EP1791624A1 - Dispositif de separation de gaz et procede pour produire un tel dispositif - Google Patents

Dispositif de separation de gaz et procede pour produire un tel dispositif

Info

Publication number
EP1791624A1
EP1791624A1 EP05774386A EP05774386A EP1791624A1 EP 1791624 A1 EP1791624 A1 EP 1791624A1 EP 05774386 A EP05774386 A EP 05774386A EP 05774386 A EP05774386 A EP 05774386A EP 1791624 A1 EP1791624 A1 EP 1791624A1
Authority
EP
European Patent Office
Prior art keywords
layer
functional layer
pore diameter
thickness
functional
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Withdrawn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
EP05774386A
Other languages
German (de)
English (en)
Inventor
Wilhelm A. Meulenberg
Ralf Hansch
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 EP1791624A1 publication Critical patent/EP1791624A1/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Withdrawn legal-status Critical Current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
    • 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
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • 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
    • B01D69/106—Membranes in the pores of a support, e.g. polymerized in the pores or voids
    • 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
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B01D2325/022—Asymmetric 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
    • B01D2325/022—Asymmetric membranes
    • B01D2325/0232—Dense layer on both outer sides of the membrane
    • 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
    • B01D2325/22—Thermal or heat-resistance properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/30—Chemical resistance
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495—Thickness [relative or absolute]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249961—With gradual property change within a component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249978—Voids specified as micro
    • Y10T428/249979—Specified thickness of void-containing component [absolute or relative] or numerical cell dimension
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249978—Voids specified as micro
    • Y10T428/24998—Composite has more than two layers

Definitions

  • the invention relates to a device for gas separation, particularly for the separation of N 2/0 2, CO 2 / H 2 and N 2 / CO mixtures Gasmi ⁇ 2. Furthermore, the invention relates to a method for producing such a device.
  • membranes A distinction is made between so-called mesoporous membranes, ie those with pore diameters between 2 and 50 nm, and microporous membranes which have pores with a pore diameter of less than 2 nm.
  • microporous membranes eg. As silica membranes, known from the literature.
  • the separation of the gases is based on the principle of molecular sieving, whereby a first gas from the gas mixture can pass through the membrane, but not another because of the larger kinetic molecular diameter.
  • the driving force for the separation process is the pressure difference between the two gas spaces.
  • the most important characteristics of gas separation membranes are their permeability and separation factors. These properties give the separation performance and the membrane requirements for a separation task.
  • a flow J (unit: kg m "2 s ' 1 ) sets in at steady-state conditions under the driving force of a partial pressure difference for a particle through a membrane piece with the area A.
  • the permeability P of a membrane is normalized as a gas flow per membrane area, time and partial pressure difference for the permeating gas indicated (unit: Nm 3 (STP) m "2 h “ 1 bar “1 , STP: O 0 C, 101325 Pa, 22.414 1 Molvolu ⁇ men).
  • the separation efficiency of a membrane material is indicated by the separation factor ⁇ .
  • the separation factor for a gas pair is defined as the ratio of the gas permeabilities P. It depends on the temperature, the feed pressure and the pressure difference across the membrane as well as the pore diameter and the pore distribution. Separation factors are approximately not dependent on the membrane thickness. Exceptions are membranes with very thin separation layers ( ⁇ 0.1 ⁇ m) compared to isotropic films (100 ⁇ m).
  • Gas permeation separates gas streams into streams of different components. As established industrial applications, it has the separation of hydrogen from the process gas, the nitrogen / oxygen separation from air and the recovery of organic vapors such as, for example, gasoline vapors from gas / air mixtures.
  • microporous membranes such as multilayer silica membranes (amorphous SiO 2 ), zeolite membranes or carbon membranes, as well as metal membranes (eg PdAg alloy) or perovskite membranes as mixed-conducting dense membranes.
  • metal membranes eg PdAg alloy
  • perovskite membranes as mixed-conducting dense membranes.
  • Their fields of application are versatile and different. They have in common their applicability under difficult process conditions, such as, for example, high temperature and / or high pressure.
  • the typical applications of gas permeation with inorganic membranes are, in particular, the necessary purification of gas streams with regard to subsequent process steps (eg risk of catalyst poisoning), the shift of the reaction equilibrium by selective separation of products or by-products and the concentration of product streams to reduce the energy requirement subsequent finishing steps.
  • Membrane systems often have a modular design and can therefore be adapted variably to different problems. Fer ⁇ ner can be driven in a simple manner different throughputs. They do without moving parts and are usually relatively lightweight and compact.
  • IKTS Fraunhofer Institute for Ceramic Technologies and Sintered Materials
  • Ceramic filtration membranes for liquid filtration and gas separation are produced by, in part, multiple applications of thin layers each of finer porosity on a coarsely porous substrate. Such membranes are also called asymmetric membranes.
  • Typical substrates are tubes or multi-channel elements. In the case of disks as substrates, the so-called flat membranes are obtained.
  • IKTS Sintered Materials
  • polymer membranes with layer thicknesses adjustable between 1 and 5 ⁇ m which are produced by coating the substrate with a specially prepared silicon-organic precursor and subsequent polymer pyrolysis.
  • a precursor system gives, for example, a pore diameter of about 1.5 nm with a low distribution and BET surface areas of up to 600 m 2 / g.
  • the pyrolysis of other polymer classes leads, depending on the molecular structure and the thermolysis conditions. different pore diameters between 4 and 20 nm with a narrow pore size distribution.
  • polymer membranes are currently being developed for the separation in the low temperature range.
  • Exist for applications at higher temperatures up to 500 0 C for example, water-serstoffpermeable AgPd membranes and amorphous microporous silica membranes.
  • dense ionic, mixed or proton conductors are also under discussion.
  • the chemical processes generally have a high loss of efficiency, while the polymer membranes are limited to applications at low temperatures.
  • the maximum Einsharmalia for expensive AgPd membranes and silica membranes is about 500 0 C.
  • the disadvantage react these membranes also sensitive to water.
  • the object of the invention is to provide a device with which a gas separation of technically relevant gases, such as, for example, H 2 , N 2 , O 2 or CO 2 from a gas mixture, is possible, especially at higher temperatures. Furthermore, it is the object of the invention to provide a method for producing such a device.
  • the objects of the invention are achieved by a device with all the features according to the main claim, and by methods with the entirety of features according to the independent claims. Advantageous embodiments of the method and the device can be found in the respective dependent claims.
  • a thin membrane comprising a metallic and / or ceramic support layer and an oxide functional layer disposed thereon has an effective separation factor for the separation of gases.
  • the carrier layer advantageously effects the mechanical stability of the membrane.
  • it can be made of a steel, for. B. 316 L stainless steel and / or a ceramic.
  • the thickness of the carrier layer is dependent on the separation protolem, and may vary between 100 ⁇ m and 1 mm.
  • the thickness of the carrier layer influences the degree of permeation, and should therefore be configured 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 a better 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 these average pore diameters can be carried out in particular by SEM (scanning electron microscopy) or with smaller pore diameters via TEM (transmission electron microscopy). The pores are markedly larger than those of the adjoining func- tion layer.
  • the carrier layer should be used for mechanical stabilization. care, but if possible, avoid any flow resistance.
  • a functional layer is arranged which has an average pore diameter as a function of the separation problem to be solved of less than 1 nm, in particular less than 0.8 nm and particularly preferably Partly less than 0.5 nm.
  • the functional layer causes the actual separation of the gas molecules. Theoretically, the average pore diameter should be between those of the gas molecules to be separated. However, it has been shown that even slightly larger pore diameters lead to a very good degree of separation.
  • the functional layer comprises in particular TiO 2 or ZrO 2 and can be made particularly thin. advantageous
  • Layer thickness are in the range of a few to a few hundred nm.
  • the embodiment depends on the separation problem and the separation performance to be achieved.
  • the selectivity increases regularly with decreasing pore diameter of the functional layer.
  • the flow is significantly reduced by very small pores, in particular in connection with ⁇ nd_t a larger layer thickness of the functional layer.
  • the separation .alpha always involves a balance between selectivity and permeation and is adapted by the person skilled in the art to the separation sample to be dissolved.
  • this intermediate layer comprises oxide systems, in particular ceramics.
  • Advantageous materials for the intermediate layer are, for example, TiO 2 , ZrO 2 or Al 2 O 3 .
  • the intermediate layer is likewise porous throughout.
  • the average pore diameter of the intermediate layer is advantageously between that of the carrier layer and that of the functional layer, in particular between 2 and 100 nm.
  • the intermediate layer advantageously has a layer thickness in the range between 100 nm and 50 ⁇ m.
  • a functional layer is disposed on both sides of the carrier layer.
  • the symmetrical arrangement is to be selected in particular when the individual layers are made very thin, since then the bilateral, symmetrical arrangement advantageously leads to an additional stability of the separation device.
  • the symmetrical structure minimizes distortion during the sintering process.
  • the functional layer if appropriate together with an intermediate layer, is present as a graded layer.
  • the properties of the abovementioned intermediate layer are then present in particular at the boundary layer carrier layer / graded layer, while the properties of the abovementioned functional layer are present in particular on the free surface of the layer system. This means that the average pore diameter from the carrier layer to the free surface gas / functional layer decreases in principle continuously or else in a stepped manner.
  • a layer with coarser pores on the outer functional layer with a very small pore diameter for stability reasons.
  • a porous ke ⁇ ramische or metallic foil with a layer thickness zwi ⁇ rule 200- 500 microns thickness is provided as the support layer first.
  • a CerMet is also conceivable as a carrier layer.
  • the porosities are in the ⁇ m range.
  • One or more ceramic intermediate layers having pores in the range from 2 to 100 nm are applied thereon, for example, on one side or on both sides.
  • the two-sided coating with the intermediate layer is particularly useful if a delay of a very thin designed carrier layer during the heat treatment is to be prevented ver ⁇ .
  • the functional layer required for the actual gas separation can advantageously be applied by means of a sol-gel method.
  • CVD chemical vapor deposition
  • PVD physical vapor deposition
  • the setting of the porosity in the functional layer is achieved by means of a sol composition, pyrolyzing condition, that is to say the burnout of the organic components, and the sintering conditions.
  • the devices according to the invention for gas separation regularly have high permeability, high selectivity and good stability under conditions of use. They are thus particularly suitable for the gas separation of technically relevant gases such as N 2 , O 2 , CO 2 , H 2 , He and CH 4 from gas mixtures.
  • the functional layer of TiO 2 or alternatively ZrO 2 is applied.
  • a sol gel from an organic precursor z For example, titanium propylate, zirconium propylate and acetylacetone and an ⁇ -type carboxylic acid used which is applied by spin coating or a dipping process.
  • the pyrolysis takes place (eg. As at 600 ° C / l hour) of the organic components of the sol and the final sintering of the sample at temperatures up to 1000 0 C.

Landscapes

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

Abstract

La présente invention concerne un procédé pour produire un dispositif de séparation de gaz comprenant un système à couches. Selon cette invention, une couche fonctionnelle en TiO2 et/ou en ZrO2 présentant un diamètre de pore moyen inférieur à 1 nm est appliquée sur au moins une face d'une couche support poreuse continue. La couche support présente une épaisseur située de préférence entre 100 νm et 1 mm et présente des pores traversants avec un diamètre de pore moyen situé dans le domaine du νm. La couche fonctionnelle appliquée directement ou sur une ou plusieurs couches intermédiaires présente des pores traversants avec un diamètre de pore moyen inférieur à 1 nm, notamment inférieur à 0,8 nm. La couche fonctionnelle peut avantageusement être conçue sous forme de couche graduée. Cette invention est particulièrement avantageuse de par la conception symétrique du dispositif, selon laquelle des couches fonctionnelles se trouvent des deux côtés de la couche support, éventuellement sur une ou plusieurs couches intermédiaires.
EP05774386A 2004-09-24 2005-08-13 Dispositif de separation de gaz et procede pour produire un tel dispositif Withdrawn EP1791624A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200410046310 DE102004046310A1 (de) 2004-09-24 2004-09-24 Vorrichtung zur Gasseparation sowie Verfahren zur Herstellung einer solchen Vorrichtung
PCT/DE2005/001442 WO2006032230A1 (fr) 2004-09-24 2005-08-13 Dispositif de separation de gaz et procede pour produire un tel dispositif

Publications (1)

Publication Number Publication Date
EP1791624A1 true EP1791624A1 (fr) 2007-06-06

Family

ID=35063117

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05774386A Withdrawn EP1791624A1 (fr) 2004-09-24 2005-08-13 Dispositif de separation de gaz et procede pour produire un tel dispositif

Country Status (8)

Country Link
US (1) US8016924B2 (fr)
EP (1) EP1791624A1 (fr)
JP (1) JP2008514387A (fr)
CN (1) CN101031352A (fr)
AU (1) AU2005287770B2 (fr)
CA (1) CA2581419A1 (fr)
DE (1) DE102004046310A1 (fr)
WO (1) WO2006032230A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IL175270A0 (en) * 2006-04-26 2006-09-05 Acktar Ltd Composite inorganic membrane for separation in fluid systems
WO2009067171A1 (fr) * 2007-11-20 2009-05-28 Corning Incorporated Structure membranaire conductrice d'ions oxygène
DE102008016158A1 (de) * 2008-03-28 2009-10-01 Forschungszentrum Jülich GmbH Sauerstoff durchlässige Membran sowie Verfahren zu dessen Herstellung
US8834604B2 (en) * 2010-09-16 2014-09-16 Volt Research, Llc High temperature gas processing system and method for making the same
CN103521074B (zh) * 2013-10-18 2015-05-20 北京中天元环境工程有限责任公司 双面分离膜
CN103521089B (zh) * 2013-10-18 2015-08-05 北京中天元环境工程有限责任公司 分离膜

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WO2005023403A1 (fr) * 2003-09-04 2005-03-17 Korea Research Institute Of Chemical Technology Membrane composite a base de titane pour la separation eau/alcool, et sa preparation

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JP2000233119A (ja) * 1999-02-12 2000-08-29 Toyota Motor Corp 水素精製膜
JP3660850B2 (ja) * 2000-03-24 2005-06-15 新日本製鐵株式会社 複層セラミックス材料および酸素分離装置
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US4935139A (en) * 1988-05-24 1990-06-19 Alcan International Limited Composite membranes
WO2005023403A1 (fr) * 2003-09-04 2005-03-17 Korea Research Institute Of Chemical Technology Membrane composite a base de titane pour la separation eau/alcool, et sa preparation

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Title
See also references of WO2006032230A1 *

Also Published As

Publication number Publication date
US8016924B2 (en) 2011-09-13
DE102004046310A1 (de) 2006-04-06
US20090193975A1 (en) 2009-08-06
AU2005287770B2 (en) 2010-02-04
CA2581419A1 (fr) 2006-03-30
JP2008514387A (ja) 2008-05-08
AU2005287770A1 (en) 2006-03-30
CN101031352A (zh) 2007-09-05
WO2006032230A1 (fr) 2006-03-30

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