Investigation of the Methane Adsorption Characteristics of Marine

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Investigation of the Methane Adsorption Characteristics of Marine Shale: A Case Study of Lower Cambrian Qiongzhusi Shale in Eastern Yunnan Province, South China Ang Li, Wenlong Ding,* Xuehui Zhou, Xiangyu Cao, Min Zhang, Fuquan Fu, and En Chen School of Energy Resources, China University of Geosciences, Beijing 100083, China Key Laboratory for Marine Reservoir Evolution and Hydrocarbon Abundance Mechanism, Ministry of Education, China University of Geosciences, Beijing 100083, China Key Laboratory for Shale Gas Exploration and Assessment, Ministry of Land and Resources, China University of Geosciences, Beijing 100083, China ABSTRACT: Marine organic-rich shale in South China has considerable exploration potential, and the shale adsorption capacity has a great impact on the accumulation of shale gas. To study the methane adsorption capacity of marine shale, ten shale samples from the Lower Cambrian Qiongzhusi Formation in eastern Yunnan province were investigated by organic geochemical analysis (total organic carbon content, thermal maturity, and kerogen type), X-ray diffraction (XRD) analysis, field emission scanning electron microscopy (FE-SEM), and low-pressure nitrogen adsorption and methane adsorption experiments. Based on the different adsorption mechanisms of various pores, the Dubinin−Radushkevich and Langmuir−Freundlich models were used to construct a supercritical adsorption model of shale. Combined with this model, the mechanisms and characteristics of shale adsorption under supercritical conditions were analyzed. The maximum absolute methane adsorption capacities of micropores (V1) and mesopores-macropores (V2) were also calculated. Not only have the relationships between organic geochemistry, mineral compositions, pore structure parameters, and maximum absolute methane adsorption capacity (both V1 and V2) been discussed but the impact of moisture on the methane adsorption capacity of shale has also been investigated. The results show that the maximum adsorption capacity of mesopores−macropores is greater than that of micropores. Both V1 and V2 are positively correlated with the TOC content, and V2 is more correlated with the TOC content than V1. High maturity is not conducive to methane adsorption of shale. The maximum absolute methane adsorption amounts of per-unit organic matter have positive correlations with the clay mineral content, but show negative correlations with the quartz content. Different clay minerals have different methane adsorption capacities. Both V1 and V2 increase with increasing specific surface area. V1 has a positive correlation with the micropore volume, but V2 has no apparent relationship with the mesopore−macropore volume. Moreover, shale samples with higher moisture contents have lower methane adsorption capacity. It is anticipated that the results of this study will provide guidance for the adsorption characteristics and influence factors of high maturity marine shale. and (2) a product of increasing kerogen aromaticity.10−12 The organic matter abundance is one of the key factors for shale gas potential. Organic matter is not only the source of hydrocarbon gases but also greatly affects the adsorbed methane amount.13−15 Ross and Bustin16 suggested that shale samples with higher maturity have stronger methane adsorption capacity with similar TOC and moisture contents. However, Chalmers and Bustin17 held the view that the increasing maturity of shale would reduce the TOC content, thus weakening the methane adsorption capacity. In addition, clay minerals contribute differently to adsorbed gas capacity, the amount of which is dependent on clay type.18−20 Shale pores can be divided into three types based on the definition provided by the International Union of Pure and Applied Chemistry (IUPAC): micropores (diameter I/S > kaolinite > chlorite > Illite.20 The clay minerals in shale samples are mainly Illite, I/S, and chlorite. The relationships between different clay minerals and the maximum absolute methane adsorption amounts of perunit organic matter are illustrated in Figure 8. V′1 and V′2 show positive correlations with the Illite and I/S contents, but the chlorite content has no correlation with V′1 and a negative correlation with V′2. Multiple factors, such as moisture, diagenesis, and filling, result in the medium−poor correlations between different clay minerals and methane adsorption capacity.58 In particular, a low content and specific surface area cause an ambiguous correlation or even a negative correlation between chlorite and adsorption capacity. Hence, different degrees of diagenetic evolution also significantly affect the methane adsorption of shale. For some low maturity or organic−lean shale samples, clay minerals are the major contributors to gas adsorption space.7 4.3. Effect of pore structure parameters on methane adsorption capacity. Figure 9 shows the relationships between pore structure parameters and maximum absolute adsorption amount (V1 and V2). The maximum absolute adsorption amounts of micropores and mesopores−macropores are both positively correlated with specific surface area; namely, shale with a greater surface area has stronger adsorption capacity. A similar experimentally determined H

DOI: 10.1021/acs.energyfuels.6b03168 Energy Fuels XXXX, XXX, XXX−XXX

Article

Energy & Fuels

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moisture content would have a lower methane adsorption capacity, suggesting that moisture has a negative impact on shale adsorption.

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Postal address: School of Energy Resources, China University of Geosciences, Beijing 100083, China. Tel.: +86 10 82320629. Fax: +86 10 82326850. ORCID

Wenlong Ding: 0000-0002-5328-7629 Notes

The authors declare no competing financial interest.

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Figure 10. Relationships between maximum absolute adsorption capacity (V1 and V2) and moisture content.

adsorption capacities of moisture-equilibrated samples were up to 40% lower than those for dry samples. The absorption capacity of pure clay minerals (montmorillonite, Illite, and kaolinite) will be reduced by 80−95% under moist conditions, which implies that moisture is one of the primary factors that influence the adsorbed gas capacity of clay minerals in shale.6,63 Consequently, the high moisture content in shale reservoirs is not conducive to the accumulation of shale gas.

ACKNOWLEDGMENTS This research was supported by the National Natural Science Foundation of China (Project Nos. 41072098 and 41372139) and the Important National Science and Technology Specific Projects of China (Nos. 2016ZX05046-003, 2011ZX05018001-002 and 2011ZX05009-002-205). The authors would like to thank the staff of all of the laboratories that cooperated in performing the tests and analyses. We are also grateful to the reviewers, whose comments improved the quality of this manuscript.

5. CONCLUSION In this paper, the supercritical methane adsorption mechanisms and characteristics of 10 shale samples from the Lower Cambrian Qiongzhusi Formation in eastern Yunnan Province, South China, were investigated using various experiments and methane adsorption models. Moreover, the factors influencing shale adsorption were also discussed. The following conclusions can be drawn: (1) Based on the different adsorption mechanisms of various pore sizes, a supercritical methane adsorption model is proposed to calculate the maximum absolute methane adsorption amounts of micropores (V1) and mesopores− macropores (V2). V2 is greater than V1, indicating that mesopores and macropores in shale greatly contribute to methane adsorption. (2) The two maximum absolute methane adsorption amounts (V1 and V2) are positively correlated with the TOC content with a good fit, suggesting that the organic matter content is the main controlling factor of shale methane adsorption. V2 has a better fit with the TOC content than V1 because the organic matter pores developed in the organic matter and clay aggregate account for a significant proportion in shale. Moreover, excessive maturity would weaken the adsorption ability of shale. (3) A high quartz content is not conducive to shale adsorption, while clay minerals enhance the adsorption ability. Different clay minerals have different methane adsorption capacities, and clay mineral adsorption will be weakened by multiple factors, such as moisture, diagenesis, and filling. (4) V1 increases with increasing micropore specific surface area and micropore volume, while V2 increases with increasing mesopore−macropore specific surface area but exhibits no apparent relationship with the mesopore− macropore volume. Additionally, shale with a higher

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DOI: 10.1021/acs.energyfuels.6b03168 Energy Fuels XXXX, XXX, XXX−XXX