GAS STREAM MULTI-POLLUTANTS CONTROL SYSTEMS AND METHODS

• US 20110226989A9
• Filed: 03/02/2010
• Published: 09/22/2011
• Est. Priority Date: 03/02/2009
• Status: Active Grant

• Current Assignee: Arelac, Inc.
• Original Assignee: Calera Corporation
• Inventors: Seeker, William Randall, Constantz, Brent, Khosla, Vinod
• Granted Patent: US 8,883,104 B2
• Time in Patent Office: Days
• US Class Current: 252/182.33
• CPC Class Codes: B01D 2251/304 of sodium
• CPC Class Codes: B01D 2251/404 of calcium
• CPC Class Codes: B01D 2251/606 Carbonates
• CPC Class Codes: B01D 2257/2045 Hydrochloric acid
• CPC Class Codes: B01D 2257/2047 Hydrofluoric acid
• CPC Class Codes: B01D 2257/302 Sulfur oxides
• CPC Class Codes: B01D 2257/404 Nitrogen oxides other than dinitrogen oxide
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 2257/60 Heavy metals or heavy metal compounds
• CPC Class Codes: B01D 2257/602 Mercury or mercury compounds
• CPC Class Codes: B01D 53/1418 Recovery of products
• CPC Class Codes: B01D 53/44 Organic components
• CPC Class Codes: B01D 53/502 characterised by a specific solution or suspension
• CPC Class Codes: B01D 53/56 Nitrogen oxides B01D53/60 takes precedence
• CPC Class Codes: B01D 53/62 Carbon oxides
• CPC Class Codes: B01D 53/64 Heavy metals or compounds thereof, e.g. mercury
• CPC Class Codes: B01D 53/78 with gas-liquid contact
• CPC Class Codes: Y02C 20/40 of CO2
• CPC Class Codes: Y02E 20/32 Direct CO2 mitigation
• CPC Class Codes: Y10T 436/235 In an aqueous solution [e.g., TOC, etc.]

Abstract

In some embodiments, the invention provides systems and methods for removing carbon dioxide and/or additional components of waste gas streams, comprising contacting the waste gas stream with an aqueous solution, removing carbon dioxide and/or additional components from the waste gas stream, and containing the carbon dioxide and/or additional components, in one form or another, in a composition. In some embodiments, the composition is a precipitation material comprising carbonates, bicarbonates, or carbonates and bicarbonates. In some embodiments, the composition further comprises carbonate and/or bicarbonate co-products resulting from co-processing SOx, NOx, particulate matter, and/or certain metals. Additional waste streams such as liquid, solid, or multiphasic waste streams may be processed as well.

Claims

1. A method of treating an industrial waste gas, wherein the gas comprises carbon dioxide and at least one other component selected from the group consisting of

(a) SOx;

(b) NOx;

(c) a metal;

(d) a non-carbon dioxide acid gas;

(e) an organic; and

(f) particulate matter, comprising contacting the gas with a liquid under conditions adapted to cause at least some of the carbon dioxide and the other component or components to exit the gas and enter the liquid, wherein the method is carried out in a single processor.

2. The method of claim 1, wherein the gas is not pre-treated prior to entering the processor to remove some or all of the carbon dioxide or any of the other components.

3. The method of claim 1, wherein the gas is pre-treated prior to entering the processor to remove particulate matter.

4. The method of claim 1, wherein the gas comprises at least two other components, and wherein the two other components exit the gas and enter the liquid.

5. The method of claim 4, wherein the two other components are SOx and a metal.

6. The method of claim 5 wherein the metal comprises a heavy metal.

7. The method of claim 5, wherein the metal is selected from the group consisting of antimony, arsenic, barium, beryllium, boron, cadmium, chromium, cobalt, copper, lead, manganese, mercury, molybdenum, nickel, radium, selenium, silver, strontium, thallium, vanadium, and zinc.

8. The method of claim 7, wherein the metal is mercury.

9. The method of claim 4, wherein the two other components are SOx and a non-carbon dioxide acid gas.

10. The method of claim 4, wherein the two other components are a metal and a non-carbon dioxide acid gas.

11. The method of claim 4, wherein the two other components are SOx and particulate matter.

12. The method of claim 4, wherein the gas is not pre-treated prior to entering the processor to remove some or all of the carbon dioxide or any of the other components.

13. The method of claim 1, wherein the liquid comprises an aqueous solution.

14. The method of claim 13, wherein the aqueous solution comprises divalent cations.

15. The method of claim 13, further comprising

processing the aqueous solution to produce a composition comprising carbonates, bicarbonates, or a combination thereof, and the other component or a derivative thereof, or the other components and/or derivatives thereof, wherein the carbonates, bicarbonates, or the combination thereof, is at least partially derived from the carbon dioxide.

16. The method of claim 15, wherein the composition comprises a slurry comprising a solid and a supernatant.

17. The method of claim 16, wherein the solid comprises carbonates, bicarbonates, or a combination thereof.

18. The method of claim 17, wherein the solid further comprises the other component or a derivative thereof, or the other components and/or derivatives thereof.

19. The method of claim 16, further comprising separating the solid from the supernatant.

20. The method of claim 17 or 19, wherein the solid, when subjected to a leaching process consisting essentially of

preparing 2×

1 L of an extraction fluid consisting essentially of an aqueous solution of acetic acid, wherein each 1 L of the extraction fluid consists essentially of 5.7 mL acetic acid in deionized water;

grinding the solid such that particles of ground solid are less than 1 cm in the narrowest dimension if the particles are not already less than 1 cm in the narrowest dimension;

placing 100 g of the ground solid into an extraction vessel with 2 L of the extraction fluid to produce an extraction composition;

rotating the extraction vessel in an end-over-end fashion for 18±

2 hours at room temperature;

filtering the extraction composition through borosilicate glass fiber with a pore size of 0.6 μ

m to 0.8 μ

m to produce a leachate; and

adjusting pH of the leachate with 1N nitric acid to a pH of pH 2 or less than pH 2, produces a leachate comprising less than 0.2 mg/L of mercury.

21. The method of claim 20, wherein the leaching process produces a leachate comprising less than 5.0 mg/L arsenic.

22. The method of claim 20, wherein the leaching process produces a leachate comprising less than 100 mg/L barium.

23. The method of claim 20, wherein the leaching process produces a leachate comprising less then 1.0 mg/L cadmium.

24. The method of claim 20, wherein the leaching process produces a leachate comprising less than 5.0 mg/L chromium.

25. The method of claim 20, wherein the leaching process produces a leachate comprising less than 5.0 mg/L lead.

26. The method of claim 20, wherein the leaching process produces a leachate comprising less than 1.0 mg/L selenium.

27. The method of claim 20, wherein the leaching process produces a leachate comprising less than 5.0 mg/L silver.

28. The method of claim 17 or 19, wherein the solid, when subjected to a carbon dioxide release protocol consisting essentially of

grinding the solid such that particles of ground solid are less than 1 cm in the narrowest dimension if the particles are not already less than 1 cm in the narrowest dimension and

immersing the solid in a solution having a pH between pH 4.8 and pH 5.2 and a temperature between 60 and 80°

C. for 48 hours,

produces no more than 5 grams carbon dioxide per 100 grams solid.

29. The method of claim 20, wherein the solid, when subjected to a carbon dioxide release protocol consisting essentially of

grinding the solid such that particles of ground solid are less than 1 cm in the narrowest dimension if the particles are not already less than 1 cm in the narrowest dimension and

immersing the solid in a solution having a pH between pH 4.8 and pH 5.2 and a temperature between 60 and 80°

C. for 48 hours,

produces no more than 5 grams carbon dioxide per 100 grams solid.

30. The method of claim 1, wherein the contacting is carried out under conditions adapted to cause at least 50% of the carbon dioxide and at least 50% of the other component or components to exit the gas and enter the liquid.

62. A composition produced by any method of claims 1-61.

31. A method comprising:

(i) contacting a gas stream with an aqueous solution, wherein the gas stream comprises carbon dioxide and at least one other component selected from the group consisting of

(a) SOx;

(b) NOx;

(c) a metal;

(d) a non-carbon dioxide acid gas;

(e) an organic; and

(f) particulate matter, under conditions adapted to cause at least some of the carbon dioxide and the other component or components to exit the gas stream and enter the aqueous solution; and

(ii) processing the aqueous solution to produce a composition comprising carbonates, bicarbonates, or a combination of carbonates and bicarbonates, and the other component or a derivative thereof, or the other components and/or derivatives thereof, wherein the carbonates, bicarbonates, or the combination of carbonates and bicarbonates, is at least partially derived from the carbon dioxide.

32. The method of claim 31, wherein the other component is selected from the group consisting of SOx, a metal, a non-carbon dioxide acid gas, and an organic.

33. The method of claim 31, wherein the other component is selected from the group consisting of SOx and a metal.

34. The method of claim 31, wherein the gas stream comprises at least two other components and the processing produces a composition comprising carbonates, bicarbonates, or a combination of carbonates and bicarbonates, and the two other components and/or derivatives thereof.

35. The method of claim 34, wherein the two other components are SOx and a metal.

36. The method of claim 35, wherein the metal comprises a heavy metal.

37. The method of claim 35, wherein the metal is selected from the group consisting of antimony, arsenic, barium, beryllium, boron, cadmium, chromium, cobalt, copper, lead, manganese, mercury, molybdenum, nickel, radium, selenium, silver, strontium, thallium, vanadium, and zinc.

38. The method of claim 35, wherein the metal comprises mercury or mercury derivative.

39. The method of claim 31, wherein the gas stream comprises at least three other components and the processing produces a composition comprising carbonates, bicarbonates, or a combination of carbonates and bicarbonates, and the three other components and/or derivatives thereof.

40. The method of claim 39, wherein the three other components are SOx, a metal, and a non-carbon dioxide acid gas.

41. The method of claim 40, wherein the metal comprises mercury or mercury derivative.

42. The method of claim 40 or 41, wherein the non-carbon dioxide acid gas is selected from the group consisting of hydrogen chloride, hydrogen fluoride, and SO₃.

43. The method of claim 39, wherein the three other components are SOx, a metal, and an organic.

44. The method of claim 43, wherein the metal comprises mercury or mercury derivative.

45. The method of claim 31, wherein the composition comprises a solution.

46. The method of claim 31, wherein the composition comprises a slurry comprising a solution and a solid.

47. The method of claim 46, further comprising separating the solid from the solution.

48. The method of claim 47, wherein the solid, when subjected to a leaching process consisting essentially of

preparing 2×

1 L of an extraction fluid consisting essentially of an aqueous solution of acetic acid, wherein each 1 L of the extraction fluid consists essentially of 5.7 mL acetic acid in deionized water;

grinding the solid such that particles of ground solid are less than 1 cm in the narrowest dimension if the particles are not already less than 1 cm in the narrowest dimension;

placing 100 g of the ground solid into an extraction vessel with 2 L of the extraction fluid to produce an extraction composition;

rotating the extraction vessel in an end-over-end fashion for 18±

2 hours at room temperature;

filtering the extraction composition through borosilicate glass fiber with a pore size of 0.6 μ

m to 0.8 μ

m to produce a leachate; and

adjusting pH of the leachate with 1N nitric acid to a pH of pH 2 or less than pH 2, produces a leachate comprising less than 0.2 mg/L of mercury.

49. The method of claim 47 or 48, wherein the solid, when subjected to a carbon dioxide release protocol consisting essentially of

grinding the solid such that particles of ground solid are less than 1 cm in the narrowest dimension if the particles are not already less than 1 cm in the narrowest dimension and

immersing the solid in a solution having a pH between pH 4.8 and pH 5.2 and a temperature between 60 and 80°

C. for 48 hours,

produces no more than 5 grams carbon dioxide per 100 grams solid.

50. The method of claim 31, wherein the gas stream comprises gas produced in an industrial process.

51. The method of claim 50, wherein the gas stream is a waste gas stream.

52. The method of claim 51, wherein the waste gas stream is produced at a power plant, a chemical processing plant, a mechanical processing plant, a refinery, a cement plant, or a steel plant.

53. The method of claim 31, wherein the gas stream is not processed to remove carbon dioxide or the other component or components prior to entering the aqueous solution.

54. The method of claim 53, wherein the gas stream comprises a metal or metal derivative and wherein the gas stream is processed to convert the metal or metal derivative to a form that is more easily taken up by the aqueous solution.

55. The method of claim 31, wherein the non-carbon dioxide acid gas comprises a gas selected from the group consisting of hydrogen chloride, hydrogen fluoride, and SO₃.

56. The method of claim 31, wherein at least 50% of the carbon dioxide and at least 50% of the other component exit the gas and enter the liquid.

57. The method of claim 31, wherein at least 50% of the carbon dioxide and at least 80% of the other component exit the gas and enter the liquid.

58. The method of claim 31, wherein at least 70% of the carbon dioxide and at least 70% of the other component exit the gas and enter the liquid.

59. The method of claim 31, wherein the contacting and processing are carried out sequentially.

60. The method of claim 31, wherein the contacting and processing are carried out simultaneously.

61. The method of claim 31, wherein the contacting and processing are carried out in the same unit.

63. A composition comprising carbonates, bicarbonates, or a combination thereof, and a sulfur-containing compound, wherein the carbonates, bicarbonates, or combination thereof have a relative carbon isotope composition (δ

¹³C) value less than −

5.00‰

, and wherein the composition, when subjected to a leaching process consisting essentially of

preparing 2×

1 L of an extraction fluid consisting essentially of an aqueous solution of acetic acid, wherein each 1 L of the extraction fluid consists essentially of 5.7 mL acetic acid in deionized water;

grinding the solid such that particles of ground solid are less than 1 cm in the narrowest dimension if the particles are not already less than 1 cm in the narrowest dimension;

placing 100 g of the ground solid into an extraction vessel with 2 L of the extraction fluid to produce an extraction composition;

rotating the extraction vessel in an end-over-end fashion for 18±

2 hours at room temperature;

filtering the extraction composition through borosilicate glass fiber with a pore size of 0.6 μ

m to 0.8 μ

m to produce a leachate; and

adjusting pH of the leachate with 1N nitric acid to a pH of pH 2 or less than pH 2, produces a leachate comprising less than 2.0 mg/L of mercury.

64. The composition of claim 63, wherein the leachate comprises less than 1.5 mg/L of mercury.

65. The composition of claim 64, wherein the leachate comprises less than 1.0 mg/L of mercury.

66. The composition of claim 65, wherein the leachate comprises less than 0.5 mg/L of mercury.

67. The composition of claim 66, wherein the leachate comprises less than 0.2 mg/L of mercury.

68. The composition of claim 67, wherein the leachate comprises less than 0.05 mg/L of mercury.

69. The composition of claim 63, wherein the composition comprises mercury, a mercury derivative, or a combination thereof.

70. The composition of claims 69, wherein the relative carbon isotope composition value is less than 10.00‰

.

71. The composition of claim 70, wherein the composition relative carbon isotope composition (δ

¹³C) value less than −

15.00‰

.

72. The composition of claim 71, wherein the composition relative carbon isotope composition (δ

¹³C) value less than −

20.00‰

.

73. The composition of claim 63, wherein the composition comprises at least 90% carbonates.

74. The composition of claim 73, wherein the composition comprises a calcium:

magnesium ratio of 5;

1.

75. The composition of claim 63, wherein the solid, when subjected to a carbon dioxide release protocol consisting essentially of

grinding the solid such that particles of ground solid are less than 1 cm in the narrowest dimension if the particles are not already less than 1 cm in the narrowest dimension and

immersing the solid in a solution having a pH between pH 4.8 and pH 5.2 and a temperature between 60 and 80°

C. for 48 hours,

produces no more than 5 grams carbon dioxide per 100 grams solid.

76. A composition comprising carbonates, bicarbonates, or a combination thereof, and mercury, a mercury derivative, or a combination thereof, wherein the carbonates, bicarbonates, or the combination thereof have a relative carbon isotope composition (δ

¹³C) value less than -5.00‰

, and wherein the composition, when subjected to a leaching process consisting essentially of preparing 2×

1 L of an extraction fluid consisting essentially of an aqueous solution of acetic acid, wherein each 1 L of the extraction fluid consists essentially of 5.7 mL acetic acid in deionized water;

grinding the solid such that particles of ground solid are less than 1 cm in the narrowest dimension if the particles are not already less than 1 cm in the narrowest dimension;

placing 100 g of the ground solid into an extraction vessel with 2 L of the extraction fluid to produce an extraction composition;

rotating the extraction vessel in an end-over-end fashion for 18±

2 hours at room temperature;

filtering the extraction composition through borosilicate glass fiber with a pore size of 0.6 μ

m to 0.8 μ

m to produce a leachate; and

adjusting pH of the leachate with 1N nitric acid to a pH of pH 2 or less than pH 2 produces a leachate comprising less than 2.0 mg/L of mercury.

77. The composition of claim 76, wherein the leachate comprises less than 1.5 mg/L of mercury.

78. The composition of claim 77, wherein the leachate comprises less than 1.0 mg/L of mercury.

79. The composition of claim 78, wherein the leachate comprises less than 0.5 mg/L of mercury.

80. The composition of claim 79, wherein the leachate comprises less than 0.2 mg/L of mercury.

81. The composition of claim 80, wherein the leachate comprises less than 0.05 mg/L of mercury.

82. The composition of claim 76, wherein the composition, when subjected to a carbon dioxide release protocol consisting essentially of

grinding the composition such that particles of ground composition are less than 1 cm in the narrowest dimension if the particles are not already less than 1 cm in the narrowest dimension and

immersing the ground composition in a solution having a pH between pH 4.8 and pH 5.2 and a temperature between 60 and 80°

C. for 48 hours,

produces no more than 5 grams carbon dioxide per 100 grams composition.

83. A composition comprising carbonates, bicarbonates, or a combination thereof, mercury, a mercury derivative, or a combination thereof, and sulfur-containing compound, wherein the composition,

(i) when subjected to a leaching process consisting essentially of

preparing 2×

1 L of an extraction fluid consisting essentially of an aqueous solution of acetic acid, wherein each 1 L of the extraction fluid consists essentially of 5.7 mL acetic acid in deionized water;

grinding the solid such that particles of ground solid are less than 1 cm in the narrowest dimension if the particles are not already less than 1 cm in the narrowest dimension;

placing 100 g of the ground solid into an extraction vessel with 2 L of the extraction fluid to produce an extraction composition;

rotating the extraction vessel in an end-over-end fashion for 18±

2 hours at room temperature;

filtering the extraction composition through borosilicate glass fiber with a pore size of 0.6 μ

m to 0.8 μ

m to produce a leachate; and

adjusting pH of the leachate with 1N nitric acid to a pH of pH 2 or less than pH 2, produces a leachate comprising less than 0.2 mg/L of mercury; and

(ii) when subjected to a carbon dioxide release protocol consisting essentially of

grinding the composition such that particles of ground composition are less than 1 cm in the narrowest dimension if the particles are not already less than 1 cm in the narrowest dimension and

immersing the ground composition in a solution having a pH between pH 4.8 and pH 5.2 and a temperature between 60 and 80°

C. for 48 hours,

produces no more than 5 grams carbon dioxide per 100 grams composition.

84. A system comprising

(i) a source of an industrial waste gas operably connected to

(ii) a processor configured to

(a) process the gas to at least partially remove carbon dioxide from the gas and also to at least partially remove at least one other component from the gas, wherein the other component is selected from the group consisting of SOx, NOx, a metal, particulate matter, a non-carbon dioxide acid gas, and an organic and

(b) produce a composition comprising a product comprising at least a portion of the carbon dioxide, or one or more derivatives thereof, in combination with at least a portion of the other component or one or more derivatives thereof, wherein the composition is suitable for placement in the environment.

85. The system of claim 84, wherein the composition comprises carbonates, bicarbonates, or a combination thereof.

86. The system of claim 84 or 85, wherein the other component is SOx or a metal selected from the group consisting of antimony, arsenic, barium, beryllium, boron, cadmium, chromium, cobalt, copper, lead, manganese, mercury, molybdenum, nickel, radium, selenium, silver, strontium, thallium, thorium, uranium vanadium, and zinc;

particulate matter;

or a combination thereof.

87. The system of claim 86, wherein the composition is suitable for placement in the environment in compliance with Toxicity Characteristic Leaching Procedure, Extraction Procedure Toxicity Test, Synthetic Precipitation Leaching Procedure, California Waste Extraction Test, Soluble Threshold Limit Concentration, American Society for Testing and Materials Extraction Test, Multiple Extraction Procedure, or a combination thereof.

88. The system of claim 87, wherein the composition is suitable for placement in the environment in compliance with Toxicity Characteristic Leaching Procedure.

89. The system of claim 84, wherein the system further comprises a composition conveyor for disposal of at least a portion of the composition.

90. The system of claim 89, wherein the composition conveyor is configured to dispose of at least a portion of the composition underground.

91. The system of claim 84, wherein the processor comprises a gas-liquid contactor, a gas-liquid-solid contactor, a reactor, a settling tank, or a combination thereof.

92. The system of claim 91, wherein the processor is further configured to produce a processed waste gas stream.

93. The system of claim 92, wherein the processed waste gas stream is suitable for placement in the environment in compliance with Reasonably Available Control Technology;

Best Available Control Technology;

Maximum Achievable Control Technology;

Lowest Achievable Emission Rate, or a combination thereof.

94. The system of claim 84, wherein the system further comprises a treatment system.

95. The system of claim 94, wherein the treatment system comprises a liquid-solid separator for concentrating at least a portion of the composition and producing a concentrated composition and a supernatant.

96. The system of claim 95, wherein the supernatant is suitable for placement in the environment.

97. The system of claim 95, wherein the treatment system is configured to recirculate at least a portion of the supernatant back to the processor.

98. The system of claim 95, wherein the concentrated composition is suitable for placement in the environment in compliance with Toxicity Characteristic Leaching Procedure, Extraction Procedure Toxicity Test, Synthetic Precipitation Leaching Procedure, California Waste Extraction Test, Soluble Threshold Limit Concentration, American Society for Testing and Materials Extraction Test, Multiple Extraction Procedure, or a combination thereof.

99. The system of claim 95, wherein the system further comprises a manufacturing system for manufacturing a building material from at least a portion of the concentrated composition.

100. The system of claim 99, wherein the manufacturing system is configured for manufacturing cement, supplementary cementitious material, fine aggregate, mortar, coarse aggregate, concrete, pozzolan, or a combination thereof from the concentrated composition.

101. The system of claim 95, wherein the system further comprises a concentrated composition conveyor for disposal of at least a portion of the concentrated composition.

102. The system of claim 101, wherein the concentrated composition conveyor is configured to dispose of the concentrated composition underground.

103. The system of claim 84, wherein the system further comprises an electrochemical system for producing hydroxide for processing the gas in the processor.

104. The system of claim 103, wherein the electrochemical system comprises an anode and a cathode.

105. The system of claim 104, wherein the hydroxide is produced at the cathode.

106. The system of claim 105, wherein chlorine is not formed at the anode.

107. The system of claim 105, wherein oxygen is not formed at the anode.

108. The system of claim 84, wherein the processor is operably connected to an industrial plant comprising a power plant, a chemical processing plant, a mechanical processing plant, a refinery, a cement plant, or a steel plant.

109. The system of claim 108, wherein a gas conveyor operably connects the processor to the industrial plant.

110. The system of claim 109, wherein the system is configured to be powered down during a period of high demand on the industrial plant.

111. The system of claim 110, wherein the system, the industrial plant, or a combination of the system and the industrial plant remain in compliance with Reasonably Available Control Technology;

Best Available Control Technology;

Maximum Achievable Control Technology;

Lowest Achievable Emission Rate, or a combination thereof.

112. A system comprising:

(i) a source of an industrial waste gas comprising carbon dioxide and one or more other components selected from the group consisting of SOx, NOx, a metal, a non-carbon dioxide acid gas, an organic, and particulate matter;

(ii) a processor configured to remove at least a portion of the carbon dioxide and the other component or components from the gas in a single processing unit; and

(iii) a conduit operably connecting the source of industrial waste gas and the processor, wherein the conduit is configured to direct at least a portion of the industrial waste gas to the processor.

113. The system of claim 112, wherein the system does not comprise a pre-processor between the source of the industrial waste gas and the processor wherein the pre-processor is configured to remove one or more of the other components of the gas before the gas is passed to the processor.

114. The system of claim 112, wherein the gas comprises at least two of the other components and wherein the processor is configured to remove at least a portion of the carbon dioxide and the other components from the gas in a single processing unit.