Combined NMR and Theoretical Investigation of Alkylation Reactions on Solid Acids

这是一个由NSF-EPA环境研究伙伴关系共同资助的项目。它将产生必要的基础知识，为石油工业提供hf催化烷基化过程的替代催化剂。从污染防治的角度来看，固体酸催化是目前被认为是正确的选择，但这些催化剂选择性差，失活速度快。为了进一步开发这些催化剂，需要更好地了解机理和催化材料。J.F. Haw教授将与J.B. Nicholas博士（太平洋西北国家实验室）合作，研究在酸性固体上催化烃类的烷基化反应，即磺化氧化锆、BF3/氧化铝和沸石β。他们将运用互补技术、流动微反应器中的反应动力学、固态核磁共振和密度泛函数理论，研究选定固体酸（磺化氧化锆、BF3/氧化铝和沸石β）烷基化过程中的基本催化问题。研究的总体目标是确定酸位结构和反应活性，确定反式-2-丁烯与异丁烷烷基化的机理，确定催化剂失活的机理。活性中间体、过渡态、失活途径等的性质将通过光谱、理论和动力学测量进行研究。

This is a grant co-funded by the NSF-EPA Partnership for Environmental Research. It will generate fundamental knowledge necessary to provide the petroleum industries with alternative catalysts for the HF-catalyzed alkylation processes. Transition to solid-acid catalysis is currently considered the correct alternative from pollution prevention standpoints but these catalysts have poor selectivity and fast deactivation rate. Better understanding of mechanisms and catalytic materials is needed in order to develop further these catalysts. Prof. J.F. Haw in collaboration with Dr. J.B. Nicholas (Pacific Northwest National Laboratory) will investigate the catalyzed alkylation of hydrocarbons on acidic solids, namely sulfonated zirconia, BF3/alumina, and zeolite Beta. They will apply complementary techniques, reaction kinetics in flow microreactor, solid state NMR, and density-functional theory, to investigate fundamental catalysis issues in alkylation over selected solid acids: sulfonated zirconia, BF3/alumina, and zeolite Beta. The overall goal of the research will be the determination of acid site structure and reactivity, mechanism of alkylation of trans-2-butene with isobutane, and mechanism of catalyst deactivation. The nature of active intermediates, transition states, deactivation pathways, etc., will be investigated spectroscopically, theoretically, and by kinetics measurements.