SBA-15接枝有机胺官能团催化剂的制备、表征及在醇醛缩合反应中的应用  

Preparation and Characterization of Amine Grafted SBA-15 Catalysts and Their Application in Aldol Condensation Reaction

作　　者：任洪清 谢建军[2,3] 刘华财[2,3] 阴秀丽[2,3] 吴创之[2,3] 

机构地区：[1]中国科学技术大学热科学和能源工程系,安徽合肥230026 [2]中国科学院广州能源研究所 [3]中国科学院可再生能源重点实验室,广东广州510640

出　　处：《林产化学与工业》2014年第2期1-8,共8页Chemistry and Industry of Forest Products

基　　金：国家高技术研究发展计划(863计划)资助项目(2012AA051803);国家自然科学基金资助项目(50906091)

摘　　要：采用后接枝法对介孔分子筛载体SBA-15接枝伯胺基（PA）、仲胺基（SA）、叔胺基（TA）和哌嗪基（PP）4种有机胺官能团制得4种催化剂,用XRD、BET、TG、SEM和元素分析仪对所制备的固体碱催化剂进行表征,以糠醛、丙酮为生物油模型化合物研究了4种催化剂的醇醛缩合反应性能,考察了接枝环境、接枝剂官能团、溶剂及温度对糠醛转化率及糠叉丙酮（ FA）与二糠叉丙酮（ F2 A）选择性的影响。结果表明,XRD及SEM图谱显示后接枝法胺基化改性SBA-15保留了载体高度有序的孔道结构,BET分析结果表明接枝后SBA-15比表面积从829 m^2/g下降至292 m^2/g（哌嗪基SBA-15）,经TG与元素分析计算得到N的接枝量为0.6-1.0 mmol/g；采用N2保护条件进行接枝反应可提高催化剂的催化性能,使用质子型溶剂、升高反应温度均有利于提高糠醛转化率和目标产物选择性,4种碱性官能团中伯胺基具有最高的催化活性和产物选择性。 N2保护环境下以H2 O为溶剂,糠醛和丙酮在 PA/SBA-15催化下80℃经8 h反应后,糠醛转化率为82.6%,FA和F2 A选择性分别为41.4%、8.7%。Solid basic catalysts were synthesized by post-grafting four different organic amines, i. e. primary amine （ PA ） , secondary amine（SA）, tertiary amine（TA） and piperazidine（PP） to mesoporous SBA-15. The samples were characterized by X-ray diffraction, nitrogen adsorption, thermogravimetric analysis, scanning electron microscopy and elemental analysis. The activity of prepared catalysts was tested in aldol condensation reaction of bio-oil model compounds （furfural and acetone）. The influence of graft reaction conditions, different functional groups of amine, solvents and temperature on conversion of furfural and selectivity of FA and F2 A were investigated. The results indicated that the prepared samples retain excellent ordered mesoporous structure with the amino loading at 0. 6 - 1. 0 mmol/g. The catalytic activity increased when strict N2-pretected grafting condition, protic solvent and higher temperature were used. The catalyst containing primary amine （ N2-pretected grafting condition） shows the best catalytic activity. The highest conversion of furfural （82. 6%） and product selectivity of FA （41.4%） and F2 A（8. 7%） can be achieved after reaction at 80 ℃ for 8 h in H2O solvent.

关 键 词：生物油 SBA-15 醇醛缩合 胺 后接枝 

分 类 号：TQ35[化学工程]