CN103638831A - Preparation method of polyvinylidene fluoride hollow fiber ultra-filtration membrane for drinking water treatment - Google Patents
Preparation method of polyvinylidene fluoride hollow fiber ultra-filtration membrane for drinking water treatment Download PDFInfo
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Abstract
The invention relates to a preparation method of a polyvinylidene fluoride hollow fiber ultra-filtration membrane for drinking water treatment and belongs to the technical field of membrane separation and drinking water treatment. The preparation method comprises the following steps: respectively drying polyvinylidene fluoride and polyarylene sulfide sulfone in a drying machine; proportionally weighing the polyvinylidene fluoride, the polyarylene sulfide sulfone, tetraglycol, N-methyl-2-pyrrolidinone and polyvinylpyrrolidone, and putting into a stirring kettle for stirring and dissolving to obtain a uniform blended high polymer solution; extruding the uniform blended high polymer solution through a filter and a spinning pump, and then extruding a hollow nascent fiber from an annular opening mold; performing cooling and solidification through a cold extraction solution; soaking into reverse osmosis water to remove a membrane diluent mixture, and performing airing to obtain a hollow fiber ultra-filtration membrane product. According to the hollow fiber ultra-filtration membrane prepared through the method, raw materials are safe, sanitary and environment-friendly, and are high in heat resistance and chemical stability. The polyvinylidene fluoride hollow fiber ultra-filtration membrane is high in retention, stable in performance and suitable for being applied to municipal drinking water treatment, produced water is good in quality, and when the membrane is used, yarns are not broken.
Description
Technical field
The present invention relates to a kind of preparation method of the polyvinylidene fluoride hollow fiber ultrafiltration membrane for drinking water treatment, relate in particular to a kind of thermally induced phase separation (being called for short hot method) and prepare the hollow-fibre membrane of Kynoar (PVDF) and polyaryl thioether sulfone (PASS) blend, for municipal drinking water, process, belong to film separation 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 turbidity appear in some areas.Traditional coagulation-precipitation-filtration-sterilization process filtering accuracy is low, and disinfectant and coagulant use amount are high, large to water quality impact, and the water after processing can not meet the requirement of 106 drinking water standards of new national standard.Membrane separation technique is to carry out now drinking water deep purification, ensures the important new technology of water quality safety.The water treatment technology that the milipore filter of take is core has developed into third generation drinking water purification process, and the group technology of it and other technology, can process the drinking water of production high-quality effectively to micro polluted source.
Hollow-fibre membrane, intensity that traditional non-solvent phase method processed (abbreviation wet method) is produced are low, toughness is poor, in use easily fracture of wire, life-span short, be unsuitable for applying in large-scale drinking water treatment engineering.In the urgent need to exploitation, be suitable for large flux that municipal drinking water processes, high strength, antipollution, hollow fiber ultrafiltration membrane cheaply.
Summary of the invention
The object of the invention is to propose a kind of preparation method of the polyvinylidene fluoride hollow fiber ultrafiltration membrane for drinking water treatment, hollow-fibre membrane with preparation high strength, high tenacity, large flux, and make it have stronger contamination resistance, there is higher cost performance, for municipal drinking water, process engineering product guarantee is provided.
The preparation method of the polyvinylidene fluoride hollow fiber ultrafiltration membrane for drinking water treatment that the present invention proposes, comprises the following steps:
(1) Kynoar and polyaryl thioether sulfone are dried respectively in dryer, bake out temperature is 80～90 ℃, and 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:
After Kynoar, polyaryl thioether sulfone, tetraethylene glycol, 1-METHYLPYRROLIDONE and polyvinylpyrrolidone are weighed according to the above ratio, be placed in stirred tank, at the temperature of 150～170 ℃, stir, dissolve, mixing time is 14～16 hours, 90～110 revs/min of speeds of agitator, obtain 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, and the temperature of 6 sections of extruder is identical, is 150～170 ℃, extrusion temperature is 150～170 ℃, and screw speed is 90～120 revs/min;
(3-2) blended polymer solution is after double screw extruder is extruded, successively after filter and spinning pump, from the annular die of spinning-drawing machine, extrude, form hollow as-spun fibre, the external diameter of described annular die is 5 millimeters, internal diameter is 4.2 millimeters, and annular die center passes into nitrogen, and nitrogen pressure is 30～60 millimeter of water (mmH
2o);
(3-3) above-mentioned hollow as-spun fibre in being the air of 15～30 ℃, temperature is lowered the temperature, the distance that sky is walked is 20～40 centimetres, then enter in cold extraction liquid bath through cold extraction liquid cooling curing, through winder rolling, make hollow-fibre membrane intermediate, rolling speed is 15～20 ms/min, described cold extraction liquid is the two mixed liquor of water and tetraethylene glycol, in cold extraction mixed liquor, the mass percent concentration of water is 0～50wt%, the mass percent concentration of tetraethylene glycol is 50～100wt%, and the temperature of cold extraction mixed liquor is 20～40 ℃;
(4) the hollow-fibre membrane intermediate prepared by step (3) immerses in ultra-pure water, removes the first diluent in film and the mixture of the second diluent. and water temperature is 30～50 ℃, and leaching time is 12～15 hours, and ultrapure electrical conductivity of water is 10 μ S/cm;
(5) the hollow-fibre membrane intermediate that has removed diluent of step (4) is at room temperature dried, after drying, obtain hollow fiber ultrafiltration membrane.
The preparation method of the polyvinylidene fluoride hollow fiber ultrafiltration membrane for drinking water treatment that the present invention proposes, its advantage is:
1, the polyvinylidene fluoride hollow fiber ultrafiltration membrane adopting in preparation method of the present invention prepare material, 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 high-end drinking water treatment membrane materials of function admirable.
The preparation of the polyvinylidene fluoride hollow fiber ultrafiltration membrane that 2, prepared by the inventive method, its external diameter is 1.3～1.6mm, wall thickness is 270～379 μ m.Its section is co-continuous network, asymmetric pore structure, and hole height connects, is evenly distributed, and outer surface aperture is in 20～40 nanometers.In temperature, be 25 ℃, under 0.1MPa pressure, pure water flux is 250～1020L/m
2h, tensile strength of fiber 5.0～9.1MPa, elongation at break 80～110%.The structure of film and performance show after tested, and hot method doughnut alloy ultrafiltration membrane of the present invention is adapted at application in municipal drinking water processing.Film hold back height, to produce water water quality good, fracture of wire not in use, stable performance.
3, the polyvinylidene fluoride hollow fiber ultrafiltration membrane that prepared by the inventive method, film good hydrophilic property, has good antifouling property.In Practical Project, use proof, film is difficult for polluting, and the regular maintenance cleaning frequency is 2～3 times of other similar film product, and maintenance operation expense is low.
Accompanying drawing explanation
Fig. 1 is the outer surface electromicroscopic photograph of the polyvinylidene fluoride hollow fiber ultrafiltration membrane prepared of the inventive method.
Fig. 2 is the section electromicroscopic photograph of the polyvinylidene fluoride hollow fiber ultrafiltration membrane prepared of sharp the inventive method.
Fig. 3 is the section outward flange electromicroscopic photograph of the polyvinylidene fluoride hollow fiber ultrafiltration membrane prepared of the inventive method.
The specific embodiment
The preparation method of the polyvinylidene fluoride hollow fiber ultrafiltration membrane for drinking water treatment that the present invention proposes, comprises the following steps:
(1) Kynoar and polyaryl thioether sulfone are dried respectively in dryer, bake out temperature is 80～90 ℃, and 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:
After Kynoar, polyaryl thioether sulfone, tetraethylene glycol, 1-METHYLPYRROLIDONE and polyvinylpyrrolidone are weighed according to the above ratio, be placed in stirred tank, at the temperature of 150～170 ℃, stir, dissolve, mixing time is 14～16 hours, 90～110 revs/min of speeds of agitator, obtain 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, and the temperature of 6 sections of extruder is identical, is 150～170 ℃, extrusion temperature is 150～170 ℃, and screw speed is 90～120 revs/min;
(3-2) blended polymer solution is after double screw extruder is extruded, successively after filter and spinning pump, from the annular die of spinning-drawing machine, extrude, form hollow as-spun fibre, the external diameter of described annular die is 5 millimeters, internal diameter is 4.2 millimeters, and annular die center passes into nitrogen, and nitrogen pressure is 30～60 millimeter of water (mmH
2o);
(3-3) above-mentioned hollow as-spun fibre in being the air of 15～30 ℃, temperature is lowered the temperature, the distance that sky is walked is 20～40 centimetres, then enter in cold extraction liquid bath through cold extraction liquid cooling curing, through winder rolling, make hollow-fibre membrane intermediate, rolling speed is 15～20 ms/min, described cold extraction liquid is the two mixed liquor of water and tetraethylene glycol, in cold extraction mixed liquor, the mass percent concentration of water is 0～50wt%, the mass percent concentration of tetraethylene glycol is 50～100wt%, and the temperature of cold extraction mixed liquor is 20～40 ℃;
(4) the hollow-fibre membrane intermediate prepared by step (3) immerses in ultra-pure water, removes the first diluent in film and the mixture of the second diluent. and water temperature is 30～50 ℃, and leaching time is 12～15 hours, and ultrapure electrical conductivity of water is 10 μ S/cm;
(5) the hollow-fibre membrane intermediate that has removed diluent of step (4) is at room temperature dried, after drying, obtain hollow fiber ultrafiltration membrane.
Above-mentioned preparation method, in described blended polymer solution:
Polyaryl thioether sulfone: Kynoar=1:(0.1～0.4),
Tetraethylene glycol: 1-METHYLPYRROLIDONE=1:(0.35～0.6),
(Kynoar+polyaryl thioether sulfone): (Kynoar+polyaryl thioether sulfone+tetraethylene glycol+1-METHYLPYRROLIDONE+polyvinylpyrrolidone)=1:(0.275～0.435),
Polyvinylpyrrolidone/(Kynoar+polyaryl thioether sulfone)=1:(0.029～0.09).
Above-mentioned preparation method, the weight average molecular weight of described Kynoar is 370000, the weight average molecular weight of polyaryl thioether sulfone is 70000, the weight average molecular weight 1100000 of polyvinylpyrrolidone.
In the preparation method of Pvdf Microporous Hollow Fiber Membrane of the present invention, the chemical structural formula of poly arylidene thio-ester is as follows:
Hot method Kynoar provided by the invention (PVDF) hollow fiber ultrafiltration membrane, the formula of its masking and content thereof by percentage to the quality:
The first polymer P
1: Kynoar (PVDF) 20～35wt%
The second polymer P
2: polyaryl thioether sulfone (PASS) 2.5～10wt%
The first diluent D
1: tetraethylene glycol (C8H18O5) 14～20wt%
Second diluent D2:N-methyl pyrrolidone (NMP) 34～51wt%
Additive A: polyvinylpyrrolidone (PVPK90) 1～3wt%
Wherein, the weight average molecular weight of described Kynoar is 370000; The weight average molecular weight of polyaryl thioether sulfone is 70000, the weight average molecular weight 1100000 of polyvinylpyrrolidone.
Meanwhile, wherein the mass ratio of each composition is:
P
2/P
1=0.1～0.4，D
1/D
2=0.35～0.6，（P
1+P
2）/（P
1+P
2+D
1+D
2+A）=（27.5～43.5）wt%，A/（P
1+P
2）=0.029～0.09
Kynoar (PVDF) good toughness that the present invention adopts, having the characteristics such as good chemical stability, resistance to solvent, acid and alkali-resistance, resistance to oxidation, is the preferred material of municipal drinking water treatment process.
The tensile break strength of PVDF material is low, for strengthening the tensile strength of pvdf membrane, adopts polyaryl thioether sulfone (PASS) as the material of preparing alloy film in the present invention.Polyaryl thioether sulfone (PASS) is the important kind in poly arylidene thio-ester (PPS) class special engineering plastics, is a kind of modified product of PPS resin.PASS material has high strength, fabulous dimensional stability, good decay resistance, and PASS resin has excellent toughness simultaneously, and its vitrification point is up to 220 ℃, and Heat stability is good, is a kind of novel high-performance material of preparing.Adopt PVDF and PASS blend to prepare alloy film, be convenient to performance advantage separately, obtain the hollow fiber ultrafiltration membrane of function admirable.
The present invention, by PVDF and PASS blend, by the ratio of telomerized polymer, prepares high strength, anti-pollution, the corrosion resistant hollow fiber alloy film of the different pore size of three-dimensional interpenetrating polymer network structure.Compatibility by research alloy system is determined blend ratio, at PASS/PVDF blending ratio P
2/ P
1be that under 10/90,20/80,30/70,40/60,50/50,60/40,70/30 condition, experimental study shows, this co-mixing system is the compatible system of part, works as P
2/ P
1miscibility variation during >0.5, film forming difficulty, so P in the present invention
2/ P
1< 0.5.
The present invention adopts PVPK90 as masking additive, is in order to utilize the hydrophily of PVP, improves the contamination resistance of film.
Raw material Kynoar, polyaryl thioether sulfone, tetraethylene glycol, 1-METHYLPYRROLIDONE and the polyvinylpyrrolidone using in the inventive method is all commercial goods, wherein the manufacturer of Kynoar is SOLVAY(Su Wei) company, the manufacturer of polyaryl thioether sulfone is Kuching, Inner Mongol logical new high-tech material Co., Ltd, and 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 Kynoar PVDF(molecular weight 370000), polyaryl thioether sulfone (molecular weight 70000) is dried respectively in dryer, 85 ℃ of the temperature of oven dry.
(2) preparation of blended polymer solution:
By the Kynoar P of having dried
1, polyaryl thioether sulfone P
2, tetraethylene glycol D
1, 1-METHYLPYRROLIDONE D
2and after additive PVPK90 weighs by mass percentage, being placed in batching kettle, its mass percent (wt%) is respectively P
1: P
2: D
1: D
2: A=30:6:20:42:2.0 carries out stirring and dissolving at the temperature of 165 ℃, mixing time 15 hours, and speed of agitator is 100 revs/min, is dissolved into uniform blended polymer solution;
(3) the extruding, be shaped of hollow-fibre membrane:
(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 6 sections of extruder is all set unanimously, and extrusion temperature is 165 ℃, screw speed is 100 revs/min, and die temperature is 165 ℃;
(3-2) blended polymer solution, after double screw extruder is extruded, passes through successively filter, spinning pump, from annular die, extrudes, and forms the as-spun fibre of hollow.5 millimeters of the external diameters (mm) of described annular die, internal diameter is 4.2 millimeters (mm).The pressure that annular die center passes into nitrogen is 40 millimeter of water (mmH
2o);
(3-3) above-mentioned hollow as-spun fibre is lowered the temperature in temperature is the air of 25 ℃, and the distance that sky is walked is 40 centimetres (cm), enters in cold extraction liquid bath through cold extraction liquid cooling curing, through winder rolling, makes hollow-fibre membrane intermediate.15 ms/min of rolling speed; Described cold extraction liquid is the two mixed liquor of water and tetraethylene glycol, and the temperature of cold extraction mixed liquor is 40 ℃, and in cold extraction mixed liquor, the mass percent concentration of water is 0, and the mass percent concentration of tetraethylene glycol is 100wt%;
(4) the hollow-fibre membrane intermediate in (3) is immersed in reverse osmosis water, remove the diluent mixture in film, water temperature is 50 ℃, and leaching time is 13 hours;
(5) doughnut removing after diluent in (4) is at room temperature dried, obtain hollow fiber ultrafiltration membrane goods.
The film outer surface average pore size of these goods is 40nm, and fiber external diameter is 1.6mm, and wall thickness is 370 μ m.Through scanning electronic microscope observation, film section is three-dimensional interpenetrating polymer network, asymmetric pore structure, as shown in Figure 1.Figure 2 shows that the section electromicroscopic photograph of polyvinylidene fluoride hollow fiber ultrafiltration membrane.As can be seen from Figure 2, the section structure of PVDF alloy film is continuous, even aperture distribution, and hole height connects.Fig. 3 is outward flange electromicroscopic photograph, can find out that PVDF alloy film outward flange aperture is less than film section hole, and bore diameter gradient distributes, outer little, interior large, can effectively remove colloid, microorganism in water, macromolecular substances.Illustrate, the contamination resistance of film strengthens, and is convenient to clean.Under temperature is 25 ℃, 0.1MPa pressure, pure water flux is 590L/m
2h, tensile strength of fiber is 7.0MPa, elongation at break 95%.
Below in conjunction with table 1, provide main preparation process condition and the film properties of embodiment of the present invention 2-6, 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 are described as necessary condition.For the present invention, the content of core is to improve film formula of liquid, and therefore, other parameters that list file names with in table 1 are just in order to provide in more detail about technical information of the present invention, be all preferred condition, as necessary condition of the present invention, described.
Table 1: embodiment 2 ?6 formulation ratio, main preparation process condition and film properties
Claims (3)
1. for a preparation method for the polyvinylidene fluoride hollow fiber ultrafiltration membrane of drinking water treatment, it is characterized in that, the method comprises the following steps:
(1) Kynoar and polyaryl thioether sulfone are dried respectively in dryer, bake out temperature is 80～90 ℃, and 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:
After Kynoar, polyaryl thioether sulfone, tetraethylene glycol, 1-METHYLPYRROLIDONE and polyvinylpyrrolidone are weighed according to the above ratio, be placed in stirred tank, at the temperature of 150～170 ℃, stir, dissolve, mixing time is 14～16 hours, 90～110 revs/min of speeds of agitator, obtain 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, and the temperature of 6 sections of extruder is identical, is 150～170 ℃, extrusion temperature is 150～170 ℃, and screw speed is 90～120 revs/min;
(3-2) blended polymer solution is after double screw extruder is extruded, successively after filter and spinning pump, from the annular die of spinning-drawing machine, extrude, form hollow as-spun fibre, the external diameter of described annular die is 5 millimeters, internal diameter is 4.2 millimeters, and annular die center passes into nitrogen, and nitrogen pressure is 30～60 millimeters of water;
(3-3) above-mentioned hollow as-spun fibre in being the air of 15～30 ℃, temperature is lowered the temperature, the distance that sky is walked is 20～40 centimetres, then enter in cold extraction liquid bath through cold extraction liquid cooling curing, through winder rolling, make hollow-fibre membrane intermediate, rolling speed is 15～20 ms/min, described cold extraction liquid is the two mixed liquor of water and tetraethylene glycol, in cold extraction mixed liquor, the mass percent concentration of water is 0～50wt%, the mass percent concentration of tetraethylene glycol is 50～100wt%, and the temperature of cold extraction mixed liquor is 20～40 ℃;
(4) the hollow-fibre membrane intermediate prepared by step (3) immerses in ultra-pure water, removes the first diluent in film and the mixture of the second diluent. and water temperature is 30～50 ℃, and leaching time is 12～15 hours, and ultrapure electrical conductivity of water is 10 μ S/cm;
(5) the hollow-fibre membrane intermediate that has removed diluent of step (4) is at room temperature dried, after drying, obtain hollow fiber ultrafiltration membrane.
2. preparation method as claimed in claim 1, is characterized in that in wherein said blended polymer solution:
Polyaryl thioether sulfone: Kynoar=1:(0.1～0.4),
Tetraethylene glycol: 1-METHYLPYRROLIDONE=1:(0.35～0.6),
(Kynoar+polyaryl thioether sulfone): (Kynoar+polyaryl thioether sulfone+tetraethylene glycol+1-METHYLPYRROLIDONE+polyvinylpyrrolidone)=1:(0.275～0.435),
Polyvinylpyrrolidone/(Kynoar+polyaryl thioether sulfone)=1:(0.029～0.09).
3. preparation method as claimed in claim 1, the weight average molecular weight that it is characterized in that wherein said Kynoar is 370000, the weight average molecular weight of polyaryl thioether sulfone is 70000, the weight average molecular weight 1100000 of polyvinylpyrrolidone.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116272433A (en) * | 2023-04-28 | 2023-06-23 | 常州工程职业技术学院 | Modified polyvinylidene fluoride water treatment film and preparation method thereof |
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