Catalyst treatment

Abstract

Molybdenum - vanadium - oxygen oxidation catalyst for producing maleic anhydride from benzene is regenerated and stabilized by the addition of a compound of Mo, Ni, Co, Mn or U, preferably a volatile compound, to the catalyst, after a decline in activity.

The invention claimed is: 
     
       1. In a process for the vapor phase oxidation of C 4  to C 8  hydrocarbons to dicarboxylic .[.acids.]. .Iadd.anhydrides .Iaddend.wherein said hydrocarbon is contacted with a vanadium-molybdenum-oxygen catalyst wherein said catalyst gradually decreases in activity, the improvement comprising adding to said catalyst, after said decrease in activity, .Iadd.a compound of a phosphorus halide or an organo-phosphorus compound selected from the group consisting of ##STR2##.Iaddend.  wherein R is phenyl or an alkyl radical of one to 6 carbon atoms and X is H or R, and thereafter adding to said catalyst a volatilized compound of molybdenum, nickel, cobalt, manganese, uranium or mixtures thereof. 
     
     
       2. The process according to claim 1 wherein said compound .Iadd.of molybdenum, nickel, cobalt, manganese, uranium, or mixtures thereof .Iaddend.has volatilization temperature of 250° C. or less. 
     
     
       3. The process according to claim 1 wherein said compound .Iadd.of molybdenum, nickel, cobalt, manganese, uranium, or mixtures thereof .Iaddend.is an inorganic molybdenum compound. 
     
     
       4. The process according to claim 3 wherein said inorganic compound is molybdenum dibromide, molybdenum tetrabromide, molybdenum tribromide, molybdenum carbonyl, molybdenum pentachloride, molybdenum tetrachloride, molybdenum trichloride, molybdenum hexafluoride, molybdenum oxytetrachloride, molybdenum trichloride, molybdenum oxypentachloride or molybdenum oxytetrafluoride. 
     
     
       5. The process according to claim 4 wherein said inorganic compound is molybdenum hexafluoride. 
     
     
       6. The process according to claim .[.3.]. .Iadd.1 .Iaddend.wherein said .[.inorganic.]. compound is molybdenum dibromide, molybdenum tetrabromide, molybdenum tribromide, molybdenum carbonyl, molybdenum pentachloride, molybdenum tetrachloride, molybdenum trichloride, molybdenum hexafluoride, molybdenum oxtetrachloride, molybdenum oxytrichloride, molybdenum oxypentachloride, molybdenum oxytetrafluoride, nickel acetate, nickel carbonyl, nickel nitrate hexahydrate, cobalt nitrosyl carbonyl, manganese nitrate, uranium hexafluoride, uranium tribromide or .[.manyl.]. .Iadd.uranyl .Iaddend.nitrate. 
     
     
       7. The process according to claim 1 wherein said catalyst has an atomic ratio of molybdenum to vanadium in the range of 0.05 to 0.95 to 1. .[.8. The process according to claim 1 wherein prior to adding said inorganic compound to said catalyst, a compound of a phosphorus halide or an organo-phosphorus compound selected from the group consisting of ##STR3##  wherein R is phenyl or an alkyl radical of one to 6 carbon atoms and X is 
     
     
        H or R, is added to said catalyst..]. 9. The process according to claim .[.8.]. .Iadd.1 .Iaddend.wherein said phosphorus compound is 
     
     
        volatilizable. 10. The process according to claim .[.8.]. .Iadd.1 
     
     
        .Iaddend.wherein said inorganic compound is molybdenum hexafluoride. 11. The process according to claim 1 wherein said compound .Iadd.of molybdenum, nickel, cobalt, manganese, uranium or mixtures thereof .Iaddend.is added to said catalyst during the vapor phase oxidation of hydrocarbons to produce dicarboxylic .[.acids.]. 
     
     
        .Iadd.anhydrides.Iaddend.. 12. The process according to claim 1 wherein said hydrocarbons have 4 to 6 carbon atoms and said maleic anhydride is 
     
     
        the principal product. 13. The process according to claim 12 wherein the 
     
     
        hydrocarbon is benzene. 14. In a process for oxidizing benzene to maleic anhydride which comprises contacting a vaporous stream of benzene with a vanadium-molybdenum-oxygen catalyst, wherein the yield of maleic anhydride diminishes with time, the improvement comprising adding .Iadd.a volatilized compound of a phosphorus halide or an organo-phosphorus compound selected from the group consisting of ##STR4##.Iaddend. wherein R is phenyl or an alkyl radical of one to 6 carbon atoms and X is H or R, followed by adding a volatilized inorganic molybdenum compound to said vaporous stream of benzene while maintaining said catalyst at a temperature of 340° to 500° C.