文献类型：期刊文献

中文题名：碱促进剂在Ru/CNFs催化山梨醇氢解制备二元醇中的作用

英文题名：Hydrogenolysis of sorbitol to glycols over carbon nanofibers-supported ruthenium catalyst:The role of base promoter

作者：周静红[1];刘国才[1];隋志军[1];周兴贵[1];袁渭康[1]

机构：[1]华东理工大学化学工程联合国家重点实验室,上海200237

年份：2014

卷号：35

期号：5

起止页码：692

中文期刊名：催化学报

外文期刊名：Chinese Journal of Catalysis

收录：CSTPCD;;EI(收录号：20142017730677);Scopus;北大核心:【北大核心2011】；CSCD:【CSCD2013_2014】；

基金：国家重点基础研究发展计划(973计划;2014CB239702);国家自然科学基金(21106047)~~

语种：中文

中文关键词：山梨醇;氢解;碱促进剂;二元醇;钌催化剂

外文关键词：Sorbitol;Hydrogenolysis;Base promoter;Glycol;Ruthenium catalyst

摘要：研究了NaOH,KOH,Mg(OH)_2,Ba(OH)_2和CaO等5碱促进剂在Ru/CNFs催化山梨醇氢解过程中的作用机制.结果表明,这些碱均能显著提高山梨醇的转化率,但生成二元醇的选择性随碱种类而有所差异,其中以CaO促进的催化剂二元醇选择性最高.CaO提供了用以催化C—C键断裂的OH^-,同时与中间产物形成络合物从而影响反应历程.提出了CaO作为促进剂时山梨醇氢解生成二元醇的反应历程,并由此进一步优化了山梨醇浓度、Ru催化剂用量和碱促进剂用量之间的匹配以达到更高的二元醇产率.
Sorbitol hydrogenolysis over carbon nanofibers-supported Ru （Ru/CNFs） was carried out with different bases （NaOH, KOH, Mg（OH）2, Ba（OH）2, and CaO） to investigate the role of base promoter. The results indicated that all the bases used significantly enhanced the sorbitol conversion while the glycol selectivities varied with the base type and amount. CaO was the best base in terms of glycol selectivity for two reasons. CaO provided OH-for the base-promoted cleavage of C-C bonds, while it also supplied Ca2＋ for complexation with the intermediate aldehydes, thus affecting the reaction pathways. We identified an optimum ratio among sorbitol concentration, Ru/CNFs catalyst, and CaO to achieve favorable glycol selectivities in sorbitol hydrogenolysis. Reaction pathways for sorbitol hydrogenolysis into glycols in aqueous solution in the presence of CaO have been proposed based on the mechanistic study.