Experimental Investigation on Hydrothermal Reduction of Sulfates to H₂S and Organic Sulfides by Ethene  

作　　者：Chao Han Kangle Ding Yan Liu Fujia Guan Mei Zou Zhenzhen Yu Yi Wu Chao Han;Kangle Ding;Yan Liu;Fujia Guan;Mei Zou;Zhenzhen Yu;Yi Wu(Key Laboratory of Exploration Technologies for Oil and Gas Resources, Ministry of Education, Yangtze University, Wuhan Campus, Wuhan, China;Shandong Provincial Key Laboratory of Depositional Mineralization & Sedimentary Mineral, Shandong University of Science and Technology, Qingdao, China;College of Chemistry and Environmental Engineering, Yangtze University, Jingzhou, China;College of Resources and Environment, Yangtze University, Wuhan Campus, Wuhan, China;College of Petroleum Engineering, Yangtze University, Wuhan Campus, Wuhan, China)

机构地区：[1]Key Laboratory of Exploration Technologies for Oil and Gas Resources, Ministry of Education, Yangtze University, Wuhan Campus, Wuhan, China [2]Shandong Provincial Key Laboratory of Depositional Mineralization & Sedimentary Mineral, Shandong University of Science and Technology, Qingdao, China [3]College of Chemistry and Environmental Engineering, Yangtze University, Jingzhou, China [4]College of Resources and Environment, Yangtze University, Wuhan Campus, Wuhan, China [5]College of Petroleum Engineering, Yangtze University, Wuhan Campus, Wuhan, China

出　　处：《Open Journal of Yangtze Oil and Gas》2020年第4期188-199,共12页长江油气（英文版）

摘　　要：The kinetic characteristics of alkenes involved in thermochemical sulfate reduction (TSR) have been never reported in geological literature. In this study, TSR by ethene under hydrothermal conditions was performed in the constrained simulation experiments. Typical TSR products consisted of H₂S, CO₂, mercaptans, sulfides, thiophenes derivatives and benzothiophene. The apparent activation energy <i>E</i> and apparent frequency factor <i>A</i> for TSR by ethene were determined as 76.370 kJ/mol and 4.579 s^-1, respectively. The lower activation energy for ethene involved in TSR relative to ethane suggested that the reactivity of ethene is much higher than that of ethane, in accordance with the thermodynamic analysis. Rate constants were determined experimentally using first-order kinetics extrapolate to MgSO₄ half-lives of 67.329 years - 3.053 years in deep burial diagenetic settings (120°C - 180°C). These values demonstrate that the reaction rate for TSR by ethene is extraordinarily fast in high-temperature gas reservoirs (120°C - 180°C). Consequently, the newly formed ethene from thermal cracking and TSR alteration of natural gas and/or petroleum could not survive after TSR process and were rarely detected in natural TSR reservoirs.The kinetic characteristics of alkenes involved in thermochemical sulfate reduction (TSR) have been never reported in geological literature. In this study, TSR by ethene under hydrothermal conditions was performed in the constrained simulation experiments. Typical TSR products consisted of H₂S, CO₂, mercaptans, sulfides, thiophenes derivatives and benzothiophene. The apparent activation energy <i>E</i> and apparent frequency factor <i>A</i> for TSR by ethene were determined as 76.370 kJ/mol and 4.579 s^-1, respectively. The lower activation energy for ethene involved in TSR relative to ethane suggested that the reactivity of ethene is much higher than that of ethane, in accordance with the thermodynamic analysis. Rate constants were determined experimentally using first-order kinetics extrapolate to MgSO₄ half-lives of 67.329 years - 3.053 years in deep burial diagenetic settings (120°C - 180°C). These values demonstrate that the reaction rate for TSR by ethene is extraordinarily fast in high-temperature gas reservoirs (120°C - 180°C). Consequently, the newly formed ethene from thermal cracking and TSR alteration of natural gas and/or petroleum could not survive after TSR process and were rarely detected in natural TSR reservoirs.

关 键 词：Thermochemical Sulfate Reduction (TSR) ETHENE Simulation Experiments Thermodynamic Analysis First-Order Kinetics 

分 类 号：O62[理学—有机化学]