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

清洁化工工艺是工业可持续发展的关键技术之一。沸石是实现这一目的的最重要的候选者。寻找具有大孔结构的新型沸石对开创沸石催化新时代具有重要意义。1)在H-丝光沸石(HM)催化联苯异丙基化反应中观察到4，4‘-二异丙基联苯(4，4’-DIPB)择形生成。形状选择性由HM孔中过渡态的空间限制决定。4，4‘-DIPB的选择性受SiO_2/Al_2O_3比、反应温度等多种因素的影响。2)由于HM孔内的择形催化作用，包埋产物中4，4’-DIPB的选择性较高。4，4‘-二异丙苯的选择性随温度的升高而降低，这归因于4，4’-二异丙苯在外部交流…上的异构化3)用两种有机模板作为SDA合成了全硅MTW，得到了不同堆积顺序的MTW晶体。4)1，1‘-丁二烯(4-氮杂-1-氮杂-2，5-二甲基双环[2.2.2]辛烷)作为合成沸石的结构导向剂(SDA)。从全硅晶体中获得了ZSM-12相中的新相(GUS-1)。GUS-1为正交晶系，晶格常数为a=16.4206(4)，b=20.0540(4)，c=5.0464(1)Å。5)用干凝胶转化法合成高硅[Al]-SSZ-31沸石，发现合成的高硅[Al]-SSZ-31沸石依赖于初始凝胶的碱浓度，在最佳碱浓度下观察到从BEA到SSZ-31再到MFI的相变。当晶化温度从150→C改变到175→C时，观察到了从BEA到SSZ-31的相变。

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