EP1483042A1 - Membrane hybride, et procede de fabrication et d'utilisation de ladite membrane - Google Patents

Membrane hybride, et procede de fabrication et d'utilisation de ladite membrane

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Publication number
EP1483042A1
EP1483042A1 EP03742923A EP03742923A EP1483042A1 EP 1483042 A1 EP1483042 A1 EP 1483042A1 EP 03742923 A EP03742923 A EP 03742923A EP 03742923 A EP03742923 A EP 03742923A EP 1483042 A1 EP1483042 A1 EP 1483042A1
Authority
EP
European Patent Office
Prior art keywords
polymer
membrane
composite material
hybrid membrane
hybrid
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Withdrawn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
EP03742923A
Other languages
German (de)
English (en)
Inventor
Volker Hennige
Christian Hying
Gerhard HÖRPEL
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.)
Evonik Operations GmbH
Original Assignee
CREAVIS GESELLSCHAFT fur TECHNOLOGIEUND INNOVATION MBH
CREAVIS GES fur TECHNOLOGIEUN
Creavis Gesellschaft fuer Technologie und Innovation mbH
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 CREAVIS GESELLSCHAFT fur TECHNOLOGIEUND INNOVATION MBH, CREAVIS GES fur TECHNOLOGIEUN, Creavis Gesellschaft fuer Technologie und Innovation mbH filed Critical CREAVIS GESELLSCHAFT fur TECHNOLOGIEUND INNOVATION MBH
Publication of EP1483042A1 publication Critical patent/EP1483042A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific 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
    • B01D69/10—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
    • B01D69/122—Separate manufacturing of 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
    • B01D69/1411—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing dispersed material in a continuous matrix
    • 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
    • B01D71/24—Rubbers
    • 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
    • B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
    • B01D71/381—Polyvinylalcohol
    • 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
    • B01D71/56—Polyamides, e.g. polyester-amides
    • 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
    • B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
    • B01D71/701—Polydimethylsiloxane

Definitions

  • the invention relates to a hybrid membrane made of an organic / inorganic permeable carrier material with an organic selectively acting separating layer.
  • Ceramic membranes have been known for more than 10 years and, due to their still very high price, are 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 also 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 are not stable for long periods at temperatures above 80 ° C.
  • membranes based on polymer materials can be dissolved or dissolved by solvents or oils, or that the oils have a softening effect. These three effects all lead to the fact that the separating capacity of the membrane is impaired or that the membrane is compacted even at very low temperatures. Ultimately, compacting always means that the membrane has a lower flow rate or becomes unusable due to insufficient flow.
  • 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 polymeric support structure of the membranes.
  • the polymeric asymmetrical carrier membranes (with pore sizes of up to 5 ⁇ m) 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.
  • DE 101 39 559 describes for the first time a hybrid membrane with a selective separation layer, the membrane having an inorganic permeable carrier material and polymeric material, which is characterized in that the selective separation layer is formed by the polymeric material.
  • the carrier material consists of microglass fiber nonwovens, metal nonwovens, dense glass fiber fabrics or metal fabrics, but also ceramic or carbon fiber nonwovens or fabrics, which are provided with a ceramic coating.
  • a hybrid membrane is a polymer Separating layer and an organic / inorganic ceramic carrier composite has the separation properties of a polymer membrane and largely the chemical resistance and pressure resistance of a ceramic membrane. It has also surprisingly been found that the methods of producing polymeric membranes can be very easily applied to a flexible organic / inorganic, chemically stable and pressure-stable carrier material.
  • the present invention therefore relates to a hybrid membrane according to spoke 1, with a selective separating layer, the membrane having a permeable composite material and polymeric material, which is characterized in that the selective separating layer is formed by the polymeric material and the composite material on a permeable carrier , which has polymer fibers, is based on and / or in which inorganic components are present.
  • the present invention also relates to a method for producing a hybrid membrane with a selective separating layer, the membrane having a permeable composite material and polymeric material, the selective separating layer being formed by the polymeric material and the composite material being based on a permeable carrier which has polymer fibers , on and / or in which inorganic components are present, which is characterized in that a solution of an organic polymer is applied to the inorganic composite material and a polymer layer is formed on the composite material.
  • the present invention also relates to the use of a hybrid membrane according to the invention as a membrane in pressure-driven membrane processes, in nanofiltration, reverse osmosis or ultrafiltration, in pervaporation or in steam permeation, in a membrane reactor or as a membrane in gas separation.
  • the hybrid membranes according to the invention have the advantage that they are substantially more stable in temperature and shape than pure organic polymer membranes, polymer membranes
  • Polymer carriers or as polymer membranes to which inorganic substances have been added are Polymer carriers or as polymer membranes to which inorganic substances have been added.
  • the desired selectivity and remains in the membranes of the invention the flow of the separating layer is maintained even at temperatures of up to 150 ° C. and at higher pressure, ie 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 also has an organic / ceramic support structure which is based on ceramic-coated polymer fibers, which 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. Due to the pronounced flexibility of the hybrid membrane according to the invention, it withstands mechanical loads much better than hybrid membranes based on inorganic supports.
  • the hybrid membranes according to the invention also have the advantage that they are extremely inexpensive to manufacture, since polymer fabrics or nonwovens are significantly cheaper than metal or glass nonwovens or fabrics of these materials. In contrast to glass fibers, the polymer fibers are also significantly less brittle, which is why the handling of the starting material is also significantly simplified and therefore cheaper.
  • the hybrid membrane according to the invention with a selective separating layer is characterized in that the selective separating layer is formed by the polymeric material and the composite material is based on a permeable carrier which has polymer fibers, on which and / or in which inorganic components are present.
  • the inorganic components form a porous ceramic coating.
  • the hybrid membranes according to the invention preferably have composite materials which have a flat, flexible substrate provided with a multiplicity of openings with a coating located on and in this substrate, the material of the substrate is selected from woven or non-woven fibers of polymers and the coating is a porous ceramic coating. It can be advantageous if the hybrid membranes have composite materials that have a thickness of less than 200 ⁇ m.
  • the hybrid membranes preferably have permeable composite materials with a thickness of less than 100 ⁇ m, particularly preferably a thickness of 20 to 100 ⁇ m.
  • the thickness of the hybrid membrane is also very small.
  • the small thickness of the hybrid membrane enables a high transmembrane flow.
  • the material of the substrate is selected from woven or non-woven polymer or natural fibers.
  • Woven polymer or natural fibers can e.g. B. be tissue.
  • Nonwoven polymer or natural fibers can e.g. B. knitted fabrics, fleeces or felts.
  • the material of the flexible substrate is particularly preferably a nonwoven made of polymer fibers or a nonwoven having polymer fibers.
  • a fleece preferably a very thin and homogeneous fleece material, a uniform transmembrane flow is achieved.
  • Nonwovens also have the advantage that they have a significantly higher porosity than comparable fabrics.
  • the composite material preferably has a substrate which has a thickness of 10 to 200 ⁇ m. It can be particularly advantageous if the composite material has a substrate which has a thickness of 30 to 100 ⁇ m, preferably 25 to 50 ⁇ m and particularly preferably 30 to 40 ⁇ m.
  • the small thickness of the substrate used also means that the transmembrane flow through the composite material and thus through the membrane is greater than in the case of conventional membranes.
  • the polymer fibers are preferably selected from polyacrylonitrile, polyamides, polyimides, polyacrylates, polytetrafluoroethylene, polyesters, such as, for. B. polyethylene terephthalate and / or polyolefms such. B. polypropylene, polyethylene or mixtures of these polymers. But also all other known polymer fibers and many natural fibers, such as. B. flax fibers, cotton or hemp fibers are conceivable.
  • the membrane according to the invention preferably has polymer fibers which have a softening temperature of greater than 100 ° C. and a Have a melting temperature of greater than 110 ° C. The application areas are also reduced for polymer fibers with lower temperature limits.
  • Preferred membranes can be used up to a temperature of up to 150 ° C., preferably up to a temperature of 120 to 150 ° C. and very particularly preferably up to a temperature of 121 ° C. It can be advantageous if the polymer fibers of the substrate of the composite material have a diameter of 1 to 25 ⁇ m, preferably 2 to 15 ⁇ m. If the polymer fibers are significantly thicker than the areas mentioned, the flexibility of the substrate and thus that of the membrane suffers.
  • polymer fibers are also understood to mean fibers of polymers which have been chemically or structurally changed in part by thermal treatment, such as, B. partially carbonized polymer fibers.
  • the ceramic coating located on and in the substrate preferably has an oxide, the metals Al, Zr, Si, Sn, Ti and / or Y.
  • the coating located on and in the substrate particularly preferably has an oxide of the metals Al, Zr, Ti and / or Si as an inorganic component.
  • the membrane according to the invention has a coating which has at least two grain size fractions of at least one inorganic component. It can also be advantageous if the coating has at least two grain size fractions of at least two inorganic components.
  • the grain size ratio can be from 1: 1 to 1: 10000, preferably from 1: 1 to 1: 100.
  • the quantitative ratio of the grain size fractions in the composite material can preferably be from 0.01: 1 to 1: 0.01.
  • adhesion promoters are organofunctional silanes, such as those from Degussa under the Trade names "Dynasilan” are offered, but also pure oxides such as ZrO 2 , TiO 2 , SiO 2 or Al 2 O 3 can be suitable adhesion promoters for some fiber materials.
  • the adhesion promoters can still be present in the membrane according to the invention .
  • such a membrane has a nonwoven, preferably a polymer nonwoven, the fibers of which are provided with a thin layer of an adhesion promoter (such as a metal oxide or an organosilane compound).
  • an adhesion promoter such as a metal oxide or an organosilane compound.
  • the porous ceramic material is located in and on the polymeric, pre-coated carrier.
  • 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. from polydimethylsiloxane (PDMS), polyvinyl alcohol, methyl cellulose, polyimide, polyamide, polyurethane, polyester, polyether or copolymers or block copolymers of these polymers or cellulose acetate or a polymer mixture which comprises at least one of the compounds mentioned, or these compounds or modifications thereof Have connections.
  • PDMS polydimethylsiloxane
  • polyvinyl alcohol methyl cellulose
  • polyimide polyamide
  • polyurethane polyester
  • polyether or copolymers or block copolymers of these polymers or cellulose acetate or a polymer mixture which comprises at least one of the compounds mentioned, or these compounds or modifications thereof Have connections.
  • the polymeric starting materials to form the gas-tight layers can contain crosslinkable, in particular UV or thermally crosslinkable, groups.
  • the gas-tight polymer layers have inorganic additives such as zeolites, polyacids, zeolites such as ZSM-5, mordenite or zeolite-Y, but also metal salts, which have the desired separation properties of the polymer layer, for example by increasing the sorption of preferred compounds ( Hydrophiles in polyacids, mordenite, zeolite-Y and metal salts or hydrophobes in ZSM-5 zeolites).
  • the proportion of inorganic additives in the gas-tight polymer layers is preferably less than 20 % By weight, preferably less than 10% by weight and very particularly preferably less than 5% by weight.
  • the hybrid membranes according to the invention preferably have a polymer layer with a thickness of 0.1 to 10 ⁇ m, preferably 0.2 to 5 ⁇ m.
  • Preferred gas-tight polymer layers have layer thicknesses of less than 5 ⁇ m, preferably from 0.1 to 3.75 ⁇ m and very particularly preferably from 0.3 to 2.75 ⁇ m.
  • the membranes according to the invention are distinguished by the fact that they have a tensile strength of at least 1 N / cm, preferably 3 N / cm and very particularly preferably greater than 6 N / cm.
  • the membranes according to the invention are preferably flexible and can be bent without damage down to any radius down to 100 m, preferably down to 50 mm and very particularly preferably down to 2 mm.
  • the good flexibility of the membrane according to the invention has the advantage that when used in filtration, pervaporation or gas separation, sudden pressure fluctuations through the membrane can be tolerated without damage to the membrane.
  • the hybrid membrane according to the invention is preferably produced by means of the method according to the invention for producing a hybrid membrane with a selective separating layer, the membrane having a permeable composite material and polymeric material, the selective separating layer being formed by the polymeric material and the composite material on a permeable carrier, the woven or comprises non-woven polymer fibers, on which and in which inorganic components are present, which is characterized in that a layer comprising an organic polymer is applied to the composite material.
  • This can e.g. B. take place in that a solution of an organic polymer is applied to the inorganic composite material and a polymer layer is formed on the composite material.
  • polymer layers which have arisen from interfacial polycondensation or thin polymer layers produced on fluid surfaces can be applied to the composite material. This can be carried out by leading the composite material to be coated out of the fluid, or the lower phase in the interfacial polycondensation, through the polymer layer, so that it adheres to the upper side. After drying the coated membrane can then be wound up.
  • 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 permeable composite material is used instead of the polymeric carrier membrane.
  • This composite material is preferably such that the pores, meshes or openings are less than 2 ⁇ m in diameter.
  • the composite material is particularly preferably flexible and has a correspondingly good tensile strength in the machine direction, preferably a tensile strength of at least 1 N / cm, particularly preferably of at least 3 N / cm.
  • the composite material very particularly preferably has a tensile strength of at least 6 N / cm in the machine direction, in particular when polymer fiber nonwovens are used as the substrate of the composite material.
  • Membranes in particular micro- and ultrafiltration membranes, are preferably used as composite materials.
  • B. are obtainable by the method described below. These membranes are obtainable by a process which is characterized in that a flat, flexible, provided with a plurality of openings
  • the substrate in and on this substrate is provided with a coating, the material of the substrate being selected from nonwovens of polymer or natural fibers, the nonwovens preferably having a porosity of greater than 50% and the coating being a porous, ceramic coating based on the substrate by applying a suspension which has at least one oxide, the metals Al, Zr, Si, Sn, Ti and / or Y and a sol, on the
  • Substrate is solidified, is applied.
  • the suspension can have further inorganic components, in particular those as already mentioned above as inorganic
  • the suspension can e.g. B. by printing, pressing, pressing, rolling, knife coating, spreading, dipping, spraying or pouring onto and into the substrate.
  • the material of the substrate is preferably selected from nonwovens of polymer fibers with a thickness of 10 to 200 ⁇ m. It can be particularly advantageous if the membrane according to the invention has a substrate which has a thickness of 30 to 100 ⁇ m, preferably 25 to 50 ⁇ m.
  • the polymer fibers are preferably selected from polyacrylonitrile, polyamides, polyimides, polyacrylates, polytetrafluoroethylene, polyesters, such as, for. B. polyethylene terephthalate and / or
  • the membrane preferably has polymer fibers which have a softening temperature of greater than 100 ° C. and a melting temperature of greater than 110 ° C. at
  • Polymer fibers with lower temperature limits also reduce the areas of application. These membranes can be used up to a temperature of up to 150 ° C., preferably up to a temperature of 120 to 150 ° C. and very particularly preferably up to a temperature of 121 ° C. It can be advantageous if the polymer fibers have a diameter of 1 to 25 ⁇ m, preferably 2 to 15 ⁇ m. Are the
  • the suspension used to produce the coating which has at least one inorganic component, preferably has at least one inorganic oxide of aluminum, titanium, silicon and / or zirconium and at least one sol, at least one semimetal oxide sol or at least one mixed metal oxide sol or a mixture of these sols, and is made by suspending at least one inorganic component in at least one of these brines.
  • the sols are hydrolyzed by at least one compound, preferably at least one metal compound, at least one semimetal compound or at least one
  • the compound to be hydrolyzed is preferably at least one metal nitrate, one metal chloride, one metal carbonate Hydrolysed metal alcoholate compound or at least one semimetal alcoholate compound, particularly preferably at least one metal alcoholate compound.
  • An alcoholate compound of the elements Zr, Al, Si, Ti, Sn, and Y or at least one metal nitrate, metal carbonate or metal halide is preferably selected from the metal salts of the elements Zr, Al, Ti, Si, Sn, and Y as the metal alcoholate compound or semimetal alcoholate compound hydrolyzed as a metal compound.
  • the hydrolysis is preferably carried out in the presence of water, steam, ice, or an acid or a combination of these compounds.
  • particulate sols are produced by hydrolysis of the compounds to be hydrolyzed. These particulate sols are characterized by the fact that the compounds formed in the sol by hydrolysis are present in particulate form.
  • the particulate sols can be produced as described above or as described in WO 99/15262. These brines usually have a very high water content, which is preferably greater than 50% by weight. It may be advantageous to add the compound to be hydrolyzed to alcohol or an acid or a combination of these liquids before the hydrolysis.
  • the hydrolyzed compound can be treated with at least one organic or inorganic acid, preferably with a 10 to 60% organic or inorganic acid, particularly preferably with a mineral acid selected from sulfuric acid, hydrochloric acid, perchloric acid, phosphoric acid and nitric acid or a mixture of these acids become.
  • the particulate sols produced in this way can then be used for the production of suspensions, the production of suspensions for application to natural fiber nonwovens or polymer fiber nonwovens pretreated with polymeric sol being preferred.
  • polymeric sols are produced by hydrolysis of the compounds to be hydrolyzed. These polymeric sols are distinguished by the fact that the compounds formed in the sol by hydrolysis are polymeric (ie crosslinked in a chain over a larger space).
  • the polymeric sols usually have less than 50% by weight, preferably very much less than 20% by weight, of water and / or aqueous acid.
  • the hydrolysis is preferably so carried out that the compound to be hydrolyzed is hydrolyzed with 0.5 to 10 times the molar ratio and preferably with half the molar ratio of water, steam or ice, based on the hydrolyzable group, the hydrolyzable compound.
  • the amount of water can be used with very slow hydrolyzing compounds such as. B. be used in tetraethoxysilane.
  • Very quickly hydrolyzing compounds such as zirconium tetraethylate can already form particulate sols under these conditions, which is why 0.5 times the amount of water is preferably used for the hydrolysis of such compounds.
  • Hydrolysis with less than the preferred amount of water, steam, or ice also gives good results. However, falling below the preferred amount of half a molar ratio by more than 50% is possible but not very useful, since if this value is not reached the hydrolysis is no longer complete and coatings based on such brine are not very stable.
  • Both the particulate sols and the polymeric sols can be used as sols in the process according to the invention for producing the suspension.
  • commercially available brines such as e.g. B. zirconium nitrate sol or silica sol can be used.
  • the process for the production of membranes by applying and solidifying a suspension to a support in itself is known from WO 99/15262, but not all parameters or starting materials can be transferred to the production of the membrane according to the invention.
  • sols or suspensions which has been adapted to the polymers in terms of wetting behavior completely soaks the nonwoven materials and thus flawless coatings are obtainable.
  • the wetting behavior of the sol or suspension is therefore preferably adjusted in the method according to the invention.
  • This adjustment is preferably carried out by the production of polymeric sols or suspensions from polymeric sols.
  • These sols contain one or more alcohols, such as. B. methanol, ethanol or propanol or mixtures which comprise one or more alcohols and preferably aliphatic hydrocarbons.
  • solvent mixtures are also conceivable which can be added to the sol or the suspension in order to adapt them to the substance used in terms of crosslinking behavior.
  • the suspension as an inorganic component, at least one oxide selected from the oxides of the elements Y, Zr, Al, Si, Sn, and Ti is suspended in a sol.
  • an inorganic component the at least one compound selected from aluminum oxide, titanium dioxide, zirconium oxide and / or silicon dioxide, is suspended.
  • the mass fraction of the suspended component is preferably 0.1 to 500 times, particularly preferably 1 to 50 times and very particularly preferably 5 to 25 times the sol used.
  • the use of inorganic components which have an average grain size of 250 to 1250 nm results in a particularly suitable flexibility and porosity of the membrane.
  • adhesion promoters such as e.g. B. organofunctional silanes or pure oxides such as ZrO 2 , TiO 2 , SiO 2 or Al 2 O 3 .
  • adhesion promoters in particular to suspensions based on polymeric sols, is preferred.
  • adhesion promoters in particular compounds selected from the octylsilanes, the fluorinated octylsilanes, the vinylsilanes, the amine-functionalized silanes and / or the glycidyl-functionalized silanes, such as, for. B.
  • the Dynasilane from Degussa can be used.
  • Particularly preferred adhesion promoters for polytetrafluoroethylene (PTFE) are e.g. B. fluorinated octylsilanes, for polyethylene (PE) and polypropylene (PP) it is vinyl, methyl and octylsilanes, where the exclusive use of methylsilanes is not optimal, for polyamides and polyamines it is amine-functional silanes, for polyacrylates and polyesters Glycidyl-functionalized silanes and for polyacrylonitrile it is also possible to use glycidyl-functionalized silanes.
  • B. fluorinated octylsilanes for polyethylene (PE) and polypropylene (PP) it is vinyl, methyl and octylsilanes, where the exclusive use of methylsilanes is not optimal, for polyamides and polyamines it is amine-functional silanes,
  • adhesion promoters can also be used, but these have to be matched to the respective polymers.
  • methyltriethoxysilane described in WO 99/15262 to the sol system in the coating of polymeric carrier materials is a comparatively poor solution to the problem of the adhesive strength of ceramic on polymer fibers.
  • the drying time of 30 to 120 min at 60 to 100 ° C in the described sol systems is not sufficient to obtain hydrolysis-resistant ceramic materials. This means that these materials will dissolve or be damaged if stored in water-containing media for a long time.
  • the temperature treatment of over 350 ° C. described in WO 99/15262 would burn the polymer fleece used here and thus destroy the membrane.
  • adhesion promoters must therefore be selected so that the solidification temperature is below the melting or softening point of the polymer and is below its decomposition temperature.
  • Suspensions according to the invention preferably have significantly less than 25% by weight, preferably less than 10% by weight, of compounds which can act as adhesion promoters.
  • An optimal proportion of adhesion promoter results from the coating of the fibers and / or particles with a monomolecular layer of the adhesion promoter.
  • the amount of adhesion promoter required in grams can be obtained by multiplying the amount of oxides or fibers used (in g) by the specific surface area of the materials (in m 2 g _1 ) and then dividing by the specific space requirement of the adhesion promoter (in m 2 g "1 ) are obtained, the specific space requirement often being in the order of 300 to 400 m 2 g " 1 .
  • the following table contains an exemplary overview of adhesion promoters that can be used on the basis of organofunctional Si compounds for typical polymers used as nonwoven material.
  • AMEO 3-aminopropyltriethoxysilane
  • DAMO 2-aminoethyl-3-aminopropyltrimethoxysilane
  • GLYMO 3-glycidyloxytrimethoxysilane
  • the coatings according to the invention are applied to the substrate by solidifying the suspension in and on the substrate.
  • the suspension present on and in the substrate can be solidified by heating to 50 to 350 ° C. Since the maximum temperature is predetermined by the substrate when using polymeric substrate materials, this must be adjusted accordingly.
  • the suspension present on and in the substrate is solidified by heating to 100 to 350 ° C.
  • the suspension is particularly preferably heated for solidification to a temperature of 110 to 300 ° C., very particularly preferably at a temperature of 110 to 280 ° C. and preferably for 0.5 to 10 minutes.
  • the composite can be heated according to the invention by means of heated air, hot air, infrared radiation or by other heating methods according to the prior art.
  • the abovementioned adhesion promoters are applied to the substrate, in particular the polymer fleece, in an upstream step.
  • a suitable solvent such as. B. dissolved ethanol.
  • This solution can also contain a small amount of water, preferably 0.5 to 10 times the amount based on the molar amount of the hydrolyzable group, and small amounts of an acid, such as. B. HC1 or HNO 3 , as a catalyst for the hydrolysis and Condensation of the Si-OR grapples included.
  • an acid such as. B. HC1 or HNO 3
  • adhesion-promoting layers are applied in a pretreatment step in which a polymeric sol is applied and solidified.
  • the application and solidification of the polymeric sol is preferably carried out in the same way as the application and solidification of the suspensions.
  • the substrates in particular the polymer nonwovens, are equipped with an oxide of Al, Ti, Zr or Si as an adhesion promoter, which makes the substrate hydrophilic.
  • Substrates equipped in this way can then be provided with a porous coating in accordance with the prior art described in WO 99/15262 or as described above, with the pretreatment allowing a significantly better adhesion of the coating, in particular to polymer nonwovens, to be observed.
  • a typical polymeric sol for a pretreatment is about a 2 to 10% by weight alcoholic solution of a metal alcoholate (such as titanium ethylate or zirconium propylate), which additionally contains 0.5 to 10 molar parts of water and small amounts of an acid can contain as a catalyst.
  • a metal alcoholate such as titanium ethylate or zirconium propylate
  • the substrates are treated at a temperature of at most 350 ° C. This creates a dense film of a metal oxide around the substrate fibers, which makes it possible to infiltrate the substrate with a suspension or a slip based on a commercial zirconium nitrate sol or silica sol without wetting difficulties.
  • the membranes must be dried at temperatures above 150 ° C so that the ceramic material is a receives sufficient good adhesive strength on the carrier.
  • Particularly good adhesive strengths can be achieved at a temperature of at least 200 ° C and very particularly good strengths at a temperature of at least 250 ° C.
  • temperature-stable polymers are then absolutely necessary, such as polyethylene terephthalate (PET), polyacrylonitrile (PAN), polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF) or polyamide (PA).
  • PET polyethylene terephthalate
  • PAN polyacrylonitrile
  • PTFE polytetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • PA polyamide
  • the membrane can be pre-consolidated by pre-drying at a lower temperature (up to 100 ° C).
  • the ceramic layer acts as a support for the support, so that the substrate can no longer melt away.
  • both types of application of an adhesion promoter before the actual application of the suspension can improve the adhesion behavior of the substrates, in particular with respect to aqueous, particulate sols, which is why substrates pretreated in this way with suspensions based on commercially available sols, such as, for. B. zirconium nitrate sol or silica sol can be coated according to the invention.
  • this procedure of applying an adhesion promoter also means that the manufacturing process of the membrane according to the invention must be expanded by an intermediate or pretreatment step. This is feasible, however, also more complex than the use of adapted brines to which adhesion promoters have been added, but also has the advantage that better results are also achieved when using suspensions based on commercially available brines.
  • the inventive method can, for. B. be carried out so that the substrate is unrolled from a roll, at a speed of 1 mh to 2 m / s, preferably at a speed of 0.5 m / min. up to 20 m / min and very particularly preferably at a speed of 1 m / min to 5 m / min through at least one apparatus which brings the suspension onto and into the support, such as, for. B. a roller and at least one other apparatus which allows the solidification of the suspension on and in the support by heating, such as. B. passes through an electrically heated oven and the so produced 03 00 330
  • Membrane is rolled up on a second roll. In this way it is possible to manufacture the membrane according to the invention in a continuous process.
  • the pre-treatment steps can also be carried out in a continuous process while maintaining the parameters mentioned.
  • Materials or membranes which have average pore sizes of less than 1 ⁇ m, particularly less than 500 nm and very particularly preferably less than 100 nm are preferably used as the composite material.
  • the composite materials preferably used have a pore size of 1 to 1000 nm, preferably 2 to 500 nm and very particularly preferably 3 to 100 nm.
  • the coating of the composite material with a solution according to a preferred embodiment of the method according to the invention which has at least one polymer.
  • the composite material can be coated with a solution 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 300 ⁇ m, particularly preferably less than 200 ⁇ m and very particularly preferably less than 100 ⁇ m.
  • the application thickness can e.g. B. can be influenced by so-called recoating systems.
  • the polymer layer is formed by removing the solvent at a temperature of 50 to 350 ° C, preferably at a temperature of 50 to 125 ° C
  • a solution of is preferably used as the polymer solution Polydimethylsiloxane (PDMS), polyvinyl alcohol, methyl cellulose, polyamide, polyimide, polyether, polyurethane, polyester or copolymers or block copolymers of these polymers or cellulose acetate or a polymer mixture which contains at least one of the compounds mentioned, or these compounds or modifications of these compounds , Suitable solvents are the known solvents, which are able to dissolve the polymers mentioned, such as. B. toluene, gasoline fractions, THF, alcohols but also water and other known solvents.
  • the solutions used which have at least one polymer, preferably have from 0.1 to 10% by weight, particularly preferably from 0.5 to 5% by weight, of polymers or cellulose acetate.
  • the polymer solution has compounds or components which enable the polymers to crosslink during film or layer formation, but also after layer formation.
  • the known crosslinkers or crosslinking systems suitable for crosslinking the polymers mentioned can be used as crosslinkers or crosslinking systems.
  • Typical crosslinkers are e.g. B. connections such. B. Peroxides or epoxy groups or diisocyanate groups containing compounds.
  • the polymer or the polymer material that is used for the formation of the polymer layer can be chemically changed by the temperature treatments mentioned but also by an additional temperature treatment.
  • a chemical change can e.g. B. a 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.
  • B. by UV radiation if the starting polymer layers contain UV-crosslinkable grapples or by low-energy electron beams.
  • the hybrid membrane is then dried and rolled up. Depending on which carrier is used, this process must be repeated one or more times.
  • the composite material can also be guided past the polymer film from above, but this often results in somewhat thicker films.
  • the polymer films on a fluid surface can e.g. B. generated by the polymer of the selectively acting layer of the hybrid membrane is dissolved in a non-water-soluble solvent in a concentration of 0.1 to 5% and this solution is applied to a water surface. After evaporation of the solvent, a very thin gas-tight film is obtained which floats on the water surface and can now be applied to the membrane using the method described above.
  • 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 and ultrafiltration. Applications as a membrane reactor are also conceivable, even at higher temperatures.
  • the hybrid membranes according to the invention can therefore, for. B. as a membrane in pressure-driven membrane processes, in nanofiltration, in reverse osmosis or in ultrafiltration.
  • 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. It is also possible to use a 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 pressures from 20 to 100 bar in nanofltration applications, most polymer membranes are very compact and therefore the flows through the membrane are significantly lower than they would be from the selective separation layer alone.
  • Example la Production of an S100PAN as a composite material
  • the slip is rolled onto the fleece with a roller that moves in the opposite direction to the belt direction (direction of movement of the fleece).
  • the fleece then runs through an oven at the specified temperature.
  • the same method or arrangement is used in the subsequent experiments.
  • a microfiltration membrane with an average pore size of 100 nm is obtained.
  • Example lb Production of an S100PET as a composite
  • an inorganic, flexible composite material from example la is presented as the material to be coated.
  • 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% by weight of PDMS, 1.37% by weight of crosslinker and 0.084% by weight of a catalyst in THF.
  • Example 2b In a subsequent step, the membrane obtained according to Example 2a is irradiated with a radiation dose of 69kGy from a low-energy accelerator of the LEA type (Institute for Surface Modification Leipzig e.V.) in an air atmosphere.
  • a PDMS membrane which was insoluble in organic solvents and had no tendency to delaminate and which can be used for gas separation but also in nanofiltration in organic solvents was obtained.
  • the cutt-off (determined with polystyrene as a 1% solution in cyclohexane, the respective molecular weight distributions being determined by means of gel permeation chromatography) of this membrane is 10,000 g / mol.
  • Example 2c An approximately DIN A4 piece of a composite material according to Example 1b was treated with a P VA solution in the dip-coating technique.
  • the solution consists of: 2.5% polyvinyl alcohol and 1.0% ⁇ -cyclodextrin in an aqueous sodium hydroxide solution which has a pH of 9.
  • the membrane is crosslinked for another 1 hour at 150 ° C and can then be used in pervaporation.
  • DE 199 25 475 AI See DE 199 25 475 AI.
  • Example la An approximately A4 sized piece of a composite material according to Example la was obtained, was provided with a coating of cis-polyisoprene (Aldrich) by making a 2.5% solution of the polymer in toluene. This was placed on a water surface, with the water used being degassed beforehand. After the solvent had evaporated, this film was applied to the composite material produced according to Example 1a by carefully moving it from below to the polymer film and then adhering it. After drying at 100 ° C., the separation factor was determined from the clean gas permeabilities of oxygen and nitrogen with a value of 3.1.
  • cis-polyisoprene Aldrich
  • Example 2e A 5% by weight solution of adipic acid dichloride (Merck) in chloroform is placed in a bowl and carefully covered with a thin layer of an aqueous and weakly basic 5% by weight solution of hexamethylene diamine (Merck). A polymer film immediately forms at the interface of the two phases.
  • This is applied to a composite material according to Example 1a by slowly moving the composite material from above (with the aid of a roller with a 180 ° loop) to the surface of the polymer layer and then slowly transporting the composite material further to the phase boundary.
  • the composite material that is led out of the shell with a polymer layer is then dried at 120 ° C. To the extent that the polymer layer on the composite material is transported away with the roller, the polymer layer is imitated immediately.
  • Example 2a 14% by weight of a very low-aluminum zeolite-Y (from Zeolyst) are additionally added to a coating solution as described in Example 2a.
  • the membrane thus produced in accordance with Example 2a was then characterized by means of a sorption experiment. It was found that this showed a sorption for n-hexane which was 50% higher than in Example 2a. (This was determined by tracking the membrane weights when the samples were stored in a saturated atmosphere.) A 50% increase in sorption always leads to a significant increase in the flow (also called permeability) for this component.
  • a membrane produced according to Example 2b was used to retain polystyrene with a molar mass of 2000 g / mol to 100000 g / mol.
  • the polystyrene was present in tetrahydrofuran as a solvent.
  • the retention rate was 99.2% with a material flow of 10 L n ⁇ i ' Hja 1 at a pressure of 20 bar.
  • the retention rate of a ceramic nanofiltration comparison membrane was significantly lower at 92%.
  • Polymer solvent-resistant nanofiltration membranes always had a retention of> 99% at the beginning. However, this fell over time (after 2 days) to values below 90% retention. This was always accompanied by one significant river drop.
  • a membrane produced according to example 2a was used for the same separation task as in example 3a.
  • the polymer layer dissolved very quickly and no separation was observed.
  • Example 2b A membrane produced according to Example 2b was used for the same separation task as in Example 3a. In contrast to Example 2b, a composite material was used that according to
  • Example la obtained was used, using a PVDF fleece instead of the PAN fleece
  • Example 3d A membrane produced according to example 2b was used for the same separation tasks as in example 3a.
  • a composite material which was obtained according to Example Ia was used, with a polyolefin nonwoven made of polyethylene and polypropylene fibers (FS 2202-03, Freudenberg) having a thickness of instead of the PAN nonwoven for the production of the composite about 30 ⁇ m was used.
  • the retention rate was 98% with a material flow of 3 L nr 'bar 1 . However, this deteriorated after 48 h because the carrier material was slowly attacked by the solvent.
  • a membrane produced according to Example 2c was used for the separation of water and acetonitrile in the pervaporation at 70 ° C.
  • the flow of water was 0.24 kg m "2 h " 1 with a separation factor of 2300.
  • a membrane produced according to example 2e is characterized in its cut-off by means of a polyethylene glycol mixture. This is 370 g / mol at a flow of 10 kg m " h " 1 . Even after a longer running time of 125 h of this membrane at a pressure of more than 50 bar, no flow drop can be measured. Comparative Example:
  • a membrane produced according to Example 2c with a polyethylene (PE) support (manufacturer: Cellgard) instead of the composite material was used for the separation of water and acetonitrile in the pervaporation at 70 ° C.
  • the flow of water was 0.14 kg m ⁇ h "1 with a separation factor of 2390, with a further decrease in flow being observed over the following 3 hours.

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Abstract

Membrane hybride qui associe les avantages des membranes inorganiques, tels que la résistance aux solvants et la stabilité, aux avantages des membranes en matière organique. La membrane hybride selon la présente invention est constituée d'une couche de support céramique déposée sur un support contenant des fibres polymères, ainsi que d'une couche organique de séparation sélective. Les propriétés de séparation des membranes peuvent être ajustées spécifiquement par variation des polymères ou par traitement des substances polymères ou par les conditions de production de la couche polymère de séparation sélective.
EP03742923A 2002-02-26 2003-01-15 Membrane hybride, et procede de fabrication et d'utilisation de ladite membrane Withdrawn EP1483042A1 (fr)

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DE10208278 2002-02-26
DE10208278A DE10208278A1 (de) 2002-02-26 2002-02-26 Hybridmembran, Verfahren zu deren Herstellung und die Verwendung der Membran
PCT/EP2003/000330 WO2003072232A1 (fr) 2002-02-26 2003-01-15 Membrane hybride, et procede de fabrication et d'utilisation de ladite membrane

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AU2003248331A1 (en) 2003-09-09
WO2003072232A1 (fr) 2003-09-04
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JP2005525224A (ja) 2005-08-25
TW200303233A (en) 2003-09-01

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