强酸性SnO_(2)/SiO_(2)催化山梨醇脱水制异山梨醇  

Dehydration of sorbitol to isosorbide over highly acidic SnO_(2)/SiO_(2)catalyst

作　　者：曹麒 韩玉福 董运洋 郭佳星 王新承 宋永吉[1] CAO Qi;HAN Yufu;DONG Yunyang;GUO Jiaxing;WANG Xincheng;SONG Yongji(Beijing Key Laboratory of Enze Biomass Fine Chemicals,College of New Materials and Chemical Engineering,Beijing Institute of Petrochemical Technology,Beijing 102617,China)

机构地区：[1]北京石油化工学院新材料与化工学院恩泽生物质精细化工北京市重点实验室,北京102617

出　　处：《石油化工》2023年第8期1039-1046,共8页Petrochemical Technology

基　　金：国家自然科学基金项目(21908009)。

摘　　要：通过硅改性的方法制备了SnO_(2)/SiO_(2)复合氧化物,经酸化后得到强酸性SnO_(2)/SiO_(2)(Sn-Si)催化剂;通过NH3-TPD、FTIR、吡啶吸附FTIR、Raman光谱等对Sn-Si催化剂进行了表征,将催化剂用于无溶剂体系中山梨醇直接催化脱水制异山梨醇的反应,并对反应条件进行了优化;考察了SO_(4)^(2-)/Sn-Si催化剂的重复使用性,并分析了催化机理。实验结果表明,在SO_(4)^(2-)/Sn-Si催化剂用量10%(w)、150℃下反应1 h的条件下,山梨醇可完全转化,异山梨醇和1,4-失水山梨醇收率分别为73.25%和18.45%,且催化剂具有良好的重复使用性。B酸和L酸协同催化有助于抑制副反应,提高异山梨醇的收率。研究结果对异山梨醇非均相催化体系的开发及产业化应用有较好的借鉴意义。SnO_(2)/SiO_(2)composite oxides were prepared by silicon modification,and acid modified to obtain the strong acidic SnO_(2)/SiO_(2)(Sn-Si)catalyst.The catalyst was characterized by NH3-TPD,FTIR,pyridine-FTIR,and Raman spectroscopy analysis.The reaction conditions for the dehydration of sorbitol to isosorbide in solvent-free system over the Sn-Si catalyst were optimized.The reusability of SO_(4)^(2-)/Sn-Si catalyst was investigated and the catalytic mechanism was analyzed.The experimental results show that sorbitol can be completely converted under the conditions of SO_(4)^(2-)/Sn-Si catalyst amount 10%(w),reaction temperature 150℃and reaction time 1 h,and the yield of isosorbide and 1,4-sorbitan is 73.25%and 18.45%,respectively.The catalyst has good reusability.It was proposed that the co-catalysis of B acid and L acid was helpful to inhibit side reactions,leading to high isosorbide yield.This study could be a good reference for the development and industrial application of heterogeneous catalytic system of isosorbide.

关 键 词：二氧化锡 酸改性 山梨醇 催化脱水 异山梨醇 

分 类 号：TQ032.41[化学工程]