WO2013142000A1

WO2013142000A1 - Device and process for producing a reinforced hollow fibre membrane

Info

Publication number: WO2013142000A1
Application number: PCT/US2013/026979
Authority: WO
Inventors: Steven Kristian Pedersen; John David Ireland
Original assignee: General Electric Co
Current assignee: General Electric Co
Priority date: 2012-03-22
Filing date: 2013-02-21
Publication date: 2013-09-26
Anticipated expiration: 2014-09-22
Also published as: TWI583437B; CN104203376A; KR20140147839A; TW201406451A; DE112013001583T5; US8999454B2; CN104203376B; US20130251909A1

Description

TITLE: DEVICE AND PROCESS FOR PRODUCING A REINFORCED HOLLOW

FIBRE MEMBRANE

FIELD

[0001 ] This specification relates to devices and processes for producing reinforced hollow fiber membranes, for example hollow fiber membranes for use in microfiltration or ultrafiltration.

BACKGROUND

[0002] Hollow fiber membranes can be made from a variety of polymers by different methods. One method involves non-solvent induced phase separation (NIPS) as taught for example in US Patents 3,615,024; 5,066,401 ; and, 6,024,872. Another method involves thermally induced phase separation (TIPS) as taught for example in US Patents 4,702,836 and 7,247,238. The membranes may have separation layers on their inner surfaces or their outer surfaces and may be used, for example, for microfiltration (MF) or ultrafiltration (UF).

[0003] The strength of a hollow fiber membrane can be increased by coating a membrane dope on a pre-formed tubular braid. US Patents 5,472,607 and 6,354,444 to Mahendran et al. teach coating a membrane on the outside of a braid with limited penetration. US Patent 4,061 ,861 to Hayano et al., US Patent 7,267,872 to Lee et al., and US Patent 7,306,105 to Shinada et al. also teach braid supported membranes. Hollow fiber membranes made according to the teachings of Mahendran et al. have been successfully commercialized.

[0004] Another approach that has been proposed for making a reinforced hollow fiber membrane involves embedding fibers within the wall of a hollow fiber while the hollow fiber is being cast. US Publication 2002/0046970 to Murase et al., International Publication WO 03/097221 to Yoon et al. and US Patent 6,454,943 to Koenhen describe methods of embedding a monofilament or a multi-filament yarn longitudinally within the wall of a hollow fiber. INTRODUCTION

[0005] The following introduction is intended to introduce the reader to the detailed description to follow and not to limit or define the claims.

[0006] This specification will describe an alternative device and process for making a reinforced membrane in which one or more reinforcing yarns are embedded in the walls of the hollow fibre membrane. The resulting membrane may be used, for example, to provide water treatment by microfiltration or ultrafiltration.

[0007] A hollow fibre spinning nozzle described in the specification discharges one or more reinforcing yarns from one or more yarn passages with openings at or near a plane where the dope exits the nozzle. Alternatively or additionally, a discharge opening of a yarn passage may be in or near the same plane as a discharge opening of dope passage. A dope passage may be located inside of the one or more yarn passages, outside of the one or more yarn passages, or both. There is no dope inlet to the one or more yarn passages and, preferably, there is essentially no dope in the one or more yarn passages when the nozzle is in use.

[0008] A reinforcing yarn is typically a multifilament yarn, but may also be a monofilament. If there are multiple reinforcing yarns, there may be multiple discrete yarn discharge openings spaced in a ring around a longitudinal axis of the nozzle. Optionally, a reinforcing yarn comprises filaments having a polymer, at least on the outer surface of the filaments, that is wetted by the dope; a surface treatment that increases wetting by the dope; or, both. Optionally, a reinforcing yarn may be wetted with a solvent before it contacts the dope. [0009] In some of the prior art methods of making reinforced hollow fibre membranes, the reinforcement is pulled into a passage through a spinneret, passes through dope that is injected into the same passage, and then exits the passage with some of the dope. In these prior art methods, dope tends to leak out of the spinneret from an inlet orifice where the reinforcement enters the spinneret. This problem is inherent because the dope is under pressure and the reinforcement enters the spinneret from ambient atmospheric pressure. Attempting to solve this problem with sealing devices is complicated and can cause fraying and damage to the reinforcement. In contrast, discharging a reinforcing yarn from a yarn passage at or near a plane where the dope exits a nozzle, or in or near the plane of a discharge opening of a dope passage, as described in this specification, places the reinforcing yarn in communication with the dope where the dope is at or near atmospheric pressure. This at least reduces the tendency for dope to leak out of the nozzle through the yarn passage.

[0010] Some of the prior art methods pass reinforcements through an annular dope passage. Although the reinforcements may enter the dope passage with a preferred spacing or placement, the reinforcements may move relative to each other in the annular dope passage. Accordingly, multiple reinforcements do not necessarily exit the spinneret equally spaced from each other. Optionally discharging multiple reinforcing yarns through discrete spaced openings at or near a plane where the dope exits the nozzle, as described in this specification, tends to result in more evenly spaced reinforcing yarns.

[001 1 ] The inventors have also observed that a material amount of force is required to pull a reinforcement through a passage filled with dope in a spinneret. The cross section of a membrane made from such a spinneret also tends to be distorted relative to a desired annular cross section. Without intending to be limited to any particular theory, the inventors believe that tension applied to a forming membrane as it passes around a roller in a coagulation bath tends to distort the cross section of the resulting hollow fibre membrane. Since the dope is viscous, pulling the reinforcement through a reservoir of dope that is not flowing at the membrane making line speed puts the reinforcing yarns under a material amount of tension. A nozzle tested in this specification resulted in a significant reduction in the force required to pull reinforcing yarns through the nozzle at a given line speed. These results suggest that a nozzle that discharges a reinforcing yarn from a yarn passage at or near a plane where the dope exits the nozzle, or in or near the plane of a discharge opening of a dope passage, without injecting dope into the yarn passage, will help produce a hollow fibre membrane with an embedded reinforcing yarn and a generally annular cross section. BRIEF DESCRIPTION OF FIGURES

[0012] Figure 1 is an isometric view of a nozzle for making a reinforced hollow fibre membrane, with the nozzle cut along its longitudinal axis.

[0013] Figure 2 is a back view of another nozzle for making a reinforced hollow fibre membrane.

[0014] Figure 3 is a side view of the nozzle of Figure 2.

[0015] Figure 4 is a front view of a nozzle of Figure 3.

[0016] Figure 5 is a cross section of the nozzle of Figure 2 along the line A-A in Figure 2. [0017] Figure 6 is a cross section of the nozzle of Figure 2 along the line B-B in Figure 2.

[0018] Figure 7 is a cross section of the nozzle of Figure 2 along the line C-C in Figure 2.

[0019] Figure 8 is an enlarged view of the area G shown in Figure 4. [0020] Figure 9 is an enlarged view of the area H shown in Figure 5.

[0021 ] Figure 10 is a cross section of a hollow fibre membrane that may be produced from the nozzle of Figure 1 or the nozzle of Figures 2 to 9.

[0022] Figure 1 1 is a schematic view of a coagulation bath with a tension guage used in an experimental example. DETAILED DESCRIPTION

[0023] Figure 1 shows a nozzle 100 cut open along a plane parallel to its longitudinal axis 102. Internal passages in the nozzle 100 provide a number of zones for moving different materials through the nozzle 100. These passages all discharge through discharge openings located in a common plane defined by the front face 104 of the nozzle 100. The nozzle 100 is typically located in use with its front face 104 oriented horizontally. The different materials are discharged vertically downwards from the nozzle 100 and fall through an air gap into a coagulation bath to form a membrane. [0024] Starting at the longitudinal axis 102, the first zone A carries a bore fluid along the longitudinal axis 102. The bore fluid may be a liquid or a gas, such as air, and is used to form a lumen within the resulting membrane.

[0025] The second zone B carries a membrane dope. In general, the dope is a mixture of one or more polymers which will form the membrane wall in a solvent. There may also be other minor ingredients such as a non-solvent or weak non-solvent and a hydrophilic additive.

[0026] The third zone C carries one or more reinforcing yarns. The reinforcing yarns are described further below in relation to Figure 10. Zone C is preferably subdivided, at least where it opens to the front face 104 of the nozzle 100, into a plurality of discrete passages. Typically, one or more reinforcing yarns pass through each discrete passage although one or more of the passages may optionally be left empty. The passages in zone C also communicate with a solvent passage 106. The solvent passage 106 is used to inject a solvent, typically the same solvent that is used in the membrane dope, into the reinforcing yarn passages. This solvent pre-wets the reinforcing yarns, reduces a flow of air through zone C, and also helps prevent dope from entering the reinforcing yarn passages.

[0027] The fourth zone D carries a second flow of membrane dope. Optionally, zones B and D may be in communication with each other inside of the nozzle 100 so that one dope inlet can feed both of zones B and D. Dope can be injected into the nozzle 100 from a pot pressurized with nitrogen, or using a positive displacement pump. The dope may be provided at a temperature in the range of about 15 to 200 degrees C and at a pressure in the range of about 20 to 400 kPa.

[0028] In use, annular streams of membrane dope are discharged from zones B and D through the front face 104 of the nozzle 100. At the same time, one or more reinforcing yarns are pulled through the nozzle by a force applied by a take up winder on the resulting membrane. The one or more reinforcing yarns are discharged from the front face 104 of the nozzle 100 between the two dope flows. The two dope flows merge with each other immediately outside of the nozzle 100 to form a single annular flow of dope. The one or more reinforcing yarns are embedded in the dope.

[0029] The dope and reinforcing yarn drop through an air gap into a coagulation bath. The coagulation bath is typically a tank equipped with rollers at the bottom and at the top as is known for membrane coagulation. A powered take-up winder receives the membrane emerging from the coagulation bath, optionally after the membrane passes through other unit processes such as a rinsing bath. The take up winder typically has a traverse guide to evenly populate a bobbin. The take up winder operates at an adjustable speed, typically between 1 and 30 m/min, that is matched to the downward velocity of dope being discharged through the nozzle 100. The take up winder also pulls the one or more reinforcing yarns through the nozzle 100. This results in the one or more reinforcing yarns being under tension between the nozzle 100 and the take up winder in an amount equal to the force required to pull the one or more reinforcing yarns through the nozzle 100.

[0030] Figures 2 to 9 show a second nozzle 1 10. The second nozzle 1 10 is similar to nozzle 100 but it has an additional plate 1 12 at the front of the second nozzle 1 10. The front face 104 of the second nozzle 1 10 is defined by the front of the plate 1 12. A bore fluid needle 1 14, providing a zone A, is also extended to the front of the plate 1 12. Zones B, C and D as described in relation to the nozzle 100 of Figure 1 are also provided in the second nozzle 1 10. However, the discharge openings for zones B, C and D are set back from the front face 104 by the thickness of the plate 1 12. Other features of the detailed construction of the second nozzle 1 10 shown in Figure 2 to 9 are also used with the nozzle 100 of Figure 1 .

[0031 ] Referring for example to Figures 2 and 3, the primary components of the second nozzle 1 10 are a main body 1 16, the bore fluid needle 1 14, a first insert 120, a second insert 122 and the plate 1 12. The bore fluid needle 1 14 threads into the main body 1 16 from the back. The first insert 120, second insert 122 and plate 1 12 are inserted into a recess at the front of the main body 1 16 and held in with screws (not shown) to be threaded into screw holes 124. A bypass connector 126 is drilled into the side of the main body 1 16 to connect zones D and B inside of the main body 1 16 and then plugged.

[0032] Referring to Figure 2, a dope inlet 130 provides dope to both of zones B and D. A bore fluid inlet 132 allows bore fluid to be provided to the needle 1 14. Reinforcing yarns enter the main body through ceramic guides 134, one for each distinct reinforcing yarn passage. Solvent enters the main body 1 16 through a plurality of solvent inlets 136. Referring primarily to Figures 8 and 9, bore fluid exits the needle 1 14 from a bore fluid outlet 140. Dope exits zones B and D through first and second dope passage discharge outlets 142 and 144 respectively. Reinforcing yarns exit zone C through yarn discharge outlets 146. Dope from the two zones B and D merges together around the reinforcing yarns in an annular space between the needle 1 14 and an outlet bore 148 in the plate 1 12.

[0033] Referring to Figures 1 to 9, both nozzles introduce reinforcement yarns into the membrane dope from yarn passages that are not connected to a supply of dope. The yarn discharge openings 146 are at or near the plane where the dope exits the nozzle 100, 1 10 at the front face 104, for example within 5 mm of the front face 104. Alternatively or additionally, the yarn discharge openings 146 are at or near to the dope discharge openings 142, 144, for example within 3 mm of the dope discharge openings 142, 144. When multiple reinforcement yarns are deployed they can be discharged from discrete yarn discharge openings 146 spaced evenly around the needle 1 14 at or near the front face 104 of the nozzle 100, 1 10.

[0034] The two nozzles 100, 1 10 differ in that in the second nozzle 1 10 the yarn discharge openings 146 are setback from the front face 104, which defines the discharge plane of the second nozzle 1 10 as a whole. Without setback, as in nozzle 100, the reinforcing filaments are introduced to the dope at the discharge plane of the nozzle. In this case, the reinforcing yarns exit from their passageways where the dope pressure is essentially atmospheric. As the yarn discharge openings 146 and dope discharge openings 142, 144 are moved back from the discharge plane, as in the second nozzle 1 10, the reinforcing yarn is discharged into an area of higher dope pressure. Some dope pressure may be desirable to minimize air entrained into the product membrane with the reinforcing yarn. However, the dope pressure at the yarn discharge openings 146 is preferably kept below a threshold at which the dope would flow back through the reinforcing yarn passage when the nozzle is in operation. [0035] Referring to Figure 10, a hollow fiber membrane 10 produce from either of the nozzles 100, 1 10 has a membrane wall 16 made from the dope of zones B and D. The membrane wall 16 has one or more reinforcing yarns 12 embedded in it. The reinforcing yarns 12 may be made up of individual filaments 14. Individual filaments 14 are preferably long continuous filaments rather than, for example, staple fibres.

[0036] The specific membrane 10 shown in Figure 1 has one reinforcing yarn 12, but there may be a plurality of reinforcing yarns 12, for example between two and eight. Each reinforcing yarn 12 is preferably a multi-filament yarn made of continuous thermoplastic filaments 14. The filaments are preferably grouped together but without sufficient twisting to be classified as a twisted yarn. Other types of yarns or threads, or a monofilament, might also be used but they are not preferred.

[0037] Filaments 14 can be made from polymeric fibers such as polyethylene, polypropylene, polyester, nylon or PVDF. Filaments 14 can be bi- component filaments with a first part, preferably a complete outer layer or sheath, made of a first polymer that is wetted by a membrane forming dope. For example, a reinforcing filament 14 may have an outer layer or other part made of a polymer that is soluble in a solvent used in the membrane dope. In particular, the outer layer or other part may comprise a polymer that is also present in the membrane dope. A second part, for example a core, of a bi-component filament 14 may be made of second polymer that is provides an improvement over using the first polymer alone. For example, the second polymer may be stronger, or less expensive, or both, relative to the first polymer.

[0038] The filaments 14 shown in Figure 1 are bi-component fibers spun with a core of polyethylene terephthalate (PET) and a sheath of polyvinyl idene fluoride (PVDF). The core is about 70-90% of the cross-sectional area. The PET is a strong material that has mechanical characteristics suitable for reinforcing or supporting membranes. PVDF by comparison is a relatively weak material. However, the PVDF sheath has an affinity for a PVDF and NMP based membrane dope. Such a dope may be used to form the membrane wall 16 using a NIPS process. [0039] The affinity between the outer surface polymer of the filaments 14 and the dope discourages air bubbles and encourages contact between the filaments 14 and the membrane wall. Alternatively, the surface of filaments 14 may also be modified or treated to promote bonding to the membrane dope. Such treatments can include, for example, plasma or chemical etching. The treatment is chosen to be appropriate for the materials of the filament 14 and the dope. Alternatively or additionally, as described above, filling the reinforcing filament passages with a solvent compatible with the dope also discourages air bubbles and encourages contact between the filaments 14 and the polymer wall.

EXAMPLE [0040] Figure 1 1 shows a modified coagulation bath 200 that was used in experimental tests. A tank 202 was filled with a quenching solution 204, primarily water, to form membranes from a PVDF in NMP based dope by a NIPS process. Experimental coating nozzles 208 was placed over the tank 202 and oriented such that a precursor fibre 206 would fall vertically through an air gap 210 and then into the quenching solution 204. In the tank 202, the precursor fibre 206 passed over a tension gauge 214 and a lower roller 216. After leaving the tank, the product fibre 212 passed over an upper roller before being taken up on a winder 218. The winder 218 applied the force necessary to pull reinforcing yarns through the experimental nozzles 208 at a constant line speed. The tension gauge 214 measured the applied force, and therefore the tension on the precursor fibre 206.

[0041 ] Three nozzles 208 were tested. The first two nozzles were generally as shown in US Patent Application Serial Number 13/328,761 filed on December 16, 201 1 , which is incorporated by reference. In these nozzles, reinforcing yarns pass through a middle passage containing dope. The middle passage ends in a first annular region located around a bore fluid needle and upstream of the exit plane of the nozzle. Dope wetted filaments pass from the first annular region into a downstream second annular region surrounding the bore fluid needle. A second flow of dope is injected into this second annular region. The dope with embedded reinforcing filaments leaves the second annular region and the exit plane of the nozzle. A third nozzle was a modified version of a second of the first two nozzles. In this modified nozzle, (a) the first annular region carrying reinforcing filaments from the middle passage was extended to the exit plane of the nozzle, (b) the supply of dope to the middle passage and first annular region was stopped, and (c) the bore fluid needle was replaced with an inner dope needle. Accordingly, the third nozzle resembled the nozzle 100 of Figure 1 except that it had no bore fluid needle and so produced a solid fibre rather than a hollow fibre. Although it produces a solid fibre, the third nozzle confirms that two flows of dope can envelope a reinforcing yarn when both flows of dope and the reinforcing yarn are discharged from a common plane.

[0042] In preliminary tests, it was determined that there was no material tension (less than 10 g) when passing reinforcing yarns alone through the first or third nozzle, and when passing dope alone through the first nozzle. However, when two reinforcing yarns and dope were passed through the nozzles at a line speed of 90 feet per minute (fpm), the first and second nozzles required a tension of about 1 18 and 130 g respectively. The third nozzle, however, required a tension of only about 22 g. At a line speed of 50 fpm with two reinforcing yarns, the first nozzle required a tension of about 93 fpm and the third nozzle required a tension of about 17 g. The second nozzle was not tested under these conditions. These tests indicated that the third nozzle resulted in a significant reduction in tension on the precursor fibre 206. [0043] In one other test, the second nozzle was used with one reinforcing yarn at a line speed of 90 fpm and required about 62 g of tension. The first nozzle was tested with one reinforcing yarn at a line speed of 50 fpm and required about 58 g of tension. Considered in combination with the tests described above, these tests indicate that for a given nozzle the required tension is influenced mostly by, and roughly proportional to, the number of reinforcing yarns. Tension is also influenced by line speed, although to a lesser extent. Overall, these tests suggest that the primary cause of tension is the movement of a reinforcing yarn at line speed through a relatively slow moving volume of dope in a chamber or passage of the nozzle.

[0044] The experiments also demonstrated that changing to the third nozzle design resulted in a greater reduction in tension than either a reduction in line speed or a reduction in the number of reinforcing yarns. We expect that this will result in less distortion of a hollow fibre membrane particularly as it is pulled around a lower roller 216. Alternatively, a faster line speed or reduced coagulation tank depth could be used with the third nozzle while producing a similar quality membrane compared to the first or second nozzle. It was also observed that no dope leaked out of the third nozzle through the inlets to the reinforcing yarn passages even though no seals were provided at the reinforcing yarn inlets.

[0045] This written description uses examples to disclose the invention and also to enable any person skilled in the art to practice the invention. The scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art.

Claims

CLAIMS:

1 . A nozzle for making a hollow fiber membrane comprising, a) a bore fluid passage passing through the nozzle and having a bore fluid discharge outlet; b) a dope passage through the nozzle and having a dope discharge outlet; and, c) a reinforcing yarn passage through the nozzle and having a reinforcing yarn outlet, wherein the dope discharge outlet and the reinforcing yarn outlet are both located (a) in or near the same plane or (b) at or near a front face of the nozzle.

2. The nozzle of claim 1 wherein the reinforcing yarn passage is not in communication with a dope passage except at the reinforcing yarn outlet.

3. The nozzle of claim 1 wherein the dope discharge outlet and the reinforcing yarn outlet are both located (a) in or near the same plane and (b) at or near a front face of the nozzle.

4. The nozzle of claim 1 wherein the dope discharge outlet and the reinforcing yarn outlet are both located (a) within 3 mm of each other along a longitudinal axes of the nozzle or (b) at or within 5 mm of the front face of the nozzle.

5. The nozzle of claim 1 wherein the dope discharge outlet and the reinforcing yarn outlet are both located in about the same plane.

6. The nozzle of claim 1 wherein the dope discharge outlet and the reinforcing yarn outlet are both located within 5 mm of the front face of the nozzle.

7. The nozzle of claim 1 having a plurality of discrete reinforcing yarn passages.

8. The nozzle of claim 1 having two annular dope passage discharge outlets, one located inside of the reinforcing yarn outlet and one located outside of the reinforcing yarn outlet.

9. The nozzle of claim 1 having a solvent inlet in communication with the reinforcing yarn passage.

10. A process for making a hollow fiber membrane comprising the steps of, a) passing a bore fluid through a nozzle and discharging the bore fluid from at or near a front face of the nozzle; b) passing a dope through a dope passage of the nozzle and discharging the dope from the dope passage in a ring around the bore fluid from at or near the front face of the nozzle; and, c) introducing a reinforcing yarn into contact with the dope at or near the front face of the nozzle.

1 1 . The process of claim 10 wherein the reinforcing yarn is first introduced into contact with the dope within 5 mm of the front face of the nozzle.

12. The process of claim 10 wherein the reinforcing yarn is a multifilament yarn, a monofilament or a thread.

13. The process of claim 12 wherein the reinforcing yarn is a multifilament yarn.

14. The process of claim 13 wherein the reinforcing yarn comprises filaments comprising a polymer that is wetted by the dope or filaments that are surface treated to encourage wetting by the dope.

15. The process of claim 13 wherein the reinforcing yarn is a generally untwisted yarn of generally continuous filaments.

16. The process of claim 10 wherein the reinforcing yarn comprises a polymer that is also present in the dope.

17. The process of claim 10 wherein the reinforcing yarn is wetted with a solvent before it contacts the dope.

18. The process of claim 10 further comprising passing additional dope through the nozzle and discharging the additional dope in a second ring around the bore fluid from the front face of the nozzle, wherein the reinforcing yarn is discharged between the ring of dope and the second ring of additional dope.

19. The process of claim 10 comprising introducing multiple reinforcing yarns into contact with the dope each from a separate discharge outlet.

20. The process of claim 10 wherein the reinforcing yarn is discharged from a reinforcing yarn passage located within 3 mm along the length of the nozzle from where the dope is discharged from the dope passage.

21 . The process of claim 10 wherein any dope or bore fluid in communication with the reinforcing yarn is maintained at a pressure insufficient to cause the dope or bore fluid to flow through a reinforcing yarn passage of the nozzle.