A Study On Non-precious Metal(Ni,Fe,Co) Catalysts For Furfural Hydrogenation

Furfural,as one of the most important biomass platform compounds,can realize the conversion of furfural to furfuryl alcohol and other important chemical products through the hydrogenation process of molecular hydrogen catalytic hydrogenation and"non-additional H₂"catalytic transfer hydrogenation.In this paper,Ni-P@C,Fe₃O₄@C,CoO@C and Fe₃O₄/C catalysts were prepared.The hydrogenation of furfural over these catalysts was investaged with external molecular hydrogen or alcohols as hydrogen donors.The main researches are as follows:?1?Ni-P@C catalyst based on metal organic frameworks?MOFs?was prepared by hydrothermal method,and unsupported Ni-P catalyst was prepared by co-precipitation method.The effects of calcination temperature and reaction conditions on catalytic performance of Ni-P@C and Ni-P were studied using hydrogenation of furfural with molecular hydrogen.The results show that Ni-P@C catalyst prepared with calcined at 973 K for 4 h exhibited high catalytic hydrogenation activity and reusability.Ni-P@C catalyst exhibited a much higher catalytic activity for hydrogenation of furfural than Ni-P catalyst,and the conversion of furfural increased from 88.7%to 99.9%.Further extension of the reaction time has a great influence on the distribution of products.?2?Fe₃O₄@C catalyst was prepared by solvothermal method with using ethylene glycol as reducting agent.The effects of solvothermal and calcination conditions on the performance of Fe₃O₄@C catalyst were investigated to determine the optimal preparation conditions and formation mechanism.The effects of hydrogen donor species and reaction conditions on the performance of Fe₃O₄@C catalyst for furfural catalytic transfer hydrogenation were investigated.Under the optimal reaction conditions,the conversion of furfural and the selectivity of furfuryl alcohol were 93.6%and 98.9%,respectively.Furthermore,the Fe₃O₄@C catalyst can be easily collected with an external magnet and reused without significant loss in catalytic activity.The mechanism of catalytic transfer hydrogenation of furfural by Fe₃O₄@C catalyst obeys the Meerwein-Ponndorf-Verley?MPV?reaction on a Lewis acid site?Fe₃O₄?.?3?The CoO@C catalyst was prepared with hydrothermal method.Effects of Co valence state,hydrothermal condition and calcination condition on the catalyst performance were investigated to determine the optimal preparation condition.A possible mechanism for the formation mechanism of the catalyst was proposed.The effects of hydrogen donor species and reaction conditions on the performance of CoO@C catalyst for furfural catalytic transfer hydrogenation were studied.Under the optimal reaction conditions,the conversion of furfural and the selectivity of furfuryl alcohol were 91.5%and 99.2%,respectively.CoO@C catalyst showed good magnetic recoverability and reusability.The reaction was similar to the MPV mechanism.?4?Fe₃O₄/C catalyst based on MOFs structure was prepared with solvothermal method.The effects of solvents,organic ligands,solvothermal conditions and calcination conditions on Fe3O4/C catalyst were investigated to determine the preparation conditions and formation mechanism of the catalyst.The effects of hydrogen donor species and reaction conditions on the performance of furfural catalytic transfer hydrogenation over Fe₃O₄/C catalyst were studied.Under the optimal reaction conditions,the conversion of furfural and the selectivity of furfuryl alcohol were 76.4%and 98.5%,respectively.The Fe₃O₄/C catalyst has a good magnetic recovery and reusability.The reaction obeys the MPV mechanism on a Lewis acid site?Fe₃O₄?.