US 4,608,133 AGrant
Means and Method for the Electrochemical Reduction of Carbon Dioxide to Provide a Product
Issue Date:1986-08-26
•48 Claims
•1 Drawing Sheets
Abstract
Apparatus and method for the electrochemical reduction of carbon dioxide to a product includes a housing divided into two sections by a membrane. An electrolyte solution including a non-aqueous electrolyte and a supporting electrolyte is provided to the two sections of the housing. A cathode is located in one section of the housing while an anode is located in the other section. Carbon dioxide is provided to the section having the cathode. A direct current voltage is provided to the cathode and to the anode to cooperate in a reaction between the carbon dioxide and the electrolyte solution to provide a product.
Metadata
Assignee
- Texaco Inc.
Inventors
- Abraham Morduchowitz
- Peter G. P. Ang
Application Information
Application Number:US 7431236
Filing Date:1985-06-10
Priority Date:1985-06-10
Art Unit:112
Classifications
IPC:
C25B 300
Field of Search:
20472;75;237;242;252;263;264;265;59 R
Patent Drawings (1 sheets)
Description
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to apparatus and method for the reduction of carbon dioxide to a product in general and, more particularly, to electrochemical apparatus and methods.
SUMMARY OF THE INVENTION
Apparatus and method for the electrochemical reduction of carbon dioxide to a product includes a housing divided into two sections by membrane. An electrolyte solution including a non-aqueous electrolyte and a supporting electrolyte is provided to the two sections of the housing. A cathode is located in one section of the housing while an anode is located in the other section. Carbon dioxide is provided to the section having the cathode. A direct voltage is provided to the cathode and to the anode so that a current can pass and cooperate in a reaction between the carbon dioxide and the electrolyte solution to provide a product.
The objects and advantages of the invention will appear more fully hereinafter, from a consideration of the detailed description which follows, taking together the accompanying drawing, when one embodiment is illustrated by way of example. It is to be expressly understood, however, that the drawing is for illustrative purposes only, and it is not to be construed as defining the limits of the invention.
DESCRIPTION OF THE DRAWING
The drawing is in partial block diagram form and partial mechanical drawing form shows apparatus, constructed in accordance with the present invention, for the reduction of carbon dioxide to provide a product.
DESCRIPTION OF A PREFERRED EMBODIMENT OF THE INVENTION
Referring to the FIGURE, there is shown a housing 1 made of suitable material to contain an electrolyte solution having a electrolyte permeable membrane 3. The membrane 3 will pass ions. Contained within housing 1 is an electrolyte solution 8 including a non-aqueous electrolyte selected from the following: dimethylformamide or magnesium perchlorate, and a supporting electrolyte selected from the following: tetrabutylammonium perchlorate, lithium perchlorate and ammonium perchlorate.
A biasing circuit 12 has a positive terminal connected to an anode 16 and a negative terminal connected to a cathode 19. Anode 16 may be a carbon base or graphite base electrode. Cathode 19 may be, made from p-silicon, gold or lead. A source 24 provides carbon dioxide through a valve 26, using a pump 30, to housing 1. A source 42 provides the electrolyte solution to housing 1 through a valve 44 aided by a pump 46. The electrolyte leaving housing 1 is returned to electrolyte source 42 by way of a line 48.
With cathode 19 being made of either gold or lead and anode 16 being a carbon base or graphite base electrode an electrolyte including a non-aqueous electrolyte solution 8 such as dimethylformamide with a supporting electrolyte selected from the following group of supporting electrolytes: tetrabutylammonium, lithium perchlorate or ammonium perchlorate, yielded substantial formate as a product.
When cathode 19 is made from p-silicon, and the non-aqueous electrolyte is dimethylformamide with a supporting electrolyte of one of the three aforementioned supporting electrolytes, the product is an oxalate. When cathode 19 is either lead or gold, the non-aqueous electrolyte is dimethylformamide with a supporting electrolyte of one of the three aforementioned electrolytes, the product is formate. The gold electrode also results in another product of formaldehyde in a lesser quantity.
When cathode 19 is made from lead and the non-aqueous electrolyte is magnesium perchlorate with a supporting electrolyte from one of the three aforementioned supporting electrolytes, the product is substantially formate with a lesser quantity of oxalate.
Cathode 19 may have its operation enhanced by the use of a catalyst with the material of cathode. Suitable catalysts are Group IV elements (germanium, carbon, tin) and metals such as mercury cadmium, bismuth and indium.
The apparatus and method hereinbefore reduces carbon dioxide to either formate, oxalate, formate with formaldehyde or formate with oxalate.
Claims
What is claimed is:
1. Apparatus for the electrochemical reduction of carbon dioxide to provide a product comprising: housing means for containing an electrolyte solution including a non-aqueous electrolyte with a supporting electrolyte, means for dividing the housing means into two sections while permitting the electrolyte solution to move between the two sections, means for providing carbon dioxide to one section of the housing means, a cathode located in the section of the housing means receiving the carbon dioxide, an anode located in the section of the housing not receiving the carbon dioxide, means for providing a direct current voltage to the cathode and to the anode, to cooperate in a reaction between the carbon dioxide in the electrolyte solution to provide a product, and means for removing the product from the housing means.
2. Apparatus as described in claim 1 in which the non-aqueous electrolyte is selected from the group consisting of dimethylformamide and magnesium perchlorate.
3. Apparatus as described in claim 2 in which the supporting electrolyte is selected from the group consisting of tetrabutylammonium perchlorate, lithium perchlorate and ammonium perchlorate.
4. Apparatus as described in claim 3 in which the product is an oxalate.
5. Apparatus as described in claim 4 in which the non-aqueous electrolyte is dimethylformamide, the cathode material is p-silicon and the anode is a carbon-graphite composition.
6. Apparatus as described in claim 5 in which the supporting electrolyte is lithium perchlorate.
7. Apparatus as described in claim 5 in which the supporting electrolyte is ammonium perchlorate.
8. Apparatus as described in claim 5 in which the supporting electrolyte is tetrabutylammonium perchlorate.
9. Apparatus as described in claim 3 in which the product is a formate.
10. Apparatus as described in claim 9 in which the product also includes formaldehyde.
11. Apparatus as described in claim 10 in which the non-aqueous electrolyte is dimethylformamide and the cathode material is gold.
12. Apparatus as described in claim 11 in which the supporting electrolyte is lithium perchlorate.
13. Apparatus as described in claim 11 in which the supporting electrolyte is ammonium perchlorate.
14. Apparatus as described in claim 11 in which the supporting electrolyte is tetrabutylammonium perchlorate.
15. Apparatus as described in claim 9 in which the product also includes oxalate.
16. Apparatus as described in claim 15 in which the non-aqueous electrolyte is magnesium perchlorae, and the cathode is lead.
17. Apparatus as described in claim 16 in which the supporting electrolyte is lithium perchlorate.
18. Apparatus as described in claim 16 in which the supporting electrolyte is ammonium perchlorate.
19. Apparatus as described in claim 16 in which the supporting electrolyte is tetrabutylammonium perchlorate.
20. Apparatus as described in claim 9 in which the non-aqueous electrolyte is dimethylformamide, and the cathode material is lead.
21. Apparatus as described in claim 20 in which the supporting electrolyte is lithium perchlorate.
22. Apparatus as described in claim 20 in which the supporting electrolyte is ammonium perchlorate.
23. Apparatus as described in claim 20 in which the supporting electrolyte is tetrabutylammonium perchlorate.
24. Apparatus as described in claim 1 in which the cathode has a catalyst selected from the group consisting of germanium, carbon, tin, mercury, cadmium, bismuth, antimony and indium.
25. A method for electrochemically reducing carbon dioxide to provide a product comprising the steps of: contianing an electrolyte solution including a non-aqueous electrolyte with a supporting electrolyte, dividing the electrolyte into two portions with a membrane, providing carbon dioxide to one portion of the electrolyte, placing a cathode in the portion of the electrolyte means receiving the carbon dioxide, placing an anode in the portion of the electrolyte not receiving the carbon dioxide, and providing a direct current voltage to the cathode and to the anode, to cooperate in a reaction between the carbon dioxide and the electrolyte solution to provide a product.
26. A method as described in claim 25 in which the non-aqueous electrolyte is selected from the group consisting of dimethylformamide and magnesium perchlorate.
27. A method as described in claim 26 in which the supporting electrolyte is selected from the group consisting of tetrabutylammonium perchlorate, lithium perchlorate and ammonium perchlorate.
28. A method as described in claim 27 in which the product is an oxalate.
29. A method as described in claim 28 in which the non-aqueous electrolyte is dimethylformamide, the cathode material is p-silicon.
30. A method as described in claim 29 in which the supporting electrolyte is lithium perchlorate.
31. A method as described in claim 29 in which the supporting electrolyte is ammonium perchlorate.
32. A method as described in claim 29 in which the supporting electrolyte is tetrabutylammonium perchlorate.
33. A method as described in claim 27 in which the product is a formate.
34. A method as described in claim 33 in which the product also includes formaldehyde.
35. A method as described in claim 33 in which the product also includes oxalate.
36. A method as described in claim 35 in which the non-aqueous electrolyte is magnesium perchlorate, and the cathode material is lead.
37. A method as described in claim 36 in which the supporting electrolyte is lithium perchlorate.
38. A method as described in claim 36 in which the supporting electrolyte is ammonium perchlorate.
39. A method as described in claim 36 in which the supporting electrolyte is tetrabutylammonium perchlorate.
40. A method as described in claim 34 in which the non-aqueous electrolyte is dimethylformamide and the cathode material is gold.
41. A method as described in claim 40 in which the supporting electrolyte is lithium perchlorate.
42. A method as described in claim 40 in which the supporting electrolyte is ammonium perchlorate.
43. A method as described in claim 40 in which the supporting electrolyte is tetrabutylammonium perchlorate.
44. A method as described in claim 33 in which the non-aqueous electrolyte is dimethylformamide, and the cathode material is lead.
45. A method as described in claim 44 in which the supporting electrolyte is lithium perchlorate.
46. A method as described in claim 44 in which the supporting electrolyte is ammonium perchlorate.
47. A method as described in claim 44 in which the supporting electrolyte is tetrabutylammonium perchlorate.
48. A method as described in claim 25 in which the cathode has a catalyst selected from the group consisting of germanium, carbon, tin, mercury, cadmium, bismuth, antimony and indium.