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Characterization of Oil−Water Emulsion and Its Use in Enhanced Oil

Recovery

Article  in  Industrial & Engineering Chemistry Research · December 2010

DOI: 10.1021/ie101589x

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12756 Ind. Eng. Chem. Res. 2010, 49, 12756–12761

Characterization of Oil-Water Emulsion and Its Use in Enhanced Oil Recovery

Ajay Mandal,* Abhijit Samanta, Achinta Bera, and Keka Ojha
Department of Petroleum Engineering, Indian School of Mines, Dhanbad-826 004, India

Oil-in-water emulsions are important in the petroleum industry as a displacing fluid for enhanced oil recovery
(EOR). To investigate the efficiency of oil-water emulsions in EOR, experiments were performed to
characterize the emulsions in terms of their physicochemical properties and size distribution of the dispersed
oil droplet in water phase. In the present study commercially available gear oil was used to prepare oil-in-
water emulsions. Flooding experiments were also carried out to evaluate the effectiveness of the emulsion as
displacing fluid for enhanced oil recovery. Substantial additional recoveries (more than 20% of original oil
in place) over conventional water flooding were obtained in the present investigation.

1. Introduction enhances the oil extraction performance. Khmbharatana et al.17

In view of increasing demand of energy of the world and, in
contrast, depleting oil and gas resources, it is important to
increase the production from existing reservoirs by introducing
new technologies for EOR. These technologies will also help
in addressing challenges to recover oil from subsea, deep-sea
reservoirs and also from formations where the mobility of the
in situ oil being recovered is significantly less than that of drive
fluid used to displace the oil. One of the suggested routes is to
use oil-water microemulsions as a promising drive fluid to
improve oil recovery of moderately viscous oils from the
formations.1,2 This oil-water emulsion flooding technology may
be more effective than some, if not all, other chemical EOR
techniques such as pure polymer flooding.3-5
Oil and water form emulsions under favorable conditions in
presence of extraneous materials.6,7 Emulsions are suspensions
of droplets (greater than 0.1 µm) of one immiscible fluid
dispersed in another fluid. Their kinetic stability is a consequence
of small droplet size and the presence of an interfacial film
around oil droplets.8 An emulsifying agent must be present to
form stable oil-in-water emulsions.9 Such agents include clay
particles, added chemicals, or crude oil components like
asphaltenes, waxes, resins, and napthenic acids. These stabilizers
suppress the mechanism involved in emulsion breakdown.10
Oil-water emulsions in the presence of surface-active agent
or emulsifier significantly reduces the interfacial tension between
trapped oil and displacing fluid and stabilizes the interface
against coalescence, once it is formed. The emulsions with
dispersed phase drops effectively block the more permeable
paths and force the displacing fluid to flow through the unswept
regions, which increase the overall sweep and displacement
efficiency,leadingtoanincreaseinoilrecovery.11-13 McAuliffe14,15
carried out experiments on injection of crude oil-water emul-
sions as a selective plugging agent to improve the oil recovery
in water floods. He reported that the most effective emulsion
for flooding is one in which the droplet diameters are slightly
larger than the pore-throat constriction in porous media. Bragg16
developed a method for recovering hydrocarbons from a
subterranean formation by injecting an emulsion, comprising
oil and water, into the formation for enhanced recovery of oil.
Austad and Strand1 observed that very low interfacial tensions
may be reached with microemulsion systems. These micro-
emulsions flow more easily through the porous medium, which
* To whom correspondence should be addressed. E-mail:
mandal_ajay@hotmail.com.
10.1021/ie101589x  2010 American Chemical Society
Published on Web 11/05/2010
discussed the physical mechanisms of stable emulsion flows in
Berea sandstone and Ottawa sand pack systems of comparable
droplet and pore sizes. Zeidani et al.18 showed that an oil-in-
water emulsion was effective in sealing unconsolidated cores
for long periods of time. A number of researchers19-23 have
discussed the flow mechanics of emulsions in a porous medium.
The emulsions also improve the mobility ratio by increasing
the viscosity of the displacing fluid.24-26 The success of the
proposed method in field application is closely related to proper
slug design and injection scheme depending on properties and
distributions of fluid and rock.
The objective of the present study is to characterize the oil-
in-water microemulsions and their application in enhanced
recovery of oil after conventional water flooding. The effect of
composition of microemulsions on additional recovery was also
studied.
2. Experimental Section
2.1. Preparation of Emulsion. In the present study gear oil
(EPX 90) available in the market with sp. gravity 0.905 and
kinematic viscosity 197 centistokes (cSt) at 40 °C and 17.3 cSt
at 100 °C was used for preparation of emulsion in distilled water.
Quality of lubricating oil is often improved by adding detergent,
dispersant, etc.,27,28 which enable formation of a milky emulsion
when properly mixed with water. Oil-in-water emulsion was
prepared at 30 °C with a standard three-blade propeller. For
oil-in-water emulsion distilled water was used as the continuous
phase and oil was used as the dispersed phase. The emulsion
was left to stand in a separation flask for 6 h and the bottom
part was separated out. The separation flask can easily lead to
the separation of two different density fluids based on their
density. For preparation of emulsion, the oil-water mixtures
were stirred at different rpm and time as the characteristics of
emulsions are very much dependent on the stirring speed and
time.29
2.2. Characterization of Emulsion. Emulsions are charac-
terized by analysis of their stability, drop size, rheological
properties, temperature effects, etc. It has been found that the
stability and hence the characteristics of emulsion are very much
dependent on the stirring speed and time during formation.
Surface tension measurements were carried out using an auto
tentiometer (model 6801ES with platinum ring) under atmo-
spheric pressure by the ring method. The viscosity of the
emulsion was measured in a viscometer (Brookfield DV II+),
 Ind. Eng. Chem. Res., Vol. 49, No. 24, 2010 12757

Figure 1. Schematic diagram of crude oil flooding system.

and a microscopic picture of the emulsion was taken by

Olympus BX-60 microscope and analyzed by image processing
software (Olympus Microsuite Basic).
2.3. Flooding Experiments. The experimental setup (Figure
1) for sand pack flooding tests consisted of four components:
sand pack holder, displacement pump (Teledyne Isco), cylinders Figure 2. Variation of surface tension with the quality of oil-water emulsion
for holding crude oil, and chemical slug and fraction collectors. at 30 °C.
The crude oil used in the flooding experiments was collected
from Ahmedabad oil-field (India). The oil had a total acid
number of 0.038 mg KOH/g, gravity of 38.86° API, and
viscosity of 119 mPa.s at 30 °C.
The sand pack holder was first tightly packed with sand using
brine solution. Before use, the sand particles (40-60 meshes)
were cleaned thoroughly and dried. For each test, fresh sand
was packed to ensure the same wettability for all tests. Then it
was completely saturated with water by continuous flooding.
The sand pack was then completely saturated with brine solution,
and absolute permeability was measured by injecting brine
solution at constant pressure of 25 psig. It was next flooded
with crude oil with an injection pressure of 500 psig to
irreducible water saturation and initial oil saturation (Soi) was
measured by material balance. The sand pack was allowed to
rest for one day at this stage. It was then water-flooded with
300 psig injection pressure and continued to flood until water
cut reached above 95%. A substantial amount of oil was
recovered during this water/brine flooding. The remaining oil
was recovered by different emulsions flooding at 300 psig
followed by chase water flooding. The recovered fluids were Figure 3. Variation of viscosity with the quality of oil-water emulsion at
collected by switching the fraction collector at regular intervals. 30 °C: 9, 5% oil; b, 10% oil; 2, 20% oil; 1, 30% oil.
The effective permeability to oil (ko) and effective permeability
to water (kw) were measured at irreducible water saturation (Swi) displacement of oil by increasing the sweep efficiency. Figure
and residual oil saturation (Sor), respectively, using Darcy’s law 3 compares the viscosity vs shear rate curves for emulsions with
equation. different composition showing pseudoplastic behavior. The
viscosity of emulsion increases with increase in concentration
3. Results and Discussion of oil in the emulsion.
Too correlate the emulsion data with literature values, the
3.1. Emulsion Characteristics. Physicochemical Proper- relative viscosity, the ratios of the emulsion viscosity (µr) to
ties of Emulsion. Very low interfacial tension between oil and that of the continuous phase, at shear rate of 46 s-1 were
water is the primary requirement for emulsion formation. calculated and plotted against oil volume fraction (Figure 4).
Lowering of interfacial tension recovers additional oil by The data have been correlated with Mooney’s equation:30
reducing the capillary forces that leave the oil behind any
immiscible displacement. This trapping is best expressed as a
competition between viscous forces which mobilize the oil, and
capillary forces which trap the oil. Figure 2 shows that the
µr ) exp
[ 2.5φ
1 - a mφ ] (1)

surface tension decreases with increase in oil concentration in
the emulsion due to presence of higher surface-active agent or
emulsifier in the emulsion. This reduction of surface tension
plays an important role in additional oil recovery.
Viscosity of the displacing fluid is also an important parameter
in enhanced oil recovery. Increase in viscosity of the displacing
fluid improves the mobility ratio, which increases the overall
where the parameter am is between 1.35 and 1.91. Figure 4
shows that the model (am ) 1.5) deviates uniformly from the
entire range of the experimental data. This may be due to the
fact that Mooney’s model was developed for Newtonian fluids
whereas the emulsions under study exhibit non-Newtonian
behavior. This discrepancy is corrected by incorporating a factor
in Mooney’s equation as follows:
12758 Ind. Eng. Chem. Res., Vol. 49, No. 24, 2010

Figure 5. Microscopic picture (magnification 430×) of oil-in-water emulsion

Figure 4. Comparison of relative viscosity of oil-water emulsion with (5% oil + 95% water).
Mooney’s Model (1951) at 46 s-1 shear rate: 9, experimental data; O,
Mooney’s correlation; ∆, modified Mooney’s correlation.

µr ) A + exp
[ 2.5φ
1 - amφ ] for 0.05 e φ e 0.3 (2)

where A is constant and the above model (eq 2) fits the

experimental data well for the value of A equals 0.85 as shown
in Figure 4. The experimental results are found to satisfy the
modified correlation adequately (with goodness of fit equal to
0.995).
Microscopic picture of a typical oil-in-water emulsion is
shown in Figure 5. The figure shows the size distribution of
dispersed oil droplets. Various analytical distribution functions
were tested by statistical software (SAS) for their adequacy in
representing the observed droplet size distributions. It was found
that the logarithmic normal distribution provided the most
reasonable fitting. The probability function for logarithmic
normal distribution f(db) of oil droplet diameter (db) is given
by the expression

{ ( )}
Figure 6. Size-range histogram and density distribution of injected emulsion:
1 log db - µdb
2
1 emulsion: 5% oil + 95% water; sample data: 147.
f(db) ) exp - (3)
dbσdb√2π 2 σdb
3.2. Flooding Tests. To evaluate the performance of emul-
where, µdb is the sample mean and σd2b
is the sample variance as sion flooding, four sets of flooding experiments were conducted
defined by eqs 4 and 5, respectively. with sandpack in a horizontal orientation. These experiments
investigated the displacement of crude oil by water flooding
n and subsequent emulsion flooding. The emulsion flooding
µdb )
1
n ∑d bi (4) process involves a complex interplay of several mechanisms.31
i)1 The overall oil recovery by an emulsion flooding is dependent
on so many process parameters, viz. composition of injected
and emulsion, drop size distribution of the injected emulsion,
n emulsion size to be injected, absolute permeability of reservoir
σd2b )
1
n-1 ∑ (d bi - µdb)2 (5) rock, viscosity of oil being displaced, etc.
Prior to emulsion injection, steady state absolute permeability
i)1
was measured for each core plug. The details of these three
where n stands for number of drops of oil in the emulsion and systems (porosity, Φ, and permeability, k) are given in Table
147 numbers of data have been considered for the distribution. 1. Since in the present work, all the experiments were carried
Figure 6 shows the frequency distribution curve of oil droplet out in sandpack with higher porosity (∼ 37%) and permeability
size as shown in Figure 5. The size distributions of the oil droplet (441-478 mD), the water flood recovers almost 50% of the
size were found to deviate from a normal distribution with original oil in place. During water flooding as the water-cut
skewness toward the larger droplet sizes. Figure 7 shows a reaches above 95%, it was subsequently flooded with different
typical Lognormal probability plot with mean and standard emulsion slugs followed by chase water. The recovery of oil
deviation 1.816 and 1.414, respectively. The size distribution and water-cut with pore volume injected for the four different
of the oil droplets was found uniform throughout the entire systems are presented in Figures 8 through 11. The curve of
emulsion. waterflood oil recovery shows an early breakthrough and
 Ind. Eng. Chem. Res., Vol. 49, No. 24, 2010 12759

Figure 9. Production performance of emulsion (10% oil) flooding: 9, %

oil recovery; b, % water cut.

Figure 7. Lognormal P-P plot of drop size.

Figure 10. Production performance of emulsion (20% oil) flooding: 9, %

Figure 8. Production performance of emulsion (5% oil) flooding: 9, % oil
recovery; b, % water cut.
channel flow which causes much lower oil recovery. After water
starts to produce the water-cut sharply increases above 90% in
each case. The crude oil used for flooding experiments was
viscous enough (119 mPa.s) at the test temperature. So the long
transient production during waterflood may be due to the
unfavorable mobility ratio between the injected water and crude
oil. During injection of emulsion slug, the water-cut declines
gradually, and then again reaches to 100% at the end of flooding.
To compare the efficiency of the four systems, same volumes
(0.5 PV) of slugs having different composition were injected.
A comparative picture of oil recovery is shown in Figure 12.
During the waterflooding of the viscous oil only about 15% of
the injected water enters the lower-permeability zone.32 After
Table 1. Flooding Results of the Different Systems
permeability, k (Darcy)
sand pack
sample porosity kw (Sw ) 1) ko (Swi) kw (Sor) design of chemical slug for flooding
oil recovery; b, % water cut.
the high-permeability zone is flooded out, significant oil still
remains in the low-permeability zone. With the emulsion flood
more flow is routed to the low-permeability zones of the
sandpack. The emulsified oil droplets are also captured in the
high-permeable zone and reduce its permeability, which in term
increases the sweep efficiency. On the other hand, since
emulsions are more viscous than the constituent oil, it signifi-
cantly reduces the mobility ratio, which plays an important role
in the displacement of heavy oil by higher viscosity W/O
emulsion phase.33,34 Emulsions with higher percentage of oil
result in better additional recovery due to significant decrease
in interfacial tension between oil and water and improvement
of mobility ratio. The detailed results of the different systems
are given in Table 1.
Conclusion
Based upon this investigation, the following conclusions can
be drawn: (1) Characterization of emulsion shows that it follows
saturation, % PV
recovery of oil after additional
water flooding at 95% recovery
water cut (% OOIP) (% OOIP) Swi Soi Sor

sample 1 37.72% 0.441193 0.00198 0.02902 0.5 PV 5% emulsion + chase water 49.5714 20.714 14.64 85.36 25.36
sample 2 36.80% 0.47797 0.002786 0.027809 0.5 PV 10% emulsion + chase water 50.5294 20.941 15.04 84.96 24.25
sample 3 36.80% 0.47797 0.002778 0.02987 0.5 PV 20% emulsion + chase water 51.542 21.678 13.75 86.25 22.87
sample 4 37.72% 0.441193 0.002567 0.02880 0.5 PV 30% emulsion + chase water 50.7143 23.144 14.63 85.37 22.92
12760 Ind. Eng. Chem. Res., Vol. 49, No. 24, 2010
Figure 11. Production performance of emulsion (30% oil) flooding: 9, %
oil recovery; b, % water cut.
Figure 12. Comparative production performance of emulsion flooding: O,
emulsion with 5% oil; ), emulsion with 10% oil; 0, emulsion with 20%
oil; ∆, emulsion with 30% oil.
pseudoplastic behavior and drop size of dispersed oil phase
follows log-normal distribution. (2) Dilute oil-water emulsions
are shown to aid in the displacement of viscous oils by
decreasing the mobility of the aqueous displacing phase and
reducing interfacial tension between oil and water. (3) After
water starts to produce the water-cut sharply increases above
90% in each case due higher permeability of the sandpack and
unfavorable mobility ratio between the injected water and the
crude oil. (4) The flooding behavior with water and subsequent
emulsions were found to be identical; only a little higher
recovery was observed with higher emulsion concentration. (5)
Recovery efficiency is more than 20% of original oil in place
over the conventional water flooding, which may be due to
reduced interfacial tension, improved mobility ratio, and
increased sweep efficiency caused by the injected emulsions.
Acknowledgment
Financial support through projects from Council of Scientific
and Industrial Research (CSIR, 424/07) and University Grant
Commission [37-203/2009 (SR)] are gratefully acknowledged.
Literature Cited
(1) Austad, T.; Strand, S. Chemical Flooding of Oil Reservoir-4. Effects
of Temperature and Pressure on the Middle Phase Solubilization parameters
close to optimum Flood Conditions. Colloids Surf., A 1996, 108, 243–52.
(2) Santanna, V. C.; Curbelo, F. D. S.; Castro Dantas, T. N.; Dantas
Neto, A. A.; Albuquerque, H. S.; Garnica, A. I. C. Microemulsion flooding
for enhanced oil recovery. J. Pet. Sci. Eng. 2009, 66, 3–4, 117-120.
(3) Daripa, P. Instability and Its Control in Oil Recovery Problems.
Proceedings of 6th IMACS Int. Symp. on Computer Methods for Part. Diff.
Eq.-VI; Vichnevetsky, R., Ed., Bethlehem, PA, 1987; pp 411-418.
(4) Daripa, P.; Glimm, J.; Lindquist, B.; McBryan, O. Polymer Floods:
A Case Study of Nonlinear Wave Analysis And of Instability Control In
Tertiary Oil Recovery. SIAM J. Appl. Math 1988, 48, 353–373.
(5) Daripa, P.; Glimm, J.; Lindquist, B.; Maesumi, M.; McBryan, O.
On The Simulation of Heterogeneous Petroleum Reservoirs, Numerical
Simulation in Oil Recovery. In IMA Vol. Math. Appl., 11; Springer, New
York, 1988; pp 89-103.
(6) Gewers, C. W. W. Colloid and Surface Chemical Problems in Non-
Conventional Heavy Oil Recovery. Can. J. Pet. Technol. 1968, 7, 2–85.
(7) Rupesh, M. B.; Prasad, B.; Mishra, I. M.; Kailas, L. Wasewar Oil
field effluent water treatment for safe disposal by electroflotation. Chem.
Eng. J. 2008, 137, 503–509.
(8) Murray, B. S.; Dickinson, E.; Wang, Y. Bubble stability in the
presence of oil-in-water emulsion droplets: Influence of surface shear versus
dilatational rheology. Food Hydrocolloids 2009, 23 (4), 1198–1208.
(9) Sjoblom, J.; Mingyuan, L.; Christy, A. A.; Gu, T. Water-in-Crude
oil emulsions from Norwegian continental shelf 7. Colloids Surf. 1992, 66,
55–62.
(10) Fingas, M.; Fieldhouse, B. Formation of water-in-oil emulsions and
application to oil spill modelling. J. Hazard. Mater. 2004, 107, 37–50.
(11) Thomas, S.; Farouq Ali, S. M. Flow of emulsions in porous media,
and potential for enhanced oil recovery. J. Pet. Sci. Eng. 1989, 3, 121–
136.
(12) Shindy, A. M.; Darwich, T. D.; Sayyouh, M. H.; Osman, A. A.
Development of an Expert System for EOR Method Selection; SPE 37708;
Society of Petroleum Engineers, 1997; pp 291-298.
(13) Babadagli, T. Mature Field Development - A review; SPE 93884;
Society of Petroleum Engineers, 2005; pp 1-20.
(14) McAuliffe, C. D. Crude oil-in-water emulsions to improve fluid
flow in an oil reservoir. J. Pet. Technol. 1973, 721.
(15) McAuliffe, C. D. Oil-in-water emulsions and their flow properties
in porous media. J. Pet. Technol. 1973, 727.
(16) Bragg, J. R. Oil recovery method using an emulsion. U.S. Patent
5927404, 1998.
(17) Khambharatana, F.; Thomas, S.; Nad Farouq Ali, S. M. Macro-
emulsion rheology and drop capture mechanism during flow in porous
media. Paper SPE 48910 In Proceedings SPE International Oil and Gas
Conference and Exhibition, Beijing, China, 1998; pp 2-6.
(18) Zeidani, K.; Polikar, M.; Huang, H.; Boyd, J. Heavy Oil-in-Water
Emulsion as a Novel Sealant in the Near Well Bore Region. Canadian
International Petroleum Conference, Calgary, Alberta, 2007.
(19) Devereux, O. F. Emulsion flow in porous solids. I: A flow model.
Chem. Eng. J. 1974, 7, 121.
(20) Devereux, O. F. Emulsion flow in porous solids. II: Experiments
with a crude oil- in-water emulsion in porous sandstone. Chem. Eng. J.
1974, 7, 129.
(21) Soo, H.; Radke, C. J. The Flow Mechanism of Dilute, Stable
Emulsions in Porous Media. Ind. Eng. Chem. Fundam. 1984, 23, 342.
(22) Soo, H.; Radke, C. J. A filtration model for the flow of dilute, stable
emulsions in porous media. I. Theory. Chem. Eng. Sci. 1986, 41 (2), 263.
(23) Soo, H.; Williams, M. C.; Radke, C. J. A filtration model for the
flow of dilute stable emulsions in porous media. II. Parameter evaluation
and estimation. Chem. Eng. Sci. 1986, 41 (2), 273.
(24) Krieger, I. M.; Dougherty, T. J. A mechanism for non-Newtonian
flow in suspensions of rigid spheres. Trans. Soc. Rheol. 1959, 3, 137–152.
(25) Pal, R. A novel method to correlate emulsion viscosity data. Colloids
Surf., A 1998, 137, 275–286.
(26) Pal, R. Evaluation of theoretical viscosity models for concentrated
emulsions at low capillary numbers. J. Chem. Eng. 2001, 81, 15–21.
(27) Atkins, D. C.; Baker, H. R.; Murphy, C. M.; Zisman, W. A.
Development of additives and lubricating oil compositions. Ind. Eng. Chem.
1947, 39, 491–497.
(28) Miller, A. The chemistry of lubricating oil additives. J. Chem. Educ.
1956, 33, 308–312.
(29) Mandal, A.; Kumar, P.; Ojha, K.; Maity, S. K. Characterization
and Separation of Oil-in-Water Emulsion. AdV. Sustainable Pet. Eng. Sci.
(ASPES) 2010, 1, 4.

(30) Mooney, M. The viscosity of concentrated suspensions of spherical
particles. J. Colloid Sci. 1951, 6, 162–170.
(31) Sharma, H. K.; Mani, B. B.; Jha, K. Evaluation of emulsified solvent
flooding for heavy oil recovery. J. Can. Pet. Technol. 1998, 37, 55–62.
(32) Schmidt, D. P.; Radke, C. J. Linear oil displacement by the emulsion
entrapment process. SPE J. 1984, 11333-PA, 351–360.
(33) Dong, M., Liu, Q., Li, A. Micromodel study of the displacement
mechanisms of enhanced oil recovery by alkaline flooding, SCA 2007-47,
in International Symposium of the Society of Core Analysts, 2007, Calgary,
AB Canada.
View publication stats
Ind. Eng. Chem. Res., Vol. 49, No. 24, 2010 12761
(34) Farouq Ali, S. M.; Figueroa, J. M.; Azuaje, E. A.; Farquharson,
R. G. Recovery of lloydminster and morichal crudes by caustic, acid and
emulsion floods. J. Can. Pet. Technol. 1979, 53–59.
ReceiVed for reView July 26, 2010
ReVised manuscript receiVed October 20, 2010
Accepted October 21, 2010
IE101589X