Composite oxygen transport membrane

• US 9,492,784 B2
• Filed: 07/03/2014
• Issued: 11/15/2016
• Est. Priority Date: 12/15/2011
• Status: Active Grant

• Current Assignee: Praxair Technology Incorporated (Linde Plc)
• Original Assignee: Praxair Technology Incorporated (Linde Plc)
• Inventors: Christie, Gervase Maxwell, Lane, Jonathan A.
• Primary Examiner(s): Shumate, Anthony
• Application Number:
  US14/322,981
• Publication Number:
  US 20140311346A1
• Time in Patent Office: 866 Days
• US Class Current: 1/1
• 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: 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 35/04 : based on magnesium oxide
• 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 35/443 : Magnesium aluminate spinel
• 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 38/00 : Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof treating slag with gases or gas generating material C04B5/06 ; expanded graphite C04B35/536
• CPC Class Codes: C04B 38/0074 : expressed as porosity percentage
• 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 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. 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 (La_0.8Ca_0.2)_0.95Cr_0.5Mn_0.5O_3-δ for the porous fuel oxidation and optional porous surface exchange layers and (La_0.8Sr_0.2)_0.95Cr_0.5Fe_0.5O_3-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

1. A method of producing an oxygen ion composite membrane comprising:

forming a first layer on a porous support, the first layer comprising a first mixture of particles of (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

and doped zirconia 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 between about 0.9 and 1.1;

x is between about 0.1 and 0.4 and y is between about 0.1 and 0.6;

forming a second layer on the first layer, the second layer comprising a second mixture of particles 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 Sr; and

B is Fe, Mn, Co, Al, Ti or combinations thereof;

w is between about 0.9 and 1.1;

x is between about 0.1 and 0.4 and y is between about 0.1 and 0.6; and

sintering the porous support, the first layer and the second layer in air at temperatures of greater than about 1300°

C. to produce the oxygen ion composite membrane;

wherein the produced oxygen ion composite membrane comprises the porous support, a porous fuel oxidation layer of the first layer and a dense separation layer of the second layer.

2. The method of claim 1 wherein the first layer is substantially free of pore formers.

3. The method of claim 1 wherein the sintered first layer further comprises (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

and doped zirconia in a first volume ratio of between 2 to 3 and 4 to 1 on a volume percentile basis.

4. The method of claim 1 wherein the sintered second layer further comprises (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

and doped zirconia in a second volume ratio of between 1 to 4 and 3 to 2 on a volume percentile basis.

5. The method of claim 1 further comprising a step of heating or firing the porous support to a low temperature so that it is not fully sintered prior to forming the first layer on the porous support.

6. The method of claim 5 further comprising a step of heating or firing the first layer after having been formed on the porous support at a temperature greater than about 950°

C. to remove any binder from the first mixture.

7. The method of claim 6 wherein the steps of sintering the porous support, the first layer and the second layer in air at temperatures of greater than about 1300°

C. to produce the oxygen ion composite membrane are performed after heating or firing the porous support and the first layer.

8. The method of claim 1 wherein B is a combination of Fe and Co.

9. The method of claim 1 wherein within the second layer x is 0.1 to 0.3.

10. The method of claim 1 further comprising the steps of:

forming a third layer on the second layer, the third layer comprising a third mixture of particles of (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

and doped zirconia, 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 between about 0.9 and 1.1;

x is between about 0.1 and 0.4 and y is between about 0.1 and 0.6;

wherein the oxygen ion composite membrane comprises the porous support, the porous fuel oxidation layer, the dense separation layer, and a porous surface exchange layer of the third layer.

11. The method of claim 10 wherein the third layer contains (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

and doped zirconia in a third volume ratio of between 1 to 3 and 3 to 1 on a volume percentile basis.

12. The method of claim 10 further comprising a step of sintering the third layer after having been formed on the second layer, wherein the sintering is performed in air at a temperature of greater than about 1300°

C.

13. The method of claim 11 wherein the third volume ratio is about 1 to 1.

14. The method of claim 1 wherein the first layer further comprises Ce_1-xA_xO₂, where A is Gd or Sm;

and x is between about 0.1 and 0.4.

15. The method of claim 1 wherein the doped zirconia is 10 mol % Scandia and 1 mol % Yttria Stabilized Zirconia (10Sc1YSZ).

16. The method of claim 1 wherein the porous support is formed from doped zirconium oxide or a mixture of MgO and MgAl₂O₄.

17. The method of claim 3 wherein the first volume ratio is about 3 to 2.

18. The method of claim 4 wherein the second volume ratio is about 2 to 3.

19. The method of claim 1 wherein the porous support is of a tubular configuration.

20. The method of claim 10 wherein first layer, the second layer, and the third layer are formed by a slurry coating process.

21. An oxygen ion composite membrane comprising:

a porous support;

a first layer disposed on the porous support providing a porous fuel oxidation layer, the first layer comprising a mixture of (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

and doped zirconia, 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 between about 0.9 and 1.1;

x is between about 0.1 and 0.4 and y is between about 0.1 and 0.6;

wherein the first layer further comprises (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

and doped zirconia in a first volume ratio of between about 2 to 3 and 4 to 2 on a volume percentile basis;

a second layer disposed on the first layer and providing a dense separation layer, the second layer comprising a mixture of (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

and doped zirconia, where Ln is La, Y, Pr, Ce or Sm;

A is Sr; and

B is Fe, Mn, Co, Al or combinations thereof;

w is between about 0.9 and 1.1;

x is between about 0.1 and 0.4 and y is between about 0.1 and 0.6;

wherein the second layer further comprises (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

and doped zirconia in a second volume ratio of between about 1 to 4 and 3 to 2 on a volume percentile basis.

22. The oxygen ion composite membrane of claim 21 further comprising a third layer disposed on the second layer to form a porous surface exchange layer, the third layer also comprises a 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, Ti or combinations thereof;

w is between about 0.9 and 1.1;

x is between about 0.1 and 0.4 and y is between about 0.1 and 0.6;

wherein the third layer comprises (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

and doped zirconia in a third volume ratio of between about 1 to 3 and 3 to 1 on a volume percentile basis.

23. The oxygen ion composite membrane of claim 22 wherein the first mixture also contains particles of Ce_1-xA_xO₂ where A is Gd or Sm and x is between about 0.1 and 0.4.

24. The oxygen ion composite membrane of claim 23 wherein the doped zirconia is 10 mol % Scandia and 1 mol % Yttria Stabilized Zirconia (10Sc1YSZ).

25. The oxygen ion composite membrane of claim 24 wherein within the second layer x is 0.1 to 0.3.

26. The oxygen ion composite membrane of claim 22 wherein the porous support is of a tubular configuration and wherein the first volume ratio is about 3 to 2, the second volume ratio is about 2 to 3 and the third volume ratio is about 1 to 1.

27. An oxygen ion composite membrane produced by the process comprising the steps of:

forming a first layer on a porous support, the first layer providing a porous fuel oxidation layer and comprising a first mixture of particles of (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

and doped zirconia 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 between about 0.9 and 1.1;

x is between about 0.1 and 0.4 and y is between about 0.1 and 0.6;

wherein the first layer further comprises (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

and doped zirconia in a first volume ratio of between about 2 to 3 and 4 to 2 on a volume percentile basis;

forming a second layer on the first layer, the second layer providing a dense separation layer and comprising a second mixture of particles 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 Sr; and

B is Fe, Mn, Co, Al, Ti or combinations thereof;

w is between about 0.9 and 1.1;

x is between about 0.1 and 0.4 and y is between about 0.1 and 0.6;

wherein the second layer further comprises (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

and doped zirconia in a second volume ratio of between about 1 to 4 and 3 to 2 on a volume percentile basis; and

sintering the porous support, the first layer and the second layer in air at prescribed sintering temperatures to produce the oxygen ion composite membrane.

28. The oxygen ion composite membrane produced by the process of claim 27 further comprising a step of:

forming a third layer on the second layer, the third layer providing a porous surface exchange layer and comprising a third mixture of particles of (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

and doped zirconia, 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 between about 0.9 and 1.1;

x is between about 0.1 and 0.4 and y is between about 0.1 and 0.6;

wherein the third layer comprises (Ln_1-xA_x)_wCr_1-yB_yO_3-δ

and doped zirconia in a third volume ratio of between about 1 to 3 and 3 to 1 on a volume percentile basis.

29. The oxygen ion composite membrane produced by the process of claim 27 further comprising a step of heating or firing the porous support at temperatures of about 1000°

C. or more prior to applying the first layer.

30. The oxygen ion composite membrane produced by the process of claim 27 further comprising a step of heating or firing the porous support and first layer at temperatures of about 950°

C. or more prior to applying the second layer.

31. The oxygen ion composite membrane produced by the process of claim 27 wherein the step of sintering the porous support further comprises fully sintering the porous support prior to applying the first layer.

32. The oxygen ion composite membrane produced by the process of claim 27 wherein the steps of sintering further comprise sintering the porous support and the first layer prior to applying the second layer.