Electrochemical co-production of chemicals utilizing a halide salt

• US 8,692,019 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: Kaczur, Jerry J., Tearney, Kyle
• Primary Examiner(s): Zucker, Paula A
• Application Number:
  US13/724,807
• Publication Number:
  US 20130137898A1
• Time in Patent Office: 473 Days
• US Class Current: 562/597
• 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 co-producing a first product and a second product. The system may include a first electrochemical cell, at least one second reactor, and an acidification chamber. The method and system for co-producing a first product and a second product may include co-producing a carboxylic acid and at least one of an alkene, alkyne, aldehyde, ketone, or an alcohol while employing a recycled halide salt.

Claims

1. A method for co-producing M-carboxylate and a halogen, the method comprising the steps of:

contacting a first region of an electrochemical cell having a cathode with a catholyte comprising carbon dioxide;

contacting a second region of the electrochemical cell having an anode with an anolyte comprising an MX where M is at least one cation and X is selected from the group consisting of F, Cl, Br, I and mixtures thereof;

applying an electrical potential between the anode and the cathode of the electrochemical cell sufficient to produce the M-carboxylate recoverable from the first region of the electrochemical cell and the halogen recoverable from the second region of the electrochemical cell;

reacting the halogen from the second region of the electrochemical cell with one of an alkane, an alkene, or an aromatic to produce a halogenated compound and HX, the HX being recycled back to an acidification chamber;

reacting the M-carboxylate with the HX via the acidification chamber to produce a carboxylic acid and MX, the MX being recycled to an input of the second region of the electrochemical cell.

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

reacting the halogenated compound via a third reactor to produce the second product and HX, the HX being recycled to the acidification chamber.

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

4. The method according to claim 1, wherein the halogenated compound includes at least one of a brominated compound, benzyl bromide, (1-bromethyl) benzene, perhalo carbon, bromoethane, vinyl chloride, dichloroethane, allyl chloride, chlorophenol, bromobenzene, vinyl bromide, vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, difluoromethane, or pentafluoroethane.

5. The method according to claim 2, wherein the second product is at least one of an alkane, an alkene, an alkyne, an alcohol, an aldehyde, or a ketone.

6. The method according to claim 2, wherein the third reactor includes water.

7. The method according to claim 1, wherein the carboxylic acid is oxalic acid.

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

feeding the carboxylic acid to a thermal hydrogenation chamber, the thermal hydrogenation chamber comprising H₂; and

forming a third product in the thermal hydrogenation chamber.

9. The method according to claim 8, wherein the third product includes at least one of glyoxylic acid, glycolic acid, glyoxal, glycolaldeyde, ethylene glycol, ethanol, acetic acid, acetaldehyde, ethane, or ethylene.

10. The method according to claim 1, wherein the cathode and the anode of the first electrochemical cell and the second electrochemical cell are separated by an ion permeable barrier that operates at a temperature less than 600 degrees C.

11. The method according to claim 1, wherein the ion permeable barrier includes one of a polymeric or inorganic ceramic-based ion permeable barrier.

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

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

reacting the carboxylic acid with H₂ to form a third product via a thermal hydrogenation chamber;

reacting the halogenated compound with a caustic compound via a third reactor to produce the second product and MX, the MX being recycled to an input of a second region of a second electrochemical cell, the second electrochemical cell comprising a first region having a cathode and the second region having an anode;

contacting the first region of the second electrochemical cell with a catholyte comprising water;

contacting the second region of the second electrochemical cell with the MX from the third reactor;

applying an electrical potential between the anode and the cathode of the second electrochemical cell sufficient to produce H₂ and the caustic compound recoverable from the first region of the second electrochemical cell and a halogen recoverable from the second region of the second electrochemical cell;

feeding the H₂ from the second electrochemical cell to the thermal hydrogenation chamber;

feeding the caustic compound from the second electrochemical cell to the third reactor;

feeding the halogen recoverable from the second region of the second electrochemical cell to the second reactor.

14. The method according to claim 13 wherein the second product is at least one of an alcohol, an alkene, an alkyne, an aldehyde, a ketone, an alkane, and mixtures thereof.

15. The method according to claim 8, wherein the third product includes at least one of glyoxylic acid, glycolic acid, glyoxal, glycolaldeyde, ethylene glycol, ethanol, acetic acid, acetaldehyde, ethane, or ethylene.

16. A method for co-producing M-carboxylate and a halogen, the method comprising the steps of:

contacting a first region of a first electrochemical cell having an cathode with a catholyte comprising carbon dioxide;

contacting a second region of a first electrochemical cell having an anode with an anolyte comprising an MX where M is at least one cation and X is selected from the group consisting of F, Cl, Br, I, and mixtures thereof;

applying an electrical potential between the anode and the cathode of the electrochemical cell sufficient to co-produce the M-carboxylate recoverable from the first region of the first electrochemical cell and the halogen recoverable from the second region of the first electrochemical cell;

reacting the halogen with at least one of an alkane, alkene, or aromatic to form a halogenated compound and HX via a secondary reactor, the HX being recycled to an input of a second region of an electrochemical acidification cell;

reacting the halogenated compound with a caustic compound to form MX and the second product via a third reactor, the MX recycled to an input of the second region of the electrochemical cell;

contacting a first region of the electrochemical acidification cell having an cathode with a catholyte comprising water;

contacting a second region of the electrochemical acidification cell having an anode with an anolyte comprising HX;

contacting an acidification region of the electrochemical acidification cell with M-carboxylate;

applying an electrical potential between the anode and the cathode of the electrochemical acidification cell sufficient to produce the first product, a carboxylic acid, recoverable from the acidification region of the electrochemical acidification cell, a halogen recoverable from the second region of the electrochemical acidification cell, H₂ recoverable from the first region of the electrochemical acidification cell, and a caustic compound, the caustic compound recycled as an input to the third reactor.

17. The method according to claim 16, further comprising:

reacting the carboxylic acid and the H₂ from the electrochemical acidification cell in a thermal hydrogenation chamber to produce a third product.

18. The method according to claim 17, wherein the third product includes at least one of glyoxylic acid, glycolic acid, glyoxal, glycolaldeyde, ethylene glycol, ethanol, acetic acid, acetaldehyde, ethane, or ethylene.

19. The method according to claim 16, wherein the second product is at least one of an alcohol, an alkene, an alkyne, an aldehyde, a ketone, an alkane, and mixtures thereof.

20. The method according to claim 16, wherein the cathode and the anode of the electrochemical cell and the cathode and the anode of the electrochemical acidification cell are separated by at least one ion permeable barrier that operates at a temperature of less than 600 degrees C.

21. The method according to claim 20, wherein the at least one ion permeable barrier includes one of a polymeric or inorganic ceramic-based ion permeable barrier.

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

23. The method according to claim 16, wherein the caustic compound is MOH.

24. A method for co-producing M-carboxylate and bromine, the method comprising the steps of:

contacting a first region of an electrochemical cell having a cathode with a catholyte comprising carbon dioxide;

contacting a second region of the electrochemical cell having an anode with an anolyte comprising an MBr where M is at least one cation;

applying an electrical potential between the anode and the cathode of the electrochemical cell sufficient to produce the M-carboxylate recoverable from the first region of the electrochemical cell and the bromine recoverable from the second region of the electrochemical cell;

reacting the bromine from the second region of the electrochemical cell with an alkane to produce a halogenated compound and HBr, the HBr being recycled back to an acidification chamber;

reacting the M-carboxylate with the HBr via the acidification chamber to produce a carboxylic acid and MBr, the MBr being recycled to an input of the second region of the electrochemical cell.

25. The method as claimed in claim 24, wherein the alkane is ethane.

26. The method as claimed in claim 25, wherein the halogenated compound is bromoethane.

27. The method as claimed in claim 26, wherein M is tetrabutylammonium.