Seed-Assisted Synthesis and Catalytic Performance of Nano-sized ZSM-5 Aggregates in a One-Step Crystallization Process

Hierarchical nano-sized ZSM-5 aggregates were successfully synthesized via a seed-assisted method in the presence of cetyltrimethylammonium bromide(CTAB)through a facile one-step crystallization process.Commercial ZSM-5 zeolites with a SiO2/Al2O3 ratio comparable to that of ZSM-5 products were treated with alkali and used as the seed particles.The influences of crystallization conditions were investigated,and the possible synthesis mechanism was proposed.ZSM-5 zeolites with diff erent amounts of CTAB added were characterized using many techniques and evaluated in toluene alkylation with methanol.The results showed that a trace amount of CTAB signifi cantly promoted the crystallization of ZSM-5 zeolite,with the morphology changing from hexagonal-shape crystals to uniform spherical aggregates.CTAB may act as the structure-directing agent and assemble the primary crystallites to generate hierarchical ZSM-5 aggregates.The ZSM-5 zeolite with the smallest primary particles of 50-80 nm exhibited large specific surface area,abundant mesopores,and the greatest microporosity.The hierarchical nano-sized ZSM-5 aggregate showed higher toluene conversion and a longer lifetime without compromising the selectivity to xylene and p-xylene in toluene alkylation with methanol.

Polycrystalline ZSM-5 Aggregates Induced by Seed and Catalytic Performance in Methanol to Hydrocarbon

Synthesis of ZSM-5 zeolite typically utilizes small molecule polyamines or quaternary ammonium salts as organic structure guiding agent(OSDA).By contrast,the OSDA-free hydrothermal synthesis system eliminates the use of organic templates and the subsequent calcination procedure.This not only reduces the cost of synthesis,but also prevents environmental pollution from the combustion of organic templates,representing an eco-friendly approach.Despite this,literature suggests that even so-called template-free synthesis systems often involve trace amount of organic substances like alcohol.In the present work,a calcined commercial ZSM-5 zeolite was served as seed,with sodium aluminate as aluminum source and silica sol as silicon source,ensuring an entirely template-free synthesis system.Polycrystalline ZSM-5 aggregates consisted of rod-like nanocrystals were successfully prepared in the completely OSDA-free system.Effects of the Si/Al ratio in ZSM-5 seed,dosage and crystallization conditions such as crystallization temperature and crystallization time on ZSM-5 synthesis were investigated.The results show that a highly crystallinity ZSM-5 aggregate consisting of primary nano-sized crystals less than 100 nm is produced from a gel precursor with 5.6%(in mass)seed after hydrothermal treatment for 48 h.Furthermore,the Si/Al ratio in ZSM-5 seed has little effect on the topological structure and pore structure of the synthesized samples.However,the seeds with a low Si/Al ratio facilitate faster crystallization of zeolite and enhance the acidity,especially the strong acid centers,of the catalyst.The catalytic performance of the synthesized polycrystalline ZSM-5 was evaluated during dehydration of methanol and compared with a commercial reference ZSM-5r.The results exhibit that as compared with the reference catalyst,the fabricated sample has a longer catalytic lifetime(16 h vs 8 h)attributed to its hierarchical pores derived from the loosely packed primary nanoparticles.Additionally,the prepared polycrystalline catalyst also exhibits a higher aromatics selectivity(28.1%-29.8%vs 26.5%).

Facile One-Pot Synthesis of ZSM-5 Aggregates with Interand Intra-Crystalline Mesopores for Methanol to Gasoline Conversion

ZSM-5 aggregates consisting of superfine and hierarchical nanocrystals(combined with micropores and intra-crystalline mesopores) with an average size of 30 nm were prepared through one-pot synthesis with the assistance of anionic polyacrylamide(APAM). The resultant zeolites(AHN-ZSM-5) were characterized by XRD, ICP-OES, SEM, TEM, BET, NH_3-TPD, Py-IR, and TG analyses and evaluated in the methanol to gasoline(MTG) reaction. Characterization results show that the hierarchical ZSM-5 aggregates possessed two kinds of mesopores, namely inter-and intra-crystalline mesopores. The amount of APAM considerably influenced the mesoporosity and textural properties of AHN-ZSM-5 zeolites. With the addition of APAM in the synthesis, the AHN-ZSM-5 zeolites exhibited large mesopore volume, large external surface area, and appropriate acidity. When applied in the MTG reaction, AHN-ZSM-5 demonstrated a catalytic lifetime that was 1.6 times longer than that of conventional ZSM-5 synthesized in the absence of APAM.