Furfural Hydrogenation to Furfuryl Alcohol over Bimetallic Ni–Cu Sol–Gel Catalyst: A Model Reaction for Conversion of Oxygenates in Pyrolysis Liquids

• Published in: Topics in catalysis 2016-09, Vol.59 (15-16), p.1413-1423
• Main Authors: Khromova, S. A., Bykova, M. V., Bulavchenko, O. A., Ermakov, D. Yu, Saraev, A. A., Kaichev, V. V., Venderbosch, R. H., Yakovlev, V. A.
• Format: Article
• Language: English
• Subjects: Aldehydes; Bimetals; Catalysis; Catalysts; Characterization and Evaluation of Materials; Chemistry; Chemistry and Materials Science; Copper; Copper converters; Decanol; Furfural; Furfuryl alcohol; Hydrogenation; Industrial Chemistry/Chemical Engineering; Ketones; Nickel; Original Paper; Pharmacy; Physical Chemistry; Pyrolysis; Sol-gel processes; Solvents; X ray photoelectron spectroscopy
• ISSN: 1022-5528; 1572-9028
• DOI: 10.1007/s11244-016-0649-0

High metal loading NiCu-based catalyst of Picula™ series produced by sol–gel technique was applied to furfural hydrogenation in the presence of hydrogen. This reaction represents the stabilization of pyrolysis oil that involves the selective reduction of aldehydes and ketones to alcohols and unsaturated C–C double bonds of pyrolysis oils components. The catalysts were pre-reduced at 250 and 300 °C. According to XRD analysis results, copper is mainly in the metallic state, and Ni is mostly in the form of oxide and silicate. XPS measurements reveal that hydrogen treatment at 250 °C leads to the partial reduction of Ni to the metallic state (6 %) while further reduction at 300 °C leads to an increase in this proportion up to 39 %. A 100 % selectivity towards furfuryl alcohol was achieved at 130 °C and 5 MPa of hydrogen in a batch reactor using decyl alcohol as a solvent. In the experiments with i -propanol as a solvent at 110–170 °C the main product was furfuryl alcohol, but minor components traced back were tetrahydrofurfuryl alcohol, 2-methylfuran and isopropyl furfuryl ether. The lower catalyst reduction temperature promotes the formation of isopropyl ester, while a higher reduction temperature favors further furfuryl alcohol hydrogenation.