Levulinic Acid Derived Reusable Cobalt-Nanoparticles-Catalyzed Sustainable Synthesis of γ-Valerolactone

Abstract

The effective utilization of levulinic acid, a renewable feedstock derived from sugar biomass, is of central importance for the preparation of value-added chemicals as well as catalytic materials. Specifically, the production of γ-valerolactone, a key platform molecule, from levulinic acid represents one of the pivotal processes in converting lignocellulose-based biomass into renewable fuels and chemicals. Compared to synthetic valorization, the use of levulinic acid for the preparation of catalytically active nanomaterials is scarcely explored. Here, we report the use of levulinic acid for the preparation of cobalt-based nanocatalysts as well as for the synthesis of γ-valerolactone. The template synthesis of cobalt–levulinic acid on commercial silica and subsequent pyrolysis resulted in the formation of cobalt nanoparticles as highly active and selective catalysts for the hydrogenation of levulinic acid to γ-valerolactone under industrially viable and scalable conditions. Applying this optimal catalyst, other lactones starting from different oxo carboxylic acids have also been prepared in good to excellent yields. Synthetic and practical utility of this Co-based valerolactone synthesis protocol has been demonstrated by performing synthesis on the scale of 20 g and recycling of catalyst.

Contribution to the production and use of biomass-derived solvents – a review

“…The highly efficient catalytic system was composed of commercially available cobalt salt, Co(BF4)2 2O and a tetradentate phosphine ligand P(CH2CH2PPh2)3, 2 pressure. Cobalt was also used as catalyst for GVL synthesis by Murugesan et al [123], which applied LA for the preparation of cobalt-based nanocatalysts. These nanoparticles created reusable catalysts (up to 4 times) for the hydrogenation of LA, achieving 97% GVL yield in the following reaction conditions: 30 bar H2, 1,4-Another approach to produce GVL is using a one-step co and hydrogenation catalyst are required for the conversion of carbohydrates into GVL in the one-step method [124,125] sted acid catalysts is determined by its dissociation constant (pKa), but also dependent on the solvent.…”

Ru@hyperbranched Polymer for Hydrogenation of Levulinic Acid to Gamma-Valerolactone: The Role of the Catalyst Support

“…Among numerous heterogeneous catalysts developed for LA transformation such as supported catalysts based on Ru [ 10 , 11 , 12 , 13 , 14 ], Co [ 15 ], Pt [ 16 ], Pd [ 17 ], Cu [ 18 , 19 ], and Ni [ 20 , 21 ], and Ru-containing systems are shown to be the most active. Typically, catalytically active metal is deposited on different supports including activated carbon [ 12 , 22 ], metal oxides [ 10 , 11 , 18 ], silica [ 14 , 17 , 21 ], and polymers [ 23 , 24 ].…”

Aldol Condensation of Biomass-Derived Levulinic Acid and Furfural over Acid Zeolites

“…Levulinic acid (LA) is a very interesting bioplatform molecule. , Several alternative production routes are reported in the literature, the most promising ones being the Biofine process and its production via furfuryl alcohol, with final yields higher than 70% using commercial zeolites. , LA is proposed as starting compound of many different processes, most of them involving its internal cyclization and the subsequent hydrogenation to γ-valerolactone, − a reaction known in principle since the 1930s . Typically, the carboxylic group of LA plays a key role in the mechanism, with other routes involving the activity of the carbonyl group being scarcely investigated, as is the case of aldol condensation.…”