Abrasion-proof filtration membrane and method of producing said membrane

Abstract

A filtration membrane (1) is provided that includes a porous support (4) and a membrane layer having a first and a second zone (2, 3). The first zone (2) has a thickness of 5 to 15 m and an average pore opening size of smaller/equal 0.4 and the second zone (3) has a thickness of 5 to 40 m and an average pore opening size of 0.5 to 5.0 m. The filtration membrane (1) is produced by forming a single- or -double-layer coating on the porous support (4).

Claims

1. A filtration membrane comprising a porous support, a membrane surface for receiving feed, and a membrane layer with a first and second zone, wherein the first zone has a thickness of 5 to 15 m and a mean pore size of less than or equal to 0.4 m and the second zone has a thickness of 5 to 40 m and a mean pore size of 0.4 to 5.0 m and wherein, said support is a textile nonwoven, wherein the filtration membrane has a clean water permeability of 200 to 2000 L/(m.sup.2.Math.h.Math.bar).

2. The filtration membrane as claimed in claim 1, wherein the first zone has a thickness of 8 to 12 m.

3. The filtration membrane as claimed in claim 1, wherein the first zone has a mean pore size of less than or equal to 0.3 m.

4. The filtration membrane as claimed in claim 1, wherein the second zone has a thickness of 5 to 30 m.

5. The filtration membrane as claimed in claim 1, wherein the second zone has a mean pore size of 0.4 to 2.0 m.

6. The filtration membrane as claimed in claim 1, wherein in the first zone the mean pore size increases with increasing distance from said membrane surface and said first zone is placed next to said membrane surface.

7. The filtration membrane as claimed in claim 6, wherein in the second zone, the mean pore size increases with increasing distance from said membrane surface.

8. The filtration membrane as claimed in claim 6, wherein the second zone is comprised of polysulfone and polyvinylpyrrolidone.

9. The filtration membrane as claimed in claim 1, wherein said filtration membrane has, after an abrasion test lasting 450 h, a mean pore diameter of 0.05 to 0.2 m.

10. A filtration device comprising a filtration membrane as claimed in claim 1.

11. The filtration membrane as claimed in claim 1, wherein the filtration membrane has a clean water permeability of 300 to 2000 L/(m.sup.2.Math.h.Math.bar).

12. The filtration membrane as claimed in claim 1, wherein the filtration membrane has a clean water permeability of 500 to 1000 L/(m.sup.2.Math.h.Math.bar).

13. The filtration membrane as claimed in claim 4, wherein the second zone has a thickness of 10 to 20 m.

14. The filtration membrane as claimed in claim 9, wherein said filtration membrane has, after an abrasion test lasting 450 h, a mean pore diameter of 0.08 to 0.15 m.

15. The filtration membrane as claimed in claim 7, wherein said second zone is placed between said first zone on one side and said porous support on the side opposite said first zone such that the porous support is placed away from said membrane surface.

16. A flat filtration membrane comprising a nonwoven porous support and a membrane layer with a first and second zone and a membrane surface for receiving feed; wherein the first zone is placed next to said membrane surface and said second zone is placed between said first zone on one side and said nonwoven porous support on the side opposite said first zone such that said nonwoven porous support is placed away from said membrane surface; and wherein in the first zone, the mean pore size increases with a mean gradient of 20 to 80 nm per 1 m distance from said membrane surface and in the second zone, the mean pore size increases with increasing distance from said membrane surface; and wherein the first zone has a thickness of 5 to 15 m and a mean pore size of less than or equal to 0.4 m and the second zone has a thickness of 5 to 40 m and a mean pore size of 0.4 to 5.0 m; and wherein the first zone and the second zone are comprised of polysulfone and polyvinylpyrrolidone, and the filtration membrane has a clean water permeability of 200 to 3000 L/(m.sup.2.Math.h.Math.bar).

17. The filtration membrane as claimed in claim 1, wherein the filtration membrane is flat, the membrane surface for receiving feed is comprised within the first zone, the nonwoven is a mechanical stabilizer and said membrane comprises polyvinylpyrollidone.

18. The filtration membrane as claimed in claim 1, wherein the filtration membrane is flat, the membrane surface for receiving feed is comprised within the first zone and in the first zone the mean pore size increases with a mean gradient of 20 to 80 nm per 1 m distance from said membrane surface and in the second zone and the mean particle size increases with a mean gradient of 200 to 800 nm per 1 m distance from said membrane surface, the mean pore size increasing with increasing distance from said membrane surface; and said membrane comprised of a single polymer layer.

Description

BRIEF DESCRIPTION OF THE FIGURES

(1) FIG. 1 is a schematic sectional view of an exemplary inventive membrane;

(2) FIGS. 2 and 3 represent scan lines on an electron micrograph;

(3) FIG. 4 is a graphical illustration of the mean pore diameter as a function of distance from the membrane surface for an exemplary inventive membrane;

(4) FIG. 5 is a graphical illustration of the mean pore size diameter versus distance from the membrane surface for a membrane of prior art;

(5) FIG. 6 is a graphical illustration of the dry and wet capillary flows of an inventive filtration membrane;

(6) FIG. 7 is a graphical illustration of the pore diameter distribution derived from the measurement curves of FIG. 6;

(7) FIGS. 8a and 8b are sectional schematic views of a device for testing abrasion resistance of filtration membranes; and

(8) FIG. 9 is a schematic illustration of an exemplary device for the production of inventive filtration membranes.

DETAILED DESCRIPTION OF ADVANTAGEOUS EMBODIMENTS OF THE INVENTION

(9) Further embodiments of the filtration membrane according to the invention are characterized in that: the first zone has a thickness of 8 to 12 m; the first zone has a mean pore size (mean pore opening diameter) of less than or equal to 0.3 m; the second zone has a thickness of 5 to 30 m; the second zone has a thickness of 10 to 20 m; the second zone has a mean pore size of 0.4 to 2.0 m; in the first zone, the mean pore size (mean pore opening diameter) increases with increasing distance from a surface of the filtration membrane; in the first zone, the mean pore size (mean pore opening diameter) increases with a mean gradient of 20 to 80 nm per 1 m distance from the surface of the filtration membrane; in the second zone, the mean pore size (mean pore opening diameter) increases with increasing distance from a surface of the filtration membrane; in the second zone, the mean pore size (mean pore opening diameter) increases with a mean gradient of 200 to 800 nm per 1 m distance from the surface of the filtration membrane; the filtration membrane has a mean pore diameter of 0.04 to 0.2 m; the filtration membrane has a mean pore diameter of 0.08 to 0.15 m; the filtration membrane has a clean water permeability of 200 to 3000 L/(m.sup.2.Math.h.Math.bar); the filtration membrane has a clean water permeability of 300 to 2000 L/(m.sup.2.Math.h.Math.bar); the filtration membrane has a clean water permeability of 500 to 1000 L/(m.sup.2.Math.h.Math.bar); the filtration membrane, after an abrasion test lasting 450 h, has a clean water permeability of 500 to 3000 L/(m.sup.2.Math.h.Math.bar); the filtration membrane, after an abrasion test lasting 450 h, has a clean water permeability of 800 to 1500 L/(m.sup.2.Math.h.Math.bar); the filtration membrane, after an abrasion test lasting 450 h, has a mean pore diameter of 0.05 to 0.2 m; the filtration membrane, after an abrasion test lasting 450 h, has a mean pore diameter of 0.08 to 0.15 m; the first zone consists of polysulfone and polyvinylpyrrolidone; the second zone consists of polysulfone and polyvinylpyrrolidone; and/or the support is a textile nonwoven.

(10) Essentially, the first and second zones of the membrane layer differ in mean pore size or mean pore diameter, which is determined by the production process. According to the invention, the membrane layer can also be produced by precipitation of a single-layer polymer solution so that the first zone has a seamless transition to the second zone.

(11) In the context of the present invention, the term mean gradient refers to the slope of a regression line for the mean pore size (mean pore opening diameter) applied as a function of distance from the surface of the filtration membrane, as shown for example in FIG. 4.

(12) The invention also concerns a filtration device that includes one or more filtration membranes of the type described above.

(13) A further object of the present invention is to provide a process for the production of filtration membranes of the type described above.

(14) This object is achieved by means of a first process comprising the following steps: Preparation of a porous support in sheet form; Optionally, coating of the support with a first polymer solution of one or more polymers and a first solvent, wherein the concentration of the polymer in the first solvent has a value C1; Coating of the support with a second polymer solution of one or more polymers and a second solvent, wherein the concentration of the polymer in the second solvent has a value C2 that is larger than C1; Application to the surface of the second polymer solution of a first vaporous precipitation bath; and Precipitation of the second and optionally the first polymer solution, wherein the support coated with the second and optionally the first polymer solution is fed through a second liquid precipitation bath.

(15) Advantageous embodiments of the first process according to the invention are characterized in that: the first and second solvent are identical; the polymer or polymers of the first and second polymer solution have an identical chemical composition; concentration C1 is in the range of 15-19%; concentration C2 is in the range of 17-21%; the polymers of the first and second polymer solution are the same or different and are selected from the group comprising polyethersulfone, polysulfone, polyvinylpyrrolidone, polyvinylidene fluoride, and mixtures thereof; the first and second solvent are the same or different and are selected from N-methylpyrrolidone, N-ethylpyrrolidone, dimethylacetamide, dimethylformamide, acetone, or mixtures thereof; the first precipitation bath is evaporated by heating or converted into an aerosol by means of a sputtering device; and/or the first and second precipitation baths are the same or different and constitute water or a mixture of water with one or more solvents selected from the group comprising N-methylpyrrolidone, N-ethylpyrrolidone, dimethylacetamide, dimethylformamide, acetone, or mixtures thereof.

(16) An alternative second process for the production of the filtration membrane according to the invention comprises the following steps: Preparation of a porous support in sheet form; Coating of the support with a polymer solution of one or more polymers and a first solvent; and Transport of the support with the polymer solution through a first precipitation bath composed of a first precipitant, a second solvent, and optionally additives, over a segment L measuring 0.4 to 2.0 m, wherein the concentration of the second solvent decreases over segment L from a starting value of 10 to 40 vol % to an end value of 0.5 to 5 vol %.

(17) Advantageous embodiments of the second process according to the invention are characterized in that: the support coated with the polymer solution is passed through a second precipitation bath, wherein the second precipitation bath consists of a second precipitant, optionally a third solvent, and optionally additives; the first, second, and third solvent are identical; the first and second precipitant are identical; the polymers of the polymer solution are selected from the group comprising polyethersulfone, polysulfone, polyvinylpyrrolidone, polyvinylidene fluoride, and mixtures thereof; the first, second, and third solvent are the same or different and are selected from N-methylpyrrolidone, N-ethylpyrrolidone, dimethylacetamide, dimethylformamide, acetone, or mixtures thereof; the concentration of the polymers in the polymer solution is 15 to 21 wt. %.; the concentration of the first solvent in the first precipitation bath decreases over segment L with a gradient of 2.5 to 98.8 vol %.Math.m.sup.1, preferably 10 to 98.8 vol %.Math.m.sup.1, and more preferably 20 to 98.8 vol %.Math.m.sup.1; the support coated with the polymer solution is transported at a rate of 1 to 120 m/min, and preferably 4 to 30 m/min, through the first precipitation bath; the first precipitant is water; the concentration of the first precipitant in the first precipitation bath varies within a range of 60 to 99.5 vol %; the second precipitant is water; and/or the concentration of the second precipitant in the second precipitation bath is 80 to 99.9 vol %, preferably 90 to 99.5 vol %, and more preferably 95 to 99.5 vol %.

(18) The invention is described in greater detail below with reference to figures. The figures are as follows:

(19) FIG. 1 is a schematic sectional view of a membrane;

(20) FIGS. 2-3 show scan lines on an electron micrograph;

(21) FIG. 4 shows the mean pore size (mean pore opening diameter), determined by means of electron microscopic sectional images, of a membrane according to the invention as a function of distance from the membrane surface;

(22) FIG. 5 shows the mean pore size (mean pore opening diameter) of a membrane of prior art;

(23) FIG. 6 shows measurement curves of the dry and wet capillary flow of a filtration membrane of the invention according to ASTM F 316-03 (2011);

(24) FIG. 7 shows the pore diameter distribution derived from the measurement curves of FIG. 6;

(25) FIGS. 8a-8b show sectional views of a device for testing abrasion resistance of filtration membranes; and

(26) FIG. 9 shows a device for the production of filtration membranes.

(27) In the present application, the filtration membranes according to the invention are described based on parameters that are measured directly or derived from measured values. Here, morphological terms such as number, shape, size, volume, inner surface, and arrangement of pores are not to be taken literally, but are to be understood as the direct or indirect result of a measurement, taking into consideration the models and mathematical methods used to analyze the measurement results.

(28) The filtration membranes according to the invention are characterized in particular by the following four parameters: mean pore size (or mean pore opening diameter), mean pore diameter, clean water permeability, and abrasion resistance,
which are explained in greater detail in the following.

(29) FIG. 1 shows a schematic sectional view of a filtration membrane 1 according to the invention, comprising a membrane layer (2, 3) with surface 9 and a porous support 9, which is preferably a nonwoven composed of synthetic fibers.

(30) Mean Pore Size (Mean Pore Opening Diameter)

(31) The mean pore size or mean pore opening diameter is determined using membrane microtome sections by screen transmission electron microscopyreferred to in the following as RTEM or STEMin combination with computerized image analysis. For this purpose, a piece of the filtration membrane to be examined having dimensions within a few centimeters is punched out, cooled with liquid nitrogen, and cut using an ultramicrotome into a thin section sample oriented perpendicular to the membrane surface 9 with a thickness of 400 to 600 nm. The thin section sample is arranged on a copper grid coated with Formvar provided by sputtering with a platinum layer about 5 nm in thickness. The copper grid with the platinum-coated thin section sample is mounted on the sample holder of an RTEM, e.g. the Philips CM 12. The sample chamber of the RTEM is then evacuated to a pressure of about 10.sup.6 mbar and an image of the thin section sample is captured. A photographic film or the bright field detector of the RTEM is used to capture the image. The beam power of the RTEM and the current intensity of the electron beam in particular are minimized in order to avoid damage to the thin section sample to a large extent.

(32) The surface of the thin section sample imaged by RTEM is rectangular, with a first rectangular side H running perpendicular to the membrane surface 9 and a second rectangular side B running parallel to the membrane surface 9. The lengths of the rectangular sides H and B are at least 10 m and 30 m respectively, so that the imaged surface has an area of at least 300 m.sup.2.

(33) The maximum lateral resolution of the RTEM is in the range of 0.5 to 1 nm and is largely sufficient to reliably resolve pores with a diameter as small as 10 nm. At a resolution of about 1 nm, the images captured with the RTEM contain at least 310.sup.8 picture elements or pixels, which corresponds to a data volume of 300 MB for a grayscale image with 8 bit color depth or 256 gray levels. If the bright field detector of the RTEM is used to capture the image, the signals or image data during screen scanning of the electron beam are written to a DRAM-based frame buffer and transferred to a hard disk. Alternatively, the image may be captured using photographic film.

(34) The thin section samples include platinum-coated membrane material that is interspersed with pore openings. The electron beam passes through the pore openings unhindered and is detected with maximum intensity, while the platinum-coated membrane material almost completely absorbs the primary electron beam, so that no intensity is detected. For this reason, the image of a thin section sample captured by RTEM is characterized by high contrast. Because of the high RTEM contrast, the gray value histogram of the RTEM images has a bimodal profile with a sharply pronounced minimum G.sub.Min, wherein dark image areas or pixels with a gray value less than G.sub.Min represent membrane material and light pixels with a gray value greater than G.sub.Min represent pore openings. In this manner, in image analysis using the gray value minimum G.sub.Min, each image area or each pixel can be clearly identified as membrane material or a pore opening. The RTEM images of the thin section samples essentially correspond to binary images in which each pixel is either black (gray value 0) or white (gray value 255).

(35) If photographic film is used for capturing the RTEM images rather than the bright field detector, the film negatives or prints produced therefrom are digitized by means of a scanner. A commercially available flat bed or negative scanner with an optical resolution of 4800 dpi or 7200 dpi is used for this purpose.

(36) The digital images obtained by RTEM or the optical photo scan are subjected to computer-aided image analysis that includes the following steps: Determination of the gray value histogram and determination of the minimum G.sub.Min, i.e., determination of the gray value with the lowest frequency or the smallest number of pixels with this gray value; Conversion to a binary image with the previously determined minimum G.sub.Min as the threshold, wherein all pixels with a color value less than or equal to G.sub.min are assigned the gray value 0 (=black) and all other pixels are assigned the gray value 255 (=white); (in order to reduce the amount of data by , it is advantageous to represent the gray value with the number or the bit 1); Line-by-line analysis of the binary image with scan lines running parallel to the membrane surface 9, by the following method: (i) all pixel values of the scan line are added, with the sum of the pixel values corresponding to the total length of all white line segments (or 255 times the total length if the gray value white is represented by the number 255); (ii) a copy shifted by one pixel is subtracted from the scan line and the sum of the difference line is calculated, with said sum of the difference line corresponding to the number (or 255 times the number) of the white segments in the scan line; (iii) the quotient of the sums determined in steps (i) and (ii) is calculated; this quotient represents the mean length of the white segments of the scan line; Repetition of steps (i) to (iii) for all other scan lines running parallel to the membrane surface 9.

(37) The scan lines of the binary image running parallel to the membrane surface 9 correspond to vectors or n-tuples.

(38) For example, a scan line can be given the gray value shown in FIG. 2, with the first and second white segments having lengths of 6 and 8 respectively. Accordingly, the first and second white segments contribute the summands 6 and 8 to the sum of the scan line calculated according to step (i).

(39) FIG. 3 illustrates step (ii), in which the number of white segments of the scan line is determined, with a copy shifted by one pixel being subtracted from the scan line, with the proviso that the pixel difference 01 is assigned the result 0.

(40) The number of white segments of the scan line is then determined from the sum of the pixel values of the difference line.

(41) Steps (i) through (iii) for line-by-line calculation of the mean length of the white segments, i.e., the mean pore size or mean pore diameter, can easily be conducted using software. Using a commercially available PC from Intel or AMD with a multicore microprocessor and 4 GB of internal memory, an RTEM image of a thin section sample with an image file size of 600 MB can be analyzed in under 10 seconds.

(42) The mean pore size or mean pore diameter determined by the above method represents the pore size available for the passage of a liquid flowing through the filtration membrane in the plane of the thin section sample and perpendicular to the membrane surface 9. The mean pore size or mean pore diameter provides insufficient information on three-dimensional pore structure; it constitutes a reduction of the three-dimensional pore morphology to a two-dimensional parameter.

(43) FIG. 4 shows the result of an analysis of a thin section sample of a filtration membrane according to the invention. FIG. 5 shows, for comparison purposes, the result of an analysis of a high asymmetric membrane known from prior art.

(44) Mean Pore Diameter

(45) Mean pore diameter depends on the determination method. In the application, this parameter is understood to mean the pore diameter commonly referred to in the English-speaking world as mean flow pore diameter, which is determined by capillary flow porometry according to the standard ASTM F 316-03 (2011). This mean pore diameter represents the mean value of the equivalent diameter of the narrowest site of all of the pores interspersed in the filtration membrane through which a liquid can flow. Completely closed and impermeable pores that have dead ends are omitted from capillary flow porometry measurements.

(46) The measurements according to ASTM F 316-03 (2011) can be conducted, for example, using capillary flow porometers manufactured by the firms IB-FT, Quantachrome, or Porous Materials Inc.

(47) In the present case, a capillary flow porometer of the type POROLUX 1000 manufactured by IB-FT is used. POREFIL (surface tension 16 mN/m) from Benelux Scientific is used for wetting the membranes. FIGS. 6 and 7 show the porometry measurement curves of a filtration membrane according to the invention having a mean pore diameter of about 46 nm.

(48) Clean Water Permeability

(49) The clean water permeability of the membranes according to the invention is measured with purified water (PW) at a temperature of 20 C. in a pressure range of 0.1 to 1 bar using conventional centrifugal filter units (e.g. Millipore's AMICON).

(50) Abrasion Resistance

(51) Abrasion resistance is determined by a specially developed, highly application-oriented test method. This involves a miniature MBR reactor without vacuum extraction of the permeate. The reactor is operated with water and cleaning granules, with this mixture being caused to circulate and act abrasively on the membrane surface by blowing air into the reactor. The specific volume of granules and specific air volume is extremely high compared to actual application in order to accelerate abrasion and obtain conclusive results within a short period.

(52) FIGS. 8a and 8b show schematic sectional views of the test equipment from a lateral perspective and in plan view. The test equipment includes flat membrane samples that are stretched onto supports 2 mm in thickness, such as PVC sheets. Each of the supports is 21 cm wide and 30 cm high. In order to allow simultaneous testing of multiple samples, four supports are arranged parallel to each other in a housing having a rectangular base surface and an open top and bottom, i.e., arranged with a cross section through with material can freely flow in a vertical direction such that the upper surfaces of the supports or the flat membrane samples stretched onto the supports are vertically oriented. The free gaps or distances between adjacent membranes or supports and between the outer membranes and the wall of the housing are 8 mm respectively. The free gaps form channels for water, air bubbles, and cleaning granules to flow upward. A ventilation system for blowing air in is mounted at a distance of 4 cm below the membranes or the lower edge of the supports. This system consists of 4 copper tubes arranged evenly over the width of the housing having outer diameters of 10 mm. In order to blow in air, holes 0.5 mm in diameter are installed at intervals of 5 mm from one another in the upward flow area, i.e., on the upper side of the copper tubes. The four aeration tubes are connected via a common air manifold and are supplied with compressed air via a connector. The housing with the membranes and the aeration system is completely submerged in a water-filled tank. The tank is dimensioned in such a way that the horizontal distance between the inner walls of the tank and the outer walls of the housing is 20 mm in each case. The free gaps between the inner walls of the tank and the outer walls of the housing form outflow channels in which water and cleaning granules flow downward.

(53) The test equipment is operated with drinking water and cleaning granules composed of polyurethane-based thermoplastic elastomers. The density of the granules is 1.02-1.04 kg/L. The granules have a lenticular (ellipsoid) shape, with a minimum diameter of about 3.5 mm and a maximum diameter of about 5 mm. The reactor is charged with 60 kg of cleaning granules per m.sup.3 of water and is larger than in actual application by a factor of approximately 10.

(54) The equipment is operated at a total air flow rate of 6 m.sup.3/h. The ratio of the air volume to the entire cross-sectional area it flows over is also referred to as superficial velocity, and it is approx. 0.18 m/s and is therefore greater than in actual application by a factor of 4. Because of the high air volume, water is discharged. A constant water level is maintained by constant addition and overflow of water.

(55) The equipment is operated continuously for 450 h under the above-mentioned conditions. The membrane samples are then removed and characterized according to the above-described methods (clean water permeability, mean pore diameter).

(56) FIG. 9 shows a device 100 for the production of filtration membranes according to the second production method of the invention. The device 100 includes a plurality of rollers 141, 142, 143, 144, and 145 for the supply or unwinding, transport and winding of a porous support in sheet form 4. The unwinding, transport, and winding of the support 4 are indicated by arrows 146. The rate at which the support is transported is 1 to 120 m/min, and preferably 4 to 30 m/min. By means of a known spraying device, a gravure roll, or a pouring device 150, a polymer solution is applied to the support 4 and molded by means of a doctor blade 151 into a layer of essentially constant thickness. It is advantageous to install, underneath the spraying device, gravure roll or pouring device 150 and the doctor blade 151, an essentially planar and smooth bearing 152 over which the support 4 slides. The thickness of the layer of polymer solution applied to the support 4 is adjusted in a known manner via the gap and/or the force with which the doctor blade 151 is pressed against the bearing 152.

(57) After application of the polymer solution, the support coated with polymer solution 4 is fed via an air gap A into a first precipitation bath 160. The length of the line L running from the support 4 in the first precipitation bath 160 is 0.4 to 2.0 m. The first precipitation bath 160 is provided in a channel 161 having a small volume. The channel 161 is configured in the form of a flat tube of rectangular cross section and is bounded by two walls 162 and 163 in the drawing plane of FIG. 9. The distance or clearance between the walls 162 and 163 is 5 to 50 mm, and preferably 5 to 20 mm, in order to keep the volume of the first precipitation bath as low as possible. The walls 162 and 163 are inclined with respect to the vertical, i.e., at an angle with 1080, and preferably 2070 in the drawing plane of FIG. 9.

(58) The channel 161 is provided with one or more supply lines 164, 165, 166 and at least one discharge line 167. The supply lines 164, 165 and 166 are preferably arranged along line L at a constant distance D from each other. Each of the supply lines 164, 165, 166 is connected to a precipitation liquid storage tank, not shown in FIG. 9, with the concentration of solvent in the precipitation liquid decreasing along line L in the transport direction of the support 4. Preferably, the supply lines 164, 165, 166 are equipped with electronically controlled valves, not shown in FIG. 9, which make it possible to control the volume of precipitation liquid supplied from the respective storage tank to the channel 161 per unit time with a preset concentration of solvent.

(59) In an advantageous embodiment of the device 100, one or more electrochemical or spectroscopic in-line sensors are also arranged inside the channel 160, said sensors being used to measure the concentration of solvent in the first precipitation bath along line L and send the corresponding measured values as input signals to a programmable logic controller (PLC). In this type of embodiment of the device according to the invention 100, the electronically controllable valves in the supply lines 164, 165, 166 are connected to the programmable logic controller so as to provide a control circuit for adjusting the solvent concentration in the first precipitation bath 160.

(60) The minimum of one discharge line 167 is advantageously arranged at the end of line L or close to the lowest point of the channel 161 and connected to a collecting tank not shown in FIG. 9 and optionally to a device for solvent recovery or treatment and recirculation of the first precipitation bath 160. In an advantageous embodiment of the device 100, the discharge line 167 is connected to a suction pump, which creates a slight vacuum at the end of line L and reduces fluid transfer from the first precipitation bath 160 to a subsequent second precipitation bath 180.

(61) The channel 161 is connected to a second precipitation bath 180 which is kept in a container 181. The first precipitation bath 160 is in fluid communication with the second precipitation bath 180 via an opening 182. The support 4 coated with the polymer solution is fed through the opening 182. The opening 182 is dimensioned such that the distance between the support 4 and the edge bordering the opening 182 is 3 to 15 mm, preferably 3 to 10 mm, and more preferably 3 to 8 mm, and such that fluid transfer from the first precipitation bath 160 to the second precipitation bath 180 is minimized.

(62) After leaving the second precipitation bath 180, the support 4 with the membrane layer created by precipitation of the polymer solution is optionally fed through a dryer and/or impregnation device not shown in FIG. 9 and wound onto the roller 145.