Hydrogenation Of Γ-valerolactone Research Articles

Cobalt Catalysts Derived from Layered Double Hydroxide/g-C3N4 Composite in the Hydrogenation of γ-Valerolactone into 1,4-Pentanediol

Cobalt Catalysts Derived from Layered Double Hydroxide/g-C3N4 Composite in the Hydrogenation of γ-Valerolactone into 1,4-Pentanediol

Heterogeneously Catalyzed γ-Valerolactone Hydrogenation into 1,4-Pentanediol in Milder Reaction Conditions

Hydrogenation of γ-valerolactone (GVL) in polar solvents (n-butanol, 1,4-dioxane) to 1,4-pentanediol (PDO) and 2-methyltetrahydrofuran (MTHF) was performed at 363–443 K in a fixed bed reactor under overall H2 pressure of 0.7–1.3 MPa. Preliminary screening in a batch reactior was performed with a series of Ru, Ir, Pt, Co, and Cu catalysts, earlier efficiently applied for levulinic acid hydrogenation to GVL. The fresh catalysts were analyzed by transmission electron microscopy (TEM), X-ray fluorescent analysis (XRF), temperature programmed reduction by H2 (H2-TPR), and N2 physisorption. Cu/SiO2 prepared by reduction of copper hydroxosilicate with chrysocolla mineral structure provided better selectivity of 67% towards PDO at 32% GVL conversion in a continuous flow reactor. This catalyst was applied to study the effect of temperature, hydrogen pressure, and contact time. The main reaction products were PDO, MTHF, and traces of pentanol, while no valeric acid was observed. Activity and selectivity to PDO over Cu/SiO2 did not change over 9 h, indicating a fair resistance of copper to leaching.

Preparation of Cu/MgO catalysts for γ-valerolactone hydrogenation to 1,4-pentanediol by MOCVD

The laminar MgO with high specific area and the organometallic precursor Cu(acac)2 were used for the successful synthesis of Cu/MgO catalysts by metal-organic chemical vapor deposition (MOCVD) method. The copper supported on MgO catalysts were characterized by means of X-ray diffraction, Fourier-transform infrared (FT-IR) spectroscopy, field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and N2-physisorption. Characterization results indicated that the organic precursor was successfully deposited onto MgO and the crystal structure of MgO remained intact after deposition. The hydrogenation of γ-valerolactone (γ-GVL) was employed to evaluate the catalytic performance of the Cu/MgO catalysts. It was found that the 18% Cu/MgO catalyst exhibited excellent catalytic activity (90.5%) and selectivity (94.4%) for 1,4-PDO at 473 K and 10 MPa, and the catalytic activity of Cu/MgO did not diminish significantly after cycling for three times.

Hydrogenation of γ-valerolactone in ethanol over Pd nanoparticles supported on sulfonic acid functionalized MIL-101

A ligand-based solid solution approach is employed to incorporate sulphonic acid functional groups into the porous coordination polymer Cr-MIL-101. Loaded with Pd nanoparticles these Pd/MIL-101-SO3H materials act as bifunctional catalysts for the one-pot conversion of γ-valerolactone into ethyl valerate (up to 83% yield). The catalysts were extensively characterized before and after reaction. The influence of the sulfonic acid group density and the reaction conditions on the catalytic activity was systematically investigated and the reaction network for γ-valerolactone upgrading was discussed.