In order to prepare non-noble metal supported hydroisomerization catalyst with high catalytic performance, this work first proposed a novel three-stage crystallization method to synthesize small-crystal and hierarchical SAPO-11 molecular sieve, and prepared the corresponding NiWS supported catalyst for the hydroisomerization of n-hexadecane. The physicochemical properties of the small-crystal and hierarchical SAPO-11 molecular sieve and the NiWS supported catalyst were analyzed via a series of characterization methods. It was found that the crystal size of SAPO-11-S was reduced to 21.8 nm and the particle size was reduced to 70–140 nm. SAPO-11-S was superior to SAPO-11-C in pore properties and acidity. The reason for the increase of the number of medium-strong B acid sites in SAPO-11-S was investigated by 29 Si MAS NMR characterization, and the formation mechanism of SAPO-11-S was proposed by tracking and analyzing the crystallization process of SAPO-11-S. The decrease of crystal size of SAPO-11 molecular sieve effectively improved the sulfidation degree of active metals and the dispersion degree of the active phase of the catalyst, and promoted more active phases to form “type II active phase”. Compared with NiW/SAPO-11-C, NiW/SAPO-11-S showed higher catalytic activity and isomerization selectivity, and the maximum i-hexadecane yield of NiW/SAPO-11-S was 44.77% higher than that of NiW/SAPO-11-C.
Wenjing Zhao,Hongxia Yang,Zhihui Li,Longli Zhang,Xufeng Lin,Hui Fu,Zhen Liu,Chuangye Wang
This work reports that the polyvinyl alcohol successfully templates the intracrystal mesoporous structure of hierarchical SAPO-11 molecular sieves. The structures of prepared hierarchical SAPO-11 materials and a conventional SAPO-11 simultaneously synthesized are characterized by X-ray diffraction, N2 adsorption/desorption, scanning electron microscopy and high resolution transmission electron microscopy. The characterizations demonstrate that this synthesized hierarchical SAPO-11 possesses a mesopore structure with a much regular pore size distribution. Importantly, these mesopores are intracrystal but not intercrystal. The bifuntional isomerization catalyst with this hierarchical SAPO-11 as support shows a high selectivity in hydroisomerization reaction of hexane, evidencing that the catalytic selectivity is improved by introduction of mesopore structure into the SAPO-11 crystal. The templating mechanism of polyvinyl alcohol in formation of mesopores is well discussed at the ending. This work provides a potential template to prepare hierarchical catalyst materials.
危险品化学品经营许可证（带存储）