CN100546702C - Strengthen capillary-pipe film and preparation method thereof - Google Patents
Strengthen capillary-pipe film and preparation method thereof Download PDFInfo
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- CN100546702C CN100546702C CNB2007100569169A CN200710056916A CN100546702C CN 100546702 C CN100546702 C CN 100546702C CN B2007100569169 A CNB2007100569169 A CN B2007100569169A CN 200710056916 A CN200710056916 A CN 200710056916A CN 100546702 C CN100546702 C CN 100546702C
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Abstract
A kind of enhancing capillary-pipe film and preparation method thereof.Strengthen capillary-pipe film, be made of capillary braid supporter and film, the density of capillary braid changes in gradient.Coating coating liquid and make it to be penetrated into the inside of capillary braid on the braid adopts the method for wet method inversion of phases, and freezing film in coagulating bath forms and strengthens capillary-pipe film.Coating liquid is by 5～35 parts in polymer (parts by weight), additive 0-35 part, and 30～80 parts of solvents, pore-foaming agent are mixed for 1～40 part and form.This enhancing capillary-pipe film has the mechanical strength height, and tension is effective, and pure water permeability is higher, can adapt to high strength, big flow backwash operation.Particularly can avoiding in use, the decortication phenomenon of film takes place.The manufacture method of the present invention advanced person that possesses skills, fast, characteristics such as steady quality, safety and environmental protection.The enhancing capillary-pipe film that the present invention prepares can be made into pillar membrane module or immersed membranes device, is suitable for water purification and wastewater treatment and reuse.
Description
[technical field]
The invention belongs to the membrane separation technique field, particularly a kind of enhancing capillary-pipe film that is used as miillpore filter or milipore filter and preparation method thereof.Be applicable to water purification and wastewater treatment and reuse.
[background technology]
Membrane separation technique is a kind of separation of material in liquid or the gas medium, isolation technics that concentrates and purify of being widely used in.Be used for the extremely trickle micropore that gathers on the membranous wall of fluid separation applications, during the side by film, solvent and low molecule solute see through membranous wall to be become through liquid stoste under pressure, and big molecule solute tunicle is held back, thereby reaches the purpose of feed separation or purifying.Membrane technology is a kind of advanced person's a isolation technics, and many advantages are arranged.For example separation accuracy height, selectivity are strong, at normal temperatures the no phase-state change of operation, energy consumption is low, automaticity is high, pollution is little etc.
Doughnut is a kind of important form of diffusion barrier.Compare with other form membrane modules, filling film area doughnut is maximum in the unit volume.Characteristics such as hollow-fibre membrane has the separative efficiency height, cleans easily, simple in structure, easy to operate, cost performance height, thereby be widely used.
When particularly being applied to membrane bioreactor, owing to the vigorous stirring effect of gas, there is the problem of bad mechanical strength in present commercial hollow-fibre membrane in water treatment and waste water treatment applications process, the phenomenon of rupture of film generation in use often takes place.Hollow-fibre membrane during this require to use not only has high permeance property, good stalling characteristic, and will have than higher in the past mechanical performance.
Canada Zenon environment Co., Ltd proposes in United States Patent (USP) (5472607): coat polyvinylidene fluoride film in the hollow textile surface, but under the environment of high-intensity oscillation, exist the problem that perforated membrane easily peels off from textile surface.Can not adopt the cleaning method of high strength backwash, the cleaning of film and recovery effects are restricted.
Mitsubishi Li Yang Co., Ltd. proposes in the disclosed patent of China (number of patent application 200380102726.6): imbed fortifying fibre in the Kynoar porous plastid, this scheme might cause the flux of film to reduce, and causes the porous body to break easily under violent tensile force effect.
Mitsubishi Li Yang Co., Ltd. proposes in disclosed another patent of China (number of patent application 200380102726.6): in order to improve the stripper-resistance of film, adopt the scheme of duplicature, but there is the process complexity in this scheme, is difficult to control.In addition, can not adopt the cleaning method of big flow, high strength backwash, fail from the caducous problem of basic solution film.
Yiming Filtering Technology Co., Ltd., Shanghai has proposed a kind of enhancement mode hollow fiber ultrafiltration membrane and preparation method thereof in its disclosed patent (number of patent application 200510024195.4).The concrete property that does not relate to braid in its application for patent, the aperture of film is confined to the milipore filter scope, fails anti-burst aspect performance indications to the characterization of membrane such as burst pressure of membrane, is difficult to judge whether solved present already present problem.
[summary of the invention]
The objective of the invention is to solve the prior art above shortcomings, a kind of enhancing capillary-pipe film and preparation method thereof is provided.
Enhancing capillary-pipe film provided by the invention is made of capillary braid supporter and film, and the capillary braid is to be formed by fibrage, the density of capillary braid changes in gradient, density reduces from the inside to surface, and the ratio that density gradient changes is 1.5-10, preferred 2-6.The inside that coating coating liquid and making it is penetrated into the capillary braid on the capillary braid forms and strengthens capillary-pipe film, and the degree of depth that wherein enters is the 10-80% of capillary braid supporter thickness, and the thickness that strengthens capillary-pipe film is 0.1-1.0mm.
The internal diameter of capillary braid is 0.5-3.0mm, external diameter 1.0-5.0mm, dense side mesh aperture 5-100 micron, preferred 10-50 micron.The braid shape of a mesh can be a kind of in the shapes such as irregular rhombus, rectangle.
The average pore size of film is positioned at milipore filter or micro-filtration membrane scope, generally gets the 0.001-0.45 micron, and its compacted zone is at outer surface.
The cilium numerical control of described capillary braid is built in every meter below 10, and is preferred below 2.
The hot water shrinkage of described capillary braid is controlled in 10%, in preferred 5%; Elongation at break is lower than 40%, in preferred 15%.
Described coating liquid is mixed by following ratio of weight and number by polymer, pore-foaming agent, solvent, additive and forms: 5～35 parts in polymer, additive 0-35 part, 30～80 parts of solvents, 1～40 part of pore-foaming agent.
Wherein polymer can be at least a in polyether sulfone, polysulfones, polyvinyl chloride, chliorinated polyvinyl chloride, Kynoar, SPSF, polyether-ketone, polyacrylonitrile or its copolymer, or the blend between them.
Described additive can be inorganic particle such as zirconia, aluminium oxide, iron oxide or molecular sieve, or organic granular such as powder ion exchange resin, macroporous absorbent resin, graphite powder or CNT, the granularity 0.05-50 micron of particulate.
Described solvent can be at least a in N-methyl pyrrolidone, dimethylacetylamide, dimethyl formamide, dimethyl sulfoxide (DMSO) or the oxolane, or the mixture between them.
Described pore-foaming agent adopts in polyethylene glycol, PVP, SPSF, partial hydrolysis polyvinyl acetate, surfactant, unit alcohols, polyalcohol, the polyalcohol condensation polymer at least a.Surfactant is one or more mixtures in anionic, the cationic and nonionic surface active agent.
The ratio of additive and polymer is controlled in the scope of 0.1-5.0 in the described coating liquid, preferred 0.5-2.5.
The ratio of pore-foaming agent and polymer is controlled in the scope of 0.05-5.0 in the described coating liquid, preferred 0.3-3.0.
Described fiber is a kind of in composite filament, monofilament, the short fiber, preferred composite filament.The quantity of composite filament is 30-200, and the fiber number of composite filament is 400-1200dtx (dtex), preferred 500-900dtx.
Described fibrous material is a kind of in polyester, nylon, polyamide fibre, Wei Lun, cotton fiber, cellulose, glass fibre, carbon fiber or the metallic fiber.Polyester fiber intensity is good, drug resistance is high and inexpensive, so the preferred polyester fiber.
A kind of preparation method of above-mentioned enhancing capillary-pipe film comprises the steps:
(1) making of gradient capillary shape braid: adopt the compound braider of 4-32 head to weave capillary with density gradient, the ratio that density gradient changes is 1.5-10, the internal diameter of capillary braid is 0.5-3.0mm, external diameter 1.0-5.0mm, braid mesh aperture 5-100 micron;
(2) preparation of coating liquid: polymer, pore-foaming agent, solvent, additive are mixed by following ratio of weight and number: 5～35 parts in polymer, additive 0-35 part, 30～80 parts of solvents, 1～40 part of pore-foaming agent; Mixture was stirred 4～12 hours down at 20～80 ℃, and standing and defoaming made the coating liquid that mixes after 24～48 hours under the normal temperature;
(3) film: under 20～80 ℃, the coating liquid that makes at capillary braid outer surface coating one deck preparation liquid, through behind 0.5-100 centimetre the air section, is placed on solidification forming in the coagulating bath of 20～90 ℃ of temperature, makes the enhancing capillary-pipe film; The thickness of described enhancing capillary-pipe film is 0.1-1.0mm;
(4) post processing: soak into the enhancement mode capillary-pipe film 8～48 hours of gained with the glycerine water solution of 5～50wt%, make and strengthen the capillary-pipe film finished product.
Coagulating bath can be the mixture of water or water and solvent, and the solvent strength in the coagulating bath is 1-80%, and the temperature of coagulating bath is 20～90 ℃.The washing temperature of film is controlled at 10-90 ℃, preferred 20-60 ℃.
Advantage of the present invention and beneficial effect:
The enhancing capillary-pipe film of the present invention's preparation has the mechanical strength height, and tension is effective, and pure water permeability is higher, can adapt to high strength, big flow backwash operation, and contamination resistance is strong.Particularly can avoiding in use, the decortication phenomenon of film takes place.Test shows: the pure water flux that the present invention strengthens capillary-pipe film can reach 175-3000L/m
2H.0.1MPa, controllable adjustment in the 0.001-0.45 micrometer range of aperture, and clean easily and regenerate.The enhancing capillary-pipe film that the present invention prepares can be made into pillar membrane module or immersed membranes device, is suitable for water purification and wastewater treatment and reuse.
Compare with the preparation method of prior art, the manufacture method of the present invention advanced person that possesses skills, fast, characteristics such as steady quality, safety and environmental protection.
[specific embodiment]
Embodiment 1,
The mass percent prescription of coating liquid is: the 15wt% polyether sulfone; The 15wt% polyethylene glycol; 5wt% degree of hydrolysis 50% polyvinyl acetate and 65wt% dimethylacetylamide mix described each component, stir 8 hours down at 70 ℃, and standing and defoaming made uniform coating liquid after 24 hours under the normal temperature.
Strengthen the manufacturing process of capillary-pipe film: the polyester filaments bundle of selecting fiber number 750tdx for use, adopt the capillary of the composite braided internal diameter 0.9mm/ of braider external diameter 1.8mm, working out density capillaceous reduces from the inside to the outside gradually, form gradient density capillary, internal layer/outer density ratio is about 3.0, and capillary inner surface mesh aperture is 10 microns.The capillary cilium numerical control of braiding is built in every meter below 2.The hot water shrinkage 3% of capillary braid.The capillary importing of braiding in advance is coated with in the membrane module, the supply of control coating liquid, coating liquid is immersed in 0.15mm in the capillary, the capillary that the surface scribbles coating liquid enters after through 10 millimeters air sections in 20 ℃ of coagulating baths that contain 5% dimethylacetylamide, in 40 ℃ of water after the washes clean, soak into the enhancement mode capillary-pipe film 24 hours of gained with the glycerine water solution of 30wt%, standby after the air dry.
The inner/outer diameter of the enhancing capillary-pipe film of gained is about 0.9mm/1.9mm, the pure water flux 1500L/m of film
2H.0.1MPa, burst pressure is greater than 0.55MPa, and film is 10% to the rejection of the bovine serum albumin of relative molecular mass 67000,0.10 micron of the average pore size of film.
Embodiment 2,
The mass percent prescription of coating liquid is: the 20wt% polyether sulfone; The 20wt% polyethylene glycol; 0.5%OP-10 surfactant and 59.5wt% dimethylacetylamide.Described each component is mixed, stirred 10 hours down at 70 ℃, standing and defoaming made uniform coating liquid after 36 hours under the normal temperature.
Strengthen the manufacturing process of capillary-pipe film: the polyester filaments bundle of selecting fiber number 850tdx for use, adopt the capillary of the composite braided internal diameter 1.0mm/ of braider external diameter 1.8mm, working out density capillaceous reduces from the inside to the outside gradually, form gradient density capillary, internal layer/outer density ratio is about 3.5, and capillary inner surface mesh aperture is 15 microns.The capillary cilium numerical control of braiding is built in every meter below 2.The hot water shrinkage 2% of capillary braid.The capillary importing of braiding in advance is coated with in the membrane module, the supply of control coating liquid, coating liquid is immersed in 0.10mm in the capillary, the capillary that the surface scribbles coating liquid enters 50 ℃ after through 50 millimeters air sections and solidifies in the bath water, in 60 ℃ of water after the washes clean, soak into the enhancement mode capillary-pipe film 24 hours of gained with the glycerine water solution of 30wt%, standby after the air dry.
The inner/outer diameter of the enhancing capillary-pipe film of gained is about 0.95mm/2.05mm, the pure water flux 420L/m of film
2H.0.1MPa, burst pressure is greater than 0.6MPa, and the average pore size that the fluid removal method detects film is 0.005 micron, and film is 95% to the rejection of the bovine serum albumin of relative molecular mass 67000.
Embodiment 3,
The mass percent prescription of coating liquid is: the 10wt% polyether sulfone; The 15wt% polyethylene glycol; 10wt% polyvinylpyrrolidone and 65wt% dimethyl formamide.Described each component is mixed, stirred 6 hours down at 70 ℃, standing and defoaming made uniform coating liquid after 24 hours under the normal temperature.
Strengthen the manufacturing process of capillary-pipe film: the polyester filaments bundle of selecting fiber number 900tdx for use, adopt the capillary of the composite braided internal diameter 1.0mm/ of braider external diameter 1.85mm, working out density capillaceous reduces from the inside to the outside gradually, form gradient density capillary, internal layer/outer density ratio is about 4, and capillary inner surface mesh aperture is 5 microns.The capillary cilium numerical control of braiding is built in every meter below 2.The hot water shrinkage 2% of capillary braid.The capillary importing of braiding in advance is coated with in the membrane module, the supply of control coating liquid, coating liquid is immersed in 0.2mm in the capillary, the capillary that the surface scribbles coating liquid enters 70 ℃ after through 80 millimeters air sections and solidifies in the bath water, in 80 ℃ of water after the washes clean, soak into the enhancement mode capillary-pipe film 24 hours of gained with the glycerine water solution of 30wt%, standby after the air dry.
The inner/outer diameter of the enhancing capillary-pipe film of gained is about 0.9mm/1.95mm, the pure water flux 3000L/m of film
2H.0.1MPa, burst pressure is greater than 0.45MPa, and film is 5% to the rejection of the bovine serum albumin of relative molecular mass 67000,0.45 micron of the average pore size of film.
Embodiment 4,
The mass percent prescription of coating liquid is: the 25wt% polyether sulfone; 10% polyethylene glycol; 15wt% two contract TEG and 50wt%N-methyl pyrrolidone.Described each component is mixed, stirred 10 hours down at 70 ℃, standing and defoaming made uniform coating liquid after 24 hours under the normal temperature.
Strengthen the manufacturing process of capillary-pipe film: the polyester filaments bundle of selecting fiber number 750tdx for use, adopt the capillary of the composite braided internal diameter 1.0mm/ of braider external diameter 1.9mm, working out density capillaceous reduces from the inside to the outside gradually, form gradient density capillary, internal layer/outer density ratio is about 5.0, and capillary inner surface mesh aperture is 15 microns.The capillary cilium numerical control of braiding is built in every meter below 2.The hot water shrinkage 2% of capillary braid.The capillary importing of braiding in advance is coated with in the membrane module, the supply of control coating liquid, coating liquid is immersed in 0.15mm in the capillary, the capillary that the surface scribbles coating liquid enters 50 ℃ after through 10 millimeters air sections and solidifies in the bath water, in 90 ℃ of water after the washes clean, soak into the enhancement mode capillary-pipe film 24 hours of gained with the glycerine water solution of 30wt%, standby after the air dry.
The inner/outer diameter of the enhancing capillary-pipe film of gained is about 1.0mm/2.05mm, the pure water flux 175L/m of film
2H.0.1MPa, burst pressure is greater than 0.6MPa, and the average pore size that the fluid removal method detects film is 0.001 micron, and film is 96% to the rejection of the bovine serum albumin of relative molecular mass 67000.
Embodiment 5,
The mass percent prescription of coating liquid is designed to: the 15wt% polyether sulfone; 15wt% particulate oxide aluminium powder, average grain diameter 3 μ m; The 10wt% polyethylene glycol; The 2wt% polyvinylpyrrolidone; 0.5% Tween-80 and 57.5wt% dimethylacetylamide.Described each component is mixed, and 60 ℃ of following high-speed stirred 12 hours, standing and defoaming made uniform coating liquid after 48 hours under the normal temperature.
The process of making the enhancing capillary-pipe film is with example 1, and the inner/outer diameter of the enhancing capillary-pipe film of gained is about 0.9mm/2.0mm, the pure water flux 560L/m of film
2H.0.1MPa, burst pressure is greater than 0.55MPa, and film is 95% to the rejection of the bovine serum albumin of relative molecular mass 67000.
Embodiment 6,
The mass percent prescription of coating liquid is designed to: the 15wt% polyether sulfone; 20wt% cationic ion-exchange resin powder, average grain diameter 15 μ m; The 10wt% polyethylene glycol; 5wt% polyvinylpyrrolidone and 55wt% dimethyl sulfoxide (DMSO).Described each component is mixed, and 65 ℃ of following high-speed stirred 10 hours, standing and defoaming made uniform coating liquid after 24 hours under the normal temperature.
The process of making the enhancing capillary-pipe film is with example 1, and the inner/outer diameter of the enhancing capillary-pipe film of gained is about 0.9mm/2.1mm, the pure water flux 260L/m of film
2H.0.1MPa, burst pressure is greater than 0.5MPa, and film is 94.5% to the rejection of the bovine serum albumin of relative molecular mass 67000.
Embodiment 7
The mass percent prescription of coating liquid is designed to: the 18wt% Kynoar; The 15wt% polyethylene glycol; The 1.0%OP-10 surfactant; 0.5% lithium chloride and 65.5wt% dimethylacetylamide.Described each component is mixed, stirred 12 hours down at 80 ℃, standing and defoaming made uniform coating liquid after 24 hours under the normal temperature.
The process of making the enhancing capillary-pipe film is with example 1, and the inner/outer diameter of the enhancing capillary-pipe film of gained is about 0.9mm/2.0mm, the pure water flux 430L/m of film
2H.0.1MPa, burst pressure is greater than 0.45MPa, and film is 88% to the rejection of the bovine serum albumin of relative molecular mass 67000.
Embodiment 8
The mass percent prescription of coating liquid is designed to: the 13.5wt% Kynoar; The 20wt% propane diols; The 2wt% polyvinylpyrrolidone; 0.5% lithium chloride and 64wt% dimethylacetylamide.Described each component is mixed, stirred 10 hours down at 70 ℃, standing and defoaming made uniform coating liquid after 24 hours under the normal temperature.
The process of making the enhancing capillary-pipe film is with example 1, and the inner/outer diameter of the enhancing capillary-pipe film of gained is about 0.9mm/1.96mm, the pure water flux 1450L/m of film
2H.0.1MPa, burst pressure is greater than 0.40MPa, and film is 15% to the rejection of the bovine serum albumin of relative molecular mass 67000,0.2 micron of the average pore size of film.
Embodiment 9
The mass percent prescription of coating liquid is designed to: the 14wt% Kynoar; 14wt% particulate Zirconium dioxide powder, average grain diameter 5 μ m; 10wt% ethylene glycol; The 5wt% polyvinylpyrrolidone; 0.1% dodecyl sodium sulfate and 56.9wt% dimethylacetylamide.Described each component is mixed, and 60 ℃ of following high-speed stirred 12 hours, standing and defoaming made uniform coating liquid after 24 hours under the normal temperature.
The process of making the enhancing capillary-pipe film is with example 1, and the inner/outer diameter of the enhancing capillary-pipe film of gained is about 0.9mm/1.95mm, the pure water flux 650L/m of film
2H.0.1MPa, burst pressure is greater than 0.45MPa, and film is 78% to the rejection of the bovine serum albumin of relative molecular mass 67000.
Embodiment 10
The mass percent prescription of coating liquid is designed to: the 15wt% polyvinyl chloride; The 10wt% polyethylene glycol; 5% propane diols and 70wt% dimethylacetylamide.Described each component is mixed, stirred 10 hours down at 60 ℃, standing and defoaming made uniform coating liquid after 24 hours under the normal temperature.
The process of making the enhancing capillary-pipe film is with example 1, and the inner/outer diameter of the enhancing capillary-pipe film of gained is about 0.9mm/1.95mm, the pure water flux 400L/m of film
2H.0.1MPa, burst pressure is greater than 0.5MPa, and film is 85% to the rejection of the bovine serum albumin of relative molecular mass 67000.
Embodiment 11
The mass percent prescription of coating liquid is designed to: the 16wt% chliorinated polyvinyl chloride; The 5wt% polyvinylpyrrolidone; 5wt% ethylene glycol and 74wt% dimethylacetylamide.Described each component is mixed, stirred 12 hours down at 70 ℃, standing and defoaming made uniform coating liquid after 24 hours under the normal temperature.
The technology of system film is with example 1, and the inner/outer diameter of the enhancing capillary-pipe film of gained is about 0.9mm/1.98mm, the pure water flux 435L/m of film
2H.0.1MPa, burst pressure is greater than 0.55MPa, and film is 89% to the rejection of the bovine serum albumin of relative molecular mass 67000.
Claims (6)
1, a kind of enhancing capillary-pipe film, constitute by capillary braid supporter and film, it is characterized in that, the capillary braid is to be formed by fibrage, and the internal diameter of capillary braid is 0.5-3.0mm, external diameter 1.0-5.0mm, dense side mesh aperture 5-100 micron, the density of capillary braid changes in gradient, and density reduces from the inside to surface, and the ratio that density gradient changes is 1.5-10; The inside that coating coating liquid and making it is penetrated into the capillary braid on the capillary braid forms and strengthens capillary-pipe film, and the degree of depth that wherein enters is the 10-80% of capillary braid supporter thickness, and the thickness that strengthens capillary-pipe film is 0.1-1.0mm.
2, enhancing capillary-pipe film according to claim 1, it is characterized in that, described coating liquid is mixed by following ratio of weight and number by polymer, additive, solvent and pore-foaming agent and forms: 5～35 parts in polymer, additive 0-35 part, 30～80 parts of solvents, 1～40 part of pore-foaming agent.
3, enhancing capillary-pipe film according to claim 2 is characterized in that,
Described polymer is at least a in polysulfones, polyvinyl chloride, chliorinated polyvinyl chloride, Kynoar, SPSF, polyether-ketone, the polyacrylonitrile;
Described additive is an inorganic particle, be zirconia, aluminium oxide, iron oxide, molecular sieve, graphite powder or CNT, or organic granular, be powder ion exchange resin, macroporous absorbent resin, the granularity 0.05-50 micron of described inorganic particle or organic granular;
Described solvent is at least a in N-methyl pyrrolidone, dimethylacetylamide, dimethyl formamide, dimethyl sulfoxide (DMSO) or the oxolane;
Described pore-foaming agent adopts in SPSF, partial hydrolysis polyvinyl acetate, surfactant, unit alcohol, polyalcohol, the polyalcohol condensation polymer at least a.
4, enhancing capillary-pipe film according to claim 3 is characterized in that, described surfactant is polyethylene glycol or PVP.
5, enhancing capillary-pipe film according to claim 1 is characterized in that, described fiber is a kind of in composite filament, monofilament, the short fiber, described composite filament, and its quantity is the 30-200 root, the fiber number of composite filament is 400-1200dtx;
A kind of as in polyester, nylon, polyamide fibre, Wei Lun, cotton fiber, cellulose, glass fibre, carbon fiber or the metallic fiber of the material that described fiber uses.
6, the preparation method of the described enhancing capillary-pipe film of a kind of claim 1 is characterized in that comprising the steps:
(1) making of gradient capillary shape braid: adopt the compound braider of 4-32 head to weave capillary with density gradient, the ratio that density gradient changes is 1.5-10, the internal diameter of capillary braid is 0.5-3.0mm, external diameter 1.0-5.0mm, braid mesh aperture 5-100 micron;
(2) preparation of coating liquid: polymer, additive, solvent and pore-foaming agent are mixed by following ratio of weight and number: 5～35 parts in polymer, additive 0-35 part, 30～80 parts of solvents, 1～40 part of pore-foaming agent; Mixture was stirred 4～12 hours down at 20～80 ℃, and standing and defoaming made the coating liquid that mixes after 24～48 hours under the normal temperature;
(3) film: under 20～80 ℃, the coating liquid that makes is applied one deck preparation liquid at capillary braid outer surface,, be placed on the solidification forming in the bath water that solidifies of 20～90 ℃ of temperature, make the enhancing capillary-pipe film through behind 0.5-100 centimetre the air section; The thickness of described enhancing capillary-pipe film is 0.1-1.0mm;
(4) post processing: soak into the enhancing capillary-pipe film 8～48 hours of gained with the glycerine water solution of 5～50wt%, make and strengthen the capillary-pipe film finished product.
Strengthen capillary-pipe film and preparation method thereof
[technical field] the invention belongs to the membrane separation technique field, particularly a kind of enhancing capillary-pipe film that is used as miillpore filter or milipore filter and preparation method thereof.Be applicable to water purification and wastewater treatment and reuse.
[background technology] membrane separation technique is a kind of separation of material in liquid or the gas medium, isolation technics that concentrates and purify of being widely used in.Be used for the extremely trickle micropore that gathers on the membranous wall of fluid separation applications, during the side by film, solvent and low molecule solute see through membranous wall to be become through liquid stoste under pressure, and big molecule solute tunicle is held back, thereby reaches the purpose of feed separation or purifying.Membrane technology is a kind of advanced person's a isolation technics, and many advantages are arranged.For example separation accuracy height, selectivity are strong, at normal temperatures the no phase-state change of operation, energy consumption is low, automaticity is high, pollution is little etc.
Doughnut is a kind of important form of diffusion barrier.Compare with other form membrane modules, filling film area doughnut is maximum in the unit volume.Characteristics such as hollow-fibre membrane has the separative efficiency height, cleans easily, simple in structure, easy to operate, cost performance height, thereby be widely used.
When particularly being applied to membrane bioreactor, owing to the vigorous stirring effect of gas, there is the problem of bad mechanical strength in present commercial hollow-fibre membrane in water treatment and waste water treatment applications process, the phenomenon of rupture of film generation in use often takes place.Hollow-fibre membrane during this require to use not only has high permeance property, good stalling characteristic, and will have than higher in the past mechanical performance.
Canada Zenon environment Co., Ltd proposes in United States Patent (USP) (5472607): coat polyvinylidene fluoride film in the hollow textile surface, but under the environment of high-intensity oscillation, exist the problem that perforated membrane easily peels off from textile surface.Can not adopt the cleaning method of high strength backwash, the cleaning of film and recovery effects are restricted.
Mitsubishi Li Yang Co., Ltd. proposes in the disclosed patent of China (number of patent application 200380102726.6): imbed fortifying fibre in the Kynoar porous plastid, this scheme might cause the flux of film to reduce, and causes the porous body to break easily under violent tensile force effect.
Mitsubishi Li Yang Co., Ltd. proposes in disclosed another patent of China (number of patent application 200380102726.6): in order to improve the stripper-resistance of film, adopt the scheme of duplicature, but there is the process complexity in this scheme, is difficult to control.In addition, can not adopt the cleaning method of big flow, high strength backwash, fail from the caducous problem of basic solution film.
Yiming Filtering Technology Co., Ltd., Shanghai has proposed a kind of enhancement mode hollow fiber ultrafiltration membrane and preparation method thereof in its disclosed patent (number of patent application 200510024195.4).The concrete property that does not relate to braid in its application for patent, the aperture of film is confined to the milipore filter scope, fails anti-burst aspect performance indications to the characterization of membrane such as burst pressure of membrane, is difficult to judge whether solved present already present problem.
[summary of the invention] the objective of the invention is to solve the prior art above shortcomings, and a kind of enhancing capillary-pipe film and preparation method thereof is provided.
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| KR101589746B1 (en) * | 2009-04-13 | 2016-01-28 | 코오롱인더스트리 주식회사 | Hollow fiber membrane and method for manufacturing the same |
| WO2011004786A1 (en) * | 2009-07-06 | 2011-01-13 | 積水化学工業株式会社 | Polymer membrane for water treatment |
| CN102762285B (en) * | 2009-08-03 | 2016-06-08 | 索尔维特殊聚合物意大利有限公司 | For the method preparing ethylene/CTFE thin polymer film |
| KR20120059755A (en) * | 2010-12-01 | 2012-06-11 | 엘지전자 주식회사 | Method for manufacturing a hollow fiber membrane for water treatment using cellulose resin |
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2007
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