CN105664728A - Filter element, manufacturing method for same, modified filter membrane preparation method, water filter device and application thereof - Google Patents
Filter element, manufacturing method for same, modified filter membrane preparation method, water filter device and application thereof Download PDFInfo
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- CN105664728A CN105664728A CN201610132480.6A CN201610132480A CN105664728A CN 105664728 A CN105664728 A CN 105664728A CN 201610132480 A CN201610132480 A CN 201610132480A CN 105664728 A CN105664728 A CN 105664728A
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- filter
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- filter core
- water
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- 239000012528 membrane Substances 0.000 title claims abstract description 366
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 27
- 230000004048 modification Effects 0.000 claims abstract description 59
- 238000012986 modification Methods 0.000 claims abstract description 59
- 239000010410 layer Substances 0.000 claims description 123
- 239000004743 Polypropylene Substances 0.000 claims description 66
- 238000001914 filtration Methods 0.000 claims description 66
- 229920000742 Cotton Polymers 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 57
- 239000000178 monomer Substances 0.000 claims description 53
- 238000001338 self-assembly Methods 0.000 claims description 42
- 239000002346 layers by function Substances 0.000 claims description 34
- 238000005538 encapsulation Methods 0.000 claims description 26
- 241000894006 Bacteria Species 0.000 claims description 19
- -1 polypropylene Polymers 0.000 claims description 18
- 230000000844 anti-bacterial effect Effects 0.000 claims description 16
- 229920002521 macromolecule Polymers 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- 150000001450 anions Chemical class 0.000 claims description 13
- 238000001179 sorption measurement Methods 0.000 claims description 13
- 230000009881 electrostatic interaction Effects 0.000 claims description 12
- 230000005855 radiation Effects 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- 206010034960 Photophobia Diseases 0.000 claims description 9
- 208000013469 light sensitivity Diseases 0.000 claims description 9
- 229920001155 polypropylene Polymers 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 5
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- 230000008569 process Effects 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 20
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- 238000010521 absorption reaction Methods 0.000 description 11
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- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 230000001235 sensitizing effect Effects 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
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- 238000005406 washing Methods 0.000 description 8
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- 238000010586 diagram Methods 0.000 description 7
- 229920001223 polyethylene glycol Polymers 0.000 description 7
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 6
- 210000002469 basement membrane Anatomy 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000003456 ion exchange resin Substances 0.000 description 6
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- 229910021645 metal ion Inorganic materials 0.000 description 6
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical class [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 230000003373 anti-fouling effect Effects 0.000 description 4
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- 229910052742 iron Inorganic materials 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
- 229920000447 polyanionic polymer Polymers 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000003651 drinking water Substances 0.000 description 3
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- 238000007873 sieving Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
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- 229910021641 deionized water Inorganic materials 0.000 description 2
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- 229920000578 graft copolymer Polymers 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229940059939 kayexalate Drugs 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
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- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 102000035195 Peptidases Human genes 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
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- 229920008285 Poly(ether ketone) PEK Polymers 0.000 description 1
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- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/24—Dialysis ; Membrane extraction
- B01D61/28—Apparatus therefor
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Urology & Nephrology (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a filter element, a manufacturing method for the same, a modified filter membrane preparation method, a water filter device and application thereof. The filter element is applied to a water filter device and comprises at least one modified filter membrane, wherein the surface of the filter membrane presents a pre-set charge property, so that the water is filtered by virtue of the electrostatic effect of the charges, the surface modification is carried out on the modified filter membrane, and higher filter precision and higher screening performance to ions are obtained.
Description
Technical field
The present invention relates to water purifier field, further, relate to filter core and manufacture method, modified filter membranes preparation sideMethod and water treatment plant and application thereof.
Background technology
Water is Source of life, along with the raising of people's living standard, more and more payes attention to healthy water problem. And it is cleanHydrophone/water filter is a kind of important purifier being widely used growing up in the last few years. Ultrafiltration is cleanHydrophone is the wherein a kind of purifier with superior function developing at present.
Ultra-filtration water purifier, adopts hyperfiltration technique water to be carried out to the equipment of purified treatment. With other purifierDifference is, in ultra-filtration water purifier, conventionally uses and has a kind of milipore filter. Ultrafiltration is that one is utilized membrane separation technique sievePoint process, taking the pressure differential of film both sides as driving force, taking milipore filter as filter medium, under certain pressure,When stoste flows through film when surface, the many tiny micropore gathering in milipore filter surface only allows to be less than preliminary dimensionMolecule sees through, and the material that in stoste, volume is greater than film surface apertures is trapped within the liquid feeding side of film, thereby realThe now purification to stoste, separation and concentrated object.
In the multistage filtering layer that the filter core of existing ultra-filtration water purifier adopts, conventionally have 1 to 2 grade of meeting and selectPP (polypropylene) cotton fiber and/or milipore filter. The effect of fibrous filter layer is mainly that former water is carried out to tentatively mistakeFilter, removes compared with coarse granule impurity, dirt, colloid, suspended material etc., and the effect of milipore filter is mainly to removeSmall size impurity, as impurity such as bacterium, iron rust, colloid and organic matters. No matter be PP cotton or ultrafiltrationThe filter core that film is made, its principle adopting is all the principle based on adsorption filtration, only by the aperture size of filmScreen.
PP cotton based on adsorption filtration principle or milipore filter during as filter element of water purifier, have numerous unfavorable factors.
First, in adsorption filtration process, the impurity that can sieve depends primarily on the aperture of film, aperture largeThe little precision that determines screening. And aperture is less, higher for the performance requirement of material, and at screening impurityOr when harmful ion, need to ensure hydrone flux, make film there is good permeability, and existing skill simultaneouslyArt haves much room for improvement aperture size aspect on the one hand, and the balance of screening precision and hydrone flux aspect is considered less.
Secondly, because existing filter core is only that the mode of sieving by absorption is filtered, therefore, various assortedMatter all can be piled up in filter core, and is attached on PP cotton or milipore filter. On the one hand, make the use of filter coreLife-span is very short, conventionally only has about 3 months to half a year; On the other hand, the method for this absorption causes filter core assortedMatter cannot be cleaned utilization again, and the wasting of resources is more.
The 3rd, traditional filter core antifouling property is poor, and in the process of filtering, suspended contamination is deposited inPP cotton or milipore filter, filter core itself is easily contaminated, and long-term piles up that to cause bacteria breed easily to cause follow-upPollution again.
In addition, traditional filter core only sieves taking aperture as basis, therefore can not sieve well heterogeneityImpurity, such as, poor for the filter capacity of metal harmful ion.
Summary of the invention
One object of the present invention is to provide a kind of filter core, and its filter membrane surface is electric charge, utilizes electrostatic effectThe sieve performance of effect modified filter membranes.
Another object of the present invention is to provide a kind of filter core, the aperture size of its filter membrane is less, and filtering accuracyHigh.
Another object of the present invention is to provide a kind of filter core, it has in impurity in effective filtered waterGood permeation flux.
Another object of the present invention is to provide a kind of filter core, it has good anti-soil with antibacterial macromoleculeDye, antibacterial ability.
Another object of the present invention is to provide a kind of filter core, its antipollution and recycling capable of washing, therefore toolThere is longer service life.
Another object of the present invention is to provide a kind of filter core preparation method, prepared by its mode by surface modificationFilter membrane, improves traditional filter membrane performance.
Another object of the present invention is providing a kind of filter core preparation method, and it is by making cartridge surface performance predeterminedElectric charge is electrical, realizes the surface modification of filter core, in basic screening principle, introduces the electrostatic interaction between electric charge,Thereby improve the filtering accuracy of filter core and to the holding back of characteristic ion, filtration.
Another object of the present invention is to provide a kind of filter core preparation method, it is by the mode of ultraviolet radiation graft,Make filter membrane surface with negative electrical charge.
Another object of the present invention is to provide a kind of filter core preparation method, its mode by self assembly is layer by layer inhaledAttached antibacterial macromolecule, thus make filter membrane there is good bacteriostasis property.
Another object of the present invention is to provide a drainage method, it is by the screening of aperture, by tableThe charged effect of face is filtered, and improves water filtering performance.
Another object of the present invention is to provide a drainage method, it,, through antibacterial macromolecular filtering, suppresses residualGrowing of bacterium.
Another object of the present invention is to provide an equipment for filtering water, the filter core that it adopts through surface modification, hasHigher filtering accuracy, obtains the drinking water of high-quality more.
Another object of the present invention is to provide an equipment for filtering water, it adopts the filter core through surface modification, in filterWhen water, remove harmful metal ion, obtain the drinking water of high-quality, health more.
In order to realize above goal of the invention, an aspect of of the present present invention provides a filter core, for water treatment plant, and its bagDraw together: at least one modified filter membranes, described filter membrane surface is predetermined charge, carries out with the electrostatic interaction by electric chargeFiltered water, thereby modified filter membranes described in surface modification.
According to one embodiment of the invention, described in described filter core, modified filter membranes surface is negative electrical charge or positive electricityLotus property, anion or cation in Coulomb repulsion water, thereby in the time of described filter element filtering water anion in trap waterOr cation.
According to one embodiment of the invention, described in described filter core, modified filter membranes surface is positive charge, staticRepel metal ion, thus in the time of described filter element filtering water metal ion in trap water.
According to one embodiment of the invention, described in described filter core, modified filter membranes surface has antibacterial macromolecule layer,Thereby suppress the bacteria breed of described modified filter membranes.
According to one embodiment of the invention, modified filter membranes described in described filter core comprises a base membrane layer and a functionLayer, described functional layer is adsorbed in described modified filter membranes surface, with to described base membrane layer surface modification.
According to one embodiment of the invention, functional layer described in described filter core comprises a grafting sublayer, described in connectBranch layer grafts on described base membrane layer surface by modified monomer and forms, and is electric charge, to make described modificationFilter membrane obtains predetermined charge.
According to one embodiment of the invention, described in described filter core, base membrane layer has light sensitivity, is suitable for carrying out purpleOuter photo-grafting.
According to one embodiment of the invention, the light sensitivity of base membrane layer described in described filter core is by adsorption lightQuick catalyst and obtaining.
According to one embodiment of the invention, described in described filter core, grafting sublayer is by the mode of ultraviolet radiation graftGraft on described base membrane layer.
According to one embodiment of the invention, described in described filter core, the modified monomer of grafting sublayer is selected from combination:One or more in polystyrene-based sodium sulfonate, polyacrylic acid and aforementioned the two copolymer.
According to one embodiment of the invention, functional layer described in described filter core comprises a self assembly sublayer, described inSelf assembly sublayer is assembled in described grafting sublayer, to make described modified filter membranes obtain assembling thing function.
According to one embodiment of the invention, self assembly sublayer described in described filter core is by the side of self assembly layer by layerFormula is assembled in described grafting sublayer.
According to one embodiment of the invention, self assembly sublayer described in described filter core is antibacterial macromolecule layer, withMake described modified filter membranes there is bacteria resistance function.
According to one embodiment of the invention, self assembly sublayer described in described filter core is modification of chitosan or poly-leftRevolve lysine.
According to one embodiment of the invention, base membrane layer described in described filter core is milipore filter, and described functional layer is inhaledInvest described ultrafiltration surface, thereby described milipore filter is carried out to surface modification.
According to one embodiment of the invention, described in described filter core, base membrane layer is selected from combination: PVDF milipore filter,One in polypropylene PP cotton and polyether sulfone PES, described functional layer is adsorbed in described base membrane layer surface, therebyDescribed base membrane layer is carried out to surface modification.
According to one embodiment of the invention, described in described filter core, the structure of base membrane layer is selected from combination: hollow fibreOne in dimension structure, plate armature, rolled structure and tubular structure.
According to one embodiment of the invention, base membrane layer described in described filter core is the cotton filter membrane of PP, described functionLayer is adsorbed in the cotton filter membrane of described PP surface, thereby to the cotton filter film surface modifying of described PP.
According to one embodiment of the invention, described filter core comprises an encapsulation external member, multiple described modified filter membranes endsPortion is packaged in described encapsulation external member, is packaged in described encapsulation external member to make described bunchy.
Another aspect of the present invention provides a filter core manufacture method, comprises step:
S11: obtain the modified filter membranes described in: and
S12: by described modified filter membranes end portion encloses in an encapsulation external member,
According to one embodiment of the invention, described filter core manufacture method comprises step: bending bunchy ground is arrangedDescribed modified filter membranes, makes it be loop.
Another aspect of the present invention, provides a modified filter membranes preparation method, comprises step:
S21: photoactivate one base membrane layer; With
S22: form a functional layer to photoactivated described base membrane layer.
According to one embodiment of the invention, step S21 described in described modified filter membranes preparation method comprises and passing throughBase membrane layer described in the mode photoactivate of absorption light-sensitive catalyst.
According to one embodiment of the invention, described in described modified filter membranes preparation method, light-sensitive catalyst isTiO2 or ZnO.
According to one embodiment of the invention, described in described modified filter membranes preparation method, step S21 is for choosing lightQuick property base membrane layer.
According to one embodiment of the invention, described in described modified filter membranes preparation method, step S22 comprises: purpleOuter Modification of Photo-grafting Copolymerization monomer, to described base membrane layer, forms a grafting sublayer of described functional layer, thereby makes described baseRete has electric charge.
According to one embodiment of the invention, modified monomer Selection and Constitute described in described modified filter membranes preparation method:One in kayexalate, polyacrylic acid and aforementioned the two copolymer.
According to one embodiment of the invention, described in described modified filter membranes preparation method, step S22 comprises: layerThe antibacterial macromolecule of layer self assembly, to described base membrane layer, forms a self assembly sublayer of described functional layer, thereby makes instituteState base membrane layer and there is bacteria resistance function.
According to one embodiment of the invention, described in described modified filter membranes preparation method, base membrane layer is selected from combination:One in PVDF milipore filter, PP face filter membrane and polyether sulfone PES, described functional layer is adsorbed in described basement membraneLayer surface, thus described base membrane layer is carried out to surface modification.
Another aspect of the present invention provides a drainage method, comprises step: by the electrostatic interaction mistake of surface chargeDrainage.
Comprise step according to the drainage method described in one embodiment of the invention: aperture screening filtered water.
Another aspect of the present invention provides a water treatment plant, comprises at least one aforementioned described filter core.
Brief description of the drawings
Fig. 1 is according to the schematic perspective view of the filter core of first preferred embodiment of the present invention.
Fig. 2 is according to the schematic cross-section of the filter core of first preferred embodiment of the present invention.
Fig. 3 is according to the explosive view of the filter core of first preferred embodiment of the present invention.
Fig. 4 A, 4B are the drainage principle schematic according to the filter core of first preferred embodiment of the present invention.
Fig. 5 is the modified filter membranes structure sheaf schematic diagram according to the filter core of first preferred embodiment of the present invention.
Fig. 6 is real according to first distortion of the modified filter membranes of the filter core of first preferred embodiment of the present inventionExecute example.
Fig. 7 is real according to second of the modified filter membranes of the filter core of first preferred embodiment of the present invention distortionExecute example.
Fig. 8 is real according to the 3rd of the modified filter membranes of the filter core of first preferred embodiment of the present invention the distortionExecute example.
Fig. 9 is the filter core manufacture method block diagram according to above preferred embodiment of the present invention.
Figure 10 is the filter core manufacture process schematic diagram according to above-mentioned preferred enforcement of the present invention.
Figure 11 is the modified filter membranes preparation method block diagram according to above preferred embodiment of the present invention.
Figure 12 is the reaction unit signal according to the modified filter membranes preparation method of above preferred embodiment of the present inventionFigure.
Figure 13 changes according to the modified filter membranes preparation method's of above preferred embodiment of the present invention modified filter membranesContrast.
Figure 14 is the drainage method block diagram according to above preferred embodiment of the present invention.
Figure 15 is the water treatment plant block diagram according to above preferred embodiment of the present invention.
Detailed description of the invention
Below describe and be used for disclosing the present invention so that those skilled in the art can realize the present invention. In below describingPreferred embodiment only as an example, it may occur to persons skilled in the art that other apparent modification. WithThe general principle of the present invention defining in lower description can be applied to other embodiments, deformation program, improvement sideCase, equivalent and do not deviate from the other technologies scheme of the spirit and scope of the present invention.
As shown in Figures 1 to 5, be the filter core according to first preferred embodiment of the present invention. Described filter core is usedIn water treatment plant, alone or coordinate other parts filtered water of water treatment plant, thereby purify water, make throughThe water filtering reaches predetermined requirement, such as reaching drinking water standard. According to a preferred embodiment of the invention, rightTraditional filter core carries out the improvement such as surface modification, and the performance of filter core self and the performance of filtered water are all obtainedImprove and optimize. Such as, filter core in one embodiment of this invention, makes filter core phase of the present invention on the one handThere is higher filtering accuracy and the Rejection to ion than traditional filter core, thereby obtain more excellent water quality;On the other hand, improve the antifouling property of filter core self, increase the service life; And after modification, make thisThe filter core functionalization of invention, obtains predetermined performance, such as antibiotic property.
As shown in Figure 1 to Figure 3, be to show according to the different conditions of the filter core of first preferred embodiment of the present inventionIntention. According to this embodiment of the invention, described filter core comprises at least one modified filter membranes 10 and a package coverPart 20.
Described modified filter membranes 10 is packaged in described encapsulation external member 20, makes the position of described modified filter membranes 10Fixing. That is to say, in the time that described filter core is installed in water treatment plant, fixing by described encapsulation external member 20The installation site of described filter core. And in a kind of application mode, described in former water is close by described modified filter membranes 10Encapsulation external member 20 one end enter described filter core and filter.
According to one embodiment of the invention, described filter core comprises multiple described modified filter membranes 10, each described modificationFilter membrane 10 directions as one man arrange, and end encapsulates fixingly by described external member 20, make described modified filter membranesBe fixed in described encapsulation external member 20 10 bunchys, realize the filtration of predetermined amount of flow. It is worth mentioning that instituteState external member 20 for middle part perforation external member, the end of each described modified filter membranes 10 is packaged in by a bridging agent 30The middle part of the perforation of described external member 20. Especially, in one embodiment of this invention, described bridging agent 30For colloid. That is to say, in this embodiment, the end of each described modified filter membranes 10 is by described glueBody encapsulation is fixed in described external member 20, and the remainder of described modified filter membranes 10 protrudes from described external member 20,Extend to described external member 20 1 sides.
It is worth mentioning that, in one embodiment, described encapsulation external member 20 adopts food stage ABS material, noContain hazardous substance, nonpoisonous and tasteless, intensity is high and durable. The sealing glue of described bridging agent 30 is selected food stageHigh-quality epoxy glue, viscosity is high, and sealing is firm, free from extraneous odour.
According to one embodiment of the invention, the end of described modified filter membranes 10 is embedded in described bridging agent 30, quiltDescribed bridging agent 30 is fixing, and described bridging agent 30 by former water with purify waste water isolatedly, make former water arrive instituteWhile stating encapsulation external member 20 position, can only enter described modified filter membranes 10, through described modified filter membranes 10Filtration after enter stream of cleaned water.
According to one embodiment of the invention, described bridging agent 30 by casting process by described modified filter membranes 10Be packaged in described external member 20. Described bridging agent 30 forms a side grain with described external member 20 surfaces, makes instituteState cartridge surface smooth, attractive in appearance. Especially, in one embodiment, the end of described modified filter membranes 10 is evenBe distributed in described bridging agent 30, make current enter equably each described modified filter membranes 10.
Further, according to one embodiment of the invention, each described modified filter membranes 10 forms loop and encapsulates instituteState encapsulation external member 20. That is to say, the both ends of each described Modified Membrane 10 are all packaged in described external member 10,In the time of filtered water, described in current are entered by the both ends of described modified filter membranes 10 by the top of described external member 20Filter core.
According to one embodiment of the invention, described modified filter membranes 10 is milipore filters, that is to say described modificationFilter membrane is the milipore filter of modification, and in other words, traditional milipore filter carries out modification and obtains described modified filter membranes 10.Described modified filter membranes 10 is to utilize membrane separation technique to sieve, with the pressure differential of described modified filter membranes 10 both sidesFor driving force, taking described modified filter membranes 10 as filter medium, under certain pressure, described in Dang Yuanshui flows through, the many tiny micropore gathering in described modified filter membranes 10 surfaces only allows water and little when on modified filter membranes the 10 surfaceMolecular substance is purified waste water by becoming, and the material that in former water, volume is greater than film surface micropore footpath is trapped withinThe influent side of film, becomes concentrate, thereby realizes former water purification, separation and concentrated object. Milipore filterMembrane material mainly contain cellulose and derivative thereof, Merlon, polyvinyl chloride, Kynoar, polysulfones,The polyvinyl alcohol of polyacrylonitrile, polyamide, polysulfonamides, SPSF, interlinkage, modified acrylic polymerDeng.
In one embodiment of this invention, on the described modified filter membranes 10 of every meter long, approximately have 6,000,000,000 0.01 micro-The micropore of rice, its aperture only allows beneficial mineral matter and the trace element in hydrone, water to pass through, and minimum thinThe volume of bacterium all more than 0.02 micron, therefore bacterium and the colloid more much bigger than bacterium volume, iron rust,Suspension, silt, larger molecular organics etc. can be retained down by milipore filter, thereby have realized purification process.
Further, with reference to Fig. 2, Fig. 4 A, 4B. According to one embodiment of the invention, described modified filter membranes10 is the hollow-fibre membrane in milipore filter, and described hollow-fibre membrane has a membranous wall 101, the middle passage that forms102, micropore 103 gathers on described membranous wall. According to one embodiment of the invention, in described modified filter membranes 10 isPressure type hollow fiber film, in the process of filtered water, former water enters by port and enters in described hollow-fibre membrane,Enter in described path 10 2, drive through pressure differential, former water radially penetrates described membranous wall from inside to outsideThereby 11 become and purify waste water, the impurity filtering is stayed the inside of described hollow-fibre membrane. According to the present inventionAnother embodiment, described modified filter membranes is external pressing type hollow fibrous membrane, in the process of filtered water, former water existsThe flows outside of filter membrane, by the pressure of former water itself, as water supply pipe internal pressure, or passes through filter membraneInside applies negative pressure, and as suction type negative pressure, making to purify waste water sees through described membranous wall 101, from described modified filter membranes10 internal-internal flows away, and pollutant is retained in the outer surface of filter membrane 10 described in film, this kinds of structuresFilter membrane be convenient to carry out periodic cleaning.
It is worth mentioning that, as shown in Figure 4 A, for the filtration and infiltration principle schematic of inner pressed filter membrane, formerWater, in the internal flow of film silk, through the filtration of filter membrane, is purified waste water and is flowed out from appearance; And as shown in Figure 4 B,For the filtration and infiltration principle schematic of external-compression type filter membrane, former water is in film silk flows outside, through the filtration of filter membraneEffect, purifies waste water and flows out from inner surface. Those skilled in the art should be understood that, the structure of described filter membraneType is not restriction of the present invention, and described modified filter membranes of the present invention can manufacture inner pressed filter membrane, also canTo make external-compression type filter membrane, particular type, can penetration theory and infiltration direction as required select, and changesProperty surface location with need infiltration type corresponding.
Those skilled in the art should be understood that, in the accompanying drawing in this embodiment of the present invention, with inThe structure of hollow fiber film is that example describes, but the type of described modified filter membranes 10 and planform are not theseThe restriction of invention, in other embodiments of the invention, described modified filter membranes can also be PP (polypropylene)The dissimilar filter membranes such as cotton fiber, flat plate ultrafiltration membrane, rolling ultrafiltration membrane, tubular ultra-filtration membrane.
Those skilled in the art should be understood that, the shape of described modified filter membranes is not restriction of the present invention,Such as doughnut formula, flat, rolling, tubular type, the filter membrane of various shapes can pass through table of the present inventionFace modification and become modified filter membranes.
The integral layout shape that those skilled in the art it is to be further understood that described modified filter membranes 10 is notBe restriction of the present invention, in this embodiment of the present invention, each described modified filter membranes 10 is in the mode of doublingBe packaged in the described bridging agent 30 in described external member 20, thereby form two-port all towards described external member 20The loop in outside. In the time of drainage, current are by the port of described modified filter membranes 10 that is positioned at described external member 20 positionsEnter in described modified filter membranes 10, along in the mobile process of the described path 10 2 of described modified filter membranes 10,Hydrone and small-molecule substance see through the micropore on described membranous wall 101 and see through described modified filter membranes 10, andLarge molecular impurity is trapped within described modified filter membranes 10, thereby reaches the object of purifying waste water. And at thisIn other bright embodiment, described modified filter membranes 10 can also be set to other different layouts and shape knotStructure, such as straight-through mode but not bending.
It is worth mentioning that, in actual application, different filter membranes are applicable to filtering the water quality of various criterion. RatioAs tubular type is applicable to processing the water that pollutant is many, doughnut is moderate, and rolling can only the high water of processing accuracy. And rootAccording to described filter core of the present invention, it has higher filtering accuracy, the therefore less water of filtering contaminants preferably,Or the less water quality of impurity screening size preferably. For some poor water quality, such as sediment charge is largerTime, easily there is the phenomenons such as obstruction, be therefore not suitable for filtering this type of water quality. That is to say, can be according to mistakeThe shape that described modified filter membranes need to be set and the integral layout structure of filter precision. Such as, drink when being applied toWater treatment plant time, the shape of described modified filter membranes can be selected doughnut formula or rolling, and selects hollow fibreWhen dimension formula, the described modified filter membranes of bunchy can bend by end overall package. While selecting rolling, multilayer instituteState modified filter membranes 10 overlapping, suitable higher filtering accuracy.
Described filter core further comprises a net 40, is socketed on the outside of described modified filter membranes 10. That is to say,By described cover net 40, the described modified filter membranes of bunchy is retrained, make described modified filter membranes 10 not fugitiveDisorderly. And in the time changing or described filter core is installed, described cover net 40 makes described filter core be easy to be mounted, easilySlide in the tube wall along installing, the described modified filter membranes 10 of described filter core is not subject to extraneous obstruct and disperses.
Further, with reference to Fig. 5, Figure 13, described modified filter membranes 10 comprises a base membrane layer 11 and a functional layer12, described functional layer 12 is attached to described base membrane layer 11. According to this embodiment of the invention, described basement membraneLayer 11 can be formed by the filter membrane of different structure shape, as PP cellucotton, hollow fiber ultrafiltration membrane, dull and stereotyped superThe different film such as filter membrane, tubular ultra-filtration membrane, rolling ultrafiltration membrane composition, and described in described functional layer 12 is attached toBase membrane layer 11, therefore, compares traditional filter membrane, and described modified filter membranes 10 carries out on the basis of original performanceModification, obtains the performance that dominance energy more or traditional filter membrane do not possess.
According to one embodiment of the invention, described functional layer 12 comprises a grafting sublayer 121, described graftingLayer 121 grafts on described base membrane layer 11 and forms graft copolymer. Further, described functional layer 12 described inThe graft of grafting layer 121 is polyelectrolyte. Especially, in one embodiment, the connecing of described functional layer 12Branch thing is kayexalate (PSS).
The mode grafting of uv photo initiated grafting is passed through by a grafted monomers in the described grafting sublayer 121 of described functional layer 12Form in described base membrane layer 11. In the time detecting, can see after grafting on film surface by electron microscopeCan form the relatively fine and close functional layer of one deck micron order thickness. That is to say, compare traditional filter membrane, described inModified filter membranes in the time of micro-detection, grafting sublayer 121 described at least many one decks, and described grafting sublayer 121 changesBecome the function of surface of described base membrane layer 11, and can not change the essence of described base membrane layer 11, realize surfaceModification.
Grafted monomers can be chosen as required, and that can choose mainly contains three types, and wherein one is hydrophilicProperty polar monomer, as acrylic acid (AA), butenoic acid (CA), methacrylic acid (MAA), acrylamide(AM), polyacrylic acid (PAA) etc., its general formula is: R～CH2=C (R ')-COR ", wherein R=CnH2n+1，N3; R '=H or CH3; R "=OH or NH2. Another kind is to contain sulfonic monomer, as polystyrene-based sulphurAcid sodium (PSS), SSS (SSS), ALS (SAS), methacrylic acid-3-sulfonic acidPotassium propyl ester (SPMA), 2-acrylamide-2-methyl propane sulfonic (AMPS) etc.
Also have a kind of be any can with the polarity of aforesaid monomer copolymerization or nonpolar alkenes compounds. AsThe copolymer of PSS and PAA.
In another embodiment, the graft of the described grafting sublayer 121 of described functional layer 12 is PSS and PAACopolymerization product, and the quality of the two is between 1:20 to 20:1.
Further, described functional layer 12 is with predetermined charged. Especially, described grafted monomers, as PSS,PAA and AA are electronegative, therefore make described functional layer 12 embody elecrtonegativity. And holding back the mistake of filtrationCheng Zhong, due to described modified filter membranes 10 except the sieve effect based on aperture, the grafted chain institute on filmElectrostatic repulsion between anion in negative electrical charge and the solution of band, and because electrostatic repulsion hasCertain operating radius, therefore makes to sieve reducing of aperture, thereby makes the aperture of described modified filter membranes 10Reduce simultaneously, to have improved the charge density on film surface, described modified filter membranes 10 is revealed high price anion formGood Rejection, this point is the not available function of traditional filter membrane, traditional milipore filter does not have ionRetention functions, because in the time that screening aperture is very little, certainly will affect water flux less, therefore aperture screening does not reachTo the screening of ion.
It is worth mentioning that, detect surface contact angle, can find, with respect to traditional filter membrane, grafting instituteThe surface contact angle of stating the described modified filter membranes of grafting sublayer 121 reduces, and therefore, makes described modified filter membranes10 hydrophily increases substantially, thereby improves antifouling property. Especially, detect and find by experiment, withSSS is that the described modified filter membranes 10 of grafted monomers is with respect to the described modified filter membranes 10 taking AA as grafted monomersThere is less surface contact angle. For example, in one embodiment, when the SSS with 10% carries out after grafting,Recording surface water contact angle only has 12.1 °, is far smaller than 67.3 ° of contact angles while thering is no grafting. Contact angleSize affects the hydrophilicity of filter membrane, and good hydrophilic property is conducive to improve contamination resistance. Contact angle is less,Hydrophily is better, and therefore, the filter membrane after modification has good hydrophily, and contamination resistance is strong.
Further, described functional layer 12 comprises a self assembly sublayer 122,122 layers of described self assembly sublayersBe adsorbed in to layer self assembly described grafting layer 121. Especially, in one embodiment of this invention, described from groupDress sublayer 122 is antibacterial macromolecule, thereby increases the anti-microbial property of described modified filter membranes 10. That is to say,In the time of filtered water, impurity is retained in described modified filter membranes 10 inner sides, such as bacterium, and due to described from groupThe bacteriostasis of dress sublayer 122, is difficult for causing bacteria breed when impurity is piled up, thereby reduces described modificationThe pollution level of filter membrane and pollute speed, extends service life of described filter core. Especially, described self assemblySublayer 122 comprises one deck or above antibacterial macromolecule.
Self assembly layer by layer (layer-by-layerself-assembly, LBL) utilizes charged substrate at the contrary electricity of bandLayer-by-layer self-assembly multilayer film in the medium of lotus. Can see thus, need to be by the process of self assemblyThe condition of opposite charges, because described grafting sublayer 121 is electronegative, and described self assembly sublayer 122 press downBacterium macromolecule is all positively charged conventionally, thereby has realized the condition of self assembly, makes the molecule of self assembly canFirmly absorption assembling.
In this embodiment of the present invention, described self assembly sublayer 122 is antibacterial macromolecule, thereby makes instituteState modified filter membranes 10 and possess anti-microbial property, make its functionalization. Those skilled in the art should be understood that,Described antibiotic property is not restriction of the present invention, in other embodiments of the invention, and can also be by adsorbing otherDifferent media, makes described modified filter membranes 10 possess other estimated performance, as the function of ion exchange resin.
Also can see that thus the mode of self assembly can realize by original electric charge environment on the one handThe process of self assembly layer by layer, makes assembling effect firm; On the other hand, the mode of self assembly is layer by layer adjusted converselySave original electric charge, thereby can control the electric charge that it presents, thereby utilize described in electrostatic effect regulatesThe rejection of modified filter membranes 10. Those skilled in the art should be understood that, in the time regulating charge character,Can select the mode of self assembly, can obtain functional after self assembly layer by layer simultaneously, but be not thisBright restriction, that is to say, in other embodiments of the invention, can also regulate by other means formerSome electric charges, the electric charge that its performance is expected.
According to embodiments of the invention, between the screening aperture of described modified filter membranes 10 and electrostatic effect, have onePlant matching relationship, can obtain higher rejection in predetermined condition, there is larger flux simultaneously, such asSuitable percent grafting, pH-value and electronegativity.
It is worth mentioning that the aperture screening of described modified filter membranes 10 of the present invention and the common work of electrostatic effectWith under, the rank of screening can reach nanoscale, thereby greatly improves the filtering accuracy of filter membrane, obtains more excellentPurifying waste water of matter, and do not reach such requirement for the filtering accuracy of traditional milipore filter, especially drinkingWater purification field.
According to one embodiment of the invention, described self assembly sublayer 122 is preferably modification of chitosan or poly-left-handed relyingPropylhomoserin (PLL).
It is worth mentioning that, common antibacterial macromolecule is all positively charged, therefore, and when the antibacterial son of positively chargedLayer 122 is while being adsorbed in to self assembly layer by layer electronegative described grafting sublayer 121, by between different electric chargesNeutralization, regulates the character of the surface charge of described modified filter membranes 10, makes the table of described modified filter membranes 10Face performance positive charge or negative electrical charge. And when the electric weight of described self assembly sublayer 122 is greater than described grafting sublayer 121Time, described modified filter membranes surface shows the electrical of described self-chambering sublayer 122, i.e. electropositive; When described self assemblyWhen the electric weight of sublayer 122 is less than described grafting sublayer 121, performance described grafting sublayer, described modified filter membranes surface121 electrically, i.e. electropositive. Thus, also can see, same mode can make described modified filter membranesSurface performance neutral, but now described modified filter membranes still show described grafting sublayer 121 and described fromAssembling sublayer 122 bring electrically outside other performances.
That is to say, the negative electrical charge separately by described grafting sublayer 121 and described self assembly sublayer 122 andThe electric weight of positive charge, can regulate, control the surface charge character of described modified filter membranes 10, thereby makes its tableThe electric charge of existing expection. Such as, electropositive, elecrtonegativity, neutrality. Especially, when described modified filter membranes10 while being elecrtonegativity, compares traditional filter membrane, and described modified filter membranes 10 has higher filtering accuracy, and forHigh price anion has good Rejection; In the time that described modified filter membranes 10 is electropositive, compare traditional filterFilm, described modified filter membranes 10 has higher filtering accuracy, and has preferably and cut for harmful metal ionThe property stayed. Thereby make selectively functionalization of described modified filter membranes 10, and traditional filter core shows neutrality conventionallyOr approach neutrally, therefore, can not realize the selective of electric charge, and electric charge is for the modifying function filtering, thisThe performance of sample is that traditional filter element of water purifier is not available.
Those skilled in the art should be understood that, Fig. 5, and Figure 13 is described modification filter as an example onlyThe simplified structure of film, and be not concrete material. Described in the structure of described modified filter membranes and described functional layerActual structural relation between grafting sublayer 121 and described self assembly sublayer 122 and described base membrane layer 12Be not limited to laminated construction. The thickness of concrete functional layer and structure can be due to percent grafting and assembled layers thicknessAnd produce various variations.
Also it is worth mentioning that, by detect surface contact angle can find, compare traditional filter membrane, described in changeProperty filter membrane 10 surface water contact angles are much smaller, and described modified filter membranes 10 has better hydrophily, thereby carriesThe high antifouling property of described modified filter membranes 10.
Also it is worth mentioning that, milipore filter used after a period of time, the bacterium that is retained down, iron rust, colloid,The harmful substance such as suspension, larger molecular organics can be attached to the inner surface of milipore filter, makes the aquifer yield of milipore filterDecline gradually, when severe water pollution, more easily cause the obstruction of milipore filter, regularly to milipore filter especially from the beginningRinse the aquifer yield that can have efficient recovery film. Described modified filter membranes 10 can carry out periodic cleaning, to keepCertain membrane permeate flux, and extend service life of film. Cleaning method is generally according to the character of film and processing materialThe character of liquid is determined. Normally, can first clean with waterpower, then according to circumstances adopt different chemistry to washWash agent and clean, for example, can select the solubilizer containing ion to electropaining material, can to water-soluble organic coatingTo use " bridged bond " type solvent. In food industry, protein precipitation can be with proteinase solvent or phosphate, silicateThe alkaline detergent on basis. The chelating agent of available EDTA of precipitation that film surface is formed by inorganic salts and so on or acid,Alkali is dissolved. For difform membrane module, can select different cleaning methods, as tubular module canTo carry out mechanical cleaning with sponge ball, doughnut formula assembly can be with back flush etc. Use for food industryFilm also needs disinfection (with NaOH and H2O2Deng).
Further, can utilize the power of apparatus to remove the pollutant on film surface, be not special for general fenestraTiny removable ultra-filtration element, can directly take apart and rinse with clear water on one side with soft material side polished. SeparatelyCan clean with sponge ball on the one hand, according to film pipe diameter, select suitable sponge ball, utilize special establishingStandby logical filmed passing tube carries out wiping cleaning, can Reusability. Also can water be heated to by hot water injection's method(30～40 DEG C), then flushing membrane surface, removes those impurity effects sticky or thermosol better. ThisPhysical cleaning method is without any chemical reaction, fairly simple, convenient, health.
According to embodiments of the invention, there is anti-microbial property on the one hand, therefore make described modified filter membranes grow carefullyThe probability of bacterium is less, keeps for a long time good environment for use; Can pass through on the other hand periodic cleaning, make instituteStating modified filter membranes can reuse, and therefore described modified filter membranes of the present invention is compared traditional filter membrane and had longerService life. Especially, through verification experimental verification, the service life of described modified filter membranes 10 of the present invention canTo reach more than 1 year, and conventionally only have 3 to 6 months the service time of traditional filter membrane.
With reference to Fig. 6, it is first variant embodiment according to above preferred embodiment of the present invention. With above-mentioned realityExecute routine difference and be, described filter core is a modification rolled film filter core. Described modification rolled film filter core comprises oneDescribed modified filter membranes 10A and an interlayer 50A, described modified filter membranes 10A and described interlayer 50A stacked ring aroundAnd formation rolled film. That is to say, radially, described modified filter membranes and described interlayer 50A compartment of terrain arrange.Especially, in one embodiment, described interlayer is netted interlayer. Described modified filter membranes 10A is around forming onePath 10 2A, in the time purifying waste water, former water is entered in described filter core by the port of described path 10 2A, passes throughThe filtration of the described modified filter membranes 10A of lamination and reach described filter core outside, becomes and purifies waste water.
With reference to Fig. 7, be according to second of above preferred embodiment of the present invention variant embodiment. Described filter coreIt is a modification flat sheet membrane filter core. Described modification flat sheet membrane filter core comprises at least one modified filter membranes 10B and an encapsulationExternal member 20B, described modified filter membranes is tabular to be fixed by described encapsulation external member 20B. That is to say, described inThe marginal position of modified filter membranes 10B is plane earth by described encapsulation external member to be fixed. In the time filtering, former water is by instituteA side of stating dull and stereotyped filter membrane arrives opposite side and becoming and purifies waste water, thereby is filtered by described modified filter membranes 10B.
With reference to Fig. 8, be according to the 3rd of above preferred embodiment of the present invention the variant embodiment, described filter coreBe the cotton filter core of a MODIFIED PP, the cotton filter core of described MODIFIED PP comprises a modified filter membranes 10C, described modified filter membranes10C is obtained by the cotton filter core modification of PP. That is to say the described base membrane layer 11C of described modified filter membranes 10CBe the cotton layer of a PP, described functional layer 12C grafts on the cotton layer of described PP, thereby the cotton layer of described PP is changedProperty, obtain and be better than the performance that the cotton filter core performance of traditional PP and traditional cotton filter core of PP do not possess.
With reference to Fig. 9,10, it is the filter core manufacture method schematic diagram according to above preferred embodiment of the present invention. InstituteState filter core manufacture method 900 and comprise step:
S11: obtain a modified filter membranes 10;
S12: by modified filter membranes end portion encloses in an encapsulation external member 20.
Water purifying principle by filter core can recognize, for identical water quality, the water purification performance of filter core depends on filterThe performance of film, different filter membranes, precision, water flux and the functional difference of filtration, therefore, choose, prepareFilter membrane suitable or high-quality is the basis that filter core is manufactured. According to above preferred embodiment of the present invention, compare traditionFilter membrane, described modified filter membranes 10 is after surface modification, surface is electric charge, shows electropositive or negativeElectrically, and unconventional neutrality, therefore, in the time purifying waste water, for screening ionization difference, be not onlyBased on aperture sieve effect, there is the interactional screening of electric charge simultaneously, improve filtering accuracy, and forSome characteristic ions, such as high price anion, metal harmful ion, have special retention functions. Further,In certain embodiments, described modified filter membranes also has antimicrobial macromolecule layer, described modified filter membranes is had anti-Bacterium performance.
In described step S11, described modified filter membranes can be that modification hollow fiber ultrafiltration membrane, modification are dull and stereotyped superFilter membrane, the cotton filter membrane of MODIFIED PP.
Taking modification hollow fiber ultrafiltration membrane as example, obtaining, after described modified filter membranes 10, obtaining film silk, enterAnd by described modified filter membranes 10 bunchys arrange, obtain the film silk of bunchy, described filter core is realized certainFiltration flux. And the quantity of described modified filter membranes 10 can arrange according to the size of predetermined flux.
Therefore described step S11 comprises step: described modified filter membranes is arranged on bunchy ground.
In one embodiment of this invention, described modified filter membranes is the layout of loop, and both ends are all packaged in instituteState in encapsulation external member 20, thereby in the process of filtering, former water is entered by the two-port of described modified filter membranes,Increase filtration flux, meanwhile, impurity is all retained in described modified filter membranes 10 inside. , surpassing bunchyFilter membrane silk is made by described modified filter membranes 10, described encapsulation external member 20 and described connection after casting processThe described filter core that agent 30 3 parts form.
Therefore, described step S11 comprises step: the described modified filter membranes 10 of bending bunchy, makes it be loop.The impurity being filtered is all retained in described modified filter membranes inside, and can not flow out in water purification stream with current.
Especially, in one embodiment, can doubling described in modified filter membranes 10, make its two-port be positioned at one end,Thereby facilitate encapsulation process.
In described step S12, in one embodiment, the end of described modified filter membranes 10 is connected by oneAgent 30 is packaged in described encapsulation external member 20. Especially, in one embodiment, described bridging agent 30 is glueBody. By casting mode by the end portion encloses of described modified filter membranes 10 in described encapsulation external member 20. In encapsulationTime, two-port position is placed in described encapsulation external member 20, further as the interior cast of described encapsulation external member 20 instituteState bridging agent 30, treat that described bridging agent 30 solidifies, sizing, completed the preliminary of described modified filter membranes 20Encapsulation process. Especially, described encapsulation external member 20 adopts epoxy resin to form, and described bridging agent 30 has been filledSpace between film silk and film silk, form former water and purify waste water between separation layer, described in first former water enter, changeIn the port of property filter membrane 10, after the filtration of described modified filter membranes 10, become and purify waste water, prevented former water withoutFilter and directly enter into and purify waste water.
In the time encapsulating by glue, the end of described modified filter membranes 10 protrudes from described encapsulation external member 20 outsidesPart, in order to make described filter core upper surface smooth, need excision to protrude from the portion of described encapsulation external member 20Point, comprise the described bridging agent of protrusion and the described modified filter membranes 10 of protrusion, therefore, described step S12 bagDraw together step: excision protrudes from the part of described encapsulation external member 20, makes its upper surface smooth.
It is worth mentioning that, excision process is carried out after described bridging agent solidifying and setting, each described modificationThe position of filter membrane is relatively definite, thus prevent from excising described in process influence that the port of modified filter membranes 10 is arranged andThe packaging effect of described bridging agent 30.
With reference to Figure 11, according to above preferred embodiment of the present invention, the invention provides a modified filter membranes preparation sideMethod, described preparation method carries out modification to traditional filter membrane, is better than the performance of traditional filter membrane and obtains thereby obtainObtain the performance that traditional filter membrane does not possess. Described modified filter membranes preparation method 1100 comprises step:
S21: photoactivate base membrane layer 11; With
S22: form a functional layer 12 to photoactivated described base membrane layer 11.
In above-mentioned steps S21, be intended to obtain photosensitive material, so that while being follow-up interpolation functional layerProcess of Surface Modification provides basis. That is to say, described functional layer 12 is suitable for making an addition to the material with light sensitivityMaterial surface therefore, first needed to form light sensitivity basis before carrying out surface modification. And according to reality of the present inventionExecute example, photosensitive material obtained two kinds of modes, wherein a kind of mode is at described base membrane layer 11 adsorptionsSensitising agent, such as TiO2Nano particle, ZnO nano particle etc.; Another kind of mode is, choose self be with photosensitiveThe described base membrane layer 11 of property, normally main chain or side chain are with carboxyl, sulfuryl or benzophenone structural unitPolymer, as polysulfones (PS), polyether sulfone (PES), polyether-ketone (PEK), containing the polyether-ketone of phenolphthalein base(PEK-C), containing the polyether sulfone (PES-C) of phenolphthalein base or blend or the copolymer etc. of aforementioned polymer.
That is to say, in the time that the described base membrane layer 11 of choosing does not have light sensitivity, need to be by adsorptionSensitising agent is adsorbed in described base membrane layer 11 by mode. Now, described step S21 comprises step: urge photosensitiveAgent is adsorbed in described base membrane layer 11.
When the described basement membrane of choosing is during with light sensitivity, described step S11 is and chooses light sensitivity base membrane layer. ThisTime, S21 comprises step: choose base membrane layer 11 described in light sensitivity.
It is worth mentioning that, traditional milipore filter that is applied to water treatment plant does not possess light sensitivity conventionally, therefore existsWhile carrying out surface modification, conventionally need to make its photoactivate, carry out the adsorption of sensitising agent.
In one embodiment, realize photoactivate in the mode of light-sensitive catalyst adsorption. Detailed process is: willDescribed base membrane layer 11 is soaked in the scheduled time in the suspension that contains light-sensitive catalyst and nano particle dispersant,And act on described suspension with supersonic generator simultaneously, prevent cohesion, and then put into clear water and moistenWash 1 to 2 time, by the not firmly sensitising agent particle of absorption removal.
Preferably, the sensitising agent that can select has photosensitive titanium dioxide (TiO2) nano particle, photosensitized oxidation zinc(ZnO) nano particle etc.
It is worth mentioning that, in the time carrying out the adsorption of sensitising agent, need to add nano particle dispersant, makeSensitising agent fully disperses in solution, and by ul-trasonic irradiation in suspension, to prevent suspension cohesion.The nano particle dispersant that can select comprises macromolecule dispersant of type, as polyethylene glycol (PEG), moleculeWeight range 200～10000, PEG solution optimum concentration range 0.1%～10%; And inorganic dispersant, as chlorineChange sodium, dispersant optimum concentration range 0.01%～5%. In addition the knot of macromolecule dispersing agent and inorganic dispersant,Close also and use as dispersant. Preferably, the mass ratio of described sensitising agent and described nano particle dispersant is positioned at50:1 is between 5:1.
It is worth mentioning that, the effect of described sensitising agent is to prepare for grafting process, therefore, does not need to inhaleAttached a large amount of sensitising agent just can be realized its function. Normal conditions, 0.1% adsorption rate just can realize
In one embodiment, choose TiO2As sensitising agent, the particle size scope that photolytic activity is the highest is5～100nm, sensitising agent solution concentration is 0.1%～20%, chooses macromolecule sexual type dispersant PEG and disperses,PEG molecular weight ranges 200～10000, PEG solution optimum concentration range 0.1%～10%. By described base membrane layer11 are immersed in and contain TiO2With in the suspension of PEG more than 1 hour, and use supersonic generator effect simultaneouslyPrevent its cohesion in suspension, then put into clear water rinse 1～2 time, will go for the nano particle of firmly absorptionRemove.
Further, described step S21 comprises step: ultraviolet radiation graft modified monomer is in described base membrane layer 11,Form a grafting sublayer of described functional layer, thereby make described base membrane layer there is electric charge.
It is worth mentioning that, described modified monomer chooses grafted monomers in order to obtain expection surface modification performance,Thereby make base membrane layer 11 can obtain the spy who is brought by described modified monomer grafting after by uv photo initiated graftingProperty, thus make the surface modification of base membrane layer 11. Grafted monomers can be chosen as required, can chooseMainly contain three types, wherein one is hydrophily polar monomer, as acrylic acid (AA), butenoic acid (CA),Methacrylic acid (MAA), acrylamide (AM), polyacrylic acid (PAA) etc., its general formula is:R～CH2=C (R ')-COR ", wherein R=CnH2n+1, n3; R '=H or CH3; R "=OH or NH2. Another kind ofTo contain sulfonic monomer, as polystyrene-based sodium sulfonate (PSS), SSS (SSS), alkenePropyl sulfonic acid sodium (SAS), methacrylic acid-3-potassium sulfonate propyl ester (SPMA), 2-acrylamide-2-methyl-propSulfonic acid (AMPS) etc.
Also have a kind of be any can with the polarity of aforesaid monomer copolymerization or nonpolar alkenes compounds. AsThe copolymer of PSS and PAA.
Mode by ultraviolet radiation graft is at the dissimilar modified monomer of described base membrane layer 11 grafting, thereby canTo realize the surface modification of described base membrane layer 11 by described modified monomer, make it in the time being applied in filter core,Make the water filtering performance of filter core, as filtering accuracy, high price salt ion filter, the filtration of harmful metal ion etc.,And the serviceability of self, as service life, be all optimized.
In one embodiment of this invention, in ultraviolet radiation graft process, be:
The device of uv photo initiated grafting reaction as shown in figure 12. Described base membrane layer 11 is installed in one first reactor 5,At the graft modification monomer solution that adds predetermined concentration above described base membrane layer 11 above described base membrane layer 11Predetermined altitude, as 1～6cm. Place copper/saturated copper sulphate solution on one second reactor 2 tops, to predetermined levelHighly, as 0.8～1.2cm, the homopolymerization for the UV light below elimination wavelength 300nm with inhibition grafted monomers.One uviol lamp 3 is arranged at described the second reactor 2 top positions, and makes described uviol lamp 3 and described baseRete 11 be preset distance, as 5～8cm. With ultraviolet light intensity instrumentation must be at described membrane surface wavelength 365nmUltraviolet ray intensity be 8.7mWcm-2. Predose leads to the nitrogen scheduled time to described the first reactor, as 4～6min,To remove the micro amount of oxygen in modified monomer solution. Ultraviolet irradiation is grafted on and in blanket of nitrogen, carries out certain hour. ReactionAfter end, take out from container the described base membrane layer 11 after grafting, described base membrane layer 11 is placed on to ethanol/water moltenIn liquid, in ultrasonic washing agent, wash the scheduled time, as 10～20min, repeatedly, as 3～6 times,Taking remove unreacted modified monomer and stick to described base membrane layer 11 surfaces and aperture as homopolymers. Use again matterThe NaSO that amount mark is predetermined value4Solution, as 3%～6% soak the scheduled time, as 1.5～2.5 hours, carry out fromSon exchange, makes saponification. Then clean with distilled water, put into deionization through the described basement membrane of said method and processingIn water, soak stand-by. Obtain thus the described base membrane layer 11 of uv photo initiated grafting, the surperficial shape of described base membrane layer 11Become the described functional layer 12 of grafting, form herein the described grafting sublayer 121 of described functional layer 12.
After uv photo initiated grafting, described base membrane layer 11 forms the described grafting sublayer 121 of described functional layer 12,Bring modified function thereby there is described grafting sublayer 121, such as the elecrtonegativity due to described grafting sublayer, makeObtain the improvement in performance of described modified filter membranes. Especially, in grafting after electronegative described modified monomer, byIn the electrostatic interaction of electric charge, in the time sieving, and there is electrostatic repulsion between anion in former water,Therefore, be not only the screening based on aperture to the filtration of water, also there is electrostatic interaction, electrostatic interaction tool simultaneouslyThe radius that has certain effect, makes to sieve aperture and reduces, thereby has improved the screening precision of described modified filter membranes,Electrostatic interaction shows good Rejection to high price anion simultaneously.
Embodiment 1: choose polypropylene (Polypropylene, PP) cotton as described base membrane layer 11, modification listBody is sodium p styrene sulfonate (SSS), and the pure water flux of the cotton filter membrane of PP is issued at 0.1Mpa pressure500L/m2/h。
The adsorption of light-sensitive catalyst: will described in state the cotton filter membrane of PP and be immersed in and contain TiO2Suspension with PEGIn more than 1 hour, and simultaneously with supersonic generator act on suspension prevent its cohesion, then put into clear waterMiddle rinse 1～2 time, removes the nano particle that is firmly absorption.
Ultraviolet radiation graft modified monomer: the cotton filter membrane of described PP is installed in one first reactor 5, at described PPThe graft modification monomer SSS solution of the top interpolation 10% of cotton filter membrane is high to the cotton filter membrane of the described PP predetermined 4cm in topDegree. Place copper/saturated copper sulphate solution on one second reactor 2 tops, to predetermined level height 1cm, for filterGo UV light below wavelength 300nm to suppress the homopolymerization of grafted monomers. One uviol lamp 3 is arranged at described secondReactor 2 top positions, and make described uviol lamp 3 and the cotton filter membrane of described PP for distance be 7cm. WithUltraviolet light intensity instrumentation must be 8.7mWcm at the ultraviolet ray intensity of the cotton filter membrane of described PP surface wavelength 365nm-2。Predose is to the logical nitrogen 5min of described the first reactor, to remove the micro amount of oxygen in modified monomer solution. Ultraviolet spokeIn blanket of nitrogen, carry out certain hour according to being grafted on. After finishing, reaction takes out from container the described PP cotton after graftingFilter membrane, is placed on cotton described PP filter membrane in ethanol/water solution, in ultrasonic washing agent, washs the scheduled time,15min, repeats 3 times, taking remove unreacted modified monomer and stick to described base membrane layer 11 surfaces and aperture asHomopolymers. The NaSO that is 5% with mass fraction again4Solution soaks 2h, carries out ion-exchange, makes saponification. SoClean with distilled water afterwards, put into deionized water through the described basement membrane of said method and processing and soak stand-by.
Embodiment 2: choose polypropylene (Polypropylene, PP) cotton as described base membrane layer 11, the cotton filter of PPThe pure water flux of film is 500L/m under 0.1Mpa pressure2/ h. Modified monomer is acrylic acid (AA).
The adsorption of light-sensitive catalyst: will described in state the cotton filter membrane of PP and be immersed in and contain TiO2Suspension with PEGIn more than 1 hour, and simultaneously with supersonic generator act on suspension prevent its cohesion, then put into clear waterMiddle rinse 1～2 time, by the not firmly nano particle of absorption removal.
Ultraviolet radiation graft modified monomer: the cotton filter membrane of described PP is installed in one first reactor 5, at described PPThe graft modification monomer A A solution of the top interpolation 5% of cotton filter membrane is high to the cotton filter membrane of the described PP predetermined 4cm in topDegree. Place copper/saturated copper sulphate solution on one second reactor 2 tops, to predetermined level height 1cm, for filterGo UV light below wavelength 300nm to suppress the homopolymerization of grafted monomers. One uviol lamp 3 is arranged at described secondReactor 2 top positions, and make described uviol lamp 3 and the cotton filter membrane of described PP for distance be 7cm. WithUltraviolet light intensity instrumentation must be 8.7mWcm at the ultraviolet ray intensity of the cotton filter membrane of described PP surface wavelength 365nm-2。Predose is to the logical nitrogen 5min of described the first reactor, to remove the micro amount of oxygen in modified monomer solution. Ultraviolet spokeIn blanket of nitrogen, carry out certain hour according to being grafted on. After finishing, reaction takes out from container the described PP cotton after graftingFilter membrane, is placed on cotton described PP filter membrane in ethanol/water solution, in ultrasonic washing agent, washs the scheduled time,15min, repeats 3 times, taking remove unreacted modified monomer and stick to the cotton filter membrane surface of described PP and aperture asHomopolymers. The NaSO that is 5% with mass fraction again4Solution soaks 2h, carries out ion-exchange, makes saponification. SoClean with distilled water afterwards, put into deionized water through the described basement membrane of said method and processing and soak stand-by.
Embodiment 3: choose polyvinyladine floride (PolyvinylideneFluoride, PVDF) milipore filter as describedBase membrane layer 11, modified monomer is sodium p styrene sulfonate (SSS). The pure water flux of PVDF milipore filter is at 0.1MpaPressure is issued to 500L/m2/h。
The adsorption of light-sensitive catalyst: described PVDF milipore filter is immersed in and contains TiO2Suspension with PEGIn liquid more than 1 hour, and act on suspension with supersonic generator simultaneously and prevent its cohesion, then put into clearlyRinse 1～2 time in water, by the not firmly nano particle of absorption removal.
Ultraviolet radiation graft modified monomer: described PVDF milipore filter is installed in one first reactor 5, describedThe graft modification monomer SSS solution of the top interpolation 10% of PVDF milipore filter is predetermined to the cotton filter membrane of described PP top4cm height. Place copper/saturated copper sulphate solution on one second reactor 2 tops, to predetermined level height 1cm,Homopolymerization for the UV light below elimination wavelength 300nm with inhibition grafted monomers. One uviol lamp 3 is arranged at instituteState the second reactor 2 top positions, and what make described uviol lamp 3 and described PVDF milipore filter is distanceFor 7cm. With ultraviolet light intensity instrumentation must be at the ultraviolet ray intensity of the cotton filter membrane of described PP surface wavelength 365nm8.7mW·cm-2. Predose is to the logical nitrogen 5min of described the first reactor, to remove micro-in modified monomer solutionAmount oxygen. Ultraviolet irradiation is grafted on and in blanket of nitrogen, carries out certain hour. After finishing, reaction takes out from container after graftingDescribed PVDF milipore filter, described PVDF milipore filter is placed in ethanol/water solution, in ultrasonic washing agentThe middle washing scheduled time, 15min, repeats 3 times, to remove unreacted modified monomer and to stick to described PVDFThe homopolymers that milipore filter surface and aperture are. The NaSO that is 5% with mass fraction again4Solution soak 2h, carry out fromSon exchange, makes saponification. Then clean with distilled water, put into deionization through the described basement membrane of said method and processingIn water, soak stand-by.
Embodiment 4: choose polyvinyladine floride (PolyvinylideneFluoride, PVDF) milipore filter as describedBase membrane layer 11, modified monomer is acrylic acid (AA). The pure water flux of PVDF milipore filter is under 0.1Mpa pressureReach 500L/m2/h。
The adsorption of light-sensitive catalyst: described PVDF milipore filter is immersed in and contains TiO2Suspension with PEGIn liquid more than 1 hour, and act on suspension with supersonic generator simultaneously and prevent its cohesion, then put into clearlyRinse 1～2 time in water, removes the nano particle that is firmly absorption.
Ultraviolet radiation graft modified monomer: described PVDF milipore filter is installed in one first reactor 5, describedThe graft modification monomer A A solution of the top interpolation 5% of PVDF milipore filter is predetermined to the cotton filter membrane of described PP top4cm height. Place copper/saturated copper sulphate solution on one second reactor 2 tops, to predetermined level height 1cm,Homopolymerization for the UV light below elimination wavelength 300nm with inhibition grafted monomers. One uviol lamp 3 is arranged at instituteState the second reactor 2 top positions, and what make described uviol lamp 3 and described PVDF milipore filter is distanceFor 7cm. With ultraviolet light intensity instrumentation must be at the ultraviolet ray intensity of the cotton filter membrane of described PP surface wavelength 365nm8.7mW·cm-2. Predose is to the logical nitrogen 5min of described the first reactor, to remove micro-in modified monomer solutionAmount oxygen. Ultraviolet irradiation is grafted on and in blanket of nitrogen, carries out certain hour. After finishing, reaction takes out from container after graftingDescribed PVDF milipore filter, described PVDF milipore filter is placed in ethanol/water solution, in ultrasonic washing agentThe middle washing scheduled time, 15min, repeats 3 times, to remove unreacted modified monomer and to stick to described PVDFThe homopolymers that milipore filter surface and aperture are. The NaSO that is 5% with mass fraction again4Solution soak 2h, carry out fromSon exchange, makes saponification. Then clean with distilled water, put into deionization through the described basement membrane of said method and processingIn water, soak stand-by.
According to above-mentioned reaction condition, respectively the cotton filter membrane of PP and PVDF milipore filter are carried out to connecing of variable concentrationsThe surface modification of branch monomer, then characterizes the cotton filter membrane of the described PP after modification and PVDF milipore filterAnalyze, carry out respectively the nanofiltration performance of ATR-FITR analysis, mensuration graft copolymer membrane, the surface electrical of mensuration Modified MembraneLotus density, the relative molecular weight that passes through gel permeation chromatography copolymer, mensuration film surface contact angle and batTake the photograph the SEM image of film section etc., thus the superior function possessing by the known Modified Membrane of different detection modes.
Such as, can find the cotton filter membrane of PP and PVDF before modification by the mensuration of surface charge densityMilipore filter is electroneutral substantially, and the cotton filter membrane of PP after modification and PVDF milipore filter all have certain surfaceElectric charge, and be electric charge. Detection by film surface contact angle can find, the filter membrane after modification is not with respect toThe filter membrane surface contact angle of modification obviously reduces, and has good hydrophily. Contrast variable concentrations, dissimilarThe nanofiltration performance of modified filter membranes of grafted monomers, can find: traditional water purifier filter membrane does not have ion substantiallyHave crown_interception, and modified filter membranes after modification possesses ion rejection effect, and the aperture of film and the static of electric chargeBetween effect, have matching relationship, when conforming to a predetermined condition be, modified filter membranes has good water flux, simultaneouslyPossess good rejection, and traditional filter membrane between the two in opposed relation.
Further, in order to make described modified filter membranes there is more feature functionality, such as antibiotic property, make described filterFilm can be resisted germ contamination, reduces growing of bacterium. According to this preparation method of the present invention, described stepS21 also comprises step S212: described in self assembly layer by layer, self assembly sublayer 122 is to described base membrane layer 11. Logical122 absorption of described self assembly sublayer are added into described base membrane layer by the mode of crossing self-chambering, thereby make modified filter membranesThere is functional that described self-chambering sublayer 122 brings. Further, described self assembly sublayer 122 with instituteState grafting sublayer 122 contrary electrically, thereby the condition of self assembly is provided, by the alternating deposit of opposite chargesEffect, prepares described self assembly sublayer 122. Especially, described self assembly sublayer 122 is antibacterial heightMolecular layer, thus make described modified filter membranes 10 possess anti-microbial property. Being worth mentioning is, common antibacterial high scoreSon is all positively charged, and described grafting sublayer 121 is electronegative, therefore can meet the condition of self assembly layer by layer.
On the other hand, described self-chambering sublayer 122 contrary electrically can with the electrical phase of described grafting sublayer 121Regulate, thereby regulate the surface charge of described modified filter membranes 10 entirety, make the electric charge of its performance expection.
Especially, described step S212 layer by layer self assembling process generally to choose harmless modification shell poly-Sugar and PLL, the polyanion that coordinates multilayer absorption to use carries out self assembly layer by layer. Polyanion asSulfonic group cyclodextrin, sodium alginate.
Further, the detailed process of self assembly is layer by layer:
By described base membrane layer 11 with the film of described grafting sublayer immerse alternately contain polycation or poly-cloudy fromIn the aqueous solution of son 15 minutes, after immersing, need vibration simultaneously or make described from group by ul-trasonic irradiationDress sublayer 122 is evenly in conjunction with described grafting sublayer 121, until obtain the assembling number of plies of expection. Immersion alternatelyThe aqueous solution (being all that one deck cation, one deck anion are alternately put into conventionally) of polycation or polyanionOperating procedure it is also to be noted that, needs to put into clear water and wash after the complete one deck of every assembling, will not haveThere are polycation or the polyanion of strong bonded to wash off, the thickness of each assembled layers and fastness are all arrivedEnsure.
Further, in other embodiments of the invention, before adding polycation or polyanion, can addEnter TRITC-BSA, carry out fluorescence labeling, thereby be convenient to judge the filtering accuracy of assembled layers. It is worth mentioning that,Carrying out, after uv photo initiated grafting, proceeding self assembly layer by layer, thereby completing by the charge environment of uv photo initiated graftingSelf assembling process, makes to assemble thing and is assembled in securely described base membrane layer 11, thereby makes described base membrane layer 11Possess functional that assembling thing brings.
Can see from above, in the time manufacturing described filter core, can be by preparation method's preparation of described modified filter membranesDescribed modified filter membranes, thus the described modified filter membranes of superior performance obtained, make to manufacture by described manufacture methodThe described filter core obtaining is compared traditional filter core and is had more advantages, such as higher filtering accuracy, cloudy to high priceThe crown_interception of ion or harmful metal ion etc.
With reference to Figure 14, according to above preferred embodiment of the present invention, the invention provides a drainage method 1400,Described drainage method, taking the work principle of filter of above-mentioned modified filter membranes 10 as basis, on the basis of aperture screening, is drawnEnter electrostatic interaction, especially, also there is functionally selected crown_interception, therefore, with respect to traditional drainage sideMethod, can obtain the water quality of high-quality more by described method of the present invention.
Described drainage method 1400 comprises step S31: by the electrostatic interaction filtered water of surface charge. Be worthOne carries, and for traditional drainage method, is especially applied in the drainage method in water purifier field, mainMultistage filtering is carried out in aperture sieving actoion by the cotton filter core of PP and/or milipore filter, thereby is purified water, andAccording to drainage method of the present invention, introduce electrostatic effect, be applied in the middle of the process of filtered water, on the one handCan, based on electrostatic repulsion, like charges ion be held back, on the other hand by electrostatic repulsionThe operating radius of the existence in the middle of process, improves aperture screening precision. Thereby realize traditional aperture screeningNot available effect in filter method.
In an embodiment method, further comprise, in the electrostatic repulsion filtered water by surface negative chargeAnion. Such as, SO4 2-。
When electrostatic interaction filters, sieve filtration by aperture, make hydrone and other useful pointSon is by aperture, and the effect that realization is filtered. Therefore, further comprise step S32: aperture screening is filteredWater.
Further, after filtration, impurity and bacterium are trapped, and easily cause again growing of bacterium, and rootAccording to method of the present invention, described drainage method comprises: suppress bacteria breed in water by antibacterial macromolecule.
With reference to Figure 15, according to above preferred embodiment of the present invention, the invention provides a water treatment plant 100, shouldWith the described filter core in above-described embodiment. With respect to traditional water purifier, described water treatment plant adopts institute of the present inventionState filter core, therefore, it has higher filtering accuracy in the time of filtered water, can filter high price salt ion, mistakeNumerous advantages such as filter metal harmful ion. Described water treatment plant comprises multi-stage filter core, in described multi-stage filter core at leastOne-level filter membrane is through surface modification.
According to one embodiment of the invention, the multi-stage filter core of described water treatment plant 100 comprises at least one-level modificationPP cotton 101, the filter membrane of described MODIFIED PP cotton 101 obtains through above-mentioned filter membrane preparation method. NamelySay, the filter membrane of described first order filter core 101 is described modified filter membranes.
It is worth mentioning that, the common effect of the cotton filter core of PP in traditional water purifier is that former water is carried out to just mistakeFilter, removing in water more slightly can impurity, mud, colloid, suspended material etc., and filtering accuracy is lower on the one hand,On the other hand, almost there is no filtration for some salt ions, metal ion, conventionally need to pass through the second levelGranular activated carbon come peculiar smell in adsorbed water, heterochromatic, organic matter etc. And first order filter according to the present inventionCore 101 is the cotton modification filter core of PP, that is to say, described PP has added described functional layer in cotton surface, and this makesObtain the filtering accuracy that improves on the one hand described PP cotton, on the other hand, due to after surface modification, surface bandHave electric charge, high price anion is had to good Rejection, and these are all the traditional cotton filter core of first order PP institutesDo not possess. That is to say, described first order filter core 101 has been realized the part of existing active carbon filter coreFunction.
Further, described water treatment plant 100 comprises the cotton filter core of multistage described MODIFIED PP, is arranged at respectively differenceFiltration grade, such as being arranged at respectively the first order and the third level. By multistage filtering deep purifying, further goThe removal of impurity, and further improve filtering accuracy by multistage filtering, for follow-up filtration provides preferably water quality.The type that one skilled in the art will appreciate that each described filtration grade in described water treatment plant 100 is notRestriction of the present invention. In another embodiment of the present invention, of the described filtration grade of described filter 100One-level is the cotton filter core of described MODIFIED PP, and the third level is ion exchange resin, thereby can be by described MODIFIED PPCotton and/or described ion exchange resin is removed the part heavy metal ion in former water.
According to one embodiment of the invention, the multi-stage filter core of described water treatment plant comprises a modified ultrafiltration membrane, usesThe impurity such as bacterium, iron rust colloid and the organic matter in removing water. It is worth mentioning that described modification ultrafiltrationFilm carries out surface modification through preparation method of the present invention, and therefore surface has functional layer, such as grafting sublayer,Self assembly sublayer, therefore, on the basis of ultrafiltration principle, further filters by electrostatic interaction, reduces holeFootpath size, raising filtering accuracy, have especially the crown_interception to anion, and these are and traditional ultrafiltrationFilm is diverse.
Further, the multi-stage filter core of described water treatment plant comprises at least one grade particles active carbon, for adsorbed waterMiddle peculiar smell, heterochromatic, chlorine residue, organic matter, part heavy metal etc. The multi-stage filter core of described water treatment plant comprises oneLevel post active carbon, for improving mouthfeel. Described granular activated carbon level and described post active carbon level coordinate otherLevel filter core completes by effect.
According to one embodiment of the invention, the described multi-stage filter core of described water treatment plant comprises at least one ion-exchangeResin bed, for removing the part heavy metal ion of former water in the mode of ion-exchange. Especially, described fromSub-exchange resin layer and described granular activated carbon combination, peculiar smell in described granular activated carbon adsorbed water, heterochromatic, more thanChlorine and organic matter etc., and described ion exchange resin is removed part heavy metal ion in water.
It is worth mentioning that, in different embodiment, multistage described filtration grade optionally arranges, as requiredPosition is separately set, that is to say, the cotton filter core level of described MODIFIED PP, described granular activated carbon level and instituteState post active carbon level and optionally arrange, to meet different filtration needs.
For example, in a kind of arrangement, can be arranged as successively: the first order is the cotton filter of described MODIFIED PPCore, the second level is described granular activated carbon, the third level is the cotton filter core of described MODIFIED PP or ion exchange resin,The fourth stage is described post active carbon, and level V is described modified ultrafiltration membrane.
Certainly, in other embodiments, can also add different filtration grades to meet the different requirements of filtering, thanAs accurate extruded activated carbon level, reverse osmosis membrane, weak alkali energy rod etc. Also can combine with traditional filter coreApplication, such as PP cotton, milipore filter.
Those skilled in the art should be understood that, the arrangement of described multi-stage filter core and the shape of filter coreBe not restriction of the present invention, in different embodiments of the invention, can choose as required different filter coresBe distributed in different filtration grades, also can as required described filter core be designed to the suitable shape being mounted.
One skilled in the art will understand that the conduct of the embodiments of the invention shown in foregoing description and accompanying drawingDo not limit for example the present invention. Object of the present invention is complete and realization effectively. Function of the present invention andStructural principle is shown in an embodiment and is illustrated, is not deviating under described principle embodiments of the present inventionCan there be any distortion or amendment.
Claims (10)
1. a filter core, for water treatment plant, is characterized in that, comprising: at least one modified filter membranes, described filterFilm surface is predetermined charge, carries out filtered water, thereby change described in surface modification with the electrostatic interaction by electric chargeProperty filter membrane.
2. filter core according to claim 1, wherein said modified filter membranes surface is negative electrical charge or positive electricityLotus property, anion or cation in Coulomb repulsion water, thereby in the time of described filter element filtering water anion in trap waterOr cation.
3. want its filter core described in 1 according to right, wherein said modified filter membranes surface has antibacterial macromolecule layer,Thereby suppress the bacteria breed of described modified filter membranes.
4. filter core according to claim 1, wherein said modified filter membranes comprises a base membrane layer and a functionLayer, described functional layer is adsorbed in described modified filter membranes surface, with to described base membrane layer surface modification.
5. filter core according to claim 4, wherein said functional layer comprises a grafting sublayer, described in connectBranch layer grafts on described base membrane layer surface by modified monomer and forms, and is electric charge, to make described modificationFilter membrane obtains predetermined charge.
6. filter core according to claim 4, wherein said base membrane layer has the light that is suitable for ultraviolet radiation graftQuick property, the light sensitivity of wherein said base membrane layer obtains by adsorption light-sensitive catalyst, described photocatalysisAgent is selected from TiO2, one in ZnO or the mixture of the two.
7. filter core according to claim 4, wherein said grafting sublayer is by the mode of ultraviolet radiation graftGraft on described base membrane layer, the modified monomer of described grafting sublayer is selected from combination: polystyrene-based sodium sulfonate, poly-One or more in acrylic acid and aforementioned the two copolymer.
8. filter core according to claim 5, wherein said functional layer comprises a self assembly sublayer, described inSelf assembly sublayer is assembled in described grafting sublayer, to make described modified filter membranes obtain assembling thing function, described fromAssembling sublayer is assembled in described grafting sublayer by the mode of self assembly layer by layer, and subgroup dress sublayer has biocidal property,Described self assembly sublayer is modification of chitosan or PLL.
9. according to the arbitrary described filter core of claim 4 to 8, wherein said base membrane layer is selected from combination: PVDFOne in milipore filter, polypropylene PP cotton and polyether sulfone PES, and described functional layer is adsorbed in described base membrane layerSurface, thus described base membrane layer is carried out to surface modification.
10. a filter core manufacture method, is characterized in that, comprises step:
S11: obtain the arbitrary described modified filter membranes of a claim 1 to 12: and
S12: by described modified filter membranes end portion encloses in an encapsulation external member.
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