催化学报

催化学报 ›› 2020, Vol. 41 ›› Issue (9): 1311-1319.DOI: 10.1016/S1872-2067(20)63586-0

• 综述 • 上一篇    下一篇

Pt-W催化剂上甘油选择性氢解制备1,3-丙二醇研究进展

王佳a, 杨曼b,d, 王爱琴b,c   

  1. a 西北农林大学林学院, 陕西杨凌 712100;
    b 中国科学院大连化学物理研究所, 航天催化材料重点实验室, 辽宁大连 116023;
    c 中国科学院大连化学物理研究所, 催化基础国家重点实验室, 辽宁大连 116023;
    d 中国科学院大学, 北京 100049
  • 收稿日期:2020-02-21 修回日期:2020-03-16 出版日期:2020-09-18 发布日期:2020-08-08
  • 通讯作者: 王爱琴
  • 基金资助:
    国家自然科学基金（21706215，21690084，21673228）；陕西省自然科学基金（2018JQ2034）；中央高校基本科研业务费专项资金（Z109021701）.

Selective hydrogenolysis of glycerol to 1,3-propanediol over Pt-W based catalysts

Jia Wanga, Man Yangb,d, Aiqin Wangb,c   

  1. a College of Forestry, Northwest A&F University, Yangling 712100, Shaanxi, China;
    b CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
    c State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
    d University of Chinese Academy of Sciences, Beijing 100049, China
  • Received:2020-02-21 Revised:2020-03-16 Online:2020-09-18 Published:2020-08-08
  • Supported by:
    This work was supported by the National Natural Science Foundation of China (21706215, 21690084, 21673228), Natural Science Basic Project of Shaanxi Province (2018JQ2034), and the Fundamental Research Funds for the Central Universities (Z109021701).

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摘要： 生物柴油产业迅猛发展导致甘油大量过剩；另一方面，1，3-丙二醇在聚酯工业中有着重要应用.因此，甘油氢解反应制1，3-丙二醇反应具有重要的应用价值.但是由于热力学和空间位阻的限制，该反应仍存在很大的挑战.目前，用于该过程的催化体系主要包括铱-铼催化体系和铂-钨催化体系两类.本文重点介绍了Pt-W体系在甘油氢解制备1，3-丙二醇的研究进展.
首先比较了钨酸和杂多酸/杂多酸盐、负载型Pt-W和Pt/介孔钨等三类催化剂体系反应性能及其构效关系，总结了影响Pt-W催化剂性能的几因素：（1）WOx的分散状态：亚单层分散的中等尺寸的WOx有利于Pt的分散和产生更多的B酸位，从而有利于甘油仲羟基的断裂生成1，3-丙二醇.（2）Pt的分散度：H2的解离速率和对不饱和中间物种的加氢与Pt的分散度呈现密切的关系.（3）Pt-WOx间的强相互作用：有利于氢溢流和原位B酸的形成.所以，通过优化合成方法、预处理方法、反应条件等来调变这三种因素，以获得高选择性、高活性和稳定性的新型Pt-W催化体系，是未来应着力探索的方向之一.
此外总结了目前存在的三种基于Pt-W体系的催化剂机理，其中一些研究者认为，B酸主要来源于WOx表面的本征酸位，而另一些人则认为源自Pt-WOx界面原位H2的异裂，且是Pt-W基催化剂表现出较高1，3-丙二醇选择性的真正原因.因此，能直观检测中间产物的原位表征技术的发展与应用乃是解决这一争议的未来方向.为了满足实际应用的需要，应从分子尺度上理解失活机制，从而大力提高催化剂的耐久性.
综上，希望本文能够为甘油选择性氢解制1，3-丙二醇高效催化剂的开发提供有用的信息.

关键词: 甘油, 氢解, 1,3-丙二醇, 铂-氧化钨基催化剂

Abstract: The selective hydrogenolysis of glycerol to 1,3-propanediol (1,3-PDO) is an attractive reaction due to the high demand for valorization of huge excess amounts of glycerol supply as well as the important application of 1,3-PDO in polyester industry. Nevertheless, the formation of 1,3-PDO is thermodynamically less favorable than 1,2-PDO, which necessitates the development of efficient catalysts to manipulate the reaction kinetics towards the 1,3-PDO formation. Among others, Pt-W based catalysts have shown promising activities and selectivities of 1,3-PDO although the reaction mechanism is not well addressed at the molecular level. In this short review, we have compared the performances of different Pt-W based catalysts and discussed the key factors influencing the activity and selectivity. Three possible reaction mechanisms have been discussed in terms of the synergy between Pt and WOx and the origin of acid sites. Finally, the long-term stability of the Pt-W catalysts has been discussed. We hope this review will provide useful information for the development of more efficient catalysts for this important reaction.

Key words: Glycerol, Hydrogenolysis, 1,3-propanediol, Pt-W based catalysts