CN102814126A - Preparation method of high-flux antioxidant nanofiltration membrane - Google Patents
Preparation method of high-flux antioxidant nanofiltration membrane Download PDFInfo
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- CN102814126A CN102814126A CN2011101532543A CN201110153254A CN102814126A CN 102814126 A CN102814126 A CN 102814126A CN 2011101532543 A CN2011101532543 A CN 2011101532543A CN 201110153254 A CN201110153254 A CN 201110153254A CN 102814126 A CN102814126 A CN 102814126A
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- nanofiltration membrane
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Abstract
The invention relates to a preparation method of a high-flux antioxidant nanofiltration membrane. The nanofiltration membrane prepared by the method has high-flux and antioxidant characteristics. The preparation method is mainly characterized by including steps of adding phenylene diamine or a short-chain ortho-alkyl-derivative which serves as a crosslinking agent into aqueous-phase solution containing piperazine and surfactants; performing interfacial polymerization reaction with organic-phase solution containing trimesoyl chloride; and heating to prepare a layer of antioxidant composition nanofiltration membrane made of polyamide materials on a porous carrier supporting layer. Rejection rate and pure water flux of the nanofiltration membrane can be controlled flexibly by controlling concentration of the phenylene diamine or short-chain ortho-alkyl-derivative added into the aqueous-phase solution. The nanofiltration membrane prepared by the method is applicable to the field of water treatment utilizing conventional nanofiltration membrane technology; and the application field of the nanofiltration membrane can be expanded by flexibly controlling the molecular weight cutoff.
Description
Technical field
The present invention relates to the preparation method of the anti-oxidant NF membrane of a kind of high flux; The NF membrane that makes can also be controlled its molecular cut off flexibly through the change crosslinker concentration and expand the NF membrane application except the water treatment field that is applicable to conventional NF membrane technology.
Background technology
Membrane technology is applied to the particulates such as suspended particulate, colloid, dissolved organic matter and ion of branch in dried up as isolation technics of new generation and has obtained development rapidly in decades in the past.Especially be widely used in nanofiltration and reverse osmosis technology, bitter softening and the seawater desalination at drinking water.Utilizing interface polymerization reaction to generate PA membrane at present is the method that mainly prepares composite nanometer filtering film; But in practical engineering application because the pollution of film; Need frequent Chemical cleaning, use the liquor natrii hypochloritis to clean nanofiltration or reverse osmosis membrane especially repeatedly after, the polyamide composite bed is by chemical degradation; Desalting effect worsens, and influences the life-span of effluent quality and film.In addition, some contain oxidation unit operation water treatment technology in because common NF membrane resistance to oxidation not needs other processing units of extra increase, limited the development of NF membrane in this field, increased processing cost.
For improving the oxidation resistance of NF membrane, need do modification to PA membrane and handle.Common modification technology is at the oxidation resistant film of aramid layer surface-coated one deck or grafting one deck sludge proof material.Application number is China's invention application open " a kind of anti-oxide composite reverse osmosis membrane " (publication number: be that openly " anti-oxide composite reverse osmosis membrane " (publication number: CN 10130155A) of application is openly invented by China of 200610051200.5 with application number CN 101147846A) of 200610051219.X; Disclose a kind of with persulfate solution post processing aramid layer; Change aramid layer Surface Physical chemical property, reach oxidation resistant purpose.Although this method has increased the hydrophily of film, aramid layer configuration of surface and salt rejection rate all worsen to some extent, and have increased the complexity and the cost of original production technology, are unfavorable for the quality control of producing.
Application number is 97193174.7 Chinese disclosure of the Invention application open " reverse osmosis composite membrane and carry out the method for reverse-osmosis treated with it " (publication number: CN1213985A); The polyvinyl alcohol (PVA) that discloses at aramid layer surface recombination one deck 99% improves surface hydrophilicity, and the oxidation resistance of film is also improved.Yet this PVA layer is incomplete and aramid layer is crosslinked, and in the use of film, the PVA layer breaks away from from the film surface easily gradually, loses the effect of protection polyamide composite bed.
Usually the not anti-oxychloride of polyamide material mainly be because amide-type the nitrogen-atoms of urethane bonds combine with hydrogen atom, hydrogen atom by the chlorine replacement, causes the C-N bond fission of polyurethane easily, influences the rejection of PA membrane material.Therefore, if can be with the primary amine and the acyl chloride reaction of amino polyfunctional group of secondary amine class or chemical steric hindrance, its non-oxidizability will improve greatly, thereby expands the NF membrane application.
Summary of the invention
The preparation method who the purpose of this invention is to provide the anti-oxidant NF membrane of a kind of high flux.Technology of the present invention is simple, and is easy to operate, and automaticity is high, and raw material is easy to get, and cost is low, can realize serialization production.
The present invention provides the preparation method of polyamide nanofiltration membrane, and it may further comprise the steps:
1) aqueous solution of piperazine and phenylenediamine or its short-chain alkyl derivative is provided, piperazine is 0.5%-5% at the mass percent of aqueous phase in the said aqueous solution; The mass percent of phenylenediamine or its short-chain alkyl derivative is 0.1%-0.8% in the said aqueous solution; What contain mass fraction in the said aqueous solution and be 0.025%-0.5% plays the surfactant that is uniformly distributed with the water effect between water and porous support membrane; Containing mass fraction in the said aqueous solution is 0.5%-0.5% quaternary ammonium strong acid salt; The pH of the said aqueous solution is 8-14;
2) flooded porous carrier 1-5 minute with the said aqueous solution, on said porous carrier, form even liquid film, and remove unnecessary water with the soft and smooth roller bearing of material;
3) make the many empty carriers through dipping contact 10-70 second with containing the pyromellitic trimethylsilyl chloride organic facies, carry out interface polymerization reaction, the mass percent of said pyromellitic trimethylsilyl chloride in organic facies is 0.025%-0.5%.
The present invention also provides a kind of polyamide nanofiltration membrane, and it comprises porous carrier and the aramid layer that obtains through interface polymerization reaction, and described NF membrane uses following method to make:
1) aqueous solution of piperazine and phenylenediamine or its short-chain alkyl derivative is provided, piperazine is 0.5%-5% at the mass percent of aqueous phase in the said aqueous solution; The mass percent of phenylenediamine or its short-chain alkyl derivative is 0.05%-0.8% in the said aqueous solution; What contain mass fraction in the said aqueous solution and be 0.025%-0.5% plays the surfactant that is uniformly distributed with the water effect between water and porous support membrane; Containing mass fraction in the said aqueous solution is 0.5%-0.5% quaternary ammonium strong acid salt; The pH of the said aqueous solution is 8-14;
2) flooded porous carrier 1-5 minute with the said aqueous solution, on said porous carrier, form even liquid film, and remove unnecessary water;
3) make the many empty carriers through dipping contact 10-70 second with containing the pyromellitic trimethylsilyl chloride organic facies, carry out interface polymerization reaction, the mass percent of said pyromellitic trimethylsilyl chloride in organic facies is 0.025%-0.5%.
The practical implementation method is following: the concentration of said aqueous phase piperazine is 0.5%-5%, is preferably 1.5%-3%; Said phenylenediamine or its short chain alkanes derivative are m-phenylene diamine (MPD), p-phenylenediamine (PPD), and 2, the 6-diaminotoluene, 2, the 4-diaminotoluene, the 4-methoxy-m-phenylenediamine is preferably 2, the 6-diaminotoluene, mass percent is 0.05%-0.8%, is preferably 0.1%-0.5%; The mass fraction of said aqueous phase surfactant is 0.025%-0.5%, is preferably 0.1%-0.25%, and said surfactant is a neopelex; Containing mass fraction in the said aqueous solution is 0.5%-0.5% quaternary ammonium strong acid salt, and said quaternary ammonium salt is an etamon chloride; The pH of the said aqueous solution is 8-14, and said pH conditioning agent is a triethylamine.
Said porous carrier materials is polysulfones, polyether sulfone, sulfonated polyether sulfone or SPSF, and molecular cut off is below 300,000 dal, is preferably 4000dal-50000dal.
Said porous carrier dip time is 1-5 minute, is preferably 1-3 minute, preferred 2 minutes.
The mass percent that the organic facies that porous carrier said and the dipping water reacts contains trimesoyl chloride is 0.025%-0.5%; Be preferably 0.15%-0.25%; The organic facies solvent is the alkane or the cycloalkane of a contained 5-12 carbon atom, is preferably the mixture of n-hexane, normal heptane, cyclohexane or above alkane; Said water and organic facies time of contact are 10-70 second, are preferably 15-45 second.
The specific embodiment
Embodiment 1:
Use the PES milipore filter of molecular cut off as 20000dal; Immersion contain mass fraction be 2% piperazine, 0.2% dodecyl sodium sulfate, 2% etamon chloride, 0.23% 2; 6-diaminotoluene and pH are in the aqueous solution between 11 ~ 12, fully soak into 2 minutes, remove the unnecessary aqueous phase solution in membrane surface surface; Be the basement membrane that has water that the organic phase solution of 0.15% pyromellitic trimethylsilyl chloride contacts 45s with containing mass fraction then; Organic solution is n-hexane, and reaction finishes to be placed in 65 ℃ the baking oven and kept 12 minutes, can obtain the anti-oxidant composite nanometer filtering film of described high flux.
Under the pressure of 0.3MPa, measure the rejection 94.2% of this NF membrane, pure water flux 8.22L/ (m with the aqueous sodium persulfate solution of 2000ppm
2H).
With deionized water rinsing film 5min, soak 10h with the liquor natrii hypochloritis of 2000ppm then after, rejection and the pure water flux of measuring film once more are respectively 94.2% and 8.28 L/ (m
2H).
Embodiment 2:
Use the PES milipore filter of molecular cut off as 10000dal; Immersion contain mass fraction be 2% piperazine, 0.2% dodecyl sodium sulfate, 2% triethylamine camsilate, 0.15% 2,6-diaminotoluene and pH are in the aqueous solution between 11 ~ 12, fully soak into 2 minutes; Remove the unnecessary aqueous phase solution in membrane surface surface; Be the basement membrane that has water that the organic phase solution of 0.15% pyromellitic trimethylsilyl chloride contacts 45s with containing mass fraction then, organic solution is n-hexane and normal heptane mixture, and volume ratio is 2:1; Reaction finishes to be placed in 65 ℃ the baking oven and kept 12 minutes, can obtain the anti-oxidant composite nanometer filtering film of described high flux.
The aqueous sodium persulfate solution of use 2000ppm is measured this NF membrane under the pressure of 0.3MPa rejection is 93.1%, pure water flux 9.18L/ (m
2H).
With deionized water rinsing film 5min, soak 10h with the liquor natrii hypochloritis of 2000ppm then after, rejection and the pure water flux of measuring film once more are respectively 92.8% and 9.23 L/ (m
2H).
Claims (4)
1. the preparation method of the anti-oxidant NF membrane of high flux is characterized in that it comprises the steps:
1) aqueous solution of piperazine and phenylenediamine or its short-chain alkyl derivative is provided, piperazine is 0.5%-5% at the mass percent of aqueous phase in the said aqueous solution; Be 0.1%-0.8% as the phenylenediamine of crosslinking agent or the mass percent of its short-chain alkyl derivative in the said aqueous solution; What contain mass fraction in the said aqueous solution and be 0.025%-0.5% plays the surfactant that is uniformly distributed with the water effect between water and porous support membrane; Containing mass fraction in the said aqueous solution is 0.5%-0.5% quaternary ammonium strong acid salt; The pH of the said aqueous solution is 8-14;
2) flooded porous carrier 1-5 minute with the said aqueous solution, on said porous carrier, form even liquid film, and remove unnecessary water with the soft and smooth roller bearing of material;
3) make the many empty carriers through dipping contact 10-70 second with containing the pyromellitic trimethylsilyl chloride organic facies, carry out interface polymerization reaction, the mass percent of said pyromellitic trimethylsilyl chloride in organic facies is 0.025%-0.5%.
2. be that the mass percent of phenylenediamine or its short-chain alkyl derivative is 0.1%-0.8% according to the described aqueous phase of claim 1 as the material of crosslinking agent.
3. be that phenylenediamine or its short-chain alkyl derivative are m-phenylene diamine (MPD) according to the described aqueous phase of claim 2 as the material of crosslinking agent, p-phenylenediamine (PPD), 2,6-diaminotoluene, 2,4-diaminotoluene, 4-methoxy-m-phenylenediamine.
4. be that the mass percent of phenylenediamine or its short-chain alkyl derivative is 0.1%-0.8% according to the described aqueous phase of claim 2 as the material of crosslinking agent; Under the situation that does not change other conditions; Change the concentration of said crosslinking agent, can control molecular cut off and flux flexibly.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104474927A (en) * | 2014-12-17 | 2015-04-01 | 北京碧水源净水科技有限公司 | Method for preparing structure and performance controllable super nanofiltration membrane |
| CN105771700A (en) * | 2014-12-15 | 2016-07-20 | 华东理工大学 | Mixed diamine monomer adopted chlorine-resistant nanofiltration membrane and preparation method therefor |
| CN106178996A (en) * | 2016-08-03 | 2016-12-07 | 中国科学院城市环境研究所 | A kind of super-hydrophobic nano particle polyamide nano complex reverse osmosis membrane and preparation method thereof |
| CN106474933A (en) * | 2016-10-28 | 2017-03-08 | 河南华禹环保科技有限公司 | The preparation method of hollow fiber ultrafiltration membrane |
| CN106914156A (en) * | 2017-04-10 | 2017-07-04 | 浙江工业大学 | A kind of preparation method of Novel polyvinyl alcohol NF membrane |
| CN108636141A (en) * | 2018-06-13 | 2018-10-12 | 贵州永合益环保科技有限公司 | A kind of preparation method of graphene desalination film |
| CN114699930A (en) * | 2022-03-01 | 2022-07-05 | 郑州大学 | Polyazacyclic amide membrane for dye wastewater treatment and preparation method thereof |
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| CN101381125A (en) * | 2008-10-13 | 2009-03-11 | 浙江大学 | Method for improving reverse osmosis compound film separating property |
| CN101874989A (en) * | 2009-12-18 | 2010-11-03 | 北京时代沃顿科技有限公司 | Microbial contamination resistance composite reverse osmosis membrane and preparation method thereof |
| CN102019149A (en) * | 2010-12-01 | 2011-04-20 | 杭州水处理技术研究开发中心有限公司 | Method for preparing solvent-resistant modified polyamide nanofiltration membrane |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105771700A (en) * | 2014-12-15 | 2016-07-20 | 华东理工大学 | Mixed diamine monomer adopted chlorine-resistant nanofiltration membrane and preparation method therefor |
| CN104474927A (en) * | 2014-12-17 | 2015-04-01 | 北京碧水源净水科技有限公司 | Method for preparing structure and performance controllable super nanofiltration membrane |
| CN106178996A (en) * | 2016-08-03 | 2016-12-07 | 中国科学院城市环境研究所 | A kind of super-hydrophobic nano particle polyamide nano complex reverse osmosis membrane and preparation method thereof |
| CN106474933A (en) * | 2016-10-28 | 2017-03-08 | 河南华禹环保科技有限公司 | The preparation method of hollow fiber ultrafiltration membrane |
| CN106914156A (en) * | 2017-04-10 | 2017-07-04 | 浙江工业大学 | A kind of preparation method of Novel polyvinyl alcohol NF membrane |
| CN106914156B (en) * | 2017-04-10 | 2019-09-17 | 浙江工业大学 | A kind of preparation method of polyvinyl alcohol nanofiltration membrane |
| CN108636141A (en) * | 2018-06-13 | 2018-10-12 | 贵州永合益环保科技有限公司 | A kind of preparation method of graphene desalination film |
| CN108636141B (en) * | 2018-06-13 | 2021-08-10 | 贵州永合益环保科技有限公司 | Preparation method of graphene desalination film |
| CN114699930A (en) * | 2022-03-01 | 2022-07-05 | 郑州大学 | Polyazacyclic amide membrane for dye wastewater treatment and preparation method thereof |
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Application publication date: 20121212 |