SPE 139703

CO2 and C1 Gas Injection for Enhanced Oil Recovery in

Fractured Reservoirs
H.Karimaie, SPE and O. Torster, SPE, Norwegian University of Science and Technology
(NTNU)

Copyright 2010, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE International Conference on CO2 Capture, Storage, and Utilization held in New Orleans, Louisiana, USA, 1012
November 2010.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
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Abstract

The purpose of the experiments described in this paper is to investigate the efficiency of
oil recovery by CO2 and C1 in fractured carbonate rock after tertiary gravity drainage in
reservoir condition. Samples with different type of wettability have been selected and
tertiary gas injection experiments were performed on 20 cm long and low permeable
outcrop core surrounded with a fracture established with a novel experimental set-up. A
mixture of live oil (C1- C7) with a known composition has been selected and PVT
properties of the sample such as density, bubble point pressure, interfacial tension
between the phases were measured in reservoir condition prior to experiment. The matrix
block was saturated using the live oil, while the fracture was filled with a sealing material
to obtain a homogeneous saturation. The sealing material was then melted and removed
by increasing the temperature which in turn creates the fracture surrounding the core.
Water was injected into the fracture at pressure above the bubble point to measure oil
recovery by imbibition. After reaching to final oil recovery equilibrium gas was injected
to the fracture in two successive stages where interfacial tension was reduced from 0.37
mN/m to 0.15 mN/m in order to measure oil recovery by gravity drainage. Non-
equilibrium gas (CO2 and C1) were then injected in the last part of the experiment to
study the effect of composition on final oil recovery. Results from tertiary gas injection
experiments show that additional oil recovery could be obtained by injection of non-
equilibrium gas, where diffusion and gravity drainage were the main elements of the
displacement mechanism. Results also reveal that CO2 injection is a very efficient
recovery method while injection of C1 can also improve the oil recovery.
2 SPE 139703

Introduction

Gas injection is an efficient improve oil recovery (IOR) method increasingly applied as a
secondary or tertiary oil recovery scheme, especially for fractured reservoirs. It has been
reported that large amount of oil may be trapped in fractured reservoirs due to capillary
forces and gas injection could be an efficient recovery method for such reservoirs. In this
case, gravity drainage is a mechanism that would help to recover the oil. A matrix block
surrounded by gas, will undergo a gravity drainage process when the gravitational forces
exceed the capillary forces. The density difference between the gas in the fracture and the
oil in the matrix is the main driving force, which is counteracted by the matrix capillary
pressure. In this process, recovery rate is characterized by an initial period of a constant
maximum rate, with gradually decline toward zero.
Very few laboratory works describing the flow mechanism taking place in gas injection
has been published. Cardwell and Parson (1) were the first researchers to describe the
concept of gas injection theoretically. Dumore and Schols (2) reported low residual oil
saturation of 5% in high permeability sandstone subjected to gravity drainage. Hagoort (3)
found that gravity drainage could be a very effective oil recovery process and reported
several measured recovery-time curves for different core samples using a centrifuge. He
also proposed a new method for calculating oil relative permeability in gravity drainage
process. Firoozabadi et al. (4) performed several experiments for a variety of samples
using centrifuge. The samples were saturated with water and then displaced with pure
heptane in their experiments. The measured early points of the recovery curves are
somewhat below the values expected in their experiment. The experiments have been
simulated by Firoozabadi and Aziz (5) using a least squares technique and varying the
Corey exponent n.
Thiebot and Sakthikumar (6) performed gas-oil gravity drainage experiments under
reservoir conditions in fractured system using cylindrical cores having both lateral and
horizontal faces open to flow. They used a permeable limestone (60 mD) with a 40 cm
length and equilibrium gas was injected to the system at 18.3 MPa and 132 C . They also
modified the core holder in order to allow a removable lateral coating around the core.
This coating was used during initial saturation of the sample and removed before gas
injection, creating a fracture or a dead volume full of reservoir oil around the core.
However, they did not mention about the type of lateral coating and the methodology
which was used for the purpose. The experiments were simulated using a fully
compositional single porosity simulator.
Sajjadian et al. (7) performed laboratory studies of gravity drainage in fractured rock
investigating the effect of capillary continuity and re-infiltration. Irrespective of their
results, experimentation in atmospheric conditions using synthetic oil and air as test fluids
was the weakness of their laboratory work.
However, performance of gravity drainage is limited by threshold height and matrix
block size. This is the case in the low permeability chalks of the North Sea implying that
gravity drainage may not be an efficient recovery mechanism. In this case, if the reservoir
pressure is increased and a non-equilibrium gas is injected to the reservoir, oil recovery
will increase. Among different types of dry gas, CO2 has a strong attraction to oil and is
very effective for displacing oil from a matrix block. CO2 could offer a good opportunity
to recover the remaining oil in the final (tertiary) phase of reservoir. Holm and Josendal
SPE 139703 3

(8)
found that CO2 has a great depth of vaporization and extraction of hydrocarbons from
crude oil. It can extract the heavier components (C6-C30) and can be miscible with crude
oils that have little C2-C6 components. This feature makes the CO2 injection applicable to
many reservoirs which are no longer suitable for lean gas injection, but they can still be a
good candidate for secondary and tertiary CO2 injection.

Very few laboratory works describing the flow mechanism taking place in CO2 injection
has been published. Li et al. (9) performed CO2 injection experiment on artificially
fractured core after waterflooding in a dead-oil system. Gravity drainage was the
dominant recovery mechanism in these tests, with significant tertiary oil recovery after
water flooding. According to their results, efficiency of CO2 gravity drainage declines as
the rock compressibility deceases and initial water saturation increases. Hujun et al. (10)
investigated CO2 gravity drainage in artificially fractured core using dead oil at the
reservoir temperature of 58.9 oC and concluded that CO2 gravity drainage could
significantly enhance oil recovery after waterflooding in the naturally fractured Spraberry
Trend Area. In their experiment artificial fracture was defined as the gap between two
pieces of the core. Most recently Dravish et al. (11) performed CO2 injection experiments
at reservoir conditions concluding that diffusion effect could be the main recovery
mechanism during CO2 injection.

Lean gas injection is also an attractive recovery option. Saidi (12) confirmed that lean gas
injection is also capable of mobilization of residual oil after waterflooding in fractured
reservoirs. Morel et al. (13) experimentally studied the combined effect of gas diffusion
and stripping in the matrix blocks of light oil fractured reservoirs subjected to methane or
nitrogen gas flooding. They concluded oil recovery was about twice as fast with methane
as with nitrogen. Le Romancer (14) performed similar experiments in 1-D conditions on a
chalk core in the presence of different water saturation. The saturation profile in their
experiment showed a strong capillary end effect for nitrogen injection with an
accumulation of oil near the fracture.

However, very few laboratory works on CO2 and C1 gas injection on fractured rock
samples using live oil have been reported in the past and as can be seen, the bulk of the
experimental studies on gas injection were performed using dead (synthetic) oil in
atmospheric condition which is usually not related to reservoir condition. Therefore the
scarcity of experimental data and difficulty encountered in obtaining such data, have
made laboratory work at reservoir conditions attractive for this process.
In this paper results of experiments to investigate the effect of type of gas on oil recovery
in a fractured rock subjected to water flooding are reported. The present work was begun
by water injection followed by equilibrium gas injection in samples having different
wettability state. After doing carefully conducted gravity drainage tests and obtaining the
final recovery, non-equilibrium gas; i.e. CO2 and / or C1 was injected to the system to
understand the compositional effect. The aim of the investigation is to quantify the effect
of type of gas on oil recovery in fractured media at high pressure, high temperature
conditions.
4 SPE 139703

Fluid and rock properties

Experimental studies have been carried out on Faxe outcrop which has similar rock
properties to the North Sea chalk as a representative of a water-wet rock and Asmari
limestone as a representative of a mix-wet sample with low permeability. However in
order to make sure the wettability state of the samples, some preliminary experiments
have been performed on Asmari limestone samples (15). Three plugs were prepared from
the long cores used in gas injection experiments and the results from the plug analyses
were used to understand the large scale behavior. Table 1 represents the physical
properties of the samples. The core plugs, having a diameter of 3.7 cm and length of 4-5
cm, were cleaned by use of methanol and toluene. All cleaned samples were placed in an
oven at a temperature of 120 oC for 48 h. A helium porosimeter and an air permeameter
were used for porosity and absolute permeability measurements. The selected samples
were limestone (grainstone packstone) with abundant coralline algae and 15-20%
porosity (Figure 1). The left-hand picture shows moldic and vuggy porosity (blue);
sparitic calcite cement is shown as white color. The right-hand picture depicts a dark
coating around some of the larger fossil grains, possibly organic material indicating early
oil-staining which later has been partly replaced by pyrite. This coating might be the
reason for the observed weak water wettability of the samples.

Amott wettability tests were performed on the plug samples to determine the water
wettability index. After achieving Swi the samples were submerged in brine for 2 months
and the amount of produced oil was recorded versus time. The samples were centrifuged
under brine for measuring the oil extraction under forced brine displacement. The end
point oil recovery by spontaneous imbibition and forced water displacement was used to
calculate the Amott index to water. Results are shown in Table 1. It is clear that the
samples are showing slightly water-wet behavior. No spontaneous uptake of oil was
observed at residual oil saturation.
Drainage and imbibition capillary pressure were obtained by the centrifuge method. The
cores were saturated with brine and rotated in the centrifuge while they were surrounded
by the non-wetting phase (n-decane) at increasing speeds. The cores were then removed
and submerged in brine for at least 20 days. The amount of spontaneously produced oil
was recorded. In order to obtain the negative capillary pressure curve, the cores were
rotated in the centrifuge while surrounded by water at increasing speed. Capillary
pressure and saturation were determined and corrected by the Hassler-Brunner (16) method
in each step.

Imbibition relative permeability was measured by the unsteady state method under
constant differential pressure (15 bara). Initially the cores were 100 % saturated with
brine and absolute permeability was measured. The cores were oil flooded to reach
connate water saturation, after which, oil was displaced by brine until no more oil
production was observed. Relative permeability was calculated using the Jones-Roszelle
(17)
graphical technique. S w is equal to 0.55 at krw=kro which confirms the Amott test
results regarding the wettability state of the sample which is slightly water-wet. The
capillary pressure and relative permeability curves are shown in Fig. 2.
SPE 139703 5

The porous medium used in gas injection experiments were cylindrical core sample of
Chalk and Asmari limestone with a length of around 20.0 cm and 3.8 cm in diameter.
Table 2 provides an overview of the core samples properties.

All gas injection tests were performed with synthetic binary mixture as live oil,
equilibrium and non-equilibrium gas as gas phase. Equilibrated gas was used as an
injection gas while CO2 and C1 were used at the final stages of the experiment as non-
equilibrium gas. The fluid used in all experiments was a binary mixture of C1 and C7. We
chose to use such a binary system of hydrocarbon fluids because the thermodynamic
properties are well known. Interfacial tension between the phases, oil formation volume
factor, phase densities, phase volumes at different pressures and bubble point pressure
were the parameters measured experimentally. However, the published experimental data
by Reamer et al. (18) is also used to verify and predict some other parameters. These PVT
data are necessary to tune the EOS model to produce the accurate and reliable results.

Constant composition expansion experiment was performed at constant temperature 85

o
C shown in Figure 3. As clearly observed the bubble point of the mixture is around
229.5 bar at 85 oC. Phase densities and oil formation volume factor were also measured at
three different pressures close to bubble point. Tables 3 and 4 summarizes the properties
of the system C1-nC7 at 85 oC.

Tuning of Equation of State (EOS) model

Laboratory data were used to tune the phase behavior model prior to gas injection tests.
Critical pressure, temperature and bubble point pressure at some certain temperature and
different C1 mole% are known (18). Regressions have been done based on available data to
find the properties at desired temperature and C1 mole%. The critical point and bubble
point data have been simulated to obtain the properties at different pressures and
temperatures. Results are given in Figures 4 and 5.

Tuning of the EOS model was done using a PVT simulator. The Soave-Redlich-Kwong
(SRK) equation of state (19) with temperature dependent Peneloux Volume correction (20)
was used as the equation of state. Five model parameters were tuned: the critical
pressures and temperatures of methane and n-heptane and the interaction coefficient kij.
Results for the phase behavior of the system using tuned and non-tuned EOS model is
given in Figure 6. Results show that tuning is essential for attaining the correct phase
behavior.

IFT Measurements

Interfacial tension between the phases was measured by pendant drop method which is
based on injecting a drop of heptane into the equilibrated gas phase. Figure 7 shows
typical drop shape at three experimental pressures. In such a system consisting of two
pure components (no surfactants), a relatively small drop of heptane could be expected to
equilibrate with the surrounding gas phase in short time. The IFT value was calculated
6 SPE 139703

from the density difference between the coexistent phases, the drop size, and the full
contour of the drop.

Measured IFT values at 85 oC are presented in Figure 8 in which simulated data are
included for comparison. The simulated IFT data were calculated using the procedure of
Weinaug and Katz (1943) (21) which requires the following input: the Parachor of the pure
components, which are constants, the molar density of the equilibrium phases and the
molar composition of the phases. The molar density and composition of the phases were
established by PVT simulator. The broken line in Figure 8 shows simulated IFTs for the
mixture, based on non-tuned SRK Peneloux EOS. The curve shape does not fit the
measured data points because the simulation overestimates the bubble point pressure and
the critical temperature of the system. The solid line represents the simulation after tuning
the equation of state to experimental data. The tuning is seen to be essential for attaining
a better fit to the measured IFT data.
The simulated IFT curve in Figure 8 obtained by use of the tuned EOS model can be
expressed by the relationship:

IFT = 0.0005 p 2 0.244 p + 28.834 (1)

Where the IFT takes units of mN/m for pressure values, p, entered in units of bara. This
relationship can be used for interpolation between the measured IFT values and probably
also for extrapolation towards the bubble point pressure.

Description of equipment and experimental procedure

A diagram of the experimental equipment is given in Figure 9. It was designed for water
and gas injection in fractured porous media under high pressure and temperature.
Initializing the sample with live oil and maintaining the pressure to prevent compositional
change, is very important and a difficult issue in gas injection projects. The normal
procedure for saturating the core can not be used for a fractured system due to large
permeability differences between matrix and fracture. Oil would flow through the high
permeable fracture leaving the core incompletely saturated with the live oil. To overcome
this problem, a method for initialization of the core with live oil has been developed to
ensure the homogeneous saturation of the core plug (22). A unique feature of the apparatus
used in gas injection experiments, was the capability for initializing the sample with live
oil while it is surrounded with fracture.

The dried core was placed into a steel tube having a diameter of 42 mm, and the core was
centralized inside. A 2 mm gap between the core and tube is simulating the fracture
space. The fracture between the sample and tube was filled with a meltable alloy (melting
temperature=70 oC) which is able to coat the core and fill the fracture space between the
core and tube without having any effect on the surface area of the core and fluid (11). The
alloy was poured under high temperature (120 oC) into the annular space between the
core and tube. After cooling, the artificial fracture filled with sealing material had zero
permeability and permeability measurements confirmed the core to hold its initial
permeability of 5 mD.
SPE 139703 7

The steel tube and core were assembled into a core holder. The porous medium contained
no initial water and all displacement tests were vertical and downward. The core was
evacuated and saturated with dead C7 and the pore volume of the core was measured. The
absolute permeability of the sample was measured by injecting the oil at several injection
rates while measuring the pressure difference between the top and bottom of the sample.
The differential pressure through the core sample was measured by a sensitive differential
pressure transducer. The whole system was then pressurized and live oil injected to the
core at a rate of 0.1 cm3/min whilst pressure was kept constant above the bubble point
pressure, using a back pressure regulator. Three pore volumes of live oil were injected to
ensure the saturation of the sample.

After core initialization, the system was heated to 85 oC at a constant pressure. At this
condition the sealing material was melted and displaced from the fracture by live oil and
drained from the bottom of the core using a specially designed end cap. This process
leads to the creation of the fracture surrounding the cylindrical core, fully saturated with
the mixture. In the final step, oil in the fracture was displaced by water and then gas in
tertiary experiments.

Special attention was given to the fluid production. The production was flashed directly
to atmospheric pressure via a backpressure regulator and fed into a separator. The
standard volumes of liquid and gas obtained were measured after passing two step
condensers at a constant temperature of 5 oC and -4 oC respectively to condense any heavy
hydrocarbons that may have been carried along with it. The gas volume is measured by a
wet test meter kept at constant temperature and pressure (25 oC, 1bar).

Totally four experiments have been performed on water wet chalk and mix wet
limestone. All experiments consisted of four stages:

Water injection at a pressure above the bubble point

Injection of equilibrium gas at 210 bar (IFT=0.37 mN/m)
Re-pressurization to 220 bar (IFT=0.15 mN/m)
CO2 and/or C1 injection at the final stage

A summary of the experiments can be found in Table 5.

The experimental procedure was the same for all experiments as described earlier. After
mounting the core and fracture system into the modified core holder, permeability of the
sample was measured by passing 3 pore volumes C7. After that, core was initialized using
the live oil at a pressure above the bubble point. After removing the sealing material from
the fracture, by injection of live oil, synthetic brine (3 % NaCl), with the density of 1.03
g/cm3 and viscosity of 1.07 mPas, was quickly injected into the bottom of the system at a
rate of 5 cm3/min, while pressure was kept constant above the bubble point pressure.
Injection rate was then decreased to 1 cm3/min and continued for 1-2 days, to attain
ultimate oil recovery. Spontaneous imbibition of water was then measured at high
pressure and temperature. This mechanism, mostly affected by water imbibition and
gravity driven forced imbibition into the matrix block, leads to residual oil saturation.
8 SPE 139703

Thereafter equilibrium gas at 210 bar (IFT= 0.37 mN/m) was injected at high rate (5
cm3/min) from the top of the system to drain all the water in the fracture very quickly.
The rate was then decreased to 0.1 cm3/min. The process was continued until reaching to
the ultimate recovery. The system was re-pressurized to 220 bar (IFT= 0.15 mN/m) to
study the effect of IFT reduction on recovery. In the final stage, non-equilibrium gas such
as CO2 and C1 were injected to the system to recover the remaining oil.

Experimental Results and Discussion

Experiments 1 & 2-Tertiary Gas Injection in Water Wet Chalk

The first experiment was started by initializing the core with live oil as described.
Afterwards, water injection has been performed and spontaneous imbibition of water was
then measured at high pressure and high temperature until attaining the ultimate recovery.
Nearly 60% of oil was produced during water injection. Thereafter equilibrium gas was
injected in two successive stages where pressure was increased from 210 bar to 220 bar.
Around 13% and 6% of original oil in place was produced respectively and results are
given in Figure 10.
Normally when a matrix-fracture system is undergoing re-pressurization, some changes
in fluid properties may occur. Examples are as follows:

Gas density increases and oil density decreases due to more gas in solution which
in turn cause the change in density difference. The density difference changed
from 0.2325 to 0.1804 g/cm3 when the system was re-pressurized from 210 to 220
bar.
The interfacial tension between oil and gas decreases which in turn cause
reduction in capillary hold up. In this case especially when the interfacial tension
drops below 1 mN/m, the residual oil saturation above the new hold up zone will
also start to decrease.
The viscosity of the oil decreases and its formation volume factor increases.

Therefore in our experiment both swelling and reduction of interfacial tension could
cause a more efficient drainage and lower threshold could be achieved. When the
interfacial tension drops to a value of less than 1 mN/m, the reduction of residual oil
becomes important (23).

In the last stage, non-equilibrium gas (CO2) was injected to the matrix-fracture system to
attain more oil recovery. The density difference between CO2 and oil was calculated to be
0.2 g/ cm3 at 220 bar and 85 oC. The recovery in this experiment might be due to
swelling, diffusion and gravity drainage processes. However, the measured oil recovery is
plotted versus time in Figure 10 which shows that almost 6% of original oil in place was
produced during CO2 injection.

To understand the effect of component exchange more precisely, the second experiment
was run under the same condition using known hydrocarbons, in equilibrium and not in
equilibrium with each other. Methane was used as a non-equilibrium gas instead of CO2.
After initialization, water was injected from the bottom to the top of the core. Around
SPE 139703 9

58% oil was recovered during water injection. Equilibrium gas was then injected at 210
bar (IFT=0.37 mN/m) and oil started to produce. 16% of original oil in place was
recovered after 2 days experiment in which gravity drainage was the main recovery
mechanism during displacement. The matrix-fracture system was then re-pressurized to
220 bar (IFT=0.15 mN/m) which causes 5% additional oil recovery. Experimental results
are shown in Figure 11.
In order to investigate the effect of non-equilibrium gas injection on oil production, the
last part was accompanied with C1 injection. The density difference between C1 and oil in
the matrix was calculated to be 0.28 g/cm3 at the above pressure and temperature. The
results clearly show that lean gas injection offers a valuable oil recovery potential in
fractured chalk reservoirs. Recoveries from 79-83% of original oil in place have been
observed when injecting lean gas.

Results of the CO2 and C1 injection are also shown in Figure 12 for comparison. The
recovery may be due to one or a combination of three different effects: Gravity drainage,
swelling of oil and diffusion. Because of the nature of the apparatus, it was impossible to
distinguish between the three production mechanisms.

Experiments 3 & 4- Tertiary Gas Injection in Mix-Wet Chalk

It is a common belief that if a formation is preferentially oil-wet, the matrix will retain oil
by capillarity during waterflooding. This is the case for Asmari limestone which is the
main producing formation in southern part of Iran. The results of water injection
experiments indicated that oil recovery efficiency was quite low under atmospheric
condition. Full details of water injection experiments on this type of rock are given in
reference 15.

The long core consisted of 2 pieces cut from an Iranian Asmari limestone outcrop. Each
piece was carefully machine cut to 3.7 cm in diameter. They were cleaned with hot
toluene to dissolve possible precipitation of paraffin and wax in the pores. The cores were
dried in an oven at a temperature of about 180 oC. The measured average permeability
and porosity of the long core were respectively 15 mD and 22.3%. Two sets of
experiments were performed using a similar oil, gas and similar procedure as for the
outcrop chalk. Both experiments were started by initializing the sample with the same
mixture of C1-C7 with a bubble point pressure around 210 bar and using special alloy and
methodology described previously. Water injection tests were performed in both
experiments using 3% NaCl brine at pressure above the bubble point of the oil. Less than
8% of the original oil in place was produced.
The low oil recovery achieved by water injection in the first stage indicates the extents of
oil wetness of the Asmari matrix block due to a very low water imbibition.
Oil recovery based on original oil in place at different times for experiments 3 and 4 are
shown in Figures 13 and 14 respectively. More than 90% of original oil was left after
water injection, resulting in a very high potential for oil recovery by gas-oil gravity
drainage. System was then undergo to equilibrium gas injection at 210 bar (IFT= 0.37
mN/m) and re-pressurization to 220 bar (IFT=0.15 mN/m) to attain additional oil
recovery.
10 SPE 139703

The equilibrium gas injection continued until reaching to ultimate recovery.

Figures 13-14 shows significant oil recovery achieved during the two successive stages of
gravity drainage which is due to the low IFT gravity drainage. The ultimate recovery in
both experiments clearly indicates almost the same recovery efficiency under gravity
drainage. Based on the results of the experiments, it is confirmed that tertiary gas-oil
gravity drainage in Asmari limestone can be utilized for higher oil recovery.

The increase of oil recovery as the pressure increases could be attributed to two
processes, increase of oil formation volume factor ( Bo ), and a lower residual saturation
due to the reduction of gas-oil interfacial tension. Bardon and Langeron(23) also found a
decreasing residual oil saturation using C1-C7 mixtures at high pressures when measuring
gas oil relative permeability.

In the next step, the same procedure as described in Experiments 1 & 2 was employed for
mix-wet limestone matrix block. CO2 and C1 were injected to the matrix-fracture system
as a non-equilibrium gas in experiments 3 & 4 respectively. The fourth part of the
production curve in Figures 13 and 14 portrays the non-equilibrium gas injection stage.
To better evaluate the performance of the type of dry gas injected, the oil recovery
efficiency for the two experiments shown in Figure 15 were calculated based on original
oil in place. Compare to the CO2 injection experiment, lower oil recovery was noticed
during C1 injection which is in line with the results from outcrop chalk matrix block.

Conclusions

In this research a novel setup was designed to study the gas injection in fractured media
at reservoir conditions. Experiments performed on outcrop chalk and Asmari limestone
with a synthetic binary mixture of C1-C7 subjected to equilibrium gas injection into a
fractured media gave the following results:

1- Gas-oil gravity drainage at low interfacial tension was found to be a very effective oil
recovery method from mix-wet and water-wet fractured media.

2- Re-pressurization by gas injection resulted in higher oil recovery in both chalk and
Asmari limestone. Reduction of IFT is the key factor for increased oil recovery.

3- The study reveals that tertiary gas injection is capable of mobilizing waterflood
residual oil and thus reducing the residual oil saturation.

4- The tertiary oil recovery results in water-wet chalk sample suggest that a combination
of waterflooding followed by gas injection is very efficient while in the case of mix-wet
sample waterflooding prior to gas injection is not an efficient recovery process.

5- CO2 injection is a very efficient recovery method while C1 injection can also improve
the oil recovery
SPE 139703 11

Acknowledgment

We acknowledge the financial support provided by StatoilHydro. All PVT experiments in

this paper were performed at SINTEF petroleum research (23). We gratefully acknowledge
the help of all laboratory personnel.
Nomenclature
Bo= oil formation volume factor, rv/stc v
EOS= Equation of state
IFT= interfacial tension, mN/m
IOR= improved oil recovery
Pb= bubble point pressure, bar
OOIP=original oil in place

References
1. Cardwell, W.T. and Parson, L.L. Gravity Drainage Theory, AIME Trans. 1948, 174,
p.199.
2. Dumore, J.M. and Schols, R.S. Drainage Capillary Pressure Function and Influence of
Connate Water, SPEJ (October 1974), 437.
3. Hagoort, J. Oil Recovery by Gravity Drainage SPE paper, June 1980.
4. Firoozabadi, A., Soroosh, H. and Hassanpour, G. Drainage Performance and Capillary
Curve Utilizing a New Centrifuge Journal of Petroleum Technology (July 1988) 913-
919.
5. Firoozabadi, A. and Aziz, K. Relative Permeabilities from Centrifuge Data Journal
of Canadian Petroleum Technology (Sept.-Oct. 1991) 33-42.
6. Thiebot, B.M., and Sakthikumar, S.S., Cycling Fractured Reservoirs Containing
Volatile Oil: Laboratory Investigation of the Performance of Lean Gas or Nitrogen
Injection paper SPE 21427 presented at the SPE Middle East Oil Show held in
Bahrain, 16-19 November 1991.
7. Sajjadian, V.A., Danesh, A., and Tehrani, D.H. Laboratory study of Gravity Drainage
Mechanism in Fractured Carbonate Reservoir- Reinfiltration paper SPE 54003,
presented at the 1999 SPE Latin American and Caribbean Petroleum Engineering
Conference held in Caracas, Venezuela, 21-23 April 1999.
8. Holm, L.W. and Josendal, V.A.: Mechansim of Oil Displacement by Carbon Dioxide
J.Pet.Tech. (Dec. 1974) 1427.
9. Li, H., Putra,E., Schechter, D.S. and Grigg, R.B.2000. Experimental Investigation of
CO2 Gravity Drainage in a Fractured System. Paper SPE 64510 presented at the SPE
Asia Pacific Oil and Gas Conference and Exhibiiton, Brisbane, Australia, 16-18
October.
10. Hujun, L., Putra, E., Schechter, D. and Grigg, R. Experimental Investigation of CO2
Gravity Drainage in a Fractured System paper SPE 64510 presented at the SPE Asia
Pacific Oil and Gas Conference and Exhibition held in Brisbane, Australia, 16-18
October 2000.
11. Darvish, G.R, Lindeberg, E., Holt, T., and Utne, S.A.Laboratory Experiments of
Tertiary CO2 Injection into a Fractured Core paper SPE 99649 presented at the 2006
SPE/DOE Symposium on Improved Oil Recovery in Tulsa, Oklahoma, U.S.A., 22-26
April 2006.
12 SPE 139703

12. Saidi, A.M. Reservoir Engineering of Fractured Reservoirs Total Edition Press,
1987.
13. Morel, D.D., Bourbiaux B., Latil, M. and Thiebot, B. Diffusion effects in gas
flooded light oil fractured reservoirs, paper SPE 20516, presented at the 65th SPE fall
meeting, New Orleans, September 1990.
14. Le Romancer, J.F.X, Defives, D.F. and Fernandes, G. Mechansim of Oil Recovery
by Gas Diffusion in Fractured Reservoir in Presence of Water, paper SPE 27746
presented at the SPE/DOE ninth Symposium on Improved Oil Recovery held in Tulsa,
U.S.A., 17-20 April 1994.
15. Karimaie, H. and Torster, O. Effect of injection rate, initial water saturation and
gravity on water injection in slightly water-wet fractured porous media.
Journal of Petroleum Science and Engineering (JPSE) 58 (2007) 293-308.
16. Hassler G.L. and Brunner E. Measurement of Capillary Pressure in Small Core
Samples. AIME, Vol. 160, 1945, 114-123.
17. Jones, S.C. and Ruszelle, W.O. Graphical Techniques for Determining Relative
Permeability From Displacement Experiments, J.Pet. Tech. 1978 May 807-817.
18. Reamer, H.H., Sage, B.H., Lacey, W.N. Phase Equilibria in Hydrocarbon Systems.
Volumetric and phase behavior of methane-n-heptane system, Chem.Eng.Data, 1, 1956,
29-42
19. Soave, G. Equilibrium constants from a Modified Redlich-Kwong Equation of
state, Chem.Eng. Sci., 27-1972:1197-1203.
20. Peneloux, A., E. Rauzy., and R. Freze. A Consistent Correction for Redlich-Kwong-
Soave Volumes. Fluid Phase Equilibrium 1982, 8, 7 -27.
21. Weinaug, C.F. and Katz, D.L. Surface Tension of Methane-Propane Mixtures, Ind.
Eng. Chem., 35, 1943, 239-246.
22. H.Karimaie, G.R. Darvish, E. Lindeberg and O. Torster. Secondray and Tertiary
Gas Injection in Fractured Carbonate Rock SPE 107187. Presented in EAGE-SPE
EUROPEC Conference held in London June 2007.
23. Bardon, C., and Langeron, D.G. Influence of Very Low Interfacial Tensions on
Relative Permeability Paper SPERE October 1980. P 391-401.
 SPE 139703 13

Table 1: Rock properties and Amott indices for Asmari limestone samples (15)
Sample No. Permeability Porosity Displacement of oil by water
(md) (%)
Spontaneous Forced Amott water
production production index
3 3
Vosp (cm ) Vod (cm )
1 0.5 14.0 2.6 2.5 0.51
2 0.8 14.6 1.1 1.5 0.42
3 1.0 15.8 1.5 1.0 0.60

Table 2. Properties of porous media

Exp. Permeability Porosity Length Pore
No. (mD) % (cm) Volume
(cm3)
1 4.7 0.44 19.6 99.0
2 4.7 0.44 19.6 98.0
3 14.4 0.23 19.0 50.5
4 15.0 0.23 19.0 50.5

Table 3. Densities, oil formation volume factors and IFT

at different pressure and constant temperature (85 C )
Pressure Oil Gas density Bo IFT
(bara) Density (g/ cm3) rv/stc v mN/m
(g/ cm3)

220 0.407 0.223 2.28 0.15

210 0.433 0.198 2.1 0.374

200 0.452 0.178 1.98 0.686

Table 4. Composition (mole %) of oil and gas phase
Pressure Oil Phase Gas phase
(bar)
C1 C7 C1 C7

220 0.7034 0.2966 0.8825 0.1175

210 0.6690 0.3310 0.8967 0.1033

200 0.6375 0.3625 0.9073 0.0927

 14 SPE 139703

Table 5: Summary of the experiments

Water Equilibrium Equilibrium CO2 C1
Experiment Injection gas gas injection injection
injection at injection at
210 bar 220 bar
1- Outcrop Chalk ------

2- Outcrop Chalk -----

3-Asmari limestone ------

4-Asmari limestone -----

Figure 1.: Optical micrograph of Asmari limestone outcrops showing moldic and vuggy porosity (blue-left
(15)
one) and a dark coating around some of the larger fossil grains (right one) .

1 15

0.8 Drainage
krw 10
kro Imbibition
0.6
5
Pc (bar)
kr

0.4
0
0.2 0 0.2 0.4 0.6 0.8 1
-5
0
0 0.2 0.4 0.6 0.8 1 -10
Sw Sw

(15)
Figure 2: Typical capillary pressure and relative permeability curves for Asmari limestone .
 SPE 139703 15

250 300

240 250
P r e s s u r e (b a r)

200

Pressure (bar)
230
Pb 150 Tuned EOS Model
220 Non-Tuned EOS Model
100
210
50

200 0
0.96 0.98 1 1.02 1.04 1.06 -50 0 50 100 150 200 250
Relative volume Temperature,C

Figure 3: Pressure-volume plot of mixture at Figure 6. Phase behavior of the system based on
85 C . tuned and non-tuned EOS model for C1-C7 mixture.
300 300

250 250

200 200
Pressure, bara

Pc
150 Tc
150

100 100

50 50

0 0
0 0.2 0.4 0.6 0.8 1
C1, mole %
Figure 4. Critical point simulation of methane & Figure 7. Pendant drop of heptane rich phase
heptane system. surrounded by methane rich phase at 85 C from
left: 220 bara, 210 bara, and 200 bara.
1.0
236
Simulation based on SRK-
Peneloux EOS tunned to
234 0.8 experimental data
Bubble point pressure (bara)

Simulation based
232 on non-tuned SRK-
IFT, mN/m

0.6 Peneloux EOS

230
0.4
228
Measurement
226 0.2

224
0
222 190 200 210 220 230
40 60 80 100 120 Pressure, bara
Temperature (oC)

Figure 8. Interfacial tension between coexisting

Figure 5. Bubble point simulation of methane & phases in methane/heptane system measured at
heptane system. 85 C compared with simulated data.
 16 SPE 139703

13
4 Oven 1

Water
10 0,8 injection

Recovery, fraction of OOIP

6 7
2 3 Start of C1.
0,6 Repressurization injection
12 to 220 bar
9 Gas injection
11 0,4 at 210 bar
5
0,2
1

8 0
0 2 4 6 8 10 12
Time (day)
Figure 9- Schematic of apparatus. Figure 11. Production as a function of time (Exp.
1- Quizix pump.
2). Tertiary gas injection into water-wet sample,
followed by C1 injection.
2,3-Isolated cells for oil and gas.
4- Isolated constant temperature tube for transferring the oil 0,07

and gas. 0,06

Recovery, fraction of OOIP
5- Pressure transmitter.
0,05
6-Steel tube containing matrix and fracture.
0,04
7- By-pass system.
8- Sealing material accumulator. 0,03 C1 injection
CO2 injection
9-Back pressure regulator. 0,02
10- Condenser.
0,01
11- Separator.
12-Gas wet test meter. 0
0 1 2 3 4
13- Gas chromatograph. Time (day)

Fig.12.Comparison between CO2 and C1 in the

last stage of the experiments on water-wet chalk.
1
1
Water
Recovery, fraction of OOIP

0,8 injection Start of CO2

0.8
Recovery, fraction of OOIP

Injection

0,6 Start of CO2 0.6

Repressurization injection
0,4 Gas injection to 220 bar Re-pressurization
at 210 bar 0.4 Water to 220 bar
Injection
0,2 Gas injection
0.2 at 210 bar

0
0
0 1 2 3 4 5 6 7
Time (day) 0 1 2 Time (day) 3 4 5

Fig.13. Production as a function of time (Exp. 3).

Fig.10. Production as a function of time (Exp.
Tertiary gas injection into mix wet sample followed
1). Tertiary gas injection into water-wet sample
by CO2 injection.
followed by CO2 injection.
 SPE 139703 17

1 0,18
0,16
Recovery, fraction of OOIP

0,8 Start of C1 0,14

Recovery, fraction
Injection 0,12
0,6
0,1
0,08 C1 injection
0,4 CO2 injection
Re-pressurization 0,06
Water
to 220 bar
Injection 0,04
0,2
Gas injection at 0,02
210 bar
0
0
0 0,2 0,4 0,6 0,8 1 1,2
0 1 2 3 4 5 6 Time (day)
Time (day)

Figure 14. Production as a function of time Figure 15.Comparison between CO2 and C1
(Exp. 4). Tertiary gas injection into mix wet injection in mixed-wet limestone
sample followed by C1 injection.