JOURNAL OF GEOPHYSICAL RESEARCH, VOL. 110, B01311, doi:10.

1029/2004JB003314, 2005

Measuring and modeling thermal conductivity

of gas hydrate-bearing sand
Duzi Huang1 and Shuanshi Fan
Guangzhou Center for Gas Hydrate Research, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences,
Guangzhou, China
Received 11 July 2004; revised 4 November 2004; accepted 19 November 2004; published 25 January 2005.

[1] Effective thermal conductivity (ETC) of both tetrahydrofuran (THF) and methane

hydrate-bearing sandy porous media was measured by the Hot Disk Thermal Constant
Analyser. Thermal conductivity of methane hydrate is 0.575 W m
1 K
1 at 0
C and
6.6 MPa (methane gas pressure), which is close to THF hydrates 0.51 W m
1 K
1 at 0
C
and 0.1 MPa (atmosphere pressure). However, the measured 1 W m
1 K
1 ETC of
methane hydrate-bearing sand is significantly lower than that of THF hydrate-bearing sand
at 2 W m
1 K
1. This is because the methane hydrate formed with a sodium dodecyl
sulfate (SDS) solution in sand at our laboratory has a wall creeping growth
characteristic and consequently a large part of the pores were filled with methane free gas.
ETCs of sand containing gas hydrates were also calculated using a renormalization
method. The process involves sample partitioning, labeling, initial value assignments,
and renormalization calculations. A Monte Carlo analysis was applied to sample
laboratory-scale gas hydrate-bearing sand assemblies. We found that the
renormalization modeling results agreed well with measured ETCs when each photo of
a 1.3 mm  1.3 mm subsample was divided into 16 or more blocks.
Citation: Huang, D., and S. Fan (2005), Measuring and modeling thermal conductivity of gas hydrate-bearing sand, J. Geophys. Res.,
110, B01311, doi:10.1029/2004JB003314.

1. Introduction
[2] Large natural gas (mainly methane) hydrate deposits
are found world wide in sediments of outer continental
margins and polar permafrost areas [Kvenvolden, 2000]. It
has been estimated that naturally occurring methane
hydrates contain at least twice as much combustible
carbon as in all other fossil fuels on the Earth [Sloan,
1994]. Besides being a potentially promising future energy
source [Holder and Angert, 1981; Holder et al., 1984;
Kvenvolden, 1988; Max and Lowrie, 1996; Haq, 1999;
Collett, 2002], natural gas hydrates stability may play an
important role in global warming [Hatzikiriakos and
Englezos, 1993; Makogon et al., 1998] and as a geohazard
[Ergun and Cifci, 1999; Kvenvolden and Lorenson, 2001;
Zhang, 2003]. Combined with predictive models of
hydrate dissemination and concentration, Xu and Ruppel
[1999] constrain the migration of hydrate dissociation fronts
in marine sediments. Thus the thermal property measurement of hydrate-bearing sediments provide necessary inputs
for assessing seafloor stability, global climate change,
sedimentation, erosion, submarine slide formation and other
processes [Ruppel, 2000]. Evaluating the effect of present1
Also at Department of Thermal Science and Energy Engineering,
University of Science and Technology of China, Hefei, China.

Copyright 2005 by the American Geophysical Union.

0148-0227/05/2004JB003314$09.00

day climate change on hydrate stability may also require

estimates of thermal conductivity in hydrate-bearing sediment [Revil, 2000]. So, it is critical to use reliable thermal
properties when evaluating the response of gas hydrate to
environmental changes and exploitation operations.
[3] In spite of having crystal-like structures, gas hydrates
exhibit peculiar glass-like behavior in the dependence of
thermal conductivity on temperature [Ross et al., 1981;
Dharma-wardana, 1983; Andersson and Ross, 1983; Tse,
1988; Andersson and Suga, 1996]. Most thermal conductivity measurements were done for THF hydrate since laboratory-made THF hydrate is usually very uniform. Thermal
conductivity of natural gas hydrate or hydrate-bearing systems and their dependence on temperature are not well
constrained [Waite et al., 2002a; Kumar et al., 2004]. Cook
and Leaist [1983] measured thermal conductivity of
methane hydrate using a needle probe and their result was
0.49 W m
1 K
1 at
10
C with corrections to account for
the fact that 43% of methane hydrate decomposed to water
ice in their experiment. Stoll and Bryan [1979] systematically measured physical properties of sediments containing
propane gas hydrates and found that thermal conductivity
of sediment tends to decrease rather than increase when
the water in sediment was replaced by gas hydrate. This, in
turn, would affect the interpretation of various geophysical
measurements, such as heat flow. Waite measured the
thermal conductivity of well-characterized pure methane
hydrate [Waite et al., 2002a] and methane hydrate in quartz
sand [Waite et al., 2002b]. The results show clear relation-

B01311

1 of 10

HUANG AND FAN: THERMAL CONDUCTIVITY OF HYDRATES

B01311

B01311

Figure 1. Schematic of gas hydrate formation and measurement system (not to scale). The cell is made
of stainless steel with 250 mm height and 50 mm width (inner diameter). The sample volume can be
adjusted, and the maximal sample volume is 200 mL.
ships of effective thermal conductivity (ETC) to porosity and
gas pressure, but they are not mathematically described.
[4] Various models and formulae have been proposed for
predicting ETC for two-phase systems and all of them
predict ETC as function of thermal conductivities of individual phases and their volume fraction [de Vries, 1952;
Maxwell, 1954; Woodside and Messmer, 1961; Krupiczka,
1967]. Volume fraction based methods are easy to use but
can be inaccurate because individual phases are usually not
uniformly distributed. Consequently, they have various
applicable ranges and may yield different values even at
equivalent conditions. Revil [2000] modeled the ETC by up
scaling the local equations using a differential effective
medium approach. Revils model accounts for the pore
space distribution and complexity of the thermal flow lines
through the porous material by introducing a thermal
formation factor. Some researchers began to use new
technique to resolve ETC of porous media. On the
basis of the self-similar characteristic of porous media, the
fractal theory [Mandelbrot, 1982] was first used in
the research of the ETC for unidirectional fibrous composites by Pitchumani and Yao [1991]. Wang et al. [2003]
used the fractal theory to predict the ETC of liquid with
suspension of nanoparticles. King [1989] and Fernandes et
al. [1996] have used the renormalization technique to
calculate effective permeability, but it has not yet been
applied to ETC problems. In this work, we first measure
the thermal conductivities of sand particles, methane and
THF hydrates and then use a space renormalization technique to model the ETC of sand containing THF hydrate.

2. Experiments
2.1. Apparatus
[5] The experimental system includes two parts, one for
gas hydrate formation, and the other for thermal conductiv-

ity measurement. A schematic of the system is shown in

Figure 1. There are five functioning units in the hydrate
formation part. The gas tank, the gas flux monitor and the
vacuum pump (not shown in Figure 1) are responsible for
gas input and output. The alcohol bath and the temperature
controller (not shown in Figure 1) form the temperature
controlling section. The hand pump and the piston, which is
located at the inner bottom of the cell, perform hydraulic
functions. Data of the gas flow and the temperature inside of
the cell are collected at points A and B respectively, and
logged by the Agilent 34901A. Figure 1 shows the detail of
the stainless steel cell. Sample volume can be changed using

Figure 2. Hot Disk probe used in the experiment. The

standard probe of Hot Disk Thermal Constants Analyzer is
also shown in the white frame, and the diameter of double
spiral disk is 14 mm. See color version of this figure in the
HTML.

2 of 10

B01311

HUANG AND FAN: THERMAL CONDUCTIVITY OF HYDRATES

B01311

Figure 3. Renormalization procedure: (a) labeled blocks, (b) first step of renormalization, and (c) second
step of renormalization.
the piston at the bottom of the cell. The piston is hydraulically driven by the hand pump. The whole cell is immersed in the temperature controlled alcohol bath. The
thermal conductivity measurement probe is also shown in
Figure 1. Thermal conductivity of the sample is measured
by the Hot Disk Thermal Constant Analyser system. This
system is manufactured by Sweden Hot Disk AB Company
and it is based on the transient plane source (TPS) technique
of Gustafsson et al. [1979, 1986]. The Hot Disk probe is
specially designed for this investigation. As Figure 2 shows,
it is sandwiched by two polymethyl methacrylate (PMMA)
shells with a hole on each of them, through which the probe
can make a contact with the sample. This design also
protects and supports the soft probe.
2.2. Hot Disk TPS Technique
[6] On the basis of the theory of TPS technique, the
Hot Disk Thermal Constants Analyzer utilizes a sensor
element in the shape of a double spiral. As Figure 2
shows, this Hot Disk sensor acts both as a heat source for
increasing the temperature of the sample and a resistance
thermometer for recording the time-dependent temperature
increase. The sensor element is made of a 10-mm-thick
Nickel-metal double spiral, with precisely designed
dimensions (width, number of windings, and their radii).
This spiral is supported by a plate to protect its particular
shape, give it mechanical strength and keep it electrically
insulated. The plate, made of the polyimide Kapton
can be used throughout the temperature range from 10 K
to 500 K.
[7] The encapsulated Ni-spiral sensor is then sandwiched
between two halves of the sample (solid samples), or
embedded in the sample (powders, liquids). During a preset
time, 200 resistance recordings are taken and from these the
relation between temperature and time is established. A few
parameters, like the power output to increase the tem-

perature of the spiral, the measuring time for recording

200 points and the sensor size are used to optimize the
experimental settings so thermal conductivities from 0.01 to
400 W m
1 K
1 can be measured. The TPS principle,
procedure, and method have been discussed in detail by
Gustafsson et al. [1979, 1986], Log and Gustafsson [1995],
and Nagai et al. [2000].
2.3. Sample Description
[8] The sediment used in the experiment is construction
sand with quartz as the primary component. The sand is
sieved by a 60/120 mesh (300 125 mm) sieve. Porosities of
loosely packed dry sand, water saturated sand, ice saturated
sand and THF hydrate saturated sand are around 50%,
47%, 49% and 53%, respectively. A THF solution of 21%
THF to 79% water in mass ratio [Ross and Andersson,
1982], which is larger that the ideal THF hydrate ratio of
20:80, was used to form THF hydrate and avoid the effect
of ice. The THF hydrate thus formed is very uniform and
may be viewed as an end-member state since no such ideal
mixture of hydrate and sediment is found in nature. We also
found that it is hard to form methane hydrate via reaction
of pure water with methane gas because of the low gas
solubility and a long induction period. On the basis of
Zhong and Rogers [2000] work, instead of pure water, a
280-ppm sodium dodecyl sulfate (SDS) aqueous solution
was used to enhance hydrate formation.
2.4. Procedure
[9] Before each experiment, the cell was first filled with
the liquid solution (of either THF or SDS), sand was then
slowly put into the liquid solution with the guidance of a
glass rod, and any superfluous liquid above the top of the
sand was pumped out. Temperature and pressure were 0
C
and 0.1 MPa (atmospheric) for THF hydrate formation and
0
C and 6.6 MPa (methane gas pressure) for methane

Figure 4. Equivalent heat resistance distribution of a renormalization group.

3 of 10

B01311

HUANG AND FAN: THERMAL CONDUCTIVITY OF HYDRATES

Figure 5. Equivalent heat resistance distribution of the

renormalization group after transformation.
hydrate formation. THF hydrates formed from the THF
solution itself, while methane gas was added to the cell to
form methane hydrates with the SDS solution. After the
formation of gas hydrate, samples were kept for aging at the
same pressure and temperature conditions for 3 days to
stabilize the thermal conductivity [Stoll and Bryan, 1979].
In situ ETC measurements were then carried out at various
temperatures as the sample was heated and the measurements were repeated as the sample was cooled down after
the heating was stopped. The mean value of the two
measurements at the same temperature was taken as the
samples ETC at that temperature.

Hoshen and Kopelman [1976] applied this technique to

study percolation and cluster distribution processes, calling
it a labeling technique. The third hypothesis has been
widely used. For instance, the famous Maxwell formula
[Maxwell, 1954] was derived in a similar way.
[12] On the basis of the analogy between conductive heat
transfer and electrical conduction, a four-block renormalization group is treated as a combination of eight heat
conductors as shown by Figure 4, where ka, kb, kc, and kd
are the assigned thermal conductivities of the blocks, and
the resistances of the heat conductors are
R1

1
1
1
1
1
1
; R2

; R3
; R4

2ka
2ka 2kb
2kb
2ka 2kc
1

1
1
1
1
1
1
R5

; R6
; R7

; R8
:
2kb 2kd
2kc
2kc 2kd
2kd

After transferring triangle connection to star connection

[King, 1989], the final heat resistance connection of the
renormalization group as shown in Figure 5 is obtained,
where

3. Modeling and Programming

Ra

[10] The renormalization method is shown in Figure 3. A

given area is partitioned into several blocks, each with its
own characteristic value or initial value, such as thermal
conductivity, resistance or permeability, etc. On the basis of
certain rules, the adjoining four blocks are treated as a
renormalization group to form a new block, which is shown
in Figure 3b. The whole process is repeated until the final
block is obtained as shown in Figure 3c. We then consider
the final value K as the renormalization result of the whole
sample. It is important to construct a valid rule to perform a
renormalization process for the particular problem to be
solved. For a simple example of such rules, assume Ka1,
Ka2, Ka3 and Ka4 are the properties of one district, and the
value of Ka1, Ka2, Ka3 is A, but Ka4s value is B. The first
renormalization step yields Ka, and its value must be A
because A:B in the district is 3:1; that is, A has higher
mathematical expectation than that of B in the district. The
renormalization zone in Figure 3 is two-dimensional space.
When it comes to three-dimensional space renormalization,
the number of adjoining blocks is eight. From above
analysis, we conclude that it is necessary to form 4n (n
equals 0 or positive integer) blocks in an original twodimensional space and 8n blocks in a three-dimensional
space.
[11] Three assumptions or approximations are made for
this study: (1) Heat transfer across a porous, saturated sand
is more or less isotropic with no large distortion of heat
flow. (2) Before the renormalization procedure starts, blocks
with more than half their area occupied by sand are assigned
the intrinsic thermal conductivity of the sand, and the
rest have the thermal conductivity of the pore material.
(3) Conductive heat resistance is analogous to electrical
resistance. The first assumption leads to a nearly isotropic
porous medium and enables us to treat the heat transfer
through the porous medium as a two-dimensional process.
The error introduced by the second approximation is negligible when the size of divided blocks is sufficiently small.

B01311

1
1
1
1
1
; Rc

; Rd
; Rb
4ka kc
4ka
2ka 2kb
4kb
2

1
1
1
1
1
Re
; Rg

; Rh
:
; Rf
4kb kd
4kc
2kc 2kd
4kd

The ETC of the renormalization group k is calculated as

k f4ka kc kb kd kb kd ka kc ka kc kb kd
g
 fkb kd ka kc ka kc kb kd
ka kb kc kd
3ka kb kc kd ka kc kb kd g
1 :

Formula (3) is the core rule of our renormalization process.

A computer program was developed to perform the labeling
and the renormalization processes.

Figure 6. Symmetry characteristic and the direction

characteristic of renormalization group with two blocks
different showing (a) parallel distribution of two kinds
of different blocks, (b) series distribution of two kinds of
different blocks, and (c) random distribution of two kinds of
different blocks.

4 of 10

B01311

HUANG AND FAN: THERMAL CONDUCTIVITY OF HYDRATES

B01311

Figure 7. Proportionality characteristic of renormalization method for (a) 2-rank renormalization unit
with one block different, (b) 4-rank renormalization unit with four blocks different, and (c) 8-rank
renormalization unit with sixteen blocks different.
[13] Color photos of the samples were taken using a
digital electron microscope and processed into black and
white images. Since sand particles have a lower light
transmittance, they are always brighter than the other phase
and appear white on the images while the pore phase
appears black. Our labeling program counts the total number of white and black pixels. If the total number of white
pixels in a block is larger than that of black pixels, the block
is labeled as white, and otherwise it is labeled as black. This
procedure maps the distribution of sand and gas hydrate,
and assigns thermal conductivity value to each of the 4n
blocks initially. The renormalization program treats each
adjoining four blocks as a renormalization group and
calculates its ETC according to the rule expressed by
equation (3). After the first renormalization process, the
total number of blocks reduces to 4n
1. The renormalization
process is repeated until the ETC of the whole sample is
obtained.
[14] For the two-phase systems, the two-dimensional
model expressed by equation (3) has three basic characteristics. The first is symmetry. If only one block differs from
the others, the final ETC of the four-block group is
independent of which block is different. Similarly, though

the ETCs differ between Figures 6a, 6b, and 6c, within
Figures 6a, 6b, and 6c the pair of renormalization groups
have the same ETC. This characteristic means the symmetrical change of blocks in the renormalization group will not
affect the final ETC, providing strong stability and fault
tolerance.
[15] The second characteristic of the method is direction.
As Figure 6 shows, all three configurations have the same
porosity of 50% and would have the same ETC according to
a porosity-based method. In fact, the parallel configuration
(Figure 6a) has the largest ETC, the serial configuration
(Figure 6b) has the lowest ETC, and the third and random
configuration (Figure 6c) has an intermediate ETC. Our
method successfully resolved the problem by using the pore
space distribution, providing a significant advantage over
the traditional porosity-based methods.
[16] The last characteristic of the method is proportionality. As Figure 7 indicates, the renormalization group
(Figures 7a, 7b, and 7c) holds the same ETC according to
equation (3), showing the ETC calculation is free of scale.
When modeling, the ETC is analogous to resistance. ETC is
an intensive property, while resistance is extensive; thus we
have to take into account the change in dimensions of the

Figure 8. Measured ETC of water saturated sand

assembly. Thermal conductivity of water is taken from
Ma et al. [1986]. The thermal conductivity data of sand
itself are calculated using equation (4).

Figure 9. Thermal conductivity of THF hydrate measured

from
10
C to
2
C at 0.1 MPa, fitted by l = 0.5092 +
0.00163T (R = 0.993), compared with Cook and Laubitzs
[1981] results.

5 of 10

B01311

HUANG AND FAN: THERMAL CONDUCTIVITY OF HYDRATES

B01311

of thermal conductivity to the porous medium itself, or the

intrinsic thermal conductivity of the sand. On the basis of
the analogy of electrical conductivity and thermal conductivity, Woodside and Messmer [1961] proposed a model to
predict the ETC of a porous medium saturated with a fluid:
ke

aks kf
ckf ;
ks 1
d dkf

where ke is the ETC, ks and kf are the thermal conductivities

of the solid phase and the fluid respectively. For c = f

0.03, a = 1
c and d = (1
f)/a, where f is the porosity,
the predicted ETC values were in fair agreement with those
observed for unconsolidated sands. Figure 8 shows our
measured ETCs of sand saturated with water from 0
C to
20
C at 0.1 MPa. The intrinsic thermal conductivity of sand
is calculated using (4). The thermal conductivity of water is
taken from Ma et al. [1986]. The thermal conductivity of
our sand, as calculated using equation (4), can be
represented by a linear dependence of the thermal
conductivity on temperature:
Figure 10. Image of a THF hydrate-bearing sand sample
taken by a digital electron microscope at
2
C (not to
scale). The white parts on the image represent sand
particles.

renormalized block. The third characteristic of our method

indicates the ETC model still has the intensive property, and
the model is stable.

4. Results and Discussion

4.1. Thermal Conductivity of Sand
[17] One difficulty in modeling the ETC of a hydratebearing porous medium is the assignment of a proper value

ks 5:004
0:0075T

R
0:967;

where T is temperature (
C). To validate this determination

of the thermal conductivity of sand, we used equation (5)
and our ETC renormalization technique described in section
4.3, and successfully resolved the ETC of sand saturated
with water. The calculated ETC of water saturated sand is
2.00 W m
1 K
1 at 0
C and 0.1 MPa, which is very close to
the measured value of 2.08 W m
1 K
1 (Figure 8).
4.2. Thermal Conductivity of THF Hydrate
[18] Figure 9 shows the thermal conductivity of pure
THF hydrate measured at temperatures from
10
C to

2
C. The results are obtained from two independent
experiments. Cook and Laubitzs [1981] result is also shown
for comparison. The results show a well-defined positive

Figure 11. Six levels of renormalization partition for the sample shown in Figure 10 (not to scale).
6 of 10

B01311

HUANG AND FAN: THERMAL CONDUCTIVITY OF HYDRATES

Figure 12. Relation of sample number to ETC.

B01311

Figure 14. Measured and calculated ETC of THF hydratebearing sand.

temperature dependence similar to that of a glass-like

material, which agrees well with previous studies [Ross
and Andersson, 1982]. This may be explained because
clathrates encapsulated atoms that can rattle inside the
voids and that such a phonon-glass and electron-crystal
material tends to have glass-like thermal transport characteristics [Slack, 1995, 1997; Iversen et al., 2000]. Because of
the glass-like behavior of THF hydrate thermal conductivity, we can safely assume that the effect of anisotropy
resulting from the crystalline structure of THF hydrates on
thermal conductivity is minor.
4.3. ETC of Sand Containing Hydrate
[19] Figure 10 shows the black and white image of a
THF hydrate saturated sand porous medium at
2
C and
0.1 MPa, and the image is 40 times of original 1.3 mm 
1.3 mm sample zone. Figure 11 shows six levels of the
labeling process performed for the image. The result of the

64-rank labeling process, i.e., dividing the sample into 64 

64 blocks, represents the original image pretty well. On a
5 cm  5 cm sample, photos were taken at 60 places based
on a Monte Carlo analysis [Heermann, 1986]. The relation
of random sampling number to ETC is shown in Figure 12.
It indicates that the ETC attenuates and stabilizes when
more than 30 photos are used for the 5 cm  5 cm sample,
validating our use of 60 photos per sample. The stabilization
of the ETC result based on photos covering only 0.07% of
the 5 cm  5 cm sample also indicates the homogeneous
nature of our samples. Then each photo was processed at
all six renormalization levels. The results are shown in
Figure 13 with each data point representing the maximum
mathematical expectation of the 60 subsamples at the same
renormalization rank. Note that the calculated ETC
decreases quickly as renormalization rank increases and
stabilizes starting at rank 16.

Figure 13. Calculated ETC and correspondent variance of

the THF hydrate-bearing sand sample at
2
C and 0.1 MPa
done at six renormalization ranks.

Figure 15. Measured thermal conductivity of sand containing methane hydrates formed from a SDS solution and
methane gas.

7 of 10

B01311

HUANG AND FAN: THERMAL CONDUCTIVITY OF HYDRATES

B01311

the random model, the Krupiczka [1967] model, and the

Maxwell [1954] model give lower results than those of
experiment. The Woodside and Messmer [1961] model
agrees well with the experimental results with a maximal
relative error of 1.9%, indicating this model is reasonable to
use for unconsolidated two-phase systems.

5. Conclusions

Figure 16. Sample of sand containing methane hydrates

formed with a 280-ppm SDS solution. The white parts are
methane hydrates, and gray parts are sand coated thinly by
methane hydrate.

[20] The ETCs of THF hydrate-bearing sand porous

media calculated using the rank 64 renormalization process
is compared with those measured using the Hot Disk
Thermal Constant Analyzer in Figure 14. The partitioning
and renormalization method prediction is within 0.8% of the
measured value in the temperature range from
15
C to
0
C.
[21] Figure 15 plots the ETC of a methane hydratebearing sand sample measured at 6.6 MPa, which shows a
slight increase with increasing temperature. The results are
obtained from three independent experiments, and the
measurements were carried out on methane hydrate formed
with a 280ppm SDS solution. The measured ETCs are much
lower than those of THF hydrate-bearing sand. For example, the measured ETC of methane hydrate-bearing sand
sample is about 1 W m
1 K
1 at 0
C and 6.6 MPa, while
that of THF hydrate-bearing sand is close to 2 W m
1 K
1
at 0
C and 0.1 MPa. Considering that THF hydrate has a
similar thermal conductivity to that of methane hydrate, the
experimental data shown in Figure 15 are a bit surprising.
This phenomenon may be related to the surfactant effect
introduced by using the SDS solution in our experiment.
Zhong and Rogers [2000] found that gas hydrates formed
with SDS solution formed concentric shells on cell walls. In
our experiments the same surfactant effect, which led to
enhanced precipitation of gas hydrate on solid walls,
resulted in (1) methane hydrates enwrapped sand particles,
and (2) large amount methane hydrates accumulated at the
top of the porous sand (Figure 16). The latter process
extracted a certain amount of pore water and caused gas
to fill the vacated pores. We call this the wall creeping
hydrate growth phenomenon. The gas-filled pores have a
negligible thermal conductivity compared to that of gas
hydrate or sand and lower the samples ETC significantly.
[22] Figure 17 shows the ETCs of THF hydrate-bearing
sand porous media calculated by our method with those of
classical methods. Six different models have been applied to
predict the thermal conductivity of this dispersion, and their
mathematical equations are shown in Figure 18. It is
indicated that the series model and parallel model have
the minimal and maximal calculated ETC respectively, and

[23 ] ETC of sand containing THF or methane gas

hydrates was measured using the Hot Disk Thermal Constant Analyzer. We present a model to calculate the ETC of
a sand assembly saturated with gas hydrates based on the
theory of renormalization and a labeling technique. The
labeling technique is applied for block partitioning and
assigning initial values, and the renormalization process is
used to calculate the ETC. Though we used a 64  64 grid
to characterize the grain and pore distribution, even a 16 
16 grid provides sufficient resolution for accurately estimating a samples ETC. The ETC of a large sample can be
obtained using a Monte Carlo analysis of several ETCs
calculated from several random locations within the sample.
[24] Our study found that (1) thermal conductivity of
THF hydrate has a well-defined positive temperature dependence (i.e., glass-like behavior) from
10
C to
2
C at
0.1 MPa; (2) ETC of THF hydrate-saturated sand calculated
using the renormalization method agrees well with measurement; (3) despite the fact that THF and methane
hydrates have similar thermal conductivities, the methane
hydrate-bearing sand sample has a lower ETC than that of
the sand assembly saturated with THF hydrates; this is
attributed to the presence of gas in the pore space; (4) of the
porosity-based models, the Woodside model [Woodside and
Messmer, 1961] most closely predicts our measured ETC;
and (5) the theoretical discussion here provides a method-

Figure 17. Method comparing with those of porositybased classical methods: left pointing triangle, parallel
model; solid circle, this work experimental results; open
circle, this work calculated; right pointing triangle, Woodside model; triangle, random model; cross, Krupiczka
model; inverted triangle, Maxwell model; square, series
model.

8 of 10

B01311

HUANG AND FAN: THERMAL CONDUCTIVITY OF HYDRATES

B01311

Figure 18. Classical thermal conductivity models.

ology for accurately estimating thermal conductivity in twophase systems.

[25] Acknowledgments. We would like to express our heartfelt
thanks to Wenyue Xu for spending so much time on correcting this paper
and improving the clarity of its expression. We benefited greatly from
discussions with him. Financial assistance from National Natural Science
Foundation of China (50176051, 90410003) is gratefully appreciated.

References
Andersson, O., and H. Suga (1996), Thermal conductivity of normal and
deuterated tetrahydrofuran clathrate hydrates, J. Phys. Chem. Solids,
57(1), 125 132.
Andersson, P., and R. G. Ross (1983), Effect of guest molecule size on the
thermal conductivity and heat capacity of clathrate hydrates, J. Phys. C,
16, 1423 1432.
Collett, T. S. (2002), Energy resource potential of natural gas hydrates,
AAPG Bull., 86(11), 1971 1992.
Cook, J. G., and M. J. Laubitz (1981), The thermal conductivity of two
clathrate hydrates, paper presented at 17th International Thermal Conductivity Conference, Natl. Inst. of Stand. and Technol., Gaithersburg,
Md.
Cook, J. G., and D. G. Leaist (1983), An exploratory study of the thermal
conductivity of methane hydrate, Geophys. Res. Lett., 10, 397 399.
de Vries, D. A. (1952), A nonstationary method for determining thermal
conductivity of soil in situ, Soil Sci., 73(2), 83 89.
Dharma-wardana, M. W. C. (1983), Thermal conductivity of the ice polymorphs and the ice clathrates, J. Phys. Chem., 87, 4185 4190.
Ergun, M., and G. Cifci (1999), Gas-saturated shallow sediments in the
eastern Black Sea and geohazard effects, paper presented at the Annual
Offshore Technology Conference, Offshore Technol. Conf., Houston,
Tex.
Fernandes, C. P., F. S. Magnani, P. C. Philippi, and J. F. Daan (1996),
Multiscale geometrical reconstruction of porous structures, Phys. Rev. E,
54(2), 1734 1741.
Gustafsson, S. E., E. Karawacki, and M. N. Khan (1979), Transient hotstrip method for simultaneously measuring thermal conductivity and thermal diffusivity of solids and fluids, J. Phys. D, 12, 1411 1421.
Gustafsson, S. E., E. Karawacki, and M. A. Chohan (1986), Thermal transport studies of electrically conducting materials using the transient hotstrip technique, J. Phys. D, 19, 727 735.
Haq, B. U. (1999), Methane in the deep blue sea, Science, 285, 543 544.
Hatzikiriakos, S. G., and P. Englezos (1993), The relationship between
global warming and methane gas hydrate in the Earth, Chem. Eng.
Sci., 48(23), 3963 3969.

Heermann, D. W. (1986), Computer Simulation Methods in Theoretical

Physics, Springer, New York.
Holder, G. D., and P. Angert (1981), Methane hydrate as a gas resource,
paper presented at Intersociety Energy Conversion Engineering Conference, Atlanta, Ga.
Holder, G. D., V. A. Kamath, and S. P. Godbole (1984), Potential of natural
gas hydrates as an energy resource, Annu. Rev. Energy, 9, 427 445.
Hoshen, J., and R. Kopelman (1976), Percolation and cluster distribution.
I. Cluster multiple labeling technique and critical concentration algorithm, Phys. Rev. B, 14(8), 3438 3445.
Iversen, B. B., et al. (2000), Why are clathrates good candidates for thermoelectric materials, J. Solid State Chem., 149, 455 458.
King, P. R. (1989), The use of renormalization for calculating effective
permeability, Transp. Porous Media, 4, 37 58.
Krupiczka, R. (1967), Analysis of thermal conductivity in granular materials, Int. Chem. Eng., 7(1), 122 144.
Kumar, P., D. Turner, and E. D. Sloan (2004), Thermal diffusivity measurements of porous methane hydrate and hydrate-sediment mixtures, J. Geophys. Res., 109, B01207, doi:10.1029/2003JB002763.
Kvenvolden, K. A. (1988), Methane hydrate-a major reservoir of carbon in
the shallow geosphere, Chem. Geol., 71, 41 51.
Kvenvolden, K. (2000), Natural gas hydrate: Introduction and history of
discovery, in Natural Gas Hydrate in Oceanic and Permafrost Environments, edited by M. D. Max, pp. 9 16, Springer, New York.
Kvenvolden, K. A., and T. D. Lorenson (2001), Global occurrences of gas
hydrate, paper presented at the 11th International Offshore and Polar
Engineering Conference, Nor. Conoco, Stavanger, Norway.
Log, T., and S. E. Gustafsson (1995), Transient plane source technique for
measuring thermal transport properties of building materials, Fire Mater.,
19, 43 49.
Ma, Q. F., R. S. Fang, L. C. Xiang, and S. Ni (1986), Handbook of Applied
Thermal Properties (in Chinese), China Agric. and Mech. Press, Beijing.
Makogon, Y. F., J. C. Holste, and S. A. Holditch (1998), Natural gas
hydrates and global change, paper presented at the International Offshore
and Polar Engineering Conference, Montreal, Que., Canada.
Mandelbrot, B. B. (1982), TheFractal Geometry of Nature, W. H. Freeman,
New York.
Max, M. D., and A. Lowrie (1996), Oceanic methane hydrates: A frontier
gas resource, J. Pet. Geol., 19(1), 41 56.
Maxwell, J. C. (1954), A Treatise on Electricity and Magnetism, 3rd ed.,
Dover, Mineola, N. Y.
Nagai, H., Y. Nakata, T. Tsurue, and H. Minagawa (2000), Thermal conductivity measurement of molten silicon by a hot-disk method in shortduration microgravity environments, Jpn. J. Appl. Phys., 39, 1405 1408.
Pitchumani, R., and S. C. Yao (1991), Correlation of thermal conductivities
of unidirectional fibrous composites using local fractal techniques,
J. Heat Transfer, 113, 788 796.

9 of 10

B01311

HUANG AND FAN: THERMAL CONDUCTIVITY OF HYDRATES

Revil, A. (2000), Thermal conductivity of unconsolidated sediments with

geophysical applications, J. Geophys. Res., 105, 16,749 16,768.
Ross, R. G., and P. Andersson (1982), Clathrate and other solid phases in
the tetrahydrofuran-water system: Thermal conductivity and heat capacity
under pressure, Can. J. Chem., 60, 881 892.
Ross, R. G., P. Andersson, and G. Backstrom (1981), Unusual PT dependence of thermal conductivity for a clathrate hydrate, Nature, 290, 322
323.
Ruppel, C. (2000), Thermal state of the gas hydrate reservoir, in Natural
Gas Hydrate in Oceanic and Permafrost Environments, edited by M. D.
Max, pp. 29 42, Springer, New York.
Slack, G. A. (1995), CRC Handbook of Thermoelectrics, edited by D. M.
Rowe, 401 pp., CRC Press, Boca Raton, Fla.
Slack, G. A. (1997), Design concepts for improved thermoelectric materials, in Thermoelectric Materials: New Directions and Approaches, MRS
Symp.Proc., vol. 478, edited by T. M. Tritt et al., p. 47, Mater. Res. Soc.,
Pittsburgh, Pa.
Sloan, E. D. (1994), Conference overview, Ann. N. Y. Acad. Sci., 715, 1
23.
Stoll, R. D., and G. M. Bryan (1979), Physical properties of sediments
containing gas hydrates, J. Geophys. Res., 84, 1629 1634.
Tse, J. S. (1988), Origin of glassy crystalline behavior in the thermal properties of clathrate hydrates: A thermal conductivity study of tetrahydrofuran hydrate, J. Phys. Chem., 92, 5006 5011.
Waite, W. F., J. Pinkston, and S. H. Kirby (2002a), Preliminary laboratory
thermal conductivity measurements in pure methane hydrate and methane
hydrate-sediment mixtures: A progress report, paper presented at the

B01311

Fourth International Conference on Gas Hydrate, Mitsui Eng. and Shipbuild., Yokohama, Japan.
Waite, W. F., et al. (2002b), Thermal conductivity measurements in porous
mixtures of methane hydrate and quartz sand, Geophys. Res. Lett.,
29(24), 2229, doi:10.1029/2002GL015988.
Wang, B. X., L. P. Zhou, and X. F. Peng (2003), A fractal model for
predicting the effective thermal conductivity of liquid with suspension
of nanoparticles, Int. J. Heat Mass Trans., 46, 2665 2672.
Woodside, W., and J. H. Messmer (1961), Thermal conductivity of porous
media. I. Unconsolidated sands, J. Appl. Phys., 32(9), 1688 1699.
Xu, W., and C. Ruppel (1999), Predicting the occurrence, distribution, and
evolution of methane gas hydrate in porous marine sediments, J. Geophys. Res., 104, 5081 5095.
Zhang, Y. (2003), Methane escape from gas hydrate systems in marine
environment, and methane-driven oceanic eruptions, Geophys. Res. Lett.,
30(7), 1398, doi:10.1029/2002GL016658.
Zhong, Y., and R. E. Rogers (2000), Surfactant effects on gas hydrate
formation, Chem. Eng. Sci., 55, 4175 4187.

S. Fan, Guangzhou Center for Gas Hydrate Research, Guangzhou

Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou
510640, China. ([email protected])
D. Huang, Department of Thermal Science and Energy Engineering,
University of Science and Technology of China, Hefei 230026, China.

10 of 10