Chemical Engineering Journal 342 (2018) 9–29

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Chemical Engineering Journal

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Review

A review of gas hydrate growth kinetic models T

a,b a b a,⁎
Zhenyuan Yin , Maninder Khurana , Hoon Kiang Tan , Praveen Linga
a
Department of Chemical and Biomolecular Engineering, National University of Singapore, 117585, Singapore
b
Lloyd's Register Singapore Pte. Ltd., 138522, Singapore

H I G H L I G H T S

• AModel
comprehensive review of open literature on gas hydrate growth kinetic models is presented.
• In-depthbased kinetic rate parameters, and mass and heat transport parameters are summarized.
• analysis of model results are provided with future research directions highlighted.

A R T I C L E I N F O A B S T R A C T

Keywords: Research on gas hydrates has progressed over the past several decades as a technology enabler for several
Gas hydrates innovative applications in the areas of water, energy, and environmental aspects. In this review, we present a
Hydrate growth systematic review of literature on the kinetic models describing the behaviour of gas hydrate growth. We re-
Kinetic models viewed a total of 27 classical and state-of-the-art models with their variations. These models were categorized
Heat transfer
into groups according to their controlling mechanism postulated (heat transfer, mass transfer, or intrinsic kinetic
Mass transfer
Fluids flow
reaction), solution methods adopted (semi-empirical, analytical, or numerical) and reactor configurations
Porous medium (stirred-tank, packed-bed, flow reactor or hydrate film). We examined in-depth the main features of each kinetic
Numerical modelling model including its formulation, assumptions, governing equations, solution method, strengths and limitations.
Semi-empirical models In addition, we have summarized the critical transport parameters of heat and mass transfer, and the intrinsic
kinetic rate parameters associated with hydrate growth in these models. Knowledge gap still exists in under-
standing the controlling mechanism of gas hydrate growth, which is further augmented by the dynamic beha-
viour of multiphase fluids flow, the thermodynamics of hydrate-forming system, and the compounding inter-
facial phenomena. Future efforts need to be devoted to recognize the coupling effect of heat and mass transfer,
fluids flow, and gas hydrate phase change behaviour (i.e. its intrinsic kinetics) from multiscale.

1. Introduction
Gas hydrates are solid crystalline compound, which consist of water
and gas molecules. Water molecules form cage-like crystal lattice
through hydrogen bonds encaging the guest gas molecule, and the latter
of which is stabilised by van der Waal’s forces [1,2]. The size of typical
guest gas molecule that can fill the hydrate cages varies between 3.8
and 6.95 Å [3,4]. These include small-size hydrocarbon molecules (e.g.
CH4, C2H6, C3H8, etc.) as well as H2S, N2, CO2 in nature. Depending on
the number and structure of hydrate cavity and the size of guest mo-
lecule, three primary gas hydrate structures are identified so far, i.e.
cubic structure I (sI), cubic structure II (sII) and hexagonal structure H
(sH) [5]. Based on the phase diagram of hydrate forming gas + H2O,
gas hydrates are stable at suitable low temperature and high pressure
conditions. Being non-flowing crystalline solids, gas hydrates have the
capability to contain gas molecules effectively (1 vol gas hydrate may
contain up to 160–180 vol of hydrate-forming gases under STP [6]
depending on the hydration number). Thus, they have given rise to
numerous applications since their discovery. Major applications of gas
hydrates are in the area of flow assurance [7–10], energy storage and
transportation [11–15], natural gas hydrate (NGH) recovery for energy
[16–21], gas separations [22–27], CO2 sequestration [28–31], water
desalination [32–36] and several other environmental aspects (global
warming [37–40] and geo-hazards [41–44]) .
A review of industrial and academic hydrate-related problems
shows that the most challenging and intriguing process is the behaviour
of hydrate formation and dissociation with respect to time, i.e. its ki-
netic behaviour [2]. Compared with the time-independent studies of
gas hydrate properties since 1960s [45], the focus has shifted more
towards understanding the kinetic behaviour of hydrate formation and

⁎
Corresponding author.
E-mail address: praveen.linga@nus.edu.sg (P. Linga).

https://doi.org/10.1016/j.cej.2018.01.120
Received 2 October 2017; Received in revised form 23 December 2017; Accepted 22 January 2018
Available online 31 January 2018
1385-8947/ © 2018 Elsevier B.V. All rights reserved.
Z. Yin et al. Chemical Engineering Journal 342 (2018) 9–29

Nomenclature SH saturation of hydrate phase

T temperature
a, b empirical parameters ΔT degree of sub-cooling
j guest gas component Vx fluid velocity in x-direction
m, n, q order of reaction with reaction to species x mole fraction of gas
as total surface area of gas-water interface X(t) spatial position of hydrate interface
A lumped pre-exponential constant
Ag-l interface area between gas and liquid Greek Letters
Ap hydrate particle surface area
As water droplet surface area α conversion of hydrate
B.C. boundary condition α∗ initial conversion of hydrate
cw0 initial water concentration αw thermal diffusivity of water
C concentration δ film thickness
Cr gas concentration in saturated water µ viscosity of fluid
D diffusion coefficient γ overall order of the reaction
ΔEa apparent energy of activation for hydrate formation µ0 zeroth moment of the particle size distribution
f fugacity of guest gas µ1 first moment of the particle size distribution
G hydrate particle growth rate µ2 second moment of the particle size distribution
G.E. governing equation γ Hatta number
h heat convection coefficient σ surface tension
h(z,t) hydrate saturation as a function of both position and time ψ parameter fitted in the hydrate film growth rate correla-
H Henry’s law constant tion
ΔH latent heat of hydrate formation Φ porosity
I.C. initial condition λH heat of hydrate dissociation
k absolute permeability of medium ρw density of water
kd mass transfer coefficient ρH density of hydrate
kr lumped reaction rate constant Ρice density of ice
kH-L mass transfer coefficient in hydrate layer τ1 time constant for initial reaction of methane gas with ice
kw thermal conductivity of water τ2 time constant for methane gas diffusion
k’(h) relative permeability function τ3 time constant for methane gas reaction
K∗ overall kinetic rate constant
Kh heat transfer coefficient Superscripts and Subscripts
KO-L mass transfer coefficient at oil-water interface
L height of the multiphase mixture in the reactor b bulk
M molecular weight eq equilibrium
NH hydration number exp experiment condition
P pressure g gas phase
r hydrate particle radius H hydrate component
rH rate of hydrate film growth sys flow system
R universal gas constant tb turbidity point
t time l liquid phase
SA saturation of aqueous phase w water component
SG saturation of gas phase

dissociation since mid-1980s [46,47]. A number of comprehensive re-
views, which mainly focus on gas hydrate thermodynamic properties,
e.g. molecular structures and phase equilibria, have been published in
journals [1,5,6,48,49] and book chapters [2,4]. However, only a
handful of review papers are devoted to the understanding of the time-
dependent behaviour of gas hydrate formation and dissociation
[50–55].
A good understanding of hydrate formation kinetics is beneficial for
three main reasons: (i) to increase the rate of gas hydrate formation,
which is critical in most hydrate-related technologies, e.g. hydrate
based gas storage, hydrate based gas separation [56,57], and CO2 se-
questration [58]; (ii) to depress the rate of gas hydrate formation,
which is instrumental in hydrate kinetic inhibition and hydrate risk
management in the area of flow assurance [59]; and (iii) to understand
the location and rate of formation for naturally occurring gas hydrates
in geological environment (i.e. marine and permafrost locations)
[60,61].
In comparison with gas hydrate dissociation [52], the study on the
kinetic behaviour of gas hydrate formation is more complicated, partly
because hydrate formation involves two coupled processes, a stochastic
hydrate nucleation process and a hydrate growth process [2]. Besides, it
is a comprehensive subject, which requires analysis of multicomponent
distribution in multiphase under various liquid-gas contact patterns at
multiscale over time. A detailed understanding of hydrate formation
behaviour requires knowledge of thermodynamics [62], heat and mass
transport phenomena [63], colloid science [64], reaction engineering
[65], multiphase fluids flow in porous media [66] and flow lines [67] in
addition to mathematical modelling [68] and numerical simulation
[69]. It is these well-established underlying sciences that lay the
foundation of the governing equations and the constitutional relation-
ships that accurately describes the behaviour of gas hydrate formation.
The investigation of the behaviour of gas hydrate growth practically
started from laboratory experiments, where gas hydrates were formed
inside high-pressure vessels with formation rate measured [50]. Sub-
sequently, a kinetic model was formulated to capture the physics albeit
with assumptions. Numerical or analytical solution of the governing
equations in the proposed model was obtained in order to validate the
model results against the experimental observations. More often, semi-
empirical kinetic parameters in the model need to be fitted due to the
lack of prior knowledge. Analysis on model performance including its

10
Z. Yin et al.
limitation and applicability were only discussed in some papers
[70–72]. With the advancement of both instrumentation and com-
puting power during the past ten years, models proposed in an earlier
time have been improved further by incorporating newly observed
phenomena, more sophisticated physics, better quantified parameters
or superior solution methods. Thus, in order to provide a holistic view
of the advancement of this research topic, it is necessary to review those
classical gas hydrate growth kinetic models together with their varia-
tions, which is an aim of this paper. This is also a complementary paper
to our recent review on kinetic models and numerical simulations of gas
hydrate dissociation [52].
With focus on the macroscopic-scale behaviour of gas hydrate
growth, we started from introducing the general concepts of gas hy-
drate formation process. Hydrate growth kinetic models were subse-
quently reviewed with special emphasis on their controlling me-
chanism, types of hydrate-forming gas and the configurations of
reactor. We examined in-depth the main features of each kinetic model
including its formulations, assumptions, driving force, governing
equations and the associated initial and/or boundary conditions, solu-
tion methods and model-based conclusions. In addition, critical kinetic
parameters obtained in each model were summarized for benchmarking
and future application. Moreover, we presented instructive figures to
explain the relevant phenomena, mechanisms, modelling approaches,
and solution techniques. The objective of this work is to provide re-
searchers an updated and comprehensive knowledge accumulated in
the current body of literature on kinetic modelling the behaviour of gas
hydrate growth. Additionally, we assessed both the strengths and lim-
itations of each model and identified several major challenges to tackle.
In summary, this review aim to direct researchers to the most re-
presentable model when describing the kinetic behaviour of hydrate
growth is required. In addition, the suggested areas of improvement
also warrant future research efforts.
2. General concepts on gas hydrate formation
Gas hydrates formation is similar to the crystallization process and
can be described by two steps: hydrate nucleation and hydrate growth.
Hydrate nucleation is an intrinsically stochastic process that involves
the formation and growth of gas-water clusters to critical-sized hydrate
nuclei. Whereas, hydrate growth process involves the continuous
growth of a stable hydrate nuclei to solid hydrates until reaching a
stable condition [50]. To illustrate the idea of hydrate formation more
intuitively, Fig. 1 shows a typical gas uptake curve for the hydrate
formation process in a laboratory-scale stirred tank reactor [70]. The
rate of gas consumption represents the hydrate formation rate which is
controlled by the process of gas dissolution and induction, hydrate
nucleation and growth processes. Gas dissolution and hydrate nuclea-
tion period is marked as Region 1 in Fig. 1. This period includes the
hydrate nucleation induction, which is the time taken from the at-
tainment of supersaturation till the first hydrate crystal nuclei to be
visible or detected at macroscopic level [73,74]. Whereas, Regions 2, 3
and 4 denotes the different stages during hydrate growth. In Region 2, a
very rapid hydrate growth occurs and a significant increase in gas
consumption can be observed. During the hydrate growth period, gas
molecules are being transported from vapour phase to liquid phase and
densely packed in the hydrate cages. As the water and gas molecules are
consumed during hydrate formation, the rate of hydrate formation
gradually decreases with time and finally flattens at the end of the
hydrate formation process, which is denoted in Region 3. The attained
stead state in Region 4 could be due to the complete consumption of
hydrate-forming component (i.e. water or gas) inside the reactor or the
limitation of mass transfer or heat transfer, which results in small
driving forces and slow hydrate formation rate. At the point of E, the
formed hydrate is deemed to be stable, which could be extracted for
laboratory testing or used for dissociation experiments.
11
Chemical Engineering Journal 342 (2018) 9–29
3. Kinetic models of gas hydrate growth
The growth of gas hydrates practically takes place right after the
nucleation, and is considered as a complicated interfacial phenomena,
which involves multicomponent (i.e. water, gas and hydrate) distribu-
tion in multiphase (i.e. aqueous, gas and hydrate) at multiscale level
(i.e. molecular-scale and macroscopic-scale) [50]. The analysis of this
phenomena requires the understanding of heat and mass transfer, fluids
flow and intrinsic kinetics of phase change. At macroscopic level, the
rate of gas hydrates growth was typically quantified based on the gas
consumption rate calculated from the measurement of pressure (P) and
temperature (T) [75–78] as well as other direct visualization techniques
on the hydrate film thickness and morphology [79,53,80,81]. At mi-
croscopic level, hydrates growth can be considered as a combination of
three different factors [2]:
a) Mass transfer of water and gas molecules to the growing hydrate
surface
b) The intrinsic kinetics of hydrate growth at the hydrate surface
c) Transport of the heat released from the exothermic hydrate forma-
tion reaction away from the growing crystal surface
Accordingly, a kinetic model can be structured based on the parti-
cular controlling mechanism postulated: (i) mass transfer; (ii) intrinsic
kinetics; (iii) heat transfer or a combination of them. Since hydrates
growth is generally considered as an interfacial phenomena [82], the
movement of guest gas molecule from one phase to another should be
considered in the rate equation. Thus, the common rate expression ty-
pically incorporated mass transfer rate terms in additional to the
commonly known “intrinsic kinetics” [46,70,83,84]. In addition, heat
transfer analysis stemmed from classical nucleation theory also pro-
vided insight into the thickness and growth rate of the initial gas hy-
drate film [79,85]. These mechanisms are often coupled and either one
of them could be dominating during the process of hydrate growth
depending on the hydrate formation condition.
A considerate amount of literature has been published on this sub-
ject during the past ten years. In Table 1, we summarized a total of 27
well-known hydrate growth kinetic models with their variations de-
veloped since the 1980s. These models were categorized based on their
governing physics, types of hydrate-forming gas, configurations of hy-
drate reactors and solution methods. In addition, we have included the
key features of each model together with their proposed driving force
and model based equations. From revisiting these models, it was found
that most of the models listed are not derived from first principles and
the model formulation depends largely on the configurations of hydrate
Fig. 1. Typical gas uptake curve during gas hydrate formation in a stirred tank reactor.
Z. Yin et al. Chemical Engineering Journal 342 (2018) 9–29

Table 1
Summary of hydrate growth kinetic models categorized by controlling mechanisms, model features, driving force or rate equation, types of guest gas, solution methods, and reactor
configurations.

Controlling mechanism Model features/driving force/rate equation Guest gas Solution method Reactor Reference Year

Reaction kinetics Arrhenius-type rate equation CH4 Semi-empirical Semi-batch STR [47,83] 1983
r = Aas exp(−
ΔEa a
)exp(− b ) P γ C2H6
RT ΔT
Five pseudo-elementary reactions with rate constants CH4 CSTR [91] 1993
Arrhenius-type rate equation with sub-cooling as driving force CH4 Flow line (oil- [92,93] 2009
r = uk1exp(−
k2
) As (Teq−Tsys ) dominated)
RT
First order rate law in terms of mole fraction of hydrate CO2 Flow reactor [96] 2011
forming gas
r = KR × x G (t )

Mass transfer Fugacity difference of gas phase with population balance CH4 Analytical/Semi- Semi-batch STR [84,270] 1987
model C2H6 empirical
2
r = ∑1 K ∗j AP (f −feq )j
Concentration difference between gas and liquid phase CH4 Numerical/Semi- [72] 1993
r = kL Ag − l cw 0 (x int −x b) C2H6 empirical
Concentration difference with advanced nucleation model CH4 CSTR [105] 1999
r = k g (Cb−Ceq)
Concentration difference with particle size analysis CO2 Semi-batch STR [103] 2005
Concentration difference of CH4 between oil phase and CH4 CSTR [109] 2009
equilibrium (water-in-oil)
eq
r = k g − o Ag − o (CCH 4,o
−CCH 4,o)

Heat transfer 1D conductive heat transfer model CO2 Analytical Hydrate film [143] 1999
1D convective and conductive heat transfer model/ CO2 [144] 2000
vf δ = ΔT3/2
1D convective heat transfer model/ CH4 [79] 2007
vf = ψΔT 5/2
2D transient heat conduction model CO2 Numerical [85] 2006

Mass transfer and Concentration difference with mass transfer and reaction CH4 Analytical/Semi- CSTR [106] 2002
Reaction kinetics kinetics empirical Semi-batch STR [108]
r = K (Csol−Ceq)
1 1 1
= +
K kL Ag kS A c
Mass transfer at liquid-vapour interface and reaction kinetics C3H8 [110] 2007

r=
1
Ap ( 1
kH − L
+
1
kr ) +
1
kG − L
Shrinking core model with diffusion or reaction coupled CH4 Ice particle to hydrate [131,136,271,133] 1998
(2k )1/2
(1−α )1/3 = (− )(t −t ∗)1/2 + (1−α∗)1/3
r0
Molecular diffusion with 1st order formation kinetics of H2O CO2 Numerical Hydrate film [111,112,114] 1993
Molecular diffusion with 1st order formation and dissociation CO2 [115] 1994
kinetics of H2O
Molecular diffusion with 1st order formation kinetics of CO2 CO2 Analytical [116] 1994
Reaction-limited and diffusion-limited schemes with CH4 Numerical/Semi- Hydrate film (water-in- [117] 2009
induction time empirical oil)

Heat transfer and Kinetic rate coupled with heat transfer model THF Semi-empirical Hydrate film [145] 2000
Reaction kinetics dX
=
ΔT
dt ⎛ 1 1 ⎞
ρh λ ⎜ n + havg (t ) ⎟
⎝ k ΔT ⎠
Kinetic rate coupled with heat convection model CH4 [141] 2001
dX Teq − Tbulk
= 1 1
dt
ρh λ ⎛ + ⎞
⎝k h⎠
Surface kinetic rate coupled with heat transfer model CH4 Hydrate film (water-in- [149] 2013
Teq − Tbulk oil)
r= ΔH 1
+
kh Ah kr Ar
Equilibrium model in sandy porous medium CH4 Analytical/ Geological reservoir [157,159,160,162] 1997
Numerical
Fluid flow Heat flow and Kinetic rate equation for both hydrate formation and CH4 Numerical [164] 2008
Reaction kinetics dissociation CO2
Kinetic rate equation based on model of Kim et al. [46] CH4 Geological reservoir and [167] 2003
packed bed reactor
Simple Slug flow model coupled with kinetic rate and heat CH4 Flow line Flow loop [186] 2013
flow

reactor, the contact patterns of the multiphase fluids (gas-liquid-hy-
drate, liquid-liquid-hydrate) and the gas hydrate formation techniques.
It should be noted that there is no uniform model that could account for
all the observed hydrate grow kinetic behaviour so far. Thus, the pri-
mary objectives of reviewing these models are: (i) to direct researchers
to the most appropriate model based on their applications; (ii) to ana-
lyse in-depth the strengths and limitations of these models; and (iii) to
put forward some future directions for further investigation on this
subject.

12
Z. Yin et al.
3.1. Models based on chemical reaction
Vysniauskas and Bishnoi carried out experiments in a semi-batch
stirred tank reactor to investigate the kinetic rate of CH4 and C2H6
hydrate formation after the commencement of nucleation [47,83]. The
hydrate formation process was described as a two-step process, which
began with the formation of a crystallization nucleus at the gas-water
interface followed by the subsequent growth of hydrate crystal around
the formed nucleus. A three-step reaction mechanism was proposed in
their formulation of a semi-empirical model. The 3-step rate equations
were constructed accordingly based on Arrhenius type of equation de-
scribing Eqs. (1)–(3):
M + H2 O + (H2 O) y − 1 ⇄ M … (H2 O) y (1)
M + H2 O + M (H2 O)z ⇄ M . (H2 O)c
(2)
M + H2 O + M (H2 O)m ⇄ M … (H2 O)n (3)
To further illustrate: an initial clustering process was described by
Eq. (1); the formation of a critical cluster was represented by Eq. (2);
and the growth of the hydrate crystal around a stable nucleus was de-
picted by Eq. (3). By combining the proposed mechanisms, the rate of
hydrate formation became a function of the concentrations of critical
cluster, H2O monomer and CH4 monomer at the interface, and the total
surface area of the gas-water interface, which was expressed in Eq. (4).
r = kr as [H2 O]m [H2 O]nc [M ]q (4)
where kr is the lumped Arrhenius type reaction rate constant, as is the
total surface area of the gas-water interface, m, n and q are parameters
indicating the order of reaction with respect to each component, and
subscript c represents the critical size cluster. Results from their ex-
perimental measurement revealed that the formation kinetics were
dependent on the interfacial surface area (as), P, T, and the degree of
sub-cooling (ΔT). An increase in P will increase the rate of hydrate
growth, whereas a corresponding increase in T will decrease the growth
rate. The degree of sub-cooling affected the concentration of the critical
size hydrate cluster in crystallization process. Thus, a growth rate
equation was further proposed based on these critical measurable
parameters shown in Eq. (5).
ΔE a
r = Aas exp ⎛− a ⎞ exp ⎛− b ⎞ P γ
⎝ RT ⎠ ⎝ ΔT ⎠ (5)
where A is a lumped pre-exponential constant, ΔEa represents the ap-
parent activation energy for hydrate formation, a and b are two em-
pirical parameters, P is the total pressure of the system, γ equals the
overall order of the reaction and ΔT represents the degree of sub-
cooling. The interface area was estimated at a fixed stirring speed of
500 rpm. In total, there were five empirical parameters to be fitted in
the model (A, ΔEa, a, b, and γ). This semi-empirical model was also used
by Vysniauskas and Bishnoi in 1984 to evaluate the kinetic rate of C2H6
hydrate formation [83]. Table 2 summarizes the kinetic rate parameters
for CH4 and C2H6 hydrate fitted in their semi-empirical model based on
the chemical reaction formulation.
The value of γ = 2.986 for CH4 hydrate suggests an overall order of
the reaction with respect to P is three. The estimated
ΔEa = −106.204 kJ/mol is also supported by the sum of enthalpy of
water molecule reorganization and gas-water interactions for CH4-H2O
system, which were −87.152 kJ/mol and −18.02 kJ/mol, respectively.
For C2H6 hydrate, the value of γ = 2.804 also suggests that the order of
the reaction with respect to P is around three, similar to that observed
for CH4 hydrates. The ΔEa estimated for C2H6 hydrates was
−133.015 kJ/mol [83]. Compared with the activation energy of CH4
hydrate, it implies that the magnitude of interaction between water and
C2H6 molecules is larger than CH4 molecules when both forming sI
structure hydrates. Thus, the C2H6 hydrates resulted in a larger mag-
nitude of the activation energy for hydrate formation.
13
Chemical Engineering Journal 342 (2018) 9–29
The semi-empirical model developed by Vysniauskas and Bishnoi
was adopted by different researchers in the years following. Topham
[86] adopted this model to study the growth of gas hydrates on hy-
drocarbon gas bubbles rising in seawater. By combing the model with
mass balance equation and transport properties of a gas bubble, a
number of rising bubble properties were derived, including bubble
lifetime and bubble radius against water depth [87]. The information
gained on hydrate growth in a single rising bubble was further adopted
to develop a complete bubble plume model later [88] and the results
were applied to study a hypothetical oil-well blowout situation.
Elperin and Fominykh [89] analysed cases of gas hydrate growth at
the surface of a gas slug in a channel filled with liquid. An expression of
the length of gas slug against time was derived by solving the mass
balance equation of gas. The gas consumption rate was described by the
Vysniauskas-Bishnoi chemical reaction model [83]. Additionally, a
model was further developed by incorporating both heat and mass
conservation equations during gas hydrate growth at the gas-liquid
interface for a gas-liquid slug. An analytical formula for the optimum
length of a slug flow reactor was suggested in their work based on the
residence time of a liquid slug to convert 95% of the gas slugs into
hydrates [90]. However, no experimental study was carried out to va-
lidate their predictions, i.e. the temporal change of the length of a gas
slug in a gas-liquid two phase flow system.
Another group of researchers who modelled CH4 hydrate formation
in liquid water by using a reaction kinetic approach were Lekvam and
Ruoff [91]. In 1993, based on their experimental studies, they proposed
a reaction model consisting of five pseudo-elementary processes de-
picting the three dynamic steps of hydrate formation: (i) the dissolution
of methane gas into water phase; (ii) the build-up of methane hydrate
precursor; and (iii) the growth of methane hydrate by an autocatalytic
process. The five written rate equations involved nine rate constants in
total. Two of the nine rate constants were involved in initial methane
gas dissolution and were estimated from experimental measurements.
The other seven rate constants were obtained by fitting the experi-
mental data. A very close agreement between computed simulation
results and experimental data were found in their work with the in-
duction period predicted well. Given the number of fitting constants
available, the agreement with the experiments is expected. The pre-
dictive capabilities of the model, however, cannot be concluded from
the study.
One kinetic model which was developed to account for gas hydrate
growth in oil-dominated flow lines also adopted the idea of intrinsic
kinetic reaction originally proposed by Vysniauskas and Bishnoi [47].
Under the assumption of immediate hydrate nucleation under a specific
sub-cooling (ΔT = 6.5 K), the hydrate growth can be calculated with
k
( )
the following equation r = uk1exp T2 As (Teq−Tsys ) with two adjustable
rate constants [92]. The kinetic rate constant was first fitted against the
laboratory data of Bishnoi’s group [70,47] and further adjusted to fit
the experimental data of two flow loop facilities (ExxonMobil and the
University of Tulsa) with a correction factor of 1/500 to the kinetic rate
constant. The reduction of kinetic rate constant suggests that hydrate
growth in flow loops could be limited by mass or heat-transfer, rather
than intrinsic kinetics. This intrinsic kinetic model was further im-
plemented in the CSMHyk-OLGA (a commercial flow assurance
Table 2
Summary of kinetic parameter for CH4 and C2H6 hydrate formation in semi-empirical
chemical reaction model.
Hydrate-forming Kinetic rate parameters
gas
A (cm3/cm2 min ΔEa (kJ/mol) γ a b
barγ)
CH4 2.400 × 10−29 −106.204 2.986 0.0778 2.411
C2H6 4.552 × 10−26 −133.015 2.804 0.0778 2.411
Z. Yin et al.
software) as a module to predict hydrate volume fraction [93], hydrate
agglomerate diameter [94], pressure drop and viscosity of the hydrate
slurry [95] in flow lines.
To depict CO2 hydrate formation in a tubular continuous flow re-
actor, a first-order rate law in terms of mole fractions of hydrate
forming gas (r = KR × x G (t )) CO2 in this case was also proposed [96].
The overall rate constant, KR depends on the interfacial area between
the phases, temperature, pressure, and lumped implicit effects of other
transport processes. From experimental observation and measurement,
KR was found to be dependent on the multiphase flow regime (annular
flow, slug or plug flow) established in the flow reactor, which varies
between 0.01 and 0.45 s−1. In addition, both kinetic-based model and
heat transfer model were able to represent the global hydrate growth
rate in the same continuous flow reactor [97].
The work of Vysniauskas and Bishnoi [47,83] marked the first at-
tempt to model gas hydrate formation kinetic rate quantitatively with
good match of experimental data. Their experimental apparatus (i.e. a
stirred semi-batch reactor) was widely adopted in many studies in-
vestigating both gas hydrate formation [70,98] and dissociation
[46,99] kinetics in the decades following. However, it is worth to note
that possible inherent errors may exit in their model, mainly because of
the difficulty to accurately quantify the interfacial area of the gas-liquid
interface (as) in the semi-batch stirred tank reactor, especially when
hydrate slurry is formed.
To further explain this point, the estimation of the gas-liquid in-
terface area depended strongly on the stirring speed in their experi-
ment. The stirring speed of 500 rpm was justified as the operating
condition only based on the visual observation: Above 600 rpm, ex-
cessive ripples formed at the surface are undesirable to estimate the
effective surface area of contact. Whereas below 400 rpm, it was not
able to remove the hydrate crystals formed at the surface. Thus, the
kinetic parameters obtained were still apparatus-dependent and may
not be applicable in a large apparatus where mass transfer resistance
could not be easily reduced by stirring. In addition, the kinetic para-
meters (a and b) had a very large confidence interval during curve
fitting. It was also suggested in their study that the kinetic model was
very sensitive to the concentration of the critical-size nucleus. This
sensitivity issue was also reported in the Englezos-Bishnoi kinetic
model, which was based on the fugacity difference [70], where de-
termining the turbidity point and the initial gas concentration were
required.
In addition, in the model of Lekvam et al. [91] and Vysniauskas
et al. [47,83], if these elementary reaction rate constants could be
further verified and estimated from a fundamental statistical mechanics
Fig. 2. Schematic of Englezos-Bishnoi hydrate growth model [70]. (a): Concentration profile at the gas-liquid interface where two film theory applies. (b): Schematic of stirred tank semi-
batch reactor where hydrate slurry forms. (c): Fugacity profile in the diffusion and adsorption layer around a growing hydrate particle.
14
Chemical Engineering Journal 342 (2018) 9–29
method (e.g. molecular-level quantum mechanism model or transition
state theory [82,100]), it would be a more powerful tool bridging the
gap between microscopic-level molecular behaviour and macroscopic-
level hydrate formation kinetic rate. It will also provide a strong proof
that the reaction of hydrate growth can be represented as a proxy of
“chemical reaction”, where technically no chemical bonds are de-
stroyed and reformed during hydrate growth.
3.2. Models based on mass transfer
3.2.1. Models based on fugacity difference
Englezos et al. presented an intrinsic kinetic model with only one
adjustable parameter for the formation of CH4 and C2H6 gas hydrates in
1987 [70]. The driving force in their study was defined as the fugacity
difference between the dissolved gas and the hydrate three-phase
equilibrium at the experimental T. The kinetic model was formulated
based on the crystallization growth theory for hydrate particle coupled
with the two-film theory describing the mass transfer at the gas-liquid
interface (see Fig. 2). The population balance model was adopted to
evaluate the second moment of the particle size distribution, which was
also proportional the gas consumption rate. Unlike the chemical reac-
tion models, where the rate of hydrate formation was a strong function
of T, it was found in their study that rate constants indicated a very
weak dependence on T.
According to the proposed model, the following two consecutive
steps of hydrate particle growth were proposed:
a) diffusion of the dissolved gas from bulk of solution to the crystal-
liquid interface.
b) adsorption process that incorporate the gas molecules into the water
molecules and the subsequent stabilization of the framework of the
structured water.
A schematic of the dissolved gas fugacity profile in the diffusion and
adsorption layers around a growing hydrate particle in solution is
shown in Fig. 2(c). It was assumed in the model that the hydrate par-
ticles were spherical and uniformly distributed in the liquid phase. In
the diffusion layer, the dissolved gas fugacity changed from value fb to
value fs. In the adsorption layer, the fugacity value decreased from fs
(fugacity value at hydrate particle surface) to feq (equilibrium fugacity
value at the experiment/bulk temperature). With the overall driving
force defined as the fugacity difference between the dissolved gas in the
bulk and at fugacity at experimental temperature, the rate of growth
per particle were expressed by Eqs. (6) and (7).
Z. Yin et al. Chemical Engineering Journal 342 (2018) 9–29

dn ∂ϕ ∂ (Gϕ)
= K ∗Ap (fb −feq ) + = θφ (r )
dt (6) ∂t ∂r (13)

1 1 1 dμ0
= + = α2 μ 2 I. C. 1: μ0 (0) = μ00
K∗ kr kd (7) dt (14)
∗
where Ap is the hydrate particle surface area, K is the overall kinetic dμ1
rate constant, which incorporates both the effect of absorption “reac- = Gμ0 I. C. 2: μ1 (0) = μ10 = 2rc μ00
dt (15)
tion” rate kr and mass transfer rate kd described in steps (a) and (b),
respectively. The global reaction rate for all particles was calculated by dμ 2
= 2Gμ1 I. C. 3: μ 2 (0) = μ20 = 4rc2 μ00
integrating the rate per particle for all particles of any size, where ϕ is dt (16)
the hydrate particle size distribution and µ2 is the second moment of the
Another critical parameter, which was the critical size of the hy-
hydrate particle size distribution.
drate nucleus, was calculated using the homogeneous nucleation theory
which took account of the Gibbs free energy of the system due to the
⎛ dn ⎞ ϕ (r ,t ) dr = 4πK ∗μ 2 (f −feq )
∞
Ry (t ) = ∫0 ⎝ dt ⎠ (8) creation of an interface and the formation of a new phase described in
Eq. (17), where σ is the surface tension of hydrate in water, vH and vW
∞
μ2 = ∫0 r 2ϕ (r ,t ) dr (9)
are the molar volumes of water and hydrate respectively. The initial
number of particles µ00 was obtained from a mass balance of the gas
Two-film theory was adopted to describe the phenomena when gas consumed at the turbidity point using Eq. (18), where MH and ρH re-
phase is brought into contact with liquid phase shown in Fig. 2(a). In present the molecular weight and the density of hydrate, ntb is the
the two-film theory, quasi-steady-state condition was assumed with no amount of gas that has been dissolved and neq is the amount of gas that
accumulation term in liquid film. Thus, gas diffusion rate from the gas- would be dissolved at three-phase equilibrium pressure. With the above
liquid interface to the liquid film was balanced with the gas con- governing equations, an average hydrate growth rate can be defined as
sumption rate from the liquid film to the bulk solution. The mass bal- follows with only one unknown parameter (K∗).
ance of the gas molecule in a slice of liquid film with thickness δ was −1
expressed in Eq. (10) together the associated boundary conditions: RTexp ⎞−1 ⎧ fb n w vw (Pexp−Peq) ⎫
rc = 2σ ⎛ ⎜ ln
⎟ +
⎝ vH ⎠ ⎨ ⎩
feq RTexp ⎬
⎭ (17)
d 2C
D = 4πK ∗μ 2 (t )(f −feq )
dy 2 (10) 3MH (ntb−neq)
μ00 =
B.C. 1: C (0) = Ceq 4πVL ρH rc3 (18)

B.C. 2: C (δ ) = Cb K ∗MH ⎞ ⎛ (fg + fb −2feq )(coshγ −1)

Gavg = ⎜⎛ ⎟ ⎜y
L + (L−δ )(fb −feq )⎞⎟
Upon adopting Henry’s law to relate fugacity to gas concentration ⎝ ρL ⎠ ⎝ γsinhγ ⎠ (19)
∗
and solving the ordinary differential equation (ODE) in Eq. (10) using The combined rate parameters K was fitted using least-square es-
analytical method, the fugacity profile of gas in the liquid film was timation for both methane and ethane under each temperature, where
obtained in Eq. (11). In addition, the flux of gas being transported to the stirring speed of 400 rpm was selected to eliminate the mas transfer
liquid phase at the interface could be derived at the boundary with gas resistance around the hydrate particles. Gas uptake profiles were
liquid surface area Ag-l given in Eq. (12). plotted for both experimental results and model fitted curves, which
showed good agreement between the two. From the fitted values of K∗,
1 ⎞⎧ y y
f (y ) = feq + ⎛⎜ ⎟ (fg −feq )sinh ⎛γ ⎛1− ⎞ ⎞ + (fb −feq )sinh ⎛γ ⎞ ⎫ it was observed that there is a very weak dependence of the parameters
⎝ sinhγ ⎠⎩⎨ ⎝ ⎝ δ ⎠ ⎠ ⎝ δ ⎠⎬
⎭ on T argued by the statement that “no chemical reaction is involved
(11) during hydrate formation”. Table 3 summarized the values of combined
rate constant for both CH4 and C2H6 hydrate at different T between
dn D∗γAg − l ⎞ ((fg −feq ) coshγ −(fb −feq ))
= Jy = 0 Ag − l = ⎛ ⎜ ⎟ 274 K and 282 K and different P ranging from 0.636 to 8.903 MPa. No
dt ⎝ δ ⎠ sinhγ (12) relationship between K∗ and T was developed in their work. These va-
lues could be used as a quick reference for benchmarking and com-
4πK ∗μ 2 Dc w0 parisons with other rate parameters.
γ=δ D∗ =
D∗ H The kinetic model developed for pure CH4 and C2H6 hydrate was
where γ is the Hatta number, which indicates how rapidly the reaction further extended to describe the formation from mixtures of the two
proceeds compared with the diffusion rate through the hydrate film; H gases by Englezos et al. [84]. The mechanism and driving force of the
is the Henry’s law constant; D is the diffusion coefficient of gas in the formation from mixtures was postulated to be the same as the pure
liquid phase and cw0 is the initial water concentration; fg is the fugacity
Table 3
of pure gas at the operating condition and fb is the gas fugacity in the
Summary of kinetic rate parameters for hydrate growth in fugacity model: Ka for CH4 and
liquid bulk. C2H6 in the model of Englezos et al. [270]; Kb for CH4 and CO2 hydrate kinetic parameter
To estimate µ2, population balance model was adopted with the in the model of Malegoankar et al. [102]; Kc for CO2 hydrate kinetic parameter in the
assumptions that the linear growth rate was independent of the crystal model of Clarke and Bishnoi [103]
size and the secondary nucleation rate was proportional to the second
a
T (K) K CH 4 × 10
5 b
K CH 4 × 10
4 K Ca2H 6 × 105 b
K CO 2 × 10
3 c
K CO 2 × 10
2
moment of the particle size distribution. Thus, the general population
(mol/ (mol/ (mol/ (mol/ (mol/
balance equation shown in Eq. (13) could be simplified to three ODEs in m2 s MPa) m2 s MPa) m2 s MPa)
m2 s MPa) m2 s MPa)
Eqs. (14)–(16). They were solved with the associated initial conditions
to obtain μ2(t). In order to tune the model with only one fitted para- 274 0.65 0.31 0.12 0.49 0.64
meter, the nucleation rate constant (α2) was set equal to 10−3 which 276 0.55 0.21 0.11 0.19 0.48
278 – – – 0.35 –
implied that there was no secondary nucleation due to crystal breakage.
279 0.57 0.28 0.13 – 0.53
It was also argued by the author that the model predictions are not 282 0.58 0.29 0.14 – –
sensitive to the values of α2 up to 1012.

15
Z. Yin et al.
gases.
The following assumptions were made to derive the rate of hydrate
particle growth:
a) Both CH4 and C2H6 form only structure I gas hydrates.
b) Both CH4 and C2H6 interact with water molecules using the same
mechanism in the hydrate phase.
c) The incorporation of gas molecules into structured water framework
depends mainly on their molecular size.
The overall formation rate was estimated as a summation of in-
dividual rates as given by Eq. (20).
2 2
(
dn
)P = ∑ ⎛ dnj ⎞ =
⎜ ⎟ ∑ K ∗j AP (f −feq )j
dt 1 ⎝ dt ⎠P 1 (20)
where Kj∗ is the individual kinetic rate constant determined for pure gas
component (see Table 3). The global rate of formation depended on the
total surface area of the particles expressed by the second moment of
the particle size distribution.
Overall, the modelled gas uptake rate correlated well with the ex-
perimental observation with an average prediction error of 11.3%. The
mixture composition had a strong effect on the fugacity driving force in
two ways: (a) it altered the gas-phase fugacity of each component; (b) it
changed the three-phase equilibrium pressure at a given temperature.
The three phase equilibrium pressure was reported to increase with
increasing methane concentration in the gas mixture. Hence, even for
the same experimental P and T, the driving force was found to decrease
with increasing methane concentration [84].
Dholabhai et al. applied the fugacity model to investigate CH4 hy-
drate formation in the aqueous solution of NaCl and KCl in 1993 [101].
The kinetic rate constant used in their model was the same as the ones
obtained for CH4 hydrate formation in pure water. Whereas, the effect
of electrolytes was considered by re-computation of the three-phase
equilibrium condition, Henry’s constant and the diffusivity of CH4 gas
in aqueous electrolyte solutions. Interestingly, the model predictions
match the experimental data well with prediction error less than 10%.
Malegoankar et al. in 1997, corrected a minor inconsistency in the
fugacity model [102]. There is no change on the model formulation,
basis, assumptions and governing equations. The only modification was
to adopt the particle diameter rather than the radius in the population
balance model when writing the initial conditions for the first and
second moments of the particle size distribution shown in Eqs.
(14)–(16). With this modification, the kinetic model was further ap-
plied to investigate CO2 hydrate growth kinetics and to re-estimate of
the kinetic rate parameter of CH4 hydrate. It should be noted that the
re-estimated kinetic rate constant for CH4 hydrate is one order of
magnitude larger than the rate constant in the model of Englezos-
Bishnoi [70]. In addition, CO2 hydrate formation rate constant is one
order of magnitude larger than the rate constant for CH4 hydrate in-
dicating a faster formation rate of CO2 hydrate (see Table 3).
Clarke and Bishnoi [103] further improved the kinetic model by
implementing an in-situ particle size analysis during hydrate formation.
The second moment of hydrate particle size distribution were measured
directly from instrumentation, rather than estimated by the population
balance model. In both models of Englezos et al. and Malegoankar
et al., the nucleation rate constant was set low to satisfy the assumption
that there is no secondary nucleation due to crystal breakage or ag-
glomeration. However, under real laboratory conditions, hydrate par-
ticles are expected to break or agglomerate locally. The addition of the
in-situ particle size measurement eliminated the need to solve the three
coupled ODEs for the second momentum of particle size distribution.
The intrinsic rate constant estimated for CH4 hydrate in their study
varied from 3.2 to 6.4 × 10−3 mol/m2·MPa·s between temperatures of
274 to 279 K and pressures of 1.6 to 3.0 MPa. By comparison, the results
were almost an entire order of magnitude larger than the results
16
Chemical Engineering Journal 342 (2018) 9–29
obtained by Malegoankar et al. [102]. It was reasoned that the actual
surface area of all particles in the stirred tank reactor is less than what
was estimated by Malegoankar et al. and Bishnoi et al. [70,102]. It was
further identified that the critical radius of hydrate particle measured in
experiment was in the order of 1 µm [103], whereas, the calculated
initial hydrate particle radius was in the order of 0.02 µm [102].
The Englezos-Bishnoi fugacity model was a pioneer work in mod-
elling hydrate growth based on fugacity difference as the driving force.
However, it is worthwhile to highlight some of the limitations of the
model in terms of application.
a) The kinetic rate constants obtained from fitting experimental data
were all for sI type of gas hydrates (i.e. CH4, C2H6 and CO2). Thus,
the model along with the rate constant should be used carefully for
sI type of hydrate only. While, kinetic rate constants for sII and sH
types of hydrate still require further quantification. These hydrate-
forming gas molecules may interact with the water molecules in a
different manner to form a more stable hydrate lattice. Essentially,
their unique molecular structures may result in different clathration
rates of gas [14].
b) The kinetic rate constants were fitted with experimental data all
from the laboratory of Bishnoi, where a stirred tank reactor was
employed with an optimal stirring speed selected to disperse the
hydrate particles and eliminate the mass transfer resistance at the
gas-liquid interface. However, this resulted in the problem of esti-
mation of the liquid gas interface area and hydrate particle surface
area. Future improvement, such as by employing microfluidic flow
reactor with controlled gas-liquid interfacial area and well-quanti-
fied mass transfer rate, may be superior in terms of quantifying
hydrate formation intrinsic kinetic rate [104].
c) It was argued that the kinetic model developed was most likely to be
apparatus-dependent, which may not be the intrinsic kinetics of
hydrate growth [6]. Thus, it is also critical to identify that the rate-
limiting step first (i.e. hydrate formation step, or mass transfer
across the gas-liquid interface, or mass transfer at the hydrate par-
ticle surface) before adoption of such kinetic growth model.
3.2.2. Models based on concentration difference
Skovborg and Rasmussen [72] reviewed the fugacity driving force
model proposed by Englezos-Bishnoi and pointed out several limita-
tions of the model with a sensitivity study on two critical parameters:
intrinsic rate constant and initial amount of gas absorbed in the water
phase. After analysing the model, a simplified model was suggested
based on the assumption that the transport of gas molecules from gas
phase to liquid phase was the rate-determining step in the overall hy-
drate formation process. Thus, particle population balance model was
removed and replaced by a simple relation between the total surface
area of hydrate particles and the amount of as consumed. The rate of
mass transfer can be described accordingly using the following equa-
tion:
dn
= kL Ag − l c w0 (x int −xb)
dt (21)
where xint is the mole fraction of gas in the water phase at the water-gas
interface in equilibrium with the gas phase at system P and T; xb is the
mole fraction of gas in the bulk water phase in equilibrium with hydrate
phase at system P and T. To apply this model, temporal evolution of the
gas mole fractions at the interface and in the liquid bulk need to be
evaluated. A solution procedure incorporating a flash calculation was
developed for the simplified model and tested on gas update experi-
mental data for CH4, C2H6 and the combined gas mixtures measured by
Englezos et al. [70,84]. It was also pointed out in their work that the
proposed model results were largely influenced by the mole fraction
calculated. Thus, a relative error term in the driving force was included
at low driving force conditions. The calculated mass transfer coefficient
(kL) had an average deviation of 22% for CH4 hydrate, 14% for C2H6
Z. Yin et al.
hydrate based on the interfacial area estimated by Englezos et al. [70].
Skovborg and Rasmussen provided a good analysis for Englezos-Bishnoi
fugacity model; however, their model was not widely adopted mainly
because the rate-limiting mass transfer step at interface assumed only
applied to a stirred tank reactor with substantial mass transfer re-
sistance at the interface. Similar to the fugacity model, a critical ana-
lysis should be carried out to identify the controlling term of the three
processes, (i) mass transfer at gas-liquid interface; (ii) mass transfer at
hydrate film; and (iii) reaction rate at liquid-hydrate interface in a
stirred tank reactor.
Herri et al. [105] further examined into the population balance
model used in the kinetic model proposed by Bishnoi and co-workers
[47,70,83] in a stirred tank reactor. Recognizing the rate limiting step
as the mass transfer in the liquid-gas film region rather than at the
hydrate particle crystallization region proposed by Skovborg and Ras-
mussen [72], a mass conservation for dissolved methane in the bulk is
adopted including two terms describing mass transfer rate and hydrate
growth rate. The highlight of this model was the formulation of PBEs,
which captured both “birth rate” due to primary nucleation, secondary
nucleation, breakage, and agglomeration and “death rate” due to ag-
glomeration. Moreover, each term in the PBE was analysed and ex-
pressed explicitly based on mass transfer and advanced crystallization
theory. In the end, a set of eight PDEs were derived and solved nu-
merically for results. It was found in their study that the simplified
model of primary nucleation/growth was sufficient to explain the in-
fluence of stirring rate on initial hydrate particle number and diameter.
Furthermore, secondary nucleation caused by attrition was identified to
be dominating at a high stirring rate, whereas agglomeration did not
offer good explanation on the increase in hydrate mean diameter.
Mork and Gudmundsson [106] developed a bubble-to-crystal model
to predict the rate of hydrate formation in a continuous stirred tank
reactor for both CH4 hydrate and NGH. It was again verified from ex-
perimental studies that the system was mass transfer (diffusion)
dominated rather than hydration reaction. Thus, in the formulation of
rate equation, mass transfer including both gas dissolution and trans-
port to crystal surface were incorporated. The highlight of the model
was instead of quantifying the individual coefficients, the overall mass
transfer coefficient was represented by a correlation [107] using mea-
surable parameters (power consumption and superficial gas velocity).
Thus, parameters used in the empirical equations were fitted against the
experimental data by regression. Although the proposed model was
semi-empirical and apparatus-dependent, it had usefulness in terms of
engineering application and could be adopted in a mass-transfer
dominated system, e.g. a semi-batch reactor or a low speed stirred tank
reactor.
3.3. Models based on combination of mass transfer and chemical reaction
3.3.1. Molecular diffusion and reaction
Based on the growth model of Englezos et al. [70], Hashemi et al.
[108] reformulated the model based on a concentration driving force
with hydrate formation kinetics. The global rate of reaction for N-
component gas mixtures is expressed in Eqs. (22) and (23).
N 1.92 × 10−7 m/s by adopting the population balance method. Again,
R (t ) = πμ 2 ∑ K i∗ (C −Ceq)i
1 (22)
1 1 1
= +
K∗ kr ks (23)
where kr and ks are the intrinsic kinetic rate constant and the mass
transfer coefficient for the diffusion of the dissolved gas from the bulk
of solution to hydrate-liquid interface respectively. µ2 is the second
moment of particle size distribution, which was obtained from the
proposed population balance model. A brief analysis on the tempera-
ture difference across the liquid film at the vapour-liquid interface was
provided in their study to show that ΔT inside the hydrate film is
17
Chemical Engineering Journal 342 (2018) 9–29
minimal. Thus, the driving force for hydrate growth should be based on
the two-phase (L-H) equilibrium rather than the three-phase equili-
brium condition (G-L-H).
Gas consumption data and transport parameters from Clarke’s study
[103] were fitted with hydrate physical properties obtained from the
work of Malegoankar et al. [102] in the model. The calculated intrinsic
kinetic rate constant (kr) for CO2 hydrate had a large variation: (i)
1.2 × 10−8 m/s by the simplified population balance model; and (ii)
4.25 × 10−5 m/s based on the measured particle surface area. This
deviation was attributed to the difference in the hydrate nuclei dia-
meter: the predicted theoretical diameter of hydrate nuclei was around
48 nm, which was around 10 times smaller than the particle size ana-
lyser can measure. With interface area lumped in the kinetic parameter,
the calculated mass transfer coefficient was on the order of 10−3 s−1,
one order of magnitude smaller than the reaction rate constant
10−2 s−1, which indicated mass transfer resistance dominated over the
hydration reaction.
Turner et al. [109] in 2009, proposed a kinetic model for the water/
oil system – an inward growing shell model for CH4 hydrate growth in
water-in-oil dispersions. Similar like fugacity model, it accounts for
simultaneous CH4 mass transfer resistance at the gas-oil and oil-water
drop boundaries. Methane transfer rate from gas phase to oil phase was
expressed based on concentration driving force. The rate of methane
gas transfer into the water/hydrate phase from the oil phase was pre-
sented by a shrinking core model. By solving the two governing equa-
tions simultaneously together with the mass conservation of methane
using very small time steps, gas uptake profile against time was ob-
tained. The average droplet radius was measured and the methane
diffusivity through hydrate was regressed to the experimental data. The
obtained diffusivity in their work was 1.4 × 10−16 m2/s. It was con-
cluded that hydrate growth in water-in-oil dispersion also appeared to
be controlled by mass transfer at the CH4 hydrate shells. The rate for
hydrate to agglomerate was more likely to control the rate of plug
formation than hydrate particle formation and growth itself.
Bergeron and Servio [110] further improved on the capability of
particle size analyser with smallest measurable particle diameter down
to 0.6 nm. The kinetic rate of C3H8 hydrate formation was studied in a
closed loop system with a newly developed kinetic model. The proposed
rate equation described in Eq. (24) included the mass transfer resistance
at the vapour-liquid interface as well as the mass transfer resistance at
the hydrate-liquid interface and reaction kinetic rate.
1 ⎛ 1 1 1
R= ⎜ + ⎞+
⎟
Ap ⎝ kH − L kr ⎠ K OL (24)
It was argued in their work that mass diffusivity through the hydrate
layer was in the order of 10−10 m2/s, which will result in kH-L on the
order of 10−5 m/s, much larger than the formation rate constant re-
ported at 10−8 m/s by Clarke and Bishnoi [103] for CO2 hydrate. Thus,
mass transfer resistance can be assumed to be negligible compared to
the reaction rate term. The growth rate constant for C3H8 hydrate was
determined to be 2.15 × 10−7 m/s at 274.2 K by measuring the particle
radius. In the same study, the growth rate constant was estimated to be
this suggested that quantification of hydrate surface area using different
methods largely affected the obtained reaction rate constant. Another
critical comment for the application of these models is to compare the
relative importance of mass transfer rate and intrinsic kinetic rate of
formation (4.25 × 10−5 m/s for CO2 [108] and 2.15 × 10−7 for C3H8)
under the experimental condition. This may result in different rate-
controlled regimes, where mass transfer effect cannot be neglected.
Shindo et al. [111,112] formulated a kinetic model for CO2 hydrate
formation by coupling both molecular diffusion and the effect of in-
trinsic kinetics. It was assumed in the model that hydrate formation
occurred mainly in the liquid-CO2 phase but not in the aqueous phase.
A three-step processes were proposed during CO2 hydrate formation:
 Z. Yin et al.

Table 4
Summary of diffusion-reaction hydrate formation kinetic models.

Diffusion-kinetic models Shindo-Komiyama [111,112] Teng-Kinoshita [116] Shindo-Komiyama [114] Lund-Shindo [115]

Schematic of hydrate concentration profiles

18
Governing equation ∂CW ∂2CW α ∂θ ∂2θ ∂CW 1 ∂ ∂CW α ∂CW ∂2CW
=D −nkCW =D −kθ = −D (r 2 )−nkCW = Dw −Rd
∂t ∂x 2 ∂t ∂x 2 ∂t r 2 ∂r ∂r ∂t ∂x 2
∂CH α rCW ∂CH α ∂Ch
= kCW θ= ∂t
= kCW = Rf −Rd
∂t Cr ∂t
C
C x = r −r0 CW = (1− H−1 ) Cr ∂CCO2 ∂2CCO2
⎜
CW = ⎛1− H−1 ⎞ Cr ⎟ ρM = Dc −Rf
∂t ∂x 2
⎝ ρH MH ⎠
Initial conditions 0 < x ⩽ ∞: 0 < x ⩽ ∞: 0 < r ⩽ ∞: 0 < x ⩽ ∞:
Cr = 0 θ (0,x ) = 0 Cr = 0 CH = 0
CH = 0 CH = 0 CW = 0
−1
CW = ρW MW
CCO2 = 0
−1
CCO2 = ρCO2 MCO 2
Boundary conditions t > 0,x = 0 : θ (t ,x ) = 0 t > 0,r = 0 : x = −∞,x = ∞:
Cr = s θ (t ,∞) = r0 e−γt Cr = s ∂CW ∂CCO2
= =0
t > 0,x = ∞: kCr t > 0,r = ∞: ∂x ∂x
γ=
∂Cr H ∂Cr
=0 =0
∂x ∂r
∂CH ∂CH
=0 =0
∂x ∂r
Solution method Numerical Analytical Numerical Numerical
Chemical Engineering Journal 342 (2018) 9–29
Z. Yin et al.
(a) water dissolved into liquid CO2 at the interface between water and
liquid CO2; (b) water diffused in liquid CO2 and reacted with CO2 to
form hydrate obeying 1st order kinetics of the concentration of water;
(c) CO2 hydrate formed blocked the dissolution and diffusion of water
in liquid CO2. 1-D mass conservation equations for water and hydrate
considering both diffusion and reaction were then expressed with semi-
infinite boundary conditions and initial conditions specified.
The governing equation of their kinetic model was solved numeri-
cally with four key parameters estimated: (a) the reaction rate constant;
(b) the order for formation reaction; (c) the mass diffusion coefficient;
and (d) solubility of water into CO2. It was shown that the thickness of
CO2 hydrate film was proportional to the diffusion coefficient D and
inversely proportional to reaction rate constant k. By perturbing reac-
tion rate constant from 10 to 100 s−1 and the diffusion coefficient from
0.5 to 5.0 × 10−9 m2·s−1, the calculated hydrate film thickness varied
from 1 to 10 μm, which agreed well with many observations on the CO2
hydrate formation articles [113]. The kinetic model of Shindo et al.
[111,112] was simple in a way that it approached the problem using
traditional reaction engineering concepts by coupling diffusion and
reaction kinetics, which are two controlling steps in many surface re-
actions (e.g. combustion). A modified version of the model in spherical
coordinates using dimensionless equations were derived by Shindo
et al. to investigate the CO2 hydrate growth on the surface of a liquid
CO2 droplet immersed in water [114]. With the same key parameters
assumed, hydrate formation time was calculated to be 0.434 s with a
thickness of 3.39 µm. The apparent thickness of the CO2 hydrate film
was speculated to be greater than the calculated value with a mixture of
colloidal CO2 hydrate and water assumed coexisting in the hydrate film.
It was also suggested in his work that the dimensionless group (β =
krp2/D) controlled the thickness of CO2 hydrate film.
Lund et al. further improved the model of Shindo by proposing a
mechanism of continuous hydrate formation and decay [115]. The
model proposed included four major mechanisms: (i) the diffusion of
water to CO2 phase, (ii) the formation of hydrate in CO2-hydrate in-
terface, (iii) the decay of hydrate in the water-hydrate interface, and
(iv) the diffusion of CO2 through the water phase. Based on his as-
sumptions, a set of one dimensional mass conservation equations were
derived for all three components-water, hydrate and CO2 with reaction
rate term defined in all three phases (water, hydrate and CO2). The
governing equations were solved numerically with four critical para-
meters estimated in the model: (a) the diffusion coefficient for water in
CO2; (b) the diffusion coefficient for CO2 in water; (c) the hydrate
formation rate constant; and (d) the hydrate decay rate constant. It was
concluded in their work that the values of diffusion coefficient were in a
wide range of 10−11–10−9 m2/s, which again compared reasonably
well to typical liquid diffusion coefficient in liquids. In addition, reac-
tion constant values were derived to be in the range of 0.1–50 s−1. The
film thickness predicted was between 25 and 35 µm and less influenced
by the variations of critical parameters.
Teng and Kinoshita [116] reviewed the kinetic model developed by
Shindo et al. and challenged that hydrate film was more prone to form
in the water phase rather than in the liquid-CO2 phase based on the
argument of relative solubility and molecular structures of CO2 hydrate.
Based on their new assumption that CO2 molecules migrated to the
crystal face to sustain the hydrate growth, a pseudo-chemical reaction
equation was described based on the concentration of CO2. The mass
conservation equation of CO2 droplet in water was employed in sphe-
rical coordinates to formulate the model. The governing PDE was
solved using an analytical (Laplace transform) method with critical
parameters identified similar to the work of Shindo [111,112,114]. The
final hydrate film thickness estimated was 36 µm, formed within a rapid
formation time of 1.91 s. In summary, reaction rate constant and the
solubility of CO2 controlled the CO2 hydrate formation time; whereas,
the thickness of hydrate film again was controlled by the diffusion
coefficient and the reaction rate constant. It was verified that the
thickness of hydrate layer became independent of droplet size if the
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Chemical Engineering Journal 342 (2018) 9–29
droplet radius was large enough (ro > > δ).
Dalmazzone et al. [117] adopted the reaction-diffusion model and
further improved by incorporating a model to predict the induction
time to investigate the formation of CH4 hydrate in water-in-oil emul-
sion. A mass conservation equation for CH4 is solved with both mass
transfer and reaction kinetics terms expressed. Two fitted parameters in
the model are the growth rate constant in the reaction term and the
super-saturation of gas in the water phase. A normal distribution of
induction time was assumed with two additional semi-empirical para-
meters, i.e. average and standard deviation of the induction time dis-
tribution. By tuning these four parameters, a good agreement between
experimental observation and model prediction was found. However, it
is worthy to note that by eliminating fitted parameters with existing
nucleation theory (for parameters predicting induction time) can be an
improvement.
In summary, Table 4 presents the schematic of various diffusion-
reaction models with their governing equations and the associated in-
itial and boundary conditions and solution method. Critical comments
on Shindo-Komiyama model were also given by Mori [71], pointing out
the possible mathematical and physical inconsistencies owing to their
assumptions. The inconsistencies are mainly based on the structure and
location of the hydrate film as well as the formulation to calculate
hydrate film thickness and formation time. Thus, it further efforts are
necessary to accurately quantify the behaviour of hydrate film growth
in controlled laboratory conditions and to further validate the model
predictions with experimental observations [112].
Another note is that the diffusion coefficient used in the models was
practically on the order of 10−9 m2 s−1, which was a typical value for
liquid diffusion coefficient in liquids. However, hydrate film tends to be
in form of ice-like solid or colloid with properties of resembling porous
material. Thus, an appropriate effective diffusion coefficient value for
gases and liquids in ice or solid, which is typically on the order of
10−21–10−16 m2/s from experimental measurement [118–120] or
10−16–10−12 calculated by molecular dynamics (MD) and Monte Carlo
(MC) simulations [121–123], may better characterize the molecular
diffusion behaviour in the gas hydrate film. This difference proposed by
us may have a significant effect on the kinetic rate parameters obtained
for the diffusion-reaction models. Moreover, the dissolution rate of li-
quid CO2 droplet in water with hydrate film has been measured by Hirai
et al. [124] under different P, T, and flow conditions. These measure-
ments from his study supported our suggestion and could be used to re-
estimate the reaction rate parameters in these models.
3.3.2. Shrinking-core model
Besides the early measurements and kinetic models developed for
hydrate growth from liquid water, hydrate formation from ice has also
been intensively investigated in the community during the past two
decades. Though the formation rate may be slow, ice surface area can
be more easily quantified than gas-water interface in the model.
Besides, it was also suggested that hydrate formation from ice was
unique as the facility of available hydrogen bonds in melting ice pro-
vides different kinetics than formation from water without such a
substantial structure [125]. A number of kinetic models and their var-
iations describing hydrate formation from ice were reviewed in this
work. In summary, the approach of employing shrinking core model
under diffusion-rate controlled scheme in hydrate layer was widely
adopted to correlate with experimental measurements.
Henning et al. investigated CO2 hydrate formation on the surface of
ice grains [126]. A quantitative kinetic rate expression between con-
version and time was developed by adopting the idea of diffusion-rate
controlled of the accumulating hydrate layer, which was qualitatively
proposed by Hwang et al. [127] and Stern et al. [128]. However, an
initial time (t∗) and initial conversion (α∗ = ∼20%) had to be guessed to
use Eq. (25) for rate constants analysis.
Z. Yin et al.
(2k ) 1/2
(1−α )1/3 = ⎛− ⎞ (t −t ∗)1/2 + (1−α∗)1/3
⎜ ⎟
⎝ r0 ⎠ (25)
Thus, it suggested that the proposed model may only work when a
substantial layer of hydrate had formed, when reaction kinetics was no
longer controlling the process. The activation energy calculated from
this work by correlating kinetic rate constant with temperature using
Arrhenius type of equation is 27.1 kJ/mol. This value is comparable to
the activation energy of diffusion by the translational motion of H2O
molecules in the quasi-liquid layer, which was reported to be 23.5 kJ/
mol [129].
Wang et al. studied the kinetics of CH4 hydrate formation from
polycrystalline ice by employing the shrinking core model [130]. The
kinetic model captured the diffusion process of CH4 gas through an
outer hydrate layer to react with the inner core of ice based on physical
observations. In this more complex model, the overall reaction of CH4
with ice particle consisted of three stages in series: (a) the initial re-
action of methane with the surface of ice particle, with time constant τ1;
(b) the growth of hydrate layer and inner diffusion of methane gas, with
time constant τ2; (c) the reaction of methane gas with ice at the un-
reacted ice core, with time constant τ3. A relation between reaction time
(t) and CH4 hydrate fraction (α) was derived to be:
t = τ1 (1−(1−α )2/3) + τ2 (1−3(1−α )2/3 + 2(1−α )) + τ3 (1−(1−α )1/3) (26)
Subsequently, an abbreviated reaction time was obtained for dif-
fusion-limited kinetic equation:
td = τ2 (1−3(1−α )2/3 + 2(1−α )) (27)
r 2ρice
τ2 =
6NH De CCH4 (28)
where r is the particle radius, De is the diffusion coefficient of methane
in the hydrate layer, CCH4 is the concentration of methane at the ice
particle surface, ρ is the molar density of the ice particle and the me-
thane hydration number NH = 5.8. An activation energy of 61.5 kJ/mol
was obtained from a semi-logarithm liner fit of kinetic rate constant
against 1/T. This value was greater than the activation energy of CO2
hydrate system reported to be 27.1 kJ/mol [126]. However, it was
smaller than the activation energy for CH4 hydrate dissociation, which
was reported by Clarke et al. [99] to be 81.2 kJ/mol in their fugacity
model. From the good agreement between the proposed model results
and experimental measurements, it was further concluded that the
hydrate formation from ice was a diffusion-controlled process, where
methane molecule diffuse slowly through the hydrate layer to sustain
the inward growth into the core of the ice particle.
Staykova et al. further improved on the model of Salamantin et al.
[131,132] and formulated a phenomenological kinetic model of gas
hydrate formation from mono-dispersed ice powder [133]. The high-
light of their model was that it acknowledged the idea that hydrate
formation rate could be controlled by either the clathration reaction
kinetics or the diffusion through the hydrate shells depending on the
corresponding formation stages. Moreover, the proposed model ac-
counted for the effect of hydrate volume expansion and the macro-pore
structure of the hydrate film. The estimated activation energy of the
CH4 hydrate clathration reaction was 33–40 kJ/mol and the activation
energy of the diffusion-limited clathration was 59.8 kJ/mol, which was
comparable with the value obtained by Wang et al. [130].
Kuhs et al. extended the work of Staykova et al. [133] and presented
an improved model for CH4 hydrate growth in an ensemble of randomly
packed ice spheres with different radius [134]. The model considered
the size difference of the spherical ice particles that could result in
different rates of hydrate conversion. A permeation rate constant was
derived from the analysis of sample structure and diffusive mass
transport through the hydrate shell. It was shown in their model results
that diffusion mechanism only became a limiting step at temperature
above 263 K. In addition, both diffusion and clathration reaction could
20
Chemical Engineering Journal 342 (2018) 9–29
be dominating at temperatures lower than 263 K. The permeation
coefficient estimated was 4.1 × 10−16 m2/s with an activation energy
of 52.1 kJ/mol. It was also in good agreement with the estimate of
Wang for CH4 hydrate (61.5 kJ/mol) [130] and Genov’s estimate for
CO2 hydrate (54.6 kJ/mol) [135].
Falenty et al. applied the shrinking-core model [133–136] to in-
vestigate CO2 hydrate formation at a lower temperature from both
monosized and polydispersed ice powders [137]. The activation energy
was calculated as 19 kJ/mol for T below 225 K, and around 46 kJ/mol
for higher T. Their results suggested that the rate-limiting step at lower
temperature could be the CO2 molecule diffusion rate via a “hole-in-the-
cage” mechanism. It should be noted that the application of shrinking
core models for gas hydrate formation from ice particle using a well-
characterized geometry could facilitate the quantification of certain
rate-limiting process. However, it has been verified that hydrate growth
from ice and hydrate growth from water may have different kinetics
and pathways [130,134,135]. Thus, these models should be used with
careful examination on the type of process and application. In analogy,
the shrinking core model developed for hydrate growth from gas using
ice particles could also be adopted in a gas+H2O system with a con-
trolled geometry of H2O in advanced microfluidic reactor system [104].
Susilo et al. [138] investigated CH4 hydrate growth from ice into sH
crystals using various large molecule guest substances as sH hydrate
formers. In his study, the Avrami equations [139,140] was adopted to
fit the kinetic rate during stage I, which is a fast hydrate growth process
and the shrinking core models shown in Eq. (25) was adopted in stage
II, which is a mass transfer controlled region. A good agreement be-
tween model predictions and experimental observations were attained
with the value of α∗, t∗ and k tabulated (Table 5 in [138]) for different
hydrate formers. This study again confirms the applicability of shirking
core model in describing the growth rate of gas hydrate of different
structures under a mass-transfer controlled regime.
3.4. Models based on heat transfer
Freer et al. employed a high pressure visual cell and optical mi-
croscopy technique to measure the rate of CH4 hydrate film growth at
the CH4-H2O interface under P range of 3.55–9.06 MPa and T range of
274.2–277.2 K [141]. A growth kinetic model was proposed with
driving force defined as sub-cooling (ΔT). The kinetic model accounted
for both heat transfer effect and the hydrate formation intrinsic ki-
netics. In total, three unknown parameters (two kinetic rate parameters
and one heat transfer coefficient) were regressed from the experimental
measurement. Molecular attachment kinetics were assumed to follow
the Arrhenius behaviour, and the heat transfer coefficient was assumed
constant.
The model of Freer was based on continuous growth mechanism
with high interfacial driving forces (ΔT) proposed by Tiller [46]. In
their model, mass transfer was assumed to be negligible and the effect
of heat transfer dominated the crystallization and growth phenomena.
A moving boundary model was first developed based on the 1D energy
conservation equation. A schematic of the hydrate film growth at the
interface of CH4-H2O was shown in Fig. 3(c). The hydrate film was
modelled as a moving boundary in the liquid phase parallel to the in-
terface. Key assumptions of the model were: (a) T at the moving
boundary equal to the Teq; (b) ΔT is negligible within the hydrate phase;
and (c) complete wetting of hydrate film by water. With the assump-
tions made above, governing equation with the associated boundary
conditions and initial condition can be expressed as follows in Eqs.
(29)–(32):
Table 5
Summary of kinetic parameters obtained in the heat transfer model of Freer et al. [141].
Kinetic parameter k0 (W/m2 K) Ea (kJ/mol) h (W/m2 K)
Regressed Value 1.6057 × 1036 171 42325
Z. Yin et al. Chemical Engineering Journal 342 (2018) 9–29

∂T (t ,X (t )) dX
B.C. 2: −k w = ρH λH
∂x dt (32)

where Tbulk is the temperature of the bulk water phase, Vx is the fluid
velocity in the x-direction, αw is the thermal diffusivity of water, ρw is
the density of water, λH is the heat of hydrate dissociation, dX/dt is the
velocity of the moving interface and kw is the thermal conductivity of
water. The PDE was solved analytically for the moving boundary ve-
locity and compared with the measured hydrate growth rate. However,
large disparity between the two results was identified and attributed to
the additional heat transfer occurred through convection (i.e. thermo-
capillary convection).
Subsequently, a model combining both convective heat transfer
effect and interfacial growth kinetics effect was proposed to describe
the growth rate through Eqs. (33)–(35).
dX
λH ρH = K (Teq−Tbulk )
dt (33)

1 1 1
= +
K k h (34)

Ea
k = k 0exp(− )
RTeq (35)

Least-square method was employed to fit the kinetic parameters

with values summarized in Table 5. The kinetic model accounting for
the effect of convective heat transfer fitted well with the experimental
data under different driving forces. In addition, the estimated heat
transfer coefficient due to convection agreed well with the values cal-
culated using a thin-wire approximation model [142].
Bollavaram et al. [145] designed experiments and modelled tetra-
hydrofuran (THF) sII hydrate growth kinetics by removing mass
transfer effect. Both heat transfer and hydrate growth kinetics were
incorporated in their proposed rate equation. The rate of THF hydrate
crystal growth was measured in their experiments. Heat transfer coef-
ficient was calculated from Nusselt number using convective potential
flow correlation [146]. As a result, reaction kinetic rate constant was
calculated and fitted with Arrhenius plot against temperature. It was
also suggested in their work that a careful assessment of heat transfer
coefficient is vital for accurate quantification of hydrate kinetics, which
was previously ignored in many works investigating crystal growth.
Uchida et al. [143] observed hydrate film growth at the interface of
CO2/H2O and proposed that the rate-determining process is the heat
diffusion step from the reaction sites shown in Fig. 3(a). The estimated
CO2 hydrate film initial thickness was 0.13 µm using the heat diffusion
model (P = 1.8–7.2 MPa and ΔT = 0.1–10.7 K). Mori further proposed
a simple convective heat-transfer model with a schematic shown in
Fig. 3(b) and predicted that the lateral growth rate of hydrate film is
proportional to the power of 1.5 with respect to the effective tem-
perature driving force (ΔT1.5) [144]. The estimated initial hydrate film
thickness was 0.3–0.6 µm based on the experimental conditions of
Uchida et al. [143].
Mochizuki and Mori adopted the postulation of conductive heat-
transfer as major effect but only considered the film front to the sur-
roundings as the rate-controlling step [85], which was previously ne-
Fig. 3. Schematic of hydrate film growth kinetic models based on heat transfer analysis glected by Freer et al. [141]. A kinetic model was subsequently de-
developed by (a) Uchida et al. [143] (b) Mori [144] (c) Freer et al. [141] (d) Mochizuki veloped by employing transient conductive heat-transfer model for two
and Mori [85]. (Reproduced from Mochizuki, T., Mori, Y.H., J. Cryst. Growth, 290, 642 2D hydrate film geometries, one with a straight hydrate film front and
(2006), with permission from Elsevier). the other with a semi-circular hydrate film front shown in Fig. 3(d).
Numerical solution for the governing PDEs was obtained and the esti-
∂T ∂T ∂ 2T mated film thickness was 10–20 µm at P = 9.06 MPa for CH4 hydrate
G.E. : + Vx = αw 2
∂t ∂x ∂x (29) and 0.5 µm at P = 5.0 MPa for CO2 hydrate. However, one counter-in-
tuitive result obtained in this study is that both CO2 and CH4 hydrate
I.C. : T (0,x ) = Tbulk (30) films showed a tendency to thinning with an increase in the system sub-
cooling (ΔT).
B.C. 1: T (t ,X (t )) = Teq Peng et al. [79] improved on Mori’s convective heat transfer model
(31)
with the assumption that the thickness of hydrate films was inversely

21
Z. Yin et al.
proportional to the driving force, ΔT. The lateral hydrate film growth
rate was thus derived to be proportional to the power of 2.5 with re-
spect to the temperature driving force. This proposed model agreed well
with the measured data for CH4, C2H6, CO2 and mixtures of gases with
initial hydrate film thickness on the order of 1 µm. Later, Li et al. [81]
measured the initial hydrate film thickness and growth of CH4, C2H6
and CH4-C2H6 mixtures under different sub-cooling conditions by ex-
posing a single gas bubble to water. The thickness of the hydrate film
was on the order of 10 µm and the lateral growth rate of hydrate film
correlated well with ΔT5/2. Table 6 summarized the fitted parameter (ψ)
in the relation between hydrate film growth rate (r) and sub-cooling
(ΔT) to the power of 2.5.
Same technique was applied by Taylor et al. [147] to quantify cy-
clopentane-water and methane-water hydrate film growth rate under
different sub-cooling conditions in laboratory. The measured hydrate
film thickness was on the order of ∼10 µm. However, only two quali-
tative mechanisms for hydrate formation at the hydrocarbon/water
interface and at the water droplet interface were proposed based on
their observations with no quantification modelling effort.
Sun et al. [148] further studied CH4 hydrate film growth with SDS
as promoter. Rather than using ΔT as driving force, molar Gibbs free
energy difference between experimental condition and equilibrium
condition was defined as the driving force. An exponential correlation
between lateral hydrate film growth rate and the driving force, Δg, was
obtained in their study.
Mu et al. [149] adopted both heat transfer and intrinsic kinetics as
the formation driving mechanisms and developed a kinetic model for
CH4 hydrate formation in water-in-oil emulsions. By combining the
heat transfer resistance and reaction kinetic resistance in series, a rate
equation could be derived shown in Eq. (36).
dn 1 [81,154,155,148,80,156] coupled with thermal measurement equip-
= ΔH 1
(Teq−Texp)
dt + ment, e.g. differential scanning calorimetry (DSC) are needed to pro-
Kh Ap Kr A s (36)
where ΔH denotes the heat of hydrate formation, Kh is the heat transfer
coefficient, Ap is the heat transfer area and equal to the total surface
area of hydrate particles, Kr is the hydrate formation rate constant, As is
the total surface area of water droplets, Teq is the hydrate formation
temperature at system pressure and Texp is the experimental tempera-
ture. The model formulation and rate equation resembled the model of
Freer et al. [141] although the reactor configuration is a semi-batch
hydrate slurry reactor instead of a film reactor. Instead of measurement
of the hydrate film, total hydrate particle surface area and total water
droplet surface area need to be quantified in the semi-batch reactor
used in the work of Mu et al. [149]. Both heat transfer coefficient and
reaction rate constant were obtained by fitting the experimental data.
An Arrhenius type of correlation was identified for the reaction rate
constant. The calculated activation energy was 50.19 kJ/mol, which
was in the range of typical surface reaction (40–60 kJ/mol) controlled
regime [150].
Another simple heat balance model was proposed by Meindinyo
et al. [151] to analysis CH4 hydrate growth in a stirred-tank reactor
under constant P. The model was based on the energy conservation
equation, which incorporated heat of hydrate formation, heat transfer
rate at the reactor wall as well as the heat accumulation rate inside the
reactor. It was argued that heat transfer coefficient varied along the
hydrate formation process, thus the values of heat transfer coefficient
can be fitted against the experimental measurement of T. A good
agreement was found between the gas consumption predicted by the
model and measured in the experimental. However, the limitations of
such semi-empirical kinetic model are: (a) it is limited to the experi-
mental apparatus employed in that particular study; (b) it depends
significantly on the fitted parameters.
In summary, the variation of different heat-transfer dominated ki-
netic models proposed is primarily due to the different geometry of
reactor, the position of the hydrate film relative to the interface and the
22
Chemical Engineering Journal 342 (2018) 9–29
dominating method of heat transfer (conduction or convection). Fig. 3
presents a schematic summarizing these aspects in four mostly adopted
models. These are the kinetic models by Freer et al. [141], Uchida et al.
[143], Mori [144], and Mochizuki and Mori [85], which offered a heat-
transfer perspective of analysing the kinetic behaviour of hydrate film
growth. The driving forces defined in these models are common, which
is the temperature difference between the hydrate film and the equili-
brium temperature. This deviates from the traditional driving force
defined as fugacity or concentration difference, which are typically
used in mass-transfer based models.
It is undeniable that heat transfer plays a significant role during the
process of hydrate growth due to its strong exothermic nature of re-
action related with high enthalpy change [152,153]. However, it is also
evident that the results obtained from these kinetic models have lim-
itations, which strongly depends on the boundary conditions and initial
conditions assumed. These conditions are very difficult to validate with
the current experimental techniques (due to its small dimension and
fast time scale), and can be unrealistic sometimes. In addition, it was
also pointed out that the inner structure of the hydrate film was not
clear yet [53], which may result in a transient nature of thermal
properties, heat transfer coefficients [151] and limit the applicability of
these proposed models. It is also worthy to note that these selected
kinetic models investigating the fundamental heat transfer mechanism
of hydrate growth and estimating the rate of hydrate growth mainly
focus on the interface of water and hydrocarbon phases. Understanding
the fundamental concepts of these models, in particular heat transfer
coefficient, kinetic rate constant and hydrate surface area, is also of
great value for the research, design and development of novel techni-
ques of the management of gas hydrates in oil and gas flow lines
[92,93,97]. Thus, more observations on the hydrate film morphology
and growth (initial thickness and lateral growth rate)
vide more insights into the kinetic models developed based on heat
transfer analysis.
3.5. Models for gas hydrate formation in porous media
Rempel and Buffet in 1997 investigated hydrate growth rate and
spatial distribution in uniform porous media [157]. The liquid-gas
mixtures were modelled as an incompressible fluid with constant dy-
namic viscosity µ, travelling at velocity u through a fixed, homogeneous
porous medium with permeability k. Thus, momentum conservation
can be described by Darcy’s law in Eq. (37).
k
u = −k′ (h) ∇P
μ (37)
where k′(h) is the relative permeability function that accounts for the
reduction in effective permeability due to clogging of pores by solid
hydrate. In addition, the fluid density and the hydrate density generally
differ; hence, the rate of volume change associated with the phase
transition will induce a divergence of flow. The mass balance was ex-
pressed by Eq. (38).
Table 6
Summary of ψ in the heat transfer model of rH = ψΔT5/2 describing the growth rate of
hydrate film [79,81].
T (K) Hydrate growth rate parameter (ψ)
CH4 C2H4 CO2 C2H6
273.4 2.76 4.07 35.73 —
275.4 3.31 4.91 43.61 —
277.4 3.86 5.63 52.80 —
280.0 0.96 — — 6.62
279.4 4.46 6.63 63.80 —
Z. Yin et al. Chemical Engineering Journal 342 (2018) 9–29

∂h hydrate accumulation in sediments and the rate of CH4 hydrate accu-

ρf ∇ • u = ϕ (ρf −ρh )
∂t (38)
Energy conservation equation was employed in Eq. (39) considering
the heat transport by advection, dispersion as well as thermal con-
duction through the bulk matrix. The latent heat released by the exo-
thermic of hydrate formation acted as a heat source term in the energy
equation. The heat capacity expression in Eq. (40) took into account all
three components (hydrate, fluid and the sand medium).
∂T ρ ϕL ∂h
C (h) + u·∇T = ∇ ·(κ (h) ∇T ) + h
∂t ρf Cf ∂t (39)
ρf Cf ϕ (1−h) + ρh Ch ϕh + ρs Cs (1−ϕ)
C (h) =
ρf Cf (40)
In addition, hydrate formation required a transfer of gas from the
fluid into the hydrate. Assuming mass fraction of gas ch in hydrate
structures was constant and mass fraction of gas c in the fluid was de-
pleted with time as the hydrate grows. Thus, mass conservation of gas
considering advection, convection and diffusion transport was de-
scribed in Eq. (41).
∂c 1 ρ ∂h
(1−h) + u·∇c = ∇ ·[(1−h) D∇c ]− h (ch−c )
∂t ϕ ρf ∂t (41)
The above governing equations together with the thermodynamic
equilibrium condition provided a complete description of hydrate for-
mation in uniform porous media. A schematic showing the calculation
domain with initial and boundary conditions was presented in Fig. 4. In
this numerical model, it involved a homogeneous medium with porosity
Φ. The boundary was cooled to a temperature T0, which was below the
hydrate equilibrium temperature Teq. A hydrate layer developed with
an advancing interface defined by z = a(t). The hydrate saturation h
(z,t) in the layer is a function of both position and time. The initial
temperature and gas concentration are denoted by T∞ and c∞. Scaling
analysis was used to identify the lead-order terms and a reduced set of
equations were developed with the advection term neglected based on
the assumption that chemical diffusion was primarily responsible for
gas transport in porous media system. Analytical solution to the PDEs
for gas concentration profile, temperature profile and hydrate growth
rate was derived using similarity method.
In addition, a kinetic model considering the non-equilibrium effects
shown in Eq. (42) was also included based on the gas consumption rate
equation proposed by Englezos et al. [70].
dc
= −K (c−ceq)
dt (42)
mulation as a function of depth in diffusive and advective controlled
environment.
Davie and Buffet [160] presented a more comprehensive numerical
model to predict the volume and distribution of gas hydrate in marine
sediments. The highlight of the model was that the concentration of
dissolved CH4 in the pore fluid was accounted in addition to in-
corporating a simple model accounting for the biological production
CH4. By further quantifying the supply of CH4 with regard to the source
of carbon, several other key parameters (e.g. the rate of sedimentation,
quantity and quality of the organic material and the rate constant that
characterizes the biological productivity) were determined to be critical
for hydrate distribution and accumulation in marine locations.
Chen and Cathles constructed a kinetic model to simulate hydrate
formation from a gas stream in 2003 [161]. The model differed dra-
matically from the previous models published by Rempel and Buffet
[157] and Xu and Ruppel [159] in a way that hydrate formation in
nature was considered as a kinetic reaction controlled by solid surface
processes characterized by ΔE/R = ∼10,000 K. In their model, the ki-
netic rate equation incorporated the mass fraction difference between
the gas phase and the hydrate phase as the driving force and adopted an
Arrhenius-type of formulation. The thermodynamic equilibrium of
C3+C4 hydrate was constructed using CSMHYD program of Sloan [2]
and the kinetic parameter K was obtained from fitting the vent gas
composition. The presented model was a highly simplified empirical
model without considering the effects of hydrate nucleation, multi-
phase fluids flow behaviour within porous media and all the other ef-
fects of interfacial phenomena (e.g. capillary pressure). However, it was
argued in their work that too much subsurface data need to be im-
plemented for a detailed model.
Liu and Flemings developed a multicomponent, multiphase, fluid
and heat flow model to describe the hydrate formation behaviour in
marine sediments in 2007 [162]. The 1D and 2D model accounted for
the dynamic effects of hydrate formation on salinity, temperature,
pressure and hydraulic properties. The governing equations of the
model included mass transfer equation with Darcy’s law depicting the

Numerical solution was obtained to compare with the analytical

solution from the aforementioned equilibrium model. For K greater
than 100, numerical results are in reasonably good agreement with the
analytical solution. It was argued that the time scale of K for CH4 hy-
drate formation was around 108 s−1 in marine environment with a ty-
pical length scale of 100 m. Thus, it was reasonable to neglect the non-
equilibrium effects in natural environment, however, they may be im-
portant in laboratory experiments where physical dimension was much
smaller, which was around 0.1 m.
The application of Rempel-Buffet kinetic model in assessing hydrate
formation conditions and accumulation rate in marine environment
was signification in the years following. The calculated theoretical
hydrate layer thickness (80–100 m) was also consistent with both
geophysical and geochemical estimation [158]. Xu and Ruppel [159]
extended the work of Rempel and Buffet [157] by adding the fluid
advection and the CH4 supply rate terms in the coupled mass, mo-
mentum and energy conservation equations. Interpretation and analysis
of naturally occurring marine hydrate systems was obtained from the
analytical results derived. The results included the location of the CH4 Fig. 4. Schematic of hydrate formation in porous media kinetic model of Rempel and
Buffet [157].
hydrate zone boundaries, critical rates of CH4 supply, timescale for

23
Z. Yin et al.
two-phase flow within porous media, heat transfer equation and hy-
drate thermodynamic relation in salinity. The solution method adopted
was a numerical finite difference method with a primary variable
switching technique for different phases. A series of 1D and 2D cases
were simulated to study the effect of gas flux, water flux in porous
media as well as the effect of capillary pressure in gas chimney in terms
of hydrate formation. It should be noted that after careful examination,
the numerical model developed for hydrate formation are analogous to
the working principle of the reservoir simulators developed for hydrate
dissociation (e.g. the TOUGH+Hydrate family of codes developed by
Moridis [163]). However, it is still debatable whether equilibrium
model or kinetic model best describes the behaviour of gas hydrate
formation.
Uddin et al. incorporated the hydrate formation and dissociation
rate equation into the multiphase-multicomponent hydrate reservoir
simulator (CMG STARS®) to investigate gas hydrate formation in a
geological reservoir in 2008 [164]. The adopted hydrate formation rate
equation was derived from the model of Kim et al. [46] for hydrate
decomposition. Both CH4 and CO2 gas hydrate formation were simu-
lated under different P, T, and reservoir conditions. This again enabled
the state-of-the-art hydrate reservoir simulators (e.g. the TOUGH
+Hydrate family of codes [163], HydrateResSim [165] and CMG
STARS® [166]) to emerge as a suitable numerical simulator to in-
vestigate the gas hydrate formation behaviour in porous media with gas
diffusion and intrinsic kinetic rate terms included. This is expected
because the underlying physics for gas hydrate growth and dissociation
are the same, except that hydrate formation involved an addition nu-
cleation process.
In addition, several works had been reported by employing nu-
merical codes (TOUGH+Hydrate [78,167] or other in-house simulators
[168]) to investigate the behaviour of hydrate formation in laboratory-
scale reactors, including the spatial distribution of various phases
during the formation process. However, it has been reported that var-
ious hydrate formation techniques existed in the community, including
excess-gas method [75,76,169], excess-water method [170–173], dis-
solved-gas method [174–177] and ice-to-hydrate method [178,179].
Thus, it required further analysis of these multi-stage gas formation
methods in details by means of numerical modelling accounting for all
steps involved in order to provide more insight into the possible het-
erogeneous spatial distribution of SH, which was already observed in
many experimental studies [174,175,180–182]. In addition, simulating
hydrate formation in porous media serve as the most accurate in-
itialization step for hydrate dissociation simulation studies [52].
However, this has rarely been investigated in most hydrate dissociation
simulation studies, where the initial saturation in hydrate reactors was
always homogeneous and uniformed distributed inside the reactor
[183–185].
Fig. 5. Various aspects of gas hydrate formation experiments, hydrate growth rate quantification and hydrate growth kinetic model development.
24
Chemical Engineering Journal 342 (2018) 9–29
Besides hydrate formation in sandy porous media, a slug flow model
combining multiphase fluid flow, heat flow and reaction kinetics to
depict hydrate growth in flow lines was developed by Zerpa et al.
[186]. This first-principle model couples the simple gas-liquid slug flow
model [187] with hydrate growth intrinsic kinetics proposed by Boxall
et al. [188] and solves the coupled flow, heat and kinetic equations
numerically using a finite difference method. The modelled results are
compared with the flow loop experiments [189] and able to capture
more details of flow regime transitions and slugging dynamics, in-
cluding the temperature evolution against time and distribution of
water and hydrate hold-up along the flow line at different times. Similar
approach that couples all three mechanisms (fluid flow, heat flow and
intrinsic kinetics) is also strongly recommend for investigation of hy-
drate growth in flow lines for other types of flow regimes[190], e.g.
stratified flow, bubbly flow and annual flow [191].
4. Future perspectives
4.1. Modelling studies on gas hydrate growth
There has been considerable advancement in our understanding of
the kinetics of gas hydrates growth during the last 30 years. The various
semi-empirical and analytical models [70,83,47,143,116,141,103,136]
developed from mass transfer, heat transfer and intrinsic kinetics per-
spectives listed in Table 1 allowed us to reproduce the experimental
data and to predict the rate of hydrate growth within a comfortable
margin. However, most models to a large extend were still limited to
one or more fitted semi-empirical parameters describing the rate of heat
and mass transfer or intrinsic kinetics. These parameters are mostly
dependent on the dimension and geometry of the experimental appa-
ratus, time scale and the fluid contact pattern. Thus, it is always ad-
visable to formulate the model from a first principle basis combining
the effect of both heat and mass transfer [192] and to perform scaling
analysis of the governing equations to identify the lead-order term for
recognizing the controlling mechanism (i.e. mass transfer controlled,
heat transfer controlled, or reaction kinetics controlled) and to extend
the applicability of the model with some non-dimensionless number
defined. It should be noted that hydrate formation does not involve
formation of new chemical bonds, and technically should be considered
as a physical reaction. However, the adoption of Arrhenius type rate
equation as a proxy to describe the intrinsic kinetic rate of hydrate
growth had been widely accepted. One postulation worth of further
investigation is that the intrinsic kinetic rate model of hydrate growth
proposed in these works may actually depict the molecular diffusion
rate of hydrate-forming gas in the hydrate film, which could also follow
Arrhenius type of equation [193].
The applications of numerical simulator in modelling hydrate
Z. Yin et al.
formation in porous medium [167,162,157] (see Table 1) are powerful
in terms of revealing and predicting a number of geological phenomena
(e.g. the location and depth of the gas hydrate stability zone, the rate of
gas hydrate formation in marine locations) and laboratory observations
(e.g., film growth rate, evolution of spatial distribution of T, P, SA, SG,
SH, gas and water consumption rate). However, major challenges still
exist: (i) the pore-scale behaviour due to the anisotropic nature of most
sandy porous media; (ii) the implementation of equilibrium model
against kinetic model describing the phase change behaviour; (iii) the
lack of knowledge on the kinetic rate parameters in different types of
porous media; (iv) the knowledge gap on Peq-Teq relationship con-
sidering the nucleation process (e.g. the metastability zone) and (v) the
Peq-Teq-X relationship for hydrate formation with different gas compo-
nents and inhibitor concentrations. Thus, further experimental studies
and validation between simulation prediction and experiments are
strongly needed.
4.2. Experimental studies on gas hydrate growth
Revisiting gas hydrate growth kinetic models has shown that most
of these models are mechanistic and phenomenological models, which
are directly derived from experimental observations and measurements.
Thus, to improve the predictability and applicability of these models,
gas hydrate formation experiments in laboratory play a vital role for
enhancing our understanding on the behaviour of gas hydrate growth.
Fig. 5 shows the various aspects to consider for the development of
hydrate growth model, namely (i) the experimental method to form gas
hydrate; (ii) the quantitation method for the rate of gas hydrate growth,
and (iii) the controlling mechanisms proposed for hydrate growth ki-
netic model.
Given the various types of hydrate-forming gas (e.g. CH4, C2H6,
C3H8, CO2 and their mixtures), together with the addition of various
thermodynamic and kinetic promoters and inhibitors (e.g. THF
[194–198], SDS [199–203], TBAB [204–207], cyclopentane [208–212],
and amino acid [213–217] etc.) that can enhance or inhibit the kinetics
of gas hydrate formation, a wide range of experiments could be de-
signed to investigate gas hydrates growth in laboratories. In addition,
the selection of hydrate reactor configuration (e.g. stirred tank reactor
[70,47,99,218,219], flow reactor [96,189,220,221], bubble/droplet
reactor [124,148,141,222], packed bed [98,173,223–225], capillary
tubing [104,226,227]) will affect the liquid-gas contact pattern and in
turn influence the heat flow, fluids flow and kinetic rate in the reactor
and flow lines. Furthermore, gas hydrate formation kinetic rate is also
dependent on the different types of porous medium employed (e.g.
sandy medium [75,78,224,228–230], silica gel [231–235], glass beads
[236–239], PU foam [240], metallic foam [241–243], hydrogels
[244–246] or nanoparticles [247–252]), where mass transfer rate and
fluids flow rate is altered. During gas hydrate formation in porous
medium, various formation techniques (e.g. excess-water method
[171–173], excess-gas method [75,169,253], dissolved-gas method
[174–177,237], ice-to-hydrate method [126,130,254–256]) are pro-
posed so far to synthesize gas hydrates in sediments mimicking natu-
rally occurring hydrate bearing sediments. However, the observed hy-
drate formation kinetic rates are largely dependent on the detailed
experimental procedures, the location and rate of cooling, the ther-
mophysical properties of the porous media. Different formation tech-
niques applied are very likely to result in unique formation kinetics and
may lead to spatially heterogeneous hydrate distribution inside the
reactor [223].
In addition to the experimental conditions that are critical to the
rate of hydrate growth, quantification of the growth rate of gas hydrate
is also paramount in the development of a kinetic model. It requires
continuous tracking on the gas hydrate film or the operating parameters
of the hydrate reactor, including T, P, thickness of film, radius of par-
ticle, saturation of phases at different time and length scales [257]. Gas
consumption is a common measure indicating the rate of hydrate
25
Chemical Engineering Journal 342 (2018) 9–29
growth in stirred tank and packed bed hydrate reactor. However, it only
reflects the overall growth rate from a bulk perspective. Whereas, hy-
drate nucleation and growth are exothermic surface reaction and may
be more prominent at the location of temperature sink and gas/liquid
interface with high mass transfer rate. Thus, measurement on gas up-
take rate augmented by phase saturation visualization or hydrate par-
ticle size measurements could reveal more information.
These recent techniques developed including X-ray computed to-
mography (CT) scan [181,223], magnetic resonance imaging (MRI) and
nuclear magnetic resonance (NMR) spectroscopy [224,258–263], atte-
nuated total reflection infrared (ATR-IR) spectroscopy [264,265] and
electrical resistivity tomography (ERT) [174,175,266,267] have de-
monstrated their capability in revealing more kinetic phenomena. In
addition, measurement on the thickness of hydrate film provides direct
visual evidence on the hydrate growth down to micron level. A number
of interfacial phenomena on the surface of gas-hydrate, liquid-hydrate
and gas-liquid-hydrate could be investigated extensively to elucidate its
growth kinetics [143,268,269,141]. A large body of research is carried
out worldwide focusing these perspectives of gas hydrate formation
behaviour in different laboratories. These valuable experimental data
sets and intriguing phenomena observed at multi-scale level are the
fundamental building blocks for the development of hydrate growth
kinetic models.
5. Conclusion
Over the past three decades, studies on the kinetic behaviour of gas
hydrate growth has made considerable progress in laboratories, which
has led to a number of hydrate growth kinetic models developed from
different chemical engineering perspectives, including mass transfer,
heat transfer, intrinsic kinetic reaction, surface chemistry and multi-
phase fluids flow. In summary, this review systematically examines
both the classical semi-empirical and analytical models, and the state-
of-the-art numerical models associated with the hydrate growth from
these perspectives. In addition, we provide future perspectives on both
modelling and experimental studies of the most intriguing behaviour of
gas hydrate growth. Despite the various models proposed, a unified
model is yet to be developed connecting all the physical behaviour
observed from different domains. This would require a combination of
multiscale physics in the model formulation. Models based on fitted
semi-empirical parameters can be more practical in the design of hy-
drate reactors for industrial application; however, these empirical
parameters must be examined carefully before application for scale-up
apparatus. Numerical modelling of hydrate formation in porous media
and flow lines can be powerful, but it still requires calibration and
validation from experimental and field data to instil its confidence in
the predication. We believe that the advancement of knowledge on gas
hydrate growth in laboratories and the development of next-generation
growth models will foster the application of hydrate-based technologies
to breakthrough from laboratories to industry.
Acknowledgement
The work was funded in part under the Energy Innovation Research
Programme (EIRP, Award No. NRF2015EWTEIRP002-002), admini-
strated by the Energy Market Authority (EMA), Singapore. Zhenyuan
Yin would like to thank Lloyd’s Register Global Technology Centre
(LRGTC) and Economic Development Board (EDB) for the industrial
postgraduate programme (IPP) scholarship.
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