Nickel containing mixed metal-oxide/carbon bulk hydroprocessing catalysts and their application

Abstract

The current invention relates a process for making and using a bulk catalyst precursor (i.e. no support material is added as such) comprising Ni and Mo and/or W and an organic component, wherein the molar ratio of C:(Mo+W) ranges from 1.5 to 10. The bulk catalyst precursor is prepared from a mixture of metal-precursors with an organic agent. The organic agent is partly decomposed to form a mixed metal-oxide/C phase which is in effect the bulk catalyst precursor. This bulk catalyst precursor (i) is effectively insoluble in water (ii) does not have any appreciable pore volume or surface area and (iii) does not contain a (nano)crystalline metal-oxide phase as characterized by XRD.

1 . A process for hydroprocessing of a hydrocarbon feedstock comprising sulphur and nitrogen containing organic compounds comprising the step of contacting the hydrocarbon feedstock with a NiW, NiMo or NiMoW oxidic bulk catalyst obtained from a NiW, NiMo or NiMoW bulk catalyst precursor composition comprising nickel oxide, and molybdenum oxide or tungsten oxide or mixtures thereof, and an organic component prepared from an organic additive, wherein the total amount of molybdenum oxide and tungsten oxide is at least 30 wt %, the molar ratio of nickel to molybdenum plus tungsten is higher than 0.05, the molar ratio of carbon to molybdenum plus tungsten is between 1.5 and 10; and wherein the organic additive is selected from Acetic acid, Aspartic acid, Citric acid, Formic acid, Fumaric acid, Gluconic acid, Glutamic acid, Glyoxylic acid, Ketoglutaric acid, Maleic acid, Malic acid, Oxaloacetic acid, Propionic acid, Pyruvic acid, Succinic acid, Fructose, Glucose, Lactose, Saccharose, Sorbitol, Xylitol, Serine and mixtures thereof where the bulk catalyst precursor further comprises Ni-crystals detected by transmission electron microscopy technique (TEM), the catalyst comprising a minimum metal loading of 2.0 moles of molybdenum plus tungsten per liter reactor, wherein the molar ratio of nickel to molybdenum plus tungsten is higher than 0.05, a molar ratio of carbon to molybdenum plus tungsten between 1.5 and 10. 
     
     
         2 . The process of  claim 1  wherein the catalyst further comprises a peak at 45° 2 theta in the XRD pattern recorded using X-ray radiation with a wavelength of 1.54 Å. 
     
     
         3 . The process of  claim 1  wherein the catalyst further comprises Ni-crystals detected by transmission electron microscopy technique (TEM). 
     
     
         4 . The process according to  claim 1  wherein the catalyst comprises an inorganic binder comprising silica, silica-alumina, alumina, titania, titania-coated alumina, zirconia, bentonite, attapulgite, or mixtures thereof. 
     
     
         5 . The process of  claim 1  wherein the metal loading of molybdenum plus tungsten per liter reactor is between 3.0 and 7.0. 
     
     
         6 . The process of  claim 1  wherein the molar ratio of carbon to molybdenum plus tungsten between 1.5 and 7.0. 
     
     
         7 . The process of  claim 1  wherein the molar ratio of nickel to molybdenum plus tungsten is between 0.10 and 1.05. 
     
     
         8 . The process of  claim 1  wherein the molar ratio of nickel to molybdenum plus tungsten is between 0.20 and 0.75. 
     
     
         9 . A process for the manufacture of a mixed metal oxide organic phase catalyst precursor, the process comprising:
 a. forming a solution in protic liquid of one or more soluble metal compounds comprising nickel and molybdenum or tungsten or mixtures thereof and one or more organic compound, wherein the molar ratio of nickel to molybdenum plus tungsten is higher than 0.05;   b. evaporating the protic liquid;   c. partially decomposing the metal-organic phase to form the mixed metal oxide organic phase catalyst precursor wherein the molar ratio of carbon to molybdenum plus tungsten is between 1.5 and 10;
 i. wherein the one or more organic compound is Acetic acid, Aspartic acid, Citric acid, Formic acid, Fumaric acid, Gluconic acid, Glutamic acid, Glyoxylic acid, Ketoglutaric acid, Maleic acid, Malic acid, Oxaloacetic acid, Propionic acid, Pyruvic acid, Succinic acid, Fructose, Glucose, Lactose, Saccharose, Sorbitol, Xylitol, Serine and mixtures thereof. 
   
       wherein the resulting catalyst precursor is a NiW, NiMo or NiMoW bulk catalyst precursor composition comprising nickel oxide, and molybdenum oxide or tungsten oxide or mixtures thereof, and an organic component prepared from an organic additive, wherein the total amount of molybdenum oxide and tungsten oxide is at least 30 wt %, the molar ratio of nickel to molybdenum plus tungsten is higher than 0.05; wherein the bulk catalyst precursor further comprises Ni-crystals detected by transmission electron microscopy technique (TEM) 
     
     
         10 . The process of  claim 9  wherein the one or more organic compound is an organic acid or a sugar. 
     
     
         11 . A process for the manufacture of a sulphidic catalyst comprising sulphiding the bulk catalyst of  claim 9 . 
     
     
         12 . The process of  claim 9  wherein the shaping of the bulk catalyst precursor comprises forming an extrudate with an inorganic binder and water and then drying the extrudates at a temperature of at least 120° C. 
     
     
         13 . A process for the manufacture of an oxidic catalyst comprising shaping of the bulk catalyst precursor of  claim 9 .