CN102350227B - Preparation method of fluorion selective nanofiltration membrane - Google Patents
Preparation method of fluorion selective nanofiltration membrane Download PDFInfo
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- CN102350227B CN102350227B CN 201110267305 CN201110267305A CN102350227B CN 102350227 B CN102350227 B CN 102350227B CN 201110267305 CN201110267305 CN 201110267305 CN 201110267305 A CN201110267305 A CN 201110267305A CN 102350227 B CN102350227 B CN 102350227B
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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 refer to the preparation method of the selective NF membrane of a kind of fluorine ion.
Technical background
Fluorine element is the trace element of needed by human, but just can even cause acute poisoning by harmful to human when in drinking-water, fluorine content surpasses 4ppm.Drinking Water in China standard code fluorinated volume is 1ppm; In sewage drainage standard regulation trade effluent, the highest permission discharge capacity of fluorine element is 10ppm.At present rural areas in our country have surpass that 7,000 ten thousand people drink that fluorinated volume exceeds standard water.Tradition removing fluorine from water 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 the advantage such as space.Film separation defluorination aspect, China is main counter-infiltration, electrodialysis or the multistage nano filtering process of using at present.The 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.The people such as Lv Jianguo adopt domestic N90 NF membrane to set up the multisection type nanofiltration device in the brackish water desalination engineering of Qingyang District, Gansu Province, can reach 93.6% to the removal efficiency of fluorine, and the single-stage removal efficiency is 70.6%.The NF membrane of the human kayexalate such as Seong Uk Hong and the preparation of polypropylene amine hydrochloride is only 73.2% to the removal efficiency of fluorine.NF membrane of the present invention removal efficiency to fluorine in the single-stage nanofiltration device just can reach 89.7%, contrasts common NF membrane, to selectively significantly improving of fluorine ion.In addition, nano filtering process is compared the saving energy consumption with electrodialysis with counter-infiltration, higher efficiency-cost ratio is arranged, so the present invention has application prospect more widely.
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 by the following technical programs:
A kind of preparation method of fluorion selective nanofiltration membrane, its feature comprises the steps:
1, a kind of preparation method of fluorion selective nanofiltration membrane, its feature comprises the steps:
(1) with mass content be the N of 14-18% polysulfones, the polysulfones support membrane that the N-dimethylacetamide solution is made, put into mass concentration and be m-phenylene diamine (MPD) aqueous solution 0.5-3 minute of 0.1%-0.5%, wherein contain mass concentration and be 0.05% dodecyl sodium sulfate;
(2) the support membrane rubber rollers roll extrusion after m-phenylene diamine (MPD) solution soaks, remove unnecessary solution;
(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 in n-hexane, normal heptane or IsoparG;
(4) after solvent is done, then be that the polyethyleneimine: amine aqueous solution of 0.01%-1% contacts 20-100 second with containing mass concentration;
(5) above-mentioned film is placed in the vacuum drying oven of 80-100 ℃ and kept 9-14 minute, dry getting final product.
As preferably, in above-mentioned step (4), the molecular weight of polymine is 600-750000.
As preferably, in above-mentioned step (4), polymine time of contact is 30-60 second.
As preferably, in above-mentioned step (4), the polyethyleneimine: amine aqueous solution needs to stir 5-10 minute with the rotor agitator at 30-40 ℃.
As preferably, in above-mentioned step (5), oven temperature is 80-90 ℃.
As preferably, in above-mentioned step (5), the retention time is 10-13 minute.
Step (4) has vital effect 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 is emphasis of the present invention especially, has incomparable property in similar substance.
Beneficial effect: the prepared NF membrane of the present invention has higher selective for fluorine ion, 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 for setting forth the present invention, and is not used in interpretation protection scope of the present invention.
Embodiment 1
Use contains the polysulfones support membrane that the DMA solution of 15% polysulfones is made, and puts into mass concentration and be 0.5%, pH value and be the aqueous solution 2 minutes of 8 m-phenylene diamine (MPD); Wherein contain mass concentration and be 0.05% dodecyl sodium sulfate.Support membrane rubber rollers roll extrusion after m-phenylene diamine (MPD) solution soaks, removing unnecessary solution is that 0.5% pyromellitic trimethylsilyl chloride solution contacts 20 seconds with it with containing mass concentration again, organic solvent is n-hexane.The vacuum drying oven that this film is placed in 90 ℃ kept 12 minutes, made 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 infiltration coefficient of fluorine ion (B) is defined as follows:
In formula: Δ c is that in stoste and penetrating fluid, fluorinion concentration is poor, and J is the seepage flow quality of solute;
Water flux is 9.218L/h/m
2/ Mpa.
Embodiment 2
Use contains the polysulfones support membrane that the DMA solution of 15% polysulfones is made, and puts into mass concentration and be 0.2%, pH value and be the aqueous solution 3 minutes of 7 m-phenylene diamine (MPD); Wherein contain mass concentration and be 0.05% dodecyl sodium sulfate.Support membrane rubber rollers roll extrusion after m-phenylene diamine (MPD) solution soaks, removing unnecessary solution is that 0.4% pyromellitic trimethylsilyl chloride solution contacts 30 seconds with it with containing mass concentration again, organic solvent is normal heptane.Be that 0.05% molecular weight is that 600 polyethyleneimine: amine aqueous solutions contact 30 seconds with it with containing mass concentration after organic solvent is done, above-mentioned film is placed in 85 ℃ of baking ovens maintenances 11 minutes.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 polysulfones support membrane that the DMA solution of 18% polysulfones is made, and puts into mass concentration and be 0.4%, pH value and be the aqueous solution 1 minute of 9 m-phenylene diamine (MPD); Wherein contain mass concentration and be 0.05% dodecyl sodium sulfate.Support membrane rubber rollers roll extrusion after m-phenylene diamine (MPD) solution soaks, removing unnecessary solution is that 0.3% pyromellitic trimethylsilyl chloride solution contacts 40 seconds with it with containing mass concentration again, organic solvent is IsoparG.Be that 0.1% molecular weight is that 600 polyethyleneimine: amine aqueous solutions contact 40 seconds with it with containing mass concentration after organic solvent is done, above-mentioned film is placed in 80 ℃ of baking ovens maintenances 10 minutes.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 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 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. the preparation method of a fluorion selective nanofiltration membrane, its feature comprises the steps:
(1) be the polysulfones support membrane that the DMA solution of 14-18% polysulfones is made with mass content, put into mass concentration and be m-phenylene diamine (MPD) aqueous solution 0.5-3 minute of 0.1%-0.5%, wherein contain mass concentration and be 0.05% dodecyl sodium sulfate;
(2) the support membrane rubber rollers roll extrusion after m-phenylene diamine (MPD) solution soaks, remove unnecessary solution;
(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 in n-hexane, normal heptane or IsoparG;
(4) after solvent is done, then be that the polyethyleneimine: amine aqueous solution of 0.01%-1% contacts 20-100 second with containing mass concentration;
(5) film that step (4) is obtained is placed in the vacuum drying oven of 80-100 ℃ and kept 9-14 minute, dry getting final product.
2. the preparation method of a kind of fluorion selective nanofiltration membrane according to claim 1, is characterized in that the concentration of polymine in described step (4) is 0.03%-0.5%.
3. the preparation method of a kind of fluorion selective nanofiltration membrane according to claim 1, is characterized in that the molecular weight of polymine in described step (4) is 600-750000.
4. the preparation method of a kind of fluorion selective nanofiltration membrane according to claim 1 is characterized in that in described step (4) that polymine time of contact is 30-60 second.
5. the preparation method of a kind of fluorion selective nanofiltration membrane according to claim 1, is characterized in that in described step (4), the polyethyleneimine: amine aqueous solution stirred 5-10 minute with the rotor agitator at 30-40 ℃.
6. the preparation method of a kind of fluorion selective nanofiltration membrane according to claim 1, is characterized in that in described step (5), oven temperature is 80-90 ℃.
7. the preparation method of a kind of fluorion selective nanofiltration membrane according to claim 1, is characterized in that in described step (5), the retention time is 10-13 minute.
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| 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
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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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