期刊
ORGANIC GEOCHEMISTRY
卷 152, 期 -, 页码 -出版社
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.orggeochem.2020.104175
关键词
Short alkanes; Hydrogen sulphide; Thiols; Thiophenes; Pyrolysis; Ab-initio; Equilibrium; Kinetic isotopic effect; Thermal degradation
资金
- Air Liquide
- Israeli Science Foundation [3195/19]
The study investigates the formation and degradation mechanisms of VOSC through pyrolysis experiments, exploring the variations of sulfur compounds under different conditions.
Volatile organic sulfur compounds (VOSC) are found in petroleum natural gas and condensates at trace levels. The abundance and delta S-34 values of VOSC were proposed as a proxy for thermal processes such as oil and gas generation during thermal maturation, thermochemical and microbial sulfate reduction, migration and expulsion. The understanding of VOSC formation and degradation mechanisms is needed to refine the use of delta S-34 values of VOSC as proxies for thermal processes over geological timescales in the subsurface. We therefore conducted pyrolysis experiments at 360 degrees C for 4,12 and 72 h using pentane and H2S or pentanethiol as model compounds to study the formation and degradation pathways of VOSC and associated variations in delta(4S) values. The main products of these experiments are C1-C4 alkanes along with a variety of thiols and thiophenes, the most dominant VOSC formed. Most thiols were in equilibrium with H2S after 4 h based on their 834S values. Thiophenes were first S-34 depleted relative to H2S and only reached equilibrium at the 72 h experiment. The products and 34S fractionations in the pyrolysis experiment of pentanethiol at 360 degrees C and 12 h were similar to those of the experiment with H2S and pentane at the same conditions. This similarity suggests that pentanethiol is an intermediate product in the formation of aromatic VOSC during pyrolysis of pentane and H2S. Benzoand dibenzothiophenes (BTs and DBTs) were formed in the liquid phase and their 34S depleted values relative to H2S indicated that they had not reached equilibrium. Ab-initio calculations of the thermodynamic properties of thiols, thiolanes, thiophenes BTs and DBTs were used to explain the relative abundance of products in the system and predict their abundance and S isotopic signature at reservoir conditions. The thermodynamic data suggests that at equilibrium, only small quantities of thiols and even smaller quantities of thiolanes can exist under our experimental conditions. Unlike thiols, the free energy of formation of thiophenes, BTs and DBTs is negative under these conditions indicating that the formation of these compounds is thermodynamically favored. The result suggests that the delta S-34 values of thiols are controlled by a very rapid equilibrium isotopic effect (EIE). On the other hand, aromatic sulfur compounds can preserve the delta S-34 value of the kinetic isotopic effect (KIE) associated with their formation for longer. However, under typical petroleum reservoir conditions, the formation of aromatic VOSC in the gas phase from short alkanes (
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据