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Effect of CO2 injection on interfacial tension of oil-formation water

system under high temperature and pressure
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EEEP 2019 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 467 (2020) 012010 doi:10.1088/1755-1315/467/1/012010

Effect of CO2 injection on interfacial tension of oil-formation

water system under high temperature and pressure

Xin Wang1,2,3, Zengmin Lun1,2, Rui Wang1,2, Chengyuan Lv1,2, Yongqiang Tang1,2
and Wei Hu1,2
1
Sinopec Key Laboratory of Marine Oil& Gas Reservoirs Production, Beijing, China;
2
Sinopec Exploration & Production Research Institute, Beijing, China
3
Email: [email protected]

Abstract. The interfacial interaction between CO2 and oil and water is one of the important
factors affecting the effect of CO2 enhanced oil recovery. Taking dead oil in Zhoucheng
Oilfield as an example, the variation of interfacial tension between crude oil-carbonated water
two-phase system and oil-formation water two-phase system was studied by pendant drop
method. The influence of different CO2 saturation on the equilibrium interfacial tension of oil-
formation water system and changes of equilibrium interfacial tension between crude oil-
carbonated water system and crude oil-formation water system were analyzed. Moreover,
previous studies did not reflect the experimental phenomena of extracting light hydrocarbons
from oil droplets by CO2 through gas-water interface. This paper provides experimental
research and analysis for this experimental phenomenon. The results show that the equilibrium
interfacial tension of crude oil-carbonated water system decreases with the increase of pressure,
and the dissolution and diffusion of the system becomes more and more obvious with the
increase of pressure. The medium exchange occurs between oil and carbonated water, and the
phenomenon of partial miscibility occurs. There is a threshold pressure value between crude oil
and formation water with different CO2 saturation. Each group of samples has its threshold
pressure and optimum CO2 injection rate. It's not that the more CO2 injection, the better oil
displacement effect. This research provides a reference for us to save the cost of CO2 flooding.

1. Introduction
In recent years, with the rapid development of the global economy and population explosion, carbon
dioxide (CO2) emissions have increased year by year. CO2 flooding can not only effectively improve
oil recovery, but also reduce greenhouse gas emissions, which is of great significance to improve the
environment [1-2]. For the reservoirs in the middle and later stages of development, there are still a
large number of remaining oil remaining in the reservoirs after water flooding, and it is difficult to
further improve oil recovery [3-5]. CO2 flooding has been widely used because it can effectively
improve recovery and carbon sequestration after water flooding. In the development of American
oilfields, CO2 flooding can increase oil recovery by 10%-20% [6-8]. China has already applied CO2
flooding in North China, Jilin and Shengli oilfields, and achieved good development results [9-11]
In CO2 enhanced recovery technologies such as CO2 flooding and CO2 huff and puff, the interfacial
interaction of CO2-oil-water is one of the important factors affecting the development effect of oil
wells [12-15]. At present, the mechanism of CO2 EOR technology is mainly focused on the interfacial
tension characteristics of CO2-crude oil system. The interfacial interaction characteristics and
mechanism of CO2-formation water-oil system are less studied. Previous studies did not show the
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EEEP 2019 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 467 (2020) 012010 doi:10.1088/1755-1315/467/1/012010

experimental phenomena of extracting light hydrocarbons from oil droplets by CO2 through gas-water
interface [16-18], and this paper provides experimental research and analysis for this experimental
phenomenon. Moreover, the variation of interfacial tension of crude oil-carbonated water system
under different reservoir pressures and different CO2 solubility was measured accurately [19-22]. The
variation of equilibrium interfacial tension of crude oil-formation water system and crude oil-
carbonated water system were compared. Each group of samples has its threshold pressure and
optimum CO2 injection rate, these two parameters are conducive to reducing the cost of CO2 flooding.

2. Experiment

2.1. Experimental samples

The crude oil used in the experiment is degassed crude oil from Zhoucheng Oilfield. The density of
crude oil is 0.9224 g/m3, and the viscosity is 156.55cp. The experimental temperature is 74 ℃. The
purity of CO2 and nitrogen used in the experiment are 99.995% and 99.9995% respectively.
The composition of brine is shown in Table 1:

Table 1. The composition of brine.

Water pH Cationic （mg/L) Anion (mg/L) Total Water
temperature Na+ K+ Mg2+ Ca2+ Sr2+ Ba2+ Cl- SO42- CO32- HCO3- salinity type
(℃) mg/L
33.20 6.90 7451.00 45.48 54.73 66.38 15.66 0.89 12386.12 4091.12 0.00 1427.23 25522.06 CaCl2
Produ-ced
water

2.2. Experimental equipment and mechanism

The high temperature and high-pressure interfacial tensiometer manufactured by Sanchez
Technologies was used. The working temperature is 0-200℃ and the working pressure is 0-70 MPa.
The diameter of the needle is 0.82 mm in the experiment. The densitometer produced by Anton Paar
Company was used in the experiment. The maximum pressure is 70 MPa and the maximum
temperature range is 200℃. The experimental installation is shown in Figure 1.

Figure 1. The schematic for the determination of interfacial tension by pendent drop method.

The mechanism of measuring the interfacial tension by pendant drop method is [23-25]:
∆𝜌g𝑑
𝛾
𝐻
In the formula: 𝛾 is two phase interfacial tension, △ρ is the difference of fluid density, kg/m3; de is
the largest diameter of pendent droplets, m; 1/H is a function describing the shape factor of pendent
droplets and related to the shape factor S.

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EEEP 2019 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 467 (2020) 012010 doi:10.1088/1755-1315/467/1/012010

Shape factor S is defined as S D ⁄D . 𝐷 is the diameter of droplets, and 𝐷 is the diameter of

droplets plane that the distance from the plane to the bottom is equal to 𝐷 .
The interfacial tension can be calculated by measuring the 𝐷 , 𝐷 of the droplets in the experiment.
The meaning of these specific parameters is shown in the figure 2.

Figure 2. The mechanism for determination of inter-facial tension by pendent drop method.

2.3. Experimental methods

2.3.1. Interfacial tension test procedures

a) The experimental system of petroleum ether cleaning was used. After cleaning, residual
petroleum ether was purged with nitrogen.
b) Use alcohol and distilled water to wash needles, then dry them, and install the needles on the
suspension device.
c) The air in the reactor is pumped out by a vacuum pump and maintained at -0.1 MPa for more than
30 minutes.
d) Transfer the oil sample into the crude oil injection pump.
e) Start heating the whole interface tensiometer by the heater system and use electric heater to heat
oil injection pump, until the reactor and the oil injection pump both reach the experimental
temperature (74℃)
f) Inject the formation water into the high temperature and high pressure reactor from the bottom
valve until the reactor filled with formation water, then inject CO2 at constant experimental
pressure into the reactor from the top valve. Constant pressure pump, CO2 container and reactor
stay connected, and keep the pressure at experimental pressure for 24 hours to make sure the
formation water saturated with CO2.
g) Turn off the valves of the reactor.
h) Ensure that the needle immersed in the water phase to form an upper pendent oil drop. Every
pressure point need to be stable for 24 hours to make sure the formation water saturated with CO2.
At least three droplets were photographed at each pressure point, each droplet should be stable for
30 minutes, and each droplet should take at least three photos.
i) Adjust the experimental pressure, repeat step f, g, h, until the end of the experiment.

2.3.2. Density measurement. In the process of calculating interfacial tension, it is necessary to

determine the density of saturated carbonate water and crude oil under different pressures. Density is
measured by high temperature and high-pressure densitometer.
The high temperature and high-pressure densitometer is connected with the drop chamber through
a pipeline, and the temperature when measuring the density is 74 ℃. Under each experimental

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EEEP 2019 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 467 (2020) 012010 doi:10.1088/1755-1315/467/1/012010

pressure condition, the saturated carbonate water in the suspension chamber was introduced into the
densitometer through the pipeline, and the density of the saturated carbonate water in the suspension
chamber was measured in real time. After the experiment complete, the crude oil in the crude oil
injection pump was introduced into the high temperature and high-pressure densimeter to measure the
density of crude oil at the experimental pressure point.

2.3.3. Flash evaporation experiment. The saturated carbonated water was transferred into the flash
bottle and the volume and pressure of the sample were recorded. Connect the flash bottle with the gas
meter, slowly release the gas into the gas meter, keep the pressure of the gas meter unchanged, record
the volume change and temperature change of the gas meter. The mass changes before and after
degassing in flash bottle were recorded, and the carbonate saturation was calculated by the measured
data

3. Results and discussion

3.1. Experiment phenomenon

3.1.1. Two-phase interface characteristics of crude oil-formation water system. Figure 3 (a), (b) and
(c) are interface pictures of crude oil-formation water system under temperature of 74 ℃ and under
pressure of 10MPa, 20MPa and 35MPa, respectively. It can be found that there is no dissolution and
extraction phenomena between crude oil and formation water system under different pressure
conditions with the increase of pressure. There are no obvious light hydrocarbon layers in the three
groups of experiments, which indicates that there is no medium transfer between crude oil and
formation water.

(a) Interface characteristics under (b) Interface characteristics (c) Interface characteristics
10MPa. under 20MPa. under 35MPa.
Figure 3. Crude oil-formation water interactions.

3.1.2. Three-phase interface characteristics of oil-co2-formation water system. Figure 4 shows a mass
transfer between oil-carbonated water systems under temperature of 74 ℃. It can be seen in figure 4(a)
that when the pressure is 5 MPa, there is no dissolution and extraction phenomena phenomenon
between the oil droplets and the carbonate water system. When the pressure rises to 14 MPa, as can be
seen in Figure 4 (b), a thin layer of light hydrocarbons can be found at the interface between oil
droplets and carbonated water. In the oil-gas-water three-phase system, CO2 first contacts the gas-
water interface, and then dissolves and extracts oil droplets through the interface. As the pressure rises,
the extraction of light components in oil increases. As shown in Figure 4 (c), when the pressure rises
to 30 MPa, the light component column mentioned by CO2 extraction is more obvious at the top of the
oil drop, and the light hydrocarbon layer around the oil drop is thicker. It can be seen that increasing
pressure is helpful to accelerate the passage of CO2 at the gas-water interface and to the extraction of

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EEEP 2019 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 467 (2020) 012010 doi:10.1088/1755-1315/467/1/012010

light components in the oil phase. Previous studies did not find the experimental phenomena of
extracting light hydrocarbons from oil droplets by CO2 through gas-water interface.

(a) Interface characteristics (b) Interface characteristics (c) Interface characteristics

under 5MPa under 14MPa under 30MPa
Figure 4. Interaction between crude oil and formation water saturated with CO2.

3.1.3. Difference analysis of interface characteristics. There is no mass transfer between crude oil and
water system, and the change of pressure has no obvious effect on the interface characteristics between
oil and water, so crude oil and formation water are completely immiscible in the reservoir. For the
crude oil-carbonated water system, CO2 will first diffuse into the crude oil through the gas-water
interface, and then extract the light components from the crude oil in free gas form that previous
studies did not show the experimental phenomena. Medium exchange occurs between crude oil and
carbonated water, and there exists partial miscibility, which increases with the change of pressure.

3.2. Analysis of experimental results

3.2.1. Effect of different saturation of CO2 on interfacial tension of oil-water system. The equilibrium
interfacial tension between crude oil and carbonated water with different saturation is shown in the
Figure 5. The equilibrium interfacial tension of the system decreases significantly with the increase of
pressure. This shows that CO2 can reduce oil-water interfacial tension, improve oil-water interfacial
characteristics and enhance oil displacement efficiency. When P < 17.09MPa, the interfacial tension of
water balance in crude oil-saturated CO2 formation tends to decrease gradually. When P > 17.09MPa,
the interfacial tension of water balance in crude oil-saturated CO2 formation decreases slowly and
basically remains unchanged.

14
The equilibrium interfacial tension mN/m

14
13
13
12
12
11
11
10
0 5 10 15 20 25
Pressure /MPa

Figure 5. The equilibrium interfacial tension of oil-saturation carbonated water.

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EEEP 2019 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 467 (2020) 012010 doi:10.1088/1755-1315/467/1/012010

Through a single degassing experiment of carbonated water under different pressure, the solubility
chart of CO2 in formation water was obtained. As shown in Figure 6, the solubility of CO2 in water
increases with the increase of system pressure. When P < 17.09 MPa, the solubility increased rapidly,
and when P > 17.09 MPa, the solubility increased slowly and almost saturated. At the same time,
compared with Figure 5 and Figure 6, it can be seen that with the increase of system pressure, the
amount of dissolved CO2 gas increases and the interfacial tension between oil and water decreases.
When the system pressure reaches the threshold pressure of 17.09MPa, the amount of dissolved CO2
almost reaches the maximum. When the pressure reaches 17.09 MPa, the solubility of CO2 increases
slowly, and the interfacial tension of water balance between crude oil and saturated CO2 formation
decreases slowly and basically remains unchanged.

1.6
1.4
1.2
Solubility mol/kg

1
0.8
0.6
0.4
0.2
0
0 10 20 30 40
Pressure MPa

Figure 6. The solubility of CO2 in the formation water under different pressure.

The experimental results show that when the pressure reaches 23 MPa, the interfacial tension
between CO2 and formation water can reach 12 mN/m, which indicates that the interaction between
formation water and CO2 system is difficult to achieve miscibility.
The threshold pressure exists in the system of crude oil and carbonated water with different
saturation. When pressure is higher than the threshold pressure, the increase of dissolved CO2 gas is
slow, and the interfacial tension of the system will not decrease obviously with the increase of
pressure. So it's not that the larger the CO2 injection, the better the oil displacement effect. There is an
optimum CO2 injection in this system. For Zhoucheng crude oil and saturated carbonate water system,
when the gas-liquid ratio is 23.69 and the solubility of CO2 is 1.06 mol/kg, the interfacial tension is
better and the cost is lower.

3.2.2. Comparison of the changes of equilibrium interfacial tension of two systems. As shown in
Figure 7, the equilibrium interfacial tension of crude oil-formation water system remains basically
unchanged with the increase of pressure. The equilibrium interfacial tension of crude oil-carbonated
water system decreases obviously with the increase of pressure and the increase of CO2 solubility.
After dissolving CO2 in formation water, the interfacial tension of crude oil-saturated CO2 carbonate
system is lower than that of non-carbonated system, and the difference between the two systems
increases with the increase of pressure. The interfacial tension of oil-water balance decreased by 13.94%
after CO2 injection. It can be seen that CO2 injection can effectively reduce the interfacial tension of
oil-water balance.

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EEEP 2019 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 467 (2020) 012010 doi:10.1088/1755-1315/467/1/012010

1.2

Absolute value of the interfacial

1.1
1
0.9
tension
0.8
0.7
0.6
oil‐carbonate water
0.5 oil‐formation water
0.4
0 5 10 15 20 25 30 35 40
Pressure, MPa

Figure 7. Absolute value of Interfacial tension of two systems under different pressure.

4. Conclusions
(1) There is no obvious transfer between oil and formation water systems. In the oil-carbonated water
system, the extraction of crude oil by CO2 is gradually enhanced, when the pressure becomes higher,
and the medium exchange between oil and carbonate water occurs, resulting in partial miscibility.
(2) There is a threshold pressure in the crude oil-carbonated water system with different saturation.
When the pressure is lower than the threshold value, the amount of dissolved CO2 gas increases and
the interfacial tension between oil and water decreases with the increase of the system pressure. When
the pressure is higher than the threshold value, the amount of dissolved CO2 gas increases slowly, and
the interfacial tension of the system will not decrease obviously with the increase of the pressure.
(3) The interfacial tension of oil and non-carbonated formation water is higher than that of oil-
saturated CO2 water system. With the increase of pressure, the interfacial tension of oil-saturated CO2
water system increases gradually, and the interfacial tension of oil-formation water system basic
maintain unchanged. Injecting CO2 can effectively reduce the interfacial tension of oil-water system.

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IOP Conf. Series: Earth and Environmental Science 467 (2020) 012010 doi:10.1088/1755-1315/467/1/012010

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