国家冰川冻土沙漠科学数据中心

元数据

名称	Pyrolysis involving n-hexadecane, water and minerals: Insight into the mechanisms and isotope fractionation for water-hydrocarbon reaction
科技资源标识	CSTR:11738.14.NCDC.XDA14.PP4336.2024
DOI	10.1016/j.jaap.2018.01.009
数据共享方式	开放下载
摘要	To ascertain the effects of minerals and dissolved salts on gas generation from water-hydrocarbon reaction, a series of pyrolysis of n-C16 with water and different minerals or salt solutions at 330–420 °C and 50 MPa were conducted in a gold-tube pyrolysis apparatus. It was shown that both calcite and montmorillonite exhibited evidently catalytic effects on gas generation in pyrolysis of hydrocarbon involving water at elevated temperature. The evident higher D/H ratios of methane in hydrous pyrolysis using deuterated water demonstrate that water provided H or D for hydrocarbon gas generation in water-hydrocarbon reaction. Meanwhile, the presence of two minerals resulted in the distinct distribution of the isomeric index (i-C4/n-C4) and carbon isotopic compositions for gas products. In addition, there was a negative correlation between gas yields/isomeric index and NaCl/KCl concentrations in hydrous pyrolysis of n-C16. Theoretical calculations based on density functional theory (DFT) and transition states (TS) revealed that the activation energies for reactions between alkenes and H+ or water are much lower than those involving water and other organic compounds. The water-hydrocarbon reaction in this study should mainly occur via ionic mechanism, though free radical reaction between alkyl radicals and water also presented. Moreover, it was demonstrated that ionic and free radical mechanisms dominated the water-hydrocarbon reaction with montmorillonite and calcite, respectively. The effects of dissolved salts on water-hydrocarbon reaction can be interpreted by the evolution of H+ concentration with salt concentration in aqueous solutions at elevated temperature. In addition, the differences in carbon isotope fractionation for methane generation from water-hydrocarbon reaction via free radical and ionic mechanisms were addressed. Hydrogen isotope fractionation for methane during water-hydrocarbon reaction or hydrogenation by water was also elucidated by thermodynamic calculations. Finally, a model for the prediction of hydrogen isotopic ratios of methane after hydrogen transfer equilibrium between water and methane is proposed.
学科分类	170.50
关键词	Hydrous pyrolysis Water-hydrocarbon reaction Thermodynamic Isotope fractionation
作者	Kun He,Shuichang Zhang,Jingkui Mi,Wenlong Zhang
数据量	1.1 MiB
论文类型：	journal
论文网址：	https://doi.org/10.1016/j.jaap.2018.01.009
期刊名称：	Journal of Analytical and Applied Pyrolysis
出版时间：	2018-03-01

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数据引用

Kun He,Shuichang Zhang,Jingkui Mi,Wenlong Zhang. Pyrolysis involving n-hexadecane, water and minerals: Insight into the mechanisms and isotope fractionation for water-hydrocarbon reaction. 国家冰川冻土沙漠科学数据中心(http://www.ncdc.ac.cn), 2024. https://cstr.cn/CSTR:11738.14.NCDC.XDA14.PP4336.2024.

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本作品采用知识共享署名 4.0 国际许可协议进行许可。

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项目信息详情

项目名称：深层油气形成与分布预测
项目编号：XDA14010000
项目类别：中国科学院战略性先导科技专项（A类）