EP2125173A1 - Membrane échangeuse d'ions renforcée composée d'un support et d'un film polymère appliqué en couche sur le support - Google Patents

Membrane échangeuse d'ions renforcée composée d'un support et d'un film polymère appliqué en couche sur le support

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Publication number
EP2125173A1
EP2125173A1 EP07703267A EP07703267A EP2125173A1 EP 2125173 A1 EP2125173 A1 EP 2125173A1 EP 07703267 A EP07703267 A EP 07703267A EP 07703267 A EP07703267 A EP 07703267A EP 2125173 A1 EP2125173 A1 EP 2125173A1
Authority
EP
European Patent Office
Prior art keywords
polymeric film
exchange membrane
ion
reinforced ion
reinforced
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Withdrawn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
EP07703267A
Other languages
German (de)
English (en)
Inventor
Erik Middelman
Jörg Henning Balster
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.)
REDSTACK BV
Original Assignee
REDSTACK BV
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 REDSTACK BV filed Critical REDSTACK BV
Publication of EP2125173A1 publication Critical patent/EP2125173A1/fr
Withdrawn legal-status Critical Current

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    • 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
    • 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
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/422—Electrodialysis
    • 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
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/422—Electrodialysis
    • B01D61/423—Electrodialysis comprising multiple electrodialysis steps
    • 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
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • 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
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • B01D61/54—Controlling or regulating
    • 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
    • B01D71/52—Polyethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D71/06—Organic material
    • B01D71/52—Polyethers
    • B01D71/522—Aromatic polyethers
    • B01D71/5222—Polyetherketone, polyetheretherketone, or polyaryletherketone
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    • B01D71/68—Polysulfones; Polyethersulfones
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    • B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/02—Layered products comprising a layer of synthetic resin in the form of fibres or filaments
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2275—Heterogeneous membranes
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1044—Mixtures of polymers, of which at least one is ionically conductive
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1053—Polymer electrolyte composites, mixtures or blends consisting of layers of polymers with at least one layer being ionically conductive
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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    • H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
    • H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H—ELECTRICITY
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    • H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/26—Electrical properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/06—Polysulfones; Polyethersulfones
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    • H01M8/0289—Means for holding the electrolyte
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • 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
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Definitions

  • the present invention relates to a reinforced ion- exchange membrane comprised of a porous support matrix and, laminated thereon, a polymeric film. More specifically, the present invention relates to a reinforced cationic or anionic exchange membrane. The present invention further relates to a reinforced ion-exchange membrane for use in (reverse) electrodialysis and a method for preparing said reinforced ion-exchange membrane.
  • a membrane is defined as a permselective barrier separating two phases. Certain compounds can pass through the membrane under the influence of a driving force while others are excluded from passing. Because of this, such a membrane has a capacity of selectively transporting (transferring, separating) compounds from one phase (feed) to another (permeate) .
  • a schematic presentation of this process is shown in figure 1.
  • the membranes or barriers according to the present invention are charged polymeric membranes capable of transporting (transferring, separating) charged particles, such as ions or other charged compounds or particles, through an electric potential difference between two phases (solutions) .
  • Such membranes are also designated as ion- exchange membranes, although not specifically limited to ion separations whereby ions are small inorganic charged compounds such as Na + or Cl " .
  • Ion-exchange membranes can generally be divided in two different types depending on the charge of the membrane, i.e., cation-exchange membranes (negative charge, cem) and anion-exchange membranes (positive charge, aem) .
  • Cation-exchange membranes (cem) generally have negatively charged moieties fixed thereon.
  • anion-exchange membranes (aem) generally have positively charged moieties fixed thereon.
  • cation-exchange membranes commonly use charge providing sulfonic acids moieties, i.e., compounds comprising one or more -SO 3 " groups, or carboxylic acids moieties, i.e., compounds comprising one or more -COO " groups, fixed (adhered, cross-linked, connected, bonded) to their basic polymeric films.
  • Cation-exchange membranes are used for various electrically driven membrane based processes. For example, they may serve in electrodialysis as separators between concentrate and diluate compartments, in fuel cells, as proton conductors, and as a cation permeable layer of bipolar membranes selectively permeable for protons and water while retaining anions .
  • anion-exchange membranes commonly use charge providing quaternary ammonium moieties, i.e., compounds comprising one or more -R 3 N + groups, fixed (adhered, cross-linked, connected, bonded) to their basic polymeric film, wherein R represents an alkyl or aryl, linear or branched, substituted or not substituted, of C 1 to C 20 carbon atoms chains such as -C 2 H 5 or -C 4 H 9 .
  • These positively and negatively charged moieties represent strong acids and bases, respectively, and are substantially dissociated, i.e., charge providing, over a broad pH range for example pHs of 2 to 12.
  • Ion-exchange membranes can be used for electrodialysis . Electrodialysis involves a selective transport (transfer, separation) , against the concentration gradient, of ions from one, for example, aqueous solution to another, for example, aqueous solution, under the influence of an electrical potential gradient as the driving force.
  • an ion-exchange membrane When placed in an electrolyte solution, the affinity of an ion-exchange membrane for positively and negatively charged ions in the electrolyte solution is different depending on the charge of the moieties fixed thereon.
  • a cationic ion-exchange membrane i.e., a membrane with negatively charged moieties
  • negatively charged particles such as anions are excluded (stopped, prevented from passing) by cation-exchange membranes because their electrical charge being the same as the charge of the fixed moieties on the membrane. This despite an electric potential difference over the cation- exchange membrane .
  • FIG 3 A specific embodiment of an electrodialysis process is provided in figure 3.
  • an aqueous salt solution is fed to an electrodialysis stack consisting of a series of cation and anion exchange membranes between two working electrodes.
  • the positively charged cations migrate towards the cathode and the negatively charged anions in the opposite direction towards the anode .
  • the cations pass easily through the negatively charged cation-exchange membranes, in contrast with the excluded anions. As shown in figure 3, this results in the separation of the feed solution into a solution enriched in ions (the concentrate) and a solution depleted of ions (the diluate) .
  • Electrodialysis can also, for example, be used in desalination of water, desalination in food and pharmaceutical industry, separation of amino acids and production of salts .
  • a special form of electrodialysis is reverse electrodialysis.
  • a reverse electrodialysis cell is comprised of monopolar ion-exchange membranes arranged in the same order as in conventional electrodialysis.
  • the potential drop is used, which develops when a membrane separates two electrolyte solutions differing in concentrations.
  • the compartments contain therefore alternately high and low concentrations of the electrolyte.
  • the generated current can be taken from this process, i.e., the generation of electric power.
  • the generation of electric power depends on the number of cells.
  • the efficiency of the process also depends on the membrane resistance and their permselectivities .
  • the efficacy or usefulness of ion-exchange membranes is determined by several parameters such as a) a high permselectivity (ion selectivity) b) a low electrical resistance c) a good mechanical strength, and d) a high chemical stability.
  • the properties of ion-exchange membranes are also influenced by the basic polymer film and the type and concentration of the fixed charged moieties.
  • the basic polymer film determines to a large extent the mechanical, chemical and thermal stability of the membrane.
  • such basic polymeric films are made of hydrophobic polymers such as polystyrene, polyethylene or polysulfone .
  • these polymers are largely insoluble in water and show a low degree of swelling, through the introduction of charged moieties ionic groups, they may become water soluble. Thus, the basic polymers are often crosslinked.
  • the swelling (when placed in an aqueous environment) and the chemical and thermal stability are also influenced by the degree of crosslinking.
  • the type and the concentration of the fixed charged moieties influence the permselectivity and the electrical resistance of the membrane, but they also have a significant effect on the swelling and the mechanical properties of the membrane.
  • Another important aspect is the relation between the mechanical strength of the ion-exchange membrane and its thickness. For example, when the thickness of the membrane is increased also the mechanical strength is increased. However, the electric resistance will be undesirably increased.
  • reinforced membranes have been proposed such as for example in WO 95/16730. These membranes are comprised of a support matrix providing the required mechanical strength while the selective ion-exchange is provided by the polymeric film.
  • these reinforced ion-exchange membranes still require a relatively thick ion-exchange membrane or film, for example in the range of 100 to 250 micrometers, to provide the required ion selectivity. Inherently, this increased thickness does not only increases the electric resistance of the reinforced membrane, but also its costs.
  • Another objective of the present invention is to provide a reinforced ion-exchange membrane wherein mechanical strength is substantially provided by the reinforcement and the ion-selectivity is provided by a relatively thin ion- exchange membrane as compared to the prior art .
  • a reinforced ion-exchange membrane comprising a porous support matrix and, laminated on at least on side thereof, a polymeric film, wherein the porous support matrix has no electric resistance as measured in the six compartment configuration and wherein the polymeric film comprises a polymer functionalized with charged moieties in a degree of at least 50%, such as 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% and 100%.
  • the polymeric film comprises a polymer functionalized with charged moieties in a degree of at least 50%, such as 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% and 100%.
  • Preferred is a degree of functionalization between 55% to 85%, such as 60%, 65%, 70%, 75% and 80%.
  • the electrical resistance of the porous support matrix according to the present invention is measured in the six compartment configuration.
  • This measurement is performed with a six compartment cell with a four electrode arrangement, as shown in figure 4, under direct current using a 0.5 M NaCl solution.
  • the porous support matrix is first equilibrated in the measurement solution for more than 24 hours.
  • the measurement solution is added in the compartments 3 and 4, next to the porous support matrix to be investigated, with calomel reference electrodes.
  • an NaCl solution with the same concentration is used as in the measurement compartments to reduce the influence of the electrode reactions at the working electrodes.
  • a current is applied through the working electrodes in the compartments 1 and 6 whereas the electrical potential is measured close to the surface of the porous support matrix in the compartments 3 and 4 with the calomel reference electrodes .
  • the area resistance between the calomel reference electrodes is determined from the current-voltage curve (i-v curve) and is measured with and without the porous support matrix.
  • the difference of the two resistances is considered as the porous support electric resistance (R) . This difference is substantially zero for the porous support matrices according to the present invention.
  • the degree of functionalization (SD) of the polymer comprised in the polymeric film according to the present invention can be measured using the equation 1:
  • M Wff is the molecular weight of the functional group including the counter ion
  • M W(P the molecular weight of the non-functional polymer repeat unit
  • IEC the ion echange capacity
  • the IEC of the polymeric films is determined by titration as decribed by Wilhelm et al . , Journal of Membrane Science 199 (2002), 167-176. Briefly, in case of an illustrative cationic polymeric film, the polymeric film is first brought in the H + form by immersion into IM HCl solution for 24 h (the solution is replaced in between for total ion exchange) .
  • the membrane is soaked in water and is then brought into the Na + form by immersing in 2 M NaCl solution. To ensure a complete exchange, the NaCl solution is renewed several times. The collected solutions are combined and titrated with NaOH to determine the proton content .
  • the IEC is calculated as the ratio of total charge by the dry weight of the polymeric film.
  • the present invention relates to a reinforced ion-exchange membrane, wherein the polymeric film comprises a blend of a functionalized polymer and a non-functionalized polymer.
  • the functionalized polymer is a sulphonated poly (ether ether ketone) functionalized polymer.
  • non-functionalized polymer is used herein to encompass any polymer which is not functionalized with charged moieties providing ionic selectivity to the reinforced ion-exchange membrane according to the present invention.
  • the non- functionalized polymer is poly (ethersulphon) non- functionalized polymer.
  • the reinforced ion-exchange membrane according to the present invention comprises a polymeric film comprising 50% to 90%, such as 55%, 60%, 65%, 70%, 75%, 80% and 85% by weight, functionalized polymer and 50% to 10%, such as 45%, 40%, 35%, 30%, 25%, 20% and 15%, by weight non- functionalized polymer.
  • the reinforced ion-exchange membrane according to the present invention comprises a polymeric film comprising 60% to 85%, such as 65%, 70%, 75% and 80%, by weight functionalized polymer and 40% to 15%, such as 35%, 30%, 25% and 20% by weight, non-functionalized polymer.
  • the reinforced ion-exchange membranes according to the present invention preferably comprise charged moieties selected from the group consisting of sulfonic acids, carboxylic acids, and ammonium moieties providing a charge to the polymeric film over a broad pH range. More preferably, the charged moieties are sulfonic acids.
  • porous support matrix can be any nonconducting porous support matrix
  • porous support matrices comprised of a non-woven fabric comprised of a material selected from the group consisting of glass, silica, polyolefins, polypropylene, polyethylene, polyurethane, polystyrene, polybutylene and co-polymers thereof. More preferred are non-woven fabrics comprised of polypropylene and polyethylene.
  • the reinforced ion-exchange membrane according to the present invention comprises a porous support matrix, as defined above, with a thickness of between 30 to 150 micrometers and, laminated thereon, a polymeric film, as defined above, with a thickness of between 5 to 15 micrometers .
  • a reinforced ion-exchange membrane comprising a porous support matrix, as defined above, with a thickness of between 40 to 130 micrometers and, laminated thereon, a polymeric film, as defined above, with a thickness of between 8 to 11 micrometers .
  • the present invention also relates to a method for preparing a reinforced ion-exchange membrane comprising: a) providing a polymeric film according to the present invention and a porous support matrix according to the present invention; b) covering the polymeric film with a solvent for said polymeric film or a solution of a monomer of which said polymeric film is comprised; c) pressing said porous support matrix onto the polymeric film; and d) removing said solvent or solution to provide a reinforced ion-exchange membrane according to the present invention.
  • the reinforced ion-exchange membranes according to the present invention a particularly useful when used for (reverse) electrodialysis .
  • the present invention also relates to the use of a present reinforced ion-exchange membrane for electrodialysis or reverse electrodialysis applications .
  • Particular examples of applications of electrodialysis or reverse electrodialysis applications are, but not limited thereto, desalination of water, desalination in food and pharmaceutical industry, separation of amino acids, production of salt, fuel cells, electric power generation and immediate and sustained release carriers for pharmaceuticals .
  • Fig. 1 is a schematic drawing of a membrane separation
  • Fig. 2 is a schematic presentation of a cation-exchange membrane next to an electrolyte solution
  • Fig. 3 shows the principle of electrodialysis
  • Fig. 4 shows a six compartment cell for the determination of electric resistance
  • Fig. 5 shows a chronopotentiometric curve of a CMX cation exchange membrane
  • Fig. 6 shows the experimental setup of an impedance measurement
  • ' Fig. 7 shows the conductivity and water content of various
  • S-PEEK/PES blends with a degree of 61% and 83% sulphonation (SD) ;
  • Fig. 8 shows the permselectivity (ion selectivity) versus the thickness of two S-PEEK/PES blends, i.e., 60/40 and 80/20, respectively, with a degree of sulphonation (SD) of 80%.
  • Example 1 a polymeric film suitable for a reinforced cation-exchange membrane according to the present invention
  • Sulphonated poly (ether ether ketone), S-PEEK, was chosen as the functionalized polymer in the cation exchange polymeric film. This material is blended with the non- functionalized polymer poly (ethersulphone) , PES, to improve membrane properties.
  • PES non-functionalized polymer poly
  • PEEK 450PF from Victrex As precursor polymer PEEK 450PF from Victrex was used. PEEK is an amorphous polymer, with low water absorption and high solvent resistance. The polymer was dried for more than 24 hours in a vacuum oven, at 100 0 C.
  • reaction vessel was immersed in an ice bath to stop the reaction.
  • the sulphonated polymer (S-PEEK) was precipitated in demineralized water of maximum 5 0 C and washed until the pH was 7. Subsequently, the polymer was dried in air at room temperature and in a vacuum oven at 100 0 C.
  • the polymer solution was filtered over a 40 micrometer metal filter.
  • the films were prepared by the evaporation technique. Briefly, the solutions were cast on glass plates with different casting knifes. The films were dried in an N 2 atmosphere at 40-80 0 C for 1 week.
  • the polymeric films obtained were washed with water and placed in a vacuum oven at 3O 0 C for one week.
  • the dry polymeric films were stored in 0.5 M NaCl solution and their thickness in wet state (d wet ) was measured.
  • Non-woven as polymeric film support Two different non-woven fabrics from Freudenberg (Viledon) , made from polypropylene/polyethylene, were used as polymeric film support matrix:
  • Viledon non-woven thickness 120 micrometers 2. Viledon non-woven, thickness 45 micrometers
  • the prepared polymeric films were characterized by measurements of the ion exchange capacity (IEC) , water uptake (w) , electrical resistance (R) , and the permselectivity (S) .
  • IEC ion exchange capacity
  • w water uptake
  • R electrical resistance
  • S permselectivity
  • the IEC of the membranes was determined by titration. For this, the polymeric film was first brought in the H + form by immersion into 1 M HCl solution for 24 hours (the solution was replaced in between for total ion exchange) .
  • the polymeric film was soaked in water and was then brought into the Na + form by immersing in 2 M NaCl solution. To ensure complete exchange, the NaCl solution was renewed several times .
  • the collected solutions were combined and titrated with NaOH to determine the proton content.
  • the IEC was calculated as the ratio of total charge by the dry weight of the polymeric film .
  • the degree of sulphonation was calculated according to equation 1 :
  • M w,p is the molecular weight of the polymer non-functional repeat unit and M W/f is the molecular weight of the functional group including the counter ion (-SO 3 Na) .
  • the water uptake of the polymeric films was measured in different ionic forms following the weighing procedure.
  • the polymeric film was first brought into the desired ionic form (H + , Na + or Ca 2+ and the weight of the wet (m ⁇ ,.) and dry (m dry ) sample was measured.
  • the water uptake of the polymeric film is given by equation 2:
  • the charge density (x) of the polymeric film can be calculated by equation 3:
  • the permselectivity was determined by static membrane potential measurement.
  • the test system consisted of two cells separated by the polymeric film sample. Two calomel reference electrodes (Schott B2810) were placed into the solutions on either side of the polymeric film and were used to measure the potential difference across the polymeric film.
  • the permselectivity (S) of the polymeric film is given by the ratio of the measured potential difference ( ⁇ V raeas ) and the potential difference calculated by equation 4 for a 100% permselective polymeric film ( ⁇ V calc ) :
  • the electrical resistance of the polymeric films was measured in a six compartment cell with a four electrode arrangement (figure 4) under direct current using a 0.5M NaCl solution.
  • the polymeric film was first equilibrated in the measurement solution for more than 24 hours.
  • the measurement solution was added in the compartments 3 and 4, next to the investigated polymeric film with the calomel reference electrodes.
  • a NaCl solution with the same concentration was used as in the measurement compartments to reduce the influence of the electrode reactions at the working electrodes.
  • the current was applied through the working electrodes in the compartments 1 and 6, whereas the electrical potential was measured close to the polymeric film surface in the compartments 3 and 4 with the calomel reference electrodes.
  • the area resistance between the calomel reference electrodes was determined from the current-voltage curve (i-v curve) and was measured with and without the polymeric film. The difference of the two resistances was considered as the polymeric film area resistance (R) .
  • the specific conductivity was then calculated using equation 5:
  • the cell has a Teflon interior with two circular gold or stainless steel electrodes, surface area of 0.28 cm 2 . Both electrodes are connected with two wires, one for carrying the current and one for acting as a potential probe.
  • the cell was connected to a frequency response analyzer (Solatron 1255) .
  • the polymeric film sample was sandwiched between two gold electrodes. The impedance spectrum was measured in the frequency range of 100 Hz to 0.2 MHz with a potential of 0.01 V at 25 0 C and a 100% relative humidity.
  • the resistance value associated with the polymeric film conductivity was determined from the high frequency intercept of the impedance with the real axis. The conductivity was calculated using the equation 5.
  • Another way to measure the transport number and therefore the selectivity of the polymeric films under an applied electric field is chronopotentiometry . This is an electrochemical characterization method that measures the electric potential response of a system to an imposed current.
  • Chronopotentiometric measurements are active measurements performed in the same configuration as the resistance measurements (see figure 4) in a 0.1 M NaCl solution. A constant current density is applied and the voltage drop between the electrode and a reference electrode is measured as a function of time.
  • a typical example of a chronopotentiometric curve, measured with a CMX membrane in a 0.1 M NaCl solution when applying a current density above the limiting current density of the system, can be seen in figure 6.
  • the chronopotentiometric curve has four distinct regions. The experiment is started without applying a current. Because the solutions on either side of the polymeric film are equal, the voltage drop remains zero. A fixed current density, which is higher than the limiting current density of the system, is applied at point A.
  • i is the current density
  • C 0 is the concentration of the solution
  • z is the valence of the ion
  • F is the Faraday constant
  • D is the diffusion coefficient
  • t + and t are the diffusion coefficient
  • This equation is called Sand equation. This equation was used to calculate the transport number and therefore the selectivity of the membrane under an applied current density.
  • the S-PEEK/PES blends show a constant permselectivity with decreasing film thickness. Only the thinnest film of approximately 9 micrometers shows a slightly reduced permselectivity. Therefore, the S-PEEK/PES blends provide a suitable polymeric film for a reinforced cation-exchange membrane .
  • polymeric films with various thicknesses were prepared from made from the different S-PEEK solutions (see table 2) .
  • Table 2 Measured properties of the prepared S-PEEK based polymeric films.
  • the relation between the thickness of the polymeric films obtained and the ion selectivity is shown in figure 8.
  • the S-PEEK/PES blends show very high permselectivities even with very thin polymeric films.
  • the 9 and 10 micrometers layers of both S-PEEK/PES blends lose less than 2% of selectivity compared to the thick ones.
  • the thin S-PEEK/PES 60/40 film (9 micrometers) was pressed onto the support material (non-woven comprised of polypropylene and polyethylene) and investigated.
  • the S-PEEK/PES solution (60% S-PEEK) was casted directly over the nonwoven support material (Viledon, 0.12 mm thick polyester, obtained by Freudenberg, UK) and dried as described in the experimental section.
  • the S-PEEK/PES membranes were prepared as described in the experimental section. After drying, the surface of the membrane is covered with a thin layer of solvent (NMP) and the support is pressed onto this membrane.
  • NMP solvent
  • S-PEEK/PES membranes were prepared as described in the experimental section. After drying, the surface of the membrane is covered with a thin layer of S-PEEK solution (in NMP) and the support is pressed onto this membrane.
  • the first method does not result in selective membranes.
  • the S-PEEK/PES solution sinks inside the support, without forming a selective layer. Therefore this method is not suited to prepare the reinforced ion-exchange membranes according to the present invention.
  • the other two methods i.e., layering a polymeric film onto the porous support matrix yield the supported ion- exchange membranes according to the present invention.
  • H 2 SO 4 13 euro/L from Merck (95-97%)
  • For the sulphonation of 1 kg PEEK 16.7 liters H 2 SO 4 is needed, resulting in 286.7 euroC/kg S-PEEK. Because the S-PEEK has to be washed with water and the wastewater has do be disposed, a total cost is assumed of 500 euro/kg for the production of S-PEEK.
  • the averaged density of the S-PEEK/PES blend is 1306 kg/m 3 . Therefore one square meter of a 10 micrometers S-PEEK/PES (60/40) polymeric film would cost about 5 euro.
  • the properties, i.e., mechanical strength and ion- slectivity, of the S-PEEK/PES blends based reinforced ion- exchange membranes and the production cost are very advantegous compared to reinforced ion-exchange memebranes according to the prior art.
  • Thin S-PEEK/PES films with high selectivity and low resistance can be produced.
  • the relative high ratio of PES provides high selectivities and decreases the production costs of the membranes.
  • the tested Viledon support (non-woven comprised of polypropylene and polyethylene) can be advantegously used as porous polymeric support.

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Abstract

La présente invention concerne une membrane échangeuse d'ions renforcée, composée d'une matrice de support poreuse et d'un film polymère appliqué en couche sur la matrice de support poreuse. La présente invention concerne plus précisément une membrane échangeuse d'ions renforcée, composée d'une matrice de support poreuse et d'un film polymère appliqué en couche sur au moins un des côtés du support. La matrice de support poreuse n'a aucune résistance électrique, dans des mesures réalisées dans la configuration à six compartiments. Le film polymère comprend un polymère fonctionnalisé comportant au moins 50% de groupes caractéristiques chargés.
EP07703267A 2007-02-05 2007-02-05 Membrane échangeuse d'ions renforcée composée d'un support et d'un film polymère appliqué en couche sur le support Withdrawn EP2125173A1 (fr)

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US11502323B1 (en) 2022-05-09 2022-11-15 Rahul S Nana Reverse electrodialysis cell and methods of use thereof
US11502322B1 (en) 2022-05-09 2022-11-15 Rahul S Nana Reverse electrodialysis cell with heat pump
US11855324B1 (en) 2022-11-15 2023-12-26 Rahul S. Nana Reverse electrodialysis or pressure-retarded osmosis cell with heat pump

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EP2508554A4 (fr) * 2009-12-04 2013-11-20 Prudent Energy Inc Membrane échangeuse de protons en mélange de polymères et procédé de préparation associé
NL2008538C2 (en) * 2012-03-26 2013-09-30 Stichting Wetsus Ct Excellence Sustainable Water Technology Energy generating system using capacitive electrodes and method there for.
JP2019509600A (ja) * 2016-03-17 2019-04-04 スリーエム イノベイティブ プロパティズ カンパニー 膜アセンブリ、電極アセンブリ、膜電極アセンブリ並びにこれらによる電気化学セル及び液体フロー電池
KR102280150B1 (ko) * 2019-08-16 2021-07-21 도레이첨단소재 주식회사 1가 음이온 선택성 이온 교환막

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US5447636A (en) * 1993-12-14 1995-09-05 E. I. Du Pont De Nemours And Company Method for making reinforced ion exchange membranes
WO2001070857A2 (fr) * 2000-03-22 2001-09-27 Victrex Manufacturing Limited Matieres d'echange ionique

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US11502323B1 (en) 2022-05-09 2022-11-15 Rahul S Nana Reverse electrodialysis cell and methods of use thereof
US11502322B1 (en) 2022-05-09 2022-11-15 Rahul S Nana Reverse electrodialysis cell with heat pump
US11563229B1 (en) 2022-05-09 2023-01-24 Rahul S Nana Reverse electrodialysis cell with heat pump
US11611099B1 (en) 2022-05-09 2023-03-21 Rahul S Nana Reverse electrodialysis cell and methods of use thereof
US11699803B1 (en) 2022-05-09 2023-07-11 Rahul S Nana Reverse electrodialysis cell with heat pump
US11855324B1 (en) 2022-11-15 2023-12-26 Rahul S. Nana Reverse electrodialysis or pressure-retarded osmosis cell with heat pump

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