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

清洁化工过程是工业可持续发展的关键技术之一。因此，Zeolites是最重要的候选人。寻找新型大孔分子筛对开创分子筛催化的新纪元具有重要意义。本论文致力于合成新型分子筛，并对分子筛催化机理进行深入研究。1）在H-丝光沸石（HM）催化下，联苯异丙基化反应中4，4 '-二异丙基联苯（4，4'-DIPB）的择形生成。形状选择性由HM孔中过渡态的空间限制决定。SiO_2/Al_2O_3比、反应温度等因素对4，4 '-DIPB的选择性有影响。2）HM孔内的择形催化作用使4，4'-DIPB在包埋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，这种降低是由于4，4 ′-DIPB在外磁场作用下发生异构化反应所致 ...更多信息 3）以两种有机模板剂为SDA合成了全硅MTW晶体，得到了不同堆积顺序的MTW晶体。这是由于有机-二氧化硅相互作用以及其他无机因素相关的性质差异。4）1，1 '-亚丁基二（4-氮杂-1-氮鎓-2，5-二甲基双环[2.2.2]辛烷）被用作沸石合成的结构导向剂（SDA）。在ZSM-12相中，由全硅晶体得到一个新相（GUS-1）。GUS-1在正交晶系中被索引，具有精细晶格常数a=16.4206（4）、B=20.0540（4）和c=5.0464（1）π。GUS-1的骨架拓扑结构在IZA的沸石结构数据库（Database of Zeolite Structures）中以代码GON进行了报道。5）通过干凝胶转化法合成高硅[Al]-SSZ-31沸石被发现依赖于初始凝胶的碱浓度，并且在最佳碱浓度下观察到随着时间的推移从SiO2到SSZ-31再到MFI的相变。当晶化温度从150 ℃变化到175 ℃时，观察到了从Al 2 O3到SSZ-31的相变。少

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