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.

本论文主要研究了新型分子筛的合成与调控以及介孔材料的功能化，以期寻找到适合于绿色化工过程的微孔催化剂。1）合成了含氧化镧和氧化铈的新型沸石（La-CeO 2和Ce-CeO 2），并将其应用于烃类转化反应。2）以TEAOH和十六烷基三甲基氯化铵为双温剂合成了纳米尺寸的MCM-68分子筛，以提高30-50 nm分子筛孔道的利用率; 3）以12-10-10-合成了MR通道系统，并将其应用于联苯（BP）的异丙基化反应，选择性地生成4，4 '-二异丙基联苯（4，4'-DIPB）。4）FeCl_3·6H_2O、AlCl_3·6H_2O、ZrOCl_2·6H_2O等多价金属盐对脂肪酸与脂肪醇的酯化反应具有催化活性。催化物种负载在多价金属盐水解形成的阳离子簇上。簇合物阳离子负载在介孔氧化硅上，提高了催化剂的活性.多价金属盐对月桂酸与甘油的酯化反应也有活性。5）在超临界CO_2介质中，考察了H-Y分子筛和Sc（OTf）_3催化苯酚叔丁基化反应，发现H-Y分子筛和Sc（OTf）_3催化苯酚叔丁基化反应的产率分别为2，4-二叔丁基苯酚和2，4，6-三叔丁基苯酚。与汽相和液相相比，超临界CO_2介质中的产率高，这是由于在超临界CO_2介质中生焦量低。

项目成果

Standardization of catalyst preparation using reference catalyst: ion exchange of mordenite type zeolite: 1. Remarkable dealumination accompanying ion exchange

• DOI: 10.1016/j.apcata.2004.12.036
• 发表时间: 2005-04
• 期刊: Applied Catalysis A-general
• 影响因子: 5.5
• 作者: N. Katada;T. Takeguchi;Tatsuya Suzuki;Toshihisa Fukushima;Kinya Inagaki;S. Tokunaga;H. Shimada;Koich Sato;Y. Oumi;T. Sano;K. Segawa;K. Nakai;H. Shoji;Peng Wu;T. Tatsumi;T. Komatsu;T. Masuda;K. Domen;E. Yoda;J. Kondo;T. Okuhara;Yasuyoshi Kageyama;M. Niwa;M. Ogura;M. Matsukata;E. Kikuchi;N. Okazaki;Motoi Takahashi;A. Tada;S. Tawada;Y. Kubota;Y. Sugi;Y. Higashio;M. Kamada;Yukiyo Kioka;Kohei Yamamoto;T. Shouji;Y. Arima;Y. Okamoto;H. Matsumoto

Standardization of catalyst preparation using reference catalyst: ion exchange of mordenite type zeolite: 2. Origin of dealumination and recommended standard conditions

• DOI: 10.1016/j.apcata.2005.01.026
• 发表时间: 2005-04
• 期刊: Applied Catalysis A-general
• 影响因子: 5.5
• 作者: N. Katada;T. Takeguchi;Tatsuya Suzuki;Toshihisa Fukushima;Kinya Inagaki;S. Tokunaga;H. Shimada;Koich Sato;Y. Oumi;T. Sano;K. Segawa;K. Nakai;H. Shoji;Peng Wu;T. Tatsumi;T. Komatsu;T. Masuda;K. Domen;E. Yoda;J. Kondo;T. Okuhara;Takahide Kanai;M. Niwa;M. Ogura;M. Matsukata;E. Kikuchi;N. Okazaki;Motoi Takahashi;A. Tada;S. Tawada;Y. Kubota;Y. Sugi;Y. Higashio;M. Kamada;Yukiyo Kioka;Kohei Yamamoto;T. Shouji;S. Satokawa;Y. Arima;Y. Okamoto;H. Matsumoto

Layered silicate PLS-1: A new solid base catalyst for C-C bond forming reactions

• DOI: 10.1016/j.catcom.2006.08.015
• 发表时间: 2007-04-01
• 期刊: CATALYSIS COMMUNICATIONS
• 影响因子: 3.7
• 作者: Komura, Kenichi;Kawamura, Toshiya;Sugi, Yoshihiro
• 通讯作者: Sugi, Yoshihiro