CN102350227A - Preparation method of fluorion selective nanofiltration membrane - Google Patents
Preparation method of fluorion selective nanofiltration membrane Download PDFInfo
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- CN102350227A CN102350227A CN2011102673055A CN201110267305A CN102350227A CN 102350227 A CN102350227 A CN 102350227A CN 2011102673055 A CN2011102673055 A CN 2011102673055A CN 201110267305 A CN201110267305 A CN 201110267305A CN 102350227 A CN102350227 A CN 102350227A
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Abstract
The invention discloses a preparation method of a composite membrane, particularly a preparation method of a fluorion selective nanofiltration membrane. A common base membrane contacts an organic solution containing 1,3,5-benzenetricarbonyl trichloride and a water solution containing polyethyleneimine to obtain the nanofiltration membrane. The nanofiltration membrane has the advantages of high selectivity for fluorions and high consumption ratio; and the preparation method is simple and convenient to operate. The membrane prepared by the method disclosed by the invention has wide applicability in high-fluorine regions.
Description
Technical field
The present invention relates to a kind of preparation method of composite membrane, specifically be meant a kind of preparation method of fluorine ion selectivity NF membrane.
Technical background
Fluorine element is the trace element of needed by human, but just can harmful to human when fluorine content surpasses 4ppm in the drinking-water even cause acute poisoning.Drinking Water in China standard code fluorinated volume is 1ppm; The highest permission discharge capacity of fluorine element is 10ppm in the sewage drainage standard regulation trade effluent.At present China rural area have surpass that 7,000 ten thousand people drink that fluorinated volume exceeds standard water.Tradition water body defluorination method has the precipitation method, absorption method, membrane separation process etc.Membrane separation process is compared with the above two to have high efficiency, saves advantage such as space.Film separates the defluorination aspect, main at present counter-infiltration, electrodialysis or the multistage nano filtering process of using of China.People such as Wang Yukun have studied Cangzhou, Hebei rural area brackish water desalination engineering, and wherein electroosmose process can reach 77% to the removal efficiency of fluorine, and hyperfiltration reaches as high as 100% to the removal efficiency of fluorine.But the energy consumption of electrodialysis and hyperfiltration is all higher, and efficiency-cost ratio is lower.People such as Lv Jianguo adopt homemade N90 NF membrane to set up the multisection type nanofiltration device in the brackish water desalination engineering in Qingyang, Gansu, can reach 93.6% to the removal efficiency of fluorine, and the single-stage removal efficiency is 70.6%.The NF membrane of human kayexalate such as Seong Uk Hong and the preparation of polypropylene amine hydrochloride only is 73.2% to the removal efficiency of fluorine.NF membrane according to the invention removal efficiency to fluorine in the single-stage nanofiltration device just can reach 89.7%, contrasts common NF membrane, and the selectivity of fluorine ion is significantly improved.In addition, nano filtering process and counter-infiltration and electrodialysis savings in comparison energy consumption higher efficiency-cost ratio is arranged, so the present invention have the comparison application prospects.
Summary of the invention
The present invention is directed to the weak point of present nanofiltration technology of Fluoride Removal, propose the higher NF membrane of a kind of fluorine removing rate.The present invention is achieved through following technical scheme:
A kind of fluorine ion is selected the preparation method of NF membrane, and its characteristic comprises the steps:
1, a kind of fluorine ion is selected the preparation method of NF membrane, and its characteristic comprises the steps:
(1) with mass content be the N of 14-18% polysulfones, the polysulfones support membrane that the N-dimethylacetamide solution is processed is put into mass concentration and is m-phenylene diamine (MPD) aqueous solution 0.5-3 minute of 0.1%-0.5%, wherein contains mass concentration and be 0.05% dodecyl sodium sulfate;
(2) excessive solution is removed in the rubber rollers roll extrusion of the support membrane after the m-phenylene diamine (MPD) solution soaking;
(3) be that the pyromellitic trimethylsilyl chloride solution of 0.05%-0.5% contacts 10-240 second with the polysulfones support membrane with containing mass concentration, organic solvent wherein is a kind of among n-hexane, normal heptane or the IsoparG;
(4) treat that solvent is done after, be that the polyethyleneimine: amine aqueous solution of 0.01%-1% contacts 20-100 second with containing mass concentration again;
(5) above-mentioned film is placed 80-100 ℃ vacuum drying oven kept 9-14 minute, dry getting final product.
As preferably, the molecular weight of polymine is 600-750000 in the above-mentioned step (4).
As preferably, polymine time of contact is 30-60 second in the above-mentioned step (4).
As preferably, the polyethyleneimine: amine aqueous solution needs to stir 5-10 minute with the rotor agitator at 30-40 ℃ in the above-mentioned step (4).
As preferably, oven temperature is 80-90 ℃ in the above-mentioned step (5).
As preferably, the retention time is 10-13 minute in the above-mentioned step (5).
Step (4) has crucial effects in the present invention, and the polyethyleneimine: amine aqueous solution contacts processing procedure with film be to guarantee that film finally can change fluorine ion through optionally changing; And the selection of polymine emphasis of the present invention especially has incomparable property in similar substance.
Beneficial effect: the prepared NF membrane of the present invention has higher selectivity for fluorine ion, and water flux is high, have higher consumption ratio, and the preparation method is simple, and is easy to operate.
The specific embodiment
Following Example is used to set forth the present invention, and is not used in interpretation protection scope of the present invention.
Embodiment 1
Use contains the N of 15% polysulfones, the polysulfones support membrane that the N-dimethylacetamide solution is processed, and putting into mass concentration is 0.5%, the pH value is the aqueous solution 2 minutes of 8 m-phenylene diamine (MPD); Wherein contain mass concentration and be 0.05% dodecyl sodium sulfate.The rubber rollers roll extrusion of support membrane after the m-phenylene diamine (MPD) solution soaking, removing excessive solution is that 0.5% pyromellitic trimethylsilyl chloride solution contacts 20 seconds with it with containing mass concentration again, organic solvent is a n-hexane.Place 90 ℃ vacuum drying oven to keep 12 minutes this film, make PA membrane.Initial performance with sodium fluoride aqueous solution test membrane under 2MPa pressure of 500mg/L; This film is 2.139 to the infiltration coefficient of fluorine ion; Infiltration coefficient has wherein directly determined the selection permeability of film to fluorine ion, and wherein the definition of the infiltration coefficient of fluorine ion (B) is following:
In the formula: Δ c is that fluorinion concentration is poor in stoste and the penetrating fluid, and J is the seepage flow quality of solute;
Water flux is 9.218L/h/m
2/ Mpa.
Embodiment 2
Use contains the N of 15% polysulfones, the polysulfones support membrane that the N-dimethylacetamide solution is processed, and putting into mass concentration is 0.2%, the pH value is the aqueous solution 3 minutes of 7 m-phenylene diamine (MPD); Wherein contain mass concentration and be 0.05% dodecyl sodium sulfate.The rubber rollers roll extrusion of support membrane after the m-phenylene diamine (MPD) solution soaking, removing excessive solution is that 0.4% pyromellitic trimethylsilyl chloride solution contacts 30 seconds with it with containing mass concentration again, organic solvent is a normal heptane.Treat that organic solvent is that 0.05% molecular weight is that 600 polyethyleneimine: amine aqueous solutions contact 30 seconds with it with containing mass concentration after doing, and places 85 ℃ of baking ovens maintenances 11 minutes with above-mentioned film.With the initial performance of sodium fluoride aqueous solution test membrane under 2MPa pressure of 500mg/L, this film is 1.916 to the infiltration coefficient of fluorine ion, and water flux is 9.677L/h/m
2/ MPa.
Embodiment 3
Use contains the N of 18% polysulfones, the polysulfones support membrane that the N-dimethylacetamide solution is processed, and putting into mass concentration is 0.4%, the pH value is the aqueous solution 1 minute of 9 m-phenylene diamine (MPD); Wherein contain mass concentration and be 0.05% dodecyl sodium sulfate.The rubber rollers roll extrusion of support membrane after the m-phenylene diamine (MPD) solution soaking, removing excessive solution is that 0.3% pyromellitic trimethylsilyl chloride solution contacts 40 seconds with it with containing mass concentration again, organic solvent is IsoparG.Treat that organic solvent is that 0.1% molecular weight is that 600 polyethyleneimine: amine aqueous solutions contact 40 seconds with it with containing mass concentration after doing, and places 80 ℃ of baking ovens maintenances 10 minutes with above-mentioned film.With the initial performance of sodium fluoride aqueous solution test membrane under 2MPa pressure of 500mg/L, this film is 1.610 to the infiltration coefficient of fluorine ion, and water flux is 7.359L/h/m
2/ MPa.
Embodiment 4-9
All the other steps all adopt the 1 same operation method with embodiment except that final step uses polymine concentration difference, and preparation composite membrane and test obtain result such as following table:
| Embodiment | 4 | 5 | 6 | 7 | 8 | 9 |
| Polymine concentration | 0.03％ | 0.05％ | 0.1％ | 0.2％ | 0.3％ | 0.5％ |
| The fluorine ion infiltration coefficient | 2.027 | 1.916 | 1.663 | 1.659 | 1.546 | 1.348 |
| Water flux L/h/m 2/MPa | 8.887 | 8.378 | 9.651 | 9.371 | 10.211 | 11.179 |
Embodiment 10-13
All the other steps all adopt the 1 same operation method with embodiment except that final step uses polymine molecular weight difference, and preparation composite membrane and test obtain result such as following table:
| Embodiment | 10 | 11 | 12 | 13 |
| The polymine molecular weight | 600 | 10000 | 75000 | 750000 |
| The fluorine ion infiltration coefficient | 1.610 | 1.460 | 1.528 | 1.483 |
| Water flux L/h/m 2/MPa | 7.359 | 8.098 | 7.894 | 8.148 |
Claims (7)
1. a fluorine ion is selected the preparation method of NF membrane, and its characteristic comprises the steps:
(1) with mass content be the N of 14-18% polysulfones, the polysulfones support membrane that the N-dimethylacetamide solution is processed is put into mass concentration and is m-phenylene diamine (MPD) aqueous solution 0.5-3 minute of 0.1%-0.5%, wherein contains mass concentration and be 0.05% dodecyl sodium sulfate;
(2) excessive solution is removed in the rubber rollers roll extrusion of the support membrane after the m-phenylene diamine (MPD) solution soaking;
(3) be that the pyromellitic trimethylsilyl chloride solution of 0.05%-0.5% contacts 10-240 second with the polysulfones support membrane with containing mass concentration, organic solvent wherein is a kind of among n-hexane, normal heptane or the IsoparG;
(4) treat that solvent is done after, be that the polyethyleneimine: amine aqueous solution of 0.01%-1% contacts 20-100 second with containing mass concentration again;
(5) above-mentioned film is placed 80-100 ℃ vacuum drying oven kept 9-14 minute, dry getting final product.
2. a kind of fluorine ion according to claim 1 is selected the preparation method of NF membrane, it is characterized in that the concentration of polymine in the described step (4) is 0.03%-0.5%.
3. a kind of fluorine ion according to claim 1 is selected the preparation method of NF membrane, it is characterized in that the molecular weight of polymine in the described step (4) is 600-750000.
4. a kind of fluorine ion according to claim 1 is selected the preparation method of NF membrane, it is characterized in that in the described step (4) that polymine time of contact is 30-60 second.
5. a kind of fluorine ion according to claim 1 is selected the preparation method of NF membrane, it is characterized in that the polyethyleneimine: amine aqueous solution stirred 5-10 minute with the rotor agitator at 30-40 ℃ in the described step (4).
6. a kind of fluorine ion according to claim 1 is selected the preparation method of NF membrane, it is characterized in that oven temperature is 80-90 ℃ in the described step (5).
7. a kind of fluorine ion according to claim 1 is selected the preparation method of NF membrane, it is characterized in that the retention time is 10-13 minute in the described step (5).
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| CN101569836A (en) * | 2009-03-27 | 2009-11-04 | 上海应用技术学院 | High-flux composite reverse osmosis membrane and preparation method thereof |
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| CN102008905A (en) * | 2010-06-18 | 2011-04-13 | 山东东岳神舟新材料有限公司 | Proton exchange film as well as preparation method and application thereof |
| CN102120149A (en) * | 2011-01-30 | 2011-07-13 | 杭州方然滤膜技术有限公司 | Method for preparing acid-proof polysulfonamide nanofiltration composite film |
| CN102125811A (en) * | 2011-01-10 | 2011-07-20 | 杭州水处理技术研究开发中心有限公司 | Method for preparing polyvinyl alcohol-chitosan nano filtration membrane |
| CN102133506A (en) * | 2011-02-28 | 2011-07-27 | 浙江理工大学 | Polyamide composite nanofiltration membrane |
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- 2011-09-09 CN CN 201110267305 patent/CN102350227B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101569836A (en) * | 2009-03-27 | 2009-11-04 | 上海应用技术学院 | High-flux composite reverse osmosis membrane and preparation method thereof |
| CN101559334A (en) * | 2009-05-14 | 2009-10-21 | 杭州水处理技术研究开发中心有限公司 | Method for preparing high-flux nanofiltration membrane |
| CN101757863A (en) * | 2009-12-10 | 2010-06-30 | 山东东岳神舟新材料有限公司 | Fluorine-containing crosslinking ionic membrane reinforced by fibre and preparation method thereof |
| CN102008905A (en) * | 2010-06-18 | 2011-04-13 | 山东东岳神舟新材料有限公司 | Proton exchange film as well as preparation method and application thereof |
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