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Adsoprtion of Methane on Coals Under Simulated Deep Burial Conditions

Lijuan Zhao1,2, Wanli Gong2, Hongfei Duan3, Caifang Wu1, Yong Qin1, Geoff Wang2
1

Key Laboratory of the Ministry of Education China for CBM Resource and Reservoiring Process, China University of Mining and Technology, Xuzhou, Jiangsu 221116, P. R. China Email: l.zhao3@uq.edu.au 2 School of Chemical Engineering, the University of Queensland, St Lucia, Qld 4072, Australia 3 Datang Tashan Coal Mine, Datong Coal Mine Group Co., Ltd, Datong, Shanxi 037003, P. R. China

temperature and pressure below 50 C and 20 MPa, Abstract In order to understand the adsorption respectively. [1] Most researches only focused on shallow coal adsorption under low temperature and pressure, placing much less attention on deep burial conditions because of cost, difficulties in drilling deep wells or other safety issues. Coal adsorption studies carried out by many researchers, which indicated that many factors can influence the adsorbability of methane on coal, such as coal rank, coal macerals, coal deformation structures, coal moisture content and ambient temperature and pressure of the coal reservoir. Since temperature and pressure are generally correlated with depth, the adsorbability depends on depth in coal reservoir. [2] It is common that an increase in pressure boosts the amount of adsorption, while a rise of temperature decreases the amount of adsorption, because gas adsorption is an exothermic process. [3]As a result, a better understanding of the adsorption isotherm of methane on coals under deep burial conditions has great positive impact on coalbed methane recovery. II. EXPERIMENTALS A. Coal Samples Four coal samples which have been nominated as standard samoles in China were selected from the related Keywords- deep coal; coalbed methane; adsorption characteristics; high temperature and pressure I. INTRODUCTION Currently, the commercial depth limit for coalbed methane recovery is less than 1200 m, with corresponding reservoir coal mines in Eastern Ordos Basin of Shanxi Group, Upper Permian (Table 1). Experimental coal samples were crushed into 60~80 meshes, and were processed by a balanced moisture method, but data from the experimental results was converted to air dried basis in order to avoid the effect of characteristics of deep coal, four groups of coals were studied with methane isothermal adsorption experiments at high pressures up to 31 MPa under temperatures from 30 C to 100 C. The experiments were designed to simulate the deep burial conditions of coal seam and provide insight into methane isotherms of deep coals. Impact of the coal properties such as coal rank, mineral composition (vitrinite/inertinite) and ash etc. should be considered. The adsorption isotherms of methane have been analyzed comparatively. The particularity of the adsorption behavior of deep coal was also investigated by comparing with ones of shallow coals. The results show that the adsorption characteristics of deep coal exhibit some distinguished features compared with shallow coals, largely influenced by temperature and pressure. For deep coals, the adsorbability of methane is significantly reduced compared with shallow coals. The adsorbability of shallow coals is less affected by the coal rank, coal macerals and ash content compared with deep coals under given temperature conditions. It implies temperature and pressure are the determinant factors that control the adsorbability of coals.

adsorption moisture of coalbed methane.


TABLE I.
Coal Sample YP NY MZQ XS

BASIC PROPERTY OF COAL SAMPLES USED


Coal Seam No. / Position 5/Ps1 5/Ps1 5/Ps1 5/Ps1 Ro,max (%) 0.57 1.18 1.76 2.18 Proximate Analysis Mad (%) 5.77 0.81 0.95 1.20 Ad (%) 5.18 11.37 13.93 9.62 Coal Sample Conditions W (g) 100.98 88.06 104.74 94.92 Wb (g) 92.78 82.47 93.99 87.99 Me (%) 8.12 6.35 10.26 7.30

Sampling Sites Yang Poquan Mine in Shanxi Nan Yu Mine in Shanxi Mao Zequ Mine in Shanxi Xiangshan Mine in Shanxi

Mad-air dried basis moisture; Ad-dried basis ash content; G-weight of coal samples; Gb-weight of balance water coal samples; Me-percentage of the balance water

III. RESULT AND DISCUSSION B. Setup and Procedure Isothermal adsorption simulation experiment is processed with volumetric method, using the ISO-300 isothermal adsorption equipment. The temperature of the manufacturer is from room temperature to 120 , heating with oil bath; the maximum pressure is 70 MPa; and the volume of sample cylinder and comparison cylinder is 150 ml. The methane was used as adsoprtion gas with the concentration of 99.9 %. Data is analyzed according to the Langmuir monolayer adsorption model. In this paper, the depth of coal reservoir in Ordos is 1000~3000 m, the geothermal temperature is 90 C, and the reservoir pressure is under 31 MPa at the maximum buried depth. [4] Thus, the temperatures of the experiment are designed at 30 C, 50 C, 70 C, 85 C and 100 C, respectively. The maximum adsorption pressure is 30 MPa. A. Adsorption Behavior of Coals at Various Coal Ranks The maximum reflectance of vitrinite of coal (coal 5) in Eastern Ordos Basin was below 2.5 %. With the increase of coal rank, Langmuir volume increases (Fig. 1) while Langmuir pressure decreases (Fig. 2). Moreover, from long flame coal to meagre coal, as the increasing of coal rank, the slopes of Langmuir volume are 6.53 at 30 C; 5.60 at 50 C; 5.34 at 70 C; 3.48 at 85 C, and -0.09 at 100 C respectively (Figure 1), the increment of Langmuir volume with coal rank under high temperature is less than that under low temperature. As a result, the rate of Langmuir volume decreases at higher temperature under deep burial condition so that the effect of coal rank on adsorbability is weaker, and the effort of temperature is stronger on adsorbability of coal.

30 30
VL (cm g-1) 30
y = 6.525x + 11.093 R2 = 0.9002

50
y = 5.5955x + 9.3128 R2 = 0.868

25 VL (cm g )
-1 3

25 20 15 10 5

15 10 5 0.5 1.0 1.5 Ro,max (%) 2.0 2.5

20

0.5

1.0

1.5 Ro,max (%)

2.0

2.5

70 30 25 VL (cm g )
-1 3

85 30 25 VL (cm g )
-1 3

y = 5.3368x + 6.4484 R2 = 0.9814

y = 3.4799x + 7.9123 R2 = 0.7599

20 15 10 5 0.5 1.0 1.5 Ro,max (%) 2.0 2.5

20 15 10 5 0.5 1.0 1.5 Ro,max (%) 2.0 2.5

100 10 9 VL (cm g )
-1 3

y = -0.0908x + 8.1816 R2 = 0.0014

8 7 6 5 0.5 1.0 1.5 2.0 2.5

Ro,max (%)
Figure 1. The variation of Langmuir volume (VL) for coals with coal ranks

30 10 8 PL (Mpa) 6 4 2 0 0.5 1.0 1.5 Ro,max (%) 2.0 2.5


y = -3.5494x + 10.359 R2 = 0.8662

50 12 10 PL (Mpa) 8 6 4 2 0 0.5 1.0 1.5 Ro,max (%)


85 16 14 12 10 8 6 4 2 0 0.5 1.0
y = -5.7984x + 14.906 R2 = 0.6936

y = -4.4214x + 11.999 R2 = 0.7583

2.0

2.5

70 12 10 PL (Mpa) 8 6 4 2 0 0.5 1.0 1.5 Ro,max (%) 2.0 2.5


PL (Mpa)
y = -3.8505x + 11.035 R2 = 0.793

1.5 Ro,max (%)

2.0

2.5

100 16 14 12 10 8 6 4 2 0 0.5
y = -7.4471x + 15.413 R2 = 0.6494

PL(Mpa)

1.0

1.5 Ro,max (%)

2.0

2.5

Figure 2. The variation of Langmuir pressure (PL) for coals with coal ranks

B. Effect of Temperature and Pressure The increase of pressure benefits the adsorption of coal samples to methane [5]. To be specific, adsorbability increases linearly as the increase of the pressure before 5 MPa, then the adsorbability increases slowly (Fig. 3). In brief, the adsorbability increases as pressuring with other conditions being equal. Coal samples with different metamorphic degrees have different adsorbabilities, and the pressures required by saturation adsorbability are different. The increase of temperature goes against the adsorption of coal samples to methane [6]. The adsorbability decreases with

the increase of the temperature according to the experiment results of the coal samples as other conditions being equal. All these four coal samples illustrate that adsorbability decreases with growing temperature, adsorption curve at low temperature is always above that at high temperature, and Langmuir volume reduction degree is different in temperature range, so the reduction rate of Langmuir volume increases gradually with temperature growing (Fig. 3).

16 14 Adsorption content V( cm 3g-1) 12 10 8 6 4 2

20

YP (Ro,max =0.57)

Adsorption content V(cm g )

30 50 70 85 100

18
-1

NY (Ro,max =1.18)

16 14 12 10 8 6 4 2 0

30 50 70 85 100

Pressure(Mpa)
0 0 5 10 15 20 25 30 35 40

Pressure( Mpa)
0 5 10 15 20 25 30 35 40

25

30

Adsorption content V( cm g )

MZQ (Ro,max =1.76)


Adsorption content V(cm g )
-1 3

20

15

30 50 70 85 100

XS (Ro,max =2.18)
-1

25

20

30 50 70 85 100

15

10

10

Pressure( Mpa)
0 0 5 10 15 20 25 30 35 40

Pressure( Mpa)

0 0 5 10 15 20 25 30 35 40

Figure 3. Methane isothermal adsorption curves with air dried basis under different coal ranks

C. Influences of Coal Maceral and Ccomposition 1) Coal maceral Fig. 4 shows the relationship between Langmuir volume and coal maceral of coal samples under different temperature in the experiments in Eastern Ordos. The adsorbability of inertinite to methane is greater than vitrinite. Specifically, the slope of Langmuir volume increases with the increase of the inertinite

content (0.60), and the slope of Langmuir volume decreases with the increase of the vitrinite content (0.62) at 30 C. However, the slope of Langmuir volume goes up with the growth of the inertinite content (0.03), while the slope of Langmuir volume decreases with the increase of the vitrinite content (0.38) at 100 C (Fig. 4). Hence, coal maceral has a minor impact on adsorbability at high temperature under burial condition.

30 25 V L (cm 3 g -1 ) 20 15 10 5 10

30

Inertinite Vitrinite

25 20 V L (c m 3 g -1 ) 15 10

50

Inertinite Vitrinite

y = 0.6013x + 3.8201

y = -0.6246x + 59.874

y = -0.5739x + 53.564 y = 0.4985x + 3.5488

30 50 70 Vitrinite/Inertinite Content(%)

90

10

30 50 70 Vitrinite/Inertinite Content(%)

90

21 19 17 15 13 11 9 7 5 10

70

Inertinite Vitrinite

25 20 V L ( c m 3 g -1 ) 15 10 5

85
y = 0.565x - 2.6944

Inertinite Vitrinite y = -0.5425x + 47.17

V L (cm 3 g- 1 )

y = 0.4769x + 0.6543

y = -0.4039x + 39.323 90

30 50 70 Vitrinite/Inertinite Content(%)

10

30 50 70 Vitrinite/Inertinite Content(%)

90

12 10 VL (cm 3 g -1 ) 8

100
y = -0.3763x + 31.846

Inertinite Vitrinite

y = 0.0289x + 7.2556 6 4 10 30 50 70 Vitrinite/Inertinite Content(%) 90

Figure 4. Langmuir volume (VL) changes with vitrinite/inertinite contents at different temperatures

2) Ash content The adsorbability of ash is relatively weak; it affects the adsorbability through affecting organic materials in the coal. The existence of the ash often closes up micro pores, causing the decrease of effective adsorption area, and making the adsorbability decrease. [7] From the results of the experiments, there is certain relevance between ash content and Langmuir volume in deep coal, Langmuir volume decreases with the increase of ash content (Fig. 5).

CONCLUSIONS In conclusion, high temperature and pressure under deep burial condition become the governing factors influencing adsorption behavior. While other geological factors play a secondary role. Langmuir volume of methane adsorption on coals under high pressure and temperature is less than that under low pressure and temperature, which means that the absorbability of deep coals is weaker than that under shallow coal. The temperature has a significant impact on the adsorption behavior under a given pressure. It is common that higher coal rank tends to promote the

28 26 24 22 20 18 16 14 12 10 8 4 5 6 7 8

y = -1.7126x + 35.487 R = 0.8709


2

adsorption amount. Nonetheless, it might have minor impact under deep burial conditions. As mentioned above, the effects of coal rank, coal maceral and ash content on adsorption of coalbed methane are not significant under deep burial conditions. ACKNOWLEDGMENT This work is financially supported by the Scientific

VL / cm g

-1

9 Ad / %

10

11

12

13

14

Research Innovation Projects of University Graduate Student of Jiangsu Province (CXZZ12-0947) and the National Science-technology Support Plan Projects

Figure 5. Relationships between ash content (Ad) and Langmuir volume (VL)

(2012BAK04B00).

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