Catalyst used for resource utilization of a fixed bed aniline distillation residue and method for preparing said catalyst

Abstract

The present invention relates to a catalyst for fixed bed aniline rectification residue recycling and preparation method thereof. Based on the total weight of the catalyst, the catalyst comprises the following components in percentage by weight: 5-40% of an active component, 2-30% of a first cocatalyst component, 10-30% of a second cocatalyst component and the balance of carrier, wherein the active component is NiO; the first cocatalyst component is one or more of Fe, Mo, Cr or Co oxide; and the second cocatalyst component is one or more of La, Zr, Y or Ce oxide. The catalyst is prepared through co-precipitation. The catalyst shows high activity and stability in the waste liquid treatment process, and can still maintain high rectification residue cracking rate after reaction of 200 hours.

1 . A catalyst for fixed bed aniline rectification residue recycling, wherein said catalyst comprises the components described below based on the total weight of the catalyst:
 5-40 wt % of NiO as an active component,   2-30 wt % of one or more selected from oxides of Fe, oxides of Mo, oxides of Cr and oxides of Co as a first cocatalyst component,   10-30 wt % of one or more selected from oxides of La, oxides of Zr, oxides of Y and oxides of Ce as a second cocatalyst component,   the remaining portion being the support.   
     
     
         2 . The catalyst according to  claim 1 , wherein said catalyst comprises the components described below based on the total weight of the catalyst:
 15-30 wt % of NiO as the active component,   5-25 wt % of one or more selected from oxides of Fe, oxides of Mo, oxides of Cr and oxides of Co as the first cocatalyst component,   15-25 wt % of one or more selected from oxides of La, oxides of Zr, oxides of Y and oxides of Ce as the second cocatalyst component,   the remaining portion being the support.   
     
     
         3 . The catalyst according to  claim 1 , wherein the support is SiO 2 . 
     
     
         4 . A method of preparing the catalyst of  claim 1 , wherein said method comprises:
 A) dissolving nickel nitrate, the nitrates of the metals comprised in the first and second cocatalyst components in water to form the mixing solution of the metal nitrates, and adding dropwise the mixing solution, alkali solution and aqueous sodium silicate solution in a sedimentation tank separately or together in the manner of parallel flow; or   dissolving nickel nitrate, sodium silicate, and the nitrates of the metals comprised in the first and second cocatalyst components in water to form the mixing solution, and adding dropwise the mixing solution and alkali solution in a sedimentation tank separately or together in the manner of parallel flow; or   dissolving nickel nitrate, the nitrates of the metals comprised in the first and second cocatalyst components in water to form the mixing solution of the metal nitrates, and adding dropwise the mixing solution and alkali solution containing dissolved sodium silicate in a sedimentation tank separately or together in the manner of parallel flow; and   B) precipitating the mixture in the sedimentation tank at controlling pH of 7-8, aging, filtering, drying and calcining the resulting precipitate, and then molding and pulverizing it.   
     
     
         5 . The method according to  claim 4 , wherein the concentration of the metal ions in said mixing solution of metal nitrates is controlled at 0.3-5 mol/L. 
     
     
         6 . The method according to  claim 4 , wherein the alkali solution is aqueous Na 2 CO 3  solution, aqueous NaOH solution or aqueous solution of ammonia, and its concentration is 0.5-10 mol/L. 
     
     
         7 . The method according to  claim 4 , wherein the temperature in the sedimentation tank is controlled at 50-70° C. 
     
     
         8 . The method according to  claim 4 , wherein the aging temperature is 60-80° C. and the aging time is 4-8 h; the drying temperature is 100-150° C. and the drying time is 8-15 h; and the calcination temperature is between 300-700° C. and the calcination time is 4-6 h. 
     
     
         9 . The use of the catalyst of  claim 1  for fixed bed aniline rectification residue recycling, wherein the aniline rectification residue is treated by gas phase hydrogenation to obtain cyclohexyl amine and dicyclohexyl amine, using monofunctional saturated alcohol as the diluent, under the catalysis of the catalyst, at a certain temperature and pressure. 
     
     
         10 . (canceled) 
     
     
         11 . The use according to  claim 9 , wherein the monofunctional saturated alcohol/aniline rectification residue in mass ratio of 0.1-0.7:1 is introduced to a fixed bed reactor, wherein the liquid phase volume space velocity is 0.6-1.5 h −1 , the reaction pressure is 1-4 MPa, the reaction temperature is between 250-320° C., and the volume ratio of the hydrogen amount and the amount of aniline rectification residue is 500-3000:1.