Methods for deoxygenating biomass-derived pyrolysis oils

Abstract

Methods for deoxygenating treated biomass-derived pyrolysis oil are provided. The treated biomass-derived pyrolysis oil is exposed to a catalyst having a neutral catalyst support such as a non-alumina metal oxide support, a theta alumina support, or both. The non-alumina metal oxide support may be a titanium oxide (TiO 2 ) support, a silicon oxide support, a zirconia oxide (ZrO 2 ) support, a niobium oxide (Nb 2 O 5 ) support, or a support having a mixture of non-alumina metal oxides. The catalyst may include a noble metal or a Group VIII non-noble metal and a Group VIB non-noble metal on the neutral catalyst support. The treated biomass-derived pyrolysis oil is introduced into a hydroprocessing reactor in the presence of the catalyst under hydroprocessing conditions to produce low oxygen biomass-derived pyrolysis oil.

1 . A method for deoxygenating treated biomass-derived pyrolysis oil, comprising the step of:
 exposing the treated biomass-derived pyrolysis oil to a catalyst having a neutral catalyst support.   
     
     
         2 . The method of  claim 1 , wherein the step of exposing comprises exposing the treated biomass-derived pyrolysis oil to a catalyst having a theta alumina support. 
     
     
         3 . The method of  claim 1 , wherein the step of exposing comprises exposing the treated biomass-derived pyrolysis oil to a catalyst having a carbon support, a non-alumina metal oxide support, or a support comprising a combination of carbon and non-alumina metal oxide. 
     
     
         4 . The method of  claim 3 , wherein the step of exposing comprises exposing the treated biomass-derived pyrolysis oil to a catalyst having a non-alumina metal oxide support selected from the group consisting of a titanium oxide (TiO 2 ) support, a silicon oxide support, a zirconia oxide (ZrO 2 ) support, a niobium oxide (Nb 2 O 5 ) support, and a support comprising mixtures of non-alumina metal oxides. 
     
     
         5 . The method of  claim 1 , wherein the step of exposing comprises exposing the treated biomass-derived pyrolysis oil to a catalyst comprising a noble metal on the neutral catalyst support, the noble metal selected from the group consisting of rhodium (Rh), palladium (Pd), gold (Au), ruthenium (Ru), and combinations thereof. 
     
     
         6 . The method of  claim 1 , wherein the step of exposing comprises exposing the treated biomass-derived pyrolysis oil to a catalyst comprising a Group VIII non-noble metal and a Group VIB non-noble metal on the neutral catalyst support, the Group VIII non-noble metal comprising cobalt, nickel, or both, and the Group VIB non-noble metal comprising molybdenum or tungsten, wherein the Group VIB and Group VIII non-noble metals are optionally sulfided. 
     
     
         7 . The method of  claim 6 , wherein the step of exposing comprises exposing the treated biomass-derived pyrolysis oil to a catalyst comprising nickel and molybdenum on a neutral catalyst support, the nickel comprising about 0.5 to about 5 weight percent of the catalyst and the molybdenum calculated as an oxide comprising about 5 to about 20 weight percent of the catalyst. 
     
     
         8 . The method of  claim 6 , wherein the step of exposing comprises exposing the treated biomass-derived pyrolysis oil to a catalyst comprising nickel and tungsten on a neutral catalyst support, the nickel comprising about 0.5 to about 5 weight percent of the catalyst and the tungsten comprising about 5 to about 20 weight percent of the catalyst. 
     
     
         9 . The method of  claim 6 , wherein the step of exposing comprises exposing the treated biomass-derived pyrolysis oil to a catalyst comprising nickel, cobalt, and molybdenum or tungsten on a neutral catalyst support, the nickel comprising about 0.1 to about 5 weight percent of the catalyst, the cobalt calculated as an oxide comprising about 0.5 to about 5 weight percent of the catalyst, and the molybdenum or tungsten comprising about 5 to about 20 weight percent of the catalyst, the molybdenum calculated as an oxide. 
     
     
         10 . The method of  claim 6 , wherein the step of exposing comprises exposing the treated biomass-derived pyrolysis to a catalyst comprising cobalt and molybdenum or tungsten on a neutral catalyst support, the cobalt calculated as an oxide comprising about 0.5 to about 5 weight percent of the catalyst, and the molybdenum or tungsten comprising about 5 to about 20 weight percent of the catalyst, the molybdenum calculated as an oxide. 
     
     
         11 . A method for deoxygenating treated biomass-derived pyrolysis oil, the method comprising the steps of:
 providing a catalyst comprising a metal on a carbon support, a non-alumina metal oxide support, a theta alumina support, or a combination thereof; and   introducing treated biomass-derived pyrolysis oil into a hydroprocessing reactor in the presence of the catalyst under hydroprocessing conditions to produce low oxygen biomass-derived pyrolysis oil.   
     
     
         12 . The method of  claim 11 , wherein the step of providing a catalyst comprises providing a catalyst having a non-alumina metal oxide support selected from the group consisting of a titanium oxide (TiO 2 ) support, a silicon oxide support, a zirconia oxide (ZrO 2 ) support, a niobium oxide (Nb 2 O 5 ) support, and a support comprising a mixture of non-alumina metal oxides. 
     
     
         13 . The method of  claim 11 , wherein the step of providing a catalyst comprises providing a catalyst comprising a noble metal on the non-alumina metal oxide support, the theta alumina support, or on a support comprising a mixture of a non-alumina metal oxide and theta alumina, the noble metal selected from the group consisting of rhodium (Rh), palladium (Pd), gold (Au), ruthenium (Ru), and combinations thereof. 
     
     
         14 . The method of  claim 11 , wherein the step of providing a catalyst comprises providing a catalyst comprising a Group VIII non-noble metal and a Group VIB non-noble metal on the non-alumina metal oxide support, the theta alumina support, or on a support comprising a mixture of a non-alumina metal oxide and theta alumina, the Group VIII non-noble metal comprising cobalt, nickel, or both, and the Group VIB non-noble metal comprising molybdenum or tungsten, wherein the Group VIB and Group VIII non-noble metals are optionally sulfided. 
     
     
         15 . The method of  claim 14 , wherein the step of providing a catalyst comprises providing a catalyst comprising nickel and molybdenum on the non-alumina metal oxide support, the theta alumina support, or on a support comprising a mixture of a non-alumina metal oxide and theta alumina, the nickel comprising about 0.5 to about 5 weight percent of the catalyst and the molybdenum calculated as an oxide comprising about 5 to about 20 weight percent of the catalyst, or a catalyst comprising nickel and tungsten on the non-alumina metal oxide support, the theta alumina support, or on a support comprising a mixture of a non-alumina metal oxide and theta alumina, the nickel comprising about 0.5 to about 5 weight percent of the catalyst and the tungsten comprising about 5 to about 20 weight percent of the catalyst. 
     
     
         16 . The method of  claim 14 , wherein the step of providing a catalyst comprises providing a catalyst comprising nickel, cobalt, and either molybdenum or tungsten on a non-alumina metal oxide support, a theta alumina support, or a support comprising a mixture of a non-alumina metal oxide and theta alumina, the nickel comprising about 0.1 to about 5 weight percent of the catalyst, the cobalt calculated as an oxide comprising about 0.5 to about 5 weight percent of the catalyst, and the molybdenum or tungsten comprising about 5 to about 20 weight percent of the catalyst, the molybdenum calculated as an oxide. 
     
     
         17 . The method of  claim 14 , wherein the step of providing a catalyst comprises providing a catalyst comprising cobalt and either molybdenum or tungsten on a neutral catalyst support, the cobalt calculated as an oxide comprising about 0.5 to about 5 weight percent of the catalyst, and the molybdenum or tungsten comprising about 5 to about 20 weight percent of the catalyst, the molybdenum calculated as an oxide. 
     
     
         18 . A method for deoxygenating treated biomass-derived pyrolysis oil, the method comprising the steps of:
 providing a catalyst comprising a metal on a carbon support, a non-alumina metal oxide support, a theta alumina support, or a support comprising combinations thereof; and   exposing the treated biomass-derived pyrolysis oil to the catalyst at hydroprocessing conditions sufficient to at least partially deoxygenate the treated biomass-derived pyrolysis oil;   wherein the non-alumina metal oxide support is selected from the group consisting of a titanium oxide (TiO 2 ) support, a silicon oxide support, a zirconia oxide (ZrO 2 ) support, a niobium oxide (Nb 2 O 5 ) support, or a support comprising a mixture of non-alumina metal oxides.   
     
     
         19 . The method of  claim 18 , wherein the step of providing a catalyst comprises providing a catalyst comprising a noble metal, the noble metal selected from the group consisting of rhodium (Rh), palladium (Pd), gold (Au), ruthenium (Ru), and combinations thereof. 
     
     
         20 . The method of  claim 18 , wherein the step of providing a catalyst comprises providing a catalyst comprising a Group VIII non-noble metal and a Group VIB non-noble metal, the Group VIII non-noble metal comprising cobalt, nickel, or a combination thereof, and the Group VIB non-noble metal comprising molybdenum or tungsten, wherein the Group VIB and Group VIII non-noble metals are optionally sulfided.