Two stage process for producing renewable biofuels

Abstract

A process for treating bio-oil or pyrolysis oil used to produce renewable biofuel. In a first stage, solids and/or organic reactive molecules within the feedstream are reduced without substantially deoxygenating the organic reactive molecules in the feedstream. The resulting feedstream is then introduced into a second hydrotreatment stage to produce deoxygenated bio-oil or pyrolysis oil.

What is claimed is: 
     
         1 . A process for treating bio-oil or pyrolysis oil used to produce renewable biofuel, the process comprising:
 (a) introducing a feedstream containing bio-oil or pyrolysis oil to a first stage and reducing solids and/or organic reactive molecules within the feedstream in the first stage without substantially deoxygenating the organic reactive molecules in the feedstream;   (b) introducing the feedstream having reduced solids and/or reduced organic reactive molecules to a second stage, wherein the second stage is a hydrotreatment stage, and further wherein the temperature in the second stage is greater than the temperature in the first stage and the pressure in the first stage is less than or equal to the pressure in the second stage and producing deoxygenated bio-oil or pyrolysis oil in the second stage.   
     
     
         2 . The process of  claim 1 , wherein the first stage is a hydrotreatment stage. 
     
     
         3 . The process of  claim 2 , wherein the first stage and the second stage are housed within the same hydrotreater reactor. 
     
     
         4 . The process of  claim 1 , in which the entire liquid and gaseous effluent from the first stage is passed through to the second stage. 
     
     
         5 . The process of  claim 3 , wherein the pressure in the hydrotreater reactor is from about 1,500 psig to about 2,000 psig. 
     
     
         6 . The process of  claim 1 , wherein the first stage and the second stage are housed in different reactors. 
     
     
         7 . The process of  claim 6 , wherein the feedstream is heated by an exothermic reaction upon entry into the hydrotreater of the second stage. 
     
     
         8 . The process of  claim 2 , wherein the feedstream prior to entry into the hydrotreater in the second stage is exposed to hydrogen to generate an exothermic reaction without substantially deoxygenating the reactive species in the feedstream. 
     
     
         9 . The process in  claim 1 , where a reactive species is added to the feedstream and further wherein heat generated by the addition of the added reactive species causes at least part of the increase in temperature needed for the second stage. 
     
     
         10 . The process of  claim 9 , wherein the reactive species is an olefin or an alcohol. 
     
     
         11 . The process of  claim 2 , wherein the pressure in the hydrotreater reactor housing the first stage is between from about 500 to about 1,000 psig and the pressure in the hydrotreater reactor housing the second stage is between from about 500 psig to about 2,000 psig. 
     
     
         12 . The process of  claim 6 , wherein the feedstream introduced into the first stage or second stage is heated in a controlled pre-treatment heat exchanger. 
     
     
         13 . The process of  claim 1 , wherein the amount of organic reactive molecules deoxygenated in the first stage is less than 5 percent. 
     
     
         14 . The process of  claim 13 , wherein the amount of organic reactive molecules deoxygenated in the first stage is less than 3 percent. 
     
     
         15 . The process of  claim 14 , wherein the amount of organic reactive molecules deoxygenated in the first stage is less than 0.1 percent. 
     
     
         16 . The process of  claim 2 , wherein the temperature at the entry of the first stage is from about 120° F. to about 350° F. 
     
     
         17 . The process of  claim 1 , wherein the temperature of the feedstream entering the second stage does not exceed 500° F. 
     
     
         18 . The process of  claim 1 , wherein the space velocity within the first stage is from about 0.5 to about 6. 
     
     
         19 . The process of  claim 1 , wherein greater than 80 percent of oxygen has been removed from the feedstream exiting the second stage. 
     
     
         20 . The process of  claim 19 , wherein greater than 90 percent of oxygen has been removed from the feedstream exiting the second stage. 
     
     
         21 . The process of  claim 20 , wherein greater than 95 percent of oxygen has been removed from the feedstream exiting the second stage. 
     
     
         22 . The process of  claim 1 , wherein the temperature at the exit of the second stage is between from about 650° F. to about 850° F. 
     
     
         23 . The process of  claim 1 , wherein the space velocity within the second stage is less than 5. 
     
     
         24 . The process of  claim 1 , wherein the feedstream is a bio-oil containing feedstream. 
     
     
         25 . The process of  claim 24 , wherein the bio-oil containing feedstream is separated into bio-oil and an aqueous phase. 
     
     
         26 . The process of  claim 24 , wherein the bio-oil containing feedstream is separated into bio-oil and an aqueous phase prior to step (a). 
     
     
         27 . The process of  claim 6 , wherein step (a) occurs in a slurry bed reactor. 
     
     
         28 . The process of  claim 1 , wherein step (a) occurs in a fixed bed reactor. 
     
     
         29 . The process of  claim 4 , wherein step (b) occurs in a fixed bed reactor. 
     
     
         30 . The process of  claim 27 , wherein solids are separated from the slurry prior to step (b). 
     
     
         31 . The process of  claim 25 , wherein the bio-oil containing feedstream is separated into bio-oil and an aqueous phase between step (a) and step (b). 
     
     
         32 . The process of  claim 25 , wherein the ratio of the specific gravities of the oil phase to the aqueous bio-oil phase is less than 1.0. 
     
     
         33 . The process of  claim 25 , wherein at least a portion of the solids are removed from the bio-oil prior to step (a). 
     
     
         34 . The process of  claim 33 , wherein the removal of the at least a portion of the solids from the bio-oil occurs in a desalter, settler and/or separator. 
     
     
         35 . The process of  claim 25 , wherein the bio-oil is subjected to fractionation to produce bio-naphtha. 
     
     
         36 . The process of  claim 35 , wherein fractionation occurs prior to step (a). 
     
     
         37 . The process of  claim 35 , wherein at least a portion of the bio-naphtha is blended with the bio-oil containing feedstream. 
     
     
         38 . The process of  claim 2  wherein the first stage reactor contains a catalyst selected from the group consisting of NiMo, CoMo or NiW, sulfided transition metals, reduced metals and nobel metals. 
     
     
         39 . The process of  claim 2  wherein the first stage reactor contains a catalyst having an acid functionality. 
     
     
         40 . The process of  claim 39 , wherein the catalyst is a silica-alumina, sulfated oxide, supported phosphoric acids or a mixture thereof. 
     
     
         41 . The process of  claim 38 , wherein the sulfided transition metals are selected from the group consisting of sulfided NiMo and sulfided CoMo. 
     
     
         42 . The process of  claim 1 , wherein at least a portion of the organic reactive molecules are subjected to a condensation reaction in step (a). 
     
     
         43 . A process for producing renewable biofuel from bio-oil or pyrolysis oil comprising:
 (a) introducing a feedstream containing bio-oil or pyrolysis oil and containing solids and organic reactive materials into a first stage wherein the temperature at the entrance is from about 120° F. to about 350° F.;   (b) reducing the amount of solids and/or reactive species in the bio-oil or pyrolysis oil without substantially deoxygenating the organic reactive molecules at elevated temperature and pressure in the first stage, wherein the temperature at the entry port of the first stage does not exceed 450° F.;   (c) introducing the bio-oil or pyrolysis oil having reduced solids into a second stage, wherein the second stage is a hydrotreatment stage, and deoxygenating the bio-oil or pyrolysis oil within the second stage, wherein the temperatures and pressure in the second stage is an amount sufficient to produce a deoxygenated bio-oil or pyrolysis oil; and   (d) producing renewable biofuels from the deoxygenated bio-oil or pyrolysis oil.   
     
     
         44 . The process of  claim 43 , wherein the first stage is a hydrotreatment stage. 
     
     
         45 . The process of  claim 44 , wherein the pressure in the first stage and the pressure in the second stage are the same and wherein the first stage and the second stage are housed in the same hydrotreater reactor. 
     
     
         46 . The process of  claim 44 , wherein the first stage and the second stage are housed in separate hydrotreater reactors. 
     
     
         47 . The process of  claim 44 , wherein the pressure in the first stage does not exceed 1,000 psig. 
     
     
         48 . The process of  claim 43 , wherein the space velocity within the first stage is from about 1 to about 6 and wherein the space velocity within the second hydrotreatment stage is less than 2. 
     
     
         49 . The process of  claim 43 , wherein the bio-oil or pyrolysis oil originates from a biomass converted feedstream. 
     
     
         50 . The process of  claim 49 , wherein the biomass converted feedstream is separated into bio-oil and an aqueous phase prior to introducing the bio-oil into the first stage. 
     
     
         51 . The process of  claim 43 , wherein the bio-oil is subjected to fractionation prior to prior to step (a). 
     
     
         52 . The process of  claim 43 , wherein bio-naphtha is separated from the bio-oil during fractionation and further wherein at least a portion of the separated bio-naphtha is blended with the biomass converted feedstream. 
     
     
         53 . The process of  claim 43 , wherein at least a portion of the organic reactive molecules are subjected to a condensation reaction in step (a). 
     
     
         54 . A process for producing renewable biofuels from bio-oil or pyrolysis oil comprising:
 (a) reducing solids in the bio-oil or pyrolysis oil in a first stage while minimizing hydrogenation of organic reactive molecules in the bio-oil or pyrolysis oil, wherein:
 (i) the temperature in the first stage at the port of entry is from about 120° F. to about 350° F. and wherein the temperature at the exit port of the first stage does not exceed 450° F.; 
 (ii) the pressure in the first stage is less than about 1,000 psig; 
 (iii) the space velocity within the first stage is from about 0.2 to about 6; and 
 (iv) the amount of organic reactive molecules in the first stage is less than 5 percent; and 
   (b) deoxygenating the product of step (a) in a second stage to render deoxygenated bio-oil or pyrolysis oil, wherein:
 (i) the temperature at the exit port of the second stage is from about 650° F. to about 850° F.; 
 (ii) the pressure in the second stage is between from about 500 to about 2,000 psig; 
 (iii) the space velocity within the second stage is less than 2; and 
   (c) generating renewable biofuels from the deoxygenated product of step (b).   
     
     
         55 . The process of  claim 54 , wherein the first stage is a hydrotreatment stage. 
     
     
         56 . The process of  claim 55 , wherein the first stage and the second stage are housed in the same hydrotreater reactor. 
     
     
         57 . The process of  claim 55 , wherein the first stage and the second stage are housed in separate hydrotreater reactors. 
     
     
         58 . The process of  claim 54 , wherein at least a portion of the organic reactive molecules are subjected to a condensation reaction in step (a).