CN112957926A - Ultrafiltration membrane for sewage treatment process and preparation method thereof - Google Patents
Ultrafiltration membrane for sewage treatment process and preparation method thereof Download PDFInfo
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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
- 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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- 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
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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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
- B01D2323/02—Hydrophilization
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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
- B01D2325/36—Hydrophilic membranes
Abstract
The invention discloses an ultrafiltration membrane for a sewage treatment process and a preparation method thereof, belongs to the technical field of ultrafiltration membranes, and discloses an ultrafiltration membrane, which comprises the following components in parts by weight: inorganic membrane-making material, wherein the inorganic membrane-making material comprises inorganic nano particles, and the particle size of the inorganic nano particles is 10-30 nm; the functional film-making material comprises graphene oxide; the substrate membrane material is PVDF; the inorganic film-making material and the functional film-making material are distributed in the substrate film material. The ultrafiltration membrane obtained by the invention has high membrane flux, and the membrane flux of the ultrafiltration membrane is 400L/(m)2H) above; the rejection rate is good, and the rejection rate of the ultrafiltration membrane is more than 89%; the anti-pollution capacity is good, and the anti-pollution capacity of the ultrafiltration membrane is more than 60%; the mechanical strength is good, the tensile strength of the ultrafiltration membrane is more than 15N, and the elongation at break of the ultrafiltration membrane is more than 4.5%.
Description
Technical Field
The invention belongs to the technical field of ultrafiltration membranes, and particularly relates to an ultrafiltration membrane for a sewage treatment process and a preparation method thereof.
Background
An ultrafiltration membrane is a microporous separation membrane having a pore size in the range of 0.01 to 0.1 μm, the pore size of which is generally characterized by molecular weight cut-off. Ultrafiltration membranes have been used to remove large molecular weight substances such as bacteria, emulsified oils, metal oxides, colloids, proteins, etc. from water or other solutions.
The polyvinylidene fluoride has excellent weather resistance and chemical stability, and the performance of the polyvinylidene fluoride is basically unchanged after the polyvinylidene fluoride is irradiated for one year under the ultraviolet ray with the wavelength of 200-400 nm; the solvent is not corroded by strong oxidants such as acid and alkali and halogen at room temperature, is stable to organic solvents such as aliphatic hydrocarbon, aromatic hydrocarbon, alcohol and aldehyde, and is only dissolved in strong polar solvents such as N-methylpyrrolidone (NMP), dimethylacetamide (DMAc) and the like. Polyvinylidene fluoride (PVDF) is widely used in the field of membrane separation because of its many excellent properties. However, due to the hydrophobicity of the PVDF membrane, the PVDF membrane is easy to generate pollutant adsorption in the process of separating oil-containing pollutants, so that membrane pollution is caused, and the application of the PVDF membrane in the field of sewage separation is limited. Therefore, modification of PVDF membranes to enhance their separation performance and stain resistance has become a major research direction. The PVDF modification method mainly comprises a surface modification method and a blending modification method.
Disclosure of Invention
The invention aims to provide an ultrafiltration membrane which can be used for sewage treatment, has high membrane flux, good rejection rate, good pollution resistance and good mechanical strength.
The technical scheme adopted by the invention for realizing the purpose is as follows:
an ultrafiltration membrane, comprising:
the substrate membrane material is PVDF;
inorganic membrane-making material, wherein the inorganic membrane-making material comprises inorganic nano particles, and the particle size of the inorganic nano particles is 10-30 nm;
the functional film-making material comprises graphene oxide;
the proportion relation between the inorganic film-making material and the functional film-making material in the base film material is as follows, the mass ratio is 8: 1-8. A large number of oxygen-containing functional groups (hydroxyl, carboxyl and epoxy) are distributed on the surface of the graphene oxide carbon layer, so that the graphene oxide carbon layer has good hydrophilicity, and the graphene oxide carbon layer and PVDF are blended to prepare a membrane, so that the hydrophilicity of the membrane can be improved, and the organic pollution resistance of the membrane is further improved. The inorganic nano particles can reduce the surface contact angle of the PVDF ultrafiltration membrane, increase the hydrophilicity of the PVDF ultrafiltration membrane and improve the pollution resistance of the PVDF ultrafiltration membrane. The PVDF has good stability and corrosion resistance, and provides the ultrafiltration membrane with excellent stability and corrosion resistance.
Preferably, the inorganic nanoparticles are at least one of titanium dioxide, aluminum oxide, silicon dioxide and ferroferric oxide.
Preferably, the functional film-making material further comprises at least one of polyethylene glycol, PVP and diethyl 3, 4-vinyldioxypyrrole-2, 5-dicarboxylate. The ultrafiltration membrane is prepared by blending polyethylene glycol, PVP, 3, 4-vinyl dioxypyrrole-2, 5-dicarboxylic acid diethyl ester and the materials, so that the hydrophilicity of the ultrafiltration membrane is further improved, the membrane flux of the ultrafiltration membrane is improved, the rejection rate of the ultrafiltration membrane is improved, the pollution resistance of the ultrafiltration membrane is improved, and the mechanical property of the ultrafiltration membrane is improved.
The invention discloses application of the ultrafiltration membrane in sewage treatment.
The invention aims to provide a preparation method of an ultrafiltration membrane which can be used for sewage treatment, has high membrane flux, good rejection rate, good pollution resistance and good mechanical strength.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a method of making an ultrafiltration membrane, comprising: preparing an ultrafiltration membrane by using an inorganic membrane preparation material, a functional membrane preparation material, a substrate membrane material and a solvent through an immersion precipitation phase inversion method; the immersion precipitation phase inversion method comprises the steps of material mixing, water bath stirring, ultrasonic treatment, standing and curing, film scraping, water bath solidification and film forming.
Preferably, the inorganic membrane making material is added into a solvent, the substrate membrane material is added after ultrasonic dispersion, the functional membrane making material is added after stirring and mixing, a homogeneous membrane casting solution is formed after stirring for 8-24h, standing and defoaming are carried out for 8-24h, a membrane scraper is used for scraping a liquid membrane, then a glass plate is immersed into deionized water at 15-30 ℃ to complete phase exchange, and then the membrane is taken out and is placed into the deionized water to be immersed for 18-54h to remove residual solvent.
Preferably, the solvent is 70-85 wt% DMF.
Preferably, the inorganic film-forming material is an inorganic nanoparticle.
More preferably, the inorganic nanoparticles have a particle size of 10-30 nm.
More preferably, the inorganic nanoparticles are at least one of titanium dioxide, aluminum oxide, silicon dioxide and ferroferric oxide.
Preferably, the amount of the inorganic film-forming material added is 0.2 to 1.6 wt% of the solvent.
More preferably, the functional film-making material comprises graphene oxide and at least one of: polyethylene glycol, PVP, 3, 4-vinyl dioxypyrrole-2, 5-dicarboxylic acid diethyl ester.
Still more preferably, the addition amount of polyethylene glycol is 20 to 100 wt% of graphene oxide.
Still more preferably, the amount of PVP added is 20 to 80 wt% of the graphene oxide.
Still more preferably, diethyl 3, 4-vinyldioxypyrrole-2, 5-dicarboxylate is added in an amount of 40 to 120 wt% of graphene oxide.
Preferably, the addition amount of the functional film-forming material is 0.2 to 1.6 wt% of the solvent.
Preferably, the substrate film material is PVDF.
Preferably, the addition amount of the base film material is 18 to 25 wt% of the solvent.
More preferably, the temperature at which the base film material is added is 50-70 ℃.
The ultrafiltration membrane is prepared by adopting the inorganic membrane preparation material, the functional membrane preparation material and the substrate membrane material, so the ultrafiltration membrane has the following beneficial effects: the membrane flux is high, and the membrane flux of the ultrafiltration membrane is 400L/(m)2H) above; the rejection rate is good, and the rejection rate of the ultrafiltration membrane is more than 89%; the anti-pollution capacity is good, and the anti-pollution capacity of the ultrafiltration membrane is more than 60%; the mechanical strength is good, the tensile strength of the ultrafiltration membrane is more than 15N, and the elongation at break of the ultrafiltration membrane is more than 4.5%. Therefore, the invention is a preparation method of the ultrafiltration membrane which can be used for sewage treatment, has high membrane flux, good rejection rate, good pollution resistance and good mechanical strength.
Drawings
FIG. 1 is a flux graph of an ultrafiltration membrane;
FIG. 2 is a graph of ultrafiltration membrane rejection;
FIG. 3 is an anti-fouling diagram for an ultrafiltration membrane;
FIG. 4 is a graph of ultrafiltration membrane tensile strength;
FIG. 5 is a graph of the elongation at break of the ultrafiltration membrane.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
example 1:
a method for preparing an ultrafiltration membrane, which comprises the steps of,
adding an inorganic membrane making material into a solvent, performing ultrasonic dispersion, adding a substrate membrane material, stirring and mixing, adding a functional membrane making material, stirring for 12 hours to form a homogeneous membrane casting solution, standing and defoaming for 12 hours, scraping a liquid membrane by using a membrane scraping machine, then soaking a glass plate into deionized water at 20 ℃ to complete phase exchange, then taking out the membrane, and soaking in the deionized water for 36 hours to remove residual solvent; the inorganic film-making material is titanium dioxide nano particles, the particle size is 20nm, and the addition amount of the inorganic film-making material is 0.8 wt% of the solvent; the solvent was 80 wt% DMF; the substrate film material is polyvinylidene fluoride, the addition amount of the substrate film material is 21 wt% of the solvent, and the temperature when the substrate film material is added is 60 ℃; the functional film material is graphene oxide, and the addition amount of the functional film material is 0.6 wt% of the solvent.
Example 2:
in this example, only the difference from example 1 is that the inorganic film-forming material is alumina nanoparticles.
Example 3:
this example is different from example 1 only in that the inorganic film-forming material is silica nanoparticles
Example 4:
compared with the embodiment 1, the difference of the embodiment is only that the functional film-making material is graphene oxide and polyethylene glycol, and the addition amount of the polyethylene glycol is 60 wt% of the graphene oxide.
Example 5:
the present example is different from example 1 only in that the functional film-forming material is graphene oxide and PVP, and the amount of PVP added is 60 wt% of the graphene oxide.
Example 6:
this example is different from example 1 only in that the functional film-forming material is graphene oxide and diethyl 3, 4-vinyldioxypyrrole-2, 5-dicarboxylate, and the amount of diethyl 3, 4-vinyldioxypyrrole-2, 5-dicarboxylate added is 60 wt% of graphene oxide.
Example 7:
the ultrafiltration membrane is prepared by mixing the membrane preparation material and the base membrane material together, the internal porosity of the PVDF ultrafiltration membrane can be increased, the pore structure is improved, the hydrophilicity is enhanced, the membrane flux is increased, and the performance of the ultrafiltration membrane can be further improved by pretreating the membrane preparation material. The invention further adopts the pretreatment solution containing the silane coupling agent, the caffeic acid dopamine and the acrylic acid quinoline ester to treat the inorganic membrane-making material and the functional membrane-making material for 10-60min, and finds that the caffeic acid dopamine and the acrylic acid quinoline ester are used in the pretreatment solution, so that the membrane flux of the ultrafiltration membrane is further improved, the mechanical strength of the ultrafiltration membrane is improved, the tensile strength is improved, the breaking elongation is improved, but the interception rate and the anti-pollution capacity of the ultrafiltration membrane are not greatly influenced. In the pretreatment solution, a silane coupling agent is KH560, the mass fraction of the silane coupling agent is 10-25 wt% of the pretreatment solution, the mass fraction of caffeic acid dopamine is 1-10 wt% of the pretreatment solution, the mass fraction of acrylic acid quinoline ester is 1-8 wt% of the pretreatment solution, and a solvent is water and acetone in a mass ratio of 1: mixing at a ratio of 0.3-3.
A method for preparing an ultrafiltration membrane, which comprises the steps of,
pretreatment of an inorganic membrane-making material: the titanium dioxide nano particles are soaked in a pretreatment solution containing a silane coupling agent, caffeic acid dopamine and acrylic acid quinoline ester for 20 min. In the pretreatment solution, a silane coupling agent is KH560, the mass fraction of the silane coupling agent is 15 wt% of the pretreatment solution, the mass fraction of caffeic acid dopamine is 3 wt% of the pretreatment solution, the mass fraction of acrylic acid quinoline ester is 2 wt% of the pretreatment solution, and a solvent is water and acetone in a mass ratio of 1: mixing at a ratio of 0.6.
Pretreatment of a functional film-making material: and soaking the graphene oxide in a pretreatment solution containing a silane coupling agent, dopamine caffeate and quinoline acrylate for 20 min. In the pretreatment solution, a silane coupling agent is KH560, the mass fraction of the silane coupling agent is 15 wt% of the pretreatment solution, the mass fraction of caffeic acid dopamine is 3 wt% of the pretreatment solution, the mass fraction of acrylic acid quinoline ester is 2 wt% of the pretreatment solution, and a solvent is water and acetone in a mass ratio of 1: mixing at a ratio of 0.6.
Adding an inorganic membrane making material into a solvent, performing ultrasonic dispersion, adding a substrate membrane material, stirring and mixing, adding a functional membrane making material, stirring for 12 hours to form a homogeneous membrane casting solution, standing and defoaming for 12 hours, scraping a liquid membrane by using a membrane scraping machine, then soaking a glass plate into deionized water at 20 ℃ to complete phase exchange, then taking out the membrane, and soaking in the deionized water for 36 hours to remove residual solvent; the inorganic film-making material is titanium dioxide nano particles, the particle size is 20nm, and the addition amount of the inorganic film-making material is 0.8 wt% of the solvent; the solvent was 80 wt% DMF; the substrate film material is polyvinylidene fluoride, the addition amount of the substrate film material is 21 wt% of the solvent, and the temperature when the substrate film material is added is 60 ℃; the functional film-making material is graphene oxide and diethyl 3, 4-vinyldioxypyrrole-2, 5-dicarboxylate, the addition amount of the diethyl 3, 4-vinyldioxypyrrole-2, 5-dicarboxylate is 60 wt% of the graphene oxide, and the addition amount of the functional film-making material is 0.6 wt% of the solvent.
Example 8:
the difference between this example and example 7 is that the mass fraction of caffeic acid dopamine in the pretreatment solution is 6 wt% of the pretreatment solution, and the mass fraction of quinolinyl acrylate is 6 wt% of the pretreatment solution.
Example 9:
this example is different from example 8 only in that quinoline acrylate was not added to the pretreatment solution.
Example 10:
this example is different from example 8 only in that caffeic acid dopamine was not added to the pretreatment solution.
Example 11:
this example is different from example 8 only in that caffeic acid dopamine and quinolinyl acrylate were not added to the pretreatment solution.
The thickness of the ultrafiltration membrane used for testing is 50-500 μm.
Test example 1:
1. membrane flux test
Test samples: the ultrafiltration membranes obtained in the examples were prepared with a thickness of 200 μm.
The testing steps are as follows: and cutting the ultrafiltration membrane which is placed in the purified water for 48 hours into a membrane sheet which accords with the size of the ultrafiltration cup. The membranes were statically pressed for 30min at a pressure of 0.1MPa, then the membrane flux was measured at a pressure of 0.1MPa and the amount of water passing over the specified time was recorded.
The calculation formula is as follows:
J＝V/(AT)。
j: membrane flux, L/(m) at a pressure of 0.1MPa2H); v: the volume of the solution passing through the ultrafiltration membrane in a specified time is mL; a: effective water passing area of ultrafiltration membrane in cm2(ii) a T: the time elapsed for the water volume V, s.
The results of the membrane energy test are shown in FIG. 1, in which the membrane flux of example 1 is 482L/(m)2H) the membrane flux of example 2 was 411L/(m)2H) the membrane flux of example 3 was 456L/(m)2H); example 4 shows an increase in membrane flux of the ultrafiltration membrane obtained by adding polyethylene glycol compared to example 1; example 5 compared to example 1, it is shown that the addition of PVP increases the membrane flux of the ultrafiltration membrane; example 6 in comparison to example 1, it was shown that the addition of diethyl 3, 4-vinyldioxypyrrole-2, 5-dicarboxylate increased the membrane flux of the ultrafiltration membrane; examples 7 to 8 showed that the membrane flux of the ultrafiltration membrane obtained by treating the inorganic membrane-forming material and the functional membrane-forming material with the pretreatment solution containing the silane coupling agent, dopamine caffeate and quinolinylacrylate was higher than that of example 6, and example 8 showed that the ultrafiltration membrane obtained by adding caffeic acid and the caffeic acid to the inorganic membrane-forming material and the functional membrane-forming material together was higher than that of examples 9 to 10The membrane flux of the ultrafiltration membrane obtained after the pretreatment liquid of the dopamine and the quinoline acrylate is used for treating the inorganic membrane making material and the functional membrane making material is superior to the membrane flux of the ultrafiltration membrane obtained after the pretreatment liquid only containing the dopamine caffeate or the quinoline acrylate is used for treating the inorganic membrane making material and the functional membrane making material. Compared with example 11, example 8 shows that caffeic acid dopamine and acrylic acid quinoline ester are added into the pretreatment liquid, and the membrane flux of the ultrafiltration membrane obtained after the treatment of the inorganic membrane-making material and the functional membrane-making material is improved.
The membrane flux of the ultrafiltration membrane obtained by the invention is 400L/(m)2H) above.
2. Rejection rate test
Test samples: the ultrafiltration membranes obtained in the examples were prepared with a thickness of 200 μm.
The testing steps are as follows: preparing a Bovine Serum Albumin (BSA) solution standard curve, drying BSA in a drying oven at 100 ℃ for 3 hours until the BSA reaches a constant weight (the mass difference between the two times is less than 0.020g), preparing 100mg/L BSA solution, taking 2.0mL, 4.0mL, 6.0mL, 8.0mL and 10.0mL BSA solutions respectively, fixing the volume by using a 10mL volumetric flask, preparing 20.0mg/L, 40.0mg/L, 60.0mg/L, 80.0mg/L and 100.0mg/L BSA standard solutions, wherein the linear relation of the standard curve is as follows: 1283.7x-3.0158 and R as the correlation coefficient2＝0.9992。
Detecting UV of the pre-filtered water and the post-filtered water of the test sample by using an ultraviolet visible spectrophotometer280The value is obtained.
The retention rate is calculated as follows:
R＝(1-C2/C1)×100％。
r is the rejection rate of the membrane; c1The stock solution concentration of BSA, mg/L; c2The concentration of BSA solution after filtration was mg/L.
The retention test results are shown in fig. 2, in which the retention of example 1 is 92%, the retention of example 2 is 89%, and the retention of example 3 is 91%; example 4 shows an increase in rejection of ultrafiltration membranes obtained by addition of polyethylene glycol compared to example 1; example 5 compared to example 1, it is shown that the addition of PVP increases the rejection of the ultrafiltration membrane; example 6 in comparison to example 1, it is shown that the addition of diethyl 3, 4-vinyldioxypyrrole-2, 5-dicarboxylate increases the rejection of ultrafiltration membranes; examples 7 to 8 show that the difference in retention rate of the ultrafiltration membrane obtained by treating the inorganic membrane-forming material and the functional membrane-forming material with the pretreatment solution containing the silane coupling agent, the caffeic acid dopamine and the quinolinyl acrylate is not significant as compared with example 6, and example 8 shows that the difference in retention rate of the ultrafiltration membrane obtained by treating the inorganic membrane-forming material and the functional membrane-forming material with the pretreatment solution containing both caffeic acid dopamine and quinolinyl acrylate is not significant as compared with the ultrafiltration membrane obtained by treating the inorganic membrane-forming material and the functional membrane-forming material with the pretreatment solution containing only caffeic acid dopamine or quinolinyl acrylate as compared with examples 9 to 10. Compared with example 11, the results show that the retention rates of the ultrafiltration membranes obtained after the inorganic membrane-making material and the functional membrane-making material are treated are not greatly influenced by adding the caffeic acid dopamine and the acrylic acid quinoline ester into the pretreatment liquid.
The retention rate of the ultrafiltration membrane obtained by the invention is more than 89%.
3. Anti-contamination capability test
Test samples: the ultrafiltration membranes obtained in the examples were prepared with a thickness of 200 μm.
The testing steps are as follows: and (3) stirring and cleaning the applied ultrafiltration membrane for 20min, and back washing for 10 min. And then carrying out a water purification membrane flux test under 0.1 MPa.
The anti-pollution capability calculation formula is as follows:
R＝J2/J1×100％。
J1the membrane flux before filtration, mg/L; j. the design is a square2The membrane flux after filtration, mg/L; r is the anti-pollution capacity of the ultrafiltration membrane percent.
The results of the anti-contamination capability test are shown in FIG. 3, in which the anti-contamination capability of example 1 is 63%, the anti-contamination capability of example 2 is 61%, and the anti-contamination capability of example 3 is 62%; example 4 shows that the anti-contamination capability of the ultrafiltration membrane obtained by adding polyethylene glycol is improved compared with example 1; example 5 compared to example 1, it is shown that the addition of PVP improves the anti-fouling capacity of the ultrafiltration membrane; example 6 in comparison to example 1, it is shown that the addition of diethyl 3, 4-vinyldioxypyrrole-2, 5-dicarboxylate increases the anti-fouling capability of the ultrafiltration membrane; examples 7 to 8 show that the anti-contamination capability of the ultrafiltration membrane obtained by treating the inorganic membrane-making material and the functional membrane-making material with the pretreatment solution containing the silane coupling agent, the caffeic acid dopamine and the quinolinyl acrylate is improved compared with example 6, and example 8 shows that the anti-contamination capability of the ultrafiltration membrane obtained by treating the inorganic membrane-making material and the functional membrane-making material with the pretreatment solution containing both caffeic acid dopamine and quinolinyl acrylate is superior to the anti-contamination capability of the ultrafiltration membrane obtained by treating the inorganic membrane-making material and the functional membrane-making material with the pretreatment solution containing only caffeic acid dopamine or quinolinyl acrylate, compared with examples 9 to 10. Compared with example 11, example 8 shows that the anti-pollution capability of the ultrafiltration membrane obtained after the inorganic membrane-making material and the functional membrane-making material are treated is improved by adding caffeic acid dopamine and acrylic acid quinoline ester into the pretreatment liquid.
The anti-pollution capacity of the ultrafiltration membrane obtained by the invention is more than 60%.
4. Mechanical Strength test
The mechanical strength of the membrane is one of the important indicators for evaluating the usefulness of the membrane, and the value of the mechanical strength is determined by the chemical properties of the membrane material and the reinforced material thereof. The inorganic nanoparticles having high strength are dispersed in the polymeric organic film, which has an influence on the mechanical strength of the film. The mechanical strength of the membrane, including the tensile strength and the elongation at break of the ultrafiltration membrane, was determined by a tensile test method.
Test samples: the ultrafiltration membranes obtained in the examples were prepared with a thickness of 200 μm.
Testing an instrument: model W56 universal electronic tester.
And (3) testing conditions are as follows: the test temperature is room temperature (about 25 ℃), the stretching speed is 5mm/min, and the results of the tensile strength and the breaking elongation are taken as the average value of 5 test data.
The mechanical strength test includes tensile strength and elongation at break, and the tensile strength test results are shown in fig. 4, wherein the tensile strength of example 1 is 15.9N, the tensile strength of example 2 is 15.5N, and the tensile strength of example 3 is 15.7N; example 4 shows an improvement in tensile strength of the ultrafiltration membrane obtained by adding polyethylene glycol compared to example 1; example 5 compared to example 1, it is shown that the addition of PVP improves the tensile strength of the ultrafiltration membrane; example 6 in comparison to example 1, it is shown that the addition of diethyl 3, 4-vinyldioxypyrrole-2, 5-dicarboxylate increases the tensile strength of the ultrafiltration membrane; examples 7 to 8 show that the tensile strength of the ultrafiltration membrane obtained by treating the inorganic membrane-forming material and the functional membrane-forming material with the pretreatment solution containing the silane coupling agent, the caffeic acid dopamine and the quinolinyl acrylate is improved compared with example 6, and example 8 shows that the tensile strength of the ultrafiltration membrane obtained by treating the inorganic membrane-forming material and the functional membrane-forming material with the pretreatment solution containing both caffeic acid dopamine and quinolinyl acrylate is superior to the tensile strength of the ultrafiltration membrane obtained by treating the inorganic membrane-forming material and the functional membrane-forming material with the pretreatment solution containing only caffeic acid dopamine or quinolinyl acrylate, compared with examples 9 to 10. Compared with example 11, example 8 shows that the tensile strength of the ultrafiltration membrane obtained after the inorganic membrane-making material and the functional membrane-making material are treated is improved by adding caffeic acid dopamine and acrylic acid quinoline ester into the pretreatment liquid.
The tensile strength of the ultrafiltration membrane obtained by the invention is more than 15N.
The elongation at break test results are shown in fig. 5, where the elongation at break of example 1 is 15.9N, the elongation at break of example 2 is 15.5N, and the elongation at break of example 3 is 15.7N; example 4 shows an increase in elongation at break of the ultrafiltration membrane obtained by adding polyethylene glycol compared to example 1; example 5 compared to example 1, it is shown that the addition of PVP increases the elongation at break of the ultrafiltration membrane; example 6 in comparison to example 1, it is shown that the addition of diethyl 3, 4-vinyldioxypyrrole-2, 5-dicarboxylate increases the elongation at break of the ultrafiltration membrane; examples 7 to 8 show that the elongation at break of the ultrafiltration membrane obtained by treating the inorganic membrane-forming material and the functional membrane-forming material with the pretreatment solution containing the silane coupling agent, the caffeic acid dopamine and the quinolinyl acrylate is improved compared with example 6, and example 8 shows that the elongation at break of the ultrafiltration membrane obtained by treating the inorganic membrane-forming material and the functional membrane-forming material with the pretreatment solution containing both caffeic acid dopamine and quinolinyl acrylate is superior to the elongation at break of the ultrafiltration membrane obtained by treating the inorganic membrane-forming material and the functional membrane-forming material with the pretreatment solution containing only caffeic acid dopamine or quinolinyl acrylate compared with examples 9 to 10. Compared with example 11, example 8 shows that the elongation at break of the ultrafiltration membrane obtained after the inorganic membrane-making material and the functional membrane-making material are treated is improved by adding the caffeic acid dopamine and the acrylic acid quinoline ester into the pretreatment liquid.
The elongation at break of the ultrafiltration membrane obtained by the invention is more than 4.5%.
The above embodiments are merely illustrative, and not restrictive, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, all equivalent technical solutions also belong to the scope of the present invention, and the protection scope of the present invention should be defined by the claims.
Claims (10)
1. An ultrafiltration membrane, comprising:
the substrate membrane material is PVDF;
the inorganic film-making material comprises inorganic nanoparticles, and the particle size of the inorganic nanoparticles is 10-30 nm;
a functional film-making material comprising graphene oxide;
the inorganic film-making material and the functional film-making material are distributed in the substrate film material, and the proportion relationship between the inorganic film-making material and the functional film-making material is that the mass ratio is 8: 1-8.
2. An ultrafiltration membrane according to claim 1 wherein: the inorganic nano particles are at least one of titanium dioxide, aluminum oxide, silicon dioxide and ferroferric oxide.
3. An ultrafiltration membrane according to claim 1 wherein: the functional film-making material also comprises at least one of polyethylene glycol, PVP and diethyl 3, 4-vinyl dioxypyrrole-2, 5-dicarboxylate.
4. Use of an ultrafiltration membrane according to any of claims 1 to 3 in the treatment of wastewater.
5. The method of preparing the ultrafiltration membrane of claim 1, comprising: preparing an ultrafiltration membrane by using an inorganic membrane preparation material, a functional membrane preparation material, a substrate membrane material and a solvent through an immersion precipitation phase inversion method; the immersion precipitation phase inversion method comprises the steps of material mixing, water bath stirring, ultrasonic treatment, standing and curing, film scraping, water bath solidification and film forming.
6. The method for producing an ultrafiltration membrane according to claim 5, wherein: the solvent is 70-85 wt% DMF.
7. The method for producing an ultrafiltration membrane according to claim 5, wherein: the addition amount of the inorganic film-forming material is 0.2-1.6 wt% of the solvent.
8. The method for producing an ultrafiltration membrane according to claim 5, wherein: the addition amount of the functional film-making material is 0.2-1.6 wt% of the solvent.
9. The method for producing an ultrafiltration membrane according to claim 5, wherein: the addition amount of the substrate membrane material is 18-25 wt% of the solvent.
10. The method for producing an ultrafiltration membrane according to claim 5, wherein: the functional film-making material comprises graphene oxide and/or at least one of the following materials: polyethylene glycol, PVP, 3, 4-vinyl dioxypyrrole-2, 5-dicarboxylic acid diethyl ester.
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