Crude Oil Refining

This book provides an overview of crude oil refining processes and presents a deep
analysis of the current context and challenges imposed on players in the downstream
industry. Crude Oil Refining: A Simplified Approach covers traditional processes of
the refining industry, the impact of current trends, and technological routes available
to help these players survive in a highly competitive environment.

FEATURES

• Offers a simplified approach to crude oil refining processes

• Discusses economic information related to the downstream business,
­including refining margins and profitability
• Introduces newer trends in the industry, such as petrochemical integration,
crude-to-chemicals refineries, and renewables coprocessing in crude oil
refineries
• Presents the challenges related to these new trends and offers technological
solutions to overcome them for profitable and sustainable operations
• Describes how the use of biofuels can minimize the environmental impact
of transportation fuel in nations of high demand like Brazil

Offering a contemporary view of current challenges and opportunities in the

­downstream oil and gas business, this practical book is aimed at readers working in
the fields of petroleum and chemical engineering.
Crude Oil Refining
A Simplified Approach

Marcio Wagner da Silva

First edition published 2023
by CRC Press
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© 2023 Marcio Wagner da Silva
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ISBN: 978-1-032-27212-2 (hbk)
ISBN: 978-1-032-27215-3 (pbk)
ISBN: 978-1-003-29182-4 (ebk)
DOI: 10.1201/9781003291824
Typeset in Times
by Apex CoVantage, LLC
Contents
Preface����������������������������������������������������������������������������������������������������������������������� ix
Acknowledgments����������������������������������������������������������������������������������������������������� xi
Author��������������������������������������������������������������������������������������������������������������������� xiii

Chapter 1 Crude Oil���������������������������������������������������������������������������������������������� 1

1.1.Introduction������������������������������������������������������������������������������� 1
1.2. Primary Treating Processes of Crude Oil���������������������������������� 4
1.3. Crude Oil Derivatives���������������������������������������������������������������� 7

Chapter 2 Crude Oil Distillation������������������������������������������������������������������������� 15

2.1. Crude Oil Distillation Units����������������������������������������������������� 15
2.2. Vacuum Distillation Section���������������������������������������������������� 19

Chapter 3 Thermal Conversion Processes����������������������������������������������������������� 23

3.1. Visbreaking Process����������������������������������������������������������������� 23
3.2. Delayed Coking Process���������������������������������������������������������� 25
3.3. Solvent Deasphalting Technologies����������������������������������������� 30

Chapter 4 Catalytic Conversion Processes���������������������������������������������������������� 35

4.1. Fluid Catalytic Cracking (FCC) Units������������������������������������� 35
4.2. Residue Fluid Catalytic Cracking (RFCC)
Technologies���������������������������������������������������������������������������� 39
4.3. The FCC Catalyst: Converting Residues to
Added-Value Derivatives��������������������������������������������������������� 42
4.4. Meeting the Market Demand through FCC
Optimization���������������������������������������������������������������������������� 43
4.5. The Petrochemical FCC Alternative: Raising
Competitive Advantage����������������������������������������������������������� 45
4.5.1. Propylene Production from FCC������������������������������� 46
4.6. Catalytic Reforming Technologies������������������������������������������ 49
4.6.1. Aromatics Separation Section: Ensuring
­Maximum Added Value��������������������������������������������� 52
4.6.2. Improving the Yield of Light Aromatics:
­Molecular Management�������������������������������������������� 54
4.7. Naphtha Alkylation Technologies�������������������������������������������� 56
4.8. Naphtha Isomerization������������������������������������������������������������� 60
4.9. Light Olefin Condensation������������������������������������������������������ 64
4.10. Etherification Technologies����������������������������������������������������� 66
4.11. Light Paraffin Dehydrogenation���������������������������������������������� 69
v
vi Contents

Chapter 5 Hydroprocessing Technologies���������������������������������������������������������� 73

5.1. Naphtha Hydrotreating Technologies�������������������������������������� 77
5.1.1. Coker Naphtha Hydrotreating����������������������������������� 77
5.1.2. FCC Naphtha Hydrotreating Technologies��������������� 79
5.1.2.1 A Special Challenge: Diene
(Diolefin) Control������������������������������������� 81
5.2. Diesel Hydrotreating Units������������������������������������������������������ 82
5.3. Bottom Barrel Hydrotreating Technologies
(Residue Upgrading)��������������������������������������������������������������� 84
5.4. Atmospheric Residue Desulfurization: A Special Case���������� 88
5.5. Hydrocracking Technologies��������������������������������������������������� 91
5.6. The Hydroprocessing Catalysts����������������������������������������������� 99
5.7. Deactivation of Hydroprocessing Catalysts��������������������������� 100

Chapter 6 Lubricating Production Refineries��������������������������������������������������� 105

6.1. Closing the Sustainability Cycle: Used Lubricating Oil
Recycling������������������������������������������������������������������������������� 110
6.1.1. Used Lubricating Recycling Technologies������������� 111
6.2. A Glance over the Brazilian Lubricating Market������������������ 114

Chapter 7 Refining Configurations������������������������������������������������������������������� 119

7.1. Nelson Complexity Index������������������������������������������������������ 125
7.2. The Effect of Crude Oil Slate over the Refining
Scheme���������������������������������������������������������������������������������� 126
7.2.1. Heavier Crude Oil Processing��������������������������������� 126
7.2.2. Light Crude Oil Processing������������������������������������� 133

Chapter 8 Hydrogen Production����������������������������������������������������������������������� 137

8.1. Hydrogen and Syngas Production Routes����������������������������� 137
8.2. Renewable Hydrogen Generation Routes: Fundamental
Enabler to the Energy Transition������������������������������������������� 141
8.3. Hydrogen Network and Management Actions���������������������� 142
8.3.1. The Role of Catalytic Reforming Units
in the Refineries’ Hydrogen Balance���������������������� 143

Chapter 9 Caustic Treating Processes��������������������������������������������������������������� 147

9.1. Caustic Treating Technologies����������������������������������������������� 147
9.2. Bender Treating Technologies����������������������������������������������� 152
Contents vii

Chapter 10 Environmental Processes������������������������������������������������������������������ 155

10.1. Sour Water Stripping Technologies��������������������������������������� 155
10.2. Amine Treating Technologies������������������������������������������������ 158
10.3. Sulfur Recovery Technologies����������������������������������������������� 160
10.4. Water and Wastewater Treatment Technologies�������������������� 165
10.4.1. Oily Sewer��������������������������������������������������������������� 167
10.4.2. Stormwater Sewer��������������������������������������������������� 167
10.4.3. Domestic Sewage���������������������������������������������������� 169
10.4.4. Steps of Effluent Treatment������������������������������������� 169
10.4.5. API Oil-Water Separator����������������������������������������� 169
10.4.6. Dissolved Air Flotation������������������������������������������� 169
10.4.7. Biological Treatment����������������������������������������������� 170
10.4.8. Membrane Bioreactors (MBR)������������������������������� 170

Chapter 11 A New Downstream Industry����������������������������������������������������������� 173

11.1. What Is Petrochemical Integration?�������������������������������������� 175
11.2. More Added Value to the Processed Crude: Integrated
Refining Schemes������������������������������������������������������������������ 177
11.3. Crude Oil to Chemicals: Zero Fuel and Maximum Added
Value�������������������������������������������������������������������������������������� 178
11.3.1. Available Crude-to-Chemicals Routes�������������������� 189
11.3.2. The Residue Upgrading Technologies in the
Integration of Refining and Petrochemical Assets��� 190
11.3.3. Closing the Sustainability Cycle: Plastic
Recycling Technologies������������������������������������������ 192
11.4. Renewables Coprocessing in Crude Oil Refineries��������������� 194
11.4.1. Biofuel Production in Brazil����������������������������������� 195
11.4.2. Challenges of Renewables Coprocessing in
Crude Oil Refineries������������������������������������������������ 196
11.4.3. The Hydrotreated Vegetable Oil (HVO): An
Attractive Route to Reach “Green Diesel”�������������� 199

Chapter 12 The Propylene Production Gap�������������������������������������������������������� 203

12.1. Propylene: A Fundamental Petrochemical Intermediate������� 204
12.2. Propylene Production Routes������������������������������������������������ 205
12.2.1. The Maximum Olefin Operation Mode������������������ 207
12.2.2. The Petrochemical FCC Alternative����������������������� 209
12.2.3. Steam Cracking Units��������������������������������������������� 211
12.2.4. Propane Dehydrogenation��������������������������������������� 211
12.2.5. Olefin Metathesis���������������������������������������������������� 214
12.2.6. Methanol-to-Olefin Technologies (MTO)��������������� 214
viii Contents

Chapter 13 Gas-to-Liquid Processing Routes����������������������������������������������������� 219

13.1. Gas-to-Liquid Technologies�������������������������������������������������� 219
13.1.1. Available Technologies������������������������������������������� 221
13.2. Ammonia Production Process: An Overview������������������������ 224
13.2.1. Ammonia Production Technologies:
Some Commercial Processes���������������������������������� 225

Chapter 14 Business Strategy Models Applied to the Downstream

Industry��������������������������������������������������������������������������������������������� 229
14.1. Porter’s Competitive Forces in the Downstream
Industry���������������������������������������������������������������������������������� 230
14.2. Changing the Focus: More Petrochemicals and
Less Fuel�������������������������������������������������������������������������������� 236
14.2.1. Petrochemical and Refining Integration
as a Differentiation Strategy������������������������������������ 237

Chapter 15 Corrosion Management in Refining Assets�������������������������������������� 241

15.1. Naphthenic Corrosion: General Overview���������������������������� 241
15.2. Corrosion in Sour Water Stripping Units������������������������������� 243
15.3. Corrosion Process in Amine Treating Units�������������������������� 246
15.4. Corrosion Processes in FCC Units���������������������������������������� 248
15.4.1. The Petrochemical FCC: Raising Competitive
Advantage x Corrosion Attention���������������������������� 250
15.5. Corrosion Management in Hydroprocessing Units��������������� 251

Chapter 16 Energy Management and the Sustainability of the

Downstream Industry����������������������������������������������������������������������� 257
16.1. Introduction and Context������������������������������������������������������� 257
16.2. Simple and Available Alternatives to Energy
Optimization�������������������������������������������������������������������������� 258
16.3. The Impact of the Energy Management on the
Greenhouse Gas Emissions��������������������������������������������������� 262

Index���������������������������������������������������������������������������������������������������������������������� 265
Preface
Despite new and cleaner energy sources, crude oil is still fundamental to sustaining
the economic development of nations and the technological development of society.
In recent decades, we have observed an increasing pressure on the crude oil industry
to reduce the environmental impact of their processes and derivatives as a fundamen-
tal part of global efforts to reach a more efficient, cleaner, and sustainable society.
In this book, we deal with the processes applied to ensure higher added value to
crude oil and the refining processes that are currently known as the downstream indus-
try. The current scenario imposes great challenges to the players of the ­downstream
industry, both due to the growing pressure to reduce the environmental footprint of
their derivatives and the reduction in the demand for fossil transportation fuels.
Some trends and technologies, such as the electrification of automobile fleet and
additive manufacturing, have the potential to destroy demand for crude oil deriva-
tives, and this technological development requires high-quality derivatives, such as
the base oils applied to produce lubricants, and these facts put refiners under pres-
sure and squeeze the refining margins, leading players to look for new routes and
processes to ensure high added value to processed crude oil. The objective of this
book is to review classic crude oil refining processes and present an overview of the
current scenario of the downstream industry and how the players can survive in this
transitive period of the crude oil refining sector.

ix
Acknowledgments
It’s impossible to achieve any good result alone, and this book is no different. In
this sense, I would like to start by giving my thanks to God! Without the support
I  received from my family, especially my wife, Ana Glaucia, and my daughter,
Manuela, this book simply would not exist. I’m also grateful to the professionals
with whom I had opportunities to exchange experiences and knowledge, especially
Mr. Suleyman Ozmen, a real friend and an outstanding professional, as well as
Mr. Romain Roux of Axens.
In my developing journey, I had the opportunity to learn at the State University of
Maringa (UEM) and the State University of Campinas (UNICAMP), so I would like
to express my thanks to all the good professors of the chemical engineering courses
of both universities. The construction of this book relied on the contribution of some
of the main technology developers to the crude oil refining industry, among them
Chevron Lummus Global, Honeywell UOP, Axens, and Haldor Topsoe, as well as
some of the most relevant trend/consultancy companies, such as IHS Markit, Wood
Mackenzie, International Energy Agency (IEA), and the Catalyst Group companies.
For all these companies, I offer my thanks.

xi
Author
Marcio Wagner da Silva, PhD, is a process engineer and stockpiling manager in
the crude oil refining industry based in São José dos Campos, Brazil. He earned a
bachelor’s in chemical engineering at the University of Maringa (UEM), Brazil, and
a PhD in chemical engineering at the University of Campinas (UNICAMP), Brazil.
Dr. da Silva has extensive experience in research, design, and construction in the
oil and gas industry, including developing and coordinating projects for operational
improvements and debottlenecking to bottom barrel units. Moreover, he earned an
MBA in project management at the Federal University of Rio de Janeiro (UFRJ) in
digital transformation at PUC/RS, and he is certified in business from the Getulio
Vargas Foundation (FGV).
Recently Dr. da Silva has dedicated his efforts to learning and sharing knowledge
about the crude oil refining industry and taking part as an industry adviser to the
International Association of Certified Practicing Engineers (IACPE), a member of
the advisory board of The Catalyst Review Magazine from the Catalyst Group, and
a member of the advisory board of the Global Energy Transition Forum, which is
strictly committed to minimizing the environmental impact of the energy industry in
a realistic and sustainable manner.

xiii
 1 Crude Oil

1.1 INTRODUCTION
Crude oil is a complex mixture of hydrocarbons, which occur naturally in the earth.
Crude oil can be separated into fractions through distillation to achieve the most
useful derivatives for society, like fuel and petrochemicals.
Choosing an adequate crude oil slate is among the most relevant decisions of
refiners. Refining assets are designed considering a narrow range of characteristics of
crude oil to be processed. However, over the useful life of the assets, crude oil slates
to be processed can undergo great changes either due to a shortage of crude oil with
certain characteristics or by supply difficulties linked to geopolitical issues.
The characterization and classification of different types of crude oil aim to estab­
lish its value primarily in relation to reference crudes like Brent and WTI (West
Texas Intermediate), as well as define the technological and refining routes to ade­
quate processing. Crude oil consists basically of a mixture of hydrocarbons and asso­
ciated impurities. These impurities normally refer to sulfur, nitrogen, oxygen, and
metals. The concentration of these impurities significantly raises the technological
challenges of crude oil processing, leading to a reduction in the crude oil prices
according to the concentration of the impurities. The determination of the crude slate
to be processed in a refinery is based on a blending of crude oil, aiming to achieve an
adequate composition of hydrocarbons and contaminants that allow the processing
in a reliable and profitable manner. Figure 1.1 presents the main variables considered
in the choice of crude oil slate to be processed in a refining asset.
Some scenarios, such as the discovery of abundant reserves of crude oil with
characteristics different from those suitable for a given refining asset, can support the
decision of capital investments aiming to adapt the refining assets to the processing
of a certain type of crude oil. This fact is common when a refiner is an importer and
oil reserves are discovered in the local market.
In relation to hydrocarbons, crude oil contains paraffinic, naphthenic, and aro­
matic molecules that confer the chemical and physical characteristics of crude oil.
Crude oil can be classified according to the physical and chemical characteris­
tics of the hydrocarbons found in the geological reservoir, one of the most common
classifications is the API grade, which is based on the specific gravity of crude oil as
described in Equation 1.1.

141, 5
API = - 131, 5 (1.1)
p

Where ρ = specific gravity of crude oil

Table 1.1 presents an example of crude oil classification based on API. It’s import­
ant to note that the API grade is a basic classification parameter of crude oil.

DOI: 10.1201/9781003291824-1 1
2 Crude Oil Refining

FIGURE 1.1  Schematic Representation of the “Blending Space” of Crude Oil

TABLE 1.1
Crude Oil Classification Based on API Grade
Classification API Grade
Light crude API > 31,1
Medium crude 22, 3 > API < 31,1
Heavy crude 10,0 > API < 22,3
Extra-heavy crude API < 10,0

Source: Adapted from Guidelines for Application of the Petroleum Resources Management System, 2011

A very relevant characteristic of oils for refining hardware is naphthenic acidity.

Naphthenic acidity is determined based on the amount of KOH required to neutralize
1 gram of crude oil. Normally, a mixture of crude oil is sought in the refinery load
so that it does not exceed 0.5 mg KOH/g. Above this reference, the bottom sections
of the distillation units can undergo a severe corrosive process, leading to shorter
periods of the operational campaign and higher operating costs in addition to prob-
lems associated with integrity and safety. Naphthenic acidity is directly linked to the
concentration of oxygenated compounds in crude oil that tend to be concentrated in
heavier fractions, giving instability and odor to the intermediate currents.
Crude Oil 3

Another relevant characteristic of crude oil is the salt (NaCl) content. The pres-
ence of salt in the oil leads to serious corrosion problems, mainly in atmospheric
distillation units. The salt content after desalting in atmospheric distillation units is
controlled to be below 3 ppm.
Sulfur content is also one of the variables used in the characterization of crude
oil in view of their impact on the emissions of harmful gases when using derivatives
as fuels. In addition, sulfur compounds increase the polarity of raw oils, leading to
stabilization of emulsions and greater difficulties in the desalting process. Normally,
oils are classified as high in sulfur when they have levels above 0,5% by weight and
low in sulfur below this reference. High-sulfur oils require greater hydrotreating
capacity to meet the current environmental requirements for the commercialization
of oil products. The presence of contaminants like sulfur, nitrogen, and oxygen is
another relevant parameter to classify crude oil and has a great impact on defining
the required processes needed to produce the required crude oil derivatives. Nor-
mally, the lighter crudes present higher yields of added-value streams like naphtha
and diesel and less contaminant content, which lead these crudes to achieve higher
prices in the international market. Nowadays, crude oil with low sulfur content tends
to be more valuated in the market, especially due to the regulation IMO 2020 (the
International Maritime Organization’s rule on limiting sulfur emissions).
This regulation established that after 2020, the maximum sulfur content in the
maritime transport fuel oil (bunker) is 0,5% (m.m) against the past 3,5% (m.m). The
main objective is to reduce the SOx emissions from maritime fleets, significantly
decreasing the environmental impact of this business.
Maritime fuel oil, known as bunker, is a relatively low-viscosity fuel oil applied in die-
sel cycle engines to a ship’s movement. Before 2020, the bunker was produced through
the blending of residual streams as vacuum residue and deasphalted oil with dilutants
like heavy gas oil and light cycle oil (LCO). Due to the new regulation, a major part of
the refiners will not be capable of producing low-sulfur bunker through a simple blend.
Due be produced from residual streams with high molecular weight, there is a
tendency for contaminants accumulation (sulfur, nitrogen, and metals) in the bunker.
This fact makes it difficult to meet the new regulation without additional treatment
steps, which should lead to an increased production cost of this derivative and the
necessity for modifications in the refining schemes of some refineries.
The first alternative to meet the IMO 2020 is the control of the sulfur content in
crude oil that will be processed in the refinery. However, this solution limits the refin-
ery’s operational flexibility and restricts crude slate suppliers, which can be a threat
in scenarios with geopolitical instabilities and crude oil price volatility.
According to related by Fitzgibbon et al. (2017), just only a small part of crude oil
is capable of producing an atmospheric residue that meets the new requirement of the
bunker sulfur content.
Due to the limitation in the supply of low-sulfur crudes, the use of residue upgrad-
ing technologies aiming to adequate the contaminants contained in the streams
applied in the production of the bunker is an effective strategy.
Despite the challenges imposed by IMO 2020, some refiners and crude oil pro-
ducers are positively exposed to the new regulation, like the Brazilian crudes from
pre-salt reserves, Russian Ural reserves, and Britannic North Sea reserves.
4 Crude Oil Refining

The Brazilian pre-salt reserves offer low-sulfur crude oil, with sulfur content
varying from 0,3% to 0,67% (in mass). These characteristics of the Brazilian crudes
represent a great competitive advantage not only to the downstream sector, but it’s
important to consider the valuation of these crudes in the market considering the
restrictions imposed by IMO 2020. Nowadays, the pre-salt reserves represent the
main crude oil source for Brazilian refineries, and the Brazilian downstream sector
can produce bunker in compliance with the IMO 2020 since 2019.
Nitrogen content is also a relevant characteristic of crude oil to be considered
when choosing castings for processing at refineries. Nitrogen compounds tend to sta-
bilize emulsions, leading to greater difficulties in desalting oil. In addition, they are
responsible for imparting chemical instability to derivatives, leading to the forma-
tion of polymers and color changes, especially in aviation kerosene. Excess nitrogen
compounds can also lead to the deactivation of the acid function of catalysts in deep
conversion processes, such as FCC.
The metal content in crude oil is a relevant variable since, like other contami-
nants, it tends to be concentrated in heavier fractions of oil. These fractions tend to
be processed in deep conversion units, such as hydrocracking and catalytic cracking,
and they tend to plug the pores of the catalysts, leading to the rapid deactivation of
these catalysts, significantly increasing operating costs, and requiring the installation
of guard beds to protect the active catalysts.
As previously mentioned, crude oil considered light tends to be more valued in
the market, especially in the current market scenario in which there is a tendency to
increase the demand for petrochemical intermediaries to the detriment of transpor-
tation fuels.
The adequate characterization of crude oil allows for establishing the main chal-
lenges for its processing and the mixture of crude oil necessary to reach an ade-
quate cast for each refining hardware, in terms of either profitability or the maximum
contaminant levels allowed for reliable processing, and that ensures the integrity of
operational assets.

1.2  PRIMARY TREATING PROCESSES OF CRUDE OIL

The reliability of the processing units is fundamental to allow refiners to achieve the
desired reliability and keep the competitiveness and the consumer market supply.
The operational continuity of a refinery relies on some factors and a strong manage-
ment system. However, the quality of the raw material (crude oil) is one of the main
factors in ensuring the reliability and integrity of the refining processes. Normally,
crude oil that will be processed in the refineries must meet some quality require-
ments aiming to preserve the separation and conversion processing units, mainly the
atmospheric distillation unit. The maximum water and sediment content in crude oil
is controlled so that it will be lower than 1% in volume. Other relevant parameters are
diluted salt content and the total acid number (TAN), which is defined as the quantity
of KOH (potassium hydroxide) needed to neutralize 1 gram of crude oil.
To achieve these requirements, crude oil undergoes a series of treatments. This
“primary treatment” aims to ensure the life cycle of the downstream and midstream
assets. These processes are generally focused on separating water, gas, and oil phases
Crude Oil 5

FIGURE 1.2  Steps of the Primary Treatment of Crude Oil

still in the upstream assets. Figure 1.2 shows the basic steps of the primary treatment
of crude oil through a block diagram.
Crude oil is drawn from the reservoir, and the separation of gas and liquid phases
is carried out through pressure reduction. In the next step, the liquid phase is pumped
into a separator drum to promote the separation of oil and water phases by decanta-
tion. In this step, only the free water is separated from the oil. A part of the water is
emulsified. Subsequently, the mixture undergoes a new treatment step by applying
an electrical field and demulsifier addition beyond the heating that aims to reduce the
viscosity and allow better phase separation.
The water-oil phase separation is carried out in decantation vessels, which can
be two-phase, when it is realized just by the separation of gas and liquid (water +
oil) phases, or three-phase, when it involves the separation of free water from oil
additionally. Due to the high superficial area, the separation vessels have a normally
horizontal configuration. However, in upstream units with great production flow rate
oscillations and large sediment content, the vertical configuration is adopted.
In the oil-water-separation step, the emulsion is broken through the application of
a high-intensity electrical field that promotes the water droplet polarization and, con-
sequently, decantation. Unlike what occurs in the refineries during the crude desalt-
ing process, the electrical treaters used in the upstream assets are low-speed. In this
case, the emulsion is fed in the bottom and distributed under a laminar regime to the
internals of the separation vessel.
After the separation step, the water is directed to a treatment system. A simplified
configuration of a typical water treatment unit is presented in Figure 1.3.
The brine coming from electrostatic treaters is pumped to degassing vessel to
remove dissolved gases. After this step, the oily residue is directed to the tank where
the phase separation occurs. The aqueous phase is sent to a new treating cycle
6 Crude Oil Refining

FIGURE 1.3  Oily Water Treatment Process

while the oily phase is pumped to storage. The oily water is directed to a water-
oil-­separation treatment step, which normally applies API separators. However, in
modern sites, hydrocyclones are used due to their higher efficiency. After a flotation
step, the treated water can be directed to be disposed of or to be reinjected into the
reservoir to improve the recovery of crude oil.
Natural gas produced is directed to treatment steps aiming to reduce the humidity
content and sour gases removing. The dehydrating process is carried out through the
absorption process with TEG (triethylene glycol), while the sour gases (H2S + CO2)
are removed through amine treatment.
The produced gas stream still undergoes treatment steps aiming to remove heavier
compounds (C3 to C5+) that are considered condensable in natural gas. This process
consists basically of the controlled refrigeration of the gas to condense the heavier
fractions. The processes generally employed are the Joule-Thomson expansion, sim-
ple refrigeration, and turbo expansion. The obtained stream has a great added value
and can be applied as a petrochemical feed stream due to its high paraffin content or,
according to the consumer market, be directed to the refineries to improve the yield
of LPG and gasoline.
As aforementioned, an adequate treatment of crude oil is fundamental to ensure
the reliability and availability of the downstream industry. High salt and water con-
tent in the crudes leads to higher corrosion and deposition rates in the processing
units, reducing the life cycle and increasing operational costs due to unplanned shut-
downs. Other assets that experience strong degradation due to the failures in the
primary treatment steps are the storage tanks and pipelines. In this sense, the inte-
gration between upstream and downstream systems is a key factor in ensuring the
sustainability of the crude oil production chain.
When some of the controlled parameters are out of specification, it is necessary to
blend different crudes to keep the feed stream to the crude oil distillation unit under
controlled conditions. This fact raises the operational costs related to unnecessary
operational handling that could be avoided.
Adequate asset management is an important step in the current transformation of
the downstream industry. The management system needs to be based on two driving
Crude Oil 7

engines: the first is focused on keeping the current operations once they sustain the
planned future, and the second is focused on innovative actions to ensure the peren-
niality of the business. This is an important consideration related to what is called
digital transformation. This phenomenon is not only related to technology. Techno-
logical advancements make easy access to data possible, but we need a modern and
strong management system able to ensure that the right questions will be done to
transform these data into information, knowledge, and finally, wisdom.

1.3  CRUDE OIL DERIVATIVES

Crude oil processing produces a series of derivatives with distinct demands and
added values. Figure  1.4 presents a simplified process flow diagram for a typical
atmospheric crude oil distillation unit and the main derivatives produced in this unit.
The stream considered as fuel gas is normally composed of hydrocarbons in the
range C1 to C2 and is applied as fuel in the fired heaters and boilers in the own
refinery.
The main quality parameters controlled in the fuel gas are the humidity and
hydrogen sulfide (H2S) content. These requirements are normally controlled in
dehydration units using propylene glycol and amine treating units, respectively. The
­concentration of H2S is controlled to be below 1% in volume and humidity content.
LPG is normally composed of paraffinic and olefinic hydrocarbons in the range
of C3 to C4 and is applied as domestic and transportation fuel in specific cases. The
LPG can contain low quantities of light and heavy hydrocarbons (C2 and C5). How-
ever, the concentration of these compounds needs to be minimized, aiming not to
lose the quality requirements. The concentration of light hydrocarbons is controlled
through the Reid vapor pressure (RVP), which is determined by the LPG heating at
37,8°C. The light content is controlled for security reasons, aiming to keep the LPG
volatility under safe values to allow storage and handling. The RVP of commercial
LPG is controlled to be below 1430 kPa. Once LPG is normally burned into closed
environments, the control of burning residue is one of the most important quality
requirements of this derivative. The heavy content is controlled through weathering
test that evaluates the difficulty in vaporization of LPG. Measuring in an indirect
way, the content of C5+ in the mixture is normally defined by the boiling temperature
of 95% in volume of the mixture under atmospheric pressure and is normally con-
trolled to be below 2°C.
The naphtha streams are normally directed to the refinery gasoline pool accord-
ing to the refining configuration and the demand of the market where the refiner is
inserted. The streams that compose the gasoline pool also depend on the refining
scheme. However, it’s common for the composition of gasoline pool with straight-run
naphtha, cracked naphtha from FCC units, reformed naphtha from catalytic reform-
ing units, isomerized naphtha from isomerization units, and alkylated naphtha pro-
duced in catalytic alkylation units.
The gasoline is composed by the blending of these streams containing hydro-
carbons with a boiling range of 30–215°C (C4 to C10). Among the main quality
requirements of the gasoline are the antiknock capacity, volatility, corrosivity,
­
­pollutants emissions, and the tendency of combustion residue formation in the
 8
Crude Oil Refining

FIGURE 1.4  Typical Process Arrangement of an Atmospheric Crude Oil Distillation Unit
Crude Oil 9

engines. The gasoline antiknock capacity is measured through the octane number
that is determined by applying isooctane (2,2,4-trimethyl pentane) as standard with
octane number 100 and the n-heptane with octane number 0. The octane number
represents a volumetric percentage of isooctane in a mixture with n-heptane, which
burns with the same antiknock quality of the analyzed gasoline (measured through
sound intensity), the tests to determine the octane number can be the MON (motor
octane number) test and the RON (research octane number) test. Common automo-
tive gasoline has an octane number close to 85. The naphtha streams that add higher
antiknock capacity to the gasoline are the cracked naphtha from FCC units due to
the high olefin content, the reformed naphtha due to the high aromatic concentra-
tion, and the naphtha from catalytic alkylation due to the ramified characteristics of
the produced kinds of paraffin. However, the aromatic and olefin contents are nor-
mally controlled in the final gasoline due to the toxicity and high volatility of these
compounds.
The volatility of gasoline is related to the light content in the mixture being
directly responsible for the cold starting facility of the internal combustion engines.
Gasoline Reid vapor pressure (PVR) indirectly measures the amount of light present
in the blend, and for LPG, the gasoline PVR is determined at 37,8°C (100°F) at 1 atm
and is usually controlled to be below 55 kPa.
The corrosivity and emissions of the gasoline are controlled through the sulfur
content in the final product. Currently, the sulfur content in the gasoline is controlled
to be below 50 ppm. For this reason, it’s practically impossible to meet this specifi-
cation without hydrotreating units. Selective hydrotreating units are applied mainly
to treat cracked naphtha aiming to reduce the sulfur content with minimum loss of
antiknock capacity (due to olefin saturation). The resistance of deposit formation is
directly related to the olefin content in the mixture. These compounds are chemically
unstable and undergo polymerization, forming polymers that produce deposits and
inefficient combustion. The use of antioxidant additives and detergents in the final
gasoline can minimize these effects.
A special case of commercialized gasoline is the aviation gasoline that is applied
to airplanes equipped with Otto cycle engines. In this case, the hydrocarbons that
compose the gasoline have a stricter boiling range (30–170°C) containing ramified
paraffin produced by catalytic alkylation processing units.
According to the market to be supplied and the interaction level of petrochemical
and refining operations, the light straight-run naphtha can be commercialized as pet-
rochemical naphtha. In this case, it’s necessary to guarantee a paraffin content higher
than 65%. This alternative tends to be even more applied face with the tendency for a
reduction of transportation fuel demand. Furthermore, in markets with high demand
by middle distillates, the heavy straight-run naphtha can be directed to compose the
diesel or jet fuel pool.
In its turn, jet fuel is a mixture of hydrocarbons between C5 and C15 with a boil-
ing range of 150–300°C; it is applied as fuel to jet turbines, normally applied in
aviation. Due to the severity of use conditions, jet fuel has quality requirements quite
restricted. The combustion needs to be the cleaner possible to avoid depositions.
For this reason, the polyaromatic content is controlled. This is achieved through the
smoke point test.
10 Crude Oil Refining

The characteristics of flow under low temperatures are fundamental to jet fuel due
to the operational conditions that can achieve temperatures of −50°C. The maximum
freezing point for commercial jet fuel is −47°C. For this reason, it’s fundamental
to ensure an adequate cut point in the distillation step to avoid the drag of heavy
paraffin to the intermediate kerosene. The thermal stability is measured through the
JFTOT (jet fuel thermal oxidation test), which simulates the operational conditions
that the fuel is submitted to.
The corrosivity and chemical stability in relation to the materials applied to the
construction of turbines are controlled through the content of total sulfur, mercaptan
sulfur, and H2S. Normally, jet fuel is submitted to a caustic treating step to control
these compounds. In modern refining units, this step is carried out in hydrotreat-
ing units. The flash point (minimum 40°C) and the electric conductivity are other
requirements directly related to the security in the derivative handling.
Diesel is a crude oil derivative that had the most increased demand in the last
decades. This derivative is mainly used as a transportation fuel by vehicles equipped
with diesel cycle engines and is composed of hydrocarbons between C10 and C25 with
a boiling range of 150–380°C. The diesel ignition quality is measured through the
cetane number that corresponds to a volumetric percentage of cetane (­n-­hexadecane)
in a mixture with heptamethylnonane, which burns with the same ignition quality as
the analyzed diesel. The linear paraffinic hydrocarbons are the compounds that most
contribute to the diesel ignition quality, raising the cetane number while the presence
of aromatics reduces this parameter and harms the ignition quality. Currently, the
minimum cetane number of commercial diesel is 48. In some countries, like Brazil,
the addition of biodiesel in the final product is mandatory, with a minimum concen-
tration of 10% in volume.
The diesel volatility is controlled, aiming to ensure the cold start performance
and safety during the handling. The minimum flash point of 38°C and the tempera-
tures of distillation curve correspondent to 50%, 85%, and 95% recovered in volume
are controlled in determined limits to ensure the total vaporization in the working
conditions. These parameters limit the quantity of naphtha added to the diesel pool.
Another important parameter controlled in the diesel is the plugging point that
aims to control the content of linear paraffin that tends to crystallize under low
temperatures harm the fuel supply to the engine. The plugging point is determined
according to the weather conditions in the region of application. In Brazil, the plug-
ging point is controlled in the range of 0–10°C.
The diesel emissions control is carried out by managing the fuel density aim-
ing to control the content of heavy compounds, especially polyaromatics. Currently,
the density of commercial diesel is controlled in the range of 830–865 kg/m3 to
­ultra-low-sulfur diesel (ULSD). This parameter is controlled to be below 850 kg/m3.
In the last decades, there have been great efforts to reduce the environmental damage
produced by diesel burn. Nowadays, environmental regulations require the commer-
cialization of low-sulfur diesel with a maximum sulfur content of 10 ppm. However,
in some markets, mainly in developing countries, there is still commercialized diesel
with higher sulfur content (500 ppm), but this will change soon. This requirement led
to the necessity of refiners to expand their hydrotreating capacity.
Crude Oil 11

The viscosity is also a controlled parameter in the diesel, aiming to ensure an

adequate nebulization in the combustion chamber. High viscosities can be bad due
to the poor dispersion of the fuel, while low viscosities lead to excessive disper-
sion. Normally, the diesel viscosity is controlled in a range of 2–5 mm2/s. The diesel
lubricity is measured to control the wear due to the friction of the pieces in contact
with diesel and is determined by specific tests. The lubricity and the electric conduc-
tivity are directly related to the concentration of polar compounds that are reduced
after the hydrotreating step. For ULSD, additives are normally used to correct these
parameters.
The control of water content and sulfur, nitrogen, and aromatic compounds aims
to avoid the proliferation of microorganisms that lead to the filters plugging and add
corrosivity to the derivative, as well as raise the stability of oxidation and deposit
formation.
Adequate management of crude oil derivative quality requirements is fundamen-
tal to achieving the desired goals of performance, safety, and environmental impact.
Ensuring the efficiency and reliability of the process responsible for controlling
these parameters is a key factor in achieving competitiveness and sustainability in
the refining industry.
The fuel oil formulation is carried out by adding diluents to vacuum residue, aim-
ing to achieve a specified viscosity according to the application. Commonly, diluents
applied are the gas oil streams from vacuum distillation or streams from deep con-
version units like FCC (light cycle oil) or delayed coking (light and heavy gas oils).
In some cases, diesel is applied as diluent. The main quality parameters controlled
in the fuel oil production are sulfur content, viscosity, the content of sediments and
water, vanadium concentration, flash point, and pour point.
The fuel oil is considered a low-sulfur fuel when the maximum concentration of
this contaminant is 1% is mass and high-sulfur fuel when the maximum sulfur con-
centration is 2,5%. The sulfur content control aims to impose a limit on the emissions
of harmful gases during the derivative burning. The viscosity control in the fuel oil
aims to minimize the transfer costs and ensure adequate flow and vaporization in
the burners. The kinematic viscosity of industrial fuel oils (measured at 60°C) is
controlled in the range of 600–950 mm2/s.
The limit of water and sediment content aims to minimize the fouling, deposition,
and corrosion in the process equipment and damage to the burners. Furthermore, the
water presence reduces the calorific value once part of the released energy is applied
to vaporize the water and can provoke flame instability. The maximum vanadium
content control aims to minimize the effects of the chemical attack of this metal
on the refractory of boilers and fired heaters, as well as metallurgic damages. The
maximum vanadium content in the fuel oil is 200 ppm. In its turn, the flash point is
applied to control the fugitive emissions and add security during the derivative han-
dling, while the pour point aims to ensure the flow under low temperatures. The pour
point specification relies on the weather conditions in the application region.
In some cases, it’s necessary to mix different fuel oils to meet the quality require-
ments. In these cases, it’s important to consider the compatibility between the
fuel oils. Oils from highly paraffinic crudes show chemical incompatibility with
12 Crude Oil Refining

oils produced from crude oil with high asphaltene content, once the presence of
­paraffin precipitates the asphaltenes due to the resin solubilization that stabilizes the
asphaltenes in the solution.
Asphalt is considered a residual fraction of crude oil, normally composed of mol-
ecules predominantly aromatic. Asphalt is produced from the vacuum residue that is
obtained in the bottom of the vacuum tower, as stated earlier, or from the dilution of
the asphaltic residue obtained from the solvent deasphalting process.
The main application of asphalt is the composition of road pavements. Among the
asphalt quality requirements are consistency, hardness, ductility, thermoplasticity,
viscoelasticity, thermal susceptibility, and durability.
The determination of consistency and hardness of the asphalt aims to define the
handling capacity of the derivative. This variable is evaluated by the penetration test,
which is performed using a standard needle under specific conditions of loading,
temperature, and time. The ductility measures the ability of the asphalt to elongate
before rupture. This requirement is directly linked to the strength of the material
when applied to the pavement composition.
The thermoplasticity and the viscoelasticity are controlled, aiming at the pos-
sibility of hot application of the asphalt and the restoration of the properties of the
material after cooling. Thermal susceptibility gives the asphalt the ability to with-
stand temperature variations without the loss of properties such as consistency and
ductility. In turn, the durability test is performed under an aggressive atmosphere
of exposure to air and heat, and the other properties are subsequently re-evaluated.
The asphalt flash point is controlled to be below 235°C to allow safe handling of the
derivative.
The marine fuel oils, called bunkers, are produced from the bottom residue of
vacuum distillation. These derivatives are applied as fuels to large ships that operate
with diesel cycle engines. Thus, despite also being produced from vacuum residue,
the bunker oils have quality requirements different and more severe than the indus-
trial fuel oils.
Due to the bunker’s use in diesel engines, it is necessary to control the ignition
quality of the bunker. This requirement is evaluated indirectly through the CCAI
(calculated carbon aromaticity index), which is evaluated from the density and vis-
cosity parameters that are controlled.
Viscosity is an extremely important variable for the bunker since it is directly
related to the ease of nebulization of the derivative in the combustion chamber.
High-viscosity oils require a higher heating rate before firing. The bunker viscosity
is generally controlled between 2 and 11 mm2/s (measured at 40°C). Another import-
ant feature is the pour point of the bunker. This variable depends on the climatic
conditions in the region of application since it is related to the capacity to flow at
reduced temperatures, and the bunker pour point is normally controlled between
−6°C and 6°C.
The density of the commercial bunker is controlled between 877 and 897 kg/m3,
while the minimum flash point is 60°C to limit fugitive emissions and give safety
to the handling of the product. The maximum water and sediment content for the
commercialization of the bunker is 0,4% by volume to avoid corrosion and waste
deposition in equipment and storage tanks.
Crude Oil 13

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Hydrogen Production
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Caustic Treating Processes

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A New Downstream Industry

The Catalyst Group . Advances in Catalysis for Plastic Conversion to Hydrocarbons, The
Catalyst Group (TCGR), 2021.
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Honeywell UOP Company, Presented in 12th Asian Downstream Summit, 2019.
Cui, K. Why Crude to Chemicals is the Obvious Way Forward, Wood Mackenzie, 2019.
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Frecon, J. , Le Bars, D. , Rault, J. Flexible Upgrading of Heavy Feedstocks, PTQ Magazine,
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Lambert, N. , Ogasawara, I. , Abba, I. , Redhwi, H. , Santner, C. HS-FCC for Propylene:
Concept to Commercial Operation, PTQ Magazine, 2014.
Maller, A. , Gbordzoe, E. High Severity Fluidized Catalytic Cracking (HS-FCC™): From Concept
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Murphy, J.J. , Payn, C.F. Oil to Chemicals: New Approaches, PTQ Magazine, 2019.
Refinery-Petrochemical Integration (Downstream SME Knowledge Share), Wood Mackenzie
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Reinventing the Refinery through the Energy Transition and Refining-Petrochemical Integration,
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Silva, M.W. More Petrochemicals with Less Capital Spending, PTQ Magazine, 2020.
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Operation, and Optimization. 1st edition, Wiley Press, 2017.
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Silva, M.W. , Clark, J. Delayed Coking as a Sustainable Refinery Solution, PTQ Magazine,
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The Propylene Production Gap

Gary, J.H. , Handwerk, G.E. Petroleum Refining: Technology and Economics. 4th edition,
Marcel Dekker, 2001.
Marsh, M. , Wery, J. On-Purpose Propylene Production, PTQ Magazine, 2019.
Mukherjee, M. , Vadhri, V. , Revellon, L. Step-Out Propane Dehydrogenation Technology for the
21st Century, The Catalyst Review, 2021.
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Gas-to-Liquid Processing Routes

Gary, J.H. , Handwerk, G.E. Petroleum Refining: Technology and Economics. 4th edition,
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IEA (International Energy Agency) . Primary Chemical Production in the Sustainable
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Silva, M.W. An Alternative to Crude Oil, Hydrocarbon Engineering Magazine, 2020.

Business Strategy Models Applied to the Downstream Industry

The Catalyst Group . Advances in Catalysis for Plastic Conversion to Hydrocarbons, The
Catalyst Group (TCGR), 2021.
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Cui, K. Why Crude to Chemicals Is the Obvious Way Forward, Wood Mackenzie, 2019.
Frecon, J. , Le Bars, D. , Rault, J. Flexible Upgrading of Heavy Feedstocks, PTQ Magazine,
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Silva, M.W. More Petrochemicals with Less Capital Spending, PTQ Magazine, 2020.
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Corrosion Management in Refining Assets

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API 571/2011 . Damage Mechanisms Affecting Fixed Equipment in the Refining Industry,
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Harston, J.D. , Ropital, F. Corrosion in Refineries. 1st edition, CRC Press, 2007.
Speight, J.G. Oil and Gas Corrosion Prevention—From Surface Facilities to Refineries. 1st
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Energy Management and the Sustainability of the Downstream Industry

Karatas, Z. , Turkoglu, S. A Refinery’s Journey to Energy Efficiency, PTQ Magazine 2016.
Rikhtegar, F. , Sadighi, S. Optimization of Energy Consumption, PTQ Magazine 2015.
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