Selective production of γ-valerolactone and ethyl valerate from ethyl levulinate using unsupported nickel phosphide

Unsupported nickel phosphide catalyst containing Ni 2 P phase was applied in the hydrodeoxygenation of ethyl levulinate in ethanol medium for the first time. The obtained catalyst was investigated by XRF, XRD, NH 3 –TPD, XPS and TEM techniques. γ-valerolactone and ethyl valerate were obtained as the hydrodeoxygenation products. Varying the temperature and the reaction time it was possible to obtain these products with high selectivity. γ-valerolactone was selectively formed at 200–250 °C and ethyl valerate was selectively formed at temperatures of 300–350 °C. Increase in reaction time was contributed to ethyl valerate formation. The highest selectivity of ethyl valerate was 100% at full ethyl levulinate conversion at 350 °C after 6 h. 100% γ-valerolactone selectivity was reached at low conversion of ethyl levulinate. The highest yield of γ-valerolactone reached 41.7% after 6 h of the reaction at 250 °C. The selectivity of γ-valerolactone was 86.9% and the conversion of ethyl levulinate was 48.0%. • The HDO of ethyl levulinate in ethanol was investigated over unsupported Ni 2 P. • γ-valerolactone and ethyl valerate was obtained in the HDO of ethyl levulinate. • Ethyl valerate was produced with 100% selectivity at full conversion at 350 °C. • The high activity of the nickel phosphide catalyst is remaining after 10 cycles.