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.

我们研究新型沸石的合成和制备以及介孔材料的功能化，以寻找微孔材料作为绿色化学过程的催化剂。本工作的主要结果如下：1)合成了新型含氧化镧和二氧化铈的BEA沸石（La-BEA和Ce-BEA），并将其应用于烃类转化。使用这些沸石作为催化剂减少了焦炭形成，导致其催化过程中的失活率较低。 2）采用TEAOH和十六烷基三甲基氯化铵作为双温剂合成纳米BEA，以提高通道的可用性。粒径为30-50 nm的沸石。3)合成了具有12-10-10-MR通道体系的三维MCM-68沸石并应用于联苯（BP）的异丙基化，导致选择性形成4,4'-二异丙基联苯（4,4'-DIPB）。这是由于通道的限制将4,4'-DIPB与其其他DIPB异构体区分开来。4)多价金属盐，例如FeCl_3·6H_2O、AICI_3·6H_2O、ZrOCl_2·6H_2O，对脂肪族化合物的酯化具有活性。酸与脂肪醇。催化物质位于由多价金属盐水解形成的阳离子簇上。通过在介孔二氧化硅上负载簇阳离子来提高催化活性。多价金属盐对于月桂酸与甘油的酯化也具有活性。利用这些盐在过量甘油存在下得到单月桂酸甘油酯和二月桂酸甘油酯。5)在超临界CO_2介质中,在H-Y沸石和Sc(OTf)_3上考察了苯酚的叔丁基化反应,得到了高产率的2,4-二月桂酸甘油酯。 H-Y 沸石上的对叔丁基苯酚和介孔二氧化硅上负载的 Sc(OTf)_3 上的 2,4,6-三叔丁基苯酚。与气相和液相相比，这些高产率是由于超临界CO_2介质中焦炭形成率低。