Experimental and theoretical approaches are combined for optimizing Ru catalysts for hydrogenation of levulinic acid (LA) with formic acid (FA) as a hydrogen source into γ-valerolactone (GVL). Particle size and influence of Ru precursor are considered as crucial parameters.
The pyrolysis of lignocellulosic biomass is one of the most promising methods of alternative fuels production. However, due to the low selectivity of this process, the quality of the obtained bio-oil is usually not satisfactory and does not allow for its direct use as an engine fuel. Therefore, there is a need to apply catalysts able to upgrade the composition of the mixture of pyrolysis products. Unfortunately, despite the increase in the efficiency of the thermal decomposition of biomass, the catalysts undergo relatively fast deactivation and their stability can be considered a bottleneck of efficient pyrolysis of lignocellulosic feedstock. Therefore, solving the problem of catalyst stability is extremely important. Taking that into account, we presented, in this review, the most important reasons for catalyst deactivation, including coke formation, sintering, hydrothermal instability, and catalyst poisoning. Moreover, we discussed the progress in the development of methods leading to an increase in the stability of the catalysts of lignocellulosic biomass pyrolysis and strengthening their resistance to deactivation.
1 February 2014 in Applied Catalysis B: Environment and Energy
Gamma-valerolactone (GVL) is one of the key products of future biorefineries. We show here for the first time the superior activity of Ni-based, Au doped catalysts in levulinic acid hydrogenation towards GVL using formic acid as a hydrogen source. Their performances are strongly influenced by the preparation method, and the highest GVL yield is achieved for bimetallic Au–Ni catalysts prepared via co-impregnation of both metallic salts with a reductive thermal treatment under hydrogen. The very high catalytic activity is explained by the use of DFT calculations and the extensive characterization of the catalyst surface and bulk properties. We highlight the pivotal role played by the incorporated isolated metallic Ni atoms within Au nanoparticles. The nano-alloy composition is determined. It allows establishment of a surface model of such an alloy, thanks to which the high activity can be explained by the presence of an optimum energetic span of FA adsorption. The existence of strong interaction between Au and Ni in a surface alloy, Au–Ni, favors selective and fast decomposition of formic acid into hydrogen that consequently facilitates strongly the combined hydrogenation process.