化工学报 ›› 2018, Vol. 69 ›› Issue (6): 2512-2518.DOI: 10.11949/j.issn.0438-1157.20171262

• 催化、动力学与反应器 • 上一篇    下一篇

Cu2O/TiO2催化甲醛乙炔化反应的载体效应

李海涛, 牛珠珠, 杨国峰, 张鸿喜, 王志鹏, 赵永祥   

  1. 山西大学化学化工学院, 精细化学品教育部工程研究中心, 山西 太原 030006
  • 收稿日期:2017-09-18 修回日期:2017-11-10 出版日期:2018-06-05 发布日期:2018-06-05
  • 通讯作者: 赵永祥
  • 基金资助:

    国家自然科学基金项目(21503124);山西省科技攻关计划项目(工业)(20140321013-02)。

Effect of Cu2O/TiO2 catalyst support in formaldehyde ethynylation

LI Haitao, NIU Zhuzhu, YANG Guofeng, ZHANG Hongxi, WANG Zhipeng, ZHAO Yongxiang   

  1. Engineering Research Center of Ministry of Education for Fine Chemicals, School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, Shanxi, China
  • Received:2017-09-18 Revised:2017-11-10 Online:2018-06-05 Published:2018-06-05
  • Supported by:

    supported by the National Natural Science Foundation of China (21503124) and the Project of Scientific and Technological Research in Shanxi Province (Industry)(20140321013-02).

摘要:

以不同温度焙烧的TiO2为载体,CuCl2·2H2O为铜源,NaOH为沉淀剂,L-抗坏血酸钠为还原剂,采用液相还原-沉积沉淀法制备了Cu2O/TiO2,借助X射线粉末衍射(XRD)、H2程序升温还原(H2-TPR)、N2-物理吸附、透射电镜(TEM)、X射线光电子能谱(XPS)等手段,研究了TiO2载体焙烧温度对Cu2O/TiO2甲醛乙炔化反应性能的影响。结果表明,低温焙烧得到的TiO2载体以锐钛矿相存在,与Cu2O物种间具有弱的相互作用,使得Cu2O被过度还原为金属Cu,催化活性较低。随着载体焙烧温度的升高,TiO2中出现金红石相,Cu2O与载体间相互作用增强,Cu2O高效转变为乙炔亚铜活性物种,使催化剂表现出最佳的催化性能。

关键词: 催化, 载体, Cu2O/TiO2, 甲醛乙炔化, 1,4-丁炔二醇

Abstract:

A series of Cu2O/TiO2 catalysts were prepared by liquid reduction-deposition-precipitation technique from copper chloride as copper source, sodium hydroxide as precipitant, sodium L-ascrobate as reducer, and TiO2 calcined at different temperatures as support. The catalysts were characterized by X-ray diffraction (XRD), H2-temperature programmed reduction (H2-TPR), nitrogen physisorption, transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The catalytic activity of these catalysts were studied in formaldehyde ethynylation. The results showed that calcination temperature of TiO2 support had great influence on the catalytic activity of Cu2O/TiO2. TiO2 calcined at low temperature presented mainly as anatase phase and had weak interaction with Cu2O, which could cause over reduction of active Cu2O to inactive metal Cu and result in the decrease of catalytic activity. With the increase of calcination temperature, anatase TiO2 gradually transformed to rutile TiO2 which could inhibit over reduction of active Cu2O due to its strong interaction with Cu2O. As a result of efficient conversion of Cu2O to active Cu (I) ethynlate, the Cu2O/TiO2 catalyst with TiO2 support calcined at high temperatures had the best catalytic activity.

Key words: catalysis, support, Cu2O/TiO2, formaldehyde ethynylation, 1,4-butynediol

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