ABSTRACT

Glycerol is one of the top 12 platform chemicals obtained from biomass. Its surplus availability as a by-product of biodiesel, fat-splitting and soap manufacturing industries and affordable price lends significant opportunity for its valorization, using solid catalysts, into propanediols (PDOs), particularly to 1,3-propanediol (1,3-PDO), by selective hydrogenolysis. 1,3-PDO is an important chemical with wide applications including that as a precursor in polymers manufacturing. However, the synthesis of 1,3-PDO by selective cleavage of the secondary C-O bond of glycerol in the presence of hydrogen (instead of the primary C-O bond yielding 1,2-PDO) is highly challenging. Of late, supported Pt and Ir catalysts in combination with a reducible oxide (WO_x or ReO_x) were found selective for 1,3-PDO formation. Support, metals composition and additives (co-added metals) affect the performance of these catalysts. Detailed investigations revealed that metal dispersion, electronic connectivity between metal and metal oxide/support, hydrogen activation/spillover and Brönsted acidity are some parameters that influence the activity and selectivity of these bi-functional, metal-metal oxide catalysts. This review summarizes the latest advances in these solid catalysts for selective hydrogenolysis of glycerol to 1,3-PDO, a monomer for advanced polymers.

摘要

甘油是从生物质中获得的 12 大平台化学品之一。其作为生物柴油、脂肪分解和肥皂制造行业的副产品的过剩可用性以及可承受的价格为其利用固体催化剂转化为丙二醇 (PDO)，尤其是 1,3-丙二醇 (1,3- PDO)，通过选择性氢解。1,3-PDO 是一种具有广泛应用的重要化学品，包括作为聚合物制造中的前体。然而，通过在氢存在下选择性裂解甘油的二级 CO 键（而不是产生 1,2-PDO 的主要 CO 键）来合成 1,3-PDO 是非常具有挑战性的。最近，负载型 Pt 和 Ir 催化剂与可还原氧化物（WO _x或 ReO _x) 被发现对 1,3-PDO 形成有选择性。载体、金属成分和添加剂（共同添加的金属）会影响这些催化剂的性能。详细研究表明，金属分散、金属与金属氧化物/载体之间的电子连接性、氢活化/溢出和布朗斯台德酸度是影响这些双功能金属-金属氧化物催化剂的活性和选择性的一些参数。本综述总结了这些用于将甘油选择性氢解为 1,3-PDO（一种先进聚合物单体）的固体催化剂的最新进展。