Methods and apparatus for enhancing the energy content of carbonaceous materials from pyrolysis

• US 10,611,977 B2
• Filed: 11/03/2017
• Issued: 04/07/2020
• 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:
  US15/802,716
• Publication Number:
  US 20180127672A1
• Time in Patent Office: 886 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

Processes and systems for converting biomass into high-carbon biogenic reagents that are suitable for a variety of commercial applications. Pyrolysis in the presence of an inert gas is employed 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) in a pyrolysis zone, pyrolyzing the feedstock in the presence of a substantially inert gas for at least 10 minutes at a pyrolysis temperature from about 250°

C. to about 700°

C., thereby generating hot pyrolyzed solids, condensable vapors, and non-condensable gases;

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

(d) in a cooling zone, cooling the hot pyrolyzed solids, in the presence of the substantially inert gas for at least 5 minutes at a cooling temperature less than the pyrolysis temperature, thereby generating warm pyrolyzed solids;

(e) subsequently passing at least a portion of the condensable vapors and/or at least a portion of the non-condensable gases from step (c) across the warm pyrolyzed solids, thereby forming enhanced pyrolyzed solids with increased carbon content; and

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

2. The process of claim 1, further comprising drying the feedstock to remove at least a portion of moisture contained within the feedstock to thereby produce dried feedstock, and/or deaerating the dried feedstock to remove at least a portion of interstitial oxygen contained within the feedstock to thereby produce deaerated feedstock.

3. The process of claim 1, further comprising, in step (e), passing:

at least a portion of the condensable vapors from step (c), in vapor and/or condensed form, across the warm pyrolyzed solids, thereby producing enhanced pyrolyzed solids with increased carbon and/or energy content;

at least a portion of the non-condensable gases from step (c) across the warm pyrolyzed solids, thereby producing enhanced pyrolyzed solids with increased carbon and/or energy content; and

/or

at least a portion of the condensable vapors from step (c), in vapor and/or condensed form, across the cool pyrolyzed solids, thereby producing enhanced pyrolyzed solids with increased carbon and/or energy content.

4. The process of claim 1, further comprising recovering energy from the condensable vapors and/or from the non-condensable gases for use in the process.

5. The process of claim 1, further comprising introducing an intermediate feed stream comprising at least a portion of the condensable vapors and at least a portion of the non-condensable gases, obtained from step (c), to a separation unit configured to generate a first output stream and a second output stream.

6. The process of claim 1, further comprising introducing into the process an additive.

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

8. The process of claim 1, wherein the pyrolysis temperature is from about 350°

C. to about 600°

C.

9. The process of claim 1, further comprising pyrolyzing the feedstock in the presence of a substantially inert gas from about 0.5 hours to about 4 hours.

10. The process of claim 1, further comprising pyrolyzing the feedstock in the presence of a substantially inert gas for about 2 hours, and wherein the pyrolysis temperature is about 600°

C.

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

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

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

C. to about 700°

C., thereby generating hot pyrolyzed solids, condensable vapors, and non-condensable gases;

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

(d) in a cooling zone, cooling the hot pyrolyzed solids, in the presence of the substantially inert gas for at least 5 minutes at a cooling temperature less than the pyrolysis temperature, thereby generating warm pyrolyzed solids;

(e) in a cooler, cooling the warm pyrolyzed solids to generate cool pyrolyzed solids;

(f) subsequently passing at least a portion of the condensable vapors and/or at least a portion of the non-condensable gases from step (c) across the warm pyrolyzed solids and/or the cool pyrolyzed solids, thereby forming enhanced pyrolyzed solids with increased carbon content; and

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

12. The process of claim 11, further comprising drying the feedstock to remove at least a portion of moisture contained within the feedstock to thereby produce dried feedstock, and/or deaerating the dried feedstock to remove at least a portion of interstitial oxygen contained within the feedstock to thereby produce deaerated feedstock.

13. The process of claim 11, further comprising, in step (e), passing:

at least a portion of the condensable vapors from step (c), in vapor and/or condensed form, across the warm pyrolyzed solids, thereby producing enhanced pyrolyzed solids with increased carbon and/or energy content;

at least a portion of the non-condensable gases from step (c) across the warm pyrolyzed solids, thereby producing enhanced pyrolyzed solids with increased carbon and/or energy content;

at least a portion of the condensable vapors from step (c), in vapor and/or condensed form, across the cool pyrolyzed solids, thereby producing enhanced pyrolyzed solids with increased carbon and/or energy content

at least a portion of the non-condensable gases from step (c) across the cool pyrolyzed solids, thereby producing enhanced pyrolyzed solids with increased carbon and/or energy content;

substantially all of the condensable vapors from step (c), in vapor and/or condensed form, across the cool pyrolyzed solids, thereby producing enhanced pyrolyzed solids with increased carbon and/or energy content;

substantially all of the non-condensable gases from step (c) across the cool pyrolyzed solids, thereby producing enhanced pyrolyzed solids with increased carbon content.

14. The process of claim 11, further comprising recovering energy from the condensable vapors and/or from the non-condensable gases for use in the process.

15. The process of claim 11, further comprising introducing an intermediate feed stream comprising at least a portion of the condensable vapors and at least a portion of the non-condensable gases, obtained from step (c), to a separation unit configured to generate a first output stream and a second output stream.

16. The process of claim 11, further comprising introducing into the process an additive.

17. The process of claim 11, further comprising monitoring and controlling the process with at least one reaction gas probe or with at least two reaction gas probes.

18. The process of claim 11, wherein the pyrolysis temperature is from about 350°

C. to about 600°

C.

19. The process of claim 11, further comprising pyrolyzing the feedstock in the presence of a substantially inert gas from about 0.5 hours to about 4 hours.

20. The process of claim 11, further comprising pyrolyzing the feedstock in the presence of a substantially inert gas for about 2 hours, and wherein the pyrolysis temperature is about 600°

C.