Three-stage energy-integrated product gas generation method

• US 10,286,431 B1
• Filed: 03/25/2016
• Issued: 05/14/2019
• Est. Priority Date: 03/25/2016
• Status: Active Grant

• Current Assignee: Thermochem Recovery International, Inc.
• Original Assignee: Thermochem Recovery International, Inc.
• Inventors: Chandran, Ravi, Burciaga, Daniel A., Leo, Daniel Michael, Freitas, Shawn Robert, Newport, Dave G., Miller, Justin Kevin, Harrington, Kaitlin Emily, Attwood, Brian Christopher
• Primary Examiner(s): Chandler, Kaity V
• Application Number:
  US16/086,365
• Publication Number:
  US 20190118234A1
• Time in Patent Office: 1,145 Days
• CPC Class Codes: B09B 3/40 involving thermal treatment, e.g. evaporation processes using mineral binders involving a melting or softening step B09B3/29; involving radiation B09B3/50
• CPC Class Codes: B09B 3/45 Steam treatment, e.g. supercritical water gasification or oxidation
• CPC Class Codes: C10B 27/06 Conduit details, e.g. valves
• CPC Class Codes: C10B 3/02 with heat-exchange devices
• CPC Class Codes: C10B 47/04 in shaft furnaces
• CPC Class Codes: C10B 47/18 with moving charge
• CPC Class Codes: C10B 49/16 with moving solid heat-carriers in divided form
• CPC Class Codes: C10B 51/00 Destructive distillation of solid carbonaceous materials by combined direct and indirect heating
• CPC Class Codes: C10B 53/07 of solid raw materials consisting of synthetic polymeric materials, e.g. tyres waste in general, e.g. household waste C10B53/00; recovery or working-up of waste materials of organic macromolecular compounds or compositions based thereon by dry-heat treatment for obtaining partially depolymerised materials C08J11/10; production of liquid hydrocarbon mixtures from rubber or rubber waste C10G1/10
• CPC Class Codes: C10J 2200/00 Details of gasification apparatus
• CPC Class Codes: C10J 2200/15 Details of feeding means
• CPC Class Codes: C10J 2300/0913 Carbonaceous raw material
• CPC Class Codes: C10J 2300/094 Char
• CPC Class Codes: C10J 2300/0956 Air or oxygen enriched air
• CPC Class Codes: C10J 2300/0959 Oxygen
• CPC Class Codes: C10J 2300/1223 by burners
• CPC Class Codes: C10J 2300/1253 by injecting hot gas
• CPC Class Codes: C10J 2300/1861 Heat exchange between at least two process streams
• CPC Class Codes: C10J 2300/1892 with one stream being water/steam
• CPC Class Codes: C10J 3/48 Apparatus; Plants
• CPC Class Codes: C10J 3/503 : for gasifiers with stationary fluidised bed
• CPC Class Codes: C10J 3/54 : Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
• CPC Class Codes: C10J 3/66 : by introducing them into the gasification zone
• CPC Class Codes: C10J 3/721 : Multistage gasification, e.g. plural parallel or serial gasification stages
• CPC Class Codes: C10J 3/86 : combined with waste-heat boilers
• CPC Class Codes: Y02E 20/16 : Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
• 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

Abstract

A multi-stage product gas generation system converts a carbonaceous material, such as municipal solid waste, into a product gas which may subsequently be converted into a liquid fuel or other material. One or more reactors containing bed material may be used to conduct reactions to effect the conversions. Unreacted inert feedstock contaminants present in the carbonaceous material may be separated from bed material using a portion of the product gas. A heat transfer medium collecting heat from a reaction in one stage may be applied as a reactant input in another, earlier stage.

Claims

1. A method for producing a H2, CO, and CO2 from a carbonaceous material using a first reactor, a second reactor, and a third reactor, the method comprising:

(a) reacting carbonaceous material with a steam reactant in the first reactor and producing a first reactor product gas containing char;

(b) introducing at least a portion of the char generated in step (a) into the second reactor;

(c) reacting the char of step (b) with an oxygen-containing gas in the second reactor and producing a second reactor product gas;

(d) transferring the first reactor product gas generated in step (a) and the second reactor product gas generated in step (c) to the third reactor, to form a combined product gas;

(e) reacting the combined product gas with an oxygen-containing gas in the third reactor to generate a third reactor product gas and heat;

(f) transferring heat generated in step (e) to a heat transfer medium contained within a third reactor heat exchanger in thermal contact with the interior of the third reactor;

(g) transferring at least some of the heat transfer medium which has passed through the third reactor heat exchanger, to a second reactor heat exchanger in thermal contact with the interior of the second reactor; and

(h) introducing a first portion of the heat transfer medium which has passed through the second reactor heat exchanger, into the first reactor as the steam reactant of step (a).

2. The method of claim 1, further comprising transferring a second portion of the heat transfer medium which has passed through the second reactor heat exchanger, into the second reactor as a reactant.

3. The method of claim 1, further comprising transferring an oxygen-containing gas to the first reactor, said oxygen-containing gas reacting with the carbonaceous material and the steam.

4. The method of claim 1, further comprising separating char from the first reactor product gas prior to step (b).

5. The method of claim 1, wherein the first reactor product gas of step (a) further comprises H2, CO, CO2, semi-volatile organic compounds (SVOC) and volatile organic compounds (VOC).

6. The method of claim 1, wherein the char in the first reactor product gas has a carbon content of about 10% carbon to about 90% carbon on a weight basis.

7. The method of claim 1, wherein the char in the first reactor product gas has an ash content range from about 90% ash to about 10% ash on a weight basis.

8. The method of claim 1, wherein:

the second reactor product gas of step (c) further comprises solids.

9. The method of claim 8, wherein the solids contained within second reactor product gas comprises about 0% to about 90% carbon on a weight basis.

10. The method of claim 9, wherein the solids contained within second reactor product gas comprises about 5% to about 30% carbon on a weight basis.

11. The method of claim 8, wherein the solids contained within second reactor product gas comprises about 10% to about 100% ash on a weight basis.

12. The method of claim 11, wherein the solids contained within second reactor product gas comprises about 70% to about 95% ash on a weight basis.

13. The method of claim 1, wherein the carbon conversion rate in the first reactor is in the range from about 50% to about 99%.

14. The method of claim 13, wherein the carbon conversion rate in the first reactor is in the range from about 75% to about 95%.

15. The method of claim 1, wherein the second reactor converts into said second reactor product gas, 50% to 99% of the carbon contained within char transferred from the first reactor to the second reactor.

16. The method of claim 1, wherein the first reactor product gas generated in step (a) and the second reactor product gas generated in step (c) are combined, prior to being transferred into the third reactor.

17. The method of claim 1 wherein, in step (e):

the combined product gas includes SVOC, VOC and char from the first reactor product gas, and

said SVOC, VOC and char reacts with said oxygen-containing gas to generate said third reactor product gas and heat.

18. The method of claim 1 wherein, in step (e), the third reactor product gas comprises H2, CO, and CO2.

19. The method of claim 18 wherein, in step (e), the oxygen-containing gas is superstoichiometric.

20. The method of claim 19, comprising combusting the superstoichiometric oxygen-containing gas with a first hydrocarbon stream to produce a first portion of the CO2 in the third reactor product gas.

21. The method of claim 20, wherein the first hydrocarbon stream is natural gas.

22. The method of claim 19, comprising combusting the superstoichiometric oxygen-containing gas with a second hydrocarbon stream to produce a second portion of the CO2 in the third reactor product gas.

23. The method of claim 22, wherein the second hydrocarbon stream comprises naphtha transferred from a downstream Upgrading System.

24. The method of claim 19, comprising combusting the superstoichiometric oxygen-containing gas with a third hydrocarbon stream to produce a third portion of the CO2 in the third reactor product gas.

25. The method of claim 24, wherein the third hydrocarbon stream is an off-gas transferred from a downstream Upgrading System.

26. The method of claim 1, comprising:

combining and combusting together a hydrocarbon stream and an oxygen-containing gas stream in an annulus type burner connected to the third reactor and expelling a combustion stream into the third reactor, the combustion stream including uncombusted oxygen-containing gas;

wherein

all the oxygen-containing gas used in the reaction of step (e) with the combined product gas comprises uncombusted oxygen-containing gas from the combustion stream.

27. The method of claim 26 where the burner accepts a hydrocarbon stream and oxygen-containing gas stream through concentric ports, wherein the oxygen-containing gas is injected into an annular port, and the hydrocarbon stream is injected to the central port.

28. The method of claim 27, wherein the combustion stream exits the nozzle of the burner within the range of 200 feet per minute (ft/m) to the speed of sound.

29. The method of claim 28, wherein the combustion stream exits the nozzle of the burner within the range of about 50 feet per second (ft/s) to about 300 feet per second (ft/s).

30. The method of claim 26, wherein the burner operates as a Helmholtz pulse combustion resonator.

31. The method of claim 30, wherein the combustion stream exits the nozzle of the burner at an average flow velocity greater than 300 ft/s.

32. The method of claim 30, wherein the sound intensity in the burner is within the range of about 110 dB to about 190 dB.

33. The method of claim 26, wherein a portion of the combustion stream exits the burner to contact a portion of the combined product gas.

34. The method of claim 33, wherein the combustion stream reacts with the combined product gas at an average reaction time ranging from about 0.0001 seconds to about 5.0 seconds.

35. The method of claim 1, comprising superheating the heat transfer medium, when it is in the second reactor heat exchanger.

36. The method of claim 35, comprising introducing superheated heat transfer medium into the second reactor to help generate the second reactor product gas.

37. The method of claim 1, wherein:

(i) the first reactor product gas (122) has a first H2 to CO ratio;

(ii) the second reactor product gas (222) has a second H2 to CO ratio;

(iii) the third reactor product gas (322) has a third H2 to CO ratio;

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

(v) the second H2 to CO ratio is greater than the third H2 to CO ratio.

38. The method of claim 1, wherein:

(i) the first reactor product gas (122) has a first CO to CO2 ratio;

(ii) the second reactor product gas (222) has a second CO to CO2 ratio;

(iii) the third reactor product gas (322) has a third CO to CO2 ratio;

(iv) the third CO to CO2 ratio is greater than the second CO to CO2 ratio; and

(v) the second CO to CO2 ratio is greater than the first CO to CO2 ratio.

39. The method of claim 1, further comprising:

combusting a fuel source in a first reactor heat exchanger to form a combustion stream, said combustion stream indirectly heating particulate heat transfer material present in the first reactor.

40. The method of claim 39, further comprising superheating the heat transfer medium which has passed through the third reactor heat exchanger, with heat from the combustion stream.

42. The method according to claim 1, comprising:

operating the first reactor at a first pressure;

operating the second reactor at a second pressure which is lower than the first pressure; and

,

operating the third reactor at a third pressure which is lower than the second pressure.

43. The method of claim 1, comprising providing particulate heat transfer material in the first reactor to promote the reaction between the carbonaceous material and steam.

44. The method according to claim 43, comprising transferring particulate heat transfer material from the second reactor to the first reactor.

45. The method according to claim 43, wherein:

the particulate heat transfer material (105) is comprised of Geldart Group A solids; and

the Geldart Group A solids comprise one or more from the group consisting of inert material, catalyst, sorbent, and engineered particles.

46. The method according to claim 45, wherein the engineered particles comprise one or more from the group consisting of alumina, zirconia, sand, olivine sand, limestone, dolomite, catalytic materials, microballoons, and microspheres.

47. The method according to claim 43, wherein:

the particulate heat transfer material (105) is comprised of Geldart Group B solids;

the Geldart Group B solids comprise one or more from the group consisting of inert material, catalyst, sorbent, and engineered particles.

48. The method according to claim 47, wherein the engineered particles comprise one or more from the group consisting of alumina, zirconia, sand, olivine sand, limestone, dolomite, catalytic materials, microballoons, microspheres, and combinations thereof.

49. The method according to claim 43, wherein:

the particulate heat transfer material (105) is comprised of both Geldart Group A and B solids; and

the Geldart Group A and B solids together comprise one or more from the group consisting of inert material, catalyst, sorbent, and engineered particles.

50. The method according to claim 49, wherein the engineered particles comprise one or more from the group consisting of alumina, zirconia, sand, olivine sand, limestone, dolomite, catalytic materials, microballoons, and microspheres.

51. The method of claim 1, comprising operating the first reactor at a temperature between 320°

C. and 569.99°

C. to endothermically react the carbonaceous material in the presence of steam to produce the first reactor product gas.

52. The method of claim 1, comprising operating the first reactor at a temperature between 570°

C. and 900°

C. to endothermically react the carbonaceous material in the presence of steam to produce the first reactor product gas.

53. The method of claim 1, comprising operating the second reactor at a temperature between 500°

C. and 1,400°

C. to exothermically react the char in the presence of an oxygen-containing gas to produce the second reactor product gas.

54. The method of claim 1, comprising operating the third reactor at a temperature between 1,100°

C. and 1,600°

C. to exothermically react a portion of the first reactor product gas in the presence of an oxygen-containing gas to produce the third reactor product gas.

55. The method of claim 1, wherein the first reactor (100) has a steam to carbonaceous material weight ratio in the range of about 0.125:

1 to about 3;

1.

56. The method of claim 1, wherein the first reactor (100) has a carbon dioxide to carbonaceous material weight ratio in the range of about 0:

1 to about 1;

1.

57. The method of claim 1, wherein the first reactor (100) has an oxygen-containing gas to carbonaceous material weight ratio in the range of about 0:

1 to about 0.5;

1.

58. The method of claim 1, wherein the second reactor (200) has a steam to char-carbon weight ratio in the range of about 0:

1 to about 2.5;

1.

59. The method of claim 1, wherein the second reactor (200) has an oxygen-containing gas to char-carbon weight ratio in the range of about 0:

1 to about 2;

1.

60. The method of claim 1, wherein the second reactor (200) has a carbon dioxide to char-carbon weight ratio in the range of about 0:

1 to about 2.5;

1.

61. The method of claim 1, wherein the first reactor (100) and second reactor (200) operate at a superficial fluidization velocity range between 0.5 ft/s to about 25.0 ft/s.

62. The method of claim 1, wherein the first reactor (100) operates at a superficial fluidization velocity range between 0.6 ft/s to about 1.2 ft/s.

63. The method of claim 62, wherein the first reactor (100) operates at a superficial fluidization velocity range between 0.8 ft/s to about 1 ft/s.

64. The method of claim 1, wherein the second reactor (200) operates at a superficial fluidization velocity range between 0.2 ft/s to about 0.8 ft/s.

65. The method of claim 64, wherein the second reactor (200) operates at a superficial fluidization velocity range between 0.3 ft/s to about 0.5 ft/s.

66. The method of claim 1, comprising providing at least two first reactors in fluid communication with one common third reactor, each first reactor producing first reactor product gas.

67. The method of claim 1, comprising feeding the first reactor with about 500 tons carbonaceous material, per day.

68. The method of claim 1, comprising providing at least two second reactors in fluid communication with one common third reactor, each second reactor producing second reactor product gas.

69. The method of claim 1, further comprising:

equipping at least one of the second reactors with a particulate classification chamber; and

removing agglomerates or inert feedstock contaminants via the particulate classification chamber.

70. A method for converting carbonaceous material into at least one liquid fuel, the method comprising:

(i) combining the carbonaceous material and carbon dioxide in a feedstock delivery system;

(ii) producing a third reactor product gas in accordance with the method of claim 1;

(iii) compressing at least a portion of the third reactor product gas to thereby form a compressed product gas;

(iv) removing carbon dioxide from the compressed product gas, and supplying a first portion of the removed carbon dioxide to the feedstock delivery system for combining with the carbonaceous material in step (i);

(v) reacting the compressed product gas with a catalyst after removing carbon dioxide; and

(vi) synthesizing at least one liquid fuel from the compressed product gas, after reacting the compressed product gas with a catalyst.

71. The method of claim 70 wherein the liquid fuel comprises Fischer-Tropsch Products.

72. The method of claim 70 further comprising, upgrading the liquid fuel into chemical compounds selected from the group consisting of diesel, jet fuel, and naphtha and combinations thereof.

73. The method of claim 72 further comprising, transferring a portion of the naphtha to the third reactor.

41. The method of step 67, comprising introducing the superheated heat transfer medium to a steam turbine having an integrated generator to produce power.