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

职业：新型脱铝沸石基催化剂的合成、表征和催化评价，用于异丁烷与 2-丁烯的烷基化

• 批准号: 9702081
• 负责人: Panagiotis Smirniotis
• 金额: $ 31万
• 依托单位: University of Cincinnati Main Campus
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1997
• 资助国家: 美国
• 起止时间: 1997-06-01 至 2002-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9702081&HistoricalAwards=false
• 关键词: CAREER; Synthesis; Characterization; Catalytic; Evaluation

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.

摘要 提案标题：用于异丁烷与 2-丁烯烷基化的新型脱铝沸石催化剂的合成、表征和催化评估。 提案编号：CTS-9702081 首席研究员：Panagiotis Smirniotis 机构：Univ.辛辛那提脱铝 ZSM-12 是一种大孔、一维、高硅、12 元环沸石，将用于异丁烷与 2-丁烯的烷基化反应。由于焦化形成量低，预计会产生高稳定性，本研究的目标是了解焦化机制和导致稳定性的沸石特征。 将研究结构选择的铝的脱铝作为改善抗结焦行为的手段。为此，将使用含有连接大空腔的长通道的 L 型沸石。 Al 在通道与空腔连接处的选择性脱铝将受到沸石空腔内产生的 5-溴甲基-间苯二甲酸二聚体的影响。二聚化将由合适的自由基引发剂引发。沸石的表征将涉及 X 射线衍射、27Al NMR 来区分骨架与非骨架 Al、SEM、吸附碱的红外光谱以确定布朗斯台德和路易斯酸度、XPS 来区分骨架 Al 类型、氨 TPD 来测量其酸度，和 EXAFS 来调查 Al 协调和位置。将通过环戊烷异构化来评估从 L 型沸石的通道-空腔交叉点中去除 Al 的情况。通过可溶性焦的重量分析和质谱分析来研究结焦机理，并从动力学上研究烷基化机理。该研究对燃料行业具有重要意义，并可实现对环境无害的工艺。