THREE-STAGE ENERGY-INTEGRATED PRODUCT GAS GENERATION METHOD

• US 20190118234A1
• Filed: 03/25/2016
• Published: 04/25/2019
• 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
• Granted Patent: US 10,286,431 B1
• Time in Patent Office: 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

1-27. -27. (canceled)

28. 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;

(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).

29. The method of claim 28, 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.

30. The method of claim 28, further comprising transferring an oxygen-containing gas to the first reactor, said oxygen-containing gas reacting with the carbonaceous material and the steam.

31. The method of claim 28, further comprising separating char from the first reactor product gas prior to step (b).

32. The method of claim 28, wherein the first reactor product gas of step (a) further comprises H2, CO, CO2, semi-volatile organic compounds (SVOC) and volatile organic compounds (VOC).

33. The method of claim 28, 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.

34. The method of claim 28, 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.

35. The method of claim 28, wherein:

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

36. The method of claim 35, wherein the solids contained within second reactor product gas comprises about 0% to about 90% carbon on a weight basis.

37. The method of claim 36, wherein the solids contained within second reactor product gas comprises about 5% to about 30% carbon on a weight basis.

38. The method of claim 35, wherein the solids contained within second reactor product gas comprises about 10% to about 100% ash on a weight basis.

39. The method of claim 38, wherein the solids contained within second reactor product gas comprises about 70% to about 95% ash on a weight basis.

40. The method of claim 28, wherein the carbon conversion rate in the first reactor is in the range from about 50% to about 99%.

41. The method of claim 40, wherein the carbon conversion rate in the first reactor is in the range from about 75% to about 95%.

42. The method of claim 28, 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.

43. The method of claim 28, 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.

44. The method of claim 28 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.

45. The method of claim 28 wherein, in step (e), the third reactor product gas comprises H2, CO, and CO2.

46. The method of claim 45 wherein, in step (e), the oxygen-containing gas is superstoichiometric.

47. The method of claim 46, 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.

48. The method of claim 47, wherein the first hydrocarbon stream is natural gas.

49. The method of claim 46, 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.

50. The method of claim 49, wherein the second hydrocarbon stream comprises naphtha transferred from a downstream Upgrading System.

51. The method of claim 46, 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.

52. The method of claim 51, wherein the third hydrocarbon stream is an off-gas transferred from a downstream Upgrading System.

53. The method of claim 28, 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.

54. The method of claim 53 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.

55. The method of claim 54, 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.

56. The method of claim 55, 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).

57. The method of claim 53, wherein the burner operates as a Helmholtz pulse combustion resonator.

58. The method of claim 57, wherein the combustion stream exits the nozzle of the burner at an average flow velocity greater than 300 ft/s.

59. The method of claim 57, wherein the sound intensity in the burner is within the range of about 110 dB to about 190 dB.

60. The method of claim 53, wherein a portion of the combustion stream exits the burner to contact a portion of the combined product gas.

61. The method of claim 60, 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.

62. The method of claim 28, comprising superheating the heat transfer medium, when it is in the second reactor heat exchanger.

63. The method of claim 62, comprising introducing superheated heat transfer medium into the second reactor to help generate the second reactor product gas.

64. The method of claim 28, 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.

65. The method of claim 28, 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.

66. The method of claim 28, 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.

67. The method of claim 66, further comprising superheating the heat transfer medium which has passed through the third reactor heat exchanger, with heat from the combustion stream.

69. The method according to claim 28, 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.

70. The method of claim 28, comprising providing particulate heat transfer material in the first reactor to promote the reaction between the carbonaceous material and steam.

71. The method according to claim 70, comprising transferring particulate heat transfer material from the second reactor to the first reactor.

72. The method according to claim 70, 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.

73. The method according to claim 72, 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.

74. The method according to claim 70, 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.

75. The method according to claim 74, 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.

76. The method according to claim 70, 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.

77. The method according to claim 76, 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.

78. The method of claim 28, 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.

79. The method of claim 28, 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.

80. The method of claim 28, 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.

81. The method of claim 28, 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.

82. 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 28;

(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.

83. The method of claim 82 wherein the liquid fuel comprises Fischer-Tropsch Products.

84. The method of claim 82 further comprising, upgrading the liquid fuel into chemical compounds selected from the group consisting of diesel, jet fuel, and naphtha and combinations thereof.

85. The method of claim 84 further comprising, transferring a portion of the naphtha to the third reactor.

86. The method of claim 28, 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.

87. The method of claim 28, 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.

88. The method of claim 28, 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.

89. The method of claim 28, 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.

90. The method of claim 28, 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.

91. The method of claim 28, 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.

92. The method of claim 28, 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.

93. The method of claim 28, wherein the first reactor (100) operates at a superficial fluidization velocity range between 0.6 ft/s to about 1.2 ft/s.

94. The method of claim 93, wherein the first reactor (100) operates at a superficial fluidization velocity range between 0.8 ft/s to about 1 ft/s.

95. The method of claim 28, wherein the second reactor (200) operates at a superficial fluidization velocity range between 0.2 ft/s to about 0.8 ft/s.

96. The method of claim 95, wherein the second reactor (200) operates at a superficial fluidization velocity range between 0.3 ft/s to about 0.5 ft/s.

97. The method of claim 28, comprising providing at least two first reactors in fluid communication with one common third reactor, each first reactor producing first reactor product gas.

98. The method of claim 28, comprising feeding the first reactor with about 500 tons carbonaceous material, per day.

99. The method of claim 28, comprising providing at least two second reactors in fluid communication with one common third reactor, each second reactor producing second reactor product gas.

100. The method of claim 28, 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.

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

101. A method for converting municipal solid waste (MSW) into at least one liquid fuel, the MSW containing Geldart Group D inert feedstock contaminants, the method comprising:

(a) combining the MSW and carbon dioxide in a feedstock delivery system;

(b) introducing, into a first interior of a first reactor containing bed material, steam and the combined MSW and carbon dioxide from the feedstock delivery system;

(c) reacting, in the first reactor, the MSW with steam and carbon dioxide, in an endothermic thermochemical reaction to generate a first reactor product gas containing char and leaving unreacted Geldart Group D inert feedstock contaminants in the bed material;

(d) cleaning the bed material with carbon dioxide to remove said unreacted Geldart Group D inert feedstock contaminants;

(e) introducing, into a second reactor containing a second particulate heat transfer material, an oxygen-containing gas and a portion of the char;

(f) reacting, in the second reactor, the char with the oxygen-containing gas, in an exothermic thermochemical reaction to generate a second reactor product gas;

(g) introducing, into a third reactor, an oxygen-containing gas and the first reactor product gas generated in step (c) and the second reactor product gas generated in step (f);

(h) reacting, in the third reactor;

the product gas with the oxygen-containing gas, in an exothermic thermochemical reaction to generate a third reactor product gas;

(i) compressing the first and/or second reactor product gas to thereby form a compressed product gas;

(j) 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 MSW in step (a); and

supplying a second portion of the removed carbon dioxide to clean the bed material in step (d);

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

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

wherein;

the Geldart Group D inert feedstock contaminants comprise whole units and/or fragments of one or more from the group consisting of allen wrenches, ball bearings, batteries, bolts, bottle caps, broaches, bushings, buttons, cable, cement, chains, clips, coins, computer hard drive shreds, door hinges, door knobs, drill bits, drill bushings, drywall anchors, electrical components, electrical plugs, eye bolts, fabric snaps, fasteners, fish hooks, flash drives, fuses, gears, glass, gravel, grommets, hose clamps, hose fittings, jewelry, key chains, key stock, lathe blades, light bulb bases, magnets, metal audio-visual components, metal brackets, metal shards, metal surgical supplies, mirror shreds, nails, needles, nuts, pins, pipe fittings, pushpins, razor blades, reamers, retaining rings, rivets, rocks, rods, router bits, saw blades, screws, sockets, springs, sprockets, staples, studs, syringes, USB connectors, washers, wire, wire connectors, and zippers.

102. A municipal solid waste (MSW) energy recovery system for converting MSW containing inert feedstock contaminants, into a product gas (122), the system comprising:

(a) a first reactor (100) comprising;

a first reactor interior (101) suitable for accommodating a bed material and endothermically reacting MSW in the presence of steam to produce product gas;

a first reactor carbonaceous material input (104) for introducing MSW into the first reactor interior (101);

a first reactor reactant input (108) for introducing steam into the first interior (101);

a first reactor product gas output (124) through which product gas is removed;

a classified recycled bed material input (A27) in fluid communication with an upper portion of the first reactor interior (101);

a particulate output (A2A) connected to a lower portion of the first reactor interior, and through which a mixture of bed material and unreacted inert feedstock contaminants selectively exits the first reactor interior; and

(b) at least one particulate classification vessel (A1A) in fluid communication with the first reactor interior, the vessel comprising;

(i) a mixture input (A5A) connected to the particulate output (A2A), for receiving said mixture from the first reactor interior;

(ii) a classifier gas input (A6A) connected to a source of classifier gas (A16A), for receiving classifier gas to promote separation of said bed material from said unreacted inert feedstock contaminants within said vessel;

(iii) a bed material output (A7A) connected to the classified recycled bed material input (A27) of the first reactor interior (101) via a classifier riser conduit (A17), for returning bed material separated from said mixture to the first reactor interior; and

(iv) a contaminant output (A9A) for removing unreacted inert feedstock contaminants (A19A) which have been separated from said mixture, within the vessel;

wherein;

a mixture transfer valve (V9A) is positioned between the particulate output (A2A) and the mixture input (A5A), to selectively control transfer of said mixture from the first reactor to the vessel;

a gas distributor valve (V91) is positioned to separate the classifier interior (INA) into a classifier zone (INA1) and a gas distribution zone (INA2);

a classification gas transfer valve (V10A) is positioned between the source of classifier gas (A16A) and the classifier gas input (A6A), to selectively provide said classifier gas to the vessel;

a bed material riser recycle transfer valve (V11A) is positioned between the bed material output (A7A) and the classified recycled bed material input (A27), to selectively return bed material separated from said mixture, to the first reactor interior; and

an inert feedstock contaminant drain valve (V13A) configured to selectively remove unreacted inert feedstock contaminants (A19A) which have been separated from said mixture.

103. The system according to claim 102, wherein:

the gas distributor valve (V91) has perforations so as to permit the valve to be in the closed position and still allow (a) classifier gas (A16) to pass up through the valve (V91), and (b) inert feedstock contaminants and bed material to not pass down through the valve.

104. The system of claim 103, wherein perforations in the gas distributor valve (V91) range from about 10 to about 100 microns.

105. The system according to claim 102, wherein:

the vessel further comprises a classifier depressurization gas output (A8A); and

a depressurization vent valve (V12A) connected to the classifier depressurization gas output (A8A) to selectively vent the vessel.

106. The system according to claim 103, further comprising:

a master controller configured to operate the system in any one of a plurality of states, including;

a first state in which the mixture transfer valve (V9A), gas distributor valve (V91), classification gas transfer valve (V10A), bed material riser recycle transfer valve (V11A), and inert feedstock contaminant drain valve (V13A) are closed;

a second state in which the mixture transfer valve (V9A) is open and the remainder of said valves are closed, to allow said mixture to enter the vessel;

a third state in which the classification gas transfer valve (V10A) and the bed material riser recycle transfer valve (V11A) are open and the remainder of said valves are closed, to promote separation of said bed material from said mixture and recycling of separated bed material back into the first reactor;

a fourth state in which the depressurization vent valve (V12A) is open and the remainder of said valves are closed, to allow the vessel to vent; and

a fifth state in which the gas distributor valve (V91) and inert feedstock contaminant drain valve (V13A) are open and the remainder of said valves are closed, to remove unreacted inert feedstock contaminants from the vessel.

107. The system according to claim 106, wherein the classifier gas is carbon dioxide.

108. The system according to claim 107, wherein:

the product gas (122) comprises carbon dioxide; and

a first portion of the carbon dioxide in the product gas (122) is introduced into the vessel as the classifier gas.