Bubbling bed catalytic hydropyrolysis process utilizinig larger catalyst particles and small biomass particles featuring an anti-slugging reactor

• US 9,512,364 B2
• Filed: 09/22/2014
• Issued: 12/06/2016
• Est. Priority Date: 04/18/2011
• Status: Active Grant

• Current Assignee: Gas Technology Institute
• Original Assignee: Gas Technology Institute
• Inventors: Marker, Terry L., Felix, Larry G., Linck, Martin B., Roberts, Michael J.
• Primary Examiner(s): Warden, Jill
• Assistant Examiner(s): Woodard, Joye L
• Application Number:
  US14/492,840
• Publication Number:
  US 20150141716A1
• Time in Patent Office: 806 Days
• Field of Search: 201/2.5, 201/31, 201/36, 585/240, 585/241, 585/242
• US Class Current: 1/1
• CPC Class Codes: B01J 2208/00061 of the reactants
• CPC Class Codes: B01J 2208/00115 with heat exchange elements inside the bed of solid particles
• CPC Class Codes: B01J 2208/00548 Flow
• CPC Class Codes: B01J 2208/0084 inside the bed, e.g. baffles
• CPC Class Codes: B01J 2219/00252 Formation of deposits other than coke
• CPC Class Codes: B01J 23/755 Nickel
• CPC Class Codes: B01J 23/882 and cobalt
• CPC Class Codes: B01J 8/1809 Controlling processes
• CPC Class Codes: B01J 8/34 with stationary packing material in the fluidised bed, e.g. bricks, wire rings, baffles
• CPC Class Codes: C10G 1/002 in combination with oil conversion- or refining processes
• CPC Class Codes: C10G 1/06 by destructive hydrogenation
• CPC Class Codes: C10G 1/086 Characterised by the catalyst used
• CPC Class Codes: C10G 1/10 from rubber or rubber waste
• CPC Class Codes: C10G 2300/1003 Waste materials
• CPC Class Codes: C10G 2300/1014 of vegetal origin
• CPC Class Codes: C10G 2300/1018 of animal origin
• CPC Class Codes: C10G 2300/202 Heteroatoms content, i.e. S, N, O, P
• CPC Class Codes: C10G 2400/02 Gasoline
• CPC Class Codes: C10G 2400/04 Diesel oil
• CPC Class Codes: C10G 2400/08 Jet fuel
• CPC Class Codes: C10G 3/45 : containing iron group metals or compounds thereof
• 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 3/57 : according to the fluidised bed technique
• CPC Class Codes: C10L 1/04 : essentially based on blends of hydrocarbons
• CPC Class Codes: C10L 2200/0469 : Renewables or materials of biological origin
• CPC Class Codes: C10L 2290/02 : Combustion or pyrolysis
• CPC Class Codes: Y02E 50/10 : Biofuels, e.g. bio-diesel
• CPC Class Codes: Y02E 50/30 : Fuel from waste, e.g. synthetic alcohol or diesel
• CPC Class Codes: Y02P 30/20 : using bio-feedstock

Abstract

This invention relates to a process for thermochemically transforming biomass or other oxygenated feedstocks into high quality liquid hydrocarbon fuels. In particular, a catalytic hydropyrolysis reactor, containing a deep bed of fluidized catalyst particles is utilized to accept particles of biomass or other oxygenated feedstocks that are significantly smaller than the particles of catalyst in the fluidized bed. The reactor features an insert or other structure disposed within the reactor vessel that inhibits slugging of the bed and thereby minimizes attrition of the catalyst. Within the bed, the biomass feedstock is converted into a vapor-phase product, containing hydrocarbon molecules and other process vapors, and an entrained solid char product, which is separated from the vapor stream after the vapor stream has been exhausted from the top of the reactor. When the product vapor stream is cooled to ambient temperatures, a significant proportion of the hydrocarbons in the product vapor stream can be recovered as a liquid stream of hydrophobic hydrocarbons, with properties consistent with those of gasoline, kerosene, and diesel fuel. Separate streams of gasoline, kerosene, and diesel fuel may also be obtained, either via selective condensation of each type of fuel, or via later distillation of the combined hydrocarbon liquid.

Claims

1. A method for hydropyrolyzing an oxygenated organic feedstock, the method comprising:

(a) introducing the oxygenated organic feedstock and a fluidizing gas comprising hydrogen into a fluidized bed hydropyrolysis reactor comprising a fluidized bed of solid particles, including catalyst, under hydropyrolysis conditions sufficient to generate product vapors from thermal decomposition and hydropyrolysis of the oxygenated organic feedstock; and

(b) recovering from the product vapors a product stream containing substantially fully deoxygenated hydrocarbon species, wherein the product stream comprises less than about 4% oxygen by mass;

wherein the fluidized bed of solid particles has a depth of greater than two reactor diameters and includes lateral inserts selected from the group consisting of obstructions, obstacles, constrictions, and combinations thereof, spaced at axial intervals from about one to about two reactor diameters in a manner such that slugging does not occur within the fluidized bed hydropyrolysis reactor.

2. The method of claim 1, wherein an average particle size of the catalyst is greater than an average particle size of the oxygenated organic feedstock.

3. The method of claim 1, wherein entrained solids exit the fluidized bed hydropyrolysis reactor, the method further comprising separating the entrained solids from a mixture of the fluidizing gas and the product vapors.

4. The method of claim 1, wherein, in step (b), the product stream is recovered by condensation of the product vapors.

5. The method of claim 1, wherein, in step (b), the product stream containing substantially fully deoxygenated hydrocarbon species is recovered following further hydrogenation of the product vapors using a hydroconversion catalyst, in an integrated hydropyrolysis and hydroconversion process.

6. The method of claim 1, wherein the fully deoxygenated hydrocarbon species include hydrocarbons with atmospheric-pressure boiling points consistent with those of at least one of gasoline, kerosene, and diesel fuel.

7. The method of claim 1, wherein the hydropyrolysis conditions include a hydrogen partial pressure from about 200 psig to about 600 psig.

8. The method of claim 7, wherein the hydropyrolysis conditions further include a temperature from about 650°

F. to about 1100°

F.

9. The method of claim 1 wherein the hydropyrolysis conditions include a superficial velocity of the fluidizing gas, sufficient to maintain a bubbling fluidized bed.

10. The method of claim 1 wherein the oxygenated organic feedstock comprises lignocellulosic biomass.

11. The method of claim 1 wherein the feedstock comprises solid particles of an oxygenated polymer.

12. The method of claim 1 wherein the oxygenated organic feedstock comprises a wholly or partially dewatered, high-lipid algae.

13. The method of claim 1 wherein the oxygenated organic feedstock comprises waste organic material of animal origin.

14. The method of claim 1 wherein the oxygenated organic feedstock comprises an oxygenated organic liquid, which undergoes hydropyrolysis in the fluidized bed hydropyrolysis reactor.

15. The method of claim 1, wherein positions of the lateral inserts are varied, in a manner preventing a single, open axial passage extending within the fluidized bed for a distance of more than two reactor diameters.

16. The method of claim 1, wherein slugging in the fluidized bed is prevented via the use of equipment for incorporating the lateral inserts centrally about the interior of the fluidized bed hydropyrolysis reactor.

17. The method of claim 1 wherein upper surfaces of the lateral inserts are at least one of rounded, peaked, and sloped, in order to prevent the solid particles from coming to rest on the upper surfaces.

18. The method of claim 1 wherein upper surfaces of the lateral inserts are porous to allow the passage of the product vapors, in order to prevent the solid materials from coming to rest on the upper surfaces.

19. The method of claim 1 wherein upper surfaces of the lateral inserts comprise abrasion-resistant sintered glass ceramic material.

20. The method of claim 1 wherein surfaces of the lateral inserts are catalytically active and facilitate hydropyrolysis.

21. The method of claim 1, wherein the product stream is recovered in an amount of at least about 24% by mass of the oxygenated organic feedstock.

22. A method for hydropyrolyzing an oxygenated organic feedstock, the method comprising:

(a) introducing the oxygenated organic feedstock and a fluidizing gas comprising hydrogen into a fluidized bed hydropyrolysis reactor comprising a fluidized bed of solid particles, including catalyst, under hydropyrolysis conditions sufficient to generate product vapors from thermal decomposition and hydropyrolysis of the oxygenated organic feedstock; and

(b) condensing from the product vapors a liquid product stream containing substantially fully deoxygenated hydrocarbon species, wherein the liquid product stream comprises less than about 4% oxygen by mass and is condensed as a separate phase from a primarily water-containing phase, also condensed from the product vapors;

wherein the fluidized bed of solid particles has a depth of greater than two reactor diameters and includes lateral inserts selected from the group consisting of obstructions, obstacles, constrictions, and combinations thereof, spaced at axial intervals from about one to about two reactor diameters in a manner such that slugging does not occur within the fluidized bed hydropyrolysis reactor.

23. The method of claim 22, wherein in step (b), the product stream containing substantially fully deoxygenated hydrocarbon species is condensed following further hydrogenation of the product vapors using a hydroconversion catalyst, in an integrated hydropyrolysis and hydroconversion process.

24. The method of claim 22, wherein the primarily water-containing phase contains less than 5% by mass dissolved total organic carbon (TOC).

25. The method of claim 22, wherein the liquid product stream is recovered in an amount of at least about 24% by mass of the oxygenated organic feedstock.