Synthesis of New Types of Zeolite, and their Application to Catalysis

新型沸石的合成及其催化应用

• 批准号: 10450303
• 负责人: SUGI Yoshihiro
• 金额: $ 1.92万
• 依托单位: Faculty of Engineering, 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: 1998
• 资助国家: 日本
• 起止时间: 1998 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-10450303/
• 关键词: Zeolite; Catalysis; Shape-selective catalysis; Isopropylation; H-Mordenite; Zeolite Synthesis; SDA; GON

Clean chemical processes are one of key technologies for sustainable growth of industry. Zeolites are the most important candidate for the purpose. It is important to find new types of zeolite with large pores to establish new era of the zeolite catalysis, . We devote to synthesize new types of zeolite and to understand the mechanism of zeolite catalysis.1) Shape-selective formation of 4,4'-diisopropylbiphenyl (4,4'-DIPB) was observed in the isopropylation of biphenyl over H-mordenite (HM). The shape-selectivity was governed by spatial restriction at transition states in HM pores. The selectivity for 4,4'-DIPB was influenced by many factors such as SiO_2/Al_2O_3 ratio, reaction temperature.2) The high selectivities for 4,4'-DIPB in encapsulated products were observed because of shape-selective catalysis inside HM pores. The decrease of the selectivity for 4,4'-DIPB occurred with the increase of temperature : The decrease was ascribed to the isomerization of 4,4'-DIPB at the external ac … More id sites.3) Two organic templates were used as SDA for the synthesis of all-silica MTW.These templates gives MTW crystals with different stacking sequences. This is ascribed to the difference in the properties related to organic-silica interaction as well as other inorganic factors.4) 1,1'-Butylenedi (4-aza-1-azonia-2,5-dimethylbicyclo [2.2.2] octane) was used as structure-directing agent (SDA) for zeolite synthesis. A new phase (GUS-1) within ZSM-12 phase is obtained from all-silica crystal. GUS-1 is indexed in the orthorhombic crystal class with refined lattice constants a=16.4206(4), b=20.0540(4), and c=5.0464(1) Å. Framework topology of GUS-1 was reported in the Database of Zeolite Structures by IZA under the code GON.5) Synthesis of high-silica [Al]-SSZ-31 zeolite by dry-gel conversion method was found to be dependent on the alkali concentration of the initial gel, and a phase change from BEA to SSZ-31 to MFI was observed with time course at optimum alkali concentration. A phase transformation from BEA to SSZ-31 was observed when the crystallization temperature was changed from 150→C to 175→C. Less

清洁化工工艺是实现工业可持续发展的关键技术之一。沸石是最重要的候选材料。寻找新型的大孔沸石对开创沸石催化新时代具有重要意义。我们致力于新型沸石的合成和沸石催化机理的研究。1)联苯在h -丝光沸石（HM）上发生异丙化反应时，可选择性生成4,4′-二异丙基联苯（4,4′-DIPB）。HM孔隙的形状选择性受过渡态的空间限制。对4,4′-DIPB的选择性受SiO_2/Al_2O_3比、反应温度等因素的影响。2)由于HM孔内的形状选择性催化作用，4,4'-DIPB在包封产物中具有较高的选择性。随着温度的升高，4,4′-DIPB的选择性降低，这主要是由于4,4′-DIPB在外部的异构化。3)采用两种有机模板作为SDA合成全二氧化硅MTW。这些模板给出了具有不同堆叠序列的MTW晶体。这是由于有机硅相互作用性质的不同以及其他无机因素的影响。4)以1,1′-丁烯二烯（4-氮杂-1-氮杂-2,5-二甲基双环[2.2.2]辛烷）为结构导向剂（SDA）合成沸石。从全硅晶体中获得了ZSM-12相内的新相（GUS-1）。GUS-1的晶格常数为a=16.4206(4), b=20.0540(4), c=5.0464(1) Å。5)用干凝胶法合成高硅[Al]-SSZ-31沸石与初始凝胶的碱浓度有关，在最佳碱浓度下观察到从BEA到SSZ-31再到MFI的相变随时间的变化。当晶化温度从150→C升高到175→C时，发现BEA向SSZ-31相变。少

项目成果

Y.Sugi: "Shape-Selective Alkylation of Biphenyl Catalyzed by H-Mordenites"Korean J. Chem Eng.. 17. 1-11 (2000)

Y.Sugi：“H-丝光沸石催化联苯的形状选择性烷基化”韩国 J. Chem Eng.. 17. 1-11 (2000)

Y.Sugi, K.Nakajima, S.Tawada, J.-H.Kim, T.Hanaoka, T.Matsuzaki, Y.Kubota, and K.Kunimori: "Effects of ceria-modification of H-mordenite on the isopropylation of naphthalene and biphenyl"Porous Materials in Environmentally Friendly Processes (Stud.Surf.Sci

Y.Sugi、K.Nakajima、S.Tawada、J.-H.Kim、T.Hanaoka、T.Matsuzaki、Y.Kubota 和 K.Kunimori：“H-丝光沸石的二氧化铈改性对异丙基化的影响

Y.Kubota, M.Hayakawa, N.Sugimoto, Y.Fukushima, and Y.Sugi: "Synthesis of High-Silica Zeolites using Dibenzylmethylammonium Cation, Industriaal Applications of Zeolites"Proceedings Oct.22-25, 2000, Brugge, Belgium, ed.G.F.Froment, and P.A.Jacobs, Technolog

Y.Kubota、M.Hayakawa、N.Sugimoto、Y.Fukushima 和 Y.Sugi：“使用二苄基甲基铵阳离子合成高硅沸石，沸石的工业应用”论文集，2000 年 10 月 22-25 日，比利时布鲁日，

R.Bandyophadhyay, R.K.Ahedi, Y.Kubota, M.Ogawa, Y.Goto, Y.Fukushima, and Y.Sugi: "Synthesis of High-silica [Al]-SSZ-31 by Steam-assisted Conversion Method and its Catalytic Performance in the Isopropylation of Biphenyl"submitted to J.Mater.Chem..

R.Bandyophadhyay、R.K.Ahedi、Y.Kubota、M.Okawa、Y.Goto、Y.Fukushima 和 Y.Sugi：“蒸汽辅助转化法合成高硅 [Al]-SSZ-31 及其催化

K. Nakajima: "Deactivation of External Acid Sites of H-Mordenite with Ceria Modification in the Isopropylation of Biphenyl"Chem. Lett.. 215-216 (1999)

K. Nakajima：“联苯异丙基化中二氧化铈改性的 H-丝光沸石的外部酸位点失活”Chem。