CN1029822C - Composite membranes and their manufacture and use - Google Patents
Composite membranes and their manufacture and use Download PDFInfo
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- CN1029822C CN1029822C CN 88106070 CN88106070A CN1029822C CN 1029822 C CN1029822 C CN 1029822C CN 88106070 CN88106070 CN 88106070 CN 88106070 A CN88106070 A CN 88106070A CN 1029822 C CN1029822 C CN 1029822C
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Abstract
The present invention relates to a method for manufacturing composite hollow fibrous membranes using dilute solution of a membrane-forming composition containing membrane forming material and a solvent to coat porous hollow fiber base material. Thus, the porous hollow fiber base material contacts the composition, the solvent is partially evaporated from the coated porous hollow fiber base material, the partial coated porous hollow fiber base material which is dried contacts solidified liquid, and the composite porous hollow fibrous membranes are recovered. The present invention also comprises the composite hollow fibrous membranes manufactured by the method, and an application as a permeable membrane of at least one kind of fluid and at least the other kind of fluid in fluid mixture separation.
Description
The present invention relates to be used for the new preparation method of the permeable membrane of separation of the fluid (as gas).More particularly, it relates to the production of the compound infiltration hollow-fibre membrane with improved infiltration and selective power.
Optionally the permeable membrane of a component of osmotic fluid mixture (no matter being liquid or gas) is considered to habitually practise in this technical field, and its potential great advantages is that the fluid that is used for realizing ideal separates.For the industrialization of reality operation, permeable membrane must can reach the acceptable selective power of gas contained in the individual stream or liquid and can reach the high productive capacity of desirable fluid separation simultaneously.
In the art,, various types of permeable membranes had been proposed for carrying out all gases lock out operation.These films generally can be divided into (1) homogeneous pattern, (2) asymmetric sexual type or (3) compound.So-called homogeneous pattern and asymmetric sexual type film mainly are made up of the single permeable membrane material of required component in the separating gas mixture optionally.The homogeneous pattern film has identical density on its whole thickness.This film generally has the shortcoming of poor permeability, and in other words, because the thickness of film is thicker, contact must be that permeation flux is low with it.The feature of asymmetric membrane is to exist two kinds of different morphology areas in the structure of film.Zone comprises optionally thin, the fine and close semi-transparent top layer of a component in the permeate gas mixture of one deck.Another zone then comprises the not too supporting area of densification, porous and non-selectivity of one deck, and its effect is to prevent that the thin list layer of film is destroyed under pressure.
Composite membrane generally comprises the thin layer or the coating of a kind of suitable permeable membrane material superimposed on porous substrate.The divided thin film absciss layer of the stalling characteristic of decision composite construction is preferably extremely thin, so that desirable high osmosis recited above is provided.Base material only is used for providing supporting role to position thin layer thereon.
Because the advantage of pay attention to day by day permeable membrane in the prior art, the performance requirement of this film has been improved too.Therefore, prior art is just turning to separation with desirable permeance property and don't sacrifice doughnut or other permeable membrane structure or the very thin film of selecting performance.Therefore, the gas at various industrialization meanings separates more and more hope realization permeability and the more favourable combination of selectivity.Also wish to promote and improve the used method of deposition film separating layer on porous substrate, and the uniformity of improving porous substrate upper film separating layer.
As mentioned above, the homogeneous pattern film generally is unsuitable for reaching this requirement.On the other hand, asymmetric membrane can be developed the gas that is used for this reality and separate use, but they do not have and make it to realize optimized inherent adaptability for concrete gas separates to use easily.Though can do thin, the fine and close semi-permeable layer of specific asymmetry membrane material thinner for increasing permeability, unless but carry out modification with specific treatment technology, otherwise the selectivity of described material might also not reach each component of in concrete the application, separating pending gas enough degree.
Have been found that the United States Patent (USP) 3,133 at Loeb, the thin top layer of this class asymmetric membrane described in 132 often is not perfectly, but comprises various defectives.These are with residual hole, and the defective that forms such as little pin hole exist has constituted the hole of large-size, and will preferentially go over from these orifice flows through the feed gas of the film made by this material.As a result, owing in membrane structure, exist these defectives will cause the interaction of feed gas and permeable membrane material itself, just make the fractional dose of gas reduce greatly.Under the situation of asymmetry polysulfone hollow fibre, the feasible selectivity (defining as the back) to air of these defectives is about 1, and in contrast, its selectivity of flawless polysulfones is about 6.In to the solution that this problem proposed, people such as Henis are at United States Patent (USP) 4, disclose a kind of method with coating material coating asymmetric membrane in 230,463, these coating materials have score from the little intrinsic separation factor of determining of the intrinsic separation factor of membrane material.The coating process that people such as Henis use is at United States Patent (USP) 4,230, and the table X VI in 463 51 and 52 hurdles is narrated to some extent.These methods comprise with porous hollow fiber membrane not diluted or in the liquid coating material of solvent dilution, flood, allow excessive liquid coating material drip then; Under the situation that has solvent to exist, allow solvent evaporate.When making in this way, selectivity being approximately 2 polysiloxanes is coated on the polysulfone hollow fibre, so that its selectivity increases to 2～6 by above-mentioned 1～1.5, such selectivity generally is to approach 6, the permeability of this polysiloxanes/polysulfones composite (such as hereinafter definition) be lower, promptly about 0.2 or lower, this just causes the requirement to thinner film, promptly need thin dense skin, particularly owing to the requirement that operation increases day by day to high flux in the prior art more needs so.Yet, relatively Bao film cause those need repair with reach acceptable can the increasing of number of defects.Be not interrupted though improve the effort of the method, in the prior art other method still had a kind of requirement, to reach selectivity and infiltrative desired binding in the actual industrial operation.Therefore, use, separate, providing maximum possibility aspect selectivity and the infiltrative desired binding for realizing for the specific gas that the industrialization meaning is arranged to required gas separates the composite membrane that the special membrane material of selecting is made.It should be noted that composite membrane not only must include very thin film in order to reach desirable in the prior art performance requirement, and must be included as the required the most favourable separating layer-matrix structure of gas lock out operation that reaches desirable.A kind of like this application of essential industry meaning is arranged is air separation, and specifically, in the method, optionally permeated oxygen is as oxygen enrichment infiltration gas and reclaim for membrane material, and nitrogen-enriched stream is discharged from as non-infiltration gas.Therefore, the needs and the requirement of a reality are arranged in the prior art, develop a kind of compound film that is particularly suitable for air separation and other desired gas lock out operation exactly, for example from ammonia swept-off gases and refinery's air-flow, reclaim hydrogen, and in various operations (such as three back production) separating carbon dioxide and methane.
Separate the pellicle that had proposed a large amount of various materials and shape for carrying out these in the prior art.So-called composite membrane has been proposed, in this film, the suitable semipermeable membrane material of superimposed skim on relative base material than porous.This separating layer is film very preferably, so that above-mentioned desired high flux is provided.Base material provides supporting for superimposed fragile and very thin infiltration rete or coating on it.Narrated this class structure of composite membrane in people's such as people's such as Salemme United States Patent (USP) 4,155,793 and Klass United States Patent (USP) 3,616,607, still, structure of composite membrane is not produced by method of the present invention.
What should draw attention is, for the film of some separation methods like this, no matter is liquid or gas, all requires film to have the perfection of height in film or separating layer.In the middle of gas separating technology, pervaporation, Perstruction etc., if rete without any residual hole or other defective, clearly can obtain best result.On the other hand, rete requires to make thin as much as possible and even, so that obtain desired high infiltration rate, thereby obtains high total points from process productivity ratio.In these cases, in the thin separating layer of composite membrane, usually find the morphologic defective that occurs with forms such as residual hole, little pin holes.These defectives may be introduced the film system making the various typical phases of film (as reel off raw silk from cocoons, the combination manufacturing operation of curtain coating, coating, curing and film).
For the problem of fix the defect, Browall is at United States Patent (USP) 3,980, disclose a kind of method in 456, promptly used the coating of the second layer, sealing on very thin film, to cover because the defective that particulate contamination causes.The composite construction of handling so substantially is a plyability, in addition, uses the superimposed very thin film of one deck generally can not provide desirable separation selectivity under flux that does not reduce infiltration gas or infiltrative situation on the supporting substrate of porous.Yet this patent does not disclose the method for applicant's coated film separating layer on porous substrate.
United States Patent (USP) 4 people such as Ward, disclose a method in 214,020, it is by a branch of doughnut is dipped in the coating solution, and the outer surface of coating doughnut combined films is exerted pressure so that coating solution is driven to the fiber to inside from the outside of doughnut then.This method makes and form a pantostrat/coating on the outside of doughnut, as described in people's such as above-mentioned Henis patent, the asymmetric membrane that this method is particularly suitable for having with the coating of the coating solution of high gas permeable material some residual holes prepares the high-selective gas diffusion barrier, but this is not a method of the present invention.
United States Patent (USP) 4 people such as Arisak, 127, a kind of method of asymmetric hollow fibre is disclosed in 625, the outer tube spinning that it is the spinning solution that will become fiberized resin by a double-tube type spinning head enters in the water coagulating bath forming doughnut, and the interior pipe by spinning head injects the inside of the aqueous solution with the contact doughnut simultaneously.Immerse in the warm water it and drying then.Applicant's clotting method when this patent is not disclosed in the film separating layer that coating approaches on the preformed hollow porous substrate surface.
United States Patent (USP) 4 people such as Riley, 243, a kind of method that forms the film of the non-porous permeable membrane of one deck on the surface of porous supporting mass is disclosed in 701, it is the solution that the porous supporting mass is formed by a kind of halogenated hydrocarbon solvent that contains the prepolymer that forms permeable membrane and crosslinking agent, from solution, take out coated porous supporting mass, thereby at high temperature make the crosslinked formation of prepolymer composite membrane then.
In people's such as Coplan United States Patent (USP) 4,467,001, disclose a kind ofly be used for applying, dry and solidify the method and apparatus of multifilament.Liquid coating is applied on the long filament in the U-shaped pipe, and carries out drying and curing in gas atmosphere.For using coagulating agent on base material, to form the divided thin film absciss layer without any list of references.
In people's such as Kraus european patent application 0175688AI, a kind of method to porous substrate coating divided thin film absciss layer is disclosed.It is by with porous substrate with solvent impregnated to be full of hole, coat polymers solution is immediately then realized to form a divided thin film absciss layer on by the surface of solvent impregnated porous substrate.Solvent in the porous substrate hole prevents that polymer solution from entering in the hole of base material.Remove dry this composite membrane of two kinds of solvents (the dipping solvent of solvent and solution) by evaporation then.
Article " composite hollow fiber membrane " J.App.Polym.Scl. at J.Cabasso and A.P.Tamvakis, 23,1509-1525(1979), the production of compound doughnut has been discussed, wherein, has been drained Toluene-2,4-diisocyanate between immersion then with rare polyethyleneimine: amine aqueous solution coating hollow polysulfone fibre, 4, in the vulcabond, at air drying about 10 minutes, crosslinked 10 minutes at 100～110 ℃.Also disclose the method with furane resins coatings hollow polysulfone fibre, it is with sulfuric acid (2%(weight)) make furfuryl alcohol (4%(weight) aqueous solution) polymerization, then 150 ℃ of curing down.The method of the disclosure is not the application's a method.
The present invention relates to produce the method for composite hollow fiber membrane, and the application of film own, this method is by the porous hollow fiber base material is contacted with coating material solution, by contacting the coating material of deposit is solidified then, thereby produce composite hollow fiber membrane with coagulating bath.This method can be used for doughnut, spiral twines or any other desirable formation.
The invention provides a kind of one deck method of the coating of uniform divided thin film absciss layer basically that on porous substrate, applies.Use optionally to separate and be present in that the membrane material of each component is well-known in the fluid mixture.They are used to fluid composition, for example divide dried uply from saline solution, as reclaiming drinking water from seawater or half salty water source, or are used for gas composition, for example all gases in the separation of air optionally.Method of the present invention can be used to make the pellicle that is applicable to any separation process; Yet for convenience's sake, the present invention will be described to use the hollowfibre semi-permeable membrance Composite Preparation to can be used to the material of each component of gas separated from one another.
For the method for coating divided thin film absciss layer on the porous hollow fiber base material, disclosed document is sufficient.Prevailing in all these are open is a kind of like this method, in this method, the solution of filmogen is coated on the surface of porous hollow fiber base material, and the composite drying that will handle then is with except that desolvating.Another kind method is that porous substrate is dipped in the pre-polymer solution, will soak good composite then and drain, and contact with cross-linked composition, and this final composite is placed under the high temperature so that coating curing.These basic skills have been done many improvement, attempted to solve some defectives that run into, as cavity, pin hole, non-homogeneous deposit etc.Other method comprises with various technology dipping porous fibre bundles.
According to the present invention, provide coating porous substrate surface to be suitable for the method for the composite semipermeable membrane of fluid separation with production.These methods comprise the surface with the weak solution coating porous substrate of solvent and filmogen, the porous substrate that was coated with is carried out the part drying, make it then to contact with solidifying solution, this solution is non-solvent to filmogen, and be solvent to the solvent of solution, reclaim composite membrane then.
The coating that generally on the porous substrate that does not have hole and pin hole substantially, has more uniform divided thin film absciss layer or filmogen with the composite membrane of the inventive method manufacturing.Because coating is more even, it is believed that also obviously more smooth also thinner than the coating that makes with previously known method.In the evaporation coating technology that formerly has, the surface that it is believed that the material that coating is crossed is a up-and-down surface, just look like see on the grassland that rises and falls such, many parts that fall in and protrude are arranged, and this is because the hydrodynamics of coating and because in the inhomogeneous evaporation of drying stage solvent or owing to the inhomogeneous coating of coating material on porous substrate or crosslinking agent causes.In the method for the invention, owing to make the porous substrate that scribbles filmogen by coagulating bath, in containing the shearing that produces between solvent filmogen and the liquid coagulating bath and can make the surface of filmogen more smooth on the porous substrate, and filled up the hole and the pin hole that may exist usually, thereby produced the basic defective of in many composites made from described prior art method, often not finding, the composite membrane of more even coating.Therefore do not need post processing.Also often can obtain thinner coating with method of the present invention.
Method of the present invention also allows to use the solvent that kind is numerous, quantity is different to be prepared into coating solution.These solvents must be gentle in the method that formerly has, because they will be removed through evaporation, this evaporation both can be in room temperature, and in most of the cases usually was at high temperature to carry out.Yet, no matter use which type of temperature conditions, it must enough hang down so that can not influence porous substrate.In the method, temperature is not important factor, because solvent removes in coagulating bath, and this preferably at room temperature carries out.Like this, in the method for prior art,, it can produce adverse effect and the solvent that can't use generally can use in the method for the invention to porous substrate because removing.Therefore, an advantage of method of the present invention is, in the past since when drying base material can degrade and some porous substrates that can not apply, can apply now.
Below further narration the present invention, for sake of convenience, specifically with reference to doughnut or polysulfone hollow fibre composite membrane.Yet, should be appreciated that scope of the present invention is not limited to use the composite membrane of doughnut form.Use any composite membrane composition of preparation as described herein to be used for required fluid lock out operation all among scope of the present invention.In addition, according to the present invention, such composite membrane composition can the spiral winding, plain film or the form of other hope and the form manufacturing of described doughnut.
The professional that present technique is skilled will understand that porous substrate has any of these form, and they have noticed that the many suitable method and the commerce thereof of producing these base materials supply property.For convenience doughnut will be discussed.Disclosed as people such as Ward, for the fluid stream of continuity between surfaces externally and internally, doughnut has continuous passage.The averga cross section diameter in hole is often less than about 20,000 dusts, and in some doughnut, the cross section average diameter is less than about 1000 or 5000 dusts.
Particularly advantageous doughnut is influential gas when separating especially for the material of doughnut wherein to the live part that separates, and is for example disclosed in the patent application that people top such as Henis is quoted, about 5 to 200 dusts of the averga cross section diameter in its hole.The total surface area of doughnut often is to be at least about 10: 1 with the ratio of total hole sectional area.For being used for the film that gas separates, particularly can influence in the film of live part of separation at the material of those doughnuts, the total surface area of doughnut is at least about 10 with the ratio of total hole sectional area
3: 1, and the ratio of some doughnut can reach about 10
3: 1 to 10
8: 1.
Preferably the wall of doughnut is enough thick, so that need not to process them with special equipment.Often can have an appointment 20 to 1000 microns external diameter of doughnut, such as, about 50 to 1000 microns, for example about 250 to 1000 microns, and wall thickness is at least about 5 microns.The wall thickness of some doughnut reaches as high as about 200 or 300 microns.In order to guarantee desired flux by doughnut, when particularly using wall thickness to be at least about those doughnuts of 50 microns, doughnut can have sizable voidage.The space is the zone that does not have the doughnut material in the inside of hollow fiber walls.Like this, when the space existed, the density of doughnut was just less than the density of doughnut bulk material.When hope had the space to exist, based on the surface volume of doughnut (being the volume that is comprised in the nominal dimension), the voidage of doughnut was usually up to about 90%, such as about 10 to 80%, was about 20 or 30 to 70% sometimes.The density of doughnut can be essentially identical in its whole thickness range, the homogeneous of also saying so, perhaps this doughnut can have such feature, promptly within its wall thickness, has a dense zone at least, the fluid stream that flows through hollow fiber walls there is iris action, that is to say that this doughnut is a heterogeneous body.In general, the dense zone of heterogeneous body doughnut is the outside that is in doughnut substantially, and coating preferably contacts this dense zone.
The used material of doughnut can be solid natural materials or synthetic.Select the material of doughnut can be, and separation process and this material of appointment that will use this doughnut material be with the other factors that operating condition limited that bears based on hear resistance, solvent resistance and/or the mechanical strength of doughnut.Therefore, for example, whether selection doughnut material can based on planning to allow the material convection cell separation of doughnut have a significant impact, and whether the material of doughnut has effective separating property in which type of process, perhaps plan to allow coating influence fluid and separate.Doughnut can be soft or be hard basically.The material that is used for doughnut can be the inorganic matter of the glass fibre that forms hollow for example, ceramic fibre, cermet fiber, sintered metal fiber etc.Under the situation of polymer, comprise no matter secondary operations is addition polymerization or polycondensation polymer with what porous hollow fiber was provided in any suitable method.Organic material or with organic polymer that inorganic material (as filler) is mixed, be used to make doughnut.Typical polymer can be that replace or unsubstituted polymer, and can be selected from following polymer: polysulfones, polystyrene type, comprise and contain cinnamic copolymer (acrylonitritrile-styrene resin for example, SB and styrene-ethylene base benzyl halide copolymer), poly-sulfuric acid ester, cellulosic polymer (cellulose acetate for example, cellulose acetate-butyrate, cellulose propionate, ethyl cellulose, methylcellulose, nitrocellulose etc.), polyamide and polyimide, comprise aromatic polyamide and aryl polyimide, polyethers, polyarylene ethers (for example polyphenylene oxide and polyxylene ether), the polyesteramide vulcabond, polyurethanes, polyesters (comprising polyarylate) is PETG for example, polyalkyl methacrylate, polyalkyl acrylate, poly terephthalic acid phenylene ester etc., polysulfide, the polymer that obtains by the monomer except that above-mentioned with α alkene unsaturation, polyethylene for example, polypropylene, PB Polybutene-1, poly 4-methylpene-1, vinylic polymers is (as polyvinyl chloride, polyvinyl fluoride, polyvinylidene chloride, polyvinylidene fluoride, polyvinyl alcohol, the polyvinylesters class is polyvinyl acetate and poly-vinyl propionate for example, polyvinylpyridine, PVP, polyvinyl ether, the polyvinyl ketone, the polyvinyl aldehydes is polyvinyl formal and polyvinyl butyral resin for example, the polyvinyl amide-type, the polyvinyl amine, the polyvinyl carbamates, the polyvinyl ureas, polyphosphoric acid vinyl esters and poly-sulfuric acid vinyl ester class), polyene propyl group class, polyphenyl and benzimidazole, polyhydrazide class polyoxadiazole class, the polytriazoles class, polybenzimidazoles, polycarbodiimide, polyphosphazene etc., and copolymer, comprise the ternary block polymer that contains above-mentioned repetitive (for example acrylonitrile-bromine ethene-to the terpolymer of sulfophenyl methallyl ethers sodium salt) and contain the graft copolymer and the blend of above-mentioned any material.Provide the typical substituting group of substituted polymer to comprise halogen (as fluorine, chlorine and bromine), hydroxyl, low alkyl group, lower alkoxy, monocyclic aryl, lower acyl etc.
The divided thin film absciss layer or the film forming matter that are deposited on the porous substrate generally are to be coated with as the solution in suitable solvent to apply.These professional those skilled in the art notice, can obtain many such materials, and have some materials that some fluid mixture is shown selectivity other are not then had selectivity.This is not a conclusion of the present invention, because method of the present invention is at producing composite membrane.People's such as Ward patent has comprised very comprehensive open to film forming organic synthesis thing, and this material can be used for the present invention to prepare suitable solution.
Typical useful materials is can be substituted or unsubstituted polymer.This material comprises synthetic rubber, natural rubber, than higher molecular weight and/or high boiling liquid, the organosilicon prepolymer polymers, polysiloxanes (siloxane polymer), polysilazane, polyurethanes, Hydrin, the polyamine class, poly-imines class, polyamide-based, contain acrylonitrile copolymer (as poly-α-Lv Bingxijing copolymer), polyesters (comprising poly-lactam class and polyarylate class) is polyalkyl acrylate and polyalkyl methacrylate (wherein alkyl has such as about 1 to 8 carbon) for example, poly-sebacate, poly-succinic ester and alkyd resins, the cellulosic polymer class, polysulfones, the polysulfones of fatty base particularly, PAG is (as polyethylene glycol, polypropylene glycol etc.), the polyalkylene multi-sulfate, polypyrrole alkane ketone, the polymer that makes by monomer with α alkene unsaturation, for example TPO is (as polyethylene, polypropylene, polybutadiene, poly-2, the 3-dichloroprene, polyisoprene, polychlorobutadiene, polystyrene, comprise for example SB of polystyrene copolymer), vinyl class in polymer such as polyvinyl alcohol, polyvinyl aldehyde (for example polyvinyl formal and polyvinyl butyral resin), polyvinyl ketone (for example poly-methyl vinyl ketone), polyvinylesters (for example polyphenyl formic acid vinyl esters), polyvinylhalide (for example polyvinyl bromide), poly-vinylidene halide, the polymerized thylene carbonate vinyl esters, poly N-vinyl maleimide etc., poly-1, the 5-cyclo-octadiene, poly-methyl isopropenyl ketone, the ethylene fluoride copolymer analog, polyarylene ethers (as polyxylene ether), the Merlon polyphosphate is (as gathering methyl acid phosphate glycol ester etc., and any copolymer, comprise the block copolymer that contains above-mentioned repetitive and the graft copolymer and the blend that contain the monomer of above-mentioned any polymer and above-mentioned polymer.
Other utility comprises polysiloxanes.Typical polysiloxanes can comprise aliphatic series or aromatic series part, and its repetitive often contains 1 to about 20 carbon atoms.The molecular weight of polysiloxanes can change in very wide scope, but generally at least about 1000.When being used for hollow-fibre membrane, polysiloxanes often has about molecular weight of 1000 to 300,000.Common aliphatic series and fragrant polysiloxanes comprise poly-single siloxanes and poly-two siloxanes that replaces of replacing; for example; wherein substituting group is the low fat base; for example low alkyl group (comprising cycloalkyl), particularly methyl, ethyl and propyl group, lower alkoxy; aryl (comprises monocycle or bicyclic aryl; comprising phenylene, naphthalene etc.), rudimentary monocycle and with the ring aryloxy group, acyl group (comprising rudimentary aliphatic acidyl and rudimentary aromatic acyl) etc.Aliphatic series or aromatic substituent can be substituted, and for example use halogen (as fluorine, chlorine, bromine), hydroxyl, low alkyl group, lower alkoxy, lower acyl etc.Some polysiloxanes can not fully soak into doughnut (as polysulfone hollow fibre), therefore can not make it by desired contact like that more fully.But if polysiloxanes dissolving or be dispersed in the solvent of polysiloxanes, and this solvent is to polysulfones not influence basically, facilitates to reach contact.Appropriate solvent generally comprises liquid alkane (as pentane, cyclohexane etc.), fatty alcohol (as methyl alcohol), some alkyl halides and halo dialkyl ether, dialkyl ether etc., and their mixture.
Just as noted earlier, filmogen is to be that film forming solution is applied to the lip-deep of porous substrate by solution, this generally by with the porous substrate surface by or immerse solution and carry out.Should be understood that porous substrate can be dry, also can be to use the solvent compatible liquid used with being prepared into coating solution to prewet.Any suitable solvent or the solution mixture of filmogen can use, and these professional those skilled in the art understand and understand that for what solvent of concrete filmogen be suitable.Solvent is the material that can be dissolved into membrane material, and can be also organic matter of inorganic matter, and it can obtain homogeneous phase or solution uniformly.The solvent that is used to be prepared into membrane material solution also can be the mixture that one or more non-solvents that can be dissolved into the solvent of membrane material and one or more filmogens are formed.Such mixture generally is preferably.Be to use single solvent also to be to use the mixture of solvent and non-solvent, what mainly consider is the preferably a kind of homogeneous phase basically of solution or the homogeneous solution of filmogen.The viscosity of this solution should enough be hanged down feasible be easy to paint a kind of smooth coating and the moistening porous substrate of energy surface on the porous substrate surface.Viscosity under serviceability temperature can change until being lower than about 50 centipoises, and generally is about 0.05 to about 10～20 centipoises.The concentration of filmogen can be in about 0.25 to 10%(weight of described solution in the film forming solution) scope in change.
The examples of material that can be used for preparing solution is liquid aliphatic hydrocarbon and aromatic hydrocarbon (as benzene, toluene, pentane, hexane, 2-ethyl hexane, pentamethylene, methyl cyclopentane, cyclohexane etc.), alkanol (as methyl alcohol, ethanol, propyl alcohol class, butanols class, cyclopentanol, cyclohexanol, phenmethylol etc.), ketone (as acetone, dimethyl ketone, metacetone, methyl ethyl ketone etc.), acids (as acetate, propionic acid, hydrochloric acid etc.), water, ester class (as ethyl acetate etc.), alkyl halide and halo dialkyl ether, dialkyl ethers etc. also can use their mixture.In some example, one of material described in the mixture can be the solvent of filmogen, and the another kind of described material can be a non-solvent; In some other example, two kinds of components can all be the solvents of filmogen.
Can be used to determine a kind of specific material whether to be suitable as and be used for to carry out like this to the preliminary experiment chamber test of solvent that porous substrate is coated with the film forming solution of application layer, promptly single material to be measured is coated onto on the porous substrate, then with treated base material by coagulating bath.Suitable material can not have a significant effect to base material, and inappropriate material will have a significant effect to base material.Use such test, can select to be used for method of the present invention but and be not suitable for the material of prior art method, formerly having needs heating to remove vehicle substance from the porous substrate surface, because heating often has injurious effects, particularly when the temperature that requires is too high in the technical method.When nonvolatile solvent.For example strong inorganic acid or high boiling substance are that this test also allows to select for use them, because can at an easy rate they be removed with coagulating bath when being suitable for being dissolved into the only solvent of membrane polymer material.
Just as noted earlier, after with filmogen solution coating porous substrate, at last with the porous substrate that coats by coagulating bath.It is non-solvent and be the liquid substance of solvent to the solvent that is used to prepare polymer film-forming material solution that this coagulating bath includes polymer film-forming material.In other words, the solvent of coating material will dissolve in the coagulating bath, and polymer film-forming material is insoluble in the coagulating bath basically.For these professional those skilled in the art, this solidification phenomenon is known, as it to any common scientist.Therefore, in case know with what solvent and be dissolved into membrane material, common professional science and technology personnel can be that suitable coagulating agent is selected in coagulating bath without a doubt.In general, when the mixture that uses solvent and non-solvent was prepared into the solution of membrane material, coagulating bath can be same non-solvent.Therefore, the concrete composition of coagulating bath will change along with being coated to the concrete composition on the porous substrate, and this is the conspicuous fact to the people who is familiar with this solidification phenomenon.
A mode of the inventive method is implemented in following narration representative.Clearly, this is not the sole mode of so doing, and should so not think yet; And, use porous hollow fiber for sake of convenience.
It is by as previously described at about 0 ℃ or more be low to moderate about 70 ℃ or higher temperature (the being preferably room temperature) solution of the filmogen of preparation down the porous hollow fiber of wetting or predrying mistake that this method begins.As long as guarantee porous substrate or coating not to be produced adverse effect, any temperature all can be used.This fiber, is drawn downwards as the fiber that separates by a suitable wire drawing die device from including the container bottom of filmogen solution, and in other words, they are drawn with single fiber, and do not contact each other.This wire drawing die device is known in prior art and can have bought or make easily.The fiber separated from one another of drawing from wire drawing die continues to enter drying stage downwards, preferably by the air under the room temperature about 1 to about 80 seconds, preferably about 10 to about 20 seconds.As long as guarantee product not to be caused injurious effects, any other gas atmosphere also can use.The length that this drying period continues will change with the temperature of carrying out drying with the used concrete system of coating on porous substrate, to a certain extent because if desired, the temperature that is below or above room temperature all can be used.The evaporation or the drying of certain solvent importantly will take place, and it is also important that not generation is dry completely.Vital feature is, when entering coagulating bath, remains with some residual from film forming solution solvents on the coated porous substrate, generally is about 10 to 90%(weight), the most often be about 30 to 70%(weight).It is also of significant importance that, during drying, the good fiber of the coating that moves downward is drawn from the wire drawing die device after by coagulating bath at them, can not contact each other, can not contact with other surface of solids, otherwise on the good porous substrate of coating, can form defective.Along with this brief drying stage, the fiber of separation enters coagulating bath.This coagulating bath also can be below or above under the condition of room temperature, such as from about 0 ℃ or more be low to moderate about 75 ℃ or higher, but room temperature is best.This coagulating bath will have enough sizes so that be coated in the lip-deep filmogen of porous substrate the porous substrate that coats with solidify fully before the surface of solids contacts.Solidify therewith simultaneously, the solvent that is present in the film forming solution is dissolved in the coagulating bath.After having realized solidifying, the fiber roll of this separation is crossed the pulley that is positioned at the coagulating bath bottom, puts upside down its direction, promotes and draw coagulating bath.This fiber is drawn by pulley and fiber separation device then, and or at hygrometric state or after drying stage, this hollow fiber composite membrane is collected on the reel spool.
In order in the fluid separation process of use, best benefit to be arranged, generally like applying porous substrate with the coating material of high selectivity by the composite membrane of the inventive method manufacturing.They all have high selective value, and have many all on the books in " polymer handbook " (Polymer Handbook) of John Wiley Sons publishing house New York publication in 1975.Yet, when the needs high flux, can select to use to have low optionally material.These situations of membrane technology are that these professional those skilled in the art are known.
The thickness that is coated on the lip-deep film of porous substrate with method of the present invention is about 500～7000 dusts, and preferably about 750 to about 2000 dusts.
In the middle of the accessible advantage of method of the present invention, have make than the getable film of institute is all thin so far permeable membrane, have the film on more uniform surface and do not have substantially the film of hole and pin hole ability, coat and can be produced that the used solvent of membrane coat solution damages or the ability of the solvent that the boiling point of the ability of dissolved polymers and use film-forming composition is higher.As a result, composite membrane has generally all improved selectivity, flux and infiltration rate.
As used, should be understood that in the selectivity of film or film assembly or the mixture that separation factor is represented to be separated that than the ratio of the infiltration rate of the component that is easier to permeate with the infiltration rate of the component that relatively is not easy to permeate, permeability is with foot here
3(standard temperature and pressure (STP))/foot
2Day pound/inch
2
Following example is used for further specifying the present invention.
Example 1
Polysulfones porous hollow fiber through spinning is in about 115 ℃ of dryings, and by an about hot-air oven of 182 ℃, the time of staying was 10 seconds then.Make the asymmetry base material with this method.
At the 50/50(volume) acetate and the mixed solvent of isopropyl alcohol in preparation acetate fiber cellulose content 1.5%(weight) film forming solution, filter then to enter and be equipped with in the container of porous wire drawing die in its bottom.Apply the polysulfones porous hollow fiber of above-mentioned preparation as previously mentioned, at room temperature make they with the speed of 5 feet per minutes by cellulose acetate solution applying this fiber, and draw from nib.The compound doughnut that scribbles solution is drawn by the single hole of its wire drawing die, and enters air downwards, at room temperature through 14 seconds with evaporating solvent, can not contact each other during this and can not contact with any surface of solids.Then it is immersed at room temperature in 10 liters of containers as the isopropyl alcohol of coagulating bath.Isopropyl alcohol is the non-solvent of cellulose acetate, but the solvent of acetate-isopropyl alcohol mixed solvent.After solidifying, reclaim the compound polysulfones porous hollow fiber membrane that scribbles cellulose acetate as previously mentioned.
With customary way this composite hollow fiber membrane is made 16 strands of 8 inches long fluid separating assemblies to be used for test.
Be used in 200 pounds/inch
2With 25 ℃ under by the 30.5%(volume) hydrogen and 69.5%(volume) the mist formed of the nitrogen gas separating property of testing this compound polysulfones porous hollow fiber membrane assembly.The average selectivity of separation of hydrogen is 59 between nitrogen and hydrogen, and the average infiltration rate (p/t) of hydrogen is 0.92 foot
3(normal temperature-pressure)/foot
2Day pound/inch
2
Under the coating speed that changes, apply same polysulfone hollow fibre to change the air evaporation time with the cellulose acetate film forming solution.Prepare fluid separating assembly and press above-mentioned same method test.The results are summarized in table 1
Table 1
Criticize the coating speed air and steam selectivity p/t
(feet per minute) sends out the time (on average) (on average)
(second)
a 5 14 59 0.94
b 10 7 44 1.2
c 20 3.5 44.5 1.2
As what we saw, can obtain the selectivity between hydrogen and the nitrogen and the best synthesis result of infiltration rate (p/t) with 14 seconds air dryings or air evaporation time.Selectivity is lower more in short-term drying time for air, but infiltration rate is higher.
Comparative experiment A
For sake of comparison, prepare assembly, just do not apply the acetate fiber element coating, and press example 1 described test hydrogen separating property with the asymmetric polysulfones porous hollow fiber in the example 1.Average selectivity between hydrogen and the nitrogen is 3.3, and average infiltration rate is 100.92 feet
3(normal temperature-pressure)/foot
2Day pound/inch
2This separation is at 25 pounds/inch
2With carry out under 26 ℃ the condition.
Contrast experiment B
For sake of comparison, prepare assembly, carry out heating steps then, but do not apply the acetate fiber element coating with the polysulfones porous hollow fiber of example 1, and by the described test hydrogen of Comparative experiment A separating property.Average selectivity between hydrogen and the nitrogen is 1.3, and average infiltration rate is 140 feet
3(normal temperature-pressure)/foot
2Day pound/inch
2
Comparison shows that of the infiltration rate of Comparative experiment A and example 1, contrast experiment's infiltration rate or flux are much higher.Yet selectivity is just much low, is 3.3 in Comparative experiment A, and is about 44 to about 59 in experiment 1.Therefore, when target is (being that hydrogen is separated with nitrogen in this example) when a kind of gas is separated with another kind of gas, far better with the film that the inventive method is made, high flux or high infiltration rate can not provide satisfied separation.
Example 2
At the 50/50(volume) acetate and the mixed solvent of isopropyl alcohol in preparation acetate fiber cellulose content be 1.0%(weight) film forming solution.Apply example 1 described polysulfones porous hollow fiber according to the method described in the example 1 with this solution.Use the prepared compound polysulfones porous hollow fiber membrane that scribbles cellulose acetate to prepare fluid separating assembly, and test gas separating property between its hydrogen and the nitrogen by example 1 described method.Data and the results are summarized in the table 2.
Table 2
Criticize the coating speed air and steam selectivity p/t
(feet per minute) sends out the time (on average) (on average)
(second)
a 5 14 59.5 .76
b 10 7 50 .82
c 20 3.5 47 1.25
Can observe, along with the air evaporation time shortens, selectivity descends, and the film for use this system preparation by the inventive method shows best choice when the air evaporation time is 14 seconds.
Example 3
At the 50/50(volume) acetate and the mixed solvent of isopropyl alcohol in preparation acetate fiber cellulose content be 0.75(weight) film forming solution of %.Method according to described in the example 1 is coated in the polysulfone hollow fibre described in the example 1 with this solution.Use the prepared compound polysulfones porous hollow fiber membrane that scribbles cellulose acetate to prepare fluid separating assembly, and measure gas separating property between its hydrogen and the nitrogen according to the method described in the example 1.Data and the results are summarized in the table 3.
Table 3
Criticize the coating speed air and steam selectivity p/t
(feet per minute) sends out the time (on average) (on average)
(second)
a 5 14 56.5 1.2
b 10 7 49.5 1.1
c 20 3.5 40 1.35
Can notice that along with the shortening of air evaporation time, selectivity descends, the film for adopting body series to make by the inventive method shows best choice when the air evaporation time is 14 seconds.
It is further noted that, the concentration of cellulose acetate is to the selectivity or the few of influence of the permeability not influence fully in other words of the compound polysulfones porous hollow fiber membrane made by the inventive method in the film forming solution, and, in all situations, selectivity ratios be the selectivity that should contrast experiment B be reached of Comparative experiment A all.
Example 4
Preparation bromo polyphenylene oxide content in carbon tetrachloride is 1.5%(weight) film forming solution, and filter, be placed in its bottom then and be equipped with in the container of porous wire drawing die.According to the method described in the example 1,, adopt at room temperature 14 seconds air evaporation time with the polysulfone hollow fibre described in this solution coating example 1.Use the prepared compound polysulfones porous hollow fiber membrane that scribbles bromo polyphenylene oxide to prepare fluid separating assembly, and be that feed gas is at 25 ℃ and 100 pounds/inch with air
2Test the gas separating property between oxygen and the nitrogen down.The average selectivity that oxygen separates between oxygen and nitrogen is 4.2, and the average infiltration rate of oxygen is 0.17 foot
3(normal temperature-pressure)/foot
2Day pound/inch
2
Example 5
At the 50/50(volume) in the mixed solvent of 1,1,1 trichloroethanes and carbon tetrachloride preparation tetramethyl bisphenol a polysulfone polymer content be 1.5%(weight) film forming solution and filter.According to the method described in the example 1, with the polysulfones porous fibre of this solution coating described in example 1, at room temperature in drying 14 seconds and 10 liters of containers of immersion as the isopropyl alcohol of coagulating bath.Isopropyl alcohol is the non-solvent of tetramethyl bisphenol a polysulfone, but 1,1, the solvent of 1 trichloroethanes/carbon tetrachloride mixed solvent.The compound polysulfones porous hollow fiber membrane that use scribbles the tetramethyl bisphenol a polysulfone prepares fluid separating assembly, and with air as feed gas at 25 ℃ and 100 pounds/inch
2Test the gas separating property between oxygen and the nitrogen down.The average selectivity that oxygen between oxygen and the nitrogen separates is 3.9, and the average infiltration rate of oxygen is 0.11 foot
3(normal temperature-pressure)/foot
2Day pound/inch
2
Claims (30)
1, be used for the manufacture method of the composite hollow fiber membrane of fluid separation, it comprises:
(i) use film-forming composition to apply preformed porous hollow fiber base material, therefore, described composition is coated on the described porous hollow fiber base material by the solution composition that contains filmogen and its solvent;
The porous hollow fiber base material that (ii) will scribble described composition transmits by gas atmosphere so that the part in the described composition rather than all solvent from the surface evaporation of described coated porous hollow fiber base material;
(iii) with this part drying, when described film-forming composition solution is coated on the porous hollow fiber substrate surface, its coated surfaces as yet not the porous hollow fiber base material that has applied of the contacted surface of solids to send into filmogen be a kind of non-solvent but be in the liquid coagulating bath of solvent to film-forming composition solution, wherein filmogen is solidified with a kind of thin and level and smooth separating layer and the solvent of described film-forming composition solution is dissolved in the liquid coagulating bath simultaneously; And
(iv) be recovered in to have applied on the porous substrate and have described composite hollow fiber membrane thin and level and smooth, that minimum thickness can reach the film separating layer of 500 dusts, described thin and level and smooth separating layer is not contain hole or pin hole substantially.
2, the method for the manufacturing composite hollow fiber membrane described in claim 1, wherein said solvent solution comprises the solvent of one or more filmogens.
3, the method for the manufacturing composite hollow fiber membrane described in claim 1, wherein said solvent solution comprises the solvent of one or more filmogens and the non-solvent of one or more filmogens.
4, the method for the manufacturing composite hollow fiber membrane described in claim 1, the temperature of wherein said film-forming composition are about 0 ℃～70 ℃.
5, the method for the manufacturing composite hollow fiber membrane described in claim 1, the temperature of wherein said film-forming composition is a room temperature.
6, the method for the manufacturing composite hollow fiber membrane described in claim 1, wherein drying stage (ⅱ) is about 1～80 second.
7, the method for the manufacturing composite hollow fiber membrane described in claim 1, wherein drying stage (ⅱ) is about 10～20 seconds.
8, the method for the manufacturing composite hollow fiber membrane described in claim 1, the temperature of wherein said liquid coagulating bath are about 0 ℃～75 ℃.
9, the method for the manufacturing composite hollow fiber membrane described in claim 1, the temperature of wherein said liquid coagulating bath is a room temperature.
10, the method for the manufacturing composite hollow fiber membrane described in claim 1, wherein film-forming composition comprises about 0.25%～10%(weight) filmogen.
11, the process of claim 1 wherein that filmogen is a cellulose acetate.
12, the method for claim 1, wherein filmogen is a bromo polyphenylene oxide.
13, the method for claim 1, wherein filmogen is a tetramethyl bisphenol a polysulfone polymer.
14, the process of claim 1 wherein that with before described film-forming composition contacts, preformed porous hollow fiber substrate surface is soaked in advance.
15, the process of claim 1 wherein that the porous hollow fiber base material is a polysulfones.
16, be used for the composite hollow fiber membrane that fluid separates, it comprises an one deck coating and a porous hollow fiber base material, and described composite hollow fiber membrane is made by the following method:
(ⅰ) use film-forming composition to apply preformed porous hollow fiber base material, therefore, described composition is coated on the described porous hollow fiber base material by the solution composition that contains filmogen and solvent;
(ⅱ) the porous hollow fiber base material that will scribble described composition transmits by gas atmosphere, so that the part in the described composition but be not the surface evaporations of whole solvents from described coated porous hollow fiber base material;
(ⅲ) with this part drying, when described film-forming composition solution is coated on the porous hollow fiber substrate surface, its coated surfaces as yet not the porous hollow fiber base material that has applied of the contacted surface of solids to send into filmogen be a kind of non-solvent but be in the liquid coagulating bath of solvent to film-forming composition solution, wherein filmogen is solidified with a kind of thin and level and smooth separating layer and the solvent of described film-forming composition solution is dissolved in the liquid coagulating bath simultaneously; And
(ⅳ) be recovered in to have applied on the porous substrate and have described composite hollow fiber membrane thin and level and smooth, that minimum thickness can reach the film separating layer of 500 dusts, described thin and level and smooth separating layer is not contain hole or pin hole substantially.
17, be used for the composite hollow fiber membrane that fluid separates described in claim 16, the film-forming composition that wherein is used for making described composite hollow fiber membrane comprises the solvent of a kind of filmogen and one or more filmogens.
18, be used for the composite hollow fiber membrane that fluid separates described in claim 16, the film-forming composition that wherein is used for making described composite membrane comprises the non-solvent of a kind of filmogen and one or more filmogens.
19, the composite hollow fiber membrane that is used for the fluid separation described in claim 16, wherein filmogen is a cellulose acetate.
20, the composite hollow fiber membrane that is used for the fluid separation described in claim 16, wherein filmogen is that the bromo polyphenyl is poly-.
21, the composite hollow fiber membrane that is used for the fluid separation described in claim 16, wherein filmogen is a tetramethyl bisphenol a polysulfone polymer.
22, the composite hollow fiber membrane that is used for the fluid separation described in claim 16, wherein the porous hollow fiber base material is a polysulfones.
23, the composite hollow fiber membrane of claim 16 is passing through selectively penetrating, with the application during one other fluid is separated at least at least a fluid in the fluid mixture and the described fluid mixture, comprise allowing fluid mixture contact with the permselective compound porous hollow-fibre membrane of being made up of an one deck coating and a porous hollow fiber base material, described composite hollow fiber membrane is produced as follows:
(ⅰ) use film-forming composition to apply preformed porous hollow fiber base material,, described composition is coated on the described porous hollow fiber base material for this reason by the solution composition that contains filmogen and solvent;
(ⅱ) the porous hollow fiber base material that will scribble described composition transmits by gas atmosphere, so that the part in the described composition but be not whole solvents from the surface evaporation of described coated porous hollow fiber base material;
(ⅲ) with this part drying, when described film-forming composition solution is coated on the porous hollow fiber substrate surface, its coated surfaces as yet not the porous hollow fiber base material that has applied of the contacted surface of solids to send into filmogen be a kind of non-solvent but be in the fluid coagulating bath of solvent to film-forming composition solution, wherein filmogen is solidified with a kind of thin and level and smooth separating layer and the solvent of described film-forming composition solution is dissolved in the fluid coagulating bath simultaneously; And
(ⅳ) be recovered in the described composite hollow fiber membrane that has applied the separating layer with thin and level and smooth, that minimum thickness can reach 500 dusts film on the porous substrate, described thin and level and smooth separating layer is not contain hole or pin hole substantially.
24, described in claim 23 with at least a fluid in the fluid mixture with as described in the application that separates of one other fluid at least in the fluid mixture, the film-forming composition that wherein is used for making described composite hollow fiber membrane comprises a kind of filmogen and solvent solution thereof.
25, described in claim 23 with at least a gas in the admixture of gas with as described in another kind of at least gas separates in the admixture of gas application, the film-forming composition that wherein is used for making described composite hollow fiber membrane comprises the solvent of a kind of filmogen and one or more filmogens.
26, described in claim 23 with at least a fluid in the fluid mixture with as described in the application that separates of one other fluid at least in the fluid mixture, the film-forming composition that wherein is used for making described composite hollow fiber membrane comprises the solvent of a kind of filmogen, one or more filmogens and the non-solvent of one or more filmogens.
27, described in claim 23 with at least a fluid in the fluid mixture with as described in the application that separates of one other fluid at least in the fluid mixture, wherein said porous hollow fiber base material is a polysulfones.
28, described in claim 23 with at least a fluid in the fluid mixture with as described in the application that separates of one other fluid at least in the fluid mixture, wherein filmogen is a cellulose acetate.
29, described in claim 23 with at least a fluid in the fluid mixture with as described in the application that separates of one other fluid at least in the fluid mixture, wherein filmogen is a bromo polyphenylene oxide.
30, described in claim 23 with at least a fluid in the fluid mixture with as described in the application that separates of one other fluid at least in the fluid mixture, wherein filmogen is a tetramethyl bisphenol a polysulfone polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88106070 CN1029822C (en) | 1987-07-10 | 1988-08-15 | Composite membranes and their manufacture and use |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/072,056 US4826599A (en) | 1987-07-10 | 1987-07-10 | Composite membranes and their manufacture and use |
| CN 88106070 CN1029822C (en) | 1987-07-10 | 1988-08-15 | Composite membranes and their manufacture and use |
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|---|---|
| CN1040328A CN1040328A (en) | 1990-03-14 |
| CN1029822C true CN1029822C (en) | 1995-09-27 |
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|---|---|---|---|
| CN 88106070 Expired - Fee Related CN1029822C (en) | 1987-07-10 | 1988-08-15 | Composite membranes and their manufacture and use |
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Cited By (1)
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| CN101269301B (en) * | 2008-05-09 | 2010-07-28 | 天津膜天膜工程技术有限公司 | Method for preparing internal air pressure type hollow fiber compound film component |
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| JP4588286B2 (en) * | 2001-09-28 | 2010-11-24 | 帝人株式会社 | Manufacturing method of composite porous membrane |
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1988
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269301B (en) * | 2008-05-09 | 2010-07-28 | 天津膜天膜工程技术有限公司 | Method for preparing internal air pressure type hollow fiber compound film component |
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