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Energy Conversion and Management 49 (2008) 22072213

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In situ hydrate dissociation using microwave heating: Preliminary study

Li Dong-Liang a,c, Liang De-Qing a,*, Fan Shuan-Shi b, Li Xiao-Sen a,
Tang Liang-Guang a, Huang Ning-Sheng b
a
Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, PR China
b
Guangzhou Center for Gas Hydrate Research, Chinese Academy of Sciences, Guangzhou 510640, PR China
c
Graduate University of Chinese Academy of Sciences, Beijing 100083, PR China

Received 12 June 2007; accepted 31 January 2008

Available online 21 March 2008

Abstract

In this work, we investigate the dissociation behavior of natural gas hydrate in a closed system with microwave (MW) heating and hot
water heating. The hydrate was formed at temperatures of 14 C and pressures of 4.55.5 MPa. It was found that the gas hydrate dis-
sociated more rapidly with microwave than with hot water heating. The rate of hydrate dissociation increased with increasing microwave
power, and it was a function of microwave power. Furthermore, the temperature of the hydrate increased linearly with time during the
microwave radiation.
2008 Elsevier Ltd. All rights reserved.

Keywords: Microwave heating; Natural gas hydrate; Methane; Dissociation

1. Introduction into the reservoirs. Saeger et al. [2] suggested another

The gas hydrate is an ice like substance composed of
small molecules (e.g. CH4, C2H6, CO2) trapped inside cages
of water molecules. It often forms under higher pressure
and lower temperature, with deposits found underneath
permafrost in Arctic regions and beneath deep ocean oors.
Because only 10% of the recovered energy is required for
dissociation, hydrate reservoirs have been considered as a
substantial future energy resource [1]. It is estimated that
the total amount of gas stored in this form may surpass
the energy content of the total fossil fuel reserves by as
much as a factor of two. With the recognized reservoirs of
natural gas hydrates in continental margins and in perma-
frost regions, a question arises about the feasibility and eco-
nomics of recovery of gas from these reservoirs. Many
methods have been proposed for gas recovery from in situ
hydrates, and one of them is the thermal stimulation
method. The typical method is to inject hot water or vapor
*
Corresponding author. Tel./fax: +86 20 87057669.
E-mail address: liangdq@ms.giec.ac.cn (D.-Q. Liang).
approach by placing an electromagnetic heater inside the
dissociation zone. Some other methods of heat transfer
are considered in detail in the monograph of Sloan [3],
where ame ows of microwave eects was oered.
Microwaves belong to the portion of the electromag-
netic spectrum with wavelengths ranging from 1 mm to
1 m, corresponding to frequencies between 300 MHz and
300 GHz. The two most commonly used frequencies are
0.915 and 2.45 GHz for industry purposes. Conventionally,
in heat transfer processes, energy is transferred to the mate-
rial through convection, conduction and radiation due to
thermal gradients. However, microwave energy is delivered
directly to materials through their molecular interaction
with the electromagnetic eld. Microwave heating is the
transfer of electromagnetic energy to thermal energy. This
dierence can result in a great many potential advantages
in using microwaves for processing materials. Because
microwaves can penetrate materials and deposit energy,
heat can be generated throughout the volume of the mate-
rial. So, it can reduce processing times and prove to be
energy saving [4]. In the past, microwave irradiation has

0196-8904/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.enconman.2008.01.031
2208 D.-L. Li et al. / Energy Conversion and Management 49 (2008) 22072213
been successfully used in many areas of the petroleum
industry [57].
The decomposition of hydrates with microwaves was
investigated by Rogers [8] rstly and also studied by Zhang
[9]. The results indicated that microwave heating was very
eective for hydrate dissociation. Another experimental
investigation was reported by Fatykhov and Bagautdinov
[10]. Nevertheless, few experimental data obtained by this
method are available in the literatures.
This study aims at identifying the features of the decom-
position of gas hydrate under conditions of volumetric
heating by MW electromagnetic radiation and discussing
the possibility of gas recovery from in situ hydrate using
microwave heating.
2. Experimental
2.1. Apparatus
Fig. 1 shows a schematic drawing of the experimental set
up. The cell consists of a stainless shell and cylindrical
quartz tube with a volume of 100 dm3, in which the micro-
wave is introduced. The stainless shell has two windows, on
the front and the back. Hydrate formation and dissociation
temperatures are measured trough a Pt100 RTD probe
inserted in the cell from the bottom. The uncertainty of
the RTD is 0.1 K. The pressure sensor used in the pipe
is a SPTA CZ-3 with an active range from 0 MPa to
10 MPa. The repeatability of the sensor is 0.028%, and
the accuracy is 0.115%. The pressure and temperature of
the system are continuously recorded on the computer dur-
ing the experiments. The cell is immersed in the water bath,
which has a working temperature range of 263368 K.
Fig. 1. Schematic diagram of the experimental set up.
Table 1
Experimental materials in this work
Materials Purity/composition Supplier
Methane 99.99% Fushan Kede Gas Co.
SDS >98 wt% Guangzhou Chemical Agent Co.
Distilled water Distilled
The microwave generator and transmission system was
made in Guangzhou Huayuan Co. Ltd. The output power
of the microwave source with the frequency of 2.45 GHz
can be adjusted linearly from 0 W to 750 W. Power mea-
surement is accomplished through the directional couplers,
which are designed so that a small amount of forward and
reected waves are separated and measured by power
meters. In the three port circulator, one port is connected
to the microwave source, another is connected to the direc-
tional couplers and the third port is connected to a water
load. The power that is reected back to the magnetron
is diverted, and the water load absorbs the reected power.
2.2. Materials
In order to reduce free water and quicken the test
process [11,12], 300 ppm of SDS was used in the following
tests. The materials used in this work are described in Table
1.
Before the test, the SDS-water solution was pumped
into the cell. When the system was cooled to about 4 C,
the cell was vacuum pumped and the hydrate forming
gas was pressed in the cell. In order to reduce the eect
of free water, the dissociation test started after the hydrates
had grown slowly for about four days.
 D.-L. Li et al. / Energy Conversion and Management 49 (2008) 22072213 2209

Fig. 2. Variation of the pressure and temperature with time during hydrate formation.

3. Results and discussion 3.2. Typical procedure of hydrate dissociation

3.1. The procedure of hydrate formation
The temperature in the water bath and solution and the
pressure in the cell during the hydrate formation procedure
were measured and are given in Fig. 2. As seen in Fig. 2, at
around 6 h, the temperature increased and the pressure
decreased sharply, which indicated the formation.
Fig. 3 illustrates the change of pressure and temperature
with time during the natural gas hydrate dissociation pro-
cedure under microwave irradiation.
Point a represents the time of microwave injection. The
hydrate begins to dissociate at point b. The temperature
increased but the pressure did not change from a to b. At
point c, the hydrate was dissociated completely. The

Fig. 3. Variation of the pressure and temperature with time during hydrate dissociation.
2210 D.-L. Li et al. / Energy Conversion and Management 49 (2008) 22072213

Fig. 4. Hydrate dissociation procedure under dierent microwave power radiation.

temperature increased linearly with time during the micro-
wave radiation from b to c. The time from a to b varied in
the dierent tests, so we discuss the process from b to c.
Here, the total time of hydrate dissociation was dened
from b to c, which characterized the rate of hydrate
dissociation.
3.3. Eects of dierent power of microwave on the methane
hydrate dissociation
about 60 W. The power input of microwave power is
150 W, and 60% of the power was reected by the cell bot-
tom because the sample was too small to absorb the total
microwave power. The value of the reected power can
be indicated by directional couplers. The results show that
the pressure decreased slightly after microwave injection or
bath heating. The pressure decrease may be because part of
the free water was transformed into gas hydrate. In this
test, the total time of hydrate dissociation was 30 min

Fig. 4 shows the hydrate dissociation process under dif-

ferent microwave power radiations.
Fig. 5 shows the total time of hydrate dissociation as a 100
function of microwave power. The rate of hydrate dissoci-
90
ation increased with increasing microwave power, and the
relationship between the total time of hydrate dissociation
80
and microwave power can be described by the following
t/min

equation: 70
b
t kw 1
60
Here, k is 687.07 and b is 0.5132 by tting the experi-
mental data. The related coecient R2 is 0.99. 50

3.4. Energy ratio comparisons with water bath heating 40

0 50 100 150 200 250

Fig. 6 shows the process of hydrate dissociation under
W/watts
microwave irradiation and water bath heating. The powers
of the microwave heating and the water bath heating were Fig. 5. Eects of dierent power of microwave.
 D.-L. Li et al. / Energy Conversion and Management 49 (2008) 22072213 2211

Fig. 6. The process of microwave irradiation and water bath heating: (a) microwave irradiation and (b) water bath heating.

under microwave irradiation. However, the time required study, but it illustrates that microwave heating can speed
under water bath heating was 50 min. up hydrate dissociation relative to bath heating.
Energy ratio comparisons of microwave irradiation and
water bath heating are described in Table 2. Here, the nom-
inal heating value of the gas was 37,250 kJ/m3, and the heat Table 2
Energy eciency comparisons of microwave and hot water heating
capacities of stainless steel and quartz glass are 0.05 J/g K
and 0.772 J/g K, respectively. In the cell, the weight of Microwave Water-bath
heating heating
stainless steel is 7443 g and the weight of quartz glass is
1022 g. By preliminary calculation, the energy ratio of Evolving water of the sample (g) 50 50
Heating power (W) 60 60
microwave heating is 3.17. It is greater than that of water Gas content (V/V) 150 150
bath heating, but it is lower than the value of thermal stim- Total time of hydrate dissociation (min) 30 50
ulation production reported by Tang et al. [13]. Temperature rise of the cell during the 18 10
Because of the laboratory condition, the system was not hydrate dissociation (K)
in thermal insulation and much of the heat was lost. The Absorption heat of cell (kJ) 19.98 11.61
Energy ratio 3.17 1.66
energy ratio described in Table 2 is only a preliminary
2212 D.-L. Li et al. / Energy Conversion and Management 49 (2008) 22072213

3.5. Microwave energy conversion
The dielectric properties of gas hydrates in combination
with the applied electromagnetic elds result in the conver-
sion of electromagnetic energy to heat. The power that is
transmitted to an object can be determined by the use of
the Poynting vector theorem [14], which can be derived
from the Maxwell equations. The power that is transmitted
across the surface, S, of a volume, V, is given by the real
portion of the following equation:
I the penetration depth is given by the following equation:
1
W E  H  dS 2
2 s
Here, W is the density of heat sources. E  H* is the Poyn-
ting vector and the *, in this case, denotes the complex con-
jugate. Using the divergence theorem, Maxwell equations
and by assuming the hydrates properties for the volume,
the following equation can be obtained for the real portion
of the Poynting power theorem
Z ties of gas hydrate are unknown. It is generally agreed that
1
W xlH  H  xe00 E  E rE  E dV 3 the dielectric constant of gas hydrate is 58 [15]. It is also
2
Here, l represents the imaginary component of the mag-
netic permeability and r is the conductance. In dielectric
materials, the magnetic permeability is usually small, and
the rst term can be neglected. In addition, xl can be con-
sidered as an equivalent conductance. If the electric eld is
assumed to be uniform throughout the volume, the follow-
ing simplied equation for the power, W, absorbed per unit
volume can be obtained from Eq. (4)
e00
W pf e0 e0 tan dE2 ; tan d 
e0
Here, e0 is the permittivity of vacuum; e0 and e00 denote the
real and imaginary parts of the permittivity of the medium,
respectively; tand is the tangent of the dielectric loss angle
of the medium; and f is the electromagnetic wave
frequency.
As energy is absorbed within the material, the electric
eld decreases as a function of the distance from the sur-
face of the material. Therefore, Eq. (4) is valid for only very
thin materials. The penetration depth is dened as the dis-
tance from the sample surface where the absorbed power is
1/e of the absorbed power at the surface. Beyond this
depth, volumetric heating due to microwave energy is neg-
ligible. Assuming the dielectric constant of free space is e0,
ce0
d 5
2pf e00
The penetration depth and knowledge of how the elec-
tric eld decreases from the surface are particularly impor-
tant in processing thick materials. If the penetration depth
of the microwave is much less than the thickness of the
material, only the surface is heated. The dielectric proper-
reported that the average dielectric constant of the hydrate
zones is 9, ranging from 5 to 20 in the Mallik 5L-38 Well in
the Mackenzie Delta, Canada [16]. Generally, the dielectric
constant of ice is 94 and the penetration depth is 70 cm.
When the microwave frequency is 2.45 GHz, therefore,
the penetration depth of gas hydrate is more than 70 cm,
so we think the microwave eld is uniform throughout
the volume in this test. The velocity of the temperature
increase is given by the following equation:
Qh M  C p T  T 0
4 w 6
t t
During the test, the microwave power is invariable, and
Cp is considered a constant at a small temperature varia-
tion. The rate of hydrate dissociation increased with

Fig. 7. The scheme for gas recovery from in situ hydrate use microwave heating: (1) microwave generator, (2) microwave transducer, (3) transmission line
on ground, (4) gas storage equipment, (5) gas ow line, (6) platform surface, (7) exterior pipe, (8) sleeve, (9) interior pipe (transmission line in well), and
(10) receiving antenna.
 D.-L. Li et al. / Energy Conversion and Management 49 (2008) 22072213
increasing microwave power, and the temperature
increased linearly with time during the microwave radia-
tion (Fig. 4).
On dierent powers of microwave radiation, the end
temperature at complete dissociation of the gas hydrate is
related to the microwave power. The relation can be writ-
ten as follows:
T /W
In accordance with Eq. (6), the total time of hydrate dis-
sociation can be given by the following equation:
tdissociation  k  W b
Here, k is a constant related to M, Cp, T0 and the temper-
ature of phase equilibrium. b is a constant related to the
microwave absorption ratio.
3.6. The concept of gas recovery from in situ hydrate using
microwave heating
Based on the results of these studies, the scheme of gas
recovery from in situ hydrate using microwave heating
(Fig. 7) was put forward. Microwave equipment is placed
on the platform. Microwave output heat can be collected
by the hydrate in the reservoir through the receiving
antenna placed in the well. The wellhead device gathers
the gas from the hydrate dissociation.
4. Conclusions
In this paper, a set of laboratory facilities is described. It
has been demonstrated that the impact of MW heating
causes a quick decomposition of gas hydrate compared to
bath heating under the same heating power. During the
microwave radiation, the temperature increased linearly
with time. The rate of hydrate dissociation increased with
increasing microwave power, and it was a function of
microwave power.
By preliminary calculation, the energy ratio of micro-
wave heating is 3.17. It is greater than that of water bath
heating, but it is much lower than the theoretical value of
thermal stimulation production. Microwave heating is an
eective method. The developed experimental facility and
the investigation may be employed to validate the use of
the MW electromagnetic stimulation technique for the pur-
2213
pose of recovering natural gas from in situ hydrate
reservoirs.
Acknowledgements
This work was supported by The National Natural Sci-
ence Foundation of China (50676097) and the Guangdong
7 Natural Science Foundation (05200113).
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