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Pyrite-hydrocarbon Interaction under Hydrothermal Conditions: an Alternative Origin of H2S and Organic Sulfur Compounds in Sedimentary Environments
Authors:DING Kangle  MEI Ping and LUO Yue
Institution:1 Key Laboratory of Exploration Technologies for Oil and Gas Resources of Ministry of Education, Yangtze University, Jingzhou 434023, Hubei, China 2 State Key Laboratory of Petroleum Resources and Prospecting, China University of Petroleum, Beijing 102249, China 3 School of Chemistry and Environmental Engineering, Yangtze University, Jingzhou 434023, Hubei, China,3 School of Chemistry and Environmental Engineering, Yangtze University, Jingzhou 434023, Hubei, China and 3 School of Chemistry and Environmental Engineering, Yangtze University, Jingzhou 434023, Hubei, China
Abstract:Sulfate rocks and organic sulfur from sedimentary organic matter are conventionally assumed as the original sulfur sources for hydrogen sulfide (H2S) in oil and gas reservoirs. However, a few recent experiments preliminarily indicate that the association of pyrite and hydrocarbons may also have implications for H2S generation, in which water effects and natural controls on the evolution of pyrite sulfur into OSCs and H2S have not been evaluated. In this study, laboratory experiments were conducted from 200 to 450°C to investigate chemical interactions between pyrite and hydrocarbons under hydrothermal conditions. Based on the experimental results, preliminary mechanism and geochemical implications were tentatively discussed. Results of the experiments showed that decomposition of pyrite produced H2S and thiophenes at as low as 330°C in the presence of water and n-pentane. High concentrations of H2S were generated above 450°C under closed pyrolysis conditions no matter whether there is water in the designed experiments. However, much more organic sulfur compounds (OSCs) were formed in the hydrous pyrolysis than in anhydrous pyrolysis. Generally, most of sulfur liberated from pyrite at elevated temperatures was converted to H2S. Water was beneficial to breakdown of pyrite and to decomposition of alkanes into olefins but not essential to formation of large amounts of H2S, given the main hydrogen source derived from hydrocarbons. In addition, cracking of pyrite in the presence of 1-octene under hydrous conditions was found to proceed at 200°C, producing thiols and alkyl sulfides. Unsaturated hydrocarbons would be more reactive intermediates involved in the breakdown of pyrite than alkanes. The geochemistry of OSCs is actually controlled by various geochemical factors such as thermal maturity and the carbon chain length of the alkanes. This study indicates that the scale of H2S gas generated in deep buried carbonate reservoirs via interactions between pyrite and natural gas should be much smaller than that of thermochemical sulfate reduction (TSR) due to the scarcity of pyrite in carbonate reservoirs and the limited amount of long-chained hydrocarbons in natural gas. Nevertheless, in some cases, OSCs and/or low contents of H2S found in deep buried reservoirs may be associated with the deposited pyrite-bearing rock and organic matters (hydrocarbons), which still needs further investigation.
Keywords:laboratory experiments  pyrite  hydrocarbon  H2S  OSCs  geochemical implications
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