CN103638833B - A kind of preparation method of the large flux hollow fiber membranes for drink water purifying - Google Patents
A kind of preparation method of the large flux hollow fiber membranes for drink water purifying Download PDFInfo
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- CN103638833B CN103638833B CN201310713103.8A CN201310713103A CN103638833B CN 103638833 B CN103638833 B CN 103638833B CN 201310713103 A CN201310713103 A CN 201310713103A CN 103638833 B CN103638833 B CN 103638833B
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- hollow fiber
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- 239000012528 membrane Substances 0.000 title claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 27
- 230000004907 flux Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 31
- 239000000835 fiber Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 238000000605 extraction Methods 0.000 claims abstract description 17
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 15
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 15
- 239000003085 diluting agent Substances 0.000 claims abstract description 13
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims abstract description 10
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000009987 spinning Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 8
- 239000012498 ultrapure water Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 5
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 8
- 238000005096 rolling process Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000002386 leaching Methods 0.000 claims description 5
- 230000000873 masking effect Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000003651 drinking water Substances 0.000 abstract description 9
- 235000020188 drinking water Nutrition 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 2
- 230000006750 UV protection Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000004224 protection Effects 0.000 abstract description 2
- 230000005855 radiation Effects 0.000 abstract description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 9
- 239000002033 PVDF binder Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 4
- 238000011109 contamination Methods 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- -1 Kynoar Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 239000002384 drinking water standard Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000002145 thermally induced phase separation Methods 0.000 description 1
- 229940126680 traditional chinese medicines Drugs 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Abstract
The present invention relates to a kind of preparation method of the large flux hollow fiber membranes for drink water purifying, belong to UF membrane and technical field of drinking water treatment.Polysulfones and Kynoar are dried, by Kynoar, polysulfones, PEG400, N, carry out after N-dimethylacetylamide and polyvinyl alcohol weigh in proportion stirring, dissolving, after feeding double screw extruder is extruded, through filter and spinning pump, extrude from spinning-drawing machine annular die, form the as-spun fibre of hollow, put it into cooling curing in cold extraction liquid bath, then immerse in ultra-pure water, remove diluent mixture, dry and obtain large flux hollow fiber membranes.This method uses materials safety health, and environmental protection, has higher heat resistance and chemical stability, outstanding weatherability, resistance to ozone, ultraviolet resistance radiation and chemical resistance, is the membrane material high-end used for purifying drinking water of function admirable.
Description
Technical field
The present invention relates to a kind of preparation method of the large flux hollow fiber membranes for drink water purifying, particularly relate to a kind of thermally induced phase separation (being called for short hot method) to prepare blended large logical of polysulfones (PSF) and Kynoar (PVDF) and manage hollow-fibre membrane, for drink water purifying, belong to UF membrane and technical field of drinking water treatment.
Background technology
The existing water source of China is generally subject to organic pollution, and the combined pollutions such as high organic matter, high concentrtion appear in some areas.Traditional coagulation-precipitation-filtration-sterilization process filtering accuracy is low, disinfectant and coagulant use amount high, large to water quality impact, the water after process can not meet the requirement of new national standard 106 drinking water standards.Membrane separation technique carries out drinking water deep purification now, ensures the important new technology of water quality safety.Be that the water treatment technology of core has developed into third generation drinking water purification process with milipore filter, the group technology of it and other technology, can process micro polluted source, the drinking water of production high-quality effectively.
Traditional non-solvent phase method (abbreviation wet method) produce hollow-fibre membrane, intensity is low, toughness is poor, easy fracture of wire in using, life-span be short, be unsuitable for applying in large-scale drinking water treatment engineering.The hollow fiber ultrafiltration membrane of the large flux of municipal drinking water process, high strength, antipollution, low cost is suitable in the urgent need to exploitation.
Summary of the invention
The object of the invention is the preparation method proposing a kind of large flux hollow fiber membranes for drink water purifying, prepare the hollow-fibre membrane of large flux, and make it have stronger contamination resistance, have higher cost performance, for drink water purifying provides product guarantee.
The preparation method of the large flux hollow fiber membranes for drink water purifying that the present invention proposes, comprises the following steps:
(1) polysulfones and Kynoar are carried out drying respectively in dryer, the temperature of oven dry 80 ~ 90 DEG C, drying time is 24 ~ 36 hours;
(2) for the preparation of the blended polymer solution of masking:
In blended polymer solution, the mass percent of each component is:
By Kynoar, polysulfones, PEG400, N, after N-dimethylacetylamide and polyvinyl alcohol weigh according to the above ratio, be placed in stirred tank, carry out stirring, dissolving at the temperature of 100 ~ 110 DEG C, mixing time is 14 ~ 16 hours, speed of agitator 90 ~ 110 revs/min, makes uniform blended polymer solution;
(3) the extruding and be shaped of hollow-fibre membrane, detailed process is as follows:
(3-1) the blended polymer solution of step (2) is sent in double screw extruder by spinning pump, the charging rate of raw material is 15 ~ 20Kg/ hour, the temperature of extruder 6 sections all sets unanimously, it is 100 ~ 110 DEG C, extrusion temperature is 100 ~ 110 DEG C, and screw speed is 90 ~ 120 revs/min;
(3-2) blended polymer solution is after double screw extruder is extruded, successively through filter and spinning pump, extrude from spinning-drawing machine annular die, form the as-spun fibre of hollow, the external diameter of described annular die is 5 millimeters, internal diameter is 4.2 millimeters, and annular die center passes into air, and the pressure of air is 20 ~ 30 millimeter of water (mmH
2o);
(3-3) above-mentioned hollow as-spun fibre is lower the temperature in the air of 20 ~ 25 DEG C in temperature, the distance that sky is walked is 2 ~ 5 centimetres, then enter in cold extraction liquid bath through cold extraction liquid cooling curing, through winder rolling, make hollow-fibre membrane intermediate, the rolling speed of winder 20 ~ 30 ms/min, described cold extraction liquid is water, and the temperature of cold extraction liquid is 50 ~ 70 DEG C;
(4) immersed in ultra-pure water by the hollow-fibre membrane intermediate in step (3), remove the mixture of the first diluent and the second diluent in film, the water temperature of ultra-pure water is 25 ~ 30 DEG C, and ultrapure electrical conductivity of water is 10 μ S/cm, and leaching time is 6 ~ 10 hours;
(5) the hollow-fibre membrane intermediate removing diluent in step (4) is at room temperature dried, obtain large flux hollow fiber membranes.
The preparation method of the large flux hollow fiber membranes for drink water purifying that the present invention proposes, its advantage is:
1, in the inventive method, prepare the material that large flux hollow fiber membranes adopts, safety and sanitation, environmental protection, there is higher heat resistance and chemical stability, outstanding weatherability, resistance to ozone, ultraviolet resistance radiation and chemical resistance are the membrane materials high-end used for purifying drinking water of function admirable.
2, the large flux hollow fiber membranes prepared of the inventive method, its external diameter is 1.0 ~ 1.2mm, and wall thickness is 230 ~ 285 μm.Its section is co-continuous network, asymmetric pore structure, and hole height is through, be evenly distributed, and outer surface aperture is at 0.08 ~ 0.1 μm.Be 25 DEG C in temperature, under 0.1MPa pressure, pure water flux is 890 ~ 1500L/m
2h.The Structure and Properties of film shows after tested, and large flux hollow fiber membranes of the present invention is adapted at applying in drink water purifying.
Accompanying drawing explanation
Fig. 1 is the outer surface electromicroscopic photograph of hot method Pvdf Microporous Hollow Fiber Membrane prepared by the inventive method.
Fig. 2 is the section electromicroscopic photograph of hot method Pvdf Microporous Hollow Fiber Membrane prepared by the inventive method.
Fig. 3 is the section outward flange electromicroscopic photograph of hot method Pvdf Microporous Hollow Fiber Membrane prepared by the inventive method.
Detailed description of the invention
The preparation method of the large flux hollow fiber membranes for drink water purifying that the present invention proposes, comprises the following steps:
(1) polysulfones and Kynoar are carried out drying respectively in dryer, the temperature of oven dry 80 ~ 90 DEG C, drying time is 24 ~ 36 hours;
(2) for the preparation of the blended polymer solution of masking:
In blended polymer solution, the mass percent of each component is:
By Kynoar, polysulfones, PEG400, N, after N-dimethylacetylamide and polyvinyl alcohol weigh according to the above ratio, be placed in stirred tank, carry out stirring, dissolving at the temperature of 100 ~ 110 DEG C, mixing time is 14 ~ 16 hours, speed of agitator 90 ~ 110 revs/min, makes uniform blended polymer solution;
(3) the extruding and be shaped of hollow-fibre membrane, detailed process is as follows:
(3-1) the blended polymer solution of step (2) is sent in double screw extruder by spinning pump, the charging rate of raw material is 15 ~ 20Kg/ hour, the temperature of extruder 6 sections all sets unanimously, it is 100 ~ 110 DEG C, extrusion temperature is 100 ~ 110 DEG C, and screw speed is 90 ~ 120 revs/min;
(3-2) blended polymer solution is after double screw extruder is extruded, successively through filter and spinning pump, extrude from spinning-drawing machine annular die, form the as-spun fibre of hollow, the external diameter of described annular die is 5 millimeters, internal diameter is 4.2 millimeters, and annular die center passes into air, and the pressure of air is 20 ~ 30 millimeter of water (mmH
2o);
(3-3) above-mentioned hollow as-spun fibre is lower the temperature in the air of 20 ~ 25 DEG C in temperature, the distance that sky is walked is 2 ~ 5 centimetres, then enter in cold extraction liquid bath through cold extraction liquid cooling curing, through winder rolling, make hollow-fibre membrane intermediate, the rolling speed of winder 20 ~ 30 ms/min, described cold extraction liquid is water, and the temperature of cold extraction liquid is 50 ~ 70 DEG C;
(4) immersed in ultra-pure water by the hollow-fibre membrane intermediate in step (3), remove the mixture of the first diluent in film and the second diluent, the water temperature of ultra-pure water is 25 ~ 30 DEG C, and ultrapure electrical conductivity of water is 10 μ S/cm, and leaching time is 6 ~ 10 hours;
(5) the hollow-fibre membrane intermediate removing diluent in step (4) is at room temperature dried, obtain large flux hollow fiber membranes.
In above-mentioned preparation method, in described blended polymer solution, the mass ratio of each component is:
Kynoar/polysulfones=0.1 ~ 0.25,
PEG400/DMA=0.5 ~ 0.9,
(Kynoar+polysulfones)/(Kynoar+polysulfones+PEG400+DMA+polyvinyl alcohol)=0.22 ~ 0.30,
Polyvinyl alcohol/(Kynoar+polysulfones)=0.053 ~ 0.1.
In above-mentioned preparation method, the weight average molecular weight of described polysulfones is 70000; The weight average molecular weight of Kynoar is 370000, and the average degree of polymerization of polyvinyl alcohol is 1750.
Large flux hollow fiber membranes provided by the invention, the formula of its masking and content thereof by percentage to the quality:
Wherein, the weight average molecular weight of described polysulfones is 70000; The weight average molecular weight of Kynoar is 370000; The average degree of polymerization of polyvinyl alcohol is 1750.
Meanwhile, wherein the mass ratio of each composition is:
P
2/P
1=0.1～0.25，D
1/D
2=0.5～0.9，（P
1+P
2）/（P
1+P
2+D
1+D
2+A）=（22～30）wt%，A/（P
1+P
2）=0.053～0.1
The polysulfones (PSF) that the present invention adopts is the engineering material that a kind of temperature tolerance is good.Intensity is high, and the pH value scope of application is wide, and can apply in the system of PH=1 ~ 13, resistance to oxidation, chemically-resistant is cleaned, and chlorine resistance is good, and free chlorine can reach 200mg/l.Have good chemical stability, the characteristics such as solvent resistant, acid and alkali-resistance, resistance to oxidation are the preferred material of drink water purifying treatment process.
PSF material toughness is poor, is to improve the toughness of film, and the present invention adopts that PSF and PVDF is blended prepares alloy film, is convenient to the advantage that performance is respective, obtains the hollow fiber ultrafiltration membrane of function admirable.
The present invention is blended by PSF and PVDF, by the ratio of telomerized polymer, prepares the high strength of the different pore size of three-dimensional interpenetrating polymer network structure, anti-pollution, corrosion resistant hot method Pvdf Microporous Hollow Fiber Membrane.Blending ratio is determined, at PVDF/PSF blending ratio P by the compatibility studying alloy system
2/ P
1be experimental study display under 10/90,20/80,30/70,40/60,50/50,60/40,70/30 condition, this co-mixing system is partially compatible system, works as P
2/ P
1during >0.25, Miscibility is deteriorated, film forming difficulty, therefore P in the present invention
2/ P
1≤ 0.25.
The present invention adopts PVA as masking additive, being the hydrophily in order to utilize PVA, improving the contamination resistance of film.
In the inventive method, the polysulfones, Kynoar, PEG400, the N that use, N-dimethylacetylamide and polyvinyl alcohol are all commercial goods, wherein the manufacturer of polysulfones, Kynoar is U.S. SOLVAY(Su Wei) company, the purchase shop of other raw material is traditional Chinese medicines group chemical reagent Beijing Co., Ltd.
Below introduce embodiments of the invention:
Embodiment 1:
(1) pretreatment of polymeric material:
By polysulfones (molecular weight 70000), Kynoar PVDF(molecular weight 370000) in dryer, carry out drying respectively, the temperature of oven dry 85 DEG C.
(2) preparation of blended polymer solution:
By the polysulfones P of having dried
1, Kynoar P
2, PEG400 D
1, DMA D
2and after additive PVA weighs by mass percentage, be placed in batching kettle, its mass percent (wt%) is respectively P
1: P
2: D
1: D
2: A=20:2:36:40:2, at the temperature of 100 DEG C, carry out stirring and dissolving, mixing time 15 hours, speed of agitator is 100 revs/min, is dissolved into uniform blended polymer solution;
(3) the extruding of hollow-fibre membrane, be shaped:
(3-1) the blended polymer solution in step (2) is sent in double screw extruder by spinning pump, the charging rate of raw material is 15 kgs/hour, and the temperature of extruder 6 sections all sets unanimously, and extrusion temperature is 100 DEG C, screw speed is 100 revs/min, and die temperature is 100 DEG C;
(3-2) blended polymer solution is after double screw extruder is extruded, and successively through filter, spinning pump, extrude from the annular die of spinning-drawing machine, forms the as-spun fibre of hollow.The external diameter 3 millimeters (mm) of described annular die, internal diameter is 2.4 millimeters (mm).The pressure that annular die center passes into air is 20 millimeter of water (mmH
2o);
(3-3) above-mentioned hollow as-spun fibre is lower the temperature in the air of 20 DEG C in temperature, and the distance that sky is walked is 2 centimetres (cm), to enter in cold extraction liquid bath through cold extraction liquid cooling curing, through winder rolling, makes hollow-fibre membrane intermediate.Rolling speed 2.5 meter per second; Described cold extraction liquid is water, and the temperature of cold extraction liquid is 70 DEG C;
(4) leaching of diluent: immersed in ultra-pure water by the hollow-fibre membrane intermediate in (3), remove the diluent mixture in film, water temperature is 25 DEG C, and leaching time is 6 hours;
(5) dry: at room temperature drying removing the doughnut after diluent in (4), obtaining hollow fiber ultrafiltration membrane goods.
The film outer surface average pore size of these goods is 0.1 μm, and fiber outer diameter is 1.0mm, and wall thickness is 230 μm.Through scanning electronic microscope observation, film section is three-dimensional interpenetrating polymer network, asymmetric pore structure, as shown in Figure 1.As can be seen from Fig. 2 and Fig. 3, the section structure of large flux hollow fiber membranes is continuous, even aperture distribution, hole height is through, and film outward flange aperture is less than film section hole, and bore diameter gradient distributes, little, greatly interior outward, effectively can remove the colloid in water, microorganism, macromolecular substances.Illustrate, the contamination resistance of film strengthens, and is convenient to cleaning.Temperature be 25 DEG C, under 0.1MPa pressure, pure water flux is 1500L/m
2h.
Main preparation process condition and the film properties of embodiment of the present invention 2-6 is provided below in conjunction with table 1, but the content of each composition of the present invention is not limited to listed numerical value in this table, and it should be noted that, although listed file names with some other parameter in table 1, these Parameter Conditions have been described as necessary condition.For the present invention, the content of core is to improve film formula of liquid, and therefore, other parameters listed file names with in table 1 are just in order to provide about technical information of the present invention in more detail, be all preferred condition, described as necessary condition of the present invention.
The formulation ratio of table 1: embodiment 2-6, main preparation process condition and film properties
Claims (3)
1., for a preparation method for the large flux hollow fiber membranes of drink water purifying, it is characterized in that the method comprises the following steps:
(1) polysulfones and Kynoar are carried out drying respectively in dryer, the temperature of oven dry 80 ~ 90 DEG C, drying time is 24 ~ 36 hours;
(2) for the preparation of the blended polymer solution of masking:
In blended polymer solution, the mass percent of each component is:
By Kynoar, polysulfones, PEG400, N, after N-dimethylacetylamide and polyvinyl alcohol weigh according to the above ratio, be placed in stirred tank, carry out stirring, dissolving at the temperature of 100 ~ 110 DEG C, mixing time is 14 ~ 16 hours, speed of agitator 90 ~ 110 revs/min, makes uniform blended polymer solution;
(3) the extruding and be shaped of hollow-fibre membrane, detailed process is as follows:
(3-1) the blended polymer solution of step (2) is sent in double screw extruder by spinning pump, the charging rate of raw material is 15 ~ 20Kg/ hour, the temperature of extruder 6 sections all sets unanimously, it is 100 ~ 110 DEG C, extrusion temperature is 100 ~ 110 DEG C, and screw speed is 90 ~ 120 revs/min;
(3-2) blended polymer solution is after double screw extruder is extruded, successively through filter and spinning pump, extrude from spinning-drawing machine annular die, form the as-spun fibre of hollow, the external diameter of described annular die is 5 millimeters, internal diameter is 4.2 millimeters, and annular die center passes into air, and the pressure of air is 20 ~ 30 millimeters of water;
(3-3) above-mentioned hollow as-spun fibre is lower the temperature in the air of 20 ~ 25 DEG C in temperature, the distance that sky is walked is 2 ~ 5 centimetres, then enter in cold extraction liquid bath through cold extraction liquid cooling curing, through winder rolling, make hollow-fibre membrane intermediate, the rolling speed of winder 20 ~ 30 ms/min, described cold extraction liquid is water, and the temperature of cold extraction liquid is 50 ~ 70 DEG C;
(4) immersed in ultra-pure water by the hollow-fibre membrane intermediate in step (3), remove the mixture of the first diluent in film and the second diluent, the water temperature of ultra-pure water is 25 ~ 30 DEG C, and ultrapure electrical conductivity of water is 10 μ S/cm, and leaching time is 6 ~ 10 hours;
(5) the hollow-fibre membrane intermediate removing diluent in step (4) is at room temperature dried, obtain large flux hollow fiber membranes.
2. the preparation method of large flux hollow fiber membranes as claimed in claim 1, is characterized in that the mass ratio of each component in wherein said blended polymer solution is:
Kynoar/polysulfones=0.1 ~ 0.25,
PEG400/DMA=0.5 ~ 0.9,
(Kynoar+polysulfones)/(Kynoar+polysulfones+PEG400+DMA+polyvinyl alcohol)=0.22 ~ 0.30,
Polyvinyl alcohol/(Kynoar+polysulfones)=0.053 ~ 0.1.
3. the preparation method of large flux hollow fiber membranes as claimed in claim 1, is characterized in that the weight average molecular weight of wherein said polysulfones is 70000; The weight average molecular weight of Kynoar is 370000, and the average degree of polymerization of polyvinyl alcohol is 1750.
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| CN103638833B true CN103638833B (en) | 2016-01-20 |
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| CN114653229A (en) * | 2022-03-17 | 2022-06-24 | 福州福龙膜科技开发有限公司 | Preparation method of PVDF hydrophilic membrane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101143304A (en) * | 2007-07-17 | 2008-03-19 | 天津工业大学 | Hollow fiber membrane and its preparing process |
| CN101961648A (en) * | 2010-11-05 | 2011-02-02 | 天津森诺过滤技术有限公司 | Membrane adsorbent for removing heavy metal ions from drinking water effectively and preparation method thereof |
| CN103272494A (en) * | 2013-05-30 | 2013-09-04 | 苏州膜华材料科技有限公司 | Preparation method of polyvinylidene fluoride alloy membrane for wastewater treatment during high-salinity food processing |
-
2013
- 2013-12-20 CN CN201310713103.8A patent/CN103638833B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101143304A (en) * | 2007-07-17 | 2008-03-19 | 天津工业大学 | Hollow fiber membrane and its preparing process |
| CN101961648A (en) * | 2010-11-05 | 2011-02-02 | 天津森诺过滤技术有限公司 | Membrane adsorbent for removing heavy metal ions from drinking water effectively and preparation method thereof |
| CN103272494A (en) * | 2013-05-30 | 2013-09-04 | 苏州膜华材料科技有限公司 | Preparation method of polyvinylidene fluoride alloy membrane for wastewater treatment during high-salinity food processing |
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