SPE-174567-MS

A Novel Technique for Enhanced Oil Recovery: In-Situ CO2-Emulsion

Generation
Fawaz M. AlOtaibi, Xianmin Zhou, Sunil L. Kokal, Balasubramanian Senthilmurugan, Almohannad A. Alhashboul,
and Amin M. AlAbdulwahab, Saudi Aramco

Copyright 2015, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Enhanced Oil Recovery Conference held in Kuala Lumpur, Malaysia, 1113 August 2015.
This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
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any position of the Society of Petroleum Engineers, its officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written
consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may
not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract
Carbon dioxide miscible flooding is a proven EOR method. It faces two significant challenges: gravity
override and early CO2 break through. Many researchers have investigated different methods to control
CO2 mobility and improve its sweep efficiency. This paper, for the first time, investigates the use of a new
and unique CO2-foam (emulsion) to control CO2 mobility and also as a conformance control technique
in heterogeneous reservoirs with high permeability contrast within carbonate rocks.
The new CO2-emulsion system consists of 50-70 vol% supercritical CO2, 50-30 vol% of water-based
polysaccharide linear polymer and a foaming agent (surfactant). Several experiments were conducted
using HPHT visual cell to assess the CO2-emulsion stability as a function of temperature, pressure and
time. In addition, the rheological properties of the CO2-emulsions were investigated at different shear
rates, different pressures and mixing ratios, and at an operating temperature of 220F. Special dual core
flooding experiments were conducted using live oil at reservoir conditions to investigate the effectiveness
of CO2-emulsion system in enhancing oil recovery. Several experiments were conducted to explore the
effect of injection rate, injection mode and slug volume on incremental oil recovery. These experiments
were performed using dual core holders with different permeable carbonate composite stacks, and
permeability contrasts up to 35.
Results based on this study have shown that the CO2-emulsion system is stable at 210F for extended
periods of time without any emulsion breakage or phase separation. The effective viscosity of CO2 was
increased by 3-4 orders of magnitude and approached 100 cP at reservoir conditions. Results also show
the emulsions ability to severely reduce permeability of the higher permeable cores resulting in
significant incremental oil recovery from the lower permeable cores. This new and unique emulsion
system has the ability to be created in-situ to provide better mobility control of the injected CO2.
Additionally, this paper provides optimal design parameters of the new emulsion system to behave as a
conformance control agent, and also to enhance the recovery of oil following water and CO2 floods.

Introduction
Carbon dioxide as an injection fluid into oil reservoirs has been tested widely, and has become a proven
Enhanced Oil Recovery (EOR) method. CO2 dissolves easily into oil, reducing its viscosity, and

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extracting the oils light components at moderate pressures, and it can become miscible with oil at
relatively low pressures (Abdassah et al. 2000). The minimum miscibility pressure (MMP) for CO2 is
significantly lower compared to other gases. For most crude oils, CO2 is in the near-critical or supercritical
state and the dense CO2 acts as a good solvent.
Oil production from CO2 has continued to grow over the past few decades and is anticipated to increase
further, propelled by the current movement toward CO2 sequestration (Hite et al. 2004, Mungan 1991,
Abdassah et al. 2000, Alvarado and Manrique 2010). Carbon dioxide has some very important technical
and economic reasons for its use as an injection gas for oil recovery. CO2 is easier to handle, is cheaper
and an environmentally better candidate than others (Enick et al. 1988, Christensen et al. 1998, Bayraktar
and Kiran 2000).
The CO2-EOR process is handicapped by several challenges. The first challenge is the gravity override
of the injected CO2 due to density differences between the injected CO2 and resident fluids in the
reservoir. The CO2, being lighter, tends to rise to the top of the reservoir thereby bypassing some of the
remaining oil, Figure 1, and resulting in poor oil recovery in the lower portion of the reservoir. This
problem is especially acute in thick formations (Campbell 1985, Masalmeh et al. 2010, Chakravarthy, et
al. 2004). The second challenge is viscous fingering that is caused by the lower viscosity of the injected
CO2. Typical dense CO2 viscosity at reservoir conditions is in the range of 0.05-0.1 cP, which is much
lower than the viscosity of resident oil and brine. The resulting unfavorable mobility ratio leads to viscous
fingering causing early CO2 breakthrough, high CO2 utilization factors, poor sweep efficiency and low
overall oil recoveries (Campbell 1985, Masalemh et al. 2010, Chakravarthy, et al. 2004). The third
challenge associated with CO2-EOR is reservoir geology and heterogeneities including high permeability
streaks and fractures that can negatively impact the sweep efficiency of a CO2-EOR flood.

Figure 1CO2 Gravity override during CO2-EOR

Most of these challenges have been tackled using water-alternating-gas (WAG) process. Although the
WAG process improves the mobility of CO2, the process loses its effectiveness in controlling CO2
mobility deep into the reservoir and beyond a certain distance from the wellbore. Another technique that
provides excellent alternative to WAG for controlling the CO2 mobility is the CO2-foam (emulsion). The
main purpose of using CO2-foams is to increase the viscosity of the CO2 and therefore reduce its mobility
through the reservoir. This emulsion is generated using water-soluble surfactants, CO2-soluble surfactants
or nano-particles (Enick 1998, Dalland and Hanssen 1996, Enick and Olsen 2012, Adkins et al. 2007,

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Dandge and Heller 1987). A field demonstration of CO2-foam application was started at East Vacuum
Grayburg-San Andres Unit (EVGSAU) in 1992. The objective of this field test was to show the potential
of CO2-foam for mobility control or fluid diversion in a CO2 flood. The laboratory study on evaluation
of surfactants for generating CO2-foam in this field was started in early 1991 at the Petroleum Recovery
Research Center (PRRC) and the Bartlesville laboratory of Phillips Petroleum Company (Jyun-Syung et
al. 1994). The EVGSAU CO2-foam field trial proved that a strong foam could be formed in situ and that
the apparent in-situ mobility of CO2 after foam generation was approximately one-third of that observed
during the baseline CO2 injection. Production of incremental oil occurred, and gas cycling decreased
dramatically in the offending well as a direct result of surfactant injection (Martin et al 1994). Another
field demonstration of CO2-foam project was done at Kinder Morgans SACROC field. A new conformance solution was developed to help producers reach and recover more oil from existing wells. Dow
Chemicals ELEVATETM CO2 EOR Conformance Solution was utilized in this field trial. The single
injector stage was completed successfully and showed a significant reduction in the CO2 injectivity as well
as a 30% increase in oil production at an offset producer. By injecting surfactant into the CO2 phase
directly after water cycle, the CO2 injectivity deceased by more than 50% compared to CO2 injection
alone (Aaron et al. 2012). The results through the end of the project indicated that the optimized injection
strategy has a positive effect on the pilot area.
Many researchers have investigated different methods to control CO2 mobility and enhance its sweep
efficiency. In this paper we will be investigating the use of gelling CO2 water emulsions, stabilized by
surfactants and polymers, to control the mobility of CO2 and also as a conformance control technique in
heterogeneous reservoirs with high permeability contrast. In addition, the stability, compatibility and the
rheological properties at different shear rates, different pressures and mixing ratios of this emulsion were
investigated. This investigation highlighted the optimal CO2/liquid ratio, conenctration of both surfactant
and polymer, and volume of CO2 emulsion slug for maximum oil recovery of core plugs with high
permeability contrast.

Experimental Studies
Materials
A commercial foaming agent was provided by a service/chemical company. The main function of the
foaming agent is to enhance CO2 viscosity in well treatments. It consist of a gelling agent that is
polysaccharide-based and a foaming agent or surfactant that is added to stabilize the emulsion between
CO2 and base gel. The concentrations of each additive are listed in Table 1.

Table-1Commercial CO2 Base Gel Formula

Formula

Polymer (gpt)

Surfactant
(gpt)

Stabilizer
(gpt)

8.9

7.0

0.0

Three types of brines were used in this study: field connate water, seawater and formation water. The
components of these brines are listed in Table 2. A dead crude oil from a carbonate reservoir was used
in this study to set up initial water saturation (Swi). Separator crude oil and gas were collected from the
same reservoir and recombined to prepare the live crude oil sample, which was used in the coreflood
apparatus for water flooding and sc-CO2 miscible flooding experiment. The viscosity and density of dead
and live crude oils at reservoir temperature are listed in Table 3. Molecular weight of recombined live
crude oil in this study was 121.

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Table-2Recipes of Field Connate Water, Seawater and Formation Water

Component

Field Connate
Water (g/l)

Seawater (g/l)

Formation
Water (g/l)

NaCl
CaCl2.2H2O
MgCl2.6H2O
Na2SO4
NaHCO3

150.446
69.841
20.396
0.518
0.487

41.041
2.384
17.645
6.343
0.165

0.0133
0.4879
0.4349
0.0000
0.3291

Table-3Fluid Properties
Reservoir Condition, 210 F & 3200 psi
Fluids
Dead Crude Oil
Live oil
Supercritical CO2

Density (g/cc)
0.8230
0.7550
0.5337

Viscosity (cP)
2.50
0.73
0.045

Sc-CO2 was also used as a displacing agent for tertiary oil recovery at a pressure of 3200 psi and
temperature of 210F. The CO2 was miscible with the live oil at these conditions. Laboratory study on the
MMP has been reported in detail by AlOtaibi et al. (2012). For this study, the MMP between sc-CO2 and
live oil is about 2600psi.
Stability Test
The stability of the emulsion (base gel with sc-CO2) was investigated. The emulsion stability was tested
using 70:30 ratios of CO2 to base gel solution (Formula 1), at 210F and 3,200 psi for 24 hours. The test
was conducted using specialized equipment able to handle pressure, temperature as well as having a
viewing window for the observation of foam. The test procedure was conducted as follows:

A sample of 500 ml base gel is prepared by adding the gelling agent into approximately 500 ml
of formation water. The solution is stirred vigorously in a beaker until totally mixed.
The surfactant and stabilizer are then added and mixed for 5 minutes until totally dispersed.
CO2 and the base gel were injected in a batch mode in a visual PVT cell at different injected
gas-base gel mixture ratios.
The solution was mixed to obtain a homogenous fluid (emulsion).
The mixer was stopped and the height of foam at the test temperature and pressure was monitored
with time.

Viscosity Measurements
A Chandler Engineering Model 5550 Viscometer (Figure 2) was used to measure the apparent viscosity
of the base gel at different shear rates and temperatures. This viscometer utilized a standard R1/B5 bob
and rotor combinations that required a sample volume of 52 cc. Chandler viscometer uses a sliding carbon
block for dry heating and the temperature sensor is mounted on the stator/bob to control sample
temperature. A pressure of 1,000 psi was applied to minimize evaporation of the sample, and to the sample
in liquid state.

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Figure 2High pressure and high temperature rheometer

Following the viscosity measurements of the base gel (Formula 1), the emulsion with CO2 is tested at
high pressure and temperatures (220-280F). Viscosity measurement was performed under different shear
rates to simulate the emulsion flow through production tubulars and inside the formation matrix.
Additionally, the effect of temperature on the viscosity of this emulsion was investigated. The shear rate
range was between 25 to 100 s1 and the temperature values ranged from 220 to 280F.
Experimental Procedures for Coreflooding
Several experiments were conducted using a dual core setup and the details were described earlier by
Zhou et al. 2015. These included (a) secondary mode-seawater flooding, (b) tertiary mode - initial sc-CO2
miscible flooding, (c) foam/gel diverter injection and (d) 2nd sc-CO2 miscible flooding. These also are
described below.
Coreflooding Apparatus A dual core flooding apparatus was custom designed to perform tests on
stacked or composite core plug samples to determine the impact of reservoir heterogeneities such as
permeability contrast and gravity override on oil recovery performance. A schematic of the coreflooding
apparatus is presented in Figure 3 (Zhou et al. 2015). The core holders were placed horizontally with a
high permeable composite plug (HPCP) on top of the low permeable composite plug (LPCP) coreholder.
The tests can be run at overburden pressures up to ~10,000 psi, pore pressures up to 9,500 psi and
temperatures up to 150C. The system is designed to be extremely versatile. All pore fluid wetted parts
are constructed from corrosion-resistant materials including Hastelloy C-276, Viton, and Teflon except
for the pressure transducers that are constructed from stainless steel. Oil, brines, sc-CO2 and a gel/foam
diverter are supplied from high-pressure floating piston accumulators that are driven by external highpressure pumps. These pumps have a high accuracy digital control. Fluid injection was accomplished

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through a metering pump connected by a valve ahead of the core. The pore pressure of core plugs was
maintained by two back pressure regulators (BPRs) at the core outlet, and controlled through pressurized
N2 accumulators, respectively. Absolute and differential pressure, temperatures, flow rates and other
parameters are measured and recorded through an elaborate data acquisition system during the dual core
flooding test. Graduated glass tubes are used to measure individually the produced oil from HPCP and
LPCP composites during seawater and sc-CO2 miscible flooding.

Figure 3Flow chart for dual core flooding set up at reservoir conditions

Core plugs properties Core plugs were selected from a carbonate reservoir and scanned to ensure
consistency, i.e., no fractures or permeability barriers in single core plug. NMR analysis was also
conducted to ensure that all core plugs have a similar rock type. Based on NMR and CT-scan results two
core plugs were selected for each of the HPCP and LPCP composites. Routine core analysis was
conducted to measure the dimensions, air permeability, porosity and helium pore volume of core plugs.
The core plugs were saturated with brine and the pore volume was calculated by material balance method.
The dimensions and properties of the core plugs used in this study are shown in Table 4. The HPCP
composite contained two core plugs, #35 and #36 with average air permeability of 832 mD and porosity
of 28.6% and the LPCP composite was composed of two core plugs, #285 and #286 with average air
permeability of 69 mD and porosity of 22%.
Table 4 Routine Data of Core Plugs and Composites
Composite ID
Composite #1
(HPCP)
Composite #2
(LPCP)

Sample ID

Length (cm)

Diameter (cm)

Pore Volume
(cc)

Porosity (%)

Air Permeability
(mD)

35
36
3536
285
286
285286

3.030
3.364
6.394
2.878
3.140
6.018

3.8
3.8
3.8
3.8
3.8
3.8

9.50
11.06
20.56
6.25
7.84
14.09

28.1
29.1
28.6
19.4
24.3
21.9

917.3
746.0
831.7
51.5
86.5
69.0

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Seawater flooding Once both the composites were aged with live oil at reservoir conditions and initial
oil saturation, seawater was injected simultaneously into both HPCP and LPCP at injection rates of 0.5,
1.0 and 2.0 cc/min until water cut reached 99%. The recovered oil was collected separately from the two
composites as a function of pore volumes of seawater injected. The differential pressures were also
recorded across both composites.
Initial sc-CO2 miscible flooding After the initial seawater flooding, the composites were isolated and
stabilized. All the lines filled with seawater were first displaced with sc-CO2. Thereafter the two
composites were opened and sc-CO2 was injected into both simultaneously at a rate of 0.2 cc/min. The
recovered oil was collected separately from the two composites and the differential pressures were
recorded across both.
Chemical foam slug injection (diverting system) To investigate the effect of permeability contract and
to mitigate its impact on oil recovery, a slug of the base gel was injected into the HPCP composite using
Formula 1 in Table 1. In this study, the LPCP was isolated and 0.4 PV of the base gel was only injected
into the HPCP at 0.5 cc/min. In-situ CO2-emulsion was generated and able to plug the high permeable
zone and then improve both areal and vertical sweep efficiencies by stabilizing viscous fingering and
gravity override issues.
2nd sc-CO2 miscible flooding After accomplishing the base gel injection, both HPCP and LPCP composites were opened for the 2nd sc-CO2 miscible flooding at injection rate of 0.2 cc/min. Oil production
and differential pressure across composites were recorded individually for HPCP and LPCP.

Results and Discussion

Stability Test
The emulsion of the base gel (Formula 1) with CO2 has been tested at 210F and 3,200 psi. The photos
of the sample before and after heating are shown in Figure 4. The test continued for 24 hours without any
emulsion breakage or phase separation. The base gel was prepared using formation waters, and no sign
of precipitation or phase separation was observed.

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Figure 4 Emulsion stability using base gel (Formula 1) with CO2 at 210F and 3,200 psi

Viscosity Measurements
The base gels using Formula 1 in Table 1 was tested at temperatures of 250F by using Chandler 5550
viscometer. The samples were pressurized with nitrogen to 600-800 psi to prevent evaporation or
oxidation. This test was conducted to establish a base line for viscosity without mixing with CO2. Figure
5 shows the viscosities of base gel at 250F. The viscosity was steady in the 250F test after the initial
heating. The viscosity values of base gel at a shear rate of 100 sec-1 were around 77 at 250 F.

SPE-174567-MS

Figure 5The viscosity measurement of base gel (Formula 1) at 250F

The viscosity of the emulsion using a mixture of base gel (Formula 1) and CO2 at a 60:40 volume ratio
is shown in Figure 6. The initial viscosity values at 100 sec-1 at 220 and 280F were 107 cP at both
temperatures. The viscosity was steady after contact of more than 4 hours at 280F. The CO2 emulsion
has both a higher thermal stability and viscosity compared to the base gel.

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Figure 6 The viscosity measurement of base gel (Formula 1) with CO2 at 220 and 280F

Oil recovery by seawater flooding

Table 5 provides the initial conditions of water and oil saturations for both HPCP and LPCP cores at the
beginning of seawater injection (Zhou et al. 2015). Once both the composites were aged with live oil at
reservoir conditions and initial oil saturation was established, seawater was injected simultaneously into
both HPCP and LPCP at injection rates of 0.5, 1.0 and 2.0 cc/min until water cut reached 99%. Water
flooded oil recovery was 41.1 and 50.8 % OOIC for LPCP and HPCP, respectively. The lower oil recovery
from LPCP compared to that from the HPCP by seawater flooding is primarily due to the permeability
effect and water preferentially travels through the high permeable paths first. The capillary forces, which
arise from the interfacial tension between oil and water, act to trap a significant portion of the oil as
isolated droplets.
Table 5Initial Data of Live Oil Flooding at Reservoir Conditions
Composite ID
Composite #1 (HPCP)
Composite #2 (LPCP)

Brine Permeability (mD)

Swi (%)

Soi (%)

Keo at Swi (mD)

966.7
22.3

24.64
17.56

75.36
82.44

104
3

Swi Initial water saturation, Soi: Original oil saturation and Keo: Effective oil Permeability at Swi.

Oil recovery by initial sc-CO2 miscible flooding

In this study, sc-CO2 was used to displace remaining oil after the initial seawater flood. Sc-CO2 was
injected at 0.2cc/min into the two composites simultaneously. Final oil recovery by initial sc-CO2 flooding
was 47.4 and 21.8% OOIC for HPCP and LPCP composites respectively. Residual oil saturation was less
than 2% OOIC for HPCP and 37% OOIC for the LPCP composites at the end of in initial supercritical
CO2 injection. This significant recovery difference in HPCP and LPCP can be attributed to the perme-

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11

ability contract between the cores and is the primary reason for diversion and bypass in reservoirs with
such heterogeneities.
Performance of foam injection
The results after the initial CO2 injection indicate that most of the oil was produced from the HPCP
composites and a significant amount was left behind in the LPCP composite. To recover this remaining
oil and improve displacement efficiency from LPCP, a slug of the base gel (about 0.4 PV) was injected
into the HPCP composite at an injection rate of 0.5cc/min. The maximum injection pressure recorded was
more than 200 psi for diverting system at reservoir conditions. Differential pressure measurement showed
stronger in-situ CO2-emulsion generated. Figure 7 shows profile of injection pressure build-up.

Figure 7The profile of injection pressure building up for HPCP during base gel slug injection (Formula 1)

Oil recovery by second sc-CO2 miscible flooding

As stated above, the oil recovery from the HPCP by initial sc-CO2 flooding was 47.4% OOIC. Only 21.8%
OOIC was recovered from LPCP. The low recovery from LPCP was due to sc-CO2 bypassing through the
higher permeable core plug. To prevent sc-CO2 from bypassing the oil in the LPCP, a base gell was
injected in the HPCP. As a result of that, in-situ CO2-emulsion was generated that blocks the HPCP.
Second sc-CO2 was injected again into both composites to determine the oil recovery performance from
the LPCP. The CO2 emulsion formed in the HPCP diverted the CO2 to flow through the LPCP. The
cumulative oil recovery from second sc-CO2 flooding in the LPCP was 19% of OOIC. This is additional
incremental oil recovery beyond water and initial sc-CO2 flooding. This oil was recovered from LPCP
during the first 1.0 PV of sc-CO2 injected.
Figure 8 shows the overall oil recovery by seawater, sc-CO2 before and after the base gel slug injection
against total pore volume injected under each mode of injection. The results indicate that in situations with
high permeability contrast or gravity override situations, the blocking of the high permeability streaks can
result in forcing the CO2 through the lower permeable regions, thereby increasing the recovery of the
bypassed oil. Additional corefloods are being conducted to understand this phenomenon in greater detail.

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Figure 8 Overall oil recovery by seawater, initial sc-CO2 and second sc-CO2 flooding after base gel slug injection (Formula 1) at
reservoir conditions

Conclusion
1. The emulsion was stable at 210F and 3,200 psi and for 24 hours without any emulsion breakage
or phase separation.
2. The base gel viscosity at shear rate (100 sec-1) and 250F was 77 cP.
3. The emulsion viscosity at shear rate (100 sec-1) and at 220 was 107 cP. The emulsion has
evidently increased the viscosity.
4. Poor sweep efficiency in lower permeable zone caused by bypassing of fluids through higher
permeable core plugs is experimentally evidenced during seawater and sc-CO2 flooding and can
be improved by injecting blocking or diverting agents. This can improve the recovery of bypassed
oil.
5. In-situ CO2-emulsion (diverting system) demonstrated an excellent blocking agent to improve
sweep efficiency in heterogeneous carbonate reservoirs.

Acknowledgement
The authors would like to thank Saudi Aramco and EXPEC Advanced Research Center for the permission
to publish this paper. Special thanks to Faris AlGhamdi for the preparation of Core flooding experiments.

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