导　　师： 林励吾;田志坚

学科专业： G0304

授予学位： 博士

作　　者： ;

机构地区： 中国科学院大连化学物理研究所

摘　　要： 由于分子筛在众多领域(尤其是催化领域)都有着广泛的应用,因此开展有关分子筛合成及应用的研究具有重要的意义.离子热合成法是一种非常有前景的材料合成新方法,本论文研究了磷酸铝分子筛及杂原子磷酸铝分子筛的离子热合成以及在异构化反应中的应用. 首次在1-丁基-3-甲基溴化咪唑离子液体体系中考察了分子筛的离子热合成过程,结果表明离子液体结构对产物结构具有重要影响.有机胺的加入可以明显改变分子筛的离子热晶化过程,有利于得到纯相的alpo<,4>-5分子筛,这表明有机胺在磷酸铝分子筛的离子热合成过程中具有结构导向作用.在加入有机胺的情况下,采用离子热合成法可以在280℃的高温下合成出高结晶度的纯相alpo<,4>-25分子筛,这大大扩展了离子热合成的温度范围.此外,将微波加热方法同分子筛的离子热合成相结合可以明显缩短反应的时间,提高产物的选择性以及合成过程中的安全性. 首次采用离子热合成法成功地合成出了四种不同的杂原子取代的meapo-11(me=mg,si,zn,mn)分子筛,并考察了其在正构烷烃临氢异构化反应中的性能.结果表明,pt/mgapo-11催化剂具有最佳的异构化反应性能. 重点考察了合成条件对于mgapos分子筛的异构化反应性能的影响.研究发现,mg的引入量以及有机胺的加入对于分子筛的晶相、孔结构、酸性以及异构化反应性能都有明显的影响.通过反应条件的优化,得到了具有优异的异构化性能的pt/mgapo-11催化剂,其在280℃,h<,2>-c<,12>(mol)=15.0,whsv=0.3h<'-1>,p<,total>=1atm的条件下正十二烷的转化率为92.8﹪,选择性为94﹪. Owing to the widely application of molecular sieves in much scientific area, it is of great importance to investigate the synthesis and applications of molecular sieves. Recently, a very promising method, ionothermal synthesis, for preparing materials has been developed by Morris et al. In this work, the ionothermal synthesis of aluminophosphate molecular sieves has been studied. Several MeAPO molecular sieves have been synthesized ionothermally and their catalytic performance in the hydroisomerization of n-alkane has been evaluated. The ionothermal synthesis of molecular sieves in 1-butyl-3-methylimidazolium bromide ionic liquid has been studied for the first time. The results indicate that the structure of ionic liquid has a major influence on the products structure. In the presence of amine, the dynamics of the ionothermal crystallization process is changed, leading to the formation of pure AFI structure. This shows that the amine have a structure-directing effect in the ionothermal synthesis of aluminophosphate molecular sieves. In addition, another pure ATV structure can be synthesized ionothermally at 280°C with the addition of amine. This finding extends the temperature range of ionothermal synthesis. The ionothermal synthesis of molecular sieves was also carried out under microwave conditions, namely the microwave-enhanced ionothermal synthesis of molecular sieves, which combines the advantages of both microwave heating and ionothermal synthesis. Four different MeAPO-11/(Me=Mg, Si, Zn, Mn/) have been successfully prepared using the ionothermal synthesis for the first time. The hydroisomerization performance of the Pt//MeAPO-11 catalysts has been investigated. The results show that the hydroisomerization activity of Pt//MgAPO-11 is the highest. The influence of the reaction variables on the hydroisomerization performance of MgAPOs was studied. It was found that the structure, BET area, acidity, and hydroisomerization performance can be affected by increasing the

关 键 词： 离子热合成 有机胺 结构导向作用 临氢异构化 分子筛 异构化反应

领　　域： [化学工程]