Method for removal of SO.sub.2 from gases

• US 4,107,015 A
• Filed: 07/18/1977
• Issued: 08/15/1978
• Est. Priority Date: 07/18/1977
• Status: Expired due to Term

• Current Assignee: The Graver Company
• Original Assignee: Allied Chemical Corporation (Honeywell International Inc.)
• Inventors: Chlanda, Frederick P., Liu, Kang-Jen, Nagasubramanian, Krishnamurthy
• Primary Examiner(s): Prescott, Arthur C.
• Application Number:
  US05/816,566
• Time in Patent Office: 393 Days
• Field of Search: 204/180 P, 204/301, 423/242, 423/519, 423/520, 423/539
• US Class Current: 204/538
• CPC Class Codes: B01D 53/501 by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
• CPC Class Codes: B01D 61/445 with bipolar membranes; Water splitting

Abstract

Removal of sulfur dioxide from an aqueous solution containing the same is effected by subjecting the solution to electrodialytic water splitting. In particular SO₂ is removed from dilute gas streams by means of alkaline solution scrubbing, regeneration of the scrubbing solution and liberation of concentrated SO₂ by means of a membrane water splitter. Waste sulfate produced in the process may be converted to sulfuric acid in a separate membrane water splitter or otherwise processed by conventional means.

Claims

1. Method for direct generation of SO₂ and a liquor which is capable of absorbing SO₂ from an aqueous SO₂ -containing salt solution in which soluble sulfites and bisulfites are present which comprises:

(a) dividing said solution into two streams A and B;

(b) subjecting said streams to electrodialytic water splitting in a two-compartment water splitter comprised of alternating cation and a bipolar module consisting of a combination of anion and cation membranes functioning as a bipolar membrane, wherein one of said streams is introduced into the water splitter compartments between the cation membranes and the anion membranes of the bipolar membrane combination;

(c) introducing the other stream, A, into the compartments of said splitter between the cation sides of said bipolar module and the cation membranes;

(d) passing a direct current through the water splitter thereby effecting the acidification of the stream A and the basicification of the stream B and the transfer of cations from stream A to stream B and producing an aqueous solution comprised of SO₂ derived from stream A and a solution comprised of base capable of absorbing SO₂ derived from stream B.

8. The process of claim 1 comprising the further step of separating the SO₂ from the relatively more acidic effluent of the water splitter by heating the effluent and volatilizing the SO₂.

9. The process of claim 1 comprising the further step of separating the SO₂ from the relatively more acidic effluent of the water splitter by passing air through the stream to remove the SO₂.

10. The process of claim 1 comprising the further step of separating the SO₂ from the more acidic effluent of the water splitter by subjecting it to fractional distillation under pressure to recover liquid SO₂.

11. The process of claim 1 wherein SO₂ is recovered from the relatively more acidic effluent of the water splitter by fractionation under subatmospheric pressure.

12. The process of claim 1 in which a pressure greater than atmospheric is maintained in the water splitter thereby enhancing the solubility of the SO₂.

17. The process of claim 1 wherein the product stream derived from the water splitter is purged of sulfate by evaporating at least a portion of the stream to recover sulfate salt.

2. A method for removing SO₂ from a gas which comprises:

(a) absorbing SO₂ from said gas by contact with a basic aqueous solution thereby forming an aqueous SO₂ -containing salt solution in which soluble sulfites and bisulfites are present;

(b) dividing said solution into two streams A and B;

(c) subjecting said streams to electrodialytic water splitting in a two-compartment water splitter comprised of alternating cation and a bipolar module consisting of a combination of anion and cation membranes functioning as a bipolar membrane, wherein one of said streams is introduced into the water splitter compartments between the cation membranes and the anion membranes of the bipolar membrane combination;

(d) introducing the other stream, A, into the compartments of said splitter between the cation sides of the bipolar module and the cation membranes;

(e) passing a direct current through the water splitter thereby effecting the acidification of the stream A and the basicification of the stream B and the transfer of cations from stream A to stream B and producing an aqueous solution comprised of SO₂ derived from stream A and a solution comprised of base capable of absorbing SO₂ derived from stream B.

3. The process of claim 2 in which the absorbing solution contains as a source of supporting electrolyte, a salt selected from the group consisting of sodium, potassium and ammonium.

4. The process of claim 3 in which the supporting electrolyte salt is a sulfate.

5. The process of claim 2 in which the gas from which SO₂ has been derived is the combustion gas from a boiler which burns a sulfur containing fuel.

6. The process of claim 2 in which the gas from which SO₂ is removed is the effluent from a sulfuric acid plant.

7. The process of claim 2 in which the gas from which SO₂ is removed is the effluent from a smelter.

13. The process of claim 2 in which sulfate produced by oxidation of sulfite is purged from the water splitter effluent subsequent to removal of SO₂ by subjecting the sulfate stream from which SO₂ has been removed to water splitting in a three-compartment water splitting unit containing cation, anion and a combination of cation and anion membranes which function as a bipolar membrane to generate H₂ SO₄ and base.

14. The process of claim 2 in which sulfate produced by oxidation of sulfite is purged, in the case of a weak base scrubbing solution, by subjecting the water splitter effluent subsequent to removal of SO₂, to water splitting in a two-compartment water splitter containing alternating combinations of cation and anion membranes functioning as bipolar membranes and anion membranes to produce sulfuric acid and base streams.

15. The process of claim 2 in which the sulfate from the water splitter effluent stream after removal of SO₂ is converted, by subjecting this stream, to water splitting in a two-compartment water splitter containing alternating cation and combinations of cation and anion membranes functioning as bipolar membranes, to bisulfate and base streams.

16. The process of claim 15 in which the bisulfate stream is subsequently treated with a base, selected from calcium and barium that forms an insoluble sulfate, to effect a conversion of the bisulfate to calcium sulfate and soluble sulfate and lessening the respective residual calcium or barium concentration in solution by further treatment of the solution with a carbonate or sulfite.

18. The process of claim 4 in which the water splitting is effected until the scrubbing solution contains HSO₄^-, followed by the separation of SO₂ from the water splitter product stream, followed by removal of the SO₂ and subsequent treatment of the stream from which SO₂ has been extracted with calcium base to produce calcium sulfate and soluble sulfate and lessening the calcium concentration in solution by further treatment of the solution with a carbonate or sulfite.

20. The process of claim 15 in which the soluble sulfate is selected from the group of Na₂ SO₄, K₂ SO₄, and (NH₄)₂ SO₄ and the base generated comprises a product selected from the group consisting of NaOH, KOH, NH₄ OH, a mixture of NaOH/Na₂ SO₃, KOH/K₂ SO₃, NH₄ OH/(NH₄)₂ SO₃, Na₂ SO₃, K₂ SO₃ or (NH₄)₂ SO₃, a mixture of Na₂ SO₃ /NaHSO₃, K₂ SO₃ /KHSO₃ or (NH₄)₂ SO₃ /NH₄ HSO₃ and the calcium base is lime or limestone.

19. A process for converting a soluble sulfate to insoluble CaSO₄ and base by subjecting an aqueous solution of the soluble sulfate to treatment in a two-compartment water splitter containing combinations of cation and anion membranes functioning as a bipolar membrane and cation membranes, converting at least a portion of the soluble sulfate to the bisulfate, thereby also generating a base, thereafter treating the acidified stream with a calcium base to form insoluble CaSO₄ and soluble sulfate and recycling said soluble sulfate to the water splitter.