不同温度下噻吩与氢化镁反应路径分析  

Reaction path of thiophene and magnesium hydride at different temperature

作　　者：刘博古 张莉华[1] 李淑芳[1] 蒋瑞乾 刘晓静[1] 李辛元 周仕学[1] 

机构地区：[1]山东科技大学化学与环境工程学院,青岛266590

出　　处：《化工新型材料》2017年第5期124-126,共3页New Chemical Materials

基　　金：国家自然科学基金(21176145);山东科技大学研究基金(2014TDJH105;2014RCJJ019);青岛博士后应用研究项目(201518)

摘　　要：以球磨法制备镁基储氢材料,并作为供氢体对噻吩进行加氢脱硫研究。程序升温脱附(TPD)和差示扫描量热(DSC)测试表明,材料放氢峰温为320℃,可与噻吩加氢温度匹配。噻吩加氢脱硫实验表明,当反应温度为350℃时,噻吩加氢反应转化率最高;反应温度继续升高,转化率则随之下降。加氢脱硫反应产物分析表明,由于温度升高,储氢材料中的活性氢将直接结合生成氢气分子,从而使加氢反应较难进行,噻吩转化率下降。第一性原理计算结果表明,MgH_2直接对噻吩加氢的能量位垒为62.65kJ/mol,而由MgH_2所放出的氢气对噻吩加氢的2个位垒为275.36kJ/mol和365.36kJ/mol。MgH_2与噻吩直接反应更有利于加氢脱硫反应的进行。The Mg-based hydrogen storage material prepared by reactive ball-milling was used as the hydrogen donator in the hydrodesulphurization of thiophene. The temperature programmed desorption （TPD） and differential scanning calorimetry （DSC） analyse of hydrogen storage material showed that the peak temperature of material was 320℃, which can be used to determine the hydrodesulphurization temperature of thiophene. The results of hydrodesulphurization of thiophene showed that the conversion efficiency of thiophene will reach maximum at 350℃ and will reduce when the tempera ture exceeded 350℃. The analysis of reaction products showed that the active H from hydrogen storage material will form H2 molecule preferentially and cannot reacted with thiophene because of the high reaction temperature, which was unfavourable for the hydrodesulphurization. Theoretical study suggested that the energy barrier of hydrodesulphurization of thiophene reacted with MgH2 was 62.65kJ/mol,and the energy barriers of Hz desorption from MgH2 and hydrodesulphurization of thiophene reacted with H2 were 275.36 and 365.36kJ/mol, respectively. This meaned thiophene reacted with MgH2 directly was beneficial for the hydrodesulphurization reaction.

关 键 词：噻吩 加氢脱硫 氢化镁 第一性原理 

分 类 号：O621.25[理学—有机化学]