Fuel 83 (2004) 21152121

www.fuelfirst.com

Effect of additives on formation of natural gas hydrate

C.S. Zhang, S.S. Fan*, D.Q. Liang, K.H. Guo
Guangzhou Center for Gas Hydrate Research, Guangzhou Institute of Energy Conversion, The Chinese Academy of Sciences,
No.1 Nengyuan Road, Wushan, Tianhe District, Guangzhou 510640, China
Available online on 2 July 2004

Abstract
The formation of natural gas hydrate (NGH) is studied in this work. Kinetics data of hydrate formation with no agitation were collected at
various concentrations of the aqueous solutions with different additives such as alkylpolyglucside, sodium dodecyl benzene sulfonate and
potassium oxalate monohydrate. Various kinds of additive increased the formation rates of NGH and its storage capacity and reduced the
induction time of NGH formation. Moreover, the storage capacity, the induction time and the hydrate formation rate were influenced by the
concentration of the aqueous solution.
q 2004 Elsevier Ltd. All rights reserved.
Keywords: Natural gas hydrate; Additive; Formation rate; Storage capacity; Induction time

1. Introduction Gas hydrate formation is generally divided into two

Gas hydrates (or clathrate hydrates) are ice-like non-
stoichiometric compounds formed when light gases such
as methane, ethane, come into contact with water at high
pressure and/or low temperatures. There are three main
crystallographic structures I (sI), II (sII), and H (sH),
which differ in cavity size and shape [1 6]. Gas hydrate
has high storage capacity, namely l m3 methane hydrates
contains about 170 m3 methane gas. As natural gas
hydrate (NGH) can be maintained at about 2 20 8C and
atmospheric pressure [7], there are increasing concerns on
NGH and necessities for the collection of experiment data.
The researches are undertaken from the viewpoint of not
only fundamental physical properties but also practical use
of them. For example, NGH as vehicle fuel has been
studied in America, Japan and Norway and is considered
as a feasible fuel [8]. Hydrate formation process can be
used as a method to separate or enrich certain gases (H2S
and O2, etc.) from gas mixtures [9 12] and to condense
aqueous solutions [13]. Recently, gas hydrate has drawn
much attention as a new means for natural gas (NG)
storage and as an alternate for safe transportation of NG
[14 16].
* Corresponding author. Tel.: 86-20-87057670; fax: 86-20-
87057365.
E-mail address: fanss@ms.giec.ac.cn (S.S. Fan).
0016-2361/$ - see front matter q 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2004.06.002
consecutive steps. The first step involves the nuclei
formation and the second step is growth process. Gas
dissolution, formation of nuclei and growth of new nucleus
are mainly affected by pressure and temperature conditions
of the system. In addition, the agitation of water increases
the water gas interfacial area and improves hydrate
formation [17 18]. Presently, some researchers applied
water spraying into a guest gas phase as a practical means
of rapid hydrate formation [19]. Among the techniques to
increase the hydrate formation rate and the storage capacity
of gas in the hydrate, the additives as a promoter were often
used. If an additive such as tetrahydrofuran is added to the
water/methane system, a hydrate of sII may form at a
pressure that is 30%, or even less, of the pressure required
for the formation of sI methane hydrate. However, the
methane storage capacity in the sII hydrate is estimated,
based on a statistical thermodynamic model, to be less than
60% of that of the sI methane hydrate [19]. Mostly liquid
hydrocarbons of large molecule such as 1,3-dimethylcy-
clohexane and methylcyclohexane, might be introduced to
methane/water system in order to lower the hydrate
formation pressure without reducing the storage capacity
of gas to a certain extent in the case of sH hydrate [3,5,19].
The pressure to form a sH hydrate is usually 30 80% of
that of the sI methane hydrate which depends on the
species of liquid hydrocarbons used as an additive [19].
2116 C.S. Zhang et al. / Fuel 83 (2004) 21152121
Nomenclature
M molecular weight of hydrate former gas
MH molecular weight of hydrate
n hydration number
Ni molecular fraction of ith hydrate former gas
component
p pressure
T temperature
VG molecular volume of gas
VGH volume of gas stored in a unit volume of hydrate
Vi specific volume of water in hydrate formed by
component i
Methane gas storage capacity in sH hydrate with 0.1 wt%
polyvinylpyrrolidone (PVP) as hydrate promoter was more
than without the presence of PVP (i.e. in the case of pure
water) at comparable concentration [5]. Some surfactants
including anionic surfactants (sodium dodecyl sulfate) and
biosurfactants (polysaccharide lipid complex, glycolipids,
lipoprotein lipopeptides, and phospholipides) were
reported to have effects on hydrate formation rate and
hydrate induction time [14,20 21]. However, the hydrate
formation data in non-ionic surfactant or non-surfactant
aqueous solutions are hardly reported in the literature.
The main objective of this paper is to study the influence
of additives such as alkylpolyglucoside (APG), sodium
dodecyl benzene sulfonate (SDBS) and potassium oxalate
monohydrate (POM), on hydrate formation rate, hydrate
induction time, storage capacity at a constant pressure,
4.50 ^ 0.01 MPa and a constant temperature,
275.4 ^ 0.1 K (i.e. constant water bath temperature) in a
quiescent system (without agitation). APG and SDBS used
in the experiments were non-ionic surfactant and anionic
surfactant, respectively. APG was chosen as a promoter of
hydrate formation for the following reasons: (1) it is a novel
surfactant with the characteristics of non-ionic and anionic
surfactant; (2) it is also a strong active nontoxic substance
and one of green-surfactants; (3) it is widely used in
various industries. SDBS was selected because it is a
representative and inexpensive surfactant. POM is neither
a non-ionic surfactant nor an anionic surfactant. It is a
colourless or off-white crystal powder and it is selected as an
additive for two reasons: (1) POM is a salt compound and
the salt solution with low concentrations may promote the
hydrate formation; (2) a chemical reaction formula in POM
aqueous solution is as follows:
VSGH volume of gas stored in a unit volume of hydrate
at standard conditions
Z compression factor
r density
Subscripts
0 standard conditions
i component of gas mixtures
G gas
GH gas in hydrates
H hydrate
SGH gas in hydrates at standard conditions
where [K] and [OH2] can make the formation of the
microcavities of a crystal lattice easier and facilitate the
hydrate formation because they are the frameworks up
which the hydrates can grow. At the same time, we pro-
posed that could become the template of hydrate
formation and was called as templating agent. So, POM can
provide the suitable environment for the formation of
hydrate.
2. Experimental
2.1. Apparatus
The experimental apparatus, as shown in Fig. 1, mainly
consists of a stainless-steel reactor, refrigeration system,
water bath, mass flow meter, and pressure regulator and
check valve. The reactor which is enclosed with insulation,
has a diameter of 2.50 cm and an effective volume of
23.60 cm3 and is designed to be operated at pressure up to
20 MPa and temperature in the range of 253.15
323.15 K. Water bath temperature, which is read by a PT-
100 thermocouple (within the refrigeration system) with an
accuracy of ^ 0.1 K, was kept constant by the refrigeration
system, thus the reactor temperature was regulated
indirectly. A platinum resistance thermocouple was used
to measure the solution temperature in the reactor, whose
accuracy is ^ 0.1 K. A pressure transducer within 0.01 MPa
in accuracy measured the pressure inside the reactor.
A pressure regulator can maintain constant pressure in
the reactor within 0.01 MPa. A model D07-11A mass flow
meter from Peking Jianzhong Instrument Inc. was used to
measure gas added into the reactor during NGH formation.
The flow meter has a capacity of 0 100 sccm (standard
cubic centimeter per minute), at an accuracy with ^ 1% of
full scale and a repeatability of within 0.2% of the flow rate.
There is a data collection to record the pressure and
temperature of the reactor and the flow rate of NG supplied
to the reactor.
 C.S. Zhang et al. / Fuel 83 (2004) 21152121 2117

Fig. 1. Schematic diagram of NGH formation apparatus.

2.2. Materials used and temperature is calculated by the expression [22]:

103 VG rH
The experiment materials in this work were presented in VGH 1
MH
Table 1. The additives were weighed on an electronic
balance with a readability of ^ 0.1 mg. Distilled water was The density of hydrate formed by gas mixtures is given
used in all experiments. The aqueous solutions of additives by the expression:
were weighed on an electronic balance with a readability of P
Ni Mi 18:02ni
^ 0.01 g. The composition of NG was analyzed by means of rH P 2
18:02Ni Vi ni
a model 6890 Hewlett-packard gas chromatography.
The molecular weight of hydrate MH is defined as
2.3. Procedure MH M 18:02n 3

Supplying 10.00 ^ 0.01 g aqueous solution, which The volume of gas stored in a unit volume of hydrate at
standard temperature and pressure conditions (STP) is
contained certain concentration of APG or SDBS or POM
defined by the equation:
aqueous solution, into the reactor commenced each
experimental run. The reactor was evacuated in advance. VGH pT0
VSGH 4
After the reactor was cooled to 275.4 ^ 0.1 K, NG was Zp0 T
delivered into the reactor, then the pressure was maintained
at 4.50 ^ 0.01 MPa.
Throughout each experimental run, the mass flow meter
3. Results and discussion
measured the rate of NG flowing into the reactor
continuously. Hydrate formation was followed by tempera-
3.1. Hydrate formation rate in pure water and aqueous
ture, pressure, and gas mass flows which were recorded and
solution of additives
displayed on a computer.
Fig. 2 shows a typical example of the data records of NG
2.4. Storage capacity of natural gas in hydrates supply in the respective experimentsan increase in the
total amount of NG supplied to the reactor over time after
The volume of gas stored in a unit volume of hydrate the hydrate formation. The time when the hydrate formation
at the hydrate formation conditions of pressure

Table 1
Experiment materials used in this work

Component Purity/composition Supplier

NG 83.92 wt% C1, Fushan Kede Gas Co.

8.65% C2, 7.43% C3
APG 98% Guangzhou Chemical
Reagent Co.
SDBS $98% Guangzhou Chemical
Reagent Co.
POM 99.8% Guangzhou Chemical
Reagent Co.
Water Distilled Fig. 2. Time evolution of NG supply (STP) into the reactor after the initial
hydrate formation.
2118 C.S. Zhang et al. / Fuel 83 (2004) 21152121
Fig. 3. Time evolution of storage process of NG (STP) in hydrate in
1000 ^ 1 ppm concentration.
was first recognized was determined by the flow meter
observations. There is an initial sharp increase in the flow
rate of NG through the flow meter when the hydrate starts to
form, which is considered as the origin of the time scale of
the hydrate formation. The slope of the plot in the figure
corresponds to the rate of hydrate formation, which was
found to be nearly constant up to 30 min after the start of
hydrate formation. The hydrate was steadily formed in
500 ^ 1 ppm SDBS aqueous solution.
The NGH formation rate curves against time in both cases
of pure water and additives aqueous solutions
(1000 ^ 1 ppm) are shown in Fig. 3. Fig. 3 does not include
any information on the variation of the induction period
before the hydrate formation that will be discussed later.
Storage capacity in the Y-axis means the NGs volume
formed NGH at STP per 1 cm3 hydrate volume in the reactor.
Fig. 3 illustrates that APG and POM have the same effect as
SDBS on the hydrate formation in 1000 ^ 1 ppm solutions.
They all could evidently increase the formation rate of gas
hydrate and the storage capacity. However, hydrate for-
mation was very slow in the system of pure water.
3.2. Effect of additives on storage capacity of NG in hydrate
Storage capacity of NG in hydrate is affected not only
by the kinds of additives but also the concentrations of
Table 2
Storage capacity of hydrate in SDBS solutions
Concentration (ppm) 0 200
Storage capacity in hydrate (vol/vol) 51.7 131.4
Terminal error of experiment (vol/vol) ^2.1 ^0.9
Table 3
Storage capacity of hydrate in APG solutions
Concentration (ppm) 0 200
Storage capacity in hydrate (vol/vol) 51.7 61.4
Terminal error of experiment (vol/vol) ^2.1 ^2.1
the aqueous solutions of additives when the reactor system
is maintained at constant temperature and pressure.
Tables 2 4 show the storage capacity of NG in hydrate in
SDBS, APG and POM solution systems as well as pure
water system, respectively. Table 2 reveals that the storage
capacity tends to decrease with the concentration of SDBS
solution. When the concentration was 200 ^ 1 ppm, the
storage capacity was 131.4 ^ 0.9 vol/vol, while
2000 ^ 1 ppm, only 97.3 ^ 0.9 vol/vol. The lower concen-
trations of SDBS solution might promote the hydrate
formation. The function of the storage capacity of APG on
hydrate formation is not the same as SDBS, as was seen
from Table 3. Higher concentrations of APG solution such
as 800 1200 ^ 1 ppm made the storage capacity of NG
higher. Though POM is not surfactant, its effect is nearly the
same as APG as the promoter of hydrate formation, as was
seen from Table 4. When POM concentration was
1000 ^ 1 ppm, the storage capacity of NGH was as much
as 137.2 ^ 0.9 vol/vol.
The additives of SDBS, APG and POM can increase the
storage capacity of NG in hydrate, compared to the storage
capacity 51.7 ^ 2.1 vol/vol in pure water system. It
illustrates that water in the reactor can change into hydrate
more in the presence of additives. Moreover, the concen-
trations of the aqueous solutions of additives have an effect
on the storage capacity. With regard to the possible
mechanism of hydrate formation with the presence of
sodium dodecyl sulfate (SDS), Zhong and Rogers proposed
that the hydrate formation rates depend on SDS concen-
tration and that the hydrates formed in a SDS micellar
solution were easily adsorbed onto a metal surface at the
gas water interface, which improves the initial rate of
hydrate formation until near the conversion of all free water
and thus most water changes into the hydrates [20].
However, they did not explain why the storage capacity of
hydrate also depend on the surfactant concentration. More-
over, some non-surfactant substances such as calcium
hypochlorite [23] also can improve the hydrate formation
(i.e. the hydrate formation rate and the storage capa-
city, etc.). Based on the authors actual knowledge,
400 600 800 1000 1600 2000
117.5 119.2 124.5 123.5 99.3 97.3
^0.6 ^0.9 ^0.6 ^0.6 ^0.6 ^0.9
400 600 800 1000 1200 1600
91.3 107.4 120.4 137.3 143.8 138.3
^1.8 ^2.1 ^2.4 ^1.5 ^0.9 ^1.5
 C.S. Zhang et al. / Fuel 83 (2004) 21152121
Table 4
Storage capacity of hydrate in POM solutions
Concentration (ppm) 0 200 500 1000 1500
Storage capacity 51.7 91.8 99.5 137.2 86.5
in hydrate (vol/vol)
Terminal error of ^2.1 ^2.1 ^0.9 ^0.9 ^1.2
experiment (vol/vol)
the mechanism of hydrate formation with the presence of
additive appears to be very complicated and cannot be fully
explained. But it may be affected by the molecular structure,
physical and chemical property of additive (especially non-
surfactant substance).
3.3. Effect of additives on hydrate formation rate
In order to study hydrate formation rate in the reactor, the
hydrate formation rate curves against reaction time as the
example of APG and SDBS were drawn in Figs. 4 and 5.
The hydrate formation rate was first large, and then became
smaller in every curve. Furthermore, in one or two places of
the curve, the hydrate formation rate increased and
decreased sharply.
Fig. 4 illustrates that the hydrate formation rate of
400 ^ 1 ppm APG solution reaches 4.98 (vol/vol)/min up
to 5.70 min after the start of hydrate formation and then
tends to decrease. When the hydration reaction is close to
end, the hydrate formation rate fluctuates a little. The curves
of hydrate formation rate against reaction time in 200, 600,
800 and 1000 ^ 1 ppm APG solutions are similar to the
curve of the hydrate formation rate against reaction time of
400 ppm APG solution. However, the maximum values of
the hydrate formation rate after the hydrate formation are
different, respectively, and the ranges of fluctuation of the
hydrate formation rate are unlike each other.
Fig. 5 illustrates that the hydrate formation rate of
200 ^ 1 ppm SDBS solution reaches 5.80 (vol/vol)/min up
to 4.00 min after the hydrate formation and then start
to decrease. From about 8.00 to 32.00 min after the
hydrate formation, the hydrate formation rate remains
Fig. 4. Relation between hydrate formation rate and reaction time in APG
aqueous solutions.
2119
2000
88.5
^0.9
Fig. 5. Relation between hydrate formation rate and reaction time in SDBS
aqueous solutions.
3.30 (vol/vol)/min or so and then starts to decrease after
32.00 min of the hydrate formation. The curves of the
hydrate formation rate against reaction time of others
concentration of SDBS solutions are similar to the curve of
the hydrate formation rate against reaction time in
200 ^ 1 ppm SDBS solution. However, the maximum
values of the hydrate formation rate after the hydrate
formation are different, respectively, and the ranges of
fluctuation of the hydrate formation rate from up to 10.00 to
30.00 min after the hydrate formation are unlike each other.
Figs. 4 and 5 show that the effect of SDBS system on the
hydrate formation rate is dissimilar to that of APG system.
First, the hydration reaction time in the APG solutions is
longer than that in the SDBS solutions as a whole and so the
average hydrate formation rate of SDBS system is less than
that of APG system. Second, the time range of the rapid
formation of the hydrate in SDBD system is usually from
10.00 to 30 min after the hydrate formation. However, the
time range of the rapid formation of the hydrate in APG
system is not very clear.
Figs. 4 and 5 also seem to show two stages of the hydrate
formation. This phenomenon may be explained from the
following discussion. There is an increase of hydrate
nucleus concentrations in the aqueous solutions at the end
of the nucleation phenomenon, especially at the gas water
interface, thus the hydrate nucleus grow into the hydrate
crystal when the size of the hydrate nucleus reach at or/and
exceed the critical size, which allows the initial high rate of
hydrate formation. As the hydrate formation goes on, the
bulk solution temperature increases, which results from the
reaction heat of hydrate formation. The difference between
the freezing point and the bulk aqueous solution temperature
for the hydrate crystal growth (in fact, the actual driving
force of the reaction is the difference between the solution
freezing point and the crystal surface temperature) [24]
starts to decrease and so the hydrate formation rate starts to
decrease accordingly. However, the conductive removal of
hydration reaction heats by the colder metal will contribute
to the higher rate of hydrate formation and thus the hydrate
formation rate increase again, which leads to the fluctuation
of the hydrate formation rate.
2120 C.S. Zhang et al. / Fuel 83 (2004) 21152121
Fig. 6. Relation between temperature of solution and reaction time in
1000 ^ 1 ppm concentration.
Fig. 6 shows the change of solution temperature as a
result of the reaction heat in hydrate formation process in
the presence of additives. The solution temperature changes
with the reaction time in 1000 ^ 1 ppm SDBS, APG and
POM solutions, it shows that the reaction heat is emitted
when the gas hydrate forms fast. When the heat cannot be
drove off with time at first, the solution temperature
increases rapidly. However, the solution temperature hardly
has any change in pure water system because the hydrate
formation rate is very slow. Figs. 4 6 also show that the
increase of the solution seems to be positive proportion with
the hydrate formation rate. But the increase of the solution
temperature in the hydration reaction system is not
beneficial to the fast formation of hydrate, seen from the
kinetics of hydrate formation. How to drive off the reaction
heat fast is a very important way to accelerate the hydrate
formation further in the system of additives.
3.4. Effect of additives on induction time of hydrate
formation
The induction time in this study is called as the time it
takes for the introduction of the gas to the initial formation
of hydrate. A series of experiments in the present work show
that the induction time of hydrate formation was greatly
shortened by the addition of additives. In the case of pure
water, the induction time was long as much as 2600 min.
Fig. 7 shows that at higher concentrations (800
1600 ^ 1 ppm), the aqueous solutions of APG formed
NGH very fast and the induction time was only 15 ^ 3 min
or so. However, for SDBS system, hydrate induction time
was very short (about 25 30 min) at 100 ^ 1 or
200 ^ 1 ppm concentration. Compared with APG and
SDBS, the induction time of hydrate formation in POM
solutions all were longer1000 min or so.
The three-run experiments for the solution with each
concentration were made. The shorter hydrate crystal
induction time and its good reproducibility in the additives
solutions were found. The results may be explained as the
following discuss. On one hand, the induction time may be
Fig. 7. Relation between induction time of hydrate formation and additives
concentration.
influenced by the molecular disorder of the hydrate reaction
system. The additives solution system with an appropriate
concentration is lower in the degree of molecular disorder
than one without any additives as a result of molecular
appetencies and the spatial sites of the hydrate nuclei appear
to be of uniformity. Moreover the degree of this appetency
and uniformity may be affected by the concentrations of
additives solution, which may lead to an effect of additive
concentration on the induction time of hydrate formation
that is reproductive at a certain concentration of additive.
On the other hand, the additives can promote the dissolution
of NG in the liquid phase prior to the hydrate formation
(about 200 450 cm3 NG at STP) and make the number of
gas molecules increase when there is a dynamic balance
between the gas and the liquid phase. The more the gas
molecules are in the liquid phase, the more opportunity they
have to collide and even combine with the cages formed by
hydrate bonded water molecules that facilitate the formation
of hydrate nuclei. As noted, the mechanism that the additive
concentration affects the induction time of hydrate for-
mation needs further detailed investigation.
4. Conclusions
In this work, the effects of small amount of additives on
the hydrate formation were determined and the answers to
some problems regarding rapid and abundant storage of NG
in hydrate were provided. By using the additivesAPG,
SDBS and POM, formation processes of gas hydrate were
improved: (1) NGH was formed rapidlyseveral 100 times
faster than without additives; (2) the induction time of NGH
formation was shortened greatlyshort as much as 15 min
in the aqueous solution in a quiescent system; (3) free water
trapped between hydrate particle is fully utilized to give
higher storage capacity and 87.2% of the maximum storage
capacity can be achieved within 2 or 3 h of hydrate
initiation; (4) the relations of hydrate formation rate,
hydrate storage capacity, hydrate formation induction time
with the concentrations of additives were given
quantitatively.
 C.S. Zhang et al. / Fuel 83 (2004) 21152121
Acknowledgements
The authors are grateful to the National Natural Science
Foundation of China for research grant 50176051 and the
Major State Basic Research Program Grant G2000026306.
References
[1] Sloan ED. Clathrate hydrates of natural gases, 2nd ed. New York:
Marcel Dekker; 1997.
[2] Ripmeester JA, Tse JS, Ratcliffe CI, Powell BM. A new clathrate
hydrate structure. Nature 1987;325:135 8.
[3] Ripmeester JA, Ratcliffe CI. 129Xe NMR studies of clathrate hydrate:
new guest for structure II and structure H. J Phys Chem 1990;94:
87736.
[4] Peter E. Clathrate hydrates. Ind Eng Chem Res 1993;32:1251 74.
[5] Khokhar AA, Gudmundsson JS, Sloan ED. Gas storage in structure H
hydrates. Fluid Phase Equilib 1998;151152:38392.
[6] Jager MD, De Deugd RM, Peters CJ, de Swaan A, Sloan ED.
Experimental determination and modeling of structure II hydrates in
mixtures of methane water 1,4-dioxane. Fluid Phase Equilib
1999;165:209 23.
[7] Gudmundsson JS, Borrehaug A. Frozen hydrate for transport of
natural gas. Second International Conference on NGH, Toulouse,
France; 1996. p. 41522.
[8] Fan SS, Guo TM. Natural gas hydrates as energy utilization and
natural gas vehicle. New Energy 1998;20(12):711.
[9] Yoshitaka Y, Takeshi K, Taro K, Yamamoto Y, Komai T, Kawamura
T, Yoon J, Kang S, Okita S. Studies on separation and purification of
guest component. Fourth International Conference on NGH, Japan;
2002. p. 42832.
[10] Ballard AL, Sloan ED. Hydrate separation processes for close-boiling
compounds. Fourth International Conference on NGH, Japan; 2002.
p. 1007 11.
[11] Taku O, Akihiro Y, Fumio K, Okano T, Yamasaki A, Kiyono F, Fujii M,
Yanagisawa Y. A novel separation process of hydro chlorofluorocarbons
2121
(HCFCs) and hydro fluorocarbons (HFCs) by using clathrate hydrate
formation. Fourth International Conference on NGH, Japan; 2002.
p. 101215.
[12] Chen GJ, Sun CY, Ma CF, Guo TM., A new technique for
separating (hydrogen methane) gas mixtures using hydrate
technology. Fourth International Conference on NGH, Japan;
2002. p. 1016 20.
[13] Ngan YT, Englezos P. Concentration of mechanical pulp mill
effluents and NaCl solutions through propane hydrate formation. Ind
Eng Chem Res 1996;35:1894 900.
[14] Rogers RE, Zhong Y. Feasibility of storing natural gas in hydrates
commercially. Second International Conference on NGH, Toulouse,
France; 1996. p. 843 72.
[15] Gudmundsson JS, Borrehaug A. Natural gas hydratean alternative
to liquefied natural gas. Pet Rev May 1996;2325.
[16] Yevi GY, Rogers RE. Storage of fuel in hydrates for natural gas
vehicles. J Energy Resour Technol 1996;118:209 13.
[17] Vysniauskas A, Bishnoi PR. A kinetics of ethane hydrate formation.
Chem Eng Sci 1983;38(7):1061 72.
[18] Narita H, Uchida T. Studies on formation/dissociation rates of
methane hydrates. Second International Conference on NGH,
Toulouse, France; 1996. p. 19197.
[19] Ohmura R, Kashiwazaki S, Shiota S, Tsuji H, Mori YH. Structure-I
and structure-H hydrate formation using water spraying. Energy Fuels
2002;16:1141 7.
[20] Zhong Y, Rogers RE. Surfactant effects on gas hydrate formation.
Chem Eng Sci 2000;55(19):417587.
[21] Rogers RE, Kothapalli C, Lee MS. Influence of microbes on gas
hydrate formation in porous media. Fourth International Conference
on NGH, Japan; 2002. p. 547 52.
[22] Makogon YF. Hydrates of hydrocarbons. Oklahoma: PennWell
Publishing Company; 1997.
[23] Guo YK, Fan SS, Guo KH, Chen Y. Methane storage via hydrate
formation using calcium hypochlorite as additives. J Chem Ind Eng
(China) 2002;53(5):452 3.
[24] Glew DN, Haggett ML. Kinetics of formation of ethylene oxide
hydrate. Part II. Incongruent solutions and discussion. Can J Chem
1968;46:3867 77.