Journal of Natural Gas Science and Engineering 35 (2016) 1362e1387

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Journal of Natural Gas Science and Engineering

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Review of gas hydrate dissociation kinetic models for energy recovery

Zhenyuan Yin a, b, Zheng Rong Chong a, Hoon Kiang Tan b, Praveen Linga a, *
a
Department of Chemical and Biomolecular Engineering, National University of Singapore, 117585, Singapore
b
Lloyd's Register Global Technology Centre Pte Ltd, 138522, Singapore

a r t i c l e i n f o a b s t r a c t

Article history: In this work, a comprehensive review of gas hydrate dissociation kinetic models and hydrate reservoir
Received 13 February 2016 simulators are provided. The main features of the dissociation kinetic models are summarized, with
Received in revised form model formulation, assumptions, governing equations, solution method and limitations highlighted. A
5 April 2016
clear relationship between different kinetic models is identified according to the driving mechanisms
Accepted 19 April 2016
Available online 22 April 2016
and the progression of each hydrate dissociation kinetic model is presented to capture major im-
provements. Besides, key intrinsic kinetic parameters used in the kinetic models are extracted, which
could be applied directly in future hydrate dissociation modelling study. Various aspects of hydrate
Keywords:
Gas hydrates
reservoir simulator, including its theoretical basis, computational algorithms and applications have also
Hydrate dissociation been reviewed to provide a holistic view on the development of reservoir simulation for energy recovery
Kinetic models from natural gas hydrates. Finally, further developments are suggested for improving the hydrate
CFD modelling dissociation models relevant to practical applications of clathrate hydrates.
Reservoir simulators © 2016 Elsevier B.V. All rights reserved.
Energy recovery
Intrinsic kinetics

1. Introduction recent decade by using gas hydrates as a technology enabler. These

Gas hydrates are solid crystalline compounds that consist of
water and gas molecules. Water molecules form cage-like crystal
lattice through hydrogen bonds encaging guest gas molecules,
which is stabilized by van der Waal's forces at certain temperature
and pressure conditions (Davidson, 1973; Englezos, 1993; Sloan and
Koh, 2008). In total, about 60 gas species form gas hydrates,
including the most commonly seen methane, ethane, propane, and
carbon dioxide etc. (Sloan, 2003b). The three main hydrate struc-
tures identified so far are cubic structure sI, cubic structure sII and
hexagonal structure sH (Ripmeester et al., 1987; Sloan and Koh,
2008). Natural gas hydrates are usually found under deep sea and
permafrost environment where the temperature is low and pres-
sure is high. One key feature of clathrate hydrate is that it possesses
the ability to contain large number of gas molecules effectively,
resulting in a significantly high volumetric gas storage capacity: 1
volume of methane hydrate may contain ~170 volume of methane
(STP) (Sloan and Koh, 2008) in theory. Thus, gas hydrates have
given rise to numerous applications in major areas of water, energy
and environment. Several novel applications are being explored in
* Corresponding author.
E-mail address: praveen.linga@nus.edu.sg (P. Linga).
include CO2 capture (Babu et al., 2013; Duc et al., 2007; Kang and
Lee, 2000; Komatsu et al., 2013; Kumar and Kumar, 2015; Li et al.,
2010; Linga et al., 2007; Park et al., 2013), seawater desalination
(Babu et al., 2014; Javanmardi and Moshfeghian, 2003; Kang et al.,
2014; Park et al., 2011), energy storage (Chatti et al., 2005; Englezos
and Lee, 2005; Florusse et al., 2004; Gudmundsson et al., 1994; Sun
et al., 2003; Veluswamy et al., 2016), refrigeration (Darbouret et al.,
2005; Douzet et al., 2013; Fournaison et al., 2004; Obara et al., 2011;
Xie et al., 2010), and other separation applications (Cha et al., 2010;
Seo and Lee, 2001; Seo et al., 2004). Fundamental information on
gas hydrates is available in a book (Sloan and Koh, 2008) and in
some targeted specific review papers (Babu et al., 2015; Chong
et al., 2016; Davidson, 1973; Englezos, 1993; Eslamimanesh et al.,
2012; Koh, 2002; Koh et al., 2012; Kumar et al., 2015; Sum et al.,
2009; Veluswamy et al., 2014; Xu and Li, 2014).
The study of gas hydrate is comprehensive, involving multi-
scale analysis. The understanding of gas hydrates started from
molecular level whereby researchers investigated the different
types of gas hydrate structures; then their time-independent
thermodynamic properties and phase equilibrium (Davidson,
1973; Englezos, 1993; Sloan and Koh, 2008). Subsequently, the
investigation of gas hydrate formation and dissociation process is
approached from both microscopic and macroscopic level to
develop kinetic models to fully simulate the physics behind the

http://dx.doi.org/10.1016/j.jngse.2016.04.050
1875-5100/© 2016 Elsevier B.V. All rights reserved.
 Z. Yin et al. / Journal of Natural Gas Science and Engineering 35 (2016) 1362e1387
process (Bishnoi and Natarajan, 1996; Englezos et al., 1987; Kim
et al., 1987; Vysniauskas and Bishnoi, 1983). Production of natural
gas from hydrate reservoir and application of gas hydrate as a
medium, such as flow assurance, hydrate-based seawater desali-
nation and energy storage, build upon the macroscopic-level un-
derstanding of hydrates formation and dissociation, which also
involve other large-scale process design parameters.
Examining most hydrate related industrial and academic prob-
lems, most of the time it boils down to the most challenging and
intriguing question e how gas hydrates form and dissociate against
time. Compared with time-independent studies investigating hy-
drate thermodynamic property, molecular structures and phase
equilibrium (Sloan, 1998, 2003a), the endeavour to use kinetic
models to understand the time-dependent behaviour of hydrate
formation and dissociation only started in mid 1980s (Englezos
et al., 1987; Kim et al., 1987; Vysniauskas and Bishnoi, 1983,
1985). Even until now, the kinetic behaviour of hydrate formation
and dissociation is still not completely understood compared with
its thermodynamic behaviour. Besides, the mechanisms behind the
kinetic behaviour of hydrate formation and dissociation still need
to be elucidated at multiple scales.
A good knowledge of hydrate formation kinetics could benefit
us in two folds: to promote the hydrate formation rate, which is
favourable from energy storage and other technological applica-
tions perspective; to inhibit the hydrate formation rate, which is
beneficial in hydrate plug formation and hydrate risk management
from flow assurance perspective. Similarly, a better understanding
of hydrate dissociation kinetics can assist in natural gas production
from energy recovery perspective and hydrate plug remediation
from flow assurance perspective. In comparison, the study of hy-
drate formation process is more complicated than hydrate disso-
ciation process, partly because hydrate formation involves two
inter-related processes: a stochastic hydrate nucleation process
and a hydrate growth process controlled by kinetics, heat and mass
transfer limitations (Sloan and Koh, 2008). A complete under-
standing of hydrate formation requires the incorporation of
nucleation theory into traditional heat and mass transfer problem;
whereas hydrate dissociation process is essentially a multiphase-
multicomponent heat and mass transfer problem coupled with
intrinsic kinetics and fluid flow behaviour (Sloan and Koh, 2008).
The focus of this review is on the development of gas hydrate
dissociation kinetic models towards the evolution of hydrate
reservoir simulators in the recent decades. General concept of hy-
drate dissociation and the benefit of understanding the process will
be introduced first before proceeding to the detailed review on
hydrate dissociation kinetic models and reservoir simulators. The
formulation of various kinetic models, key assumptions, governing
equations, solution method, and limitations are summarized with
the relationship between various models identified according to
the main driving mechanism. Key issues and knowledge gaps for
currently available kinetic models are pointed out with possible
directions for further work suggested. Upon appreciating the
development of various kinetic models, the review proceeds to-
wards the development of reservoir simulation tools, which in-
cludes an overview of their theoretical basis, computational
algorithm, and application in various production tests.
2. Hydrate dissociation
2.1. General concept and modelling of hydrate dissociation
Hydrate dissociation is an endothermic process in which heat
must be supplied to break the hydrogen bonds between water
molecules and the van der Waals interaction forces between guest
molecule and water molecule of the hydrate lattice. The product of
1363
the hydrate dissociation process is water (host) and gas (guest)
molecules. Several conventional methods have been proposed for
the production of natural gas from hydrate reservoir, including
depressurization, thermal stimulation, chemical inhibitor injection,
or a combination of these methods (Collett et al., 2015; Englezos,
1993; Haligva et al., 2010; Makogon, 1997; Sloan and Koh, 2008;
Sum et al., 2009). The first and most popular method is depres-
surization, which involves reducing the pressure below the hydrate
stability zone. The second method is thermal stimulation, which
requires increasing the temperature above the natural gas hydrate
equilibrium temperature at the prevailing pressure. The third
method is chemical inhibitor injection, which can be differentiated
into two different types: thermodynamic inhibitor and kinetic in-
hibitor injection (Sloan and Koh, 2008). Chemical inhibitor injec-
tion calls for the addition of strong hydrogen-bonding chemicals
(such as methanol or ethylene glycol), leading to a shift in gas hy-
drate equilibrium curve. In contrast, kinetic inhibition allows sys-
tem to exist within the hydrate stability zone, while small crystals
are stabilized without agglomerating into larger hydrate mass (Koh
et al., 2002; Lederhos et al., 1996; Notz et al., 1996; Sloan et al.,
1998). Current research is shifting from hydrate avoidance using
thermodynamic inhibitors towards hydrate risk management,
whereby kinetic hydrate inhibitors (KHI) and anti-agglomerates
(AA) are preferred to delay hydrate formation and prevent the
adherence of hydrate particles respectively (Sloan, 2005; Sum et al.,
2009).
Hydrate reservoir exploration and field production tests from
hydrate reservoirs are another major area related to hydrate
dissociation process. Field tests have been carried out in both
onshore and offshore environment. These hydrate field tests
include the Mount Elbert well test (Hunter et al., 2003), Ignik
Sikumi field trials in Alaska North Slope by CH4eCO2 exchange
(White and Lee, 2014), Malik gas hydrate site test in Canada
(Yamamoto and Dallimore, 2008a) and MH-21 Japan Nankai Trough
hydrate well test by depressurization (Tsuji et al., 2004). These field
trials involve high capital investment, long planning and execution
period, arduous working environment and unpredictable opera-
tions, therefore require strong collaboration effort between gov-
ernment, corporations and research institutions. Therefore, there is
a critical need to pursue cutting edge research developments in a
laboratory setting at multi-scale levels to understand the hydrate
dissociation characteristics to devise the methods and equipment
for realizing the potential of energy recovery from natural gas hy-
drates. The most critical issue before the execution of any field test
is the selection of appropriate hydrate bearing zones and the esti-
mation of gas production behaviour under different production
strategies. Therefore, fundamental understanding of hydrate
dissociation kinetic models is essential to model hydrate reservoir
dissociation process for energy recovery from natural gas hydrates.
Over the past four decades, several mathematical models and
numerical codes have been developed to investigate methane hy-
drate decomposition and methane gas production behaviour. For a
mathematical model to be representative, it should couple all the
primary dissociation mechanisms, including heat and mass trans-
fer, gas and water flow behaviour, intrinsic decomposition kinetics
in pure hydrate system or effective decomposition rate for hydrate
dissociation in porous medium. These three mechanisms involved
during hydrate dissociation are of equal importance; coupled with
each other and either of them could be the limiting factor under
different conditions. Intrinsic decomposition rate of methane hy-
drate is controlled by temperature, pressure, interfacial area and
the intrinsic rate constant (Kim et al., 1987). It affects the heat
transfer rate from surrounding to hydrate core due to the endo-
thermic characteristics of the reaction. In addition, flow of the
decomposed gas and water through the porous media could also be
1364 Z. Yin et al. / Journal of Natural Gas Science and Engineering 35 (2016) 1362e1387

limiting if the permeability of the porous media is low or the flow
path is long (Hong et al., 2003).
In the first section, a total of 14 hydrate dissociation kinetic
models with different degrees of complexity are reviewed on the
macroscopic level; followed by an overview on the molecular dy-
namics (MD) simulation of hydrate dissociation. The process
formulation, assumptions, governing equations, solution method,
and limitations of major models are described in detail with
highlights presented. The relationship between different kinetic
models is identified from the main driving mechanism, and the
evolution of each kinetic model is also presented with the modi-
fication carried out by different research groups. Further
improvement is proposed at the end of each section. In addition,
key hydrate dissociation intrinsic kinetic rate parameters are
summarized, which could be directly applied for future modelling
efforts. The classical hydrate dissociation kinetic models are also
the fundamental building block for hydrate CFD simulation and
hydrate reservoir modelling, which will be discussed in the sub-
sequent sections.
2.2. Hydrate dissociation kinetic models
Major models simulating hydrate dissociation process since
1980s are summarized in Table 1. These models are divided into
three different categories in terms of the solution method, namely
analytical, numerical and theoretical. Analytical solution gives the
closed-form solutions of the differential equations employed to
describe the dissociation system, while numerical solution applies
discretization method to solve the differential equations and the
results are affected by the time and space discretization method
used. It is obvious that hydrate dissociation computational fluid
dynamic (CFD) modelling falls in the category of numerical solu-
tion. Theoretical solution model is purely derived based on theory
without any semi-empirical correlation (Windmeier and Oellrich,
2013a, 2013b). Besides, the models reviewed are also differenti-
ated by its dissociation mechanisms, namely intrinsic kinetics, heat
transfer, mass transfer and fluid flow. Table 1 gives a summary of
the kinetic models’ capability to simulate hydrate dissociation in
porous media or in bulk hydrate system.
The progress of hydrate dissociation kinetic model development
over the last three decades (shown in blue), including major
milestones in reservoir simulation (shown in green), is also illus-
trated in chronological order in Fig. 1. Two different research groups
started to model hydrate dissociation process from two different
mechanisms since mid-1980s: Selim and Sloan (1985) presented
the Selim-Sloan hydrate dissociation model which treated the
dissociation process as a moving boundary ablation problem under
constant heat flux; whereas Kim et al. (1987) conducted hydrate
dissociation experiments and developed Kim-Bishnoi intrinsic ki-
netic model to describe the kinetics of hydrate decomposition
without heat and mass transfer limitation. Jamaluddin et al. (1989)
presented his model which successfully coupled intrinsic kinetics
with heat transfer rates. Selim and Sloan (1987) further extended
their model to describe hydrate dissociation in porous medium
under thermal stimulation in 1990. Yousif et al. (1991) coupled
mass and momentum equations of three phases (gas, water, hy-
drate) with intrinsic kinetics to model the hydrate dissociation in
porous media. With the advancements in scientific computing to
solve sets of differential equations numerically with better effi-
ciency, analytical solution is not necessarily required to describe
the system behaviour. Thus, numerical solutions are given for most
mathematical models to depict hydrate decomposition in recent
decade using various numerical simulators. Mathematical models
and numerical simulators which could couple all three primary
mechanisms and reservoir modelling for gas production started to
thrive in the late 1990s and gradually became mature in decades of
time (Gamwo and Liu, 2010; Hong and Pooladi-Darvish, 2005;
Moridis, 2003). Modelling hydrate dissociation using CFD software
(Nazridoust and Ahmadi, 2007; Sean et al., 2007a, 2007b) and
reservoir modelling (Ahmadi et al., 2004; Hong and Pooladi-
Darvish, 2005; Moridis, 2003; Vafaei et al., 2014) are fruits of the
advancements on hydrate kinetic models, and these numerical
tools are still evolving to provide a more accurate depiction of hy-
drate dissociation under different boundary conditions and scales.
2.2.1. Kim-Bishnoi hydrate decomposition intrinsic kinetic model
Kim et al. (1987) conducted experiments to study the kinetics of
methane hydrate decomposition using a semi-batch stirred-tank
reactor and proposed a mathematical model to simulate hydrate
decomposition. Hydrate decomposition was accomplished by
reducing the pressure on hydrate slurry in water isothermally. The
proposed model correlated the decomposition rate with hydrate
particle surface area and the difference in fugacity of methane at
equilibrium pressure and the decomposition pressure. Fig. 2 shows
the mechanism of hydrate decomposing process. The hydrate par-
ticle was surrounded by a cloud of gas and the driving force was
defined as the methane fugacity difference between the hydrate
equilibrium phase and the gas phase. According to the proposed
model, the overall process of hydrate decomposition involved two
steps:

Table 1
Summary of gas hydrate dissociation kinetic models.

Model/Researcher Heat transfer Fluid flow Intrinsic kinetics Porous media Solution method Reference

Conductive Convective Gas Water

Kim-Bishnoi e e e e √ e Analytical (1987)

Selim-Sloan √ e √ e e √ Analytical (1989)
Jamaluddin et al. √ e e e √ e Numerical (1989)
Yousif et al. e e √ √ √ √ Numerical (1991)
Tsypkin √ √ √ e e √ Analytical (1993)
Makogon et al. e √ √ e e √ Analytical (1997)
Moridis et al. √ √ √ √ √ √ Numerical (2003)
Hong et al. √ √ √ √ √ √ Analytical (2003)
Ahamadi et al. √ √ √ e e √ Numerical (2004)
Sean et al. √ √ √ √ √ e Numerical (2007a)
Nazridoust et al. √ √ √ √ √ √ Numerical (2007)
Oyama et al. √ √ e e √ √ Theoretical (2009)
Gamwo et al. √ √ √ √ √ √ Numerical (2010)
Windmeier et al. e e e e √ e Theoretical (2013a)
 Z. Yin et al. / Journal of Natural Gas Science and Engineering 35 (2016) 1362e1387 1365

Fig. 1. Timeline of the development of hydrate dissociation kinetics and reservoir models.

Fig. 2. Schematic of the mechanism for hydrate decomposition. Reprinted with permission from Bishnoi and Natarajan (1996).

(1) destruction of the clathrate host lattice at the surface of a defined as the difference between the fugacity of methane at the
particle; equilibrium, fe and the fugacity of methane at the solid surface, f. It
(2) desorption of the guest molecule (methane) from the surface was also assumed that the rate of hydrate decomposition rate is
proportional to the combined surface area of the decomposing
The above-mentioned steps occurred at the solid surface, not particles, As and decomposition rate constant, kd. As a result, the
within the bulk of the solid and the decomposition rate is propor- rate of hydrate decomposition
dn dt
H
was expressed as:
tional to driving force that exists. Mass transfer was not considered
due to the high stirring rates and heat transfer resistance was also
dn
assumed negligible as the hydrate particle temperature was the
H ¼ kd As ðfe
f Þ (1)
dt
same as that of the water. The driving force in this model was
To simplify the model, the area of the particles As, was expressed
1366 Z. Yin et al. / Journal of Natural Gas Science and Engineering 35 (2016) 1362e1387
as a function of nH with the following assumptions:
(1) The hydrate is invariant in composition and contains rH
moles of methane per unit volume;
(2) All hydrate particles have the same volume and a uniform
decomposition rate;
(3) The number of particles does not change during
decomposition;
(4) The particles could be non-spherical;
(5) The hydrate particles have the same diameter D0 before
decomposition begins;
With the above assumptions, the decomposition rate equation
was simplified to:
dn 1=3 2=3

H ¼ kn0 nH
dt


6 ~8 mm with a standard deviation of approximately 3 mm. This
k ¼ kd ðfe
f Þ
4rH D0
where 4 is the sphericity factor and k is the rate constant and has
the dimension of (time)
1. By combining Arrhenius temperature
dependence into the rate constant, the rate constant k can also be
expressed as follows:
k ¼ k0 e
DE=RT ðfe
f Þ
where k0 is independent of the pressure and temperature, but is
dependent on the initial particle geometry. To calculate the
intrinsic decomposition rate constant, k0d , which is independent of
the temperature, pressure and particle geometry, the geometry and
size of the hydrate particles should be estimated. In Kim-Bishnoi
model developed in 1986, the size and geometry measurement of
hydrate particles was not available in the laboratory. Therefore this
information was estimated from a force balance in the Stokes flow
region with hindered settling time measured and the size of the
particle was estimated to be about 16 mm. The experimental kinetic
data was fitted using non-linear least squares method and the
intrinsic decomposition rate constant k0d was estimated to be
1.24  105mol/m2Pa s with activation energy DE determined as
78.3 kJ/mol.
This is the first time that the intrinsic kinetics of hydrate
decomposition was studied with heat and mass transfer effects
neglected. It was shown that methane hydrate decomposition ki-
netics was dependent on the pressure, temperature and particle
surface area. The intrinsic rate equations obtained can also be
combined with the equations of heat and mass transfer to obtain
the global rate equations that could be used in design and reservoir
simulation. The Kim-Bishnoi decomposition model remains as the
most classical model to understand hydrate kinetic dissociation
process to date. It is incorporated in almost all kinetic models of
hydrate dissociation developed later, be it reservoir modelling or
CFD modelling (Hong and Pooladi-Darvish, 2005; Jamaluddin et al.,
1989; Moridis, 2003; Yousif et al., 1991).
Based on Kim-Bishnoi intrinsic kinetic model, the kinetics of
ethane hydrate decomposition was further studied using an
isothermal/isobaric semi-batch stirred-tank reactor (Clarke and
Bishnoi, 2000b, 2001a). The improvement in the mathematical
model accounts for the distribution of particle sizes by using an
external online particle size analyser in the hydrate phase. In
addition, population balance model was also included assuming no
breakage or agglomeration during the decomposition of the hy-
drate particles. Both heat and mass transfer were neglected to make
sure the decomposition process was limited by intrinsic kinetics.
The new model was able to describe the intrinsic rate of decom-
position of gas hydrates of any arbitrary shape and it superseded
the Kim-Bishnoi model on particle size estimation in terms of ac-
curacy. From the experimental kinetic data, the ethane hydrate
decomposition intrinsic kinetic rate constant ðk0d Þ was estimated to
be 2.56 108mol/m2Pa s with an activation energy (DE) of 104 kJ/
mol. Clarke et al. (Clarke and Bishnoi, 2001a) also employed the
same experimental apparatus and procedure to re-estimate the
decomposition kinetics of methane hydrate. It was found that the
methane hydrate decomposition intrinsic rate constant was
3.6 104 mol/m2Pa s with an activation energy of 81 kJ/mol, which
differed from the results first reported by Kim et al. (1987). The
intrinsic rate constant was almost 4 times smaller and activation
energy is larger by 3 kJ/mol. The reason for the deviation was
attributed to the difference in the particle size estimation. While
Kim et al. assumed that the hydrate particles have the same initial
(2)
diameter and estimated to be 16 mm from Stokes Law, Clarke and
Bishnoi (2001a) measured that the hydrate particles distributed
(3)
indicated that the work of Kim et al. (1987) underestimated the
total surface area available for the decomposition process and
caused an overestimation of the intrinsic rate constant.
The Kim-Bishnoi kinetic model was further extended to study
the gas hydrate decomposition rate formed from mixture of
methane and ethane by Clarke and Bishnoi (2001b) instead of pure
gas system. The kinetic parameter for methane hydrate formed in
(4) structure II was also derived from the study with the assumption
that ethane only enters the large cavity in both structure I and
structure II, so that the rate constant for ethane decomposition is
the same in both structures. The experiments were carried out with
methane composition within the range of 71% e 99.3% where sII
hydrate were stable (Subramanian et al., 2000). The regression
from the kinetic data showed that the rate constant for methane
hydrate in sII was 8.06 103 mol/m2 Pa s and the activation energy
was 77.33 kJ/mol. The activation energy for methane hydrate
decomposition in sII was shown to be slightly lower than in sI,
which indicates sII methane hydrate decomposes faster than sI
methane hydrates. However, the reason for this difference was not
provided and could be further analysed from the difference be-
tween different hydrate structures.
Besides CH4 and C2H6 hydrates, Clarke and Bishnoi (2005) also
carried out a study to determine the intrinsic rate constant and the
activation energy of CO2 hydrate decomposition. The improvement
of the experimental apparatus includes applying in-situ particle
size analyser rather than an external particle size analyser (Clarke
and Bishnoi, 2000b, 2001a) when measuring the hydrate particle
surface area. The application of in-situ particle size analyser
enabled a more accurate particle size measurement less than 5 mm,
which could not be completed in earlier study where extrapolation
had to be performed. To examine the Kim-Bishnoi model
assumption that no breakage or agglomeration of hydrate particles
happened during the dissociation process, the impact of breakage
of particles on the intrinsic rate constant and activation energy was
also investigated in this study (Clarke and Bishnoi, 2004). By
comparing measurement of the second moment of hydrate parti-
cles and the model prediction, it was found that some breakage of
the particles did occur. However, from the hydrate re-stabilising
and re-initiating decomposition process, it was found that the
impact of breakage due to porosity, or any other mechanism, was
insignificant on the values of the intrinsic rate constant and acti-
vation energy determined. The study concluded that CO2 hydrate
particle had a median size of 4.5 mm and the intrinsic rate constant
was 1.83 108 mol/m2 Pa s with an activation energy of 102.88 kJ/
mol Table 2 summarizes gas hydrate decomposition intrinsic ki-
netic data used in Kim-Bishnoi model.
 Z. Yin et al. / Journal of Natural Gas Science and Engineering 35 (2016) 1362e1387 1367

Table 2
Gas hydrate decomposition intrinsic kinetic data in Kim-Bishnoi Model.

Guest Molecule hydrate type Intrinsic rate constant ðk0d Þ mol/m2 Pa s Activation energy (DE) kJ/mol Reference

CH4 e sI 1.24  105 78.3 (Kim et al., 1987)

CH4 e sI 3.6  104 81.0 (Clarke and Bishnoi, 2001a)
CH4 e sII 8.06  103 77.3 (Clarke and Bishnoi, 2001b)
C2H6 2.56  108 105.0 (Clarke and Bishnoi, 2000b)
CO2 1.83  108 102.9 (Clarke and Bishnoi, 2005)

Following Kim-Bishnoi-Clarke hydrate dissociation model, mathematical model for hydrate dissociation under thermal stim-
Giraldo and Clarke (2013) proposed a simplified approach to model ulation. Their model assumed the decomposition of a pure hydrate
the kinetics of gas hydrate decomposition from mixed gases. This block using a constant heat flux employed on a planar semi-infinite
technique removed the need to acquire the intrinsic rate constant medium with constant physical properties. With the critical
of gas hydrate decomposition for each component in the mixture, assumption that water formed during the dissociation process was
rather with only a single intrinsic rate constant, it is able to model blown away by the gas, the dissociation process was treated as a
the decomposition kinetics. The essence of the model is that with moving-boundary ablation problem and there would be no liquid
the introduction of a reference component, the rate of gas libera- phase over the dissociation surface.
tion of any component i can be related to the rate of the gas pro- The mathematical model was based upon a planar, one-
duction of the reference component, so that the mathematical dimensional semi-infinite system with the physical situation pre-
formula for rate of decomposition could be simplified as follows: sented in Fig. 3(a) and (b). The hydrate body was at uniform tem-
    perature Ti and occupied the semi-infinite region 0 < x < ∞. At time
dn u dn t ¼ 0, constant heat flux qs was applied to the boundary surface at
¼ i (5)
dt u1 dt 1 x ¼ 0. The temperature of the boundary surface was expected to
rise from Ti to Ts, which was the temperature in equilibrium with
   
u 
dn 1 u u the prevailing pressure as shown in Fig. 3(a). Dissociation would

¼ AP K1 feq
fg þ 2þ 3þ/
dt P u1 u1 u1 start and the boundary surface moved in the positive x direction as
  shown in Fig. 3(b). The temperature of the moving boundary still
¼ AP K1 feq
fg u (6) remained constant at Ts. With the assumption that water was

X
NC
uj
u¼ (7)
1
ui

where ui value is the stoichiometric coefficient of each hydrate-

forming compound in the hydrate phase. The rest of the model
formulation is identical to that used by Clarke and Bishnoi (Clarke
and Bishnoi, 2000b, 2001a, 2005). The population balance model
was included with the initial values of the zeroth, first and second
moments of particles size distribution inferred from experimental
measurement from particle size analyser. The new model was
tested to examine the kinetics of gas hydrate decomposition from
two mixtures and the results were compared against both experi-
mental data and the model results from the Clarke-Bishnoi model.
It was found that the numerical accuracy of the predictions ob-
tained from the new model has slight improvement over those
obtained using Clarke-Bishnoi model (2001b).
However, there is still limitation in the newly proposed model as
the stoichiometric coefficient ui may be dependent on time and
hydrate structure types. In that experimental apparatus, it was not
possible to measure the relationship between the stoichiometric
coefficients against time. Thus, it was assumed to be constant along
the dissociation process. In addition, the calculation of gas phase
fugacity did not take into account of the variation in both tem-
perature and gas-phase composition as it was not possible to
measure the real-time gas phase composition with the current
setup. Therefore a time-averaged gas phase composition was
assumed in the current model to compute the fugacity difference.
These constraints in the model could be removed for better accu-
racy with more sophisticated experimental measurements or by
establishing correlations using theoretical analysis.

2.2.2. Selim-Sloan hydrate dissociation kinetic model

Parallel to the Kim-Bishnoi intrinsic kinetic model proposed for Fig. 3. Hydrate dissociation process with moving boundary (a) Pre-dissociation (b)
hydrate decomposition, Selim and Sloan (1985) also developed a During Dissociation. Redrawn from Selim and Sloan (1989).
1368 Z. Yin et al. / Journal of Natural Gas Science and Engineering 35 (2016) 1362e1387
completely removed from the surface immediately on formation,
the problem was simplified as an ablation problem and only heat
transfer in the undissociated solid phase was considered.
Assuming tsd as the time required for the boundary surface to
reach the equilibrium temperature Ts. For large values of heat input,
when t < tsd, the problem was a fixed-boundary problem, while for
t > tsd the problem became a moving-boundary problem. The fixed
boundary problem was treated as a heat transfer problem before
dissociation occurred. Fourier's law of heat transfer and energy
balance equation were applied to describe the system with initial
and boundary conditions given as follows with symbols reference
to Fig. 3(a) and (b):
For t < tsd
vT v2 T
¼ a 2 0 < x < ∞; t > 0
vt vx
vT

k ¼ qs x ¼ 0; t > 0
vx
T ¼ Ti x ¼ ∞; t > 0
T ¼ Ti 0 < x < ∞; t ¼ 0
For t > tsd
vT v2 T
¼ a 2 XðtÞ < x < ∞; t > 0
vt vx
T ¼ Ts x ¼ XðtÞ; t > 0
vT dX

k þ rl ¼ qs x ¼ XðtÞ; t > 0
vx dt
T ¼ Ti x ¼ ∞; t > 0
T ¼ f ðxÞ 0 < x < ∞; t ¼ tsd
The solution of the problem was first proposed by Goodman
(1958) utilizing the heat-balance integral method with a second-
degree polynomial approximation for the temperature profile.
Selim and Sloan (1985) similarly applied a fourth degree poly-
nomial to approximate the exact solution in this study to improve
the solution accuracy. The final results yielded a relationship for the
dimensionless position of the moving front X* as a function of
dimensionless time t. It was also found that the speed of the
dissociation front decreased with time and eventually attained a
constant value. Despite all the assumptions made for this model, it
was the first time hydrate dissociation process being modelled as a
moving-boundary ablation problem with thermal stimulation as
the driving force and also provides a solution to describe the
moving boundary. It could be used to determine the amount of
hydrate dissociated as a function of time, one key parameter in
hydrate dissociation kinetic modelling. Ullerich et al. (1987) con-
ducted experiments on methane hydrate dissociation with a con-
stant heat flux to validate the proposed model by Selim and Sloan
(1985). The rate of dissociation of methane hydrate was measured
from hydrate mass loss. The dissociation front was measured and
compared with the results from Selim and Sloan (1985) with 3
different samples. The difference between the experimental data
and the model prediction was within 10% and acceptable consid-
ering the laxity of the model. Although no intrinsic decomposition
kinetic rate and mass transfer limitation were considered in the
model, it still lays the foundation of the study of heat transfer effect
and dissociation front of the hydrate dissociation process. Besides,
it contributes to model hydrate dissociation within porous media,
where heat transfer via both heat conduction and advection plays a
much dominant role.
Based on their own model, Selim and Sloan (Selim and Sloan,
1987, 1989) extended the mathematical model to describe hy-
drate dissociation under thermal stimulation in porous media. The
model viewed the dissociation as a process whereby gas and water
were produced at a moving boundary. This boundary separated the
dissociated zone (containing gas and water) from the undissociated
zone (containing hydrate). One major assumption of the model is
that water remained motionless within the pores of the dissociated
zone. This assumption limited the model analysis to hydrate satu-
ration values of ~0.3. Besides, the thermophysical properties of each
phase were assumed to be constant. Viscous dissipation, reversible
(8)
work of compression, inertial effects and the possibility of mutual
or external energy transmission were all neglected for simplicity
(Selim and Sloan, 1989). To create the model, differential equations
(9) of mass and energy balances were set up to describe the dissocia-
tion process. In addition, the momentum equation of gas in the
dissociated phase was included by Darcy's Law. Boundary and
initial conditions were given to describe the dissociation front
respectively. The set of differential equations were solved analyti-
cally by introducing the Boltzmann transformation and it was
concluded that the dissociation front was a constant-temperature
boundary moving at a rate proportional to t
1/2. The model was
applied to simulate two different conditions with heat flux, tem-
(10) perature profile and pressure profile plotted against distance with
time variation (Selim and Sloan, 1987). A new concept of overall
energy efficiency ratio (FE), which is the ratio of heating value of gas
produced and total heat added to the system, was introduced to
evaluate the potential of gas production from hydrate reserves
through thermal stimulation. The values of FE reported in the study
(11)
ranged between 6.2 and 11.4, with a value ~9 for practical tem-
perature and pressure condition to justify the value of natural gas
production from reservoir. A parametric study was also carried out
to examine the effects of various parameters on the dissociation
rate including: porosity, permeability, gas viscosity, thermal diffu-
sivity and conductivity of both hydrate zone and dissociated zones
(Selim and Sloan, 1987). The three main conclusions drawn from
the study were:
(1) Higher dissociation rates resulted from an increase in the
thermal diffusivity and thermal conductivity of the dissoci-
ation region; but a lower thermal diffusivity and thermal
conductivity in hydrate-region was required;
(2) The dissociation rate was independent of the permeability of
the porous medium and the viscosity of the flowing gas;
(3) The dissociation rate decreased with an increasing porosity
of hydrate phase.
The Selim-Sloan model of hydrate dissociation in sediment in
1990 was a great extension of the in-situ dissociation model
developed in 1985. Although the primary mechanism of the
dissociation was still thermal stimulation without considering
intrinsic kinetic rate and fluid flow behaviour, the model success-
fully considered the moving boundary of the dissociated phase in
porous media. It was shown that thermal properties of the system
and the porosity of the porous medium had a strong impact on the
dissociation rate. However, the conclusion drawn from the study
was questionable and even contrary to what was reported later
from the parametric study on gas hydrate reservoir modelling
carried out by Ji et al. (2001) and Hong and Pooladi-Darvish (2005).
The relationship between hydrate dissociate rate and hydrate layer
conductivity, porosity and permeability still needs to be further
 Z. Yin et al. / Journal of Natural Gas Science and Engineering 35 (2016) 1362e1387 1369

studied. Nonetheless, the model proposed by Selim and Sloan shed
light on modelling hydrate dissociation process in porous media
and is useful for reservoir modelling attempts later.
2.2.3. Jamaluddin-Bishnoi hydrate dissociation kinetic model
Based on Selim-Sloan hydrate dissociation model under thermal
stimulation and Kim-Bishnoi hydrate decomposition intrinsic ki-
netic model, Jamaluddin et al. (1989) coupled the two models and
developed a mathematical model to consider the effect of both heat
transfer and intrinsic kinetics. The proposed model also considered
hydrate block as a planar, one dimensional semi-infinite body. The
rate of hydrate decomposition was expressed in the form of
intrinsic kinetic rate, which was a function of the fugacity differ-
ence of methane, intrinsic kinetic rate constant, activation energy
and surface roughness factor. This was coupled in the heat transfer
rate equation and the correlation was established which involved
both temperature correlation and intrinsic kinetic parameters. The
initial temperature profile was solved analytically using the
method proposed by Selim and Sloan (1985). However, to solve the
sets of ordinary differential equations to find the temperature
profile, method of lines (MOL) was employed to create the dis-
cretization and Newton-Raphson method was applied to give the
solution numerically. Parametric study was also carried out with
the model to study the effect of activation energy, surface rough-
ness factor and system pressure of the dissociation process. The
results from the simulation elucidated that activation energy had a
significant effect on the rate of decomposition and by varying the
surface roughness factor and system pressure, it is possible to move
from a heat transfer controlled regime to a regime where both heat
transfer and intrinsic kinetics control the global rate of decompo-
sition. In the study, Jamaluddin et al. also attempted to apply the
newly developed model to validate the experimental results pub-
lished by Ullerich et al. (1987). However, the model only showed a
good agreement with the experimental data when the heat flux is
20% more than the experimental condition. One thing to note is
that the intrinsic kinetic parameter used in this study is extracted
from Kim-Bishnoi model in 1987. This could be further improved by
employing the kinetic parameter provided by Clarke and Bishnoi
(2001a) for better accuracy.
In summary, Jamaluddin-Bishnoi model is the first model to
couple heat transfer effect with intrinsic kinetics to simulate the
decomposition of a core methane hydrate and proves that the
dissociation of hydrate can move from a heat transfer controlled
regime to a regime where both heat transfer and intrinsic kinetics
have a significant effect on the global rate of decomposition. Be-
sides, it also provides guidance for further researchers to include
other primary mechanisms including gas and liquid phase fluid
flow behaviour, mass transfer rate to simulate hydrate dissociation
process.
Several key assumptions of the Makogon model should be
emphasized before introducing the model. One is that at the
dissociation front, temperature and pressure were at equilibrium.
Furthermore, when solving the temperature field equations, heat
conduction term was neglected considering that the conductive
heat flow in a porous medium was several orders of magnitude less
than the convective flow (Makogon, 1997). The other assumptions
were that (1) during hydrate decomposition, the front was the
source of mass that released water and methane gas; (2) the
movement of water in porous medium was neglected and (3) the
permeability of the hydrate layer was assumed constant. The linear
one-dimensional mathematical model of hydrate decomposition in
porous medium during depressurization was formulated as follows
with schematic shown in Fig. 4. The distribution of pressure in the
layer was described by the equation of gas filtration:
2mn mn vPn v2 Pn2
¼ (12)
kn vt vx2
where
m1 ¼ ð1
aÞm;
m2 ¼ ð1
bÞm;
where m is viscosity of gas, k is gas permeability in the zone, m is
porosity, a is water saturation and b is hydrate saturation. In Eq.
(12) and the subsequent analysis, n ¼ 1 corresponded to the region
0 < x < l(t), which was the dissociation layer, and n ¼ 2 referred to
the region l(t) < x < ∞, which was the hydrate layer. l(t) was the
distance of dissociation front from the origin. The boundary con-
ditions were:
P1 ð0; tÞ ¼ PG ; P2 ðx; 0Þ ¼ P2 ð∞; tÞ ¼ Pe
P1 ðlðtÞ; tÞ ¼ P2 ðlðtÞ; tÞ ¼ PD ðTD Þ
T1 ðlðtÞ; tÞ ¼ T2 ðlðtÞ; tÞ T2 ðx; 0Þ ¼ Tð∞; tÞ ¼ Te
where Pn and Tn are the pressure and temperature in Zone 1 or 2
respectively, PD and TD is pressure and temperature at the decom-
position front. Pe and Te are pressure and temperature at the
reservoir condition. With the model assumption, PD and TD are the
equilibrium pressure and temperature for methane hydrate. The
relationship between methane hydrate equilibrium pressure and
temperature was obtained from an empirical correlation from
Makogon (1997).

2.2.4. Makogon hydrate dissociation kinetic model

Makogon (1997) published his model of hydrate decomposition
in porous medium during depressurization. In this work, Makogon
described that the decomposition of hydrates in porous medium
happened in a certain narrow zone which was treated as a surface,
rather than the whole volume. However, it was believed that the
rate of hydrate decomposition was determined by the movement of
the decomposition front, but not by the kinetics of the process,
which is controversial to the intrinsic kinetic model proposed by
Kim et al. (1987). The movement of the front depends on the
magnitude of heat flow though it and on the specific heat of hydrate
formation. Thus, Makogon first addressed the problem of hydrate
decomposition by a pressure decrease using an analogy of the
classical Stefan's problem for melting with a self-similar solution Fig. 4. Schematics of hydrate reservoir for the one-dimensional model. Reproduced
obtained after linearization of equations of the gas filtration. from Ji et al. (2001).
1370 Z. Yin et al. / Journal of Natural Gas Science and Engineering 35 (2016) 1362e1387
log10 PD ¼ aðTD
T0 Þ þ bðTD
T0 Þ2 þ c
where T0 ¼ 273.15 K, a ¼ 0.0342/K, b ¼ 0.0005/K2, c ¼ 6.4804
The mass balance for gas at the decomposition front was ob-
tained as follows from the work of Verigin et al. (1980):
dl
r1 v1
r2 v2 ¼
½bεr3
ð1
aÞr1 þ ð1
bÞr2 m
dt
where r1 and r2 are the densities of natural gas in Zone 1 and 2, r3 is
the density of hydrate, ε is the mass fraction of gas in methane
hydrate, v1 and v2 are the velocities of natural gas in Zone 1 and 2.
Since gas is of the same composition both on the right and on the
left, thus, by using the continuity of pressure at the dissociation
front and the equation of state for gas, the densities of natural gas
was expressed as:
PD T0
r1 ðl; tÞ ¼ r2 ðl; tÞ ¼ r0
zPo TD
where z is the gas compressibility, and r0 is the gas density at at-
mospheric pressure Po and T0.
With this expression, the equation of gas balance at the
decomposition front was simplified:


r Po TD dl
v1 ðl; tÞ
v2 ðl; tÞ ¼
bε 3
ðb
aÞÞ m
r0 PD T0 dt
The mass balance equation for water released from a hydrate
was:
rW ma ¼ ð1
εÞr3 mb
With the assumption that water density and porosity remain as
constant, the water saturation in Zone 1 during decomposition was
determined by gas hydrate composition and saturation. The tem-
perature field of a gas-saturated layer is governed by the equations
as follows which takes into account both convective, conductive
heat flows and temperature change caused by throttling and
adiabatic effects.
 
v2 Tn vTn cv kn vPn vTn vPn mn cv vPn
an ¼

d
h
vx2 vt cn m vx vx vx cn vt
where an and cn is the thermal diffusivity and heat capacity of
respective zone, cv is the volume heat capacity of gas, d and h is the
throttling and adiabatic coefficients of gas.
To find solution of the above mathematical mode, linearization
was applied to simplify the differential equations and a self-similar
solution was given by Makogon (1997) to find the temperature and
pressure in each zone and the dissociation front against time. Be-
sides, the rate of hydrate decomposition, production rate of gas and
water content of the layer during hydrate decomposition could all
be determined from the solution. Based on his model, Ahmadi et al.
(2000) represented the model and solved the system numerically
to evaluate the distribution of temperature and pressure in porous
layer of methane hydrate and in the gas region for different well
pressures and temperatures. The distance of decomposition front
from the well to the natural gas output as a function of time, time
evolution of the resulting temperature and pressure were all solved
and presented graphically.
The common conclusion drawn from this study was that for a
fixed reservoir temperature and pressure, the gas production rate
decreased and the motion of the decomposition front slowed down
as the reservoir pressure increased. For a fixed reservoir pressure,
the gas production rate decreased significantly with a decrease in
the reservoir temperature. The distance of decomposition front
(13) from the well increased in a direct proportion to the square root of
time, and production rate decreased in inverse proportion of time.
Ji et al. (2001) applied Makogon model and extended his work to
a sensitivity analysis for time evolutions of pressure and tempera-
ture profiles, methane gas production rate and location of dissoci-
ation front with respect to zone permeability and reservoir
(14) porosity. Both ideal condition and Kozeny-Carman equation of
permeability-porosity correlation proposed by Kaviany (1995) was
applied to account for the effect of porosity changes to permeability
in the study. It was concluded from the study that reservoirs with
higher permeability had higher production rate and the decom-
position front penetrated faster into the reservoir for a fixed
porosity. Both temperature and pressure profiles were self-similar
with the variation of permeability. However, when Kozeny-
Carman correlation was applied, increasing reservoir porosity
increased gas output, while the speed of decomposition front
motion decreased. The variation of reservoir porosity also altered
(15) the temperature and pressure profile significantly.
One limitation of the model is that heat conduction term in the
energy equation was neglected and this does not satisfy energy
balance at the dissociation front. Ahmadi et al. (2004) improved on
Makogon's model by including both heat conduction and advection
in the energy equation. The governing equations were solved using
a finite-difference numerical scheme. This warrants the detailed
study on the role of both convective and conductive heat fluxes on
(16)
the hydrate dissociation system. The results from the study were
compared with those obtained by the linearization method which
was proposed by Makogon and the shortcoming of the linearization
method was discussed.
It should be highlighted from the results that conductive heat
(17)
flux plays a dominant role in supplying heat for hydrate dissocia-
tion. This study closed the assumption made by Makogon (1997)
that conductive heat transfer is several orders less than convec-
tive heat transfer in his model development and it is worthwhile to
further elucidate the effects of conductive and convective heat
transfer in hydrate dissociation within porous media. Compared to
the linearization method used in Makogon dissociation model, the
numerical solution method of the governing equation provides a
more accurate description for the process.
Besides the linear one dimensional analysis of hydrate decom-
(18)
position in a Cartesian coordinate, Ji et al. (2003) further extended
the study to an axisymmetric condition in the case of a radial co-
ordinate. The mathematical formulation for evaluation of pressure
and temperature fields were based on the method proposed by
Makogon (1997). Linearization and self-similar solution for the set
of differential equations were given to understand the time evo-
lution of pressure and temperature profiles in the hydrate reservoir.
Time variations of location of the dissociation front were also
evaluated with gas production rates analysed. However, the limi-
tations in using the linearization approach to solve the system
equations are that the heat conduction term has to be neglected
and the energy balance of the dissociation front is not possible to be
enforced. Thus, a numerical solution of the set of governing equa-
tions were performed by Ahmadi et al. (2007), which gave a more
accurate description of the process with analysis of heat fluxes at
the dissociation front. Yet, one drawback of the model is that the
intrinsic kinetics of the dissociation process is not included and this
could affect the time evolution of the dissociation front dramati-
cally when heat and mass transfer are not the limiting factors.
2.2.5. YousifeSloan hydrate dissociation kinetic model
Yousif et al. (1991) first presented a three-phase 1D model to
simulate the process of gas production under depressurization
mechanism. The highlight of the model is that it was the first to
 Z. Yin et al. / Journal of Natural Gas Science and Engineering 35 (2016) 1362e1387
include flow equations in the hydrate zone complement to the
equations of mass and energy. Both mass and momentum for each
of the three phases (gas, water and hydrate) were presented in the
porous media. This model implemented Kim-Bishnoi intrinsic ki-
netic model and the flow of water associated with hydrate disso-
ciation was also considered by applying Darcy's Law. The set of
nonlinear mass conservation and momentum conservation equa-
tions were linearized and solved numerically with an iterative
method. The time and space derivatives were approximated by a
block-centred finite-difference scheme. Results attained from this
model included the pressure profile; hydrate saturation profile,
permeability and porosity profile, dissociation front location of the
hydrate layer and the cumulative gas and water production profile
against time.
The model was employed to verify the experimental results
from methane hydrate dissociation in Berea sandstone cores.
Although the mathematical model provided a satisfactory match to
the experimental data in terms of predicting methane gas produced
and dissociation front location, there was some limitations on the
handling of absolute permeability and relative permeability within
the porous media. The initial absolute permeability was set to vary
linearly from the outlet to the hydrate core, which was an
assumption not based on measurement. The relationship between
relative permeability of water/gas and saturation of water was also
modified to make the system more permeable to both water and
gas without measurement. In addition, the dissociation reaction
rate constant was also reduced by an order of 105 to 10
16 from the
value reported by Kim et al. (1987) for pure hydrate dissociation
where mass transfer resistance was not considered. Thus, it is
imperative to understand better what is the impact of porous
media on hydrate dissociate rate, where both intrinsic kinetics and
mass transfer resistance have an effect on the overall rate constant.
2.2.6. Tsypkin hydrate dissociate kinetic model
Tsypkin (1993) suggested a complete system of equations to
correlate the phenomena of heat and mass transfer with gas hy-
drate dissociation. The formulation of the model allowed the ex-
istence of hydrate dissociation and phase transition fronts. The
advantage of this model is that by including the moving boundary,
it allows the formation of an extended dissociation zone or for-
mation of an ice-gas region located between hydrate dissociation
and ice melting fronts when describing the dissociation process,
which most numerical and analytical models may not account for.
The formulation of the problem and the governing equations
consists of mass conservation laws for gas, water (ice) and hydrate;
Darcy's laws; the energy conservation law for the mixture; the
Clapeyron equation for gas; and the thermodynamic relationships.
The essential part of the mathematical description is the specifi-
cation of boundary conditions. The set of non-linear differential
equations were solved using a linear approach for analytical solu-
tion. It was necessary to obtain a closed analytical form for the
nonlinear differential equations. Three different cases were
considered in the study: dissociation of gas hydrates in saturated
form; dissociation of gas hydrates saturated with excess gas; and
dissociation of gas hydrates saturated with water and gas. In each
scenario, the model was applied and it was shown that beyond
certain permeability limit, the dissociation front temperature may
fall below the water crystallization temperature. Interestingly, a
few years later, two experimental works reported this behaviour
and also observed an increase in hydrate decomposition rate
(Haligva et al., 2010; Zhou et al., 2009). Thus, formation of extended
hydrate dissociation should be taken into account in this situation.
The study also elucidated the effect of permeability on dissociation
fronts. However, Tsypkin's model was constructed considering
mass and energy conservation with gas flow described; whereas
1371
the intrinsic dissociation kinetics which could dominate the
dissociation front was not considered. Besides, the momentum
conservation equations for hydrate, water, gas and porous media
were not included in the model. Yet, the highlight of this model is
that it emphasized that hydrate dissociation front could fall below
water crystallization temperature, which cannot be described with
the typical formulation. An intrinsic hydrate dissociation model
that describes hydrates decomposing into gas and ice could be
developed and incorporated in Tsypkin's model.
2.2.7. Hong-Pooladi-Darvish hydrate dissociation kinetic model
Hong et al. presented a simple analytical model to simulate gas
production from hydrate decomposition in porous media by
depressurization method (Hong and Pooladi-Darvish, 2003, 2005;
Hong et al., 2003). Heat transfer to the decomposing zone, intrinsic
kinetics of hydrate decomposition and gas-water two-phase flow
were considered as the three primary mechanisms involved during
hydrate decomposition in porous media. In the study, the decom-
position rates controlled by heat transfer, intrinsic kinetics and by
fluid flow were quantified respectively to determine which of these
mechanisms was the rate controlling steps in realistic range of
physical properties of hydrate reservoir.
The formulation of hydrate decomposition rate by heat transfer
was analogous with the melting boundary problem. The analytical
solution for the temperature profile in hydrate zone and the loca-
tion of the hydrate interface profile was similar to the heat con-
duction process given by Ozisik (1993). The velocity of the interface
was derived as well for parametric studies of decomposition rate.
Preliminary conclusion drawn was that a larger value of Stephan
number (Ste) resulted in a larger interface velocity. With Ste of
porous media estimated to be about ten times of pure hydrate, it
was expected that the interface movement in porous medium to be
faster than that of pure hydrate with only heat transfer considered.
The formulation of decomposition rate controlled by intrinsic ki-
netics is analogous to the intrinsic kinetic model proposed by Kim
et al. (1987). Methane was assumed to behave as an ideal gas so that
the fugacity could be simplified as gas partial pressure. Mass bal-
ance was employed to derive the hydrate-gas decomposition
interface, which was later used for parametric study. Decomposi-
tion rate controlled by fluid flow was obtained by combining the
continuity equation for water and Darcy's law. The relationships for
the interface velocity for both water and methane gas were derived
(Hong et al., 2003).
After deriving the interface velocity during hydrate decompo-
sition, a set of hydrate thermal, physical properties and intrinsic
kinetic rate parameters were used to estimate the rate of decom-
position. The calculated results suggested that the rates controlled
by water and gas flow were ~1e2 orders of magnitude higher than
the rates controlled by heat transfer or intrinsic kinetics. With this
conclusion, an analytical model coupling intrinsic decomposition
and heat transfer mechanisms were further developed neglecting
the effect of water and gas flow behaviour. The governing equation
of the model consists of heat conduction, heat balance, kinetic rate
equation, decomposition rate constant equation and gas phase
equilibrium equation. Dimensionless variables were proposed and
nonlinear terms from the differential equations were linearized to
give the analytical solution. Detailed analysis of the analytical terms
on intrinsic kinetics and heat transfer was provided: at the early
time of hydrate dissociation, the intrinsic kinetics was the rate-
limiting mechanism as the surroundings had not been cooled
down and rate of heat flow was high; at later time of hydrate
dissociation, when rate of heat transfer decreased, heat flow
became the controlling mechanism. Temperature profile and
hydrate-gas interface velocity profile were plotted with both
analytical and numerical solution method with good agreement.
1372 Z. Yin et al. / Journal of Natural Gas Science and Engineering 35 (2016) 1362e1387
The constructed model was also applied to estimate the production
rate of a well drilled with a 10-m thickness of hydrate cap (Hong
and Pooladi-Darvish, 2003).
To extend their study, a 2D cylindrical simulator for gas pro-
duction from hydrate reservoir was constructed using the proposed
model (Hong and Pooladi-Darvish, 2005). A systematic sensitivity
study was also carried out to investigate the effect of various pa-
rameters on gas production rate, including rock permeability and
thermal conductivity. The simulated results showed that large
thermal conductivity promoted heat influx for faster hydrate
decomposition. It was also demonstrated that heat conduction and
the sensible heat of hydrate zone played dominant role in gas
production. Porous media permeability was found important in
production of free gas whereby high permeability could promote
the production rate; whereas the cumulative gas production was
predominantly limited by the availability of heat.
However, there are some assumptions and limitations of the
proposed model that is worthwhile to highlight before application
on other works. First, although the parameters used in the study
was close to hydrate reservoir real condition, the porosity and
permeability used was assumed constant throughout dissociation
process without considering the effect of hydrate decomposition on
the changes in porosity and permeability. Besides, from the para-
metric study, fluid flow was reported to have the smallest effect on
the overall decomposition and may be ignored when the porous
media permeability is higher than 1 mD. Under the situation where
rock permeability is extremely low, or the fluid flow region is very
long, there may be cases where fluid flow may be dominant in the
overall decomposition rate. Thus, new schemes which could couple
fluid flow with intrinsic kinetic rate or heat transfer are in need. In
addition, the kinetic rate constant used in the model was from Kim-
Bishnoi model which was constructed for pure methane hydrate.
There is a limitation to apply this rate constant in porous media, as
the kinetic rate constant is not only affected by the intrinsic rate,
but also by mass transfer to a large extent. The decomposition
surface area is also smaller as hydrate decomposition can only
occur at the sharp interface between hydrate and the movable
fluids in porous media rather than the whole region in pure hydrate
case. This could be further improved using the results of reaction
kinetic parameters of methane hydrate dissociation in porous
media published by Moridis et al. (2005b).
2.2.8. Hydrate dissociation kinetic modelling with CFD software
Given that the hydrate dissociation process is a heat and mass
transfer process in porous media with multi-phase flows and re-
action, computational fluid dynamics (CFD) technique could be an
excellent tool to investigate the problem. Nazridoust and Ahmadi
(2007) first attempted to use commercial CFD software FLUENT™
to simulate hydrate dissociation in a sandstone core. The axisym-
metric model consisted of three separate phases: methane hydrate,
methane gas and liquid water. The governing equations of the
model include continuity equations of mass for each species and
energy balance equations. Flow behaviour was described using
Darcy's law. Permeabilities of water and gas were evaluated by
Corey's formula. Besides, the hydrate intrinsic kinetic rate equation
was included by employing Kim-Bishnoi model (Kim et al., 1987)
and the kinetic parameter reported by Clarke and Bishnoi (2001a).
Volume of fluid (VOF) model was used for the simulation of water
and gas flows. To highlight, Users' Defined Subroutine (UDS) code
was written to account for source and sink terms, including the rate
of dissociation, amount of heat absorbed and the gas and water
generated. Besides, the UDS also included the effect of relative
permeability and effective porosity of the system. The 2-D simu-
lator was able to simulate hydrate dissociation against time, and the
production profile was compared with the experimental data from
Masuda et al. (1999), which shows good agreement. In addition, a
parametric study was also carried out with the model to describe
the relationship between dissociation rate and surrounding air
temperature, outlet pressure condition and permeability.
The significance of the work is that it utilized the existing
commercial CFD tool with developed code to study hydrate disso-
ciation. It has a potential to be further developed into a 3D model
for real reservoir condition. However, some limitation of the study
is that ideal gas model was used for the gas phase in the simulation,
which is not true for high pressure system, where methane hydrate
dissociates. This could be improved by employing more sophisti-
cated equation of state model, e.g. Peng-Robinson or Redlich-
Kwong model for model accuracy. Secondly, in the source and
sink terms, mass transfer effect, which is a multiphase diffusion
term, was not included. This could be improved by employing the
diffusion formulation presented in TOUGH þ HYDRATE (Moridis,
2014). Thirdly, for the computation of permeabilities of gas and
water, Corey's model (Corey, 1954) was employed and can be
improved by employing the modified Stone's equation (Stone,
1970) or Parker equation (Parker et al., 1987).
Another CFD modelling attempt on methane hydrate dissocia-
tion was carried out by Sean et al. (Sean et al., 2007a, 2007b). In
their study, both experimental and simulation work was employed
to study the process. Unlike the other kinetic models, the driving
force in the study was defined as the Gibbs free energy difference
between the hydrate phase and the ambient aqueous phase. The
dissociation rate constant was derived from the experimental re-
sults and it was found the rate constant was independent of pres-
sure and could be described by an Arrhenius-type equation with an
activation energy of 98.3 kJ/mol. The objective of CFD modelling in
this study was to investigate how the hydrate ball dissociation
behaves under flow condition. The simulation results verified that
the dissociation process occurred under an isothermal condition
and heat transfer was not the rate-determining step for the disso-
ciation. This in turn backs up the derivation of kinetic parameters
from the proposed hydrate dissociation rate equation. The rate
equations proposed were also extended to describe dissociation
process induced by different methods, namely depressurization,
increased temperature or simultaneous changes in temperature
and pressure (Sean et al., 2007b). It was shown that the driving
force used in the model is universal in different cases and the
prediction of dissociation rate agreed well with experimental data.
In summary, the study carried out by Sean et al. (2007a) investi-
gated the fundamental hydrate dissociation intrinsic kinetics and
the proposed model could be applied in further CFD simulation on
gas production.
2.2.9. Oyama-Narita dissociation kinetic model
Oyama et al. (2009) presented a theoretical model of methane
hydrate dissociation in sediments. The model took into account the
heat transfer effect and deviation from chemical equilibrium. The
key formulation of the model consists two parts: hydrate dissoci-
ation reaction and heat transfer effect. In the model, hydrate
dissociation process was divided into four different stages accord-
ing to the reference points on the hydrate equilibrium curve. The
schematic diagram of depressurization process is shown following
A/D trajectory in Fig. 5.
Hydrate dissociation was depicted as an equilibrium reaction
with three key assumptions. To derive the overall dissociation rate
constant, the dissociation process was assumed to be a first order
reaction of methane hydrate. Secondly, the forward and backward
reaction rate constant was derived to give the overall reaction rate
constant. Thirdly, the relationship between the forward and back-
ward reaction rate constant was established at equilibrium point
condition. Thus through assumptions and simplification, the overall
 Z. Yin et al. / Journal of Natural Gas Science and Engineering 35 (2016) 1362e1387
Fig. 5. Schematic diagram of the depressurization process on P-T diagram. Reproduced
from Oyama et al. (2009).
reaction rate constant considering only reaction was expressed as
follows:
kf
MH ! CH4 þ hW H2 O
kb
(  hW þ1 )
z T P
koverall ¼ kf 1
B B C
zC TC PB
where kf is the forward reaction rate constant, T and P refers to
temperature and pressure, z is the compressibility factor of
methane gas, hw is the hydration number of methane hydrate,
subscripts B and C refer to the condition at P-T schematic in Fig. 5.
To consider the heat transfer effect, a simplified energy balance
equation was used with the key assumption that heat transfer from
ambient environment caused methane hydrate to dissociate in pore
spaces. In addition, the relationship between time-dependent pa-
rameters was assumed to be weak. This led to a linear approxi-
mation coefficient of kf.
Qaround
kf  4
DH ðTC Þ½MHC0
where Qaround is the total heat input, 4 is the percentage of
contribution to the dissociation of Qaround, DH (TC) is the latent heat
of hydrate dissociation, [MH]C0 is the initial methane hydrate con-
centration at production pressure. Combining the above 2 equa-
tions, the overall dissociation rate constant was described with the
following correlation:
( rate of breakup. The diffusion process also shown an Arrhenius
 hW þ1 )
Qaround zB TB PC
koverall  4  1

DH ðTC Þ½MHC0 zC TC PB
To validate the model, the overall reaction rate constant was
plotted with selected 4 with experimental results scattered against
different production pressure. It was found that the 4 value of 0.35
results in the best fit to experimental results, which indicated that
~35% of the heat input from surrounding area was consumed to
dissociate the core sediments. It strengthened the statement that
during hydrate dissociation in porous media, heat transfer from
surrounding is the dominant factor, which is also reported later by
Oyama et al. (2012) and Zhao et al. (2015).
The model developed by Oyama-Narita is a simplified model
1373
with only one fitted parameter required to fit for overall reaction
rate constant. However, one limitation of the model is that there
was no consideration of the flow behaviour. In porous media, it is
expected that as the flow path is long, the porosity and the
permeability of the porous media has significant effect on the flow
behaviour, which could in turn limits the mass transfer rate (Hong
et al., 2003; Moridis et al., 2005b). Thus, omitting this factor could
result in overestimation of the overall reaction rate constant. Be-
sides, in the model formulation, only simple mass balance and heat
balance equations were employed with the time-dependent vari-
able being neglected. Thus, it is only possible to evaluate the overall
dissociation process with less information provided on time-
dependent variables, e.g. temperature profile, gas production pro-
file, dissociation interface movement profile. To improve, a full form
of mass and energy conservation equations needs to be included.
2.3. MD simulation on gas hydrate dissociation
Molecular dynamic (MD) simulation is another useful tool to
investigate clathrate hydrate microscopic structures and dynamics
within fine time resolutions (Barnes and Sum, 2013; English and
MacElroy, 2015). The MD simulation results can provide molecu-
lar insights on gas hydrates, such as hydrate structures (Alavi et al.,
2005, 2007), thermodynamic properties (Rosenbaum et al., 2007),
equilibrium properties (Jacobson and Molinero, 2010), hydrate
nucleation (Jacobson et al., 2010; Nguyen et al., 2012; Sarupria and
Debenedetti, 2012), crystal growth (Jacobson et al., 2010; Vatamanu
and Kusalik, 2006; Walsh et al., 2009b), inhibition of formation
(19) (Anderson et al., 2005) and decomposition (Alavi and Ripmeester,
2010; Bagherzadeh et al., 2013; Sarupria and Debenedetti, 2011).
Besides, MD simulation has the capability to depict phenomena
occurring at the nanometre and nanosecond scales, which is chal-
lenging to obtain from the current experimental approaches.
However, it should be noted that MD simulations in general are
carried out at extremely high driving forces with regards to over
pressure and over temperature in the interests of computational
times and experimental validation/verification of the findings
arising from MD simulations is needed.
Dissociation mechanisms of gas hydrates have been extensively
studied with MD simulations. These studies provide much insight
into the dissociate of hydrates, such as the sequential dissociation
mechanisms, the effect of guest molecule occupancies on the
dissociation rate, heat transfer during the dissociation and the
(20)
activation energy of cage breaking. English and MacElroy (2004)
first employed non-equilibrium MD simulation to investigate
methane hydrate crystallization under external electromagnetic
fields; English and Phelan (2009) performed non-equilibrium MD
simulation to investigate the thermal-driven breakup of both
spherical methane hydrate nanocrystallines and planar hydrate
interface. It was found that the diffusion of methane into the sur-
round aqueous phase was the limiting step controlling the overall
temperature dependence with activation energies varied for
(21) different hydrate crystal shape. Ding et al. (2007) employed NPT
method to simulate the microscopic dissociation process on type I
methane hydrate under isothermal and isobaric conditions. The MD
simulation results revealed that the dissociation process happened
at 2 stages at the molecular level: diffusive behaviour of host
molecule that led to the fracture of the lattice structure; followed
by the escape of methane molecule from the cavities and aggregate.
This mechanism was in accordance with the two-step dissociation
mechanism proposed by Kim et al. (1987). Sarupria and
Debenedetti (2011) investigated the dissociation behaviour of CO2
hydrates from isothermal-isobaric (NPT) MD simulation. From the
results on CO2 release rate and the velocity of the hydrate-water
1374 Z. Yin et al. / Journal of Natural Gas Science and Engineering 35 (2016) 1362e1387
interface, the effect of cage occupancy on the rate of hydrate
dissociation was determined. It was concluded that hydrate disso-
ciation rate not only depended on the overall, but also on the case-
specific occupancy. Another significant series of MD simulation
work to investigate hydrate dissociation is from Ripmeester's
group. Alavi and Ripmeester (2010) first applied non-equilibrium,
constant energy, constant volume (NVE) MD simulation to eluci-
date the hydrate dissociation process in molecular level. It was
observed that rows of clathrate decomposed in steps and simul-
taneous release of methane gas could form methane micro-bubbles
in the water phase. Temperature gradient up to 20 K was also
observed across the solid and solution phase. Bagherzadeh et al.
(2012b) reiterated the two limitations of macroscopic-level
intrinsic kinetic reaction model for hydrate dissociation: non-
isothermal condition between phases and apparatus specific ki-
netic parameters. Constant volume (NVE) MD simulation was
employed under non-equilibrium conditions to quantify the pre-
dicted rate of methane hydrate decomposition during different
stages. Bagherzadeh et al. (2012a) applied the same technique to
simulate methane hydrate dissociation in contact with silica sur-
face. Different hydrate dissociation zones were identified and the
dissociation rate in contact with silica surface was found to be faster
than water-methane hydrate system.
Bagherzadeh et al. (2013) reported by tracing the evolution of
methane during hydrate dissociation that methane molecules
aggregated and formed spherical regions of high concentration of
methane, which was identified to be nano-bubbles in the liquid
phase. Yagasaki et al. (2014) also investigated on the effect of
bubble formation during methane hydrate dissociation process
with MD simulation with a large system size. The simulation results
revealed that as hydrate dissociation proceeded, the dissociation
rate slowed down due to an increase in methane concentration in
the liquid phase. Recently, MD simulation was employed by
Bagherzadeh et al. (2015) to further investigate the conditions for
methane nano-bubble formation during dissociation and the effect
of nano-bubbles on gas hydrate dissociation rate. Recently, an
experimental work carried out by Veluswamy et al. (2016) on
mixed methane/THF hydrates reported the aggregation and for-
mation of a large number of spherical shapped bubbles that were
stable in aqueous liquid phase for a longer duration of time after the
dissociation of hydrates.
2.4. Discussion
The presented analysis of the literature on hydrate dissociation
kinetic models demonstrates that knowledge in this particular area
has evolved from understanding one single dissociation mecha-
nism to multiple mechanisms and their coupling effects, e.g.
intrinsic kinetic rate, heat transfer effect, water and gas flow
behaviour. In terms of the solution method, with the aid of scien-
tific computing, analytical solution of the problem is not necessary.
Instead, numerical solution of the model is often obtained at much
faster speed and higher accuracy; and the application of numerical
simulator to predict field scale production behaviour will be
covered in the next section. Besides constructing the numerical
codes to solve the large sets of partial differential equations, com-
mercial computational fluid dynamics software tool has also been
employed to simulate the process with good accuracy.
Given the increasing capacity in solving differential equations
describing the system, the question for a reliable and accurate hy-
drate dissociation kinetic modelling lies back to how accurate the
physical models and equations that we employ could capture the
process. Besides, how to make critical assumptions to avoid over-
simplification of the process is of great importance. Through
examining the literature, there are several technical perspectives
we have identified that is worthwhile to highlight for future hy-
drate dissociation kinetic modelling study.
Firstly, the intrinsic kinetics of hydrate dissociation is yet to be
elucidated, especially in porous media system. Kim-Bishnoi model
(Kim et al., 1987) and the kinetic parameters tested by Clarke et al.
(Clarke and Bishnoi, 2000a, 2000b, 2001a, 2001b, 2004, 2005) still
remained as the fundamental building block for most of the kinetic
models up till now. However, the applicability of these parameters
to describe hydrate dissociation in porous media still remains
questionable. It is imperative to gain a comprehensive under-
standing on how the intrinsic kinetic rate is affected by the porous
media and to what extent. Besides, to unify the driving force from
concentration gradient to chemical potential gradient is of great
interest as well.
Secondly, to describe the gas and water flow behaviour in hy-
drate dissociation, Darcy's Law is applied to all existing models
rather than solving the full form of Navier-Stokes equation. This is
generally true, however, to note, the assumption behind is that the
porous media is homogeneous, isotropic and the flow behaviour is
slow and viscous. With this assumption, it limits our modelling
effort in considering how the size of the porous media particle and
the deformation of porous media could impact the fluid flow
behaviour, which is one of the key driving mechanisms for hydrate
dissociation.
Thirdly, hydrate dissociation behaviour is yet to be thoroughly
explained from microscopic level. In Kim-Bishnoi model, dissocia-
tion was proposed to be a two-step process: destruction of lattice
followed by release of gas. However, recent theoretical studies
carried out by Windmeier and Oellrich (2013a, 2013b) proposed the
opposite order. With the dissociation rate now derived from the
fundamental molecular-level thermodynamic theories, it would be
even more meaningful to see the bridging of the microscopic model
prediction to macroscopic-level modelling.
Fourthly, the current literature review only covers hydrate
dissociation kinetic models developed in core and porous media
condition for energy production. Hydrate plug dissociation rate in
pipeline is of great interest to investigate in the context of flow
assurance (Davies et al., 2006; Kelkar et al., 1998; Sloan et al., 2010).
Thus, to integrate the currently available hydrate dissociation
intrinsic kinetics with consideration on heat and mass transfer
inside pipeline would be another advancement for gas hydrate
research relevant to the industry.
From MD simulation point of view, it can be expected that with
the advancements of computational modelling, more molecular-
level details on hydrate dissociation process will be revealed;
which will in turn assist in the validation of key assumptions made
and identify the necessary information required in macroscopic-
level modelling. In addition, from bridging the modelling effort
from both microscopic and macroscopic level, a more accurate and
close-to-reality mesoscale modelling approach can be developed.
3. Reservoir simulators for NGH bearing sediments
Although a large variety of theoretical models have been
developed, they are specific to the apparatus and procedures
applied in each study and have limited applicability to reservoir-
level studies (Kim et al., 1987; Selim and Sloan, 1985). Reservoir
simulators are computational tools applied to simulate the pro-
duction behaviour from a hydrocarbon field over an extended time
scale (NRC, 2009). Given the overwhelming abundance of methane
sequestered in NGH deposits, it is essential to evaluate potential
reservoirs and devise production strategies suitable for each case.
Resource potential evaluation is a staged process involving data/
parameter acquisition, numerical simulation and data post-
processing (Moridis et al., 2011a). The first stage of the evaluation
 Z. Yin et al. / Journal of Natural Gas Science and Engineering 35 (2016) 1362e1387
employs advanced geological and geophysical tools to characterize
the reservoir (e.g. the type and concentration of hydrate accumu-
lation, hydraulic properties, local temperature etc.). With the ac-
quired data, reservoir simulators provide an estimate of the gas
production scenario from the field under different well configura-
tion and production strategies before executing full-scale produc-
tion. Therefore, a key to realize energy recovery from NGH is to
accurately simulate the production behaviour, thereby assessing
the potential recovery and economics of the exploitation plan
(Boswell et al., 2013; Kurihara et al., 2010; Moridis et al., 2009a).
Various NGH reservoir simulators have been developed over the
years by different research groups, some of which are summarized
in Table 3. These simulators are capable of depicting the complex
interplay of highly coupled transport equations, the reaction ki-
netics, phase transition that occurs frequently within the systems,
and the physical and chemical properties of the hydrate bearing
media (which is dependent on the hydrate saturation and
morphology). After a conceptual model was consolidated, different
simulators may apply individual mathematical algorithms to
compute the production behaviour for a particular production case.
Depending on the assumptions and algorithms to solve the cases,
discrepancies may arise from different simulators for the same
problem (Collett et al., 2015).
3.1. TOUGH family reservoir modelling
One of the most widely applied reservoir models for the eval-
uation of NGH production is TOUGH (‘Transport Of Unsaturated
Groundwater and Heat’) family simulation code. TOUGH codes
were developed in 1980s to simulate the coupled transport of
water, vapour, gas and heat within porous and fractured media.
Apart from simulating hydrate deposits, TOUGH codes have also
been used for a wide spectrum of applications, including nuclear
waste disposal, energy production from geothermal, oil and gas
reservoirs, geological carbon sequestration and other applications.
In this review, we first look into the evolution of TOUGH codes in
hydrate reservoir modelling, followed by their working principles
and the input requirements. Upon appreciating the principles of the
simulator, we proceed with the application of this code in pre-
dicting production profiles from different hydrate deposits around
the world.
3.1.1. Evolution of TOUGH family hydrate reservoir simulators
The earlier version of TOUGH simulator for hydrate related
application was TOUGH2/EOSHYDR. EOSHYDR was developed by
Moridis et al. (1998) as a module for TOUGH2 general purpose
simulator to depict non-isothermal gas release, phase transition as
well as fluid flow during methane hydrate dissociation under
Table 3
List of relatively matured codes for hydrate reservoir simulation.
Simulator Developers
TOUGH Family Codes LBNL, NETL
HydrateResSim Freeware, an earlier version of TOUGH þ Hydrate
TOUGH2/EOSHYDR2 Earlier code with different code architecture
TOUGH-Fx/HYDRATE Transition period code
Serial TOUGHþ/ First publicly available reservoir model
HYDRATE
Parallel TOUGHþ/
HYDRATE
MH-21 HYDRES National Institute of Advanced Industrial Science and Technology; Japan Oil Engineering Co., Ltd (Kurihara et al., 2011a)
& University of Tokyo
STOMP-HYD The Pacific Northwest National Laboratory
CMG-STARS Computer Modelling Group
1375
equilibrium conditions (Pruess et al., 1999). The EOSHYDR module
was enhanced into EOSHYDR2 module (Moridis, 2003) capable of
simulating formation and dissociation of binary hydrates under
both kinetic and equilibrium conditions. The enhanced features
allowed TOUGH2/EOSHYDR to predict gas production from hy-
drates under different geologic conditions around the world
(Moridis and Collett, 2004, 2002, 2003; Moridis et al., 2004).
In 2005, TOUGH2/EOSHYDR2 code was reengineered into a
transitional code TOUGH-Fx/HYDRATE, whereby the computa-
tional architecture was changed drastically (Moridis et al., 2005a).
Written in FORTRAN 95/2003 language, the new simulation
framework adhered to the tenets of object-oriented programming
(OOP) and incorporated modular structure to describe each objects.
Modular structure of the new TOUGH-Fx enhanced data trace-
ability and provided channels for data expansion, allowing it to be
applied to simulate production from different classes of hydrate
reservoirs (Moridis and Kowalsky, 2006; Ruan et al., 2012) as well
as to acquire the thermal properties and intrinsic rate constants
from laboratory scale studies (Moridis et al., 2005b; Tang et al.,
2007). The modular framework of the transitional TOUGH-Fx
code was inherited in TOUGH þ HYDRATE (abbreviated as T þ H
hereafter), which was first released in 2008 (v1.0) and updated in
2012 (v1.2) (Moridis, 2014; Moridis et al., 2008). To reduce the
execution times and facilitate the convergence of simulator, T þ H
made the following simplification from its predecessor TOUGH2/
EOSHYDR2:
(1) Removed gas tracking options which separates free gas and
gas from dissociation; and
(2) Eliminated binary hydrates simulation as the phase equi-
librium is complicated by concentrations of different guest
species.
To date, TOUGH þ HYDRATE has been adapted by 8 interna-
tional oil & gas companies and more than 40 research organizations
across 18 countries.
3.1.2. Assumptions and the underlying principles of T þ H
T þ H code is capable of describing the flow of gas and liquids in
the geological formation, occurrence of phase changes, heat ex-
change via conduction, advection and radiation, enthalpy changes
during phase transition, kinetics of hydrate related reactions (under
kinetic models), and the effects of inhibitors on hydrate bearing
sediments under any method of hydrate dissociation (including
depressurization, thermal stimulation and chemical injection). To
simplify the large pools of models, the following assumptions/re-
strictions were made:
Refs.
(Moridis et al., 1998)
(Moridis et al., 2005a)
(Moridis, 2014; Moridis et al., 2008)
(Zhang and Moridis, 2008)
(Phale et al., 2006; White, 2012; White and
Oostrom, 2006)
1376 Z. Yin et al. / Journal of Natural Gas Science and Engineering 35 (2016) 1362e1387
1. The simulation conditions are within Darcy's law's validity;
2. The dissolved gas and inhibitors are transported via convection;
3. The compressibility and thermal expansivity of hydrates are
identical to that of ice;
4. Dissolved salts do not precipitate during water freezing;
5. The dissolved inhibitor does not affect the thermophysical
properties of aqueous phase;
6. Non-volatility of inhibitor; and
7. The maximum pressure modelled is 100 MPa.
After these simplifications, appropriate models to describe the
thermophysical properties and flow properties were selected, and
the reservoir model was constructed based on the general conser-
vation equation. To simplify the large quantity of governing equa-
tions employed in the program, we presented a selection of the
fundamental equations in Fig. 6, with their nomenclature as listed
in Nomenclature section. Accordingly, the system is modelled into
four mass components, namely H2O, CH4, hydrate and water sol-
uble inhibitors (salts or alcohols) which are partitioned among 4
possible phases (liquid, gas, ice and hydrate phase). Note that the
simulator takes in heat as a component and applied the same
framework to simultaneously solve for the general conservation
equation. The general conservation equation comprises of three
terms: accumulation terms, flux term and the source/sink term.
In T þ H, MH formation and dissociation can be simulated in
equilibrium or kinetic models (Kowalsky and Moridis, 2006), with
kinetic model requiring an additional component. The difference
between equilibrium and kinetic reaction model lies on the
approach to handle hydrate dissociation reaction. For the mass
accumulation term in equilibrium model, hydrate phase is made up
from water and methane (k ¼ w, m) according to their mass
fraction:
Wm m
b ¼ H; XHw ¼ ; X ¼ 1
XHw ; XHi ¼ 0
Wh H
whereas for kinetic model, hydrate phase does not contain w and m,
and the mass accumulation term for hydrate phase is directly
Fig. 6. Summary of conservation equations for equilibrium and kinetic models applied in T þ H.
computed from Kim-Bishnoi model (Kim et al., 1987):
   
vM h DEa
Qh ¼ ¼
K0 exp FA A feq
fv
vt RT
Another difference between equilibrium and kinetic model lies in
the term which takes into account the heat of hydrate dissociation:
In equilibrium model, the reaction heat was accounted for in the
heat accumulation term according to the changes in hydrate phase
quantity, D(fSHrHDH0); whereas in kinetic model, the dissociation
heat was considered in the source/sink term, which is dependent
on the hydrate formation/dissociation rates predicted from Kim-
Bishnoi model: QHDH0. On the other hand, the computation
models for heat and mass flux terms are the same between kinetic
and equilibrium model. In general, it is found that for large-scale
system, the use of equilibrium and kinetic reaction model does
not make significant difference; whereas for modelling of short-
termed process or small scale simulation, kinetic limitations can
be dominant and should not be neglected.
The thermophysical properties of each component, including
the enthalpies, densities, thermal expansivity, fugacity etc. and flow
properties (e.g. permeability, porosity changes) are coded in
different code segments using appropriate database or correlations
(Dickens and Quinby-Hunt, 1997; Huppert, 1992; Kamath, 1984;
Marion and Jakubowski, 2004; Pape et al., 1999; Peng and Rob-
inson, 1976; Ruan et al., 2012; Scheidegger, 1958; Verma and Pruess,
1988; Xu et al., 2004). As discontinuity exists for certain properties
(e.g. quadruple points), data smoothing around the small region of
discontinuity is applied (Moridis, 2003).
T þ H is also capable of assessing the geomechanical phenom-
enon encountered during production from NGH sediment through
its coupling with FLAC3D through a central coupled thermal-
hydrological-mechanical (THM) model (Holditch, 2006; Kim
et al., 2011; Rutqvist and Moridis, 2007, 2008; Rutqvist et al.,
2012). As illustrated in Fig. 7 (Rutqvist and Moridis, 2007), FLAC3D
transmits mechanical properties (e.g. effective stress and strain) to
T þ H for an updated porosity, pore pressure and its effect on fluid
flow; and T þ H supplies the updated data from heat, mass and
 Z. Yin et al. / Journal of Natural Gas Science and Engineering 35 (2016) 1362e1387
momentum equations (including temperature, pressure and phase
saturation) to FLAC3D to estimate their impact on the effective
stress, thermal and swelling strain, and other changes in mechan-
ical properties.
3.1.3. Implementation of T þ H: input and output
Upon appreciating the basic theories behind T þ H, we proceed
with the computational algorithm of the simulator. In T þ H, the
reservoir space (V) is discretized into small volumes (Vn) employing
integral finite difference (IFD) method, whereas time is discretized
by first-order finite difference method, tkþ1¼tkþDt (Narasimhan
and Witherspoon, 1976). The discretization steps convert the gen-
eral conservation equation into sets of non-linear algebraic func-
tions with a residual term:
! at a specific time etc. can also be acquired from the simulator as
k;kþ1 k;kþ1 k;k Dt X k;kþ1 k;kþ1
Rn ¼ Mn
Mn
Anm Fnm þ Vn qn
Vn m
Note that each element volume (Vn) consists of Nk equations.
Therefore, if a reservoir is divided into NE gridblocks, there is a total
of Nk  NE coupled non-linear equation for each time step. Taking
the case demonstrated in Fig. 8 as an example, the hydrate bearing
layer (HBL) were discretized into 8280 active gridblocks under
equilibrium mode (Nk ¼ 3), resulting in a total equation of 24,840
for each time step (Rutqvist and Moridis, 2007). The residuals were
iteratively solved by the in-built mathematical solver in T þ H till it
was below the preset convergence threshold of 10
5 according to
the default setting. An implication of space discretization is that
each Vn has no reference to the global system. Therefore, the ac-
curacy of solution is highly dependent on the accuracy of interface
properties.
To execute the simulator, 14 code segments for different func-
tions (e.g. codes for water properties, medium properties etc.) are
compiled in a fixed sequence. The input of data into T þ H solver is a
keyword based procedure, and the essential input data blocks of
T þ H are summarized in Table 4. In addition to those listed in
Table 4, a multitude of optional data blocks are also available to
specify or select models for various properties (e.g. relative
permeability, diffusivity of components and initial conditions for
domains). Interested readers are prompted to refer to the user
manual for more detailed description (Moridis et al., 2008).
As discussed so far, it is clear that T þ H requires the compu-
tation of thermophysical properties for individual grid blocks,
assembling residual vectors and solving the equation systems for
each Newton-Raphson iteration step. Therefore, it can be expected
that for a large problems with more than thousands of grids, the
computational load will be huge, leading to undesirably long
execution time. As such, the simulator offered different methods to
Fig. 7. Direct and indirect coupling of T þ H with FLAC3D to depict changes in geomechanical behaviour. Reprinted with permission from Rutqvist et al. (2012).
1377
solve the linear equation systems, including direct method which is
the most reliable approach but requires longer execution time and
iterative method which is suitable for larger problem size. Upon
successful simulation, the standard output data from the simulator
includes:
1. The distribution of pressure, temperature, phase saturation and
equilibrium conditions;
2. Production rates and compositions at wells;
3. Volume and mass balances of phases and components;
4. Time dependent variation of important variables for specified
elements, connections and source/sink.
Other output information, such as the mass fractions of com-
ponents in different phases, fluxes across gridblock, reservoir data
prompted.
3.1.4. Applications
A major application of numerical simulation is to select suitable
reservoir and devise optimal production strategy for different hy-
drate reservoirs. To evaluate the production potential and aid in the
selection of potential reservoir, it is necessary to categorize the
huge variety of reservoirs around the world. In numerical simula-
tion studies, the hydrate accumulation is typically categorized into
four classes (Class 1 to Class 4) according to the overlying and un-
derlying strata around the sediment and their hydrate saturation
(Moridis and Collett, 2003; Moridis et al., 2004, 2009a). In this
section, the application of T þ H in simulating reservoir production
behaviour for each class is reviewed according to their classes. Due
to the low possibility of production from Class 4 sediments, which
comprise the range of dispersed, low saturation marine hydrate
deposits without bounding formations (Moridis et al., 2009a), they
are not included in the discussions in this section.
3.1.4.1. Class 1 accumulation. Class 1 hydrate accumulation com-
prises a hydrate-bearing layer (HBL) and an underlying two-phase
fluid zone with mobile gas. Typically, the base of hydrate stability
zone (BHSZ) coincides with the bottom of the hydrate interval,
making Class 1 hydrate an attractive reservoir as it is in proximity
with hydrate equilibrium (Moridis and Collett, 2004). Fig. 8 shows
an example of the simulation of Class 1G accumulation (Hydrate
saturation, SH ¼ 0.7; Gas saturation, SG ¼ 0.3) using reservoir
properties retrieved from Mallik site (Moridis and Collett, 2004;
Moridis and Kowalsky, 2006; Rutqvist and Moridis, 2007). The
30 m thickness active region containing HBL and mobile fluid zone
was discretized into 8280 uneven gridblocks (Rutqvist and Moridis,
2007). Production was induced mainly by depressurization and a
1378 Z. Yin et al. / Journal of Natural Gas Science and Engineering 35 (2016) 1362e1387

Fig. 8. Simulation production profile for Class 1 hydrate deposit with properties retrieved from Mallik Site, Canada. Compiled from simulation results from Moridis et al. (2007).

Table 4
List of the essential keywords identified by T þ H and their functions.

Keyword Data carried

Title Simulation title

Memory Dynamic memory allocation block, where users select equilibrium or kinetic model to be applied and define various basic information (e.g. the number of
components, phases, equations, elements, connections, source and sinks). Number of reservoir media are also defined in this data block. The information
supplied in MEMORY should be consistent with the subsequent input files.
Hydrate To specify hydrate properties and behaviour (e.g. guest type, hydration number, correlations for estimation of thermal conductivity, density and specific heat,
and the effect of inhibitor)
Rocks To depict medium properties, including the rock type, grain density, porosity, absolute permeability, heat conductivity, specific heat, grain radius, tortuosity
factor, pore compressibility and expansivity)
Eleme To specify the location for the centroids ofeach volume elements (grids), their volume and interface area
Conne To define the flow connections between individual grids, distance between common interface of the two elements.
Param To describe the computational parameters (e.g. time steps, maximum number of iterations, convergence criteria)
Endcy To end the simulation

wellbore heating of 200 W/m was supplied to prevent hydrate
formation around the well. The gas release profile indicated that
hydrate dissociation rate exhibited an increasing trend across the
production duration of 30 years; and the rate-replenishing-ratio
(RRR), which quantifies the fraction of gas production rate due to
hydrate dissociation, increased to an impressive 75% at the end of
the simulation. On the other hand, the occurrence of steep drops in
the gas release rate and RRR at different instances is an effect of
discretization when dissociation is complete for a particular layer
(endothermic nature of hydrate dissociation and Joule-Thompson
effect when gas is removed from the layer). The water produced
from this deposit was an order of magnitude lower as compared to
Class 1W deposit (Hydrate saturation, SH ¼ 0.7; Water saturation,
SA ¼ 0.3 in the HBL), which makes this class of accumulation
attractive for production. The evolution of spatial distribution of
hydrate distribution (Fig. 8(C)) further support the continuous gas
release profile, as continuous destruction of hydrate was found to
occur in the simulated environment. The hydrate saturation profile
clearly demonstrated the development of horizontal hydrate
dissociation front. Note that the simulation predicted secondary
hydrate formation in the later years at location further from the
well, as shown in the bands of high SH.
Although Class 1 accumulation is generally the most desirable
class for exploitation due to its proximity to the hydrate
equilibrium (i.e. small changes in pressure and temperature can
induce dissociation), care has to be taken to prevent the tempera-
ture of HBS from falling drastically, inducing the formation of hy-
drate or ice that would adversely impedes the permeability of the
sediment and subsequently, the gas production (Moridis and
Collett, 2004).
3.1.4.2. Class 2 accumulation. Class 2 hydrate reservoir comprises a
HBL and an underlying free water zone (without free gas), which is
the most common class in nature (Moridis et al., 2009b). Unlike
Class 1 accumulation, the bottom of HBL does not mark the BHSZ.
For Class 2 hydrates, production through depressurization is typi-
cally achieved by removing underlying free water, which may cause
the dissociated gas to accumulate on the top of the HBS instead of
the production well. Therefore the simulation work also studied
alternative well configurations and their improvements from the
conventional well design.
The production behaviour from oceanic Class 2 deposits in
Shenhu Area was simulated through vertical well depressurization
(Su et al., 2012a) and huff and puff method (Su et al., 2012b) in
separate studies. This particular hydrate deposit has an overlying
and underlying mobile water zone, and was not bounded by
impermeable strata. As such, the average gas production and water
production rates were found to be 211 ST m3/d and 52 m3/
 Z. Yin et al. / Journal of Natural Gas Science and Engineering 35 (2016) 1362e1387
d respectively for the case of depressurization, which were deemed
insufficient for industrial exploration (Su et al., 2012a). Simulation
results from huff-and-puff method revealed that the amount of
methane released via hydrate dissociation was less than that con-
verted into secondary hydrates due to the elevated pressure during
the process, rendering it not feasible for gas production as well (Su
et al., 2012b). Despite that the simulation study concluded a low
production potential for this reservoir, it was reported that the
production rate can be significantly enhanced by increasing reser-
voir permeability and imposing impermeable boundaries through
sensitivity analysis.
Production from permafrost-associated (PA) Class 2 accumula-
tions was reported to be more challenging than the marine hy-
drates due to the absence of salt and lower temperature conditions
which reduce sensible heat available to fuel hydrate dissociation
(Moridis and Reagan, 2011a, 2011b). In a simulation study
employing conventional vertical well design, the occurrence of
cavitation (characterized by rapid pressure drop within the well)
was observed due to secondary hydrate formation that blocked the
flow path which resulted in the inability of the reservoir to match
the withdrawal rate. Therefore, cyclic production with a period of
reduced withdrawal rate is advised for the operation of such de-
posit (Moridis and Reagan, 2011a). In a follow up study, alternative
well configurations (e.g. a longer production intervals extended
into the HBL & wellbore heating) were simulated, which reported a
higher production rate than the conventional design (Moridis and
Reagan, 2011b). The heated wellbore configuration is recom-
mended as a feasible production strategy from PA-Class 2 deposit as
it prevented secondary hydrate barriers around the well (Moridis
and Reagan, 2011b).
Recently, the first field-scale simulation from a deep ocean hy-
drate reservoir (38 km2 extent) comprised of up to 2.5 M grids was
conducted with the parallel version of T þ H code under a collab-
oration with Statoil (Reagan et al., 2013, 2014). Different sets of well
configurations, including vertical and horizontal well perforated at
different intervals have been simulated to compare the production
profile under a constant pressure of 3 MPa up to 3 years. The
simulated results highlighted the inherent challenges for NGH re-
covery, including the difficulty in depressurization (which caused
poor rates of hydrate dissociation) and undesirable water produc-
tion issues. This large scale simulation also emphasized on the
importance of several properties to the numerical simulator,
including boundary permeability, adjacent layers to the HBL and
local temperature, which should be carefully considered during
reservoir evaluation.
3.1.4.3. Class 3 accumulation. Class 3 accumulation describes the
type of HBL without any underlying mobile fluid zones. Prudhoe
Bay Unit C and D hydrate deposits are examples of this kind, with
impermeable boundaries sandwiching the HBL (Kim et al., 2012;
Moridis et al., 2011c). Fig. 9 shows a compilation of the produc-
tion profiles and sensitivity analysis for temperature and SH simu-
lated for Unit D. By comparing the gas release and production
profiles employing vertical and horizontal well configuration,
horizontal well was found to enhanced gas production by 2 orders
of magnitude. Although water production for horizontal well was
higher than a vertical well, it was confined within a narrow,
manageable range (between 0.9 and 1.3 kg/s). As horizontal well
yielded a better performance over the vertical well, sensitivity
analysis was conducted based on the horizontal well configuration.
It was demonstrated that the gas production can be increased by 8-
fold with 1 K increase in reservoir temperature, and a lower hydrate
saturation of 0.35 is more favourable for gas production, since it
enhanced keff (Moridis et al., 2011c). On the other hand, the simu-
lation for Unit C included geomechanical analysis, which enabled a
1379
more holistic depiction of the production scenario. The study
demonstrated the difference between one-way and two-way
coupling with FLAC3D, highlighting the necessity of employing
two-way coupling to accurately depict the production profile (Kim
et al., 2012). Geological stability analysis revealed that the
maximum strain simulated was 2% (<5% threshold), justifying
wellbore stability under this case (Kim et al., 2012).
Simulation of oceanic Class 3 hydrate deposit was conducted for
SH7 in Shenhu Area (Li et al., 2011) and Tigershark area (Moridis
and Reagan, 2007). For Shenhu Class 3 deposits, production via
single horizontal well through huff and puff method was simulated.
Although the production was unsatisfactory due to the absence of
impermeable bounding layers, the study demonstrated the
diminishing and enlargement of hydrate dissociation front during
the huff and puff cycle due to secondary hydrate formation. For
Tigershark deposit, geomechanical analysis during production
revealed that depressurization would result in a vertical subsidence
depending on the magnitude of depressurization as well as the
elastoplastic properties of the sediment (Rutqvist et al., 2012). Both
studies concluded that thermal stimulation has limited effect on
production profile as compared to depressurization, as heat trans-
fer is localized around wellbore whereas pressure reduction fronts
can spread to a larger extent (Li et al., 2011; Moridis et al., 2009a;
Moridis and Reagan, 2007).
The production behaviour from UBGH2-6, which was classified
as a hybrid of Class 2 and Class 3 reservoir had also been simulated
to investigate the feasibility of production from this marine hydrate
accumulation (Moridis et al., 2013). The reservoir has a layered
stratigraphy, with alternating hydrate-free mud and hydrate-rich
sand layers, which necessitates the use of vertical wellbore. The
simulation indicated that although gas production was technically
feasible, the gas production rate was modest (< 1.45 ST m3/s). In
addition, it was also reported that the effect of porosity and initial
hydrate saturation on cumulative production was not monotonic
(i.e. better production performance at a lower initial hydrate
saturation). Through coupling with FLAC3D, the preliminary geo-
mechanical analysis indicated a significant subsidence along a large
part of the wellbore due to a large portion of muds around the
reservoir.
3.1.4.4. Other applications of T þ H. Apart from simulating hydrate
reservoirs, T þ H had also been applied to simulate the production
behaviour in laboratory scale (Birkedal et al., 2014; Kneafsey and
Moridis, 2014). As laboratory scale production is conducted under
a more controlled manner, the matching of simulation results and
experimental results enables the validation of various parameters
and identify possible phenomenon which could affect the model
accuracy. For example through the matching of T þ H results and
dissociation kinetics measured by MRI, it was demonstrated that
kinetic model dominates short term dissociation as non-
equilibrium exists in the system due to changes in contact area,
mineral actions and interaction between phases and the porous
media (Birkedal et al., 2014). The simulator had also been applied to
simulate the dissociation of shallow hydrate deposits at low-
saturation under possible scenarios of global warming (Reagan
et al., 2011).
In summary, T þ H has been applied as a tool to evaluate the
production potential from several hydrate deposits around the
world. These simulation studies aided in identifying the key char-
acteristics of potential reservoirs, including a coarse porous media
(high porosity and permeability), proximity to equilibrium (esp.
Class 1 hydrates), high reservoir temperature and pressure, pres-
ence of impermeable boundary around the sediment, and inter-
mediate hydrate saturation (around 0.5e0.6 range) (Moridis et al.,
2011b). Alternative well configurations have also been tested to
1380 Z. Yin et al. / Journal of Natural Gas Science and Engineering 35 (2016) 1362e1387
Fig. 9. Simulation results from T þ H for Class 3 hydrate deposit with properties retrieved from Mt. Elbert Gas Hydrate Stratigraphic Test Well, Alaska. Compiled with permission
from Moridis et al. (2011c).
devise possible way of recovering methane suitable for deposits of
different classes (Moridis et al., 2011b).
3.2. Other simulators
Apart from T þ H, a variety of other simulators capable of
simulating hydrate reservoir behaviour have also been developed.
The principles of these simulators are similar to those outlined in
the previous section and will not be reiterated. In this section, the
application of these simulators is discussed in brief.
3.2.1. MH-21 HYDRES
MH-21 Hydrate Reservoir Simulator (MH21-HYDRES) is another
widely applied and validated code for hydrate reservoir simulation
developed by Japanese research team. MH21-HYDRES can take in
five phases (gas, water, ice, salt and hydrate) and six components
(methane, nitrogen, CO2, water, methanol, salt) using appropriate
theories and models, whereby the detailed description is available
(Kurihara et al., 2011a, 2011b; Masuda et al., 2008). The simulator
had been applied to validate the reservoir properties obtained from
Mt. Elbert site via Modular Dynamic Tester (MDT) (Kurihara et al.,
2011c), to predict gas production from Mallik site (Yamamoto and
Dallimore, 2008b), Eastern Nankai Trough (Kurihara et al., 2009)
and in a huff-and-puff based gas production using methanol
(Masuda et al., 2008). According to MH21-HYDRES, the threshold
effective permeability required for an effective depressurization
was found to be 1e10 mD for a high SH Class 3 deposit (Konno et al.,
2010a). In a follow up study, the simulator was applied to match the
dissociation behaviour from a hydrate-bearing core retrieved from
Eastern Nankai Trough (Konno et al., 2010b). The study successfully
demonstrated that the permeability of the core (and extended to
the sediment) was above the threshold value, and hydrates were
formed in a pore-filling manner within the sediment. In a recent
study, the simulator was employed to study gas production below
quadruple point along with experimental evidence (Konno et al.,
2012). The study observed an enhanced gas production rate with
ice formation; and the sensitivity analysis revealed an improved gas
production rate at a higher rate of ice formation (Konno et al.,
2012). In summary, MH21-HYDRES identified similar characteris-
tics for favourable reservoir characteristics as T þ H: Class 1, high
temperature, and pore-filling hydrates which result in higher
permeability (Kurihara et al., 2011b).
3.2.2. STOMP-HYD
STOMP-HYD (Subsurface Transport Over Multiple Phases) is a
Fortran 90 based simulator developed by Pacific Northwest Na-
tional Laboratory under support from Korea-U.S. Gas Hydrate Joint
Program (White and Oostrom, 2006). On top of modelling hydrate
 Z. Yin et al. / Journal of Natural Gas Science and Engineering 35 (2016) 1362e1387
reservoir behaviour under thermal stimulation, depressurization
and inhibitor injection, STOMP-HYD is capable of depicting pro-
duction through CO2 exchange (White et al., 2011). The simulator
has evolved from the earlier version (STOMP-HYD) which consid-
ered equilibrium model into STOMP-HYDT-KE, which has the
capability to model CH4/CO2/N2 guest molecule exchange in a ki-
netic model through the incorporation of an innovative hybrid
tabular-cubic equation of state to resolve convergence issue for the
mixture equilibrium (White, 2012). STOMP-HYD has been
employed to study CO2 exchange approach in a Class 1 permafrost
deposit and demonstrated a reduced water production and limited
injectivity due to secondary hydrate formation (White and McGrail,
2009). STOMP-HYDT-KE was also employed to interpret Ignik
Sikumi field test and determined that the kinetics of gas exchange
in field test is of the order of 10 times slower than that in laboratory
scale which can be due to ice formation or other unknown mech-
anisms (Anderson et al., 2014; White and Suk Lee, 2014).
3.2.3. CMG-STARS
CMG-STARS (Computer Modelling Group's Steam, Thermal and
Advanced Process Reservoir Simulator) is a commercial oil reser-
voir simulator. Incorporated with robust reaction kinetics and
geomechanic tools, it is one of the most complete and flexible
reservoir simulators which can be applied for hydrate reservoir
simulation. CMG-STARS was applied as a preliminary simulator by
Statoil to investigate large scale oceanic hydrate deposit (Reagan
et al., 2014). In a long term production simulation study from Mt.
Elbert test well, heterogeneity in hydrate saturation was modelled
by CMG-STARS, which revealed the superior production perfor-
mance from a heterogeneous HBL as compared to homogeneous
HBL due to presence of high permeability channels (Anderson et al.,
2011). The simulator was also employed to perform an economic
analysis from permafrost hydrate deposit (Walsh et al., 2009a).
On top of the simulators in Table 3, other simulators have also
been applied in individual field trial (Myshakin et al., 2012). For
instance, an internally developed ‘Cell-to-Cell model’ was devel-
oped by Conocophilips for Ignik Sikumi field trial involving the
injection of N2/CO2 mixture into the hydrate bearing sediment in
Alaska North Slope (Schoderbek et al., 2013).
3.3. Validation of simulators
After reviewing the theories and application of reservoir simu-
lators to evaluate reservoir performance, it is clear that careful
validation is necessary to ensure the reliability and robustness of
the simulator. In this section, two approaches to verify reservoir
codes are reviewed.
3.3.1. History matching & calibration of simulator
Reservoir model can be validated through history matching
with the available field production data. As illustrated in Fig. 10,
history matching is an iterative process involving the adjustment of
parameters or assumptions such that the simulated results
matched reasonably with the observed data (Kurihara et al., 2011a).
Both T þ H and MH21-HYDRES have been calibrated with pro-
duction data obtained from Mallik 2002 field trial (Collett et al.,
2010), whereas the production profile from Mt. Elbert Modular
Dynamic Formation Test was matched with 5 simulators: CMG-
STARS, HydrateResSim, MH-21 HYDRES, STOMP-HYD and T þ H
(Anderson et al., 2008). On the other hand, Mallik 2007 & 2008
winter tests were matched with MH-21 (Kurihara et al., 2011a) and
CMG-STARS (Uddin et al., 2012; Wright et al., 2011). The production
profile was close to the simulated results from MH21 and CMG-
STARS simulator through appropriate adjustments of reservoir pa-
rameters, including the generation of high permeability conduits in
1381
the early stage and the collapse of such conduit at the latter stage of
the field test (Kurihara et al., 2011a). CMG-STARS simulation study
found conventional parametric adjustment unsatisfactory and
proposed a non-equilibrium gas exsolution model to depict gas
transport through the reservoir, which achieved good match with
the field data (Wright et al., 2011). The gas exsolution theory pro-
posed that continuous gas flow pathways from reservoir to well-
bore were formed by the coalescence of small bubbles (in pore
water) into larger bubbles, followed by the connection of larger
bubbles across the pore throats (Wright et al., 2011).
History matching also allows for the modification of underlying
assumptions. For instance, through history matching in Ignik
Sikumi Field trials (Fig. 11), the Cell-to-Cell model was found unable
to depict the initial rapid increase in methane concentration and
significantly underestimated the amount of water produced due to
potential free water production from the near-well region. Through
revisiting the initial assumptions, it was found that some of them
were not applicable to the system, including (1) insignificant heat
transfer from confining strata; (2) rapid reaction (i.e. equilibrium
model); (3) homogeneous composition throughout the production
zone; (4) negligible gravity effect during production; and (5) sta-
tionary solid phase (Schoderbek et al., 2013). Subsequently, step-
by-step model recombination was carried out taking into account
the effect of flow heterogeneity and solid hydrate production,
enabling the simulated results to match the measured field outputs.
Another way to match the simulation result is by comparing the
simulation results with laboratory tests conducted in a large scale
reactor (Feng et al., 2015; Li et al., 2012a, 2012b, 2014a, 2014b), or
from cores recovered from known reservoir. For instance, the
production profile from a 202.5 mm  88.9 mm hydrate core
recovered from Mt. Elbert site was dissociated in laboratory scale,
and the production profile was found to achieve a good match with
that predicted by T þ H (Kneafsey and Moridis, 2014). A matching as
such not only validated the model, but also affirmed the applica-
bility of various parameters obtained from field study.
3.3.2. Comparison of simulated results between different simulators
Code comparison is another way to validate the reservoir
simulation and build confidence to each simulator. Discrepancies in
modelling result also promote the exchange of information be-
tween different developers, which could aid in better elucidating
the complex phenomena during hydrate dissociation. Code com-
parison studies have been conducted to predict production
behaviour for seven problem cases (Anderson et al.; Gaddipati,
2008; Liu and Gamwo, 2009). Wilder et al. led the first interna-
tional, interagency effort in hydrate simulator code comparison
(Wilder et al., 2008). All the simulators employed (T þ H, CMG
STARS, HydrateResSim, MH-21 HYDRES, and STOMP-HYD) gener-
ated consistent results to depict the hydrate dissociation process. In
addition, all simulators in the study showed that gas and water
production rate increased in the presence of mobile water phase.
However, discrepancy in simulator prediction was found when ice
formation occurred.
Subsequently, these distinctive simulators were applied to
model the long term production profile from Mount Elbert well for
three cases (Anderson et al., 2011). As seen from Fig. 12(A), the code
comparison study began with a problem statement with the same
reservoir information and the grid design. Although the average
long term production rate predicted by different simulators for this
case shows some deviation, the predictions are of the same order of
magnitude, showing some extent of confidence towards the
applicability of the simulators. Some uncommon production
behaviour, such as lag time for gas production, has also been
consistently simulated by most of the simulators. A comparison
across different cases in this study also demonstrated consistent
1382 Z. Yin et al. / Journal of Natural Gas Science and Engineering 35 (2016) 1362e1387

Fig. 10. Workflow of reservoir model construction and history matching from Mallik 2007/2008 Test. Modified from Kurihara et al. (2011a).

Fig. 11. History matching during Ignik Sikumi Field Trial. Figures reproduced from Schoderbek et al. (2013).

Fig. 12. Specifications and results from code comparison study for Prudhoe Bay-like Class 3 reservoir. (A) The radially-symmetric reservoir grid design; and (B) 10-year and 50-year
average gas production rates. Compiled with permission from Anderson et al. (2011).
 Z. Yin et al. / Journal of Natural Gas Science and Engineering 35 (2016) 1362e1387 1383

conclusions attained from different simulators on the effect of effect of different driving mechanisms in depth and verify the as-
temperature, intrinsic permeability, and heterogeneity in hydrate sumptions made in the existing kinetic models. For experimental
saturation (Anderson et al., 2011). study, empirical correlations could be established and applied in
the future modelling work directly. There is no doubt that more
3.4. Future directions accurate, faster and robust simulators incorporating all hydrate
dissociation mechanisms will be developed for engineering and
Reservoir models have been applied to aid in the selection of industry application. There is a need to develop reliable and
productive reservoir, identification of favourable characteristics of detailed reservoir models in conjunction with the development of
reservoir, and development of production strategies for short term representative dissociation models that mimic natural sediments of
NGH production tests (Beaudoin et al., 2014). Through reservoir hydrates dissociate in nature. This will lead to the eventual
modelling, some features of potential hydrate reservoirs for gas exploitation and production of natural gas from natural gas
production has been identified: including (1) sandy reservoir of hydrates.
high porosity and permeability; (2) intermediate SH; (3) high
reservoir temperature and proximity to the BHSZ; and (4) an un-
Acknowledgement
derlying free gas layer (Class 1 reservoir) (Collett et al., 2010).
Reviewing various work done in the last decade, significant
The financial support from the National University of Singapore
improvement is seen in reservoir modelling e from equilibrium
(R-261-508-001-646 and R-261-508-001-733) is greatly appreci-
model to the incorporation of kinetic model (Moridis et al., 2005a,
ated. Zheng Rong Chong is grateful for the presidential fellowship.
2008); from simplified one-way coupling with geomechanical
Zhenyuan Yin would like to thank the industrial postgraduate
model to a more realistic two-way coupling (Kim et al., 2011); from
programme (IPP) for the scholarship. This review is dedicated to
reduced scale simulation (coarse grids) to a full 3D simulation
Professor Raj Bishnoi (University of Calgary) for his outstanding
encompassing 2.5 M gridblocks (Reagan et al., 2014). Nonetheless,
contributions to gas hydrate research.
it is essential to move on towards a more holistic and accurate
depiction of hydrate bearing sediments during production stage to
harness the huge amount of energy stored in NGH. The accuracy of Nomenclature
a reservoir model can be improved with:
a,b,c empirical constant in equation
(1) Improved knowledge on various parameters and models A reactive surface
describing the physical processes, reaction kinetics and Anm interfacial area between grid n and m
thermophysical properties. For instance, it is critical to AP surface area per unit volume of a gas hydrate particle (m2/
accurately depict phase equilibrium of methane hydrate in m3 )
natural conditions, which is complicated by pore-water AS combined surface area of the decomposing particles, m2
chemistry, pore size distribution, presence of mineral ions cn heat capacity of zone n, J/K Kg
and other minor guest constituents (Collett et al., 2015); cv volume heat capacity of gas, J/K Kg
(2) The availability of long term field production test data for CR Specific heat capacity of rock
matching and validation (NRC, 2009); D0 hydrate particle initial diameter, m
(3) Advancement in geomechanical modelling, which is still in a DE/DEa activation energy, J/mol
rudimentary stage of development requiring more experi- fe /feq fugacity of methane at three-phase equilibrium
mental data to construct, calibrate and validate the geo- pressure, Pa
mechanical models (NRC, 2010; Rutqvist and Moridis, 2007). fv gas phase fugacity at grid T
(4) Well placement optimization. Upon the development of a f fugacity of methane at the solid surface, Pa
robust model, incorporation of well placement optimization fs radiance emittance factor
tools can further escalate the potential production from NGH. FA area adjustment factor
FE overall energy efficiency ratio
4. Conclusion Fnm flux across the boundary of n and m blocks
g gravitational acceleration vector
In this review, the modelling of hydrate dissociation process in hW hydration number of methane hydrate
both classic and state-of-the-art hydrate reservoir simulators were Hb specific enthalpy of phase b
outlined and the technical gaps in existing kinetic models were k decomposition rate coefficient, s
1
examined with suggestions for further improvement. In summary, DH latent heat of hydrate dissociation per mole, J/mol
the understanding of hydrate dissociation kinetic process has DH0 specific enthalpy of hydrate dissociation/formation
advanced since 1980s. Although there are still barriers to conquer, k0 pre exponential factor
with more sophisticated experimental techniques and fast-growing kb backward reaction rate constant, s
1
computational power, it is expected that more details of hydrate k0d intrinsic kinetic rate constant, mol/m2 Pa s
dissociation behaviour will be elucidated both experimentally and kd decomposition rate constant, mol/m2 Pa s
from computational modelling. Understanding and employing the kf forward reaction rate constant, s
1
accurate physical model to simulate the process is the key. In the koverall overall reaction rate constant, s
1
near future, two different approaches to advance the understand- kn phase permeability of gas in zone n, md
ing of hydrate dissociation kinetic behaviour can be expected: One k thermal conductivity of hydrate, W/m K
is through applying fundamental theory to validate the assump- kr rock intrinsic permeability
tions made in the current existing kinetic models to reveal more K0 intrinsic rate constant for hydrate reactions
details of the process. With the aid of computational modelling, K1 rate constant of gas hydrate decomposition for
there could be phenomena predicted that may not be observed component 1, mol/m2 Pa s
from current experimental work. The other approach is through KR the thermal conductivity of rock
more advanced experimental apparatus to further understand the Kb the thermal conductivity of rock of phase b
1384 Z. Yin et al. / Journal of Natural Gas Science and Engineering 35 (2016) 1362e1387

l(t) the distance of decomposition front away from the well, s0 Stefan-Boltzmann constant
m
m porosity References
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nH total moles of methane contained in the hydrate particles, Alavi, S., Ripmeester, J., Klug, D., 2007. Molecular dynamics study of the stability of
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Alavi, S., Ripmeester, J.A., 2010. Nonequilibrium adiabatic molecular dynamics
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