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WO2025176635A1 - Installation et procédé de production d'une fibre à partir d'une solution polymère - Google Patents

Installation et procédé de production d'une fibre à partir d'une solution polymère

Info

Publication number
WO2025176635A1
WO2025176635A1 PCT/EP2025/054281 EP2025054281W WO2025176635A1 WO 2025176635 A1 WO2025176635 A1 WO 2025176635A1 EP 2025054281 W EP2025054281 W EP 2025054281W WO 2025176635 A1 WO2025176635 A1 WO 2025176635A1
Authority
WO
WIPO (PCT)
Prior art keywords
fiber
station
unit
tempering
emitter
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.)
Pending
Application number
PCT/EP2025/054281
Other languages
German (de)
English (en)
Inventor
Giuseppe GENDUSO
Marcel Schmengler
Julian HILLINGER
David Quast
Lars Peters
Jörg LEISTNER
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
Evonik Operations 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
Application filed by Evonik Operations GmbH filed Critical Evonik Operations GmbH
Publication of WO2025176635A1 publication Critical patent/WO2025176635A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • 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
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0083—Thermal after-treatment
    • 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
    • B01D67/0095—Drying
    • 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
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • 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
    • B01D69/08—Hollow fibre membranes
    • B01D69/087—Details relating to the spinning process
    • B01D69/0871—Fibre guidance after spinning through the manufacturing apparatus
    • 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
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/08—Specific temperatures applied
    • B01D2323/081—Heating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/34—Use of radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/42—Details of membrane preparation apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/24—Mechanical properties, e.g. strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/28—Degradation or stability over time
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0016—Coagulation

Definitions

  • At least one post-treatment unit comprising a thermal treatment unit with at least one thermal treatment station, wherein downstream of the exchange unit, at least one thermal treatment station of the thermal treatment unit is provided, which is designed as a tempering station, comprising at least one tempering furnace, wherein the at least one tempering furnace comprises at least one infrared emitter (IR emitter), wherein the fiber can be at least temporarily received and/or passed through the at least one tempering furnace.
  • IR emitter infrared emitter
  • the tempering furnace is designed and adjustable in such a way that the at least temporarily received and/or passed through fiber and wherein the tempering furnace is designed to heat the at least temporarily received and/or passed through fiber for a defined time (tempering time) to a temperature that is below the glass softening temperature (TG), in particular and also i) is in the range up to 80 °C below the glass softening temperature (TG), and/or ii) is in the range greater than 250 °C.
  • TG glass softening temperature
  • ii is in the range up to 80 °C below the glass softening temperature (TG)
  • ii is in the range greater than 250 °C.
  • the tempering furnace is designed and adjustable to heat the at least temporarily received and/or passable fiber i) for a defined time (tempering time) up to a limit temperature which is max. 1 °C to 4 °C below the glass softening temperature (TG), in particular to a limit temperature in the range from 70 °C to 1 °C below the glass softening temperature, preferably in the range from 65 °C to 1 °C and/or ii) to heat the fiber to a temperature of greater than 250 °C to 450 °C, preferably 280 °C to 450 °C.
  • TG glass softening temperature
  • the system is designed to always maintain a distance of 1 °C to 4 °C from the glass softening temperature (TG) with regard to the at least temporarily accommodated and/or passable fiber, in order not to damage the structure, in particular the desired porosity, of the hollow fiber.
  • TG glass softening temperature
  • the system is designed such that, instead of the aforementioned 1 °C distance from the TG, a distance of 1.5 °C, 2 °C, 2.5 °C, 3 °C, or 3.5 °C can be provided.
  • max. 1 °C, in particular max. 4 °C means that it is particularly advantageous if the distance of at least 1 °C, preferably 4 °C, from the respective glass softening temperature (TG) of the fiber material (polymer substrate) is maintained in order not to damage the structure, in particular the desired porosity, of the hollow fiber.
  • At least one further thermal treatment unit is arranged, comprising a drying station upstream of the tempering station.
  • the fiber is thus annealed in the annealing station or annealing furnace directly or indirectly by the IR radiation of at least one IR emitter.
  • "Indirectly” means that the IR radiation can reach an individual fiber through neighboring individual fibers and/or via reflectors.
  • annealing means heating the fiber for a defined time (annealing time) up to a limit temperature that is max. 1 °C to 4 °C below the glass softening temperature (TG), in particular in the limit temperature range from 80 °C to 1 °C below the glass softening temperature, preferably in the range from 70 °C to 1 °C, particularly preferably in the range from 65 °C to 4 °C below the glass softening temperature.
  • the glass softening temperature TG can be determined by different dynamic differential calorimetry (DSC), also called differential scanning calorimetry (DSC), in particular according to the method of DIN 53765.
  • DSC dynamic differential calorimetry
  • DSC differential scanning calorimetry
  • the decomposition temperature (Tz) of a fiber and/or fiber material (polymer substrate) can also serve as the upper limit temperature and limit temperature range, depending on which effect—decomposition or glass softening—occurs first when the fiber and/or fiber material (polymer substrate) is heated.
  • Decomposition can, for example, consist of burning, incineration, cracking, embrittlement, or other destructive effects.
  • the limit temperature should be lower than Tz.
  • the system should advantageously be designed to always maintain the distance to Tz in a manner analogous to the limit temperature with respect to the at least temporarily absorbed and/or passable fiber, in order to avoid negatively affecting, in particular, the fiber dimensions (macrostructure) and/or the pore structure (microstructure) of the fiber.
  • Fiber materials exhibiting pronounced degradation at temperatures below and above Tz include PIM-1 polymers with high intrinsic microporosity.
  • An example of a PIM is the polycondensation product of 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,T-spirobisindane (CAS No. 77-08-7) and 1,4-dicyanotetrafluorobenzene (CAS No. 1835-49-0).
  • This degradation temperature Tz can be determined by thermographic analysis in a nitrogen atmosphere (Konnertz, N. et al, Molecular mobility of the high performance membrane polymer PIM-1 as investigated by dielectric spectroscopy, ACS Macro Lett. 2016, 5, 528-532).
  • a temperature of more than 250 °C, in particular more than 280 °C, is achieved in the tempering oven by means of the IR radiators for the polymer materials in question, whereby the aforementioned material-dependent distance is maintained.
  • Solutions of polymers exhibiting intrinsic microporosity generally, solutions of polymers suitable for the production of membranes for gas separation, in particular for the production of (spun) hollow fiber membranes; cellulose-based solutions suitable for the production of membranes for gas separation.
  • PIMs intrinsic microporosity
  • a “bundle” can be fixed and formed against each other at least temporarily on one or two sides by a fixing element, such as a banderol, a lacing, a clamp.
  • in intended operation refers to the state of the annealing furnace, in particular a largely mechanically closed state of the annealing furnace, in which the annealing of a fiber inserted in the annealing chamber takes place.
  • open to the atmosphere means that a wall opening and/or a feed channel is provided through which the fiber or fiber bundle can be introduced into the annealing chamber and, in parallel, a gas or gas mixture, especially air, can flow into the annealing chamber.
  • the tempering station serves in particular to finally temper the (raw) fiber that is (externally) wet or has (internally) residual moisture from, for example, detergent, solvent and/or exchange medium, so that the expert can provide a corresponding plant location at which the fiber arrives wet, i.e. undried or with a defined residual moisture after passing through a drying station.
  • a processing unit is arranged downstream of the tempering station.
  • the processing unit can, in particular, comprise at least one winding wheel or a bundling tool and/or an applicator.
  • the term "processing unit” should not be understood in a restrictive sense and describes a unit in which any type of temporary or permanent connection of individual fibers takes place.
  • individual fibers or a fiber bundle can be wound continuously, uncut, using the winding wheel until the winding wheel is fully loaded, and then cut and subsequently cut to a defined length and/or processed in some other way.
  • a bundling tool can additionally or alternatively be used to temporarily or permanently bundle a (sub)group of fibers.
  • the uncut fibers are wound inline and, if necessary, tensioned against one another.
  • a tape, a banderol, or other wrapping means can be looped around the fiber group and suitably secured.
  • the finishing unit can be fully or partially enclosed by the post-treatment unit or connected to the post-treatment station.
  • the bundled groups of individual fibers (fiber bundles) can advantageously be cut in the area of the wrapping, although this is not intended to be limiting. The cut can be made in front of, behind, or through the tape, band, or wrapping material in the transport direction of the fiber bundle.
  • the assembly unit comprises a cutting device for the fibers or the fiber group.
  • a cutting device by means of which the conveyed fibers or fiber group can be cut inline.
  • the bundling tool and/or the cutting device can be moved and/or pivoted in the conveying direction of the fiber in order to avoid interruption of fiber production.
  • the assembly unit can further be designed to form a (final) bundle consisting of y x n fibers or the y sub-bundles from a plurality of y sub-bundles each consisting of n fibers and to fix this at least temporarily.
  • the formation of such (partial) or (final) bundles from a plurality of fibers is followed by gluing (potting) and final processing, i.e. formation of the filter cartridge, or the production of the filter module with insertion of the filter cartridge.
  • the post-treatment unit of the system comprises a coating station, wherein the coating station is used to apply at least one coating to the separation layer made of, for example, a polymer material on the base fiber, wherein the separation layer with the coating and the entire fiber or the at least one fiber bundle must subsequently be subjected to annealing in the annealing oven in order to set the desired separation properties of the hollow fiber membrane.
  • polydimethylsiloxane can be applied as a coating agent in the coating station (coating step), for example, using a spray device or an immersion bath.
  • the PDMS serves Coating, for example, can be used to seal surface defects in the separation layer and may also slightly influence the separation properties of the separation layer.
  • a fiber coated in this way is then advantageously dried in a drying station and subsequently annealed downstream. During the annealing step, the desired separation properties of the hollow fiber are formed using IR radiation.
  • each coating station is followed by a drying station.
  • the hollow fibers used for gas separation can be of two basic types: i) ISA membranes
  • the separation layer or the fiber with the said separation layer is coated with at least one polymer material that is different from the base fiber (coating step), in particular with the polymer material polydimethylsiloxane (PDMS).
  • PDMS polydimethylsiloxane
  • Asymmetric composite membrane comprising a base fiber as a basic or support structure and an applied outer separation layer, which may include at least one further coating layer.
  • a porous base fiber is spun in a spinning device and the subsequent exchange steps, which, in contrast to the ISA membrane, does not yet have an outer separation layer.
  • This base fiber is then coated with at least one material different from the base fiber as an outer separation layer in an application station (coating step).
  • the base fiber and/or the separation layer of an AK membrane according to i) or ii) can be provided with a coating, in particular polydimethylsiloxane (PDMS), in a manner similar to the ISA membrane.
  • PDMS polydimethylsiloxane
  • At least one application station or coating step can be provided for applying a separation layer to a base fiber to produce an AK membrane. Furthermore, at least one coating station can be provided, as described above.
  • the two aforementioned basic types of hollow fiber membrane are finally annealed in the annealing oven using IR radiation, whereby the desired high separation properties are formed.
  • a drying station is located immediately downstream of the at least one application station and/or the at least one coating station, in particular a drying station is provided immediately downstream of each application station and/or coating station.
  • the exchange step may comprise at least one fixing step with a liquid fixing medium and/or at least one washing step in/with a washing medium, in particular in a basin with a washing medium, wherein the washing step may in particular follow the fixing step,
  • At least one drying step comprising a tempering step in which the fiber is heated to a temperature below the glass softening temperature of the polymer substrate, wherein the fiber is heated, i.e. tempered, in the tempering step by means of at least one continuously operated tempering furnace (251) by IR emitters.
  • the fiber is tempered or heated in such a way that the fiber is heated for a defined time (tempering time), also called tempering time, to a temperature which is below the glass softening temperature (TG), in particular and also i) is in the range up to 80 °C below the glass softening temperature (TG), and/or ii) is in the range greater than 250 °C.
  • tempering time also called tempering time
  • the fiber is tempered or heated during the tempering step in such a way that the fiber is heated for a defined time (tempering time) i) to a limit temperature which is max. 1 °C, in particular max. 4 °C below the glass softening temperature (TG), in particular to a limit temperature in the range from 70 °C to 1 °C below the glass softening temperature (TG), preferably to heat in the range from 65 °C to 1 °C and/or ii) the fiber is heated to a temperature of greater than 280 °C to 450 °C and below the glass softening temperature (TG).
  • a limit temperature which is max. 1 °C, in particular max. 4 °C below the glass softening temperature (TG), in particular to a limit temperature in the range from 70 °C to 1 °C below the glass softening temperature (TG), preferably to heat in the range from 65 °C to 1 °C and/or ii) the fiber is heated to a temperature of greater than
  • TG glass softening temperature
  • the respective max. temperature distance from the TG can be provided depending on the respective fiber material and on the system and/or the process.
  • the fiber can be annealed using the IR emitter with an IR radiation power related to the emitter length in meters (IDE) of At least 5.0 kW/rriE, preferably at least 7.5 kW/rriE, and ideally at least 10 kW/rriE. It may also be advantageous if the IR radiation output is max. 100 kW/rriE, advantageously max. 50 kW/rriE, and ideally max. 35 kW/rriE.
  • IDE IR radiation power related to the emitter length in meters
  • the total annealing time using an IR emitter for a bundle of up to 80 individual fibers requires only 0.1% of the annealing time, for example, compared to a conventional annealing oven, such as a forced-air or convection oven.
  • the annealing time can thus be in the range of 0.1 to 60 s, preferably 0.5 to 30 s, ideally 1 to 20 s.
  • heating step in which the IR radiation power is in the range of 5 to 25% of the maximum IR radiation power, advantageously 7.5 to 15%, ideally 10%;
  • the duration of the heating step is advantageously 1/6 to 1/3 of the power step, wherein the power step is advantageously in the range of approximately 0.1 to 60 s, preferably 0.5 to 30 s, ideally 1 to 20 s.
  • annealing step is sometimes also used synonymously with the “power step”, in which the maximum radiation power is emitted by the IR emitter.
  • the tempering furnace i) is open to the atmosphere, in particular has an inlet or outlet opening for the fiber and a passive gas or air introduction takes place with the conveyed fiber into the tempering furnace and/or ii) comprises or can be connected to a ventilation station, via which a gas mixture), in particular air, N2 and/or CO2, is introduced into the interior (tempering chamber) of the tempering furnace.
  • a gas mixture in particular air, N2 and/or CO2
  • gas is guided via locks.
  • the tempering furnace is open to the atmosphere.
  • atmospheric gas air
  • air can be passed through the fiber inlet and/or the fiber outlet as an inlet or outlet opening for a continuous process.
  • no lock chamber is provided.
  • a lock chamber can be provided, in particular a heatable lock chamber, via which a first tempering of the fiber and shielding of the interior of the tempering furnace takes place.
  • a heating gas is introduced into the lock chamber in order to limit the entry of cold or strongly fluctuating ambient air or to reduce the thermal stress on the fiber at the outlet.
  • the lock chamber can comprise a heating element.
  • the heating gas can be a gas mixture, such as Air, an O2-containing gas mixture.
  • the gas (mixture) may comprise at least one inert gas, such as nitrogen (N2) or carbon dioxide (CO2).
  • the direct gas introduction provides a degree of freedom for controlling and regulating the furnace for the process and effectively protects the fiber in the event of, for example, temporary overheating of the components of the annealing furnace, without interrupting the process.
  • the IR emitter can also be a batch unit, so that the fibers, a fiber bundle, or a group of fiber bundles are tempered in batch operation using at least one IR emitter.
  • the fibers are advantageously cut to a desired length before tempering and/or advantageously fixed at least temporarily as (partial) bundles, analogous to the treatment units of the systems described herein.
  • batch tempering it is generally advantageous to temper the individual fibers or fiber bundles while hanging vertically in the axial direction, so that the individual fibers remain largely aligned parallel to one another.
  • Absorption is a measure of the attenuation of the intensity of light or radiation, including IR radiation, through adsorption or scattering after the beam has passed through a material. Absorption is measured using spectrometers.
  • Fig. 1 the system in a first embodiment
  • Fig. 2 the system in a second embodiment
  • Fig. 3 the system in a third embodiment
  • Fig. 5 the system in a fifth embodiment
  • Fig. 6 two variants for the transport of the fiber in the annealing station
  • Fig. 7 shows the experimental setup as a schematic representation
  • Fig. 8 shows a graph comparing the temperature curves from the tests with the known tempering
  • Fig. 9 shows a graph of extinction versus IR spectral radiation of an emitter and nine characteristic curves
  • Fig. 10 four graphs in two partial representations I., II., comparing bundles of 10 and 80 individual fibers with regard to permeance and selectivity;
  • Fig. 11 two graphs for different fiber bundles, as normalized permeance; selectivity against the introduced radiation energy and
  • the storage and feed unit 140 is also only shown in outline and comprises tanks 142 or a tank storage facility for media, in particular for the polymer solution 102 from which the fiber 110 is formed, as well as process media 104, a pump (unit) 146, and an (inert) gas reservoir. These are connected to the spinning unit 106 in a media-conducting manner.
  • the fiber 110 is formed in the spinning unit 106 in a manner not described in detail, as described, for example, for a hollow fiber from a polymer solution in WO 2014/202324 A1. Alternatively, the fiber can also be obtained from a polymer melt, in particular as a hollow fiber.
  • the process media 104 are in particular the process media required during the spinning process, such as in particular the core fluid for forming the inner cavity of the respective individual fiber 110.
  • the freshly formed fiber 110 is introduced into the fixing medium, a non-solvent, of the fixing unit 150 and guided out of the basin of the fixing unit 150 via guide rollers 108.
  • the individual fibers 110 are oriented in the y-direction at a defined spacing from one another by means of comb-like or multi-finger-shaped lane guides 109.
  • the washing unit 160 comprises a plurality of guide rollers 108 arranged below the fluid level of the washing liquid and by means of which the fibers 110 are held in the washing liquid, in particular in an organic washing liquid, for a defined running time in order to remove the non-solvent from the fiber 110.
  • the washing unit 160 can comprise several basins connected in series.
  • the drying station 210 is connected downstream of the washing unit 160.
  • the fibers 110 are gathered into a bundle 112 and guided as a strand through the drying stations via diverter rollers 108.
  • the drying station 210 is connected to a gas supply line 212 and a gas discharge line 214, with a heat exchanger 216 for heating the supply line C being connected to the gas supply line 212.
  • the supply line C is, in particular, dehumidified air.
  • the bundle 112 is deflected several times as a strand by deflector rollers 108, while the heated gas flows around it and dries it.
  • the deflection rollers 108 are usually static bodies over which the conveyed fiber 110 or the bundle 112 is pulled, wherein in embodiments not shown it may be advantageous to drive at least individual deflection rollers 108 in such a way that they rotate about their own longitudinal axis and in the direction of the fiber longitudinal axis AF and thus reduce the tension within the fiber 110 or the bundle 110.
  • the tempering station 250 connected in the main conveying direction A, comprises a tempering furnace 251 as the central element with an IR emitter 252 and a reflector 254, both of which are arranged in a housing 256 of the tempering furnace 251.
  • the tempering furnace 251 is designed as a channel and continuously receives the pre-dried bundle 112 at the inlet side for a tempering time (throughput time) of approximately 10 s, wherein the tempering time can be divided into two or more sub-steps, such as a heating step and a power step.
  • the annealing station 250 or the annealing furnace 251 is connected to a gas supply unit 270 and a gas discharge unit 272, with a compressor 226 and a gas filter unit 274 being part of the gas discharge unit 272.
  • the gas supply and discharge lines 270, 272 are part of a ventilation unit, with the gas supply line 270 being connected to an inert gas source.
  • a conveying means 280 is arranged, which is designed as a forming and conveying unit and conveys the (fiber) bundle 112 in a compressed state to the assembly unit 180.
  • the bundle 112 can be guided vertically (z-direction) in sections (multiple times) by corresponding deflections 108, or, as shown in Figure 3, horizontally (multiple times) (x-direction).
  • vertical or “horizontal” refers to the main orientation and also includes (slightly) inclined orientations.
  • the assembly unit 180 comprises a fixing station 182, a cutting station 184, a lifting unit 186 and a transport element 188.
  • the bundle 112 is transported to the assembly unit 180 via the conveyor 280 and there fixed as a group (fiber bundle) at the free end and/or in the separating or cutting area of the bundle with at least one fixing means (not shown in detail), such as a band, a ribbon, a cord, etc., in particular wrapped several times and thus fixed as a group.
  • the bundle 112 is grasped by the lifting unit 186, which in the illustrated embodiment is designed as an xyz lifting and gripping unit.
  • a bundle 112 is cut to a desired length from the bundle strand, which is then temporarily stored or stacked as a finished bundle 112.
  • the assembled bundles 112 are then discharged from the assembly unit 180 in the forwarding direction B by means of the transport means 188.
  • the system 100 shown in Figure 2 differs from the system shown in Figure 1, particularly in that no drying station 210 is provided. Instead, the fibers 110, after the washing unit 150, are fed directly into the tempering station 250 or the tempering oven 251, which can essentially be designed analogously to the aforementioned tempering station 250 from Figure 1.
  • the tempering station 250 is connected downstream of the washing unit 160.
  • the fibers 110 are gathered into a bundle 112 and guided as a strand in a straight line, i.e., without further deflection, through the tempering station 250.
  • a dehumidification station 220 is arranged on the outgoing conveyor line and above the washing unit 160, which, in the area of the deflection roller 108 there, drives the liquid adhering to the fiber 110 back into the basin of the washing unit 160 by means of the nozzle units 222.
  • the lower detailed illustration shows the top view of the guidance of the fibers 110 at the transition from the washing unit 160 to the tempering station 250 and the grouping station 260 there.
  • Two further, analogous top views are shown in Figure 6.
  • the fibers are spaced apart from one another in the y-direction by means of the lane guide 109 and compressed downstream by the lateral guide rails 262 of the grouping station 260 into a bundle 112 of the then touching individual fibers 110.
  • the compaction takes place in the y-direction and in the z-direction, whereby additional height guides (not shown) analogous to the lateral guide rails 262 can be provided in order to carry out the compaction in the z-direction in a mechanically defined manner and to avoid deformations of the hollow fiber geometry.
  • additional height guides analogous to the lateral guide rails 262 can be provided in order to carry out the compaction in the z-direction in a mechanically defined manner and to avoid deformations of the hollow fiber geometry.
  • at least two groups of the fibers to be bundled are guided through such height guides at different heights (z-direction) for a defined conveying distance before they are deposited on top of one another in the z-direction and formed into a common bundle 112.
  • drying station 210 The elimination of drying station 210 and the associated pipes and units will result in significant energy savings and a significant reduction in the space required by the plants.
  • the assembled and cut fiber bundles 112, in particular a plurality of at least temporarily assembled fiber bundles 112, are annealed batchwise in a annealing oven 251 of the annealing station 250 downstream of the assembly unit 180 by means of an IR emitter (not shown).
  • the annealing furnace 251 of the annealing station 250 is arranged upstream of the assembly unit 180.
  • the spaced-apart individual fibers 110 or the at least one fiber bundle 112 are continuously transported and annealed through the annealing furnace 251.
  • the transport speed and/or the length of the annealing furnace 251 are dimensioned and/or coordinated such that the required residence time (annealing time) of the individual fibers 110 or the at least one fiber bundle 112 in the area of influence of the IR emitter (not shown) can be maintained.
  • the invention additionally includes a fiber storage 230, which is arranged upstream of the tempering station 250 as part of the thermal treatment unit 200.
  • a storage step for the fibers 110 or the bundle 112 can take place before the tempering step.
  • the fiber storage 230 has two opposing groups of deflection elements 232, which can be dynamically driven individually or as a group to change their relative position. In this way, a defined fiber length or bundle length can be stored, while, for example, downstream of the fiber storage 230, the fibers 110 or the fiber bundle 120 are transported more slowly or temporarily stopped than is the case upstream of the fiber storage 230.
  • the system has a first conveyor section F1, in which the fibers can be conveyed at a first conveyor speed v1, in particular can be conveyed continuously, and a second conveyor section F2, in which the fibers can be conveyed at a second conveyor speed v2, in particular can be conveyed discontinuously and/or at a variable speed, wherein a (dynamic) fiber storage 230 is arranged between and/or in the transition from the conveyor section F1 and the conveyor section F2.
  • the conveyor line F1 comprises the spinning unit 106, the fixing unit 150, and the washing unit 160
  • the conveyor line F2 comprises the tempering station 250 with the tempering furnace 251.
  • a strand drive can be provided in the area of the conveyor line F1 and/or F2 (in each case) to draw the fibers 110 or the bundle 122.
  • the strand drive serves to completely or partially empty the fiber storage 230 and/or to accelerate the fibers 110 or the bundle(s) 112, as an acceleration means out of the tempering station 250.
  • the storage capacity of the motor-driven fiber storage 230, the possible acceleration and transport speed of the fiber storage 230 during the accelerated removal of the stored fibers 110, 112 and the length of the tempering furnace 251 are dimensioned and/or coordinated with one another in such a way that the required residence time (tempering time) of the individual fibers 110 or of the at least one fiber bundle 112 in the area of influence of the IR emitters (not shown) can be maintained.
  • Figure 6 shows a plan view of two further embodiments of grouping stations 260 and the alignments and positions of individual fibers 110 produced thereby in the annealing station 250.
  • Partial view I shows grouping station 260, which essentially consists of two comb-like or multi-finger-like lane guides 109, wherein the two opposing lane guides 109 have different spacings between the individual fingers or individual guides. Both lane guides have the same number of individual fingers, or the number of individual fingers depends on the number of parallel-guided individual fibers 110. Depending on the cross-sectional area and geometry of the individual fingers, individual fibers 110 can be located on each side of individual fingers.
  • the lane guide 109 arranged at the entrance of the annealing station 250 and the annealing furnace 251 brings the individual fibers 110 closer to each other to within a few millimeters, for example to within 2 mm to 3 mm. No compression takes place until the parallel individual fibers 110 touch each other, and the individual fibers 110 essentially span a common plane.
  • this embodiment is structurally the most complex, it allows for the shortest annealing times for the fibers 110 and thus requires the shortest extension of the annealing station 250 in the main conveying direction (x-direction).
  • a second grouping station 260 can be arranged downstream, by means of which the final bundle is formed.
  • Partial view II shows the grouping station 260 (here 260.1), which also essentially consists of two comb- or multi-finger-like lane guides 109, whereby the two opposing lane guides 109 also have different spacings between the individual fingers or individual guides.
  • the lane guide 109 arranged at the inlet of the tempering station 250 has a significantly smaller number of individual fingers or individual guides than the lane guide 109 at the exit to the washing unit 160 or the drying station 210. This is due to the fact that the grouping station 260 and the incoming lane guide 109 form several partial bundles 112 from the total number of individual fibers 110, and the subsequent partial bundles 112 are guided through the tempering station 250.
  • three sub-bundles 112.1, 112.2, and 112.3 are formed, which are annealed parallel to one another at a distance from one another in the annealing station 250 and transported through this annealing station 250.
  • the sub-bundles 112.1, 112.2, and 112.3 can subsequently be combined into a (final) bundle 112 in a second grouping station 260.2.
  • the tests were carried out using an annealing station 250, as shown in Figure 7.
  • the annealing station comprised, as its central element, an annealing furnace 251 having a closed housing 256 and in which an IR emitter 252 extended longitudinally.
  • the housing 256 had a base element and a head element and was designed as an elongated cuboid-shaped body whose longitudinal axis was aligned perpendicular to the horizontal in laboratory operation.
  • the IR emitter 252 was arranged off-center on one side, which had a length of approximately 21 cm.
  • the emitter 252 was surrounded by curved metallic reflectors 254, which had an extension of approximately 27 cm in the direction of the longitudinal axis and protruded upwards and downwards on both sides beyond the IR emitter 254.
  • the housing 256 had a central IR radiation chamber and a rear chamber, with essentially no IR radiation entering the rear chamber.
  • the housing 256 was divided longitudinally and connected by hinges, so that it could be opened to insert or remove individual fibers or a fiber bundle (not shown in Fig. 7).
  • a fixing unit 258 was arranged on the head element, which was designed to hold individual fibers 110 or a fiber bundle 112 suspended.
  • the individual fibers 110 or the fiber bundle 112 were clamped at the free, lower end with a weight 259, so that a constant tensile force could be applied to the individual fiber 110 or the fiber bundle 112.
  • the weight 259 was held suspended on the fibers at a slight distance above the foot element.
  • the fixing unit 258 and the weight 259 were arranged in the rear space, for which purpose the reflectors in the head and foot areas had a corresponding feedthrough opening.
  • a lateral guide and contact surfaces for the weight are also arranged so that a fiber bundle can be twisted or wound around the longitudinal axis once or several times as required and can be tempered in such a twisted or wound arrangement of the individual fibers in the fiber bundle.
  • a gas supply line 270 consisting of two lines led into the interior of the housing, through which a constant volume flow of nitrogen (N2) could be introduced.
  • the N2 volume flow was discharged from the interior of the housing, usually continuously, via a central gas discharge line 272.
  • the IR emitter 252 was connected to a control unit 134 for power control, whereby the control software was stored in a connected control and regulation unit 130 and operated by a processor unit there, which in laboratory operation was a commercially available PC.
  • the fixing unit 258 and the weight 259 were designed to fix a fiber bundle 112 of up to 100 individual fibers 110 and to hold it under constant tensile force.
  • the tests were conducted in batch mode. Furthermore, a closed water cooling system was installed in the housing, which was connected to a corresponding cooling circuit.
  • the supplied volume flow of N2 as inert gas was 300 ml/min and the O2 content was ⁇ 100 ppm in the interior of the housing 256.
  • the following parameters were monitored by sensors: the N2 volume flow of the gas supply and gas outlet, the O2 concentration in the gas outlet, the temperature in the interior of the housing in the head space and in the foot space, the volume flow of the cooling water and the shrinkage of the fibers.
  • the weight used was 12g per 10 individual fibers, and 40 l/h of water was passed through the water cooling system as cooling water flow.
  • the exposure (annealing step) of the fibers to IR radiation took place in two steps:
  • the separation properties in particular the permeance and selectivity of the hollow fibers and the filter modules made from them, which had been annealed by means of IR radiation in such a short period of time, were in the range of the known, conventionally annealed hollow fibers, as explained in detail below.
  • Figure 8 shows a graph comparing the two annealing methods.
  • the maximum emitter power applied is normalized to 1 (left y-axis)
  • the maximum temperature in the convection oven is also normalized to 1 (right y-axis)
  • the inventive annealing method using IR radiation is shown essentially on the left in the graph and as a solid line.
  • the comparative test with a conventional electric furnace (convection oven), in which the fibers were also annealed while suspended under constant tensile weight in an inert atmosphere, is shown as a dashed line.
  • a heating step 300 was maintained for 1 s
  • a ramp-up 302 of the IR emitter power was also maintained for 1 s
  • a power step 304 was maintained for 4 s. This was followed by a cooling step 306, which occurred through the opening of the housing 256 to the atmosphere.
  • the ramp-up 302, or the time required for this, essentially results from the device-specific delay time to provide the maximum IR emitter power, based on the power level of the heating step.
  • a preheating phase 400 of approximately 30 minutes was carried out, followed by a ramp-up phase 402 of the convection furnace to maximum conduction and temperature of approximately 2 hours, an annealing phase at the annealing temperature for approximately 2.0 hours and a subsequent cooling phase 406 before opening the electric furnace of approximately 0.8 hours.
  • the hollow fibers produced according to the invention are particularly suitable for the gas separation of CO2, O2, CH4 and N2, in particular for the gas separation of air or biogases.
  • Permeance is the ratio of permeability to the thickness of the fiber or membrane wall and represents a measure of the gas flow through the fiber wall or membrane, thus providing an indicator of the structure and permeability of the hollow fiber or fiber bundle.
  • Gas permeabilities are given in Barrers ( 10 -10 cm 3 cm -2 cm s' 1 cmHg' 1 ).
  • the permeances of hollow-fiber membranes for gases are given in GPU (Gas Permeation Unit, 10 -6 cm 3 cm- 2 s' 1 cmHg- 1 ) or derived units.
  • Permeance is the ratio of permeability to substrate thickness (membrane thickness) in appropriate units, such as the unit I nr 2 h 1 bar 1 .
  • the permeability of gases is measured using the pressure increase method.
  • a flat foil with a thickness between 10 and 70 ⁇ m is exposed to a gas or gas mixture on one side.
  • a vacuum approximately 10-2 mbar
  • the pressure increase on the permeate side is then recorded over time.
  • the permeability of the polymer (substrate) can be calculated according to the following formula: P Permeability in Barrer (IO -10 cm 3 (STP) cm) / (cm 2 s cmHg)
  • Tables 1a and 1b show the comparative test (V1) and two tests according to the invention with two nominally different IR emitters (V2, V3).
  • the annealed fibers were taken from an electric convection oven (V1) of an existing production process (comparative test). These were compared with fibers from the aforementioned experimental or laboratory device (V2, V3), which were annealed using IR emitters in a batch process. In tests V2 and V3, a bundle of 80 individual fibers was annealed using IR radiation in one batch run.
  • Table 1 a Test conditions of tests V1 to V3 (TS - tempering step)
  • the duration of the annealing process could be reduced from approximately 6 hours to less than 10 seconds with IR annealing, with the same and partly improved separation performance, permeance and selectivity of the fibers.
  • the IR emitter powers were measured for the outermost characteristic curve 310.
  • the other eight characteristic curves 312 to 328 show the IR emitter power reduced by 10% each, as follows:
  • Curve 330 shows the position of the maximum of characteristic curves 310 to 328, which follows Wien's law. It was found that for all characteristic curves 310 to 328, the polyimide substrate is virtually transparent to IR radiation, particularly in the wavelength ranges of the maxima of characteristic curves 310 to 328, and exhibited an extinction of less than 0.4.
  • extinction is defined as the ratio of outgoing to transmitted IR radiation of a wavelength or in a wavelength range, as explained above.
  • Figure 12 shows the measured transmittance values comparing an isotropic film and a membrane made of the same polymer substrate, polyimide.
  • the graph is plotted as transmittance in percent [%] (y-axis) against the wavelengths from 900 nm to 4900 nm (x-axis).
  • the membrane proved to be slightly less transparent than the isotropic film, which can be considered an aspect of its heatability using IR radiation.
  • the two partial representations I. and II. differ in that in partial representation I. a fiber bundle of 10 individual fibers was annealed by the two IR emitters and in partial representation II. fiber bundles of 80 individual fibers were annealed in the two IR emitters.
  • the corresponding measured values are shown as small circles in the graphs of Figure 11; for the fiber bundles with 80 individual fibers, the corresponding measured values are shown as “x” in the graphs of Figure 11.
  • the corresponding measured values are shown as “x” in the graphs of Figure 11.
  • the reasons for the high, homogeneous separation performance of the hollow fiber annealed according to the invention are seen as follows: i) The high transparency (low extinction) of the fibers towards IR radiation, especially at the wavelength in the maximum power range of the IR emitter ( ⁇ 5% extinction (IR absorption)), ii) Refraction of the IR radiation and relatively uniform scattering and transmission to neighboring fibers (radiation homogenization) and iii) strong convective energy transport in the annealing furnace through the gas flow (convective-thermal homogenization in the annealing furnace). ...

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Abstract

L'invention concerne une installation de production d'une fibre, en particulier d'une fibre filée, à partir d'au moins une solution polymère, comprenant une unité de commande et de régulation, une unité d'approvisionnement et d'alimentation en produits, une unité d'alimentation en produits, et une unité de filage pour former la fibre. Au moins les unités d'installation suivantes sont fournies, dans la séquence spécifiée, en aval de l'unité de filage afin de traiter la fibre : a. une unité d'échange de solvant, dans laquelle ou à travers laquelle la fibre peut être introduite ou passée immédiatement après l'unité de filage, et b. au moins une unité de post-traitement, comprenant une unité de traitement thermique ayant au moins une station de traitement thermique. Au moins une station de traitement thermique de l'unité de traitement thermique est disposée en aval de l'unité d'échange, ladite station de traitement thermique étant une station de régulation de température et comprenant un émetteur IR, et la fibre peut être au moins temporairement reçue dans et/ou guidée à travers la station de régulation de température. L'invention concerne en outre un procédé de production comprenant une étape de régulation de température à l'aide d'un émetteur IR.
PCT/EP2025/054281 2024-02-19 2025-02-18 Installation et procédé de production d'une fibre à partir d'une solution polymère Pending WO2025176635A1 (fr)

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