Bulk catalyst composition comprising bulk metal oxide particles

Abstract

The invention relates to a process for preparing bulk metal oxide particles comprising the steps of combining in a reaction mixture (i) dispersible nanoparticles having a dimension of less than about 1 μm upon being dispersed in a liquid, (ii) at least one Group VIII non-noble metal compound, (iii) at least one Group VIB metal compound, and (iv) a protic liquid; and reacting the at least one Group VIII non-noble metal compound and the at least one Group VIB metal in the presence of the nanoparticles. It also relates to bulk metal hydroprocessing catalysts obtainable by such method.

1 . A process for preparing bulk metal oxide particles comprising the steps of combining in a reaction mixture (i) dispersible nanoparticles having a dimension of less than about 1 μm upon being dispersed in a liquid, (ii) at least one Group VIII non-noble metal compound, (iii) at least one Group VIB metal compound, and (iv) a protic liquid; and reacting the at least one Group VIII non-noble metal compound and the at least one Group VIB metal in the presence of the nanoparticles, wherein said nanoparticles are different in composition from said at least one Group VIII non-noble metal compound and said at least one Group VIB metal compound. 
     
     
         2 . The process according to  claim 1 , wherein the nanoparticles are clay mineral particles. 
     
     
         3 . The process according to  claim 1  or  claim 2 , wherein at least one Group VIII non-noble metal compound and at least two Group VIB metal compounds are combined in the reaction mixture. 
     
     
         4 . The process according to any one of  claim 1  or  2 , wherein the reaction mixture further comprises a Group V metal compound. 
     
     
         5 . The process according to any one of  claim 1  or  2 , wherein the metal compounds are at least partly in the solid state during the process. 
     
     
         6 . The process according to any one of  claims 1  or  2 , wherein the nanoparticles are added to the reaction mixture after the metal compounds. 
     
     
         7 . The process according to  claim 5 , wherein the reaction mixture is prepared by:
 a) preparing a first suspension of at least one Group VIII non-noble metal compounds in a protic liquid;   b) preparing a second suspension of at least one Group VIB metal compounds in a protic liquid, and   c) combining the first and second suspensions together,   
       wherein either the first, second, or both suspensions contain nanoparticles and wherein said nanoparticles are different in composition from said at least one Group VIII non-noble metal compound and said at least one Group VIB metal compound. 
     
     
         8 . The process according to  claim 7 , wherein the at least one Group VIII non-noble metal compound comprises nickel (hydroxy) carbonate precipitated in the presence of nanoparticles. 
     
     
         9 . The process according to any one of  claim 1  or  2 , wherein the nanoparticles comprise platelets having a thickness of 0.1 to 1.5 nm, an aspect ratio of 100 to 1500 and a surface area greater than 250 m 2 /g. 
     
     
         10 . The process according to any one of  claims 1  or  2 , wherein the nanoparticles are clay mineral particles selected from the group consisting of synthetic clays of the smectite family, layered silicic acids, kaolinite, laponite, halloysite and mixtures thereof. 
     
     
         11 . The process according to  claim 10 , wherein the clay mineral nanoparticles consist essentially of laponite. 
     
     
         12 . A bulk catalyst composition comprising bulk metal oxide, sulfide, or a combination of oxide and sulfide particles having (i) dispersible nanoparticles having a dimension of less than about 1 μm upon dispersion in a liquid, (ii) at least one Group VIII non-noble metal compound, and (iii) at least one Group VIB metal compound, obtainable by the process according to any one of  claims 1  to  11  wherein said nanoparticles are different in composition from said at least one Group VIII non-noble metal compound and said at least one Group VIB metal compound. 
     
     
         13 . A bulk catalyst composition comprising bulk metal oxide, sulfide, or a combination of oxide and sulfide particles comprising (i) dispersible nanoparticles having a dimension of less than about 1 μm upon dispersion in a liquid, (ii) at least one Group VIII non-noble metal compound, and (iii) at least one Group VIB metal compound, wherein the bulk metal oxide particles are prepared by combining in a reaction mixture the nanoparticles, at least one Group VIII non-noble metal compound, at least one Group VIB metal compound, and a protic and reacting the at least one Group VIII non-noble metal compound and the at least one Group VIB metal compound in the presence of the nanoparticles, wherein said nanoparticles are different in composition from said at least one Group VIII non-noble metal compound and said at least one Group VIB metal compound. 
     
     
         14 . A bulk catalyst composition comprising bulk metal oxide and/or sulfide particles, wherein the bulk metal particles comprise:
 from about 50 wt. % to about 99.5 wt. % (calculated as metal oxide weight relative to the total weight of the bulk metal oxide and/or sulfide catalyst particles) of at least one Group VIII non-noble metal and at least one Group VIB metal, the metals being the form of oxides and/or sulfides, and   from about 0.5 wt. % to about 15 wt. % (relative to the total weight of the bulk metal particles) of nanoparticles having a dimension of less than 1 μm upon dispersion in a liquid, wherein said nanoparticles are different in composition from said at least one Group VIII non-noble metal compound and said at least one Group VIB metal compound.   
     
     
         15 . The bulk catalyst composition of  claim 14 , wherein the at least one Group VIII non-noble metal is cobalt and/or nickel. 
     
     
         16 . The bulk catalyst composition of  claim 15 , wherein nickel and/or cobalt represent at least about 90 wt. %, calculated as oxide, of the total of the Group VIII non-noble metals. 
     
     
         17 . The bulk catalyst composition according to any of  claims 14  to  16 , wherein the at least one Group VIB metal is molybdenum and/or tungsten. 
     
     
         18 . The bulk catalyst composition according to any of  claims 14  to  17 , wherein the only Group VIII non-noble metal is nickel and the only Group VIB metal is tungsten. 
     
     
         19 . The bulk catalyst composition of  claim 14 , wherein the bulk metal oxide and/or sulfide particles comprise molybdenum and tungsten, and wherein the molar ratio of molybdenum:tungsten is in the range from about 3:1 to about 1:6. 
     
     
         20 . The bulk catalyst composition according to any of  claims 14  to  18 , characterized by a molar ratio of Group VIB metals to Group VIII non-noble metals in the range from about 3:1 to about 1:3. 
     
     
         21 . The bulk catalyst composition according to any of  claims 14  to  20 , further comprising a Group V metal. 
     
     
         22 . The bulk catalyst composition of  claim 21 , wherein the molar ratio of Group V metals to Group VIB metals is between about 0.01 and about 5.