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Publication numberUS20010020306 A1
Publication typeApplication
Application numberUS 09/731,901
Publication dateSep 13, 2001
Filing dateDec 8, 2000
Priority dateDec 10, 1999
Also published asDE19959532C1
Publication number09731901, 731901, US 2001/0020306 A1, US 2001/020306 A1, US 20010020306 A1, US 20010020306A1, US 2001020306 A1, US 2001020306A1, US-A1-20010020306, US-A1-2001020306, US2001/0020306A1, US2001/020306A1, US20010020306 A1, US20010020306A1, US2001020306 A1, US2001020306A1
InventorsRudiger Leibnitz, Lars Kreye, Heinz-Joachim Muller
Original AssigneeRudiger Leibnitz, Lars Kreye, Heinz-Joachim Muller
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Process and device for producing filtration-active fibers
US 20010020306 A1
Abstract
A process and a device for producing filtration-active fibers is described. An aqueous suspension is produced from a homopolymer of polyacrylonitrile, polyamide or cellulose acetate and the suspension is heated in a tank to a temperature T which is at least 60 above the boiling point of the water and at least 30 C. below the softening temperature of the polymer. The at least plasticized polymer mass which has been obtained in this way is discharged through at least one nozzle means at least using the autogenous pressure of superheated water. The device calls for that the suspension is prepared in a storage tank, that a mixing tank is connected to the storage tank and is made for heating an aqueous polymer suspension under pressure, and that furthermore there is a nozzle means for discharge of the plasticized polymer mass located at the output of the mixing tank.
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Claims(24)
1. Process for producing filtration-active fibers, in which an aqueous suspension of a hydrophilic polymer which is both free of additives and which also has no organic solvents is heated in a tank and then discharged from the tank, characterized in that homopolymers from polyacrylonitrile, polyamide or cellulose acetate are used as the polymers, that the suspension is heated in a tank to a temperature T which is at least 60 above the boiling point of the water and at least 30 C. below the softening temperature of the polymer, and the at least plasticized polymer mass which has been obtained in this way is discharged through at least one nozzle means at least using the autogenous pressure of superheated water.
2. Process as claimed in
claim 1
, wherein polyamide 6 or polyamide 6, 6 is used as the polyamide.
3. Process as claimed in
claim 1
, wherein cellulose diacetate or cellulose triacetate is used as the cellulose acetate.
4. Process as claimed in
claim 3
, wherein the cellulose acetate has an acetic acid content from 52 to 56%.
5. Process as claimed in one of
claims 1
to
4
, wherein the suspension is kept at the temperature T for a maximum 240 sec.
6. Process as claimed in one of
claims 1
to
5
, wherein the suspension is continuously mixed during heating.
7. Process as claimed in one of
claims 1
to
6
, wherein the polymer concentration in the suspension is 1 to 10% by mass.
8. Process as claimed in one of
claims 1
to
7
, wherein the fibers are discharged in a space with a pressure≦atmospheric pressure.
9. Process as claimed in one of
claims 1
to
8
, wherein the suspension is exposed to a pressure between 15 and 25 bar during heating.
10. Process as claimed in one of
claims 1
to
9
, wherein a polymer powder with grain sizes between 20 and 100 microns is used for the suspension.
11. Use of the fibers produced as claimed in
claim 1
for liquid filtration or for gas filtration.
12. Use as claimed in
claim 11
in microfiber networks.
13. Use as claimed in
claim 11
in a matrix of coarser fibers or as a precoat material.
14. Device for continuous production of filtration-active fibers of PAN, PA or cellulose acetate with a storage tank (2) for preparing the suspension, with a mixing tank (10) which is connected to the storage tank and which is made for heating an aqueous polymer suspension under pressure, and with a nozzle means (16) for discharge of the plasticized polymer mass located at the output of the mixing tank (10).
15. Device as claimed in
claim 14
, wherein the nozzle means (16) has at least one capillary nozzle (24 a, b, c), one pneumatic nozzle, one needle valve or one binary nozzle.
16. Device as claimed in
claim 14
or
15
, wherein there are at least three capillary nozzles (24 a, b, c) adjacent to one another, with their outlet openings (26 a, b, c) aligned at an acute angle to one another.
17. Device as claimed in one of
claims 14
to
16
, wherein the diameter of the capillary nozzles is preferably 0.1 to 10 mm.
18. Device as claimed in one of
claims 14
to
17
, wherein the ratio of the length to the diameter of the capillary nozzle (24 a, b, c) is 30-50.
19. Device as claimed in one of
claims 14
to
18
, wherein the mixing tank (10) is an extruder.
20. Device as claimed in one of
claims 14
to
18
, wherein the mixing tank (10) has a dispersing means.
21. Device as claimed in one of
claims 14
to
20
, wherein a coarse mixer (8) is connected upstream of the mixing tank (10).
22. Device as claimed in one of
claims 14
to
21
, wherein behind the nozzle means (16) there is a discharge tank (15) in which a pressure≦atmospheric pressure can be set.
23. Device as claimed in one of
claims 14
to
22
, wherein there is a metering pump (12) in front of the nozzle means (16).
24. Device as claimed in one of
claims 14
to
23
, wherein in front of the mixing tank (10) there is a heat exchanger (6).
Description
  • [0001]
    The invention relates to a process for producing filtration-active fibers, in which an aqueous suspension of a hydrophilic polymer which is both free of additives and which also has no organic solvents is heated in a tank and then discharged from the tank. The invention also relates to a device as claimed in claim 14.
  • [0002]
    Various processes are known for producing fiber materials. Thus, for example grinding of natural fibers or staple fibers which can be fibrillated in disk refiners or cone refiners is current technology in the paper industry. Grinding influences dewatering behavior on a Fourdrinier paper machine and the strength of the paper web. In particular, wet compaction action by convolution of the fibrils is current practice in the production of deep filter media for liquid filtration. For this application, in addition to natural fibers (cellulose fibers) also staple fibers from cellulose regenerates which are characterized by high fibrillation capacity, for example Lyocell fibers (WO 95/35400), have been used. Ideally the parent fibers first remain, while the fibrils are peeled sideways up to complete fibrillation of the fibers.
  • [0003]
    In this process it is disadvantageous that the extensive fibrillation of the fibers requires long grinding times. As the grinding time increases however shortening of the parent fibers occurs more intensely up to pulverization of the fibers. Exact adherence to the grinding conditions under which shortening to the benefit of fibrillation is for the most part repressed, can be accomplished in practice only with uneconomically low material concentrations and high demands for homogeneity of the initial fibers. In addition the process for natural fibers is limited to fiber types with suitable cell wall architecture and for synthetic fibers is limited to suitable materials (for example acrylonitrile polymers).
  • [0004]
    Production of extremely fine fiber structures from melts of polymer materials is used within the framework of melt-down technology in an industrial scope for producing deep filter materials (for example U.S. Pat. No. 5,681,469). In this process a polymer melt is extruded through a special nozzle. A hot air flow is superimposed on the emerging polymer flow at the nozzle output; in the turbulence field of the hot air flow the polymer filament solidifies as it stretches and frays. The fiber morphology can be influenced via the temperature, delivery speed of the polymer and the air flow intensity. The fibers produced in this way can be used without further processing and can be immediately deposited after spinning as nonwoven or filter elements ready for use.
  • [0005]
    Since the turbulence forces for fiber spinning can act only on the outer surface of the extruded polymer filament and at the same time with impact of the gas flow the solidification of the polymer is caused, finer fiber diameters require a disproportionally stronger air flow. The unduly high energy requirement and cost which are necessary for fiber diameters of dp<3 microns oppose the good availability of the fiber material.
  • [0006]
    Furthermore, the process is limited to materials which when heated pass into a homogenous, low-viscosity melt and are relatively sensitive to thermal stress.
  • [0007]
    In the splicing process a binary polymer melt is extruded. The extrudate contains two polymer fibers which are deposited within and next to one another, with diameters below the diameter of the extrudate. The individual filaments can be isolated by mechanical treatment (grinding) or by application of compressed air to the extrudate. U.S. Pat. No. 3,402,231 describes the coextrusion of PAN and hydroxymethyl cellulose from a hot suspension. In a similar process the target polymer is extruded jacketed by an auxiliary polymer. Stretching the extrudate drastically reduces the diameter of the inside filament of the target polymer.
  • [0008]
    Those polymers which have mutual adhesive forces which are low enough to enable subsequent exposure of the extremely fine fibers by mechanical action are suited to the process. Additives are necessary to prevent overly intimate connection of the polymers.
  • [0009]
    Processes which work with precipitation from a homogenous solution are known for polystyrene (PS), vinyl chloride (VC) and their copolymers (U.S. Pat. No. 4,224,259) and mainly cellulose acetate (for example, U.S. Pat. No. 5,071,599, DE-OS 196 16 010). For reasons of better reprocessing, preferably highly volatile solvents are used (methylethyl ketone, dioxane, tetrohydrofuran) in these processes. A homogenous solution of the polymer is combined in a shear field with a nonsolvent (“precipitation agent”). Nonsolvents and solvents are completely miscible with one another, so that at the instant of meeting of the polymer solution and the precipitation agent instantaneous precipitation of the polymer takes place as a result of dilution of the solvent. Under suitable conditions the polymer precipitates with strong stretching as the extremely fine fiber. The required shear field can be effected by spraying the solution into a precipitation bath (U.S. Pat. No. 3,441,473, U.S. Pat. No. 4,047,862), the use of Venturi nozzles (U.S. Pat. No. 4,192,838, U.S. Pat. No., EP-OS 533 005) or rotor-stator systems (Dispax reactors; U.S. Pat. No. 4,224,259, DO-OS 196 16 010). The attainable fiber morphology corresponds to the requirements for an auxiliary agent in liquid filtration.
  • [0010]
    The disadvantage of this process is that in the first process step large volumes of solvent-containing fiber pulp are produced. In this stage the solvent is in a low concentration in the liquid, but in part also in the fibers. Due to the remaining content of solvent until its final removal there is always the danger of influencing the fiber morphology. Careful separation methods are therefore required (steam distillation).
  • [0011]
    The cost for solvent recovery is reduced with the flash spinning process in which fiber formation is achieved by vaporization of the solvent. Depending on the pretreatment of the polymers different process sequences can be distinguished. The polymer is placed in solution or is dissolved in situ under process conditions. The polymer solution is heated to temperatures above the boiling point of the solvent or solvent system and relieved through a suitable nozzle system using at least the autogenous pressure (expansion spinning).
  • [0012]
    U.S. Pat. No. 3,740,940 describes for example expansion spinning of cellulose acetate (CA) to highly fibrillated yarns with high water absorption capacity. The CA is first homogeneously dissolved at an elevated temperature and at high pressure in an alcohol/freon mixture and then released through a 0.4 to 0.7 micron-wide opening to atmospheric pressure. The halogenated hydrocarbon in this system does not contribute to the dissolution of the polymer, but acts as an inert propellant. According to this process fiber qualities with a specific surface up to 0.4 m2/g (BET) can be achieved.
  • [0013]
    The disadvantage is that the use of halogenated hydrocarbons for reasons of environmental protection is associated with high equipment cost (complete encapsulation of the system). In general the use of halogenated hydrocarbons should be evaluated critically with respect to climate protection.
  • [0014]
    Another version of obtaining extremely fine fibers by flash spinning processes proceeds from a polymer suspension which is heated under pressure. Adding softeners causes plasticization of the polymer without a genuine polymer solution being obtained. The suspension agent is used as a carrier substance for the softener and due to its spontaneous vaporization at the outlet causes a turbulence field which ultimately produces the extremely fine fibers. For cellulose acetate, softeners are known from the production of CA moldings.
  • [0015]
    For the preferred application of liquid filtration it is a disadvantage that well-suited polymers, especially cellulose alkanoate (cellulose acetate/butyrate), polyacrylonitrile (PAN and copolymers) and polyamides (PA-6, PA-66) can be kept in the molten state over a longer time only with the addition of additives.
  • [0016]
    A heavily studied polymer class is acrylonitrile polymerizates and copolymerizates (for example methacrylate, vinyl chloride, vinyl acetate, styrene are suitable as copolymers) which are combined below under the name PAN. There have been attempts to spin acrylonitrile polymer filaments from mixtures of acrylonitrile polymers and water. These attempts as are described in U.S. Pat. No. 3,402,231 and U.S. Pat. No. 258,544 have however led to fibrinous materials which are suitable for paper production or to strand materials of molten and sintered or foamed particles, but not to textile filaments.
  • [0017]
    Thermoplastic deformation of this material in the presence of water is described for example in DE 23 43 571. Here the process is used to produce extruded textile filaments from a superheated melt of hydrated PAN (single phase melt). In addition to water, by adding an organic solvent (0.5 to 10% by mass relative to the polymer) or inorganic components (ZnCl2 or nitric acid) plasticization at elevated temperature and pressure is achieved. P 71.39396 describes the production of fibrous structures, so-called “plexifilaments”, with a specific surface of 0.6−3 m2/g from PAN and PA 6 which are produced by heating an aqueous suspension of the polymer using a stabilizer (silica gel or aluminosilicates) and an inert tenside (for example Triton X).
  • [0018]
    According to DE-OS 41 18 298 A1 and DE-PS 41 22 994, to produce extremely fine fibers (fiber diameters between 0.1 and 100 microns) from a supercooled melt of PAN with at least 75% acrylonitrile portion even the organic solvent can be abandoned. In doing so a mixture of PAN and water is heated to a temperature above the melting point under closed conditions to form an amorphous melt. Then the amorphous melt is cooled to a temperature below the melting point of the supercooled phase and extruded in the temperature range between the melting point and the solidification temperature of the melt to form an extrudate. Water acts as the co-melting material which interacts with the polar nitrile groups of the PAN and cancels the helical twisting of the PAN molecule chains so that this melt can be spun in the supercooled state. Additives of any type should be critically evaluated especially for applications in which release of additives from the polymer into liquid should be avoided as much as possible.
  • [0019]
    While plasticization in water is known for copolymerizates of acrylonitrile and has been used to produce textile fibers (DE OS 22 48 244), for fibers of cellulose acetate (if not noted otherwise, the term “cellulose acetate” designates an acetyl cellulose ester with an acetic acid content between 52 and 55%) a production process in which softeners or organic solvents can be abandoned is not known to date. Generally fibers are obtained by precipitation from a homogenous solution or by extrusion of a melt which contains at least proportionally an organic solvent, softener or stabilizers.
  • [0020]
    U.S. Pat. No. 3,952,081 describes a process for producing extremely fine fibers from a CA suspension which is obtained by suspension of the polymer in a mixture of water and an organic solvent (acetone, methanol, ethanol, etc). A homogeneous solution is achieved by heating the suspension. This melt can be spun into filament yarn by suitable extrusion elements (4.75 Denier/filament or 2.6 Denier/filament).
  • [0021]
    U.S. Pat. No. 4,040,856 discloses that cellulose acetate dissolves at an elevated temperature and elevated pressure homogeneously in aqueous acetone solutions in which it is insoluble under normal conditions. In doing so the polymer passes through a plasticized state in which it can be converted into fibers by spinning nozzles below the temperature at which a homogenous solution is present. The content of organic solvent components can vary over the range between 1 to 60% by mass. In addition to acetone, also methanol, ethanol, and methylethyl ketone are suitable as solvents; a comparable solution behavior is also described for other cellulose alkanoates such as cellulose triacetate, cellulose acetate/propionate or cellulose acetate/butyrate. By releasing the system via a suitable nozzle a fiber pulp can be produced from the plasticized mass. One such process requires for solvent recovery an additional low pressure space from which the solvent can be exhausted and can be sent to reprocessing, and thus high equipment cost.
  • [0022]
    The object of the invention is to devise a process and a device with which fibers, especially extremely fine fibers, can be produced for filtration purposes, and additives or organic solvents will be abandoned and the process can be carried out economically.
  • [0023]
    This object is achieved with a process in which as the polymers homopolymers of polyacrylonitrile, polyamide or cellulose acetate are used, the suspension is heated in a tank to a temperature T which is at least 60 above the boiling point of the water and at least 30 C. below the softening temperature of the polymer and at which the at least plasticized polymer mass which has been obtained in this way is discharged through at least one nozzle means at least using the autogenous pressure of superheated water.
  • [0024]
    It has been ascertained unexpectedly that under these conditions a degree of plasticization of the polymer material is achieved which allows extrusion by suitable nozzle systems. An at least plasticized polymer mass is defined as a polymer mass which can contain dissolved portions. It cannot be precluded and is in part even advantageous that at least some of the polymer under the given pressures and temperatures is in a dissolved state, the water acting as the solvent. To achieve fine fibers a dissolved state of the polymer is advantageous. But it has been found that establishing a completely dissolved state of the polymer is very complex with respect to plant configuration and process guidance. Since proceeding from a predominantly plasticized state the required fiber finenesses can be achieved, the latter state represents a more economical version. By partially dissolving the polymer material the fiber strength and thus the strength of the fiber agglomerates produced from them can be increased.
  • [0025]
    Fibers are formed at the nozzle outlet by stretching the plasticized polymer mass in a shear field of the spontaneously vaporizing water. Stabilization of shape is achieved by the instantaneous cooling of the fibers as a result of removal of the vaporization heat of the superheated water.
  • [0026]
    The fibers are thus shaped by the configuration of the nozzle means, especially a capillary nozzle via which the superheated fluid is released into a area of much lower pressure and lower temperature.
  • [0027]
    The extremely fine fibers are produced predominantly for use in filter media for liquid filtration. Accordingly the fiber quality is assessed according to the filtration behavior of the deep filter papers. Their use is not however limited to this area. Their use is conceivable in nonwoven materials, for example in filter nonwovens for air filtration or as additives to special papers. Due to their large specific surface they can be used to advantage in chromatographic processes or selective adsorption processes in which they can be used as a carrier material for specific ligands. Compared to particular carrier materials microfiber networks due to their pores through which flow can take place offer the advantage that a large portion of the surface is made accessible to the flowing medium and thus the contact time necessary for formation of specific interactions is shortened.
  • [0028]
    The application liquid filtration substantiates the minimum requirements which must be met by the fibers produced as claimed in the invention: Very fine fiber dimensions (the fiber diameter should be less than 5 microns, preferably below 1 micron) are required which go along with a high specific surface from 5 to 30 m2/g (determined using the BET process). If these fibers are combined into networks or agglomerates with dimensions which are orders of magnitude greater than the fiber dimensions, a highly porous system is formed.
  • [0029]
    A filter layer can be produced by homogenous embedding of microfibers or their agglomerates into a matrix of coarser fibers (for example, cellulose pulp) or when used as a precoat material; this filter layer allows mechanical separation of particular sediments of unstable shape (for example, microorganisms) up to a size of 0.2 microns. By adsorption the minimum separable particle size can be further reduced. A homogenous distribution of the microfibers in the matrix presupposes a narrow range of variation in fiber diameters which is maintained by the process as claimed in the invention.
  • [0030]
    In the preferred application of clear filtration it must be ensured that the filtration medium is completely inert to the filtered material. This is achieved by the use of a suspension without organic solvents and additives which does not contain components which can be eluted by aqueous or alcohol solutions, for example softeners, solvent residues, but also hydrolysis products which could lead to contamination in an adverse case. For applications in less critical domains than in the pharmaceutical or food industry also small residues of softeners among others can be tolerated. In this way the use of economical raw materials is optionally possible. The advantage of the process that no solvents need be circulated and thus cannot be contained in the product is preserved. Furthermore the polymer can be easily wetted to keep the flow resistance of the filter medium low and to ensure a homogenous flow-through and thus uniform loading of the filter material.
  • [0031]
    In the area of deep filter layer production the microfibers enable replacement of mineral auxiliary filter agents such as kieselguhr, perlites or aluminosilicates.
  • [0032]
    In applications other than liquid filtration the replacement of glass fibers in air filter nonwovens is conceivable; their very fine types represent a health hazard due to the ease of their reaching the lungs. This enumeration is intended for example to represent the use of extremely fine fibers without precluding an application beyond it.
  • [0033]
    This temperature provided as claimed in the invention is advantageous in that in this way a corresponding pressure can be built up in the pressure vessel and the water is superheated to the extent that when the plasticized mass emerges from the capillary nozzle the desired shear field is built up.
  • [0034]
    Furthermore, it is advantageous if the aqueous suspension is heated only to a maximum 30 C. below the softening temperature of the respective polymer in order to prevent overly strong melting of the polymer.
  • [0035]
    Preferably polyamide 6 or polyamide 6, 6 is used as the polyamide.
  • [0036]
    The softening temperatures of the polymers are as follows:
  • [0037]
    PAN: 305-310 CA (diacetate): 225-250
  • [0038]
    PA 6: 215-220 CA (triacetate): 290-310
  • [0039]
    PA 6, 6: 255-260
  • [0040]
    Preferably cellulose diacetate or cellulose triacetate is used as the cellulose acetate. The degree of acetylation is preferably 2.5 for diacetate and 2.9 to 3 for triacetate.
  • [0041]
    Advantageously the cellulose acetate has an acetic acid content of 52-56%.
  • [0042]
    It has been shown that by means of the process as claimed in the invention polymers such as PAN, which normally cannot be extruded, can also be extruded because the water assumes the function of a lubricant.
  • [0043]
    The suspension is preferably kept at the temperature T for a maximum 240 sec. The preferred maximum times for the individual polymers are as follows:
  • [0044]
    Cellulose diacetate: max. 60 seconds
  • [0045]
    Cellulose triacetate: max. 90 seconds
  • [0046]
    PA: max. 120 seconds
  • [0047]
    PAN: max. 240 seconds
  • [0048]
    While PAN and PA have low susceptibility to thermal damage, it is of special importance in cellulose acetate not to exceed an interval of 60 seconds and 90 seconds. In cellulose acetate decomposition by hydrolysis and oxidation occurs under certain circumstances. Hydrolysis can begin at 200 C. due to easy water repellency. Cellulose acetate at high pressures and temperatures can intercalate water molecules between the polymer molecules. Due to the presence of water it has been surprisingly found that cellulose acetate can be quickly heated even into the area of the softening point and can be extruded jointly with water without the cellulose acetate being seriously damaged.
  • [0049]
    Preferably the suspension is continuously mixed during heating.
  • [0050]
    Preferably the polymer concentration in the suspension is 1 to 10% by mass.
  • [0051]
    Preferably the fibers are discharged in a space with a pressure≦atmospheric pressure. It is complex to establish a fine vacuum and entails only few advantages with respect to turbulence for fiber formation. Practicable vacuum values are preferably up to 0.8 bar.
  • [0052]
    Advantageously the suspension is exposed to a pressure between 15 and 25 bar during heating.
  • [0053]
    Preferably a polymer powder with grain sizes between 20 and 100 microns is used. So-called flakes can also be used with dimensions up to 10 mm.
  • [0054]
    The device for continuous production of filtration-active fibers from PAN, PA or cellulose acetate has a storage tank for preparing the suspension and a mixing tank which is connected to the storage tank and which is made for heating an aqueous polymer suspension under pressure. At the output of the mixing tank there is a nozzle means for discharge of the plasticized polymer mass.
  • [0055]
    The nozzle means has at least one capillary nozzle, one pneumatic nozzle, one needle valve or one binary nozzle. In the binary nozzle the channel which discharges the suspension is surrounded by an annulus through which steam is expelled at the same time. In this way, on the one hand cooling of the polymers is slowed down and on the other hand turbulence is increased; both have a beneficial effect on fiber formation.
  • [0056]
    Preferably there are three capillary nozzles adjacent to one another; their outlet openings are aligned at an acute angle to one another. This arrangement has the advantage that the turbulence field is intensified at the site of formation of extremely fine fibers. The diameter of the capillary nozzles is preferably 0.1-10 mm.
  • [0057]
    For example, for production of fibers with a diameter of 1-10 microns capillary nozzles with a diameter of 1 mm are suited. The ratio of the length to the diameter of the capillary nozzle is preferably 30-50.
  • [0058]
    Preferably the mixing tank is an extruder.
  • [0059]
    According to another embodiment the mixing tank can have a dispersing means.
  • [0060]
    Advantageously a coarse mixer is connected upstream of the mixing tank.
  • [0061]
    Advantageously behind the nozzle means there is a discharge tank in which a pressure≦atmospheric pressure can be set.
  • [0062]
    In addition there can be another metering pump in front of the nozzle means.
  • [0063]
    Advantageously another heat exchanger can be connected upstream of the mixing tank.
  • [0064]
    The process can be carried out both in batches and also continuously. Fundamentally for both types of processes the same structure of the device can be used, and in batch operation delivery means in front of the mixing tank can be abandoned.
  • [0065]
    One sample embodiment of the device is detailed below using the drawings.
  • [0066]
    The figure schematically shows a device for producing extremely fine fibers. The aqueous suspension is prepared in the storage tank 2. The polymer material is used in powdered form and is suspended in water. The grain size and the maximum content of polymers are chosen such that the suspension remains flowable. The grain size of the powder used is therefore preferably between 20 and 100 microns. For reasons of economic efficiency the polymer concentration should be set as high as possible. In practice a polymer proportion in the suspension between 1 and 10% by mass is chosen. At an overly low polymer concentration the space-time yield of the process is no longer economically acceptable. Higher polymer concentrations generally lead to an overly highly viscous mass which can no longer be discharged through the nozzle systems used which are still to be described.
  • [0067]
    By means of a pump 4 the suspension is supplied to a heat exchanger 6 which preheats the suspension so that in the following coarse mixer 8 with the mixing tank 10 the required process temperature is reached as quickly as possible. Although the mixing tank 10 can be heated, preplasticization is necessary because due to the structural length of the mixing tank 10 the suspension could traverse the mixer section too quickly without the process temperature, for example 200 C., being reached. In the continuous process the device should therefore be dimensioned such that a sufficiently high residence time of the suspension at the process temperature is ensured. The homogeneous distribution of the polymer plasticized by heating is ensured by the mixing means in the mixing tank 10.
  • [0068]
    In addition or instead, a suitable dispersing unit, for example a thermostatically controlled Dispax reactor in the mixing tank 10, can also be used. With one such homogenizer an emulsion can be produced which has a beneficial effect on the homogeneity of the fiber dimensions.
  • [0069]
    By heating in the closed mixing tank 10 a correspondingly high pressure from 15 to 25 bar is built up. This pressure ensures that the plasticized polymer mass can be discharged by a nozzle means 16. Advantageously however a metering pump 12 can also be connected in between.
  • [0070]
    The nozzle means 16 consists, as can be seen in the enlargement, of an outlet pipe 18 into which a nozzle head 22 is screwed. Accordingly the outlet pipe 18 has an inner thread 28 and the nozzle head 22 has an outer thread 30. Within the nozzle head 22 there are three capillary nozzles 24 a, b, and c with their outlet openings 26 a, b, and c. The capillary nozzles are made partially curved on their outlet end so that the outlet openings 26 a, b and c meet one another at an acute angle.
  • [0071]
    The morphology of the fibers is largely influenced by the shear field on these outlet openings. In continuous operation the composition of the outlet must moreover ensure that in the system pressure fluctuations are prevented which cause undefined flow conditions. Suitable capillary nozzles therefore have a ratio of length to diameter (L/D ratio) of at least 30 or slit nozzles with an outlet opening which is matched to the internal pressure prevailing in the system.
  • [0072]
    Furthermore also at least a protective screen 20 can be located in front of the capillary nozzles 24 a, b, c, which screen prevents the clogging of the capillary nozzles.
  • [0073]
    Spontaneous vaporization of the superheated water at the outlet openings 26 a to c yields a field of high turbulence in which the plasticized polymer mass is torn into extremely fine fibers. Shaping occurs by stretching and simultaneous cooling of the polymer mixture. The shear field in the case of binary nozzles can be intensified by lateral introduction of superheated steam or hot air. It has been found to be very efficient to group the outlet capillaries and to align at least two outputs at a time at an acute angle to one another.
  • [0074]
    The fibers emerging from the outlet openings 26 a to c into the discharge tank 14 are captured as pulp or deposited on a movable screen 14. The heat which has been released by the fibers is returned via a line 15 to the heat exchanger 6 to preheat the initial suspension. A gradual release of the fibers in a second interposed pressure tank (not shown) can also be done; its pressure is below the process pressure but above the normal pressure.
    TABLE 1
    Parameters for solvent-free production of extremely fine
    CA fibers (process examples)
    Equipment parameters
    Example Sample
    No. Polymer weight Content Nozzle type Note
    3 CA 250 5% needle valve
    4 CA 250 5% needle valve
    5 CA 250 5% pneum. nozzle
    6 CA 750 5% needle valve
    7 CA 750 5% needle valve
    Process parameters
    Tin Tout p flow resid. time in Post- Fiber
    in in in in min treat- dmt.
    C. C. bar 1/h Mixer WT total ment [μm]
    137 205 21 n.b. Ultra- 1-8
    turrax
    134 203 23  24 29 7 36 n.b.
    139 203 23 157 amorph
    145 213 22 n.b. Ultra- amorph
    turrax
    141 200 20 n.b. Ultra- 0.4-2
    turrax
    Equipment parameters
    Example Sample Nozzle
    No. Polymer weight Content type Note
     8 CA 250 5% pneum.
    nozzle
     9 CA 300 1% a) steam
    10 CA 500 10%  a) steam
    11 CA 500 5% a) compressed
    air/steam
    12 CA 200 5% a) compressed
    air/steam
    13 CA 3000  5% needle flow cell
    valve
    a) binary nozzle with discharge mandrel
    Process parameters
    Tin Tout p flow Post- Fiber
    in in in in rsd. time in min treat- dmt..
    C. C. bar 1/h Mixer WT total ment [μm]
    139 198 15 n.b amorph
     /1-7
    136 195 19 n.b   1-3
    135 200 20 n.b.   1-10
    134 198 22 30 23 6 29 Ultra- 0.4-4
    turrax/
    pulper
     49 173 21 40 17 4 21 2
    84  8 2 10 Ultra- 0.1-5
    turrax
    Equipment parameters
    Example Sample Nozzle
    No. Polymer weight Content type Note
    14 CA 125 3% a)
    15 CA 500 2% b)
    16 CA 500 2% c) steam
    17 CA 500 2% c) steam
    a) binary nozzle with discharge mandrel; b) individual capillary;
    c) individual capillary with prefilter, binary nozzle with
    discharge nozzle
    Process parameters
    Tin Tout p flow Fiber
    in in in in rsd. time in min Post- dmt.
    C. C. bar 1/h Mixer WT total treatment [μm]
    25 187 19 90b  8 2 10 amorph
    103  200 20 27b 25 6 31 strips
    42 202 22 17 41 10  51 Pulper, 0.1-1
    refiner
    92 199 21 25 28 7 35 Pulper, amorph
    refiner
    Equipment parameters
    Example Sample
    No. Polymer weight Content Nozzle type Note
    18 CA 750 5% needle valve
    19 CA 750 5% needle valve
    20 CA 200 1% capillary a)
    group +
    needle valve
    21 CA 200 1% capillary a)
    group
    22 CA 1000  5% focussed a)
    capillary
    group
    a) 3 to 60 1 mm (heated)
    Process parameters
    Tin Tout p flow Post- Fiber
    in in in in rsd. time in min treat- dmt.
    C. C. bar 1/h Mixer WT total ment [μm]
     28 201 20 45 15 4 19 a) 0.2-1
     29 199 19 57 12 3 15 a) 1-2
     32 200 20 25 28 7 35 amorph
    136 197 20 100   7 2  9 Pulper n.b.
    138 199 20 105   7 2  9 a) 0.4-5
    a) Pulper, refiner, homogenizer
    Equipment parameters
    Example Sample Nozzle
    No. Polymer weight Content type Note
    23 CA 2000 10% focussed 3 to 35 1
    capillary mm (heated)
    group
    24 CA 2000 10% focussed 3 to 53
    capillary 0.7 mm
    group (heated)
    25 CA  100  1% needle
    valve
    Process parameters
    Tin Tout p flow Fiber
    in in in in rsd. time in min Post- dmt.
    C. C. bar 1/h Mixer WT total treatment [μm]
    138 196 20 87  8 2 10 Pulper,   1-10
    refiner
    HDH
    134 196 22 45 15 4 19 Pulper, 10
    refiner
    HDH
    max. 15 batch 20 0.06-5
    195
  • [0075]
    As is shown in Table 1, different nozzle types were used. Here Tin and Tout are the temperatures in front of the mixing tank and behind the mixer. MI is the mixer, WT is the heat exchanger, and HDH is the high pressure homogenizer.
  • [0076]
    The advantage of the capillary nozzle is that they are very well suited for homogenous discharge of fibers. Needle valves offer the advantage that they are invulnerable to clogs, especially when plasticization has not taken place optimally.
  • [0077]
    The binary nozzles can be operated with steam or with compressed air, the steam or the compressed air emerging through the ring slit. Furthermore, in some examples the length and the nozzle diameter are given in mm.
  • [0078]
    In example 15 fibers with a strip-like appearance were produced.
    TABLE 2
    Process guidance
    Cell. triacet.
    Cell. (No. 18 from
    Parameter diacet. Table 1) PA 6 PAN
    Weighed sample in g 750 450 450 450
    Content in %  5  3  3  3
    Nozzle type Needle valve
    T(in) in C.  28  27  27  26
    T(out) in C. 201 255 187 269
    Pressure p in bar  20  23  22  23
    Flow in L/h  45  43  45  40
    Residence time in  4  4.2  4  4.5
    heat exchanger in
    min.
    Residence time in  15  16  15  17
    mixing tank in min.
    Residence time  19  20.2  19  21.5
    total in min.
    Posttreatment Pulper/refiner/homogenizer
    Attained fiber  0.2 to  0.5 to  0.4 to  0.7 to
    diameter in microns  1  2  1.5  3
  • [0079]
    The residence time in the mixing tank is roughly three times as long as the time during which the suspension is at the temperature T. This can be attributed to the fact that first of all the required heating must take place in the mixing section.
    Reference numbers
     2 storage tank
     4 pump
     6 heat exchanger
     8 coarse mixer
    10 mixing tank
    12 pump
    13 discharge tank
    14 screen
    15 discharge tank
    16 nozzle means
    18 outlet pipe
    20 filter screen
    22 nozzle head
    24a, b, c capillary nozzle
    26a, b, c discharge opening
    28 inner thread
    30 outer thread
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US7566014Mar 30, 2007Jul 28, 2009Kx Technologies LlcProcess for producing fibrillated fibers
US8444808Mar 30, 2007May 21, 2013Kx Industries, LpProcess for producing nanofibers
US20080054107 *Mar 30, 2007Mar 6, 2008Kx Industries, LpProcess for producing fibrillated fibers
US20080057307 *Mar 30, 2007Mar 6, 2008Kx Industries, LpProcess for producing nanofibers
WO2008027094A1 *May 29, 2007Mar 6, 2008Kx Industries LpProcess for producing fibrillated fibers
Classifications
U.S. Classification8/115.51
International ClassificationD01F6/60, D01F6/18, D01D5/11, D01F2/28
Cooperative ClassificationD01F2/28, D01D5/11, D01F6/18, D01F6/60
European ClassificationD01F2/28, D01F6/18, D01F6/60, D01D5/11
Legal Events
DateCodeEventDescription
Mar 26, 2001ASAssignment
Owner name: SEITZ-FILTER-WERKE GMBH, GERMANY
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:LEIBNITZ, RODIGER;KREYE, LARS;MULLER, HEINZ-JOACHIM;REEL/FRAME:011637/0657
Effective date: 20001227
May 21, 2001ASAssignment
Owner name: SEITZSCHENK FILTERSYSTEMS GMBH, GERMANY
Free format text: CHANGE OF NAME;ASSIGNOR:SEITZ FILTER WERKE GMBH;REEL/FRAME:011827/0287
Effective date: 20010331