氮改性对乙炔氢氯化反应催化剂吸附性能的影响  

Effect of N-modification on the Adsorption Performance of Acetylene Hydrochlorination Catalyst

作　　者：张善正[1] 康丽华[1] 代斌[1] 

机构地区：[1]石河子大学化学化工学院/新疆兵团化工绿色过程重点实验室/省部共建国家重点实验室培育基地,石河子832003

出　　处：《石河子大学学报（自然科学版）》2013年第4期494-498,共5页Journal of Shihezi University(Natural Science)

基　　金：国家重点基础研究发展计划(973计划)项目(2012CB720302);教育部长江学者和创新团队发展计划(IRT1161)

摘　　要：基于密度泛函理论计算方法,对乙炔氢氯化反应中的催化剂AuCl3二聚体和碳载体分别进行了氮改性,并对其改性前、后的分子分别进行建模优化,比较其分子空间结构的变化,以及对HCl、C2H2、C2H3Cl的吸附能的影响。实验结果表明:氮改性后的AuCl3二聚体与乙二胺的络合物与改性前的AuCl3二聚体相比,Au3+离子之间的距离从3.627增至5.446;对HCl的吸附能从-3.241kJ/mol增至22.926kJ/mol,对C2H2、C2H3Cl的吸附能影响不大。氮改性后的碳载体与改性前相比,对HCl的吸附能从6.898kJ/mol增至9.615kJ/mol,对C2H2、C2H3Cl的吸附能影响较小。计算结果表明:改性后的AuCl3二聚体与乙二胺的络合物和碳载体,可降低催化剂发生团聚的可能性,延长了其使用寿命。Based on density functional theory（DFT）,the catalyst AuCla dimer and carbon carrier of acetylene hydrochlorination reaction and their nitrogen-modified molecules were conducted for modeling optimization, respectively, and compared the molecular changes in the structure of space and the adsorption energy on HC1,Ce He ,C2 H3 C1. Results showed that,compared with the AuCl3 dimer, the distance between Aua＋ ion of the nitrogen-modified AuCla dimer with ethylenediamine complexes increased from 3. 627A to 5. 446A; the adsorp tion energy of the nitrogen-modified AuCl3 dimer with ethylenediamine complexes on HC1 increased from -- 3. 241 kJ/mol to 22. 926 kJ/mol, and it had little effect on C2 H2 and C2 Ha CI. The nitrogen-modified carbon carrier was more conducive to increase the adsorption on HCl（from 6. 898 kJ/mol to 9. 615 kJ/mol）. The calculation results showed that AuCl3 dimer modified with ethylenediamine complex and the nitrogen-modified carbon carrier with could reduce the possibility of catalyst reunion and prolong its life.

关 键 词：乙二胺 氮改性 AuCl3 乙炔氢氯化 碳载体 

分 类 号：O643.31[理学—物理化学]