Dejin Kong

Synthesis of ZSM-5 with intracrystal or intercrystal mesopores by polyvinyl butyral templating method.

Three facile routes were utilized to synthesize ZSM-5 materials with intracrystal or intercrystal mesopores, where the polyvinyl butyral gel served as mesopore directing template. The three routes were divided into two synthesis strategies: the hydrothermal treatment of silica/PVB composite and re-crystallization of preformed zeolite precursor with the assistance of PVB gel. The fabrication of silica/PVB composite was accomplished by two routes including sol-gel process and impregnation method. The resulting composite was undergone hydrothermal treatment. During the crystallization PVB was occluded in the ZSM-5 crystal, creating intracrystal mesopores in the zeolite. The last route for the synthesis of mesoporous ZSM-5 was realized by re-crystallization of preformed ZSM-5 zeolite in the presence of PVB. This route involved the pre-crystallization of the amorphous aluminosilicate to produce the pre-formed ZSM-5 precursor. Upon further crystallization of the mixture of PVB gel and pre-formed ZSM-5, the ZSM-5 precursor was transformed into ZSM-5 aggregate of nanocrystals, while the PVB gel was occluded in the ZSM-5 particles. Removal of the template generated the typical microporosity associated with ZSM-5 structure along with intercrystal mesoporosity produced from the PVB. The mesoporous ZSM-5 exhibited enhanced catalytic activity in the toluene disproportionation and transalkylation with C(9) and C(10) aromatics.

A comparative computational study on the synthesis prescriptions, structures and acid properties of B-, Al- and G-incorporated MTW-type zeolites

The B-, Al- and Ga-incorporated H-, NH4-, Li-, Na- and K-forms MTW zeolites were comparatively studied to understand the crystallization thermochemistry, structure stabilities and acid properties using dispersion corrected density functional theory. Substitution energies were introduced to evaluate the synthesis prescriptions for MTW zeolites. The calculated results show that the trivalent and alkaline metal ions for the synthesis of the MTW zeolites are favored in the following order: Al > Ga > B and Na > K > Li > NH4 > H. The B–O, Si–O and O–H bonds have a covalent character while Al–O bonds show an obvious ionic character. However, the character of Ga–O bonds fall in between that of Al–O and B–O bonds. Introducing alkaline metal ions significantly changes the cell volumes. As a result, the cell volumes of the H-form B-, Al- and Ga-incorporated MTW zeolites are larger than Li-form, and smaller than K-form MTW zeolites. Further investigation of their properties show that the Bronsted acid sites of the zeolites follow the order of HAl-MTW > HGa-MTW > HB-MTW. The Lewis acidity of HB-MTW is similar to that of HAl-MTW, and weaker than that of HGa-MTW. These results are in good agreement with the previous experiments and provide new insights for the MTW zeolites.

Continuous hydrogenation of ethyl levulinate to γ-valerolactone and 2-methyl tetrahydrofuran over alumina doped Cu/SiO2 catalyst: the potential of commercialization

Hydrogenation of levulinic acid (LA) and its esters to produce γ-valerolactone (GVL) and 2-methyl tetrahydrofuran (2-MTHF) is a key step for the utilization of cellulose derived LA. Aiming to develop a commercially feasible base metal catalyst for the production of GVL from LA, with satisfactory activity, selectivity, and stability, Al2O3 doped Cu/SiO2 and Cu/SiO2 catalysts were fabricated by co-precipitation routes in parallel. The diverse physio-chemical properties of these two catalysts were characterized by XRD, TEM, dissociative N2O chemisorptions, and Py-IR methods. The catalytic properties of these two catalysts were systematically assessed in the continuous hydrogenation of ethyl levulinate (EL) in a fixed-bed reactor. The effect of acidic property of the SiO2 substrate on the catalytic properties was investigated. To justify the potential of its commercialization, significant attention was paid on the initial activity, proper operation window, by-products control, selectivity, and stability of the catalyst. The effect of reaction conditions, such as temperature and pressure, on the performance of the catalyst was also thoroughly studied. The development of alumina doped Cu/SiO2 catalyst strengthened the value-chain from cellulose to industrially important chemicals via LA and GVL.

Shape selective catalysis in methylation of toluene: Development, challenges and perspectives

Toluene methylation with methanol offers an alternative method to produce p-xylene by gathering methyl group directly from C1 chemical sources. It supplies a “molecular engineering” process to realize directional conversion of toluene/methanol molecules by selective catalysis in complicated methylation system. In this review, we introduce the synthesis method of p-xylene, the development history of methylation catalysts and reaction mechanism, and the effect of reaction condition in para-selective technical process. If constructing p-xylene as the single target product, the major challenge to develop para-selective toluene methylation is to improve the p-xylene selectivity without, or as little as possible, losing the fraction of methanol for methylation. To reach higher yield of p-xylene and more methanol usage in methylation, zeolite catalyst design should consider improving mass transfer and afterwards covering external acid sites by surface modification to get short “micro-tunnels” with shape selectivity. A solid understanding of mass transfer will benefit realizing the aim of converting more methanol feedstock into para-methyl group.