EP0500708A4 - Solid state oxygen compressor - Google Patents
Solid state oxygen compressorInfo
- Publication number
- EP0500708A4 EP0500708A4 EP19900917179 EP90917179A EP0500708A4 EP 0500708 A4 EP0500708 A4 EP 0500708A4 EP 19900917179 EP19900917179 EP 19900917179 EP 90917179 A EP90917179 A EP 90917179A EP 0500708 A4 EP0500708 A4 EP 0500708A4
- 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- Withdrawn
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.
- 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 electrochemically. It has long been known that various solids such as zirconia, ceria, and bismuth-oxide will conduct oxygen ions when subjected to an electrical potential gradient across such solid oxides but will remain electronic insulators. Furthermore, some of these materials possess high strength.
- 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 dis ⁇ closed. 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 electrodes.
- the half reactions occurring at each interface are:
- the net chemical potential at each interface is the sum of the chemical potentials of the individual species at that interface.
- the net chemical potential difference of oxygen between interfaces 1 and 2 can be affected by controlling the electronic potential difference of electrons between interfaces 1 and 2.
- the chemical potential of oxygen at a gas-solid interface is direct function of oxygen partial pressure in the gas. Therefore, the oxygen partial pressure difference in the gas phase at the two interfaces can be affected by controlling the electronic potential difference.
- 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; and FIG. 7 is graphical illustration of the rate of oxygen pressure increase achieved by the compressor illustrated in FIG. 6.
- 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 disclosed and described in U.S. Patent 4,725,346 infra, the description thereof being incorporated herein by reference.
- 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 are constructed in such a way as to create a mechanical barrier between a low pressure oxygen reservoir and a confined volume.
- electromotive force EMF
- 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 properties that makes it well suited for application in practical devices. These include high oxygen ion conductivity, especially at temperatures greater than 800°C, high strength, and sinterability which facilitate ease of fabrication of useful shapes, such as tubes, cups, cylinders, open-ended cylinders, flat plates and the like.
- useful shapes such as tubes, cups, cylinders, open-ended cylinders, flat plates and the like.
- the essence of the art in this field of technology is net shape fabrication techniques, processing parameters, microstructure control, type and amounts of dopants to control conductivity, electrode materials, electrode -5-
- Example 1 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 atmosphere by a hole in the top flange into which the compression fitting was welded.
- a teflon ferrule was used to create the seal.
- 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 pressure vessel reached 137,900 newtons per square meter -6-
- 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 compressor was operated in the same manner as in example 1 except that the pressure caused by heating was released to atmospheric pressure before applying the potential across the electrolyte.
- the pressure inside the vessel was brought from 0 newtons per square meter (0 psig) to 1,172,000 newtons per square meter (170 psig) in approximately 570 minutes.
- the pressure increase developed as a function of time is plotted in Figure 5.
- An electrochemical oxygen compressor was fabricated as depicted in FIG. 6.
- the design of the compressor was changed to minimize the volume of the design.
- a closed end stabilized zirconia (92 mole % (percent) ZrO. - 4 mole % (percent) Y 2 0- - 4 mole % (percent) Yb O ) tube 0.95 centimeters outer diameter x 0.67 centimeters inner diameter x 24.13 centimeters long (0.375 inches outer diameter x 0.266 inches inner diameter x 9.5 inches long) was used as the electrolyte.
- the pressure vessel was des.igned so that the internal wall of the pressure vessel was close fitting to the zirconia tube. In this case a -7-
- the 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 anganite 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 diameter of the zirconia tube was exposed to the atmosphere by a hole in the top flange into which the compression fitting was welded into.
- a teflon ferrule was used to create the seal.
- Air was pumped through an 0.31 centimeters outer diameter (0.125 inches outer diameter) alumina tube and out through the annulus between the alumina tube and zirconia tube.
- the zirconia tube was heated to 800°C. . Internal pressure due to heating was released at this point. A potential of one volt was applied across the electrolyte.
- the vessel was pressurized to 1,379,000 newtons per square meter (200 psi) in approximately 18 minutes. The pressure as a function of time is plotted in FIG. 7.
- 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 commercial availability.
- 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.
- 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 -8-
- a feature of the present solid state compressor is a low ratio of the pressure chamber volume to electrolyte area.
- 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.
- providing a small annular space between the interior of the pressure shell and the exterior of the electrolyte causes a rapid buildup of pressure within the pressure chamber.
- 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. Thus, at an operating voltage of one volt or more the back EMF is minimal. -9-
- 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 phosphate, strontium cerate, etc.
- chlorine and fluorine gases may be readily ionized and transported through chlorine ion conductors such as SrCl -Al O and fluorine ion conductors such as LaF or PbF .
- chlorine ion conductors such as SrCl -Al O
- fluorine ion conductors such as LaF or PbF .
- These protons conductors may be readily substituted for the oxygen ion transporting electrolytes described hereinabove and illustrated in the attached drawings.
- both oxygen and hydrogen may be extracted from water vapor. Under appropriate conditions, water vapors disassociates into hydrogen and oxygen. In the presence of an oxygen ion-transporting electrolyte, oxygen may be separated and using the techniques of the instant invention, readily compressed. For example, serial compression of oxygen and hydrogen may be readily accomplished. 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 by ⁇ product 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. Alternatively, the byproduct stream from the oxygen compressor could be fed to a condenser to condense the water vapor, recover pure hydrogen which could be -10-
- 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 manganite.
- 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 coefficient of thermal expansion similar to that of the electrolyte and are generally unaffected by the oxidizing condition to which the electrodes are subjected.
- LSM lanthanum strontium manganite
- 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.
- One technique useful in the instant invention is to form a cylinder of nickel or Inconel wire mesh then force an LSM coated tubular electrolyte into the interior of the mesh cylinder.
- the metal mesh may be heated to an elevated temperature to cause expansion of the mesh before it is put over the electrolyte. Upon cooling, the mesh achieves intimate contact between the electrode and electrolyte by -11-
- An overcoat of electrode material such as silver or LSM is preferably added to ensure intimate secure contact between the mesh and the electrode.
- the internal electrode of a tubular 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 substituted for zirconia.
- Lanthanum strontium cobaltite is an especially effective electrode for use with ceria.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic 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)
- Inorganic Chemistry (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US43239089A | 1989-11-06 | 1989-11-06 | |
US432390 | 1995-05-01 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0500708A1 EP0500708A1 (en) | 1992-09-02 |
EP0500708A4 true 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 (en) |
AU (1) | AU6742490A (en) |
WO (1) | WO1991006691A1 (en) |
Families Citing this family (15)
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 (en) * | 1992-04-16 | 1996-11-06 | Invacare Corporation | Oxygen concentrator utilizing electrochemical cell |
FR2699912B1 (en) † | 1992-12-30 | 1995-01-27 | Cryotechnologies | On-board oxygen supply installation on vehicle. |
FR2770149B1 (en) * | 1997-10-29 | 1999-12-17 | Air Liquide | PROCESS FOR SEPARATING OXYGEN FROM A GAS MIXTURE CONTAINING SAME AND DEVICE FOR CARRYING OUT SAID METHOD |
US6502419B2 (en) | 2000-04-13 | 2003-01-07 | Sun Microsystems, Inc. | Electro-desorption compressor |
DE10156349B4 (en) * | 2001-11-16 | 2006-01-26 | Ballard Power Systems Ag | fuel cell plant |
WO2004106590A1 (en) * | 2003-05-28 | 2004-12-09 | Pirelli & C. S.P.A. | Electrochemical oxygen separator cell |
US10024590B2 (en) | 2011-12-21 | 2018-07-17 | Xergy Inc. | Electrochemical compressor refrigeration appartus with integral leak detection system |
US9738981B2 (en) | 2011-12-21 | 2017-08-22 | Xergy Inc | Electrochemical compression system |
GB2548689A (en) * | 2016-01-28 | 2017-09-27 | Xergy Ltd | Electrochemical compressor refrigeration apparatus with integral leak detection system |
GB2550018B (en) | 2016-03-03 | 2021-11-10 | Xergy Ltd | 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 (en) * | 2019-07-27 | 2019-09-17 | 北京汉华元生科技有限公司 | With the field hospital's electrochemistry ceramic membrane oxygen generation system for filling bottle function |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4671080A (en) * | 1986-01-13 | 1987-06-09 | The Boeing Company | Closed cryogenic cooling system without moving parts |
Family Cites Families (7)
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 (en) * | 1985-02-14 | 1986-08-14 | Bbc Brown Boveri & Cie | METHOD FOR MEASURING THE OXYGEN CONTENT IN THE EXHAUST GAS FROM COMBUSTION ENGINES |
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 |
-
1990
- 1990-11-06 EP EP19900917179 patent/EP0500708A4/en not_active Withdrawn
- 1990-11-06 WO PCT/US1990/006423 patent/WO1991006691A1/en not_active Application Discontinuation
- 1990-11-06 AU AU67424/90A patent/AU6742490A/en not_active Abandoned
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4671080A (en) * | 1986-01-13 | 1987-06-09 | The Boeing Company | Closed cryogenic cooling system without moving parts |
Non-Patent Citations (1)
Title |
---|
See also references of WO9106691A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO1991006691A1 (en) | 1991-05-16 |
EP0500708A1 (en) | 1992-09-02 |
AU6742490A (en) | 1991-05-31 |
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Legal Events
Date | Code | Title | Description |
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PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
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17P | Request for examination filed |
Effective date: 19920518 |
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RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: STUFFLE, KEVIN Inventor name: JOSHI, ASHOK, V. Inventor name: NACHLAS, JESSE, A. |
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A4 | Supplementary search report drawn up and despatched |
Effective date: 19930203 |
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Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN |
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18W | Application withdrawn |
Withdrawal date: 19941010 |