催化学报

催化学报 ›› 2013, Vol. 34 ›› Issue (11): 2066-2074.DOI: 10.1016/S1872-2067(12)60656-1

• 研究论文 • 上一篇    下一篇

甲酸为氢源的甘油催化选择氢解

袁静, 李舒爽, 于磊, 刘永梅, 曹勇   

  1. 复旦大学化学系, 上海市分子催化和功能材料重点实验室, 上海200433
  • 收稿日期:2013-05-19 修回日期:2013-07-11 出版日期:2013-10-18 发布日期:2013-10-18
  • 通讯作者: Yong Cao
  • 基金资助:

    国家自然科学基金(21273044).

Efficient catalytic hydrogenolysis of glycerol using formic acid as hydrogen source

Jing Yuan, Shushuang Li, Lei Yu, Yongmei Liu, Yong Cao   

  1. Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, China
  • Received:2013-05-19 Revised:2013-07-11 Online:2013-10-18 Published:2013-10-18
  • Contact: Yong Cao
  • Supported by:

    This work was supported by the National Natural Science Foundation of China (21273044).

PDF

793

被引次数

7

摘要：

以甲酸作为氢源, 采用铜基复合金属氧化物催化剂, 催化氢解甘油制备1,2-丙二醇, 其中液相甲酸的高选择性分解是实现甘油氢解的必要和关键步骤. 活性测试表明, 高分散的铜和ZrO2载体间的协同作用对甲酸分解和甘油到1,2-丙二醇的转化至关重要, 20%Cu/ZrO2催化剂的活性最佳. 由于避免使用相对昂贵的化石燃料氢, 因而该催化体系在生物质的高值利用方面具有潜在的应用前景.

关键词: 铜, 二氧化锆, 氢解, 甘油, 甲酸

Abstract:

We describe a sustainable, cost-effective, and highly efficient H2-free protocol for catalytic hydrogenolysis of glycerol to 1,2-propanediol (1,2-PDO) using formic acid (FA) as the H2 source. The process is catalyzed by an earth-abundant and robust Cu-based metal oxide catalyst, in which the high performance of the Cu catalyst for the in situ generation of H2 gas in the system by highly selective decomposition of FA in an aqueous medium is essential. The activity test results showed that a synergy effect of well-dispersed Cu and amphoteric ZrO2 is essential for FA decomposition as well as for glycerol conversion to 1,2-PDO. The Cu content of the Cu/ZrO2 catalyst prepared by the oxalate gel method has a significant role in the FA-mediated glycerol conversion to 1,2-PDO, and a Cu content of 20 wt% on ZrO2 was identified as the optimum Cu content. Moreover, the creation and maintenance of high component dispersion is essential for high glycerol hydrogenolysis activity of the Cu/ZrO2 system. Because selective hydrogenolysis with minimum use of external fossil-fuel H2 is a critical issue in the realization of biorefinery concepts, the procedure described here is expected to be of broad applicability in biomass use.

Key words: Copper, Zirconium dioxide, Hydrogenolysis, Glycerol, Formic acid