Hydration of aliphatic nitriles to amides using copper metal catalysts

Abstract

Aliphatic nitriles are converted to the corresponding amides by contacting the nitrile in the presence of water with a cupreous catalyst containing copper metal.

We claim: .[.1. In the process for converting an aliphatic nitrile to the corresponding amide by reacting the nitrile with water in the presence of a heterogeneous catalyst, the improvement comprising: using a catalytic amount of a catalyst consisting essentially of copper metal..]. .[.2. The process of claim 1 wherein the nitrile is an olefinic nitrile of 3 to 6 carbon atoms..]. .[.3. The process of claim 1 wherein the nitrile is acrylonitrile..]. .[.4. The process of claim 1 wherein the catalyst is protected from contact with oxygen prior to or during the hydration..]. .[.5. The process of claim 1 wherein the reaction is run in the liquid phase..]. .[.6. The process of claim 1 wherein the temperature is about 25° to about 200° C..]. .[.7. The process of claim 1 wherein the catalyst has a surface area of at least about 0.2 square meter per gram..]. .[.8. The process of claim 3 wherein the catalyst has a surface area of at least about 0.5 square meter per gram..]. .[.9. The process of claim 8 wherein the reaction is run in the liquid phase at a temperature 
     
        of about 25° to 200° C..]. .Iadd.10.  In a process for converting acrylonitrile to acrylamide by reacting the acrylonitrile with water in the presence of a heterogeneous catalyst, the improvement comprising using a catalytic amount of a catalyst consisting essentially of copper metal, which catalyst is protected from contact with oxygen by protecting the catalyst from contact with an oxygen-containing gas after activation and by removing substantially all of the dissolved oxygen from the feed stream of nitrile and water and under further conditions such that the yield of acrylamide is at least 91 percent. .Iaddend. .Iadd.11. The process of claim 10 wherein the catalyst consisting essentially of copper metal is prepared by reducing copper hydroxide or a copper salt. .Iaddend. .Iadd.12. The process of claim 10 wherein the catalyst consisting essentially of copper metal is prepared by reducing a copper salt selected from copper salts having nitrogen-containing anions, having halogen-containing anions, having sulfur-containing anions or having 
     
     
        organic carboxylic acid-containing anions. .Iaddend. .Iadd.13.  The process of claim 12 wherein the copper salt is selected from copper nitrate, copper acetate, copper carbonate, copper oxidate, copper sulfide and copper chloride. .Iaddend. .Iadd.14. The process of claim 12 wherein the copper salt is CuCO 3  and the nitrile is acrylonitrile. .Iaddend. .Iadd.15. The process of claim 12 wherein the copper salt is Cu(NO 3 ) 2  and the nitrile is acrylonitrile. .Iaddend. .Iadd.16. The process of claim 12 wherein the copper salt is Cu(C 2  H 3  O 2 ) 2  and the nitrile is acrylonitrile. .Iaddend. .Iadd.17. The process of claim 12 wherein the copper salt is CuC 2  O 4  and the nitrile is acrylonitrile. .Iaddend. .Iadd.18. The process of claim 12 wherein the copper salt is copper tartarate and the nitrile is acrylonitrile. .Iaddend. .Iadd.19. The process of claim 12 wherein the copper salt is CuCl 2  and the nitrile is acrylonitrile. .Iaddend. 
     
     
        .Iadd.20.  The process of claim 10 wherein the catalyst consisting essentially of copper metal is prepared by contacting, under aqueous conditions, a soluble copper salt with an active metal reducing agent. .Iaddend. .Iadd.21. The process of claim 20 wherein the active metal reducing agent is zinc. .Iaddend. .Iadd.22. The process of claim 10 wherein the catalyst consisting essentially of copper metal is mounted on an inert support. .Iaddend. .Iadd.23. The process of claim 10 wherein the catalyst consisting essentially of copper metal has a surface area of at 
     
     
        least about 0.2 square meter per gram. .Iaddend. .Iadd.24.  The process of claim 13 wherein the catalyst has a surface area of at least about 0.5 meter per gram. .Iaddend. .Iadd.25. The process of claims 11, 12, 20, 22 or 23 wherein the reaction is run in the liquid phase at a temperature of about 25° C. to 200° C. .Iaddend. .Iadd.26. The process of claim 10 wherein the reaction is run in the liquid phase at a temperature 
     
     
        of about 25° C. to 200° C. .Iaddend. .Iadd.27.  The process of claim 10 wherein the process is carried out under conditions in which -hydroxypropionitrile is yielded at less than one percent. .Iaddend. .Iadd.28. The process of claim 10 wherein the process is carried out under conditions such that little or no by-products are formed. .Iaddend. .Iadd.29. The process of claim 10 wherein the process is carried out under conditions such that of the acrylonitrile converted at least 97.8 percent is converted to acrylamide. .Iaddend. .Iadd.30. The process of claim 10 wherein the process is carried out under conditions such that the acrylonitrile is converted to acrylamide without significant amounts of by-products. .Iaddend. .Iadd.31. The process of claim 10 wherein the process is carried out under conditions such that little or no acidic 
     
     
        compounds are formed. .Iaddend. .Iadd.32.  In a process for converting acrylonitrile to acrylamide by reacting the acrylonitrile with water in the presence of a heterogeneous catalyst, the improvement comprising using a catalytic amount of a catalyst consisting of copper metal, which catalyst is protected from contact with oxygen by protecting the catalyst from contact with an oxygen-containing gas after activation and by removing substantially all of the dissolved oxygen from the feed stream of nitrile and water and under further conditions such that the yield of 
     
     
        acrylamide is at least 91 percent. .Iaddend. .Iadd.33.  In a process for converting acrylonitrile to acrylamide by reacting the acrylonitrile with water in the presence of a heterogeneous catalyst, the improvement comprising using a catalytic amount of a catalyst consisting essentially of copper metal, which catalyst is protected from contact with oxygen by protecting the catalyst from contact with an oxygen-containing gas after activation and by removing substantially all of the dissolved oxygen from the feed stream of nitrile and water and under further conditions such that β-hydroxypropionitrile is yielded at less than one percent. .Iaddend. .Iadd.34. In a process for converting acrylonitrile to acrylamide by reacting the acrylonitrile with water in the presence of a heterogeneous catalyst, the improvement comprising using a catalytic amount of a catalyst consisting essentially of copper metal, which catalyst is protected from contact with oxygen by protecting the catalyst from contact with an oxygen-containing gas after activation and by removing substantially all of the dissolved oxygen from the feed stream of nitrile and water and under further conditions such that at least 97.8 percent of the acrylonitrile converted is converted to acrylamide. .Iaddend.