CO 2 utilization in electrochemical systems

• US 8,357,270 B2
• Filed: 07/15/2009
• Issued: 01/22/2013
• Est. Priority Date: 07/16/2008
• Status: Active Grant

• Current Assignee: Eleryc Incorporated
• Original Assignee: Calera Corporation
• Inventors: Gilliam, Ryan J., Albrecht, Thomas A., Jalani, Nikhil, Knott, Nigel Antony, Decker, Valentin, Kostowskyj, Michael, Boggs, Bryan, Gorer, Alexander, Farsad, Kasra
• Primary Examiner(s): Smith, Nicholas A.
• Application Number:
  US12/503,557
• Publication Number:
  US 20100230293A1
• Time in Patent Office: 1,287 Days
• Field of Search: 204/263, 205/637
• US Class Current: 204/263
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 2313/08 Flow guidance means within the module or the apparatus
• CPC Class Codes: B01D 2313/16 Specific vents
• CPC Class Codes: B01D 2313/26 Specific gas distributors or gas intakes
• CPC Class Codes: B01D 53/326 in electrochemical cells
• CPC Class Codes: B01D 61/422 Electrodialysis
• CPC Class Codes: B01D 61/44 Ion-selective electrodialysis
• CPC Class Codes: B01D 61/46 Apparatus therefor
• CPC Class Codes: B01D 61/463 comprising the membrane sequence AC or CA, where C is a cation exchange membrane
• CPC Class Codes: C01B 7/01 Chlorine; Hydrogen chloride
• CPC Class Codes: C01D 1/40 by electrolysis
• CPC Class Codes: C01D 7/07 Preparation from the hydroxides
• CPC Class Codes: C01F 11/18 Carbonates
• CPC Class Codes: C01F 5/24 Magnesium carbonates
• CPC Class Codes: C02F 1/46109 Electrodes
• CPC Class Codes: C02F 1/68 by addition of specified substances, e.g. trace elements, for ameliorating potable water medicinal water A61K
• CPC Class Codes: C02F 2001/46166 Gas diffusion electrodes
• CPC Class Codes: C02F 2201/46115 Electrolytic cell with membranes or diaphragms
• CPC Class Codes: C02F 2201/4613 Inversing polarity
• CPC Class Codes: C02F 2201/46135 Voltage
• CPC Class Codes: C02F 2201/46185 : Recycling the cathodic or anodic feed
• CPC Class Codes: C02F 2209/06 : pH
• CPC Class Codes: C02F 2301/046 : Recirculation with an external loop
• CPC Class Codes: C25B 1/00 : Electrolytic production of inorganic compounds or non-metals
• CPC Class Codes: C25B 1/02 : Hydrogen or oxygen
• CPC Class Codes: C25B 1/04 : by electrolysis of water
• CPC Class Codes: C25B 1/14 : Alkali metal compounds
• CPC Class Codes: C25B 1/16 : Hydroxides by simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine C25B1/34
• CPC Class Codes: C25B 1/20 : Hydroxides
• CPC Class Codes: C25B 1/26 : Chlorine; Compounds thereof by simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine C25B1/34
• CPC Class Codes: C25B 15/08 : Supplying or removing reactants or electrolytes; Regeneration of electrolytes
• CPC Class Codes: Y02C 20/40 : of CO2
• CPC Class Codes: Y02E 60/36 : Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
• CPC Class Codes: Y02P 20/151 : Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Abstract

A low-voltage, low-energy electrochemical system and method of removing protons and/or producing a base solution comprising hydroxide and carbonate/bicarbonate ions, utilizing carbon dioxide in a cathode compartment that is partitioned into a first cathode electrolyte compartment and a second cathode electrolyte compartment such that liquid flow between the cathode electrolyte compartments is possible, but wherein gaseous communication between the cathode electrolyte compartments is restricted. Carbon dioxide gas in one cathode electrolyte compartment is utilized with the cathode electrolyte in both compartments to produce the base solution with less that 3V applied across the electrodes.

Claims

1. An electrochemical system comprising:

(a) a cathode compartment comprising a cathode electrolyte in contact with a cathode, wherein the cathode produces hydrogen gas, and wherein the cathode compartment is operatively connected to a system selected from an industrial waste gas system that delivers carbon dioxide derived from combusting fossil fuels or cement plants to the cathode compartment;

a gas/liquid contactor operatively connected to the industrial waste gas system wherein the gas/liquid contactor contacts the cathode compartment with carbon dioxide from the industrial waste gas system;

or combination thereof;

(b) an anode compartment comprising an anode electrolyte in contact with an anode;

(c) the cathode electrolyte comprising bicarbonate ions wherein the anode electrolyte and the cathode electrolyte have a pH differential of between 6-12;

(d) a hydrogen gas delivery system configured to direct hydrogen gas from the cathode to the anode; and

a Nernst cell voltage of less than 0.8V across the anode and the cathode.

2. The system of claim 1, wherein the system is configured to absorb the carbon dioxide gas into the cathode electrolyte, and further wherein the cathode electrolyte comprises hydroxide ions, carbonic acid, carbonate ions, or any combination thereof.

3. The system of claim 1, wherein the cathode compartment is partitioned into a first cathode electrolyte compartment and a second cathode electrolyte compartment by a partition such that on placing the cathode electrolyte in the cathode compartment, there is a liquid flow between the cathode electrolyte in the first cathode electrolyte compartment and the cathode electrolyte in the second cathode electrolyte compartment and wherein the carbon dioxide gas is isolated from the cathode electrolyte in the second cathode electrolyte compartment such that the carbon dioxide gas is prevented from contacting the cathode.

4. The system of claim 1, wherein the system is configured to produce hydroxide ions in the cathode electrolyte with less than 0.6V across the anode and cathode.

5. The system of claim 1, wherein the system does not produce a gas at the anode.

6. The system of claim 3, wherein the system is configured to migrate hydroxide ions from the second cathode electrolyte compartment to the first cathode electrolyte compartment.

7. The system of claim 1, wherein the cathode compartment is operatively connected to a hydroxide, carbonate and/or bicarbonate precipitation system, wherein the precipitation system is configured to utilize the cathode electrolyte to produce hydroxide, divalent cation carbonates and/or divalent cation bicarbonate.

8. The system of claim 1, further comprising at least one ion exchange membrane between the anode compartment and the cathode compartment.

9. The system of claim 8, wherein the at least one ion exchange membrane comprises a cation exchange membrane separating the cathode electrolyte from a third electrolyte, an anion exchange membrane separating the anode electrolyte from the third electrolyte, or both the cation exchange membrane separating the cathode electrolyte from a third electrolyte and the anion exchange membrane separating the anode electrolyte from the third electrolyte.

10. The system of claim 9, wherein the third electrolyte comprises sodium ions and chloride ions and wherein the system is configured to migrate the sodium ions from the third electrolyte to the cathode electrolyte through the cation exchange membrane, and migrate the chloride ions from the third electrolyte to the anode electrolyte through the anion exchange membrane, and further wherein the system is configured to produce hydrochloric acid in the anode electrolyte.

11. The system of claim 10, wherein the system is configured to produce sodium hydroxide, sodium carbonate and/or sodium bicarbonate in the cathode electrolyte and partially desalinated water in the third electrolyte.

12. The system of claim 1, wherein the gas/liquid contactor comprises the cathode electrolyte withdrawn from the cathode compartment that is contacted with the carbon dioxide from the industrial waste gas system.

13. The system of claim 12, wherein the cathode electrolyte comprising carbon dioxide is returned to the cathode compartment.

14. An electrochemical method comprising:

contacting an anode electrolyte with an anode in an anode compartment wherein the anode oxidizes hydrogen gas to hydrogen ions;

contacting a cathode electrolyte with a cathode in a cathode compartment wherein the cathode produces hydroxide ions and hydrogen gas;

directing hydrogen gas produced at the cathode to the anode;

directing an industrial waste gas comprising carbon dioxide into the cathode electrolyte in the cathode compartment or directing carbon dioxide into the cathode electrolyte from a gas/liquid contactor that is in contact with an industrial waste gas;

converting bicarbonate ions to carbonate ions in the cathode electrolyte and producing a pH differential between the anode electrolyte and the cathode electrolyte of between 6-12; and

applying a Nernst cell voltage of less than 0.8V across the cathode and the anode.

15. The method of claim 14, comprising producing hydroxide ions, carbonic acid, carbonate ions, and/or bicarbonate ions in the cathode electrolyte.

16. The method of claim 14, wherein the voltage applied across the anode and the cathode is less than 0.6V.

17. The method of claim 15, further comprising producing hydrogen ions at the anode wherein a gas is not produced at the anode.

18. The method of claim 14, further comprising separating the cathode electrolyte from a third electrolyte by a cation exchange membrane, separating the anode electrolyte from the third electrolyte by an anion exchange membrane, or both.

19. The method of claim 18, wherein the third electrolyte comprises sodium ions and chloride ions.

20. The method of claim 19, further comprising migrating the sodium ions from the third electrolyte to the cathode electrolyte across the cation exchange membrane, and migrating the chloride ions from the third electrolyte to the anode electrolyte across the anion exchange membrane, producing an acid in the anode electrolyte, and producing sodium carbonate, sodium bicarbonate or sodium hydroxide in the cathode electrolyte.

21. The method of claim 20, further comprising contacting the cathode electrolyte with a divalent cation solution to produce divalent cation hydroxide, carbonate and/or bicarbonate compounds, wherein the divalent carbonate and/or bicarbonate compounds comprise calcium, magnesium, or both calcium and magnesium.