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Research Papers: Energy Systems Analysis

Equilibrium and Kinetics of Water Vapor Adsorption on Shale

[+] Author and Article Information
Shuo Duan

School of Mining and Geomatics,
Hebei University of Engineering,
Handan 056038, China
e-mail: duans10@sina.com

Guodong Li

School of Mining and Geomatics,
Hebei University of Engineering,
Handan 056038, China
e-mail: 344073216@qq.com

1Corresponding author.

Contributed by the Advanced Energy Systems Division of ASME for publication in the JOURNAL OF ENERGY RESOURCES TECHNOLOGY. Manuscript received January 25, 2018; final manuscript received May 24, 2018; published online July 2, 2018. Assoc. Editor: Esmail M. A. Mokheimer.

J. Energy Resour. Technol 140(12), 122001 (Jul 02, 2018) (10 pages) Paper No: JERT-18-1071; doi: 10.1115/1.4040530 History: Received January 25, 2018; Revised May 24, 2018

Water vapor adsorption and desorption isotherms and kinetics studies on three Sichuan Basin shale samples were performed at 298 K by an accurate gravimetric method. The adsorption equilibrium data were fitted using both Dent model and Modified Dent model to estimate the adsorption characteristic of water on the primary and secondary sites. The primary site adsorption is restricted to a monolayer while the secondary site adsorption is associated with multilayer sorption. A positive correlation was found between clay mineral content and monolayer sorption content. The isosteric heats of sorption of water were determined from the equilibrium data and they decreased with the increase of adsorption amount. The adsorption/desorption hysteresis were studied with the pore structure. The kinetics of water vapor adsorption was studied with the unipore model and linear driving force mass transfer (LDF) model. The effective diffusivity and kinetic rate constant varied with the increase of relative pressure, which suggested diffusion of water vapor on shale corresponding to a combination of adsorption on primary sites, adsorption on secondary sites, formation of water clusters, and capillary condensation.

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Figures

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Fig. 1

X-ray diffraction pattern of shale samples: (a) Yy, (b) Cn-wf, and (c) Cn-lmx. (1-quartz, 2-orthoclase, 3-Pyrite, 4-dolomite, 5-calcite, 6-siderite, 7-kaolinite, 8-illite, 9-smectite, 10-chlorite).

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Fig. 2

Adsorption isotherms measured and fitting curves of water vapor on shale sample at 298 K: (a) Yy, (b) Cn-wf, and (c) Cn-lmx

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Fig. 3

Adsorption of water vapor on primary and secondary sites at 298 K: (a) Yy, (b) Cn-wf, and (c) Cn-lmx

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Fig. 4

The relationship between monolayer adsorption contents and clay minerals and TOC contents

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Fig. 5

Isosteric heats of sorption as a function of water sorption content

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Fig. 6

Adsorption kinetics curves and fitting curves of water vapor by the unipore model at the relative pressure of 0.5

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Fig. 7

Effective diffusivity coefficients of water calculated using the unipore model

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Fig. 8

Adsorption kinetics curves and fitting curves of water vapor by the LDF model at the relative pressure of 0.5

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Fig. 9

Kinetic rate constant of water calculated using the LDF model

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Fig. 10

Adsorption/desorption isotherms of water vapor on shale: (a) Yy, (b) Cn-wf, and (c) Cn-lmx

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Fig. 11

The pore structure distribution before and after water sorption experiment for shale samples: (a) Yy, (b) Cn-wf, and (c) Cn-lmx

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