CN103223308B - Composite nanofiltration membrane prepared based on aliphatic sulfonate condensation product - Google Patents
Composite nanofiltration membrane prepared based on aliphatic sulfonate condensation product Download PDFInfo
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Abstract
The invention relates to a composite nanofiltration membrane, especially relates to a composite nanofiltration membrane employing an aliphatic sulfonate condensation product as an anion polyelectrolyte. The composite nanofiltration membrane comprises a basal membrane layer and a composite membrane layer in order, and the composite membrane layer is formed by static self assembly of the cation polyelectrolyte and the anion polyelectrolyte, wherein, the anion polyelectrolyte is an aliphatic sulfonate condensation product solution. The aliphatic sulfonate condensation product is used as an anion polyelectrolyte, and compared with the present anion polyelectrolyte and aliphatic sulfonate condensation product has a lower cost, thereby reducing the cost of the prepared composite nanofiltration membrane, and improving the separating performance for Ni2+, Ca2+ divalent metal ions and xylenol orange, rhodamine B and other dye molecules in heavy metal ion waste water and dye waste water by the prepared composite nanofiltration membrane.
Description
Technical field
The present invention relates to a kind of composite nanometer filtering film, particularly relating to a kind of aliphatic sulfonate condensation product that adopts is composite nanometer filtering film prepared by anionic polyelectrolyte.
Background technology
NF membrane is a kind of new membrane isolation technics between ultrafiltration and counter-infiltration.The preparation of composite nanometer filtering film is better in intensity mostly, the membrane surface that flux is larger covers the very thin selective separation layer of one deck, its preparation method mainly contains cladding process, phase inversion (patent as publication number CN102091539A), interfacial polymerization is (as publication number CN101254419A, CN101559334A, the patent of CN101934201A), surface grafting method is (as publication number CN102000511A, CN102068912A, the patent of CN1586702A) etc., the preparation of commercial nanofiltration membrane many employings interfacial polymerization is (if publication number is CN102641667A, CN102151499A, the patent of CN1806901A), but the requirement of these methods to basement membrane is higher, side reaction is many, be difficult to the NF membrane obtaining superthin layer.
LBL self-assembly method utilizes electrostatic self-assembled technique alternately assembling polyanion and polycation electrolyte multilayer film, as ultra-thin parting absciss layer, thus obtain composite nanometer filtering film on basement membrane.The method technique is simple, film forming matter is abundant, by substrate restriction and can effective controlling diaphragm Rotating fields, get more and more people's extensive concerning.At present, the cationic polyelectrolyte that LBL self-assembly method uses mainly contains polymine, poly-divinyl propyl ammonium chloride, polyvinylamine, poly-N, N ' dimethyl diallyl ammonium chloride (patent as publication number CN102553461A, CN101274222A, CN101053780A, CN101298026A, CN102580550A), poly-4-vinyl arsenic pyridine (patent as publication number CN102688701A), publication number CN1724128A patent also disclose polyvinyl alcohol, collagen, shitosan and poly-D-lysine etc. as cationic polyelectrolyte solution, and anionic polyelectrolyte mainly contains kayexalate and Sodium Polyacrylate (as publication number CN102553461A, CN101053780A, CN101298026A, the patent of CN102580550A), kayexalate-maleic acid (salt) copolymer (patent as publication number CN101274222A), the patent of publication number CN1724128A also discloses employing polyvinyl sulfonate simultaneously, sulfuric acid glucose sugar, chondroitin sulfate, sodium alginate and polymethylacrylic acid etc. are as anionic polyelectrolyte solution.But never adopt aliphatic sulfonate condensation product as the relevant report of anionic polyelectrolyte solution.
Summary of the invention
For the weak point of above-mentioned technology, the invention provides a kind of is that anionic polyelectrolyte prepares composite nanometer filtering film with aliphatic sulfonate condensation product.
A kind of composite nanometer filtering film, comprise base membrane layer, polyelectrolyte composite bed successively, described polyelectrolyte composite bed is that cationic polyelectrolyte and anionic polyelectrolyte are formed through electrostatic self-assembled, and wherein, described anionic polyelectrolyte is aliphatic sulfonate condensation product solution.
Further, described basement membrane is the milipore filter that molecular weight is less than 100,000.
Preferably, described basement membrane is polyacrylonitrile ultrafiltration film, cellulose-acetafolic, polysulphone super-filter membrane, aluminium oxide ceramics milipore filter.
Preferably, described cationic polyelectrolyte comprises polymine (PEI), poly-divinyl propyl ammonium chloride (PDDA), polyvinylamine (PVA).
Preferably, described anionic polyelectrolyte comprises sulfonated acetone formaldehyde condensation products, sulfonation cyclohexanone formaldehyde condensation products, sulfonation acetophenone furfural condensation product, sulfonation MEK formaldehyde condensation products.
Beneficial effect of the present invention is, the anionic polyelectrolyte used is aliphatic sulfonate condensation product, aliphatic sulfonate condensation product is a class sulfonated ketone aldehyde condensate, it is the aliphatic macromolecule that carbonyls and aldehyde compound are condensed under proper condition, and open carbonyl by sulfonating reaction, a family macromolecule condensation product of hydrophilic sulfonic acid group is introduced in strand, because introducing hydrophilic sulfonic group in aliphatic sulfonate condensation product strand, make it can use as anionic polyelectrolyte, and compare existing anionic polyelectrolyte, the cost of aliphatic sulfonate condensation product is lower, reduce the cost preparing composite nanometer filtering film, Ni in the composite nanometer filtering film heavy metal ion waste water simultaneously prepared and waste water from dyestuff
2+, Ca
2+the dye molecules such as bivalent metal ion and dimethyl phenol orange, rhodamine B all have good separating property.
Accompanying drawing explanation
Fig. 1 is flow chart of the present invention.
Detailed description of the invention
Below in conjunction with accompanying drawing, the present invention is described in further detail.
A kind of composite nanometer filtering film, comprise base membrane layer, composite film successively, described composite film is that cationic polyelectrolyte and anionic polyelectrolyte are formed through electrostatic self-assembled, and wherein, described anionic polyelectrolyte is aliphatic sulfonate condensation product solution.
Further, described basement membrane is the milipore filter that molecular weight is less than 100,000.
Preferably, described basement membrane is polyacrylonitrile ultrafiltration film, cellulose-acetafolic, polysulphone super-filter membrane, aluminium oxide ceramics milipore filter.
Preferably, described cationic polyelectrolyte comprises polymine (PEI), poly-divinyl propyl ammonium chloride (PDDA), polyvinylamine (PVA).
Preferably, described anionic polyelectrolyte comprises sulfonated acetone formaldehyde condensation products, sulfonation cyclohexanone formaldehyde condensation products, sulfonation acetophenone furfural condensation product, sulfonation MEK formaldehyde condensation products.
Described composite nanometer filtering film, is prepared by following steps, as shown in Figure 1:
Step 101: take milipore filter as basement membrane, being immersed concentration is in the cationic polyelectrolyte solution of 1.0 ~ 10.0mg/mL, takes out, fully clean by deionized water after dipping 10 ~ 30min;
Step 102: film step 101 obtained is transferred in the aliphatic sulfonate condensation product solution of 1.0 ~ 20.0mg/mL, after dipping 10 ~ 30min, takes out, uses washed with de-ionized water.Described step repeats step can obtain described composite nanometer filtering film 2-8 time.
Embodiment 1
A kind of composite nanometer filtering film is prepared as follows:
Step 101: take polyacrylonitrile ultrafiltration film as basement membrane, being immersed concentration is in the polymine polyelectrolyte solution of 10.0mg/mL, takes out, fully clean by deionized water after dipping 10min;
Step 102: film step 101 obtained is transferred in the sulfonation cyclohexanone formaldehyde condensation products solution of 20.0mg/mL, after dipping 10min, takes out, uses washed with de-ionized water.
Repeat above-mentioned steps 2 times, described composite nanometer filtering film can be obtained.
Embodiment 2
A kind of composite nanometer filtering film is prepared as follows:
Step 101: take cellulose-acetafolic as basement membrane, being immersed concentration is in the polymine polyelectrolyte solution of 1.0mg/mL, takes out, fully clean by deionized water after dipping 30min;
Step 102: film step 101 obtained is transferred in the sulfonation cyclohexanone formaldehyde condensation products solution of 1.0mg/mL, after dipping 30min, takes out, uses washed with de-ionized water.
Repeat above-mentioned steps 8 times, described composite nanometer filtering film can be obtained.
Embodiment 3
A kind of composite nanometer filtering film is prepared as follows:
Step 101: take polyacrylonitrile ultrafiltration film as basement membrane, being immersed concentration is in the polymine polyelectrolyte solution of 5.0mg/mL, takes out, fully clean by deionized water after dipping 20min;
Step 102: film step 101 obtained is transferred in the sulfonation cyclohexanone formaldehyde condensation products solution of 8.0mg/mL, after dipping 15min, takes out, uses washed with de-ionized water.
Repeat above-mentioned steps 5 times, described composite nanometer filtering film can be obtained.
Embodiment 4:
The present embodiment is roughly the same with embodiment 3, unlike adding 100 steps before step 101, specific as follows:
Step 100: be less than the fine milipore filter of polypropylene of 100,000 for basement membrane with molecular cut off, after the NaOH solution process 30min of 2mol/L, spends deionized water to neutral;
Step 101: it is in the polyvinylamine polyelectrolyte solution of 5.0mg/mL that the polyacrylonitrile ultrafiltration film after step 100 being processed immerses concentration, takes out after dipping 20min, fully cleans by deionized water;
Step 102: film step 101 obtained is transferred in the sulfonated acetone formaldehyde condensation products solution of 8.0mg/mL, after dipping 20min, takes out, uses washed with de-ionized water.
Repeat above-mentioned steps 6 times, described composite nanometer filtering film can be obtained.
Embodiment 5:
The present embodiment is roughly the same with embodiment 4, different unlike the basement membrane adopted in step 100, specific as follows:
Step 100: be less than the polysulphone super-filter membrane of 100,000 with molecular cut off for basement membrane, after fully washing, soaks 2h with deionization;
Step 101: it is in the polymine polyelectrolyte solution of 6.0mg/mL that the polysulphone super-filter membrane after step 100 being processed immerses concentration, takes out after dipping 20min, fully cleans by deionized water;
Step 102: film step 101 obtained is transferred in the sulfonation MEK formaldehyde condensation products solution of 8.0mg/mL, after dipping 20min, takes out, uses washed with de-ionized water.
Repeat above-mentioned steps 6 times, described composite nanometer filtering film can be obtained.
Embodiment 6:
The present embodiment is roughly the same with embodiment 4, different unlike the basement membrane adopted in step 100, specific as follows:
Step 100: be less than the aluminium oxide ceramics milipore filter of 100,000 for basement membrane with molecular cut off, after fully washing, soaks 2h with deionization;
Step 101: it is in the poly-divinyl propyl ammonium chloride polyelectrolyte solution of 5.0mg/mL that the aluminium oxide ceramics milipore filter after step 100 being processed immerses concentration, takes out after dipping 20min, fully cleans by deionized water;
Step 102: film step 101 obtained is transferred in the sulfonation acetophenone furfural condensation product solution of 8.0mg/mL, after dipping 20min, takes out, uses washed with de-ionized water.
Repeat above-mentioned steps 7 times, described composite nanometer filtering film can be obtained.
Composite nanometer filtering film prepared by embodiment 1-6 under 0.6MPa pressure, to Ni
2+, Ca
2+ion and dyestuff dimethyl phenol orange, the rejection of rhodamine B and flux are tested, as shown in table 1.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Composite nanometer filtering film prepared by table 1 the present invention is separated bivalent metal ion and dye solution
。
Claims (4)
1. the composite nanometer filtering film prepared based on aliphatic sulfonate condensation product, comprise base membrane layer, composite film successively, described composite film is that cationic polyelectrolyte and anionic polyelectrolyte are formed through electrostatic self-assembled, it is characterized in that, described anionic polyelectrolyte is sulfonated acetone formaldehyde condensation products, sulfonation cyclohexanone condensation product, sulfonation acetophenone furfural condensation product or sulfonation MEK formaldehyde condensation products.
2. composite nanometer filtering film as claimed in claim 1, it is characterized in that, described basement membrane is the milipore filter that molecular weight is less than 100,000.
3. composite nanometer filtering film as claimed in claim 2, it is characterized in that, described basement membrane is polyacrylonitrile ultrafiltration film, cellulose-acetafolic, polysulphone super-filter membrane, aluminium oxide ceramics milipore filter.
4. composite nanometer filtering film as claimed in claim 1, is characterized in that, described cationic polyelectrolyte comprises polymine PEI, poly-divinyl propyl ammonium chloride PDDA, polyvinylamine PVA.
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| CN103449735B (en) * | 2013-08-26 | 2015-11-18 | 北京工业大学 | A kind of nanometer hydrated calcium silicate super-hydrophilic thin film and preparation method thereof and application |
| CN104028120B (en) * | 2014-05-16 | 2015-12-02 | 浙江大学 | Sodium carboxymethylcellulose compound fills the preparation method of polyamide nanofiltration membrane |
| CN104028119B (en) * | 2014-05-16 | 2015-12-02 | 浙江大学 | A kind of preparation method of carboxylic acid betaine type complex compound modified polyamide NF membrane |
| CN106256839B (en) * | 2015-06-18 | 2019-02-19 | 中国石油化工股份有限公司 | A kind of method that surface thermal polymerization prepares ion blotting composite membrane |
| CN106334447A (en) * | 2016-09-28 | 2017-01-18 | 东莞市联洲知识产权运营管理有限公司 | Anti-pollution composite nano filtering membrane for direct dye waste liquid treatment |
| CN107486026B (en) * | 2017-08-18 | 2021-04-02 | 清华大学 | Separation membrane resistant to biological contamination and method for preparing same |
| CN110787644B (en) * | 2019-10-15 | 2020-12-18 | 华中科技大学 | Loose nanofiltration membrane based on branched polyethyleneimine, and preparation and application thereof |
| CN111036097B (en) * | 2019-12-31 | 2022-04-05 | 宁波日新恒力科技有限公司 | Polyelectrolyte coating nanofiltration composite membrane for treating electroplating wastewater and application thereof |
| CN111423877B (en) * | 2020-03-12 | 2022-05-13 | 太原理工大学 | Sulfonated acetone-formaldehyde compound with ratio type pH fluorescence response and preparation method thereof |
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| CN1724128A (en) * | 2005-06-22 | 2006-01-25 | 南京工业大学 | Process for preparing organic and inorganic composite film by autoassembling tech |
| EP1832629A1 (en) * | 2006-03-10 | 2007-09-12 | MPG Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | Corrosion inhibiting pigment comprising nanoreservoirs of corrosion inhibitor |
| WO2008133672A2 (en) * | 2006-12-22 | 2008-11-06 | Drexel University | Nanowires and coatings of self-assembled nanoparticles |
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| CN1724128A (en) * | 2005-06-22 | 2006-01-25 | 南京工业大学 | Process for preparing organic and inorganic composite film by autoassembling tech |
| EP1832629A1 (en) * | 2006-03-10 | 2007-09-12 | MPG Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | Corrosion inhibiting pigment comprising nanoreservoirs of corrosion inhibitor |
| WO2008133672A2 (en) * | 2006-12-22 | 2008-11-06 | Drexel University | Nanowires and coatings of self-assembled nanoparticles |
| CN102580550A (en) * | 2012-03-05 | 2012-07-18 | 中国海洋大学 | Method for producing polyelectrolyte self-assembly composite nanofiltration membrane |
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