CIESC Journal ›› 2016, Vol. 67 ›› Issue (2): 540-548.DOI: 10.11949/j.issn.0438-1157.20151512

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Effect of silica chemistry on structure of Ir-Re bimetallic catalysts and catalysis for glycerol hydrogenolysis

LENG Li, ZHANG Hong, REN Xin, ZHOU Jinghong, SUI Zhijun, ZHOU Xinggui   

  1. State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
  • Received:2015-09-30 Revised:2015-12-22 Online:2016-02-05 Published:2016-02-05
  • Supported by:

    supported by the National Natural Science Foundation of China (21106047).

氧化硅载体对Ir-Re双金属的结构及其催化甘油氢解的影响

冷莉, 张宏, 任鑫, 周静红, 隋志军, 周兴贵   

  1. 华东理工大学化学工程联合国家重点实验室, 上海 200237
  • 通讯作者: 周静红
  • 基金资助:

    国家自然科学基金项目(21106047)。

Abstract:

As an alternative process to petroleum based processes, hydrogenolysis of biomass-derived glycerol to 1, 3-propanediol (1, 3-PD) can be effectively catalyzed by bimetallic Ir-Re catalyst. However it still suffers from low selectivity of 1, 3-PD and low reaction rate. With extension of our previous study, silica was selected as a promising catalyst support to investigate the role of silica chemistry in the Ir-Re catalyst for glycerol hydrogenolysis. Bimetallic Ir-Re catalysts supported on three kinds of silica supports of KIT-6, G-6 and FS were prepared for glycerol hydrogenolysis to produce desired 1, 3-PD. The structure of catalysts were characterized by varied techniques of N2 adsorption-desorption, transmission electron microscopy (TEM), X-ray diffraction (XRD), H2 temperature-programmed reduction (H2-TPR), in-situ CO adsorption diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature-programmed desorption (TPD) of ammonia. Also, the structure-activity relationship of the catalysts was discussed. It showed that the bimetallic catalysts on three silica supports possessed alloy structure of Ir-Re on surface, of which the order of alloy degree follows Ir-Re/KIT-6 > Ir-Re/FS > Ir-Re/G-6. Hydroxyl groups on support surfaces significantly affected the degree of metal dispersion and the interaction between active metallic components and support. The Ir-Re/FS catalyst possessed the highest degree of metal dispersion and exhibited the best initial activity but the worst stability for glycerol hydrogenolysis, while the Ir-Re/KIT-6 catalyst featured the highest degree of alloy thus showed excellent catalytic performance and the highest selectivity to 1, 3-PD of desired product.

Key words: biomass, catalyst support, glycerol, hydrogenation, alloy

摘要:

采用3 种氧化硅载体KIT-6、G-6 和FS 制备了Ir-Re 双金属催化剂,并应用于甘油选择性氢解制备1,3-丙二醇,采用TEM、XRD、H2-TPR、CO-DRIFTS 和NH3-TPD 等手段详细表征了催化剂结构,并探讨其构效关系。研究结果表明: 3 种催化剂表面的Ir-Re 双金属催化剂均形成了Ir-Re 合金结构, 合金化程度为Ir-Re/KIT-6 > Ir-Re/FS > Ir-Re/G-6;载体表面羟基含量显著影响Ir-Re 纳米粒子的分散度及其与载体的相互作用。Ir-Re/FS 的金属分散度最高,甘油氢解的初始活性最高但稳定性最差;而具有良好合金结构的Ir-Re/KIT-6 在甘油氢解中表现出良好的氢解活性和最高的1,3-丙二醇选择性。

关键词: 生物质, 催化剂载体, 甘油, 加氢, 合金

CLC Number: