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

• US 8,841,495 B2
• Filed: 04/18/2011
• Issued: 09/23/2014
• 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., Roberts, Michael J., Linck, Martin B.
• Primary Examiner(s): Warden, Jill
• Assistant Examiner(s): WOODARD, JOYE L
• Application Number:
  US13/089,010
• Publication Number:
  US 20120260563A1
• Time in Patent Office: 1,254 Days
• Field of Search: 585/240, 585/242, 201/2.5, 201/25, 201/31, 201/36, 422/139
• US Class Current: 585/240
• 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 of hydropyrolysis comprising:

a. introducing an oxygenated organic feedstock into a fluidized bed reactor, wherein said feedstock is rapidly heated from ambient temperature to the temperature of the fluidized bed, and is thereby devolatilized;

b. introducing a stream of fluidizing gas comprising mostly molecular hydrogen into the fluidized bed reactor, creating conditions under which rapid mixing and heat transfer occur throughout the fluidized bed;

c. maintaining a deep bed of solid particles of catalyst, the depth of which is significantly greater than 2 reactor diameters, in a state of vigorous motion, to promote reactions resulting in deoxygenation and chemical stabilization of vapors produced when the feedstock is devolatilized;

d. removing solid residues, remaining after devolatilization and hydropyrolysis of the feedstock, from the fluidized bed reactor via entrainment in the stream of fluidizing gas and product vapors exiting the fluidized bed reactor;

e. removing attritted residues of catalyst, but not intact particles of catalyst, or particles of catalyst that have been minimally attritted, from the fluidized bed reactor via entrainment in the stream of fluidizing gas and product vapors exiting the fluidized bed reactor;

f. separating the solid residues, entrained in the stream of fluidizing gas and product vapors exiting the fluidized bed reactor, from the stream of fluidizing gas and product vapors exiting the fluidized bed reactor;

g. recovering a product stream of hydrocarbon vapors comprising hydrocarbon species with atmospheric-pressure boiling points, consistent with those of at least one of gasoline, kerosene and diesel fuel, from the hydropyrolysis process as condensed liquid;

h. releasing enough exothermic heat from the deoxygenation reactions occurring during hydropyrolysis of the feedstock to supply process heat required by endothermic processes occurring during hydropyrolysis of the feedstock, including chemical reactions, heating of feedstock, and evaporation of liquids; and

i. dispersing one or more modifications to an interior of the reactor vessel, in such a manner that slugging does not occur within the fluidized bed reactor.

2. The method of claim 1 wherein the fluidized-bed reactor is maintained at a partial pressure of hydrogen of about 200 psig to 600 psig.

3. The method of claim 1 wherein the recovered stream of condensed liquid contains less than 4% by mass of oxygen.

4. The method of claim 1 wherein the temperature of the fluidized bed reactor is between approximately 343 degrees Celsius (650 degrees Fahrenheit) and approximately 593 degrees Celsius (1100 degrees Fahrenheit).

5. The method of claim 1 wherein the relationship between a volumetric feed rate of solid feedstock particles and a volume of the fluidized bed reactor is such that the Volume Hourly Space Velocity (VHSV) of the reactor is between approximately 1 and approximately 40.

6. The method of claim 1 wherein a density of particles of catalyst is in the range of approximately 0.5 kilograms per liter to 2 kilograms per liter.

7. The method of claim 1 wherein the feedstock is prepared in such a way that solid residues, remaining after hydropyrolysis of the feedstock, are substantially smaller, in their largest dimension, than the solid catalyst particles that form the fluidized bed.

8. The method of claim 1 wherein the feedstock contains no water.

9. The method of claim 1 wherein the feedstock is only partly dewatered, and contains some water.

10. The method of claim 1 wherein the feedstock comprises particles of solid biomass.

11. The method of claim 1 wherein the feedstock comprises solid particles of an oxygenated polymer, such as polyethylene terephthalate.

12. The method of claim 1 wherein the feedstock comprises a wholly or partially dewatered biomass feedstock that is high in lipid content, such as high-lipid algae.

13. The method of claim 1 wherein the feedstock comprises organic material of an aquatic origin such as fish, fish parts and wastes from fish processing.

14. The method of claim 1 wherein the feedstock comprises materials manufactured or otherwise obtained from biomass, such as paper products and residues rejected as waste streams by paper mills.

15. The method of claim 1 wherein the feedstock comprises organic material of animal origin, such as offal, fats, greases, and tissues.

16. The method of claim 1 wherein the feedstock comprises waste organic material of animal origin, such as manure or sewage sludge.

17. The method of claim 1 wherein the feedstock is introduced to the reactor as a stream comprising solid particles entrained in a rapidly-moving transport gas stream, and wherein the transport of feedstock into the fluidized bed is accomplished primarily via the action of the transport gas on solid particles of feedstock.

18. The method of claim 1 wherein the feedstock comprises a slurry of solid particles, suspended in a carrier liquid that evaporates when it is introduced into the reactor.

19. The method of claim 1 wherein the feedstock comprises an oxygenated organic liquid, which undergoes hydropyrolysis in the hydropyrolysis process.

20. The method of claim 1 wherein a superficial velocity of fluidizing gas passing through the fluidized bed reactor, is sufficient to create a state consistent with that of a bubbling fluidized bed.

21. The method of claim 1 wherein a superficial velocity of fluidizing gas passing through the fluidized bed reactor is no higher than the minimum needed to create a state consistent with that of a bubbling fluidized bed.

22. The method of claim 1 wherein the solid particles of catalyst are spherical.

23. The method of claim 1 wherein the solid particles of catalyst are attrition-resistant.

24. The method of claim 1 wherein the solid particles of catalyst are porous and include a large internal surface area within the outer surface of the particle.

25. The method of claim 1 wherein the solid particles of catalyst have properties consistent with those of a highly active hydrotreating catalyst.

26. The method of claim 1 wherein the solid particles of catalyst comprise an alumina-based substrate, impregnated with a sulfided nickel-molybdenum catalyst or sulfided cobalt-molybdenum catalyst.

27. The method of claim 1 wherein the solid particles of catalyst comprise an alumina-based substrate, impregnated with a metal such as nickel, or cobalt, or iron, or other metals that can be used as catalysts in hydrotreating.

28. The method of claim 1 wherein the solid particles of catalyst comprise an aluminiosilicate-based substrate, impregnated with a metal such as nickel, or cobalt, or iron, or other metals that can be used as catalysts in hydrotreating.

29. The method of claim 1 wherein the solid particles of catalyst comprise a glass-ceramic-based substrate, impregnated with a metal such as nickel, or cobalt, or iron, or other metals that can be used as catalysts in hydrotreating.

30. The method of claim 1 wherein the solid particles of catalyst comprise two or more catalysts which differ by at least one of density, aerodynamic size and aerodynamic diameter but are otherwise physically similar, and are disposed throughout the fluidized bubbling bed and by virtue of having different properties tend to segregate and stratify, becoming vertically ordered by property so as to create regions within the bed that differ in catalytic activity.

31. The method of claim 1 wherein a mean diameter of catalyst particles is greater than approximately 3200 microns (3.2 millimeters).

32. The method of claim 1 further comprising separating metallic catalyst fines from char, the separation effected with a barrier filter that incorporates a remotely energized and de-energized magnetic field to retain magnetic catalyst particles until they can be discharged by backpulsing when the magnetic field is de-energized.

33. The method of claim 32 wherein char can be separated from the product stream and removed by backpulsing while the magnetic field remains energized and magnetic material is retained on the filtering surface.

34. The method of claim 1 further comprising separating metallic catalyst fines from char, wherein the separation is effected by a virtual impactor that diverts a stream of heavier catalyst fines to a downstream collection stage.

35. The method of claim 34 wherein the downstream collection stage is a barrier filter that can be cleaned by periodic backpulsing.

36. The method of claim 34 wherein the downstream collection stage is a barrier filter that incorporates a remotely energized magnetic field to retain magnetic catalyst particles the until they can be discharged when the magnetic field is deenergized and the filter is cleaned by backpulsing.

37. The method of claim 1 wherein slugging in the fluidized bed is controlled via the use of equipment incorporating lateral obstructions, obstacles, or constrictions, an axis or centerline of the equipment intersecting a centerline of the fluidized bed reactor.

38. The method of claim 37 wherein a cross-sectional area of the obstructions, obstacles, or constrictions, when seen from a top of the fluidized-bed reactor, is equal to approximately 40% of the cross-sectional area of the fluidized bed reactor.

39. The method of claim 37 wherein the obstructions, obstacles, or constrictions, are equipped with at least one of temperature-sensing means and means by which heat may be removed from or added to the fluidized bed, in such a manner that the temperature of the fluidized bed around the obstructions, obstacles, or constrictions can be monitored and/or regulated.

40. The method of claim 37 wherein the obstructions, obstacles, or constrictions, are installed at vertical locations along the fluidized bed reactor that are separated from one another by one to two reactor diameters.

41. The method of claim 37 wherein the orientations of the obstructions, obstacles, or constrictions, are varied, when seen from a top of the reactor, so that a single, open passage, running the length of the reactor for a distance of more than two reactor diameters, is not present.

42. The method of claim 37 wherein upper surfaces of the obstructions, obstacles, or constrictions, are at least one of rounded, peaked and sloped in order to prevent bed material from coming to rest on said surface.

43. The method of claim 37 wherein the upper surfaces of the obstructions, obstacles, or constrictions, are porous and constructed so that gas can pass through the upper part of the obstruction in order to prevent bed material from coming to rest on said surface.

44. The method of claim 37 wherein the upper surfaces of the obstructions, obstacles, or constrictions, are uniformly porous and constructed of a highly abrasion-resistant sintered glass ceramic material so that gas can pass through the exterior of the obstruction in order to prevent bed material from coming to rest on said surface.

45. The method of claim 37 wherein the equipment is highly-abrasion resistant.

46. The method of claim 37 wherein the equipment is at least partially constructed of an extremely hard ceramic or glass-ceramic material.

47. The method of claim 37 wherein the equipment is at least partially coated with one of a highly abrasion-resistant coating and an extremely hard ceramic or glass-ceramic material.

48. The method of claim 37 wherein the surfaces of the equipment are catalytically active, and facilitate hydropyrolysis reactions.

49. The method of claim 37 wherein the equipment comprises an insert with a centrally located support, running along the central axis of the fluidized bed reactor, to which the obstructions, obstacles, or constrictions, are attached.

50. The method of claim 37 wherein the equipment comprises an insert with a circumferential support, disposed around the circumference of the fluidized bed reactor, to which the obstructions, obstacles, or constrictions, are attached.

51. The method of claim 37 wherein the equipment comprises an insert with a circumferential support, disposed around the circumference of the fluidized-bed reactor, with gas paths available to connect with locations to where porous obstructions, obstacles, or constrictions are attached.

52. The method of claim 37 wherein the equipment comprises obstructions, obstacles, or constrictions that are directly attached to, supported by, and in communication with the wall of the fluidized bed reactor.

53. The method of claim 37 wherein the equipment comprises obstructions, obstacles, or constrictions that molded or cast into a molded or cast refractory lining of the fluidized bed reactor.

54. The method of claim 1 wherein the modifications that control slugging in the fluidized bed reactor incorporate internal heat-exchanging flow pathways connected to external piping that is isolated from the internal environment of the reactor through which liquids and gases can be passed to extract heat from the reactor.

55. The method of claim 1 wherein all required process heat is supplied from the deoxygenation reactions occurring during hydropyrolysis of the feedstock.