Pre-processing Bio-oil Before Hydrotreatment

Patent metadata

Field	Value
Publication number	US-2016257889-A1
Application number	US-201615062059-A
Country	US
Kind code	A1
Filing date	Mar 5, 2016
Priority date	Mar 5, 2015
Publication date	Sep 8, 2016
Grant date	—

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.

First claim

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.

Assignees

• Battelle Memorial Institute

Inventors

• Abdullah Zia
• Taha Rachid
• Garbark Daniel
• Wang Huamin
• Lee Guo-Shuh J

Classifications

• C10G3/50 Primary

  in the presence of hydrogen, hydrogen donors or hydrogen generating compounds · CPC title

• C10G3/46

  in combination with chromium, molybdenum, tungsten metals or compounds thereof · CPC title

• C10G2300/1011

  Biomass · CPC title

• Y02P30/20

  using bio-feedstock · CPC title