Pre-processing Bio-oil Before Hydrotreatment

Abstract

Described are methods and systems for preparing stabilized bio-oil suitable for subsequent hydrotreatment and forming a hydrocarbon product from a stabilized bio-oil. For example, preparing stabilized bio-oil suitable for subsequent hydrotreatment may include filtering bio-oil effective to remove at least a portion of particles having an effective particulate diameter greater than about 10 micrometers; treating the bio-oil effective to remove at least a portion of inorganic species from the bio-oil; and catalytically stabilizing the bio-oil to provide the stabilized bio-oil suitable for subsequent hydrotreatment. Forming a hydrocarbon product from a stabilized bio-oil may include hydrotreating the stabilized bio-oil by, for example, contacting the stabilized bio-oil to a hydrotreatment catalyst in the presence of hydrogen, thereby providing the hydrocarbon product. Also included are stabilized bio-oil and hydrocarbon products derived therefrom.

1 . A method  200  for forming a stabilized bio-oil suitable for subsequent hydrotreatment, comprising:
   202  providing the bio-oil; 
   204  filtering the bio-oil effective to remove at least a portion of particles having an effective particulate diameter greater than about 10 micrometers; 
   206  treating the bio-oil effective to remove at least a portion of inorganic species from the bio-oil; and 
   208  catalytically stabilizing the bio-oil, 
 
       thereby providing the stabilized bio-oil suitable for subsequent hydrotreatment. 
     
     
         2 . The method of  claim 1 , providing the bio-oil comprising pyrolyzing biomass to produce the bio-oil in a downflow reactor. 
     
     
         3 . The method of  claim 1 :
 providing the bio-oil comprising pyrolyzing the biomass in a downflow reactor to produce a bio-oil vapor; and   filtering the bio-oil comprising in-line filtering the bio-oil vapor produced by the pyrolysis effective to remove at least a portion of the particles having the effective particulate diameter greater than about 10 micrometers.   
     
     
         4 . The method of  claim 1 , filtering the bio-oil comprising:
 a first filtering process effective to remove at least a portion of the particles having an effective particulate diameter greater than about 10 micrometers; and   a second filtering process effective to remove at least a portion of the particles having an effective particulate diameter in micrometers greater than one or more of about: 5, 4, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, and 0.1.   
     
     
         5 . The method of  claim 4 , the second filtering process conducted using one or more of:
 a pressure differential in pounds per square inch of at least about one or more of: 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, 125, 150, 175, and 200; and   a temperature in ° C. of at least about one or more of: 30, 40, 50, 60, 70, 80, 90, and 100.   
     
     
         6 . The method of  claim 1 , treating the bio-oil effective to remove at least a portion of inorganic species from the bio-oil comprising contacting the bio-oil to one or more of: an ion exchange resin, a zeolite, and activated carbon. 
     
     
         7 . The method of  claim 1 , treating the bio-oil effective to remove at least a portion of inorganic species from the bio-oil comprising reducing the amount of one or more inorganic species in the bio-oil to a concentration in parts per million of less than one or more of about: 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, and 1. 
     
     
         8 . The method of  claim 1 , catalytically stabilizing the bio-oil comprising contacting the bio-oil to a stabilizing catalyst comprising a metal dispersed on a solid support. 
     
     
         9 . The method of  claim 1 , further comprising:
 contacting the bio-oil to a diluting medium to form a diluted bio-oil, and   catalytically stabilizing the bio-oil comprising contacting the diluted bio-oil to a stabilizing catalyst.   
     
     
         10 . The method of  claim 9 , the diluting medium comprising one or more of: an organic solvent, a petroleum fuel, water, and a portion of the stabilized bio-oil. 
     
     
         11 . The method of  claim 10 , further comprising removing at least a portion of the solvent comprising one or more of: the organic solvent, the petroleum fuel, and the water from the diluted bio-oil after catalytically stabilizing the diluted bio-oil. 
     
     
         12 . The method of  claim 1 , catalytically stabilizing the bio-oil comprising contacting the bio-oil to a stabilizing catalyst comprising a zeolite. 
     
     
         13 . The method of  claim 1 , catalytically stabilizing the bio-oil comprising contacting the bio-oil to a stabilizing catalyst under conditions comprising one or more of:
 a temperature in ° C. of about one or more of: 40 to 300, 100 to 280, 120 to 270, 130 to 250, 140 to 225, 150 to 200, 160 to 180, and 170;   a pressure in PSI of about one or more of: 500 to 2500, 750 to 2250, 1000 to 2000, 1250 to 1750, 1400 to 1600, and 1500; and   a presence of hydrogen.   
     
     
         14 . The method of  claim 1 , catalytically stabilizing the bio-oil comprising one or more of:
 flowing the bio-oil past a stabilizing catalyst at a liquid hourly space velocity (LHSV) of between about 0.05 hr −1  to 1 hr −1 ; and   contacting the bio-oil to the stabilizing catalyst for a Time On Stream (TOS) in hours of at least about one or more of: 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1,100, 1,200, 1,300, 1,400, 1,500, 1,750, 2,000, 3,000, 4,000, 5,000, 6,000, 7,000, 8,000, 12,000, and 16,000.   
     
     
         15 . The method of  claim 1 , catalytically stabilizing the bio-oil comprising flowing the bio-oil past a stabilizing catalyst, the method further comprising regenerating the stabilizing catalyst, comprising one or more of:
 rinsing the stabilizing catalyst with an organic solvent; and   contacting the stabilizing catalyst with hydrogen at a temperature in ° C. of about one or more of: 250 to 550, 300 to 500, 325 to 475, 350 to 450, 375 to 425, and 400.   
     
     
         16 . The method of  claim 1 , comprising filtering the bio-oil effective to remove at least a portion of particles having an effective particulate diameter greater than about 1 micrometer. 
     
     
         17 . A method  350  for forming a hydrocarbon product from a bio-oil, comprising:
   352  providing the bio-oil; 
   354  filtering the bio-oil effective to remove at least a portion of particles having an effective particulate diameter greater than about 10 micrometers; 
   356  treating the bio-oil effective to remove at least a portion of inorganic species from the bio-oil; 
   358  catalytically stabilizing the bio-oil to provide a stabilized bio-oil; and 
   360  hydrotreating the stabilized bio-oil comprising contacting the stabilized bio-oil to a hydrotreatment catalyst in the presence of hydrogen, 
 
       thereby providing the hydrocarbon product. 
     
     
         18 . The method of  claim 17 , the hydrotreatment catalyst comprising one or more of: an active metal catalyst and a sulfided catalyst. 
     
     
         19 . The method of  claim 17 , hydrotreating the stabilized bio-oil comprising contacting the stabilized bio-oil to a hydrotreatment catalyst in the presence of a substantial excess of hydrogen at a pressure in pounds per square inch gauge of one or more of: 100 to 2000, 500 to 1800, and 1000 to 1500. 
     
     
         20 . The method of  claim 17 , hydrotreating the stabilized bio-oil comprising contacting the stabilized bio-oil to the hydrotreatment catalyst under conditions comprising one or more of:
 a liquid hourly space velocity (LHSV) of between about 0.05 hr −1  to 1 hr −1 ; and   in the presence of hydrogen for a Time On Stream (TOS) in hours of at least about one or more of: 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1,100, 1,200, 1,300, and 1,400, 1,500, 1,750, 2,000, 3,000, 4,000, 5,000, 6,000, 7,000, 8,000, 12,000, and 16,000.   
     
     
         21 . The method of  claim 17 , comprising filtering the bio-oil effective to remove at least a portion of particles having an effective particulate diameter greater than about 1 micrometer.