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Thermal sulfate reduction by ammonium ion (NH4 +): implications for inorganic origin of H2S and N2 in sedimentary basins

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Abstract

In this study, thermal reduction of MgSO4 by NH4Cl was operated in the presence of water at 350 °C for 168 h. It was found that NH4Cl reacted with MgSO4 to produce H2S, N2 and MgCl2 as the main products. Based on the experimental results and the assumption that the MgSO4–NH4Cl reaction could approach a state of chemical equilibrium in natural environments over geological time scales, thermochemical program HSC 6.0 was utilized to model this geochemical process occurring in sedimentary basins. The results indicate that NH4 + thermodynamically more easily participates in the reduction of SO4 2− than C1–C30 normal alkanes of oil and gas at reservoir temperatures. The heat liberated from the reaction of MgSO4–NH4Cl was estimated as 200.40–270.50 J/mol MgSO4 in typical oil and gas reservoirs (100–200 °C), which is much smaller than previous studies. In comparison with the minimum temperature range (100–140 °C) for conventional thermochemical sulfate reduction (TSR) using hydrocarbons, the inferred threshold temperature for initiating reduction of SO 2−4 by NH4 + in geological settings is only about 50–60 °C. The present study shows NH4 + may play an additional role in TSR process by serving as an inorganic reductant, which has substantial implications for the formation of H2S and N2 in sedimentary basins.

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Acknowledgments

The constructive comments of the reviewer were greatly appreciated. The author wishes to thank the National Natural Science Foundations of China (Ratification No.: 40902034), PetroChina Innovation Foundation (No.: 2012D-5006-0104), Young talent project of Hubei Provincial Department of Education (Ratification No.: Q20121206) and the Earmarked Fund of the Key Laboratory of Tectonics and Petroleum Resources of Ministry of Education, China University of Geosciences (No. TPR-2011-29) for the financial support. Thanks are also due to Dr. Dekun Ji, Department of Chemical Engineering, Beijing Institute of Petrochemical Technology for his kind support during the research work.

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

    Kangle Ding

  2. School of Chemistry and Environmental Engineering, Yangtze University, Jingzhou, 434023, Hubei, China

    Kangle Ding

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Ding, K. Thermal sulfate reduction by ammonium ion (NH4 +): implications for inorganic origin of H2S and N2 in sedimentary basins. Carbonates Evaporites 30, 273–279 (2015). https://doi.org/10.1007/s13146-014-0208-3

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