Studies on Microporous Materials towards Green Chemical Catalysis

微孔材料的绿色化学催化研究

• 批准号: 16310056
• 负责人: SUGI Yoshihiro
• 金额: $ 10.11万
• 依托单位: Gifu University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2004
• 资助国家: 日本
• 起止时间: 2004 至 2006
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-16310056/
• 关键词: green chemical process; solid acid catalyst; esterification of fatty acid; zeolite; mesoporous silica; alkylation; nano-sized zeolite; zeolite framework; 骨格; 環境調和性; 形状選択性; メソポーラスシリカ; 多価金属塩; 超臨界CO_2; フェノールのt-ブチル化; 触媒; メタン酸化; ピリジン-遷移金属錯体

We studied on the synthesis and tuning of preparation of new type of zeolites and functionalization of mesoporous materials in order to find microporous materials as catalysts for green chemical processes. Principal results in this work are as follows :1) New type of BEA zeolite containing lanthana and ceria (La-BEA and Ce-BEA) were synthesized and applied for the hydrocarbon conversion. The decrease in coke-formation by using these zeolites as catalysts resulted in the low deactivation during their catalysis.2) The synthesis of nano-sized BEA was synthesized by using TEAOH and cetyltrimethylammonium chloride as dual temperate in order to enhance the availability of channels of zeolites with particle size of 30-50 nm.3) Three dimensional MCM-68 zeolite with 12-10-10-MR channel system was synthesized and applied for the isopropylation of biphenyl (BP), resulting in the selective formation of 4,4'-diisopropylbiphenyl (4,4'-DIPB). This is due to the discrimination of 4,4'-DIPB from its other DIPB isomers by the restriction in channels.4) Multi-valent metal salts, such as FeCI_3 6H_2O, AICI_3 6H_2O, ZrOCl_2 6H_2O, were active for the esterification of fatty acid with fatty alcohol. The catalytic species are bore on the cationic cluster formed by the hydrolysis of multi-valent metal salt. The catalytic activity as improved by the loading of cluster cation on mesoporous silica. Multi-valent metal salts were also active for the esterification of lauric acid with glycerin. Monolaurin and dilaurin were obtained in presence of excess glycerin by using these salts.5) The t-butylation of phenol was examined over H-Y zeolite and Sc(OTf)_3 in supercritical CO_2 medium, resulting in the high yield of 2,4-di-t-butylphenol over H-Y zeolite and 2,4,6-tri-t-butylphenol over Sc(OTf)_3 supported on mesoporous silica. These high yields compared to those in vapor and liquid phases are due to low coke-formation in supercritical CO_2 medium.

我们研究了新型沸石的合成和调整以及介孔材料的功能化，以便找到微孔材料作为绿色化学过程的催化剂。这项工作中的主要结果如下：1）合成的新型Bea Zeolite含有Lanthana和Ceria（La-Bea和Ce-Bea）的新型Bea沸石被合成并应用于碳氢化合物转换。通过使用这些沸石作为催化剂，可口可乐形成的减少导致其催化过程中失活的失活较低。2）通过使用TeaOH和cetyltyyltrimenymonium氯化物合成纳米尺寸BEA的合成，以增强30-50的Zeolientions Zeolities Zeolities的可用性30-50。与12-10-10-MR通道系统合成并应用于双苯基（BP）的异丙基化，从而选择性形成4,4'-二异丙基苯基苯基（4,4'-DIPB）。这是由于通过通道的限制对4,4'-DIPB从其其他DIPB异构体中歧视。4）多价金属盐，例如FECI_3 6H_2O，AICI_3 6H_2O，ZROCL_2 6H_2O，可用于脂肪酸与脂肪酸的酯化活性。催化物种是由多价金属盐的水解形成的阳离子簇上的孔。催化活性通过介孔二氧化硅上的簇阳离子的加载改善。多价金属盐也有活性，用于用甘油酯化月桂酸的酯化。通过使用这些盐在过量的甘油存在下获得单龙蛋白和dilaurin。在介孔二氧化硅上。与蒸气和液相相比，这些高产量是由于超临界CO_2培养基中的焦气形成较低。