CN105498554A - Preparation method of UV-irradiation grafting modified nanofiltration membrane with high retention rate - Google Patents
Preparation method of UV-irradiation grafting modified nanofiltration membrane with high retention rate Download PDFInfo
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- CN105498554A CN105498554A CN201610068390.5A CN201610068390A CN105498554A CN 105498554 A CN105498554 A CN 105498554A CN 201610068390 A CN201610068390 A CN 201610068390A CN 105498554 A CN105498554 A CN 105498554A
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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
- B01D67/0002—Organic membrane manufacture
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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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/009—After-treatment of organic or inorganic membranes with wave-energy, particle-radiation or plasma
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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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
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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
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/34—Use of radiation
- B01D2323/345—UV-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/38—Graft polymerization
- B01D2323/385—Graft polymerization involving radiation
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- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Nanotechnology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a preparation method of a UV-irradiation grafting modified nanofiltration membrane with a high retention rate, and belongs to the field of nanofiltration membrane preparation. The preparation method comprises the following steps: firstly, placing a polyacrylonitrile ultrafiltration merebrane in a sodium hydroxide solution for soaking, washing the soaked membrane with deionized water, placing the well washed merebrane in a modified polyether sulfone imide solution for soaking, taking out the soaked membrane, placing the soaked membrane in an anionic sodium polystyrenesulfonate aqueous solution, washing the membrane with deionized water, drying the well washed membrane, mixing the dried membrane with an ammonium bicarbonate solution, carrying out mineralization reaction, flatly laying the membrane after mineralization reaction in a culture dish, adding an acrylonitrile monomer to ensure that the nanofiltration membrane is fully soaked, performing ultraviolet radiation on the soaked nanofiltration membrane for modified treatment, collecting the nanofiltration membrane after modified treatment, placing the collected nanofiltration membrane in an ethanol solution, carrying out ultrasonic cleaning, and drying to obtain the UV-irradiation grafting modified nanofiltration membrane. According to the preparation method of the UV-irradiation grafting modified nanofiltration membrane with the high retention rate, the retention rate of substances such as sodium chloride reaches 80% or above, the water flux reaches 120-155 L/(m<2>.h.MPa), the antifouling property is good, the preparation technology is simple and reliable, and the industrial applicability is further achieved.
Description
Technical field
The present invention relates to a kind of preparation method of irradiation uv photo initiated grafting modification high rejection NF membrane, belong to NF membrane preparation field.
Background technology
NF membrane is the pressure drive membrane of a kind of performance between ultrafiltration and counter-infiltration.NF membrane has following feature: molecular cut off, between 200 ~ 1000Da, is suitable for the dissolved constituent removing about about 1nm; Operating pressure is low, lower than the pressure required by counter-infiltration, therefore also referred to as " low-pressure reverse osmosis membrane "; There is ion selectivity, the feature that of NF membrane is very large is that membrane body is with electric charge, pass through electrostatic interaction, the divalence in the aqueous solution and multivalent ion can be removed, to the rejection of divalence and multivalent ion more than 90%, 80% is less than to the rejection of monovalent ion, therefore can realizes the separation of different valence state ion.Because NF membrane has above feature, therefore the industry-by-industries such as environmental protection, water resource, food, medicine and chemical industry are widely used in.
In membrane technology, can accomplish to increase the water flux of film and not reduce it selective be very difficult.The rejection of usual diffusion barrier is higher, or molecular cut off is lower, and the flux of film is lower.Because temperature affects mobility and the membrane pore size size of solvent viscosity, diffusion coefficient and polymer chain, the therefore general permeation flux increasing film by improving feed temperature, but rejection decreases with the rising of film permeation flux usually.In addition, in some cases, although it is simple actual infeasible to add hot feed, as large-scale water treatment procedure and seawater desalination process.
Summary of the invention
Technical problem to be solved by this invention: simultaneously can not have both rejection and the high shortcoming of film infiltration capacity for current NF membrane, provide a kind of polyacrylonitrile ultrafiltration film alkali leaching modification and prepare basement membrane, electrolysis subsequently to its modification, and under the condition not adding any light trigger or sensitising agent, pass through UV-irradiation, modification membrane surface generation free radical grafting is reacted, the polymer chain of electrochemistry bonding is formed in modification basement membrane film surface and film surface micropore, it is made to introduce hydroxyl, sulfonic group, carboxylic acid group's isoreactivity group, it is made to present good rejection and infiltration capacity, the rejection of irradiation uv photo initiated grafting modification high rejection NF membrane to materials such as sodium chloride prepared by the present invention reaches more than 80%, water flux reaches 120 ~ 155L/ (m
2hMPa), antifouling property is good, and preparation technology is simple and reliable, is applicable to industrialization.
For solving the problems of the technologies described above, the present invention adopts technical scheme as described below to be:
(1) choose the polyacrylonitrile ultrafiltration film that molecular cut off is 100,000, be placed in 2.2 ~ 2.5mol/L sodium hydroxide solution, immersion treatment 50 ~ 60min, after immersion completes, being taken out and spending deionized water to pH is 7.0, is prepared into modification basement membrane;
(2) by solid-liquid mass ratio 1:15,0.05mol/L calcium carbonate soln is added in the polyether sulfone imide liquor of 5mg/L, be uniformly mixed and be prepared into cation-modified polyether sulfone imide liquor, subsequently the modification basement membrane of above-mentioned preparation is placed in modified poly (ether-sulfone) imide liquor, makes its immersion treatment 20 ~ 30min;
(3) after immersion completes, take out basement membrane, it is placed in again the anionic polystyrene sodium sulfonate aqueous solution immersion treatment 20 ~ 30min of 5mg/L, again take out basement membrane subsequently, spend deionized water pH to 7.0, at 40 ~ 50 DEG C, dry 6 ~ 8h, is prepared into electrolysis basement membrane;
(4) the electrolysis basement membrane of above-mentioned preparation is placed in sealable stainless steel cauldron, continuing subsequently to add mass concentration is in 20% ammonium bicarbonate soln, ensure complete for electrolysis basement membrane submergence, at reactor being placed in 25 ~ 30 DEG C after mineralising reaction 3 ~ 5h, electrolysis basement membrane is taken out and dry 2 ~ 3h at being placed in 45 ~ 50 DEG C, be prepared into pre-modification high rejection NF membrane;
(5) the pre-modification high rejection NF membrane of above-mentioned preparation is collected, tiled in culture dish, add graft copolymer solution acrylonitrile monemer subsequently, it is made NF membrane to be soaked completely, subsequently culture dish is placed in the irradiation box with 300W uviol lamp and exhaust fan, control uviol lamp and culture dish distance are 10 ~ 15cm;
(6) after lamp distance to be adjusted, to passing into nitrogen deaeration in irradiation box, open uviol lamp subsequently, make its ultraviolet irradiation graft modification process 25 ~ 30min, after grafting completes, collecting NF membrane and being placed in mass fraction is 30% ethanolic solution, in 200 ~ 300W sonic oscillation, clean 5 ~ 10min, collect NF membrane subsequently and vacuum drying 6 ~ 8h at being placed in 40 ~ 50 DEG C, a kind of irradiation uv photo initiated grafting modification high rejection NF membrane can be prepared into.
Application process of the present invention: the irradiation uv photo initiated grafting modification high rejection NF membrane of above-mentioned preparation is applied to the processing technology field such as wastewater from chemical industry, be placed in salt chemical engineering waste water, every 1 ~ 1.5m, a film device is set, controlled pressure is 3 ~ 4MPa, temperature is 35 ~ 40 DEG C, pending complete after, record and more than 80% reached to the rejection of sodium chloride, reach more than 82% to the rejection of sodium sulphate, water flux reaches 120 ~ 155L/ (m
2hMPa).
The present invention is compared with additive method, and Advantageous Effects is:
(1) be applied to technical field of membrane separation, rejection reaches more than 80%, and water flux reaches 120 ~ 155L/ (m
2hMPa);
(3) the irradiation uv photo initiated grafting modification high rejection NF membrane preparation process prepared of the present invention is simple, and required cost is low.
Detailed description of the invention
First choose the polyacrylonitrile ultrafiltration film that molecular cut off is 100,000, be placed in 2.2 ~ 2.5mol/L sodium hydroxide solution, immersion treatment 50 ~ 60min, after immersion completes, being taken out and spending deionized water to pH is 7.0, is prepared into modification basement membrane; By solid-liquid mass ratio 1:15,0.05mol/L calcium carbonate soln is added in the polyether sulfone imide liquor of 5mg/L, be uniformly mixed and be prepared into cation-modified polyether sulfone imide liquor, subsequently the modification basement membrane of above-mentioned preparation is placed in modified poly (ether-sulfone) imide liquor, make its immersion treatment 20 ~ 30min; After immersion completes, take out basement membrane, it is placed in again the anionic polystyrene sodium sulfonate aqueous solution immersion treatment 20 ~ 30min of 5mg/L, again take out basement membrane subsequently, spend deionized water pH to 7.0, at 40 ~ 50 DEG C, dry 6 ~ 8h, is prepared into electrolysis basement membrane; The electrolysis basement membrane of above-mentioned preparation is placed in sealable stainless steel cauldron, continuing subsequently to add mass concentration is in 20% ammonium bicarbonate soln, ensure complete for electrolysis basement membrane submergence, at reactor being placed in 25 ~ 30 DEG C after mineralising reaction 3 ~ 5h, electrolysis basement membrane is taken out and dry 2 ~ 3h at being placed in 45 ~ 50 DEG C, be prepared into pre-modification high rejection NF membrane; Collect the pre-modification high rejection NF membrane of above-mentioned preparation, tiled in culture dish, add graft copolymer solution acrylonitrile monemer subsequently, it is made NF membrane to be soaked completely, subsequently culture dish is placed in the irradiation box with 300W uviol lamp and exhaust fan, control uviol lamp and culture dish distance are 10 ~ 15cm; After lamp distance to be adjusted, to passing into nitrogen deaeration in irradiation box, open uviol lamp subsequently, make its ultraviolet irradiation graft modification process 25 ~ 30min, after grafting completes, collecting NF membrane and being placed in mass fraction is 30% ethanolic solution, in 200 ~ 300W sonic oscillation, clean 5 ~ 10min, collect NF membrane subsequently and vacuum drying 6 ~ 8h at being placed in 40 ~ 50 DEG C, a kind of irradiation uv photo initiated grafting modification high rejection NF membrane can be prepared into.
Example 1
First choose the polyacrylonitrile ultrafiltration film that molecular cut off is 100,000, be placed in 2.5mol/L sodium hydroxide solution, immersion treatment 60min, after immersion completes, being taken out and spending deionized water to pH is 7.0, is prepared into modification basement membrane; By solid-liquid mass ratio 1:15,0.05mol/L calcium carbonate soln is added in the polyether sulfone imide liquor of 5mg/L, be uniformly mixed and be prepared into cation-modified polyether sulfone imide liquor, subsequently the modification basement membrane of above-mentioned preparation is placed in modified poly (ether-sulfone) imide liquor, makes its immersion treatment 30min; After immersion completes, take out basement membrane, it is placed in again the anionic polystyrene sodium sulfonate aqueous solution immersion treatment 30min of 5mg/L, again take out basement membrane subsequently, spend deionized water pH to 7.0, dry 8h at 50 DEG C, is prepared into electrolysis basement membrane; The electrolysis basement membrane of above-mentioned preparation is placed in sealable stainless steel cauldron, continuing subsequently to add mass concentration is in 20% ammonium bicarbonate soln, ensure complete for electrolysis basement membrane submergence, at reactor being placed in 30 DEG C after mineralising reaction 5h, electrolysis basement membrane is taken out and dry 3h at being placed in 50 DEG C, be prepared into pre-modification high rejection NF membrane; Collect the pre-modification high rejection NF membrane of above-mentioned preparation, tiled in culture dish, add graft copolymer solution acrylonitrile monemer subsequently, it is made NF membrane to be soaked completely, subsequently culture dish is placed in the irradiation box with 300W uviol lamp and exhaust fan, control uviol lamp and culture dish distance are 15cm; After lamp distance to be adjusted, to passing into nitrogen deaeration in irradiation box, open uviol lamp subsequently, make its ultraviolet irradiation graft modification process 30min, after grafting completes, collecting NF membrane and being placed in mass fraction is 30% ethanolic solution, in 300W sonic oscillation, clean 10min, collect NF membrane subsequently and vacuum drying 8h at being placed in 50 DEG C, a kind of irradiation uv photo initiated grafting modification high rejection NF membrane can be prepared into.The irradiation uv photo initiated grafting modification high rejection NF membrane of above-mentioned preparation is applied to the processing technology field such as wastewater from chemical industry, be placed in salt chemical engineering waste water, every 1.5m, a film device is set, controlled pressure is 4MPa, temperature is 40 DEG C, pending complete after, record and 82% reached to the rejection of sodium chloride, reach 83% to the rejection of sodium sulphate, water flux reaches 120L/ (m
2hMPa)
Example 2
First choose the polyacrylonitrile ultrafiltration film that molecular cut off is 100,000, be placed in 2.2mol/L sodium hydroxide solution, immersion treatment 50min, after immersion completes, being taken out and spending deionized water to pH is 7.0, is prepared into modification basement membrane; By solid-liquid mass ratio 1:15,0.05mol/L calcium carbonate soln is added in the polyether sulfone imide liquor of 5mg/L, be uniformly mixed and be prepared into cation-modified polyether sulfone imide liquor, subsequently the modification basement membrane of above-mentioned preparation is placed in modified poly (ether-sulfone) imide liquor, makes its immersion treatment 20min; After immersion completes, take out basement membrane, it is placed in again the anionic polystyrene sodium sulfonate aqueous solution immersion treatment 20min of 5mg/L, again take out basement membrane subsequently, spend deionized water pH to 7.0, dry 6h at 40 DEG C, is prepared into electrolysis basement membrane; The electrolysis basement membrane of above-mentioned preparation is placed in sealable stainless steel cauldron, continuing subsequently to add mass concentration is in 20% ammonium bicarbonate soln, ensure complete for electrolysis basement membrane submergence, at reactor being placed in 25 DEG C after mineralising reaction 3h, electrolysis basement membrane is taken out and dry 2h at being placed in 45 DEG C, be prepared into pre-modification high rejection NF membrane; Collect the pre-modification high rejection NF membrane of above-mentioned preparation, tiled in culture dish, add graft copolymer solution acrylonitrile monemer subsequently, it is made NF membrane to be soaked completely, subsequently culture dish is placed in the irradiation box with 300W uviol lamp and exhaust fan, control uviol lamp and culture dish distance are 10cm; After lamp distance to be adjusted, to passing into nitrogen deaeration in irradiation box, open uviol lamp subsequently, make its ultraviolet irradiation graft modification process 25min, after grafting completes, collecting NF membrane and being placed in mass fraction is 30% ethanolic solution, in 200W sonic oscillation, clean 5min, collect NF membrane subsequently and vacuum drying 6h at being placed in 40 DEG C, a kind of irradiation uv photo initiated grafting modification high rejection NF membrane can be prepared into.The irradiation uv photo initiated grafting modification high rejection NF membrane of above-mentioned preparation is applied to the processing technology field such as wastewater from chemical industry, be placed in salt chemical engineering waste water, every 1m, a film device is set, controlled pressure is 3MPa, temperature is 35 DEG C, pending complete after, record and 81% reached to the rejection of sodium chloride, 84% is reached to the rejection of sodium sulphate.Water flux reaches 155L/ (m
2hMPa).
Example 3
First choose the polyacrylonitrile ultrafiltration film that molecular cut off is 100,000, be placed in 2.2mol/L sodium hydroxide solution, immersion treatment 55min, after immersion completes, being taken out and spending deionized water to pH is 7.0, is prepared into modification basement membrane; By solid-liquid mass ratio 1:15,0.05mol/L calcium carbonate soln is added in the polyether sulfone imide liquor of 5mg/L, be uniformly mixed and be prepared into cation-modified polyether sulfone imide liquor, subsequently the modification basement membrane of above-mentioned preparation is placed in modified poly (ether-sulfone) imide liquor, makes its immersion treatment 25min; After immersion completes, take out basement membrane, it is placed in again the anionic polystyrene sodium sulfonate aqueous solution immersion treatment 25min of 5mg/L, again take out basement membrane subsequently, spend deionized water pH to 7.0, dry 7h at 45 DEG C, is prepared into electrolysis basement membrane; The electrolysis basement membrane of above-mentioned preparation is placed in sealable stainless steel cauldron, continuing subsequently to add mass concentration is in 20% ammonium bicarbonate soln, ensure complete for electrolysis basement membrane submergence, at reactor being placed in 27 DEG C after mineralising reaction 4h, electrolysis basement membrane is taken out and dry 2h at being placed in 47 DEG C, be prepared into pre-modification high rejection NF membrane; Collect the pre-modification high rejection NF membrane of above-mentioned preparation, tiled in culture dish, add graft copolymer solution acrylonitrile monemer subsequently, it is made NF membrane to be soaked completely, subsequently culture dish is placed in the irradiation box with 300W uviol lamp and exhaust fan, control uviol lamp and culture dish distance are 12cm; After lamp distance to be adjusted, to passing into nitrogen deaeration in irradiation box, open uviol lamp subsequently, make its ultraviolet irradiation graft modification process 27min, after grafting completes, collecting NF membrane and being placed in mass fraction is 30% ethanolic solution, in 250W sonic oscillation, clean 7min, collect NF membrane subsequently and vacuum drying 7h at being placed in 45 DEG C, a kind of irradiation uv photo initiated grafting modification high rejection NF membrane can be prepared into.The irradiation uv photo initiated grafting modification high rejection NF membrane of above-mentioned preparation is applied to the processing technology field such as wastewater from chemical industry, be placed in salt chemical engineering waste water, every 1m, a film device is set, controlled pressure is 3MPa, temperature is 37 DEG C, pending complete after, record and 82% reached to the rejection of sodium chloride, reach 83% to the rejection of sodium sulphate, water flux reaches 130L/ (m
2hMPa).
Claims (1)
1. a preparation method for irradiation uv photo initiated grafting modification high rejection NF membrane, is characterized in that concrete preparation process is:
(1) choose the polyacrylonitrile ultrafiltration film that molecular cut off is 100,000, be placed in 2.2 ~ 2.5mol/L sodium hydroxide solution, immersion treatment 50 ~ 60min, after immersion completes, being taken out and spending deionized water to pH is 7.0, is prepared into modification basement membrane;
(2) by solid-liquid mass ratio 1:15,0.05mol/L calcium carbonate soln is added in the polyether sulfone imide liquor of 5mg/L, be uniformly mixed and be prepared into cation-modified polyether sulfone imide liquor, subsequently the modification basement membrane of above-mentioned preparation is placed in modified poly (ether-sulfone) imide liquor, makes its immersion treatment 20 ~ 30min;
(3) after immersion completes, take out basement membrane, it is placed in again the anionic polystyrene sodium sulfonate aqueous solution immersion treatment 20 ~ 30min of 5mg/L, again take out basement membrane subsequently, spend deionized water pH to 7.0, at 40 ~ 50 DEG C, dry 6 ~ 8h, is prepared into electrolysis basement membrane;
(4) the electrolysis basement membrane of above-mentioned preparation is placed in sealable stainless steel cauldron, continuing subsequently to add mass concentration is in 20% ammonium bicarbonate soln, ensure complete for electrolysis basement membrane submergence, at reactor being placed in 25 ~ 30 DEG C after mineralising reaction 3 ~ 5h, electrolysis basement membrane is taken out and dry 2 ~ 3h at being placed in 45 ~ 50 DEG C, be prepared into pre-modification high rejection NF membrane;
(5) the pre-modification high rejection NF membrane of above-mentioned preparation is collected, tiled in culture dish, add graft copolymer solution acrylonitrile monemer subsequently, it is made NF membrane to be soaked completely, subsequently culture dish is placed in the irradiation box with 300W uviol lamp and exhaust fan, control uviol lamp and culture dish distance are 10 ~ 15cm;
(6) after lamp distance to be adjusted, to passing into nitrogen deaeration in irradiation box, open uviol lamp subsequently, make its ultraviolet irradiation graft modification process 25 ~ 30min, after grafting completes, collecting NF membrane and being placed in mass fraction is 30% ethanolic solution, in 200 ~ 300W sonic oscillation, clean 5 ~ 10min, collect NF membrane subsequently and vacuum drying 6 ~ 8h at being placed in 40 ~ 50 DEG C, a kind of irradiation uv photo initiated grafting modification high rejection NF membrane can be prepared into.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112739450A (en) * | 2018-03-30 | 2021-04-30 | 海德奥克赛斯控股有限公司 | Asymmetric composite membranes and modified substrates used in their preparation |
| CN113244794A (en) * | 2021-05-11 | 2021-08-13 | 燕山大学 | Preparation method of nanofiltration membrane for intercepting nitrate and resource utilization of concentrated solution |
| CN114307649A (en) * | 2021-11-16 | 2022-04-12 | 中国科学院生态环境研究中心 | Modification method of polyamide composite nanofiltration membrane for selectively intercepting divalent salt ions |
| CN114832652A (en) * | 2022-04-25 | 2022-08-02 | 上海师范大学 | Functional polymer nanofiltration membrane material and preparation method thereof |
| CN115837085A (en) * | 2022-11-10 | 2023-03-24 | 广州华大洁特生物技术有限公司 | Radiation sterilization method of culture dish for assisted reproduction |
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2016
- 2016-02-01 CN CN201610068390.5A patent/CN105498554A/en not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112739450A (en) * | 2018-03-30 | 2021-04-30 | 海德奥克赛斯控股有限公司 | Asymmetric composite membranes and modified substrates used in their preparation |
| CN113244794A (en) * | 2021-05-11 | 2021-08-13 | 燕山大学 | Preparation method of nanofiltration membrane for intercepting nitrate and resource utilization of concentrated solution |
| CN113244794B (en) * | 2021-05-11 | 2022-04-19 | 燕山大学 | Preparation method of nanofiltration membrane for intercepting nitrate and resource utilization of concentrated solution |
| CN114307649A (en) * | 2021-11-16 | 2022-04-12 | 中国科学院生态环境研究中心 | Modification method of polyamide composite nanofiltration membrane for selectively intercepting divalent salt ions |
| CN114832652A (en) * | 2022-04-25 | 2022-08-02 | 上海师范大学 | Functional polymer nanofiltration membrane material and preparation method thereof |
| CN114832652B (en) * | 2022-04-25 | 2024-05-31 | 上海师范大学 | Functional polymer nanofiltration membrane material and preparation method thereof |
| CN115837085A (en) * | 2022-11-10 | 2023-03-24 | 广州华大洁特生物技术有限公司 | Radiation sterilization method of culture dish for assisted reproduction |
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