Development Of Efficient Non-noble Metal Catalyst And Its Catalytic Performance For Hydrogenation Of 1-nitronaphthalene

As a very important aromatic amine organic compound,1-naphthylamine is widely used in medicine,dye and other fields.At present,the catalyst used in the process route of preparing 1-naphthylamine with 1-nitronaphthalene as a raw material is mainly noble metal catalyst,and the production cost is high.In this project,low-cost non-precious metal nickel,cobalt,and copper are used as hydrogenation active components to develop high-efficiency non-precious metal-based catalysts to reduce catalyst costs.The subject research has very important research significance and industrial application prospects.First,a silica-supported carbon-nitrogen-coated cobalt-nickel metal catalyst Co_xNi_y@NC/Si O₂ with strong thermal stability and good cyclability was prepared by using room temperature stirring method and high-temperature calcination reduction post-treatment method.It was applied to the liquid-phase hydrogenation reaction of 1-nitronaphthalene,and the experimental results showed that the Co₂Ni₁@NC/Si O₂catalyst exhibited excellent hydrogenation ability when the cobalt-nickel ratio was 2:1,even under mild reaction conditions（90℃,0.6MPa,5.5h）,the yield of 1-naphthylamine can reach more than 99%,and the catalyst also performs well in the stability test.Through various characterization analysis,it is proved that the reason for the improvement of the hydrogenation capacity of the catalyst is the increase of the specific surface area and the improvement of the dispersion of the metal active center of the catalyst,and the synergistic effect between the cobalt and nickel bimetals has a positive impact on the hydrogenation activity of the catalyst.Secondly,Ni_xCu_y@C,a carbon-coated nickel-copper alloy catalyst with higher catalytic activity compared with Co₂Ni₁@NC/Si O₂ catalyst,was prepared by one-step pyrolysis method and applied to catalyze the liquid phase of 1-nitronaphthalene.Hydrogenation reaction to prepare 1-naphthylamine,The experimental results show that the Ni₁Cu₁@C catalyst prepared when the ratio of nickel to copper is 1:1 exhibits relatively optimal catalytic hydrogenation ability,Under milder reaction conditions（60°C,0.6MPa,5hours）,the yield of 1-naphthylamine can reach more than 99%,and it also shows good catalytic hydrogenation activity at low temperature（30°C）.Combined with the analysis of catalytic characterization,it is proved that the high hydrogenation activity of the catalyst is mainly due to the high dispersion of the metal active center of the catalyst and the formation of nickel-copper alloy,which promotes the synergistic effect between nickel-copper bimetals.In addition,the kinetics of the hydrogenation of 1-nitronaphthalene catalyzed by Ni₁Cu₁@C were also investigated.According to the Haber mechanism,the reaction kinetic model was constructed.Through reasonable theoretical derivation and Matlab fitting of various parameters in the reaction kinetic model,the apparent activation energy of the catalytic reaction was calculated to be 48.6 KJ/MOL.The fitting and verification show that the constructed kinetic model is of high reliability,and this model can be used to simulate and calculate the hydrogenation reaction of 1-nitronaphthalene catalyzed by Ni₁Cu₁@C catalyst.