HYDROPYROLYSIS OF BIOMASS FOR PRODUCING HIGH QUALITY LIQUID FUELS

• US 20100256428A1
• Filed: 01/11/2010
• Published: 10/07/2010
• Est. Priority Date: 04/07/2009
• Status: Active Grant

• Current Assignee: Gas Technology Institute
• Original Assignee: Gas Technology Institute
• Inventors: Marker, Terry L., Linck, Martin B., Felix, Larry G.
• Granted Patent: US 8,492,600 B2
• Time in Patent Office: Days
• US Class Current: 585/240
• CPC Class Codes: C01B 2203/0205 containing a reforming step
• CPC Class Codes: C01B 2203/0283 containing a CO-shift step, i.e. a water gas shift step
• CPC Class Codes: C01B 2203/042 Purification by adsorption on solids
• CPC Class Codes: C01B 2203/043 Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
• CPC Class Codes: C01B 2203/0475 the impurity being carbon dioxide
• CPC Class Codes: C01B 2203/0811 by combustion of fuel
• CPC Class Codes: C01B 2203/0822 the fuel containing hydrogen
• CPC Class Codes: C01B 2203/0827 at least part of the fuel being a recycle stream
• CPC Class Codes: C01B 2203/1241 Natural gas or methane
• CPC Class Codes: C01B 2203/1247 Higher hydrocarbons
• CPC Class Codes: C01B 2203/1258 Pre-treatment of the feed
• CPC Class Codes: C01B 2203/148 involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
• CPC Class Codes: C01B 3/16 using catalysts
• CPC Class Codes: C01B 3/34 by reaction of hydrocarbons with gasifying agents
• CPC Class Codes: C10G 1/06 by destructive hydrogenation
• CPC Class Codes: C10G 2300/1011 Biomass
• CPC Class Codes: C10G 2300/4018 Spatial velocity, e.g. LHSV, WHSV
• CPC Class Codes: C10G 2300/4081 Recycling aspects
• CPC Class Codes: C10G 2300/807 Steam
• CPC Class Codes: C10G 2400/02 Gasoline
• CPC Class Codes: C10G 2400/04 : Diesel oil
• CPC Class Codes: C10G 3/46 : in combination with chromium, molybdenum, tungsten metals or compounds thereof
• CPC Class Codes: C10G 3/50 : in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
• CPC Class Codes: C10G 3/60 : Controlling or regulating the processes
• CPC Class Codes: C10G 47/02 : characterised by the catalyst used
• CPC Class Codes: Y02P 20/10 : Process efficiency
• CPC Class Codes: Y02P 20/145 : the feedstock being materials of biological origin
• CPC Class Codes: Y02P 20/52 : using catalysts, e.g. selective catalysts
• CPC Class Codes: Y02P 30/20 : using bio-feedstock

Abstract

A self-sustaining process for producing high quality liquid fuels from biomass in which the biomass is hydropyrolyzed in a reactor vessel containing molecular hydrogen and a deoxygenating catalyst, producing a partially deoxygenated hydropyrolysis liquid, which is hydrogenated using a hydroconversion catalyst, producing a substantially fully deoxygenated hydrocarbon liquid and a gaseous mixture comprising CO and light hydrocarbon gases (C₁-C₃). The gaseous mixture is reformed in a steam reformer, producing reformed molecular hydrogen, which is then introduced into the reactor vessel for hydropyrolizing the biomass. The deoxygenated hydrocarbon liquid product is further separated to produce diesel fuel, gasoline, or blending components for gasoline and diesel fuel.

Claims

1. A process for producing liquid products from biomass comprising the steps of:

a) hydropyrolyzing biomass in a hydropyrolysis reactor vessel containing molecular hydrogen and a deoxygenating catalyst, producing CO₂, CO and C₁-C₃ gas, a partially deoxygenated hydropyrolysis liquid and char;

b) removing said char from said partially deoxygenated hydropyrolysis liquid;

c) hydroconverting said partially deoxygenated hydropyrolysis liquid in a hydroconversion reactor vessel using a hydroconversion catalyst in the presence of the CO₂, CO and C₁-C₃ gas generated in step a), producing a substantially fully deoxygenated hydrocarbon liquid and a gaseous mixture comprising CO, CO₂, and light hydrocarbon gases (C₁-C₃);

d) steam reforming a portion of said gaseous mixture using water produced in step a) and step c), producing reformed molecular hydrogen; and

e) introducing said reformed molecular hydrogen into said reactor vessel for hydropyrolizing said biomass, wherein steps a) and c) are operated at conditions under which about 30-70% of oxygen in said biomass is converted to H₂O and about 30-70% of said oxygen is converted to CO and CO₂.

2. The process of claim 1, wherein a portion of said substantially fully deoxygenated hydrocarbon liquid created in step c) is recycled to said hydropyrolysis reactor vessel or said hydroconversion reactor vessel to control temperature therein.

3. The process of claim 1, wherein at least one of said deoxygenating catalyst and said hydroconversion catalyst is a glass-ceramic material.

4. The process of claim 1, wherein a hydrocracking catalyst is disposed at least one of upstream of, downstream of, within, and parallel with said hydroconversion reactor vessel.

5. The process of claim 4, wherein said hydrocracking catalyst is an acidic, metal-containing catalyst which provides both a hydrogenation function and an acidic function.

6. The process of claim 1, wherein said hydroconversion catalyst is replaced by a hydrocracking catalyst.

7. The process of claim 1, wherein said hydroconversion catalyst catalyzes both a water-gas-shift reaction and hydroconversion.

8. The process of claim 1, wherein all of said steps a), c), and d) are carried out at a substantially same pressure.

9. The process of claim 4, wherein all of said steps a), c), and d) are carried out at a substantially same pressure.

10. The process of claim 8, wherein said pressure is in a range of about 100 to about 800 psig.

11. The process of claim 9, wherein said pressure is in a range of about 100 to about 800 psig.

12. The process of claim 1, wherein said hydropyrolysis is carried out at a temperature in a range of about 500°

F. to about 1000°

F. and said hydroconversion is carried out at a temperature in a range of about 500°

F. to about 850°

F.

13. The process of claim 1, wherein said hydropyrolysis is carried out at a weight hourly space velocity of about 0.2 to about 10 gm biomass/gm catalyst/hr.

14. The process of claim 1, wherein said hydroconversion is carried out with a weight hourly space velocity of about 0.2 to about 3 gm biomass/gm catalyst/hr.

15. The process of claim 2, wherein said substantially fully deoxygenated hydrocarbon liquid is separated into diesel and gasoline fractions suitable for use as transportation fuel.

16. The process of claim 1, wherein said hydropyrolysis reactor vessel is a fluidized bed reactor containing a fluidized bed, and a gas residence time in said hydropyrolysis reactor vessel is less than about one minute.

17. The process of claim 16, wherein said char is removed from said fluidized bed reactor substantially only from above said fluidized bed.

18. The process of claim 1, wherein char is removed from said partially deoxygenated hydropyrolysis liquid by bubbling gases output by said hydropyrolysis through a recirculating liquid using a high boiling point portion of said substantially fully deoxygenated hydrocarbon liquid.

19. The process of claim 1, wherein output from said process consists essentially of liquid product and CO₂.

20. The process of claim 17, wherein said deoxygenation catalyst is granulated and sufficiently resistant to attrition such that it attrits said char, thereby enabling removal of said char from said fluidized bed reactor substantially only from above said fluidized bed.

21. The process of claim 1, wherein said hydropyrolysis reactor vessel is a fluidized bed reactor containing a fluidized bed and said char is removed from said fluidized bed reactor by energetic char separation employing at least one of an inertial, electrostatic, and magnetic process.

22. The process of claim 21, wherein said deoxygenating catalyst is a glass-ceramic material.

23. A process for producing liquid products from biomass comprising the steps of:

pyrolyzing said biomass in a hydropyrolysis reactor vessel in the presence of H₂ and a deoxygenating catalyst at a hydropyrolysis pressure in a range of about 100 psig to about 800 psig, producing a hydropyrolysis process output comprising partially deoxygenated hydropyrolysis liquid and char;

separating said char from said hydropyrolysis process output;

hydroconverting said partially deoxygenated hydropyrolysis liquid in a hydroconversion reactor vessel in the presence of a hydroconversion catalyst at a hydroconversion pressure in a range of about 100 psig to about 800 psig, producing substantially fully deoxygenated hydrocarbon liquid and a gaseous mixture comprising CO and C₁-C₃ light hydrocarbon gases;

steam reforming a portion of said gaseous mixture, producing reformed H₂; and

recirculating said reformed H₂ into said reactor vessel for hydropyrolyzing additional biomass.

24. The process of claim 23, wherein in a range of about 30-70% of oxygen in said biomass is converted to H₂O and about 30-70% of said oxygen is converted to CO and CO₂.

25. The process of claim 23, wherein a hydrocracking catalyst is disposed at least one of upstream of, downstream of, within, and parallel with said hydroconversion reactor vessel.

26. The process of claim 25, wherein said hydrocracking catalyst is an acidic, metal-containing catalyst which provides both a hydrogenation function and an acidic function.

27. The process of claim 23, wherein said hydroconversion catalyst catalyzes both a water-gas-shift reaction and hydroconversion.

28. The process of claim 23, wherein said hydropyrolyzing is carried out at a hydropyrolysis temperature in a range of about 500°

F. to about 1000°

F. and said hydroconverting is carried out at a hydroconversion temperature in a range of about 500°

F. to about 850°

F.

29. The process of claim 23, wherein said substantially fully deoxygenated hydrocarbon liquid is separated into diesel and gasoline fractions suitable for use as transportation fuel.

30. The process of claim 23, wherein said reactor vessel is a fluidized bed reactor containing a fluidized bed.

31. The process of claim 23, wherein output from said process consists essentially of liquid product and CO₂.

32. The process of claim 23, wherein said hydroconversion catalyst is replaced entirely by a hydrocracking catalyst.

34. The process of claim 23, wherein said hydropyrolysis catalyst is replaced entirely by a hydrocracking catalyst.