Method and system for the electrochemical co-production of halogen and carbon monoxide for carbonylated products

• US 8,691,069 B2
• Filed: 12/21/2012
• Issued: 04/08/2014
• 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., Shirtum, Robert Page
• Primary Examiner(s): Wong, Edna
• Application Number:
  US13/724,996
• Publication Number:
  US 20130134049A1
• Time in Patent Office: 473 Days
• Field of Search: 560/1, 560/355, 560/358, 562/400, 570/101, 585/379, 585/654, 205/555, 205/618, 205/619
• US Class Current: 205/555
• 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 a step of contacting the first region with a catholyte including carbon dioxide and contacting the second region with an anolyte including a recycled reactant. The method may further include applying an electrical potential between the anode and the cathode sufficient to produce carbon monoxide recoverable from the first region and a halogen recoverable from the second region.

Claims

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

contacting the first region of the electrochemical cell with a catholyte comprising carbon dioxide;

contacting the second region of the electrochemical cell with an anolyte comprising a recycled reactant, wherein the recycled reactant is HX, where X is selected from the group consisting of F, Cl, Br, and I; and

applying an electrical potential between the anode and the cathode of the electrochemical cell sufficient to reduce the carbon dioxide and co-produce the carbon monoxide recoverable from the first region of the electrochemical cell and the halogen recoverable from the second region of the electrochemical cell.

2. The method according to claim 1, wherein the halogen includes at least one of F₂, Cl₂, Br₂ or I₂.

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

drying the carbon monoxide recovered from the first region and the halogen recovered from the second region to less than 0.10 percent water by weight.

4. The method according to claim 3, further comprising:

reacting the carbon monoxide recovered from the first region, the halogen recovered from the second region and an additional reactant to form a third product and the recycled reactant.

5. The method according to claim 4, wherein the additional reactant includes at least one of an amine, methyl amine, butyl amine, aniline, a diamine, di amino toluene, diamino benzene, 4,4′

-methylene diphenyl diamine, hexamethylenediamine, meta-tetramethylxylylene-diamine, and toluenediamines, or at least one of an alcohol, methanol, and ethanol, and mixtures thereof.

6. The method according to claim 4, wherein the third product includes one of isocyanate, methyl isocyanate, butyl isocyanate, phenyl isocyanate, diisocyanate, methylene-diphenylisocyanate, phenyl-diisocyanate, hexamethylene-diisocyanate, toluene-diisocyanate, meta-tetramethylxylylene-diisocyanate, alkyl carbonate, dimethyl carbonate, ethylmethyl carbonate or diethyl carbonate.

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

reacting the halogen recovered from the second region and an additional reactant to form a third product and the recycled reactant.

8. The method according to claim 7, wherein the additional reactant is a halocarbon and the third product is a dihalogenated hydrocarbon.

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

converting the dihalogenated hydrocarbon to acetylene and the recycled reactant via a dehydrohalogenation reaction.

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

reacting the carbon monoxide recovered from the first region, acetylene, and one of water or alcohol to form one of acrylic acid or acrylic acid esters.

11. 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.

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

14. The method according to claim 13, wherein the liquid phase of the catholyte liquid phase is an aqueous solution including an electrolyte including one or more of alkali metal sulfates, carbonates, chlorides, phosphates, borates, nitrates, and nitrites.

15. The method of claim 13, wherein the catholyte further includes an aqueous solvent which is more than 5% by weight water.

16. The method of claim 13, wherein the catholyte further includes a non-aqueous solvent which is less than 5% by weight water.

17. The method of claim 13, where the catholyte further includes at least one of water, a protic solvent, or an aprotic solvent.

18. The method of claim 1, wherein the catholyte further includes a homogeneous catalyst.

19. The method of claim 18, wherein the homogeneous catalyst includes at least one of unsubstituted pyrimindine, substituted pyridine, imidazole, dinitrogen heterocyclic amine, azole, imidazole, indole, oxazole or thiazole.