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Hydroisomerization of n-dodecane over bi-porous Pt-containing bifunctional catalysts: Effects of alkene intermediates' journey distances within the zeolite micropores

机译:双孔含铂双功能催化剂上正十二烷的加氢异构化:烯烃微孔在沸石微孔中的行程距离的影响

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In this study, three micro/mesoporous composites with MCM-41 materials overgrowing on external surfaces of Y zeolite crystals were prepared. For the three composites, average crystal particle sizes of their zeolite components differed from each other, resulting from the different levels of alkali-treatments to the original Y zeolite before the composite synthesis. Hydroisomerization of n-dodecane (n-C12) was used to evaluate the catalytic performances of bi-porous Pt-loaded composite catalysts with similar metal-acid balances but different average zeolite crystal particle sizes, which leaded to the distinction of alkene intermediates' journey distances inside the acid-rich micropores between two accessible Pt metal sites on three catalysts. The number of protonic sites encountered by alkene intermediates along their diffusion paths, determining the skeletal transformation frequencies, was considered to be proportional to the above-mentioned intermediates' journey distances. Results showed that bifunctional catalysts with smaller average zeolite crystal particle sizes outperformed the catalyst containing the original Y zeolite in the regard of isomerization selectivity. This implied the significant effect of intermediates' journey distances within the microporous arrays between two Pt sites on bifunctional behaviors of catalysts. It can be confirmed that shortening this distance within certain limits indeed contributed to inhibiting secondary reactions, including the skeletal multiple branching and cracking.
机译:在这项研究中,制备了三种微孔/中孔复合材料,它们在Y沸石晶体的外表面上过量生长了MCM-41材料。对于这三种复合材料,其沸石成分的平均晶体粒径互不相同,这是由于在复合合成之前对原始Y沸石的碱处理水平不同。正十二烷(n-C12)的加氢异构化用于评估具有相似金属-酸平衡但具有不同平均沸石晶体粒径的双孔负载Pt的复合催化剂的催化性能,从而区分了烯烃中间体的行程三种催化剂上两个可及的Pt金属位点之间的富酸微孔内部的距离。烯烃中间体沿着其扩散路径遇到的质子位点的数量,决定了骨架的转化频率,被认为与上述中间体的行进距离成正比。结果表明,就异构化选择性而言,具有较小平均沸石晶体粒径的双功能催化剂的性能优于含原始Y沸石的催化剂。这暗示了中间体在两个Pt位点之间的微孔阵列中的行进距离对催化剂的双功能行为具有重大影响。可以确认的是,在一定范围内缩短该距离确实有助于抑制二次反应,包括骨骼的多个分支和破裂。

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