CN115010214B - Sewage treatment membrane, preparation method of sewage treatment membrane and membrane separation equipment - Google Patents
Sewage treatment membrane, preparation method of sewage treatment membrane and membrane separation equipment Download PDFInfo
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- CN115010214B CN115010214B CN202210767135.5A CN202210767135A CN115010214B CN 115010214 B CN115010214 B CN 115010214B CN 202210767135 A CN202210767135 A CN 202210767135A CN 115010214 B CN115010214 B CN 115010214B
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- 239000012528 membrane Substances 0.000 title claims abstract description 129
- 239000010865 sewage Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000926 separation method Methods 0.000 title claims abstract description 13
- 239000004715 ethylene vinyl alcohol Substances 0.000 claims abstract description 67
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims abstract description 66
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000004744 fabric Substances 0.000 claims abstract description 31
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 238000004132 cross linking Methods 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 230000002378 acidificating effect Effects 0.000 claims abstract description 6
- 238000005470 impregnation Methods 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 claims abstract 14
- 239000000243 solution Substances 0.000 claims description 54
- 239000011259 mixed solution Substances 0.000 claims description 45
- 238000005266 casting Methods 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 30
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 15
- 239000004745 nonwoven fabric Substances 0.000 claims description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 14
- 238000007789 sealing Methods 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 14
- 229920003081 Povidone K 30 Polymers 0.000 claims description 11
- 229920003082 Povidone K 90 Polymers 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- 239000005977 Ethylene Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000003892 spreading Methods 0.000 claims description 6
- 230000007480 spreading Effects 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000001728 nano-filtration Methods 0.000 claims description 3
- 238000001223 reverse osmosis Methods 0.000 claims description 3
- 238000000108 ultra-filtration Methods 0.000 claims description 3
- 238000004065 wastewater treatment Methods 0.000 claims 1
- 230000004907 flux Effects 0.000 abstract description 14
- 238000004090 dissolution Methods 0.000 abstract description 3
- 230000008961 swelling Effects 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical group OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 53
- 239000002585 base Substances 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 239000002202 Polyethylene glycol Substances 0.000 description 7
- 230000006872 improvement Effects 0.000 description 7
- 229920001223 polyethylene glycol Polymers 0.000 description 7
- 239000005708 Sodium hypochlorite Substances 0.000 description 4
- 238000005485 electric heating Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000007790 scraping Methods 0.000 description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- 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
- B01D69/04—Tubular membranes
-
- 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
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a sewage treatment membrane, a preparation method of the sewage treatment membrane and membrane separation equipment. The sewage treatment membrane comprises a base cloth and an active component attached to the base cloth, wherein the active component is obtained by crosslinking EVOH and glutaraldehyde. The preparation method comprises the following steps: obtaining a base fabric attached with EVOH; immersing the base fabric attached with EVOH in an acidic glutaraldehyde solution; after the impregnation is completed, taking out the base cloth and performing heat treatment; and cleaning after the heat treatment is finished to obtain the sewage treatment membrane. According to the invention, the active component with a three-dimensional network structure is formed by crosslinking the EVOH and glutaraldehyde, and compared with a pure EVOH membrane, the obtained sewage treatment membrane has obviously better dissolution and swelling resistance, mechanical property and heat resistance, and the membrane flux is obviously improved; the preparation process is simple and controllable, and the production cost is low; when the device is applied to membrane separation equipment such as coiled membrane equipment or disc tubular membrane equipment for sewage treatment, the service life of the equipment can be obviously prolonged, and the cleaning frequency is reduced.
Description
Technical Field
The invention relates to the technical field of sewage treatment membranes, in particular to a sewage treatment membrane, a preparation method of the sewage treatment membrane and membrane separation equipment.
Background
At present, membrane pollution problems such as membrane hole blockage, formation of a mud cake layer on the surface of a membrane and the like become key factors for restricting the further development of membrane separation technology. The main reasons for such contamination include the hydrophobicity of the membrane material, and the greater susceptibility of the membrane to adsorption by impurities, which can result in contamination. Many researchers delay the problem of membrane pollution by hydrophilic modification of membranes, but the modified membranes have poor stability and serious radical shedding, so that the wide application of the modified membranes is restricted.
In recent years, ethylene vinyl alcohol (EVOH) is a highly semi-crystalline random copolymer composed of hydrophobic ethylene and hydrophilic vinyl alcohol segments, and has been widely used in the fields of foods, textiles, medical materials, etc. because of its excellent gas-barrier, oil-resistant, organic solvent-resistant, and antistatic properties. It is found that although EVOH chain contains a large amount of hydroxyl groups and has good hydrophilicity, EVOH material has small flux, low heat resistance and weak mechanical properties after film formation, and hydrophilic film material is easily swelled and dissolved, so that the application of the material in many aspects is limited. Therefore, the EVOH is modified so as to improve the flux, the dissolution and swelling resistance, the mechanical property and the heat resistance, and is the best means for improving the application prospect of the EVOH.
Disclosure of Invention
The invention mainly aims to provide a sewage treatment membrane, a preparation method of the sewage treatment membrane and membrane separation equipment, so as to solve the technical problem that EVOH water treatment performance is not ideal in the prior art.
In order to achieve the above object, according to a first aspect of the present invention, there is provided a sewage treatment membrane, comprising:
the sewage treatment membrane comprises a base cloth and an active component attached to the base cloth, wherein the active component is obtained by crosslinking EVOH and glutaraldehyde.
As a further improvement of the first aspect of the invention: the base cloth is non-woven fabric.
In order to achieve the above object, according to a second aspect of the present invention, there is provided a method for preparing a sewage treatment membrane, comprising the steps of:
the preparation method of the sewage treatment membrane comprises the following steps:
obtaining a base fabric attached with EVOH;
immersing the base fabric attached with EVOH in an acidic glutaraldehyde solution;
after the impregnation is completed, taking out the base cloth and performing heat treatment;
and cleaning after the heat treatment is finished to obtain the sewage treatment membrane.
As a further improvement of the second aspect of the invention: the method for obtaining the substrate with the EVOH attached thereto comprises the following steps:
obtaining a casting solution, wherein the casting solution contains EVOH;
coating the casting solution on the base cloth, and taking out after water bath for a certain time to obtain the base cloth attached with the EVOH.
As a further improvement of the second aspect of the invention: the method for obtaining the casting solution comprises the following steps:
heating the DMSO aqueous solution to 80-100 ℃, and adding EVOH to obtain a first mixed solution;
stirring the first mixed solution to reduce the temperature of the first mixed solution to 60-70 ℃ and the total stirring time is 24-36 h;
adding PEG and PVP to form a second mixed solution, and continuously stirring for 12-24 h;
and (5) carrying out vacuum defoaming to obtain the casting film liquid.
As a further improvement of the second aspect of the invention: the mass fraction of water in the DMSO aqueous solution is 5-15%; the mass fraction of ethylene in the EVOH is 30-35%, and the mass fraction of EVOH in the first mixed solution is 15-20%; the PEG is PEG-2000, and the mass fraction of the PEG-2000 in the second mixed solution is 4-6%; PVP is PVP-K30 and/or PVP-K90, and the mass fraction of PVP in the second mixed solution is 5-10%; the vacuum defoaming temperature is 40-60 ℃, and the defoaming time is 10-14 h; the casting solution is preserved at 30-60 ℃.
As a further improvement of the second aspect of the invention: spreading the casting film liquid on the base cloth by a scraper; the water bath temperature is 10-60 ℃ and the water bath time is 2-300 min.
As a further improvement of the second aspect of the invention: the mass fraction of glutaraldehyde in the glutaraldehyde solution is 1-50%, and the pH value is 1-6; the soaking time is 3-10 min; and taking out the product after the soaking is finished, placing the product in a self-sealing bag, and performing heat treatment after sealing.
As a further improvement of the second aspect of the invention: the heat treatment temperature is 80-100 ℃, and the heat treatment time is 30-90 min.
In order to achieve the above object, according to a third aspect of the present invention, there is provided a membrane separation apparatus, comprising:
the membrane separation equipment is ultrafiltration membrane equipment, nanofiltration membrane equipment or reverse osmosis membrane equipment, and adopts the sewage treatment membrane of the first aspect or adopts the sewage treatment membrane prepared by the preparation method of the second aspect.
According to the invention, through the crosslinking of the EVOH and glutaraldehyde, the active component with a three-dimensional network structure is formed, and through verification, the active component with the three-dimensional network structure enables the sewage treatment membrane to have obviously better dissolution swelling resistance and obviously improved membrane flux compared with a pure EVOH membrane; the preparation process is simple and controllable, and the production cost is low; when the device is applied to membrane separation equipment such as coiled membrane equipment or disc tubular membrane equipment for sewage treatment, the service life of the equipment can be obviously prolonged, and the cleaning frequency is reduced; therefore, the sewage treatment membrane, the preparation method of the sewage treatment membrane and the membrane separation equipment have extremely strong practicability.
The invention is further described below with reference to the drawings and detailed description. Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The accompanying drawings, which form a part hereof, are shown by way of illustration and not of limitation, and in which are shown by way of illustration and description of the invention. In the drawings:
fig. 1 is a low-magnification SEM photograph (A1) and a high-magnification SEM photograph (A2) of the EVOH base film of example 4.
FIG. 2 shows a low-magnification SEM photograph (B1) and a high-magnification SEM photograph (B2) of the sewage treatment membrane sheet of example 4.
Detailed Description
The present invention will now be described more fully hereinafter with reference to the accompanying drawings. Those of ordinary skill in the art will be able to implement the invention based on these descriptions. Before describing the present invention with reference to the accompanying drawings, it should be noted in particular that:
the technical solutions and technical features provided in the sections including the following description in the present invention may be combined with each other without conflict.
In addition, the embodiments of the present invention referred to in the following description are typically only some, but not all, embodiments of the present invention. Therefore, all other embodiments, which can be made by one of ordinary skill in the art without undue burden, are intended to be within the scope of the present invention, based on the embodiments of the present invention.
Terms and units in relation to the present invention. The terms "comprising," "having," and any variations thereof in the description and claims of the invention and in the relevant sections are intended to cover a non-exclusive inclusion.
The specific implementation mode of the preparation method of the sewage treatment membrane comprises the following steps:
1. obtaining a casting solution, wherein the casting solution contains EVOH; the method specifically comprises the following steps:
1.1. heating DMSO (dimethyl sulfoxide) water solution to 80-100 ℃, and adding EVOH (ethylene-vinyl alcohol) to obtain a first mixed solution;
the temperature may be, but is not limited to, any one of 80 ℃, 85 ℃, 90 ℃, 95 ℃ and 100 ℃;
the water content in the DMSO aqueous solution is 5-15%, and may be any one of 5%, 7.9%, 8.6%, 10.3%, 11.5%, 12.7%, 14% and 15%, but not limited to the above;
the mass fraction of ethylene in the EVOH is 30-35%, and the EVOH can be any one of 30%, 31%, 32%, 33%, 34% and 35% by weight; the mass fraction of the EVOH in the first mixed solution is 15-20%, and the EVOH may be any of 15%, 15.8%, 16.7%, 17.9%, 18.7%, 19% and 20%, but is not limited to the values;
1.2. stirring the first mixed solution to reduce the temperature of the first mixed solution to 60-70 ℃ and the total stirring time is 24-36 h;
the temperature can be any one of 60 ℃, 62 ℃, 64 ℃, 66 ℃, 68 ℃ and 70 ℃ but not limited to the temperature, and the total stirring time can be any one of 24 hours, 26 hours, 28 hours, 30 hours, 32 hours, 34 hours and 36 hours;
1.3. adding PEG (polyethylene glycol) and PVP (polyvinylpyrrolidone) to form a second mixed solution, and continuously stirring for 12-24 h;
the stirring time can be any one of 12h, 14h, 16h, 18h, 20h, 22h and 24h;
the PEG is PEG-2000, the mass fraction of the PEG-2000 in the second mixed solution is 4-6%, and the PEG can be any one of 4%, 4.3%, 4.6%, 4.9% and 5% by weight; PEG-2000 refers to polyethylene glycol having a molecular weight of 2000;
the PVP is PVP-K30 and/or PVP-K90, and the mass fraction of PVP in the second mixed solution is 5-10%, and the PVP can be any one of 5%, 6.3%, 7%, 8.3%, 8.8%, 9.1% and 10% by weight; PVP-K30 is polyvinylpyrrolidone with a K value of 30, PVP-K90 is polyvinylpyrrolidone with a K value of 90, and K represents the viscosity specification;
1.4. vacuum defoamation is carried out to obtain casting film liquid;
the vacuum defoaming temperature is 40-60 ℃, and the defoaming time is 10-14 h; the vacuum defoaming temperature may be any one of 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃ and the defoaming time may be any one of 10h, 11h, 12h, 13h, 14h;
the casting solution is stored at 30-60 ℃, and can be any one of 30 ℃, 40 ℃, 50 ℃ and 60 ℃ without limitation;
2. coating the casting solution on the base cloth by using a scraper, and taking out after water bath for a certain time to obtain the base cloth attached with the EVOH;
the water bath temperature is 10-60 ℃ and the water bath time is 2-300 min; the water bath temperature can be any one of 10 ℃, 20 ℃, 25 ℃, 30 ℃, 40 ℃, 50 ℃ and 60 ℃ and the water bath time can be any one of 2min, 10min, 50min, 100min, 150min, 200min, 250min and 300min;
before the coating is completed and the water bath is carried out, the base cloth needs to volatilize in the air for 30-60 s, and the base cloth can be any one of 30s, 35s, 40s, 45s, 50s, 55s and 60 s;
3. immersing the base fabric attached with EVOH in an acidic glutaraldehyde solution;
the mass fraction of glutaraldehyde in the glutaraldehyde solution is 1-50%, and can be any one of 1%, 5%, 10%, 18%, 25%, 32%, 38, 43% and 50% by weight; the pH of glutaraldehyde solution is 1-6, but not limited to any of values 1, 2, 3, 4, 5, 6;
the soaking time is 3-10 min, and can be any one of 3min, 4min, 5min, 6min, 7min, 8min, 9min and 10min;
4. taking out the bag after the soaking is finished, placing the bag in a self-sealing bag, and performing heat treatment after sealing;
the heat treatment temperature is 80-100 ℃, and the heat treatment time is 30-90 min; the heat treatment temperature may be any one of 80 ℃, 85 ℃, 90 ℃, 95 ℃ and 100 ℃ and the heat treatment time may be any one of 30min, 40min, 50min, 60min, 70min, 80min and 90min;
5. and cleaning after the heat treatment is finished to obtain the sewage treatment membrane.
The advantageous effects of the present invention are described below by way of specific examples.
Example 1
146g of DMSO and 23.8g of deionized water (the mass fraction of the deionized water is 14%) are added into a three-neck flask, the three-neck flask is put into an electric heating sleeve, stirring is started, and when the temperature reaches 80 ℃, 40g of EVOH (the ethylene content is 32%) is added to form a first mixed solution with the mass fraction of the EVOH being 19%;
stirring the first mixed solution, reducing the temperature to 70 ℃, and stirring for 24 hours;
adding 11g of PEG-2000, 10g of PVP-K30 and 10g of PVP-K90 to form a second mixed solution, and then continuing stirring for 12 hours; the mass fraction of PEG-2000 in the second mixed solution is 4.6%, and the total mass fraction of PVP-K30 and PVP-K90 is 8.3%;
and (3) placing the second mixed solution into a vacuum oven at 50 ℃, carrying out vacuum defoaming for 12 hours to obtain casting solution, and storing the casting solution in a constant temperature oven at 30 ℃.
Spreading and fixing the non-woven fabric on a glass plate, pouring the obtained casting solution at one end of the non-woven fabric, then scraping the casting solution by using a scraper, wherein the moving speed of the scraper is 10m/min, and obtaining a uniform flat film; and taking the non-woven fabric coated with the casting solution off the glass plate, volatilizing in air for 40s, and then carrying out water bath at the water bath temperature of 10 ℃ for 10min to obtain the EVOH base film.
Preparing glutaraldehyde solution with pH=5 and mass fraction of 25%, and then soaking the EVOH base film in the glutaraldehyde solution for 4min; and taking out the membrane after the soaking is finished, sealing the membrane in a self-sealing bag belt, and then performing heat treatment for 60min in a 90 ℃ oven to obtain the sewage treatment membrane, wherein the active components of the sewage treatment membrane are obtained by crosslinking EVOH and glutaraldehyde.
The thickness of the obtained sewage treatment membrane is 243 mu m, and the flux of the EVOH base membrane is 320L/(m) under the pressure of 0.01MPa 2 And (h) the flux of the sewage treatment membrane is 550L/(m) 2 And (h) a step of. The sewage treatment membrane is soaked in NaOH solution with the mass fraction of 1% for 15 hours, and the mass loss rate of the sewage treatment membrane is only 1.3%, which indicates that the sewage treatment membrane has better alkali resistance.
Example 2
146g of DMSO and 13.8g of deionized water (the mass fraction of the deionized water is 8.6%) are added into a three-neck flask, the three-neck flask is put into an electric heating sleeve, stirring is started, and when the temperature reaches 90 ℃, 30g of EVOH (the ethylene content is 32%) is added to form a first mixed solution with the mass fraction of EVOH being 15.8%;
stirring the first mixed solution, reducing the temperature to 70 ℃, and stirring for 24 hours;
adding 11g of PEG-2000, 10g of PVP-K30 and 10g of PVP-K90 to form a second mixed solution, and then continuing stirring for 12 hours; the mass fraction of PEG-2000 in the second mixed solution is 5%, and the total mass fraction of PVP-K30 and PVP-K90 is 9.1%;
and (3) placing the second mixed solution into a vacuum oven at 50 ℃, carrying out vacuum defoaming for 12 hours to obtain casting solution, and storing the casting solution in a constant temperature oven at 30 ℃.
Spreading and fixing the non-woven fabric on a glass plate, pouring the obtained casting solution at one end of the non-woven fabric, then scraping the casting solution by using a scraper, wherein the moving speed of the scraper is 10m/min, and obtaining a uniform flat film; and taking the non-woven fabric coated with the casting solution off the glass plate, volatilizing in air for 40s, and then carrying out water bath at the water bath temperature of 10 ℃ for 10min to obtain the EVOH base film.
Preparing glutaraldehyde solution with pH=5 and mass fraction of 25%, and then soaking the EVOH base film in the glutaraldehyde solution for 4min; and taking out the membrane after the soaking is finished, sealing the membrane in a self-sealing bag belt, and then performing heat treatment for 60min in a 90 ℃ oven to obtain the sewage treatment membrane, wherein the active components of the sewage treatment membrane are obtained by crosslinking EVOH and glutaraldehyde.
The thickness of the obtained sewage treatment membrane is 265 mu m, and the flux of the EVOH base membrane is 410L/(m) under the pressure of 0.01MPa 2 And (h) the flux of the sewage treatment membrane is 730L/(m) 2 And (h) a step of. The sewage treatment membrane is soaked in NaOH solution with the mass fraction of 1% for 15 hours, and the mass loss rate of the sewage treatment membrane is only 1.7%. The sewage treatment membrane is soaked in 3% of citric acid for 15 hours, and the mass loss rate of the sewage treatment membrane is only 1.2%, which indicates that the sewage treatment membrane has better tolerance under acidic and alkaline conditions.
Example 3
160g of DMSO and 13.8g of deionized water (mass fraction of deionized water is 7.9%) are added into a three-neck flask, the three-neck flask is put into an electric heating sleeve, stirring is started, and when the temperature reaches 80 ℃, 40g of EVOH (ethylene content is 32%) is added to form a first mixed solution with the mass fraction of EVOH of 18.7%;
stirring the first mixed solution, reducing the temperature to 70 ℃, and stirring for 24 hours;
adding 11g of PEG-2000 and 15g of PVP-K3 to form a second mixed solution, and then continuing stirring for 12 hours; the mass fraction of PEG-2000 in the second mixed solution is 4.6%, and the total mass fraction of PVP-K30 and PVP-K90 is 6.3%;
and (3) placing the second mixed solution into a vacuum oven at 50 ℃, carrying out vacuum defoaming for 12 hours to obtain casting solution, and storing the casting solution in a constant temperature oven at 30 ℃.
Spreading and fixing the non-woven fabric on a glass plate, pouring the obtained casting solution at one end of the non-woven fabric, then scraping the casting solution by using a scraper, wherein the moving speed of the scraper is 10m/min, and obtaining a uniform flat film; and taking the non-woven fabric coated with the casting solution off the glass plate, volatilizing in air for 40s, and then carrying out water bath at the water bath temperature of 10 ℃ for 10min to obtain the EVOH base film.
Preparing glutaraldehyde solution with pH=5 and mass fraction of 25%, and then soaking the EVOH base film in the glutaraldehyde solution for 4min; and taking out the membrane after the soaking is finished, sealing the membrane in a self-sealing bag belt, and then performing heat treatment for 60min in a 90 ℃ oven to obtain the sewage treatment membrane, wherein the active components of the sewage treatment membrane are obtained by crosslinking EVOH and glutaraldehyde.
The thickness of the obtained sewage treatment membrane is 255 mu m, and the flux of the EVOH base membrane is 350.2L/(m) under the pressure of 0.01MPa through test 2 And (h) the flux of the sewage treatment membrane is 590.6L/(m) 2 And (h) a step of. The sewage treatment membrane is soaked in NaOH solution with the mass fraction of 1% for 15 hours, and the mass loss rate of the sewage treatment membrane is only 2.7%. The sewage treatment membrane is soaked in 3% of citric acid for 15 hours, the mass loss rate of the sewage treatment membrane is only 2.2%, and the sewage treatment membrane is soaked in 5% of sodium hypochlorite for 15 hours, the mass loss rate of the sewage treatment membrane is only 1.12%, which indicates that the sewage treatment membrane is acid-alkali resistant and has better tolerance to sodium hypochlorite.
Example 4
140g of DMSO and 20.3g of deionized water (the mass fraction of the deionized water is 12.7%) are added into a three-neck flask, the three-neck flask is put into an electric heating sleeve, stirring is started, and when the temperature reaches 100 ℃, 35g of EVOH (the ethylene content is 32%) is added to form a first mixed solution with the mass fraction of the EVOH of 17.9%;
stirring the first mixed solution, reducing the temperature to 70 ℃, and stirring for 24 hours;
adding 11g of PEG-2000 and 20g of PVP-K30 to form a second mixed solution, and then continuing stirring for 12 hours; the mass fraction of PEG-2000 in the second mixed solution is 4.9%, and the total mass fraction of PVP-K30 and PVP-K90 is 8.8%;
and (3) placing the second mixed solution into a vacuum oven at 50 ℃, carrying out vacuum defoaming for 12 hours to obtain casting solution, and storing the casting solution in a constant temperature oven at 30 ℃.
Spreading and fixing the non-woven fabric on a glass plate, pouring the obtained casting solution at one end of the non-woven fabric, then scraping the casting solution by using a scraper, wherein the moving speed of the scraper is 10m/min, and obtaining a uniform flat film; and taking the non-woven fabric coated with the casting solution off the glass plate, volatilizing in air for 40s, and then carrying out water bath at the water bath temperature of 25 ℃ for 10min to obtain the EVOH base film.
Preparing glutaraldehyde solution with pH=1 and mass fraction of 10%, and then soaking the EVOH base film in the glutaraldehyde solution for 4min; and taking out the membrane after the soaking is finished, sealing the membrane in a self-sealing bag belt, and then performing heat treatment for 60min in a 90 ℃ oven to obtain the sewage treatment membrane, wherein the active components of the sewage treatment membrane are obtained by crosslinking EVOH and glutaraldehyde.
The thickness of the obtained sewage treatment membrane is 276 mu m, and the flux of the EVOH base membrane is 223.5L/(m) under the pressure of 0.01MPa through test 2 And (h) the flux of the sewage treatment membrane is 333.9L/(m) 2 And (h) a step of. The sewage treatment membrane is soaked in NaOH solution with the mass fraction of 1% for 15 hours, and the mass loss rate of the sewage treatment membrane is only 1.8%. The sewage treatment membrane is soaked in 3% of citric acid for 15 hours, the mass loss rate of the sewage treatment membrane is only 1.98%, and the sewage treatment membrane is soaked in 5% of sodium hypochlorite for 15 hours, the mass loss rate of the sewage treatment membrane is only 1.56%, which indicates that the sewage treatment membrane is acid-alkali resistant and has better tolerance to sodium hypochlorite.
Fig. 1 is a low-magnification SEM photograph (A1) and a high-magnification SEM photograph (A2) of the EVOH base film of example 4. FIG. 2 shows a low-magnification SEM photograph (B1) and a high-magnification SEM photograph (B2) of the sewage treatment membrane sheet of example 4.
As shown in figures 1-2, the surface of the sewage treatment membrane obtained by crosslinking EVOH and glutaraldehyde forms a convex structure of about 10-100 nm, which indicates that EVOH and glutaraldehyde are successfully crosslinked to form a three-dimensional network structure.
In the above embodiment, the flux test is performed by dead-end filtration, and the calculation formula is j=v/(a·t), where J is the flux, V is the water quantity (L) passing through the membrane, T is the test time (h), and a is the effective area (m 2 ) The filtration pressure was controlled by a nitrogen cylinder.
The embodiment of the membrane separation equipment is ultrafiltration membrane equipment, nanofiltration membrane equipment or reverse osmosis membrane equipment, wherein tubular, coiled or disc-tubular membranes are arranged in the equipment, and the membranes are the sewage treatment membranes in any one embodiment.
The content of the present invention is described above. Those of ordinary skill in the art will be able to implement the invention based on these descriptions. Based on the foregoing, all other embodiments that may be obtained by one of ordinary skill in the art without undue burden are within the scope of the present invention.
Claims (8)
1. The sewage treatment membrane comprises base cloth and an active component attached to the base cloth, and is characterized in that: the active component is obtained by crosslinking EVOH and glutaraldehyde;
the preparation method comprises the following steps:
heating the DMSO aqueous solution to 80-100 ℃, and adding EVOH to obtain a first mixed solution;
stirring the first mixed solution to reduce the temperature of the first mixed solution to 60-70 ℃ and the total stirring time is 24-36 h;
adding PEG and PVP to form a second mixed solution, and continuously stirring for 12-24 h;
vacuum defoamation is carried out to obtain casting film liquid;
coating the casting solution on the base cloth, and taking out after water bath for a certain time to obtain the base cloth attached with the EVOH;
immersing the base fabric attached with EVOH in an acidic glutaraldehyde solution;
after the impregnation is completed, taking out the base cloth and performing heat treatment;
and cleaning after the heat treatment is finished to obtain the sewage treatment membrane.
2. The wastewater treatment membrane of claim 1, wherein: the base cloth is non-woven fabric.
3. The method for preparing the sewage treatment membrane according to claim 1 or 2, comprising the steps of:
heating the DMSO aqueous solution to 80-100 ℃, and adding EVOH to obtain a first mixed solution;
stirring the first mixed solution to reduce the temperature of the first mixed solution to 60-70 ℃ and the total stirring time is 24-36 h;
adding PEG and PVP to form a second mixed solution, and continuously stirring for 12-24 h;
vacuum defoamation is carried out to obtain casting film liquid;
coating the casting solution on the base cloth, and taking out after water bath for a certain time to obtain the base cloth attached with the EVOH;
immersing the base fabric attached with EVOH in an acidic glutaraldehyde solution;
after the impregnation is completed, taking out the base cloth and performing heat treatment;
and cleaning after the heat treatment is finished to obtain the sewage treatment membrane.
4. A method of preparation as claimed in claim 3, wherein: the mass fraction of water in the DMSO aqueous solution is 5-15%; the mass fraction of ethylene in the EVOH is 30-35%, and the mass fraction of EVOH in the first mixed solution is 15-20%; the PEG is PEG-2000, and the mass fraction of the PEG-2000 in the second mixed solution is 4-6%; PVP is PVP-K30 and/or PVP-K90, and the mass fraction of PVP in the second mixed solution is 5-10%; the vacuum defoaming temperature is 40-60 ℃, and the defoaming time is 10-14 h; the casting solution is preserved at 30-60 ℃.
5. A method of preparation as claimed in claim 3, wherein: spreading the casting film liquid on the base cloth by a scraper; the water bath temperature is 10-60 ℃ and the water bath time is 2-300 min.
6. A method of preparation as claimed in claim 3, wherein: the mass fraction of glutaraldehyde in the glutaraldehyde solution is 1-50%, and the pH value is 1-6; the soaking time is 3-10 min; and taking out the product after the soaking is finished, placing the product in a self-sealing bag, and performing heat treatment after sealing.
7. A method of preparation as claimed in claim 3, wherein: the heat treatment temperature is 80-100 ℃, and the heat treatment time is 30-90 min.
8. The membrane separation equipment is ultrafiltration membrane equipment, nanofiltration membrane equipment or reverse osmosis membrane equipment, and is characterized in that: a sewage treatment membrane sheet according to claim 1 or 2, or a sewage treatment membrane sheet produced by the production method according to any one of claims 3 to 7.
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