CN104479167A - Waste polyvinylidene fluoride hollow fiber membrane filament recycling method - Google Patents
Waste polyvinylidene fluoride hollow fiber membrane filament recycling method Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
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Abstract
The invention belongs to the field of recycling and reuse of high polymer materials, and in particular relates to a waste polyvinylidene fluoride hollow fiber membrane filament recycling method which comprises the following waste filament pretreatment steps in sequence: washing, namely, washing waste filaments generated in the manufacturing process, including soaking for 12-24 hours by using 1500-2500ppm sodium hypochlorite at 35-45 DEG C, washing for 2-4 hours by using water at 30-50 DEG C, and subsequently drying for 4-8 hours at 60-95 DEG C till the water content of the waste filaments is less than or equal to 1.5%; washing waste filaments replaced from sewage plants, namely, rinsing with clean water, and subsequently pickling for 12-24 hours, wherein 0.15-0.35wt% or 1-2wt% of citric acid is used as acid for pickling; soaking for 12-24 hours by using a mixed liquid of 1500-2500ppm sodium hypochlorite and 0.05-0.15wt% of sodium hydroxide at 35-45 DEG C, further washing for 2-4 hours at 30-50 DEG C, and drying for 4-8 hours at 60-95 DEG C till the water content of the waste filaments is less than or equal to 1.5%; dissolving and curing by using gel; drying, crushing and pelleting. By adopting the method, a polyvinylidene fluoride raw material can be effectively washed, recycled and reused, and the environment pollution caused by waste membranes is avoided.
Description
Technical field
The invention belongs to the recycling field of macromolecular material, particularly relate to Pvdf Microporous Hollow Fiber Membrane waste silk recoverying and utilizing method.
Background technology
Along with the development of membrane technique, hollow fiber separating film has obtained in fields such as the separation of gas, liquid mixture applying increasingly extensively.In order to improve the work-ing life of hollow-fibre membrane, mould material is generally selected from the macromolecular material of chemical stability and good weatherability, do not corroded by acid, alkali, strong oxidizer or halogen at normal temperatures, outdoor can be exposed to for a long time and without catabiosis, therefore also give and widely apply the useless film silk process produced to bring a difficult problem.
Polyvinylidene difluoride (PVDF) (PVDF) is as a kind of semicrystalline polymer, and crystalline region is given film and had good thermostability and physical strength, and its pars amorpha makes film more pliable and tougher.In addition, polyvinylidene difluoride (PVDF) (PVDF) has good chemical stability, at room temperature not sour, strong oxidizer and halogen corroded, also very stable to organic solvents such as aliphatic hydrocarbon, aromatic hydrocarbon, alcohols and aldehydes, and gamma ray resistant and ultraviolet radiation, can be exposed to outdoor and for a long time without catabiosis.These characteristics of polyvinylidene difluoride (PVDF) (PVDF) make it be paid attention to gradually in membrane separation technique and apply, and are widely used in foodstuffs industry, biochemical engineering, pharmaceutical industries and water treatment at present, the sewage disposal that especially working conditions is very severe.
The consumption growth of polyvinylidene difluoride (PVDF) (PVDF) in water treatment field is exceedingly fast, the production capacity of the current whole world annual polyvinylidene difluoride (PVDF) (PVDF) hollow-fibre membrane reaches more than one hundred million square metres, and be about 3-8 its work-ing life, change along with annual mould material, a large amount of useless film silk will be produced.Because polyvinylidene difluoride (PVDF) (PVDF) has extremely strong stability, ordinary method process can not be used, as buried and burning, deal with improperly and will cause serious environmental pollution.The inventive method is by recycling polyvinylidene difluoride (PVDF) (PVDF) hollow-fibre membrane, and the environmental pollution avoiding its useless film to cause, farthest make use of resource.
Patent of invention CN101422708B (2011-8-31) provides a kind of recovery method of Pvdf Microporous Hollow Fiber Membrane, mainly comprises following steps: a. PVDF gives up the pre-treatment of film silk: comprise rinsing, dry and pulverize; B. the preparation of spinning solution; C. cross and filter solids in PVDF coating solution and impurity; D. with dry-wet spinning technology, PVDF spinning solution is spun into hollow-fibre membrane.But this patent of paramount importance preprocessing process in polyvinylidene difluoride (PVDF) waste silk removal process is not elaborated.
Summary of the invention
The object of this invention is to provide and a kind ofly effectively can utilize the Pvdf Microporous Hollow Fiber Membrane waste silk recoverying and utilizing method of the polyvinylidene difluoride (PVDF) raw material in tubular fibre waste silk by clean and reuse.
Above-mentioned technical purpose of the present invention is achieved by the following technical programs:
A kind of Pvdf Microporous Hollow Fiber Membrane waste silk recoverying and utilizing method, it comprises following waste silk pre-treatment step successively:
A. clean: comprise the waste silk cleaning produced in manufacturing processed and/or the waste silk cleaning of replacing Sewage Plant;
Wherein, the waste silk cleaning produced is comprised first use 1500-2500ppm 35-45 DEG C of clorox immersion treatment 12-24 hour in manufacturing processed, then at 30-50 DEG C of washing 2-4 hour, then little of waste silk water ratio≤1.5% at 60-95 DEG C of dry 4-8;
The waste silk cleaning of replacing Sewage Plant comprises pickling 12-24 hour after clear water rinsing, and pickling acid used is 0.15-0.35wt% hydrochloric acid or 1-2wt% citric acid; Then use 1500-2500ppm clorox and 0.05-0.15wt% sodium hydroxide mixed solution at 35-45 DEG C of immersion treatment 12-24 hour, then with 30-50 DEG C of washing 2-4 hour, then little of waste silk water ratio≤1.5% at 60-95 DEG C of dry 4-8;
B. dissolve and gel solidification: waste silk and the dimethyl formamide after cleaning is mixed being incorporated in 70-80 DEG C and dissolving according to mass ratio 1:0.8-1.2 proportioning, then enter gel solidification in 50-70 DEG C of pure water after the centrifuging of 150-250 order;
C. dry: gained gel solidification thing is little of water ratio≤0.5% at 60-95 DEG C of dry 6-12;
D. pulverize;
E. granulation: 180-200 DEG C extruding pelletization, obtains the polyvinylidene difluoride (PVDF) reclaimed materials grain of particle size diameter 0.5-2mm, length 0.5-2.5mm.
The present invention adopts specific waste silk purging method, especially different purging methods is adopted to the waste silk produced in manufacturing processed with to the waste silk of replacing after Sewage Plant use, thus obtain degree of cleaning higher, waste silk that PVDF content is larger, be conducive to follow-up dissolving, filtration and gel solidification, thus recovery acquisition can carry out follow-up PVDF tubular fibre film preparation PVDF recovery pellet used, effectively avoids the detrimentally affect that the film silk of the impurity in waste silk to the film preparation of follow-up PVDF tubular fibre causes; Thus while alleviating environmental pollution, greatly can reduce production cost prepared by film silk.
As preferably, the waste silk cleaning produced is comprised first use 2000ppm 40 DEG C of clorox immersion treatment 12-24 hour in manufacturing processed, then at 40 DEG C of washing 2-4 hour, then little of waste silk water ratio≤1.5% at 60-95 DEG C of dry 4-8; Then waste silk and the dimethyl formamide after cleaning is mixed according to mass ratio 1:1 proportioning and is incorporated in 75 DEG C and dissolves, then after centrifuging in water gel solidification.
Employing the method more effectively removes the impurity in the waste silk produced in manufacturing processed, reclaims the effective PVDF composition in waste silk.
As preferably, the waste silk cleaning of replacing Sewage Plant comprises pickling 12-24 hour after clear water rinsing, and pickling acid used is 0.2wt% hydrochloric acid or 1-2wt% citric acid; Then use 2000ppm clorox and 0.1wt% sodium hydroxide mixed solution at 40 DEG C of immersion treatment 12-24 hour, then with 40 DEG C of washing 2-4 hour, then little of waste silk water ratio≤1.5% at 60-95 DEG C of dry 4-8; Then waste silk and the dimethyl formamide after cleaning is mixed according to mass ratio 1:1 proportioning and is incorporated in 75 DEG C and dissolves, then after centrifuging in 50-70 DEG C of pure water gel solidification.
Adopt the method more effectively to remove impurity in the waste silk that Sewage Plant replaces, reclaim the effective PVDF composition in waste silk.
As preferably, described waste silk recoverying and utilizing method also comprises the polyvinylidene difluoride (PVDF) reclaimed materials grain utilizing waste silk pretreatment process to obtain and prepares Pvdf Microporous Hollow Fiber Membrane;
Wherein preparation liquid comprises polyvinylidene difluoride (PVDF), pore-creating agent, low molecular weight additives and solvent; Described polyvinylidene difluoride (PVDF) accounts for the 15-35% of described preparation liquid quality;
Described pore-creating agent accounts for the 2-20wt% of described preparation liquid quality;
Described low molecular weight additives accounts for the 0.5-1.5wt% of described preparation liquid quality.
Described polyvinylidene difluoride (PVDF) reclaimed materials grain quality accounts for the 50-100wt% of polyvinylidene difluoride (PVDF) total mass in preparation liquid.
Adopt the polyvinylidene difluoride (PVDF) reclaimed materials grain that waste silk clean and reuse obtains, can the excellent PVDF hollow-fibre membrane of processability.
As preferably, described pore-creating agent comprise in polyvinylpyrrolidone, polyoxyethylene glycol or polyvinyl alcohol one or more.
As preferably, described low molecular weight additives comprise in lithium chloride, lithium nitrate, SODIUMNITRATE, magnesium chloride, water, glycerol and ethylene glycol one or more.
As preferably, described solvent comprise in dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO) and triethyl phosphate one or more.
As preferably, described Pvdf Microporous Hollow Fiber Membrane preparation method comprises and is added in dissolution kettle by described preparation liquid, 60-80 DEG C is stirred 10-20 hour, through filtering net after vacuum defoamation 10-15 hour, adopt dry-wet spinning, film-casting liquid temperature is 60-70 DEG C, air section height is 1-4 centimetre, core liquid adopts the solvent aqueous solution of 40-50wt%, and precipitation bath is the solvent aqueous solution of 25-35wt%, and coagulation bath temperature is 40-50 DEG C.
More preferably, described filtering net adopts 150-250 order.
As preferably, the hollow-fibre membrane the key technical indexes that described Pvdf Microporous Hollow Fiber Membrane preparation method obtains is as follows: film silk aperture 20-100nm; Pure water flux is 200-1500 L/m2hbar25 DEG C; Porosity is 70%-90%; Monofilament pulling force 3-5N; Stretch percentage elongation is 100-150%.In sum, the present invention has following beneficial effect: can recycle the polyvinylidene difluoride (PVDF) raw material in tubular fibre waste silk, designed by composition and engineering, prepare Pvdf Microporous Hollow Fiber Membrane, avoid the environmental pollution that useless film causes, farthest make use of the Pvdf Microporous Hollow Fiber Membrane waste silk of resource.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of Pvdf Microporous Hollow Fiber Membrane waste silk recoverying and utilizing method of the present invention.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail.
Embodiment one
As shown in Figure 1, waste silk pre-treatment: to the waste silk cleaning produced in manufacturing processed;
The waste silk cleaning produced in manufacturing processed comprises first uses 1500ppm 35 DEG C of clorox immersion treatment 12 hours, then 30 DEG C of washings 2 hours, then little of waste silk water ratio≤1.5% 60 DEG C of dryings 8;
Dissolve and gel solidification: waste silk and the dimethyl formamide after cleaning is mixed being incorporated in 70 DEG C and dissolving according to mass ratio 1:0.8 proportioning, then enter gel solidification in 50 DEG C of pure water after 150 order centrifugings;
Dry: gained gel solidification thing is little of water ratio≤0.5% 60 DEG C of dryings 12;
Pulverize;
Granulation: 180 DEG C of extruding pelletizations, obtains the polyvinylidene difluoride (PVDF) reclaimed materials grain of particle size diameter 0.5-2mm, length 0.5-2.5mm.
Then the polyvinylidene difluoride (PVDF) reclaimed materials grain utilizing waste silk pretreatment process to obtain prepares Pvdf Microporous Hollow Fiber Membrane:
Preparation liquid comprises polyvinylidene difluoride (PVDF), pore-creating agent, low molecular weight additives and solvent;
Polyvinylidene difluoride (PVDF) accounts for 15% of preparation liquid quality;
Pore-creating agent accounts for the 2wt% of preparation liquid quality;
Low molecular weight additives accounts for the 0.5wt% of preparation liquid quality; All the other are solvent.
Polyvinylidene difluoride (PVDF) reclaimed materials grain quality accounts for the 50wt% of polyvinylidene difluoride (PVDF) total mass in preparation liquid.
Pore-creating agent comprises polyvinylpyrrolidone; Low molecular weight additives comprises lithium chloride; Solvent comprises N,N-DIMETHYLACETAMIDE.
Pvdf Microporous Hollow Fiber Membrane preparation method comprises and is added in dissolution kettle by described preparation liquid, 60 DEG C are stirred 10 hours, vacuum defoamation after 10 hours through 150 order filtering nets, adopt dry-wet spinning, film-casting liquid temperature is 60 DEG C, and air section height is 1 centimetre, and core liquid adopts the dimethylformamide in water of 40wt%, precipitation bath is the dimethylformamide in water of 25wt%, and coagulation bath temperature is 40 DEG C.
Final obtained hollow-fibre membrane the key technical indexes is as follows: film silk aperture 70nm; Pure water flux is 900 L/m2hbar25 DEG C; Porosity is 80%; Monofilament pulling force 4N; Stretch percentage elongation is 120%.
Embodiment two
As shown in Figure 1, waste silk pre-treatment: to the waste silk cleaning produced in manufacturing processed;
The waste silk cleaning produced in manufacturing processed comprises first uses 2500ppm 45 DEG C of clorox immersion treatment 24 hours, then 50 DEG C of washings 4 hours, then little of waste silk water ratio≤1.5% 95 DEG C of dryings 4;
Dissolve and gel solidification: waste silk and the dimethyl formamide after cleaning is mixed being incorporated in 80 DEG C and dissolving according to mass ratio 1:1.2 proportioning, then enter gel solidification in 70 DEG C of pure water after 250 order centrifugings;
Dry: gained gel solidification thing is little of water ratio≤0.5% 95 DEG C of dryings 6;
Pulverize;
Granulation: 200 DEG C of extruding pelletizations, obtains the polyvinylidene difluoride (PVDF) reclaimed materials grain of particle size diameter 0.5-2mm, length 0.5-2.5mm.
Then the polyvinylidene difluoride (PVDF) reclaimed materials grain utilizing waste silk pretreatment process to obtain prepares Pvdf Microporous Hollow Fiber Membrane:
Preparation liquid comprises polyvinylidene difluoride (PVDF), pore-creating agent, low molecular weight additives and solvent;
Polyvinylidene difluoride (PVDF) accounts for 35% of preparation liquid quality;
Pore-creating agent accounts for the 20wt% of preparation liquid quality;
Low molecular weight additives accounts for the 1.5wt% of preparation liquid quality.
Polyvinylidene difluoride (PVDF) reclaimed materials grain quality accounts for the 100wt% of polyvinylidene difluoride (PVDF) total mass in preparation liquid.
Pore-creating agent comprises polyoxyethylene glycol; Low molecular weight additives comprises lithium nitrate; Solvent comprises N-Methyl pyrrolidone.
Pvdf Microporous Hollow Fiber Membrane preparation method comprises and is added in dissolution kettle by described preparation liquid, 80 DEG C are stirred 20 hours, vacuum defoamation after 15 hours through 250 order filtering nets, adopt dry-wet spinning, film-casting liquid temperature is 70 DEG C, and air section height is 4 centimetres, and core liquid adopts the dimethylacetamide amine aqueous solution of 50wt%, precipitation bath is the dimethylacetamide amine aqueous solution of 35wt%, and coagulation bath temperature is 50 DEG C.
Final obtained hollow-fibre membrane the key technical indexes is as follows: film silk aperture 20nm; Pure water flux is 200L/m2hbar25 DEG C; Porosity is 70%; Monofilament pulling force 3N; Stretch percentage elongation is 100%.
Embodiment three
The waste silk cleaning produced in manufacturing processed is comprised and first uses 2000ppm 40 DEG C of clorox immersion treatment 20 hours, then 40 DEG C of washings 3 hours, then little of waste silk water ratio≤1.5% 85 DEG C of dryings 6; Then waste silk and the dimethyl formamide after cleaning is mixed according to mass ratio 1:1 proportioning and is incorporated in 75 DEG C and dissolves, then after centrifuging in water gel solidification.
Then waste silk and the dimethyl formamide after cleaning is mixed according to mass ratio 1:1.1 proportioning and be incorporated in 75 DEG C and dissolve, then enter gel solidification in 60 DEG C of pure water after 200 order centrifugings;
Dry: gained gel solidification thing is little of water ratio≤0.5% 75 DEG C of dryings 8;
Pulverize;
Granulation: 190 DEG C of extruding pelletizations, obtains the polyvinylidene difluoride (PVDF) reclaimed materials grain of particle size diameter 0.5-2mm, length 0.5-2.5mm.
Then the polyvinylidene difluoride (PVDF) reclaimed materials grain utilizing waste silk pretreatment process to obtain prepares Pvdf Microporous Hollow Fiber Membrane:
Preparation liquid comprises polyvinylidene difluoride (PVDF), pore-creating agent, low molecular weight additives and solvent;
Polyvinylidene difluoride (PVDF) accounts for 25% of preparation liquid quality;
Pore-creating agent accounts for the 15wt% of preparation liquid quality;
Low molecular weight additives accounts for the 1.2wt% of preparation liquid quality.
Polyvinylidene difluoride (PVDF) reclaimed materials grain quality accounts for the 80wt% of polyvinylidene difluoride (PVDF) total mass in preparation liquid.
Pore-creating agent is polyvinyl alcohol; Low molecular weight additives comprises SODIUMNITRATE; Solvent comprises dimethyl sulfoxide (DMSO).
Pvdf Microporous Hollow Fiber Membrane preparation method comprises and is added in dissolution kettle by described preparation liquid, 70 DEG C are stirred 15 hours, vacuum defoamation after 12 hours through 200 order filtering nets, adopt dry-wet spinning, film-casting liquid temperature is 65 DEG C, and air section height is 3 centimetres, and core liquid adopts the dimethylformamide in water of 45wt%, precipitation bath is the dimethylformamide in water of 28wt%, and coagulation bath temperature is 45 DEG C.
Final obtained hollow-fibre membrane the key technical indexes is as follows: film silk aperture 100nm; Pure water flux is 1500 L/m2hbar25 DEG C; Porosity is 90%; Monofilament pulling force 5N; Stretch percentage elongation is 150%.
Embodiment four
With embodiment one, be reclaim to obtain from the waste silk that Sewage Plant is replaced unlike PVDF reclaimed materials grain used during masking, the waste silk cleaning of replacing from Sewage Plant to comprise after clear water rinsing pickling 12 hours, and pickling acid used is 0.15wt% hydrochloric acid; Then use 1500ppm clorox and 0.05wt% sodium hydroxide mixed solution 35 DEG C of immersion treatment 12 hours, then with 30 DEG C of washings 2 hours, then little of waste silk water ratio≤1.5% 60 DEG C of dryings 8.
Embodiment five
With embodiment two, be reclaim to obtain from the waste silk that Sewage Plant is replaced unlike PVDF reclaimed materials grain used during masking, the waste silk cleaning of replacing from Sewage Plant to comprise after clear water rinsing pickling 24 hours, and pickling acid used is 1-2wt% citric acid; Then use 2500ppm clorox and 0.15wt% sodium hydroxide mixed solution 45 DEG C of immersion treatment 24 hours, then with 50 DEG C of washings 3 hours, then little of waste silk water ratio≤1.5% 95 DEG C of dryings 4.
Embodiment six
With embodiment three, be reclaim to obtain from the waste silk that Sewage Plant is replaced unlike PVDF reclaimed materials grain used during masking, the waste silk cleaning of replacing Sewage Plant comprises pickling 12-24 hour after clear water rinsing, and pickling acid used is 0.25wt% hydrochloric acid; Then use 2000ppm clorox and 0.1wt% sodium hydroxide mixed solution at 40 DEG C of immersion treatment 12-24 hour, then with 40 DEG C of washings 4 hours, then little of waste silk water ratio≤1.5% 80 DEG C of dryings 5; Then waste silk and the dimethyl formamide after cleaning is mixed according to mass ratio 1:1 proportioning and is incorporated in 75 DEG C and dissolves, then after centrifuging in water gel solidification.
Embodiment seven
Select the polyvinylidene difluoride (PVDF) waste silk produced in spinning process to soak 12 hours in the chlorine bleach liquor of 2000ppm, then use 40 DEG C of clear water rinsings 4 hours, put into baking oven 60 DEG C of dryings after 8 hours water ratio be 1.2%.Waste silk complete for drying is dissolved in dimethyl formamide according to the mass ratio of 1:1, heated and stirred 12 hours at 75 DEG C, then gel solidification in 60 DEG C of pure water is entered by 200 order centrifugings, by solidification after film liquid put into 95 DEG C of baking oven inner dryings after 6 hours water ratio be 0.3%, then broken, material after fragmentation enters forcing machine in 200 DEG C of extruding pelletizations, and obtaining diameter is 0.5mm, and length is the recovery polyvinylidene difluoride (PVDF) particle of 0.5mm.
Film-casting liquid configures according to following proportioning: 21wt% polyvinylidene difluoride (PVDF) (be entirely and reclaim particle), 5wt% polyvinylpyrrolidone, 6wt% polyoxyethylene glycol, 1.5wt% lithium chloride, 66.5wt% N,N-DIMETHYLACETAMIDE, above material is added in dissolution kettle, 70 DEG C are stirred 12 hours, vacuum defoamation is through 200 order filtering nets after 12 hours, and adopt dry-wet spinning, film-casting liquid temperature is 65 DEG C, air section height is 2 centimetres, core liquid adopts the dimethylformamide in water of 45wt%, and precipitation bath is the dimethylformamide in water of 30wt%, and coagulation bath temperature is 45 DEG C.Obtained hollow-fibre membrane internal-and external diameter is respectively 0.7/1.3mm, and pure water flux is 480l/m
2h.bar, mean pore size is 38nm, porosity 76%, and filament strength is 3.6N, unit elongation 136%.
Embodiment eight
Select the polyvinylidene difluoride (PVDF) waste silk produced in spinning process to soak 24 hours in the chlorine bleach liquor of 2000ppm, then use 40 DEG C of clear water rinsings 2 hours, put into baking oven 95 DEG C of dryings after 4 hours water ratio be 0.7%.Waste silk complete for drying is dissolved in dimethyl formamide according to the mass ratio of 1:1, heated and stirred 12 hours at 75 DEG C, then gel solidification in 60 DEG C of pure water is entered by 200 order centrifugings, by solidification after film liquid put into 60 DEG C of baking oven inner dryings after 12 hours after water ratio be 0.5%, it is broken, material after fragmentation enters forcing machine in 180 DEG C of extruding pelletizations, and obtaining diameter is 2.0mm, and length is the recovery polyvinylidene difluoride (PVDF) particle of 2.5mm.
Film-casting liquid configures according to following proportioning: 15wt% polyvinylidene difluoride (PVDF) (be entirely and reclaim particle), 7wt% polyvinyl alcohol, 8wt% polyoxyethylene glycol, 5wt% polyvinylpyrrolidone, 1.0wt% lithium nitrate, 64wt%N-methyl-2-pyrrolidone, above material is added in dissolution kettle, 70 DEG C are stirred 18 hours, vacuum defoamation after 12 hours through 200 order filtering nets, adopt dry-wet spinning, film-casting liquid temperature is 65 DEG C, air section height is 3 centimetres, core liquid adopts the dimethylacetamide amine aqueous solution of 40wt%, precipitation bath is the dimethylacetamide amine aqueous solution of 28wt%, coagulation bath temperature is 45 DEG C.Obtained hollow-fibre membrane internal-and external diameter is respectively 0.7/1.3mm, and pure water flux is 1420l/m
2h.bar, mean pore size is 98nm, porosity 88%, and filament strength is 3.2N, unit elongation 106%.
Embodiment nine
Select in casting cycle cut end produce polyvinylidene difluoride (PVDF) waste silk soak 18 hours in the chlorine bleach liquor of 2000ppm, then use 40 DEG C of clear water rinsings 2 hours, put into baking oven 75 DEG C of dryings after 6 hours water ratio be 1.0%.Waste silk complete for drying is dissolved in dimethyl formamide according to the mass ratio of 1:1, heated and stirred 12 hours at 75 DEG C, then gel solidification in 60 DEG C of pure water is entered by 200 order centrifugings, by solidification after film liquid put into 75 DEG C of baking oven inner dryings after 10 hours water ratio be 0.4%, then broken, material after fragmentation enters forcing machine in 190 DEG C of extruding pelletizations, and obtaining diameter is 1.0mm, and length is the recovery polyvinylidene difluoride (PVDF) particle of 1.5mm.
Film-casting liquid configures according to following proportioning: (50wt% is for reclaiming particle for 32wt% polyvinylidene difluoride (PVDF), 50wt% is polyvinylidene difluoride (PVDF) virgin material), 2wt% polyvinylpyrrolidone, 2.5wt% polyoxyethylene glycol, 0.5wt% lithium chloride, 63wt% dimethyl formamide, above material is added in dissolution kettle, 70 DEG C are stirred 15 hours, vacuum defoamation after 12 hours through 200 order filtering nets, adopt dry-wet spinning, film-casting liquid temperature is 65 DEG C, air section height is 4 centimetres, core liquid adopts the dimethylacetamide amine aqueous solution of 45wt%, precipitation bath is the dimethylacetamide amine aqueous solution of 30wt%, coagulation bath temperature is 45 DEG C.Obtained hollow-fibre membrane internal-and external diameter is respectively 0.7/1.3mm, and pure water flux is 240l/m
2h.bar, mean pore size is 22nm, porosity 71%, and filament strength is 4.8N, unit elongation 148%.
Embodiment ten
Select polyvinylidene difluoride (PVDF) that Sewage Plant changes to give up film clear water rinsed clean, soak 12 hours in the hydrochloric acid soln of 0.2wt%, then 40 DEG C of immersion treatment 12 hours in 2000ppm clorox+0.1wt% sodium hydroxide solution, use 40 DEG C of clear water rinsings 3 hours again, put into baking oven 80 DEG C of dryings after 5 hours water ratio be 1.1 %.Waste silk complete for drying is dissolved in dimethyl formamide according to the mass ratio of 1:1, heated and stirred 12 hours at 75 DEG C, then gel solidification in 60 DEG C of pure water is entered by 200 order centrifugings, by solidification after film liquid put into 90 DEG C of baking oven inner dryings after 6 hours water ratio be 0.3%, then broken, material after fragmentation enters forcing machine in 200 DEG C of extruding pelletizations, and obtaining diameter is 1.5mm, and length is the recovery polyvinylidene difluoride (PVDF) particle of 1.8mm.
Film-casting liquid configures according to following proportioning: (70wt% is for reclaiming particle for 20wt% polyvinylidene difluoride (PVDF), 30wt% is polyvinylidene difluoride (PVDF) virgin material), 6wt% polyvinylpyrrolidone, 8wt% polyoxyethylene glycol, 1.2wt% lithium chloride, 64.8wt% N,N-DIMETHYLACETAMIDE, above material is added in dissolution kettle, 70 DEG C are stirred 12 hours, vacuum defoamation after 12 hours through 200 order filtering nets, adopt dry-wet spinning, film-casting liquid temperature is 65 DEG C, air section height is 3 centimetres, core liquid adopts the dimethylformamide in water of 45wt%, precipitation bath is the dimethylformamide in water of 30wt%, coagulation bath temperature is 45 DEG C.Obtained hollow-fibre membrane internal-and external diameter is respectively 0.7/1.3mm, and pure water flux is 520l/m
2h.bar, mean pore size is 46nm, porosity 78%, and filament strength is 3.5N, unit elongation 126%.
Embodiment 11
Select polyvinylidene difluoride (PVDF) that Sewage Plant changes to give up film clear water rinsed clean, soak 24 hours in the citric acid solution of 1.5wt%, then 40 DEG C of immersion treatment 24 hours in 2000ppm clorox+0.1wt% sodium hydroxide solution, use 40 DEG C of clear water rinsings 4 hours again, put into baking oven 70 DEG C of dryings after 7 hours water ratio be 0.9 %.Waste silk complete for drying is dissolved in dimethyl formamide according to the mass ratio of 1:1, heated and stirred 12 hours at 75 DEG C, then gel solidification in 60 DEG C of pure water is entered by 200 order centrifugings, by solidification after film liquid put into 85 DEG C of baking oven inner dryings after 8 hours water ratio be 0.3%, then broken, material after fragmentation enters forcing machine in 195 DEG C of extruding pelletizations, and obtaining diameter is 1.2mm, and length is the recovery polyvinylidene difluoride (PVDF) particle of 1.5mm.
Film-casting liquid configures according to following proportioning: (60wt% is for reclaiming particle for 24wt% polyvinylidene difluoride (PVDF), 40wt% is polyvinylidene difluoride (PVDF) virgin material), 5wt% polyvinylpyrrolidone, 8wt% polyoxyethylene glycol, 1.2wt% lithium chloride, 61.8wt% N,N-DIMETHYLACETAMIDE, above material is added in dissolution kettle, 70 DEG C are stirred 12 hours, vacuum defoamation after 12 hours through 200 order filtering nets, adopt dry-wet spinning, film-casting liquid temperature is 65 DEG C, air section height is 2 centimetres, core liquid adopts the dimethylformamide in water of 40wt%, precipitation bath is the dimethylformamide in water of 30wt%, coagulation bath temperature is 45 DEG C.Obtained hollow-fibre membrane internal-and external diameter is respectively 0.7/1.3mm, and pure water flux is 410l/m
2h.bar, mean pore size is 32nm, porosity 73%, and filament strength is 3.8N, unit elongation 137%.
This specific embodiment is only explanation of the invention; it is not limitation of the present invention; those skilled in the art can make to the present embodiment the amendment not having creative contribution as required after reading this specification sheets, as long as but be all subject to the protection of patent law in right of the present invention.
Claims (10)
1. a Pvdf Microporous Hollow Fiber Membrane waste silk recoverying and utilizing method, is characterized in that comprising following waste silk pre-treatment step successively:
A. clean: comprise the waste silk cleaning produced in manufacturing processed and/or the waste silk cleaning of replacing Sewage Plant;
Wherein, the waste silk cleaning produced is comprised first use 1500-2500ppm 35-45 DEG C of clorox immersion treatment 12-24 hour in manufacturing processed, then at 30-50 DEG C of washing 2-4 hour, then little of waste silk water ratio≤1.5% at 60-95 DEG C of dry 4-8;
The waste silk cleaning of replacing Sewage Plant comprises pickling 12-24 hour after clear water rinsing, and pickling acid used is 0.15-0.35wt% hydrochloric acid or 1-2wt% citric acid; Then use 1500-2500ppm clorox and 0.05-0.15wt% sodium hydroxide mixed solution at 35-45 DEG C of immersion treatment 12-24 hour, then with 30-50 DEG C of washing 2-4 hour, then little of waste silk water ratio≤1.5% at 60-95 DEG C of dry 4-8;
B. dissolve and gel solidification: waste silk and the dimethyl formamide after cleaning is mixed being incorporated in 70-80 DEG C and dissolving according to mass ratio 1:0.8-1.2 proportioning, then enter gel solidification in 50-70 DEG C of pure water after the centrifuging of 150-250 order;
C. dry: gained gel solidification thing is little of water ratio≤0.5% at 60-95 DEG C of dry 6-12;
D. pulverize;
E. granulation: 180-200 DEG C extruding pelletization, obtains the polyvinylidene difluoride (PVDF) reclaimed materials grain of particle size diameter 0.5-2mm, length 0.5-2.5mm.
2. a kind of Pvdf Microporous Hollow Fiber Membrane waste silk recoverying and utilizing method according to claim 1, it is characterized in that: the waste silk cleaning produced in manufacturing processed is comprised and first uses 1500-2500ppm 35-45 DEG C of clorox immersion treatment 12-24 hour, then at 30-50 DEG C of washing 2-4 hour, then little of waste silk water ratio≤1.5% at 60-95 DEG C of dry 4-8; Then waste silk and the dimethyl formamide after cleaning is mixed according to mass ratio 1:0.8-1.2 proportioning and is incorporated in 70-80 DEG C and dissolves, then after centrifuging in water gel solidification.
3. a kind of Pvdf Microporous Hollow Fiber Membrane waste silk recoverying and utilizing method according to claim 1; it is characterized in that: the waste silk cleaning of replacing Sewage Plant comprises pickling 12-24 hour after clear water rinsing, pickling acid used is 0.15-0.35wt% hydrochloric acid or 1-2wt% citric acid; Then use 1500-2500ppm clorox and 0.05-0.15wt% sodium hydroxide mixed solution at 35-45 DEG C of immersion treatment 12-24 hour, then with 30-50 DEG C of washing 2-4 hour, then little of waste silk water ratio≤1.5% at 60-95 DEG C of dry 4-8; Then waste silk and the dimethyl formamide after cleaning is mixed according to mass ratio 1:0.8-1.2 proportioning and is incorporated in 70-80 DEG C and dissolves, then after centrifuging in 50-70 DEG C of pure water gel solidification.
4. a kind of Pvdf Microporous Hollow Fiber Membrane waste silk recoverying and utilizing method according to any one of claim 1-3, is characterized in that: described waste silk recoverying and utilizing method also comprises the polyvinylidene difluoride (PVDF) reclaimed materials grain utilizing waste silk pretreatment process to obtain and prepares Pvdf Microporous Hollow Fiber Membrane;
Wherein preparation liquid comprises polyvinylidene difluoride (PVDF), pore-creating agent, low molecular weight additives and solvent; Described polyvinylidene difluoride (PVDF) accounts for the 15-35% of described preparation liquid quality;
Described pore-creating agent accounts for the 2-20wt% of described preparation liquid quality;
Described low molecular weight additives accounts for the 0.5-1.5wt% of described preparation liquid quality;
Described polyvinylidene difluoride (PVDF) reclaimed materials grain quality accounts for the 50-100wt% of polyvinylidene difluoride (PVDF) total mass in preparation liquid.
5. a kind of Pvdf Microporous Hollow Fiber Membrane waste silk recoverying and utilizing method according to claim 4, is characterized in that: described pore-creating agent comprise in polyvinylpyrrolidone, polyoxyethylene glycol or polyvinyl alcohol one or more.
6. a kind of Pvdf Microporous Hollow Fiber Membrane waste silk recoverying and utilizing method according to claim 5, is characterized in that: described low molecular weight additives comprise in lithium chloride, lithium nitrate, SODIUMNITRATE, magnesium chloride, water, glycerol and ethylene glycol one or more.
7. a kind of Pvdf Microporous Hollow Fiber Membrane waste silk recoverying and utilizing method according to claim 6, is characterized in that: described solvent comprise in dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO) and triethyl phosphate one or more.
8. a kind of Pvdf Microporous Hollow Fiber Membrane waste silk recoverying and utilizing method according to claim 7, it is characterized in that: described Pvdf Microporous Hollow Fiber Membrane preparation method comprises and is added in dissolution kettle by described preparation liquid, 60-80 DEG C is stirred 10-20 hour, through filtering net after vacuum defoamation 10-15 hour, adopt dry-wet spinning, film-casting liquid temperature is 60-70 DEG C, air section height is 1-4 centimetre, core liquid adopts the dimethylformamide in water of 40-50wt%, precipitation bath is the dimethylformamide in water of 25-35wt%, and coagulation bath temperature is 40-50 DEG C.
9. a kind of Pvdf Microporous Hollow Fiber Membrane waste silk recoverying and utilizing method according to claim 8, is characterized in that: described filtering net adopts 150-250 order.
10. a kind of Pvdf Microporous Hollow Fiber Membrane waste silk recoverying and utilizing method according to claim 8, is characterized in that: the hollow-fibre membrane the key technical indexes that described Pvdf Microporous Hollow Fiber Membrane preparation method obtains is as follows: film silk aperture 20-100nm; Pure water flux is 200-1500 L/m
2hbar25 DEG C; Porosity is 70%-90%; Monofilament pulling force 3-5N; Stretch percentage elongation is 100-150%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106589447A (en) * | 2016-12-06 | 2017-04-26 | 天津工业大学 | Treating method and recycling method for waste PVDF hollow fiber membranes |
| CN108690415A (en) * | 2017-02-17 | 2018-10-23 | 天津工业大学 | A method of preparing paint for lines on road surface with waste and old Pvdf Microporous Hollow Fiber Membrane |
| CN109092066A (en) * | 2018-10-08 | 2018-12-28 | 湖北中泉环保技术有限公司 | A kind of ultrafiltration membrane using useless ultrafiltration membrane filaments preparation |
| CN110253789A (en) * | 2019-06-13 | 2019-09-20 | 天津汉晴环保科技有限公司 | A kind of pvdf membrane silk waste silk recycling system of processing |
| CN114875500A (en) * | 2022-04-30 | 2022-08-09 | 江苏阿代尔新材料科技有限公司 | Production process of waste silk regenerated polyester filament yarn |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101422700A (en) * | 2007-10-31 | 2009-05-06 | 中国石油化工股份有限公司 | Chemical cleaning method of ultrafiltration membrane |
| CN101422707A (en) * | 2008-11-26 | 2009-05-06 | 北京碧水源膜科技有限公司 | Scratch tape liner type polyvinylidene fluoride hollow fiber membrane |
| CN101422708A (en) * | 2008-11-26 | 2009-05-06 | 北京碧水源膜科技有限公司 | Recovery method of polyvinylidene fluoride hollow fiber membrane |
-
2014
- 2014-12-02 CN CN201410716155.5A patent/CN104479167B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101422700A (en) * | 2007-10-31 | 2009-05-06 | 中国石油化工股份有限公司 | Chemical cleaning method of ultrafiltration membrane |
| CN101422707A (en) * | 2008-11-26 | 2009-05-06 | 北京碧水源膜科技有限公司 | Scratch tape liner type polyvinylidene fluoride hollow fiber membrane |
| CN101422708A (en) * | 2008-11-26 | 2009-05-06 | 北京碧水源膜科技有限公司 | Recovery method of polyvinylidene fluoride hollow fiber membrane |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106589447A (en) * | 2016-12-06 | 2017-04-26 | 天津工业大学 | Treating method and recycling method for waste PVDF hollow fiber membranes |
| CN108690415A (en) * | 2017-02-17 | 2018-10-23 | 天津工业大学 | A method of preparing paint for lines on road surface with waste and old Pvdf Microporous Hollow Fiber Membrane |
| CN109092066A (en) * | 2018-10-08 | 2018-12-28 | 湖北中泉环保技术有限公司 | A kind of ultrafiltration membrane using useless ultrafiltration membrane filaments preparation |
| CN110253789A (en) * | 2019-06-13 | 2019-09-20 | 天津汉晴环保科技有限公司 | A kind of pvdf membrane silk waste silk recycling system of processing |
| CN110253789B (en) * | 2019-06-13 | 2023-11-28 | 天津汉晴环保科技有限公司 | PVDF membrane silk waste silk recovery processing system |
| CN114875500A (en) * | 2022-04-30 | 2022-08-09 | 江苏阿代尔新材料科技有限公司 | Production process of waste silk regenerated polyester filament yarn |
| CN114875500B (en) * | 2022-04-30 | 2023-08-11 | 江苏阿代尔新材料科技有限公司 | Production process of waste silk regenerated polyester filament yarns |
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