Jingce Bi,Qingfeng Zhan,Yujing Chen,Zhiqiang Liang,Ningning Liu,Xia Zhang,Zhuopeng Wang,Yide Han
At present, the construction of hierarchically porous ZSM-5 molecular sieves using only cetyltrimethylammonium bromide (CTAB) as the template represents a major challenge in the field of molecular sieve synthesis. In this work, hierarchically porous ZSM-5 zeolite was synthesized via a straightforward conventional static hydrothermal method, employing CTAB as the sole template agent derived from CTAB-encapsulated silica sphere precursors. By controlling the dissolution rate of silica spheres, the release rate of CTAB is regulated, enabling the synthesis of pure-phase hierarchical porous ZSM-5 zeolite. The influences of alkalinity, aging time, Si/Al ratio, CTAB content and addition method, and crystallization time on the construction of hierarchically porous ZSM-5 molecular sieves were examined. The experimental results indicate that the crystallization process in this system proceeds in the order: MFI → MFI + kenyaite → MFI + quartz. Additionally, by managing the crystallization process, we systematically examined the formation process of impurities and established the optimal conditions for synthesizing pure-phase hierarchically porous ZSM-5 molecular sieves in this system. Moreover, the as-prepared hierarchically porous ZSM-5 molecular sieves demonstrated enhanced selectivity towards light olefins in the MTP reaction.
Herein, a specific core–shell MFI zeolite was designed for the methanol to propylene (MTP) reaction. The core–shell structure of Al-ZSM-5@B-ZSM-5 and Al-ZSM-5@silicalite-1 were easily obtained via a two-step procedure, in which Al-ZSM-5 aggregate acted as the core and B-ZSM-5 or silicalite-1 as the shell. Their core–shell structures, acidity distribution and pore properties were characterized systemically, and new insights were gained into the synergetic effect of acid property and diffusion on the MTP reaction. The Al-ZSM-5@B-ZSM-5 zeolite exhibited a superior catalytic performance with a lifetime of 350 h (WHSV = 3 h−1), propylene selectivity of 49% and high turnover number of 4.3 × 106, while for the Al-ZSM-5 core, the corresponding values were 210 h, 43% and 5.2 × 105, respectively. Al-ZSM-5@silicalite-1 displayed the second best performance with the values of 250 h, 45% and 2.9 × 106, respectively. Gradient strong acid reduction from the core to the shell via the epitaxial growth of the silicalite-1 or B-ZSM-5 shell combined with an appropriate strong/weak acid ratio plays a vital role in inhibiting the hydrogen transfer reaction and thus gives a low consumption of propylene and low coke deposition. For the hydrogen transfer reaction of alkenes to form alkanes and aromatics, strong acid sites are required. Moreover, the acid sites originally existing on the external surface of the Al-ZSM-5 core were converted into internal acid sites due to the formation of an interface zone in the core–shell zeolite, possessing micropore characteristics, which in turn improve the shape selectivity and suppress coke deposition. Especially, the Al-ZSM-5@B-ZSM-5 zeolite displayed more weak acid sites and few strong acid sites on its shell surface, which are beneficial for the low formation of external coke and also account for the highest utilization of acid sites in the MTP reaction, high propylene selectivity and long lifetime.
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