硼改性Cu/Al<sub>2</sub>O<sub>3</sub>催化甘油氢解反应合成1,2-丙二醇

摘要

采用分步浸渍法制备了硼改性Cu/Al₂O₃催化剂,利用XRD、FTIR、UV-Vis、N₂吸附、H₂-TPR、NH₃-TPD和N₂O解离吸附等方法对其结构进行了表征,研究了硼改性对催化剂结构及其催化甘油氢解反应性能的影响.结果表明,先浸渍硼再浸渍Cu时,随硼含量提高,催化剂酸量和Cu分散度增加,Cu与硼物种的相互作用增强.先浸渍Cu后浸渍硼时,催化剂的酸量提高、Cu物种分散程度变化不明显.先浸渍硼明显提高了Cu/Al₂O₃活性及1,2-丙二醇选择性.在220 ℃、3 MPa、质量空速2.0 h^-1及H₂/甘油比为20的条件下,随硼含量提高,甘油转化率及1,2-丙二醇选择性呈现增大趋势,其中硼含量为2%的催化剂上甘油转化率及1,2-丙二醇选择性分别达到99.9%和96.2%.硼改性对Cu/Al₂O₃催化性能的促进作用与催化剂酸性提高及Cu与B之间的相互作用有关.

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	石恒
	赵兰兰
	陈吉祥

关键词：甘油氢解；铜催化剂；硼； 1,2-丙二醇；酸性；分散度

Abstract：

Boron modified Cu/Al₂O₃ catalysts were prepared by the stepwise impregnation method. The catalyst property was characterized by XRD, FTIR, UV-Vis, N₂-sorption, H₂-TPR, NH₃-TPD and dissociative N₂O adsorption. The effects of the impregnation sequence and the boron content on the catalyst structure and performance were investigated. It was found that the addition of boron to Cu/Al₂O₃ can not only increase catalyst acidity but also enhance the Cu dispersion. It is obvious as the boron species was first introduced to the catalyst. Meanwhile, a strong interaction was formed between the boron and Cu species. However, the strong interaction reduced the number of the surface Cu atoms due to the coverage with the B species. This was more serious when the boron species was impregnated after Cu. In the hydrogenolysis of glycerol to 1,2-propanediol, the addition of boron before Cu more favored the performance of Cu/Al₂O₃. Under the condition of 220 ℃, 3.0 MPa, weight hourly space velocity of 2.0 h^-1, and the H₂/glycerol ratio of 20, with increasing the boron mass content from 0 to 2%, the glycerol conversion and the selectivity to 1,2-PDO increased from 17.1% to 99.9% and from 83.7% to 96.2%, respectively. The promotion effect of boron was found to correlate with the increased acidity and the interaction between Cu and B species.

Keywords： glycerol hydrogenolysis； copper catalyst； boron； 1,2-propanediol； acidity； dispersion

Received 2013-05-02;

Corresponding Authors: 陈吉祥,E-mail: jxchen@tju.edu.cn. Email: jxchen@tju.edu.cn

About author: 石恒(1986-),男,硕士生,从事多相催化加氢研究.

引用本文:

石恒, 赵兰兰, 陈吉祥.硼改性Cu/Al₂O₃催化甘油氢解反应合成1,2-丙二醇[J]. 化学工业与工程, 2015,32(6): 13-17

Shi Heng, Zhao Lanlan, Chen Jixiang.Hydrogenolysis of Glycerol to 1,2-Propanediol on Boron Modified Cu/Al₂O₃ Catalysts[J]. Chemcial Industry and Engineering, 2015,32(6): 13-17

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