SPE-180434-MS

Predicting the Effects of Acid Gas on Enhanced Oil Recovery in

Hydrocarbon Gas Injection
Sanbo Lv, Xinwei Liao, Hao Chen, Zhiming Chen, and Xianwei Lv, China University of Petroleum; Xiaojin Zhou,
PetroChina Southwest Oil&GasField Company Engineering Technology Research Institute

Copyright 2016, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Western Regional Meeting held in Anchorage, Alaska, USA, 23–26 May 2016.

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Abstract
Hydrocarbon gas injection is one of the major EOR methods. Hydrocarbon gas has some similar
properties with the oil in reservoir, which has no damage to the formation. In addition, there is a beneficial
mass transfer between hydrocarbon gas and crude oil, when achieving miscibility, the residual oil
saturation where the area is affected by hydrocarbon gas is very low. The effects of the components of
hydrocarbon gas as well as its impurities on enhanced oil recovery have been researched. However, in
some fields, injected gas is from the produced gas with large amounts of acid gas. The corresponding EOR
effects of hydrocarbon gas with high acid gas content are rarely mentioned in the literatures. Thus it is
necessary to study it when hydrocarbon gas with acid gas is injected.
In this paper, acid gas consisting two common components (78.11% of H2S and 21.89% of CO2
respectively) is studied. The oil sample from typical block in K oil reservoir is selected to investigate the
EOR effects of hydrocarbon gas with the above acid gas. The slim-tube experiments are performed with
different percentages of acid gas in injected gas at different displacement pressures. The acid gas
percentages are respectively 0%, 10%, 20%, 30%, 40%, 50%. The experimental procedure is that firstly
the slim tube is saturated with oil, then it is displaced by hydrocarbon gas with one certain percentage of
acid gas at constant temperature and displacement pressure. The ultimate oil recovery which is also
considered to be the displacement efficiency is obtained after injecting 1.2 pore volumes of gas or when
there is no oil production. Similarly, the experiments at different pressures are also conducted.
The experimental results show that under the same temperature, oil composition and gas composition,
the displacement efficiency increases as the displacement pressure increases. However, displacement
efficiency is no longer increasing when displacement pressure increases to one certain value. This pressure
point, that is to say, is minimum miscibility pressure (MMP). It means, when the pressure is higher than
MMP, the effects of displacement pressure on the oil recovery would not be significant. The experimental
results also indicate that under the same temperature, oil composition and displacement pressure,
displacement efficiency increases as the percentage of acid gas in the injected gas increases.
From the work here, MMP can be predicted. The effects of acid gas on enhanced oil recovery can also
be estimated. In the oil field, all the results can be for reference in hydrocarbon gas injection with high
2 SPE-180434-MS

acid gas content. In a word, this work is very meaningful, which provides a new perspective on enhancing
oil recovery as well as cutting the pollution of acid gas. It is a win-win work.
Keywords: Acid gas · Hydrocarbon gas · EOR · Displacement Pressure · Displacement Efficiency

Introduction
Hydrocarbon gas flooding is being conducted in many reservoirs worldwide. The aim of using hydro-
carbon gas for displacing oil is to improve the mass transfer between hydrocarbon gas and crude oil to
achieve miscibility to enhance the oil recovery (Alston et al., 1983; Zick, 1986; Lee et al., 1988;
Shyeh-Yung et al., 1994; Shen et al., 1998; Chen et al., 2013). The important technological areas of the
hydrocarbon gas flooding included the phase behavior and miscibility, sweepout, displacement efficiency,
and process design variations (Stalkup, 1983). Among them, the miscibility and displacement efficiency
are the two key factors, which many studies are performed on.
As for miscibility, it’s important to understand the miscible mechanism first before studying the factors
influencing the miscibility. The major miscible processes with oil were studied and developed, which
were first-contact miscible, condensing-gas drive, vaporizing-gas drive. The three miscible processes can
be separated and combined with each other in different miscible displacement. For example, according to
the experimental observation and equation of state (EOS) predictions, it’s belived that a combined
condensing/vaporizing-gas drive mechanism, rather than the traditionally believed condensing-gas drive
mechanism, may be responsible for the miscible process of rich-gas with reservoir oil in the displacement
(Zick, 1986). This miscibility mechanism of multiple-contact-miscible (MCM) drives was developed and
corrected later by Novosad et al. (1987), which demonstrated that the rich-gas displacement in low-
temperature reservoirs were mostly condensing processes, while the vaporizing-gas drive mechanism
prevailed in high-temperature reservoirs based on the experimental data and equation-of-state simulations.
After that, the mechanism of component mass transfer among the phases in EOR processes was
determined by slim-tube experiments. And that the mechanism through which hydrocarbon gas drive
occurs was the dual action of evaporation and condensation, with the former as the primary mechanism.
The intermediate component of the produced gas exhibited a decreasing and then increasing trend. (Lai
et al., 2014) Additionally, through analyses of the simulation results, in particular the phase-composition
information predicted, the factors governing the rich gas displacement mass transfer mechanisms were
obtained by Lee et al. (1988). They were related to the thermodynamic variables, i.e. the compositions of
the reservoir fluid and injected gases, reservoir pressure and temperature, displacement pressure. Among
them, almost all of the researchers had studied the effects of the compositions of the injectant gases and
displacement pressure on enhanced oil recovery.
In hydrocarbon gas flooding, MMP as one of the most important parameters to control and evaluate the
misbility, not only can accurately account for the complex condensing/vaporizing (CV) displacement
processes of hydrocarbon gas with oil, but also has great influences on the displacement efficiency of the
crude oil. The components of the injected gases as one of the most important parameters to influence the
MMP are very important to the oil recovery. Hence, the effects of the components of hydrocarbon gas as
well as its impurities (such as CO2) on enhanced oil recovery have been researched by many researchers.
The effects of hydrocarbon injectant compositions and displacement pressure on oil displacement
efficiency were investigated in the laboratory. Lower oil-recovery efficiencies and lower injectant
mobilities had been observed at lower enrichment levels and/or at lower pressures. (Shyeh-Yung et al.,
1994) The effects of gas enrichment in reservoir-scale enriched-gas-drive displacements were also
examined through predictions made with compositional simulation and analytical solutions. (Stalkup,
1990; Johns et al., 1994) In their work, oil recovery efficiency increased only marginally when enrichment
was somewhat greater than the minimum enrichment for miscibility (MME), but increased quickly for
enrichments near the MME. Furthermore, a critical gas enrichment (CGE) above MME was defined that
separates the multicontact miscibility region into two regions: MCM1 (the gas enrichment below CGE)
SPE-180434-MS 3

and MCM2 (the gas enrichment above CGE). For the gas enrichment, when in the MCM1, oil recovery
could increase significantly with enrichment, or oil recovery was not as sensitive to enrichment.
Meanwhile, displacements in the MCM1 region exhibited a combined condensing and vaporizing
mechanism, whereas displacements in the MCM2 region were purely condensing. (Johns et al., 1999)
The effects of CO2 content in the produced gas on the oil recovery were studied through slim-tube
experiments by Chen et al. (2013) and Yin et al. (2014). In their papers, displacement efficiency increased
almost linearly with the increasing CO2 content in the produced gas and with increasing displacement
pressure under immiscible conditions. In addition, the effects of gas composition on the measured MMP
and first-contact miscibility pressure were studied by Gu et al. (2013) using the vanishing interfacial
tension (VIT) technique. They suggested that pure CO2 could be added into the produced gas (CO2 ⫹
HCs) so that the reinjected produced gas was miscible or at least near-miscible with the reservoir oil under
the reservoir conditions. Oppositely, the effects of hydrocarbon gas, which was as impurity, on the CO2
flooding were also studied. The MMP in CO2 flooding could increase unfavourablely as the CH4
concentration increased in the CO2 stream, and could decrease as the C2 and/or C3 concertration increased
in the CO2 stream. Alston et al. (1983), Dong et al. (1999) and Zhang et al. (2004) achieved the above
similar conclusion by using different methods. Addditonally, a promising correlation had been developed
that can be used to predict miscible residual oil saturation, Sorm, for a wide range of injected gases, and
pressure conditions. The correlation can be used to predict roughly the effects of changes in pressure, or
injected gas composition on residual oil saturation. At the same time, a new method to predict MMP based
on the solubility parameter concept was also described. (Lange, 1996)
The effects of H2S, which was as impurity, on the CO2 flooding were also studied. The MMP in CO2
flooding could decrease as the H2S concertration increased in the CO2 stream (Alston et al., 1983).
Morevover, H2S was generally more effective than either CO2 or CO2-H2S mixtures in displacing oil from
a linear sand pack. Utilizing a light synthetic oil, miscible displacement was apparently achieved at lower
pressures with H2S than with CO2. And also, H2S was substantially more effective than CO2 in displacing
the viscous oil. Last but not the least, H2S could be employed as the displacing fluid after gas
breakthrough because oil recovery at this time was greater. (Harvey et al., 1977)
However, in some fields, injected gas is from the produced gas with large amounts of acid gas. The
corresponding EOR effects of this hydrocarbon gas with high acid gas content (especially H2S) are rarely
mentioned in the literatures. Thus it is necessary to study it.
From the above literature reviews on the hydrocarbon gas flooding, the similar experiments and
analysis methods were borrowed and applied to evaluate the effects of acid gas on enhanced oil recovery
in hydrocarbon gas injection. In this paper, an oil sample of typical block in K oil field is selected. Slim-
tube experiments are applied to determine the MMPs and measure the displacement efficiency of the crude
oil-hydrocarbon gas (containing acid gas) system at different experimental conditions.

Experimental Section
This experiment is directed towards the laboratory evaluation of the performance on enhanced oil recovery
with the mixed gases under different experimental conditions.

Experimental Apparatus
The major component of the experimental apparatus for the slim tube experiments which is shown in Fig.1
is a long (20m) coiled slim tube packed with proper packing materials (e.g., the quartz sands or glass
beads).
4 SPE-180434-MS

Figure 1—The schematic of slim-tube experiment

Materials
The compositional analysis result of the crude oil is given in Table 1. The experimental gas
composition is listed in Table 2. Table 3 shows the physical properties of the crude oil in K oil reservoir.
The injected gases which is shown in Table 4 are used in the slim-tube experiments.

Table 1—The compositional analysis result of the crude oil

Cn Mole fraction Cn Mole fraction

N2 0.0142 C15 0.0071

C1 0.5938 C16 0.0055
C2 0.0902 C17 0.0046
C3 0.0546 C18 0.0042
iC4 0.0106 C19 0.0038
nC4 0.0238 C20 0.0032
iC5 0.0110 C21 0.0027
nC5 0.0108 C22 0.0025
C6 0.0156 C23 0.0021
C7 0.0202 C24 0.0018
C8 0.0232 C25 0.0016
C9 0.0203 C26 0.0014
C10 0.0164 C27 0.0012
C11 0.0129 C28 0.0011
C12 0.0103 C29 0.0010
C13 0.0096 C30⫹ 0.0111
C14 0.0076 total 1.0000
SPE-180434-MS 5

Table 2—The experimental gas composition

Cn Hydrocarbon gas mole fraction Acid gas mole fraction

H2S 0 0.7811
CO2 0 0.2189
N2 0.0177 0
C1 0.7408 0
C2 0.1121 0
C3 0.0669 0
iC4 0.0124 0
nC4 0.0267 0
iC5 0.0101 0
nC5 0.0084 0
C6 0.0041 0
C7 0.0008 0
total 1.0000 1.0000

Table 3—Physical properties of crude oil

Parameters Amounts Units

Reservoir condition Pressure 42.4 MPa

Temperature 97 °C
Fluid properties Saturation pressure 28.4 MPa
Gas-oil ratio 619.9 m3/m3
Volume coefficient of the oil 2.937 m3/m3
Oil density(Reservoir condition) 0.547 g/cm3
Oil viscosity(Reservoir condition) 0.18 cp

Table 4 —The mixed gases with different percentages of acid gas and hydrocarbon gas
(1-n)HGⴙ nAG Gas 1 Gas 2 Gas 3 Gas 4 Gas 5 Gas 6

N 0% 10% 20% 30% 40% 50%

Note: n — acid gas content

Procedure
Slim tube filled with the crude oil is displaced by the injected gas under different experimental
conditions. Displacement efficiency of the mixed gases after 1.2 pore volumes gas injection or when there
is no oil production under different displacement pressures is measured in the experiments. Slim-tube
experiments were conducted according to SY/T6573-2003 (China National Standard).
Results and discussions
Slim-tube experiments for reservoir fluid with six different mixed gases were conducted under different
displacement pressures, and the ultimate oil recovery was considered to be the displacement efficiency.
Results indicate that MMPs of the crude oil-hydrocarbon gas-acid gas system are about 36.3 MPa, 32.1
MPa, 28.4 MPa, 25.1MPa, 22.3MPa, and 19.7MPa when the percentages of acid gas are 0%, 10%, 20%,
30%, 40%, and 50% respectively.
Minimum Miscibility pressure
Miscible gas flooding is widely employed for enhancing oil recovery for many oil reservoirs. A key
parameter used for assessing the applicability of the process for a reservoir is the MMP. Therefore,
obtained the MMP for oil reservoir with injecting the mixed gases containing acid gas is of utmost
necessary.
6 SPE-180434-MS

The MMPs are all measured by slim-tube experiments with six different mixed gases at reservoir
temperature. The process of achieved the MMPs is shown in Fig.2. Through the comparison of the six
graphs in the Fig.2, we can found that the blue dotted line moves close to the vertical axis gradually as
the percentage of acid gas increases. That is, the MMP drops with the increase of acid gas content. This
conclusion also can be demonstrated in Table 5. The mechanism of mass transfer between the crude oil
and acid gas especially H2S can account for this point.

Figure 2—Measured the MMPs with different acid gas content under different displacement pressures
SPE-180434-MS 7

Table 5—Measured the MMPs with different acid gas content

Acid gas content (%) 0 10 20 30 40 50
MMP (MPa) 36.3 32.1 28.4 25.1 22.3 19.7

Fig.3 shows the curves of the MMPs and acid gas content for hydrocarbon gas flooding (97°C), which
perfectly confirms linear relationship. And the correlation coefficients is over 0.99.

Figure 3—MMPs with different acid gas contents

Therefore, to reduce the MMP in hydrocarbon gas injection, fully burning some hydrocarbon gas or
mixed with some acid gas especially H2S in hydrocarbon gas to some extent is helpful.
Displacement Efficiency
When the hydrocarbon gas containing acid gas is injected into the reservoir, there is a beneficial mass
transfer between the mixed gases and crude oil. Before gas breakthrough, the production gases are the
solution gas of reservoir oil; and then after gas breakthrough acid gas would be produced along with the
solution gases. A combined condensing/vaporizing-gas drive mechanism must be responsible for the EOR
process of hydrocarbon gas with the crude oil in the displacement. During this process, displacement
pressure and acid gas content are two important factors affecting displacement efficiency.
Displacement Efficiency Versus Displacement Pressure Fig.4 shows the comparisons of displacement
efficiency and injection volumes of different acid gas contents under different displacement pressures.
Obviously, the higher the displacement pressure, the higher the displacement efficiency and the later the
gases breakthrough. However, for the same injection volume after gas breakthrough, when displacement
pressure is larger than MMP, the larger the displacement pressure, the less the increase trend of the
displacement efficiency; when displacement pressure is less than MMP, the increase trend of the ultimate
displacement efficiency becomes stronger with the increase of displacement pressure. Comparisons of six
figures in Fig.4, we can see that the displacement efficiency increases as the percentage of acid gas
increases when the displacement pressure is constant. From another angle to analyze the Fig.4, the residual
oil saturation also can be measured. And also the laws of changes in displacement pressure, or injected
gas composition on the residual oil saturation are predicted and opposite to the laws of the displacement
efficiency. Hence, a new MMP correlation based on the solubility parameter concept can also be derived.
(Lange, 1996)
8 SPE-180434-MS

Figure 4 —Comparisons of displacement efficiency at different conditions

Displacement Efficiency Versus Acid Gas Content Fig.5 shows the relationships of displacement ef-
ficiency and displacement pressure for the hydrocarbon gas flooding (97 °C). From the Fig.5a), the
displacement efficiency increases as displacement pressure increases when the acid gas content is
SPE-180434-MS 9

constant. From the Fig.5b), the displacement efficiency and displacement pressure perfectly confirms
linear relationship when the displacement pressure is less than MMP. When the percentages of acid gas
of the hydrocarbon gas are 20%, and 40%, the correlation coefficients are all over 0.99. Meanwhile, the
slope of these two curves increases as the acid gas content in the mixed gases increases. Similarly, the
experiments with injecting the mixed gases with the other acid gas content are also conducted. Law is the
same.

Figure 5—Displacement efficiency versus Displacement pressure

Fig.6 shows the relationships of displacement efficiency and the percentages of acid gas when the
displacement pressure is constant (97°C). From the Fig.6a), when the displacement pressure is constant,
displacement efficiency increases as the acid gas content increases. From the Fig.6b), the displacement
efficiency and acid gas content confirms linear relationship before achieving the miscibility. When the
displacement pressure is 20MPa, and 25MPa, the correlation coefficients are all over 0.97. Meanwhile, the
slope of these two curves increases as the displacement pressure increases. Similarly, the experiments with
injecting the mixed gases with the other acid gas content are also conducted. Law is the same.

Figure 6 —Displacement efficiency versus Acid gas content

10 SPE-180434-MS

Therefore, when the hydrocarbon gas contains acid gas or the produced gas contains acid gas, the
mixed gases can directly inject into the oil reservoir without separating the acid gas. This not only can save
the processing costs but also reduce the amount of pollution to the environment; and not only can make
acid gas storage cometure but also enhance displacement efficiency more effectively. Furthermore, to
prevent significant displacement efficiency declination, at the same time of the mixed gas injection,
enhancing displacement pressure and acid gas content within a certain range are a good choice.

Conclusions
In this article, slim-tube experiments were conducted under different displacement pressures using the
mixed gases with different acid gas contents.
MMP has been predicted when the mixed gases were injected into the crude oil. With the increase of
acid gas content, the MMP decreases. In hydrocarbon gas flooding, when the MMP is larger than the
formation pressure or the displacement pressure cannot meet the requirement, fully burning some
hydrocarbon gas or mixed with some acid gas especially H2S in hydrocarbon gas to some extent are very
useful.
The displacement efficiency increases with the increase of acid gas content in the mixed gases when
the displacement pressure is constant. Similarly, the displacement efficiency increases with the increase
of displacement pressure when the percentage of acid gas in mixed gas is constant. Besides, the higher the
displacement pressure, the later the gas breakthrough. Meanwhile, displacement pressure and acid gas
content are two important factors to displacement efficiency. The experimental data indicates that the
displacement efficiency increases linearly with them. Consequently, during the production process, after
gas breakthrough, enhancing displacement pressure in the permitted range or mixed with some acid gas
especially H2S in hydrocarbon gas are a good approach to prevent displacement efficiency declination.
This study can open possibilities for future hydrocarbon gas flooding when hydrocarbon gas contains
different acid gas content to improve miscibility and recovery of oil. This work also provides a new
perspective on enhancing oil recovery as well as cutting the pollution of acid gas, it is very meaningful.

Acknowledgements
We are grateful to the all the people for improving the manuscript. This work is supported by National
Basic Research 973 Program of China (2015CB250905).

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12 SPE-180434-MS

Appendix
For the acid gas in the experiments has the characteristic of strong corrosive, the materials of all
equipment using in slim-tube experiments must be Hastelloy. In addition, owing to the highly toxic of
H2S, experimenter need wear a gas mask, and also laboratory should keep ventilated at the same time.