Fe^(2+)抑控煤中α硫酚结构氧化机理及效果  

Mechanism and effect of Fe^(2+) on restraining oxidation of a-thiophenol structure in the coal

作　　者：邓存宝[1,2] 戴凤威[1,2] 邓汉忠[3] 王钰博[4] 王雪峰[1] 

机构地区：[1]辽宁工程技术大学安全科学与工程学院,辽宁阜新123000 [2]辽宁工程技术大学安全工程技术研究院,辽宁阜新123000 [3]辽宁工程技术大学材料科学与工程学院,辽宁阜新123000 [4]辽宁工程技术大学矿业学院,辽宁阜新123000

出　　处：《安全与环境学报》2017年第1期58-62,共5页Journal of Safety and Environment

基　　金：国家自然科学基金项目(51274112;51174108);国家科技支撑计划项目(2013BAK06B00)

摘　　要：应用Gaussian 03程序,采用密度泛函方法,在B3LYP/6-31G(d,p)水平下,分析Fe^(2+)抑制煤中α位硫酚结构氧化的效果,从而为阻化剂的配制与优选提供数值依据。首先,根据自然键轨道理论分析煤的特征结构C_(10)H_7SH与过渡金属Fe^(2+)形成配合物的成键本质,并结合分子中的原子理论分析其稳定性;然后,分别计算C_(10)H_7SH结构和[FeSH_8CC_(10)]^(2+)配合物吸附O_2的反应过程,得到反应过程所需活化能,以此活化能为指标,表征Fe^(2+)抑控煤中α位硫酚结构氧化的效果。计算结果表明,Fe^(2+)与C_(10)H_7SH结构中的S原子间形成了配位键,根据电子密度拓扑分析得其键能E_(S-Fe)为-128.56 kJ/mol,C_(10)H_7SH结构吸附O_2的反应过程所需活化能为E_C=62.71 kJ/mol,[FeSH_8C_(10)]^(2+)配合物吸附O_2的反应过程所需活化能与其相比增加了35.60 kJ/mol。研究表明,Fe^(2+)对煤中α位硫酚结构氧化具有明显的控制作用。In this paper,we would like to present our analysis results of the inhibitive function of Fe^2＋ on a-thiophenol structure oxidation in the coal by using Gaussian 03 program based on the density functional theory（DFT） in hoping to provide a numerical basis for preparing and selecting the inhibitor at B3LYP/6- 31G（d,p） level.And,it is just for this purpose that we have,first of all,been attempting to optimize the geometries of the characteristic structure of the coal C10H7SH and its complex compound[FeSH8C10]^2＋ and work out the vibration frequencies at the same level so as to make out if they are the stationary points with no imaginary frequency.And,then,we have made an exploration of the essence of the bond forming from transition metal Fe^2＋ and C10H7SH in accordance with the natural bond orbital theory.Furthermore,we have also made an analysis of the bond structure stabilization in accordance with the atoms in molecular theory.Thus,we have made it clear how to control the oxidation and spontaneous combustion of the coal by restraining the chemical adsorption of O2 in the coal,for the initial stage of the coal oxidation should be taken as a process of chemical adsorption of O2 by coal.And,then,we have made the activation energy of the reaction process of O2 adsorption by C10H7SH and[FeSH8C10]^2＋,in which it would be possible for us to make a comparison between the effect of Fe^2＋ restraining oxidation of a-thiophenol structure of the coal.Thus the results show that Fe^2＋ tends to result in a coordinated bond with S atom in C10H7SH structure,which is in accord with the topological analysis results of the electron charge density,with its bond energy being- 128.56 kJ/mol.Thus,it can be concluded that the activation energy of the reaction of O2adsorption by C10H7SH structure proves to be equal to EC =62.71kj/mol whereas the activation energy of the reaction of O2 adsorption by[FeSH8C10]^2＋ complex compound is ET =98.31 kj/mol.Thus,the formulation of the complex compound tends to increase the ac

关 键 词：安全工程 阻化 煤 α位硫酚 吸附 活化能 

分 类 号：X43[环境科学与工程—灾害防治]