Catalysts and processes for the manufacture of lower aliphatic alcohols from syngas

Abstract

There are disclosed catalyst formulations and methods for the preparation of oxygenated lower aliphatic compounds. The methods comprise applying a mixture of carbon monoxide and hydrogen to a catalyst formulation under reaction conditions, wherein the catalyst formulation is a solid which may comprise: an active metal, a mixed metal component comprising one or more of a metal A, a metal B, a metal C, and a promoter. In certain embodiments one or more of the metals and the promoter may be present as compounds. In a first embodiment the catalyst comprises a noble metal and an alkali metal promoter, mixed oxides of cerium, zirconium and molybdenum, and an alkali metal promoter. Carbon monoxide and hydrogen may be reacted in the presence of the catalysts disclosed to produce mixtures enriched in lower aliphatic alcohols and particularly ethanol. Various catalyst preparation methods are disclosed including autoignition and gel-sol methods.

1 - 29 . (canceled)  
     
     
         30 . A method of making a catalyst formulation comprising: 
 (a) an active metal wherein said active metal is Pd, Pt, Rh, Os or Ir;    (b) a mixed metal component wherein said mixed metal component comprises two or more of: 
 (i) a metal A compound, said metal A being selected from the group consisting of La, Ce, and Sm;  
 (ii) a metal B compound, said metal B being selected from the group consisting of Ti, Zr, and Hf; and  
 (iii) a metal C compound, said metal C being selected from the group consisting of Mo, Cr and W; and  
   (c) a promoter compound selected from the group consisting of compounds of Li, Na, K, Rb and Cs; 
 said method comprising  
   (d) mixing powdered oxides, carbonates or hydroxycarbonates of two or more of said metal A, said metal B and said metal C; and    (e) impregnating said mixture with a solution of a soluble salt of said active metal.    
     
     
         31 . A method of making a catalyst formulation wherein said catalyst formulation comprises: 
 (a) an active metal, said active metal being selected from the group consisting of Pd, Pt, Rh, Os and Ir;    (b) a mixed metal component wherein said mixed metal component comprising two or more components selected from: 
 (i) a metal A compound, said metal A being selected from the group consisting of La, Ce, Sm  
 (ii) a metal B compound, said metal B being selected from the group consisting of Ti, Zr, Hf; and  
 (iii) a metal C compound, said metal C being selected from the group consisting of Mo, Cr and W and  
   (c) a promoter compound selected from the group consisting of compounds of Li, Na, K, Rb and Cs 
 said method comprising mixing a solution of a soluble salt of at least one of said metal A, said metal B, and said metal C; with an alkaline salt of at least one of the others of said metal A, said metal B and said metal C to form a precipitate; and impregnating said precipitate with a solution of a soluble salt of said active metal.  
   
     
     
         32 . A method of making a catalyst formulation wherein said catalyst formulation comprises: 
 (a) an active metal, said active metal being selected from the group consisting of Pd, Pt, Rh, Os and Ir;    (b) a mixed metal component wherein said mixed metal component comprising two or more components selected from: 
 (i) a metal A compound, said metal A being selected from the group consisting of La, Ce, Sm  
 (ii) a metal B compound, said metal B being selected from the group consisting of Ti, Zr, Hf; and  
 (iii) a metal B compound selected from the group consisting of Mo, Cr and W and  
   (c) a promoter compounds selected from the group consisting of compounds of Li, Na, K, Rb and Cs 
 said method comprising autoigniting a mixture of salts of metal A and metal B, and impregnating the resulting preparation with suitable forms of said active metal, said metal C and said promoter.  
   
     
     
         33 . A method of making a catalyst formulation wherein said catalyst formulation comprising: 
 (a) an active metal, said active metal being selected from the group consisting of Pd, Pt, Rh, Os and Ir;    (b) a mixed metal compound wherein said mixed metal component comprising two or more components selected from: 
 (i) a metal A compound, said metal A being selected from the group consisting of La, Ce, Sm  
 (ii) a metal B compound, said metal B being selected from the group consisting of Ti, Zr, Hf; and  
 (iii) a metal C compound selected from the group consisting of Mo, Cr and W and  
   (c) a promoter compound selected from the group consisting of compounds of Li, Na, K, Rb and Cs 
 said method comprising the steps of:  
   (d) mixing solutions of soluble salts of said metal A and said metal B    (e) gelling said mixture with an acid; and    (f) impregnating the resulting preparation with said metal C, said active metal and said promoter.    
     
     
         34 . The method of any one of  claim 30  wherein said metal C is Mo.  
     
     
         35 . The method of any one of  claim 30  wherein said metal A is Ce and said metal B is Zr.  
     
     
         36 . The method of any one of  claim 30  wherein most of said active metal is deposited at the surface of said catalyst formulation  
     
     
         37 . The method of any one of  claim 30  further comprising calcining and reducing said catalyst formulation.  
     
     
         38 . The method of  claim 37  wherein said reduction is carried out by exposing said catalyst formulation to a gas comprising hydrogen or carbon monoxide  
     
     
         39 . The method of any one of  claim 30  further comprising depositing said catalyst formulation on a support.  
     
     
         40 . The method of  claim 39  wherein said support is a metal oxide.  
     
     
         41 . The method of  claim 40  wherein said support has a surface area of between 100 and 500 m 2 /g.  
     
     
         42 - 46 . (canceled)  
     
     
         47 . The catalyst formulation made according to any one of  claim 30.