CN105413479A - Preparation method of nano separation membrane - Google Patents
Preparation method of nano separation membrane Download PDFInfo
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- CN105413479A CN105413479A CN201510926321.9A CN201510926321A CN105413479A CN 105413479 A CN105413479 A CN 105413479A CN 201510926321 A CN201510926321 A CN 201510926321A CN 105413479 A CN105413479 A CN 105413479A
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- diffusion barrier
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/60—Polyamines
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- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
Abstract
The invention discloses a preparation method of a nano separation membrane. The preparation method comprises steps as follows: a glutaraldehyde-crosslinked polyethylenimine solution is prepared; a porous nanowire membrane with the thickness of 160-240 nm is prepared on a substrate; the crosslinked polyethylenimine solution is diluted in 100-500-fold deionized water, then the diluted polyethylenimine solution is poured to the surface of the porous nanowire membrane, deposited for 2-6 hours and dried, the porous nanowire membrane is removed after being dissolved in a 10-15 mmol/L strong acid solution, and accordingly, the polyethylenimine separation membrane capable of separating nano particles is formed on the substrate. The preparation method is simple, the membrane forming efficiency is high, and the prepared separation membrane has the capacity of efficiently separating particles in a water solution and has wide popularization and application prospects.
Description
Technical field
The present invention relates to diffusion barrier technology of preparing, especially relate to a kind of preparation method of nanometer diffusion barrier.
Background technology
Nanometer diffusion barrier refers to that membrane aperture is nano level diffusion barrier.Its main object point can run under ultralow pressure 0.4 ~ 0.7MPa, and its permeability rate is greater than 1 ~ 2 times of high pressure reverse osmosis membrane, can reach more than 98%, as glucose and fructose can reach 98% for molecular weight its rejection of material about 200 dalton; Can 98% be reached, and to its rejection of sodium chloride and permeability rate inversely, from 15% to 85% not etc. to magnesium sulfate.The salt content of this film water inlet requires lower than 1000mg/kg, is mainly used in water correction, the removing of total organic carbon in water, the decolouring of water, water-oil separating, and metal, protein, enzyme recovery, the concentrated and amino acid whose purifying of sugar.
The preparation method of existing nanometer diffusion barrier is more, and one of them filters construction from part, dispersion liquid is deposited on perforated substrate and forms the very thin film of one deck on the ground.But the aperture of substrate is comparatively large, will form the especially very little macromolecule of nano level film or nanometer particle film in substrate, be that prior art is badly in need of one of technical barrier solved.
Summary of the invention
For overcoming the defect of prior art, the present invention proposes a kind of preparation method of nanometer diffusion barrier, and preparation is simple, and film forming efficiency is high and the thickness of diffusion barrier facilitates adjustment.
A preparation method for nanometer diffusion barrier, it comprises step:
The volume mixture of glutaraldehyde water solution by 1:1 of to be the cladodification aq. polyethyleneimine of 1wt% and concentration by concentration be 2.5wt%, crosslinked after 60-240 minute, obtain the polyethylenimine solution of glutaraldehyde cross-linking;
Appropriate cadmium hydroxide nanowires solution is poured on the surface of substrate, cadmium hydroxide nanowires is deposited in substrate, and cadmium hydroxide nanowires is mutually piled up and formed surfacing and thickness is the nano wire porous membrane of 160 ~ 240nm in filter process;
The polyethylenimine solution got after above-mentioned being cross-linked is diluted in the deionized water of 100 ~ 500 times, then the polyethylenimine solution after dilution is poured on the surface of nano wire porous membrane, deposition 2-6 hour, after drying, use 10-15mmol/L strong acid solution to dissolve removing nano wire porous membrane, thus in substrate, form the diffusion barrier with the polyethyleneimine: acid amides of separating nano-particles.
Wherein, substrate is Merlon perforated membrane.
Wherein, on nano wire porous membrane the pore-size distribution of hole at 4-10nm.
Wherein, by regulating the concentration of polyethylenimine solution after dilution and the thickness of the adjustable diffusion barrier prepared.
Wherein, the cadmium chloride solution of 0.35mmol/L and the ethylenediamine solution of 0.7mmol/L are pressed the volume mixture of 1:1, stirred at ambient temperature prepares cadmium hydroxide nanowires solution in 10 minutes.
Compared with prior art, the present invention has following beneficial effect:
The application by the porous membrane formed in substrate as support membrane, the sub-amide solution of deposited polyethylene on porous membrane, removing support membrane is dissolved finally by strong acid solution, form the diffusion barrier with the polyethyleneimine: acid amides of efficient separating nano-particles, and by changing the concentration of polyethyleneimine: amide solution after dilution and the thickness of the adjustable diffusion barrier prepared.The application is prepared simply, and film forming efficiency is high, and the diffusion barrier of preparation can 5nm and above particle in the quick separating aqueous solution, and separating rate hands over existing diffusion barrier to provide 5-10 doubly, has the fast and advantage that separating effect is good of separating rate.
Detailed description of the invention
The application proposes a kind of preparation method of nanometer diffusion barrier, (the application illustrates using " Merlon perforated membrane " as substrate to utilize wide-aperture substrate, other substrates well known to those skilled in the art can certainly be adopted) filter cadmium hydroxide nanowires solution, cadmium hydroxide nanowires is deposited on Merlon perforated membrane and forms removable support membrane, deposited polyethylene imines (Polyethyleneimine on support membrane, PEI) solution, after removing support membrane, form the diffusion barrier with the polyethyleneimine: acid amides of efficient separating nano-particles.
The application comprises the steps: (1) by the cadmium chloride solution of 0.35mmol/L and the ethylenediamine solution of the 0.7mmol/L volume mixture by 1:1, and stirred at ambient temperature prepares cadmium hydroxide nanowires solution in 10 minutes.(2) volume mixture of glutaraldehyde water solution by 1:1 of to be the cladodification aq. polyethyleneimine of 1wt% and concentration by concentration be 2.5wt%, crosslinked after 60-240 minute, obtain the polyethylenimine solution of glutaraldehyde cross-linking.(3) using Merlon perforated membrane as substrate, appropriate cadmium hydroxide nanowires solution is poured on the surface of Merlon perforated membrane, cadmium hydroxide nanowires is deposited on Merlon perforated membrane, cadmium hydroxide nanowires mutually piles up the nano wire porous membrane (i.e. support membrane) that the pore-size distribution that forms hole is 160 ~ 240nm at 4-10nm, thickness in filter process, the surfacing of this nano wire porous membrane.(4) polyethylenimine solution after getting above-mentioned being cross-linked is diluted in the deionized water of 100 ~ 500 times, then the polyethylenimine solution after dilution is poured on the surface of support membrane, filter with above-mentioned support membrane, polyethylenimine solution is at the surface deposition 2-6 hour of above-mentioned support membrane, after drying, use 10-15mmol/L strong acid solution (than example hydrochloric acid, sulfuric acid or nitric acid) to wash above-mentioned support membrane off, thus in substrate, form the diffusion barrier with the polyethyleneimine: acid amides of efficient separating nano-particles.Further, by regulating the concentration of polyethylenimine solution after dilution and the thickness of the adjustable diffusion barrier prepared.Thicker diffusion barrier is higher to the particle entrapment ability that particle is less, but separating rate reduces.
Wherein, relevant cadmium hydroxide nanowires be prepared as prior art, the application is not described in detail.
Embodiment 1
The volume mixture of glutaraldehyde water solution by 1:1 of to be the cladodification aq. polyethyleneimine of 1wt% and concentration by concentration be 2.5wt%, crosslinked after 60 minutes, obtain the polyethylenimine solution of glutaraldehyde cross-linking.Substrate is prepared the nano wire porous membrane (i.e. support membrane) that thickness is the cadmium hydroxide nanowires of 160nm.The polyethylenimine solution getting 20 μ L is diluted to the deionized water of 10mL, then be poured on the surface of support membrane, filter and after depositing 2 hours, after drying, use the above-mentioned support membrane of sulfuric acid dissolution of 10mmol/L, obtain the diffusion barrier that average thickness is the polyethyleneimine: acid amides of 120nm.
To the diffusion barrier of above-mentioned preparation, the copper nano particles solution of 2nm, 3nm and 5nm is adopted to carry out filtration test respectively, test result shows, above-mentioned average thickness is the diffusion barrier of the polyethyleneimine: acid amides of 120nm, is 12%, 29% and 100% respectively to the interception capacity of the copper nano particles of 2nm, 3nm and 5nm.Further, compared with the existing diffusion barrier of identical separation ability (i.e. identical interception capacity), the separating rate of the diffusion barrier of the present embodiment is 12 times of existing diffusion barrier.
Embodiment 2
The volume mixture of glutaraldehyde water solution by 1:1 of to be the cladodification aq. polyethyleneimine of 1wt% and concentration by concentration be 2.5wt%, crosslinked after 120 minutes, obtain the polyethylenimine solution of glutaraldehyde cross-linking.Substrate is prepared the nano wire porous membrane (i.e. support membrane) that thickness is the cadmium hydroxide nanowires of 240nm.The polyethylenimine solution getting 40 μ L is diluted to the deionized water of 10mL, then be poured on the surface of support membrane, filter and after depositing 6 hours, after drying, use the above-mentioned support membrane of nitric acid dissolve of 15mmol/L, obtain the diffusion barrier that average thickness is the polyethyleneimine: acid amides of 230nm.
To the diffusion barrier of above-mentioned preparation, the copper nano particles solution of 2nm, 3nm and 5nm is adopted to carry out filtration test respectively, test result shows, above-mentioned average thickness is the diffusion barrier of the polyethyleneimine: acid amides of 120nm, is 53%, 89% and 100% respectively to the interception capacity of the copper nano particles of 2nm, 3nm and 5nm.Further, compared with the existing diffusion barrier of identical separation ability (i.e. identical interception capacity), the separating rate of the diffusion barrier of the present embodiment is 8 times of existing diffusion barrier.
Embodiment 3
The volume mixture of glutaraldehyde water solution by 1:1 of to be the cladodification aq. polyethyleneimine of 1wt% and concentration by concentration be 2.5wt%, crosslinked after 120 minutes, obtain the polyethylenimine solution of glutaraldehyde cross-linking.Substrate is prepared the nano wire porous membrane (i.e. support membrane) that thickness is the cadmium hydroxide nanowires of 200nm.The polyethylenimine solution getting 100 μ L is diluted to the deionized water of 10mL, then be poured on the surface of support membrane, filter and after depositing 4 hours, after drying, use the above-mentioned support membrane of dissolving with hydrochloric acid of 12mmol/L, obtain the diffusion barrier that average thickness is the polyethyleneimine: acid amides of 420nm.
To the diffusion barrier of above-mentioned preparation, the copper nano particles solution of 2nm, 3nm and 5nm is adopted to carry out filtration test respectively, test result shows, above-mentioned average thickness is the diffusion barrier of the polyethyleneimine: acid amides of 120nm, is 86%, 93% and 100% respectively to the interception capacity of the copper nano particles of 2nm, 3nm and 5nm.Further, compared with the existing diffusion barrier of identical separation ability (i.e. identical interception capacity), the separating rate of the diffusion barrier of the present embodiment is 5 times of existing diffusion barrier.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (5)
1. a preparation method for nanometer diffusion barrier, is characterized in that, comprises step:
The volume mixture of glutaraldehyde water solution by 1:1 of to be the cladodification aq. polyethyleneimine of 1wt% and concentration by concentration be 2.5wt%, crosslinked after 60-240 minute, obtain the polyethylenimine solution of glutaraldehyde cross-linking;
Appropriate cadmium hydroxide nanowires solution is poured on the surface of substrate, cadmium hydroxide nanowires is deposited in substrate, and cadmium hydroxide nanowires is mutually piled up and formed surfacing and thickness is the nano wire porous membrane of 160 ~ 240nm in filter process;
The polyethylenimine solution got after above-mentioned being cross-linked is diluted in the deionized water of 100 ~ 500 times, then the polyethylenimine solution after dilution is poured on the surface of nano wire porous membrane, deposition 2-6 hour, after drying, use 10-15mmol/L strong acid solution to dissolve removing nano wire porous membrane, thus in substrate, form the diffusion barrier with the polyethyleneimine: acid amides of separating nano-particles.
2. the preparation method of a kind of nanometer diffusion barrier according to claim 1, it is characterized in that, substrate is Merlon perforated membrane.
3. the preparation method of a kind of nanometer diffusion barrier according to claim 1, it is characterized in that, on nano wire porous membrane, the pore-size distribution of hole is at 4-10nm.
4. the preparation method of a kind of nanometer diffusion barrier according to claim 1, is characterized in that, by regulating the concentration of polyethylenimine solution after dilution and the thickness of the adjustable diffusion barrier prepared.
5. the preparation method of a kind of nanometer diffusion barrier according to claim 1, it is characterized in that, the cadmium chloride solution of 0.35mmol/L and the ethylenediamine solution of 0.7mmol/L are pressed the volume mixture of 1:1, stirred at ambient temperature prepares cadmium hydroxide nanowires solution in 10 minutes.
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| CN201510926321.9A CN105413479A (en) | 2015-12-11 | 2015-12-11 | Preparation method of nano separation membrane |
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| CN201510926321.9A CN105413479A (en) | 2015-12-11 | 2015-12-11 | Preparation method of nano separation membrane |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110917911A (en) * | 2019-12-09 | 2020-03-27 | 南京惟新环保装备技术研究院有限公司 | One-step formed hollow fiber nanofiltration membrane yarn and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102151501A (en) * | 2011-02-24 | 2011-08-17 | 浙江大学 | Preparation method of organic-inorganic nano composite separation membrane |
| CN103223299A (en) * | 2013-05-17 | 2013-07-31 | 厦门大学 | Macromolecular negative-charge ultrafiltration membrane and preparation method thereof |
| CN103977709A (en) * | 2014-04-30 | 2014-08-13 | 宁波欧琳厨具有限公司 | Modification method of hollow fiber ultrafilter membrane by employing gelatin protein and hydroxide nanowire |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102151501A (en) * | 2011-02-24 | 2011-08-17 | 浙江大学 | Preparation method of organic-inorganic nano composite separation membrane |
| CN103223299A (en) * | 2013-05-17 | 2013-07-31 | 厦门大学 | Macromolecular negative-charge ultrafiltration membrane and preparation method thereof |
| CN103977709A (en) * | 2014-04-30 | 2014-08-13 | 宁波欧琳厨具有限公司 | Modification method of hollow fiber ultrafilter membrane by employing gelatin protein and hydroxide nanowire |
Non-Patent Citations (1)
| Title |
|---|
| 彭新生等: "超薄聚乙烯亚胺膜的制备及分离性能", 《中国科技论文在线》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110917911A (en) * | 2019-12-09 | 2020-03-27 | 南京惟新环保装备技术研究院有限公司 | One-step formed hollow fiber nanofiltration membrane yarn and preparation method thereof |
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Application publication date: 20160323 |