物理化学学报 >> 2014, Vol. 30 >> Issue (12): 2315-2322.doi: 10.3866/PKU.WHXB201410152

催化和表面科学 上一篇    下一篇

Pd-Cu/γ-Al2O3催化苯乙炔选择性加氢反应

王沾祺1, 周志明1, 张锐2, 李莉3, 程振民1   

  1. 1. 华东理工大学化学工程联合国家重点实验室, 上海 200237;
    2. 华东理工大学大型工业反应器工程教育部工程研究中心, 上海 200237;
    3. 华东理工大学化学工程研究所, 上海 200237
  • 收稿日期:2014-08-20 修回日期:2014-10-14 发布日期:2014-11-27
  • 通讯作者: 周志明 E-mail:zmzhou@ecust.edu.cn
  • 基金资助:

    教育部新世纪优秀人才支持计划(NCET-13-0801)和中央高校基本科研业务费(222201313011)资助

Selective Hydrogenation of Phenylacetylene over Pd-Cu/γ-Al2O3 Catalysts

WANG Zhan-Qi1, ZHOU Zhi-Ming1, ZHANG Rui2, LI Li3, CHENG Zhen-Min1   

  1. 1. State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, P. R. China;
    2. Engineering Research Center of Large Scale Reactor Engineering and Technology, Ministry of Education, East China University of Science and Technology, Shanghai 200237, P. R. China;
    3. Institute of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, P. R. China
  • Received:2014-08-20 Revised:2014-10-14 Published:2014-11-27
  • Contact: ZHOU Zhi-Ming E-mail:zmzhou@ecust.edu.cn
  • Supported by:

    The project was supported by the Program for New Century Excellent Talents in University, China (NCET-13-0801) and Fundamental Research Funds for the Central Universities, China (222201313011).

摘要:

为了提高苯乙炔加氢反应中的苯乙烯选择性, 本文采用“胶体-等体积浸渍”两步法制备了Pd-Cu/γ-Al2O3双金属催化剂. 利用高分辨率透射电镜(HRTEM)、X射线光电子能谱(XPS)、CO脉冲化学吸附、N2物理吸附、电感耦合等离子体原子发射光谱(ICP-AES)等技术表征了Pd-Cu/γ-Al2O3的结构性质, 考察了Cu/Pd 摩尔比、Pd负载量以及金属引入顺序对Pd-Cu/γ-Al2O3催化苯乙炔选择性加氢性能的影响. 结果表明, 与Pd/γ-Al2O3单金属催化剂相比, Pd-Cu/γ-Al2O3的苯乙烯选择性大幅度提高, 尤其是当Pd负载量为0.3%(w), 且Cu/Pd摩尔比为0.6时, Pd-Cu/γ-Al2O3表现出优异的加氢选择性; 在0.1 MPa和40 ℃下, 当苯乙炔转化率为90%时, 双金属催化剂的苯乙烯选择性可达95%; 当转化率达到99%以上时, 苯乙烯选择性仍保持在82%左右. 分析表明, Pd-Cu/γ-Al2O3中形成了Pd-Cu合金, 但是两种金属间不存在电子转移, Cu对Pd的几何效应才是导致Pd-Cu/γ-Al2O3苯乙烯选择性增加的主要原因.

关键词: Pd-Cu/γ-Al2O3, 选择性加氢, 苯乙炔, 苯乙烯, 结构-性能关系

Abstract:

A two-step method combining colloid synthesis and incipient wetness impregnation was developed for the preparation of bimetallic Pd-Cu/γ-Al2O3 catalysts, with the aim of increasing the selectivity to styrene in the selective hydrogenation of phenylacetylene. The structural properties of the catalysts were characterized using high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), CO-pulse chemisorption, N2 physisorption, and inductively coupled plasma atomic emission spectrometry (ICPAES). The effects of changing the Cu/Pd molar ratio, the Pd loading, and the order in which the Pd and Cu were introduced into the catalysts on the catalytic activity and selectivity were investigated. The results showed that Pd-Cu/γ-Al2O3 exhibited much higher selectivity toward styrene than Pd/γ-Al2O3. In particular, Pd-Cu/γ-Al2O3 with a Pd loading of 0.3%(w) and a Cu/Pd molar ratio of 0.6 displayed excellent performance at 40℃under 0.1 MPa H2, with a high selectivity of 95% at a conversion of 90%, and a selectivity of approximately 82%, even at conversions of higher than 99%. The increased selectivity of Pd-Cu/γ- Al2O3 was ascribed mainly to the geometrical effects of the Pd-Cu bimetallic alloys, rather than the electronic effects, since no electron transfer occurred between Pd and Cu.

Key words: Pd-Cu/γ-Al2O3, Selective hydrogenation, Phenylacetylene, Styrene, Structureperformance relationship

MSC2000: 

  • O643