The application of non-noble metal supported catalysts in the hydroisomerization of long-chain n-alkanes is a novel field, and there is currently not any research available on the deactivation process of these catalysts. We investigated into the deactivation mechanism of NiWS/SAPO-11 catalyst in the hydroisomerization of n-hexadecane in this work for the first time. Specifically, coke deposition behavior and active phase migration were investigated. The reduction of catalytic efficiency of the catalyst was partially aided by the decrease in specific surface area, pore volume, and acid density. From the perspective of the active phase, the clusters of NiWS active phase migrated as the reaction time increased, mostly resulting in an increase in both the stacking number and the length of active phase slabs. The migration of active phase increased the distance between active phase clusters and metal sites, and decreased the utilization ratio of active metal atoms. From the perspective of coke deposition, the coke formed on the catalyst includes soft coke and hard coke. The formation and evolution of coke on the catalyst were investigated. The soft coke (aliphatic compounds) progressively transformed into hard coke (polycyclic aromatic hydrocarbons and graphite-like), and the coke gradually migrated from the external surface of the catalyst to the pore channels as the reaction time increased. It is expected to provide theoretical basis and reference value for the deactivation research and design of non-noble metal supported hydroisomerization catalyst.
SAPO-11 molecular sieves with different crystal sizes and particle sizes, especially nanosized small-crystal SAPO-11 molecular sieves, were successfully synthesized, and the corresponding NiWS-supported catalysts were prepared for the hydroisomerization of n-hexadecane. XRD, SEM, N2 adsorption–desorption, Py-IR, and HRTEM were used to analyze the effects of crystal size and particle size of the supports on their physicochemical properties, active phase properties, and catalytic performance of the catalysts. Through reaction evaluation and analysis of isomeric products, the effects of the size change of the support on the hydroisomerization performance of the catalyst and the hydroisomerization depth of n-hexadecane were determined. Through comprehensive analysis of the cracking products, it was determined that secondary cracking occurred when the conversion of n-hexadecane on the NiW/SAPO-11-S catalyst reached about 42.7%, and the secondary isomerization occurred when the conversion of n-hexadecane reached about 80%. The hydroisomerization reaction network of n-hexadecane over the NiWS/SAPO-11 catalyst was studied emphatically, and it was found for the first time that the secondary cracking of n-hexadecane during hydroisomerization followed the C3-β-scission mechanism.
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