CN111013401A - PVDF separation membrane and preparation method thereof - Google Patents
PVDF separation membrane and preparation method thereof Download PDFInfo
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- CN111013401A CN111013401A CN201911423739.2A CN201911423739A CN111013401A CN 111013401 A CN111013401 A CN 111013401A CN 201911423739 A CN201911423739 A CN 201911423739A CN 111013401 A CN111013401 A CN 111013401A
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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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/36—Polytetrafluoroethene
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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
- B01D67/0016—Coagulation
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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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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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
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
Abstract
The invention relates to the technical field of membrane separation, in particular to a PVDF separation membrane and a preparation method thereof. The PVDF separation membrane comprises a PVDF basal membrane and a chitosan coating compounded on the basal membrane; the PVDF basal membrane consists of a PVDF polymer and an additive; the additive is one or more of polyvinylpyrrolidone, polyvinyl alcohol, polyethylene oxide, polyethylene glycol, lithium chloride, diethyl ether or ethylene glycol; the chitosan coating consists of chitosan and acid; the chitosan has deacetylation degree of 95%, and the acid is one or more of formic acid, acetic acid, hydrochloric acid, benzoic acid, and acrylic acid. The surface of the PVDF-based film is compounded with a chitosan coating, so that the PVDF-based film has antibacterial property and can effectively inhibit the pollution of microorganisms such as protein and organic matters such as humic acid. The chitosan layer compounded by the method is directly compounded in the post-treatment process, is simple and effective, and is suitable for industrial continuous production. The method has simple process, environmental protection and easy operation, and has wide industrial application prospect.
Description
Technical Field
The invention relates to the technical field of membrane separation, in particular to a PVDF separation membrane and a preparation method thereof.
Background
The membrane separation technology has the characteristics of simple and convenient operation, compact equipment, safe working environment, energy consumption and chemical reagent saving, no phase change, no pollution and the like, is widely applied to various industries, particularly in the field of water treatment, and is generally applied to treatment of domestic sewage, industrial wastewater, domestic drinking water and the like.
Polyvinylidene fluoride (PVDF) has good chemical stability, thermal stability and mechanical strength, and is a widely-used separation membrane material, but the PVDF membrane material has relatively low surface energy and relatively strong hydrophobic property, so that the surface of the PVDF membrane is extremely easy to be polluted by microorganisms such as protein and organic matters such as humic acid in the water treatment process, the membrane flux is reduced, the membrane operation cleaning and maintenance cost is increased, the service life of the membrane is shortened, and the practical application of the PVDF membrane in the industry is greatly limited. Therefore, how to select a simple and feasible method and solve the problems of stability, high performance and production feasibility in the hydrophilic modification process of the PVDF membrane is the direction of continuous efforts of researchers.
CN102652904A discloses a method for preparing a PVDF membrane surface cross-linked chitosan hydrophilic membrane. The PVDF base layer is firstly subjected to alkali treatment and then compounded with a chitosan solution. Its advantages are high firmness of composite layer; the disadvantages are that: PVDF after alkali treatment has large brittleness and reduces mechanical strength; and the alkali treatment is not favorable for large-scale mechanized production.
CN103785365A discloses a preparation method of a metal ion selective separation composite membrane, which is characterized in that chitosan and PVDF are blended and stirred to prepare a membrane, but the method can not collect the effective functional groups of chitosan on the surface of the membrane, thereby influencing the exertion of the inherent performance of the chitosan; meanwhile, the chitosan dissolution needs to be carried out by using an acid aqueous solution, and water is a poor solvent of PVDF, so that the PVDF is easy to solidify in advance, the uniformity and the film forming property of the casting film liquid are influenced, and the large-scale mechanical production is not facilitated.
Disclosure of Invention
In view of the above, the present invention provides a PVDF separation membrane and a method for preparing the same. The PVDF separation membrane has high mechanical strength, and the effective functional groups of the chitosan are gathered on the surface of the membrane, thereby being beneficial to the exertion of the inherent performance of the chitosan and having good uniformity and film forming property.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a PVDF separation membrane, which comprises a PVDF base membrane and a chitosan coating compounded on the base membrane;
the PVDF basal membrane consists of a PVDF polymer and an additive; the additive is one or more of polyvinylpyrrolidone, polyvinyl alcohol, polyethylene oxide, polyethylene glycol, lithium chloride, diethyl ether or ethylene glycol;
the chitosan coating consists of chitosan and acid; the chitosan has deacetylation degree of 95%, and the acid is one or more of formic acid, acetic acid, hydrochloric acid, benzoic acid, and acrylic acid.
Preferably, the mass ratio of the PVDF polymer to the additive in the PVDF base film is (8-13): (0.5 to 12); the thickness of the PVDF base film is 0.03-0.05 mm;
preferably, the mass ratio of chitosan to acid in the chitosan coating is (0.01-2): (0.05-5).
Preferably, the mass ratio of chitosan to acid in the chitosan coating is (0.2-0.5): (0.5-2).
Preferably, the PVDF polymer has a weight average molecular weight of 400 to 600 kda.
The invention also provides a preparation method of the PVDF separation membrane, which comprises the following steps:
sequentially dissolving an additive and a PVDF polymer in an organic solvent to obtain a membrane casting solution; after the membrane casting solution is subjected to membrane scraping, solidifying in water to obtain a PVDF base membrane;
mixing chitosan, the dissolved solution and water to obtain a solution containing chitosan; the dissolving solution is an acid water solution;
and (3) coating a solution containing chitosan on the PVDF base membrane, and drying to obtain the PVDF separation membrane.
Preferably, the mass percentage of the additive, the PVDF polymer and the organic solvent is as follows: 8 to 13 percent of PVDF polymer, 0.5 to 12 percent of additive and organic solvent which is complemented to 100 percent.
Preferably, the mass percentages of the additive, the PVDF polymer and the organic solvent are as follows: 12% of PVDF polymer, 8% of additive and the balance of organic solvent to 100%.
Preferably, the organic solvent is one or more of dimethylformamide, dimethylacetamide, N-dimethylpyrrolidone, dimethylsulfoxide, or gamma-hydroxybutyric lactone.
Preferably, the chitosan-containing solution comprises the following components in percentage by mass: 0.01 to 2 percent of chitosan, 0.02 to 5 percent of dissolving solution and water which is complemented to 100 percent.
Preferably, the chitosan-containing solution comprises the following components in percentage by mass: 0.2 to 0.5 percent of chitosan, 0.5 to 2 percent of dissolving solution and water which is complemented to 100 percent.
Preferably, the concentration of the acid in the solution is 30% to 99%.
In the embodiment provided by the invention, the mass percentage concentration of the hydrochloric acid is 36%.
In the examples provided by the present invention, the mass percentage concentration of acetic acid was 99%.
Preferably, the dissolving temperature of the PVDF polymer is 60-80 ℃, and the dissolving time is 3-6 h.
Preferably, the PVDF polymer has a dissolution temperature of 70 ℃ and a dissolution time of 3 h.
Preferably, the scraping film adopts polyester material non-woven fabric as a supporting layer; the thickness of the scraping film is 0.03-0.05 mm, and the speed of the scraping film is 10-23 m/min.
Preferably, the solidification temperature is 0 to 20 ℃.
Preferably, the temperature of solidification is 10 ℃.
Preferably, the environmental humidity is 30-70%;
preferably, the drying temperature is 30-80 ℃, and the drying speed is 2-8 m/min.
Preferably, the drying temperature is 40-50 ℃, and the drying speed is 3-3.5 m/min.
The invention provides a PVDF separation membrane and a preparation method thereof. The PVDF separation membrane comprises a PVDF basal membrane and a chitosan coating compounded on the basal membrane; the PVDF basal membrane consists of a PVDF polymer and an additive; the additive is one or more of polyvinylpyrrolidone, polyvinyl alcohol, polyethylene oxide, polyethylene glycol, lithium chloride, diethyl ether or ethylene glycol; the chitosan coating consists of chitosan and acid; the chitosan has deacetylation degree of 95%, and the acid is one or more of formic acid, acetic acid, hydrochloric acid, benzoic acid, and acrylic acid. The invention has the technical effects that:
1. according to the invention, the surface of the PVDF base membrane is compounded with the chitosan coating, and the chitosan has excellent hydrophilicity and antibacterial activity, so that the hydrophilicity of the membrane is enhanced, a smoother membrane surface layer is endowed with the membrane, pollutants such as proteins, organic matters and the like are not easy to deposit on the membrane surface, the membrane running flux is maintained at a higher level, and the membrane flux can be recovered after simple hydraulic cleaning. The chitosan separation layer compounded on the membrane surface layer has antibacterial property, and can effectively inhibit the pollution of microorganisms such as protein and organic matters such as humic acid.
2. The PVDF separation membrane prepared by the method has good mechanical strength and impact strength, and is widely applicable to various water environments;
3. the chitosan layer compounded by the method is directly compounded in the post-treatment process, is simple and effective, and is suitable for industrial continuous production.
4. The method has simple process, environmental protection and easy operation, and has wide industrial application prospect.
Detailed Description
The invention discloses a PVDF separation membrane and a preparation method thereof, and a person skilled in the art can appropriately improve process parameters by referring to the content. It is expressly intended that all such similar substitutes and modifications which would be obvious to one skilled in the art are deemed to be included in the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
The technical problem to be solved by the invention is to provide a PVDF separation membrane which has good hydrophilicity and strong pollution resistance.
The invention discloses a PVDF separation membrane, comprising: PVDF basal membrane and chitosan coating compounded on the basal membrane;
the invention also discloses a preparation method of the ultrafiltration membrane, which comprises the following steps:
(A) providing a base membrane, wherein the base membrane is a PVDF micro-filtration membrane;
(B) coating a solution containing chitosan on the base membrane to obtain an ultrafiltration membrane;
the solution containing chitosan comprises chitosan, a dissolving solution and water;
the mass fraction of the chitosan is 0.01-2%;
the mass fraction of the dissolving solution is 0.02-5%;
preferably, the dissolving solution is one or more of formic acid, acetic acid, hydrochloric acid, benzoic acid and acrylic acid.
Preferably, in the step (a), the base film is prepared by a method comprising:
dissolving PVDF polymer and an additive in an organic solvent to obtain a membrane casting solution; the mass fraction of the PVDF polymer is 8-13%; the weight average molecular weight of the PVDF polymer is 400-600 kda;
and after the membrane casting solution is subjected to membrane scraping, performing coagulation bath in pure water to obtain the PVDF microfiltration base membrane.
Preferably, the additive is one or more of polyvinylpyrrolidone, polyvinyl alcohol, polyethylene oxide, polyethylene glycol, lithium chloride, diethyl ether and ethylene glycol.
Preferably, the mass fraction of the PVDF polymer is 8-13%, the mass fraction of the additive is 0.5-12%, the mass fraction of the chitosan is 0.01-2%, the deacetylation degree of the chitosan is greater than 95%, and the mass fraction of the dissolving solution is 0.02-5%.
In the process of preparing the PVDF microfiltration membrane, firstly, an additive is dissolved in an organic solvent and stirred for 30-100 min, and after the additive is completely dissolved, a PVDF polymer is added and stirred for 3-6 h at the temperature of 60-80 ℃ to obtain a membrane casting solution. The mass fraction of the PVDF polymer is 8-13%. The additive is one or more of polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, lithium chloride, diethyl ether and ethylene glycol. The mass fraction of the additive is preferably 0.5-12%. The organic solvent is preferably one or more of dimethylformamide, dimethylacetamide, N-dimethylpyrrolidone, dimethylsulfoxide, and gamma-hydroxybutyric lactone (GBL).
And after obtaining the membrane casting solution, defoaming the membrane casting solution, cooling to a certain temperature, scraping the membrane, and solidifying in pure water to obtain the PVDF micro-filtration membrane. In the film scraping process, polyester material non-woven fabric is selected as a supporting layer. The thickness of the scraping film is preferably 0.03-0.05 mm, and the film forming speed is preferably 10-23 m/min. After the film was scraped, the film was solidified in pure water. The temperature of the coagulating bath is preferably 0-20 ℃, and the environmental humidity is preferably 30-70%.
According to the invention, after the PVDF base film is obtained, the base film is coated with a solution containing chitosan on the surface of the base film in the drying process, and the drying temperature and speed are controlled to obtain the uniform PVDF separation film. The solution containing chitosan is coating solution, and comprises chitosan, dissolving solution and water; the mass fraction of the chitosan is 0.01-2%; the mass fraction of the dissolving solution is 0.02-5%; preferably, the dissolving solution is one or more of formic acid, acetic acid, hydrochloric acid, benzoic acid and acrylic acid. The drying temperature is 30-80 ℃; the drying speed is 2-8 m/min.
According to the preparation method, the PVDF separation membrane with high hydrophilic antibacterial performance is obtained by controlling the components of the membrane casting solution and the coating solution and combining the two factors.
The PVDF separation membrane provided by the invention has the advantages that the sludge running flux, the contact angle and the antibacterial performance are tested, and the result shows that the running flux of the PVDF separation membrane in an MBR reactor reaches 40-50 LMH, the contact angle is 62-70 degrees, and the antibacterial rate to Escherichia coli is 85-91%.
The PVDF separation membrane and the reagent used in the preparation method thereof provided by the invention are all commercially available.
The invention is further illustrated by the following examples:
example 1
Dissolving 4 parts of LiCl (lithium chloride) and 4 parts of PVP (polyvinylpyrrolidone) in 80 parts of DMAC (dimethylacetamide) solvent, stirring for 60min, adding 12 parts of PVDF polymer, raising the stirring temperature to 70 ℃, stirring for 3h to obtain a casting solution, defoaming the casting solution, cooling to 15 ℃, scraping the film on polyester non-woven fabric, and solidifying in pure water at 10 ℃ to obtain the PVDF micro-filtration membrane.
0.2% chitosan solution: firstly, 0.2 percent of chitosan by mass is dissolved in 0.5 percent of hydrochloric acid by mass and 40 percent of water by mass under stirring, then the water is supplemented to 100 percent by mass, and the chitosan solution is stirred for 20min and mixed evenly, thus finishing the preparation of the chitosan solution.
And (3) immersing the PVDF micro-filtration membrane into 0.2% chitosan solution for 15s in the drying process, controlling the drying temperature to be 50 ℃ and the drying speed to be 3m/min, and obtaining the uniform PVDF separation membrane.
The sludge running flux of the PVDF separation membrane is 43LMH (liter/hour per square meter), the contact angle is 62 degrees, and the Escherichia coli inhibition rate is 87 percent.
Example 2:
dissolving 4 parts of LiCl and 4 parts of PVP in 80 parts of DMAC solvent, stirring for 60min, adding 12 parts of PVDF polymer, raising the stirring temperature to 70 ℃, stirring for 3h to obtain a membrane casting solution, defoaming the membrane casting solution, cooling to 15 ℃, scraping the membrane on a polyester non-woven fabric, and solidifying in pure water at 10 ℃ to obtain the PVDF micro-filtration membrane.
0.5% chitosan solution: firstly, stirring and dissolving chitosan with the mass fraction of 0.5% in acetic acid with the mass fraction of 2% and water with the mass fraction of 40% completely, then supplementing the water with the mass of 100%, stirring for 20min and uniformly mixing to complete the preparation of the chitosan solution.
And (3) immersing the PVDF micro-filtration membrane into a 0.5% chitosan solution for 12s in the drying process, controlling the drying temperature to be 40 ℃ and the drying speed to be 3.5m/min, and obtaining the uniform PVDF separation membrane.
The sludge running flux of the PVDF separation membrane is 45LMH, the contact angle is 68 degrees, and the Escherichia coli inhibition rate is 88.1 percent.
Comparative example 1
PVDF-based membranes were prepared by the method of example 1, and the PVDF membrane surface cross-linked chitosan hydrophilic membrane was prepared by referring to CN102652904A in example 1 of Chinese patent.
Test example 1 measurement of mechanical Strength
The impact resistance of the film was measured in examples 1 to 2 and comparative example 1. The determination method comprises the following steps: taking a square membrane to be tested with the side length of 12cm, soaking in pure water, and testing under the conditions that the distance between compressed air and the membrane is 5cm, the air pressure is 0.8mpa, continuously shooting the test membrane by the compressed air at a positive angle for 10min, and recording the time when the surface of the membrane begins to be damaged. The larger the impact strength is, the more compact and firm the separation surface layer of the membrane is in the sludge aeration use environment, so that the membrane is less prone to damage and has longer service life and washing resistance life. The results are as follows:
TABLE 1 impact resistance test results for different membranes
| Test items | Example 1 | Example 2 | Comparative example 1 |
| Breakage time(s) | - | - | 540 |
From the test results, it can be seen that the PVDF obtained in comparative example 1 after alkali treatment is highly brittle and has reduced impact strength; and the alkali treatment is not favorable for large-scale mechanized production.
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 (10)
1. The PVDF separation membrane is characterized by comprising a PVDF base membrane and a chitosan coating compounded on the base membrane;
the PVDF base film consists of a PVDF polymer and an additive; the additive is one or more of polyvinylpyrrolidone, polyvinyl alcohol, polyethylene oxide, polyethylene glycol, lithium chloride, diethyl ether or ethylene glycol;
the chitosan coating consists of chitosan and acid; the chitosan has a deacetylation degree of more than 95%, and the acid is one or more of formic acid, acetic acid, hydrochloric acid, benzoic acid and acrylic acid.
2. The PVDF separation membrane according to claim 1, wherein the mass ratio of the PVDF polymer to the additive in the PVDF-based membrane is (8-13): (0.5 to 12); the thickness of the PVDF base film is 0.03-0.05 mm;
the mass ratio of chitosan to acid in the chitosan coating is (0.01-2): (0.05-5).
3. The PVDF separation membrane according to claim 1 or 2, wherein the PVDF polymer has a weight average molecular weight of 400 to 600 kda.
4. A method for producing the PVDF separation membrane according to any one of claims 1 to 3, comprising the steps of:
sequentially dissolving an additive and a PVDF polymer in an organic solvent to obtain a membrane casting solution; after the membrane casting solution is subjected to membrane scraping, solidifying in water to obtain a PVDF base membrane;
mixing chitosan, the dissolved solution and water to obtain a solution containing chitosan; the dissolving solution is an acid aqueous solution;
and coating a solution containing chitosan on the PVDF base membrane, and drying to obtain the PVDF separation membrane.
5. The preparation method according to claim 4, wherein the mass percentages of the additive, the PVDF polymer and the organic solvent are as follows: 8 to 13 percent of PVDF polymer, 0.5 to 12 percent of additive and organic solvent which is complemented to 100 percent.
6. The method according to claim 4, wherein the organic solvent is one or more of dimethylformamide, dimethylacetamide, N-dimethylpyrrolidone, dimethylsulfoxide, or gamma-hydroxybutyric lactone.
7. The preparation method according to claim 4, wherein the solution containing chitosan comprises the following components in percentage by mass: 0.01 to 2 percent of chitosan, 0.02 to 5 percent of dissolving solution and water which is complemented to 100 percent.
8. The preparation method according to claim 4, wherein the PVDF polymer is dissolved at a temperature of 60-80 ℃ for 3-6 h.
9. The preparation method according to claim 4, wherein the scraping film adopts a polyester material non-woven fabric as a supporting layer; the thickness of the scraping film is 0.03-0.05 mm, and the speed of the scraping film is 10-23 m/min.
10. The preparation method according to any one of claims 4 to 9, wherein the solidification temperature is 0-20 ℃, and the ambient humidity is 30-70%;
the drying temperature is 30-80 ℃, and the drying speed is 2-8 m/min.
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| CN114682107A (en) * | 2022-04-07 | 2022-07-01 | 中山大学 | Anti-pollution ultrafiltration membrane and preparation method and application thereof |
| CN116808848A (en) * | 2023-03-21 | 2023-09-29 | 江苏大学 | Organic/inorganic MOF hybrid mixed matrix membrane with high separation performance, preparation method and application |
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| CN116808848A (en) * | 2023-03-21 | 2023-09-29 | 江苏大学 | Organic/inorganic MOF hybrid mixed matrix membrane with high separation performance, preparation method and application |
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