Simulation of Hydrate Dynamics in

Reservoirs
M.T. Vafaei, B. Kvamme, A. Chejara, and K. Jemai, University of Bergen
Summary
Gas hydrates in reservoirs are generally not in thermodynamic
equilibrium, and there may be several competing phase transitions
involving hydrate. Formation of carbon dioxide (CO
2
) hydrates
during aquifer storage of CO
2
involves roughly 10 vol% increase
compared with groundwater. Dissociation of hydrate toward
undersaturated uid phases involves the same level of contraction.
Hydrate phase transitions are generally fast (scales of seconds)
compared with mineral dissolution and precipitation, and it is
unlikely that a time-shifted explicit coupling to geomechanical
analysis will be able to capture the appropriate dynamic couplings
between ow and changes in stress. The need for geomechanical
integrity of the storage site therefore requires a reservoir simulator
with an implicit solution of mass ow, heat ow, and geome-
chanics. And because CO
2
involved in hydrate is also involved in
different geochemical reactions, we propose a scheme where all
possible hydrate formation (on water/ CO
2
interface, from water
solution, and from CO
2
adsorbed on mineral surfaces) and all dif-
ferent possible dissociations are treated as pseudoreactions, but
with kinetics derived from advanced theoretical modeling. The
main tools for generating these models have been phase-eld-
theory (PFT) simulations, with thermodynamic properties derived
from molecular modeling. The detailed results from these types of
simulations provide information on the relative impact of mass
transport, heat transport, and thermodynamics of the phase transi-
tion, which enable qualied simplications for implementation
into RetrasoCodeBright (RCB) (Saaltink et al. 2004). The primary
step was to study the effect of hydrate growth or dissociation with
a certain kinetic rate on the mechanical properties of the reservoir.
Details of the simulator and numerical algorithms are discussed,
and relevant examples are shown.
Introduction
Natural-gas hydrate in the reservoir is continuously attracting the
attention of more researchers around the world, and the reason is
its importance from different aspects, ranging from a potential
energy resource to environmental threat. Hydrate can occur in
sediments below the oceanic oor or in the permafrost, wherever
the thermodynamic conditions are suitable and water and guest
molecules are available. Investigations show that there are huge
resources of natural-gas hydrate in the Earth, which because of
the high volumetric concentration of methane gas per hydrate vol-
ume is considered as a substantial energy resource. Besides, meth-
ane (CH
4
) combustion releases less CO
2
per unit energy release
compared with both coal and oil, which means a cleaner fuel from
an environmental point of view. On the other hand, CH
4
can be
more than 20 times more aggressive than CO
2
in trapping the heat
in the atmosphere, and its leakage from sediments affects the ma-
rine life and the climate substantially. Another attractive aspect of
sediment gas hydrates is the potential of storing CO
2
in the form
of CO
2
hydrate. Disposal of the CO
2
below the seabed is consid-
ered as one of the most promising and safe options for storage of
CO
2
(Koide et al. 1997; Zatsepina and Pooladi-Darvish 2011).
There are several scenarios for CH
4
production from natural-
gas-hydrate reservoirs. Depressurization is the one of these meth-
ods in which the hydrate stability condition is disturbed by pres-
sure reduction according to the water/gas/hydrate equilibrium
curve, resulting in hydrate dissociation and release of CH
4
. It has
been investigated by many research groups through both simula-
tion and experimental studies. Thermal stimulation is another
method, based on moving out from the stability region by temper-
ature increase. The third method is to use inhibitors such as meth-
anol or brine to shift the equilibrium curve and dissociate hydrate.
The nal method is injection of CO
2
into CH
4
-hydrate reservoirs.
CO
2
hydrate is more stable than CH
4
hydrate. Therefore CO
2
-
hydrate formation will provide the necessary heat to dissociate
CH
4
hydrate, and it can be considered both as a natural-gas-pro-
duction method and a CO
2
-sequestration process (Graue et al.
2008). In this method, the two primary mechanisms for CO
2
to
convert in-situ CH
4
hydrate are (1) solid-state conversions and (2)
new CO
2
hydrate being formed from free liquid water in the
pores. Both of these mechanisms have been proved theoretically
as well as experimentally (Kvamme et al. 2007; In press). Mecha-
nism (1) can hardly be viewed as any of the three classical
mechanisms mentioned previously because the enthalpy change is
limited and it is dominated by entropy changes. Therefore, it is
considered as an independent method.
Regarding the second mechanism, direct conversion of CH
4
hydrate to a mixed hydrate (in which some CH
4
remains in small
cavities and CO
2
dominates lling of the large cavities) is a slow
process. According to publications on molecular studies of this
process, as well as advanced kinetic modeling of the process
(PFT), this mechanism is restricted by solid-phase mass transport
with diffusivity coefcients on the order of 10
16
m
2
/s (Buanes
et al. 2006; Svandal et al. 2006a, b; Tegze et al. 2006a, b; Buanes
et al. 2009; Kvamme et al. 2006a, b; 2007; 2009; Svandal and
Kvamme 2009).
Creation of new hydrate from free water surrounding the
hydrate is typically also mass-transport limited (as we have shown
through several publications), but liquid-state transport with diffu-
sivity coefcients is on the order of 10
8
m
2
/s. Heat transport in
water/hydrate systems is roughly two orders of magnitude faster.
Practically, this implies that dissociation of CH
4
hydrate caused
by released heat from new CO
2
-hydrate formation is liquid-state-
transport limited, and several orders of magnitude faster than the
direct solid state conversion (Kvamme et al. In press). During
more than 2 decades, many researchers have tried to study CH
4
production from hydrate reservoirs, and more recently storage of
CO
2
in the form of hydrates in the sediments through modeling
and simulation techniques. The progress has been considerable,
but there are still many uncertainties involved in these phenom-
ena. A review of the past studies of hydrate with the approach of
modeling and simulation is presented in this section. The purpose
here is mainly to recognize major tools developed for studying
hydrate in the reservoir, specically in the form of simulators, and
to distinguish some of their differences, specically with respect
to the thermodynamic approach used in these tools.
Holder and Angert (1982) considered a system of stratied
hydrate and gas surrounded by impermeable layers from bottom
and top to build a 3D model for studying the hydrate-dissociation
effect on gas production caused by depressurization. Several
assumptions were made to simplify the calculations. They consid-
ered the dissociation to happen only at the interface between
hydrate and gas phase, and only conduction was considered to
Copyright VC 2014 Society of Petroleum Engineers
This paper (SPE 167259) was revised for publication from paper IPTC 14609, rst presented
at the International Petroleum Technology Conference, International Petroleum Technology
Conference, Bangkok, Thailand, 1517 November 2011. Original manuscript received for
review 21 October 2011. Revised manuscript received for review 21 August 2013. Paper
peer approved 27 August 2013.
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April 2014 SPE Journal 215
nd temperature distribution in the gas phase. They concluded
that hydrate can contribute signicantly in gas production from
such reservoirs (Holder and Angert 1982).
Burshears et al. (1986) developed a two-phase, 3D numerical
model to study gas production from a system of hydrate formation
and dissociation in the reservoir. Their model consisted of water
and any mixture of CH
4
, ethane, and propane. They considered ra-
dial ow and equilibrium conditions in the gas/hydrate interface.
Water ow was present in their model, but only heat conduction
was considered (Burshears et al. 1986).
Yousif et al. (1991) developed a 1D model to simulate isother-
mal depressurization of hydrate in Berea sandstone samples. The
model considered three phases of water, gas, and hydrate and used
the kinetics model of Kim et al. for dissociation of hydrate (Kim
et al. 1987; Yousif et al. 1991). It also considered the water ow
caused by hydrate dissociation, which according to experimental
and numerical results was considerable. The variations in porosity
and permeability of the gas phase were taken into account. Finally,
they validated their model with experimental data.
Xu and Ruppel (1999) developed an analytical formulation to
solve the coupled momentum, mass, and energy equations for the
gas-hydrate system, consisting of two components (water and
CH
4
gas) and three phases (gas hydrate, free gas, water and dis-
solved CH
4
). They made several assumptions, such as ignoring
capillary effects and ignoring kinetics of the phase transition
between hydrate and aqueous phase (Xu and Ruppel 1999).
Swinkels and Drenth (2000) used an in-house 3D thermal res-
ervoir simulator and modied the pressure/volume/temperature
(PVT) tool to study hydrate-production scenarios as well as heat
ow and compaction in the reservoir and hydrate cap. They repre-
sented the reservoir uid by a gaseous, a hydrate, and an aqueous
phase. Their system consisted of three components including two
hydrocarbons and a water component. Heat was considered as an
extra component for all phases internally in the simulator. Joule-
Thomson cooling effect was also considered automatically (Swin-
kels and Drenth 2000).
Davie and Buffet (2001) proposed a numerical model for cal-
culation of gas-hydrate volume and distribution in marine sedi-
ments. They considered the organic material from sedimentation
as the main source of carbon supply to the hydrate stable region.
The rate of sedimentation, the quantity and quality of organic ma-
terial, and biological productivity were considered as key parame-
ters in this model. Hydrate formation and dissociation were
controlled by thermodynamic conditions and driving force from
equilibrium concentration. A rst-order model with a large rate
constant was used to account for the reaction rate. They compared
their results with observations from the practical eld. Their
model was dependent on the available data of sedimentation rate
and organic content (Davie and Buffet 2001).
Goel et al. (2001) developed a single-phase-ow model to pre-
dict the performance of an in-situ gas hydrate. The gas-with-
drawal rate was assumed to be constant, and the reservoir was
assumed to be innite. It used an nth-order kinetics rate coupled
with gas ow in the porous media (Goel et al. 2001).
Moridis (2003) introduced a new module for the TOUGH2
simulator named EOSHYDR2. TOUGH2 is a 3D, multicompo-
nent, multiphase-ow simulator for subsurface purposes (Law-
rence Berkeley National Laboratory 2013). EOSHYDR2 is
designed to model hydrate behavior in both sediments and labora-
tory conditions. It is able to consider up to four phases of gas, liq-
uid, ice, and hydrate and up to nine components of water, CH
4
hydrate, CH
4
as native and from hydrate dissociation, a second
native and dissociated hydrocarbon, salt, water-soluble inhibitors,
and heat as a pseudocomponent. It includes both equilibrium and
kinetic models for hydrate formation and dissociation. It uses the
hydrate reaction model of Kim et al. (1987) for kinetic studies.
Moridis studied four test cases of CH
4
production and concluded
that both depressurization and thermal stimulation can a produce
substantial amount of hydrate; he suggested that the combination
of both can be desirable. He has used just the equilibrium
approach because of a lack of enough suitable data necessary for
the parameters of the kinetic model, although he mentioned that
slower processes such as depressurization follow kinetic dissocia-
tion (Moridis 2003).
Hong et al. (2003) presented a 2D cylindrical model to study
gas production from hydrate reservoirs. They used both analytical
and numerical approaches. The numerical model considered the
equations for gas and water two-phase ow, and for conductive
and convective heat ow, and treated hydrate decomposition
kinetically by use of the Kim et al. (1987) model. In the analytical
approach they did not consider the uid ow. They studied the
effect of the hydrate zone on the gas production from the gas layer
and also the importance of the intrinsic kinetics of hydrate decom-
position with respect to equilibrium assumptions. They concluded
that the kinetic equation was affected only when it was considered
ve orders of magnitude lower than the values found by Kim
et al. (1987) in a PVT cell (Hong et al. 2003; Hong and Pooladi-
Darvish 2005).
Xu (2004) has modeled dynamic gas-hydrate systems consid-
ering two main elements. The rst element provides a model to
account for dynamic phase transitions of marine gas hydrates by
considering the effects of uid pressure, temperature, and salinity
changes on hydrate stability, solubility, and uid densities and
enthalpies. This allows describing coexistence of three phases
hydrate, gas, and liquid solution at equilibrium. The model con-
sists of three components (water, gas, and salt) and four phases
(free gas, liquid solution, gas hydrate, and solid halite). He con-
sidered thermodynamic equilibrium for and among individual
phases. The second element of the model consists of the numeri-
cal tool to solve for uid-ow and -transport equations in porous
media. It considers four components and up to ve phases. He has
studied the response of the model to the pressure-drop and tem-
perature-rise scenarios at the seaoor (Xu 2004).
Ahmadi et al. (2004) developed a 1D model to study CH
4
pro-
duction from hydrate dissociation in a conned reservoir by use
of a depressurization method. They considered heat of dissocia-
tion and conduction and convection in both gas and hydrate phase.
They considered equilibrium conditions at the dissociation front
and neglected water ow in the reservoir and the Joule-Thomson
cooling effect (Ahmadi et al. 2004).
Sun and Mohanty (2006) developed a 3D simulator by use of
the Kim et al. (1987) kinetic model to study formation and disso-
ciation of hydrate in porous media. They considered four compo-
nents (hydrate, CH
4
, water, and salt) and ve phases (hydrate,
gas, aqueous, ice, and salt precipitate). Water freezing and ice
melting are considered, assuming equilibrium phase transitions.
Mass transport including uid ow and molecular diffusion, plus
heat transport including conduction and convection, is solved im-
plicitly (Sun and Mohanty 2006).
Phirani and Mohanty (2010) upgraded the simulator to account
for CO
2
as a new component and CO
2
hydrate as a new phase.
The purpose was to study CO
2
ooding of CH
4
-hydrate-bearing
sediments. They used the model of Kim et al. (1987) for kinetics
of dissociation and constant rates for hydrate formation (Phirani
and Mohanty 2010).
Uddin et al. (2006) developed a general kinetic model of
hydrate formation and decomposition on the basis of the Kim
et al. (1987) model to study CO
2
sequestration in CH
4
-hydrate
reservoirs along with CH
4
production. The model consisted of
ve components: water in aqueous phase, CH
4
and CO
2
in gas
phase, and CO
2
hydrate and CH
4
hydrate in solid phase. The gas-
hydrate model was coupled with a compositional thermal reser-
voir simulator (STARS; Computer Modelling Group 2013) to
study dynamics of hydrate formation and decomposition in the
reservoir. It was concluded that the effect of kinetic rate constant
on hydrate decomposition was signicant in the case where it was
lowered a few orders of magnitude. Reservoir permeability also
has a great impact on the decomposition rate (Uddin et al. 2006).
Nazridoust and Ahmadi (2007) developed a computational
hydrate module for ANSYS FLUENT (2013) code. It provides
the possibility to study hydrate dissociation for complex 3D geo-
metries. They used the kinetics rate of dissociation proposed by
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Kim et al. (1987), and they included the heat of reaction, effects
of water and gas permeabilities, and effective porosity with possi-
bility of variation with time. They found that the production pro-
cess was sensitive with respect to temperature, pressure, and core
permeability. They also compared their results with experimental
data (Nazridoust and Ahmadi 2007).
Liu et al. (2008) developed a 1D model to study hydrate disso-
ciation by depressurization in porous media. They used a moving
front to separate the hydrate zone from the gas zone. They consid-
ered conductive and convective heat transfer and mass transfer in
gas and hydrate zones and energy balance at moving front. They
considered equilibrium at the front and concluded that the
assumption of stationary water phase results in overprediction of
dissociation-front location and underprediction of gas production
in the well. They also found that reservoir permeability and well
pressure can highly affect the production rate (Liu et al. 2008).
Gamwo and Liu (2010) have presented a detailed theoretical
description of the open-source reservoir hydrate simulator Hydra-
teResSym (NETL 2013) developed previously by Lawrence
Berkeley National Laboratory. They have also applied it to a sys-
tem of three components (CH
4
, water, and hydrate) and four
phases (aqueous, gas, hydrate, and ice). Darcys law is used for
multiphase ow of mass in porous media, and local thermal equi-
librium is considered in the code. It considers both kinetic and
equilibrium approaches by use of the Kim et al. (1987) scheme as
the kinetic model of hydrate dissociation. The studied model has
been validated by use of the TOUGH-HYDRATE simulator (Law-
rence Berkeley National Laboratory 2013). They concluded
that HydrateResSim is a suitable freeware, open-source code for
simulating CH
4
-hydrate behavior in the reservoir. They found
that the equilibrium approach usually overpredicts the hydrate disso-
ciation compared with the kinetic approach (Gamwo and Liu 2010).
From the presented literature review, it is clear that the
hydrate-dissociation process in the reservoir is mostly treated as
an equilibrium reaction, and in fewer cases as kinetics. The major-
ity of kinetic approaches are modeled after the kinetic model of
Kim et al. (1987), developed according to laboratory experiments:

dn
H
dt
= k
d
A
s
(f
e
f ): (1)
In this paper, a different approach according to the nonequili-
brium nature of hydrate phase transitions in the reservoir will be
presented. In spite of some recommendations by previous
researchers who consider the equilibrium assumption as a suitable
simplication for hydrate modeling in certain conditions, the ki-
netic approach is used in this study, as explained in the Theory
section. On the basis of this approach, a new reservoir hydrate
simulator will be introduced that is developed on a former reac-
tive-transport reservoir simulator: RCB (Saaltink et al. 2004). The
module is designed so that it can easily work according to the
nonequilibrium thermodynamic package that is being developed
in this group. The ultimate goal is to develop the simulator for the
following main purposes:
1. Hydrate production (depressurization, thermal stimulation,
CO
2
/CH
4
exchange).
2. Hydrate formation during aquifer storage of CO
2
in reser-
voirs with cold zones.
3. Dissociation of natural-gas hydrates caused by contact with
undersaturated groundwater through fractures and channels.
4. Dynamics of new hydrate formation from groundwater and
upcoming natural gas from sources below through fracture
systems.
5. Combination of Points 3 and 4 that leads to situations of net
uxes of natural gas to ecosystems outside (water, air).
At this stage, kinetic models of hydrate formation and dissoci-
ation from phase-eld simulations are used to examine the per-
formance of the module through example cases.
Theory
When a clathrate hydrate comes into contact with an aqueous so-
lution containing its own guest molecules (CH
4
or CO
2
), the num-
ber of the degrees of freedom available to the new system of three
phases (aqueous, gas, hydrate) will be decreased compared with
the two-phase system (aqueous, gas) because of the Gibbs phase
rule:
F = N p 2; (2)
where F is the degree of freedom, N the number of components,
and p the number of phases. From a fundamental point of view in
thermodynamics, a phase is unique if density, composition, and
structure are different from other coexisting phases. In the ulti-
mate limit of this, hydrate can never ll pore space more than
thermodynamics permits. Every mineral imposes specic structur-
ing of surrounding water molecules related to the partial charges
of the mineral surface, which will never be compatible with par-
tial charges on structured water molecules in the hydrate surface
(Svandal et al. 2006a, b; Kvamme et al. 2009; Kvamme and Kuz-
netsova 2010; Kvamme et al. 2012; Van Cuong et al. 2012a, b). It
is similar for the hydrate, in which the fairly rigid distribution of
partial charges on oxygen and hydrogen will have a structuring
impact on surrounding uids. The absolute minimum number of
phases for a system of one hydrate former and water is three,
which gives one degree of freedom, and the system cannot reach
equilibrium. Practically, there will always also be uid phase(s) in
the system because of the fact that hydrates in nature are open sys-
tems. No hydrate reservoir reaches innity in any direction. There
is a bottom line at which hydrate is in contact with uids and/or
clay at a temperature for given depth where hydrate cannot be sta-
ble. In the horizontal directions, the hydrate reservoir may enter
fracture systems that bring the hydrate in contact with ground-
water that dissociates hydrate and/or other boundaries where frac-
ture systems bring fresh hydrocarbon feed into the hydrate zones.
In summary, this implies that all hydrate reservoirs are open sys-
tems. Natural hydrate resources are not even close to 100% in
hydrate saturation, according to estimates published for different
parts of the world (Collett 2009; Wanga et al. 2013; Xiao et al.
2013). Full thermodynamic equilibrium is therefore impossible
for hydrates in a reservoir. The situation does not change if there
are more hydrate formers in the system. According to the rst and
second laws of thermodynamics, the most-stable hydrate will
form rst and result in a range of different hydrates with gradually
increasing free energies proportional to depletion of the best
hydrate formers. These hydrates have different compositions and
are by denition different phases. Furthermore, there is no direct
mechanism to make these hydrates uniform because the most-sta-
ble hydrates cannot rearrange to less-stable hydrates without con-
tradicting the rst and second laws. So in summary, there is no
possibility for reaching true thermodynamic equilibrium. The
implementation of kinetic models for the different competing
phase transitions in the reservoir is in its initial phase, so at this
stage it is not possible to quantitatively evaluate the impact of
nonequilibrium thermodynamics compared with the very oversim-
plied 2D pressure vs. temperature equilibrium evaluation. One
example that is not captured in that approach is the dissociation of
hydrate toward undersaturated groundwater, which can be quite
signicant for the initial stages of production in reservoirs without
a gas cap. Solid surfaces are efcient nucleation sites for hydrate
formation, so reformation of hydrate can be facilitated by the min-
eral surfaces. But there are many other examples. The bottom line
is that hydrates in porous media are complex systems that are
unique for every distinct reservoir, and there are no real cases
with sufcient monitoring for comparison purposes. For this rea-
son, we should strive toward making the physical description as
good as possible. The contribution from this work is a proposed
methodology to incorporate appropriate thermodynamics of the
multiphase system of hydrate/water/gas/minerals.
A comparison between a two-phase system and a three-phase
system is made here for further clarication of the nonequilibrium
concept. For a two-phase system comprising two components,
water and gas, there will be two degrees of freedom, whereas in a
three-phase system with hydrate as an additional phase, there will
be only one degree of freedom. As a result, when both
. . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . .
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temperature and pressure are specied, as is the case in reservoir
conditions, the system is overdetermined and may be unable to
reach three-phase equilibrium. The system will, however, always
tend toward the minimum free energy, and when the hydrate is
inside its pressure/temperature stability region, this means that its
free energy is lower than that of the aqueous solution (Svandal
et al. 2006a). In case of hydrate formation and dissociation in the
reservoir, the system will be even more complex because hydrate
can form from, or dissociate toward, phases with different free
energies, which will produce different phases. Consequently,
degree of freedom will decrease further and there will be no equi-
librium condition, and competing phase-transition reactions of
hydrate formation, dissociation, and reformation among different
phases will rule the system. The main factor in such a system is
therefore the minimum free energy of the system and kinetics of
competing reactions. Looking at hydrate in porous media, three
phases (gas, aqueous, and hydrate) are evident. The total inde-
pendent thermodynamic variables in this system are temperature,
pressure, and compositions of all coexisting phases. Locally, tem-
perature and pressure are xed (given by ow) in every point of
the reservoir. From Gibbs phase rule (which is the conservation
of mass under constraints of equilibrium), only two phases can be
at equilibrium for water and one hydrate former. For water and
two hydrate formers, the most-favorable hydrates are formed rst
and a distribution of hydrate compositions will be formed, which
may be slow in reorganization, if possible at all. Furthermore, if
the system is not at equilibrium,that also implies that chemical
potentials of hydrate formers in different phases are not uniform
(equal). From statistical mechanics (the van der WaalsPlatteeuw
theory), this implies different free energies for different hydrates
that are formed (hydrate from liquid water and gas hydrate for-
mer, hydrate formed from adsorbed hydrate former on mineral
surfaces, and so on). Even a hydrate lm formed on a water/
hydrate interface will not be uniform because in a very short time
the hydrate lm will be so slow in transport that further growth
will happen from the solution on one side and from gas on the
other side.
According to Fig. 1, main phase-transition scenarios caused by
hydrate dissociation and reformation for a system of water and
one hydrate former can be summarized as
v Hydrate dissociation toward free bulk gas free bulk
liquid water original hydrate left (DG
1
)
v Hydrate dissociation caused by sublimation (little water in
gas phase) (DG
2
)
v Hydrate dissociation toward liquid water caused by unsatu-
rated CH
4
in water (DG
3
)
v Hydrate reformation from free bulk gas free bulk liq-
uid water (DG
4
)
v Hydrate reformation on gas/water interface (DG
5
)
v Hydrate reformation from dissolved CH
4
in aqueous solution
(DG
6
)
v Hydrate reformation from water and CH
4
adsorbed on min-
eral surfaces (DG
7
)
where
DG
i
= x
H;i
w
(l
H;i
w
l
p
w
) x
H;i
CH
4
(l
H;i
CH
4
l
p
CH
4
): (3)
In Eq. 3, H represents hydrate phase; i represents any of the
seven phase-transition scenarios; p represents liquid, gas, and
adsorbed phases; x is composition; and l is chemical potential.
It should be noted that hydrate is not uniform and there can be
many hydrate phases with different compositions, depending on
which phase the hydrate formers come from and which phase the
water comes from. For example, if a hydrate phase is formed
slightly outside of a mineral, the hydrate surface itself is an
adsorption side with specic properties as such. To analyze this
. . . . . . . .
Hydrate Phase
Transitions
Reformation
From:
Dissociation
Towards:
CH
4
in the gas
+
Water in liquid
Dissolved CH
4
+
Water in liquid
Dissolved CH
4
+
Water in liquid
CH
4
in the gas
+
Water vapor
CH
4
in the gas
+
Water vapor
Water and CH
4
adsorbed on mineral
surfaces
CH
4
in the gas
+
Water in liquid
Fig. 1Possible hydrate phase-transition scenarios in porous media.
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system all impossible (DG > 0) and unlikely ([DG[e) cases must
be disregarded. Taking into account the mass-transport-limited
cases, all realistic phase-transition scenarios will be determined.
The purpose of this study is to develop a hydrate reservoir sim-
ulator that has the possibility to consider the free-energy changes
of all phase-transition scenarios and take into account the effect
of the realistic ones on the ow and the properties of the porous
media through advanced kinetic models.
Kinetic Model
The results from phase-eld simulations (Baig 2009) have been
modied to be used in the kinetic model. Phase-eld simulations
are modeled after the minimization of Gibbs free energy on the
constraint of heat and mass transport. Extensive research has been
ongoing in the same group on application of PFT in prediction of
hydrate-formation and -dissociation kinetics, which is still in pro-
gress (Svandal et al. 2006a, b; Svandal 2006; Tegze et al. 2006a,
b; Baig 2009; Kivela et al. 2012; Qasim et al. 2011). In this study,
the simulation results of such studies have been extrapolated and
used as the constant rate of the kinetic model in the numerical tool.
Numerical Tool
For reservoirs where hydrate may form in some regions, hydrate
formation involves roughly 10 vol% increase of water. In parallel
to this, there are chemical reactions that can for example supply
extra CO
2
through dissolution of carbonates in regions of low pH,
and also regions of high pH where transported ions may precipitate
and even extract CO
2
from water and hydrate. The formed hydrate
will not be in equilibrium because of Gibbs phase rule, as men-
tioned previously. Neither will it attach to the mineral surfaces
because of incompatibilities of hydrogen bonds in hydrate and
interactions with atomic partial charges on the mineral surfaces.
For this reason, there is a need for a logistic system that can handle
competing processes of formation and dissociation. A reactive-
transport simulator can handle that. Implicit geomechanics are
needed to handle competing phase transitions that are very rapid
(seconds) and are dynamically coupled to geochemical reactions
that can be fairly fast (hours to days). For this purpose RCB, a re-
active-transport reservoir simulator, is used in this study and
extended with hydrate phase transitions as pseudoreactions.
RCB is capable of realistic modeling of the reaction rates for min-
eral dissolution and precipitation, at least to the level of available
experimental kinetic data. In contrast to some oil and gas simula-
tors, the simulator has ow description ranging from diffusion to
advection and dispersion (Saaltink et al. 1997, 2004) and as such is
able to handle ow in all regions of the reservoir, including the
low-permeability regimes of hydrate-lled regions.
The equations for the system are highly nonlinear and are
solved numerically. The numerical approach can be viewed as di-
vided into two parts: spatial and temporal discretizations. The
nite-element method is used for the spatial discretization, while
nite differences are used for the temporal discretization. The
NewtonRaphson method is adopted for the iterative scheme
(Saaltink et al. 1997, 2004).
A brief overview of independent variables, constitutive equa-
tions, and equilibrium restrictions are given in Tables 1 through
3, respectively. More details can be found in Appendix A of this
study, and in the mentioned references.
The Independent Variables. The governing equations for noni-
sothermal multiphase ow of liquid and gas through porous
deformable saline media have been established. Variables and
corresponding equations are tabulated in Table 1.
Constitutive Equations and Equilibrium Restrictions. Asso-
ciated with this formulation is a set of necessary constitutive and
equilibrium laws. Tables 2 and 3 present a summary of the consti-
tutive laws and equilibrium restrictions that should be incorpo-
rated in the general formulation. The dependent variables that are
computed by use of each law are also included.
RCB is a coupling of a reactive transport code, Retraso, with a
code for simulation of multiphase ow of material and heat, Code-
Bright. CodeBright contains an implicit algorithm for solution of
material-ow, heat-ow, and geomechanical-model equations (Oli-
vella et al. 1994, 1996, 1997). The Retraso extension of CodeBright
involves an explicit algorithm for updating the geochemistry (Saal-
tink et al. 1997, 2004), as shown in Fig. 2. This new coupled tool
RCB is capable of handling both saturated and unsaturated ow, as
well as heat transport and reactive transport in both liquid and gas. It
is a user-friendly code for ow, heat, geomechanics, and geochemis-
try calculations. It offers the possibility of computing only the cho-
sen unknowns of the users interest, such as hydromechanical,
hydrochemical/mechanical, hydrothermal, hydrothermal/chemical/
mechanical, thermomechanical, and so forth.
It can handle problems in one, two, and three dimensions (Oli-
vella et al. 1994, 1996, 1997; Saaltink et al. 1997). An important
advantage of RCB is the implicit evaluation of geomechanical dy-
namics. According to Fig. 2, ow, heat, and geomechanics are
solved initially in the CodeBright module through the Newton
Raphson iteration, and then the ow properties are updated
according to the effects of reactive transport on porosity and salin-
ity in a separate NewtonRaphson procedure but for the same
timestep (Saaltink et al. 1997). This makes it possible to study the
implications of fast kinetic reactions, such as hydrate formation or
dissociation, more realistically.
Modifications in RCB. The Retraso part of the code has a built-
in, state-of-the-art geochemical solver, as well as the capabilities
of treating aqueous complexation (including redox reactions) and
adsorption. The density of CO
2
plumes that accumulate under
traps of low-permeability shale or soft clay depend on depth and
local temperature in each unique storage scenario. The difference
between that density and the density of the groundwater results in
a buoyancy force for penetration of CO
2
into the caprock. And
even if the solubility of water into CO
2
is small, dissolution of
water into CO
2
may also lead to the drying out of clay. Mineral
reactions between CO
2
and shale minerals are additional effects
that eventually may lead to embrittlement. Linear geomechanics
TABLE 2CONSTITUTIVE EQUATIONS
Constitutive Equation Variable Name
Darcys law Liquid and gas advective ux
Ficks law Vapor and gas nonadvective ux
Fouriers law Conductive heat ux
Retention curve Liquid-phase degree of saturation
Mechanical constitutive model Stress tensor
Phase density Liquid density
Gas law Gas density
TABLE 3EQUILIBRIUMRESTRICTIONS
Equilibrium Restrictions Variable Name
Henrys law Air-dissolved mass fraction
Psychometric law Vapor mass fraction
TABLE 1EQUATIONS AND INDEPENDENT VARIABLES
Equation Variable Name
Equilibrium of stresses Displacements
Balance of liquid mass Liquid pressure
Balance of gas mass Gas pressure
Balance of internal energy Temperature
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April 2014 SPE Journal 219
may not be appropriate for these effects. Clay is expected to ex-
hibit elastic nonlinear contributions to the geomechanical proper-
ties. Different types of nonlinear models are already implemented
in the CodeBright part of the code, and the structure of the code
makes it easy to implement new models derived from theory and/
or experiments. The current version of RCB has been extended
from ideal gas into handling of CO
2
according to the Soave
RedlichKwong equation of state (EOS) (Kvamme and Liu
2008b). This EOS is used for density calculations and for fugac-
ities of the CO
2
phase as needed in the calculation of dissolution
of the CO
2
into the groundwater (Hellevang and Kvamme 2007;
Kvamme and Liu 2008a, b). The equations for the system are
highly nonlinear and are solved numerically (Saaltink et al. 1997,
2004). The NewtonRaphson method used in the original RCB
also has been modied to improve the convergence of the numeri-
cal solution while increasing the range of working pressure in the
system (Kvamme and Liu 2008b).
The following modications are additional in this study. To
account for nonequilibrium thermodynamics of hydrate and to
determine the kinetic rates of different competing scenarios in
each node and each timestep according to the temperature, pres-
sure, and composition of the system, CO
2
and CH
4
hydrates are
added into the simulator as pseudomineral components with a con-
stant kinetic rate for hydrate formation and dissociation. Hydrate
formation and dissociation can be observed directly through poros-
ity changes in the specic areas of the porous media. Porosity
reduction indicates hydrate formation, and porosity increase indi-
cates hydrate dissociation. Temperature, pressure, and CO
2
/CH
4
concentrations in all possible phases are three factors that inu-
ence hydrate formation or dissociation. The kinetic rate used in
this study is calculated from extrapolated results of PFT simula-
tions by Baig (2009). In the next stage, it will be replaced by a
thermodynamic code, which is already in the nal stages, to
account for all different competing reactions. In the mixed hydrate
system, the two resulting phases from CO
2
/CH
4
splits will have
signicant free-energy benet differences in terms of hydrate for-
mation, and it is therefore also not implemented yet. However, the
fundamental kinetic modeling of these processes is being con-
ducted for later implementation.
Hydrate reaction is considered on the basis of Eq. 4. The
energy balance for the gas phase is modied from ideal gas (id) to
real gas (gas) according to Eq. 5 by use of the SoaveRedlich-
Kwong EOS to calculate fugacity coefcient and derivatives:
8
CH
4
CO
2
_ _
46 H
2
O Hydrate; (4)
H = H
(id;gas)
RT
2
d(lnU)
dT
: (5)
The energy balance for solid phase is also modied according
to the hydrate reaction enthalpy of Table 4. The enthalpy of CH
4
hydrates, CO
2
hydrates, and mixed hydrates are readily available
from Kvamme and Tanaka (1995) through simple classical ther-
modynamic relationships between free energy and enthalpy. Note
in particular that empty hydrate water chemical potential is
available and has been veried through other separate studies to
reproduce experimental equilibrium curves without adjustable pa-
rameters; similar circumstances hold for liquid water (or ice)
entering the hydrate reaction in Eq. 4. Furthermore, Eq. 5 com-
plements the enthalpy from the gas(es) entering the hydrate.
Released heat by hydrate formation or consumed heat by hydrate
dissociation is therefore trivially available and incorporated. The
reaction heat will appear as a source or sink term in the heat-
ow equation, and the enthalpy that follows the mass transport is
trivially incorporated into the heat ux equation. The heat that dis-
tributes to (or consumes) surroundings by conduction (only a sim-
plied conduction model is implemented so far) is so far simplied
through an average heat conductivity on the basis of all surrounding
phases. At present, this has not been a major focus but it is on the
agenda for a follow-up project. As such, the heat transport may be
interpreted with some caution, although the incorporated descrip-
tion seems to be on the same level as other hydrate simulators.
Heat transport in a dynamically owing system undergoing solid/
uid phase transitions is very complex. We therefore plan to use
PFT with implicit hydrodynamics to conduct pore-scale modeling
of hydrate phase transitions under different ow regions and differ-
ent impacts of mineral surfaces. Strategies for this have already
been discussed by Kvamme et al. (2013, In press).
Model Description
A system of CO
2
injection into the aquifer presented in Fig. 3 is
selected for evaluating the simulator. It consists of a 2D model of
3001000 m at the depth of 100 m. The pressure gradient in the
reservoir is 1 MPa/100 m, and the temperature gradient is 3.6

C/
100 m. The model is discretized into 1,500 elements with dimen-
sions of 1020 m. CO
2
is injected at constant pressure of 4 MPa
at the specied location on Fig. 3. The equation proposed by Phir-
ani and Mohanty (2010) is used to describe CO
2
hydrate equilib-
rium conditions in the model. Choice of conditions is intentional
to allow hydrate formation in certain areas of the system, as
. . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . .
Independent Variables
(Temperature, Gas Pressure, Liquid
Pressure, Deformation)
Dependent Variables
(Flux of Liquid, Flux of Gas, Hydraulic
Saturation, Porosity...)
Newton Raphson
Iteration
Converged
Newton Raphson
Iteration
Converged
Copy Relative Variables for
Retraso
Update Flow Properties Affected by
Reactive Transport, Including Porosity and
Salinity
No
No
Go To the Next
Time Step
Yes
C
o
d
e
B
r
i
g
h
t
(
F
l
o
w
,

H
e
a
t
,

G
e
o
m
e
c
h
a
n
i
c
s
)
R
e
t
r
a
s
o
(
R
e
a
c
t
i
v
e

T
r
a
n
s
p
o
r
t

M
o
d
u
l
e
)
Yes
Fig. 2RCB solves the integrated equations sequentially in
one timestep.
P
Top
= 1 MPa, T
Top
= 273.35K
P
Bottom
= 4 MPa, T
Bottom
= 284.15K
1000 m
Injection well
400 m
100 m
y
x z
Fig. 3Details of the simulation model.
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220 April 2014 SPE Journal
presented in Fig. 4. Tables 4 through 6 present the information
regarding available species in different phases, initial and bound-
ary conditions, and material properties, respectively. The system
is closed laterally by mechanical boundary conditions.
Results and Discussion
The simulation results processed by RCB are visualized by use of
GiD visual window (GiD, International Center for Numerical
Methods in Engineering, Technical University of Catalonia, Bar-
celona, Spain; more information is available at http://gid.cimne
.upc.es/). Fig. 4 presents the suitable thermodynamic conditions
for CO
2
-hydrate formation according to initial conditions of the
reservoir. Figs. 5 through 10 show gas pressure, porosity changes,
temperature prole, liquid- and gas-phase uxes, and liquid satura-
tion, respectively, after 1, 100, 500 and 1,000 days. Porosity
changes caused by the hydrate-formation process start after 54
days and below the original possible zone of Fig. 4, and extend to
regions above this zone. This can be explained by the pressure pro-
le presented in Fig. 5. According to pressure increase in and
above the injection zone, thermodynamic conditions for hydrate
formation are achieved outside the initial region.
The exothermic enthalpy of hydrate formation appears as tem-
perature increase near Day 500, as demonstrated in Fig. 7. It
affects the hydration process. According to Fig. 6, the porosity in
the area where temperature increase is noticeable has decreased
less than that in the upper area.
Both liquid- and gas-phase ux gures show the effect of po-
rosity change on the ow. This is more obvious in Fig. 9, where
some scattered pattern of ow is found after 500 days in the
region where hydrate formation has happened. The impact of dif-
ferent phase transitions on the local permeability calls for devel-
opment of new permeability correlations as well as new strategies
for efcient CO
2
injection.
It should be mentioned that geomechanics have not been a
focus for this paper, but received more attention in the form of an
effective-stress prole in other publications on hydrates from the
same simulator (Kvamme et al. 2011).
TABLE 4AQUIFER, ROCK, AND HYDRATE PROPERTIES
Youngs modulus (GPa) 0.5
Poissons ratio 0.25
Zero-stress porosity 0.1
Zero-stress permeability (m
2
) 1.010
13
Van Genuchtens gas-entry pressure
(at zero stress) (kPa)
196
Van Genuchtens exponent 0.457
Thermal conductivity of dry
medium [W/(mK)]
0.5
Thermal conductivity of saturated
medium [W/(mK)]
3.1
Solid-phase density (kg/m
3
) 2163
Rock specic heat [J/(kgK)] 874
CO
2
-hydrate molecular weight (g/mol) 147.5
CO
2
-hydrate density (kg/m
3
) 1100
CO
2
-hydrate specic heat [J/(kgK)] 1,376
CO
2
-hydrate reaction enthalpy (J/mol) 51,858
CO
2
-hydrate kinetic formation rate constant
(mol/Pam
2
s)
1.44110
12
Hydrate stable region
170 m
290 m
Fig. 4Thermodynamically suitable area for CO
2
-hydrate for-
mation, according to initial conditions of the reservoir.
TABLE 5CHEMICAL SPECIES IN THE MEDIA
Phase Species
Aqueous H
2
O, HCO
3

, OH

, H

, CO
2
(aq), CO
3
2
Gas CO
2
(g)
TABLE 6INITIAL AND BOUNDARY CONDITIONS
Pressure at the top (MPa) 1.0
Pressure at the bottom (MPa) 4.0
Temperature at the top (K) 273.35
Temperature at the bottom (K) 284.15
Initial mean stress at the top (MPa) 2.33
Initial mean stress at the bottom (MPa) 8.76
CO
2
-injection pressure (MPa) 4.0
Pres.
4.0003
3.6669
3.3336
3.0002
2.6668
2.3335
2.0001
1.6667
1.3334
1
y
x z
Fig. 5Gas pressure (MPa) after 1, 100, 500, and 1,000 days.
Porosity
0.1
0.099922
0.099844
0.099767
0.099689
0.099611
0.099533
0.099456
0.099378
0.0993
y
x z
Fig. 6Porosity after 1, 100, 500, and 1,000 days.
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April 2014 SPE Journal 221
Conclusion
A new hydrate simulator is developed on the basis of the available
reactive-transport code of RCB. It consists of a system of three
phases including solid phase (mineral), liquid phase (water and dis-
solved gas), and gas phase (CO
2
and water vapor). Three compo-
nents (water, CO
2
, and heat) are considered in the balance
equations. Hydrate is dened as a pseudomineral, meaning that
although it is considered as part of the solid phase, regarding the
energy balance it is considered independently for both internal
energy and reaction enthalpy. At this stage, heat-transport proper-
ties of hydrate are not considered as different from solid phase. The
kinetic approach is used in this study, and the kinetic rates obtained
from PFT simulations are used. Because of the nonequilibrium na-
ture of hydrate in the reservoir, the ultimate purpose is to study the
dynamics of hydrate in the reservoir by considering all possible
phase-transition scenarios. The reactive-transport module in this
simulator along with the hydrate denition in the system as a pseu-
domineral gives this opportunity to reach this goal by coupling the
code with a nonequilibrium thermodynamic module.
The main purpose of this paper has been to discuss the general
concept, not to demonstrate all features that will be opened up by
it. One example that will be implemented next is the reaction of
hydrate with pure water (or, groundwater with some salinity),
which results in dissociation of hydrates caused by undersaturated
water. This will contribute substantially to dissociation of hydrate
in initial stagesmaybe even more than pressure reduction at
these stages in reservoirs without underlying gas phase. Other
examples are refreezing of hydrate caused by cooling, which can
be very complex and can consist of signicant hydrate formation
from several phases (heterogeneous hydrate nucleation from
adsorbed hydrate former on mineral surfaces are favorable, as are
hydrate formation from aqueous solution and from water/hydrate-
former interface). These different phase transitions have funda-
mentally different kinetic rates. Hydrate formation from solution
is mainly mass-transport controlled and characterized by a Ficks-
type law. Interface formation is complex because of competitions
Temperature
17.798
15.843
13.887
11.932
9.9767
8.0213
6.066
4.1107
2.1553
0.2
y
x z
Fig. 7Temperature (

C) after 1, 100, 500, and 1,000 days.

|Liq Ph. Flux|
5e07
4.4446e07
3.8891e07
3.3337e07
2.7782e07
2.2228e07
1.6673e07
1.1119e07
5.5644e08
1e10
|Liq Ph. Flux|
5e08
4.4456e08
3.8911e08
3.3367e08
2.7822e08
2.2278e08
1.6733e08
1.1189e08
5.6444e09
1e10
y
x z
y
x z
Fig. 8Liquid-phase ux (m/s) after 1, 100, 500, and 1,000 days (for better illustration, the color range for the two top gures is dif-
ferent from that of the two bottom ones).
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222 April 2014 SPE Journal
of different cores when the interface closes in by the hydrate.
Hydrate formation from adsorbed hydrate-former is very fast in
nucleating and might produce many active nuclei for rapid
growth. None of these features are possible in existing hydrate
codes, and they are not currently implemented in RCBbut work
is in progress.
Nomenclature
a
Pmki
= catalytic effect
A
s
= surface area, L
2
, m
2
b = vector of body force per unit volume, ML
2
T
2
,
Nm
3
C = concentration, NL
3
, molm
3
E
a,m
= activation energy, ML
2
T
2
N
1
, Jmol
1
E
i
= internal energy per unit mass in solid (i=s), liquid
(i=l), and gas (i=g) phase, L
2
T
2
, Jkg
1
f = fugacity, ML
1
T
2
, Pa
f
a
= supply term for gas component a, ML
3
T
1
,
kgm
3
s
1
f
e
= fugacity, ML
1
T
2
, Pa
f
Q
= internal/external energy supply, ML
1
T
3
, Jm
3
s
1
f
W
= external supply of water, ML
3
T
1
, gm
3
s
1
F = degree of freedom in phase rule
g = gravity acceleration, LT
2
, ms
2
G = molar Gibbes free energy, ML
2
T
2
N
1
, kgm
2
s
2
mol
1
H = molar enthalpy, ML
2
T
2
N
1
, kgm
2
s
2
mol
1
H
(id,gas)
= molar enthalpy of ideal gas, ML
2
T
2
N
1
,
kgm
2
s
2
mol
1
i
c
= conduction energy ux, MT
3
, Jm
2
s
1
j
Ei
= advective energy ux in solid (i=s), liquid (i=l) and
gas (i=g) phase, MT
3
, Jm
2
s
1
j
/a
g
= mass ux of gas component a in gas phase, ML
2
T
1
,
kgm
2
s
1
j
/a
l
= mass ux of gas component a in liquid phase,
ML
2
T
1
, kgm
2
s
1
j
w
g
= mass ux of water in gas phase, ML
2
T
1
, kgm
2
s
1
j
w
l
= mass ux of water in liquid phase, ML
2
T
1
,
kgm
2
s
1
j
s
= ux of solid, ML
2
T
1
, kgm
2
s
1
k
d
= kinetic rate constant, NM
1
TL
1
, molPa
1
m
2
s
1
k
mk
= experimental rate constant, NL
2
T
1
, molm
2
s
1
k
ra
= relative permeability
K = equilibrium constant
n = shape factor
n
H
= number of hydrate moles, N, mole
N = number of components in phase rule
P
f
= partial pressure of the fth species in the gas phase,
ML
1
T
2
, Pa
P = pressure, ML
1
T
2
, Pa
q
a
= advective ux of volumetric ow in liquid (a=l) and
gas (a=g) phase, LT
1
, ms
1
r
m
= mineral dissolution rate, NL
3
T
1
, molm
3
s
1
R = gas constant, ML
2
T
2
N
1
I
1
, gm
2
s
2
m
1
1K
1
1
S
g
= gas saturation
S
l
= liquid saturation
t = time, T, s
T = temperature, I, K
u = solid displacement, L, m
x
w
= composition of water
c = activity coefcient
h
a
g
= mass of gas component per unit volume in gas phase,
ML
3
, kgm
3
h
a
l
= mass of gas component per unit volume in liquid
phase, ML
3
, kgm
3
h
w
g
= mass of water per unit volume of gas in gas phase,
ML
3
, kgm
3
h
w
l
= mass of water per unit volume of liquid in liquid phase,
ML
3
, kgm
3
h
s
= mass of solid per unit volume of solid, ML
3
, kgm
3
l = chemical potential, ML
2
T
2
N
1
, kgm
2
s
2
mol
1
l
a
= viscosity of liquid (a=l) and gas (a=g) phase,
ML
1
T
1
, Pas
v = stoichiometric coefcient
n
m
= factor to determine mineral precipitation (=l) or disso-
lution (=l)
p = number of phases in phase rule
q
i
= density in solid (i=s), liquid (i=l), and gas (i=g)
phase, ML
3
3, kgm
3
r = stress, ML
1
T
2
, Pa
r
m
= reactive surface, L
1
, m
2
m
3
/ = porosity
U = fugacity coefcient
X
m
= ratio of the ion-activity product for the real concentra-
tions to the corresponding equilibrium constant
Acknowledgments
We acknowledge the grant and support from Research Council of
Norway through the following projects: SSC-Ramore, Subsurface
storage of CO
2
Risk assessment, monitoring and remediation,
project No. 178008/I30; FME-SUCCESS, project No. 804831; and
PETROMAKS, CO
2
injection for extra production, Research
Council of Norway, project No. 801445.
|Gas Ph. Flux|
5.396e05
4.7964e05
4.1969e05
3.5973e05
2.9978e05
2.3982e05
1.7987e05
1.1991e05
5.9956e06
0
y
x z
Fig. 9Gas-phase ux (m/s) after 1, 100, 500, and 1,000 days.
Liq. Sat.
1
0.91911
0.83821
0.75732
0.67642
0.59553
0.51463
0.43374
0.35284
0.27195
y
x z
Fig. 10Liquid saturation after 1, 100, 500, and 1,000 days.
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April 2014 SPE Journal 223
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Appendix A
Governing Equations in RCB. The mass balance of solid is
@
@t
[h
s
(1 /)[ \ (j
s
) = 0; (A-1)
where h
s
is the mass of solid per unit volume of solid, j
s
is the
ux of solid, and / is porosity. From Eq. A-1, an expression for
porosity variation is obtained as
D
s
/
Dt
=
1
h
s
(1 /)
D
s
h
s
Dt
_ _
(1 /)\
du
dt
; (A-2)
where u is solid displacements.
The mass balance of water is
@
@t
(h
w
l
S
l
/ h
w
g
S
g
/) \ (j
wa
l
j
wa
g
) = f
w
; (A-3)
where h
w
l
and h
w
g
are mass of water per unit volume of liquid in
the liquid phase and mass of water per unit volume of gas in
the gas phase, respectively; S
l
and S
g
are degree of saturation of
liquid and gas phases (i.e., fraction of pore volume occupied by
each phase), respectively; j
w
l
and j
w
g
are mass ux of water in liq-
uid and gas phase, respectively; and f
w
is the external supply of
water that also includes water from hydrate.
The mass balance of gas is
@
@t
(h
a
l
S
l
/ h
a
g
S
g
/) \ (j
/a
l
j
/a
g
) = f
a
; (A-4)
where h
a
l
and h
a
g
are mass of gas component (CH
4
, CO
2
,..) per unit
volume in liquid and gas phase, respectively; j
/a
l
and j
/a
g
are mass
ux of gas component a in liquid and gas phase relative to the
solid phase, respectively; and f
a
is a supply term that, similar to
water phase, also considers hydrate formers from hydrate phase.
Momentum Balance of the Medium. The momentum balance
reduces to the equilibrium of stresses if the inertial terms are
neglected:
\ r b = 0; (A-5)
where r is the stress tensor and b is the vector of body force.
The Internal-Energy Balance of the Medium. The equation for
internal-energy balance for the porous medium is established by
taking into account the internal energy in each phase (E
s
, E
l
, E
g
):
@
@t
[E
s
q
s
(1 /) E
l
q
l
S
l
/ E
g
q
g
S
g
/[
\ (i
c
j
Es
j
El
j
Eg
) = f
Q
;
(A-6)
where i
c
is energy ux caused by conduction through the porous
medium; the other uxes (j
Es
; j
El
; j
Eg
) are advective uxes of
energy caused by mass motions; and f
Q
is an internal/external
energy supply.
Constitutive Equations and Equilibrium Laws. The set of nec-
essary constitutive and equilibrium laws as mentioned in Tables 2
and 3, respectively, associates the previously discussed balances.
Some of the most important of these laws are described here.
Generalized Darcys law is used to compute the advective ux
q of the a phase (a = l for liquid, a = g for gas). It is expressed as:
q
a
=
Kk
ra
l
a
(\P
a
q
a
g);
(A-7)
where K is the tensor of intrinsic permeability, k
ra
is the relative
permeability of the phase, l
a
is the phases dynamic viscosity
(Pas), and g is the gravity vector (ms
2
).
Van Genuchtens retention curve expressing saturation as a
function of liquid or gas pressure is given by
S = 1
P
g
P
l
P
0
_ _ _ _
1
1 n
_
_
_
_
_
_
n
; where S
g
= 1 S
l
;
(A-8)
. . . . . . . . . . . . . . . .
. . . . . . .
. . . . . . .
. . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . .
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April 2014 SPE Journal 225
and where P
0
and n are scale pressure and shape parameters,
respectively. The relative permeability k
ra
depends on saturation
(S
l
), which in turn depends on P
l
and P
g
.
Chemical Reactions. The equilibrium solid/liquid interactions
are
X
m
c
m
K
m
=

N
C
i=1
(c
v
p
ml
i
c
v
p
ml
i
); (A-9)
where X
m
is the molar fraction of the mth solid phase; c
m
is its
thermodynamic activity coefcient (X
m
and c
m
are taken equal to
unity for pure phases); c
i
and c
i
are the concentration and activity
coefcient of the ith species, respectively; is the stoichiometric
coefcient in the dissolution reaction of the mth solid phase; and
K
m
is the corresponding equilibrium constant.
The kinetic solid/liquid interactions are
r
m
= r
m
n
m
exp
E
a;m
RT
_ _

N
k
k=1
k
mk

N
s
i=1
a
pmki
i
(X
hmk
m
1)
g
mk
;
(A-10)
where
X
m
=
1
K
m

N
C
i=1
a
v
p
ml
i
; (A-11)
and
k
m
= k
0
exp
E
a;m
RT
_ _
; (A-12)
where r
m
is the mineral-dissolution rate (moles of mineral per vol-
ume of rock and unit time), k
mk
is the experimental rate constant,
and X
m
is the ratio of the ion-activity product for the real concen-
trations to the corresponding equilibrium constant. The parame-
ters h and g must be determined by tting to experimental data.
E
a,m
is the apparent activation energy of the overall reaction pro-
cess and k
0
is a constant. r
m
is the reactive surface. The term a
Pmki
accounts for the catalytic effect of some species (particularly of
H

). Factor n
m
takes on values of 61 depending on whether X
m
is
larger or smaller than unity (precipitation or dissolution), respec-
tively. At equilibrium X
m
=1, and therefore r
m
=0.
The kinetic equation for hydrate is according to Eq. 1, where
the rate constant is obtained from PFT simulations.
The aqueous complexation reactions are
logK
a
= S
a
logC
a
S
a
logc
2
(C
2
); (A-13)
where K
a
is the equilibrium-constant vector, which depends on T
and P. S
a
is the stoichiometric-coefcient matrix for aqueous
complexation reactions. C
a
is the molar-concentration vector of
aqueous species, and c
a
is the vector of thermodynamic-activity
coefcients.
The gas/liquid interactions are
p
f
c
f
K
f

N
c
i=1
c
vf 1
i
c
vf 1
i
; (A-14)
where p
f
is the partial pressure of the fth species in the gas phase; c
f
is its activity coefcient; c
i
and c
i
are the concentration and activity
coefcients of the ith dissolved primary species, respectively;

is
the stoichiometric coefcient of the ith species in the exsolution
reaction of uid f; and K
f
is the equilibrium constant of the reaction.
Mohammad Taghi Vafaei holds bachelors and masters
degrees in chemical engineering from Shiraz University, Shiraz,
Iran. He joined the Enhanced Oil Recovery Excellence
Research Center at Shiraz University in 2005 and wrote his mas-
ters thesis on simulation of effective mechanisms in the
steam-assisted-gravity-drainage process. Vafaei started his
PhD studies in process technology at University of Bergen, Ber-
gen, Norway, in 2009 under supervision of Bjrn Kvamme and
Tatiana Kuznetsova. He has been working on simulation of
hydrate dynamics in the reservoir since then, and has been
participating in development of a new hydrate simulator for
studying different aspects of hydrates in the reservoir (for
example, during CO
2
storage or CH
4
production). The results
of these studies are presented in international conferences
and published in different scientific journals.
Bjrn Kvamme holds a masters degree in chemical engineer-
ing and a PhD degree in chemical engineering from the Nor-
wegian University of Technology and Natural Sciences,
Trondheim, Norway. He has been with SINTEF in Trondheim. In
1987, Kvamme was appointed as a full professor and was a
pioneer in beginning the masters and doctoral programs in
process engineering in Telemark, Norway, now implemented
as a part of Telemark University College. He has been affiliated
with the Department of Chemistry at the University of Bergen
since 1998 and entered a position as Professor in Gas Process-
ing at the Department of Physics in March 2000. Kvamme is
the author/coauthor of more than 200 reviewed publications,
plus several book chapters and proceedings contributions. His
main research effort has been in thermodynamics and statisti-
cal thermodynamics. Topics include natural-gas-hydrates
equilibrium, stability, and kinetics; polar solutions and electro-
lyte solutions; kinetics of phase transitions; oil in water emul-
sions; separation; gas cleaning; and seawater chemistry; more
recently, he has focused on natural-gas hydrate in general
and hydrate as an energy source. Kvammes ideas have
resulted in collaboration with ConocoPhillips and other
researchers, which 10 years later resulted in the first full-scale
pilot-plant investigation of gas-hydrate energy production
with simultaneous safe long-term storage of CO
2
. In addition
to various ongoing projects, he is part of an application for the
Centre of Excellence in environmentally friendly energy (FME-
SUCCESS). Development of a new reactive-transport simulator
for CO
2
storage with implicit geomechanical analyses is cur-
rently an important issue. This also includes state-of-the art
implementation of hydrate dynamics in the simulator.
Kvamme is currently the leader of a research group compris-
ing professors, graduate students, and a varying number of
international guest researchers and guest students.
Ashok Kumar Chejara holds a bachelors degree in chemical
engineering and a masters degree in process engineering
and design from Indian Institute of Technology, Delhi, India. He
previously worked with Reliance Industries, Mumbai, in the field
of petrochemical manufacturing. Chejara has worked on his
PhD research for 3 years under the guidance of Bjrn Kvamme
in the Department of Physics and Technology, University of Ber-
gen, from May 2009 to May 2012. His area of research has
been gas hydrates, and he has worked on CO
2
-gas-hydrate-
formation and CH
4
-gas-hydrate-dissociation reactions in aqui-
fers. Chejara has published his results in scientific journals and
has submitted his thesis for the consideration of a PhD degree.
Currently, he is working as a senior petrophysicist with Statoil
ASA, Bergen, Norway.
Khaled Jemai completed his bachelors degree in petroleum
technology and masters degree in applied mathematics at
the University of Bergen in 2004. He is currently working as a
lecturer of mathematics and physics at Os High School, Oslo,
Norway. As a PhD candidate at the University of Bergen,
Jemai is a member of a research group working in simulations
of hydrate dynamics in the reservoir.
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J167259 DOI: 10.2118/167259-PA Date: 9-April-14 Stage: Page: 226 Total Pages: 12
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226 April 2014 SPE Journal