WO2003063995A2

WO2003063995A2 - Spiraled surface hollow fiber membranes

Info

Publication number: WO2003063995A2
Application number: PCT/US2003/002580
Authority: WO
Inventors: Attila Herczeg
Original assignee: Amersham Biosciences Membrane Separations Corp.
Priority date: 2002-01-29
Filing date: 2003-01-28
Publication date: 2003-08-07
Also published as: EP1469929A4; CA2473246A1; WO2003063995A3; US20030140790A1; EP1469934A2; EP1469934A4; US6805730B2; AU2003209418A1; AU2003209410A1; EP1469929A2

Abstract

Porous asymmetric hollow polymer fiber membranes having spiraled inner and/or outer surfaces, as well as filters and filter devices comprising one or more of the hollow fiber membranes, the filter and devices preferably being arranged to direct fluid flow from the inner surface of the membranes to the outer surface, and methods of using the filters and filter devices, are disclosed.

Description

SPIRALED SURFACE HOLLOW FIBER MEMBRANES

FIELD OF THE INVENTION [0001] This invention pertains to porous hollow fiber membranes.

BACKGROUND OF THE INVENTION [0002] Hollow fiber membranes are generally defined as having an inside surface, an outside surface, and defining a wall and a hollow cavity or bore. They are typically arranged in a filter device as a plurality or bundle of fibers, and utilized for a variety of filtration applications. In some filtration applications, referred to as "inside-out" flow applications, the hollow fiber membranes in the filter device each have small pores at the inner surface and large pores at the outer surface, and the fluid to be filtered is passed through the inlet of the device into the bores of the membranes such that a portion of the fluid is passed from the inside surface of the fiber to the outside surface and through one outlet of the device, and another portion passes tangentially or parallel to the inside surface and through another outlet of the device. The fluid passing into the device and bore of the membrane is commonly referred to as the feed (the feed contains various sized molecules and/or species and possibly debris), the fluid passing from the inside surface to the outside surface is commonly referred to as the permeate or the filtrate (the permeate or filtrate contains the smaller molecules and/or species that will pass through the pores of the membrane), and the fluid passing parallel to the inside surface of the membrane without passing to the outside surface is commonly referred to as the retentate (the retentate contains the larger molecules that do not pass through the pores of the membrane). [0003] Conventional hollow fiber membranes used in inside-out applications have suffered from a number of deficiencies, particularly due to fouling of the inside surface. Fouling typically refers to the accumulation of material on the inside surface of the membrane. This accumulated material can block the pores of the membrane, thus preventing or reducing the passage of the desired product or molecules into the permeate. Once the surface is fouled, filtration efficiency is decreased, and the fibers need to be cleaned or replaced. Additionally, some membranes are difficult to clean. These problems can be magnified in filter devices including a plurality of hollow fibers, since some fibers can become more heavily fouled than others, resulting in uneven flow.

[0004] The present invention provides for ameliorating at least some of the disadvantages of the prior art. These and other advantages of the present invention will be apparent from the description as set forth below.

BRIEF SUMMARY OF THE INVENTION [0005] In accordance with an embodiment of the invention, a hollow fiber membrane is provided comprising a spiraled inner and/or outer surface, preferably, wherein the spiral is continuous along at least about one third of the length of the membrane. The spiral can be formed as a depression or groove in the surface, or the spiral can protrude from the surface. In a preferred embodiment, the hollow fiber membrane has a spiraled inner surface, wherein the spiral protrudes from the surface. [0006] Hollow fiber membranes according to embodiments of the invention comprising spiraled inner surfaces have improved efficiency over typical hollow fiber membranes in that the inventive membranes promote turbulence of fluid flow therethrough, and the increased turbulence serves to clean the membrane and/or reduce fouling. The spiraled surface typically increases the surface area of the membrane available for filtration. The spiraled surfaces are permeable, e.g., active, in that fluid can pass through the spiraled structure.

[0007] Membranes according to the invention are particularly useful in filter devices used for tangential flow filtration applications, wherein the devices include filters having a plurality of hollow fibers, wherein turbulence is increased without including additional separate structures such as flow mixers.

[0008] In accordance with the invention, methods for making hollow fiber membranes having at least one spiraled surface are also provided.

BRIEF DESCRIPTION OF THE DRAWINGS [0009] Figure 1 shows a perspective diagrammatic internal view of an embodiment of a hollow fiber membrane having a spiraled inner surface according to the present invention, wherein the spiral includes five individual lobes fl-f5. The membrane has an outside diameter D, a spiral having a frequency of dimension L, and the distance of the spiral to the opposite side is 1/2L.

[0010] Figure 2 is a partial cross-sectional side view of an extrusion head for preparing hollow fiber membranes according to the invention.

[0011] Figure 3 is an enlarged cross-sectional view of the tip of the extrusion head shown in Figure 2.

[0012] Figures 4-6 are partial diagrammatic cross-sectional bottom views of extrusion heads for preparing hollow fiber membranes according to embodiments of the invention. The extrusion head shown in Figure 4 is suitable for preparing a hollow fiber membrane with a spiraled inner surface, the extrusion head shown in Figure 5 is suitable for preparing a hollow fiber membrane with a spiraled outer surface, and the extrusion head shown in Figure 6 is suitable for preparing a hollow fiber membrane with spiraled inner and outer surfaces.

DETAILED DESCRIPTION OF THE INVENTION [0013] In accordance with an embodiment of the present invention, a membrane is provided comprising a hollow fiber having an inner surface and an outer surface, wherein at least one of the surfaces comprises a spiraled surface. The membrane can include a spiraled inner surface and/or a spiraled outer surface. As noted above, the spiraled porous surfaces are permeable, e.g., active, in that fluid passes through the spiraled structure and the surfaces. Accordingly, the spirals provide active surface area available for filtration.

[0014] The spiral can have any suitable appearance, and one or more lobes. For example, Figure 1 shows a hollow fiber having an inner opening that is generally star-shaped. Typically (using Figure 1 for reference), wherein the inner surface of the membrane is spiraled, and the spiral projects from the inner surface, the spiral includes at least two lobes, and can include three, four, or five lobes (five lobes are shown), or more. In some embodiments, one or two lobes are preferred. [0015] As noted earlier, the spiraled surface provides fluid flow turbulence as the fluid passes across the inner or outer surface of the membrane mder conditions of flow. For the purpose of visualization, the spiraled surface is similar to the rifling in a gun barrel. The turbulence (sometimes referred to as eddy currents) can reduce or control the formation of a fouling layer on the surface of the membrane. [0016] Hollow fiber membranes according to embodiments of the invention have improved capacity over typical hollow fiber membranes in that the inventive membranes have increased resistance to fouling. In preferred embodiments, the membranes efficiently retain the larger molecules or species while allowing the smaller molecules or species of interest to pass through at a high concentration or throughput.

[0017] In accordance with an embodiment of the invention, a filter device comprises a housing having an inlet, a first outlet and a second outlet, the housing defining a first fluid flow path between the inlet and the first outlet, and a second fluid flow path between the inlet and the second outlet, a plurality of porous hollow polymer fiber membranes disposed across the first fluid flow path and substantially parallel to the second fluid flow path, each porous hollow fiber membrane having a spiraled inside surface, and an outer surface, wherein the housing is arranged to direct a portion of fluid (preferably, a permeate) from the inlet, through the spiraled inner surface and the outer surface of the porous hollow fibers, and through the first outlet, and direct another portion of fluid (preferably, a retentate) from the inlet, along the spiraled inner surface, and through the second outlet.

[0018] A method for processing a fluid suspension according to an embodiment of the invention comprises providing at least one porous hollow polymer fiber membrane having an inner spiraled porous surface and an outer porous surface; contacting the inner surface of the membrane with a feed fluid comprising larger and smaller macromolecules, and passing a permeate containing the smaller macromolecules from the inner surface to the outer surface. In a more preferred embodiment, the method also comprising passing a retentate containing the larger macromolecules along the bore of the membrane. Embodiments of the method comprise dead end filtration and tangential flow filtration. [0019] In accordance with another embodiment, a method of separating a fluid into a retentate and a permeate comprises directing a feed suspension comprising larger macromolecules and smaller macromolecules into the central bore of a hollow fiber membrane, the membrane having an inner porous spiraled surface and an outer porous surface; passing a permeate containing the smaller macromolecules from the inner surface to the outer surface; and passing a retentate containing the larger macromolecules along the central bore of the membrane.

[0020] In accordance with another embodiment, a method of separating a fluid into a retentate and a permeate comprises directing a feed suspension comprising larger species and smaller species into the central bore of a hollow fiber membrane, the membrane having an inner porous spiraled surface and an outer porous surface; passing a permeate containing the smaller species from the inner surface to the outer surface; and passing a retentate containing the larger species along the central bore of the membrane.

[0021] In accordance with yet another embodiment of the invention, a method of preparing a hollow fiber membrane comprises providing a spinning dope comprising a first polymer, a solvent, and a nonsolvent, in ratios sufficient to form a homogenous solution or a colloidal dispersion; extruding the dope in the form of a hollow pre-fiber from a nozzle having a rotating inner or outer element, the pre-fiber having an inside surface and an outside surface; contacting the outside surface of the pre-fiber with a coagulating medium; and coagulating the pre-fiber from the outside surface to the inside surface to provide a hollow fiber membrane having a spiraled inner and/or outer surface.

[0022] In accordance with another embodiment of the invention, a method of preparing a hollow fiber membrane comprises providing a spinning dope comprising a first polymer, a solvent, and a nonsolvent, in ratios sufficient to form a homogenous solution or a colloidal dispersion; extruding the dope in the form of a hollow pre-fiber from a nozzle having a rotating inner or outer element, the pre-fiber having an inside surface and an outside surface; contacting the inside surface of the pre-fiber with a coagulating medium; and coagulating the pre-fiber from the inside surface to the outside surface to provide a hollow fiber membrane having a spiraled inner and/or outer surface.

[0023] Some embodiments of the method comprise forming a progressively asymmetric membrane having at least one spiraled surface. Preferably, the spinning dope comprises a first polymer and a second polymer, more preferably, wherein the first polymer comprises a sulfone polymer or polyvinylidene fluoride, and the second polymer is polyvinyl pyrrolidone. In a more preferred embodiment, the method further comprises collecting the hollow fiber membrane on a receiving plate, more preferably, a rotating receiving plate.

[0024] Typically, the hollow fiber membranes according to the invention are prepared by phase inversion, preferably, via melt-spinning, wet spinning or dry-wet spinning. Phase inversion can be achieved in several ways, including evaporation of a solvent, addition of a non-solvent, cooling of a solution, or use of a second polymer, or a combination thereof. [0025] In conventional dry-wet and wet-wet spim ing processes, a viscous polymer solution containing a polymer, solvent and sometimes additives (e.g., at least one of a second polymer, a pore former, a nonsolvent and, if desired, a surfactant) is pumped through a spinneret (sometimes referred to as the spinning nozzle or extrusion head), the polymer solution being mixed and stirred to provide a homogenous solution or a colloidal dispersion, filtered, and degassed before it enters the extrusion head. A bore injection fluid is pumped through the im er orifice of the extrusion head. In a dry- wet spimiing process, the fiber extruded from the extrusion head, after a short residence time in air or a controlled atmosphere, is immersed in a nonsolvent bath to allow quenching throughout the wall thickness substantially uniformly, and the fiber is collected. In a wet-wet spinning process, the extruded fiber does not have residence time in air or a controlled atmosphere, e.g., it passes from the extrusion head directly into a nonsolvent bath to allow quenching throughout the wall thickness substantially uniformly.

[0026] However, in accordance with preferred embodiments of the invention, the extruded fiber is not immersed in a coagulation medium. Rather, as explained in more detail below, a coagulation medium is passed from the extrusion head and is placed in contact with the outer surface of the extrudate (or pre-fiber) as the extrudate passes from the extrusion head (while an inner or outer element of the extrusion head is rotated). As the extrudate is contacted only with the outside surface, coagulation proceeds from the outside surface of the fiber toward the inside surface. [0027] The coagulation medium facilitates gelation of the polymer solution, i.e., the transition of the polymer from a solution state to a gel state. The coagulation medium has a reduced or no solubility for the polymer. As the polymer solution extrudate is contacted (on the outside surface) with the coagulation medium, the solvent diffuses out of the extrudate and at the same time, the coagulation medium diffuses into the extrudate. As a result, the molecular mobility of the polymer chain becomes restricted. A porous microstructure forms characteristic of the volume occupied by the solvent.

[0028] The coagulation medium is typically a non-solvent, e.g., water. Preferably, the coagulation medium contains, in addition to a non-solvent, additives such as a solvent, a swelling agent, a wetting agent, or a pore-former. These additives contribute to bring the solubility parameter of the coagulation medium close to that of the polymer solution such that when the contact occurs, the gelation is imminent, and at the same time, that the exchange of solvent and coagulation medium is at a rate suitable to produce the porous structure.

[0029] Preferably, the extrudate is passed, via force and/or gravity, from the extrusion head to a receiving plate. The extrusion head used to prepare membranes according to the invention can have a plurality of orifices, e.g., a central bore and at least two surrounding passageways, as shown in Figures 2 and 3 for example. Illustratively, in preparing a membrane in accordance with a wet spinning processes, the bore injection fluid is passed through the inner passageway 1 of the extrusion head 100, the viscous polymer solution is passed through a first passageway 2 surrounding the inner passageway, and a nonsolvent (coagulation medium or quench solution) is passed through a second (or outer) passageway 3 surrounding the first passageway. The extrusion head can have additional passageways (not shown), e.g., a concentric passageway for another fluid between the passageways for the polymer solution and the coagulation medium. [0030] In accordance with preferred embodiments of the invention, the extrusion head has at least one orifice or passageway (typically, at least the orifice or passageway through which the spinning dope passes, e.g., orifice 2 shown in Figures 2-6) having a non-round or non-oval inner and/or outer wall, e.g., the orifice bore is irregular. When viewed in bottom cross-section (e.g., as shown in Figures 4-6) the orifice can have a variety of shapes and configurations, e.g., the orifice can be lobate (preferably having two or more lobes), or star-shaped. [0031] Preferably, the extrusion head has at least one element (preferably, comprising a wall of an orifice) that rotates while the other element(s) of the head remain stationary. Accordingly, membranes can be produced having, for example, a spiraled inner surface (e.g., wherein the inner orifice is rotated while the pre-fiber is extruded).

[0032] As noted above, the extrusion head preferably has a plurality of passageways. For example, with reference to Figures 2-6, the bore injection fluid is passed through the inner irregularly shaped orifice or passageway 1, the spinning dope is passed through the orifice 2 surrounding the inner passageway (e.g., wherein the inner surface of the passageway for the dope is the irregular outer surface of the extrusion head orifice), and a coagulation medium is passed through the outer orifice or passageway 3. Additionally, or alternatively, the extrusion head can have at least one passageway arranged to provide a membrane having a spiraled outer surface, e.g., wherein the outer surface of the passageway for the polymer solution has an irregular surface.

[0033] In accordance with one embodiment, a method for making the membrane comprises extruding a polymer spinning dope (polymer, solvent, and nonsolvent solution) into a quenching environment (e.g., non-solvent for the polymer or temperature change causing polymer precipitation) either introduced within the fiber, or on its outside, wherein the extruder has been modified to include a convoluted surface, a spiraled surface and/or a multilobal structure, e.g., having bi, tri, terra, penta, or higher lobes. The spin dope is appropriately quenched so that the spiraled surface will be incorporated into the hollow fiber during extrusion. If desired, a spiraled structure can be provided by turning the interior (or exterior) portion of the extruder as the extrusion of the pre-fiber proceeds.

[0034] In some embodiments, particularly those wherein the membrane is skinned and the spiraled surface is not the skinned surface, the spirals can be made directly during coagulation. Illustratively, fast coagulation during which the coagulant penetrates the membrane surface creates large intrusions or macrovoids. Alternatively, a mixture of a membrane forming polymer and a pore former can be melt-extruded through a suitably modified die, and the pore former leached to produce a fiber.

[0035] In accordance with a preferred embodiment of the invention, a method for making the membrane comprises extruding a polymer spinning dope (e.g., polymer, solvent, and nonsolvent solution) such that the outside surface of the fiber contacts a coagulation medium to allow porous skin formation on the outside (the outside skin being the fine pored side of the membrane constituting the coagulation medium-dope interface) while introducing a bore injection fluid through the inside bore to prevent the collapse of the bore of the membrane. Accordingly, this embodiment includes coagulating the polymer spinning dope with a coagulation medium on the outer surface of the fiber by extruding the coagulation medium from an outer orifice of the extrusion head simultaneously with the extrusion of the spinning dope from an inner orifice (the spinning dope orifice being arranged between the orifice for the bore injection fluid and the orifice for the coagulation medium) wherein the orifices are aligned to allow the coagulation medium to contact the outside surface of the fiber as it passes from the spinning dope orifice, and while an interior or exterior element of the extrusion head is rotated. Coagulation migrating from the outside porous skin toward the center progressively creates a less dense structure terminating with the open structure on the interior (inside) surface and (in a preferred embodiment) having a progressively asymmetric, graded structure between the inside surface and the outside surface.

[0036] If desired, in some embodiments of the invention the hollow pre-fiber leaves the extrusion head completely formed, and there is no need for any further formation treatment except for removing the solvent, and, in some embodiments, placing the membrane in a bath (e.g., containing glycerine and/or polyethylene glycol) to improve the mechanical properties, e.g., the pliability, of the membrane. [0037] In accordance with another embodiment of a method for making a membrane according to the invention, a hollow fiber leaving the extrusion head is passed a desired distance (e.g., via gravity) to a radially rotating receiving plate, allowing the fiber to be easily collected in a desired orientation or configuration (e.g., a coil), more preferably while the fiber on the plate is washed with water. An advantage of this embodiment includes collecting the fiber, preferably in the form of a single coil, without pulling or stretching it, thus reducing stress to the fiber. Additionally, or alternatively, if the fiber breaks, additional fiber can be collected without the labor-intensive effort of threading, weaving or winding the new fiber into the various spools, drums and/or dancer arms of conventional collecting equipment. [0038] If desired, the formed membrane can be placed in a water bath (e.g., to leach the remaining solvent), and/or otherwise processed, e.g., placed in a glycerine/water bath to prevent collapse during storage. Typically, the membrane is dried before storage. The membrane can be stored at any suitable temperature, e.g., in the range of from about 4 °C to about 25 °C, more preferably in the range of from about 4 °C to about 15 °C. If desired, the membrane can be stored in any suitable storage agent, e.g., buffer or saline solution, aqueous alcohol, sodium hydroxide, or glycerin and sodium azide.

[0039] Hollow fiber membranes according to the invention can be produced from any suitable material, e.g., ceramic, metal, or more preferably, a polymer or combinations of polymers. Suitable polymers include, for example, polyaromatics, sulfones (such as polysulfone, polyarylsulfone, polyethersulfone, polyphenylsulfone), polyolefins, polystyrenes, polycarbonates, polyamides, polyimides, fluoropolymers, cellulosic polymers such as cellulose acetates and cellulose nitrates, and PEEK. Other examples include, polyetherimide, acrylics, polyacrylonitrile, polyhexafluoropropylene, polypropylene, polyethylene, polyvinylidene fluoride, poly(tetrafluoroethylene), polymethyl methacrylate, polyvinyl alcohol, polyvinyl pyrrolidone (PNP), polyvinyl chloride, polyester, poly(amide imides), and polydiacetylene, and combinations thereof. Any of these polymers can be chemically modified.

[0040] In some embodiments wherein the polymer solution comprises a first polymer and a second polymer, the first polymer is polysulfone (more preferably, polyethersulfone) or polyvinylidene fluoride, and the second polymer is PVP. Typically, PVP is utilized as a pore former and morphology enhancer, and is substantially removed during the preparation of the membrane. [0041] The polymers can have any suitable average molecular weight. However, in some embodiments wherein the polymer (or the first polymer) is a sulfone (e.g., polysulfone, polyethersulfone, polyphenylsulfone, and polyarylsulfone), the polysulfone has an average molecular weight in the range of from about 30,000 to about 60,000 daltons. In some embodiments wherein the second polymer is PVP, the PVP has an average molecular weight in the range of from about 5,000 to about 120,000 daltons, preferably, in the range of from about 10,000 to about 15,000 daltons.

[0042] A variety of suitable solvents, pore formers, nonsolvents, surfactants, and additives are known in the art. Suitable solvents can be protic or aprotic. Acceptable aprotic solvents include, for example, dimethyl formamide, N-methyl pyrrolidone (NMP), dimethyl sulfoxide, sulfolane, and dimethyl acetamide (DMAC). Acceptable protic solvents include, for example, formic acid and methanol. Other suitable solvents include, for example, dioxane, chloroform, tetramethyl urea, tetrachloroethane, and MEK.

[0043] Suitable pore formers (generally, the concentration of the pore former influences the pore size and pore distribution, including the asymmetry ratio, in the final membrane) include, for example, polyvinyl pyrrolidone (PVP), polyethylene glycol (PEG), and glycerin.

[0044] Suitable nonsolvents can be solids or liquids. In general, the concentration of the nonsolvent influences the pore size and pore distribution, and, when utilized as the coagulation medium or quench solution, causes phase inversion (precipitation). Exemplary liquid nonsolvents include, for example, aliphatic alcohols, particularly polyhydric alcohols, such as ethylene glycol, glycerine; polyethylene oxides and polypropylene oxides; surfactants such as alkylaryl polyether alcohols, alkylaryl sulfonates and alkyl sulfates; triethylphosphate, formamide; and aliphatic acids such as acetic or propionic acid. Other suitable liquid nonsolvents include, for example, 2-methoxyethanol, t-amyl alcohol, methanol, ethanol, isopropanol, hexanol, heptanol, octanol, acetone, methylethylketone, methylisobutylketone, butyl ether, ethyl acetate, amyl acetate, diethyleneglycol, di(ethyleneglycol)diethylether, di(ethyleneglycol)dibutylether, and water. Exemplary solid nonsolvents include polyvinyl pyrrolidone, citric acid, and salts such as zinc chloride and lithium chloride. [0045] One preferred embodiment of a spinning dope comprises from about 10 to about 30 wt.% first polymer, more preferably from about 15 to about 22 wt.% first polymer; in the range of from about 8 to about 25% nonsolvent, preferably in the range of from about 10 to about 13 wt.% nonsolvent; in the range of from about 10 to 40 wt.% second polymer, more preferably about 18 to 25 wt.% second polymer; and in the range of from about 35 to about 65 wt.% solvent, more preferably in the range of from about 40 to about 55 wt.% solvent.

[0046] The spinning dope should have sufficient viscosity to provide adequate strength to the fiber extrudate as it is extruded from the extrusion head. The viscosity of the spinning dope at the extrusion temperature can be any suitable viscosity, and is typically at least about 1000 centipoise, more typically at least about 5,000 centipoise, and preferably in the range of from about 10,000 to 1,000,000 centipoise. [0047] A variety of spinnerets or extrusion heads are suitable for carrying out the invention. Preferably, the extrusion head is a multi-orifice type, e.g., as shown in cross-sectional side view in Figures 2 and 3, and cross-sectional bottom view in Figures 4-6. Typical orifice diameters are in the range of from about .01 cm to about 0.5 cm, preferably in the range of from about .02 cm to about .3 cm. However, as is known in the art, the orifice diameters selected will generally depend on the desired hollow fiber dimensions and intended application. For example, using the illustrative heads shown in Figures 2-6 for reference, the central orifice or bore 1 in the extrusion head 100 should be large enough to permit sufficient flow of the bore fluid to yield a fiber of the desired size, the orifice 2 through which the spinning dope is extruded is typically sufficient to permit sufficient flow of the spinning dope while provide the desired membrane wall thickness, and the orifice 3 through which the coagulation medium is passed is typically sufficient to permit sufficient flow of the coagulation medium so that it will contact the fiber as it passed from the orifice 2. In some embodiments of the invention, the central orifice or bore has a general diameter in the range of from about .03 cm to about .15 cm.

[0048] Preferably, the extrusion head has an inner or outer element that rotates while one or more other elements of the head do not. For example, an element including the central orifice 1 can rotate, while the other element(s) remain stationary, an element including the inner or outer wall of orifice 2 can rotate while the other element(s) remain stationary, or an element including the outer wall of orifice 3 can rotate while the other element(s) remain stationary.

[0049] The spinning dope is delivered to the extrusion head from a supply source by any means known in the art (e.g., via one or more pumps or gas pressure) that will provide a consistent flow at the desired rate. Typical flow rates are, for example, in the range of from about 0.5 cc/min to about 20 cc/min, more typically, in the range of from about 1 cc/min to about 10 cc/min. However, as is lαiown in the art, the flow rate for a given viscosity is dependent upon the size of the extrusion head and the number and size of the orifices.

[0050] Similarly, the bore injection fluid (sometimes referred to as the "core fluid") is also delivered to the spinneret or extrusion head from a supply source by any means lαiown in the art. Alternatively, in some embodiments involving a dry-wet process, the pressure differential between the bore of the orifice in the spinneret and the subatmospheric pressure within the chamber that encases the spinneret can be sufficient to aspirate the core fluid into the spinneret. A variety of bore injection fluids (gas or liquid) can be utilized, and the fluid can include a mixture of components. Preferably, in those embodiments wherein the pores on the inside surface of the membrane are larger than those on the outside surface, the bore injection fluid is not a quenching fluid, e.g., the injection fluid can be, for example, air, nitrogen, CO₂, a fluid without strong capacity to impart precipitation, or a fluid with a sufficiently high concentration of solvent so that coagulation does not occur. However, in other embodiments, e.g., wherein the pores on the inside surface are smaller than those on the outside suiface, the bore injection fluid can be a quenching fluid.

[0051] The coagulation medium is also delivered to the spinneret or extrusion head from a supply source by any suitable means. Preferably, however, the coagulation medium is directed through an orifice aligned with the outside of the spimiing dope such that the coagulation medium contacts the outer surface of the extruded pre-fiber as it exits the extrusion head. Typical flow rates are, for example, in the range of from about 40 cc/min to about 150 cc/min. Preferably, the flow rate is in the range of from about 60 to about 120 cc/min.

[0052] Typically, the temperatures of each of the spinning dope, the core fluid, and the coagulation medium are controlled (in some embodiments, separately controlled) as is lαiown in the art.

[0053] The membranes can have any suitable pore structure, and can be used in microfiltration, ultrafiltration, and reverse osmosis applications. [0054] The hollow fiber membranes according to any embodiments of the invention can be skinned or unskinned. Alternatively, or additionally, the hollow fiber membranes can be symmetric or asymmetric. For example, in some embodiments the hollow fiber membrane comprises an unskinned membrane, preferably a polymeric unskinned membrane, the membrane can include a spiraled inside surface, and a substantially smooth outside surface or a spiraled outside surface. Alternatively, the membrane can include an inside substantially smooth surface and a spiraled outside surface. In another embodiments comprising unskinned membranes, the hollow fiber membrane can include a spiraled outside surface, and a substantially smooth inside surface or a spiraled inside suiface. Alternatively, the membrane can include a substantially smooth outside surface and a spiraled inside suiface. In accordance with any of these embodiments, the hollow fiber membrane can be symmetric or asymmetric. In those embodiments wherein the membrane is an asymmetric membrane, the more open area can face the inner surface or the outer surface. [0055] In accordance with other illustrative embodiments wherein the hollow fiber membrane comprises a skinned membrane, preferably a polymeric skinned membrane, the membrane can include an inside skin having a spiraled surface, and a substantially smooth outside surface or a spiraled outside surface. Alternatively, the membrane can include an inside skin having a substantially smooth surface and a spiraled outside surface. In another embodiments comprising skinned membranes, the hollow fiber membrane can include an outside skin having a spiraled surface, and a substantially smooth inside surface or a spiraled inside surface. Alternatively, the membrane can include an outside skin having a substantially smooth surface and a spiraled inside surface.

[0056] In some of those embodiments of the invention wherein the membranes are asymmetric, the membranes have larger size pores at the inside surface of the hollow fiber, and smaller size pores at the outside surface. In accordance with some embodiments of the invention, the membranes have a progressive asymmetric structure across the cross-section between the inside surface and the outside surface. Accordingly, the pore distribution, with the largest size pores arranged at or adjacent to the inside surface, and the pores becoming gradually smaller toward the outside surface, can be compared to a funnel. In other embodiments, the membranes have an isotropic structure for at least a portion of the thiclαiess of the membrane between the inside surface and the outside surface. Preferred embodiments of asymmetric membranes according to the invention do not have "hourglass-shaped" pores. [0057] In conventional hollow fiber membranes typically used in inside-out flow applications, the inside surface of the membrane has a smaller pore size than in the outside surface, as it is believed the smaller pores at the inner surface prevent large molecules and debris from entering the pores, thus reducing fouling of the membrane. In contrast, in accordance with some of the embodiments of asymmetric membranes of the present invention, i.e., having at least one spiraled surface, the average pore size on the inside surface (the inside surface being spiraled or non-spiraled) and in the inner portion is larger than the pores on the outside surface (the outside surface being spiraled or non-spiraled) and in the outer portion, surprisingly resulting in membranes providing efficient filtration (retaining and/or capturing larger molecules, species and debris, while allowing the smaller molecules and species to pass in the permeate) and advantageously providing increased capacity and resistance to fouling. [0058] In some embodiments of asymmetric membranes according to the invention, the membranes have relatively large pores at the inside surface and relatively small pores at the outside surface wherein the pores generally decrease in size across the cross-section of the membrane from the inner surface to the outer surface, and wherein the membrane is substantially free of macrovoids. In some embodiments, the average pore size gradually decreases, or is more or less constant, and then decreases more rapidly across the cross-section of the membrane from the inner surface to the outer surface.

[0059] In typical embodiments of asymmetric hollow fiber membranes according to the invention, the ratio of the inside surface pore structure, e.g., the average pore size rating, the average pore diameter, the average pore size, the mean flow pore size (for example, as estimated by one or more of scanning electron microscopy (SEM) analysis, porometry analysis, particle challenge, molecular weight challenge with molecular markers, nitrogen absorption/deabsorption analysis, and bubble point measurement), to the outer surface pore structure is at least about 5 to 1 (this can also referred to as an asymmetry ratio of at least about 5), more preferably, a ratio of the inside surface pore structure to the outer surface pore structure of at least about 10 to 1 (asymmetry ratio of at least about 10). However, asymmetry can be gradual or abrupt within the thickness of the membrane, and two membranes can have similar ratios of inside surface to outside surface pore structures (e.g., 10 to 1), but with very different internal structures, depending on whether there is a steady gradient of increasing pore sizes, or different regions within the membrane having different gradients of pore size changes.

[0060] For microfiltration and ultrafiltration membranes, the ratio of the inside surface pore structure to the outside surface pore structure is more preferably at least about 100 to 1 (asymmetry ratio of at least about 100). In some embodiments, membranes according to the invention have a ratio of the inside surface pore structure to the outside surface pore structure of at least about 1000 to 1 or more (asymmetry ratio of at least about 1000), even at least about 10,000 to 1 (asymmetry ratio of at least about 10,000).

[0061] As noted above, some embodiments of membranes according to the invention, having larger pores at the inner surface and in the inner portion of the membrane and smaller pores at the outer surface and outer portion of the membrane, provide an increased capacity and resistance to fouling when compared to conventional membranes for inside-out flow applications, i.e., wherein such conventional membranes have smaller pores at the inner surface and larger pores at the outer surface. Accordingly larger molecules and/or species can be rejected or retained in the inner portion while smaller molecules and/or species pass in the permeate. [0062] With respect to pore structure, ultrafiltration membranes are typically categorized in terms of molecular weight exclusion cutoff (MWCO) values, which can be based on the efficiency of membrane retention of substances having lαiown molecular weights, e.g., polysaccharides or proteins. Accordingly, inventive ultrafiltration membranes can have MWCOs in the range of about 1 kDA (1000 daltons), or less, to about 1,000 kDa (1,000,000 daltons), or more. Illustratively, ultrafiltration membranes according to the invention can have MWCOs of, for example, about 10 kDa or less, about 30 kDa, about 50 l Da, about 100 kDa, or more. [0063] Microfiltration membranes are typically categorized in terms of the size of the limiting pores in the membranes, which, in accordance with the invention, are typically in the outside surface of the membrane and/or adjacent the outside surface of the membrane. Accordingly, microfiltration membranes according to embodiments of the invention can have, for example, limiting pores, mean flow pore sizes, or average pore sizes of about 0.02 microns or more, e.g., in the range of from about 0.03 microns to about 5 microns. Illustratively, inventive microfiltration membranes can have limiting pores, mean flow pore sizes, or average pore sizes of 0.05 microns, 0.1 microns, 0.2 microns, 0.45 microns, 0.65 microns, 1 micron, 2 microns, or larger. [0064] The hollow fiber membrane can have any suitable dimensions, and the dimensions can be optimized for the particular application. [0065] The membranes can have any suitable inside diameter and outside diameter. The outside diameter of the membrane can be, for example, at least about 100 μm (microns), e.g., in the range of from about 150 microns to about 3000 microns, or more. Typically, the outside diameter is in the range of from about 500 microns to about 1800 microns. The inside diameter of the membrane can be, for example, about 500 microns (0.5 mm), about 1000 microns (1 mm), or about 1500 microns (1.5 mm).

[0066] The membranes can have any suitable wall (and/or support region) thickness. Typically, hollow fiber membranes according to the invention have a wall thickness in the range of from about 100 to about 600 microns, more preferably 200 to about 400 microns. However, other embodiments can have thicker or thinner wall thicknesses.

[0067] In accordance with preferred embodiments of the invention, the hollow fiber is substantially free of macro voids, which are finger-like projections or voids that are materially larger in size than the largest pores in the membranes. An advantage of substantially macrovoid membranes according to the invention is that the membranes can be integrity tested, preferably air integrity tested.

[0068] In preferred embodiments, the membranes are integral, i.e., they do not have a plurality of layers laminated together. In a more preferred embodiment, the integral membrane is all of one composition.

[0069] Filters according to embodiments of the invention can have any number of hollow fiber membranes, and a filter can include hollow fiber membranes with different characteristics. While a filter according to an embodiment of the invention can comprise a single hollow fiber, typically, the filter comprises at least two, preferably, about 10 or more, hollow fiber membranes.

[0070] Preferably, hollow fiber membranes according to the invention (as well as filters and filter devices including the membranes) are sterilizable in accordance with protocols lαiown in the art. For example, polysulfone and polyethersulfone membranes according to the invention are typically steam sterilizable. [0071] Some embodiments of hollow fiber membranes according to the invention (and filter devices including the membranes) can be cleaned (and the devices flushed) in accordance with general protocols lαiown in the art. For example, devices according to the invention are typically flushed with buffer or spent filtrate, and the membranes cleaned with caustic solutions such as sodium hydroxide solutions (e.g., about 0.1 -0.5NNaOH).

[0072] Some embodiments of membranes (and filters and devices including the membranes), particularly some embodiments including larger pores on the inside surface than the outside surface, can be backwashed, wherein the wash fluid passes from the outside small pores through the inside large pores, thus directing the larger contaminants away from the smaller pores, into the bore of the membrane, and through an end of the membrane. As a result, the potential for plugging the membrane caused by pushing the larger contaminants into the smaller pores is reduced.

[0073] Membranes according to the invention have a variety of applications, particularly when utilized in filter devices (e.g., modules, cartridges, and cassettes). Typically, the filter device comprises a housing having an inlet and at least one outlet, and a filter comprising one hollow fiber, preferably, two or more hollow fibers, disposed in the housing. While the membranes are preferably used in tangential flow devices, they can also be used in dead end flow devices. They can be used in single pass and multiple pass applications, and can be adapted for inside-out and outside-in flow applications. [0074] Embodiments of filter devices comprising a single hollow fiber membrane, or a few hollow fiber membranes (e.g., 2, 3, or 4 membranes), can be especially for those applications wherein a small volume of fluid is to be filtered. [0075] Applications include gas and/or liquid filtration, for example, water filtration (e.g., particulate and/or microorganism removal from municipal water, or preparation of pure water for microelectronics), filtration of paint, waste water, and particulate, pyrogen, virus and/or microorganism removal from other fluids, including biological fluids such as blood. In preferred embodiments, the membranes are useful in filtering fluids for protein concentration and purification, e.g., for biopharmaceutical applications, e.g., to isolate cell expression products from cells and undesirable cellular matter. Other applications include, for example, cell-virus separation, cell-macromolecule separation, virus-macromolecule separation, macromolecule-macromolecule separation, species-species separation, and macromolecule-species separation.

[0076] As noted above, hollow fiber membranes according to some embodiments of the invention, i.e., having pores in the inner surface and inner portion that are larger than the pores at the outer surface and outer portion, provide efficient filtration (rejecting, retaining and/or capturing larger molecules, species and/or debris, while allowing the smaller molecules and/or species to pass in the permeate) and advantageously providing increased capacity and resistance to fouling. In preferred embodiments, the membranes efficiently retain the larger molecules or species while allowing the smaller molecules or species of interest to pass through at a high concentration or throughput. [0077] Additionally, membranes according to embodiments of the invention can be used to fractionate molecules that differ in size in a ratio of about 5 to 1 (i.e., fractionating larger molecules from smaller molecules wherein the larger molecules are about 5 times larger in size than the smaller molecules) or less. More preferably, some embodiments can be used to fractionate molecules that differ in size in a ratio of about 3 to 1 or less, and in some embodiments, can be used to fractionate molecules that differ in size in a ratio of about 2 to 1, or even less.

[0078] When compared to conventional hollow fiber devices (having smooth surfaced membranes with smaller pores on the inside surface and larger pores on the outside surface) used in similar applications, embodiments of the invention (wherein the pore size of the inventive membranes is the same as that of the conventional hollow fiber membrane) have at least one of higher fluxes, higher macromolecule transmissions, and higher species transmissions, in some embodiments, about 1.5 or even 2 times greater, that of conventional devices. Moreover, these improvements can be achieved without substantially increasing the transmembrane pressure (TMP). [0079] With respect to capacity, e.g., volume of permeate generated per unit area of the membrane, embodiments of the invention provide higher capacities, in some embodiments, about 2, 4, 5, or even about 6 times that of such conventional devices used in the same applications and having the membranes with the same pore sizes. [0080] The invention also provides filters and filter devices including the hollow fiber membranes for both inside-out flow applications, and outside-in applications. [0081] Embodiments of filter devices according to the invention comprise at least one, more typically, a plurality, of hollow fibers disposed in a housing, the housing including at least one inlet and at least one outlet. For example, one filter device, preferably utilized in dead end filtration applications, comprises a housing having an inlet and an outlet and defining a fluid flow path between the inlet and the outlet, and a filter comprising one or more porous hollow fiber membranes disposed across the fluid flow path, each porous hollow fiber having a spiraled inner surface and an outside surface; wherein the housing is arranged to direct fluid from the inlet, through the spiraled inside surface and the outside surface of the porous hollow fibers, and through the outlet.

[0082] In another embodiment of a filter device for dead end filtration applications according to the invention, the device comprises a housing having an inlet and an outlet and defining a fluid flow path between the inlet and the outlet, and a filter comprising one or more porous hollow fiber membranes disposed across the fluid flow path, each porous hollow fiber having a spiraled outer surface and an inside surface; wherein the housing is arranged to direct fluid from the inlet, through the spiraled outside surface and the inside surface of the porous hollow fibers, and through the outlet.

[0083] Another filter device, preferably utilized in tangential flow filtration (TFF) applications, comprises a housing having an inlet, a first outlet and a second outlet, the housing defining a first fluid flow path between the inlet and the first outlet, and a second fluid flow path between the inlet and the second outlet; a filter comprising one or more porous hollow fibers disposed across the first fluid flow path and substantially parallel to the second fluid flow path, each porous hollow fiber having an inner spiraled porous surface and an outer porous surface; wherein the housing is arranged to direct a portion of fluid from the inlet, through the inside surface and the outside surface of the porous hollow fibers, and through the first outlet, and direct another portion of fluid from the inlet, along the spiraled inner surface and the central bore of the membrane, and through the second outlet.

[0084] In another embodiment of a device for TFF applications, wherein the device comprises an inlet, first and second outlets, and a filter comprising at least one fiber, each porous fiber has an outer spiraled porous surface and an inner surface, and the housing is arranged to direct a portion of fluid (preferably, the permeate) from the inlet, through the outside surface and the inside surface of the porous hollow fibers, and along the central bore and through the second outlet, and direct another portion of fluid (preferably, the retentate) from the inlet, along the spiraled outer surface and through the first outlet.

[0085] In one exemplary embodiment, wherein the filtration device comprises a cylindrical filtration assembly having a bundle of fibers therein wherein the fluid is fed from the shell side (permeate collected within the bore), fibers having spiraled outer surfaces can be densely packed in the bundle while allowing sufficient space between the fibers for improved feed distribution, more preferably without including fiber spacer elements such as solid filaments in the bundle or textile weaving to create space between the fibers.

[0086] Housings for filter devices can be fabricated from any suitable impervious material, preferably a rigid material, such as any thermoplastic material, which is compatible with the fluid being processed. For example, the housing can be fabricated from a metal, or from a polymer. In a preferred embodiment, the housing is a polymer, preferably a transparent or translucent polymer, such as an acrylic, polypropylene, polystyrene, or a polycarbonated resin. Such a housing is easily and economically fabricated, and allows observation of the passage of the liquid through the housing.

[0087] The hollow fiber membrane(s) can be sealed or potted in the housing as is lαiown in the art. Typical sealants or potting materials include, for example, an adhesive such as urethane and/or epoxy.

[0088] Typical embodiments of systems according to the invention include at least one filter device as described above, a plurality of conduits, at least one pump (in some embodiments, e.g., involving cell and/or virus separation wherein the filtrate rate is controlled and/or metered, systems typically include at least one additional pump), and at least one container or reservoir. More typically, an embodiment of the system for tangential flow filtration includes a feed reservoir and a filtrate reservoir. [0089] All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.

[0090] The use of the terms "a" and "an" and "the" and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., "such as") provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.

[0091] Preferred embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Of course, variations of those preferred embodiments will become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.

Claims

WHAT IS CLAIMED IS:

1. A membrane comprising: a hollow fiber having an inside surface and an outside surface, wherein at least one of the surfaces comprises a spiraled surface.

2. The membrane of claim 1, comprising a spiraled inside surface.

3. The membrane of claim 1, including a spiraled outside surface.

4. The membrane of claim 1, including a skinless membrane.

5. The membrane of claim 1 , including a skinned membrane.

6. The membrane of claim 1, including a symmetric membrane.

7. The membrane of claim 1, including an asymmetric membrane.

8. The membrane of claim 1, adapted to allow fluid flow from the outside surface to the inside surface.

9. The membrane of claim 1 , adapted to allow fluid flow from the inside surface to the outside surface.

10. The membrane of claim 1 , wherein the hollow fiber has an inner opening that is star-shaped.

11. The membrane of claim 1 , wherein the hollow fiber has an imier opening that is tri-lobed.

12. The membrane of claim 1, having a progressively asymmetric structure from the inside surface to the outside surface.

13. A filtration assembly comprising a filter, the filter comprising two or more hollow fiber membranes of claim 1.

14. A filter device comprising: a housing having an inlet and an outlet and defining a fluid flow path between the inlet and the outlet, and a plurality of porous hollow polymer fiber membranes of claim 2 disposed across the fluid flow path, each porous hollow fiber membrane having an inner surface and an outer surface; wherein the housing is arranged to direct fluid from the inlet, through the inner surface and the outer surface of the porous hollow fiber membranes, and through the outlet.

15. A filter device comprising: a housing having an inlet and an outlet and defining a fluid flow path between the inlet and the outlet, and a plurality of porous hollow polymer fiber membranes of claim 2 disposed across the fluid flow path, each porous hollow fiber membrane having an inner surface and an outer surface; wherein the housing is arranged to direct a portion of fluid from the inlet, through the inside surface and the outside surface of the porous hollow fibers, and tlirough the first outlet, and direct another portion of fluid from the inlet, along the inner surface and the central bore of the membrane, and through the second outlet.

16. The membrane of claim 1, wherein the membrane is a microfiltration membrane.

17. The membrane of claim 1 , wherein the membrane is a microfiltration membrane.

18. A method for processing a fluid suspension containing a macromolecule of interest comprising: providing at least one porous hollow polymer fiber membrane having a spiraled inside porous surface and an outside porous surface; contacting the inside spiraled surface of the membrane with the fluid suspension and passing the type of macromolecule of interest from the inside surface to the outside surface while retaining any undesirable material between the inside and outside surfaces.

19. A method of separating a fluid into a retentate and a permeate comprising: directing a feed suspension comprising larger macromolecules and smaller macromolecules into the central bore of a hollow fiber membrane, the membrane having an inside porous spiraled surface and an outside porous surface; passing a permeate containing the smaller macromolecules from the inside surface to the outside surface; and passing a retentate containing the larger macromolecules along the inside surface and the central bore of the membrane.

20. A method of preparing a hollow fiber membrane comprising: providing a spinning dope comprising a first polymer, a solvent, and a nonsolvent, in ratios sufficient to form a homogenous solution or a colloidal dispersion; extruding the dope in the form of a hollow pre-fiber from a nozzle, the pre-fiber having an inside surface and an outside surface, the nozzle including an inner or outer rotating element; contacting the outside surface of the pre-fiber with a coagulating medium; and coagulating the pre-fiber from the outside surface to the inside surface to provide a hollow fiber membrane with a spiraled inside and/or outside surface.

21. A method of preparing a hollow fiber membrane comprising : providing a spinning dope comprising a first polymer, a solvent, and a nonsolvent, in ratios sufficient to form a homogenous solution or a colloidal dispersion; extruding the dope in the form of a hollow pre-fiber from a nozzle, the pre-fiber having an inside surface and an outside surface, the nozzle including an inner or outer rotating element; contacting the inside surface of the pre-fiber with a coagulating medium; and coagulating the pre-fiber from the inside surface to the outside surface to provide a hollow fiber membrane with a spiraled inside and/or outside surface.

22. The method of claim 20, wherein the spinning dope also comprises an additional polymer.

23. The method of claim 22, wherein the additional polymer is polyvinyl pyrrolidone (PVP).

24. The method of claim 20, wherein the first polymer is a sulfone polymer.

25. The method of claim 20, further comprising collecting the hollow fiber membrane on a receiving plate.

26. The method of claim 21 , wherein the spiiming dope also comprises an additional polymer.

27. The method of claim 26, wherein the additional polymer is polyvinyl pyrrolidone (PVP).

28. The method of claim 27, wherein the first polymer is a sulfone polymer.

29. The method of claim 21 , further comprising collecting the hollow fiber membrane on a receiving plate.