沉积盆地热化学硫酸盐还原作用评述

doi:10.11867/j.issn.1001-8166.2005.10.1100

川东天然气藏H₂S 气体泄露而导致重大伤亡事故后，热化学硫酸盐还原作用（TSR）成为了国内研究的热点。在油气储层条件下，尽管甲烷是最稳定的烃类，但TSR被诱发后，因为甲烷浓度远高于其它烃类,水溶甲烷能与硫酸根离子反应产生H₂S 气体。同时，发现在参与TSR反应的有机质、起始温度、硫同位素分馏效应等方面，实验模拟结果均与地质实例观察结果有较大的差异，可能与TSR反应的催化剂等方面认识不足有关。并认为，TSR成因的H₂S或元素硫可以在晚成岩期合并入有机质中，形成新的有机含硫化合物。但在自然界中，这类化合物很少被鉴别出来。

关键词: 硫同位素, 有机硫化物, 热化学硫酸盐还原作用, 实验模拟, 甲烷

Thermochemical sulfate reduction (TSR) has become a hot topic in China after a heavy casualty caused by H₂S leakage from natural gas reservoir in East Sichuan Basin. It is frequently observed that methane gas anhydrite mineral H₂S gas coexist in the same reservoir.Therefore, reaction of methane with solid anhydrite was proposed to generate H₂S under petroleum reservoir conditions (Yue et al., 2003). However, methane is the most stable hydrocarbon under petroleum reservoir conditions. Simulation experiment has shown that it is expected to take 10¹⁷ years for 10% anhydrite solid to react with methane, the reaction being not significant in terms of geological time. However, our data show that there exists a positive correlative relationship between methane carbon isotope and the degree to sulfate reduction in the Triassic Jianlingjia Formation and Fexiangguan Formation, East Sichuan basin. The relationship suggests that aqueous sulfate may have reacted with dissolved methane and generated H₂S. After TSR is initiated by heavier hydrocarbons, natural gas is expected to have much higher partial pressures of methane and much higher concentrations of dissolved methane than heavier hydrocarbons. Relative ¹²C-rich methane preferentially reacts with sulfate due to a kinetic fractionation, resulting in residual ¹³C-rich methane. Based on a great number of experimental simulation, we find that organic matter involved in TSR, TSR initiation temperature and sulfur isotope fractionation during TSR are significantly different from case studies, respectively. One possibility among others is some unknown catalysis involved in TSR. Many lines of evidence have shown that H₂S or/and elemental sulfur generated during TSR have been incorporated into organic matter, but rare newly generated sulfur-containing organic compound has been separated and identified in nature.

Key words: Thermochemical sulfate reduction, Experimental simulation, Methane, Sulfur isotope, Organic sulfur compound.

中图分类号:

TE12

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摘要

THERMOCHEMICAL SULFATE REDUCTION IN SEDIMENTARY-BASINS:A REVIEW