New perspectives on supercritical methane adsorption in shales and associated thermodynamics

Tang, Xu; Ripepi, Nino; Rigby, Sean P.; Mokaya, Robert; Gilliland, Ellen

doi:10.1016/j.jiec.2019.06.015

Cited by 38 publications

(57 citation statements)

References 87 publications

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“…Ad-/desorption behaviors of methane molecules in shale pores are controlled by many factors. Many experimental results have confirmed that the total organic carbon (TOC) in shale is positively correlated with an amount of methane adsorption. − The type of organic matter also affects the methane adsorption behavior. The Langmuir pressure is the highest for type I organic matter, followed by type II, and finally the lowest for type III .…”

Section: Introductionmentioning

confidence: 99%

“…Increasing illite content also typically results in less methane adsorption with shale . Yet, the maximum absolute adsorption amount of methane in shale is independent of temperature and pressure, although increased temperatures and pressures lead to a decrease in the adsorption rate …”

Section: Introductionmentioning

confidence: 99%

“…14 Increasing illite content also typically results in less methane adsorption with shale. 17 Yet, the maximum absolute adsorption amount of methane in shale is independent of temperature and pressure, 16 although increased temperatures and pressures lead to a decrease in the adsorption rate. 18 The differences in the adsorption behavior of water molecules by kaolinite, illite, and montmorillonite are mainly attributed to the distribution of adsorption sites on the solid surface.…”

Section: Introductionmentioning

confidence: 99%

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Impact of the Water Adsorption Monolayer on Methane Ad-/Desorption Behavior in Gas Shale Nanopores

Bai

Kang

Chen

et al. 2021

Ind. Eng. Chem. Res.

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When a fracturing fluid invades a nanoscale shale pore structure, it will inevitably affect the ad-/desorption behavior of methane adsorbed on a shale pore wall, impacting the overall methane production of a well. In this work, methane ad-/desorption experiments were conducted on the Longmaxi formation shale with varying levels of relative humidity (0, 0.1, 0.2, 0.3). In addition, the mechanisms and efficiency of methane replacement by water molecules were analyzed. The results indicate that water molecules occupy the adsorption sites of methane molecules in shale nanopores, thus reducing the methane adsorption volume and increasing the difficulty of adsorption. With an increase in the water content, the Langmuir volume of methane adsorption decreases linearly. At high pressures (greater than 8 MPa), a higher water content results in a lower hysteresis index, while at pressures less than 8 MPa, the hysteresis index increases and results in increasing methane desorption compared to dry shale samples. The efficiency of methane replacement by water molecules increases with an increase in the water content and decreases with an increase in pressure. The results of calculating the disjoining pressure of a shale surface-methane adsorption layer-water film system show that the stability of a water film on a shale surface is far greater than that of a methane adsorption layer on a shale surface. These insights will be helpful for analyzing the influence of an imbibition fracturing fluid on shale gas production under in situ conditions.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Impact of the Water Adsorption Monolayer on Methane Ad-/Desorption Behavior in Gas Shale Nanopores

Bai

Kang

Chen

et al. 2021

Ind. Eng. Chem. Res.

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“…The shale in Yichang is a fine-grained sedimentary rock, generally characterized by large specific surface area and high porosity. Most previous studies are conducted with a focus on methane adsorption behavior on shale matrix [11]. To the best of our knowledge, there is no data available in literature about the removal of pyridines by shale.…”

Section: Introductionmentioning

confidence: 99%

Adsorptive Removal of Pyridine from Aqueous Solution Using Natural Shale

Wu¹,

Ding²,

Zou³

et al. 2021

OJOGas

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The discharge of pyridine bearing wastewater into water bodies without a prior satisfactory treatment would pose significant public health risk as well as serious threat to the aquatic ecosystems. In this study, a natural shale from Yichang, China is investigated to determine its potential as a low-cost adsorbent for trace pyridine removal from wastewaters. The prepared shale samples without surface modification are characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and scanning electron microscope (SEM). Kinetics and isotherms of pyridine from aqueous solutions onto shale are investigated on the basis of the experimental data. It is found that the shale samples with well-developed porosity are mainly composed of illite, quartz, calcite, chlorite and sericite. Several kinetic models (viz. pseudo-first-order, pseudo-second-order, two-constant rate, intra-particle diffusion and Elovich) as well as isotherm models (Langmuir, Freundlich and Temkin) are applied to test the experimental data for pyridine removal. The kinetics of the adsorption of pyridine by shale follows a pseudo-second-order rate law with the adsorption data being best described by the Freundlich isotherm model. The preliminary study shows that natural shale obtained from sedimentary basins may be used as a potential low-cost adsorbent for the removal of trace pyridine from effluents.

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“…According to relevant research, shale gas reserves in 41 countries or regions in the world have been estimated at approximately 35,782 trillion cubic feet available for exploitation. 3 The main component of shale gas is CH 4 , which is usually stored in underground shale in three different states: free state, adsorbed state, and dissolved state, 4 where the amount of adsorbed gas accounts for up to 85% of the total shale gas reservoir. 5 At a depth of 1500−2500 m underground in Longmaxi Formation shale gas field in China, it was found that the reservoir temperature was approximately 330−360 K, and the gas pressure could well reach 38 MPa.…”

Section: Introductionmentioning

confidence: 99%

Study on the Adsorption and Thermodynamic Characteristics of Methane under High Temperature and Pressure

Gao

et al. 2020

Energy Fuels

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The understanding of the adsorption and thermodynamic characteristics of methane adsorbed by shale under high pressure and high temperature (HPHT) is of great significance for evaluating deep shale gas reserves and for optimizing shale gas development. In this study, a strict framework for analyzing the adsorption−thermodynamic characteristics of methane adsorption in shale under HPHT conditions was proposed. Further, data processing and explanation of the framework were carried out through reference to published experimental data. When real gas behavior and phase density changes were considered, the temperaturedependent parameters were corrected on the dual-site Langmiur model (DSL) model to reflect the absolute adsorption isotherm at each temperature. These were successfully calculated by combining those with the global fitting method. Compared with other adsorption models that reflected surface heterogeneity, the modified DSL model was found to well characterize the adsorption behavior of shale under HPHT conditions. The thermodynamic potentials of the methane adsorption process were further calculated from the results obtained from the modified DSL model. It was found that in the two groups of shale samples with different total organic carbon (TOC) contents, the change law of isosteric enthalpy with adsorption capacity was different. The abnormal entropy change behavior of methane adsorption in shale with higher TOC content was explained, and a new position concerning the long-standing controversy relating to entropy change was put forward. In addition, both the total entropy and internal energy during the methane adsorbed phase under HPHT increased with an increase in adsorption capacity, and the total entropy in the adsorbed phase revealed a positive relationship with temperature. By introducing a thermodynamic graphic method to draw a clearer and more intuitive U a −n a −S a three-dimensional surface, more thermodynamic potential information could be obtained. The framework proposed in this study could also be used to help future research on the influence of basic physical parameters on adsorption and thermodynamic properties and to provide a foundation for improving the evaluation of deep shale gas reserves.

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New perspectives on supercritical methane adsorption in shales and associated thermodynamics

Cited by 38 publications

References 87 publications

Impact of the Water Adsorption Monolayer on Methane Ad-/Desorption Behavior in Gas Shale Nanopores

Impact of the Water Adsorption Monolayer on Methane Ad-/Desorption Behavior in Gas Shale Nanopores

Adsorptive Removal of Pyridine from Aqueous Solution Using Natural Shale

Study on the Adsorption and Thermodynamic Characteristics of Methane under High Temperature and Pressure

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