Gao Junhua, Zhou Hao, Zhang Fucan, Ji Keming, Liu Ping, Liu Zenghou, Zhang Kan
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China.
State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China.
Materials (Basel). 2022 Mar 17;15(6):2206. doi: 10.3390/ma15062206.
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, Al NMR, SEM-EDS, ICP, low-temperature N adsorption and desorption, NH-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.
采用水热法合成了一种纳米ZSM-5沸石晶体,并通过酸交换得到HZSM-5沸石粉末。以拟薄水铝石为粘结剂,除采用湿挤成型法和机械混合法外,通过将粘结剂含量调整在20%至50%之间,制备了一系列用于甲醇制烃(MTH)的HZSM-5沸石催化剂。采用XRD、Al NMR、SEM-EDS、ICP、低温N吸附脱附、NH-TPD、Py-FTIR、FT-IR、TG和元素分析等方法对新鲜催化剂和积炭催化剂的性能进行了表征。然后,在连续流动固定床反应器中评价了MTH催化性能。表征和评价结果表明,成型过程中加入稀硝酸增加了中等强度酸的量,形成了分级孔分布,有助于降低裂化、芳构化和氢转移的反应能力,改善催化剂的扩散性能,减缓积炭速率。采用稀硝酸湿挤法制备的粘结剂含量为30%的催化剂性能最佳,其MTH活性稳定性提高了96 h,高于其他催化剂,积炭速率较慢,这是由于酸强度和B/L比分布最适宜,分级孔结构最明显。