Catalyst containing oxygen transport membrane

• US 9,561,476 B2
• Filed: 11/09/2012
• Issued: 02/07/2017
• Est. Priority Date: 12/15/2010
• Status: Active Grant

• Current Assignee: Praxair Technology Incorporated (Linde Plc)
• Original Assignee: Praxair Technology Incorporated (Linde Plc)
• Inventors: Sarantopoulos, Christos, Lane, Jonathan A., Wilson, Jamie R., Christie, Gervase Maxwell, Petigny, Nathalie
• Primary Examiner(s): Menon, Krishnan S
• Assistant Examiner(s): Huang, Ryan B
• Application Number:
  US13/672,975
• Publication Number:
  US 20130072375A1
• Time in Patent Office: 1,551 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: B01D 2325/021 Pore shapes
• CPC Class Codes: B01D 2325/0214 Tapered pores
• CPC Class Codes: B01D 2325/10 Catalysts being present on the surface of the membrane or in the pores
• CPC Class Codes: B01D 53/228 characterised by specific membranes
• CPC Class Codes: B01D 69/12 Composite membranes; Ultra-thin membranes
• CPC Class Codes: B01D 69/1216 Three or more layers
• CPC Class Codes: B01D 71/024 Oxides
• CPC Class Codes: B01D 71/0271 Perovskites
• CPC Class Codes: B01J 23/002 Mixed oxides other than spinels, e.g. perovskite
• CPC Class Codes: B01J 23/10 of rare earths
• CPC Class Codes: B01J 23/862 Iron and chromium
• CPC Class Codes: B01J 2523/00 Constitutive chemical elements of heterogeneous catalysts
• CPC Class Codes: B01J 2523/24 Strontium
• CPC Class Codes: B01J 2523/35 Scandium
• CPC Class Codes: B01J 2523/36 Yttrium
• CPC Class Codes: B01J 2523/3706 Lanthanum
• CPC Class Codes: B01J 2523/3712 Cerium
• CPC Class Codes: B01J 2523/375 Gadolinium
• CPC Class Codes: B01J 2523/48 Zirconium
• CPC Class Codes: B01J 2523/55 Vanadium
• CPC Class Codes: B01J 2523/67 : Chromium
• CPC Class Codes: B01J 2523/72 : Manganese
• CPC Class Codes: B01J 2523/842 : Iron
• CPC Class Codes: B01J 29/10 : containing iron group metals, noble metals or copper
• CPC Class Codes: B01J 35/30 : characterised by their physical properties
• CPC Class Codes: B01J 35/40 : characterised by dimensions, e.g. grain size in a colloidal state B01J35/23; crystallite size B01J35/77
• CPC Class Codes: B01J 35/59 : Membranes
• CPC Class Codes: B01J 35/69 : bimodal
• CPC Class Codes: B01J 37/0201 : Impregnation
• CPC Class Codes: B01J 37/0213 : Preparation of the impregnating solution
• CPC Class Codes: C01B 13/0255 : characterised by the type of membrane
• CPC Class Codes: C01B 2210/0046 : Nitrogen
• CPC Class Codes: H01M 4/8621 : containing only metallic or ceramic material, e.g. made by sintering or sputtering
• CPC Class Codes: H01M 4/885 : followed by reduction of the catalyst salt precursor
• CPC Class Codes: H01M 4/9033 : Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
• CPC Class Codes: H01M 8/1246 : the electrolyte consisting of oxides
• CPC Class Codes: Y02E 60/50 : Fuel cells
• CPC Class Codes: Y02P 70/50 : Manufacturing or production processes characterised by the final manufactured product

Abstract

A composite oxygen transport membrane having a dense layer, a porous support layer and an intermediate porous layer located between the dense layer and the porous support layer. Both the dense layer and the intermediate porous layer are formed from an ionic conductive material to conduct oxygen ions and an electrically conductive material to conduct electrons. The porous support layer has a high permeability, high porosity, and a microstructure exhibiting substantially uniform pore size distribution as a result of using PMMA pore forming materials or a bi-modal particle size distribution of the porous support layer materials. Catalyst particles selected to promote oxidation of a combustible substance are located in the intermediate porous layer and in the porous support adjacent to the intermediate porous layer. The catalyst particles can be formed by wicking a solution of catalyst precursors through the porous support toward the intermediate porous layer.

Claims

1. A composite oxygen transport membrane, said composite oxygen transport membrane comprising:

a porous support layer comprised of an fluorite structured ionic conducting material having a porosity of greater than 20 percent and a microstructure exhibiting bi-modal, multi-modal or substantially uniform pore size distribution throughout the porous support layer;

an intermediate porous layer capable of conducting oxygen ions and electrons to separate oxygen from an oxygen containing feed, the intermediate porous layer applied adjacent to the porous support layer and comprising a mixture of a fluorite structured ionic conductive material and electrically conductive materials to conduct the oxygen ions and electrons, respectively;

a dense layer capable of conducting oxygen ions and electrons to separate oxygen from an oxygen containing feed, the dense layer applied adjacent to the intermediate porous layer and also comprising a mixture of a fluorite structured ionic conductive material and electrically conductive materials to conduct the oxygen ions and electrons, respectively; and

catalyst particles or a solution containing precursors of the catalyst particles located in pores of the porous support layer and intermediate porous layer, the catalyst particles containing a catalyst selected to promote oxidation of a combustible substance in the presence of the separated oxygen transported through the dense layer and the intermediate porous layer to the porous support layer, wherein said catalyst is gadolinium doped ceria.

2. The composite oxygen transport membrane of claim 1, further comprising a porous surface exchange layer applied to the dense layer opposite to the intermediate porous layer.

3. The composite oxygen transport membrane of claim 1, wherein:

the intermediate porous layer has a thickness of between 10 and 40 microns, a porosity of between 20 percent and 50 percent and an average pore diameter of between 0.5 and 3 microns;

the dense layer has a thickness of between 10 and 50 microns;

the porous surface exchange layer has a thickness of between 10 and 40 microns, a porosity of between 30 percent and 60 percent and a pore diameter of between 1 and 4 microns; and

the porous support layer has a thickness of between 0.5 and 4 mm.

4. The composite oxygen transport membrane of claim 1,

wherein:

the intermediate porous layer contains a mixture of about 60 percent

by weight of (La_0.825Sr_0.175)_0.96Cr_0.76Fe_0.225V_0.015O_3-δ

or (La_0.8Sr_0.2)_0.95Cr_0.7Fe_0.3O_3-δ

with the remainder 10Sc1YSZ or 10Sc1CeSZ, wherein 10Sc1YSZ is 10 mol % scandia, 1 mol % yttria stabilized zirconia, and 10Sc1CeSZ is 10 mol % scandia, 1 mol % ceria stabilized zirconia;

the dense layer contains a mixture of about 40 percent by weight of (La_0.825Sr_0.175)_0.94Cr_0.72Mn_0.26V_0.02O_3-δ

or (La_0.8Sr_0.2)_0.95Cr_0.5Fe_0.5O_3-δ

, with remainder 10Sc1YSZ or 10Sc1CeSZ;

the porous surface exchange layer is formed by a mixture of about 50 percent by weight of (La_0.8Sr_0.2)_0.98MnO_3-δ

or La_0.8Sr_0.2FeO_3-δ

, remainder 10Sc1YSZ or 10Sc1CeSZ;

the porous support layer has a thickness of between 0.5 and 4 mm and is formed from a mixture comprising 3YSZ and a polymethyl methacrylate based pore forming material.

5. The composite oxygen transport membrane of claim 1,

wherein:

the intermediate porous layer contains a mixture of about 60 percent

by weight of (La_uSr_vCe_1-u-v)_wCr_xM_yV_zO_3-δ

where u is from 0.7 to 0.9, v is from 0.1 to 0.3 and (1-u-v) is greater than or equal to zero, w is from 0.94 to 1, x is from 0.5 to 0.77, M is Mn or Fe, y is from 0.2 to 0.5, z is from 0 to 0.03, and x+y+z=1, with the remainder Zr_x′

Sc_y′

A_z′

O_2-δ

, where y′

is from 0.08 to 0.3, z′

is from 0.01 to 0.03, x′

+y′

+z′

=1 and A is Y or Ce or mixtures of Y and Ce, and the intermediate porous layer has a thickness of between 10 and 40 microns, and a porosity of between 25 percent and 40 percent;

the dense layer contains a mixture of about 40 percent by weight of (La_uSr_vCe_1-u-v)_wCr_xM_yV_zO_3-δ

where u is from 0.7 to 0.9, v is from 0.1 to 0.3 and (1-u-v) is greater than or equal to zero, w is from 0.94 to 1, x is from 0.5 to 0.77, M is Mn or Fe, y is from 0.2 to 0.5, z is from 0 to 0.03, and x+y+z =1, with the remainder Zr_x′

Sc_y′

A_z′

O_2-δ

, where y′

is from 0.08 to 0.3, z′

is from 0.01 to 0.03, x′

+y′

+z′

=1 and A is Y or Ce or mixtures of Y and Ce, and the dense layer has a thickness of between 10 and 50 microns;

the porous surface exchange layer is formed by a mixture of about 50 percent by weight of (La_x′

″

Sr_1-x′

″

)_y′

″

MO_3-δ

, where x′

″

is from 0.2 to 0.9, y′

″

is from 0.95 to 1, M is Mn or Fe, with the remainder Zr_x^ivSc_y^ivA_z^ivO_2-δ

, where y^iv is from 0.08 to 0.3, z^iv is from 0.01 to 0.03, x^iv+y^iv+z^iv=1 and A is Y, Ce or mixtures of Y and Ce; and

the porous support layer has a thickness of between 0.5 and 4 mm and is formed from 3YSZ.

6. The composite oxygen transport membrane of claim 1 made by the process comprising:

fabricating a porous support layer comprised of an fluorite structured ionic conducting material, the fabricating step including a pore forming enhancement step such that the porous support layer has a porosity of greater than about 20 percent and a microstructure exhibiting bi-modal, multi-modal or substantially uniform pore size distribution throughout the porous support layer;

applying an intermediate porous layer on the porous support layer, the intermediate porous layer capable of conducting oxygen ions and electrons to separate oxygen from an oxygen containing feed, the intermediate porous layer comprising a mixture of a fluorite structured ionic conductive material and electrically conductive materials to conduct the oxygen ions and electrons, respectively;

applying a dense layer on the intermediate porous layer, the dense layer capable of conducting oxygen ions and electrons to separate oxygen from an oxygen containing feed, the dense layer also comprising a mixture of a fluorite structured ionic conductive material and electrically conductive materials to conduct the oxygen ions and electrons, respectively; and

introducing catalyst particles or a solution containing precursors of the catalyst particles to the porous support layer and intermediate porous layer, the catalyst particles containing a catalyst selected to promote oxidation of a combustible substance in the presence of the separated oxygen transported through the dense layer and the intermediate porous layer to the porous support layer.

7. The composite oxygen transport membrane of claim 6 wherein the pore forming enhancement process comprises mixing a polymethyl methacrylate based pore forming material with the fluorite structured ionic conducting material of the porous support layer.

8. The composite oxygen transport membrane of claim 6 wherein the pore forming enhancement process comprises use of hollow spherical particles of the fluorite structured ionic conducting material of the porous support layer.

9. The composite oxygen transport membrane of claim 6, further comprising the step of applying a porous surface exchange layer to the dense layer opposite to the intermediate porous layer.

10. The composite oxygen transport membrane of claim 6, wherein the step of introducing catalyst particles or a solution containing precursors of the catalyst particles to the porous support layer and intermediate porous layer further comprises adding catalyst particles to the mixture of fluorite structured ionic conductive material and electrically conductive materials in the intermediate porous layer.

11. The composite oxygen transport membrane of claim 6, wherein the step of introducing catalyst particles or a solution containing precursors of the catalyst particles to the porous support layer and intermediate porous layer further comprises:

applying a solution containing catalyst precursors to the porous support layer on a side thereof opposite to the intermediate porous layer so that the solution infiltrates pores within the porous support layer and the intermediate porous layer with the solution containing catalyst precursors; and

heating the composite oxygen transport membrane after the solution containing catalyst precursors infiltrates the pores and to form the catalyst from the catalyst precursors.

12. A method of producing the catalyst containing composite oxygen transport membrane of claim 1, said method comprising:

forming a composite oxygen transport membrane in a sintered state, said composite oxygen transport membrane having a plurality of layers comprising a dense separation layer, a porous support layer, and an intermediate porous layer located between the dense separation layer and the porous support layer;

applying a solution containing catalyst precursors to the porous support layer on a side thereof opposite to the intermediate porous layer, the catalyst precursors selected to produce a catalyst capable of promoting oxidation of the combustible substance in the presence of the separated oxygen;

infiltrating or impregnating the porous support layer with the solution containing catalyst precursors so that the solution containing catalyst precursors wicks through the pores of the porous support layer and at least partially infiltrates or impregnates the intermediate porous layer; and

heating the composite oxygen transport membrane after infiltrating or impregnating the porous support layer and the intermediate porous layer such that the catalyst is formed from the catalyst precursors

wherein each of the dense separation layer and the intermediate porous layer are capable of conducting oxygen ions and electrons at an elevated operational temperature to separate oxygen from an oxygen containing feed;

wherein the dense separation layer and the intermediate porous layer comprising mixtures of a fluorite structured ionic conductive material and electrically conductive materials to conduct oxygen ions and electrons, respectively;

wherein the porous support layer comprises a fluorite structured ionic conducting material having a porosity of greater than about 20 percent and a microstructure exhibiting bi-modal, multi-modal, or substantially uniform pore size distribution throughout the porous support layer.

13. The method of claim 12, wherein the solution containing catalyst precursors is an aqueous metal ion solution containing 20 mol % Gd(NO₃)₃ and 80 mol % Ce(NO₃)₃ that when sintered forms Gd_0.8Ce_0.2O_2-δ

.

14. The method of claim 12, wherein the catalyst is gadolinium doped ceria.

15. The method of claim 12, wherein a pressure is established on the second side of the support layer to assist in the infiltration or impregnation of porous support layer and intermediate porous layer with the solution containing catalyst precursors or wherein the pores can first be evacuated of air using a vacuum to further assist in wicking of the solution containing catalyst precursors and prevent the opportunity of trapped air in the pores preventing or inhibiting wicking of the solution containing catalyst precursors through the porous support layer to the intermediate porous layer.

16. The method of claim 12, wherein the pores in the porous support layer are formed using a polymethyl methacrylate based pore forming material mixed with the fluorite structured ionic conducting material of the porous support layer.

17. The method of claim 12, wherein the pores in the porous support layer are formed using of hollow spherical particles of the polymethyl methacrylate based pore forming material or the fluorite structured ionic conducting material of the porous support layer.

18. The composite oxygen transport membrane of claim 1 which comprises a porous support layer having a microstructure exhibiting substantially uniform pore size distribution throughout the porous support layer.

19. The method of claim 12 wherein said composite oxygen transport membrane comprises a porous support layer having a microstructure exhibiting substantially uniform pore size distribution throughout the porous support layer.