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Effect of different surfactants on methane hydrate formation rate, stability

and storage capacity

Article in Fuel · February 2007

DOI: 10.1016/j.fuel.2006.07.032

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 Fuel 86 (2007) 434–441
www.fuelfirst.com

Effect of different surfactants on methane hydrate formation

rate, stability and storage capacity
H. Ganji a,b, M. Manteghian a,*, K. Sadaghiani zadeh b,
M.R. Omidkhah a, H. Rahimi Mofrad b
a
Department of Chemical Engineering, Faculty of Engineering, Tarbiat Modares University, Tehran, Iran
b
Department of Engineering and Development, Research Institute of Petroleum Industry, Tehran, Iran

Received 23 November 2005; received in revised form 20 July 2006; accepted 26 July 2006
Available online 8 September 2006

Abstract

The effects of anionic surfactants sodium dodecyl sulfate (SDS) and linear alkyl benzene sulfonate (LABS), cationic surfactant cetyl
trimethyl ammonium bromide (CTAB) and non-ionic surfactant ethoxylated nonylphenol (ENP) on the formation, dissociation and
storage capacity of methane hydrate have been investigated. Each surfactant was tested with 3 concentrations 300, 500 and 1000 ppm
and it has been found that SDS, when prepared with these three concentrations speeds up the hydrate formation rate effectively. LABS
increases the hydrate formation rate at 500 and 1000 ppm but decreases it at 300 ppm. CTAB and ENP have promotion effect on hydrate
formation rate at 1000 ppm but decrease it at 300 and 500 ppm. Hydrate stability tests have been performed at three temperatures 268.2,
270.2 and 272.2 K with and without surfactant promoters. The results show that all tested additives increase the dissociation rate of
methane hydrate below the ice point. CTAB has the minimum and LABS the maximum effect on the methane hydrate dissociation rate.
Experimental results on hydrate gas content revealed that maximum storage capacity of 165 V/V is obtained with 1000 ppm of CTAB in
water.
Ó 2006 Elsevier Ltd. All rights reserved.

Keywords: Gas hydrates; Surfactants; Formation rate

1. Introduction lize in 3 structures, I, II and H, depending on the nature

Natural gas hydrates are ice-like crystalline compounds,
formed from water and certain natural gas molecules at
appropriate pressures and temperatures. Molecules of
water, through hydrogen bonding, form a framework con-
taining relatively large cavities that can be occupied by the
guest molecules with favorable shapes and sizes. The
hydrate structure is thermodynamically stabilized through
non-bonded interaction between the encaged molecules
and the water lattice. These hydrates are known to crystal-
*
Corresponding author. Tel.: +982188011001; fax: +982188005040.
E-mail addresses: ganjih@ripi.ir (H. Ganji), manteghi@modares.ac.ir
(M. Manteghian).
and the size of the guest molecule [1,2].
After the discovery of hydrate self-preservation [3,4],
which allows hydrate to remain metastable at atmospheric
pressure and a few degrees below the ice point, scientists
have become interested in studying the storage and trans-
portation of gas in the form of hydrate. Research in this
area started at the beginning of 1990s by Gudmundsson
and his group at Norwegian University of Science and
Technology. This group and other researchers reported
results of production, storage and transportation of gas
hydrates investigations [5–10].
Slow formation rate of natural gas hydrate has been
considered to be a critical problem hindering the industrial
application of gas hydrates for storage and transportation
of natural gas. In recent years, researchers have reported

0016-2361/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2006.07.032
 H. Ganji et al. / Fuel 86 (2007) 434–441
the promotion effect of some additives on gas hydrate for-
mation and hydrate gas content [11–20].
Kalogerakis et al. [11] in investigating the inhibition
effect of surfactants on hydrate formation found that at
some concentrations these additives can promote the pro-
cess. Zhong and Rogers [12] reported that sodium dodecyl
sulfate (SDS), above its critical micelle concentration
(CMC), increases the rate of ethane hydrate formation in
a quiescent system by a factor greater than 700. They
found CMC of sodium dodecyl sulfate to be 242 ppm at
the hydrate formation condition. Han et al. [13] studied
sodium dodecyl sulfate effect on natural gas containing
90 wt% methane. They found that at a concentration of
300 ppm, there is a peak in the hydrate gas content. Gou
et al. [14] investigated the effect of calcium hypochlorite
on the methane hydrate formation rate and storage capac-
ity. Calcium hypochlorite reduced the induction time and
increased the hydrate gas content. Karaaslan et al. [15]
studied the effect of linear alkyl benzene sulfonic acid on
the formation rate of hydrates with structures I and II.
The research revealed that this compound increases the
rate of production of both types of hydrate, but its effect
on structure I is more significant. Sun et al. [16] studied
the effect of an anionic surfactant (sodium dodecyl sulfate),
a non-ionic surfactant (dodecyl polysaccharide glycoside)
and cyclopentane on the gas content of the hydrate formed
from natural gas containing 92 mol% methane. The effect
of the anionic surfactant was more pronounced compared
to the non-ionic surfactant. Cyclopentane reduced the
induction time but could not improve the storage capacity.
Sun et al. [17] obtained similar results for methane hydrate.
Gnanendran and Amin [18] used various concentrations of
para-toluene sulfonic acid as hydrate promoter and found
that its optimum concentration for hydrate formation is
3.5 g/l Link et al. [19] found that by addition of sodium
dodecyl sulfate, the gas content of methane hydrate could
reach 97% of the theoretical maximum value. Zhang
et al. [20] reported that alkylpolyglycuside, sodium dodecyl
benzene sulfonate and potassium oxalate monohydrate
increase the formation rate of natural gas hydrate and its
storage capacity.
Not only high formation rate and gas content of natural
gas hydrate are very important in commercializing the
technology of storage and transportation of gas hydrates,
but also the stability of the hydrate formed is vital for long
distance and period transportations. As mentioned above,
the effect of some additives on hydrate formation rate
and gas content has been investigated, but the stability of
the hydrate formed at the presence of such additives has
not been the subject of much investigation. An exception
is the work of Lin et al. [21], in which stability of methane
hydrate formed at the presence of SDS was studied and
compared with that of the pure methane hydrate. The
results showed that the presence of SDS increases the dis-
sociation rate of methane hydrate below the ice point.
In this study, formation and dissociation rates and stor-
age capacities of the hydrates formed in presence of 3 clas-
435
ses of surfactants (anionic, cationic and non-ionic) have
been studied. The aim has been to find an additive which
increases the hydrate formation rate and its storage capac-
ity followed by a prolonged stability of the product.
2. Experimental
2.1. Materials
Methane with purity of 99.9% was used to form hydrate
with de-ionized water. Surfactants used in the experiments
were: sodium dodecyl sulfate (Merck, Germany) with
chemical formula C12H25O4SNa, linear alkyl benzene sul-
fonate(RIPI, Iran) with chemical formula C18H30SO3Na,
cetyl trimethyl ammonium bromide (Merck, Germany)
with chemical formula C19H42BrN and 9 molar ethoxy-
lated nonylphenol (Hansa chemie, Germany) with chemical
formula C33H60O10.
2.2. Apparatus
The schematic diagram of the experimental apparatus
used is shown in Fig. 1. It consisted of a high-pressure reac-
tor with internal diameter of 6.2 cm, a height of 10 cm and
a total volume of 300 cm3. The reactor was equipped with a
four-bade mixer and could sustain a pressure of 13.8 MPa.
A thermocouple with a division scale of 0.1 K and a
pressure transducer with a division scale of 1 psi were
connected to the reactor to measure the temperature and
pressure. The reactor had some valves for injecting and
venting the gas. The reactor was placed into a water/ethyl-
ene glycol cooling medium and the temperature was
adjusted using a controllable circulator.
2.3. Procedure
2.3.1. Hydrate formation
The reactor was washed and rinsed with de-ionized
water. 75 cm3 aqueous solution of additive was charged
into the reactor for each experiment. The reactor was
purged with methane. Then it was pressurized with meth-
ane to 8.3 MPa at 298.2 K. After reaching equilibrium at
the initial temperature and pressure, the system was cooled
to the hydrate formation temperature (276.2 K). The mixer
8
5
4
7 6
1) 300 cm3 Reactor
2) Cooling bath
3 3) Gas cylinder
4) Stirrer
5) Sampling tube
6) Thermocouple
7) Pressure transducer
1 8) Vent
2
Fig. 1. Schematic diagram of the experimental apparatus.
436
was then started at a rate of 200 rpm to initiate hydrate
formation. The temperature and pressure were recorded
during hydrate formation. To obtain the amount of gas
consumed during hydrate formation, the following equa-
tion has been used:
n ¼ PV =ZRT
In which P, V and T are the gas pressure, volume, and tem-
perature respectively. R is the gas constant and Z is the
compressibility factor obtained from Peng Robinson equa-
tion of state.
When the system pressure reached to the 3-phase
equilibrium pressure at 276.2 K, the hydrate formation
stopped. At this point the gas valve was opened and the
system pressure was allowed to reach to 8.3 MPa and the
hydrate formation was repeated. When the system pressure
became constant at above its equilibrium point, the system
has been reached to its maximum conversion.
2.3.2. Hydrate dissociation
After hydrate formation was completed, the tempera-
ture was lowered to 268.2 K. The system was left for 10 h
for equilibrium. The vent valve was then opened and the
remaining gas was purged. The system was allowed to
remain at that temperature for 10 h for hydrate decompo-
sition while variation of pressure with time was recorded
and the amount of gas released from the hydrate was cal-
culated. The temperature was then raised to 270.2 K and
then to 272.2 K. At each temperature, dissociation of the
hydrate was studied for 10 h.
2.3.3. Hydrate storage capacity
After stability test at 272.2 K, the cell was allowed to
warm to room temperature, causing the hydrate to com-
pletely decompose and release its total entrapped methane.
The hydrate gas content was determined based on the max-
imum pressure inside the cell. The amount of methane
Pure water
0.6
0.5
Moles methane consumed
0.4
0.3
0.2
0.1
0
0 1
Fig. 2. Methane hydrate formation rate with and without SDS in 4.17 mol water.
H. Ganji et al. / Fuel 86 (2007) 434–441
entrapped was calculated and compared with the theoreti-
cal value to obtain the hydrate storage capacity.
In structure I, the theoretical ratio of water to gas in
hydrate is 5.75 mol/mol with all cavities filled with gas mol-
ecules. At this condition, each volume of hydrate contains
ð1Þ 180 volumes of gas at standard condition [1,22]. In these
experiments 75 g (4.17 mol) of water was used which can
encapsulate 0.725 mol (11.6 g) of methane theoretically.
3. Results and discussion
3.1. Hydrate formation rate
Two anionic surfactants (sodium dodecyl sulfate, SDS
and linear alkyl benzene sulfonate, LABS), a cationic sur-
factant (cetyl three methyl ammonium bromide, CTAB)
and a non-ionic surfactant (9 molar ethoxilated nonylphe-
nol, ENP) were selected and their promotion effect on
hydrate formation rate was investigated. The temperature,
initial pressure and stirrer speed were fixed at 276.2 K,
8.3 MPa and 200 rpm for each experiment, while 3 concen-
trations of 300, 500 and 1000 ppm were used for each sur-
factant. Variation of pressure with time was recorded and
related to the amount of gas consumed by Eq. (1). For
comparison, formation of methane hydrate from pure
water was also studied. Fig. 2 compares the rate of hydrate
formation at presence of SDS and pure water. At concen-
trations of 300, 500 and 1000 ppm, SDS increases the
hydrate formation rate effectively. As Fig. 2 shows, at
SDS concentration of 500 ppm hydrate formation rate is
maximized and the hydrate attains steady state in about
1 hour and the induction time is very short. At 300 ppm
the induction time is short similar to that of 500 ppm but
the formation rate is lower. At 1000 ppm induction time
is one hour and hydrate formation terminates in about 3 h.
In Fig. 3, effect of LABS on methane hydrate formation
rate has been shown and compared with that of pure water.
SDS (300 ppm) SDS (500 ppm) SDS (1000 ppm)
2 3 4 5
Time (hr)
 H. Ganji et al. / Fuel 86 (2007) 434–441 437

0.6 Pure water LABS (300 ppm) LABS (500 ppm) LABS (1000 ppm)

Moles methane consumed

0.5

0.4

0.3

0.2

0.1

0
0 2 4 6 8 10 12 14 16 18 20 22 24
Time (hr)
Fig. 3. Methane hydrate formation rate with and without LABS in 4.17 mol water.

It is revealed that at the concentration of 300 ppm, LABS
has inhibition effect on methane hydrate formation but at
500 and 1000 ppm it increases the rate of hydrate formation.
The promotion effect of LABS at 500 ppm is much lower
than the SDS effect and the induction time of hydrate forma-
tion is about 8 h while maximum conversion is reached after
24 h. At 1000 ppm, LABS promotion effect is comparable
with that of SDS at 500 ppm. Induction time is very
short and the hydrate attains steady state in about 2 h.
Similar graphs for CTAB and ENP (Figs. 4 and 5) indi-
cate that at 300 and 500 ppm these compounds lower the
hydrate formation rate but at 1000 ppm they slightly
increases the rate of hydrate formation. As Fig. 4 shows,
for 1000 ppm solution of CTAB the induction time is 18 h
and it takes 40 h for hydration to reach its completion. In
the case of ENP at 1000 ppm solution concentration, the
induction time is about 14 h and the completion time is 40 h.
The key function expected from a methane hydrate-pro-
moting agent is to improve the solubility of the hydrate
forming gas in water. It has been observed that above the
critical micelle concentration (CMC) of surfactants, the
solubility of methane increases while at surfactant concen-
trations below or around the CMC, the gas solubility
remains similar to that of pure water [18].
CMC of a surfactant solution by standard definition is
the concentration at which a sharp change in physical prop-
erties such as surface tension occurs [23]. Some hydrate
researchers have defined the CMC as the surfactant concen-
tration beyond which the induction time of hydrate forma-
tion is minimized [12]. CMC of a surfactant solution
depends on temperature, pressure and the nature of the
hydrate forming gas and may be well below the CMC mea-
sured by the standard method at atmospheric pressure and
room temperature. Zhong and Rogers [12] measured the
surface tension of SDS solutions with different concentra-
tions at the atmospheric pressure and ambient temperature
and a CMC of approximately 2725 ppm was obtained.
However at hydrate forming condition of ethane gas, they
measured the induction time of SDS solutions with different
concentrations and at a SDS concentration of 242 ppm a
significant change in induction time occurred which defines
the CMC at that hydrate condition.

Pure water CTAB (300 ppm) CTAB (500 ppm) CTAB (1000 ppm)
0.7
Moles methane consumed

0.6

0.5

0.4

0.3

0.2

0.1

0
0 5 10 15 20 25 30 35 40
Time (hr)
Fig. 4. Methane hydrate formation rate with and without CTAB in 4.17 mol water.
438 H. Ganji et al. / Fuel 86 (2007) 434–441

Pure water ENP (300 ppm)

0.7 ENP (500 ppm) ENP (1000 ppm)

0.6
Moles methane consumed
0.5

0.4

0.3

0.2

0.1

0
0 5 10 15 20 25 30 35 40 45
Time (hr)
Fig. 5. Methane hydrate formation rate with and without ENP in 4.17 mol water.

In our experiments with a SDS solution with a con-
centration of 300 ppm, methane hydrate formation rate
increased effectively showing that at methane hydrate con-
dition, 300 ppm is above SDS CMC concentration. In the
case of LABS, the CMC should be above 300 ppm at meth-
ane hydrate condition because at this concentration LABS
did not increase the hydrate formation rate or reduce the
induction time.
3.2. Hydrate dissociation rate
The hydrate formation experiments with and without
selected surfactants revealed their effect at various concen-
trations. Promotion effects were observed with SDS at
300, 500 and 1000 ppm, LABS at 500 and 1000 ppm,
CTAB and ENP at 1000 ppm. Fig. 6 compares the disso-
ciation pressure of hydrate formed with and without pro-
moters at temperatures 268.2 K, 270.2 K and 272.2 K.
Mole percentages of hydrate dissociated at these three
temperatures have been plotted in Fig. 7. For all hydrate
samples at each constant temperature, the maximum dis-
sociation rate occurs at the beginning of dissociation
stages and then the rate decreases. The finding may be
interpreted by considering two factors. Firstly a phenom-
enon called the self-preservation must be taken into
account. It is well established that during hydrate dissoci-
ation an ice layer forms around hydrate crystals that pre-
vents the hydrate from further dissociation [3,24,25].
Secondly, as dissociation takes place in a closed system,
the exit of methane results in an increase in the vessel
pressure. This pressure increase can then slow the rate
of hydrate dissociation.

Pure water SDS (300 ppm) SDS (500 ppm)

SDS (1000 ppm) LABS (500 ppm) LABS (1000 ppm)
3 CTAB (1000 ppm) ENP (1000 ppm) Temperature
Dissociation pressure (MPa)

2.5 272.2
Temperature (K)

2
270.2
1.5

1
268.2

0.5

0 266.2
0 5 10 15 20 25 30
Time (hr)
Fig. 6. Hydrate dissociation pressure profiles with and without promoters after 30 h at temperatures 268.2, 270.2 and 272.2 K.
 H. Ganji et al. / Fuel 86 (2007) 434–441 439

Pure water SDS (300 ppm) SDS (500 ppm)

SDS (1000 ppm) LABS (500 ppm) LABS (1000 ppm)
50 CTAB (1000 ppm) ENP (1000 ppm) Temperature

45
272.2
40
Dissociation (mol%)

Temperature (K)
35
30 270.2
25
20
15 268.2
10
5
0 266.2
0 5 10 15 20 25 30
Time (hr)
Fig. 7. Hydrate dissociation mole percentage profile with and without promoters after 30 h at temperatures 268.2, 270.2 and 272.2 K.

As Fig. 7 shows, all tested promoters increase the using stepwise temperature increase as discussed earlier.
hydrate dissociation rate below the ice point. Similar CTAB has the minimum effect on the hydrate stability
results have been reported by Lin et al. [21] for dissociation and when adding it at 1000 ppm, 11.9 mol% of hydrate dis-
of methane hydrate at the presence of SDS at 650 ppm. sociates after 30 h. The hydrate formed at the presence of
Two factors can be considered for increasing hydrate disso- LABS at the concentration of 1000 ppm has the maximum
ciation rate at the presence of surfactants: The first one is effect on the stability and 45.5 mol% of hydrate formed dis-
the finer size of hydrate particles formed at the presence sociates after 30 h.
of surfactants than pure water [21]. This leads to much lar- At 272.2 K the effect of SDS and CTAB on the hydrate
ger surface area and higher dissociation rate. The next fac- stability is higher than that obtained at 268.2 K. This
tor influencing dissociation rate is that the hydrate formed means that at higher temperatures the self-preservation
at presence of surfactants has higher gas content (Fig. 8). phenomenon of hydrate is affected more severely with these
Higher gas content means less stability and faster dissocia- surfactants. On the other hand, at higher temperature
tion. A similar finding was made by Giavarini [25] who (272.2 K), it is quite plausible that the addition of surfac-
investigated the dissociation rates of samples of methane tants could cause a decrease in the freezing point of the
hydrate and concluded that those with more gas/water solution, resulting in an inhibition of ice formation on
ratio dissociated more quickly. the hydrate outer surface (weakness of the hydrate self-
When dissociating hydrate formed with pure water (with- preservation property). In the case of ENP and LABS
out promoter), after 30 h, 7 mol% of hydrate dissociates the stability of hydrate is very low even at 268.2 K.

180

160

140
Storage capacity (V/V)

120
CTAB (1000 ppm)

ENP (1000 ppm)

SDS (500 ppm)

LABS (1000 ppm)

SDS (300 ppm)

SDS (1000 ppm)

100
LABS (500 ppm)

80

60
pure water

40

20

Fig. 8. Storage capacity of hydrate formed with and without promoters.

440 H. Ganji et al. / Fuel 86 (2007) 434–441
3.3. Hydrate storage capacity
Following the stability test at 272.2 K, the cell was
allowed to warm slowly to room temperature and the
hydrate released its total absorbed methane. The gas con-
tent of hydrate was determined using Eq. (1) based on
the maximum pressure by the released methane inside the
cell. As mentioned in section 2.3.3, when using 75 g of
water to obtain hydrate with structure I, the maximum the-
oretical amount of methane in hydrate is 0.725 mol and the
theoretical storage capacity of hydrate is 180 V/V at stan-
dard condition. Based on this theoretical value, the storage
capacity of hydrates formed with and without promoters
have been calculated and shown in Fig. 8. As this figure
shows, all surfactant promoters increase the storage capac-
ity of methane hydrate. Due to low solubility of gas in
water, hydrates are commonly formed at the interface of
water and gas in pure water system. Since methane hydrate
is less dense than water, hydrates cover the gas- water inter-
face blocking further conversion of water to hydrate even
when stirring is applied. Using surfactants the solubility
of the gas in water increases and finer hydrate particles
are formed with pure water. This causes a higher surface
area and therefore a higher mass transfer rate. On the other
hand, surfactants are anti-agglomerants that prevent
hydrate crystals to agglomerate causing less free water to
entrap between solid hydrates. The largest amount of stor-
age capacity observed was for CTAB at the concentration
of 1000 ppm (165 V/V). This value is 91.7% of the theoret-
ical maximum storage capacity.
4. Conclusion
The effect of anionic surfactants sodium dodecyl sulfate
(SDS) and linear alkyl benzene sulfonate (LABS), cationic
surfactant cetyl trimethyl ammonium bromide (CTAB)
and non-ionic surfactant 9 molar ethoxylated nonylphenol
(ENP) on the formation, stability below the ice point and
storage capacity of methane hydrate have been investigated
experimentally. Each surfactant was tested at 3 concentra-
tions of 300, 500 and 1000 ppm and the following conclu-
sions were obtained:
1. SDS at concentrations of 300, 500 and 1000 ppm
increased the methane hydrate formation rate
effectively.
2. Maximum promotion effect of SDS on methane
hydrate was observed at the concentration of
500 ppm.
3. LABS increased hydrate formation rate at 500 and
1000 ppm but decreased it at 300 ppm.
4. Maximum promotion effect of LABS was observed at
1000 ppm, which was comparable with that of SDS at
300 ppm.
5. CTAB increased the hydrate formation rate at
1000 ppm but did not have promotion effect at 300
and 500 ppm.
6. 2.3 mol% of hydrate formed with pure water (without
surfactants) dissociated after 10 h at 268.2 K.
7. All surfactants decreased the hydrate stability below
the ice point.
8. Minimum decrease in stability observed at the pres-
ence of CTAB at 1000 ppm and 4.24 mol% of hydrate
dissociated after 10 h at 268.2 K.
9. Maximum decrease in stability observed at the pres-
ence of LABS at 1000 ppm and 35.4 mol% of hydrate
dissociated after 10 h at 268.2 K.
10. Maximum gas storage capacity observed at the pres-
ence of CTAB (165 V/V at standard condition) that is
91.7% of the maximum theoretical value for structure
I. It should be emphasized that there is not much dif-
ference between CTAB and ENP in this respect.
As the final conclusion, among the surfactants tested,
SDS is the best one for utilizing methane hydrates for stor-
age and transportation of gas. This surfactant has the max-
imum promotion effect on hydrate production rate while
the stability of hydrate formed is satisfactory at 268.2 K
and hydrate storage capacity is high (about 155 V/V).
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