Reforming and Hydrogenolysis of Glycerol over Ni/ZnO Catalysts Prepared by Different Methods

Reforming and Hydrogenolysis of Glycerol over Ni/ZnO Catalysts Prepared by Different Methods
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不同方法制备的Ni/ZnO催化剂上甘油的重整和氢解

DOI:
10.1016/s1872-2067(11)60405-1
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发表时间:
2012-07
影响因子:
16.5
通讯作者:
Fan Kangnian
Fan Kangnian
中科院分区:
化学1区
文献类型:
--
作者:
Hu Jiye;Liu Xiaoyu;Wang Bin;Pei Yan;Qiao Minghua;Fan Kangnian

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甘油向1,2-丙二醇(1,2-PDO)的催化转化通常在高压釜中在高压H2存在下分批进行。报道了在连续流动固定床反应器中,在Ni/ZnO催化剂上,在不加H2的情况下,甘油重整和氢解制1,2-PDO。采用浸渍法(WI)、共沉淀法(CP)、水热法(HT)和碳微球硬模板法(CT)制备了Ni/ZnO催化剂。采用X射线衍射(XRD)、程序升温还原(TPR)、透射电镜(TEM)和氢滴定等手段对催化剂进行了表征。当甘油空速较低时,1,2-PDO在Ni分散度较高的催化剂上降解为乙醇和气相产物,而当甘油空速较高时,1,2-PDO的选择性受到丙酮醇中间体加氢的限制。在优化的WHSV下,具有较高Ni分散度的催化剂对1,2-PDO具有更高的选择性,并且在具有最高Ni分散度的Ni/ZnO催化剂上,在WHSV为0.84 h-1时,在甘油转化率为85.4%时获得了对1,2-PDO的最高选择性54.9%。
The catalytic conversion of glycerol to 1,2-propanediol (1,2-PDO) is generally conducted batch-wise in an autoclave in the presence of high pressure H2. The reforming and hydrogenolysis of glycerol to 1,2-PDO over Ni/ZnO catalysts in a continuous flow fixed-bed reactor without added H2was reported. The Ni/ZnO catalysts were prepared by wetness impregnation (WI), co-precipitation (CP), hydrothermal treatment (HT), and carbon microsphere hard-templating (CT) methods. The catalysts were characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), transmission electron microscopy (TEM), and H2titration. At a low weight hourly space velocity (WHSV) of glycerol, the 1,2-PDO produced got degraded to ethanol and gas phase products over catalysts with high Ni dispersion, while at a high WHSV, the selectivity for 1,2-PDO was limited by the hydrogenation of the acetol intermediate. At the optimized WHSV, the catalyst with a higher Ni dispersion was more selective for 1,2-PDO, and over the Ni/ZnO catalyst with the highest Ni dispersion, the highest selectivity of 54.9% for 1,2-PDO was obtained at a glycerol conversion of 85.4% at the WHSV of 0.84 h−1.
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