Distinct coking depth in steam reforming of oxygen-containing organics and hydrocarbons.

In steam reforming of organics in a fixed-bed reactor, catalyst particles in varied location of catalyst bed will experience different history of contacting with reactants/products. This may affect accumulation of coke in varied section of catalyst bed, which are investigated in steam reforming of some typical oxygen-containing organics (acetic acid, acetone and ethanol) and hydrocarbons (n-hexane and toluene) in a fixed-bed reactor with double layers of catalyst bed for investigating coking depth at 650 °C over Ni/KIT-6 catalyst in this study. The results indicated that the intermediates derived from the oxygen-containing organics in steam reforming could hardly penetrate the upper-layer catalyst to form coke in the lower-layer catalyst. In converse, they reacted quickly over the upper-layer catalyst via gasification or coking, forming coke almost exclusively in the upper-layer catalyst. The hydrocarbon intermediates from the dissociation of hexane or toluene could easily penetrate and reach the lower-layer catalyst to form even more coke therein than the upper-layer catalyst. The characterization showed that the insufficient gasification of *CxHy species led to their aggregation/integration to form more aromatic coke, especially from n-hexane. The aromatic-ring containing intermediates from toluene tended to integrate with *OH species to form ketones that further involved in coking, forming coke of less aromatic nature than that from n-hexane. Steam reforming of oxygen-containing organics also produced oxygen-containing intermediates and coke of higher aliphatic nature, lower carbon to hydrogen (C/H) ratio, lower crystallinity and thermal stability.

Alloying nickel and cobalt with iron on ZSM-5 for tuning competitive hydrogenation reactions for selective one-pot conversion of furfural to gamma-valerolactone.

One-pot conversion of furfural, a biomass-derived platform chemical, to gamma-valerolactone (GVL), a fuel additive and green solvent, involves multiple steps of hydrogenation. Among these reactions, the deep hydrogenation of the furan ring in furfural interrupts GVL formation over Ni or Co-based catalysts. In this study, a method of alloying Ni and Co with Fe over a ZSM-5 support was proposed for tackling excessive activity of the catalyst for hydrogenation. The results indicated that the formation of binary NiFe and CoFe alloys in Ni-Co-Fe/ZSM-5 enhanced the dispersion of metallic species, reduction of metal oxides, formation of more Lewis acidic sites, and the adsorption of the C-O functionality of the furan ring, while lowering the capability for adsorption/activation of H2 and the adsorption of the CC group of the furan ring. These factors together reduced the activity for the hydrogenation of the furan ring in furfural, but enhanced the hydrogenation of the CO in ethyl levulinate (EL). The kinetic study confirmed that the hydrogenation of EL was the rate-determining step. The coordination of the dual alloys, NiFe and CoFe, in the bifunctional Ni-Co-Fe/ZSM-5 catalyst rendered superior activity for selective one-pot conversion of furfural to GVL with a yield of 85.7%.

Pyrolysis of furfural residues: Property and applications of the biochar.

Furfural residue (FR) is a solid waste generated during the production of furfural from corn cobs. The chemical energy and material potential of FR can be potentially recovered via pyrolysis. In this study, the pyrolysis of FR at the temperature ranging from 350 to 650 °C at the varied heating rate was investigated, aiming to understand the characteristics of the pyrolysis products. The results indicate that the organic components of FR tend to be cracked to form biochar and gases as the dominate products, due to the high ash content of FR. The FR-derived bio-oil also contained abundant organics derived from cellulose and lignin. Increasing pyrolysis temperature favored formation of the organics with fused ring structures. Lower heating rate in pyrolysis also formed biochar with higher thermal stability and higher fixed carbon content by enhancing the extent of deoxygenation. Additionally, the transformation of -OH via dehydration, -C-H into = C-H via dehydrogenation, and the cracking of CO during carbonization of biochar in the pyrolysis were also observed during pyrolysis of FR. Activation of the FR-derived biochar generated abundant micropores and mesopores, rendering the activated carbon with superior specific capacitance as electrodes of electrocapacitors (329 Fg-1) and the excellent adsorption efficiency of phosphate (up to 98.81%).