SPE-190057-MS

Asphaltenes Contribution in Emulsion Formation During Solvent-Steam

Processes

A. Ng, Texas A&M University; C. Ovalles and I. P. Benson, Chevron Energy and Technology Center; B. Hascakir,
Texas A&M University

Copyright 2018, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Western Regional Meeting held in Garden Grove, California, USA, 22-27 April 2018.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
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any position of the Society of Petroleum Engineers, its officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written
consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may
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Abstract
The objective of this paper is to enhance the produced oil quality during solvent-steam flooding processes
by using asphaltenes precipitants and environmentally friendly solvents as injection fluid. This way, it is
aimed to increase the asphaltene deposition tendency and decrease the emulsion formation severity.
Eight one-dimensional core flood experiments were conducted; one steam flooding, three solvent
flooding, and four solvent-steam flooding. Five different solvents were tested; propane, n-hexane, toluene,
Benzoyl peroxide (BP), and a plant-based environmentally friendly solvent (MS). Solvent and water
injection, oil and water production, and temperature along the core flood were continuously measured
during each experiment. Both produced oil and residual oil samples were further analyzed to investigate
the quality of produced oil samples and the amount of asphaltenes deposited on spent rock. An ASTM
method which uses n-pentane was implemented to separate asphaltenes from both produced and residual oil
samples. The water content of produced and residual oil samples was determined through thermogravimetric
analysis (TGA) and the water-in-oil emulsion content of produced oil samples was visualized with an optical
microscope. To understand the impact of each SARA (Saturates, Aromatics, Resins, and Asphaltenes)
fractions on produced oil quality during solvent-steam processes, every fraction was exposed to liquid or
vapor water and examined under a microscope.
It has been observed that stability of asphaltenes and emulsions varies in the presence of vapor or
liquid water. Aromatics and Resins fractions are the main contributors of water-in-oil emulsion formation,
and emulsion formation is enhanced with the addition of asphaltenes. Vapor-water (steam) promotes the
formation of more severe emulsions than liquid-water. Hence, the emulsion formation mechanism was
predicted to start with a foam-formation step in where the vapor steam diffuses into the liquid crude before
condensing to form liquid water droplets, and then, forming an emulsion at lower temperatures. Since
asphaltenes insoluble solvents were used, diffusion of steam occurs mostly in deasphalted oil and mainly
in aromatics and resins.
2 SPE-190057-MS

Introduction
Enhanced Oil Recovery (EOR) projects peaked during the mid-1980s in the U.S. with about 500 active
projects. 200 of them were thermal EOR projects of which 90% were steam injection processes alone (Hama
et al. 2014). Steam injection is the most commonly used thermal EOR method due to mainly its reliability
(Prats, 1982; Morrow et al., 2014). It is used to extract heavy oil and bitumen due to its effectiveness to
enhance the mobility of oil by reducing the viscosity (Willman et al., 1961) and its usefulness in wettability
alteration towards water-wet (Morte and Hascakir, 2016a; Kar et al., 2015; Stape and Hascakir, 2016).
Despite the efficiency of steam injection to extract low API gravity and high viscosity hydrocarbon
resources, the steam generation poses several environmental challenges; such as greenhouse gas emissions,
excessive use of freshwater resources, and high volumes of produced water (Mukhametshina et al., 2014).
For instance, the Steam Assisted Gravity Drainage (SAGD) projects are reported to emit average of 26 kg of
CO2 per one bbl of oil produced and during SAGD, and a minimum one bbl of water consumption is required
to produce one bbl of oil (Law, 2004). Whenfull-field scale projects are considered, the produced gas and
water volumes generate significant environmental concerns. Moreover, if the contaminants in produced
water are not treated safely the health concerns may also arise (Hunt, 1976; Jamaluddin and Vandamme,
1994).
Co-injection of solvent with steam was proposed in 1972 and further investigated in 1976 to increase
bitumen recovery due to additional viscosity reduction maintained by the solvents which also helps to
reduce the environmental impact and health concerns of steam injection projects alone. (Hernandez and
Farouq Ali, 1972; Farouq Ali and Abad 1976). However, the handling problems of solvents associated with
their toxicity make solvent injections undesirable (Mukhametshina et al., 2014; Janks and Cadena, 1991;
Todd et al., 1999). Another problem is the interaction of solvents with crude oil components. Asphaltenes
are the heaviest fraction of the crude oil which are insoluble in normal alkanes but soluble in aromatics
(Yen et al., 1961). Most of the solvents used in solvent-steam processes are asphaltenes insoluble such
as paraffinic solvents which will lead asphaltenes precipitation in the reservoir or production pipelines
(Leontaritis et al. 1994; Kharrat et al., 2007; Gaspar et al., 2012). As a result, the solvent selection is very
critical for the success of a solvent-steam process due to anticipated mutual interactions with asphaltenes,
the deasphalted oil fractions of crude oils, and with the reservoir rock (impact on wettability) (Unal et al.,
2015; Mukhametshina et al., 2014). Undesirably, since asphaltene is the most polar component, it has the
highest tendency to interact with the polar water molecules to stabilize and form water-in-oil emulsions
(Kilpatrick, 2012; Yarranton et al., 2007). However, the solvents may reduce the interfacial forces between
water and oil and decrease the severity of the formed emulsions due to steam injection (Kar and Hascakir,
2015, 2016; Kar et al., 2016).
Many researchers have investigated the use of a solvent in a steam-solvent hybrid flooding (Hascakir,
2016b; Kar et al., 2017). However, there is a lack of study done on finding alternative solvents considering
that current paraffinic and aromatic solvents are creating environmental issues as well as forming emulsions
in produced oil which increases surface processing cost. Besides that, it is also unclear on the emulsion
formation mechanism (Coelho et al., 2016; Kar et al., 2017); whether it is driven by the asphaltene alone
or by the mutual interaction of crude fractions. Thus, this paper aims to investigate the potential of an
environmentally friendly solvent to reduce the dependency on steam alone and replace the toxic solvents as
well as to understand the emulsion formation mechanism at the microscopic level.

Materials and Methods

Feasibility of solvent-steam injection into a bitumen reservoir from Canada was investigated in this study.
First, API gravity and viscosity of the initial sample were measured by following ASTM D-1250-08 and
ASTM D-2196-15 methods, respectively (ASTM, 2013,2015). Then, the amount of SARA (Saturates,
Aromatics, Resins, and Asphaltenes) fractions in the initial sample was determined through ASTM-
SPE-190057-MS 3

D2007-11 which uses n-pentane to separate asphaltenes. The characterization of the bitumen sample is
summarized in Table 1.

Table 1—Characterization of bitumen sample used in this study

SARA Fractions, wt%

API gravity Viscosity, cP
Saturates Aromatics Resins Asphaltenes

9.6 290,000 19 20.9 35.7 24.4

For EOR, experiments, first, reservoir rock samples were prepared by using 20-40 mesh size Ottawa
Sand which corresponds to 39.1 % porosity. 84 vol% of the pore space was filled with bitumen and 16
vol% with deionized water to replicate initial oil and water saturation in the core samples (Bayliss and
Levinson, 1976; Hamm and Ong, 1995). Prepared reservoir rock sample was packed into 20 cm length
and 5.4 cm diameter, stainless steel core holder. The inlet of the core holder was connected to the injection
pipelines that were connected to the steam generator and the solvent tank. The outlet of the core holder was
connected to a separator in which liquids (water and hydrocarbons), condensable gases (steam, solvents,
and light hydrocarbon components of oil), and non-condensable gases were separated. The experimental
pressure was maintained through nitrogen injection at 75 psig back pressure. The temperature of the cores
during the experiments was monitored by thermocouples placed at the center of the core sample through
a thermowell and temperature values were recorded every 2 seconds. Figure 1 shows the schematic of the
experimental set-up.

Figure 1—Schematic representation of solvent-steam set-up

In total, eight EOR experiments were conducted. Table 2 summarizes the initial and experimental
conditions of all EOR experiments.
E1 is the only steam injection experiment. E2, E5, E6, and E8 are the solvent-steam injection experiments.
E3, E4, and E7 are the solvent (miscible flooding) injection experiments. 18 mL/min (cold water equivalent)
steam injection rate was used in E1, E2, E5, E6, and E8 at 165°C with 100% steam quality. 2mL/min solvent
injection rate was used in E2, E3, E4, E5, E6, E7, and E8 at room temperature. Five different solvents
were tested; n-hexane (C6), propane (C3), toluene, Benzoyl Peroxide (BP), and an environmentally friendly
solvent (MS). Apart from toluene, all other solvents are known as asphaltenes insoluble (Yen et al., 1961).
In all experiments, total experiment time was decided based on the oil recovery rate observed in E1.
Once the oil rate decreased drastically, or cumulative oil recovery reached a plateau, experiments were
4 SPE-190057-MS

continued for 30 minutes more and then, terminated due to a reduction in oil production and increase in water
production. For the rest of the experiments, the same experimental time was applied for proper comparison
purposes. However, because BP is a solid phase hydrocarbon and it is also insoluble in asphaltenes,
asphaltenes precipitation was induced in E5, and the outlet pipelines were blocked with precipitated
hydrocarbons and caused an increase in pressure of the system. Hence, E5 had to be terminated after 140
minutes. Also, in E2, due to minor n-C6 leak in the vapor phase in the separator, E2 was terminated early.

Table 2—Summary of the experimental conditions for all experiments (C6 is n-hexane,
C3 is propane, BP is Benzoyl Peroxide, and MS is an environmentally friendly solvents)

Experiments Injected Fluid Type Injection Rate Total experiment time, min

E1 Steam 18 mL/min 240

E2 Steam + C6 18 mL/min + 2 mL/min 160ǂ

E3 C6 2 mL/min 240

E4 Toluene 2 mL/min 240

E5 Steam + BP* + C3 18 mL/min +2mL/min + 2 mL/min 140#

E6 Steam + MS** + C3 18 mL/min +2mL/min + 2 mL/min 240

E7 C3 2 mL/min 240

E8 Steam + C3 18 mL/min + 2 mL/min 240

* Benzoyl peroxide is in solid state solvent and dissolved in the ratio of 0.25g BP: 1ml dichloromethane: 6ml n-hexane.
** MS is an environmentally friendly solvent.
ǂ Due to minor n-C6 leak in vapor phase in separator, E2 was terminated early
ǂ BP or BP+Asphaltenes precipitated and/or crystallized in production lines and blocking the pipelines, due to a sudden increase in pressure, E5 was terminated
early.

During all experiments, temperature profiles were monitored every two seconds, and produced liquids
were collected around every 20 minutes.
Postmortem analyses of the spent rock from all eight EOR experiments were achieved by residual oil
separation burning the oil remained on a small amount of spent rock samples by the thermogravimetric
analyzer and differential thermal analyzer (TGA/DTA). The asphaltene content of the produced and residual
oil samples was measured by using n-pentane separation (ASTM D2007-11).
At the end of each experiment, produced oil samples were analyzed through a Meiji Techno Japan optical
microscope with a ProgRes CT5 Camera to observe the existence and severity of the formed water-in-oil
emulsions.
For emulsion characterization observed in produced oil samples, several additional control experiments
were conducted to find the role of bitumen fractions in the emulsion formation. All SARA fractions were
exposed to either steam or liquid water for 10 minutes, and then, emulsions were characterized by optical
microscopy at 40X magnification.

Results and Discussions

Figure 2 provides the summary of microscopic images at 40X magnification of collected produced oil
samples at the top and the visual inspection of spent rock samples at the bottom from all eight EOR
experiments.
SPE-190057-MS 5

Figure 2—Top pictures are the microscopic images of produced oil samples at 40X
magnification, and bottom pictures are postmortem pictures of spent rock samples just after
each experiment (note that on postmortem pictures, injection direction is from top to bottom)

Kokal in 2005 reported that the smaller the emulsion droplet size, the longer the residence time thus,
requiring a larger surface separation setup. Thus, comparing all the experiments, because the emulsions are
the mixture of fine and large size water droplets, E2 in which steam was coinjected with n-hexane yielded
the lowest quality of produced oil with the most severe emulsions.
It is observed from the spent rock samples’ pictures that while E6 yielded the greatest oil displacement,
E1 in which steam was injected alone showed the most reduced performance among all EOR experiments
due to its consolidated structure and dark color. The corresponding microscopic image of the produced oil
samples for E6 in which steam was coinjected with the environmentally friendly solvent (MS) shows non-
severe emulsion due to water droplet sizes and the amount of water bubbles present in the microscopic area.
The use of benzoyl peroxide (BP) in E5 showed severe emulsion formation as well. To better explain the
mechanisms observed in E5, an additional control experiment was conducted, and asphaltenes from initial
bitumen sample were blended with the same solvent mixture used in E5 (0.25 g benzoyl peroxide + 1 ml
dichloromethane + 6 ml n-hexane). Their interaction was investigated under an optical microscope as shown
in Figure 3. It is observed that the interaction of benzoyl peroxide with asphaltenes results in the formation of
complex crystalline structures which might be the reason behind induced asphaltenes precipitation observed
in E5 that caused pipe blockage in E5.

Figure 3—Optical Microscopy image of benzoyl peroxide interaction with

initial asphaltenes from the original bitumen sample at 40X magnification.
6 SPE-190057-MS

The produced oil and spent rock samples shown in Figure 2 from all experiments were further analyzed
(Table 3).
The residual oil amount in weight% is determined through the TGA/DTA analysis. Through TGA/DTA,
two spent rock samples were taken from the inlet and outlet each for all eight experiments which are
subjected to heating at 10 K/min heating rate under 50 mL/min of air injection rate. The heating under
air injection was continued until reaching the final temperature of 900 °C. At the thermal decomposition
temperature of oil (measured at around 450 °C), the TGA graph which represents the weight loss graph
is used to determine the amount of residual oil left behind on the spent rock. Each TGA result from the
inlet and outlet were then averaged to find the representative residual oil content from each experiment
(Table 3). The residual oil weight% was then converted into pore volume by using the initial oil weight
percent (17.3%) which corresponds to 84% pore volume. Sweep efficiency given in Table 3 was calculated
by subtracting the initial oil volume percent (84%) from the residual oil volume percent and dividing this
number to initial oil volume percent (Green and Wilhite, 1998). The asphaltenes reported in Table 3 were
measured by following the ASTM-D2007-11 method which uses n-pentane to separate asphaltenes.

Table 3—Spent rock and produced oil samples analyses for all experiments

Spent Rock Analyses Asphaltenes, wt%

Experiments Residual Residual Sweep In Produced
In Residual Oil
oil, wt% Oil, vol% Efficiency, vol% Oil

E1 6.6 32.05 61.85 27.90 26.57

E2 2.38 11.56 86.24 19.01 23.42

E3 8.78 42.63 49.25 27.42 20.92

E4 2.48 12.04 85.66 26.04 30.20

E5 3.93 19.08 77.28 16.77 23.79

E6 0.80 3.88 95.38 22.27 27.74

E7 15.70 76.23 9.25 26.66 19.04

E8 3.51 17.04 79.71 27.20 28.10

In general, E2, E5, E6, and E8 which are all solvent-steam processes have very promising sweep
efficiencies with E6 being the best of all. The added benefit of E6 is, in this experiment, the environmentally
friendly solvent (MS) was coinjected with steam, and it even outperformed E4 in which toluene was used.
Note that toluene is known to be an excellent solvent for crude oils. These results confirm that solvent-steam
processes perform better in crude extraction compared to just steam or solvent alone processes. Because, in
a hybrid solvent-steam process, the solvent can reduce the interfacial tension of the crude which improves
miscibility while steam dilutes and reduces the crude’s viscosity at the same time (Farouq Ali, 1976).
The asphaltenes amounts reported in Table 3 are further normalized for better comparison, and these
normalized values are given in Figure 4.
SPE-190057-MS 7

Figure 4—Normalized asphaltene weight percent deposited on spent

rock and produced in oil for 100-unit mass of total asphaltenes

It is a known fact that as the carbon number decreases in n-alkane, the deposited asphaltene amount
increases due to the lower solubility parameter (Mullins, 2008; Shkalikov et al., 2010). In E3, normal-hexane
(n-C6) and in E7, propane (C3) was used as solvents. Because n-hexane has more carbons than propane,
n-hexane injection (E3) resulted in the lower amount of asphaltene deposition than propane injection (E7)
experiment. Also, toluene is an excellent solvent, and asphaltenes are soluble in toluene. Thus, E4 (in
which toluene was used as solvent) resulted in the least asphaltenes deposition among all solvent injection
processes (E3, E4, and E7). Steam injection alone (E1) also caused significant asphaltenes deposition (37
wt%). Coinjection of solvent with steam (E2, E5, E6, and E8) resulted in reduced asphaltene deposition
on the rock surface. The least asphaltenes deposition was observed for E6 (in which the environmentally
friendly solvent (MS) was used) and the greatest for E5 (in which BP was used).
E6 proves to be the ideal conditions to reduce asphaltene precipitation on the spent rock. However, that
means that the produced oil contained the highest asphaltene wt.%, and this behavior might lead to surface
processing and pipeline plugging issues. Thus, the effect of the high asphaltene content in produced oil is
investigated in the following section.
Asphaltenes being the fraction with the highest solubility parameter of crude oil is thought to be
responsible for the emulsion formation due to expected interaction with the polar liquid water molecules
(Kilpatrick, 2012; Punase and Hascakir, 2017; Yen et al., 1961). Because E3, E4, and E7 experiments were
only solvent injection experiments, no emulsion formation in those experiments was observed regardless
their asphaltenes content. The emulsion characterization and interpretations were achieved for steam (E1)
and solvent-steam experiments (E2, E5, E6, and E8) only. Moreover, we could not find direct correlations
between asphaltenes and water amount present in the produced oil samples. Hence, we concluded that the
emulsion formation mechanism should be more complex than just depending on the role of asphaltene
as surfactants. Thus, we conducted some additional control experiments to clarify the role of each SARA
fraction on emulsion formation mechanism.

Additional Control Experimental Results and Discussions

First, initial bitumen and its fractions were visualized through optical microscopy. Then, these samples have
been exposed to either liquid water at room temperature or vapor water for 10 minutes, and several optical
microscopic images were acquired to observe the interaction of oil fractions with either steam or liquid
water. The optical microscopy images are summarized in Figure 5.
8 SPE-190057-MS

Figure 5—The optical microscopic images of initial bitumen and its fractions
after interaction with either liquid or vapor water (steam) at 40X magnification

After 10 minutes of exposure to steam, the aromatics and resins fractions resulted in triple emulsion
formation. While similar behavior has been observed for bitumen, it has not been observed for asphaltenes.
Interestingly, emulsion formation only occurred for the steam case but not for liquid water case. These
observations may lead to two findings. First, the aromatic and resin fractions have relatively higher solubility
parameters than the saturate counterparts. This situation makes the first two partially soluble in water. Thus,
it can be proposed that the aromatic and resin fractions could behave as surfactants to stabilize oil-in-water
emulsions as it has been reported for the asphaltenes (Prakoso et al., 2015; Kilpatrick, 2012; Punase and
Hascakir, 2017; Yen et al., 1961). Second, initially foamy oil forms when steam diffuses into the deasphalted
oil (portion of oil without asphaltene) and then when steam condenses the liquid water traps inside oil
fractions and forms emulsions.
To further investigate the mutual interactions of aromatics with other crude oil fractions, aromatics were
blended with resins and resins + asphaltenes, and these blends with liquid and vapor water were investigated
by optical microscopy. Results are given in Figure 6. The mutual interaction of aromatic and resin blend
results in more severe emulsion formation with smaller and more number of bubbles. It is proposed that the
interactions of aromatics, resins, and asphaltenes caused more dispersed water bubbles with more complex
emulsion formation (triple emulsions). This situation could indicate that resins and aromatics induced the
formation of emulsions while asphaltenes stabilized the already formed emulsion. In addition, since resins
are confirmed to have polar bonding which also play a critical role in f emulsion formation.
SPE-190057-MS 9

Figure 6—Visualization of mutual interaction of aromatics with other bitumen fractions under
optical microscopy in the presence of either liquid or vapor water (steam) at 40X magnification

Conclusions
In this study, we aim to find a green alternative injection solvent to mitigate environmental and health issue
about to the use of current commercial grade solvents. At the same time, the co-injection of solvent with
steam is known to reduce the formation of emulsion due to the reduction of interfacial forces between
water and crude fractions. Thus, we also aim to understand the role of SARA fractions in the formation
of emulsions.
From this work, we were able to prove the potential reliability of a green solvent which produced non-
severe emulsion and had an encouraging oil displacement at the lab scale. This finding could help reduce
our environmental footprint as well as create a safer working environment.
Other than that, by suggesting that asphaltenes are not the primary contributor to emulsion formation, we
could better design injection fluids to tackle the main contributors instead. This finding also could potentially
shed light on the asphaltene physical and chemical characteristics which are still mostly unknown.

Acknowledgement
We acknowledge the financial support and the opportunity provided by Chevron and the Heavy Oil, Oil
shales, Oil sands, & Carbonate Analysis and Recovery Methods (HOCAM) Research Team at Texas A&M
University, Petroleum Engineering Department.

Nomenclature
API – American Petroleum Institute
ASTM – American Society for Testing and Materials
bbl – US barrel
BP – Benzoyl peroxide
CO2 – Carbon dioxide
C3 – Propane
C6 – n-Hexane
10 SPE-190057-MS

cP – Centipoise
EOR – Enhanced Oil Recovery
MS – Ethicalchem MS environmentally friendly solvent
SAGD – Steam-assisted gravity drainage
SARA – Saturate, Aromatics, Resins, and Asphaltenes
St – Steam
TGA/DTA – ThermoGravimetric Analyzer and Differential Thermal Analyzer
Tol – Toluene
vol% – Volume percent
wt% – Weight percent

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