SPE 106402
Oilfield Surfactants Improve Recovery by Imbibition
W.W. Weiss and X. Xie, SPE, Correlations Co.
Copyright 2007, Society of Petroleum Engineers
This paper was prepared for presentation at the 2007 SPE International Symposium on Oilfield
Chemistry held in Houston, Texas, U.S.A., 28 February–2 March 2007.
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Abstract
Most carbonate reservoirs are naturally fractured and typically
produce less than 10% OOIP during primary recovery. Spontaneous
imbibition is an important oil recovery mechanism from these types of
reservoirs. In some situations, imbibition of water can be promoted by
chemical stimulation with surfactants to alter the reservoir wettability
toward water-wetness such that oil is expelled at an economic rate
from the rock matrix into fractures. Here, we investigated the use of
chemicals to modify the wettability of reservoir rock to a more water-
wet state in order to produce additional oil via imbibition. Five
chemicals that effectively improved water-wetness were used in the
imbibition tests: two nonionic surfactants Tomadol T91-8 and Pluronic
L-64, two anionic surfactants Rhodacal A-246L and Rhodapex CD 128,
and an amphoteric surfactant Mirataine CB.
The San Andres formation in the Permian Basin of Texas and New
Mexico is a great oil-producing formation in the United States. An
estimated 50,000 wells produce oil from this oil-wet carbonate
reservoir. Laboratory imbibition tests were conducted on core plugs
and fluids from the Fuhrman Masho and Eagle Creek fields. Thin
section analysis indicated that both fields contain dolomite, calcite, and
anhydrite. The core plugs were soaked in imbibition cells containing
formation water at a reservoir temperature of 40°C (104°F). For
Fuhrman Masho cores, maximum oil recovery via water alone was less
than 4% of the original oil in place (OOIP). After the oil production
stopped, the water was replaced with a surfactant solution at a
concentration of 1500 to 3500 ppm. The imbibition process then
continued until no oil was produced. The incremental oil recovered
varied from 0 to 48% OOIP; higher permeability and bulk volume of oil
in the cores resulted in higher oil recovery by surfactant imbibition. No
oil was produced by brine imbibition for some Eagle Creek cores;
however, others produced up to 34% of the OOIP. Surfactant
treatment did not improve oil recovery every core. The laboratory tests
indicated that the improved oil recovery by surfactant treatment
depended on rock mineralogy, porosity, permeability, and pore
heterogeneity. Each field must be individually evaluated.
Introduction
Spontaneous imbibition can be especially important to oil recovery
from fractured reservoirs. However, spontaneous imbibition does not
take place if rocks are oil-wet or neutral-wet. Spontaneous imbibition
only occurs when the pore surfaces are effectively water-wet so that
water imbibes into the rock matrix, and oil is expelled into the fractures
where the oil can be flushed along the fractures toward the production
wellbore. The focus of this project was to investigate the use of
chemicals for modifying the wettability of reservoir rock to a more
water-wet state in order to produce additional oil via spontaneous
imbibition. The significance of spontaneous imbibition as a recovery
mechanism was first recognized for the naturally fractured Spraberry
field of west Texas in the early 1950s.1 Oil recovery by spontaneous
2
imbibition from the Spraberry field is still being promoted.
Surfactants have been used to alter the rock surface to a more
water-wet state in order to promote imbibition of water into the matrix.
3
Craig showed that surfactants could alter the rock surface from oil-wet
to surfactant-wet, thus allowing oil to be displaced from the pores.
4
Stone et al. improved oil recovery by altering the rock surface to oil-
5
wet. Spinler et al. and Austad and coworkers have reported extensive
laboratory research on improved oil recovery from carbonate cores by
6–8
imbibition of cationic and nonionic surfactant solutions. The
surfactant interacts with and removes the adsorbed organic materials
from the rock surface, which then becomes water-wet, and imbibition is
9
enhanced. Chen et al. reported the use of a nonionic surfactant to
stimulate oil wells in the San Andres reservoir of the Yates field. The
average oil-production rate for one well increased from 35 to 67 barrels
per day for an incremental 17,000 barrels of oil at the time of
publication. Improved recovery was ascribed to altering the wettability
of the rock surface and/or gravity segregation of oil and water between
10
the fracture and the matrix. Hirasaki and Zhang have proposed the
use of anionic surfactant with sodium carbonate. At a high pH, the
carbonate ion is the potential determinant and reverses the charge of
the carbonate surface so that the problem of adsorption is mitigated.
Previous laboratory work conducted by Correlations Company
demonstrated that altering the wettability of core samples from the
Phosphoria formation with either a non-ionic or a cationic surfactant
11–12
produced incremental oil. One possible mechanism of improved
recovery by imbibition for surfactant solutions may be the release of
the adsorbed organic materials from the rock surface, which then
6
becomes more water-wet and the imbibition rate is increased. Also
important is that surfactants lower the interfacial tension, thereby
decreasing the capillary pressure The corresponding increase in the
Bond number, N a = ρgr 2 / σ , probably contributed to improved oil
9
recovery through gravity segregation.
Experimental
Reservoir cores. Reservoir cores from the San Andres formation in
two fields were used for the laboratory tests (Tables 1A, 1B, and 1C).
All the cores were 1.5” in diameter and about 3” in length. One batch
was from the W. Boner B and C zones, Well No. 40 of the Fuhrman-
Masho (FM) field in Andrew County, Texas. As shown in Fig. 1a, the
porosities of most cores from both the B and C zones were all around
10%. The permeability of cores from the B zone ranged from 0.2 to 25
md, and those from the C zone ranged from 5 to 880 md. Another
batch of cores was from the Eagle Creek (EC) field in Eddy County,
New Mexico. The porosity and permeability were in the range of 3 to
14% and 0.1 to 26 md, respectively (Fig. 1b). EC cores were tighter
and less permeable than FM cores.
Thin sections of FM and EC rocks are shown in Fig. 2. Mineralogy
analysis of the rock via thin sections showed that the FM rock
consisted of grainstone dolomite containing minor anhydrite and calcite
(Fig. 2a); EC rock consists of wackestones or packstones containing
dolomite, calcite, and some anhydrite (Fig. 2b).
2 SPE 106402
Brine composition. Three brines were used in the laboratory tests:
synthetic reservoir brine based on FM reservoir water analysis,
designated as FM brine; synthetic reservoir brine that represented the
average EC reservoir brine concentration, designated as EC brine;
synthetic SW based on North Sea water analysis, designated as SW
brine. All brine compositions are listed in Table 2.
Synthetic SW was used to avoid emulsion in surfactant solutions.
Except for T91-8, emulsion appeared in all other surfactant brine
solutions because of the high salinity of the FM and EC brines.
Synthetic SW was used to make the surfactant solutions.
Crude oil. The properties of the two crude oils used in the lab tests
are shown in Table 3. The reservoir temperature of the San Andres
field was 40°C. Crude oils were filtered before use to avoid any
material particles and degassed to avoid component change during the
course of experiments.
Surfactants and interfacial tension measurements. According to
previous laboratory and field experience, nonionic surfactants T91-8
and L-64, anionic surfactants RA-246L and CD-128, and the
amphoteric surfactant MCB have been used as oil recovery chemicals
(Table 4). The surfactant solutions were a mixture of the designated
synthetic reservoir brine with each surfactant at a certain
concentration. The specific surfactant used for each core is listed in
Table 1a–c; the concentration of 3000 ppm was used for most cores
except for those indicated. The San Andres reservoir temperature of
40°C was used as the test temperature. Interfacial tensions between
crude oil and surfactant solutions are listed in Table 5.
Laboratory procedure. Reservoir cores with different permeabilities
and initial water content, Swi, were tested for spontaneous imbibition,
both in synthetic reservoir brine and surfactant solutions. The test
procedure for systems with initial water saturation S wi > 0 is as
follows:
1) saturate the cores with brine and soak them in brine for at least 7
days for ion equilibrium;
2) displace the brine from the core with crude oil until a certain initial
water saturation Swi is reached or no water can be displaced;
3) age the cores for 10 days at 40°C;
4) displace the aged crude oil from the aged core with fresh crude oil
at 40°C;
5) immerse the cores in test brine for imbibition until no oil is
produced;
6) immerse the cores in surfactant brine solution for imbibition.
For the S wi = 0 cases, the cores were saturated with crude oil
directly by vacuum followed by high-pressure displacement. Then the
above procedure was followed starting from step 3).
Results and Discussion
FM rock/crude oil/FM brine and/or synthetic SW. Oil recovery
versus spontaneous imbibition time was recorded for FM cores soaked
in brine and surfactant solutions. The oil recovery by imbibition from
brine for most cores was below 10%. The cores responded differently
when soaked in different surfactant solutions. The improved oil
recovery varied from 0 to 48%, as listed in the right column of Tables
1A and B. No difference in oil recovery was observed for FM brine or
synthetic SW.
Some examples of oil recovery versus spontaneous imbibition time
were plotted in Figs. 3 and 4. Imbibition curves for cores from the C
zone are plotted in Fig. 3, and those from the B zone are plotted in Fig.
4. Fig. 3a shows the oil recovery of C zone cores in brine and in T91-8
brine solution. Additional oil was produced from those cores after
soaking in T91-8 solution, indicating sound response to stimulation
with the nonionic surfactant T91-8. Other surfactants generally did not
affect improved oil recovery except for MCB (Fig. 3b). It gave mixed
results for improved oil recovery by 26% for core #4378.3 and 2.4% for
core #4379.8.
However, the effect of the surfactants on cores from the B zone was
much different. Almost no oil was produced after the cores from the B
zone were soaked in any surfactant solutions (Fig. 4).
Previous studies indicate that T91-8 effectively enhanced oil
11
recovery from dolomite rocks. FM rock mainly consisted of
grainstone dolomite, and the sound response of the C zone cores to
T91-8 was consistent with the past findings. Although the mineralogy
of cores from both the C and B zones was similar, the permeability of
cores from the B zone was much less than that from the C zone (Fig.
1a). Permeability might be the most important factor affecting the
13
amount of oil recovered by surfactants. The surfactant solution
imbibes more readily into a rock with high permeability and contacts
more rock surface, while the imbibition rate of low permeability rock is
much less. The permeability versus improved oil recovery with
surfactants is plotted in Fig. 5. It suggests that permeability should be
greater than 1 md to improve oil recovery.
Shown in Fig. 6 is the incremental oil (%OOIP) by surfactants versus
bulk volume oil (BVO) for the cores from the B and C zones. BVO is
the product of porosity,φ, and oil saturation, 1− Swi ,
BVO = φ (1 − S wi ) * 100 .
The trend suggests that the greater the BVO (more oil available), the
more oil recovered.
EC rock/crude oil/brine.
EC crude oil/EC brine. As listed in Table 1C, EC crude oil and EC
brine were used for 10 EC core samples. Because of the emulsion
problem as mentioned earlier, only T91-8 was used as the surfactant.
For cores with no initial water saturation (Swi = 0), oil recovery by brine
imbibition ranged from 3 to 25%. For cores with initial water saturation
(Swi > 0), the oil recovery by brine imbibition was erratic. Spontaneous
imbibition of the cores in the T91-8 solution after soaking in brine did
not result in any extra oil recovery (Fig. 7). T91-8 had no effect on the
imbibition oil recovery of EC cores.
FM crude oil/synthetic SW. Simply for the convenience of comparing
the effect of surfactants on FM rock and EC rock, FM crude oil and
synthetic SW were used for some EC core samples. Again the results
were erratic. For Swi = 0, some cores had oil recovery up to 34% by
SW imbibition and an additional 6% oil recovery by surfactant
imbibition. But some cores had no oil recovery by imbibition either in
SW or surfactant solutions, indicating the heterogeneous nature of the
carbonate rocks. Using core #1388.8 as an example, oil recovery by
SW imbibition was 13.16%, whereas additional oil recovery by
imbibition in the L-64 solution was about 6%. However, for core
#1298.1, SW imbibition produced no oil, while oil recovery was only
1.8% via soaking in the L-64 surfactant solution (Fig. 8). For Swi > 0,
SW imbibition recovered oil only in cores #1352.9 and #1353.0, though
the recovery was very small. None of the other cores produced
additional oil by either SW or surfactant imbibition. In these cases,
none of the five surfactants improved oil recovery.
Core #1387.5 was used to measure the Amott index used to quantify
the rock wettability. After soaking a core in T9108, the Amott index of
the core was I w−o = −0.49 , meaning that the core was medium oil-
wet. It seems that soaking in T91-8 did little to alter the oil-wetness of
the core. This core imbibed water while it was soaked in brine, and it
behaved like it was oil-wet after soaking in the T91-8 solution.
Therefore, improving oil recovery from EC cores by the surfactants
tested was not effective. The heterogeneity of the rock increased the
complexity of the problem. Lithologically, the EC rock consisted of
wackestones or packstones containing dolomite, calcite, and some
anhydrite (Fig. 2b). One possible reason for the ineffectiveness of the
surfactants is that the relatively large surface area of the rock minerals
adsorbed and consumed all the surfactants, while the wettability of the
rocks remained unchanged. The low permeability of the rock also
contributed to the poor performance of the surfactants.
Summary
Oil recovery by brine imbibition from FM cores was in the range of 0
to 4% of the OOIP, indicating that the cores were very weakly water-
wet. The laboratory results imply that the C zone is a good candidate
for surfactant stimulation. The nonionic surfactant T91-8 and the
amphoteric surfactant MCB improved oil recovery in the FM C zone
systems. Oil recovery was increased up to 38%. More oil was
produced for cores with a higher bulk volume of oil and permeability.
Most of the core samples from the B zone did not respond to surfactant
soaking, indicating that the B zone is not an ideal candidate for
stimulation with the surfactants evaluated. The anionic surfactants
RA246 and CD128 did not improve oil recovery from the FM cores.
SPE 106402
None of the surfactants tested had positive effects on EC reservoir
cores. For both the EC cores/EC crude oil/EC brine and the EC
cores/FM crude oil/SW systems, oil recovery by spontaneous
imbibition was poor in water and various surfactant solutions. One
core appeared oil-wet after soaking in the T91-8 solution. Therefore,
the tested surfactants are not suitable for improving oil recovery in EC
field.
Rock mineralogy and permeability play important roles in surfactant
stimulation to improve oil recovery. Formations of dolomite rocks with
high permeability respond better to surfactant treatment. It is essential
that target oilfields be evaluated individually in the laboratory for the
effectiveness of any specific surfactant treatment before field treatment
is scheduled.
Nomenclature
C = surfactant concentration, ppm
Kg = air permeability, md
Na = Bond number
r = pore radius
Swi = initial water saturation
R = oil recovery, %OOIP
ρ = density, g/ml
σ = interfacial tension, mN/m
φ = porosity
Acknowledgement
This project was supported by DOE SBIR Grant No. DE FG26-
4NT15527. Encore Acquisition Company, Ft. Worth, Texas, and Yates
Petroleum Corporation, Artesia, New Mexico, supplied the rocks and
crude oil. The laboratory tests and thin section analysis were
performed at the University of Wyoming.
3
References
1. Graham, J.W. et al.: “Method of Increasing Oil Production,” U.S.
Patent No. 2792894 (1953).
2. Putra, E., Fidra, Y. and Schechter, D.S.: “Study of Waterflooding
Process in Naturally Fractured Reservoirs from Static and
Dynamic Imbibition Experiments,” Proc., International Symposium
of the Society of Core Analysts, Golden, CO (August 1999).
3. Craig, M.D.: “Oil Recovery Process Employing Cyclic Wettability
Alteration,” U.S. Patent No. 4842065 (1988).
4. Stone H.L., Graham, J.W., and Blackwell, R.J.: “Oil Recovery
from Fractured Matrix Reservoirs,” U.S. Patent No. 3498378
(1970).
5. Spinler, E.A. et al.: “Enhancement of Oil Recovery Using a Low
Concentration of Surfactant to Improve Spontaneous and Forced
Imbibition in Chalk,” paper SPE 59290 presented at the 2000
SPE/DOE Improved Oil Recovery Symposium, Tulsa, Oklahoma,
3–5 April.
6. Standnes, D.C. and Austad, T.: “Wettability Alteration in Chalk 2.
Mechanism for Wettability Alteration from Oil-Wet to Water-Wet
Using Surfactants,” J. Petr. Sci. Eng. (2000) 28 ,123.
7. Standnes, D.C. et al. : “An Evaluation of Spontaneous Imbibition
of Water into Oil-Wet Carbonate Reservoir Cores Using a
Nonionic and a Cationic Surfactant,” Energy & Fuels (2002), 16,
1557-1564.
8. Austad, T.: “Seawater as IOR Fluid in Fractured Chalk,” paper
SPE 93000 presented at the 2005 SPE International Symposium
on Oilfield Chemistry, Houston, Texas, 2–4 February.
9. Chen, H.L. et al.: “Laboratory Monitoring of Surfactant Imbibition
Using Computerized Tomography,” paper SPE 59006 presented
at the 2000 International Petroleum Conference and Exhibition,
Villahermosa, Mexico, 1–3 February.
10. Hirasaki, G. and Zhang, D.L.: “Surface Chemistry of Oil Recovery
from Fractured, Oil-Wet, Carbonate Formation,” paper SPE 80989
presented at the 2003 SPE International Symposium on Oilfield
Chemistry, Houston, Texas, 5–8 February.
11. Xie, X. and Weiss, W. W.: “Chemical Stimulation of Oil Wells
Producing from Carbonate Reservoirs,” Phase II annual report,
Contract No. DE-FG03-01ER83226, U.S. DOE SBIR Program,
May 2003.
12. Xie, X. et al.: “Improved Oil Recovery from Carbonate Reservoirs
by Chemical Stimulation,” SPEJ (September 2005) 276.
13. Xie, X. and Weiss, W. W.: “Chemical Stimulation of Oil Wells
Producing from Carbonate Reservoirs,” Phase II final report,
Contract No. DE-FG03-01ER83226, U.S. DOE SBIR Program,
May 2004.
4 SPE 106402

TABLE 1A—FM RESERVOIR CORES FROM C ZONE

R by FM imb. R by surf. imb.
Core kg, md Swi, % ,% Brine %OOIP Surfactant, C %OOIP

4378 560.0 0 16.5 FM 1.6 T91-8, 1500ppm 32.5

4390.3 91.0 0 13.9 FM 3.0 T91-8,3500ppm 38.8

4389.9 98.0 0 14.3 FM 1.5 T91-8, 1500ppm 27.9

4378.8 154.0 0 13.0 FM 1.5 T91-8,3500ppm 23.5

4377.9 483.0 0 16.3 FM 2.0 T91-8,3500ppm 45.6

4378.2b 407.0 0 16.0 FM 1.1 T91-8, 1500ppm 16.7

4391b 623.0 0 20.0 FM 1.7 T91-8, 1500ppm 38.0

4391a 359.0 0 16.6 FM 1.5 T91-8,3500ppm 32.9

4384.3 5.1 59.1 19.6 FM 0.0 T91-8,3500ppm 9.4

4384.2 5.4 38.2 18.9 FM 0.0 T91-8, 1500ppm 10.0

4390b 48.0 31.9 15.0 FM 0.0 T91-8,3500ppm 21.8

4390a 80.0 25.4 13.9 FM 0.0 T91-8, 1500ppm 16.6

4378.3 19.6 0 14.7 SW 6.9 MCB 26.0

4379.8 55.0 17.7 10.3 SW 1.0 MCB 2.4

4379.3 100.0 21.1 10.1 SW 0.0 MCB 6.9

4378.2a 58.0 22.2 10.3 SW 0.0 T91-8 19.0

4377.8 524.0 17.3 17.1 SW 0.0 T91-8 48.2

4383.9 887.0 13.4 17.4 SW 0.0 T91-8 31.1

4379.7 25.2 17.8 9.8 SW 0.0 CD-128 0.7

4379.5 6.4 0 9.6 SW 5.9 RA246 0.0

4379.1 147.0 20.2 12.6 SW 0.0 RA246 5.0

4379.2 141.0 19.94 11.7 SW 1.2 RA246 0.0

4385.2a 3.4 0 14.8 FM 13.2 T91-8 12.4

4384.6b 1.7 0 14.5 FM 34.8 T91-8 2.6

4384.5b 2.3 0 15.9 FM 27.1 T91-8 7.8

4385.4b 17.4 0 15.2 FM 22.0 T91-8 12.6

4385.4a 19.3 0 15.2 FM 11.8 T91-8 15.0

SPE 106402 5

TABLE 1B—FM RESERVOIR CORES FROM B ZONE

R, FM imb. R, surf. imb.
Core # kg, md Swi, % ,% Brine brine,%OOIP Surfactant %OOIP

4340.5 14.0 0 11.8 FM 3.0 T91-8,3500ppm 5.5

4340.6 27.0 0 12.6 FM 2.2 T91-8, 1500ppm 4.8

4341.3 0.3 0 5.6 SW 0.0 T91-8 0.0

4341.6 0.2 0 1.1 SW 0.0 T91-8 0.0

4341.7 0.2 0 0.5 SW 0.0 T91-8 0.0

4341.2 3.6 0 7.3 SW 5.4 MCB 0.0

4340.4 7.5 0 10.8 SW 5.6 RA246 0.0

4349.3 13.1 0 9.0 FM 7.6 T91-8 0.0

4329.9 3.4 21.1 7.8 FM 0.8 T91-8,3500ppm 0.0

4329.8a 12.0 11.9 8.8 FM 0.0 T91-8, 1500ppm 0.0

4329.8b 10.5 0 8.8 SW 6.9 T91-8 0.0

4328.3 5.0 0 7.4 SW 6.2 L-64 0.0

4328.0 3.7 0 6.8 SW 9.8 T91-8 0.0

4327.8 2.9 0 5.4 SW 5.9 CD-128 0.0

4328.4 4.1 0 7.2 SW 8.3 L-64 0.0

4329.1 13.9 0 9.8 SW 8.3 CD-128 0.0

4327.9 5.2 19.0 7.0 SW 0.0 T91-8 0.0

4329.6 5.0 25.2 8.6 SW 0.0 L-64 0.0

4328.9 10.4 20.9 8.5 SW 1.6 L-64 1.1

4328.8 25.1 19.2 9.5 SW 0.4 CD-128 0.0

4327.7a 0.6 0 4.7 FM 8.1 T91-8 0.0

4327.1a 3.4 0 5.2 FM 4.0 T91-8 0.0

4327.8b 8.4 0 6.8 FM 5.5 T91-8 0.0

4327.1b 5.5 0 6.3 FM 4.1 T91-8 0.0

4329.7 14.0 0 9.1 FM 5.7 MCB 1.0

4327.6b 0.3 0 2.9 FM 2.5 MCB 0.0

4327.2a 4.8 0 6.0 FM 3.0 MCB 0.0

4327.6a 1.3 0 4.4 FM 10.4 MCB 0.0

4329.9b 1.0 0 6.1 FM 4.4 T91-8 0.0

4329.7b 13.1 0 9.7 FM 7.4 T91-8 0.0

6 SPE 106402

TABLE 1C—EC RESERVOIR CORES

Core # kg, md Swi, φ, %
% R, brine imb. Surfactant R, surf. imb.
Brine used Oil used ,%OOIP %OOIP
1300 1 0 10.33 EC EC 19.44 T91-8 0
1352.8 2.6 0 10.31 EC EC 25 T91-8 0
1387.0 6.1 0 10.94 EC EC 3.47 T91-8 0
1387.2 12.8 0 12.19 EC EC 3.47 T91-8 0
1387.5 34 0 13.37 EC EC 3.03 T91-8 0
1299.5 1.2 48.4 11.7 EC EC 1.3 T91-8 0
1352.0 18.1 13.0 13.1 EC EC 0 T91-8 0
1354.8 6.4 8.5 11.2 EC EC 0 T91-8 0
1354.9 6.2 8.2 10.2 EC EC 0 T91-8 0
1354.0 1.1 15.5 7.5 EC EC 0 T91-8 0
1351.1 0.4 0 6 SW FM 3.96 T91-8 1.66
1351.3 0.5 0 6 SW FM 1.9 T91-8 1.27
1388.8 0.7 0 9.8 SW FM 13.77 L-64 6.07
1298.1 0.3 0 3.7 SW FM 0 L-64 1.79
1299.0 0.6 0 9.2 SW FM 29.46 CD-128 0.63
1298.9 0.2 0 3.1 SW FM 1.26 CD-128 1.73
1299.2 0.7 0 10.8 SW FM 33.79 MCB 0
1298.0 0.3 0 3.7 SW FM 2.25 MCB 0
1304.5 0.1 0 4.7 SW FM 7.67 RA246 0
1304.3 0.3 0 6.7 SW FM 0 RA246 0
1387.8 26.4 6.6 13.95 SW FM 0 T91-8 0
1352.9 1.5 30.8 10.44 SW FM 5.78 T91-8 0
1355.0 6.8 8.1 10.25 SW FM 0 L-64 0
1386.0 1.6 9.8 7.34 SW FM 0 L-64 0
1386.8 3.4 7.5 9.31 SW FM 0 CD-128 0
1388.4 1.7 15.4 8.5 SW FM 0 CD-128 0
1388.1 7.6 6.0 10.26 SW FM 0 MCB 0
1386.2 5.2 3.4 8.95 SW FM 0 MCB 0
1353.0 6.7 9.5 10.13 SW FM 2.06 RA246 0
1352.7 7.2 16 13.8 SW FM 0 RA246 0
SPE 106402 7

TABLE 2—TEST BRINE COMPOSITION AND CONCENTRATION (G/L)

Composition FM brine SW brine EC brine
NaCl 61.773 28 64.3
KCl 0 0.935 0
CaCl2 5.944 1.19 8.8835
MgCl2 1.788 5.368 5.88
Na2SO4 6.284 0 3.0
NaHCO3 2.093 0 0
Total dissolved solids, ppm 77,882 35,493 82,064

TABLE 3—CRUDE OIL PROPERTIES

Crude oil API° Viscosity at Asphaltene content, Wax content, wt%
40°C, cp wt%
FM 27.13 9.9 1.0 0.6
EC 36.15 4.2 - -

TABLE 4—PHYSICAL AND CHEMICAL PROPERTIES OF FOUR OF THE SURFACTANTS TESTED

Product name L64 (Pluronic) Tomadol 91-8 Rhodacal A Rhodapex CD 128i Mirataine CB
246 L
Chemical name Ethylene and Poly (2.5 or 6 or 8) Sodium Ammonium C6-10 Cocamidopropyl
propylene oxyethylene C9-11 alpha-olefin alkyl ether sulfate betaine
oxide alcohol sulfonate
Type nonionic nonionic anionic anionic amphoteric
Designated as L64 T91-8 RA-246L CD-128 MCB
Chemical HO(C2H4O)a(C ROCH2CH2O)nH Emulsifier Foam stablizer agent -
formula 3H6O)b(C2H4O) R = C9/C10/C11
CH
Chain length 14 9–11 14 - 16 - -
Equivalent 2900 524 - - -
weight
Commercial ~ 100 ~ 100 39 ~ 56 - 60 -
concentration,
(wt%)

TABLE 5—CRUDE OIL PROPERTIES AND RELATED INTERFACIAL TENSIONS (MN/M)

Crude oil EC crude oil FM crude oil
Measurement temperature, °C 40 40
Brine EC brine FM brine SW brine
no surfactant added 30.2 17.2 20.9
3000 ppm T91-8 added 3.6 2.0 2.6
3000 ppm L-64 added - - 0.2
3000 ppm RCD-128 added - - 1.5
3000 ppm RA-246L added - - 0.28
3000 ppm MCB added - - 1.6
8 SPE 106402

Fig. 1a—Distribution of permeability and porosity of FM cores.

Fig. 1b—Distribution of permeability and porosity of EC cores.

SPE 106402 9

Fig. 2a—Thin sections of FM rock.

Fig. 2b—Thin section of EC rocks.

10 SPE 106402

60
Core # Swi, % T91-8 concentration
4390.3 0 C = 3500 ppm
50 4389.9 0 C = 1500 ppm
4385.4a 0 C = 3000 ppm
4390b 31.9 C = 3500 ppm
4390a 25.4 C = 1500 ppm
40 4377.8 17.3 C = 3000 ppm
R, %OOIP

30

20

10

0
0 10 20 30 40 50 60 70 80
Imbibition time, day

Fig. 3a—Spontaneous imbibition of cores from C zone in brine and T91-8 solution.

35
Core # Swi, % Surfactant (C = 3000 ppm)
4378.3 19.6 MCB
30 4379.3 21.1 MCB
4379.7 17.8 CD-128
4379.1 20.2 RA246
25

20
R, %OOIP

15

10

0
0 10 20 30 40 50 60 70 80
Imbibition time, day

Fig. 3b—Spontaneous imbibition of cores from C zone in brine and

surfactant solutions.
SPE 106402 11

20

Core # Swi, % Surfactant

4340.5 0 T91-8, 3500 ppm
4340.6 0 T91-8, 1500 ppm
4341.2 0 MCB, 3000 ppm
4340.4 0 RA246, 3000 ppm
15 4327.9 19.0 T91-8, 3000 ppm
4328.8 19.2 CD-128, 3000 ppm
4328.9 20.9 L-64, 3000 ppm
R, %OOIP

10

0
0 20 40 60 80
Imbibition time, day

Fig. 4—Spontaneous imbibition of cores from B zone in brine and surfactant

solutions.

50
C zone cores
B zone cores

40
R by surfactant, %OOIP

30

20

10

0
0.1 1.0 10.0 100.0 1000.0
C ore perm eability, m d

Fig. 5—Permeability versus improved oil recovery by surfactants.

12 SPE 106402

50
C zone cores
B zone cores

40
R by surfactants, %OOIP

30

20

10

0
0 5 10 15 20 25
BVO, %

Fig. 6—Improved oil recovery by surfactants versus bulk volume of oil in the
cores.

20

Core# Swi, % Surfactant (C = 3000 ppm)

1352.8 0 T91-8
1387.5 0 T91-8
15 1352.0 18.1 T91-8
1354.8 8.5 T91-8
Oil Recovery, %OOIP

10

0
0 10 20 30 40 50
Imbibition time, days

Fig. 7—Imbibition of EC cores with EC crude oil/brine and T91-8 as

surfactant.
SPE 106402 13

50
Core# Surfactant (C = 3000 ppm)
1351.1 T91-8
1388.8 L-64
1299.0 CD-128
40
1299.2 MCB
1304.5 RA246

Swi = 0%
30
R, %OOIP

20

10

0
0 10 20 30 40 50 60
Imbibition time, days

Fig. 8—Effect of surfactant solutions on oil recovery of EC cores/FM crude

oil/SW.