Thermochemical sulfate reduction a review
Thermochemical sulfate reduction a review
复制标题
DOI：
10.1007/bf02547004
复制
发表时间：
1994-07
期刊：
影响因子：
--
通讯作者：
T. P. Goldstein;Z. Aizenshtat
中科院分区：
文献类型：
--
作者：
T. P. Goldstein;Z. Aizenshtat
在许多油气田中发现的高浓度硫化氢被认为是由硫酸盐氧化石油烃产生的，这一反应降低了资源的价值。为了更好地了解油田沉积物中TSR反应的地球化学，本文综述了1991年以来硫酸盐热化学还原（TSR）的有关资料。本文综述了TSR反应的理论和实验研究（包括硫和碳同位素研究），并讨论了它们对地球化学体系的意义。目前的审查同意以前的建议，即硫酸盐的生物化学还原在低于120°C的沉积环境中占主导地位，并支持在175°C以上的温度下，在地球化学合理的反应期间，活性硫物种将以有意义的速率氧化某些有机分子的可能性。我们的结论是，在典型的石油储层反应条件下，元素硫和多硫化物都能够在碱性条件下氧化某些有机分子。但是，除非存在较低氧化态硫，否则单独的硫酸盐不会反应。研究了低价态硫与硫酸盐相互作用形成TSR活性氧化剂的可能性。在TSR系统中，H2S和SO 42-都是形成活性多硫化物还原剂（例如硫代硫酸盐或连多硫酸盐）所必需的。这样的中间体可以用于降低通过硫酸盐经由热生成硫自由基氧化烃的总活化能，硫自由基可以在许多油田沉积物中充当TSR活性氧化剂。我们建议，一些建议的化学机制TSR需要实验验证和结果重新解释地质系统中的TSR关系。
The high concentrations of hydrogen sulfide found in many oil and gas fields is thought to arise from the oxidation of petroleum hydrocarbons by sulfate—a reaction that reduces the value of the resource. This review, undertaken in order to better understand the geochemistry of TSR reaction in oil field sediments, covers the relevant information on thermochemical sulfate reduction (TSR) to 1991. The theoretical and experimental aspects of TSR reactions (including sulfur and carbon isotope studies) are reviewed and their significance to the geochemical system discussed. The present review agrees with previous suggestions that biochemical reduction of sulfate dominates in sedimentary environments below 120°C, and supports the possibility that reactive sulfur species will oxidize certain organic molecules at meaningful rates in geochemically reasonable reaction periods at temperatures above 175°C. We conclude that under typical petroleum reservoir reaction conditions, both elemental sulfur and polysulfides are capable of oxidizing some organic molecules under basic conditions. But that sulfate alone will not react unless lower oxidation state sulfur is present. The possible interaction of low-valence-state sulfur with sulfate to form TSR active oxidants is examined. both H2S and SO42−are required for the formation of active polysufide reductants (e.g. thiosulfate or polythionates) in TSR systems. Such intermediates can serve to lower the overall activation energy of the oxidation of hydrocarbons by sulfate via thermal generation of sulfur radicals that can function as TSR active oxidants in many oil field sediments. We suggest that some proposed chemical mechanisms for TSR need to be experimentally verified and the results re-interpreted with respect to TSR relations in geologic systems.