Use of Surfactant to Reduce CO2 Mobility

in Oil Displacement
George G. Bernard, SPE, Union Oil Co. of California
L. W. Holm, SPE, Union Oil Co. of California
Craig P. Harvey, Union Oil Co. of California

Abstract
This paper presents results from a study designed to tertiary oil production from linear cores appears to
improve effectiveness of CO 2 flooding by reducing be limited to CO 2 extraction. Approximately the
CO 2 mobility. In the course of reaching this ob- same oil recovery was obtained either by continuous
jective we (1) screened surfactants for their ability to CO 2 injection after a surfactant slug or by alternate
generate an effective and stable emulsion with CO 2 slugs of CO 2 and surfactant solution. It was found
under reservoir conditions, (2) determined the that oil recovery efficiency increased when surfactant
co.ncentration range over which surfactants were was used with CO 2 and that efficiency increased with
effective, (3) examined chemical stability of the flooding pressure.
surfactants at reservoir conditions, (4) determined One anionic surfactant was found to be superior
the extent to which emulsifying action alters gas and for this purpose. This surfactant emulsified CO 2
liquid mobilities in carbonate and sandstone cores, well, was least adsorbed on carbonate rocks, and
(5) determined that surfactant can enhance the greatly reduced CO 2 mobility in linear cores at
production of residual oil from watered-out car- concentrations of 0.1 to 1070.
bonate cores by CO 2 , and (6) showed that the The study indicates that effectiveness of CO 2
permeability reduction caused by surfactant can be miscible flooding can be increased by alternate in-
dissipated. jection of CO 2 and aqueous surfactant slugs into the
At reservoir conditions required for miscible reservoir.
displacement, carbon dioxide exists in its critical state
as a very dense fluid whose viscosity is about one- Introduction
eighth that of crude oil. Generally, this unfavorable The basic principles of CO 2 flooding have been
viscosity and mobility ratio produces inefficient oil studied for the past 25 years by many investigators. 1-
displacement. This study shows that surfactant 4 Numerous laboratory studies have demonstrated
reduces CO 2 mobility and should improve oil that CO 2 , at elevated pressures, can recover oil
displacement by CO 2 , presumably by reducing flow unrecoverable by conventional methods and that
through the most permeable zones, thus increasing super-critical CO 2 develops multicontact misciblity
areal and vertical sweep efficiencies. with many crude oils, with a very efficient oil
All three classes of surfactants (anionic, cationic, displacement, approaching 100% of the contacted
and nonionic) were found to be stable under con- oil. Generally, oil recoveries with CO 2 have been
ditions encountered during a CO 2 flood in limestone much higher in the laboratory than in the field
formation; however, only a few surfactants had because field conditions are more severe for all oil
proper adsorption and emulsifying properties. recovery processes.
Surfactant generated foams or emulsions with CO 2 A principal problem in CO 2 flooding is the low
at reservoir conditions (1,000 to 3,000 psi and 135°F) viscosity of CO 2 compared with that of crude oil. 5,6
dramatically reduced CO 2 flow through sandstone At reservoir conditions, CO 2 viscosity is often 10 to
and carbonate cores. Surfactant reduced the amount 50 times lower than oil viscosity. At these un-
of CO 2 used to recover a given volume of oil, favorable viscosity (mobility) ratios, CO 2 has a great
especially from watered-out cores. The mechanism of potential to channel through the oil. Added to this is
0197·7520/80/0008·8370$00.25 the inherent tendency of a highly mobile fluid to flow
Copyright 1980 Society of Petroleum Engineers preferentially through the more permeable rock
AUGUST 1980 281
 TABLE 1- SURFACTANTS USED IN TESTS The specific objectives of our experimental
program were to (1) screen surfactants for their
No. Chemical Type
ability to generate an effective and stable foam or
1 Ammonium sulfate ester (Ali pal CO-128)
2 Fatty-trimethyl ammonium chloride emulsion in presence of CO 2 , (2) determine the
3 Polyoxyethylene alkyl phenol concentration range over which the surfactants are
4 Polyoxyethylene polyol effective, (3) examine the chemical stability of
5 Modified ammonium lauryl sulfate ester
6 Ammonium sulfate ester surfactants at reservoir conditions, (4) determine the
extent to which the surfactant alters gas (C0 2 ) and
liquid mobilities in carbonate and sandstone cores,
(5) examine the effect of the surfactant on
sections. These two basic factors - permeability production of residual oil from watered-out car-
variations and unfavorable mobility ratios - greatly bonate cores, and (6) show that flow reduction
reduce the effectiveness of field CO 2 floods and caused by the surfactant is not permanent and
often make then uneconomic. reduced flow rates can be restored to near original
Because CO 2 is a costly fluid compared with values.
water, various methods have been used to minimize Screening of Surfactants for Foaming
the amount of CO 2 required to recover a barrel of
oil. In one method, a slug of CO 2 is used rather than
Ability and Chemical Stability
continuous CO 2 injection. The CO 2 slug is displaced Selection of Surfactant Candidates
by water. In another method, CO 2 slugs are injected An almost limitless number of surface active agents
with the production wells shut in to avoid severe are manufactured for a variety of applications. As no
pressure sinks and accompanying channeling. 7 In theoretical basis currently exists for choosing a
still another method, alternate slugs of CO 2 and surfactant having the optimum foaming properties,
water are used. 8 ,9 The objective here is to reduce the selection process was based on manufacturers'
CO 2 fingering by reducing CO 2 mobility. This claims and the past experience of our research group.
method has both positive and negative effects. The Several foaming agents were evaluated, but many
water reduces CO 2 mobility, but it also traps oil, were found unsuitable because of their insolubility in
increases water flow, and decreases extraction of the injection brine or their inability to foam or
hydrocarbons from oil by CO 2 . emulsify the CO 2 . Six agents were selected for
Our experience in laboratory and field studies consideration; these represent all three classes of
indicated that foam potentially presents a more surfactants (anionics, cationics, and nonionics).
efficient method of reducing CO 2 mobility. 10,11 The Their general description is listed in Table 1. .
inherent advantage of foam over water for mobility Sulfate Ester 1 (used in our core tests) is Alipal
improvement is that a foam is 85 to 95% gas. This CD-128, which is commercially available as a
means that a relatively small amount of water can be viscous, yellow liquid of 58070 activity. It is a mixture
used to decrease CO 2 mobility. Furthermore, foam of aliphatic sulfate esters. Literature predicts ex-
possesses other properties that are favorable for oil cellent foaming activity for sulfate esters, such as
recovery, particularly by CO 2 flooding. Foam CD-128, that have a terminal sulfate group.lO
viscosity is greater than the viscosity of its com- Previous studies have shown that CD - 128 is
ponents and foam viscosity increases with the somewhat unique in being only mildly adsorbed by
capillary diameter. Both of these factors are solids. However, it has been reported that this
favorable for greater oil recovery because increased foaming agent readily hydrolyzes at elevated tem-
viscosity is reflected in improved mobility ratio. peratures and under acidic conditions.
It has also been shown that foam increases trapped Surfactant 5, an ammonium lauryl sulfate ester,
gas saturation. lO ,l1 As gas saturation increases, oil was found to be only sparingly soluble in many
saturation decreases. In addition, a high trapped gas brines, so that its use would be quite restricted.
saturation usually reduces gas mobility. However, it was sufficiently soluble to be included in
Still another beneficial effect of foam in oil subsequent laboratory tests.
recovery results from its surface activity, which Surfactant 6 is another sulfate ester whose ap-
lowers water/oil interfacial tension and promotes plicability is doubtful because its commercial
wetting of oil-wet surfaces. Finally, foam has been availability is questionable.
found to form more readily where oil saturation is Surfactant 2 is a quaternary ammonium salt and
low (water saturation high) and thereby tends to have was included because such compounds tend to be
the greatest effect in waterflooded zones. chemically stable under nonalkaline conditions.
All of theses unique properties of foam indicated However, they are strongly adsorbed by solids and
that it should be useful in CO 2 flooding. However, it readily undergo cationic exchange.
was not known whether the beneficial properties of a Nonionic surfactants are considered to be low-to-
foam would exist at the very high flooding pressures moderate foamers, but these have minor problems
used in this experimental program wherein the associated with adsorption or chemical degradation.
density of CO 2 is as high as 0.6 g/cm 3 . Also, at these Two members of this class (Surfactants 3 and 4) were
high densities, CO 2 is considered to be a dense fluid, selected for evaluation.
resembling a liquid more than a gas. Thus, the term
"emulsion" is more descriptive of the true state of Preliminary Testing of Foaming Ability
the mixture than the term "foam." The first criterion used to judge the relative foaming
282 SOCIETY OF PETROLEUM ENGINEERS JOURNAL
 TABLE 2 - COMPARISON OF FOAMING ACTIVITY TABLE 3 - EMULSION STABILITY
(Atmospheric Pressure) WITH C0 2 /CH 4 MIXTURE
Pressure Emulsion Stability (seconds)
Foam Height (ml)
Surfactant (psig) Pure CO 2 90% CO 2 , 10% CH 4
Surfactant 1 % Concentration 0.1 % Concentration
Alipal CD·128 1,500 135 60
1 125 75 2,500 150 195
2 98 57
3 83 49
6 68
4 60 43
5 39 45

abilities of these surfactants was the height of foam the range of 2,500 to 2,600 psig at temperatures that
generated with air by shaking an aqueous solution of varied from 135 to 140°F.
each surfactant. Foam height was determined by Before and at the conclusion of this aging period,
shaking a 20-cm 3 sample of a surfactant solution in a the surfactant solution was tested for pH, surface
100-cm 3 graduated cylinder for 15 seconds and tension, emulsion height, and emulsion height of the
measuring the height of the foam 60 seconds after the solution diluted 1: 10 with injection brine. These tests
shaking period. The results of this test showed CD- revealed no significant decline in the emulsifying
128 to be the best foamer at both 1 and 0.10,10 con- ability of the surfactant. Chromatographic analyses
centrations. Test results are presented in Table 2. of the Alipal CD-128 solution showed that the initial
concentration of the surfactant was undiminished
CO 2 Emulsifying Ability and Stability after the 3-month aging period. These results suggest
Test at Reservoir Conditions that the surfactant is chemically stable for a suitable
This experiment was designed to determine relative length of time at the temperature, pressure, pH, and
emulsifying ability and emulsion stabilities using electrolyte concentrations existent in the formation
CO 2 at reservoir conditions. simulated.
A Jerguson cell was charged with equal volumes
(20 cm 3) of CO 2 and injection brine containing 5,000 Surfactant Aging Test: Chemical Stability
vol ppm of surfactant. A small amount of crude oil vs. Solution pH
(1 cm 3) and carbonate rock (- 500 mg) was added. The surfactant was subjected to a second aging test to
The system was pressured to 1,500 to 2,500 psig at a examine surfactant chemical stability dependence
temperature of 135°F. The cell then was shaken for upon solution acidity. Three 1% solutions of the
15 seconds, and the time required for the total surfactant were prepared in synthetic brine and
collapse of any emulsion was measured. The acidified with hydrochloric acid to initial pH's of 3,
emulsion stability of the CD-128 solution proved to 4, and 5. These solutions then were stored at a
be superior to that of the other surfactants at both temperature of 130 to 135°F for 164 days. During
pressures. this period, the surfactant solutions were examined
The gas available for injection at many locations periodically for foam height, surface tension, pH,
may not be pure carbon dioxide; it may contain as and concentration using liquid chromatography.
much as 10% methane. To determine the effect of
this impurity on emulsion stability, the test was Anionic Surfactants
repeated using a gas of 90% CO 2 and 10% CH 4 . Test results for the Alipal CD-128 solutions showed
Emulsion still was generated in each case; however, that all solutions experienced hydrolysis as evidenced
with the exception of the CD-128 solution at 2,500 by the precipitous drops in pH. A hydronium activity
psig, the presence of methane was detrimental to of 10 - 5 was sufficient to initiate hydrolysis. The
emulsion stability. Test results are shown in Table 3. hydrolysis reaction is autocatalyzed by the formation
The stability of emulsion was better at the higher of sulfuric acid; thus, the degradation of the sur-
pressure. factant is accelerated progressively as the hydrolysis
proceeds and the pH drops. The mechanism of acid-
Surfactant Aging Test at Reservoir Conditions promoted hydrolysis involves the fission of the
These tests demonstrated that Alipal CD-128, a sulfur/oxygen bond, as shown below.
sulfate ester, is a superior surfactant. However, the R-OS0 3(-) + H(+).= R-(+)0-S03(-)ROH + S03
properties of a surfactant solution can be affected
adversely if it undergoes chemical degradation during H / H20
reservoir use. Another experiment was designed to 2H(+) + S04(=) .=H 2 S0 4
examine the chemical stability of the surfactant
under simulated reservoir conditions. Analyses by thin-layer chromatograhpy indicated
Samples (40 mL) of 1% solutions of surfactant in that after 140 days the sulfate ester concentrations
the injection brine were placed in 75-cm 3 pressure were only about 18% of the original. These analyses
vessels. Following the addition of approximately 250 also detected the formation of lighter materials-
mg carbonate rock, the vessel was pressured with presumably aliphatic alcohols that are also sur-
CO 2 to 2,500 psig at a temperature of 135°F. During factants but of lesser foaming ability. Despite the
the next 91 days, the pressure was maintained within approximately 90% decline in sulfate ester con-
AUGUST 1980 283
 centrations, the CD-I28 solutions exhibited moderate
emulsifying activity after nearly 6 months of aging.
Core Studies Involving Emulsions
Generated With Surfactant Solutions
and CO 2
CORE
Five series of experiments examined the effectiveness
PRESSURE
REGULATOR of Alipal CD-l28 in altering the flows of gas and
liquid through linear carbonate and sandstone cores.
With some variations, the experimental procedure
outline below was followed.
COMPRESSED
C02 PISTON
1. Measure core's initial permeability to brine.
PUMP GRADUATED 2. Saturate core with crude oil.
RECEIVER
3. Waterflood with injection brine to residual oil
Fig. 1 - Apparatus for testing adsorption of surfactants on content ( - 25070 PV for carbonate and - 32% PV for
cores. sandstone).
4. Inject 1 PV of brine containing 0- to I-vol %
TABLE 4 - CRUDE OIL PROPERTIES surfactant.
5. Inject CO 2 to displace reservoir fluids. Observe
Gravity, °API 37.0 gas breakthrough, CO 2 mobilities, gas/liquid
Viscosity at 140°F, cp 0.75
at 210°F, cp 0.63 production ratios, and oil recovery rate.
6. Following CO 2 flood, inject brine to dissipate
Distillation emulsion and reduce gas saturation. Observe im-
(gas-chromatograph simulated)
(vol %) of provement in the permeability of core to brine.
5 160 7. Depressure core to remove CO 2 , and backwash
10 197 with brine to remove any restrictions in lines and core
20 253 interfaces.
30 319
40 396 8. Flush with solvents [benzene, Skelly B
50 472 (naphtha), isopropanol, and finally a 1.5% NaCl,
60 561
70 650 0.2% CaCl 2 aqueous solution] to remove the sur-
80 767 factant and remaining crude oil.
90 914 9. Saturate core with brine to restore it to its
95 1020
original state, and then begin next test at Step 1.
These experiments were conducted under
representative reservoir conditions.
TABLE 5 - WATER-COMPOSITION The core temperature was held constant at 135°F.
The carbon dioxide was injected at pressures of
Component mg/L
1,000, 2,500, and 3,050 psig with a 10 to 100 psi drop
MgCI 2 10,418 maintained across the core.
CaCI 2 17,600
NaHC0 3 991
Na2S04 1,479
Experimental Procedure
NaCI 40,426
for Adsorption Determination
TOS 70,914
A schematic diagram of the adsorption apparatus is
shown in Fig. 1. Briefly, it consists of a cylinder of
compressed CO 2 equipped with a pressure regulator,
a constant-rate piston displacement pump, a con-
solidated core mounted in a core holder, a gas flow
C02
WET TEST
rate meter, and a liquid receiver.
Kg
METER The experiments were carried out with the
following sequence of steps: (1) the core was
saturated with 1% NaCI solution so that porosity and
permeability were measured, (2) a small slug (0.1 PV)
of 1% Alipal CD-l28 surfactant solution was in-
jected, and (3) CO 2 and 1% NaCI solution were
KEROSENE OVERBUROEN injected into the core so that the volumetric ratio of
SURFACTANT
KYORAULICLY PRESSURED. CO 2 to water at the core outlet was 100.
ELECTRICALLY KEATED VESSEL
SOLUTION The core effluent was analyzed for the presence of
Alipal CD-l28. The concentration of surfactant in
Fig. 2 - Core experiment apparatus. the core effluent was determined by measuring the
surface tension and comparing it with the surface
tension of a previously prepared calibration curve
and by an independent chemical analytical method.
284 SOCIETY OF PETROLEUM ENGINEERS JOURNAL
Equipment and Materials TABLE 6 - SU RFACTANT RETARDS GAS
BREAKTHROUGH
The tests were conducted in Berea sandstones and in
carbonate cores of unknown origin. The fluids used CO 2 Saturation at Breakthrough
in these experiments were industrial grade carbon Core Fluid (% PV)
dioxide, reservoir oil, and injection brine. Brine Brine without surfactant 27
composition and properties of the oil are presented in 1.0% CD-128 40
Tables 4 and 5.
A schematic of the experimental apparatus is
400r---------------------~
presented in Fig. 2. w • NO SURFACTANT
::E o NO SURFACTANT
Carbon Dioxide Floods in Absence of Crude Oil o 1.0% ALIPAL CD-128
::J 350
..J
Carbonate Core A: 1,000 psig CO 2 Inlet Pressure. o
The first series of tests was conducted in a 3-ft x 2- >
in. carbonate core of 15.3070 porosity. The pristine w 300
brine mobility through the core was 157 md/cp at a:
135 of; no irreversible reduction in brine mobility
oD-
250
occurred during the course of the runs. Three CO 2 ~
floods were performed to examine the effectiveness Z
w
of the surfactant in the absence of oil (Steps 2 and 3 o 200
were omitted). The carbon dioxide was injected at a:
1,000 psig with a 50-psi drop maintained across the w
D-
core. One pore volume of surfactant was used. These 150
CO 2 floods demonstrated the following. C
L The surfactant retards gas breakthrough. Fig. 3 ....W
depicts CO 2 injection vs. CO 2 saturation in the core; ow 100
the point at which CO 2 injection exceeds saturation ..,
reflects the point of gas breakthrough. The 1% CD- Z
50
128 solution was very effective in retarding gas N
breakthrough; the CO 2 saturations just before o
breakthrough are shown in Table 6.
o
2. The surfactant decreases the mobility of the 00 10 20 30 40 50
core to carbon dioxide as shown in Fig. 4. CD-128 at C02 SATURATION, PERCENT
a 1% concentration reduced the CO 2 mobility by at PORE VOLUME
Fig_ 3 - Effect of surfactant on CO 2 injection and
least 85% at high gas saturations. saturation in carbonate Core A.
3. The gas/liquid production ratio is lowered by
the presence of the surfactant. Fig. 5 shows that
gas/liquid ratio was decreased markedly by the 400
presence of CD-128.
• NO SURFACTANT
Berea Sandstone B: 2,500 psig CO 2 Inlet Pressure. o NO SURFACTANT
Surfactant effectiveness in the absence of oil also was 350 o 1.0% ALI PAL CD-128
examined in a 4-ft x 1.5-in. Berea sandstone. This
consolidated core had a porosity of 19.35% and an 300
initial brine mobility of 560 md/cp at 135°F. Two D-
CO 2 floods were conducted to compare fluid flows O
in the absence and presence of surfactant. The CO 2 C 250
injection pressure was 2,500 psig with a lO-psi drop ::E
maintained across the core in the former case and a
variable pressure drop of 10 to 100 psi in the latter. ~ 200
..J
As shown in Figs. 6 through 8, the effects of a 1070
CD-128 solution were much more pronounced in this ~ 150
more permeable core. The presence of surfactant ::E
delayed gas breakthrough by more than 40% PV
CO 2 injected; the core's CO 2 saturation exceeded oN 100
80% PV at gas breakthrough. The action of sur-
o
factant caused a drastic reduction in the core's 50
permeability . to carbon dioxide; at high gas
saturations,the CO 2 mobility was decreased by
99% - from about 750 md/cp to less than 10 md/cp.
o L--...L--'---'--__L....-...I...-....L...--L..--.::I'--.L.-....I
Brine injection following the CO 2 flood using the o 10 20 30 40 50
CD-128 solution demonstrated that emulsion C02 SATURATION,
blockage can be at least partially dissipated. Fig. 9 PERCENT PORE VOLUME
shows that the injection of 21 PV of brine reduced Fig. 4 - Effect of surfactant on CO 2 mobility and
the CO 2 saturation from 82% to 16% PV and saturation in carbonate Core A.

AUGUST 1980 285

 900~----------------------,
10000~--------------~~---'

800
0 • NO SURFACTANT
0........ o NO SURFACTANT
0 o 1.0% ALI PAL CD-128 Q. 700
0 1000
o........
0 c 600
::E
I-
c:a::~ > 500
a: I- I-
Zc:a:: ....I
0.,.... 100 m 400
i=ofJ o
00
~
~ 300
Oil) N
ON o
a: o 200
0. • NO SURFACTANT
10 ... 1.0% ALI PAL CD-128
0 100
~
a 10
::::i
N
0 1 O~~~ __~~~__~~__~~
0 0 10 20 30 40 50 o 10 20 30 40 50 60 70 80 90
C02 SATURATION, PERCENT C02 SATURATION, PERCENT
PORE VOLUME PORE VOLUME
Fig. 5 - Surfactant effectiveness in reducing gas/liquid Fig. 7 - Surfactant effectiveness in reducing permeability
ratio in carbonate Core A. of Berea sandstone Core B to CO 2 .

160 o 100000 . " . . - - - - - - - - - - - - - - ,

w o
~ ......
~ o
....I 140 o
0 o 10000
> i=
w 120 cC~
a: a: I-
0 ZcC
Q.
0..... 1000
I- 100 i=oa
Z
0
U.I go
80 Oil'!
a: OM
w
Q.
N
a:
0.
C 60 C
w ::J
I-
0
a
..,w 40 :J
• NO SURFACTANT
Z S
o
o 1.0% ALI PAL CD-128
N 20 1~~~__~~__~~~__~~
0 o 10 20 30 40 50 60 70 80 90
0
0 C02 SATURATION, PERCENT
0 10 20 30 40 50 60 70 80 90 PORE VOLUME
C02 SATURATION, PERCENT Fig. 8 - Surfactant effectiveness in reducing gas/liquid
PORE VOLUME ratio in Berea sandstone Core B.
Fig. 6 - Effect of surfactant on CO 2 injection and
saturation in Berea Core B.

286 SOCIETY OF PETROLEUM ENGINEERS JOURNAL

restored the brine mobility to 60070 of its original Gomparison purposes the CO 2 flood with surfactant
value. present was made between those with no surfactant.
A temperature of 135°F, a CO 2 injection pressure of
Carbon Dioxide Floods in Presence of Residual Oil 2,500 psig, and a pressure drop of 50 psi were
Carbonate Core C: 2,500 psig CO 2 Inlet Pressure. maintained during these floods. A final test involving
Surfactant effectiveness in the presence of oil first 0.1070 CO-128 solution was conducted at 3,050 psig
was examined in a 3-ft x 2-in. x 2-in. carbonate inlet and 100 psi fl.p. During the course of these tests,
core of 14.8070 porosity. The procedure followed in the core appeared to tighten progressively, and
this series of experiments was somewhat less involved repeated backwashes were necessary to maintain the
than that described earlier. initial brine mobility of about 94 md/cp at 100070
Three CO 2 floods (without surfactant, 0.1070 CO- saturation. All four floods were performed at a
128 solution, and 1070 CO-128 solution) were con- residual oil contents of 21 to 25070. Initial oil
ducted at 2,500 psig inlet with a 50-psi drop main- saturations for each flood were as follows: no sur-
tained across the core: In between these floods, the factant, 24.4070; Alipal CO-128, 24.7070; Alipal CO-
oil content of the core was not replenished to the 128 at 3,050 psig injection pressure, 21.5070; and no
watered-out residual level (Steps 8, 9, and 1 through surfactant, 25.3070. A 1 PV slug of surfactant
3 were omitted). Thus, in the latter floods, the oil solution was used.
saturations were low, and the oil that remained was a These experiments demonstrated again that (1)
fraction of higher asphaltene content not extracted surfactant delays CO 2 breakthrough in carbonate
by the carbon di'oxide. cores. This can be seen in Fig. 13, and (2) surfactant
This carbonate core was first acidified with dilute reduces carbon dioxide mobility and the gas/liquid
HCl and then saturated with injection brine. The production ratio. Figs. 14 and 15 show CO-128 to be
brine mobility at 100070 saturation was 207 md/cp at very effective. The action of CO-128 seems to be even
135°F. Following the injection of crude oil, and the more effective at the higher pressure (3,050 psig).
subsequent waterflood to a residual oil content of The rate of oil production was monitored during
20.0070 PV, the brine mobility was measured at 46.3 these floods. In all cases, the recovery of oil com-
md/cp. menced with CO 2 breakthrough. As shown in Fig.
After the injection of 1 PV of brine without 16, the presence of surfactant necessitated a greater
surfactant, the first CO 2 flood was conducted. At CO 2 input for the production of the first few percent
the termination of this flood, the oil saturation had pore volumes of oil, but much less CO 2 injection was
been reduced to 7.1070 PV, and the brine mobility had required for the recovery of the bulk of the residual
increased to 138 md/cp. Next, 1 PV of a 0.1070 CO- oil. These curves again reflect the effectiveness of the
128 solution was injected into the core and driven CO-128 surfactant. Oil production vs. CO 2
with carbon dioxide. At the conclusion of this flood, saturation in the core is presented in Fig. 17 and Fig.
the oil saturation was 4.6070 PV and the brine 18 shows the extent to which the cumulative gas/oil
mobility 102 md/cp. A 1070 PV solution of CO-128 production ratio was decreased by the presence of
was used in the final CO 2 flood. surfactant.
Test results are presented in Figs. 10 through 12.
These CO 2 floods demonstrated that the surfactant Berea Sandstone E - Effect of Surfactant on WAG
activity persists in the presence of oil. Surfactant Process. The final series of floods compared the
retarded gas breakthrough by as much as 30070 PV performance of the water-alternating-gas (WAG)
CO 2 injected, drastically reduced the permeability of method with and without surfactant. These tests were
the core to carbon dioxide, and greatly reduced the conducted at 2,500 psig in a 4-ft x 1.5-in. x 1.5-in.
gas/liquid production ratio. These effects are shown Berea sandstone of 19.4070 porosity.
in Table 7. In each of two runs, Step 4 was omitted and the
As Table 7 shows, the 1070 surfactant solution was CO 2 injection was alternated periodically with brine
much more effective than the 0.1070 solution; both injection. For the test without surfactant, alternate
CO 2 floods were performed at about the same oil slugs of 5.4070 PV CO 2 and 5.4070 PV brine were
saturation. injected into the core. In the case involving 1070 CO-
Following these three tests, the core was removed 128, the aqueous slugs were cut in half to 2.7070 PV in
from the overburden pressure vessel, and ap- anticipation of superior performance with surfactant
proximately 2 in. of rock was sawed off each end of present.
the core. It was thought that much of the restriction Fig. 19 shows that surfactant increases efficiency
to fluid flow was occurring at the core inlet/exit and of WAG process in at least two ways. CO 2 mobility
that this action partially would alleviate core is two to three times greater when WAG is conducted
tightening in subsequent tests. without surfactant. Also, when surfactant is present,
much less fluid is needed to reach a given CO 2 pore
Carbonate Core D: 2,500 psig CO 2 Inlet Pressure. saturation. Both of these factors clearly show that
The dimensions of this abbreviated carbonate core surfactant enhances the oil recovery potential of the
were now 32.5 x 2 x 2 in. A series of three CO 2 WAG process.
floods were performed following the nine-step
procedure outlined earlier. The first three floods Adsorption of Surfactant
were made in the absence of surfactant (two runs) It is well-known that surfactants are adsorbed from
and in the presence of 0.1070 CO-128 solutions. For solution on reservoir minerals and that such ad-
AUGUST 1980 287
 TABLE 7 - EFFECT OF SURFACTANT
ON CO 2 SATURATION AND MOBILITY
CO 2 Saturation CO 2 Mobility at
at Breakthrough High Gas Saturation
Core Fluid (%PV) (md/cp) 160
Brine without
surfactant 18 150
140
0.1% CD-128 31 60
1.0% CD-128 48 5
~ 120
0.......
100~------------------------~

z
o 80 EMULSION GENERATED BY C02 IN
C
== 100
PRESENCE OF 1% ALI PAL CD-l28
C'<I~> 60 >
o a:::I:L !:: 80 • NO SURFACTANT
o ~~ 40 ..J o 0.1% ALI PAL CD-128

5 20 In
0
"" 1.0% ALI PAL CD-128

O~------------~~----------~ 60
==N
0
>' 0 40
...:::i 300
250
w-
! ~ci200 20
a:::w~
ID~ 150
a::: O~~~~~~~~~~~MCLJ
~ 100
50
o 10 20 30 40 50 60
C02 SATURATION, PERCENT
O~~~~~-J__L-~~-L~-J~
o 2 4 6 8 10 12 14 16 18 20 22
PORE VOLUME
BRINE INJECTED, NUMBER OF Fig. 11- Surfactant effectiveness in reducing permeability
• of carbonate Core C to CO 2 ,
PORE VOLUMES
Fig. 9 - Dissipation of emulsion by brine injection into
Berea sandstone.

10000 ~----------~

w 160
==
::l
o
..J
• NO SURFACTANT
o 0.1% ALI PAL CD-128
SOR = 20% i=:e
0 140 SOR = 7.1% <1: ...
"" 1.0% ALIPAL CD-128 = 4.6% IC <I: 1000
> SOR
z,..
w 2aa
a: 120
0
~
tio
~&n
....z 100 eM
ON 100
w IC
Q.
0 o
a: 80 90
w ~u
~

c 20
w 60 ..J 10
N
t- o • NO SURFACTANT
O o
..,w 40 o 0.1% ALiPAL CD-128
... 1.11% ALI PAL CD-128
Z
1~.L...-.L...-"""".L...-L...-L...-L...-L...-L...-L...-L........J
N 20
0
0
o 10 20 30 40 50 60
C02 SATURATION,
0 PERCENT PORE VOLUME
0 10 20 30 40 50 60
C02 SATURATION, PERCENT Fig. 12 - Surfactant effectiveness in reducing gaslliquid
ratio in carbonate Core C.
PORE VOLUME
Fig. 10 - Effect of surfactant on the relationship between
volume of CO 2 injected and saturation in car-
bonate Core C.

288 SOCIETY OF PETROLEUM ENGINEERS JOURNAL

w160r-----------------------~

::E
::J • NO SURFACTANT
140
5
>
... 0.1% ALI PAL CD-128
b. NO SURFACTANT
o 0.1% ALI PAL CD-128 (J • NO SURFACTANT
(J ... 0.1% ALIPAL CD-128
~ 120 (3 L::. NO SURFACTANT
o 0.1% ALI PAL CD-128
oQ. (J

o
t- 100
zw ~:I
a:~

~ 80
zcr:
0 ....
w
Q. ~oes 100
(J(J
C 60 ::lan
C·
w O~
t- a:
frl.., 40 Q..
C 10
Z ::l
N 20 a
o ::::i
.",
o o(J 1~~~~-L__L--L__L--L~
OD'~--~~~--~~~--~~~
o 10 20 30 40 50 o 10 20 30 40
C02 SATURATION, PERCENT C02 SATURATION, PERCENT
PORE VOLUME
PORE VOLUME
Fig. 13 - CO 2 injection vs. CO 2 saturation for carbonate Fig. ·15 - Surfactant reduces C0 2 11iquid ratio in carbonate
Core D. CoreC.

100
140
• NO SURFACTANT
... 0.1% ALIPAL CD-128
80 L::. NO SURFACTANT 120
Q..
o 0.1% ALI PAL CD-128 w
(J :I • NO SURFACTANT
....... ::l 100
M...J ... 0.1% ALIPAL CD-128
C
:I CO L::. NO SURFACTANT
60 w> o 0.1% ALI PAL CD-128
>=
~
~w
(Ja: 80
::::i ~O
ZQ..
m 60
0 -~
:I 40 NZ
Ow
N (J(J
0 a: 40
(J w
Q..
20 20
o ~-L __~~__~~__~~__~

oL-L-L-~~~~~~ o 10 20 30 40
o 10 20 30 40 RESIDUAL OIL PRODUCED,
C02 SATURATION, PERCENT PERCENT PORE VOLUME
PORE VOLUME
Fig. 16- Effect of emulsified CO 2 on oil recovery from
Fig. 14 - Surfactant reduces permeability of carbonat~
carbonate Core D.
Core C to CO 2 ,

AUGUST 1980 289

 sorption can be prohibitively costly. While many
studies have been reported on adsorption from
solution, much less work has been done on ad-
12 sorption from foam or emulsion. It is quite con-
ceivable that because the liquid/gas/rock system has
• NO SURFACTANT
.4 0.1% ALIPAL CD-128 three phases with unusual configurations, adsorption
/J. NO SURFACTANT may be less from a foam or emulsion than from
10 o 0.1% ALI PAL CD-128 solution.
CLLI Three adsorption tests using 1010 CD-128 sur-
LLI:!: factant in natural carbonate cores were performed.
O::J
::J...I 8 In each test a 0.1 PV of 1010 CD-128 was displaced
Co from a core by a mixture of CO 2 and water. About
0>
O:LLI 100 PV of CO 2 were used per volume of water. This
0.0: procedure simulated the alternating CO 2/H 20
::!o 6 (WAG) process.
00.
...It- Experimental data showed that 67 to 100010 of the
cz injected surfactant was produced from each core.
::J LLI This indicated that less than 0.11 Ibm of CD-128 were
cO 4
-0: adsorbed permanently per barrel of pore space. It
Cl)LLI
LLla. also was found that CD-128 moves rapidly
0:
throughout the carbonate cores and that more than
2 50010 of the injected CD-128 is produced in the first 2
PV. A typical desorption curve for CD-128 in a
natural core is shown in Fig. 20.
o ~~--~~~~~~--~--~~
o 10 20 30 40 Discussion
C02 SATURATION, The foam or emulsion emplacement process l2 ,13
PERCENT PORE VOLUME involves the injection of an aqueous surfactant
Fig. 17 - Effect of surfactant on relationship between CO 2 solution into a reservoir followed by CO 2 injection.
saturation and residual oil production from As CO 2 and the surfactant solution are mixed in-
carbonate Core D.
timately in the reservoir, a foam or emulsion is
generated, thereby reducing the mobility of CO 2 . 14
This study presents experimental data that show the
:!: 24 process can improve oil recovery efficiency of high-
t- pressure CO 2 floods.
C 22
.... • NO SURFACTANT
At reservoir pressures required for miscible-type
~ .4 0.1% ALI PAL CD-128 displacement, carbon dioxide exists in a critical state
20 /J. NO SURFACTANT as a very dense fluid with a relatively low viscosity.
0
an
M 18
o 0.1% ALI PAL CD-128 • Our studies have shown that at these elevated
pressures and temperatures and in the presence of
N
16 crude oil, the dense CO 2 will generate a stable
...I emulsion when mixed with a surfactant solution .
m Several studies 15-17 have shown that the presence
m
.......
14
LL of surfactant decreases the permeability of porous
0 12 media to water and to various gases. Foam has been
:!: shown to be extremely effective in reducing gas
10 mobilities, the effectiveness of foaming action being
0:
0 more pronounced in the more permeable porous
8
">
LLI
6
media. Permeability reduction is enhanced with
increasing surfactant concentration, but foaming
ability of a surfactant solution is retarded somewhat
t-
C 4 in the presence of oil.
...I
::J The need to reduce C02 mobility has been shown
:!: 2 clearly by a recent report 18 on a tertiary CO 2 flood
::J at SACROC. In this project very rapid passage of
0
00 30 40 CO 2 from injection to producing wells was noted
with the resultant relatively low oil recovery.
C02 SATURATION, % PORE VOLUME Residual oil recovered by CO 2 was estimated to be 3
to 5.8010 of the original oil saturation. Volumetric
Fig. 18 - Surfactant reduces gas/oil ratio in carbonate
Core D. sweep efficiency was calculated to be about 0.33, and
estimated CO 2 requirement for tertiary recovery is 15
to 20 MscflSTB oil. The data in our study indicate
that performance of such tertiary CO 2 floods should
290 SOCIETY OF PETROLEUM ENGINEERS JOURNAL
be improved by use of surfactant to reduce CO 2
mobility.
The primary requirement for control of CO 2
mobility is a surfactant with proper chemical
stability, adsorption characteristics and foaming or
emulsifying capability. After screening a large
number of surfactants, we found one (Alipal CD-
128) that appears to be especially well-suited for use
in CO 2 floods. This surfactant performs well in a
CO 2 /H 2 0/oil system, remains chemically stable in a
CO 2 /rock system for long time periods and is ad-
sorbed to a minimal degree.
The effectiveness of this surfactant was tested
under reservoir pressure and temperature in various
CO 2 drives. In one group of experiments, the sur-
factant was used to reduce CO 2 mobility in an oil-
free system. In such systems (both in sandstone and
limestone), it was exceedingly effective in reducing
CO 2 mobility. The surfactant reduced CO 2 mobility
by up to 90%.
In another group of experiments, the surfactant
was used to reduce CO 2 mobility in an oil/water
system. Alipal CD-l28 also was effective in reducing
CO 2 mobility, but the mobility reduction was
somewhat less than in the oil-free system. An ad-
vantage of this difference is selective mobility
reduction. It is highly desirable to attain greatest
mobility reductions in reservoir zones free of oil, and
lesser reductions in oil saturated zones. The- process
appears to have a potential to accomplish this 20 40 60 80 100
purpose. FLUIDINJECTED,PERCENT
One of the commonly used methods of reducing PORE VOLUME
CO 2 mobility is by alternating slugs of water and Fig. 19 - Surfactant reduces CO 2 mobility in Berea sand-
CO 2 (WAG). However, the large amounts of water stone using the WAG injection process.
usually used in this process tend to reduce oil
recovery. Our data show that when surfactant is
incorporated into the WAG process, less water is
needed to reduce CO 2 mobility. This should result in 350
higher oil recovery. :::E
Better mobility control should increase oil 11. INJECTED 0.1 PV OF 1% ALI PAL CD-128
11. 300 RECOVERED 94.8% OF INJECTED ALI PAL CD-128
recovery, particularly from heterogeneous systems. ..: ADSORPTION =18 LBS ALiPALlIOOO BBLS PV
Because linear, fairly homogeneous cores were used z PERMEABILITY =23.3 md
w
in this study, we did not expect to see very large U-::J 250 POROSITY =17.2%
0...1
improvements in oil recovery from injection of z:t
surfactant. This expectation was borne out by ex- ow
perimental results. For example, it is shown in Fig. 16 j::w 200
«II:
that a drive with 0.1070 Alipal CD-128 recovers 9070 of 11:0
1-0
residual oil after injection of 40070 PV of CO 2 . When Zz
the same experiment was conducted without CD-l28, w_ 150
Oco
about 120070 PV of CO 2 was needed to get the same ZN
o~
oil recovery. This shows that CD-l28 should improve 06 100
both displacement efficiency and conformance in a 0
...I
CO 2 flood. «
11.
In all the experiments with residual oil saturation, ::::i 50
oil recovery began with CO 2 breakthrough. Ap- «
parently no oil bank was formed in these short
O~~~~~~~~~-L-L__
porous systems. This conclusion is supported by o
comparing the densities and distillation curves of
reservoir oil and produced oil. All of the oil cuts PORE VOLUMES OF PRODUCED BRINE
collected during the CO 2 floods were found to be
0 Fig. 20 - Adsorption/desorption of Alipal CD-128 in core.
lighter than the 37.0 API reservoir oil. This indicates
that the primary mechanism of residual oil
production was CO 2 extraction of light and middle
range hydrocarbons.
AUGUST 1980 291
Conclusions 7. Holm, L.W. and O'Brien, L.J.: "Carbon Dioxide Test at the
Mead-Strawn Field," J. Pet. Tech. (April 1971) 431-442.
1. Alipal CD-l28 can reduce CO 2 mobility under 8. Caudle, B.H. and Dyes, A.B.: "Improving Miscible
reservoir conditions by up to 850/0. Mobility Displacement by Gas-Water Injection," Trans., AIME (1958)
213,281-284.
reduction is greatest in oil-free or water-swept sands. 9. Blackwell, R.J., Terry, W.M., Rayne, J.R., Lindley, D.C.,
This makes the process self-regulating, in that the and Henderson, J.R.: "Recovery of Oil by Displacemems
surfactant tends to retard flow where flow rates are with Water-Solvent Mixtures," Trans., AIME (1960) 219,
greatest and CO 2 is not wasted in oil-free zones. 293-300.
2. A number of surfactants generate stable 10. Bernard, G.G. and Holm, L.W.: "Effect of Foam on Per-
meability of Porous Media to Gas," Soc. Pet. Eng. J. (Sept.
emulsions with CO 2 at reservoir conditions. 1964)267-274; Trans., AIME, 231.
However, one surfactant, a low-molecular-weight 11. BeJnard, G.G., Holm, L.W., and Jacobs, W.L.: "Effect of
ethoxylated sulfate was found to be superior for this Foam on Trapped Gas Saturation and as Permeability of
purpose. This compound had the proper com- Porous Media to Water," Soc. Pet. Eng. J. (Dec. 1965) 295-
bination of chemical stability, low adsorption, and 300; Trans., AIME, 234.
12. Bernard, G.G. and Holm, L.W.: "Enhanced Oil Recovery
high mobility reduction effectiveness. Process," U.S. Patent No. 4,113,011, (Sept. 12, 1978).
3. Permeability reductions caused by surfactant 13. Bernard, G.G. and Holm, L.W.: "Method for Recovering Oil
are not permanent and can be removed by passage of from Subterranean Formations," U.S. Patent No. 3,342,256
several pore volumes of water. (Sept. 19, 1967).
4. Adsorption of a surfactant on natural cores 14. Albrecht, R.A. and Marsden, S.S. Jr.: "Foams as Blocking
Agents in Porous Media," Soc. Pet. Eng. J. (March 1970) 51-
from CO 2 /H 2 0 emulsion was found to be about 55.
0.11 Ibm/bbl of pore space. 15. Raza, S.H.: "Foam in Porous Media: Characteristics and
5. Efficiency of the presently used WAG process Potential Applications," Soc. Pet. Eng. J. (Dec. 1970) 328-
336; Trans., AIME, 249.
injection water. When WAG CO 2 /H 2 injection is°
can be increased substantially by adding surfactant to

used with surfactants, CO 2 mobility is reduced 50070

16. Holm, L.W.: "The Mechanism of Gas and Liquid Flow
Through Porous Media in the Presence of Foam," Soc. Pet.
Eng. J. (Dec. 1968) 359-369; Trans., AIME, 243.
more than if plain WAG is used and considerably less 17. Holm, L.W.: "Foam Injection Test in the Siggins Field,
water injection is required. Illinois," J. Pet. Tech. (Dec. 1970) 1499-1506.
18. Graue, D.J. and Blevins, T.R.: "SACROC Tertiary CO2 Pilot
Acknowledgment Project," paper SPE 7090 presented at SPE Fifth Symposium
on Improved Methods for Oil Recovery, Tulsa, OK, April 16-
We thank the management of Union Oil Co. of 19,1978.
California for the opportunity to prepare and publish
this paper. SI Metric Conversion Factors
atm x 1.013 250* E+02 kPa
References bbl x 1.589 873 E-Ol m3
1. Whorton, L.P., Brownscombe, E.R., and Dyes, A.B.: cp x 1.0* E-03 Pa·s
"Method for Producing Oil by Means of Carbon Dioxide," degree API 141.5/(131.5 + °API) g/ cm 3
U.S. Patent No. 2,623,596 (Dec. 30,1952). degree F (OF - 32)/1.8 =oC
2. Holm, L.W.: "Carbon Dioxide Solvent Flooding for In- ft x 3.048* E-Ol m
creased Oil Recovery," Trans., AIME (1959) 216, 225-231.
3. Holm, L.W.: "C02 Slug and Carbonated Water Oil Recovery m. X 2.54* E+OO cm
Process," Prod. Monthly (Sept. 1963) 6. Ibm x 4.535 924 E-Ol kg
4 .Holm, L.W. and Josendal, V.A.: "Mechanisms of Oil psi x 6.894 757 E+OO kPa
Displacement by Carbon Dioxide," J. Pet. Tech. (Dec. 1974) scf x 2.863 640 E-02 std m 3
1427-1436; Trans., AIME, 257. ·Conversion factor is exact.
5. Kennedy, J .T. and Thodos, G.: "The Transport Properties of SPEJ
Carbon Dioxide," A IChE Jour. (Dec. 1961).
Original manuscript received in Society of Petroleum Engineers office Aug. 3,
6. Doscher, T.M. and Wise, F.A.: "Enhanced Crude Oil 1979. Paper accepted for publication March 14, 1980. Revised manuscript
Recovery Potential- An Estimate," J. Pet. Tech. (May 1976) received May 9,1980. Paper (SPE 8370) first presented at the SPE 54th Annual
575-585. Fall Technical Conference and Exhibition, held in Las Vegas, Sept. 23·26, 1979.

292 SOCIETY OF PETROLEUM ENGINEERS JOURNAL