Biomass:polystyrene co-pyrolysis coupled with metal-modified zeolite catalysis for liquid fuel and chemical production

Biomass and waste polystyrene plastic (ratio 1:1) were co-pyrolysed followed by catalysis in a two-stage fixed bed reactor system to produce upgraded bio-oils for production of liquid fuel and aromatic chemicals. The catalysts investigated were ZSM-5 impregnated with different metals, Ga, Co, Cu, Fe and Ni to determine their influence on bio-oil upgrading. The results showed that the different added metals had a different impact on the yield and composition of the product oils and gases. Deoxygenation of the bio-oils was mainly via formation of CO2 and CO via decarboxylation and decarbonylation with the Ni–ZSM-5 and Co–ZSM-5 catalysts whereas higher water yield and lower CO2 and CO was obtained with the ZSM-5, Ga–ZSM-5, Cu–ZSM-5 and Fe–ZSM-5 catalysts suggesting hydrodeoxygenation was dominant. Compared to the unmodified ZSM-5, the yield of single-ring aromatic compounds in the product oil was increased for the Co–ZSM-5, Cu–ZSM-5, Fe–ZSM-5 and Ni–ZSM-5 catalysts. However, for the Ga–ZSM-5 catalyst, single-ring aromatic compounds were reduced, but the highest yield of polycyclic aromatic hydrocarbons was produced. A higher biomass to polystyrene ratio (4:1) resulted in a markedly lower oil yield with a consequent increased yield of gas.

Diffusion anisotropy descriptor revealing morphology effect of H-ZSM-5 zeolite for olefin catalytic cracking

Zeolite morphology is vital in determining catalytic activity, selectivity and stability in zeolite catalysis, while quantitative description of morphology effect is great challenging but highly desirable. Herein, a descriptor to elucidate the morphology effect is proposed by revealing the diffusion anisotropy in straight and sinusoidal channels of H-ZSM-5 zeolite for olefin catalytic cracking. A series of H-ZSM-5 zeolites with similar nano-sheet morphology were precisely synthesized in which only the length in c-axis varies. It is unexpectedly demonstrated that the catalytic activity and stability can be obviously improved by employing samples with longer length in c-axis. Combining time-resolved in-situ FT-IR spectroscopy with molecular dynamic simulations, we revealed that the difference in catalytic performance can be attributed to the intracrystalline diffusive propensity in different channels. This work not only provides a clear descriptor revealing morphology effect, but also offers deep insight into design of highly effective zeolite catalysts for olefin catalytic cracking.

Hierarchy in zeolite catalysis: The influence of enhanced mesoporosity on the synthesis of renewable fuels and bio-based platform chemicals

Faujasite (FAU), ZSM-5 (MFI), beta (BEA) and mordenite (MOR) zeolites were admitted to a variety of chemical treatments accompanied by surfactant templating strategy, aiming to introduce the intracrystalline mesoporosity effectively. The resulting materials were tested as solid acid catalysts for esterification of the oleic acid as a common model impurities found in bio-oil feedstoks. It was found that the esterification of oleic acid can be enhanced by the presence of strong acid sites in zeolites and their improved accessibility. Overall, mesostructured FAU zeolite demonstrated an improved catalytic performance as a result of increasing accessibility of the zeolite active sites.