Electrochemical reduction of CO;with co-oxidation of an alcohol

• US 8,845,875 B2
• Filed: 12/21/2012
• Issued: 09/30/2014
• 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: Teamey, Kyle, Kaczur, Jerry J., Cole, Emily Barton, Majsztrik, Paul, Sivasankar, Narayanappa, Bocarsly, Andrew B.
• Primary Examiner(s): Wong, Edna
• Application Number:
  US13/724,231
• Publication Number:
  US 20130140187A1
• Time in Patent Office: 648 Days
• Field of Search: 205/440, 205/443, 205/446, 205/448, 205/450, 205/455, 205/456, 205/462, 205/555, 205/413, 205/464
• US Class Current: 205/413
• 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 is 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 the step of contacting the first region of the electrochemical cell with a catholyte comprising an alcohol and carbon dioxide. Another step of the method may include contacting the second region of the electrochemical cell with an anolyte comprising the alcohol. 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.

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, the anolyte comprising an alcohol, the anolyte comprising the alcohol is in a gaseous phase; and

applying an electrical potential between the anode and the cathode sufficient to produce the first product recoverable from the first region and the second product recoverable from the second region, the anode including a metal substrate and an electrocatalytic coating on the metal substrate, the metal substrate includes at least one of titanium, tantalum, zirconium or niobium and the electrocatalytic coating includes a metal oxide, the metal oxide includes at least one of ruthenium, iridium, platinum or gold.

2. The method according to claim 1, wherein the anolyte is free of halide ions.

3. The method according to claim 1, wherein the alcohol includes at least one of methanol, ethanol, ethylene glycol, glycerol, 1-propanol, 2-propanol, phenol, 1-butanol, 2-butanol, isopropanol, benzyl alcohol, allyl alcohol, a glycol, or a polyol.

4. The method according to claim 1, wherein the cathode and the anode are separated by an ion permeable barrier.

5. The method according to claim 4, wherein the ion permeable barrier includes at least one of a solid polymer conductor electrolyte material, a perfluorinated sulfonic acid based membrane, a sodium super-conducting ionic conductor ceramics, zirconium-yttria ceramics or beta-alumina based ceramics.

6. The method according to claim 1, wherein the anode including the electrocatalytic coating is configured for oxidation of the alcohol.

7. The method according to claim 1, wherein the catholyte further comprises an electrolyte.

8. The method according to claim 7, wherein the electrolyte includes at least one of alkali metal bicarbonate, carbonate, sulfate, phosphate or borate.

9. The method according to claim 1, wherein the catholyte further comprises a homogeneous catalyst.

10. The method according to claim 9, wherein the homogeneous catalyst includes an aromatic heterocyclic amine.

11. The method according to claim 1, wherein the catholyte further comprises said alcohol.

12. The method of claim 1, wherein a molar ratio of alcohol to the second product is in a range of 500:

1 to 2;

1.

13. 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, the anolyte comprising an alcohol, the anolyte comprises an aqueous solution of the alcohol, the aqueous solution of the alcohol includes at least 5% water; and

applying an electrical potential between the anode and the cathode sufficient to produce the first product recoverable from the first region and the second product recoverable from the second region, the anode including a metal substrate and an electrocatalytic coating on the metal substrate, the metal substrate includes at least one of titanium, tantalum, zirconium or niobium and the electrocatalytic coating includes a metal oxide, the metal oxide includes at least one of ruthenium, iridium, platinum or gold.

14. The method according to claim 13, wherein the anolyte is free of halide ions.

15. The method according to claim 13, wherein the alcohol includes at least one of methanol, ethanol, ethylene glycol, glycerol, 1-propanol, 2-propanol, phenol, 1-butanol, 2-butanol, isopropanol, benzyl alcohol, allyl alcohol, a glycol, or a polyol.

16. The method according to claim 13, wherein the cathode and the anode are separated by an ion permeable barrier.

17. The method according to claim 16, wherein the ion permeable barrier includes at least one of a solid polymer conductor electrolyte material, a perfluorinated sulfonic acid based membrane, a sodium super-conducting ionic conductor ceramics, zirconium-yttria ceramics or beta-alumina based ceramics.

18. The method according to claim 13, wherein the anode including the electrocatalytic coating is configured for oxidation of the alcohol.

19. The method according to claim 13, wherein the catholyte further comprises an electrolyte.

20. The method according to claim 19, wherein the electrolyte includes at least one of alkali metal bicarbonate, carbonate, sulfate, phosphate or borate.

21. The method according to claim 13, wherein the catholyte further comprises a homogeneous catalyst.

22. The method according to claim 21, wherein the homogeneous catalyst includes an aromatic heterocyclic amine.

23. The method according to claim 13, wherein the catholyte further comprises said alcohol.

24. The method of claim 13, wherein a molar ratio of alcohol to the second product is in a range of 500:

1 to 2;

1.