A systematic study of the comparative performances of different metal-impregnated HZSM-5 catalysts (Zn, Ga, Mo, Co, and Zr) for propane conversion is presented. The physicochemical properties of catalysts were characterized by means of XRD, BET, SEM, TEM, FTIR, XPS, 27Al MAS NMR, NH3-TPD and Py-FTIR. It was found that the acidities of the catalysts were significantly influenced by loading metal. More specifically, Mo-, Co- or Zr-modified catalysts showed a large metal size and low acidic density, resulting high olefin selectivity, while Zn- or Ga-modified catalysts maintained their small metal size and acidic density, and mainly reduced B/L due to the Lewis acid sites created by Zn or Ga species, resulting in high aromatics selectivity. Experimental results also showed that there is a balance between metals size and medium and strong acidity on propane conversion. Moreover, based on the different acidity of metal-modified HZSM-5 catalysts, the mechanism of propane conversion was also discussed.
A kind of nano-ZSM-5 zeolite crystal was synthesized by the hydrothermal method, and HZSM-5 zeolite powder was obtained via acid exchange. By using pseudoboehmite as a binder, a series of HZSM-5 zeolite catalysts for methanol-to-hydrocarbons (MTH) were prepared through adjusting the binder content between 20 and 50% in addition to the molding method of wet extrusion and mechanical mixing. XRD, 27Al NMR, SEM-EDS, ICP, low-temperature N2 adsorption and desorption, NH3-TPD, Py-FTIR, FT-IR, TG and elemental analyses were used to characterize the properties of fresh catalysts and coke-deposited catalysts. Then, MTH catalytic performance was evaluated in a continuous-flow fixed-bed reactor. The characterization and evaluation results showed that the addition of dilute nitric acid during the molding process increased the amount of moderate-strength acid and formed a hierarchical pore distribution, which helped to reduce the reaction ability of cracking, aromatization and hydrogen transfer, improve the diffusion properties of the catalyst and slow down the coke deposition rate. The catalyst with a binder content of 30% made by wet extrusion with dilute nitric acid had the best performance, whose activity stability of MTH increased by 96 h, higher than other catalysts, and the coke deposition rate was slower, which was due to the most suitable distribution of acid strength and B/L ratio as well as the most obvious hierarchical pore structure.