Department of Applied Chemistry, School of Engineering, Tohoku University, 6-6-07, Aoba, Aramaki, Sendai 980-8579, Japan.
ChemSusChem. 2012 Oct;5(10):1991-9. doi: 10.1002/cssc.201200121. Epub 2012 Aug 3.
The hydrogenolysis of erythritol using an Ir-ReO(x)/SiO(2) catalyst was performed for the production of butanediols, which are widely used as a raw material of polymers. The activity and selectivity to butanediols on Ir-ReO(x)/SiO(2) was much higher than that on conventional hydrogenolysis catalysts. The maximum selectivity to 1,4- and 1,3-butanediols reached 33 and 12 % at 74 % conversion, respectively. The erythritol conversion and selectivity to butanediols was almost maintained during four repeating tests if small amounts of acid were added to the reaction and the catalyst was calcined again. The reaction kinetics, reactivity trends, and characterization results indicate a direct hydrogenolysis mechanism in which the hydride species on the Ir metal surface attacks the alkoxide species on the 3D ReO(x) clusters. Based on the production of erythritol by the fermentation of glucose and glycerol, erythritol hydrogenolysis may be a promising pathway for the production of biobutanediols.
使用 Ir-ReO(x)/SiO(2)催化剂对赤藓糖醇进行氢解反应，可生产广泛用作聚合物原料的丁二醇。Ir-ReO(x)/SiO(2) 对丁二醇的活性和选择性远高于传统氢解催化剂。在 74%的转化率下，1,4-和 1,3-丁二醇的最大选择性分别达到 33%和 12%。如果在反应中加入少量酸并再次煅烧催化剂，则赤藓糖醇的转化率和丁二醇的选择性在四次重复测试中几乎保持不变。反应动力学、反应性趋势和表征结果表明存在直接氢解机制，Ir 金属表面上的氢化物物种攻击 3D ReO(x) 簇上的烷氧基物种。基于葡萄糖和甘油发酵生产赤藓糖醇，赤藓糖醇氢解可能是生物丁二醇生产的有前途的途径。
