Composite oxygen transport membrane

• US 9,486,735 B2
• Filed: 09/16/2015
• Issued: 11/08/2016
• Est. Priority Date: 12/15/2011
• Status: Active Grant

• Current Assignee: Praxair Technology Incorporated (Linde Plc)
• Original Assignee: Praxair Technology Incorporated (Linde Plc)
• Inventors: Lu, Zigui, Plonczak, Pawel J., Lane, Jonathan A.
• Primary Examiner(s): SHUMATE, ANTHONY R
• Application Number:
  US14/856,038
• Publication Number:
  US 20160001221A1
• Time in Patent Office: 419 Days
• US Class Current: 1/1
• CPC Class Codes: B01D 2255/204 Alkaline earth metals
• CPC Class Codes: B01D 2255/2063 Lanthanum
• CPC Class Codes: B01D 2255/20738 Iron
• CPC Class Codes: B01D 2255/20784 Chromium
• CPC Class Codes: B01D 2255/40 Mixed oxides
• CPC Class Codes: B01D 2255/402 Perovskites
• CPC Class Codes: B01D 2255/407 Zr-Ce mixed oxides
• CPC Class Codes: B01D 2255/902 Multilayered catalyst
• CPC Class Codes: B01D 2256/12 Oxygen
• CPC Class Codes: B01D 2257/104 Oxygen
• CPC Class Codes: B01D 2258/06 Polluted air
• CPC Class Codes: B01D 2325/023 Dense layer within the membrane
• CPC Class Codes: B01D 53/228 characterised by specific membranes
• CPC Class Codes: B01D 67/00411 by sintering
• CPC Class Codes: B01D 69/02 characterised by their properties
• CPC Class Codes: B01D 69/1216 Three or more layers
• CPC Class Codes: B01D 71/0271 Perovskites
• CPC Class Codes: B01J 19/2475 Membrane reactors
• CPC Class Codes: B01J 2219/24 Stationary reactors without moving elements inside
• CPC Class Codes: C01B 13/0255 characterised by the type of membrane
• CPC Class Codes: C04B 2111/00612 : as one or more layers of a layered structure
• CPC Class Codes: C04B 2111/00801 : Membranes; Diaphragms
• CPC Class Codes: C04B 2111/0081 : as catalysts or catalyst carriers
• CPC Class Codes: C04B 2235/3208 : Calcium oxide or oxide-forming salts thereof, e.g. lime
• CPC Class Codes: C04B 2235/3217 : Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
• CPC Class Codes: C04B 2235/3222 : Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
• CPC Class Codes: C04B 2235/3224 : Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
• CPC Class Codes: C04B 2235/3225 : Yttrium oxide or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3227 : Lanthanum oxide or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3229 : Cerium oxides or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3232 : Titanium oxides or titanates, e.g. rutile or anatase
• CPC Class Codes: C04B 2235/3234 : Titanates, not containing zirconia
• CPC Class Codes: C04B 2235/3243 : Chromates or chromites, e.g. aluminum chromate, lanthanum strontium chromite
• CPC Class Codes: C04B 2235/3246 : Stabilised zirconias, e.g. YSZ or cerium stabilised zirconia
• CPC Class Codes: C04B 2235/3262 : Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
• CPC Class Codes: C04B 2235/3268 : Manganates, manganites, rhenates or rhenites, e.g. lithium manganite, barium manganate, rhenium oxide
• CPC Class Codes: C04B 2235/3272 : Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
• CPC Class Codes: C04B 2235/3274 : Ferrites
• CPC Class Codes: C04B 2235/3275 : Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
• CPC Class Codes: C04B 2235/5445 : submicron sized, i.e. from 0,1 to 1 micron
• CPC Class Codes: C04B 2235/768 : Perovskite structure ABO3
• CPC Class Codes: C04B 2235/80 : Phases present in the sintered or melt-cast ceramic products other than the main phase
• CPC Class Codes: C04B 35/01 : based on oxide ceramics
• CPC Class Codes: C04B 35/016 : based on manganites
• CPC Class Codes: C04B 35/2633 : containing barium, strontium or calcium
• CPC Class Codes: C04B 35/42 : based on chromites C04B35/047 and C04B35/105 take precedence
• CPC Class Codes: C04B 35/44 : based on aluminates
• CPC Class Codes: C04B 35/462 : based on titanates
• CPC Class Codes: C04B 35/48 : based on zirconium or hafnium oxides, zirconates, zircon or hafnates
• CPC Class Codes: C04B 35/488 : Composites
• CPC Class Codes: C04B 38/0074 : expressed as porosity percentage
• CPC Class Codes: C04B 38/02 : by adding chemical blowing agents
• CPC Class Codes: 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.]
• CPC Class Codes: Y10T 428/24997 : Of metal-containing material
• CPC Class Codes: Y10T 428/24999 : Inorganic

Abstract

A method is described 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 (Ln_1-xA_x)_wCr_1-yB_yO_3-δ and a doped zirconia. Preferred materials are (La_0.8Sr_0.2)_0.95Cr_0.7Fe_0.3O_3-δ for the porous fuel oxidation layer, (La_0.8Sr_0.2)_0.95Cr_0.5Fe_0.5O_3-δ for the dense separation layer, and (La_0.8Sr_0.2)_0.95Cr_0.3Fe_0.7O_3-δ for the porous surface exchange layer. Firing the said fuel activation and separation layers in nitrogen atmosphere unexpectedly allows the separation layer to sinter into a fully densified mass.

Claims

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 (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

and doped zirconia and pore formers, where Ln is La, Y, Pr, Ce or Sm, A is Ca or Sr, B is Fe, Mn, Co, Al, Ti or combinations thereof, w is from about 0.9 to about 1.0, x is from about 0.1 to about 0.3 and y is from about 0.1 to about 0.6;

the first mixture containing the (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

and the doped zirconia such that when sintered, the first layer will contain the (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

and the doped zirconia in a first volume percentage of (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

of from about 30% to about 70% of the total solid mass;

forming a second layer on the first layer that contains a second mixture of particles of (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

and the doped zirconia and that does not contain pore formers, where Ln is La, Y, Pr, Ce or Sm, A is Ca or Sr, B is Fe, Mn, Co, Al, Ti or combinations thereof, w is from about 0.9 to about 1.0, x is from about 0.1 to about 0.3 and y is from about 0.3 to about 0.7;

the second mixture containing the (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

and the doped zirconia such that when sintered, the second layer will contain the (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

and the doped zirconia in a second volume percentage of (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

of from about 30% to about 70% of the total solid mass;

heating the first layer, the second layer and the porous support in nitrogen atmosphere 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.

2. The method of claim 1, wherein:

a third layer is formed on the second layer containing a third mixture of particles of (Ln_1-xC_x)_wCr_1-yB_yO_3-δ

, the doped zirconia and pore formers, where Ln is La, Y, Pr, Ce or Sm, A is Ca or Sr, B is Fe, Mn, Co, Al, Ni or combinations thereof, w is from about 0.9 to about 1.0, x is from about 0.1 to about 0.3 and y is from about 0.4 to about 0.8;

the third mixture having a third volume ratio of the (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

and the doped zirconia such that when sintered, the third layer will contain the (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

and the doped zirconia in a third volume percentage of (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

of from about 30% to about 70% of the total solid mass; and

the third layer is heated 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.

3. The method of claim 2, wherein the doped zirconia is 10Sc1YSZ or 10Sc1CeSZ.

4. The method of claim 3, wherein:

the (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

within the first mixture of particles is (La_1-xSr_x)_wCr_1-yFe_yO_3-δ

, where w is 0.95, x is 0.2 and y is 0.3;

the (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

within the second mixture of particles is (La_1-xSr_x)_wCr_1-yFe_yO_3-δ

, where w is 0.95, x is 0.2 and y is 0.5;

the (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

within the third mixture of particles is (La_1-xSr_x)_wCr_1-yFe_yO_3-δ

, where w is 0.95, x is 0.2 and y is 0.7; and

the porous support is formed from doped zirconium oxide or a mixture of MgO and MgAl₂O₄.

5. The method of claim 4, wherein the first volume percentage of (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

is about 60% of the total solid mass, the second volume percentage of (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

is about 50% of the total solid mass and the third volume percentage of (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

is about 60% of the total solid mass.

6. The method of claim 5, wherein the porous support is of tubular or planar configuration.

7. The method of claim 6, wherein:

the porous support is formed of 4YSZ and fired at a temperature of about 1050°

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 dried at ambient temperature prior to coating the second layer on the first layer; and

the first layer, the second layer and the porous support are sintered at a temperature of about 1400°

C. in nitrogen.

8. The method of claim 7, wherein the third layer is sintered at a temperature of from about 1250°

C. to about 1350°

C. in air.

9. The method of claim 6, wherein the first layer, the second layer and the third layer are sintered at a temperature of about 1400°

C. in nitrogen, and wherein said first layer, second layer and/or said third layer are optionally formed by slurry coating.

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

11. The method of claim 10, wherein the doped zirconia is 10Sc1YSZ or 10Sc1CeSZ.

12. The method of claim 11, wherein the porous support is 4YSZ.

13. 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 (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

and doped zirconia, where for the first of the layers, Ln is La, Y, Pr, Ce or Sm, A is Ca or Sr, B is Fe, Mn, Co, Al, Ti or combinations thereof, w is 0.9-1.0, x is 0.1-0.3 and y is 0.1-0.6 and for the second of the layers, Ln is La, Y, Pr, Ce or Sm, A is Ca or Sr, and B is Fe, Mn, Co, Al or combinations thereof, w is 0.9-1.0, x is 0.1-0.3 and y is 0.3-0.7;

the first of the layers containing the (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

and the doped zirconia in a first volume percentage of (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

of from about 30% to about 70% of the total solid mass; and

the second of the layers containing the (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

and the doped zirconia in a second volume percentage of (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

of from about 30% to about 70% of the total solid mass.

14. The oxygen ion composite membrane of claim 13, wherein:

a third layer is situated on the second layer to form a porous surface exchange layer and that also contains the mixture of (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

and the doped zirconia, where Ln is La, Y, Pr, Ce or Sm, A is Ca or Sr, B is Fe, Mn, Co, Al, Ni or combinations thereof, w is from about 0.9 to about 1.0, x is from about 0.1 to about 0.3 and y is from about 0.4 to about 0.8; and

the third layer containing the (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

and the doped zirconia in a third volume percentage of (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

of from about 30% to about 70% of the total solid mass.

15. The oxygen ion composite membrane of claim 14, wherein the doped zirconia is 10Sc1YSZ or 10Sc1CeSZ.

16. The oxygen ion composite membrane of claim 15, wherein:

the (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

within the first layer is (La_1-xSr_x)_wCr_1-yFe_yO_3-δ

, where w is 0.95, x is 0.2 and y is 0.3;

the (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

within the second layer is (La_1-xSr_x)_wCr_1-yFe_yO_3-δ

, where w is 0.95, x is 0.2 and y is 0.5;

the (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

within the third layer is (La_1-xSr_x)_wCr_1-yFe_yO_3-δ

, where w is 0.95, x is 0.2 and y is 0.7; and

the porous support is formed from stabilized zirconia oxide or a mixture of MgO and MgAl₂O₄.

17. The oxygen ion composite membrane of claim 13 or claim 16, wherein the first volume percentage of (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

is about 60% of the total solid mass, the second volume percentage of (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

is about 50% of the total solid mass and the third volume percentage of (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

is about 60% of the total solid mass.

18. The oxygen ion composite membrane of claim 16, wherein the porous support is of tubular or planar configuration.

19. The oxygen composite membrane of claim 17, wherein the porous support is formed from 4YSZ.