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

doi:10.3969/j.issn.0253-2417.2014.02.001

林产化学与工业 ›› 2014, Vol. 34 ›› Issue (2): 1-8.doi: 10.3969/j.issn.0253-2417.2014.02.001

• 研究报告 • 下一篇

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

任洪清^{1 2}, 谢建军², 刘华财², 阴秀丽², 吴创之²

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;中国科学院可再生能源重点实验室, 广东广州 510640

收稿日期:2013-04-08 出版日期:2014-04-25 发布日期:2014-04-26
通讯作者: 阴秀丽，女，研究员，博士生导师，主要从事生物质能源转化研究；E-mail：xlyin@ms.giec.ac.cn。 E-mail:xlyin@ms.giec.ac.cn
作者简介:任洪清（1987-），男，云南玉溪人，硕士生，研究方向为生物油（水相催化）提质
基金资助:
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）

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

REN Hong-qing^{1 2}, XIE Jian-jun², LIU Hua-cai², YIN Xiu-li², WU Chuang-zhi²

1. Department of Thermal Science & Energy Engineering, University of Science and Technology of China, Hefei 230026, China;
2. Key Laboratory of Renewable Energy, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China

Received:2013-04-08 Online:2014-04-25 Published:2014-04-26

摘要/Abstract

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（F₂A）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 m²/g 下降至 292 m²/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H₂O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F₂A选择性分别为 41.4%、 8.7%。

关键词: 生物油, SBA-15, 醇醛缩合, 胺, 后接枝

Abstract: 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 F₂A 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 F₂A(8.7%) can be achieved after reaction at 80 ℃ for 8 h in H₂O solvent.

Key words: bio-oil, SBA-15, aldol condensation, amine, post-grafting

中图分类号:

TQ35

任洪清, 谢建军, 刘华财, 阴秀丽, 吴创之. 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[J]. 林产化学与工业, 2014, 34(2): 1-8.

REN Hong-qing, XIE Jian-jun, LIU Hua-cai, YIN Xiu-li, WU Chuang-zhi. Preparation and Characterization of Amine Grafted SBA-15 Catalysts and Their Application in Aldol Condensation Reaction[J]. Chemistry and Industry of Forest Products, 2014, 34(2): 1-8.

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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

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