Co-processing hydrothermal liquefaction oil and co-feed to produce biofuels

Abstract

The present disclosure relates to processes for producing biofuel compositions by processing hydrocarbon co-feed and a bio-oil obtained via hydrothermal liquifaction (HTL) of a cellulosic biomass to form an HTL oil. The cellulosic mass can be processed at an operating temperature of about 425° C. or less and an operating pressure of about 200 atm or less. The HTL oil is co-processed with a hydrocarbon co-feed (e.g., petroleum fraction) in a cracking unit, such as an FCC unit, a coker unit or a visbreaking unit, in the presence of a catalyst to produce a cracked product (biofuel). The bio content of the cracked product provides RIN credits for the cracked product.

1 . A method for forming a biofuel composition, comprising:
 introducing separately a hydrothermal liquefaction (HTL) oil derived from cellulosic material, a hydrocarbon co-feed and a cracking catalyst into a cracking unit to form a mixture; and   processing the mixture at a temperature of about 350° C. or greater to form a cracked product.   
     
     
         2 . The method of  claim 1 , wherein the cracked product is not fractionated. 
     
     
         3 . The method of  claim 1 , wherein the cracking unit comprises two or more injection nozzles coupled with the cracking unit. 
     
     
         4 . The method of  claim 1 , further comprising blending the cracked product with one or more fuel additive components, wherein the biofuel composition comprises one or more fuel additive components. 
     
     
         5 . The method of  claim 4 , wherein the one or more fuel additive components are selected from an anti-oxidant, a corrosion inhibitor, an ashless detergent, a dehazer, a dye, a lubricity improver, a mineral fuel component, a petroleum derived gasoline, a diesel, and a kerosene. 
     
     
         6 . The method of  claim 1 , wherein the biofuel composition has a water content of about 5% or less. 
     
     
         7 . The method of  claim 1 , further comprising introducing the hydrocarbon co-feed into the cracking unit using a first nozzle and introducing the HTL oil into the cracking unit using a second nozzle. 
     
     
         8 . The method of  claim 1 , wherein the hydrocarbon co-feed comprises one or more of a straight run (atmospheric) gas oil, a flashed distillate, a vacuum gas oil, a light cycle oil, a heavy cycle oil, a hydrowax, a coker gas oil, a gasoline, a naphtha, a diesel, a kerosene, an atmospheric residue, a vacuum residue, or a combination thereof. 
     
     
         9 . The method of  claim 1 , wherein the hydrocarbon co-feed is a vacuum gas oil. 
     
     
         10 . The method of  claim 8 , wherein the ratio of the amount of cracking catalyst to the total amount of hydrothermal liquefaction oil and hydrocarbon co-feed is from about 2/1 to about 10/1. 
     
     
         11 . The method of  claim 1 , further comprising introducing a catalyst additive to the cracking unit. 
     
     
         12 . A method for forming a biofuel composition, comprising:
 introducing a cellulosic material to a solvent in the presence of a catalyst at a temperature of about 350° C. or greater and an operating pressure of about 200 atm or greater to form a first liquefied product;   hydrotreating the first liquefied product with a source of hydrogen in the presence of a hydrotreatment catalyst to produce a second liquefied product;   introducing the second liquefied product and a cracking catalyst to a fluidized catalytic cracking unit at a temperature of about 350° C. or greater to form a cracked product;   hydrotreating the cracked product with a source of hydrogen in the presence of a hydrotreatment catalyst to produce a hydrotreated cracked product; and   blending the hydrotreated cracked product with one or more fuel additive components to form a biofuel composition.   
     
     
         13 . The method of  claim 12 , wherein the cracked product is not fractionated before blending with the one or more fuel additive components. 
     
     
         14 . The method of  claim 12 , wherein the one or more fuel additive components are selected from an anti-oxidant, a corrosion inhibitor, an ashless detergent, a dehazer, a dye, a lubricity improver, a mineral fuel component, a petroleum derived gasoline, a diesel, and a kerosene. 
     
     
         15 . The method of  claim 12 , wherein the biofuel composition comprises the one or more fuel additive components from about 0.1 wt % to about 3 wt %, based on the total weight of the biofuel composition. 
     
     
         16 . The method of  claim 12 , wherein the biofuel composition has a water content of about 5% or less. 
     
     
         17 . The method of  claim 12 , further comprising introducing a hydrocarbon co-feed into the fluidized catalytic cracking unit, wherein the liquefied product is introduced using a first nozzle to the fluidized catalytic cracking unit and the hydrocarbon co-feed is introduced using a second nozzle to the fluidized catalytic cracking unit. 
     
     
         18 . The method of  claim 17 , wherein the hydrocarbon co-feed comprises one or more of a straight run (atmospheric) gas oil, a flashed distillate, a vacuum gas oil, a light cycle oil, a heavy cycle oil, a hydrowax, a coker gas oil, a gasoline, a naphtha, a diesel, a kerosene, an atmospheric residue, a vacuum residue, or a combination thereof. 
     
     
         19 . The method of  claim 17 , wherein the hydrocarbon co-feed is a vacuum gas oil. 
     
     
         20 . The method of  claim 12 , wherein the solvent is a petroleum oil. 
     
     
         21 . The method of  claim 12 , wherein hydrotreating the first liquefied product comprises introducing a hydrogen source and a hydrogenation catalyst to the liquefaction unit at a temperature of about 150° C. or greater. 
     
     
         22 . The method of  claim 12 , wherein the first and/or second liquefied product comprises one or more of gamma-valerolactone, levulinic acid, tetrahydrofufuryl, tetrahydropyranyl, furfural hydroxymethylfurfural, mono-alcohol, di-alcohol, mono-ketone, di-ketone, guaiacol, or syringol. 
     
     
         23 . The method of  claim 12 , wherein the ratio of the amount of cracking catalyst to the amount of second liquefied product is from about 2/1 to about 10/1. 
     
     
         24 . The method of  claim 18 , wherein the ratio of the amount of cracking catalyst to the total amount of second liquefied product and hydrocarbon co-feed is from about 2/1 to about 10/1. 
     
     
         25 . The method of  claim 12 , further comprising introducing a catalyst additive to the fluidized catalytic cracking unit.