Method of removing sulfur dioxide and nitrogen oxides from a gaseous stream

• US 5,785,841 A
• Filed: 04/19/1996
• Issued: 07/28/1998
• Est. Priority Date: 05/04/1995
• Status: Expired due to Fees

• Current Assignee: Carmeuse North America Services Incorporated (Carmeuse Holding SA)
• Original Assignee: Dravo Lime, Inc.
• Inventors: Tseng, Shiaw C.
• Primary Examiner(s): Gorgos, Kathryn L.
• Assistant Examiner(s): Wong, Edna
• Application Number:
  US08/635,330
• Time in Patent Office: 830 Days
• Field of Search: 205/763, 205/770, 423/235, 423/242.3, 423/243.07, 423/244.07
• US Class Current: 205/763
• CPC Class Codes: B01D 53/1425 Regeneration of liquid absorbents
• CPC Class Codes: B01D 53/326 in electrochemical cells
• CPC Class Codes: C25B 11/03 perforated or foraminous
• CPC Class Codes: C25B 11/031 Porous electrodes
• CPC Class Codes: C25B 15/08 Supplying or removing reactants or electrolytes; Regeneration of electrolytes
• CPC Class Codes: C25B 9/19 with diaphragms
• CPC Class Codes: C25C 7/02 Electrodes consumable anodes for the refining the metals C25C1/00 - C25C5/00; Connections thereof

Abstract

A method for removing sulfur dioxide and nitrogen oxides from a gaseous stream using a magnesium-enhanced lime scrubbing slurry containing a ferrous chelate where oxidized ferrous chelate is regenerated by electrochemical treatment. The spent scrubbing solution containing ferric chelates is passed as a catholyte, at an acidic pH of 4.0-6.5 through a cathode compartment while an anolyte solution containing magnesium sulfate, at a pH of 1.5 to 6.5 is passed through an anode compartment, the compartments separated by a microporous separator. An electrical current is passed from the cathode compartment to the anode compartment and ferric chelates are regenerated to ferrous chelates.

Claims

1. In a method of removing sulfur dioxide and nitrogen oxides from a gaseous stream wherein said gaseous stream is contacted with an aqueous scrubbing medium containing sulfites which react with and remove sulfur dioxide therefrom and ferrous chelates which react with and remove nitrogen oxides therefrom to form a spent aqueous scrubbing medium containing solids and a solution of ferric chelates, the improvement comprising:

separating the solids from said spent aqueous scrubbing medium to provide the aqueous solution of ferric chelates;

passing said aqueous solution of ferric chelates as a catholyte, at an acidic pH of 4.0-6.5, to a cathode compartment of an electrochemical cell containing said cathode compartment and an anode compartment separated from said cathode compartment by a separator, said electrochemical cell having a corrosion resistant anode, and an anolyte feed solution in said anode compartment having an acidic pH of 1.5 to 6.5 and containing magnesium sulfate;

passing an electrical current from said cathode compartment to said anode compartment to reduce ferric chelates in said catholyte to ferrous chelates and form a regenerated ferrous chelate solution; and

recycling said regenerated ferrous chelate solution to said contacting step for use as said ferrous chelates.

2. The method of removing sulfur dioxide and nitrogen oxides from a gaseous stream as defined in claim 1 wherein said sulfites which react with and remove sulfur dioxide are selected from the group comprising calcium sulfite, calcium bisulfite, magnesium sulfite, magnesium bisulfite and mixtures thereof.

3. The method of removing sulfur dioxide and nitrogen oxides from a gaseous stream as defined in claim 1 wherein said ferrous chelates are ferrous ethylenediaminetetraacetic acid (ferrous-EDTA).

4. The method of removing sulfur dioxide and nitrogen oxides from a gaseous stream as defined in claim 1 wherein the acidic pH of said catholyte is between 5.0 and 6.0.

5. The method of removing sulfur dioxide and nitrogen oxides from a gaseous stream as defined in claim 1 where the acidic pH of said anolyte feed solution is between 2.0 and 4.0.

6. The method of removing sulfur dioxide and nitrogen oxides from a gaseous stream as defined in claim 1 wherein effluent from said anode compartment is at a pH of greater than 1.5.

7. The method of removing sulfur dioxide and nitrogen oxides from a gaseous stream as defined in claim 1 wherein said cathode compartment contains titanium metal cathodes.

8. The method of removing sulfur dioxide and nitrogen oxides from a gaseous stream as defined in claim 1 wherein said anode compartment contains a corrosion resistant anode comprising a precious metal oxide coated titanium.

9. The method of removing sulfur dioxide and nitrogen oxides from a gaseous stream as defined in claim 1 wherein said separator comprises a synthetic, electrolyte permeable diaphragm.

10. The method of removing sulfur dioxide and nitrogen oxides from a gaseous stream as defined in claim 1 wherein said anolyte feed solution contains between about 1-20 percent magnesium sulfate as MgSO₄.7H₂ O.

11. In a method of removing sulfur dioxide and nitrogen oxides from a gaseous stream wherein said gaseous stream is contacted with an aqueous magnesium-enhanced lime scrubbing medium containing sulfites which react with and remove sulfur dioxide therefrom and ferrous ethylenediaminetetraacetic acid (ferrous EDTA) which react with and remove nitrogen oxides therefrom to form a spent aqueous scrubbing medium containing solids and a solution of ferric ethylenediaminetetraacetic acid (ferric EDTA), the improvement comprising:

separating the solids from said spent aqueous scrubbing medium to provide the aqueous solution of ferric EDTA;

passing said aqueous solution of ferric EDTA as a catholyte, at an acidic pH of 4.0-6.5, to a cathode compartment of an electrochemical cell containing said cathode compartment and an anode compartment separated from said cathode compartment by a microporous separator, said electrochemical cell having a corrosion resistant anode, and an anolyte feed solution in said anode compartment having an acidic pH of 1.5 to 6.5 and containing magnesium sulfate;

passing an electrical current from said cathode compartment to said anode compartment to reduce ferric EDTA in said catholyte to ferrous EDTA and form a regenerated ferrous EDTA solution; and

recycling said regenerated ferrous EDTA solution to said contacting step for use as said ferrous EDTA.

12. The method of removing sulfur dioxide and nitrogen oxides from a gaseous stream as defined in claim 11 wherein the acidic pH of the catholyte is between 5.0 and 6.0 and the acidic pH of the anolyte feed solution is between 2.0 and 4.0.

13. The method of removing sulfur dioxide and nitrogen oxides from a gaseous stream as defined in claim 11 wherein said anode compartment contains a corrosion resistant anode comprising a precious metal oxide coated titanium.

14. The method of removing sulfur dioxide and nitrogen oxides from a gaseous stream as defined in claim 11 wherein said separator comprises a synthetic, electrolyte permeable diaphragm.

15. The method of removing sulfur dioxide and nitrogen oxides from a gaseous stream as defined in claim 11 wherein effluent from said anode compartment is at a pH of greater than 1.5.

16. The method of removing sulfur dioxide and nitrogen oxides from a gaseous stream as defined in claim 11 wherein said anolyte feed solution contains between about 1-20 percent magnesium sulfate as MgSO₄.7H₂ O.