EP2257364A1 - Membrane perméable à l'oxygène et son procédé de fabrication - Google Patents

Membrane perméable à l'oxygène et son procédé de fabrication

Info

Publication number
EP2257364A1
EP2257364A1 EP09724584A EP09724584A EP2257364A1 EP 2257364 A1 EP2257364 A1 EP 2257364A1 EP 09724584 A EP09724584 A EP 09724584A EP 09724584 A EP09724584 A EP 09724584A EP 2257364 A1 EP2257364 A1 EP 2257364A1
Authority
EP
European Patent Office
Prior art keywords
layer
composite membrane
range
intermediate layer
membrane according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09724584A
Other languages
German (de)
English (en)
Inventor
Stefan Baumann
José Manuel SERRA ALFARO
Wilhelm Albert Meulenberg
Hans Peter Buchkremer
Detlev STÖVER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Forschungszentrum Juelich GmbH
Original Assignee
Forschungszentrum Juelich GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Forschungszentrum Juelich GmbH filed Critical Forschungszentrum Juelich GmbH
Publication of EP2257364A1 publication Critical patent/EP2257364A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/024—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/024—Oxides
    • B01D71/0271—Perovskites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0048—Inorganic membrane manufacture by sol-gel transition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0072—Inorganic membrane manufacture by deposition from the gaseous phase, e.g. sputtering, CVD, PVD
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/108—Inorganic support material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/1216—Three or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/0229—Purification or separation processes
    • C01B13/0248—Physical processing only
    • C01B13/0251—Physical processing only by making use of membranes
    • C01B13/0255—Physical processing only by making use of membranes characterised by the type of membrane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/46—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B01D2325/0283—Pore size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/04—Characteristic thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/24—Mechanical properties, e.g. strength

Definitions

  • the invention relates to an oxygen-permeable membrane, in particular for use for CO 2 -Atrennung in power plants, and a method for its preparation.
  • low-concentration CO 2 is removed from the low-temperature exhaust gas stream of the energy conversion plants (separation task: CO 2 / N 2 ).
  • the fossil fuel before the actual combustion of the carbon is removed by the fuel is converted by a partial oxidation or reforming in CO 2 and hydrogen gas (separation task: CO 2 / H 2 ), combustion of hydrogen.
  • the CO 2 can be washed out by physical or chemical washing solutions. Again, the separation of CO 2 from the designed Gas mixture easier than described under point a), since there are also significantly higher concentrations and pressures for the CO 2 .
  • Ceramic membranes have high chemical and thermal stability and can be used in all three power plant routes. However, existing ceramic membranes have insufficient permeation or separation rates or are not stable under process conditions.
  • the permeation rate represents the volume flow per unit time of the permeating component, based on the membrane surface, [ml / (cm 2 min)].
  • the selectivity is described by the so-called separation factor, which is given by the ratio of the permeation rate of the gases to be separated, and is infinite in dense, but oxygen-semipermeable membranes.
  • the asymmetric membranes In the case of membranes, a distinction is also made between the so-called bulk membranes and the asymmetric membranes. While the bulk membrane (monolithic membrane) has a single material layer, the asymmetric membrane has a layer structure with at least two different layers, a release layer and a porous support layer.
  • Conceivable is the production of asymmetric membranes with separation layer thicknesses of less than 100 microns from materials that have the highest permeation rates, such as Bao. 5 sro. 5 CO. 8 Fe 0 . 2 0 3 . ⁇ ).
  • these materials due to their exceptional thermal and chemical expansion behavior, these materials necessarily require a support of the same material as the release layer. However, this material often has only low chemical and mechanical stability, and is also relatively expensive.
  • the invention has for its object to provide a semipermeable membrane, in particular an oxygen-permeable membrane, for use for gas separation, which overcomes the prescribed disadvantages of the prior art. Furthermore, it is the object of the invention to provide a corresponding manufacturing method for such a membrane.
  • a thin membrane with a total layer thickness of less than 1 mm comprising a porous support layer, one or more porous intermediate layers and a functional layer having a layer thickness of less than 1 ⁇ m arranged thereon has an effective separation efficiency for the oxygen separation having.
  • the carrier layer advantageously effects the mechanical stability of the membrane.
  • it can be made of a steel, for. B. 316 L stainless steel, a structural ceramic (eg Al 2 O 3 or ZrO 2 ) or a cermet (mixture of ceramic and metal) exist.
  • the thickness of the carrier layer depends on the separation problem, and may vary between 100 ⁇ m and 1 mm.
  • the thickness of the carrier layer influences the degree of permeation, and should therefore be designed in principle as thin as possible, in particular smaller than 1 mm.
  • layer thicknesses of at least 100 ⁇ m, better 200 ⁇ m are desirable.
  • metallic carrier layers generally have better mechanical stability than ceramic layers with a comparable layer thickness.
  • the carrier layer itself is designed to be porous throughout and has pores in the ⁇ m range on average. The determination of this average pore diameter can be in particular by SEM (scanning electron microscopy) or with smaller pore diameter via TEM (transmission electron microscopy). The pores are chosen to be significantly larger than those of the adjacent intermediate layer.
  • the carrier layer should provide for the mechanical stability, but if possible no flow resistance.
  • the carrier can also be designed graded if necessary.
  • this intermediate layer comprises oxide systems, in particular ceramics.
  • Advantageous materials for the intermediate layer are, for example, TiO 2 , ZrO 2 or doped CeO 2 .
  • the materials of the intermediate layer are said to undergo neither chemical reactions with the carrier material nor with the functional layer, which could adversely affect the functionality of the overall system in long-term operation.
  • the intermediate layer has essentially the task to adjust the pore structure and surface quality (roughness, etc.) of the carrier to the needs of the release layer.
  • a catalytically active layer for example, has only a limited Mischleitrichrange, but a high catalytic activity for oxygen incorporation.
  • a suitable material would be, for example, Cei-x Gd x O 2 (CGO), Lai-x Sr x -y Coi Feyo 3- ⁇ (LSCF) or a mixture thereof, which may additionally with a noble metal, such. B. Pt, Pd is impregnated.
  • the total layer thickness of the intermediate layer or all intermediate layers should not be thicker than 30 .mu.m, in particular not thicker than 20 .mu.m, to ensure maximum fürström- availability.
  • the intermediate layer is also designed to be porous throughout.
  • the average pore diameter of the intermediate layer is advantageously between 2 and 200 nm, in particular between 10 and 100 nm.
  • the intermediate layers are graduated and the pore diameter gradually decreases from the carrier layer toward the functional layer as a result of the arrangement of the plurality of intermediate layers ,
  • the functional layer arranged on the intermediate layer effects the actual separation the gas molecules.
  • the functional layer itself is gas-tight, which means impermeable to gases.
  • the oxygen transport through this layer takes place exclusively via the incorporation and further transport of oxygen in ionic form and the simultaneous return transport of the corresponding electrons. Therefore, this functional layer must have a mixed conductive material, such as perovskite, a fluorite or a K 2 Ni 0 4 structure.
  • the total layer thickness of this functional layer is advantageously less than 1 .mu.m, in particular less than 500 nm, and particularly advantageously between 25 and 400 nm. The small layer thickness advantageously leads to a saving in material costs.
  • the functional layer is so elastic that even the different thermal expansions of the various layers involved regularly cause no problems.
  • the maximum permeation rate can be realized in this way for the respective material.
  • perovskite materials such as Ba 1-x Sr x Co 1 "yFe y O 3- s (BSCF) or La 1-x Sr x Coi-yFe y O 3-8 (LSCF) mentioned .
  • materials with K 2 Ni 0 4 -structure for example based on La 2 NiO 4 + S are applicable.
  • the functional layer is in the form of a graded layer.
  • the properties of the abovementioned intermediate layer are then present in particular at the carrier layer / graded layer interface, while the properties of the abovementioned functional layer, in particular on the free surface of the layer system, are present. This means that the average pore diameter of the carrier layer towards the free surface gas / functional layer decreases in principle continuously or else in a stepped manner.
  • a further thin protective layer can also be arranged on the separating layer.
  • the protective layer generally has a layer thickness of less than 50 nm, advantageously even less than 25 nm, depending on the porosity.
  • a porous, catalytically active layer in order to overcome kinetic obstacles in oxygen incorporation or expansion.
  • a porous ceramic or metallic foil having a layer thickness between 200 and 1000 ⁇ m in thickness is firstly provided as the carrier layer.
  • a cermet is also conceivable as a carrier layer. The pore sizes of this carrier layer are in the micron range.
  • one or more intermediate ceramic layers with pores in the range from 1 to 200 nm, in particular with pores in the range from 2 to 100 nm, are applied to the carrier layer on one side.
  • the coating with the intermediate layer is particularly useful if a delay of a very thin designed carrier layer to be prevented during the heat treatment.
  • different intermediate layers may be arranged such that a decreasing degree of porosity in the direction of the functional layer is achieved.
  • the intermediate layer or layers can advantageously be applied to the carrier by conventional application methods, for example by wet powder spraying or else by screen printing.
  • Sol-gel processes, in which a sol-gel precursor is first applied and subsequently pyrolyzed, are also particularly suitable for layers with small pores.
  • the functional layer required for the actual gas separation can also advantageously be applied by means of a sol-gel method.
  • CVD chemical vapor deposition
  • PVD physical vapor deposition
  • the adjustment of the porosity in the functional layer is achieved by the sol composition, the pyrolysis condition, that is, the burnout of the organic components, and the sintering condition.
  • a single or multi-layer application using sol-gel method may prove necessary.
  • the sol usually consists of stabilized particles of an O 2 -permeable, crystalline phase, such as a perovskite, or a precursor of this phase with an average particle size between 5 and 200 nm.
  • the small particle size increases the sintering activity such that a densification of the Layer at even low sintering temperatures (600 - 900 ° C) is made possible.
  • the small layer thickness of the functional layer ensures sufficient elasticity, so that the differences in the thermal expansion do not play a disadvantageous role.
  • the maximum permeation rate can be realized in this way for the respective material.
  • the ceramic membrane has stability problems under normal operating conditions, for example because it reacts with constituents of the adjacent gas phase, or if it decomposes at a low partial pressure of oxygen, an additional, very thin protective layer of another mixed-conducting material can optionally be applied to the functional layer become.
  • this protective layer are also methods such as the sol-gel process or a deposition from the gas phase, for. B. via PVD, CVD or PLD (Pulsed Laser Deposition) possible and suitable.
  • a further, porous, catalytically active, thin layer can be applied to the functional layer, which has the function of overcoming kinetic obstacles in the incorporation and removal of oxygen ions from the adjacent gas phase into the material .
  • a layer would be advantageous by screen printing, spraying, sol-gel process or PVD / CVD can be applied.
  • a material with the aforementioned desirable catalytic properties for example, Ce 1-x Gd x O 2 (CGO) / La 1-x Sr ⁇ Co 1-y FeyO 3- s (LSCF) would be mentioned, which additionally with a noble metal, eg. B. Pt, Pd is impregnated.
  • the ceramic membranes according to the invention regularly have high permeability, high selectivity and good stability under use conditions. It is particularly suitable for gas separation of oxygen from gas mixtures. Special description part
  • FIGS. 1 to 3 show schematically three different embodiments of the membrane according to the invention. In this mean:
  • a second intermediate layer of ZrO 2 , TiO 2 or Cei -x Gd x ⁇ 2 (CGO) is applied.
  • a sol-gel precursor of an organic precursor, z As titanium propylate, zirconium propylate, and acetylacetone and an ⁇ -carboxylic acid used which is applied by spin coating or a dipping process. This is followed by pyrolysis (eg at 600 ° C./1 hour) of the organic constituents of the sol.
  • the functional layer sol eg Laj x Sr x Coj y y Fe y Os-a, LSCF
  • a solution of the corresponding metal nitrates, sodium linolate and ethanol is prepared.
  • autoclaving for example at 80 ° C./24 h
  • a liquid / liquid extraction with xylene is carried out.
  • the result is a sol of LSCF particles in xylene.
  • the application of the functional layer takes place by means of spin coating or a dipping process.
  • a sintering of the sample is carried out at temperatures up to 900 0 C, which ensures sufficient compaction and crystallinity of the layer.
  • Embodiment 2 Embodiment 2:
  • a presintered porous substrate of ZrO 2 or alternatively Al 2 O 3 is prepared.
  • a second intermediate layer of ZrO 2 , TiO 2 or Cei -x Gd x O 2 (CGO) is applied by means of sol-gel V experienced.
  • a sol-gel precursor of an organic precursor, z As titanium propylate, zirconium propylate and acetylacetone and an ⁇ -standing carboxylic acid used, which is applied by spin coating or a dipping process.
  • a thin catalytically active layer eg, perovskite
  • the particle size is chosen sufficiently large so that the layer does not sinter tightly in the further course of the process.
  • porous layer impregnated with Pt Lai-x Sr x Fe y Coi y O 3- ⁇ is applied by means of sol-gel process and sintered.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention concerne une membrane composite pour la séparation sélective de gaz. Cette membrane comprend un système de couches comportant une couche support poreuse mécaniquement stable à pores traversants, présentant une taille moyenne de pores de l'ordre du μm, au moins une couche intermédiaire poreuse à pores traversants disposée sur la couche support, présentant une taille moyenne de pores comprise entre 2 et 200 nm, ainsi qu'une couche fonctionnelle étanche aux gaz disposée sur la couche intermédiaire, cette couche fonctionnelle étant composée d'une matière à conductivité mixte et présentant une épaisseur maximale de 1 μm. La couche support se compose d'une céramique structurale, d'un métal ou d'un cermet et présente une épaisseur inférieure ou égale à 1 mm. La couche intermédiaire présente une épaisseur totale inférieure ou égale à 100 μm et une taille moyenne de pores comprise entre 10 et 100 nm. La couche fonctionnelle se compose d'une perovskite, d'une fluorine ou d'un matériau à structure K2NiF4, comme par exemple La1-xSrxCo1-yFeyO3-8 (LSCF). L'épaisseur de la couche fonctionnelle est inférieure ou égale à 50 nm, en particulier comprise entre 25 et 400 nm. Cette membrane composite est fabriquée par application d'au moins une couche intermédiaire poreuse présentant une taille moyenne de pores comprise entre 2 et 200 nm sur une couche support poreuse mécaniquement stable à pores traversants présentant une taille moyenne de pores de l'ordre du μm, puis par application d'une couche fonctionnelle étanche aux gaz additionnelle, composée d'une matière à conductivité mixte et présentant une épaisseur maximale de 1 μm, sur la couche intermédiaire.
EP09724584A 2008-03-28 2009-02-21 Membrane perméable à l'oxygène et son procédé de fabrication Withdrawn EP2257364A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008016158A DE102008016158A1 (de) 2008-03-28 2008-03-28 Sauerstoff durchlässige Membran sowie Verfahren zu dessen Herstellung
PCT/DE2009/000256 WO2009117978A1 (fr) 2008-03-28 2009-02-21 Membrane perméable à l'oxygène et son procédé de fabrication

Publications (1)

Publication Number Publication Date
EP2257364A1 true EP2257364A1 (fr) 2010-12-08

Family

ID=40802233

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09724584A Withdrawn EP2257364A1 (fr) 2008-03-28 2009-02-21 Membrane perméable à l'oxygène et son procédé de fabrication

Country Status (4)

Country Link
US (1) US8486184B2 (fr)
EP (1) EP2257364A1 (fr)
DE (1) DE102008016158A1 (fr)
WO (1) WO2009117978A1 (fr)

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DE102008016158A1 (de) 2009-10-01
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US20110020192A1 (en) 2011-01-27

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