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Carbon-initiated sulfate reduction in a closed hydrous system: implications for the formation of H2S in deeply buried petroleum reservoirs

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Abstract

Sulfate reduction by activated carbon (AC), a model compound for solid bitumen (pyrobitumen) without gas generative potential, was studied experimentally for the first time. The simulation experiments show that hydrogen sulfide (H2S) is produced from hydrothermal reduction of calcium sulfate (CaSO4) by AC at elevated temperatures. This result demonstrates that water can also act as a hydrogen source for H2S generation in addition to hydrocarbons. The formation mechanism of H2S may undergo a three-stage sequential process with calcium sulfide (CaS) as the unstable intermediate. The reactivity of carbon is thermodynamically higher than that of methane at ≥ 150 oC but lower than that of ethane or propane in sedimentary basins. Carbon-initiated sulfate reduction follows a zero–order reaction with an apparent activation energy Ea of 172.36 kJ/mol. When extrapolated to the temperature range of typical oil and gas reservoirs (100–200 oC), the order of the rate constant is determined as propane > ethane > solid bitumen > methane in the TSR of CaSO4. Although solid bitumen contributes little to hydrocarbon gas generation, H2S derived from carbon-initiated sulfate reduction may act as an indispensable catalyst for the consequent alteration of methane by TSR in deep buried gas reservoirs with high dryness coefficient.

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Acknowledgments

We gratefully acknowledge financial support by the National Natural Science Foundation of China (Nos. 41730424, 418110156, 41472095), the Open Fund of Key Laboratory of Exploration Technologies for Oil and Gas Resources (Yangtze University), Ministry of Education (No. K2018-05) and the Open Fund of Shandong Provincial Key Laboratory of Depositional Mineralization & Sedimentary Minerals, Shandong University of Science and Technology (Grant No. DMSM2018041). Two anonymous reviewers are thanked for their critical and constructive reviews of our paper. Associate Editor Dr. Barry Jay Katz is gratefully acknowledged for his helpful review and instructions.

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Authors and Affiliations

  1. Key Laboratory of Exploration Technologies for Oil and Gas Resources, Ministry of Education, Yangtze University, Jingzhou, 434023, Hubei, China

    Kangle Ding

  2. Shandong Provincial Key Laboratory of Depositional Mineralization & Sedimentary Mineral, Shandong University of Science and Technology, Qingdao, 266590, Shandong, China

    Kangle Ding

  3. College of Chemistry and Environmental Engineering, Yangtze University, Jingzhou, 434023, Hubei, China

    Kangle Ding, Zhenzhen Yu & Yi Wu

  4. College of Resources and Environment, Yangtze University, Wuhan Campus, Wuhan, 430100, China

    Yan Liu

  5. College of Petroleum Engineering, Yangtze University, Wuhan Campus, Wuhan, 430100, China

    Fujia Guan

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  1. Kangle Ding
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  3. Fujia Guan
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  4. Zhenzhen Yu
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Correspondence to Kangle Ding.

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Ding, K., Liu, Y., Guan, F. et al. Carbon-initiated sulfate reduction in a closed hydrous system: implications for the formation of H2S in deeply buried petroleum reservoirs. Arab J Geosci 14, 736 (2021). https://doi.org/10.1007/s12517-021-07087-2

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