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Journal of Natural Gas Science and Engineering 26 (2015) 587-594 PDF
Journal of Natural Gas Science and Engineering 26 (2015) 587-594 PDF
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.
588
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
Dn n0 ni
Dt
Dt
PV
ZRT
0
PV
ZRT
Dt
(2)
Component
Chemical
formula
Purity
Supplier
Carbon dioxide
Methane
Water
CO2
CH4
H2O
99.99%
99.99%
Deionized-distilled
S. Khosharay et al. / Journal of Natural Gas Science and Engineering 26 (2015) 587e594
589
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.
590
S. Khosharay et al. / Journal of Natural Gas Science and Engineering 26 (2015) 587e594
dn
eq
Kcw0 xint xint
dt
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
g4 rS
Psi xSi
(7)
(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)
S. Khosharay et al. / Journal of Natural Gas Science and Engineering 26 (2015) 587e594
n o
P f T; rS ; xSi
(8)
xS1 xS2 1
(9)
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)
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.
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)
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
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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