SELF-COILING HOLLOW FIBRE MEMBRANE

Abstract

A hollow fibre membrane having a coiled, a hemihelix, a helical or an undulated native form, in which the membrane can be stretched by up to 4-times its original length with no plastic deformation, and wherein the native form of the membrane is produced by the asymmetric flow of liquid polymer through an opening of a die or nozzle.

Claims

1-41. (canceled)

42. A hollow fibre membrane having a coiled, a hemihelix, a helical or an undulated native form, in which the membrane can be stretched by up to 4-times its original length with no plastic deformation.

43. A hollow fibre membrane of claim 42, wherein the native form of the membrane is produced by the asymmetric flow of liquid polymer through an opening of a die or nozzle.

44. A hollow fibre membrane according to claim 42, wherein the opening of the die or nozzle has a diameter at least 1.01- to 2-times that of the outer diameter of the hollow fibre membrane.

45. A hollow fibre membrane according to claim 42, wherein the membrane is produced by an extrusion process, a spinning process or by Thermally Induced Phase Separation (TIPS) or Solvent Induced Phase Separation (SIPS) processes.

46. A hollow fibre membrane of claim 42, wherein when placed under tension, the hollow fibre membrane has its pitch altered so that the hollow fibre membrane goes from a non-linear form to a substantially linear form.

47. A hollow fibre membrane of claim 42, wherein the hollow fibre membrane is gas permeable.

48. A hollow fibre membrane of claim 42, wherein the hollow fibre membrane comprises pores of less than 5 m.

49. A hollow fibre membrane of claim 42, wherein the hollow fibre membrane is a dense membrane and substantially free of pores.

50. A hollow fibre membrane of claim 42, wherein an internal diameter of the hollow fibre membrane is between 50 m and 10 mm.

51. A hollow fibre membrane of claim 42, wherein the hollow fibre membrane has a cylindrical inner and outer cross section or a cylindrical inner and non-cylindrical outer cross section; wherein when the hollow fibre membrane has a cylindrical inner and non-cylindrical outer cross section, the hollow fibre membrane has optionally an outer surface that is uneven or irregular, including projections or ridges extending outward from the outer surface of the membrane or with indentations extending inwards.

52. A hollow fibre membrane of claim 42, wherein the membrane is made from a liquid polymer selected from Poly-dimethyl-siloxane (PDMS), silicone, polymethylpentene (PMP), Polyvinylidene fluoride (PVDF), Polyethersulfone (PES), Polypropylene (PP), Polyethylene, Polysiloxanes or other polymeric plastic, elastic or rubber.

53. A hollow fibre membrane of claim 42, wherein the membrane is a silicone membrane and has an outer surface that is uneven or irregular comprising projections or ridges extending outward from the outer surface of the membrane, and wherein the native form of the membrane is produced by the asymmetric flow of liquid polymer through an opening of a die or nozzle.

54. An array of vertically aligned, hollow fibre membranes having a coiled, a hemihelix, a helical or an undulated native form, or a combination thereof, in which the membrane can be stretched by up to 4-times its original length with no plastic deformation, and wherein the native form of the membrane is produced by the asymmetric flow of liquid polymer through an opening of a die or nozzle, wherein the membranes are attached at either end to a manifold, and wherein the lumen of the membrane is in communication with an inner space of the manifold and the manifold can be used to supply or remove liquid or gas to or from the lumen of the membrane.

55. An array of hollow fibre membranes according to claim 54, wherein when the membranes have a helical form, the membrane fibres have a fixed length with a variable distance in pitch.

56. An array of hollow fibre membranes according to claim 54, wherein when the membranes have a coiled form, the membrane fibres have an adjustable coil diameter.

57. An array of hollow fibre membranes of claim 54, wherein tension applied to the hollow fibre membranes is controlled by at least one manifold adapted to move in a reversible vertical direction relative to the opposite end of the array.

58. A method of manufacturing the hollow fibre membrane having a coiled, a hemihelix, a helical or an undulated native form, in which the membrane can be stretched by up to 4-times its original length with no plastic deformation, and wherein the native form of the membrane is produced by the asymmetric flow of liquid polymer through an opening of a die or nozzle, the method comprising the steps of passing the liquid polymer through a die opening and around a needle which are asymmetrically aligned, wherein the opening produces an asymmetric flow of liquid polymer as its exits the die or the nozzle to produce a coiled, hemihelical, helical or undulated membrane.

59. A method according to claim 58, in which the hollow fibre membrane is made by a process of extrusion, spinning, casting, Thermally Induced Phase Separation (TIPS) or Solvent Induced Phase Separation (SIPS).

60. A method according to claim 58, in which the hollow fibre membrane is made by a process of extrusion, spinning, casting, Thermally Induced Phase Separation (TIPS) or Solvent Induced Phase Separation (SIPS) and wherein when the process is extrusion, an additional stress is imparted by extruding the hollow fibre membrane onto a conveyor running at a higher speed than the fluid polymeric membrane exiting the die or the nozzle.

61. A method according to claim 58, in which the hollow fibre membrane is made by a process of extrusion, spinning, casting, Thermally Induced Phase Separation (TIPS) or Solvent Induced Phase Separation (SIPS) and in which when the process is spinning, TIPs or SIPs, the angle of the die or nozzle is tilted at least about 2 to 30 from the vertical axis Y of the hollow fibre membrane.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0079] The invention will be more clearly understood from the following description of an embodiment thereof, given by way of example only, with reference to the accompanying drawings, in which:

[0080] FIG. 1 illustrates the theory of how a liquid boundary layer develops over the surface of a membrane.

[0081] FIG. 2 illustrates a coil section of a coiled membrane. This drawing illustrates that the boundary layer thickness is minimised over the length of the membrane regardless of the direction of the water flow.

[0082] FIG. 3 Graphic illustration of the short contact distance between the water and the membrane. The figure (A) shows a plan view and the figure (B) shows a horizontal perspective of the coiled membrane.

[0083] FIG. 4 illustrates the behaviour of coiled membranes in a bundle. (A) Fibres with exactly the same pitch and coil direction will tend to nest together, as shown, independent of the applied tension. (B) When the coils have different pitch and coil direction, they tend to naturally push each other apart and spread laterally as the tension is reduced.

[0084] FIG. 5: Shows a photograph of a single hollow fibre membrane which is under 4 different tensions. (a) The new helix shaped hollow fibre membrane when it is under no tension; (b) the new helix shaped hollow fibre membrane when it is hung under its own weight; (c) the new helix shaped hollow fibre membrane under tension and (d) the new helix shape hollow fibre membrane when it is under enough tension to be pulled straight.

[0085] FIG. 6 is a photograph of an array of self-coiling membrane (A) under no additional tension and (B) under tension with weight attached to the end.

[0086] FIG. 7 is a graph representing the experimentally measured Oxygen Transfer Rate of an array of 550 naturally coiled hollow fibre PDMS membranes with an array of 550 straight hollow fibre PDMS membranes.

[0087] FIG. 8 illustrates an example of cross-sectional profiles of membranes with result from asymmetrical flow through a die nozzle. t=nominal membrane thickness, and t.sub.1>t where the thickness is greater than the nominal thickness.

[0088] FIG. 9 illustrates the die nozzle arrangement for symmetrical flow (linear) and asymmetrical flow (non-linear) for use in the extrusion process of manufacturing hollow fibre membranes.

[0089] FIG. 10 illustrates how an asymmetrical flow is generated in a TIPS, SIPS or spinning process utilising a symmetrical die nozzle arrangement.

DETAILED DESCRIPTION

[0090] The membranes of the subject invention can take on an irregular helical, a helical or coiled or curled shape that varies in pitch length and coil diameter when tension is applied. When the tension is low, the membrane looks like a spring or helix with the coils having a very small pitch (coils close together) and a coil diameter between 2 and 50 times the outer diameter of the membrane. As the tension on the membrane increases, or the length of the membrane is increased, the pitch distance from one coil to the next also increases, and the coils move further apart with the diameter of the coil reduced. In the extreme, under sufficient tension, the membrane becomes linear. If the ends of the hollow fibre membranes are potted, then the tension on the coiled membranes will increase as the potted ends are moved further apart. If the membrane is both coiled and elastic it can also be stretched beyond its nominal length. For example, a 1 m long hollow fibre membrane may only be 0.5-0.75 m in length when coiled and in its natural curled or coiled state (no tension, its predisposed/native state). Yet, if the membrane is elastic, it may also be stretched beyond its nominal length to a length of, for example, 1.1 m-1.50 m. The membrane may also be stretched up to 4-times its nominal length without causing any damage to the elasticity of the membrane. The membrane will always return to its original length retaining its elasticity and returning to its natural curled or coiled state. Thus, the shape and effective length of the membrane can be modified by changing the distance between the upper and lower manifolds to which the potted ends of the hollow fibres are secured.

[0091] The impact of the helical or coiled shape of the membranes on boundary layer development is best illustrated by viewing FIG. 2 and FIG. 3. In FIG. 2, a single coil of a helically-shaped hollow fibre membrane is shown and the arrows indicate examples of horizontal and vertical fluid flow over the membrane surface. Regardless of the direction of flow, the fluid is only in contact with a short length of the membrane surface and this does not allow a thick boundary layer to form. This effect is clarified in FIG. 3. FIG. 3A shows a plan view of a vertically aligned coiled membrane with a coil-diameter of D.sub.coil and FIG. 3B shows an elevation perspective of the coiled membrane. The helical shape takes on a circular aspect in a plan view and a horizontal fluid flow across the coiled membrane would have lengths of contact with the membrane as illustrated by the horizontal lines marked 1, 2 and 3 in FIG. 3A. Line 1 represents the shortest contact length, which is equal to the diameter of the membrane, and 3 represents the longest possible contact length and is approximately equal to the diameter of the coil. FIGS. 2 and 3B also show that if the fluid is flowing vertically through the coiled membrane then the fluid is traversing the diameter of the hollow fibre membrane at an angle that is pitch-dependent and the contact distance between the fluid and membrane is also short.

[0092] When bundles of coiled hollow fibre membranes are potted into manifolds, it is important to ensure that the coiled fibres do not nest together as illustrated in FIG. 4A. When the fibres nest in this way, the fibres remain very close together and in contact with each other, regardless of the tension on the membranes. This nesting behaviour hinders mass transfer by reducing the effective surface area of the membranes and hindering the flow of fluid around and between the individual hollow fibres. This nesting behaviour can be avoided by potting self-coiling hollow fibre membranes, which have slightly different pitch, as well as by mixing fibres coiled in different directions (clockwise and counter-clockwise). FIG. 4B illustrates the desired bundle behaviour. When the fibres are potted in this manner, the individual hollow fibres tend to push each other apart and therefore spread laterally. The result is a much more open structure which exposes more membrane area for mass transfer. In addition, the more porous structure of the membrane bundle encourages better fluid flow into the bundle and between the hollow fibres.

[0093] The lateral width of the fibre bundle shown in FIG. 4B, that is, is subject to changes in length when stretched by increasing the distance between the upper and lower manifold. Under tension, the three fibres illustrated in FIGS. 4A and 4B will revert to a linear form having the same lateral width. However, as the tension is relaxed, that is when the distance between the upper and lower manifold is decreased, the fibres in FIG. 4B will spread much further apart laterally, while the fibres in FIG. 4A will have little to no tendency to move apart, only the pitch will change.

[0094] Typically, when large numbers of large bundles of fibres are used, as is common in commercial full-scale systems, it is difficult to achieve uniform fluid contact with all of the membranes in a reactor. For example, slack hollow-fibre membranes tend to be either pushed together (in cross-flow applications) or fluid delivery to the centre of vertical bundles in parallel flow is poor and the fluid preferentially flows around the fibre bundles instead of through them. These effects tend to reduce the overall mass transfer performance of the membranes. This situation is ameliorated by the use of coiled membranes as shown in FIG. 4B. The open structure of the membrane bundles together with their coiled structure leads to effective membrane-fluid contact and superior mass transfer.

[0095] Another aspect of this membrane is that this coiled nature is an inherent property of the membrane and is imparted to the membrane due to the method of manufacture whether that be by extrusion, spinning or casting. The undulating nature is not created in a separate post-fabrication step, such as by crimping, or winding or post-production heating of the membrane while held in a coiled state.

[0096] In one embodiment, the hollow membrane is manufactured by extrusion of the polymer, e.g. PDMS or silicone, through a die. The die has an opening of between 1.01- and 2-times the outer diameter of the final hollow fibre membrane. The fluid annulus which leaves the die has a larger diameter with a thicker wall than the desired final hollow fibre membrane. The fluid PDMS or silicone is forced through the die in an asymmetric flow and when it passes through the high temperature oven, the PDMS or silicone molecules crosslink and result in the solidification of the fluid PDMS or silicone. The fluid annulus leaving the die creating the asymmetric flow, the solidification of the PDMS or silicone fibre membrane and the speed of the conveyor receiving the solidified membrane creates a coiled/helical membrane when under no tension, that is, when in its natural, relaxed state.

[0097] The TIPS process involves heating of the polymer and spinning the hollow fibre through a die nozzle into a bath of cool liquid (usually water) to cool. The polymer sets and hardens when cooled. The die nozzle has an opening of between 1.01- and 2-times the outer diameter of the final hollow fibre membrane. The fluid annulus which leaves the die has a larger diameter with a thicker wall than that of the desired final hollow fibre membrane, and can also have a thicker wall on one side, creating an asymmetric flow. As the fluid is spun through the die having this arrangement, the membrane is predisposed to adopt a coiled configuration when it cools.

[0098] The SIPS process involves dissolving the polymer in a solvent and which is then cast from a die nozzle into a bath of water. The die nozzle has an opening of between 1.1 and 2 times the outer diameter of the final hollow fibre membrane. In this instance, the fluid annulus which leaves the die has a larger diameter with a thicker wall than that of the desired final hollow fibre membrane, and a thicker wall on one side, creating an asymmetric flow. The solvent is removed from the solvent/polymer solution in the water as the solvent is miscible in water but the polymer is immiscible, the polymer then crystalizes, and the resulting hollow fibre membrane adopts a coiled/helical configuration without applying any tension. In other words, the membrane is predisposed to adopt a coiled/helical configuration.

[0099] In each of the methods of manufacture of the membrane, the feature of a flexible coil/helix-like structure is created by a combination of the opening of the die being between 1.01- and 2-times the outer diameter of the final hollow fibre membrane, the speed and asymmetric nature of the flow of the membrane material leaving the die and the solidification of the polymeric material through thermosetting, cooling or crystallization. For the extrusion process, the speed of the conveyor accepting the extruded solidified polymeric material runs faster than the extrusion speed; which contributes to the membrane adopting a coiled/helical configuration.

[0100] In FIG. 5(a), a helical (coiled) hollow fibre membrane is under no tension and is in its natural state. In FIG. 5(b) the hollow fibre is suspended and the upper part of the helix is elongated under the tension caused by the weight of the mass of the lower membrane (or the perceived vertical movement of the lower manifold in a direction opposite to that of the upper manifold). In FIG. 5(c) an additional tension is being placed on the fibre by extending both ends of the fibre (where the vertical movement of the upper and lower manifolds move away from each other). In FIG. 5(d) the fibre is placed under enough tension that its helical structure has been lost and the hollow fibre has become straight. These effects are reversible so that when the tension is relaxed (that is, when distance between the lower and upper manifolds decreases), the fibre reverts back to the form shown in 5(a).

[0101] FIG. 6A shows a bundle of coiled hollow fibre membranes simply hanging under its own weight, while FIG. 6B shows the same membrane module under tension. This figure illustrates how the membranes spread out laterally as the tension is relaxed on the fibres. The relaxed fibre bundle (FIG. 6A) has a more open structure, which makes it easier for water to flow into and through the hollow fibres in the bundle. FIG. 6 also illustrates the change in the bundle shape as the distance between the upper and lower ends of the bundle changes. The distance between the upper and lower ends of the membrane bundle shown in FIG. 6B is 15% greater than that shown in FIG. 6A.

[0102] FIG. 7 demonstrates the improvement in the oxygen transfer rate that can be achieved with the use of tension-sensitive self-coiling membranes under conditions in which the mass transfer is limited by diffusion through the liquid boundary layer surrounding the membranes. Measurements were taken by placing an array of membranes in a vertical tank of clean water, which was mixed by means of a recirculation pump and all of the dissolved oxygen was initially removed by the addition of excess sodium sulphite. A dissolved oxygen probe was then used to monitor the increase in dissolved oxygen concentration in the water as air was supplied to the lumen of the hollow-fibre membrane. The specific rate of oxygen transfer was then calculated based on the external surface area of the membranes and the results shown are normalized relative to straight, non-tension sensitive hollow fibre membranes.

[0103] FIG. 8 illustrates examples of cross-sectional profiles of hollow fibre membranes of the invention which result from the asymmetrical flow of plastic polymer from the nozzle/die during the manufacturing process. The hollow fibre membrane has a nominal outer wall thickness, t, and also a thickness, t.sub.1, which is greater than the thickness, t. In some instances, ridges or indentations may form on the outer circumference of the membrane wall. This difference in the outer membrane wall thicknesses around the circumference of the fibre membrane lumen provides the stresses that cause the membranes to adopt a curly, coiled, helical, hemihelical or undulated native form without the need for post-processing interference.

[0104] FIG. 9 illustrates the nozzle/die and needle arrangement which produces both the linear membranes of the prior art and the non-linear membranes described herein. The arrangement 1 in (A) shows a needle 2 situated in the centre of an opening 3 of a nozzle/die 4. The central arrangement of the needle 2 produces a symmetrical flow of liquid polymer 5 through the opening 3, which creates a hollow fibre membrane 6 with an outer wall 7 having a symmetrical thickness.

[0105] In (B), there is illustrated an arrangement 100 in which steps or parts described with reference to (A) above are assigned the same numerals. In the arrangement 100, the needle 2 is aligned off-centre of the opening 3 of the nozzle/die 4. The off-central arrangement of the needle 2 produces an asymmetrical flow of liquid polymer 5 through the opening 3, which creates a hollow fibre membrane 10 with an outer wall 11 having an asymmetrical thickness (t.sub.1>t).

[0106] FIG. 10 there is illustrated an arrangement 200 in which steps or parts described with reference to (A) and (B) above in FIG. 9 are assigned the same numerals. In the arrangement 200, the angle of the nozzle/die 4 is tilted when used during the TIPS, SIPS or spinning processes. The nozzle/die 4 is titled at an angle of between 2 to 30 from the vertical axis Y with an optimal range of between 5 and 15. The tilt of the nozzle/die 4 creates an asymmetrical flow during the TIPS, SIPS or spinning process, which creates the hollow fibre membrane 10 with an outer wall 11 having an asymmetrical thickness.

Membrane Applications:

Liquid Filtration

[0107] During filtration, the particulates, colloids, large molecular weight compounds and microorganisms, which are retained by the membrane, tend to concentrate in the boundary layer at the external membrane surface. Commercial membrane filtration systems are designed to ensure that the water surrounding the membranes is well mixed, and that the mixing conditions, which create good fluid flow past the surface of the membranes, encourage removal of the retained contaminants from the surface of the membrane. Aeration is also used to both encourage membrane movement and to create localized turbulence, which can help disrupt the boundary layer and minimize concentration polarization. When poor mixing conditions and low shear conditions prevail, contaminants, particles and microorganisms rapidly attach to the membrane surface, which causes the external surface of the membranes to become coated in a chemical/biological layer that impedes filtration. This process is referred to as membrane fouling. Fouling is an expensive problem since it reduces the filtration performance of the membrane. Reversible fouling is removed from the surface of the membrane by periodically backwashing the membrane with permeate. This fouling layer on the surface of the membrane is then removed. Irreversible fouling can also occur and contributes to reduced membrane life. Irreversible fouled membranes must be taken out of service and chemically cleaned to remove the foulant layer. Good mixing conditions can substantially reduce fouling.

Gas Diffusion

[0108] In membrane modules for gas diffusion, the boundary liquid layer typically becomes the rate limiting step for mass transfer or flux between the membrane lumen and the bulk liquid. The boundary layer effectively increases the distance through which gas molecules must diffuse to permeate from the gas phase inside the membrane to the dissolved phase in the bulk liquid. The boundary layer therefore represents a resistance to mass transfer and the thickness of the boundary layer affects the overall mass transfer coefficient. The thicker the boundary layer, the lower the mass transfer and the slower the rate of mass transfer. Many attempts have been made to develop methods of breaking up these liquid boundary layers including introducing spacers to promote static mixing (Pentair X-Flow helix, Liqui-Cel placing baffles inside membrane modules), changing or reversing flow direction, or the introduction of bubbles or other turbulences into the liquid around the membrane. Most of these developments rely on either an addition to the membrane module or a periodic change to the operating conditions to break up the boundary layer.

[0109] The advantage of using the tension-sensitive membranes which can take on a helical, spring-like configuration, as described herein, is that they achieve high mass transfer rates by minimizing boundary layer development and creating a liquid penetrable 3D structure which provides a torsional and dynamic flow path. They do this when used as self-expanding fibre bundles and which take on a configuration that encourages frequent boundary layer disruption and a correspondingly thin boundary layer. The fibre bundles using the membranes described herein will provide superior mass transfer performance to existing membrane module designs. In addition, the actual shape and behaviour of the bundles will be tension sensitive so that the mass transfer performance of the system can be manipulated to minimize the energy requirements for air and fluid flows for fouling control and gas transfer.

REFERENCES

[0110] X. Yang, R. Wang, A. G. Fane; Novel designs for improving the performance of hollow fibre membrane distillation modules. J. Membr. Sci. 248, (2011) 52-62. [0111] X. Yang, E. O. Fridjonsson, M. L. Johns, R. Wang, A. G. Fane, A non-invasive study of flow dynamics in membrane distillation hollow fiber modules using low-field nuclear magnetic resonance imaging (MRI), J. Membr. Sci. 451 (2014) 46-54. [0112] Luelf, Tobias & Bremer, Christian & Wessling, Matthias. (2016). Rope coiling spinning of curled and meandering hollow-fiber membranes. Journal of Membrane Science. 506 . . . 10.1016/j.memsci.2016.01.037. [0113] P. Moulin, J. Rouch, C. Serra, M. Clifton, P. Aptel; Mass transfer improvement by secondary flows: Dean vortices in coiled tubular membranes. J. Membr. Sci., 114 (1996), pp. 235-244