Investigation into the crystallization of molecular sieve DNL-6

Crystallization of DNL-6, a silicoaluminophosphate (SAPO) based molecular sieve with the RHO topology, was investigated under both the hydrothermal synthesis (HTS) and dry-gel conversion (DGC) conditions. Crystallization of DNL-6 under the HTS conditions is rather fast. But a combination of crystallization under the DGC conditions and reducing reaction temperature slow down the reactions, allowing for intermediates to be captured. Under the DGC conditions, DNL-6 crystallizes through a semi-crystalline layered phase. The nature of this intermediate is aluminophosphate (AlPO) rather than SAPO with most P atoms having a local environment of P(–O–Al)3(OH). The surfactant (cetyltrimethylammonium chloride) used for synthesis appears to be part of the layered intermediate. Si is directly incorporated in the DNL-6 framework via SM II mechanism when the semi-crystalline AlPO phase is transforming to DNL-6 with the assistance of a very small amount of water. Both the structure directing agent and the surfactant play a role in the formation of DNL-6, as they were found within the final synthesized products. SEM data show that hydrothermal synthesis produces a much more crystalline product. The facts that the semi-crystalline layered phase was also observed in the powder X-ray diffraction patterns of the solid samples obtained under the HTS conditions and that the evolution of the local structure around P and Al in the intermediate phases are similar imply that under the reaction conditions employed in the present study, the formation pathways of DNL-6 under the HTS and DGC conditions appear to have some similarities.

Zn-P Co-Modified Hierarchical ZSM-5 Zeolites Directly Synthesized via Dry Gel Conversion for Enhanced Methanol to Aromatics Reaction

A unique method to prepare Zn-P co-modified hierarchical ZSM-5 zeolites was developed. The ZSM-5 zeolite was directly synthesized by a dry gel conversion without adding any templates or seeds. Afterwards, the hierarchical structure was endowed to the ZSM-5 zeolite by the sequential desilication-dealumination. Zn and P species were then introduced into the hierarchical ZSM-5 zeolites by the impregnation method and their activity in methanol to aromatics process was investigated. It was found that the Zn-P co-modified hierarchical ZSM-5 zeolites possessed more Zn-related Lewis acid sites, and the ratio of Zn(OH)+/ZnO was increased. The catalytic evaluation results revealed that the benzene, toluene and xylene (BTX) and aromatics selectivity were significantly improved from 20.59% and 29.41% of pristine ZSM-5 zeolite to 28.12% and 41.88% of Zn-P co-modified hierarchical counterpart (1.5Zn0.3P/HZSM-5), respectively. Owing to the introduced highly stable Zn-P co-modified hierarchical structures, the lifetime (conversion not less than 99%) of ZSM-5 zeolite during methanol to aromatics reaction was increased from 6 h to 18 h.

Synthesis of nano-ZSM-5 zeolite via a dry gel conversion crystallization process and its application in MTO reaction

Nano-sized ZSM-5 with superior catalytic properties was synthesized from LAPONITE® as one of the Si sources by a dry gel conversion method.

On the Anti-Corrosion Property of Dry-Gel-Conversion-Grown MFI Zeolite Coating on Aluminum Alloy

MFI zeolite film coated on AA6061 alloy was prepared from fumed silica modified with/without n-octyldecyltrimethoxysilane (ODS) by means of dry gel conversion (DGC) method. The DGC-grown MFI zeolite film could form a strong barrier to protect AA6061 surface against the corrosion from NaCl solution. By using fumed silica as a starting material, the hydrophilicity and anti-corrosion capability of the MFI zeolite film declined with increasing humidity in the DGC synthesis. By silanization with ODS, the surface hydrophobicity of the MFI zeolite film increased, leading to substantial enhancement in anti-corrosion capability. On the other hand, MFI film grown from ODS-modified fumed silica exhibited low hydrophilicity and a much improved anti-corrosion protection property by four orders of magnitude, even stronger than the ODS post-treated MFI film. The strong anti-corrosion capability is attributed to the “thick layer” surface hydrophobicity of zeolite crystal.