文献类型：期刊文献

英文题名：Boosting the Long-Term Stability of Hydrotalcite-Derived Catalysts in Hydrogenolysis of Glycerol by Incorporation of Ca(II)

作者：Gong, Honghui[1];Zhao, Xiuge[1];Li, Xiyu[1];Chen, Manyu[1];Ma, Yuan[1];Fang, Jian[1];Wei, Xinjia[1];Peng, Qingpo[1];Hou, Zhenshan[1]

机构：[1]East China Univ Sci & Technol, Sch Chem & Mol Engn, Res Inst Ind Catalysis, Key Lab Adv Mat, Shanghai 200237, Peoples R China

年份：2021

卷号：9

期号：5

起止页码：2246

外文期刊名：ACS SUSTAINABLE CHEMISTRY & ENGINEERING

收录：;EI(收录号：20210709920195);WOS:【SCI-EXPANDED(收录号:WOS:000618670600025)】；

基金：The authors are grateful for support from the National Natural Science Foundation of China (21773061, 21978095) and the Innovation Program of Shanghai Municipal Education Commission (15ZZ031).

语种：英文

外文关键词：Glycerol; Hydrogenolysis; CaCO3; Basic sites; 1,2-Propanediol

摘要：Selective hydrogenolysis of biomass-derived glycerol into 1,2-propanediol (1,2-PDO) is of practical importance to upgrade the huge amounts of surplus glycerol derived from renewable biomass. Herewith, we report that hydrotalcite-derived catalysts have been employed for selective hydrogenolysis of glycerol into 1,2-PDO under aqueous phase and base-free conditions. In particular, the catalyst of Co-2-Ca-4-Al-3 was recorded as a good catalyst with an optimum glycerol conversion of 100% and 1,2-PDO selectivity of 90.5% in glycerol hydrogenolysis. Meanwhile, it exhibited high stability in consecutive catalytic recycles under batch-wise operation conditions. Furthermore, the catalyst also demonstrated high glycerol conversion (ca. 95.0%) and selectivity to 1,2-PDO (ca. 90.0%) with a long-term catalytic stability (280 h) by a continuous-flow fixed-bed reactor. Additionally, the catalyst can be further extended to selective hydrogenolysis of some other sugar polyols to 1,2 PDO (selectivity up to 50.5% 68.5%). The activity tests and characterizations demonstrated that Co-0 existing in the catalysts acted as active sites in glycerol hydrogenolysis. Also, the further characterization by XRD, HRTEM, and EDS element maps revealed that the distribution of Co was basically consistent with that of Al, while Ca species were adjacent to Co and Al species. The mixed metal oxides CaO-CoAl2O4 were generated arising from a strong interaction between Co(II) and Ca(II) oxides species, which endowed more electron-deficient Co(II) sites and also led to large amounts of moderate basic sites, being favorable for enhancing catalytic activity and selectivity. Notably, the forming CaCO3 phase played a crucial role in preventing the leaching of moderate basic sites and metal species by covering CaO-CoAl2O4 mixed metal oxides, which was the crucial reason that the present Co-2-Ca-4-Al-3 catalyst showed the remarkable catalytic stability under aqueous phase reaction conditions. On the basis of the results above, the reaction pathway has been discussed as well.