Solvent-free γ-valerolactone hydrogenation to 2-methyltetrahydrofuran catalysed by Ru/C: a reaction network analysis

Abstract

2-Methyltetrahydrofuran (2-MTHF) is considered to be an attractive biomass based platform chemical with high potential as a biofuel compound and as a green solvent. 2-MTHF can be synthesised from bio-based levulinic acid (LA) and γ-valerolactone (GVL). Herein the optimum reaction conditions for the hydrogenation of GVL over Ru/C have been studied. A full conversion of GVL has been obtained under solvent free conditions with a maximum yield of 2-MTHF of 43%. The optimized conditions have been employed in a mechanistic study of the synthesis of 2-MTHF. Several side reactions have been investigated to explore the full reaction network of this heterogeneously catalysed system and to elucidate the factors influencing product selectivity. Additionally an efficient solvent-free hydrogenation reaction of LA into 2-MTHF could be achieved delivering 90% conversion of LA with a yield of 2-MTHF of 61% by removing water from the system in a two-step approach

Hydrogenation of levulinic acid to γ-valerolactone over anatase-supported Ru catalysts: Effect of catalyst synthesis protocols on activity

“…SiO 2 has the tendency to be converted into silica gel at all pH values, whereas Al 2 O 3 is well-known to convert into boehmite (AlO(OH)) at pH values between 4.5 and 11.5. TiO 2 , calculated to be stable over the entire pH range, and ZrO 2 are attractive alternatives [28], even though hydrated Zr(OH) 4 was found to be the thermodynamically most stable phase in water. Indeed, a screening study on LA hydrogenation involving 50 catalysts in a flow reactor system revealed that Pt on TiO 2 (P25 from Degussa) and ZrO 2 performed best, with constant GVL yields for runtimes exceeding 100 h (> 95 mol% at 200°C and 40 bar H 2, 11 wt.% LA in GVL) [28].…”

“…The family of LA derivatives is large and some have much potential for commercialization. For instance, LA can be converted to 2-methyltetrahydrofuran (MTHF) and various levulinate esters, which may be used as gasoline and biodiesel additives, respectively [3][4][5][6][7][8]. δ-Aminolevulinic acid is a well-known herbicide and β-acetylacrylic acid has been proposed as a (co-)monomer for novel acrylate polymers [1].…”

Homogeneous Catalyzed Reactions of Levulinic Acid: To γ‐Valerolactone and Beyond

“…[15][16][17][18][19] The high energy density, lower flammablity, hydrophobic nature, low toxicity and high specific gravity of 2-MTHF make it suitable for use as fuel; thus 2-MTHF has been identified a nonpetroleum liquid fuel which can be substituted for or blended with gasoline. 2-MTHF has also been reported to be a better blend with gasoline than methanol and can be more easily integrated into the distribution stream of a refinery.…”

“…[14] 2-MTHF is a green alternative to THF that favourable physical and chemical characteristics such as higher boiling point (80.2 o C), water immiscibility, reactivity and biodegredation pathways. [15][16][17][18][19] 2-MTHF can be used a component of P-series fuel, a non-petroleum liquid fuel which can be substituted for or blended with gasoline. [7,16] The transformation of LA to GVL and beyond typically involves a series of consecutive catalytic dehydration and reduction steps; although oxidative pathways are also possible.…”

Recent Trends in the Production, Combustion and Modeling of Furan-Based Fuels

“…Al-Shaal et al [105] investigated the hydrogenation of GVL to 2-MTHF over Ru/C. The results indicated that GVL was fully converted, and a maximum 2-MTHF yield of 43% was achieved using no solvent.…”