EP1159060A2 - Membranes multicouches et leur procede de fabrication - Google Patents

Membranes multicouches et leur procede de fabrication

Info

Publication number
EP1159060A2
EP1159060A2 EP00922423A EP00922423A EP1159060A2 EP 1159060 A2 EP1159060 A2 EP 1159060A2 EP 00922423 A EP00922423 A EP 00922423A EP 00922423 A EP00922423 A EP 00922423A EP 1159060 A2 EP1159060 A2 EP 1159060A2
Authority
EP
European Patent Office
Prior art keywords
groups
layer
carrier material
polyelectrolyte
individual layers
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Withdrawn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
EP00922423A
Other languages
German (de)
English (en)
Inventor
Jochen Meier-Haack
Theresia Rieser
Wolfgang Lenk
Siegfried Berwald
Dieter Lehmann
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.)
Leibniz Institut fuer Polymerforschung Dresden eV
Original Assignee
Leibniz Institut fuer Polymerforschung Dresden eV
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 Leibniz Institut fuer Polymerforschung Dresden eV filed Critical Leibniz Institut fuer Polymerforschung Dresden eV
Publication of EP1159060A2 publication Critical patent/EP1159060A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
    • B01D61/362—Pervaporation
    • B01D61/3621—Pervaporation comprising multiple pervaporation steps
    • 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
    • B01D69/107—Organic support material
    • B01D69/1071—Woven, non-woven or net mesh
    • 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
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/80—Block polymers

Definitions

  • Multi-layer membranes and process for their manufacture are Multi-layer membranes and process for their manufacture
  • the invention relates to the fields of chemistry, the converting industry, biotechnology and the food industry and relates to multilayer membranes, such as those used for the separation of aqueous alcohol mixtures by means of pervaporation, and methods for their production.
  • the general aim is to produce membranes with the thinnest possible active layers.
  • the phase inversion method is used for the production of such membranes (S. Loeb, S. Sourirajan, Adv. Chem. Ser. 38, 117 (1962)), which provides asymmetrical membranes with an integrated, separation-active layer.
  • the desired membranes can also be created using a composite structure, e.g. by the deposition of polyelectrolyte complex layers on a carrier material.
  • This symplex is applied to a non-ionic microporous support layer to ensure mechanical stability. In this process, only one complex layer is built up. However, since the porous carrier material has to be sealed, high mass inserts (2-5% by mass) of the symplex-forming components are necessary with this method, which lead to relatively high layer thicknesses (a few 100 nm) due to the manufacturing technique.
  • a pervaporation and gas separation membrane composed of a polyelectrolyte complex multilayer system has been described (L. Krasemann, B. Tieke J. Membr. Sei., 150, 23-30 (1998)).
  • the porous carrier material used was subjected to a technically complex plasma treatment before the polyelectrolyte multilayer complex was built up.
  • ionic groups are generated on the surface, which ensure improved adhesion of the adsorbed polyelectrolyte multilayer complex to the support material through electrostatic interaction.
  • Due to the porosity of the carrier material a high number of polyelectrolyte complex layers (> 30 double layers corresponding to> 60 single layers) is necessary in order to obtain a defect-free, separation-active layer and thus an effective membrane.
  • a further disadvantage of this membrane in addition to the necessary plasma pretreatment of the carrier material and the high number of polyelectrolyte complex layers, is the insufficient stability of the polyelectrolyte multilayer system with water contents of> 24% by mass in the feed.
  • the object of the present invention is to provide a multi-layer membrane with a defect-free separation-active layer and a high separation performance and to produce this by a more easily manageable and inexpensive method.
  • the multilayer membranes according to the invention consist of a dense or microporous support material and a separating layer applied thereon, this separating layer being composed of at least one individual layer.
  • the carrier material is at least chemically constructed in the same way.
  • it is chemically uniform and structurally asymmetrical.
  • the carrier material is constructed chemically and structurally in the same way throughout. In any case, the carrier material itself can also be active with regard to the separation problems to be processed.
  • the separation-active layer is in the form of a polyelectrolyte complex multilayer system in which the carrier material is connected to a single layer by a polyelectrolyte complex or, in the case of several individual layers on the carrier material, these individual layers are also connected to one another by a polyelectrolyte complex.
  • the individual layers applied one above the other alternately consist of at least one anionic and at least one cationic polyelectrolyte material which, after application, forms a complex bond with the previously applied individual layer.
  • two such individual layers originally charged differently are referred to as double layers.
  • the anionic polyelectrolyte materials are sulfonic acid groups and / or their salts and / or phosphonic acid groups and / or their salts and / or phosphoric acid groups and / or their salts and / or carboxyl groups and / or their salts and / or sulfate groups Homopolymers and / or copolymers of olefinically unsaturated monomers and / or polysaccharides containing carboxyl groups and / or their salts and / or polypeptides containing carboxyl groups and / or their salts.
  • the cationic polyelectrolyte materials are polymeric amine and / or ammonium or phosphine and / or phosphonium compounds.
  • the number of individual layers applied is considerably less than according to the prior art.
  • the layer thicknesses of the individual individual layers of the separation-active layer are also located in the area of the thinner layer thicknesses from the area of the known layer thicknesses.
  • thin layers in small numbers are sufficient to achieve an equally good or substantially improved separating effect compared to that of the prior art.
  • polyelectrolyte material is still predominantly covering the surface of the carrier material.
  • the amount applied is advantageously 5 to 500 ⁇ g / cm 2 carrier surface, more preferably 50 to 300 ⁇ g / cm 2
  • Carrier material instead, but at least partially extends deeper.
  • the carrier material is constructed in a uniform manner at least chemically and advantageously also structurally throughout.
  • the membrane according to the invention is used for dewatering organic substances, for example solvents, or mixtures of substances (aldehydes, ketones, ethers, alcohols, amines, acids) or for separating organics / organics * by means of pervaporation or for removing water vapor and / or hydrogen sulfide from substances or Mixtures of substances, such as water vapor and / or hydrogen sulfide from methane, by means of gas separation.
  • the membrane according to the invention should only be used for the separation of substances or mixtures of substances which are inert towards the membrane.
  • the anionic polyelectrolyte component is preferably homopolymers and / or copolymers and / or their salts, such as, for example, water-soluble sulfonic acid groups.
  • Poly (styrene sulfonic acid), poly (styrene sulfonic acid-old maleic anhydride), poly (vinyl sulfonic acid) sodium salt, poly (styrene sulfonic acid) sodium salt, and / or homo- and / or copolymers and / or their salts such as e.g. Poly (vinylphosphonic acid) and / or phosphoric acid groups containing homopolymers and / or copolymers and / or their salts, e.g.
  • Water-soluble nitrogen-containing polymer compounds and / or their salts such as e.g. Polyallylammonium chloride, polydimethyldiallylammonium chloride, polyvinylpyridinium salts, polyethyleneimine, tetraalkylammonium salt groups containing polymer compounds and / or polyvinyl compounds with quaternizable and / or quaternized nitrogen atoms, amino-functionalized poiysaccharides such as e.g. Chitosan and their salts and / or polypeptides containing amino groups (e.g. polylysine) and / or their salts are used.
  • Polyallylammonium chloride polydimethyldiallylammonium chloride, polyvinylpyridinium salts, polyethyleneimine, tetraalkylammonium salt groups containing polymer compounds and / or polyvinyl compounds with quaternizable and / or quaternized nitrogen atoms
  • the polyelectrolytes or polyelectrolyte components are preferably present in an aqueous solution and are applied to the carrier material.
  • the aqueous solution may optionally contain additional ionic and / or nonionic additives, such as low molecular weight electrolytes such as NaCl.
  • the carrier material can be a dense or microporous sheet or a membrane, in particular a sheet which is preferably non-porous. This carrier material consists of a water-insoluble polymer with carboxyl and / or amino and / or sulfonic acid groups and / or phosphonic acid groups and / or
  • the carrier material advantageously consists of one or more carboxyl-functionalized polyamide (s) and / or one or more carboxyl-functionalized homo- and / or copolymer of olefinically unsaturated monomers and / or of one or more reaction product (s) made of carboxyl-functionalized polyolefin (s) and / or homo - and / or copolymer of olefinically unsaturated monomers and polyamide (s).
  • Such a polymer is either used directly as a carrier material for the production of the membranes according to the invention or is applied to a nonwoven as a carrier material consisting of polyamide, polypropylene, polyester, polyphenylene sulfide or a fine silk fabric, preferably from solution.
  • the inventive multilayer membrane is produced by applying at least one single layer made of at least one anionic or at least one cationic polyelectrolyte material or from at least one separately produced non-stoichiometric polyelectrolyte complex by consecutively alternating application of the oppositely charged polyelectrolyte materials on the carrier material.
  • the order in which the individual polyelectrolyte components are applied to the carrier results from the charge of the carrier material used.
  • the individual layers are advantageously applied by immersing the carrier material, possibly with the individual layers already applied, into a solution which contains the respective anionic or cationic polyelectrolyte material (s) or the non- contains stoichiometric polyelectolyte complex (s) and possibly additional ionic and / or nonionic additives.
  • the production of the multilayer membrane according to the invention can likewise advantageously also be carried out in the finished module by rinsing the module with the corresponding polyelectrolyte solutions.
  • the carrier material is introduced into a module and connected accordingly.
  • the module At least immediately before use of the multilayer membrane, depending on the charge of the support material, the module must be rinsed with at least one solution which contains oppositely charged polyelectrolyte components or a non-stoichiometric polyelectrolyte complex. To apply several individual layers, one must alternately rinse with a solution that contains differently charged polyelectrolyte components or complexes. Between the application of the individual layers, the module is rinsed and / or dried with a liquid for washing, advantageously with water.
  • the individual layers are preferably applied at elevated temperatures.
  • the temperature is advantageously not chosen above the boiling point of the solvent used. It is particularly advantageous to apply the individual layers at temperatures in the range or above the glass transition temperature T g of the support material.
  • the mass fraction of the polyelectrolyte components in the solutions is between 0.01 and 5% by mass, preferably between 0.03 and 3% by mass.
  • the carrier material is a dense or microporous material functionalized with ionic and / or ionizable groups.
  • the multilayer membrane according to the invention is preferably washed with water or with a mixture of water and an organic solvent, preferably alcohol and in particular in a mixing ratio of 4: 1.
  • the multilayer membranes can be dried after the application of one and / or all of the individual layers and after washing. It has proved to be advantageous in that the multilayer membrane is dried after each coating step.
  • the polyelectrolyte complex layers applied to the support represent the actual release-active layer.
  • the support material can also contribute to the release effect.
  • the multilayer membranes according to the invention can be immersed in an aqueous solution containing the polyelectrolyte components, or by other known ways of applying a thin layer, such as e.g. Spraying or spin coating can be obtained.
  • a thin layer such as e.g. Spraying or spin coating can be obtained.
  • the multilayer membranes according to the invention are distinguished in that the use of a carrier material functionalized with ionic and / or ionizable groups ensures particularly good adhesion between the polyelectrolyte complex multilayer system and the carrier material. Furthermore, the multilayer membranes according to the invention are distinguished by a high water (steam) permeability or permeability of hydrophilic components and by a good selectivity for water and water vapor and for hydrophilic components in relation to other components. They can also be used multiple times, have high mechanical stability and are easy to handle. Furthermore, the multi-layer membrane production process is characterized by a low use of polyelectrolytes and the formation of very thin, defined separating layers that enable a high permeate flow.
  • the permeate flow J in kg / m 2 h under the given test conditions (temperature, composition of the feed, permeate-side pressure) and the separation factor ⁇ of the multilayer membranes are used for the permeate-related characterization of the multilayer membranes.
  • the ⁇ value is dimensionless Size that is defined as the concentration ratio of the binary mixtures in the permeate to that in the feed.
  • test conditions were as follows: permeate-side pressure: 2000 Pa temperature: 50 ° C
  • a polyelectrolyte complex multilayer system is applied to the polymeric carrier material, consisting of a carboxyl-functionalized polyamide-6 with a carboxyl group concentration of 207 ⁇ mol / g.
  • the multi-layer system is made by consecutive alternating immersion of the carrier material in aqueous
  • the polymer carrier is washed with water between each coating step.
  • Polyacrylic acid or polyethyleneimine serve as the polyanion or polycation component.
  • the concentration of the solutions is in each case 20 mmol / l, based on the monomer unit of the polyelectrolyte components.
  • the polyanion and the polycation material alternately apply 6 individual layers, ie a total of 12 single layers or 6 double layers.
  • the amount of layer material applied to the carrier surface is approximately 60 ⁇ g / cm 2 per individual layer.
  • the layer thickness of the entire release-active layer on the carrier material is approximately 7 nm.
  • Example 1 procedure, the after the application of the last polyelectrolyte layer
  • Multi-layer membrane is dried at 70 ° C.
  • Example 1 the polycation being polydimethyldiallylammonium chloride
  • the multilayer membrane according to the invention is produced as in Example 1, the polyanion being poly (styrene sulfonic acid) sodium salt Place of polyacrylic acid is used and a total of 10 double layers are applied.
  • Example 1 procedure, poly (styrene sulfonic acid) sodium salt being used as the polyanion and polydimethyldiallylammonium chloride being used as the polycation. A total of 10 double layers are applied.
  • Procedure 1 wherein the carrier material consists of a modified polyacrylonitrile. 3 double layers are applied.
  • Example 1 the support material consisting of a modified polyacrylonitrile and the application of the polyelectrolyte layers at 80.degree. It will be one

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention se rapporte au domaine de la chimie et concerne des membranes multicouches, telles que celles utilisées, par exemple, pour la division de mélanges d'alcools aqueux par pervaporation. L'objectif de la présente invention est de créer une membrane multicouche présentant une couche de séparation sans défaut et une capacité de séparation élevée. Cet objectif est atteint par la création de membranes multicouches constituées d'un matériau support compact ou microporeux et d'au moins une couche individuelle, appliquée sur ce matériau et liée à celui-ci par des complexes polyélectrolytiques, quelques couches individuelles étant appliquées et la première couche individuelle recouvrant la majeure partie de la surface dudit matériau support. L'objectif de l'invention est atteint grâce à un procédé de production de membranes multicouches, selon lequel, sur un matériau support compact ou microporeux, fonctionnalisé avec des groupes ioniques et/ou ionisables, est appliquée au moins une couche individuelle constituée d'au moins un matériau polyélectrolytique anionique ou d'au moins un matériau polyélectrolytique cationique, de façon alternée, ou bien d'au moins un complexe polyélectrolytique non stoechiométrique.
EP00922423A 1999-03-06 2000-02-25 Membranes multicouches et leur procede de fabrication Withdrawn EP1159060A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19909841 1999-03-06
DE19909841A DE19909841A1 (de) 1999-03-06 1999-03-06 Mehrschichtmembranen und Verfahren zu ihrer Herstellung
PCT/DE2000/000707 WO2000053296A2 (fr) 1999-03-06 2000-02-25 Membranes multicouches et leur procede de fabrication

Publications (1)

Publication Number Publication Date
EP1159060A2 true EP1159060A2 (fr) 2001-12-05

Family

ID=7899901

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00922423A Withdrawn EP1159060A2 (fr) 1999-03-06 2000-02-25 Membranes multicouches et leur procede de fabrication

Country Status (4)

Country Link
EP (1) EP1159060A2 (fr)
AU (1) AU4284500A (fr)
DE (2) DE19909841A1 (fr)
WO (1) WO2000053296A2 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7799467B2 (en) 2002-04-08 2010-09-21 Massachusetts Institute Of Technology Solid polymer electrolytes from ethylene oxide-containing, layer-by-layer assembled films
US7101947B2 (en) 2002-06-14 2006-09-05 Florida State University Research Foundation, Inc. Polyelectrolyte complex films for analytical and membrane separation of chiral compounds
US8679308B2 (en) * 2006-03-15 2014-03-25 Honeywell International Inc. Biosensor membrane and methods related thereto
DE102006036496A1 (de) 2006-07-28 2008-02-07 Leibniz-Institut Für Polymerforschung Dresden E.V. Sulfonierte Polyarylverbindungen, Membranmaterial daraus, Verfahren zu ihrer Herstellung und Verwendung
CN105056767B (zh) * 2015-08-14 2017-07-11 浙江大学 一种荷正电聚电解质络合物均质渗透汽化膜的制备方法
CN108043236A (zh) * 2017-12-20 2018-05-18 哈尔滨工业大学 一种新型陶瓷-聚酰胺复合纳滤膜及其制备方法
CN111992040B (zh) * 2020-09-10 2022-05-10 德州学院 一种聚电解质纳滤膜制备方法
CN115364691B (zh) * 2022-08-12 2023-08-25 中国科学院上海高等研究院 一种基于静电层层自组装技术制备的纤维素纳米纤维空气过滤复合膜及其制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5087367A (en) * 1987-12-02 1992-02-11 Japan Represented By Ministry Of International Trade And Industry, Director-General Basic Industries Bureau Hydrolyzed membrane and process for the preparation of the same
DD292846A5 (de) * 1989-10-11 1991-08-14 Akad Wissenschaften Ddr Verwendung von symplexmembranen fuer die pervaporation
JPH0691949B2 (ja) * 1992-04-23 1994-11-16 通商産業省基礎産業局長 ポリイオンコンプレックス製分離膜
KR100224471B1 (ko) * 1997-08-25 1999-10-15 김충섭 이중구조를 갖는 폴리이온콤플렉스 분리막

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0053296A3 *

Also Published As

Publication number Publication date
DE10080521D2 (de) 2002-07-25
WO2000053296A2 (fr) 2000-09-14
WO2000053296A3 (fr) 2000-12-28
AU4284500A (en) 2000-09-28
DE19909841A1 (de) 2000-09-07

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