Reaction Mechanism of One-Step Conversion of Ethanol to 1,3-Butadiene over Zn-Y/BEA and Superior Catalysts Screening  

Zn-Y/BEA上乙醇一步法制1,3-丁二烯的反应机理及优异催化剂筛选

作　　者：Shu-Xuan Dang Han-Xuan Liu Tao Ban Xin Gao Zheng-Qing Huang Dong-Yuan Yang Chun-Ran Chang 党舒轩;刘寒轩;班涛;高新;黄正清;杨东元;常春然(西安交通大学化学工程与技术学院,陕西省能源化工过程强化重点实验室,西安710049;榆林学院化学与化工学院,陕西省低变质煤清洁利用重点实验室,榆林719000;陕西延长石油(集团)有限责任公司,西安710065)

机构地区：[1]Shaanxi Key Laboratory of Energy Chemical Process Intensification,School of Chemical Engineering and Technology,Xi’an Jiaotong University,Xi’an 710049,China [2]Shaanxi Key Laboratory of Low Metamorphic Coal Clean Utilization,School of Chemistry and Chemical Engineering,Yulin University,Yulin 719000,China [3]Shaanxi Yanchang Petroleum(Group)Corp.Ltd.,Xi’an 710065,China

出　　处：《Chinese Journal of Chemical Physics》2022年第4期600-610,I0004-I0009,I0149,共18页化学物理学报（英文）

基　　金：This work was supported by the National Natural Science Foundation of China(No.22078257,No.22038011,and No.22108213);the National Key R&D Program of China(No.2020YFA0710000);the China Postdoctoral Science Foundation(No.2018T111034 and No.2021M692548);the Rising Star Program in Science and Technology of Shaanxi Province(No.2020KJXX-079).Chun-Ran Chang also acknowledges the support from the K.C.Wong Education Foundation.The calculations were performed by using the HPC Platform at Xi’an Jiaotong University。

摘　　要：The one-step conversion of ethanol to 1,3-butadiene has achieved a breakthrough with the development of beta zeolite supported dual metal catalysts.However,the reaction mechanism from ethanol to butadiene is complex and has not yet been fully elucidated,and no catalyst screening effort has been done based on central metal atoms.In this work,density functional theory(DFT)calculations were employed to study the mechanism of one-step conversion of ethanol to butadiene over ZnY/BEA catalyst.The results show that ethanol dehydrogenation prefers to proceed on Zn site with a reaction energy of 0.77 eV in the rate-determining step,and the aldol condensation to produce butadiene prefers to proceed on Y site with a reaction energy of 0.69 eV in the rate-determining step.Based on the mechanism revealed,six elements were selected to replace Y for screening superior combination of Zn-M/BEA(M=Sn,Nb,Ta,Hf,Zr,Ti;BEA:beta polymorph A)for this reaction.As a result,Zn-Y/BEA(0.69 eV)is proven to be the most preferring catalyst compared with the other six ones,and Zn-Zr/BEA(0.85 eV),Zn-Ti/BEA(0.87 eV),and Zn-Sn/BEA(0.93 eV)can be potential candidates for the conversion of ethanol to butadiene.This work not only provides mechanistic insights into one-step catalytic conversion of ethanol to butadiene over Zn-Y/BEA catalyst but also offers more promising catalyst candidates for this reaction.

关 键 词：ETHANOL 1 3-BUTADIENE Zn-Y/BEA Aldol condensation Density functional theory 

分 类 号：TQ221.223[化学工程—有机化工] O643.36[理学—物理化学]