The Effect of Oil Properties on the Supercritical CO 2 Diffusion Coefficient under Tight Reservoir Conditions

In this paper, a generalized methodology has been developed to determine the diffusion coefficient of supercritical CO2 in cores that are saturated with different oil samples, under reservoir conditions. In theory, a mathematical model that combines Fick’s diffusion equation and the Peng-Robinson equation of state has been established to describe the mass transfer process. In experiments, the pressure decay method has been employed, and the CO2 diffusion coefficient can be determined once the experimental data match the computational result of the theoretical model. Six oil samples with different compositions (oil samples A to F) are introduced in this study, and the results show that the supercritical CO2 diffusion coefficient decreases gradually from oil samples A to F. The changing properties of oil can account for the decrease in the CO2 diffusion coefficient in two aspects. First, the increasing viscosity of oil slows down the speed of the mass transfer process. Second, the increase in the proportion of heavy components in oil enlarges the mass transfer resistance. According to the results of this work, a lower viscosity and lighter components of oil can facilitate the mass transfer process.


Introduction
Insufficient oil and gas supplies and global warming have aroused interest in enhanced oil recovery (EOR) with CO 2 and geological CO 2 storage [1][2][3].CO 2 is usually injected into geological formations to improve oil recovery and to store and sequester the greenhouse gas in the atmosphere through the interaction of CO 2 with the crude oil, which restricts CO 2 molecules in the pores of the rock, and the reaction of CO 2 molecules with mineral grains.The main purpose of CO 2 EOR is to produce more hydrocarbons from oil reservoirs [4][5][6][7][8].Therefore, a full understanding of the behavior of CO 2 under reservoir conditions has always been one of the main interests of researchers and the petroleum industry.There are several processes involved in the CO 2 EOR, i.e., diffusion of CO 2 into the crude oil in the porous rocks [9][10][11][12][13][14][15][16][17][18][19], the chemical reaction of CO 2 with formation minerals [20,21], and rock mechanics caused by pore pressure changes [22].Only the first process of CO 2 diffusion in porous media is considered in this study, which has theoretical importance and meaning for applications in the petroleum industry.
Diffusion is a spontaneously dispersing process of molecules or ions [23], which is caused by the concentration difference in solutions or dispersions.The quantitative description of the rate of the diffusion process is usually expressed by the diffusion coefficient [24][25][26][27].There have been several Energies 2018, 11, 1495 3 of 20 has been employed to determine the diffusion coefficient.The pressure of the CO 2 phase in the annular space of the diffusion cell was monitored and recorded during the mass transfer process of CO 2 into the oil-saturated low-permeable cores.Once the difference between the tested and calculated pressure decay curves reached a minimum value, the diffusion coefficient of CO 2 could be determined.In addition, the influence of oil properties on the CO 2 diffusion coefficient has also been analyzed.

Materials
The oil samples used in the present work were obtained by mixing kerosene and crude oil in various ratios to form a series of oil samples with different viscosities and component proportions.The kerosene was purchased from the China University of Petroleum (East China) and has a density and viscosity of 802.1 kg/m 3 and 1.34 mPa•s under 50 • C and atmospheric pressure, respectively.The crude oil used in this work was collected from Changji Oilfield in Xinjiang Province (China).The crude oil sample is dead oil without sands and brine, whose density measured with a densitometer (DMA 4200M, Anton Paar, Graz, Austria) was 936.8 kg/m 3 under 50 • C and atmospheric pressure.The viscosity, which was measured by a rheometer (MCR 302, Anton Paar), is 1770.91 mPa•s under the same conditions.The component distributions of both the kerosene and crude oil were determined with gas chromatography (GC), and the result is depicted in Figure 1.The CO 2 used in this work was purchased from Tianyuan Co., Ltd.(Qingdao, China) and has a purity higher than 99.99 mol %.Artificial cores with a permeability that ranged from 0.096 to 0.103 mD were used as porous media in this work and were compressed with sand particles.The diameters of the sand particles in the cores were restricted to a tiny range, which can ensure the homogeneity and isotropy of the cores.The parameters of the cores used in this work are tabulated in Table 1.
Real reservoirs are heterogeneous and anisotropic, which makes the mass transfer process in reservoirs complicated [51][52][53]; however, this paper concentrates on the effect of oil properties on the CO 2 diffusion coefficients.To simplify the model and analysis, artificial cores are introduced to eliminate the influence of this factor.Therefore, the effects of heterogeneity and anisotropy are ignored in this study.
Energies 2018, 11, x FOR PEER REVIEW 3 of 20 mass transfer process of CO2 into the oil-saturated low-permeable cores.Once the difference between the tested and calculated pressure decay curves reached a minimum value, the diffusion coefficient of CO2 could be determined.In addition, the influence of oil properties on the CO2 diffusion coefficient has also been analyzed.

Materials
The oil samples used in the present work were obtained by mixing kerosene and crude oil in various ratios to form a series of oil samples with different viscosities and component proportions.The kerosene was purchased from the China University of Petroleum (East China) and has a density and viscosity of 802.1 kg/m 3 and 1.34 mPa•s under 50 °C and atmospheric pressure, respectively.The crude oil used in this work was collected from Changji Oilfield in Xinjiang Province (China).The crude oil sample is dead oil without sands and brine, whose density measured with a densitometer (DMA 4200M, Anton Paar, Graz, Austria) was 936.8 kg/m 3 under 50 °C and atmospheric pressure.The viscosity, which was measured by a rheometer (MCR 302, Anton Paar), is 1770.91 mPa•s under the same conditions.The component distributions of both the kerosene and crude oil were determined with gas chromatography (GC), and the result is depicted in Figure 1.The CO2 used in this work was purchased from Tianyuan Co., Ltd.(Qingdao, China) and has a purity higher than 99.99 mol %.Artificial cores with a permeability that ranged from 0.096 to 0.103 mD were used as porous media in this work and were compressed with sand particles.The diameters of the sand particles in the cores were restricted to a tiny range, which can ensure the homogeneity and isotropy of the cores.The parameters of the cores used in this work are tabulated in Table 1.
Real reservoirs are heterogeneous and anisotropic, which makes the mass transfer process in reservoirs complicated [51][52][53]; however, this paper concentrates on the effect of oil properties on the CO2 diffusion coefficients.To simplify the model and analysis, artificial cores are introduced to eliminate the influence of this factor.Therefore, the effects of heterogeneity and anisotropy are ignored in this study.According to Table 1, the characteristics (porosity and permeability) of the cores are not exactly the same.The artificial cores are compressed with sand particles and crosslinker; therefore, two factors contribute to the variable characteristics of the cores.First, the sand particles are not identical; thus, the inner structure of the cores is not totally regular.Second, the distribution of crosslinker may influence the properties of the cores; for instance, the layer of crosslinker on the particle surface can decrease the diameter of the pores.However, the properties of the cores that are employed in this work are so similar that the influence of different cores can be ignored.

Apparatus
The schematic diagram of the apparatus used in this paper was illustrated in our previously published work and again in Figure 2 [54,55].The CO 2 diffusion experiments are conducted in a diffusion cell located in a water bath to keep a constant temperature for all the experiments.The core is placed in the center of the diffusion cell, and CO 2 is introduced into the cylinder.The pressure of the CO 2 decreases due to the diffusion of CO 2 into the core.The pressure decay of the CO 2 in the diffusion cell during each experiment is monitored and recorded by a pressure transducer, which can be used for diffusion coefficient calculation.According to Table 1, the characteristics (porosity and permeability) of the cores are not exactly the same.The artificial cores are compressed with sand particles and crosslinker; therefore, two factors contribute to the variable characteristics of the cores.First, the sand particles are not identical; thus, the inner structure of the cores is not totally regular.Second, the distribution of crosslinker may influence the properties of the cores; for instance, the layer of crosslinker on the particle surface can decrease the diameter of the pores.However, the properties of the cores that are employed in this work are so similar that the influence of different cores can be ignored.

Apparatus
The schematic diagram of the apparatus used in this paper was illustrated in our previously published work and again in Figure 2 [54,55].The CO2 diffusion experiments are conducted in a diffusion cell located in a water bath to keep a constant temperature for all the experiments.The core is placed in the center of the diffusion cell, and CO2 is introduced into the cylinder.The pressure of the CO2 decreases due to the diffusion of CO2 into the core.The pressure decay of the CO2 in the diffusion cell during each experiment is monitored and recorded by a pressure transducer, which can be used for diffusion coefficient calculation.

Experimental Procedures
The experimental procedures used in this study to test the CO2 diffusion coefficients in the oil-saturated cores are described as follows:

Experimental Procedures
The experimental procedures used in this study to test the CO 2 diffusion coefficients in the oil-saturated cores are described as follows:

Diffusion Model in Porous Media
The physical model used in this study is shown in Figure 3 [54,55].The two end faces of the core sample are sealed with aluminum foil with epoxy resin, just as we did in our previous work [55], which makes the end faces impermeable.Thus, CO 2 can diffuse only in the radial direction of the core.The mathematical model used in this study includes Fick's diffusion equation and PR EOS to describe the diffusion process from the CO 2 phase to the cores being saturated with different oil samples.The mass transfer of CO 2 is considered by the diffusion equation, while the phase behavior between CO 2 and the oil sample is described by PR EOS.Several assumptions that were adopted for this mathematical model are elaborated below: (1) Cores are homogenous and isotropic, i.e., the influences of different cores are ignored.
(3) CO 2 concentration at the side surface of the core is constant during the diffusion process.(4) The extraction effect of CO 2 on oil is negligible.(The literature has reported that the extraction effect of CO 2 on hydrocarbons that are heavier than C 9 is tiny [56], and Figure 1 shows that it is reasonable to ignore extraction in this study.)(5) The convection flow caused by the density difference is ignored.(6) The CO 2 transfer process occurs only in the radial direction.(7) There is no heat exchange during the diffusion process.

Diffusion Model in Porous Media
The physical model used in this study is shown in Figure 3 [54,55].The two end faces of the core sample are sealed with aluminum foil with epoxy resin, just as we did in our previous work [55], which makes the end faces impermeable.Thus, CO2 can diffuse only in the radial direction of the core.The mathematical model used in this study includes Fick's diffusion equation and PR EOS to describe the diffusion process from the CO2 phase to the cores being saturated with different oil samples.The mass transfer of CO2 is considered by the diffusion equation, while the phase behavior between CO2 and the oil sample is described by PR EOS.Several assumptions that were adopted for this mathematical model are elaborated below: (1) Cores are homogenous and isotropic, i.e., the influences of different cores are ignored.
(3) CO2 concentration at the side surface of the core is constant during the diffusion process.(4) The extraction effect of CO2 on oil is negligible.(The literature has reported that the extraction effect of CO2 on hydrocarbons that are heavier than C9 is tiny [56], and Figure 1 shows that it is reasonable to ignore extraction in this study.)(5) The convection flow caused by the density difference is ignored.(6) The CO2 transfer process occurs only in the radial direction.(7) There is no heat exchange during the diffusion process.In the cylindrical coordinates system, Equation ( 1) is used to describe the radial diffusion process of CO2 in oil-saturated porous media.A velocity item is introduced into the equation to consider the influence of oil swelling due to CO2 dissolution: In the cylindrical coordinates system, Equation ( 1) is used to describe the radial diffusion process of CO 2 in oil-saturated porous media.A velocity item is introduced into the equation to consider the influence of oil swelling due to CO 2 dissolution: where c is the concentration of CO 2 in the oil sample, mol/m 3 , t is diffusion time, s, u is the flow velocity that is generated by the volume expansion of the oil sample, m/s, r is the distance to the central axis of the core, m, and D is the effective diffusion coefficient of CO 2 in the oil-saturated core, m 2 /s.
To facilitate the solution of the mathematical model, Equation ( 2) is used to nondimensionalize the diffusion equation, which can be expressed as Equation ( 3): where r is the dimensionless distance, r 0 is the radius of the core, m, c is the dimensionless concentration, c 0 is the saturation concentration of CO 2 in crude oil under experimental conditions, mol/m 3 , τ is dimensionless time and u is the dimensionless velocity.
According to the characteristics of diffusion, the side surface of the core can be considered the Dirichlet boundary, and the central axis of the core can be considered a closed boundary.The boundary conditions and initial conditions of the mathematical model can be represented by Equations ( 4) and ( 5), respectively.The full implicit finite difference method is employed to solve the above model.In the discrete process, the derivative of the concentration and velocity with space is a second-order central difference scheme, and the derivative of concentration with time is a first-order forward difference scheme:

Peng-Robinson Equation of State (PR EOS)
The CO 2 pressure of the diffusion cell is recorded for the pressure decay method, and the pressure prediction thus affects the accuracy of the CO 2 diffusion coefficient.PR EOS is introduced in this paper, and the interaction between CO 2 and the oil sample is considered, which increases the calculation accuracy of the annular pressure and diffusion coefficient.PR EOS is a third-order equation with two constants that were proposed by Peng and Robinson [57].It is a semi-empirical model that is widely applied in the petrochemical industry, and it describes the phase behavior and phase equilibrium of multicomponent systems.PR EOS requires the specific parameters of the components in the system and the binary interaction parameters (BIPs) between each component.PR EOS can be expressed by Equations ( 6) and ( 7): where P is the system pressure, Pa, R is the general gas constant, 8.314 J/mol/K, T is the system temperature, K, V is the molar volume, m 3 /mol, T c is the critical temperature, K, and P c is the critical pressure, Pa.α is a function of the relative temperature and acentric factor.The composition of the oil sample is complex.Although PR EOS sets no restriction on the number of components in the mixture, the computing load sharply increases with the number of components.Thus, it is important to simplify the calculation process with the prerequisite of ensuring a high accuracy of calculation.In this study, several pseudo-components are introduced as substitutes for all hydrocarbon components in the oil sample, which can efficiently decrease the calculation load of PR EOS without influencing the computing accuracy [56][57][58].Specifically, in this work, hydrocarbons with a single carbon number (SCN) are lumped into three pseudo-components, which have been tested as having a good result on the oil/CO 2 system [59,60].The parameters of the pseudo-components were determined with a series of empirical models [61][62][63][64][65][66][67][68], and the specific data are listed in the results section.

Determination of the Diffusion Coefficients
The CO 2 diffusion coefficient is determined by fitting the experimental and calculated data with particle swarm optimization (PSO).The calculated pressure-time (p-t) curve can be adjusted to minimize the error with a measured p-t curve by optimizing the value of the diffusion coefficient, according to Equation (2).The CO 2 diffusion coefficient is determined once the value of the objective function reaches a minimum, which is shown in Equation ( 8): where PN is the data number of the p-t curve, and t Ei and t Ci are the experimental and calculated times, respectively.For the calculated p-t curve, the pressure values can be determined with the following steps: (1) Determine CO 2 concentration distribution in the core.
(2) Calculate the mole composition in the annular space of the diffusion cell according to the amount of swelled oil and dissolved CO 2 .(3) Determine the pressure value by solving PR EOS with data that are obtained in step 2.
Moreover, global regression and piecewise regression are employed to determine the CO 2 diffusion coefficients.In a global regression, all experimental data points are used, and a constant coefficient is obtained to describe the average rate of mass transfer.In the early stage and later stage regressions, part of the data points is employed to calculate the diffusion coefficients, and two diffusion coefficients are obtained to describe the rate of mass transfer in the early and later stages, respectively.The relevant contents will be elaborated in the Results section.

Characterization of the Oil Samples
Six groups of oil samples, which were prepared by mixing kerosene and crude oil under different volume ratios, are used in the diffusion experiments to study the influence of oil properties on the CO 2 diffusion coefficient.The viscosity-temperature curves of the oil samples are presented in Figure 4, and the viscosity of each oil sample at the experimental temperature is marked in the figure (the pentagram symbols).The carbon distributions of the oil samples that were determined with the method in the literatures [55,59] are illustrated in Figure 5.It is notable that the carbon distributions of kerosene and Energies 2018, 11, 1495 8 of 20 crude oil are determined with the above method, and the carbon distribution of mixed oil is determined by combining the carbon distribution of the two oils according to their mixing ratio.The detailed process can be described with Equation ( 9): where z i , z c i and z k i are the mole friction of component i in the mixed oil, crude oil and kerosene samples, respectively, and n c and n k are the mole numbers of crude oil and kerosene, respectively.
Six groups of oil samples, which were prepared by mixing kerosene and crude oil under different volume ratios, are used in the diffusion experiments to study the influence of oil properties on the CO2 diffusion coefficient.The viscosity-temperature curves of the oil samples are presented in Figure 4, and the viscosity of each oil sample at the experimental temperature is marked in the figure (the pentagram symbols).The carbon distributions of the oil samples that were determined with the method in the literatures [55,59] are illustrated in Figure 5.It is notable that the carbon distributions of kerosene and crude oil are determined with the above method, and the carbon distribution of mixed oil is determined by combining the carbon distribution of the two oils according to their mixing ratio.The detailed process can be described with Equation ( 9): where zi, and are the mole friction of component i in the mixed oil, crude oil and kerosene samples, respectively, and n c and n k are the mole numbers of crude oil and kerosene, respectively.

Characterization of the Oil Samples
Six groups of oil samples, which were prepared by mixing kerosene and crude oil under different volume ratios, are used in the diffusion experiments to study the influence of oil properties on the CO2 diffusion coefficient.The viscosity-temperature curves of the oil samples are presented in Figure 4, and the viscosity of each oil sample at the experimental temperature is marked in the figure (the pentagram symbols).The carbon distributions of the oil samples that were determined with the method in the literatures [55,59] are illustrated in Figure 5.It is notable that the carbon distributions of kerosene and crude oil are determined with the above method, and the carbon distribution of mixed oil is determined by combining the carbon distribution of the two oils according to their mixing ratio.The detailed process can be described with Equation ( 9): where zi, and are the mole friction of component i in the mixed oil, crude oil and kerosene samples, respectively, and n c and n k are the mole numbers of crude oil and kerosene, respectively.Figure 5 shows that the components lighter than C 9 account for a tiny part of those oil samples (<1%), which means that there is no obvious extraction effect during the mass transfer process [56,59,60].The components of the CO 2 phase were analyzed by a GC method after the diffusion experiments, and no hydrocarbons were found in the CO 2 phase.The GC analysis result agrees with our previous work [55] and proves that neglecting the extraction effect is reasonable.According to the figure, from oil samples A to E, the number of light components (C 9 -C 15 ) decreases, while the amount of heavy components (heavier than C 18 ) increases gradually.Multiple pseudo-components are introduced in this work to replace the entire carbon distribution to characterize the oil samples, which greatly Energies 2018, 11, 1495 9 of 20 reduces the computational cost [60].The pseudo-component parameters are tabulated in Table 2.The tendencies and values of the data in Table 2 are analogous to our previous work [55], which proves the reliability of the parameters.The binary interaction parameter (BIP) matrix is listed in Table 3 and describes the interactions among the components in the system.BIPs between hydrocarbons are set at 0 according to [61,69].Moreover, only the parameters of oil sample A are given in Tables 2 and 3; the parameters of the other oil samples are presented in the Appendix A.

Solution of the Diffusion Model in the Oil-Saturated Cores
The features of the CO 2 diffusion process in the oil-saturated porous media can be characterized by concentration and velocity profiles, which are obtained by solving the diffusion mathematical model that is proposed in Section 3.1 [54,55].The CO 2 concentration profile during the diffusion process is presented in Figure 6, where black curves identify the CO 2 concentrations at different space and time grids.
Figure 5 shows that the components lighter than C9 account for a tiny part of those oil samples (<1%), which means that there is no obvious extraction effect during the mass transfer process [56,59,60].The components of the CO2 phase were analyzed by a GC method after the diffusion experiments, and no hydrocarbons were found in the CO2 phase.The GC analysis result agrees with our previous work [55] and proves that neglecting the extraction effect is reasonable.According to the figure, from oil samples A to E, the number of light components (C9-C15) decreases, while the amount of heavy components (heavier than C18) increases gradually.Multiple pseudo-components are introduced in this work to replace the entire carbon distribution to characterize the oil samples, which greatly reduces the computational cost [60].The pseudo-component parameters are tabulated in Table 2.The tendencies and values of the data in Table 2 are analogous to our previous work [55], which proves the reliability of the parameters.The binary interaction parameter (BIP) matrix is listed in Table 3 and describes the interactions among the components in the system.BIPs between hydrocarbons are set at 0 according to [61,69].Moreover, only the parameters of oil sample A are given in Tables 2 and 3; the parameters of the other oil samples are presented in the Appendix A.

Solution of the Diffusion Model in the Oil-Saturated Cores
The features of the CO2 diffusion process in the oil-saturated porous media can be characterized by concentration and velocity profiles, which are obtained by solving the diffusion mathematical model that is proposed in Section 3.1 [54,55].The CO2 concentration profile during the diffusion process is presented in Figure 6, where black curves identify the CO2 concentrations at different space and time grids.The area between a curve and the x-axis characterizes the total CO 2 amount in the core at a specific time point, and the area between two curves can characterize the increment of CO 2 during this period of time.According to Figure 6, the CO 2 concentration at the central axis (r = 0) almost reaches 0.5 when dimensionless time is 0.2, and the area between the curve and the x-axis show that Energies 2018, 11, 1495 10 of 20 the average CO 2 concentration was above 0.7 at this moment (the red dashed line in Figure 6).The tendency shows that most of the CO 2 diffuses into the oil-saturated core at the early stage of the diffusion process.Moreover, the area of the colored region between two curves decreases with the increase in dimensionless time, which shows that the increase in CO 2 in the core gradually slows down, i.e., the speed of mass transfer slows down.Therefore, the diffusion process is divided into two stages, namely, an early stage with a high diffusion rate and a later stage with a lower diffusion rate, which is identical to our previous work [55].
The velocity profile caused by oil volume swelling is illustrated in Figure 7.The trend of Figure 7 shows that the velocity of oil is relatively high at the early stage (τ < 0.2), which means that the fast volume expansion of oil, i.e., the diffusion rate of CO 2 , is relatively high.The following decrease in velocity characterizes the relatively slow diffusion rate in the later stage.Thus, Figures 6 and 7 complement and confirm one another.It should be noted that the velocity difference between the outer part and inner part of the core is obvious at an early stage; then, the difference decreases gradually, which shows CO 2 diffusing from the outer part to the inner part of the core.More details have already been elaborated in our previous work.The area between a curve and the x-axis characterizes the total CO2 amount in the core at a specific time point, and the area between two curves can characterize the increment of CO2 during this period of time.According to Figure 6, the CO2 concentration at the central axis ( ̅ = 0) almost reaches 0.5 when dimensionless time is 0.2, and the area between the curve and the x-axis show that the average CO2 concentration was above 0.7 at this moment (the red dashed line in Figure 6).The tendency shows that most of the CO2 diffuses into the oil-saturated core at the early stage of the diffusion process.Moreover, the area of the colored region between two curves decreases with the increase in dimensionless time, which shows that the increase in CO2 in the core gradually slows down, i.e., the speed of mass transfer slows down.Therefore, the diffusion process is divided into two stages, namely, an early stage with a high diffusion rate and a later stage with a lower diffusion rate, which is identical to our previous work [55].
The velocity profile caused by oil volume swelling is illustrated in Figure 7.The trend of Figure 7 shows that the velocity of oil is relatively high at the early stage (τ < 0.2), which means that the fast volume expansion of oil, i.e., the diffusion rate of CO2, is relatively high.The following decrease in velocity characterizes the relatively slow diffusion rate in the later stage.Thus, Figures 6 and 7 complement and confirm one another.It should be noted that the velocity difference between the outer part and inner part of the core is obvious at an early stage; then, the difference decreases gradually, which shows CO2 diffusing from the outer part to the inner part of the core.More details have already been elaborated in our previous work.

Effect of the Oil Properties on the Diffusion Coefficient
A pressure decay experiment is employed in this paper to study the CO2 diffusion process in oil-saturated tight cores under reservoir conditions.The diffusion coefficient of CO2 is determined with the experimental pressure recording and mathematical model that is listed in Section 3, and the pressure curves of the diffusion experiments with different oil samples are depicted in Figure 8. Except for the experimental data, the global fitting (red line) with a constant diffusion coefficient and the piecewise fitting (blue and violet dashed lines) with variable diffusion coefficients are also given in Figure 8.Although there are some differences between the results of the global regression of the different experiments (see Figure 8a,b), which can be attributed to experimental and calculation errors, the value of the goodness-of-fit in each set of experiments shows that both regression methods have acceptable accuracy.This value also shows that the piecewise regression has a better result than the global regression.The highly precise result of the piecewise fitting agrees with the literature [70,71] that suggests that the diffusion coefficient is a variable during the diffusion process, and it also proves the reliability of the conclusions in Section 4.2.

Effect of the Oil Properties on the Diffusion Coefficient
A pressure decay experiment is employed in this paper to study the CO 2 diffusion process in oil-saturated tight cores under reservoir conditions.The diffusion coefficient of CO 2 is determined with the experimental pressure recording and mathematical model that is listed in Section 3, and the pressure curves of the diffusion experiments with different oil samples are depicted in Figure 8. Except for the experimental data, the global fitting (red line) with a constant diffusion coefficient and the piecewise fitting (blue and violet dashed lines) with variable diffusion coefficients are also given in Figure 8.Although there are some differences between the results of the global regression of the different experiments (see Figure 8a,b), which can be attributed to experimental and calculation errors, the value of the goodness-of-fit in each set of experiments shows that both regression methods have acceptable accuracy.This value also shows that the piecewise regression has a better result than the global regression.The highly precise result of the piecewise fitting agrees with the literature [70,71] that suggests that the diffusion coefficient is a variable during the diffusion process, and it also proves the reliability of the conclusions in Section 4.2.
decreases gradually from oil samples A to F, and the decreasing tendency can be attributed to the following two factors: viscosity of the liquid phase has an obvious influence on the diffusion coefficient [59,[72][73][74][75].The effect of oil viscosity on the CO2 diffusion coefficient is depicted in Figure 10.The figure shows that a lower viscosity can facilitate the CO2 diffusion process, which agrees with the negative relationship between the two parameters that are proposed in the literature [59,[74][75][76].Moreover, Figures 9 and 10 also show the obvious tendency of the diffusion coefficients at different stages.The diffusion coefficient at the early stage is always higher than the average level (global regression), while the diffusion coefficient at the later stage is always lower than the average level.The coefficient that is determined without PR EOS is minimal because it ignores the interaction of oil and CO2.It is notable that the experimental data form a good linear trend in the semilogarithmic coordinate system.Hayduk and Cheng [77] tested a large amount of the experimental data in the literature to reveal the relationship between the diffusion coefficient and the viscosity of the solvent.They indicated that any diffusing substance has a specific exponential correlation between its diffusion coefficient and the viscosity of the solvent (or pure liquid phase), which is irrelevant to the components of the solvent.Their conclusion is summarized as equation 10, where μ is the viscosity of the solvent or pure liquid phase: (1) The increase in the viscosity of the oil samples.Numerous scholars have indicated that the viscosity of the liquid phase has an obvious influence on the diffusion coefficient [59,[72][73][74][75].The effect of oil viscosity on the CO 2 diffusion coefficient is depicted in Figure 10.The figure shows that a lower viscosity can facilitate the CO 2 diffusion process, which agrees with the negative relationship between the two parameters that are proposed in the literature [59,[74][75][76].Moreover, Figures 9 and 10 also show the obvious tendency of the diffusion coefficients at different stages.The diffusion coefficient at the early stage is always higher than the average level (global regression), while the diffusion coefficient at the later stage is always lower than the average level.The coefficient that is determined without PR EOS is minimal because it ignores the interaction of oil and CO 2 .It is notable that the experimental data form a good linear trend in the semilogarithmic coordinate system.
Energies 2018, 11, x FOR PEER REVIEW 12 of 20 (1) The increase in the viscosity of the oil samples.Numerous scholars have indicated that the viscosity of the liquid phase has an obvious influence on the diffusion coefficient [59,[72][73][74][75].The effect of oil viscosity on the CO2 diffusion coefficient is depicted in Figure 10.The figure shows that a lower viscosity can facilitate the CO2 diffusion process, which agrees with the negative relationship between the two parameters that are proposed in the literature [59,[74][75][76].Moreover, Figures 9 and 10 also show the obvious tendency of the diffusion coefficients at different stages.The diffusion coefficient at the early stage is always higher than the average level (global regression), while the diffusion coefficient at the later stage is always lower than the average level.The coefficient that is determined without PR EOS is minimal because it ignores the interaction of oil and CO2.It is notable that the experimental data form a good linear trend in the semilogarithmic coordinate system.Hayduk and Cheng [77] tested a large amount of the experimental data in the literature to reveal the relationship between the diffusion coefficient and the viscosity of the solvent.They indicated that any diffusing substance has a specific exponential correlation between its diffusion coefficient and the viscosity of the solvent (or pure liquid phase), which is irrelevant to the components of the solvent.Their conclusion is summarized as equation 10, where μ is the viscosity of the solvent or pure liquid phase: Hayduk and Cheng [77] tested a large amount of the experimental data in the literature to reveal the relationship between the diffusion coefficient and the viscosity of the solvent.They indicated that any diffusing substance has a specific exponential correlation between its diffusion coefficient and the viscosity of the solvent (or pure liquid phase), which is irrelevant to the components of the solvent.Their conclusion is summarized as equation 10, where µ is the viscosity of the solvent or pure liquid phase: Equation ( 10) is employed to fit the diffusion coefficient data in Figure 10, which are obtained from the global regression.Moreover, a linear fitting method in a semi-logarithmic coordinate system is also introduced, because of the obvious linear relationship between the diffusivity and viscosity in Figure 10.The experimental data and two fitting lines are illustrated in Figure 11.As seen, both fitting methods have a satisfactory goodness-of-fit.The similar trend of experimental data and the classic exponential model (the blue dash-and-dotted line in Figure 11) proves that the data in this paper are reliable and that the viscosity of the liquid phase greatly influences the diffusion process.However, the linear fitting of D and lnµ shows a better result than the exponential model, and the deviation between the two fitting lines increases gradually as the viscosity increases.This finding may reveal that for a complex liquid such as petroleum, viscosity is not the exclusive factor that affects the diffusion process.Equation ( 10) is employed to fit the diffusion coefficient data in Figure 10, which are obtained from the global regression.Moreover, a linear fitting method in a semi-logarithmic coordinate system is also introduced, because of the obvious linear relationship between the diffusivity and viscosity in Figure 10.The experimental data and two fitting lines are illustrated in Figure 11.As seen, both fitting methods have a satisfactory goodness-of-fit.The similar trend of experimental data and the classic exponential model (the blue dash-and-dotted line in Figure 11) proves that the data in this paper are reliable and that the viscosity of the liquid phase greatly influences the diffusion process.However, the linear fitting of D and lnμ shows a better result than the exponential model, and the deviation between the two fitting lines increases gradually as the viscosity increases.This finding may reveal that for a complex liquid such as petroleum, viscosity is not the exclusive factor that affects the diffusion process.(2) The increasing proportion of heavy components in the oil samples.As shown in Figure 5, from oil samples A to F, the proportion of heavy components increases gradually.Several scholars have suggested that the components of oil also directly influence the diffusion process of CO2 [73,75].(2) The increasing proportion of heavy components in the oil samples.As shown in Figure 5, from oil samples A to F, the proportion of heavy components increases gradually.Several scholars have suggested that the components of oil also directly influence the diffusion process of CO 2 [73,75].
The solubility of CO 2 in each oil sample, which is determined with a two-phase equilibrium calculation [78][79][80], is presented in Figure 12 and reflects the capacity of oil to accommodate CO 2 .Furthermore, the CO 2 solubility of each pseudo-component at 15.3 MPa and 70 • C is depicted in Figure 13.Figures 12 and 13 show that the CO 2 solubility decreases with the increase in the proportion of heavy components in oil, i.e., the resistance for CO 2 diffusing into oil increases [55].Thus, the increase in the proportion of heavy components restricts the diffusion process from two aspects.First, it improves the viscosity of oil, which indirectly decreases the diffusion coefficient [81].Second, heavy components directly increase the mass transfer resistance.Moreover, the resistance effect of heavy components also accounts for the deviation between the experimental data and the exponential model in Figure 11.(2) The increasing proportion of heavy components in the oil samples.As shown in Figure 5, from oil samples A to F, the proportion of heavy components increases gradually.Several scholars have suggested that the components of oil also directly influence the diffusion process of CO2 [73,75].The solubility of CO2 in each oil sample, which is determined with a two-phase equilibrium calculation [78][79][80], is presented in Figure 12 and reflects the capacity of oil to accommodate CO2.Furthermore, the CO2 solubility of each pseudo-component at 15.3 MPa and 70 °C is depicted in Figure 13.Figures 12 and 13 show that the CO2 solubility decreases with the increase in the proportion of heavy components in oil, i.e., the resistance for CO2 diffusing into oil increases [55].Thus, the increase in the proportion of heavy components restricts the diffusion process from two aspects.First, it improves the viscosity of oil, which indirectly decreases the diffusion coefficient [81].Second, heavy components directly increase the mass transfer resistance.Moreover, the resistance effect of heavy components also accounts for the deviation between the experimental data and the exponential model in Figure 11.

Comparison
The data of the CO2 diffusion coefficient in this paper are compared with the data in the literature, and both are listed in Table 4.

Comparison
The data of the CO 2 diffusion coefficient in this paper are compared with the data in the literature, and both are listed in Table 4.
According to the data in the table, the CO 2 diffusivity that was obtained in this paper is somewhat larger than the CO 2 diffusivity in the literature.However, it is still within a reasonable range, and the differences in the data in the different papers can be attributed to several reasons.First, the experimental pressure and temperature in this work are higher than the experimental pressure and temperature in the literature [59,60,75,76].Thus, the larger diffusion coefficient in this study agrees with the theory that an increase in pressure or temperature facilitates the diffusion process.Second, the viscosities of the oil samples used in this work are lower than the viscosities of the heavy oils used in the literature, which contributes to the high diffusion rate.Third, the proportion of heavy components in the oil samples used in this paper is smaller (by comparing Figure 1 and other works [59,60]); thus, the resistance for CO 2 diffusing into oil is small [55].Moreover, the interaction between CO 2 and the oil samples is characterized by PR EOS in this work, and the data that were obtained with this model are more precise.

Conclusions
A generalized methodology was developed in this paper to determine the diffusion coefficient of supercritical CO 2 in cores saturated with different oil samples, under reservoir conditions.A mathematical model that describes the mass transfer process of CO 2 in oil-saturated cores was established.The pressure decay method was used to determine the diffusion process.The results show that the supercritical CO 2 diffusion coefficient decreases gradually from oil samples A to F. It decreases from 128.92 × 10 −10 to 74.97 × 10 −10 m 2 /s at the early stage, decreases from 89.46 × 10 −10 to 39.38 × 10 −10 m 2 /s at the later stage, and decreases from 107.89 × 10 −10 to 55.33 × 10 −10 m 2 /s with the global regression method.The changing properties of oil can account for the decrease in the CO 2 diffusion coefficient in two aspects.First, the increasing viscosity of oil slows down the speed of the mass transfer process.Second, the increase in the proportion of heavy components in oil enlarges the mass transfer resistance.These findings can provide direction in predicting CO 2 storage potential in reservoirs and the effect of CO 2 EOR.Moreover, these findings can also help to optimize engineering techniques in oil fields.

Figure 1 .
Figure 1.The component distributions of kerosene and the crude oil.Figure 1.The component distributions of kerosene and the crude oil.

Figure 1 .
Figure 1.The component distributions of kerosene and the crude oil.Figure 1.The component distributions of kerosene and the crude oil.

Figure 2 .
Figure 2. The schematic diagram of the apparatus used in the CO2 diffusion experiment.
(a) Clean and dry the core for the experiment, put it into an intermediate container and vacuum for 10.0 h.Then, the oil sample is injected into the intermediate container at room temperature until the pressure of the oil sample reaches 15.0 MPa; maintain this pressure for 48.0 h to ensure that the core pores are completely saturated with crude oil.(b) Seal the two ends of the oil-saturated core with epoxy resin and aluminum foil to ensure that CO2 can diffuse only through the side surface of the core.

Figure 2 .
Figure 2. The schematic diagram of the apparatus used in the CO 2 diffusion experiment.
(a) Clean and dry the core for the experiment, put it into an intermediate container and vacuum for 10.0 h.Then, the oil sample is injected into the intermediate container at room temperature until the pressure of the oil sample reaches 15.0 MPa; maintain this pressure for 48.0 h to ensure that the core pores are completely saturated with crude oil.(b) Seal the two ends of the oil-saturated core with epoxy resin and aluminum foil to ensure that CO 2 can diffuse only through the side surface of the core.Connect the apparatus that is required for the diffusion experiment according to Figure 2.After testing the air tightness of the diffusion cell, place the core in it.Replace the air in the diffusion cell with low pressure CO 2 .(d) Put the diffusion cell and CO 2 container into the water bath at the required temperature for 4.0 h, and open valve 5 to monitor the pressure in the CO 2 container.(e) When the pressure inside the CO 2 container is stable, open valves 2, 3 and 4 to inject CO 2 into the diffusion cell.Close valves 3 and 4 quickly after the pressure in the diffusion cell and CO 2 container reach a balance, and record the pressure decay in the diffusion cell.(f) When the pressure in the diffusion cell does not change, finish the diffusion experiment.Slowly open all valves, release the fluid in the diffusion cell, and clean the equipment for the next set of experiments.

Energies 2018 ,
11, x FOR PEER REVIEW 5 of 20 (c) Connect the apparatus that is required for the diffusion experiment according to Figure 2.After testing the air tightness of the diffusion cell, place the core in it.Replace the air in the diffusion cell with low pressure CO2.(d) Put the diffusion cell and CO2 container into the water bath at the required temperature for 4.0 h, and open valve 5 to monitor the pressure in the CO2 container.(e) When the pressure inside the CO2 container is stable, open valves 2, 3 and 4 to inject CO2 into the diffusion cell.Close valves 3 and 4 quickly after the pressure in the diffusion cell and CO2 container reach a balance, and record the pressure decay in the diffusion cell.(f) When the pressure in the diffusion cell does not change, finish the diffusion experiment.Slowly open all valves, release the fluid in the diffusion cell, and clean the equipment for the next set of experiments.

Figure 3 .
Figure 3.The diagram of the physical model for CO2 diffusion.

Figure 3 .
Figure 3.The diagram of the physical model for CO 2 diffusion.

Figure 4 .
Figure 4. Viscosity-temperature curves of the oil samples (the pentagram symbols are the viscosities of the oil samples under experimental conditions.).

Figure 5 .
Figure 5.The composition analysis of the oil samples.

Figure 4 .
Figure 4. Viscosity-temperature curves of the oil samples (the pentagram symbols are the viscosities of the oil samples under experimental conditions.).

Figure 4 .
Figure 4. Viscosity-temperature curves of the oil samples (the pentagram symbols are the viscosities of the oil samples under experimental conditions.).

Figure 5 .
Figure 5.The composition analysis of the oil samples.

Figure 5 .
Figure 5.The composition analysis of the oil samples.

Figure 6 .
Figure 6.CO2 concentration profile of the cores in the diffusion process (the red line reflects the average CO2 dimensionless concentration in the core at τ = 0.2.).Figure 6. CO 2 concentration profile of the cores in the diffusion process (the red line reflects the average CO 2 dimensionless concentration in the core at τ = 0.2.).

Figure 6 .
Figure 6.CO2 concentration profile of the cores in the diffusion process (the red line reflects the average CO2 dimensionless concentration in the core at τ = 0.2.).Figure 6. CO 2 concentration profile of the cores in the diffusion process (the red line reflects the average CO 2 dimensionless concentration in the core at τ = 0.2.).

Figure 7 .
Figure 7. Velocity of oil in the cores caused by volume swelling.

Figure 7 .
Figure 7. Velocity of oil in the cores caused by volume swelling.

Figure 10 .
Figure 10.The effect of oil viscosity on the CO2 diffusion coefficient.

Figure 10 .
Figure 10.The effect of oil viscosity on the CO2 diffusion coefficient.

Figure 10 .
Figure 10.The effect of oil viscosity on the CO 2 diffusion coefficient.

DFigure 11 .
Figure 11.The effect of oil viscosity on the CO2 diffusion coefficient.

Figure 12 .
Figure 12.CO2 solubility of the oil samples at 70 °C.

Figure 11 .
Figure 11.The effect of oil viscosity on the CO 2 diffusion coefficient.

Figure 11 .
Figure 11.The effect of oil viscosity on the CO2 diffusion coefficient.

Table 1 .
Detailed parameters of the artificial cores.

Table 1 .
Detailed parameters of the artificial cores.

Table 2 .
Parameters of the pseudo-components of oil sample A.

Table 3 .
BIP matrix for the CO 2 and pseudo-components.

Table 2 .
Parameters of the pseudo-components of oil sample A.

Table 3 .
BIP matrix for the CO2 and pseudo-components.

Table 4 .
Data in the literature of the CO2 diffusion coefficient in porous media saturated with oil.

Table 4 .
Data in the literature of the CO 2 diffusion coefficient in porous media saturated with oil.

Table A2 .
BIP matrix of oil sample B.

Table A3 .
BIP matrix of oil sample C.

Table A4 .
BIP matrix of oil sample D.

Table A5 .
BIP matrix of oil sample E.

Table A6 .
BIP matrix of oil sample F.