CAREER: Synthesis, Characterization and Catalytic Evaluation of Novel Dealuminated Zeolite-based Catalysts for the Alkylation of i-Butane with 2-Butene

摘要 提案标题： 四氢呋喃的合成、表征及催化性能评价 新型脱铝沸石基催化剂的研究 异丁烷与2-丁烯的烷基化反应 提案编号：CTS-9702081主要研究者： Panagiotis Smirniotis机构： 辛辛那提大学 脱铝ZSM-12是一种大孔、一维、高硅、十二元环沸石，将用于异丁烷与2-丁烯的烷基化反应。高的稳定性预期作为低焦化形成的结果，并且本研究的目标是了解焦化机理和导致稳定性的沸石特征。 将研究结构选择的Al的脱铝作为改善抗焦化行为的手段。为此，将使用沸石L，其包含连接大空腔的长通道。在通道-腔连接处的Al的选择性脱铝将受到在沸石腔内部产生的5-溴甲基-间苯二甲酸的二聚体的影响。二聚将由合适的自由基引发剂引发。沸石的表征将包括X射线衍射，27 Al NMR以区分骨架与非骨架Al，SEM，吸附碱的红外光谱以确定布朗斯台德和刘易斯酸性，XPS以区分骨架Al的类型，氨TPD以测量其酸性，和EXAFS以研究Al配位和位置。将用环戊烷异构化来评估从沸石L中的通道-腔交叉点去除Al。通过重量分析和可溶性焦炭的质谱分析研究了结焦机理，并对烷基化反应机理进行了动力学研究。该研究对燃料工业具有重要意义，并导致环境友好的过程。

ABSTRACT Proposal Title: Synthesis, Characterization and Catalytic Evaluation of Novel Dealumination Zeolite-based Catalysts for the Alkylation of i-Butane with 2-Butene. Proposal Number: CTS-9702081 Principal Investigator: Panagiotis Smirniotis Institution: Univ. of Cincinnati Dealuminated ZSM-12, a large-pore, one-dimensional, high-silica, 12-member ring zeolite, will be studied for the alkylation of i-butane with 2-butene. High stability is expected as a consequence of low coking formation, and it is the goal of this research to understand the coking mechanism and the zeolite features leading to stability. Dealumination of structurally selected Al will be studied as a means to improve anti-coking behavior. For this purpose, zeolite L, which contains long channels connecting large cavities, will be utilized. Selective dealumination of Al at channel-to-cavity connections will be effected by the dimer of 5-bromomethyl-m-phthalic acid produced inside the zeolite cavity. The dimerization will be initiated by a suitable radical initiator. Characterization of the zeolite will involve X-ray diffraction, 27Al NMR to distinguish framework from non-framework Al, SEM, infrared spectroscopy of adsorbed bases to determine Bronsted and Lewis acidity, XPS to distinguish types of framework Al, ammonia TPD to measure their acidity, and EXAFS to investigate Al coordination and location. The removal of Al from channel-cavity intersections in zeolite L will be assessed with cyclopentane isomerization. The coking mechanism will be studied by gravimetry and by mass spectrometry of soluble coke, and the alkylation mechanisms will be studied kinetically. The research is significant to the fuel industry and leads to environmentally benign processes.