CN101254420A - Reinforced tubular porous body compound film, method of preparing the same and use thereof - Google Patents
Reinforced tubular porous body compound film, method of preparing the same and use thereof Download PDFInfo
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- CN101254420A CN101254420A CNA2008101038195A CN200810103819A CN101254420A CN 101254420 A CN101254420 A CN 101254420A CN A2008101038195 A CNA2008101038195 A CN A2008101038195A CN 200810103819 A CN200810103819 A CN 200810103819A CN 101254420 A CN101254420 A CN 101254420A
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Abstract
The invention discloses a reinforced tubular porous composite film, as well as a preparation method and an application thereof. The composite film consists of a tubular porous body, a first polymer material film and a second polymer material film. The composite film is obtained by coating the first polymer material film and the second polymer material film on the tubular porous body. The reinforced tubular porous composite film has the advantages of no surface defect, high water permeability, high tensile strength, wide selection range of the tubular porous body and easy production.
Description
[technical field]
The present invention relates to a kind of reinforcement tubular porous body composite film, the preparation method of described film and purposes.
[background technology]
Film separation unit has been widely used in the regeneration of the purifying and the sewage of water because of it is energy-efficient.In large-scale sewage disposal, require film that certain intensity should be arranged, certain permeability rate is arranged again.But film strength and permeability rate are runed counter to, and its intensity is directly proportional with thickness, and permeability rate and thickness are inversely proportional to.A kind of effective ways that solve this contradiction are to make composite membrane, i.e. the film of being made up of functional layer and supporting layer.This functional layer mainly plays centrifugation, and supporting layer mainly plays humidification.The form of film mainly contains two kinds: flat and doughnut formula.The membrane material that uses is macromolecular material, ceramic material, metal material etc.Wherein macromolecular material is low because of its price, pliability good, easily process and be main membrane material.Hollow fiber polymer membrane is bigger because of its surface area, loading density is high becomes main form membrane, and the development of composite hollow fiber membrane also more and more is subjected to people and extensively payes attention to.In order to adapt to the needs of sewage disposal, many research workers have attempted adopting diverse ways to prepare described hollow fiber composite membrane, and the method that wherein has the meaning represented mainly is following several method:
First method is that fortifying fibre and polymer material film liquid are passed through spinning head together, then through making hollow-fibre membrane (for example CN1695777A) behind the coagulating bath gel.Fortifying fibre vertically is embedded in the wall of hollow-fibre membrane in this film.
Second method is to spin out hollow-fibre membrane with polymer material film liquid earlier, immerse again in the polymer material film liquid after this film outside is woven into net with synthetic fibers then, strengthen hollow-fibre membrane (for example CN1864828A) through making reticular fibre behind the coagulating bath gel.Netted braid is embedded in the wall of hollow-fibre membrane in this film.
The third method is that polymer material film liquid is coated on the hollow support material, immerses to make hollow-fibre membrane (for example patent CN1683059) in the coagulating bath again.
The 4th kind of method is that hollow braid and film liquid are spun into hollow-fibre membrane (for example patent US4061821) by spinning head together.In this film, the polyacrylonitrile material is filled in the hole of hollow braid, can overcome the permeability rate reduction problem that the polyacrylonitrile hollow-fibre membrane causes because of contraction when high temperature uses.
The 5th kind of method is that hollow braid and film liquid with special construction are spun into hollow-fibre membrane (for example patent US 5472607) by spinning head together.The hole of hollow braid will be controlled at moderate level, if the space is too big, film liquid can infiltrate braid too much, and the result causes the inner chamber of hollow braid to stop up; If the space is too little, film liquid can not infiltrate braid, and the film that the result forms is easy to come off from the braid that supports.In this film, the thickness that film liquid infiltrates accounts for 1/3rd of braid thickness.
The 6th kind of method is that hollow braid with special construction and film liquid are passed through spinning head together, and makes hollow-fibre membrane through behind the coagulation bath; Again this hollow-fibre membrane and film liquid are spun into hollow-fibre membrane (for example patent US 7306105) by spinning head for the second time.Wherein the intermembranous interconnective area of second layer polymer material film and ground floor macromolecular material is about the 1-50% of the contact-making surface gross area.
The 7th kind of method is that hollow braid, adhesive and film liquid are spun into hollow-fibre membrane (for example patent US 7165682) by spinning head together.Wherein adhesive is coated on the hollow braid, and film liquid covers on the adhesive.The effect of adhesive is the bond strength that increases between film and braid.
The 8th kind of method is that hollow braid, core liquid and film liquid are spun into hollow-fibre membrane (for example EP1658889A1 and CN101068613A) by spinning head together.The main effect of core liquid is to immerse the hollow braid earlier, and fills up the inner chamber of hollow braid, with the too much infiltration of block film liquid.Can reduce hole requirement like this, enlarge the range of choice of hollow braid the hollow braid.
Above-mentioned preceding four kinds of method defectives are that fortifying fibre or fleece are embedded in the film fully, are difficult to improve the permeability rate of film.Five, six, seven kind of method be too strict to the requirement of hollow braid, subject matter is that film liquid easily penetrates braid too much, stops up the inner passage of braid.The 8th kind of film that method is made is easy to generate defective.
Therefore, also need to adopt new preparation method at present, overcome the various defectives that prior art exists,,, made the present invention finally so the inventor has carried out a large amount of experimental studies to satisfy actual needs to desalt and recycling sewage generated by making.
[summary of the invention]
[the technical problem to be solved in the present invention]
The objective of the invention is a kind of reinforcement tubular porous body composite film, it has the advantage that permeability rate height, intensity height, polymer material film liquid are difficult for penetrating, being difficult for producing defective.
Another object of the present invention provides a kind of preparation method of reinforcement tubular porous body composite film.
Another object of the present invention is the purposes of reinforcement tubular porous body composite film in municipal wastewater, sanitary sewage, Industrial Wastewater Treatment.
[technical scheme]
Purpose of the present invention mainly be solve in the prior art existing in strengthening the hollow-fibre membrane preparation process polymer material film liquid easily penetrate the hollow braid, stop up the braid inner passage, and made film easily produces the problem of defective.The problem that described polymer material film liquid easily penetrates the hollow braid can solve by following method: fill full core liquid earlier in the hollow braid, outside braid, be coated with the polymer material film liquid that one deck system film is used again, and make hollow-fibre membrane through the coagulating bath gel solidification.The problem that film easily produces defective can apply one deck polymer material film liquid again on the basis of above-mentioned film, and solves through the coagulating bath gel solidification.After above-mentioned two kinds of methods are combined, can overcome simultaneously that polymer material film liquid easily penetrates the hollow braid and made film easily produces two problems of defective, thus the hollow-fibre membrane that obtains high flux, high strength, zero defect, easily produces.
Usually, the preparation method of described hollow fiber composite membrane is dissolved in macromolecular material earlier to make polymer material film liquid in the solvent, polymer material film liquid is coated on the hollow braid again.Between the hole of this viscosity that just requires polymer material film liquid and hollow braid suitable cooperating will be arranged, promptly the hole of hollow braid can not be too big, can not be too little.If hole is too big, polymer material film liquid will penetrate braid too much, and stops up the inner chamber of hollow braid.If the space is too little, polymer material film liquid just is difficult to infiltrate braid, thereby causes the film behind the gel solidification to come off from braid.
For addressing the above problem, can in core liquid, soak the hollow braid earlier, allow core liquid be full of the inner chamber of hollow braid, and then be coated with one deck polymer material film liquid.This core liquid can be solvent, also can be non-solvent, or their mixture.In order to stop polymer material film liquid to penetrate the hollow braid too much, in the process of coating polymer material film liquid, core liquid should be retained in the hole and inner passage of braid.This just requires core liquid that certain viscosity will be arranged.For improving the viscosity of core liquid, can in core liquid, add some tackify materials.Preferably, these tackify materials are water-soluble substanceses, so that water washes these substance dissolves in film-forming process or behind the system film.More preferably, these water-soluble substanceses are water-soluble polymers, for example polyethylene glycol, polyvinylpyrrolidone, polymethylacrylic acid, CMC, hydroxypropyl cellulose, polyvinyl alcohol, polyacrylamide etc.
If the hollow-fibre membrane of preparation external-compression type, what the aperture of doughnut inboard should be than the outside is big.Therefore core liquid preferably selects to reduce the liquid of polymer material film lyogel speed, and these liquid comprise solvent and alcohols material, as ethanol, propyl alcohol, glycerine, ethylene glycol etc.
The present invention relates to a kind of reinforcement tubular porous body composite film, it is made up of tubulose porous body and ground floor polymer material film and second layer polymer material film, described tubulose porous body is perforated pipe shape thing or a hollow braid on the wall, its aperture is the 0.1-10 micron, porosity is 10-70%, the thickness of described ground floor polymer material film and second layer polymer material film is the 0.05-0.5 millimeter, and the intermembranous joint face of ground floor polymer material film and second layer macromolecular material is the long-pending 50-100% of entire contact surface.
Described tubulose porous body can be perforated pipe shape thing or a hollow braid on the wall.Perforated pipe shape thing for example is selected from polyamide or polyester on the described wall; The aperture of this tube is the 0.1-10 micron, and porosity is 10-70%; Described hollow braid for example is selected from polyethylene, polypropylene, polyamide or polyester.Preferably, described hollow braid is polyamide or polyester; The aperture of this hollow braid is the 0.2-8 micron, and porosity is 20-60%.
Described macromolecular material is selected from polyacrylonitrile, polysulfones, polyether sulfone, Kynoar, polyvinyl chloride or cellulose acetate.
For guaranteeing that made hollow-fibre membrane has preferable performance, the thickness of this hollow-fibre membrane, promptly from the outside of hollow braid to the outside of hollow-fibre membrane, should be in certain scope, preferably between the 0.05-0.5 millimeter.If thickness is lower than 0.05 millimeter, film easily produces defective; If thickness is greater than 0.5 millimeter, the permeability rate of film will be lower.The thickness of ground floor polymer material film can be the 0.02-0.3 millimeter, and the thickness of second layer polymer material film can be the 0.2-0.5 millimeter.
In hollow-fibre membrane of the present invention (referring to accompanying drawing 3), between ground floor polymer material film and the second layer polymer material film enough joint faces should be arranged, if it is too little to connect area, second layer polymer material film easily comes off from hollow-fibre membrane.For guaranteeing enough adhesive strengths between ground floor polymer material film and the second layer polymer material film, it connects area should account for the long-pending 50-100% of entire contact surface.
In the present invention, described contact area should be appreciated that it is interfacial area between ground floor macromolecular material and the second layer macromolecular material.
Described connection area should be appreciated that it is in the interface, the area that the ground floor macromolecular material is bonded in second layer macromolecular material.
The present invention relates to a kind of preparation method of reinforcement tubular porous body composite film, it is characterized in that this method comprises the steps:
A, soak the tubulose porous body: allow the tubulose porous body pass the inner chamber of the spinning head of filling core liquid, and make core liquid infiltrate the tubulose porous body with core liquid.
B, coating ground floor polymer material film: allow polymer material film liquid I and the above-mentioned tubulose porous body that soaked core liquid extrude simultaneously, enter then in the outer coagulating bath by spinning head.
C coating second layer polymer material film: allow polymer material film liquid II and the above-mentioned tubulose porous body that has been coated with the ground floor polymer material film extrude simultaneously, and enter in the outer coagulating bath, make the reinforcement tubular porous body composite film behind the gel forming by spinning head.
Allow the tubulose porous body pass the inner chamber of the spinning head of filling core liquid, and make core liquid infiltrate the tubulose porous body, be full of the hole of tubulose porous body.
Preferably, described tubulose porous body is a perforated pipe shape thing on hollow braid or the wall.The material of described hollow braid is selected from polyethylene, polypropylene, polyamide, polyester etc.Perforated pipe shape thing is selected from polyamide, polyester etc. on the described wall.
On meaning of the present invention, core liquid should be appreciated that it is the hollow shape that can help to keep doughnut, and can impel the liquid of film lyogel.
Described core liquid is made up of solvent, non-solvent or their mixture, water-soluble polymer, alcohol, and their ratio is respectively in described core liquid gross weight, solvent 0-90% wherein, non-solvent 10-100%, water-soluble polymer 0-10%, pure 0-90%.Preferably, solvent 0-80%, non-solvent 20-100%, water-soluble polymer 0-10%, pure 0-80%.More preferably, solvent 0-70%, non-solvent 30-100%, water-soluble polymer 0-10%, pure 0-70%.
Described water-soluble polymer is selected from polyethylene glycol, polyvinylpyrrolidone, polymethylacrylic acid, CMC, hydroxypropyl cellulose, polyvinyl alcohol or polyacrylamide.
Described alcohol is selected from ethanol, propyl alcohol, glycerine or ethylene glycol.
In the present invention, described film liquid comprises polymer material film liquid I and II, and their composition is identical or different, and they are made up of macromolecular material, solvent, pore former and surfactant.
In a kind of specific embodiment, described macromolecular material is selected from polyacrylonitrile, polysulfones, polyether sulfone, Kynoar, polyvinyl chloride, cellulose acetate etc.In wastewater treatment, particularly in the application of membrane bioreactor, Kynoar has bigger advantage, because its good toughness, drug resistance is good.
Described solvent is selected from acetone, oxolane, butanone, tetramethylurea, dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), trimethyl phosphate, N-methyl pyrrolidone or their mixture.
Described pore former is selected from inorganic salts, inorganic molecules, macromolecule pore former or their mixture.Wherein said inorganic salts pore former is selected from lithium nitrate, calcium nitrate, sodium nitrate, lithium chloride, calcium chloride, sodium chloride etc.Described inorganic molecules pore former is selected from water, acetone, glycerine, ethylene glycol, ethanol, methyl alcohol etc.Described macromolecule pore former is selected from polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol etc.Described surfactant is selected from dodecyl sodium sulfate, lauryl sodium sulfate, tween 30, polysorbate60, Tween 80, N, N-dimethyl lauryl amine second lactone etc.
In the present invention, described macromolecular material, solvent, pore former, the ratio of surfactant in described polymer material film liquid are respectively in described polymer material film liquid gross weight 10-25%, 50-80%, 5-20% and 0-5%; Preferably, 10-22%, 55-80%, 8-20% and 0-5%; More preferably, 12-20%, 53-78%, 8-20% and 0-3%.
In the present invention, described coagulating bath should be appreciated that it is the liquid that can impel the film lyogel to solidify.
Contain non-solvent in the described coagulating bath, for example water, acetone, glycerine, ethylene glycol, ethanol, methyl alcohol etc.Preferably, described non-solvent is water or glycerine, ethylene glycol, ethanol, methyl alcohol.In order to regulate the gelation rate of feed liquid, can also in coagulating bath, add a certain proportion of solvent, for example acetone, oxolane, butanone, tetramethylurea, dimethyl formamide, dimethylacetylamide, methyl-sulfoxide, trimethyl phosphate, N-methyl pyrrolidone or their mixture.
In the present invention, the ratio of non-solvent and solvent is in described coagulating bath gross weight in the described coagulating bath, non-solvent 10-100% wherein, solvent 0-90%; Preferably, non-solvent 20-100%, solvent 0-80%; More preferably, non-solvent 30-100%, solvent 0-70%.
Prepare the enhancement mode hollow-fibre membrane, need with special spinning head.The schematic diagram of spinning head as shown in Figure 1, wherein (a) is profile, (b) is upward view.1 is the inlet of hollow braid, and 2 are core liquid inlet, and 3 are polymer material film liquid inlet, and 4 are the outlet of polymer material film liquid, and 5 is the outlet of hollow braid and core liquid.The hollow braid 1 enters spinning head from entering the mouth, and comes out from exporting 5.Simultaneously, core liquid 2 flows to spinning head from entering the mouth, and infiltrates the tube wall of hollow braid in spinning head, fills the inner chamber of hollow braid.When the hollow braid when the outlet 5 of spinning head is come out, the excessive core liquid of braid exterior can be scraped off.Meanwhile, polymer material film liquid 3 enters spinning head from entering the mouth, and comes out from exporting 4, and is coated in from exporting the outside of the 5 hollow braids that come out.
The spinning technique flow process of implementing described enhancement mode hollow-fibre membrane as shown in Figure 2.Feed liquid still 7 is equipped with polymer material film liquid I, and feed liquid still 17 is equipped with polymer material film liquid II, and core flow container 8 is equipped with core liquid.Twining the hollow braid on the wire wrapping wheel 9.Polymer material film liquid I enters spinning head 10 from polymer material film liquid inlet under the nitrogen pressure of steel cylinder 6, described core liquid enters spinning head from core liquid inlet, and described hollow braid enters spinning head from hollow braid inlet.Described polymer material film liquid, core liquid and hollow braid are extruded simultaneously through spinning head 10, enter then in the coagulating tank 11.By with the exchange of coagulating bath, the solvent in the described spinning solution enters coagulating bath mutually with pore former, and coagulating bath diffuses in the spinning solution.Polymer in the described spinning solution is separated out because of solubility reduces by the phase transfer precipitation, and attached on the hollow braid, the doughnut of this moment is called doughnut a.Doughnut a enters spinning head 16 through guide wheel 15, and extrudes simultaneously through spinning head 16 with the polymer material film liquid II that comes out from feed liquid still 17, enters then in the coagulating tank 12, thereby is spun into the reinforcement tubular porous body composite film.Made hollow fiber composite membrane is wrapped on the wire wrapping wheel 21 through guide wheel 20.Wire wrapping wheel is in rotation process, and hollow-fibre membrane is through the further gel solidification of deionized water in the wrapping wire rinse bath 13.The above-mentioned hollow-fibre membrane that makes soaks after 12 hours in 50 weight % glycerine water solutions, and room temperature is dried, and stores for future use.
The invention still further relates to reinforcement tubular porous body composite film of the present invention, or the purposes of reinforcement tubular porous body composite film in municipal wastewater, sanitary sewage, Industrial Wastewater Treatment prepared according to the methods of the invention.
[beneficial effect]
The invention has the advantages that: the hole and the inner chamber that soak and be full of the tubulose porous body earlier with core liquid, guaranteed in the process of preparation enhancement mode hollow-fibre membrane, polymer material film liquid can not infiltrate the tubulose porous body too much, thereby makes the inner chamber after the film forming keep unimpeded.Add the secondary of hollow-fibre membrane and film, guaranteed the integrality (or zero defect) of doughnut film outer surface.And the reinforcement tubular porous body composite film permeability rate that makes is big, the hot strength height; The range of choice broad of tubulose porous body is convenient to produce.
[description of drawings]
Fig. 1 is the spinning head structural representation, and wherein (a) is profile, (b) is upward view.1 is the inlet of hollow braid, and 2 are core liquid inlet, and 3 are polymer material film liquid inlet, and 4 are the outlet of polymer material film liquid, and 5 are the outlet of core liquid.
Fig. 2 is the spinning technique flow process of enhancement mode doughnut spinning-drawing machine.Wherein: 6,18: the nitrogen pressure steel cylinder; 7,17: the feed liquid still; 8: the core flow container; 9: hollow braid wire wrapping wheel; 10,16: spinning head; 11,12: coagulating tank; 13: the wrapping wire rinse bath; 14,15,19,20: the hollow-fibre membrane guide wheel; 21: wire wrapping wheel.
Fig. 3 is the section structure schematic diagram of reinforcement tubular porous body composite film, wherein, and 31, inner chamber; 32, hollow braid; 33, first tunic; 34, second tunic.
[specific embodiment]
Following non-limiting example illustrates in greater detail the present invention.
The pure water flux of described hollow-fibre membrane is measured under 20 ℃ of conditions according to People's Republic of China's ocean industry standard " doughnut miillpore filter method of testing HY/T 051 1 1999 ".
Average pore size is that the model that adopts U.S. Merck ﹠ Co., Inc to produce is that the micropore Structure Analysis instrument (mercury injection apparatus) of 9310 types is measured.
Internal diameter and external diameter are to use the light microscope determining of band scale, and used light microscope is that the XTT that Beijing section instrument electric light instrument plant produces becomes times stereomicroscope.
The commodity that hot strength is to use Shijiazhuang Zhongshi Detection Equipment Co., Ltd. to sell are called the product of WDT-5 electronics pulling experiment machine.Its hot strength is to measure according to the operating condition of described instrument operation instructions regulation.
Embodiment:
The hollow braid is that the 110 polyester monofilaments braiding by 130 dtexs forms, and its internal diameter is 1.0 millimeters, and external diameter is 2.2 millimeters.
Polymer material film liquid I's is composed as follows: 14 weight % Kynoar, 8 weight % polyvinylpyrrolidones, 6 weight % polyethylene glycol, 0.5 weight % lithium chloride, 1 weight % tween, 0.5 weight % water, 70 weight %N, N-dimethylacetylamide.
Polymer material film liquid II's is composed as follows: 18 weight % Kynoar, 9 weight % polyvinylpyrrolidones, 8 weight % polyethylene glycol, 1 weight % lithium chloride, 2 weight % tweens, 0.5 weight % water, 61.5 weight %N, N-dimethylacetylamide.
Consisting of of core liquid: 10 weight % polyvinylpyrrolidones, 90 weight %N, N-dimethylacetylamide.
Consisting of of coagulating bath: 20 weight % dimethylacetylamides, 80 weight % water.
Soak the hollow braid and apply the ground floor polymer material film:
The inner chamber that the hollow braid passes spinning head by the inlet 1 and the outlet 5 of spinning head (accompanying drawing 1); Simultaneously core liquid 2 enters the inner chamber of spinning head from entering the mouth, and infiltrates in the hollow braid, comes out from the outlet 5 of spinning head together with the hollow braid then.Meanwhile, polymer material film liquid I passes the exocoel of spinning head by the inlet 3 and the outlet 4 of spinning head, and is coated on the hollow braid, enters the coagulating bath gel forming then, and the doughnut of this moment is called doughnut a.
Coating second layer polymer material film:
Allow the above-mentioned doughnut a that makes continue through guide wheel by another one spinning head (the similar accompanying drawing 1 of its structure, but without core liquid), and and polymer material film liquid II extrude simultaneously through spinning head, enter the coagulating bath gel forming then.Film after the moulding is after the glycerine water solution of 50 weight % soaks 24 hours, and room temperature is dried, and makes reinforcement tubular porous body composite film b.
Film properties:
The internal diameter of the above-mentioned hollow-fibre membrane b that makes is 1.0 millimeters, and external diameter is 2.6 millimeters, and average pore size is 0.09 micron, and the hot strength of single hollow-fibre membrane is 136N.Pure water flux under 20 ℃ and 0.04MPa transmembrane pressure is 520L/h.m
2When being used to filter the second pond water outlet of sewage treatment plant, the sewage flux is 75L/m
2.h (20 ℃, 0.04MPa, external pressure moves 30 minutes, air water backwash 1 minute).
Comparative example:
Select for use and the similar spinning head of the foregoing description structure, but inner chamber is replaced by central tube, and preparation during hollow-fibre membrane without enhancement layer.Polymer material film liquid adopts the polymer material film liquid II in the foregoing description.The composition of coagulating bath is same as the previously described embodiments, and core liquid is selected the aqueous solution of 50 weight % dimethylacetylamides for use.
Polymer material film liquid II is extruded simultaneously by the spinning head and the core liquid in the pore of spinning head center of doughnut spinning-drawing machine, enter then in the outer coagulating bath.Film after the moulding is after the glycerine water solution of 50 weight % soaks 24 hours, and room temperature is dried, and makes hollow-fibre membrane c.
The internal diameter of hollow-fibre membrane c is 0.7 millimeter, and external diameter is 1.3 millimeters, and average pore size is 0.09 micron, and the hot strength of single hollow-fibre membrane is 2.6N.Pure water flux under 20 ℃ and 0.04MPa transmembrane pressure is 460L/h.m
2When being used to filter the second pond water outlet of sewage treatment plant, the sewage flux is 64L/m
2.h (20 ℃, 0.04MPa, external pressure moves 30 minutes, air water backwash 1 minute).
Claims (8)
1, a kind of reinforcement tubular porous body composite film, it is characterized in that it is made up of tubulose porous body and ground floor polymer material film and second layer polymer material film, described tubulose porous body is perforated pipe shape thing or a hollow braid on the wall, its aperture is the 0.1-10 micron, porosity is 10-70%, the thickness of described reinforcement tubular porous body composite film is the 0.05-0.5 millimeter, and the intermembranous joint face of ground floor polymer material film and second layer macromolecular material is the long-pending 50-100% of entire contact surface.
2, reinforcement tubular porous body composite film according to claim 1 is characterized in that described hollow braid is selected from polyethylene, polypropylene, polyamide, polyester; Perforated pipe shape thing is selected from polyamide or polyester on the described wall.
3, reinforcement tubular porous body composite film according to claim 1 is characterized in that described macromolecular material is selected from polyacrylonitrile, polysulfones, polyether sulfone, Kynoar, polyvinyl chloride or cellulose acetate.
4, a kind of preparation method of reinforcement tubular porous body composite film is characterized in that the step of this method is as follows:
A. soak the tubulose porous body with core liquid: allow the tubulose porous body pass the inner chamber of the spinning head of filling core liquid, and make core liquid infiltrate the tubulose porous body.
B. apply the ground floor polymer material film: allow polymer material film liquid I and the above-mentioned tubulose porous body that soaked core liquid extrude simultaneously, enter then in the outer coagulating bath by spinning head.
C. apply second layer polymer material film: allow polymer material film liquid II and the above-mentioned tubulose porous body that has been coated with the ground floor polymer material film extrude simultaneously by spinning head, and enter in the outer coagulating bath, make the reinforcement tubular porous body composite film behind the gel forming, soak after 12 hours in glycerine water solution, room temperature is dried again.
5, production method according to claim 4, it is characterized in that described core liquid is made up of solvent, non-solvent or their mixture, water-soluble polymer, alcohol, their ratio is respectively in described core liquid gross weight solvent 0-90%, non-solvent 10-100%, water-soluble polymer 0-10%, pure 0-90%; Described water-soluble polymer is selected from polyethylene glycol, polyvinylpyrrolidone, polymethylacrylic acid, CMC, hydroxypropyl cellulose, polyvinyl alcohol or polyacrylamide, and described alcohol is selected from ethanol, propyl alcohol, glycerine or ethylene glycol.
6, production method according to claim 4 is characterized in that described polymer material film liquid I and II are made up of macromolecular material, solvent, pore former and surfactant; Described macromolecular material is selected from polyacrylonitrile, polysulfones, polyether sulfone, Kynoar, polyvinyl chloride or cellulose acetate; Described solvent is selected from acetone, oxolane, butanone, tetramethylurea, dimethyl formamide, dimethylacetylamide, methyl-sulfoxide, trimethyl phosphate, N-methyl pyrrolidone or their mixture; Described pore former is selected from inorganic salts, inorganic molecules, macromolecule pore former or their mixture; Described inorganic salts pore former is selected from lithium nitrate, calcium nitrate, sodium nitrate, lithium chloride, calcium chloride or sodium chloride; Described inorganic molecules pore former is selected from water, acetone, glycerine, ethylene glycol, ethanol or methyl alcohol; Described macromolecule pore former is selected from polyvinylpyrrolidone, polyethylene glycol or polyvinyl alcohol; Described surfactant is selected from dodecyl sodium sulfate, lauryl sodium sulfate, tween 30, polysorbate60, Tween 80 or N, N-dimethyl lauryl amine second lactone.
7, production method according to claim 4 is characterized in that described coagulating bath is the mixture of non-solvent and solvent; Described non-solvent is selected from water, acetone, glycerine, ethylene glycol, ethanol or methyl alcohol; Described solvent is selected from acetone, oxolane, butanone, tetramethylurea, dimethyl formamide, dimethylacetylamide, methyl-sulfoxide, trimethyl phosphate, N-methyl pyrrolidone or their mixture, the ratio of non-solvent and solvent is in described coagulating bath gross weight non-solvent 10-100%, solvent 0-90% in the described coagulating bath.
8, reinforcement tubular porous body composite film according to claim 1 or according to the purposes of reinforcement tubular porous body composite film in municipal wastewater, sanitary sewage, Industrial Wastewater Treatment of the described method of arbitrary claim among claim 4-7 preparation.
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