CN106139931A - A kind of hollow-fibre membrane going heavy metal ion and preparation method thereof - Google Patents
A kind of hollow-fibre membrane going heavy metal ion and preparation method thereof Download PDFInfo
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- CN106139931A CN106139931A CN201510175833.6A CN201510175833A CN106139931A CN 106139931 A CN106139931 A CN 106139931A CN 201510175833 A CN201510175833 A CN 201510175833A CN 106139931 A CN106139931 A CN 106139931A
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Abstract
It is an object of the invention to provide a kind of Pvdf Microporous Hollow Fiber Membrane and preparation method thereof, this hollow-fibre membrane is made up of following raw material, parts by weight are Kynoar 15～20 parts, polyacrylonitrile 18～20 parts, polyvinylpyrrolidone 15～25 parts, attapulgite modified 10～20 parts, styrene 1～5 part, ammonium persulfate 1～3 part, solvent 100～155 parts, additive 3～5 parts；Wherein attapulgite modified preparation method is: will purify attapulgite and add in hydrochloric acid solution, being heated to 80 DEG C after stirring, carrying out sonic oscillation after stirring 1～3h, after 0.5h, suction filtration removes liquid, with distilled water by filtrate washing to neutral, grind after being dried and obtain modified attapulgite scholar.The hollow-fibre membrane using the method to prepare has the ability of heavy metal ion, and intensity is high, good hydrophilic property, and preparation technology is simple, and low cost is suitable for industrialized production.
Description
Technical field
The present invention relates to hollow-fibre membrane, offer is a kind of especially has the poly-inclined of heavy metal ion ability
PVF hollow-fibre membrane and preparation method thereof.
Background technology
Hollow-fibre membrane (hollow fiber membrane) is one outer image threadiness, has self-supporting
The film of effect.It is the one of anisotropic membrane, and its compacted zone can be located at the outer surface of fiber (such as reverse osmosis
Permeable membrane), it is possible to it is positioned at the inner surface (such as microfiltration membranes, NF membrane and milipore filter) of fiber.Hollow-fibre membrane
It is used as membrane for water treatment owing to having the many advantages such as loading density height, self-supporting, at present widely
It is applied to the fields such as Industrial Wastewater Treatment, sewage reuse, seawater desalinization pretreatment.Doughnut
Film mainly produces raw material to be had Kynoar (PVDF), polyether sulfone (PES), polysulfones (PS), gathers
The macromolecules such as acrylonitrile (PAN), polyvinyl chloride (PVC), polypropylene (PP), polyethylene (PE)
Material, due to the difference of material, the hollow-fibre membrane of production is distinct.PVDF crystallizes as one
The high polymer of type, headed by the advantages such as its fine corrosion resistance, mechanical strength height, radiation hardness become
Select membrane material.
The contaminated wastewater containing heavy metal ion in recent years is on the rise, exploitation have Adsorption of Heavy Metals from
The hollow-fibre membrane of sub-ability becomes study hotspot, in addition, Pvdf Microporous Hollow Fiber Membrane is using
During repeatedly to stand great deal running water in High-Pressure Water and cleaning process, air-flow disturbance impact,
Easily there is the problems such as fracture distress, and then reduce treatment effeciency, affect result.Water flux is also
Being the major criterion weighing membrane for water treatment, Kynoar is the conventional raw material of hollow-fibre membrane, its tool
Have extremely strong hydrophobicity, the material such as easy adhesion protein of membrane for water treatment being made from thus block fiber
Film, therefore, need to carry out hydrophilic modification to Pvdf Microporous Hollow Fiber Membrane.But, have at present
Adsorption of Heavy Metal Ions ability, and be provided simultaneously with in the Kynoar of high intensity, high water flux feature
Hollow fiber film but rarely has report.
Content of the invention
It is an object of the invention to provide a kind of Pvdf Microporous Hollow Fiber Membrane and preparation method thereof, adopt
There is with the hollow-fibre membrane that the method prepares the ability of heavy metal ion, and intensity is high, parent
Aqueous good, preparation technology is simple, low cost, is suitable for industrialized production.
The present invention specifically provides a kind of hollow-fibre membrane with heavy metal ion ability, its feature
Being, this hollow-fibre membrane is made up of following raw material, and parts by weight are Kynoar 15～20 parts,
Polyacrylonitrile 18～20 parts, polyvinylpyrrolidone 15～25 parts, attapulgite modified 10～20 parts,
Styrene 1～5 part, ammonium persulfate 1～3 part, solvent 100～155 parts, additive 3～5 parts；Optimum
Proportioning is Kynoar 15 parts, polyacrylonitrile 18 parts, polyvinylpyrrolidone 20 parts, modified recessed
15 parts of convex rod soil, styrene 1 part, ammonium persulfate 3 parts, diphenyl sulphone (DPS) 100 parts, zinc chloride 3 parts.
Wherein attapulgite modified preparation method is: first will purify attapulgite and add hydrochloric acid solution
In, it is heated to 80 DEG C after stirring, after stirring 1～3h, carry out sonic oscillation, after 0.5h, suction filtration removes liquid,
With distilled water by filtrate washing to neutrality, grinding after being dried obtains attapulgite modified.
The hollow-fibre membrane going heavy metal ion of the present invention, it is characterised in that: described additive is
Silica, cupric oxide, lithium chloride, sodium chloride, magnesium chloride, zinc chloride one or more.
The hollow-fibre membrane going heavy metal ion of the present invention, it is characterised in that: also can be in described
It is filled with glass fibre on hollow fiber film inwall, to improve doughnut film strength, described glass fibers
The diameter of dimension is preferably 0.5～5 μm.
The hollow-fibre membrane going heavy metal ion of the present invention, it is characterised in that: in described raw material also
Poly-second containing the methylacryoyloxyethyl-n-hexadecyl-ditallowdimethyl ammonium bromide of 5～9 parts and 2～5 parts
Glycol, to improve the contamination resistance of hollow-fibre membrane.
The preparation method of the hollow-fibre membrane of heavy metal ion is gone, its feature described in present invention also offers
Being, concrete preparation method is:
(1), first will purify attapulgite to add in hydrochloric acid solution, after stirring, be heated to 80 DEG C,
Carrying out sonic oscillation after stirring 1～3h, after 0.5h, suction filtration removes liquid, with distilled water by filtrate washing to neutrality,
Grinding after drying obtains attapulgite modified, standby；
(2), all raw materials in addition to attapulgite modified are added in reactor and (to require as with stirring
Mix and stir the reactor of heater), dissolve stirring and make preparation liquid, filter deaeration；By modified attapulgite
In preparation liquid after soil addition deaeration, set aside for use after stirring sonic oscillation；
(3), introduce glass fibre in preparation liquid, and by wet spinning by preparation liquid and glass fibers
Dimension ejection from annular spinning head together；
(4) fiber, spraying step (3) immerses in coagulating bath and is frozen into hollow-fibre membrane；
(5), step (4) gained hollow-fibre membrane is put into glycerin solution soaks and protect hole, then
Put into water soaks and remove excess of solvent, after drying, obtain going the hollow-fibre membrane of heavy metal ion.
Wherein, described solvent is dimethyl sulfoxide (DMSO), diphenyl sulphone (DPS), phenol, dimethylformamide, diformazan
One or more of yl acetamide.Described coagulating bath is water, ethanol, phenol, cyclohexanone, four chloroethenes
One in alkane, dimethyl sulfoxide (DMSO).
Beneficial effects of the present invention:
(1), attapulgite modified by adding, make Pvdf Microporous Hollow Fiber Membrane of the present invention
Possess heavy ion adsorption capacity, and by the mass ratio of rational solvent and additive, make to be obtained
Hollow-fibre membrane possesses high intensity and high water-flowing amount.
(2), Pvdf Microporous Hollow Fiber Membrane pure water flux of the present invention is higher than 3000L m-2·h-1,
There is excellent hydrophily, thus reduce the suction-operated to materials such as albumen for the hollow-fibre membrane, enter
And avoid the blocking of film.
(3), the present invention with the addition of glass fibre in Pvdf Microporous Hollow Fiber Membrane, thus strengthens
Fiber film strength, and then avoid the problems such as fracture distress, improve the use of hollow-fibre membrane
Life-span.
(4), Pvdf Microporous Hollow Fiber Membrane of the present invention also has superelevation antifouling property, energy
Enough prevent adhesion in film for the microorganism and growth, thus reduce hollow-fibre membrane in use
Sterilization wash number, reduces the use cost of film.
Detailed description of the invention
The preparation process of embodiment of the present invention Pvdf Microporous Hollow Fiber Membrane is:
(1), 50g is purified in the hydrochloric acid solution that attapulgite adds 500mL, 1mol/L, stirring
Being heated to 80 DEG C after 10min, carrying out sonic oscillation after stirring 1h, after sonic oscillation 0.5h, suction filtration removes liquid,
With distilled water by filtrate washing to neutrality, grinding after being dried obtains attapulgite modified, standby；
(2), all raw materials in addition to attapulgite modified are added in reactor, dissolve stirring and make
Preparation liquid, filters deaeration；By in the preparation liquid after attapulgite modified addition deaeration, stirring is simultaneously ultrasonic
Set aside for use after vibration；
(3), introduce glass fibre in preparation liquid, and by wet spinning by preparation liquid and glass fibers
Dimension ejection from annular spinning head together；
(4) fiber, spraying step (3) immerses in coagulating bath and is frozen into hollow-fibre membrane；
(5), step (4) gained hollow-fibre membrane is put into glycerin solution soaks and protect hole, then
Put into water soaks and remove excess of solvent, after drying, obtain going the hollow-fibre membrane of heavy metal ion.
Embodiment 1
The parts by weight preparing Pvdf Microporous Hollow Fiber Membrane raw material are:
Kynoar 15 parts, polyacrylonitrile 18 parts, polyvinylpyrrolidone 20 parts, modified concavo-convex
15 parts of rod soil, styrene 1 part, ammonium persulfate 3 parts, diphenyl sulphone (DPS) 100 parts, zinc chloride 3 parts.
Embodiment 2
The parts by weight preparing Pvdf Microporous Hollow Fiber Membrane raw material are:
Kynoar 18 parts, polyacrylonitrile 20 parts, polyvinylpyrrolidone 25 parts, modified concavo-convex
10 parts of rod soil, styrene 3 parts, ammonium persulfate 1 part, phenol 120 parts, silica 5 parts.
Embodiment 3
The parts by weight preparing Pvdf Microporous Hollow Fiber Membrane raw material are:
Kynoar 20 parts, polyacrylonitrile 18 parts, polyvinylpyrrolidone 15 parts, modified concavo-convex
20 parts of rod soil, styrene 5 parts, PEG400 2 parts, methylacryoyloxyethyl-n-hexadecyl-two
Methyl bromide ammonium 9 parts, ammonium persulfate 3 parts, diphenyl sulphone (DPS) 100 parts, zinc chloride 3 parts.
Embodiment 4
The parts by weight preparing Pvdf Microporous Hollow Fiber Membrane raw material are:
Kynoar 15 parts, polyacrylonitrile 18 parts, polyvinylpyrrolidone 20 parts, modified concavo-convex
15 parts of rod soil, styrene 1 part, PEG600 5 parts, methylacryoyloxyethyl-n-hexadecyl-two
Methyl bromide ammonium 5 parts, ammonium persulfate 2 parts, dimethylformamide 100 parts, 3 parts of sodium chloride.
Embodiment 5
The parts by weight preparing Pvdf Microporous Hollow Fiber Membrane raw material are:
Kynoar 15 parts, polyacrylonitrile 19 parts, polyvinylpyrrolidone 20 parts, modified concavo-convex
20 parts of rod soil, styrene 1 part, PEG600 5 parts, methylacryoyloxyethyl-n-hexadecyl-two
Methyl bromide ammonium 5 parts, ammonium persulfate 2 parts, dimethylformamide 155 parts, 3 parts of sodium chloride.
Embodiment gained hollow-fibre membrane internal diameter is 0.1～2.0mm, and wall thickness is 0.1～0.5mm, aperture
50～300nm, at 0.1MPa is 25 DEG C, pure water flux is at 3000～3500lmh, intensity at 2～5N,
Porosity 80～90%.Gained hollow-fibre membrane is put into waste water (each heavy metal containing heavy metal ion
Content is shown in Table 1) in absorption 1 hour, experimental result is shown in Table 2.
Each content of beary metal (μ g/mL) in table 1 waste water
| Heavy metal | Cr | Cd | Cu | Pb | As | Hg |
| Concentration in waste water | 100 | 100 | 100 | 100 | 5.0 | 0.5 |
Table 2 hollow-fibre membrane adsorbs heavy metal ions in wastewater content (μ g/mL) after 1 hour
| Heavy metal | Cr6+ | Cd2+ | Cu2+ | Pb2+ | As3+ | Hg2+ |
| Embodiment 1 | 25 | 33 | 68 | 43 | 2.0 | 0.005 |
| Embodiment 2 | 34 | 46 | 65 | 48 | 3.0 | 0.011 |
| Embodiment 3 | 41 | 35 | 73 | 61 | 2.6 | 0.009 |
| Embodiment 4 | 40 | 51 | 62 | 53 | 2.1 | 0.015 |
| Embodiment 5 | 38 | 60 | 69 | 58 | 2.5 | 0.019 |
As shown in Table 1, hollow-fibre membrane of the present invention has superpower heavy-metal ion removal ability,
Wherein the ability of embodiment 1 gained hollow-fibre membrane heavy-metal ion removal is the strongest, and it is to mercury ion
Adsorption rate is up to 99%, can be used for selective removal mercury ion.
Above-described embodiment is only technology design and the feature that the present invention is described, its object is to allow and is familiar with this
The personage of item technology will appreciate that present disclosure and implements according to this, can not limit the present invention with this
Protection domain.All equivalences made according to spirit of the invention change or modify, and all should cover
Within protection scope of the present invention.
Claims (9)
1. the hollow-fibre membrane going heavy metal ion, it is characterized in that, this hollow-fibre membrane is made up of following raw material, and parts by weight are: Kynoar 15～20 parts, polyacrylonitrile 18～20 parts, polyvinylpyrrolidone 15～25 parts, attapulgite modified 10～20 parts, styrene 1～5 part, ammonium persulfate 1～3 part, solvent 100～155 parts, additive 3～5 parts；
Wherein attapulgite modified preparation method is: first will purify attapulgite and add in hydrochloric acid solution, being heated to 80 DEG C after stirring, carrying out sonic oscillation after stirring 1～3h, after 0.5h, suction filtration removes liquid, with distilled water by filtrate washing to neutrality, grinding after being dried obtains attapulgite modified.
2. according to the hollow-fibre membrane going heavy metal ion described in claim 1, it is characterised in that: described additive be silica, cupric oxide, potassium chloride, sodium chloride, magnesium chloride, zinc chloride one or more.
3. according to the hollow-fibre membrane going heavy metal ion described in claim 1 or 2, it is characterised in that: on described hollow-fibre membrane inwall, it is filled with glass fibre.
4. according to the hollow-fibre membrane going heavy metal ion described in claim 3, it is characterised in that: a diameter of 0.5～5 μm of described glass fibre.
5. according to the hollow-fibre membrane going heavy metal ion described in claim 1 or 4, it is characterised in that: possibly together with the polyethylene glycol of the methylacryoyloxyethyl-n-hexadecyl-ditallowdimethyl ammonium bromide of 5～9 parts and 2～5 parts in described raw material.
6. according to the hollow-fibre membrane going heavy metal ion described in claim 1 or 4, it is characterized in that, the parts by weight of described hollow-fibre membrane composition are: Kynoar 15 parts, polyacrylonitrile 18 parts, polyvinylpyrrolidone 20 parts, attapulgite modified 15 parts, styrene 1 part, ammonium persulfate 3 parts, diphenyl sulphone (DPS) 100 parts, zinc chloride 3 parts.
7. go the preparation method of the hollow-fibre membrane of heavy metal ion described in a claim 5, it is characterised in that concrete preparation method is:
(1), first will purify attapulgite to add in hydrochloric acid solution, and be heated to 80 DEG C after stirring, after stirring 1～3h, carry out sonic oscillation, after 0.5h, suction filtration removes liquid, with distilled water by filtrate washing to neutrality, grinding after being dried obtains attapulgite modified, standby；
(2), all raw materials in addition to attapulgite modified are added in reactor, dissolve stirring and make preparation liquid, filter deaeration；By in the preparation liquid after attapulgite modified addition deaeration, stir and set aside for use after sonic oscillation；
(3), introduce glass fibre in preparation liquid, and by wet spinning ejection from annular spinning head together with glass fibre by preparation liquid；
(4) fiber, spraying step (3) immerses in coagulating bath and is frozen into hollow-fibre membrane；
(5), step (4) gained hollow-fibre membrane is put into glycerin solution soaks and protect hole, be then placed in water soaking and remove excess of solvent, after drying, obtain going the hollow-fibre membrane of heavy metal ion.
8. the preparation method according to the hollow-fibre membrane going heavy metal ion described in claim 7, it is characterised in that: described solvent be dimethyl sulfoxide (DMSO), diphenyl sulphone (DPS), phenol, dimethylformamide, dimethylacetylamide one or more.
9. the preparation method according to the hollow-fibre membrane going heavy metal ion described in claim 7, it is characterised in that: described coagulating bath is water, ethanol, phenol, cyclohexanone, tetrachloroethanes, the one in dimethyl sulfoxide (DMSO).
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510175833.6A CN106139931A (en) | 2015-04-15 | 2015-04-15 | A kind of hollow-fibre membrane going heavy metal ion and preparation method thereof |
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| CN201510175833.6A CN106139931A (en) | 2015-04-15 | 2015-04-15 | A kind of hollow-fibre membrane going heavy metal ion and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109554221A (en) * | 2017-09-27 | 2019-04-02 | 广西南宁胜祺安科技开发有限公司 | A method of utilizing ultraviolet-magnesium silicate gel column joint removing aflatoxin |
| CN113134336A (en) * | 2021-04-16 | 2021-07-20 | 浙江凯圣氟化学有限公司 | Method for removing arsenic and free chlorine in hydrochloric acid |
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| CN103055714A (en) * | 2013-01-14 | 2013-04-24 | 北京碧水源膜科技有限公司 | Method for preparing hydrophilic electrical charge separation film by using one-step method as well as product and application thereof |
| CN103191655A (en) * | 2013-04-01 | 2013-07-10 | 杭州求是膜技术有限公司 | Composite hollow fiber film and preparation method thereof |
| JP2013173139A (en) * | 2013-04-09 | 2013-09-05 | Asahi Kasei Chemicals Corp | Manufacturing method of porous hollow fiber membrane |
| CN104174303A (en) * | 2014-08-26 | 2014-12-03 | 云南云天化股份有限公司 | Enhanced hollow polyvinylidene fluoride fiber ultrafiltration membrane and preparation method thereof |
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2015
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102527261A (en) * | 2011-08-31 | 2012-07-04 | 天津工业大学 | Heavy metal ion adsorption type polyvinylidene fluoride (PVDF) hollow fiber membrane |
| CN103055714A (en) * | 2013-01-14 | 2013-04-24 | 北京碧水源膜科技有限公司 | Method for preparing hydrophilic electrical charge separation film by using one-step method as well as product and application thereof |
| CN103191655A (en) * | 2013-04-01 | 2013-07-10 | 杭州求是膜技术有限公司 | Composite hollow fiber film and preparation method thereof |
| JP2013173139A (en) * | 2013-04-09 | 2013-09-05 | Asahi Kasei Chemicals Corp | Manufacturing method of porous hollow fiber membrane |
| CN104174303A (en) * | 2014-08-26 | 2014-12-03 | 云南云天化股份有限公司 | Enhanced hollow polyvinylidene fluoride fiber ultrafiltration membrane and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109554221A (en) * | 2017-09-27 | 2019-04-02 | 广西南宁胜祺安科技开发有限公司 | A method of utilizing ultraviolet-magnesium silicate gel column joint removing aflatoxin |
| CN113134336A (en) * | 2021-04-16 | 2021-07-20 | 浙江凯圣氟化学有限公司 | Method for removing arsenic and free chlorine in hydrochloric acid |
| CN113134336B (en) * | 2021-04-16 | 2022-08-23 | 浙江凯圣氟化学有限公司 | Method for removing arsenic and free chlorine in hydrochloric acid |
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