沉积物中烯烃化合物的硫化反应机理——基于1-十六烯和角鲨烯的硫化反应模拟实验  

Mechanism of sulfurization of olefin compounds in sediments--Based on simulation experiment of n-hexadecene and squalene

作　　者：马建华 廖玉宏[1,2,3] 蒋彬[1,2,3] 史权 MA Jianhua;LIAO Yuhong;JIANG Bin;SHI Quan(State Key Laboratory of Deep Earth Processes and Resources,Guangzhou Institute of Geochemistry,Chinese Academy of Sciences,Guangzhou 510640,Guangdong,China;CAS Center for Excellence in Deep Earth Science,Guangzhou 510640,Guangdong,China;University of Chinese Academy of Sciences,Beijing 100049,China;China University of Petroleum(Beijing),Beijing 102249,China)

机构地区：[1]中国科学院广州地球化学研究所,深地过程与战略矿产资源全国重点实验室,广东广州510640 [2]中国科学院深地科学卓越创新中心,广东广州510640 [3]中国科学院大学,北京100049 [4]中国石油大学(北京),北京102249

出　　处：《地球化学》2025年第2期188-199,共12页Geochimica

基　　金：国家自然科学基金项目(42173056、41872156)资助。

摘　　要：早成岩阶段,沉积有机质与无机还原硫之间的硫化反应是有机硫化物形成的主要途径之一。烯烃化合物是沉积有机质中的重要活性组分,也是硫化反应的重要前体物,但对于其硫化反应机理及动力学过程的研究较少。本研究以1-十六烯和角鲨烯作为有机质底物,以硫单质、NaHS以及二者的混合物为硫源,模拟早成岩阶段沉积有机质的硫化反应过程,监测不同反应条件下有机质底物和硫化产物的组成和浓度的时间变化,并在此基础上分别计算1-十六烯和角鲨烯形成不同类型有机硫化物的动力学参数,分析硫化反应的影响因素,探讨沉积物中烯烃化合物的硫化反应机理。结果表明:在温和条件下,多价态无机硫混合物相对于硫单质或NaHS更活跃,可以与烯烃快速发生硫化反应;硫化反应中,单个或孤立的双键更容易形成硫醇,而共轭双键倾向于形成含硫杂环,如1-十六烯的硫化产物主要为十六烷基-2-硫醇,而角鲨烯的硫化产物主要为含有1~3个含硫杂环的化合物。除受双键数目的限制外,硫化反应速率与硫化产物类型还受空间位阻效应的影响;1-十六烯和角鲨烯与多价态无机硫混合物发生的硫化反应均符合一级反应动力学模型。角鲨烯的硫化反应呈现出阶段性特征,即先形成含硫杂环较少的化合物,然后形成含有多个含硫杂环的化合物,形成的产物中含硫杂环数量越多,反应速率常数越小。The natural sulfurization between sedimentary organic matter and inorganic reduced sulfur is one of the main formation pathways of organic sulfur compounds.Olefin compounds are important active components of organic matter deposition and precursors of sulfurization reactions.However,few studies have focused on the reaction mechanism and its kinetics.In this study,the sulfurization reaction process of organic matter deposited in early diagenesis was simulated with n-hexadecene and squalene as organic matter substrates,together with elemental sulfur,sodium hydrosulfide,and polyvalent inorganic sulfur mixture(elemental sulfur+sodium hydrosulfide)as the sulfur source.The changes in the compositions and concentrations of the organic substrates and sulfurization products were then monitored under different reaction conditions and reaction times.On this basis,the kinetic parameters of different types of organic sulfides formed from n-hexadecene and squalene were calculated,the factors affecting the sulfurization reaction were analyzed,and the sulfurization reaction mechanism of olefin compounds in sediments was discussed.The results show that under mild conditions,polyvalent inorganic sulfur mixtures are more active sulfur sources than elemental sulfur or sodium hydrosulfide and can react with alkenes rapidly.Single or isolated double bonds are more likely to form mercaptan,while conjugated double bonds tend to form sulfur-containing heterocyclic rings.For example,the product of n-hexadecene is mainly 2-hexadecylmercaptan.The sulfurization products of squalene are mainly compounds containing 1–3 heterocycles containing sulfur.In addition to the number of double bonds,the rate of sulfurization and the type of sulfurization products are also affected by the steric hindrance effect caused by the location of double bonds.The sulfurization reaction of and squalene with a polyvalent inorganic sulfur mixture conforms to a first-order reaction kinetics model.The sulfurization reaction of squalene is characterized by several s

关 键 词：1-十六烯 角鲨烯 有机硫化物 硫化反应 

分 类 号：P593[天文地球—地球化学]