Dispersed metal sulfide-based catalysts

Abstract

The invention provides a catalyst composition, which includes an emulsion of an aqueous phase in an oil phase, wherein the aqueous phase comprises an aqueous solution containing a group 6 metal and a group 8, 9 or 10 metal. The metals can be provided in two separate emulsions, and these emulsions are well suited for treating hydrocarbon feedstocks.

1 . A catalyst composition of the general formula:
   B x M y S [(1.1 to 4.6)y+(0.5 to 4)x]     where B is a group 8, 9 or 10 (group VIIIB, CAS version) non-noble metal and M is a group 6 (group VIB, CAS version) metal, and wherein the ratio y/x is greater than or equal to 0.05 and less than or equal to 15.   
   
   
       2 . The composition of  claim 1 , wherein the ratio y/x is greater than or equal to 0.2 and less than or equal to 6. 
   
   
       3 . The composition of  claim 1 , wherein the ratio y/x is 3. 
   
   
       4 . A catalyst composition of the general formula:
   B x M1 y M2 z O (2 to 3)z S [(0.3 to 2)y+(0.5 to 4)x]     where B is a group 8, 9 or 10 (group VIIIB, CAS version) non-noble metal and M1 and M2 are group 6 (group VIB, CAS version) metals, and wherein the ratio y/x is greater than or equal to 0.05 and less than or equal to 15, and the ratio z/x is greater than or equal to 1 and less than or equal to 14.   
   
   
       5 . The composition of  claim 4  wherein the ratio y/x is greater than or equal to 0.2 and less than or equal to 6. 
   
   
       6 . The composition of  claim 4  wherein the ratio z/x is greater than or equal to 10 and less than or equal to 14. 
   
   
       7 . The composition of  claim 6  wherein the ratio z/x is 12. 
   
   
       8 . The composition of  claim 4  wherein the ratio z/x is greater than or equal to 1 and less than or equal to 5. 
   
   
       9 . The composition of  claim 8  wherein the ratio z/x is 3. 
   
   
       10 . The composition of  claim 1  or  claim 4 , wherein the catalyst composition is an ultradispersed suspension within a hydrocarbon solvent. 
   
   
       11 . The composition of  claim 10  wherein the ultradispersed suspension is characterized by a median particle diameter between 30 nm and 6,000 nm. 
   
   
       12 . The composition of  claim 10  wherein the ultradispersed suspension is characterized by a median particle diameter between 60 nm and 2,500 nm. 
   
   
       13 . A catalyst composition, comprising:
 an emulsion of an aqueous phase in an oil phase, wherein the aqueous phase comprises an aqueous solution containing a group 6 metal and a group 8, 9 or 10 metal.   
   
   
       14 . The composition of  claim 13 , wherein the group 6 metal is a metal sulfide. 
   
   
       15 . The composition of  claim 13 , wherein the group 6 metal is a salt precursor to a metal sulfide. 
   
   
       16 . The composition of  claim 15 , wherein the salt precursor comprises an organometallic compound. 
   
   
       17 . The composition of  claim 16 , wherein the organometallic compound is selected from the group consisting of naphthenates, acetates, metal oxides and combinations thereof. 
   
   
       18 . The composition of  claim 13 , wherein the group 6 metal is selected from the group consisting of molybdenum, tungsten and mixtures thereof. 
   
   
       19 . The composition of  claim 13 , wherein the group 6 metal is molybdenum. 
   
   
       20 . The composition of  claim 13 , wherein the group 8, 9 or 10 metal is selected from the group consisting of iron, cobalt, nickel and mixtures thereof. 
   
   
       21 . The composition of  claim 13 , wherein the group 8 metal is nickel. 
   
   
       22 . The composition of  claim 13 , wherein the group 6 metal is molybdenum and the group 8 metal is nickel. 
   
   
       23 . The composition of  claim 13 , wherein an atomic ratio of nickel to combined nickel and molybdenum is greater than 0 and less than 0.2. 
   
   
       24 . The composition of  claim 23 , wherein the atomic ratio is 0.1. 
   
   
       25 . The composition of  claim 13 , wherein the oil phase comprises a hydrocarbon selected from the group consisting of HVGO, HHGO and combinations thereof. 
   
   
       26 . The composition of  claim 13 , wherein the emulsion has a ratio by weight of aqueous phase to oil phase of between 5 and 25 wt %. 
   
   
       27 . The composition of  claim 13 , wherein the emulsion has an average droplet size of between 0.1 and 20 μm. 
   
   
       28 . The composition of  claim 13 , wherein the emulsion has a ratio by weight of surfactant to total emulsion of greater than 0 and less than or equal to 0.1. 
   
   
       29 . The composition of  claim 13 , wherein the emulsion has a ratio by weight of oil phase to combined oil and water phase of between 0.70 and 0.94. 
   
   
       30 . The composition of  claim 13 , wherein the emulsion comprises a first emulsion containing said group 6 metal and a second emulsion containing said group 8, 9 or 10 metal. 
   
   
       31 . A method for preparing an at least bi-metallic ultradispersed catalyst comprising the steps of:
 preparing at least one first precursor solution containing a metal salt of a metal of groups 8, 9 or 10 (Group VIII B, CAS version);   preparing a second precursor solution containing a group 6 metal salt (Group VI B, CAS version);   admixing the first and second precursor solutions with a hydrocarbon feedstock to form separate first and second microemulsions; and   exposing the first and second microemulsions to heat so as to decompose the first and second precursor solutions and form the catalyst.   
   
   
       32 . The method of  claim 31 , wherein the exposing step comprises exposing the first and second microemulsions to the feedstock to be treated and to heat. 
   
   
       33 . The method of  claim 31  further comprising the step of adding a surfactant to any one of or a combination of the first and second precursor solutions. 
   
   
       34 . The method of  claim 31  wherein the bi-metallic microemulsion mixture is subjected to a decomposition process to form an ultradispersed catalyst composition. 
   
   
       35 . The method of  claim 31  wherein the bi-metallic microemulsion mixture is introduced into a reaction process to form an ultradispersed catalyst composition within the reaction process. 
   
   
       36 . The method of  claim 31 , wherein the step of preparing the second precursor solution further includes admixing a sulfuring agent to form group 6 metal sulfide salt. 
   
   
       37 . The method of  claim 36 , wherein the sulfuring agent is selected from the group consisting of H 2 S, CS 2 , ammonium sulfide and combinations thereof. 
   
   
       38 . The method of  claim 31  wherein preparing the second precursor solution further includes admixing ammonium sulfide under controlled conditions of pH to form thio salts. 
   
   
       39 . The method of  claim 31  further comprising the step of adding a surfactant after addition of the hydrocarbon feedstock to enhance microemulsion formation. 
   
   
       40 . The method of  claim 34  wherein the decomposition temperature is between 150° C. and 450° C. 
   
   
       41 . The method of  claim 34  wherein the decomposition temperature is between 225° C. and 325° C. 
   
   
       42 . The method of  claim 34  wherein the decomposition pressure is between 1 atm and 70 atm. 
   
   
       43 . The method of  claim 34  wherein the decomposition pressure is between 14 atm and 28 atm. 
   
   
       44 . The method of  claim 31 , wherein the hydrocarbon feedstock is selected from the group consisting of HVGO, HHGO and combinations thereof. 
   
   
       45 . The method of  claim 31 , wherein the first precursor solution comprises a metal aqueous solution containing metal salts in an amount between 7 and 14% by weight of the solution. 
   
   
       46 . The method of  claim 31 , wherein the second precursor solution comprises a metal aqueous solution containing metal salts in an amount between 1 and 14% by weight of the solution. 
   
   
       47 . The method of  claim 31 , wherein the step of preparing the first precursor solution comprises mixing nickel acetate with water, and wherein the step of preparing the second precursor solution comprises mixing ammonium heptamolybdate with water and a sulfuring agent. 
   
   
       48 . The method of  claim 31 , wherein the first precursor solution has an average droplet diameter of 2.7 microns, and a droplet size distribution of between 1.5 and 7 microns. 
   
   
       49 . The method of  claim 31 , wherein the second precursor solution has an average droplet diameter of 3.6 microns, and a droplet size distribution of between 0.3 and 13.4 microns. 
   
   
       50 . A process for upgrading a hydrocarbon feedstock, comprising:
 exposing the feedstock to an emulsion of an aqueous phase in an oil phase, wherein the aqueous phase comprises an aqueous solution containing a group 6 metal and a group 8, 9 or 10 metal; and   thermally decomposing the emulsion to produce a dispersed catalyst of the group 6 metal and the group 8, 9 or 10 metal, whereby the dispersed catalyst reacts with the feedstock to produce an upgraded hydrocarbon product.   
   
   
       51 . The process of  claim 50 , wherein the exposing step comprises exposing the feedstock to a first emulsion containing the group 6 metal and a second emulsion containing the group 8, 9 or 10 metal.