energies

Article
Miscible CO2 Flooding for EOR in the Presence of
Natural Gas Components in Displacing and
Displaced Fluids
Aly A Hamouda * and Sidra Chughtai
Department of Energy and Petroleum Engineering, University of Stavanger, 4036 Stavanger, Norway;
sidrachughtai20@gmail.com
* Correspondence: aly.hamouda@uis.no; Tel.: +47-9570-2604

Received: 1 December 2017; Accepted: 5 February 2018; Published: 8 February 2018

Abstract: Carbon dioxide (CO2 ) flooding is a complicated process as it involves phase behavior.
The objective of this work was to understand the mass transfer mechanisms during flooding with CO2
and CO2 /C1/C3 (CO2 /HC) based on experimental and simulated composition changes. Three model
oil compositions were used (n-C10, n-C10/C1, and n-C10/C1/C3). For a comparison, crude oil from
a North Sea field was included. The second part of the investigation was to compare the effect of the
combined light components (C1/C3) with CO2 as a displacing fluid on enhanced oil recovery (EOR).
Equation of State EOS SRK–Peneloux was used for the simulations to predict composition changes.
The highest recovery was obtained from model oil (n-C10) displaced with CO2 compared to model
oil containing light components with the highest recovery recorded from model oil/C1 (live oil A)
compared to model oil/C1/C3 at all of the tested temperatures. The presence of light components
(C1/C3) in the injected CO2 at miscible conditions increased the oil recovery for crude oil compared
to flooding only with CO2 . Transverse dispersion of CO2 helps in eliminating/reducing the effect
of viscous instabilities by shortening fingering travel/widening the fingers. The collected samples
contained water, although the flooding was done on dry sandstone cores. Possible mechanisms are
discussed in a later section.

Keywords: CO2 flooding; enhanced oil recovery (EOR); effect of light components; sandstone;
supercritical CO2 ; water extraction by Super critical CO2 (ScCO2 )

1. Introduction
Most of the mature fields are approaching tail production/declining phase. This decline has
inclined researchers towards opting for enhanced oil recovery (EOR). CO2 flooding, which lies in
both secondary and tertiary recovery stages, is considered a promising EOR technique. Patents and
papers by Beeson and Ortloff [1], Holm and Josendal [2], and Holm [3] have laid the foundation of
the CO2 oil recovery processes. Initially, when the EOR method was introduced, immiscible flooding
was under discussion as an alternative water-based EOR process. The increased application of CO2
for EOR demonstrates the potential for EOR and storing of CO2 . Ferguson et al. [4] and Hamouda
and Pranoto [5] took the advantage of the CO2 water dissolution trapping and showed that instead of
following one regime for the whole injection period, using different regimes could enhance the storage
capacity, eliminate the limitation associated with the initial water in the storage site, and enhance
the oil recovery. Hamouda and Pranoto [6] addressed the synergy between CO2 and low-salinity
water. Fai-Yengo et al. [7] performed various experiments using different compositions of methane
(C1) and ethane (C2) in the injected CO2 gas (displacing fluid) and concluded that an acceleration of
the incremental oil recovery was observed in the case of the richer gas. Jin [8] studied the impact of
CO2 impurity on minimum miscible pressure (MMP). Hamouda and Tabrizy [9] investigated the effect

Energies 2018, 11, 391; doi:10.3390/en11020391 www.mdpi.com/journal/energies

Energies 2018, 11, 391 2 of 12

of recombined light components with CO2 as a displacing fluid for asphaltenic oil and concluded that
the presence of light components reduces oil recovery in the presence of asphaltene.
Three major processes take place with the injection of CO2 into the oil. These are diffusion/mass
transfer, solubility, and dispersion. Other factors that also affect the displacement efficiency with CO2
injection include density, viscosity difference between displacing and displaced fluids, mobility ratios,
relative permeability, wetting properties of the rock, and injection and production rates and their
changes during the injection period.
Moortgat et al. [10] investigated the overall CO2 composition (mole fraction) distribution for
vertical and horizontal cores.
This work addresses oil recovery from both stabilized and live oils from sandstone reservoirs
and the dynamic changes in their composition following flooding with CO2 alone and CO2 with
light hydrocarbon. It is stated in the literature, (Jin. L, 2016), [8] that injection of pure CO2 does not
necessarily lead to the best recovery. It was, therefore, decided to address the effect of light components
in the model oil n-C10 compared to crude oil (from the North Sea) at 200 bars by flooding with CO2
and CO2 /C1/C3 at different temperatures. Sampling and analysis of the components during flooding
are tedious and time consuming. The work approach was to test combining EOS (PVT simulation) in
order to ease the work and fulfil missing data.

2. Materials and Methods

Core flood experiments were performed using outcrop Bentheimer sandstone and Berea sandstone
as indicated in Table 1. The two types of sandstone have almost the same physical and chemical
properties. Both sandstone (outcrops) cores used in this work were acquired from Koucurek Industries
Inc., Caldwell, TX, USA. In the comparison experiments, Berea sandstone cores were used. The cores
were 9–10 cm in length and 3.8 cm in diameter. The porosity of the core was between 20% and 25% and
the permeability was 900–1200 mD. Table 1 depicts the details of the core characteristics, the associated
fluid used, and the flooding conditions. Table 2 shows the composition of the model oils (stabilized
n-C10, live oil A (n-C10/C1), and live oil B (n-C10/C1/C3)). The composition of the light components
in live oil A and live oil B were almost the same (about 20 mole %). The composition of the North Sea
crude oil is given in Table 3.

Table 1. Characteristics of cores along with associated fluid and flooding conditions.

Porosity Length Displacing Flooding

Exp. No. Core Type Saturating Fluid
(%) (cm) Fluid Temp. (◦ C)
1 Bentheimer 21.70 5.07 Live-oil A CO2 50
2 Bentheimer 21.25 9.00 Live-oil A CO2 70
3 Berea 19.30 8.96 Live-oil A CO2 90
4 Bentheimer 23.24 9.00 Live-oil B CO2 50
5 Bentheimer 23.30 9.00 Live-oil B CO2 70
6 Berea 19.60 9.09 Live-oil B CO2 90
7 Bentheimer 20.20 8.90 Dead-oil CO2 50
8 Bentheimer 21.05 9.00 Dead-oil CO2 70
9 Bentheimer 21.97 8.90 Dead-oil CO2 90
10 Berea 21.68 9.00 Model oil (Crude) CO2 + C1 + C3 70
11 Berea 21.88 9.00 Crude-oil CO2 + C1 + C3 70
12 Berea 21.22 9.00 Crude-oil CO2 70

Table 2. Oil composition.

Oil Type C1 (Mole %) C3 (Mole %) n-decane (Mole %)

Live Oil A 20.14 - 79.86
Live Oil B 9.86 11.9 78.23
Dead oil - - 100
Energies 2018, 11, 391 3 of 12
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Table3.3.Composition
Table Compositionofofthe
theNorth
NorthSea
Seacrude
crudeoil.
oil.

Component Mole (%)

Component Mole (%)
i-C5 0.0018
i-C5n-C5 0.0018
0.0117
n-C5 0.0117
C6 C6 0.0024
0.0024
C7 C7 1.390
1.390
C8 C8 3.961
3.961
C9 C9 6.287
6.287
C10+ 88.171
C10+ 88.171

2.1.
2.1.Experimental
ExperimentalProcedure
Procedure
Figure
Figure11represents
representsaaschematic
schematicflow flowdiagram
diagramof ofthe
theexperimental
experimentalsetup setup for
forthe
theCOCO22 flooding.
flooding.
The main components of the setup were the core holders, inlet and outlet gas
The main components of the setup were the core holders, inlet and outlet gas flowmeters, pressure flowmeters, pressure
regulators,
regulators,Gilson
Gilsonpump,
pump,pressure
pressuremanometers,
manometers,graduated
graduatedgas/oil
gas/oilseparator,
separator,andandthe theCOCO2 2and
andlive
liveoil
oil
piston
pistoncylinders.
cylinders.LabVIEW
LabVIEWversion
version7.17.1was
wasused
usedforfordigital
digitaldata
dataacquisition.
acquisition.TheThecores
coreswere
wereinitially
initially
saturated
saturated with
with synthetic model oil
synthetic model oiland/or
and/orcrudecrude oil.
oil. TheThe cores
cores were
were aged aged forleast
for at at least
two two
weeks.weeks.
Two
Two weeks of aging at 50 ◦ C was proven to be sufficient for altering the wettability. The aged cores
weeks of aging at 50 °C was proven to be sufficient for altering the wettability. The aged cores were
were inserted
inserted into into a rubber
a rubber sleeve
sleeve andand then
then mounted
mounted in in a coreholder.
a core holder.InInthe
thecase
case of
of live-oil
live-oil experiments,
experiments,
about
about two pore volumes (PVs) of dead oil was displaced by live oil at a slow rate(0.05–0.09
two pore volumes (PVs) of dead oil was displaced by live oil at a slow rate (0.05–0.09mL/min)
mL/min)
and
andfurther
further22PVsPVswere
weredisplaced
displacedatataafaster
fasterrate
rate(0.1–0.5
(0.1–0.5mL/min).
mL/min). Once
Once thethe cores
coreswere
werefully
fullysaturated
saturated
with ◦ C,
withlive
liveoil
oil(after
(afteraatotal
totalof
ofabout
about44PVs),
PVs),CO CO22flooding
floodingstarted
startedatat200
200barbarand
andtemperatures
temperaturesof of50
50 °C,
70 ◦ C, or ◦
70 °C, or90 C. The
90 °C. Theschematic
schematicdiagram
diagramof ofthe
theCO
CO22 flooding
flooding system
system isis shown
shown in in Figure
Figure1.1.

Figure 1. Schematic of the CO2 flooding system.

Figure 1. Schematic of the CO2 flooding system.
Energies 2018, 11, 391 4 of 12
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2.2. Sampling
2.2. Sampling
Three
Three flooding
flooding experiments
experiments with with CO were done
CO22 were done for for each
each of of live
live oil
oil A,
A, live
live oil
oil B,
B, and
and deaddead oiloil
n-C10 at 50, 70, and 90 ◦ C. Two flooding experiments were performed on each crude oil and dead
n-C10 at 50, 70, and 90 °C. Two flooding experiments were performed on each crude oil and dead oil
oil (n-C10)
(n-C10) sample;
sample; the the floodings
floodings were were
donedone using
using CO2CO and 2 and
a CO a2 CO 2 mixture
mixture (C1 and(C1 and
C3). C3).
During During
each
each experiment, three sets of samples were analyzed. The samples were
experiment, three sets of samples were analyzed. The samples were collected at the initial stage of collected at the initial stage
of ◦ C at 200 bar for comparison reasons.
thethe experiment.
experiment. The
The temperature
temperature waswas kept
kept constantatat7070°C
constant at 200 bar for comparison reasons.
The
The final set of samples was taken after the gas breakthrough. The samples
final set of samples was taken after the gas breakthrough. The samples werewere analyzed
analyzed for for CO
CO22
by discharging the gas from the sample into the absorption cell. The fluid
by discharging the gas from the sample into the absorption cell. The fluid in the absorption cell was in the absorption cell was
NaOH.
NaOH. The The absorbed
absorbed CO CO22 waswas then
then analyzed
analyzed by by volumetric titration while
volumetric titration while the
the natural
natural gas gas content
content
from the samples was passed through the absorption cell into the gas collection
from the samples was passed through the absorption cell into the gas collection bag and was analyzed bag and was analyzed
using
using gas gas chromatography
chromatography(GC). (GC).MostMostofofthethe
COCO 2 was
2 was
captured
captured by by
thethe absorber
absorber andandany any
traces traces
of CO of2
CO
left 2inleft
the ingas
the was
gas was obtained
obtained withwith
the the natural
natural gas gas
by the by the
GC.GC.TheThe COCO 2 absorber
2 absorber
setup
setup is shown
is shown in
in Figure 2. The setup also shows the gas collection bag. The liquid part
Figure 2. The setup also shows the gas collection bag. The liquid part of the sample was drained and of the sample was drained
and the volume
the volume waswas thenthen measured.
measured. In In
thethe collected
collected liquidsamples,
liquid samples,various
variousvolumes
volumesof of water
water werewere
observed depending on
observed depending on thethetemperature,
temperature,although
althoughall allthe
theexperiments
experimentshad haddrydry cores.
cores. TheThe amount
amount of
of water was found to increase with the flooding temperature. In the case of oil A at 70 ◦ C, about
water was found to increase with the flooding temperature. In the case of oil A at 70 °C, about 10.8 mL
10.8 mL of
of water waswater was produced
produced in the second
in the second sample,sample,
which was which wasclose
taken takentoclose to the breakthrough
the breakthrough and about and
about
5.3 mL5.3 ofmL of water
water in theinthird
the third
sample,sample,
whichwhich was taken
was taken duringduring the decline
the decline stagestage
(i.e., (i.e.,
afterafter the
the gas
gas breakthrough). In the case of the dead oil at 90 ◦ C, about 31.2 mL of water was collected with the
breakthrough). In the case of the dead oil at 90 °C, about 31.2 mL of water was collected with the
samples
samples in in the
the third
third sample.
sample.

Figure 2. CO2 absorber and gas bag system setup.

Figure 2. CO2 absorber and gas bag system setup.

3. Results and Discussions

3. Results and Discussions
This section compares the oil recovery by injection of CO2 and CO2/HC (C1&C3) for model oils
This section compares the oil recovery by injection of CO2 and CO2 /HC (C1&C3) for model
(n-C10) and crude oil (North Sea). Possible flooding mechanism(s) based on the experimental
oils (n-C10) and crude oil (North Sea). Possible flooding mechanism(s) based on the experimental
compositional analysis and simulation and phase behavior are addressed.
compositional analysis and simulation and phase behavior are addressed.
3.1. Effect
3.1. Effect of
of Temperature on Oil
Temperature on Oil Recovery
Recovery at
at aa Constant
Constant Pressure
Pressureofof200
200Bar
Bar
Flooding was
Flooding was performed
performed onon the
the sandstone
sandstonecores
coressaturated
saturatedwith
withthe
thesynthetic
syntheticlive
live(n-C10/C1/C3)
(n-C10/C1/C3)
and dead oil (stabilized, n-C10) at 50 °C,
◦ 70 °C,
◦ and 90 °C,
◦ as shown in Table 2. Higher recovery was
and dead oil (stabilized, n-C10) at 50 C, 70 C, and 90 C, as shown in Table 2. Higher recovery was
observed at 90 °C for all of the model oil types, as illustrated in Figure 3. This may be related to a
reduction in the viscosity of the displaced fluid (i.e., improved oil mobility).
Energies 2018, 11, 391 5 of 12

observed at 90 ◦ C for all of the model oil types, as illustrated in Figure 3. This may be related to a
reduction
Energies
Energies
in10,the
2018,
2018, 10,
viscosity
x FOR PEER
x FOR
of the displaced fluid (i.e., improved oil mobility).
PEERREVIEW
REVIEW 5 of5 12
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Figure 3. Comparison of ultimate oil recovery for model live oils A&B and dead oil (n-C10) at 50 °C,
Figure 3. Comparison of ultimate oil recovery for model live oils A&B and dead oil (n-C10) at 50 ◦ C,
Figure
70 °C,3.and
Comparison
90 °C. of ultimate oil recovery for model live oils A&B and dead oil (n-C10) at 50 °C,
70 ◦ C, and 90 ◦ C.
70 °C, and 90 °C.
3.2. Effect of Added Light Components to CO2 as a Displacing Fluid on Oil Recovery
3.2. Effect
3.2. Effect of
of Added
Added LightLight Components
Components to to COCO22 as as aa Displacing
Displacing Fluid Fluid onon Oil Oil Recovery
Recovery
In these experiments, the temperature was set at 70 °C. Flooding with CO2 was taken as a
In these ◦ C. Flooding with CO was taken as a
reference
In theseforexperiments,
the comparison.
experiments, theFigure
the temperature
4 compares
temperature was
wasoilset
set at
at 70
recoveries.
70 °C. The highest oil
Flooding recovery
with was obtained
CO22 was taken as a
reference
reference for
for the
by flooding comparison.
thecomparison.
the dead oil (n-C10). Figure
Figure 44 compares
Figure compares
4 showsoil oil
thatrecoveries. The highest
the oil recoveries
recoveries. The highest oil
of theoil recovery
model was obtained
oil (n-C10)
recovery was obtained
with
by flooding
CO 2 and COthe2 dead
/C 1 /C 3 oil
were(n-C10). Figure
approximately 4 shows
the same that
(aboutthe oil
82%). recoveries
by flooding the dead oil (n-C10). Figure 4 shows that the oil recoveries of the model oil (n-C10)was
However, of the
the model
ultimate oil (n-C10)
recovery with
with
CO and
reached COat /C1/C3
about 15 were
and approximately
36 injected PVs the
for same
CO /C (about
/C and 82%).
CO
CO22 and CO22/C1/C3 were approximately the same (about 82%). However, the ultimate recovery was
2 1 3 2 , However,
respectively. the ultimate
This agreesrecovery
with was
the
conclusion
reached
reached at by [7].
at about
about 15 On
15 andandthe
36 other
36injected
injected hand,
PVsPVsthe
forforrecoveries
CO CO2 /C1/C3 of flooded
and COcrude oil with CO
, respectively. 2 and
This
2/C1/C3 and CO2,2 respectively. This agrees with the
CO2with
agrees /C1/C3the
conclusion by [7]. On the other hand, the recoveries of flooded crude oil with CO2 and CO2/C19
were
conclusionaboutby 65%
[7]. and
On 76%,
the respectively,
other hand, where
the the
recoveries ultimate
of recovery
flooded crude was reached
oil with after
CO 2 about
and CO 7 2and
/C1/C31/C3
injected
were aboutPVs 65%ofand
and CO76%,
2 andrespectively,
CO2/C1/C3, respectively.
wherethe Jin L, 2016
theultimate
ultimate [8] investigated
recovery was reachedthe after
impact of CO
about 7 and
2
were about 65% 76%, respectively, where recovery was reached after about 7 and 19
19 impurity
injected (C1)
PVs on
of MMP
CO andand CO stated that
/C1/C3, the purest
respectively. CO 2 does
Jin L, not
2016 lead
[8] to the best
investigated oil recovery
the impact at
ofthe
CO
injected PVs of CO2 and CO2/C1/C3, respectively. Jin L, 2016 [8] investigated the impact of CO22
2 2
same period.
impurity (C1) on onThe paperand
MMP suggested
stated that that the
that the reason for thedoes
difference is due to compressibility of at
the
impurity (C1) MMP and stated the purest
purest CO CO22 does not lead
not lead to the
to the best oil
best oil recovery
recovery at the
the
lightperiod.
same hydrocarbon,
The paper where
paper practically
suggested that methane
the reason usually
reason for hasthe the largest content.
difference is due
due to
same period. The suggested that the for the difference is to compressibility
compressibility of of the
the
light hydrocarbon,
light hydrocarbon, where where practically
practically methane methane usually
usually has has the
the largest
largest content.
content.

Figure 4. Comparison between the recovery of crude and model oils flooded with CO2 and CO2/C1/C3
at 70 °C and 200 bar.

Figure 4. Comparison between the recovery of crude and model oils flooded with CO2 and CO2/C1/C3
3.3.Figure 4. Comparison
Comparison between theCompositional
of the Experimental recovery of crude and model
Analysis oils
and the flooded with CO2 and CO2 /C1/C3
Simulation
at
at 70
70 °C
◦ C and
and 200
200 bar.
bar.
In this section a comparison is made between the experimental and simulated compositions to
3.3.verify the use of
Comparison ofthe
theExperimental
simulation for a later stage Analysis
Compositional of this work.
and the Simulation
In this section a comparison is made between the experimental and simulated compositions to
verify the use of the simulation for a later stage of this work.
Energies 2018, 11, 391 6 of 12

3.3. Comparison of the Experimental Compositional Analysis and the Simulation

In this section a comparison is made between the experimental and simulated compositions to
verify the use of the simulation for a later stage of this work.
A comparison of the experimental composition (spot samples obtained during the flooding and
analyzed by GC and CO2 absorber) and the dynamic simulation was done at the corresponding
temperature and pressures of the sample. Table 4 compares the analytical data for model oil (n-C10)
and live oil B flooded with CO2 /C1/C3. The experimental and simulated data are numbered according
to their sampling sequence to capture the sampling pressures at 70 ◦ C. The samples were taken at the
start of the flooding and then at different times (PVs). The % difference between the simulated and
experimental data are shown in the tables for each component. The total average difference between
the experimental and the simulation was between 21% and 39%. In other words, the agreement was
within about 70% as an average, with minimum and maximum agreement of about 33% and 91%,
respectively. The differences were not surprising since the experimental process included various steps;
for example, the CO2 went through absorption and was then analyzed volumetrically and by GC.
The used hydrocarbon reference for the GC was kept constant—that is, the reference did not reflect
the changes in the composition of the components that corresponded to the samples, which may have
contributed to the differences. However, the comparison indicates that the dynamic simulation using
PVTsim simulator (CALSEP A/S, Lyngby, Denmark) with EOS SRK–Peneloux and the experimental
results were close. The miscibility was determined by EOS SRK–Peneloux (PVTsim simulator).

Table 4. (a) Comparison between the experimental and the simulation results for the flooded model oil
(n-C10) with CO2 /C1/C3. The total average difference is about 21%. Note that the negative values
indicate exp. data > sim. data. (b) Comparison between the experimental and the simulation results for
the flooded live model oil B (n-C10/C1/C3) with CO2 /C1/C3. The total average difference is about
39%. Note that the negative values indicate exp. data > sim. data.

(a)
Components Exp. 1 Sim. 1 Exp. 2 Sim. 2 Exp. 3 Sim. 3 % Diff. 1 % Diff. 2 % Diff. 3 % Avg/Comp.
CO2 0.1 0.198 3.7 3.93 49.3 53.47 49.5 5.9 7.9 21
C1 0.012 0.012 0.59 0.481 20.24 5.53 0 −22.7 72.7 32
C3 0.02 0.015 0.573 0.58 7.8 10.3 −33 1.7 24.27 20
nC10 99.8 99.8 95.1 95.0 22.7 30.7 0 −0.11 26.1 9
(b)
Components Exp. 1 Sim. 1 Exp. 2 Sim. 2 Exp. 3 Sim. 3 % Diff. 1 % Diff. 2 % Diff. 3 % Avg/Comp.
CO2 10.48 99.0 52.64 52.61 97.1 50.2 89.4 −0.03 −46.9 45
C1 8.84 8.8 4.67 4.67 0.29 0.08 −0.45 0 >−200 67
C3 10.65 10.6 5.64 5.64 0.35 0.56 −0.05 0 37.5 12.6
n-C10 70.03 69.9 37.05 37.08 2.27 49.15 −0.13 0.081 95.4 31

3.4. Dynamic Composition Change in Experiments and Simulations during Flooding

Figure 5 shows the sequence (dynamic) composition changes during the flooding of live oil B with
CO2. This was done to compare the obtained dynamic composition and the experimental data (spot)
as a function of injected PV. The experimental and simulation trends are in a good agreement; hence,
a reasonable mechanism of the flooding may be deduced based on the change of the compositions
and the trends. This figure may be simplified as all the liquid components decrease (except for the
last experimental points for C10 and CO2 ) indicating evaporation processes were taking place as the
CO2 was injected. The last experimental point of the CO2 trend and C10 deviated from the simulation.
The content of CO2 at this point was high after the breakthrough and a minor error in sampling could
have caused the deviation; however, the discrepancy may be due to the small volume of n-C10 at
the end of the experiment. Both discrepancies influence each other since they affect the total mole
percent. However, the composition of all the components, excluding the end experiment composition
of CO2 and n-C10, agrees well. Therefore, it was concluded that based on the component changes, the
Energies 2018, 11, 391 7 of 12

dynamic simulation approach can reflect reasonably well the flooding mechanism/mass transfer and
Energies 2018, 10, x FOR PEER REVIEW 7 of 12
can give
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10, x FOR the effect
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Figure 5. Dynamic changes in the composition in the liquid phase as a function of the injected pore
Figure 5.
volume
Figure 5.(PV)
Dynamic changes
for livechanges
Dynamic in the
the
Oil B (78.23
in composition
mole in
% n-C10/9.86
composition the liquid
mole
in the phase as
% C1/11.9
liquid phase as aa function
mole function of the
the injected
% C3) flooded
of injected
with CO pore
2.
pore
volume (PV) for live Oil B (78.23 mole % n-C10/9.86 mole % C1/11.9 mole % C3) flooded with CO2. .
volume (PV) for live Oil B (78.23 mole % n-C10/9.86 mole % C1/11.9 mole % C3) flooded with CO
2
3.5. Effect of Light Components (C1&C3) in the Displacing Fluid of CO2 on the Recovery of Model and
3.5. Effect
Crude Oilsof Light Components (C1&C3) in the Displacing Fluid of CO2 on the Recovery of Model and
3.5. Effect of Light Components (C1&C3) in the Displacing Fluid of CO2 on the Recovery of Model and
Crude Oils
Crude Oils
3.5.1. Model Oil (n-C10) Flooded with CO2/C1/C3
3.5.1. Model Oil (n-C10) Flooded with CO22/C1/C3 /C1/C3
Figure 6a,b represents the simulated composition changes in the oil and vapor phases,
Figure 6a,b
Figure
respectively, 6a,b
duringrepresents
represents
floodingthe the
of simulated
simulated
the model oilcomposition
composition changes
with CO changes
2/C1/C3. in the inand
As oil
the thevapor
oil and
displacing vapor
phases,
fluid phases,
respectively,
contacts the
respectively,
during flooding during
of flooding
the model of
model oil, CO2/C1/C3 condensates into theoilthe model
with CO oil with
/C1/C3. COAs 2 /C1/C3.
the As the
displacing displacing
fluid fluid
contacts
2 oil phase (Figure 6a). Condensation of CO2 from the contacts
the model the
oil,
model
CO
injectionoil,
2 /C1/C3 CO
fluid 2/C1/C3 condensates
condensates
was into the oilinto
more pronounced phasethe(Figure
not only oil phase
6a).of
because (Figure
its high6a).
Condensation Condensation
of CO
content 2 from
in the of CO
the 2 from
injection
injection gas the
butfluid
also
injection
was more fluid was
pronounced more notpronounced
only becausenot only
of its because
high of
content its
inhigh
the content
injection in the
gas
because of its diffusion and solubility into n-C10 [11,12]. As the injection continued, the C1 and C3 injection
but also gas
becausebut also
of its
because
diffusion of
contents and its diffusion
solubility
increased and
in into solubility
the n-C10 into
[11,12].
oil phase n-C10
As the
while [11,12].
theinjection As the
continued,
C10 content injection
(molethe%) continued,
C1was
and C3 the C1
contentsThe
reduced. and C3
increased
vapor
contents
in the oil increased
phase whilein the
the oil
C10 phase
content while
(mole the
%) C10
was content
reduced. (mole
The
composition is shown in Figure 6b and indicates the development of the two-phase with %)
vapor was reduced.
composition The
is shownvaporin
the
composition
Figure 6b and is shown
indicates
displacing and displaced fluids. in
the Figure 6b
development andof indicates
the the
two-phase development
with the of
displacing the two-phase
and displaced with the
fluids.
displacing and displaced fluids.

Figure 6.
Figure 6. Cont.
Cont.
Figure 6. Cont.
Energies 2018, 11, 391 8 of 12
Energies 2018, 10, x FOR PEER REVIEW 8 of 12

Energies 2018, 10, x FOR PEER REVIEW 8 of 12

Figure
Figure 6.
6. Dynamic composition changes
Dynamic composition changes as
as aa function
functionof
ofthe
theinjected
injectedpore
porevolume
volumeofofCO
CO/C1/C3
2/C1/C3 into
into
2
model oil (n-C10), (a) in liquid phase and (b) in the vapor phase.
model oil (n-C10), (a) in liquid phase and (b) in the vapor phase.
Figure 6. Dynamic composition changes as a function of the injected pore volume of CO2/C1/C3 into
3.5.2. Crudemodel
Oil Flooded
oil (n-C10),with
(a) in CO
liquid
2 phase and (b) in the vapor phase.
3.5.2. Crude Oil Flooded with CO2
Compositional
3.5.2. Crude Oilchanges of crude
Flooded with CO2 oil with CO2 flooding are shown in Figure 7a,b. At the first
Compositional changes of crude oil with CO2 flooding are shown in Figure 7a,b. At the first
contact, COCompositional
2 condenses/dissolves/disperses in the oil, as shown in the case of the model oil. Within
changes of crude oil with
contact, CO2 condenses/dissolves/disperses in CO flooding
the2 oil, are shown
as shown in case
in the Figure
of7a,b. At the first
the model oil. Within
about 2 contact,
PVs injected,
CO two phases developed. The
2 condenses/dissolves/disperses in thevapor
oil, as composition
shown in the is shown
case of the in Figure
model 7b. At about
oil. Within
about 2 PVs injected, two phases developed. The vapor composition is shown in Figure 7b. At about
3 PVs, the CO22PVs
about content reached
injected, about
two phases 99.6 mole
developed. The %vapor
and the rest wasiscomposed
composition of the
shown in Figure 7b.other vaporized
At about
3 PVs, the CO2 content reached about 99.6 mole % and the rest was composed of the other vaporized
3 PVs,
crude oil the CO2 content reached about 99.6 mole % and the rest was composed of the other vaporized
components.
crude oil components.
crude oil components.

Figure 7. Dynamic composition changes as a function of the injected pore volume of CO2 into crude
Figure 7. Dynamic composition changes as a function of the injected pore volume of CO2 into crude
oil (a) in liquid phase and (b) in vapor phase.
oil (a) in liquid phase and (b) in vapor phase.

Figure 7. Dynamic composition changes as a function of the injected pore volume of CO2 into crude
oil (a) in liquid phase and (b) in vapor phase.
Energies 2018, 11, 391 9 of 12
Energies 2018, 10, x FOR PEER REVIEW 9 of 12

3.5.3. Crude
3.5.3. Crude Oil
Oil Flooded
Flooded with
with CO
CO22/C1/C3
/C1/C3
Similar to
Similar tothe
theabove
aboveflooding,
flooding,Figure 8a,b8a,b
Figure shows component
shows tracking
component for crude
tracking foroil during
crude oilflooding
during
with CO /C1/C3. At the first contact, the displacing fluid CO
flooding 2with CO2/C1/C3. At the first contact, the displacing fluid CO 2 2/C1/C3 condenses, then by
/C1/C3 condenses, then the
by the
extraction process
extraction process crude
crude oil
oil components
components are are then
then transferred
transferred into
into the
the vapor
vapor phase.
phase. Two
Two phases
phases were
were
established at about 3.5 PV of injection.
established at about 3.5 PV of injection.

Figure
Figure 8.
8. Dynamic composition as
Dynamic composition as aa function
function of
of injected
injectedpore
porevolume
volumeofofCO
CO2/C1/C3
/C1/C3 into
intocrude
crude oil
oil (a)
(a)
2
in liquid phase and (b) in vapor phase.
in liquid phase and (b) in vapor phase.

3.5.4. Displacement Mechanisms and the Effect of the Light Components on Recovery
3.5.4. Displacement Mechanisms and the Effect of the Light Components on Recovery
In the previous sections, higher oil recovery was shown to be by flooding with CO2/C1/C3 than
In the previous sections, higher oil recovery was shown to be by flooding with CO2 /C1/C3 than
with CO2. When CO2 contacts oil, diffusion, dissolution and dispersion processes take place. These
with CO2 . When CO2 contacts oil, diffusion, dissolution and dispersion processes take place. These
processes cause the swelling of the oil to different degrees. The relative increase in the volume
processes cause the swelling of the oil to different degrees. The relative increase in the volume swelling
swelling depends on pressure, temperature, and oil composition. Continuing injection leads to
depends on pressure, temperature, and oil composition. Continuing injection leads to component
component extraction from the oil and the development of two phases. Figure 7b illustrates the
extraction from the oil and the development of two phases. Figure 7b illustrates the composition of
composition of the extracted components in the vapor phase. The extracted components from oil are
the extracted components in the vapor phase. The extracted components from oil are relatively small
relatively small and hence have an unnoticeable effect on the magnitude of the swelling [13].
and hence have an unnoticeable effect on the magnitude of the swelling [13]. Similarly, when flooding
Similarly, when flooding with CO2/C1/C3, the components of the displacing fluid condense as they
with CO2 /C1/C3, the components of the displacing fluid condense as they contact the oil. Figure 8a
contact the oil. Figure 8a shows the increase of the injected gas components in the crude oil. The two
shows the increase of the injected gas components in the crude oil. The two phases were established at
phases were established at about 3.5 injected PV (i.e., about 1.5 PV later than in the case of CO2
about 3.5 injected PV (i.e., about 1.5 PV later than in the case of CO2 injection). This is consistent with
injection). This is consistent with Figure 4 where the ultimate recovery took longer to reach than in
the case of CO2. It also shows higher oil recovery compared to the CO2 phase.
Energies 2018, 11, 391 10 of 12

Figure 4 where the ultimate recovery took longer to reach than in the case of CO2 . It also shows higher
oil recovery compared to the CO2 phase.
Figure 9a shows the changes in the viscosities of the displacing fluids with CO2 and CO2 /C1/C3
during the flooding at the corresponding pressures and 70 ◦ C. Figure 9b compares the viscosities
Energies 2018, 10, x FOR PEER REVIEW 10 of 12
(obtained by EOS SRK–Peneloux) between crude oil flooded with CO2 and CO2 /C1/C3 and model
oil flooded withFigureCO 2 /C1/C3.
9a shows For model
the changes oil and crude
in the viscosities oil flooded
of the displacing with
fluids CO
with 2 /C1/C3,
CO the pressure
2 and CO2/C1/C3

changedduring
from the the flooding
injectionatpressure of 200 topressures
the corresponding about 100 andbar
70 at
°C.the end9b
Figure of compares
the experiments. In the case
the viscosities
(obtained by EOS SRK–Peneloux) between crude oil flooded with CO and
of the crude oil flooded with CO2 , the pressure changed from 200 to about 70 bar. It is interesting
2 CO 2 /C1/C3 and model oil to
flooded with CO 2/C1/C3. For model oil and crude oil flooded with CO2/C1/C3, the pressure changed
see the changes in the viscosity. In the case of the crude oil, a sharp decline in the viscosity occurred
from the injection pressure of 200 to about 100 bar at the end of the experiments. In the case of the
during the flooding conditions compared to that with the model oil. In the cases of crude oil/CO2
crude oil flooded with CO2, the pressure changed from 200 to about 70 bar. It is interesting to see the
and crude oil/CO
changes 2 /C1/C3,
in the viscosity. the viscosities
In the case of thewere
crudereduced
oil, a sharpfrom about
decline in the2.2viscosity
to 0.42occurred
and 0.2 during
after about 3
and 5 PVs, respectively.
the flooding Thecompared
conditions minima represent
to that withtransition
the model oil.points
In the(TPs)
cases after
of crude which
oil/COcrude oil becomes
2 and crude

lean in oil/CO /C1/C3, the viscosities

light 2components and the were reducedincreases.
viscosity from about 2.2 In to 0.42 and
other words,0.2 after
as theabout 3 and 5 PVs,
injection continues,
respectively. The minima represent transition points (TPs) after which crude
evaporation–condensation processes occur around the TPs. The average viscosities were 1.3 and 1.2 cP oil becomes lean in light
for CO2components
and CO2 /C1/C3, and the viscosity increases. In other words, as the injection continues, evaporation–
respectively. This may explain the reason for almost the same recovery of
condensation processes occur around the TPs. The average viscosities were 1.3 and 1.2 cP for CO2
about 82% in both cases for the model oil. The difference in the oil viscosities of the crude oil flooded
and CO2/C1/C3, respectively. This may explain the reason for almost the same recovery of about 82%
with COin2 both
and cases
CO2 /C1/C3
for the modelwasoil.
about 0.2 cP. The
The difference difference
in the in the
oil viscosities recovery
of the crude oil(of aboutwith
flooded 65% COand
2 76%,
for CO2and and CO CO 2 /C1/C3,
2/C1/C3 was respectively)
about 0.2 cP. The may not
difference inbe
the explained
recovery (ofbased
about only
65% andon the
76%, difference
for CO 2 and in the
CO /C1/C3, respectively) may not be explained based only on the difference in
viscosities. As the injected fluid contacts the oil, different processes such as solubility, dispersion, and
2 the viscosities. As the
injected fluid contacts
condensation/extraction the oil,
take place [12].different
Transverse processes
dispersionsuchhelps
as solubility,
to eliminate dispersion,
the effectand of viscous
condensation/extraction take place [12]. Transverse dispersion helps to eliminate the effect of viscous
instabilities by shortening the fingering travel/widening the fingers [14]. This may resemble the case
instabilities by shortening the fingering travel/widening the fingers [14]. This may resemble the case
with COwith
2 /C1/C3
CO2/C1/C3injection into
injection the
into thecrude
crude oil.
oil.

Figure 9. (a) Viscosity of the displacing fluids as a function of the experimental pressures and (b)
Figure 9. (a) Viscosity of the displacing fluids as a function of the experimental pressures and (b)
comparison between viscosities of crude oil flooded with CO2 and (CO2/C1/C3) CO2 and the viscosity
comparison between
of model viscosities
oil flooded of 2crude
with (CO oil flooded with CO2 and (CO2 /C1/C3) CO2 and the viscosity
/C1/C3).
of model oil flooded with (CO2 /C1/C3).
Energies 2018, 11, 391 11 of 12

3.5.5. Water Produced from Flooded Dry Sandstone Cores

The three hydroxyl groups on the silica surface are classified as isolated, hydrogen bonded, and
inaccessible [15], where the fraction of the two first groups participate in the surface reaction. They also
found that CO2 penetrated the regions containing the inaccessible groups, in addition to the ability of
the supercritical CO2 to remove the adsorbed water layer on silica. Kim, Y et al. 2012 [16] investigated
the de-wetting of silica surfaces upon reactions with supercritical CO2 . They stated that the brine
contact angle increased from 0◦ to 80◦ . The above may explain the observed water production from dry
core saturated with oil during the flooding, whereas examples (among other recorded water volumes)
of about 8.1 mL of water was observed in the sample taken in the case of model oil flooded with
CO2 /C1/C3.

4. Summary and Conclusions

This section is organized to briefly state the observed phenomena with possible explanations to
elucidate the relevant conclusions.
Compositional changes during the flooding were compared with the simulation as a cross-check
and were shown to be in a good agreement. This encourages applying simulation in this work to fill
gaps due to insufficient sampling and reduce the number of reference samples for GC analysis.

1. In general, as the temperature increases with miscible CO2 flooding at a constant pressure of
200 bar, oil recovery increases. The highest recovery was obtained with model oil (n-C10).
The presence of light components in the model oil phase reduced the recovery. Lower recovery
was observed in the presence of C1 and C3 (live oil B) compared to only C1 (live oil A). This may
be explained by more CO2 diffusing into the oil in the case of live oil A since methane is
readily transferred into the vapor phase due to its limited solubility and exchanged with the
higher soluble CO2 . In turn, the more CO2 available, the larger the increase of the hydrocarbon
swelling—that is, more oil recovery compared to oil containing C1/C3 where C3 is more soluble
in C10 than in C1; hence less CO2 mass transfer.
2. An opposite case was investigated where the light components (C1/C3) were combined with
CO2 as displacing fluid (CO2 /C1/C3). Comparisons were made of crude oil flooded with the
two displacing fluids (CO2 and CO2 /C1/C3) and model oil (n-C10) displaced with CO2 /C1/C3.
In general, recovery from the model oil was higher than from the crude oil, which may be due to
the differences between their mobility. There was almost no difference in the recovery of model
oil (≈82%) with the two displacing fluids. However, in the case of crude oil, the recoveries were
65 and 76% for the displacing fluids of CO2 and CO2 /C1/C3, respectively. As the injected fluid
contacts the oil, different processes, such as solubility, dispersion, and condensation/extraction,
take place. Transverse dispersion of CO2 helps in eliminating/reducing the effect of viscous
instabilities by shortening fingering travel/widening the fingers, as discussed earlier. A sharp
decline in viscosity was also shown during the flooding of the crude oil with CO2 compared to a
lesser declining slope in the case of CO2 /C1/C3. The sharp decline in viscosity may cause the
early formation of fingers and promote their growth and hence the lower recovery. In addition,
the ultimate recovery with CO2 was reached earlier than that with CO2 /C1/C3. Injected light
components with CO2 showed a relatively slower rate to reach minimum system viscosity
compared to that for CO2 flooding, which may promote transverse dispersion of the displacing
fluid and hence less traveling of fingers. A longer flooding time may also promote the lateral
growth of fingers.
3. An additional interesting observation was the water production in the obtained samples from the
flooded dry sandstone cores. This may be explained by the ability of CO2 to penetrate regions
containing the inaccessible hydroxyl groups, in addition to the ability of the supercritical CO2 to
remove the adsorbed water layer on silica.
Energies 2018, 11, 391 12 of 12

Acknowledgments: Authors acknowledge Krzystof Nowicki, laboratory assistant, for technical support during
the experiments and for pressure testing of the equipment, Per Eirik Krossgått Widvey for mechanical help,
and Kim Andre Nesse Vorland for help with LabVIEW and data collection. Thanks to Inger Johanne for ordering
the needed chemicals and parts and for the setup.
Author Contributions: Aly Hamouda and Sidra Chughtai conceived and designed the experiments;
Aly Hamouda and Sidra Chughtai performed the experiments; Aly Hamouda and Sidra Chughtai analyzed the
data; Aly Hamouda and Sidra Chughtai wrote the paper.
Conflicts of Interest: The authors declare no conflict of interest. The funding sponsors had no role in the design
of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, and in the
decision to publish the results.

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