SPE-171076-MS

The Role of Asphaltenes in Emulsion Formation for Steam Assisted

Gravity Drainage (SAGD) and Expanding Solvent - SAGD (ES-SAGD)
Taniya Kar, Matthew Williamson, and Berna Hascakir, Texas A&M University

Copyright 2014, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Heavy and Extra Heavy Oil Conference - Latin America held in Medellin, Colombia, 24 –26 September 2014.

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Abstract
Steam Assisted Gravity Drainage (SAGD) and Expanding Solvent SAGD (ES-SAGD) have previously
been compared and ES-SAGD has shown improved oil recovery with lower energy and water require-
ments and significant oil upgrading. However, solvent selection is the key factor which determines the
performance of ES-SAGD due to the asphaltene-solvent interaction. The change in asphaltene stability
with the solvent type can have several drawbacks during ES-SAGD. Stable emulsion formation is one of
these problems which have not been investigated thoroughly for ES-SAGD. In this study, we character-
ized both water-in-oil and oil-in-water type of emulsions originating from SAGD, SAGD with n-hexane
and SAGD with n-hexane and toluene mixture experiments. These three experiments were conducted on
8.65 °API Canadian bitumen with 34.3 wt% asphaltene content. Structural changes in produced oil,
produced water, and spent rock samples were analyzed with Fourier Transform Infrared (FTIR) spec-
troscopy. Emulsions in produced oil and water samples were determined with microscopic images. The
differences in emulsions were interpreted with the wettability change determined on spent rock samples.
Moreover, the asphaltene fraction of produced oil samples is further analyzed with FTIR and zeta potential
measurements. For produced oil, the greatest asphaltene content with more severe emulsion formations
were detected on the sample originating from SAGD. In terms of stability, because the asphaltenes
originating from both ES-SAGD experiments have higher zeta potential values, lower emulsion stability
has been observed for the produced oil originating from ES-SAGD. In summary, the role of asphaltenes
on emulsion formation has been studied for SAGD and ES-SAGD for bitumen extraction. ES-SAGD with
asphaltene soluble solvents leads to the formation of less stable emulsions.
Introduction
The unconventional oil resources account for 55% of the total world reserves which include heavy oil,
extra-heavy oil, and bitumen. The total bitumen resources from 598 deposits, located in 23 different
countries, are estimated around 3.38 trillion barrels which is reported to be 2.6 times more than the
conventional oil reserves (Attanasi et al. 2010). Around 70% of the world’s bitumen resources are
deposited in Western Alberta. Surface mining is applicable only to 20% of the total Alberta’s bitumen, and
in-situ cold production can only be effective to recover the 5% of the remaining 80% of the reserve. This
low extraction yield mainly stems from the high viscosities of bitumen. Because the flow resistance of
2 SPE-171076-MS

high viscosity crudes can be reduced by increasing the temperature of the reservoirs, extraction of these
resources can be accomplished effectively with the application of thermal recovery methods. Thermal
Enhanced Oil Recovery (EOR) has been the most successfully applied till date, mainly because it does not
require direct contact between the oil in place and injected element. It upgrades oil in-situ by viscosity
reduction, oil swelling and wettability alteration by means of heat transfer through conduction and
convection (Kovscek et al, 2012).
However, the environmental, economic, and technical challenges of bitumen extraction with thermal
methods limit their application. As conventional resources are declining and bitumen resources are
enormous, it is essential to address those challenges of thermal recovery methods to extract the massive
bitumen resources by developing new and innovative technologies or by alternating the existing methods.
In general, hot water and steam injection processes are preferred due to their simplicity, reliability, and
easy to apply features. Steam Assisted Gravity Drainage (SAGD), due to its different well configuration,
is the most effective steam injection process for bitumen recovery (Butler, 1991 and Butler, 1998). Even
though, SAGD presents promising oil recovery results from bitumen reservoirs, the environmental and
economic drawbacks of steam generation make the alternatives of SAGD more attractive. Expanding
Solvent-SAGD is one of the most pronounced alternative SAGD technologies which reduces steam
generation cost, greenhouse gas (GHG) emissions due to steam generation, and increase the oil recovery
(Nasr, et al., 1991). However, the adverse effects of ES-SAGD have not been studied fully in terms of
produced water treatment and oil processing.
The major problems of steam injection processes are associated with water production. Water is
produced separately from the oil and/or in emulsion form within the oil. The separation of water from the
emulsified oil might be required to accomplish on site to find a proper market for the produced oil.
Emulsion is a colloidal mixture of two immiscible liquids-with one liquid (called dispersed phase)
suspended in the form of small droplets throughout the other liquid (called continuous phase or dispersion
medium). In case of bitumen recovery, emulsions can be of three main types: water-in-oil, oil-in-water,
and complex emulsions. In water-in-oil emulsions, water is the dispersed phase, oil is the continuous
medium. In oil-in-water emulsions, oil is the dispersed phase, water is the continuous medium. In the
complex emulsions, oil-in-water-in-oil or water-in-oil-in-water type of emulsions can be observed.
Emulsifiers, which are the stabilizing agents, form an interfacial film around the droplets of the
dispersed phase and act as a buffer between the two phases, thus, preventing the coalescence of the
dispersed phase droplets and stabilizing the emulsions (Kokal, 2005). The interfacial film formed by the
emulsifier reduces the interfacial tension between the oil and water phases, creating a steric hindrance for
the combining of the dispersed phase droplets, which increases the interfacial viscosity. These emulsifiers
are either naturally present in the reservoir that contains high boiling point and high molecular weight
fractions like resins and asphaltenes; high amount of fine solid particles (inorganic) like clays, sand, and/or
contains corrosion products; or are those which are added during various stages of oil production like
drilling fluids-drilling mud, inhibitors added for asphaltenes, waxes, scale and corrosion control.
The stable emulsion formation during bitumen extraction should be mainly due to asphaltene content
of bitumen itself along with the ratio of asphaltenes to other petroleum fractions (deasphalted oil fractions;
saturates, aromatics, and resins). During oil production, a large pressure reduction from reservoir to
wellhead alters the solubility of fluid and mostly causes asphaltene precipitation. A minor portion of the
asphaltene particles gets suspended in the crude oil, is attracted to the oil-water interface and forms stable
emulsions (Sjoⱊⱊblom et al., 2007).
On precipitation, the aggregates get adsorbed on the oil-water interface and form a highly stable
visco-elastic film around the water droplets. Asphaltene aggregation is due to high aromaticity; intermo-
lecular ␲-␲ and hydrogen bonding between monomers (Deo and Hanson, 1993 and Spiecker et al., 2002).
The high strength of the film is a result of heavy aggregation of particles and cross linking. In some cases,
resins aid in asphaltene emulsion stability by acting as a solvent for asphaltenes and provide temporary
SPE-171076-MS 3

stability during migration of asphaltenes (Mullins et al., 2007 and Fingas, 2014). However, after a point
of maximum stability, further addition of resins destabilizes the emulsions by reducing aggregate size of
asphaltenes (Spiecker et al., 2002). The degree of asphaltene-resin association also depends on the crude
oil composition, type of asphaltene (i.e. the precipitating agent used to separate asphaltenes) and
temperature (Al-Maamari, et al., 2003 and Zhao et al., 2009).
Apart from asphaltenes, for clay containing bitumen, the clay particles can also stabilize or enhance the
stability of emulsions (Sztukowski and Yarranton, 2004). Inside the reservoir, the positively charged
asphaltenes flocculate and react with the negatively charged clay minerals to get deposited on the rock.
Clay particles and fines are dispersed by the asphaltene flocs and get combined with the crude oil due to
their oil-wet nature (Leontaritis et al., 1994). These fines, along with the asphaltenes, can further increase
the stability of oil-water interface in the produced oil, thus, strengthening the water-in-oil emulsions.
In this paper, water-oil emulsions in the produced oil obtained from three experiments (one SAGD and
two ES-SAGD) are characterized and the relative emulsion stabilities are compared. Further, the cause of
these emulsions is investigated by analyzing the produced water, produced oil, spent rock samples, and
asphaltene content and structure by wettability analysis, Fourier Transform Infrared Spectroscopy,
rheology study, viscosity and zeta potential measurements.

Materials and Methods

One SAGD and two ES-SAGD experiments on a Canadian bitumen (8.65 ˚API gravity and 34.3
weight% asphaltene content) were previously conducted at the Texas A&M University, Petroleum
Engineering Department laboratories (Mukhametshina and Hascakir, 2014). In that study, experimental
samples were prepared by mixing 85 weight percent 20-40 mesh-size Ottawa sand with 15 weight percent
clay (90% kaolinite and 10% illite). This mixture corresponds to 32% porosity. The pore space of the
unconsolidated sand samples was saturated with 16 volume percent distilled water and 84 volume percent
original bitumen. All experiments were conducted in identical experimental conditions (75 psig at 165˚
C) and at a constant water injection rate; 18 L/min. In the two ES-SAGD experiments, constant; 2 L/min,
solvent injection rate was used. The Two ES-SAGD experiments were varied only with the injected
solvent type; n-hexane and n-hexane-toluene mixture in equal amount were injected in these two
experiments.
The scope of this study is to investigate the emulsion formation mechanism for these three experiments.
Therefore, produced oil, produced water, and the spent rock samples originated from base SAGD (E1),
ES-SAGD with co-injection of n-hexane (E2), and ES-SAGD with co-injection of n-hexane and toluene
(E3) experiments are analyzed in this study to develop an understanding for the emulsion formation
mechanism for SAGD and ES-SAGD. However, more detailed description of the experimental procedure
for SAGD and ES-SAGD can be found in the previously published technical papers (Mukhametshina and
Hascakir, 2014, and Mukhametshina et al., 2014).
The water-in-oil emulsions in produced oil samples and oil-in-water emulsions in produced water
samples are observed in all three experiments. The photographs of these samples are provided in Figure
1. In this figure, the first image shows the produced water sample originated from E1 (base SAGD) and
the second and third images provide for the visual inspection of samples originated from E2 (ES-SAGD
with n-hexane).
The produced emulsions and the spent rock samples from all experiments are analyzed with various
techniques.
Meiji Techno Japan-Microscope (100X magnification) and ProgRes CT5-Camera are used to visualize
the emulsion types in 100X magnitude. The rheological behavior of the fluids is determined with a
Brookfield Rheometer. The residual oil from spent rock is obtained using toluene extraction (Amyx et al.,
1960). Asphaltenes originated from original bitumen, produced oil, and residual oil are separated using
4 SPE-171076-MS

Figure 1—Oil-water emulsions in produced water and oil sapmles obtained from SAGD and ES-SAGD processes

Figure 2—Microscopic images of and distilled water (a) and produced water samples for (b) E1, (c) E2 and (d) E3

Figure 3—Microscopic images of (a) Original bitumen and emulsions observed in produced oil for (b) E1, (c) E2 and (d) E3

ASTM Standard D2007-11 method. According to this standard, asphaltenes are the n-pentane insoluble
portion of bitumen (ASTM, 2011). Therefore, throughout the manuscript, asphaltene nomenclature will be
used for the n-pentane insoluble portion of the bitumen.
The role of asphaltenes in emulsion formation is investigated both with the weight percent of
asphaltenes and the molecular structures of asphaltenes originated from the produced oil samples of all
experiments. Structural analyses of asphaltenes and bulk produced oil, water, and spent rock samples are
attained with Agilent Fourier Transform Infrared (FTIR) spectroscopy. Solid-wettability of spent rock
samples is measured using DSA Drop shape analyzer equipment from Kruss. The stability of asphaltenes
is determined by zeta potential measurements by using the Zeta PALS Brookhaven instrument.

Experimental Results and Discussion

Type of Emulsions
The produced water and oil samples are analyzed under the microscope with 100X magnification. Figure
2 provides the microscopic images of produced water from the three experiments along with the
microscopic image for distilled water (Figure 2-a) as reference. The oil-in-water emulsions are not
significant in produced water samples. However, the solid concentration in water is noted in the produced
water samples. This solid content should be due to clay, sand, and organic matter contents of the produced
water samples. The highest solid content is observed for E2 (Figure 2-c).
Figure 3 shows the microscopic images of produced oil samples from the three experiments. Figure 3-a
gives the microscopic image of the original bitumen to better characterize the emulsions in produced oil
samples by comparing them with the image of the initial bitumen sample. Even though, the original
SPE-171076-MS 5

Table 1—Measured viscosities of produced water and oil samples

Viscosity (cP)

Experiment Of produced water at T ⴝ 25˚C Of produced oil at T ⴝ 35˚C

E1:Base SAGD 0.99 45955

E2:ES-SAGD with hexane co-injection 0.94 11415
E3:ES-SAGD with hexane ⫹ toluene (co-injection) 1.02 3549

Table 2—Rheological behavior of produced oil from the three experiments compared to original bitumen
Rheology at varying temperatures

Samples Temperature (°C) Power Law Equation K n R2

Original Bitumen 35 ␴ ⫽ 133.35␥0.6888 133.35 0.6888 0.8576

45 ␴ ⫽ 31.254␥0.9762 31.254 0.9762 1
55 ␴ ⫽ 11.789␥0.9907 11.789 0.9907 0.9909
E1:Base SAGD 35 ␴ ⫽ 504.44␥0.9117 504.44 0.9117 1
45 ␴ ⫽ 176.36␥0.9445 176.36 0.9445 1
55 ␴ ⫽ 75.49␥0.9623 75.49 0.9623 0.9999
E2:ES-SAGD with 35 ␴ ⫽ 126.06␥0.9578 126.06 0.9578 1
hexane co-injection 45 ␴ ⫽ 45.935␥0.9688 45.935 0.9688 1
55 ␴ ⫽ 18.68␥0.99 18.68 0.99 1
E3:ES-SAGD with 35 ␴ ⫽ 36.881␥0.9843 36.881 0.9843 1
hexane⫹ toluene 45 ␴ ⫽ 16.394␥0.9995 16.394 0.9995 1
55 ␴ ⫽ 7.2404␥1.0419 7.2404 1.0419 0.9992

bitumen sample contains 6 volume % water (Kudryavtsev and Hascakir, 2014), in the microscopic images,
we could not detect any emulsions in original bitumen (Figure 3-a). Nevertheless, the produced oil
samples show stable emulsions with different sizes and types. Emulsions originated from the base SAGD
experiment have the biggest droplet size and this emulsion is a triple emulsion which is an oil-in-water-
in-oil emulsion (Figure 3-b). The size of the water droplet is getting smaller in E2, and the smallest water
droplets are obtained with E3 (Figure 3-d).
Produced Water and Oil Viscosities
Viscosities of produced oil and water samples are measured and the results are summarized in Table 1.
The viscosity of produced oil could not be measured at room temperature due to its low mobility.
Therefore, while the viscosity measurements of produced water are achieved at 25°C, the produced oil
viscosities are acquired at 35°C.
The produced water viscosity for E3 is slightly higher than the other viscosity values of produced water
samples, but they are all very close to 1 cP. For the produced oil samples, readings show that ES-SAGD
results in much more upgraded oil compared to SAGD in terms of viscosity reduction. The solvents help
in dissolving the heavier oil components, resulting in considerably less viscous produced oil.
The rheological behavior of the produced oil from the three experiments is further studied by
measuring their apparent viscosities as a function of shear stress to shear rate with increasing temperature.
The results are compared to original bitumen and are provided in Table 2.
Power-law model, represented by ␴ ⫽ K␥n relation in Table 2, is used to describe the rheology of the
fluid. In the above table, ␴ ⫽ shear stress and ␥ ⫽ shear rate. The ratio ␴/␥ gives apparent viscosity at
a given temperature. K is the flow consistency index and n refers to flow behavior index (Green and
Willhite, 1998). R represents the correlation coefficient which indicates the degree of linear relationship
between the two variables. A value of R2 near or equal to 1 indicates that the rheology fits into the power
law model. The rheological behavior of original bitumen and produced oil for all experiments are similar.
6 SPE-171076-MS

Table 3—Characterization of produced water samples

Experiment pH TDS (ppm) Conductivity (␮S) Particle Size (nm) Zeta Potential (mV)

E1 7.84 46.3 93.3 423.33 -51.50

E2 6.94 44.7 88.1 581.58 -43.33
E3 7.07 33.8 68.0 1001.53 -52.35

Figure 4 —Postmortem analyses of experiments with contact angle measurements; in each analysis, upper contact angle measurement provides the
contact angle of the initially packed oil sand samples, lower measurements provide contact angle of postmortem (spent rock) after the experiment.
Lower left measurements are from the region away from the steam chamber and lower right measurements belong to the region inside the steam
chamber

However, the apparent viscosities for E2 and E3 are much lower (indicated by a proportional decrease in
values of K), indicating highly upgraded oil. With increasing temperature and shear stress, the apparent
viscosity is seen to decrease for all cases. Value of “n” less than 1 in all cases (with the exception of E3
@ 45°C, which might be an experimental error) indicates pseudoplastic (shear-thinning) behavior of
produced oil (decrease in viscosity with increasing shear stress).
In all the cases, the Power law model has been constructed with three readings each of viscosity change
with change in shear rate. With more number of readings, slight differences in the model are expected.
Produced Water Characterization
The characterization of the produced water samples obtained from the three experiments is completed by
measuring pH, total dissolved solids (TDS), conductivity, particle size, and zeta potential. The results are
summarized in Table 3. pH is measured using the Oaklon Instruments pH meter, conductivity and TDS
by the Oaklon Conductivity-meter, particle size by 90Plus Particle Size Analyzer Brookhaven and zeta
potential by Zeta PALS Brookhaven. The biggest particle size is measured for E3 which is believed to
account for the slightly higher viscosity (1.02 cP, Table 1) for this case.
The particle sizes given in Table 3 indicate that the system in produced water samples is a colloidal
system (Hascakir and Dolgen, 2008).
The stability of the colloids is described by the zeta potential measurements which provide information
on the settling characteristics of the particles. For the colloidal stability, zeta potential results indicate a
decrease for E2. Therefore, the repulsion forces on the particles of E2 is less than those of E1 and E2. In
other words, the particles in E2 have a higher tendency for settlement than the particles in E1 and E3.
Solid-Wettability characteristics of spent rock
The wettability determination on the postmortem samples both from the inside and the outside steam
chamber is achieved by the contact angle measurements. The water-air contact angles as measured by
DSA 30 Drop Shape Analyzer are found to bear a linear relationship to the water-oil contact angle (Grate
et al, 2012). A higher value of measured contact angle shows more oil-wet behavior compared to a lower
contact angle value. The measurements are illustrated in Figure 4. In general, the postmortem samples
SPE-171076-MS 7

Table 4 —Weight% and zeta potential measurements of asphaltenes in produced oil (Para-Barraza et al, 2003)
Experiment Amount of asphaltene in produced oil (wt%) Zeta Potential of Asphaltene (mV)

Original bitumen 34.3 -14.0

E1 43.91 -9.87
E2 24.09 -18.77
E3 31.07 -16.08

Table 5—Weight% of residual oil and asphaltenes for postmortem samples inside and outside steam chamber (S.C.)
Asphaltene content (wt%) Asphaltene content (wt%)
Experiment Zone Residual Oil (wt%) in terms of spent rock in terms of residual oil

E1 Inside S.C. 22.83 7.91 34.64

Outside S.C. 18.94 4.78 25.24
E2 Inside S.C. 16.69 6.10 36.55
Outside S.C. 17.75 7.01 40.00
E3 Inside S.C. 13.73 4.87 35.47
Outside S.C. 14.86 3.65 24.56

(spent rock) for E1, E2, and E3 are found to be slightly oil-wet inside the steam chamber and
intermediate-wet outside the steam chamber.
These analyses provide valuable information on the wetting characteristics of solid samples which will
be used in later sections to explain the emulsion mechanism.
Asphaltene content of produced oil and postmortem samples
The asphaltene separation from the produced oil samples originated from all three experiments, original
bitumen, and the residual oil is carried out by following ASTM Standard D2007-11 method. Table 4
summarizes the amount of asphaltenes and zeta potential measurements of asphaltenes obtained from
original bitumen and produced oil samples.
For the asphaltenes left behind on postmortem samples, first, the residual oil is separated from the solid
samples by washing the postmortem samples with toluene, then, the ASTM standard is used for asphaltene
separation. The solvent toluene is used since it is a strong solvating agent and can completely dissolve
even the heaviest oil components (asphaltenes) and successfully separate all the residual oil from spent
rock (Amyx et al., 1960). These analyses are conducted on the samples collected from the regions defined
in Figure 4.
The weight% of residual oil is measured by subtracting the weight of spent rock after oil removal from
the original weight. The weight% of asphaltenes is calculated by subtracting the weight of deasphalted oil
(DAS) from residual oil. The results are provided in Table 5.
The following discussions can be produced with the results summarized in Table 4 and Table 5;
1. Asphaltenes of produced oil originated from Base SAGD have a lower zeta potential value (i.e,
more oil-wet nature-Figure 4) compared to the rest of the samples. Hence, the asphaltenes of E1
show a higher tendency for precipitation, because of its lower stability. The highest stability is
observed for E2. But the overall precipitation tendency of the asphaltene samples originated from
original bitumen and produced oil are exceptionally high. This tendency can be understood better
with the comparison of the zeta potential values given for produced water samples in Table 3 with
the values provided for asphaltenes in Table 4. Thus, it can be concluded that asphaltenes have
extremely low stabilities.
2. The asphaltene content of produced oil is significantly higher for E1. This might be due to
clay-asphaltene interactions which will be discussed in FTIR section later. Because n-hexane is
asphaltene non-solvent, the lowest asphaltene content is observed in the produced oil samples of
8 SPE-171076-MS

Figure 5—FTIR of (a) Distilled water and produced water for (b) E1, (c) E2 and (d) E3

E2 (Table 4). The produced oil asphaltenes in this case are more water-wet compared to original
bitumen and E1 (Figure 4). This increased water wetness could be a factor in the reduced
interaction between asphaltenes and clays. Co-injection of toluene and n-hexane with steam results
in the higher asphaltene content in produced oil than E2. This is because toluene is an asphaltene
solvent.
3. The asphaltene weight percent in produced oil and in the left behind oil (residual oil) varies
(compare asphaltenes in Table 4 with Table 5). While the lowest asphaltene content is detected for
the produced oil originated from E2, the residual oil asphaltenes of E2 yields the highest amount
for both from inside and outside the steam chamber (Table 5). This finding can be explained again
with the solubility of asphaltenes in n-hexane. The produced oil originated from E2 has less
asphaltene content, since asphaltenes are deposited on sand particles.
4. Because lower residual oil saturations are obtained with ES-SAGD experiments, the sweep
efficiency is higher for the ES-SAGD cases. Also, the effectiveness of steam chamber develop-
ment is better for ES-SAGD; because for Base SAGD case, the residual oil inside steam chamber
is higher than the outside steam chamber. This might be due to the interactions of clay, steam, and
asphaltenes and this interaction might be reduced away from the injection well.
SPE-171076-MS 9

Figure 6 —FTIR of (a) Original bitumen and produced oil for (b) E1, (c) E2 and (d) E3

FTIR Results
Beside the quantitative analyses summarized in above sections, qualitative characterization studies are
conducted on produced water, produced oil, spent rock, and asphaltene samples with Fourier Transform
InfraRed (FTIR) spectroscopy. Infrared spectroscopy (IR) is an important tool which offers information
on the molecular structure of the components.
Produced Water
The FTIR spectrums of produced water samples are shown in Figure 5. For reference, the FTIR spectrum
of distilled water is included (Figure 5-a). The characteristic distilled water peaks are O-H stretch at 3293
cm-1 and absorption peak at 1637 cm-1. Figure 5 shows that the peaks obtained from the produced water
of E1, E2, and E3 have similar distinctive peaks of the distilled water FTIR peaks. This explains the less
severe emulsions observed in Figure 2; implementing low organic content. At E3 (Figure 5-d), trace
amounts of organic content are detected as indicated by small peaks around 2911 cm-1. These peaks are
originated from CH stretch, and this can explain the slightly higher viscosity of produced water for E3
compared to other cases (Table 1).
Produced Oil
Figure 6 shows the FTIR spectrums of produced oil from the three experiments compared to a reference
10 SPE-171076-MS

Figure 7—FTIR of (a) Ottawa sand, (b) clay, and (c) postmortem inside steam chamber (d) postmortem outside steam chamber

FTIR spectrum of the original bitumen sample used (Figure 6-a). For original bitumen, peaks at 2953,
2924 and 2853 cm-1 indicate CH aliphatic stretches. Absorption peaks at 1458 and 1376 cm-1 are because
of CH2 and CH3 bends (Aleksandrov et al., 2014). The presence of polar components is represented by
OH and/or NH stretches at 3345, 1700 and 1604 cm-1 (He et al., 2013). A small peak around 2730 cm-1
is indicative of an aldehyde group along with the peaks observed around 1700 cm-1. Heteroatoms like
sulfur and chlorine are indicated by small peaks in the fingerprint region between 1000 and 600 cm-1
(Coates 2000). Comparing all the FTIR graphs, the produced oil samples show similar hydrocarbon peaks
like original bitumen. E1 Base SAGD shows the highest trace of water content as indicated by peaks at
3323, 1618, and 649 cm-1 (Reference Fig 5-a). This is a strong indication that the triple emulsions
observed in produced oil of E1 (Figure 3-b) are mainly due to the high water content. For the produced
oil samples, additional peaks (more prominent for E1) at 3692, 1011, 917, 746 cm-1 indicate presence of
clay and some sand which migrated into the produced oil. For reference, the FTIR spectrums of Ottawa
sand and clay have been provided in Figure 7-a and Figure 7-b respectively. Asphaltene and polar oil
component deposition in the rock causes dispersion of clays and fines, making them oil-wet and
promoting their outflow with the produced oil (Leontaritis et al, 1994; Pang et al, 2010). The presence of
clays and significant amount of water in the produced oil are believed to have a combined effect in
stabilizing the emulsions.
SPE-171076-MS 11

Figure 8 —FTIR of asphaltenes in (a) Original bitumen and produced oil for (b) E1, (c) E2 and (d) E3

Postmortem (spent rock)

The FTIR spectrums for the postmortem samples (both inside and outside steam chamber zones combined
into two graphs) are provided in Figure 7-c and Figure 7-d. For reference and easy understanding, FTIR
spectrums have been obtained for the Ottawa sand and clay (90% kaolinite and 10%illite) which were used
in all the experiments, as shown in Figure 7-a and Figure 7-b, respectively. FTIR of sand shows peaks
mainly in the fingerprint region, significantly at 1734, 1469, 1093, 779, and 694 cm-1. Characteristic clay
peaks are at 3688, 3651, 3621, 1115, 1026, 1003, and 910 cm-1. The peaks observed in the fingerprint
region from 1026-600 cm-1 represent Si-O and Al-OH functional groups (Saikia and Parthasarathy, 2010).
For the postmortem samples, the hydrocarbon presence is indicated by peaks at 2924, 2853, and 1458,
1376 cm-1 (Figure 6-a). Peaks at 3692, 3621 and 1003 cm-1 indicate clay and 1029, 910, 750, and 690 cm-1
show presence of both sand and clay as seen from reference graphs (Figure 7-a and Figure 7-b). The
postmortem FTIR spectrums for all three experiments are very similar. The absence of O-H peaks at
around 3293 and 1627 cm-1 (Figure 5-a) indicate the oil-wet nature of the spent rock which is also
determined by contact angle measurements (Figure 4).
Asphaltenes obtained from produced oil
For further analysis to understand the role of asphaltenes in emulsion formation in produced oil, FTIR
spectrums are obtained for asphaltenes separated from produced oil, and shown in Figure 8. Again, for
12 SPE-171076-MS

reference, these FTIR spectrums are compared to that of asphaltenes from original bitumen (Figure 8-a)
to determine the molecular level changes in the asphaltene composition obtained after each experiment.
The peaks around 3370, 1637, and 649 cm-1 indicate the presence of water in the asphaltenes (reference
Figure 5-a). The CH2 and CH3 peaks are similar to those observed in produced oil in Figure 6. The FTIR
of asphaltenes of produced oil compared to original bitumen show the presence of clay at 3692, 1029,
1007, 750, and 690 cm-1 (Figure 7-b). The peaks observed in the fingerprint region between 1093 and
1024 cm-1 indicate the Si-O-Si stretching vibrations. These peaks (indicative of clay and sand) are most
prominent for E1, Base SAGD, and least prominent for E3, ES-SAGD with co-injection of n-hexane and
toluene. This explains that the most severe emulsions in produced oil for E1 and least severe emulsions
for E3 (Figure 3) are affected by the clay and sand migration into produced oil. This migration is observed
also for E2, however, with the addition of solvent, wettability characteristics favor this interaction more
in the water phase, hence, the produced water of E2 (Figure 2-c) has the high solid content (Table 3).

Conclusion
The emulsions originated from SAGD and ES-SAGD are characterized in the scope of this study.
For produced water, the oil-in-water emulsions observed are not severe. In these cases, oil particles in
water can be removed using a centrifuge.
For produced oil, the more severe emulsions observed in base SAGD compared to ES-SAGD have
been attributed to the action of asphaltenes which are present in greater amount (and more oil-wet) in base
SAGD produced oil. The asphaltene aggregates form a strong interfacial film around the water droplets,
thereby stabilizing the water-in-oil emulsions. There can also be a role of clays which were found to be
significantly present in the produced oil for base SAGD. It is being further investigated through XRD
analysis and SEM.
For spent rock, oil-wet nature was determined by contact angle measurements for both SAGD and
ES-SAGD cases, which was reaffirmed by FTIR. Highest residual oil was calculated for base SAGD and
lowest for ES-SAGD with co-injection of hexane and toluene. This implies the best sweep efficiency for
ES-SAGD with hexane and toluene (due to asphaltene solubility in toluene). Lowest asphaltene precip-
itation was found for ES-SAGD with co-injection of hexane and toluene. This correlates with lowest
residual oil, i.e., better oil recovery.
In ES-SAGD, the type of solvent plays a major role in the process efficiency. Although similar less
severe emulsions were observed in the produced oil for both the ES-SAGD cases, the residual oil was
lower (better sweep efficiency) and asphaltene precipitation was lesser for ES-SAGD with co-injection of
hexane and toluene compared to co-injection with only hexane.
ES-SAGD was found to be more efficient than SAGD in terms of less severe emulsions in produced
oil, lesser asphaltene precipitation in the reservoir and better oil recovery.
This paper was selected for presentation by an SPE program committee following review of informa-
tion contained in an abstract submitted by the author(s). Contents of the paper have not been reviewed by
the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not
necessarily reflect 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 not be copied. The abstract must contain conspicuous acknowl-
edgment of SPE copyright.

Acknowledgements
We acknowledge the financial support and opportunity provided by Texas A&M University to conduct
experiments in Ramey Thermal Recovery Laboratory. We also acknowledge the member of Heavy Oil,
SPE-171076-MS 13

Oil shales, Oil sands, & Carbonate Analysis and Recovery Methods (HOCAM) Research Team at Texas
A&M University, Petroleum Engineering Department, for their helps.

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