SPE 93773
CO2 Injection in Carbonates
O. Izgec and B. Demiral, METU; H. Bertin, Laboratoire TREFLE, and S. Akin, METU
Copyright 2005, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the 2005 SPE Western Regional Meeting held in
Irvine, CA, U.S.A., 30 March – 1 April 2005.
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Abstract
Started as an EOR technique to produce oil, injection of
carbon dioxide which is essentially a greenhouse gas is
becoming more and more important. Although there are a
number of mathematical modeling studies, experimental
studies are limited and most studies focus on injection into
sandstone reservoirs as opposed to carbonate ones. This study
presents the results of computerized tomography (CT)
monitored laboratory experiments to characterize relevant
chemical reactions associated with injection and storage of
CO2 in carbonate formations. Porosity changes along the core
plugs and the corresponding permeability changes are reported
for differing CO2 injection rates and with differing salt
concentrations. CT monitored experiments are designed to
model fast near wellbore flow and slow reservoir flows. It
was observed that permeability initially increased and
decreased for slow injection cases. As the salt concentration
decreased the porosity and thus the permeability decrease was
less pronounced. The experiments were modeled using a
commercial simulator where solution and deposition of calcite
were considered by means of chemical reactions. The
calibrated model was then used to analyze field scale
injections. It was observed that solubility storage of CO2 is
larger compared to mineral trapping.
Introduction
Anthropogenic greenhouse gases, such as carbon dioxide
(CO2), are considered a major contributor to global warming1.
Sequestration of power plant generated CO2 by injection into
groundwater aquifers and (petroleum and gas) reservoirs has
been proposed as a possible alternative for the reduction of
excessive greenhouse gases in the atmosphere. Ideally,
injected CO2 will migrate through an aquifer from injection
wells to remote storage sites, and remain isolated from the
atmosphere for a considerable period of time. CO2 has been
used for enhanced oil recovery (EOR) purposes since the
1950’s (the first carbonated water floods were tested as early
as 1951 and slugs of pure CO2 for oil displacement were tested
as early as 19632. Research on use of CO2 for EOR continues
with an ever growing interest; however, research concerning
terrestrial sequestration of CO2 for environmental purposes is
relatively recent3.
Fundamental topics of interest in
sequestration research have concerned not just scientific and
technical aspects, but practical concerns such as the economic
feasibility of storage, safety, and the maximum possible
amount of CO2 storage globally and for specified regions1.
Fundamental research questions include the following: Can
typical regional scale aquifers and depleted oil and gas
reservoirs provide the residence time needed to achieve stated
global temperature reduction goals; what geologic conditions,
e.g., rock properties, depositional environments, structure, etc.,
provide optimal CO2 flow and transport, and optimal storage
in a sedimentary basin?
CO2 can be sequestrated in geological formations like
saline aquifers by three mechanisms: solubility trapping
through dissolution in the formation water1, mineral trapping
through geochemical reactions with the aquifer fluids2, 4 and
rocks, and hydrodynamic trapping of CO2 plume1. These
mechanisms lead to storage of CO2 as free-phase gas in pore
spaces, dissolved phase CO2 in formation water and CO2
converted to rock matrix.
Geological disposal of CO2 would ideally be made at
supercritical conditions (31.04 ˚C and 1070.7 psi), in order to
avoid adverse effects of prior separation of CO2 into liquid and
gas phases in the injection system1. The desire of supercritical
injection limits minimum depths to approximately 800 m to
sustain a supercritical regime5. Although supercritical injection
and storage of CO2 would be ideal, for all practical reasons, it
is not a necessary condition.
Injection of CO2 in geological media includes variety of
strongly coupled physical and chemical process as multiphase
flow, solution-dissolution kinetics, solute transport,
hydrodynamic instabilities due to displacement of less viscous
brine with more viscous CO2 (viscous fingering), and upward
movement of CO2 due to gravity (gravity override)1 From an
engineering perspective, the main issues for injection of CO2
in geological formations relate to: the rate at which CO2 can be
disposed, the available storage capacity, the presence of a low
permeable caprock, the potential for CO2 leakage, uncertainty
and possibility of failure due to incomplete knowledge od
subsurface conditions and process and the corrosion resistance
of materials to be used in the system5, 6. Chemical kinetics is
another important physical concept that should be studied.
Reactions among the formation rock, the aquifer fluid and CO2
2 SPE 93773
may lead to change in the formation permeability and the
effective porosity, thus the storage capacity of the formation.
Change in the rock permeability and effective porosity result
from dissolution of rock minerals, transportation and later
precipitation of them. Continuous dissolution of reactant
minerals alters the concentration of aquifer fluid, thus in later
times leading to precipitation of product phases. While
dissolution of rock minerals brings about an increase in the
formation permeability, precipitation of those minerals leads
to decrease in the formation permeability and the effective
porosity.
Although there are plenty of numerical modeling and a
number of semi analytical and analytical7, 8 studies related to
injection of CO2 in geological formations, experimental
studies are limited and most studies focus to sandstone
aquifers as opposed to carbonate ones. For a carbonate system
kinetically controlled reactions could be defined as9:
H2O + CO2 + CaCO3 ↔ Ca(HCO3)2 (1)
Mechanisms by which a precipitate reduce permeability
include solid deposition on the pore walls due to attractive
forces between the particles and the surfaces of the pores,
individual particles blocking pore throats, and several particles
bridging across a pore throat6. In a carbonate formation major
cause of reduction in rock properties is precipitation of
Ca(HCO3)2 and NaCl. Pressure drop through the flow paths
affects the precipitation rate, thus leads to variations in rock
properties by changing the solubilities of substances.
Assuming there is Darcian flow in the porous media, it can be
said that there is a linear relationship between the pressure
drop and the axial distance in the direction of flow.
Considering this relationship and solute transport concept, it
should be expected that permeability increases in near well
bore region and then gradually decreases through to flow
direction9. It is previously reported that permeability decline
caused by only scale formation in the porous bed can reach to
%90 of the initial permeability, depending on solution
composition, initial permeability, temperature, and flow rate
and solution injection period10. On the other hand Omele and
Osaba9 reported increase in the permeability of dolomite cores
by 3.5 to 5 percent after similar CO2 treatments while
reduction in permeability was observed for other experiments.
Those results suggest that the process strongly depends on the
distribution of the rock minerals.
As can be seen experimental studies are limited in number.
Most of the studies focused on hydrodynamic and solubility
trapping of CO2. Mineral trapping and the effects of change in
rock properties and their impact on CO2 sequestration are not
well studied. In this study, first CT monitored laboratory
experiments where porosity and permeability change as a
result of CO2 injection will be presented. Then calibration of a
simulation model by matching the observed permeability and
porosity changes using a commercial simulator where
permeability and porosity change as a result of aforementioned
chemical reactions and adsorption will be reported. Then
potential application of CO2 sequestration in a regional aquifer
located in South East Turkey will be discussed by using a
calibrated simulation model.
Experimental Apparatus and Procedure
The experimental apparatus consisted of, X-ray CT scanner
(3rd generation Philips Tomoscan TX60), injection system,
core holder, and data recording system (Figure 1). The
injection system was made up of a constant displacement
pump, CO2 bottle, gas flow meter controller, and a pressure
transducer. For horizontally aligned experiments a Hassler
type X-ray transparent aluminum core holder wrapped with
Fiberfrax insulation and carbon fiber materials to minimize x-
ray scanning artifacts11 is used. For vertically oriented
experiments a core holder placed in a water jacket that enabled
fast adjustment of the system temperature at a constant level
was used. Carbonate core plugs drilled from Midyat
formation located in Diyarbakir, South East Turkey, were used
in all experiments. Midyat rock is mainly a heterogeneous
carbonate with vugs and fractures. The core plugs contained
mainly calcite with 5% alteration. For vertically aligned
experiments epoxy coated core plugs of 10.7 cm long and 4.72
cm in diameter as opposed to 7 cm long and 3.81 cm ones in
horizontal experiments were used. Table 1 gives physical
properties of the core plugs used in the experiments. The
system confining pressure was kept at 500 psi using a
manually operated hydraulic pump. The temperature of the
system was kept at the desired temperature using an electronic
temperature controller with an accuracy of 0.1°C and a heating
rod. In all experiments prior to start CO2 was injected into the
core plug in order to remove possible air stuck in pores. Core
plug was then saturated with NaBr brine. NaBr brine as
opposed to NaCl brine allowed an accurate determination of
the porosity. Breakthrough time and pore volume of the core
plug were determined at this stage. Pressure readings obtained
from a pressure transducer (accuracy % 0.1) were recorded
when the brine flow reached steady conditions using a data
logger. Prior to each experiment reference dry CT scans
(Table 2) of 8 equally separated volume elements (slices) were
acquired and after each CO2 injection period (approximately
10 pore volumes) permeability and porosity of the core plugs
were measured. At the end of each CO2 injection period the
core plugs were re-saturated with brine and reference wet CT
scans were shot at the same locations. Porosity of each slice
was then obtained by averaging porosities obtained in a
circular region of interest that is slightly smaller than the
diameter of the core plug. The porosity for a slice was
obtained using the following equation11.
CTwr − CTar
φ= (2)
CTw − CTa
In this equation subscripts w and a represent brine and CO2
CT numbers, whereas wr and ar refer to brine-saturated and
CO2-saturated rock, respectively. The distribution of
porosities and raw CT images (Fig. 2) showed the
heterogeneous nature of the core plugs. Experiments were
conducted at differing injection rates (3, 6 and 60 cc/min),
temperatures (20, 35 and 50ºC) and brine salinities (0, 2.5, 5
and 10 weight percent).
SPE 93773 3

Table 1. Physical properties of the core plugs used in the Horizontal Oriented, %10 NaBr, 18 C, 3-6-60 m l/m in
experiments 1,60 1,40
Initial φ Initial K 1,40 1,20

Permeability ratio, k/ki

Plug D cm L cm % md

Porosity ratio, phi/phii

1,20
1,00
1 4.72 10.7 24 44 1,00
0,80
2 4.72 10.7 11 23.4 0,80
0,60
3 3.81 7 22.3 451.9 0,60
0,40
4 4.72 10.7 21 19.9 0,40
Permeability ratio_experimental 0,20
5 4.72 10.7 26.8 58.7 0,20 Pemeability ratio_Carmen&Kozeny
Porosity ratio_experimental
0,00 0,00
6 4.72 10.7 24.4 38.6 0,00 50,00 100,00 150,00
7 3.81 7 10.3 2.9 Inj ected Pore Volume of CO2

8 3.81 7 30 79.0

Table 2. CT scan parameters used in the experiments

Scan time 3 seconds
Field of view 16 cm
Current 250 mA
Voltage 130 kV
Slice thickness 10mm
Positioning
accuracy ±1 mm

Sleeve
Temperature Control

In Out Horizontal Oriented, %10 NaBr, 50 C, 60 ml/min

Core plug
1,2 1,06
1,04
Perm eab ility ratio , k/k i

Po ro sity ratio , p h i/p h ii

p
1,02
Gantry 0,8
CO2 1
CO2 Brine
Back
Transfer
cell
p Pressure 0,6 0,98
p
MF Pump
Core 0,96
High Pressure
0,4
Seperator 0,94
Permeability raito_experimental
Patient Table 0,2 Pemeability ratio_Carmen&Kozeny 0,92
Porosity ratio_experimental
0 0,9
Figure 1. Experimental setup. 0 20 40
Injected Pore Volume of CO2

Figure 3. Effect of temperature on permeability and porosity

change.

Figure 2. Locations of CT slices and sample CT images taken
along the core plug (injection is from left to right).
Results and Discussions
Figures 3 through 6 presents the results of experiments
conducted with varying temperatures (Fig 3), brine salinities
(Fig 4), core orientations (Fig 5) and injection rates (Fig 6).
General observations
In general for vertically oriented core plug experiments, it
was observed that the permeability increased and then
decreased after a certain pore volume regardless of the salinity
and injection rate (Fig. 5). On the other hand, for horizontally
oriented core plugs the permeability initially decreased and
then after a certain injection stabilized. Porosity observations
however did not one to one match the permeability behavior
but showed similar trends. In horizontally aligned cases the
porosity stayed above the original level for a long time.
Results of these experiments suggest that orientation of cores
have a strong impact on permeability and porosity alteration
trends. In vertically oriented core plugs due to gravitational
forces CO2 easily moves to the top of the core. This in turn
increases the contact area of the CO2 in pores near the inlet
and increases chemical reaction frequency leading to the
formation of carbonic acid. As the injection continues some
of the dissolved calcite blocks the smaller pores along the flow
path and thus results in a decrease in permeability later during
the experiment. On the other hand, for horizontally aligned
4 SPE 93773

core plug experiments injected carbon dioxide does not move different temperatures (18° and 50°C). For the 35°C
easily to the end of the core plug and forms carbonic acid near experiment, permeability stayed constant for a while and then
the inlet. This results in an increase in porosity near the inlet increased. The porosity trends for these experiments followed
only. Calcite particles then deposit along the flow path the permeability trends. The permeability calculated from
especially near the exit which results in a decrease in porosity using a Cozeny type equation (CMG, 2004) given
permeability. CT derived porosity values support this theory below did not exactly match the observed permeability but the
as shown in Fig 7. Later in the experiment permeability keeps trend was similar.
on decreasing until an equilibrium state where no longer c 2
alteration in permeability and porosity is observed. These ⎛φ ⎞ ⎛ 1 − φ0 ⎞
observations are in accord with the ones reported by Omole K f = K 0 ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ (3)
and Osoba9. ⎝ φ0 ⎠ ⎝ 1−φ ⎠
In this equation, K0 and φ0 are the original or initial
Ve rtical Oriente d, Distille d Wate r, 18 C, 60 m l/m in
permeability and porosity, and c is a user defined power that is
1.6 adjusted to have a match with the experimental data. Note that
permeability calculated from porosity using the above
Permeability ratio, k/ki

1.4
1.2
equation assumes that turtousity is constant. In practice;
1
0.8 however, as carbonic acid dissolves calcite and the calcite
0.6 particles deposit, the turtousity should change continuously.
0.4
0.2
Permeability norm_exp For the experiments where the Cozeny type model represents
0 the permeability change it could be speculated that the
0 20 40 60 80 turtousity does not change or stays nearly constant.
Inje cte d Pore Volum e of CO2

Ho r iz o n tal Or ie n te d , %10 NaBr , 18 C , 3 m l/m in

Vertical Orie nted, %2.5 NaBr, 18 C 60 m l/m in
1 ,6 0 1 ,4 0
1,4
1 ,4 0 1 ,2 0
P e rm e a bility ra tio, k

1,2

P oros ity r a tio, phi/p

1 ,2 0
Permeability ratio, k/ki

1 ,0 0
1
1 ,0 0
0 ,8 0
0,8 0 ,8 0
0 ,6 0
0,6 0 ,6 0
0 ,4 0
0,4 0 ,4 0
P erm e abilit y ra t io _ ex p erim en t al
0 ,2 0 P em eab ilit y ra t io _C a rm e n& K oze ny 0 ,2 0
0,2 Permeability norm_exp P oro s it y ra t io_e x pe rim ent al
0 ,0 0 0 ,0 0
0
0 ,0 0 2 0 ,0 0 4 0 ,0 0 6 0 ,0 0 8 0 ,0 0
0,00 50,00 100,00 Inj e c te d P ore V olum e of CO 2
Inj ected Pore Volume of CO2
Ve rtical Oriente d, %10 NaBr, 18 C, 3 m l/m in
Ve rtical Orie nted, %5 NaBr, 18 C, 60 m l/m in 3 1,4
1,4
2,5 1,2

Porosity ratio,phi/phii
1,2
Permeability ratio, k/ki

1
Permeability ratio k/ki

2
1
0,8
0,8 1,5
0,6
0,6 1
0,4
0,4 0,5 Permeability norm_exp
0,2
Pemeability norm_Carmen&Kozeny
Porosity norm_exp
0,2 Permeability norm_exp
0 0
0 100 200 300
0
Inje cted Pore Volum e of CO2
0,00 10,00 20,00 30,00
Inj ected Pore Volume of CO2 Figure 5. Effect of orientation on permeability and porosity
Figure 4. Effect of salinity on permeability and porosity change. change.

Salinity and rate effect

Temperature effect
The effect of temperature on calcite scaling was analyzed
using three experiments conducted at 18°C, 35°C and 50°C.
The latter is a typical temperature observed in shallow
geothermal reservoirs in Turkey. The CO2 injection rates
covered a wide range (3 to 60 ml/min) corresponding to slow
reservoir flows to fast near wellbore flows. In horizontally
oriented core plugs the permeability decreased to 40% of the
initial permeability after CO2 injection then stabilized around
this value for a while (Fig 3). Then it started to decrease
again. This behavior was observed for two experiments with
It was observed that salinity (Fig 4) and injection rate (Fig.
5) of CO2 has no drastic effect on changes in rock properties
as the salinity was increased from 0 to 5% by weight and
injection rate of CO2 was increased from 3 ml/min to 60
ml/min. It was observed that when distilled water was used
the permeability increase was 40% more compared to saline
cases, 20%. As the salt content of the brine increased
permeability drop was pronounced more. The duration of CO2
– rock contact time and the amount of area contacted by CO2
seems to have a more pronounced effect compared to rate
effect.
SPE 93773 5

Effect of heterogeneity and pH

25
The effect of heterogeneity was also analyzed. The
homogeneous core was a carbonate coming from a French
quarry (St. Maximin). This carbonate is known to be quite 22.5

Porosity, %
homogeneous with high porosity and permeability (0.417 and
1.02 Darcy respectively). The core was in parallelepipedic 20
shape (5 x 5 x 20 cm3) and placed vertically. The experiment
was conducted using distilled water and CO2 was introduced 17.5 Initial
from the bottom of the core plug. Permeability continuously 20.4 PV CO2
increased following the the injection (Fig 9). Dissolution of 15
the carbonate rock by CO2 dissolved in water is shown 0 2 4 6 8 10
through permeability change (45%) but porosity increase Slice
(0.417 to 0.432) was not so high. It looks from those results
Figure 7.Porosity change observed during a horizontal
that the rock is not dissolved in a continuous way but that
experiment (10% NaBr, 18°C, 3ml/min).
preferential channels (worm holes) are generated in the rock.
Assuming the pore size distribution is unimodal and that the The change in pH of the aqueous phase was also studied
pores and pore throats are evenly distributed and large, it (Fig. 8). It was observed that pH of the effluent was basic as
could be speculated that the calcite particles never find a opposed to acidic in many instances. In essence the pH of the
chance to deposit along the core. On the other hand for effluent closely followed the porosity change. Thus these
heterogeneous Midyat core plugs since the pore size results are in accord with the aforementioned observation, i.e.,
distribution is bimodal and the pores and throats have small to for horizontal experiments injected carbon dioxide does not
large values, the calcite particles could deposit along the flow move freely to the end of the core plug and forms carbonic
path. acid near the inlet. This results in an increase in porosity near
the inlet only. Calcite particles then deposit along the flow
Ho r iz o n tal Or ie n te d , %10 NaBr , 18 C , 3 m l/m in
1 ,6 0 1 ,4 0
1 ,4 0 1 ,2 0
path especially near the exit which results in a decrease in
permeability and an increase in pH.
P e rm e a bility ra tio, k

P oros ity r a tio, phi/p

1 ,2 0 1 ,0 0
1 ,0 0
0 ,8 0
0 ,8 0
0 ,6 0
0 ,6 0
0 ,4 0
0 ,4 0
P erm e abilit y ra t io _ ex p erim en t al
0 ,2 0 P em eab ilit y ra t io _C a rm e n& K oze ny 0 ,2 0
P oro s it y ra t io_e x pe rim ent al
0 ,0 0 0 ,0 0
0 ,0 0 2 0 ,0 0 4 0 ,0 0 6 0 ,0 0 8 0 ,0 0
Inj e c te d P ore V olum e of CO 2

Horizontal Oriented, %10 NaBr, 18 C, 6 m l/m in

2,7
2,7 Permeability ratio_experimental
Pemeability ratio_Carmen&Kozeny
Porosity ratio_experimental 2,2
Permeability ratio, k/ki

2,2
1,7
1,7
1,2 Figure 8. pH change observed during a horizontal experiment
1,2 (10%NaBr, 35°C, 6 ml/min).
0,7 0,7
2500
0,2 0,2 Experiment simulation
0 10 20 30 40 2000
Injected Pore Volum e of CO2
permeability, md

Hor iz ontal Or ie nte d, %10 NaBr , 18 C, 60 m l/m in 1500

1,4 1,40
Perm eability ratio, k/ki

1000
Porosity ratio, p hi/ph

1,2 1,20
500
1 1,00
0
0,8 0,80
0 5 10 15 20 25 30 35 40 45
time, days
0,6 Perm eability ratio_ex perim ental 0,60
Pem eability ratio_C arm en&Kozeny
Poros ity ratio_ex perim ental
Figure 9. Permeability change observed in homogeneous core
0,4 0,40 plug (Distilled water, 21°C, 7 ml/h).
0 10 20 30 40
Inje cte d Por e V olum e of CO2 Numerical Model
Figure 6. Effect of flow rate on permeability and porosity change. Experiments were modeled using STARS multicomponent,
non-isothermal process simulator12. Radial gridblock system
6 SPE 93773
with 14x25x24 blocks was used to model the laboratory
experiments. Core plugs were considered to be heterogeneous
and initial porosity obtained from CT scans were designated to
each block corresponding to a slice (Fig. 2). The remaing
porosities were distributed using an inverse-distance squared
distribution function. Power law relative permeabilities were
used. The solution and deposition reactions given by Eqn 1
are treated separately. The reaction model's heterogeneous
mass transfer (source and sink) terms were applied to the
nonequilibrium capture and release of calcite particles by the
porous rock. This requires that the reaction rate constants
depend upon permeability, to account for the changes in
capture efficiency as the calcite particle size to pore throat size
ratio changes. To specify the dependence of chemical
reactions and nonequilibrium mass transfer on permeability an
effective permeability reaction rate factor table was used
(Table 3). Thus, permeability change was controlled by
reaction frequencies (1/min-kPa) of the solution and
deposition reactions and Carman-Kozeny coefficient given by
Eqn. 3. Calibration of the simulation model was conducted by
changing the following parameters: reaction frequencies of the
solution and dissolution reactions, Carman-Kozeny
coefficient, initial concentrations of solid phase carbonate and
aqueous phase bicarbonate, aqueous phase sodium bromide
particles and adsorption rate of CO2. Adsorption of CO2 was
assumed to be of Langmuir type. Figure 9 and 10 show
sample matches to one of the vertically oriented Midyat
carbonate plug experiments and the homogeneous core plug
experiment. It can be seen that the proposed chemical reaction
and adsorption model can capture the physics of the
experiments quite well. In order to obtain a match for the
heterogeneous experiment solution and reaction frequencies
were set to 200 and 56 respectively. On the other hand these
numbers were 30 and 0 for the vertically oriented
homogeneous core plug experiment. It was observed that for
the vertically oriented experiments deposition reaction
frequency numbers were smaller than that of for the
horizontally oriented experiments.
Table 3. Dependence of reaction or mass transfer rate on
permeability.
Effective permeability, md Reaction rate factor, 1/min
100 2.5
450 1.0
750 0.75
1000 0.5
1.4
simulation
Permeability, md
1.2
experiment
1 deposition sites slightly differed and mainly concentrated in
0.8
0.6
0.4
0.2
0
0 100 200 300 400
Time, minutes
Figure 10. Comparison of simulation results with experimental
ones: heterogeneous core plug (10%NaBr, 18°C, 60 ml/min).
Field Simulation
Midyat aquifer is located in south eastern part of Turkey
(Fig 11). At the center of the aquifer is the largest town
(population: 1’362’708) that is the primary source of CO2
production and potential target for CO2 sequestration
applications in this region13. Average depth of the aquifer is
750 – 800 m in north, 750 m in south and 550 m in west. The
minimum depth is 510 m, the average thickness of the
formation is 200 to 350 m and total area covered by the
aquifer is 19855 km2. Cartesian grid system with 67x42x3
grid blocks (20x20km) was used to model the aquifer (Fig 12).
The aquifer recharge zones are mainly from north and south.
The recharge amounts (496 mm/year at the center near
Diyarbakir, 450-500 mm/year at the East boundary, 700-750
mm/year at the north and south respectively) were calculated
using data acquired from meteorological stations. The
recharge of the aquifer is modeled using a boundary aquifer
with a relatively small thickness, 100 m. History matching of
the production data covered a period of more than 25 years.
Fig 13 gives matches obtained for several wells located in
north west (well #2), center (well #7) and south west (well
#13) of the field. The CO2 injection process was modeled
using the aforementioned chemical reaction and adsorption
model. The total amount of CO2 injected from Diyarbakir
region was equal to 200 mid size power plants’ (200x109 kg
CO2/year) yearly production14.
Region of interest
Figure 11. Location of the Midyat aquifer.
Two cases were considered: gaseous (6183 kPa) and CO2
supercritical injection (7689 kPa) for 100 years. For the
gaseous and supercritical injection the breaktrough of CO2
occurred after 75 and 93 years of injection respectively. It was
observed that supercritical CO2 injection resulted in longer
residence time. The results of simulation also showed that for
the gaseous and supercritical CO2 injection pH has increased
to 10.4 and 14.9 respectively (Fig 14) which are both higher
than the experimentally observed values. Major calcite
east and south east for the gaseous CO2 injection and both
north east and east for the supercritical CO2 injection. These
sites coincided with pH change locations and the number of
deposition sites was larger for supercritical CO2 injection.
500 600
Similar to observations made during the experiments CO2
sequestered by mineral deposition (0.05%) was significantly
less than hydrodynamic and solubility trapping. Gas mass
density and water mass densities observed at the end of 95
years of supercritical CO2 injection is given in Fig. 15. At the
SPE 93773 7

end of 95 years CO2 has mainly invaded top portions of the 6. Numerical simulations showed that supercritical CO2
aquifer; however, virgin zones are still observed. injection is better than gaseous CO2 injection as it
provides longer residence time.
7. pH observed in the numerical simulations were
somewhat more than those observed in the
experiments.
8. CO2 sequestration via mineral deposition (0.05%) is
significantly less than solubility trapping and
hydrodynamic trapping.

8000
7500
7000

Pressure, kPa
6500
observed
6000
model
5500
5000
4500
4000
1960 1970 1980 1990 2000
Time, years

8000
7500
7000
Pressure, kPa

6500
observed
6000
model
5500
5000
4500
Figure 12. Aquifer model pressures (kPa) observed for 1971 (top) 4000
and 2004 (bottom). 1960 1970 1980 1990 2000
Time, years
Conclusions
Results of CT monitored CO2 injection experiments showed
that: 8000
1. Calcite scaling is mainly influenced by orientation 7500
and horizontal flow resulted in larger calcite 7000
Pressure, kPa

deposition compared to vertical flow. 6500

2. The duration of CO2 – rock contact and the amount of observed
6000
area contacted by CO2 seems to have a more model
pronounced effect compared to rate effect. 5500
3. For the temperature range studied (18°C – 50°C) 5000
permeability and porosity alteration trends were 4500
similar. 4000
4. Once the porosity is known the permeability behavior 1960 1970 1980 1990 2000
could be predicted by a Cozeny type equation.
Time, years
5. A numerical model that uses chemical reactions to
describe permeability and porosity changes as a result Figure 13. History match of wells # 2 (top), #7 (middle) and #13
of CO2 injection successfully represented the (bottom).
experiments conducted. It was observed that the
solution and deposition reaction frequencies and
Karman-Kozeny coefficient are the major parameters
that need to be calibrated to obtain a match.
8 SPE 93773

Figure 14. pH change observed during gaseous CO2 (top) and Figure 15. Gass mass density and water mass density observed at
supercritical CO2 (bottom) injection. the end of 95 years of supercritical CO2 (bottom) injection.

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We are grateful to TUBITAK (Turkey) and CNRS (France) 3. Jessen, K., Sam-Olibale, L.C., Kovscek, A.R., Orr, F.M.:
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SPE 93773 9

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