Process for producing high-carbon biogenic reagents

• US 10,174,267 B2
• Filed: 06/13/2016
• Issued: 01/08/2019
• Est. Priority Date: 04/15/2011
• Status: Active Grant

• Current Assignee: Carbon Technology Holding LLC
• Original Assignee: Carbon Technology Holdings LLC
• Inventors: Mennell, James A., Despen, Daniel J.
• Primary Examiner(s): Toomer, Cephia D
• Application Number:
  US15/180,650
• Publication Number:
  US 20170037333A1
• Time in Patent Office: 939 Days
• CPC Class Codes: B01J 21/18 Carbon
• CPC Class Codes: C01B 32/312 Preparation
• CPC Class Codes: C01B 32/318 characterised by the starting materials
• CPC Class Codes: C10B 39/00 Cooling or quenching coke
• CPC Class Codes: C10B 39/02 Dry cooling outside the oven
• CPC Class Codes: C10B 41/00 Safety devices, e.g. signalling or controlling devices for use in the discharge of coke
• CPC Class Codes: C10B 43/02 Removing incrustations
• CPC Class Codes: C10B 45/00 Other details
• CPC Class Codes: C10B 47/30 in rotary ovens or retorts
• CPC Class Codes: C10B 49/02 with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge
• CPC Class Codes: C10B 53/02 of cellulose-containing material production of pyroligneous acid C10C5/00
• CPC Class Codes: C10B 57/02 Multi-step carbonising or coking processes
• CPC Class Codes: C10B 57/06 containing additives
• CPC Class Codes: C10B 57/10 Drying
• CPC Class Codes: C10L 2200/0204 Metals or alloys
• CPC Class Codes: C10L 2200/025 Halogen containing compounds
• CPC Class Codes: C10L 2200/0469 Renewables or materials of biological origin
• CPC Class Codes: C10L 2290/02 Combustion or pyrolysis
• CPC Class Codes: C10L 2290/06 Heat exchange, direct or indirect
• CPC Class Codes: C10L 2290/08 Drying or removing water
• CPC Class Codes: C10L 2290/145 : of air
• CPC Class Codes: C10L 2290/28 : Cutting, disintegrating, shredding or grinding
• CPC Class Codes: C10L 2290/30 : Pressing, compressing or compacting
• CPC Class Codes: C10L 2290/50 : Screws or pistons for moving along solids
• CPC Class Codes: C10L 2290/52 : Hoppers
• CPC Class Codes: C10L 2290/58 : Control or regulation of the fuel preparation of upgrading process
• CPC Class Codes: C10L 2290/60 : Measuring or analysing fractions, components or impurities or process conditions during preparation or upgrading of a fuel
• CPC Class Codes: C10L 5/04 : Raw material of mineral origin to be used; Pretreatment thereof pretreatment of fuels of non-mineral origin C10L5/40
• CPC Class Codes: C10L 5/36 : Shape
• CPC Class Codes: C10L 5/363 : Pellets or granulates
• CPC Class Codes: C10L 5/365 : Logs
• CPC Class Codes: C10L 5/366 : Powders
• CPC Class Codes: C10L 5/442 : Wood or forestry waste
• CPC Class Codes: C10L 5/447 : Carbonized vegetable substances, e.g. charcoal, or produced by hydrothermal carbonization of biomass
• CPC Class Codes: C21B 13/0066 : Preliminary conditioning of the solid carbonaceous reductant
• CPC Class Codes: C21B 5/007 : Conditions of the cokes or characterised by the cokes used
• CPC Class Codes: C21C 5/52 : Manufacture of steel in electric furnaces C21C5/005 takes precedence; electric heating per se H05B
• CPC Class Codes: C22B 4/02 : Light metals C22B4/005 takes precedence
• CPC Class Codes: H01B 1/04 : mainly consisting of carbon-silicon compounds, carbon or silicon
• 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: Y02E 60/10 : Energy storage using batteries
• CPC Class Codes: Y02P 10/143 : of methane [CH4]
• CPC Class Codes: Y02P 20/129 : Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
• CPC Class Codes: Y02P 20/133 : Renewable energy sources, e.g. sunlight
• CPC Class Codes: Y02P 20/145 : the feedstock being materials of biological origin
• CPC Class Codes: Y02W 10/30 : Wastewater or sewage treatment systems using renewable energies
• CPC Class Codes: Y02W 10/37 : using solar energy

Abstract

This invention provides processes and systems for converting biomass into high carbon biogenic reagents that are suitable for a variety of commercial applications. Some embodiments employ pyrolysis in the presence of an inert gas to generate hot pyrolyzed solids, condensable vapors, and non-condensable gases, followed by separation of vapors and gases, and cooling of the hot pyrolyzed solids in the presence of the inert gas. Additives may be introduced during processing or combined with the reagent, or both. The biogenic reagent may include at least 70 wt %, 80 wt %, 90 wt %, 95 wt %, or more total carbon on a dry basis. The biogenic reagent may have an energy content of at least 12,000 Btu/lb, 13,000 Btu/lb, 14,000 Btu/lb, or 14,500 Btu/lb on a dry basis. The biogenic reagent may be formed into fine powders, or structural objects. The structural objects may have a structure and/or strength that derive from the feedstock, heat rate, and additives.

Claims

1. A process for producing a high-carbon biogenic reagent, the process comprising:

(a) providing a carbon-containing feedstock comprising biomass;

(b) optionally drying the feedstock to remove at least a portion of moisture contained within the feedstock;

(c) optionally deaerating the feedstock to remove at least a portion of interstitial oxygen, if any, contained with the feedstock or the dried feedstock;

(d) in a pyrolysis zone, pyrolyzing the feedstock in the presence of a substantially inert gas for at least 10 minutes and with a pyrolysis temperature selected from about 250°

C. to about 700°

C., to generate hot pyrolyzed solids, condensable vapors, and non-condensable gases;

(e) separating at least a portion of the condensable vapors and at least a portion of the non-condensable gases from the hot pyrolyzed solids;

(f) in a cooling zone, cooling the hot pyrolyzed solids, in the presence of the substantially inert gas for at least 5 minutes and with a cooling zone temperature less than the pyrolysis temperature, to generate warm pyrolyzed solids;

(g) in an optional cooler that is separate from the cooling zone, cooling the warm pyrolyzed solids to generate cool pyrolyzed solids; and

(h) recovering a high-carbon biogenic reagent comprising at least a portion of the cool pyrolyzed solids.

2. The process of claim 1, the process comprising drying the feedstock to remove at least a portion of moisture contained within the feedstock.

3. The process of claim 1, the process comprising deaerating the feedstock to remove at least a portion of interstitial oxygen contained with the feedstock.

4. The process of claim 1, the process further comprising, prior to step (d), preheating the dried feedstock in a preheating zone in the presence of the substantially inert gas for at least 5 minutes and with a preheating temperature selected from about 80°

C. to about 500°

C.

5. The process of claim 4, wherein the preheating temperature is selected from about 80°

C. to about 150°

C.

6. The process of claim 1, wherein the pyrolysis temperature is selected from about 400°

C. to about 600°

C.

7. The process of claim 1, wherein pyrolysis in step (d) is carried out for at least 20 minutes.

8. The process of claim 1, wherein pyrolysis conditions of step (d) are selected to maintain the structural integrity or mechanical strength of the high-carbon biogenic reagent relative to the feedstock.

9. The process of claim 1, wherein the cooling zone temperature is selected from about 150°

C. to about 350°

C.

10. The process of claim 1 or 4, wherein each of the zones is located within a single reactor.

11. The process of claim 1 or 4, wherein each of the zones is located in a separate reactor.

12. The process of claim 1, wherein the substantially inert gas is selected from the group consisting of N₂, Ar, CO, CO₂, H₂, CH₄, and combinations thereof.

13. The process of claim 1, wherein at least some of the substantially inert gas includes one or more non-condensable gas species recycled from step (e).

14. The process of claim 1, wherein the pyrolysis zone and the cooling zone each comprise a gas phase containing less than 5 wt % oxygen.

15. The process of claim 14, wherein the pyrolysis zone and the cooling zone each comprise a gas phase containing about 1 wt % oxygen or less.

16. The process of claim 1 or 4, wherein the process is continuous or semi-continuous.

17. The process of claim 16, wherein the inert gas flows substantially countercurrent relative to the direction of solids flow.

18. The process of claim 16, wherein the inert gas flows substantially concurrent relative to the direction of solids flow.

19. The process of claim 1 or 4, the process further comprising monitoring and controlling the process with at least one reaction gas probe.

20. The process of claim 19, wherein at least two reaction gas probes are utilized to monitor and control the process.

21. The process of claim 19, wherein the monitoring and controlling the process improves process energy efficiency.

22. The process of claim 19, wherein the monitoring and controlling the process improves a product attribute associated with the high-carbon biogenic reagent.

23. The process of claim 22, wherein the product attribute is carbon content.

24. The process of claim 22, wherein the product attribute is energy content.

25. The process of claim 22, wherein the product attribute is structural integrity or mechanical strength.

26. The process of claim 1 or 4, the process further comprising process gas heating of at least a portion of the condensable vapors with an oxygen-containing gas.

27. The process of claim 26, wherein the process gas heating is assisted with combustion of natural gas.

28. The process of claim 26, wherein the process comprises drying the feedstock to remove at least a portion of moisture contained within the feedstock, and wherein heat produced from the process gas heating is utilized, at least in part, for the drying.

29. The process of claim 26, wherein heat produced from the process gas heating is utilized, at least in part, to heat the substantially inert gas.

30. The process of claim 29, wherein at least a portion of the substantially inert gas is heated and then introduced to the pyrolysis zone.

31. The process of claim 1 or 4, the process further comprising combining at least a portion of the condensable vapors, in at least partially condensed form, with the cooled pyrolyzed solids, to increase the carbon content of the high-carbon biogenic reagent.

32. The process of claim 1 or 4, the process further comprising combining at least a portion of the condensable vapors with the warm pyrolyzed solids, to increase the carbon content of the high-carbon biogenic reagent.

33. The process of claim 1, the process further comprising introducing at least one additive selected from acids, bases, or salts thereof.

34. The process of claim 33, wherein the additive is selected from the group consisting of sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, and combinations thereof.

35. The process of claim 1, the process further comprising introducing at least one additive selected from the group consisting of a metal, a metal oxide, a metal hydroxide, a metal halide, and combinations thereof.

36. The process of claim 35, wherein the additive is selected from the group consisting of magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, magnesium oxide, dolomite, dolomitic lime, fluorite, fluorospar, bentonite, calcium oxide, lime, and combinations thereof.

37. The process of claim 33 or 35, wherein the additive is selected to maintain the structural integrity or mechanical strength of the high-carbon biogenic reagent relative to the feedstock.

38. The process of claim 33 or 35, wherein the presence of the additive in the process increases the carbon content of the high-carbon biogenic reagent compared to an otherwise-identical process without introduction of the additive.

39. The process of claim 33 or 35, wherein the presence of the additive in the process increases the energy content of the high-carbon biogenic reagent compared to an otherwise-identical process without introduction of the additive.

40. The process of claim 33 or 35, wherein the additive is introduced prior to or during step (b).

41. The process of claim 33 or 35, wherein the additive is introduced prior to or during step (d).

42. The process of claim 33 or 35, wherein the additive is introduced during step (f), during step (g), between steps (f) and (g), or after step (g).

43. The process of claim 33 or 35, wherein the additive is introduced to the warm pyrolyzed solids.

44. The process of claim 43, wherein the additive is introduced in an aqueous solution, vapor, or aerosol to assist with cooling of the warm pyrolyzed solids in step (g).

45. The process of claim 33 or 35, wherein the additive is introduced to the cool pyrolyzed solids to form the high-carbon biogenic reagent containing the additive.

46. The process of claim 1 or 4, the process further comprising introducing at least a portion of the cool pyrolyzed solids to a separate unit for additional pyrolysis, in the presence of a second substantially inert gas for at least 30 minutes and with a pyrolysis temperature selected from about 200°

C. to about 600°

C., to generate a solid product having higher carbon content than the cool pyrolyzed solids.

47. The process of claim 46, the process further comprising process gas heating of at least a portion of the condensable vapors with an oxygen-containing gas;

wherein heat produced from the process gas heating is utilized, at least in part, to heat the second substantially inert gas prior to introduction to the separate unit for additional pyrolysis.

48. The process of claim 46, wherein the second substantially inert gas is selected from the group consisting of N2, Ar, CO, CO2, H2, CH4, and combinations thereof.

49. The process of claim 46, wherein at least some of the second substantially inert gas includes one or more non-condensable gas species recovered from step (e).

50. The process of either one of claim 2 or 28, the process further comprising operating the cooler to cool the warm pyrolyzed solids with steam, thereby generating the cool pyrolyzed solids and superheated steam;

wherein the drying is carried out, at least in part, with the superheated steam derived from the cooler.

51. The process of claim 50, wherein the cooler is operated to first cool the warm pyrolyzed solids with steam to reach a first cooler temperature, and then with air to reach a second cooler temperature, wherein the second cooler temperature is lower than the first cooler temperature and is associated with a reduced combustion risk for the warm pyrolyzed solids in the presence of the air.

61. The process of claim 1, 52, or 57, wherein the high-carbon biogenic reagent contains at least 35% of the carbon contained in the feedstock.

62. The process of claim 61, wherein the high-carbon biogenic reagent contains at least 50% of the carbon contained in the feedstock.

63. The process of claim 62, wherein the high-carbon biogenic reagent contains at least 70% of the carbon contained in the feedstock.

64. The process of claim 1, 52, or 57, wherein the high-carbon biogenic reagent contains at least 70 wt % carbon on a dry basis.

65. The process of claim 64, wherein the high-carbon biogenic reagent contains at least 80 wt % carbon on a dry basis.

66. The process of claim 65, wherein the high-carbon biogenic reagent contains at least 90 wt % carbon on a dry basis.

67. The process of claim 66, wherein the high-carbon biogenic reagent contains at least 95 wt % carbon on a dry basis.

68. The process of claim 64, wherein the carbon includes fixed carbon and carbon from volatile matter.

69. The process of claim 68, wherein the high-carbon biogenic reagent contains at least 90 wt % fixed carbon on a dry basis.

70. The process of claim 69, wherein the high-carbon biogenic reagent contains at least 95 wt % fixed carbon on a dry basis.

71. The process of claim 1, 52, or 57, wherein the high-carbon biogenic reagent has an energy content of at least 11,000 Btu/lb on a dry basis.

72. The process of claim 71, wherein the high-carbon biogenic reagent has an energy content of at least 12,000 Btu/lb on a dry basis.

73. The process of claim 72, wherein the high-carbon biogenic reagent has an energy content of at least 13,000 Btu/lb on a dry basis.

74. The process of claim 73, wherein the high-carbon biogenic reagent has an energy content of at least 14,000 Btu/lb on a dry basis.

75. The process of claim 74, wherein the high-carbon biogenic reagent has an energy content of at least 14,500 Btu/lb on a dry basis.

76. The process of claim 75, wherein the high-carbon biogenic reagent has an energy content of at least 14,700 Btu/lb on a dry basis.

77. The process of claim 1, 52, or 57, wherein the high-carbon biogenic reagent is formed into a fine powder by particle-size reduction.

78. The process of claim 1, 52, or 57, wherein the high-carbon biogenic reagent is formed into a structural object by pressing, binding, pelletizing, or agglomeration.

79. The process of claim 1, 52, or 57, wherein the high-carbon biogenic reagent is in the form of structural objects whose structure and/or strength substantially derive from the feedstock.

80. The process of claim 79, wherein the high-carbon biogenic reagent is in substantially the same structural form as the feedstock.

81. The process of claim 1, 52, or 57, the process further comprising operating the pyrolysis zone at a pressure of from about 1 kPa to about 101 kPa.

52. A process for producing a high-carbon biogenic reagent, the process comprising:

(a) providing a carbon-containing feedstock comprising dry biomass;

(b) optionally drying the feedstock to remove at least a portion of moisture, if any, contained within the feedstock;

(c) optionally deaerating the feedstock to remove at least a portion of molecular oxygen, if any, contained with the feedstock;

(d) in a preheating zone, preheating the feedstock in the presence of a substantially inert gas for at least 5 minutes and with a preheating temperature selected from about 80°

C. to about 500°

C.;

(e) in a pyrolysis zone, pyrolyzing the feedstock in the presence of a substantially inert gas for at least 10 minutes and with a pyrolysis temperature selected from about 250°

C. to about 700°

C., to generate hot pyrolyzed solids, condensable vapors, and non-condensable gases;

(f) separating at least a portion of the condensable vapors and at least a portion of the non-condensable gases from the hot pyrolyzed solids;

(g) in a cooling zone, cooling the hot pyrolyzed solids, in the presence of the substantially inert gas for at least 5 minutes and with a cooling temperature less than the pyrolysis temperature, to generate warm pyrolyzed solids;

(h) in a cooler that is separate from the cooling zone, cooling the warm pyrolyzed solids to generate cool pyrolyzed solids; and

(i) recovering a high-carbon biogenic reagent comprising at least a portion of the cool pyrolyzed solids;

wherein the process further comprises introducing at least one additive into the process.

53. The process of claim 52, wherein the at least one additive is selected from acids, bases, or salts thereof.

54. The process of claim 53, wherein the at least one additive is selected from the group consisting of sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, and combinations thereof.

55. The process of claim 52, wherein the at least one additive is selected from the group consisting of a metal, a metal oxide, a metal hydroxide, a metal halide, and combinations thereof.

56. The process of claim 55, wherein the at least one additive is selected from the group consisting of magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, magnesium oxide, dolomite, dolomitic lime, fluorite, fluorospar, bentonite, calcium oxide, lime, and combinations thereof.

57. A process for producing a high-carbon biogenic reagent, the process comprising:

(a) providing a carbon-containing feedstock comprising biomass;

(b) optionally drying the feedstock to remove at least a portion of moisture contained within the feedstock;

(c) optionally deaerating the feedstock to remove at least a portion of interstitial oxygen, if any, contained with the feedstock or the dried feedstock;

(d) in a pyrolysis zone, pyrolyzing the feedstock in the presence of a substantially inert gas for at least 10 minutes and with a pyrolysis temperature selected from about 250°

C. to about 700°

C., to generate hot pyrolyzed solids, condensable vapors, and non-condensable gases;

(e) separating at least a portion of the condensable vapors and at least a portion of the non-condensable gases from the hot pyrolyzed solids;

(f) in a cooling zone, cooling the hot pyrolyzed solids, in the presence of the substantially inert gas for at least 5 minutes and with a cooling zone temperature less than the pyrolysis temperature, to generate warm pyrolyzed solids;

(g) in a cooler that is separate from the cooling zone, cooling the warm pyrolyzed solids to generate cool pyrolyzed solids;

(h) recovering a high-carbon biogenic reagent comprising at least a portion of the cool pyrolyzed solids; and

(i) forming a fine powder from the high-carbon biogenic reagent.

58. The process of claim 57, wherein the process includes introducing at least one additive to the process prior to step (i).

59. The process of claim 57, wherein the process includes introducing at least one additive to the high-carbon biogenic reagent during step (i).

60. The process of claim 57, wherein the process includes introducing at least one additive to the high-carbon biogenic reagent after step (i).