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Experiment of gas diffusion and its diffusion

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ARTICLE in INTERNATIONAL JOURNAL OF MINING SCIENCE AND TECHNOLOGY NOVEMBER 2012
DOI: 10.1016/j.ijmst.2012.12.007

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International Journal of Mining Science and Technology 22 (2012) 885889

Contents lists available at SciVerse ScienceDirect

International Journal of Mining Science and Technology

journal homepage: www.elsevier.com/locate/ijmst

Experiment of gas diffusion and its diffusion mechanism in coal

Li Xiangchun, Nie Baisheng , Zhang Ruming, Chi Leilei
School of Resource and Safety Engineering, China University of Mining & Technology, Beijing 100083, China
State Key Laboratory of Coal Resources and Safe Mining, Beijing 100083, China

a r t i c l e

i n f o

Article history:
Received 8 April 2012
Received in revised form 3 May 2012
Accepted 6 June 2012
Available online 29 January 2013
Keywords:
Gas
Coal
Diffusion
Pressure
Temperature

a b s t r a c t
In coal, the gas mainly exists in a free or an adsorption state. When the coal containing gas is damaged,
gas desorption and diffusion will occur which can result in gas disaster. This research on gas desorption
and diffusion provides a theoretical basis for gas disaster mechanism and prevention. The inuence of
pressure and temperature on gas diffusion is studied by the experiment. And the mechanism of pressure
and temperature on gas diffusion is also analysed. The research results indicate that gas diffusion capacity
increases with increasing temperature under the same pressure for the same coal sample. This is mainly
because the temperature increases, gas molecular hot motion is severer, kinetic energy of gas molecular
increases, and gas desorption quickens, therefore gas diffusion capacity changes stronger. Under other
unchanged conditions, the greater gas adsorption balance pressure, the more gas adsorption content,
and the higher the initial gas concentration. When gas diffusion begins, the greater the gas concentration
gradient, the faster the gas diffusion speeds.
2013 Published by Elsevier B.V. on behalf of China University of Mining & Technology.

1. Introduction
Many gas accidents have occurred during exploitation. Now, the
most effective measure for preventing gas accidents is gas drainage.
As estimated by Zhang et al. in China, within 2000 m burying depth,
the total capacity of coal-bed methane is (3035)  1012 m3, which
is equivalent to that of conventional natural gas [1]. Gas drainage
cannot only control gas disasters in the mine but also make use of
gas resources. For smooth gas exploitation, gas adsorption nature,
diffusion and ow laws must be understood. Dubianyiwen et al.
analyzed the methane adsorption dynamic law of coal particles with
different sizes and at different adsorption pressure at 25 C, and
tested the diffusion coefcients [2,3]. In 1986, Yang et al. analysed
and applied the law of gas diffusion [4]. What is more, Yang et al.
drew a conclusion experimentally that coal seam is an aggregate
composed of ultimate particles with pore resistance kept constant
in the interior of ultimate particles [4,5]. In addition, he pointed
out that pore resistance of large particles is smaller than that of
the small particles, and measured the ultimate particle size of some
coal samples. Shao analysed the common cinder gas desorption
empirical formula, and explained the intrinsic relation between
the formulas [6]. Chen put forward a three-parameter diffusion control model, and calculated the diffusion coefcient and activation
energy of coal samples experimentally [7]. The inuence of coal particle size to the gas diffuses in coal was studied by Marecka, and a
conclusion was that the relation expression of specic surface area
of coal and coal particle size is basically of logarithmic relationship;
Corresponding author. Tel.: +86 10 82375620.
E-mail address: chinalixc123@163.com (N. Baisheng).

and by experiment, it can be known that micro-porosity in the coal

and metamorphic grade plays an important role on the gas desorption [8]. In 2007, Cao et al. conducted experiment of different coal
particle size on gas desorption intensity and attenuation coefcient,
and studied the inuences of particle size on desorption intensity
[9]. In 2008, Wei et al. studied gas desorption law of tectonic soft
coal with different extent of damage in the same condition, and
determined gas desorption characteristics of tectonic soft coal in
different gas adsorption pressures [10]. In 2010, Lv et al. did an
experiment of Tiandiwangpo Mine in Jincheng on its desorption
and deformation, and drew a relationship of pore pressure with
gas desorption quantity and stress [11]. In 2010, Chen studied gas
desorption laws of coal samples in different moisture conditions
with the changing of metamorphic degree, damage types and gas
adsorption equilibrium pressures [12]. In 2011, Ma et al. carried
out experiment of six sets of different coal samples to research
methane isothermal adsorption/desorption, and established accurate tting equation of desorption effect of coal-bed gas in decompression conditions [13]. Thus, on the basis of the study results of
other researchers, the experiment of gas diffusion and the diffusion
mechanism of gas in coal seam are conducted in this paper.
2. Experimental
2.1. Collection and preparation of coal samples
(1) Collection of coal samples
A region of higher gas emission was selected for sample collection. In order to study the universal mechanism, coal samples were
collected from No. 3 soft stratication in Yangquan Coal Mine of

2095-2686/$ - see front matter 2013 Published by Elsevier B.V. on behalf of China University of Mining & Technology.
http://dx.doi.org/10.1016/j.ijmst.2012.12.007

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L. Xiangchun et al. / International Journal of Mining Science and Technology 22 (2012) 885889

Table 1
Data of coal samples industrial analysis and the determination results of porosity.
Coal sample

Yangquan

Industry analysis (%)

water

Ash

Volatile

Ad

Fixed carbon

1.38

10.56

8.34

10.71

79.72

True density (g/m3)

Apparent density (g/cm3)

Porosity (%)

1.43

1.365

4.55

11

5
2

13
12

1
7
8

10

1. Separator balls; 2. Drying tube; 3. Vacuum pump; 4. High-pressure valve; 5. Pressure gauge; 6. Triple valve;
7. Coal sample tank; 8. Constant temperature trough; 9. Large capacity burette;
10. Saturated salt water equilibrium bottle; 11. Two-way valve; 12. Small capacity Burette;
13. Mercury equilibrium bottle

14

Q (mL/g, combustible basis)

Q (mL/g, combustible basis)

Fig. 1. Schematic of experimental measuring device for gas emission.

12
10
8
25
30
35

6
4

, 1.30 MPa
, 1.56 MPa
, 1.47 MPa

2
0

100

200

300

400 500

600

700

800

t (min)

(a) 0.16-0.316 mm coal sample

14
12
10
8
6

35
30
25

4
2
0

100

200

300

400

, 1.33 MPa
, 1.53 MPa
, 1.37 MPa

500

600

700

800

t (min)

(b) 0.316-0.63 mm coal sample

Fig. 2. Gas diffusion amount curves of Yangquan coal samples at different temperatures.

Shanxi province. The samples were taken from a typical area and
rigorously packaged.
(1) Preparation of coal samples
Grind the coal samples with coal grinder and sieve particle size
of 0.160.316 mm and 0.3160.63 mm with standard sieve. Dry
the coal samples 23 h at 4550 C. Preserve the coal samples in
ground sampling plasma bottles.
2.2. Procedure
(1) Industrial analysis of coal samples
The results of industrial analysis of the coal samples are shown
in Table 1.
(1) Devices
Experimental devices depend on volumetric method. The schematic diagram is shown in Fig. 1.
2.3. Results and discussion
(1) Inuence of temperature on gas diffusion

The gas diffusion amount of Yangquan and Jincheng coal samples changed over time at different temperatures and is depicted
in Figs. 2 and 3. Due to pretty much the same temperature and different pressure, the characteristics shown are not obvious. With
temperature increasing, gas molecules0 kinetic energy increases,
the opportunity of gaining more adsorption barrier energy increases, and residence time on the surface of coal pores shortens,
thus adsorption capacity decreases. For the same coal sample and
under the condition of the same size and the adsorption equilibrium pressure, with temperature increasing, thermal motion of
gas molecules accelerates, thus diffusion capacity is enhanced,
and diffusion velocity is accelerated. This basically corresponds
with the law revealed in the experimental data. It can also be seen
from the Figs. 2 and 3 that, for the same coal sample, its diffusion
curve has the same tendency and law. Yangquan coals slower initial diffusion velocity and atter diffusion curve reect the ow of
gas in the coal, the difculty degree of diffusion and the coal pore
interconnectivity.
(1) Inuence of adsorption pressure on gas diffusion
With gas adsorption equilibrium pressure increasing, the probability of gas molecules impacting coal pore surface increases, and
the disposed degree of density of gas molecules on the surface of

887

30

Q (mL /g, combustible basis)

Q (mL/g, combustible basis)

L. Xiangchun et al. / International Journal of Mining Science and Technology 22 (2012) 885889

25
20
15

25
30
35

10

, 3.03 MPa
, 3.69 MPa
, 3.31 MPa

5
0

100

200

300

400

500

600

30
25
20
15
35
30
25

10
5
0

700

100

200

300

400

, 2.38 MPa
, 2.90 MPa
, 3.43 MPa
500

600

700

t (min)

t (min)

(a) 0.16-0.316 mm coal sample

(b) 0.316-0.63 mm coal sample

18
16
14

Q (mL/g, combustible basis)

Q (mL/g, combustible basis)

Fig. 3. Gas diffusion amount curves of Jincheng coal samples at different temperatures.

12
10
8
6

2.39 MPa
1.56 MPa
0.98 MPa

4
2
0

100

200

300

400 500
t (min)

600

700

800

14
12
10
8
6

2.69 MPa
1.53 MPa
0.79 MPa

4
2
0

100

(a) 0.16-0.316 mm coal sample

200 300 400 500 600 700

t (min)

800 900

(b) 0.316-0.63 mm coal sample

Fig. 4. Gas diffusion amount curves of Yangquan coal samples at three pressures.

10d

= (0.1 ~ 10)d

0.1d

(a) Fick diffusion

(b) Knudsen diffusion

(c) Transitional diffusion

Fig. 5. Diffusion modes of porous gas.

coal pores also increases, thus the gas adsorption amount

increases. Fig. 4 shows the gas diffusion amount curves of
0.160.316 mm and 0.3160.63 mm particle coal samples of Yangquan Coal Mine at three different pressures and temperature of
30 C with time. It can be known from Fig. 4 that in the same gas
diffusion time, the greater the gas adsorption pressure, the larger
the cumulative gas diffusion. At the beginning of gas diffusion,
the gas adsorption equilibrium pressure is higher and the gas
concentration gradient greater, thus the gas diffusion velocity is
faster.

3. Diffusion mechanism of gas in coal

3.1. Gas diffusion modes in coal
From molecule migration, it is known that the nature of gas diffusion is the result of non-uniform heat movement of gas molecules. Coal is a typical porous medium. According to the study on
the micro-mechanism of gas diffusion in porous media, gas diffusion can be divided into Fick diffusion, Knudsen diffusion, transitional diffusion by use of Knudsen which expresses the size of
pore diameter and mean molecule free path [14]. The number of
Knudsen can be expressed as follows:

Kn

d
k

where d is the mean pore diameter, m; and k the mean molecule

free path, m.
When Kn is larger than 10, pore diameter is far more than mean
molecule free path. Collision of gas molecules occurs mainly between the free pore gas molecules. There is little chance of collision
between molecules and capillary walls. Thus, this gas diffusion can
be regarded as Fick diffusion. When Kn is smaller than 0.1, pore
diameter is far less than mean molecule free path. Collision of
gas molecules occurs mainly between molecules and capillary
walls. Little chance of collision between the free pore gas molecules occurs. Thus, this gas diffusion can be regarded as Knudsen
diffusion. When Kn is between 0.1 and 10, pore diameter is equivalent to the mean molecule free path. It is the same important for
collision between gas molecules and collision as well as between
molecules and capillary walls. Thus, gas diffusion can be regarded
as transitional diffusion (Fig. 5).
Because of the porous structure of coal and coal macromolecules, coal is a good adsorbent. When the pore gas molecules are
strongly absorbed in the solid coal surface and because coal surface
has adsorption potential energy barrier intensity Ea, when the energy of pore gas molecules is equivalent to the surface energy DEa,

L. Xiangchun et al. / International Journal of Mining Science and Technology 22 (2012) 885889

Surface energy
of coal (J/m2)

888

Ea

surface of the coal which is the corresponding size of Kn 6 0.1,

gas will be followed by Knudsen diffusion, transitional diffusion,
Fick diffusion into the cracks system of coal.

Ea

4. Mechanism analysis of temperature and pressure on gas

diffusion capacity
Section of coal

Because gas diffusion models are related to pore diameter and

mean molecule free path, it should be known for mean molecule
free path of gas molecules.
According to thermodynamics theory, it can be known that gas
molecules move at all the times. But its movement has a limit. This
is because a large number of molecules exist in any space and
movement of any molecule will have the opportunity to collide
with other molecules. The straight distance of molecule movement
before the collision between molecules is regarded as molecule
free path. According to molecule movement theory, k that is the
mean molecule free path can be expressed as follows:

Fig. 6. Surface diffusion of gas on coal surface.

the surface diffusion of gas molecules in the coal surface is formed,

as shown in Fig. 6. For strong adsorption coal, surface diffusion has
important inuence on diffusion velocity. When the pore diameter
is equivalent to the size of gas molecules and gas pressure is large
enough, gas molecules enter the micro-pore and gas molecules are
in a solid solution. The crystal diffusion occurs in the above course.
It can be seen from Fig. 5 that, the more difcult gas diffusion is,
the bigger gas diffusion resistance is with the increment of the
number of Knudsen. Gas diffusion capacity can be improved by
enhancing the number of crack and pore in coal seam or reducing
mean molecule free path.

kT
k p 2
2pd0 p

where k is the Boltzmann constant, 1.38  1023, J/K; T the absolute

temperature, K; d0 the molecular effective diameter, nm; and p the
gas pressure, MPa.
It can be seen from Eq. (2) that the mean molecule free path is
directly proportional to temperature and inversely proportional to
pressure.
Because gas pressure is usually far greater than atmospheric
pressure in actual coal seam, the real mean molecule free path is
much smaller. Fig. 7a displays the relationship between mean molecule free path and gas pressure obtained according to Eq. (2) under normal temperature. Fig. 7a shows that, k decreases with
pressure increment, but k decreases rapidly with pressure increment, ranging between 0.1 and 1 MPa. After gas pressure is more
than 1 MPa, k stabilizes. Because the gas diffusion model changes
from Knudsen diffusion into Fick diffusion or transitional diffusion
in some pores of coal under increment of gas pressure, for the same
mode, the greater gas pressure in coal pore, the stronger gas diffusion capacity. But, after gas pressure is more than 1.5 MPa, increment of gas diffusion capacity is slight.
The mean molecule free path is related to temperature. Fig. 7b
shows the relationship between mean molecule free path and temperature obtained according to Eq. (2). It can be seen that k increases linearly with the increment of temperature. However, on
the whole, the temperature has little impact on the increment of
k. Actually, the impact of temperature is more evident than that
of pressure on gas diffusion. The reason may be that the increment
of temperature decreases gas adsorption capacity, and increases
free gas and gas pressure. In addition, when temperature increases,
so does gas pressure under the same volume according to ideal gas
equation. Thus, the two reasons make the decrease of k more than

3.2. Diffusion course of gas in coal

During exploitation, free gas in coal joints ows into the exposed coal under the effect of gas pressure gradient. Then gas ows
from micro-pore in coal seams, that is, gas ows from the small
particles to the fracture system of coal seam under the effect of
gas concentration gradient. At last, gas in the inner surface of coal
transforms from adsorption gas to free gas. The stage of the slowest
movement determines ow velocity of the course. The research
shows that because gas desorption is very fast, it does not affect
the gas emission rate [15]. Because the pore size is equivalent to
mean molecule free path, the process of gas ow from micro-pore
to ssure is diffusion process. The gas ow seeps in the ssure and
follows Darcys law. Thus, gas migration rate depends on the rst
two stages and nally is controlled by the stage of slow migration.
Because of development of micro-pore, some time of gas diffusion
by coal particles is needed and the diffusion resistance cannot be
ignored.
When gas diffusion occurs in micro-pore of coal, it can be
known as follows: when Kn is large than 10, gas diffusion can be
regarded as Fick diffusion; when Kn is less than 0.1, gas diffusion
can be regarded as Knudsen diffusion; and when Kn is between
0.1 and 10, gas diffusion can be regarded as transitional diffusion.
At the same time, due to the difference of absorption intensity in
pore surface of coal, different degrees of surface diffusion occur,
which quickens the speed of gas diffusion in coal pore. Because
of the difference of the size of coal pore, several modes of gas diffusion all occur. After gas desorption occurs in the micro-porous

120

80
60

CH4

40

N2
CO2

20

Mean molecule free

walk (nm)

Mean molecule free

walk (nm)

100

100
80
60
40
20
0

p (MPa)

(a) Gas pressure

273

323

373

T (K)

(b) Temperature

Fig. 7. Relationship between mean molecule free path with gas pressure (T = 293 K) and temperature (p = 0.1 MPa).

L. Xiangchun et al. / International Journal of Mining Science and Technology 22 (2012) 885889

the increment of k caused by temperature, which strengthens gas

diffusion capacity.
5. Conclusions
(1) By the experiment of gas diffusion, the inuence of pressure
and temperature on gas diffusion is veried. The research
results show that with the increment of pressure and temperature, gas diffusion capacity increases. Gas diffusion
capacity increases with temperature increasing under the
same pressure for the same particle coal samples. This is
mainly gas diffusion capacity changes stronger with the
temperature increasing, gas molecular hot motion enhancing, kinetic energy of gas molecular increasing and gas
desorption quickening.
(2) Under other unchanged conditions, the greater gas adsorption balance pressure, the more gas adsorption content,
and the higher the initial gas concentration. When gas diffusion begins, the greater the gas concentration gradient, the
faster the gas diffusion speeds.
(3) After gas desorption occurs in micro-pore of coal, gas will
follow by Knudsen diffusion, transitional diffusion, Fick diffusion into the crack system of coal. And the mechanism of
pressure and temperature on gas diffusion is analysed.

Acknowledgments
The authors gratefully acknowledge foundation by the State Key
Basic Research Program of China (No. 2011CB201202), the Basic

889

Science Research Special Foundation of China University of Mining

& Technology (Beijing) (No. 2009KZ03), and the Basic Science Research Special Foundation of China University of Mining & Technology (Beijing) (No. 2009QZ09).
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