Continuous hydrogenolysis of glycerol to 1,2-propanediol on highly active Cu/SiO2 catalysts

doi:10.11949/j.issn.0438-1157.20150812

Abstract

Abstract:

Cu/SiO₂ catalysts with different Cu loading were prepared by an ammonia-evaporation method for the glycerol hydrogenolysis in a fixed-bed reactor. The catalysts were characterized by nitrogen adsorption desorption, X-ray powder diffraction, transmission electron microscope, and N₂O-H₂ titration. It was found that the copper phyllosilicate phase was formed during the preparation of the Cu/SiO₂ catalysts. The copper phyllosilicate phase is considered as the dominated contribution to the special characters of the catalyst, such as large surface area, high Cu dispersion as well as strong metal support interactions. As a result, a significant high space-time yield of 4.5 g·g^-1·h^-1 for 1,2-propanediol and rarely good stability were achieved in the hydrogenolysis of glycerol. Moreover, the strongly adsorbed glycerol at the condition of lower conversion was observed to be one of the important reasons for Cu particle growth, and this negative effect was more remarkable than that of water.

Key words: glycerol, hydrogenolysis, 1,2-propanediol, copper phyllosilicates, deactivation, biomass, catalysis

摘要：

采用蒸氨法制备了不同Cu负载量的Cu/SiO₂催化剂,并在连续固定床上催化甘油氢解。通过氮气物理吸附、X射线衍射、透射电镜、氧化亚氮-氢气滴定等手段对催化剂进行了表征。结果表明制备过程中形成的层状硅酸铜使催化剂具有大比表面积、较高的铜分散度以及较强的金属载体相互作用,因而在甘油氢解反应中表现出较好的时空收率和稳定性。此外,研究发现水对催化剂稳定性具有负面作用,而低转化率的情况下催化剂表面冗余的甘油可能是导致催化活性降低的一个重要因素。

关键词: 甘油, 氢解, 1,2-丙二醇, 层状硅酸铜, 失活, 生物质, 催化

CLC Number:

ZHOU Wei, ZHAO Yujun, MA Xinbin. Continuous hydrogenolysis of glycerol to 1,2-propanediol on highly active Cu/SiO₂ catalysts[J]. CIESC Journal, 2015, 66(8): 2999-3006.

周维, 赵玉军, 马新宾. 高活性Cu/SiO₂催化剂上甘油氢解制1,2-丙二醇[J]. 化工学报, 2015, 66(8): 2999-3006.

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Continuous hydrogenolysis of glycerol to 1,2-propanediol on highly active Cu/SiO₂ catalysts

高活性Cu/SiO₂催化剂上甘油氢解制1,2-丙二醇

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