Journal of Industrial and Engineering Chemistry 77 (2019) 198–208

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Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

The role of IFT and emulsification in recovering heavy oil during S/SP
flooding
MingChen Dinga,b , Yefei Wanga,b,* , Zongyang Lia,b,c, Dong Zhonga,b , Fuqing Yuanc ,
Yangwen Zhuc
a
Key Laboratory of Unconventional Oil & Gas Development (China University of Petroleum (East China)), Ministry of Education, Qingdao 266580, PR China
b
Shandong Key Laboratory of Oilfield Chemistry, School of Petroleum Engineering, China University of Petroleum (East China), Qingdao 266580, PR China
c
Exploration and Development Research Institute of Shengli Oilfield, Dongying 257100, PR China

A R T I C L E I N F O A B S T R A C T

Article history: Six surfactant (S) and surfactant-polymer (SP) systems (with different interfacial tension (IFT) and
Received 20 February 2019 emulsification behaviors) were compared for their ability to recover heavy oil. Attention is paid to their
Received in revised form 26 March 2019 emulsifying capacity, emulsion stability, heavy-oil viscosity reduction, microscopic displacement, and
Accepted 20 April 2019
final oil recovery. It is found that the advantages in emulsion stability, oil-viscosity reduction, and more-
Available online 27 April 2019
enlarged sweep volume (observed in microscopic displacements), make the non-ultra-low IFT systems
more powerful in recovering heavy oil compared to other ultra-low-IFT systems, indicating the dominant
Keywords:
role of emulsion stability over ultra-low-IFT for SP systems when enhancing heavy oil (657.0 mPa s)
Heavy oil
Oil recovery
recovery.
Chemical flooding © 2019 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
Interfacial tension reserved.
Emulsification

Introduction these cases, application of chemical flooding becomes promising

As light-oil reservoirs draw to the end of their development life,
more attention has been paid to the heavy oil reserves that are
needed to meet increasing demand for crude oil. China has rich
heavy oil reserves of about 15  108 t, mainly distributed across the
Liaohe, Xinjiang, Shengli, and Henan Oilfields [1,2]. According to
statistics from the China Petroleum and Chemical Corporation,
one-third of heavy-oil resources are developed by water flooding
[3]. Owing to the high mobility ratio of water and heavy oil, only
about 5%–10% of the oil can be recovered by such water injection
[1]. The other two most commonly used methods of developing
heavy oil are thermal recovery (including hot water flooding,
steam flooding, or steam huff and puff injection) and fire methods
that are mainly designed to reduce the viscosity of the heavy oil by
heating (referring to the significant sensitivity of heavy oil viscosity
to temperature), thus to recover it: however, they become
inapplicable to deep, thin reservoirs due to significant heat loss
during injection. Additionally, as energy consumption and demand
increase, sometimes, such an amount of fuel is not able to generate
enough steam for those thermal recovery processes to work. For
* Corresponding author at: Petroleum Engineering, China University of Petro-
leum East China, No.66, West Changjiang Road, Qingdao, 266580, PR China.
E-mail address: Wangyf@upc.edu.cn (Y. Wang).
and has indeed proved successful when recovering light oil.
Chemical flooding includes polymer flooding, alkali flooding,
composite flooding, etc. Polymer flooding has been used for
recovering oil since the 1960s. It enhanced oil recovery mainly by
thickening water to improve the water/oil mobility ratio, thus
inhibiting viscous fingering. By 2015, there were 11 heavy oil
polymer flooding projects in operation worldwide. In order to
promote the displacement efficiency of heavy oil in addition to the
better mobility control of a single polymer, an alkaline or
surfactant is usually added to form alkaline-polymer (AP),
surfactant-polymer (SP), and alkaline-surfactant-polymer (ASP)
systems. Actually, systems with alkaline (such as AP and ASP)
constituents attract much attention among those interested in
heavy oil recovery processes because of their excellent perfor-
mance in reducing IFT and emulsifying crude oil [4–8]. The injected
alkali reacts with natural petroleum acids to form the in situ
surfactant which has a synergistic effect with the injected
surfactant in reducing IFT [7]. According to a survey of the Shengli
Oilfield, by 2015, there were more than 30 flooding projects using
chemical systems containing alkaline (among about 37 chemical
combination flooding projects) worldwide: unfortunately, chemi-
cal flooding with alkaline suffers from severe scaling problems that
cause frequent clamping in pumps, wellbore blockages, and oil-
layer scaling, finally, causing a decline in well productivity and an
increase in operating costs [9]. People tend to choose the SP system

https://doi.org/10.1016/j.jiec.2019.04.036
1226-086X/© 2019 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
 M.C. Ding et al. / Journal of Industrial and Engineering Chemistry 77 (2019) 198–208
to overcome these problems. With the development of some
highly effective surfactants, SP systems also behave as well as
ultra-low IFT (equal to or less than 10 3 mN/m) in the absence of
alkaline [10].
Mechanisms of SP flooding have been much researched since
the discovery of chemical compound flooding technology in the
1980s. They have been recognized as viscosification, low IFT,
emulsification, and wettability alternation [4,10–13]. Follow the
research and development of chemical flooding in conventional-
light oil reservoirs, researchers have investigated the IFT behaviors
of heavy oil-chemical systems (especially the chemical systems
with alkaline) [4–8]. An ultra-low IFT is usually suggested for heavy
oil recovery applications, however, some studies found that
formation of emulsions is also a possible recovery mechanism
for heavy oil. Researchers proposed that oil-in-water (O/W) or
water-in-oil (W/O) emulsions may plug water flooded channels,
resulting in improved volumetric sweeping of the reservoir [14–
16]. McAuliffe [17,18] found a larger amount of emulsion entered
more permeable regions: the flow of such emulsions became
restricted due to the Jamin effect. As a result, the water flowed into
less permeable regions, leading to extended sweep volume. By
investigating the current situation of heavy oil chemical flooding,
Pei [1] believed that it is more important to expand the sweep
volume than improve displacement efficiency for recovering heavy
oil because of the lower sweep efficiency in the previous water
flooding of heavy oil. Yu [19,20] using a fine emulsion system,
found it exhibits well-plugging and sweep-volume-enlargement
behaviors. In addition, researchers also pointed out that formation
of O/W emulsion can significantly reduce heavy oil viscosity, which
is bound to help the flow of heavy oil. Chen [6] considered that
enhancement in emulsifying ability leads to improvement of the
oil washing ratio. Using a fine emulsion flooding system, Feng [21]
recently found that emulsification can both improve the displace-
ment efficiency and the sweep efficiency. Qi [22] developed a
smart chemical agent (consisting of interfacially active and pH
responsive polymer-coated nanoparticles) to reversibly stabilize,
recover, and break oil/water emulsions through variation of
solution pH.
The aforementioned studies remind us of the importance of
emulsification in recovering heavy oil. That being the case, a
natural question arises with respect to the optimization of
chemical flooding systems, that is, which one is more important
in chemical flooding for enhancing heavy oil recovery: conven-
tional ultra-low IFT or emulsification? Based only on
current results, this remains unclear. Therefore, it is of
significant importance and practical interest to address this
issue for optimization of SP systems in displacing heavy oil. In
this work, six surfactant (S) and surfactant-polymer (SP)
systems (with different interfacial tension (IFT) and emulsifi-
cation behaviors) were designed and compared for their
ability to recover heavy oil. They are the non-ultra-low-IFT
but fine-emulsion-stability S #1 and SP #4, ultra-low-IFT but
Table 1
Chemical systems used for recovering heavy oil and their measured properties.
System no. Types Chemical formula
#1 S 0.3%S (anionic and nonionic surfactant)
#2 S 0.3%S (anionic and nonionic surfactant)
#3 S 0.3%S (polyether sulfonate, polyether aminopropyl sodium,
alkanolamide, and fatty alcohol polyoxyethylene ether)
#4 SP 0.3%S(#1) + 0.18%P
#5 SP 0.3%S(#2) + 0.18%P
#6 SP 0.3%S(#3) + 0.18%P
199
poor-emulsion-stability S #2 and SP #5, and ultra-low-IFT and
medium-emulsion-stability S #3 and SP #6. The comparisons
were initiated from the evaluation of their IFT, emulsifying
capacity, and emulsion stability. Then, considering that surfac-
tants with different IFT and emulsification properties would
behave differently in reducing heavy oil viscosity (that is very
important for heavy oil mobilization as reported [23]), the in situ
viscosity of heavy oil and chemical solution mixtures was tested by
using flow tests in cores. Thereafter, visual displacement experi-
ments were carried out to enable microscopic displacement
characteristic investigation of those surfactants (#1, #2, and #3).
Finally, oil recovery factors were determined by macroscopic
displacing tests in sand-packs (using #4, #5, and #6). By these
systematic comparisons, the potential of a SP system with non-
ultra-low IFT but fine emulsion stability for recovering heavy oil
could be determined, more importantly, we can identify which
aspect of an SP system is more important (ultra-low IFT or fine
emulsification?).
Experimental work
Fluid and chemicals
A heavy oil was collected from the Shengli oil field, Dongying,
China and used for all experiments referring to crude oil. The
measured density and viscosity of the sample were 969.2 kg/m3 (at
70  C, 0.101 MPa) and 657.0 mPa s (at 70  C, 0.101 MPa), respective-
ly. Three types of surfactant (#1–#3) were designed in the
laboratory with their specific compositions summarized in Table 1.
The polymer used in SP system preparation is a partially
hydrolyzed polyacrylamide (HPAM) with a molecular weight
2000  104. Its viscosity, at a concentration of 1800 mg/L and
shearing rate of 7.34 s 1, is 33.5 mPa s. In addition, the salinity of
the simulated formation water is 9754.0 mg/L (Table 2).
Interfacial tension measurement
Measurement of IFT between chemical solutions (#1–#6) and
heavy oil was performed at 70  C using the spinning drop method
in a Texas-500C tensiometer. With an image-capture device and
image-acquisition software equipped, this equipment could
automatically measure and record the dynamic IFT. For this part,
IFT dependence on testing time was investigated with respect to
the three-chosen surfactants and their corresponding SP systems.
Emulsification property evaluation
Emulsifying capacity
Emulsifying capacity (used to describe the degree of difficulty in
emulsion generation by chemicals) of surfactants and correspond-
ing SP systems were measured using an oscillating method in an
IKA KS 4000i oscillating instrument (Fig. 1). The reagent bottles,
Measured properties
IFT (mN/m) Emulsifying capacity Emulsion stability
1
3.0  10 weak Strong
3
1.2  10 Strong weak
3
1.0  10 Medium Medium
1
4.5  10 Weak Strong
3
1.2  10 Strong weak
3
1.2  10 Medium Medium
200 M.C. Ding et al. / Journal of Industrial and Engineering Chemistry 77 (2019) 198–208

Table 2
The composition of Shengli Oilfield formation water.

Ion type Cl SO42 CO32 HCO3 Na++K+ Ca2+ Mg2+ Total

Concentration (mg/L) 5423.0 0.0 0.0 656.0 3414.0 193.0 68.0 9754.0

heavy oil and only brine or polymer was also tested. Thus,
viscosity-reduction performances can be compared among chemi-
cal solutions.

Microscopic flooding tests

A visual glass-etched model was used as porous medium to

investigate the microscopic displacement characteristics of the
three-chosen mixtures. Fig. 2 illustrates a schematic of the
microscopic oil displacement experimental apparatus. The specific
steps for this micro-model flooding tests are as follows: (1) after
heating to 70  C, the brine was pumped into the model from a
transfer vessel for water saturation; (2) then, oil saturation was
established by using an oil-displacing-water method; (3) after-
wards, water flooding was initiated and continued until a high
Fig. 1. IKA KS 4000i oscillating instrument used for emulsifying. water cut up to 98% was reached; (4) to observe the microscopic
displacement characteristics of different surfactants (#1–#3), their
solutions were continuously injected at a rate of 0.001 mL/min; (5)
containing the same amount of 7 mL heavy oil and testing fluid
video and photography of water flooding and surfactant flooding
(#1–#6), were fixed to a shaking bed in the instrument. After
processes were recorded by using a digital video camera and all
heating to 70  C, a horizontal-circumferential oscillation was
such images were stored in a computer connected thereto.
initiated with a discontinuous growth in frequency from 200 to
400 oscillations per min. The oscillation at constant frequency was
Macroscopic flooding tests
maintained for 2 min. This oscillation would disturb the oil–water
interface, and then develop into emulsification. Also, the fluids in
The sand-packs used for macroscopic flooding tests were 2.5 cm
the bottle would form a rotating flow induced by this oscillation. At
in diameter and 30 cm in length. Fig. 3 shows a schematic
the same time, the oil and water would flow at different rates due
representation of the layout of the macroscopic flooding test
to their different viscosities and adhesions to the bottle wall, thus
apparatus. The experimental procedures are as follows: first, the
forming relative flowing and shearing at the oil–water interface,
wet-packed sand-pack was flooded by water for permeability
helping emulsification. Such shearing is indeed one of the main
measurement; then, temperature of the system was increased to
causes of emulsification in reservoirs [24]. By increasing the
70  C, after which crude oil was pumped into the model to displace
oscillation frequency, a stronger emulsifying power was provided,
the water to allow oil saturation. Afterwards, the model was
during which an early occurrence of emulsification indicates a
flooded with water until oil production became negligible (water
more powerful chemical system for emulsifying heavy oil.
cut 98%). Then, 0.3 pore volume (PV) SP solutions (#4–#6) were
injected to displace the oil, followed by post-water flooding until
Emulsion stability
the volume of oil gathered in the collector became negligible. The
Bottle tests were conducted to compare the emulsion stability
specific parameters of the sand-packs and the corresponding oil
of different chemical solutions on heavy oil. At an ambient
recovery factors are summarized in Table 3.
temperature of 70  C, 5 mL testing solution (#1–#6) was put into a
set of bottles and, then, 5 mL oil was added. After shaking, these
bottles were maintained at the experimental temperature for
precipitated water observation. An index of water segregation rate
(WSR), defined as the volume ratio of precipitated water to that of
initial water, was used for emulsion-stability evaluation. Addition-
ally, emulsions formed by different chemical solutions (#1–#6)
were also observed throughs a digital microscope at different
times to allow judgment of emulsion morphology and stability.

In situ viscosity measurement of heavy oil and chemical solution

mixture

To obtain the capacity of surfactant and SP (performing

different IFT and emulsification behaviors) in improving heavy
oil mobility by reducing its viscosity, heavy oil and surfactant or SP
(with oil–water ratio of a first 2:8, and then 5:5 by controlling their
injection rate Qw and Qo) were simultaneously injected into a core
(permeability ~1300 mD, 2.5 cm in diameter, 10 cm in length) for
injection pressure measurement, based on which the in situ
viscosity of such mixtures could be calculated according to Darcy’s
law. In addition to the chemical solution tests, a blank injection of Fig. 2. Schematic of the microscopic flooding test apparatus.
 M.C. Ding et al. / Journal of Industrial and Engineering Chemistry 77 (2019) 198–208
Fig. 3. Schematic of the macroscopic flooding test apparatus.
Experimental results and discussion
IFT measurement
IFT has always been the focus of research for compound system
flooding and is closely related to the formation and stability of an
emulsion [2–8]. The dynamic IFT behaviors observed to act
between heavy oil and chemical solutions were analyzed with the
measured IFTs plotted as a function of test duration (Fig. 4). As
expected, the collected S #1 and its corresponding SP #4 systems
perform as a non-ultra-low IFT of~10 1 mN/m with heavy oil. While
S #2, #3, and corresponding SP #5, #6 systems behave well with
regard to reducing IFT with such heavy oil: that significantly
decreases at ultra-low values of~10 3 mN/m over time. As reported,
such ultra-low values would contribute to EOR processes of
chemical flooding [2–8]. If an ultra-low IFT is the main indicator for
surfactant selection, these two would be the most promising
candidates, however, people are becoming more aware of the
importance of emulsification (in addition to such conventional
ultra-low IFT index) for enhancing heavy oil recovery [14–21].
Whether these S #2, #3 and their corresponding SP #5, #6 systems
with ultra-low IFTs perform best in recovering heavy oil, needs
further evaluation. So by these IFT measurements, as expected, we
have found six chemical systems with different IFT behaviors in
heavy oil for further comparative study.
Emulsification of heavy oil and chemical systems with different IFT
Emulsifying capacity
At present, emulsification-property evaluation of a chemical
system mostly focuses on its emulsion stability by using bottle test
method as described previously. However, researchers believed
that emulsifying capacity (referring to the emulsion-generation
capacity by chemicals) is also important for oil displacement. Luan
and Hou [25,26] defined an emulsification index with which to
characterize the emulsifying capacity and emulsion stability. Ge
[27] found that a surfactant with which it is easy to form an
emulsion has a better oil-displacement performance. Here, using
an oscillating method, the emulsifying capacities of the chosen
Table 3
Physical properties of the sand-packs and their corresponding oil recovery factors.
Flooding system Permeability (mD) Initial oil saturation (%)
#4 1300 72.7
#5 1300 72.7
#6 1310 76.4
201
Fig. 4. Dynamic IFT curves of heavy oil and S, SP systems.
surfactant and corresponding SP systems were elucidated. The
acquired emulsification state of the heavy oil and chemical systems
(#1–#6) under different oscillating frequencies is shown in Fig. 5.
As Fig. 5 shows, it is difficult for the surfactant and heavy oil
system to emulsify at lower oscillation frequencies of 200 and 250
oscillations per min because of the lower energy input. Using these
low frequencies, we oscillated the system for 10 min (rather than
the 2 min used to date), but to no avail: emulsification did not
occur. It can be inferred that there is a basic energy input
requirement for emulsification by such disturbance and shearing
during oscillating: only when this is met, can chemical agent and
heavy oil systems be emulsified.
By increasing the frequency to 300 oscillations per min, the S #2
and heavy oil system emulsified first, followed by S #3 at 350 per
min, and S #1 at 400 per min. The ability to emulsify heavy oil in a
descending order is: #2, #3, and #1. Combined with the IFT results
(Fig. 4), it is found that systems with an ultra-low IFT (#2 and #3)
are more powerful in emulsifying or dispersing heavy oil than
those with non-ultra-low IFT (S#1). Theoretically, an emulsion is a
thermodynamically unstable system. Emulsification is accompa-
nied by an increased energy at the oil–water interface. The lower
the IFT, the smaller the increased interfacial energy upon
emulsification, thus, emulsification becomes much easier for S
#2 and #3. Further evidence to support this may be seen for SP #5,
and #6 systems, with ultra-low IFTs (10 3 mN/m), that emulsify
heavy oil before system #4 with its high IFT (10 1 mN/m).
Additionally, it is found that presence of a polymer is conducive to
emulsification. SP #5, #6 and heavy oil systems start to emulsify at an
oscillating frequency of 250 oscillations per min, while that happens
at a greater frequency of 300 per min for their corresponding S #2 and
#3 systems. That may be a result of the intensified interfacial
shearing effect in the presence of a polymer additive, as the viscosity
of the water phase is increased in its presence.
Emulsion stability
Fig. 6 depicts the measured WSR plotted as a function of test
duration using chemical solutions #1–#6 in bottle tests. As shown
in Fig. 6(a), in the first 20 min (or so), the WSR of surfactant and
Oil recovery factor (%)
Water flooding Chemical flooding Total
39.1 15.6 54.7
38.8 10.5 49.3
38.8 10.0 48.8
202 M.C. Ding et al. / Journal of Industrial and Engineering Chemistry 77 (2019) 198–208
Fig. 5. Emulsification state of heavy oil and chemical solutions under different oscillating frequencies.
heavy oil systems increased over time, indicating a rapid
destruction of emulsions. Afterwards, this increase decelerated
and stabilized at high values of 96% and 100% for emulsions formed
by S #2 and #3, but a lower value of~80% for that formed by S #1. It
is interesting to see that S #1 with the highest IFT (Fig. 4) and
lowest emulsifying capacity (Fig. 5), generated the most stable
emulsions. Meanwhile, S #2 and #3 with the lowest IFT (Fig. 4) and
strongest emulsifying capacity (Fig. 5), generated the least stable
emulsions. In other words, an ultra-low IFT and strong emulsifying
power may not necessarily lead to a more stable emulsion for
surfactants.
Microscopic observation of the emulsified oil droplets
(Fig. 6(a)) further proves a more stable emulsion was formed by
S #1. After 2 min, the emulsion formed by S #1 is smaller (in oil-
droplet size terms) and more dispersed in the water phase; but for
S #2 and #3, a small number of large oil droplets were observed,
emulsion coalescence occurred, and the consequent oil belt
appeared. This observation was in line with the WRS results,
further confirming the best emulsion stability of S #1, followed by
those of S #3, and S #2.
Fig. 6(b) demonstrates the WSR of SP systems #4–#6. As
reported, the addition of polymer to surfactant solution consider-
ably could improve the stability of emulsions. Almost no
segregated water was observed between 80 and 110 min for SP
#4, #5, and #6. Researchers mainly attribute this stability
improvement to the weakened velocity of water film efflux and
reduced collisions of oil droplets by viscosity increase of the water
phase [28]. Afterwards, the WRS increases gradually, but SP #4
(containing S #1) still returns the lowest WRS value and the best
emulsion stability. Its final WRS at 560 min is 52%, while those of SP
#5 and #6 are 96% and 94%, respectively.
Fig. 6. Water segregation rate (WSR) of chemical solution and heavy oil systems plotted as a function of test duration, together with macroscopic and microscopic images-
magnification: 40 times: (a) S #1–#3, and (b) SP #4–#6.
As before, the morphologies of emulsified oil droplets formed
by SP #4–#6 were photographed after different test durations
(Fig. 7). Initially, emulsions are all of small size and are well
dispersed in the water phase; slight coalescence occurs in the
emulsions formed by SP #5 and #6. Afterwards, severe coalescence
occurs in these two systems when tested for 30 and 90 min. Very
large oil droplets, and even a continuous flaky oil belt, are visible,
evincing the relatively weak power of SP #5 and #6 in stabilizing
emulsions. As for SP #4, the oil droplets remain small and well
dispersed when tested for 90 min. These microscopic observations
are consistent with the WSR results in Fig. 6(b), once again,
suggesting the most powerful surfactant for stabilizing emulsions
is S #1, followed by S #3, then S #2. In addition, the emulsions are
seen to coalesce slightly faster in these visual observations of tests
(in comparison with data shown in Fig. 6(b)). That may be
influenced by the pressure exerted by the cover glass during
sample preparation.
In general, systems (#2, #3, #5 and #6) with ultra-low IFTs,
perform poorly when stabilizing emulsions, while systems (#1 and
#4) having non-ultra-low IFTs, can perfectly stabilize such an
emulsion. This may imply that ultra-low IFT is not conducive to
emulsion stability, which can be further understood in the
following ways: (1) a sudden oil–water-interface increase occurs
readily under ultra-low IFT conditions, which would cause an
instant decrease in the density of the adsorbed-surfactant in oil–
water interface, thus, weaken such an interfacial film, reduce
electrostatic repulsion among oil droplets, and finally, help their
coalescence [29]. (2) a solvated water layer is present outside the
surfactant-adsorption layer due to solvation of surfactant-hydro-
philic groups, increasing the stability of oil droplets: however, with
reduced density of such adsorbed surfactant, this solvated water
 M.C. Ding et al. / Journal of Industrial and Engineering Chemistry 77 (2019) 198–208 203

Fig. 7. Microscopic images of morphology of emulsions formed by SP #4, #5, and #6 at different testing times (magnification: 40 times).

layer would be simultaneously weakened, resulting in reduced
stability of oil droplets [12]; (3) such an easily extended oil–water
interface (in ultra-low IFT conditions), on the one hand, increases
the contact and collision opportunities of emulsions [19,20], on the
other hand, results in rapid growth of the oil droplets, but emulsion
stability is inversely proportional to the size of the dispersed
droplets [21,30]; (4) when ultra-low IFT is achieved, the surfactant
adsorbed at the oil/water interface usually reaches a hydrophile-
lipophile balance (or one with HLB = 7) [31]. In this case, the
interface tends to be planar rather than curved, whereas a stable
emulsion needs a curved interface. Therefore, the emulsion may be
unstable when ultra-low IFT is achieved. In addition to those
aforementioned effects of ultra-low IFT on emulsion stability,
different surfactants (#1–#6) may generate interfacial films of
different strengths (by their adsorption), which also influence the
stability [32].
In situ viscosity of heavy oil and chemical solution mixtures
Emulsification is one of the main mechanisms for improving
heavy oil recovery by forming O/W emulsion, reducing the oil
viscosity and enhancing the flowability of heavy oil [22,23].
Considering the different performances of six surfactant and SP
systems in IFT, emulsifying capacity, and emulsion stability, they
may behave differently with regard to viscosity reduction in heavy
oil. Therefore, it is worthwhile to deduce which chemical is best at
reducing heavy oil viscosity or, more importantly, to find which
property of surfactant is critical for improving the flow capacity of

Fig. 8. The injection pressure of heavy oil and chemicals plotted as a function of injection volume: (a) S-heavy oil and (b) SP-heavy oil.
204 M.C. Ding et al. / Journal of Industrial and Engineering Chemistry 77 (2019) 198–208
heavy oil (ultra-low IFT, strong emulsifying capacity, or good
emulsion stability?). For this purpose, heavy oil and chemical
solution (#1–#6) were simultaneously injected into a core for
injection pressure measurement and in situ viscosity calculation
(Figs. 8 and 9).
Considering the fact that chemical flooding is usually initiated
when the heavy oil reservoir approaches a high-water-cut stage, a
low-oil-content condition (20 wt% oil) was adopted in these flow
tests. The Heavy oil+#1 system has a lower stable injection
pressure (0.08 MPa) than the blank Heavy oil + Brine system
(0.14 MPa), indicating the excellent performance of S #1 in
reducing heavy oil viscosity. According to an approximate
calculation (based on Darcy’s formula), Heavy oil+#1 exhibits a
reduced in situ viscosity of 52.2 mPa s in comparison with the
initial 103.4 mPa s of a Heavy oil + Brine system (Fig. 9(a)). Heavy oil
+#2 and Heavy oil+#3 have higher injection pressures than the
blank Heavy oil + Brine system. As a result, they exhibit no
viscosity-decreasing effect and have in situ viscosities of 176.9 mPa
s and 114.9 mPa s (Fig. 9(a)). In general, S #1 best reduces the
viscosity of heavy oil by oil-in-water emulsification, followed by
#3, and lastly #2. This is still true at a high oil content (50 wt% oil).
Heavy oil+#1 system still has the lowest injection pressure of
0.23 MPa, compared to the 0.3 MPa, 0.5 MPa, and 0.43 MPa for
Heavy oil + Brine, Heavy oil+#2, and Heavy oil+#3 systems,
respectively (Fig. 8(a)). Accordingly, its in situ viscosity is the
lowest at 176.2 mPa s, compared to the 229.8 mPa s, 383.0 mPa s,
and 329.4 mPa s of the other systems (Fig. 9(a)).
Generally, S #1 behaves as a non-ultra-low IFT, and has the
poorest emulsifying capacity but best emulsion stability, and is
most powerful in reducing heavy oil by O/W emulsification, which
indicates that emulsion stability is more important than IFT and
emulsifying capacity with regard to oil-viscosity reduction. Further
evidence to support this notion lies in the results of SP systems in
Fig. 9. The calculated in situ viscosity data of heavy oil and chemicals mixtures: (a) S-heavy oil and (b) SP-heavy oil.
Figs. 8(b) and 9 (b), where SP #4 that also has non-ultra-low IFT,
poorest emulsifying capacity, but the best emulsion stability, again
performs best in reducing heavy oil viscosity. In addition, due to
the improved emulsion stability caused by polymer addition to
such SP systems (Fig. 6), SP #5 and #6 start to exhibit some
viscosity-decreasing effects (Fig. 9(b)) while their corresponding
surfactants (#2 and #3) do not (Fig. 9(a)). Such improvement also
narrows the difference in oil-viscosity-decreasing capacity among
SP #4, #5, and #6 (in comparison with that among their
corresponding surfactants S#1, #2, and #3).
Microscopic displacements in the surfactant system
Enhancing heavy oil recovery is the ultimate goal of chemical
selection and evaluation. Differences in IFT (Fig. 4), emulsifying
capacity (Fig. 5), emulsion stability (Fig. 6), and heavy-oil-
viscosity-reducing effect (Fig. 9), would inevitably lead to different
displacement characteristics of chemicals. To address this differ-
ence, a series of microscopic oil displacement experiments were
conducted using S #1–#3.
Emulsification of heavy oil in porous media
An observed typical emulsion morphology (formed by S #1–#3)
is shown in Fig. 10. We can see that a small amount of oil droplets
emerge during water flooding (Fig. 10(a)), and such oil droplets
become more numerous during S #1 injection, showing its good
emulsification capacity, but for S #2 and #3 flooding, although they
have the most powerful emulsifying capacity in bottles (Fig. 4),
almost no emulsified oil droplets could be found in this porous
model. Crude oil is more likely to be stripped and flow in a form of
oil wires (Fig. 10(c) and (d)) owing to the ultra-low IFT and the
consequent easy oil–water-interface extension. Even if oil droplets
are instantly formed by shearing or stick-break effect, they readily
 M.C. Ding et al. / Journal of Industrial and Engineering Chemistry 77 (2019) 198–208
Fig. 10. Images showing the emulsion morphology of heavy oil in porous media during water and surfactant flooding: (a) water, (b) S #1, (c) S #2, (d) S #3.
gather and form oil wires or belts due to the poor system stability
(Figs. 6 and 7). This also indicates that the strong emulsifying
capacity of a chemical in the bottle tests (Fig. 5 and elsewhere [25–
27]) does not mean that it can form a large number of stable
emulsified oil droplets in porous media.
Such O/W emulsions during S #1 flooding become more
prevalent than S #2, #3, which partly explains their differences in
reducing heavy oil viscosity (Figs. 8 and 9). More interestingly,
combined with the results of emulsification performance evalua-
tion (Figs. 6 and 7), we find that emulsion stability is more
important for heavy oil emulsification in porous media than the
emulsifying capacity (evaluated in bottle tests (Fig. 5)).
In addition, the inducement to formation of a new-emulsified
oil droplet by previously generated oil droplets was observed
during S #1 flooding (Fig. 11). Specifically, as the previously-
formed No. 1 oil droplet is transported to a pore throat, the flow
velocity on the side of the droplet is increased, owing to a
significantly reduced flow of water passing the partial
volume occupation by the oil droplet therein (Fig. 11(a)). This
increased flowing velocity enhances the scouring force of water
on the residual oil, thus, driving it forward to form half-droplet
No. 2 (Fig. 11(b)). Once formed, a direct-displacement force
causes it to continue to creep forward, occupying the next pore
throat, and finally, breaking into a new oil droplet (Fig. 11(c)).
Then, this newly formed oil droplet will trigger the formation of
the next-new oil droplet. This is why a large number of oil
droplets appear in the S #1 flooding process. The formation of
these oil droplets can, on the one hand, expand the sweep
volume of the flooding process by the well-known Jamin effect,
on the other hand, peel off residual oil from the rock wall to
improve flooding efficiency, but for S #2 and #3 flooding
processes the peeled crude oil is more likely to form oil wires or
belts instead of isolated droplets.
Displacement characteristics
The different IFT and emulsification properties will inevitably
result in differences in oil displacement characteristics of different
surfactants. The differences among S #1, #2, and #3 are illustrated
in Figs. 12 and 13.
Fig. 11. Images illustrating the generation of an oil droplet and its corresponding EOR mechanism acquired during S #1 flooding.
205
In Fig. 12(b) and (c), S #2 and #3 (acting as ultra-low IFT with
heavy oil) are powerful when removing residual oil from water-
swept regions. Almost all the crude oil in these regions is washed
out by surfactant solution. This proves once again the importance
of ultra-low IFT in improving oil displacement efficiency (as
reported), and is also the main consideration for those pursuing
ultra-low IFT in chemical flooding processes. As to S #1 flooding
(Fig. 12(a)), the oil could never be washed out as clear as that in S
#2 and #3 flooding because of its relatively high IFT with heavy oil:
however, through inspection of the overall residual-oil distribu-
tions (Fig. 13), we find a significantly enlarged sweep volume
during S #1 injection, the crude oil on the non-mainstream line
area (the lower left and upper right corners of the image) has been
effectively swept clean. This is mainly attributed to the excellent
emulsion stability (in Figs. 6 and 7), the development of emulsified
oil droplets in porous media (Fig. 10), and the consequent Jamin
effect appearing during the flow of these emulsified oil droplets
[19,20]. For ultra-low IFT cases, S #2 and #3 tend to mobilize the
residual oil in the form of oil wires or belts instead of emulsified oil
droplets (Fig. 10), which can effectively remove almost all residual
oil from the water-swept area but never expand the sweep volume
as effectively as S #1. As a result, a significant amount of crude oil is
still stripped in the non-mainstream line area after S #2 and #3
flooding. Generally, from the point of view of the remaining oil
after surfactant flooding, S #1 (with the best emulsion stability)
outperforms S #2 and #3, showing the importance of emulsion
stability in expanding sweep volume.
Macroscopic displacements of SP system
According to the aforementioned analysis, the S #1 with
relatively high IFT, weak emulsifying capacity, but strong emulsion
stability, performs poorly when trying to remove heavy oil from
initially-water-swept regions, but behaves best when extending
the sweep volume which is of importance to recovery of heavy oil
[1]. Flooding tests in the visual model in Fig.13 have already proved
the advantage of S #1 in recovering heavy oil over S #2 and #3, but
for the SP flooding of heavy oil, the addition of the polymer can play
a certain role in enlarging the sweep volume due to its improved
206 M.C. Ding et al. / Journal of Industrial and Engineering Chemistry 77 (2019) 198–208

Fig. 12. Residual oil distributions in the swept regions of surfactant flooding.

Fig. 13. Residual oil distributions in the whole model after surfactant flooding (lower right corner injection, upper left corner output).

mobility ratio. In this case, the expansion of sweep volume by
emulsified oil droplets (through the Jiamin effect) may become less
important than in the previous surfactant flooding. So for further
confirmation of the superiority of SP #4, macroscopic displace-
ment tests were conducted for oil-recovery measurement with SP
#4, #5, and #6 (containing the corresponding S #1, #2, and #3).
With continued water flooding, the heavy oil gradually flows
from the outlet, resulting in a rapid increase in oil recovery
(Fig. 14): the flow in the model changes from a pure heavy oil flow
to a two-phase oil–water flow. As a result the injection pressure
decreases (Fig. 15). At the same time, the injected water quickly
breaks through from the outlet when 0.2PV water is injected
because of the high water–oil mobility ratio, which leads to a
significant increase in water cut (Fig. 16).
During SP injection, the injection pressure significantly
increases due to the enhanced viscosity of the water phase arising
from addition of the polymer component in the SP system (Fig. 15).
The pressure drop during SP #4 flooding is noteworthy, while those
in SP #5 and #6 keep growing during system injection. This
pressure declination during SP #4 injection is in accordance with
the pressure drop observed in the oil–water mixture flow tests
(Fig. 8), which once again proves the outstanding ability of SP #4

Fig. 14. Oil recovery factors plotted as a function of injection volume during water, SP (#4–#6), and post-water flooding.
 M.C. Ding et al. / Journal of Industrial and Engineering Chemistry 77 (2019) 198–208 207

Fig. 15. Pressure drops plotted as a function of injection volume during water, SP (#4–#6), and post-water flooding.

Fig. 16. Water cuts plotted as a function of injection volume during water, SP (#4–#6), and post-water flooding.

Fig. 17. Images of the emulsified oil droplets in the produced water phase during SP flooding.
208 M.C. Ding et al. / Journal of Industrial and Engineering Chemistry 77 (2019) 198–208
(its corresponding S #1) in reducing heavy oil viscosity, thus,
improving its fluidity through emulsification. In addition to oil
viscosity reduction, formation of such O/W emulsions during SP #4
flooding also helped to expand the sweep volume (Fig. 13).The
presence of a large number of emulsified oil droplets in the
produced water phase during SP #4 flooding (Fig. 17) directly
proves the excellent emulsification properties of SP #4 and
confirms the explanations above. As a result, under those dual
actions, the SP #4 system generated a larger and longer drop in
water cut (Fig. 16), and produced the greatest incremental oil
recovery factor of 15.6% (Fig. 13 and Table 3) compared to the 10.5%
and 10.0% achieved with SP #5 and #6, respectively.
Discussion
S #1 and SP #4 systems, with non-ultra-low IFT, the weakest
emulsifying capacity, but strongest emulsion stability, perform
best in reducing heavy oil viscosity, expanding sweep volumes, and
enhancing heavy oil recovery compared to other ultra-low IFT
systems. Emulsion stability seems to be more dominant during SP
flooding than IFT and emulsifying capacity with regard to recovery
of heavy oil under these experimental conditions; however,
beyond the scope (heavy oil viscosity 657.0 mPa s and SP solution
viscosity 33.5 mPa s) of this study, we think the importance of such
emulsion stability to SP flooding is not constant. That may be
influenced by two factors: (1) the specific mobility ratio of water
and heavy oil. For example, for a less viscous crude oil and more
viscous SP solution system, the mobility ratio would be much
improved, thus generating an excellent sweep volume, then, such
an extend-sweep-volume effect of emulsions arising as a result of
the Jiamin effect would be reduced, therefore, the importance of
emulsification or emulsion stability would diminish. As a result, oil
recovery of a less viscous oil is related to the ultra-low IFT instead
of the emulsion stability. (2) In addition to the effect of mobility
ratio, the permeability heterogeneity of reservoir rock also controls
the sweep efficiency of chemical flooding, and severe heterogene-
ity usually results in poor sweep volumes. Considering the
plugging effect of the emulsified oil droplets and their enlarging
sweep volume performance (Fig. 13 and elsewhere [19,20]), the
emulsification would become increasingly important for SP
flooding in heterogeneous reservoirs.
So we cannot conclude in general terms that emulsion stability
is of significant importance over ultra-low IFT for all heavy oil
flooding cases: it depends on the specific mobility ratio (of heavy
oil and SP solution) and reservoir heterogeneity. Generally, a low
mobility ratio and heterogeneous conditions, and the consequent
poor sweep efficiency, require a more powerful chemical agent
when stabilizing emulsions for recovering heavy oil.
It would be of interest, in future research, to determine the best S
or SP systems (e.g., the non-ultra-low IFT but good emulsion stability
system versus a conventional ultra-low IFT system) for enhancing
heavy oil recovery under different mobility ratio and heterogeneity
conditions. Furthermore, development of a system with an ultra-
low IFT, as well as a strong profile-control capacity, would be useful
when trying to improve heavy oil recovery by chemical flooding.
Conclusion
Six surfactant and surfactant-polymer systems, each with
different IFT and emulsification behaviors, were compared for their
ability to recover heavy oil. The following conclusions can be drawn:
(1) Ultra-low IFT helps oil–water interface expansion, making S
#2, and #3, and SP #5, and #6 outperform S #1 and SP #4 in
terms of their emulsifying capacity in bottle tests; however,
such ultra-low IFT and strong emulsifying power may not
necessarily result in a more stable emulsion, and S #1 and SP
#4 systems form more stable emulsions than the former
systems.
(2) Considering the most outstanding viscosity-reduction perfor-
mance of S #1 and the most stable O/W emulsions formed by S
#1, it can be inferred that emulsion stability is more important
for chemical solutions used to decrease heavy oil viscosity than
conventional ultra-low IFT and emulsifying capacity.
(3) The conventional ultra-low-IFT S #2, #3 systems indeed
outperform the non-ultra-low-IFT S #1 in removing residual
oil from the water-swept regions: however, the excellent
viscosity-reduction capacity, and the significantly-enlarged
sweep volume arising from the Jamin effect, make S #1 and SP
#4 the most powerful heavy oil recovery agents to replace
conventional ultra-low-IFT systems. It also indicates that
emulsion stability is more dominant than ultra-low-IFT for
SP flooding of heavy oil (657.0 mPa s).
Acknowledgements
The authors wish to thank the National Science and Technology
Major Project of China (2016ZX05058-003-003), the National
Natural Science Foundation of China (Grant No. 51504275), and the
Fundamental Research Funds for the Central Universities
(17CX02076) for their financial support.
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