Steering the Ester and γ-Valerolactone Selectivities in Levulinic Acid Hydrogenation

Abstract

Both alkyl esters and γ-valerolactone (GVL) derived from levulinic acid (LA) have applications as renewable transportation fuel/fuel additives. Non-noble metal cobalt supported on La2O3 catalyst was developed for efficient cascade LA hydrogenation to GVL via esterification. LA hydrogenation in methanol alone yielded methyl levulinate (MeLA) as a major product along with 43% of GVL. Interestingly, hydrogenation in water gave almost complete selectivity to GVL; nevertheless, it was associated with significant metal leaching. Suppression of metal leaching and enhancement in selectivity to GVL could be achieved by a methanol/water (95:5) solvent system. XRD analysis of La2O3-supported catalysts evidenced the characteristic peaks of a mixture of La2O3 and La­(OH)3 phases. Basicity, as well as acidity, of the catalyst as determined by CO2 and NH3 TPD was due to these La2O3, Co–La, and La­(OH)3 phases which played an important role in directing the product selectivity in levulinic acid hydrogenation. At the low temperature of 160 °C, almost equal selectivities of MeLA (47%) and GVL (43%) were observed, while higher temperature (200 °C) favored further hydrogenation of MeLA to GVL (75%). Similarly, with an increase in reaction time to 9 h, the GVL selectivity achieved was as high as 80%. The selectivity to MeLA and GVL in LA hydrogenation over Co/La2O3 catalyst can be altered by suitably adjusting the reaction conditions.

Efficient Vapor‐Phase Selective Hydrogenolysis of Bio‐Levulinic Acid to γ‐Valerolactone Using Cu Supported on Hydrotalcite Catalysts

“…Through the characterization of NH 3 ‐TPD and N 2 O decomposition techniques, both acidity and the amount of active Cu sites on Hydrotalcite were analyzed and reported in this study. Similar phenomena are reported in the previous studies …”

Promotion effects of PrPO4 for the hydrogenation transformation of biomass-derived compounds over Pr–Ni–P composites

“…Considering that the corruption effect from acid reactant would greatly depress the application potential of Ni involved catalysts, [11][12][13][14][15] we employed levulinic acid (LA) as the primary reactant to investigate the catalytic hydrogenation performance of prepared literature works, so the amount of desorbed H-atom or the numbers of active site on our typical catalysts were also estimated by the method. In addition, it should be pointed out that the metal active site in an oxidized state (being not functional to raise Hadsorption-desorption signal) should be previously reduced and then measured with above H 2 -TPD method, for Ni based compound, the method is the widely accepted and the most reliable one to determine Ni site on surface; but for Ni 2 P, the method is not practical due to that Ni 2 P is difficult to be reduced even with pure H 2 to treat 4 h under 873 K, so we had to measure the site number of Ni 2 P by calibrating its specific area to the surface molecular density of Ni 2 P crystalline.…”

“…Nobel metals like Pt, Pd, Ru have been testified to be efficient and stable catalyst for hydrogenation transformations of levulinic-acid and furfural under relatively mild conditions. [6][7][8][9] Considering the cost limitation of precious metal for scaled-up application, some researchers paid attentions to cheap transition metal catalysts such as Cu, Co and Ni, [10][11][12][13][14][15][16] and attractive catalytic performance over the deliberately fabricated metallic catalysts mostly in fashion of diverse nanostructures were shown in literature. For example, Liu et al prepared a Ni-embedded hierarchicallyporous carbon catalyst for hydrogenation of LA to GVL, 17 the exquisite design of protecting highly-dispersed Ni nanoparticle in carbon coverage prevented the Nileakage in reaction mixture and maintained catalytic performance in reuse processes.…”

An overview of the obtaining of biomass-derived gamma-valerolactone from levulinic acid or esters without H2 supply

“…On the other hand, 4-HPA can be used for polyester production (Gorenflo et al 2001). In this respect, if levulinate ester or 4-HPA are generated as by-products, it would still be interesting to obtain both LE and GVL, varying the process conditions (Kasar et al 2018).…”

“…The sugar platform using lignocellulosic biomass as feedstock harnesses cellulose and hemicelluloses C5/C6 sugar fractions (Cherubini et al 2009). By using a set of concatenated reactions, they can then be transformed into valuable compounds with industrial applications such as 5-hydroxymethylfurfural (HMF) (Antonetti et al 2016(Antonetti et al , 2017Licursi et al 2017), furfural (FUR) (Mariscal et al 2016), levulinic acid (LA) (Antonetti et al 2015;Licursi et al 2018b;Rivas et al 2015Rivas et al , 2018, gamma-valerolactone (GVL) (Alonso et al 2013), and others (Heeres et al 2009;Lange et al 2010;Fábos et al 2014;Cen et al 2018;Kang et al 2018;Kasar et al 2018;Kim et al 2020a;Lilga et al 2018).…”