Method for producing a product gas having component gas ratio relationships

• US 10,350,574 B2
• Filed: 09/10/2018
• Issued: 07/16/2019
• Est. Priority Date: 10/24/2017
• Status: Active Grant

• Current Assignee: Thermochem Recovery International, Inc.
• Original Assignee: Thermochem Recovery International, Inc.
• Inventors: Chandran, Ravi, Newport, Dave G., Burciaga, Daniel A., Leo, Daniel Michael, Miller, Justin Kevin, Harrington, Kaitlin Emily, Attwood, Brian Christopher
• Primary Examiner(s): Seifu, Lessanework
• Application Number:
  US16/126,207
• Publication Number:
  US 20190118157A1
• Time in Patent Office: 309 Days
• CPC Class Codes: B01J 19/20 in the form of helices, e.g. screw reactors
• CPC Class Codes: B01J 19/245 placed in series
• CPC Class Codes: B01J 2219/00162 controlling the pressure
• CPC Class Codes: B01J 2219/00164 controlling the flow
• CPC Class Codes: B01J 2219/24 Stationary reactors without moving elements inside
• CPC Class Codes: B01J 4/001 Feed or outlet devices as such, e.g. feeding tubes
• CPC Class Codes: B01J 4/007 provided with moving parts
• CPC Class Codes: B01J 8/0045 by means of a rotary device in the flow channel
• CPC Class Codes: C10G 2/30 from carbon monoxide with hydrogen
• CPC Class Codes: C10G 2/34 Apparatus, reactors
• CPC Class Codes: C10J 2200/154 Pushing devices, e.g. pistons
• CPC Class Codes: C10J 2200/158 Screws
• CPC Class Codes: C10J 3/007 Screw type gasifiers
• CPC Class Codes: C10J 3/721 Multistage gasification, e.g. plural parallel or serial gasification stages
• CPC Class Codes: C10J 3/723 Controlling or regulating the gasification process
• CPC Class Codes: Y02E 20/16 Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
• CPC Class Codes: Y02E 50/30 Fuel from waste, e.g. synthetic alcohol or diesel

Abstract

A liquid fuel product system is configured to produce liquid fuels from carbonaceous materials. The liquid fuel product system includes a plurality of feedstock delivery systems, a plurality of first stage product gas generation systems, a plurality of second stage product gas generation systems, a plurality of third stage product gas generation systems, a primary gas clean-up system, a compression system, a secondary gas clean-up system, and a synthesis system that includes one or more from the group consisting of ethanol, mixed alcohols, methanol, dimethyl ether, and Fischer-Tropsch products.

Claims

1. A method of producing a third reactor product gas, the method comprising:

(a) providing a source of carbonaceous material including one or more materials selected from the group consisting of agricultural residues, agro-industrial residues, animal waste, biomass, cardboard, coal, coke, energy crops, farm slurries, fishery waste, food waste, fruit processing waste, lignite, municipal solid waste, paper, paper mill residues, paper mill sludge, paper mill spent liquors, plastic, refuse derived fuel, sewage sludge, tires, urban waste, wood products, wood wastes, and combinations thereof;

(b) after step (a), reacting the carbonaceous material with steam to produce a first reactor product gas having a first H₂ to CO ratio and a first CO to CO₂ ratio;

(c) after step (b), substoichiometrically oxidizing at least a portion of the first reactor product gas to form a second reactor product gas having a second H₂ to CO ratio and a second CO to CO₂ ratio;

(d) after step (c), mixing the first reactor product gas and second reactor product gas to form a combined product gas; and

(e) after step (d), reacting the combined product gas with an oxygen-containing gas to produce a third reactor product gas having a third H₂ to CO ratio and a third CO to CO₂ ratio;

wherein;

(I) the first H₂ to CO ratio is greater than the second H₂ to CO ratio;

(II) the second CO to CO₂ ratio is greater than the first CO to CO₂ ratio;

(III) the third H₂ to CO ratio is lower than both the first H₂ to CO ratio and the second H₂ to CO ratio; and

(IV) the third CO to CO₂ ratio is greater than both the first CO to CO₂ ratio and the second CO to CO₂ ratio.

2. The method according to claim 1, comprising, in step (b):

steam reforming the carbonaceous material to produce CO, and subjecting the CO to a water gas shift reaction to produce CO₂.

3. The method according to claim 2, comprising:

steam reforming the carbonaceous material at a superficial fluidization velocity ranging between 0.6 ft/s to 25 ft/s.

4. The method according to claim 2, comprising,

in step (c), substoichiometrically oxidizing char present in the first reactor product gas to thereby form excess heat in addition to said second reactor product gas, and heating steam with the excess heat to form heated steam;

and

using at least a portion of the heated steam as a steam reforming reactant.

5. The method according to claim 1, comprising,

in step (c), substoichiometrically oxidizing char present in the first reactor product gas to thereby form excess heat in addition to said second reactor product gas, and heating a particulate heat transfer material with the excess heat to form a heated particulate heat transfer material;

and using at least a portion of the heated particulate heat transfer material to promote the reaction of step (b).

6. The method according to claim 1, further comprising:

after step (a) and before step (b), analyzing the carbonaceous material to determine one or more parameters selected from the group consisting of mass flow rate, ultimate analysis, proximate analysis, energy content, and water content.

7. The method according to claim 1, further comprising:

analyzing the carbonaceous material with one or more sensors selected from the group consisting of an optical sensor, an x-ray sensor, and a proximity sensor.

8. The method according to claim 1, further comprising:

in step (e), reacting the combined product gas with a hydrocarbon stream including one or more selected from the group consisting of Fischer Tropsch tail gas, natural gas, naphtha, product gas, landfill gas, and combinations thereof.

9. The method according to claim 1, further comprising:

in step (b), heating at least a portion of the carbonaceous material with a heat exchanger to produce the first reactor product gas;

wherein;

the heat exchanger includes one or more selected from the group consisting of a pulse heater, tailpipes, electrical heater rods in thermowells, fuel cells, heat pipes, fire-tubes, annulus-type heat exchangers, radiant tubes, and combinations thereof.

10. The method according to claim 1, wherein:

the first reactor product gas of step (b) further comprises semi-volatile organic compounds (SVOC) and volatile organic compounds (VOC).

11. The method according to claim 1, further comprising:

(f) after step (e), reducing the temperature of the third reactor product gas to form a reduced-temperature product gas;

(g) after step (f), removing water from the reduced-temperature product gas to form a water-depleted product gas which has a reduced amount of water relative to the reduced-temperature product gas;

(h) after step (g), increasing the pressure of the water-depleted product gas to form a compressed product gas which has a pressure greater than the water-depleted product gas;

(i) after step (h), removing carbon dioxide from the compressed product gas to form a carbon-dioxide-depleted-product-gas which has a reduced amount of carbon dioxide relative to the compressed product gas; and

(j) after step (i), catalytically synthesizing a synthesis product from the carbon-dioxide-depleted-product-gas, the synthesis product includes one or more products selected from the group consisting of ethanol, mixed alcohols, methanol, dimethyl ether, and Fischer-Tropsch products.

12. The method according to claim 11, further comprising:

combining at least a portion of the carbon dioxide removed in step (i) with the carbonaceous material.

13. The method according to claim 12, further comprising:

reducing the temperature of the carbon dioxide, prior to combining the carbon dioxide with the carbonaceous material.

14. The method according to claim 13, further comprising:

after reducing the temperature of the carbon dioxide, removing water from the carbon dioxide, prior to combining the carbon dioxide with the carbonaceous material.

15. A method of making a synthesis product selected from the group consisting of ethanol, mixed alcohols, methanol, dimethyl ether, and Fischer-Tropsch products, and mixtures thereof, the method comprising:

forming a third reactor product gas in accordance with steps (a)-(e) of claim 1; and

then;

(f) after step (e), reducing the temperature of the third reactor product gas to form a reduced-temperature product gas;

(g) after step (f), removing water from the reduced-temperature product gas to form a water-depleted product gas which has a reduced amount of water relative to the reduced-temperature product gas;

(h) after step (g), increasing the pressure of the water-depleted product gas to form a compressed product gas which has a pressure greater than the water-depleted product gas;

(i) after step (h), removing carbon dioxide from the compressed product gas to form a carbon-dioxide-depleted-product-gas which has a reduced amount of carbon dioxide relative to the compressed product gas; and

(j) after step (i), catalytically synthesizing the synthesis product from the carbon-dioxide-A depleted-product-gas.

16. A method of making a synthesis product selected from the group consisting of ethanol, mixed alcohols, methanol, dimethyl ether, and Fischer-Tropsch products, and mixtures thereof, the method comprising:

(a) providing a source of carbonaceous material including one or more materials selected from the group consisting of agricultural residues, agro-industrial residues, animal waste, biomass, cardboard, coal, coke, energy crops, farm slurries, fishery waste, food waste, fruit processing waste, lignite, municipal solid waste, paper, paper mill residues, paper mill sludge, paper mill spent liquors, plastic, refuse derived fuel, sewage sludge, tires, urban waste, wood products, wood wastes, and combinations thereof;

(b) after step (a), reacting the carbonaceous material with both steam and carbon dioxide to produce a first reactor product gas having a first H₂ to CO ratio and a first CO to CO₂ ratio;

(c) after step (b), substoichiometrically oxidizing at least a portion of the first reactor product gas to form a second reactor product gas having a second H₂ to CO ratio and a second CO to CO₂ ratio;

(d) after step (c), mixing the first reactor product gas and second reactor product gas to form a combined product gas;

(e) after step (d), reacting the combined product gas with an oxygen-containing gas to produce a third reactor product gas having a third H₂ to CO ratio and a third CO to CO₂ ratio;

(f) after step (e), reducing the temperature of the third reactor product gas to form a reduced-temperature product gas;

(g) after step (f), removing water from the reduced-temperature product gas to form a water-depleted product gas which has a reduced amount of water relative to the reduced-temperature product gas;

(h) after step (g), increasing the pressure of the water-depleted product gas to form a compressed product gas which has a pressure greater than the water-depleted product gas;

(i) after step (h), removing carbon dioxide from the compressed product gas to form a carbon-dioxide-depleted-product-gas which has a reduced amount of carbon dioxide relative to the compressed product gas; and

(j) after step (i), catalytically synthesizing the synthesis product from the carbon-dioxide-depleted-product-gas;

wherein;

(I) the first H₂ to CO ratio is greater than the second H₂ to CO ratio;

(II) the second CO to CO₂ ratio is greater than the first CO to CO₂ ratio;

(III) the third H₂ to CO ratio is lower than both the first H₂ to CO ratio and the second H₂ to CO ratio; and

(IV) the third CO to CO₂ ratio is greater than both the first CO to CO₂ ratio and the second CO to CO₂ ratio.

17. The method according to claim 16, comprising, in step (b):

steam reforming the carbonaceous material to produce CO.

18. The method according to claim 17, comprising:

steam reforming the carbonaceous material at a superficial fluidization velocity ranging between 0.6 ft/s to 25 ft/s.

19. The method according to claim 17, comprising,

in step (c), substoichiometrically oxidizing char present in the first reactor product gas to thereby form excess heat in addition to said second reactor product gas, and heating steam with the excess heat to form heated steam;

and

using at least a portion of the heated steam as a steam reforming reactant.

20. The method according to claim 16, comprising,

in step (c), substoichiometrically oxidizing char present in the first reactor product gas to thereby form excess heat in addition to said second reactor product gas, and heating a particulate heat transfer material with the excess heat to form a heated particulate heat transfer material;

and using at least a portion of the heated particulate heat transfer material to promote the reaction of step (b).

21. The method according to claim 16, further comprising:

after step (a) and before step (b), analyzing the carbonaceous material to determine one or more parameters selected from the group consisting of mass flow rate, ultimate analysis, proximate analysis, energy content, and water content.

22. The method according to claim 16, further comprising:

analyzing the carbonaceous material with one or more sensors selected from the group consisting of an optical sensor, an x-ray sensor, and a proximity sensor.

23. The method according to claim 16, further comprising:

in step (e), reacting the combined product gas with a hydrocarbon stream including one or more selected from the group consisting of Fischer Tropsch tail gas, natural gas, naphtha, product gas, landfill gas, and combinations thereof.

24. The method according to claim 16, further comprising:

in step (b), heating at least a portion of the carbonaceous material with a heat exchanger to produce the first reactor product gas;

wherein;

the heat exchanger includes one or more selected from the group consisting of a pulse heater, tailpipes, electrical heater rods in thermowells, fuel cells, heat pipes, fire-tubes, annulus-type heat exchangers, radiant tubes, and combinations thereof.

25. The method according to claim 16, wherein:

the first reactor product gas of step (b) further comprises semi-volatile organic compounds (SVOC) and volatile organic compounds (VOC).

26. The method according to claim 16, further comprising:

combining at least a portion of the carbon dioxide removed in step (i) with the carbonaceous material.

27. The method according to claim 26, further comprising:

reducing the temperature of the carbon dioxide, prior to combining the carbon dioxide with the carbonaceous material.

28. The method according to claim 27, further comprising:

after reducing the temperature of the carbon dioxide, removing water from the carbon dioxide, prior to combining the carbon dioxide with the carbonaceous material.