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Processing of
Heavy Crude Oils

Challenges and Opportunities
Edited by Ramasamy Marappa Gounder

Processing of Heavy Crude
Oils - Challenges and
Opportunities
Published in London, United Kingdom

Supporting open minds since 2005
Processing of Heavy Crude Oils - Challenges and Opportunities
http://dx.doi.org/10.5772/intechopen.74912
Contributors
Samuel Sojinu, Onome Ejeromedoghene, Abdelaziz Nasr El-Hoshoudy, Saad M. Desouky, Emad Soliman,
Sayeed Rushd, Rasel A Sultan, Shahriar Mahmud, Tarek Ganat, Cs Khor, Hazlina Husin, Mysara
Mohyaldinn, Pradip Mandal, Nurul Aini Amran, Shafirah Samsuri, Mohd Afnan Ahmad, Feyisayo Victoria
Adams, Chikaodili Chukwuneke, Bolade Agboola, Mahshad Pazouki, Faith Uchenna Uchenna Babalola,
Alfred Susu, Ching Thian Tye, Ramasamy Marappa Gounder
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Meet the editor
Dr. M. Ramasamy is currently an Associate Professor in the

Chemical Engineering Department, Universiti Teknologi
PETRONAS (UTP). He has been in teaching and research for
more than 30 years. He is specialized in process simulation,
optimization and control. His current research interests include
advanced process control, heat exchanger fouling, thermal
management of crude oil pipelines and energy management in
oil and gas industries. He has supervised 7 PhD and 5 M.Sc. students. He has also
published several research articles in reputed international journals, book chapters
and a book. He has also delivered several invited lectures and short courses. He ob-
tained his B.Tech. degree in Chemical Engineering from Madras University, India;
his M.Tech. from the Indian Institute of Technology, Kharagpur and his PhD from
the Indian Institute of Technology, Madras. He is a Chartered Engineer (Engineer-
ing Council, UK), Senior Professional Engineer (Engineering Council, India) and a
Certified Energy Manager (GreenTech, Malaysia).
Contents
Preface XIII
Chapter 1 1
Introductory Chapter: Heavy Crude Oil Processing - An Overview
by Ramasamy Marappa Gounder
Chapter 2 7
Methods for Enhancing Recovery of Heavy Crude Oil
by Mohd Afnan Ahmad, Shafirah Samsuri and Nurul Aini Amran
Chapter 3 23
PVT Properties of Black Crude Oil
by Abdelaziz El-Hoshoudy and Saad Desouky
Chapter 4 47
Pumping System of Heavy Oil Production
by Tarek Ganat
Chapter 5 73
Modeling Friction Losses in the Water-Assisted Pipeline Transportation of
Heavy Oil
by Sayeed Rushd, Rasel A. Sultan and Shahriar Mahmud
Chapter 6 95
Ablation of Oil-Sand Lumps in Hydrotransport Pipelines
by Mahshad Pazouki and Sayeed Rushd
Chapter 7 115
Evaluation of Asphaltenes Deposition Inhibition Factors in Heavy Crude
Oil Pipelines
by Hazlina Husin, Mysara Eissa Mohyaldinn Elhaj and Colin D. Wood
Chapter 8 125
Flow of Heavy Oils at Low Temperatures: Potential Challenges and Solutions
by Emad Soliman
Chapter 9 153
Challenges during Operation and Shutdown of Waxy Crude Pipelines
by Mysara Eissa Mohyaldinn, Hazlina Husin, Nurul Hasan,
Mohamed M.B. Elmubarak, Ahmed M.E. Genefid and Mahmood E.A. Dheeb
Chapter 10 167
Pre-Treatment of Heavy Crude Oils for Refining
by Faith Uchenna Babalola and Alfred Akpoveta Susu
Chapter 11 185
Recent Techniques for the Removal of Naphthenic Acid from Heavy
Crude Oils
by Feyisayo Victoria Adams, Chikaodili E. Chukwuneke and Bolade O. Agboola
Chapter 12 197
Nickel Tetraphenylporphine Extraction from Model Heavy Oil Using
Ionic Liquids
by Pradip Chandra Mandal
Chapter 13 211
Catalysts for Hydroprocessing of Heavy Oils and Petroleum Residues
by Ching Thian Tye
Chapter 14 229
A Model-Based Investment Assessment for Heavy Oil Processing in the
Petroleum Refining Industry
by Cheng Seong Khor
Chapter 15 241
Environmental Challenges Associated with Processing of Heavy Crude Oils
by Samuel O. Sojinu and Onome Ejeromedoghene
XII
Preface
I am delighted to present this book titled Processing of Heavy Crude Oils - Challenges
and Opportunities in an attempt to present the current status and technologies in
this field.
It is envisaged that heavy crude oils will become a major energy source in the
near future, replacing the conventional light crude oils, the reserves of which
are depleting steadily over time. Heavy crude oils present several technological
challenges in extraction, pumping, pipeline transportation and processing.
Very high viscosity impedes the mobility of the crude oil thereby introducing
difficulties in production and transportation. Chapter 1 is an introductory
chapter. Chapter 2 presents methods for enhancing the recovery of heavy crude
oils. Chapter 3 discusses the laboratory analysis of PVT properties of black oils.
Chapters 4 to 9 deal with pumping and pipeline transportation techniques.
Pre-treatment and removal of impurities/metals from heavy crude oils are

presented in Chapters 10 to 12. Catalysts for hydrocracking and hydrotreating of
heavy crude oils are discussed in Chapter 13. Chapter 14 presents the optimization
of petroleum refinery configuration to process heavy crude oils. Processing of
heavy crude oils generates different types of toxic organic and inorganic pollutants
and Chapter 15 describes the potential environmental challenges that arise due to
these pollutants.
I am very grateful to the editorial team at IntechOpen for their excellent and
continuous support from the beginning to the end of this book project.
I am deeply indebted to my wife Chandragandhi and children, Ramadevi and

Hemanand, for their unwavering support in all my activities.
Ramasamy Marappa Gounder

Universiti Teknologi Petronas,
Malaysia
Chapter 1
Introductory Chapter: Heavy

Crude Oil Processing - An
Overview
Ramasamy Marappa Gounder
1. Introduction
The demand for crude oil as an energy source is continuously increasing driven
by the ever-growing population and economic development. Globally, over 80 mil-
lion barrels per day of crude oil is produced currently out of which about 11 million
barrels are classified as heavy crude oils. It has been well recognized that reservoirs
of light conventional crude oils are decreasing and heavy crude oils are replacing
them in the pool of crude oil feedstock in refineries which process the crude oils
into various value-added products such as gasoline, diesel, liquefied petroleum gas,
petrochemical feedstock, etc. The contribution of heavy crude oils in the crude oil
pool is predicted to increase over the years from the current ~10%. An oil industry
expert, Professor Emeritus Peter Odell, suggested that by 2100, the oil industry
will be larger than in 2000 but up to 90% dependent on unconventional crude oils
(high-acid crude oils, heavy crude oils, bitumen, and oil sand) [1].
Heavy crude oil reserves are proven to be abundant, and the active heavy
oil-producing countries include Canada, Venezuela, United States, Mexico,
Brazil, Russia, Indonesia, China, Colombia, Ecuador, Iraq, Kuwait, Saudi Arabia,
Chad, and Angola. Heavy oils are relatively cheaper than light conventional crude
oils, and, therefore, they present an economic opportunity to petroleum refiners to
take advantage of their low cost to increase the refiner’s profit margins. Heavy crude
oils represent an important energy resource and require an unusually high levels
of effort and expertise to economically produce and process. But as the energy
demands grow, the economics of heavy oil production and processing will improve.
The production and processing of heavy oils will be influenced by the effectiveness
of available technologies.
Heavy crude oils are defined as any liquid petroleum with an API gravity in the
range of 10–22.3° [2]. The fundamental characteristics of heavy crude oils are high
viscosity and density, chemical complexity, high acidity, high sulfur, increased
level of metal and heteroatom impurities, high asphaltenes content, low American
Petroleum Institute (API) gravity, and low H/C ratio [3]. Due to these unfavorable
characteristics, heavy crude oils are termed low-quality crude oils, and they pose
many technological challenges in their production, transportation, and processing
to both the producers and the refiners. Extracting and processing of heavy crude
oil require large amounts of water and energy and can potentially cause extreme
damages to surrounding environment.
This chapter will provide an overview on the challenges posed by heavy crude
oils due to their unfavorable characteristics. Extraction of heavy oils is presented in
Section 2. Section 3 will discuss in the flow assurance issues due to the high viscosity
1
of heavy crude oils and techniques. Section 3 discusses the technological chal-
lenges that are encountered while processing the heavy crude oils in the refineries.
Section 4 provides a summary of the issues discussed in this chapter. These issues
are dealt in more details in the subsequent chapters of the book.
2. Extraction
Cold extraction and surface mining would be preferred for the recovery of
heavy crude oils. However, as the depth of the reservoir increases, and due to
the very high viscosities, recovery becomes extremely difficult. Water flooding
becomes ineffective due to their huge differences in their viscosities. In order to
increase the recovery factor, enhanced oil recovery methods are to be followed. As
oil viscosity decreases with the increase of temperature, external thermal sources
can be introduced to heat the oil and reduce the viscosity. Steam is generally used
as a thermal source. Once the viscosity gets reduced, recovery techniques using
chemicals and gases can be implemented to improve the displacement efficiency.
Cyclic steam stimulation, steam flooding, steam assisted gravity drainage, in situ
combustion, chemical injection, gas injection, and in situ catalytic upgrading are
some of the typically applied methods to enhance the recovery of heavy crude
oils. These methods require large volumes of water and energy on the wellheads to
successfully implement. In situ catalytic recovery of heavy oil has many advantages
over the steam, gas, and chemical injections. Milder operating conditions, reduced
waste products with higher extend of upgrading, minimization of surface upgrad-
ing facilities, and reduced environmental impacts are some of the advantages [4].
3. Flow assurance
The viscosity of heavy crude oils is in the range of 100–10,000 cp, while the
extra-heavy crude oils have viscosities greater than 10,000 cp. As the viscosity
increases, flow characteristics of heavy crude oils dramatically change to very low
mobility. The mobility of heavy crude oils reduces to such an extent that conven-
tional pumping techniques fail to achieve any flow from the well bottom to the
wellhead or in the transportation pipelines from the platforms to the receiving
centers. In addition, wax and asphaltene depositions on the walls of the pipelines
as temperature drops also hinder the flow through the pipelines. Such depositions
can lead to multiphase flow, clogging of pipelines, high pressure drops, and occa-
sional pipeline stoppages. Flow assurance is a technique through which the crude
oil is transported from the wellbore to the processing facilities while mitigating all
the risks and guaranteeing a manageable and profitable flow. The flow assurance
techniques are generally classified into three approaches, namely, viscosity reduc-
tion, drag minimization, and in situ crude oil upgrading [5].
3.1 Viscosity reduction techniques
There are several methods in practice to reduce the viscosity of heavy crude oils
in an effort to increase their mobility. These methods include (i) heating, (ii) dilu-
tion with light liquid hydrocarbons, (iii) oil-in-water emulsion formation, and
(iv) depression of pour point [5, 6].
Heating is one of the common methods employed for pipeline transportation
of heavy oils. Viscosity of heavy oils are highly dependent on temperature, and an
increase in temperature produces a significant drop in viscosity. The pipelines are
2
DOI: http://dx.doi.org/10.5772/intechopen.90425
generally well insulated, and the temperature is maintained by providing external

heating. Thermal management of production and transportation pipelines is
very important, and there are several approaches to provide external heat in the
pipelines, e.g., bundled pipelines in which a heating fluid is circulated through a
pipeline within a carrier pipe and electrically heated subsea pipelines. For high
wax crude oils, in addition to thermal management through heating/insulation,
chemical inhibitor injection also helps in reducing crystallization of wax
and thus viscosity.
Dilution is another method of reducing the viscosity of the heavy oil. It involves
the addition of lighter liquid hydrocarbons such as condensates from natural gas
production, conventional lighter crude oils, and product streams such as kerosene
from the refinery. In some cases, up to 30 wt.% of kerosene is required to suffi-
ciently reduce the viscosity. The disadvantage is that this uses up large quantities of
valuable commercial products, and, moreover, the added product is to be processed
again through the refinery along with the heavy crude oil. This, in turn, reduces the
plant production capacity and at the same time reduces the plant energy efficiency.
The addition of lighter liquid hydrocarbons may also affect the stability of wax and
asphaltenes leading to pipeline clogging. Sometimes, the dilution is also necessary
to meet the API requirements of the existing refineries.
Emulsion of oil-in-water is an alternative to the method of dilution to reduce the
viscosity of heavy oils. When the heavy oil is dispersed in water, the flow character-
istics improve tremendously. However, additional substances such as surfactants or
stabilizing agents are added to ensure the stability of the emulsions.
Pour point depressants, also known as wax crystal modifiers, are the chemical
additives that prevent nucleation and crystallization of paraffin. They reduce the
viscosity and yield stress of the crude oil appreciably enabling the transportation of
waxy crude oils.
3.2 Drag reduction techniques
Developing a core annular flow of heavy oils with a thin film of water or an
aqueous solution between the core and the wall of the pipe reduces the pressure
drop due to friction in the pipeline. This is akin to lubricating the inner core of the
heavy oils and thus reducing the pressure drops. But, it is quite difficult to maintain
the stability of the core through the length of the commercial pipelines.
3.3 In situ crude oil upgrading
Physicochemical upgrading of heavy oils produces a synthetic oil or syncrude

with higher API gravity and low viscosity. Upgrading of crude oil involves in situ
production of a solvent through separation, distillation, and thermal cracking, a
part of the heavy oil to produce lighter fractions. The lighter fractions can be used to
dilute the heavier fractions to upgrade their mobility.
4. Heavy crude oil refining
The processing of heavy oils in refineries, especially in the existing refineries,

presents many difficulties due to their unfavorable characteristics. Due to very low
H/C ratios, the yields of straight-run gasoline, kerosene, and diesel are very poor
due to high levels of heavier components such as asphaltenes. A major fraction
of the heavy crude oil after fractionation in an atmospheric distillation column is
expected to report to the residue stream as the feed to the vacuum distillation unit.
3
The economic value of the residue stream is very low, and therefore, conversion
techniques are required to upgrade them to maximize the production of value-
added streams. The upgrading of the residue streams is generally done in one of the
two methods, namely, hydrogen addition (e.g., hydrotreating or hydrocracking)
or carbon rejection (e.g., deasphalting, delayed coking, visbreaking, and thermal/
catalytic cracking) [7–9]. Fluidized catalytic cracking (FCC) and residue fluid-
ized catalytic cracking (RFCC) convert heavy oils into more valuable gasoline and
lighter products. These technologies enable the effective utilization of crude oils.
FCC and RFCC process technologies have become the heart of modern refineries
for upgrading heavy oils by upgrading atmospheric and vacuum residue streams.
Refineries require a high flexibility in residue processing facilities like FCC and
RFCC to cater to the highly varying nature of feedstocks.
There are several operational difficulties that arise in these upgrading processes.
For example, very high operating temperatures in the range of 500–1000°C in
thermal cracking units favors extensive coking [7, 10]: large amounts of expensive
solvents for separating high-molecular-weight components in solvent deasphalting
with relatively low yields of recovered deasphalted oil [11]. Catalytic deactivation
caused by coking and metals (e.g., Ni, V, Ca, and Fe) and requirements of expensive
hydrogen are major drawbacks of the hydrogen addition methods [11].
Except the heavy oil reserves from Africa, the rest of the heavy oil reserves have
been characterized to contain high levels of sulfur. Desulfurization is therefore
necessary in order to (i) meet the fuel specifications on sulfur content (e.g., 10 ppm
limits on gasoline and diesel according to Euro 5 standards) and (ii) to protect
catalysts from getting poisoned by sulfur. Hydrotreating removes materials such
as sulfur, nitrogen, and metals harmful to the catalysts, and hydrotreaters are
required to be located before the reformer, hydrocracker, and FCC units. Heavy
metals also poison the catalysts used for the conversion techniques mentioned
above and, thus, makes it imperative to pretreat crude oils to remove the metal
contaminants almost completely.
Higher fractions of asphaltenes in crude oils contribute to heavy fouling in crude
preheat train which affects the delicate balance of heat integration and stable opera-
tion of the atmospheric distillation column. Fouling is also pronounced with the
presence of sulfur and naphthenic acid in the crude oil. High-acid crude oils require
the removal of acid contents below certain threshold levels to safeguard the assets
from corrosion effects.
5. Conclusion
Heavy crude oils will steadily replace the conventional light crude oils as energy
sources to meet the increasing energy demands. The characteristics of heavy oils
render the existing extraction and refining processes ineffective. This chapter
enlisted some of the technological challenges faced by the oil producers and
refiners. Flow assurance is a much challenging issue in producing and transporting
heavy crude oils. Due to the low quality of the crude oil, the refining processes
face enormous challenges. Issues such as fouling, corrosion, excessive coking,
catalyst poisoning, increased contaminants in end products, the requirement of
large hydrogen resources, environmental pollutions, high operating and mainte-
nance costs, etc. require to be addressed with adequate and effective technologies.
The synthesis of new catalysts for refining processes which are tolerant to the
impurities present in heavy oils is also very crucial for the improved economics of
refineries.
4
Author details
Ramasamy Marappa Gounder1,2
1 Department of Chemical Engineering, Universiti Teknologi PETRONAS,

Seri Iskandar, Perak D.R, Malaysia
2 Centre for Process Systems Engineering, Institute of Autonomous Systems,

Universiti Teknologi PETRONAS, Seri Iskandar, Perak D.R, Malaysia
*Address all correspondence to: [email protected]
© 2019 The Author(s). Licensee IntechOpen. Distributed under the terms of the Creative
Commons Attribution - NonCommercial 4.0 License (https://creativecommons.org/
licenses/by-nc/4.0/), which permits use, distribution and reproduction for
non-commercial purposes, provided the original is properly cited.
5
References
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University Press; 2009. p. 130 2008;87:1623-1627
[2] Huc AY. Heavy Crude Oils: From [11] Speight J. Heavy and Extra-Heavy
Geology to Upgrading: An Overview. Oil Upgrading Technologies. 1st ed. UK:
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[3] He L, Lin F, Li X, Sui H, Xu Z.

Interfacial sciences in unconventional
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Rendón BZ, Juárez EM, Huicochea CB,
Clavel-López JC, et al. Transportation
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[6] Santos RG, Loh W, Bannwart AC,

Trevisan OV. An overview of heavy
oil properties and its recovery and
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[7] Rana MS, Samano V, Ancheyta J,

Diaz J. A review of recent advances
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[8] Khan MK, Kwek W, Kim J. Upgrading

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[9] Canıaz RO, Erkey C. Process

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6
Chapter 2
Methods for Enhancing Recovery

of Heavy Crude Oil
Mohd Afnan Ahmad, Shafirah Samsuri
and Nurul Aini Amran
Abstract
The methods of enhancing recovery of heavy crude oil explore the importance of
enhanced oil recovery and how it has grown in recent years due to the increased needs to
locate unconventional resources such as heavy oil, shale, and bitumen. Unfortunately,
petroleum engineers and managers are not always well-versed in the enhancement
methods available when needed or the most economically viable solution to maximize
their reservoir’s productivity. Various recovery methods have been explored to extract
heavy oil from deep reservoirs or oil spills. This chapter summarizes the details of
methods, namely nanoparticle technology, carbon dioxide injection, thermal recovery
and chemical injection, which include the methodology as well as the findings.
Keywords: enhancing oil recovery, nanoparticle, carbon dioxide injection,

thermal recovery, gas injection
1. Introduction
The production of oil is classified into three phases; primary, secondary, and
tertiary. First, the primary recovery involves the extraction of hydrocarbon which
naturally rises to the surface. Then, for the second phase, water and gas are injected
into the well to push oil to the surface [1]. After the second phase is done, there
is still about 60–80% of oil left inside the well [2]. Thus, the implementation of
enhanced oil recovery (EOR) during the last phase which is the tertiary phase
can contribute up to 30% of original oil in place (OOIP) that can be extracted.
Therefore, EOR can be represented by a few techniques namely nanoparticle tech-
nology, carbon dioxide injection, thermal recovery and chemical injection.
Heavy oils have the American Petroleum Institute (API) gravity of between 10
and 20 API and a viscosity greater than 100 cP with the characteristics of being
asphaltic, dense and viscous. More energy demands are required for the elevated vis-
cosity and the density of these crude oils in their production, and upgraded as well
for transportation. Recovery of heavy oil is expected to make an important contribu-
tion towards environmental protection as well as energy and resource conservation.
2. Nanoparticle technology
Nanotechnology is one of the methods which attracts great attention nowadays in

enhancing oil recovery because it is cost-effective and environmentally friendly [3].
7
Commonly, the size of nanoparticles for oil recovery is in a range of 1 to 100 nm.

The size may slightly differ from any other international organization. First and
foremost, the metallic oxide nanoparticles explaining the nature of the metal element
which has low ionization potential and low electronegativity shows that it is a reactive
and unstable element. The metal element can easily lose an electron, and form a stable
state when in contact or react with oxygen. There are a few examples of metal oxide
nanoparticles that have been studied lately such as aluminum oxide, copper(II) oxide,
iron oxide, nickel oxide, magnesium oxide, tin oxide, titanium oxide and zinc oxide [4].
In enhancing oil recovery (EOR) with nanoparticles, the most influential
factor is the interfacial tension (IFT). This parameter contributes to decreasing the
capillary force, thereby increasing the oil recovery. Several studies show that IFT
reduction between the oil and aqueous phase when mixed with nanofluids increase
oil recoveries [5–7]. The trapped oil droplets may have deformed whilst the IFT
between the oil and aqueous phase reduced, and it may pass the pore throats easily
[5, 8]. Another parameter is the wettability, as it is measured by the complex
interface boundary conditions acting within the pore space of sedimentary rocks
[9, 10]. The alteration via wettability happens if nanoparticles are absorbed on the
surface of grains. The most recommended metal oxide nanoparticles as enhancing
oil recovery agent for heavy oil reservoirs is aluminum oxide (Al2O3) nanofluid. It
can decrease the oil-brine IFT and oil viscosity. Spontaneous imbibition recovery
in sandstone cores shows the highest recovery when the Al2O3 nanoparticles are
dispersed in diesel [11]. Other than that, an experiment conducted by researchers
found that Al2O3 nanoparticles can de-stabilize water drops which reduce the water
in oil emulsion. This case indicates that Al2O3 may decrease the emulsion viscos-
ity [12, 13]. However, it concludes that higher concentration of nanoparticles can
block pore throats due to the aggregation of particles around the pores, and this
may lead to prevention of oil recovery. This proves that in the study by Alomair
et al., [12] the lowest concentration of 38.5% of oil recovery is obtained due to the
IFT reduction and emulsion viscosity. Since iron oxide has a unique magnetism
nature and low toxicity, iron oxide particles can reduce the viscosity of crude oil
[14]. As iron oxide spreads in brine, it can be a good oil recovery agent in sandstone
reservoirs. For unprompted imbibition in sandstone rocks, it shows that when
diesel is selected as a dispersing agent, iron oxide can act as a better oil recovery
candidate with instances of 82.5% of total oil recovery. Researchers have experi-
mented with iron oxide to coat polymer in the separation of water and oil [15].
Polyvinylpyrrolidone (PVP) is the polymer used and coated with this nanoparticle,
and results in near 100% of oil recovery due to the PVP that has the tendency to
absorb both aliphatic and aromatic components of oil component, and the iron
oxide acts as a structural support which allows magnetic separation from aqueous
phase easily.
On the other hand, nickel oxide (Ni2O3) nanoparticles also show the same nature
as Al2O3 nanoparticles. The effects of dispersed nanoparticles in heavy oil show
the recovery of up to 85% of the asphaltenes in the original solution. According to
Ogolo et al. [4], spontaneous imbibition and core flood experiments are seen on
sandstone rock samples at room condition. The observation for spontaneous imbi-
bition experiments which result in aluminum, nickel, and iron oxides are best found
in oil recovery agents especially when diesel is selected as the dispersing agent. In
the case of the core flooding experiments, nickel oxide nanoparticles are found to
increase oil recovery when injected into sandstone cores after waterflooding. The
recovery factor is found to be higher particularly when brine is used as the disper-
sant for nickel oxide particles. The study claims that the nickel oxide nanoparticles
can increase the viscosity of the displacing fluid, and decrease the viscosity of the
displaced oil.
8
Furthermore, magnesium oxide (MgO) and zinc oxide (ZnO) nanoparticles are
used during core flood tests which spread in brine or ethanol. It can cause perme-
ability impairment in sandstone rocks. It is found that soaking the rock samples in
ethanol and magnesium oxide nanoparticle solution could significantly reduce the
oil viscosity. For ZnO, the investigation of the applications of this inorganic com-
pound in enhancing oil recovery processes are very limited. As stated by Ogolo et al.
[4], similar to magnesium oxide, when ZnO is used as an enhancing oil recovery
agent in sandstone, it shows a negative effect on the permeability of the samples
used. The study claims that the problem initiated by agglomeration of the zinc oxide
nanoparticles at the injection point can block the pores.
Other than that, Zirconium oxide (ZrO2) nanoparticles are rarely used in the oil
and gas industry and in enhancing the oil recovery process. Ogolo et al. [4] inject
metal oxide as an enhancing oil recovery agent at room temperature into a sand-
stone core sample. It results in a small increase in oil recovery compared to the injec-
tion of distilled water alone. When brine or ethanol is used as dispersing agents, it
reduces the recovery factor to less than that achieved in the absence of nanoparticles
[4]. Tin oxide (SnO2) nanoparticles are investigated by Naje et al. [16]. SnO2
nanoparticles have recently attracted a lot of attention from researchers in various
fields. Generally, SnO2 is not used in oil recovery processes extensively. Studies are
done by Ogolo et al. [4] on the potential of SnO2 as oil recovery agent. The results
obtained by these researchers show that SnO2 performs like zirconium oxide and
increases oil recovery in sandstone cores while spread in distilled water [16].
For TiO2 nanoparticles, an analysis using these nanoparticles for water flooding
are done, and 80% of oil recovery from oil-wet Berea sandstone in the EOR process
comes out. After that, the test is done again, but with the absence of nanoparticles
which show a result of 49% in amount [17]. However, the tendency of these par-
ticles to aggregate and precipitate results in a milky solution and impossible to mea-
sure the IFT [11]. They also conduct a coreflood experiment with TiO2 and achieve
76% points of original oil in place (OOIP) with 0.05%wt of concentration by using
povidone as dispersant since it reduces the particles plugged at inlet points [11].
Instead of the use of metal oxide nanoparticles, researchers also found organic
and inorganic nanoparticles that may contribute to the EOR system. For organic
nanoparticles, a study found the use of Multiwall Carbon Nano-tubes (MWNT)
potential fluid for EOR agent in a high-temperature condition and high-pressure
reservoirs [18]. There are two results which are in the absence and presence of
electromagnetic waves. For the absence of electromagnetic waves, it shows 36%
of oil recovery after the injection of the MWNT nanofluids, while in assistance of
electromagnetic fields, it shows almost double the recovery. The higher results have
been directly related to the oil viscosity reduction associated with the electromag-
netic field. Also, the application of these nanotubes has been reported to increase
the efficiency of drilling fluids [19].
In inorganic nanoparticles, the prominent element used is silica. The SiO2
nanoparticles as proposed by Ogolo et al., [4] shows that the application of SiO2 in
water-wet sandstone reservoirs with this type of nanoparticles can be considered
as a suitable EOR agent for this type of rock. Researches reveal that the specific
surface area of the SiO2 powders almost have no change even when it is heated to
various temperature of up to 65°C, and proven with good thermal stability [20]. It
also does not need a stabilizer compared to metal oxide by forming a more stable
emulsion in 3%wt NaCl brine, and achieving higher oil-brine IFT compared to a
mixture of brine and stabilizer on its own, resulting in higher oil recovery from
Berea sandstone [9].
Researchers investigate that SiO2 nanoparticles on the bubble surface enhance
the foam stability against film rupture and Ostwald ripening [21]. The bubbles
9
Nanoparticles Findings References
Aluminum • Mostly used nanoparticles in enhancing oil recovery (EOR) [4, 11, 12]
oxide (Al2O3) process.
nanofluid
• Al2O3 decreases oil brine interfacial tension (IFT).
• Total recovery due to nanoparticles (distilled water as dispersing
agent) is 12.5%.
• Total recovery due to nanoparticles (brine as dispersing agent) is
5.0%.
• Al2O3 decreases oil viscosity.
Iron oxide • Has a unique magnetism characteristic. [4, 14, 15]
• Can reduce oil viscosity.
agent) is 9.2%.
• Diesel as a dispersing agent reached 82.5% of oil recovery.
Nickle oxide • Has the same characteristics as Al2O3. [3, 4]

(Ni2O3)
agent) is 2.0%.
• Total recovery due to nanoparticles (brine as dispersing agent) is
1.7%.
• The oil recovery reached up to 85%.
Magnesium • Cause permeability impairment in sandstone rocks. [3, 4]

oxide (MgO)
• Reduce oil viscosity when soaking the rock sample in ethanol with
MgO.
agent) is 1.7%.
Zinc oxide • Very limited use in EOR. [3, 4]

(ZnO)
• These nanoparticles can block the pores, showed a negative result.
agent) is 3.3%.
Zirconium oxide • Rarely used in EOR. [4, 16]

(ZrO2)
• Show small recovery of oil compared to distilled water alone.
agent) is 4.2%.
Tin oxide (SnO2) • Same characteristics as zirconium oxide. [4, 16]

• Increases oil recovery while spreading in distilled water.
agent) is 3.3%.
Titanium dioxide • Recover 80% of the oil from oil wet Berea sandstone. [11, 17,]
(TiO2)
• Reduce the oil brine IFT.
• Achieved higher oil recovery in wet formation compared to SiO2.
Multiwall carbon • Absence of electromagnetic (EM) wave shows 36% of oil recovery. [18, 19]
nanotubes
• The presence of EM waves shows 72% of recoveries.
(MWNT)
SiO2 • Less oil recovery at room temperature. [4, 9, 20–22]

• Considered as suitable EOR agent in all different wettability
conditions.
• Forming stable foam, more stable bubbles penetrate further inside
the pore which can displace more oil.
10
Nanoparticles Findings References
Hydrophobic • The small size of these particles in the range of several to tens [3, 4]
silicon oxide of nanometres reduces the risk of blocking the pore in an EOR
(SiO2) process.
Inorganic • Can reduce IFT. [23, 24]

silica core or
• Increasing the viscosity at critical concentrations.
polymer-shell
nanocomposite • Can be an excellent EOR agent for sandstone reservoirs, especially
when dispersed in ethanol.
Table 1.
Summary of nanotechnology method in EOR process.
are more stable than foam when they meet the residual oil due to bigger bubbles
being flushed and squeezed into smaller ones towards the dead-end. The more
stable bubbles penetrate further inside the pore which can displace more oil. When
the stable bubbles invade the dead-end pore, the microforces acting on the oil
droplet also help to recover more oil. The attached nanoparticles on the bubbles
reduce the surface area available for interbubble gas diffusion, which stabilize
foam against Ostwald ripening [22]. Other than that, the use of SiO2 nanoparticles
during core-floods conducted at room temperature result in less recovery, and it is
still considered as a suitable EOR agent in all different wettability conditions from
water-wet to intermediate and oil-wet. Researchers explain that alumina coated
silica nanoparticles on the SiO2 nanoparticles entirely alter their properties.
The coating creates a positive charge on the surface of a nanoparticle. The study
proves that alumina coated with SiO2 possesses higher surface area compared to
those without coating, and when disposed into the environment, it shows lower
toxicity. The study also comes out with fascinating results in which alumina coated
silica nanoparticles with modified surface form a more stable foam and result in
good oil recovery from sandstone cores compared to the bare nanoparticle or any
surfactant flooding. For hydrophobic silicon oxide nanoparticles, it is demonstrated
with addition of silanol (Si-OH) group into the silica nanoparticles surface, and
completed with a satisfying result, showing that it is a better EOR agent in sand-
stone reservoir compared to the metal oxide nanoparticles [4].
Other than that, most researchers use the spherical fumed silica nanoparticles as
a stabilizing agent for oil/water emulsion [23]. In EOR studies, it has limited direct
use in flooding experiment and has not been studied yet. However, the size of the
nanoparticles is suitable for EOR activities which can reduce the risk of blocking the
pores. After that, as for inorganic silica core or polymer-shell nanocomposite, its
build is illustrated as SiO2 nanoparticles in the core covered with a shell of synthetic
polyacrylamide polymer. The composite nature of the nanoparticles is suitable to be
applied for higher temperature and salinity with the presence of hard ion that can
be found in offshore reservoir [24]. Table 1 show the summary of nanotechnology
method in EOR process.
3. Carbon dioxide injection
Another effort in increasing the production of oil from the reservoir is the type
of method in the EOR process. In secondary production including water flood-
ing and gas injection, it is employed to increase production by boosting depleted
pressure in formation. After the oil and natural gas in a formation is produced, the
11
remaining trapped hydrocarbon in the reservoir due to the pressure in the forma-
tion is reduced. Therefore, the production is either slow dramatically or stop alto-
gether [25]. In the secondary phase, gas injection is used on a reservoir in enhancing
waning pressure within the formation. It will systematically spread throughout the
field, and the gas-injection reservoir is used to inject gas and effectively sweeps the
formation for remaining petroleum and boosts production [26].
The gas injection, also known as miscible flooding, maintains the reservoir
pressure and improves the oil displacement due to the reducing interfacial ten-
sion between water and oil. The techniques remove the interface between the two
interacting fluids, and this allows for total displacement efficiency [27]. The gasses
used are carbon dioxide (CO2) and natural gas or nitrogen, but CO2 is commonly
used for miscible displacement because it reduces the oil viscosity and cheaper [28].
Oil displacement by CO2 injection depends on the mixtures of the gas and the crude
phase behavior, which are strongly dependent on reservoir temperature, pressure
and crude oil composition.
The use of CO2 as an injection fluid in oil reservoirs has been widely investigated
[29]. The characteristics of CO2 include ease to dissolve oil, can reduce the viscos-
ity of the oil, use moderate pressure to extract the oil’s light component, and can
form heterogeneously with oil at relatively small pressure [30]. Besides, CO2 has
minimum miscibility pressure (MMP) compared to other gasses. From the study,
oil recovery has been improved by manipulating injection pressure (3000, 3144
and 3400 psi) for both horizontal and 450 down dip displacement processes. It can
also be said that oil recovery and displacement efficiency increase with the increase
of injection pressure. Thus, high pressure can produce maximum displacement
efficiency and oil recovery.
The solvent-based process such as cyclic solvent injection has shown a signifi-
cant contribution in enhancing heavy oil recovery. The examples of solvent are
CO2, flue gas, and light hydrocarbon gases such as natural gas, methane, ethane,
propane, and butane. The cyclic solvent injection is an initiative for cyclic steam
injection for heavy oil. This is done by injecting the gas into a well (huff cycle),
followed by a short shut-in time and then the well is returned to production after
a soaking time to allow solvent interaction with oil formation (puff cycle) [31].
Firouz and Torabi [31] investigate the efficiency of the huff-and-puff recovery
technique through eight sets of cyclic injection experiments at different operating
pressure, utilizing pure CO2 and pure methane to enhance heavy oil recovery. 71%
of oil recovery is obtained by injecting pure CO2 at the near supercritical condition
of 7239 kPa and 28°C, while 50% of oil recovery is obtained by using pure methane
at the highest operating pressure of 6895 kPa. The production is contributed by
several governing mechanisms such as solution gas drive, viscosity reduction,
extraction of lighter components, the formation of foamy oil and to a lesser degree
of diffusion process.
Consequently, a study is also done via a long core in the CO2 huff “n” puff
process. When the CO2 is injected into the core, diffusion occurs to prove viscosity
reduction and oil swelling. The IFT between the CO2 and heavy oil declines [32, 33].
The mobility then increases, and oil recovery enhances significantly. The ultimate
heavy oil recovery factors are as high as 32.75%, which is a very good production
performance for a cold heavy oil production process [34]. Another study is done in
which the CO2 injection is compared with the injection of nitrogen gas. Both gases
show a positive result in oil recoveries and the recoveries are led with the injection
of CO2 gas with 15.8% based on OOIP.
When CO2 is in the soaking stage, it can also lower the viscosity, and alter the
relative permeability hysteresis of higher oil recovery. Then, by using this gas
injection, the recovery obtained is ultimately higher at 85.9% based on OOIP
12
compared to the injection of nitrogen gas at 64.7%. In 2017, further study was
done and the team investigated the probability of improving oil recoveries for
21 samples at reservoir conditions. The oil transportability in the small pores
improves, then the CO2 can extract oil from the unconventional core samples by
diffusion. The result proves that by injecting this gas, it is able to recover up to 99%
of oil samples in 24 hours under reservoir condition exposure, and it summarizes
that the CO2 could be injected to highly fractured tight reservoirs through fractures
to recover oil [35, 36].
Particularly, injecting the CO2 in a supercritical state is effective in reservoirs
with depth of about 2000 feet. It can be applied in high pressure with lighter oil, as
a result of oil swelling, in reducing the viscosity and possible in reducing IFT with
the reservoir rock. For low pressure or heavy oils case, CO2 will form an immiscible
fluid, or it can only partially mix with the oil. Some oil may be swelling and signifi-
cantly the oil viscosity still can be reduced [37]. In this application, there is about
one-half and two-third of injected CO2 return with the produced oil. Usually, it is
reinjected into the reservoir to minimize the cost. Thus, the use of CO2 as a solvent
is beneficial for being more economical than other similar miscible fluids such as
propane and butane [38].
Besides that, water-alternating-gas (WAG) is another method implemented in
the EOR process. As water mixing with CO2 is used, the saline solution is used to not
disturb the carbonate formation in the reservoir. Water mixed with CO2 is injected
into the reservoir for a larger recovery as the mixture has lower miscibility with oil.
The use of both water and CO2 also lowers the mobility of CO2 gas, for instance,
making the gas more effective at displacing the oil in the reservoir [39]. The
researcher states that using a small slug of both CO2 and water allows for a quick
recovery of the oil. Additionally, in a study done by Saxena K. [40], using water
Findings References
• CO2 can easily dissolve in oil. [30]

• Injecting CO2 can reduce the oil viscosity in the reservoir.
• Only requires moderate pressure to be applied for oil recovery.
• CO2 can form heterogenous when mixing with oil in the reservoir.
• The diffusion occurs when CO2 injected into the reservoir and this leads reduction of [32, 33]
viscosity and oil swelling.
• The mobility of oil increases after the injection of CO2. [34]

• Heavy oil recovery achieved as high as 32.75% when CO2 is injected.
• The injection of CO2 gas able to recover up to 99% of oil samples. [35, 36]
• The CO2 could be injected on to highly fractured tight reservoirs through fractures to
recover oil.
• CO2 gas will form an immiscible fluid for low pressure or heavy oils case. [37]
• The gas only partially mixes with the oil then some oil may be swelling, and the oil
viscosity still can be reduced.
• CO2 gas is more economical than other miscible gas such as propane and butane. [38]
• Water-alternating-gas (WAG) making the gas more effective at displacing the oil in the [39]
reservoir.
• Using water allows for greater oil removal and greater geochemical interactions in [40]
WAG.
Table 2.
Summary of carbon dioxide injection method in EOR process.
13
with lower salinity allows for greater oil removal, and greater geochemical interac-
tions [40]. Table 2 show the summary of CO2 injection method in EOR process.
4. Thermal recovery
Thermal EOR is another technique used for more than 50% in the EOR pro-
cess. Steam injection is the most common method in thermal EOR including the
in-situ combustion [41]. This process involved by heating the reservoir and then
the injected high-oxygen gas mixture was burnt to create the combustion front.
Basically, for the steam injection, it is applied in a shallow reservoir containing
high viscosity oil usually for heavy crude oil, for example, the reservoir in the San
Joaquin Valley of California or the oil sands of Alberta, Canada [42]. In the 1960s,
steam injection is commercially used and well understood by the researchers in
EOR. Steam injecting heats the crude oil in the formation whilst lowering the oil
viscosity and at the same time the steam will vaporize some of the oil to increase
its mobility.
Besides, when the crude oil viscosity decreases the surface tension also reduces.
It increases the permeability of oil and improves the reservoir seepage condition.
When oil vaporizes, it allows the oil flowing freely through the reservoir and forms
a better quality of oil once it has been condensed. The steam injection EOR varies
with two distinct categories: cyclic steam stimulation and steam flooding [43].
For cyclic steam stimulation, the same reservoir is used for steam injection and oil
production. Firstly, the steam is injected for a period from a couple of weeks to a
couple of months. The introduction of the steam into the reservoir immediately
allows the oil to heat up through convective heating, and at the same time it is
lowering the oil viscosity. After the targeted oil viscosity is achieved, the steam
injection stops to allow the heat to redistribute evenly in the formation. By doing
that, it can contribute by increasing the amount of oil recovered after this stage.
These steps are repeated when the reservoir temperature drops and the viscosity of
oil increases again.
Other than that, steam flooding injection and production wells vary from each
other. Steam is introduced through the injection wells and move towards the oil by
physically displace while heating the oil to reduce its viscosity. The steam flood-
ing is in the continuous form which allows the steam to drive the oil towards the
production wells. Compared to cyclic steaming, this steam flooding is more costly
due to this method which requires more steam during the process. Nonetheless, this
method usually recovers a big portion of oil. In some cases, both methods can be
implemented together for cyclic stimulation followed by steam flooding [44].
Thermal Oil Recovery is by far the most popular method used in the world dur-
ing the tertiary stage of oil recovery. Steam injection is the most common method
Findings References
• Using steam injection to heat the crude oil in lowering the oil viscosity. [41]
• The steam injection was applied in a shallow reservoir containing high viscosity oil [42]
which usually suitable for heavy crude oil.
• Thermal recovery method used to recover a big portion of oil. [44]

• Both methods can be implemented in cyclic stimulation followed by steam flooding in
EOR.
Table 3.
Summary of thermal recovery method in EOR process.
14
used in thermal EOR. It helps produce up to 30% of OOIP. Steam injection does not
pose as many environmental risks as other EOR methods might have. This helps
implement this technology in different countries, even with strict regulations. The
economy is the main factor that determines if this technology should be imple-
mented in one field or the other. Table 3 shows the summary of thermal recovery
method in EOR process.
5. Chemical injection
Usually, the injection of any type of chemical as a dilute solution is used in

mobility aid and the reduction of IFT. The injection of an alkaline or caustic
solution into the reservoir with oil which consists of organic acids that occur
in the oil naturally will produce a soap that may reduce the IFT, and sufficient
to increase the production of oil [45]. Other than that, water-soluble polymer
diluted solution is injected to increase the viscosity of injected water in the
reservoir which can improve the amount of oil recovered in some formations.
For example, the use of petroleum sulfonates as surfactant or biosurfactant
such as rhamnolipids in dilute solutions can lower the IFT or capillary pressure
that impedes oil droplets from moving through the reservoir. So then, this is
analyzed in terms of the number of the bond, relating the capillary forces to
gravitational ones.
Special formulations of oil, water, surfactant and microemulsions can be
particularly effective in reducing interfacial tension. Concerning this application
of these methods, they are usually limited by the cost of the chemicals and their
adsorption and loss onto the rock of the oil-containing formation. All the chemi-
cals are injected into several reservoirs and the production occurs in other nearby
wells. These methods include the polymer flooding, microbial injection, and
plasma pulse.
For polymer flooding, it consists of long-chain polymer molecules mixed with
the injected water to improve the water viscosity. It also implements the vertical
and areal sweep efficiency to improve the water/oil mobility ratio [46]. The sur-
factant may be used in conjunction with polymer, it decreases the IFT between oil
and water. This reduces the residual oil saturation and improves the macroscopic
efficiency of the process [47]. Primary surfactants usually need the addition of co-
surfactant, activity booster and co-solvent in fixing the stability of the formulation.
As caustic flooding is the addition of sodium hydroxide into the injection of water,
therefore, it lowers the IFT, reversing the rock wettability, oil emulsification, the oil
mobility and aids in drawing the oil out of the rock.
Other than that, the microbial injection which is part of microbial EOR is a
method rarely used due to the higher cost and not preferable. These microbes help
in EOR by generating biosurfactant in partially digesting long hydrocarbon mol-
ecules or by emitting CO2 gas. There are a few studies in achieving this microbial
injection. Bacterial cultures are mixed with food source such as molasses injected
into the reservoir. Then, the second approach is where the nutrients are injected
into the ground to nurture the existing microbial bodies. The bacteria tend to help
in increasing the production of natural surfactants which they normally used to
metabolize the underground crude oil [48]. After the injected nutrients are utilized,
the microbes will be terminated where their exterior surface will become more
hydrophilic. At the same time, the microbes will migrate to the oil-water interface
area where it will cause the oil droplets to form a larger oil mass. Thus, making the
droplets to be more likely to migrate to the wellhead. Table 4 shows the chemical
injection method in the EOR process.
15
Findings References
• The injection of an alkaline or caustic solution into the reservoir with oil produces a [45]
soap that can reduce the IFT.
• Water-soluble polymer diluted solution also can be used in reducing the IFT.
• This may lead in increasing the production of oil.
• Polymer flooding consists of long-chain polymer molecules mixed with the injected [46]
water can improve the water viscosity.
• It implements the vertical and areal sweep efficiency due to improving the water/oil
mobility ratio in the reservoir.
• The surfactants may be used in conjunction with polymer, it decreases the IFT [47]
between oil and water.
• This will reduce the residual oil saturation and improves the macroscopic efficiency
of the process.
• Using microbial injection in generating the biosurfactant or emitting CO2 in [48]
decreasing the IFT of oil.
• Nutrients are injected into the ground to nurture the existing microbial bodies
and these nutrients cause the bacteria to help increase the production of natural
surfactant which they normally used to metabolize crude oil underground.
• Causing the oil droplets to form from the larger oil mass and making the oil move to
the reservoir surface.
Table 4.
Summary of chemical injection method in EOR process.
6. Conclusion
Most studies show that nanoparticles can be used in increasing the oil recovery
from an oil reservoir in which this nanotechnology in displacement fluid can
lower the interfacial tension, change the wettability of rock to a more water-water
state. It also lowers the adsorption of surfactant on reservoir rock, but the stabil-
ity of nanoparticles is the most challenging problem as well as the aggregation
of nanoparticles. Besides, there is a nanoparticle technology that has not been
discovered and needs further investigation in EOR. The most concerning problem
in nanoparticle technology is costly in the application and its effects on the environ-
ment. Nevertheless, using the recommended nanofluid to flush a depleted reservoir
or using ethanol itself may boost or improve the oil recovery.
After that, the CO2 injection has the potential in the application for enhancing
heavy oil recovery with CO2 injection, and it is increasing in reservoir pressure and
driving higher forces to produce more oil. Sometimes injected gas mixes and dis-
solves in oil. Thus, the oil viscosity decreases because oil moves easier than before
and oil production improves. Therefore, the prominent benefits using CO2 gas is
the miscibility of gas in crude oil, less expensive and is an excellent method in EOR
where the injection may improve oil recovery at the same time, the greenhouse gas
profile is improved as well.
Besides, thermal EOR is a commonly used method in the world during the
tertiary stage which helps improve the production of oil about 30% of OOIP. It
also does not contribute to any environmental risk or pollution as another method
in EOR might have. For the chemical injection, this method uses many types of
chemicals including polymers and surfactants. It can reduce the IFT and increase
the flooded water viscosity. This method is used followed by the waterflood where
it captures residual oil then the production of oil is up to 15% incremental. In a nut-
shell, both nanoparticles, CO2 injection, thermal recovery and chemical injection
16
in enhancing oil recovery are reviewed. The results are promising and there is still a
chance for these methods to become better.
Acknowledgements
The authors would like to acknowledge the Centre for Biofuel and Biochemical
Research (CBBR) and Chemical Engineering Department, Universiti Teknologi
PETRONAS for the support.
Conflict of interest
The authors declare no conflict of interest.
Author details
Mohd Afnan Ahmad1,2, Shafirah Samsuri1,2* and Nurul Aini Amran1,2
1 Chemical Engineering Department, Universiti Teknologi PETRONAS,

Seri Iskandar, Perak, Malaysia
2 Centre for Biofuel and Biochemical Research, Universiti Teknologi PETRONAS,

Seri Iskandar, Perak, Malaysia
17
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21
Chapter 3

Abdelaziz El-Hoshoudy and Saad Desouky
Abstract
Precise PVT studies and behavior of phase-equilibrium of petroleum reservoir

fluids are essential for describing these fluids and appraising their volumetric
behavior at several pressure stages. There are numerous laboratory studies that can
be performed on a reservoir sample. The amount of data desired determines the
number of tests to be performed in the laboratory. Generally, there are three
laboratory tests which characterize hydrocarbon fluids, namely primary study,
constant mass depletion, and differential vaporization test. Generally, PVT proper-
ties are determined either experimentally or calculated theoretically through
published correlations. This chapter presents different PVT laboratory tests that are
required to understand the phase behavior of black oils.
Keywords: PVT experiments, black oil properties, petroleum reservoirs
1. Introduction
Petroleum (an equivalent term is a crude oil) is a complex mixture consisting

predominantly of hydrocarbons and containing sulfur, nitrogen, oxygen, and
helium as minor constituents. The physical and chemical properties of crude oils
vary considerably and depend on the concentration of the various types of hydro-
carbons and minor constituents present. Crude oil reservoirs are classified
according to initial reservoir pressure into the following categories: (1) under-
saturated oil reservoir; in which initial reservoir pressure is greater than the bubble
point pressure of reservoir fluid; (2) saturated oil reservoir; in which initial reser-
voir pressure is equal to the bubble point pressure of reservoir fluid; (3) gas-cap
reservoir; in which initial reservoir pressure is below the bubble point pressure of
reservoir fluid, so reservoir is termed as gas-cap or two-phase reservoir, since the
gas or vapor phase is underlain by an oil phase. Petroleum hydrocarbons exist as
gaseous or liquid phase depending on reservoir temperature. If it is higher than the
critical temperature of the fluid, the reservoir fluid is gas. Otherwise, the reservoir
fluid is oil [1]. Black oil reservoir is considered as one of the most precious reservoir
fluids. It constitutes the majority of oil reservoirs and exists in every basin. An
accurate description of physical properties of crude oils is of considerable impor-
tance in the fields of both applied and theoretical science and, especially, in the
solution of petroleum reservoir engineering problems. Some of these physical
properties are of primary interest in petroleum engineering studies and detected
through PVT tests which aim to determine reservoir fluid behavior at simulated
reservoir conditions. Data on these fluid properties is usually determined by labo-
ratory experiments performed on samples of actual reservoir fluids. In the absence
of experimentally measured properties of crude oils, it is necessary for the petro-
leum engineer to determine the properties from empirically derived correlations.
23
However; correlations are approximations and may be useful only in regional geo-
logical provinces.
Crude oils cover a wide range of physical properties and chemical compositions
and are classified into black oils and near-critical or volatile-oils [2] depending on
their phase behavior. The phase diagrams of two reservoir types are illustrated in
Figures 1 and 2, while their physical properties are indicated in Table 1 according
to classifications established by Moses [1], McCain [3], Whitson and Brule [4].
From the phase diagram, following the pressure reduction path as indicated by the
vertical line EF, the iso-lines are scattered uniformly around the reservoir tempera-
ture which can be located at any region between points C&F. It is apparent that the
Figure 1.
Typical phase diagram for black oil [8].
Figure 2.
Typical phase diagram for volatile oil [8].
24
Property Black oil [7, 9] Volatile oil [1]
Fluid color Deep black Light colored turn to

slightly reddish
Mole % of heptane >17.5% up to 26.5% 12.5–17.5%

plus (C7+)
(GOR) 1500–1750 & up to 2000 scf/STB 2000–3000 scf/STB
API <45° 40° or higher

6 1
Co 3–150 10 psi (under-saturated to highly ……
saturated GOR oils)
βo <2 rbbl/STB >2 rbbl/STB
Table 1.
Criteria of black and volatile oil reservoirs.
reservoir temperature (Tres) in black oil reservoirs is less than the critical tempera-
ture (Tc). Moreover, the liberated gas below the bubble point pressure is considered
as lean gas for industrial applications [5]. While in volatile oils, Tres is closest to the
critical temperature. Another important differentiation lies in the volume of
evolved gas below bubble point which is much greater in volatile oil than that
observed for black oils [6]. Another important factor comprising gas oil ratio
(GOR), and mole % of C7+, where GOR is obtained from field data and the mole %
of C7+ is obtained from composition analysis. PVT properties for black oils in almost
all reservoirs are required for production and surface facilities calculations to man-
age, develop, and forecast oil field behavior [7], as well as maximizing economic
profit.
PVT analysis is utilized by reservoir engineers to distinguish physical properties
of reservoir fluids and variations in the volume and phase state that occurs during
oil production [10, 11]. The phase envelope is characterized by some physical
criteria such as oil formation volume factor, saturation pressure, gas oil ratio, oil
density, oil viscosity, and oil isothermal compressibility. This phase envelope may
be drawn through experimental data points or via software packages like PVTp,
PVTsim, Eclipse and so on, based on the differential equation of states. The impor-
tance of PVT properties for reservoir performance analysis makes a dire need to
develop a convenient way to predict these properties mathematically either by
empirical correlations or equations of state. These empirical relations comprise two
types. The first one belongs to the black oil type which forecast PVT behavior from
the available PVT data, including saturation pressure, reservoir temperature, oil
API index, gas-oil ratio, and reservoir pressure. The second one belongs to compo-
sitional models which rely on the equation of states and its hybrids. In these models
besides PVT parameters, other measurements including fluid composition, critical
temperature, molar masses and components acentric factor are utilized [12, 13].
Although accuracy of the empirical PVT correlations is often limited due to varia-
tions and complexity of multicomponent reservoir fluid systems, these correlations
still used on field scale [14–17].
2. PVT physical parameters and black oil modeling
In a black oil reservoir, the oil and gas formation volume factors, gas densities,
the solution gas-oil ratio, and the viscosities of oil and gas are measured at reservoir
temperature as a function of pressure. Once these measurements are, they can be
25
applied in empirical correlations to obtain the relative in situ amounts of oil and gas
during the production life of the reservoir.
2.1 Crude oil API gravity
Crude oil density is defined as the mass of a unit volume of the crude at a
specified pressure and temperature and expressed in g/cc. In typical oil reservoirs,
the oil density decreases with pressure depletion until it reaches the lowest value at
the bubble point. The higher oil density at higher pressures resorts to the high oil
molecules compressing per the unit volume. By reducing pressure beneath the
bubble-point pressure, the gas is ejected from the solution which forms a free gas.
The released gas is saturated with some of oil intermediate components, while the
heavier one remains in the reservoir. These intermediates release results in the
density reversal trend versus pressure beneath the saturation pressure. It is calcu-
lated either by compositional models or by correlating parameters. The API gravity
is the preferred gravity scale, and related to the specific gravity which is defined as
the ratio of the oil density to water density at 60°F and atmospheric pressure by the
following relation:
141:5
API ¼ � 131:5 (1)
γo
2.2 Solution gas specific gravity
It is a dimensionless property that represents the ratio between hydrocarbon gas

density and the air density at standard conditions. It is ascribed practically by the
weighted average of the specific gravities of the separated gas from each separator,
and expressed by the following relation:

Σni¼1 Rsep i γ sep þ Rst γ st
γg ¼ i (2)
Σni¼1 Rsep i þ Rst
2.3 Gas solubility
It is defined as the number of standard cubic feet of gas that dissolve in one
stock-tank barrel of crude oil at certain pressure and temperature and defined in
SCF/STB [18].

Vg P, T
Rs ¼ (3)
ðV o Þsc
At standard conditions, dissolved gas is completely released from the oil, and
therefore the oil contains no gas. Gas solubility increase with pressure increasing
until it reaches the maximum value at saturation pressure. Below the bubble point
pressure, gas is evolved with reduction in pressure and the gas solubility also
decreases. Generally, the lighter the oil the higher the gas solubility, therefore
volatile oils often has a higher solution GOR than black oils.
2.4 Bubble point pressure
It is defined as the highest pressure at which a bubble of gas is first liberated

from the oil, and is determined experimentally by conducting a constant mass
26
depletion test or estimated from empirical correlations. By reservoir pressure

depletion beneath the saturation pressure, a released gas is formed in the reservoir.
Since gas mobility is greater than the oil mobility, the produced GOR increase with
continual pressure depletion beneath the saturation pressure. Other PVT properties
are also greatly affected by reservoir pressure depletion.
2.5 Isothermal oil compressibility
It is the change in the fluid volume with respect to the change in pressure at
isothermal conditions, expressed in psi�1 and calculated above the bubble point
pressure from Eqs. (4 and 5).
1 dv
Co ¼ � (4)
dv dp

1 ∂Bo ∂Rs
Co ¼ � � Bg (5)
Bo ∂P T ∂P T
Oil compressibility is determined during constant mass depletion test. In that

procedure, the oil in the PVT cell is allowed to expand by reducing the pressure, and
both the increase in oil volume and the decrease in oil pressure are measured. Oil
compressibility above the saturation pressure greatly affects the material balance
calculations for estimating volumetric reserve in oil reservoirs, as well as pressure
transient analysis for under-saturated oils. Moreover, it is used in the estimation of
vertical lift performance.
2.6 Gas compressibility factor
It is a dimensionless quantity used for gas correction at higher pressures and

temperature, calculated from the basic equation of state as
PV
Z¼ (6)
nRT
2.7 Oil formation volume factor, Bo
It is defined as the ratio of oil volume either at the reservoir or separator

condition to the volume of oil at standard conditions.
ðV o Þðp;TÞres
ðBo Þres ¼ (7)
ðV o Þsc
ðV o Þðp;TÞsep
ðBo Þsep ¼ (8)
ðV o Þsc
The oil formation volume factor is expressed in units of reservoir volume over
standard volume (bbl/STB). At the surface, the oil loses the dissolved gas it
contained under high pressure and temperature in the reservoir. By pressure decline
from reservoir to surface conditions, the following scenarios are generated:
(1) The oil weight decrease owing to the loss of dissolved gas by pressure decrease;
(2) The oil volume reduced slightly owing to the temperature reduction, however,
the oil slightly expands owing to the pressure decrease. The volume reduction and
expansion due to temperature and pressure successively usually cancel each other
and no significant changes occur. Practically, (Bo) is determined from residual oil
27
volume at 60°F at the end of differential liberation. The increase in Bo above bubble
point pressure represents oil expansion by pressure decline so the oil volume at P & T
(the numerator in Eq. 8) increase and consequently Bo increase. Below bubble point,
the oil shrinkage due to gas evolving tends to overcome its expansion by pressure
reduction, consequently Bo decline steeply.
2.8 Gas formation volume factor, Bg
Defined as the ratio of the gas volume at the temperature and pressure of any
stage below the bubble point and the volume of the same gas at standard conditions
# Property Input parameters
1 Bubble point pressure (Pb) Reservoir temperature (Tres); API; gas solubility (Rs); the
specific gravity of the solution gas (γg); oil specific gravity
(γo); separator gas gravity (γg sep); reservoir pressure (Pres);
separator pressure (Psep); separator temperature (Tsep)
2 Crude oil gravity (API) The specific gravity of the solution gas (γg); oil specific
gravity (γo)
3 The specific gravity of the solution Separator GOR (Rsp); separator gas gravity (γsep); GOR from
gas (γg) the stock tank (Rst); gas gravity from the stock tank (γst)
4 Oil density (ρo) The molecular weight of the stock tank oil (MSTO); API;
gas solubility (Rs); the specific gravity of the solution gas
(γg); reservoir temperature (Tres); reservoir pressure (Pres)
5 Gas solubility (Rs) Reservoirtemperature(Tres);reservoirpressure(Pres);oil

density(ρo);API;thespecificgravityofthesolutiongas(γg);
oilspecificgravity(γo);separatorpressure(Psep);separator
temperature(Tsep);oilformationvolumefactor(Bo)
6 Oil formation volume factor (Bo) Reservoir temperature (Tres); reservoir pressure (Pres);
oil density (ρo); API; specific gravity of the solution gas
(γg); oil specific gravity (γo); separator pressure (Psep);
separator temperature (Tsep); isothermal compressibility
(Co); bubble point pressure (Pb); gas solubility (Rs)
7 Isothermal Above bubble Reservoir pressure (Pres > Pb); oil density (ρo); API;
compressibility point (Pb) specific gravity of the solution gas (γg); separator pressure
(Co) (Psep); separator temperature (Tsep); bubble point pressure
(Pb); gas solubility at the bubble point pressure (Rs)
Below bubble Reservoir temperature (Tres); reservoir pressure (Pres

point (Pb) < Pb); API; specific gravity of the solution gas (γg); oil
specific gravity (γo); oil formation volume factor (Bo);
gas formation volume factor (Bg); bubble point pressure
(Pb); gas solubility (Rs)
8 Oil viscosity (μo) Dead oil viscosity Reservoir temperature (Tres); API
(μod)
Saturated oil Reservoir temperature (Tres); reservoir pressure (Pres); API;

viscosity (μob) specific gravity of the solution gas (γg); oil specific gravity
(γo); bubble point pressure (Pb); gas solubility (Rs); oil
density at bubble point (ρob); dead oil viscosity (μod)
Under-saturated Reservoir pressure (Pres); API; bubble point pressure

oil viscosity (μou) (Pb); gas solubility (Rs); dead oil viscosity (μod);
saturated oil viscosity (μob)
Table 2.
Major input parameters for PVT equations.
28
through differential liberation (Eq. 9). Bg can also be calculated from composition
analysis as a function of Z-factor as stated in Eq. 10.

V g P, T
Bg ¼ (9)
V g sc
0:028269Z ðT ÞR
Bg ¼ (10)
ðPÞpsia
2.9 Crude oil viscosity
It is defined as the resistance of the fluid to flow, expressed in centipoise (cp). It

is affected by the oil composition, GOR, and reservoir temperature. Oil viscosity
represents internal dynamic fluid friction relevant to fluid layers. Higher and lower
viscosity depends on the gas/oil ratio. The behavior of viscosity is similar to that of
density since oil viscosity shrinks with pressure decrease, owing to reduced friction
between fluid layers, and reaches its minimal at the saturation pressure. With
further pressure depletion more and more gas escaped from the oil, so the oil
becomes denser and more viscous owing to loss of lighter components. Practically
oil viscosity is measured by falling ball viscometer.
Table 2 summarizes some of the input physical parameters used to characterize
black oil reservoirs.
3. Experimental PVT analysis
Crude oil samples can be obtained from downhole using a wireline sampling
chamber, or at the separator, using separation facilities [19]. To carry a successful
PVT analysis, the samples should be generated through the following procedure:
3.1 Sample handling
The pressurized liquid sample is heated to 200°F and stabilized in single phase
prior to removal of any sample in order to ensure sample integrity and avoid any
wax precipitation.
3.2 Sample validation
Carried out for both surface and bottom hole samples to ensure that no leakage
occurs for the samples and the fluid virtually represents the reservoir.
3.2.1 Surface samples obtained from separator
They are subjected to assuring cylinders integrity during transportation through

measurement of opening pressures of the separator oil cylinder and separator gas
cylinder at ambient temperature and separator temperature. If the measured pres-
sure equals the separator pressure, the sample is valid, otherwise, the sample is
invalid. Moreover, quality control of separator samples carried out through mea-
surement of the saturation pressure (bubble point) of the separator oil sample at the
separator temperature and compared with the separator pressure. The sample was
then transferred to the Lab cylinder, and the amount of water if present in the
separator oil was determined, and discharged.
29
3.2.2 Bottom hole sample
Also, check cylinders’ integrity during transportation and sampling carried out
by measurement of sample opening pressures at transferring temperature and
reservoir temperature. The sample cylinder was then agitated and transferring to
Lab cylinder at reservoir temperature and pressure of 1000 psi above reservoir
pressure.
3.3 Primary study
3.3.1 Surface samples obtained from separator
A primary study carried only for surface samples is as follows:
3.3.1.1 Atmospheric flashing of separator oil
A portion of the separator oil sample was charged to a high-pressure visual PVT
cell and thermally expanded to the separator temperature till equilibrium. The
sample was subjected to flash separation from separator conditions to standard
conditions of 14.73 psia and 60°F. Dissolved gas-oil ratio and oil formation volume
factor were calculated using the volumetric data obtained so that the supplied stock-
tank oil rate could be adjusted to separator oil rate for the well-stream calculations.
The density and API gravity of the stock-tank oil were also measured using density
meter. The dissolved gas composition was determined using extended gas chroma-
tography and the flashed liquid by high-resolution capillary gas chromatography.
The two analyses were then mathematically recombined according to the dissolved
gas-oil ratio to get the composition of separator oil. Figure 3 illustrates the primary
study procedure.
Figure 3.
Diagram of the primary study steps.
30
3.3.1.2 Composition analysis of stock-tank oil
The compositions of paraffins and aromatics in liquid samples were determined

using Clarus 500 Perkin Elmer Gas Chromatograph connected with flame ioniza-
tion detector (FID) using selective PIONA capillary column of 100 m in length and
0.25 mm internal diameter. Suitable sample capacity was injected into split /
splitless injector through a microsyringe according to both response and linear
range of FID detector. Nitrogen gas was used as carrier gas at its optimum flow rate.
The system enables to detect the composition up to C36+. Further oil analysis
includes density, viscosity, pour point, and distillation analysis, in addition to
water, basic sediment (BS) and sulfur contents, in order to determine the oil
quality.
3.3.1.3 Gas composition analysis
The analysis of both separator gas and dissolved gas were determined according
to ASTM 1945, using Clarus 500 PerkinElmer Gas Chromatograph online with the
condensate cell utilizing four packed columns connected in series with thermal
conductivity detector and DP-1 capillary column matched with flame ionization
detector. Helium was used as carrier gas and the oven isothermal temperature 100°C
in order to provide highly efficient detection of aromatics and hydrocarbons paraffin
(normal and iso) from methane (C1) up to undecane (C11) components and non-
hydrocarbons including H2S, CO2, and N2. Once repeatability is verified, the vali-
dated bottle generated to proceed the complete PVT analysis, which, in the case of
the reservoir fluid be a black oil, is composed by three main assays; constant mass
depletion (CMD), differential liberation (DL), and separator test.
3.3.1.4 Measurement of density
The density of oil is measured by Anton Paar Density Meter. The density
meter is calibrated with air and distilled water. The procedure reference is ASTM
D-4052.
3.3.1.5 Measurement of molecular weight
The average molecular weight number is determined by using cryoscopy,

(freezing point depression of benzene).
3.3.1.6 Corrected and adjustment of field separator GOR
Adjustment of field GOR carried out in the lab through the following equations,
owing to higher deviations of the measured field gas deviation factor (Zf)

ρf � Z f 0:5
corrected separator GOR ¼ field GOR � (11)
ρl � Z l
0:5
1
Zf ¼ (12)
fpv
corrected separator GOR
adjusted separator GOR ¼ (13)
Bo
31
Figure 4.
Hofmann QC-plot.
3.3.1.7 Quality control of primary study
Carried out by applying Hoffmann method to data of separator oil & gas
through plotting of (Ki Psep) against [1/Bi(1/Tbi � 1/Tsep)] on a Cartesian scale which
results in a straight line, as shown in Figure 4.
where,
yi
Ki ¼ (14)
xi
Bi ¼ log ðPci =14:7 Þ=ð1=T bi � 1=T ci Þ (15)
3.3.1.8 Physical recombination of well stream
The samples were physically recombined at separator conditions (Psep & Tsep)
using the corrected separator (GOR), (Bo) and (Bg) to form the wellstream. The
wellstream composition can mathematically be determined by applying material
balance equation to the separator product compositional analysis and their physical
properties such as corrected separator GOR, dissolved GOR, Bo, the density of stock
tank oil, separator oil and gas densities as well as Bg.
3.3.2 Bottom hole sample (BHS)
A known portion of the reservoir fluid was charged from (BHS) cylinder to a
high-pressure visual cell and thermally expanded to the reported reservoir temper-
ature and pressure. After establishing thermal equilibrium, the fluid sample was
subjected to a flash separation at standard conditions (P = 14.7 psia & T = 60°F).
The flashed data were then checked using Hoffmann method.
3.4 Constant mass depletion (CMD)
An integrated and automated mercury free system (PVT-cell) is used for PVT
analysis of black-oil and volatile oil. A portion of the sample is pumped into the cell,
and the volume and, therefore, pressure of the sample chamber are controlled with
a piston. Most sample chambers are equipped with a magnetic stirrer to ensure that
the system is well mixed. Constant mass depletion also known as flash liberation, in
which a set of volume measurements as a function of pressure at fixed reservoir
32
temperature are performed within the PVT cell. The recombined well stream was
pressurized and heated to reservoir temperature and pressure. A portion of the
sample (100 cc of live oil) was charged to a high-pressure visual PVT cell and
thermally expanded to the reservoir temperature and the pressure was adjusted
to a pressure of 1000 psi higher than the reservoir pressure. The measurements of
pressures and volumes were recorded and then used to determine the bubble
point pressure of the under-saturated reservoirs at reservoir temperature. Above
bubble point pressure, the relative volume, oil formation volume factor, oil
compressibility, density, and viscosity were determined, while below bubble point
pressure the Y-Function is calculated at each pressure step.
3.5 Differential liberation (DL)
After the constant composition mass depletion, the sample was pressurized and
equilibrated to a single phase condition. A differential vaporization procedure is
then performed for the purpose of measuring two-phase properties as a function of
reservoir pressure depletion. As with the flash expansion test, the volume of the
sample chamber is increased incrementally; however, in this case, the evolved
solution gas is withdrawn from the sample chamber after each incremental expan-
sion. At each pressure depletion, the oil formation volume factor, gas formation
volume factor, two-phase volume factor, gas gravity, gas solubility, density, and
viscosity were determined. The viscosity of the evolved gas is usually calculated
through Lee et al. correlations rather than measured. While the viscosity
Figure 5.
Schematic illustration of (a) constant mass depletion and (b) differential liberation [6].
33
Figure 6.
Multistage separator test.
measurement for both live and dead oil is carried out over a wide range of high
pressure and temperature by a rolling ball viscometer (RUSKA). Schematic repre-
sentation of CMD and differential liberation are shown in Figure 5.
3.6 Separator test
Separator test is used to determine the effect of surface separation parameters on

the gas-oil ratio, stock tank oil gravity and formation volume factor at separator
conditions. About 100 cc of the recombined sample is raised to the saturation
pressure at the reservoir temperature. Then the sample condition is lowered and
adjusted to the separator conditions, where the oil and gas volumes are measured. In
presence of the second separator, the sample is adjusted to the second separator
temperature and pressure, where the oil and gas volumes are also measured. After
testing all separator stages, the sample is flashed to stock tank conditions, where the
volumes of stock tank oil and gas are monitored. The separator test volumetric data
and the compositional analysis of the evolved gases from each pressure stage are
reported. The separator test data were then used to adjust differential vaporization
result to the surface conditions used in the separator test. Schematic representation
of the multistage separator test is represented in Figure 6.
4. PVT correlations and software
Numerous correlations to calculate PVT properties for oils have been developed.
The correlations are usually simple expressions (equations) that allow engineers to
calculate the PVT properties from readily available inputs in case of absence of
experimentally measured data. Correlations are generated from PVT Datasets asso-
ciated with the particular geographical region. The most commonly known geo-
graphical correlations are Al-Marhoun [20] correlations for Saudi Arabian crudes;
Standing [21] for California crudes; Petrosky [22] for Gulf of Mexico crudes;
Hanafy et al. [23] for Egyptian crudes; and Omar and Todd [24] for Malaysian
crudes. Some developed correlations use common oil samples of worldwide origin.
The correlation is usually developed by fitting a predetermined form of an equation
(or more) with the measured data and calculating the equation(s) parameters by
use of multiple regression analysis. It is essential to note that the accuracy of
correlation performance and applicability is associated with the range of data used
in correlation development. PVT correlations developed as a function of PVT prop-
erties, or as groups of correlations developed from the same dataset for several PVT
properties. Table 3 gives a detailed survey on the published PVT correlations.
Numerous software were developed for prediction of PVT phase behavior and
physical properties such as PVTp, PVTsim, Eclipse E100, Eclipse E300, Petrel, and
Ecrin. A detailed description of this software will be described elsewhere.
34
Correlation name Pb Rs Cob Bob ρob μob Cou (GOR)STO Bou μou μod
Abdul-Majeed and Salman [25] ✓
Abdul-Majeed et al. [26] ✓ ✓
Abu-Khamsim and Al-Marhoun [27] ✓
Ahmed [28] ✓ ✓ ✓ ✓
Ahmed [29] ✓
Al-Khafaji et al. [30] ✓ ✓ ✓
Al-Marhoun [31] ✓
Al-Marhoun [20] ✓ ✓
Al-Marhoun [32] ✓ ✓ ✓ ✓
Al-Marhoun [33] ✓ ✓
Al-Marhoun [34] ✓
Al-Mehaideb [35] ✓ ✓ ✓ ✓ ✓
Al-Najjar et al. [36] ✓ ✓
Al-Shammasi [37] ✓ ✓ ✓
Andrade [38] ✓
Frick [39] ✓
Asgarpour et al. [40] ✓ ✓
Asgarpour et al. [40] ✓
Beal [41] ✓ ✓
Beggs and Robinson [42] ✓ ✓ ✓
Bennison [43] ✓
Bergman [44] ✓ ✓ ✓
Bergman and Sutton [45] ✓
Sutton and Bergman [46] ✓ ✓
Bolondarzadeh et al. [47] ✓ ✓
Calhoun [48] ✓
Casey and Cronquist [49] ✓ ✓
Chew and Connally [50] ✓ ✓
De Ghetto et al. [51] ✓ ✓ ✓ ✓ ✓ ✓
Dindoruk and Christman [52] ✓ ✓ ✓ ✓ ✓ ✓ ✓ ✓
Doklah and Osman [53] ✓ ✓ ✓
Elam [54] ✓ ✓
El-Banbi et al. [55] ✓ ✓
Elmabrouk et al. [56] ✓ ✓ ✓
Elsharkawy and Alikhan [57] ✓ ✓ ✓ ✓ ✓
Elsharkawy and Alikhan [58] ✓ ✓
Elsharkawy and Gharbi [59] ✓
Farshad et al. [60] ✓ ✓ ✓ ✓
Fitzgerlad [61] ✓
Glaso [62] ✓ ✓ ✓ ✓ ✓ ✓
35
Hanafy et al. [23] ✓ ✓ ✓ ✓ ✓
Hassan [63] ✓ ✓
Hemmati and Kharrat [64] ✓ ✓ ✓
Hossain et al. [65] ✓ ✓ ✓
Ikiensikimama et al. [66] ✓ ✓ ✓ ✓ ✓
Ikiensikimama and Azubuike [67] ✓
Ikiensikimama and Ogboja [68] ✓ ✓ ✓
Karimnezhad et al. [69] ✓ ✓
Kartoatmdjo and Schmidt [70] ✓ ✓ ✓ ✓ ✓ ✓ ✓
Kartoatmdjo and Schmidt [71] ✓ ✓ ✓ ✓ ✓ ✓ ✓
Kaye [72] ✓
Khairy et al. [73] ✓ ✓
Khamehchi et al. [74] ✓ ✓ ✓
Khan et al. [75] ✓ ✓ ✓
Khazam et al. [76] ✓ ✓ ✓ ✓ ✓ ✓ ✓
Knopp and Ramsey [77] ✓ ✓
Kouzel [78] ✓
Labedi [79] ✓ ✓ ✓ ✓ ✓ ✓ ✓
Labedi [80] ✓ ✓
Labedi [81] ✓ ✓ ✓ ✓
Lasater [82] ✓ ✓
Levitan and Murtha [83] ✓ ✓
Macary and El Batanony [84] ✓ ✓ ✓
Mazandarani and Asghari [85] ✓ ✓ ✓
McCain [14] ✓ ✓ ✓ ✓ ✓ ✓ ✓ ✓
McCain et al. [86] ✓ ✓
Mehran and Movagharnejad [87] ✓ ✓
Moradi et al. [88] ✓
Moradi et al. [89] ✓
Mehran and Movagharnejad [87] ✓
Naseri et al. [90] ✓ ✓ ✓
Naseri et al. [91] ✓
Ng and Egbogah [92] ✓
Obomanu and Okpobiri [93] ✓ ✓
Okeke and Sylvester [94] ✓
Okoduwa and Ikiensikimama [95] ✓
Omar and Todd [24] ✓ ✓
Osorio [96] ✓
Ostermann and Owolabi [97] ✓ ✓
Owolabi [98] ✓ ✓
36
Oyedeko and Ulaeto [99] ✓
Petrosky [22] ✓ ✓ ✓ ✓ ✓ ✓ ✓
Petrosky and Farshad [100] ✓ ✓ ✓ ✓ ✓ ✓ ✓
Petrosky and Farshad [101] ✓ ✓ ✓
Petrosky and Farshad [102] ✓ ✓ ✓ ✓ ✓ ✓ ✓
Rollins et al. [103] ✓
Sattarina et al. [104] ✓
Spivey et al. [105] ✓
Standing [21] ✓ ✓ ✓ ✓ ✓ ✓ ✓ ✓
Standing [106] ✓ ✓
Standing [107] ✓ ✓ ✓ ✓ ✓ ✓ ✓
Sim [108] ✓ ✓ ✓ ✓
Sulaimon et al. [109] ✓
Twu [110] ✓
Oyedeko and Ulaeto [99] ✓
Valko and McCain [111] ✓
Vasquez and Beggs [112] ✓ ✓ ✓ ✓ ✓
Velarde et al. [113] ✓ ✓
Whitson and Brule [4] ✓
Table 3.
Summary of the published PVT correlations.
5. Conclusion
PVT studies are very critical and precious for reservoir engineers to monitor the
phase behavior of petroleum fluids and generating material balance calculations.
Traditionally, PVT experiments are carried out through high pressurized PVT-cell,
but in case of unavailability of experimental facilities, we resort to empirically
derived correlations. Several empirical correlations were published depending on
geographical provinces. In this chapter, a brief description of the phase diagram for
black and volatile oil was introduced as well as the importance of PVT properties in
predicting petroleum fluids behavior. Then PVT physical parameters and its mean-
ings were briefly illustrated and a summary of the input parameters in their pre-
dictions as well as a survey of the published correlations were provided. Moreover, a
detailed description of the experimental PVT procedures and tests were illustrated
to help engineers and analysts in conducting such tests.
Nomenclature
(GOR)STO stock-tank gas/oil ratio

μob saturated oil viscosity (at or below bubble point)
μod dead oil viscosity correlations
μou under-saturated oil viscosity
bbl/STB barrel/stock tank barrel
37
Bg gas formation volume factor

Bo oil formation volume factor, bbL/STB
Bob oil formation volume factor at the bubble point
Bou under-saturated oil formation volume factor
Co oil compressibility
Cob saturated oil compressibility (at or below bubble point)
Cou under-saturated oil compressibility (above bubble point)
GOR producing gas-oil ratio
Ki the equilibrium constant of component i in the recombined sample
N number of separators
Pb bubble point pressure
Pci critical pressure of component i in the recombined sample
PVT pressure-volume-temperature
Rs gas solubility
Rsp separator GOR, scf/STB
Rst GOR from the stock-tank, SCF/STB
Scf/STB standard cubic foot/stock tank barrel
Tbi true boiling point temperature of component i in the recombined
sample
Tci the critical temperature of component i in the recombined sample
xi the mole fraction of component i in the separator oil
yi the mole fraction of component i in the separator gas
Z gas compressibility factor
Zf gas compressibility factor measured at the field
Zl gas compressibility factor measured at PVT lab
γg solution gas specific gravity
γsep separator gas gravity
γst gas gravity from the stock-tank
ρf gas gravity measured at the field
ρl gas gravity measured at PVT lab
ρob oil density at the bubble point
Author details
Abdelaziz El-Hoshoudy1,2* and Saad Desouky1
1 Production Department, Egyptian Petroleum Research Institute, Naser City,

Cairo, Egypt
2 Faculty of Energy and Environmental Engineering, British University in Egypt,

Elshorouk City, Cairo, Egypt
–NC
38
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Chapter 4
Pumping System of Heavy Oil

Production
Tarek Ganat
Abstract
The geological features of the hydrocarbon reservoir and the inconsequential

mobility of the heavy oil make the recovery process challenging. Recently,
commercial interest has been developed in heavy oil production systems with the
advent of improved drainage area by drilling multilateral and horizontal wells and
highly deviated wells at shallow reservoirs. Moreover, other new recovery methods
were developed such as downhole technologies that include cold or thermal pro-
duction. Commonly, artificial lift techniques are utilized when the well cannot
offload naturally at its economical rate. This is applicable for heavy oil reservoirs,
where high viscosity along with the reservoir pressure drop will avoid the wells to
produce naturally. Producing heavy oil together with associated water from the
reservoir can create emulsions, which may cause high loads on artificial lift
methods, along with high power consumption and requirements of expensive
chemicals. The optimization and the selection of handling viscous oils; had a fun-
damental impact on the development of pimps. This chapter reviews the applica-
tions and types of pumping systems as an artificial lift in the heavy oil production
process and reviews the pumping system performance, and its future development,
as well as the expected technical challenges.
Keywords: artificial lift, pump systems, multiphase flow, heavy oil, oil recovery
1. Introduction
Globally, the heavy oil reserves have become more important as a future energy
source. An excess of 50% of the world’s hydrocarbons have an oil gravity of
<20° API. These hydrocarbon assets are normally bitumen and heavy oil, where
most of these deposits are located in China, Canada, Venezuela, and Russia. Typi-
cally, the heavy oil viscosity is varied within the range of 500 and 15,000 cP, and for
bitumen, it’s about 100,000 cP. Such crudes are usually found in shallow reservoirs
(300–600 m depths), and normally the average flow rate of an individual well can
be from 1 to 70 m3/day. Therefore, to reach economic production rates, all oil wells
need to be pumped at low bottom-hole pressures. Besides, hydrocarbons are
typically produced from unconsolidated reservoirs which are susceptible to sand
production that can exceed above 30% by volume.
Typically, 60% of producing oil wells need some additional lift systems to pump
the reservoir oil. Conventionally, heavy oil wells are using beam pumping as an
artificial lift system. However, beam pump is used for low flow rate wells; besides
this pump has many operating problems. Alternatively, there are many types of
47
pumps which are recently employed as a primary option in heavy oil wells, such as
progressing cavity pump (PCP), jet pumps, and electric submersible pump (ESP).
These wells are normally producing at low bottom-hole pressure, low gas-oil ratio,
and low bubble-point pressure, high water-cut, or low °API oil gravity. This chapter
reviews the application of different pumping systems as an artificial lift in the heavy
oil production process. The main focus of the chapter is on types of pump and
their applications and reviews the pumping system performance, and its future
development, as well as the expected technical challenges.
2. Production of heavy oils
Heavy oil production is a developing skill for producing heavy oil in economical
amounts. There are several ways to produce heavy oil and bring to the surface such
as primary, secondary, and tertiary recovery. Since oil mobility is a function of
effective permeability and oil viscosity, the efficiency of a well production is related
to the delivery of reservoir zone thickness and mobility [2]. Figure 1 displays the oil
recovery mechanism as identified by Pinczewski [3] and Ershagi (1994) [c], and
Figure 2 shows the expected recovery factor from every method. The enhanced oil
recovery (EOR) processes can be categorized into three main groups as stated
below. The approaches have their own characteristics and mostly linked to the kind
of oil remaining in the reservoir and reservoir characteristics.
1. Chemical
a. Surfactant flooding
b.Micellar polymer flooding
c. Polymer flooding
d.Alkaline atau caustic flooding
Figure 1.
Oil recovery mechanism (source: Pinczewski (1993)) [3].
48
Figure 2.
Oil recovery from each stage (source: DALEEL) [4].
2. Thermal
a. Steam flooding
b.Fire flooding
3. Miscible
a. Carbon dioxide flooding
b.Nitrogen and flue gas flooding
c. Enriched hydrocarbon gas flooding
Things that are essential to be considered in the EOR method
1. Physical properties
2. Reservoir type
3. Structure and physical properties of porous media
4.Fluid condition in porous media
5. Mobilization of oil remaining
6. Adsorption process
2.1 Primary recovery
2.1.1 Natural flow
The first oil extraction process from the reservoir rock is known as primary
recovery (utilizing the natural energy). It’s the first production phase of hydrocar-
bons, where the well depends on the natural flow of the oil because of pressure
differences between reservoir pressure and the well bottom-hole pressure. Besides,
using pumping lift systems such as an electrical submersible pump is also known as
49
a primary recovery technique. These approaches are normally named as natural

drive mechanism. The recovery factor from conventional oil production is above
30%, but for heavy oil, it is within 5–10% [5]. When natural lift pressure is not
enough to move the oil to the wellbore or to lift the oil to the surface, once the
reservoir depleted, then the primary recovery stage has reached its maximum
extraction limit. Normally, heavy oils cannot be produced via natural flow from the
reservoir to surface. There are some heavy oil wells which that can be produced
naturally, but at a very low production rate (20 stb/d), with recovery factor
within the low range of 6–9% of the oil in place; specific to densities ranging
between 9 to 20° API, and viscosities range from 1000-13,000 cP or more, together
with low reservoir pressures.
2.2 Secondary recovery
Once primary recovery methods seize to produce the oil naturally, secondary
recovery methods will kick off which is the next phase of producing the oil from the
reservoir and to bring the oil to the surface. Basically, these approaches include
injecting additional energy sources (supplementary energy) into the reservoir to
maintain and increase the reservoir pressure. These artificial approaches contain
natural gas reinjection, water injection, and CO2 injection as show in Figures 3 and 4.
With time the artificial pressure loses efficiency as the residual heavy oil is extremely
viscous to flow and is detained by sandstone in the reservoirs [6]. The total recovery
factor of the heavy oil including the primary recovery approaches will be within the
range of 10–25% [7].
Figure 3.
Enhanced oil recovery using CO2 injection (source: NETL (2010)) [8].
50
Figure 4.
Illustrating waterflooding technique of secondary recovery (source: NETL (2010)) [8].
2.3 Tertiary recovery
Tertiary recovery is generally denoted as enhanced oil recovery. It is an

approach of extracting oil through thermal and nonthermal processes after most of
the oil has been extracted by primary and secondary recovery methods [9]. Mainly,
EOR is used to extract the heavy oil trapped in porous media of reservoir rock which
is too viscous to flow. The most common approaches for tertiary recovery are
thermal, chemical, and miscible enhanced recovery.
For nonthermal approaches, chemicals and microbes are used to release trapped
heavy oil and carbon dioxide under pressure. However, thermal approaches are
generally steam injection which is the most effective means of decreasing viscosity
and mobilizing heavy oil [7].
2.4 Thermal methods of recovery steam-based processes
2.4.1 Steam injection
Steam injection is commonly used for high viscous oil. The main objective of the
steam injection is to heat up and force the oil to the wellbore by the pressurized steam
depicted in Figure 5. Generally, the EOR methods are costly because of the required
external energy resources and materials. Consequently, the volume of heavy oil to be
extracted from a reservoir rock is a function of economics [10]. As a result of this,
engineers must start to study in more details the reservoir rock permeability, pore
media, and oil viscosity, together with the reservoir heterogeneity, where all these
issues affect the success of any recovery technique. Overall steam injection efficacy is
the product of the sweeping capability and displacement competence.
2.4.2 Cyclic steam stimulation
Cyclic steam stimulation (CSS) is one of the main EOR approaches for heavy oil
production. The notion of the CSS is that the steam is injected into the reservoir via
a production well for a period of time. Then the well is closed and permitted to soak
by steam for some period of time before it returns to production. CSS was applied in
51
Figure 5.
Illustrating the thermal flooding technique (source: Steam EOR 1.Jpg (2008)) [8].
many heavy oil wells in the Middle East. Various cycles were done in these wells.
However, the total amount of produced water for each cycle was considerably less
than estimated.
2.4.3 Steam-assisted gravity drainage
Steam-assisted gravity drainage (SAGD) comprises pairs of a high-angle injec-

tion wells with an adjacent production well drilled along a parallel trajectory
depicted in Figure 6. Normally, steam is injected via the upper well. Once the steam
rises and spreads, it will heat up the heavy oil trapped in the porous media,
decreasing its viscosity. Then assisted by the gravity forces, the oil will be drained
into the lower well where it is produced [11]. Generally, the steam injection involves
two core approaches, cyclic steam injection, and steam flooding.
2.4.4 Cyclic steam injection
The fundamental idea of the cyclic steam injection (CSC) is to inject hot steam
through a single well for a period of time. A CSC method contains three phases (see
Figure 7). The first phase is injection, through which a slug of steam is injected into
the reservoir. The second phase requires that the well is shut for some days to permit
equal heat spreading to thin the oil. Finally, throughout the third phase, the thinned
oil is produced over the same well. The same cycle process is repeated many times as
far as oil production is still profitable. Commonly, the cyclic steam injection process is
used widely in heavy oil reservoirs and tar sands and also can be used to enhance
injectivity prior to steam flood process and in combustion processes. Steam injection
52
Figure 6.
Illustrating steam-assisted gravity drainage (source: Markham Hislop (2017)) [12].
Figure 7.
Cyclic steaming processes. First, steam is injected at high pressure; second, the steam thins the viscous oil; and
third, the oil is produced up to the surface (source: Lyz Hoffman (2014)) [13].
is typically used in both horizontal and vertical wells producing high viscosity as high
as 100,000 cP. Normally in CSC wells, oil can be both viscous and solid. Usually, CSC
is termed “steam soak” or the “huff ‘n puff” (slang) technique. Normally, CSC
recovery factor is within the range of 10–20% of the initial oil in place [13].
53
2.4.5 Continuous steam injection (steam flooding)
Continuous steam injection is a new method to manage heat flow in the reservoir
and to decrease the temperature of the fluids at production wells in that way
avoiding shut-in made by high temperature (Figure 8). The best injection plan with
different pressure and fixed steam quality has shown to have the biggest oil recov-
ery given the same quantity of energy injected under various reservoir sets. Steam is
injected at high temperature and high pressure via an injector well. The oil recovery
of this technique is more than the cyclic steam injection method, and it’s more
practical and efficient. It has lower thermal efficacy than CSC and needs a larger
surface area. This method needs one well for steam injection and another well for oil
production [15]. Typically, the recovery factor of the steam flooding method is
about 50% of the initial oil in place [9].
2.4.6 Combustion processes
The combustion process, also referred as fire flooding, challenges the recovery
of more heavy oil by a flare-up of a part of the oil in place by injecting either
oxygen, air, or chemical or by electrical shock (see Figure 9). This decreases the
heavy oil viscosity and heats the oil in place, and the oil is moved out by a combi-
nation of steam, hot water, and gas drive. This method appeared always to be very
suitable, mainly when we need to recover bitumen from tar sand deposits.
Normally, the temperature of the combustion process can reach up to 700°C. This
temperature can be observed at the combustion front [17–23]. Typically, the com-
bustion technique is applied to hydrocarbon reservoirs of low API gravity oil. By
using the combustion method, the heavy oil gravity can be upgraded from 2 to
6° API (Ramey et al., 1992). Forward combustion includes a drive of the burning
front in a similar direction as the injected air; where the reverse combustion
includes a drive of the burning front opposite to the direction of the injected air.
Figure 8.
Diagram shows steam flooding (source: Alhakiki (2012)) [16].
54
Figure 9.
Schematic of combustion processes (source: Rob Kendall (2009)) [23].
Figure 10.
Schematic of downhole diluent injection method (source: Arnaud Hoffmann (2016)) [25].
2.5 Downhole diluent injections for a heavy oil field
Many previous studies proved the diluent injection with ESP can be an efficient
artificial lift method for heavy oil reservoirs. It consists of injecting a light hydro-
carbon liquid to reduce the oil density and viscosity depicted in Figure 10. This
recovery method makes use of several kinds of diluents injected downhole to
decrease heavy oil viscosity in the reservoir. Normally the diluents used such as
kerosene, naphtha, and light oil or may be injected into the drain and blended with
heavy oil. Numerous field experiences show that the use of diluents allows the
viscosity of the heavy oil to decrease from 100,000 to <1000 cP. The diluted fluid
is then returned back to the surface by a downhole pump such as progressive cavity
pumps (PCP). There are many diluent injection operations that extracted heavy oil
of 7.5–9° API. The API quality of heavy oil has been upgraded to high commercial
quality (32° API). For instance, a case study for extra heavy oil is produced from the
1300 meter horizontal section through downhole ESP pumps. The diluent fluid used
has 46° API gravity of naphtha. In the diluent fluid injected at the bottom of the
slotted liner, the diluent fluid transfers gradually in the horizontal part of the drain
55
through the influence of the pressure differential created by pump process. The
heavy oil gradually moves from the reservoir to the liner and reaches the pump
intake section with decreased heavy oil viscosity that is suitable for the pump
efficiency. The heavy oil viscosity at reservoir conditions was 10,000 cP at 50°C,
but once mixed with 20% naphtha, the viscosity value decreased down to 200 cP.
The mixed pumped fluid viscosity can be simply attuned by the rate of diluent
injected downhole through the injection line.
3. Artificial lift systems
Well artificial lift plan is a strategic aspect in the production of heavy oils.
Obviously, some types of artificial lift was required in order for the oil to flow and
return the flow rate of the oil to their normal rates to maximize the ultimate oil
recovery. The choice of which artificial lift technique is to be used is very significant
for the long-term profitability of the oil field. An inappropriate selection of artificial
lift can decrease production and raise the operating cost significantly. After a
decision has been taken, it can be hardly changed whether or not the technique
selected was suitable for the existing conditions.
The selection procedure of the lifting method to be used, which are confined to
the operating life of surface and downhole equipment, maintenance, environmental
concerns, and cost. Therefore, there are several configurations of downhole oil
pump systems including pumps and drivers as described below.
3.1 Hydraulic pumping systems
Hydraulic pumping is one of the artificial lift methods used since the early 1930s.
Hydraulic pumping systems can be used at different oil well production conditions
(Figure 11). This type of pump was installed at different setting depths ranging
from 400 to 20,000 ft. with varying production flow rates from 80 to more than
20,000 STB/D. The pump has surface speed drive box ranging from 15 to 625 hp.
which makes the downhole pumping rate to be controlled on the surface.
The basic operating process of the pump is that the power fluid is pumped from
the surface facilities to activate the downhole piston together with a reciprocating
piston pump (refer to Figure 12). The power fluid acts on a piston like a steam
engine, and the power fluid could be oil or water. The power fluid transfers to the
piston and returns back to surface over another pipe if a closed loop power fluid is
used. In the open power fluid design, the power fluid is combined with the produc-
tion once flowing to the surface. To control the corrosion, chemicals can be injected
downhole along with the power fluid. The advantage of using this pump is the
power fluid which can be heated for handling heavy oil. The pump is appropriate
for deviated wells which might be difficult for other artificial lift methods. The
pump surface facilities have a small footprint and can be assembled into one main
battery to service many wells. Commonly, hydraulic pumps are applied primarily in
very deep oil wells that are producing at great volumes which cannot be handled by
using beam pump systems.
3.1.1 Types of hydraulic pump systems
Generally, it can be used in low API oil gravity wells and in wells with high
paraffin contents. Also used in the wells that failed to use any other artificial lift
techniques or, because of well conditions. It’s used in deep and deviated wells
including sandy and corrosive wells. Hydraulic pumping systems are quite
56
Figure 11.
A schematic of the downhole assembly piston pump (source: Cholet H, 2004) [26].
expensive, but they may have a good application where other artificial lift tech-
niques may not be possible.
3.1.1.1 Piston pump
A piston pump includes a motor at one end and a plunger pump at the other end
(Figure 13). Hydraulic fluid is forced down the completion string at very high
pressure and goes in a reciprocating motor. The motor mechanism is piston-like
pump which is forces the produced hydrocarbons to the surface throughout the
57
Figure 12.
Diagram of hydraulic pumping surface facility system (source: SPE) [27].
Figure 13.
Hydraulic piston pumps (source: Conoco Inc., 1990 [29]).
casing annulus. Normally, the hydraulic fluid is used as a power fluid. Once both
hydraulic fluid and produced fluids reach the surface, the hydraulic fluid is
separated and reused again as the power fluid.
3.1.1.2 Jet pump
Jet pumps have been applied in the oil industry for more than 75 years. A jet
pump is one of artificial lift methods, and it can be applied when depth and
deviation of producing wells increase and reservoir pressure depleted (Figure 14).
A jet pump is used in thermal production as it’s not directly affected by the high
temperature of the fluids. This pump can considerably reduce the risk of equipment
failure in the wellbores because it has no moving parts. These pumps are in the
family of thermo-compressors, and they are categorized as “eductors” as they are
considered for a liquid to pump a liquid (incompressible liquid). The pump is set
downhole and pulled up the well for retrieval by using pressurized fluid.
58
Figure 14.
Typical jet pump system (source: Cholet H, 2004) [26].
Normally, this process is using a pump at the surface to generate high-pressure

power fluid to be transmitted downhole via tubing or through an annular casing.
The power fluid moves into the pump and goes via a nozzle, where almost the
whole pressure of the power fluid is transformed into a velocity head if no loss
happens. The velocity of the power fluid can reach up to 70 m/s from the nozzle
outlet section into the production inlet chamber linked to the pump intake section.
Both production fluid and power fluid returned back to the surface over the pro-
duction pipes. Comparing with other pump systems, hydraulic efficacies of jet
pumps are lower in the range of 20–30%. A jet pump can produce high rates and can
handle free gas as well, though it’s not as efficient as a positive displacement pump,
therefore needing higher horsepower requirements at the surface [28].
A jet pump is very suitable in specific conditions, for instance, when high
production rates are preferred. The pump is suitable for handling viscous, corrosive,
and heavy crude oils. Besides, locations where beam pumping units cannot be
installed, such as inhabited regions, offshore oil fields, and gas lift, are not accessi-
ble. The pump is attractive in horizontal, deviated, deep, and high-temperature
wells. Also, it has excellent solid-handling capabilities and has long operational life
(average of 4 years). Moreover, it has tolerance for gas and solids production, and it
has low installation and workover costs.
3.2 Beam pump systems
Beam pump is an artificial lift pumping system applying power source at a

surface to transmit the energy to a downhole pump assembly. Producing heavy oil
from shallow reservoirs using beam pump systems needs accurate design mainly for
downhole assembly to get maximum production performance and maximize the
run life.
A beam and crank assembly creates reciprocating motion in a sucker rod string
that attaches to the downhole pump assembly. The pump comprises a plunger and
59
valve assembly to transform the reciprocating motion to vertical fluid movement.

Figure 15 shows typical beam pumps.
3.2.1 Classification
The hollow sucker rod electric heating device can be divided into a pumping unit
device, subsurface pump and screw pump hollow sucker rod device. Tables 1–3
show the sucker rod electric technical data.
3.3 Progressive cavity pump systems
PCP was developed in 1930. Currently, this pump is used to produce heavy oil in
any kind of wells: vertical, deviated, or horizontal. A PCP is essentially made of two
helical gears, one inside the other (Figure 16). Table 4 displays the lift selection
guidelines. The suitable use of each lift type is reliant to the type of the reservoir
fluid, reservoir pressure, and production rate as estimated by inflow and outflow
system.
The metallic rotor is a single helical “rotating” inside the stator based on a double
helical elastomer-lined nitrile in most cases. The external gear or stator has a double
helical shape, one more than the internal single helical gear rotor. When the rotor
is rotating, the fluid transfers together with the pump axis inside the cavities
Figure 15.
Typical beam pumps (source Conoco, 1990) [29].
Rod outer diameter 34 mm 36 mm 42 mm
Rod thickness 5.0 and 5.5 mm 5.5, 6.0 and 6.5 mm 6.0 mm
Coupling outer diameter 50 mm 50 mm 60 mm
Thread size 1–9/16" 1–9/16" 1–7/8”
Grade D
Table 1.
Hollow sucker rod.
60
Heating core sectional area mm2 3 8.4 mm2
Outer diameter of cable 18–20 mm
Outer protect layer Stainless steel wire armor weave
Withstand voltage ≥2500 V
Length Underground length + ground length
Temperature-resist grade Long-time working temperature: 200°C (C grade)
Electrical performance Insulation resistance >50 MΩ, AC withstand voltage test 2500 V
Tensile strength ≥50 Mpa
Table 2.
Heating cable.
Rated power KVA 35, 50, 75, 100, 135
Input voltage Three phase 380 V 5%，50HZ，three phase 440 V 5%, 60 HZ
Output voltage Single phase 160–900 is available
Power factor cos θ ≥ 0.95
Three phase imbalance percent ≤10%
Table 3.
Electric control cabinet.
present between the rotor and stator. The flow rate is a function of many parame-
ters, for example, pumps eccentricity, rotor diameter, length of the stator pitch, and
rotation speed. Manufacturers can provide a catalog of pumps with a wide range of
well conditions as a function of reservoir fluid types, flow rates, pressure heads, and
for any type of fluid viscosity.
PCP is normally driven at the surface, but it can be driven by a downhole
electrical submersible motor. When PCPs are driven from the surface (refer to
Figure 17), the stator is screwed at the tubing extremity, and the rotor is fixed to the
drive string of sucker rods. On the surface, the drive head, absorbing the force of
the sucker rods, is operated by an electric motor and a speed reducer. Most of the
downhole assembly is driven in this way.
The PCP pumps can operate at high efficiency for high viscosity cruds, high
sand, low productivity wells, and in horizontal and deviated wells. Besides, it has a
small footprint on the surface. Besides, the pump has some disadvantages, where
the pump has restricted production rate, lift depth, and temperature tolerance. In
the case of horizontal and deviated well profile, where malfunction can cause tubing
leaks made by wear or failure of the sucker rod drive shaft, the PCP is not allowed to
pump dry, and the completion string must be pulled out of the well to change the
pump.
3.4 Electrical submersible pump
An ESP is a centrifugal pump driven by a downhole electrical motor (see

Figure 18). ESP surface facilities contain power system and transformers and con-
nectors to the wellhead. Normally, ESP pumps are installed for high flow rates
(from 150 to 150,000 bopd) dependent on size and pressure gain and variable speed
controllers. These pumps are not suitable for very viscous untreated oil, but ESPs
can be applied to lift oil production after injection of diluents fluids (reduced the
61
Figure 16.
Progressive cavity pump (source: John Martinez (2017)) [28].
viscosity). An example of the electric submersible pump/motor assembly is given in

Figure 18. The efficiency of the pump is very dependent on the design of the flow
rate which must carefully be optimized based on the reservoir deliverability. More-
over, the wellhead of the ESP system needs to have an electric cable entering. The
downhole electrical submersible assembly contains an electrical power cable,
motor, motor protector, and centrifugal pump.
Thermal recovery offers several limitations for ESP pumps because of the high
temperature applied to the electric motor, electric parts, power cable, and pump
assemblies. ESP manufacturers present different designs for high-temperature
62
63
Rod lift Progressing cavity Gas lift Plunger lift Hydraulic piston Hydraulic jet Electric
submersible
Operating depth (ft) To 16,000 TVD To 6000 TVD To 15,000 TVD To 19,000 TVD To 17,000 TVD To 15,000 TVD To 15,000 TVD
Operating volume To 5000 BPD To 4500 BPD To 30,000 BPD To 50 BPD 50–4000 BPD 300–>15,000 BPD 200–30,000 BPD
Operating 100/500°F 75/250°F 100/400°F 120/500°F 100/500°F 100/500°F 100/400°F

temperature
Corrosion handling Good to excellent Fair Good to excellent Excellent Good Excellent Good
Gas handling Fair to good Fair Excellent Excellent Fair Good Poor to fair
Solid handling Fair to good Excellent Good Poor to fair Poor Good Poor to fair
Fluid gravity >8° API <35° API >35° API GLR required 300scf/bbl./10000 >8° API >8° API >10° API
depth
Servicing Workover or pulling Workover or pulling Wireline or Wellhead catcher or wireline Hydraulic or Hydraulic or Workover or pulling
rig rig workover wireline wireline rig
Prime mover Gas engine or Gas engine or Compressor Wells’ natural energy Gas engine or Gas engine or Electric motor
electric electric electric electric
Offshore application Limited Good Excellent N/A Good Excellent Excellent
Overall system 40–60% 40–70% 10–30% N/A 45–55% 10–30% 35–60%

efficiency
Table 4.
Lift selection guidelines (John Martinez (2017)) [28].
Figure 17.
Typical progressing cavity pumping system (source: SPE) [27].
reservoir fluids, for example, “hotline production” equipment with operating

temperature ratings up to 550°F for the power cable and motor.
3.5 Gas lift systems
Gas lift is a type of artificial lift techniques used to lower the producing bottom-
hole pressure to achieve a higher oil production rate. The principle of gas lift method
is that gas injected into the tubing string decreases the density of the fluids in the pipe
and lets the two-phase mixture to flow up to the surface. There are two main kinds of
gas lift techniques being applied today which are continuous and intermittent flow.
Typically, natural gas is continuously injector under high pressure through tubing or
through the annular between casing and production pipe into the pocket mandrels
along the production tubing. At high-temperature the multiphase flow will be pro-
duced at the surface (refer to Figure 19). Normally, gas compressor pressure and rate
parameters are modified based on the gas lift constraint depicted in Figure 20. Gas
lift is commonly used with SAGD heavy oil production in Canada.
3.5.1 Applications of gas lift
Gas lift is mainly appropriate for lifting fluids in wells that have a low amount of
gas produced with the oil. Gas compressors are almost mounted to collect the
64
Figure 18.
Typical electric submersible pump (source: John Martinez (2017)) [28].
produced gas and designed to be used for the gas lift system. The flexibility of gas
lift, in terms of production rates and depth of lift, can seldom be matched by other
methods of artificial lift if adequate injection gas pressure and volume are available.
Gas lift is very suitable for highly deviated wells which produce sand and high gas-
liquid ratios. There is no other method that suitable for through-flowline ocean-
floor completions as a gas lift system. Besides, wireline-retrievable gas lift valves
can be replaced without killing a well or pulling the tubing. Individual well
downhole tools are low-cost. The surface gas lift facilities for injection gas control
are simple and need low maintenance and nearly no space for installation. Usually,
the reported high overall reliability and lower effective costs for a gas lift method
are more to other techniques of lift.
65
Figure 19.
Diagram of injection gas cycle for gas lifting well (courtesy of Schlumberger).
Figure 20.
Diagram of a gas lift system (courtesy of Schlumberger).
66
4. Future development of pumping system performance
Pump monitoring is a crucial factor in prolonging the working life of all kinds of
downhole pump systems. Currently, it is feasible to measure the downhole and
surface pressure and temperatures using sensors that are connected to data control-
lers to decrease the risk of “pump off”: a lack of fluid to lubricate the pump,
allowing heat to build up which would damage the elastomer stator of any type of
pump. Advanced controller alarms can set parameters to reduce risk, extend pump
working life and improve the total oil produced.
The pumping system needs more development to handle the operating cost,
mainly for operation and maintenance either for single equipment or the whole
system. Regularly, oil producers are just focused on the instant demands of the
equipment, and they do not realize how the system parameters are affecting this
equipment. A system method studies for both supply and demand sides of the
system and how they can act together, shifting the attention from a single compo-
nent to the total pumping system performance. Normally, most types of pump
failure are leakage, fouling, valve failure, and cracks in pipe chains. Assessing
pumping system performance is required to solving such pump failure and finding
enhancement opportunities. In endeavoring to find out solutions or search for
techniques to develop pump performance, assessing only the components instead of
the entire pumping system can cause analysts to manage potential cost savings. For
instance, although a pump may be functioning efficiently, it could be producing
more flow than the system needs. Therefore, it is essential to evaluate system
efficacy based on how the end uses are worked by the pumps.
In the future, pumps need to be more reliable and proficient in functioning for a
long time before requiring maintenance. Pumps must be safer to work, use less
space, use less power, less noise and temperature. Additionally, the need to improve
corrosion resistance and as well as the reliability of working in the high-temperature
environment. Consequently, pumps will be friendlier to the environment and run-
ning with less power to decrease their carbon footprint. As well, the use of more
recycled materials with fewer consumables, in that way helping to decrease whole
pumps costs. Pumps are required to be easier to clean, overhaul, and reconstructed.
Generally, there are several chances to increase the reliability, performance, and
efficacy of pumping systems in the oil industry. Definitely, the next generation of
important savings for pump operators belongs to a broader pumping system opti-
mization method. This certainly needs a middle way, taking the proper mix of the
best suitable available technology combinations for certain applications.
5. Technical challenges
Engineers and facilities and pump designers will encounter enormous challenges
in developing heavy oil reservoirs, such as crude oil properties and composition,
flow assurance, lifting process, and operations.
5.1 Fluid properties and composition
Proper experimental methods are required to properly characterize heavy oil

emulsions at conditions that will come across in the actual production process.
Correctly describing the apparent viscosity of an emulsion phase is an even bigger
challenge. The viscosity of the crude could be very important description tool than
the API gravity. Transport of high viscosity crudes can be a major flow assurance
67
challenge for future developments. Skills at many fields in the design phase are
important trends in heavy crude properties and description needs. Therefore, high
oil viscosity, low reservoir energy, and cold ambient temperatures make recovery
and transport of heavy oils a challenge. Heavy crudes have a lower market value due
to low oil gravity, high sulfur content, and higher TAN numbers. Crude oil
upgrading processes have CAPEX and OPEX intensives. With the vapor extraction
process, a vaporized hydrocarbon solvent is injected into the reservoir to dilute the
heavy crude and extract the lighter components while leaving the heavier ends
behind. This technology essentially performs in situ upgrading of the heavy crude.
The possibility of organizing any upgrading process will be technically and eco-
nomically challenging.
Typically, some of the reservoirs are producing heavy oil and water. This can
create emulsions, which generate high loads on lifting systems with more chemical
and energy consumption. The capability to drive sand together with high viscosity
fluids has made the pump systems the best alternative option for managing heavy
oil production. Many challenges will meet pump designers to develop heavy oil
reservoirs that have high viscosity and low initial pressure and temperature.
Besides, heavy oil producers may face possible gas and water inflow on low-
producing mature fields.
5.2 Reservoir characterization
The main challenge related to the characterization of deepwater and heavy oil
reservoirs is that this must be accomplished with quite fewer reservoir penetrations.
This means having to address and manage more uncertainties and risks with less
information. This is a function of the greater drilling costs in deep water and the
more marginal economics of these types of developments. Fewer well penetrations
mean fewer database available such as logs, cores, tests, and fluid samples that are
very significant in characterizing, measuring, and managing heavy oil reservoir
uncertainty and risk. Consequently, deepwater heavy oil reservoirs are integrally
characterized not only by greater unit development and production costs and lower
product cost but also by greater reservoir uncertainty and well performance risk.
5.3 Impact of heavy oil on flow assurance mitigation strategies
The reservoir describes the main flow assurance challenges based upon reservoir
fluid properties, phase behavior, composition, and initial reservoir conditions. Other
ecological elements such as water depth, offset distance, ambient conditions, and
development model also influence the approaches and processes employed to control
flow assurance risks. Hydrate formation is a probability in essentially all offshore
production systems if water is existing and ambient temperatures are cool. Reservoir
fluid composition impacts the potential for wax and asphaltene problems. For steady-
state conditions, the heavy oil viscosities should be controllable with proper protec-
tion. Appropriate modeling of transient operations could pose a bigger challenge.
5.4 Operations
There are several operational concerns that are essential to be considered when
designing lift systems for viscous crudes. These contain start-up and gravity segrega-
tion. Starting up a system full of viscous heavy crude may be very challenging, if not
impossible, for most lift systems. This is particularly true in cold or deep water. For
ESPs and PCP pump systems, this has to be considered during the design phase to
certify the required horsepower is installed for start-up. Equipment failure can simply
68
happen when a downhole pump is made to turn from 0 to 3500 rpm in <1 second in a
high viscous condition. Fluid’s resistance and gravity segregation are the main prob-
lems with start-up in heavy oils in gas lift process. Even if a system may have
sufficient gas lift injection pressure to flow gas over the operating valve, it does not
offer greatly in terms of reducing the mixture density if the gas segregates to the high
side of the tubulars. The gravity segregation can cause severe slugging. Using tran-
sient multiphase simulation programs during the design phase could predict slug
volumes. Besides, the programs can propose solutions for slug mitigation. The injec-
tion of diluents may help to decrease the mixture viscosity, but some completion
components, if elastomeric, might react by swelling and losing mechanical strength.
Both gas lift equipment, ESPs, and PCPs contain elastomers, and exposure to diluents
has to be cautiously assessed during the lift selection and design process.
6. Conclusions
Internationally, the heavy oil reserves have become more important as a future
energy source. There are three techniques to produce heavy oil and bring to the surface
which are primary, secondary, and tertiary recovery. The EOR processes can be cate-
gorized into three main groups, chemical, thermal, and miscible. Commonly, artificial
lift techniques are utilized when the well cannot produce naturally at its economical
rate. This is applicable for heavy oil reservoirs, where high viscosity along with the
reservoir pressure drop will avoid the wells to produce naturally. Conventionally,
heavy oil wells are using beam pump as primary artificial lift system. However, beam
pumps are used for low flow rate wells; besides this pump has many operating prob-
lems. Alternatively, there are several pump systems currently employed as the first
option in heavy oil wells, such as PCP, hydraulic pumps, and ESP.
The pumping system needs more development to handle the operating cost,
mostly for operation and maintenance either for single equipment or the whole
system. In the future, pumps need to be more reliable and capable of running for a
long time before requiring maintenance. Pumps must be safer to work, use less
space, use less power, and have less noise and high temperature. Accordingly,
pumps will be friendlier to the environment and running with less power to
decrease their carbon footprint. Pump designers and the technology are faced with
enormous challenges in developing heavy oil reservoirs that have high viscosity and
low initial pressure and temperature. Besides, heavy oil producers may also face
possible gas and water inflow on low-producing mature fields.
Acknowledgements
The authors wish to thank the Universiti Teknologi PETRONAS, Malaysia, for
supporting this work. A special thanks to the production technology team of
PETRONAS Carigali. Last but not least, a special thanks to Mr. Taha S. Abouargub
for his generous assistance and for providing technical support, collaboration, and
words of encouragement on the success of this chapter.
The corresponding author confirms that there have been no involvements that
might raise the question of bias in the work reported or in the conclusions or
implications.
69
Author details
Tarek Ganat
Universiti Teknologi PETRONAS, Seri Iskandar, Perak, Malaysia
–NC
70
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72
Chapter 5
Modeling Friction Losses in

the Water-Assisted Pipeline
Transportation of Heavy Oil
Sayeed Rushd, Rasel A. Sultan and Shahriar Mahmud
Abstract
In the lubricated pipe flow (LPF) of heavy oils, a water annulus acts as a
lubricant and separates the viscous oil from the pipe wall. The steady state position
of the annular water layer is in the high shear region. Significantly, lower pumping
energy input is required than if the viscous oil was transported alone. An important
challenge to the general application of LPF technology is the lack of a reliable model
to predict frictional pressure losses. Although a number of models have been
proposed to date, most of these models are highly system specific. Developing a
reliable model to predict pressure losses in LPF is an open challenge to the research
community. The current chapter introduces the concept of water lubrication in
transporting heavy oils and discusses the methodologies available for modeling the
pressure drops. It also includes brief descriptions of most important pressure loss
models, their limitations, and the scope of future works.
Keywords: lubricated pipe flow, continuous water-assisted flow, core annular flow,
CFD, friction factor, data analysis
1. Introduction
1.1 Background
The reserve of nonconventional heavy oils is one of the most important

petroleum resources in the current world [1, 2]. These oils are highly asphaltic,
dense, and viscous compared to conventional oils, such as Brent and West Texas
Intermediate [3, 4]. The density is comparable to that of water, and the viscosity
can be greater than that of water by more than five orders of magnitude at room
temperature [5, 6]. This type of highly viscous oils is produced using a variety of
mining and in situ techniques [7]. After extraction, the oil is delivered from the
production site to a central processing/upgrading facility. A number of pipeline
transportation methods are available for the transportation. The conventional
transporting technologies involve viscosity reduction through heating or dilution
[1, 3, 4, 8].
The focus of the current chapter is the lubricated pipe flow (LPF) of heavy oils,
where a water annulus separates the viscous oil-core from the pipe wall. It is an
alternative flow technology, which is more economic and environmentally friendly
than conventional heavy oil transportation technologies [9, 10]. The benefit of LPF
73
is that it is a specific flow regime in which a continuous layer of water can be found
near the pipe wall. As wall shear stresses are balanced by pressure losses in any kind
of pipeline transportation, this flow system requires significantly less pumping
energy than would be required to transport the viscous oil alone at comparable
process conditions [10, 11–17].
A number of industrial scale applications of LPF are reported in the literature.
For example, a 38.9-km long lubricated pipeline having 6 inch diameter was
successfully operated by Shell for more than 12 years in California [18]. The
frictional pressure loss for this pipeline was not only orders of magnitude less than
that for transporting heavy oil but also quite comparable to the loss for transporting
water [6]. The pipeline was operated by adding up to 30 vol% water. A number of
water lubricated pipelines were used to transport heavy oil at Lake Maracaibo in
Venezuela [1]. One of the challenges the operators faced to run these pipelines was
cumulative wall fouling. Different operational measures, such as increasing water
fraction or water flow rate and changing the water composition were taken to
control the fouling. However, these measures were never sufficient to stop wall
fouling. Water lubricated pipe flow technology was also used in Spain for the
purpose of transporting heavy fuel oil [6]. Syncrude Canada Ltd. transported
bitumen froth (a mixture of 60% bitumen, 30% water, and 10% solids) from a
remote extraction plant to upgrading facility; they used a 35-km long and 36-inch
diameter lubricated pipeline [12, 19, 20]. The lubrication process in the Syncrude
pipeline produced a fouling layer of oil on the pipe wall. The thickness of the fouling
layer was approximately 5% of the pipe’s internal diameter [12, 19]. At present,
Brazilian oil producers are in the process of producing viscous oils from off-shore
reservoirs with the application of water lubricated flow in vertical pipelines [21, 22].
A concerning phenomenon during the lubricated pipe flow of viscous heavy oil
or bitumen is wall fouling [1, 3]. The probable LPF regime is presented in Figure 1.
A wall fouling layer of oil is shown to surround a water annulus lubricating the
viscous oil core. Although a number of experimental studies demonstrated the
fouling layer to be a natural and inevitable consequence of the lubrication process,
the mechanism of wall fouling in LPF has not been studied in detail [7, 12, 17, 19].
The application of LPF where the phenomenon of wall fouling must be accepted
under regular operating conditions is sometimes referred to as “continuous water
assisted flow (CWAF)” [13].
1.2 Lubricated pipe flow
Successful operation of a water lubricated pipeline is dependent on a few critical

flow conditions. The preliminary requirement for establishing LPF is the simul-
taneous pumping of heavy oil and water in the pipeline. This kind of pumping into a
horizontal pipeline can result in different flow regimes, depending upon the super-
ficial velocities and the properties of oil [18, 24, 25]. The prominent flow regimes
Figure 1.
Hypothetical presentation of the flow regime in a water lubricated pipeline [23].
74
Modeling Friction Losses in the Water-Assisted Pipeline Transportation of Heavy Oil
are dispersed, stratified flow, bubbles, slugs, and lubricated flows. The boundaries
between the flow regimes are not well defined [7, 18]. It is possible to describe
qualitatively the transition from a flow regime to the other one on the basis of
similar regime transitions in gas-liquid flow systems [13]. At lower flow rates of the
fluids, stratified flow can be expected [26, 27]. The relative positions of the oil and
water in this kind of flow regime are controlled by the effect of gravity, that is, the
difference between the liquid densities. If the density of water is higher than that of
oil, oil is to float on water and vice versa. By increasing the water flow rate, the
stratified flow regime may be transformed into bubble or slug flow. The increased
flow rate is likely to increase the kinetic energy and turbulence of the water, which
results in waves at the oil-water interface and, ultimately, transforms the stratified
oil into bubbles or slugs. Further increase in the water flow rate may split bubbles or
slugs into smaller droplets of oil. Contrariwise, increasing the oil flow rate at a
constant water flow can promote coalescence of bubbles or slugs, which may
produce the water lubricated flow regime [24, 25].
The minimum velocity for the mixture of heavy oil and water required to obtain
the water lubricated flow regime in a horizontal pipeline has been reported as
0.1–0.5 m/s for different applications [10, 12, 13, 15, 28]. In addition to the minimum
velocity criterion, sustainable lubricated pipe flow also requires a minimum water
fraction, typically between 10 and 30% [1]. A greater percentage of lubricating
water does not cause a significant reduction in the pressure loss; even if it reduces
the pressure loss to some extent, it also reduces the amount of oil transported per
unit of energy consumed [10, 13, 20]. Water lubrication is usually identified from
pressure loss measurements [13]. The establishment of lubricated pipe flow is
typically associated with a significant and nearly instantaneous reduction in
frictional pressure losses [20].
As mentioned earlier, a significant concern during the application of lubri-
cated pipe flow is that a minor fraction of the transported oil tends to adhere to
the pipe wall, which eventually leads to the formation of an oil layer on the pipe
wall [1, 3, 12, 13, 15, 18, 19, 29]. Frictional pressure losses in a “fouled” pipe, that
is, with an oil coating on the wall, are higher compared to those for transportation
of the same mixture in an unfouled pipe [15, 30]. Nevertheless, the frictional
losses with wall fouling are substantially lower than that would be expected for
transporting only heavy oil [10, 20, 29].
Wall fouling is practically unavoidable in the water lubricated pipeline trans-
portation of viscous oils [10, 12, 13, 15, 20]. Varying degrees of wall fouling are
experienced in the applications of this pipe-flow technology. Different descriptions
have been used in the literature to classify these applications, for example:
a. Core annular flow [11, 30]
b.Self-lubricated flow [12]
c. Continuous water assisted flow [10, 13]
Lubricated pipe flow has been used in this chapter to refer to any of these flow
types, despite the fact that they exhibit quite different characteristics.
Core annular flow (CAF) primarily denotes an idealized version of lubricated
pipe flow. It involves a core of viscous oil lubricated by a water annulus through a
pipe with a clean (unfouled) wall [11, 29, 31]. Many research studies published in
the 1980s and 1990s focused exclusively on CAF, for example, [11, 31, 32]. In most
of these studies, wall fouling was either minimized or avoided through prudent
selection of operating conditions, such as water cut and construction material of
75
pipe. In pilot-scale and industrial operations, attempts to operate CAF pipeline

usually required expensive mitigation strategies to handle wall fouling. In most
published cases, it was impossible to avoid wall fouling (see, for example [15, 33]).
The self-lubricated flow (SLF) and continuous water assisted flow (CWAF) are
the commonly applied forms of LPF in the industry. As mentioned earlier, the SLF
refers to the water lubricated pipeline transportation of a viscous mixture known as
bitumen froth containing approximately 60% bitumen, 30% water, and 10% solids
by volume [12, 19, 20]. The water fraction in the froth lubricates the flow; addi-
tional water is usually not added. In a SLF pipeline, water assist appears to be
intermittent, and the oil core may touch the pipe wall at times [10, 12, 29]. Contin-
uous water assisted flow denotes the pipeline transportation of heavy oil or bitumen
when the water lubrication is more stable and the oil core touches the pipe wall
infrequently [10, 13, 34]. Approximately 20–30 vol% water required to produce
lubricated flow is supplier from an external source to a CWAF pipeline. Both SLF
and CWAF involve wall fouling. For example, the thickness of fouling layer was
measured from 5.5 to 8.5 mm in a 150-mm SLF pipeline transporting bitumen froth
at 25°C [19]. Similar thicknesses in a 100-mm CWAF pipeline were found to vary
from 1 to 5 mm depending on the operating temperature and mixture velocity
[10, 23].
1.3 Modeling LPF pressure losses
Lubricated pipe flow has been applied in a specific industrial context for
transporting viscous oils like heavy oil and bitumen with limited success in many
cases [1, 3, 9, 18, 20, 21]. A challenge to the broader application of LPF technology is
the lack of a reliable model to predict frictional pressure losses, even though
numerous empirical (e.g., [12, 13]), semi-mechanistic or phenomenological
(e.g., [10, 11, 15]) and idealized models (e.g., [14, 32, 33, 35–37]) have been
proposed to date. The existing models were developed based on either single-fluid
or two-fluid approach. A critical analysis of these models is important to underscore
their limitations and to realize the scope of developing new approach to model
LPF frictional losses.
1.3.1 Single-fluid approach
Single-fluid models are also known as equivalent fluid models. This kind of
models generally takes an engineering approach to predict the pressure gradients.
The flow system is modeled by considering the flow of a hypothetical fluid under
comparable LPF process conditions. In some cases, this hypothetical fluid is water
[10, 12, 13, 15]. In other cases, the properties of this fluid are determined using the
mixture properties [11]. The flow regime in a single-fluid model is assumed to be in
turbulent state, and the friction factor is recognized as inversely proportional to the
nth power of a representative Reynolds number (Re), that is, f = K/Ren. The
constants K and n are either determined empirically or simply assigned. The
Reynolds number is defined with respect to the properties of the hypothetical liquid
and the pipeline conditions: an equivalent density (ρ) and viscosity (μ) of the
hypothetical liquid, the pipe diameter (D), and the average mixture velocity (V).
The famous Blasius formula (f = 0.079/Re0.25) is often the basis of single-fluid
modeling approach. This empirical law was originally proposed for the turbulent
flow of water in a smooth pipe. The value of K in Blasius formula (K = 0.079) can be
tweaked to take into account the equivalent hydrodynamic roughness produced by
the pipe-wall and/or wall fouling layer. Thus, single-fluid models take an empirical
approach to predict pressure loss for lubricated pipe flow; the actual physical
76
mechanisms governing pressure losses in a water lubricated pipeline are mostly

disregarded.
1.3.2 Two-fluid approach
There are a few two-fluid models available in the literature [23, 32, 33, 38].
However, most of these were proposed for smooth pipe CAF, that is, this kind of
models does not take into account the hydrodynamic roughness. As a result, these
models are not suitable for SLF or CWAF. However, these models do have an
advantage over single-fluid models. The actual mechanism of frictional pressure
loss is addressed to some extent while developing a two-fluid model. The modeling
approach is described in details with two examples as follows.
Oliemans et al. [32] described the mechanism of frictional losses in their
pioneering model developed for a CAF system. They identified the shear in the
turbulent water annulus as the major contributing factor to pressure losses.
However, they had to empirically address two important aspects of core annular
flow: physical roughness on the oil core and water holdup. They also used a couple
of idealized concepts like Reynold’s lubrication theory and Prandtl’s mixing length.
This two-fluid model systematically underpredicted the CAF pressure losses. Also,
the implementation of the model is not straightforward.
Ho and Li [31] adapted the key features of Shi et al. [33] to develop another
two-fluid model. They recognized the major source of frictional pressure loss in
CAF to be the shear in the turbulent water annulus and modeled the turbulence
based on the concept of Prandtl’s mixing length. They also considered the oil core to
be a plug having a rough surface. However, instead of empirically quantifying this
roughness like [33], the complexity of physical roughness was simplified in [32]
based on the concept of hydrodynamic roughness. An idealized core annular flow
regime was subdivided into four hypothetical zones as presented in Figure 2, which
also depicts the dimensionless distances of these zones from the stationary pipe
wall. The velocity profiles in the sublayers are usually presented using these
nondimensional terms. The relationships of flow rate and pressure drops were
obtained by integrating these velocity profiles with respect to the dimensionless
distance. The equations are presented in Table 1.
Figure 2.
Hypothetical subdivision of perfect or ideal core annular flow into four zones showing dimensionless distances
from the pipe wall [31].
77
Zone (Figure 2) Equations Range

+ +
Laminar sublayer u1 = y 0 ≤ y+ ≤ 11.6
(1)
Turbulent layer (2) u2+ = 2.5ln(y+) + 5.5 11.6 ≤ y+ ≤ yc+ 5
Laminar sublayer u3+ = 2.5ln(yc+ 5) yc+ + 10.5 + y+ yc+ 5 ≤ y+ ≤ yc+

(3)
Plug core (4) u4+ = 2.5ln(yc+ 5) + 10.5 yc+ ≤ y+ ≤ R+
(1) + (2) + (3) Qw = 2π(νw2/v*)[(2.5R+yc+ 1.25yc+2)ln 0 ≤ y+ ≤ yc+

(yc+ 5) + 3R+yc+ 2.125yc+2 – 13.6R+]
(4) Qo = π(νw2/v*)(R+ yc+)2[2.5(lnyc+ 5) + 10.5] yc+ ≤ y+ ≤ R+
Table 1.
Velocity profiles and equations relating flow rates and pressure losses [31].
The principal focus of Ho and Li [31] was the water annulus in a CAF pipeline.
The annular thickness was the most important parameter in the two-fluid model.
However, they had to determine this thickness empirically. Moreover, they used the
idealized concept of perfect CAF, that is, the perfectly concentric orientation of the
oil core in the pipe, even though the orientation is more likely to be eccentric
[29, 33]. The eccentricity of the oil core has a consequential effect on the CAF
pressure losses [39].
Even after involving a number of simplifications, the Ho and Li model very
closely addresses the physical mechanism of CAF pressure losses. This model allows
predicting the pressure gradients using the values of oil and water flow rates. As
expected, this two-fluid model underpredicts the CWAF friction losses consistently.
This is because a CWAF system involves considerable wall fouling and oil core
eccentricity, while the two-fluid model was developed for the perfect CAF in a
hydrodynamically smooth pipe.
Adapting the modeling methodology described in [32], a physics-based
approach to model CWAF pressure losses was proposed in [38]. Please refer to
Ref. [23] for the details of the development. It is a semi-mechanistic two-fluid
model, which requires simulating the turbulent flow of annular water on the fouling
oil layer in a lubricated pipeline. The turbulence in the water annulus is modeled
with the anisotropic ω-RSM model instead of the standard isotropic models. It can
capture the effects of the thickness of the wall fouling layer, the equivalent
hydrodynamic roughness produced by the viscous oil layer on the pipe wall, and the
water holdup. The model was validated using actual CWAF data collected by
varying pipe diameter, oil viscosity, water fractions, and flow rates. Compared to
existing CFD models, this model is more robust as it not only produces better
predictions but also requires significantly fewer computing resources. Although a
promising development, the current version of the model involves some simplifi-
cations and is difficult to implement.
2. Descriptions of selected models
2.1 CAF model
Arney et al. [11] performed a comprehensive study on the core annular flow in a
horizontal pipeline involving both experiments and theoretical analysis. Their pri-
mary objective was to enrich the CAF database and introduce a simple approach to
calculate the frictional pressure losses.
78
For the experiments, Arney et al. [11] used two oils: waxy crude oil (ρ = 985 kg/m3
and μ = 0.6 Pa s) and No. 6 fuel oil (ρ = 989 kg/m3 and μ = 2.7 Pa s). The experimental
setup consisted of three pipeline segments made of a glass pipe having 15.9 mm inner
diameter (ID). The 6.35-m long first part was used for flow visualization using a Spin-
Physics SP2000 high-speed video system and a 35 mm camera. The second part of the
pipeline was used to connect two pressure tap. 1.42 m apart. The last part of the pipe
was 1.47 m long and utilized to measure the in situ volume fraction of water, that is,
water holdup.
Two important parameters used for this study were the water holdup (Hw) and
input water fraction of (Cw). It was observed that the Hw was consistently larger
than the Cw. That is, the oil core in CAF was moving faster than the annular water
phase. Similar experimental finding was also reported in [23]. Areny et al. [11] then
collated all the previous CAF experimental data from the literature with their own
measurements to propose the following correlation between Hw and Cw:
Hw ¼ Cw ½1 þ 0:35ð1 � Cw Þ� (1)
They also measured the pressure losses for a variety of flow conditions. Based on
the data, they proposed a single-fluid model. The friction factor (f) was correlated
to a system specific Reynolds number (Rea):
f ¼ 0:079=Re0:25
a , Rea . 4000 (2)
Rea ¼ ρc DV=μw (3)
2
ΔP=L ¼ f ρc V =2D (4)
where ΔP/L is the pressure gradient, μw is the water viscosity, and ρc is an

equivalent fluid density. The viscosity of the equivalent liquid was considered to be
equal to that of water (μw). Empirical expression used to correlate the density of this
hypothetical liquid (ρc) to the densities of oil (ρo) and water (ρw) is as follows:
ρc ¼ Hw ρw þ ð1 � Hw Þρo (5)
Using this model, it was possible to predict a large number of CAF pressure drop
data sets with a reasonable accuracy. The model showed good conformance with
friction factor values at high Reynolds number. However, there was significant
under prediction when Reynolds number was low. This was due to the fact that at
low Reynolds number, the core annular flow was slightly unstable.
2.2 SLF model
Joseph et al. [12] investigated the “Self-Lubrication” phenomenon of Bitumen

froth (approximately 60% bitumen, 30% water, and 10% solids by volume), which
was extracted using Clark’s hot water extraction process from the oil sands of
Athabasca. The water in the froth, while transporting through the pipelines, was
released due to high shear resulting in a lubricating layer near the wall. This is just
another form of CAF where the annular water comes from the mixture itself.
Two different setups were used to experimentally study the phenomenon of
self-lubrication. First, a setup of 6 m long 25 mm ID pipe loop was used at the
University of Minnesota. The froth was continuously recirculated. The duration of
the experiments varied from 3 to 96 hours. The velocities for which pressure
gradients were measured ranged from 0.25 to 2.5 m/s. Water volume fractions were
kept within 20–40%, and the froth temperature ranged between 35 and 55°C. From
the collected pressure gradient data at different flow rates, it was observed that
79
there was a critical velocity range (from 0.5 to 0.7 m/s) below which the self-
lubrication was being lost. The longest experimental time in this setup was 96 hours.
This test was conducted in an already fouled pipeline. Despite the residual fouling,
no further fouling was observed during the experiment. The authors suggested that
this may be due to the clay particles (Kaolinite) from the released water protecting
the oil core from accumulating to the pipe wall. The researchers also observed that
heating the froth to a higher temperature would not necessarily improve the lubri-
cation. This was due to the opposing effects of lowered bitumen viscosity at high
temperature and reabsorption of the released water into the core. The other test
setup (0.6 m ID and 1000 m long pipeloop) was at Syncrude (Canada), where pilot-
scale tests were performed.
Based on the experimental data, a single-fluid model for the SLF of bitumen
froth was proposed. In this model, a “Blasius-type” equation was used to correlate
the f with a water equivalent Reynolds number (Rew):
f ¼ 0:079K j =Re0:25
w (6)
In Eq. (6), the complex flow behavior of self-lubricated flow is addressed with
an empirically determined value of Kj. It was assumed to be a function of tempera-
ture only (Kj = 23 when temperature ranges 35–47°C and Kj = 16 when temperature
ranges 49–58°C). Water content was considered to have negligible effect on Kj.
Frictional pressure losses are 15–40 times greater when predicted using the above
model than those for water flowing alone under identical flow conditions. The
application of this model for predicting LPF pressure losses is extremely limited
according to previous researches [10, 13].
2.3 CWAF model 1
McKibben et al. [13] carried out the investigation to examine free water-crude
oil flows and, specifically, to establish a correlation for predicting the pressure
gradients in continuous water assisted flow.
The experiments were conducted using the followings:
a. A 53-mm ID pipeline consisting of approximately 60 m long horizontal

insulated section;
b.The water fractions between 0.10 and 0.36;
c. The temperatures ranging from 18 to 39°C
d.The average velocities of the mixtures between 0.5 and 1.2 m/s;
e. Four different oils with the viscosities of 91.6, 24.9, 7.1, and 5.8 Pa s.
On the basis of the CWAF data sets at different water equivalent Reynolds
number, the correlation of Fanning friction factor was found as:
1410
f ¼ (7)
Rew
dP
� dL D
f ¼ (8)
2ρw V 2
80
DVρw
Rew ¼ (9)
μw
The inverse relationship between friction factor and water Reynolds number
suggested that friction was controlled by a very thin water layer. A water layer of
this type formed the lubrication region surrounding the oil core and provided the
lubricating force required to overcome the effect of natural buoyancy.
2.4 CWAF model 2
Rodriguez et al. [15] mainly focused on lab- and pilot-scale experimental mea-
surements. They also took a semi-mechanistic approach to model frictional pressure
losses of horizontal core annular flows in pipes having both fouled and clean walls.
That is, the model was actually developed for the CWAF systems.
Lab-scale tests were conducted with a 27-mm ID PVC pipe and a crude oil
having a viscosity of 0.5 Pa s at 20°C. For the pilot-scale experiments, a steel
pipeline (77 mm ID and 274 m length) was used to pump a highly viscous crude oil
(36.95 Pa s and 972.1 kg/m3 at 20°C). A freshwater network was used to control the
water injection. A piston pump pumped the water, and its flow rate was adjusted via
a calibrated frequency inverter. The water superficial velocity was kept constant at
0.24 m/s, and three oil superficial velocities, 0.80, 1.00, and 1.10 m/s, were tested.
In the experiments, a wavy core of viscous oil was observed, and the annular
flow of water was mostly turbulent (Reynolds number for the water
flow: 1000 , Re2 , 14; 500, Re2 ¼ ρ2 Vμ 2 D). The proposed model first defined the
2
irreversible hydrodynamic component of the frictional pressure gradient (ΔP

L ):

ΔP ρm VD �n ρm V 2
¼b (10)
L μm 2D
where D is the pipe ID, V is the mixture velocity, ρm is the mixture density, μm is
the mixture viscosity, and b is an empirical constant. The μm was obtained by
evaluating the ratio between the wall shear stress in core-annular flow (τo ) and the
wall shear stress if the annular water was flowing alone in the pipe at mixture flow
rate (τw ). Assuming the phases have the same density and use the same power law
to express the friction factors in both flows, the shear stress ratio (Rτ ) was expressed
as:
�n 2
b ρ2 Vμ 2 D
ρ2 V 2
τo 2 1

Rτ ¼ ¼
2
�n 2 ¼ (11)
n
τw ρ0 ¼ρ2 b ρ2μVD ρ2 V ð1 � εÞ ½1 þ ðs � 1Þε�2�n
2 2
1
ε¼ (12)
1 þ s VV2
where V 2 is the average in-situ water velocity. Also, Rτ is the ratio between the
corresponding pressure drops, and from Eq. (11), one obtains
�n
ΔP μ2
L
Rτ ¼ ΔP ¼ (13)
L 2, o μm
ρ1 ¼ρ2
where ΔPL 2, o is the extrapolated pressure drop for the annulus fluid alone in the
pipe at mixture flow rate:
81

ΔP ΔP ρ VD �n ρ2 V 2
¼ lim ¼b 2 (14)
L 2, 0 ε!0 L μ2 2D
From Eqs. (13) and (14), the mixture viscosity can be expressed as:
μ2
μm ¼ (15)
ð1 � εÞ½1 þ ðs � 1Þε�ð2�nÞ=n
Eq. (15) shows that the mixture viscosity is affected by the slip ratio: the faster
the core moves relative to the annulus, the lower the mixture viscosity and pressure
drop. For the simple case of perfect core annular flow (PCAF), putting n = 1 and
s = 2, Eq. (15) can be transformed into:
1 1 � ε2
¼ (16)
μm μ2
The final form of the pressure drop model was obtained by introducing a two-
phase multiplier defined as
ΔP
∅2, o ¼ ΔPL (17)
L 2, 0
Using Eq. (10), (13), and (14), the above equation becomes
1�n
ρm
∅2, o ¼ Rτ (18)
ρ2
which becomes using Eq. (12) and ρm ¼ ερ1 þ ð1 � εÞρ2 :

1�n
ρ1
∅2, o ¼ 1� 1� ε ð1 � εÞ�n ½1 þ ðs � 1Þε�n�2 (19)
ρ2
The hydrodynamic component of frictional pressure gradient can be

expressed as
1�n
ΔP ρ JD �n ρ2 J 2 ρ
¼b 2 1� 1� 1 ε ð1 � εÞ�n ½1 þ ðs � 1Þε�n�2 (20)
L μ2 2D ρ2
or
1�n
ΔP ρ1
¼ φQ 2�n
1� 1� ε ð1 � εÞ½1 þ ðs � 1Þε�n�2 (21)
L ρ2
n�2 1�n n n�5
where φ ¼ b2 4π ρ2 μ2 D , and Q is the mixture flow rate.
The proposed model can be used to analyze, correlate, and generalize pressure
drop data. Along with that, the model allows for the satisfactory representation of
different annulus flow regimes, kinematic effects, and wall conditions, including
fouling. The model accounts for effects of buoyancy on the core. However, it cannot
provide reliable predictions without regressing the values of b and n on the basis of
reliable data set.
82
2.5 CWAF model 3
In continuation of the previous research [13], McKibben et al. [10] carried out
an extensive experimental investigation of CWAF. The tests were conducted at the
Saskatchewan Research Council (SRC), Saskatoon, Canada using 25, 100, and
260 mm steel pipe flow loops. The average thickness of wall fouling (tc) was
estimated using a special double-pipe heat exchanger [19]. The estimations were
validated by using a hot-film probe to measure the physical thickness of the fouling
oil layer. Heavy oils having viscosities in the range of 0.62–91.6 Pa s were used
for the experiments. The input water fraction was within the range of 30–50%.
Additional details of the experimental facilities are available in [23].
Based on the experimental study, a new empirical correlation for the Fanning
friction factor was proposed as follows:
� pffiffiffiffiffiffi��0:5
1:3 0:32 �1:2
f ðCWAFÞ ¼ 15 V= gD f CF f OIL CCF (22)
where V is the average mixture velocity, g is the gravitational acceleration, D is

the pipe diameter, fCF is the friction factor of aqueous phase, fOIL is the friction
factor of oil phase, and CCF is the total volume fraction of water in the mixture. It is
a phenomenological model, which is claimed to take into account the effects of
inertia, gravity, lubricating water, wall fouling, and viscous oil in CWAF. A large
data set comprising more than 300 data points were used for the empirical deriva-
tion of the model constants.
2.6 CFD models
A scientific methodology of modeling single phase turbulent flow is to use

computational fluid dynamics (CFD) [40]. In general, this modeling approach
decomposes the turbulent flow into two parts: (i) time-averaged mean motion;
(ii) time-independent fluctuations. The product of such decomposition is the
transformation of Navier-Stokes (NS) equations into Reynolds Averaged Navier
Stokes (RANS) equations [41]. In course of the mathematical transformation, addi-
tional terms of turbulent stresses are produced to make the matrix of equations
“unclosed”; that is, the number of unknowns is higher than the number of equa-
tions. Various turbulent stresses in RANS equations are necessarily modeled empir-
ically for the “closure” of the matrix [42]. The continuity and RANS equations can
be presented with the following simplified differential equations:
∂U i
¼0 (23)
∂xi
� �
∂U i ∂U i 1 ∂p ∂ μ ∂U i
þ Uj ¼� þ � τij þ Si (24)
∂t ∂xj ρ ∂xi ∂xj ρ ∂xj
where xi represents the coordinate axes, Ui is the mean velocity, p is the

pressure, ρ is the density, μ is the viscosity, Si is the sum of body forces, and τij
represents the components of the Reynolds stress tensor. The available models for τij
can be divided in the categories of eddy-viscosity models and Reynolds stress
models [43, 44].
Eddy-viscosity models were developed based on the concept of a hypothetical
term known as eddy-viscosity (μt), which is considered to produce turbulent
stresses caused by macroscopic velocity fluctuations [41]. These models can further
83
be divided into three major groups, namely zero-equation, one-equation, and two-
equation models [43, 44]. Two-equation models, instead of zero- and one-equation
models, are generally used at present to solve complex engineering problems
[43, 45]. The most commonly used two-equation models are the k-ε and k-ω models
[44]. A significant limitation of this group of models is that they are meant to
describe isotropic turbulence [46, 47]. That is, only the significant components of
the Reynolds stresses can be computed with the two-equation models. As a result,
the group of two-equation models is practically limited to flows where anisotropy is
not important [47, 48]. It should be mentioned that the turbulent water annulus in a
CWAF pipeline can experience both anisotropy and rough surfaces [10, 12, 15, 30].
These models are also not suggested for turbulent flow in narrow channels and over
very rough surfaces [49, 50].
Anisotropic turbulence can be addressed using Reynolds Stress Models (RSM),
in which the hypothetical concept of eddy-viscosity is discarded [46]. An example
of anisotropic model is ω Reynolds Stress Model (ω-RSM) [45]. In this model, the
closure for Reynolds stresses is obtained by using seven differential transport
equations [42]. It is a higher level and more elaborate modeling approach compared
to the isotropic two-equation models. This kind of models is more widely applicable
compared to eddy-viscosity models [43–46]. However, this flexibility is gained
through a high degree of complexity in the computational system. The solution of
an increased number of transport equations requires significantly higher computa-
tional resources compared to the applications of different two-equation models.
Even so, a Reynolds stress model was successfully applied to simulate flow condi-
tions that involve anisotropy and rough surfaces [47–51].
To acknowledge the superiority of a Reynolds stress model, a study of the
equivalent hydrodynamic roughness (ks) produced by a wall fouling/coating layer
of viscous oil (μo 21 kPa.s) was conducted using a rectangular flow cell [23]. The
oil surface became rough when turbulent water (Rew > 104) was pumped through
the flow cell. The rough viscous surface produced very large values of ks compared
to the similar values produced by a clean surface. The relative performance of k-ω
model and ω-RSM is presented in Figure 3. The ω-RSM can provide reliable
predictions of the measured values of friction losses, while the k-ω model yields
significant under predictions. This is because the process conditions involved
turbulent flow, a hydrodynamically rough surface, and a narrow flow channel,
which produced anisotropic turbulence. Comparable analysis was also conducted
involving various rough surfaces like solid wall, sandpapers, wall-biofouling layers,
and wall-coating layers of heavy oils in different flow cells. Invariably, the ω-RSM
always allowed for reliable predictions, while the k-ω model failed to do so. This
analysis along with the supporting literature evidently prove that a RSM would be a
better choice than a two-equation model to simulate flow conditions, which involve
anisotropy and hydrodynamically rough surface.
It should be mentioned that turbulence is a complex subject. Even though RANS
methodology is feasible to computationally resolute the phenomenon of turbulence,
it averages the process variables with a steady-state assumption in course of solving
NS equations. The minor scale unsteady features of turbulence are usually neglected
in this kind of averaging [44]. Most important of these features is the turbulent
eddies. The scale of these eddies can vary over orders of magnitude [46]. The CFD
solution of taking the effect of these eddies into account is computing differential
NS equations without any kind of modeling. The available methods for the purpose
are Large Eddy Simulation (LES) and Direct Numeric Simulation (DNS). However,
these two simulation techniques demand extremely high computational resources
[44]. At a computing rate of 1 gigaflop, the requirement of computational time for
DNS is of the order of the Reynolds number to the third power (Re3). Similar
84
Figure 3.
Comparison of experimental pressure gradients with simulation results: 25.4 � 15.9 � 2000 mm rectangular
flow cell; average coating thickness, tc = 1.0 mm; equivalent hydrodynamic roughness, ks = 3.5 mm; 104 < Rew
< 105 [23].
requirement in LES is generally ten times less than DNS. As an industrial flow
system like CWAF pipeline can involve Re in the order of 105 or higher, application
of LES or DNS is not realistic for CWAF at this point.
Two-fluid CFD modeling approach to predict frictional pressure losses of
core annular flow was used in different studies [14, 35, 36]. They considered the
water annulus to be turbulent and the viscous core to be a laminar plug. Usually, the
annular turbulence was modeled with standard k-ε and k-ω models using commercial
CFD packages like ANSYS CFX. CFD simulations were also conducted using FLUENT
for horizontal oil-water flow with viscosity ratio ðμo =μw Þ ¼ 18.8 in different flow
regimes, namely core annular flow, oil plugs/bubbles in water, and dispersed flow
[37]. In FLUENT, the volume of fluid (VOF) model of multiphase flow and the SST
k-ω scheme of turbulence closure was applied to simulate the oil-water flow. The
SST k-ω turbulence scheme at the interface provided better predictions than the
standard k-ε and re-normalization group (RNG) k-ε models. Although these turbu-
lence models might show some superiority over Prandtl’s mixing length model used in
[32], they are meant for isotropic turbulence and are not suggested for the turbulent
flow that involves anisotropy or very rough surfaces [49–51]. In addition, this model-
ing approach is also expensive computationally as it requires solving the governing
equations for both phases of oil and water. Using an anisotropic model makes this
modeling approach even more expensive from a computational perspective. More-
over, the interphase transfer of mass and momentum is modeled in this methodology
by using the default mixture model ANSYS CFX or FLUENT. The correlations used
for these models are not validated for the interfacial mixing of LPF systems.
3. Comparative analysis
The performance of existing models in predicting friction losses is analyzed by

comparing the experimental results collected for a lab-scale LPF system with the
corresponding results obtained using five different models in Figure 4. The water
equivalent friction factor (fw) and Reynolds number (Rew) defined as follows are
presented in this figure:
85
ΔP D
fw ¼ (25)
L 2ρw V 2
DU w ρw
Rew ¼ (26)
μw
where ΔP/L is the pressure gradient, D is the internal pipe diameter, V is the
bulk velocity, Uw is the water superficial velocity, and ρw and μw represent water
density and viscosity, respectively. The experiments were conducted in a 26-mm
horizontal PVC pipeline to collect data under typical CWAF operating conditions
[7, 34]. The heavy oils used for the experiments had densities and viscosities in the
ranges of 900–950 kg/m3 and 3.3–16.0 Pa s, respectively. Although different flow
patterns were observed in course of the experiments, the core annular flow with oil
fouling on pipe wall, that is, the CWAF was the dominant regime under a wide
range of flow conditions. The results shown in Figure 4 reveal the major limitation
of the existing models to be their system specificity.
The CAF model proposed by Arney et al. [11] significantly under predicts the
experimental results for CWAF tests. The model was developed based on the
experiments conducted in a 15.9-mm glass pipeline, which was selected for the
purpose of controlling wall fouling and visualizing the flow regime. Compared to
the CAF model, higher predictions of fw-values by the SLF model and CWAF
model 2 can be seen in Figure 4. These three models were developed for CAF
systems having different degrees of wall fouling and intermittent lubrication. It is
interesting to note that the trends of the results produced by all of these three models
are similar to that of Blasius law predictions, which represent the frictional losses as
only water flows through a pipe. This is because these models were developed based
on the Blasius correlation. Clearly, the methodology of modeling CWAF friction
losses by modifying Blasius law is not a successful approach. On the other hand, the
CWAF model 1 also fails to provide satisfactory predictions. It was developed by
modifying the standard f correlation for laminar flow regime (f = 64/Re).
Among the models presented in Figure 4, the CWAF model 3 demonstrates
superiority in predicting both the magnitude and the trend of CWAF friction
factors. The performance of the model tends to be better at higher flow rates. The
reason is, most likely, the difficulty in establishing the lubricated flow regime at
lower flow rates. The improved predictions of this model can be attributed to the
following facts:
Figure 4.
Comparison of experimental and predicted values of water equivalent friction factor with respect to an
equivalent Reynolds number.
86
i. Instead of a purely empirical reasoning, the model was developed based on

phenomenological observations. The physics of frictional pressure losses in a
CWAF pipeline dominated the modeling approach. It can be considered as
an empirical two-fluid model.
ii. Special attention was paid to the contribution of wall fouling in increasing
CWAF pressure drops.
iii. A large data set covering a wide variety of process conditions was used to
regress out the model constants.
However, it should be emphasized that the CWAF model 3 needs further vali-
dation with multiple independent data sets. Producing more quality data of CWAF
pressure losses would be essential for the purpose.
As demonstrated here, the existing models generally adopt an empirical
approach to predict LPF friction losses. The effects of operating conditions in these
models are usually accounted for with empirical constants. The actual physical
mechanisms that govern the pressure losses in an LPF pipeline are almost entirely
disregarded. As a result, the models developed for a CAF system cannot be applied
to a CWAF system and vice versa. More rigorous studies are essential to develop a
fully mechanistic approach to model the LPF friction losses. The CFD can be
expected to play a significant role in the process.
4. Challenges and opportunities
The lab-scale applications reported in the literature and a few commercial suc-
cesses prove that continuous water assisted flow is a reliable method for the long-
distance transportation of heavy oil. One of the major barriers to spread commercial
applications of this flow technology is the lack of a viable model to predict frictional
losses on the basis of operating parameters, such as pipe diameter, flow rates, fluid
properties, and water fraction. A new model capable of dealing with the hydrody-
namic effects produced by the “wall fouling” layer in a CWAF pipeline is required
to facilitate wider industrial implementation of this pipeline transportation tech-
nology. The phenomenon of wall fouling has not been thoroughly probed till now,
although it is an important characteristic of CWAF technology. Therefore, the
future researches should be focused on the investigation of the hydrodynamic
effects produced by the wall fouling layer.
The oil core touching the pipe wall in a large water-assisted pipeline is another
unaddressed phenomenon. Experiments conducted at Saskatchewan Research
Council suggest that this phenomenon is significant for intermittent water assist
when the bulk velocity is less than 1 m/s and the water fraction is less than 30%
[10]. More devoted research works are necessary to determine the contribution of
intermittent core/wall contact to the LPF pressure loss.
The presence of solids like sands or clays in a CWAF pipeline is another impor-
tant issue. The solids embedded on the wall fouling layer and the oil core may
increase the equivalent roughness. In some cases, the fine particles in the lubricating
water can change its apparent viscosity and the nature of contact between the oil-
covered wall and the oil core (see [12] for additional details). Future work in this
field would help to characterize the effects of solid fraction on the pressure losses in
CWAF pipelines.
87
5. Conclusions
The objective of the current chapter is to provide a brief introduction to the

water lubricated transportation of heavy oil. The contents are summarized as
follows:
i. Lubricated pipe flow is an alternative technology for long distance

transportation of heavy oil. This kind of water assisted pipeline
transportation is more economic and environmentally friendly than the
conventional viscous oil transportation technologies. Its applications can be
categorized as core annular flow, self-lubricated flow, and continuous water
assisted flow. From an engineering perspective, CWAF is more significant
than CAF or SLF.
ii. A technical challenge to the field-scale application of CWAF is the absence of

a reliable model to predict friction losses.
iii. The models proposed to date for CWAF friction losses can be categorized as
single-fluid and two-fluid models. In general, the methodology followed to
develop a two-fluid model is more mechanistic, while a single-fluid model is
an empirical development.
iv. Applicability of an existing model for a specific set of flow conditions

cannot be justified at present without a comparative analysis based on a
reliable data set.
v. The most important research opportunities to develop a more reliable model

for CWAF friction losses are related to the following subjects:
a. Wall fouling
b.Intermittent water lubrication
c. Solid laden CWAF
d.CFD modeling
e. Enrichment of the CWAF database
Acknowledgements
A part of the manuscript was the outcome of a research project that was funded
by the NSERC Industrial Research Chair in Pipeline Transport Processes (RSS). We are
grateful to Canada’s Natural Sciences and Engineering Research Council (NSERC)
and the Industrial Sponsors: Canadian Natural Resources Limited, CNOOC-Nexen
Inc., Saskatchewan Research Council Pipe Flow Technology Centre™, Shell Canada
Energy, Suncor Energy, Syncrude Canada Ltd., Total, Teck Resources Ltd. and
Paterson & Cooke Consulting Engineers Ltd. We are especially thankful to
Dr. Sanders (Professor, Department of Chemical and Materials Engineering,
University of Alberta) for his kind advisory role in the research project.
88
The authors certify that they have no affiliations with or involvement in any
organization or entity with any financial interest (such as honoraria, educational
grants, participation in speakers’ bureaus, membership, employment, consultan-
cies, stock ownership, or other equity interest, and expert testimony or patent-
licensing arrangements), or nonfinancial interest (such as personal or professional
relationships, affiliations, knowledge or beliefs) in the subject matter or materials
discussed in this manuscript.
Other declarations
A part of the manuscript is adapted from the corresponding author’s PhD

dissertation.
Author details
Sayeed Rushd1*, Rasel A. Sultan2 and Shahriar Mahmud3
1 King Faisal University, Al Ahsa, Saudi Arabia
2 Del Tech Manufacturing, Prince George, BC, Canada
3 Bangladesh University of Engineering and Technology, Dhaka, Bangladesh
–NC
89
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93
Chapter 6
Ablation of Oil-Sand Lumps in

Hydrotransport Pipelines
Mahshad Pazouki and Sayeed Rushd
Abstract
Oil-sand ore is a kind of heavy crude oil found primarily in Canada. The surface
mining of this petroleum resource requires expensive 400-ton capacity trucks to
transport the ore to the slurry plant. The slurry prepared with the crushed ore is
usually conditioned in a hydrotransport pipeline prior to extracting bitumen. As the
elimination of the mammoth trucks has a tremendous economic and environmental
incentive, it is of industrial interest to employ new processes capable of condition-
ing oil-sand right at the mine face. This would demand an accelerated rate of
conditioning compared to what is achieved at present in the industry. One of the
significant steps of the conditioning process is oil-sand lump ablation (OSLA). An
understanding of the fundamental concepts associated with OSLA is essential to
achieve any industrial-scale change in the current conditioning method. A number
of parameters such as temperature, lump size, pipe diameter, pipe length, flow rate,
and shear influence the ablation process. The current chapter introduces the con-
cept of OSLA. It also includes a comprehensive review of the most important
models available to predict the ablation rate and the scope of future works.
Keywords: heavy oil, bitumen, transportation, conditioning, ablation rate,

modeling
1. Introduction
About 15–20% of the Canadian oil-sand reserve containing 140 billion barrels
of bitumen can be found at a depth less than 75 m, where surface mining is
economically feasible [1]. The remaining 80–85% buried at higher depths can
possibly be recovered with underground-type mining employing in situ techniques.
The Great Canadian Oil Sands, now known as Suncor Energy Inc., developed an
open-pit mine, a hot water extraction plant and an upgrading complex in 1967.
Their operation was followed in 1979 by Syncrude Canada Ltd.’s open-pit mine at
Mildred Lake. Currently, Suncor Energy Inc., Syncrude Canada Ltd., Albian Sands
Energy Inc., and Canadian Natural Resources Ltd. employ surface mining [1–3].
A typical surface mining operation, as shown in Figure 1, includes the following
steps [1, 2]:
1. Removal of overburden using shovels and trucks
2. Mining oil-sand with hydraulic or electric shovels
3. Transport of oil-sand ore from the mine face to the crushers with trucks
95
Figure 1.
Major steps for bitumen recovery in surface mining operation [1].
4. Crushing of large oil-sand lumps into smaller parts
5. Oil-sand conditioning
6. Gravity separation of bitumen froth
7. Diluted froth treatment to separate water and solids
8. Supplemental solvent recovery from tailings
9. Dewatering and concentrating the tailings
Among the above mentioned steps, oil-sand conditioning is probably the most
important phase that can further be divided into three stages [1, 3]:
i. Oil-sand lump ablation or size reduction
ii. Liberation of bitumen from sand grains
iii. Aeration of bitumen droplets
Oil-sand ore carried from the mine with conveyors was originally conditioned
with rotating drums or tumblers [1]. Investigations into the possibility of replacing
conveyors and tumblers with pipelines began at the Syncrude Research Center in
the early 1980s [3, 4]. The idea was based on the examination of the pipelines
transporting tailings from the separation vessels to the tailing ponds. Subsequently,
a large-scale prototype of an oil-sand hydrotransport system known as the extrac-
tion auxiliary production system was commissioned in 1993. It became a successful
commercial unit that could digest up to 5000 ton of oil-sand per hour. Since then,
hydrotransport pipelines are being used in other commercial extraction plants to
simultaneously transport and condition oil-sand ore. Roughly 60, 000 ton of oil-
sand flowing as slurry of about 60 wt% solids is digested per hour to produce ½
million barrels of bitumen per day at present [3, 5]. Commercial applications of
hydrotransport pipelines enabled the conditioning process to be carried out at
considerably lower temperatures [6]. Syncrude Aurora now operates their 5 km
hydrotransport line at 35–40°C [7].
96
The use of hydrotransport pipelines improved the oil-sand conditioning at lower

temperatures [1]. As the efficiency of the conditioning process significantly influ-
ences the final recovery of the bitumen, achieving an efficient method for the
conditioning has always been the target among oil-sand producers [1, 3]. In addi-
tion, reducing the production cost and greenhouse gas emissions has also been
ongoing targets in the industry [1]. Continued process improvements have led to
more economic bitumen production process and reduced environmental footprint
[8]. Presently, oil-sand companies aim to eliminate the use of expensive trucks to
transport the ore to the slurry plant by conditioning the oil-sand slurry at the mine
face [2]. This kind of onsite conditioning would demand a consequent reduction of
pipeline length, which would potentially cause incomplete conditioning and could
especially affect lump ablation [2]. In order to resolve the problem, an accelerated
conditioning process would be required. Before implementing any significant
changes in the oil-sand conditioning, a better understanding on the fundamentals of
OSLA must be developed.
As the first step of conditioning, the crushed and screened oil-sand lumps (size
range, 50–150 mm) are ablated or digested inside the hydrotransport pipeline [9].
The ablation occurs due to the dual effects of heat transfer and mechanical energy
[6]. Generally, bitumen acts as a glue to hold the matrix of sand grains together. It
should be mentioned that the viscosity of bitumen is a strong function of tempera-
ture. As a result, the viscosity of the bitumen on the surface layer of the lump
reduces considerably as an oil-sand lump is exposed to the hot slurry medium. The
softened surface layer is then sheared away due to the shearing inside the
hydrotransport pipeline, and, thereby, a new lump surface is exposed to the hot
medium. The new surface undergoes the same mechanism. This process repeats
itself to the point that the entire lump is ablated. The heat transfer from the slurry
and the contacts of a lump to neighboring lumps as well as the pipe wall control the
rate of ablation [10]. The parameters that mostly affect OSLA can be identified as
temperature and composition of the slurry, size and temperature of the initial lump,
and mechanical shear imparted to the lump [1, 11].
The current chapter aims to contribute to the better understanding of the lump
ablation process. It would assist to identify the important parameters that affect the
OSLA and to recognize the way in which each one of these parameters influences
the ablation process. The oil-sand conditioning process can be improved by chang-
ing one or more of these factors to achieve accelerated ablation and conditioning as
required. Previous studies of oil-sand lump ablation are also described, and impor-
tant areas not covered by those investigations are identified. In addition, some
background theory needed in the development of improved ablation models is
introduced.
2. Effects of operating parameters on ablation
As mentioned previously, the ablation of oil-sand lumps is the result of two

important phenomena: heat transfer and shear forces [1]. Any factor that affects
these phenomena would have an effect on the ablation process. The most important
of this kind of parameters, viz., slurry temperature, initial lump size, pipeline
diameter, and pipeline velocity or shear stress, are discussed here.
2.1 Slurry temperature
Since the commissioning of the first commercial oil-sand mining and bitumen
extraction operation, attempts to reduce bitumen production costs and environ-
mental impacts have driven process improvements and flowsheet changes [6]. One
97
way to reduce both simultaneously is to operate the process at a lower slurry

temperature. Slurry temperature is effectively the most important parameter in the
extraction of bitumen from Athabasca oil-sand, as it affects all three steps of
oil-sand conditioning, i.e., oil-sand lump ablation, bitumen liberation, and air
attachment.
Bitumen, because of its high viscosity, holds the mixture of sand grains and fine
minerals together within an oil-sand lump [6]. The viscosity of bitumen decreases
sharply with increasing temperature as shown in Figure 2. Since the viscosity is
above 105 mPa.s at room temperature (T = 20°C), bitumen looks like a solid, and it
is essentially impossible to separate bitumen from the sand grains at this tempera-
ture. When the temperature increases to 50°C, bitumen viscosity reduces by more
than one order of magnitude, i.e., to the order of 103 mPa.s. The separation of
bitumen from sand grains occurs relatively quickly at such temperature. Lower
viscosity of bitumen must be attained in order to reduce the lump size and liberate
bitumen from sand grains efficiently [6, 12]. It should be mentioned that froth
quality and bitumen recovery are also dependent on slurry temperature as the
temperature influences the air bubble-bitumen attachment. Although oil-sand pro-
ducers ultimately wish to operate hydrotransport pipelines at low temperatures
due to the reduced operating costs and environmental impacts, they are well aware
that a balance between bitumen recovery and temperature reduction must be
attained. At this point, operating temperatures between 40 and 55°C are common
in the industry [6].
2.2 Initial lump size
The heat transfer to an oil-sand lump is an important factor in ablation process

[13]. The thickness of the layer softened and ablated away is equal in essence for all
lump sizes under comparable thermal conditions. Therefore, the fraction of lump
mass that is removed decreases as the lump size increases. In other words, the time
necessary for complete digestion of a lump increases with the initial lump size [1].
2.3 Pipeline diameter
Pipeline diameter is a key parameter in the ablation of an oil-sand lump. For a

specific slurry flow rate, more energy is dissipated in a pipe having smaller
Figure 2.
Viscosity of Athabasca bitumen as a function of temperature [1].
98
diameter, and this leads to the higher interparticle shear stresses [1]. The relation-
ship between energy dissipation and pipe diameter can be expressed as follows [14]:

ɛ ¼ 2f f V 3 =D (1)
where,
ɛ is the volumetric average of energy dissipation in the pipeline (m2/s3),V is the
bulk velocity (m/s), D is the pipe diameter (m), and ff is the Fanning friction factor.
According to Eq. (1), energy dissipated in a pipe inversely varies with the
diameter of the pipe. Consequently, higher energy dissipation, i.e., higher ablation
rate, is expected in smaller pipelines. On the other hand, the residence time of an
oil-sand lump inside a smaller pipe will be shorter as the bulk velocity is higher in
the pipe for a constant slurry flow rate. A shorter residence time is likely to result in
a lower ablation rate [1]. A balance must be sought between the residence time and
the energy dissipation in order to achieve an acceptable ablation rate. That is, the
pipeline diameter should be optimized for a specific flow condition.
2.4 Shear stress
An oil-sand lump moves at a different velocity than the surrounding slurry and
contacts with the pipe wall as well as other lumps present in the slurry. The
difference in the velocities results in a shear stress on the lump surface [1]. In a
pipeline, the shear force acting on the lump surface is expected to increase with
increasing mixture velocity and concentration. Higher slurry concentrations pro-
mote particle-particle interactions and particle-wall interactions [1, 3]. Thus, all
steps of the oil-sand slurry conditioning process depend on the slurry velocity in a
hydrotransport pipeline [5]. However, more research has been conducted to study
the effect of shear exposure on bitumen liberation and bitumen aeration than lump
ablation. Clearly, this area demands further investigations.
3. Examples of previous studies
Important examples of previous experimental and modeling studies on lump

ablation are briefly discussed in this section. The parameters considered in each
study are summarized, and the parameters that need further investigations are
identified.
3.1 Traynis wheel test stand
Traynis [15] studied the grinding or crushing of coal particles using a wheel test
stand (WTS). It was experimentally demonstrated that the pressure losses for slurry
in a WTS agree quite well with that in a horizontal pipeline. This agreement was a
result of the similarities in energy dissipation mechanisms of moving solid particles
in both systems. The mechanism of energy dissipation was found to determine the
process of the particle crushing.
Most of the tests reported in [15] were completed using a WTS made of a
200-mm diameter pipe. Three runs were repeated with another WTS made of
300-mm diameter pipe to investigate the effect of pipe size on particle crushing or
grinding. Pipes were polished using abrasive materials like quartz to ensure that
the pipe wall was smooth when the experiments were started. The apparatus was
filled up to 1/3 of the total volume with a mixture of water and coal. For each run
99
using the smaller WTS, 10–40 kg of coal was loaded. Coal particles from two
different hydraulic mines were used for the experiments. At certain time intervals,
the degree of size reduction of the coal particles was determined by measuring the
particle size distribution of the remainder of the particles. To reconfirm that the
WTS system was representative of the horizontal pipeline, a number of experi-
ments were replicated by circulating slurry in 4 and 1.3-km long pipelines. The
effects of slurry velocity and concentration, pipe diameter, coal particle size, exis-
tence of abrasive rocks, pipe length, and mechanical properties (strength and
hardness) of the coal particles on the size reduction of the coal particles were
investigated. The outcomes of the experimental investigation can be summarized
as follows:
1. The results obtained using short pipelines (10 km) agreed with those of the
wheel test stand experiments. However, transporting the coal particles for a
long distance (>20 km) resulted in faster crushing. This is probably because
the mixture passed through the feed pump many times. It caused more rapid
size reduction of the coal particles. The effect was more evident when the
initial coal particle size was large.
2. The slurry velocity was changed from 1.8 to 6 m/s for experiments with
different coal types. In all cases, velocity had an insignificant effect on the
crushing of coal particles.
3. Slurry concentrations were varied from 1:16 to 1:2 (mass of solid, mass of
liquid). These experimental runs showed that size reduction of the coal
particles was independent of slurry concentration.
4. The pipe size of the wheel test stand did not affect the extent of size reduction
of the coal particles.
5. For coal particles having initial diameters in the ranges of 3–6 or 50–100 mm,
the degree of size reduction was only affected by the initial particle size. For
particles smaller than 3 mm, increasing the initial particle size resulted in more
visible increase in the intensity of crushing.
6. The existence of abrasive rocks, which were 50–100 mm in diameter initially but
were crushed to the 3–6 mm size range in the slurry, caused more rapid size
reduction of particles. Considerable crushing was observed within the first 15 km.
7. The crushing rate was higher in the first few kilometers of the pipe, and it
decreased as coal particles moved along the pipeline. This must be because of
the fact that shear stress decreases as particle size decreases, which would be
expected when the particle slip velocity decreases. Rounding of the edges of
the particles within the first kilometers of the pipe might be another reason for
reduction of the crushing rate with pipeline length.
8. Experiments using coal particles with initial size in the range of 6–13 mm
showed that as the strength factor of the coal particles increased, the crushing
rate decreased. Strength factor is an indicator of the grindability of the coal
particles.
One of the strengths of this study is that it introduces a new experimental

method for studying the mass loss of solid particles. In addition, this is the only
100
study done on the effect of slurry velocity and concentration on the particle mass
loss in slurry pipelines. However, one cannot directly apply the results of this
research to oil-sand hydrotransport pipeline. This is because the nature of coal
particles is very different from oil-sand lumps. Coal is a brittle organic sedimentary
rock that contains varying amounts of carbon, hydrogen, nitrogen, oxygen, and
sulfur [16]. On the other hand, oil-sand contains bitumen, sand grains, clays, and
small amount of water, and the viscosity of bitumen highly varies with temperature
[1]. As coal is brittle, coal particles tend to break down into smaller particles when
they are exposed to the shear forces. However, mass loss from oil-sand lumps occurs
by gradual mass removal from the surface of the lump. The amount of mass loss
from an oil-sand lump depends on many parameters, although temperature seems
to be the most important factor. Thus, one cannot study oil-sand lump ablation
without considering the slurry temperature. Additionally, because the nature of the
two materials is different, the effect of slurry concentration and velocity on their
mass loss can be expected to be different.
3.2 Law et al. experimental study
Law et al. [17] examined the ablation of frozen mixtures of water and paraffin
wax (octadecane) with solid particles such as kaolinite clay, titanium oxide, alumi-
num powder, and sand. Because the ablation of oil-sand samples was complex, they
chose to study the ablation of less complex materials. This investigation was
conducted with the purpose of obtaining information from a well-controlled system
and applying it for designing the rotating drums, which were used for oil-sand lump
ablation at that time. A turbulent axisymmetric water jet, whose velocity varied
between 1.7 and 2.8 m/s, was used. The temperature of the jet was changed from 32
to 60°C depending on the material being tested. The water temperature was chosen
based on the sample’s melting point, which was 26–29°C for octadecane. Cylindrical
samples (L = 150 mm, d = 11 mm) were manufactured and immediately frozen in
liquid nitrogen. The samples were then placed in front of the jet using a sliding
platform. The sliding platform was moved up and down by using a stepping motor.
Before the start of the experimental run, the front of the sample was placed in-line
with a certain point called the melt front pointer. During an experimental run, the
sample was never moved from this point. Instead, the sliding platform was lowered
at a speed equal to the ablation rate of the frozen sample. The downward movement
of the sliding platform against time was recorded and plotted. The slope of this line,
for each set of the experiments, was considered to be the ablation rate. It was
observed that for each operating condition, the slope of the plotted line remained
constant with time. The results of this study can be summarized as follows:
1. For all samples, an increase in the jet temperature increased the ablation rate.
For instance, ablation rate of lumps made from octadecane and 60 (vol%) sand
at V = 2.8 m/s and T = 60°C was equal to 4.4 103 m/s, whereas it was equal
to 3 103 m/s at T = 50°C.
2. Increasing the jet velocity from 1.7 to 2.8 m/s increased the ablation rate
equivalent to that of raising the jet temperature by approximately 10°C (from 50
to 60°C). This is because surface shear stress on the sample is proportional to V2.
3. Addition of solid particles to the samples affected the ablation rate in a

complex way. The effect depended on the type of the solid particles and the
lump material because thermal conductivity of the solid particles was
different, so the heat transfer coefficient within the sample differed depending
101
on the solid particles. In the case of octadecane-kaolinite samples, at a certain

jet velocity and temperature (V = 2.06 m/s, T = 50 and 60°C), ablation rate
gradually increased for solid content up to 17 vol%, and, for solids content
beyond 17%, the ablation rate increased significantly. The reasons for this
observation were mentioned to be the increase of the heat transfer area due to
the roughening of the melting surface and the ablation of the sample as clusters
instead of layers at high solid contents. That is, ablation can also depend on the
type and components of the oil-sand ore.
Although this experimental study could provide a good indication of the way
different parameters influence ablation, the study had some limitations such as:
i. Viscosities of the samples were significantly different from that of bitumen.
ii. Sample was stationary and was exposed to water only from one face.
iii. Ablation with only water was investigated.
iv. The number of experimental runs using samples manufactured with sand
particles was very limited.
More investigations need to be conducted on actual OSLA using a system that

better represents the actual conditioning medium. These experiments are necessary
to develop a predictive model applicable for all operating conditions.
3.3 SRC experimental study
In 1996, an experimental study on the ablation of actual oil-sand lumps was

conducted at the Saskatchewan Research Council (SRC) Pipe Flow Technology
Centre™ [10]. Lump ablation at various operating conditions were investigated by
loading a certain amount of lumps to a 264 mm pipe loop using a feeder close to the
pump discharge. At certain time intervals, lumps were trapped with a basket before
discharging into the storage tank. The trapped lumps were weighed and put back
into the loop. The SRC experiments showed the following results:
1. For all types of the oil-sand lumps, the time or pipeline length required to
reach a certain ablation rate was strongly dependent on the slurry temperature.
As shown in Figure 3, the time required for the complete ablation at T = 50°C
was one third of that at T = 30 and 18°C for soft lumps. It is worth noting that
the effect of temperature on the ablation rate was found to be qualitatively
similar for various oil-sand ores [1, 10].
2. The ablation rate was faster for lumps with lower initial temperature at higher
slurry temperatures (T = 30 and 50°C)
This experimental study is very valuable, as it is the first available research on the
ablation of actual oil-sand lumps. However, the research did not include the effects of
important parameters such as slurry velocity and concentration on ablation.
3.4 Masliyah ablation model
Masliyah ablation model (model 1) was developed for the ablation of oil-sand
lumps based on the fact that crushed oil-sand lumps and sand particles form a
moving layer at the bottom of the pipe, while the fine solids—water blend known as
102
the carrier fluid, exist within the whole pipe cross section [1, 6, 10]. The height of
the bottom layer reduces with axial position along the pipeline when lump size
reduces. It was assumed that the heated surface layer of the lump peeled off because
of the shear stress inside the pipe. This process was presumed to repeat up to the
point when 95% of the lump mass would be removed. The SRC two-layer model
was used to estimate the velocities of top and bottom layers of the flow. An average
value of the shear stress on the lumps was calculated using the slurry viscosity and
the axial flow velocity [1, 6]. The model was validated with the data available
in [10]. The predicted effects of mixture velocity, pipeline diameter, slurry
temperature, initial lump size, slurry density, and pipeline length are discussed
as follows [1]:
1. Raising the slurry velocity does not cause any significant enhancement in the
oil-sand lump ablation rate. As shown in Figure 4, the beneficial effects of
increasing velocity are offset by the reduced residence time of the lump.
2. The rate of lump digestion reduces with the increasing pipe diameter at
T = 25°C (Figure 5A). As a result, longer pipelines are needed for complete
ablation. At T = 50°C, however, the effect of pipe diameter is not very
Figure 3.
SRC Experimental results showing the effect of slurry temperature on the ablation time of soft lumps [10].
Figure 4.
Effect of mixture bulk velocity on the oil-sand lump ablation (T = 50°C; T0L = 5°C; d = 20 mm) [1].
103
significant (Figure 5B). This is probably because heat transfer is the dominant
factor in the ablation of an oil-sand lump. At a higher temperature, the
viscosity of the bitumen and the surface shear stress required for consequent
removal of the soft surface layer reduce significantly.
3. Increasing the slurry density increases the ablation rate at a fixed temperature
(Figure 6). This is because an increment in slurry density is caused by a
reduced water flow rate, i.e., an increased residence time. For the same reason,
ablation rate reduces with decreasing slurry density.
4. Smaller oil-sand lumps ablate more rapidly (Figure 7). A given mass of oil-sand
ore in the form of smaller lumps is digested much faster than the same mass of
ore in the form of larger lumps due to the larger surface area of the former.
Although model 1 is one of the pioneer models that can be used for industrial-
scale ablation of oil-sand lumps, it has a number of limitations. Some of the limita-
tions are identified as follows:
i. Only one set of experimental data was available for validating this model. The
data was also limited to a certain pipeline size and a set of velocities.
Figure 5.
Effect of pipe diameter on the ablation of oil sand lumps (T0L = 5°C; V = 3.8 m/s; ρm = 1550 kg/m3;
d = 20 mm): (A) T = 25°C; (B) T = 50°C [1].
104
Figure 6.
Effect of slurry density on the ablation of oil sand lumps (T0L = 0°C; D = 710 mm; d = 100 mm and T = 40°C) [1].
Figure 7.
Effect of initial lump size on the ablation of oil-sand lumps (T0L = 0°C; D = 710 mm; ρm = 1548 kg/m3 and
T = 40°C) [1].
ii. A part of the model, namely, the method of estimating surface shear force on
the lumps is yet to be verified.
iii. The version of the SRC two-layer model used for the modeling is out-of-date.
The SRC model has been improved lately. However, the improvements were
never integrated into model 1.
iv. According to model 1, the bulk velocity was used to calculate the shear stress
acting on the oil-sand lumps. However, the velocity of the lumps in slurry is
about 90% of the bulk velocity. This means, the relative velocity causing the
shear stress on the lump is likely to be only 10% of the velocity. Therefore, the
shear stress used in Model 1 might be overestimated.
3.5 Eskin et al. ablation model
Eskin et al. model (Model 2) was developed for the ablation of a spherical oil-
sand lump using a hypothesis similar to that of Masliyah model [13]. The following
assumptions were used for the purpose:
1. The effects of shear stresses and heating were integrated with respect to a
surface critical temperature. The critical temperature remained constant
105
during the ablation and was related to the minimum adhesive strength of the
bitumen. This model-specific temperature was determined using the
experimental results available in [17].
2. The lump was considered to retain its spherical shape during ablation.
Based on the assumptions, the complex phenomena were simplified as a

one-dimensional heat conduction problem for a shrinking sphere. The critical
temperature was used as an input to the applied convection boundary condition.
A correlation between the reduction of sphere size and the critical temperature was
found by simplifying the boundary condition-based equations. The heat conduction
equations were also included in the model. The model was applied to study the
effect of lump size and initial temperature on OSLA.
Although the fundamental concepts used for model 2 agree with general
hypothesis of how individual oil-sand lumps ablate, the way of integrating shear
stress to a critical temperature is debatable. Moreover, the effects of slurry velocity
and slurry concentration on ablation cannot be investigated with the model. Most
importantly, the model was never validated against any experimental data.
3.6 Pazouki study
Pazouki [18] applied an innovative method by using strain gauge technology for
online tracking of the mass loss of the anchored oil-sand lumps. Four small strain
gauges looped in a full-bridge circuit were used for the measurements. The new
method also allowed measuring the drag force on ablating and non-ablating objects.
The accuracy of the drag force measuring technique was evaluated by comparing
the measured drag force with the calculated drag force on the number of smooth
spheres in water.
As part of the experiment, an idealized oil-sand lump was anchored in a basket
at the height of 40DL, where DL is the diameter of the cylindrical lump. Artificially
manufactured oil-sand lumps were used for the experiments. Slurries (C = 0.15 and
0.30) were prepared by mixing pre-weighed industrial quartz (d50 = 0.190 mm)
with water. The flow temperature was adjusted using a double-pipe heat exchanger
located in the vertical section of the pipeline loop. DASYlab 10.0 software was used
to the readings of strain gauges, temperature, and flow meter.
In addition to experimentation, Pazouki [18] also developed a new modeling
approach. The overall outcomes of this study can be summarized as follows:
1. The online measurement method and the experimental apparatus built at SRC
provide the opportunity to test OSLA at many different operating conditions.
The strain gauge measurement method also enables measuring the drag force
on the ablating oil-sand lump.
2. The data obtained using the artificially produced oil-sand lumps were
repeatable.
3. The OSLA was enhanced significantly with the increasing flow temperature.
Heat transfer played a more important role for ablation in the slurry where
surface shear stresses can be expected to be lower.
4. The slurry velocity was found to affect OSLA appreciably. The ablation rate
increased with Vn, where n = 2–4.7. The value of n was a function of
temperature.
106
Figure 8.
Comparison of measured and predicted ablation rate for slurry (C = 0.30) at T = 45°C [18].
5. Ablation in water occurred at a slower rate than that in the slurry. However,
an increase of slurry concentration from 15 to 30% at T = 30°C reduced the
ablation rate. This reduction was most likely related to the turbulence
modulation in slurries that could affect both shear force and heat transfer.
6. For the range of concentrations used for the study, the slurry concentration
did not have a significant influence on the ablation of oil-sand lumps.
7. The drag force acting on a lump depended on the slurry concentration.
8. The equivalent fluid model was found to be most appropriate for simulating
the drag force. In this model, the slurry is treated like a single-phase fluid with
density and viscosity related to the solid concentration.
9. The proposed model demonstrated the ablation rate to be a primary function

of surface shear force and temperature. In the model, the effect of
temperature was implemented as the change in the bitumen viscosity.
10.The model was validated with respect to the experimental measurements. An

example of the validation results is presented in Figure 8. In course of the
validation, it was found to better predict the ablation rate than other existing
models.
Even though the study advanced both experimentation and modeling of OSLA,
it suffers from the similar limitations of previous studies. It neither clarifies the
procedure to apply the experimental findings to the actual hydrotransport pipelines
nor verifies the model with industrial-scale data.
4. Theory and modeling
In order to estimate the ablation rate of the oil-sand lumps inside the
hydrotransport pipeline, the shear stress acting on the lumps and the temperature
profile of the lump at different times must be determined. The most relevant
models for the estimation are follows:
1. SRC two-layer model
2. Shear stress decay law
107
The benefits and drawbacks of each model are discussed in the subsequent
sections.
4.1 SRC two-layer model
Recall that an early version of SRC model was used to estimate the shear stress
acting on the oil-sand lump(s) in model 1. If one intends to use a similar approach, it
would be advisable to use a more recent version of the model. The theory behind the
development of the SRC two-layer model is explained in this section. Also, the
validity of this approach for calculating the shear stress acting on a lump is
discussed.
In a slurry pipeline similar to the hydrotransport pipeline, fine particles (parti-
cles <0.074 mm) are considered to augment the viscosity and density of the
suspending liquid, i.e., the carrier fluid. The coarse particles that are suspended by
fluid turbulence are assumed to be at a constant volume fraction throughout the
flow domain. The other part of the coarse particles, that is, the fraction not effec-
tively suspended by fluid turbulence, is supposed to transmit the immersed weight
to the pipe wall. These particles are found in the lower layer and contribute Cou-
lombic or sliding bed friction [11]. The continuous concentration profile of the
coarse particles was simplified to a step-change, i.e. two layers for the purpose of
writing force balance equations. The velocity within each layer was assumed to be
constant. Figure 9 shows the idealized concentration and velocity distributions.
The SRC two-layer model was developed using mass and force balances for the
two layers of the slurry. The force balance produces an equation for the axial
pressure gradient in horizontal slurry as a function of friction losses in top layer,
bottom layer, and the interface between the layers [19].
To estimate the ablation rate of an oil-sand lump, the actual shear stress on the
lump needs to be estimated. If one assumes an oil-sand lump is located at the
interface between the two layers, the surface shear stress acting on this lump can be
assumed to be equal to the shear stress at the interface. The shear stress at the
interface is calculated using the following correlation [11]:
1
τ12 ¼ f 12 ðV 1 � V 2 ÞjV 1 � V 2 jρ1 (2)
2
where ρ1 denotes the slurry density in the upper layer and f12 is the interfacial
friction factor that can be estimated from a modified Colebrook friction factor equation:
2ð1 þ Y Þ
f 12 ¼ 2 (3)
4 log 10 ðD=dÞ þ 3:36
Figure 9.
Idealized concentration and velocity distributions used in the SRC two-layer model [19].
108
where Y is the 0 for d/D < 0.0015 and Y is calculated using the following
equation when 0.0015 < d/D < 0.15:
Y ¼ 4 þ 1:42 log 10 ðd=DÞ (4)
Equation (4) has been formulated based on the data taken at Archimedes num-
ber, Ar < 3 � 105.
It is inferred from Eq. (2) that the shear stress acting on a lump is proportional to
(V1 � V2)2. Calculating the velocity of the layers using the SRC two-layer model
shows that V2 is substantially small compared to V1 and (V1 � V2) is approximately
equal to the slurry bulk velocity (V). On the other hand, other research conducted
at the Saskatchewan Research Council showed that the velocity of a large particle
in horizontal slurry flow was about 0.9 V. That is, the shear stress on the oil-sand
lump would be proportional to (0.1 V)2, which is considerably smaller than (V1 �
V2)2. In other words, the shear stress calculated using Eq. (2) might overestimate
the shear stress acting on an individual lump.
4.2 Shear stress decay law
In order to estimate the effects of slurry velocity and concentration on OSLA, a

simplified approach can be taken instead of using complex two-layer model. The
following assumptions are necessary to apply the method:
1. The oil-sand lump is stationary compared to the slurry flow in the

hydrotransport pipe.
2. Slurry flow has reached steady state.
3. Slurry density is constant throughout the pipe.
Based on the assumptions, the local shear stress where the solid particle is
located in the hydrotransport pipeline can be estimated using the shear stress decay
law [11]:
2s τw
τrz ¼ (5)
D
where s is the distance from pipe axis (m), τrz is the shear stress at y (Pa), τw is
the pipe wall shear stress (Pa), and D is the pipe diameter (m).
For a known value of the wall shear stress, the shear stress at any radial position
of the pipe can be calculated using Eq. (5). However, calculating the wall shear
stress for a hydrotransport pipeline is complex as wall shear stress and flow density
are not constant around the pipe.
Flow is not uniform throughout the cross section in a hydrotransport pipeline at
all. Significant concentration and velocity gradients can exist, particularly, if oper-
ating velocity is just higher than the deposition velocity (Vc) [10]. However, the
concentration profile was found to be nearly uniform for highly concentrated set-
tling slurries at velocities significantly higher than Vc, and, for these slurries, Cou-
lombic friction was also found to be negligible relative to kinematic friction [19].
Moreover, Coulombic friction is typically negligible as long as the particle diameter
is not too large (d50 ≤ 0.3 mm), and the mixture velocity is high (say, V > 2Vc) [11].
It is therefore worthwhile to consider the so-called kinematic friction loss compo-
nent of the SRC pipe flow model [Eqs. (6) and (7)] to calculate the wall shear stress
109
for such systems [10, 11]. Using this model, the kinematic friction loss component
is determined so that it accounts for the friction associated with the flow of the
carrier fluid, the friction related to particle collisions and the tempering effect of
near-wall lift. If the Coulombic friction can be assumed to be negligible, then only
the kinematic friction is important, and the τw can be calculated using the following
equations [10, 11, 20]:
� �
τw ¼ 0:5 V 2 f f ρf þ f s ρs (6)
� � � �
f s ¼ λ1:25 A Ln dþ þ B (7)
for d + ≤ 21: A ¼ �1:1 � 10�4 and B ¼ 4:2 � 10�4

for d + ≥ 21:A ¼ �5:6 � 10�5 and B ¼ 2:6 � 10�4
� �0:5
d v ∗ ρf d f f =2 V ρf
dþ ¼ ¼ (8)
μf μf
"� � #�1
Cmax 1=3
λ¼ �1 (9)
C
The estimation of kinematic friction provides a tool for realistic assessment of

the effects of slurry velocity and concentration on the local shear stress. To
Term Value
D (mm) 103
s (mm) 20
3
ρf (kg/m ) 1000
μf (Pa.s) 0.001
d50 (mm) 0.120
ρs (kg/m3) 2650
Table 1.
Input parameters for estimating shear stress inside a pipe.
Figure 10.
Pipeline local shear stress at different slurry velocities and concentrations.
110
demonstrate the application, a model system is considered here. The system prop-
erties are chosen on an arbitrary basis and outlined in Table 1.
The local shear stress is shown in Figure 10 as a function of mixture velocity for
two different solid concentrations. The graph indicates that, for a solid particle
placed 20 mm from the center of a 103 mm pipe, the surface shear stress on the
particle increases substantially at higher mixture velocities. It should be noted that
the graph indicates the effect of velocity and concentration on shear stress qualita-
tively. The results do not represent the actual shear stress on the oil-sand lumps.
This example shows the application of shear stress decay law for a simplified case,
where the solid particle is stationary. However, in the actual hydrotransport pipe-
lines, oil-sand lumps move along the pipe axis. In order to estimate the shear stress
acting on the lump, the slip velocity of the lump must be considered.
5. Conclusions
A limited number of studies on the ablation of large particles exist in open

literature. Among these studies, only a few looked at the effect of velocity and
concentration on the ablation. Slurry concentration and velocity were experimen-
tally demonstrated to have minimum effect on the grinding or crushing of the coal
particles [15]. The effect of slurry velocity on OSLA was also shown to be insignif-
icant with the application of model 1 [1]. Interestingly, increasing velocity was
found to cause a considerable increase in the ablation rate for stationary samples
[17, 18]. An estimate of pipe local shear stress based on a simplified application of
shear stress decay law likewise shows that increasing slurry velocity enhances the
shear stress inside the pipeline. That is, the velocity is likely to have a positive
impact on OSLA. However, an increase in slurry concentration appears to have a
more substantial effect on the increase of local shear stress at low slurry velocities.
Rigorous investigations are required to clarify the impacts of slurry velocity and
concentration on OSLA. To the best of authors’ knowledge, no significant research
has been done until now to study the effect of slurry velocity and concentration on
the ablation of actual oil-sand lumps. Also, a publicly available model that can
estimate the ablation rate of the oil-sand lump as a function of shear stress forces is
not available to date, although such a model is highly required for engineering usage
in the industry.
Acknowledgements
A part of the manuscript was the outcome of a research project that was funded
by the NSERC Industrial Research Chair in Pipeline Transport Processes (RSS). We
are grateful to Canada’s Natural Sciences and Engineering Research Council
(NSERC) and the Industrial Sponsors: Canadian Natural Resources Limited,
CNOOC-Nexen Inc., Saskatchewan Research Council Pipe Flow Technology Cen-
tre™, Shell Canada Energy, Suncor Energy, Syncrude Canada Ltd., Total, Teck
Resources Ltd., and Paterson & Cooke Consulting Engineers Ltd. We are especially
thankful to Dr. Sanders (Professor, Department of Chemical and Materials Engi-
neering, University of Alberta) for his advisory role in the research project.
Other declarations
A part of the manuscript is adapted from the first author’s PhD dissertation.
111
Nomenclature
A area (m2)
Ar Archimedes number ()
C solid volume concentration ()
D pipe diameter (m)
DL lump diameter (m)
dp particle diameter (m)
d50 mean particle diameter (m)
d+ dimensionless particle diameter ()
ff Fanning friction factor ()
fs solid friction factor ()
L length (m)
R radius (m)
s distance from pipe center (m)
s+ dimensionless distance from pipe center ()
T temperature (°C)
T0L lump initial temperature °C
t time (s)
V bulk velocity (ms1)
Vs solid object velocity (ms1)
Vc deposition velocity (ms1)
v local velocity (ms1)
μ viscosity (Pa.s)
ρ density (kgm3)
τ shear stress (Pa)
τw wall shear stress (Pa)
τwp wall shear stress on solid object (Pa)
Author details
Mahshad Pazouki1 and Sayeed Rushd2*
1 TransCanada, Calgary, Alberta, Canada
2 King Faisal University, Al Ahsa, Saudi Arabia
–NC
112
References
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Bitumen Recovery from Athabasca Oil
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[2] Flint L. Bitumen Recovery Canadian Journal of Chemical
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[10] Shook CA, Gillies RG, Sanders RS.
[3] Sanders RS, Schaan J, McKibben MM. Pipeline hydrotransport: With
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[4] Sanders RS, Ferre AL, Principles and Practice. Amsterdam,
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oil sands ores [thesis]. University of
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Vinogradov O. A model of oil sand lump
[6] Masliyah J, Zhou ZJ, Xu Z, digestion. Minerals engineering. 2002;
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[7] Schaan J, Cook N, Sanders RS. On-
line wear measurements for [15] Traĭnis VV. Parameters and Flow
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bench-scale study of conditioning
behaviour in oil sands slurries. The [17] Law HS, Masliyah JH, Nandakumar K.
Canadian Journal of Chemical Ablation of ice-solids and wax-solids
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114
Chapter 7
Evaluation of Asphaltenes
Deposition Inhibition Factors in
Heavy Crude Oil Pipelines
Hazlina Husin, Mysara Eissa Mohyaldinn Elhaj
and Colin D. Wood
Abstract
Asphaltenes deposition is considered as Achilles’s heel in the oil industry. The

nucleation, precipitation and deposition of asphaltenes reduce the production rate
significantly in affected wells and sometimes it can completely block the flow by
plugging the flowlines, tubing and process facilities, in severe cases. This chapter
evaluates the extrinsic and the intrinsic (thermodynamic) factors within the heavy
crude oil production system. The main consequences of asphaltenes deposition are
discussed such as the solvent-to-crude oil dilution ratio, crude oil physical proper-
ties (cloud point, pour point and API gravity), chemical solvent type (carbon
number, functional group), agitation time and temperature changes. This chapter
is expected to become the means for understanding the factors affecting the
asphaltenes nucleation, precipitation and deposition.
Keywords: heavy crude oil, flow assurance, asphaltenes, deposition, inhibition
1. Introduction
Oil industry has been increasing its activities of crude oil production in subsea
environments, deep waters and cold environments [1]. However, the physical and
chemical conditions of these unconventional reservoirs have been challenging in
which oil industry needs to overcome flow assurance issue such as asphaltenes
deposition [2].
Asphaltenes deposition will affect the oil production rate at all oil production
stages [3]. For example, when asphaltenes deposit in reservoir rock, they change
the rock wettability hence decrease the chances of having an effective oil recov-
ery [4, 5]. In some enhanced oil recovery (EOR) methods such as carbon dioxide
injection [6] and chemical (cEOR) [7], the guest chemical would interact with
asphaltenes in crude oil and subsequently result in asphaltenes deposition.
Crude oil which flows in flowlines, tubing or process facilities will create a tem-
perature gradient within a specified boundary [8, 9]. This temperature change
will weaken the molecular interactions of resins which hold the asphaltenes
molecule in crude oil. Due to its polarity, asphaltenes molecule will accumulate
and subsequently start to nucleate. In general, asphaltenes deposition is consid-
ered as the major problem for oil industries as it occurs in upstream, midstream
and downstream.
115
Figure 1.
Asphaltenes molecular structure.
Asphaltenes are the heaviest, polar hydrocarbon substances containing hetero-

atoms such as nitrogen, sulfur and oxygen. Asphaltenes have an average molecular
weight, MWave of 750 g/mol. Figure 1 shows a schematic structure of the continen-
tal-model asphaltenes which obtained using MolView software v2.4.
There are several approaches for inhibiting deposition of asphaltenes such as via
physical removal, use of dispersant and use of chemical solvent. Physical removal
is done by using a pigging tool. It is however uneconomical because the collected
solid asphaltenes must be properly disposed and the production must halt for the
workers to conduct pigging. The use of dispersant is also uneconomical as the oil
industry will need to use a large amount of dispersant for a long period of time.
Chemical solvent such as benzene, toluene, chlorate or xylene as asphaltenes inhibi-
tor is widely used as the base component of commercial chemical inhibitor. But, due
to their low flash point and high toxicity level, these chemical solvents require extra
safety precaution during handling and storage.
Since asphaltenes have a complex structure, differ depending on oil reservoirs
and are not in any well-defined chemical group, it is difficult to predict the reason
why asphaltenes became unstable and deposited out from crude oil [10]. Previous
studies have revealed that asphaltenes deposition is a function of various param-
eters [11, 12]. Hence, this chapter evaluates the effect of asphaltenes deposition
inhibition factors such as solvent-to-crude oil dilution ratio, crude oil physical prop-
erties (cloud point, pour point and API gravity), the chemical solvent type (carbon
number, functional group), agitation time and temperature change on two types of
Malaysia crude oils. The findings from this study are desirable to develop prevention
and remediation methods for asphaltenes deposition problem.
2. Materials and methods
Pre-treated crude oil samples were collected from Malaysia oilfield with proper-
ties listed in Table 1. The crude oil samples contain negligible water and solids (such
as sand, clay and corrosion debris).
Different types of liquid solvent were bought from Fisher Chemicals with a
reported purity of 98–99%. The molecular structures of the solvents are shown in
Table 2, used to control asphaltenes precipitation. Mixtures of solvent-to-crude oil
dilution ratio of 1:1, 5:1, 10:1 and 15:1 were prepared for each solvent.
The method used to deposit the asphaltenes particles from crude oil is called
“standard direct experimental” method. This method follows the modified ASTM
2007/ASTM D6560 standard procedure [13, 14]. Once the solvent and the crude
116
Evaluation of Asphaltenes Deposition Inhibition Factors in Heavy Crude Oil Pipelines
Properties Sample 1 Sample 2
Cloud point (°C) 33.8 15.0
Pour point (°C) −2.0 −18.0
API gravity (°API) 37.4 12.5
Wax content (%) 4.0 10.0
Phase Liquid Liquid
Color Dark brown Dark brown
Table 1.
Crude oil properties for the study.
Solvent Molecular formula (MW) Molecular structure
n-Pentane C5H12 (72.15 g/mol)
Benzene C6H6 (78.11 g/mol)
n-Hexane C6H14 (86.18 g/mol)
Toluene C7H8 (92.14 g/mol)
Heptane C7H16 (100.21 g/mol)
Table 2.
Molecular structure and molecular weight (MW) of solvents used for the study, in increasing carbon number.
oil were mixed together according to the desired dilution ratio, the resulted mix-
ture was then placed in a water bath at room temperature and left for 3 h under
agitation condition. Then, the aliquot was placed in a container and centrifuged
at 10,000 rpm (SIGMA 3-18K, United Kingdom) with relative centrifugal force
(RCF) of 16,000 times gravity. The deposited asphaltenes were filtered by using
a Whatman® filter paper, grade number 42. Finally, the asphaltenes particles
were dried in a vacuum oven at 100°C for 30 min and then weighed (with digital
117
instrument precision: ±0.001 g) to determine the amount of asphaltenes precipi-

tated. The entire procedure was repeated for different agitation time (6 and 9 h)
and temperature (50 and 75°C).
3. Results and discussion
The observable deposited asphaltenes particle is shown in Figure 2. There have

been a wide range of asphaltenes particle size as reported in literatures; 2–5 nano-
micron [11] and 34–113 micron [13]. It is proposed that asphaltenes tend to self-
aggregate by π-π interactions and originate the asphaltenes “nucleus” which consist
of stacked nanoaggregates.
Figure 3a and b shows the plots for the deposited asphaltenes particles when
n-pentane was used as the solvent type. Systematically, n-pentane is selected as the
first stage of this study as recommended by the modified ASTM 2007 procedure.
At 1:1 dilution ratio, the amount of asphaltenes deposited was 0.860 g when the
agitation time was 3 h (as shown in Figure 3a). At 15:1 dilution ratio, the amount of
asphaltenes deposited was 3.100 g, at the same agitation time. Result showed that
the amount of deposited asphaltenes particle is increased with solvent-to-crude
oil dilution ratio. This is due to the increasing formation of unstable asphaltenes
aggregates. It is expected that a maximum asphaltenes yield would be produced at a
dilution ratio of 40:1 [15].
The same trend was found at longer agitation time, i.e., 6 and 9 h. The increas-
ing amount of deposited asphaltenes particles at higher dilution ratio was veri-
fied with published results [16, 17]. In the presence of n-pentane solvent, the
asphaltenes particles became unstable and precipitated as primary particles. At
higher volume of the solvent and longer agitation time, more resins which respon-
sible for asphaltenes solubility in crude oil are “washed off ” that lead to rapid
aggregation of asphaltenes molecules. Consequently, macroparticles (i.e., heavier
particles) asphaltenes are formed.
Interestingly, at lower region of dilution ratio (1:1 and 5:1), the amount of
asphaltenes deposited from sample A crude oil having agitation time of 3 h is the
same as that of 6 h (as in Figure 3a). As one may see, Figure 3b shows the same
behavior despite having different physical properties. This indicates that the
Figure 2.
Filtered asphaltenes particles.
118
Figure 3.
Amount of deposited asphaltenes at selected solvent-to-crude oil dilution ratio and different agitation time. The
conditions of experiment were: chemical solvent type = n-pentane and T = 30°C. (a) Sample A and (b) sample B.
solubility of asphaltenes in n-pentane solvent is approximately constant at low

solvent concentration or in this case lower region of solvent dilution ratio. We
proposed that this observation is due to the rapid diffusion and aggregation of
asphaltenes molecules hence resulting in high precipitation rate at short mixing
times. It is worth highlighting that future asphaltenes deposition studies should
distinct between the lower and higher regions of solvent dilution ratio. Note that
the kinetic effect is ignored here since the agitation time is constant (either at 3
or 6 h).
To evaluate the effect of the properties of the crude oil such as the cloud
point, pour point and density (reflected by the API gravity of crude oil), plots in
Figure 3a and b were compared. Although sample B having higher wax content and
heavier, i.e., more dense than sample A, both plots showed similar trend of incre-
ment of deposited asphaltenes particles at higher volume of solvent (i.e., higher
region of solvent dilution ratio). At 1:1 dilution ratio, we found that the magnitude
of increment for both sample A and sample B is 2.2–2.5, when the agitation time is
3–9 h. Surprisingly, at 5:1, 10:1 and 15:1 dilution ratio, the magnitude of increment is
constant, i.e., ~1.7 when the agitation time is 3–9 h. Previous study [13] showed that
119
the amount of deposited asphaltenes was either reached a plateau value or reduced,
when the dilution volume is higher than 15:1.
Figure 4a–d shows the plots for the deposited asphaltenes particles when differ-
ent types of liquid solvent were added to sample A. For the molecular structure of
these solvents, see Table 2. This study shows the effect of increment carbon number
(n-pentane, C5, n-hexane, C6 and n-heptane, C7) and the effect of functional
group (i.e., alkane group and benzene-ring group). Firstly, we observed the influ-
ence of n-pentane, n-hexane and n-heptane at 30°C (as in Figure 4a). At dilution
ratio 1:1, 0.860 g of asphaltenes were deposited when n-pentane and n-heptane
were added. A slight reduced (0.710 g) amount was observed when n-hexane was
added. This result suggests that the solubility of asphaltenes decreases when higher
solvent carbon number was used. As the viscosity of the solvent increases with
carbon number, asphaltenes diffusion is slower. Subsequently, fewer asphaltenes-
asphaltenes collision which then leads to lesser amount of deposited asphaltenes.
Meanwhile, at dilution ratio from 5:1 to 15:1 (as in Figure 4b–d), we observed that
the highest amount of asphaltenes was obtained when n-pentane was added, followed
by n-hexane and lastly n-heptane. Interaction between the long, planar molecules
of n-heptane and the planar, supramolecular asphaltenes compound would have
resulted in lower steric effect, and thus leading to a decrease in aggregation size [18].
Secondly, we found that both benzene and toluene do not significantly influ-
ence the deposition of asphaltenes, having measurements of less than 0.005 g.
Despite typically reported by authors worldwide, the asphaltenes deposition was
not affected by thermodynamic temperature variation. The reason anchoring this
observation is due to the solvent chemical properties. Asphaltenes are known to
be miscible in benzene (1 benzene ring) and toluene (1 benzene ring and 1 methyl
branch), or other similar structure compounds such as ethylbenzene (1 benzene
Figure 4.
Amount of deposited asphaltenes as a function of solvent type and temperature. The conditions of experiment
were: crude oil type = sample A, agitation time = 3 h. (a) 1:1, (b) 5:1, (c) 10:1, and (d) 15:1 dilution ratio.
120
ring and 1 ethyl branch) and xylene (1 benzene ring, 2 methyl branches). These
solvents would interact with asphaltenes and give similar value of enthalpy of
mixing (+ΔHmix = 0.5 ± 0.2 kJ) [19]. In asphaltenes mitigation strategy application,
these benzene-based chemicals are applied as dispersants.
Temperature factor plays an important role in preventing or reducing
asphaltenes deposition [20]. Figure 4a illustrates that 0.860, 0.980 and 0.960 g
of asphaltenes particles were deposited at 30, 50 and 75°C, respectively when
n-pentane was added. Consecutively, n-hexane follows the same trend, while
n-heptane had resulted in 0.710, 0.690 and 0.550 g of asphaltenes deposits at
30, 50 and 75°C, respectively. In general, it was noted that a discontinuity incre-
ment in the amount of deposited asphaltenes occurs at increasing temperature.
Heating process or existence of sufficient thermal energy hinders the mechanism
of asphaltenes aggregation. This is due to the weak force of interparticle attraction
between asphaltenes molecules and between asphaltenes and constituents (such
as saturates and resins) [21] hence lowers the ability for the asphaltenes particles
to coalesce. The influence of temperature effect on asphaltenes deposition was
similar with earlier study [13].
4. Conclusions
For the two samples of Malaysia crude oil, the amount of deposited asphaltenes
increased as the solvent-to-crude oil dilution ratio and the agitation time
increased. Similar trend was observed for both samples despite having distinctive
physical properties (cloud point, pour point and API gravity). Results also showed
that the amount of deposited asphaltenes is solvent-dependent (carbon number
and functional group) and temperature-dependent. Also, we suggest that future
studies on asphaltenes deposition should be linked to low/high region of solvent
dilution ratio.
Acknowledgements
The authors would like to thank Universiti Teknologi PETRONAS (UTP) for the
financial support given through the YUTP 015-LC0-064 grant.
Nomenclature
MW molecular weight, g/mol

CP cloud point, °C
PP pour point, °C
API The American Petroleum Institute gravity
RCF relative centrifugal force, g
ΔHmix enthalpy of mixing, J/mol
Abbreviations
cEOR chemical enhanced oil recovery

API The American Petroleum Institute gravity
ASTM American Society for Testing and Materials
121
Author details
Hazlina Husin1*, Mysara Eissa Mohyaldinn Elhaj1 and Colin D. Wood2
1 Universiti Teknologi PETRONAS, Ipoh, Malaysia
2 Commonwealth Science and Industrial Research Organization, Kensington,

Australia
122
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124
Chapter 8
Flow of Heavy Oils at Low

Temperatures: Potential
Challenges and Solutions
Emad Soliman
Abstract
Global demand for non-conventional heavy and extra-heavy oil has been mar-
ginal until the end of twentieth century because of their composition complexity
and high viscosity that cause many operational difficulties in the production with
decline of their economic viability. However, growing energy demands in the
beginning of the twenty-first century motivate many countries to handle such
non-conventional resources. Heavy extra-heavy crudes usually have higher pour
points due to high content of high molecular weight components, such as waxes,
asphaltenes, and resins. The structural changes for these components cause
abrupt rise in oil viscosity and simultaneous deposition of wax and asphaltene on
the inner walls of pipelines. This can cause clogging of pipes accompanying oil
flowability reduction with extra burden on the pumping system and consequently
increases its power requirement and cost. This chapter presents technological
challenges in transportation, describing the different mitigation strategies that
have been developed to improve the low-temperature flow properties of heavy
crude oils (heating, dilution, oil-in-water emulsion, and upgrading and core
annular flow).
Keywords: heavy crude oils, cold flow, heating, dilution, oil-in-water emulsion,
upgrading, core annular flow
1. Introduction
The continual global demand for petroleum fuels led to the decrease in sup-
ply from conventional reservoirs. Where, the conventional light oils had typically
been produced at a high rate and a low cost. Therefore, the plateau in conventional
oil production and the corresponding increase in the demand for liquid fuels have
motivated markets to respond with higher oil prices and subsequently have stimu-
lated in the global oil industry the advancement in technologies for the exploitation
of reservoirs of transitional and unconventional oils [1, 2]. An array of these new oils
including oil sands, tight oil, heavy oils (including extra-heavy oils and bitumen),
deep water oil, and eventually oil shale are projected to fill the gap through the next
few decades and that could continue to be revised upward as new technologies are
developed so that they could dominate the liquid-fuel supplies through the endings
of the twenty-first century especially regarding the global abundance of these new
oil supplies.
125
The oil industry is expected to invest huge sums in petroleum production and oil
infrastructure in the years ahead, up to an estimated $1 trillion over the next decade
alone. Without a concerted policymaking effort, these investments will likely
continue to flow disproportionately toward unconventional oils. The involvement
of unconventional crude oils in the international energy markets faces serious dif-
ficulties that need certain technological developments in the production, refining
and transportation [3].
As conventional crude oil supplies have peaked and leveled off globally in recent
years, oil has begun to transition, the makeup and geography of the new or tomor-
row’s oil, however, will be dramatically different from the current ones. Generally,
the International Energy Agency defines conventional oil as “a mixture of hydro-
carbons that exist in liquid phase under normal surface conditions”. Meanwhile,
unconventional oils are defined as those oils obtained by unconventional produc-
tion techniques because they cannot be recovered through pumping in their natural
state from an ordinary production well without being heated or diluted. By other
words, unconventional oils require new, highly energy intensive production tech-
niques and new processes to deal with their inaccessible placements or unusual
compositions. In this context, the U.S. Department of Energy divides unconven-
tional oil into four types: heavy oil (HO), extra-heavy oils (EHO), bitumen, and oil
shale. Moreover, some analysts include oils produced from natural gas or coal using
gas-to-liquids (GTL) processes and coal-to-liquids (CTL) processes in the uncon-
ventional oil category. These unconventional oil-processing techniques broaden
the feedstock of unconventional oils to include unconventional natural gas, such as
tight gas, shale gas, coal-bed methane, and methane hydrates [4] (Figure 1).
These new oils are an abundant untapped potential energy source, which
is expected to be a large contributor to the world’s energy needs in the future.
Figure 1.
Transformation of liquid fuels.
126
However, these oils tend to be less valuable than conventional crude in addition to
the technological costs per barrel that are currently much higher than for conven-
tional resources, which is readily transformed into the most marketable petroleum
products by today’s standards.
2. Physico-chemical properties of new crude oils
Crude oil is a mixture of different compounds consisting of hydrocarbons,

heteroatoms, and metals. The various compounds can differ widely in molecular
structure, volatility, density and viscosity. These compounds are usually divided
into fractions: saturates, aromatics, resins and asphaltenes (SARA). The saturate
fraction is non-polar and includes linear, branched and cyclic alkanes. Long-chain
linear alkanes (>C20) are known as waxes, or paraffinic waxes, and can make oil
recovery challenging as the wax becomes solid at low temperatures. Aromatics are
slightly more polar and consist of one or more aromatic rings connected by double
bonds. Saturates and aromatics constitute the majority of the crude oil. Resins
and asphaltenes are the most polar heavy molecules and complex components in
crude oil. The majority of heteroatoms and metals are found in these fractions.
Conventional oils are hydrogen-rich compounds with relatively short hydrocarbon
chains, fewer carbon atoms (C1–C60), and lower molecular weights than most
unconventional oils (around 200) where hydrogen packs all of the energy while
carbon goes along for the ride [5]. The physical properties and grade of oil depends
on the dominance of one of the hydrocarbons or its fractions in its composition.
The light conventional crude oil has low density where several of the molecules are
volatile, while the unconventional heavy oils have high density and high viscosity
where resins, paraffins and asphaltenes are found at a higher amount than those in
light crude oil [6, 7]. These oils require special treatments for their extraction and
transportation according to their content of these compounds. Regarding the close
relation between the physical properties of crude oil with these content, it is worthy
to mention that the crude oils can be categorized based on the paraffin content into;
less paraffin-oils (paraffins < 1.5%), paraffinic or waxy oils (paraffins = 1.5–6%)
and high paraffin- oils (paraffins > 6%). Also, the crude oils can be categorized
based on their content of resins into; less resins-oils (resins < 8%), resinous oils
(resins = 8–25%) and high resins-oils (resins > 25%). Additionally, sulfur and vana-
dium are present in high concentrations in heavy oils and lead to reduce its quality
and cause many problems through extraction, transportation, storage, and refining
of these oils as a result of the side reactions of these compounds causing the corro-
sion effects on pipelines, boilers, and storage tanks. In this context, the crude oils
can be also categorized based on their content of the sulfur compounds into; sweet
oils (total sulfur level < 0.5%), sour oils (total sulfur level > 0.5–1.9%) and highly
sour oils (total sulfur level > 1.9%). These sour crude oils containing larger amounts
of the impurity sulfur, an extremely corrosive element that is difficult to process,
and deadly when released hydrogen sulfide gas.
Generally, transitional oils have compositions comparable for that of conven-
tional oils; however, they are extracted by unconventional means. As conventional
oils become less accessible, new, more technical, energy-intensive methods are
being developed for their recovery, from ultra-deep wells drilled miles below the sea
to fracturing shale rock in order to tap oil trapped in low-permeability siltstones,
sandstones, and carbonates deep in the earth. Meanwhile, heavy oils are tricky to
extract, requiring gas injection and other invasive techniques due to their high,
molasses-like viscosities that approach those of unconventional oils. On other
hand, the unconventional oils are typically much heavier and sourer than even the
127
Table 1.
The composition of crude barrel originating from various regions.
lowest-quality conventional oil, where the heavier oils such as, oil sand (bitumen)
and oil shale (kerogen), are the more carbon laden, higher in sulfur, and filled with
toxic impurities. And therefore, conventional light oils tend to deliver more produc-
tivity with less waste than unconventional oils.
Crude oil make-up is highly dependent on the origin and depth of reservoir.
Whereat no two sources are alike, no two crudes are exactly alike or have the same
make-up. However, there can be a great deal of variation within a range. The natural
resources range from high-quality “light, sweet” crudes to lower-quality “heavy,
sour” crudes based on their region (Table 1).
The physical properties of crude oils are highly related to their make-up.
Furthermore, the technological conditions applied during exploration, drill-
ing, transportation and storage of these oils can affect strongly their physical
properties. On the other side, the physical parameters have to be in the allowable
ranges to achieve the highest potential yield technologically and economically.
Density and viscosity are the most important physical properties affecting the
flowability of the crudes. Such flowability has a great and clear impact through
the transportation and storage of these liquid hydrocarbons, especially for new
unconventional ones. Where, some of these new hydrocarbon resources are
effectively solid and must be removed through mining or heated in place (in
situ) until they flow. Extra-heavy, impure oils also require very large energy
inputs to upgrade and preprocess into synthetic crude oil that is then processed
by a refinery (known as feedstock). Therefore, such key properties determine
the economics of a heavy oil field development. Generally, heavy oil sells at a
lesser price than lighter hydrocarbons, as it will have to go through an energy
intensive upgrading process before use. On the other hand, high viscosity values
lead to lower production and more expensive enhanced oil recovery (EOR)
investments.
The density of the oils is measured on a scale known as API gravity developed by
the American Petroleum Institute and the National Bureau of Standards developed
a scale of the density of liquid petroleum products. The gravity scale is calibrated in
terms of API degrees, which equals:
(141.5 / Specific gravity (SG) at 60 F) − 131.5

°
(1)
The lighter crudes have the higher API gravity. If the API gravity is greater
than 10, the oil is lighter and floats on water; if less than 10, it is heavier and sinks.
Generally, API gravity of light crudes exceeds 38°. However, it is commonly below
22° for heavy crudes. Intermediate crudes fall between 22 and 38°. Extra-heavy oils
are below 10; the API gravity of bitumen approaches zero.
128
Viscosity is measured in centipoises (cP) that represents the oil’s resistance to

flow; the higher the value, the higher the viscosity. Viscosity is the property that
most affects production and recovery operations where it complicates its produc-
tion and pipeline transportation, due to its poor fluidity and high pressure dif-
ferentials generated with values between 20 cP and more than 1 × 106 cP [8, 9]. The
heavy oil in terms of viscosity was defined as the class of oils ranging from 50 to
5000 cP. Among the different compounds of crude oil, asphaltenes are usually most
responsible for the high viscosities in HO and EHO.
The high viscosity restricts the easy flow of oil at the reservoir temperature and
pressure [10]. The viscosity of heavy crudes is strongly affected by temperature
variations. For this reason, thermal recovery methods are commonly used in heavy
oil production. Figure 2 shows the relationship between viscosity and temperature
for two Athabasca bitumen samples. There is no universal relationship between
oil density and viscosity. However, oils are generally found to be more viscous
when density increases. This relation can be greatly attributed to the presence of
asphaltenes, which are high molecular weight polycyclic hydrocarbons that tend to
aggregate. Indeed, it has been shown that the viscosity of oils increases exponen-
tially with asphaltene content [11].
Figure 3 is a graph relating viscosity and API ratings and it can be observed that
the heavy oil region lies in the high viscosity range.
The high density and viscosity of unconventional oils at atmospheric conditions
has traditionally made their recovery very energy demanding compared to lighter
crudes and has resulted in very low recovery factors, which means that these oils
tend to result in higher carbon emissions and other societal impacts. Mnemonically,
when other factors being equal, the lower the API gravity, the oil will be more expen-
sive to extract and process, and simultaneously the obtained oil will have lower price.
The rheological properties are highly controlling all processes in which fluids
are transferred from one location to another such as in, the migration of crude oil
within the oil reservoir and transportation of the crude oil from oil wells and the
refining units. Therefore, the unconventional oils are required to have the fluid
viscosity of the migrating conventional oils [13]. The viscosities of the uncon-
ventional crude oils (i.e. heavy oil and bitumen/tar sands) at 25°C might reach
more than 105 cP. The extremely low flowability due to high viscosity at reservoir
Figure 2.
Viscosity—temperature relationship of an Athabasca bitumen [12].
129
Figure 3.
General relationship of viscosity to API gravity [2].
conditions, especially in offshore conditions alongside asphaltene deposition,

heavy metals, sulfur and brine or salt content making these kinds of oils more
challenging to produce, transport as well as refine by conventional means without
firstly upgrading them to meet conventional light crude oil properties [14, 15].
It is well known that pipelines are the most effective means of transporting
crude oil from the producing field to the refinery because of their low expense
and environmentally convenient. As such, transportation of the heavy crude oil
via pipeline is a major challenge for petroleum industries, where conventional
pipelining is not adequate because of the huge energy (i.e. high pumping power)
is required to overcome the high pressure drop in the pipeline, owing to their high
viscosity. Therefore, to transport heavy oils economically, the pressure drop in
the pipeline must be lowered to minimize the pumping power via reducing the
viscosity [16]. Furthermore, the pumping temperature is an important affecting
factor of the flowability and consequently the pipeline transportation of crude oil.
Heavy crudes usually have higher pour points due to high content of high molecu-
lar weight components, such as waxes, asphaltenes and resins. Under conditions
in which the atmospheric temperature is below the pour point, gelation of the
crude oil occurs lowering its flow completely and causing severe transportation
problems. Especially in the cold offshore environment, waxes and asphaltenes
deposit over inner surfaces of pipelines and eventually clog the pipelines, which
decreases the accessible cross-sectional area for oil flow that causes reduction
in flow rate and rise in pressure drop and multiphase flow, may occur resulting
to further increases in the pumping cost [17, 18]. Here, it is worthy to mention
that the desired pipeline viscosity of crude oils might not exceed 400 cP at 25°C
[19–21]. However, it should be less than 200 cP at 15°C [22]. On the other side,
the presence of brine or salt in the heavy crude stimulates corrosion problems in
the pipeline [17]. In some cases, the formation of emulsion such as the oil-water
mixture produced from the reservoir poses transportation difficulty.
3. Mitigation technologies for low flowability
Sync of the ever-growing world energy demand with the decline of conven-
tional middle and light crude oil reserves and the limited supply and rising price
130
Figure 4.
Schematic diagram presenting different methods for improving flow of heavy crude oil and bitumen and
facilitating their transporting via pipelines.
of crude oil led to attract the interest the petroleum industry growingly in heavy
crude oil and bitumen/tar sands exploitation. Nevertheless, the exploitation of
these crudes is still low because of the technical challenges that face it at all stages
from recovery/production from the reservoir to transportation and refining
[23, 24]. To reduce this high-pressure drop and cost of transportation, several
technologies have been proposed to improve the flow properties of the heavy
crude oil and bitumen through pipelines and thus to meet the production volumes
projected by the market. Generally, these different technologies can be divided
into three categories (Figure 4) including (1) viscosity reduction [e.g. preheat-
ing of the heavy crude oil and bitumen and subsequent heating of the pipeline,
blending and dilution with light oils or organic solvent, emulsification through
the formation of an oil-in-water emulsion and lowering the oil’s pour point by
using pour point depressants (PPDs)]; (2) drag/friction reduction [e.g. pipeline
lubrication through the use of core-annular flow, drag reducing additive]; and
(3) in situ partial upgrading of the heavy crudes to produce synthetic crudes with
lower viscosity [23, 25].
In this chapter, various technologies available for transporting heavy crude oil
and bitumen from the production site to the processing facilities including viscosity
and friction reduction and in-situ upgrading are reviewed with extensive discus-
sion. The author provide a review of typical methods such as heating and dilution,
and also point out lubrication solutions to move heavy and extra-heavy oils, such
as core-annular flow and o/w emulsions. The advantages and disadvantages of each
technology are highlighted with the view that the chapter will provide direction
for improvement and development of novel economically viable technologies to
improve the transportation of heavy oils via pipelines. Other approaches as drag
reduction additives and pour point depressants (PPDs) may be complementarily
discussed in a later section in this work.
4. Heating
Heating technique is commonly utilized to overcome the difficulties related to

the transportation of the heavy crude oil. This technique involves preheating the
heavy crude oil followed by subsequent heating of the pipeline. Such thermal treat-
ments are based on the strong viscosity-temperature relationship, since the viscos-
ity of the heavy oils and bitumen is reduced by several orders of magnitude with
increasing temperature and subsequently the flowability of such oil is improved and
it will be easier to pump. The response of viscosity to changes in temperature for
some heavy oil and bitumen is illustrated in Figure 5 [26]. Heat should be applied
131
Figure 5.
Response of viscosity to increase in temperature [26].
to the oil to guarantee that its viscosity reaches acceptable values for transport in
pipelines. These values typically refer to a maximum viscosity of 500 cP, below
which many crude oils can be economically pumped [27, 28].
Equations proposed to represent the viscosity temperature relationship are com-
monly of logarithmical or double logarithmical forms. Many of these equations are
based on the Eyring relationship that has been proposed in 1936:
( )
N . h . exp ____
η = ____ ∆G′
(2)
V RT
where, η, ΔG′ and V represent the absolute viscosity, the Gibbs’s activation
energy and the molar volume, respectively. The parameters h, N and R are the
Planck, Avogadro and ideal gas constant parameters, respectively. Eyring’s equation
was the base for proposing many others exponential types of viscosity-temperature
relations. Among the large number of equations proposed, Walther’s equation has
been widely applied to represent the viscosity of the oil and its fractions.
Log (log η + C) = A + B . log (T) (3)
where, η is the dynamic viscosity, A and B are constants that depend on the
nature of the liquid, C is a fixed constant for most oils (C = 0.6 for viscosities above
1.5 cSt (cP/SG) and varies slightly with smaller viscosities) and T is the absolute
temperature.
The effect of temperature upon viscosity relies greatly on the composition or
volatility of the oil [29]. For pure compounds and single systems, the tempera-
ture effect on the global system is dictating by the solvent properties. However,
for complex systems, such as crude oil, a raise in temperature affects mainly the
petroleum macromolecular structures, promoting disruption of their aggregate
and maintaining monomer units scattered. Therefore, the dispersed system should
be more favorable than those of the organized macrostructures because these
organized structures of the latter system enhancing its flow resistance [30]. A
well-documented example is the pipeline Alyeska in Alaska, which transports the
crude oil at approximately 50°C. A project involving heated pipelines is not an easy
task. However, there are many considerations have to be taken into account on the
design of a heated pipeline including; (a) instability in the flow of oils as a result to
change of their rheological properties that may be possibly induced by heating the
pipeline, (b) many number of heating and pumping stations are required over long
132
distances of pipelines posing an additional cost, and (c) the heat losses along the
pipeline because of the low flow of the crude oil i.e., heat loss is present during oil
flow (the cooling effect). Therefore, heating stations should be planned anticipat-
ing gradual cooling in the line where, the pipeline is often insulated to maintain an
elevated temperature and reduce the heat losses to the surrounding water as well
as the earth lowers the efficiency of the technique. In such case when the pipeline
is vulnerable to shut-in, a heated diluent has to be injected to restart flow in the
pipeline [27]. In warmer climates where the ambient temperature does not bring
the heavy oil below the pour point, electrical heating may be used to boost produc-
tion without the need for special restart procedures. This has been demonstrated
on shorter production lines in Colombia [31]. Although widely diffused as a
method for viscosity reduction for transportation, heating is expensive due to the
high cost of heat generation, especially when applying it in cold regions. Therefore,
this technique might not be viable for transporting crude oil when it comes to
subsea pipelines, sudden expansion and contraction along the pipeline may induce
challenging problems, as well as the high rate of corrosion inside the pipeline due
to the high temperature. Consequently, the capital and operating costs will be
significantly high especially over long distances of pipelines from the oil field to
the final storage or refinery on the high side [32]. The costs of insulated pipelines
or installing heaters are less than that of dilution or upgrading.
5. Dilution
Dilution/blending of heavy crude oil and bitumen with light hydrocarbons

or organic solvents is the most commonly used oldest and preferred technique
to reduce viscosity and to improve their transportation via pipelines almost five
decades ago. The cost-effective diluents used to enhance the transportability
of heavy crude oils in pipelines are relatively cheap and readily available. The
widely used diluents include light crude oils and light to medium products from
the upgrader or refinery processes such as naphtha, kerosene, etc. as well as light
natural gas condensate, by-product of natural gas processing. However, the use of
organic solvents such as alcohol, methyl tert-butyl ether (MTBE), tert-amyl methyl
ether (TAME), and dimethyl ether (DME) has been investigated [33]. Generally, it
is well known that blending the fluids or diluents with the lower viscosity produce
the blended mixture of heavy crude and bitumen with the lower viscosity which is
easier to pump allowing transportation of a large quantity or volume of these oils
at reduced cost [34]. Furthermore, dilution helps the desalting and dehydration
operations downstream. The viscosity of the resulting blends depends on the vis-
cosities and densities of the heavy crude oil and bitumen and the used diluent, the
dilution rate, heavy oil/diluent ratio and also the operating temperature. It is worthy
to mention here that heavy crude oil and bitumen can have a viscosity of more
than 105 mPa s. However, viscosity of the diluted or blended oil must be less than
200 mPa s to transport heavy crude oils conveniently via the classical pipelines [22].
In this sense, large volume of diluents is required to achieve this pipeline viscosity
specification where, the amount of diluents required for bitumen is higher than
that for heavy crude oil where, the ratio of diluents/heavy oils in their exported
blends ranges from 0 to 20%, while it is in the range of 25–50% for diluents/bitu-
men blends. The method also suffers certain disadvantages. The dilution of heavy
crude oils is employed to enhance pipelining using two pipelines, one for the oil
and another for the diluents via two main strategies depending on whether, the
diluent is recycled or not. In both cases, a larger pipeline diameter is needed. This
demands considerable capital and operational investment in pumping and pipeline
133
maintenance. Moreover, the difficulty in prediction of solvent/oil ratio required for

achieving a reduction in viscosity owing to the large and inconsistent number of
governing parameters leads to ineffectiveness of simple mixing rules and therefore,
the diluent will command a significant hold-up. The non-recycling strategy is based
on the availability that secure the steady supply for the diluent. As the light hydro-
carbons (i.e. diluent) may be acquired from neighboring conventional oil fields that
the company owns, or from a competitor which could prove costly, something that
may not be the case at peripheral heavy oil fields. In case of recycling strategy, the
project economics are less of a subject to the price of diluent. However, this strategy
is required, as recycling facilities and constructions required to return of diluent to
the production site pose an additional capital expenditure.
Also, the oil composition has to be considered on selection of the solvent.
This consideration is due to the compatibility issues between the asphaltenes and
paraffins present in the oil with the solvent. If due care is not taken, deposition
of asphaltenes and paraffins can cause further problems as, the light condensate
recovered from natural gas (C5+ or “Pentane Plus”), a low-density and less vis-
cous mixture of hydrocarbon liquids, has been used to dilute the heavy crude oil
and bitumen in order to enhance their transportation using pipeline in Canadian
and Venezuelan oil fields. Though the efficiency of this condensate in reducing
the viscosity of the heavy crude oil and bitumen significantly, instability during
transportation and storage is observed as a result to precipitation, segregation
and aggregation of asphaltenes [35]. These findings are because of insolubility
of asphaltenes in most of condensate components involving alkanes such as
n-pentane and heptanes. Besides, asphaltenes have the tendency to interact and
aggregate in the oil-condensate blended mixture, as the condensates are known
to be paraffin rich light oil. This may result in flocculation which leads to partial
plugging of pipelines. Furthermore, the availability of condensates based on nat-
ural gas demand is one of the important limitations to its use as a heavy oil thin-
ner where, the production of condensate is not sufficient to sustain the demand
due to the growing production of heavy crude oil and bitumen [27]. Thus, light
crude oils with API gravity between 35 and 42 have also been employed for
dilution of the heavy ones, but it is less efficient than the condensate in lower-
ing their viscosity [36]. Because of decline of the reserves of conventional light
crudes, these oils suffer similar disadvantages as condensates like availability and
compatibility with asphaltenes. Also, the light hydrocarbons such as gasoline and
kerosene as distillates have been found to be effective owing to their good solvent
properties. Gasoline also helps to improve the octane number in downstream
processing. Thus, it has been shown that 15% kerosene mixed with heavy oil at
50°C achieves the same viscosity reduction achieved by 20% kerosene at room
temperature [37]. Another common diluent used is naphtha, hydrocarbons
ranging from C6 to C12 from naphtha fraction of crude oil distillates. Naphtha has
high API gravity (low density) which leads to efficient dilution of crude oil and
shows good compatibility with asphaltenes owing to the presence of aromatic
content in it. It is easily recyclable and reusable. However, the mostly used light
hydrocarbons for dilution of heavy crude oils are expensive and are not readily
available in large quantities. Therefore, the recycling is essential in despite of the
required large investments and subsequently additional operating cost.
As previously mentioned, employing of organic solvents including MTBE,
TAME and DME in thinning the heavy crude oils have been considered [33].
Recovery of DME is easier than the other solvents. Indeed, alcohols have been
found to be more effective in reducing the viscosity where, the addition of
ethyl alcohol at 10% led to reducing viscosity of the crude oil by almost 80%
at 25°C [38]. This can be due to interaction between the hydroxyl groups and
134
Figure 6.
Effect of naphtha/organic solvent blend at different volume fraction on the viscosity of the diluted heavy crude
oil.
asphaltenes [39]. The use of these solvents is prompted based on their use in

improving the octane number of gasoline. Subsequently, a mixture of hydrocar-
bons and organic solvents bearing polar groups onto their molecular structure has
slightly exhibited efficacy in viscosity reduction of heavy crude oil at constant
dilution rate [34]. Therefore, it has been proposed that a blend of naphtha and
organic solvent would reduce the amount of diluents needed to lower the viscosity
of heavy oil-to-pipeline transportation specifications [34]. The relative viscosities
of the blend of heavy oil diluted with mixtures of naphtha and organic solvents are
shown in Figure 6. The reduction of viscosity for resulting diluted heavy crude oil
is attributed to the increasing polarity or hydrogen bonding of the solvents and the
ability of the polar solvent to solubilize the asphaltenes components present in the
heavy crude oil [34]. In that case, high polarity of solvents enhances their dilution
efficiency causing greater reduction in viscosity of the heavy crude oil. However,
the solvent can be easily recycled when its viscosity is comparable for that of the
hydrocarbon as well as their boiling point.
Recently, the effect of carbon dioxide on the heavy crude oil has been studied.
The findings of this studies have showed that crude oil saturated with carbon dioxide
undergoes significant reduction in viscosity at a given temperature and pressure [40].
5.1 Prediction of resultant viscosity of the crude oil-diluents mixture
Generally, there is an exponential relationship between the viscosity of the

resulting mixture and the volume fraction of diluent, so small fractions of diluents
can cause a noticeable decline in oil viscosity. The addition of light oils or solvents
resulted in lowering the frictional pressures. The rate of this reduction is greater in
lower temperatures [30]. Up to date, a number of correlations have been developed
for prediction of resultant viscosity of the blended mixture of heavy crude oil and
diluents. But the accuracy of these relations is limited owing to the number of
parameters involved in them. A few relationships have been discussed by Gateau
and others [34]. In essence, viscosity of the resulting diluted heavy crude oil can be
135
calculated from a modified correlation developed by Lederer [41] that is similar to

the classic Arrhenius expression as follows:
log μ = (_______
αVo + Vd )
log μo + (1 − _______
αVo + Vd )
αV αV
o o
log μ d (4)
Where, Vo and Vd are the volume fraction of the heavy crude oil and diluents, μo
and μd are the viscosity of the heavy crude oil and the diluents, respectively, and α is
an empirical constant ranging from 0 to 1. Thus, an empirical formula for determin-
ing the constant α for the blend of heavy crude oil diluted with light hydrocarbons
has been proposed by Shu [42]. This relation depends on the differences in densities
of oil to diluents (i.e. light hydrocarbons) and their viscosity ratio.
0.5237 3.2745 1.6316
17.04 (ρ o − ρ d) ρo ρd
α = _____________________________
μo (5)
ln (__
μd )
where, ρo and ρd are densities of oil and solvent, respectively.

Currently, partial upgrading and dilution may be used in different stages of
heavy crudes production. In the Orinoco field developments in Venezuela, the
heavy oil is diluted at the production site for pipeline transport to a centralized
refinery. At the refinery, the heavy oil goes through and upgrading process for
further transport, while the diluent is separated from the blend and returned to the
production site for recycling.
6. In-situ upgrading
In situ upgrading has been employed at surface conditions to locate the heavy
crude oils and bitumen in viscosity conditions required for its production and
transportation. In general, partial upgrading is often preferred with regard to entire
upgrading because the cost of the process and the extension of the upgrading depend
on the cost-benefit relation. This partial upgrading uses hydroprocessing to modify
the relative proportion of the oil hydrocarbons (the composition of heavy oils) into a
field refinery to make them less viscous and subsequently more suitable for pipeline
transport without altering its refining characteristics. Hydroprocessing is a broad
term that includes hydrocracking, hydrotreating, and hydrorefining. Where, the
partial upgrading process is usually performed in two stages. In the first stage, called
hydrocracking, the heavy oils are heated along with hydrogen under high pressure to
promote the scission of macromolecular structures in the oil molecule rupture, form-
ing smaller and simpler chemical structures as smaller paraffin and olefin molecules
that change the properties of oil and the quality of its products as the viscosity of oil
that reduce and it become lighter. In the second stage, called hydrotreating, hydro-
gen is added to promote hydrogenation without breaking structures and to remove
impurities [29]. The hydrogenation process is catalyzed by metals such as nickel, pal-
ladium and platinum. Since metal catalysts are easily poisoned by sulfur containing
compounds, the operation of the process requires a refined control technique. In this
stage, the saturation of olefins and the conversion of aromatic compounds into naph-
thenics occur wherefore, the proportion of saturated carbons and aromatics increases
with reducing the amount of asphaltenes and oil resins [43, 44]. Hereby, the upgrad-
ing process produces a large unwanted byproduct of coke that has to be handled and
deposited. The potential advantage of upgrading over other techniques is to improve
the quality for both of the oil and the residue, simultaneously with increasing its
market value. Residue can represent significant portion of a crude oil barrel and its
136
disposal treatment is not yet up to the mark [45, 46]. In this view, the conversion of
residue into more consumable and valuable products is also an environmental issue.
On the other hand, the increasing fuel oil demand makes the processing and utiliza-
tion of bottom residue from atmospheric distillation and vacuum distillation columns
unavoidable. Moreover, the partial upgrading has the advantage of lower pipeline
investments, limited restart issues and no particular corrosions. Nevertheless, the
investments associated with a field refinery demands a large production.
Summarily, upgrading can be considered as a process of carbon rejection and
hydrogen addition [47]. Carbon rejection processes include visbreaking, thermal
cracking, coking, deasphalting, and catalytic cracking, while hydrogen addi-
tion processes include catalytic hydrodemetallization, hydrodesulphurization,
hydrodenitrogenation, hydrogenation, and hydrocracking in fixed bed, moving
bed, ebullating bed, or slurry phase reactors [45–48]. Hereof, it was indicated that
the partial upgrading is a hybrid approach involving a simultaneous use of several
of these technologies. The assembly used as the strategy for upgrading depends
on the product value and the SARA fraction distribution in the oil [45, 49]. Since
asphaltenes and resins are the major constituents of heavy oils, these components
present the highest impact on the method selection. So the heavy oils containing
whether high resin and low asphaltene or low resin and high asphaltene even when
both have the same API gravity, different upgrading processes must be employed
[45, 50]. Farther, other considerations beside the properties of the oil have to be
taken into account through choice of the upgrading treatments assembly such as,
regional logistics between the well-head and the refining site, operational concern,
transport distance, cost, environmental concerns and the legislation.
Example of the proper upgrading treatments developed by Association for the
Valorization of Heavy Oils (ASVAHL) are deasphalting process Solvahl, thermal
treatment Tervahl process and catalytic hydrotreatment Hyvahl processes [51].
Recently, many studies at Institut français du pétrole (IFP) aim to associate these
different processes to optimize the heavy crude conversion. The combination of
thermal cracking, solvent deasphalting and hydrocracking processes are commonly
used for the processing of heavy oils. Furthermore, the present strategy in the
petroleum industry is to integrate in situ upgrading to thermal enhanced oil recov-
ery (EOR) methods for achieving the cost, environment and energy effectiveness.
The Syncrude operations in Canada are an example of this, where surface mined 8°
API bitumen is upgraded to a 30–32° API synthetic blend. It has also been practiced
in Venezuela to export extra-heavy oil from the Orinoco belt. In situ upgrading
technologies which can be achieved during thermal recovery methods include ISC,
SAGD, CSS and subsequently the novel THAI and its add-on catalytic upgrading
process in situ (CAPRI), collectively called THAI-CAPRITM [15, 24, 52]. These
processes rely on the reduction of heavy crude oil viscosity by heat to improve its
flow from the oil reservoir to the production well. This in situ thermal cracking
process reduces the viscosity of the heavy oil and bitumen to a high order of mag-
nitude, thereby improving flow and production. However, of all these processes,
the THAI-CAPRI process integrates a catalytic upgrading process into the recovery.
Details of the above-mentioned in situ upgrading technologies for during heavy oil
recovery have been presented in a review article involving the novel extraction and
upgrading technologies for heavy oil and bitumen by Shah and others [46].
7. Coverage of heavy oils by water
Coverage of heavy oils by water to facilitate their transportation via pipelines is a

technology based on a physical phenomenon in which a less viscous phase migrates
137
to the high shear region near the pipe wall, where it lubricates the flow. Once the
pumping pressures are balanced by the wall shear stress, covered transport requires
pressures that are comparable to pumping water alone, regardless the viscosity
of oil [53, 54]. The oil and water phases can be configured in various ways during
pumping. In horizontal pipes, the most common configurations are stratified flow
based on the two phase’s density, oil-in-water emulsions (stabilized by surfactants),
and core annular flow, which are the most approaches employed in transport of
heavy oils via pipelines including elevation ducts. These configurations depend
strongly on the flow rate of oil and water [55].
7.1 Core-annular flow
Core-annular flow (CAF) is a technology to facilitate the flow of heavy crude oil
and bitumen through pipeline by reducing the pressure drop in the pipelines owing to
the friction. Where, this friction caused by the high viscosity of these fluids can make
their flow in a single-phase is so difficult or undoable. This technique was first reported
by Isaacs and Speeds in 1904 for the possibility of pipelining viscous fluids through the
lubrication of pipe walls with water [56]. However, a commercial pipeline dedicated to
transportation of heavy oil through annular flow was not in operation until the 1970s
[57, 58]. Commercial establishing for core-annular flow systems involves not only
technical questions but also operational methodologies to increase their feasibility and
flexibility. The effectiveness of the commercial implementation of core annular flow is
related to its adaptability to existing pipeline systems, in particular its capacity to share
with other types of fluids that are not incorporated in the core flow regime. Core flow
has attracted much industrial interest, being the subject of many patents to facilitate
the pipeline transportation of heavy oils [59]. Almost, the most important industrial
application among them up to date is employed in the Shell project in California, in
which a 38.6 km pipeline from North Midway Sunset reservoir to the central facilities
at Ten Section (California) operates for 12 years with 30% volumetric water with a
flow rate of 24,000 barrels per day. Other examples include the 55 km lubricated pipe-
lines from San Diego to Budare (Venezuela) used for transporting Zuata heavy crude
oil (9.6 API°) and the self-lubricated pipelines of Syncrude’s Canada Ltd. [60].
The core-annular flow technique is based on exploiting the low viscosity of water
and high density of heavy oil to form a concentric flow pattern, where thin film
of water or aqueous solution formed onto the inner wall of the pipe, “lubricating”
the flow of core fluid consisting of heavy oil. Lining the pipe with an aqueous film
is done by injecting water into the pipeline at its head (Figure 7). Accordingly, the
core-annular flow is considered one of the regimes based on flow of two-phase via
pipelines. Somewhere further down the pipeline, formation of an aqueous coating
around the core of heavy oil will stabilize the flow with reducing the friction pres-
sure loss. Where, the reduced longitudinal pressure gradient and a total pressure
drop are similar to that of volumetrically equal pure water flow [57, 58, 61]. The typi-
cal fraction of water required in this approach (10–30%) implies that the pressure
drop along the pipeline depends very closely on the viscosity of water, but weakly
on that of the heavy oils [23, 62]. Furthermore, the pressure drop reduction exceeds
90% when the flow of water as an annulus near the pipe wall surface is done around
the core of heavy crude oil comparing with that without water lubrication [57].
If the core-annular flow is assumed to be perfect and well centered, then the
pressure drop can be calculated from the following equation:
Q
∆ P = ______________
___ (6)
8 [ μw s ( μ 0 − μw )]
L __ R 4 + R 4 __
π ___ 1 ___ 1
138
Figure 7.
Illustration of the core annular flow injector configuration [57].
where ΔP/L is the pressure drop of the centered core-annular flow (Pa/m), Q is
the total flow rate (m3/s), R is the radius of the pipe (m), Rs is the core radius (m),
and μw and μo are the dynamic viscosities of water and oil, respectively (Pa s).
Despite of core annular flow capability for reducing the pressure drop to that of
moving water, achieving this perfect flow having high stability is very rare because
such perfection and great stability may only accomplish with density-matched and
immiscible fluids. i.e., have similar densities and do not form emulsion [57, 63].
Whereas, the mechanisms of hydrodynamic destabilization of the annular flow
originate from capillary forces and inertia (the difference between the interfacial
velocity of the fluids), are evidenced by the deformation of the liquid-liquid
interface. These flow velocity and capillary instability arising from surface tension
and the density difference between the liquids break the inner core into slugs at low
velocity and stratification occurs in the system. Hereby, several flow regimes may
occur depending on the properties of the oil such as density, surface tension, and
shear rate of the flow and fluid injection flow rate. Where, wavy core-annular flow,
in which waves are created at the water and oil interface can occur (Figure 8). This
flow regime is more likely to be present in the core fluid through the core annular
flow process [64]. Furthermore, a radial movement of the oil core to the upper
wall of the pipe by act of a buoyancy force can occur when the density difference
between the oil and water is large (Figure 9). On the other side, increasing the
velocity enhances the core flow stability.
Still, there are significant problems encountered in the commercial application
of annular flow for heavy oil transportation as instability of the flow regime, foul-
ing and corrosion of the pipe walls. These problems emerge the moment flow rate
drops or the pipeline is shut-in (Figure 10) where, the liquids will segregate into
two horizontal layers (stratification of the phases). If the pipeline has an elevated
section; this could lead to a permanent heavy oil plug blocking the flow. Knowingly,
many potential interruptions may occur in any normal pumping operation of crude
oil due to mechanical failure, power interruptions, and ruptures in the pipeline or
climate concerns. Ditto, interruptions occurring in the core annular flow-based
pipelining even for relatively short periods of time can lead to the stratification
of the two phases. This stratification of the two phases can be aggravated by the
difficulties of restarting the flow in case of unscheduled downtime, where high
139
Figure 8.
Schematic diagram of wavy Core annular flow [54].
Figure 9.
Radial position of the oil core: A perfect core-annular flow and b with density difference. C is the contact
perimeter between the oil phase (core) and the pipe wall.
Figure 10.
Shut-in issues occurred in core-annular flow.
pressures are required to restore the system [23]. This high pressure can cause major
failures in the pipeline as it may exceed the maximum allowable pressure. A basic
process has been proposed for restarting core flow with heavy oils after a long
standstill period in which a flow of a low viscosity fluid, water, is pumped first into
an inlet portion of the pipeline with increasing the flow gradually until reaching the
critical velocity required to develop annular flow in a steady state condition. Then,
the heavy oil is injected into the inlet portion of the pipeline, and similarly its flow
is gradually increased either by adjusting a variable speed motor to the pump or by
adjusting a control valve in a viscous oil bypass line. An increase of pressure due to
the pumping of heavy oil is much smaller than the pressure peaks observed during
the low viscosity fluid build-up stage.
Fouling as one of the main problems in implementing core annular flow caused
by the gradual adherence and accumulation of oil at the pipe walls that can cause
a blockage in the pipe section, preventing flow. The tendency of the oil to adhere
to the pipeline walls exhibited during annular flow of 9°API oil [65]. Even in the
hydro-dynamically stable annular flow which is able to maintain its structure
through various line accidents, the oil tends to embed itself in the pipe walls by
means of thermodynamic effects. Although the hydrodynamic stability of the sys-
tem can be achieved by adjusting the process parameters, the stability of the system
is still dependent on thermodynamic aspects [54, 55, 66]. In addition, formation of
140
the incrustations in pipes can occur due to the reversal of wettability of the system
caused by asphaltenes and naphthenic acids present in the oil [81]. The effects of
wettability reversal over the load loss of the system can be avoided or reduced by the
addition of sodium meta-silicate to the aqueous phase [67–69].
7.2 Emulsification
Several methods have traditionally been proposed to enhance the mobility of

heavy crudes for pipeline transportation; these include heating crude oils or dilut-
ing them with lighter fractions of hydrocarbons. However, each of these methods
has economic, technical and logistical drawbacks especially when it comes to
transportation of heavy crude oil through offshore pipelines.
Emulsions naturally occur in petroleum production and pipelining, mainly those
of water-in-oil (W/O) and more complex (double) emulsion like oil-in-water-
in-oil (O/W/O) emulsions (Figure 11). Such emulsions are detrimental for oil
production since oil’s viscosity raises, increment corrosion issues and are difficult
to break in desalting and dehydrating units before refining. Nevertheless, O/W
emulsion reduces the viscosity of heavy crude oils and bitumen and may provide
an alternative to the use of diluents or heat to reduce viscosity in pipelines [70].
Thereby, emulsification of heavy oils with water with aid of active surface additives
is considered to be one of the newest and most economical alternative techniques
to overcome flow assurance problems associated with transportation of heavy
crude oil through pipelines under the cold offshore environments. This technology
is hydraulically transporting heavy crude oil via pipeline in form of oil-in-water
(O/W) with the drop sizes in micron range can reduce the viscosity to values of
50–200 cP at 15°C [23, 25, 28], in which it can be easily pumped [37, 70–72]. The
methods used to generate the oil droplets to create the different possible emulsions
includes use of devices such as dispersing machines, mixing with rotor-stator, col-
loid mills, high-pressure homogenizers applying high shearing stresses, emulsifica-
tion by membrane and ultrasonic waves [39, 73, 74].
These oil-in-water emulsions are thermodynamically unstable where they can
be subjected to several breakdown processes like Ostwald ripening, sedimentation
and creaming due to density difference and coalescence of the drops [70]. Therefore,
a surfactant (or mixture of surfactants) suitable for varying conditions have to be
Figure 11.
The several emulsion forms used to transport heavy crude oils.
141
Figure 12.
Surfactant-stabilized emulsion.
added forming a strong interfacial film to enhance the kinetic stability of these emul-
sions and consequently improve their transportability by pipelines [75]. Besides, in
some cases additional substances as stabilizing agents (high molecular weight) to
avoid phase separation. Accordingly, cost of the surfactant, its ability to maintain the
emulsion stability during pipeline transportation and the ease of its separating from
the crude oil at the final destination (since the density of heavy oil is close to that of
water) are major challenges associated with the emulsification technology for trans-
porting heavy crude oils. Monolayer of the surfactant molecules settles onto the oil-
water interface to prevent drop growth and phase separation during transportation.
As shown in Figure 12, such interfacial monolayer is formed by directing the polar
region (i.e. hydrophilic head) of the surfactant toward the water phase and non-
polar tail (i.e. hydrophobic region) toward the oil phase. Hereof, the efficiency of
the surfactant based on the properties of this adsorbed layer (the polar hydrophilic
head and the non-polar hydrophobic tail) of surfactants that stabilize the oil-water
surface against shear and decrease the interfacial tensions, and subsequently control
the flow behavior of the emulsion [70]. However, heavy crude oil emulsion exhibits
either Newtonian behavior at high shear rate or a shear thinning rheological behavior
at low shear rate [25, 76].
Pointedly, properties of the emulsion including the rheological characteristics
and stability depend mainly on many parameters such as, drop size and their
polydispersity, temperature, salinity and the pH of the water, the components of
the heavy crude oil, mixing energy and oil/water volume ratio [39, 77]. Drop size
and their polydispersity depends on surfactant type, energy of mixing and pres-
sure. The use of a dynamic mixer as a rotor-stator mixer, may cause the formation
of small droplets with a diameter of less than 10 μm which can cause a significant
increase in the viscosity of O/W emulsion and emulsion inversion to an oil continu-
ous emulsion that are detrimental to pipelining.
The use of surfactants and water to create a stable oil-in-water emulsion with
heavy crude oil has been a topic of several investigations with a series of patents.
Stabilizing the O/W emulsion from Egyptian Geisum crude oil using an anionic
surfactant for pipeline transportation has been studied. The findings exhibited
that stability and viscosity of surfactant-stabilized O/W emulsion increased with
increasing concentration of the anionic surfactant that reduces the O/W interfacial
tension and size of dispersed droplets [78]. Similar results were found in a non-
ionic surfactant stabilized O/W emulsion [37]. Triton X-114 is one of the com-
monly used non-ionic surfactants based on their ability to withstand the salinity
of the produced water, they are also cheap, their emulsion is easy to separate, and
they do not form undesirable organic residues that affect the oil properties [79].
However, the use of anionic and non-ionic surfactants produced a synergistic effect
that allows a lower viscosity and more stable O/W emulsion. The preferred water
soluble nonionic chemical surfactants for viscous crude oils are the commercially
available ethoxylated alkyl phenols and ethoxylated alcohols; while the preferred
water-soluble anionic chemical surfactants are ethoxylated alcohol sulfates. On the
142
other side, as a water-soluble chemical surfactant, or, together with a bio-emulsifier

can absorb onto the hydrocarbon/water interfaces. Hence, “surfactant packages”
composed of water-soluble chemical and/or biological co-surfactants have been
proposed to transport viscous hydrocarbons by pipeline through the formation
of low-viscosity bio-surfactant-stabilized oil-in-water emulsions, or the so-called
hydrocarbosols. Here, hydrocarbon droplets dispersed in the continuous aque-
ous phase are substantially stabilized from coalescence by the presence of bio-
surfactants (Bio-emulsifiers), in particular, microbial surfactants [80]. Generally,
bio-emulsifiers act by orienting their molecules at the oil/water interface, avoiding
the coalescence of the oil droplets and stabilizing the resulting emulsion with
maintaining their reduced viscosity over time. The hydrocarbosols viscosities were
reduced by at least a factor of 10. Bio-emulsifiers, specifically extracellular micro-
bial polysaccharides (“emulsans”) produced by different strains of the Acinetobacter
bacteria have been extensively researched [81, 82]. Among the preferred bio-surfac-
tants are heteropolysaccharides produced by bacteria of the genus Acinetobacter and
the genus Arthrobacter, and in particular, those produced by strains of Acinetobacter
calcoaceticus. Still some heavy oils were not successfully emulsified with the surfac-
tant packages studied. Here, it is worthy to mention that fresh water, sea water or
even formation water may be available for emulsification and thus, these are very
efficient oil-in-water emulsifiers possessing a high degree of specificity in both
fresh water and sea water for emulsifying hydrocarbon substrates which contain
both aliphatic and aromatic or cyclic components. Here, the use of formation water
instead of fresh water resulted in a lower interfacial tension between crude oil and
formation water and a more viscous O/W emulsion because of the formation of
smaller crude oil droplets [71].
In this context, the heavy crude oil is a complex mixture of hundreds of thou-
sands of compounds that include the asphaltenes which act as natural emulsifiers
as well as other active surface components such as naphthenic acids, resins, por-
phyrins, etc. [70]. The presence of these component increases the complexity of
crude oil emulsion, as they can interact and reorganize at the oil-water interface.
On the other hand, the presence of natural hydrophilic particles such as clay and
silica in the crude oil may cause instability in the emulsion [70]. Additionally, the
O/W emulsion system may sometimes contain solids and gas, which increases the
complexity of the process. In general, it is worthy to mention that the behavior of
heavy crude oil-in-water emulsion is complex due to the interaction of several com-
ponents within the system and many other factors mentioned hereinabove. By the
fact that the use of surfactants can significantly increase the cost of emulsification,
the activation of surfactants naturally occurring in heavy and extra heavy crude oils
is a reliable option. The ionization of acidic groups present in fatty and naphthenic
acids as well as asphaltenes with a strong alkali can make these surfactants more
hydrophilic causing a reduction of the interfacial tension [70]. Thus, the activa-
tion of the natural molecules present in bitumen with amines serves as natural
surfactants to form a bitumen-in-water emulsion or Orimulsion® (Orimulsion®
is a bitumen-in-water emulsion and simultaneously the technology developed to
facilitate the transportation of Cerro Negro bitumen) [83]. Moreover, some works
refer to the use of the natural surfactants present in crude oil with particles such as
silica, clay, iron oxides, etc., more stable emulsions can be obtained by saturation of
surface of these particles by asphaltenes [70]. There are still many unresolved ques-
tions related to the peculiar behavior of these emulsions as result to the complexity
of the molecular composition of oil having a wide range of chemical structures and
molecular weights, the hydrophilic-lipophilic balance (HLB) values of the surfac-
tants, the multiple interactions oil-water-surfactant and the possible molecular
rearrangements at the oil/water interface.
143
Economically, pipelining of oil in form of O/W emulsion must transport as

much oil as possible and as little water as possible (high O/W volume ratio).
Notwithstanding, when the oil content in O/W exceeds 70%, the viscosity may
become too high or inverse to W/O emulsion. Meta-stable and easy-to-break O/W
emulsions should be produced with the minimum quantity of cost-effective surfac-
tant and other additives where, strategy of implementing the technology of oil-in-
water emulsions to transport heavy crude involves three stages such as producing
the O/W emulsion, transporting the formed emulsion and separating the oil phase
from the water phase. However, recovering the crude oil entails breaking the oil
in-water emulsion. Hereby, different techniques including thermal demulsifica-
tion, electro-demulsification, chemical demulsification, freeze-thaw method, pH
modification, addition of solvent and demulsification by membranes have been
developed to achieve the separation stage [73, 84].
In this technology, the surfactants should allow at the same time a simple but
efficient rupture of the O/W emulsion before crude oil refining and the separated
water should be treated in order to comply with environmental and industrial
regulations for water discharge or recycling. The demulsification produced 0.5%
BS&W for the heavy oil and less than 100 ppm oily contaminants in the sepa-
rated water. Nonetheless, O/W emulsions can be considered for applications in
improved recovery processes of heavy oils and for the increase in the recovery fac-
tor of mature fields [85], including the amounts not retrieved from the exhausted
fields of light oils [86]. Furthermore, such emulsification technology can improve
residual oil removal from mature fields that are not as efficiently recovered by
traditional methods that apply heat or diluents [87]. Also, restarting a pipeline
after an emergency shutdown and re-emulsification of oil may not pose major
problems [88].
The potential of this technology to enhance pipeline transportation of heavy
crude oil has been demonstrated in Indonesia in 1963, as well as in a 13-mile dis-
tance using 8 in. diameter pipeline in California [71]. Field-tested pipeline trans-
portation of heavy crude oil as oil-in-water emulsions containing high fractions of
oil has been proposed by Hardy and others [89]. A large number of studies, mostly
experimental in nature, have been carried out on oil-water emulsions [78, 90].
However, the results of these studies are not uniform and are sometimes contradic-
tory and thus, the results obtained from a study on a certain crude are difficult to
apply to another. This can be attributed to the complex viscosity behavior of emul-
sions which depends on several factors such as base sediment and water (BS&W),
temperature, shear rate, type and concentration of surfactant, and the components
of the crude itself. Consequently, oil companies investigate on their own the specific
crude that they produce the type of emulsion that is most appropriate allowing
simple and economical crude oil recovery at the end of the pumping process.
Transportation of emulsified heavy oil had its technological viability clearly
demonstrated by many field studies and the development of the pioneer process
of large-scale fuel emulsions, a joint project between BP Canada and the Alberta
Energy Company has developed TRANSOIL®, a technology that is comprised
of the steps of oil emulsification, characterization of transport properties, and
evaluation of storage and recovery conditions by de-emulsification [91]. The
emulsions obtained were pumped continuously for 6 days at 80 m3/day and stored
for 6 days without any sign of degradation. Besides, ORIMULSIONS® process
has been developed for the generation of energy in thermal plants by the state
owned company PDVSA (Petr oleos de Venezuela) in Venezuela in the 1980s [17]
and commercialized by its filial Bitumen’s Orinoco S.A. (BITOR) [60, 70]. Ditto,
emulsion flow rate tests performed with 13° API oil from a field in Shanjiasi (China)
showed a reduction in pressure loss by as much as 80%, which was achieved by
144
emulsions formulated with water fractions around 0.6–0.8. This reduction in

pressure occurred especially when the tests were conducted in more drastic condi-
tions, such as with extra-viscous oils and at low temperatures [14]. In another work,
emulsification of heavy oil in Sicily and the Adriatic Sea (Italy) has been tested for
application in transport and production. The trial was based on the injection of an
emulsifying aqueous phase into the well without any modification to the existing
system. The dispersed oil content in the well-produced oil-in-water emulsions was
70%. The emulsions showed a viscosity 30–50 times lower than that of the diluted
oil and oil productivity was greater four times than obtained with the conventional
diesel dilution production [92].
7.3 Heavy oil emulsions for transport in cold environments
Considering, handling difficulty for O/W emulsions in cold environments

because of phase destabilization, freezing or an increase in viscosity to a level
too high for pipeline transport, brine with a high salt content and freezing point
depressants like ethylene glycol in sufficient concentration are suggested to be used
to maintain the oil-in-brine emulsion in pipeline condition at 253.15 K or less, but
insufficient to break down the emulsion. Here, it is worthy to consider the costs of
emulsion rupture and further processing of produced water to discharge or reuse.
The emulsion is suggested to contain a small amount of 0.1–5% by weight, of a
conventional surfactant to facilitate the formation and preservation of the emul-
sion. The use of common surfactants mixes has been proposed to form the emulsion
and supplemented by use of the xanthan biopolymer to enhance the stability of
the emulsion [93]. In another research, a novel surfactant, tri-triethanolamine
monosunflower ester, was synthesized from fatty acids produced from hydrolysis of
sunflower (Helianthus annuus) oil. The resultant surfactant was used to emulsify a
heavy crude oil from the western oil field of India. The oil-in-water emulsion devel-
oped with 60% oil content and 2 wt% surfactant exhibited a decrease in viscosity
of 96% and a dramatic decrease in pour point where, the prepared emulsions were
found to be flowing even at 1°C. The high stability of the emulsion has been attrib-
uted to the large reduction in the equilibrium interfacial tension (IFT) between
the crude oil (diluted) and the aqueous phase of emulsions, which was almost nine
times lower than that of no surfactant. These results suggested that the synthesized
surfactants may be used to prepare a stable O/W emulsion for its transportation
through offshore pipelines efficiently [94].
Furthermore, heavy oils in cold environments can be efficiently transported
through a large diameter insulated pipelines at temperature below 273.15 K in the
form of oil-in-brine emulsions containing 40–70% w/w of the dispersed oil with
dissolving salts in the water phase at concentration sufficient to prevent freezing.
These operating conditions permit the insulated pipeline to be buried in the ground
without causing thawing of the permafrost, which in turn can cause damage to both
the environment and the pipeline.
8. Conclusion
The plateau in conventional oil production and the corresponding increase

in the demand for liquid fuels have motivated markets to respond with higher
oil prices. And the current economics of oil are spurring the transformation of
energy supplies, not away from oil, but toward new oils which are expected to be
the dominant supplies of liquid-fuel through the twenty-first century based on
the market forces. The amount of these new petroleum resources could continue
145
to be revised upward as new technologies are developed. In this chapter, the

mitigation technologies of low mobility of heavy crude oils used to facilitate their
pipelining were explored. These methods have been divided into three categories
based on reduction of viscosity and friction and in situ upgrading of these heavy
crudes and bitumen. Each of these treatment techniques has special advantages
and drawbacks. Therefore, there are many criteria to take into consideration on
choice of each technique including the chemical and physical properties of the
crude, regional logistics between the well-head and the refining site, operational
and environmental concerns, distance of transportation, cost, and regulatory
requirements. These criteria require that the petroleum industry tailor treatment
strategies to fit the circumstances of its systems in accordance with the quality
requirements of the pipeline operator as well as the content and quality demands
of the refinery customer. Emulsification of crudes to form O/W emulsion was an
appropriate method to reduce the viscosity of oils and enhance their flow under
offshore conditions. Currently, in situ upgrading can be achieved during thermal
enhanced oil recovery methods because this strategy characterized by the cost,
environment and energy effectiveness. Also, the introduction of bacteria and bio-
metal nanoparticles (Bio-NPs) in the reservoir to upgrade heavy oil, extra heavy
oil, and bitumen in situ is an area of active research and hold great promise for
improving flow of these crudes.
Author details
Emad Soliman
Polymer Materials Research Department, Advanced Technology and New Materials
Research Institute (ATNMRI), City of Scientific Research and Technology
Applications (SRAT-City), New Borg El-Arab City, Alexandria, Egypt
146
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152
Chapter 9
Challenges during Operation

and Shutdown of Waxy Crude
Pipelines
Mysara Eissa Mohyaldinn, Hazlina Husin, Nurul Hasan,
Mohamed M.B. Elmubarak, Ahmed M.E. Genefid
and Mahmood E.A. Dheeb
Abstract
Transportation of waxy crude oil faces great challenges due to shear and
temperature dependency. At high temperatures, waxy crude exhibits low viscous
Newtonian behavior where the resistance to flow due to friction is low, and hence
low pumping pressure is required to transport it. At low temperatures, however,
the crude exhibits shear thinning non-Newtonian behavior where its apparent
viscosity becomes shear-dependent. In such cases, the operated pipeline needs to
maintain a high pressure to guarantee a continuous flow. Moreover, due to heat
transfer between the internal pipeline and surroundings, oil temperature declines
along the pipeline. It follows that the crude viscosity and, hence, frictional resis-
tance increase. If the flow is interrupted for any reason, i.e., emergency or planned
shutdown, then the restartability of the pipeline becomes a challenge because of
the nonexistence of heating generated from friction. In this chapter, the challenges
normally facing transportation of waxy crude oil will be discussed. The chapter
will introduce the rheological properties of waxy crude oil and explain and describe
how these properties can affect the pressure losses inside the pipeline during its
operation and shutdown. The measures that need to be considered when designing
a waxy crude pipeline will be discussed.
Keywords: waxy crude, rheology, pipeline, oil transportation
1. Introduction
Flow assurance is one of the major technical challenges in oil and gas production
operations. The formation of gas hydrate, wax, halite, asphaltenes, mineral scales,
and naphthenic acids can all result in serious operational and economic concerns.
The industry needs novel and innovative techniques to reduce the costs associated
with flow assurance and to improve the overall operation performance. Nowadays,
with the decrease in conventional oil reserves, oil companies are improving uncon-
ventional oil fields where the reserved hydrocarbons are heavy and possess complex
properties. The most important consequence of these ultraheavy hydrocarbons is
that they hinder the flow through different production and transportation sys-
tems. In particular, for oil transportation through pipelines, we have to consider
153
the complexity of the fluid rheology as an important factor that needs to be fully
controlled in order to generate a smooth transportation.
The crude oil that possesses a high amount of wax, known as waxy crude oil,
can cause many operational obstacles during production, storage, and transporta-
tion. It is considered that the most important obstacle is the crystallization and
sedimentation of wax in the crude oil in the pipes during transportation. While
waxy crude oil is flowing through the pipeline, and due to continuous cooling of
the oil caused by heat transfer toward surroundings, crystals of wax form and grow
in size to form partial to total blockage of the pipe cross-sectional area. This process
continues with shutdown time, and farther the distance from the pipeline inlet, the
faster is the wax deposition on the pipe internal wall and the higher tendency of
the wax crystals to enlarge in size. This results in a continuous decrease in the pipe
internal diameter, and, as the frictional loss is inversely proportional to the pipe
diameter, higher frictional pressure loss will occur. Because of that, the pumping
pressure needs to be increased in order to preserve the desired flow rate. However,
knowing the mobility of the flow is an important issue for effective and frugal
process of a pipeline framework. The main concern of waxy crude oil is the stream
restart after delay in planned or emergency shutting down of the flow process for
any reason.
Wax precipitation and deposition also contribute significantly in changing the
original rheology of the oil. While wax crystals are precipitated and deposited,
viscosity of the crude oil rises to convert it to a high viscous fluid that adhered to the
internal pipe wall to decrease the effective cross-sectional area of the pipe. A solu-
tion to this issue can be achieved by applying various methods to lower the viscosity
and pour point. The most common methods extensively implemented are heating
of the transported crude, dilution with lighter fluid, and adding chemical addi-
tives, known as flow improvers/modifiers, to the flow stream. Each one of the three
methods has its own advantages and disadvantages; however, generally speaking,
chemical additives stay the most commonly recognized solution as compared to the
other choices.
Usually the waxy crude oil is pumped at temperatures above its wax appearing
temperature (WAT) in order to prevent forming of wax on the wall of the pipes.
The pressure pumped should be high enough to hold the stability of the fluid. When
temperature gets lower due to heat transfer, the crude becomes more viscous. And
if the temperature lowers enough to initiate wax deposition, then there will be a
double effect that results in higher frictional pressure, viz., higher viscosity and
smaller pipe diameter.
1.1 Definition of waxy crude oil
Waxy crude oil can be defined as the crude oil that contains high amount of
long-chain paraffin wax (alkanes) components, making the crude to possess a high
pour point and, may be, a low API gravity. A waxy crude oil is distinguished by the
fact that it exhibits non-Newtonian rheological behavior at low range of tempera-
ture (i.e., about 20 F above the pour point). For such non-Newtonian behaved crude
oils, the effective viscosity is not only temperature dependent but also a function of
the effective rate of shear in the pipeline. At reservoir conditions, due to high pres-
sure and temperature, wax molecules are normally dissolved in the crude oil to form
a single continuous hydrocarbon liquid phase. While flowing through pipelines,
especially in sub-sea environments, due to cooling down, wax crystals may start to
precipitate from this continuous phase, and eventually the fluid may lose its liquid-
ity behavior. This change of flow behavior normally starts to occur when the crude
temperature becomes lower than its cloud point or WAT [1].
154
1.2 Wax chemical compound formation and properties
The wax existing in crude oil mostly contains paraffin hydrocarbon (C18-C36)
recognized as paraffin wax and naphthenic hydrocarbon (C30-C60). The hydro-
carbon element of wax is able to present in several phases, i.e., gas, liquid, and
particles (solids), relying on the flow conditions, i.e., pressure and temperature.
When the temperature of wax decreases, the agglomerates and the wax crystals
from paraffin wax are recognized as microcrystalline or naphthenic hydrocarbon
[2]. Chemical flow modifiers can be used to enhance the crude flowability at flow
conditions where crystallization or gelling is expected. These flow modifiers can
delay the crude crystallization by reducing its pour point and viscosity. According
to [3], the temperature of the waxy crude oil at the time of injecting the chemical
additives is an important factor to determine their efficiency. If the temperature
is very low, surely some amount of wax will be formed, and this accumulated wax
will affect the rendering of chemicals. It has been observed that a high molecular
weight wax chemical flow modifier has better performance for lowering waxy
crude pour point. The crystal growth development rate of the lower-molecular-
weight wax inhibitor is much slower than that of the higher molecular weight wax
inhibitor.
1.3 Wax appearance temperature or cloud point
Wax appearance temperature is the temperature below which wax starts to

appear in a waxy crude liquid. When a heated waxy crude is cooled down to a
temperature lower than WAT, the wax molecules form clusters of aligned chains.
Once these nuclei reach a critical size, they become stable, and further attach-
ment of molecules leads to growth of the crystal. Formation of these nuclei causes
the fluid to take on a cloudy appearance, hence the name cloud point. This also is
referred to as the wax crystallization temperature or WAT. If the WAT of a produced
or transported waxy crude oil is found significantly higher than the temperatures
expected to be encountered during production or transportation, then wax deposi-
tion problems should be expected, and precaution measures are to be taken to avoid
the problem and lessen the consequences arisen from.
1.4 Factors controlling wax deposition
Wax deposition along the pipeline is affected by several factors that include
temperature, pressure, wax molecular weight, and the other crude oil components.
For a proper design, operation, and optimization of a waxy crude production and
transportation system, the effect of each of these factors is to be investigated care-
fully following documented experimental procedures and standards.
Wax deposition onto the production system generally requires a nucleating
agent, such as asphaltenes and inorganic solids. The wax deposits vary in consis-
tency from a soft mush to a hard brittle material. Paraffin deposits will be harder
if longer-chain n-paraffin is present. Paraffin deposits can also contain other
materials such as asphaltenes, resins, gums, fine sand, silt, clays, salt, and water.
High-molecular-weight waxes can deposit even in the higher-temperature sec-
tions of a well, while lower-molecular-weight fractions tend to deposit in lower-
temperature regions. Prior to solidification, the solid wax crystals in the liquid oil
change the flow properties from a Newtonian low viscosity fluid to a high viscous
non-Newtonian shear-dependent fluid. With further temperature reduction, the
oil may eventually turn into a very-complex-flow behavior gel with yield stress (i.e.,
becomes yield-pseudoplastic or yield-plastic non-Newtonian fluid). Regardless
155
of the rheological behavior the oil is exhibiting, oil viscosity is always inversely
proportional to the oil temperature. As the temperature of oil increases, the oil
viscosity decreases and vice versa.
The wax solubility is also directly proportional to process temperature.
According to Sadeghazad and Christiansen [4], when water is present in the crude,
wax deposition tends to reduce. This is because the water decreases the oil’s temper-
ature drop keeping the solution above the pour point temperature. They stated that
water is able to maintain the oil temperature because oil has only half the specific
heat as compared to that of water.
The second factor that affects the wax deposition is the pressure. The wax
present in oil has a positive divergence, i.e., the solubility of the wax present in
the solution decreases with the increase in applied pressure. This is because of the
intermolecular forces between molecules [4].
The third factor controlling wax deposition is the wax molecular weight. The
higher the molecular weight of the wax, the lesser its solubility because of its melt-
ing point increasing with the increase in the molecular weight [4, 5]. Al-Shafey and
his co-workers stated that the solution composition greatly affects the wax deposi-
tion as well [6]. A set of experiments conducted by Sadeghazad and Christiansen
reveals that the cloud point decreases for a wax solution with a lighter composition,
i.e., it would take longer time for the wax to deposit [4].
1.5 Wax deposition mechanism
The problem of paraffin wax may be described as a situation in which a predom-

inantly organic deposit hampers the production of crude oil. The loss of the crude
production from a well depends on the severity and location of the deposition. In
a pioneering work, Burger and others [7] investigated four wax deposition mecha-
nisms, namely, molecular diffusion of wax molecules, shear dispersion of wax
crystallites, Brownian diffusion of wax crystallites, and gravity settling. Gravity set-
tling of paraffin crystals in flow line conditions is negligible, because it’s dominated
by shear dispersion. These four wax deposition mechanisms are discussed in the
following subsections:
1.5.1 Molecular diffusion
Molecular diffusion is the deposition mechanism prevalent in well tubing.

To avoid the deposition in flowing well, the flowing oil temperature needs to
be maintained above the cloud point throughout the flow journey until the oil
reaches the wellhead [8, 9]. Deposition is enhanced as a result of radial heat
transfer from the tubing core toward the surroundings. Due to wax deposition,
a concentration gradient is formed in the oil as a result of temperature gradient
profile, due to increasing solubility of waxes with increasing temperature. The
concentration difference causes waxes in the solution to diffuse from the warmer
oil, which has a greater concentration of dissolved waxes, to the colder oil,
which has a lower concentration, resulting in molecular diffusion of the paraffin
crystals toward the surface wall. The wax concentration gradient is triggered as
the differential temperature at a cross section causes the particles near to the cold
walls to start the deposition from the oil solution and develop an initial layer of
deposit [10]. As the layer is deposited, a concentration gradient occurs between
the bulk fluid and the wall causing more wax to be trapped and oil flowing
through the wax as a porous media away from the wall, thus thickening the wax
concentration. This mechanism is the common mechanism observed for wax
deposition.
156
1.5.2 Shear dispersion
At low temperatures, shear dispersion is believed to be the most occurring

mechanism. It deals most with particles that are settling on the surface of a cold
pipe due to the grooved or rough surface as well as the intermolecular forces [11].
Yet it was concluded that the shear dispersion is not significant based on field
operating experience as well as experimental investigations.
When wax particles are moving along while transporting oil through a pipeline
on an average speed, shear dispersion occurs as a shearing effect near the wall. The
speed of the flowing fluid is less near the wall due to the shearing and friction caus-
ing a shear dispersion. Thus the crystalized precipitates move toward the wall due
to its higher weight and away from the turbulent flow of the crude. Once reaching
the wall, such precipitates form an initial layer of deposition or get trapped in the
matrix made by the molecular diffusion caused earlier [12]. Shear dispersion is
most effective when the temperature of the turbulent flow is below the WAT, thus
causing high wax precipitation. A shear dispersion coefficient expressed by Burger
and his co-workers [7] is:
a2 γ C∗
Ds = _w (1)
10
where Ds is the shear dispersion coefficient (m2/s); a is the particle diameter, m;

Cw is the wax volume fraction concentration excluding the wall, fraction; and ɤ is the
oil shear rate on the wall, s−1.
1.5.3 Brownian diffusion
When tiny solid crystals are suspended within the oil, they collide frequently
with thermally vibrant molecules. Due to such collision, a Brownian movement is
initiated. At a concentration differential of these particles, the motion will cause
diffusion. Coefficient of the Brownian diffusion is expressed as:
RT
Db = _ (2)
6𝜋𝜋𝜋𝜋aN
where R is the gas constant (J/mol.K); Ta is the absolute temperature (K); U is

the viscosity (Pa.s); a is the particle diameter (μm); and N is the Avogadro’s number
(mol).
Yet as referred by Burger et al. [7], the Brownian diffusion can be ignored.
1.5.4 Gravity settling
As the waxy crystals are denser than the oil particles, they tend to settle down
and deposit. However, according to some results, it is believed that the gravitational
deposition is insignificant toward the wax deposition. The turbulent flow or the shear
dispersion would disperse the settling particles thus eliminating the gravity settling.
1.6 Waxy crude rheology
The most commonly used parameter to describe fluids’ rheology is the vis-
cosity, defined as the amount of resistance exhibited by the fluid to start the
deformation process once shear stress is applied. As the waxes are precipitating,
the fluid changes into a non-Newtonian fluid. This generally occurs when the
process temperature decreases below the WAT [13]. Moreover, the waxy crude oils
possess high yield stresses when the temperature further declines to values below
157
the pour-point temperature. When the temperature is lower than the pour-point
temperature, the oil loses its total mobility and turns into a gel-like structure
that would require critical value of stress to flow, known as yield stress value of
the gel. At low temperatures (below WAT), waxy crude oils generally exhibit
non-Newtonian flow behavior (namely, pseudoplastic fluids). The main feature
of the pseudoplastic non-Newtonian fluid is the dependency of viscosity on
shear rate (while it is constant for Newtonian fluids). Figure 1 shows typical flow
curves of fluids exhibiting different types of rheological behavior as proposed by
Wardhaugh and others [3]. The upper curve (a) shows the variation of applied
shear stress and shear rate as measured by a viscometer. The lower curve (b)
shows the variation of fluid viscosity with shear rate. It is clear that the viscosity
of Newtonian fluid is independent of shear rate, while the viscosity of non-
Newtonian fluids decreases with increasing shear rate. Viscosity is the amount of
resistance exhibited by the fluid to start the deformation process once shear stress
is applied. Different correlations are used to derive viscosity as per the case. The
value of viscosity of crude oil depends on many factors including the composition
of oil, temperature, amount of gas dissolved, and pressure or stress. The viscosity
can be calculated as the ratio of shear stress (Pa) to shear rate (s−1); hence, the SI
unit of viscosity is Pa·s.
Figure 1.
Typical flow curves of fluids exhibiting different types of rheological behaviors [3].
158
As the fluid flows through a pipeline, it starts a deformation due to the slip-
page action occurring. Shear stress is a force that is acting parallel to the flow
propagation of the fluid. The main cause of the shear stress is the friction exerted
between the particles, which is proportionally related to the viscosity of the fluid.
Mathematically, the shear stress is the force applied on a surface divided by the
F , where τ is the shear stress in N/m2 (or Pascal), F is the applied
surface area, i.e., τ = _
A
force in N, and A is the cross-sectional area of the fluid parallel to the applied force
in m2.
The shear rate is the rate at which the deformation caused by the shear stress is
taking place. In Newtonian fluids, the shear rate increases as the flow rate increases.
As in the case of flow through pipelines, the shear rate is the gradient of change in
velocity across the radius of the pipe assuming that the top and bottom flows are
not in similar velocities. Assuming two parallel plates with one moving while the
other is stationary, the shear rate can be defined as _ v1 − v2 where v1 is the velocity
h
at the top plane, v2 is the velocity at the bottom plane, and h is the gap between
the plates. This radial velocity and shear distribution are similar to what happens
during oil flow through pipelines. While flow velocity is constant along the pipeline
(since the pipe diameter is constant), there is a radial velocity variation along the
cross-sectional area due to the effect of shear. At the pipe wall, where the shear
stress is maximum, velocity is zero, whereas the maximum velocity occurs at the
center of the pipe. Figure 2 shows an example of the radial velocity distribution at
three values of flow rates [3], where A is the highest flow rate and C is the lowest
flow rate as indicated by radial velocity distribution showing a turbulent flow and
laminar flow, respectively.
1.7 Transportation of waxy crude through pipelines
Significant percentage of pipelines worldwide transport waxy crude oils

with different amounts of wax contents and, hence, wide range of rheology
complexity. In China, for instance, more than 80% of the produced oils are
classified as waxy crude [14] with total annual production of over 100 million
tons and total annual storage of more than 70 million tons [15]. Worldwide, half
of the recoverable oil reserve is classified as heavy crude [16] with the waxy
crude contributing about 20% to the total hydrocarbons reserve [17]. There
was a noticeable increase in the production of waxy crude recently. The daily
total production rate worldwide has increased from 1 million BOPD in 1960 to
almost 24 folds (contributing to one third of the total world oil production) in
2009 [1].
Figure 2.
Radial velocity distribution in the pipeline at three values of flow rate (VA > VB > VC) [3].
159
Since pipelines are the main transportation methods of waxy crude oils, proper
precautions and measures should be adopted to ensure a safe and smooth flow at
various operating conditions. For long-distance pipelines, in particular, the tem-
perature variation along the pipeline causes axial change of the rheological behavior
which results in complexity of prediction of pressure losses at different segments
along the pipeline.
Two cases need to be considered of a waxy crude pipeline, operating conditions
and shutdown conditions.
2. Waxy crude pipeline operations
During operation, the flow of the transported waxy crude tends to facilitate the
pipeline operation due to continuous shear of the fluid, from one hand, and the
heat generation due to friction, from the other hand. The former causes reduction
of the crude viscosity, which results in the decreasing of the generated frictional
pressure losses, and hence, less pumping pressure is required. The latter adds a
significant heating to the transported fluid, which can compensate part of the
heat losses resulting from the heat transfer due to temperature difference between
Figure 3.
Temperature distributions along Higleig-Portsudan pipeline (inlet temperature 60°C and flow rate 0.33 m3/s) [18].
Figure 4.
Variation of temperature and viscosity along pipelines [19].
160
the fluid and surroundings. As a result, the temperature along the pipeline can be
maintained to be always above the WAT. Figure 3 is an example of temperature
distribution along the Sudanese Higleig-Portsudan pipeline assuming two values
of soil temperature [18]. The figure indicates that the shear action due to flow can
maintain the temperature and delay the distance at which the temperature falls
down to surrounding (soil) temperature. This distance is directly proportional to
the fluid flow rate.
Figure 4 shows a typical variation of temperature and viscosity along a waxy
crude pipeline [19]. As we go far from the inlet, temperature declines due to
heat transfer between the fluid and the pipeline surroundings. The temperature
Figure 5.
Fula pipeline profile and pressure transverse between initial and terminal pump stations [20].
Figure 6.
Fula pipeline profile and pressure transverse between pump stations (3 pump stations) [20].
161
reduction leads to increase in viscosity, which eventually results in increase in

frictional pressure loss per unit of length. The trend of the variation of pressure loss
per kilometer length follows the same trend of viscosity variation.
To maintain a smooth operation of the pipeline, the total pressure losses due to
elevation difference and friction (which is highly affected by the crude rheology)
needs to be balanced by operating one or more pump stations. To facilitate the crude
pumping, the crude rheology can be enhanced by heating or injection of chemical
flow modifiers. Figures 5 and 6 show the pressure traverse between pump stations
of another Sudanese pipeline (Fula pipeline) assuming one and three pump sta-
tions, respectively [20]. The figures indicate that the inlet pumping pressure gradu-
ally declines along the pipeline to reach the next pump station at a specific terminal
pressure, which may serve as a suction pressure to the successive pump station.
This pressure profile is affected by flow rheology and wax precipitation inside the
pipeline both of which are highly temperature dependent.
3. Waxy crude pipeline shutdown and restarting
Unlike operating pipelines, when a pipeline undergoes a planned or emergency

shutdown, it loses the positive effects of shearing and heat generation due to
continuous flow. The temperature declines steadily from the moment of shutdown
until the time at which the temperature at all points along the pipeline reaches the
surrounding temperature, which may or may not be above the WAT. Accordingly,
the crude oil inside the pipeline exhibits a specific rheological behavior throughout
the pipeline length. If the surrounding temperature is significantly higher than the
WAT, the crude oil will exhibit a Newtonian flow behavior, where it can easily be
restarted after the shutdown period. However, if the surrounding temperature is
less than the WAT, then the fluid will exhibit a non-Newtonian behavior, and high
restarting pressure is needed. Figure 7 shows the temperature distribution along
Higleig-Portsudan pipeline at the moment of shutdown and after every subsequent
12 h following the shutdown. The figure indicates that the temperature throughout
Figure 7.
Transient temperature distribution along the pipeline every 12 h after shutdown (inlet temperature 60°C, soil
temperature 42°C, flow rate 0.33 m3/s) [18].
162
the pipeline distance reaches the surrounding temperature after 2 days from the
shutdown moment.
The most worse shutdown scenario is where the crude temperature drops below
pour point and results in the gelling of the crude inside the pipeline. In such com-
plex scenario, the restartability of the pipeline becomes a challenge, and the opera-
tor may become unable to restart it. It is, therefore, essential to avoid these complex
scenarios by different measures such as heating, chemical additives, dilution of the
crude with lighter fluids, and shortening the shutdown periods to ensure that the
temperature is always at a value permitting a smooth restarting of the pipeline.
4. Conclusions
Transportation of waxy crude pipeline through pipelines can cause numerous

problems that may impose safety, economical, and technical impacts on the pipeline
operation. The severity of waxy crude-related problems is highly affected by the
complexity of its rheological properties which in turn depends on the operating
conditions (mainly temperature). During waxy crude pipeline operation, tem-
perature declines along the axial length due to heat transfer caused by temperature
difference between the transported crude and the surroundings. This temperature
decline is concurrently encountered by a raise in temperature caused by heat
generation due to friction which is proportionally related to the velocity gradients.
This temperature variation along the pipeline causes axial variation in the crude
rheological properties which results in variation in frictional pressure losses.
During planned and emergency shutdown of waxy crude pipelines, the prob-
lems will get worse due the absence of heat generation. The temperature declines
steadily from the moment of shutdown until the time at which the temperature at
all points along the pipeline reaches the surrounding temperature, which may or
may not be above the WAT. Accordingly, the crude oil inside the pipeline exhibits
a specific rheological behavior throughout the pipeline length. The problem may
get worse when the surrounding temperature is below the WAT or even below pour
point. In such case, the pipeline may need to be assisted by putting on some cost-
effective measures to facilitate restarting up of the flow.
Author details
Mysara Eissa Mohyaldinn1*, Hazlina Husin1, Nurul Hasan2, Mohamed

M.B. Elmubarak1, Ahmed M.E. Genefid1 and Mahmood E.A. Dheeb1
1 Department of Petroleum Engineering, Universiti Teknologi PETRONAS (UTP),

Perak, Malaysia
2 Petroleum and Chemical Engineering, Universiti Teknologi Brunei, Brunei
163
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165
Chapter 10
Pre-Treatment of Heavy Crude

Oils for Refining
Faith Uchenna Babalola and Alfred Akpoveta Susu
Abstract
The economic unattractiveness of heavy crude oils in the global oil market scene
is fast changing due to the looming scarcity of light oils. There are huge reserves
of heavy oils to which refiners are being reluctantly attracted. The fully developed
conventionally available refineries are, however, incapable of processing these
heavy crudes without some major modifications of both process and equipment,
which will be capital intensive. This thrust promises to be very viable and yield
great benefits since heavy oil is relatively cheap. Process and equipment modifica-
tion begins with the required pre-treatments of these heavy crudes to facilitate
efficient and cost-effective refining. Low API gravity, high amounts of impurities,
and high viscosity are the major challenges addressed in the pre-treatment section.
An option for a unit for the removal of some impurities for some special heavy oils
is proposed. This should be followed by a multi-stage desalting unit that may be
replaced with a centrifuge and a preliminary hydrotreating unit.
Keywords: heavy oil, pre-treatment, desalter, contaminants, impurities,

efficient refining
1. Introduction
With the depletion in global reserves of light crude oil over the past few decades,
the attention of refiners and researchers has been shifted to heavy and extra-heavy
crude oils in recent times. It is estimated that global heavy oil reserves are over 3
trillion bbl, which can supply the world’s energy needs for the next 100 years [1].
Refining processes for light crudes have been well developed and the products
yield high economic value; this is in contrast with the more complex and more
costly processing of refining heavy crudes which is less expensive but yields less
attractive products. The trade-off, however, lies in the fact that these heavy crudes
are currently becoming more abundant, and also with further development in
their processing technologies, higher quality products will emerge and the return
on investment will become quite attractive. It is estimated that there is twice the
quantity of heavy crude in reserves than light crude and this ratio is most likely to
increase in favor of heavier crudes.
The primary challenges in processing heavy crude oils are poor flowability
due to high viscosity, low API gravity (<20o), and the presence of higher amounts
of impurities than in light crudes. With treatments that increase flowability and
remove impurities, the refining task is reduced to mainly cracking processes to yield
desired products such as gasoline and middle distillates. Various technologies have
been employed to improve heavy oil flowability in pipelines. Due to high viscosity
167
and hence high pressure drop, pumping cost is extremely high and so energy
intensive; alternative solutions to higher pumping power include pre-heating of the
crude by heating of the pipes, dilution with light hydrocarbon fluids, oil-in-water
emulsification, and partial upgrading [2, 3]. Flowability enhancement technologies
for transporting heavy oil are outside the scope of this chapter but are available in
literature [4, 5].
Upgrading of heavy oils is achieved by either a carbon-rejection process, a
hydrogen-addition process, or a combination of both. These technologies produce
light oil fractions, which can be processed in conventional refineries and, therefore,
also fall outside the scope of this work but can be found in open literature [6]. To
enhance refining, heavy crudes are first sent to pre-treatment units either on the
drilling site or in the refinery to condition them for easy processing and render
them equipment-friendly.
2. Unconventional crude oils
With global changes in technology and economy come concomitant changes in

the definition of conventional and unconventional petroleum crudes. Generally,
today, conventional oil includes light crude oil with natural gas and its condensates,
while unconventional oil consists of a wider category, including heavy oil, extra-
heavy oil, oil sands, gas to liquids, and other liquids. Conventional oils are cheaper
and easier to produce and process than unconventional oils. These categoriza-
tions, however, may not remain fixed over time. With technological development,
resources hitherto considered unconventional may migrate to the conventional
category. According to the US Department of Energy (DOE), “unconventional oils”
have not yet been strictly defined [7]. In fact, it has been argued that common clas-
sification of unconventional oils based on production techniques is imprecise and
time-dependent. No universally accepted definition of “conventional” and “uncon-
ventional” oil has been accepted by the International Energy Agency [8].
2.1 Heavy and extra-heavy crude oils
Heavy oils are characterized as having boiling points above 650°F (343°C). These
oils are termed “heavy” because of their relatively high density or specific gravity;
they also have higher viscosity and heavier molecular composition. Heavy oils have
an API gravity of less than 20o [9], and in 2010, the World Energy Council defined
extra-heavy oils to have an API gravity of less than 10o and a reservoir viscosity of
10.000 centipoises or less [10]. Below an API of 10o, a heavy oil will sink in water
rather than float and is termed extra heavy.
Heavy oils contain asphaltenes and resins; they are dense and viscous (heavy)
due to the higher percentage of aromatics and naphthenes than alkanes. They also
contain high amounts of nitrogen, sulfur, oxygen, and heavy metals. They have a
higher proportion of compounds with over 60 carbon atoms and, hence, higher
boiling points and higher molecular weights than light oils.
2.2 Transportation of heavy crude
Most existing pipelines are designed for light crude oil transportation and so
cannot accommodate heavy oil unless they are modified. To transport heavy oil in
these existing pipelines, diluting or drag reducing agents (DRAs) are added to the
heavy oil. Sometimes, light oil is mixed with the heavy oil to enhance flowability,
which, of course, reduces the value of the light oil [5]. With modifications of the
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pre-treatment unit proposed here to adequately handle water/oil emulsions, dilu-

tion with water may be a preferred method of improving flowability.
2.3 Environmental impact
Heavy oils have higher amounts of impurities and undesirable contaminants

especially sulfur, metals, and nitrogen which impact negatively on the environment.
Sulfur causes acid rain and combines with hydrogen to form hydrogen sulfide which
is a major air pollutant. Sulfur also causes corrosion in pipelines and downstream
equipment. Heavy metals, which are present in heavy oils, cause catalyst poisoning
and fouling of process equipment and are toxic thereby posing disposal problems.
At last, more carbon dioxide is generated both in the processing of heavy oils and in
the consumption of products of heavy oil stock due to higher carbon-to-hydrogen
ratio than in light oil [11].
3. Unwanted constituents and impurities
Some impurities in heavy oil occur as natural unwanted constituents of the oil,
such as nitrogen, sulfur, oxygen, acids, and salts, while others are acquired by the
oil during production; these include water and insoluble solids. These impurities
and the processes for their removal are discussed in this section.
3.1 Effects of impurities
The impurities in heavy oil are responsible for its low economic value because
they constitute a lot of problems to the pipelines, processing equipment, and the
environment. Sulfur causes fouling in the equipment and environmental pollu-
tion in the form of hydrogen sulfide; nitrogen forms gums that lead to catalyst
deactivation; oxygen can reduce the calorific value of the fuel; heavy metals such
as nickel, vanadium, and lead are harmful to the environment and cause corrosion
in process equipment and deactivate catalysts. Salts and acids also cause fouling of
equipment, while insoluble solids cause plugging in pipes [1, 6, 7]. The list of the
effects of impurities appears endless but suffices it to state here that the removal of
these impurities is crucial to environmental preservation, process efficiency, and
product quality.
3.2 Pre-treatments
Here, the various pre-treatment processes that ensure significant reduction or

complete removal of impurities in heavy oils before they are taken to the refining
process units are discussed. These pre-treatments mitigate downstream conse-
quences which include corrosion and fouling of equipment, catalyst poisoning,
more elaborate water treatment process, and higher energy cost. It is also worthy of
note that prior to pre-treatment, the delivery system, handling and storage of the
feed (heavy oil), goes a long way to affect the pre-treatment system requirements,
efficiency, and cost [1].
3.2.1 Demulsifying
Crude oil emulsion is formed as dispersed water phase in an oil medium. The
water globules are protected by an oil layer which prevents their coalescence. This
protective oil layer increases in mechanical strength with time (aging) due to long
169
storage, thus stabilizing the emulsion. Agitation during transportation in pipes has
a yet more stabilizing effect on emulsions due to high shear, which leads to smaller
sizes of water droplets. Smaller droplets are relatively more stable than larger ones;
hence, it is more challenging to demulsify the crude oil emulsion at the refinery
than at the production site [12]. Chemical demulsifiers or emulsion breakers are
used to break the crude oil emulsion into oil and water phases. They destroy the
interfacial film and enhance the coalescence of the water droplets. Some chemical
demulsifiers include amines, polyhydric alcohols, acids, and polymers [13].
The quality of a demulsifier is determined by the rate of oil separation from
water, amount of water left in the crude oil after separation, and quality of separated
water for disposal. It is desirable to have a fast separation rate, a low amount of resid-
ual water in the crude oil, and a low percentage of oil in the separated waste water.
Both the water phase and its dissolved salt contents need to be removed because
they lead to corrosion in the refinery equipment. Dehydration in thermochemical
steel tanks at temperatures as low as 50–55°C is effective for demulsifying heavy
oil emulsions as well as stage-wise electrode-assisted desalting units [14]. Other
demulsification techniques, such as biological, membrane, electrical, and micro-
wave irradiation, have also been employed in the oil industry [15]. Low-temperature
demulsifiers in delivery and storage facilities are used to improve feedstock quality
and optimize desalter operations [16]. Some factors that need to be addressed in
order to enhance demulsification and oil-water separation are discussed here.
a. Agitation: This should be minimized during transportation, pumping, and

storage and avoided wherever possible to reduce the mechanical strength of
the interfacial film between the water and the oil phases. Mechanical chokes
and flow obstructions can be employed to reduce agitation, though a necessary
degree of agitation is required to achieve an adequate mixing of the demulsi-
fiers into the bulk of the oil-water emulsion.
b. Heat: When heat is applied to an oil-water emulsion, the viscosity of the oil is
increased to enhance its flow, water expands and breaks the interfacial film,
there is a higher rate of droplet collision leading to faster coalescence, and
density difference between the oil and the water is increased. All these result in
an increased rate of phase separation. There is, however, an optimum amount
of heat requirement beyond which it can become disadvantageous and lead to
loss of low-boiling hydrocarbons.
c. Time: The retention time, during which the emulsion is held at the treating
temperature, affects the separation efficiency. Longer retention time results
in greater separation efficiency. Conventional crudes are treated for about
10–30 minutes, while heavy oils would require a much longer retention time [12].
d.Solids: The presence of solids, whether oil-wet or water-wet, has a further

stabilizing effect on emulsions and so needs to be removed, especially fine
particles [17, 18].
3.2.2 Deasphalting
Heavy oils contain significant amounts of asphaltenes which, if not removed,

will decrease the efficiency of the refining process and reduce product quality.
Asphaltenes comprise a dark brown to black solid with no definite melting point
but foams and swells when heated leaving a carbonaceous residue. Their molecu-
lar weight can span from 1000 to 100,000 [19]. Some common solids such as
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asphaltenes and waxes may be removed with the water after being water-wetted or
dispersing them into the oil.
They contain hydrocarbons and heteroelements, namely oxygen, nitrogen, and
sulfur. In asphaltenes, hydrogen-to-carbon ratio varies over a very narrow range of
between 0.5 and 1.15%. Larger variations are seen in their heteroelement contents:
oxygen varies from 0.3 to 4.9%, sulfur varies from 0.3 to 10.3%, and nitrogen varies
from 0.6 to 3.3% [20].
The heteroatoms (sulfur, oxygen, and nitrogen) in asphaltenes cause other
problems such as corrosion, catalyst deactivation, and environmental pollution.
Solvent deasphalting processes have been used to significantly remove asphaltenes
from heavy oils at mild temperature conditions [21]. In this process, an alkane (the
solvent) is injected into the heavy oil feedstock to disrupt the dispersion of the oil
components and, hence, cause the polar constituents to precipitate. Alkane sol-
vents, most common of which is propane or a mixture of propane and butane, are
used to obtain a good yield of deasphalted oil [22].
Practically, any conventional deasphalting process and equipment can be used.
For example, the residual oil supercritical extraction (ROSE) process, which is
currently used for residue fraction as feed, may be easily adapted and modified to
accommodate the whole crude feedstocks. Some of the adaptations to address will
include increasing the solvent/oil ratio, increasing the temperature, and the mix-
ing effect, which may involve the use of pumps, mixing valves, or medium speed
centrifuges. The deasphalted whole crude, after separation, may contain some of
the solvents but has much less asphaltenes and metal content. The deasphalted
crude stream is passed through a flash vaporization step to recover the solvent for
reuse before it goes for refining [21].
The Solvahl process is a solvent deasphalting process suitable for application
to heavy oils, extra-heavy oils, tar sands, and bitumen. It removes the asphaltene
constituents, gives very high yields of deasphalted oil, and reduces metal content in
the viscous feedstock. Various solvents used in this process include liquid propane,
butane, pentane, hexane, and heptane depending on downstream process objec-
tives and feedstock properties [23].
Solvent recovery for reuse is a crucial part of the deasphalting unit because the
solvent is expensive and its ratio to the oil feed is high. Solvent recovery from the
deasphalted oil is carried out at a high temperature of about 200°C. Carbon dioxide
can be employed to effectively separate the solvent from the deasphalted oil at a
much lower temperature of about 40°C. This is achievable due to the increase in the
interaction between the CO2 and the solvent [24].
Some classes of asphaltenes, which are insoluble in paraffin solvents, are
removed using aromatic solvents. The drawback, however, is the high solvent-to-oil
ratio required to remove most of the asphaltenes and the consequent high cost of
solvent recovery. Asphaltene removal achieves sulfur content reduction, API gravity
increase, viscosity reduction, and improvement in other oil properties. Some con-
ventional deasphalting processes are done at the crude production site to upgrade
heavy oil and bitumen but may also be carried out as a pre-treatment in the refinery.
Deasphalting is achieved under high-temperature condition, which simultaneously
achieves cracking and upgrading of the heavy oil. Subsurface deasphalting may be
done for heavy oils using solvents but will not be addressed here.
3.2.3 Demetallization
Most crudes, especially heavy oils, contain various metals in different concentra-
tions ranging from 1000 to a few million ppm depending on the origin of the crude.
These metals are mainly sodium (Na), potassium (K), lithium (Li), calcium (Ca),
171
strontium (Sr), iron (Fe), cupper (Cu), silver (Ag), manganese (Mn), tin (Sn), lead
(Pb), cobalt (Co), titanium (Ti), gold (Au), chromium (Cr), vanadium (V), and
nickel (Ni). These metals are present either as inorganic salts or as organometallic
compounds such as porphyrins. They are accumulated in resins and asphaltenes
and need to be removed to their barest minimum if not completely before refining
because they lead to catalyst deactivation and corrosion in equipment and contrib-
ute to “acid rain.” The water-soluble salts, such as sodium chloride and magnesium
chloride, produce hydrochloric acid which is very corrosive. Calcium and magne-
sium combine with carboxylic acid to form soaps which act as emulsifiers and so are
undesirable. Most of these metals combine with naphthenic acids to form complex
organometallic compounds, while others are present as oil-soluble metallopor-
phyrins. These metallic complexes contain asphaltenic aggregates which have low
reactivity; thus, most conventional metal removal methods require severe condi-
tions [25]. The water-soluble salts are significantly removed during the desalting
step before refining. The most abundant of trace metals in crude oils are nickel and
vanadium which cause catalyst poisoning. It is, therefore, easier and preferable to
demetallize heavy crudes before refining. The existing methods of demetallization
can be broadly classified into three, namely:
i. thermal and chemical methods, where the nature of the organic matrix is
modified;
ii. solvent and adsorption methods, where the metal-containing compounds

are separated from the oil; and
iii. unconventional methods, where electric fields, magnetic fields, or radiation

is employed [26].
Currently, demetallization is most commonly achieved during hydrotreating,

deasphalting, and hydrocracking [27]. However, the efficiencies of these processes
are greatly hampered by the presence of the metals that poison the catalysts. It has
been reported that for greater effectiveness in metal removal, the usual hydrotreat-
ing catalysts should be dosed with very small amounts of active metals belonging to
the sixth and seventh subgroups of the periodic table [28]. The chemical reaction,
by which metals (especially the more common nickel and vanadium) are removed,
is given in Eq. (1). By a sequence of two mechanisms, the porphyrins are first
dehydrogenated to form precursor species which thereafter undergo ring-cleavage
reactions leading to metal deposition on the catalyst surface.
(MP) + H2 ⇌ (MP H2) ⟶ M + P H2 (1)
where MP is the metalloporphyrin, MPH2 is the intermediate hydrogenated

metalloporphyrin, M is the deposited metal, and PH2 is the resulting hydrocarbon.
Using chemical methods, metalloporphyrins react with an acid as given in Eq. (2):
MP + HX ⇌ MX + PH (2)
where MP is the metalloporphyrin, HX is the acid, MX is the metal-acid com-

plex, and PH is the resulting hydrocarbon [28].
It is, therefore, very necessary, especially for heavy metals, that a pre-treatment
step be employed to first reduce or remove these harmful metals. There are newer
technologies for metal removal, such as solvent extraction, by which up to 51%
vanadium and over 65% nickel can be removed using cyclohexane and other
172
organic solvents. Other methods include oxidation, electrochemical process,

immiscible ionic liquid extraction, and adsorption [29]. Some natural and synthetic
zeolites have been successfully employed to selectively remove nickel and vanadium
[25, 30]. A special challenge encountered in the removal of calcium due to the
presence of calcium naphthenate (CaNA) that is formed from calcium cation and
the anion of naphthenic acids has been reported. An aqueous solution, containing
a calcium-removal agent, was successfully employed to completely remove calcium
from heavy crude oil [31].
3.2.4 Denitrogenation
Nitrogen is one of the major heteroatoms but is also present in crudes as

nitrogen-containing compounds which need to be removed from crude oil to avoid
downstream problems. Common nitrogen-containing compounds are mainly in
form of complex structures such as porphyrins and quinolines as well as simple
ones such as pyridine (C5H5N) and pyrrole (C4H5N), which are prone to free radical
addition reactions to form gums and amines. These react with acid catalysts and
cause deactivation [32]. Nitrogen content in most conventional oils is <0.3 wt%, but
in heavy crudes, it can be as high as 1 wt% and can exceed that in some high nitrog-
enous crudes [33]. They are more thermally stable than sulfur compounds and so
require higher heat to be removed. Though organonitrogen compounds occur at
such low levels, they are undesirable because they cause catalyst poisoning in the
refining process and generate a pollutant (NOx) upon combustion [34].
Hydrotreating units serve for effective denitrogenation and are the benchmark
against which other methods are measured. Of the common heteroatoms, nitrogen
is relatively more difficult to remove [35]. Hydrodenitrogenation removes nitrogen
by forming other compounds such as ammonia, which are then separated from the
oil. This method of nitrogen removal leaves the hydrocarbon part of the nitrog-
enous compound in the oil. A typical dehydrogenation reaction removes nitrogen
in the form of ammonia as shown in Eq. (3). The common catalysts are cobalt,
nickel, and molybdenum disulfide but are combined in appropriate ratios for the
particular feedstock.
R3 N + 3 H2 ⟶ 3RH + N H3 (3)
Other methods, however, are also applicable: these remove the nitrogen-contain-
ing compounds completely from the oil thereby reducing the hydrocarbon content
of the oil itself. One such method is liquid-liquid solvent extraction that exploits
the difference in solubility parameters and employs polar solvents, acidic solvents,
ionic liquids, and deep eutectic solvents [32]. Some others are liquid-solid solvent
extraction, physical adsorption and chemisorption between the solid adsorbent
and the nitrogen-containing compound [36]. Adsorption beds can be packed with
activated carbon, silica gel, resins, polymers, and zeolites [37, 38]. Nitrogen limit
is not directly given in fuel specification but is indirectly specified as gum content,
storage stability, and thermal stability.
3.2.5 Deoxygenation
Oxygen is present as one of the heteroatoms and in other forms in oxygen-

containing compounds that are natural contaminants in crude oil. A wide variety
of oxygen-compounds have been identified in literature. More than 20 such
compounds (containing both oxygen and nitrogen) in amounts significant enough
to be regarded as above trace amounts have been reported [14]. Some of these
173
compounds, being weakly acidic, are responsible for petroleum acidity and include
carboxylic acids, cresylic acid, phenols, and naphthenic acids. Oxygen content
in crude oils can vary from 0.05 to 1.5 wt%. Generally, heavy oils contain larger
amounts of oxygen than light oils [39]. Naphthenic acids can be extracted using
dilute caustic solutions; other oxygen-containing compounds, which are non-
acidic, include esters, ketones, and amides but are quite negligible. These com-
pounds along with sulfur are simultaneously removed during hydrotreating and
other processes. Much of the unwanted oxygen is actually in the produced water,
which is removed in the desalter. There is no special process to selectively remove
oxygen alone from crude oil.
3.2.6 Desulfurization
Sulfur is a major drawback in the pricing of oil products because it contributes

most significantly to equipment fouling and environmental pollution. Sulfur-
containing compounds in crude oils vary in nature and concentration with boil-
ing range; with the heaviest fraction, it containing the highest amount of sulfur.
Compounds that contain aliphatic sulfur (sulfides and thiols) have been found
easier to remove than compounds containing aromatic sulfur (thiophenic com-
pounds), which are present in higher proportions in heavy crude oils [40]. High
percentage removal of sulfur (above 70%) can be achieved using combined oxi-
dants (KMn04-H2O2) in a formic acid catalyzed reaction system [41].
Conventional high-pressure hydrodesulfurization process is being replaced by
more effective oxidative desulfurization (ODS) at mild conditions without hydro-
gen pressure but with various catalysts. ODS is sometimes assisted and further
enhanced with ultrasound technology and the use of ionic liquids [42]. This has
become necessary due to the shift in global oil supply from light to heavy oil, which
usually has higher sulfur content. Microwave irradiation can also be used as a pre-
treatment for heavy crude oil where the sulfur content is not relatively high though
fragmentation and recombination reactions may not be avoidable [43]. Currently,
however, most desulfurization processes are carried out during refining and not as a
pre-treatment (except for crudes with very high sulfur content), and if as a pre-
treatment, then it serves also to upgrade the feedstock.
3.2.7 Desalting
The desalting process derives its name from the fact that soluble salts in the
crude oil enter the aqueous phase and are easily removed by phase separation in
the desalter. The wash water to oil ratio is 3–4 for light oils of API > 30o and 7–10
for light oils of API < 30o; a pH of 6 is ideal for the wash water and may be adjusted
using caustic soda or acid [44]. For the case of heavy oils, however, with API < 20o
but >10o, much higher water volume ratios will be required.
The desalting unit is where virtually all the aforementioned pre-treatments take
place to some extent apart from the deasphalting step. For heavy and extra-heavy
crude oils, however, there may be need to include one or more of the above specific
pre-treatment steps to be carried out before the general desalting process. This
may be warranted if the heavy oil has a peculiar need for such a step; otherwise,
a two or three stage desalting unit may very-well serve all the purposes needed to
achieve about 90% removal of contaminants from the heavy crude. This is because
heavy crudes have higher proportions and wider ranges of contaminants such that a
one-stage desalting process alone will not be adequate to pre-treat them for efficient
refining [1]. In a typical single-step desalting unit as shown in Figure 1, the crude oil
is pumped from storage through a heater, and fresh water, dosed with demulsifying
174
Figure 1.
Single-stage desalting unit.
agents, is added to the oil stream, which goes through a mixing valve for proper mix-
ing. The stream then enters the gravity settling tank, where the water phase settles by
gravity at the bottom of the tank, while the oil phase remains above it.
The separation of the oil from the water phase in the gravity settling tank is
often aided by installing two electrodes between which an electrostatic AC or
DC field is created with a potential of between 12,000 and 35,000 volts [45, 46].
These values are, however, most likely going to increase significantly in the desalt-
ing of heavy oils. The electrostatic field promotes coalescence of water globules
and enhances separation. Effluent water is sent to water treatment unit, while
the desalted crude is drawn from the top of the settling tank to the refinery for
processing.
For heavy crude oils, however, except for crudes with exceptionally low amounts
of contaminants, the desalting unit given in Figure 2 is recommended, where the
subunits in blue outlines are included for necessity. As the crude is pumped from
storage, part or all of it is first diverted to a special treatment unit as the special
need of the particular crude may require.
3.2.7.1 Special treatment unit
The traditional desalting and dehydration process was fully developed for light
crudes of relatively high API gravity and low viscosity, but with the proportional
increase in available heavier crudes, modifications have become necessary for
effectiveness and efficiency in the desalting process. Heavy oil, especially with high
contaminants, may be desalted after it is passed through its own special purification
unit to significantly reduce the particular contaminant in question. For example,
heavy oil with very high sulfur content can be first passed through a microwave
irradiation unit before desalting [43]. Also, an adsorption packed bed with appro-
priate zeolite grades could be used to selectively reduce metal ions for a heavy
crude, which is contaminated with a specific heavy metal [25]. Another possible
case is a minor deasphalting unit using solvent extraction [21].
From the special treatment, the fresh water with demulsifying agents is added
before the back-mixing by the mixing valve and then the stream flows to the first
gravity settling tank. With the obvious need for a second gravity settling tank,
the oil is sent to it for further separation, while the effluent water from the first
settling tank is sent to water treatment unit. The desalted oil from the second
tank goes to the final step in the pre-treatment section which is the hydrotreat-
ment unit before it is sent to the refinery for processing, while the water from
the bottom of the second tank is recycled as shown (Figure 2). This proposed
arrangement is expected to achieve excellent results for the pre-treatment of
175
Figure 2.
Two-stage desalting unit with special treatment option.
heavy crudes. This special treatment unit may be bypassed if it is not required for
a feedstock with minimal contaminants.
3.2.7.2 Multi-stage desalter
Heavy oils contain higher percentages of impurities and contaminants which

cannot be removed by the conventional single-stage desalter. A two- or three-stage
desalting unit will be required depending on the degree of contamination. A two-
stage desalting unit is shown in Figure 2.
3.2.7.3 High-speed centrifuge
The limitations of the desalting process when treating heavy crude oil of API
gravity of less than 20o and greater than 10o and of high viscosity can also be
overcome by using a high-speed centrifuge. Well-designed high-speed centrifuges
combine efficiency, reliability, product quality, and environmental friendliness.
Gravity settling tanks are not very effective with heavy crudes even with the aid
of an electrostatic field (AC or DC) due to their high viscosity. With a single-stage
centrifuge technology, excellent separation between the oil and water phases is
achievable [1]. The use of centrifuges leads to lower costs in energy consumption
(in the electrostatic field), lower temperature and pressure in the operating condi-
tions of the desalter, and less material and handling costs due to lower water-oil
ratio and less amounts of demulsifying agents.
3.2.8 Hydrotreating
Hydrotreating is one major way of removing sulfur and other contaminants

present in crude oil fractions. It can be applied at different stages of the refining
process to different streams as required [47]. For the pre-treatment of heavy oils,
however, hydrotreating needs to be employed primarily in its simplest form to
significantly reduce or remove sulfur which can be as high as 8% by weight [19].
This unit is recommended to be placed immediately after the desalting tank and
so serve as the last unit in the pre-treatment section before the refining process.
Here, the desalted oil is mixed with hydrogen and heated to between 340 and
425°C, pressurized to about 14 MPa, and then passed over a suitable catalyst.
Some commonly used catalysts are mainly cobalt, nickel, and molybdenum oxides
176
on alumina. Biocatalysts have also been explored but have not yet become com-
mercially attractive [32, 42, 44, 48].
In the hydrotreating unit, the primary target element is sulfur but many of the
contaminants, which have been discussed earlier, are also removed simultaneously
through several reactions as mentioned below:
• Hydrodesulfurization (HDS) reaction, which occurs between sulfur-containing

compounds and hydrogen, leads to the removal of sulfur in the form of
hydrogen sulfide. Eq. (4) shows such a reaction between ethanethiol (C2H5SH)
and hydrogen (H2). The hydrogen sulfide gas is captured and converted into
elemental sulfur and sulfuric acid.
C2 H5 SH + H2 ⟶ C2 H6 + H2 S (4)
• hydrodenitrogenation (HDN) by which nitrogen is removed mainly as ammonia;
• hydrodemetallization (HDM) by which metals are removed by being deposited

on the catalysts;
• hydrodeoxygenation (HDO) by which oxygen is removed as water; and
• hydrodearomatization (HDA) by which olefins, naphthenes, and aromatics get

saturated with hydrogen and become paraffins. Minor cracking also takes place
to produce light alkanes.
The numerous products from the hydrotreating unit (HTU) are cooled using
a series of heat exchangers then charged into a high-pressure gas separator, where
hydrogen sulfide, ammonia, and the unreacted hydrogen are separated from the
hydrotreated crude. The gases are sent to a scrubber with ethanol amine or other
basic solutions to remove hydrogen sulfide for sulfur recovery, while hydrogen is
recycled [49].
4. Modification requirements for heavy oil pre-treatment
Crude oil pre-treatment is a requirement before refining to remove contami-

nants which may be naturally part of the crude or acquired during production. A
simple single-stage desalter can achieve sufficient purity when handing light crudes
[16]. For heavy crudes, however, it is imperative to introduce some modifications
since the conventional desalter will not be adequate. These modifications begin with
the storage and pre-treatment process and extend all the way to the refining process
and equipment. In the pre-treatment unit, a packed bed to achieve a significant
degree of deasphalting, demetallization, deoxygenation, or denitrogenation should
be introduced as an option at the beginning of the process depending on the par-
ticular need of the feedstock. The gravity settling tank (desalter) should be in two
stages or may be replaced with a single high-speed centrifuge desalting tank. After
desalting and the separation of the oil from the water phase, the desalted crude
oil can then be partly hydrotreated in a mini hydrotreatment unit, particularly
for heavy crudes with very high sulfur content. This applies to heavy crudes with
>10–20o API gravity. Figure 3 shows a schematic diagram of our proposed modifi-
cation of the pre-treatment unit for efficient handling of heavy crude oil.
177
Figure 3.
Modified pre-treatment unit.
In the near future, extra-heavy crudes with an API gravity of <10o will be
desalted in units with yet further modifications. This is because the API grav-
ity of water is 10o and a crude with 10o API cannot be separated from the water
phase by gravity. For extra-heavy oil, however (API < 10o), gravity settling tanks
or centrifuges will still serve for phase separation; but in this case, waste water
will be drawn from the top of the tank, while desalted crude will be drawn from
the bottom.
5. Cost implications
Currently, heavy crude oil is more expensive to produce (upstream) but yields
less economic returns to the producer because of the challenges encountered in its
processing and the lower quality of its products; on the other hand, lighter crude
is cheaper to produce and easier to process, and therefore, it is more expensive.
With the economic turn of events lately, much of the global lighter crude reserves
have been greatly depleted, while heavy crude reserve is in over-abundance,
and refiners are now beginning to prefer to buy heavy crudes which are cheaper
and modify their processes and equipment which is capital intensive. There is,
however, a trade-off because the process modification is a one-time investment,
while the long-term good product yield eventually compensates with a high return
on investment. The development of new technologies for processing heavy oils
needs to be rapid enough to forestall the effects of the dwindling supply of con-
ventional crudes. It is also expected that in the course of process modifications,
new technologies will serve to significantly reduce anticipated cost and favor heavy
oil production. For example, in a modified desalting unit, the use of a high-speed
centrifuge eventually results in significant savings in energy and material cost.
This is due to lower temperature and pressure conditions, less amounts of required
demulsifying agents, less quantity of wash water, and therefore less waste water
generation. As refiners invest more in processing heavy oil, producers will more
likely be motivated to invest in its production. The economic face of the oil market
is likely to experience new paradigms as heavy oil processing technologies begin to
compete with light oil refineries. For light oils, cost of refining, depending on oil
configuration and refinery size, can vary widely from 4 to 15 USD/bbl, while for
heavy oils, it is in the range of 20–22 USD/bbl [50, 51].
In basic refinery economics, the cost of crude oil and the price of refined
products are highly volatile and nearly unpredictable because they are affected
by economic, political, and environmental factors. Since refiners have no control
178
over these factors, operational efficiency, which is measured by the ratio of output
to inputs, is the basis for profit maximization and can be increased through con-
tinuous innovation [50]. As a determinant of profitability, facility expansion for
complexity to handle a wider variety of feedstocks can impact on profitability up
to the tune of 0.5 USD/bbl [51]. This implies that modifying the pre-treatment sec-
tion of a refinery to handle heavy crude oils for efficient refining into “attractive”
products is economically favorable. Since heavy oils are cheaper than light oils and
the cost of crude oil is the largest input cost of a refinery, processing cheaper crudes
into higher-value products through process modification usually improves profit
margins. The increased global demand for lighter petroleum products made from
heavier crudes (quality gap) drives downstream investors toward more complex
refineries. A refinery’s complexity is measured by its range of capacities to “add
value” by its processes to a crude feedstock. The most common cost-based measure
of complexity for refineries is the Nelson Complexity Index (NCI). It provides a
relative measure of the construction cost of a refinery based upon its capacity to
upgrade. The simplest topping refinery is assigned an index of 1.0 against which
all others are measured. The higher the NCI number of a refinery, the more its
complexity, cost, and capacity to add value to crude feedstocks. Since 2005, global
trends have been toward refineries of higher complexities through newer technolo-
gies; hence, older refineries with low NCI numbers are fast fading out as lower-
value crudes (such as heavy oils) increase in relative abundance. A refinery with a
fluid catalytic cracker, alkylation, and hydrotreating units has an NCI of about 7.0,
while an inclusion of hydrocracking, coking, and reforming units can raise its NCI
number to about 14.1 [51].
For the pre-treatment section, therefore, the proposed necessary modification
here will definitely cause a minor increase in the NCI number of the refinery due
to the additional pieces of equipment. An overview of NCI numbers of complex
refineries shows a wide range from 5 to 14 [52]; therefore, it is estimated that the
pre-treatment section contributes only about 1–1.5% of the total NCI number and,
hence, total cost of the refinery. The bulk of the refinery cost is in the refining
processes and not in the pre-treatment; consequently, the pre-treatment equipment
cost is certainly less than 2% of the total cost of the refining equipment with the
modification proposed in this chapter even for pre-treating the most challenging
heavy oil feedstocks.
6. Conclusion
It can be concluded from the issues discussed in this chapter that a modifica-
tion of the conventional oil pre-treatment unit is required to ensure the adequate
removal of impurities from heavy crude oils. First, a special optional unit is intro-
duced at the beginning of the pre-treatment unit to treat crudes with any extremely
high level of a particular contaminant such as heavy metals, asphalt, or sulfur.
Second, the desalting stage is carried out in two stages aided by electrostatic fields,
and third, the desalted crude is sent to a mini pre-hydrodesulfurization unit before
it goes for proper refining. With high purity of pre-treated crude, refining processes
will be enhanced, product quality will improve, and downstream problems will be
reduced to their barest minimum or completely eliminated.
179
Appreciation
The authors thank Emmanuel O. Fajoye for assisting with the figures and
Toluwaniyi S. Babalola for handling the IT matters.
Author details
Faith Uchenna Babalola* and Alfred Akpoveta Susu

Department of Chemical and Petroleum Engineering, University of Lagos, Lagos,
Nigeria
*Address all correspondence to: [email protected];

[email protected]
180
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184
Chapter 11
Recent Techniques for the Removal

of Naphthenic Acid from Heavy
Crude Oils
Feyisayo Victoria Adams, Chikaodili E. Chukwuneke
and Bolade O. Agboola
Abstract
Naphthenic acid (NA) is one of the components of heavy crude oil. It is com-
posed of a carboxylic acid functional group attached to a hydrocarbon molecule.
Heavy crude oils with high concentration of NA are usually classified as poor
quality oil and are sold at cheaper price. The presence of high concentration of
naphthenic acid in crude oil often result in limited life span of equipment used in
exploration and refining processes due to corrosion. In order to improve the quality
of such crude oil and to save cost, it becomes very important to remove NA com-
pounds from it. Researchers, as well as the oil and gas industries, have been working
on how to overcome this challenge, and several techniques have been developed
for the removal of naphthenic acid from the crude oil. This study thus envisages to
present the various recent techniques available for the removal of NA from heavy
crude oil. It has been seen that of all the recent physical and chemical methods that
are available, catalytic-based methods are effective and their effectiveness depend
on the temperature at which the catalyst is calcined as well as the surface area of the
catalyst.
Keywords: catalysts, extraction, heavy crude oil, naphthenic acids,

petroleum refining
1. Introduction
Naphthenic acid (NA), which is a mixture of alicyclic carboxylic acid and

saturated aliphatic acid, is a component of a heavy crude oil and it is responsible for
the heavy crude oil’s acidity [1]. The presence of NA in heavy crude oil poses great
challenge in the exploration of the crude oil; this is due to the corrosiveness of the
acid. The removal of NA compounds from crude oil is known as the most important
process in upgrading heavy oil. Caustic washing and blending of heavy acidic crude
oil with conventional crude oil are two conventional methods used in the removal
of NAs from heavy crude oil. The disadvantage of blending method is in its low
efficiency with removal of about 2–3% [2] and the NAs are often not completely
removed from the blend as a result, it is often used as a corrosion mitigation tool.
Meanwhile, the limitation of caustic washing method is in the large amount of
wastewater which is usually produced during the process [2].
185
Several deacidification removal techniques have been reported in the literature.

These include catalytic destructive methods, non-catalytic destructive methods,
and non-catalytic non-destructive methods [3, 4]. Thermal decomposition, which
is an example of non-catalytic destructive methods, has shown to be ineffective in
the reduction of acidity in heavy crude oil [5]. High temperature, which is higher
than 400°C, is often used. This offers thermal cracking of the heavy crude oil,
which then resulted in coke formation [1]. Catalytic decarboxylation process [6]
has been used as an alternative to the non-catalytic destructive methods for naph-
thenic acids (NAs) removal from heavy crude oil. Polymeric compounds exhibiting
basicity characteristics, on the other hand, can be used to neutralize NAs. Although,
expensive neutralizing agents, which are difficult to recover from deacidified
products, are needed in this method.
Extractive separation is another method used in the removal of NAs from heavy
crude oils. Using this method, valuable hydrocarbons are usually removed and this
makes the process expensive. Extractive separation method requires multistage
wash using different types of solvents. A single NA compound or their derivatives
such as salt and water-oil emulsion can also be used [3]. It has been reported that
solutions of metal oxides, such as those of aluminum and magnesium, exhibit high
adsorption capacity and are able to remove more than 95% of the NAs present in a
liquid hydrocarbon feedstock at temperatures between 30 and 80°C [4, 7].
Adsorption process of NA removal from heavy crude oil can be used under low
temperature condition for distillate fractions. Strong bases, such as alkali metal
hydroxides (MOH), are often used as pre-treatment of the heavy oil prior to the
adsorption process. The MOH, however, does not only provide an alkaline environ-
ment, but it neutralizes the acidic components of NAs in the heavy crude oil. The
major challenge associated with this technique is its environmental challenge as
disposal of MOHs into the environment creates nuisance to the environment [7].
Esterification process has been used to remove NAs from heavy crude oils. The
NAs reacts with alcohol with or without the addition of a catalyst to form ester [8].
Oxides and carboxylates of metals have been successfully applied in NAs removal
from heavy crude oils [9–11] using the esterification method at reaction tempera-
tures between 250 and 350°C [12].
Organic bases such as monoethanolamine, 2-(Dibutylamino) ethanol [13],
glycolic solutions [11], or imidazole derivatives [14] as alcoholic solutions have been
used as alternative method to dilute caustic wash in the NAs removal from heavy
crude oil. However, the amount of organic bases needed for a successful extraction
is usually in excess. This results in amine been left in the petroleum phase, thus
creating problems in the downstream catalyst units which is used for oil upgrading.
On the other hand, lysine-derived amino acid ionic liquids (AAILs) have shown
better extraction efficiency compared to other AAILs, because lysine-derived
AAILs contain two amino groups which can react with carboxylic acid group to
form zwitterionic species [3].
Zeolites [3] and metal oxides [15] have been successfully applied in NAs removal
from heavy crude oil. The limitations associated with this process, however, are the
moderately high operating temperatures of 300–400°C and the use of hydrogen [5]
to increase deacidification rate, because hydrogen is often not available for the pro-
cess. The use of caustic soda (NaOH) is a known industrial method for the removal
of NAs from the kerosene/diesel fractions. The NAs are usually separated from the
oil fraction as sodium naphthenates and is dissolved in water to form soluble frac-
tion. Thereafter, acidifying sodium naphthenates with a mineral acid, will result
in the recovery of water insoluble NAs [3]. However, due to poor solubility of NAs,
their removal becomes incomplete [3].
186
Recent Techniques for the Removal of Naphthenic Acid from Heavy Crude Oils
Reactive extraction method has gained wide interest in the removal of NAs
from oil. This came in response to the extreme economic pressure NAs removal
poses on industries. Due to the decrease in efficiency and limitations of well-known
processes and the demand for inexpensive and environmentally safe and high
purity products, it is imperative to consider new processes. Thus, this work is aimed
at compiling recent techniques used in the removal of NAs from heavy crude oil.
These techniques include the physical and chemical methods which are reactive
extraction and adsorption of naphthenic acids (physical methods) and esterifica-
tion of naphthenic acids, decarboxylation of naphthenic acids, and supercritical
fluids (SCF) (chemical methods).
2. Physical methods
2.1 Reactive extraction of naphthenic acids
Reactive extraction is a separation process in which reactions between materials

to be extracted and the extractants take place. This extraction process depends on
degree of extraction and different parameters such as the loading ratio, complex-
ation equilibrium constant, distribution coefficient, type of complexes, etc. The
distribution coefficient and the degree of extraction are used to analyze the extrac-
tion process. Equation (1) is used in the calculation of the distribution coefficient,
Kd [16].
Corg
Kd = _ (1)
Caqu
where, Corg and Caqu are the total concentration of carboxylic acid in organic
phase and the total acid concentration (dissociated and un-dissociated) aqueous
phase at equilibrium, respectively.
The degree of extraction is given as the ratio of acid concentration in the
extracted phase to the initial acid concentration in aqueous solutions at equilibrium
as shown in Eq. (2) [16].
K
E = _d
× 100 (2)
(1 + Kd)
Kumar et al. [16] determined equilibrium complexation constant, extraction

mechanism, degree of extraction, and the distribution coefficients using varied
concentration of extractant (hydroxides). In this process, NA was dissolved in
0.125–0.650 mol/L of kerosene at temperature range of 301–333 K and atmospheric
pressure. The distribution coefficient (Kd) of NA was found to be about—19.84 with
degree of extraction of 56.48–95.16% at various temperature and concentration
ranges. The highest degree of extraction (95.2%) was obtained at a concentration of
0.125 mol/L and at room temperature, while it decreased with increase in concen-
tration. Meanwhile, the degree of extraction decreased as the temperature reached
60°C (333 K). It was observed that the degree of extraction increased with increase
in the pH of the extractant [16].
Liquid-liquid extraction (LLE) has been found to be effective in the removal
of NAs from heavy crude oils. However, the effectiveness of this process depends
on the extractant and the experimental conditions such as temperature, contact
time, and concentration. The use of ammonia or alcoholic alkaline solutions
(such as potassium hydroxide (KOH) in alcohol) in the removal of NAs using
LLE method is common and is effective. However, these extractants usually
187
form stable emulsions [17]. Due to this limitation, other extractants have been
proposed by several researchers [9, 18]. Liquid alkanols, ammonia in varied ratio
with water are examples of the proposed extractants. Pre-treatment of heavy
crude oil before extraction using alkoxylated amine and water has also showed
better results in the removal of NAs [19]. Also, a mixture of NaOH and ethanol
with heavy crude oil with the reagent/oil ratio being 0.4:1 (w/w) at room tem-
perature showed an optimal amount of NaOH in crude oil after extraction to be
3000 μg/g under 5 min of extraction [14]. Liquid-liquid extraction (LLE) data
were obtained for a ternary system of dodecane, naphthenic acid, and [DBU-Hex]
[SCN] under atmospheric condition [20]. The solubility of NA was found to be
higher in [DBU-Hex] [SCN] when compared to dodecane. Thus, [DBU-Hex]
[SCN] was concluded to be better extractant for the removal of NA from heavy
crude oil than dodecane.
Ionic liquids (ILs) have been considered as green solvents for extraction pro-
cesses due to their unique properties [21, 22]. The physiochemical properties of ILs
depend on the cations and anions of various ILs. The symmetry of the shape or/and
alkyl chain in the cation could have effects on the viscosity, density, and surface ten-
sion of ILs, meanwhile ILs miscibility and their thermal stability could be affected
by the anion [23]. The wide range of temperature for liquid phase and extremely
low vapor pressure of ILs give them advantage over other solvents whether polar
or non-polar organic solvents. Report has, however, showed that some ILs need
large amount for effective extraction process for the removal of NAs. Also, the
regeneration procedure for NA and ILs has been found to be complex [24, 25]. Low
ILs/oil ratios of tetra-alkylphosphonium and tetra-alkylammonium hydroxide ILs
were used in the removal of NA from a model acidic oil [26]. The results from the
experiment showed tetra-alkylammonium-based ILs to be more efficient than tetra-
alkylphosphonium-based ILs. It was observed that the longer the alkyl spacer length
on the cation, the lower the extraction performance of the hydroxide-based ILs. The
ILs used in the model acidic oil study showed a great reusability potential without
losing its activity [26].
Neutralization method was used to remove NA from Doba crude oil using ILs
([N2221][MeCO3] Triethylmethylammonium methylcarbonate) at an optimum
temperature of 338 K and a removal efficiency of 73.1% was achieved [12]. Under
the same condition, an efficiency of 80.4 and 69.6% was achieved using [N2221]
[HCO3] Triethylmethylammonium hydrgoencarbonate and [N4441][MeCO3]
Tributylmethylammonium methylcarbonate, respectively [12].
Crude oil containing dodecane and NA (TAN = 1.44 ± 0.01 mg KOH g−1) was
treated for NA removal using extraction method and 1-Decyl-3-ethylimidazolium
phenolate.[C10mim][Phe] as extractant [27]. The optimum temperature, at which
an efficiency removal of about 85.7% was achieved, was 320 K. On the other hand,
when a crude oil having dodecane and NA (TAN = 4.74 ± 0.01 mg KOH g−1) was
treated, an efficiency of 83% was achieved at a temperature of 323.15 K [26].
Neutralization method was used in this case and Tetra methyl ammonium hydrox-
ide, [N1111][OH] was used as the solvent. At a temperature of 323 K, a removal
efficiency of 25% was obtained using extraction method with 1-ethyl-3-methyl-
imidazolium ethyl sulfate [EMIM][EtSO4] as extractant [28].
Adsorption process was used for the removal of NA from crude oil con-
taining white oil and NA (TAN = 1.20 mg KOH g−1) [29], dodecane and NA
(TAN = 3.46 ± 0.01 mg KOH g−1) [24] and dodecane and NA (TAN = 2.93 ± 0.01 mg
KOH g−1) [21] at temperatures of 313 K, 360.15 K and room temperature,
respectively. A removal efficiency of 97.61, ~71.5, and 100% was achieved
in the process using 1-methylimidazole acetate [Bmim][CH3COO] [29],
188
1-decyl-1,8-diazobicycloundec-7-enethiocyanate [DBU-Dec] [SCN] [24], and Butyl

methyl imidazolium functionalized silica SilPrBmim [21] as ILs, respectively.
2.2 Adsorption of naphthenic acids
Adsorption process has recently been used for the removal of NAs from heavy
crude oils. Example of these is the removal of NAs from Sudanese crude oil using
zeolite and clay [30]. A study by Zhang et al. [31] showed that the use of a naturally
occurring clay gave adsorption capacity for NAs as high as about 70 mg-NA/g clay.
Though this process is effective and efficient, its limitation is in the disposal of the
used clay.
Lately, nanotechnology has been brought to light as the latest technique that
can be applied in reducing TAN present in solutions. Simonsen [32] synthesized
amino-functionalized iron oxide (Fe3O4) nanoparticles which has a high selectivity
for NA. Harnessing the magnetic properties of the nanoparticles, a magnetic field
is applied to the mixture for the sequestration of the NA. Among the nanoparticles
synthesized: Fe3O4, Fe3O4/SiO2, Fe3O4/SiO2 NH2/C18, the amino-functionalized
type showed a high affinity for NA and spectra from FTIR and UV-Visible
Spectrophotometer confirmed that no other crude oil components were eliminated.
This study achieved a remarkable feat of attaining a TAN reduction of 92% with this
novelty.
3. Chemical methods
3.1 Esterification of naphthenic acids
Esters are a byproduct of reacting ▬COOH with ▬OH and this reaction is
useful for NAs removal from solutions, since the major functional group for organic
acids are carboxyl groups. The general form of an esterification reaction of NA takes
the form below (Figure 1).
In the absence of any catalyst, Khan et al. [2] optimized the removal of NA from
heavy acid crude oil by varying the pressure, reaction time, crude concentration,
and temperature. A mixture of HAC Laguna and Kuwait Crude with TAN value
of 2.57 mg KOH/g was esterified with methanol in a batch reactor and under the
enhanced conditions of 250°C, 6.4 MPa, and 33.3 wt% to yield low TAN crude of
0.08 mg KOH/g (96.9% removal).
Another example of this application is observed in the esterification of Colombian
crude by Quiroga-Becerra et al. [34]. Temperature was varied to see its effect on
shrinking the TAN content and also FTIR analysis was done on products at each tem-
perature profile. At 250°C, the outcome of the study was impressive as the TAN value
fell from 7.33 to 0.47 mg KOH/g. FTIR data also support the post reaction TAN results,
as a shrinking in the carboxyl group wave number between 1705 and 1710 cm−1 was
observed. In addition, as a corollary to the esterification, a shift in the carbonyl group
band to wave numbers 1730–1740 cm−1, indicated a reduction in acidity.
Figure 1.
Esterification reaction of NA [33].
189
3.2 Decarboxylation of naphthenic acids
In catalytic decarboxylation, commercially available chemicals or self-prepared

materials are usually used as catalysts to determine their suitability and effective-
ness in removing NAs from heavy crude oils with model compound before using
them in a real situation [31]. Metal oxide catalysts have been found to be very effec-
tive in NAs catalytic decarboxylation. The beauty of catalysis lies in its ubiquitous
application as it cuts across many chemical methods of NA removal. Every chemical
reaction can be encouraged to favor NA removal by the use of active catalyst that
provides an alternative pathway that ensures the lowering of the activation energy
for the reaction to occur (Figure 2).
A study carried out by Shohaimi et al. [35] has shown the use of monometallic
alkaline earth metal oxides (Ca/Al2O3 and Ce/Al2O3) as catalysts for the removal
of NAs from acidic Petronas Penapisan Melaka refinery heavy crude oil with TAN
of 2.43 mg KOH/g to be successful. It was observed that the Ca/Al2O3 catalyst
was more effective (83.5%) in removing the NAs from crude oil compared to Ce/
Al2O3 catalyst (71.2%). In another study, other types of catalysts (Ni/Ca/Al2O3,
Ni/Ba/Al2O3, Cu/Ca/Al2O3, and Cu/Ba/Al2O3) were studied in TANX 2000 (con-
centration range of 10–50 mg/L) and ammonia solution in ethylene glycol with a
concentration range of 100–1000 mg/L to remove NAs from Petronas Penapisan
Melaka refinery Heavy Crude (TAN of 2.43 mg KOH/g), Petronas Penapisan
Melaka refinery Light Crude (TAN of 2.52 mg KOH/g) and Korean Crude oils.
The highest concentrations of TANX 2000 solution and ammonium solution in
ethylene glycol exhibited the best experimental conditions. The catalyst (Cu/
Ca(10:90)/Al2O3) with calcination temperature of 1000°C gave the most effec-
tive results for all the three types of crude oil. With the use of catalysts, there
was improvement in the removal of NAs from all the three crude oils that were
studied [36].
With the goal of removing NAs at low temperatures and on an economy
budget, rare earth metals known to possess great catalytic potential were explored
by Shukri et al. [37]. These researchers tested the use of alumina supported CeO-,
ZnO-, and SnO-based catalyst coupled with Cu, Co, Mn, and Ni as dopants to
deacidify Korean crude oil. Results showed that the calcination temperature, base
catalyst type with large surface area, and the base chemical agent do play a role
in optimizing the reduction of NA in Korean crude. The results proved CeO to be
the best catalyst and Cu (Cu/Ce (10:90)/Al2O3) as the most effective dopant, with
an optimum deacidification achieved when the aforementioned was calcined at
a temperature of 1000°C. A concentration of 1000 mg/L for 4% NH3-PEG gave
the best acidity cutback for the basic chemical agent used, but it was only able to
cut down the TAN from 8.32 to 3.65 mg KOH/g using the Ce oxide-based catalyst.
However, after it was augmented with 1% of 10 M KOH, the TAN was reduced
to 0.56 mg KOH/g thereby meeting acceptable industrial standards of crude oil
acidity [37].
The limitations involved in extant NA removal techniques such as emulsion
formations via neutralization, high cost from physical adsorption processes, and
cost of hydrogen from catalytic hydrogenation have hampered their industrial
Figure 2.
A catalytic reaction for the removal of NA [10].
190
applications. In a study in which γ-Al2O3 supported 12-tungstophosphoric acid

(TPA) catalyst was used in a fixed bed continuous flow reactor, factors such as
increased methanol/crude oil ratio, temperature, and decreased liquid hourly space
velocity (LHSV) downregulated the TAN value. Compared to other catalysts such
as SnO/Al2O3 [38] and Mg-Al Hydrotalcite [39], TPA/γ-Al2O3 has proven to enhance
the transesterification of NAs at lesser temperature (250°C). The TPA/γ-Al2O3
catalyst also decreased the Castilla crude oil TAN from 2 to <0.5 mg KOH/g with
a methanol feedstock of 2 wt%. In addition, TPA/γ-Al2O3 can remain stable for up
to 100 h of time-on-stream [40]. Table 1 shows a compilation of scholarly works,
where catalysts have been used for NA removal.
3.3 Supercritical fluids (SCF)
Improvements in chemical sciences and technology have impact in NA removal

with the advent of employing SCF especially supercritical water (SCW) and
supercritical methanol (SC-MeOH). The SCF by reason of definition are fluids
that exist at temperatures and pressures beyond their critical points. They have
been favored lately in NAs removal due to the global calls for greener processes that
would mitigate environmentally toxic materials. The SC-MeOH has been reported
to relieve refinery processes off the burden of corrosion issues associated with
NAs in heavy crude oils. In conducted pilot experiments [45], various factors such
as NA/SC-MeOH ratio, temperature, time, and pressure were studied to see their
influence on TAN reduction in Laguna and Bachaquero-13 heavy crude oil. Among
the process parameters studied, temperature was the key determinant on the TAN
reduction as a rise from 300 to 400°C lead to a TAN decline from 56 to 96.9%. Other
parameters such as pressure and NA/SC-MeOH ratio had little impact on TAN
reduction. Hence, the use of the lowest test pressure of 10 MPa and highest NA/
SC-MeOH ratio at 400°C. The aforementioned conditions are of a good report as it
allows for the process designed to handle TAN reduction operation to be made on a
low-cost budget.
Model oil Catalyst Reaction Total acid Reference

conversion (%)
China crude SnO▬Al2O3 Esterification 82 (TAN before/ [10]

after: 2.8/<0.5 mg
KOH g−1)
Cyclo pentane carboxylic MgO Decarboxylation ~100 [41]

acid, cyclo hexane
carboxylic acid, cyclo
hexane propionic acid,
and trans-4-pentyl cyclo
hexane carboxylic acid
dissolved in dodecane
Bohai oil NiAl-4-EG LDH Esterification ~90 [42]
Bitumen derived heavy ZnO Decarboxylation 8.5 [43]

vacuum gas oil (HVGO)
Heavy crude from MgO Neutralization 84.8 [44]

petronas penapisan
melaka
Table 1.
The model oil, catalyst type, reaction type, total acid conversion and the referenced work.
191
4. Conclusions
Selections of extractants and catalysts to be used for the removal of NAs from
heavy crude oil whether they are to be used in the physical methods or the chemical
methods are of utmost important. Calcination temperature, at which a catalyst is
calcined, and the surface area of the catalyst were seen to have significant effects
on its effectiveness in removing NAs from heavy crude oils. The higher the surface
area of a catalyst, the more effective it is in its capacity to remove NAs from heavy
crude oils. Also, catalysts, which are calcined at higher temperatures have been
seen to exhibit high removal efficiency. A Cu/Ce (10:90)/Al2O3 catalyst calcined at
1000°C removed about 93% of NAs from Korean crude oil using catalytic deacidi-
fication method. Removal processes in which catalysts containing 10% Cu in them
were used have been found to be effective in the removal of NAs from solutions.
Metal oxides nanoparticles have also shown to be promising in the removal of NAs
from solutions. Removal of NAs from acidic solutions dissolved in dodecane using
decarboxylation process with calcined MgO as catalyst yielded about 100% removal
of NAs from the acidic solutions. Although this was a modeled work, yet it looks
promising if applied in real life system and heavy crude oils.
Author details
Feyisayo Victoria Adams1,2*, Chikaodili E. Chukwuneke1 and Bolade O. Agboola1
1 Department of Petroleum Chemistry, American University of Nigeria, Yola,

Nigeria
2 Faculty of Engineering and the Built Environment, Department of Metallurgy,

School of Mining, Metallurgy and Chemical Engineering, University of
Johannesburg, South Africa
192
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195
Chapter 12
Nickel Tetraphenylporphine
Extraction from Model Heavy Oil
Using Ionic Liquids
Pradip Chandra Mandal
Abstract
Heavy metals containing compounds present in heavy oils create particular

problems on their upgradation and refinement processes. The aim of this work is
to extract nickel (II) tetraphenylporphine (NiTPP) from model heavy oils using
ionic liquids (ILs). Exploring open literature, four different ILs such as 1-butyl-
3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMIM]TFSI), 1-ethyl-
3-methylimidazolium octyl sulfate ([EMIM]OS), 1-butyl-3-methylimidazolium octyl
sulfate ([BMIM]OS), and 1-methyl-3-octylimidazolium tetrafluoroborate ([OMIM]
BF4) were utilized in this study. Potential experiments were conducted in a batch-type
extractor (design temperature of 250°C and pressure of 6 MPa) at temperatures of
0–180°C. The extracted samples were analyzed using UV-visible spectrophotometer
to determine the concentration of metallic compounds. The results show that NiTPP
extraction was increasing with increasing temperature and treatment time and
approximately 63% NiTPP was extracted in [BMIM]OS at a temperature of 100°C
and a treatment time of 40 min. It is also observed that NiTPP extraction was decreas-
ing above temperature 100°C. The extraction kinetics followed first-order kinetics
with respective activation energy and pre-exponential factor of 1.24 kcal per mol
and 2.156 × 10−3 s−1. Therefore, the IL, [BMIM]OS, is capable to extract NiTPP from
model heavy oils at temperatures below 100°C indicating the effectiveness of this IL
to extract NiTPP from heavy oils.
Keywords: heavy oil, heavy metal, ionic liquid, extraction kinetics, activation energy
1. Introduction
1.1 Heavy oil
Crude oil is a naturally occurring unrefined petroleum product that con-

tains hydrocarbons 50–97%, nitrogen, oxygen, and sulfur-containing organic
compounds which typically make up between 6 and 10%, while metals such as
copper, nickel, vanadium, and iron account for less than 1% of the total composi-
tion. According to Koliander [1], some of the metals found originated from the
crude itself, while others were added during production and transportation and
migration of metals into the crude oil due to corrosion of pipelines, and tasks
could also explain the existence of heavy metal in heavy oil. According to the API
gravity (degree API = 141.5/specific gravity = 131.5), crude oil can be classified as
follows:
197
Light crude oil: API gravity higher than 31.1.

Medium crude oil: API gravity from 31.1 to 22.3.
Heavy crude oil: API gravity from 22.3 to 10.
Extra-heavy crude oil: API gravity below 10.
Heavy oil is a crude oil having a viscosity generally greater than 10 cP and grav-
ity below 22.3° API [2]. It contains high-molecular-weight hydrocarbons having
more than 15 carbon atoms in its chain [3] and hence has low hydrogen-to-carbon
ratios. In addition, it has elevated levels of heteroatom-containing compounds such
as sulfur, nitrogen, oxygen, and metals. Moreover, it is highly acidic. The presence
of heavy metal in heavy oil has been identified throughout the years, and although
it only accounts for 1% of the total composition, accumulation of these metals over
a long period of time could hinder the upgrading and the refinery process.
1.2 Heavy metal removal processes
Heavy oil generally needs to undergo several processes before it can be sold to
the consumers to meet their specification. Metal removal process is one of the pro-
cesses involved in the refinery stage where the hydrocarbons are treated to remove
heavy metal before delivering into the downstream process to increase its market
value. The presence of heavy metals, such as nickel and vanadium in the heavy oil,
could lead to serious problems during any of the heavy oil refinement and upgrada-
tion processes. Hence, oil and gas companies of the world are interested in finding
ways to remove the heavy metals from the heavy oil. Some of the problems caused
by these metallic compounds are discussed below:
a. Environmental effects: Vanadium is the most common metal found in heavy oil.
It produces vanadium pentoxide when it burns during the combustion process
[4, 5]. Vanadium pentoxide is a toxic material and is harmful to the environ-
ment. In addition, less volatile metals and metal compounds can be found in
great amount in the ashes of heating oil, which also disperse into the environ-
ment which could lead to a serious environmental problem [1]. Due to the
hazardous and carcinogenic nature of heavy metal, it could have caused serious
health issues, such as nervous system damage, cancer, and, in extreme cases,
death.
b. Industrial damages: When heavy metal-containing heavy oil is burned dur-

ing combustion process, the existing heavy metals would be stored in ashes
which will result in the corrosion of the container. If heavy oil is used in power
generation, it can lead to the corrosion of the turbine which will eventually
lead to operational failure. Apart from this, once crude oil is produced, it will
then be transported to a place where it will be processed. However, corrosion
in pipelines could occur if there is a presence of heavy metal. In addition, the
effective diameter of the pipeline could also be reduced due to the deposition of
metal-containing compounds in the pipeline. In the oil industry, removal of the
heavy metal is necessary to prolong the lives of catalysts in the fluid catalytic
cracking [1].
c. Cost: As a result of decreasing amount of light hydrocarbon worldwide, oil and

gas companies have taken interest in developing heavy oil into useful products.
Generally, oil and gas companies invest a huge amount of money especially in
terms of CAPEX (capital expenditure) and OPEX (operating expenditure).
The presence of heavy metals in the heavy oil however causes spoilage to the
198
Nickel Tetraphenylporphine Extraction from Model Heavy Oil Using Ionic Liquids
equipment, hence resulting in further increment of the operating and main-

tenance costs. Thus, removal of heavy metal is a vital stage in upgrading the
heavy oil.
Nowadays, there are various methods available in removing heavy metals from
the heavy oils and its fractions which can be divided into several categories: physi-
cal, chemical, electrochemical, and catalytic hydro-treatment. Some of the methods
in the category are chemical precipitation, adsorption process, membrane filtration,
electrodialysis, and photocatalysis. These heavy metal removal processes come
with its pros and cons with some of it being high in terms of operational costs, and
other methods such as photocatalysis have a long processing time with very limited
applications to the industry. The advantages and disadvantages of conventional
heavy metal removal processes are summarized in Table 1.
Removal of heavy metals especially nickel (Ni) and vanadium (V) has been
investigated in the recent years as more and more companies have taken the inter-
est in upgrading heavy crude oil. Researchers all over the world have developed
many metal removal methods and have published their findings in open literature.
Although some of the methods have been proved to be efficient, unfortunately oth-
ers have not shown a significant result within a specified amount of time. Therefore,
further studies are essential to investigate the best way on removing heavy metal
present in heavy oil. Table 2 shows the experiments that have been done in remov-
ing heavy metal present in heavy oil under different sets of operating conditions.
Limited research works on the removal of heavy metal in heavy oil using
ionic liquid (IL) are available in open literature. Most of the written papers are
focusing on the removal of metal in wastewater or industrial effluent rather
than in heavy oil.
1.3 History of IL
Ionic liquids (ILs) are chemical compounds of ion structure which have the melt-
ing point below 100°C or even at room temperature [16]. An IL contains positively
Treatment method Advantages Disadvantages References
Photocatalysis Less harmful and toxic Limited applications [6, 7]

by-products Long removal time
Simultaneous removal of
both metals and organic
pollutants
Chemical Low initial cost Sludge generation requires [8]

precipitation Simple operation additional operational cost for its
disposal
Adsorption Low cost Production of waste products [9, 10]

Wide pH range requires additional operation cost
Simple operating conditions Low selectivity
Membrane filtration High separation selectivity Requires frequent membrane [8]

Small space requirement replacement due to membrane
fouling
Electrodialysis High separation selectivity Increased operational cost due [11]

to membrane fouling and high
energy consumption
Table 1.
Advantages and disadvantages of conventional heavy metal removal processes.
199
Experiment Operating conditions Removal References
Microwave-assisted nickel and Microwave Ni = 76.8% [12]

vanadium removal from crude oil power = 600–800 W V = 83.2%
Irradiation time = 3 min
Dosage methane sulfonic
acid = 2 wt%
Using supercritical water (SCW) to T = 450–490°C Ni = 90.64% [13]

remove nickel from Ni-EP P = 25–45 MPa
Time = 180 min
Mixed solvent (SCW) and toluene T = 410–490°C V = 80.26% [4]

without the addition of any catalyst to P = 25MPa
remove vanadium Time = 180 min
Removing nickel from NiTPP using T = 450–490°C Ni = 65.65% [14]

SCW in the presence of toluene P = 25–35 MPa
Time = 90 min
Effect of cationic starch on removal Microwave power = 300 W Iran crude oil [15]
of Ni and V from crude oils under Irradiation time = 5 min Ni = 50%,
microwave irradiation T = 60°C V = 76%
Shengli crude oil
Ni = 60%,
V = 79%
Table 2.
Methods in removing heavy metal from heavy oil.
charged cation and negatively charged anion. The commonly used cations are based
on ammonium, sulfonium, phosphonium, imidazolium, pyridinium, picolinium,
pyrrolidium, etc. with different substitutes. The generally used anions are halogen
(first-generation ILs), organic ([CH3COO]−, [CF3CO2]−, [PhCOO]−, etc.) or
inorganic ([BF4]−, [PF6]−, [AlCl4]−, etc.). Though the properties of ILs depend on
mutual fit of cation and anion, size, geometry, and charge distribution, they well fit
in the assumptions of green chemistry. In 1998, Anastas and Warner have formulated
12 principles of green chemistry [17]. ILs meet three pillars of these principles—
safer solvents (principle no. 5), provision of energy efficiency (principle no. 6), and
usage in catalytic reactions (principle no. 9) [16]. Figure 1 represents a simplified
model of an irregular system of ions present in the IL structure.
IL precursors are quaternary ammonium halide salts that are known from the
1890s. But these salts are widely used and tested in the twentieth century for differ-
ent applications such as synthesis, disinfection, fabric softener, wood preservation,
and so on. These salts are used as IL from 1996.
A low-melting organic salt has been observed as red oil in the mid-nineteenth
century for the first time. This oil was produced as a by-product in the Friedel-
Crafts reaction of benzene alkylation with aluminum chloride as a catalyst. The red
oil known as chloroaluminate, σ-complex, was structured after the popularization
of nuclear magnetic resonance technique as shown in Figure 2.
Gabriel and Weiner produced ethanolammonium nitrate with the melting point
(MP) of 52°C in 1888. Paul Walden [18–20] in 1914 produced ethylammonium
nitrate with the MP of 12°C. This compound is considered as the first IL by many
researchers [20], and Walden is known as the father of ILs. But this compound has
no use due to its high reactivity.
In 1934, US patent no. 1943176 has claimed that the cellulose has dissolved in
1-benzylpyridinium chloride, 1-ethylpyridinium chloride, and so on at the tem-
perature above 100°C. In 1948, just after World War II, 1-ethylpyridinium bromide
has appeared in another US patent [19] for the electrodeposition of aluminum
200
Figure 1.
Structure of historic ILs (ILs developed in the 20th century).
Figure 2.
Chloroaluminate, σ-complex, in the Friedel-Crafts reaction.
from aluminum (III) chloride. At that time, they were unable to investigate the IL
because of the complex mixture of bromide and chloride salts. Later, in 1975, the
physical and chemical properties of this IL were investigated by Osteryoung group
aided by Bernard Gilbert [19]. The IL attracted the international researchers in
the 1970s as aluminum chloride-based molten salts were used in the 1940s for the
formation of nuclear warhead batteries. Wilkes in 1970 has tried to develop better
batteries for nuclear warheads and space probes as they needed molten salts to oper-
ate [18]. Wilkes and Hussey have discovered an IL system which is liquid at room
temperature known as 1-ethyl-3-methylimidazolium chloride-aluminum chloride
([EMIM]Cl-AlCl3). This was the first appropriate example of IL system [19]. ILs
emerged as solvents in the late 1990s.
ILs are interesting compounds due to their variable properties such as they are not
all noncorrosive, but they can be designed to be noncorrosive [21]. Generally, ILs have
negligible vapor pressure, high thermal and chemical stability, nonflammability, and
numerous potential applications, such as microwave-assisted organic synthesis, catal-
ysis, biocatalysis, separation, extraction, electrochemistry, nanomaterial synthesis,
polymerization reactions, and corrosion inhibitors [22]. They have potential efforts to
replace and optimize the existing petroleum-based technologies and processes.
This chapter explores the capability of ILs to extract NiTPP from model heavy
oil that is not disclosed previously in open literatures.
201
2. Materials and methods
2.1 Materials
Based on literature survey, four specific ILs as stated in Table 3 were utilized
to extract nickel tetraphenylporphyrin (NiTPP) from model heavy oil. These ILs
were purchased from Sigma-Aldrich and used without any modification. The heavy
metal-containing compound, NiTPP, and the solvent, toluene, were also purchased
from Sigma-Aldrich and used without further treatment.
2.2 Model heavy oil preparation
Model heavy oil was prepared by dissolving NiTPP in toluene. For producing
250 mL 0.06 M model heavy oil solution, exactly 0.015 g of NiTPP was taken in
a beaker. Then required volume of toluene was added in the beaker at least three
occasions at a volume of 50 mL in each occasion to ensure complete and stable
mixing. The beaker was then placed on a hot plate, and the solution was stirred
using a magnetic stirrer at a temperature of 50°C and a speed of 200 rpm. After
the completion of mixing, the resultant solution was transferred into 250 mL vol-
umetric flask, and toluene was added up to the mark to make a 250 mL solution.
Table 3.
General information of four used ILs.
202
2.3 Experimental method
The ILs and model heavy oil were taken in an autoclave reactor at a ratio of 1:10
(v/v). Then the reactor was loaded into an oven which was preheated to the planned
temperatures of 0–180°C. The reactor was removed from the oven after a specific treat-
ment time of 10–40 min. and kept under a water bath to cool the reactor up to room
temperature. The samples were then collected into the separating funnel by washing the
reactor interior at least three times with toluene. Two layers were formed after allowing
sufficient time—the top is NiTPP solution portion, and the bottom is NiTPP-extracted
IL portion. The top portion was separated and made ready for analysis.
2.4 Analytical method
Out of two layers, the separated top layer was analyzed using UV-visible spec-
trophotometer (UV-VIS), Perkin Elmer Lambda 26 model, to find out the con-
centration of NiTPP. A cuvette, size of 12.5 × 12.5 × 45 mm, was used to place the
samples in the UV-VIS. Toluene is used as the reference solvent.
A calibration curve, a plot of the concentration of NiTPP vs. absorbance, was
plotted using five known samples of NiTPP at the beginning of experiments. The
best-fit curve was a straight line almost passing through the origin. After analyzing
the treated samples, the concentration of NiTPP in the samples was calculated using
the aforesaid calibration curve. The following term is used in this study.
NiTPP extraction was calculated using Eq. (1):
C −C
NiTPP extraction (%) = _____
0 t
× 100 (1)
C0
where C0 is the initial concentration of NiTPP in the toluene solution and Ct is

the concentration of NiTPP in the toluene solution at treatment time, t.
The experiments were carried out three times. The error margin of the achieved
data was less than 5 with 96% confidence level.
3. NiTPP extraction using ILs
3.1 Effect of ILs on NiTPP extraction
Four toluene (boiling point 110.6°C at 0.01 MPa and critical point 318.64°C at
4.109 MPa) insoluble imidazolium-based ILs such as [BMIM]TFSI, [EMIM]OS,
[BMIM]OS, and [OMIM]BF4 were utilized in this study to extract NiTPP from
model heavy oil as they have a capability to extract some metals. Hildebrand’s
solubility parameter (HSP) of different solvents and ILs are displayed in Table 4.
NiTPP is a purple solid crystal. Mandal et al. in 2011 [14] have disclosed that this
compound is soluble in toluene (HSP = 18.3) and xylene (HSP = 18.20) but insoluble
in water (HSP = 48.00) indicating that the HSP of this compound is close to 18.00.
The toluene-soluble NiTPP was purple in color and had intensive absorption peaks
in the visible region.
The IL, [BMIM]TFSI was not dissolved in toluene and water at room tem-
perature. It was not capable of extracting NiTPP at this temperature. Hamidova
et al. in 2015 [25] have disclosed that [BMIM]TFSI IL has a density of 1436.76 and
1385.21 kg/m3 at 25 and 80°C. When NiTPP solution was treated with [BMIM]TFSI
at a temperature of 75°C and a treatment time of 30 min, the color of [BMIM]TFSI
did not change (Figure 3a) at all, indicating that it was not able to extract NiTPP
203
Name of solvent or ILs Hildebrand’s solubility parameter (HSP)

(MPa0.5) [23, 24]
[BMIM]TFSI 26.70 at 25°C
[EMIM]OS 30.20 at 25°C
[BMIM]OS 22.83 at 25°C, 23.25 at 55°C
[OMIM]BF4 22.50 at 25°C
Toluene 18.30 at 25°C
Xylene 18.20 at 25°C
Water 48.00 at 25°C
Table 4.
HSP of different solvents and ILs.
Figure 3.
Effect of ILs on NiTPP extraction at a temperature of 75°C and a treatment time of 30 min: NiTPP extraction
using (a) [BMIM]TFSI, (b) [EMIM]OS, (c) [BMIM]OS and (d) [OMIM]BF4.
though the density of this IL was reduced with the increase of temperature. This
was probably due to the unequal HSP of NiTPP and [BMIM]TFSI.
Similarly, the IL, [EMIM]OS (density = 1095 kg/m3) was not dissolved in toluene at
room temperature. It is lighter than [BMIM]TFSI. When NiTPP solution was treated
with [EMIM]OS at a temperature of 75°C and a treatment time of 30 min., the color
of [EMIM]OS slightly changed (Figure 3b) due to some of the NiTPP being extracted
into this IL. The IL, [BMIM]OS, is insoluble in toluene. When the NiTPP solution was
treated with [BMIM]OS at a temperature of 75°C and a treatment time of 30 min.,
the color of [BMIM]OS was darker than the color of [EMIM]OS (Figure 3c). The
IL, [OMIM]BF4 (density = 1120 kg/m3), is insoluble in toluene at room temperature.
When the NiTPP solution was treated with [OMIM]BF4 at a temperature of 75°C and
a treatment time of 30 min, the color of [OMIM]BF4 was darker than the color of
[EMIM]OS (Figure 3d) but very close to [BMIM]OS. This means that [BMIM]OS and
[OMIM]BF4 are more efficient in order to extract NiTPP from the NiTPP solution. For
the next studies, [BMIM]OS is used due to its availability and cheapness.
3.2 Effect of temperature of [BMIM]OS on NiTPP extraction
Variation of NiTPP extraction in [BMIM]OS as a function of temperature is

shown in Figure 4. It is observed that NiTPP extraction was increasing with tempera-
ture up to 100°C, and after that, NiTPP extraction was decreasing with increasing
204
Figure 4.
Variation of NiTPP extraction in [BMIM]OS at a function of temperature.
Figure 5.
Variation of NiTPP extraction at a function of temperature and treatment time (symbol: ◊, at temperature of
30°C; □, at temperature of 60°C; and ∆, at temperature of 90°C).
temperature. Maximum 63% NiTPP was extracted at a temperature of 100°C and

a reaction time of 40 min. Thus, [BMIM]OS was effective to extract NiTPP at tem-
peratures below 100°C. The reason is that viscosity of IL normally reduces gradually
with the increase of temperature. Hence, NiTPP mixed well with IL by increasing the
collisions between them. Such viscosity-temperature criteria no longer exist after a
temperature exceeding 100°C for the case of IL [BMIM]OS because this IL decom-
posed at a temperature exceeding 100°C. Therefore, low temperature was favorable to
extract NiTPP using this IL.
3.3 NiTPP extraction at temperatures below 100°C
Figure 5 shows that NiTPP extraction increased with increasing reaction

temperature and time. Approximately 61% NiTPP was extracted at a temperature
of 90°C and a treatment time of 40 min. One reason for this is that NiTPP and IL
mix properly with increasing temperature, increasing their respective collisions
events and thus increasing treatment rate. Mandal et al. in 2015 [26] have disclosed
205
that IL molecules themselves could form cage structure through specific chemical
bonds with the increase of treatment time. In this cage, the objective molecules
would be captured through the formation of liquid clathrate due to the π-π interac-
tion between ILs and objective molecules. This was the reason of increasing NiTPP
extraction with the increase of treatment time.
3.4 NiTPP extraction kinetics
Extraction kinetics is important for good extractor design. To determine

the extraction order, a kinetic plot of ln(1-X), where X denotes fraction of NiTPP
extraction, versus reaction time (t, min) is constructed (Figure 6). The
NiTPP extraction was close to zero at zero treatment time. Each set of data gives
a straight line obtained with the least square method that passes almost exactly
through the origin indicating first-order kinetics with respect to NiTPP extraction,
and it follows the kinetics equation [Eq. (2)]:
ln (1 − X) = kt (2)
where k is rate constant in time−1.
Figure 6.
NiTPP extraction kinetics plot (symbol: ◊, at temperature of 30°C; ◊, at temperature of 60°C; and ∆, at
temperature of 90°C).
Figure 7.
Arrhenius plot.
206
Reaction kinetics analyses of this study were tested and evaluated to a maximum
of 61% NiTPP extraction as kinetics data were more compatible with first-order
kinetics at this extent [27]. From the slope of the straight lines of Figure 6, the
respective rate constant was determined, and an Arrhenius-type temperature depen-
dency acidity removal rate constant plot was then plotted (Figure 7). By exploring
this plot, activation energy and pre-exponential factor of the said extraction process
were estimated with respective values of 1.24 kcal per mol and 2.156 × 10−3 s−1. Thus,
the Arrhenius equation for NiTPP extraction can be rewritten as shown in Eq. (3):
−1.24
_____
kNiTPP extraction = 2.156 × 10 −3 e RT , temperature below 100 ° C (3)
4. Conclusions
The IL-based metal extraction from heavy oil process is presented in this study.
The IL, [BMIM]OS, is capable to extract NiTPP from model heavy oil, and approxi-
mately 63% NiTPP was extracted at a temperature of 100°C and a treatment time of
40 min. The extraction is dependent on temperature and treatment time at tem-
peratures below 100°C. The time dependency extraction kinetics follows first-order
kinetics with activation energy of 1.24 kcal per mol and pre-exponential factor
of 2.156 × 10−3 s−1. Therefore, IL-based metal extraction processes can attract the
researcher’s attention due to their greenness and separability tendency after using.
Acknowledgements
This work was supported by the Yayasan Universiti Teknologi Petronas (YUTP),
Universiti Teknologi PETRONAS (UTP), Malaysia.
Author details
Pradip Chandra Mandal
Department of Pipeline Construction, Titas Gas T and D Co. Ltd, Dhaka,
Bangladesh
207
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209
Chapter 13
Catalysts for Hydroprocessing of

Heavy Oils and Petroleum
Residues
Ching Thian Tye
Abstract
With the increasing demand of petroleum-derived products due to the world

population and development, upgrading of crude oil with heavier quality and
petroleum residues is unavoidable. Hydroprocessing is a preferable process for
heavy oil upgrading. The process is operated with the presence of a catalyst, and
catalysis plays an important role in the process. An overview regarding the catalyst
design such as the catalyst active metal, active phase, support properties, and
catalyst structure for heavy oil hydroprocessing is provided. There also include
some recent advancements related to catalytic hydroprocessing of heavy oils and
residue processes. Further catalyst performance improvement will likely come from
catalyst optimization and better catalyst deactivation resistance resulting from
metal poisoning and coke formation.
Keywords: heavy oil, residue, hydrocracking, hydroprocessing, mesoporous,

macroporous
1. Introduction
The increasing world population and economic growths cause significant

increases in oil demand. With the finite conventional fossil fuel reserves, the pro-
duction based on alternative renewable sources and nonconventional oils such as
heavy crude oils and tar sand bitumen is expected to increase. Heavy oil, as the
general term for nonconventional heavy feedstock, is considered as an alternate
suitable source for transportation fuels, energy, and petrochemicals to fulfill the
requirements of modern civilization [1]. This indicates that processing of heavy oils
in the petroleum refining industries is growing.
In general, heavy oil is defined as any liquid petroleum with an API gravity less
than 20°. API gravity is an expanded density scale used widely in petroleum indus-
try. Heavy oil with API gravity below 10.0°API sinks under the water as it is heavier
compared with water (10.0°API), and it is termed extra-heavy oil [2]. Compared
with conventional light oil, heavy oils have higher viscosity, higher density, and
lower API gravity. The properties of heavy oils vary according to its origin and
synthetic route.
The main issue with heavy crude oil is that it produces a lower percentage of
gasoline and diesel fuels and a higher percentage of residue fraction when distilled
by an oil refinery. In addition, heavy crude oil has more negative impacts to the
211
environment than its light counterpart, and its refining requires the use of more
advanced techniques. Petroleum residues are the heavy fraction remaining after
distilling petroleum crudes at atmospheric pressure (atmospheric residue) or at
reduced pressure of 25–100 mmHg (vacuum residue; boiling point >525°C). Petro-
leum residue has high average molecular weight (> 1000 Da number average for
vacuum residue) and higher asphaltene content [3]. Asphaltenes are insoluble in n-
alkanes such as n-pentane and n-heptane but soluble in benzene or toluene [4]. In
addition, residues have high heteroatom content such as sulfur ( 5 wt%), nitrogen,
and heavy metal (i.e., vanadium and nickel > 100 ppm). These heteroatoms tend to
poison catalysts and cause problems during processing and, therefore, need special
processing in the refinery to remove them.
Petroleum residues can be converted into lighter oil or more value-added prod-
ucts using bottom-of-the-barrel conversion processes or residue upgrading pro-
cesses [1]. No matter which type of process is used, a substantial fraction of residue
molecules can be cracked off as fragments to become liquids in the transportation
fuel and vacuum gas oil boiling ranges. However, due to the high asphaltene con-
tent, overly converted residues can push the selectivity toward the thermodynami-
cally favored but lower valued products, namely, coke and hydrocarbon gases.
Hydrogen addition and carbon rejection are the two major approaches to
upgrade petroleum residues into lighter oils in petroleum industry. Carbon rejec-
tion, such as coking process, produces a lot of cokes during the heavy oil upgrading
processes which have low or no market value. In the past few decades, hydrogen
addition approach especially hydroprocessing has gained prominence in heavy oil or
vacuum residue upgrading processes [1]. This approach upgrades heavy feeds to
distillate fractions and generates less coke.
Various hydroprocessing reactor technologies such as fixed-bed, ebullated-bed,
or slurry-phase reactors are used to upgrade heavy residues [5]. The principles of
these reactor operations are almost the same but differing with respect to some
technical minutiae and tolerance of impurities [1, 6]. Typically, hydroprocessing of
heavy oils is an upgrading process carried out at temperature around 380–480°C
and hydrogen pressure at 80–270 bar with the presence of a catalyst [7]. H-Oil™
and LC-Fining are the processes designed to convert heavy residue to lighter frac-
tions by hydroprocessing using an ebullated-bed reactor. Eni slurry technology
(EST) and CanMet by Energy Research Laboratories, Canada, are examples that are
using slurry-phase reactors.
In general, hydroprocessing involves hydrocracking and hydrotreating. The
main objective in heavy feedstock upgrading is to convert heavier residue into
lighter distillates in such a way to increase hydrogen-to-carbon (H/C) ratio of the
product. Thus, hydrocracking reaction is the main concern. Hence, sometimes
hydroprocessing of heavy oils is also called hydrocracking of heavy oils. During the
process, larger molecules such as asphaltenes and resins are cracked and being
converted to lighter liquid hydrocarbons such as gasoline, diesel, and gas oil. Mean-
time, various hydrotreating reactions such as hydrodesulfurization (HDS),
hydrodenitrogenation (HDN), and hydrodemetalation (HDM) are also occurring
during the process under the operating conditions. This leads to better product oil
quality and contributes toward hydrotreating process in the later stage.
Hydroprocessing is the most versatile of the modern heavy feed conversion
processes. The flexibility of the operating conditions with respect to both the feed-
stock and product separation has provided the most economical refinery balance
relative to supply and demand [1]. Catalyst plays an important role attributed to
this flexibility in hydroprocessing, in which upgrading the most problematic feeds
such as vacuum residue is derived from heavy crudes, as well as the direct
upgrading of the latter. During reactions, catalyst helps to reduce the activation
212
Reactor type Catalyst size, mm [8, 9] Catalyst in reactor, particle/cm3 [9]
Fixed bed 1.2–3.0 120
Ebullated bed 0.8 250
Slurry system 0.002 2.4 109
Table 1.
Typical catalyst properties for residue hydrocracking.
energies leading to higher yield and selectivity for the products in favor. Various
factors influence the product selectivity; these include reaction operating conditions
and catalyst properties such as active sites, shape, size, chemical compositions, etc.
Reaction operating conditions associate directly with the productivity. Heavy oil
hydrocracking is typically carried out at a relatively higher temperature. Since the
reaction operating conditions for different technologies are different, to ensure the
desirable yield and selectivity, it is important to consider the characteristics of the
feed, appropriate reactor system, and catalysts for the hydrocracking of vacuum
residue [1].
For different types of reactor operation, the catalyst properties especially the
catalyst particle sizes deployed also vary. The typical catalyst properties used in
different types of reactors are given in Table 1.
Generally, supported sulfide catalysts containing group VIB and VIII metals
especially cobalt, molybdenum, tungsten, or nickel are used in heavy oil upgrading
processes. However, impurities present such as heavy metals in the residues
decrease the catalytic activities [1, 10].
Establishing an understanding of the key catalyst properties that influence cata-
lyst performance in hydrocracking of heavy residue is important. This provides a
basis to develop a better-performance catalyst for heavy oil hydrocracking.
2. Catalyst design for hydroprocessing of residues
Hydrocracking reactions require a bifunction catalyst with high cracking and

hydrogenation activities. The high cracking activity is provided by an acidic sup-
port, whereas the hydrogenation activity is provided by metals on the support. The
acidic catalyst support, such as acid-treated clay, alumina, or silica-alumina, is used
to promote cracking and support the metals such as nickel, tungsten, platinum, and
palladium that supply the hydrogenation function. These highly acidic catalysts are
sensitive to the feed with high-nitrogen compound, which easily neutralizes the
acid sites. Therefore, catalyst used for heavy oil hydrocracking process is different
from the normal distillate hydrocracking process. Further, heavy oil that is derived
from different geographical areas possess different properties. Therefore, it is
important to have a specific designed catalyst that is suitable to the targeted heavy
oil hydrocracking. Here, a key challenge is to design and synthesize catalysts that
have high activity for hydroprocessing. Main components in catalyst design for
hydroprocessing of heavy oils are discussed in the following sections.
2.1 Transition metals for hydrocracking catalyst
Cracking of C▬C bonds require a high amount of energy; therefore, hydro-

cracking reactions occur significantly only at high temperature (400°C and
above). The main function of catalysts is to provide hydrogenation-
dehydrogenation reactions that lead to higher liquid hydrocarbon yield and
213
suppress coke formation. Platinum-group precious metals such as platinum and

palladium are the representative catalysts with excellent hydrogenation capacity,
and they are also commonly used in many other reactions. However, these
platinum-group precious metals showed weak resistance especially to sulfur [11].
Sulfur escapes and reacts with the catalyst during upgrading process as extra-heavy
oil containing high concentration of sulfur [12]. Therefore, in order to cope with
heavy residue, which is high in sulfur content and other impurities such as nitrogen,
and heavy metals that can easily deactivate or poison the catalyst, platinum-group
precious metals have not been used as catalysts for the upgrading of extra-heavy oil.
Mo, Ni, Co, and W are the common established transition metals used as the
active ingredient in catalyst for hydrocracking of heavy residue. Sulfides of Mo and
W are usually used, and Ni and Co are used in promoting species components in the
petroleum industry. These metal sulfides not only promote relatively high hydro-
genation but are also good in hydrotreating activities such as HDN, HDS, and HDM
during heavy residue upgrading process. The abovementioned metal sulfides are
favored as well in terms of their availability and the cost comparing to the noble
metals such as platinum and palladium. There are also studies on using other pro-
moters such as phosphorus (P), fluorine (F), and boron (B) on the catalysts [1].
The reactive metals are usually deposited on catalyst support by wet or incipient
wetness impregnation methods. The impregnated catalysts are then calcined,
reduced, and used for the hydrocracking reactions.
2.2 State of active phase
Sulfides of metals, e.g., MoS2 and WS2, have been used as the active phase in
hydrocracking catalyst. NiMo and CoMo sulfides were identified to exhibit superior
HDS activity [13, 14].
Sulfidation of supported oxidative metal catalysts is normally carried out by
thermally reacting with sulfur compound prior to hydroprocessing in order to have
the best catalyst performance. For dispersed catalyst, sulfidation of the catalyst can
be done either ex situ or in situ. Most oil-soluble catalyst metal precursors, which
are available in the oxide, can be sulfided in situ by thermally decomposing sulfur
compound in the heavy residue upon the reaction severity and transformed from
inactive oxides to sulfides during the upgrading process [15]. However, the com-
plete sulfidation of active components can be challenging [16], and incomplete
sulfidation reduces the catalyst performance to a certain degree. Dispersed metal
oxide catalyst can also be presulfided ex situ by using H2S as the sulfiding agent
followed by dispersion in oils [14].
Sulfidation is a complex reaction. Strong interaction between metal and support
can cause poor reducibility of the metal species, which eventually makes the
sulfidation of the catalyst difficult and leads to poor activity [17]. In spite of similar
activities for the hydrocracking reaction, W-based catalysts have received less
attention than Mo catalysts. This is due to their lower sulfidation ability, on which
the catalytic activation is strongly dependent [18].
Carbide catalysts are also being tested in heavy residue upgrading [19, 20].
Studies have shown that the electron distribution of the d orbitals and consequent
catalytic activity of WC are similar to those of platinum, while the resistance to
sulfur is higher than platinum [21]. Density functional theory (DFT) studies have
shown that WC can act as a catalyst with a strong hydrogenation capability without
being poisoned by sulfur [22]. However, there are problems with carbide catalysts
such as nano-sized particles of WC are difficult to obtain because of the high
temperature in the carburization process, and metal contamination occurs when
WC in bulk is obtained through a ball milling process [20, 23].
214
2.3 Properties of support material—acidity and porous structure
Catalyst support plays an important role in a catalyst. Support provides space for
the active metal to stay upon as well as acid sites for cracking activity. Large surface
area of support is generally favorable for catalyst as it can be interpreted directly
into more active sites available on the catalyst surface which normally lead to better
catalyst performance. Porous structure support exhibits large surface area. Hence,
other than the chemical composition of catalyst, textural properties of support such
as size, shape, surface area, and porosity have a great influence especially for
heterogeneous catalyst system.
2.3.1 Acidic properties of the support
Acid sites of the catalyst promote cracking activity. Materials such as alumina,
crystalline zeolite, amorphous silica-alumina, and mixture of crystalline zeolite and
amorphous oxides with high acidity (Lewis and Brønsted acid sites) are used as
catalyst base or support in order to promote more cracking activity during reac-
tions. These supports usually have a structure with numerous micropores (pore
diameter < 2 nm), which provide high surface area and acidic properties [24].
In terms of chemistry at the molecular level, zeolites and amorphous silica-
alumina share some similarities. However, zeolites, which have the crystalline
structure, offer higher activities and better controlled selectivity than the amor-
phous materials. Typically, using zeolite-based catalysts in hydrocracking results
in greater cracking activity owing to its greater acidity. In addition, the use of
zeolite-based catalyst improves thermal or hydrothermal stability and resistance to
nitrogen/sulfur compounds.
However, catalyst deactivation occurs quickly when these conventional
supported catalysts are used in heavy residue hydroprocessing. This is due to pore
blocking caused by relatively high concentrations of heteroatoms, metal poisoners,
and asphaltenes commonly found in heavy fractions. This significantly reduces the
availability and accessibility of the active sites at the catalyst surface in the pores by
the reactant molecules. Hence, conventional supports are not suitable for upgrading
of extra-heavy oils and vacuum residues. It is also believed that the catalyst sup-
port’s intrinsic acid sites (e.g., γ-Al2O3) participate in sediment or coke formation
during hydrocracking reaction [25]. To avoid pore blocking problem, this leads to
the introduction of meso (2–50 nm)/macropores and high pore volume into the
catalyst support for hydrocracking catalyst.
Therefore, greater attentions are paid to the properties of catalyst especially
support materials such as the size of the particles, pore volume and pore size
distribution, and the shape of the particles to maximize utilization of the catalyst.
2.3.2 Support material porosity and pore size distribution
High asphaltene content in heavy oils leads to a higher tendency to form coke
during processing compared to conventional light crude oils. This is due to the
accumulation of the coke precursors on both external and internal configurations of
the catalyst. In addition, rapid deposition of metallic poisons narrows down the
catalyst pore size, restricting the accessibility by reactant species and products.
These may cause complete pore blockage. As a result, the catalyst activities and
performance reduce markedly. Hence, typical good catalyst design for heavy oils
upgrading processing must offer (1) accessibility to large asphaltene agglomerates
in order to increase their diffusion and transformation and (2) catalytic active sites
or support adsorption sites that are less favorable to sediment or coke formation [3].
215
Also, it is clear that the pore structure of the catalyst has a close relationship with
the conversion, selectivity, and stability properties of the catalysts during hydro-
cracking reaction [26].
In order to overcome the difficulty of asphaltene diffusion through small pores,
the development of the porous shaped support or catalyst structure with
macropores (>100 nm) is rationalized. However, too many macropores (ca. above
30% of total pore volume) should not be created, since shaped particles could turn
fragile [3]. Mesoporous alumina is a rigid porous material with a mutually
interconnected or isolated network structure which has not only the characteristics
of a crystalline phase of alumina but also the characteristics of a porous material
[27]. Catalysts having pores between 7 and 20 nm diameter showed higher activities
than those catalysts having pores between 3 and 7 nm which was reported for
hydrocracking of Athabasca oil sand bitumen [28]. In order to retain the mechanical
strength, stability, and accessibility to large asphaltene agglomerates of the catalyst
during heavy residue hydrocracking reaction, the multimodal porous structures or
hierarchical pore system is developed in hydrocracking catalyst. Hierarchical pore
system in catalyst not only integrates different functionalities in the catalyst but also
allows the realization of a multiple step reaction in one single catalyst in a cascade
way without any separation processes.
Hydrotreating effect especially HDS of atmospheric residue is a well-established
residuum upgrading process which requires catalysts designed to remove and accu-
mulate metals and to desulfurize the feed [8]. A wide-pore NiMo/γ-alumina was
tested for its performance in a vacuum residue hydroprocessing. The catalyst
showed a remarkably high activity for HDM and asphaltene conversion reactions in
the vacuum residue hydroprocessing [29].
Other than active metal and phase, pore size distribution has been found to
affect the catalyst activity in hydroprocessing of vacuum residue. A
hydroprocessing study using Kuwait vacuum residue as feedstock has shown that
the effect of catalyst pore size was significantly different for different hydrotreating
reactions [30]. Sulfided NiMo catalysts with unimodal and bimodal distributions
with different proportions of meso- and macropores were prepared. For sulfur
removal (HDS), a unimodal pore catalyst with maximum pore volume in the
medium mesopore range (10–25 nm diameter) showed the highest activity. For
HDM and HDN reactions, large-pore catalysts, having a major proportion of pore
volume in 100–300 nm diameter pores, were found to be more effective.
2.4 Methods to create meso-/macro- and hierarchical pore system
γ-Al2O3 is the most commonly used support in catalysis for hydroprocessing.

There are methods developed to prepare mesoporous and hierarchical texture sup-
port for hydrocracking catalyst. Two most important techniques for preparation of
the material with the desired hierarchical texture are by hydrothermal and template
methods.
2.4.1 Hydrothermal method
Hydrothermal method is an approach where the mixed solution (aluminum

precursor, solvent, etc.) is poured into a sealed reactor. In the reactor, relatively high-
temperature and high-pressure conditions promote the dissolution and recrystalliza-
tion of poorly soluble or insoluble material. γ-Al2O3 is then produced by calcination of
precipitated hydroxides [27, 31]. During the hydrothermal process, under the
nonrestricted conditions, the crystal grows to its largest possible size, and its various
characteristics such as shapes, high degree of crystallinity, uniform distribution, and
216
lighter particle agglomeration are developed [32]. The hydrothermal conditions such
as water temperature, pressure, and viscosity of the solution are closely related to the
development of the crystal morphology. The same type of crystal can be produced
with different morphologies under different hydrothermal conditions [27, 33].
Stanislaus et al. [29] studied the mechanism of pore widening in γ-alumina under
hydrothermal conditions in the presence and absence of additives such as P, F,
phenol, and acetic acid. The formation and growth of boehmite into large crystallites
by rehydration of γ-alumina were found responsible for pore enlargement. Li et al.
[34] synthesized alumina from aluminum ammonium sulfate, urea, and polyglycol
2000 by hydrothermal method. It was reported that mesopore alumina of different
morphologies can be fabricated merely by adjusting hydrothermal temperature.
2.4.2 Template method
Template method is a technology which is widely applied in recent years. It is a

synthetic method for controlling the structure, particle size, and morphology of
materials through utilization of a template [27].
Mesoporous alumina is normally prepared via surfactant templates. Su et al. [35]
used Al2(SO4)3 and NaAlO2 as aluminum precursors for preparing lamellate struc-
ture mesoporous alumina with crystalline framework walls in the presence of non-
ionic surfactant PEG6000. Well-crystallized mesoporous γ-alumina was formed
after the samples were calcined at 600°C for 3 h. Mesoporous alumina prepared in
this way exhibited a large surface area (279 m2/g) and a very rich porosity with large
mesopores, and both the pore volumes and the pore sizes increased with the addi-
tion of the surfactant in the precipitation process [35].
Zhou et al. [36] used a promising strategy to prepare well-defined and uniform
pore structure (WDUPS) Al2O3 by coating specially treated SiO2 opals with Al2O3.
The pore size of the WDUPS Al2O3 was tailored in the range of meso- to macro-size
by using microspheres of different sizes to fabricate the SiO2 opal. When the SiO2
opals were coated with optimal amount of Al2O3, the obtained WDUPS Al2O3
showed a uniform acid density.
Recently, another hard template method, which uses polystyrene (PS) micro-
spheres, was used to prepare a range of hierarchically porous alumina samples. The
alumina precursor was mixed either with dry powder of PS microspheres (dry) or
PS water suspension (wet) during preparation before pelletizing and calcination.
The “wet” method gives pellets with a narrower distribution of macropores in size
and the greater material mechanical strength. The approach allows tuning textural
parameters of hierarchically porous alumina samples in different ranges of specific
surface, mesopore volume, and total pore volume [37].
In a recent review by Galadima and Muraza [38] on hierarchical zeolites in
hydrocracking catalysts, in general, the generation of the mesoporous zeolite systems
could be achieved either during the initial crystallization process or through post-
synthesis treatment processes. In either case, the resulting materials could have
hierarchical arrangement of pore system or unimodal system. Another strategy
adopted is the application of hard templates for synthesizing hierarchical zeolite. For
achieving an efficient mass transport and high catalytic performance, the design of
hierarchically porous catalytic supports is an interesting and most effective strategy.
3. Catalyst structure—activity relations
The catalytic activity is related to the structure of the catalyst. Daage and
Chianelli [39] proposed the “rim-edge” model of MoS2 for hydrotreating, in which
217
Figure 1.
Rim-edge model [39].
two kinds of exterior sites are responsible for hydrogenation (HYD) and
hydrodesulfurization (HDS) (Figure 1). MoS2 forms hexagonal or triangular slabs,
and the rim sites around the exposed basal planes contribute to both HYD and HDS,
and the exposed edge sites around the interior layers of MoS2 stacks are accepted as
active sites only in HDS.
The number of stacking layers of MoS2 was then reported to increase the hydro-
genation activity by promoting planar adsorption of aromatic rings on the edge sites
[40]. Later, Lauritsen et al. [41] proposed the “brim site” model as the active site of
HDS, based on observations of MoS2 nanoparticles using scanning tunneling
microscopy. The brim sites associated to Mo edges that are fully sulfided exhibit
electron exchange capability as in typical metal catalysts.
In 2014, Chen et al. [42] compared the structure of hexagonal and triangular
MoS2 catalysts with their activities in hydrotreating. The hexagonal MoS2 with more
Mo edge sites was reported to have higher activity in HYD, but the triangular MoS2
with more S-edge sites exhibited higher activity in HDS.
Similar catalyst structure-activity relations have also been found for W-based
catalyst. In 2016, a DFT study that seeks to understand the active sites of “W-edge”
or “S-edge” of NiWS phases showed that the surface concentration of “W-edge”
and “S-edge” sites is closely related to the intrinsic hydrogenation activity of NiWS
catalyst [43].
4. Recent advancement for heavy residue hydroprocessing
Low-quality heavy feedstock leads to quick catalyst deactivation, high coke

formation, and large pressure drop in the operation of a fixed-bed reactor. In such a
case, ebullated-bed or slurry-phase reactors can be an effective choice. These are
systems designed with continuous addition and withdrawal of catalyst which allow
one to control the catalyst deactivation due to coke formation as well as thermal
exchanges in the reactor.
Supported catalysts are usually used in a fixed-bed or ebullated-bed reactor
system for heavy oil hydroprocessing. On the other hand, nano-size unsupported
dispersed catalysts are used in a slurry-phase reactor. In this case, the catalyst is in
dispersed form such as unsupported metal particles, oil-soluble metals, or metal
precursors that form in situ active phase during the process. Slurry-phase hydro-
cracking processes exhibit high selectivity and yield toward the product. For
slurry-phase hydrocracking process of vacuum residue, both heterogeneous and
homogeneous catalysts, depending upon the physical properties of the catalyst, are
used. Catalyst development for heavy residue hydroprocessing is always ongoing
for a better-performance catalyst and a longer catalyst run-length.
218
4.1 Supported solid catalyst
Carbon or carbon black has been tested as catalyst support for hydroprocessing.
It is cheap and has a low tendency to form coke-related compounds (due to very
weak acid sites). It has an affinity for V and Ni porphyrine-like compounds, which
could be refrained from poisoning the catalyst by attacking the catalyst active sites.
Meantime, it also has high HDS and HDN activities [44] and has no micropores
below 3 nm which could be easily occluded, therefore turning active Ni and Mo
metals into inactive ones [3]. However, carbon or carbon black supports are known
for their low mechanical resistance since the structure of shaped catalyst particles
easily collapses especially when used as catalyst in the ebullated-bed reactor [3]. To
overcome the aforementioned mechanical resistance issue, a bimodal alumina
modified with (8–18 wt%) carbon black composite support, containing 11–20% of
total pore volume as macropores (>100 nm), was developed, and these prospective
supports were impregnated with Ni and Mo. The addition of carbon black to
alumina, after inert atmosphere pyrolysis, has produced strong shaped particles,
suitable for high-colliding attrition applications, as commonly found in the
ebullated-bed reactors. HDS and HDN can be enhanced when combining carbon
black and macropores. It is also noted that catalysts containing macropores were
reported more efficient in HDM than catalysts containing no macropores [3].
A series of mesoporous alumina catalysts with different textural properties were
prepared by using the sol-gel method with the varied aluminum precursor, chain
length of the surfactant, and calcination temperature. Mesoporous alumina with
large surface area (270–380 m2/g) and pore size (3–19 nm) was successfully syn-
thesized. The activity of mesoporous alumina-supported molybdenum catalysts
with different properties in hydrocracking of residual oil was determined at 400°C.
Higher conversion and higher liquid yield were achieved by using catalysts with
larger mesopore size than catalysts with smaller pore size and similar acidity [45].
Dong et al. [46] synthesized a nest-like hollow γ-AlOOH microspheres
constructed from numerous hierarchically organized nanowires via a template-free
simple hydrothermal approach, from which hierarchically porous γ-Al2O3 micro-
spheres with average macropores of 900 nm, mesopores of 20 nm, and a pore
volume of 0.93 cm3/g were obtained readily. The nest-like γ-Al2O3 microspheres
were tested as catalyst supports. The prepared MoNi/γ-Al2O3 (hierarchically pore
texture)-supported catalyst was applied for HDM catalysis. The catalysts exhibited
superior catalytic performance and longer life due to enhanced diffusion of the
reactants, compared to the catalysts prepared with the commercial γ-Al2O3.
A theoretical estimation of catalyst performance using geometrical characteris-
tics of the porous media based on Monte Carlo methods and the graph theory was
done on evolution of alumina catalyst texture during macromolecule conversion in
heavy oil hydroprocessing [47]. In this study, a unimodal mesoporous structure of
conventional catalyst and bimodal meso-/macroporous structure of the catalyst
were modeled. Deactivation was modeled by the monotonic increase of alumina
grain radius, which represented deposition of coke and metal species onto the
surface of grains. There was a correlation observed for the hierarchical texture
model and the experiment. Both the hierarchical texture in model and experiment
were with prolonged catalyst lifetime.
A series of NiMoS/γ-Al2O3 catalysts were prepared with varying Mo loading
amounts, Ni addition, P addition, and porosity of γ-Al2O3 support, in order to
design a suitable catalyst for hydrocracking of vacuum residue. Activity tests were
conducted in an autoclave batch reactor at 420°C and 10 MPa H2 in the presence of
0.26 wt% catalyst and 33.0 wt% tetralin. The amount of Mo loadings on γ-Al2O3 was
observed most favorable at 8.0 wt% with the asphaltene conversion of 62.9%. The
219
addition of Ni had minimal effect on the vacuum residue hydrocracking but

significant effect on the HDS activity. The increase in porosity of the γ-Al2O3
support reported to play an important role in enhancing the asphaltene conversion
to 68.5% [48].
These metal-supported catalysts exhibit good performance in HDM, HDS, and
hydrocracking reactions. However, when upgrading extra-heavy oil using these
metal-supported catalysts, a critical problem of a short lifetime can result from
deactivation of the active sites due to coke or sulfur deposition [14]. Hydrocracking
processes that use heterogeneous catalyst of fixed-bed, ebullated-bed, or slurry
reactors are always with the problems of feed diffusion, pressure drop, and mass
transfer. The intraparticle mass transfer between liquid and solid phases, particle
size, and mixing matter which must be taken into consideration [49]. All these
concerns make limitations to feedstock used for the commercial application. Appli-
cation of dispersed catalyst in slurry-phase hydrocracking is an alternate option to
resolve these issues.
4.2 Unsupported dispersed catalyst
Coke formation resistance is vital to a hydrocracking catalyst since it determines

the durability and lifetime of the catalyst. It is known that coke formation is
markedly inhibited when the active species are applied as dispersed nanoparticle
catalysts [14]. The application of the highly dispersed catalysts in the slurry-phase
hydroprocessing of heavy residues favors the rapid uptake of hydrogen and deacti-
vates the intermediate free radical moieties in the liquid phase, thereby suppressing
coke formation, increasing total conversion, and enhancing quality of liquid
product [50].
Dispersed catalyst can be classified into either water-soluble or oil-soluble [50].
Oil-soluble dispersed catalyst is generally preferred because it has a better catalyst
activity as it can disperse uniformly in oil. To prepare oil-soluble dispersed catalysts,
metals are usually introduced into the oil-soluble precursors to form an organome-
tallic compound [1]. The metal precursors are then homogeneously dispersed in the
reactor containing heavy oil or residue. The catalyst precursor will be activated
(sulfided) in situ by reacting with the sulfur compound in the oil. Typical oil-
soluble dispersed catalysts are such as molybdenum naphthenate and ammonium
heptamolybdate [51]. For a water-soluble catalyst, pretreatments such as disper-
sion, emulsion, and dehydration are needed [1].
Catalyst or catalyst precursor and its dispersibility in the oil during the
hydroprocessing of vacuum residue have direct correlation to the system perfor-
mance. Among the transition metals, Mo- and W-based dispersed catalysts have
been the focus of the study in hydrocracking of extra-heavy oils or vacuum residue.
For instance, exfoliated MoS2 was applied as a dispersed catalyst for Cold Lake
bitumen upgrading [52].
In [52], the exfoliated MoS2, a two-dimensional MoS2 material, was prepared via
chemical exfoliation of MoS2 particles that were dispersed in water. The results
were compared with MoS2 prepared in situ by the decomposition of molybdenum
naphthenate. Although liquid yield and coke suppression were similar among those
mentioned catalysts, a better hydrogenation activity, especially HDN, and
asphaltene and microcarbon residue (MCR) removal were obtained with the exfo-
liated MoS2 [52, 53]. The improved hydrogenation is believed to be a consequence
of increased rim-edge sites [39] associated with the exfoliated MoS2.
In the case of using tungsten, unsupported nickel tungsten sulfide (NiWS(x))
particles, where x is the actual molar ratio of Ni/W (x = 0, 0.005, 0.01, 0.02), were
applied as a dispersed catalyst for hydroprocessing of a vacuum residue (2.3 °API)
220
at 400°C with an initial H2 pressure of 70 bar. Increasing the Ni content was found
to increase the degree of sulfidation of tungsten, which promotes formation of Ni-
W-S phases and enhances the overall catalytic activity. Among the NiWS(x) dis-
persed catalysts, the NiWS(0.02) catalyst showed the highest performance in total
liquid product yield (87.0 wt.%), commercial fuel fraction yield (51.9 wt.%), and
sulfur removal (86.5%) with coke formation (4.0 wt.%) suppressed efficiently [14].
Nano-sized tungsten carbide (2.8 nm) particles were synthesized using remov-
able ceramic coating method and then were applied as dispersed catalysts to hydro-
cracking of vacuum residue, which was carried out at 400°C for 4 h with initial
hydrogen pressure of 70 bar. The temperature programmed desorption analysis
results showed that nano-sized tungsten particles are capable of superior hydrogen
adsorption (compared to bulk tungsten carbide) as well as high catalytic perfor-
mance, not only in commercial liquid yield (naphtha, middle distillate, and gas oil;
46.7 wt.%) but also in coke formation (5.9 wt.%) [20].
The effects of Co, Ni, or Mo precursors that have different oil solubility and
oxidation state on the slurry-phase hydrocracking of vacuum residue at 400°C and
9.5 MPa H2 were reported in [54]. The metal precursors were found to form
nanoscaled dispersed particles of MoS2, Co9S8, and Ni3S2, with the following vac-
uum hydrocracking performances in the order of MoS2 > Co9S8 ≫ Ni3S2, based on
the same metal loading of 0.113 mmol. Among the oil-soluble Mo precursors used,
Mo-hexacarbonyl, Mo-octoate, and Mo-naphthenate, Mo-octoate has an intermedi-
ate oxidation state forms the smallest particles of 5.8 nm in size and exhibits the best
activity in the vacuum hydrocracking.
Shin et al. [55] tested six newly synthesized metal precursors as catalysts for
hydrocracking of vacuum residue. New group VI transition metal complexes, (LM
(CO)3) (M = Mo or W, L1 = 3-phenyl-1-propyne, L2 = 4-phenyl-1-butyne, and
L3 = 5-phenyl-1-pentyne) were prepared by simply stirring M(CO)3(RCN)3
(R = Me, Et) in tetrahydrofuran solution. The catalytic activity was compared to the
commercially available material, Mo-octoate. LMo(CO)3 showed similar activities
to Mo-octoate. Among all, L3Mo(CO)3 which had the longest alkyl chain showed a
comparable result of low yield for coke and gas products [55].
Different morphologies of oil-dispersed MoS2 catalysts were obtained by a ligand
stabilization method using Mo(CO)6 as a Mo precursor and trioctylphosphine oxide
as a coordinating agent to identify the active site of MoS2 in the hydrocracking of
vacuum residue. It was observed that the MoS2 forms a nanoscaled monolayer from 5
to 10 nm in size. The effect of the oil-dispersed MoS2 catalysts with different mor-
phology on the slurry-phase vacuum residue hydrocracking process was investigated
at 400°C and 9.5 MPa H2. The turnover frequency (TOF), activity based upon the H2
consumption rate per lateral metal number, of the dispersed MoS2 catalysts in hydro-
cracking shows a good correlation with the rim-site Mo dispersion of the MoS2 slabs
based on the same metal loading of 0.113 mmol [56].
An oil-soluble W precursor, W(CO)6, was used to prepare WS2 in situ in the
hydrocracking of vacuum residue, and its activity was compared to that of oil-
dispersed MoS2 prepared using the Mo precursor. Vacuum residue was treated in a
batch reactor at 419°C at 9.5 MPa H2 with the metal loading of 0.113 mmol. The
TOF shows a higher value for WS2 (0.709 s1) than MoS2 (0.573 s1) catalyst. A
higher asphaltene conversion for WS2 (39.2%) than MoS2 (35.8%) was obtained.
These results suggest that the WS2 catalyst exhibits a higher intrinsic activity than
the MoS2 catalyst in the residue hydrocracking process. It was noted that the
dispersibility of WS2 (58.0%) was found better than MoS2 (3.3%) [17].
Liu et al. [57] proposed a simple method for the preparation of presulfided oil-
soluble MoS2 catalysts. The catalyst precursor, cetyltrimethylammonium
heptamolybdate (CTATTM), was synthesized by dissolving ammonium
221
tetrathiomolybdate in an aqueous solution containing excess cetyltrimethy-

lammonium bromide, which could be directly dissolved in a vacuum residue. The
obtained catalyst was evaluated in slurry-phase hydrocracking of vacuum residue at
410°C with an initial H2 pressure of 10 MPa for 1 h. Remarkable hydrocracking
activity was observed, with a reduction of the resin content from 25.21 to 3.54 wt%
and of the C7-asphaltene content from 6.82 wt.% to almost zero. With using the
catalyst, the liquid yield increased from 75.03 to 96.43 wt.%, coke yield and gas yield
were 0.19, and 3.38 wt.%, respectively, significantly lower than the values of 14.05
and 10.92 wt.%, respectively, obtained without using the catalyst. Additionally, with
increasing Mo content, HDM conversion increased from 42.5 to 83.4 wt%, while HDS
conversion increased from 21.6 to 59.2 wt%. The CTATTM precursor shows good
solubility and stability in heavy oil, leading to easy formation of small MoS2 particles
with stacking numbers of 1 and 2 and slab lengths of 5–11 nm. This presulfided oil-
soluble MoS2 catalyst shows a great potential for further industrial applications [57].
5. Catalyst deactivation
Hydrocracking of heavy oils differs markedly from that of light feeds owing to the
fact that the catalysts used for this process are deactivated fast due to the presence of
asphaltenes and metal containing molecules [58]. Restraining the deactivation of the
catalysts is one of the main challenges in development of hydrocracking catalysts for
heavy oil upgrading regardless of the reactor system chosen. A better understanding
of the catalyst deactivation is one of the most important aspects to improve the
catalytic performance in heavy oil and petroleum residue refining processes. A good
commercial catalyst is known by its activity, selectivity, and stability.
The main causes of loss of activity in the catalyst are due to the formation of
coke and deposition of undesirable carbonaceous products, metallic compounds,
and asphaltenes on the catalyst surface. In addition, the structural changes includ-
ing thermally or attrition of catalyst are also responsible for the deactivation [1].
In industrial catalytic processes, the loss of catalytic activity and/or selectivity
over time is a major and continuing concern. The degree of catalyst deactivation is
greatly influenced by the feed properties and the associated operating conditions.
Generally, performance of catalysts decreases with time. In order to maintain con-
stant product yields and/or quality, the loss of catalytic activity is compensated by
periodic increases of reaction temperature [7]. Though significant costs, in the
magnitude of billions of dollars annually, to industry are due to catalyst replace-
ment and process shutdown, catalysts activity decay over time is unavoidable [59].
Catalyst deactivation is a complex process. Various model equations are devel-
oped in order to model the deactivation mechanisms such as coke deposition and
metal accumulation. In the model, agents affecting the catalyst activity including
metal content and coke precursors need to be taken into consideration. To achieve
that, detailed characterizations of spent catalysts obtained at different reaction
conditions, time on stream, and reactor position need to be carried out through
various experiments. With the aforementioned information, a better deactivation
model for heavy oil hydrocracking catalyst can be developed and further applied in
reactor design, simulation, and optimization [59].
6. Conclusion
The key developments in better catalyst understanding in association with par-

ticle size, pore size distribution, and activity grading have greatly improved the
222
levels of conversion, increased run-length, and enhanced product qualities while

maintaining residue fuel stability. Further catalyst performance improvement will
likely come from catalyst optimization and better catalyst deactivation resistance
resulting from metal poisoning and coke formation. The future challenge for a
refiner will be to ensure a more efficient conversion of heavier feedstock to warrant
a cleaner transportation fuel and sustainable environment for the generations to
come.
Acknowledgements
Special thanks to Dr. Guan Tien Tan for his helpful comments, suggestions, and
support while preparing the document.
Author details
Ching Thian Tye

School of Chemical Engineering, Universiti Sains Malaysia, Nibong Tebal,
Pulau Pinang, Malaysia
–NC
223
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227
Chapter 14
A Model-Based Investment
Assessment for Heavy Oil
Processing in the Petroleum
Refining Industry
Cheng Seong Khor
Abstract
The need for heavy oil processing has increased in recent years worldwide,
backed by higher demands for petroleum products in the face of declining light
crude oil resources. The situation encourages refineries to focus more on maximiz-
ing the production of high-value outputs from this lower-value heavier feedstock.
This study purports to assess heavy oil processing potential in the refining industry
through model-based economic evaluation. We formulate a refinery model suitable
for preliminary investment decision making, which considers various cost elements
for a number of conventional commercial heavy oil processing technologies. The
formulated model is applied to a case study on the worldwide potential for heavy oil
processing. This chapter demonstrates the application of a model-based approach to
perform or assist with investment assessment.
Keywords: refinery design, optimization model, linear programming,

residue fluid catalytic cracking (RFCC), fluid coking
1. Introduction
Heavy crude oil upgrading has gained the interests of refineries as demand for
petroleum products increased in the face of declining lighter crude oil resources.
In today’s market, there are abundant heavier crude oils in the market as compared
to conventional lighter ones. However, multiple competing technologies exist with
a wide range of product yields and energy (or utility) requirements to refine these
heavy oil resources [1, 2].
Heavy crude oils contain high fractions of residue and are generally classified by
the density measure of API gravity of less than 20. The residue requires additional
upgrading processes to break the complex molecular structure in obtaining valu-
able products. Residue upgrading processes include several thermal and catalytic
processes, which can be categorized as carbon rejection or hydrogen addition.
Examples of carbon rejection processes are delayed coking (DCK), visbreaking
(VB), fluid coking (FCK), and solvent deasphalting, while hydrogen addition
technologies include fixed bed hydroprocessing (e.g., Hyvahl F) and ebullated bed
hydroprocessing (e.g., LC Fining) [3].
229
Processing of Heavy Crude Oils – Challenges and Opportunities
Integrating these technologies into refinery systems requires a systems approach-

based economic evaluation instead of relying on, for example, monovariable decision
making such as solely based on attaining the highest product yields. The increasing
demand for high-value petroleum products and declining for that of bottom distillate
products encourage refinery to give more focus on maximizing the yields on heavier
crudes. In addition to that, the price for heavy crude oils is generally lower than lighter
crude oils. Installing and operating heavy oil upgrading technologies enable refineries
to buy cheaper feedstock and still produce high-value marketable products [4].
There are available refinery optimization models of various complexities in
terms of time and space scales, which give rise to different computational require-
ments as based on the purpose and activity. For high-level decision making, linear
programming (LP) models are suitable when only preliminary results are needed
[5–8]. Nonlinear and/or mixed-integer models have been proposed for detailed
refinery design [9–12] and for operation management [13–15]. A recent review on
refinery optimization advances, which encompass developments in both academic
and industrial settings, is available in [16].
The present work attempts to contribute toward assessing heavy oil processing
potential in the petroleum refining industry by adopting a model-based economic
evaluation approach. Using product demands and crude oil feed properties as base
data, a refinery model can be developed to evaluate potentially profitable technolo-
gies including those for residue oil upgrading. For this purpose, we formulate an
optimization model suitable for a preliminary high-level investment decision making
with an appropriate economic objective function and a set of constraints that con-
sider a number of conventional commercial technologies. A case study using available
current data on market conditions is illustrated to carry out the intended assess-
ment. A secondary goal of the study is to demonstrate the use of a standard business
productivity tool (such as an Excel spreadsheet) to conduct such an assessment.
2. Problem statement
We consider the following investment decision-making problem for heavy oil

processing in refineries. Given the (a) fixed market demand for desired refinery
products and their prices, (b) available process technologies and their cost struc-
tures and capacities, and (c) cost of crude oil (single type or mixtures) and their
nominal product yields, we wish to determine the optimal process technologies or
units and their indicative processing capacities (flow rates) by minimizing the total
operating cost, which mainly consist of utility requirements on energy demand for
processing operations.
3. Optimization model formulation
A refinery model suitable for preliminary investment decision making is posed

as a linear optimization (LP) model. The model admits process parameters for
heavy oil processing including raw material availabilities, nominal product yields of
a number of representative commercial technologies, market demands and prices
for main product streams, and global processing or product capacities besides
various cost-related economic parameters. An optimum solution is determined as
a point in the solution space, which minimizes an economic-based objective func-
tion that stipulates the total operating cost for all heavy oil processing technologies
considered that is feasible in satisfying all the associated constraints encompassing
the aforementioned economic parameters.
230
A Model-Based Investment Assessment for Heavy Oil Processing in the Petroleum Refining Industry
This model uses the following notations:

Parameters
yd i,u yield of component i from unit u
ocu operating cost of unit u
nci capacity expansion cost of component i
cpu capacity of process unit u
dmi product demand of component i
Variables
Fi,u inlet flow rate of component i to unit u
Zi new capacity flow rate of component i
A compact representation of the optimization model formulation is presented

and explained as follows:
Minimize ∑ ocu Fi,u + ∑ i nci Zi (1)

i,u
Subject to ∑ yd i,u Fi,u = 0, ∀ i ∈ I (2)

u
∑ yd i,u Fi,u = 0, ∀ u ∈ U (3)

i
∑ i Fi,u ≤ cpu, ∀ u ∈ U (4)
Zi + ∑ u Fi,u ≥ dmi, ∀ i ∈ I (5)
Fi,u, Zi ≥ 0, ∀ i ∈ I (6)
where the minimizing objective function shown in Eq. 1 caters for operating cost
oc u, which consists of raw material cost on crude oils and utility cost of process units
as based on their inlet flow rates as well as capacity expansion cost nc i to meet market
demands dm i. Eq. 2 describes component balances for each material i using fixed yield
coefficients yd i,u (on mass basis), which render linear relation between the feed inputs
and product outputs of unit u that are implicitly dependent on the unit’s operating
conditions. On the other hand, Eq. 3 represents the total material balances for each
unit u. Eq. 4 ensures that the total inlet flows into unit u does not exceed its maximum
capacity cp u in determining the required processing level. Eq. 5 stipulates that total
processing rates for material i meet or exceed its demand dm iincluding a provision for
new capacity Z i (or alternatively available product imports) to cover market require-
ments. Equation 6 enforces nonnegative values for all the decision variables.
4. Case study
We consider a case study of assessing the worldwide potential for heavy oil
processing in the downstream petroleum processing sector by applying the forego-
ing model. Economic model parameters are estimated based on commercial data
available in the literature as cited for Tables 1–4. The raw material is assumed to be
a vacuum residue stream available from a vacuum distillation unit or, alternatively,
a vacuum rerun unit with comparable processing capacity.
231
Product Price ($/kg) Demand (kg/hour) Reference
Dry gas 0.0078 6000 [17, 18]
Total LPG 0.0020 30,000 [18, 19]
Gasoline 0.0097 150,000 [20, 21]
Diesel 0.0039 121,000 [18, 22]
Gas oil 0.0031 40,000 [18, 22]
Coke 0.0027 60,000 [23]
Table 1.
Model economic parameters for products used in this chapter.
The products of each process technology are categorized according to their cut
temperatures. Product yields of process technologies are typically given in volume
percentages in the literature. To make use of mass conservation principle, we
convert them to weight percentages by assuming fixed densities of the product and
feed components. The weight-based yields are then normalized as listed in Table 2
according to the process technologies for use as input-output constants in the
process unit material balances described by Eqs. (2) and (3).
Table 1 gives the product economic parameters in terms of selling prices and
market demands. The operating cost data for the heavy oil process technologies are
summarized in Tables 3 and 4. Annual operating time is taken to be 8150 hours per
year corresponding to an onstream factor of about 93% (0.9304).
The technologies considered in this case study (with their associated abbrevia-
tions in parentheses as used in Tables 3 and 4) are delayed coking (DCK); fluid
coking (FCK); fluid catalytic cracking (FCC); visbreaking (VB); ebullated bed
hydrocracking technology of LC Fining (LCF); Cherry-P (CP) and fluid thermal
cracking (FTC) technologies; residual fluid catalytic cracking (RFCC) technologies
of heavy oil treating (HOT), heavy oil cracking (HOC), and R2R (roughly stands
for residue cracking with two-step regeneration); solvent deasphalting technology
of MDS; and other residue hydrotreating and hydroconversion technologies of
asphaltenic bottoms cracking (ABC) and Hyvahl F (HF).
Further, we consider several assumptions in representing operating require-
ments of these technologies. Solvent deasphalting operation depends on the solvent
type. Visbreaking is a relatively inexpensive mild thermal cracking process that is
assumed to generate steam on a net basis, which can be sold (i.e., negative steam
cost), while its cooling utility uses air instead of water. Delayed coking requires a
furnace to heat the feed stream for coke removal; thereby, it uses a large fuel quan-
tity as compared to other technologies. Fluid coking is a catalytic operation which
uses steam for heating and air or water for cooling. Heavy oil cracking (HOC) is
similar to fluid catalytic cracking (FCC) with the capability to remove heat from the
generator, which can be recovered to produce steam, thus contributing as revenue
(i.e., negative steam cost). Hydrotreating (HDT) heavy oil consumes hydrogen
in the reaction scheme to decrease carbon-to-hydrogen ratio, in which the model
considers the worst-case operating requirements for cycle oil feed. Due to limited
literature data, cost parameters for certain technologies are approximated to similar
ones (e.g., LC fining to FCK).
We use the model to conduct a general assessment of the probable technolo-
gies required to meet heavy oil processing capacity globally. The result obtained is
graphically summarized in Figure 1. The objective value on total annualized cost of
heavy oil processing is found to be about 164.2 million US$ with total utility cost for
the selected units determined to make up 80%, while that of raw material cost only
232
233
Product Technology
DCK FCK FCC VB VB LCF CP FTC HOT HOC MDS ABC HF R2R
(lowa) (highb)
Dry gas 0.8 1.1 1.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Total LPG 12.5 11.0 15.0 2.0 2.3 2.6 0.0 0.0 0.0 12.4 0.0 0.0 0.0 0.0
Naphtha 16.8 19.2 42.1 5.5 6.2 12.0 6.6 16.5 13.0 53.7 0.0 7.5 0.0 63.0
Middle distillate 14.9 22.9 20.6 10.5 11.8 41.2 30.7 38.2 9.7 14.6 61.2 17.9 4.2 18.1
Gas oil 33.6 13.1 10.1 82.0 79.7 44.2 62.7 24.2 28.7 8.8 38.8 74.5 25.5 4.8
Coke 21.5 32.7 10.4 0.0 0.0 0.0 0.0 21.1 48.6 10.6 0.0 0.0 70.3 14.1
a
Low API feed.
b
High API feed.
Table 2.
Product yields (in normalized weight percentages) for process units used in this work [24–26].
234
Technology Electricity (kWh/b) HPS (lb/b) LPS (lb/bl) Fuel (kBtu/b) CW (gpm/ Cat (lb/b) H2 (ft3/b) Total ($/(year⋅
b/hour) (kg/hour))
MDS 0.133 60 — 80 — — — 266.4
VB 0.033 −50 — 80 — — — 265.8
DCK 0.239 — 40 120 0.6 — — 403.5
FCK 0.865 200 100 — 30 — — 273.9
FCC 0.067 — 20 80 400 0.3 — 312.2
HOC 0.017 — −80 80 — 0.25 — 267.0
HDT 0.093 — — 24 400 — 900 128.3

Notes: HPS = HP steam, LPS = LP steam, CW = cooling water, Cat = catalyst, H2 = hydrogen, unit b = barrel (0.136 barrel = 1000 kg), gpm = gallon/minute.
Table 3.
Utility requirements (base data) and cost for heavy oil process technologies [21].
235
Technology Parameter
Basis Operating cost ($⋅year−1(kg/hour)−1)
SDA VB DC FCK FCC HOC HDT

Electricity tariff 0.060 $/kWh 0.133 0.033 0.239 0.865 0.067 0.017 0.093
HP1 steam cost 0.0045 $/lb 0.299 −0.249 0.200 1.330 0.100 −0.399 0.036
2
LP steam cost 0.003 $/lb
Fuel cost 3.000 $/kBtu 266.0 266.0 399.0 0.0 266.0 266.0 79.8
Cooling water cost 0.10 $/gal 0.000 0 3.990 3.325 44.336 0.000 44.34
Catalyst cost 5.00 $/lb 0.000 0.000 0.000 0.000 1.663 1.386 0.000
3
Hydrogen cost 0.004 $/ft 0.000 0.000 0.000 0.000 0.000 0.000 3.990
Total — 266.4 265.8 403.5 273.9 312.2 267.0 312.2
Capacity (ton/hour) — 173.3 141.6 130.8 130.8 288.8 173.3 288.8

1
High pressure.
2
Low pressure.
Table 4.
Operating cost parameters [21].
Figure 1.
Model solution for the case study (all flow rates in kiloton per hour).
Figure 2.
Sensitivity analysis on effect of diesel capacity expansion cost on total operating cost.
17%. RFCC can account for nearly 31% of the available capacity, while the remain-
ing can be met by a fluid coking technology. The potential RFCC technologies
identified include HOC, HOT, and R2R [24]. It is also projected that there is demand
for 53% of capacity expansion for heavy oil processing.
In general, RFCC can be designed compactly to produce high yields of valuable
products with low maintenance cost as similar to the FCC technology that it is based
upon. Fluid coker is reported to promote reactor heat transfer, which allows it to be
236
operated at high temperature for high product yields with increased product separa-
tion into valuable products. It also uses burner operated with steam and air as utilities
as opposed to an expensive fuel, which is reflected in its low operating cost [26, 27].
We conduct sensitivity analysis to examine how the model parameter values
influence the solution. As an example, Figure 2 shows the linear effect of varying the
capacity expansion cost for diesel product output (in terms of a fixed multiplicative
factor) on the total operating cost for heavy oil processing as is considered in our case
study. Indeed, a trend of continuous high demand for distillate products (including
diesel) necessitates correspondingly increased investment in the processing cost.
The model implemented in Excel (version for Microsoft Office 365) is freely
available upon request from the author.
5. Concluding remarks
This chapter presents a model-based approach to conduct a preliminary assessment

for investment decision making in heavy oil processing for refineries. The economic
evaluation can be carried out using an Excel spreadsheet or other similar business
productivity tools. The results provide an order of magnitude indication of refining
capacity potential for this increasingly important resource in the hydrocarbon industry.
Author details
Cheng Seong Khor1,2
1 Chemical Engineering Department, Universiti Teknologi PETRONAS, Perak,

Malaysia
2 Centre for Process Systems Engineering, Institute of Autonomous Systems,

Universiti Teknologi PETRONAS, Perak, Malaysia
*Address all correspondence to: [email protected];

[email protected]
237
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239
Chapter 15
Environmental Challenges
Associated with Processing of
Heavy Crude Oils
Samuel O. Sojinu and Onome Ejeromedoghene
Abstract
The petroleum industry is one of the largest industries in the world and plays a
pivotal part in driving a nation’s economy. However, the exploration and exploita-
tion of heavy crude oil have raised series of environmental challenges and caused
increased concern for the communities where the oil refineries are cited. Activities
such as gas flaring and oil spillage have led to the release of toxic organic and inor-
ganic pollutants, which has resulted in acid rain, climate change, and contamination
of soil, water, and air. These environmental hazards have caused adverse effects
directly or indirectly to the ecosystem. This chapter offers a general overview of
the processes involved in the processing and some of the potential environmental
challenges associated with heavy crude oil processing.
Keywords: heavy crude oil, toxic pollutants, oil refinery, environment
1. Introduction
Heavy oil has been part of the natural environment for centuries. It is a sub-
stance believed to have formed over the years by the death and decomposition
of plant and animal remains that have become incorporated in the sediments of
shallow seas and later overlaid by a succession of strata of sedimentary rocks for
millions of years. These organic residues are acted upon by intense heat and pres-
sure into petroleum, migrating upwards, sometimes over extensive areas, either to
reach the surface or be occasionally trapped in what are to become oil reservoirs [1].
Heavy oil is a naturally occurring, unrefined petroleum that is basically com-
posed of hydrocarbon deposits and other organic materials. The heavy oil can be
processed into more useful products like gasoline, kerosene, jet fuel, diesel, heating
oil, and other allied products called petrochemicals by refining process.
Basically, crude oil undergoes various stages of exploration before getting to the
end consumers or retailers. The overall well-to-consumer supply chain for petro-
leum products is often described as being segmented into three main segments:
• Upstream activities: This comprises the preliminary stages. It involves explo-

ration activities of crude oil deposits leading to the production of crude oil.
Companies in this category include ExxonMobil and Shell Petroleum; they own
rights to drill. Also included in this category are companies providing support
services such as Halliburton.
241
• Midstream activities: These involve the transportation of crude oil to refinery;

the refining of crude oil into marketable products; and the onward distribu-
tion of these products to wholesalers and retailers. Included in this category
are companies that transport oil by pipeline, truck, or barge (e.g., Magellan
Pipeline, Tulsa, Oklahoma) and companies that refine crude oil (e.g., Tesoro,
San Antonio, Texas).
• Downstream activities: Similarly, these categories of activities involve the retail

end of petroleum industry. Gasoline stations are the main downstream compa-
nies; companies that supply heating oil or propane also fall into this category [2].
The American Petroleum Institute (API) classifies crude oils according to their
contents, origins, and specific gravity. Light crude oils or sweet crude are liquid
petroleum with low density and can flow freely at room temperature. They are
characterized by low viscosity (a property that defines ease of flow), low specific
gravity, and high API gravity due to the presence of a high proportion of light
hydrocarbon fractions basically from C6–C12. However, heavy crude oils are highly
viscous that cannot easily flow to production wells under normal reservoir condi-
tions. They yield more heat upon burning but have lower API gravity [3].
2. Heavy oils
In the past decades, heavy oils were formed when certain algae species degrades
hydrocarbon deposits which lead to the loss of its lighter hydrocarbon fractions,
leaving behind the heavier hydrocarbon fractions. By definition, heavy crude oil is
oil with high viscosity (approximately 10,000 centipoise). Heavy crude oil ranges
from free flowing oil to bitumen and/or tar sands “ultraheavy oil” that is actually
embedded in sand and located at depths less than 75 m [4].
Heavy oils are among the class of unconventional crude oil. They are one of
the world’s largest resources as well as a potential major contributor to the future
of energy globally. They are found all over the world with Canada and Venezuela
accounting for more than half of world deposits. Basically, the processing of heavy
crude oil is faced with challenges such as cost of extraction/processing, haulage to
refineries, and processing them into valuable products meeting market demands
while adhering to environmental requirements. In addition, the market for selling
these heavy crude oil directly is limited because only a few existing refineries are
capable of receiving and/or processing such low-quality crude oils [5].
Heavy crude oil is usually characterized by a low content of lighter cuts and
contains significantly higher contents of asphaltenes (altered fragments of organic
chemical compounds) (Tables 1 and 2), which have been reported to greatly
Fraction Weight percentage (%) Elementary composition based on C20+ (%)
C H N O S
Asphaltene 14.1 83.8 7.5 1.3 1.7 4.8
Resin 37.3 82.8 8.9 1.5 2 4.3
Aromatic 37.2 84.3 10 <0.3 1.1 4
Saturate 11.4 86.6 13 <0.3 <0.2 <0.1
Table 1.
Typical elemental composition for heavy oil [5].
242
Origin Composition (%) H/C ratio
Carbon Hydrogen Nitrogen Oxygen Sulfur

United Statesa 88.6 7.4 0.8 2.7 0.5 1
a
Kuwait 82.4 7.9 0.9 1.4 7.4 1.44
a
Venezuela 85.5 8.1 3.3 1.8 1.3 1.14
a
Mexico 81.4 8 0.6 1.7 8.3 1.18
Brazilb 83 9 2 — — 1.3
a
Italy 78 8.8 Trace 3 10.2 1.35
a
Canada 85.1 11.1 0.7 2.5 0.6 1.56
a
Data from Marcel Dekker, Inc. [8].
b
Total content of oxygen and sulfur is 6%.
Table 2.
Elemental composition of asphaltenes from several oil samples [7].
complicate the refining process. Subsequently, certain asphaltene requires that the
heavy oil also undergo a special refining process called deasphalting [6]. The impu-
rities present in heavy crude oil are in the form of compounds of sulfur, oxygen,
hydrogen, nitrogen, carbon, and the heavy metals (nickel and vanadium) [4].
The first Canadian producers of heavy bitumen known as Athabasca oil sands
used surface mining with massive equipment to mine the oil sands, separate the
bitumen from the sand, and return the sand to the excavation site. More recent
bitumen production uses the steam-assisted gravity drainage (SAGD) method
developed by the Alberta Oil Sands Technology and Research Authority in the
1980s. SAGD uses steam to heat the bitumen, allowing it to flow by gravity to a
reservoir where it is recovered [9].
Orinoco tar sand is the most common unconventional crude oil produced in
Venezuela. Typical qualities for Venezuelan unconventional crude oils are 5–15°
API gravity, 4–6 wt% sulfur, and 1–2 wt% nitrogen. There are also conventionally
produced heavy crude oils such as Ku-Maloob-Zaap oil that is very similar in quality
to unconventional heavy crudes [9].
More recently, there have been wide ranges of crude oil upgrading options that
can allow a large selection of upgraded crude oil qualities. They range from the simple
process of diluting with light sweet crude oil (naphtha or natural gas condensates) to
produce Maya crude equivalent to complex flow schemes that include delayed coking
and residue hydrocracking, as well as other various high-pressure hydrocracking tech-
nologies. Specifications for producing this crude type include a gravity target range
of around 20–25° API and a target sulfur content of around 3–4 wt%. More so, there
is currently high demand for this quality crude oil because the production of Maya
and other similar heavy crude oils has been declining in recent years. Exports of Maya
crude oil have decreased by about 1 million barrel per day over the last 7 years. Heavy
oil processing capacity has increased significantly over the same period (notably at
Reliance, Jamnagar, India; Motiva, Port Arthur, USA; and Marathon, Garyville, USA).
Creating a higher-quality, sweet synthetic crude oil with API gravity between
30 and 40° API opens up the potential market for upgraded crude oil by an order
of magnitude, because most refineries are capable of processing crude oils within
this gravity range. It may be difficult for the producer to justify the cost of the
additional upgrading required. However, this level of upgrading could be phased in,
if necessary, to accommodate potential market changes in the future. In the same
vein, creating high-quality finished products directly from unconventional crude
oils is possible but unlikely to be economically viable unless the refinery’s location
243
is near a large, high-value market for finished products, has economic logistical
options available for product movement, or has a unique specification it can meet.
For example, ultralow pour point diesel is a high-value product in Western Canada,
near the upgrader site, because of the cold winter season at that location [9].
3. Crude oil exploration and exploitation
Oil exploration and exploitation is a major revenue earner in petroleum-

producing countries [10] and serves as the driver of the economies of some of these
countries. However, like most human activities, it results in environmental hazards
that could be referred to as “slow poisons,” in that they often take a long time before
causing disease and, in extreme cases, death [11]. The usually unrecognized and
slow action of the hazards created by oil exploration and exploitation makes it
difficult to fully appreciate their contribution to the disease burden in a country like
Nigeria, especially in the oil-bearing communities [12].
4. Crude oil processing
4.1 Separation
The first step of crude oil processing involves the separation of the complex
mixtures in the heavy crude according to their molecular weight via atmospheric
distillation at atmospheric pressure. During the process, which is also referred to
as topping (refining), the oil is subjected to intense heated at the base of a 60 m
distillation column at a temperature of 350–400°C, causing it to turn to vapor. The
vapors rises inside the column, while the heaviest molecules, or residuals, remain
at the bottom. As the vapors rise, the molecules condense into liquids at different
temperatures along the length of the fractionating column. Only gases reach the
top of the column, where the temperature has dropped to about 150°C. The liquids,
which have become increasingly light, are collected on trays located at different
heights of the column. Each tray collects a different petroleum fraction, with highly
viscous hydrocarbons like asphalt (bitumen) at the bottom and gases at the top.
4.2 Conversion
The heavy fraction leftover after atmospheric distillation still retains many com-
pounds of medium density. This fraction is transferred to another column where it
undergoes a second round of distillation to recover middle distillates like heavy fuel
oil and diesel.
In the conversion process, the residual heavy hydrocarbon molecules from the
separation process are broken down into two or more lighter molecules. The conver-
sion process also known as catalytic cracking is carried out at 500°C. This converts
75% of the heavy products into gas, gasoline, and diesel. The yield can be increased
further by adding hydrogen, a process called hydrocracking, or by using deep
conversion to remove carbon. The more complex the operation, the more it costs
and the more energy it uses.
4.3 Treating
Treating entails deliberate removal of molecules that are corrosive or results in air
pollution, especially sulfur. Commencing from January 1, 2009, gasoline and diesel sold
244
in Europe cannot contain sulfur in excess of 10 parts per million (ppm) or 10 mg per kg.
The purpose of these measures is to improve air quality and optimize the effectiveness
of catalytic converters used to treat exhaust gas. For diesel fraction, desulfurization is
done at 370°C and at a pressure of 60 bar. The hydrogen employed in the process reacts
with the sulfur to form hydrogen sulfide (H2S), which is then further treated to remove
the sulfur, an important industrial material. Similarly, lighter fractions of kerosene,
butane, and propane are washed in a caustic soda (sodium hydroxide) solution to
remove thiols, also known as mercaptans. This process is referred to as sweetening [13].
5. Challenges associated with heavy crude oil processing
5.1 Gas flaring
Gas flaring has been one of the most challenging energy and environmental
problems facing the world today [14]. As a matter of fact, this act has been con-
demned in different countries of the world, but the practice has not been totally
abolished in some countries especially in the emerging economies [15]. The act
of flaring has been allowed by petroleum-producing countries with insufficient
fund and investment on structural infrastructure for the efficient utilization of the
associated gases obtained from crude oil refining processes [16]. This is in-line with
the definition of gas flaring, according to the Canadian Association of Petroleum
Producers, as the controlled burning of natural gas that cannot be processed for sale
or use because of technical or economic reasons (Figure 1) [17]. The World Bank
estimates that the annual amount of associated natural gas being flared and vented
is about 110 billion cubic meters (bcm), which is practically enough to provide the
combined annual natural gas consumption of Germany and France, with Nigeria
topping the list of highest gas flaring countries (Table 3). Also, estimates calculated
from satellite images of flares (National Oceanic and Atmospheric Administration,
(NOAA) data, reported by Global Gas Flaring Reduction Partnership (GGFR)
indicate that global gas flaring in 2012 alone was 144 bcm. This represents massive
resource wastage and a remarkable environmental problem, representing some
400 million tons in CO2 release into the environment and being at the level of one
third of EU’s gas consumption [18]. In addition, the amount is twice the annual gas
consumption of Africa and three quarters of the Russian gas export [19, 20].
Figure 1.
Flaring (A) from start-up operations on the Deepwater Atlantis platform [15] (B) in Nigeria [16].
245
2004 Country Reported flaring, 2004 Country Reported flaring,

rank 2004 rank 2004
1. Nigeria 24.1 11. U.S.A. 2.8
2. Russia 14.7 12. Kazakhstan 2.7
3. Iran 13.3 13. Libya 2.5
4. Iraq 8.6 14. Azerbaijan 2.5
5. Angola 6.8 15. Mexico 1.6
6. Qatar 4.5 16. UK 1.6
7. Algeria 4.3 17. Brazil 1.5**
8. Venezuela 3.7** 18. Gabon 1.4
9. Equatorial Guinea 3.6 19. Cameroon 1.1

10. Indonesia 3.5** 20. Canada 1.0
Total top 20 107.5

*Source: GGFR (The Global Gas Flaring Reduction Public-Private Partnership).
**These figures, expressed in billion cubic meters (bcm) may include some venting as well, due to unavailability of
segregated data [19].
Table 3.
Top 20 gas flaring countries in the world [19]*.
A flare is normally visible and generates both noise and heat. During flaring,
the burned gas generates mainly water vapor and CO2. Generally, the gases being
flared consist of a mixture of different gases; their composition depends on the
source of the gas going to the flare system. Natural gas predominantly contains
about 90% methane (CH4) with ethane and small amounts of other hydrocarbons
as well as variable amount of inert gases like N2 and CO2 [14, 21]. Efficient combus-
tion process involves achieving good mixing ratios between the fuel gas and air (or
steam) [22] and on the absence of liquids. Notably, low pressure pipe flares are not
intended to handle liquids and do not perform efficiently when hydrocarbon liquids
are released into the flare system [23].
Typical gas flaring systems are set up on onshore and offshore platforms of
production fields, on transport ships, port facilities, storage tank farms, and along
distribution pipelines to vent off trapped gas. The system consists of the flare stack
or boom and pipes which collect the gases to be flared (Figure 2) [24]. Most flaring
processes take place at the top of stack through combustion of gases with the visible
flame. However, the height of the flame depends upon the volume of released gas,
while brightness and color of the flame largely depend upon composition. The tip of
the flare at the end of the stack or boom is designed to assist entrainment of air into
the flare to improve burning efficiency. Seals located in the stack prevent flashback
of the flame, and a vessel at the base of the stack removes and conserves any liquids
from the gas passing to the flare [20].
5.1.1 Classification of flaring processes
5.1.1.1 Emergency flaring
Emergency flaring occurs in cases of fire outbreak, breakage of valves, or

compressor failures. This leads to the burning of a large volume of gas within a very
short time [20].
246
Figure 2.
Schematic flow diagrams of an overall vertical elevated flare stack system [25].
5.1.1.2 Process flaring
Process flaring usually comes with a lower rate, such as during petrochemical
process; this involves the removal and subsequent flaring of waste gases in the pro-
duction stream. The volumes of flared gas at such processes can vary during normal
functionality and plant failures from a few m3/h to thousands m3/h, respectively [26].
5.1.1.3 Production flaring
Production flaring occurs in the exploration of crude oil. Large volumes of gas
are usually combusted during the evaluation of a gas-oil potential test as an indica-
tion of the capacity of the well for production.
It has been reported that the flares contain recognized toxins, such as benzene,
which pollute the environment drastically [27].
5.2 Environmental challenges associated with gas flaring
5.2.1 Climate change
Gas flaring contributes to climate change, which has serious environmental

implications globally. The burning of fossil fuel gives off carbon dioxide, methane,
and other gases which has led to global warming with more serious environmental
challenges for developing countries, especially Africa which is highly vulnerable
with limited ability to adapt [28]. The Intergovernmental Panel on Climate Change
(IPCC), a scientific body set up in 1988 by the UN and the World Meteorological
247
Organization to consider climate change, has projected that in the twenty-first

century, the problem of climate change will get worse due to the frequent release of
greenhouse gases warming up the world.
Flaring releases carbon dioxide and methane which are the two major green-
house gases, with methane more toxic and harmful than carbon dioxide. According
to the global warming potential estimates, a kg of methane is about 21 times that of
a kg of carbon dioxide when the effects are considered over 100 years [29]. Research
shows that flaring at lower efficiency emits a higher amount of methane than car-
bon dioxide. This is because those less-efficient flares tend to have more moisture
and particles in them reflecting a high amount of heat. Consequently, they produce
similar effect on the ozone layer like aerosols [30–32].
5.2.2 Acid rain
Flaring also contributes to local and by extension regional environmental

problems, such as acid rain with attendant impact on agriculture, forests, and other
physical infrastructures [33]. The main causes of acid rain are emissions of sulfur
oxides (SOx), nitrogen oxides (NOx), and carbon dioxide which combine with
atmospheric vapor to form sulfuric acid, nitric acid, and weak carbonate acids. Acid
rain has been largely implicated in the corrosion of corrugated roofs/buildings in
the Niger Delta region of Nigeria due to excessive flaring [34]. The corrosion rate in
this region of Nigeria is faster when compared to other regions of the country.
Acid rain acidifies lakes and streams and damages vegetation. In addition,
acid rain accelerates the decay of building materials and paints. In addition, these
contaminants acidify the soil, hence depleting soil nutrient, decreasing soil fertility,
and reducing the nutritional value of crops cultivated within such flaring vicinity
[35]. The effects of the changes in temperature on crops included stunted growth,
scotched plants, and such other effects as withered young crops [36]. In some cases,
there is no vegetation (Figure 3) in the areas surrounding the flare due partly to the
tremendous heat that is produced and acidic nature of the soil pH [37].
5.2.3 Agriculture
Gas flaring has also been studied widely and reported to show negative effects
on plant growth and wildlife [20]. Studies on the effects of waste gas flares on the
surrounding vegetation in southeastern Nigeria show that the effect of flare extends
Figure 3.
Effect of acid rain on the environment [38].
248
well beyond a distance of 110 m from the stacks, with the exception of the suppres-
sion of the flowering of short-day plants [39]. It was therefore recommended that
further studies were necessary to determine the effects of the flares on the produc-
tivity of crops grown in the region (Table 4) [41]. Soils of the study area are quickly
losing their fertility and capacity for sustainable agriculture due to the acidification
of the soils by the various pollutants associated with gas flaring in the area. This is in
agreement with previous studies [35].
In one of our unpublished data, it was discovered that the carbon (13C) isotopic
composition for various categories of plants have been altered due to gas flar-
ing in the region. Studies show that gas flaring significantly affects not only the
microclimate but also the soil’s physiochemical properties of the flare sites [42].
This was reflected in the study on the effect of gas flaring on maize yield size. The
study reveals increased soil physiochemical properties (such as sand content of
the soil, pH, bulk density, air and soil temperatures) toward the flare site. It was
recommended that for an optimum yield of maize within the Niger Delta where gas
flaring is taking place, the maize must not be cultivated within 2 km of the bund
wall of the flare sites.
Furthermore, the destructive effect of gas flaring on wildlife has also been
reported [43]. The study opined that gas flaring has been associated with the
disruption of wildlife in the immediate surrounding area. As a result, the continu-
ous bright light of gas flares scares wildlife causing them to migrate to more friendly
territories or locations.
5.2.4 Health effects
Gas flaring causes the adjoining communities to suffer from increased health
risks caused by exposure to those hazardous air pollutants emitted during incom-
plete combustion of gas flare. These pollutants are associated with a variety of
adverse health impacts, including deformities in children, skin problems, cancer,
lung damage, neurological and respiratory tract diseases, reproductive and devel-
opmental effects, etc. [44–46].
Information from the World Bank on the adverse health impact of particulate
matter suggests that gas flaring from Bayelsa State, in Nigeria, would likely result
to 49 premature deaths, 4960 respiratory illness among children, and 120 asthma
attacks annually [47]. Also, the US Environmental Protection Agency (EPA) warns
that exposure to benzene causes acute leukemia and a variety of other blood-related
disorders in humans. Exposure to H2S at concentrations below the permissible limit
can cause spontaneous abortion [48].
5.3 Current trend in global gas flaring
Over the years, policies and regulations to tackle the menace of gas flaring have
been stepped up considerably by various oil-producing countries with oil and gas
companies taking active steps to plan and implement flare-reduction measures.
Distance of farmland from flare site Percentage loss in yield of crops (%)
100 m 100
600 m 45
1 km 10
Table 4.
Loss in crop yield due to gas flaring [40].
249
Globally, a decline in the volume of associated gases flared from 2005 to 2010 of
about 20% has been reported [18].
Azerbaijan’s national oil company, State Oil Company of Azerbaijan Republic
(SOCAR), had reduced her associated petroleum gas flaring and venting almost
by half to less than 300 million cubic meters within 2 years after joining the GGFR
in 2010. The key to this success was measurement (by relying on available data on
how much, where, and how gas was being flared) and planning, with the GGFR
contributing to both. The GGFR helped by providing measuring equipment and
trained the company’s staff in using it. Based on information gathered, SOCAR
in collaboration with the British Petroleum Company drafted a gas recovery plan
that put 1.6 bcm of natural gas to productive use in 5 years. This was used to power
Azerbaijan’s economy and development while ensuring a cleaner environment.
In the Al-Shaheen project, GGFR partnered with Qatar Petroleum and Maersk
and worked together to capture and use 180 million cubic feet of gas per day for
power generation. The gas, produced as a byproduct of pumping oil from 300 off-
shore wells, had been flared since oil production started at the Al-Shaheen field in
1994. This hitherto wasted gas is now being used to provide about a third of Qatar’s
electricity, and the gas emissions have been drastically reduced at the completion
of the project.
Mexico likewise reduced gas flaring by 66% in 2 years owing to collaboration
among the country’s Secretary of Energy, its national oil company, Pemex, regula-
tors, and GGFR. Pemex is committed to reducing gas flaring while strengthening
flaring and venting regulations, as well as investing in gas recovery strategies.
The government in partnership with operating companies in the Republic of
Congo developed a 350 megawatt gas-to-power project feeding two power plants
with gas from the M’Boundi oil field. The laudable initiative has reduced emissions
of greenhouse gases and increased access to electricity for some 300,000 people.
Kuwait Oil Company and GGFR worked together on a plan to reduce flaring
below 1% of the intake associated gas and reach a “technical limit” for gas flaring
reduction.
In Nigeria, huge investments from GGFR partners have also helped in reducing
gas flaring by 4 bcm in the past 5 years: from 18.6 bcm in 2006 to 14.6 bcm in 2011.
GGFR is working with the government and the oil companies to continue build-
ing on this positive trend. The World Bank also provides partial risk guarantees to
investors in gas-to-power projects [49].
5.4 Crude oil spillage
Oil spillage have been a global issue that has been occurring since the discovery
of crude oil [50]; spillage have the potentials of adversely affecting the different
spheres of the environment such as coastal and marine habitats, wildlife, fisheries,
and human activities (Figure 2) [51–53]. Crude oil spillage is simply regarded as the
unlawful release of liquid petroleum hydrocarbons within the environments, due
to accident and/or intentional human factors. This phenomenon occurs in different
forms, and it is attributed to several factors as discussed below.
5.4.1 Equipment failures
Thousands of barrels of oil have been spilt into the environment through failures
of oil pipelines and tanks in the country. This spillage is a result of lack of regular
maintenance of the pipelines, drilling rigs, and storage tanks and leakages/spills
during processing and at refining plants. Some of these facilities have been in use
for decades without replacement.
250
5.4.2 Human error/theft
Sabotage is another major cause of oil spillage in some countries like Nigeria.
Some of the citizens of the country with connivance with people from other countries
engage in oil bunkering. They damage and destroy oil pipelines in their effort to steal
oil from them. Shell Petroleum Development Company (SPDC) in 1996 claimed
that sabotage was responsible for more than 60% of all oil spilled at its facilities in
Nigeria, stressing that the percentage has increased over the years because the number
of sabotage incidents has increased adding that spills due to corrosion of pipelines
have decreased with programs to replace oil pipelines (Figure 4, Table 5). Pirates are
stealing Nigeria’s crude oil at a phenomenal rate, carting away nearly 300,000 barrels
per day, and selling it illegally to the international trade market [41, 54]. Table 6 gives
an example of the number of spills and the reported volumes of oil spilled into the
marine environment from 1997 to 2014. Nigeria’s largest spill till date was an offshore
well blowout in January 1980, when an estimated 200,000 barrels of oil (8.4 million
US gallons) spilled into the Atlantic Ocean from an oil industry facility, and that inci-
dence damaged 340 hectares of mangrove [56]. In Russia, aging and leaking pipelines
are responsible for the wastage of millions of tons of oil a year, causing widespread
environmental damage that largely goes unreported, according to Greenpeace Russia.
However, reports have it that the Russia’s 4.5 million tons of leaked oil is seven times
greater than the BP Deepwater Horizon spill in the Gulf of Mexico in 2010 [57].
Notably, in the highest oil-producing region in Russia (Khanty-Mansi region in
Northwestern Siberia), the annual oil spills from pipelines amounted to 5781.4 tons on
an area of 229.6 hectares in 2009. In 2010, the Russian Company, Rosneft, alone spilled
3738 tons, and in 2011 a total of 5289 tons of oil was spilled in the region [58, 59].
Oil spills have and are still posing major threat to the environment of the oil-
producing areas, which if not effectively checked can lead to the total destruction of
the ecosystems. During an oil spill incidence in water, the gaseous and liquid com-
ponents evaporate with time. Some other components immediately get dissolved in
the water and become oxidized, while some undergo bacterial changes and eventu-
ally sink to the bottom. Oil spills often result in contamination of surface water with
hydrocarbons and trace metals (Figure 5) [10]. Also, the soil is contaminated with a
wanton negative impact on the terrestrial inhabitants. As the continued evaporation
of the volatile and semivolatile lower-molecular-weight compounds affects aerial
life, the dissolution of the less-volatile components with the resulting emulsified
water affects aquatic life [60].
In addition, oil spill destroys plants and animals in the estuarine habitat. Oil
settles on beaches and kills organisms that live there; it also settles on ocean floor
Figure 4.
Oil pipelines in Okrika community, Niger Delta [55].
251
Causes Number (N = 135) Percentage
Mechanical failure 23 17.04
Corrosion 21 15.56
Operational error 17 12.59
Third party activity 28 20.74
Natural hazard 3 2.22
Unknown 43 31.85
Table 5.
The causes of oil pipeline failures between 1999 and 2005 [51].
Year Total number of reported spills Quantity in barrels Source
1997 339 59,272.00 [49]
1998 390 —
1999 319 —
2000 637 84,072.00
2001 412 120,967.00
2010 537 17,658.10 [50]
2011 673 66,906.84
2012 844 17,526.37
2013 522 4066.20
2014 1087 10,302.16
Table 6.
Reported oil spillage in the Niger Delta region.
Figure 5.
Impact of oil spillage on (A) loss of vegetation in Ogoni land, Niger Delta [62]. (B) Russia wasting millions of
tons of oil from leaking pipes [56].
and kills benthic (bottom-dwelling) organisms such as crabs. Oil poisons algae, dis-
rupts major food chains, and decreases the yield of edible crustaceans. It also coats
birds, impairing their flight or reducing the insulative property of their feathers,
thus making the birds more vulnerable to cold. Oil spill also endangers fish hatcher-
ies in coastal waters and as well contaminates the flesh of marketable fish. Studies
252
show that the pollution caused by oil spillage does not end with the mopping up of
the spilled oil [61].
It is now known that health risk is not averted by abstinence or nonconsumption
of fish killed by spilled oil. Some of the fishes and animals that escape death from oil
spill pollution are known to have taken in some of the toxic substances, which in turn
get into human beings that eat them as a result of bioaccumulation of these sub-
stances. This will in turn cause infections on man coupled with other “side effects”
such as genetic mutations [61]. In another study [63], the density of sandstone inter-
laced with shale, beach ridge sand, and medium-coarse sand samples was reduced
by 17.7, 13.3, and 15.0% on the average, respectively, due to oil spillage. Furthermore,
crude oil-rich beach ridge sand, sandstone interlaced with shale, and medium-coarse
sand decreased averagely by 4.4, 9.9, and 15.2%, respectively, of the original value of
the specific heat capacity of the unmixed samples, while thermal conductivity of the
crude oil beach ridge sand, medium-coarse sand, and sandstone interlaced with shale
derivative increased by 9.8, 2.6, and 12.3%, respectively, on the average.
For example, a Nigerian coastal environment housing an extensive mangrove
ecosystem has been destroyed. The mangrove was once a source of both woods
being used as fuel for the indigenous people and a habitat for the area’s biodiversity,
but it is now unable to survive the oil toxicity of its habitat. Oil spills in the Niger
Delta have been a regular occurrence, and the resultant degradation of the sur-
rounding environment has caused significant tension between the people living in
the region and the multinational oil companies operating there [64].
5.5 Noise
Noise pollution is one of the environmental impacts associated with heavy crude
processing. The main sources of noise during the production of heavy crude oil
would include compressor and pumping stations, producing wells, and vehicular
traffic [65]. It has been reported that compressor stations produce noise levels
between 64 and 86 dBA close to the station to between 58 and 75 dBA at about
1 mile (1.6 km) away from the station [66]. The direct impacts from the noise pollu-
tion would be localized disturbance to wildlife and residents.
5.6 Ecological resources
The major impacts to ecological resources during production of heavy crude oil
could occur from disturbance of wildlife from noise and human activity; exposure
of biota to contaminants; and death of biota from accidental collision with ground
facilities or vehicles [67]. The presence of production wells, ancillary facilities, and
access road can also reduce the habitat quality, disturb the biota, and thus affect
ecological resources [68]. The presence of an oil field could also interfere with
the migratory and other behaviors of some wildlife. The inappropriate discharge
of produced water onto the soil or surface water bodies can result in high salinity
which will not be able to sustain plant growth. In locations where naturally occur-
ring radioactive material (NORM)-bearing produced water and solid wastes are
generated, mismanagement of these wastes can result in radiological contamination
of soils or surface water bodies leading to more harmful effects on humans [69].
5.7 Hazardous materials and waste management
Improper handling of industrial/hazardous waste obtained from the processing

of heavy crude oil could cause an adverse effect on the ecosystem when released
into the environment. These wastes are usually produced during routine operations
253
in process plants [65]. Chemicals contained in open pits used to store wastes may
pose a threat to wildlife and livestock because of potential seepage of such chemicals
into the underground water. Sand separated from produced water should be prop-
erly disposed as it is often contaminated with oil, trace amounts of metals, or other
naturally occurring constituents. Production processes could also cause accumula-
tion of large volumes of scale and sludge wastes inside pipelines and storage vessels
[70]. These wastes may be transported to offsite disposal facilities. Produced water
can become a significant waste stream during the production of crude oil.
5.8 Air quality
The primary emission sources during the production of heavy crude oil include
compressor and pumping station operations, vehicular traffic, production well
operations, separation of oil phases, and on-site storage of the crude oil. Toxic
pollutants emitted during operations would include volatile organic compounds
(VOCs), nitrogen oxides, sulfur dioxide, carbon monoxide, benzene, toluene, eth-
ylbenzene, xylenes, polycyclic aromatic hydrocarbons (PAHs), hydrogen sulfide,
particulates, ozone, and methane which normally pose as impurities in operation
columns [71].
5.9 Health and safety
Potential impacts to general public health and safety during production include
accidental injury or death to workers and, to a lesser extent, the public. Health
impacts could also result from water contamination, air pollutions, noise, soil
contamination, and stress (e.g., associated with living near an industrial zone) [65].
Potential fires and explosions could constitute hazards. Cavitation could ignite
grass fires. Increased or reckless driving by oil or gas workers would also create
hazards. In addition, health and safety hazards include working in extreme weather
conditions and possible contact with natural hazards, such as uneven terrain and
dangerous plants, animals, or insects [72].
6. Conclusion
The processing of heavy crude oil generates different types of toxic organic and
inorganic pollutants which pose direct or indirect impacts on the environment.
Gas flaring, oil spillage, and pipeline vandalization have been some of the major
processes leading to the release of toxic pollutants into the environment. Equipment
failure and sabotage/theft have been major causes of oil spillage. These incidences
have destroyed the coastal vegetation, polluted ground/surface water, and led to
ethnic and regional crises. Other environmental impacts associated with heavy
crude oil processing include noise pollution from producing wells, interference
with ecological resources, release of hazardous materials, reduction in air quality,
and health and safety implication. It is therefore pertinent for the petroleum sector
to adopt procedures that would provide a reasonable degree of protection to the
environment. Such procedural techniques, if implemented, should be able to reduce
or eradicate those toxic pollutants.
254
Author details
Samuel O. Sojinu* and Onome Ejeromedoghene

Department of Chemistry, Federal University of Agriculture, Abeokuta, Nigeria
255
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260
Unconventional heavy crude oils are replacing the conventional light crude oils slowly
but steadily as a major energy source. Heavy crude oils are cheaper and present an
opportunity to the refiners to process them with higher profit margins. However, the
unfavourable characteristics of heavy crude oils such as high viscosity, low API gravity,
low H/C ratio, chemical complexity with high asphaltenes content, high acidity, high
sulfur and increased level of metal and heteroatom impurities impede extraction,
pumping, transportation and processing. Very poor mobility of the heavy oils, due to
very high viscosities, significantly affects production and transportation. Techniques
for viscosity reduction, drag reduction and in-situ upgrading of the crude oil to
improve the flow characteristics in pipelines are presented in this book. The heavier
and complex molecules of asphaltenes with low H/C ratios present many technological
challenges during the refining of the crude oil, such as heavy coking on catalysts.
Hydrogen addition and carbon removal are the two approaches used to improve the
recovery of value-added products such as gasoline and diesel. In addition, the heavy
crude oil needs pre-treatment to remove the high levels of impurities before the crude
oil can be refined. This book introduces the major challenges and some of the methods
to overcome them.
ISBN 978-1-83968-409-8
ISBN 978-1-83968-411-1
Published in London, UK
© 2019 IntechOpen
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Processing of

Heavy Crude Oils

Edited by Ramasamy Marappa Gounder

Published in London, United Kingdom

© The Editor(s) and the Author(s) 2019

First published in London, United Kingdom, 2019 by IntechOpen

British Library Cataloguing-in-Publication Data

Additional hard and PDF copies can be obtained from [email protected]

Processing of Heavy Crude Oils - Challenges and Opportunities

4,500+ 118,000+ 130M+

Our authors are among the

Selection of our books indexed in the Book Citation Index

Interested in publishing with us?

Dr. M. Ramasamy is currently an Associate Professor in the

Pre-treatment and removal of impurities/metals from heavy crude oils are

I am deeply indebted to my wife Chandragandhi and children, Ramadevi and

Ramasamy Marappa Gounder

Introductory Chapter: Heavy

3.1 Viscosity reduction techniques

generally well insulated, and the temperature is maintained by providing external

3.2 Drag reduction techniques

3.3 In situ crude oil upgrading

Physicochemical upgrading of heavy oils produces a synthetic oil or syncrude

4. Heavy crude oil refining

The processing of heavy oils in refineries, especially in the existing refineries,

1 Department of Chemical Engineering, Universiti Teknologi PETRONAS,

2 Centre for Process Systems Engineering, Institute of Autonomous Systems,

*Address all correspondence to: [email protected]

[3] He L, Lin F, Li X, Sui H, Xu Z.

[4] Guo K, Li H, Yu Z. In-situ heavy and

[5] Palou RM, Mosqueira ML,

[6] Santos RG, Loh W, Bannwart AC,

[7] Rana MS, Samano V, Ancheyta J,

[8] Khan MK, Kwek W, Kim J. Upgrading

[9] Canıaz RO, Erkey C. Process

Methods for Enhancing Recovery

Keywords: enhancing oil recovery, nanoparticle, carbon dioxide injection,

Nanotechnology is one of the methods which attracts great attention nowadays in

Commonly, the size of nanoparticles for oil recovery is in a range of 1 to 100 nm.

Nanoparticles Findings References

Nickle oxide • Has the same characteristics as Al2O3. [3, 4]

Magnesium • Cause permeability impairment in sandstone rocks. [3, 4]

Zinc oxide • Very limited use in EOR. [3, 4]

Zirconium oxide • Rarely used in EOR. [4, 16]

Tin oxide (SnO2) • Same characteristics as zirconium oxide. [4, 16]

SiO2 • Less oil recovery at room temperature. [4, 9, 20–22]

Nanoparticles Findings References

Inorganic • Can reduce IFT. [23, 24]

3. Carbon dioxide injection

• CO2 can easily dissolve in oil. [30]

• The mobility of oil increases after the injection of CO2. [34]

• Thermal recovery method used to recover a big portion of oil. [44]

Usually, the injection of any type of chemical as a dilute solution is used in

The authors declare no conflict of interest.

Mohd Afnan Ahmad1,2, Shafirah Samsuri1,2* and Nurul Aini Amran1,2

1 Chemical Engineering Department, Universiti Teknologi PETRONAS,

2 Centre for Biofuel and Biochemical Research, Universiti Teknologi PETRONAS,

*Address all correspondence to: [email protected]

[1] Planckaert M. Oil reservoirs and oil [8] Roustaei A, Saffarzadeh S,

[5] Shahrabadi A, Bagherzadeh H, [12] Alomair OA, Matar KM,

(GOR) 1500–1750 & up to 2000 scf/STB 2000–3000 scf/STB

API <45° 40° or higher