CN112973481A - Hollow fiber positively charged membrane and preparation method thereof - Google Patents
Hollow fiber positively charged membrane and preparation method thereof Download PDFInfo
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- CN112973481A CN112973481A CN202110531452.2A CN202110531452A CN112973481A CN 112973481 A CN112973481 A CN 112973481A CN 202110531452 A CN202110531452 A CN 202110531452A CN 112973481 A CN112973481 A CN 112973481A
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- hollow fiber
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- diamine
- charged membrane
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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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
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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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
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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
- B01D69/08—Hollow fibre membranes
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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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
Abstract
The invention belongs to the field of separation, and particularly relates to a hollow fiber positively charged membrane and a preparation method thereof, wherein the preparation method comprises the following steps: the following components in parts by mass: styrene maleic anhydride random copolymer, main material, pore-foaming agent and solvent; stirring for 24 hours at 60 ℃, standing for 24 hours to form a membrane casting solution, extruding the membrane casting solution and a core solution into a coagulating bath from a hollow fiber spinneret plate, and shaping to obtain a hollow fiber positively charged membrane containing naked amino groups; the main material is one or a mixture of a plurality of materials of polysulfone, polyethersulfone, polyvinylidene fluoride and polyvinyl chloride; when the internal pressure type hollow fiber positively charged membrane is synthesized, the core liquid contains polyamine substances; when the external pressure type hollow fiber positively charged membrane is synthesized, the coagulating bath contains polyamine substances. The hollow fiber membrane prepared by the method of the invention is obviously positively charged, and the pollution resistance (the ratio of the accumulated water yield to the water yield) is also obviously improved.
Description
Technical Field
The invention belongs to the field of separation, and particularly relates to a hollow fiber positively charged membrane and a preparation method thereof.
Background
The traditional method for preparing the electropositive membrane needs to firstly activate the hollow fiber membrane, such as strong alkali, heating, radiation and other strong conditions. The active site is then converted to a positively charged group by one or more chemical reactions. The method has complex process and violent conditions, generates a large amount of waste liquid, and is not suitable for large-scale production. And each membrane material has different activation methods, and the methods for converting the active sites are more diverse, so that the method has a narrow application range, and different modification methods need to be developed for each membrane material.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a hollow fiber positively charged membrane and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a hollow fiber positively charged membrane comprises the following steps:
under the protection of inert gas, the following components in parts by mass are mixed: 0.05-0.5 part of styrene maleic anhydride random copolymer, 22 parts of main material, 3 parts of pore-foaming agent and 100 parts of solvent; stirring for 24 hours at 60 ℃, standing for 24 hours to form a membrane casting solution, extruding the membrane casting solution and a core solution into a coagulating bath from a hollow fiber spinneret plate, and shaping to obtain a hollow fiber positively charged membrane containing naked amino groups; the main material is one or a mixture of a plurality of materials of polysulfone, polyethersulfone, polyvinylidene fluoride and polyvinyl chloride;
when the internal pressure type hollow fiber positively charged membrane is synthesized, the core liquid contains polyamine substances; when the external pressure type hollow fiber positively charged membrane is synthesized, the coagulating bath contains polyamine substances.
The styrene maleic anhydride random copolymer is prepared by the following method, under the protection of nitrogen, styrene, maleic anhydride and azobisisobutyronitrile are sequentially added into dimethylacetamide, the molar ratio of the three substances is 1:1:0.003, and the mixture is stirred for 10 hours at 60 ℃ to obtain a product.
The polyamine substances are as follows: one or more of m-phenylenediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, p-phenylenediamine, o-phenylenediamine, aminoethyl piperazine, homopiperazine, 1, 4-cyclohexanediamine, 1, 2-cyclohexanediamine, 1, 3-cyclohexanediamine, ethylene diamine, propylene diamine, butylene diamine, pentylene diamine, hexylene diamine, octylene diamine, decamethylene diamine, biphenyl diamine, naphthalene diamine, and melamine.
The core liquid temperature is as follows: 30-60 ℃; preferably, the bore fluid temperature is 30 ℃. The temperature of the coagulation bath was 30 ℃.
The concentration of the polyamine substances is 1-100 g/L.
The pore-foaming agent is one or a mixture of more of lithium chloride, polyoxyethylene 400, glycol and polyvinylpyrrolidone.
The solvent is one or a mixture of Dimethylacetamide (DMAC), Dimethylformamide (DMF) and N-methylpyrrolidone (NMP).
The invention also discloses the hollow fiber positively charged membrane obtained by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
the method for preparing the hollow fiber positively-charged membrane utilizes the active groups which are obtained by polymerizing styrene and maleic anhydride and have acid anhydride in common, the acid anhydride active groups react with amino groups in polyamine to form amide groups, and lone-pair electrons in other unreacted amino groups in the polyamine amino groups can form NH with hydrogen in water3 +So that the surface of the base membrane forms a hollow fiber positively charged membrane with positive charges;
the polyamine exists in the core liquid (internal pressure type) or the coagulating bath (external pressure type), so the polyamine is only formed on the surface of the base membrane, the property of the base membrane is not changed, meanwhile, the exposed amino group can be firmly fixed on the surface of the base membrane by adopting a chemical crosslinking method, and cannot be damaged and influenced along with the cleaning of the base membrane, so the performance of the hollow fiber charged membrane is not damaged, the hollow fiber membrane prepared by the method of the invention is obviously positively charged, and the pollution resistance (the ratio of accumulated water yield to water yield) is also obviously improved.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the following provides a detailed description of the present invention with reference to the embodiments.
Example 1: under the protection of nitrogen, 0.3g of active polymer (styrene maleic anhydride random copolymer), 22g of PVDF, 3g of lithium chloride and 100g of solvent are stirred for 24 hours at 60 ℃, and then are kept stand for 24 hours to obtain a membrane casting solution, and then the membrane casting solution and core solution are extruded into a coagulating bath by a hollow fiber spinneret plate to be shaped to obtain a hollow fiber positively charged membrane containing naked amino groups; wherein the core liquid is RO water added with 10 g/L triethylene tetramine at 30 ℃. The coagulating bath is RO water, 30 ℃; wherein the styrene maleic anhydride random copolymer is prepared by the following steps: under the protection of nitrogen, sequentially adding styrene, maleic anhydride and azodiisobutyronitrile into dimethylacetamide at a molar ratio of 1:1:0.003, and stirring at 60 ℃ for 10 hours to obtain a product.
Example 2: the core liquid is RO water at 30 ℃. The coagulating bath was RO water containing 10 g/L of triethylene tetramine and was 30 ℃. The rest is the same as in example 1.
Example 3: the main material is polysulfone, and the rest is the same as the example 1.
Example 4: the main material is PVC, and the rest is the same as the example 1.
Example 5: 100g/L of triethylene tetramine is added into the core liquid. The rest is the same as in example 1.
Example 6: 1 g/L triethylene tetramine is added into the core liquid. The rest is the same as in example 1.
Example 7: 10 g/L m-phenylenediamine was added to the core solution. The rest is the same as in example 1.
Example 8: the same procedure as in example 1 was repeated except that 0.05g of the active polymer was added to the casting solution.
Example 9: the same procedure as in example 1 was repeated except that 0.5g of the active polymer was added to the casting solution.
Example 10: the bore fluid temperature was 60 ℃ and the rest was the same as in example 1.
Comparative example 1: the same procedure as in example 1 was repeated except that the nitrogen gas was not introduced into the dope solution.
Comparative example 2: the casting solution was the same as in example 1 except that no active polymer was added.
Comparative example 3: the amine added to the core liquid was ammonia water, and the rest was the same as in example 1.
Membrane performance testing method
Testing liquid: the test was carried out using tap water.
The operation parameters are as follows: the test was performed using a membrane evaluator, pressure 0.1 MPa, 25 ℃, pH = 7.0.
Calculating the formula:
flux F = V/T, where V is the water production volume and T is the measurement time.
The surface charge amount was measured using a surface charge meter. Table 1 shows the test results of the different examples and comparative examples.
TABLE 1
From the above table, it can be seen that the hollow fiber membrane prepared by the method of the present invention is significantly positively charged, and the contamination resistance (ratio of cumulative water yield to water yield) is also significantly improved.
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 (7)
1. The preparation method of the hollow fiber positively charged membrane is characterized by comprising the following steps:
under the protection of inert gas, the following components in parts by mass are mixed: 0.05-0.5 part of styrene maleic anhydride random copolymer, 22 parts of main material, 3 parts of pore-foaming agent and 100 parts of solvent; stirring for 24 hours at 60 ℃, standing for 24 hours to form a membrane casting solution, extruding the membrane casting solution and a core solution into a coagulating bath from a hollow fiber spinneret plate, and shaping to obtain a hollow fiber positively charged membrane containing naked amino groups; the main material is one or a mixture of a plurality of materials of polysulfone, polyethersulfone, polyvinylidene fluoride and polyvinyl chloride;
when the internal pressure type hollow fiber positively charged membrane is synthesized, the core liquid contains polyamine substances; when the external pressure type hollow fiber positively charged membrane is synthesized, the coagulating bath contains polyamine substances.
2. The method for preparing the hollow fiber electropositive membrane according to claim 1, wherein the styrene maleic anhydride random copolymer is prepared by adding styrene, maleic anhydride and azobisisobutyronitrile into dimethylacetamide under the protection of nitrogen in a molar ratio of 1:1:0.003, and stirring at 60 ℃ for 10 hours to obtain the product.
3. The method for preparing a hollow fiber electropositive membrane according to claim 1, wherein the concentration of the polyamine substance is 1-100 g/L.
4. The method for preparing a hollow fiber electropositive membrane according to claim 1, wherein said polyamine is: one or more of m-phenylenediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, p-phenylenediamine, o-phenylenediamine, aminoethyl piperazine, homopiperazine, 1, 4-cyclohexanediamine, 1, 2-cyclohexanediamine, 1, 3-cyclohexanediamine, ethylene diamine, propylene diamine, butylene diamine, pentylene diamine, hexylene diamine, octylene diamine, decamethylene diamine, biphenyl diamine, naphthalene diamine, and melamine.
5. The method for preparing a hollow fiber electropositive membrane according to claim 1, wherein the pore-forming agent is one or more of lithium chloride, polyoxyethylene 400, ethylene glycol and polyvinylpyrrolidone.
6. The method for preparing the hollow fiber electropositive membrane according to claim 1, wherein the solvent is one or more of Dimethylacetamide (DMAC), Dimethylformamide (DMF), and N-methylpyrrolidone (NMP).
7. A hollow fiber electropositive membrane obtained by the preparation method of any one of claims 1 to 6.
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| US4882106A (en) * | 1987-02-27 | 1989-11-21 | Baxter Travenol Laboratories, Inc. | Methods of manufacturing nucleophilic material modified for improved biocompatibility |
| CN101961612A (en) * | 2010-09-30 | 2011-02-02 | 浙江工业大学 | Method for carrying out hydrophilic modification on hollow fiber membrane by utilizing hyperbranched polymer |
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