Process for the preparation of high activity carbon monoxide hydrogenation catalysts; the catalyst compositions, use of the catalysts for conducting such reactions, and the products of such reactions

Abstract

A process for the preparation of a catalyst useful for conducting carbon monoxide hydrogenation reactions, particularly Fischer-Tropsch reactions; the catalyst compositions, use of the catalyst compositions for conducting such reactions, and the products of these reactions. The steps of the process for producing the catalyst comprise impregnating a powder, or particulate refractory inorganic oxide solids, preferably silica, with a) a soluble compound or salt of a catalytic metal of the Iron Group, preferably cobalt, and b) a soluble compound, or salt, of a Group VIII noble metal, preferably platinum, suitably by sequential contact of the solids with a solution of (a) and a solution of (b), by sequential contact of the solids with a solution of (b) and a solution of (a), or by contact with a solution which contains both (a) and (b). The metals impregnated solids, or particulate solids precursor material, after impregnation with the Group VIII noble metal, is washed with a hydrocarbyl ammonium hydroxide or ammonium hydroxide solution, the material shaped, dried and calcined, and the metals components thereof thereafter reduced to form the finished catalyst. The catalyst formed from the hydrocarbyl ammonium hydroxide or ammonium hydroxide-washed catalyst precursor, quite surprisingly, is more active and selective in conducting a carbon monoxide hydrogenation reaction to produce hydrocarbon waxes, with lower gas make, than a catalyst of corresponding composition similarly prepared except that the catalyst was prepared from a catalyst precursor which was not washed with a hydrocarbyl ammonium hydroxide or ammonium hydroxide solution.

Having described the invention, what is claimed is:  
     
         19 . Process for preparing a supported catalyst comprising a Group VIII noble metal comprising: 
 (a) compositing a Group VIII noble metal salt on to a support,    (b) drying and calcining the composited support,    (c) washing the composited support with at least one of (i) hydrocarbyl ammonium hydroxide, or (ii) ammonium hydroxide solution,    (d) drying and calcining the composited and washed support to form a supported catalyst.    
     
     
         20 . A process according to claim  19  further comprising the step of reducing the composited support with a hydrogen or hydrogen containing gas following step (d).  
     
     
         21 . A process according to  claim 20  further comprising compositing an Iron Group metal or salt onto the support.  
     
     
         22 . A process according to  claim 21  wherein the Iron Group metal is composited onto the support prior to step (b).  
     
     
         23 . A process according to  claim 21  wherein the Iron Group metal is composited onto the support after step (d) and calcined prior to the reducing step.  
     
     
         24 . A process according to  claim 21  wherein the support is a refractory inorganic oxide.  
     
     
         25 . A process according to  claim 24  wherein the compositing is conducted by combining the refractory inorganic oxide solid, or solids, with a solution of a compound or salt of the catalytic metal of the Iron Group and a solution of a compound or salt of the Group VIII noble metal.  
     
     
         26 . The process according to  claim 21  wherein the Iron Group metal is cobalt, and the Group VIII noble metal is platinum.  
     
     
         27 . The process of  claim 21  wherein the support is further composited with at least one promoter metal.  
     
     
         28 . The process of  claim 27  wherein the promoter metal is rhenium.  
     
     
         29 . The process of  claim 21  wherein the Iron Group metal is composited upon the support in a concentration ranging from about 5 percent to about 70 percent, and the Group VIII noble metal is composited upon the support in a concentration ranging from about 0.10 percent to about 5 percent, based on the weight of the catalyst (dry basis).  
     
     
         30 . The process of  claim 29  where the concentration of the Iron Group metal ranges from about 10 percent to about 30 percent, and the concentration of the Group VIII noble metal ranges from about 0.2 percent to about 1.0 percent.  
     
     
         31 . The process of  claim 30  wherein the concentration of the Group VIII noble metal ranges from about 0.5 to about 0.7 percent.  
     
     
         32 . The process of  claim 24  wherein the refractory inorganic oxide support is silica.  
     
     
         33 . The process of  claim 32  wherein the silica is present in the finished catalyst composition in an amount sufficient to provide a concentration ranging from about 25 percent to about 90 percent, based on the weight of the catalyst (dry basis).  
     
     
         34 . The process of  claim 21  wherein the metals component of said catalyst is comprised of cobalt and platinum.  
     
     
         35 . A process according to  claim 20  further comprising repeating step (c) at least once.  
     
     
         36 . The process of  claim 24  wherein the refractory inorganic oxide support is silica, the Iron Group metal is cobalt, the Group VIII noble metal is platinum.  
     
     
         37 . A carbon monoxide hydrogenation catalyst produced according to the process of  claim 24 .  
     
     
         38 . The catalyst according to  claim 37  wherein the Iron Group metal is cobalt.  
     
     
         39 . The catalyst according to  claim 37  wherein the Iron Group metal is cobalt, the Group VIII noble metal is platinum, and the refractory inorganic oxide support is silica.  
     
     
         40 . A process for the production of hydrocarbons from hydrogen and carbon monoxide comprising contacting hydrogen and carbon monoxide, at hydrocarbon synthesis reaction conditions, with the catalyst of  claim 24 .  
     
     
         41 . A process according to  claim 40  wherein said hydrocarbons are primarily C 5 + liquids.  
     
     
         42 . A process according to  claim 41  wherein at least a portion of the C 5 + liquids are treated by fractionation or conversion.  
     
     
         43 . A process according to  claim 42  wherein the treatment is fractionation and a transportation fuel or fuel blending product is recovered.  
     
     
         44 . A process according to  claim 43  wherein the fuel or fuel blending product is a jet or diesel fuel.  
     
     
         45 . A process according to  claim 42  wherein the treatment is conversion in the absence of a catalyst.  
     
     
         46 . A process according to  claim 45  wherein the treatment is steam cracking.  
     
     
         47 . A process according to  claim 42  wherein the treatment is conversion i the presence of a catalyst.  
     
     
         48 . A process according to  claim 47  wherein the catalytic conversion is in the presence of hydrogen.  
     
     
         49 . A process according to  claim 48  wherein the catalytic conversion is hydroisomerization.  
     
     
         50 . A process according to  claim 49  wherein a fuel useful as transportation fuel or a blending stock therefor is recovered.