J Polym Res (2013) 20:61
DOI 10.1007/s10965-012-0061-9
ORIGINAL PAPER
Effects of polymers as direct CO2 thickeners on the mutual
interactions between a light crude oil and CO2
Yongan Gu & Shiyang Zhang & Yuehui She
Received: 11 September 2012 / Accepted: 19 December 2012 / Published online: 6 January 2013
# Springer Science+Business Media Dordrecht 2013
Abstract In this paper, two commercial polymers with
relatively low molecular weights, poly vinyl ethyl ether
(PVEE) and poly 1-decene (P-1-D), are tested as direct
thickeners for CO2 and their detailed effects on the mutual
interactions between a light crude oil and polymer-thickened
CO2 are experimentally studied under different reservoir
pressures. More specifically, the polymer cloud-point pres-
sures are measured at different known polymer solubilities
in supercritical CO2. The equilibrium interfacial tensions
(IFTs) and onset pressures of quick polymer dissolution into
CO2 are measured for the polymerpure CO2 systems. The
polymer-swelling effect due to pure CO2 dissolution is
observed and examined. To study the mutual interactions
between the light crude oil and polymer-thickened CO2,
their equilibrium IFTs are measured and their so-called
minimum miscibility pressures (MMPs) and onset pressures
of the initial quick light-hydrocarbons extraction by CO2 are
determined. The oil-swelling effect due to polymer-
thickened CO2 dissolution is also visualized and analyzed.
All the experimental data for polymer-thickened CO2 are
compared with those for pure CO2.
Keywords Polymer thickeners for CO2 . CO2 enhanced oil
recovery (EOR) . Polymer cloud-point pressure . Equilibrium
interfacial tension (IFT)Polymer swelling . Polymer
dissolution in CO2
Y. Gu (*) : S. Zhang
Petroleum Technology Research Centre (PTRC), Petroleum Sys-
tems Engineering, Faculty of Engineering and Applied Science,
University of Regina, Regina, Saskatchewan S4S 0A2, Canada
e-mail: Peter.Gu@Uregina.Ca
Y. She
College of Chemical and Environmental Engineering, Yangtze
University, Jingzhou, Hubei 434023, Peoples Republic of China
Introduction
In the past five decades, carbon dioxide (CO2) enhanced oil
recovery (EOR) has become increasingly important to the
petroleum industry. After the primary and secondary oil re-
covery processes, a typical residual oil saturation in a light or
medium oil reservoir is still in the range of 5060 % of the
original-oil-in-place (OOIP) [1]. For example, the total vol-
ume of unrecovered oil in the existing oil reservoirs in Canada
is approximately five billion cubic meters [2]. Therefore,
different EOR techniques are used to recover the remaining
oil in the oil reservoirs after water flooding is applied. Among
all the EOR methods developed for the light and/or medium
oil reservoirs, CO2 flooding has been successful to a large
extent under some favourable reservoir conditions [3]. The
major oil recovery mechanisms for CO2 flooding include the
oil viscosity reduction due to sufficient CO2 dissolution and
possible asphaltene precipitation, light-hydrocarbons extrac-
tion by CO2, oil-swelling effect, interfacial-tension (IFT) re-
duction, and immiscible or miscible displacement [4].
Because CO2 flooding can not only effectively enhance oil
recovery but also considerably reduce greenhouse gas emis-
sions [5], the oil industry plans to recover abundant residual
oil from its light or medium oil reservoirs through an immis-
cible, near-miscible or miscible CO2 flood.
However, one of the major technical challenges related to
CO2 flooding is its mobility control due to CO2 low dynam-
ic viscosity and high effective permeability under the actual
reservoir conditions, which lead to an early CO2 break-
through. In the past, some research work has mainly focused
on thickening CO2 by using a polymer as a direct thickener.
Heller and co-workers measured the solubilities of 53 com-
mercially available polymers in CO2 and identified a total of
17 polymers that are soluble in CO2 [6]. In particular, poly
1-decene (P-1-D) with a relatively low molecular weight has
the highest solubility in CO2 and thus can be used as an
61, Page 2 of 13 J Polym Res (2013) 20:61

effective and direct thickener for thickening CO2. Bae and polymer thickener into CO2 affects the mutual interactions
Irani found that supercritical CO2 could also be substantially between a light crude oil and polymer-thickened CO2. Two
thickened or viscosified by using some silicon-based poly- commercially available liquid polymers with low molecular
mers together with an organic co-solvent [7]. McHugh and weights, PVEE and P-1-D, are tested as direct thickeners for
co-workers reported that many fluorinated polymers are CO2. Their cloud-point pressures are measured at different
highly CO 2 -philic under high-temperature and high- known polymer solubilities in supercritical CO2. In addi-
pressure conditions [8]. Furthermore, a research team led tion, the equilibrium IFTs of the polymerpure CO2 systems
by Drs. Enick and Beckman at the University of Pittsburgh and light crude oilpure/polymer-thickened CO2 systems
studied styrenefluoroacrylate copolymers and showed that are measured and analyzed. During the IFT measurements,
they have adequate solubilities in pure CO2 and can increase several important mass-transfer processes are observed. Fur-
its viscosity by 68 times [9, 10]. The molecular design of thermore, their detailed effects are studied and their onset
nonfluorous polymers for thickening CO2 was initiated in pressures are determined accordingly.
1999 by the same research team. It was found that addition
of a side chain with oxygen-containing groups (e.g., the
carbonyl group) can increase the solubility of certain sili- Experimental
cone oligomers in CO2 [11]. A series of poly (ether-carbon-
ate) copolymers synthesized by using propylene and CO2 Materials
can readily dissolve into CO2 at relatively low pressures
[12]. Other oxygen-containing polymers with CO2-philic In this study, two liquid polymers with low molecular
compounds, such as poly vinyl ethyl ether (PVEE) [13], weights were purchased from SigmaAldrich Corporation
poly vinyl acetate (PVAc) [14], and amorphous poly lactic (USA): poly vinyl ethyl ether (PVEE), [CH2CH(OC2H5)]n,
acid (PLA) [15], were also developed to greatly increase Mw =3,800 g/mol and =0.968 g/cm3 at 25 C; and poly 1-
polymer solubility in dense CO2 and CO2 viscosity as well. decene (P-1-D), [CH2CH[(CH2)7CH3]]n, Mw =910 g/mol
Recently, it has been experimentally proven that either and =0.833 g/cm3 at 25 C. They were used as direct
PVEE or P-1-D can adequately dissolve into supercritical thickeners to thicken or viscosify pure CO2. The purity of
CO2 as its direct thickener to substantially enhance its CO2 (Praxair, Canada) used in this study was 99.998 mol.%.
viscosity and EOR performance during a miscible CO2 The CMG WinProp module (Version 2008.10, Computer
flood [16]. Modelling Group Limited, Canada) was used to predict the
It is well known that successful CO2 flooding is largely
controlled by the mutual interactions, e.g., the equilibrium
Table 1 Compositional Analysis Result of the Original Joffre Viking
interfacial tension and interfacial mass transfer, between the Light Crude Oil with Asphaltene Content of wasp =0.10 wt.% (n-Pen-
reservoir crude oil and injected CO2. These mutual interactions tane Insoluble)
determine the overall performance of a given CO2 EOR pro-
Carbon wt.% Carbon wt.% Carbon wt.%
cess. For example, when CO2 is injected into an oil reservoir at number number number
a high reservoir pressure, the interfacial tension of the crude
oilCO2 system is significantly reduced [17, 18]. In addition, C1 0.00 C18 3.00 C35 1.01
CO2 is usually not miscible with a crude oil at the first contact C2 0.00 C19 2.33 C36 0.77
but can gradually develop the so-called dynamic miscibility C3 0.00 C20 2.00 C37 0.77
with it through multiple contacts [5], which is also referred to C4 0.00 C21 2.31 C38 0.55
as the multi-contact miscibility. In the latter case, mutual mis- C5 1.10 C22 1.47 C39 0.81
cibility is achieved through the two-way interfacial mass- C6 1.90 C23 1.89 C40 0.56
transfer processes between the crude oil and CO2 [19]. This C7 6.33 C24 1.43 C41 0.56
fact indicates that the two-way interfacial mass transfer signif- C8 6.67 C25 1.71 C42 0.56
icantly changes the compositions of the crude oil and CO2 C9 5.50 C26 1.46 C43 0.63
phases and plays an important role in developing the dynamic C10 6.00 C27 1.41 C44 0.41
miscibility. In the literature, nevertheless, no experimental tests C11 4.83 C28 1.41 C45 0.41
are conducted to study the effect of a polymer as a direct C12 4.33 C29 1.20 C46 0.41
thickener on the mutual interactions between a crude oil and C13 4.08 C30 1.05 C47 0.37
polymer-thickened CO2 under the actual reservoir conditions. C14 3.58 C31 1.16 C48 0.37
This paper has the following two research objectives: C15 3.83 C32 1.05 C49 0.37
first, achieving a better understanding of how a polymer C16 3.00 C33 0.73 C50+ 11.08
thickener dissolves into CO2 at different pressures; and C17 2.83 C34 0.77 Total 100.00
second, ascertaining whether and how dissolution of a
J Polym Res (2013) 20:61
densities of pure CO2 with PengRobinson equation of state
(EOS) [20] at different reservoir pressures and a constant
reservoir temperature of interest.
The original light crude oil sample was collected from the
Joffre Viking Pool in Alberta, Canada, with the reservoir
temperature of Tres =56.0C and cleaned by applying the
centrifugal separation method. The density of the cleaned
dead light crude oil sample was oil =0.815 g/cm3, the oil
viscosity was oil =1.0 mPas at the atmospheric pressure
and 56.0C, and its asphaltene content (n-pentane insoluble)
was wasp =0.10 wt.%. The compositional analysis result of the
cleaned dead light crude oil sample was obtained by using the
standard ASTM D86 method [21] and is given in Table 1. It
can be seen from the table that there are no hydrocarbons
under C4 and that the weight percentage of the heavy hydro-
carbons (i.e., C50+) is equal to w(C50+)=11.08 wt.%.
Polymer cloud-point pressure measurement
In this study, a visual method was applied to measure the
cloud-point pressure of either liquid polymer at a known
Fig. 1 Schematic diagram of
the experimental setup used for
measuring a The polymer
cloud-point pressure in pure
CO2; and b The equilibrium
interfacial tension (IFT) be-
tween a pendant liquid (poly-
mer or oil) drop and pure/
polymer-thickened CO2 by ap-
plying the axisymmetric drop
CO2
shape analysis (ADSA) tech-
nique for the pendant drop case
P
Pressure cell
Light source
Vibration-free table
Pure CO2 at P, T
Liquid polymer
Glass plate
a b
Page 3 of 13, 61
polymer solubility in pure CO2. A schematic diagram of the
experimental setup is shown in Fig. 1. The major component
of this setup was a see-through windowed high-pressure cell
(IFT-10, Temco, USA) with a net volume of 49.5 cm3, which
is shown in Fig. 1a for the polymer cloud-point pressure
measurement. This pressure cell can sustain pressures up to
68 MPa and its maximum working temperature is equal to
177 C. A light source and a glass diffuser (240341, Dyna
Lume, USA) were used to provide sufficient and uniform
illumination for polymer-thickened CO2 or CO2 solution in-
side the pressure cell. A monochrome microscope camera
(MZ6, Leica, Germany) with a resolution of 640 480 pixels
was used to capture the digital image of CO2 solution at any
time. The high-pressure cell was positioned between the light
source and microscope camera, all of which were placed on a
vibration-free table (RS4000, Newport, USA). The digital
image of CO2 solution at each equilibrium pressure was
acquired in tagged image file (TIF) format by applying a
digital frame grabber (Ultra II, Coreco Imaging, Canada)
and stored in a personal computer. A numeric reading of the
transmitted light intensity ranging from 0 (black) to 255
Hydraulic oil
Positive displacement pump
Crude oil
Temperature controller
Syringe pump
Microscope camera
Personal computer
Pendant liquid drop
Pure/thickened CO2 at P, T
61, Page 4 of 13 J Polym Res (2013) 20:61

(white) was made available at each pixel of such an acquired

monochrome digital image of polymer-thickened CO2. Also
the corresponding digital photograph was taken by using a
Nikon digital camera (Coolpix 5700, Nikon, Japan) to depict
the appearance of the entire high-pressure cell filled with
polymer-thickened CO2.
Prior to each polymer cloud-point pressure measurement,
the see-through windowed high-pressure cell shown in Fig. 1a
was cleaned with kerosene and then dried with nitrogen. First,
a small known amount of either liquid polymer (PVEE or P-1-
D) was slowly poured and gently placed onto a small glass
plate, which was positioned horizontally inside the high-
pressure cell. Then the pressure cell was closed, sealed, and
flushed with pure CO2 for several times. A heating tape
(HT955041, Electrothermal, USA) was wrapped around
the pressure cell to heat it and its temperature was controlled
and maintained at the actual reservoir temperature of Tres =
56.0C by using a stepless temperature controller (3PN1010B,
Staco, USA) with the accuracy of 0.1C. A digital high-
precision pressure gauge (Type 2089, Ashcroft, USA) with
the accuracy of 0.05 % was used to measure the equilibrium
pressure inside the pressure cell. Afterwards, pure CO2 was
slowly introduced into the high-pressure cell to increase its
pressure by 0.2 MPa in each step at a time interval of 20 min.
It was found by trial and error that after each pressure change
of 0.2 MPa, this time interval was long enough for the CO2
polymer system to reach a new equilibrium state, which was
indicated by a new equilibrium pressure. This pressurization
process was continued until the liquid polymer on the glass
plate completely dissolved into CO2 at a sufficiently high Fig. 2 Digital photographs of P-1-D-thickened CO2 phase or CO2
equilibrium pressure. In this case, the supercritical CO2pol- solution a When it was a clear and transparent phase at Peq =
ymer mixture became a clear and transparent phase. For 20.9 MPa and Tres = 56.0C; and b When it was in the so-called
polymer cloud-point state at Pcp =20.1 MPa and Tres =56.0C
example, a transparent P-1-D-thickened CO2 phase was
formed inside the high-pressure cell at Peq =20.9 MPa and
Tres =56.0C and its digital photograph is shown in Fig. 2a. An cloud-point pressure was measured twice and found to be
average value of the numeric readings of the transmitted light within 0.2 MPa. The above-described polymer cloud-point
intensities at 25 representative pixels (i.e., 5 rows5 columns) pressure measurement procedure was repeated with a different
of the acquired digital image of P-1-D-thickened CO2 was known amount of the same liquid polymer at the beginning
equal to 250, which was used as a maximum reference value. until a total of five polymer cloud-point pressure versus solu-
Finally, the test pressure was reduced by 0.2 MPa in each bility data points at Tres =56.0 C were obtained.
step at the same time interval until polymer-thickened CO2
became cloudy and the so-called polymer cloud-point state Equilibrium IFT measurement
was reached. The corresponding test pressure was termed the
polymer cloud-point pressure (Pcp) at the known polymer In this study, the same experimental setup shown in Fig. 1
solubility in pure CO2 and actual reservoir temperature. For for measuring the polymer cloud-point pressure in pure CO2
instance, Fig. 2b shows the digital photograph of the polymer was also used to measure the equilibrium IFT between a
cloud-point state at Pcp =20.1 MPa and Tres =56.0C for P-1- polymer and pure CO2 or between a light crude oil and pure/
D-thickened CO2. In this state, an average value of the nu- polymer-thickened CO 2 at each equilibrium pressure.
meric readings of the transmitted light intensities at the same Figure 1b shows a schematic diagram of the see-through
25 representative pixels of the acquired digital image of P-1- windowed high-pressure cell used to measure the equilibri-
D-thickened CO2 was equal to 150, which was 40 % lower um IFT by applying the axisymmetric drop shape analysis
than the maximum reference value of 250 at Peq =20.9 MPa (ADSA) technique for the pendant drop case. Prior to each
and Tres =56.0C. For each CO2polymer system, the polymer IFT test, the high-pressure cell and fluids handling system
J Polym Res (2013) 20:61
were thoroughly cleaned with kerosene and dried with ni-
trogen. Then pure or polymer-thickened CO2 was intro-
duced into the high-pressure cell from its sample cylinder
to pressurize the high-pressure cell to a pre-specified test
pressure. After pure or polymer-thickened CO 2 was
injected, it usually took about 30 min for the pressure and
temperature inside the pressure cell to reach their stable
values. A small stainless steel syringe needle was installed
at the top of the pressure cell. The liquid polymer or light
crude oil was introduced from its sample cylinder (500-10-
P-316-2, DBR, Canada) by using a programmable syringe
pump (100DX, ISCO Inc., USA) to form a pendant liquid
drop at the tip of the syringe needle. Once the pendant liquid
drop was formed, its sequential digital images at different
times were acquired in TIF format by applying the digital
frame grabber and automatically stored in the personal com-
puter. The time interval for the sequential digital image
acquisition was smaller at the beginning and larger when
the pendant liquid drop and surrounding CO2 were close to
an equilibrium state.
For such an acquired digital pendant liquid drop image, a
high-precision calibration grid was used to calibrate and
correct possible optical distortions. The ADSA program
(LIA Technologies Inc., Canada) for computer image anal-
ysis and processing for the pendant drop case was executed
to analyze and process each digital image of the dynamic
pendant liquid drop at any time. The required input data
were the local gravitational acceleration and density differ-
ence between the test liquid drop and surrounding CO2
phase. The output data included the dynamic IFT and pen-
dant liquid drop volume at any time. After all the digital
images of the dynamic pendant liquid drop were processed,
the experimentally measured dynamic IFTs and pendant
liquid drop volumes at different times were obtained. More-
over, the following four important mass-transfer processes
were also observed during the dynamic IFT measurements
and quantified by measuring the dynamic pendent liquid
drop volumes at different times: the polymer-swelling and
oil-swelling effects due to CO2 dissolution, polymer disso-
lution into CO2, and light-hydrocarbons extraction by su-
percritical CO 2 . The dynamic IFT measurement was
repeated for at least three different pendent liquid drops to
achieve a satisfactory repeatability of 0.05 mJ/m2 at each
equilibrium pressure and Tres =56.0 C. Only the average
value of the equilibrium IFTs of three repeated equilibrium
IFT measurements at the same equilibrium pressure and Tres
=56.0 C was noted and is presented in this paper.
Polymerpure CO2 systems
In order to ascertain which polymer (PVEE or P-1-D) can
more easily dissolve into pure CO2, the dynamic and equi-
librium IFTs of PVEE or P-1-Dpure CO2 system were
Page 5 of 13, 61
measured from 1.0 to 6.0 MPa at 56.0C in this study. First,
pure CO2 was used to pressurize the high-pressure cell to a
pre-specified pressure at Tres =56.0 C. After the pressure
and temperature inside the pressure cell reached their stable
values, a polymer sample was introduced from the polymer
source cylinder to form a pendant polymer drop at the tip of
the syringe needle. Once a well-shaped pendant polymer
drop was formed and surrounded by pure CO2, the sequen-
tial digital images of the dynamic pendant polymer drop at
different times were acquired and processed to determine
the dynamic and equilibrium IFTs of the polymerpure CO2
system.
Light crude oilpure CO2 system
To measure the equilibrium IFTs of the light crude oilpure
CO2 system, the pressure cell was pressurized with pure
CO2 to a pre-specified pressure at Tres =56.0 C. After the
pressure and temperature inside the pressure cell reached
their stable values, the light crude oil was introduced from
the original oil sample cylinder to the high-pressure cell to
form a pendant oil drop at the tip of the syringe needle. Once
a well-shaped pendant oil drop was formed and surrounded
by pure CO2, the sequential digital images of the dynamic
pendant oil drop at different times were acquired and pro-
cessed to determine the dynamic and equilibrium IFTs of the
light crude oilpure CO2 system.
Light crude oilpolymer-thickened CO2 systems with two
fixed polymer concentrations
Based on the measured polymer cloud-point pressure data,
PVEE or P-1-D-thickened CO2 with a polymer concentra-
tion of 0.15 or 0.46 wt.% was prepared as a test solvent for
each equilibrium IFT test. First, a 500 cc high-pressure
sample cylinder was cleaned with kerosene and acetone,
dried with air, and placed inside an air bath. An electric
heater (HZ-315C, Super Electric Co., Canada) and a tem-
perature controller (Standard-89000-00, ColeParmer, Can-
ada) were used to heat the air bath and keep it at a constant
temperature of 56.0C. Second, a known amount of each
polymer was accurately measured (e.g., m p = 0.097 or
0.589 g for 0.15 or 0.46 wt.% polymer concentration) and
placed inside the sample cylinder. Then the sample cylinder
was capped, sealed, and vacuumed to remove any trapped
air. Third, pure CO2 was injected from the pure CO2 cylin-
der to pressurize the high-pressure sample cylinder by using
the programmable syringe pump. It usually took 30 min for
each polymer to completely dissolve into CO2. Thus an
equilibrium state was reached and indicated by an equilib-
rium pressure (e.g., P eq = 6.0 or 9.0 MPa for 0.15 or
0.46 wt.% polymer concentration). Afterwards, the
polymer-thickened CO2 with a fixed polymer concentration
61, Page 6 of 13 J Polym Res (2013) 20:61

was injected into the see-through windowed high-pressure Table 2 Polymer Solubility in CO2, sol, Measured Polymer Cloud-
Point Pressure, Pcp, at Tres =56.0 C
cell to pressurize it to a pre-specified pressure at 56.0C.
Finally, the light crude oil was introduced from the original Polymer sol (wt.%) Pcp (MPa)
oil sample cylinder to the high-pressure cell to form a
pendant oil drop at the tip of the syringe needle. Once a PVEEa 0.67 14.6
well-shaped pendant oil drop was formed and surrounded by 0.69 16.1
polymer-thickened CO2, the sequential digital images of the 0.73 17.1
dynamic pendant oil drop at different times were acquired 0.77 18.3
and processed to determine the dynamic and equilibrium 0.80 19.7
IFTs of each light crude oilpolymer-thickened CO2 system P-1-Db 0.56 14.7
with a fixed polymer concentration. 0.61 15.2
0.66 17.0
0.70 18.5
Results and discussion 0.81 20.1
a
PVEE: poly vinyl ethyl ether
Polymer cloud-point pressures b
P-1-D: poly 1-decene

In this study, the polymer cloud-point pressure in supercrit-

ical CO2 was measured in the following two pressure ranges
at Tres =56.0C: Pcp =14.619.7 MPa for PVEE and Pcp =
14.720.1 MPa for P-1-D. These two pressure ranges are
chosen because future CO2 EOR projects in the Joffre
Viking Pool are expectedly operated at the reservoir con-
ditions of Pres =1420 MPa and Tres =56.0C [22]. After the
approximation, Pcp (MPa) is linearly correlated to sol
(wt.%) by applying the linear regression:
Pcp 35:908c sol  9:142 for PVEE 2


0:67 wt:%  c sol  0:80wt:%; R 0:976 2

polymer cloud-point pressure is measured, the polymer sol-

ubility in CO2, sol, at the cloud-point state (Pcp and Tres =
56.0C) is determined: Pcp 23:181c sol 1:615 for P1D

3
mp 0:56 wt:%  c sol  0:81 wt:%; R2 0:958
c sol   1
m
mp CO2 Vcell  p
p

Equilibrium IFTs of polymerpure CO2 systems

where, mp and p are the known mass and density of
polymer to dissolve into CO2; CO2 is pure CO2 density at The equilibrium IFTs of each polymerpure CO2 system
Pcp and Tres =56.0C, which is predicted by using the CMG were measured at Tres =56.0 C in the equilibrium pressure
WinProp module; and Vcell is the volume of the see-through
windowed high-pressure cell, which is equal to 49.5 cm3. 21
The measured cloud-point pressures of two respective
Measured polymer cloud-point pressure Pcp (MPa)

polymers in supercritical CO2 at different known polymer 20

solubilities and Tres =56.0C are given in Table 2 and further II

19
plotted in Fig. 3. These measured polymer cloud-point pres-
sure versus solubility data show that both polymers can
18
adequately dissolve into CO2 at their cloud-point pressures
tested and Tres =56.0C. In general, PVEE has a much higher 17 I
solubility than P-1-D at the same and low polymer cloud-
point pressure. This is because PVEE has an oxygen- 16

containing ether group in the backbone of its molecular

15 Poly 1-decene
structure, whereas P-1-D is a typical hydrocarbon polymer
Poly vinyl ethyl ether
with no oxygen component. It has already been proven that
14
the oxygen-containing ether group is CO2-philic and thus 0.50 0.60 0.70 0.80 0.90 1.00
enhances the solubility of a hydrocarbon polymer in dense Polymer solubility in pure CO2 sol (wt.%)

CO2 if the ether group is attached to its backbone, such as

Fig. 3 Measured polymer cloud-point pressures, Pcp, at different poly-
PVEE [14]. With the measured polymer cloud-point pres- mer solubilities, sol, in pure CO2 and Tres =56.0 C. Line I is Eq. (2);
sure versus solubility data (symbols) in Fig. 3, as a first and line II is Eq. (3)
J Polym Res (2013) 20:61
range of Peq =1.06.0 MPa in this study. The measured
equilibrium IFTs of two polymerCO2 systems at different
equilibrium pressures and Tres =56.0 C are plotted and
compared in Fig. 4. This figure shows that the equilibrium
IFTs of PVEECO2 system are lower than those for P-1-D
CO2 system. Therefore, PVEE and pure CO2 are more
similar in comparison with P-1-D and pure CO2 and PVEE
can more easily dissolve into pure CO2 than P-1-D.
Polymer-swelling effect and quick polymer dissolution
into CO2
In the equilibrium IFT measurements for each polymer
pure CO2 system at different equilibrium pressures, it
was observed that after the pendant polymer drop was
formed and surrounded by pure CO2 inside the high-
pressure cell, its volume and shape were changed continu-
ously within a period of 20 min. Figure 5 shows the relative
pendant polymer drop volumes at different equilibrium
pressures. Here, the relative polymer drop volume at each
equilibrium pressure is defined as the ratio (Vt/V0) of the
actual pendant polymer drop volume Vt at the end of t=
1,200 s to its initial volume V0 at the beginning of t=0 s. It is
seen from this figure that there is an onset pressure (Psol) for
each polymerpure CO2 system, at which the polymer starts
to quickly dissolve into CO2. The onset pressures of quick
polymer dissolution into CO2 are found to be Psol =2.3 MPa
for PVEE and Psol =5.5 MPa for P-1-D, respectively.
At a low equilibrium pressure (Peq <Psol), the pendant
polymer drop swells and its volume is increased by as much
as 2030% till t= 20 min due to CO2 dissolution. The
sequential digital images of the dynamic pendant polymer
drop and its volumes for PVEE and P-1-D at Peq =2.0 MPa
and Tres =56.0C are shown in Fig. 6a at four different times,
t=0, 30, 100, and 1,200 s. This figure clearly indicates that
if Peq is lower than Psol, the dynamic pendant polymer drop
24
22
(mJ/m2)
20
18
eq
16
Equilibrium interfacial tension
14
12
10
8
6
4
2
0 pressure was higher than a certain pressure (e.g., 14 MPa),
0 1 2 3 4 5
Equilibrium pressure Peq (MPa)
Fig. 4 Measured equilibrium interfacial tensions, eq, of each polymer
pure CO2 system at different equilibrium pressures, Peq, and Tres =56.0 C
Page 7 of 13, 61
1.4
1.2
Relative drop volume Vt / V0
1.0
0.8
0.6
0.4
Poly 1-decene
0.2
Poly vinyl ethyl ether
0.0
0 1 2 3 4 5 6 7
Equilibrium pressure Peq (MPa)
Fig. 5 Measured relative pendant polymer drop volumes in pure CO2
at different equilibrium pressures and Tres =56.0C. Here, the relative
polymer drop volume at each equilibrium pressure is defined as the
ratio (Vt/V0) of the actual pendant polymer drop volume Vt at the end of
t=1,200 s to its initial volume V0 at the beginning of t=0 s
swells and its volume is increased gradually due to the
polymer-swelling effect, which is caused by CO2 gradual
dissolution.
At a high equilibrium pressure (Peq Psol), however, the
pendant polymer drop shrinks quickly and begins to dissolve
into CO2 as its direct thickener. The pendant polymer drop
volume is reduced by as much as 50 % because of polymer
dissolution into CO2 and finally CO2 is completely saturated
with the polymer. The sequential digital images of the dynam-
ic pendant polymer drop and its volumes for PVEE and P-1-D
at Peq =5.5 MPa and Tres =56.0C are shown in Fig. 6b at four
different times, t=0, 30, 100, and 1,200 s. This figure clearly
shows that if Peq is higher than Psol, polymer quickly dissolves
into CO2, especially at the beginning (t30 s). The subsequent
slow polymer dissolution into CO2 occurs and continues till t
=1,200 s. The pendant polymer drop volume finally reaches a
constant value and there is no further polymer dissolution into
CO2 at t>1,200 s.
Poly 1-decene
Poly vinyl ethyl ether Equilibrium IFTs of the light crude oilpure/polymer-thickened
CO2 systems
Light crude oilpure CO2 system
In this study, the equilibrium IFTs of the light crude oilpure
CO2 system at Tres =56.0 C in the equilibrium pressure
range of Peq =6.014.0 MPa were measured and are plotted
in Fig. 7. It should be noted that once the equilibrium
6 7 it became increasingly difficult to keep the dynamic pendant
oil drop at the tip of the syringe needle long enough for one
equilibrium IFT measurement to be completed. This was
because of the initial quick and subsequent slow light-
61, Page 8 of 13 J Polym Res (2013) 20:61

a b
Poly vinyl ethyl ether Poly 1-decene Poly vinyl ethyl ether Poly 1-decene

t = 0 s V0 = 6.210 mm3 t = 0 s V0 = 6.337 mm3 t = 0 s V0 = 6.511 mm3 t = 0 s V0 = 7.217 mm3

t = 30 s Vt = 6.220 mm3 t = 30 s Vt = 6.337 mm3 t = 30 s Vt = 6.389 mm3 t = 30 s Vt = 6.764 mm3

t = 100 s Vt = 7.313 mm3 t = 100 s Vt = 7.313 mm3 t = 100 s Vt = 4.858 mm3 t = 100 s Vt = 5.112 mm3

t = 1,200 s Vt = 7.793 mm3 t = 1,200 s Vt = 7.525 mm3 t = 1,200 s Vt = 3.377 mm3 t = 1,200 s Vt = 3.653 mm3

Fig. 6 a Sequential digital images of the dynamic pendant polymer dynamic pendant polymer drop surrounded by pure CO2 at Peq =
drop surrounded by pure CO2 at Peq =2.0 MPa, Tres =56.0C, and t=0, 5.5 MPa, Tres =56.0C, and t=0, 30, 100, 1,200 s, respectively
30, 100, 1,200 s, respectively. b Sequential digital images of the

hydrocarbons extraction by CO2 and quickly reduced dy- is correlated to the equilibrium pressure Peq (MPa) by ap-
namic IFT at a high equilibrium pressure. In this case, one plying the linear regression in the two pressure ranges:
has to continuously introduce the light crude oil for a long
g eq 1:709Peq 24:784 4
time (e.g., 2030 min) so that eventually a small pendent oil

drop is formed at the tip of the syringe needle. Also a small 6:0 MPa  Peq  10:7 MPa; R2 0:947
pendant oil drop can stay long (e.g., about 20 min) so that
the measured dynamic IFT at the end can be considered as
the equilibrium IFT. g eq 0:422Peq 11:087 5


It is found that the measured equilibrium IFT is reduced 10:7 MPa  Peq  14:0 MPa; R 0:949
2

almost linearly in the two distinct pressure ranges of 6.0

10.7 MPa and 10.714.0 MPa. Based on the measured For the light crude oilpure CO2 system, the linear regres-
data (symbols) in Fig. 7, the equilibrium IFT eq (mJ/m2) sion equation of the measured equilibrium IFT versus pressure
J Polym Res (2013) 20:61 Page 9 of 13, 61

16
It is found from Fig. 8a for the light crude oilPVEE-
(mJ/m2)

14 thickened CO2 system that the measured equilibrium IFT is

12
reduced almost linearly with the equilibrium pressure in two
eq

different pressure ranges: Peq =6.011.0 MPa and Peq =

Equilibrium interfacial tension

10 11.014.0 MPa. Based on the measured data (symbols) in

8
Fig. 8a, the equilibrium IFT eq (mJ/m2) is correlated to the
equilibrium pressure Peq (MPa) by applying the linear re-
6 gression in the two pressure ranges:
4
g eq 1:527Peq 20:881 7
Pmax = 26.3 MPa

2 MMP = 14.5 MPa
6:0 MPa  Peq  11:0 MPa; R 0:995 2

0
5 10 15 20 25 30
Equilibrium pressure Peq (MPa) g eq 0:524Peq 9:909 8


Fig. 7 Measured equilibrium interfacial tensions, eq, of the light 11:0 MPa  Peq  14:0 MPa; R2 0:991
crude oilpure CO2 system at different equilibrium pressures, Peq,
and Tres =56.0 C

data for the first pressure range intersects with the abscissa a 16

(i.e., eq =0) at Peq =14.5 MPa at Tres =56.0C. Therefore, the

(mJ/m2)
14
minimum miscibility pressure (MMP) of the light crude oil
pure CO2 system is determined to be MMP=14.5 MPa by 12
eq

applying the vanishing interfacial tension (VIT) technique

Equilibrium interfacial tension

10
[23, 24]. In addition, the miscibility pressure for the heavy
hydrocarbons of the original light crude oil and pure CO2 to 8

become miscible is found to be Pmax =26.3 MPa from the 6

intersection of the linear regression equation for the second
pressure range with the abscissa (i.e., eq =0), which is close to 4

the so-called first-contact miscibility pressure. 2 MMP = 13.7 MPa

Pmax = 18.9 MPa

0
Light crude oilpolymer-thickened CO2 systems with two 5 10 15 20 25 30
fixed polymer concentrations Equilibrium pressure Peq (MPa)

b 16
PVEE and P-1-D are typical hydrocarbon polymers. Thus it
(mJ/m2)

14
is expected that dissolution of either polymer into pure CO2
can reduce the equilibrium IFTs between the light crude oil 12
eq

and polymer-thickened CO2, which means that the two

Equilibrium interfacial tension

10
phases can more easily become miscible and have a lower
MMP due to polymer-induced IFT reduction. In this study, 8
the equilibrium IFTs between the light crude oil and each
6
polymer-thickened CO2 with a fixed polymer concentration
of 0.15 wt.% were measured at different equilibrium pres- 4

sures of Peq =6.014.0 MPa and Tres =56.0C. It should be Pmax = 18.7 MPa
2 MMP = 14.3 MPa
noted that 6.0 MPa was chosen to be the lower limit of the
equilibrium pressure tested because it was the lowest equi- 0
5 10 15 20 25 30
librium pressure for 0.15 wt.% P-1-D to completely dissolve
Equilibrium pressure Peq (MPa)
into CO2, whereas PVEE can easily reach 0.15 wt.% in CO2
at Peq =6.0 MPa. In addition, the polymer-thickened CO2 Fig. 8 a Measured equilibrium interfacial tensions, eq, of the light
density, sol, can be calculated from: crude oilPVEE-thickened CO2 system with a fixed PVEE concentra-
tion of 0.15 wt.% at different equilibrium pressures, Peq, and Tres =
  56.0 C. b Measured equilibrium interfacial tensions, eq, of the light
m
mp CO2 Vcell  p crude oilP-1-D-thickened CO2 system with a fixed P-1-D concentra-
sol 6
p
tion of 0.15 wt.% at different equilibrium pressures, Peq, and Tres =
Vcell 56.0 C
61, Page 10 of 13
The MMP of the light crude oilPVEE-thickened CO2
system is determined by applying the VIT technique to be
MMP=13.7 MPa. Moreover, the miscibility pressure be-
tween the heavy hydrocarbons of the original light crude
oil and PVEE-thickened CO 2 is found to be P max =
18.9 MPa.
Similarly, Fig. 8b shows that there are two different
pressure ranges, P eq = 6.012.0 MPa and P eq = 12.0
14.0 MPa, for the measured equilibrium IFTs of the light
crude oilP-1-D-thickened CO2 system. Based on the mea-
sured data (symbols) in Fig. 8b, the equilibrium IFT eq
(mJ/m2) is correlated to the equilibrium pressure Peq (MPa)
by applying the linear regression in the two pressure ranges:
g eq 1:470Peq 21:041 9

Fig. 9 Measured equilibrium interfacial tensions, eq, of the light
6:0 MPa  Peq  12:0 MPa; R2 0:997
g eq 0:555Peq 10:358 10


12:0 MPa  Peq  14:0 MPa; R2 0:998
The MMP of the light crude oilP-1-D-thickened CO2
system is determined by applying the VIT technique to be
MMP=14.3 MPa. In addition, the miscibility pressure be-
tween the heavy hydrocarbons of the original light crude oil
and P-1-D-thickened CO2 is found to be Pmax =18.7 MPa.
In this study, the equilibrium IFTs between the light crude
oil and each polymer-thickened CO2 with the polymer con-
centration of 0.46 wt.% at Tres =56.0 C were also measured
in the equilibrium pressure range of Peq =9.013.0 MPa. It
should be noted that 9.0 MPa was chosen to be the lower
limit of the equilibrium pressure tested as it was the lowest
equilibrium pressure for 0.46 wt.% P-1-D to completely
dissolve into CO2, while PVEE can reach over 0.46 wt.%
in CO2 at Peq =9.0 MPa. In order to more accurately com-
pare the effects of each polymer and its concentration on the
equilibrium IFT of each light crude oilpolymer-thickened
CO2 system, the measured equilibrium IFTs between the
light crude oil and each polymerthickened CO2 with two
fixed polymer concentrations of 0.15 and 0.46 wt.% are
plotted in Fig. 9. It is found that at the same equilibrium
pressure, the measured equilibrium IFT of the light crude
oilPVEE-thickened CO2 system is lower than that for the
light crude oilP-1-D-thickened CO2 system. Accordingly,
the miscibility of the light crude oilPVEE-thickened CO2
system is achieved at a relatively lower MMP. It is also
found that the measured equilibrium IFTs at the polymer
concentration of 0.46 wt.% are lower than those at the
polymer concentration of 0.15 wt.%. Therefore, more dis-
solution of a polymer as a direct thickener into CO2 leads to
a lower equilibrium IFT and thus a lower MMP of each light
crude oilpolymer-thickened CO2 system. In this regard,
addition of a hydrocarbon polymer thickener (e.g., PVEE
J Polym Res (2013) 20:61
16
0.15 wt.% P-1-D
(mJ/m2)
14
0.15 wt.% PVEE
0.46 wt.% P-1-D
12
0.46 wt.% PVEE
eq
Equilibrium interfacial tension
10
8
6
4
2
0
5 10 15 20 25 30
Equilibrium pressure Peq (MPa)
crude oilpolymer-thickened CO2 systems with two fixed polymer
concentrations of 0.15 and 0.46 wt.% at different equilibrium pres-
sures, Peq, and Tres =56.0 C
or P-1-D) into CO2 is very similar to addition of an inter-
mediate hydrocarbon (e.g., C3H8 or n-C4H10) into CO2, both
of which can lower the MMP of the light crude oilmodified
CO2 system. Furthermore, addition of the intermediate hy-
drocarbon into CO2 can far more considerably lower the
MMP. More importantly, this second option is much easier
and cheaper to implement in practice.
Oil-swelling effect and light-hydrocarbons extraction
by CO2
It was observed in the equilibrium IFT measurements that
after the pendant oil drop was formed and surrounded by
either pure or polymer-thickened CO2 inside the high-
pressure cell, its volume and shape were changed continu-
ously. It was also observed that some light hydrocarbons
were quickly extracted from the light crude oil to CO2 at the
beginning if the equilibrium pressure tested was higher than
a certain pressure. This threshold pressure is termed the
onset pressure (Pext) of the initial quick light-hydrocarbons
extraction by CO2 [25, 26]. In this study, it was observed
that the initial quick light-hydrocarbons extraction by CO2
occurred at Pext =8.8, 9.0, and 9.2 MPa for the light crude oil
pure CO2, PVEE- and P-1-D-thickened CO2 systems with
the polymer concentration of 0.15 wt.% at Tres =56.0C.
Dissolution of a hydrocarbon polymer (e.g., PVEE or P-1-
D) into supercritical CO2 slightly reduces its ability to
extract the light hydrocarbons from the light crude oil. Thus
the initial quick light-hydrocarbons extraction by polymer-
thickened CO2 occurs at a slightly higher onset pressure.
At a low equilibrium pressure (Peq <Pext), the pendant oil
drop first swells slightly due to pure or polymer-thickened CO2
dissolution into the crude oil and then shrinks slowly because of
the subsequent slow light-hydrocarbons extraction by CO2.
J Polym Res (2013) 20:61
The sequential digital images of the dynamic pendant oil drop
surrounded by polymer-thickened CO2 with a fixed polymer
concentration of 0.15 wt.% and its volumes at Peq =6.0 MPa
and Tres =56.0C are shown in Fig. 10a at four different times,
t=0, 30, 100, and 1,200 s. It is clearly seen from this figure that
the dynamic pendant oil drop volume is increased slightly at the
beginning (t100 s) due to the initial oil-swelling effect. After-
wards, however, the dynamic pendant oil drop volume is
reduced considerably as a result of the subsequent slow light-
hydrocarbons extraction by CO2. This indicates that although
the two-way mass transfer may occur at all times, the oil-
a b
PVEE-thickened CO2 P-1-D-thickened CO2
t = 0 s V0 = 4.733 mm3 t = 0 s V0 = 4.898 mm3
t = 30 s Vt = 4.752 mm3 t = 30 s Vt = 4.934 mm3
t = 100 s Vt = 4.965 mm3 t = 100 s Vt = 5.348 mm3
t = 1,200 s Vt = 4.436 mm3 t = 1,200 s Vt = 4.528 mm3
Fig. 10 a Sequential digital images of the dynamic pendant oil drop
surrounded by polymer-thickened CO2 with a fixed polymer concen-
tration of 0.15 wt.% at Peq =6.0 MPa, Tres =56.0C, and t=0, 30, 100,
1,200 s. b Sequential digital images of the dynamic pendant oil drop
Page 11 of 13, 61
swelling effect due to CO2 dissolution is more pronounced at
the beginning (t100 s), whereas the oil-shrinking effect due to
the subsequent slow light-hydrocarbons extraction by CO2
becomes dominant at a large time (t>100 s).
At a high equilibrium pressure (Peq Pext), the initial
quick light-hydrocarbons extraction by CO2 is observed at
the beginning and then followed by the subsequent slow
light-hydrocarbons extraction by CO2. The sequential digi-
tal images of the dynamic pendant oil drop surrounded by
polymer-thickened CO2 with a fixed polymer concentration
of 0.15 wt.% and its volumes at Peq =10.0 MPa and Tres =
PVEE-thickened CO2 P-1-D-thickened CO2
t = 0 s V0 = 4.695 mm3 t = 0 s V0 = 4.811 mm3
t = 30 s Vt = 4.573 mm3 t = 30 s Vt = 4.518 mm3
t = 100 s Vt = 4.419 mm3 t = 100 s Vt = 4.249 mm3
t = 1,200 s Vt = 3.358 mm3 t = 1,200 s Vt = 3.109 mm3
surrounded by polymer-thickened CO2 with a fixed polymer concen-
tration of 0.15 wt.% at Peq =10.0 MPa, Tres =56.0C, and t=0, 30, 100,
1,200 s
61, Page 12 of 13
56.0C are shown in Fig. 10b at four different times, t=0,
30, 100, and 1,200 s. In this case, the light hydrocarbons are
rapidly extracted from the oil drop to CO2 at the beginning
(t30 s). This initial quick light-hydrocarbons extraction
greatly accelerates the mass transfer from the crude oil to
CO2. Then the pendant oil drop keeps shrinking slowly due
to the subsequent slow light-hydrocarbons extraction by
CO2 at a large time (t>30 s). It should be noted that the
compositions of the crude oil and gas (CO2) phases are
substantially changed due to the initial quick and subsequent
slow light-hydrocarbons extraction processes at Peq Pext.
The two-way interfacial mass-transfer processes are in-
volved: CO2 dissolution into the crude oil (i.e., condensing)
and light-hydrocarbons extraction by CO2 (i.e., vaporizing).
In this way, the multi-contact dynamic miscibility between
the light crude oil and CO2 can be gradually achieved at a
higher pressure, i.e., the MMP.
Conclusions
In this study, two commercial liquid polymers with low
molecular weights, poly vinyl ethyl ether (PVEE) and poly
1-decene (P-1-D), are chosen and tested as direct thickeners
for CO2. The mutual interactions between a light crude oil
and polymer-thickened CO2 are studied by measuring the
polymer cloud-point pressures and equilibrium interfacial
tensions (IFTs) and visualizing several important mass-
transfer processes. It is found that both polymers can ade-
quately dissolve into supercritical CO2 at different reservoir
pressures and a constant reservoir temperature of interest. At
the same and low polymer cloud-point pressure, PVEE has a
much higher solubility in pure CO2 than P-1-D. In general,
the measured equilibrium IFTs of PVEEpure CO2 system
are lower than those of P-1-Dpure CO2 system. At a low
equilibrium pressure, the polymer-swelling effect due to
CO2 dissolution is observed. At a high equilibrium pressure,
however, polymer quickly dissolves into CO2. The onset
pressure of PVEE for its quick dissolution into CO2 is much
lower than that of P-1-D.
The measured equilibrium IFTs of the light crude oil
polymer-thickened CO2 systems are much lower than those
of the light crude oilpure CO2. Both PVEE and P-1-D can
substantially reduce the minimum miscibility pressure (MMP)
and miscibility pressure between the heavy hydrocarbons and
CO2. At a low equilibrium pressure, the oil-swelling effect due
to polymer-thickened CO2 dissolution occurs, which is fol-
lowed by the oil-shrinking effect due to the subsequent slow
light-hydrocarbons extraction by CO2. At an equilibrium pres-
sure higher than a threshold pressure, some light hydrocarbons
are extracted from the light crude oil to CO2 quickly at the
beginning and slowly at a large time. Through the observed
two-way interfacial mass-transfer processes: CO2 dissolution
J Polym Res (2013) 20:61
into the crude oil (i.e., condensing) and light-hydrocarbons
extraction by CO2 (i.e., vaporizing), the multi-contact dynamic
miscibility between the light crude oil and CO2 can be gradu-
ally developed at a higher pressure, i.e., the MMP. Further-
more, the miscibility pressure for the heavy hydrocarbons of
the original light crude oil and CO2 to become miscible can be
ultimately reached at an even higher pressure, which is close to
the first-contact miscibility pressure.
Acknowledgments The authors want to acknowledge the discovery
grant and collaborative research and development (CRD) grant from
the Natural Sciences and Engineering Research Council (NSERC) of
Canada and an industrial R&D fund from the PennWest Exploration to
Dr. Yongan Gu. The authors want to thank Mr. Andrew Seto and Ms.
Suzy Chen from the PennWest Exploration for their technical support.
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