Catalyst, Catalyst Support And Process For Hydrogenation, Hydroisomerization, Hydrocracking And/Or Hydrodesulfurization

Abstract

Described are catalysts for the hydrogenation, hydroisomerisation, hydrocracking and/or hydrodesulfurisation, of hydrocarbon feedstocks, the catalysts comprising a substantially binder free bead type support material comprising 5 to 60 wt. % of at least one crystalline molecular sieve material and 40 to 95 wt. % of non-crystalline, non-zeolitic silica-alumina and a catalytically active component comprising precious metals. Also described are methods for making catalyst supports by the dropwise addition of an aqueous sol of inorganic salts of aluminum and silicon, having dispersed therein the crystalline molecular sieve material, through an oil-phase to a water phase, thus providing homogeneous beads that are obtained without a separate shape-forming step.

1 . A catalyst for the hydrogenation, hydro-isomerisation, hydrocracking and/or hydrodesulfurisation of hydrocarbon feedstocks comprising:
 a substantially binder free support material comprising homogenous beads having 5 to 60 wt. % of at least one crystalline molecular sieve material and 40 to 95 wt. % of non-crystalline, non-zeolitic silica-alumina, the support having a Bronsted acidity of at least 50 μmol/g, a surface area from 25 to 1200 m 2 /g, and an average pore size of higher than 2 nm, and the silica-alumina having an X-ray diffraction pattern which does not exhibit any diffraction peaks with a width at half height less than 1.0 degree of arc when measured over the double diffraction angle; and   a catalytically active component comprising precious metals,   wherein the catalyst has a dispersion degree of at least 0.2.   
     
     
         2 . The catalyst of  claim 1 , wherein the support material consists of 10 to 50 wt. % of at least one molecular sieve material and 50 to 90 wt. % of non-crystalline, non-zeolitic silica-alumina. 
     
     
         3 . The catalyst of  claim 1 , wherein the non-crystalline, non-zeolitic silica-alumina in the support material is an acidic silica-alumina obtained by sol-gel techniques and the ratio of Si to Al is from 1:10 to 200:1. 
     
     
         4 . The catalyst of  claim 1 , wherein the molecular sieve material comprises one or more of zeolites and modified zeolites. 
     
     
         5 . The catalyst of  claim 1 , wherein the catalyst contains 0.01 to 5 wt. % of precious metal, calculated in the weight of the catalyst as catalytically active component. 
     
     
         6 . The catalyst of  claim 1 , wherein the catalytically active component comprises at least one component selected from the group of platinum, palladium, ruthenium, iridium and rhodium. 
     
     
         7 . The catalyst of  claim 6 , wherein the catalytically active component is selected from the group comprising platinum, palladium or combinations thereof. 
     
     
         8 . The catalyst of  claim 7 , wherein the catalytically active component comprises platinum and palladium in a weight ratio of 10:1 to 1:10. 
     
     
         9 . A catalyst for the hydrogenation, hydro-isomerisation, hydrocracking and/or hydrodesulfurisation of hydrocarbon feedstocks, the catalyst comprising:
 a substantially binder free bead type support material comprising 5 to 60 wt. % of at least one crystalline molecular sieve material and 40 to 95 wt. % of non-crystalline, non-zeolitic silica-alumina, the substantially binder free bead type support material obtained through dropwise addition of an aqueous sol of inorganic salts of aluminum and silicon, having dispersed therein the crystalline molecular sieve material, through an oil-phase to a water phase, providing homogeneous beads that are obtained without a separate shape-forming step; and   a catalytically active component comprising precious metals.   
     
     
         10 . The catalyst of  claim 9 , wherein the support material consists of 10 to 40 wt. % of at least one molecular sieve material and 60 to 90 wt. % of non-crystalline, non-zeolitic silica-alumina. 
     
     
         11 . The catalyst of  claim 9 , wherein the non-crystalline, non-zeolitic silica-alumina in the support material is an acidic silica-alumina, and the ratio of Si to Al is from 1:10 to 200:1. 
     
     
         12 . The catalyst of  claim 9 , wherein the molecular sieve material comprises one or more of zeolites and clay minerals. 
     
     
         13 . The catalyst of  claim 9 , the support having a Bronsted acidity of at least 50 μmol/g, a surface area from 25 to 1200 m 2 /g, and an average pore size of higher than 2 nm, and the silica-alumina having an X-ray diffraction pattern which does not exhibit any diffraction peaks with a width at half height less than 1.0 degree of arc when measured over the double diffraction angle. 
     
     
         14 . The catalyst of  claim 9 , wherein the catalyst contains 0.01 to 5 wt. % of precious metal, calculated in the weight of the catalyst as catalytically active component. 
     
     
         15 . The catalyst of  claim 9 , wherein the catalytically active component comprises at least one component selected from the group of platinum, palladium, ruthenium, iridium and rhodium. 
     
     
         16 . The catalyst of  claim 15 , wherein the catalytically active component is selected from the group comprising platinum, palladium or combinations thereof. 
     
     
         17 . A method of making a catalyst support comprising:
 providing an aqueous sol comprising inorganic salts of aluminum and silicon, wherein at least one crystalline molecular seize material is dispersed in the aqueous sol;   adding droplets of the aqueous sol to an oil phase to provide a substantially binder free bead shaped catalyst support comprising the molecular sieve material and non-crystalline, non-zeolitic silica-alumina, the beads obtained without a separate shape-forming step.   
     
     
         18 . The method of  claim 17 , wherein the substantially binder free bead shaped catalyst support comprises 5 to 60 wt. % of the crystalline molecular sieve material and 40 to 95 wt. % of the non-crystalline, non-zeolitic silica-alumina. 
     
     
         19 . The method of  claim 17 , further comprising passing the sol droplets through a water phase after adding them to the oil phase. 
     
     
         20 . The method of  claim 17 , further comprising applying a catalytically active component comprising precious metals to the catalyst support.