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ratio decreased less in organic hydroxide solution than that in inorganic hydroxide solution, resulting in negligible change of acid property after organic hydroxide treatment (Figure 12) [93]. A meso-ZSM-5 zeolite was prepared by post-treatment of ZSM-5 zeolite with tetramethylammonium hydroxide (TMAOH) or tetraethylammonium hydroxide (TEAOH) [26]. The catalytic cracking activity of the hierarchical ZSM-5 zeolites increased significantly compared with parent ZSM-5 Catalysts 2017, 7, 367 16 of 31 zeolite. Figure 12. Pictorial comparison of zeolite desilication by tetraalkylammonium hydroxides and Figure 12. Pictorial comparison of zeolite desilication by tetraalkylammonium hydroxides and sodium sodium hydroxide [93]. Copyright Elsevier, 2009. hydroxide [93]. Copyright Elsevier, 2009. 3.4.2. Fluoride Etching 3.4.2. Fluoride Etching Post-treatment of ZSM-5 zeolite with hydrofluoric acid (HF) solution is also an effective Post-treatment of ZSM-5 zeolite with hydrofluoric acid (HF) solution is also an effective approach approach to prepare the hierarchical zeolite. The crystallinity of the treated ZSM-5 zeolites does not to prepare the hierarchical zeolite. The crystallinity of the treated ZSM-5 zeolites does not change change observably. The Al species is selectively dissolved resulting in the increase of external observably. The Al species is selectively dissolved resulting in the increase of external surface area surface area and mesopore volume, and decrease of acid sites with a higher Si/Al ratio. The catalytic and mesopore volume, and decrease of acid sites with a higher Si/Al ratio. The catalytic activity activity was enhanced with the additional mesoporous after HF treatment [94]. While in NH4F-HF was enhanced with the additional mesoporous after HF treatment [94]. While in NH4F-HF mixed mixed aqueous solutions, large bifluoride ions (HF2−) generated due to chemical equilibrium, which aqueous solutions, large bifluoride ions (HF2−) generated due to chemical equilibrium, which was at was at least four to five times faster than HF in Si dissolution, as well as Al extraction least four to five times faster than HF in Si dissolution, as well as Al extraction simultaneously. As a simultaneously. As a result, the Si/Al ratio and acid sites were similar to the parent ZSM-5 zeolite, result, the Si/Al ratio and acid sites were similar to the parent ZSM-5 zeolite, and large mesopores and macropores were generated without destroying the intrinsic micropores. The interfaces between intergrown crystals which act as diffusion barriers were preferentially dissolved during NH4F-HF treatment, resulting in a higher crystalline domains (Figure 13) [95,96]. Besides, the silanols in treated samples were less than that in the parent ZSM-5 zeolite, which restrained the generation of carbon deposition on these sites [95]. As the acid property was similar with the parent ZSM-5 zeolite, the remarkably increased catalytic activity could be attributed to the high diffusion rate originated from the additional mesopores and macropores [97]. Overall, fluoride etching is an effective and fast approach to prepare hierarchical zeolite. However, HF is dangerous for human and it is troublesome when it is applied in industrial manufacture.PDF Image | Strategies to Enhance the Catalytic Performance of ZSM-5
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