BRAZILIAN JOURNAL OF PETROLEUM AND GAS | v. 11 n. 2 | p.

115-130 | 2017 | ISSN 1982-0593

FACTORS THAT AFFECT CRUDE OIL VISCOSITY AND TECHNIQUES TO

REDUCE IT: A REVIEW

a
Santos, I. C. V. M.; a Oliveira, P. F.; a,b Mansur, C. R. E. 1
a
Federal University of Rio de Janeiro (UFRJ), Institute of Macromolecules, Rio de Janeiro – RJ, Brazil
b
Federal University of Rio de Janeiro (UFRJ), Program of Materials and Metallurgy Engineering, Rio de Janeiro – RJ, Brazil
Received: 04.05.2017 / Revised: 26.06.2017 / Accepted: 30.06.2017 / Published on line: 18.07.2017

ABSTRACT
During oil extraction, the high viscosity of crude oil cause major problems, affecting negatively the oil
production rate. Many studies have focused on evaluating the properties of different crude oil grades and
their production techniques. The main causes of high viscosity are the presence of solids and high
concentrations of heavy fractions and the formation of water-in-oil (W/O) emulsions. This paper discusses
the mechanisms that seek to reduce the viscosity of oil containing high concentrations of heavy fractions,
the mechanisms of formation and destabilization of emulsions, and the use of polymers in technologies to
reduce viscosity, mainly by applying emulsion viscosity reducers (EVRs).

KEYWORDS
petroleum; viscosity; emulsion; heavy oil; extra heavy oil

1
To whom all correspondence should be addressed.
Address: Universidade Federal do Rio de Janeiro (UFRJ), Centro de Tecnologia, Bl. J, Avenida Horácio Macedo, 2030, Cidade
Universitária, Ilha do Fundão, Rio de Janeiro – RJ, Brasil.
ZIP Code: 21941-598 | e-mail: [email protected]
doi:10.5419/bjpg2017-0010

115
 BRAZILIAN JOURNAL OF PETROLEUM AND GAS | v. 11 n. 2 | p. 115-130 | 2017 | ISSN 1982-0593

1. INTRODUCTION and/or naphthenic rings attached to the benzene

ring (Castro & Vazquez, 2009). Resins are defined
Global demand for oil has been increasing over as the fraction of oil soluble in light alkanes. They
the past two decades (Ghanavati et al., 2013). Just have aromatic and polar characteristics, besides
in the last quarter of the 20th century alone, it having in their structure heteroatoms, such as
registered an increase of about 1% a year. This nitrogen and oxygen (Ashoori et al., 2017; Muraza
pace accelerated substantially with the start of the & Galadima, 2015).
21st century, mainly because of growing demands
from emerging countries like China and India. In Asphaltenes are defined as the fraction of oil
2009, global oil demand was 1.8% higher than the insoluble in n-alkanes (such as n-pentene and n-
previous year, despite the global economic slump heptane) and soluble in aromatic solvents (benzene
caused by the subprime mortgage crisis. The and toluene) (Asomaning, 2003, Garcia-Olvera et
International Energy Agency (IEA) and the World al., 2016). In addition, these are the components of
Energy Council (WEC) agree that, based on current higher polarity and higher molar mass present in
projection, the demand will grow 66% by 2030. the oil. They have a great structural complexity
International studies also predict that in the next originated from polycondensed aromatic rings
20 years, at least 80% of the world’s energy needs containing alkyl radicals of different sizes and
will be supplied by oil, natural gas, and coal functional groups formed by oxygen, nitrogen and
(Martinez-Palou et al., 2011). Therefore, despite sulfur elements, as well as metals such as
efforts to develop alternative energy sources, vanadium, nickel, and iron (Ovalles et al., 2016).
hydrocarbons will continue playing the leading role Asphaltenes are the main components of heavy
in satisfying global energy demand. However, the oil and bitumen. Reservoirs show significant
consumption of conventional light oils has resulted geological differences in producing oils with
in declining reserves of these resources (Saniere et
different SARA proportions and sulfur content. For
al., 2004). As fossil fuels will remain to be the main
example, high sulfur heavy oils mostly exist in
energy source for the coming decades, there is an
North America, South America, and Middle Eastern
urgent need to exploit alternative fossil resources
countries (Sheu et al., 1991b).
(Dusseault & Shafiei, 2011). Therefore, substantial
efforts have been devoted to the effective Heavy or extra-heavy oils are highly viscous oils
production of heavy and extra-heavy oils from that cannot easily flow to production wells at
reservoirs (i.e., natural bitumen or oil sands), which normal reservoir conditions. The definition of
account for ca. 70% of total world oil reserves “heavy” is based on the density or specific gravity,
(Dusseault & Shafiei, 2011). which is higher than that of lighter oils (i.e.
conventional oils) (Martinez-Palou et al., 2015).
Crude oil is a complex mixture of thousands of
compounds with numerous functional groups, Gravity and viscosity are the two standards used
consisting mainly of simple hydrocarbon species, to classify light, heavy, and extra-heavy oils, which
and the variation in its composition gives it are exemplified below: (1) Light oil: °API > 22,
different properties. Petroleum is characterized in viscosity < 100 cP, density < 934kg/m3; (2) Heavy
terms of the contents of the fractions denominated oil: °API 10-22, viscosity > 100 cP, density 934-
by saturated, aromatic, resins, and asphaltenes 1000Kg/m3 and (3) Extra-heavy oil (bitumen): °API
(SARA). These fractions are separated from < 10, viscosity > 10.000 cP and density > 1000
petroleum based on their polarity, using solvents Kg/m3 (Guo et al., 2016).
with different polarities and the adsorption on
active surfaces, such as silica (Varfolomeev et al., Besides viscosity, density, and °API, heavy and
2016). extra heavy oils also have other physical and
chemical properties that are very different than
Saturates are essentially non-polar and free of those of conventional crudes, such as higher
double bonds. Aliphatic hydrocarbons and alicyclic concentrations of heavy metals, high
hydrocarbons are part of this classification and carbon/hydrogen (C/H) ratios, and high
they constitute the lightest fraction of the oil. heteroatom contents (Martinez-Palou et al., 2011;
Aromatics are compounds containing one or more Saniere et al., 2004). These oils are less valuable
benzene rings, which may contain aliphatic chains because of the greater difficulty of achieving water-

116
 BRAZILIAN JOURNAL OF PETROLEUM AND GAS | v. 11 n. 2 | p. 115-130 | 2017 | ISSN 1982-0593

oil separation, transporting and refining (Kelesoglu sample containing quantities of asphaltenes
et al., 2012). They are highly viscous, and cannot ranging from 0 to 20% by mass. The author
easily flow to production wells at normal reservoir performed a scan in a sheer stress range of 0.03 -
conditions, since their consistency varies from a 596 Pa at 20 °C. The results showed that all the
paste to a solid at room temperature, with samples behaved as Newtonian fluids, and the
viscosities ranging from 102 cP to more than 105 cP viscosity increased with rising asphaltene
at room temperature. Generally, a crude oi with concentration. For example, the viscosity of the
viscosity < 400 cP has the maximum desired maltenes was about 20 000 cP while that of the
pipeline viscosity (Hasan et al., 2010). Several sample containing 17% asphaltenes reached 600
factors can influence this viscosity, such as high 000 cP (Hénaut et al., 2001).
concentration of heavy fractions such as
asphaltenes and presence of water-in-oil (W/O) According to Argiller et al. (2002), rheological
emulsions (Kessick & Denis, 1982). measurements of some mixtures of maltenes and
asphaltenes revealed that, above a critical
The formation of W/O emulsions can reduce asphaltene concentration (10% by weight), these
substantially oil production rates because of the components not only dramatically increase the
high viscosity of the emulsions, which increase with viscosity, they also intensify the elastic character of
the water content until reaching the phase the mixture.
inversion point (PIP). It is important to know both
the emulsion viscosity and the phase inversion Ghanavati et al. (2013) analyzed the effect of
point to make proper decisions on the size of lines asphaltene quantity on the viscosity of a
and equipment and to evaluate production dehydrated heavy oil. For this purpose, an initial
strategies (Kelesoglu et al., 2012). The presence of sample of crude oil was obtained from one of Iran’s
inorganic solids in crude oil can also cause main fields. The asphaltenes, composing 14.9% of
complications for transportation. If the size of the weight, were extracted with hexane, to obtain
these particles is sufficiently small (a few microns 10 asphaltene-free samples, called maltene. Then
or less), they can be adsorbed on the heavy different concentrations of asphaltenes were
fractions, such as resins and asphaltenes. These added to these samples. The results showed that in
aggregates then tend to migrate to the water-oil the diluted region (the samples with low
interface, forming extremely stable emulsions and asphaltene content) the increase in viscosity was
making the oil highly viscous, both because of the relatively linear with rising asphaltene
quantity of emulsion and the quantity of solids concentration, and it was not highly dependent on
(Abdel-Raouf, 2012). temperature. According to the authors, this was
due to the fact that the asphaltene particles are
This report intends to review the recent spaced far apart, so their interactions are weak.
progress in the factors that affect crude oil With increasing asphaltene concentration, the
viscosity, and aims to provide systematic viscosity started to deviate from linear and
knowledge about the techniques to reduce it. increased more sharply than in the diluted region
at the same temperature. This was due to the
increase in the quantity of asphaltene particles,
which increases their interactions due to
2. THE INFLUENCE OF COMPOSITION ON presenting a closer spacing than in the diluted
CRUDE OIL VISCOSITY region. After the middle region, the relative
viscosity increased more rapidly with an increase in
According to some authors (Yudin et al., 1998; asphaltene concentration, becoming the most
Fenistein et al., 1998; Sheu et al., 1991a; Acevedo evident tendency. Besides this, the separation of
et al., 1999), crude oils can be divided into non- the relative viscosity at different temperatures is
colloidal liquids, maltenes, and asphaltenes; the an indication of the stronger influence of
last being a dark brown powder that can temperature in this region.
agglomerate and increase the oil viscosity.
Luo and Gu (2005) also studied the effect of
In 2001, Hénaut studied the influence of asphaltene concentration on the viscosity of
asphaltene concentration on the viscosity of heavy reconstituted heavy oil samples at different
crudes. The tests were conducted in maltene

117
 BRAZILIAN JOURNAL OF PETROLEUM AND GAS | v. 11 n. 2 | p. 115-130 | 2017 | ISSN 1982-0593

temperatures. The viscosity of the reconstituted Hasan et al. (2010), studied different viscosity
heavy oil sample with 14.5 % by weight of reduction techniques in a heavy oil sample, with
asphaltenes was 23 199 cP at 23.9 °C, while that of the main objective of investigating the rheological
the reconstituted sample without asphaltenes (i.e., properties of the treated oil samples. The first and
only maltenes) was only 767 cP. According to the second techniques consisted of mixing the heavy
authors, this means that the high viscosity of the oil with alcohol and light oil, respectively, at
heavy oil tested was caused mainly by the different temperatures. The viscosity results of the
asphaltenes, and the viscosity increased sharply mixtures of heavy crude with 10% and 20% alcohol
when the asphaltenes started to flocculate. showed that these fluids had a similar rheological
behavior to the pure oil, but the viscosity values
2.1 Methods for reducing crude oil declined drastically, from 10 000 to 2 000 cP
viscosity (system with 10% alcohol) and from 10 000 to 9
500 cP (system with 20% alcohol). According to the
Historically, the demand for heavy and extra- authors, the alcohol acted as a diluent and the
heavy crudes has been low because their high viscosity declined due to the interactions of the
viscosity and complex composition make them hydroxyl groups with some functional groups
difficult and costly to extract, transport and refine. present in the asphaltenes. The second set of
Overcoming these challenges requires significant experiments involved mixing this oil with a light oil
technological advances. Different methods have sample, having viscosity of around 300 cP. The
been used or studied to reduce the viscosity of objective was to obtain an oil sample with lower
heavy and extra-heavy oils and thus improve their viscosity and density to enable transport through
flow through pipelines. Among these methods are: pipelines. The samples containing alcohol and light
the dilution with light oils or alcohols, heating of petroleum were prepared simply by mixing these
production lines or the oil itself, use of emulsion components with the heavy oil. The results
viscosity reducers, viscosity reducing additives of obtained with 10% and 20% light oil showed that
the oil in aqueous surfactant solution (Azodi & these fluids had a rheological behavior similar to
Nazar, 2013; Sanchez & Zakin, 1994). The current that of the pure heavy oil. The viscosity fell from 10
status of these techniques is reviewed below. 000 to 1 200 cP for the mixture with 10% light oil
and from 10 000 to 350 cP for the 20% light oil
2.1.1 Dilution of crude oil with light oils mixture (which was 26 times lower than the
or alcohols viscosity of the pure oil). The authors concluded
that this technique presented better results that
Dilution is one of the oldest and most popular the other two, since it was possible to obtain
methods to reduce the viscosity of heavy crudes. viscosity of 350 cP by adding 20% light oil to the
This technique consists of adding lighter liquid heavy crude.
hydrocarbons to the heavy oil. This is mainly used
to facilitate passage in pipelines. A solvent in the Hénaut et al. (2007) investigated the use of
proportion of 20-30% is often sufficient to avoid dimethyl ether (DME) as solvent to adjust the
high-pressure drops or the need for high viscosity and reduce pressure during transport. A
temperatures. Besides this, the dilution method major advantage of using this process is that the
can facilitate dehydration and desalinization of recovery of DME at the refinery is easier than for
these oils. That technology is the solution used other solvents.
most frequently for this purpose, but it can require
large investments for pumping and pipeline Alcohols are also being studied as solvents,
equipment due to the increased volume carried especially pentan-1-ol, which is much more
and the need to separate the solvent from the oil effective in reducing the viscosity of heavy crude
at some points (Martinez-Palou et al., 2011). than kerosene, due to the interactions generated
by the hydrogen bonds of the hydroxyl groups with
Yaghi and Al-Bemani (2002) observed that a the asphaltenes. High polarity or high degree of
mixture of heavy and light oils in a proportion of hydrogen bonding of the solvent produces greater
7:3 had viscosity of 1000 and 300 cP at reduction of the viscosity of crude oil. However,
temperatures of 30 and 50 °C, respectively, versus solvents with many hydrogen bonds generally are
15 000 cP at 20 °C for the initial heavy oil. more viscous than the hydrocarbons. Only polar

118
 BRAZILIAN JOURNAL OF PETROLEUM AND GAS | v. 11 n. 2 | p. 115-130 | 2017 | ISSN 1982-0593

solvents with few hydrogen bonds cause a 2.1.3 Mixtures with chemical viscosity-
significant reduction in the viscosity of crude oil reducing additives
(Plasencia et al., 2013).
Xie et al. (2001) investigated the effects of oil-
Furthermore, the dilution option faces some based and water-based chemicals. They found that
challenges, since any change in the oil’s the oil-based additive studied was a good viscosity
composition can affect the necessary oil/solvent reducer for crude oils with low or medium
proportion. Naphtha or light oils are interesting viscosity. Nevertheless, they found that water-
alternatives due to their high API gravity and their based additives were very good viscosity reducers
efficiency in diluting heavy oils. However, the for crude oil with high viscosity.
mixture can alter the stability of the asphaltenes
and cause them to flocculate and precipitate, in Several studies have utilized chemical additives
turn, blocking gas pipelines. Further studies are as viscosity reducers in crude oil applications, in
necessary to understand the aggregation and particular to enhance heavy crude oil recovery
flocculation of asphaltenes as well as the (Kuzmic et al., 2008; Soni et al., 2010).
crystallization and deposition of waxes (Martinez-
Palou et al., 2011). Chemical additives are highly selective, meaning
that many additives lack effectiveness for a
From an economic standpoint, the cost of the particular crude oil. To choose or develop the best
light fractions used as solvents may not be offset additive requires knowing the composition of the
by the higher value of the treated heavy oil. This oil in question. For example, some very viscous
requires careful economic analysis of the heavy heavy oils from Mexico contain high concentrations
and light oils involved in the process. of asphaltenes (> 8% by weight), low paraffin
levels, and appreciable quantities of sulfur (> 1.9%
2.1.2 Heating of production lines or the by weight), nickel, and vanadium (Castro &
crude oil Vazquez, 2009).

Heating is the second most commonly used Castro et al. (2011) studied the effect of
method to reduce the viscosity of heavy oils carried composition and molar mass of six
through pipes. The basis of this method is that thermopolymers prepared from styrene (S), n-butyl
viscosity declines with rising temperature, making acrylate (BuA), and vinyl acetate (VA) on the
it easier to pump oil. It is therefore important to apparent viscosity of a heavy oil from the Gulf of
heat the oil to a temperature at which the viscosity Mexico. The oil had the following physical
is substantially reduced. The principle is to characteristics: API density = 15.82; water content
preserve the high temperature at which the oil is = 0.10%; kinematic viscosity at 25 °C = 2984.97
extracted by insulating pipes. Insulation options mm2 s-1; and asphaltenes content = 19.92%. The
include burying traditional pipelines to preserve thermopolymer solutions were prepared at 20%
heat. However, external heating is almost always m/m in toluene and were applied in the oil at a
necessary due to heat losses caused by the slow dosage of 1000 ppm.
flow. This requires reheating at pumping stations
through direct heaters. Besides this, traditional The efficiency of a polymer as a viscosity
pipelines can be operated with low vapor pressure, reducer of dehydrated heavy oils depends mainly
near environmental pressure, to maximize their on the thermodynamic affinity of the segments of
capacity (Ghannam & Esmail, 2006). its chain with the oil’s components (saturates,
resins, asphaltenes, and aromatics). The authors
A disadvantage of the heating of production observed that all the thermopolymers reduced the
lines is the high costs for long distance operations. apparent viscosity of the crude oil and that this
This is aggravated in offshore operations because reduction depended on the molar mass of the
of the cooling exerted by the seawater and the thermopolymer used as the additive.
difficulty of installing and maintaining submerged
pumping and heating stations (Hansan et al., Polymer samples with mutually similar
2010). compositions, but very different molecular masses,
exhibited practically the same efficiency as
viscosity reducers of heavy oil. The same behavior

119
 BRAZILIAN JOURNAL OF PETROLEUM AND GAS | v. 11 n. 2 | p. 115-130 | 2017 | ISSN 1982-0593

was observed when comparing the curves of the oil pipelines. Crude oil emulsions have a pseudoplastic
containing samples with different molar masses or shear-thinning behavior, meaning that the
and different compositions, which exhibited the viscosity declines as the shear rate increases. The
same rheological behavior after a shear rate of main difficulties of using this technique are the
2 s-1. Polymers with composition rich in S were the choice and cost of the surfactants used in the
most efficient as viscosity reducers. Analysis of the emulsion. Not only must the surfactant be able to
influence of the composition of the stabilize the emulsion during transport, the cost of
thermopolymers used as viscosity reducers on the separating the oil and water phases when the fluid
rheological behavior of the crude oil revealed that reaches its destination must not be too high
the higher the S content was, the greater the (Langevin et al., 2004; Sullivan & Kilpatrick, 2002).
viscosity reduction was, regardless of the polymer’s
molar mass. Many studies have reported the rheological
characterization of emulsions (Dan & Jing, 2006;
The efficiency of these thermopolymers as flow Farah et al., 2005). In a recent study, Hoshyargar
enhancers can be explained by the following and Ashrafizadehs (2013) found that the rheology
structural effects: (1) the presence of S allows of crude oil emulsions is affected by temperature,
better interactions with the asphaltenes, resins, Na2CO3 concentration (component used to stabilize
and other compounds due to its aromatic nature; the emulsion), NaCl concentration (salinity of
(2) the presence of VA gives a polar functionality to continuous phase), oil volume fraction (ɸ), and
the thermopolymer’s structure, favoring the number of homogenizer revolutions. The
attraction forces between additive and resins; and emulsification method resulted in a reduction of
(3) the presence of BuA promotes interactions crude oil viscosity by 90-99%. The predictions were
between the thermopolymers and the paraffins in made using the Herschel-Bulkley model in all cases.
the crude oil. The optimum flow conditions were reported as T =
25 °C, Na2CO3 concentration = 2,000 ppm, NaCl
Junaki et al. (2012) developed an ionic additive concentration = 5,000 ppm, ɸ = 0.7, and revolution
named IRAN91. The effectiveness of this additive in = 22,500.
reducing the viscosity of heavy oil was investigated
by using samples from the Marun oil field, Hasan et al. (2010) investigated the dilution of a
Bangestan reservoir. They found that the presence viscous crude oil as described earlier. They also
of the ionic additive resulted in a reduction of prepared an emulsion with crude oil as the
heavy oil viscosity up to 64%. dispersed phase, and an aqueous solution of a
commercial nonionic surfactant (Triton X-100 – 4
2.1.4 Formation of heavy crude oil octylphenol polyethoxylate) as the continuous
emulsions in water (O/W) phase, at a concentration of 0.1%. The emulsions
were prepared by adding the aqueous phase to the
Oil in water (O/W) emulsions can be formed heavy oil under stirring. The initial tests of viscosity
containing high oil percentages, sufficient to make versus shear rate for the crude oil at different
the process economically attractive, especially temperatures showed a pseudoplastic behavior.
because the diluent (water) is inexpensive. The The authors also noted that the difference in
viscosity of these emulsions is much lower than viscosity of these samples was greater at lower
that of the crude oil, relatively independent of the shear rates. The explanation given was that, as the
oil type used (Hansan et al., 2010). temperature increases, the heavy oil fractions with
high molar mass, such as asphaltenes, resins and
Surfactants are used as emulsifiers by stabilizing waxes, among others, do not have a chance to
the droplets of the dispersed phase within the agglomerate and form aggregates, so the oil’s
continuous phase to avoid their coalescence, viscosity is reduced. Two different aqueous
generating stable O/W emulsions with low solution concentrations of the surfactant were
interfacial tensions. By using surfactants to form an tested (10% and 20% v/v), in the temperature
O/W emulsion, the crude oil can be suspended as range of 25 – 75 °C. At 25 °C, the viscosity values of
micro droplets stabilized in a continuous aqueous the emulsions were lower than those of the crude
phase, thus, reducing the apparent viscosity. This oil, by 20% for the emulsion prepared with 10%
can be a good alternative compared to using aqueous solution and by 35% for the 20% solution.
diluents or heating for transporting these oils in

120
 BRAZILIAN JOURNAL OF PETROLEUM AND GAS | v. 11 n. 2 | p. 115-130 | 2017 | ISSN 1982-0593

The authors also observed two distinct regions of lifting phase is the moment when the fluid is
the curves obtained by plotting viscosity in function subjected to shear forces and pressures generated,
of shear rate: the first region, at a shear rate of up for example, by electrical submersible pumps or
to 500 s-1, where the viscosity of the emulsions had gas lift (Allenson et al., 2011).
strong pseudoplastic behavior; and the second
region, with shear rate of 500 s-1, where the Researchers in the 1970s (Haeght & Ellingsen,
emulsions behaved as Newtonian fluids. For high 1977; Wang & Huang, 1979) concluded that the
shear rates, all the curves clustered together, primary reason leading to emulsion formation was
forming a “master” curve, indicating that the the increase in turbulence or mixing energy.
viscosity became independent of the shear rate According to Schubert and Armbruster et al., in
and temperature. 1992, turbulence plays an important role in the
distribution and mixing of the phases during
Langevin et al. (2004) concluded that emulsion pipeline flow of water/oil systems.
behavior is controlled largely by the properties of
the adsorbed layers that stabilize the crude oil- The presence of emulsions during production of
water surface, and that emulsions with small size crude oil is one of the main factors that influence
of dispersed droplets and a narrow particle size its viscosity. Pure hydrocarbons are not able to
distribution have high viscosities and large form stable emulsions with water or brine.
residence time. However, due to the presence of natural
surfactants in the oil and the shear that occurs
Indeed, bitumen (highly viscous crude oil) during the extraction process, there is a tendency
droplets in water have the same effect as other for emulsions to form. Among these surfactants are
types of emulsions. This is because the viscosities asphaltenes, resins, and naphthenic acids, which
of bitumen and water are very far apart. At room are amphiphilic molecules that have an interfacial
temperature, the viscosities of bitumen and water activity. These compounds contain atoms of
are 7 000 000 cP and 1 cP, respectively. Other oxygen, nitrogen and sulfur in the form of
researchers support their findings, suggesting that carboxylic acid, phenol, amide, alcohol, amine, and
dispersing bitumen in water is an efficient way to mercaptan, among others (Allenson et al. 2011).
reduce the viscosity of fluids. Similar to crude oil The molecules have a wide range of chemical
emulsions, bitumen emulsions show shear thinning structures, molar masses and hydrophilic-lipophilic
non-Newtonian behavior. The influence of shear balance (HLB) values, and can interact and/or
rate on the viscosity increases as the concentration reorganize at the water-oil interface. Petroleum
of the dispersed phase increases (Sullivan & emulsions can also contain solids and gases (Fingas
Kilpatrick, 2002; Nunez et al., 2000). & Fieldhouse, 2009; Maia Filho et al., 2012).

Making oil in water emulsion markedly Under most oil production conditions, it is
diminishes oil viscosity. However, restoration of common to observe emulsions having water as the
original hydrocarbon by breaking the emulsion is a discontinuous (or internal) suspended phase and
subject of controversy (Martinez-Palou et al., oil as the continuous (or external) phase (i.e.,
2011). In addition, choosing the best surfactant for water-in-oil or W/O emulsions). It is also possible
a given oil and aqueous phase depends on their for oil-in-water water (O/W) emulsions to form, or
composition. Most importantly, surfactants are even more complex ones composed of oil in water
expensive materials and economic considerations in oil (O/W/O), called multiple emulsions (Sefton &
may pose limitations on the amount of surfactant Sinton, 2010).
used (Sheng, 2015).
These emulsions cause a considerable increase
in the apparent viscosity and pseudoplastic
behavior of crude oil, meaning that the viscosity
3. THE INFLUENCE OF EMULSION declines with the shear rate. Due to difference of
FORMATION ON CRUDE OIL VISCOSITY the internal microstructures, it is hard to predict
the viscosities of these emulsions and their
At various times during oil production, rheological properties with any precision (Wang et
mechanical energy is transmitted to the production al., 2013).
fluids, causing the formation of emulsions. The

121
 BRAZILIAN JOURNAL OF PETROLEUM AND GAS | v. 11 n. 2 | p. 115-130 | 2017 | ISSN 1982-0593

Ariffin et al. (2016) investigated the rheological extracted, until a maximum value is reached. After
behavior of light crude oil emulsion, particularly reaching this high point, the viscosity starts to
the viscosity behavior. Experimental results decline if more water is added to the system. This
indicate that the viscosity of the emulsion drop is due mainly to the presence of free water
decreases from 0.819 to 0.0466 Pa.s as the and/or the formation of inverse emulsions (O/W).
temperature increases from 20 to 90 ° C. In The point at which this phenomenon occurs is
addition, increasing the water volume fraction called the phase inversion point (PIP) (Allenson et
from 20% to 40% results in higher viscosity and al., 2011).
characterized greater elasticity. The emulsion
viscosities were significantly influenced by the Good knowledge of the oil’s composition is
shear rate, temperature, and water content. necessary to take the proper measures to control
the formation of emulsions in all production phases
Li et al. (2015) performed an experimental (Langevin et al., 2004). Laboratory studies have
study of the influences of the temperature and indicated that the quantity of water that can be
water fraction on the elastic modulus, loss emulsified depends on the crude oil’s composition.
modulus, and loss angle. Their studies revealed Crude oils can form emulsions with between 40 to
that, increasing the temperature or reducing the 70% brine before reaching the phase inversion
water fraction, the gel structure could be point (Allenson et al., 2011).
weakened. This is reflected by the presence of a
narrower linear viscoelastic region and lower Duan et al. (2010) studied the factors that
values of the elastic modulus and loss modulus. affect the PIP of emulsions obtained from three
heavy oil samples with different densities and
Besides increased oil viscosity, emulsions can viscosities. They found that, in general, the higher
cause other problems, such as corrosion and the density and viscosity of the heavy oil sample
deposition of salt in pipelines and refining was, the lower the PIP was. This occurred because
equipment, impairment of desalinization and the content of natural surfactants (such as
dehydration (processes applied before refining), asphaltenes, resins and organic acids) in heavier oil
higher transport and storage costs, and catalyst is higher, causing more surfactant molecules to
poisoning (Al-Yaari et al., 2015). adsorb at the oil-water interface, increasing the
thickness and strength of the film. The resulting
Various factors can contribute to the viscosity of conditions were more favorable to the dispersion
emulsions, such as oil viscosity, water viscosity, of water droplets.
water concentration, temperature, droplet size and
size distribution, quantity of solids in the oil, and Anisa and Nour (2010) produced W/O
shear rate. At low water cut, when the emulsions emulsions from three crude oils having different
are diluted, the hydrodynamic forces during characteristics of API gravity and viscosity. The
collision of the droplets govern the rheological objective of the study was to assess the effects of
behavior. As the water cut increases, meaning that temperature and effects of stirring speed to the
the emulsion system is more concentrated, flow viscosity and the average droplet diameter of W/O
resistance can be induced by the deformation and emulsions. The emulsions were prepared by adding
rearrangement of the structures of the network of water to a mixture of oil and a nonionic surfactant
thin liquid films between the droplets (Plasencia et at a concentration of 0.1%, under stirring at 1500
al., 2013). This flow resistance becomes more rpm for 5 minutes. The authors observed, by
frequent as the concentration of water rises, means of micrographs, that the system containing
caused by the presence of water in the formation the highest water concentration (50% v/v) had the
(which tends to rise as the well ages due to largest droplets (average diameter of 26.60 µm)
depletion of the oil) and/or injection of water to and these were nearer to each other with a more
increase pressure in the reservoir (Shecaira et al., fragile interfacial film, rendering the system
2002). unstable and thereby enhancing coalescence. The
droplets in the emulsion with the lowest water
The emulsion’s viscosity also depends on the content (20% v/v) had an average diameter of
quantity of water emulsified in the oil. The 20.76 µm, and were spaced further apart with
apparent viscosity of the emulsion increases when more rigid films, generating an unstable system.
the water percentage increases, as the fluid is

122
 BRAZILIAN JOURNAL OF PETROLEUM AND GAS | v. 11 n. 2 | p. 115-130 | 2017 | ISSN 1982-0593

Table 1. Classification of water-in-oil mixtures.

Mesostable W/O emulsions

Stable W/O (displays the properties Entrained water-in-oil Unstable water-in-oil
emulsions between stable and unstable (not characterized as
emulsion) emulsion)
- remains intact for at - remains unbroken for less - entrained water stayed - indicates oil samples
least four weeks than three days, and are as such condition for less that do not hold a
separated into water and free than one day significant amount of
- appears as a brown
oil in around one to three days water, even when water
or reddish semi-solid - water appeared as a
is present, it stays for a
material - appear as black or brown black liquid
very short period of time
liquid
- has an average - first day it has an
water content of - has an average water content average water content
about 80% and stays of about 70% and reduced to of about 40% and
about the same after around 30% after one week reduced to around 15%
a week after one week
- viscosity 6 – 23 000 cP
- viscosity 15 – 10 000 - viscosity 2 000 – 60 000
- density 0.84 – 0.98 g/mL
cP cP
- asphaltene-to-resin ratio 0.47
- density 0.85 – 0.97 - density 0.97 – 0.99
g/mL - apparent viscosity, 45 cP at g/mL
day of emulsion formed and 30
- asphaltene-to-resin - asphaltene-to-resin
cP a week later
ratio 0.74 ratio 0.62;
- apparent viscosity, 1 - apparent viscosity, 13
100 cP at day of cP on day of emulsion
emulsion formed and formed and 3 cP s a
1 500 cP a week later week later.

Finally, varying the temperature caused changes in Johnsen and Rønningsen (2003) conducted
the emulsion stability, observed by phase inversion experiments to study the viscosity of W/O
(changing to an O/W emulsion) or by breakdown of emulsions using different crude oil samples from
the emulsions (resulting in coalescence). They also the North Sea, ranging from light to heavy. The
concluded that the average droplet diameter of authors varied the temperature from 50 °C to 70
W/O emulsions depended greatly on the viscosity °C, flow speed from 0.7 m/s to 3 m/s, water cut
as well as the behavior of the emulsions, if they are from 0% to 90%, and saturation and pressure from
Newtonian or non-Newtonian. 12 bar to 100 bar. The results showed that
although the viscosity range of the samples was
According to researchers (Fingas & Fiellhouse, very large, the changes in the relative viscosity of
2003, 2004; Wong & Lim, 2015; Fingas, 2014), the W/O emulsions were very small for water cuts
water-in-oil mixtures can be divided or grouped up to 70%. In turn, for water cuts of 80% and 90%,
into four classes: stable water-in-oil emulsions, the relative viscosity changes were substantial.
mesostable water-in-oil emulsions, entrained
water, and unstable water-in-oil emulsions. The Farah et al. (2005) studied the effect of
states of water-in-oil can be assigned to four volumetric fractions of the dispersed phase,
classes by studying the stability, appearance, and temperature, and shear rate on the viscosity of
rheological behavior of different water-in-oil W/O emulsions. They used six types of crude oils,
samples (Table 1). with densities varying from 15 ° to 40 ° API, which
were tested at temperatures from 8 °C to 50 °C,
Characterization and properties of each type of with the disperse phase ranging from 0% to 40%
emulsion have to be understood fully so that the and the shear rate from 10 s-1 to 80 s-1. The results
type of emulsions, which are more relevant to the indicated a Newtonian fluid behavior for the
oil and gas industries, can be determined. emulsions analyzed at the higher temperatures and

123
 BRAZILIAN JOURNAL OF PETROLEUM AND GAS | v. 11 n. 2 | p. 115-130 | 2017 | ISSN 1982-0593

containing the largest dispersed phase reducers (EVRs) may be applied in the borehole.
concentrations. The lower viscosity makes the production process
more efficient because the crude oil flows more
Dan and Jing (2006) carried out experiments of easily (Husin et al., 2014).
the viscosity of seven sets of W/O emulsions
formed using light and heavy crude oils from EVRs belong to the class of chemicals that
different fields. The experimental conditions were promote water-oil separation. These chemicals
processing temperature of 60 °C for the heavy oils commonly are called demulsifiers. They are
and 30 °C for the light oils, water content ranging formulated specifically for down-hole injection
from 0% to 60%, and shear rates varying between through gas lift systems, capillary tubes or
15 s-1 and 600 s-1. The results showed that the W/O umbilicals in underwater operations. They are
emulsions obtained with the oil of different mixtures of oil-soluble polymers that have
densities behaved distinctly. The W/O emulsions interfacial activity, by interacting with the natural
formed using heavy oils showed non-Newtonian emulsifiers at the oil-water interface (Allenson et
behavior, i.e., variation of viscosity with time. In al., 2011).
contrast, the W/O emulsions formed with the light
oils presented Newtonian behavior, i.e., unchanged EVRs can be formed by poly(ethylene oxide)-b-
viscosity. poly(propylene oxide) block copolymers (PEO-PPO),
ethoxylated phenols, alcohols, ethoxylated amines,
Broboana and Balan (2007) analyzed the ethoxylated resins, nonyl ethoxylated phenols, and
rheological behavior of W/O emulsions, using an sulfonic acid salts. These chemical products have a
asphaltic oil with water concentration of 30% and a range of properties. Typically, they have a strong
paraffinic oil with water content of 6%, both attraction for the oil-water interface, with the
obtained from Romanian fields. The experiments ability to destabilize the protective film around the
were performed under a temperature of 5 °C, at droplets. They also have the ability to act as
atmospheric pressure and shear rate ranging from wetting agents, changing the contact angle of
1 s-1 to 1 000 s-1, using two rheometers (Anton Paar solids; and the ability to act as flocculants,
Physica models MC 300 and MC 1). Both samples promoting film drainage, thinning the interfacial
presented non-Newtonian fluid behavior film and inducing changes in the rheological
(pseudoplasticity). properties, such as reduction of interfacial viscosity
and elasticity (Ortiz et al., 2010; Daniel-David et
Kumar and Mahto (2016) investigated the al., 2005; Follotec et al., 2010).
rheological behavior of W/O emulsions of a heavy
crude oil sampled from a western oil field in India. The mechanism of interaction between EVRs
The field was highly asphaltinic and waxy in nature, and emulsifiers at the water-oil interface remains
and it was potentially rich in resin fractions. unclear. Nevertheless, the general effect of this
Development of O/W emulsions caused interaction is to weaken the film around the
considerable decrease in viscosity even at higher oil droplets, allowing them to coalesce and form larger
content, enabling emulsions to be easily droplets (Ramalho et al., 2010).
transported through the pipes. The pour point of
the heavy oil after emulsification was decreased Allenson et al. (2011) showed that EVRs
greatly, permitting the oil to be transported weaken the film around the water droplets, making
through a pipeline under extremely low it easier for them to join into larger droplets. The
temperature conditions offshore. The addition of result is a decline in drag forces, because of the
more surfactant in the aqueous phase decreased reduction in the total surface area of the droplets
the droplet size of the emulsion and increased and the number of interactions between them,
stability, although on the other hand it increased which can transfer mechanical shear through the
slightly the viscosity of the emulsion. bulk phase of the fluid. The reduction in drag
lowers the apparent viscosity.
3.1 Effect of emulsion viscosity reducers
The effect of lowering the viscosity of an
(EVRs) emulsion by adding an EVR is illustrated in Figure 1.
To overcome problems caused by emulsions, When the EVR is added to the emulsion, it migrates
chemical products called emulsion viscosity to the oil-water interface due to the interfacial

124
 BRAZILIAN JOURNAL OF PETROLEUM AND GAS | v. 11 n. 2 | p. 115-130 | 2017 | ISSN 1982-0593

Increase in droplet size

Decrease of viscosity with larger droplet size

Figure 1. The addition of an EVR causes an increase in the size of the water droplets and reduction of the
viscosity of emulsions.

activity, where it can interact or compete with the With respect to the chemical additives used,
natural emulsifiers (such as asphaltenes). The Zhang et al. (2006) observed efficiencies near 95%
water droplets start to aggregate and coalesce into for PEO–PPO–PEO triblock copolymers with
larger droplets. Eventually, these droplets become different molar masses and PEO concentrations in
too large and combine to form free water demulsifying crude oil emulsions.
(continuous phase). During this process, the
apparent viscosity continues to decline. Some studies (Wu & Xu, 2005; Xu et al., 2005;
Zhang et al., 2004a,b) have shown that the
3.2 Application of EVRs based on polymers demulsification performance of PEO-PPO block
copolymers is correlated with the quantity of
The most suitable EVR for particular emulsion ethylene oxide (EO) and propylene oxide (PO) units
can be determined by bottle tests. In this test, in their structures.
different chemical products at different
concentrations can be analyzed. This is important Xu et al. (2005) also reported that the
because different chemicals generate varied water demulsification efficiency of commercial PEO–PPO
droplet characteristics. triblock copolymers was higher for the copolymers
with greater EO concentrations, since the PEO
Allenson et al. (2011) observed that chemical fraction in their structure forms the hydrophilic
EVRs with fast water drop activity, which promote part of the demulsifier. They observed 100%
faster breakdown of W/O emulsions, are normally efficiency of demulsifiers containing 80% EO
considered good candidates for top-side treatment groups, but the one containing 10% EO units had
(demulsification treatment at the surface), but they no demulsification effect. The authors also studied
can also have a negative effect when injected in the effect of isomerism of PEO-PPO triblock
deep wells with addition of gas lift. This happens copolymers. These were called sequential (PEO-
because this type of EVR reduces the apparent PPO-PEO) and non-sequential (PPO-PEO-PPO). The
viscosity of the fluid produced, but at the same different positions of the EO and PO groups
time provokes premature separation of the present in the structures changed the demulsifier’s
emulsion, resulting in multi-phase fluids hydrophilic-lipophilic balance, interfacial properties
(water/oil/gas) that can clog production lines. and demulsification efficiency. For those with
Combination of bottle tests with rheological tests sequential structure, the two EO blocks at the ends
can identify the best EVR. were adsorbed in the water droplets, while the
lipophilic part (PO) became oriented toward the oil

125
 BRAZILIAN JOURNAL OF PETROLEUM AND GAS | v. 11 n. 2 | p. 115-130 | 2017 | ISSN 1982-0593

phase, promoting weak steric repulsion, resulting 5. REFERENCES

in destabilization of the emulsion. The non-
sequential copolymers (PPO-PEO-PPO) maintained Abdel-Raouf, M. E.-S. Factors Affecting the
the separation of the dispersed water droplets, Stability of Crude Oil Emulsions. Chapter 10. In:
retarding their coalescence. Abdel-Raouf, M. E.-S. Crude Oil Emulsions-
Composition Stability and Characterization.
Croatia: INTECH, ISBN 978-953-51-0220-5 2012.
Available at:
4. FINAL CONSIDERATIONS <https://www.intechopen.com/books/crude-oil-
emulsions-composition-stability-and-
The increasing production of heavy and extra-
characterization/factors-affecting-the-stability-of-
heavy crude oils in North America, South America
crude-oil-emulsions>.
and Eastern Asia, more technological innovation as
well as research and development will be needed Acevedo, S.; Ranaudo, M.A.; Pereira, J.C.;
to generate specific solutions for crude oil Castillo, J.; Fernandez, A.; Perez, P.; Caetano, M.
transportation. These crude oils have high viscosity Thermo-optical studies of asphaltene solutions:
due the presence of components with high evidence for solvent–solute aggregate formation
molecular weight. Furthermore, emulsified oils also Fuel, v. 78(9), p. 997-1003, 1999.
have higher apparent viscosity, restricting flows https://doi.org/10.1016/S0016-2361(99)00027-7
through pipelines and impeding production.
Allenson, S. J.; Yen, A. T.; Lang, F. Application of
In this review, technologies and methods to Emulsion Viscosity Reducers to Lower Produced
facilitate the transport of heavy and extra-heavy Fluid Viscosity. Offshore Technology Conference,
crude oils and emulsified oils from production sites OTC-22443-MS, 4-6 October, Rio de Janeiro, Brazil,
to processing facilities were presented. The 2011. https://doi.org/10.4043/22443-ms
technologies currently in use, as well as new
methods for this purpose, are based mainly on Al-Yaari, M.; Hussein, I. A.; Al-Sarkhi, A.; Abbad,
reduction of crude oil viscosity. These technologies M., Chang, F. Effect of water salinity on surfactant-
promote many advantages, such as better flow in stabilized water–oil emulsions flow characteristics.
pipes, lower production costs, better equipment Experimental Termal and Fluid Science, v.64, p.
reliability and availability, and easier 54-61, 2015.
processing/refining. https://doi.org/10.1016/j.expthermflusci.2015.02.001

One solution to enhance the flow rate is to Anisa, A. N. I.; Nour, A. H. Affect of Viscosity and
reduce the apparent viscosity by using emulsion Droplet Diameter on water-in-oil (w/o) Emulsions:
viscosity reducers (EVRs). This application relies on An Experimental Study. International Scholarly and
thorough testing and correct data interpretation to Scientific Research & Innovation, v. 4(2), p. 213-
provide the correct chemical selection. The use of 216, 2010. https://doi.org/10.2118/79496-ms
this technology has been demonstrated in several
Argiller, J.-F.; Coustet, C.; Henaut, I. Heavy oil
field applications in different locations around the
rheology as a function of asphaltene and resin
world. Success can be measured by a variety of
content and temperature. SPE International
field parameters including flow rates, pump
Thermal Operations and Heavy Oil Symposium
temperatures, and pressures.
and International Horizontal Well Technology
Conference, SPE-79496-MS, 4-7 November,
ACKNOWLEDGMENTS Calgary, Alberta, Canada 2002.
https://doi.org/10.2118/79496-ms
The authors of this review would like to thank
Ariffin, T.S.T.; Yahya, E.; Husin, H. The rheology
Petrobras, the National Council for Scientific and
of light crude oil and water-in-oil-emulsion.
Technological Development (CNPq), the Office for
Procedia Engineering, v.148, p. 1149-1155, 2016.
Improvement of University Personnel (CAPES), and
https://doi.org/10.1016/j.proeng.2016.06.614
the Rio de Janeiro State Research Support
Foundation (FAPERJ) for the funding provided for
this research.

126
 BRAZILIAN JOURNAL OF PETROLEUM AND GAS | v. 11 n. 2 | p. 115-130 | 2017 | ISSN 1982-0593

Ashoori, S.; Sharifi, M.; Masoumi, M.; Salehi, Farah, M. A.; Oliveira, R. C.; Caldas, J. N.;
M.M. The relationship between SARA fractions and Rajagopal, K. Viscosity of water-in-oil emulsions:
crude oil stability. Egyption Journal of Petroleum, Variation with temperature and water volume
v. 26(1), p. 209-213, 2017. fraction. Journal of Petroleum Science and
https://doi.org/10.1016/j.ejpe.2016.04.002 Engineering, v. 48 (3-4), p. 169-184, 2005.
https://doi.org/10.1016/j.petrol.2005.06.014
Asomanung, S. Test methods for determining
asphaltene stability in crude oils. Petroleum Fenistein, D.; Barré, L.; Broseta, D.; Espinat, D.;
Science and Technology, v.21, p. 581-590, 2003. Livet, A.; Roux, J.-N.; Scarsella, M. Viscosimetric
https://doi.org/10.1081/LFT-120018540 and neutron scattering study of asphaltene
aggregates in mixed toluene/heptane solvents.
Azodi, M.; Nazar. A.R.S. An experimental study Langmuir, v. 14(5), p. 1013-1020, 1998.
on factors affecting the heavy crude oil in water https://doi.org/10.1021/la9709148
emulsions viscosity. Journal of Petroleum Science
Fingas, M. F. Water‐in‐oil emulsions: Formation
and Engineering, v.106, p.1-8, 2013.
and prediction. Journal of Petroleum Science and
https://doi.org/10.1016/j.petrol.2013.04.002
Engineering, v. 3(1), p. 38-49, 2014.
Broboana, D.; Balan, C. Investigations of the https://doi.org/10.1002/9781118989982.ch8
rheology of water-in-crude oil emulsions. Scientific Fingas, M.; Fieldhlur, B. Formation of water-in-
Bulletin - University Politehnica of Bucharest, oil emulsions and application to oil spill modelling.
Series B, v. 69(3), p. 35-50, 2007. Journal of Hazardous Materials, v. 107(1-2), p. 37-
50, 2004.
Castro, L. V.; Flores, E.A.; Vazquez, F. https://doi.org/10.1016/j.jhazmat.2003.11.008
Terpolymers as flow improvers for Mexican crude
oils. Energy & Fuels, v. 25(2), p. 539-544, 2011. Fingas, M.; Fieldhouse, B. Studies on crude oil
https://doi.org/10.1021/ef101074m and petroleum product emulsions: Water
resolution and rheology. Colloids and Surfaces A:
Castro, L. V.; Vazquez, F. Fractionation and
Physicochemical and Engineering Aspects, v.
characterization of Mexican crude oils. Energy &
333(1-3), p. 67-81, 2009.
Fuels, v.23, p. 1603-1609, 2009. https://doi.org/10.1016/j.colsurfa.2008.09.029
https://doi.org/10.1021/ef8008508
Fingas, M.; Fielhouse, B. Studies of the
Dan, D.; Jing, G. Apparent viscosity prediction of
formation process of water-in-oil emulsions.
non-Newtonian water-in-crude oil emulsions.
Marine Poluation Bulletin, v. 47(9-12), p. 369-396,
Journal of Petroleum Science and Engineering, v.
2003. https://doi.org/10.1016/S0025-326X(03)00212-1
53 (1-2), p. 113-122, 2006.
https://doi.org/10.1016/j.petrol.2006.04.003 Follotec, A. L.; Pezron, I.; Noik, C.; Dalmazzone,
C.; Komunjer, L. M. Triblock copolymers as
Daniel-David, D.; Pezron, I.; Dalmazone, C.;
destabilizers of water-in-crude oil emulsions.
Noik, C.; Clausse, D.; Komunjer, R. Elastic
Colloids and Surfaces A: Physicochemical
properties of crude oil/water interface in presence
Engineering Aspects, v.365 (1-3), p. 162-170, 2010.
of polymeric emulsion breakers. Colloids and
https://doi.org/10.1016/j.colsurfa.2010.02.025
Surface: A Physicochemical Engineering Aspects, v.
270-271, p. 257-262, 2005. Garcia-Olvera, G.; Reilly, T. M.; Lehmann, T. E.;
https://doi.org/10.1016/j.colsurfa.2005.06.010 Alvarado, V. Effects of asphaltenes and organic
acids on crude oil-brine interfacial visco-elasticity
Duan, L.; Jing, J.; Wang, J. Study on phase
and oil recovery in low-salinity waterflooding. Fuel,
inversion characteristics of heavy oil emulsions.
v.185, p. 151-163, 2016.
The Twentieth International Offshore and Polar
https://doi.org/10.1016/j.fuel.2016.07.104
Engineering Conference, ISOPE-I-10-364, 20-25
June, p. 83-87, 2010. Ghanavati, G.; Shojaei, M.-J.; Ramazani, A.S.A.
Effects of asphaltene content and temperature on
Dusseault, M. B.; Shafiei, A. Oil sands. Countries
viscosity of Iranian heavy crude oil: Experimental
OotPE. World oil outlook., 2011. Available at:
and modeling study. Energy Fuels, v. 27(12), p.
<http://onlinelibrary.wiley.com/doi/10.1002/1435
7217-7232, 2013. https://doi.org/10.1021/ef400776h
6007.a26_129.pub2/abstract>.

127
 BRAZILIAN JOURNAL OF PETROLEUM AND GAS | v. 11 n. 2 | p. 115-130 | 2017 | ISSN 1982-0593

Ghannam, M. T.; Esmail, N. Flow enhancement Kelesoglus, S.; Pettersen, B. H Sjoblom, J. Flow
of medium-viscosity crude oil. Petroleum Science properties of water-in-North Sea heavy crude oil
and Technology, v.24, p. 985-999, 2006. emulsions. Journal of Petroleum Science and
https://doi.org/10.1081/LFT-200048166 Engineering, v.100, p. 14 -23, 2012.
https://doi.org/10.1016/j.petrol.2012.11.006
Guo, K.; Li, H.; Yu, Z. In-situ heavy and extra-
heavy oil recovery: A review. Fuel, v. 185, p. 886- Kessick, M.A.; Denis,G.E.S. Pipeline
902, 2016. https://doi.org/10.1016/j.fuel.2016.08.047 Transportation of Heavy Crude Oil. US Patent
Haeght. T.; Ellingsen, T. The effect of Breaking 4,343,323, August 10, 1982. Available at:
Waves On Oil Spills: 1. Emulsification of crude Oil at <https://docs.google.com/viewer?url=patentimage
Sea, Publication of SINTEF, The Foundation of s.storage.googleapis.com/pdfs/US4343323.pdf>.
Scientific and Industrial Research at The University
of Trondheim, Norway, p. 23, 1977. Available at: Kumar, S.; Mahto, V. Emulsification of Indian
<https://www.sintef.no/globalassets/project/jip_oil_in_i heavy crude oil in water for its efficient
ce/dokumenter/publications/jip-rep-no-11-dispersant- transportation through offshore pipelines.
effectiveness-in-arctic-conditions-150207.pdf>. Chemical Engineering Research and Design, v. 115,
p. 34-43, 2016.
Hasan, S. W.; Ghannam, M. T.; Esmail, N. Heavy https://doi.org/10.1016/j.cherd.2016.09.017
crude oil viscosity reduction and rheology for
pipeline transportation. Fuel, v. 89(5), p. 1095- Kuzmic, A. E.; Radosevic, M.; Bogdanic, G.; Srica,
1100, 2010. https://doi.org/10.1016/j.fuel.2009.12.021 V.; Vukovic, R. Studies on the influence of long
chain acrylic esters polymers with polar monomers
Henaut, I.; Barre, L.; Argillier,J. F.; Brucy, F.;
as crude oil flow improver additives. Fuel, v. 87(13-
Bouchar, R. SPE International Symposium on
14), p. 2943-2950, 2008.
Oilfield Chemistry, SPE-65020-MS, 13-16 February,
https://doi.org/10.1016/j.fuel.2008.04.006
Houston, Texas, 2001.
Henaut, I.; Forestiere, A.; Heraud, J. P.; Argillier, Langevin, D.; Poteau, S.; Henaut, I.; Argillier, J. F.
J. F. Method of Optimizing Heavy Crude Crude oil emulsion properties and their application
Transportation by Incorporation Under Pressure of to heavy oil transportation. Oil & Gas Science and
Dimethyl Ether. US Patent Application, 2007. Technology, v. 59, p. 511-521, 2004.
Available at: https://doi.org/10.2516/ogst:2004036
<https://www.google.ch/patents/US20070295642>. Li, H.Y.; Zhang, J.J.; Song, C.F.; Sun, G.Y. Journal
Hoshyargar, V.; Ashafizadeh, S. N. Optimization of Petroleum Science and Engineering, v.135, p.
of flow parameters of heavy crude oil-in-water 476-483, 2015.
https://doi.org/10.1016/j.petrol.2015.10.010
emulsions through pipelines. Industrial and
Engineering Chemistry Research, v. 52(4), p. 1600- Luo, P.; Gu, Y. Effects of asphaltene content and
1611, 2013. https://doi.org/10.1021/ie302993m solvent concentration on heavy oil viscosity. SPE
International Thermal Operations and Heavy Oil
Husin, H.; Azizi, A.; Husna, A. An overview of
Symposium, SPE-97778-MS, 1-3 November,
viscosity reducers in heavy crude oil production.
Calgary, Alberta, Canada, 2005.
Chemeca, p. 1246-1253, 2014.
https://doi.org/10.2118/97778-ms
Johsen, E. E.; Ronningsen, H. P. Viscosity of ‘live’
Maia Filho, D.C.; Ramalho, J. B. V. S.; Spinelli, L.
water-in-crude-oil emulsions: experimental work
S.; Lucas, E. F. Aging of water-in-crude oil
and validation of correlations. Journal of
emulsions: Effect on water content, droplet size
Petroleum Science and Engineering, v. 38(1-2), p.
distribution, dynamic viscosity and stability.
23-36, 2003.
Colloids and Surfaces A: Physicochemical
https://doi.org/10.1016/S0920-4105(03)00020-2
Engineering Aspects, v. 396, p. 208-212, 2012.
Junaki, E.; Ghanaatian, S.; Zargar, G. A new https://doi.org/10.1016/j.colsurfa.2011.12.076
approach to simultaneously enhancing heavy oil
recovery and hindering asphaltene precipitation.
Iranian Journal of Oil & Gas Science and
Technology, v. 1(1), p.37-42, 2012.

128
 BRAZILIAN JOURNAL OF PETROLEUM AND GAS | v. 11 n. 2 | p. 115-130 | 2017 | ISSN 1982-0593

Martinez-Palou, R.; Mosqueira, M. L.; Zapata- Sanchez, L. E.; Zakin, J .L. Transport of viscous
Rendón, B.; Mar-Juárez, E.; Bernal-Huicocheca, C.; crudes as concentrated oil-in-water emulsions.
La Cruz, J.; Aburto, J. Transportation of heavy and Industrial & Engineering Chemistry Research, v.
extra-heavy crude oil by pipeline: A review. Journal 33(12), p. 3256-3261, 1994.
Petroleum Science Engineering, v. 75(3-4), p. 274- https://doi.org/10.1021/ie00036a047
282, 2011.
https://doi.org/10.1016/j.petrol.2010.11.020 Saniere, A.; Henauti, I.; Argillier, J. F. Pipeline
transportation of heavy oils, a strategic, economic
Martinez-Palou, R.; Reyes, J.; Ceron-Camacho, and technological challenge. Oil & gas science and
R.; Ramirez-Santiago, M.; Villanueva, D.; Vallejo, A. technology, v. 59(5), p. 455-466, 2004.
A.; Aburto, J. Study of the formation and breaking https://doi.org/10.2516/ogst:2004031
of extra-heavy-crude-oil-in-water emulsions—A
proposed strategy for transporting extra heavy Sefton, E.; Sinton, D. Evaluation of selected
crude oils. Chemical Engineering and Processing, viscosity prediction models for water in bitumen
v.98, p. 112-122, 2015. emulsions. Journal of Petroleum Science and
https://doi.org/10.1016/j.cep.2015.09.014 Engineering, v. 72(1-2), p. 128-133, 2010.
https://doi.org/10.1016/j.petrol.2010.03.010
Muraza, O.; Galadima, A. Aquathermolysis of
heavy oil: A review and perspective on catalyst Shecaira, F. S.; Branco, C. C. M.; Souza, A. L. S.;
development. Fuel, v.157, p. 219-231, 2015. Pinto, A. C. C.; Holleben, A. R. C.; Johann, P. R. S.
https://doi.org/10.1016/j.fuel.2015.04.065 IOR: The Brazilian Perspective. SPE/DOE Improved
Oil Recovery Symposium, SPE-75170-MS, 13-17
Nunez, G. A.; Sanchez, G.; Gutierrez, X.; Silva, F.; April, Tulsa, Oklahoma, 2002.
Dalas, C.; Rivas, H. Rheological behavior of
concentrated bitumen in water emulsions. Sheng, J. J. Status of surfactant EOR technology.
Langmuir, v. 16(16), p. 6497-6502, 2000. Petroleum, v. 1(2), 97-105, 2015.
https://doi.org/10.1021/la990412p https://doi.org/10.1016/j.petlm.2015.07.003

Ortiz, D. P.; Baydak, E. N.; Yarranton,H. W. Effect Sheu, E. Y.; Detar, M. M.; Storm, D. A.
of surfactants on interfacial films and stability of Rheological properties of vacuum residue fractions
water-in-oil emulsions stabilized by asphaltenes. in organic solvents. Fuel, v.70, p. 1151-1156,
Journal of Colloid and Interface Science, v. 351(2), 1991a. https://doi.org/10.1016/0016-2361(91)90236-4
p. 542-555, 2010.
Sheu, E. Y.; Storm, D. A.; De Tar, M. M.
https://doi.org/10.1016/j.jcis.2010.08.032
Asphaltenes in polar solvents. Journal of Non-
Ovalles, E.; Rogel, E.; Morazan, H.; Moir, M. E. Crystalline solids, v. 131(Part 1), p. 341-347,
Synthesis, characterization, and mechanism of 1991b. https://doi.org/10.1016/0022-3093(91)90326-2
asphaltene inhibition of phosphopropoxylated
Soni, H. P.; Kiranbala, A.; Agrawal, K.S.; Nagar,
asphaltenes. Fuel, v.180, p. 20-26, 2016.
https://doi.org/10.1016/j.fuel.2016.03.084 A.; Bharambe, D. P. Designing maleic anhydride-α-
olifin copolymeric combs as wax crystal growth
Plasencia, J.; Pettersen, B.; Nydal, O. J. Pipe flow nucleators. Fuel Processing Technology, v. 91(9), p.
of water-in-crude oil emulsions: Effective viscosity, 997-1004, 2010.
inversion point and droplet size distribution. https://doi.org/10.1016/j.fuproc.2010.02.019
Journal of Petroleum Science and Engineering, v.
101, p.35-45, 2013. Sullivan, A. P.; Kilpatrick, P. K. The effects of
https://doi.org/10.1016/j.petrol.2012.11.009 inorganic solid particles on water and crude oil
emulsion stability. Industrial & Engineering
Ramalho, J. B. V. S.; Lechuga, F. C.; Lucas, E. F. Chemistry Research, v. 41(14), p. 3389−3404,
Effect of the structure of commercial poly(ethylene 2002. https://doi.org/10.1021/ie010927n
oxide-b-propylene oxide) demulsifier bases on the
demulsification of water-in-crude oil emulsions: Varfolomeev, M. A.; Galukhin, A.; Nurgaliev, D.
elucidation of the demulsification mechanism. K.; Kok, M. V. Thermal decomposition of Tatarstan
Química Nova, v. 33(8), p. 1664-1670, 2010. Ashal’cha heavy crude oil and its SARA fractions.
https://doi.org/10.1590/S0100-40422010000800009 Fuel, v.186, p. 122-127, 2016.
https://doi.org/10.1016/j.fuel.2016.08.042

129
 BRAZILIAN JOURNAL OF PETROLEUM AND GAS | v. 11 n. 2 | p. 115-130 | 2017 | ISSN 1982-0593

Wang, H.; Huang, C. P. The effect of turbulence Xu, Y.; Wu, J.; Dabros, T.; Hamza, H. Optimizing
on oil emulsification. The Physical Behavior of Oil the polyethylene oxide and polypropylene oxide
in the Marine Environment Workshop. Princeton contents in diethylenetriamine-based surfactants
University, Princeton, New Jersey, p. 81-100, 1979. for destabilization of a water-in-oil emulsion.
Energy & Fuels, v. 19(3), p.916-921, 2005.
Wang, W.; Wang, P.; Lik, K.; Duan, J, Wu, K.; https://doi.org/10.1021/ef0497661
Gong, J. Prediction of the apparent viscosity of non-
Newtonian water-in-crude oil emulsions. Yaghi, B. M.; Al-Bemani, A. Heavy Crude Oil
Petroleum exploration and development, v. 40(1), Viscosity Reduction for Pipeline Transportation.
p. 130-133, 2013. Energy Sources, v.24, p.93-102, 2002.
https://doi.org/10.1080/00908310252774417
Wong, S. F.; Lim, J. S.; Dol, S. S. Crude oil
emulsion: A review on formation, classification and Yudin,I. K.; Nikolaenko,G. L.; Gorodetskii, E. E.;
stability of water-in-oil emulsions. Journal of Kosov, V. I.; Melikyan, V. R.; Markhashov, E. L.;
petroleum Science and Engineering, v.135, p. 498- Frot, D.; Briolant, Y. Mechanisms of asphaltene
504, 2015. https://doi.org/10.1016/j.fuel.2016.08.042 aggregation in toluene–heptane mixtures Journal
of Petroleum Science and Engineering, v. 20(3-4),
Wu, J.; Xu, Y.; Dabros, T.; Hamza, H. Effect of EO p. 297-301, 1998. https://doi.org/10.1016/S0920-
and PO positions in nonionic surfactants on 4105(98)00033-3
surfactant properties and demulsification
performance Colloids and Surfaces A: Zhang, Z.; Xu, G. Y.; Wang, F.; Dong, S. L.; Li, Y.
Physicochemical Engineering Aspects, v. 252(1), p. M. Characterization and demulsification of
79-85, 2005. poly(ethylene oxide)–block–poly(propylene oxide)–
https://doi.org/10.1016/j.colsurfa.2004.09.034 block–poly(ethylene oxide) copolymers. Journal of
Colloid and Interface Science, v. 277(2), p. 464–
Xie, H.; Zhang, F.; Dong, L. Study and application 470, 2004a.
of the viscosity reducer used in production of the
viscous crude oil. SPE International Symposium on Zhang, Z.; Xu, G.; Wang, F.; Dong, S.; Chen, Y.
Oilfield Chemistry, SPE-65382-MS, 13-16 February, Demulsification by amphiphilic dendrimer
Houston, Texas, 2001. https://doi.org/10.2118/65382- copolymers. Journal of Colloid and Interface
ms Science, v. 282(1), p.1-4, 2004b.
https://doi.org/10.1016/j.jcis.2004.08.144

130