Catalytic layer and use thereof in oxygen-permeable membranes

Patent metadata

Field	Value
Publication number	US-2017100697-A1
Application number	US-201615388550-A
Country	US
Kind code	A1
Filing date	Dec 22, 2016
Priority date	Jul 1, 2014
Publication date	Apr 13, 2017
Grant date	—

Abstract

The invention relates to a catalytic activation layer for use in oxygen-permeable membranes, which can comprise at least one porous structure formed by interconnected ceramic oxide particles that conduct oxygen ions and electronic carriers, where the surface of said particles that is exposed to the pores is covered with nanoparticles made from a catalyst, the composition of which corresponds to the following formula:
A 1-x-y B x C y O R where: A can be selected from Ti, Zr, Hf, lanthanide metals and combinations thereof; B and C are metals selected from Al, Ga, Y, Se, B, Nb, Ta, V, Mo, W, Re, Mn, Sn, Pr, Sm, Tb, Yb, Lu and combinations of same; and A must always be different from B. 0.01 <x<0.5; 0<y<0.3.

First claim

1 . A catalytic activation layer in an oxygen-permeable membrane, wherein the catalytic activation layer comprises at least one porous structure formed by particles of ceramic oxides, said particles linked to each other, conducting oxygen ions and electronic carriers, coated with nanoparticles made of a catalyst which has a composition with the following formula:
A 1-x-y B x C y O R
wherein
A is selected from Ti, Zr, Hf, lanthanide metals and combinations thereof;
B and C are metals selected from Al, Ga, Y, Sc, B, Nb, Ta, V, Mo, W, Re, Mn, Sn, Pr, Sm, Tb, Yb, Lu and combinations thereof;
A must always be different from B.
0.01≦x≦0.5;
0≦y≦0.3
and has a thickness comprised between 5 and 100 μm, a porosity comprised between 10 and 60% and pores with an average size comprised between 0.1 and 5 μm and a content of supported catalyst on the porous structure between 0.5 and 10% by weight of the porous structure.

2 . A The catalytic activation layer of claim 1 , wherein the porous structure is made of mixtures of particles having two different compositions and crystalline phases:
a first phase which is made of cerium oxide partially substituted by one element selected from the group consisting of Zr, Gd, Pr, Sm, Nd, Er, Tb and combinations thereof, and has crystalline structure of the florite type, and has an ionic conductivity greater than 0.001 S/cm under operating conditions; a second phase comprising a mixed oxide with a spinel type structure, comprising at least one metal selected from the group consisting of Fe, Ni, Co, Al, Cr, Mn and combinations thereof, and has a total conductivity greater than 0.05 S/cm under operating conditions.

3 . A The catalytic activation layer according to claim 1 , wherein the porous structure consists of mixtures of particles having two different compositions and crystalline phases:
a first phase comprising cerium oxide partially substituted by an element selected from the group consisting of Zr, Gd, Pr, Sm, Nd, Er, Tb and combinations thereof, and has a crystalline structure of the florite type, and has ionic conductivity greater than 0.001 S/cm under operating conditions; a second phase comprising a mixed oxide with perovskite type structure comprising at least one metal selected from the group consisting of lanthanides, Fe, Ni, Co, Cr, Mn and combinations thereof and has a total conductivity greater than 0.05 S/cm under operating conditions.

4 . A process for obtaining producing a catalytic activation layer described in claim 1 comprising at least one step of incorporating the catalyst into the particles surface of the porous structure by a technique selected from the group consisting of impregnation or infiltration of liquid solutions of precursors of the metals comprised in the final catalyst composition; infiltration of a nanoparticle dispersion of the catalyst; deposition in vapor phase by PVD or CVD techniques, and combinations thereof.

5 . A process for producing a catalytic activation layer according to claim 4 , characterized in that it further comprises a second thermal treatment stage at temperatures comprised between 650 and 1100° C.

6 . An oxygen-permeable membrane, comprising, at least:
a porous ceramic or metallic support (i) with a porosity between 20 and 60%, and a thickness of less than 2 mm; a non-porous layer (ii) with a thickness of less than 150 μm made of an oxide or mixtures of oxides that allows the simultaneous transport of oxygen ions and electronic carriers through it; said catalytic activation layer (iii), and produced according to the process of claims 4 .

7 . A process for producing the oxygen-permeable membrane of claim 6 , comprising at least the following steps:
a) forming the porous support (i) by a technique selected from the group consisting of uniaxial or isostatic pressing, extrusion or calendering, tape casting, conventional casting, dip coating, spin coating, roller coating or silk-screen printing, physical vapor deposition, spraying of suspensions, and/or thermal spraying; 3D printing, stereolithography, injection and combinations thereof, b) forming the non-porous layer (ii) by a technique selected from the group consisting of uniaxial or isostatic pressing; extrusion or calendering; tape casting, conventional casting, dip coating, spin coating, roller coating or silk-screen printing; physical vapor deposition; spraying of suspensions; and/or thermal spraying; 3D printing, stereolithography, injection, inkjet printing and combinations thereof, c) coating the surface of the non-porous separation layer (ii) with a material comprising ceramic oxide particles which conduct oxygen ions and electronic carriers by a technique selected from the group consisting of nebulization, atomization, thermal or pyrolytic atomization, airbrushing, dip coating, spin coating, roller coating, silk screen printing, technique of chemical or physical vapor deposition, printing by inkjet and thermal spraying, and combinations thereof, d) incorporating the catalyst into the particles surface of the porous structure that covers the non-porous separation layer (ii) by a technique selected from the group consisting of impregnation or infiltration of liquid solutions of precursors of the metals comprised in the final catalyst composition; infiltration of a nanoparticle dispersion of the catalyst; deposition in vapor phase by PVD or CVD techniques and combinations thereof.

8 . The process for producing an oxygen-permeable membrane of claim 7 , further comprising a thermal treatment step at temperatures between 900 and 1250° C. between steps c and d.

9 . The process for producing an oxygen-permeable membrane of claims 7 , further comprising a last step of thermal treatment at temperatures comprised between 650 and 1100° C.

10 . A method of preparing an oxygen-permeable membrane comprising the step of providing said catalytic activation layer produced according to the method of claim 4 , and producing oxygen-permeable membranes.

11 . A method of generating an O 2 rich stream comprising providing a membrane of claim 6 produced by the process of claim 7 and generating an O 2 rich stream.

12 . The method of claim 11 , wherein the generated O 2 stream has a purity greater than 99% by volume.

13 . The method of claim 11 , wherein the membrane comprises an entrainment gas for the permeated O 2 .

14 . The method of claim 13 , wherein the entrainment gas has an SO 2 content greater than 5 ppm.

15 . The method of claim 11 , wherein the membrane feed stream has an SO 2 content greater than 5 ppm.

16 . The method of claim 11 , wherein the membrane is integrated in an oxy-combustion system or systems which comprise oxygen enriched combustion stages.

Assignees

• Consejo Superior De Investig Cientificas (Csic)
• Univ Valencia Politecnica

Inventors

• Serra Alfaro Jose Manuel
• Garcia Fayos Julio
• Navarrete Algaba Laura
• Vert Belenguer Vicente Bernardo

Classifications

• B01D53/228 Primary

  characterised by specific membranes · CPC title

• F23L7/007

  Supplying oxygen or oxygen-enriched air · CPC title

• C01B2210/0012

  characterised by the membrane · CPC title

• B01D69/145

  containing embedded catalysts · CPC title

• B01D67/0088

  Physical treatment with compounds, e.g. swelling, coating or impregnation · CPC title