CN117547984B - Water treatment membrane of MABR aeration bioreactor and preparation method thereof - Google Patents
Water treatment membrane of MABR aeration bioreactor and preparation method thereof Download PDFInfo
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- CN117547984B CN117547984B CN202410044435.XA CN202410044435A CN117547984B CN 117547984 B CN117547984 B CN 117547984B CN 202410044435 A CN202410044435 A CN 202410044435A CN 117547984 B CN117547984 B CN 117547984B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000012528 membrane Substances 0.000 title claims abstract description 36
- UEKDBDAWIKHROY-UHFFFAOYSA-L bis(4-bromo-2,6-ditert-butylphenoxy)-methylalumane Chemical compound [Al+2]C.CC(C)(C)C1=CC(Br)=CC(C(C)(C)C)=C1[O-].CC(C)(C)C1=CC(Br)=CC(C(C)(C)C)=C1[O-] UEKDBDAWIKHROY-UHFFFAOYSA-L 0.000 title claims abstract description 28
- 238000005273 aeration Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000011347 resin Substances 0.000 claims abstract description 37
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 230000003075 superhydrophobic effect Effects 0.000 claims abstract description 37
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 15
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 15
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims description 119
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 66
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 34
- 239000007795 chemical reaction product Substances 0.000 claims description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims description 33
- 239000012153 distilled water Substances 0.000 claims description 27
- 239000012065 filter cake Substances 0.000 claims description 26
- 238000001291 vacuum drying Methods 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 20
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 20
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 16
- SGNZYJXNUURYCH-UHFFFAOYSA-N 5,6-dihydroxyindole Chemical compound C1=C(O)C(O)=CC2=C1NC=C2 SGNZYJXNUURYCH-UHFFFAOYSA-N 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000005266 casting Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012954 diazonium Substances 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims description 10
- 235000010288 sodium nitrite Nutrition 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 claims description 8
- MEXUTNIFSHFQRG-UHFFFAOYSA-N 6,7,12,13-tetrahydro-5h-indolo[2,3-a]pyrrolo[3,4-c]carbazol-5-one Chemical compound C12=C3C=CC=C[C]3NC2=C2NC3=CC=C[CH]C3=C2C2=C1C(=O)NC2 MEXUTNIFSHFQRG-UHFFFAOYSA-N 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 7
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 7
- 230000015271 coagulation Effects 0.000 claims description 7
- 238000005345 coagulation Methods 0.000 claims description 7
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 7
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 7
- 239000004745 nonwoven fabric Substances 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 7
- 238000007790 scraping Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- XHVUVQAANZKEKF-UHFFFAOYSA-N bromine pentafluoride Chemical compound FBr(F)(F)(F)F XHVUVQAANZKEKF-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 29
- 239000001301 oxygen Substances 0.000 abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 abstract description 29
- 244000005700 microbiome Species 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 7
- 239000010865 sewage Substances 0.000 abstract description 7
- 238000000746 purification Methods 0.000 abstract description 6
- 241001148470 aerobic bacillus Species 0.000 abstract description 5
- 230000004060 metabolic process Effects 0.000 abstract description 4
- 230000000903 blocking effect Effects 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 38
- 238000012360 testing method Methods 0.000 description 7
- 238000003828 vacuum filtration Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000002352 surface water Substances 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 101710082751 Carboxypeptidase S1 homolog A Proteins 0.000 description 1
- 102100023804 Coagulation factor VII Human genes 0.000 description 1
- 241000612182 Rexea solandri Species 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0016—Coagulation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/10—Packings; Fillings; Grids
- C02F3/102—Permeable membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Microbiology (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of water treatment, in particular to a water treatment membrane of an MABR aeration bioreactor and a preparation method thereof, which are used for solving the problems that water molecules are easily adsorbed in the membrane pores of the water treatment membrane of the existing MABR aeration bioreactor, so that oxygen is difficult to reach the outer wall of the membrane, sufficient oxygen cannot be provided for the growth of microorganisms, the metabolism of aerobic bacteria is further limited, and the sewage treatment effect is affected; the water treatment film comprises the following components in parts by weight: 30-35 parts of super-hydrophobic resin, 1.5-2.5 parts of polyvinylpyrrolidone and 100-110 parts of N, N-dimethylformamide; the super-hydrophobic resin has excellent hydrophobicity, and prevents moisture from blocking micropores on the water treatment membrane, so that oxygen can pass through easily, oxygen can be efficiently, quickly and largely conducted from the inner side to the outer side of the water treatment membrane, growth of microorganisms is promoted, and the purification effect and the purification efficiency of the microorganisms on sewage are improved.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a water treatment membrane of an MABR aeration bioreactor and a preparation method thereof.
Background
The aerobic biochemical technology is one of main biochemical technologies for treating wastewater, and can directly decompose organic matters and finally become water and carbon dioxide. For low COD waste water, such as polluted river water, aerobic is the most effective treatment technology for eliminating black and stink and improving water quality. The conventional aerobic biochemical technology needs to provide oxygen to the water body for the metabolism of aerobic bacteria. The current main stream is to blow air into water by a high-pressure blower, and form smaller bubbles into water by an aeration head or an aeration pipe, wherein oxygen in the bubbles is dissolved in the water. The MABR technology adopts pressureless oxygen supply, has very low energy consumption in operation, has very large application prospect, is not only used as an oxygen supply element, but also used as a growth carrier of microorganisms in the MABR system, is a core heart of the system, and the membrane materials adopted in the market at present have excellent hydrophilicity, so that the hydrophilic microporous membrane often has good microorganism affinity, is easy for the growth and attachment of microorganisms, but is extremely easy to adsorb water molecules in the membrane pores, so that oxygen is difficult to reach the outer wall of the membrane, sufficient oxygen cannot be provided for the growth of the microorganisms, further the metabolism of aerobic bacteria is limited, and the sewage treatment effect is affected.
Disclosure of Invention
In order to overcome the technical problems, the invention aims to provide a water treatment membrane of an MABR aeration bioreactor and a preparation method thereof: through adding super-hydrophobic resin, polyvinylpyrrolidone and N, N-dimethylformamide into a three-neck flask for stirring reaction, standing for defoaming to obtain casting solution, pouring the casting solution on PET non-woven fabrics for scraping, then soaking in deionized water coagulation bath, and solidifying to form a film, the water treatment film of the MABR aeration bioreactor is obtained, and the problems that water molecules are easily adsorbed in the water treatment film holes of the existing MABR aeration bioreactor, so that oxygen is difficult to reach the outer wall of the film, sufficient oxygen cannot be provided for the growth of microorganisms, the metabolism of aerobic bacteria is further limited, and the sewage treatment effect of the aerobic bacteria is affected are solved.
The aim of the invention can be achieved by the following technical scheme:
the water treatment membrane of the MABR aeration bioreactor comprises the following components in parts by weight:
30-35 parts of super-hydrophobic resin, 1.5-2.5 parts of polyvinylpyrrolidone and 100-110 parts of N, N-dimethylformamide.
As a further scheme of the invention: the super-hydrophobic resin is prepared by the following steps:
step a1: adding pentafluorobenzoic acid and absolute ethyl alcohol into a three-neck flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, stirring and reacting for 30-50min under the conditions of 25-30 ℃ and stirring speed of 400-500r/min, then dropwise adding a potassium tert-butoxide solution while stirring, controlling the dropping speed to be 1-2 drops/s, continuing stirring and reacting for 2-3h after the dripping is finished, adding a reaction product into absolute ethyl ether after the reaction is finished, then carrying out vacuum suction filtration, placing a filter cake into a vacuum drying box, and drying for 2-3h under the conditions of 30-35 ℃ to obtain an intermediate 1;
the reaction principle is as follows:
step a2: adding the intermediate 1, cuprous iodide, 1, 10-phenanthroline, pentafluorobromine and diethylene glycol dimethyl ether into a three-neck flask provided with a stirrer, a thermometer and a nitrogen inlet pipe, introducing nitrogen for protection, stirring and reacting for 20-25min under the conditions of 25-30 ℃ and 400-500r/min of stirring rate, then continuously stirring and reacting for 25-30h under the conditions of heating to 130-135 ℃, cooling the reaction product to room temperature after the reaction is finished, then adding the reaction product into ethyl acetate, then vacuum suction filtering, standing and layering filtrate, washing an organic phase with distilled water and saturated saline water for 2-3 times in sequence, then drying with anhydrous sodium sulfate, vacuum suction filtering, and rotationally evaporating the filtrate to remove the solvent to obtain an intermediate 2;
the reaction principle is as follows:
step a3: adding 4-nitroaniline and deionized water into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, dropwise adding concentrated hydrochloric acid while stirring at a temperature of-5-0 ℃ and a stirring rate of 400-500r/min, controlling the dropwise adding rate to be 1-2 drops/s, continuously dropwise adding sodium nitrite solution after dropwise adding, controlling the dropwise adding rate to be 1-2 drops/s, continuously stirring for reaction for 30-40min after dropwise adding, obtaining diazonium solution, adding p-benzoquinone, sodium bicarbonate and distilled water into the three-neck flask, dropwise adding diazonium solution while stirring at a temperature of 0-5 ℃, controlling the dropwise adding rate to be 1-2 drops/s, continuously stirring for reaction for 4-5h after dropwise adding, vacuum filtering a reaction product after the reaction, washing a filter cake with saturated saline solution for 2-3 times, then placing in a vacuum drying box, and drying for 2-3h at a temperature of 30-35 ℃ to obtain an intermediate 3;
the reaction principle is as follows:
step a4: adding the intermediate 3, zinc powder and concentrated hydrochloric acid into a three-neck flask provided with a stirrer, a thermometer, a nitrogen inlet pipe and a reflux condenser, introducing nitrogen for protection, stirring and reacting for 25-30min under the condition that the temperature is 25-30 ℃ and the stirring speed is 400-500r/min, heating to reflux, continuing stirring and reacting for 8-10h, vacuum filtering while hot, cooling filtrate to below 0 ℃, precipitating precipitate, vacuum filtering, washing a filter cake with distilled water for 2-3 times, placing in a vacuum drying box, and drying for 2-3h under the condition that the temperature is 50-55 ℃ to obtain an intermediate 4;
the reaction principle is as follows:
step a5: adding the intermediate 2, the intermediate 4, anhydrous potassium carbonate, dimethyl sulfoxide and toluene into a three-neck flask provided with a stirrer, a thermometer and a nitrogen inlet pipe, introducing nitrogen for protection, stirring and reacting for 30-40min under the condition that the temperature is 25-30 ℃ and the stirring rate is 400-500r/min, then continuously stirring and reacting for 4-5h under the condition that the temperature is raised to 140-145 ℃, then continuously stirring and reacting for 2-2.5h under the condition that the temperature is raised to 160-165 ℃, cooling the reaction product to room temperature after the reaction is finished, adding into distilled water, then carrying out vacuum suction filtration, crushing a filter cake, and then placing in a vacuum drying box, and drying for 4-5h under the condition that the temperature is 70-75 ℃ to obtain an intermediate 5;
the reaction principle is as follows:
step a6: adding the intermediate 5, triethylamine and methylene dichloride into a four-mouth flask provided with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, stirring and reacting for 15-20min under the conditions of 0-5 ℃ and stirring speed of 400-500r/min, then adding the heptafluorobutyryl chloride solution dropwise while stirring, controlling the dropping speed to be 1-2 drops/s, continuously stirring and reacting for 4-5h under the conditions of heating to 45-50 ℃ after the dripping is finished, cooling the reaction product to room temperature after the reaction is finished, rotationally evaporating to remove the solvent, washing for 2-3 times with distilled water, then placing in a vacuum drying box, and drying for 8-10h under the conditions of 65-70 ℃ to obtain the super-hydrophobic resin.
The reaction principle is as follows:
as a further scheme of the invention: the dosage ratio of the pentafluorobenzoic acid, the absolute ethyl alcohol and the potassium tert-butoxide solution in the step a1 is 10mmol:20-25mL:10mL of the potassium tert-butoxide solution is prepared from 9-10mmol of potassium tert-butoxide: 10mL of the solution was dissolved in absolute ethanol.
As a further scheme of the invention: the dosage ratio of the intermediate 1, the cuprous iodide, the 1, 10-phenanthroline, the pentafluorobromide benzene and the diethylene glycol dimethyl ether in the step a2 is 10mmol:1.2-1.3mmol:0.2-0.25g:7-8mmol:40-50mL.
As a further scheme of the invention: the dosage ratio of the 4-nitroaniline, deionized water, concentrated hydrochloric acid, sodium nitrite solution, p-benzoquinone, sodium bicarbonate and distilled water in the step a3 is 10mmol:25-30mL:5-6mL:6-8mL:10mmol:15-20mmol:40-50mL, wherein the mass fraction of the concentrated hydrochloric acid is 36-38%, and the mass fraction of the sodium nitrite solution is 15-18%.
As a further scheme of the invention: the dosage ratio of the intermediate 3, zinc powder and concentrated hydrochloric acid in the step a4 is 10mmol:35-40mmol:50-60mL, wherein the mass fraction of the concentrated hydrochloric acid is 36-38%.
As a further scheme of the invention: the dosage ratio of the intermediate 2, the intermediate 4, the anhydrous potassium carbonate, the dimethyl sulfoxide and the toluene in the step a5 is 10mmol:10mmol:13-15mmol:25-30mL:10-12mL.
As a further scheme of the invention: the dosage ratio of the intermediate 5, triethylamine, methylene chloride and heptafluorobutyryl chloride solution in the step a6 is 1g:0.3-0.5g:30-35mL:15-30mL of the heptafluorobutyryl chloride solution is heptafluorobutyryl chloride according to 0.5g:10mL of the solution was dissolved in methylene chloride.
As a further scheme of the invention: the preparation method of the water treatment membrane of the MABR aeration bioreactor comprises the following steps:
step one: weighing 30-35 parts of super-hydrophobic resin, 1.5-2.5 parts of polyvinylpyrrolidone and 100-110 parts of N, N-dimethylformamide according to parts by weight for later use;
step two: adding super-hydrophobic resin, polyvinylpyrrolidone and N, N-dimethylformamide into a three-neck flask with a stirrer and a thermometer, stirring and reacting for 15-20h under the conditions that the temperature is 25-30 ℃ and the stirring speed is 400-500r/min, and standing for removing bubbles for 10-15h to obtain a casting film liquid;
step three: pouring the casting solution on PET non-woven fabric, scraping and coating by using a scraper with a gap of 200 mu m, soaking in deionized water coagulation bath, and curing to form a film to obtain the water treatment film of the MABR aeration bioreactor.
The invention has the beneficial effects that:
the invention relates to a water treatment membrane of an MABR aeration bioreactor and a preparation method thereof, wherein super-hydrophobic resin, polyvinylpyrrolidone and N, N-dimethylformamide are added into a three-neck flask for stirring reaction, then standing is carried out for bubble removal, a casting solution is obtained, the casting solution is poured onto PET non-woven fabrics for knife coating, and then the casting solution is soaked in deionized water coagulation bath for curing and film forming, so that the water treatment membrane of the MABR aeration bioreactor is obtained; the main raw material of the water treatment membrane is super-hydrophobic resin, the super-hydrophobic resin has excellent hydrophobicity, so that the water treatment membrane is difficult to wet by water, the water treatment membrane can not easily adsorb moisture, and the water is prevented from blocking micropores on the water treatment membrane, so that oxygen can be ensured to pass easily, oxygen can be efficiently, quickly and largely conducted from the inner side to the outer side of the water treatment membrane, sufficient oxygen is provided for microorganisms, the growth of the microorganisms is promoted, and the purification effect and the purification efficiency of the microorganisms on sewage are improved;
in the process of preparing a water treatment membrane of an MABR aeration bioreactor, firstly preparing a super-hydrophobic resin, firstly utilizing pentafluorobenzoic acid to react with potassium tert-butoxide to obtain an intermediate 1, then utilizing potassium carboxy on the intermediate 1 to react with bromine atoms on pentafluorobromine to obtain an intermediate 2, wherein the intermediate 2 is of a structure with two benzene rings and a large number of fluorine atoms, then enabling 4-nitroaniline to form diazonium salt under the action of sodium nitrite, then reacting with p-benzoquinone to obtain an intermediate 3, then enabling the intermediate 3 to form an intermediate 4 under the reduction action of zinc powder, then utilizing fluorine atoms on the para position of the intermediate 2 to react with hydroxyl on the intermediate 4 to form a polymer to obtain an intermediate 5, and then utilizing acyl chloride on heptafluorobutyryl chloride to react with amino on the intermediate 5 to obtain the super-hydrophobic resin; the super-hydrophobic resin has the advantages that the molecular structure of the super-hydrophobic resin contains a large number of benzene rings, the stability and the rigidity of the benzene rings are high, the good mechanical property of the super-hydrophobic resin are endowed, a large number of fluorine atoms on the super-hydrophobic resin endow the super-hydrophobic resin with good hydrophobicity, a foundation is provided for efficient conduction of oxygen, good corrosion resistance is endowed to the super-hydrophobic resin, the super-hydrophobic resin can still keep high performance for a long time under severe environments of sewage treatment, and can bear larger air conveying flow without damage, so that the oxygen conveying amount and the conveying efficiency are further improved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
the embodiment is a preparation method of super-hydrophobic resin, comprising the following steps:
step a1: 10mmol of pentafluorobenzoic acid and 20mL of absolute ethyl alcohol are added into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, stirred and reacted for 30min under the condition that the temperature is 25 ℃ and the stirring rate is 400r/min, and then 10mL of potassium tert-butoxide is added dropwise while stirring according to 9mmol:10mL of potassium tert-butoxide solution formed by dissolving the potassium tert-butoxide in absolute ethyl alcohol is controlled to have the dropping speed of 1 drop/s, stirring is continued to react for 2 hours after the dropping is finished, a reaction product is added into absolute ethyl ether after the reaction is finished, then vacuum suction filtration is carried out, a filter cake is placed in a vacuum drying oven, and drying is carried out for 2 hours at the temperature of 30 ℃ to obtain an intermediate 1;
step a2: adding 10mmol of intermediate 1, 1.2mmol of cuprous iodide, 0.2g of 1, 10-phenanthroline, 7mmol of pentafluorobromide benzene and 40mL of diethylene glycol dimethyl ether into a three-neck flask provided with a stirrer, a thermometer and a nitrogen inlet pipe, introducing nitrogen for protection, stirring at the temperature of 25 ℃ and the stirring speed of 400r/min for reaction for 20min, heating to 130 ℃ for continuous stirring for reaction for 25h, cooling the reaction product to room temperature after the reaction is finished, adding the reaction product into ethyl acetate, vacuum filtering, standing and layering the filtrate, washing the organic phase with distilled water and saturated saline water for 2 times in sequence, drying with anhydrous sodium sulfate, vacuum filtering, and rotationally evaporating the filtrate to remove the solvent to obtain intermediate 2;
step a3: adding 10mmol of 4-nitroaniline and 25mL of deionized water into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, dropwise adding 5mL of concentrated hydrochloric acid with the mass fraction of 36% under the conditions of the temperature of-5 ℃ and the stirring rate of 400r/min, controlling the dripping rate to be 1 drop/s, continuously dropwise adding 6mL of sodium nitrite solution with the mass fraction of 15% after the dripping, controlling the dripping rate to be 1 drop/s, continuously stirring for reaction for 30min after the dripping is finished, obtaining diazonium solution, adding 10mmol of p-benzoquinone, 15mmol of sodium bicarbonate and 40mL of distilled water into the three-neck flask, dropwise adding the diazonium solution under the conditions of the temperature of 0 ℃, controlling the dripping rate to be 1 drop/s, continuously stirring for reaction for 4h after the dripping is finished, vacuum filtering the reaction product, washing the filter cake with saturated brine for 2 times, then placing the filter cake in a vacuum drying box, and drying for 2h under the conditions of the temperature of 30 ℃ to obtain intermediate 3;
step a4: adding 10mmol of intermediate 3, 35mmol of zinc powder and 50mL of 36% by mass fraction concentrated hydrochloric acid into a three-neck flask provided with a stirrer, a thermometer, a nitrogen inlet pipe and a reflux condenser, introducing nitrogen for protection, stirring and reacting for 25min under the condition of 25 ℃ and 400r/min of stirring rate, heating to reflux, continuing stirring and reacting for 8h, vacuum filtering while the mixture is hot, cooling the filtrate to below 0 ℃, precipitating precipitate, vacuum filtering, washing a filter cake with distilled water for 2 times, placing in a vacuum drying box, and drying for 2h under the condition of 50 ℃ to obtain an intermediate 4;
step a5: 10mmol of intermediate 2, 10mmol of intermediate 4, 13mmol of anhydrous potassium carbonate, 25mL of dimethyl sulfoxide and 10mL of toluene are added into a three-neck flask provided with a stirrer, a thermometer and a nitrogen inlet pipe, nitrogen is introduced for protection, stirring is carried out for reaction for 30min under the condition that the temperature is 25 ℃ and the stirring rate is 400r/min, stirring is continued for reaction for 4h under the condition that the temperature is raised to 140 ℃, stirring is continued for reaction for 2h under the condition that the temperature is raised to 160 ℃, the reaction product is cooled to room temperature after the reaction is finished, then the reaction product is added into distilled water, then vacuum filtration is carried out, the filter cake is crushed, then the filter cake is placed into a vacuum drying box, and is dried for 4h under the condition that the temperature is 70 ℃ to obtain intermediate 5;
step a6: 1g of intermediate 5, 0.3g of triethylamine and 30mL of methylene chloride were charged into a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, and reacted at a stirring rate of 400r/min at a temperature of 0℃for 15 minutes under stirring, followed by dropwise addition of 15mL of heptafluorobutyryl chloride with stirring in an amount of 0.5g:10mL of heptafluorobutyryl chloride solution formed by dissolving in dichloromethane, controlling the dropping speed to be 1 drop/s, continuously stirring and reacting for 4 hours under the condition of heating to 45 ℃ after the dropping, cooling the reaction product to room temperature after the reaction is finished, removing the solvent by rotary evaporation, washing 2 times by distilled water, and then placing in a vacuum drying box and drying for 8 hours under the condition of 65 ℃ to obtain the super-hydrophobic resin.
Example 2:
the embodiment is a preparation method of super-hydrophobic resin, comprising the following steps:
step a1: 10mmol of pentafluorobenzoic acid and 22mL of absolute ethyl alcohol are added into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, stirred and reacted for 40min under the conditions that the temperature is 28 ℃ and the stirring rate is 450r/min, and then 10mL of potassium tert-butoxide is added dropwise while stirring according to 9.5mmol:10mL of potassium tert-butoxide solution formed by dissolving the potassium tert-butoxide in absolute ethyl alcohol is controlled to have the dropping speed of 1 drop/s, stirring is continued to react for 2.5 hours after the dropping is finished, a reaction product is added into absolute ethyl ether after the reaction is finished, then vacuum suction filtration is carried out, a filter cake is placed in a vacuum drying oven, and the filter cake is dried for 2.5 hours under the condition that the temperature is 32 ℃ to obtain an intermediate 1;
step a2: 10mmol of intermediate 1, 1.25mmol of cuprous iodide, 0.22g of 1, 10-phenanthroline, 7.5mmol of pentafluorobromide benzene and 45mL of diethylene glycol dimethyl ether are added into a three-neck flask provided with a stirrer, a thermometer and a nitrogen inlet pipe, nitrogen is introduced for protection, stirring is carried out for 22min under the condition that the temperature is 28 ℃ and the stirring rate is 450r/min, then the temperature is raised to 132 ℃ for continuous stirring reaction for 28h, the reaction product is cooled to room temperature after the reaction is finished, then the reaction product is added into ethyl acetate, then vacuum suction filtration is carried out, the filtrate is kept still for layering, the organic phase is washed for 2 times by distilled water and saturated saline in sequence, then dried by anhydrous sodium sulfate, then vacuum suction filtration is carried out, and the solvent is removed by rotary evaporation of the filtrate, thus obtaining intermediate 2;
step a3: adding 10mmol of 4-nitroaniline and 28mL of deionized water into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, dropwise adding 5.5mL of concentrated hydrochloric acid with the mass fraction of 37% while stirring at the temperature of-3 ℃ and the stirring rate of 450r/min, controlling the dropping rate to be 1 drop/s, continuously dropwise adding 7mL of sodium nitrite solution with the mass fraction of 16% after the dropping, controlling the dropping rate to be 1 drop/s, continuously stirring for reaction for 35min after the dropping is finished, obtaining diazonium solution, adding 10mmol of p-benzoquinone, 18mmol of sodium bicarbonate and 45mL of distilled water into the three-neck flask, dropwise adding diazonium solution while stirring at the temperature of 2 ℃, continuously stirring for reaction for 4.5h after the dropping, washing a reaction product with saturated brine for 3 times after the reaction, then placing the reaction product into a vacuum drying box, and drying for 2.5h at the temperature of 32 ℃ to obtain an intermediate;
step a4: adding 10mmol of intermediate 3, 38mmol of zinc powder and 55mL of concentrated hydrochloric acid with mass fraction of 37% into a three-neck flask provided with a stirrer, a thermometer, a nitrogen inlet pipe and a reflux condenser, introducing nitrogen for protection, stirring and reacting for 28min under the condition of 28 ℃ and stirring speed of 450r/min, heating to reflux, continuing stirring and reacting for 9h, vacuum filtering while the mixture is hot, cooling the filtrate to below 0 ℃, precipitating precipitate, vacuum filtering, washing the filter cake with distilled water for 3 times, placing in a vacuum drying box, and drying for 2.5h under the condition of 52 ℃ to obtain intermediate 4;
step a5: 10mmol of intermediate 2, 10mmol of intermediate 4, 14mmol of anhydrous potassium carbonate, 28mL of dimethyl sulfoxide and 11mL of toluene are added into a three-neck flask provided with a stirrer, a thermometer and a nitrogen inlet pipe, nitrogen is introduced for protection, stirring is carried out for reaction for 35min under the condition that the temperature is 28 ℃ and the stirring rate is 450r/min, then stirring is continued for reaction for 4.5h under the condition that the temperature is raised to 142 ℃, then stirring is continued for reaction for 2.2h under the condition that the temperature is raised to 162 ℃, the reaction product is cooled to room temperature after the reaction is finished, then the reaction product is added into distilled water, then vacuum filtration is carried out, the filter cake is crushed, then the filter cake is placed into a vacuum drying box, and dried for 4.5h under the condition that the temperature is 72 ℃ to obtain intermediate 5;
step a6: 1g of intermediate 5, 0.4g of triethylamine and 32mL of methylene chloride were charged into a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, and reacted at a temperature of 3℃under stirring at a stirring rate of 450r/min for 18 minutes, followed by dropwise addition of 22mL of heptafluorobutyryl chloride with stirring according to 0.5g: and (3) 10mL of heptafluorobutyryl chloride solution formed by dissolving in dichloromethane, controlling the dropping speed to be 1 drop/s, continuously stirring and reacting for 4.5h under the condition of heating to 48 ℃ after the dropping, cooling the reaction product to room temperature after the reaction is finished, removing the solvent by rotary evaporation, washing 3 times by using distilled water, and then placing in a vacuum drying box and drying for 9h under the condition of 68 ℃ to obtain the superhydrophobic resin.
Example 3:
the embodiment is a preparation method of super-hydrophobic resin, comprising the following steps:
step a1: 10mmol of pentafluorobenzoic acid and 25mL of absolute ethyl alcohol are added into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, and stirred at a temperature of 30 ℃ and a stirring rate of 500r/min for 50min, and then 10mL of potassium tert-butoxide is added dropwise while stirring according to 10mmol:10mL of potassium tert-butoxide solution formed by dissolving the potassium tert-butoxide in absolute ethyl alcohol is stirred for 3 hours after the dripping is finished, the reaction product is added into absolute ethyl ether after the dripping is finished, then vacuum filtration is carried out, a filter cake is placed in a vacuum drying oven, and the filter cake is dried for 3 hours under the condition of 35 ℃ to obtain an intermediate 1;
step a2: 10mmol of intermediate 1, 1.3mmol of cuprous iodide, 0.25g of 1, 10-phenanthroline, 8mmol of pentafluorobromide benzene and 50mL of diethylene glycol dimethyl ether are added into a three-neck flask provided with a stirrer, a thermometer and a nitrogen inlet pipe, nitrogen is introduced for protection, stirring is carried out for reaction for 25min under the condition that the temperature is 30 ℃ and the stirring rate is 500r/min, then the temperature is increased to 135 ℃ for continuous stirring reaction for 30h, the reaction product is cooled to room temperature after the reaction is finished, then the reaction product is added into ethyl acetate, then vacuum filtration is carried out, the filtrate is kept still for layering, the organic phase is washed with distilled water and saturated saline water for 3 times in sequence, then dried with anhydrous sodium sulfate, then vacuum filtration is carried out, and the filtrate is subjected to rotary evaporation to remove the solvent, thus obtaining intermediate 2;
step a3: adding 10mmol of 4-nitroaniline and 30mL of deionized water into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, dropwise adding 6mL of concentrated hydrochloric acid with the mass fraction of 38% under the condition of the temperature of 0 ℃ and the stirring rate of 500r/min, controlling the dropping rate to be 2 drops/s, continuously dropwise adding 8mL of sodium nitrite solution with the mass fraction of 18% after the dropping, controlling the dropping rate to be 2 drops/s, continuously stirring for reaction for 40min after the dropping, obtaining diazonium solution, adding 10mmol of p-benzoquinone, 20mmol of sodium bicarbonate and 50mL of distilled water into the three-neck flask, dropwise adding diazonium solution under the condition of the temperature of 5 ℃, controlling the dropping rate to be 2 drops/s, continuously stirring for reaction for 5h after the dropping, vacuum filtering the reaction product after the reaction is finished, washing the filter cake with saturated brine for 3 times, then placing the filter cake in a vacuum drying box, and drying for 3h under the condition of the temperature of 35 ℃ to obtain intermediate 3;
step a4: adding 10mmol of intermediate 3, 40mmol of zinc powder and 60mL of concentrated hydrochloric acid with mass fraction of 38% into a three-neck flask provided with a stirrer, a thermometer, a nitrogen inlet pipe and a reflux condenser, introducing nitrogen for protection, stirring and reacting for 30min under the condition of 30 ℃ and stirring rate of 500r/min, heating to reflux, continuing stirring and reacting for 10h, vacuum filtering while the mixture is hot, cooling the filtrate to below 0 ℃, precipitating precipitate, vacuum filtering, washing the filter cake with distilled water for 3 times, placing in a vacuum drying box, and drying for 3h under the condition of 55 ℃ to obtain intermediate 4;
step a5: 10mmol of intermediate 2, 10mmol of intermediate 4, 15mmol of anhydrous potassium carbonate, 30mL of dimethyl sulfoxide and 12mL of toluene are added into a three-neck flask provided with a stirrer, a thermometer and a nitrogen inlet pipe, nitrogen is introduced for protection, stirring is carried out for reaction for 40min under the condition of 30 ℃ and 500r/min of stirring rate, stirring is continued for reaction for 5h under the condition of heating to 145 ℃, stirring is continued for reaction for 2.5h under the condition of heating to 165 ℃, the reaction product is cooled to room temperature after the reaction is finished, then the reaction product is added into distilled water, then vacuum filtration is carried out, the filter cake is crushed, then the filter cake is placed in a vacuum drying box, and is dried for 5h under the condition of 75 ℃ to obtain intermediate 5;
step a6: 1g of intermediate 5, 0.5g of triethylamine and 35mL of methylene chloride were charged into a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, and reacted at a temperature of 5℃under stirring at a stirring rate of 500r/min for 20 minutes, followed by dropwise addition of 30mL of heptafluorobutyryl chloride with stirring according to 0.5g: and (3) 10mL of heptafluorobutyryl chloride solution formed by dissolving in dichloromethane, controlling the dropping speed to be 2 drops/s, continuously stirring and reacting for 5h under the condition of heating to 50 ℃ after the dropping, cooling the reaction product to room temperature after the reaction is finished, removing the solvent by rotary evaporation, washing 3 times by using distilled water, and then placing in a vacuum drying box and drying for 10h under the condition of 70 ℃ to obtain the super-hydrophobic resin.
Example 4:
the embodiment is a preparation method of a water treatment membrane of an MABR aeration bioreactor, comprising the following steps:
step one: weighing 30 parts of the super-hydrophobic resin in the example 1, 1.5 parts of polyvinylpyrrolidone and 100 parts of N, N-dimethylformamide according to parts by weight for later use;
step two: adding super-hydrophobic resin, polyvinylpyrrolidone and N, N-dimethylformamide into a three-neck flask provided with a stirrer and a thermometer, stirring and reacting for 15h under the condition that the temperature is 25 ℃ and the stirring speed is 400r/min, and standing for removing bubbles for 10h to obtain a casting film liquid;
step three: pouring the casting solution on PET non-woven fabric, scraping and coating by using a scraper with a gap of 200 mu m, soaking in deionized water coagulation bath, and curing to form a film to obtain the water treatment film of the MABR aeration bioreactor with the thickness of 10 mu m.
The performance of the water treatment membrane of the MABR aerated bioreactor of example 4 was tested, and the test results showed that: the oxygen transmission amount was 2465GPU and the surface water drop contact angle was 161 °.
Example 5:
the embodiment is a preparation method of a water treatment membrane of an MABR aeration bioreactor, comprising the following steps:
step one: weighing 32 parts of the super-hydrophobic resin in the example 2, 2.0 parts of polyvinylpyrrolidone and 105 parts of N, N-dimethylformamide according to parts by weight for later use;
step two: adding super-hydrophobic resin, polyvinylpyrrolidone and N, N-dimethylformamide into a three-neck flask provided with a stirrer and a thermometer, stirring and reacting for 18h under the condition that the temperature is 28 ℃ and the stirring speed is 450r/min, and standing for removing bubbles for 12h to obtain a casting film liquid;
step three: pouring the casting solution on PET non-woven fabric, scraping and coating by using a scraper with a gap of 200 mu m, soaking in deionized water coagulation bath, and curing to form a film to obtain the water treatment film of the MABR aeration bioreactor with the thickness of 10 mu m.
The performance of the water treatment membrane of the MABR aerated bioreactor of example 5 was tested, and the test results showed that: the oxygen transmission amount was 2481GPU and the surface water drop contact angle was 163 °.
Example 6:
the embodiment is a preparation method of a water treatment membrane of an MABR aeration bioreactor, comprising the following steps:
step one: weighing 35 parts of super-hydrophobic resin, 2.5 parts of polyvinylpyrrolidone and 110 parts of N, N-dimethylformamide in example 3 according to parts by weight for later use;
step two: adding super-hydrophobic resin, polyvinylpyrrolidone and N, N-dimethylformamide into a three-neck flask provided with a stirrer and a thermometer, stirring and reacting for 20h under the condition that the temperature is 30 ℃ and the stirring speed is 500r/min, and standing for removing bubbles for 15h to obtain a casting film liquid;
step three: pouring the casting solution on PET non-woven fabric, scraping and coating by using a scraper with a gap of 200 mu m, soaking in deionized water coagulation bath, and curing to form a film to obtain the water treatment film of the MABR aeration bioreactor with the thickness of 10 mu m.
The performance of the water treatment membrane of the MABR aerated bioreactor of example 6 was tested, and the test results showed that: the oxygen transmission amount is 2502GPU, and the surface water drop contact angle is 165 degrees.
The method for testing the oxygen transmission amount comprises the following steps: the temperature in the laboratory is controlled at (23+/-2), a pretreated sample is clamped between the test chambers by using an oxygen transmittance tester OTR-D3, oxygen or air flows on one side of the film, high-purity nitrogen flows on the other side of the film, oxygen molecules penetrate through the film and diffuse into the high-purity nitrogen on the other side, the flowing nitrogen is carried to the sensor, and the oxygen transmittance is calculated by analyzing the oxygen concentration measured by the sensor: the formula for calculating the GPU is:
wherein V represents the volume of permeated gas, t represents the permeation time, A represents the area of the permeable membrane, { circumflex }>Representing a pressure difference;
the method for testing the contact angle of the surface water drop comprises the following steps: the temperature in the laboratory was controlled at (23.+ -. 2). Degree.C, the pure water contact angle of the film was measured by a contact angle measuring instrument (SPCA, hake Test Instrument, china), 0.5uL of the droplet was slowly dropped on the smooth surface of the dried flat film by adjusting the syringe, after the droplet was stabilized for 5 seconds, the contact angle was measured, and the same film sample was measured in parallel for 5 times, and the average value was obtained.
Through experimental detection, the water treatment film has excellent hydrophobicity and is easy for oxygen to pass, so the following effects are provided for the water treatment film: the water treatment membrane of this application is difficult to by the wetting of water, and then makes the water treatment membrane can not adsorb moisture easily, has avoided moisture to block up the micropore on the water treatment membrane to guaranteed that oxygen can pass through easily, can be high-efficient, quick, a large amount of with the inboard conduction of water treatment membrane to the outside, provide sufficient oxygen for the microorganism, promote the growth of microorganism, improved the purification effect and the purification efficiency of microorganism to sewage.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (2)
- The water treatment membrane of the MABR aeration bioreactor is characterized by comprising the following components in parts by weight:30-35 parts of super-hydrophobic resin, 1.5-2.5 parts of polyvinylpyrrolidone and 100-110 parts of N, N-dimethylformamide;wherein, the super-hydrophobic resin is prepared by the following steps:step a1: adding pentafluorobenzoic acid and absolute ethyl alcohol into a three-neck flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, stirring and reacting for 30-50min under the conditions of 25-30 ℃ and stirring speed of 400-500r/min, then dropwise adding a potassium tert-butoxide solution while stirring, controlling the dropping speed to be 1-2 drops/s, continuing stirring and reacting for 2-3h after the dripping is finished, adding a reaction product into absolute ethyl ether after the reaction is finished, then carrying out vacuum suction filtration, placing a filter cake into a vacuum drying box, and drying for 2-3h under the conditions of 30-35 ℃ to obtain an intermediate 1; the dosage ratio of the pentafluorobenzoic acid, the absolute ethyl alcohol and the potassium tert-butoxide solution in the step a1 is 10mmol:20-25mL:10mL of the potassium tert-butoxide solution is prepared from 9-10mmol of potassium tert-butoxide: 10mL of a solution formed by dissolving the above-mentioned materials in absolute ethyl alcohol;step a2: adding the intermediate 1, cuprous iodide, 1, 10-phenanthroline, pentafluorobromine and diethylene glycol dimethyl ether into a three-neck flask provided with a stirrer, a thermometer and a nitrogen inlet pipe, introducing nitrogen for protection, stirring and reacting for 20-25min under the conditions of 25-30 ℃ and 400-500r/min of stirring rate, then continuously stirring and reacting for 25-30h under the conditions of heating to 130-135 ℃, cooling the reaction product to room temperature after the reaction is finished, then adding the reaction product into ethyl acetate, then vacuum suction filtering, standing and layering filtrate, washing an organic phase with distilled water and saturated saline water for 2-3 times in sequence, then drying with anhydrous sodium sulfate, vacuum suction filtering, and rotationally evaporating the filtrate to remove the solvent to obtain an intermediate 2; the dosage ratio of the intermediate 1, the cuprous iodide, the 1, 10-phenanthroline, the pentafluorobromide benzene and the diethylene glycol dimethyl ether in the step a2 is 10mmol:1.2-1.3mmol:0.2-0.25g:7-8mmol:40-50mL;step a3: adding 4-nitroaniline and deionized water into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, dropwise adding concentrated hydrochloric acid while stirring at a temperature of-5-0 ℃ and a stirring rate of 400-500r/min, controlling the dropwise adding rate to be 1-2 drops/s, continuously dropwise adding sodium nitrite solution after dropwise adding, controlling the dropwise adding rate to be 1-2 drops/s, continuously stirring for reaction for 30-40min after dropwise adding, obtaining diazonium solution, adding p-benzoquinone, sodium bicarbonate and distilled water into the three-neck flask, dropwise adding diazonium solution while stirring at a temperature of 0-5 ℃, controlling the dropwise adding rate to be 1-2 drops/s, continuously stirring for reaction for 4-5h after dropwise adding, vacuum filtering a reaction product after the reaction, washing a filter cake with saturated saline solution for 2-3 times, then placing in a vacuum drying box, and drying for 2-3h at a temperature of 30-35 ℃ to obtain an intermediate 3; the dosage ratio of the 4-nitroaniline, deionized water, concentrated hydrochloric acid, sodium nitrite solution, p-benzoquinone, sodium bicarbonate and distilled water in the step a3 is 10mmol:25-30mL:5-6mL:6-8mL:10mmol:15-20mmol:40-50mL, wherein the mass fraction of the concentrated hydrochloric acid is 36-38%, and the mass fraction of the sodium nitrite solution is 15-18%;step a4: adding the intermediate 3, zinc powder and concentrated hydrochloric acid into a three-neck flask provided with a stirrer, a thermometer, a nitrogen inlet pipe and a reflux condenser, introducing nitrogen for protection, stirring and reacting for 25-30min under the condition that the temperature is 25-30 ℃ and the stirring speed is 400-500r/min, heating to reflux, continuing stirring and reacting for 8-10h, vacuum filtering while hot, cooling filtrate to below 0 ℃, precipitating precipitate, vacuum filtering, washing a filter cake with distilled water for 2-3 times, placing in a vacuum drying box, and drying for 2-3h under the condition that the temperature is 50-55 ℃ to obtain an intermediate 4; the dosage ratio of the intermediate 3, zinc powder and concentrated hydrochloric acid in the step a4 is 10mmol:35-40mmol:50-60mL, wherein the mass fraction of the concentrated hydrochloric acid is 36-38%;step a5: adding the intermediate 2, the intermediate 4, anhydrous potassium carbonate, dimethyl sulfoxide and toluene into a three-neck flask provided with a stirrer, a thermometer and a nitrogen inlet pipe, introducing nitrogen for protection, stirring and reacting for 30-40min under the condition that the temperature is 25-30 ℃ and the stirring rate is 400-500r/min, then continuously stirring and reacting for 4-5h under the condition that the temperature is raised to 140-145 ℃, then continuously stirring and reacting for 2-2.5h under the condition that the temperature is raised to 160-165 ℃, cooling the reaction product to room temperature after the reaction is finished, adding into distilled water, then carrying out vacuum suction filtration, crushing a filter cake, and then placing in a vacuum drying box, and drying for 4-5h under the condition that the temperature is 70-75 ℃ to obtain an intermediate 5; the dosage ratio of the intermediate 2, the intermediate 4, the anhydrous potassium carbonate, the dimethyl sulfoxide and the toluene in the step a5 is 10mmol:10mmol:13-15mmol:25-30mL:10-12mL;step a6: adding the intermediate 5, triethylamine and methylene dichloride into a four-mouth flask provided with a stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, stirring and reacting for 15-20min under the conditions of 0-5 ℃ and stirring speed of 400-500r/min, then adding the heptafluorobutyryl chloride solution dropwise while stirring, controlling the dropping speed to be 1-2 drops/s, continuously stirring and reacting for 4-5h under the conditions of heating to 45-50 ℃ after the dripping is finished, cooling the reaction product to room temperature after the reaction is finished, rotationally evaporating to remove the solvent, washing for 2-3 times with distilled water, then placing in a vacuum drying box, and drying for 8-10h under the conditions of 65-70 ℃ to obtain the super-hydrophobic resin; the dosage ratio of the intermediate 5, triethylamine, methylene chloride and heptafluorobutyryl chloride solution in the step a6 is 1g:0.3-0.5g:30-35mL:15-30mL of the heptafluorobutyryl chloride solution is heptafluorobutyryl chloride according to 0.5g:10mL of the solution was dissolved in methylene chloride.
- 2. A method for preparing a water treatment membrane of an MABR aerated bioreactor according to claim 1, comprising the steps of:step one: weighing 30-35 parts of super-hydrophobic resin, 1.5-2.5 parts of polyvinylpyrrolidone and 100-110 parts of N, N-dimethylformamide according to parts by weight for later use;step two: adding super-hydrophobic resin, polyvinylpyrrolidone and N, N-dimethylformamide into a three-neck flask with a stirrer and a thermometer, stirring and reacting for 15-20h under the conditions that the temperature is 25-30 ℃ and the stirring speed is 400-500r/min, and standing for removing bubbles for 10-15h to obtain a casting film liquid;step three: pouring the casting solution on PET non-woven fabric, scraping and coating by using a scraper with a gap of 200 mu m, soaking in deionized water coagulation bath, and curing to form a film to obtain the water treatment film of the MABR aeration bioreactor.
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| CN113307999A (en) * | 2021-05-27 | 2021-08-27 | 长春工业大学 | Preparation method of amino polyaryletherketone/graphene oxide composite material |
| WO2023197565A1 (en) * | 2022-04-11 | 2023-10-19 | 华南理工大学 | Fibrous root-like self-repairing and anti-pollution zno/mxene base membrane and preparation method therefor and application thereof |
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| WO2021097819A1 (en) * | 2019-11-22 | 2021-05-27 | 万华化学集团股份有限公司 | Superhydrophobic membrane and preparation method therefor, and method for concentrating and recycling mdi waste brine |
| CN113307999A (en) * | 2021-05-27 | 2021-08-27 | 长春工业大学 | Preparation method of amino polyaryletherketone/graphene oxide composite material |
| WO2023197565A1 (en) * | 2022-04-11 | 2023-10-19 | 华南理工大学 | Fibrous root-like self-repairing and anti-pollution zno/mxene base membrane and preparation method therefor and application thereof |
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