A highly efficient SAPO-34 catalyst for improving light olefins in methanol conversion: Insight into the role of hierarchical porosities and tailoring acid properties based on in situ NH3-poisoning

Hierarchical SAPO-34 zeolites with tunable porosity were hydrothermally synthesized by modulating the Si/Al molar ratios of the gel precursors, and the morphologies of SAPO-34 crystals gradually evolve from well-dispersed ultra-small nanocrystals to compactly polycrystalline aggregates, and to analogous polycrystallinites but adhered with minute amorphous debris by increasing the Si/Al ratio ranging from 0.20 to 0.67. The catalytic tests during methanol-to-olefins (MTO) reaction indicate that the Hier-SAPO-34-0.20 (Si/Al = 0.20) catalyst constructed by loosely nano-sized crystals centered at 50 nm presents prominent catalytic performances with about 2.5 times prolonged catalytic longevity and around 10 % improvement for the selectivity toward light olefins (ethylene and propylene) as compared to a reference catalyst. More interestingly, when Hier-SAPO-34-0.20 catalyst was in situ pretreated with NH3 flowing, the selectivity of light olefins can be greatly increased by 18.1 % at the initial stage and the corresponding even selectivity with time-on-stream can be elevated by 6.9 %. It founds that in situ NH3-poisoned catalysts with improved light olefins selectivity are also suitable for ZSM-5 zeolite. These results reveal that the weakened strong acid sites modified by NH3-poisoning play a pivotal role in suppressing the undesired hydrogen transfer reactions and thus giving a high selectivity for light olefins. This work highlights the importance of acidity fine-tailoring by in-situ NH3-poisoning strategy on hierarchical zeolites for the improvement of light olefin selectivity, which would be valuable guidance for industrial applications.