CN101804305B - Conductive reinforced tubular porous body composite film, preparation method thereof, and use thereof in waste water dephosphorization - Google Patents
Conductive reinforced tubular porous body composite film, preparation method thereof, and use thereof in waste water dephosphorization Download PDFInfo
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Abstract
The invention discloses a conductive reinforced tubular porous body composite film and a preparation method thereof. The film consists of a conductive tubular porous body and a polymer material and is formed by coating a layer of polymer material on the conductive tubular porous body. The reinforced tubular porous body composite film of the invention has high conductivity, high permittivity and high tensile strength and has a promising application prospect.
Description
[technical field]
But the present invention relates to a kind of conductive reinforced 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 purifying and the sewage of water because 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 to thickness, and permeability rate and thickness are inversely proportional to.A kind of effective ways that solve this contradiction are to make composite membrane, the film that namely is comprised 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 larger 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 subject 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 of representing is mainly 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) after the coagulating bath gel.Fortifying fibre vertically is embedded in the wall of hollow-fibre membrane in this film.Fortifying fibre used is terylene, and nylon 6 or nylon 66 are non-conducting material.
Second method is first to spin out hollow-fibre membrane with polymer material film liquid, then in immersing again polymer material film liquid with synthetic fibers after this film outside is woven into net, strengthen hollow-fibre membrane (for example CN1864828A) through making reticular fibre after the coagulating bath gel.Netted braid is embedded in the wall of hollow-fibre membrane in this film.The reticular fibre material therefor is nonconducting terylene.
The third method is that polymer material film liquid is coated on the hollow support material, then immerses and make hollow-fibre membrane (for example patent CN1683059) in coagulating bath.Hollow support material used is nonconducting glass, polyester and nylon.
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 Filling can overcome the permeability rate reduction problem that polyacrylonitrile hollow fiber membrane causes because of contraction when applied at elevated temperature in the hole of hollow braid.Hollow braid material therefor is nonconducting polyester, acrylonitrile polymer, nylon or polyolefin.
Lung biopsy is that hollow braid and film liquid with special construction are spun into hollow-fibre membrane (for example patent US5472607) by spinning head together.The hole of hollow braid will be controlled at moderate level, if the space is too large, film liquid can infiltrate braid too much, and 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 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.Hollow braid used is nonconducting glass fibre.
The 6th kind of method is that the hollow braid with special construction and film liquid are passed through spinning head together, and makes hollow-fibre membrane through after coagulation bath; Again this hollow-fibre membrane and film liquid are spun into hollow-fibre membrane (for example patent US7306105) 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.Hollow braid material therefor is nonconducting polyester.
The 7th kind of method is that hollow braid, adhesive and film liquid are spun into hollow-fibre membrane (for example patent US7165682) by spinning head together.Wherein applying adhesive is on the hollow braid, and film liquid covers on adhesive.The effect of adhesive is the bond strength that increases between film and braid.Hollow braid used is non electrically conductive material.
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 Function of core liquid is first to immerse the hollow braid, and fills up the inner chamber of hollow braid, with the too much infiltration of block film liquid.Can reduce like this hole requirement to the hollow braid, enlarge the range of choice of hollow braid.Hollow braid used is nonconducting polyamide, polypropylene, polyethylene, polyester.
Fortifying fibre or hollow braid used in above-mentioned all methods are electrically non-conductive material, so range of application is restricted.
Therefore, also need to adopt new preparation method at present, prepare conductive reinforcement tubular porous body composite film, to enlarge range of application, satisfy actual needs to desalt and recycling sewage generated by making, so, the inventor has carried out lot of experiments research, has finally made the present invention.
[summary of the invention]
[the technical problem to be solved in the present invention]
But the purpose of this invention is to provide a kind of conductive reinforced tubular porous body composite film.
But another object of the present invention is to provide a kind of preparation method of conductive reinforced tubular porous body composite film.
But another object of the present invention is to provide a kind of purposes of conductive reinforced tubular porous body composite film.
[technical scheme]
Purpose of the present invention is mainly to solve the nonconducting problem of existing enhancing hollow-fibre membrane in prior art.This problem can solve by following method: but first make the conductive hollow braid, but then be coated with at the conductive braided fabric beyond the region of objective existence polymer material film liquid that one deck masking is used, and make hollow-fibre membrane through the coagulating bath gel solidification.Thereby obtain conductive hollow-fibre membrane.
Usually, the preparation method of described hollow fiber composite membrane adopts nonconducting hollow braid.Made like this hollow fiber composite membrane is also non-conductive.
For addressing the above problem, can first make conductive hollow braid, and then be coated with one deck polymer material film liquid.
But the present invention relates to a kind of conductive reinforced tubular porous body composite film.But described composite membrane is comprised of conductive tubular porous body and polymer material film, but described conductive tubular porous body is conductive hollow braid with holes on wall, and the aperture in described hole is the 0.1-10 micron, and porosity is 10-70%; The thickness of described polymer material film is the 0.05-0.5 millimeter.
A preferred embodiment of the invention, described hollow braid is formed by the conductive fiber braiding, or formed by conductive fiber and non-conductive fiber mixed weaving.
According to another kind of preferred embodiment of the present invention, described conductive fiber is selected from metallic compound type conductive fiber, metal is that conductive fiber, carbon black are conductive fiber or conducting polymer fiber type; Described non-conductive fiber is selected from polyethylene, polypropylene, polyamide or polyester.
According to another kind of preferred embodiment of the present invention, described macromolecular material is selected from polyacrylonitrile, polysulfones, polyether sulfone, Kynoar, polyvinyl chloride or cellulose acetate.
But the present invention relates to a kind of preparation method of conductive reinforced tubular porous body composite film.The step of the method is as follows:
But a. preparation of conductive tubular porous body: using and being selected from metallic compound type conductive fiber, metal is that conductive fiber, carbon black are that conductive fiber or the described conductive fiber of conductive fiber or conducting polymer fiber type becomes the tubulose porous body with the non-conductive fiber mixed weaving that is selected from polyethylene, polypropylene, polyamide or polyester;
B. apply polymer material film: allow polymer material film liquid and above-mentioned tubulose porous body extrude simultaneously by spinning head, then enter in outer coagulating bath, make the reinforcement tubular porous body composite film after gel forming, then soaked 12 hours in glycerine water solution, then at room temperature dry.
According to another kind of preferred embodiment of the present invention, described outer coagulating bath is comprised of solvent, non-solvent, water-soluble polymer and alcohol, and their ratio is respectively in described coagulating bath gross weight solvent 0-90%, non-solvent 10-100%, water-soluble polymer 0-10%, pure 0-90%.
Described solvent is selected from oxolane, butanone, tetramethylurea, dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), trimethyl phosphate, 1-METHYLPYRROLIDONE or their mixture.
Described non-solvent is water.
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.
According to another kind of preferred embodiment of the present invention, described polymer material film liquid is comprised of macromolecular material, solvent, pore former and surfactant; Their ratio is respectively in described polymer material film liquid gross weight macromolecular material 10-25%, solvent 50-80%, pore former 5-20% and surfactant 0-5%.
Described macromolecular material is selected from polyacrylonitrile, polysulfones, polyether sulfone, Kynoar, polyvinyl chloride or cellulose acetate;
Described solvent is selected from oxolane, butanone, tetramethylurea, dimethyl formamide, dimethylacetylamide, methyl-sulfoxide, trimethyl phosphate, 1-METHYLPYRROLIDONE or their mixture;
Described pore former is selected from inorganic salts pore former, inorganic molecules pore former, 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.
But the invention still further relates to the purposes of conductive reinforced tubular porous body composite film of the present invention in municipal wastewater, sanitary sewage, Industrial Wastewater Treatment.
The below will explain the present invention.
But the present invention relates to a kind of conductive reinforced tubular porous body composite film.But described composite membrane is comprised of conductive tubular porous body and polymer material film, but described conductive tubular porous body is conductive hollow braid with holes on wall, and the aperture in described hole is the 0.1-10 micron, and porosity is 10-70%; The thickness of described polymer material film is the 0.05-0.5 millimeter.
Described hollow braid is formed by the conductive fiber braiding, or formed by conductive fiber and non-conductive fiber mixed weaving.
Described conductive fiber is selected from metallic compound type conductive fiber, metal is that conductive fiber or carbon black are conductive fiber.The metallic compound type conductive fiber that uses in the present invention is for example can reach by auspicious the composite conducting fiber that special plastics trade Co., Ltds sells at present on market; Metal is that conductive fiber is the stainless steel metal fibre silk of being sold by Lu Site metallic fiber factory on market at present; Carbon black is that conductive fiber is to weave the conductive carbon fibre of limited sale by the permanent high-performance fiber of China at present on market.
Preferably, to be selected from metal be that conductive fiber or carbon black are conductive fiber to described conductive fiber.
Described non-conductive fiber is selected from polyethylene, polypropylene, polyamide or polyester.
Polyethylene, polypropylene, polyamide or the polyester that uses in the present invention is the product of knowing and generally using people in the art at present.
Preferably, described non-conductive fiber is selected from polyamide or polyester.
According to another kind of preferred embodiment of the present invention, described macromolecular material is selected from polyacrylonitrile, polysulfones, polyether sulfone, Kynoar, polyvinyl chloride or cellulose acetate.
Polyacrylonitrile, polysulfones, polyether sulfone, Kynoar, polyvinyl chloride or the cellulose acetate that uses in the present invention is the product of knowing and generally using people in the art at present.
Preferably to being the 0.2-8 micron, porosity is 20-60% in the aperture of hollow braid of the present invention.
For guaranteeing that made hollow-fibre membrane has performance preferably, the thickness of this hollow-fibre membrane, namely from the outside of hollow braid to the outside of hollow-fibre membrane, should be in certain scope, 0.05-0.5 millimeter preferably.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.
But conductive reinforced tubular porous body composite film performance of the present invention can characterize with average pore size, internal diameter and external diameter, the pure water flux under 20 ℃ and 0.02MPa transmembrane pressure, the hot strength of single hollow-fibre membrane.
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 what to use with the light microscope determining of scale, and light microscope used is the XTT zoom stereomicroscope that Beijing tech electric light instrument plant produces.
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 051-1999 ".
Hot strength is to use the product of the commodity WDT-5 electronics pulling experiment machine by name of Shijiazhuang Zhongshi Detection Equipment Co., Ltd.'s sale.Its hot strength is to measure according to the operating condition of described instrument operation instructions regulation.
But the present invention relates to a kind of preparation method of conductive reinforced tubular porous body composite film.The step of the method is as follows:
But a. preparation of conductive tubular porous body: using and being selected from metallic compound type conductive fiber, metal is that conductive fiber, carbon black are that conductive fiber or the described conductive fiber of conductive fiber or conducting polymer fiber type becomes the tubulose porous body with the non-conductive fiber mixed weaving that is selected from polyethylene, polypropylene, polyamide or polyester.
Described hollow braid is formed by the conductive fiber braiding, or formed by conductive fiber and non-conductive fiber mixed weaving.
In the methods of the invention, the conductive fiber that uses or the fiber number of non-conductive fiber all should be between 80～200 dtexs.
In the present invention, described conductive fiber braiding or conductive fiber should be appreciated that it is that use normally used braider in textile industry becomes a kind of tubulose porous body with the various fibrages that the present invention uses with the non-conductive fiber mixed weaving.
The metallic compound type conductive fiber, the metal that use in the methods of the invention are that conductive fiber, carbon black are that conductive fiber, conducting polymer fiber type are those materials as previously described.
Preferably, to be selected from metal be that conductive fiber or carbon black are conductive fiber to described conductive fiber.
Described non-conductive fiber is selected from polyethylene, polypropylene, polyamide or polyester.
Polyethylene, polypropylene, polyamide or the polyester that uses in the methods of the invention is the product of knowing and generally using people in the art at present.
B. apply polymer material film: allow polymer material film liquid and above-mentioned tubulose porous body extrude simultaneously by spinning head, then enter in outer coagulating bath, make the reinforcement tubular porous body composite film after gel forming, then soaked 12 hours in glycerine water solution, then at room temperature dry.
On meaning of the present invention, described outer solidification liquid should be appreciated that it is a kind ofly can impel the very liquid of supergrip of described polymer material film liquid.
According to another kind of preferred embodiment of the present invention, described outer coagulating bath is comprised of solvent, non-solvent, water-soluble polymer and alcohol, and their ratio is respectively in described coagulating bath gross weight solvent 0-90%, non-solvent 10-100%, water-soluble polymer 0-10%, pure 0-90%.Preferably, their ratio is respectively in described coagulating bath gross weight solvent 0-80%, non-solvent 20-100%, water-soluble polymer 0-10%, pure 0-80%.More preferably, their ratio is respectively in described coagulating bath gross weight solvent 0-70%, non-solvent 30-100%, water-soluble polymer 0-10%, pure 0-70%.
Described solvent is selected from oxolane, butanone, tetramethylurea, dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), trimethyl phosphate, 1-METHYLPYRROLIDONE or their mixture.
Described non-solvent is water.
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 methods of the invention, described these solvents, non-solvent, water-soluble polymer and alcohol are all the products of at present knowing and generally using people in the art.
According to another kind of preferred embodiment of the present invention, described polymer material film liquid is comprised of macromolecular material, solvent, pore former and surfactant; Their ratio is respectively in described polymer material film liquid gross weight macromolecular material 10-25%, solvent 50-80%, pore former 5-20% and surfactant 0-5%.Preferably, their ratio is respectively 10-22%, 55-80%, 8-20% and 0-5%; More preferably, their ratio is respectively 12-20%, 53-78%, 8-20% and 0-3%.
Described macromolecular material is selected from polyacrylonitrile, polysulfones, polyether sulfone, Kynoar, polyvinyl chloride or cellulose acetate.In wastewater treatment, particularly in the application of membrane bioreactor, Kynoar has larger advantage, because its good toughness, drug resistance is good.
Described solvent is selected from oxolane, butanone, tetramethylurea, dimethyl formamide, dimethylacetylamide, methyl-sulfoxide, trimethyl phosphate, 1-METHYLPYRROLIDONE or their mixture.
Described pore former is selected from inorganic salts pore former, inorganic molecules pore former, 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.
In the methods of the invention, described these macromolecular materials, solvent, pore former and surfactant are all the products of at present knowing and generally using people in the art.
Need to use spinning head of the present invention when preparation enhancement type hollow fiber film of the present invention.The structural representation of this spinning head as shown in Figure 1, wherein (a) is profile, is (b) upward view.1 is the entrance of hollow braid, and 2 is core liquid entrance, and 3 is polymer material film liquid entrance, and 4 are the outlet of polymer material film liquid, and 5 are the outlet of hollow braid.The hollow braid enters spinning head from entrance 1, and from exporting 5 out.Meanwhile, polymer material film liquid enters spinning head from entrance 3, from exporting 4 out, is coated in from exporting 5 out the outsides of hollow braid.
Described spinning technique flow process of conducting electricity enhancement type hollow fiber film as shown in Figure 2.Feed liquid still 2 is equipped with polymer material film liquid.Be wound around the hollow braid on wire wrapping wheel 4.Polymer material film liquid enters spinning head 3 from polymer material film liquid entrance under the nitrogen pressure of steel cylinder 1, described hollow braid enters spinning head from hollow braid entrance.Described polymer material film liquid and hollow braid are extruded simultaneously through spinning head 3, then enter in coagulating tank 5.By with the exchange of coagulating bath, the solvent in described spinning solution enters coagulating bath mutually with pore former, and coagulating bath diffuses in spinning solution.Polymer in described spinning solution reduces by the phase transfer Precipitation because of solubility, and is attached on the hollow braid, thereby but is spun into conductive reinforced tubular porous body composite film.But made conductive hollow composite fiber membrane is wrapped on wire wrapping wheel 9 through guide wheel 7.Wire wrapping wheel is in rotation process, and hollow-fibre membrane is through the further gel solidification of deionized water in wrapping wire rinse bath 8.The above-mentioned hollow-fibre membrane that makes soaks after 12 hours in 50 % by weight glycerine water solutions, and room temperature is dried, and stores for future use.
But the invention still further relates to the purposes of conductive reinforced tubular porous body composite film of the present invention in municipal wastewater, sanitary sewage, Industrial Wastewater Treatment.
[beneficial effect]
The invention has the advantages that: but the conductive hollow fiber braided tube become with conductive fiber or conductive fiber with the non-conductive fiber mixed weaving, then be coated with last layer polymeric membrane liquid, make hollow fiber composite membrane after the gel pore-forming.Because the woven hollow fiber pipe conducts electricity, so the hollow fiber composite membrane of making also conducts electricity.Water treatment effect can be improved very significantly like this, the range of application of hollow fiber composite membrane can also be enlarged.
[description of drawings]
Fig. 1 is the spinning head structural representation, and wherein (a) is profile, is (b) upward view.1 is the entrance of hollow braid, and 2 is steam vent, and 3 is polymer material film liquid entrance, and 4 are the outlet of polymer material film liquid, and 5 is the outlet of hollow braid.
Fig. 2 is the spinning technique flow process of enhancement mode hollow fiber spinning machine.Wherein: 1: the nitrogen pressure steel cylinder; 2: the feed liquid still; 3: spinning head; 4: hollow braid wire wrapping wheel; 5: coagulating tank; 6,7: the hollow-fibre membrane guide wheel; 8: the wrapping wire rinse bath; 9: wire wrapping wheel.
Fig. 3 is the section structure schematic diagram of reinforcement tubular porous body composite film, wherein 10, rete; But 11 conductive hollow braids; 12, inner chamber.
[specific embodiment]
Following non-limiting example illustrates in greater detail the present invention.
Embodiment 1:
The hollow braid is to use equipment that Xuzhou permanent brightness weaving machinery Co., Ltd sells with trade name hollow rope braider by 110 tubulose porous bodies that the braiding of conductive carbon fibre monofilament forms of 130 dtexs, the internal diameter of this tubulose porous body is 1.0 millimeters, and external diameter is 2.2 millimeters.
Preparation polymer material film liquid: in described polymer material film liquid gross weight, take 18 % by weight Kynoar, 7 % by weight polyvinylpyrrolidones, 3 % by weight polyethylene glycol, 1 % by weight lithium chloride, 2 % by weight tweens, 1 % by weight water, 68 % by weight N, the N-dimethylacetylamide, stirred 12 hours at 60 ℃ after mixing, more described polymer material film liquid is made in deaeration after 12 hours.
Preparation coagulating bath: in described coagulation bath gross weight, take 10 % by weight polyvinylpyrrolidones, 90 % by weight DMAs, make described coagulating bath after mixing.
According to the technical process that accompanying drawing 1 is described, allow the hollow braid for preparing previously pass the inner chamber of spinning head by spinning head entrance 1 and outlet 5.Meanwhile, entrance 3 and outlet 4 exocoel that pass spinning head of polymer material film liquid by spinning head.Film after moulding soaked 12 hours through the glycerine water solution of 50 % by weight, then at room temperature dried, so but make conductive reinforced tubular porous body composite film.
Film to the present embodiment preparation has carried out film properties mensuration.
Assay method is the method for having described in this specification.
The internal diameter of the hollow-fibre membrane that the present embodiment makes is 1.0 millimeters, and external diameter is 2.5 millimeters, and average pore size is 0.08 micron, and the hot strength of single hollow-fibre membrane is 120N.Pure water flux under 20 ℃ and 0.02MPa transmembrane pressure is 190L/h.m
2
The hollow-fibre membrane that uses the present embodiment to make has carried out the sewage disposal test.
The conductive hollow tunica fibrosa that the present embodiment is made is as negative electrode, then uses an iron plate as anode, and in parallel insertion sanitary sewage pond, two interelectrode distances are 3 centimetres, and power supply is the direct current of 9 volts.Energising on one side is on one side from hollow-fibre membrane toward extracardiac pumping.Adopt simultaneously molybdenum blue method analysis total phosphorus content in waste water before and after processing that in the analytical chemistry field, people know.Mensuration obtains before filtration that in sewage, total phosphorus content is 5.6mg/L, and after energising was filtered, in water, total phosphorus dropped to 4.2mg/L.
Comparative example 1:
According to being filmed and the sewage disposal test with above-described embodiment the same manner, just conductive fiber is changed to non-conductive fiber.The analysis showed that, in sewage, total phosphorus content is 5.6mg/L before filtration, and after energising was filtered, in water, total phosphorus dropped to 5.2mg/L.
Embodiment 2:
According to being filmed and sewage disposal test with above-described embodiment the same manner, just the hollow fabric is to be formed by conductive carbon fibre and the polyester non-conductive fiber ratio mixed weaving in 1: 1.The analysis showed that, in sewage, total phosphorus content is 5.6mg/L before filtration, and after energising was filtered, in water, total phosphorus dropped to 4.5mg/L.
Embodiment 3:
Identical with masking and the application process of embodiment 1, just the hollow fabric is to be formed by conductive fiber and the polypropylene non-conductive fiber ratio mixed weaving in 1: 2.Made conductive hollow tunica fibrosa is used for sewage disposal, and in the front sewage of filtration, total phosphorus content is 5.6mg/L, and after energising was filtered, in water, total phosphorus dropped to 4.8mg/L.
Claims (9)
1. conductive reinforcement tubular porous body composite film, it is characterized in that but it is comprised of conductive tubular porous body and polymer material film, but described conductive tubular porous body is conductive hollow braid with holes on wall, the aperture in described hole is the 0.1-10 micron, and porosity is 10-70%; The thickness of described polymer material film is the 0.05-0.5 millimeter; Described hollow braid is formed by the conductive fiber braiding, or formed by conductive fiber and non-conductive fiber mixed weaving.
2. reinforcement tubular porous body composite film according to claim 1, is characterized in that; Described conductive fiber is selected from metallic compound type conductive fiber, metal is that conductive fiber, carbon black are conductive fiber or conducting polymer fiber type; Described non-conductive fiber is selected from polyethylene, polypropylene, polyamide or polyester.
3. but conductive reinforced 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. but the preparation method of a conductive reinforced tubular porous body composite film is characterized in that the step of the method is as follows:
But a. preparation of conductive tubular porous body: using and being selected from metallic compound type conductive fiber, metal is that conductive fiber, carbon black are that conductive fiber or the described conductive fiber of conductive fiber or conducting polymer fiber type becomes the tubulose porous body with the non-conductive fiber mixed weaving that is selected from polyethylene, polypropylene, polyamide or polyester;
B. apply polymer material film: allow polymer material film liquid and above-mentioned tubulose porous body extrude simultaneously by spinning head, then enter in outer coagulating bath, make the reinforcement tubular porous body composite film after gel forming, then soaked 12 hours in glycerine water solution, then at room temperature dry;
5. production method according to claim 4, it is characterized in that described outer coagulating bath is comprised of solvent, non-solvent, water-soluble polymer and alcohol, their ratio is respectively in described coagulating bath gross weight solvent 0-90%, non-solvent 10-100%, water-soluble polymer 0-10%, pure 0-90%.
6. production method according to claim 5, is characterized in that described solvent is selected from oxolane, butanone, tetramethylurea, dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), trimethyl phosphate, 1-METHYLPYRROLIDONE or their mixture;
Described non-solvent is water;
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.
7. production method according to claim 4, is characterized in that described polymer material film liquid is comprised of macromolecular material, solvent, pore former and surfactant; Their ratio is respectively in described polymer material film liquid gross weight macromolecular material 10-25%, solvent 50-80%, pore former 5-20% and surfactant 0-5%.
8. production method according to claim 7, is characterized in that described macromolecular material is selected from polyacrylonitrile, polysulfones, polyether sulfone, Kynoar, polyvinyl chloride or cellulose acetate;
Described solvent is selected from oxolane, butanone, tetramethylurea, dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), trimethyl phosphate, 1-METHYLPYRROLIDONE or their mixture;
Described pore former is selected from inorganic salts pore former, inorganic molecules pore former, 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; 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.
9. but the described conductive reinforced tubular porous body composite film of arbitrary claim according to claim 1-3, but or the purposes of conductive reinforced tubular porous body composite film in municipal wastewater, sanitary sewage, Industrial Wastewater Treatment of the described method preparation of arbitrary claim according to claim 4-8.
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| CN103585895B (en) * | 2013-11-26 | 2015-12-09 | 天津工业大学 | A kind of preparation method of conductive pin fabric reinforced composite membrane |
| CN103585894B (en) * | 2013-11-26 | 2015-12-02 | 天津工业大学 | A kind of conductive pin fabric reinforced composite membrane |
| CN104289114B (en) * | 2014-09-10 | 2016-10-19 | 同济大学 | A kind of conduction filter membrane and application thereof |
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| EP1658889A1 (en) * | 2004-11-19 | 2006-05-24 | "VLAAMSE INSTELLING VOOR TECHNOLOGISCH ONDERZOEK", afgekort "V.I.T.O." | Longitudinal reinforced self-supporting capillary membranes and method for manufacturing thereof |
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| CN1242715A (en) * | 1997-10-28 | 2000-01-26 | 阿莫科公司 | Composite materials for membrane reactors |
| CN1358212A (en) * | 1999-04-30 | 2002-07-10 | 托马斯·翰翎 | Composites and composite membranes |
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