Electrochemical co-production of chemicals with sulfur-based reactant feeds to anode

• US 9,303,324 B2
• Filed: 12/21/2012
• Issued: 04/05/2016
• Est. Priority Date: 07/26/2012
• Status: Active Grant

• Current Assignee: Avantium Knowledge Centre B.V. (Avantium NV)
• Original Assignee: Liquid Light, Inc. (Avantium NV)
• Inventors: Kaczur, Jerry J., Teamey, Kyle
• Primary Examiner(s): Wilkins, III, Harry D
• Application Number:
  US13/724,719
• Publication Number:
  US 20130118909A1
• Time in Patent Office: 1,201 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: C07C 1/26 starting from organic compounds containing only halogen atoms as hetero-atoms
• CPC Class Codes: C07C 29/149 with hydrogen or hydrogen-containing gases
• CPC Class Codes: C07C 29/58 by elimination of halogen, e.g. by hydrogenolysis, splitting-off C07C29/124 takes precedence
• CPC Class Codes: C07C 51/02 from salts of carboxylic acids
• CPC Class Codes: C07C 51/15 by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
• CPC Class Codes: C07C 51/367 by introduction of functional groups containing oxygen only in singly bound form
• CPC Class Codes: C07C 67/08 by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
• CPC Class Codes: C25B 1/00 Electrolytic production of inorganic compounds or non-metals
• CPC Class Codes: C25B 1/24 Halogens or compounds thereof
• CPC Class Codes: C25B 13/08 based on organic materials
• CPC Class Codes: C25B 15/00 Operating or servicing cells
• CPC Class Codes: C25B 15/08 Supplying or removing reactants or electrolytes; Regeneration of electrolytes
• CPC Class Codes: C25B 3/00 Electrolytic production of organic compounds
• CPC Class Codes: C25B 3/23 Oxidation halogenation C25B3/27
• CPC Class Codes: C25B 3/25 Reduction
• CPC Class Codes: C25B 3/27 Halogenation
• CPC Class Codes: C25B 3/29 Coupling reactions
• CPC Class Codes: C25B 9/19 with diaphragms
• CPC Class Codes: C25B 9/23 comprising ion-exchange membranes in or on which electrode material is embedded
• CPC Class Codes: Y02P 20/10 Process efficiency
• CPC Class Codes: Y02P 20/129 : Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
• CPC Class Codes: Y02P 20/133 : Renewable energy sources, e.g. sunlight
• CPC Class Codes: Y02P 20/582 : Recycling of unreacted starting or intermediate materials

Abstract

The present disclosure includes a system and method for producing a first product from a first region of an electrochemical cell having a cathode and a second product from a second region of the electrochemical cell having an anode. The method may include a step of contacting the first region with a catholyte comprising carbon dioxide. The method may include another step of contacting the second region with an anolyte comprising a sulfur-based reactant. Further, the method may include a step of applying an electrical potential between the anode and the cathode sufficient to produce a first product recoverable from the first region and a second product recoverable from the second region. An additional step of the method may include removing the second product and an unreacted sulfur-based reactant from the second region and recycling the unreacted sulfur-based reactant to the second region.

Claims

1. A method for producing a first product from a first region of an electrochemical cell having a cathode and a second product from a second region of the electrochemical cell having an anode, the method comprising the steps of:

contacting the first region with a catholyte comprising carbon dioxide;

contacting the second region with an anolyte comprising a sulfur-based reactant and a nitrogen-based reactant;

applying an electrical potential between the anode and the cathode sufficient to reduce carbon dioxide at the cathode to produce a first product recoverable from the first region and a second product recoverable from the second region;

removing the second product, an unreacted sulfur-based reactant and an unreacted nitrogen-based reactant from the second region;

recycling the unreacted sulfur-based reactant and the unreacted nitrogen-based reactant to the second region;

removing the first product from the first region;

reacting the first product with water to produce carbon dioxide; and

recycling the carbon dioxide to the first region.

2. The method according to claim 1, wherein the sulfur-based reactant includes at least one of sulfur dioxide, hydrogen sulfide, an alkali metal sulfide, an alkali metal sulfite, bisulfite, or thiosulfate.

3. The method according to claim 1, wherein the second product includes at least one of sulfur trioxide, sulfuric acid, alkali metal sulfites, alkali metal thiosulfates, or alkali metal polysulfides.

4. The method according to claim 1, wherein the first product includes carbon monoxide.

5. The method according to claim 1, further comprising:

converting the second product to a third product.

6. The method according to claim 1, wherein the anolyte and the catholyte are non-aqueous.

7. The method according to claim 6, wherein the second product comprises at least one of sodium sulfite and sodium thiosulfate.

8. The method according to claim 1, wherein the sulfur-based reactant is sulfur dioxide and the second product is sulfur trioxide.

9. The method according to claim 8, further comprising:

converting the second product to sulfuric acid.

10. The method according to claim 1, wherein the catholyte further comprises at least one of sodium bicarbonate or potassium bicarbonate.

11. The method according to claim 1, wherein the catholyte is liquid phase and the anolyte is gas phase.

12. The method according to claim 1, wherein the cathode and the anode are separated by an ion permeable barrier that operates at a temperature less than 600 degrees C and the ion permeable barrier includes one of a polymeric or inorganic ceramic-based ion permeable barrier.

13. The method according to claim 1, wherein the nitrogen-based reactant includes at least one of nitric oxide, nitrogen dioxide, nitrous oxide, ammonia, an alkali metal nitrite, or an alkali metal nitrate.

14. The method according to claim 1, wherein the second product includes nitric acid.

15. The method according to claim 1, wherein the second product includes nitric acid and at least one of sulfur trioxide, sulfuric acid, alkali metal sulfites, alkali metal thiosulfates, or alkali metal polysulfides.

16. A method for producing a first product from a first region of an electrochemical cell having a cathode and a second product from a second region of the electrochemical cell having an anode, the method comprising the steps of:

receiving a feed of carbon dioxide at the first region of the electrochemical cell;

contacting the first region with a catholyte comprising carbon dioxide;

receiving a feed of a sulfur-based reactant and a nitrogen-based reactant at the second region of the electrochemical cell;

contacting the second region with an anolyte comprising the sulfur-based reactant and a nitrogen-based reactant;

applying an electrical potential between the anode and the cathode sufficient to reduce carbon dioxide at the cathode to produce a first product recoverable from the first region and a second product recoverable from the second region;

removing the second product, an unreacted sulfur-based reactant and an unreacted nitrogen-based reactant from the second region;

recycling the unreacted sulfur-based reactant and the unreacted nitrogen-based reactant to the second region;

removing the first product from the first region;

reacting the first product with water to produce carbon dioxide; and

recycling the carbon dioxide to the first region.

17. The method according to claim 16, wherein the sulfur-based reactant includes at least one of sulfur dioxide, sodium sulfide, hydrogen sulfide, an alkali metal sulfide, an alkali metal sulfite, bisulfite, or thiosulfate.

18. The method according to claim 16, wherein the second product includes at least one of sulfur trioxide, sodium sulfite, sodium thiosulfate or sodium polysulfide.

19. The method according to claim 16, wherein the first product includes carbon monoxide.

20. The method according to claim 16, wherein the sulfur-based reactant is sulfur dioxide and the second product is sulfur trioxide.

21. The method according to claim 20, further comprising:

converting the sulfur trioxide to sulfuric acid.

22. The method according to claim 16, wherein the catholyte is liquid phase and the anolyte is gas phase.

23. The method according to claim 16, wherein the cathode and the anode are separated by an ion permeable barrier;

wherein the ion permeable barrier includes one of a polymeric or inorganic ceramic-based ion permeable barrier;

wherein the barrier operates at a temperature less than 600 degrees C.

24. A system for electrochemical co-production of products, comprising:

an electrochemical cell including;

a first region;

a cathode associated with the first region;

a second region;

an anode associated with the second region; and

a separator for selectively controlling a flow of ions between the first region and the second region;

a carbon dioxide source, the carbon dioxide source in flow communication with the first region to supply carbon dioxide to the first region;

a sulfur-based reactant source, the sulfur-based reactant source in flow communication with the second region to supply a sulfur-based reactant to said second region;

a nitrogen-based reactant source, the nitrogen-based reactant source in flow communication with the second region to supply a nitrogen-based reactant to said second region;

an energy source for applying a current across the anode and the cathode, wherein when current is applied, a first product recoverable from the first region and a second product is recoverable from the second region; and

a reactor for reacting the first product recoverable from the first region with water to produce carbon dioxide that is recycled to the first region.

25. The system according to claim 24, wherein the recycled sulfur-based reactant includes at least one of sulfur dioxide, sodium sulfide, hydrogen sulfide, an alkali metal sulfide, an alkali metal sulfite, bisulfite, or thiosulfate.

26. The system according to claim 24, wherein the second product includes at least one of sulfur trioxide, sodium sulfite, or sodium thiosulfate.

27. The system according to claim 24, wherein the first product includes carbon monoxide.

28. The system according to claim 24, wherein the sulfur-based reactant is sulfur dioxide and the second product is sulfur trioxide.

29. The system according to claim 24, wherein the separator includes an ion permeable barrier and selectively controls a flow of ions between the first region and the second region at a temperature less than 600 degrees C.

30. A method for producing a first product from a first region of an electrochemical cell having a cathode and a second product from a second region of the electrochemical cell having an anode, the method comprising the steps of:

contacting the first region with a catholyte, the catholyte consisting essentially of carbon dioxide, solvent, a catalyst and an electrolyte;

contacting the second region with an anolyte comprising a nitrogen-based reactant;

applying an electrical potential between the anode and the cathode sufficient to produce a first product recoverable from the first region and a second product recoverable from the second region;

removing the second product and an unreacted nitrogen-based reactant from the second region;

recycling the unreacted nitrogen-based reactant to the second region.

removing the first product from the first region;

reacting the first product with water to produce carbon dioxide; and

recycling the carbon dioxide to the first region.

31. The method according to claim 30, wherein the nitrogen-based reactant includes at least one of nitric oxide, nitrogen dioxide, nitrous oxide, ammonia, an alkali metal nitrite, or an alkali metal nitrate.

32. The method according to claim 30, wherein the second product includes nitric acid.

33. The method according to claim 30, wherein the cathode and the anode are separated by an ion permeable barrier that operates at a temperature less than 600 degrees C. and the ion permeable barrier includes one of a polymeric or inorganic ceramic-based ion permeable barrier.