CN1552960A - Preparing method and apparatus for hollow fibrous membrane - Google Patents

Preparing method and apparatus for hollow fibrous membrane Download PDF

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Publication number
CN1552960A
CN1552960A CNA031299881A CN03129988A CN1552960A CN 1552960 A CN1552960 A CN 1552960A CN A031299881 A CNA031299881 A CN A031299881A CN 03129988 A CN03129988 A CN 03129988A CN 1552960 A CN1552960 A CN 1552960A
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China
Prior art keywords
hollow
fibre membrane
ultrasonic
glycerine
water
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CNA031299881A
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Chinese (zh)
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吕晓龙
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MOTIANMO ENGINEERING TECHNOLOGY Co Ltd TIANJIN
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MOTIANMO ENGINEERING TECHNOLOGY Co Ltd TIANJIN
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Priority to CNA031299881A priority Critical patent/CN1552960A/en
Publication of CN1552960A publication Critical patent/CN1552960A/en
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Abstract

Tubular fiber films are produced by: a) spinning and film making; b) solidifying films in a solidifying bath to form primary tubular films; c) passing them through a supersonic cleansing bath to remove solvent and additives and to solidify completely, and d) winding up. The apparatus includes the said baths and a winder.

Description

The preparation method of hollow-fibre membrane and preparation equipment
Technical field
The present invention relates to a kind of preparation method of hollow-fibre membrane, and a kind of preparation equipment of hollow-fibre membrane.This method is applicable to wet method or does-spinning of wet method hollow-fibre membrane and fusion method spinning.
Background technology
Fig. 1 has shown that a kind of of hollow-fibre membrane of the prior art does-the wet spinning preparation method, feed liquid is injected in the spinning nozzle from spinning solution still and spinning core flow container simultaneously, through the spinning nozzle spinning membrane system, the film that makes is cured processing through coagulating tank 1, obtain hollow-fibre membrane 3, hollow-fibre membrane is transmitted to spiral filament forming machine 4 places in the wrapping wire groove 2, the coiled volume.
In the preparation method of above-mentioned hollow-fibre membrane, the film that makes is through behind the coagulating tank 1, what obtain is the hollow-fibre membrane of coming into being, in order to remove residual solvent and additive in the nascent hollow-fibre membrane, need continuous multi-stage elution groove or hollow-fibre membrane is immersed in the elution liquid for a long time, production efficiency is low.
And the processing to film is interrupted in the prior art, be through disjunct technological process each other.Spin out hollow-fibre membrane according to said method, then hollow fiber membrane bundle be immersed in the solution of specific composition again and carry out after-treatment, as be immersed in the water or acid solution, alkali lye in, to remove the additive in the nascent hollow-fibre membrane; If hollow-fibre membrane will further carry out the membrane module shaping casting, then also need be immersed in glycerine, the surfactant etc. and handle.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of disposable shaping hollow-fibre membrane, can rapidly and efficiently, fully remove residual solvent and additive in the nascent hollow-fibre membrane in the method, and can produce hollow-fibre membrane continuously, thereby improve production efficiency and production stability.This method can be used for preparing counter-infiltration (RO) hollow-fibre membrane, nanofiltration (NF) hollow-fibre membrane, micro-filtration (MF) hollow-fibre membrane and ultrafiltration (UF) hollow-fibre membrane etc.
The step that the preparation method of disposable shaping hollow-fibre membrane provided by the invention is main comprises:
A. spinning membrane system;
B. the film that makes in the spinning of coagulating bath in-tank-solidification generates nascent hollow-fibre membrane;
C. nascent hollow-fibre membrane is further removed wherein solvent and additive, thereby is solidified hollow-fibre membrane fully through ultrasonic cleaner;
D. wrapping wire rolling;
Like this with regard to the disposable hollow-fibre membrane that has been shaped.
Wherein hollow-fibre membrane can also pass through the ultrasonic Treatment groove through behind the ultrasonic cleaner, handles hollow-fibre membrane with glycerine and/or aqueous surfactant solution in the ultrasonic Treatment groove.
The present invention also provides a kind of preparation equipment of disposable shaping hollow-fibre membrane, comprising:
A. coagulating tank;
B. ultrasonic cleaner;
C. wrapping wire groove.
Wherein behind ultrasonic cleaner, before the wrapping wire groove, can further include the ultrasonic Treatment groove.
The invention effect:
1, used ultrasonic cleaner in the method for the present invention, wherein improved hollow-fibre membrane elution effect by increasing ultrasonic unit, make hollow-fibre membrane fast, film-forming fully, stable and reliable product quality, and the quality of production is controlled easily;
2, can also use the ultrasonic Treatment groove in the method for the present invention, in the hollow-fibre membrane that has been shaped, strengthen immerse glycerine, surfactant, be interrupted to soak with routine and compare, can be fast in the ultrasonic Treatment groove, soak equably, soak reliable for effect.
So the method according to this invention can rapidly and efficiently, fully remove residual solvent and additive in the nascent hollow-fibre membrane, and can produce hollow-fibre membrane continuously, thereby improve production efficiency and production stability.
Description of drawings
Fig. 1 is the flow chart of dry-wet spinning system hollow-fibre membrane commonly used in the prior art;
Fig. 2 is the preparation method's of once-forming hollow-fibre membrane of the present invention flow chart;
Fig. 3 is the preparation method's of the illustrated once-forming hollow-fibre membrane of embodiment 1 a flow chart;
Fig. 4 is the preparation method's of the illustrated once-forming hollow-fibre membrane of embodiment 2 a flow chart;
Fig. 5 is the preparation method's of the illustrated fusion method once-forming hollow-fibre membrane of embodiment 3 a flow chart.
The specific embodiment
Fig. 2 is the preparation method's of once-forming hollow-fibre membrane of the present invention flow chart.
Method technological process of the present invention can be summarized as: spinning solution jar+spinning core flow container coagulating tank 1 ultrasonic cleaner 5 ultrasonic Treatment grooves 6 spiral filament forming machines.
Acting as of above-mentioned each parts:
Coagulating tank: the film that spins out is carried out preliminary cure, form nascent hollow-fibre membrane;
Ultrasonic cleaner: nascent hollow-fibre membrane is carried out complete cured, and solvent and the additive in the hollow-fibre membrane removed in elution, wherein improves hollow-fibre membrane elution effect by increasing ultrasonic unit; Ultrasonic unit is made up of ultrasonic oscillator, and ultrasonic oscillator is evenly distributed on the both sides or the one-sided or bottom of ultrasonic wave cleaning sink;
In order to improve cleaning performance and to cut down the consumption of energy, the ultrasonic wave tank is preferably wide to be 10-200mm, and the degree of depth is 20-200mm, according to ultrasonic oscillator power and the number selected for use, and actual cleaning performance, ultrasonic wave tank length is 500-4000mm.
In spinning process, in order to improve cleaning performance, can constantly in the ultrasonic wave cleaning sink, mend Xin Shui, new water is being injected in the ultrasonic wave cleaning sink near hollow-fibre membrane effluent trough place, going into the tank place, keep the liquid level of ultrasonic wave cleaning sink by overflow discharge mode near hollow-fibre membrane.
Through coagulating tank and ultrasonic cleaner, hollow-fibre membrane has removed solvent and additive, is solidified fully, like this with regard to the disposable hollow-fibre membrane that has been shaped.If hollow-fibre membrane will further carry out the membrane module shaping casting, then hollow-fibre membrane also needs to be immersed in glycerine, the surfactant etc. and to handle through the ultrasonic Treatment groove.
Ultrasonic Treatment groove: use the aqueous solution of glycerine, surfactant or its mixing etc., hollow-fibre membrane is handled, wherein improve treatment effect by increasing ultrasonic unit; Ultrasonic unit is made up of ultrasonic oscillator, and ultrasonic oscillator is evenly distributed on the both sides or the one-sided or bottom of ultrasonic Treatment groove.
To soak effect and cut down the consumption of energy in order to improve, the ultrasonic Treatment groove is preferably wide to be 10-200mm, and the degree of depth is 20-200mm, according to ultrasonic oscillator power and the number selected for use, and the actual effect of soaking, ultrasonic wave tank length is 500-4000mm.
In spinning process, in order to improve treatment effect, can constantly in the ultrasonic Treatment groove, mend the glycerine and/or the aqueous surfactant solution of new predetermined concentration, new solution is being gone into the groove place keeps the ultrasonic Treatment groove by overflow discharge mode liquid level go out the injection of groove place near hollow-fibre membrane near hollow-fibre membrane.Glycerine and/or the surfactant solution that flows out recycled.
Spinning solution is the solution of polymer of preparation hollow-fibre membrane in the prior art, can be selected from Kynoar (PVDF), polysulfones (PS), polyacrylonitrile (PAN), polyether sulfone (PES), their polymer-modified, their copolymer or two or more the solution of mixture of above various polymer.
Spinning core liquid is the spinning core liquid that is used to prepare hollow-fibre membrane in the prior art, as water, compressed air, kerosene etc.
Liquid in coagulating tank and the ultrasonic cleaner according to the different elution requirements of spinning technique, can be water, acid solution, aqueous slkali, organic solvent etc. for the liquid that solidifies the spinning thing commonly used.
Be generally glycerine and/or aqueous surfactant solution in the ultrasonic Treatment groove, surfactant can be ion-type or nonionic surface active agent commonly used.
According to the different requirements of spinning technique, wherein the temperature of ultrasonic cleaner is 2~150 ℃, and the time of staying of hollow-fibre membrane in ultrasonic cleaner is 1~120 second; The concentration of glycerine can be 20~80wt% in the ultrasonic Treatment groove, and surfactant concentrations can be 0.01~10wt%, and the temperature of ultrasonic Treatment groove is 2~150 ℃, and the hollow-fibre membrane time of staying therein is 1~120 second.
Following examples are to further specify of the present invention, and it does not limit protection scope of the present invention.
Embodiment 1:
As shown in Figure 3, spinning solution is PVDF solution (Solef PVDF 1015 22wt%, Macrogol 6000 10wt%, dimethylacetylamide 68wt%), in coagulating tank and the ultrasonic cleaner water, time in ultrasonic cleaner is 10 seconds, constantly in the ultrasonic wave cleaning sink, mend Xin Shui, water supplement port is at close hollow-fibre membrane effluent trough place, and water discharge outlet is going into the tank place near hollow-fibre membrane, by the discharge water of overflow mode.Before last spiral filament forming machine, hollow-fibre membrane promptly solidifies fully, and system film additive is wherein washed out fully.After spun hollow-fibre membrane unloads from spiral filament forming machine, be immersed in the 30wt% glycerine water solution, soak after 12 hours, take out drying, be cast into hollow fiber film assembly.
Comparative example 1:
Handle without ultrasonic cleaner, all the other spinning conditions are with embodiment 1, after spun hollow-fibre membrane unloads from spiral filament forming machine, in soaking a groove, soak after 6 hours and change washings, washing by soaking is after 6 hours again, and hollow-fibre membrane is solidified fully, and the system film additive is washed out fully.Be immersed in the 30wt% glycerine water solution, soak after 12 hours, take out drying, be cast into hollow fiber film assembly.
Embodiment 2:
As shown in Figure 4, spinning solution is PVDF solution (Solef PVDF 1015 22wt%, Macrogol 6000 10wt%, dimethylacetylamide 68wt%), in coagulating tank and the ultrasonic cleaner water, constantly in the ultrasonic wave cleaning sink, mend Xin Shui, water supplement port is at close hollow-fibre membrane effluent trough place, water discharge outlet is going into the tank place near hollow-fibre membrane, by the discharge water of overflow mode; Hollow-fibre membrane enters ultrasonic wave glycerine treatment trough more then, time in the ultrasonic Treatment groove is 15 seconds, constantly in ultrasonic wave glycerine treatment trough, mend new glycerine water solution, mend inlet and going out the groove place near hollow-fibre membrane, outlet is being gone into the groove place near hollow-fibre membrane, discharge glycerine water solution by the overflow mode, collect the glycerine water solution of discharging, reclaim and use again; Before last wire wrapping wheel, hollow-fibre membrane is solidified fully, system film additive is wherein washed out fully, and disposed with glycerine, hollow-fibre membrane after downcutting on the wire wrapping wheel, can be dried or dry, deliver to next step casting operation and carry out the membrane module casting.
Embodiment 3
As shown in Figure 5, with spinning constituent (Solef PVDF 1015 56wt%, α-Al 2O 32~5 μ m granularity 44wt%), with twin-screw extruding spinning machine at 280 ℃ of following extruding spinnings, go into ultrasonic wave rinse bath (constituent is the 10wt% sodium hydrate aqueous solution) through the air setting groove is laggard, time in ultrasonic cleaner is 10 seconds, constantly in the ultrasonic wave cleaning sink, mend new 10wt% sodium hydrate aqueous solution, water supplement port is at close hollow-fibre membrane effluent trough place, and water discharge outlet is going into the tank place near hollow-fibre membrane, by the discharge water of overflow mode; Hollow-fibre membrane enters ultrasonic wave glycerine treatment trough more then, time in the ultrasonic Treatment groove is 25 seconds, constantly in ultrasonic wave glycerine treatment trough, mend new (40wt% glycerine+1wt% soil temperature 20) aqueous solution, mend inlet and going out the groove place near hollow-fibre membrane, outlet is being gone into the groove place near hollow-fibre membrane, discharge glycerine water solution by the overflow mode, collect the glycerine water solution of discharging, reclaim and use again; Before last wire wrapping wheel, the system film additive in the hollow-fibre membrane is washed out fully, and dispose with glycerine, hollow-fibre membrane after downcutting on the wire wrapping wheel, can be dried or dry, deliver to next step casting operation and carry out the membrane module casting.

Claims (10)

1. the preparation method of a disposable shaping hollow-fibre membrane, its step comprises:
A. spinning membrane system;
B. the film that makes in the spinning of coagulating bath in-tank-solidification generates nascent hollow-fibre membrane;
C. nascent hollow-fibre membrane is further removed wherein solvent and additive, thereby is solidified hollow-fibre membrane fully through ultrasonic cleaner;
D. wrapping wire rolling;
Like this with regard to the disposable hollow-fibre membrane that has been shaped.
2. method according to claim 1 is characterized in that:
Being water, acid solution, aqueous slkali or organic solvent in the ultrasonic cleaner, is air, water, acid solution, aqueous slkali or organic solvent in the coagulating tank.
3. method according to claim 1 is characterized in that;
Hollow-fibre membrane also passes through the ultrasonic Treatment groove through behind the ultrasonic cleaner, handles hollow-fibre membrane with glycerine and/or surfactant in the ultrasonic Treatment groove.
4. the preparation equipment of a disposable shaping hollow-fibre membrane comprises:
A. coagulating tank;
B. ultrasonic cleaner;
C. wrapping wire groove.
5. preparation equipment according to claim 4 is characterized in that:
Coagulating tank is used to solidify the film that spinning makes, and generates nascent hollow-fibre membrane.
6. preparation equipment according to claim 4 is characterized in that:
Ultrasonic cleaner is used for further removing solvent and additive wherein, thereby solidifies hollow-fibre membrane fully.
7. preparation equipment according to claim 4 is characterized in that:
Ultrasonic cleaner has water supplement port and water discharge outlet, and water supplement port is at close hollow-fibre membrane effluent trough place, and water discharge outlet, is used for constantly mending Xin Shui to the ultrasonic wave cleaning sink by the discharge water of overflow mode going into the tank place near hollow-fibre membrane.
8. preparation equipment according to claim 4 is characterized in that:
Behind ultrasonic cleaner, before the wrapping wire groove, comprise the ultrasonic Treatment groove.
9. preparation equipment according to claim 8 is characterized in that:
In the ultrasonic Treatment groove, handle hollow-fibre membrane with glycerine and/or surfactant.
10. equipment according to claim 8 is characterized in that:
The ultrasonic Treatment groove has the inlet of benefit and outlet, mend inlet and going out the groove place near hollow-fibre membrane, outlet is being gone into the groove place near hollow-fibre membrane, discharge glycerine water solution by the overflow mode, collect the glycerine water solution of discharging, reclaim usefulness again, thereby constantly in ultrasonic wave glycerine treatment trough, mend new glycerine water solution.
CNA031299881A 2003-06-05 2003-06-05 Preparing method and apparatus for hollow fibrous membrane Pending CN1552960A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102186565A (en) * 2008-10-15 2011-09-14 新加坡国立大学 Dual-layer hollow fibers with enhanced flux as forward osmosis membranes for water reuses and protein enrichment
CN102877218A (en) * 2012-10-24 2013-01-16 厦门大学 Method for preparing dewatering oil absorption silicon carbide ceramic fiber felt
CN103889561A (en) * 2011-10-20 2014-06-25 甘布罗伦迪亚股份公司 Process for continuously washing a hollow fibre membrane for depleting residuals
CN104128097A (en) * 2014-07-28 2014-11-05 北京新源国能科技有限公司 Supersonic wave technology-based hollow fiber film preparation method
CN104383817A (en) * 2014-11-28 2015-03-04 天津华清健坤膜科技有限公司 High-efficiency hollow fiber membrane production equipment
CN104437103A (en) * 2014-11-28 2015-03-25 天津华清健坤膜科技有限公司 Device with nylon skeleton for highly efficiently producing high quality hollow fiber membrane
CN108816053A (en) * 2018-05-25 2018-11-16 南京佳乐净膜科技有限公司 The preparation facilities and method of polymer film based on ultrasonic wave online processing technology
CN109603588A (en) * 2018-12-21 2019-04-12 吉林金赛科技开发有限公司 A kind of hollow fiber nanofiltration membrane and its preparation process
CN110871036A (en) * 2018-08-30 2020-03-10 中国石油化工股份有限公司 Hollow fiber membrane solidification equipment and method

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102186565A (en) * 2008-10-15 2011-09-14 新加坡国立大学 Dual-layer hollow fibers with enhanced flux as forward osmosis membranes for water reuses and protein enrichment
CN103889561B (en) * 2011-10-20 2015-11-25 甘布罗伦迪亚股份公司 For continuous wash hollow-fibre membrane to remove the method for residue
CN103889561A (en) * 2011-10-20 2014-06-25 甘布罗伦迪亚股份公司 Process for continuously washing a hollow fibre membrane for depleting residuals
CN102877218A (en) * 2012-10-24 2013-01-16 厦门大学 Method for preparing dewatering oil absorption silicon carbide ceramic fiber felt
CN102877218B (en) * 2012-10-24 2016-03-09 厦门大学 A kind of preparation method of hydrophobic oil suction silicon carbide ceramic fiber felt
CN104128097A (en) * 2014-07-28 2014-11-05 北京新源国能科技有限公司 Supersonic wave technology-based hollow fiber film preparation method
CN104437103A (en) * 2014-11-28 2015-03-25 天津华清健坤膜科技有限公司 Device with nylon skeleton for highly efficiently producing high quality hollow fiber membrane
CN104383817A (en) * 2014-11-28 2015-03-04 天津华清健坤膜科技有限公司 High-efficiency hollow fiber membrane production equipment
CN104383817B (en) * 2014-11-28 2017-07-18 天津华清健坤膜科技有限公司 A kind of high-efficiency hollow fiber membrane production equipment
CN108816053A (en) * 2018-05-25 2018-11-16 南京佳乐净膜科技有限公司 The preparation facilities and method of polymer film based on ultrasonic wave online processing technology
CN110871036A (en) * 2018-08-30 2020-03-10 中国石油化工股份有限公司 Hollow fiber membrane solidification equipment and method
CN110871036B (en) * 2018-08-30 2022-10-21 中国石油化工股份有限公司 Hollow fiber membrane solidification equipment and method
CN109603588A (en) * 2018-12-21 2019-04-12 吉林金赛科技开发有限公司 A kind of hollow fiber nanofiltration membrane and its preparation process

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