【作者】 祝刚；

【导师】 王金渠；

【作者基本信息】 大连理工大学 ， 化学工艺， 2006， 博士

【摘要】 沸石膜具有与分子尺寸相近的孔道体系，能耐高温、化学及生物侵蚀，可在分子级别上进行物质分离，实现催化分离一体化及在光电子、及化学传感器等领域中有潜在的应用前景。ZSM-35（FER型）沸石具有独特的孔道结构，是一种性能优良的催化剂且在苯／对二甲苯，正丁烷／异丁烷和水／有机酸等混合物中具有良好的分离性能，在催化和分离等过程中具有潜在的应用价值，开展ZSM-35沸石膜的制备和应用研究，合成出性能优良的FER型沸石膜具有重要的意义。本文分别采用不同的原料、以不同的载体、用不同的合成方法对ZSM-35沸石膜的合成进行了系统的研究，合成出性能良好的沸石膜，并组装成沸石膜反应器在乙苯脱氢制苯乙烯反应中对其性能进行了研究。 分别在吡咯烷，正下丁胺和乙二胺三种不同的模板剂体系中，采用不同的合成原料原位在多孔陶瓷，多孔不锈钢和多孔炭载体上水热合成出表面连续、致密、无明显缺陷的ZSM-35沸石复合膜。结果发现：（1）沸石膜表面晶粒随焙烧温度升高有沿以晶面（h00）平行于载体表面取向变化的趋势；（2）不同的硅源和模板剂对沸石膜表面的形貌和膜表面晶粒的生长取向性都有影响，乙二胺为模板剂时沸石膜表面晶粒生长呈现沿以晶面（h00）平行于载体表面的取向性；（3）SiO₂过渡层上沸石膜晶粒的生长也有以晶面（h00）平行于载体表面的取向性，常温下膜的H₂渗透率在（3.50～3.85）×10^-7mol·m^-2·s^-1·Pa^-1，H₂／C₃H₈和H₂／N₂的理想分离因数分别为6.89～7.62和4.00～4.44之间；（4）采用将载体表面制备的凝胶层直接转化为沸石膜层的新方法，合成出H₂的渗透率为（4.91～5.26）×10^-7mol·m^-2·s^-1·Pa^-1，H₂／C₃H₈和H₂／N₂的理想分离因数分别为6.93～7.33和3.99～4.69之间沸石膜，改善了粗糙载体上合成沸石膜的困难，可用于其它种类沸石膜的制备。（5）二次生长法合成的不锈钢-ZSM-35沸石复合膜管渗透性能较好，H₂的渗透率为8.85×10^-7mol·m^-2·s^-1·Pa^-1，H₂／N₂和H₂／C₃H₈的理想分离因数分别为4.02和7.03；（6）不同原料组合对炭-ZSM-35沸石复合膜的合成和渗透性能都有较大的影响，所合成膜管H₂的渗透率接近10×10^-7mol·m^-2·s^-1·Pa^-1，H₂／C₃H₈理想分离因数均高于相应的努森扩散系数。 在多孔陶瓷载体表面引入醇，详细地研究了不同结构的醇对沸石膜的合成及渗透性能的影响。结果发现：（1）醇处理未导致沸石膜中杂晶相的出现，不同醇处理后膜表面晶粒都有不同程度地表现出以晶面（h00）平行于载体表面的取向生长，结构不同的醇对晶粒取向生长的影响程度为：异丁醇＞正丁醇≈异丙醇，1-辛醇＞1-丁醇≈1-戊醇；（2）结构不同的醇对沸石膜的表面形态有影响，经由醇处理后膜层明显增厚，醇处理可能有促进沸石膜生长的作用；（3）醇处理后使沸石膜管的H₂渗透率明显地降低，H₂／C₃H₈的理想分离因数则显著地提高，最高达到10.31。选择适当的醇处理载体表面，可改善沸石膜管的渗透性能，是一种简单有效的方法。 采用研磨方法获取亚微米级晶种，以二次生长法合成出ZSM-35沸石复合膜。晶种更多还原

【Abstract】 Zeolite membranes with similar molecular-sized channel systems have potential applications in separation of different substances at molecular levels under the circumstances of high-temperature, chemical and biological corrosions and in integration of catalysis and separation processes. ZSM-35 （FER-type） zeolite possessing unique channel systems has been used as catalysts with good conversion and selectivity and recently found excellent performance in separation of benzene/p-xylene, n-butane/i-butane and water/organic acids. So it is of siginificance to conduct preparation and application studies of ZSM-35 zeolite membranes to obtain excellent-quality ZSM-35 zeolite membranes. In this dissertation, by different synthesis methods, a synthesis of ZSM-35 zeolite membranes was studied in detail respectively adopting different initial synthesis materials respectively on ceramic, stainless steel and carbon supports with different physico-chemical characteristics and ZSM-35 zeolite membrane reactors were assembled to be used in dehydrogenation of ethylbenzene to styrene to examine the as-synthesized zeolite membrane performances.Respectively using pyrrolidine, 1-butylamine and ethylenediamine as templates and different silicon resources, zeolite ZSM-35 membranes have hydrothermally been synthesized in situ respectively on the surfaces of porous ceramic, stainless-steel and carbon supports for the first time. Zeolite crystals grow continuously and compactly on the surfaces of synthesized membranes with no apparent defects. The experimental results achieved are as follows:（1） the orientation of crystals on the synthsized membranes tends to become gradually strong with crystal plane （h00） parallel to the support surface with the calcination temperatures increasing;（2） different templates and different silicon resources all have apparent influences on the morphology or the orientation of the synthesized membranes, among which the crystal growth on the membrane surfaces presents the orientation with crystal plane （h00） parallel to the support surface when ethylenediamine is used as templates;（3） the crystal growth, to some degree, takes on the orientation with crystal plane （h00） parallel to the support surface when the zeolite membrane is grown on the SiO₂ medium layer between the zeolite layer and the support, and H₂ permeation rates of the membrane grown on the SiO₂layer are （3.50-3.85）×10^-7mol·m^-2·s^-1·Pa^-1 with the ideal separation factors of H₂/ C₃H₈ and H₂/ N₂ being 6.89-7.62 and 4.00—4.44, respectively;（4） the zeolite ZSM-35 membrane has been synthesized by directly converting the gel更多还原