Fuel 83 (2004) 21152121

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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

consecutive steps. The first step involves the nuclei
Gas hydrates (or clathrate hydrates) are ice-like non- formation and the second step is growth process. Gas
stoichiometric compounds formed when light gases such dissolution, formation of nuclei and growth of new nucleus
as methane, ethane, come into contact with water at high are mainly affected by pressure and temperature conditions
pressure and/or low temperatures. There are three main of the system. In addition, the agitation of water increases
crystallographic structures I (sI), II (sII), and H (sH), the water gas interfacial area and improves hydrate
which differ in cavity size and shape [1 6]. Gas hydrate formation [17 18]. Presently, some researchers applied
has high storage capacity, namely l m3 methane hydrates water spraying into a guest gas phase as a practical means
contains about 170 m3 methane gas. As natural gas of rapid hydrate formation [19]. Among the techniques to
hydrate (NGH) can be maintained at about 2 20 8C and increase the hydrate formation rate and the storage capacity
atmospheric pressure [7], there are increasing concerns on of gas in the hydrate, the additives as a promoter were often
NGH and necessities for the collection of experiment data. used. If an additive such as tetrahydrofuran is added to the
The researches are undertaken from the viewpoint of not water/methane system, a hydrate of sII may form at a
only fundamental physical properties but also practical use pressure that is 30%, or even less, of the pressure required
of them. For example, NGH as vehicle fuel has been for the formation of sI methane hydrate. However, the
studied in America, Japan and Norway and is considered methane storage capacity in the sII hydrate is estimated,
as a feasible fuel [8]. Hydrate formation process can be based on a statistical thermodynamic model, to be less than
used as a method to separate or enrich certain gases (H2S 60% of that of the sI methane hydrate [19]. Mostly liquid
and O2, etc.) from gas mixtures [9 12] and to condense hydrocarbons of large molecule such as 1,3-dimethylcy-
aqueous solutions [13]. Recently, gas hydrate has drawn
clohexane and methylcyclohexane, might be introduced to
much attention as a new means for natural gas (NG)
methane/water system in order to lower the hydrate
storage and as an alternate for safe transportation of NG
formation pressure without reducing the storage capacity
[14 16].
of gas to a certain extent in the case of sH hydrate [3,5,19].
* Corresponding author. Tel.: 86-20-87057670; fax: 86-20- The pressure to form a sH hydrate is usually 30 80% of
87057365. that of the sI methane hydrate which depends on the
E-mail address: fanss@ms.giec.ac.cn (S.S. Fan). species of liquid hydrocarbons used as an additive [19].
0016-2361/$ - see front matter q 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2004.06.002
2116 C.S. Zhang et al. / Fuel 83 (2004) 21152121

Nomenclature VSGH volume of gas stored in a unit volume of hydrate

at standard conditions
M molecular weight of hydrate former gas
Z compression factor
MH molecular weight of hydrate
r density
n hydration number
Ni molecular fraction of ith hydrate former gas
component Subscripts
p pressure 0 standard conditions
T temperature i component of gas mixtures
VG molecular volume of gas G gas
VGH volume of gas stored in a unit volume of hydrate GH gas in hydrates
Vi specific volume of water in hydrate formed by H hydrate
component i SGH gas in hydrates at standard conditions

Methane gas storage capacity in sH hydrate with 0.1 wt% where [K] and [OH2] can make the formation of the
polyvinylpyrrolidone (PVP) as hydrate promoter was more microcavities of a crystal lattice easier and facilitate the
than without the presence of PVP (i.e. in the case of pure hydrate formation because they are the frameworks up
water) at comparable concentration [5]. Some surfactants which the hydrates can grow. At the same time, we pro-
including anionic surfactants (sodium dodecyl sulfate) and
posed that could become the template of hydrate
biosurfactants (polysaccharide lipid complex, glycolipids,
lipoprotein lipopeptides, and phospholipides) were formation and was called as templating agent. So, POM can
reported to have effects on hydrate formation rate and provide the suitable environment for the formation of
hydrate induction time [14,20 21]. However, the hydrate 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 2. Experimental
of additives such as alkylpolyglucoside (APG), sodium
dodecyl benzene sulfonate (SDBS) and potassium oxalate 2.1. Apparatus
monohydrate (POM), on hydrate formation rate, hydrate
induction time, storage capacity at a constant pressure, The experimental apparatus, as shown in Fig. 1, mainly
4.50 ^ 0.01 MPa and a constant temperature, consists of a stainless-steel reactor, refrigeration system,
275.4 ^ 0.1 K (i.e. constant water bath temperature) in a water bath, mass flow meter, and pressure regulator and
quiescent system (without agitation). APG and SDBS used check valve. The reactor which is enclosed with insulation,
in the experiments were non-ionic surfactant and anionic has a diameter of 2.50 cm and an effective volume of
surfactant, respectively. APG was chosen as a promoter of 23.60 cm3 and is designed to be operated at pressure up to
hydrate formation for the following reasons: (1) it is a novel 20 MPa and temperature in the range of 253.15
surfactant with the characteristics of non-ionic and anionic 323.15 K. Water bath temperature, which is read by a PT-
surfactant; (2) it is also a strong active nontoxic substance 100 thermocouple (within the refrigeration system) with an
and one of green-surfactants; (3) it is widely used in accuracy of ^ 0.1 K, was kept constant by the refrigeration
various industries. SDBS was selected because it is a system, thus the reactor temperature was regulated
indirectly. A platinum resistance thermocouple was used
representative and inexpensive surfactant. POM is neither
to measure the solution temperature in the reactor, whose
a non-ionic surfactant nor an anionic surfactant. It is a
accuracy is ^ 0.1 K. A pressure transducer within 0.01 MPa
colourless or off-white crystal powder and it is selected as an
in accuracy measured the pressure inside the reactor.
additive for two reasons: (1) POM is a salt compound and
A pressure regulator can maintain constant pressure in
the salt solution with low concentrations may promote the
the reactor within 0.01 MPa. A model D07-11A mass flow
hydrate formation; (2) a chemical reaction formula in POM
meter from Peking Jianzhong Instrument Inc. was used to
aqueous solution is as follows: 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

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
Fig. 3. Time evolution of storage process of NG (STP) in hydrate in hydrate formation is not the same as SDBS, as was seen
1000 ^ 1 ppm concentration. from Table 3. Higher concentrations of APG solution such
as 800 1200 ^ 1 ppm made the storage capacity of NG
was first recognized was determined by the flow meter higher. Though POM is not surfactant, its effect is nearly the
observations. There is an initial sharp increase in the flow same as APG as the promoter of hydrate formation, as was
rate of NG through the flow meter when the hydrate starts to seen from Table 4. When POM concentration was
form, which is considered as the origin of the time scale of 1000 ^ 1 ppm, the storage capacity of NGH was as much
the hydrate formation. The slope of the plot in the figure as 137.2 ^ 0.9 vol/vol.
corresponds to the rate of hydrate formation, which was The additives of SDBS, APG and POM can increase the
found to be nearly constant up to 30 min after the start of storage capacity of NG in hydrate, compared to the storage
hydrate formation. The hydrate was steadily formed in capacity 51.7 ^ 2.1 vol/vol in pure water system. It
500 ^ 1 ppm SDBS aqueous solution.
illustrates that water in the reactor can change into hydrate
The NGH formation rate curves against time in both cases
more in the presence of additives. Moreover, the concen-
of pure water and additives aqueous solutions
trations of the aqueous solutions of additives have an effect
(1000 ^ 1 ppm) are shown in Fig. 3. Fig. 3 does not include
on the storage capacity. With regard to the possible
any information on the variation of the induction period
mechanism of hydrate formation with the presence of
before the hydrate formation that will be discussed later.
sodium dodecyl sulfate (SDS), Zhong and Rogers proposed
Storage capacity in the Y-axis means the NGs volume
that the hydrate formation rates depend on SDS concen-
formed NGH at STP per 1 cm3 hydrate volume in the reactor.
tration and that the hydrates formed in a SDS micellar
Fig. 3 illustrates that APG and POM have the same effect as
solution were easily adsorbed onto a metal surface at the
SDBS on the hydrate formation in 1000 ^ 1 ppm solutions.
gas water interface, which improves the initial rate of
They all could evidently increase the formation rate of gas
hydrate formation until near the conversion of all free water
hydrate and the storage capacity. However, hydrate for-
and thus most water changes into the hydrates [20].
mation was very slow in the system of pure water.
However, they did not explain why the storage capacity of
hydrate also depend on the surfactant concentration. More-
3.2. Effect of additives on storage capacity of NG in hydrate over, some non-surfactant substances such as calcium
hypochlorite [23] also can improve the hydrate formation
Storage capacity of NG in hydrate is affected not only (i.e. the hydrate formation rate and the storage capa-
by the kinds of additives but also the concentrations of city, etc.). Based on the authors actual knowledge,
Table 2
Storage capacity of hydrate in SDBS solutions

Concentration (ppm) 0 200 400 600 800 1000 1600 2000

Storage capacity in hydrate (vol/vol) 51.7 131.4 117.5 119.2 124.5 123.5 99.3 97.3
Terminal error of experiment (vol/vol) ^2.1 ^0.9 ^0.6 ^0.9 ^0.6 ^0.6 ^0.6 ^0.9

Table 3
Storage capacity of hydrate in APG solutions

Concentration (ppm) 0 200 400 600 800 1000 1200 1600

Storage capacity in hydrate (vol/vol) 51.7 61.4 91.3 107.4 120.4 137.3 143.8 138.3
Terminal error of experiment (vol/vol) ^2.1 ^2.1 ^1.8 ^2.1 ^2.4 ^1.5 ^0.9 ^1.5
 C.S. Zhang et al. / Fuel 83 (2004) 21152121 2119

Table 4
Storage capacity of hydrate in POM solutions

Concentration (ppm) 0 200 500 1000 1500 2000

Storage capacity 51.7 91.8 99.5 137.2 86.5 88.5

in hydrate (vol/vol)
Terminal error of ^2.1 ^2.1 ^0.9 ^0.9 ^1.2 ^0.9
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- Fig. 5. Relation between hydrate formation rate and reaction time in SDBS
surfactant substance). aqueous solutions.

3.30 (vol/vol)/min or so and then starts to decrease after

3.3. Effect of additives on hydrate formation rate 32.00 min of the hydrate formation. The curves of the
hydrate formation rate against reaction time of others
In order to study hydrate formation rate in the reactor, the concentration of SDBS solutions are similar to the curve of
hydrate formation rate curves against reaction time as the the hydrate formation rate against reaction time in
example of APG and SDBS were drawn in Figs. 4 and 5. 200 ^ 1 ppm SDBS solution. However, the maximum
The hydrate formation rate was first large, and then became values of the hydrate formation rate after the hydrate
smaller in every curve. Furthermore, in one or two places of formation are different, respectively, and the ranges of
the curve, the hydrate formation rate increased and fluctuation of the hydrate formation rate from up to 10.00 to
decreased sharply. 30.00 min after the hydrate formation are unlike each other.
Fig. 4 illustrates that the hydrate formation rate of Figs. 4 and 5 show that the effect of SDBS system on the
400 ^ 1 ppm APG solution reaches 4.98 (vol/vol)/min up hydrate formation rate is dissimilar to that of APG system.
to 5.70 min after the start of hydrate formation and then First, the hydration reaction time in the APG solutions is
tends to decrease. When the hydration reaction is close to longer than that in the SDBS solutions as a whole and so the
end, the hydrate formation rate fluctuates a little. The curves average hydrate formation rate of SDBS system is less than
of hydrate formation rate against reaction time in 200, 600, that of APG system. Second, the time range of the rapid
800 and 1000 ^ 1 ppm APG solutions are similar to the formation of the hydrate in SDBD system is usually from
curve of the hydrate formation rate against reaction time of 10.00 to 30 min after the hydrate formation. However, the
400 ppm APG solution. However, the maximum values of time range of the rapid formation of the hydrate in APG
the hydrate formation rate after the hydrate formation are system is not very clear.
different, respectively, and the ranges of fluctuation of the Figs. 4 and 5 also seem to show two stages of the hydrate
hydrate formation rate are unlike each other. formation. This phenomenon may be explained from the
Fig. 5 illustrates that the hydrate formation rate of following discussion. There is an increase of hydrate
200 ^ 1 ppm SDBS solution reaches 5.80 (vol/vol)/min up nucleus concentrations in the aqueous solutions at the end
to 4.00 min after the hydrate formation and then start of the nucleation phenomenon, especially at the gas water
to decrease. From about 8.00 to 32.00 min after the interface, thus the hydrate nucleus grow into the hydrate
hydrate formation, the hydrate formation rate remains 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
Fig. 4. Relation between hydrate formation rate and reaction time in APG formation rate increase again, which leads to the fluctuation
aqueous solutions. of the hydrate formation rate.
2120 C.S. Zhang et al. / Fuel 83 (2004) 21152121

Fig. 7. Relation between induction time of hydrate formation and additives

concentration.
Fig. 6. Relation between temperature of solution and reaction time in
1000 ^ 1 ppm concentration. influenced by the molecular disorder of the hydrate reaction
Fig. 6 shows the change of solution temperature as a system. The additives solution system with an appropriate
result of the reaction heat in hydrate formation process in concentration is lower in the degree of molecular disorder
the presence of additives. The solution temperature changes than one without any additives as a result of molecular
with the reaction time in 1000 ^ 1 ppm SDBS, APG and appetencies and the spatial sites of the hydrate nuclei appear
POM solutions, it shows that the reaction heat is emitted to be of uniformity. Moreover the degree of this appetency
when the gas hydrate forms fast. When the heat cannot be and uniformity may be affected by the concentrations of
drove off with time at first, the solution temperature additives solution, which may lead to an effect of additive
increases rapidly. However, the solution temperature hardly concentration on the induction time of hydrate formation
has any change in pure water system because the hydrate that is reproductive at a certain concentration of additive.
formation rate is very slow. Figs. 4 6 also show that the On the other hand, the additives can promote the dissolution
increase of the solution seems to be positive proportion with of NG in the liquid phase prior to the hydrate formation
the hydrate formation rate. But the increase of the solution (about 200 450 cm3 NG at STP) and make the number of
temperature in the hydration reaction system is not gas molecules increase when there is a dynamic balance
beneficial to the fast formation of hydrate, seen from the between the gas and the liquid phase. The more the gas
kinetics of hydrate formation. How to drive off the reaction molecules are in the liquid phase, the more opportunity they
heat fast is a very important way to accelerate the hydrate have to collide and even combine with the cages formed by
formation further in the system of additives. 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-
3.4. Effect of additives on induction time of hydrate
mation needs further detailed investigation.
formation

The induction time in this study is called as the time it

takes for the introduction of the gas to the initial formation 4. Conclusions
of hydrate. A series of experiments in the present work show
that the induction time of hydrate formation was greatly In this work, the effects of small amount of additives on
shortened by the addition of additives. In the case of pure the hydrate formation were determined and the answers to
water, the induction time was long as much as 2600 min. some problems regarding rapid and abundant storage of NG
Fig. 7 shows that at higher concentrations (800 in hydrate were provided. By using the additivesAPG,
1600 ^ 1 ppm), the aqueous solutions of APG formed SDBS and POM, formation processes of gas hydrate were
NGH very fast and the induction time was only 15 ^ 3 min improved: (1) NGH was formed rapidlyseveral 100 times
or so. However, for SDBS system, hydrate induction time faster than without additives; (2) the induction time of NGH
was very short (about 25 30 min) at 100 ^ 1 or formation was shortened greatlyshort as much as 15 min
200 ^ 1 ppm concentration. Compared with APG and in the aqueous solution in a quiescent system; (3) free water
SDBS, the induction time of hydrate formation in POM trapped between hydrate particle is fully utilized to give
solutions all were longer1000 min or so. higher storage capacity and 87.2% of the maximum storage
The three-run experiments for the solution with each capacity can be achieved within 2 or 3 h of hydrate
concentration were made. The shorter hydrate crystal initiation; (4) the relations of hydrate formation rate,
induction time and its good reproducibility in the additives hydrate storage capacity, hydrate formation induction time
solutions were found. The results may be explained as the with the concentrations of additives were given
following discuss. On one hand, the induction time may be quantitatively.
 C.S. Zhang et al. / Fuel 83 (2004) 21152121 2121

Acknowledgements (HCFCs) and hydro fluorocarbons (HFCs) by using clathrate hydrate

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The authors are grateful to the National Natural Science
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