CN113069937B - Oil-water separation membrane for wastewater treatment and preparation method thereof - Google Patents
Oil-water separation membrane for wastewater treatment and preparation method thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000000243 solution Substances 0.000 claims abstract description 59
- 238000002347 injection Methods 0.000 claims abstract description 41
- 239000007924 injection Substances 0.000 claims abstract description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 229920000742 Cotton Polymers 0.000 claims abstract description 25
- 239000012153 distilled water Substances 0.000 claims abstract description 21
- 239000002120 nanofilm Substances 0.000 claims abstract description 21
- QARRXYBJLBIVAK-UEMSJJPVSA-N 3-[(8e,11e)-pentadeca-8,11-dienyl]benzene-1,2-diol;3-[(8e,11e)-pentadeca-8,11,14-trienyl]benzene-1,2-diol;3-[(8e,11e,13e)-pentadeca-8,11,13-trienyl]benzene-1,2-diol;3-[(e)-pentadec-8-enyl]benzene-1,2-diol;3-pentadecylbenzene-1,2-diol Chemical compound CCCCCCCCCCCCCCCC1=CC=CC(O)=C1O.CCCCCC\C=C\CCCCCCCC1=CC=CC(O)=C1O.CCC\C=C\C\C=C\CCCCCCCC1=CC=CC(O)=C1O.C\C=C\C=C\C\C=C\CCCCCCCC1=CC=CC(O)=C1O.OC1=CC=CC(CCCCCCC\C=C\C\C=C\CC=C)=C1O QARRXYBJLBIVAK-UEMSJJPVSA-N 0.000 claims abstract description 19
- 239000000835 fiber Substances 0.000 claims abstract description 18
- RMTXUPIIESNLPW-UHFFFAOYSA-N 1,2-dihydroxy-3-(pentadeca-8,11-dienyl)benzene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1O RMTXUPIIESNLPW-UHFFFAOYSA-N 0.000 claims abstract description 17
- IYROWZYPEIMDDN-UHFFFAOYSA-N 3-n-pentadec-8,11,13-trienyl catechol Natural products CC=CC=CCC=CCCCCCCCC1=CC=CC(O)=C1O IYROWZYPEIMDDN-UHFFFAOYSA-N 0.000 claims abstract description 17
- DQTMTQZSOJMZSF-UHFFFAOYSA-N urushiol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1O DQTMTQZSOJMZSF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000019441 ethanol Nutrition 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004202 carbamide Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000009987 spinning Methods 0.000 claims abstract description 10
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000003958 fumigation Methods 0.000 claims abstract description 4
- 238000007710 freezing Methods 0.000 claims abstract description 3
- 230000008014 freezing Effects 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 229960000583 acetic acid Drugs 0.000 claims description 10
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 10
- 239000012362 glacial acetic acid Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000004408 titanium dioxide Substances 0.000 claims description 10
- 239000002121 nanofiber Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 238000010257 thawing Methods 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 8
- 239000001569 carbon dioxide Substances 0.000 abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 4
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 235000019476 oil-water mixture Nutrition 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
-
- 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
-
- 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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- 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
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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)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses an oil-water separation membrane used in wastewater treatment and a preparation method thereof, wherein the preparation method comprises the steps of preparing carbon dioxide gel; adding cotton fiber into a mixed solution of sodium hydroxide, urea and distilled water, stirring for 10-20 h, placing the mixed solution in a refrigerator at-45 to-38 ℃, and freezing to obtain a clear solution; adding urushiol into absolute ethyl alcohol, stirring at room temperature, and adding the TiO 2 Adding the gel into the solution, stirring, moving to an electrostatic spinning injection pump, spinning, and obtaining a nano film on a receiving roller, wherein the film is not taken down from the receiving roller; and (2) transferring the cotton fiber solution into an injection pump, spinning on the nano film, covering a layer of fiber film on the nano film, taking down the fiber film, placing the nano film on a metal net rack in a way that the fiber film faces downwards and the nano film faces upwards, placing the metal net rack in a container filled with ethanol solution, heating to generate ethanol steam for fumigation, vacuumizing and drying to obtain the separation membrane. The membrane of the invention has excellent advantageous separation efficiency and mechanical properties.
Description
Technical Field
The invention belongs to the technical field of separation membranes, and particularly relates to an oil-water separation membrane for wastewater treatment and a preparation method thereof.
Background
The shortage of water resources and the increasingly serious water pollution have become bottlenecks that restrict social progress and economic development. Oily wastewater is a common pollution source, which is extremely harmful to environmental protection and ecological balance, and water is an important resource for production and life, so that effective separation of oil from oily wastewater is a challenging task. Among the various oil-water separation methods, the oil-water separation membrane can selectively absorb oil or water, and has the advantages of high separation efficiency, difficulty in causing secondary pollution and the like, thereby causing wide attention.
Industrial wastewater and various domestic sewage are discharged into a water body environment, oil-water separation is difficult to treat, and the problems of high adhesiveness, strong ecological environment pollution, incomplete separation and the like are always the key points of pollution prevention and control at present. In the traditional treatment means, physical separation modes such as high-speed centrifugation, physical sedimentation, solidification separation and the like have the problems of poor effect treatment, long consumed time, residual smell, occupation of a large amount of factory land area and the like, and a chemical separation method possibly has the problems of secondary pollution to the environment and the like. Based on this, a membrane separation method using a combination of physical and chemical methods has low production cost and high separation efficiency, and can satisfy the goals of environmental protection and treatment efficiency, and thus has become a hot point of extensive research.
Chinese patent document CN108744600A discloses a method for preparing an oil-water separation membrane for sewage treatment, which takes natural phenolic compounds and silane amino compounds as raw materials to prepare benzoxazine monomers, and the benzoxazine monomers are prepared into a benzoxazine solution; and coating the benzoxazine solution on a base material for manufacturing the oil-water separation membrane to obtain the oil-water separation membrane. The oil-water separation membrane has no great change in separation efficiency in complex environments such as strong acid, strong alkali, high salt and the like, has good chemical stability, is simple in preparation process, can be prepared in one step, does not contain fluorine elements, and has the advantages of wide cotton cloth source, low price, low preparation cost, energy conservation, environmental friendliness, good separation effect and the like. However, the separation membrane prepared by repeatedly soaking cotton cloth and other substances in the benzoxazine solution has poor compactness, the substances loaded on the base material are easy to lose, and the oil-water separation efficiency of the separation membrane is poor after repeated recycling.
Disclosure of Invention
The invention aims to provide an oil-water separation membrane for wastewater treatment, which has two layers, wherein the upper layer is a urushiol/titanium dioxide nano-fiber membrane, the lower layer is a cotton fiber nano-membrane, and the urushiol/titanium dioxide nano-fiber membrane on the upper layer is partially dissolved and coated on the cotton fiber nano-membrane by a steam fumigation method, so that the oil-water separation membrane has higher compactness and oil-water separation efficiency.
Another object of the present invention is to provide a method for preparing an oil-water separation membrane for wastewater treatment, comprising the steps of:
s1: preparing titanium dioxide gel.
S2: adding cotton fiber into a mixed solution of sodium hydroxide, urea and distilled water, stirring for 10-20 h, placing the mixture in a refrigerator at-45 to-38 ℃, freezing for 6-8 h, taking out the mixture every 2-3 h, thawing, stirring for 10min, and repeating the steps for 3-5 times to obtain a clear solution.
S3: adding urushiol into absolute ethyl alcohol, wherein the mass ratio of urushiol to absolute ethyl alcohol is 1 2 Adding the gel into the solution, stirring for 30-40 min, transferring the gel into an electrostatic spinning injection pump, and injecting the gel into the solution under the conditions that the injection voltage is 18-21 kV and the injection distance is 12-15 cmThe speed is 0.2-0.3 mL/min, spinning is carried out, and the nano film is obtained on the receiving roller and is not taken down from the receiving roller.
S4: and (2) transferring the cotton fiber solution in the step (S2) into an injection pump, covering a layer of fiber film on the nano film in the step (S3) when the injection voltage is 15-18 kV, the injection distance is 10-12 cm, the injection speed is 0.3-0.5 mL/min, taking down the fiber film, placing the fiber film downwards and the nano film upwards on a metal net rack, placing the metal net rack in a container filled with ethanol solution, heating to 55-65 ℃ to generate ethanol steam, heating and fumigating for 30-60 min, cooling, vacuumizing, and drying at 80-95 ℃ for 3-5 h to obtain the separation film.
Preferably, the preparation of the titanium dioxide gel comprises the following steps:
1) Slowly adding tetrabutyl titanate into the absolute ethyl alcohol solution, and stirring at room temperature, wherein the volume ratio of tetrabutyl titanate to absolute ethyl alcohol is (1-2) to (6-10.6), so as to obtain a yellow clear solution.
2) Adding glacial acetic acid and distilled water into the absolute ethyl alcohol solution, stirring for 20-30 min, wherein the volume ratio of the glacial acetic acid to the distilled water to the absolute ethyl alcohol is (1-1.5) to (1.1-1.4) to (30-56), then dripping hydrochloric acid solution, and adjusting the pH value to 2.5-3 to obtain clear solution.
3) Adding the yellow clear solution obtained in the step 1) into the clear solution obtained in the step 2), and stirring for 15-20 h at 40-50 ℃ to obtain TiO 2 And (4) gelling.
Preferably, the mass volume ratio of the cotton fiber, the sodium hydroxide, the urea and the distilled water is (1.2-1.5), (11.2-11.8), (4.2-5.6) and (64-70) mL.
Preferably, the urushiol structure is:
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the oil-water separation membrane adopts an electrostatic spinning method, a layer of urushiol/titanium dioxide nanofiber membrane is covered on the cotton fiber nano-membrane, and then the urushiol/titanium dioxide nanofiber membrane is partially dissolved under the action of gravity and is covered on the cotton fiber nano-membrane by using an ethanol steam fumigation method, so that the separation membrane has more excellent compactness and further has better oil-water separation efficiency.
Drawings
FIG. 1 is a graph showing tensile properties and impact properties of separation membranes prepared in examples 1 to 3 of the present invention;
FIG. 2 is a graph showing the separation efficiency of different oil-water mixtures of the separation membrane prepared in example 1 of the present invention;
FIG. 3 is a graph showing contact angles of the separation membrane prepared in example 1 of the present invention with water at different pH values;
FIG. 4 is a graph showing contact angles of the separation membrane prepared in example 1 of the present invention with water at different temperatures;
FIG. 5 is a graph showing the oil-water separation efficiency of the separation membrane prepared in example 1 of the present invention after 20 cycles.
Detailed Description
The following embodiments of the present invention are described in detail, and the embodiments are implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, it should be noted that, for those skilled in the art, a plurality of modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Example 1
A preparation method of an oil-water separation membrane used in wastewater treatment specifically comprises the following steps:
s1: preparing carbon dioxide gel: 1) Slowly adding tetrabutyl titanate into the absolute ethyl alcohol solution, and stirring at room temperature, wherein the volume ratio of tetrabutyl titanate to absolute ethyl alcohol is 1.
2) Adding glacial acetic acid and distilled water into an absolute ethyl alcohol solution, stirring for 20min, then dropwise adding a hydrochloric acid solution, and adjusting the pH value to 2.5 to obtain a clear solution, wherein the volume ratio of the glacial acetic acid to the distilled water to the absolute ethyl alcohol is 1.
3) Adding the yellow clear solution obtained in the step 1) into the clear solution obtained in the step 2), and stirring for 15 hours at 40 ℃ to obtain TiO 2 And (4) gelling.
S2: adding cotton fibers into a mixed solution of sodium hydroxide, urea and distilled water, wherein the mass volume ratio of the cotton fibers to the sodium hydroxide to the urea to the distilled water is 1.2g, 11.2g, 4.2g.
S3: adding urushiol into absolute ethyl alcohol, wherein the mass ratio of urushiol to absolute ethyl alcohol is 1 2 Adding the gel into the solution, stirring for 30min, transferring to an electrostatic spinning injection pump, spinning under the conditions of injection voltage of 18kV, injection distance of 12cm and injection speed of 0.2mL/min to obtain a nano film on a receiving roller, wherein the film is not removed from the receiving roller.
S4: and (3) transferring the cotton fiber solution obtained in the step (S2) into an injection pump, covering a layer of fiber film on the nano film in the spinning step (S3) under the conditions that the injection voltage is 15kV, the injection distance is 10cm and the injection speed is 0.3mL/min, taking down the fiber film, placing the fiber film downwards and the nano film upwards on a metal net rack, placing the metal net rack in a container filled with ethanol solution, heating to 55 ℃ to generate ethanol steam, heating for 30min, cooling, vacuumizing, and drying at 80 ℃ for 3h to obtain the separation film.
Example 2
A preparation method of an oil-water separation membrane used in wastewater treatment specifically comprises the following steps:
s1: preparing carbon dioxide gel: 1) Tetrabutyl titanate is slowly added into the absolute ethyl alcohol solution and stirred at room temperature, wherein the volume ratio of the tetrabutyl titanate to the absolute ethyl alcohol is 2.
2) Adding glacial acetic acid and distilled water into the absolute ethyl alcohol solution, stirring for 30min, then dropwise adding a hydrochloric acid solution, and adjusting the pH value to 3 to obtain a clear solution, wherein the volume ratio of the glacial acetic acid to the distilled water to the absolute ethyl alcohol is 1.5.
3) Adding the yellow clear solution obtained in the step 1) into the clear solution obtained in the step 2), and stirring at 50 ℃ for 20h to obtain TiO 2 And (4) gelling.
S2: adding cotton fibers into a mixed solution of sodium hydroxide, urea and distilled water, wherein the mass volume ratio of the cotton fibers to the sodium hydroxide to the urea to the distilled water is 1.5g, 11.8g, 70mL.
S3: adding urushiol into absolute ethyl alcohol, wherein the mass ratio of urushiol to absolute ethyl alcohol is 1 2 Adding the gel into the solution, stirring for 40min, transferring to an electrostatic spinning injection pump, spinning at an injection voltage of 21kV, an injection distance of 15cm and an injection speed of 0.3mL/min to obtain a nano film on a receiving roller, wherein the film is not removed from the receiving roller.
S4: and (3) transferring the cotton fiber solution obtained in the step (S2) into an injection pump, covering a layer of fiber film on the nano film when the injection voltage is 15-18 kV, the injection distance is 12cm, the injection speed is 0.5mL/min, spinning the nano film obtained in the step (S3), taking down the fiber film, placing the fiber film downwards and the nano film upwards on a metal net rack, placing the metal net rack in a container filled with ethanol solution, heating to 65 ℃ to generate ethanol steam, heating for 60min, cooling, vacuumizing, and drying for 5h at 95 ℃ to obtain the separation film.
Example 3
A preparation method of an oil-water separation membrane used in wastewater treatment specifically comprises the following steps:
s1: preparing a carbon dioxide gel: 1) Slowly adding tetrabutyl titanate into the absolute ethyl alcohol solution, and stirring at room temperature, wherein the volume ratio of tetrabutyl titanate to absolute ethyl alcohol is 1.6.
2) Adding glacial acetic acid and distilled water into the absolute ethyl alcohol solution, stirring for 25min, then dropwise adding a hydrochloric acid solution, and adjusting the pH value to 3 to obtain a clear solution, wherein the volume ratio of the glacial acetic acid to the distilled water to the absolute ethyl alcohol is 1.2.
3) Adding the yellow clear solution obtained in the step 1) into the clear solution obtained in the step 2), and stirring for 15-20 h at 40-50 ℃ to obtain TiO 2 And (4) gelling.
S2: adding cotton fibers into a mixed solution of sodium hydroxide, urea and distilled water, wherein the mass volume ratio of the cotton fibers to the sodium hydroxide to the urea to the distilled water is 1.4g, 11.6 g.
S3: adding urushiol into absolute ethyl alcohol, wherein the mass ratio of urushiol to absolute ethyl alcohol is 1 2 Adding gel into the solution, stirring for 35min, transferring into an electrostatic spinning injection pump, spinning at injection voltage of 20kV, injection distance of 14cm and injection rate of 0.25mL/min to obtain nanometer film on the receiving roller, wherein the film is not removed from the receiving roller.
S4: and (3) transferring the cotton fiber solution obtained in the step (S2) into an injection pump, covering a layer of fiber film on the nano film when the injection voltage is 16kV, the injection distance is 11cm and the injection speed is 0.4mL/min, spinning the nano film obtained in the step (S3), taking down the fiber film, placing the fiber film downwards and the nano film upwards on a metal net rack, placing the metal net rack in a container filled with ethanol solution, heating to 60 ℃ to generate ethanol steam, heating for 50min, cooling, vacuumizing, and drying at 90 ℃ for 4h to obtain the separation film.
Performance test experiments:
the separation membranes prepared in examples 1 to 3 were subjected to an impact strength test in accordance with GB/T1043.1 to 2008 and a tensile strength test in accordance with GB/T1040.2 to 2006, and the results are shown in FIG. 1,
the separation membrane prepared in example 1 was tested for separation efficiency, petroleum ether, diesel oil, kerosene, n-hexane and water were mixed at a volume ratio of 1, and then tested, and the separation efficiency was calculated according to the following formula: q = M t /M 0 X 100% where M t At the initial weight, M 0 The weight of the separated oil, the result of which is shown in FIG. 2,
the separation membrane prepared in example 1 was first soaked in solutions of different pH values for 24h, and then taken out to test its water contact angle, the results of which are shown in fig. 3; the separation membrane prepared in example 1 was heated at 100 to 200 ℃ for 2 hours, cooled, taken out, and tested for its water contact angle, the results of which are shown in fig. 4; the separation membrane prepared in example 1 was subjected to a cyclic test for the oil-water separation efficiency of diesel oil and water at a volume ratio of 1, and the results of the test are shown in FIG. 5,
as can be seen from FIG. 1, the separation membranes prepared in examples 1 to 3 had tensile strengths of 36MPa or more and impact strengths of 15KJ/m 2 The separation membrane prepared in the example 1 has good mechanical properties, and as can be seen from fig. 2, the separation efficiency of the separation membrane is about 99.2% in the separation process of four different oil-water mixtures, so that the separation membrane has an excellent oil-water separation effect; as can be seen from fig. 3 and 4, the separation membranes prepared in the examples have certain difference in water contact angle at different pH values, but the water contact angle is above 138 ° even at pH =1, and the water contact angle does not change much at different temperatures, indicating that the separation membranes have excellent stability; as can be seen from fig. 5, after 20 times of cyclic separation, the separation efficiency of the separation membrane is still above 90%, indicating that the membrane has better cyclic stability.
It should be noted that the separation membranes prepared in the other examples of the present invention have the same or similar separation efficiency as the separation membrane prepared in example 1, and need not be described herein.
Claims (3)
1. A preparation method of an oil-water separation membrane used in wastewater treatment is characterized in that the oil-water separation membrane has two layers, the upper layer is a urushiol/titanium dioxide nano-fiber membrane, the lower layer is a cotton fiber nano-membrane, and the urushiol/titanium dioxide nano-fiber membrane on the upper layer is partially dissolved and coated on the cotton fiber nano-membrane by a steam fumigation method; the preparation method comprises the following steps:
s1: preparing titanium dioxide gel;
s2: adding cotton fiber into a mixed solution of sodium hydroxide, urea and distilled water, stirring for 10-20 h, placing the mixture in a refrigerator at the temperature of-45 to-38 ℃, freezing for 6-8 h, taking out the mixture every 2-3 h, thawing and stirring for 10min, and repeating the steps for 3-5 times to obtain a clear solution;
s3: adding urushiol into absolute ethyl alcohol, wherein the mass ratio of urushiol to absolute ethyl alcohol is 1 2 Adding the gel into the solution, stirring for 30-40 min, transferring the gel into an electrostatic spinning injection pump, spinning under the conditions that the injection voltage is 18-21 kV, the injection distance is 12-15 cm, and the injection speed is 0.2-0.3 mL/min, and obtaining a nano film on a receiving roller, wherein the film is not taken down from the receiving roller;
s4: transferring the cotton fiber solution in the step S2 into an injection pump, covering a layer of fiber film on the nano film in the step S3 when the injection voltage is 15-18 kV, the injection distance is 10-12 cm and the injection speed is 0.3-0.5 mL/min, taking down the fiber film, placing the fiber film downwards and the nano film upwards on a metal net rack, placing the metal net rack in a container filled with ethanol solution, heating to 55-65 ℃ to generate ethanol steam, heating and fumigating for 30-60 min, cooling, vacuumizing, and drying at 80-95 ℃ for 3-5 h to obtain the separation film;
the preparation of the titanium dioxide gel comprises the following steps:
1) Slowly adding tetrabutyl titanate into an absolute ethyl alcohol solution, and stirring at room temperature, wherein the volume ratio of tetrabutyl titanate to absolute ethyl alcohol is (1-2) to (6-10.6), so as to obtain a yellow clear solution;
2) Adding glacial acetic acid and distilled water into an absolute ethyl alcohol solution, stirring for 20-30 min, then dropwise adding a hydrochloric acid solution, and adjusting the pH value to 2.5-3 to obtain a clear solution, wherein the volume ratio of the glacial acetic acid to the distilled water to the absolute ethyl alcohol is (1-1.5) - (1.1-1.4) - (30-56);
3) Adding the yellow clear solution obtained in the step 1) into the clear solution obtained in the step 2), and stirring for 15-20 h at 40-50 ℃ to obtain TiO 2 And (4) gelling.
2. The method for preparing the oil-water separation membrane for wastewater treatment according to claim 1, wherein the mass-volume ratio of the cotton fiber to the sodium hydroxide to the urea to the distilled water is (1.2-1.5) g, (11.2-11.8) g, (4.2-5.6) g, (64-70) mL.
3. The method for preparing the oil-water separation membrane for wastewater treatment according to claim 1, wherein the urushiol structure is:
wherein R is C 8 ～C 17 Alkyl or alkenyl groups of (a). />
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