US-12618163-B2 - Electrochemical production of carbon monoxide and valuable products

Abstract

Herein discussed is a method of producing carbon monoxide comprising: (a) providing an electrochemical reactor having an anode, a cathode, and a mixed-conducting membrane between the anode and the cathode; (b) introducing a first stream to the anode, wherein the first stream comprises a fuel; (c) introducing a second stream to the cathode, wherein the second stream comprises carbon dioxide, wherein carbon monoxide is generated from carbon dioxide electrochemically; wherein the reactor generates no electricity and receives no electricity. In an embodiment, the anode and the cathode are separated by the membrane and are both exposed to reducing environments during the entire time of operation.

Inventors

• Matthew Dawson
• Nicholas FARANDOS
• Jin Dawson
• Jason Dana

Assignees

• Utility Global, Inc.

Dates

Publication Date

20260505

Application Date

20221130

Claims (20)

1. 1 . A method of producing carbon monoxide comprising: (a) providing an electrochemical reactor having an anode, a cathode, and a mixed-conducting membrane between the anode and the cathode, wherein both the anode and the cathode comprise Ni; (b) introducing a first stream to the anode, wherein the first stream comprises a fuel; (c) introducing a second stream to the cathode, wherein the second stream comprises carbon dioxide and carbon monoxide, wherein the carbon monoxide is less than the carbon dioxide in the second stream, wherein carbon monoxide is generated from carbon dioxide electrochemically; wherein the reactor generates no electricity and receives no electricity.
2. 2 . The method of claim 1 , wherein the fuel comprises ammonia, syngas, hydrogen, methanol, carbon monoxide, or combinations thereof.
3. 3 . The method of claim 1 , wherein the cathode produces a cathode exhaust, wherein the cathode exhaust is passed through a separator, wherein the generated carbon monoxide is separated from carbon dioxide.
4. 4 . The method of claim 1 , wherein the anode and the cathode are separated by the membrane and are both exposed to reducing environments during the entire time of operation.
5. 5 . The method of claim 1 , wherein the anode and the cathode have the same elements.
6. 6 . The method of claim 1 , wherein the anode and the cathode and the membrane have the same elements.
7. 7 . The method of claim 6 , wherein the anode and the cathode and the membrane comprise Ni-YSZ or LaSrFeCr-SSZ or LaSrFeCr-SCZ.
8. 8 . The method of claim 1 , wherein the anode and the cathode comprise Ni or NiO and a material selected from the group consisting of YSZ, CGO, SDC, SSZ, LSGM, CoCGO, and combinations thereof.
9. 9 . The method of claim 1 , wherein the membrane comprises an electronically conducting phase and an ionically conducting phase.
10. 10 . The method of claim 9 , wherein the electronically conducting phase comprises doped lanthanum chromite or an electronically conductive metal or combination thereof; and wherein the ionically conducting phase comprises a material selected from the group consisting of gadolinium or samarium doped ceria, yttria-stabilized zirconia (YSZ), lanthanum strontium gallate magnesite (LSGM), scandia-stabilized zirconia (SSZ), Sc and Ce doped zirconia (SCZ), and combinations thereof.
11. 11 . The method of claim 1 , wherein the membrane comprises CoCGO or LST (lanthanum-doped strontium titanate)-stabilized zirconia.
12. 12 . The method of claim 11 , wherein the stabilized zirconia comprises YSZ or SSZ or SCZ (scandia-ceria-stabilized zirconia), and wherein the LST comprises LaSrCaTiO 3 .
13. 13 . The method of claim 1 , wherein the membrane comprises Nickel, Copper, Cobalt, or Niobium-doped zirconia.
14. 14 . A method of producing valuable products comprising: (a) providing two electrochemical reactors each having an anode, a cathode, and a mixed-conducting membrane between the anode and the cathode, wherein both the anode and the cathode comprise Ni; (b) introducing a fuel stream to each of the anodes; (c) introducing a CO 2 -containing stream to a first cathode and introducing a H 2 O-containing stream to a second cathode, wherein the first cathode produces a first cathode exhaust stream and the second cathode produces a second cathode exhaust stream, wherein the CO 2 -containing stream introduced to the first cathode also comprises carbon monoxide, wherein the carbon monoxide is less than the carbon dioxide; wherein carbon monoxide is generated from carbon dioxide electrochemically and hydrogen is generated from water electrochemically; wherein neither reactor generates electricity or receives electricity.
15. 15 . The method of claim 14 , wherein CO is separated from CO 2 from the first cathode exhaust stream and H 2 is separated from H 2 O from the second cathode exhaust stream.
16. 16 . The method of claim 15 comprising utilizing the separated CO and the separated H 2 to produce methanol, ethanol, hydrocarbons, plastic monomers, polyethylene, or combinations thereof.
17. 17 . The method of claim 14 , wherein the anodes and the cathodes are separated by the membranes respectively and are all exposed to reducing environments during the entire time of operation.
18. 18 . The method of claim 14 , wherein the membrane comprises CoCGO or LST (lanthanum-doped strontium titanate)-stabilized zirconia.
19. 19 . The method of claim 18 , wherein the stabilized zirconia comprises YSZ or SSZ or SCZ (scandia-ceria-stabilized zirconia), and wherein the LST comprises LaSrCaTiO 3 .
20. 20 . The method of claim 14 , wherein the membrane comprises Nickel, Copper, Cobalt, or Niobium-doped zirconia.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit under 35 U.S.C. 119(e) of U.S. Provisional Patent Application No. 63/284,830 filed Dec. 1, 2021 and U.S. Provisional Patent Application No. 63/289,421 filed Dec. 14, 2021, the entire disclosures of which are hereby incorporated herein by reference. TECHNICAL FIELD This invention generally relates to production of carbon monoxide (CO) and related valuable products. More specifically, this invention relates to electrochemical production of carbon monoxide (CO) and related valuable products. BACKGROUND Carbon monoxide (CO) is a colorless, odorless, tasteless, and flammable gas that is slightly less dense than air. It is well known for its poisoning effect because CO readily combines with hemoglobin to produce carboxyhemoglobin, which is highly toxic when the concentration exceeds a certain level. However, CO is a key ingredient in many chemical and industrial processes. CO has a wide range of functions across all disciplines of chemistry, e.g., metal-carbonyl catalysis, radical chemistry, cation and anion chemistries. Carbon monoxide is a strong reductive agent and has been used in pyrometallurgy to reduce metals from ores for centuries. As an example for making specialty compounds, CO is used in the production of vitamin A. Hydrogen (H2) in large quantities is needed in the petroleum and chemical industries. For example, large amounts of hydrogen are used in upgrading fossil fuels and in the production of methanol or hydrochloric acid. Petrochemical plants need hydrogen for hydrocracking, hydrodesulfurization, hydrodealkylation. Hydrogenation processes to increase the level of saturation of unsaturated fats and oils also need hydrogen. Hydrogen is also a reducing agent of metallic ores. Hydrogen may be produced from electrolysis of water, steam reforming, lab-scale metal-acid process, thermochemical methods, or anaerobic corrosion. Many countries are aiming at a hydrogen economy. In the Fischer-Tropsch process, CO and H2 are both essential building blocks, which are often produced by converting carbon-rich feedstocks (e.g., coal). A mixture of CO and H2—syngas—can combine to produce various liquid fuels, e.g., via the Fischer-Tropsch process. Syngas can also be converted to lighter hydrocarbons, methanol, ethanol, or plastic monomers (e.g., ethylene). The ratio of CO/H2 is important in all such processes in order to produce the desired compounds. Conventional techniques require extensive and expensive separation and purification processes to obtain the CO and H2 as building blocks. Clearly there is increasing need and interest to develop new technological platforms to produce these building blocks and valuable products. This disclosure discusses production of valuable products via efficient electrochemical pathways. Furthermore, the method and system as disclosed herein do not require the extensive and expensive separation and purification processes as needed in traditional technologies. SUMMARY Herein discussed is a method of producing carbon monoxide comprising: (a) providing an electrochemical reactor having an anode, a cathode, and a mixed-conducting membrane between the anode and the cathode; (b) introducing a first stream to the anode, wherein the first stream comprises a fuel; (c) introducing a second stream to the cathode, wherein the second stream comprises carbon dioxide, wherein carbon monoxide is generated from carbon dioxide electrochemically; wherein the reactor generates no electricity and receives no electricity. In an embodiment, the fuel comprises ammonia, syngas, hydrogen, methanol, carbon monoxide, or combinations thereof. In an embodiment, the cathode exhaust is passed through a separator, wherein the generated carbon monoxide is separated from carbon dioxide. In an embodiment, the second stream comprises carbon monoxide, wherein the carbon monoxide is less than the carbon dioxide. In some embodiments, the anode and the cathode are separated by the membrane and are both exposed to reducing environments during operation of the reactor. In some of these embodiments, the anode and cathode are both exposed to reducing environments during the entire time of operation of the reactor. In other of these embodiments, the anode and the cathode are both exposed to reducing environments while carbon monoxide is produced from the carbon dioxide at the cathode. In an embodiment, the anode and the cathode have the same elements. In an embodiment, the anode and the cathode and the membrane have the same elements. In an embodiment, the anode and the cathode and the membrane comprise Ni-YSZ or LaSrFeCr-SSZ or LaSrFeCr-SCZ. In an embodiment, the anode and the cathode comprise Ni or NiO and a material selected from the group consisting of YSZ, CGO, SDC, SSZ, LSGM, CoCGO, and combinations thereof. In an embodiment, the membrane comprises an electronically conducting phase and an ionically conducting phase. In an embodiment, the electr