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, especially Fischer-Tropsch reactions. The steps of the process begin with the activation, or reactivation, of a deactivated catalyst, or with the preparation and activation of a fresh catalyst. In accordance with the latter, the steps of the process comprise, first contacting, in one or more steps, a powder or preformed, particulate refractory inorganic support with a liquid, or solution in which there is dispersed or dissolved a compound, or salt of a catalytically active metal, or metals, to impregnate and deposit the metal, or metals, upon the support, or powder. The metal, or metals, impregnated support is calcined following each impregnation step to form oxides of the deposited metal, or metals. The calcined catalyst precursor is then treated with a solution of a chelating compound, preferably a poly- or multidentate chelating compound, sufficient to complex with, extract and remove a portion of the oxides of the metal, or metals. The catalyst is activated by reduction; suitably by contact with hydrogen. In the activation, or reactivation of a deactivated catalyst, the catalyst is first treated with the chelating compound to extract a portion of the oxides of the metal, or metals, and the catalyst is then reduced. In either event, the activated or reactivated catalyst has high activity, or high C 5 + selectivity, or both high activity and C 5 + selectivity in conducting carbon monoxide hydrogenation reactions. The productivity of the process is increased.

Having described the invention, what is claimed is:  
     
         1 . A process for the activation, or reactivation, of a catalyst comprising a powder or particulate solids support, and an oxide, or oxides, of a metal, or metals, catalytically active for conducting carbon monoxide hydrogenation reactions, which comprises 
 contacting, and treating the catalyst with a solution of a chelating compound sufficient to complex with, extract and remove a portion of the metal, or metals, component of the oxide, or oxides, of the metal, or metals, from said catalyst, and    reducing the residual metal, or metals components of the catalyst to activate said catalyst in conducting hydrogenation of carbon monoxide reactions.    
     
     
         2 . The process of    claim 1    wherein the support is a refractory inorganic oxide, the catalytic metal, or metals, composited with the support is comprised of a Group VIII metal, 
 from about 5 wt. percent to about 70 wt. percent of the metal, or metals, is composited with the support,  
 from about 1 percent to about 80 percent of the composited metal, or metals, is removed from the support by treatment with the solution of chelating compound, and  
 the activation, and reduction step is carried out by contact of the catalyst with hydrogen.  
 
     
     
         3 . The process of    claim 1    wherein the powder, or support is a refractory inorganic oxide, the catalytic metal, or metals, composited with the powder, or support is comprised of a Group VIII metal, 
 from about 10 wt. percent to about 30 wt. percent of the metal, or metals, is composited with the powder or support,  
 from about 25 percent to about 75 percent of the composited metal, or metals, is removed from the powder, or support by treatment with the solution of chelating compound, and  
 the activation, and reduction step is carried out by contact of the catalyst with hydrogen.  
 
     
     
         4 . The process of    claim 1    wherein the powder, or support is a crystalline aluminosilicate zeolite, natural or synthetic.  
     
     
         5 . The process of    claim 4    wherein the crystalline aluminosilicate zeolite is an A zeolite, X zeolite, Y zeolite, mordenite, ZSM-zeolite, silicalite, MCM, ALPO, or SAPO type zeolite.  
     
     
         6 . The process of    claim 1    wherein the powder, or support is a refractory inorganic oxide of average pore radius below about 100 Å.  
     
     
         7 . The process of    claim 6    wherein the average pore radius of the powder, or support ranges from about 15 Å to about 40 Å.  
     
     
         8 . The process of    claim 7    wherein the average pore radius of the powder, or support ranges from about 20 Å to about 35 Å.  
     
     
         9 . The process of    claim 1    wherein the chelating compound has a denticity of six, and comprises a nitrogen or oxygen containing compound, or nitrogen and oxygen containing compound.  
     
     
         10 . The process of    claim 1    wherein the so treated catalyst is prepared ab initio by the steps comprising 
 contacting, in one or more steps, a powder, or preformed, particulate solids support with a liquid, or solution in which there is dispersed or dissolved a compound, or salt of a metal, or metals, catalytically active for conducting carbon monoxide hydrogenation reactions, to impregnate and deposit said metal, or metals, upon said powder, or support, and  
 calcining said powder, or support following each impregnation step to form an oxide, or oxides, of the deposited metal, or metals.  
 
     
     
         11 . The process of    claim 10    wherein the catalytically active metal component of the catalyst is comprised of cobalt.  
     
     
         12 . The process of    claim 11    wherein the catalytically active metallic component of the catalyst is oxidized and calcined by contact with an oxidizing atmosphere at temperatures ranging from about 100° C. to about 700° C. and converted to an oxide.  
     
     
         13 . The process of    claim 10    wherein in forming the catalyst from about 5 wt. percent to about 70 wt. percent of the catalytic metal, as elemental metal, is composited with the powder, or solids support, the catalytic metal comprises cobalt, and the powder, or solids support comprises silica, silica-alumina, titania, or a zeolite, natural or synthetic.  
     
     
         14 . The process of    claim 13    wherein the catalyst is contacted with a solution of a chelating compound sufficient to complex with, extract and remove from about 1 percent to about 80 percent of the composited cobalt metal component from the powder, or support, the catalyst then calcined, and the catalyst then activated and reduced by contact with hydrogen.  
     
     
         15 . The process of    claim 14    wherein from about 25 percent to about 75 percent of the composited metal is removed from the powder, or support by contact and treatment with the solution of the chelating compound.  
     
     
         16 . The process of    claim 14    wherein the catalyst contacted with the solution of chelating compound is comprised of cobalt promoted with rhenium.  
     
     
         17 . The process of    claim 16    wherein the catalyst is comprised of cobalt promoted with ruthenium.  
     
     
         18 . A catalyst comprising a powder, or particulate solids support, and an oxide, or oxides, of a metal, or metals, catalytically active for conducting carbon monoxide hydrogenation reactions made in a process as characterized by any of claims  1  through  17 .  
     
     
         19 . A process useful for conducting carbon monoxide hydrogenation reactions by contact at reaction conditions with a catalyst comprising a powder, or particulate solids support, and an oxide, or oxides, of a metal, or metals, catalytically active for conducting said carbon monoxide hydrogenation reactions made by the steps comprising a process as characterized by any of claims  1  through  17 .  
     
     
         20 . A process wherein C 5 + hydrocarbons are produced from carbon monoxide and hydrogen by contact at reaction conditions with a catalyst comprising a powder, or particulate solids support, and an oxide, or oxides, of a metal, or metals, catalytically active for conducting carbon monoxide hydrogenation reactions made by the steps comprising a process as characterized by any of claims  1  through  17 , and all or a portion of the C 5 + hydrocarbons produced by said process are upgraded to more valuable products by fractionation and/or a conversion operation.  
     
     
         21 . A product comprising a hydrocarbon obtained by converting a mixture of hydrogen and carbon monoxide via a carbon monoxide hydrogenation reaction by contact, at reaction conditions, with a catalyst comprising a powder, or particulate solids support, and a metal, or metals, catalytically active for conducting said carbon monoxide hydrogenation reactions, made by the steps of a process characterized by any of claims  1  through  17 .  
     
     
         22 . A C 5 + hydrocarbon product obtained by converting a mixture of hydrogen and carbon monoxide via a carbon monoxide hydrogenation reaction by contact, at reaction conditions, with a catalyst comprising a powder, or particulate solids support, and a metal, or metals, catalytically active for conducting said carbon monoxide hydrogenation reactions, made by the steps of a process characterized by any of claims  1  through  17 .  
     
     
         23 . A hydrocarbon distillate product suitable for use as a transportation fuel which is produced by upgrading a hydrocarbon product obtained by converting a mixture of hydrogen and carbon monoxide via a carbon monoxide hydrogenation reaction by contact, at reaction conditions, with a catalyst comprising a powder, or particulate solids support, and a metal, or metals, catalytically active for conducting said carbon monoxide hydrogenation reactions, made by the steps of a process characterized by any of claims  1  through  17 .  
     
     
         24 . A lube oil, lube oil blending component, or lube oil base stock which is produced by upgrading a hydrocarbon product obtained by converting a mixture of hydrogen and carbon monoxide via a carbon monoxide hydrogenation reaction by contact, at reaction conditions, with a catalyst comprising a powder, or particulate solids support, and a metal, or metals, catalytically active for conducting said carbon monoxide hydrogenation reactions, made by the steps of a process characterized by any of claims  1  through  17 .  
     
     
         25 . A C 5 + hydrocarbon oil suitable as, or for use in the production of a drilling mud, technical or medicinal grade white oil, solvent, chemical raw material, monomer, polymer, emulsion, or specialty product produced by upgrading a hydrocarbon product obtained by converting a mixture of hydrogen and carbon monoxide via a carbon monoxide hydrogenation reaction by contact, at reaction conditions, with a catalyst comprising a powder, or particulate solids support, and a metal, or metals, catalytically active for conducting said carbon monoxide hydrogenation reactions, made by the steps of a process characterized by any of claims  1  through  17 .