CN111001310A - Preparation method of environment-friendly nanofiltration membrane - Google Patents
Preparation method of environment-friendly nanofiltration membrane Download PDFInfo
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- CN111001310A CN111001310A CN201911344440.8A CN201911344440A CN111001310A CN 111001310 A CN111001310 A CN 111001310A CN 201911344440 A CN201911344440 A CN 201911344440A CN 111001310 A CN111001310 A CN 111001310A
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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
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
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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
- B01D2323/00—Details relating to membrane preparation
- B01D2323/26—Spraying processes
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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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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a preparation method of an environment-friendly nanofiltration membrane, which is realized by the following technical scheme and comprises the following steps: firstly, adopting a photo-initiation polymerization process: uniformly spraying the coating solution on the base film, removing floating water by a scraper, and entering an irradiation area; irradiating for 20-45 minutes by a 300 nm ultraviolet lamp under the protection of nitrogen; after the irradiation is finished, the mixture stays for 10 min under the protection of nitrogen, and is soaked in RO water overnight, and the product is obtained. The method of the invention has no use of organic solvent, and is safe and environment-friendly; the method of the invention does not need explosion-proof treatment, and the cost is greatly reduced.
Description
Technical Field
The invention relates to the field of nanofiltration membrane preparation, and in particular relates to a preparation method of an environment-friendly nanofiltration membrane.
Background
The traditional method for preparing the nanofiltration membrane is interfacial polymerization and is widely adopted by the industry and academia. The method adopts the polymerization reaction at the interface of water phase and oil phase to form the film. The oil phase usually adopts organic solvents such as normal hexane, cyclohexane and isoparaffin, belongs to flammable and explosive liquid, needs to build special explosion-proof facilities, needs to carry out explosion-proof treatment in transportation, storage, use, production equipment, factory buildings and post-treatment processes, has long flow and complex process, and is strictly supervised by relevant departments such as environmental protection, safety supervision and the like. The treatment or recovery cost of the waste liquid containing the organic solvent is high, and the air containing volatile organic compounds generated in the related using process also needs to be subjected to harmless treatment, so that the cost is high.
On the other hand, interfacial polymerization requires precise control of the position of the "interface" to ensure the formation of the interface at the surface of the base membrane, so that a higher water flux can be obtained under the condition of obtaining a high rejection rate, thereby producing economic value. The important means for regulating and controlling the interface is to control the drying degree of the water phase on the surface of the basement membrane. Therefore, the interfacial polymerization process is inevitably affected by factors such as ambient humidity, temperature, etc.
The traditional method for preparing the nanofiltration membrane has complex production process, needs special explosion-proof treatment and has high cost; and a large amount of organic solvent-containing waste liquid can be generated, and the treatment and recovery costs are high; organic steam is continuously generated in the production and use processes, and the treatment cost is also very high.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing a preparation method of an environment-friendly nanofiltration membrane.
The invention relates to a preparation method of an environment-friendly nanofiltration membrane, which is realized by the following technical scheme and comprises the following steps: firstly, adopting a photo-initiation polymerization process: uniformly spraying the coating solution on the base film, removing floating water by a scraper, and entering an irradiation area; irradiating for 20-45 minutes by a 300 nm ultraviolet lamp under the protection of nitrogen; after the irradiation is finished, staying for 10 min under the protection of nitrogen, and soaking in RO water overnight to obtain a product;
the coating liquid comprises the following components in parts by mass: 2-10 parts of monomer, 20-40 parts of cross-linking agent, 2-10 parts of photoinitiator, 0.1-1 part of surfactant and 50 parts of solvent water;
the monomer comprises a negatively charged monomer, a positively charged monomer and a neutral regulator.
Such photoinitiators include, but are not limited to: 2-hydroxy-2-methyl-1-phenylpropanone (1173), 1-hydroxycyclohexyl phenyl methanone (184), 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone (907), 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), ethyl 2,4, 6-trimethylbenzoylphenylphosphonate (TPO-L), 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone (IHT-PI 910), 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone (659), Methyl Benzoylformate (MBF).
The negative charge monomer adopts (methyl) acrylic acid, (methyl) propylene sulfonic acid, (methyl) styrene sulfonic acid or 2- (methyl) acrylamide-2-methyl propane sulfonic acid; the positively charged monomer is divinylamine, diallyl dimethyl ammonium chloride, (methyl) acrylamide propyl trimethyl ammonium chloride or (methyl) acryloyl oxyethyl trimethyl ammonium chloride; the neutral regulator adopts (methyl) acrylamide, dimethylacrylamide, vinyl acetate and (methyl) hydroxyethyl acrylate methyl) glycerol acrylate.
The cross-linking agent is diethylene glycol, diethylene glycol di (meth) acrylate, oleyl ester, polyethylene glycol di (meth) acrylate or ethylene glycol di (meth) acrylate.
The surfactant is sodium dodecyl sulfate, sodium dodecyl sulfonate, dodecyl trimethyl ammonium chloride or polyethylene glycol.
Compared with the prior art, the invention has the beneficial effects that:
1. the method of the invention has no use of organic solvent, and is safe and environment-friendly.
2. The method of the invention does not need explosion-proof treatment, and the cost is greatly reduced.
3. The method of the invention has no organic waste liquid treatment process.
4. The method of the invention has no organic steam treatment flow.
5. The method has the advantages of simplified process, no environmental influence in the production process and more stability.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Coating liquid: 10 parts by mass of 2-methacrylamide-2-methylpropanesulfonic acid, 40 parts by mass of polyethylene glycol di (meth) acrylate, 5 parts by mass of TPO, 0.3 part by mass of sodium dodecyl sulfate and 50 parts by mass of water.
And (4) uniformly spraying the coating solution on the base film, removing floating water by a scraper, and entering an irradiation area. Irradiating with ultraviolet lamp (300 nm) under nitrogen protection for 30 min at power density of 3000W/m2. After the irradiation is finished, the mixture is kept for 10 min under the protection of nitrogen and then soaked in RO water overnight, and the product is obtained.
Example 2
Coating liquid: 5 parts of diallyl dimethyl ammonium chloride, 30 parts of glycerol dimethacrylate, 11736 parts of polyethylene glycol and 50 parts of water.
Irradiating with ultraviolet lamp (300 nm) for 25 min at power density of 3000W/m2. The rest is the same as in example 1.
Example 3
Coating liquid: 4 parts of methacrylic sulfonic acid, 1 part of ethylene glycol dimethacrylate, 9075 parts of sodium dodecyl sulfate and 50 parts of water.
Irradiating with ultraviolet lamp (300 nm) for 30 min at power density of 2800W/m2. The rest is the same as in example 1.
Example 4
Coating liquid: 10 parts of hydroxyethyl acrylate, 40 parts of glycerol dimethacrylate, 1848 parts of glycerol dimethacrylate, 0.5 part of sodium dodecyl sulfate and 50 parts of water.
Irradiating with ultraviolet lamp (300 nm) for 25 min at power density of 3500W/m2. The rest is the same as in example 1.
Example 5
Coating liquid: 5 parts of dimethyl acrylamide, 40 parts of glycerol dimethacrylate, 6 parts of MBF, 1 part of dodecyl trimethyl ammonium chloride and 50 parts of water.
Irradiating with ultraviolet lamp (300 nm) for 40 min at power density of 3000W/m2. The rest is the same as in example 1.
Example 6
Coating liquid: 8 parts of glycerol methacrylate, 30 parts of ethylene glycol dimethacrylate, 2 parts of ethylene glycol dimethacrylate, 0.3 part of sodium dodecyl sulfate and 50 parts of water.
Irradiating with ultraviolet lamp (300 nm) for 35 min at power density of 2700W/m2. The rest is the same as in example 1.
Example 7
Coating liquid: 10 parts of styrene sulfonic acid, 40 parts of glycerol dimethacrylate, 9107 parts of IHT-PI, 0.6 part of sodium dodecyl sulfate and 50 parts of water.
Irradiating with ultraviolet lamp (300 nm) for 25 min at power density of 4000W/m2. The rest is the same as in example 1.
Comparative example 1
Irradiation power 1000W/m2Otherwise, the same procedure as in example 1 was repeated.
Comparative example 2
The irradiation time was 5 min, and the rest was the same as in example 1.
Comparative example 3
The coating solution was the same as in example 1 except that no surfactant was added.
Nanofiltration membrane separation performance test method
Testing liquid: the test was carried out using a 2000 mg/L magnesium sulfate (MgSO 4) solution.
The operation parameters are as follows: a nanofiltration membrane evaluator is adopted for testing, the pressure is 0.5 MPa, the temperature is 25 ℃, the pH =7.0, and the recovery rate is 15%.
Calculating the formula:
the retention rate R = (CI-CO)/CI x 100%, wherein CI is water inlet conductance, and CO is water outlet conductance;
flux F = V/(a × T), where V is water production volume, a is membrane area, and T is measurement time.
TABLE 1 comparison of nanofiltration Membrane separation Performance
| Flux (LMH) | MgSO4（%） | |
| Example 1 | 32 | 91 |
| Example 2 | 29 | 85 |
| Example 3 | 35 | 89 |
| Example 4 | 32 | 88 |
| Example 5 | 33 | 89 |
| Example 6 | 34 | 87 |
| Example 7 | 30 | 90 |
| Comparative example 1 | 8 | 90 |
| Comparative example 2 | 12 | 3 |
| Comparative example 3 | 28 | 73 |
And (4) conclusion: the nanofiltration membrane with the retention rate of more than 85 percent can be obtained by adopting the method, wherein the introduction of the surfactant provides guarantee for the full dissolution of each component and is an accelerant of the retention rate (comparative example 3). Whereas the addition of non-crosslinking monomers is an important guarantee of sufficient throughput.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (5)
1. The preparation method of the environment-friendly nanofiltration membrane is characterized by comprising the following steps of: firstly, adopting a photo-initiation polymerization process: uniformly spraying the coating solution on the base film, removing floating water by a scraper, and entering an irradiation area; irradiating for 20-45 minutes by a 300 nm ultraviolet lamp under the protection of nitrogen; after the irradiation is finished, staying for 10 min under the protection of nitrogen, and soaking in RO water overnight to obtain a product;
the coating liquid comprises the following components in parts by mass: 2-10 parts of monomer, 20-40 parts of cross-linking agent, 2-10 parts of photoinitiator, 0.1-1 part of surfactant and 50 parts of solvent water;
the monomer comprises a negatively charged monomer, a positively charged monomer and a neutral regulator.
2. The method for preparing an environment-friendly nanofiltration membrane according to claim 1, wherein the photoinitiator comprises: 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenylketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone or methyl benzoylformate.
3. The method for preparing an environment-friendly nanofiltration membrane according to claim 1, wherein the negatively charged monomer is (meth) acrylic acid, (meth) acrylic sulfonic acid, (meth) styrene sulfonic acid or 2- (meth) acrylamide-2-methylpropane sulfonic acid; the positively charged monomer is divinylamine, diallyl dimethyl ammonium chloride, (methyl) acrylamide propyl trimethyl ammonium chloride or (methyl) acryloyl oxyethyl trimethyl ammonium chloride; the neutral regulator adopts (methyl) acrylamide, dimethylacrylamide, vinyl acetate and (methyl) hydroxyethyl acrylate methyl) glycerol acrylate.
4. The method for preparing an environment-friendly nanofiltration membrane according to claim 1, wherein the cross-linking agent is diethylene glycol, glycerol di (meth) acrylate, oleyl ester, polyethylene glycol di (meth) acrylate or ethylene glycol di (meth) acrylate.
5. The method for preparing an environment-friendly nanofiltration membrane according to claim 1, wherein the surfactant is sodium dodecyl sulfate, dodecyl trimethyl ammonium chloride or polyethylene glycol.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112337323A (en) * | 2020-09-28 | 2021-02-09 | 南京工业大学 | PVDF (polyvinylidene fluoride) polymer separation membrane and preparation method thereof |
| TWI792184B (en) * | 2021-02-08 | 2023-02-11 | 元智大學 | Homogeneous anion exchange membrane and biosensing membrane |
| TWI821020B (en) * | 2021-02-08 | 2023-11-01 | 元智大學 | Biosensing membrane |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112337323A (en) * | 2020-09-28 | 2021-02-09 | 南京工业大学 | PVDF (polyvinylidene fluoride) polymer separation membrane and preparation method thereof |
| TWI792184B (en) * | 2021-02-08 | 2023-02-11 | 元智大學 | Homogeneous anion exchange membrane and biosensing membrane |
| TWI821020B (en) * | 2021-02-08 | 2023-11-01 | 元智大學 | Biosensing membrane |
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