Citation: CHANG Jiang-Wei, FU Ting-Jun, ZHANG Hong-Jian, ZHOU Hao, LI Zhong. Effect of Alkaline Concentration on Mesopore Formation in Acid Pre-treated HZSM-5 Zeolite and Its Catalytic Performance in the Methanol-to-Gasoline Reaction[J]. Chinese Journal of Inorganic Chemistry, ;2015, (11): 2119-2127. doi: 10.11862/CJIC.2015.278
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Modifying of ZSM-5 molecular sieve in acid and alkaline solution was studied at 80 ℃. For the post synthesis, dealumination prior to desilication step was critical for the following mesopore formation by desilication and the effect of alkaline concentration on the crystallinity, porosity, morphology and acidity of zeolite was investigated by deep characterization of BET, XRD, FT-IR, NH3-TPD, and TEM. It was found that the microporous structure was well reserved in acid dealumination alone, alkaline desilication could promote smaller mesopore. However, acid dealumination before desilication facilitated the mesopore formation resulting in larger pore volume. When the concentration of alkaline solution was increased to 0.6 mol·L-1, both the pore volume and Sext/Smicro firstly increased and then decreased. The sample via post treatment of 2 mol·L-1 HCl and 0.4 mol·L-1 NaOHsolution was found to have higher proportion of mesopores, less amount of acid sites, especially strong acidity. Methanol conversion to gasoline reaction was carried out in a fixed reactor at 400 ℃, 0.1 MPa and WHSV=2.1 h-1. The sample subjected to 2 mol·L-1 HCl acid solution and 0.4 mol·L-1 NaOH solution exhibited greater improvement: the yield of gasoline range increased to 34wt% from 30wt%, the lifetime was prolonged to 135 h relative to parent ZSM-5 and the content of aromatics was decreased from 73wt% to 20wt%. The results were well rationalized by alterations of acidic properties, mesopore formation and improved diffusivity.
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