Method and apparatus for capturing carbon dioxide and producing sulfuric acid by sodium bisulfate

Abstract

The present invention refers to the field of flue gas purification, which discloses a method and apparatus for capturing carbon dioxide and producing sulfuric acid by sodium bisulfate; using a three-format electrodialysis apparatus to convert the desulfurized by-product NaHSO.sub.4 into H.sub.2SO.sub.4 while capturing CO.sub.2 in the flue gas in the cathode chamber. Under the action of electric field drive and ion exchange membrane, HSO.sub.4.sup.− enters the anode chamber to generate H.sub.2SO.sub.4 and is concentrated, and Na.sup.+ enters the cathode chamber to generate NaOH; the flue gas containing CO.sub.2 to be treated is introduced from the cathode chamber and absorbed by NaOH. The invention provides a simple, green, and economic proceeding method to capture the carbon dioxide in the flue gas during the comprehensive utilization of sodium bisulfate solution, which is of better environmental benefits and improvement of the flue gas treatment technology and reducing the pressure of desulfurization gypsum treatment.

Claims

1. An apparatus for producing sulfuric acid from desulfurized products, wherein the apparatus comprises an anode plate, an ion exchange membrane and a cathode plate; the anode plate and the anion exchange membrane form an anode chamber; the cathode plate and the cation exchange membrane cathode chamber; an intermediate chamber is formed between the cation exchange membrane and the anion exchange membrane; wherein the anode chamber, the cathode chamber, and the intermediate chamber comprise at least one liquid circulation tube; the anode chamber and/or the cathode chamber further comprise(s) one or more exhaust ports; the intermediate chamber is used for the storage of the desulfurized products.

2. The apparatus for producing sulfuric acid from desulfurized products of claim 1, wherein the anode chamber, the cathode chamber and the intermediate chamber comprise two or more liquid circulation tubes.

3. The apparatus for producing sulfuric acid from desulfurized products of claim 1, wherein at least one liquid circulation tube is arranged on the cathode plate and/or the anode plate.

4. The apparatus for producing sulfuric acid from desulfurized products of claim 1, wherein the cathode chamber is provided with a flue gas inlet, and the flue gas inlet is provided with an aeration device.

5. The apparatus for producing sulfuric acid from desulfurized products of claim 4, wherein the aeration device is an aeration stone and/or an aeration sieve plate.

6. The apparatus for producing sulfuric acid from desulfurized products of claim 1, wherein the apparatus further comprises a DC power supply, a desulfurized product liquid circulation tank, a cathode chamber liquid circulation tank, a circulation pump I and a circulation pump II; the DC power supply is electrically connected to the polar plate of the apparatus; one end of the circulation pump I is connected with the liquid circulation tube of the intermediate chamber, the other end of the circulation pump I is connected with the desulfurized product liquid circulation tank, and the desulfurized product liquid circulation tank is connected with the liquid circulation tube of the intermediate chamber simultaneously; one end of the circulation pump II is connected with the liquid circulation tube of the cathode chamber, the other end of the circulation pump II is connected with the liquid circulation tank of the cathode chamber, and the liquid circulation tank of the cathode chamber is connected with the liquid circulation tube of the cathode chamber simultaneously.

7. A method for producing sulfuric acid from desulfurized products, wherein the method applies to the apparatus of claim 1; on the basis of electric field driving and ion selective passage of ion exchange membrane, the sulfur-containing anion of the intermediate chamber selectively enters the anode chamber to generate sulfuric acid.

8. The method for producing sulfuric acid from desulfurized products of claim 7, wherein the cation in the intermediate chamber selectively enters the cathode chamber to generate an alkaline substance; the alkaline substance can be used for capturing acid gas.

9. The method for producing sulfuric acid from desulfurized products of claim 7, wherein desulfurized product liquid in the intermediate chamber is a solution containing sulfate and/or sulfite ions, and the desulfurized product liquid is one or more of NaHSO4, Na2SO4, Na2SO3, and NaHSO3.

10. The method for producing sulfuric acid from desulfurized products of claim 7, wherein under the action of electric field drive and ion exchange membrane, HSO4- enters the anode chamber to generate H2SO4 and is concentrated, and Na+ enters the cathode chamber to generate NaOH; the gas containing CO2 to be treated is introduced from the cathode chamber and absorbed by NaOH.

11. The method for producing sulfuric acid from desulfurized products of claim 7, wherein the anion exchange membrane is resistant to sulfuric acid at a concentration more than 40 wt %; the anion selection rate is more than 98%; the cation exchange membrane cation selection rate is more than 90%; the initial solution of anode chamber is dilute sulfuric acid of 1 wt. % to 5 wt. %, and the cathode chamber is a sodium hydroxide solution with an initial concentration of 0.05 to 0.5 mol/L.

12. The method for producing sulfuric acid from desulfurized products of claim 7, wherein the electric field is driven by a DC constant current voltage applied between the anode and the cathode, and the current density is 30 to 1000 mA/m2; the anode material is a plate-shaped ruthenium/iridium coated electrode, and the cathode is a graphite plate-shaped electrode.

13. The method for producing sulfuric acid from desulfurized products of claim 7, wherein the flue gas containing CO2 after dust removal, desulfurization and denitrification, the remaining CO2 content of the gas is 5% to 40%.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a schematic diagram of the partial structure of the three-format electrodialysis apparatus of the present invention.

(2) FIG. 2 is a schematic diagram of the system structure of the three-format electrodialysis apparatus of the present invention.

(3) Among them: 1 anode chamber; 2 intermediate chamber; 3 cathode chamber; 4 anode; 5 cathode; 6 anion exchange membrane; 7 cation exchange membrane; 8, 9, 10, 11, 12, 13 liquid circulation tube; 14 flue gas inlet; 15 cathode chamber exhaust port; 16 anode chamber exhaust port; 17 three-format electrodialysis apparatus; 18 DC power supply; 19 desulfurized product solution circulation tank; 20 circulation pump I; 21 cathode chamber liquid circulation tank; 22 circulation pump II; 23 flue gas, 24 exhaust gas.

EMBODIMENTS

(4) Embodiments will be readily understood by the following detailed description in conjunction with the accompanying drawings. To facilitate this description, like reference numerals designate like structural elements. Embodiments are illustrated by way of example and not by way of limitation in the figures of the accompanying drawings.

(5) The methods used in the examples are as described in the summary of the invention.

Embodiment One

(6) A method for capturing carbon dioxide and producing sulfuric acid by sodium bisulfate, which comprises the following steps:

(7) (1) At room temperature, the reaction chamber is divided into a cathode chamber, an intermediate chamber and an anode chamber by using an anion exchange membrane and a cation exchange membrane; the anode chamber is injected with initial solution which is 1 wt. % dilute sulfuric acid, and the cathode chamber is injected with a concentration of 0.5 mol/L NaOH solution. The desulfurized by-products (about 0.1 mol/L NaHSO.sub.4) circulate in the intermediate chamber; 100 mA/m.sup.2 DC constant current is applied between the anode and cathode; the anode material is a plate-shaped ruthenium/iridium coated electrode, and the cathode is a graphite plate-shaped electrode. Under the action of electric field drive and anion exchange membrane, HSO.sub.4.sup.− selectively enters the anode chamber, combines with H.sup.+ produced by the electrolyzed water in the anode chamber to generate H.sub.2SO.sub.4 and is concentrated.

(8) (2) At the same time, the gas containing 10% carbon dioxide after dedusting, desulfurization and denitrification is introduced from the bottom of the cathode chamber with a gas flow rate of 0.8 m.sup.3/h, and absorbed by NaOH; the exhaust gas is discharged from the exhaust port at the top. The NaOH consumed during the reaction is replenished by the OH.sup.− produced from electrolyzed water in the cathode chamber and the Na.sup.+ migrated from the intermediate chamber.

(9) During the treatment process, the capture rate of the CO.sub.2 can reach to more than 95%, and the sulfuric acid concentration recovered and concentrated by the anode chamber reaches to 35 wt. % after 7 days.

Embodiment Two

(10) A method for capturing carbon dioxide and producing sulfuric acid by sodium bisulfate, which comprises the following steps:

(11) (1) At room temperature, the reaction chamber is divided into a cathode chamber, an intermediate chamber and an anode chamber by using an anion exchange membrane and a cation exchange membrane; the anode chamber is injected with initial solution which is 5 wt. % dilute sulfuric acid, and the cathode chamber is injected with a concentration of 0.05 mol/L NaOH solution. The desulfurized by-products (about 0.5 mol/L NaHSO.sub.4) circulate in the intermediate chamber; 30 mA/m.sup.2 DC constant current is applied between the anode and cathode; the anode material is a plate-shaped ruthenium/iridium coated electrode, and the cathode is a graphite plate-shaped electrode. Under the action of electric field drive and anion exchange membrane, SO.sub.4.sup.2− selectively enters the anode chamber, combines with H.sup.+ produced by the electrolyzed water in the anode chamber to generate H.sub.2SO.sub.4 and is concentrated.

(12) (2) At the same time, the gas containing 40% carbon dioxide after dedusting, desulfurization and denitrification is introduced from the bottom of the cathode chamber, and absorbed by NaOH; the exhaust gas is discharged from the exhaust port at the top. The NaOH consumed during the reaction is replenished by the OH.sup.− produced from electrolyzed water in the cathode chamber and the Na.sup.+ migrated from the intermediate chamber.

(13) During the treatment process, the capture rate of the CO.sub.2 can reach to more than 85%, and the sulfuric acid concentration recovered and concentrated by the anode chamber reaches to 45 wt. % after 7 days.

Embodiment Three

(14) A method for capturing carbon dioxide and producing sulfuric acid by sodium bisulfate, which comprises the following steps:

(15) (1) At room temperature, the reaction chamber is divided into a cathode chamber, an intermediate chamber and an anode chamber by using an anion exchange membrane and a cation exchange membrane; the anode chamber is injected with initial solution which is 3 wt. % dilute sulfuric acid, and the cathode chamber is injected with a concentration of 0.3 mol/L NaOH solution. The desulfurized by-products (about 0.5 mol/L NaHSO.sub.4) circulate in the intermediate chamber; 1000 mA/m.sup.2 DC constant current is applied between the anode and cathode; the anode material is a plate-shaped ruthenium/iridium coated electrode, and the cathode is a graphite plate-shaped electrode. Under the action of electric field drive and anion exchange membrane, SO.sub.3.sup.2− selectively enters the anode chamber and is oxidized to SO.sub.4.sup.2−, which combines with H.sup.+ produced by the electrolyzed water in the anode chamber to generate H.sub.2SO.sub.4 and is concentrated.

(16) (2) At the same time, the gas containing 20% carbon dioxide after dedusting, desulfurization and denitrification is introduced from the bottom of the cathode chamber, and absorbed by NaOH; the exhaust gas is discharged from the exhaust port at the top. The NaOH consumed during the reaction is replenished by the OH.sup.− produced from electrolyzed water in the cathode chamber and the Na.sup.+ migrated from the intermediate chamber.

(17) During the treatment process, the capture rate of the CO.sub.2 can reach to more than 90%, and the sulfuric acid concentration recovered and concentrated by the anode chamber reaches to 40 wt. % after 7 days; the oxidation rate of sulfite ion reaches to 97%.

Embodiment Four

(18) An apparatus for producing sulfuric acid from desulfurized products, that is, a three-format electrodialysis apparatus, as shown in FIG. 1, the apparatus comprises a reactor, an anode electrode, a cathode electrode, and a power supply; the anode electrode 4 and the cathode electrodes 5 are respectively arranged at both ends of the reactor, and are connected to the power source through wires, and the anion exchange membrane 6 and the cation exchange membrane 7 are arranged in sequence in the reactor to divide the chamber of reactor into anode chamber 1, intermediate chamber 2 and cathode chamber 3; the bottom of the cathode chamber is provided with flue gas inlet 14 and an aeration sieve plate, at the top of the cathode is provided with cathode chamber exhaust port 15, and the anode chamber is provided with an anode chamber exhaust port 16; the anode chamber, the intermediate chamber and the cathode chamber are respectively provided with liquid inlet and outlet tubes for the circulation of the liquid; specifically, 8, 9, 10, 11, 12, 13 are liquid circulation tubes.

(19) Further, as shown in FIG. 2, the three-format electrodialysis apparatus further comprises circulation pump I 20 and circulation pump II 22; one end of the circulation pump I 20 is connected with the liquid circulation tube in the intermediate chamber 11, and the other end is connected to the desulfurized product solution circulation tank 19; the desulfurized product liquid circulation tank 19 is also connected to the liquid circulation tube 10 of the intermediate chamber 2; one end of the circulation pump II 22 is connected to the liquid circulation tube 12 of the cathode chamber, and the other end is connected to the cathode chamber liquid circulation tank 21, and the cathode chamber liquid circulation tank 21 is also connected to the liquid circulation tube 13 of the cathode chamber.

(20) The working principle of the apparatus of the present invention is that the desulfurized product solution is added to the desulfurized product solution circulation tank 19, meanwhile the diluted sulfuric acid as initial solution is added to the anode chamber 1 of the three-format electrodialysis apparatus while the desulfurized product solution is added into the intermediate chamber 2; the initial concentration of sodium hydroxide solution is added into the cathode chamber 3, and water or the initial concentration of sodium hydroxide solution into the cathode chamber liquid circulation tank 21. During operation, the flue gas 23 is introduced into the flue gas inlet, and the circulation pump I 20 and the circulation pump II 22 and the DC power supply 18 are started and the apparatus starts to work. During the electrolysis process, the liquid of the intermediate chamber, anode chamber and the cathode chamber enters the reacting chamber from the bottom tub, and is pumped out from the upper tube for circulation; under the action of electric field drive and anion exchange membrane, HSO.sub.4.sup.− selectively enters the anode chamber, and combines with the H.sup.+ produced by the electrolytic water in the anode chamber H.sub.2SO.sub.4, the generated O.sub.2 is discharged and collected by the anode chamber exhaust port 16; at the same time, under the action of the electric field drive and the cation exchange membrane, Na.sup.+ selectively enters the cathode chamber and combines with the OH.sup.− generated by the electrolytic water in the cathode chamber to generate NaOH; the gas containing CO.sub.2 to be treated is introduced into the flue gas inlet 14 at the bottom of the cathode chamber and absorbed by the NaOH generated, and is converted into Na.sub.2CO.sub.3 and NaHCO.sub.3. The exhaust gas 23 is discharged from the cathode chamber exhaust port 15.

(21) Although certain embodiments have been illustrated and described herein for purposes of description, a wide variety of alternate and/or equivalent embodiments or implementations calculated to achieve the same purposes may be substituted for the embodiments shown and described without departing from the scope of the present disclosure. This application is intended to cover any adaptations or variations of the embodiments discussed herein. therefore, it is manifestly intended that embodiments described herein be limited only by the claim and the equivalents thereof.