Process for the production of hydrocarbon biofuels

Abstract

A method of deoxygenating a feedstock, comprising at least one oxygenated organic compound, to form a hydrocarbon product, comprising the steps of: contacting the feedstock with a catalyst under conditions to promote deoxygenation of the at least one oxygenated compound, wherein the catalyst comprises a mixed metal oxide of the empirical formula: (M2)y(M1)O—ZnO—(Al2O3)x is disclosed. The invention is useful in the production of renewable fuels, such as renewable diesel, and jet fuel.

1 . A method of deoxygenating a feedstock, comprising at least one oxygenated organic compound, to form a hydrocarbon product, comprising the steps of:
 contacting a catalyst with a reducing agent to form a reduced catalyst,   contacting the feedstock with the reduced catalyst under conditions to promote deoxygenation of the at least one oxygenated organic compound,   
       wherein the catalyst is a mixed metal oxide consisting essentially of:
 ZnO; 
 a metal oxide M 1 , where the metal of the metal oxide M 1  is selected from the group consisting of Ag, Au, Co, Cr, Fe, Ir, Ni, Os, Pd, Pt, Rh, Ru, and W; 
 optionally a metal oxide M 2 , where the metal of the metal oxide M 2  is selected from the group consisting of Ag, Au, Co, Cr, Cu, Fe, Ir, Ni, Os, Pd, Pt, Rh, Ru, and W, but is not the same metal as the metal of the metal oxide M 1 ; and 
 optionally aluminum oxide. 
 
     
     
         2 . method of  claim 1 , wherein the mixed metal oxide consists essentially of:
 ZnO;   a metal oxide M 1 , where the metal of the metal oxide M 1  is selected from the group consisting of Ag, Au, Co, Cr, Fe, Ir, Ni, Os, Pd, Pt, Rh, Ru, and W;   a metal oxide M 2 , where the metal of the metal oxide M 2  is selected from the group consisting of Ag, Au, Co, Cr, Cu, Fe, Ir, Ni, Os, Pd, Pt, Rh, Ru, and W, but is not the same metal as the metal of the metal oxide M 1 ; and   aluminum oxide.   
     
     
         3 . The method of  claim 1 , wherein the mixed metal oxide consists essentially of:
 ZnO;   a metal oxide M 1 , where the metal of the metal oxide M 1  is selected from the group consisting of Ag, Au, Co, Cr, Fe, Ir, Ni, Os, Pd, Pt, Rh, Ru, and W; and   a metal oxide M 2  , where the metal of the metal oxide M 2  is selected from the group consisting of Ag, Au, Co, Cr, Cu, Fe, Ir, Ni, Os, Pd, Pt, Rh, Ru, and W, but is not the same metal as the metal of the metal oxide M 1 .   
     
     
         4 . The method of  claim 1 , wherein the mixed metal oxide consists essentially of:
 ZnO; and   a metal oxide M 1 , where the metal of the metal oxide M 1  is selected from the group consisting of Ag, Au, Co, Cr, Fe, Ir, Ni, Os, Pd, Pt, Rh, Ru, and W.   
     
     
         5 . The method of  claim 1 , wherein the mixed metal oxide consists essentially of comprises:
 ZnO;   a metal oxide M 1 , where the metal of the metal oxide M 1  is selected from the group consisting of Ag, Au, Co, Cr, Fe, Ir, Ni, Os, Pd, Pt, Rh, Ru, and W; and   aluminum oxide.   
     
     
         6 . The method of  claim 1 , wherein M 2  is present and the metal of the metal oxide M 2  is Ni or Co. 
     
     
         7 . The method of  claim 1 , wherein the metal of the metal oxide M 1  is Co or Ni. 
     
     
         8 . The method according to  claim 1 , wherein the metal of the metal oxide M 1  is selected from the group consisting of Co and Ni, and the metal of the metal oxide M 2  is selected from the group consisting of Ag, Au, Co, Ir, Ni, Os, Pd, Pt, Rh, and Ru. 
     
     
         9 . The method of  claim 1 , wherein the catalyst is a bulk catalyst. 
     
     
         10 . The method of  claim 1 , wherein the catalyst is a supported catalyst, and wherein the support is alumina, silica-alumina, a zeolite, aluminosilicate, a hydrotalcite, a clay, activated carbon, carbon fibre, carbon nanotube, or a metal oxide. 
     
     
         11 . The method of  claim 10 , wherein the support is activated carbon. 
     
     
         12 . The method of  claim 1 , wherein the oxygenated organic compound is a carboxylic acid, a carboxylic ester, an aldehyde, a ketone, or a mixture thereof. 
     
     
         13 . The method of  claim 12 , wherein the oxygenated organic compound is a triglyceride, a free fatty acid, a fatty acid alkyl ester, a fatty aldehyde, or a mixture thereof. 
     
     
         14 . The method of  claim 13 , wherein the oxygenated organic compound is a fatty acid methyl ester. 
     
     
         15 . The method of any one of  claim 1 , wherein a lower aliphatic alcohol is co-fed with the oxygenated organic compound to produce hydrogen in situ. 
     
     
         16 . The method of  claim 15 , wherein the lower aliphatic alcohol is methanol or ethanol. 
     
     
         17 . The method of  claim 1 , wherein the mixed metal oxide consists essentially of:
 ZnO;   a metal oxide M 1 , where the metal of the metal oxide M 1  is Co or Ni;   a metal oxide M 2 , where the metal of the metal oxide M 2  is Co or Ni, but is not the same metal as the metal of the metal oxide M 1 ; and   aluminum oxide.   
     
     
         18 . The method of  claim 1 , wherein the mixed metal oxide consists essentially of:
 ZnO;   a metal oxide M 1 , where the metal of the metal oxide M 1  is Co or Ni; and   a metal oxide M 2 , where the metal of the metal oxide M 2  is Co or Ni, but is not the same metal as the metal of the metal oxide M 1 .   
     
     
         19 . The method of  claim 1 , wherein the mixed metal oxide consists essentially of:
 ZnO;   a metal oxide M 1 , where the metal of the metal oxide M 1  is Co or Ni; and   aluminum oxide.   
     
     
         20 . The method of  claim 1 , wherein the mixed metal oxide consists essentially of:
 ZnO; and   a metal oxide M 1 , where the metal of the metal oxide M 1  is Co or Ni.