Coprocessing of biofeeds with bulk mixed metal catalysts

Abstract

This invention relates to methods for deoxygenation utilizing bulk metal catalysts feedstocks derived in part or whole from biological sources and alternatively, further hydrotreatment processing of such deoxygenated feedstocks. Feedstocks containing bio-derived feed components, and preferably additionally mineral oil feed components, are deoxygenated in a first stage or zone using a bulk metal catalyst. In additional embodiments, the deoxygenated feedstock effluent from the deoxygenation stage is further subjected to a hydrodesulfurization stage or zone.

What is claimed is: 
     
         1 . A method for hydroprocessing a biocomponent feedstock, comprising:
 exposing a biocomponent feedstock comprising at least a bio-derived fraction to a bulk mixed metal catalyst in the presence of hydrogen under effective deoxygenation conditions, the bulk mixed metal catalyst comprising at least one Group VI metal and at least one Group VIII metal; and   forming a deoxygenated effluent wherein at least 75% of the oxygen has been removed from the biocomponent feedstock compounds.   
     
     
         2 . The method of  claim 1 , wherein the biocomponent feedstock further comprises a mineral oil fraction. 
     
     
         3 . The method of  claim 2 , wherein the at least one Group VI metal is selected from Mo and W and at least one Group VIII metal is selected from Co and Ni. 
     
     
         4 . The method of  claim 3 , wherein the total amount of the Group VI metals and Group VIII metals comprise at least 80 wt % of the bulk mixed metal catalyst. 
     
     
         5 . The method of  claim 4 , wherein the bulk mixed metal catalyst contains less than 15 wt % carrier or support material. 
     
     
         6 . The method of  claim 3 , wherein the bulk mixed metal catalyst is further combined with a binder. 
     
     
         7 . The method of  claim 6 , wherein the binder is selected from silica, silica-alumina, alumina, titania, zirconia, and mixtures thereof. 
     
     
         8 . The method of  claim 7 , wherein the amount of binder is from about 5 wt % to about 95 wt % binder based on the total weight of the bulk mixed metal catalyst and the binder. 
     
     
         9 . The method of  claim 3 , wherein the bulk mixed metal catalyst is further comprised of at least one organic compound. 
     
     
         10 . The method of  claim 9 , wherein the bulk mixed metal catalyst is further sulfided prior to exposing the biocomponent feedstock to the bulk mixed metal catalyst, and the at least one organic is present on the bulk mixed metal catalyst at the time the catalyst is exposed to the sulfiding conditions. 
     
     
         11 . The method of  claim 10 , wherein the at least one organic compound is a condensation/decomposition reaction product derived from an amine, a carboxylic acid, or combinations thereof. 
     
     
         12 . The method of  claim 11 , wherein the amine, carboxylic acid, or combination thereof is subjected to a reaction temperature of from about 195° C. to about 250° C. (about 383° F. to about 482° F.) to form the condensation/decomposition reaction product. 
     
     
         13 . The method of  claim 12 , wherein the at least one Group VI metal is Mo and at least one Group VIII metal is Co. 
     
     
         14 . The method of  claim 3 , wherein the bulk mixed metal catalyst is comprised of at least two Group VI metals, such Group VI metals being Mo and W, and at least one Group VIII metal selected from Co and Ni. 
     
     
         15 . The method of  claim 14 , wherein the bulk mixed metal catalyst is further sulfided prior to exposing the biocomponent feedstock to the bulk mixed metal catalyst. 
     
     
         16 . The method of  claim 14 , wherein the bulk mixed metal catalyst is comprised of Mo, W, and Ni. 
     
     
         17 . The method of  claim 16 , wherein the bulk mixed metal catalyst is comprised of at least 90 wt % Mo, W, and Ni, and this portion of the bulk mixed metal catalyst has the formula:
   (Ni) b (Mo) c (W) d O z      wherein the molar ratio of b:(c+d) is 0.5:1 to 3:1; the molar ratio of c:d is preferably >0.01:1; the molar ratio of Mo and W is 2:3 to 3:2; and z=[2b+6(c+d)]/2.   
     
     
         18 . The method of  claim 3 , wherein the effective deoxygenation conditions include a hydrogen partial pressure of from about 200 psig (1.4 MPag) to about 2000 psig (13.8 MPag), a reaction temperature of from about 400° F. to about 750° F. (204° C. to 399° C.), a liquid hourly space velocity of from about 0.1 hr −1  to about 10 hr −1 , and a hydrogen treat gas rate from about 500 scf/B (84 Nm 3 /m 3 ) to about 10,000 scf/B (1685 Nm 3 /m 3 ). 
     
     
         19 . The method of  claim 18 , wherein the effective deoxygenation conditions include a reaction temperature of from about 400° F. to about 500° F. (204° C. to 260° C.). 
     
     
         20 . The method of  claim 18 , wherein the effective deoxygenation conditions include a reaction temperature of from about 400° F. to about 490° F. (204° C. to 254° C.). 
     
     
         21 . The method of  claim 2 , further comprising:
 exposing at least a portion of the deoxygenated effluent to a hydrodesulfurization catalyst under effective hydrodesulfurization conditions to produce a deoxygenated/desulfurized effluent having a sulfur content of about 100 wppm or less.   
     
     
         22 . The method of  claim 21 , wherein the effective hydrodesulfurization conditions include, a total pressure from about 200 psig (1.4 MPa) to about 3000 psig (20.7 MPa), a temperature of from about 450° F. (232° C.) to about 750° F. (399° C.), a liquid hourly space velocity of about 0.3 to about 5.0 hr −1 , a treat gas containing at least about 80% hydrogen, and a hydrogen treat gas rate of about 500 scf/bbl (84 m 3 /m 3 ) to about 10000 scf/bbl (1685 m 3 /m 3 ). 
     
     
         23 . The method of  claim 22 , wherein hydrodesulfurization catalyst is comprised of at least one Group VIB metal and at least one Group VIII metal deposited upon a support, wherein the support is comprised of a material selected from silica, silica-alumina, alumina, and titania. 
     
     
         24 . The method of  claim 23 , wherein the bulk mixed metal catalyst and the hydrodesulfurization catalyst are located in a common reactor. 
     
     
         25 . The method of  claim 23 , wherein the bulk mixed metal catalyst and the hydrodesulfurization catalyst are each located in separate reactors and the effective hydrodesulfurization conditions include a temperature of from about 650° F. (343° C.) to about 750° F. (399° C.).