文献类型：期刊文献

英文题名：Mechanism insight into the conversion between COS and thiophene during CO₂ gasification of carbon-based fuels

作者：Xian, Shengxian[1,2];Xie, Ye[1,2];Xu, Qing[1,2];Yang, Zhisi[1,2];Li, Haowei[1,2];Wu, Yujian[1,2]

机构：[1]Guangdong Ocean Univ, Coll Ocean Engn & Energy, Zhanjiang 524088, Peoples R China;[2]Guangdong Ocean Univ, Guangdong Prov Key Lab Intelligent Equipment South, Zhanjiang 524088, Peoples R China

年份：2024

卷号：14

期号：1

外文期刊名：SCIENTIFIC REPORTS

收录：SCI-EXPANDED(收录号：WOS:001270506400091)、、Scopus(收录号：2-s2.0-85198107849)、WOS

基金：This work was supported by the National Natural Science Foundation of China (No.52376171), Guangdong Basic and Applied Basic Research Foundation (2023A1515110541), the Program for Scientific Research Start-up Funds of Guangdong Ocean University (060302062107) and the Zhanjiang Marine Youth Talent Innovation Project (2023E0011).

语种：英文

外文关键词：Carbon-based fuel; CO2 gasification; Sulfur transformation; Conversion between COS and thiophene

外文摘要：Thiophene is the organic sulfur with good thermal stability in carbon-based fuel, clarifying the conversion mechanism between thiophene and COS is beneficial for achieving in-situ sulfur fixation during CO2 gasification of carbon-based fuels, but the mechanism has rarely been reported. Therefore, calculations based on density functional theory were performed and 16 reaction paths were proposed in this research, clarifying the decomposition mechanism of thiophene and re-fixation mechanism of COS. The attachment of CO2 will lead to the destruction of the thiophene ring and the generation of COS, and CO2 adsorption is the rate-determined step, while the carbon atom that adjacent sulfur atom is the reaction active site. However, the energy barriers of CO2 addition reactions are lower than those of CO2 adsorption reactions, and the energy barrier of reactions occurring on the aliphatics are lower than that occurring on the aromatics. The combination of CO2 and thiophene will thermodynamically lead to the generation of COS and CO. Moreover, gaseous sulfur generated from thiophene decomposition will be converted mutually, while H2S will not be converted into COS. Furthermore, COS will be captured by char, forming solid organic sulfur. The re-fixation of COS will occur on aliphatic chains from the decomposition of aromatics.