WO2003013708A2 - Membrane hybride, son procede de production et son utilisation - Google Patents

Membrane hybride, son procede de production et son utilisation Download PDF

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Publication number
WO2003013708A2
WO2003013708A2 PCT/EP2002/008697 EP0208697W WO03013708A2 WO 2003013708 A2 WO2003013708 A2 WO 2003013708A2 EP 0208697 W EP0208697 W EP 0208697W WO 03013708 A2 WO03013708 A2 WO 03013708A2
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WIPO (PCT)
Prior art keywords
membrane
hybrid
hybrid membrane
membrane according
polymer
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PCT/EP2002/008697
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German (de)
English (en)
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WO2003013708A3 (fr
Inventor
Christian Hying
Gerhard HÖRPEL
Katrin Ebert
Klaus Ohlrogge
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Creavis Gesellschaft Für Technologie Und Innovation Mbh
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Priority to AU2002321292A priority Critical patent/AU2002321292A1/en
Publication of WO2003013708A2 publication Critical patent/WO2003013708A2/fr
Publication of WO2003013708A3 publication Critical patent/WO2003013708A3/fr

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Classifications

    • 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
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0048—Inorganic membrane manufacture by sol-gel transition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/009—After-treatment of organic or inorganic membranes with wave-energy, particle-radiation or plasma
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/108—Inorganic 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
    • B01D69/12—Composite membranes; Ultra-thin 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
    • B01D69/148—Organic/inorganic mixed matrix membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/08—Specific temperatures applied
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/12—Specific ratios of components used

Definitions

  • the invention relates to a hybrid membrane, made of an inorganic permeable carrier material with an organic selective separating layer.
  • Ceramic membranes have been known for more than 10 years and due to their rather high price are always used where either good temperature resistance (> 80 ° C) or good chemical resistance must be guaranteed. These membranes are commercially available for microfiltration and for ultrafiltration applications. Various applications in pervaporation and nanofiltration have recently been reported (K.-V. Peinemann and S.P. Nunes, Membrane Technology; 2001, VCH-Verlag).
  • the ceramic materials of the separating layers which are used in the latter applications, are nanoparticulate and have a very large surface area. This and the limitation to materials such as ⁇ -aluminum oxide or silicon dioxide means that these membranes do not have the required acid or alkali resistance. Reverse osmosis membranes and membranes that separate according to the solution diffusion mechanism are not accessible from ceramic materials.
  • Polymeric membranes made from a wide variety of polymers are available relatively cheaply for wide pH ranges and many applications. However, most materials are not solvent-resistant or not resistant at temperatures above 80 ° C.
  • polymeric membrane materials can do much more than the polymeric membranes currently do.
  • the weak point of the polymeric membranes is not the materials or the selective layers. These can be tailored to the separation task by skillful selection of materials and chemical modification.
  • the weak point of the polymeric membranes is the polymer support structure of the membranes.
  • the polymeric carrier fleeces and the polymeric asymmetrical carrier membranes do not meet the requirements.
  • ion-conducting composite material which can be used as a membrane is known, the ionic conduction being achieved, inter alia, by adding ion-conducting polymers to the composite material.
  • ion-conducting polymers These are polymers However, it does not exist as a separating layer, but extends through the entire pores from one to the other side of the composite material so that ion conduction can take place.
  • WO 99/62624 describes composite materials with hydrophobic properties which can be used as a membrane and which can have polymers on the inner and outer surfaces. These polymers do not represent the release-active layer, but serve to produce the hydrophobicity of the composite material.
  • the polymers are added to the sol, from which a suspension, which is applied to a support and solidified, is added. In this way, the polymer is distributed over the entire cross section of the composite material. The pore size of this composite material is determined by the inorganic particles.
  • the task was therefore to develop a membrane with the positive separation properties of a polymer membrane, which has a sufficiently high stability at higher temperatures and when exposed to oils or solvents, and which can be manufactured inexpensively.
  • a hybrid membrane which has a polymeric separating layer and a ceramic carrier material, has the separating properties of a polymer membrane and largely the chemical resistance and the pressure resistance of a ceramic membrane. It has also surprisingly been found that the methods of producing polymeric membranes are very easily applicable to a flexible inorganic, chemically stable and pressure-stable carrier material.
  • the present invention therefore relates to a hybrid membrane according to claim 1, with a selective separating layer, the membrane having an inorganic permeable carrier material and polymeric material, which is characterized in that the selective separating layer is formed by the polymeric material.
  • the present invention also relates to a method for producing a hybrid membrane with a selective separation layer, the membrane having an inorganic permeable carrier material and polymeric material, and the selective separation layer being formed by the polymeric material, which is characterized in that a solution of an organic Polymer applied to a ceramic carrier and a polymer layer is formed on the carrier.
  • the present invention also relates to the use of a hybrid membrane as claimed in one of claims 1 to 12 as a membrane in pressure-driven membrane processes, in nanofiltration, reverse osmosis, ultrafiltration or microfiltration, in pervaporation or in vapor permeation, in a membrane reactor or as a membrane in the gas separation.
  • the hybrid membranes according to the invention have the advantage that they are significantly more temperature and shape stable than pure organic polymer membranes, polymer membranes on polymer supports or as polymer membranes to which inorganic substances have been added.
  • the desired selectivity and the flow of the separating layer are retained even at higher temperatures and at higher pressure, i.e. H. the undesirable phenomenon of compacting the membrane is avoided.
  • the hybrid membranes according to the invention are tolerant of chemicals and in particular stable against the common solvents.
  • the hybrid membrane according to the invention can also have a ceramic support structure that is thin and flexible, so that the hybrid membrane is also flexible.
  • the hybrid membranes therefore imply almost no restrictions when it comes to the choice of modules and housings compared to pure polymer membranes.
  • the hybrid membrane according to the invention with a selective separation layer the Membrane has an inorganic permeable carrier material and polymeric material, is characterized in that the selective separation layer is formed by the polymeric material.
  • inorganic permeable carrier materials are z.
  • the hybrid membranes according to the invention preferably have inorganic carrier materials which have pore sizes of less than 20 ⁇ m.
  • the carrier materials particularly preferably have a pore size of less than 1 ⁇ m and very particularly preferably less than 0.25 ⁇ m.
  • the inorganic permeable carrier material can be a ceramic composite material.
  • the inorganic carrier material preferably has an oxide selected from Al 2 O 3 , TiO 2 , ZrO 2 or SiO 2 .
  • the inorganic carrier material likewise preferably has a material selected from ceramic, SiC, Si 3 N 4 , C, glass, metal or semimetal.
  • the hybrid membrane according to the invention very particularly preferably has a flexible, inorganic, material-permeable composite material which is based on an inorganic carrier, on which and / or in which a suspension of an inorganic component and a sol has been solidified.
  • the carrier material present in the membrane according to the invention can comprise metal, glass, ceramic or a combination of these materials.
  • the permeable carrier material preferably has woven fabrics, nonwovens, sintered powder or sintered fibers made of metal, glass, ceramic or a combination of these materials.
  • the permeable carrier material can have woven or non-woven fabrics made of carbon fibers.
  • the permeable carrier material can also be a material which itself as a microfiltration membrane, ultrafiltration membrane, nanofiltration membrane or Gas separation membrane can be used. It is therefore also possible to use such material combinations as carrier materials in which a micro, nano and / or ultrafiltration membrane has been applied as a layer on and / or in a carrier or in and / or on a micro, nano and / or
  • Such composite materials are e.g. B. ceramic membranes, which are available under the name CREAFILTER from Creavis GmbH, Mari.
  • CREAFILTER Z240S; Z100S and Z25S are composite materials based on steel mesh, on which a suspension of aluminum oxide particles has been solidified in a zirconium sol. According to their type designation, these composite materials have pores with an average pore diameter of 240 nm, 100 nm and 25 nm.
  • All the composite materials described in WO 99/15262 are based on composite materials which have an inorganic or ceramic material applied to and in a porous carrier.
  • the hybrid membrane according to the invention can have both the composite materials described below and the carriers on which they are based as the carrier material.
  • the composite materials have at least one perforated and permeable support as the basis.
  • the carrier On at least one side of the carrier and in the interior of the carrier, the carrier has at least one inorganic component which essentially has at least one compound composed of a metal, a semimetal or a mixed metal with at least one element from the 3rd to 7th main group.
  • the interior of a carrier is understood to mean the cavities or pores of the carrier.
  • the composite materials can be applied by applying a suspension, the at least one
  • the carrier can have at least one material selected from carbon, metals, alloys, glass, ceramics, minerals, amorphous substances, natural products, composite materials or from at least a combination of these materials.
  • the carriers which may have the aforementioned materials, may have been modified by a chemical, thermal or mechanical treatment method or a combination of the treatment methods.
  • the composite materials preferably have a carrier which has at least one metal which can be formed by at least one mechanical deformation technique or treatment method, such as, for. B. drawing, upsetting, milling, rolling, stretching or forging was modified.
  • the composite materials very particularly preferably have at least one carrier which has at least woven, bonded, matted or ceramic-bonded fibers, or at least sintered or bonded shaped bodies, balls or particles.
  • a perforated carrier can be used.
  • Permeable supports can also be those which become permeable or have been made by laser treatment or ion beam treatment.
  • the carrier fibers from at least one material selected from carbon, metals, alloys, ceramics, glass, minerals, amorphous substances, composites and natural products or fibers from at least a combination of these materials, such as. B. asbestos, glass fibers, rock wool fibers, carbon fibers, metal wires, steel wires or coated fibers.
  • Carriers are preferably used which have at least interwoven fibers made of glass, metal or alloys. Wires can also serve as fibers made of metal.
  • the composite materials very particularly preferably have a carrier which has at least one fabric made of steel or stainless steel, such as, for. B.
  • the carrier of the composite materials can also have at least one expanded metal with a pore size of 5 to 500 ⁇ m. According to the invention, however, the carrier can also have at least one granular, sintered metal, a sintered glass or a metal fleece with a pore size of 0.1 ⁇ m to 500 ⁇ m, preferably 3 to 60 ⁇ m.
  • the composite materials preferably have a carrier which contains at least aluminum, silicon, cobalt, manganese, zinc, vanadium, molybdenum, indium, lead, bismuth, silver, gold, nickel, copper, iron, titanium, platinum, stainless steel, steel, brass, an alloy of these materials or a material coated with Au, Ag, Pb, Ti, Ni, Cr, Pt, Pd, Rh, Ru and / or Ti.
  • the inorganic component present in the composite materials can have at least one compound of at least one metal, semimetal or mixed metal with at least one element from the 3rd to 7th main group of the periodic table or at least a mixture of these compounds.
  • the compounds of the metals, semimetals or mixed metals can have at least elements of the subgroup elements and the 3rd to 5th main group or at least elements of the subgroup elements or the 3rd to 5th main group, these compounds having a grain size of 0.001 to 25 ⁇ m.
  • the inorganic component preferably has at least one compound of an element of the 3rd to 8th subgroup or at least one element of the 3rd to 5th main group with at least one of the elements Te, Se, S, O, Sb, As, P, N, Ge , Si, C, Ga, AI or B or at least one connection of an element of the 3rd to 8th subgroup and at least one element of the 3rd to 5th main group with at least one of the elements Te, Se, S, O, Sb, As , P, N, Ge, Si, C, Ga, Al or B or a mixture of these compounds.
  • the inorganic component particularly preferably has at least one compound of at least one of the elements Sc, Y, Ti, Zr, V, Nb, Cr, Mo, W, Mn, Fe, Co, B, Al, Ga, In, TI, Si, Ge , Sn, Pb, Sb or Bi with at least one of the elements Te, Se, S, O, Sb, As, P, N, C, Si, Ge or Ga, such as. B.
  • the inorganic component can also be aluminosilicates, aluminum phosphates, zeolites or partially exchanged zeolites, such as, for. B. ZSM-5, Na- ZSM-5 or Fe-ZSM-5 or amorphous microporous mixed oxides, which can contain up to 20% non-hydrolyzable organic compounds, such as. B. vanadium oxide-silica glass or alumina-silica-methyl-silicon sesquioxide glasses.
  • At least one inorganic component is preferably present in a grain size fraction with a grain size of 1 to 250 nm or with a grain size of 260 to 10,000 nm, particularly preferably from 10 to 150 nm or from 300 to 1000 nm.
  • the composite materials used have at least two grain size fractions of at least one inorganic component.
  • the grain size ratio of the grain size fractions in the composite material is from 1: 1 to 1: 10000, preferably from 1: 1 to 1: 100.
  • the quantity ratio of the grain size fractions in the composite material can preferably be from 0.01 to 1 to 1 to 0.01.
  • the permeability of the composite materials can be limited by the grain size of the inorganic component used to particles with a certain maximum size.
  • the composite material can have at least one catalytically active component.
  • the catalytically active component can be identical to the inorganic component. This applies in particular if the inorganic component has catalytically active centers on the surface.
  • the composite material which is preferably used as the carrier material in the hybrid membrane according to the invention is preferably designed to be bendable or flexible without destroying the composite material.
  • the composite material can preferably be bent to a radius down to 5 m, particularly preferably down to 500 mm and very particularly preferably down to 25 mm.
  • the hybrid membrane according to the invention can have a gas-tight polymer layer as the separating layer.
  • gas-tight is understood to mean that a gas cannot pass through the separating layer in a laminar flow. Rather, the separation takes place e.g. B. of gas mixtures at the separation layer instead of the gases of the gas mixture to be separated diffusing or being transported through the membrane at different speeds.
  • the gas-tight polymer layer can e.g. B. of polydimethylsiloxane (PDMS), polyvinyl alcohol, methyl cellulose or cellulose acetate or a polymer mixture which comprises at least one of the compounds mentioned, or these compounds or modifications of these compounds.
  • PDMS polydimethylsiloxane
  • polyvinyl alcohol polyvinyl alcohol
  • methyl cellulose or cellulose acetate polymer mixture which comprises at least one of the compounds mentioned, or these compounds or modifications of these compounds.
  • the polymeric starting materials for forming the gas-tight layers can contain crosslinkable, in particular UV-crosslinkable, groups.
  • the hybrid membrane has a porous separation layer with defined pores instead of the gas-tight separation layer.
  • the hybrid membrane preferably has a porous separating layer with pores with a size of 0.5 to 100 nm, particularly preferably from 1 to 50 nm and very particularly preferably from 1 to 10 nm.
  • the porous separating layer is preferably a polymer layer which comprises at least one polymer selected from a polyimide, a polyamide, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyolefin, polyamideimide, polyetherimide, polysulfone and / or polyether sulfone or at least another membrane-forming polymer or its Modifications.
  • a polyimide a polyamide, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyolefin, polyamideimide, polyetherimide, polysulfone and / or polyether sulfone or at least another membrane-forming polymer or its Modifications.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • the hybrid membranes according to the invention preferably have a polymer layer with a thickness of 0.5 to 10 ⁇ m, preferably 1 to 8 ⁇ m, the porous separating layers having thicker layers than the gas-tight separating layers.
  • Preferred gas-tight polymer layers have layer thicknesses from 0.5 to 5 ⁇ m, preferably from 1.25 to 3.75 ⁇ m and very particularly preferably from 1.5 to 2.75 ⁇ m.
  • Preferred porous polymer layers have layer thicknesses of 5 to 50 ⁇ m, preferably 5.5 to 20 ⁇ m and very particularly preferably from 5.5 to 10 ⁇ m.
  • the hybrid membrane according to the invention is preferably flexible, very particularly preferably the membrane according to the invention can be down to a radius of 5 m, preferably down to 500 mm, particularly preferably down to 25 mm and very particularly preferably down to a radius of 5 mm to bend.
  • the hybrid membrane according to the invention is preferably formed by means of the method according to the invention for producing a hybrid membrane with a selective separation layer, the membrane having an inorganic permeable support material and polymeric material, and the selective separation layer being formed by the polymeric material, which is characterized in that a solution of a organic polymer is applied to the inorganic carrier material and a polymer layer is formed on the carrier.
  • the method can be carried out in various ways.
  • the process is preferably carried out in the systems and devices for producing polymer membranes known from the prior art, with the difference that the inorganic carrier material is used instead of the polymer carrier membrane or instead of the polymer carrier fleece.
  • This inorganic carrier material is preferably such that the pores, meshes or openings are less than 20 ⁇ m in diameter.
  • the carrier material is particularly preferably flexible and has a correspondingly good tensile strength in the machine direction, preferably a tensile strength of at least 5 N / cm, particularly preferably of at least 20 N / cm.
  • the carrier material very particularly preferably has a tensile strength in the machine direction of at least 50 N / cm, preferably 100 N / cm, in particular when using glass or steel fabrics.
  • carrier materials with a high tensile strength means that the hybrid membrane also has a similarly high tensile strength as the carrier material.
  • Micro-fiber non-woven fabrics, metal non-woven fabrics, dense glass fiber fabrics or metal fabrics, but also ceramic or carbon fiber non-woven fabrics and fabrics are preferably used as carrier materials. It is clear to the person skilled in the art that all other known flexible materials provided with open pores or openings of the appropriate size can also be used.
  • a carrier material for the process for the production of hybrid membranes are flexible, permeable composite materials which consist of ceramic or oxide particles, preferably SiC, Si 3 N, Al 2 O 3 , TiO 2 , ZrO 2 or SiO 2 and a carrier which preferably a ceramic, carbon, a glass, a metal or a semimetal, particularly preferably in the form of fibers. These preferably have pore sizes of less than 20 ⁇ m, particularly less than 1 ⁇ m and very particularly preferably less than 0.25 ⁇ m.
  • Such carrier materials are available under the name CREAFILTER from Creavis, Mari. We mainly used the Z240S for our tests; Z100S and Z25S.
  • the carrier materials preferably used have a minimum pore size of 5 nm, preferably 10 nm and very particularly preferably 25 nm.
  • the production of such composite materials that can be used as carrier materials is used, for. B. described in detail in WO 99/15262 and is based on the application of a suspension having at least one, a compound of at least one metal, a semimetal or a mixed metal with at least one element of the 3rd to 7th main group, inorganic component and a sol has an openwork and permeable carrier, and solidifying the suspension by at least one heating, in which the suspension having at least one inorganic component is solidified on or in or on and in the carrier.
  • the carrier can have at least one material selected from carbon, metals, alloys, glass, ceramics, minerals, amorphous substances, natural products, composite materials or from at least a combination of these materials.
  • the carrier fibers from at least one material selected from carbon, metals, alloys, ceramics, glass, minerals, amorphous substances, composites and natural products or fibers from at least a combination of these materials, such as. B. asbestos, glass fibers, rock wool fibers, carbon fibers, metal wires, steel wires or coated fibers.
  • Carriers are preferably used which have at least interwoven fibers made of glass, metal or alloys. Wires can also serve as fibers made of metal.
  • the composite materials very particularly preferably have a carrier which has at least one fabric made of glass, steel or stainless steel, such as, for. B.
  • the suspension is preferably solidified at a temperature of 50 to 1000 ° C., particularly preferably at a temperature of 50 to 100 ° C. for 10 minutes. up to 5 hours or at a temperature of 101 to 800 ° C for 1 second to 10 min., very particularly preferably at a temperature of 350 to 550 ° C.
  • the coating of the carrier material with the solution, which has at least one polymer, for producing the hybrid membranes can be carried out according to the prior art by knife coating, spraying, rolling, printing or by dip-coating techniques.
  • the application thickness of the polymer solution is preferably less than 250 ⁇ m, particularly preferably less than 100 ⁇ m and very particularly preferably less than 50 ⁇ m.
  • the application thickness can e.g. B. can be influenced by so-called recoating systems.
  • the polymer layer can be formed in two different ways.
  • the polymer layer is removed of the solvent at a temperature of 50 to 350 ° C, preferably at a temperature of 50 to 125 ° C, from 126 to 250 ° C or from 251 to 350 ° C and particularly preferably at a temperature of 260 to 340 ° C.
  • a solution of polydimethylsiloxane (PDMS), polyvinyl alcohol, methyl cellulose or cellulose acetate or a polymer mixture which has at least one of the compounds mentioned is preferably used as the polymer solution.
  • Suitable solvents are the known solvents, which are able to dissolve the polymers mentioned, such as. B. toluene, gasoline fractions, THF, but also water and other known solvents.
  • the polymer layer is formed by precipitation in a precipitant bath.
  • a highly viscous solution of a polymer is applied to the inorganic carrier material and this arrangement is then placed in a precipitation bath which contains a precipitation agent, such as, for. B. water contains. Due to the contact with the precipitant, a polymer layer precipitates out of the highly viscous polymer solution. Depending on the precipitation conditions and the solvent selected, this has a certain average pore size.
  • the polymer layer is particularly preferably precipitated from a polymer solution which has at least one polymer selected from a polyimide, a polyamide, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyolefin, polyamideimide, polyetherimide, polysulfone and / or polyether sulfone.
  • Suitable solvents are all known solvents which are able to dissolve the polymers and are miscible with the precipitant in any ratio.
  • N-methylpyrrolidone, dimethylacetamide or dimethylformamide are used.
  • the precipitated polymer layer in a subsequent step at a temperature of 50 to 500 ° C, preferably at a temperature of 50 to 150 ° C, from 151 to 250 ° C or from 251 to 500 ° C and particularly preferably is dried at a temperature of 300 to 450 ° C.
  • the polymer material used to form the polymer layer can change chemically as a result of the temperature treatments mentioned in both embodiments of the method according to the invention.
  • a chemical change can e.g. B. a radical, thermal or photo-induced crosslinking reaction or a partial pyrolysis with crosslinking of the polymer.
  • This subsequent change in the polymer results in the polymer layer becoming insoluble in most solvents.
  • a subsequent crosslinking reaction as a chemical change can also be initiated by irradiation with electrons or other radiation.
  • the hybrid membranes according to the invention are used in many areas. Due to the possibility of tailoring the selective layer to a separation task, there are advantages in gas permeation, pervaporation, nanofiltration, ultrafiltration and microfiltration. Applications as a membrane reactor are also conceivable, even at higher temperatures.
  • the hybrid membrane according to the invention can therefore, for. B. as a membrane in pressure-driven membrane processes, in nanofiltration, in reverse osmosis, in ultrafiltration or in microfiltration.
  • the hybrid membrane according to the invention can also be used as a membrane in pervaporation or in vapor permeation and as a membrane in a membrane reactor.
  • hybrid membrane according to the invention in particular a hybrid membrane which has a gas-tight separation layer, as a membrane in gas separation.
  • the advantages of the hybrid membranes according to the invention lie above all in the greater resistance of the membranes at high pressures, at high temperatures or in Solvents and acids and bases.
  • the greater resistance at high pressures is used in gas separation, since the hybrid membranes according to the invention are more stable and do not compact at pressures of up to 40 bar.
  • pervaporation and vapor permeation the better resistance to various organic solvents as well as the improved temperature resistance are used.
  • Filtration applications also take advantage of the significantly better pressure resistance, since at polymer pressures of 20 bar in most nanofiltration applications, most polymer membranes are highly compact and therefore the flows through the membrane are significantly lower than they would be from the selective separation layer alone.
  • An inorganic flexible ceramic CREAFILTER membrane of the type Z25S, (Creavis GmbH, Mari) is presented as the material to be coated in a coating system.
  • An approx. 50 ⁇ m thick layer of a PDMS solution is then applied by a recoating system and then dried in a drying oven at 110 ° C. The web speed was 1.0 m / min. After drying, the membrane was rolled up again and processed further.
  • the coating solution consisted of 8.5% PDMS, 1.37% crosslinker and 0.084% of a catalyst in THF.
  • the following chemicals available from Wacker were used as feed products: Dehesive 930; Crosslinker V93 and the catalyst oil. It became a gas-tight
  • Nanofiltration in organic solvents can be used.
  • a membrane produced according to Example 2 was used to retain polystyrene with a molar mass of 2 OOOg / mol to 100,000 g / mol.
  • the polystyrene was present in tetrahydrofuran as a solvent.
  • the retention rate was 99.2% with a
  • a membrane produced according to Example 2 with a PVDF support was used for the same separation task as under I.
  • the retention rate was 98% with a material flow of 3 L m ' Vbar "1 .
  • a membrane produced according to Example 2 was used for the separation of polystyrene from an N-methylpyrrolidone solution. , The retention rate was 98% with 1 1 a material flow of 1, 2 L m " h " bar " This was constant over 48 hours.
  • a membrane produced according to Example 3 was used to separate catalyst residues (average particle size approx. 0.05 ⁇ m) from a gasoline fraction
  • Example 3 One according to Example 3 with a polypropylene carrier instead of the ceramic CREAFILTER membrane manufactured membrane was also used for the separation of catalyst residues from a gasoline fraction.
  • the retention was initially 99% with a stream of 5 lm "2 h " 1 bar "1. However, the flow increased after a few hours. This was accompanied by a decrease in the retention
  • a membrane produced according to Example 4 was used for the separation of water and acetonitrile in the pervaporation at 70 ° C.
  • the flow of water was 0.24 kg m " h " with a separation factor of 2300.
  • a membrane produced according to Example 4 with a polyacrylonitrile (PAN) support instead of the ceramic CREAFILTER membrane was used for the separation of water and acetonitrile in the pervaporation at 70 ° C.
  • the flow of water 1 was 0.18 kg m " h ' with a separation factor of 2390.
  • membranes which have a carrier material made of polymer material show significantly poorer long-term stability than the hybrid membrane according to the invention.
  • Example 1 shows the surface of a hybrid membrane according to the invention, produced according to Example 2. The unevenness of the polymer surface, which results from the ceramic particles underneath, can be clearly seen.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention concerne une membrane hybride combinant les avantages des membranes inorganiques, telles que la résistance aux solvants et la stabilité, et les avantages des matières membranaires organiques. La membrane hybride selon l'invention comporte une couche support céramique et une couche organique de séparation sélective. Les propriétés de séparation de cette membrane peuvent être régulées de manière ciblée par variation des polymères, du mode de traitement des matières polymères ou des conditions de production de la couche de séparation sélective polymère.
PCT/EP2002/008697 2001-08-10 2002-08-05 Membrane hybride, son procede de production et son utilisation WO2003013708A2 (fr)

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AU2002321292A AU2002321292A1 (en) 2001-08-10 2002-08-05 Hybrid membrane, method for the production thereof and use of said membrane

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DE10139559.0 2001-08-10
DE10139559A DE10139559A1 (de) 2001-08-10 2001-08-10 Hybridmembran, Verfahren zu deren Herstellung und die Verwendung der Membran

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WO2003013708A3 WO2003013708A3 (fr) 2004-01-29

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WO2003072232A1 (fr) * 2002-02-26 2003-09-04 Creavis Gesellschaft Für Technologie Und Innovation Mbh Membrane hybride, et procede de fabrication et d'utilisation de ladite membrane
ITPD20100189A1 (it) * 2010-06-17 2011-12-18 Univ Padova Membrane ibride inorganico-organiche a scambio protonico a base di ptfe e nanofiller a carattere acido per appicazioni in celle a combustibile ad elettrolita polimerico ed elettrolizzatori
CN102389723A (zh) * 2011-10-11 2012-03-28 常州大学 一种用于油气回收的有机/无机复合膜及其制备方法
WO2012074487A1 (fr) * 2010-11-29 2012-06-07 Nanyang Technological University Membrane à fibres creuses d'osmose directe
CN103566783A (zh) * 2013-11-13 2014-02-12 济南泰易膜科技有限公司 基于pdms底层pvdf分离层的渗透汽化膜及其制备方法
US9680141B2 (en) 2012-01-30 2017-06-13 Litarion GmbH Separator comprising an organic-inorganic adhesion promoter
CN108543427A (zh) * 2018-05-03 2018-09-18 东莞市石鼓污水处理有限公司 一种污水过滤复合膜
CN108579462A (zh) * 2018-05-03 2018-09-28 东莞市石鼓污水处理有限公司 一种高寿命污水过滤复合膜
CN108636132A (zh) * 2018-05-03 2018-10-12 东莞市石鼓污水处理有限公司 一种高稳定性污水过滤复合膜
CN109070017A (zh) * 2016-03-30 2018-12-21 日本碍子株式会社 陶瓷膜过滤器及其制造方法
CN110292865A (zh) * 2019-06-27 2019-10-01 三达膜科技（厦门）有限公司 一种自清洁氮化碳/二氧化钛/聚乙烯醇复合纳滤膜的制备方法
CN110449035A (zh) * 2019-08-20 2019-11-15 广东工业大学 一种油水分离膜及其制备方法
CN112569803A (zh) * 2019-09-30 2021-03-30 成都易态科技有限公司 复合多孔薄膜的制备方法

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DE10308110A1 (de) * 2003-02-26 2004-09-23 Hermsdorfer Institut Für Technische Keramik E.V. Keramische Nanofiltrationsmembran für die Verwendung in organischen Lösungsmitteln und Verfahren zu deren Herstellung
CN102580560B (zh) * 2012-02-24 2014-01-22 哈尔滨工业大学 纳米材料掺杂聚合物膜的制备方法
CN104096489B (zh) * 2013-12-24 2016-01-06 广州中国科学院先进技术研究所 一种无机-有机功能化聚四氟乙烯微孔膜的制备方法
CN106474947B (zh) * 2016-12-14 2020-01-03 中国科学技术大学 一种表面疏水多孔陶瓷膜的制备方法
CN106823833B (zh) * 2017-01-25 2019-05-17 厦门大学 一种抗菌纳滤膜的制备方法及其应用
CN109516589B (zh) * 2017-09-20 2020-11-17 清华大学 一种膜法处理焦化废水的工艺
EP3669973A1 (fr) 2018-12-20 2020-06-24 Evonik Operations GmbH Corps composite
EP3851183A1 (fr) 2020-01-17 2021-07-21 Evonik Operations GmbH Corps composite et son utilisation en nanofiltration organophile

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003072232A1 (fr) * 2002-02-26 2003-09-04 Creavis Gesellschaft Für Technologie Und Innovation Mbh Membrane hybride, et procede de fabrication et d'utilisation de ladite membrane
ITPD20100189A1 (it) * 2010-06-17 2011-12-18 Univ Padova Membrane ibride inorganico-organiche a scambio protonico a base di ptfe e nanofiller a carattere acido per appicazioni in celle a combustibile ad elettrolita polimerico ed elettrolizzatori
WO2012074487A1 (fr) * 2010-11-29 2012-06-07 Nanyang Technological University Membrane à fibres creuses d'osmose directe
CN102389723A (zh) * 2011-10-11 2012-03-28 常州大学 一种用于油气回收的有机/无机复合膜及其制备方法
CN102389723B (zh) * 2011-10-11 2014-02-05 常州大学 一种用于油气回收的有机/无机复合膜及其制备方法
US9680141B2 (en) 2012-01-30 2017-06-13 Litarion GmbH Separator comprising an organic-inorganic adhesion promoter
CN103566783A (zh) * 2013-11-13 2014-02-12 济南泰易膜科技有限公司 基于pdms底层pvdf分离层的渗透汽化膜及其制备方法
CN109070017A (zh) * 2016-03-30 2018-12-21 日本碍子株式会社 陶瓷膜过滤器及其制造方法
CN108543427A (zh) * 2018-05-03 2018-09-18 东莞市石鼓污水处理有限公司 一种污水过滤复合膜
CN108579462A (zh) * 2018-05-03 2018-09-28 东莞市石鼓污水处理有限公司 一种高寿命污水过滤复合膜
CN108636132A (zh) * 2018-05-03 2018-10-12 东莞市石鼓污水处理有限公司 一种高稳定性污水过滤复合膜
CN110292865A (zh) * 2019-06-27 2019-10-01 三达膜科技（厦门）有限公司 一种自清洁氮化碳/二氧化钛/聚乙烯醇复合纳滤膜的制备方法
CN110449035A (zh) * 2019-08-20 2019-11-15 广东工业大学 一种油水分离膜及其制备方法
CN112569803A (zh) * 2019-09-30 2021-03-30 成都易态科技有限公司 复合多孔薄膜的制备方法
CN112569803B (zh) * 2019-09-30 2022-08-05 成都易态科技有限公司 复合多孔薄膜的制备方法

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DE10139559A1 (de) 2003-02-20
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