Coupling experimental with simulation studies into the impact factors and reaction mechanism of sawdust char pressured hydrogasification on K-modified transition metal composite catalysts.

The utilization of biomass char was hindered by the low gasification activity due to thick ring structures and unclear gasification mechanism. Herein, the mechanism was elucidated by experimental and DFT to improve the activity. The results demonstrated that temperature increased the gasification activity but did not changed the order of gasification activity of samples. Pressure dominated the position of the highest point of instantaneous CH4 yield, and high pressure enhanced carbon conversion by 81.72 % and 7.32 times. Moreover, KNi exhibited an uppermost catalytic activity with the instantaneous CH4 yield 1.89 times higher than that of raw char at 750 °C. The formation of the CxNi structure lowered the activation barrier for the ring opening reaction. Possible transformation pathways of Ni species were as follows: Ni(NO3)2·6H2O â†’ NiO â†’ Ni. KNi changed the reaction pathways and the most energy-consuming step. The study could shed light on the hydrogasification reaction mechanism.

Supported cobalt catalysts for the selective hydrogenation of ethyl levulinate to various chemicals.

A highly active and selective cobalt catalyst was developed for the hydrogenation of biomass-derived ethyl levulinate (EL) to γ-valerolactone (GVL), ethyl 4-hydroxypentanoate (EHP), 1,4-pentanediol (1,4-PDO) and 2-methyltetrahydrofuran (2-MTHF), which are considered to be value-added chemicals and important biofuels. The effects of reaction time, reaction temperature, catalyst amount and solvent on its catalytic performance were investigated. In addition, the reaction pathway was studied as well. It was found that the selectivity of GVL, 1,4-PDO and 2-MTHF on Co/ZrO2 can be easily tuned by changing reaction conditions, and can reach as high as 94%, 78% and 77%, respectively. The product selectivity is also significantly affected by the catalyst support. With SBA-15 as the support, the selectivity of EHP can reach 90%. Moreover, Co/ZrO2 gave an extraordinarily high GVL productivity of 1.50 mol gmetal -1 h-1 and displayed excellent stability and reusability. Interestingly, coke has a positive effect on the enhancement of GVL yield. AL dimers and trimers were identified as the coke species in the hydrogenation of EL. As far as we know, this is the first work conducting the flexible transformation of EL on cobalt catalysts.