SPE 116513

Measurement of the Diffusion Coefficient of CO2 in Formation Water Under

Reservoir Conditions: Implications for CO2 Storage
M. Bahar and K. Liu, CSIRO Petroleum

Copyright 2008, Society of Petroleum Engineers

This paper was prepared for presentation at the 2008 SPE Asia Pacific Oil & Gas Conference and Exhibition held in Perth, Australia, 20–22 October 2008.
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 of the paper have not been
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Abstract

Laboratory measurements of the diffusion coefficient of CO2 into brine under both unsteady state and steady state
conditions were carried out to obtain the dissolution rates of CO2 during CO2 injection and/or flooding in short term
and for CO2 preservation at thermodynamic equilibrium in long term. The experiments used pure CO2 gas and a
synthetic brine of 2% NaCl with experimental P/T conditions at 2580 Psia and 83 oC, respectively, similar to that
of the target reservoir interval of the proposed CO2 injection well (CRC-1) in the Otway Bain, Australia. The
pressure drop in the core flooding cell during the contact of the CO2 and brine phases was used to measure the
diffusion coefficient of the system under the storage condition. The diffusion mechanism includes both a steady
state and an unsteady state component. The diffusion coefficient of the CO2 in the unsteady state appears to be
larger than that of the steady state. The duration of the unsteady state appears to strongly depend on the
pressure and temperature of the system.

Introduction
During CO2 sequestration, some CO2 may be dissolved into the formation water under reservoir conditions. The
rate of the CO2 dissolution depends on the diffusion coefficient of the CO2 in the formation water. Experimental
data on the CO2 diffusion under reservoir storage conditions is thus important for the accurate simulation of the
CO2 storage system. However, most of the commercial simulation softwares do not take into consideration of the
diffusion factor at high temperature and pressure.

In 2004 the Otway Basin in southeastern Australia was nominated for a CO2 sequestration site. CO2 was
designed to be injected into the Late Cretaceous Waarre C Sandstone at a depth of 2000 metres (Cook and
Sharma, 2006). The critical temperature and pressure of CO2 are 31.1 oC and 7.38 Mpa. Under the present
reservoir condition below 2000 m in the Otway Basin, the CO2 is in a supercritical state.
The behaviors of CO2 in formation water at atmospheric condition has been studied by many researchers (e.g.
Zhang , et al., 2006; Holder et al. 2001; Rodhakrishnan et al., 2003). However, little experimental data on the
behaviour of CO2 in formation water under reservoir conditions is available in the literature, especially regarding
the rate of dissolution and mass diffusion of CO2 in formation water during the contact between CO2 and
formation water.

Laboratory measurements of the diffusion coefficient of CO2 into the formation water under both unsteady state
and steady state conditions were carried out to obtain the dissolution rates of CO2 during CO2 injection or flooding
in short term and for CO2 Storage and preservation in relatively long term at thermodynamic equilibrium. Pure CO2
and distilled water with 2% NaCl were used in the experiment with P/T conditions at 2580 Psia and 83 oC,
repectively, similar to that of the proposed CO2 injection reservoir (CRC-1) in the Otway Bain.
In this study, the pressure drops of the CO2-formation water system at reservoir condition are used to determine
the diffusion coefficient of mass transfer for CO2 in the formation water at Otway Basin. Dissolution of the CO2
gas into the formation water causes the decrease of pressure in the system. By applying the equation of state and
Fick’s Law the diffusion coefficient for two phases can be determined.
2 SPE 116513

Laboratory experimental data from this study has also been modeled using the FlexPDE software to solve the
partial differential equations and to predict the rates of diffusion for other reservoir conditions.

Mechanisms of mass transfer in CO2 –formation water at reservoir P/T conditions

In the case of CO2 and formation water in direct contact in a cylinder the dissolution of CO2 into the liquid phase is
not instantaneous because of the slow mass transfer rate. The dissolution of CO2 depends on the carbon dioxide
volume, the contact time, the contact area, and the mass transfer rate. When some CO2 has been dissolved into
the water, the pressure inside the cylinder will be reduced based on the flux of diffusion. Over time some CO2
component will diffuse into the water and some water component will diffuse into the gas phase (Fig. 1). If the first
mechanism becomes dominant, the pressure of the system will be reduced and the water will swell (Fig. 1B). If
the second mechanism prevails, then the water will evaporate into the gas phase and the gas will be enriched
with water vapour, and accordingly the pressure of the system will be increased (Figure 1).

Figure 1, A schematic representation of CO2 and water in contact at t=0 (A); at t>0 (B) with the swelling
volume indicated and at t= ∞ (C).

The water volume increases with time during contact of the two phases. It is characterized by a sharp initial
increase in volume followed by a gradual increase toward the saturation concentration of CO2 in the liquid phase
(Fig. 1B). The extent of the variation in the swelling with time is strongly affected by the adjusted pressure.
Swelling at high pressures increases more rapidly to a larger extent compared with that at low pressures. The
extent of the swelling decreases as the solubility of CO2 decreases.

Despite a wealth of research being carried out on the mechanism of mass transfer from the gas phase into the
liquid phase after the initial contact, there is little or no information in the literature with respect to the mechanism
of mass transfer during the initial contact. It is not well understood why the mass transfer rate at the initial period
of contact between the gas and liquid phase is so high especially under high pressures. In order to explain the
high mass transfer rate during contact, attempts have been made to solve the diffusion equations under the
condition that the diffusion coefficient is not constant but varies with time. These calculations are performed to
explain further the mechanisms of mass transfer during the initial contact period.

In the literature few researchers have attempted to describe the dependency of the diffusion coefficient on the
volume-averaged concentration of a solute which changes with time. Sano and Yamamoto (1990) assumed that
the diffusion coefficient is a function of the concentration, and attempted to establish various correlations using
one or more parameters. Van der Zanden (1998) presented a numerical procedure to obtain the dependency of
the diffusion coefficient on the concentration whether the space-averaged concentration is known as a function of
time. A number of methods are available to solve equation (1) numerically when the diffusion coefficient varies as
the contacting time increases and the solution becomes more concentrated. In fact, the diffusion coefficient can
be position dependent if the properties of the media (such as viscosity, density) vary strongly with positions,
pressure and temperature and are viscosity dependent.
SPE 116513 3

Mass transfer with variable diffusion coefficients

In many systems, such as homogeneous, heterogeneous and fractured porous media or even the diffusion of
organic vapours of high-polymer substances, D in equation 1 depends on the concentration of the diffusing
substance C. In this case, and also when the medium is not homogeneous D varies from point to point as the
following (Equation 1);

∂C ∂ ⎛ ∂C ⎞ ∂ ⎛ ∂C ⎞ ∂ ⎛ ∂C ⎞
= ⎜D ⎟ + ⎜D ⎟+ ⎜D ⎟ (1)
∂t ∂x ⎝ ∂x ⎠ ∂y ⎜⎝ ∂y ⎟⎠ ∂z ⎝ ∂z ⎠

where D is a function of position (x, y, z), pressure, temperature, viscosity and C.

Measuring Diffusion Coefficients under static state conditions using a PVT Cell.

An experimental system was designed and installed as part of this study as shown in Figures 2. This equipment,
a multiphase core flooding system, can be used to conduct measurements of the diffusion coefficient at high
pressures and temperatures (under reservoir condition). The PVT cells were designed in a way that the pressure
and temperature of the system could be measured while the mass transfer phenomena were taking place. The
PVT cell enables the measurement of the liquid volume increase due to swelling as a result of the mass transfer
taking place between liquid and gas phases. The main components of the experiment are described in detail in
the following sections. High accuracy positive displacement pumps as shown to increase the pressure of the
system. Two computers with the Falcon software were used for monitoring the experiments and data collection

Figure 2– Schematic diagram illustrating the CO2 diffusion experiments

Diffusion Coefficient measurement procedure at high pressure and temperature

Pressure drop is known to have the most influence when two non equilibrium phases are in direct contact under a
static condition. A PVT cell was used to measure the diffusion coefficient under a static reservoir condition. The
pressure of the system is a function of the time and composition of each phase. The following procedure was
used to measure the diffusion coefficient by measuring the pressure drop while the two phases were in direct
contact within the PVT cell.
1. The high pressure cylinder (PVT cell) was cleaned, dried and connected to the displacement
pumps.
2. The PVT cell was then vacuumed for two hours.
4 SPE 116513

3. The PVT cell was then filled with the pre-made formation water.
4. The high pressure gas cylinder was filled with pure carbon dioxide at 345 Bars.
5. The top of the PVT cell was connected to a CO2 cylinder through a valve.
6. The valve is closed when the pressure in the PVT cell reaches to the desired target pressure of
2585 Psi.
7. The pressure drop measurement was then started once the top valve was closed.

The equipment was then left to stand for a period of time. As time passed, the pressure of the system began to
drop until it reached an equilibrium. The amount of CO2, transferred, was calculated based on the pressure drop
in the PVT cell using the method discussed above.

Mass transfer in a PVT cell under reservoir conditions

The diffusivity of a gas into a liquid phase has been repeatedly measured at low pressures and temperatures for
many media since the early 1900s. However, there are no reliable experimental data on the diffusion coefficients
available in the literature at typical reservoir P/T conditions. It is well-known that he diffusion plays the most
important role in the mass transfer that is taking place between CO2 and formation water during CO2 flooding.
As it is shown in Figure 3, the concentration of liquid and gas phases change with time when mass transfer is
occurring at the interface between the liquid and gas phases. Wittman (1923) proposed the presence of a “film” at
the interface of gas and liquid phases (both in thermodynamic equilibrium). His theory states that on either side of
the liquid-gas interface there exists a film of relatively quiet fluid, and that the gas absorbed must pass through
this “film” interface by diffusion. The rate of the gas dissolution is directly proportional to the difference in
concentrations of the diffusing gas on either side of the interface. During the contact between the gas and liquid,
the gas molecules diffuse into the liquid phase across the interface. As a result, the liquid phase swells at the
interface and moves to a new position.

Figure 3: Schematic of moving boundary during contact of phases

The pressure of the two-phase system strongly depends on the more compressible phase (e.g. gas). During the
contact between the liquid and gas phases in the closed system (e.g. the PVT Cell), if the liquid phase component
evaporates into the gas phase through the interface, the pressure of the system would increase. During the
condensation process, when the lighter components of the gas phase dissolves into the liquid phase, the
pressure of the system would decrease until equilibrium is achieved. This was clearly evidenced during the CO2
diffusion experiments. By applying the material balance calculation on each phase, the following mathematical
equation can be developed. For instance, the moles of CO2 removed from the gas phase were equal to the moles
of CO2 diffused into the liquid phase. This can be calculated using the following equations (Equation 2-4):
SPE 116513 5

V dP (t )
Number of moles removed from the gas phase per time = (2)
Z g RT dt
dC g
Number of moles diffused into the liquid phase per time = − D go A( ) (3) (7.1)
dZ

V dP (t ) dC
= − Dgo A( g ) (4)
Z g RT dt dZ

When the volume of gas and cross sections of the PVT cell are constant then
Equation (4) can be simplified as:

dP(t ) Z RT dC
=− g Dgo ( ) z = z0 (5)
dt h dZ
Where Dgl is the diffusion coefficient. It depends on the concentration, pressure, temperature, viscosity and
distance. The classical diffusion coefficients are considered to be constant under steady state conditions. In this
experiment, based on the pressure drop system shown in Figure 4, the system was divided into two main parts
(Region 1 and Region 2), represent unsteady state and steady state, respectively. In the steady state, the
diffusion coefficient can be considered to be approximately constant but in the unsteady state, diffusion coefficient
strongly depends on the parameters such as pressure, temperature, viscosity, volume and molecular weights.
During the CO2 injection into a water saturated reservoir in the case of CO2 sequestration, mass transfer would
occur under an unsteady state condition and hence the role played by the diffusion coefficient becomes important.
in order to measure the diffusion coefficient in a PVT cell, the determination of the diffusion coefficient from the
pressure–time profile was based on the mathematical analysis of the diffusion process. The initial and final molar
concentration of the gas phase was calculated with the equation of state. A significant amount of gas would be
transferred into the formation water during the unsteady state process depending on the gas solubility. The rate of
gas transfer into the formation water, however, would be controlled by the diffusion coefficient of the carbon
dioxide.

Figure 2 is a schematic representation of the experimental system with the PVT cell size of 1.5-litre volume and
the initial volume of the liquid phase of 800 cm3 and the volume of gas phase of 200 cm3. In this model, all data
were collected with high accuracy (0.001) every minute using the Falcon software and two Dell computers.
Figure 4 shows two regions based on the experimental data which were measured in the PVT cell. Region-1 is
where the unsteady state process is taking place and where the mass transfer rate is much higher than that in
Region-2 where the steady state process takes place. The diffusion coefficient, which controls the rate of
diffusion, varies with time in the unsteady state process during the experiments. Some investigators (e.g. Renner,
1988) referred the incubation period as the unsteady state region. When the pressure and temperature were low,
the incubation period was found to be short and hence had been neglected by most researchers. In this study, it
was found that the incubation period increased as the pressure and temperature of the system were increased.
6 SPE 116513

2500 Unsteady
State

2300
Figure 3 – Pressure drop during the CO2 diffusion experiment
Pressure Drop (Psia)

Steady State
2100

1900

1700

1500
0 1000 2000 3000 4000 5000 6000
Time (minute)
Figure 4: Pressure drop during the CO2 diffusion experiment
The diffusion coefficient was obtained under a static state condition, using a PVT cell, by matching the
experimental pressure drop and that predicted by the empirical correlation which was developed using the finite
elements method (Equation 6):

T 1.47 MW 2.2
Dgo = 1.3678 x10−7 (6)
V 0.5 Pμ o
where P and T are pressure and temperature of the system. MW, V, are the molecular weight, volume and
viscosity of the liquid phase, respectively.

Modelling of the system by the finite element method

There are several useful empirical correlations available for obtaining the diffusion coefficient. In this research the
following empirical correlation was used in static and dynamic conditions. This correlation was applied by
FlexPDE software to match the experimental data with the theory of the partial differential equation. The software
yielded high levels of accuracy and was user friendly. The strength of the software lies in the automatic mesh
generation, mesh refinement during the solution process, and automatic time step control.
In this study, a two dimensional spatial problem was divided into triangular elements and the variables were
approximated by third order polynomials in each element.

Results and discussion:

The concentration of the CO2 varies along the Z-axis in the liquid phase and it was considered to be constant in
the gas phase. Figure 5 shows the concentration variation in the liquid phase where diffusion mainly occurred in
the region close to the gas-liquid interface. This means that the upper region in the PVT cell achieved equilibrium
much faster than the lower region of the cell. The main diffusion occurred between the liquid and gas phases;
then self-diffusion into the liquid phase continued because of the presence of concentration gradient within the
liquid phase.
SPE 116513 7

CO2 Saturation
CO2 concentration

CO 2 Saturation Profile

Length of cell
S CO
2
in
Ot
wa
y
Fo
rm
at
ion

Diameter of Cell
Figure 5: Saturation variations of CO2 in formation water

The diffusion coefficient of carbon dioxide into the water phase was calculated from a new empirical correlation
shown in Equation 6. The variations of the diffusion coefficient with time are shown in Figure 6A. This parameter
in the oil phase strongly depended on the carbon dioxide concentration in the water phase. The distribution
coefficient varied, from the start of the contact with the interface until the end of the incubation period, between
4.5x 10-4 and 4.7 x 10-4.

Figure 6: (A) Diffusion Coefficient of CO2 in the Otway Basin formation water;
(B) Variations of CO2 in the Otway Basin formation water with time

Figure 6B shows the variations of carbon dioxide concentrations along the water phase from Z=10 to Z=0. The
modelling results showed that the CO2 concentration approached equilibrium over time (at 1300 minutes) into the
water phase. Curve ‘a’ is the top of the water phase where the gas phase diffused through the interface into the
water phase and curve ‘j’ is the bottom of the liquid cylinder which had little effect. The dissolution of the CO2 into
the water phase can result in lower viscosity, density and interfacial tension. With increasing pressure of the
system the density and viscosity of the solution may be gradually increased.
8 SPE 116513

Conclusions
The laboratory CO2-brine diffusion experiment using a reservoir P/T condition similar to the CRC-1 CO2 injection
reservoir interval in the Otway Basin, southeastern Australia indicates that the CO2 diffusion Coefficient varies
between 4.5x 10-4 and 4.7 x 10-4from the initial CO2–brine contact until when equilibrium was reached. The
experiment has also shown that
1) The Diffusion Coefficient of CO2 in reservoir formation water varies with pressures and temperatures
2) The solubility of CO2 depends on the incubation period of contact, which is in turn dependent on pressure
3) The Diffusion Coefficient of CO2 for the unsteady state appears to be higher than that for the steady state
and become constant under the steady state condition
It is suggested that CO2 diffusion under reservoir conditions should be considered when simulate CO2 flooding for
short term Enhanced Oil recovery EOR purpose and especially for long term CO2 sequestration and storage,
where the contribution of CO2 diffusion may be substantial volumetrically given the huge volume and contact
fronts involved.

Acknowledgements:
The School of Petroleum Engineering, Curtin University of Technology is thanked for allowing the access to its
core flooding facility. The work undertaken with the financial support of the Microbially Enhanced Oil Recovery
project in the CSIRO Wealth from Ocean Flagship Program.

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