CN111282552A - Membrane material for industrial wastewater treatment - Google Patents
Membrane material for industrial wastewater treatment Download PDFInfo
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- CN111282552A CN111282552A CN202010110209.9A CN202010110209A CN111282552A CN 111282552 A CN111282552 A CN 111282552A CN 202010110209 A CN202010110209 A CN 202010110209A CN 111282552 A CN111282552 A CN 111282552A
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- industrial wastewater
- membrane material
- wastewater treatment
- black phosphorus
- vinyl
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- 239000000463 material Substances 0.000 title claims abstract description 98
- 239000012528 membrane Substances 0.000 title claims abstract description 68
- 239000010842 industrial wastewater Substances 0.000 title claims abstract description 64
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 45
- -1 vinyl modified black phosphorus Chemical class 0.000 claims abstract description 69
- 239000002096 quantum dot Substances 0.000 claims abstract description 43
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 94
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 84
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 42
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 42
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical class [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 41
- 238000002360 preparation method Methods 0.000 claims description 39
- 238000002390 rotary evaporation Methods 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 29
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 21
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 21
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 17
- WHSQATVVMVBGNS-UHFFFAOYSA-N 4-[4,6-bis(4-aminophenyl)-1,3,5-triazin-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C1=NC(C=2C=CC(N)=CC=2)=NC(C=2C=CC(N)=CC=2)=N1 WHSQATVVMVBGNS-UHFFFAOYSA-N 0.000 claims description 16
- 239000004593 Epoxy Substances 0.000 claims description 15
- DELJOESCKJGFML-DUXPYHPUSA-N (e)-3-aminobut-2-enenitrile Chemical compound C\C(N)=C/C#N DELJOESCKJGFML-DUXPYHPUSA-N 0.000 claims description 14
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 14
- MFEILWXBDBCWKF-UHFFFAOYSA-N 3-phenylpropanoyl chloride Chemical compound ClC(=O)CCC1=CC=CC=C1 MFEILWXBDBCWKF-UHFFFAOYSA-N 0.000 claims description 14
- OTRAYOBSWCVTIN-UHFFFAOYSA-N OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N Chemical compound OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N OTRAYOBSWCVTIN-UHFFFAOYSA-N 0.000 claims description 14
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 14
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 14
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 230000009471 action Effects 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 230000005764 inhibitory process Effects 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 18
- 150000002500 ions Chemical class 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 239000002351 wastewater Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 4
- 229940043267 rhodamine b Drugs 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 238000007605 air drying Methods 0.000 description 3
- 238000009388 chemical precipitation Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- WOGITNXCNOTRLK-VOTSOKGWSA-N (e)-3-phenylprop-2-enoyl chloride Chemical compound ClC(=O)\C=C\C1=CC=CC=C1 WOGITNXCNOTRLK-VOTSOKGWSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000194 supercritical-fluid extraction Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- YUXBNNVWBUTOQZ-UHFFFAOYSA-N 4-phenyltriazine Chemical compound C1=CC=CC=C1C1=CC=NN=N1 YUXBNNVWBUTOQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000010893 electron trap Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910001987 mercury nitrate Inorganic materials 0.000 description 1
- DRXYRSRECMWYAV-UHFFFAOYSA-N nitrooxymercury Chemical compound [Hg+].[O-][N+]([O-])=O DRXYRSRECMWYAV-UHFFFAOYSA-N 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000010998 test method 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
-
- 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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/36—Polytetrafluoroethene
-
- 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
- B01D71/54—Polyureas; Polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a membrane material for industrial wastewater treatment, which is characterized by being prepared by polymerizing 3-6 parts of vinyl modified black phosphorus boride quantum dots, 8-12 parts of vinyl-terminated hyperbranched poly (amine-ester) and 1-3 parts of β -phenylacryloyl chloride modified 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine by free radicals through the following polymerizable monomers in parts by weight.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a membrane material for industrial wastewater treatment and a preparation method thereof.
Background
In recent years, with the development of economy and the progress of global industrialization, a large amount of industrial wastewater and urban domestic sewage containing heavy metals are discharged into the environment, which brings serious threats to the atmosphere, soil and water environment, especially human health, and if the industrial wastewater and the urban domestic sewage are not treated, the industrial wastewater and the urban domestic sewage can cause serious damage to the heart, the kidney, the liver and other important organs of the human body. Therefore, the search for effective industrial wastewater treatment technology becomes the focus of urgent attention in the industry at present.
At present, the treatment method of industrial wastewater containing heavy metals mainly comprises the following steps: chemical precipitation, electrochemical, adsorption, photocatalytic and supercritical fluid extraction. Chemical precipitation methods are mostly adopted in industry, but the chemical precipitation methods easily cause secondary pollution, are not thorough in treatment of low-concentration heavy metal ions, and are difficult to be applied to treatment of flowing water bodies; the electrochemical method has large power consumption and is not suitable for large-scale treatment; the photocatalysis method is an environment-friendly treatment method, but has higher cost, low efficiency and narrow visible light response range; although the supercritical fluid extraction method has simple flow, high extraction speed and low energy consumption, the cost is too high, and large-scale wastewater treatment cannot be realized.
In recent years, the membrane separation technology is rapidly developed as a novel water treatment process in the aspect of treating wastewater which is difficult to treat, and the membrane material with the treatment functions of adsorbing heavy metal ions and other toxic and harmful organic matters in industrial wastewater is adopted to treat the industrial wastewater, so that the industrial wastewater treatment method has the advantages of low cost, easiness in recovery and separation and high treatment efficiency. However, the membrane material for industrial wastewater treatment in the prior art has the defects of high membrane cost, poor strength, poor corrosion resistance, serious membrane pollution and the like, so that the further popularization and application of the membrane material in the treatment of industrial wastewater containing heavy metals are greatly influenced and restricted; in addition, most of the membrane materials for industrial wastewater treatment in the market only have the functions of filtering and separating wastewater, the capabilities of catalyzing organic matters in the wastewater to decompose and adsorb and separate heavy metal ions are poor, and the mechanical properties and the performance stability of the membrane materials need to be further improved.
The Chinese patent with application number 200710056397.6 discloses a heavy metal ion adsorption film and a preparation method thereof, wherein the heavy metal ion adsorption film is composed of polyvinyl alcohol and amino polymer, and the weight ratio of polyvinyl alcohol: the mass ratio of the amino polymer is (95:5) - (20: 80); the amine-based polymer is polyvinylamine, polyallylamine and branched polyethyleneimine. Introducing an amine-based polymer into a polyvinyl alcohol aqueous solution, and crosslinking by a crosslinking agent to form a three-dimensional polymer network. The method is simple and easy to implement, and no organic solvent is used in the preparation process. The introduction of the amino group effectively enhances the water swelling property of the polyvinyl alcohol membrane, and simultaneously greatly improves the adsorption capacity of the membrane to heavy metal ions. However, the method consumes a large amount of amino groups in the crosslinking process, reduces the capacity of treating heavy metal ions, and has no efficacy of catalytically decomposing toxic and harmful organic matters in industrial wastewater.
Therefore, the development of the membrane material for treating the industrial wastewater, which has good treatment effect on the industrial wastewater containing the heavy metal ions, high efficiency, good mechanical property, corrosion resistance and pollution resistance, and particularly has strong capability of catalyzing the decomposition of organic matters in the wastewater and adsorbing and separating the heavy metal ions in the wastewater, meets the market demand, has wide market value and application prospect, and has very important significance for promoting the development of the industrial wastewater treatment industry.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a membrane material for industrial wastewater treatment and a preparation method thereof, and the preparation method has the advantages of simple process, convenient operation, low energy consumption, suitability for continuous large-scale production, and higher economic value, social value and ecological value; the prepared membrane material for treating industrial wastewater has good treatment effect on the industrial wastewater containing heavy metal ions, high efficiency, good mechanical property, corrosion resistance and pollution resistance, and especially strong capability of catalyzing the decomposition of organic matters in the wastewater and adsorbing and separating the heavy metal ions in the wastewater.
In order to achieve the purpose, the invention adopts the technical scheme that the membrane material for treating the industrial wastewater is characterized by being prepared by polymerizing 3-6 parts of vinyl modified black phosphorus boride quantum dots, 8-12 parts of vinyl-terminated hyperbranched poly (amine-ester) and 1-3 parts of β -phenylacryloyl chloride modified 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine by the following polymerizable monomers in parts by weight through free radicals.
Preferably, the preparation method of the vinyl modified black phosphorus boride quantum dot comprises the following steps:
s1, placing the black phosphorus quantum dots, ammonium pentaborate, Tween 20 and ethanol in a polytetrafluoroethylene reaction kettle, preserving the heat for 8-12 hours at the temperature of 150-;
and S2, adding the black phosphorus boride quantum dot prepared in the step S1 into ethanol, adding vinyl triethoxysilane into the ethanol, stirring the mixture for 6 to 8 hours at the temperature of between 60 and 80 ℃, and then performing rotary evaporation to remove the ethanol to obtain the vinyl modified black phosphorus boride quantum dot.
Preferably, the mass ratio of the black phosphorus quantum dots, the ammonium pentaborate, the tween 20 and the ethanol in the step S1 is 1 (0.05-0.15) to 0.1 (5-10).
Preferably, the mass ratio of the black phosphorus boride quantum dot, the ethanol and the vinyltriethoxysilane in the step S2 is 1 (3-5) to (0.1-0.3).
Preferably, the preparation method of the vinyl-terminated hyperbranched poly (amine-ester) comprises the following steps: adding the third-generation epoxy end group amino hyperbranched poly (amine-ester) and 3-aminocrotonitrile into tetrahydrofuran, stirring and reacting for 6-8 hours at 50-60 ℃ under the action of oxygen inhibition, and then removing the tetrahydrofuran by rotary evaporation to obtain the vinyl-terminated hyperbranched poly (amine-ester).
Preferably, the molar ratio of the third-generation epoxy terminal group amino hyperbranched poly (amine-ester), the 3-aminocrotonitrile and the tetrahydrofuran is 1 (5-8) to (30-40).
Preferably, the third generation epoxy terminal amine hyperbranched poly (amine-ester) is prepared by the following method: chinese patent application No. 200910067539.8, example 9.
Preferably, the preparation method of β -phenylpropionyl chloride modified 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine comprises the following steps of adding β -phenylpropionyl chloride, 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine and triethylamine into tetrahydrofuran, stirring and reacting at 25-35 ℃ for 3-6 hours, removing tetrahydrofuran by rotary evaporation after the reaction is finished, extracting with water and acetone in a mass ratio of 3:1, taking an oil phase, removing water by anhydrous magnesium sulfate, filtering, and removing acetone by rotary evaporation to obtain β -phenylpropionyl chloride modified 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine.
Preferably, the mole ratio of β -phenyl acryloyl chloride, 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, triethylamine and tetrahydrofuran is 3:1 (0.4-0.7) to (12-18).
Another object of the present invention is to provide a method for preparing the membrane material for industrial wastewater treatment, which comprises the following steps: mixing all polymerizable monomers to form a mixed material, then adding the mixed material and an initiator into a high-boiling-point solvent, stirring and reacting for 1-3 hours at 70-80 ℃ in a nitrogen or inert gas atmosphere, then pouring the mixed material on a polytetrafluoroethylene template, and placing the polytetrafluoroethylene template in an air-blast drying box at 80-90 ℃ to dry to constant weight to obtain the membrane material for industrial wastewater treatment.
Preferably, the mass ratio of the mixed material, the initiator and the high-boiling point solvent is 1 (0.01-0.02) to 3-5.
Preferably, the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile.
Preferably, the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
Preferably, the inert gas is one of helium, neon and argon.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
(1) the preparation method of the membrane material for industrial wastewater treatment provided by the invention has the advantages of simple process, convenience in operation, low energy consumption, suitability for continuous large-scale production, higher economic value and proper social value and ecological value.
(2) The membrane material for industrial wastewater treatment provided by the invention overcomes the defects that the membrane material membrane for industrial wastewater treatment in the prior art is high in cost, poor in strength, poor in corrosion resistance and serious in membrane pollution, mostly only has the function of filtering and separating wastewater, is poor in the capability of decomposing organic matters in catalytic wastewater and adsorbing and separating heavy metal ions, and the mechanical property and the performance stability of the membrane material are required to be further improved.
(3) According to the film material for treating industrial wastewater, the introduction of the vinyl modified black phosphorus boride quantum dots can effectively adsorb toxic and harmful substances in the industrial wastewater and can also play a role in catalytically decomposing organic matters; the environmental stability of the black phosphorus quantum dots is improved and the electron trap state is eliminated at the same time through boronization, so that the photocatalysis efficiency is effectively improved; vinyl groups are modified on the black phosphorus boride quantum dots through the bridging action and then polymerized to form a film, so that the compatibility of the black phosphorus boride quantum dots with a polymer material and the dispersion uniformity of the black phosphorus boride quantum dots are effectively improved, and the performance stability of the film material is further improved.
(4) The membrane material for treating industrial wastewater provided by the invention has the advantages that 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine modified by β -phenyl acryloyl chloride is introduced into a phenyl triazine conjugated structure, so that the membrane material can play a role of an organic photocatalyst, the wastewater treatment effect is improved, and the membrane material enters a molecular chain of the membrane material through vinyl modification, so that the corrosion resistance, the pollution resistance and the performance stability of the membrane can be effectively improved.
(5) The membrane material for treating industrial wastewater provided by the invention is free of inorganic filler, and effectively avoids the influence of the addition of the inorganic filler on the processing fluidity and the long-term service performance stability of the membrane material, and the β -phenylpropionyl chloride modified 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine and vinyl modified boronized black phosphorus quantum dots are adopted to act synergistically, so that the catalytic efficiency is higher, the comprehensive performance of the membrane is better, and compared with the prior art in which only a triazine structure is added, a benzene ring structure is not present, only quantum dots are added, and the membrane material which is neither boronized nor modified is better in performance stability, wastewater treatment effect and efficiency.
(6) The film material for treating industrial waste water provided by the invention has the advantages that the amino group on the vinyl-terminated hyperbranched poly (amine-ester) can effectively improve the chelation effect on heavy metal ions, and further is favorable for adsorbing the heavy metal ions, the hyperbranched structure is favorable for wetting the surface and effectively adsorbing toxic and harmful substances in water, the film material is subjected to synergistic action with β -phenyl acryloyl chloride modified 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, the hydrophilic group and the hydrophobic group are reasonably arranged, so that the film material is favorable for treating waste water, can keep the pollution resistance and corrosion resistance of the film material and prolong the service life of the film material, and the film material forms a three-dimensional network structure after being polymerized, so that the mechanical property and the comprehensive property of the film material are effectively improved.
Detailed Description
In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
The preparation method of the third-generation epoxy terminal group amino hyperbranched poly (amine-ester) in the embodiment of the invention is as follows: chinese invention patent example 9 with application number 200910067539.8; other raw materials were all purchased commercially.
Example 1
A membrane material for treating industrial wastewater is prepared by polymerizing 3 parts of vinyl modified black phosphorus boride quantum dots, 8 parts of vinyl-terminated hyperbranched poly (amine-ester) and 1 part of β -phenyl acryloyl chloride modified 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine by using free radicals as polymerizable monomers.
The preparation method of the vinyl modified black phosphorus boride quantum dot comprises the following steps:
step S1, placing the black phosphorus quantum dots, ammonium pentaborate, Tween 20 and ethanol in a polytetrafluoroethylene reaction kettle, preserving the heat for 8 hours at 150 ℃, cooling to room temperature, removing the ethanol by rotary evaporation, dispersing in water, centrifuging, and drying at 85 ℃ to constant weight to obtain the boronized black phosphorus quantum dots; the mass ratio of the black phosphorus quantum dots to the ammonium pentaborate to the tween-20 to the ethanol is 1:0.05:0.1: 5;
step S2, adding the black phosphorus boride quantum dot prepared in the step S1 into ethanol, adding vinyltriethoxysilane into the ethanol, stirring the mixture for 6 hours at the temperature of 60 ℃, and then performing rotary evaporation to remove the ethanol to obtain a vinyl modified black phosphorus boride quantum dot; the mass ratio of the black phosphorus boride quantum dot to the ethanol to the vinyl triethoxysilane is 1:3: 0.1.
The preparation method of the vinyl-terminated hyperbranched poly (amine-ester) comprises the following steps: adding the third-generation epoxy end group amino hyperbranched poly (amine-ester) and 3-aminocrotonitrile into tetrahydrofuran, stirring and reacting for 6 hours at 50 ℃ under the action of oxygen inhibition, and then removing the tetrahydrofuran by rotary evaporation to obtain vinyl-terminated hyperbranched poly (amine-ester); the molar ratio of the third-generation epoxy end group amino hyperbranched poly (amine-ester), 3-aminocrotonitrile and tetrahydrofuran is 1:5: 30.
The preparation method of β -phenylpropionyl chloride modified 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine comprises the following steps of adding β -phenylpropionyl chloride, 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine and triethylamine into tetrahydrofuran, stirring and reacting for 3 hours at 25 ℃, removing tetrahydrofuran by rotary evaporation after the reaction is finished, extracting with water and acetone in a mass ratio of 3:1, taking an oil phase, removing water by anhydrous magnesium sulfate, filtering, and removing acetone by rotary evaporation to obtain β -phenylpropionyl chloride modified 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, wherein the molar ratio of β -phenylpropionyl chloride, 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, triethylamine and tetrahydrofuran is 3:1:0.4: 12.
A preparation method of the membrane material for industrial wastewater treatment comprises the following steps: mixing all polymerizable monomers to form a mixed material, then adding the mixed material and azobisisobutyronitrile into dimethyl sulfoxide, stirring and reacting for 1 hour at 70 ℃ in a nitrogen atmosphere, then pouring the mixed material on a polytetrafluoroethylene template, and placing the polytetrafluoroethylene template in a forced air drying oven at 80 ℃ to dry to constant weight to obtain the membrane material for industrial wastewater treatment; the mass ratio of the mixed material, the azodiisobutyronitrile and the dimethyl sulfoxide is 1:0.01: 3.
Example 2
A membrane material for treating industrial wastewater is prepared by polymerizing polymerizable monomers by weight through 4 parts of vinyl modified black phosphorus boride quantum dots, 9 parts of vinyl-terminated hyperbranched poly (amine-ester), and β -phenyl acryloyl chloride modified 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine by free radicals.
The preparation method of the vinyl modified black phosphorus boride quantum dot comprises the following steps:
step S1, placing the black phosphorus quantum dots, ammonium pentaborate, Tween 20 and ethanol in a polytetrafluoroethylene reaction kettle, preserving the heat for 9 hours at 155 ℃, cooling to room temperature, removing the ethanol by rotary evaporation, dispersing in water, centrifuging, and drying at 87 ℃ to constant weight to obtain the boronized black phosphorus quantum dots; the mass ratio of the black phosphorus quantum dots to the ammonium pentaborate to the tween-20 to the ethanol is 1:0.07:0.1: 6;
step S2, adding the black phosphorus boride quantum dot prepared in the step S1 into ethanol, adding vinyl triethoxysilane into the ethanol, stirring the mixture for 6.5 hours at 65 ℃, and then performing rotary evaporation to remove the ethanol to obtain a vinyl modified black phosphorus boride quantum dot; the mass ratio of the black phosphorus boride quantum dot to the ethanol to the vinyl triethoxysilane is 1:3.5: 0.15.
The preparation method of the vinyl-terminated hyperbranched poly (amine-ester) comprises the following steps: adding the third-generation epoxy end group amino hyperbranched poly (amine-ester) and 3-aminocrotonitrile into tetrahydrofuran, stirring and reacting for 6.5 hours at 52 ℃ under the action of oxygen inhibition, and then removing the tetrahydrofuran by rotary evaporation to obtain vinyl-terminated hyperbranched poly (amine-ester); the molar ratio of the third-generation epoxy end group amino hyperbranched poly (amine-ester), 3-aminocrotonitrile and tetrahydrofuran is 1:6: 32.
The preparation method of β -phenylpropionyl chloride modified 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine comprises the following steps of adding β -phenylpropionyl chloride, 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine and triethylamine into tetrahydrofuran, stirring and reacting for 4 hours at 27 ℃, removing tetrahydrofuran by rotary evaporation after the reaction is finished, extracting with water and acetone in a mass ratio of 3:1, taking an oil phase, removing water by anhydrous magnesium sulfate, filtering, and removing acetone by rotary evaporation to obtain β -phenylpropionyl chloride modified 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, wherein the molar ratio of β -phenylpropionyl chloride, 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, triethylamine and tetrahydrofuran is 3:1:0.5: 13.
A preparation method of the membrane material for industrial wastewater treatment comprises the following steps: mixing all polymerizable monomers to form a mixed material, then adding the mixed material and azobisisoheptonitrile into N, N-dimethylformamide, stirring and reacting for 1.5 hours at 73 ℃ in a helium atmosphere, then pouring the mixed material on a polytetrafluoroethylene template, and placing the polytetrafluoroethylene template in a forced air drying oven at 82 ℃ to dry to constant weight to obtain the membrane material for industrial wastewater treatment; the mass ratio of the mixed material, the azobisisoheptonitrile and the N, N-dimethylformamide is 1:0.013: 3.5.
Example 3
A membrane material for treating industrial wastewater is prepared by polymerizing vinyl modified black phosphorus boride quantum dots 4.5 parts, vinyl-terminated hyperbranched poly (amine-ester) 10 parts and β -phenyl acryloyl chloride modified 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine 2 parts by weight of all polymerizable monomers through free radicals.
The preparation method of the vinyl modified black phosphorus boride quantum dot comprises the following steps:
step S1, placing the black phosphorus quantum dots, ammonium pentaborate, Tween 20 and ethanol in a polytetrafluoroethylene reaction kettle, preserving the heat for 10 hours at 160 ℃, cooling to room temperature, removing the ethanol by rotary evaporation, dispersing in water, centrifuging, and drying at 90 ℃ to constant weight to obtain the boronized black phosphorus quantum dots; the mass ratio of the black phosphorus quantum dots to the ammonium pentaborate to the tween-20 to the ethanol is 1:0.1:0.1: 7;
step S2, adding the black phosphorus boride quantum dot prepared in the step S1 into ethanol, adding vinyltriethoxysilane into the ethanol, stirring the mixture at 70 ℃ for 7 hours, and then performing rotary evaporation to remove the ethanol to obtain a vinyl modified black phosphorus boride quantum dot; the mass ratio of the black phosphorus boride quantum dot to the ethanol to the vinyl triethoxysilane is 1:4: 0.2.
The preparation method of the vinyl-terminated hyperbranched poly (amine-ester) comprises the following steps: adding the third-generation epoxy end group amino hyperbranched poly (amine-ester) and 3-aminocrotonitrile into tetrahydrofuran, stirring and reacting for 7 hours at 55 ℃ under the action of oxygen inhibition, and then removing the tetrahydrofuran by rotary evaporation to obtain vinyl-terminated hyperbranched poly (amine-ester); the molar ratio of the third-generation epoxy end group amino hyperbranched poly (amine-ester), 3-aminocrotonitrile and tetrahydrofuran is 1:6.5: 35.
The preparation method of β -phenylpropionyl chloride modified 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine comprises the following steps of adding β -phenylpropionyl chloride, 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine and triethylamine into tetrahydrofuran, stirring and reacting for 4.5 hours at 30 ℃, removing tetrahydrofuran by rotary evaporation after the reaction is finished, extracting with water and acetone in a mass ratio of 3:1, taking an oil phase, removing water by anhydrous magnesium sulfate, filtering, and removing acetone by rotary evaporation to obtain β -phenylpropionyl chloride modified 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, wherein the molar ratio of β -phenylpropionyl chloride, 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, triethylamine and tetrahydrofuran is 3:1:0.55: 15.
A preparation method of the membrane material for industrial wastewater treatment comprises the following steps: mixing all polymerizable monomers to form a mixed material, then adding the mixed material and azobisisobutyronitrile into N, N-dimethylacetamide, stirring and reacting for 2 hours at 75 ℃ in a neon atmosphere, then pouring the mixed material on a polytetrafluoroethylene template, and placing the polytetrafluoroethylene template in a forced air drying oven at 85 ℃ to dry to constant weight to obtain the membrane material for industrial wastewater treatment; the mass ratio of the mixed material, azodiisobutyronitrile and N, N-dimethylacetamide is 1:0.015: 4.
Example 4
A membrane material for treating industrial wastewater is prepared by polymerizing the following polymerizable monomers in parts by weight through free radicals, wherein the polymerizable monomers comprise 5 parts of vinyl modified black phosphorus boride quantum dots, 11 parts of vinyl-terminated hyperbranched poly (amine-ester), and β -phenyl acryloyl chloride modified 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine 2.5 parts.
The preparation method of the vinyl modified black phosphorus boride quantum dot comprises the following steps:
step S1, placing the black phosphorus quantum dots, ammonium pentaborate, Tween 20 and ethanol in a polytetrafluoroethylene reaction kettle, preserving the heat for 11 hours at 165 ℃, cooling to room temperature, removing the ethanol by rotary evaporation, dispersing in water, centrifuging, and drying at 93 ℃ to constant weight to obtain the boronized black phosphorus quantum dots; the mass ratio of the black phosphorus quantum dots to the ammonium pentaborate to the tween-20 to the ethanol is 1:0.13:0.1: 9;
step S2, adding the black phosphorus boride quantum dot prepared in the step S1 into ethanol, adding vinyltriethoxysilane into the ethanol, stirring the mixture at 77 ℃ for 7.5 hours, and then performing rotary evaporation to remove the ethanol to obtain a vinyl modified black phosphorus boride quantum dot; the mass ratio of the black phosphorus boride quantum dot to the ethanol to the vinyl triethoxysilane is 1:4.7: 0.28.
The preparation method of the vinyl-terminated hyperbranched poly (amine-ester) comprises the following steps: adding the third-generation epoxy end group amino hyperbranched poly (amine-ester) and 3-aminocrotonitrile into tetrahydrofuran, stirring and reacting for 7.8 hours at 58 ℃ under the action of oxygen inhibition, and then removing the tetrahydrofuran by rotary evaporation to obtain vinyl-terminated hyperbranched poly (amine-ester); the molar ratio of the third-generation epoxy end group amino hyperbranched poly (amine-ester), 3-aminocrotonitrile and tetrahydrofuran is 1:7.5: 37.
The preparation method of β -phenylpropionyl chloride modified 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine comprises the following steps of adding β -phenylpropionyl chloride, 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine and triethylamine into tetrahydrofuran, stirring and reacting for 5.5 hours at 33 ℃, removing tetrahydrofuran by rotary evaporation after the reaction is finished, extracting with water and acetone in a mass ratio of 3:1, taking an oil phase, removing water by anhydrous magnesium sulfate, filtering, and removing acetone by rotary evaporation to obtain β -phenylpropionyl chloride modified 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, wherein the molar ratio of β -phenylpropionyl chloride, 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, triethylamine and tetrahydrofuran is 3:1:0.65: 17.
A preparation method of the membrane material for industrial wastewater treatment comprises the following steps: mixing all polymerizable monomers to form a mixed material, then adding the mixed material and an initiator into a high-boiling-point solvent, stirring and reacting for 2.6 hours at 78 ℃ in an argon atmosphere, then pouring the mixed material on a polytetrafluoroethylene template, and placing the polytetrafluoroethylene template in an air-blast drying oven at 88 ℃ to dry to constant weight to obtain the membrane material for industrial wastewater treatment; the mass ratio of the mixed material to the initiator to the high-boiling-point solvent is 1:0.018: 4.7; the initiator is formed by mixing azodiisobutyronitrile and azodiisoheptonitrile according to the mass ratio of 3: 5; the high boiling point solvent is formed by mixing dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone according to a mass ratio of 1:3:2: 4.
Example 5
A membrane material for treating industrial wastewater is prepared by polymerizing vinyl modified black phosphorus boride quantum dots 6 parts, vinyl-terminated hyperbranched poly (amine-ester) 12 parts and β -phenyl acryloyl chloride modified 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine 3 parts by weight of each polymerizable monomer through free radicals.
The preparation method of the vinyl modified black phosphorus boride quantum dot comprises the following steps:
step S1, placing the black phosphorus quantum dots, ammonium pentaborate, Tween 20 and ethanol in a polytetrafluoroethylene reaction kettle, preserving the heat for 12 hours at 170 ℃, cooling to room temperature, removing the ethanol by rotary evaporation, dispersing in water, centrifuging, and drying at 95 ℃ to constant weight to obtain the boronized black phosphorus quantum dots; the mass ratio of the black phosphorus quantum dots to the ammonium pentaborate to the tween-20 to the ethanol is 1:0.15:0.1: 10;
step S2, adding the black phosphorus boride quantum dot prepared in the step S1 into ethanol, adding vinyltriethoxysilane into the ethanol, stirring the mixture for 8 hours at the temperature of 80 ℃, and then performing rotary evaporation to remove the ethanol to obtain a vinyl modified black phosphorus boride quantum dot; the mass ratio of the black phosphorus boride quantum dot to the ethanol to the vinyl triethoxysilane is 1:5: 0.3.
The preparation method of the vinyl-terminated hyperbranched poly (amine-ester) comprises the following steps: adding the third-generation epoxy end group amino hyperbranched poly (amine-ester) and 3-aminocrotonitrile into tetrahydrofuran, stirring and reacting for 8 hours at 60 ℃ under the action of oxygen inhibition, and then removing the tetrahydrofuran by rotary evaporation to obtain vinyl-terminated hyperbranched poly (amine-ester); the molar ratio of the third-generation epoxy end group amino hyperbranched poly (amine-ester), 3-aminocrotonitrile and tetrahydrofuran is 1:8: 40.
The preparation method of β -phenylpropionyl chloride modified 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine comprises the following steps of adding β -phenylpropionyl chloride, 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine and triethylamine into tetrahydrofuran, stirring and reacting for 6 hours at 35 ℃, removing tetrahydrofuran by rotary evaporation after the reaction is finished, extracting with water and acetone in a mass ratio of 3:1, taking an oil phase, removing water by anhydrous magnesium sulfate, filtering, and removing acetone by rotary evaporation to obtain β -phenylpropionyl chloride modified 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, wherein the molar ratio of β -phenylpropionyl chloride, 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, triethylamine and tetrahydrofuran is 3:1:0.7: 18.
A preparation method of the membrane material for industrial wastewater treatment comprises the following steps: mixing all polymerizable monomers to form a mixed material, then adding the mixed material and azobisisobutyronitrile into N-methylpyrrolidone, stirring and reacting for 3 hours at 80 ℃ in a nitrogen atmosphere, then pouring the mixed material on a polytetrafluoroethylene template, and placing the polytetrafluoroethylene template in a blowing drying oven at 90 ℃ to dry to constant weight to obtain the membrane material for industrial wastewater treatment; the mass ratio of the mixed material, azodiisobutyronitrile and N-methylpyrrolidone is 1:0.02: 5.
Comparative example 1
The present example provides a membrane material for industrial wastewater treatment, which has a formulation and a preparation method substantially the same as those of example 1, except that vinyl modified boronized black phosphorus quantum dots are not added.
Comparative example 2
This example provides a membrane material for industrial wastewater treatment having substantially the same formulation and preparation method as in example 1, except that β -phenylpropionyl chloride was not added to modify 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine.
Comparative example 3
The present example provides a membrane material for industrial wastewater treatment, the formulation and preparation method of which are substantially the same as those of example 1, except that black phosphorus quantum dots are used instead of black phosphorus boride quantum dots in the preparation process of vinyl modified black phosphorus boride quantum dots.
Comparative example 4
The present example provides a membrane material for sewage treatment, the formulation and preparation method of which are the same as those in the embodiment 1 of the chinese patent application No. 201810179268.4.
In order to further illustrate the beneficial technical effects of the film material samples related to the embodiments of the present invention, the film material samples prepared in the embodiments 1 to 5 and the comparative examples 1 to 4 were subjected to the related performance tests, the test results are shown in table 1, and the test methods are as follows:
(1) and (3) testing the degradation rate of the dye: the dye degradation rate test selects rhodamine B solution with the concentration of 6 mg/L. Adding 25mL of rhodamine B solution and 0.04g of the prepared sample into a quartz test tube, introducing air, stirring, and taking the solution after 20min under the irradiation of a 400W ultraviolet lamp. The absorbance of the supernatant was measured by ultraviolet spectrophotometry at a wavelength of 550 nm. The degradation rate of the dye can be calculated by the following equation:
r% (degradation rate) ═ C0-Ct)/C0×100％
In the formula, C0Is the initial concentration (mg/L) of rhodamine B, CtRefers to the concentration of rhodamine B after 30 min.
(2) And (3) testing separation recovery rate: and filtering and separating the suspension of the dye and the sample, taking a solid part, and drying. The recovery of the sample after separation can be calculated by the following equation: s% (separation recovery) mt/m0X 100%, wherein m0Is the mass (mg) of the initially charged sample, mtIs the mass of the sample remaining after separation and drying.
(3) Heavy metal ion adsorption effect: the membrane materials in each example are respectively put into 25mL of lead nitrate, mercury nitrate and cadmium nitrate solution with the concentration of 100mg/L, the concentration of the solution is detected after 20min, and the adsorption quantity is calculated.
As can be seen from Table 1, the membrane material for industrial wastewater treatment disclosed in the examples of the present invention has a better wastewater treatment effect as a result of the synergistic effect of the respective monomers.
TABLE 1
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The membrane material for treating industrial wastewater is characterized by being prepared by polymerizing 3-6 parts of vinyl modified black phosphorus boride quantum dots, 8-12 parts of vinyl-terminated hyperbranched poly (amine-ester) and 1-3 parts of β -phenyl acryloyl chloride modified 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine by using free radicals.
2. The membrane material for industrial wastewater treatment as claimed in claim 1, wherein the preparation method of the vinyl modified black phosphorus boride quantum dot comprises the following steps:
s1, placing the black phosphorus quantum dots, ammonium pentaborate, Tween 20 and ethanol in a polytetrafluoroethylene reaction kettle, preserving the heat for 8-12 hours at the temperature of 150-;
and S2, adding the black phosphorus boride quantum dot prepared in the step S1 into ethanol, adding vinyl triethoxysilane into the ethanol, stirring the mixture for 6 to 8 hours at the temperature of between 60 and 80 ℃, and then performing rotary evaporation to remove the ethanol to obtain the vinyl modified black phosphorus boride quantum dot.
3. The membrane material for industrial wastewater treatment according to claim 2, wherein the mass ratio of the black phosphorus quantum dots, the ammonium pentaborate, the tween 20 and the ethanol in step S1 is 1 (0.05-0.15) to 0.1 (5-10).
4. The membrane material for industrial wastewater treatment as claimed in claim 2, wherein the mass ratio of the black phosphorus boride quantum dot, ethanol and vinyltriethoxysilane in step S2 is 1 (3-5) to (0.1-0.3).
5. The membrane material for industrial wastewater treatment according to claim 1, wherein the preparation method of the vinyl-terminated hyperbranched poly (amine-ester) comprises the following steps: adding the third-generation epoxy end group amino hyperbranched poly (amine-ester) and 3-aminocrotonitrile into tetrahydrofuran, stirring and reacting for 6-8 hours at 50-60 ℃ under the action of oxygen inhibition, and then removing the tetrahydrofuran by rotary evaporation to obtain the vinyl-terminated hyperbranched poly (amine-ester).
6. The membrane material for industrial wastewater treatment according to claim 5, wherein the molar ratio of the third-generation epoxy-terminated amino hyperbranched poly (amine-ester), 3-aminocrotonitrile and tetrahydrofuran is 1 (5-8) to (30-40).
7. The membrane material for industrial wastewater treatment as claimed in claim 1, wherein the preparation method of β -phenylpropionyl chloride modified 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine comprises the steps of adding β -phenylpropionyl chloride, 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine and triethylamine into tetrahydrofuran, stirring and reacting at 25-35 ℃ for 3-6 hours, removing tetrahydrofuran by rotary evaporation after the reaction is finished, extracting with water and acetone in a mass ratio of 3:1, taking an oil phase, removing water by anhydrous magnesium sulfate, filtering, and removing acetone by rotary evaporation to obtain β -phenylpropionyl chloride modified 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine.
8. The membrane material for industrial wastewater treatment as claimed in claim 7, wherein the molar ratio of β -phenylpropionyl chloride, 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, triethylamine and tetrahydrofuran is 3:1 (0.4-0.7) to (12-18).
9. The membrane material for industrial wastewater treatment according to any one of claims 1 to 8, wherein the preparation method of the membrane material for industrial wastewater treatment comprises the following steps: mixing all polymerizable monomers to form a mixed material, then adding the mixed material and an initiator into a high-boiling-point solvent, stirring and reacting for 1-3 hours at 70-80 ℃ in a nitrogen or inert gas atmosphere, then pouring the mixed material on a polytetrafluoroethylene template, and placing the polytetrafluoroethylene template in an air-blast drying box at 80-90 ℃ to dry to constant weight to obtain the membrane material for industrial wastewater treatment.
10. The membrane material for industrial wastewater treatment as claimed in claim 9, wherein the mass ratio of the mixed material, the initiator and the high boiling point solvent is 1 (0.01-0.02) to (3-5); the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the inert gas is one of helium, neon and argon.
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| CN202010110209.9A Withdrawn CN111282552A (en) | 2020-02-23 | 2020-02-23 | Membrane material for industrial wastewater treatment |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112058096A (en) * | 2020-09-24 | 2020-12-11 | 朱荣艳 | Nanofiltration membrane and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112058096A (en) * | 2020-09-24 | 2020-12-11 | 朱荣艳 | Nanofiltration membrane and preparation method thereof |
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