WO2000056431A1 - Membrane microporeuse comportant une matrice polymere, et son procede de production - Google Patents
Membrane microporeuse comportant une matrice polymere, et son procede de production Download PDFInfo
- Publication number
- WO2000056431A1 WO2000056431A1 PCT/DE2000/000254 DE0000254W WO0056431A1 WO 2000056431 A1 WO2000056431 A1 WO 2000056431A1 DE 0000254 W DE0000254 W DE 0000254W WO 0056431 A1 WO0056431 A1 WO 0056431A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- membrane
- membrane according
- filler
- polymer matrix
- polymer
- Prior art date
Links
- 239000011159 matrix material Substances 0.000 title claims abstract description 22
- 239000012982 microporous membrane Substances 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000012528 membrane Substances 0.000 claims abstract description 103
- 229920000642 polymer Polymers 0.000 claims abstract description 39
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000011148 porous material Substances 0.000 claims description 34
- 239000000945 filler Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 12
- 239000011256 inorganic filler Substances 0.000 claims description 11
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 229920001601 polyetherimide Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 239000004697 Polyetherimide Substances 0.000 claims 1
- 239000004721 Polyphenylene oxide Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 229920003235 aromatic polyamide Polymers 0.000 claims 1
- 229920000570 polyether Polymers 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 5
- 238000011049 filling Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 28
- 239000000243 solution Substances 0.000 description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- UJRRDDHEMZLWFI-UHFFFAOYSA-N aminitrozole Chemical compound CC(=O)NC1=NC=C([N+]([O-])=O)S1 UJRRDDHEMZLWFI-UHFFFAOYSA-N 0.000 description 5
- 238000005266 casting Methods 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 101100290380 Caenorhabditis elegans cel-1 gene Proteins 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N Oxozirconium Chemical compound [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- -1 tetrafluoroborates Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—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
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/1411—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing dispersed material in a continuous matrix
Definitions
- the invention relates to a microporous membrane with a polymer matrix made of a polymer capable of forming hydrogen bonds and to a method for the production thereof.
- Porous membranes made of chemically and thermally resistant polymers are becoming increasingly important for many separation problems. Due to their usually very good chemical and thermal resistance, they can be used in cases in which only conventional processes or inorganic membranes have been used up to now.
- Possible areas of application are, for example, the separation of narrow-boiling or azeotrope-forming liquid mix by steam permeation or pervaporation, the separation of low molecular weight substances from organic solutions by means of nanofitration and the use as a carrier for catalytically active membranes.
- Inorganic ultrafiltration membranes made of zirconium oxide (ZrO) and polysulfone are already known, for example from EP 0 241 995 B1.
- the polymer merely takes on the function of a polymer binder.
- the ratio of Zr0 2 / polymer band must be at least 80/20.
- the actual basic components of this known membrane are therefore of an inorganic nature.
- the object of the present invention is to provide a microporous membrane or a pore membrane with a polymer matrix made of a polymer capable of forming hydrogen bonds, the pore structure of which does not change or changes only slightly during drying.
- the membrane according to the invention consists of a basic matrix or a polymer matrix made of a conventional polymer capable of forming hydrogen bonds.
- Membrane-forming polymers of this type are, for example, polyamideimides, polyacrylic nitrites, polyetherimides, polyvinylidene fluorides, polyether sulfones, polyamides, polyetheramides, polyimides and non-or partially esterified Cel 1 ul osederi vate.
- the polymer matrix can consist of only one such polymer or of one Mixture of two or more such polymers can be built.
- At least one commercially available inorganic filler in particular TiO 2 is distributed in this polymer matrix.
- This filler makes up a maximum of 60% by weight and preferably a maximum of 50% by weight of the sum of the polymer or the polymer matrix and the filler.
- the filler is preferably distributed as homogeneously as possible in the polymer matrix.
- the inorganic filler preferably has a particle size of 0.05 to 10 ⁇ m and in particular an average particle size in this range. However, the particles are particularly preferably less than or equal to 5 ⁇ m.
- the inorganic filler makes up 30 to 40% by weight of the sum of polymer / polymer matrix and filler.
- a solution of the polymer used is preferably prepared in a suitable solvent. Then one or more inorganic fillers) are added to this solution and the latter are dispersed, for example by using ultrasound, by stirring or by mixing with static mixers or by a combination of these techniques.
- Additives can preferably be added to improve the wetting of the inorganic filler and to stabilize the polymer / filler solution.
- Anti-settling additives and surfactants e.g. emulsifiers, dis- pergi agent, wetting agent and stabilizing additives).
- the actual membranes are then produced by the phase inversion process known per se, in which the solution is applied to a suitable carrier, for example a fleece. Then it is precipitated with a non-solvent.
- a suitable carrier for example a fleece.
- a non-solvent it is preferred to use one which is miscible with the solvent. Water is preferably used. You can then continue to treat with water to remove residual solvents and to specifically influence the separation performance of the membrane.
- the membrane thus obtained is then dried in a conventional manner, for example in an air stream.
- the membrane according to the invention can be either a flat membrane or a hollow fiber membrane.
- the pore structure of the membrane according to the invention is retained even when it is dried, for example in an air stream.
- the membrane according to the invention can be used directly as a pore membrane for the separation of liquid and gaseous or vaporous mixtures, as a support membrane for catalytic membranes and as a support membrane for composite membranes, which will be discussed in more detail below.
- the structure of the membrane according to the invention is still stable even at a temperature of 180 ° C., so that it is particularly suitable for use as a support membrane for catalytic membranes.
- the desired catalysts are immobilized in the pores of the membrane according to the invention. All organic or inorganic catalysts can be used which can be immobilized in the pores of the polymers used and thus in the pores of the polymer matrix or can be attached there. Preference is given to using noble metal 1 compounds as catalysts.
- a precious metal salt solution with a salt content of 0.5 to 5% by weight and preferably 1 to 3% by weight, with which the pores are impregnated.
- organic solvents such as ketones and alcohols and water can be used as solvents. All soluble salts can be considered as precious etal 1 salts.
- Acetates, nitrates, tetrafluoroborates or chlorides are preferably used.
- the impregnated pores are allowed to dry slightly or completely, and the salts are reduced to suitable metal 1 cl by suitable reducing agents.
- suitable reducing agents which do not chemically / physically attack the base membrane or the polymer matrix can be used for this purpose.
- NaBH have proven to be particularly suitable. in combination with alcohols such as methanol, ethanol, iso-propanol and KBH./Wasser.
- This type of catalytic activation of the membrane according to the invention can also be carried out in a module that has already been assembled.
- These catalytically active membranes according to the invention are particularly suitable for reactions in a liquid medium.
- the thickness of the inorganic metal oxide layer can be controlled by introducing the metal alkoxide from solutions of different concentrations.
- Non-polar, aliphatic solvents for example n-hexane and i-octane, are preferably used as solvents.
- the concentration of the solutions is preferably 1 to 5% by weight and particularly preferably 1.5 to 3% by weight.
- the measure of pore reduction described above can be combined with the measure of introducing a catalyst into the pores, also described above.
- a catalyst for example, in the case of a membrane whose pores have been reduced in size as described above, impregnation of the pore system with noble metal 1 salt solutions and subsequent reduction of noble metal 1 clusters can be produced in these pores.
- the catalytically active noble metal 1 clusters are then mainly on the surface of the inorganic lining of the membrane pores localized and thus optimally accessible when the reactants flow through the pore system.
- these measures decouple the catalyst from the polymer of the membrane, which in turn contributes to increased stability of the catalyst system and ensures better activity.
- the pore structure of the membrane according to the invention stabilized by the incorporation of the filler allows the applied selective layer to be crosslinked and / or dried at higher temperatures.
- the inorganic component stabilizes the catalyst (for example palladium, platinum and ruthenium) in the membrane. Due to the high temperature resistance, the membranes according to the invention can also be used at temperatures up to 200 ° C.
- the porous membrane according to the invention has a narrow pore radius distribution and such an average pore radius that the molecules of a coating solution cannot penetrate into the pores of the porous carrier membranes.
- a casting solution of 15.7% Torion (trademark registered for Amoco) and 7.8% TiO (parts by weight based on 100 parts by weight of the solution) was prepared in dimethyl formamide (DMF).
- DMF dimethyl formamide
- This solution was applied in a layer thickness of 190 ⁇ m on a polyester carrier fleece with a membrane branzi ehmaschi ne applied and coagulated in water at 20 ° C.
- the membrane was dried at 90 ° C in an air stream. The following results were obtained with this membrane:
- a casting solution of 15.2% Torion (registered for A oco) and 10.5% Ti0 2 (parts by weight based on 100 parts by weight of the solution) in dimethyl formamide (DMF) was prepared.
- This solution was applied in a layer thickness of 190 ⁇ m to a polyester carrier fleece using a membrane drawing machine and coagulated in water at 20 ° C.
- the membrane was dried at 90 ° C in an air stream. The following results were achieved with this membrane:
- a casting solution of 15.7% Torion (registered trademark for Amoco) and 7.8% Ti0 2 (parts by weight based on 100 parts by weight of the solution) was prepared in dimethyl formamide (DMF).
- DMF dimethyl formamide
- This solution was applied in a layer thickness of 190 ⁇ m to a polyester fleece with a membrane drawing machine and co-dissolved in water at 20 ° C. acts.
- the membrane was dried at 90 ° C in an air stream. Then membrane samples were treated for 30 min at 100 ° C or 180 ° C. The following results were achieved with this membrane:
- a casting solution of 15.2% Torion (registered trademark for Amoco) and 10.5% Ti0 2 (parts by weight based on 100 parts by weight of the solution) in dimethyl formamide (DMF) was prepared.
- This solution was applied in a layer thickness of 190 ⁇ to a polyester carrier fleece using a membrane drawing machine and coagulated in water at 20 ° C.
- the membrane was dried at 90 ° C in an air stream. Then membrane samples were treated for 30 min at 100 ° C or 180 ° C. The following results were achieved with this membrane:
- a casting solution of 17% Torion (trademark registered for Amoco) (parts by weight based on 100 parts by weight of the solution) in dimethyl for amide (DMF) was prepared. This solution was applied in a layer thickness of 190 ⁇ m to a polyester carrier fleece using a membrane drawing machine and coagulated in water at 20 ° C. The membrane was dried at 90 ° C in an air stream. The following results were achieved with this comparison membrane:
- the membranes produced in this way contained 0.7% ( ⁇ 0.1) additional TiO 2 .
- the amount of Pd was 0.27% (+ 0.05). With this method, 1.7 mg of Pd could be introduced per membrane stamp (34 cm, 0.62 g). The gas flows decreased from
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
L'invention concerne une membrane microporeuse comportant une matrice polymère constituée d'un polymère pouvant former des liaisons hydrogène. Cette membrane est caractérisée en ce qu'au moins une charge inorganique est répartie dans la matrice polymère. L'addition de la charge permet à la membrane de conserver sa structure poreuse, même si elle est séchée de manière usuelle, par exemple dans un courant d'air. Cette membrane peut être utilisée directement en tant que membrane poreuse pour la séparation de mélange liquides et gazeux ou sous forme de vapeur, et en tant que membrane support pour des membranes catalytiques et des membranes composites.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19912582A DE19912582A1 (de) | 1999-03-19 | 1999-03-19 | Mikroporöse Membran mit einer Polymermatrix sowie Verfahren zu deren Herstellung |
DE19912582.1 | 1999-03-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000056431A1 true WO2000056431A1 (fr) | 2000-09-28 |
Family
ID=7901759
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/DE2000/000254 WO2000056431A1 (fr) | 1999-03-19 | 2000-01-29 | Membrane microporeuse comportant une matrice polymere, et son procede de production |
Country Status (2)
Country | Link |
---|---|
DE (1) | DE19912582A1 (fr) |
WO (1) | WO2000056431A1 (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004066428A3 (fr) * | 2003-01-20 | 2005-08-18 | Sartorius Gmbh | Unite membrane-electrodes, membranes polymeres conçues pour une unite membrane-electrodes, piles a combustible a electrolyte polymere et procedes de production correspondants |
US10618013B2 (en) | 2005-03-09 | 2020-04-14 | The Regents Of The University Of California | Nanocomposite membranes and methods of making and using same |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10047551B4 (de) * | 2000-09-22 | 2004-04-08 | Gkss-Forschungszentrum Geesthacht Gmbh | Direct Methanol Fuel Cell-Membran |
KR101228496B1 (ko) * | 2004-10-06 | 2013-01-31 | 리서치 파운데이션 어브 서니 | 고유속 및 저오염의 여과매체 |
DE102005011544A1 (de) * | 2005-03-10 | 2006-09-14 | Gkss-Forschungszentrum Geesthacht Gmbh | Verfahren zur Herstellung einer Polymermembran sowie Polymermembran |
WO2008057842A2 (fr) * | 2006-10-27 | 2008-05-15 | The Regents Of The University Of California | Structures de support micro- et nanocomposites pour membranes à couches minces d'osmose inverse |
CN101037244A (zh) * | 2007-04-23 | 2007-09-19 | 北京市百村环保科技开发有限公司 | 一种高浓度氨氮废水的处理方法和双相分离膜及其制备方法 |
DE102007029444A1 (de) | 2007-06-22 | 2008-12-24 | Goedel, Werner A., Dr. | Poröse Membran mit asymmetrischer Struktur und das Verfahren zu ihrer Herstellung |
DE102007029445A1 (de) | 2007-06-22 | 2008-12-24 | Werner A. Goedel | Verfahren zur Darstellung hierarchisch strukturierter Filme mittels Inkjet-Druck |
Citations (8)
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US3513020A (en) * | 1964-10-12 | 1970-05-19 | Leesona Corp | Method of impregnating membranes |
EP0005193A1 (fr) * | 1978-04-13 | 1979-11-14 | Sartorius GmbH. | Membranes asymétriques d'ultrafiltration à base d'hydrate de cellulose et leur procédé de fabrication |
EP0077509A1 (fr) * | 1981-10-21 | 1983-04-27 | Bayer Ag | Membranes semi-perméables |
EP0398093A2 (fr) * | 1989-05-18 | 1990-11-22 | Bayer Ag | Membranes composites, procédé de leur fabricaton et leur utilisation |
DE3927787A1 (de) * | 1989-08-23 | 1991-02-28 | Bayer Ag | Verbundmembran, ihre herstellung und verfahren zur pervaporation und gastrennung durch einsatz dieser verbundmembran |
US5130166A (en) * | 1990-12-14 | 1992-07-14 | E. I. Du Pont De Nemours And Company | Method for reducing the pore size of sintered metal filters by application of an alcoholic solution of a metal alkoxide which is converted to an insoluble hydrous metal oxide |
DE4113420A1 (de) * | 1991-04-25 | 1992-10-29 | Bayer Ag | Polyacrylnitril-hohlfaeden aus speziellen spinnloesungen nach dem dry/wet- oder nass-spinnverfahren |
DE4232496A1 (de) * | 1992-09-28 | 1994-03-31 | Geesthacht Gkss Forschung | Poly(amid-imide) und daraus gefertigte Membran |
-
1999
- 1999-03-19 DE DE19912582A patent/DE19912582A1/de not_active Withdrawn
-
2000
- 2000-01-29 WO PCT/DE2000/000254 patent/WO2000056431A1/fr active Application Filing
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US3513020A (en) * | 1964-10-12 | 1970-05-19 | Leesona Corp | Method of impregnating membranes |
EP0005193A1 (fr) * | 1978-04-13 | 1979-11-14 | Sartorius GmbH. | Membranes asymétriques d'ultrafiltration à base d'hydrate de cellulose et leur procédé de fabrication |
EP0077509A1 (fr) * | 1981-10-21 | 1983-04-27 | Bayer Ag | Membranes semi-perméables |
EP0398093A2 (fr) * | 1989-05-18 | 1990-11-22 | Bayer Ag | Membranes composites, procédé de leur fabricaton et leur utilisation |
DE3927787A1 (de) * | 1989-08-23 | 1991-02-28 | Bayer Ag | Verbundmembran, ihre herstellung und verfahren zur pervaporation und gastrennung durch einsatz dieser verbundmembran |
US5130166A (en) * | 1990-12-14 | 1992-07-14 | E. I. Du Pont De Nemours And Company | Method for reducing the pore size of sintered metal filters by application of an alcoholic solution of a metal alkoxide which is converted to an insoluble hydrous metal oxide |
DE4113420A1 (de) * | 1991-04-25 | 1992-10-29 | Bayer Ag | Polyacrylnitril-hohlfaeden aus speziellen spinnloesungen nach dem dry/wet- oder nass-spinnverfahren |
DE4232496A1 (de) * | 1992-09-28 | 1994-03-31 | Geesthacht Gkss Forschung | Poly(amid-imide) und daraus gefertigte Membran |
Non-Patent Citations (1)
Title |
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GENNE I ET AL: "EFFECT OF THE ADDITION OF ZRO2 TO POLYSULFONE BASED UF MEMBRANES", JOURNAL OF MEMBRANE SCIENCE,NL,ELSEVIER SCIENTIFIC PUBL.COMPANY. AMSTERDAM, vol. 113, no. 2, 15 May 1996 (1996-05-15), pages 343 - 350, XP000730098, ISSN: 0376-7388 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004066428A3 (fr) * | 2003-01-20 | 2005-08-18 | Sartorius Gmbh | Unite membrane-electrodes, membranes polymeres conçues pour une unite membrane-electrodes, piles a combustible a electrolyte polymere et procedes de production correspondants |
EP1722435A1 (fr) * | 2003-01-20 | 2006-11-15 | Sartorius Ag | Membrane polymère pour ensemble d'électrode à membrane et procédé de fabrication de ladite membrane |
US7682722B2 (en) | 2003-01-20 | 2010-03-23 | Elcomax Membranes Gmbh | Membrane-electrode assembly, polymer membranes for a membrane-electrode assembly, polymer electrolyte fuel cells, and methods for the production thereof |
US10618013B2 (en) | 2005-03-09 | 2020-04-14 | The Regents Of The University Of California | Nanocomposite membranes and methods of making and using same |
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