CN103585892B - Method for preparing enhanced hollow fiber membrane employing low-temperature thermal induced phase method, product, and application and equipment thereof - Google Patents
Method for preparing enhanced hollow fiber membrane employing low-temperature thermal induced phase method, product, and application and equipment thereof Download PDFInfo
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Abstract
The invention relates to a method for preparing an enhanced hollow fiber membrane employing a low-temperature thermal induced phase method. The method comprises the following steps: mixing and burdening polyvinylidene fluoride, a solvent and an additive at 80-100 DEG C according to the weight ratio of (5-20):(50-80):(1-20); evenly stirring, and defoaming at negative pressure, so as to obtain membrane feed liquid; respectively preparing a gel bath lotion, a hydrophilic modified liquid and a modified cross-linking agent; unwinding and feeding a fiber rope; coating the membrane feed liquid at 50-60 DEG C, and then drying by the gel bath lotion at 25-35 DEG C, bathing by the hydrophilic modified liquid at 45-55 DEG C, and drying again; bathing by the modified cross-linking agent at 55-65 DEG C, and then drying and winding up, so as to obtain the enhanced hollow fiber membrane.
Description
[technical field]
The present invention relates to the preparation method of hollow-fibre membrane, particularly a kind of preparation method of low temperature thermic phase method, also relates to the purposes of products obtained therefrom, and realizes the equipment of the method.
[background technology]
Along with China's rapid development of economy, water resource more and more becomes the restraining factors of economic development, therefore reduces sewage discharge, and the regeneration carrying out water has become a kind of inexorable trend.Traditional sewage treatment process cannot meet new requirement, and new technique-water treatment by membrane arises at the historic moment, and this technique is applied to the regeneration of water purification and sewage more and more.
The conventional membrane material for water treatment has polysulfones, polyacrylonitrile, polyvinyl chloride, polypropylene, Kynoar (PVDF) etc.Wherein Kynoar suitable especially sewage disposal due to the performance of its excellence.Kynoar is a kind of macromolecular material with high chemical stability and weatherability, is not corroded at normal temperatures by acid, alkali, strong oxidizer or halogen, can be exposed to outdoor for a long time and without aging phenomenon.These characteristics of PVDF make it be paid attention to gradually in membrane separation technique and apply.It is high with PVDF to be that the obtained hollow-fibre membrane of raw material has intensity, and anti-adsorption fouling is good, chemically-resistant cleaning and loading density advantages of higher, can be applicable to food industry, Biochemical Engineering, pharmaceuticals industry and water treatment, the sewage disposal that especially service condition is very severe.PVDF rises at the consumption of water treatment field and is exceedingly fast, and the current whole world reaches multi-billion dollar for the manufacture of the PVDF value of doughnut every year.
In sewage disposal, because applied environment is very poor, higher to the requirement of film-strength.The method of usual preparative separation film comprises phase separation method (being called for short " wet method ") and thermally induced phase separation (being called for short " hot method ").
The defect that common hollow-fibre membrane ubiquity intensity is low, applies and easily occurs the situations such as fracture of wire in the Sewage Environment of complexity.And the hollow-fibre membrane of Enhanced Configuration, adopt dry-wet spinning due to the more difficult film silk making uniform pore diameter of restriction of himself forming method, affect filtering accuracy.Adopt heat to phase spinning can ensure certain hole uniformity, but the hydrophily of film silk cannot be ensured.
[summary of the invention]
[technical problem that will solve]
The object of this invention is to provide a kind of preparation method having film silk intensity, hole uniformity and hydrophilic enhancement type hollow fiber film concurrently, combine low temperature thermic phase legal system for hydrophilic fortifying fibre film and dry-wet spinning basis, possesses the advantage of two kinds of forming methods simultaneously, and through hydrophilicity-imparting treatment, thus obtain the film silk of high strength, high fenestra uniformity and high-hydrophilic.
The invention still further relates to the application of enhancement type hollow fiber film in water treatment that said method obtains.
The invention still further relates to the equipment realizing said method.
[technical scheme]
The invention provides the method for a kind of low temperature thermic phase legal system for enhancement type hollow fiber film, the method comprises the steps:
A, at 80-100 DEG C, by polyvinylidene fluoride resin, solvent, additive according to weight ratio 5-20:50-80:1-20 mix, stirs, and negative pressure deaeration, obtains masking feed liquid;
Water or mass concentration are not more than the aqueous solution of the solvent of 50% as gel bath solution by B;
The aqueous solution of the polyvinyl alcohol of mass concentration 0.1-20%, acrylic acid or NVP is made hydrophilic modifying liquid by C;
D using the aqueous solution containing crosslinking agent as modified crosslinking agent; Described crosslinking agent is selected from maleic anhydride, glutaraldehyde, glyoxal, aldehyde, phthalyl chloride, phthalate anhydride, glutaric anhydride, succinic anhydride, phthalic acid, epoxychloropropane, potassium permanganate or Kocide SD;
Cordage is unreeled wire feed by E, speed 2-20 meter per second, by hydrophilic modifying bath of liquid at 45-55 DEG C, dry, then is bathed by modified crosslinking agent at 55-65 DEG C, then at 120-160 DEG C, passes through solvent vapo(u)r, completes the pretreatment to cordage;
F is applied by masking feed liquid at 50-60 DEG C through pretreated cordage, then at 25-35 DEG C, gel bath solution is passed through, dry, hydrophilic modifying bath of liquid is passed through again at 45-55 DEG C, dry again, bathed by modified crosslinking agent at 55-65 DEG C, then dry receipts silk, obtains a kind of enhancement type hollow fiber film again.
In the present invention, preferably, solvent be the mixed solvent of good solvent according to weight ratio 1 ~ 9:1 ~ 10 and poor solvent, described good solvent is selected from dimethylacetylamide, dimethyl formamide and/or 1-METHYLPYRROLIDONE; Described poor solvent is selected from GBL, triethyl phosphate and/or Merlon.
In the present invention, described additive is selected from polyvinylpyrrolidone, polyethylene glycol, hydroxy kind cellulose.
In the present invention, in the aqueous solution of described crosslinking agent, the mass concentration of the aqueous solution of glutaraldehyde, glyoxal, aldehyde or phthalyl chloride is 30-50%, the mass concentration of the aqueous solution of maleic anhydride, phthalate anhydride, glutaric anhydride, succinic anhydride, phthalic acid or epoxychloropropane is 20-30%, and the mass concentration of the aqueous solution of potassium permanganate or Kocide SD is 0.1-2%.
According to one preferred embodiment, described cordage internal diameter is 0.5-1.6 millimeter, and external diameter is 1.0-4.0 millimeter, wall thickness 0.1-1.5 millimeter.
In the present invention, described cordage is selected from PVDF polyvinylidene fluoride rope, PAN cyclization rope or PET dacron fibre rope.
The invention still further relates to the purposes of enhancement type hollow fiber film in water treatment that method described above is produced.
The present invention also provides a kind of enhancement type hollow fiber film low temperature thermic phase method production equipment, and described production is standby to be comprised wire-feed motor 1 and receives silk machine 12, and wire-feed motor 1 comprises one or more groups fiber roller 2, receives silk machine 12 and comprises one or more groups wire drawing wheel 13, described equipment also comprises: pyroreaction still 8 and the high temperature conveying pipeline 9 communicated with the material outlet of pyroreaction still 8, described high temperature conveying pipeline 9 is connected to coating device 10, described equipment also comprises gel groove 11, hydrophilic modifying groove 4 and modified crosslinking groove 6, wherein, hydrophilic modifying groove 4 and modified crosslinking groove 6 is set gradually between wire-feed motor 1 and coating device 10, gel groove 11 is set gradually between coating device 40 and receipts silk machine 12, hydrophilic modifying groove 4 and modified crosslinking groove 6, at gel groove 11, the guide roller for leading to cordage is respectively equipped with in hydrophilic modifying groove 4 and modified crosslinking groove 6, between gel groove 11 and hydrophilic modifying groove 4, forced air drying equipment 5 is respectively equipped with between hydrophilic modifying groove 4 and modified crosslinking groove 6, cordage processor 7 is also provided with between modified crosslinking groove 6 and coating device 10,
After cordage is sent by the fiber roller 2 of wire-feed motor 1, by film in coating device 6, then gel groove 7 is entered, through forced air drying equipment after deriving from gel groove 7, enter hydrophilic modifying groove 8 again, through the second cover forced air drying equipment after deriving from hydrophilic modifying groove 8, then enter modified crosslinking groove 9, after deriving from modified crosslinking groove 9, carry out receipts silk by receipts silk machine 11.
Preferably, described cordage processor 7 is high-temperature solvent steam cabin.
Technical scheme of the present invention will be described in more detail below.
Low temperature thermic phase legal system is for a method for enhancement type hollow fiber film, and the method comprises the steps:
A, at 80-100 DEG C, by polyvinylidene fluoride resin, solvent, additive according to weight ratio 5-20:50-80:1-20 mix, stirs, and negative pressure deaeration, obtains masking feed liquid;
Water or mass concentration are not more than the aqueous solution of the solvent of 50% as gel bath solution by B;
The aqueous solution of the polyvinyl alcohol of mass concentration 0.1-20%, acrylic acid or NVP is made hydrophilic modifying liquid by C;
D using the aqueous solution containing crosslinking agent as modified crosslinking agent; Described crosslinking agent is selected from maleic anhydride, glutaraldehyde, glyoxal, aldehyde, phthalyl chloride, phthalate anhydride, glutaric anhydride, succinic anhydride, phthalic acid, epoxychloropropane, potassium permanganate or Kocide SD;
Cordage is unreeled wire feed by E, speed 2-20 meter per second, by hydrophilic modifying bath of liquid at 45-55 DEG C, dry, then is bathed by modified crosslinking agent at 55-65 DEG C, then at 120-160 DEG C, passes through solvent vapo(u)r, completes the pretreatment to cordage;
F is applied by masking feed liquid at 50-60 DEG C through pretreated cordage, then at 25-35 DEG C, gel bath solution is passed through, dry, hydrophilic modifying bath of liquid is passed through again at 45-55 DEG C, dry again, bathed by modified crosslinking agent at 55-65 DEG C, then dry receipts silk, obtains a kind of enhancement type hollow fiber film again.
In the present invention, particularly in step e and F, the aqueous solution of water or solvent all can as gel bath solution, and the gelation for preparation liquid is shaped.When containing solvent, solvent is the mixed solvent of good solvent according to weight ratio 1 ~ 9:1 ~ 10 and poor solvent, and described good solvent is selected from dimethylacetylamide (DMAC), dimethyl formamide (DMF) and/or 1-METHYLPYRROLIDONE (NMP); Described poor solvent is selected from GBL, triethyl phosphate and/or Merlon.
In the present invention, described additive is selected from polyvinylpyrrolidone, polyethylene glycol, hydroxy kind cellulose.
In the present invention, described cordage should be the material that can be melted by DMAC or dissolve, such as, be selected from PVDF polyvinylidene fluoride rope, PAN cyclization rope or PET dacron fibre rope.
According to one preferred embodiment, described cordage internal diameter is 0.5-1.6 millimeter, and external diameter is 1.0-4.0 millimeter, wall thickness 0.1-1.5 millimeter.The internal diameter of this cordage and external diameter are that use is with the light microscope determining of scale, and light microscope used is the XTT zoom stereomicroscope that tech electric light instrument plant of Beijing produces.
The purposes of enhancement type hollow fiber film in water treatment that the present invention also provides said method to produce.
The present invention also provides the enhancement type hollow fiber film low temperature thermic phase method production equipment of said method, and described production is standby to be comprised wire-feed motor 1 and receives silk machine 12, and wire-feed motor 1 comprises one or more groups fiber roller 2, receives silk machine 12 and comprises one or more groups wire drawing wheel 13, described equipment also comprises: pyroreaction still 8 and the high temperature conveying pipeline 9 communicated with the material outlet of pyroreaction still 8, described high temperature conveying pipeline 9 is connected to coating device 10, described equipment also comprises gel groove 11, hydrophilic modifying groove 4 and modified crosslinking groove 6, wherein, hydrophilic modifying groove 4 and modified crosslinking groove 6 is set gradually between wire-feed motor 1 and coating device 10, gel groove 11 is set gradually between coating device 40 and receipts silk machine 12, hydrophilic modifying groove 4 and modified crosslinking groove 6, at gel groove 11, the guide roller for leading to cordage is respectively equipped with in hydrophilic modifying groove 4 and modified crosslinking groove 6, between gel groove 11 and hydrophilic modifying groove 4, forced air drying equipment 5 is respectively equipped with between hydrophilic modifying groove 4 and modified crosslinking groove 6, cordage processor 7 is also provided with between modified crosslinking groove 6 and coating device 10,
After cordage is sent by the fiber roller 2 of wire-feed motor 1, by film in coating device 6, then gel groove 7 is entered, through forced air drying equipment after deriving from gel groove 7, enter hydrophilic modifying groove 8 again, through the second cover forced air drying equipment after deriving from hydrophilic modifying groove 8, then enter modified crosslinking groove 9, after deriving from modified crosslinking groove 9, carry out receipts silk by receipts silk machine 11.
The present invention has carried out the mensuration of average pore size, intensity, infiltration angle and pure water flux to prepared hollow-fibre membrane.
The average pore size semidry method pore size determination instrument of described hollow-fibre membrane measures.
Described doughnut film strength refers to the fracture strength of single film, is by electronic universal material testing machine, and the mensuration power (unit N) broken needed for single film obtains.
The bond strength of described casting solution and film silk refers to that rete is followed the power of separating needs with woven tube, is measure rete by electronic tension tester to be obtained by with the power (unit N) of separating needs with woven tube.
The infiltration angle contact angle instrument of described hollow-fibre membrane measures.
The pure water flux flux detector of described hollow-fibre membrane is tested under 0.1MPa pressure.
According to the band base material hollow-fibre membrane that said method is produced, average pore size is 0.1 micron, and internal diameter is 0.8 millimeter, and external diameter is 1.8 millimeters.The doughnut film strength using stretching-machine to measure is 400N
The described hollow-fibre membrane measured under 0.l MPa pressure by flux detector is 300L/m at 25 DEG C and the pure water flux under 1 atmospheric pressure
2.h.
The film silk contact angle measured under normal room conditions with contact angle instrument is 40 degree.
[beneficial effect]
Production method of the present invention can solve the problem of low, the easy fracture of wire of ordinary hollow tunica fibrosa intensity, ensure that hydrophily and flux.Test is learnt, film strength, hydrophily and more much higher than prior art with the pure water flux under 1 atmospheric pressure at 25 DEG C.
[accompanying drawing explanation]
Fig. 1 is enhancement type hollow fiber film low temperature thermic phase method production equipment structural representation of the present invention;
Wherein: 1, wire-feed motor; 2, fiber roller; 3, fiber roller; 4, hydrophilic modifying groove; 5, forced air drying equipment; 6, modified crosslinking groove; 7, cordage processor; 8, pyroreaction still; 9, high temperature conveying pipeline; 10, coating device; 11, gel groove; 12, silk machine is received; 13, wire drawing wheel.
[detailed description of the invention]
The present invention can be understood better by following embodiment.
Embodiment 1
At 90 DEG C, by weight by 15 parts of polyvinylidene fluoride resins, 3 parts of PVPs, 5 parts of polyethylene glycol, 37 parts of dimethylacetylamides, 40 parts of GBL 15:3:5:37:40, mix, negative pressure deaeration, obtains masking feed liquid.Make spin gel body lotion with pure water to circulate at gel groove.The polyvinyl alcohol water solution of mass percent 5% is made hydrophilic modifying liquid circulate at hydrophilic modifying groove.The glutaraldehyde water solution of mass percent 2% is circulated as modified crosslinking agent at modified crosslinking groove.
10 volume glass cords are placed cordage to be sent on volume machine, glass fibre external diameter 1.3mm, internal diameter 0.9mm, cordage wall thickness 0.2mm; Heating plate is cuboid, and perforate is 2 row's distributions; Temperature of heating plate 50 DEG C, cordage winder rolling speed 15 ms/min.Wire-feed motor send volume speed 15 ms/min; Film pipe is 10 holes, and 1 row's distribution, aperture is 3mm.Gel groove coagulation bath temperature 30 DEG C, hydrophilic modifying groove temperature is 50 degree, and modified crosslinking groove temperature is 60 degree, and it is 15 ms/min that cutting winder receives silk speed.
Embodiment 2
Similar to Example 1, at 80 DEG C, by weight by 12 parts of polyvinylidene fluoride resins, 25 parts of dimethylacetylamides, 25 parts of GBL, 1 part of hydroxylated cellulose mix, stir, negative pressure deaeration, obtains masking feed liquid.Gel bath solution is water.Hydrophilic modifying liquid is the acrylic acid aqueous solution of mass concentration 0.1%.Modified crosslinking agent is the glyoxal water solution of mass concentration 30%.
Polyvinylidene fluoride rope is unreeled wire feed, speed 5 meter per second, by hydrophilic modifying bath of liquid at 45 DEG C, dry, then bathed by modified crosslinking agent at 65 DEG C, then at 130 DEG C, pass through solvent vapo(u)r, complete the pretreatment to cordage.
Applied by masking feed liquid at 90 DEG C again, then at 30 DEG C, pass through gel bath solution, dry, then by hydrophilic modifying bath of liquid at 50 DEG C, drier, then bathed by modified crosslinking agent at 55 DEG C, then dry receipts silk, the type that is enhanced hollow-fibre membrane.
Embodiment 3
At 100 DEG C, by weight by 10 parts of polyvinylidene fluoride resins, 10 parts of dimethyl formamides, 70 parts of triethyl phosphates, 10 parts of polyethylene glycol mixes, stir, negative pressure deaeration, obtains masking feed liquid.The aqueous solution (solvent is dimethyl formamide and the triethyl phosphate of weight ratio 1:7) of the solvent of gel bath solution mass concentration 30%.Hydrophilic modifying liquid is the polyvinyl alcohol acrylic acid aqueous solution of mass concentration 20%.Modified crosslinking agent is the Kocide SD aqueous solution of mass concentration 0.1%.
Polyvinylidene fluoride rope is unreeled wire feed, speed 5 meter per second, by hydrophilic modifying bath of liquid at 55 DEG C, dry, then bathed by modified crosslinking agent at 55 DEG C, then at 140 DEG C, pass through solvent vapo(u)r, complete the pretreatment to cordage.
Applied by masking feed liquid at 80 DEG C again, then at 25 DEG C, pass through gel bath solution, dry, then by hydrophilic modifying bath of liquid at 45 DEG C, drier, then bathed by modified crosslinking agent at 65 DEG C, then dry receipts silk, the type that is enhanced hollow-fibre membrane.
Embodiment 4
At 90 DEG C, by weight by 20 parts of polyvinylidene fluoride resins, 6 parts of 1-METHYLPYRROLIDONEs, 60 parts of Merlon, 20 parts of polyvinylpyrrolidone mixes, stir, negative pressure deaeration, obtains masking feed liquid.The aqueous solution (solvent is 1-METHYLPYRROLIDONE and the Merlon of weight ratio 1:10) of the solvent of gel bath solution mass concentration 10%.Hydrophilic modifying liquid is the NVP aqueous solution of mass concentration 10%.Modified crosslinking agent is the succinic anhydride aqueous solution of mass concentration 20%.
Polyvinylidene fluoride rope is unreeled wire feed, speed 20 meter per second, by hydrophilic modifying bath of liquid at 50 DEG C, dry, then bathed by modified crosslinking agent at 60 DEG C, then at 150 DEG C, pass through solvent vapo(u)r, complete the pretreatment to cordage.
Applied by masking feed liquid at 55 DEG C again, then at 30 DEG C, pass through gel bath solution, dry, then by hydrophilic modifying bath of liquid at 55 DEG C, drier, then bathed by modified crosslinking agent at 50 DEG C, then dry receipts silk, the type that is enhanced hollow-fibre membrane.
Embodiment 5
At 90 DEG C, by weight by 10 parts of polyvinylidene fluoride resins, 7 parts of 1-METHYLPYRROLIDONEs, 56 parts of triethyl phosphates, 10 parts of hydroxylated cellulose mixes, stir, negative pressure deaeration, obtains masking feed liquid.The aqueous solution (solvent is 1-METHYLPYRROLIDONE and the triethyl phosphate of weight ratio 1:8) of the solvent of gel bath solution mass concentration 48%.Hydrophilic modifying liquid is the polyvinyl alcohol water solution of mass concentration 0.5%.Modified crosslinking agent is the epoxychloropropane aqueous solution of mass concentration 30%.
Polyvinylidene fluoride rope is unreeled wire feed, speed 20 meter per second, by hydrophilic modifying bath of liquid at 50 DEG C, dry, then bathed by modified crosslinking agent at 60 DEG C, then at 160 DEG C, pass through solvent vapo(u)r, complete the pretreatment to cordage.
Applied by masking feed liquid at 85 DEG C again, then at 30 DEG C, pass through gel bath solution, dry, then by hydrophilic modifying bath of liquid at 55 DEG C, drier, then bathed by modified crosslinking agent at 50 DEG C, then dry receipts silk, the type that is enhanced hollow-fibre membrane.
Embodiment 6
At 85 DEG C, by weight by 17 parts of polyvinylidene fluoride resins, 30 parts of 1-METHYLPYRROLIDONEs, 30 parts of triethyl phosphates, 2 parts of polyvinylpyrrolidone mixes, stir, negative pressure deaeration, obtains masking feed liquid.The aqueous solution (solvent is 1-METHYLPYRROLIDONE and the triethyl phosphate of weight ratio 1:1) of the solvent of gel bath solution mass concentration 5%.Hydrophilic modifying liquid is the polyvinyl alcohol water solution of mass concentration 0.5%.Modified crosslinking agent is the epoxychloropropane aqueous solution of mass concentration 30%.
Polyvinylidene fluoride rope is unreeled wire feed, speed 10 meter per second, by hydrophilic modifying bath of liquid at 50 DEG C, dry, then bathed by modified crosslinking agent at 60 DEG C, then at 160 DEG C, pass through solvent vapo(u)r, complete the pretreatment to cordage.
Applied by masking feed liquid at 55 DEG C again, then at 30 DEG C, pass through gel bath solution, dry, then by hydrophilic modifying bath of liquid at 55 DEG C, drier, then bathed by modified crosslinking agent at 50 DEG C, then dry receipts silk, the type that is enhanced hollow-fibre membrane.
Embodiment 7(reference examples, does not carry out pretreatment to cordage)
At 90 DEG C, by weight by 10 parts of polyvinylidene fluoride resins, 7 parts of 1-METHYLPYRROLIDONEs, 56 parts of triethyl phosphates, 10 parts of hydroxylated cellulose mixes, stir, negative pressure deaeration, obtains masking feed liquid.The aqueous solution (solvent is 1-METHYLPYRROLIDONE and the triethyl phosphate of weight ratio 1:8) of the solvent of gel bath solution mass concentration 48%.Hydrophilic modifying liquid is the polyvinyl alcohol water solution of mass concentration 0.5%.Modified crosslinking agent is the epoxychloropropane aqueous solution of mass concentration 30%.
Polyvinylidene fluoride rope is unreeled wire feed, speed 20 meter per second, applied by masking feed liquid at 55 DEG C, then at 30 DEG C, gel bath solution is passed through, dry, then by hydrophilic modifying bath of liquid at 55 DEG C, dry again, bathed by modified crosslinking agent at 50 DEG C again, then dry receipts silk, the type that is enhanced hollow-fibre membrane.
Embodiment 8(reference examples, does not carry out pretreatment to cordage, does not carry out modification)
At 90 DEG C, by weight by 10 parts of polyvinylidene fluoride resins, 7 parts of 1-METHYLPYRROLIDONEs, 56 parts of triethyl phosphates, 10 parts of hydroxylated cellulose mixes, stir, negative pressure deaeration, obtains masking feed liquid.The aqueous solution (solvent is 1-METHYLPYRROLIDONE and the triethyl phosphate of weight ratio 1:8) of the solvent of gel bath solution mass concentration 48%.Hydrophilic modifying liquid is the polyvinyl alcohol water solution of mass concentration 0.5%.Modified crosslinking agent is the epoxychloropropane aqueous solution of mass concentration 30%.
Polyvinylidene fluoride rope is unreeled wire feed, and speed 20 meter per second, is applied by masking feed liquid at 55 DEG C, then at 30 DEG C, passes through gel bath solution, dry, receives silk, the type that is enhanced hollow-fibre membrane.
Above embodiment 1-8 is measured.
Wherein, the detection mode of the bond strength of casting solution and film silk is cut open by film silk, tests with electronic tension tester, and clamp rete with a clip of testing machine, woven tube clamped by another clip, and required power broken in record.
Claims (9)
1. low temperature thermic phase legal system is for a method for enhancement type hollow fiber film, it is characterized in that the method comprises the steps:
A, at 80-100 DEG C, by polyvinylidene fluoride resin, solvent, additive according to weight ratio 5-20:50-80:1-20 mix, stirs, and negative pressure deaeration, obtains masking feed liquid;
Water or mass concentration are not more than the aqueous solution of the solvent of 50% as gel bath solution by B;
The aqueous solution of the polyvinyl alcohol of mass concentration 0.1-20%, acrylic acid or NVP is made hydrophilic modifying liquid by C;
D using the aqueous solution containing crosslinking agent as modified crosslinking agent; Described crosslinking agent is selected from maleic anhydride, glutaraldehyde, glyoxal, phthalyl chloride, phthalate anhydride, glutaric anhydride, succinic anhydride, phthalic acid, epoxychloropropane, potassium permanganate or Kocide SD;
Cordage is unreeled wire feed by E, speed 2-20 meter per second, by hydrophilic modifying bath of liquid at 45-55 DEG C, dry, then is bathed by modified crosslinking agent at 55-65 DEG C, then at 120-160 DEG C, passes through solvent vapo(u)r, completes the pretreatment to cordage;
F is applied by masking feed liquid at 50-100 DEG C through pretreated cordage, then at 25-35 DEG C, gel bath solution is passed through, dry, hydrophilic modifying bath of liquid is passed through again at 45-55 DEG C, dry again, bathed by modified crosslinking agent at 55-65 DEG C, then dry receipts silk, obtains a kind of enhancement type hollow fiber film again.
2. method according to claim 1, it is characterized in that described solvent is the mixed solvent of good solvent according to weight ratio 1 ~ 9:1 ~ 10 and poor solvent, described good solvent is selected from dimethylacetylamide, dimethyl formamide and/or 1-METHYLPYRROLIDONE; Described poor solvent is selected from GBL, triethyl phosphate and/or Merlon.
3. method according to claim 1, is characterized in that described additive is selected from polyvinylpyrrolidone, polyethylene glycol, hydroxy kind cellulose.
4. method according to claim 1, it is characterized in that in the aqueous solution of described crosslinking agent, the mass concentration of the aqueous solution of glutaraldehyde, glyoxal or phthalyl chloride is 30-50%, the mass concentration of the aqueous solution of maleic anhydride, phthalate anhydride, glutaric anhydride, succinic anhydride, phthalic acid or epoxychloropropane is 20-30%, and the mass concentration of the aqueous solution of potassium permanganate or Kocide SD is 0.1-2%.
5. method according to claim 1, it is characterized in that described cordage internal diameter is 0.5-1.6 millimeter, external diameter is 1.0-4.0 millimeter, wall thickness 0.1-1.5 millimeter.
6. method according to claim 1, is characterized in that described cordage is selected from polyvinylidene fluoride rope, cyclization rope or dacron fibre rope.
7. the purposes of enhancement type hollow fiber film in water treatment that method described in claim is produced any one of claim 1-6.
8. the enhancement type hollow fiber film low temperature thermic phase method production equipment of method described in claim any one of claim 1-6, described production equipment comprises wire-feed motor (1) and receives silk machine (12), wire-feed motor (1) comprises one or more groups fiber roller (2), receive silk machine (12) and comprise one or more groups wire drawing wheel (13), it is characterized in that described equipment also comprises: pyroreaction still (8) and the high temperature conveying pipeline (9) communicated with the material outlet of pyroreaction still (8), described high temperature conveying pipeline (9) is connected to coating device (10), described equipment also comprises gel groove (11), hydrophilic modifying groove (4) and modified crosslinking groove (6), wherein, hydrophilic modifying groove (4) and modified crosslinking groove (6) is set gradually between wire-feed motor (1) and coating device (10), gel groove (11) is set gradually between coating device (10) and receipts silk machine (12), hydrophilic modifying groove (4) and modified crosslinking groove (6), in gel groove (11), the guide roller for leading to cordage is respectively equipped with in hydrophilic modifying groove (4) and modified crosslinking groove (6), between gel groove (11) and hydrophilic modifying groove (4), forced air drying equipment (5) is respectively equipped with between hydrophilic modifying groove (4) and modified crosslinking groove (6), cordage processor (7) is also provided with between modified crosslinking groove (6) and coating device (10),
After cordage is sent by the fiber roller (2) of wire-feed motor (1), by film in coating device (10), then gel groove (7) is entered, through forced air drying equipment after deriving from gel groove (7), enter hydrophilic modifying groove (8) again, through the second cover forced air drying equipment after deriving from hydrophilic modifying groove (8), enter modified crosslinking groove (9) again, after modified crosslinking groove (9) is derived, carry out receipts silk by receipts silk machine (11).
9. production equipment according to claim 8, described cordage processor (7) is high-temperature solvent steam cabin.
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| CN103585892A (en) | 2014-02-19 |
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