EP0500708A1 - Compresseur solide d'oxygene - Google Patents

Compresseur solide d'oxygene

Info

Publication number
EP0500708A1
EP0500708A1 EP19900917179 EP90917179A EP0500708A1 EP 0500708 A1 EP0500708 A1 EP 0500708A1 EP 19900917179 EP19900917179 EP 19900917179 EP 90917179 A EP90917179 A EP 90917179A EP 0500708 A1 EP0500708 A1 EP 0500708A1
Authority
EP
European Patent Office
Prior art keywords
electrolyte
oxygen
compressor
compressor according
high pressure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19900917179
Other languages
German (de)
English (en)
Other versions
EP0500708A4 (en
Inventor
Ashok V. Joshi
Jesse A. Nachlas
Kevin Stuffle
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ceramatec Inc
Original Assignee
Ceramatec Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ceramatec Inc filed Critical Ceramatec Inc
Publication of EP0500708A1 publication Critical patent/EP0500708A1/fr
Publication of EP0500708A4 publication Critical patent/EP0500708A4/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
    • B01D53/326—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00 in electrochemical cells

Definitions

  • This invention relates to the electrochemical compression of ionizable gases capable of electrochemical transport through a solid electrolyte and especially to the compression of oxygen.
  • Pure oxygen has numerous applications. For instance, oxygen is used in large quantities in enrichment of blast furnaces, chemical synthesis, oxy-acetylene welding, life support and other medical uses. U.S. commercial consumption exceeds 18 metric tons (20 million short tons) per year. Oxygen costs about 17.7 cents per cubic meter (5 cents per cubic foot) in small quantities, and about 10 cents per kilogram ($15/ton) in large quantities. Currently, 99% (percent) of such oxygen is prepared by liquefaction of air and about 1% (percent) by electrolysis. Efficient storage and transport requires that oxygen be prepared at high
  • the present invention offers an alternative to mechanical compression of oxygen.
  • the present invention makes use of oxygen-ion conductive solids to prepare high pressure oxygen
  • Oxygen-ion conductive solids are currently used in numerous practical devices for power generation, oxygen partial pressure measurement and oxygen separation.
  • U.S. Patent 4,725,346 an oxygen delivery device is disclosed. The specification of that patent is incorporated herein by reference.
  • FIG. 1 is an electrochemical cell.
  • the ion conductive solid is the electrolyte and the electronic conductors are the
  • the net chemical potential at each interface is the sum of the chemical potentials of the individual species at that interface.
  • the electrolyte will conduct oxygen in order to move the system toward a state of equilibrium.
  • FIG. 1 is a schematic illustration of oxygen transport through an oxygen-ion conductive electrolyte
  • FIG. 2 is a cross-sectional view of a solid state oxygen compressor illustrating one embodiment of the invention
  • FIG. 3 is a graphical illustration of the rate of oxygen pressure increase achieved by the compressor illustrated in FIG. 2;
  • FIG. 4 is a cross-sectional view of a solid state compressor similar to that illustrated in FIG. 2 which includes a heater internal to the high pressure chamber;
  • FIG. 5 is a graphical illustration of the rate of oxygen pressure increase achieved by the compressor illustrated in FIG. 4;
  • FIG. 6 is a cross-sectional view of a solid state compressor similar to that illustrated in FIG. 2 in which dead volume has been minimized and illustrates another embodiment of the invention
  • FIG. 6A is an enlarged sectional view of the end of the solid state compressor shown in Figure 6;
  • FIG. 7 is graphical illustration of the rate of oxygen pressure increase achieved by the compressor illustrated in FIG. 6.
  • An oxygen compressor utilizing a solid state oxygen ion transport membrane which transports oxygen ions when subjected to a voltage differential is disclosed.
  • Particularly useful oxygen ion transport membranes are ceramic metal oxides such as zirconia, ceria, hafnia, bismuth oxide and the like. Such electrolytes are
  • the present invention consists of an ion- conductive solid constructed in such a way as to create a mechanical barrier between a low pressure oxygen reservoir and a confined volume.
  • the barrier and confined volume must be capable of supporting high pressure gas (most particularly oxygen).
  • Electrode an electronically conductive material
  • oxygen-ion conductive solids are metal oxides, a class of ceramic materials, such as zirconia, hafnia, bismuth oxide and the like.
  • the chief solid material that is used as an oxygen ion conductor is stabilized zirconia.
  • Stabilized zirconia has a combination of
  • An electrochemical oxygen compressor was fabricated as depicted in FIG. 2.
  • a silver lead was coiled around the external electrode to form the external lead wire.
  • Another silver wire was laid along the internal wall of the tube to form the internal lead wire.
  • the open end of the zirconia tube was secured into the top flange 11 of an Inconel pressure vessel 12 (internal volume of 0.4 liters) using a compression fitting.
  • the top flange 12 was bolted into a fixed flange 12a welded to the pressure vessel 12. The internal diameter of the zirconia tube was exposed to the
  • the internal surface of the pressure vessel was lined with alumina insulation 13.
  • a heater 14 was placed along the internal diameter of the zirconia tube. This heater was fabricated by coiling nickel-chrome wire around an 0.31 centimeters outer diameter (0.125 inches outer diameter) alumina tube 15 and coating with alumina cement.
  • the alumina tube 15 also served as an air inlet and preheater. Air was pumped in through the alumina tube and out through the annulus between the alumina tube and the zirconia tube. The zirconia tube was heated to approximately 800°C. The air inside the
  • Example 1 The oxygen compressor of Example 1 was modified by installing a heater that was external to the zirconia tube as depicted in FIG. 4. A sterling silver wire was coiled in contact with the internal diameter of the electrolyte tube to serve as the lead wire.
  • the pressure vessel was designed so that the internal wall of the pressure vessel was close fitting to the zirconia tube.
  • a furnace was placed around the outside of the pressure vessel in order to heat the electrolyte to 800°C.
  • the bottom 19.1 centimeters (7.5 inches) of the zirconia tube was coated inside and out successively with lanthanum strontium manganite and silver to form the electrodes.
  • Silver wires were coiled around the electrodes to act as lead wires.
  • the zirconia tube was secured into the top flange of the pressure vessel (internal volume of 0.025 liters) using a compression fitting.
  • the internal volume of the pressure vessel internal volume of 0.025 liters
  • an oxygen compressor of the invention it is desirable to utilize an ion (oxygen ion) conducting electrolyte having excellent strength. Zirconia or hafnia are for this reason preferred electrolytes with zirconia especially preferred because of its strength and
  • the zirconia should preferably be in the shape of an elongated cylinder.
  • a cylindrical tube with one closed end and one open end is especially preferred.
  • Another feature of the invention is that the high pressure region is external to the electrolyte.
  • the pressure acts on the external surface of the tube radially toward the longitudinal axis of the tube. While it is common in metal systems to contain high pressure inside the smallest diameter member, the tendency of ceramics to fail in tension militates against
  • Ceramics generally are much stronger in compression than in tension, thus a cylindrical
  • electrolyte tube of a certain diameter and wall thickness will sustain a greater pressure on its external surface. External pressure puts the cylindrical wall under
  • a feature of the present solid state compressor is a low ratio of the pressure chamber volume to
  • the quantity of oxygen transported through a particular electrolyte is proportional to current for a given temperature.
  • oxygen compressors it is desired to achieve the operating pressure as rapidly as possible.
  • the compressor illustrated in FIG. 6 is particularly effective in rapidly reaching a desired high- pressure output.
  • the high pressure creates some back EMF which at a pressure of 13,790,000 newtons per square meter (2000 psi) amounts to about 115 millivolts.
  • ionizable diatomic gases capable of electrochemical ion transport through a solid electrolyte.
  • transportable gases include hydrogen, chlorine, fluorine and the like. Hydrogen may be readily ionized and transported through proton
  • conductors such as barium cerate, hydrogen uranyl
  • chlorine and fluorine gases may be readily ionized and transported through chlorine ion conductors such as SrCl 2 -Al 2 O 3 and fluorine ion conductors such as LaF 3 or PbF 2 .
  • protons conductors may be readily substituted for the oxygen ion transporting electrolytes described hereinabove and illustrated in the attached drawings.
  • oxygen disassociates into hydrogen and oxygen.
  • oxygen may be separated and using the techniques of the instant
  • serial compression of oxygen and hydrogen may be readily
  • Water vapor at an elevated temperature may be introduced into an oxygen compressor of the type described herein to produce high pressure oxygen and a by- product water vapor stream rich in hydrogen.
  • This byproduct stream may then be introduced into a hydrogen compressor utilizing a proton conducting electrolyte to yield high pressure hydrogen and vent gas of water vapor.
  • the byproduct stream from the oxygen compressor could be fed to a condenser to condense the water vapor, recover pure hydrogen which could be mechanically compressed, especially after the hydrogen is passed through a drier to remove any residual moisture.
  • Hydrogen compression by disassociation of hydrogen, either in pure form or in combination with other gases, is preferably done at temperatures in the range of 50° to about 1000°C for the following proton conductors: phosphate (50-100°C), barium cerate (500-1000°C).
  • Electrodes suitably used in conjunction with such proton conductors are palladium, lanthanum strontium chromite, platinum, silver and copper, lanthanum strontium
  • the preferred electrode system is composed of lanthanum strontium manganite (LSM). Multiple layers are preferably applied until an electrode thickness of about 20 microns to about 200 microns is achieved. These LSM electrodes are especially adherent to the electrolyte, have a
  • Conductive ceramic electrodes other than LSM that are useful in the instant invention are lanthanum strontium chromite, strontium iron cobaltite and the like.
  • the sheet resistance of LSM electrodes tends to be higher than that of metal electrodes such as silver.
  • An effective manner of distributing current throughout the whole area of the LSM electrode is to use a metal wire mesh in intimate contact with the electrode.
  • electrolyte may be similarly structured by forcing a wire mesh cylinder into the electrolyte tube and then coating the mesh in a similar fashion to that done on the external electrode.
  • Ceria especially ceria stabilized with calcia, strontia or yttria, may be readily substitured for
  • Lanthanum strontium cobalitte is an especially effective electrode for use with ceria.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)

Abstract

Un compresseur électronique à l'état solide d'oxygène et d'autres gaz ionisables diatomiques comprend une membrane de transport d'ions d'oxygène constituée en oxyde métallique céramique, par example la zircone, qui transporte les ions d'oxygène lorsqu'elle est exposée à un potentiel électrique.
EP19900917179 1989-11-06 1990-11-06 Solid state oxygen compressor Withdrawn EP0500708A4 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US43239089A 1989-11-06 1989-11-06
US432390 1989-11-06

Publications (2)

Publication Number Publication Date
EP0500708A1 true EP0500708A1 (fr) 1992-09-02
EP0500708A4 EP0500708A4 (en) 1993-03-24

Family

ID=23715966

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19900917179 Withdrawn EP0500708A4 (en) 1989-11-06 1990-11-06 Solid state oxygen compressor

Country Status (3)

Country Link
EP (1) EP0500708A4 (fr)
AU (1) AU6742490A (fr)
WO (1) WO1991006691A1 (fr)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5118395A (en) * 1990-05-24 1992-06-02 Air Products And Chemicals, Inc. Oxygen recovery from turbine exhaust using solid electrolyte membrane
US5169506A (en) * 1990-12-31 1992-12-08 Invacare Corporation Oxygen concentration system utilizing pressurized air
EP0565790B1 (fr) * 1992-04-16 1996-11-06 Invacare Corporation Système de concentration d'oxygène utilisant une cellule électrochimique
FR2699912B1 (fr) † 1992-12-30 1995-01-27 Cryotechnologies Installation d'alimentation en oxygène embarquée sur véhicule.
FR2770149B1 (fr) * 1997-10-29 1999-12-17 Air Liquide Procede de separation de l'oxygene d'un melange de gaz le contenant et dispositif pour la mise en oeuvre de ce procede
US6502419B2 (en) 2000-04-13 2003-01-07 Sun Microsystems, Inc. Electro-desorption compressor
DE10156349B4 (de) * 2001-11-16 2006-01-26 Ballard Power Systems Ag Brennstoffzellenanlage
CA2525682A1 (fr) * 2003-05-28 2004-12-09 Pirelli & C. S.P.A. Cellule electrochimique servant a separer de l'oxygene
US12163697B2 (en) 2009-05-01 2024-12-10 Ffi Ionix Ip, Inc. Advanced system for electrochemical cell
WO2013096890A1 (fr) 2011-12-21 2013-06-27 Xergy Incorporated Système de compression électrochimique
US10024590B2 (en) 2011-12-21 2018-07-17 Xergy Inc. Electrochemical compressor refrigeration appartus with integral leak detection system
GB2548689A (en) * 2016-01-28 2017-09-27 Xergy Ltd Electrochemical compressor refrigeration apparatus with integral leak detection system
US11173456B2 (en) 2016-03-03 2021-11-16 Xergy Inc. Anion exchange polymers and anion exchange membranes incorporating same
US10386084B2 (en) 2016-03-30 2019-08-20 Xergy Ltd Heat pumps utilizing ionic liquid desiccant
US11454458B1 (en) 2019-04-12 2022-09-27 Xergy Inc. Tube-in-tube ionic liquid heat exchanger employing a selectively permeable tube
CN110240121A (zh) * 2019-07-27 2019-09-17 北京汉华元生科技有限公司 具有充瓶功能的野战医院电化学陶瓷膜制氧系统
WO2021252464A1 (fr) 2020-06-08 2021-12-16 United States Of America As Represented By The Administrator Of Nasa Systèmes et procédés de concentration d'oxygène avec des empilements électrochimiques dans un flux de gaz série

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE28792E (en) * 1966-03-15 1976-04-27 Westinghouse Electric Corporation Electrochemical method for separating O2 from a gas; generating electricity; measuring O2 partial pressure; and fuel cell
US3669032A (en) * 1970-02-24 1972-06-13 Leoda J Gooderum Legless ironing board
US4007106A (en) * 1973-06-22 1977-02-08 Canadian Patents And Development Limited Device for measuring oxygen concentration in molten-metal
US3838021A (en) * 1973-07-18 1974-09-24 United Nuclear Corp Method and apparatus for in situ calibration of electrochemical sensors
DE3509360A1 (de) * 1985-02-14 1986-08-14 Bbc Brown Boveri & Cie Verfahren zur messung des sauerstoffgehalts im abgas von brennkraftmaschinen
US4671080A (en) * 1986-01-13 1987-06-09 The Boeing Company Closed cryogenic cooling system without moving parts
US4879016A (en) * 1986-07-25 1989-11-07 Ceramatec, Inc. Electrolyte assembly for oxygen generating device and electrodes therefor
US4725346A (en) * 1986-07-25 1988-02-16 Ceramatec, Inc. Electrolyte assembly for oxygen generating device and electrodes therefor

Also Published As

Publication number Publication date
WO1991006691A1 (fr) 1991-05-16
EP0500708A4 (en) 1993-03-24
AU6742490A (en) 1991-05-31

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