Continuous-Flow Hydrogenation of Methyl Levulinate Promoted by Zr-Based Mesoporous Materials

Abstract

Several Zr-based materials, including ZrO2 and Zr-SBA-15, with different silicon/zirconium molar ratios, and ZrO2/Si-SBA-15 (where SBA-15 stands for Santa Barbara Amorphous material no. 15), have been prepared as hydrogenation catalysts. The materials were characterized using different characterization techniques including X-ray diffraction (XRD), N2 porosimetry, scanning electron microscopy (SEM/EDX), diffuse reflectance infrared Fourier transform spectroscopy (DRIFT) of pyridine adsorption and the pulsed chromatographic method using pyridine and 2,6-dimethylpyridine as probe molecules, mainly, have been employed for the characterization of the structural, textural, and acidic properties of the synthesized materials, respectively. The catalysts have been evaluated in the hydrogenation reaction of methyl levulinate using 2-propanol as hydrogen donor solvent. The reaction conditions were investigated and stablished at 30 bar system pressure with a reaction temperature of 200 °C using around 0.1 g of catalyst and a flow rate of 0.2 mL/min flow rate of a 0.3 M methyl levulinate solution in 2-propanol. All catalysts employed in this work exhibited good catalytic activities under the investigated conditions, with conversion values in the 15⁻89% range and, especially, selectivity to Υ-valerolactone in the range of 76⁻100% (after one hour time on stream). The highest methyl levulinate conversion and selectivity was achieved by ZrO2/Si-SBA-15 which can be explained by the higher dispersion of ZrO2 particles together with a highest accessibility of the Zr sites as compared with other materials such as Zr-SBA-15, also investigated in this work.

Keywords

• SBA-15
• zirconium
• methyl levulinate
• Υ-valerolactone
• flow chemistry