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US-20260125811-A1 - METHODS OF USING A MIXED CONDUCTING MEMBRANE UNDER HIGH PRESSURES

US20260125811A1US 20260125811 A1US20260125811 A1US 20260125811A1US-20260125811-A1

Abstract

Herein discussed is a method comprising: providing a mixed conducting membrane; exposing the membrane to a reducing environment on both sides of the membrane during the entire time of operation, wherein the operation does not receive electricity or generate electricity; wherein the reducing environments on both sides of the membrane have a pressure in the range of 5-300 bar. In an embodiment, the mixed conducting membrane conducts electrons and oxide ions. In an embodiment, the reducing environments on both sides of the membrane have a pressure of no less than 10 bar or no less than 20 bar or no less than 30 bar.

Inventors

  • Nicholas FARANDOS
  • Ruofan Wang
  • Bryan M. Blackburn

Assignees

  • Utility Global, Inc.

Dates

Publication Date
20260507
Application Date
20250926

Claims (20)

  1. 1 . A method comprising: providing a mixed conducting membrane; exposing the membrane to a reducing environment on both sides of the membrane during the entire time of operation, wherein the operation does not receive electricity or generate electricity; wherein the reducing environments on both sides of the membrane have a pressure in the range of 5-300 bar.
  2. 2 . The method of claim 1 , wherein the mixed conducting membrane conducts electrons and oxide ions.
  3. 3 . The method of claim 1 , wherein the reducing environments on both sides of the membrane have a pressure of no less than 10 bar or no less than 20 bar or no less than 30 bar.
  4. 4 . The method of claim 1 , wherein the membrane comprises lanthanum chromite and a material selected from the group consisting of doped ceria, yttria-stabilized zirconia (YSZ), lanthanum strontium gallate magnesite (LSGM), scandia-stabilized zirconia (SSZ), Sc and Ce doped zirconia, and combinations thereof.
  5. 5 . The method of claim 4 , wherein the lanthanum chromite comprises undoped lanthanum chromite, strontium doped lanthanum chromite, iron doped lanthanum chromite, strontium and iron doped lanthanum chromite, lanthanum calcium chromite, or combinations thereof.
  6. 6 . The method of claim 1 , wherein the membrane comprises an electronically conducting phase and an ionically conducting phase.
  7. 7 . The method of claim 6 , 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.
  8. 8 . The method of claim 1 , wherein the membrane comprises CoCGO or LST (lanthanum-doped strontium titanate)-stabilized zirconia.
  9. 9 . The method of claim 8 , wherein the stabilized zirconia comprises YSZ or SSZ or SCZ (scandia-ceria-stabilized zirconia), and wherein the LST comprises LaSrCaTiO 3 .
  10. 10 . The method of claim 1 , wherein the membrane comprises Nickel, Copper, Cobalt, or Niobium-doped zirconia.
  11. 11 . The method of claim 1 , wherein one side of the membrane is in contact with a cathode at which steam is electrochemically reduced to produce hydrogen or carbon dioxide is electrochemically reduced to produce carbon monoxide.
  12. 12 . The method of claim 11 , wherein the cathode comprises Ni or NiO and a material selected from the group consisting of YSZ, CGO, SDC, SSZ, SCZ, LSGM, CoCGO, LST, and combinations thereof.
  13. 13 . The method of claim 12 , wherein the cathode comprises Ni—YSZ or Ni—CGO or LaSrFeCr—SSZ or LaSrFeCr—SCZ or LST (lanthanum-doped strontium titanate)-SCZ.
  14. 14 . The method of claim 11 , wherein an opposite side of the membrane is in contact with an anode that receives a fuel, wherein the fuel does not mix with cathode feed directly.
  15. 15 . The method of claim 14 , wherein the anode comprises Ni or NiO and a material selected from the group consisting of YSZ, CGO, SDC, SSZ, LSGM, and combinations thereof.
  16. 16 . The method of claim 14 , wherein the anode comprises doped or undoped ceria and a material selected from the group consisting of Cu, CuO, Cu 2 O, Ag, Ag 2 O, Au, Au 2 O, Au 2 O 3 , Pt, Pd, Ru, Rh, Ir, LaCaCr, LaSrCrFe, YSZ, CGO, SDC, SSZ, LSGM, stainless steel, and combinations thereof.
  17. 17 . The method of claim 14 , wherein the anode comprises lanthanum chromite and a material selected from the group consisting of doped ceria, yttria-stabilized zirconia (YSZ), lanthanum strontium gallate magnesite (LSGM), scandia-stabilized zirconia (SSZ), Sc and Ce doped zirconia, and combinations thereof; wherein optionally the lanthanum chromite comprises undoped lanthanum chromite, strontium doped lanthanum chromite, iron doped lanthanum chromite, strontium and iron doped lanthanum chromite, lanthanum calcium chromite, or combinations thereof.
  18. 18 . The method of claim 14 , wherein the fuel comprises a hydrocarbon or hydrogen or carbon monoxide or ammonia or combinations thereof.
  19. 19 . The method of claim 1 , wherein the membrane is tubular.
  20. 20 . The method of claim 1 , wherein the reducing environments on both sides of the membrane have a temperature of no less than 600° C., or no less than 700° C., or no less than 800° C., or no less than 900° C.

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. 63/717,734 filed Nov. 7, 2024, the entire disclosure of which is hereby incorporated herein by reference. TECHNICAL FIELD This invention generally relates to mixed conducting membranes. More specifically, this invention relates to methods of using mixed conducting membranes under high pressures. 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 for 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 an increasing need and interest to develop new technological platforms to produce these building blocks and valuable products. This disclosure discusses the production of CO and/or H2 via efficient electrochemical pathways using mixed conducting membranes. Furthermore, the method and system as disclosed herein operate at higher pressures that are contrary to conventional wisdom. SUMMARY Herein discussed is a method comprising: providing a mixed conducting membrane; exposing the membrane to a reducing environment on both sides of the membrane during the entire time of operation, wherein the operation does not receive electricity or generate electricity; wherein the reducing environments on both sides of the membrane have a pressure in the range of 5-300 bar. In an embodiment, the mixed conducting membrane conducts electrons and oxide ions. In an embodiment, the reducing environments on both sides of the membrane have a pressure of no less than 10 bar or no less than 20 bar or no less than 30 bar. In an embodiment, the membrane comprises lanthanum chromite and a material selected from the group consisting of doped ceria, yttria-stabilized zirconia (YSZ), lanthanum strontium gallate magnesite (LSGM), scandia-stabilized zirconia (SSZ), Sc and Ce doped zirconia, and combinations thereof. In an embodiment, the lanthanum chromite comprises undoped lanthanum chromite, strontium doped lanthanum chromite, iron doped lanthanum chromite, strontium and iron doped lanthanum chromite, lanthanum calcium chromite, or combinations thereof. In an embodiment, the membrane comprises an electronically conducting phase and an ionically conducting phase. In an embodiment, 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. In an embodiment, the membrane comprises CoCGO or LST (lanthanum-doped strontium titanate)-stabilized zirconia. In an embodiment, the stabilized zirconia comprises YSZ or SSZ or SCZ (scandia-ceria-stabilized zirconia), and wherein the LST comprises LaSrCaTiO3. In an embodiment, the membrane comprises Nickel, Copper, Cobalt, or Niobium-doped zirconia. In an embodiment, one side of the memb