art ic l e i nf o
a b s t r a c t
Article history:
Received 7 September 2015
Received in revised form
19 January 2016
Accepted 22 February 2016
Available online 24 February 2016
The present paper discusses emulsion ooding laboratory experiments in porous media with the application of the Filtration Theory, and a series of simulation experiments that showed the potential use of
emulsions as EOR technologies in Mexican mature elds with approximately 20 API gravity oil and high
water cut production. This method is based on the hydrophobization of sandstone rocks and the reconguration of water ow patterns, by means of O/W emulsion injections, improving and increasing the
oil recovery. Emulsion ooding laboratory experimental tests were performed with Ottawa sand and
Berea sandstones. During the oil recovery process, the additional oil recovery was above 25%. The dispersed phase of the emulsion is retained at the pore throats, leading to porous medium impediments
described by two mechanisms: (a) pore blockage by size exclusion, and (b) drop retention due to interactions between droplets and pore walls. Both mechanisms cause irreversible permeability reduction.
In order to know the general effect on this process, a ltration model describing emulsion ow through
porous media was used to obtain ltration parameters. In our work, we describe the use of a well-known
mathematical model, which consists of a differential equation system based on the Filtration Theory and
a modied Darcy equation that is characterized by three parameters: lter coefcient, ow redistribution
and local ow restriction factors. The EOR simulation model by emulsion ooding was created using
STARS by CMG. The conceptual mathematical model and tting of the experimental results concerning
the oil displacement by water and additional oil displaced by the emulsion show that the wettability
change caused by the emulsion is the main recovery mechanism.
& 2016 Elsevier B.V. All rights reserved.
Keywords:
Emulsion ooding
Enhanced oil recovery
Filtration
Wettability change
1. Introduction
When an oil reservoir has been exploited, the oil pressure declination rate is frequently reduced by injecting water. Water
ooding is the preferred secondary recovery method. However,
there are some problems related to this method such as the rapid
channeling of water from injection to production wells through
the most permeable portions of the reservoir. Water ooding typically displaces from 50% to 80% of contacted oil, so by taking into
account the volumetric sweep efciency, the average oil recovery
is 30% for conventional reservoirs (Lake, 1989).
As for mature elds, many of them produce a high water yield, and
n
Correspondence to: Instituto Mexicano del Petrleo, Gerencia de Ingeniera de
Recuperacin Adicional, Eje Central Lzaro Crdenas Norte, N 152, Col. San Bartolo
Atepehuacan, Mxico D.F. 07730, Mexico.
E-mail address: nvictoro@imp.mx (N.V. Likhanova).
http://dx.doi.org/10.1016/j.petrol.2016.02.018
0920-4105/& 2016 Elsevier B.V. All rights reserved.
236
I.I. Demikhova et al. / Journal of Petroleum Science and Engineering 143 (2016) 235244
Nomenclature
Super/subscripts
Sauter diameter
D32
Dd
drop diameter
Dp
pore diameter
HLB
hydrophilic-lipophilic balance
IL
ionic liquid
K
absolute water permeability
PV
pore volume
Sor
residual oil saturation
Z
zeta potential
molar density of trapped emulsion.
cn c
total diffusion coefcient
D
gravity vector
g
k
permeability tensor
k i, i = o, w relative permeabilities
total number of components
nc
total number of drop sizes
ne
pressure of phase = w, o.
p
capillary pressure
pc
volumetric ux of water
q w0
volumetric ux of emulsion
qw1
u
rrk1 = reaction rate
v
saturation
S
time
t
phase velocity
v
xi , i = 2, , nc 1. oil components
wi, i = 0, 1. water components
depth
z
the oil recovery above 40% (Kalfoglou, 1981; Bousaid, 1980). Likewise, there are several publications about the application of hydrophobic emulsions based on the same oil or its fractions and a
leavening agent for the oil recovery; in this sense, Mandal et al.
reported a further oil recovery up to 23% by applying o/w type
emulsions with gear oil (Mandal et al., 2010). Despite the satisfactory test results, the problem of applying the same oil-based
emulsions is the high concentrations of oil and emulsiers (over
10%) (McAuliffe 1973a, 1973b). In the case of siloxanes, due to their
poisonous effect on the reforming catalysts, their concentration is
restricted and in produced oil, it must be less than 1 ppm. Abdul
and Farouq Ali used polymers and crude-oil-based emulsions to
control the relative movement of water in the oil zone and block
the water channels (Abdul and Farouq Ali, 2003). Nevertheless,
polymers increase the water phase viscosity, but their use is restricted by many factors such as the water production ratio, salinity, and temperature of reservoirs; in addition, high injection
volumes make this technology not so attractive (Rocha De Farias
et al., 2012).
The oil recovery search through the injection of oil-in-water (O/
W) emulsions, which are free of siloxanes, prompted Jeirani et al.
to apply micro-emulsions based on triglycerides or fatty acids;
despite the attractive results in sand packages, fatty acids and
emulsier concentrations were higher than 10% (Jeirani et al.,
2013).
Another important tool necessary to describe how these
emulsions behave is the modeling of emulsion transport through
porous media, which is extremely challenging because of the interacting physical-chemical phenomena, and their interrelated
effects (Lei et al., 2008). Three traditional models have been used
to describe the emulsion ow in porous media: (a) bulk viscosity
Greek symbols
s nc
1
2
porosity
density
number of trapped emulsion moles
ltration coefcient
volume of emulsion drops retained per clean void
volume available for water ow
density of the emulsion trapped in the solid.
ow redistribution factor
ow restriction factor
viscosity
boundary with prescribed inlet ux
boundary with prescribed pressure
I.I. Demikhova et al. / Journal of Petroleum Science and Engineering 143 (2016) 235244
2. Theoretical basis
Oil mobilization in reservoirs is an important part of emulsion
ooding processes, and the adsorption of these emulsions on the
rock surfaces is an important topic for improving the oil recovery
by emulsion ooding. In this sense, there are a few studies that
describe sufciently the emulsion ooding in porous media, and as
a result, the physicochemical phenomena and inuence of emulsions are not included in the current numerical simulations of oil
recovery processes. The deep-bed ltration theory (Herzig et al.,
1970; Tien and Payatakes, 1979) is the most appropriate continuous model of emulsion ow through homogeneous porous
media according to the materials and methods used in our experimental tests, with similar drop and pore sizes, as shown in
Fig. 1. The study system consists of two phases: a uid one
(emulsion) and a solid one (rock). The emulsion has two components: a continuous one (water) and a dispersed one (oil). The oil
emulsion component is retained by the rock, so this component is
partitioned between both phases. The model consists of a set of
partial differential equations with appropriate initial and boundary conditions for the problem to be solved. For this purpose, a
dispersed component continuity equation is used:
( 0 cEo + cCo )
t
0 cEo vE
.
x
(1)
cEo
cCo
237
cCo
= o ( cCo ) cEo vE.
t
(2)
c o
o ( cCo ) = 1 C .
0
(3)
vE =
kE ( cCo, x) pE
.
E
x
(4)
kE ( cCo, x) =
k0
( cCo ).
0 0
(5)
Table 1
Phase and component matrix.
0 Water 1 Emulsion
Fig. 1. Schema of emulsion ltration through porous media (by Soo and Radke
(1986a)).
Rock
Water X
Oil
2, , nc 1 Hydrocarbon
components
nc Trapped
emulsion
X
X
X
238
I.I. Demikhova et al. / Journal of Petroleum Science and Engineering 143 (2016) 235244
linear way.
The clogging and release of the drops would be modeled by two
reactions.
Clogging reduces permeability and porosity.
S w w0 + ( w vw w0 ) = 0
t f w
(6)
S w w1 + w vw w1 + f w Dw1w1 =
t f w
f rrk1w1
(7)
So xi + ( o voxi ) = 0, i = 2, , nc 1.
t f o
(8)
Following Soo and Radke (1986a, 1986b), it was stated that the
drop capture kinetics is linearly dependent on the ow velocity:
( cn ) = vw 1 cnc/s
t V c
nc
) w1
(9)
k k ro
( po o g z)
o
k k rw
vw =
( pw w g z)
w
vo =
(10)
pc ( S w ) = po pw
(11)
S w + So = 1
n
si
So > 0,
si
S w > 0.
i =c 1 xi = 1
i =c 1 wi = 1
= o, w.
i = 1, , nc .
= o, w.
T = T0
3. Experimental section
3.1. Materials
Crude oil was purchased from a Mexican eld (20.1 API,
544 mPa s, and 0.9317 g/mL at 20 C). The decision to use this oil
was made based on the fact that Mexico is currently producing
this type of crude, which is mostly derived from mature elds, and
used to prepare the Mexican Maya crude mixed type for export
remarketing. Distilled water, brine and sea water (salinityNaCl
35276 mg/L, density20 C 1.0258, and Stiff & Davis Stability index
0.18622) were used as displacement uids. The brine solution was
prepared by using well-produced water (salinityNaCl 266881 mg/L,
density20 C 1.1764, and Stiff & Davis Stability index 1.62191), diluted three times with distilled water.
3.2. Emulsion preparation
Precursor emulsions (Em) were prepared by direct emulsication adding 70 g of the hydrophobic phase, which was represented
by a hydrophobic ionic liquid derivative of trioctylmethylammonium, into 30 g of the aqueous phase mixing with an Ultra-turrax
T25 Basic homogenizer at 16000 rpm for 8 min, where the
homogenization force comes from the rotor energy and the stator
shearing action. The aqueous phase comprised 1 g of the Igepal CO
890 (Sigma-Aldrich) hydrophilic surfactant with HLB 17, considering that for the formation of the O/W emulsion, emulsiers
with HBL 818 are needed, and 29 g of distilled water, which
contained 0.5% of Rewopol SB DO 75. The formed emulsion was an
oil-in-water-type emulsion. The diameter size of the 90% and 50%
dispersed phases, (D90) and (D50), were 3.59 and 0.24 m, respectively, and the Sauter diameter (D32) was 0.196, as measured
by using a laser diffraction Mastersizer 2000 Hydro2000S by
Malvern. The droplet size was chosen depending on the pore
throat of Berea rock (Fig. 2) to ensure that the emulsion passed
through the Berea sandstone rock. The prepared emulsion was
diluted with distilled water before being used until obtaining
1 wt% of the dispersed oil phase.
k rw
= 1 (x, t )
k0
(12)
w vwn = q w0 (t ) + qw1(t ) en 1
p = p0 en 2
And initial conditions:
(14)
(13)
Fig. 2. Rock throat diameter distribution by Hg-method measurements.
I.I. Demikhova et al. / Journal of Petroleum Science and Engineering 143 (2016) 235244
239
Table 2
Sand pack and Berea core properties featured in the tests.
Core property
Notation
Length, cm
Radius, cm
Pore volume, cm3
Initial porosity, %
Initial permeability (water), mD
Oil/Water saturation, %
L
R
PV
0
k0
So/Sw
cEo or cin
in
3.3.2
25 C
78 C
3.3.3
25 C
12.7
4.65
71.374.9a
38-39
2103a
89/11
78/22a
0.9982
0.918
1
8.7
1.91
19.06
19
33
88/12
10.0
2.54
38.21
19
65
78/22
9.4
1.91
23.96
22.36
135.4
0/100
0.9982
0.918
1
0.9982
0.918
1
0.9982
0.918
1
240
I.I. Demikhova et al. / Journal of Petroleum Science and Engineering 143 (2016) 235244
Fig. 5. Cumulative oil recovery and pressure difference during brine and 1 wt%
emulsion injections through a Berea core at 78 C.
Fig. 4. Cumulative oil recoveries during water and 1 wt% of emulsion injections
through sand packs: (a) with distilled water and 1 emulsion slug of 0.1 PV; (b) with
seawater and 2 emulsion slugs of 0.5 PV each (Test 3.3.1); and (c) with distilled
water and 1 wt% emulsion injections through a Berea core at 25 C.
Secondary
Tertiary
Total
Tertiary/Sor
Distilled water
Seawater
25 C
78 C
70.9
17.7
88.6
60.8
62.7
16.5
79.2
44.2
83.3
12
95.3
71.8
34.6
30
64.6
45.9
I.I. Demikhova et al. / Journal of Petroleum Science and Engineering 143 (2016) 235244
241
Fig. 7. Efuent relative concentration during the core emulsion injection (Test
3.3.3) and its ltration model tting.
at the end of the test (24 h), i.e. kday = 0.081536k 0 , which sets the
value of = 5.702479. The tting with the ltration model enabled
us to predict the average distribution of the dispersed phase in the
emulsion (oil droplets) through the porous medium (Berea core), as
shown in Fig. 9. Note that the ltration model predicts a limiting
value of drop retention by cComax = 0/ = 0.03601. This maximum
value is equivalent to a pore space reduction in the order of
1/ = 0.16106, while the permeability reduction is about 90%. In
addition, the saturation of the porous medium is reached at about
30 PV. Fig. 10 shows a zoom of the average distribution of drops
retained by the porous medium at short injection times, i.e., similar
Fig. 6. Pressure build-up during the core emulsion injection (Test 3.3.3).
Fig. 9. Distribution of oil drops along the core as predicted by the model.
242
I.I. Demikhova et al. / Journal of Petroleum Science and Engineering 143 (2016) 235244
(15)
(16)
The rate constant of this reaction over the rate constant of the
former one represents the ow diversion parameter at unit scale
factor. This is the result of the interception dominating the
straining capture as permeability increases.
Based on the experiment data from test 3.3.2 (Fig. 5) performed
to study the displacement of residual oil by the emulsion at 78 C,
the accumulated oil recovery vs time shows that after four hours
no more oil than 10.32 cm3 is produced, that volume amounts for
the 34.63% of the initial oil in place (29.80 cm3). Fig. 12 displays the
relative permeabilities for the water and oil phases.The critical
water saturation is 0.3, the residual oil saturation is 0.51 and the
end points are 1.0 for both curves.
After water ood, the emulsion is injected; this is specied in
the water phase composition, turning on the ltration mechanisms. The measured cumulative oil production, marked by the
orange triangles, is of 19 cm3 and the predicted recovery is of
10.76 cm3 at 10 pore volumes (Figs. 14 and 15). The additional
recovery due to blocking was of 0.34 cm3. It is necessary to assume
that the additional recovery was the result of the rock wettability
change which altered the petrophysical properties. This change is
expressed as a change in the relative permeabilities. By comparing
Figs. 12 and 13, we can see that the residual oil saturation decreases signicantly. The endpoint of the water relative permeability remained equal to 1.0 but the curvature change increased
this magnitude in a wider range. On the other hand, the oil relative
I.I. Demikhova et al. / Journal of Petroleum Science and Engineering 143 (2016) 235244
Fig. 12. Relative permeabilities of water and oil for water ooding.
Fig. 13. Water and oil relative permeabilities that reproduce the additional oil.
243
Fig. 15. Matching of the enhanced oil recovery by colloid injection using the
STARS simulator.
Acknowledgments
We would like to thank the IMP (Project D.60026) for the
provided support.
References
Fig. 14. Cumulative oil recovery including the additional oil produced by the
emulsion injection. The blue line indicates the recovery predicted by the ltration
mechanism. (For interpretation of the references to color in this gure legend, the
reader is referred to the web version of this article.)
Abdul, H.J., Farouq Ali, S.M., 2003. Combinated polymer and emulsion ooding
methods for oil reservoirs with a water leg. J. Can. Pet. Technol. 42 (2), 3540.
Abou-Kassem, J.H., Farouq Ali, S.M., 1995. Modelling of emulsion ow in porous
media. J. Can. Pet. Technol. 34 (6), 3038.
Alotaibi, M.B., Azmy, R., Nasr-El-Din, H.A., 2010. A comprehensive EOR study using
low salinity water in sandstone reservoirs. In: SPE Improved Oil Recovery
Symposium, Tulsa, Oklahoma, USA. SPE 129976, 2428 April. http://dx.doi.org/
10.2118/129976-MS.
Alvarado, D.A., Marsden Jr., S.S., 1979. Flow of oil-in-water emulsions through tubes
and porous media. SPE J. 19 (6), 369377. http://dx.doi.org/10.2118/5859-PA.
Ashraf, A., Hadia, N., Torsaeter, O., Twimukye Tweheyo, M., 2010. Laboratory investigation of low salinity waterooding as secondary recovery process: effect
of wettability. In: SPE Oil and Gas India Conference and Exhibition, Mumbai,
India. SPE-129012-MS, 2022 January. http://dx.doi.org/10.2118/129012-MS.
Bousaid, I.S., 1980. Oil Recovery Method Employing Alternate Slugs of Surfactant
Fluid and Fresh Water. U.S. Patent no. 4,230,182.
Camp, T.R., 1964. Theory of water ltration. Proc. Am. Soc. Civ. Eng. 90, 130.
Cha, D.K., Alotaibi, M.B., Yousef, A.A., 2015. Visualization and distribution of ions at
uids/rock interfaces: Angstrom Scale Study. In: SPE Asia Pacic Enhanced Oil
Recovery Conference, Kuala Lumpur, Malaysia. SPE 174676-MS, 1113 August.
Doi: 10.2118/174676-MS.
Chen, Z., Huan, G., Ma, Y., 2006. Computational Methods for Multiphase Flows in
Porous Media. SIAM, Philadelphia.
Cobos, S., Carvalho, M.S., Alvarado, V., 2009. Flow of oil-water emulsions through a
constricted capillary. Int. J. Multiph. Flow 35 (6), 507515.
244
I.I. Demikhova et al. / Journal of Petroleum Science and Engineering 143 (2016) 235244
Demikhova, I.I., Likhanova, N.V., Moctezuma, A.E., Hernandez Perez, J.R., OlivaresXometl, O.O., Lijanova I.V., 2014. Improved Oil Recovery Potential by Using
Emulsion Flooding. In: SPE Russian Oil and Gas Exploration & Production
Technical Conference and Exhibition, Moscow, Russia. SPE 171146, 14-16 October. Doi: 10.2118/171146-MS.
Devereaux, O.F., 1974. Emulsion ow in porous solids: I. a ow model. Chem. Eng. J.
7 (2), 121128. http://dx.doi.org/10.1016/0300-9467(74)85005-7.
Engelke, B., Carvalho, M.S., Alvarado, V., 2013. Conceptual Darcy-Scale Model of oil
displacement with macroemulsion. Energy Fuels 27 (4), 19671973.
Guillen, V.R., Carvalho, M.S., Alvarado, V., 2012a. Pore scale and macroscopic displacement mecha-nisms in emulsion ooding. Transp. Porous Media 94 (1),
197206.
Guillen, V.R., Romero, M.I., Carvalho, M.S., Alvarado, V., 2012b. Capillary-driven
mobility control in macro emulsion ow in porous media. Int. J. Multiph. Flow
43, 6265.
Herzig, J.P., Leclerc, D.M., LeGoff, P., 1970. Flow of suspensions through porous
media-applications to deep bed ltration. Ind. Chem. Eng. 62, 835.
Jeirani, Z., Mohamed Jan, B., Si Ali, B., Noor, I.M., See, C.H., Saphanuchart, W., 2013.
Formulation, optimization and application of triglyceride microemulsion in
enhanced oil recovery. Ind. Crop. Prod. 43, 614.
Kalfoglou, G., 1981. Surfacant waterooding oil recovery method. U.S. Patent no.
4,296,812.
Lake, L.W., 1989. Enhanced Oil Recovery. Prentice-Hall, Englewood Cliffs, NJ, USA.
Lei, Z., Yuan, S., Song, J., Yuan, J., Wu, Y.-S., 2008. A Mathematical Model for
Emulsion Mobilization and Its Effect on EOR during ASP Flooding. In: SPE
Symposium on Improved Oil Recovery, Tulsa, Oklahoma, USA. SPE 113145-MS,
2023 April. Doi: 10.2118/113145-MS.
Likhanova, N.V., Demikhova, I.I., Hernandez Perez, J.R., Moctezuma Berthier A.E.,
Olivares Xometl, C.O., Cuapantecatl Mendieta, M.A., 2014. U.S. Patent
0367098A1.
Mandal, A., Samanta, A., Bera, A., Ojha, K., 2010. Characterization of oil-water
emulsion and its use in enhanced oil recovery. Ind. Eng. Chem. Res. 49 (24),
1275612761.
McAuliffe, C.D., 1973a. Crude-oil-in-water emulsions to improve uid ow in an oil
reservoir. J. Pet. Technol. 25 (6), 721726. http://dx.doi.org/10.2118/4370-PA.
McAuliffe, C.D., 1973b. Oil-in-water emulsions and their ow properties in porous
media. J. Pet. Technol. 25, 727733. http://dx.doi.org/10.2118/4369-PA.
Nasralla, R.A., Nasr-El-Din H.A., 2011. Coreood study of low salinity water injection