盐酸溶液和水热脱铝HEU-1分子筛的表征及其催化裂解性能

Characterization and Catalytic Performance in n-Hexane Cracking of HEU-1 Zeolites Dealuminated Using Hydrochloric Acid and Hydrothermal Treatments

采用HCl溶液和/或水热处理HEU-1分子筛,利用X射线衍射、N2吸附-脱附、X射线荧光光谱、NH3程序升温脱附、吡啶吸附傅里叶变换红外光谱和铝固体核磁共振等对脱铝处理的HEU-1分子筛进行了表征,并考察了脱铝HEU-1分子筛上正己烷的催化裂解性能.结果表明,采用HCl溶液处理HEU-1分子筛,能有效脱除非骨架铝,可调变样品的弱酸中心;而水热处理HEU-1分子筛,能有效脱除骨架铝,可调变样品的强酸中心.水热处理和HCl溶液处理有效结合可以达到同时调变HEU-1分子筛的酸类型和酸密度的目的.脱铝HEU-1分子筛上正己烷催化裂解反应结果表明,氢转移反应被明显抑制,丙烯选择性提高.600°C水热处理后再用HCl溶液处理的HEU-1分子筛于625°C反应时丙烯选择性由未改性的21.9%提高到35.2%,活性稳定性也由不足10h提高到40h.

A series of modified HEU-1 zeolites were prepared using hydrochloric acid treatment, hydrothermal treatment, and a combination of these. The parent and modified HEU-1 zeolites were characterized by X-ray diffraction, N2 adsorption-desorption isotherms, X-ray fluo- rescence, temperature-programmed desorption of ammonia, Fourier-transform infrared spectroscopy of adsorbed pyridine, and 27Al solid-state magic-angle spinning nuclear magnetic resonance techniques. The catalytic cracking performances of the modified HEU-1 zeo- lites were evaluated on a fixed-bed microreactor at 625 °C, atmospheric pressure, and an n-hexane weight hourly space velocity of 2.0 h？1. The results showed that extra-framework alumina could be removed by directly treating with hydrochloric acid, and framework alumina could be removed by hydrothermal treatment. Acidity characterization showed that the weak acid sites of HEU-1 zeolites could be adjusted using acid treatment, and the number of strong acid sites could be reduced using hydrothermal treatment. The framework nSi：nAl ratio was improved by using a combination of hydrothermal treatment and acid leaching. The acidities of the HEU-1 zeolites were adjusted and both the mesopore volume and external surface area were enhanced. In n-hexane cracking reactions, the dealuminated HEU-1 zeolite obtained by hydrothermal treatment for 4 h at 600 °C and then washing with hydrochloric acid exhibited the highest propylene production as a result of suppression of the hydrogen transfer reaction. At 625 °C, the selectivity for propylene on HEU-1（HT4-HCl） increased to 35.2% from 21.9%,and the lifetime of HEU-1（HT4-HCl） was also prolonged from not more than 10 to 40 h.