Catalyst containing oxygen transport membrane

Patent metadata

Field	Value
Publication number	US-9561476-B2
Application number	US-201213672975-A
Country	US
Kind code	B2
Filing date	Nov 9, 2012
Priority date	Dec 15, 2010
Publication date	Feb 7, 2017
Grant date	Feb 7, 2017

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.

First claim

The invention claimed is:

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 0.825 Sr 0.175 ) 0.96 Cr 0.76 Fe 0.225 V 0.015 O 3-δ or (La 0.8 Sr 0.2 ) 0.95 Cr 0.7 Fe 0.3 O 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 0.825 Sr 0.175 ) 0.94 Cr 0.72 Mn 0.26 V 0.02 O 3-δ or (La 0.8 Sr 0.2 ) 0.95 Cr 0.5 Fe 0.5 O 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 0.8 Sr 0.2 ) 0.98 MnO 3-δ or La 0.8 Sr 0.2 FeO 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 u Sr v Ce 1-u-v ) w Cr x M y V z O 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 u Sr v Ce 1-u-v ) w Cr x M y V z O 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 iv Sc y iv A z iv O 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 c

Assignees

• Lane Jonathan A
• Wilson Jamie R
• Christie Gervase Maxwell
• Petigny Nathalie
• Sarantopoulos Christos
• Praxair Technology Inc

Inventors

• Lane Jonathan A
• Wilson Jamie R
• Christie Gervase Maxwell
• Petigny Nathalie
• Sarantopoulos Christos

Classifications

• B01J35/70

  characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00) · CPC title

• B01J2235/30

  Scanning electron microscopy; Transmission electron microscopy · CPC title

• B01J37/0201

  Impregnation · CPC title

• B01J2523/375

  Gadolinium · CPC title

• B01J35/109

  Operations & Transport · mapped topic