富有机质页岩-水蒸气吸附热力学与动力学特性——以鄂尔多斯盆地二叠系山西组页岩为例

doi:10.11743/ogg20210115

Abstract

Abstract:

Adsorption is one of the key mechanisms for the occurrence of connate water and formation water in shale reservoirs. A characterization of water adsorption onto organic-rich shale is of great theoretical and practical significance to tackling such geological and engineering issues as the micro-distribution of water and gas, the mechanisms of shale gas enrichment and the improvement of shale gas recovery. Shale-water vapor isothermal adsorption experiments were therefore combined with some theoretical adsorption models (7 thermodynamic models and 4 kinetics models) to study the fundamental principles of water vapor adsorption on shale. Results indicate that the adsorption/desorption isotherms are showing the typical TypeⅡcurves with hysteresis loops extending to very low relative pressure region, which may be explained by the fact of reluctant dehydration of clay minerals. Two of the models, GAB and Dent, are proven to be the most fitting to the shale-water vapor isotherm curves and reveal a two-stage water molecule adsorption on shale from forming monolayers to multilayers and capillary condensation. With p/p₀ less than 0.1, water molecules are mainly adsorbed as monolayer on one site of shale. With p/p₀ between 0.1 and 0.8, the site is gradually saturating and more layers start to build upon the first layer, thus forming a secondary adsorption site. With p/p₀ greater than 0.8, the first site is almost fully saturated and the adsorption on the secondary site continues in such a rate that capillary condensation of water occurs. Moreover, the negative values of Gibbs free energy change, enthalpy change and entropy change of the adsorption, indicate a spontaneous, exothermic and entropy-reduction process. Thus the double first-order rate model is the most suitable for describing the adsorption process of water vapor on shale. It reveals that the adsorption process can be divided into a surface adsorption dominated by an earlier external diffusion and a pore adsorption dominated by a later internal diffusion, and that the internal diffusion serves to control the adsorption rate of water vapor onto shale.

Key words: thermodynamics, adsorption kinetics, adsorption mechanism, water vapor adsorption, organic-rich shale, Shanxi Formation, Permian, Ordos Basin

CLC Number:

TE122.2

Wei Dang, Jinchuan Zhang, Fengqin Wang, Pei Li, Chang'an Shan, Ruijing Wang. Thermodynamics and kinetics of water vapor adsorption onto shale: A case study of the Permian Shanxi Formation, Ordos Basin[J]. Oil & Gas Geology, 2021, 42(1): 173-185.

Figures/Tables 12

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Table 1

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Table 2

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Table 3

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Table 4

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深度/m	有机地化特征			岩矿组成含量/%
深度/m	TOC/%	R_o/%	有机质类型	石英	长石	碳酸盐矿物	黄铁矿	粘土矿物	伊利石	高岭石	绿泥石	伊/蒙混层
3 577.87	2.28	2.45	偏生气型	42	3	—	1	54	23	11	9	11

温度/℃	DW模型						GAB模型					Dent模型
温度/℃	q₁/(mg·g^-1)	q₂/(mg·g^-1)	k₁	k₂	R²	AIC_c	q₀/(mg·g^-1)	C	k	R²	AIC_c	q₀/(mg·g^-1)	K	k	R²	AIC_c
20	6.79	10.84	10.43	0.56	0.997	-2.47	7.99	13.94	0.63	0.997	-11.09	7.99	8.83	0.63	0.997	-11.09
30	7.15	10.31	10.04	0.55	0.998	-7.67	7.96	14.98	0.61	0.998	-16.24	7.96	9.11	0.61	0.998	-16.24
40	4.75	26.59	13.47	0.33	0.998	-11.29	7.91	12.04	0.57	0.998	-15.99	7.91	6.88	0.57	0.998	-15.99

吸附量/(mg·g^-1)	斜率	截距	ΔH/(kJ·mol^-1)	ΔG/(kJ·mol^-1)	ΔS/(kJ·mol^-1·K^-1)
1	-1 164.04	0.22	-9.67	-9.14	-0.0 018
8	-798.61	1.61	-6.64	-2.72	-0.013 4
15	-536.29	1.59	-4.46	-0.59	-0.013 2

模型	拟合参数	p/p₀			T/℃
模型	拟合参数	0.05	0.30	0.90	20	30	40
拟一阶动力学模型	k₁/min^-1	0.24	0.12	0.07	0.13	0.06	0.08
	R²	0.992	0.974	0.968	0.974	0.945	0.971
	AIC_c	-205.12	-255.41	-378.46	-255.41	-230.73	-239.06
拟二阶动力学模型	k₂/(mg³·g^-1·min^-1)	0.23	0.22	0.14	0.23	0.12	0.16
	q_∞/(mg·g^-1)	2.31	1.16	1.13	1.16	1.15	1.11
	R²	0.949	0.952	0.959	0.952	0.97	0.948
	AIC_c	-150.96	-228.82	-353.51	-228.81	-257.78	-215.83
双一阶动力学模型	q₁	0.63	0.60	0.58	0.61	0.55	0.51
	q₂	0.37	0.40	0.42	0.39	0.45	0.49
	k′/min^-1	0.47	0.23	0.14	0.23	0.25	0.32
	k″/min^-1	0.02	0.05	0.06	0.06	0.03	0.06
	R²	0.995	0.995	0.994	0.992	0.993	0.992
	AIC_c	-209.66	-292.44	-466.61	-292.44	-324.83	-288.78
单孔扩散模型	(D/R²)/min^-1	0.014	0.007	0.004	0.006	0.003	0.005
	R²	0.978	0.972	0.979	0.972	0.991	0.981
	AIC_c	-174.95	-251.49	-394.77	-251.49	-303.86	-254.21

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Thermodynamics and kinetics of water vapor adsorption onto shale: A case study of the Permian Shanxi Formation, Ordos Basin

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