# US 2013/0156978 A1 · Composite oxygen transport membrane

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- Number: US 2013/0156978 A1
- Document ID: US20130156978A1
- Status: Published application
- Kind: A1
- Application number: 13/644,666
- Filed: 2012-10-04
- Published: 2013-06-20
- Earliest claimed: 2011-12-15
- Assignees: Praxair Technology, Inc.
- Inventors: Gervase Maxwell Christie; Jonathan A. Lane
- Web page: https://patentgrep.com/patent/US20130156978A1

## CPC

- B01D 53/228: {characterised by specific membranes}
- B01D 67/00411: {by sintering}
- B01D 69/02: characterised by their properties
- B01D 69/1216: {Three or more layers}
- B01D 71/0271: {Perovskites}
- C01B 13/0255: {characterised by the type of membrane}
- C04B 35/01: based on oxide ceramics
- C04B 35/016: {based on manganites}
- C04B 35/2633: {containing barium, strontium or calcium}
- C04B 35/42: based on chromites (C04B35/047 and C04B35/105 take precedence)
- C04B 35/44: based on aluminates
- C04B 35/462: based on titanates
- C04B 35/488: Composites
- C04B 38/00: Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof (treating slag with gases or gas generating material C04B5/06 {; expanded graphite C04B35/536})
- B01D 2255/402: Perovskites
- B01D 2255/407: Zr-Ce mixed oxides
- B01D 2255/902: Multilayered catalyst
- B01D 2256/12: Oxygen
- B01D 2257/104: Oxygen
- B01D 2258/06: Polluted air
- B01D 2325/023: Dense layer within the membrane
- C04B 2111/00612: {as one or more layers of a layered structure}
- C04B 2111/00801: {Membranes; Diaphragms}
- C04B 2111/0081: {as catalysts or catalyst carriers}
- C04B 2235/3208: Calcium oxide or oxide-forming salts thereof, e.g. lime
- C04B 2235/3217: Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
- C04B 2235/3222: Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
- C04B 2235/3224: Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B 2235/3225: Yttrium oxide or oxide-forming salts thereof
- C04B 2235/3227: Lanthanum oxide or oxide-forming salts thereof
- C04B 2235/3229: Cerium oxides or oxide-forming salts thereof
- C04B 2235/3232: Titanium oxides or titanates, e.g. rutile or anatase
- C04B 2235/3234: Titanates, not containing zirconia
- C04B 2235/3243: Chromates or chromites, e.g. aluminum chromate, lanthanum strontium chromite
- C04B 2235/3246: Stabilised zirconias, e.g. YSZ or cerium stabilised zirconia
- C04B 2235/3262: Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
- C04B 2235/3268: Manganates, manganites, rhenates or rhenites, e.g. lithium manganite, barium manganate, rhenium oxide
- C04B 2235/3272: Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
- C04B 2235/3274: Ferrites
- C04B 2235/3275: Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
- C04B 2235/5445: submicron sized, i.e. from 0,1 to 1 micron
- C04B 2235/768: Perovskite structure ABO3
- C04B 2235/80: Phases present in the sintered or melt-cast ceramic products other than the main phase
- Y10T 428/1314: Contains fabric, fiber particle, or filament made of glass, ceramic, or sintered, fused, fired, or calcined metal oxide, or metal carbide or other inorganic compound [e.g., fiber glass, mineral fiber, sand, etc.]
- Y10T 428/24997: Of metal-containing material
- Y10T 428/24999: Inorganic
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

A method of producing a composite oxygen ion membrane and a composite oxygen ion membrane in which a porous fuel oxidation layer and a dense separation layer and optionally, a porous surface exchange layer are formed on a porous support from mixtures of (Ln1-xAx)wCr1-yByO3-δ and a doped zirconia. In the porous fuel oxidation layer and the optional porous surface exchange layer, A is Calcium and in the dense separation layer A is not Calcium and, preferably is Strontium. Preferred materials are (La0.8Ca0.2)0.95Cr0.5Mn0.5O3-δ for the porous fuel oxidation and optional porous surface exchange layers and (La0.8Sr0.2)0.95Cr0.5Fe0.5O3-δ for the dense separation layer. The use of such materials allows the membrane to sintered in air and without the use of pore formers to reduce membrane manufacturing costs. The use of materials, as described herein, for forming the porous layers have application for forming any type of porous structure, such as a catalyst support.

## Claims

### Claim 1

A method of producing an oxygen ion composite membrane comprising:
forming a first layer on a porous support containing a first mixture of particles of (Ln1-xAx)wCr1-yByO3-δ and doped zirconia and substantially free of pore formers, where Ln is La, Y, Pr, Ce or Sm; A is Ca, B is Fe, Mn, Co, Al, Ti or combinations thereof; w is 0.9-1.1; x is 0.1-0.4 and y is 0.1-0.6;
forming a second layer on the first layer that contains a second mixture of particles of (Ln1-xAx)wCr1-yByO3-δ and the doped zirconia, where Ln is La, Y, Pr, Ce or Sm; A is Sr; and B is Fe, Mn, Co, Al, Ti or combinations thereof; w is 0.9-1.1; x is 0.1-0.3 and y is 0.1-0.6; and
heating the first layer, the second layer and the porous support so that said first layer partially sinters into a porous mass containing the first mixture of particles, thereby to provide a porous fuel oxidation layer and the second layer fully sinters into a densified mass containing the second mixture of particles, thereby to provide a dense separation layer;
wherein the partially sintered first layer contains (Ln1-xAx)wCr1-yByO3-δ and doped zirconia in a first volume ratio of between 2 to 3 and 4 to 1 on a volume percentile basis such; and
wherein the sintered second layer contains (Ln1-xAx)wCr1-yByO3-δ and doped zirconia in a second volume ratio of between 1 to 4 and 3 to 2 on a volume percentile basis.

### Claim 2 (depends on 1)

The method of claim 1, further comprising the steps of:
forming a third layer on the second layer containing a third mixture of particles of (Ln1-xAx)wCr1-yByO3-δ and doped zirconia and substantially free of pore formers, where Ln is La, Y, Pr, Ce or Sm; A is Ca; B is Fe, Mn, Co, Al, Ti or combinations thereof; w is <0.9-1.1; x is 0.1-0.4 and y is 0.1-0.6;
heating the third layer so that said third layer partially sinters into a porous mass containing the third mixture of particles, thereby to provide a porous surface exchange layer;
wherein the partially sintered third layer contains (Ln1-xAx)wCr1-yByO3-δ and doped zirconia in a third volume ratio of between 1 to 3 and 3 to 1 on a volume percentile basis.

### Claim 3 (depends on 2)

The method of claim 2, wherein the first mixture also contains particles of Ce1-xAxO2 where A is Gd or Sm; and x is 0.1-0.4.

### Claim 4 (depends on 3)

The method of claim 3, wherein the doped zirconia is 10Sc 1YSZ.

### Claim 5 (depends on 1)

The method of claim 1, wherein:
the (Ln1-xAx)wCr1-yByO3-δ within the first mixture of particles and the third mixture of particles is (La1-xCax)wCr1-yMnyO3-δ, where x is 0.2 and y is 0.5;
the (Ln1-xAx)wCr1-yByO3-δ and 10Sc 1YSZ within the second mixture of particles is (La1-xSrx)wCr1-yFeyO3-δ, where x is 0.2 and y is 0.5; and
the sintered porous support is formed from doped zirconium oxide or a mixture of MgO and MgAl2O4.

### Claim 6 (depends on 2)

The method of claim 2, wherein the first volume ratio is 3 to 2, the second volume ratio is 2 to 3 and the third volume ratio is 1 to 1.

### Claim 7 (depends on 2)

The method of claim 2, wherein the porous support is of tubular configuration.

### Claim 8 (depends on 7)

The method of claim 7, wherein:
the porous support is formed of 3YSZ and fired at a temperature of 1000° C. so that it is not fully sintered prior to forming the first layer on the porous support;
the first layer after having been formed on the porous support is fired at a temperature of 950° C. to remove binder from the first mixture; and
the first layer, the second layer and the porous support are sintered at a temperature of 1400° C.

### Claim 9 (depends on 8)

The method of claim 8, wherein the third layer is sintered at a temperature of between 1300° C. and 1400° C.

### Claim 10 (depends on 7)

The method of claim 7, wherein the first layer, the second layer and the third layer are sintered at a temperature of 1400° C.

### Claim 11 (depends on 2)

The method of claim 2, wherein the first layer, the second layer and the third layer are formed by slurry coating.

### Claim 12

A method of producing a porous material comprising:
forming a mixture of particles of (Ln1-xAx)wCr1-yByO3-δ and doped zirconia and that is substantially free of pore formers, where Ln is La, Y, Pr, Ce or Sm; A is Ca; B is Fe, Mn, Co, Al, Ti or combinations thereof; w is <0.9-1.1; x is 0.2-0.4 and y is 0.1-0.6; and
sintering the first mixture in air at a temperature of <1300° C.;
wherein the sintered first mixture contains (Ln1-xAx)wCr1-yByO3-δ and doped zirconia in a first volume ratio of between 1 to 4 and 4 to 1 on a volume percentile basis.

### Claim 13 (depends on 12)

The method of claim 12, wherein the doped zirconia is 10Sc 1YSZ.

### Claim 14

An oxygen ion composite membrane comprising:
first and second layers on a porous support providing a porous fuel oxidation layer and a dense separation layer, respectively, for the oxygen ion composite membrane;
each of the first and second layers containing a mixture of (Ln1-xAx)wCr1-yByO3-δ and doped zirconia, where for the first of the layers, Ln is La, Y, Pr, Ce or Sm; A is Ca; B is Fe, Mn, Co, Al, Ti or combinations thereof; w is <0.9-1.1; x is 0.1-0.4; and y is 0.1-0.6 and for the second of the layers, A is Sr; and B is Fe, Mn, Co, Al or combinations thereof; w is <0.9-1.1; x is 0.1-0.3; and y is 0.1-0.6;
the first of the layers containing (Ln1-xAx)wCr1-yByO3-δ and doped zirconia in a first volume ratio of between 2 to 3 and 4 to 2 on a volume percentile basis; and the second of the layers containing (Ln1-xAx)wCr1-yByO3-δ and doped zirconia in a second volume ratio of between 1 to 4 and 3 to 2 on a volume percentile basis.

### Claim 15 (depends on 14)

The oxygen ion composite membrane of claim 14, wherein:
a third layer is situated on the second layer to form a porous surface exchange layer and that also contains the mixture of (Ln1-xAx)wCr1-yByO3-δ and the doped zirconia, where Ln is La, Y, Pr, Ce or Sm; A is Ca; B is Fe, Mn, Co, Al, Ti or combinations thereof; w is <0.9-1.1; x is 0.1-0.4; and y is 0.1-0.6; and
the third layer containing (Ln1-xAx)wCr1-yByO3-δ and doped zirconia in a third volume ratio of between 1 to 3 and 3 to 1 on a volume percentile basis.

### Claim 16 (depends on 15)

The oxygen ion composite membrane of claim 15, wherein the first mixture also contains particles of Ce1-xAxO2 where A is Gd or Sm and x is 0.1-0.4.

### Claim 17 (depends on 16)

The oxygen ion composite membrane of claim 16, wherein the doped zirconia is 10Sc 1YSZ.

### Claim 18 (depends on 17)

The oxygen ion composite membrane of claim 17, wherein:
the (Ln1-xAx)wCr1-yByO3-δ within the first layer and the third layer is (La1-xCax)wCr1-yMnyO3-δ, where x is 0.2 and y is 0.5;
the (Ln1-xAx)wCr1-yByO3-δ within the second layer is (La1-xSrx)wCr1-yFeyO3-δ, where x is 0.2 and y is 0.5; and
the sintered porous support is formed from stabilized zirconia oxide or a mixture of MgO and MgAl2O4.

### Claim 19 (depends on 15)

The oxygen ion composite membrane of claim 15, wherein the porous support is of a tubular configuration and wherein the first volume ratio is 3 to 2, the second volume ratio is 2 to 3 and the third volume ratio is 1 to 1.