WO2004082810A1 - Module comprenant des plaques a membrane - Google Patents

Module comprenant des plaques a membrane Download PDF

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Publication number
WO2004082810A1
WO2004082810A1 PCT/EP2004/002844 EP2004002844W WO2004082810A1 WO 2004082810 A1 WO2004082810 A1 WO 2004082810A1 EP 2004002844 W EP2004002844 W EP 2004002844W WO 2004082810 A1 WO2004082810 A1 WO 2004082810A1
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WO
WIPO (PCT)
Prior art keywords
membrane
plates
module according
membrane module
carbon
Prior art date
Application number
PCT/EP2004/002844
Other languages
German (de)
English (en)
Inventor
Andreas Noack
Jürgen Kunstmann
Christian Gnabs
Jörg RATHENOW
Andreas Bán
Original Assignee
Blue Membranes Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE10311950A external-priority patent/DE10311950A1/de
Priority claimed from DE10335130A external-priority patent/DE10335130A1/de
Application filed by Blue Membranes Gmbh filed Critical Blue Membranes Gmbh
Publication of WO2004082810A1 publication Critical patent/WO2004082810A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/248—Reactors comprising multiple separated flow channels
    • B01J19/249—Plate-type reactors
    • 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
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/06—Tubular membrane modules
    • B01D63/061—Manufacturing thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/08—Flat membrane modules
    • B01D63/081—Manufacturing thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/08—Flat membrane modules
    • B01D63/082—Flat membrane modules comprising a stack of flat membranes
    • B01D63/0821—Membrane plate arrangements for submerged operation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/14—Pleat-type membrane modules
    • 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
    • B01D67/0072—Inorganic membrane manufacture by deposition from the gaseous phase, e.g. sputtering, CVD, PVD
    • 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
    • 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
    • B01D69/1218—Layers having the same chemical composition, but different properties, e.g. pore size, molecular weight or porosity
    • 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
    • B01D69/145—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing embedded catalysts
    • 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
    • B01D71/021—Carbon
    • B01D71/0212—Carbon nanotubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2475—Membrane reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • B01J35/59—Membranes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/0229—Purification or separation processes
    • C01B13/0248—Physical processing only
    • C01B13/0251—Physical processing only by making use of membranes
    • C01B13/0255—Physical processing only by making use of membranes characterised by the type of membrane
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
    • C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2313/00—Details relating to membrane modules or apparatus
    • B01D2313/08—Flow guidance means within the module or the apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/08—Patterned membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/24—Mechanical properties, e.g. strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00018—Construction aspects
    • B01J2219/0002—Plants assembled from modules joined together
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24—Stationary reactors without moving elements inside
    • B01J2219/2401—Reactors comprising multiple separate flow channels
    • B01J2219/245—Plate-type reactors
    • B01J2219/2451—Geometry of the reactor
    • B01J2219/2453—Plates arranged in parallel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24—Stationary reactors without moving elements inside
    • B01J2219/2401—Reactors comprising multiple separate flow channels
    • B01J2219/245—Plate-type reactors
    • B01J2219/2451—Geometry of the reactor
    • B01J2219/2456—Geometry of the plates
    • B01J2219/2459—Corrugated plates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24—Stationary reactors without moving elements inside
    • B01J2219/2401—Reactors comprising multiple separate flow channels
    • B01J2219/245—Plate-type reactors
    • B01J2219/2475—Separation means, e.g. membranes inside the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24—Stationary reactors without moving elements inside
    • B01J2219/2401—Reactors comprising multiple separate flow channels
    • B01J2219/245—Plate-type reactors
    • B01J2219/2476—Construction materials
    • B01J2219/2477—Construction materials of the catalysts
    • B01J2219/2479—Catalysts coated on the surface of plates or inserts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24—Stationary reactors without moving elements inside
    • B01J2219/2401—Reactors comprising multiple separate flow channels
    • B01J2219/245—Plate-type reactors
    • B01J2219/2476—Construction materials
    • B01J2219/2483—Construction materials of the plates
    • B01J2219/249—Plastics
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0405—Purification by membrane separation
    • C01B2203/041—In-situ membrane purification during hydrogen production
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/048—Composition of the impurity the impurity being an organic compound
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0043—Impurity removed
    • C01B2210/0046—Nitrogen

Definitions

  • the present invention relates to membrane modules comprising at least three membrane plates arranged parallel to one another, and to the use thereof for separating fluid mixtures and / or as a catalyst carrier
  • US Pat. No. 5,695,818 describes asymmetrical carbon-based membranes, wherein symmetrical hollow fiber membranes are modified using CVD methods.
  • US Pat. No. 5,925,591 also describes processes for producing symmetrical carbon membranes consisting of hollow carbon fibers. These carbon hollow fiber membranes are combined into bundles in order to produce corresponding carbon fiber bundle modules. The fiber bundle modules described are up to one meter long.
  • the cited carbon fiber membranes which are combined in modules to form bundles, prove to be problematic in particular because they require complex repairs and processes for their production in order to achieve a homogeneous carbonization of the bundled cellulose fibers from which the
  • Carbon fiber membranes are manufactured.
  • these have the Technology membrane systems and modules have the disadvantage that, due to their thickness, they build up mass transfer resistances and flow resistances that are too high, which affects the economics of separations.
  • Another object of the present invention is to provide a method for separating fluid mixtures which enables the enrichment or depletion of certain fluid components, a membrane module according to the invention being used.
  • a membrane module which comprises: a dense packing of a plurality of membrane plates arranged parallel to one another and spaced apart from one another, the regions between the membrane plates being alternately connected to one of two devices for the passage of two separate fluid flows through the respective regions, and the regions between the membrane plates being separated from one another in a fluid-tight manner, so that a mass transfer between two fluid flows through the areas between the membrane plates is essentially only possible through permeation of fluid components through the membrane plates.
  • fluid denotes substances or mixtures of substances which are in the liquid or gaseous state of aggregation at the application temperatures of the membrane module according to the invention or the separation process of the present invention.
  • the membrane module or the fluid separation process of the present invention is particularly preferred used in the separation of gases and gas mixtures.
  • This simplest basic embodiment of the membrane module of the present invention ensures two flow areas for fluid flows which lie on two sides of a membrane and can be flowed through in two different directions.
  • This arrangement ensures that a fluid flow, which is introduced into or passed through the first intermediate region and consists of one or more fluid components, comes into contact with the membrane surface, with fluid components passing through the membrane in the second
  • Intermediate area can pass, which is flowed through in a second direction by another identical or different fluid, which can be enriched in this way with the permeated fluid components.
  • intermediate area denotes a cavity through which fluid flows can be directed through the module from an inlet opening to an outlet opening of the cavity.
  • the first and second intermediate regions according to the invention consist of a multiplicity of channels which are separated or connected to one another, in most cases essentially parallel, which together form an intermediate region between two membrane plates.
  • the membrane plates used in modules according to the invention can be very thin, with a thickness of less than 1 mm, preferably less than 100 ⁇ m, particularly preferably less than 10 ⁇ m.
  • the membrane module as defined above, will be designed so that it comprises a large number of membrane plates, as a result of which a large number of alternating first and second intermediate areas are created in the module. Since the directions in which the first and second intermediate regions can flow through form an angle to one another, that is to say are not identical, the membrane module will consequently form outer surfaces on the edge side with respect to the membrane plates, first outer surfaces of this type being formed which are arranged on both sides of the open ends of the first intermediate regions and two further outer surfaces on the edge side with respect to the membrane plates, which are arranged on both sides of the open ends of the second intermediate regions.
  • the membrane module will have two further outer surfaces, each of which corresponds to the outer surface of the membrane plates that are located to the extreme.
  • this type of module construction ensures a first inflow surface of the module, which allows fluid to pass through the membrane module only through the first intermediate regions between the respective membrane plates.
  • the membrane module comprises a second inflow surface for a second fluid flow, which ensures that the fluid flow only passes through the second intermediate regions to the other end of the membrane module. Since in the interior of the module each membrane plate, with its faces on both sides, adjoins both intermediate areas and thus both fluid flows which are passed through the membrane module, a mass transfer between the first and the second intermediate area or the fluid flows guided thereby can only be achieved by the passage of individual fluid components the membrane is made by permeation.
  • the second intermediate areas can pass through
  • Applying a vacuum can be sucked off continuously or discontinuously.
  • the second Intermediate areas of the membrane module are flushed continuously or discontinuously, with fluid components of the first fluid mixture permeated through the membrane plates being removed from the first intermediate areas with the second fluid stream.
  • the second fluid stream may have the same composition as the first fluid stream or a different one before the separation begins.
  • fluid as used herein includes liquid or gaseous substances, mixtures of substances, solutions, suspensions, emulsions, aerosols and the like.
  • the membrane plates of the membrane module are structured on one or both sides, preferably on both sides.
  • a preferred structuring of the membrane plates is in the form of an embossed or otherwise introduced groove pattern with grooves or channel-like depressions arranged essentially equidistant from one another over the entire surface of the membrane plates.
  • the groove patterns can run parallel to the edges of the membrane plates, can be arranged at any angle to them, can have zigzag patterns or can be wavy.
  • the membrane plates, if structured on both sides can be identical on both sides
  • the membrane plates have a uniform complementary structure on both sides, that is to say that the groove depressions on one side of the membrane plate correspond to a corresponding increase in the profile of the other side of the membrane plate.
  • the membrane plates are arranged in the module so that the groove patterns of two adjacent membrane plates run essentially parallel to one another.
  • the membrane plates are arranged in such a way that the groove patterns of two adjacent membrane plates intersect at an angle, so that when the membrane plates are placed one on top of the other, a plurality of points of contact between the adjacent plates at the points of intersecting raised edges of the groove structures of adjacent plates. In this way, membrane modules are obtained which, due to the connection at many points corresponding to the points of contact of the intersecting groove patterns, have a significantly increased mechanical stability.
  • Groove structures are preferably chosen so that when two membrane plates are placed one on top of the other in the intermediate regions, a structure results which corresponds to a multiplicity of channels or tubes which ensure a suitable flow resistance in the module which is as low as possible.
  • the person skilled in the art will dimension and select the groove patterns in a suitable manner.
  • customary groove structures in embossed membrane plates lead to channel-like or tube-like structures in the first and second intermediate spaces, the cross-sectional area of which can be adapted to the respective intended use.
  • additional spacing elements can be introduced or provided between the membrane plates.
  • Corresponding spacer elements serve to ensure sufficiently large first and second spaces between the membrane plates, which ensure a suitable flow resistance of the module.
  • Corresponding spacer elements can be porous, open-pore flat structures in the form of intermediate layers, network structures, or also on the Membrane plates spacers arranged on the edge, which ensure a certain minimum distance between the plates.
  • the fluid-tight edge connection of two membrane plates in each case can also be connected in a suitable manner with a correspondingly dimensioned spacer, so that the plates are kept at a defined distance from one another.
  • the spacing of the membrane plates from one another is ensured in that, by appropriately dimensioned groove embossments and a crossing of the groove patterns of two adjacent membrane plates at a certain angle, as mentioned above, a large number of points of contact between the adjacent plates at the points of intersecting raised edges of the groove structures, which ensure that spaces are formed along the groove depressions in the form of a multiplicity of channel-like structures.
  • the spacing elements can also be formed by alternately providing groove embossments of different depths on the membrane plates, which leads to elevations of individual groove edges of different heights, so that the number of points of contact between the adjacent plates at the points of intersecting edges Groove structures as a whole is suitably reduced compared to the total number of groove edges present.
  • Membrane module ensures and a favorable flow resistance of the first and second intermediate areas lying between the plates.
  • the membrane module according to the invention is preferably designed such that the angle between the first and second directions through which the first and second intermediate regions can flow is greater than 0 degrees, and is preferably between 1 and 90 degrees, preferably more than 5 degrees, preferably more than 10 degrees, particularly preferably more than 30 degrees and particularly preferably 45-90 degrees.
  • the membrane plates are in the form of rectangular plates, that is to say in the form of squares or rectangles, an angle between the first and second flow direction can be ensured which is approximately 90 degrees, i.e. the two fluid streams flow through the membrane module approximately vertically to each other, the first and second intermediate areas, which are each separated by a membrane plate.
  • the angle between the first and second flow directions can be reduced accordingly and take up any range between 1 and 90 degrees.
  • the membrane plates can also have a trapezoidal shape, for example, so that in at least one direction of flow
  • Flow through the membrane module results in a narrowing or expansion in the reverse direction of the flow through the intermediate areas.
  • flow resistances and the contact times of the fluid flow used with the membrane plates can be additionally controlled and varied in a suitable manner.
  • the membrane plates used in the membrane module of the present invention consist essentially of carbon.
  • Membrane plates made of carbon-based are particularly preferred Composite material, which may contain other additives such as silicon oxides, aluminum oxides, aluminum silicates, boron oxides, glasses, titanium and zirconium oxides, ceramic materials and the like in different proportions.
  • membrane plates made of a carbon-based material, possibly also carbon composite material, which is produced by pyrolysis of carbon-containing starting materials and essentially corresponds to a type of carbon ceramic or carbon-based ceramic.
  • Appropriate materials can be produced, for example, from paper-like starting materials by pyrolysis and an exhaust gas condition at high temperatures.
  • Corresponding production processes, in particular also for carbon composite materials are described in international patent application WO 01/80981, page 14, line 10 to page 18, line 14 and can be used in the present case.
  • the carbon-based membrane plates according to the invention, or membrane modules formed therefrom, can also be produced according to those in international patent application WO 02/32558 page 6, line 5 to page 24, line 9. The disclosure of these international applications is hereby fully incorporated by reference.
  • Membrane modules according to the invention can also be obtained in a simple manner by pyrolysis of suitably prefabricated polymer films or three-dimensionally arranged or folded polymer film packages, as described in DE 103 22 182, the disclosure of which is hereby fully incorporated by reference.
  • particularly preferred embodiments of the membrane module according to the invention can be produced in particular by carbonizing corrugated cardboard, the Corrugated cardboard layers are suitably fixed to one another before carbonization, so that there is a body through which flow can occur in at least two directions.
  • preferred embodiments of the membrane module according to the invention also result from winding paper or polymer film stacks arranged in a cross-current fashion into tubes, and their subsequent pyrolysis by the above-mentioned processes.
  • These winding modules can be arranged such that the first intermediate regions extend in the pipe direction, with the pipe cross section as the first inflow surface, and the second intermediate regions extend transversely to the pipe direction.
  • the membrane modules can be parylenized by known methods before or after a carbonation step. In the case of paryleneation after carbonization, it can then be pyrolyzed again with the exclusion of oxygen. These treatment steps enable a targeted modification of the surface and porosity properties of the membrane modules according to the invention.
  • membrane modules according to the invention can be fluoridated by processes known per se, for example by lipophilic ones
  • membrane modules according to the invention can also be manufactured from membrane plates made of polycarbonate, polysulfone,
  • Polytetrafluoroethylene PTFE
  • polyacrylonitrile copolymer cellulose, cellulose acetate, cellulose butyrate, cellulose nitrate, viscose, polyetherimide, polyoctylmethylsilane, polyvinylidene chloride, polyamide, polyurea, polyfuran, polyethylene, Polypropylene and / or copolymers thereof, as well as mixed matrix systems which, in addition to the polymer component, also contain inorganic components such as activated carbon, carbon molecular sieve or zeolites.
  • inorganic components such as activated carbon, carbon molecular sieve or zeolites.
  • the fluid-tight edge connections between individual membrane plates in the membrane module according to the invention can be ensured by gluing the edges of the membrane plates by means of adhesives, glass, possibly filled epoxy resins, lacquers and polymer materials.
  • adhesives glass, possibly filled epoxy resins, lacquers and polymer materials.
  • the plate-like starting materials it is particularly preferred for the plate-like starting materials to be glued to the corresponding edges at the corresponding edges, and for the membrane module thus prefabricated to be completely subjected to pyrolysis, the actual carbon membrane module being produced becomes.
  • essentially fluid-tight edges can also be formed by fold edges along folds, in that flat starting materials are folded on top of one another in an accordion-like manner before pyrolysis, so that some of the fluid-tight edge connections are predetermined by folds and result in essentially fluid-tight connections along the folds after pyrolysis ,
  • sealing compound blocks for example made of epoxy resin, which are applied by immersion or extrusion.
  • An edge seal of the module can thus be guaranteed, or also a seal between the membrane module and, for example, a housing in which the module is installed in order to obtain a functional fluid separation device.
  • the sealing compound applied in this way can, for example, be cut or sanded at suitable points after the pyrolysis of the module precursor, so that there is on the edge-side outer surface of the module the structure according to the invention of alternating openings of the one intermediate region and the fluid-tightly closed edge regions of the other intermediate regions results.
  • the sealing compound block can also be selectively opened only at individually selected points.
  • Membrane modules according to the invention can be dimensioned in any way related to the intended application, for example with module volumes in the range from 1 cm 3 , preferably about 10 cm 3 to 1 m 3 . In cases where this is desired, the membrane modules are also significantly larger or can be dimensioned on an even smaller micro scale.
  • the present invention ensures a method for the separation of fluid mixtures by means of a membrane module according to the invention, comprising the following steps: - Application of a fluid mixture to one of the two
  • Membrane plates edge-side outer surfaces of the module, so that the fluid mixture flows through the first intermediate areas between the membrane plates in the first direction through the module; Separate removal of fluid components permeated through the membrane plates from the first into the second intermediate regions.
  • the permeated fluid components are discharged from the second intermediate regions with a second fluid stream, the rinsing stream, which is led through these intermediate regions.
  • This second fluid stream can have the same or a different composition than the applied (first) fluid mixture.
  • a continuous or discontinuous discharge of the permeated fluid components from the second intermediate areas can also be used be provided, for example by suction using vacuum or vacuum devices.
  • the fluid mixture to be separated can be applied by means of pressure or without pressure, discontinuously or preferably continuously.
  • the membrane module according to the invention and the method according to the invention can advantageously be used for a large number of fluid separation tasks or can be adapted to them.
  • fluid separation tasks include, but are not limited to, vapor permeation, pervaporation, dehumidification and / or disinfection of air and gases, or for supply or exhaust air filtration, for the production of hydrogen or methane from industrial gases, for the depletion of CO 2 from air or Exhaust gases, for humidifying or dehumidifying gases, for depleting solvent vapors from exhaust air, or for removing CO 2 from natural gas, in gas separation, preferably the separation of CO 2 from natural gas, the separation of methane and / or carbon dioxide from hydrogen Separation of oxygen and nitrogen and / or for the separation or enrichment of oxygen from oxygen-nitrogen mixtures, in particular in the presence of atmospheric moisture, and for the enrichment or depletion of hydrogen from hydrogen-containing hydrocarbon mixtures.
  • the membrane modules of the present invention are used as carrier material for immobilizing catalytic units.
  • the modules can thus be used advantageously as bioreactors in biological and / or biotechnological substance production processes.
  • catalytic unit (s) here encompasses any catalytically active substance, in particular organometallic complexes and enzymes, and in particular microorganisms, algae, bacteria, viruses and cells.
  • non-tissue-forming mammalian cells are preferred as cells, but the membrane modules can also be used for tissue culture systems can be used as a carrier for tissue-forming plant and mammalian cells.
  • the membrane modules of the present invention can have excellent biocompatibility as support materials for microorganisms or cells, are dimensionally stable and extremely variable in terms of their structure, such as pore sizes, internal structure and external shape. Furthermore, the membrane modules according to the invention can be easily sterilized and offer a good adhesive base for microorganisms and cells. Due to these properties, these membrane modules can be tailored for a variety of applications.
  • the membrane modules of the present invention essentially consist of carbon, such as activated carbon, sintered activated carbon, amorphous, crystalline or partially crystalline carbon, graphite, pyrolytic or carbon-containing material, carbon fiber or carbides, carbonitrides, oxycarbides or oxycarbonitrides from Metals or non-metals, as well as from suitable mixtures of these materials.
  • the membrane modules preferably consist of amorphous, graphitic and / or pyrolytic carbon.
  • the membrane module can contain further substances selected from organic and inorganic substances or compounds.
  • Substances such as or compounds of are preferred Iron, cobalt, copper, zinc, manganese, potassium, magnesium, calcium, sulfur or phosphorus.
  • the incorporation of these additional compounds can be used, for example, to promote the growth of certain microorganisms or cells.
  • An impregnation or coating of the membrane module with carbohydrates, lipids, purines, pyromidines, pyrimidines, vitamins, proteins, growth factors, amino acids and / or sulfur or nitrogen sources is also suitable for promoting growth.
  • the following substances can be used to stimulate cell growth: bisphosphonates (e.g. risedronate, pamidronate, ibandronate, zoledronic acid, clodronic acid, etidronic acid, alendronic acid, tiludronic acid), fluorides (disodium fluorophosphate, sodium fluoride); Calcitonin, dihydrotachystyrene, as well as all growth factors and cytokines (epidermal growth factor (EGF), platelet-derived growth factor (PDGF), fibroblast growth factors (FGFs), transforming growth factors-b TGFs-b), transforming growth factor -a (TGF-a), erythropoietin (Epo), insulin-like growth factor-I (IGF-I), insulin-like growth factor-II (IGF-II), interleukin-1 (IL-1), interleukin 2 (IL-2), Interleukin-6 (IL-6), Interleukin-8 (IL-8), Tumor
  • the average pore size of the membrane module is preferably for
  • Bioreactor systems between 2 angstroms and 1 millimeter, preferably between 1 nanometer and 400 micrometers, particularly preferably between 10 nanometers and 100 micrometers.
  • the membranes of the membrane module according to the invention for use in biological or chemical reactions are essentially impermeable for the catalytic units and the reaction products immobilized on the module and essentially permeable for the reaction medium and the reaction educts, and for the rest, if the remaining outer surface is present, if appropriate sealed.
  • chemical reactions comprises all responses without the aid of living organisms.
  • biological response includes ⁇ reactions with the aid of living organisms such as cells or microorganisms.
  • reaction medium encompasses any fluid, gaseous or liquid, such as water, organic solvents, inorganic solvents, supercritical gases and conventional carrier gases.
  • starting material comprises the starting materials for a chemical or biological reaction or nutrients, oxygen and possibly carbon dioxide, in particular in the case of biological ones
  • reaction products relate to the reaction products of a chemical reaction or the reaction products or metabolic products in the case of biological reactions, regardless of the state of aggregation.
  • reaction mixture includes a mixture of the
  • the membrane modules of the present invention have the advantage that the catalytic units can no longer leave them due to the semi-permeable separating layer and / or the sealing of the module units.
  • Membrane surfaces of the module according to the invention are particularly suitable for the immobilization of microorganisms and tissue cultures.
  • the microorganisms or tissue cultures settle on the membrane surfaces and can be supplied with liquid or gaseous nutrients via the flow channels in the intermediate areas, while metabolic products can be easily removed if necessary.
  • the catalytic units preferably microorganisms or cell or tissue cultures, are supplied with the reactants such as nutrients via the first intermediate regions of the membrane module, while the products are removed or retained via the second intermediate spaces and, if appropriate, can be separated from the module in a later step , Furthermore, the catalytic units are protected from the discharge and from possible harmful environmental influences, such as mechanical loads.
  • the corresponding modules which are loaded with different microorganisms or cell cultures, can For example, for the production of active substances, they are immersed in a single nutrient medium and after a certain time are removed from the nutrient medium and removed to remove the active substance, or the products are removed continuously.
  • the membrane modules can also be designed so that they have to be destroyed to remove the active substance or that they can be opened or closed reversibly.
  • the modules can preferably be opened and closed reversibly.
  • the membrane modules can, if desired or necessary, be cleaned, sterilized and reused.
  • the continuous embodiment has the advantage that the catalytic units can no longer leave the carrier material due to the membrane and an external seal, but a mass transfer via the semipermeable membrane is permitted.
  • the catalytic units are supplied with the reactants and the reaction products can be removed continuously or discontinuously, but the catalytic units are protected from the discharge and from possible harmful environmental influences, such as mechanical loads.
  • a large number of membrane modules can also be operated in series or in parallel.
  • the reaction educts and products each diffuse through the membrane due to a concentration gradient that builds up between the first intermediate regions on one side of the membrane and the second intermediate regions on the other side of the membrane.
  • the diffusion path is made up of the laminar boundary film on the first side of the membrane, the membrane itself and the second side of the membrane, without wishing to be bound to any particular theory Membrane together.
  • the further mass transport takes place either also by diffusion or by flow processes.
  • the concentration gradient between the first and the second gaps of the membrane module is preferably maintained by the continuous feed of educt and, if appropriate, product removal.
  • the person skilled in the art knows that the turbulent flow with increasing Reynolds (Re) number causes the laminar boundary film on the outer surface of the membranes to become thinner and the mass transfer to be faster.
  • the semipermeable membrane can be modified in a suitable manner, for example by fluoridation, parylenation, with carbon fibers, activated carbon, pyrolytic carbon, single- or multi-walled carbon nanotubes,
  • Carbon molecular sieve material deposited by means of CVD or PVD such as C, Si, metals, etc.
  • Outer surfaces of the membrane module that are not necessary for mass transport are preferably sealed in accordance with the present invention.
  • the sealing can be accomplished by an impermeable layer.
  • This impermeable layer can consist of the same materials as the membrane itself and differ from the semipermeable membrane only in the pore size.
  • any means of sealing can be used which ensures that essentially no mass transfer can take place over sealed areas, apart from the mass transfer via the semipermeable membrane.
  • the seal can be reversible or irreversible.
  • the seal is preferably irreversible.
  • the membrane modules according to the invention are before or optionally sealed after the introduction of the catalytically active peculiarities.
  • the membrane module can be loaded or equipped with catalytic units for use in biological or chemical reactions by means of a large number of measures which are usually known to the person skilled in the art. It is preferred to bring the membrane module into contact with a solution, emulsion or suspension containing the catalytic unit by immersing, spraying, coating or the like in order to cause the catalytic units to be embedded in the porous body, and then removing the solvent and optionally drying ,
  • These methods can also be used to feed only the first or only the second intermediate regions of the membrane module, and are particularly preferred in many embodiments in order to separate educts or products through the membrane from the catalytic units.
  • the module is preferably immersed in such a solution, emulsion or suspension for a period of 1 second to 90 days in order to remove the catalytic
  • the membrane modules thus produced with the catalytic units can contain from 10 "5 wt .-% to 99 wt .-% catalytic units, in particular at
  • Metal catalysts based on the total weight of the loaded module.
  • the weight of the biomass can exceed that of the module itself many times over, for example up to 10 6 times the module weight.
  • the cell density in bioreactor modules can be in the range from 1 to 10 23 cells per ml volume, in particular reactor volume, preferably up to 10 2 , preferably 10 5 , in particular up to 10 9 cells per ml.
  • the catalyst-containing membrane modules according to the invention can be used in reactors for chemical and / or biological reactions. These reactors can be operated continuously or in batches. For batch reactions, stirred tank reactors are preferred. These stirred tank reactors are equipped with an agitator and, if necessary, with a continuous educt addition device.
  • the membrane modules are optionally immersed in a container in the reaction mixture comprising the reaction medium and the starting materials. If comparatively small modules are used, they are preferably immersed in the reaction mixture in a container. Good convection is necessary in these systems. Educts must always be supplied in sufficient quantities. The person skilled in the art recognizes that measures which lead to thorough mixing and good convection are suitable for the present invention.
  • Continuous process control has the advantage that educts can be fed continuously and products can be discharged continuously. In this way, a concentration gradient between the first and the second intermediate regions of the membrane module can be maintained particularly well, as stated above.
  • the educt stream can preferably be circulated, suitable measuring and control devices being provided, for example for temperature, pH value, To control nutrient or educt concentration. Products can be withdrawn from the cycle stream continuously or discontinuously.
  • the membrane modules according to the invention can also be used in bioreactors for the preparation, separation or purification of product streams.
  • protein coatings on the membrane module can be used for the selective removal of antibodies and the like, porous bodies loaded with microorganisms can be used for cleaning waste streams, etc.
  • membrane modules according to the invention are particularly suitable for use in bioreactors, for membrane separation processes, virus separation or in online reactor systems for the production of active substances, in particular pharmaceutical active substances or vaccines, by colonizing the membrane modules with suitable active substance-producing microorganisms, cells or tissues.
  • the cross-flow arrangement of the modules according to the invention enables, for example, a particularly simple supply of the organisms with nutrients through the flow channels.
  • the discharge of products through the membrane or the flow channels can also be carried out in a simple manner with suitable material cycle management, if necessary also separately from the nutrient media.
  • the use of the membrane modules according to the invention as a substrate or carrier for colonization with microorganisms and cell cultures is therefore particularly preferred.
  • the membrane modules produced according to the invention as carrier and / or rearing systems (TAS) for the cultivation of primary cell cultures such as eukaryotic tissue, for example bones, cartilage, Liver, kidneys, as well as for the cultivation or immobilization of xenogeneic, allogeneic, syngeneic or autologous cells and cell types, and possibly also of genetically modified cell lines.
  • TAS carrier and / or rearing systems
  • the membrane modules according to the invention can also be used especially as support and rearing systems for nerve tissue. It is particularly advantageous that the modules are particularly adaptable and suitable for this, in particular through the suitable selection of the materials and manufacturing processes. For example, the use of carbon-based membrane modules enables simple adjustment of the conductivity of the modules themselves and the application of pulse currents for the cultivation of nerve tissue.
  • the membrane modules according to the invention can be particularly useful for the microorganism, cell, tissue or organ growth, in particular also by means of adjustable provision, distribution and replenishment, by suitable adjustment of the porosity, by the flow channel design and the three-dimensional shaping Nutrient solution or medium at the place of consumption, as well as by supporting or promoting cell and tissue proliferation and differentiation.
  • the membrane modules can be used as TAS for cultivation in existing bioreactor systems, e.g. B. passive systems without continuous control technology, but also active systems with gas supply, nutrient supply, product discharge and automatic setting of parameters (acidity, temperature, nutrient content), i.e. in the broadest sense reactor systems with measurement and control technology.
  • existing bioreactor systems e.g. B. passive systems without continuous control technology, but also active systems with gas supply, nutrient supply, product discharge and automatic setting of parameters (acidity, temperature, nutrient content), i.e. in the broadest sense reactor systems with measurement and control technology.
  • modules according to the invention can be used as TAS by providing suitable devices such as connections for perfusion with nutrient solutions and the Gas exchange can be operated as a reactor system, in particular also modularly in corresponding row reactor systems and tissue cultures.
  • Membrane modules according to the invention can also be used in or as ex vivo reactor systems, e.g. extracorporeal assistance systems, or used as organ reactors, e.g. so-called liver assist systems or liver replacement systems; or also in vivo or in vitro for encapsulated islet cells, e.g. B. as an artificial Pancreas, encapsulated urothelial cells, e.g. as an artificial Kidney and the like, which are preferably implantable.
  • ex vivo reactor systems e.g. extracorporeal assistance systems, or used as organ reactors, e.g. so-called liver assist systems or liver replacement systems
  • organ reactors e.g. so-called liver assist systems or liver replacement systems
  • encapsulated islet cells e.g. B. as an artificial Pancreas
  • encapsulated urothelial cells e.g. as an artificial Kidney and the like, which are preferably implantable.
  • the modules according to the invention can also be modified by impregnation and / or adsorption of growth factors, cytokines, interferons and / or adhesion factors.
  • suitable growth factors are PDGF, EGF, TGF- ⁇ , FGF, NGF, erythropoietin, TGF-ß, IGF-I and IGF-II.
  • Suitable cytokines include, for example, IL-1- ⁇ and -ß, IL-2, IL-3, IL-4, IL-5, IL-6, IL-7, IL-8, IL-9, IL-10, IL -11, IL-12, IL-13.
  • Suitable interferons include e.g. INF- ⁇ and -ß, EMF- ⁇ .
  • suitable adhesion factors are fibronectin, laminin, vitronectin, fetuin, poly-D-lysine and the like.
  • modules according to the invention can also be used as microarray systems for e.g. Drag discovery, tissue screening, tissue engineering etc.
  • FIG. 1 shows a perspective view of a section of a membrane module according to the invention with a vertical cross-flow arrangement.
  • FIG. 2 shows a perspective view of a schematic membrane module structure using cross-grooved membrane plates.
  • the module of Figure 1 consists of a plurality of membrane plates 3, which have a groove-shaped embossed pattern on both sides, which leads to a kind of honeycomb structure of the front outer surface of the module on the edge with respect to the membrane plates 3 when the plates are placed one on top of the other.
  • this front outer surface there are alternately arranged inlet openings 5 into the first intermediate areas and closed ones
  • Edge surface portions 4 (shown in dark), which correspond to the edge seals of the second intermediate areas.
  • a first fluid flow can flow through the module in a first direction x through the first intermediate regions.
  • a second fluid flow can be conducted in a second direction y, perpendicular to the first direction x, through the second intermediate regions.
  • the edge-side seals 7 of the membrane plates on the underside of the module alternate with the free openings for entry into the second, through-going spaces in the y-direction, between the membrane plates 3, which are the first
  • the optional, sealed and planned sealing surface 2 on the upper side seals the first intermediate regions upwards and simultaneously opens the second intermediate regions upwards, in the sense of an outflow surface 1 with respect to the flow in the y direction, on the module opposite the inflow surface 8 in the y direction.
  • FIG. 2 also shows a section of a membrane module according to the invention in a schematic form.
  • the module section consists of eight membrane plates 1 arranged one above the other, which are provided with a diagonally running regular pattern of semicircular recess grooves 2.
  • the membrane plates 1 are arranged one above the other in such a way that the groove structures of two adjacent plates always run crosswise, so that there are a large number of contact points 3 between the individual plates at which the plates are connected to one another.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Nanotechnology (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention concerne un module à membranes comprenant au moins trois plaques à membrane (3) parallèles entre elles, dont chacune présente au moins 4 arêtes, au moins deux arêtes de chaque plaque à membrane étant écartées l'une de l'autre deux à deux. Une première plaque à membrane est reliée (4), de manière pratiquement étanche aux fluides, à une deuxième plaque à membrane voisine le long de respectivement deux des arêtes écartées deux à deux de sorte que, entre la première plaque à membrane et la deuxième plaque à membrane, se trouve une première zone intermédiaire qui peut être traversée par un écoulement dans une première direction x. La deuxième plaque à membrane est reliée (7), de manière pratiquement étanche aux fluides, à une troisième plaque à membrane le long des deux autres arêtes de la deuxième plaque à membrane de sorte que, entre la deuxième et la troisième plaque à membrane, se trouve une deuxième zone intermédiaire qui peut être traversée par un écoulement dans une deuxième direction y formant un angle avec la première direction. L'invention concerne également l'utilisation du module à membranes selon l'invention pour la séparation de fluides, en tant que matériau support pour l'immobilisation d'unités catalytiques pour une utilisation dans des procédés chimiques, biologiques et/ou biotechnologiques de production de substances, dans des systèmes de réacteur pour la production de principes actifs pharmaceutiques, de vaccins ou pour la production de cultures de tissus.
PCT/EP2004/002844 2003-03-18 2004-03-18 Module comprenant des plaques a membrane WO2004082810A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE10311950.7 2003-03-18
DE10311950A DE10311950A1 (de) 2003-03-18 2003-03-18 Membranmodul für die Trennung von Fluidgemischen
DE10335130A DE10335130A1 (de) 2003-07-31 2003-07-31 Immobilisierung von Katalysatoren auf porösen Körpern auf Kohlenstoffbasis
DE10335130.2 2003-07-31

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WO2004082810A1 true WO2004082810A1 (fr) 2004-09-30

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EP1954382A1 (fr) * 2005-11-30 2008-08-13 3M Innovative Properties Company Module a membrane et a courant transversal
CN100462131C (zh) * 2004-10-26 2009-02-18 贡有成 一种折叠的管式膜过滤器
CN112848616A (zh) * 2019-11-28 2021-05-28 安世亚太科技股份有限公司 一种微纳米级工程立体结构材料及其制作方法
EP4223395A1 (fr) * 2022-02-07 2023-08-09 Mann+Hummel Life Sciences & Environment Holding Singapore Pte. Ltd. Module de filtre, bioréacteur à membrane et utilisation du module de filtre

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GB479840A (en) * 1935-07-10 1938-02-10 Hans Behringer Improvements in or relating to heat exchange devices for fluids of the kind comprising a pile of superposed spaced partitions between which the fluids to be subjected tointerchange are caused to flow
EP0345393A1 (fr) * 1986-06-09 1989-12-13 Arco Chemical Technology, Inc. Membrane céramique et son utilisation pour la conversion des hydrocarbures
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CN100462131C (zh) * 2004-10-26 2009-02-18 贡有成 一种折叠的管式膜过滤器
EP1954382A1 (fr) * 2005-11-30 2008-08-13 3M Innovative Properties Company Module a membrane et a courant transversal
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CN112848616A (zh) * 2019-11-28 2021-05-28 安世亚太科技股份有限公司 一种微纳米级工程立体结构材料及其制作方法
EP4223395A1 (fr) * 2022-02-07 2023-08-09 Mann+Hummel Life Sciences & Environment Holding Singapore Pte. Ltd. Module de filtre, bioréacteur à membrane et utilisation du module de filtre
WO2023148690A1 (fr) * 2022-02-07 2023-08-10 Mann+Hummel Life Sciences & Environment Holding Singapore Pte. Ltd. Module de filtration, bioréacteur à membrane et utilisation du module de filtration

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