Combined NMR and Theoretical Investigation of Alkylation Reactions on Solid Acids

这是一笔由NSF-EPA环境研究伙伴关系共同资助的赠款。它将产生必要的基础知识，为石油行业提供HF催化的烷基化过程的替代催化剂。从防止污染的角度来看，目前认为过渡到固体酸催化是正确的选择，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，需要对机理和催化材料有更好的了解。J.F.Haw教授将与太平洋西北国家实验室的J.B.Nicholas博士合作，研究碳氢化合物在酸性固体上的催化烷基化反应，即磺化氧化锆、BF3/氧化铝和Beta沸石。他们将应用互补技术、流动微反应器中的反应动力学、固体核磁共振和密度泛函理论，研究在选定的固体酸：磺化氧化锆、BF3/氧化铝和贝塔沸石上烷基化反应的基本催化问题。研究的总体目标将是确定酸位结构和反应活性，反式-2-丁烯与异丁烷的烷基化反应机理，以及催化剂失活机理。活性中间体的性质、过渡态、失活途径等将通过光谱、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.