关键词: B-Al-ZSM-5, Al-ZSM-5@B-ZSM-5, 核壳分子筛, 酸分布, 甲醇制丙烯

Abstract:

Propylene is widely used as a raw material for producing polypropylene, acrylonitrile, propylene oxide, etc. Typical manufacturing processes for propylene (steam cracking and FCC process) are over-reliant on petroleum resources and cannot meet the rapidly growing global demands. New routes for producing propylene from non-oil resources, particularly methanol-to-propylene (MTP) technology, have attracted increasingly more attention, where a fixed-bed reactor is used and ZSM-5 zeolite is the best alternative catalyst. However, structural optimization of ZSM-5 to enhance the lifetime and propylene selectivity and a deep understanding of the mechanism of the MTP reaction are still considerable challenges. For the conventional ZSM-5 zeolite, carbon deposition preferentially occurs near the outer surface of the zeolite particles because of the high acid density on the external surface, which accelerates the deactivation by blocking the outer pore openings, especially in a long-term MTP reaction. Large amounts of external strong acids also promote secondary reactions, such as hydrogen transfer reactions, resulting in a decrease in propylene selectivity. To study the effects of strong and weak acid distributions of ZSM-5 zeolite on the MTP reaction, two series of boron-modified ZSM-5 zeolites were designed: B-Al-ZSM-5 zeolites by one-step synthesis and Al-ZSM-5@B-ZSM-5 core-shell zeolites by two-step synthesis. These were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), scanning transmission electron microscopy (STEM) mapping, N₂ physical adsorption-desorption, temperature-programmed desorption of ammonia (NH₃-TPD) and 1, 3, 5-triisopropylbenzene (TIPB) cracking, and B1-Al-ZSM-5 and Al@B1-ZSM-5, B2-Al-ZSM-5 and Al@B2-ZSM-5, and B3-Al-ZSM-5 and Al@B3-ZSM-5 samples in the two series were found to have similar texture properties, acid amounts and acid strengths, but different B and Al elemental distributions and acid distributions. We used these two sets of samples to compare the effect of different strong and weak acid distributions—a uniform distribution and a gradient distribution of strong and weak acids on the performance of the MTP reaction. The results showed that samples with a uniform distribution of strong and weak acids have higher propylene selectivity due to lower strong and weak acid densities, whereas samples with a gradient acid distribution have a longer catalytic lifetime in the MTP reaction due to the absence of strong acid density and higher weak acid density on the outer surface. The different acid distributions lead to two different carbon deposition modes. Carbon deposition of the sample with the uniform acid distribution preferentially formed on the outer surface, resulting in rapid deactivation by blocking external micropores and leaving the internal active centers not fully utilized. However, for the sample with the gradient acid distribution, the carbon-blocking rate of the external surface considerably decreased, which increased the time that the reactant molecules had to enter the internal micropores. Thus, the utilization rate of the active centers and the catalytic lifetime of the Al-ZSM-5@B-ZSM-5 core-shell sample considerably increased.

Key words: B-Al-ZSM-5, Al-ZSM-5@B-ZSM-5, Core-shell zeolite, Acid distribution, Methanol to propylene