Surface supported cobalt catalysts, process utilizing these catalysts for the preparation of hydrocarbons from synthesis gas and process for the preparation of said catalysts

Abstract

A supported particulate cobalt catalyst is formed by dispersing cobalt, alone or with a metal promoter, particularly rhenium, as a thin catalytically active film upon a particulate support, especially a silica or titania support. This catalyst can be used to convert an admixture of carbon monoxide and hydrogen to a distillate fuel constituted principally of an admixture of linear paraffins and olefins, particularly a C 10+ distillate, at high productivity, with low methane selectivity. A process is also disclosed for the preparation of these catalysts.

What is claimed is:  
     
       1. A process useful for the conversion of synthesis gas to liquid hydrocarbons and less than about 10 mole % methane which comprises contacting at reaction conditions a feed comprised of carbon monoxide and hydrogen, in H 2 :CO molar ratio equal to or greater than about 0.5:1 at total pressure equal to or greater than about 80 psig, over a catalyst composition having a productivity of at least 150 hr −1  at 200° C. and which comprises cobalt dispersed as a catalytically active layer upon the outer surface of an inorganic oxide support of a thickness of less than about 200 microns, with the loading of cobalt at least about 0.04 g/cc in said catalytically active layer, calculated as metallic cobalt per packed bulk volume of catalyst. 
     
     
       2. The process of claim  1  wherein the molar ratio of H 2 :CO ranges from about 1.7:1 to about 2.5:1. 
     
     
       3. The process of claim  2  wherein the total pressure of the reaction ranges from about 140 psig to about 400 psig. 
     
     
       4. The process of claim  1  wherein the reaction conditions are defined within ranges as follows: 
       
         
           
                 
                 
                 
               
                     
                     
                 
                     
                   H 2 :CO mole ratio 
                   about 1.7:1 to 2.5:1 
                 
                     
                   Gas Hourly 
                 
                     
                   Space Velocities, V/Hr/V 
                   about 300 to 1500 
                 
                     
                   Temperature, ° C. 
                   about 190 to 220 
                 
                     
                   Total Pressure, psig 
                   about 140 to 400 
                 
                     
                     
                 
             
                
               
               
                
                
                
                
                
                
               
            
           
         
       
     
     
       5. The process of claim  1  wherein the catalytically active surface layer of the catalyst is of average thickness ranging from about 5 microns to about 200 microns with the cobalt loading ranging being at least about 0.04 g/cc in said catalytically active surface layer. 
     
     
       6. The process of claim  1  wherein the catalyst further comprises rhenium rhenium constitutes part of the catalytically active surface layer of the catalyst. 
     
     
       7. The process of claim  1  wherein the catalyst further comprises hafnium which constitutes part of the catalytically active surface layer of the catalyst. 
     
     
       8. The process of claim  1  wherein the support is comprised of silica or titania. 
     
     
       9. A process for the conversion of synthesis gas to C 10+  hydrocarbons which comprises contacting at reaction conditions a feed comprised of an admixture of carbon monoxide and hydrogen, in H 2 :CO molar ratio equal to or greater than about 1.71 at total pressure equal to or greater than about 80 psig, over a catalyst composition which comprises cobalt dispersed as a catalytically active layer upon the outer surface of a silica or titania containing support, said active layer being of a thickness of less than 200 microns, and with sufficient cobalt loading to produce a productivity of at least about 150 hr −1  at 200° C. and convert to methane less than 10 mole percent of the carbon monoxide converted. 
     
     
       10. The process of claim  9  wherein the support is comprised predominantly of silica. 
     
     
       11. The process of claim  1  wherein said process is a slurry-bed synthesis gas conversion process and said catalyst having a particle size diameter of about 10 microns to about 1 mm. 
     
     
       12. The process of claim  1  wherein said liquid hydrocarbon comprises a high quality distillate fuel. 
     
     
       13. The process of claim  1  wherein said liquid hydrocarbon comprises C 10+    hydrocarbons.   
     
     
       14. The process of claim  13  wherein said C 10+    hydrocarbons comprise C   10+    linear paraffins.   
     
     
       15. The process of claim  13  comprising the further step of producing a middle distillate fuel from said C 10+    hydrocarbons.   
     
     
       16. The process of claim  15  wherein said middle distillate fuel comprises a diesel fuel. 
     
     
       17. The process of claim  15  wherein said middle distillate fuel comprises a C 10   -C   20    product.   
     
     
       18. The process of claim  15  wherein said middle distillate fuel comprises a jet fuel. 
     
     
       19. The process of claim  13  including upgrading said C 10+    hydrocarbons.   
     
     
       20. The process of claim  19  including upgrading said C 10+    hydrocarbons to a diesel fuel.   
     
     
       21. The process of claim  19  including upgrading said C 10+    hydrocarbons to a jet fuel.   
     
     
       22. The process of claim  9  wherein said C 10+    hydrocarbons comprise C   10+    linear paraffins.   
     
     
       23. The process of claim  9  comprising the further step of producing a middle distillate fuel from said C 10+    hydrocarbons.   
     
     
       24. The process of claim  23  wherein said middle distillate fuel comprises a diesel fuel. 
     
     
       25. The process of claim  23  wherein said middle distillate fuel comprises a jet fuel. 
     
     
       26. The process of claim  23  wherein said middle distillate fuel comprises a C 10   -C   20    product.   
     
     
       27. The process of claim  9  including upgrading said C 10+    hydrocarbons.   
     
     
       28. The process of claim  27  including upgrading said C 10+    hydrocarbons to a diesel fuel.   
     
     
       29. The process of claim  27  including upgrading said C 10+    hydrocarbons to a jet fuel.