Controllable Orientation Growth of ZSM-5 for Methanol to Hydrocarbon Conversion: Cooperative Effects of Seed Induction and Medium pH Control
Ma Qian, Tingjun Fu, Kun Ren, Li Han, Lihan Jia, Zhong Li
Abstract
The growth orientation of ZSM-5 zeolites strongly affects product selectivity in methanol conversion reaction. Here, we proposed a versatile synthetic strategy by introducing seeds and controlling medium pH to achieve controllable orientation growth of ZSM-5. The systematic analysis of the crystallization process indicated that the introduction of seeds ensured successful crystallization in a quasi-neutral solution and the dissolution rate of seeds and aluminosilicate determined the growth orientation of ZSM-5. In the quasi-neutral solution, the slow dissolution of seeds and aluminosilicate enhanced growth advantages along the c axis. The ratio between the length of the c axis and b axis (Lc/Lb) of the obtained ZSM-5 at pH of 7 could reach 8.1, much higher than 1.8 obtained at pH of 11. No obvious impact of seed added amount on growth orientation was found, while with increasing seed crystal size, the obtained ZSM-5 showed preferred growth along the c axis. The Lc/Lb of the sample adding seeds with a size of 355 nm reached 7.9, much higher than 2.1 of the sample adding seeds with a size of 70 nm. The obtained ZSM-5 with specific growth orientation exhibited potential shape selectivity in methanol to aromatics and olefin reaction. This work opens new possibilities to tailor the orientation growth of ZSM-5 based on the seed-induced strategy under mild conditions.