic formations.(14,15) Crude oils are found in onshore
and offshore deposits in many regions of the world. As per the 2015 ranking of countries
with major proved oil reserves, Venezuela, Saudi Arabia, Canada, Iran, and Iraq are the
top five with proved oil reserves for each country of at least 140 billion barrels.
Petroleum fossil oil is not a renewable resource and there have expectedly been
some concerns with the rate of consumption of oil relative to the rate of frequent
discoveries of sizeable oil finds for oil replacements. Oil reserves, oil daily production
rates, and some technological advancements for producing unconventional oils such
as shale and bitumen from oil sands are reviewed in some detail later in this chapter.
1.4 CRUDE OIL RESERVES

An estimate of proved oil reserves is a moving target, as major oil discoveries made
in the last 15 years via application of innovative technologies for oil exploration and
production have significantly changed the ranking of countries. In addition, advances
in deepwater oil-production technologies have also greatly increased oil discoveries
and production. A conservative estimate is that total global proved oil reserves are
about 1.6 trillion barrels, with about 70% of that estimate in the OPEC countries as
of the first quarter of 2016. OPEC countries such as Venezuela, Saudi Arabia, Iran,
Iraq, and Kuwait dominate, with at least 100 billion barrels each in oil reserve, as
shown in Table 1.1.(12,13)
As shown in Table 1.1, OPEC countries Venezuela, Iran, Iraq, Libya, and Qatar
now own huge amounts of proved oil reserves due to major oil discoveries in the last
20 years. Data in Table 1.1 and Figure 1.1 show that Venezuela, which had 64.4 billion
barrels of proved oil reserves in 1993 and substantially lower than the 261 billion barrels
of Saudi Arabia, now owns 298 billion barrels of oil and ranks as the country with the
highest proved oil reserve in the world. Saudi Arabia’s huge oil reserves are centered
in the giant Ghawar field, whose oil reserves are estimated to be in excess of 75 billion
barrels. Venezuela owns huge extra-heavy oil reserves that are roughly estimated to
be greater than 500 billion barrels in the country’s Orinoco belt region. It is estimated
that 220 billion barrels of those have been credited as part of the 298 billion barrels of
proved oil reserve for Venezuela at this time. Due to capital and financial constraints,
political issues, and the quality of the extra-heavy oil in the Orinoco Belt region, oil
production has not been as high as it could be. Based on its massive proved oil reserves,
Venezuela has the potential to achieve much higher production rates in future.
Non-OPEC countries such as Canada, Brazil, the United States, and Russia have
also discovered huge reserves of unconventional oil and mostly bitumen from oil
sands in Canada and shale oil in the United States. As shown in Table 1.1, Canada’s
proved oil reserve grew from 39.5 billion barrels in 1993 to 175.4 billion barrels in
2013. The United States has benefited from applications of advanced oil geophysical
technologies for unlocking a number of discoveries of shale oil deposits, and that has
boosted the US oil reserves from 30.2 billion barrels in 1993 to 44 billion barrels in
2013.(12,13)
TABLE 1.1
Countries with High Proved Oil Reserves,
MMMB 1993 to 2013
Country 1993 2003 2013
Venezuela 64.4 77.2 297.7
Saudi Arabia 261.4 262.7 268.4
Canada 39.5 180.4 175.2
Iran 92.9 133.3 157.3
Iraq 100.0 116.0 150.0
Kuwait 96.5 99.0 101.5
UAE 98.1 97.6 97.8
Russia n/a 79.0 93.0
Libya 22.8 39.1 48.5
Nigeria 21.0 35.3 37.3
USA 30.2 29.4 44.0
Kazakhstan n/a 9.0 30.0
China 16.4 15.5 18.1
Qatar 3.2 27.0 25.2
Brazil 5.0 10.6 15.6
Source: Data taken from United States Energy Information

Administration Reports. Giddens, P. H., The Birth of
the Oil Industry, Porcupine Press, The Macmillan
Company, New York, 1938; Williamson, H. F., Daum,
A., Andreanoa, R., The American Petroleum Industry,
1899–1959, The Age of Energy, Northwestern
University Press, Evanston, Illinois, p. 16.(10,11)
Note: MMMB is billions of barrels.
Global proved oil reserves

350.0
1993 2003 2013
300.0
250.0
MMMB
200.0
150.0
100.0
50.0
0.0
Venezuela Saudi Arabia Canada Iran Iraq
FIGURE 1.1 Top five countries’ proved oil reserves for 1993 to 2013.
Note: MMMB is billions of barrels.
It is necessary to emphasize the ever-changing landscape and leaderboard of

proved oil reserves with time. A recent independent assessment report of proven oil
reserves as of 2016 by Rystad Energy, a Norwegian consulting company, using data
not provided by oil-producing countries, now shows that the United States has moved
ahead of Saudi Arabia, Russia, and Venezuela as the global leader in oil reserves, with
US has largest oil reserves in the world

300
250
Billions of barrels
200
150
100
50
0
s
ia
an
il
a
aq
te
bi
ad
el
az
ss
Ir
Ir
zu
a
ra
Br
n
Ru
St
Ca
A
ne
d
di
Ve
te
u
ni
Sa
U
FIGURE 1.2 Proved oil reserves July 2016 by Rystad.

From Cunningham, N., US Has World’s Largest Oil Reserve. Oil Price, 2016, http://oilprice.
com/Energy/Energy-General/US-Has-Worlds-Largest-Oil-Reserves.html.(28)
over 260 billion barrels. Rystad Energy oil reserves data are as shown in Figure 1.2.(28)
Rystad argued that there are no uniform ways to measure oil reserves and, as a result,
oil reserves assessments differ grossly. It was suggested by Rystad that the United
States holds over 260 billion barrels of oil reserves and more than 50% of that was
located in shale formations.
1.5 INTRODUCTION TO OPPORTUNITY OILS

AND UNCONVENTIONAL OILS
The goal of the review of the history of oil in this book is to share the author’s
appreciation of the rapid development of the oil business in the last 170 years.
Additionally, items covered in this introductory section should provide appropriate
background for a good understanding of the sources of crude oil, crude oil and liquid
production, crude oil consumption rate, conventional and unconventional oil qualities,
and oil prices. Opportunity oils are crude or unconventional oils and oil fractions
that become available at “opportune” times and at favorable discounted prices. For
opportunity crude oils, their prices are usually highly discounted relative to Western
Texas Intermediate (WTI) and Brent crude oils. However, opportunity oils may vary
widely with respect to the composition of their naphtha, distillate, gas oil, and residual
oil fractions and heteroatom contaminant concentrations. Furthermore, the properties
of naphtha, distillate, gas oil, and residual oil fractions from a crude distillation unit
depend on the percentages of the constituent crude and unconventional oils in the crude
slate. Since the ultimate properties of naphtha, distillate, gas oil, and residual oil feeds
to downstream processing units are highly dependent on the oils in the crude slate, it is
important to fully characterize the crude oils before purchasing and definitely before
processing the oils in refineries. Unconventional oils in this book refers to bitumen-
derived oils and tight or shale oils produced via nontraditional technologies such as
surface mining, steam-assisted gravity drainage (SAGD) and hydraulic fracking.
Where applicable, unconventional oils should be reviewed in detail, as the properties

of unconventional oils vary widely and are significantly different from the oils
produced via conventional extraction technologies. Factors that can cause variability
in the properties of unconventional oils are covered in some detail in a subsequent
chapter in this book. Factors that are relevant in the ranking of countries with respect
to oil reserves, daily oil production, and global oil consumption rates are provided.
1.6 GLOBAL OIL PRODUCTION

Crude oil production rates vary over time due to a multitude of factors. Contributory
factors include production and supply disruptions as a result of vandalism of oil
production assets, direct attacks and kidnappings of oil production personnel, regional
conflicts, political factors, and OPEC-imposed production constraints on its members.
OPEC-imposed constraints could impact the oil production rates of OPEC and
non-OPEC countries as well as prices of crude oils. The oil glut of 2015 led to the
collapse of oil prices, with negative consequences for the development and production
of unconventional oils, as their costs of production are typically higher than those of
conventional crude oils. The top-ranked daily oil-producing country has been Saudi
Arabia and, as shown in Table 1.2, Saudi Arabia maintained its position between 2003
and 2013. Saudi Arabia’s production rate has been a dominant factor with respect to some
of the oil production decisions made by OPEC. The daily production rates of petroleum
oil for the top 15 countries are listed in Table 1.2. Daily crude oil production rates of the
top five countries for the years of 2003, 2008, and 2013 are as shown in Figure 1.3.(12,13)
Oil production ranking for countries differs considerably, however, when it is
based on total petroleum and other hydrocarbon liquids, as shown in Table 1.3. Total
TABLE 1.2
Daily Crude Oil Production of Countries in
MMBPD
Country 2003 2008 2013
Saudi Arabia 10.1 10.7 11.5
Russia Federation 8.6 10.0 10.8
USA 7.4 6.8 10.0
Canada 3.0 3.2 4.0
Iran 4.0 4.4 3.6
Iraq 1.3 2.4 3.1
Venezuela 2.9 3.2 2.6
Kuwait 2.4 2.8 3.1
Nigeria 2.2 2.2 2.3
Mexico 3.8 3.2 2.9
Kazakhstan 1.1 1.5 1.8
Norway 3.3 2.5 1.8
Libya 1.5 1.7 1.0
Angola 0.9 1.8 1.8
Algeria 1.8 1.8 1.7
Top 5 oil-producing countries

14.0
2003 2008 2013
12.0
Production, MMBPD
10.0
8.0
6.0
4.0
2.0
0.0
Saudi Arabia Russia USA Canada Iran
FIGURE 1.3 Daily oil production rates in millions of barrels of oil per day (MMBPD) of
top five countries.
petroleum and other hydrocarbon liquids as defined consist of crude oils, condensates,
tight oil, extra-heavy crude oil, and bitumen produced by a country. Tight oil refers
to oils that are produced from shale formations. Special unconventional technology
referred to as hydraulic fracking is required for successful production of shale or
tight oil. Bitumen is oil derived from oil sands and produced via surface mining and
steam-assisted gravity drainage technologies. Bitumen as used in Table 1.3 represents
the sum of all bitumen-derived oils, including diluted bitumen (Dilbit) and upgraded
bitumen, and is referred to as a syncrude oil.
Diluted bitumen is bitumen that has a diluent such as water, condensate, naphtha,
or crude oil added to permit facile transportation of the bitumen. An upgraded
TABLE 1.3
Total Petroleum and Other Liquids Production
MMBPD
Country 2006 2010 2014
USA 8.3 9.7 14.1
Russia 9.7 10.3 10.9
China 3.9 4.4 4.6
Canada 3.3 3.4 4.4
UAE 3.0 2.8 3.5
Iran 4.2 4.2 3.5
Iraq 2.0 2.4 3.4
Brazil 2.2 2.7 3.0
Mexico 3.7 3.0 2.8
Kuwait 2.7 2.5 2.8
Venezuela 2.8 2.6 2.7
Nigeria 2.4 2.5 2.4
Qatar 1.3 1.8 2.1
Norway 2.8 2.1 1.9
Note: MMBPD is millions of barrels of oil per day.

bitumen oil is bitumen that has been upgraded via thermal and catalytic processes in
order to improve the qualities of the resultant oil and render it suitable for processing
in oil refineries. Synthetic crude oils are usually higher priced relative to the diluted
bitumen oil or Dilbit, which is an oil sands–derived oil that has not been subjected
to significant thermal and/or catalytic upgrading.(16,17) Details of unconventional oil
production technologies are covered later in this section. Other liquids included in the
data in Table 1.3 are natural gas plant liquid (NGPL), biofuels, gas-to-liquids (GTL),
and coal-to-liquid (CTL) products.(12)
Projected increases in the production of natural gas liquids and light tight oil
would most likely maintain the position of the United States as the top producer of
total petroleum and other liquids in the world through 2040, as shown in Figure 1.4.(12)
Total oil liquid production for the United States shows that light tight oil and
natural gas liquid production would increase significantly after 2015 and would be
much higher than conventional oil rates.
2015 total liquid and gas production for the United States, Russia, and Saudi
Arabia in Figure 1.5 shows that the United States maintained its position as the top
producer of total liquids and gas.
Unconventional oils represent a growing segment of oils from oil sands, shale rock,
and deepwater that have to be extracted via the application of innovative, nontraditional
drilling and extraction technologies. There are a variety of technologies used, and the
major ones are surface mining and steam-assisted gravity drainage for oil sands and
fracking for light tight oil from shale rock formations, as indicated previously.
Steam-assisted gravity drainage extraction is applied in addition to the extensively
used surface mining for extracting bitumen from oil sands. Current extractive
production of bitumen via surface mining is energy intensive, as only 10% of the
25
20
High resource
Million barrels per day
case
15
“Peak oil”
Light oil
10
Conventional production
5
Alaska crude
Natural gas liquids
0
1950
1955
1960
1965
1970
1975
1980
1985
1990
1995
2000
2005
2010
2015
2020
2025
2030
2035
2040
FIGURE 1.4 US total liquids through 2040.

From US Energy Information Administration [EIA] Reports; Lance, R., The Benefits of US
Crude Exports, IPAA Annual Meeting. November 13, 2014. www.conocophillips.com/files/
resource.(12,27)
Estimated petroleum and natural gas hydrocarbon production in selected countries
60 30
United States
Quadrillion British thermal units
Russia
Million barrels per day of oil

50 25
Saudi Arabia
40 20
equivalent
30 15
Natural
gas
20 10
Petro-
10 5
leum
0 0
2008 2009 2010 2011 2012 2013 2014 2015
FIGURE 1.5 Total liquids and gas production 2008–2015.

Note: Lower bar represents total hydrocarbon liquids and upper bar total gas. Units are in
million barrels per day of equivalent oil and quadrillion British thermal units. (From US
Energy Information Administration [EIA] Reports.(12))
FIGURE 1.6 Surface mining for recovery of bitumen.
sand, clay, and water is bitumen. A surface mining site is as shown in Figure 1.6, and
a schematic of the steam-assisted gravity drainage technology is shown in Figure 1.7.
In both SAGD and surface mining extractive processes, significant amounts of energy
from natural gas use and for separation of oil from sands are required to produce a
barrel of bitumen from oil sands.(17)
The need for innovative energy-efficient technology for extracting bitumen directly
from oil sands is great. Surface mining extraction is currently in use in Canada and
Mexico for the production of bitumen.
Light oils consist of tight and shale oils that are produced essentially from
impermeable shale rock type formations. Shale is fine-grained sedimentary rock that
is easily broken into parallel layers. Shale rock formations can contain large amounts
of oil and/or natural gas. A major extraction challenge is that the hydrocarbons
in the shale formation do not flow easily and must be dislodged for accessibility
and recovery. In order to extract the oil efficiently and profitably, two production
Steam-assisted gravity drainage (SAGD)-

schematic
SAGD facility –Horizontal drilling

–Moderate pressure steam (500 psi)
–50%–70% oil in place recovery
Courtesy EnCana
Oil producer Steam injector

Steam chamber
Slots
Oil sand formation
Steam flow
Oil flow
Research institute
FIGURE 1.7 Steam-assisted gravity drainage recovery of bitumen from oil sands.
technologies are used. The technologies are referred to as horizontal drilling and
hydraulic fracking. Instead of the typical vertical drilling with possibly a J-type
bend used for conventional oils, horizontal drilling involves an initial drilling in the
vertical direction for a short distance, followed by drilling horizontally and possibly
for a few miles to access oil deposits. To loosen oil deposits spread over a wide
area of sedimentary rock, water and chemicals are added at high pressure during oil
production to free the oil in the deposits. The application of hydraulic fracking has
led to record production of shale or light tight oil and shale gas in the United States.
Unfortunately, the 2015 collapse of global oil prices moderated the rate of production
of light tight oil. Similarly, applications of improved technologies for exploration and
production have led to oil finds in deepwater off the coasts of West Africa and South
America and in the Gulf of Mexico.
1.7 OIL CONSUMPTION

The US economy required the use of 20 million barrels per day in 1993, and this
has gradually been reduced to 18.9 million barrels per day by 2013 due to energy
conservation, automotive fuel efficiency, and environmental regulatory programs.
Energy conservation programs include increased use of renewable transportation
fuels, natural gas, and renewable fuels for power generation. There have been
similar modest declines in oil consumption rates for the Organization for Economic
Cooperation and Development (OECD) countries, notably for Germany, the United
TABLE 1.4
Daily Oil Consumption Rates in MMBPD
Country 2003 2008 2013
USA 20.0 19.5 18.9
China 5.8 8.3 10.8
Japan 5.5 4.4 4.6
India 2.5 3.2 3.7
Russian Federation 2.7 2.9 3.3
Brazil 2.0 2.4 3.0
Canada 2.2 2.3 2.3
Germany 2.7 2.5 2.4
UK 1.7 1.6 1.5
France 2.0 1.9 1.7
Italy 1.9 1.7 1.3
Spain 1.9 1.7 1.3
Mexico 1.9 2.1 2.0
Note: The oil consumption rates are in millions of barrels per day or MMBPD.
Kingdom, Italy, France, and Spain, as these countries have implemented energy
conservation programs. Daily oil consumption rates for selected years, 2003, 2008,
and 2013, are provided in Table 1.4. Oil demand growth for non-OECD countries
such as China and India is on the rise, though tempered slightly by slower economic
growth rates in the past two decades.(13)
Oil demand declines for the United States and other OECD countries were
partially offset by drastic demand increases of over 80% for China and over 45%
for India between 2003 and 2013 due to increased oil refining for the production of
transportation fuels and other refined products.
1.8 CRUDE OIL AND OTHER HYDROCARBON LIQUID QUALITIES

There are many types of crude oils, and they are classified broadly as sweet light,
heavy sour, extra-heavy sour, and heavy blended synthetic crude oils. Sweet and sour
are descriptive terms for crude oils that are based on the amount of organic sulfur
in the crude oils. Sweet crude oils are those with sulfur concentrations that are less
than 0.5 wt. %. Crude oils that contain greater than 0.5 wt. % sulfur are referred to
as sour oils. Heavy sour crude oils are oils with American Petroleum Institute (API)
gravity of less than 20 and concentrations of sulfur compounds that are greater than
0.5 wt. %. Extra-heavy oils are typically those with API gravities that are less than
10 API. More specifically, the World Energy Council (WEC) defined extra-heavy oil
as crude oil having a gravity of less than 10° API and a reservoir viscosity of no more
than 10,000 centipoises. When reservoir viscosity measurements are not available,
extra-heavy oil is considered by the WEC to have a lower limit of 4 API.
Note:
Gravity of oils is determined and reported as degrees API.
Specific gravity is defined as the density of an oil relative to the density of water,
where density of water is defined approximately as 1 gram/cubic centimeter.
Degrees API = (141.5/Specific gravity) − 131.5.
Based on the definitions, Louisiana Light Sweet (LLS), West Texas intermediate,
and Brent are light sweet crude oils; Arabian Light is a sour crude oil; and both
Maya and Tia Juana heavy are heavy sour crude oils. The profitability of refining a
crude oil should be fully assessed, and the assessment should incorporate expected
costs associated with processing the crude oil and relevant related asset maintenance
costs. Due to the broad properties of crude oils, a current crude oil assay database
is highly recommended. Pertinent crude oil properties such as sulfur, API gravity,
total acid neutralization number (TAN), concentrations of contaminant metals, and
concentrations of oil fractions on distillation should also be considered in estimating
the value and price of a crude oil relative to the price of the benchmark crude oil
used for setting its price. Typical benchmark crude oils include and are not limited to
Brent, West Texas intermediate, and Dubai Fateh. Another benchmark for crude oil
pricing that is favored by OPEC is what is referred to as the OPEC basket of oils. The
OPEC basket of oils price is based on the prices of a collection of seven crude oils
from Algeria, Saudi Arabia, Indonesia, Nigeria, Dubai, Venezuela, and the Mexican
isthmus.
It is worth noting that oil refiners that have the necessary bottom-of-the-barrel
upgrading processing assets in their refineries are in enviable positions to take
advantage of lower-cost crude and synthetic oils, as they can reliably and profitably
process a wide variety of purchased crude and synthetic oils. Selected oil quality
data for a small number of crude oils used in oil refineries are provided in Table 1.5.
General crude oil qualities should be taken as merely representative of analyzed
samples of the crude oils, and it should be understood that oil qualities at the time
of purchase could vary depending on the specific areas from which the oils are
produced, the degree of upgrading of the oils, chemicals used during production, and
flow enhancers for oil transportation. As indicated previously, it could be beneficial
and profitable for the oil refiner to update its database for crude oil assays as often
as feasible so as to fully take advantage of possible discounts for gross variations in
crude oil qualities when the oils are available.
Bitumen from oil sands is extra-heavy oil and usually has gravity that is less than
10 API. As discussed, a variety of extraction technologies are applied for extracting
bitumen, and two of the most favored ones are surface mining and steam-assisted
gravity drainage.(16,18) Two of the largest deposits of oil sands are in the Orinoco Belt
of Venezuela and Alberta, Canada. Bitumen is a highly viscous liquid that does not
flow easily and can be transported in pipelines only after the addition of condensate
diluent to produce Dilbit or the addition of a synthetic oil to produce Synbit. Since
bitumen usually contains high amounts of contaminants, it has to be upgraded and
blended with other oils so as to reduce its sulfur, nitrogen, nickel, vanadium, and
acidic contents and render it suitable for profitable oil refining (see Figure 1.8). The
qualities of the Hamaca from Venezuela and Athabasca bitumen from Canada, as
TABLE 1.5
Selected Properties for Crude Oils
Crude Oil LLS WTI WTS AL BR TIA/H MAYA
Gravity, API 36.1 40.8 34.1 33.4 38.3 12.3 22.2
Sulfur, wt. % 0.45 0.34 1.64 1.77 0.40 2.80 3.30
Pour point, C −37.0 −29.0 −46.0 −54.0 −42.0 −16.0 −36.0
Viscosity @100F 4.3 4.9 4.6 8.4 3.9 8.6 102.0
V, wppm 1.2 1.6 6.4 13.5 6.0 386 314.0
Ni, wppm 7.1 1.6 3.7 3.3 1.0 38.5 52.0
CCR, wt. % 1.1 1.1 3.3 3.6 2.1 11.2 12.0
TAN, mgKOH/g 0.58 0.10 0.1 0.00 0.10 3.90 0.28
Notes:
1. LLS is Light Louisiana Sweet; WTI is West Texas Intermediate; WTS is West Texas Sour; AL is Arab
Light; BR is Brent; TIA/H is Tia Juana Heavy. Maya is from Mexico.
2. Kinematic viscosity is at 100 F and the units are centistokes.
3. The crude oil characteristics are taken from a variety of sources. US Energy Information Administration
(EIA) Reports; BP Statistical Review of World Energy, June 2014; Oyekan, S. O., Torrisi, S.,
Opportunities and Challenges in Transportation Fuels Production, Paper Presented at the AIChE
Regional Process Technology Conference, Galveston, TX, October 2, 2009.(12–16)
4. CCR is Conradson Carbon and is a measure of the concentration of asphaltenes and how the heavy
the oil is.
5. TAN is total acid neutralization number and the units are in mg of KOH per gram of the oil, where
KOH is potassium hydroxide.
6. Viscosity is kinematic viscosity at 100°F.
7. Pour point is in degrees centigrade.
well as the upgraded Hamaca oil and Western Canadian Select (WCS), are given in
Table 1.6.(16,19,20) Western Canadian Select is a heavy blended crude oil comprised of
sweet synthetic (upgraded) oils, other crude oils, and condensate.
It is beneficial for oil refiners to have good and current knowledge of the qualities
of the crude oils that they are purchasing and available for processing in their
refineries so as to anticipate potential operational and reliability challenges while
taking advantage of opportunities to maximize refinery profitability. Also, since
upgraded bitumen is usually sold in synthetic mixtures containing other crude oils and
condensate, the quality of a given bitumen-derived oil is likely to vary substantially,
and an up-to-date assay database program should be utilized for profitable processing
of such oils in combination with the other crude oils in refineries.
A discussion of crude oil would be grossly incomplete without discussing the
impact of the significant increase in the production of shale or light tight oil in the
United States on crude oil prices. It is important to discuss tight oils with respect
to the challenges that should be expected in processing significant percentages
of shale oil in crude slates. Though organic sulfur, contaminant metals, and acid
concentrations of tight oils are usually similar to those of sweet crude oils, the high
paraffinic content and percentages of their oil fractions make processing of light
Refinery fuel/off gases
Recycled Naphtha
Atmospheric H/T
diluent
distillation unit Synthetic
Bitumen +
Distillate crude
diluent
H/T oil
Vacuum
distillation VGO H/T
unit VGO to refinery
Vacuum residue
FIGURE 1.8 A typical bitumen upgrader showing use of diluent and generation of synthetic
crude oil.
Note: Recycled diluent could be a naphtha or light oil. Naphtha H/T is the naphtha
hydrotreater. VGO is vacuum gas oil. (From Gray, M. R., Tutorial on Upgrading of Sands
Bitumen, University of Alberta, Canada.(17))
TABLE 1.6
Bitumens and Their Upgraded and Blended Oils
Crude Oils Hamaca Bitumen Hamaca Athabasca Bitumen WCS
Gravity, API 8.4 26 7.7–9.0 19–22
Sulfur, wt. % 3.8 1.55 4.4–5.1 2.8–3.5
Ni, wppm 115 42 69–85 46–59
V, wppm 388 152 81–218 115–140
TAN, mg KOH/g 2.8 0.7 >5.4 <1.0
tight oils more challenging than the processing of conventional oils. However, due to
favorable prices relative to WTI and Brent and reliable supply, tight oils are highly
desirable, cost-efficient oils for some United States oil refiners. A number of US oil
refiners are installing additional crude distillation units for efficient and profitable
refining of higher percentages of light tight oils in their refineries’ crude slates. The
properties of tight oils are quite different from those of other crude oils, as shown by
the properties of the Bakken and Eagle Ford oils in Table 1.7.(21,22) Bakken and Eagle
Ford oils are cost-effective replacements for imported light sweet crude oils. Tight
oils had effectively replaced most of the imported light crude oils, especially Bonny
Light from Nigeria, in oil refineries in the United States by 2016.
Since light tight oils are usually priced lower relative to benchmark WTI and
Brent, they are desirable cost-effective feedstocks for refineries. However, challenges
that have been identified in processing light tight oils include the negative impact
of its high paraffinic contents, as this causes significant precipitation of some
TABLE 1.7
Tight Oils Compared to Conventional Crude Oils
Crude Oil Eagle Ford Bakken LLS WTI AL Brent Bonny
Gravity, API 45.7 40 36.1 40.8 33.4 38.3 32.9
Sulfur, wt. % 0.04 0.2 0.45 0.34 1.77 0.40 0.2
Pour Point, C −27.4 N/a −37.0 −29.0 −54.0 −42.0 −14.4
V, wppm 0.1 0.1 1.2 1.6 13.5 6.0 0.4
Ni, wppm 0.1 0.4 7.1 1.6 3.3 1.0 4.3
CCR, wt. % 0.2 0.8 1.1 1.1 3.6 2.1 1.4
TAN, mgKOH/g 0.1 0.1 0.58 0.10 0.00 0.10 0.3
of the asphaltenes of heavier crude oils in the crude unit. Significant asphaltene
precipitation leads to increased reliability issues in atmospheric crude units and
associated equipment. Furthermore, refiners who had upgraded their refining assets to
process heavy crude oils may find that their bottom-of-the-barrel conversion units are
underutilized. A number of oil refining technologies and catalyst providers suggest
that installation of additional atmospheric distillation units, reconfiguring of refinery
oil processing schemes, and use of the fluid catalytic cracker (FCC) for processing
could be beneficial for maximizing profitability from processing high percentages of
shale oil in refineries.(22–26)
Another major factor worth emphasizing with respect to crude oil qualities are the
chemicals that are used during crude oil extraction, production, and transportation,
as the chemicals could produce metals and chlorides that are either contaminants
or corrosion agents in downstream processing of the crude oil fractions after the
atmospheric and vacuum distillation units. Examples include the use of antifoaming
agents containing silicon and condensate and naphtha used as flow improvers for
crude oils and unconventional oils. Chemicals added during production and for
transportation could undergo thermal and catalytic reactions to generate contaminant
metals that can poison precious and base metals containing catalysts in oil refining
processes. Poisoning by added contaminant metals other than the sulfur, nitrogen,
iron, nickel, and vanadium typically inherent in crude oil could lead to poor catalytic
performances of process units and underutilization of oil refining assets due to
process units’ reliability challenges.
Another class of seemingly cost-effective oil feedstocks for oil refiners are
those typically characterized as opportunity crude oils and oil fractions. Detailed
characterization of the oils should be conducted and is recommended before they are
processed in high percentages in crude slates for crude units and process units in oil
refineries. Documented cases of silicon and other poisoning events of the naphtha
hydrotreater and catalytic reforming units are discussed in subsequent chapters.
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Catalytic Naphtha

© 2019 by Taylor & Francis Group, LLC

No claim to original U.S. Government works

Printed on acid-free paper

International Standard Book Number-13: 978-1-138-03430-3 (Hardback)

Chapter 1 Introduction to Catalytic Reforming and the Oil Business................... 1

Chapter 2 Basics of Crude Oil Refining.............................................................. 19

Chapter 3 Overview of Oil Refining Process Units............................................. 63

Chapter 4 Basic Principles of Catalytic Reforming Processes.......................... 111

4.4.3 Recycle Gas Hydrogen to Hydrocarbon Molar

Chapter 5 Catalytic Reforming Catalysts.......................................................... 155

5.9 Alumina Hydrothermal Stability Test.................................... 184

Chapter 6 Catalytic Reforming Technologies.................................................... 191

Chapter 7 Catalyst and Process Management Challenges................................. 245

7.4.1 High Pressure Drop in Continuous Catalyst

Chapter 8 Special Catalytic Reforming Topics.................................................. 273

Chapter 9 Special Topics—Turnaround and Platinum Management................. 319

technologies for reducing hydrogen chloride and volatile organic compounds in

execution of turnarounds, and safety problems during catalytic reformer startups,

1.1 EARLY HISTORY OF CRUDE OIL BUSINESS

1.2 POST-1900 HISTORY OF CRUDE OIL BUSINESS

1.3 SOURCE OF CRUDE OIL

1.4 CRUDE OIL RESERVES

Source: Data taken from United States Energy Information

Global proved oil reserves

It is necessary to emphasize the ever-changing landscape and leaderboard of

US has largest oil reserves in the world

FIGURE 1.2 Proved oil reserves July 2016 by Rystad.

1.5 INTRODUCTION TO OPPORTUNITY OILS

Where applicable, unconventional oils should be reviewed in detail, as the properties

1.6 GLOBAL OIL PRODUCTION

Top 5 oil-producing countries

Note: MMBPD is millions of barrels of oil per day.

FIGURE 1.4 US total liquids through 2040.

Estimated petroleum and natural gas hydrocarbon production in selected countries

Million barrels per day of oil

FIGURE 1.5 Total liquids and gas production 2008–2015.

FIGURE 1.6 Surface mining for recovery of bitumen.

Steam-assisted gravity drainage (SAGD)-

SAGD facility –Horizontal drilling

Oil producer Steam injector

1.7 OIL CONSUMPTION

1.8 CRUDE OIL AND OTHER HYDROCARBON LIQUID QUALITIES

Refinery fuel/off gases

Overview of Oil Refining Process Units

Basic Principles of Catalytic Reforming Processes

Catalytic Reforming Catalysts

Catalytic Reforming Technologies

Catalyst and Process Management Challenges

Special Catalytic Reforming Topics

Special TopicsTurnaround and Platinum Management

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1.5 INTRODUCTION TO OPPORTUNITY OILS