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

doi:10.11949/j.issn.0438-1157.20151512

摘要/Abstract

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

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

中图分类号:

TQ203.2

冷莉, 张宏, 任鑫, 周静红, 隋志军, 周兴贵. 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[J]. 化工学报, 2016, 67(2): 540-548.

LENG Li, ZHANG Hong, REN Xin, ZHOU Jinghong, SUI Zhijun, ZHOU Xinggui. Effect of silica chemistry on structure of Ir-Re bimetallic catalysts and catalysis for glycerol hydrogenolysis[J]. CIESC Journal, 2016, 67(2): 540-548.

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