甘油与环己酮缩合反应催化剂的研究  

Investigation on the Catalysts for Condensation of Cyclohexanone with Glycerol

作　　者：张玥[1] 刘杨岷[2] 胡婉男[1] 夏咏梅[1] 

机构地区：[1]江南大学化学与材料工程学院,江苏无锡214122 [2]江南大学食品科学与技术国家重点实验室,江苏无锡214122

出　　处：《精细化工》2008年第4期366-368,391,共4页Fine Chemicals

基　　金：教育部新世纪优秀人才支持计划资助项目~~

摘　　要：通过比较Lewis酸、质子酸、无机酸酐、分子筛、酸化蒙脱土在催化甘油与环己酮缩合反应中的活性,研究了催化剂结构和性质对环己酮转化率和反应选择性的影响。结果表明,Lewis酸有较高的催化活性和稳定性,而且表现为L酸和B酸两种酸的催化形式。催化剂结构对环己酮转化率和反应选择性的影响为:(1)Lewis酸的构成:对相同阴离子的Lewis酸而言,其阳离子的L酸酸强度越强或水解程度越大,催化活性和2-羟甲基-1,4-二氧杂螺环[4,5]癸烷(产物a)的选择性越高;对相同阳离子的Lewis酸而言,其盐酸盐型的催化活性和产物a的选择性要高于硫酸盐型的;(2)水合硫酸盐的催化活性与其煅烧温度有关。催化活性和产物a的选择性最好的Lewis酸为AlCl3。当n(AlCl3)∶n(环己酮)∶n(甘油)=1∶10 000∶15 000,带水剂环己烷加入量为反应物总体积的47%,92℃回流反应2 h,环己酮转化率为97.9%;最终产物中产物a的选择性为97.8%。The condensation of cyclohexanone and glycerol catalyzed by various catalysts was investigated aiming to study the effects of catalyst＇s structure and property on the conversion of cyclohexanone and the reaction selectivity. The catalytic activities of Lewis acid, proton acid, inorganic anhydride, zeolite and montmorillonite were compared. The result indicates that the assayed Lewis acids exhibit high catalytic activity and stability in both forms of Lewis and Brcnsted acid. The main factors influencing the catalytic activities are as follows. （ 1 ） For Lewis acids with same anionic moiety, those containing cationic moieties with stronger Lewis acid intensity or larger hydrolysis equilibrium constant exhibit higher activity and higher selectivity for 2-methylol-1,4-dioxaspiro[4,5 ] decane. In addition, the catalytic activity and selectivity of hydrochlorides are higher than those of sulfates if they contain same cationic moieties. （2）The catalytic activity of the hydrated sulfates is significantly influenced by the calcination temperature. Besides, A1C13 performed the highest catalytic activity and stability among the tested Lewis acids. When the molar ratio of catalyst to reactants was n （ AlCl3 ） ： n （cyclohexanone） ：n（glycerol） = 1：10 000：15 000,the volume ratio of cyclohexane as refluxing solvent and reactants was 47% ,reaction temperature 92 ℃ and reaction time 2 h,a cyclohexanone conversion of 97.9% and a selectivity for 2-methylol-1,4-dioxaspiro [ 4,5 ] decane of 97.8% was achieved.

关 键 词：环己酮 甘油 缩酮 催化 LEWIS酸 缩合 选择性 2-羟甲基-1 4-二氧杂螺环[4 5]癸烷 

分 类 号：O643[理学—物理化学]