CN115010214A - 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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- CN115010214A CN115010214A CN202210767135.5A CN202210767135A CN115010214A CN 115010214 A CN115010214 A CN 115010214A CN 202210767135 A CN202210767135 A CN 202210767135A CN 115010214 A CN115010214 A CN 115010214A
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- 239000012528 membrane Substances 0.000 title claims abstract description 137
- 239000010865 sewage Substances 0.000 title claims abstract description 74
- 238000000926 separation method Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000004715 ethylene vinyl alcohol Substances 0.000 claims abstract description 69
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims abstract description 68
- 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 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 238000004132 cross linking Methods 0.000 claims abstract description 10
- 238000005470 impregnation Methods 0.000 claims abstract description 10
- 238000007598 dipping method Methods 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 230000002378 acidificating effect Effects 0.000 claims abstract description 5
- 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 59
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 claims description 54
- 239000011259 mixed solution Substances 0.000 claims description 41
- 238000005266 casting Methods 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 27
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 24
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000004745 nonwoven fabric Substances 0.000 claims description 14
- 238000007789 sealing Methods 0.000 claims description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 13
- 229920003081 Povidone K 30 Polymers 0.000 claims description 11
- 229920003082 Povidone K 90 Polymers 0.000 claims description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 3
- 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
- 239000004480 active ingredient Substances 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
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 239000002585 base Substances 0.000 description 14
- 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
- 230000006872 improvement Effects 0.000 description 7
- 238000002791 soaking Methods 0.000 description 7
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 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
- 238000003892 spreading Methods 0.000 description 4
- 230000007480 spreading Effects 0.000 description 4
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000004065 wastewater treatment Methods 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
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying 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
- 239000007789 gas Substances 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000036619 pore blockages Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Images
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
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- 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 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; dipping the base cloth attached with the EVOH into an acidic glutaraldehyde solution; after the impregnation is finished, taking out the base fabric and carrying out 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 EVOH and glutaraldehyde, and compared with a pure EVOH membrane, the obtained sewage treatment membrane has obviously better dissolution 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 membrane separation device is applied to membrane separation devices such as a spiral membrane device or a disc tube type membrane device for sewage treatment, the service life of the device 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, the problems of membrane pore blockage, mud cake layer formation on the membrane surface and the like become key factors for restricting the further development of the membrane separation technology. The main reasons for such contamination include that the membrane material is hydrophobic, and the membrane is more easily adsorbed by impurities, thereby causing contamination. Many researchers delay the membrane pollution problem by means of hydrophilic modification of the membrane, but the modification stability is poor, and the group shedding is serious, so that the wide application of the modified membrane is also restricted.
In recent years, ethylene-vinyl alcohol (EVOH) is a highly semicrystalline random copolymer composed of hydrophobic ethylene and hydrophilic vinyl alcohol segments, and has been widely used in the fields of foods, textiles, and medical materials because of its excellent gas barrier, oil resistance, organic solvent resistance, and antistatic properties. Research shows that although EVOH contains a large number of hydroxyl groups on a chain and has good hydrophilicity, EVOH materials have small flux and low heat resistance, the mechanical properties after film formation are not strong, and hydrophilic film materials are easy to swell and dissolve, so that the application of the hydrophilic film materials in many aspects is limited. Therefore, EVOH is modified to improve the flux, the dissolution swelling resistance, the mechanical property and the heat resistance, and is the best means for improving the application prospect of 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, and aims 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 membrane for sewage treatment, the technical solution is as follows:
the sewage treatment membrane comprises 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 membrane for sewage treatment, the method comprising:
the preparation method of the sewage treatment membrane comprises the following steps:
obtaining a base fabric attached with EVOH;
dipping the base cloth attached with the EVOH into an acidic glutaraldehyde solution;
after the impregnation is finished, taking out the base fabric and carrying out 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 EVOH attached comprises the following steps:
obtaining a casting solution, wherein the casting solution contains EVOH;
and coating the casting film liquid on the base cloth, taking out after water bath for a certain time, and obtaining the base cloth with the EVOH attached.
As a further improvement of the second aspect of the invention: the method for obtaining the casting solution comprises the following steps:
heating a DMSO (dimethyl sulfoxide) aqueous solution to 80-100 ℃, and adding EVOH (ethylene vinyl alcohol) to obtain a first mixed solution;
stirring the first mixed solution to reduce the temperature of the first mixed solution to 60-70 ℃, wherein the total stirring time is 24-36 hours;
adding PEG and PVP to form a second mixed solution, and continuously stirring for 12-24 h;
and (4) defoaming in vacuum to obtain the casting solution.
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%; the PVP is PVP-K30 and/or PVP-K90, and the mass fraction of the PVP in the second mixed solution is 5-10%; the vacuum defoaming temperature is 40-60 ℃, and the defoaming time is 10-14 h; and preserving the casting solution at 30-60 ℃.
As a further improvement of the second aspect of the invention: coating the casting solution 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 is 1-6; the dipping time is 3-10 min; taking out after the impregnation is finished, placing the soaked product in a self-sealing bag, and carrying out 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, wherein:
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 the sewage treatment membrane prepared by the preparation method of the second aspect.
According to the invention, the active component with the three-dimensional network structure is formed by crosslinking EVOH and glutaraldehyde, and 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 membrane separation device is applied to membrane separation devices such as a spiral membrane device or a disc-tube type membrane device for sewage treatment, the service life of the device 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 high practicability.
The invention is further described with reference to the following figures 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 are incorporated in and constitute a part of this specification, are included to assist in understanding the invention, and are included to explain the invention and their equivalents and not limit it unduly. In the drawings:
FIG. 1 is a low magnification SEM photograph (A1) and a high magnification SEM photograph (A2) of an EVOH-based film of example 4.
FIG. 2 shows a low power SEM photograph (B1) and a high power SEM photograph (B2) of the sewage treatment membrane of example 4.
Detailed Description
The invention will be described more fully hereinafter with reference to the accompanying drawings. Those skilled in the art will be able to practice the invention based on these descriptions. Before the present invention is described in detail with reference to the accompanying drawings, it is to be noted that:
the technical solutions and features provided in the present invention in the respective sections including the following description may be combined with each other without conflict.
Moreover, the embodiments of the present invention described in the following description are generally only some embodiments of the present invention, and not all embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
With respect to terms and units in the present invention. The terms "comprising," "having," and any variations thereof in the description and claims of this invention and in the related section 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 a DMSO (dimethyl sulfoxide) water solution to 80-100 ℃, and adding EVOH (ethylene-vinyl alcohol) to obtain a first mixed solution;
the temperature can be, but is not limited to, any one of 80 ℃, 85 ℃, 90 ℃, 95 ℃ and 100 ℃;
the mass fraction of water in the DMSO aqueous solution is 5-15%, and can be any one of 5%, 7.9%, 8.6%, 10.3%, 11.5%, 12.7%, 14% and 15% without limitation;
the mass fraction of ethylene in the EVOH is 30-35%, and the ethylene can be selected from any one of 30%, 31%, 32%, 33%, 34% and 35% without limitation; the mass fraction of the EVOH in the first mixed solution is 15-20%, and the EVOH can be any one of 15%, 15.8%, 16.7%, 17.9%, 18.7%, 19% and 20% in a value but not limited;
1.2. stirring the first mixed solution to reduce the temperature of the first mixed solution to 60-70 ℃, wherein the total stirring time is 24-36 hours;
the temperature can be but is not limited to any one of the values of 60 ℃, 62 ℃, 64 ℃, 66 ℃, 68 ℃ and 70 ℃, and the total stirring time can be but is not limited to any one of the values of 24h, 26h, 28h, 30h, 32h, 34h and 36 h;
1.3. adding PEG (polyethylene glycol) and PVP (polyvinylpyrrolidone) to form a second mixed solution, and continuously stirring for 12-24 hours;
the stirring time can be, but is not limited to, any one of 12h, 14h, 16h, 18h, 20h, 22h and 24 h;
the PEG is PEG-2000, the mass fraction of the PEG-2000 in the second mixed solution is 4-6%, and the PEG-2000 can be any one of 4%, 4.3%, 4.6%, 4.9% and 5% without limitation; PEG-2000 refers to polyethylene glycol with a molecular weight of 2000;
the PVP is PVP-K30 and/or PVP-K90, the mass fraction of the 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% in a non-limiting mode; PVP-K30 refers to polyvinylpyrrolidone with a K value of 30, PVP-K90 refers to polyvinylpyrrolidone with a K value of 90, and the K value represents the viscosity specification;
1.4. obtaining a casting solution after vacuum defoaming;
the vacuum defoaming temperature is 40-60 ℃, and the defoaming time is 10-14 h; the vacuum defoaming temperature can be but is not limited to any one of 40 ℃, 45 ℃, 50 ℃, 55 ℃ and 60 ℃, and the defoaming time can be but is not limited to any one of 10h, 11h, 12h, 13h and 14 h;
the casting solution is stored at 30-60 ℃, and can be, but is not limited to, any one of 30 ℃, 40 ℃, 50 ℃ and 60 ℃;
2. coating the casting film liquid on the base cloth by a scraper, taking out after water bath for a certain time, and obtaining 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 the values of 10 ℃, 20 ℃, 25 ℃, 30 ℃, 40 ℃, 50 ℃ and 60 ℃, and the water bath time can be any one of the values of 2min, 10min, 50min, 100min, 150min, 200min, 250min and 300 min;
before the water bath is carried out after the coating, the base cloth is required to be volatilized in the air for 30-60 s, and the value can be any one of 30s, 35s, 40s, 45s, 50s, 55s and 60s without limitation;
3. dipping the base cloth attached with the EVOH into an acidic glutaraldehyde solution;
the mass fraction of the glutaraldehyde in the glutaraldehyde solution is 1-50%, and the mass fraction can be any one of 1%, 5%, 10%, 18%, 25%, 32%, 38%, 43% and 50% without limitation; the pH value of the glutaraldehyde solution is 1-6, and the glutaraldehyde solution can be any one of 1, 2, 3, 4, 5 and 6;
the dipping time is 3-10 min, and can be, but is not limited to, any one of 3min, 4min, 5min, 6min, 7min, 8min, 9min and 10 min;
4. taking out after the impregnation is finished, placing the soaked product in a self-sealing bag, and carrying out heat treatment after sealing;
the heat treatment temperature is 80-100 ℃, and the heat treatment time is 30-90 min; the heat treatment temperature can be but is not limited to any one of 80 ℃, 85 ℃, 90 ℃, 95 ℃ and 100 ℃, and the heat treatment time can be but is not limited to any one of 30min, 40min, 50min, 60min, 70min, 80min and 90 min;
5. and cleaning after the heat treatment is finished to obtain the sewage treatment membrane.
The advantageous effects of the present invention are illustrated below by specific examples.
Example 1
Adding 146g of DMSO and 23.8g of deionized water (the mass fraction of the deionized water is 14%) into a three-neck flask, putting the three-neck flask into an electric heating sleeve, starting stirring, adding 40g of EVOH (the ethylene content is 32%) when the temperature reaches 80 ℃, and forming a first mixed solution of EVOH with the mass fraction of 19%;
stirring the first mixed solution, reducing the temperature to 70 ℃, and stirring for 24 hours in total;
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 percent, and the total mass fraction of PVP-K30 and PVP-K90 is 8.3 percent;
and (3) placing the second mixed solution into a vacuum oven at 50 ℃, and defoaming in vacuum for 12 hours to obtain a casting solution, and storing the casting solution in a thermostat at 30 ℃.
Spreading and fixing the non-woven fabric on a glass plate, pouring the obtained membrane casting solution at one end of the non-woven fabric, and then scraping the membrane casting solution by adopting a scraper, wherein the moving speed of the scraper is 10m/min, so as to obtain a uniform flat membrane; and taking the non-woven fabric coated with the film casting solution off a glass plate, volatilizing in air for 40s, and then carrying out water bath at the temperature of 10 ℃ for 10min to obtain the EVOH-based film.
Preparing a glutaraldehyde solution with the pH of 5 and the mass fraction of 25%, and then soaking the EVOH-based film in the glutaraldehyde solution for 4 min; and taking out after the impregnation is finished, sealing the impregnated membrane in a self-sealing bag belt, and then carrying out heat treatment in a 90 ℃ oven for 60min to obtain the sewage treatment membrane, wherein the active component of the sewage treatment membrane is obtained by crosslinking EVOH and glutaraldehyde.
The thickness of the obtained sewage treatment membrane is 243 mu m, and the flux of the EVOH-based membrane is 320L/(m) under the pressure of 0.01MPa 2 Coupled with water), the flux of the wastewater treatment membrane was 550L/(m) 2 And (coupling.) for another time). Soaking the sewage treatment membrane in a NaOH solution with the mass fraction of 1% for 15h, wherein the mass loss rate of the sewage treatment membrane is only 1.3%, which shows that the sewage treatment membrane has better resistance to the corrosionAnd (3) alkalinity.
Example 2
Adding 146g of DMSO and 13.8g of deionized water (the mass fraction of the deionized water is 8.6%) into a three-neck flask, putting the three-neck flask into an electric heating sleeve, starting stirring, adding 30g of EVOH (the ethylene content is 32%) when the temperature reaches 90 ℃, and forming a first mixed solution of EVOH with the mass fraction of 15.8%;
stirring the first mixed solution, reducing the temperature to 70 ℃, and stirring for 24 hours in total;
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 ℃, and defoaming in vacuum for 12 hours to obtain a casting solution, and storing the casting solution in a thermostat at 30 ℃.
Spreading and fixing the non-woven fabric on a glass plate, pouring the obtained membrane casting solution at one end of the non-woven fabric, and then scraping the membrane casting solution by adopting a scraper, wherein the moving speed of the scraper is 10m/min, so as to obtain a uniform flat membrane; taking the non-woven fabric coated with the film 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 a glutaraldehyde solution with the pH of 5 and the mass fraction of 25%, and then soaking the EVOH-based film in the glutaraldehyde solution for 4 min; and taking out after the impregnation is finished, sealing the impregnated and taken out in a self-sealing bag belt, and then carrying out heat treatment in a drying oven at 90 ℃ for 60min to obtain the sewage treatment membrane, wherein the active component of the sewage treatment membrane is obtained by crosslinking EVOH and glutaraldehyde.
The thickness of the obtained sewage treatment membrane is 265 mu m, and the flux of the EVOH-based membrane is 410L/(m) under the pressure of 0.01MPa 2 Coupled for h), flux of the wastewater treatment membrane was 730L/(m) 2 And after reaction). Soaking the sewage treatment membrane in a NaOH solution with the mass fraction of 1% for 15 hours, wherein the mass loss rate of the sewage treatment membrane is only 1.7%. Soaking the sewage treatment membrane in 3 percent citric acid for 15 hours, wherein the mass loss rate of the sewage treatment membrane is only1.2 percent, which shows that the sewage treatment membrane has better tolerance under acidic and alkaline conditions.
Example 3
160g of DMSO and 13.8g of deionized water (the mass fraction of the deionized water is 7.9%) are added into a three-neck flask, the three-neck flask is placed 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 of EVOH with the mass fraction of 18.7%;
stirring the first mixed solution, reducing the temperature to 70 ℃, and stirring for 24 hours in total;
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 percent, and the total mass fraction of PVP-K30 and PVP-K90 is 6.3 percent;
and (3) placing the second mixed solution into a vacuum oven at 50 ℃, and defoaming in vacuum for 12 hours to obtain a casting solution, and storing the casting solution in a thermostat at 30 ℃.
Spreading and fixing the non-woven fabric on a glass plate, pouring the obtained membrane casting solution at one end of the non-woven fabric, and then scraping the membrane casting solution by adopting a scraper, wherein the moving speed of the scraper is 10m/min, so as to obtain a uniform flat membrane; taking the non-woven fabric coated with the film 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 a glutaraldehyde solution with the pH of 5 and the mass fraction of 25%, and then soaking the EVOH-based film in the glutaraldehyde solution for 4 min; and taking out after the impregnation is finished, sealing the impregnated membrane in a self-sealing bag belt, and then carrying out heat treatment in a 90 ℃ oven for 60min to obtain the sewage treatment membrane, wherein the active component of the sewage treatment membrane is obtained by crosslinking EVOH and glutaraldehyde.
The thickness of the obtained sewage treatment membrane is 255 mu m, and the flux of the EVOH-based membrane is 350.2L/(m) under the pressure of 0.01MPa through testing 2 Reseparation h), flux of the wastewater treatment membrane was 590.6L/(m) 2 And (coupling.) for another time). The sewage treatment membrane is soaked in a 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 in qualityThe sewage treatment membrane is soaked in 3% citric acid for 15 hours, the mass loss rate of the sewage treatment membrane is only 2.2%, the sewage treatment membrane is soaked in 5% sodium hypochlorite for 15 hours, and the mass loss rate of the sewage treatment membrane is only 1.12%, so that the sewage treatment membrane is acid-base resistant and has good tolerance on sodium hypochlorite.
Example 4
Adding 140g of DMSO and 20.3g of deionized water (the mass fraction of the deionized water is 12.7%) into a three-neck flask, putting the three-neck flask into an electric heating sleeve, starting stirring, adding 35g of EVOH (the ethylene content is 32%) when the temperature reaches 100 ℃, and forming a first mixed solution of EVOH with the mass fraction of 17.9%;
stirring the first mixed solution, reducing the temperature to 70 ℃, and stirring for 24 hours in total;
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 percent, and the total mass fraction of PVP-K30 and PVP-K90 is 8.8 percent;
and (3) placing the second mixed solution into a vacuum oven at 50 ℃, and defoaming in vacuum for 12 hours to obtain a casting solution, and storing the casting solution in a thermostat at 30 ℃.
Spreading and fixing the non-woven fabric on a glass plate, pouring the obtained membrane casting solution at one end of the non-woven fabric, and then scraping the membrane casting solution by adopting a scraper, wherein the moving speed of the scraper is 10m/min, so as to obtain a uniform flat membrane; taking the non-woven fabric coated with the film casting solution off the glass plate, volatilizing in air for 40s, and carrying out water bath at 25 ℃ for 10min to obtain the EVOH base film.
Preparing a glutaraldehyde solution with the pH of 1 and the mass fraction of 10%, and then soaking the EVOH-based film in the glutaraldehyde solution for 4 min; and taking out after the impregnation is finished, sealing the impregnated membrane in a self-sealing bag belt, and then carrying out heat treatment in a 90 ℃ oven for 60min to obtain the sewage treatment membrane, wherein the active component of the sewage treatment membrane is obtained by crosslinking EVOH and glutaraldehyde.
The thickness of the obtained sewage treatment membrane is 276 mu m, and the flux of the EVOH-based membrane is 223.5L/(m) under the pressure of 0.01MPa 2 ﹒h)，The flux of the sewage treatment membrane is 333.9L/(m) 2 And (coupling.) for another time). The sewage treatment membrane is soaked in a 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% by mass 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% by mass of sodium hypochlorite for 15 hours, the mass loss rate of the sewage treatment membrane is only 1.56%, so that the sewage treatment membrane is acid and alkali resistant and has good tolerance to sodium hypochlorite.
Fig. 1 is a low-magnification SEM photograph (a1) and a high-magnification SEM photograph (a2) of the EVOH-based film of example 4. FIG. 2 shows a low SEM (B1) and a high SEM (B2) of the sewage treatment membrane of example 4.
As shown in FIG. 1-2, a convex structure of about 10-100 nm is formed on the surface of the sewage treatment membrane obtained by crosslinking EVOH and glutaraldehyde, which indicates that EVOH and glutaraldehyde are successfully crosslinked to form a three-dimensional network structure.
The flux in the above embodiments is measured by dead-end filtration, and the calculation formula is J ═ V/(a · T), where J is the flux, V is the amount of water passing through the membrane (L), T is the test time (h), and a is the effective area of the membrane (m) 2 ) The filtering pressure is controlled by a nitrogen cylinder.
The embodiment of the membrane separation equipment of the invention is ultrafiltration membrane equipment, nanofiltration membrane equipment or reverse osmosis membrane equipment, and a tubular, rolled or disc-tube type membrane is arranged in the equipment, and the membrane is the sewage treatment membrane of any one embodiment.
The contents of the present invention have been explained above. Those skilled in the art will be able to implement the invention based on these teachings. All other embodiments, which can be derived by a person skilled in the art from the above description without inventive step, shall fall within the scope of protection of the present invention.
Claims (10)
1. Sewage treatment membrane, including base cloth and the active ingredient that adheres to on the base cloth, its characterized in that: the active component is obtained by crosslinking EVOH and glutaraldehyde.
2. The sewage treatment membrane of claim 1, wherein: the base cloth is non-woven fabric.
3. The method for preparing a sewage treatment membrane according to claim 1 or 2, comprising the steps of:
obtaining a base fabric attached with EVOH;
dipping the base cloth attached with the EVOH into an acidic glutaraldehyde solution;
after the impregnation is finished, taking out the base fabric and carrying out heat treatment;
and cleaning after the heat treatment is finished to obtain the sewage treatment membrane.
4. The method of claim 3, wherein: the method for obtaining the base cloth with the EVOH attached comprises the following steps:
obtaining a casting solution, wherein the casting solution contains EVOH;
and coating the casting film liquid on the base cloth, taking out after water bath for a certain time, and obtaining the base cloth with the EVOH attached.
5. The method of claim 4, wherein: the method for obtaining the casting solution comprises the following steps:
heating a DMSO (dimethyl sulfoxide) aqueous solution to 80-100 ℃, and adding EVOH (ethylene vinyl alcohol) to obtain a first mixed solution;
stirring the first mixed solution to reduce the temperature of the first mixed solution to 60-70 ℃, wherein the total stirring time is 24-36 hours;
adding PEG and PVP to form a second mixed solution, and continuously stirring for 12-24 h;
and (4) defoaming in vacuum to obtain the casting solution.
6. The method of claim 5, 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%; the PVP is PVP-K30 and/or PVP-K90, and the mass fraction of the PVP in the second mixed solution is 5-10%; the vacuum defoaming temperature is 40-60 ℃, and the defoaming time is 10-14 h; and preserving the casting solution at 30-60 ℃.
7. The method of claim 4, wherein: coating the casting solution on the base cloth by a scraper; the water bath temperature is 10-60 ℃, and the water bath time is 2-300 min.
8. The method of claim 3, wherein: the mass fraction of glutaraldehyde in the glutaraldehyde solution is 1-50%, and the pH is 1-6; the dipping time is 3-10 min; taking out after the impregnation is finished, placing the soaked product in a self-sealing bag, and carrying out heat treatment after sealing.
9. The method of claim 3, wherein: the heat treatment temperature is 80-100 ℃, and the heat treatment time is 30-90 min.
10. The membrane separation equipment is ultrafiltration membrane equipment, nanofiltration membrane equipment or reverse osmosis membrane equipment, and is characterized in that: the membrane for sewage treatment according to claim 1 or 2, or the membrane for sewage treatment prepared by the preparation method according to any one of claims 3 to 9.
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