Process and high surface area electrodes for the electrochemical reduction of carbon dioxide

• US 10,287,696 B2
• Filed: 08/28/2014
• Issued: 05/14/2019
• Est. Priority Date: 07/26/2012
• Status: Active Grant

• Current Assignee: Avantium Knowledge Centre B.V. (Avantium NV)
• Original Assignee: Avantium Knowledge Centre B.V. (Avantium NV)
• Inventors: Kaczur, Jerry J., Kramer, Theodore J., Keyshar, Kunttal, Majsztrik, Paul, Twardowski, Zbigniew
• Primary Examiner(s): Wong, Edna
• Application Number:
  US14/471,152
• Publication Number:
  US 20140367273A1
• Time in Patent Office: 1,720 Days
• Field of Search: 570101, 205345, 205440, 205465, 205510, 205618, 205619, 205349, 205480
• CPC Class Codes: C25B 11/091 consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
• 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 3/25 Reduction
• 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

Abstract

Methods and systems for electrochemical conversion of carbon dioxide to organic products including formate and formic acid are provided. A method may include, but is not limited to, steps (A) to (C). Step (A) may introduce an acidic anolyte to a first compartment of an electrochemical cell. The first compartment may include an anode. Step (B) may introduce a bicarbonate-based catholyte saturated with carbon dioxide to a second compartment of the electrochemical cell. The second compartment may include a high surface area cathode including indium and having a void volume of between about 30% to 98%. At least a portion of the bicarbonate-based catholyte is recycled. Step (C) may apply an electrical potential between the anode and the cathode sufficient to reduce the carbon dioxide to at least one of a single-carbon based product or a multi-carbon based product.

Claims

1. A method for electrochemical reduction of carbon dioxide into products, comprising:

(A) introducing an acidic anolyte to a first compartment of a first electrochemical cell, the first compartment including an anode;

(B) introducing a catholyte including an alkali metal bicarbonate to a second compartment of the first electrochemical cell, the catholyte saturated with carbon dioxide, the second compartment including a high surface area cathode, the high surface area cathode including a coating containing indium and having a void volume of between about 30% to 98%, at least a portion of the catholyte including the alkali metal bicarbonate being recycled;

(C) applying an electrical potential between the anode and the cathode sufficient to reduce the carbon dioxide to an alkali metal formate;

(D) introducing the alkali metal formate to an ion exchange compartment of a second electrochemical cell;

(E) applying an electrical potential between an anode of the second electrochemical cell and a cathode of the second electrochemical cell sufficient to produce at least formic acid and an alkali metal hydroxide;

(F) introducing the alkali metal hydroxide with carbon dioxide to generate at least a portion of the alkali metal bicarbonate introduced to the second compartment of the first electrochemical cell; and

(G) separating the alkali metal formate from the alkali metal bicarbonate of the catholyte of the first electrochemical cell with a nano-filtration system, wherein the nano-filtration system separates monovalent anions from divalent anions.

2. The method of claim 1, wherein separating the alkali metal formate from the alkali metal bicarbonate of the catholyte of the first electrochemical cell with a nano-filtration system comprises:

introducing the alkali metal bicarbonate of the catholyte to an alkali metal hydroxide to convert at least a portion of the alkali metal bicarbonate to an alkali metal carbonate; and

separating the alkali metal carbonate from the alkali metal formate with a nano-filtration unit.

3. The method of claim 2, further comprising:

introducing the alkali metal carbonate with the alkali metal hydroxide and with carbon dioxide to generate at least a portion of the alkali metal bicarbonate introduced to the second compartment of the first electrochemical cell.

4. The method of claim 1, wherein at least a portion of the alkali metal hydroxide is generated by one or more of the first electrochemical cell and the second electrochemical cell.

5. The method of claim 1, wherein the formic acid is generated in the ion exchange compartment of the second electrochemical cell.

6. The method of claim 1, wherein the alkali metal hydroxide is generated in a cathode compartment of the second electrochemical cell.

7. The method of claim 1, wherein the high surface area cathode has a specific surface area of greater than 2 cm²/cm³.

8. The method of claim 1, wherein the acidic anolyte includes sulfuric acid.

9. The method of claim 1, further comprising:

generating a halogen selected from the group consisting of F₂, Cl₂, Br₂, and I₂ in at least one of the first compartment of the first electrochemical cell and the first compartment of the second electrochemical cell.

10. The method of claim 9, further comprising:

reacting the halogen with an organic compound to produce a halogenated product.

11. The method of claim 10, wherein the halogen is bromine.

12. The method of claim 9, wherein the halogen is bromine.

13. The method of claim 1, wherein the high surface area cathode includes from 5% to 99% as indium in alloy with bismuth.