Journal of Natural Gas Science and Engineering 26 (2015) 587e594

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Journal of Natural Gas Science and Engineering

journal homepage: www.elsevier.com/locate/jngse

Investigation on the kinetics of methane and carbon dioxide hydrates

by using a modied kinetic model
Shahin Khosharay, Hadi Roosta, Farshad Varaminian*
School of Chemical, Gas and Petroleum Engineering, Semnan University, Semnan, Iran

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 22 March 2015
Received in revised form
17 June 2015
Accepted 18 June 2015
Available online 9 July 2015

In this work, the experimental and modeling investigations are conducted on the formation kinetics of
methane and carbon dioxide hydrates. First, the hydrate formation experiments are done under constant
temperature and volume conditions. The experiments are also conducted at 400, 600 and 800 rpm stirrer
speeds in the presence of pure water. Subsequently, a kinetic model based on the mass transfer restriction of the gas through the liquid lm of the gaseliquid interface has been applied for describing the
kinetics of hydrate formation. This kinetic model is expressed in terms of the mole fraction of hydrate
former in the gaseliquid interface. Also, in order to determine interfacial mole fraction of hydrate former,
the parachor model in terms of interfacial properties is applied. The results of this model have been
applied for analyzing the effects of different parameters on kinetics of hydrate formation.
2015 Elsevier B.V. All rights reserved.

Keywords:
Hydrate formation
Kinetics
Methane
Carbon dioxide

1. Introduction
In recent years, clathrate hydrates or gas hydrates have been an
intriguing area of research for industrial applications. These crystalline solid structures are inclusion compounds made up of water
molecules and certain guest molecules with suitable sizes under
favorable thermodynamic conditions (elevated pressures and/or
low temperatures). The guest molecules are surrounded by water
cavities formed due to hydrogen bonding between the molecules of
water. The van der Waals forces between the guest molecules and
the cavities of water lead to thermodynamically stable structure of
gas hydrate. The crystallographic structure of gas hydrate mainly
depends on the size of cavities and guest molecules. Structure I (sI),
structure II (sII) and structure H (sH) are the three most common
structures of gas hydrates (Torre' et al., 2012; Mohebbi et al., 2012).
Gas hydrate is capable of being used as an industrial way of
water desalination, cool-energy storage, natural-gas storage, gas
separation, etc (Okutani et al., 2008). It is known that the
successful application of gas hydrate for industrial purposes
mainly depends on the hydrate formation kinetics. On the other
hand, gas hydrate formation is one of the most complex and
stochastic processes; therefore, in order to study this process,
using a kinetic model is of importance. According to the driving

* Corresponding author.
E-mail address: fvaraminian@semnan.ac.ir (F. Varaminian).
http://dx.doi.org/10.1016/j.jngse.2015.06.043
1875-5100/ 2015 Elsevier B.V. All rights reserved.

forces applied for describing hydrate formation kinetics, such

as temperature difference (Varaminian, 2000), concentration
difference (Skovborg and Rasmussen, 1994) and fugacity difference (Englezos et al., 1987), etc, different kinetic models have
been utilized for modeling the hydrate formation kinetics, for
instance, semi-empirical model versus the rate of gas consumption (Vysniauskas and Bishnoi, 1983, 1985), the mass and heat
transfer models of hydrate formation (Varaminian, 2002; Clarke
and Bishnoi, 2005), the kinetic models versus hydrate growth
(Ribeiro and Lage, 2008) and the kinetic models in terms of non
equilibrium thermodynamics such as chemical afnity (Roosta
et al., 2013; Sey Mazraeno et al., 2013; ZareNezhad and
Varaminian, 2012; Mottahedin et al., 2011).
Various modeling and experimental efforts have already been
done in order to investigate the kinetics of hydrate formation
process. Monfort et al. (2000) conducted a complete experimental
investigation on the formation kinetics of ethane and propane
hydrates in an agitated and semi-batch cell. Furthermore, they suggested new correlations for evaluating the rate of hydrate crystal
growth. Sun et al. (2003) investigated on the hydrate formation rate
of R12 (CCl2F2) at the temperature of 277.1 K and the pressures of
0.24 MPa and 0.32 MPa in a circulating ow system. By using the
material balance, they developed a mathematical model for gas
consumption, average hydrate particle size and shading ratio. Jerbi
et al. (2010) studied the kinetics of carbon dioxide hydrate formation and dissociation in semi-batch agitated cell. They concluded that
the hydrate growth rate of CO2 hydrate was approximately

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S. Khosharay et al. / Journal of Natural Gas Science and Engineering 26 (2015) 587e594

1.8
1031% hydrate s1 at the stirring velocity of 450 rpm. This
investigation indicated that for their system, by using an isothermal
circulation loop, the kinetics of hydrate formation varied from
1.8
1031 to 1.8
103% hydrate s1. Tajima et al. (2010) conducted
the experimental and modeling investigation on the HFC 134a
hydrate formation kinetics in a static mixer. They found that the
hydrate formation rate was equal to the mass transfer rate of hydrate
shedding from the gas bubble. Furthermore, they determined the
kinetic constant of hydrate formation. Bergeron et al. (2010)
performed particle size distribution measurements for methane
hydrate formation in formation in a semi-batch stirred cell. They also
applied Bergeron and Servio (2008) model to estimate the reaction
rate constant for methane hydrate formation. Al-Otaibi et al. (2010)
obtained experimental data for the kinetics of pure methane and
ethane hydrates formation in a semi-batch and stirred cell. They also
used the particle size analyzer for their experiments. By using
experimental pressure, temperature, and particle size distribution,
they determine the kinetics of pure methane and ethane hydrates
formation. ZareNezhad and Varaminian (2012) used the chemical
afnity model for hydrate formation rate in the isothermal-isochoric
cell for different gas hydrates containing CH4 (methane), C2H6
(ethane), C3H8 (propane), CO2 (carbon dioxide) R-22 (hydrocholorouorocarbon-22) and Xe (xenone). Mohebbi et al. (2012)
conducted experimental and modeling study on methane hydrate
formation rate in a stirred cell. They also applied a mass transfer
model based on Skovborg and Rasmussen (1994) model.
In this work, the modeling and experimental studies are
conducted on the kinetics of methane and carbon dioxide hydrates
in a stirred cell under constant volume and temperature conditions.
Subsequently, the hydrate formation rate is described in terms of
mass transfer through gaseliquid interface so that the kinetic
model of Skovborg and Rasmussen (1994) is expressed according to
the concentration of hydrate former in the interface phase. In the
model of Skovborg and Rasmussen (1994), the interfacial mole
fraction of hydrate former was set equal to mole fraction (solubility)
of hydrate former in the bulk liquid phase which is not true.
Therefore, to improve the kinetic model of Skovborg and
Rasmussen (1994), the mole fraction of hydrate former in the
interface phase is computed by using the parachor model based on
the work of Tjahjono and Garland (2010) and the interfacial properties. It should be mentioned that this investigation is just valid
when gas hydrate forms in pure water.
2. Experimental
2.1. Materials
Methane and carbon dioxide are supplied by Technical Gas
Services. These two hydrate formers have purities about 99.99%.
The information of hydrate formers and water used in experiments
has been listed in Table 1.
2.2. Apparatus

The total capacity of the cell was 600 cm3. The hydrate formation cell
had a four-blade mixer. It was also capable of operating in the pressures ranged (0e100) bar and the temperatures ranged
(253.15e373.15) K. The mixture of (water ethylene glycol) was used
as a coolant which was circulated by using a circulation pump
through the jacket of the cell. This controllable circulator was utilized
for adjusting the temperature of the high pressure cell with the
accuracy of 0.1 K. A PT100 thermometer (Pro-Temp Controls, Santa
Ana, California, United States) that had an accuracy of 0.1 K was used
for measuring the temperature of the high pressure cell. Furthermore,
a BD-Sensors-Str.1 pressure transmitter that had an accuracy of
0.1 bar was used for measuring the pressure of high pressure cell.
The hydrate formation cell had a data acquisition system.
2.3. Experimental procedure
Prior to conducting any hydrate formation experiment, the high
pressure cell was rinsed with de-ionized water for two times. Then
the high pressure cell was evacuated with a vacuum pump. The high
pressure cell was charged with 300 cc of de-ionized water. Subsequently, at each specied temperature, the high pressure cell was
pressurized up to 5 bar under the equilibrium pressure of methane or
carbon dioxide hydrate formation. The constant temperature bath
was turned on. After the high pressure cell reached the constant
specied temperature, the high pressure cell was pressurized up to
the specied pressure. This specied pressure was selected between
the saturation pressure of the hydrate former (gas) and the equilibrium pressure of hydrate formation. The initial operational and
equilibrium conditions of hydrate formation are shown in Figs. 2 and
3 for methane and carbon dioxide hydrates, respectively. Then the
stirrer started to work at the specied speed and pressure of high
pressure cell was recorded during the hydrate formation process until
the pressure of high pressure cell reaches to equilibrium pressure of
hydrate formation. Similar to the work of (Li et al., 2009; Mohebbi
et al., 2012; Karimi et al., 2014), based on the pressure drop in the
cell and vapor phase, the amount of hydrate former (gas) consumed
during the formation process was computed by using Eq. (1):

PV
ZRT

nci no  ni


o

PV
ZRT


(1)
i

In Eq. (1), nci is the consumed moles of hydrate former, n0 is the

initial mole of hydrate former, ni is the mole of hydrate former at
any time, P is the pressure, T is the temperature, Z is the
compressibility factor, V is the volume of hydrate former and R is
the universal constant of gases. Subscripts o and i show the initial
condition and the condition at any time, respectively.
In this study, the VTSRK EOS (Lin et al., 2006) was applied for
computing compressibility factor of methane or carbon dioxide. In
the high pressure cell, as it is shown in Eq. (2), the rate of gas
consumption during hydrate formation is considered as the
difference between initial condition of hydrate former and the
condition of the hydrate former at any time.

In this work, as it is shown in Fig. 1, the kinetic experiments of

hydrate formation were done in the cylindrical and stainless steel cell.

Dn n0  ni

Dt
Dt


PV
ZRT


0

PV
ZRT

Dt

(2)

In Eq. (2), t is the time.

Table 1
Materials used for experiments.

3. The description of model

Component

Chemical
formula

Purity

Supplier

Carbon dioxide
Methane
Water

CO2
CH4
H2O

99.99%
99.99%
Deionized-distilled

Technical gas services

Technical gas services
Bahrezolal, Iran

3.1. Kinetic model

As it is mentioned in the introduction part, different driving
forces can be considered for hydrate formation process. In this

S. Khosharay et al. / Journal of Natural Gas Science and Engineering 26 (2015) 587e594

589

Fig. 1. Experimental hydrate formation apparatus.

Fig. 2. Initial operational and equilibrium conditions of methane hydrate.

Fig. 3. Initial operational and equilibrium conditions of carbon dioxide hydrate.

study, the modication of Skovborg and Rasmussen (1994) is

applied for modeling the hydrate formation kinetics. Based on the
concentration difference as a driving force, Skovborg and
Rasmussen (1994) proposed a model for kinetics of hydrate formation as follows:

dn
Kcw0 xint  xb
dt

(3)

In Eq. (3)

K kL Agl

(4)

In Eqs. (3) and (4), Ag1 is gaseliquid interface area, cw0 shows
the initial concentration of water, xint indicates the interfacial liquid
mole fraction of the hydrate former at given pressure and
temperature, xb is bulk liquid mole fraction of the hydrate former at
equilibrium condition of hydrate formation. kL and K are the mass
transfer coefcient and kinetic constants, respectively.

In fact, Skovborg and Rasmussen (1994) considered the entire

hydrate kinetics as a mass transfer restriction of the hydrate former
through the liquid lm of the gaseliquid interface. In previous
modeling investigations, in which the Skovborg and Rasmussen
(1994) model was used, the interfacial liquid mole fraction of the
hydrate former at given pressure and temperature was set equal to
mole fraction (solubility) of hydrate former in the bulk liquid phase
at given pressure and temperature. Therefore, the following
method (see Fig. 4) was used for calculation of kinetic constant. As
it is shown in Fig. 4, rst, according to the operating temperature of
hydrate formation, the equilibrium pressure of hydrate formation
should be calculated. Subsequently, at each operating temperature
and pressure, the solubility of hydrate former in liquid water phase
should be calculated, so the kinetic constant of hydrate formation
can be determined based on experimental pressures and operating
temperature.

590

S. Khosharay et al. / Journal of Natural Gas Science and Engineering 26 (2015) 587e594

Fig. 4. Calculation method for Skovborg and Rasmussen (1994) model.

On the other hand, for (water gas) systems, the results of

several investigations (Li et al., 2008; Latte et al., 2010; Miqueu
et al., 2011; Khosharay et al., 2014; Khosharay and Varaminian,
2014) show the enrichment of gases at the wateregas interface
which describes the adsorption of gas molecules at the wateregas
interface. This proves that the interfacial mole fraction of hydrate
former is different from fraction (solubility) of hydrate former in
the bulk liquid phase. So, the simplications of previous model of
Skovborg and Rasmussen (1994) in which it was assumed that the
interfacial liquid mole fraction of the hydrate former was set equal
to mole fraction (solubility) of hydrate former in the bulk liquid
phase is not true. In this investigation, the interfacial mole fraction
of the hydrate former (gas) at given pressure and temperature is
computed based on the experimental surface tensions of
(water gas) system at given pressure and temperature. Therefore,
in this study, by calculating the interfacial mole fraction of hydrate
former on the basis of the surface tension of water/gas system, the
previous model of Skovborg and Rasmussen (1994) is improved. To
achieve this aim, the parachor method based on the work of
(Tjahjono and Garland, 2010) is used. In this investigation, the
method described in Fig. 5 is applied for modeling the kinetics of
hydrate formation. One can see in Fig. 5 that the equilibrium conditions of hydrate formation should be determined. For each
operating temperature and pressure, according to the surface tension of water/gas system at each operating temperature and pressure and the applied parachor method, the interfacial mole fraction
of hydrate former can be calculated so that the kinetic constant of
hydrate formation can be determined based on experimental
pressures and operating temperature and the surface tension of
water/gas system at each operating temperature and pressure. The
suggested model can be expressed as follows:



dn
eq
Kcw0 xint  xint
dt

Fig. 5. Calculation method for the present model.

rst point contains the operating temperature (T) and pressure (Pi).
The second point contains the operating pressure (Pi) and temperature corresponding to the equilibrium temperature for operating pressure (Teq). In fact, the driving force is computed by using
Eq. (6).


eq 
force xint T; Pi  xint Teq ; Pi

Driving

3.2. Parachor model

It is known that hydrostatic pressure changes the surface
tension of (gas water) system because of enrichment of the
interface with the gas molecules. On the other hand, Tjahjono and
Garland (2010) proposed a parachor model (Ashrazadeh and
Ameri Ghasrodashti, 2011; Ayirala and Rao, 2004; Ayirala et al.,
2006; Rao and Ayirala, 2006) in terms of surface properties for
calculating the composition of liquid mixtures in the surface phase.
In this investigation, the same equation is applied for computing
the composition of surface phase.
1

g4 rS

Psi xSi

(7)

In Eq. (7), S shows surface phase, g is the surface tension, Ps is

the parachor and r is the mole density.

(5)

In Eq. (5), xint shows the interfacial mole fraction of the hydrate
eq
former (gas) at given pressure and temperature and xint is the
interfacial mole fraction of the hydrate former at equilibrium conditions (equilibrium pressure and temperature) of hydrate formation. In this study, xint is considered at operating temperature (T)
and pressures between the initial and equilibrium pressure (Peq)
and xeq
is considered at Pi and the corresponding equilibrium
int
temperature (Teq) of Pi. These conditions are shown in Fig. 6. It can
be seen in Fig. 6 that for each operating condition, the interfacial
mole fraction of the hydrate former is calculated for two points: The

(6)

Fig. 6. The hydrate formation conditions and driving force.

S. Khosharay et al. / Journal of Natural Gas Science and Engineering 26 (2015) 587e594

In order to compute the surface composition by using Eq. (7),

the mole density of surface phase (rS ) must be related to the surface
composition (xSi ). One way to achieve this aim is to use an appropriate equation of state (Eq. (8)). In this work, the CPA EOS is
applied for this aim. All the constants and binary interaction parameters of CPA EOS are given from the work of Abolala and
Varaminian (2013).


n o
P f T; rS ; xSi

(8)

As it is shown in Eq. (9), the sum of the surface mole fractions of

components is also equal to unity.

xS1 xS2 1

(9)

The required information of this calculation is the parachors of

pure components and surface tension of (water gas) system. The
parachors of pure components (see Table 2) are computed based on
the work of Quayle (1953). By using the NewtoneRaphson method,
the set of equations (Eqs. (7)e(9)) are simultaneously solved and
the surface mole fractions of components are found.

4. Results and discussion

591

of model are presented in Table 3 and Figs. 7 and 8. Fig. 7 shows the
consumed mole of carbon dioxide versus time for carbon dioxide
hydrate at 277.15 K, initial pressure of 21.9 bar and 800 rpm stirring
rate and compares the experimental data and the results of the
model. Also, the consumed mole of methane versus time for
methane hydrate at 275.15 K, initial pressure of 54.2 bar and
800 rpm stirring rate is presented in Fig. 8. As it is mentioned in
previous part, in order to apply the present model for the kinetics of
hydrate formation, the interfacial composition of hydrate former is
needed. Table 4 shows a sample of surface tensions of water/
methane and water/carbon dioxide for different pressures and
temperatures. A sample of calculation based on parachor model has
been reported in Table 5 for methane/water and carbon dioxide/
water systems.
The experimental surface tensions of methane/water and
carbon dioxide/water systems are given from (Jho et al., 1978; Peng
et al., 2009) and (Chun and Wilkinson, 1995), respectively. For some
pressure and temperatures, no experimental surface tension exists.
In order to overcome this problem, the model in the work of
Khosharay and Varaminian (2014) has been applied to determine
the surface tension. Furthermore, the solubility of methane and
carbon dioxide in water has been calculated by using the ash
calculations (Michelsen and Mollerup, 2004). The equilibrium
conditions of methane and carbon dioxide hydrate formation are

In the presence of pure water, the experiments of hydrate formation are conducted at the temperature of 275.15 K for methane
hydrate and two different temperatures of 275.15 K and 277.15 K for
carbon dioxide hydrate. The initial pressure range of methane
hydrate formation is (48.4e58.8) bar. Also, the hydrate formation
experiments for carbon dioxide are conducted at the pressures
ranged (21.9e34.2) bar. Furthermore, these experiments are
conducted at 400, 600 and 800 rpm stirrer speeds. Also, in order to
make sure the experiments were correct and they could be
repeated, each experiment was done for three times. The experimental conditions of the experiments are presented in Table 3.
The pressure and temperature variations of high pressure cell in
terms of time are measured and shown on a computer. The results

Table 2
Parachors of the applied uids.
Fluid

Parachor

Water
Methane
Carbon dioxide

54.2
73.2
91.2

Fig. 7. Consumed mole of carbon dioxide versus time for carbon dioxide hydrate at
277.15 K, initial pressure of 21.9 bar and 800 rpm stirring rate.

Table 3
The operational conditions of hydrate formation experiments and results of kinetic model.
Hydrate former

Temperature (K)

Initial pressure (bar)

Stirrer speed (rpm)

K*108

Methane
Methane
Methane
Methane
Methane
Carbon dioxide
Carbon dioxide
Carbon dioxide
Carbon dioxide
Carbon dioxide
Carbon dioxide
Carbon dioxide
Carbon dioxide
Carbon dioxide
Carbon dioxide
Carbon dioxide
Carbon dioxide

275.15
275.15
275.15
275.15
275.15
275.15
275.15
275.15
275.15
275.15
275.15
277.15
277.15
277.15
277.15
277.15
277.15

48.4
48.4
48.4
54.2
58.8
21.9
21.9
21.9
24.0
28.2
33.0
25.8
25.8
25.8
28.0
31.3
34.2

400
600
800
800
800
400
600
800
800
800
800
400
600
800
800
800
800

0.3345
2.753
5.678
6.356
7.835
9.4604
30.306
43.662
44.386
46.861
48.581
3.602
15.089
20.879
23.454
24.234
25.992

592

S. Khosharay et al. / Journal of Natural Gas Science and Engineering 26 (2015) 587e594

Fig. 8. Consumed mole of methane versus time for methane hydrate at 275.15 K, initial
pressure of 54.2 bar and 800 rpm stirring rate.

given from (Nakamura et al., 2003; Vlahakis et al., 1972). Although

the experimental surface compositions are not available in literature, one can see in Table 5 that the mole fractions of hydrate
formers (methane and carbon dioxide) in gaseliquid interface are
greater than their mole fraction in the bulk liquid phase. These
results show the hydrate formers (methane and carbon dioxide) are
preferentially adsorbed in the interface so that the compositions of
hydrate formers (methane and carbon dioxide) in the bulk liquid

phase and interface are different. As it has been mentioned in

previous part, for (water/gas) systems, the results of gradient theory in several investigations (Li et al., 2008; Latte et al., 2010;
Miqueu et al., 2011; Khosharay et al., 2014; Khosharay and
Varaminian, 2014) prove the enrichment of gases at the wateregas interface which conrms the results of the present model.
The results of model in Table 3 show that kinetic constants of
carbon dioxide hydrate is greater than the ones for methane hydrate; therefore, carbon dioxide hydrate shows higher formation
rate than the methane hydrate. The higher formation rate for
carbon dioxide hydrate could be attributed to the lower surface
tensions of carbon dioxide/water system (see Table 4). When the
surface tension value is lower, the interaction among water molecules in gaseliquid interface is weaker and subsequently the
gas-uptake rate is higher (the mass transfer resistance in
gaseliquid interface is lower). On the other hand, as it is seen in
Table 5, the interfacial mole fractions of carbon dioxide are higher
than methane. The higher mole fraction of carbon dioxide in the
interface leads to higher driving force of hydrate formation so that
the carbon dioxide hydrate forms at higher rates. Also, the results of
modeling shows that increase in initial pressure leads to higher
hydrate formation rate for both methane and carbon dioxide
hydrates. At the pressures and temperatures applied this study and
constant temperature, as it is shown in Table 4, the surface tension
of water/gas systems decreases if the pressure increases. So, the
interaction of interfacial water molecules is weaker and absorption
of the gas in the interface is higher. Therefore, according to these
explanations, the gas uptake rate, driving force and subsequently

Table 4
Sample of surface tensions of water/methane and water/carbon dioxide for different pressures and temperatures.
System

Operating
temperature (K)

Operating
pressure (bar)

Corresponding equilibrium
temperature (K)

Surface tension at
operating condition (mN/m)

Surface tension at equilibrium

condition (mN/m)

Methane
Methane
Methane
Methane
Methane
Methane
Carbon dioxide
Carbon dioxide
Carbon dioxide
Carbon dioxide
Carbon dioxide
Carbon dioxide
Carbon dioxide
Carbon dioxide

275.15
275.15
275.15
275.15
275.15
275.15
275.15
275.15
275.15
275.15
275.15
275.15
275.15
275.15

58.8
53.1
47.9
43.3
35.5
32.2
21.9
21.37
21.03
19.51
18.48
17.17
16.13
15.1

281.24
280.24
279.23
278.24
276.22
275.25
278.2
277.8
277.6
277.2
276.5
276.2
275.4
275

65.66
67.99
69.00
70.05
71.32
72.36
59.34
60.04
60.95
61.34
62.67
63.44
64.33
65.51

65.26
67.55
68.96
69.95
71.25
72.36
60.67
60.75
61.88
62.05
63.45
64.08
65.00
66.39

Table 5
Sample of required calculations for the kinetic model.
Hydrate former

Operating
temperature (K)

Operating
pressure (bar)

Corresponding
equilibrium
temperature

x in bulk liquid
at operating
condition

x in bulk liquid
at equilibrium
condition

xint at operating
condition

xint at
equilibrium
condition

Deriving
force

Methane
Methane
Methane
Methane
Methane
Methane
Carbon dioxide
Carbon dioxide
Carbon dioxide
Carbon dioxide
Carbon dioxide
Carbon dioxide
Carbon dioxide
Carbon dioxide

275.15
275.15
275.15
275.15
275.15
275.15
275.15
275.15
275.15
275.15
275.15
275.15
275.15
275.15

58.8
53.1
47.9
43.3
35.5
32.2
21.9
21.37
21.03
19.51
18.48
17.17
16.13
15.1

281.24
280.24
279.23
278.24
276.22
275.25
278.2
277.8
277.6
277.2
276.5
276.2
275.4
275

0.00371
0.00344
0.00313
0.00288
0.00243
0.00223
0.0195
0.0191
0.0189
0.0175
0.0167
0.0155
0.0146
0.0137

0.00310
0.00293
0.00277
0.00262
0.00235
0.00223
0.0180
0.0178
0.0176
0.0166
0.0161
0.0151
0.0145
0.0137

0.0913
0.0805
0.0759
0.0711
0.0654
0.0609
0.3175
0.3086
0.2973
0.2922
0.2757
0.2662
0.2553
0.2412

0.0868
0.0763
0.072
0.0682
0.0647
0.0609
0.29
0.2904
0.2797
0.2763
0.2617
0.2549
0.2466
0.2412

0.0045
0.0042
0.0039
0.0029
0.0007
0
0.0275
0.0182
0.0176
0.0159
0.014
0.0113
0.0087
0

S. Khosharay et al. / Journal of Natural Gas Science and Engineering 26 (2015) 587e594

the hydrate formation rate are higher. The results of calculations in

Table 5 conrm these explanations. As it is concluded, the mole
fraction of gas at gaseliquid interface is higher than its mole fraction in the bulk liquid phase, so gas hydrate tends to form at the
vaporewater interface when the stirring speed is low or the system
is quiescent. Hydrate formation at the gaseliquid interface forms a
layer on the top of the water phase and hinders further conversion
of water to gas hydrate and water is occluded. Increasing stirrer
speed or high stirring speed ripples the gaseliquid interface and
increases the surface area at gaseliquid interface, so it reduces
occluded water and increases the hydrate formation rate.
5. Conclusions
In this work, the experimental and modeling studies of hydrate
formation kinetics were conducted for methane and carbon dioxide
hydrates. Also, these investigations were done at stirring rates of
400, 600 and 800 rpm. The constant volume experiments of
methane and carbon dioxide hydrates were conducted at the
temperatures of 275.15 K and 277.15 K and pressures ranged
(21.9e34.2) bar and (48.4e58.8) bar for carbon dioxide and
methane hydrates, respectively. In order to model the kinetics of
hydrate formation, the kinetic model based on interfacial concentration of hydrate former is applied. The interfacial concentration of
hydrate former was also computed by using parachor model. The
results of the present model were used for analyzing the effects of
different parameters on kinetics of hydrate formation.
Acknowledgments
This research has been supported by the Semnan Gas Province
Company. The authors would like to owe great thanks to the
Semnan Gas Province Company for nancial support of this
investigation.
Nomenclature
Ag1
c
kL
K
n
P
R
t
T
V
x
Z

gaseliquid interface area

concentration
mass transfer coefcient
kinetic constant
mole
pressure
ideal gas constant
time
temperature
volume
mole fraction
compressibility factor

Greek letters
interfacial tension
mole density

g
r

Subscripts
eq
equilibrium
i
components i
S
surface
, II
coexisting phases I and II
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