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 PDF

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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
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WO
WIPO (PCT)
Prior art keywords
membrane
membrane according
filler
polymer matrix
polymer
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.)
Ceased
Application number
PCT/DE2000/000254
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German (de)
English (en)
Inventor
Detlev Fritsch
Katrin Ebert
Regina Just
Klaus-Viktor Peinemann
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.)
GKSS Forshungszentrum Geesthacht GmbH
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GKSS Forshungszentrum Geesthacht 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.)
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Publication date
Application filed by GKSS Forshungszentrum Geesthacht GmbH filed Critical GKSS Forshungszentrum Geesthacht GmbH
Publication of WO2000056431A1 publication Critical patent/WO2000056431A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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

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  • 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.
PCT/DE2000/000254 1999-03-19 2000-01-29 Membrane microporeuse comportant une matrice polymere, et son procede de production Ceased WO2000056431A1 (fr)

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

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Publication Number Publication Date
WO2000056431A1 true WO2000056431A1 (fr) 2000-09-28

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DE (1) DE19912582A1 (fr)
WO (1) WO2000056431A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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
US8222166B2 (en) * 2004-10-06 2012-07-17 The Research Foundation Of State University Of New York High flux and low fouling filtration media
DE102005011544A1 (de) * 2005-03-10 2006-09-14 Gkss-Forschungszentrum Geesthacht Gmbh Verfahren zur Herstellung einer Polymermembran sowie Polymermembran
AU2007317516B2 (en) * 2006-10-27 2013-04-04 The Regents Of The University Of California Micro-and nanocomposite support structures for reverse osmosis thin film membranes
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
DE102007029445A1 (de) 2007-06-22 2008-12-24 Werner A. Goedel Verfahren zur Darstellung hierarchisch strukturierter Filme mittels Inkjet-Druck
DE102007029444A1 (de) 2007-06-22 2008-12-24 Goedel, Werner A., Dr. Poröse Membran mit asymmetrischer Struktur und das Verfahren zu ihrer Herstellung

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

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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)

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Title
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)

* Cited by examiner, † Cited by third party
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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