CN111732180A - Construction method and application of interface catalytic oxidation film suitable for algae-laden water separation - Google Patents
Construction method and application of interface catalytic oxidation film suitable for algae-laden water separation Download PDFInfo
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 30
- 230000003647 oxidation Effects 0.000 title claims abstract description 29
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 22
- 238000000926 separation method Methods 0.000 title claims abstract description 16
- 238000010276 construction Methods 0.000 title claims abstract description 12
- 239000012528 membrane Substances 0.000 claims abstract description 119
- 239000007864 aqueous solution Substances 0.000 claims abstract description 48
- 239000000243 solution Substances 0.000 claims abstract description 46
- 238000002791 soaking Methods 0.000 claims abstract description 42
- 241000195493 Cryptophyta Species 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 33
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 21
- 238000001914 filtration Methods 0.000 claims abstract description 21
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- 230000008569 process Effects 0.000 claims abstract description 21
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 18
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 17
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims abstract description 13
- 239000004417 polycarbonate Substances 0.000 claims abstract description 13
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 13
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 12
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 12
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 19
- 235000002639 sodium chloride Nutrition 0.000 claims description 11
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- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 10
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 7
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- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 6
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007853 buffer solution Substances 0.000 claims description 5
- 238000009295 crossflow filtration Methods 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 159000000000 sodium salts Chemical group 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 16
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 238000005374 membrane filtration Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 210000004379 membrane Anatomy 0.000 description 87
- 239000008367 deionised water Substances 0.000 description 21
- 229910021641 deionized water Inorganic materials 0.000 description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- 230000004907 flux Effects 0.000 description 8
- 230000003834 intracellular effect Effects 0.000 description 7
- 229910001414 potassium ion Inorganic materials 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 229960001701 chloroform Drugs 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000001471 micro-filtration Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 238000009285 membrane fouling Methods 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 229920001690 polydopamine Polymers 0.000 description 4
- 229920000867 polyelectrolyte Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012425 OXONE® Substances 0.000 description 3
- 210000002469 basement membrane Anatomy 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- HJKYXKSLRZKNSI-UHFFFAOYSA-I pentapotassium;hydrogen sulfate;oxido sulfate;sulfuric acid Chemical compound [K+].[K+].[K+].[K+].[K+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-] HJKYXKSLRZKNSI-UHFFFAOYSA-I 0.000 description 3
- 229920000333 poly(propyleneimine) Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- JLPUXFOGCDVKGO-TUAOUCFPSA-N (-)-geosmin Chemical compound C1CCC[C@]2(O)[C@@H](C)CCC[C@]21C JLPUXFOGCDVKGO-TUAOUCFPSA-N 0.000 description 1
- 239000001075 (4R,4aR,8aS)-4,8a-dimethyl-1,2,3,4,5,6,7,8-octahydronaphthalen-4a-ol Substances 0.000 description 1
- LFYXNXGVLGKVCJ-FBIMIBRVSA-N 2-methylisoborneol Chemical compound C1C[C@@]2(C)[C@](C)(O)C[C@@H]1C2(C)C LFYXNXGVLGKVCJ-FBIMIBRVSA-N 0.000 description 1
- LFYXNXGVLGKVCJ-UHFFFAOYSA-N 2-methylisoborneol Natural products C1CC2(C)C(C)(O)CC1C2(C)C LFYXNXGVLGKVCJ-UHFFFAOYSA-N 0.000 description 1
- 241000195649 Chlorella <Chlorellales> Species 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 108010049746 Microcystins Proteins 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- JLPUXFOGCDVKGO-UHFFFAOYSA-N dl-geosmin Natural products C1CCCC2(O)C(C)CCCC21C JLPUXFOGCDVKGO-UHFFFAOYSA-N 0.000 description 1
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229930001467 geosmin Natural products 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002186 photoelectron spectrum Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to the technical field of membrane filtration, and particularly discloses a construction method and application of an interfacial catalytic oxidation membrane suitable for algae-laden water separation. Firstly, soaking a polycarbonate membrane in an organic solvent, and then continuously soaking in a mixed aqueous solution of dopamine hydrochloride and polyethyleneimine; and after soaking, sequentially soaking in a polyacrylic acid aqueous solution and a poly (diallyl dimethyl ammonium chloride) aqueous solution, repeating the process, ensuring that the finally used soaking solution is the polyacrylic acid aqueous solution, soaking the obtained membrane in a ferrous ion solution, and then dropwise adding a sodium borohydride aqueous solution to the surface of the membrane to obtain the interface catalytic oxidation membrane. The invention loads nano zero-valent iron on the surface of the interface catalytic oxidation film to activate the peroxymonosulfate, thereby realizing the interface catalytic oxidation in the process of filtering the algae-containing water. Compared with the traditional in-situ reaction preoxidation, the method greatly reduces the rupture rate of algae cells, thereby better ensuring the water supply safety.
Description
Technical Field
The invention belongs to the technical field of membrane filtration, and particularly relates to a construction method and application of an interfacial catalytic oxidation membrane suitable for algae-laden water separation.
Technical Field
The membrane filtration technology is used for separating algae cells from water phase, and is an important means for treating algae-containing water. However, in the process of applying the membrane filtration technology, a membrane fouling phenomenon inevitably occurs, thereby greatly reducing the filtration flux and increasing unnecessary energy consumption.
In order to solve the problem of membrane pollution, a method of adding an oxidant to pre-oxidize algae-containing water is widely adopted at present. The method can oxidize extracellular polymer of algae cells and promote flocculation of algae cells, so as to form a looser filter cake layer and further improve filtration flux. However, the common strong oxidants such as sodium hypochlorite and ozone can also destroy the algae cells while oxidizing the extracellular polymeric substances, so that intracellular macromolecular organic substances inside the algae cells are released. Some of these intracellular macromolecular organic substances are toxic substances, such as microcystins and nodulotoxin; some are odorants such as geosmin, 2-methylisoborneol; still others are typical precursors of disinfection by-products, such as proteins, polysaccharides. These intracellular macromolecular organic substances are often difficult to remove by the subsequent traditional processes (coagulation, sedimentation, filtration, disinfection), thereby deteriorating the quality of the effluent. Therefore, the use of pre-oxidation technology to control film contamination has a high risk and is often limited in practical use.
The traditional preoxidation technology is a homogeneous reaction, and algae cells and extracellular polymers are fully contacted with an oxidant in a water body. In practice, however, such well-contacted oxidation is not necessary. Because membrane fouling occurs only at the membrane surface, only the cake layer consisting of algal cells and extracellular polymers deposited on the membrane surface is the main cause of membrane fouling. Therefore, if the oxidation reaction can be limited on the surface of the membrane, on one hand, the oxidation filter cake layer can be oxidized, the effect of filtering flux is improved, on the other hand, the rupture of algae cells in the water body can be greatly reduced, the subsequent treatment difficulty is reduced, and the water quality safety is ensured. Therefore, the method has great practical significance.
Disclosure of Invention
In order to solve the problem of membrane pollution in the process of treating algae-containing water by using a membrane filtration technology, the invention mainly aims to provide a construction method of an interface catalytic oxidation membrane suitable for algae-containing water separation;
the invention also aims to provide an interface catalytic oxidation film which is prepared by the method and is suitable for algae-laden water separation; to slow down membrane fouling and reduce the rupture rate of algae cells.
The invention further aims to provide the application of the interface catalytic oxidation film in algae-laden water separation.
A construction method of an interface catalytic oxidation film suitable for algae-laden water separation comprises the following steps:
(1) cleaning a polycarbonate membrane to obtain a membrane I, soaking the membrane I in an organic solvent, then placing the membrane I in a mixed aqueous solution of dopamine hydrochloride and polyethyleneimine for continuous soaking, and washing the membrane I with water to obtain a membrane II after soaking;
(2) soaking the membrane II obtained in the step (1) in a polyacrylic acid aqueous solution, and then soaking in a poly (diallyl dimethyl ammonium chloride) aqueous solution; repeating the process, and ensuring that the finally used soaking solution is polyacrylic acid aqueous solution, thereby obtaining a membrane III;
(3) soaking the membrane III obtained in the step (2) in a ferrous ion solution, washing with water after soaking is finished, dropwise adding a sodium borohydride aqueous solution to the surface of the membrane until new hydrogen bubbles are not generated, and washing the surface of the membrane with water; this procedure was repeated to give membrane IV.
The purpose of cleaning the polycarbonate membrane in the step (1) is to remove organic matters on the surface of the membrane; specifically, the Polycarbonate (PC) film is soaked in water for 12-72 hours.
Soaking the polycarbonate film in the organic solvent for 5-30 minutes in the step (1);
the organic solvent in the step (1) is at least one of ethanol, methanol and acetone.
The concentration of the dopamine hydrochloride in the mixed aqueous solution of the dopamine hydrochloride and the polyethyleneimine in the step (1) is 1-10 g/L, and the concentration of the polyethyleneimine is 1-15 g/L.
When the membrane I in the step (1) is soaked in a mixed aqueous solution of dopamine hydrochloride and polyethyleneimine, the oscillation speed is 50-200 r/min, and the oscillation time is 12-48 h. Preferably, the pH value of the mixed aqueous solution of dopamine hydrochloride and polyethyleneimine is controlled to be 7-10 by using 1-100 mM Tris-HCl buffer solution during oscillation.
The concentration of the polyacrylic acid aqueous solution in the step (2) is 1-5 g/L, 0.1-1M sodium chloride is mixed, and the pH value is 3-6; the concentration of the poly (diallyl dimethyl ammonium chloride) aqueous solution is 1-5 g/L, 0.1-1M sodium chloride is mixed, and the pH value is 3-6.
The single soaking time of the membrane II in the polyacrylic acid aqueous solution or the poly (diallyl dimethyl ammonium chloride) aqueous solution in the step (2) is independently 5-20 minutes; the process in the step (2) is repeated for 1-7 times.
The ferrous ion solution in the step (3) is a ferrous sulfate solution, a ferrous chloride solution or a ferrous nitrate solution; the concentration of the ferrous ion solution is 0.1-0.5M, and the pH value is 3-6. The concentration of the sodium borohydride aqueous solution is 0.1-0.5M, and the temperature is controlled at 1-5 ℃.
And (4) soaking the membrane III in the ferrous ion solution for 15-60 minutes.
The drying in the step (3) is preferably carried out for 12-48 h at the temperature of 25-70 ℃ in vacuum.
And (4) repeating the process in the step (3) for 1-5 times.
And (3) independently washing with water for 5-20 minutes.
An interface catalytic oxidation film suitable for algae-laden water separation is prepared by the method.
The application of the interface catalytic oxidation film in algae-laden water separation specifically comprises the following steps:
adding peroxymonosulfate into algae-containing water to obtain algae solution; then, the obtained interface catalytic oxidation membrane is used for filtering the algae liquid.
Preferably, the concentration of the peroxymonosulfate is 0.05-0.5 mM, and the peroxymonosulfate is a common salt in the field, and is more preferably a sodium salt or a potassium salt. The filtration adopts a cross-flow filtration mode, the cross-flow speed is 1-5L/min, and the pressure is 0.5-2 bar.
Principle of the invention
Firstly, cleaning a purchased polycarbonate membrane to remove organic matters on the surface, thereby being beneficial to the subsequent modification step; (2) then coating the dopamine crosslinked with the polyethyleneimine on the surface of the polycarbonate membrane by utilizing the self-polymerization of the polydopamine to ensure that the surface of the polycarbonate membrane is positively charged, thereby being beneficial to the subsequent self-assembly step; (3) coating a polyelectrolyte layer on the surface of the membrane by layer-by-layer self-assembly, and enabling free carboxyl in polyacrylic acid as the outermost layer to provide a free site for exchanging with ferrous ions; (4) after the ferrous ions and hydrogen in carboxyl in polyacrylic acid are subjected to ion exchange, reducing the ferrous ions into nano zero-valent iron particles by using a strong reducing agent sodium borohydride, and tightly adsorbing the nano zero-valent iron particles on the surface of the membrane under the action of electrostatic force; (5) the nano zero-valent iron particles are unstable and are easily oxidized by oxygen in a humid environment, so that drying treatment is needed when the nano zero-valent iron particles cannot be used in time after the film preparation work is finished, so that the nano zero-valent iron particles can be stored for later use.
Secondly, the invention adds the peroxymonosulfate into the algae-containing water, when the peroxymonosulfate is not activated, the oxidation capability is very weak, and under a certain concentration, the peroxymonosulfate hardly has influence on algae cells in the algae-containing water. The peroxymonosulfate can be activated by the nano zero-valent iron particles on the surface of the prepared membrane, so that the membrane has strong oxidizability, extracellular polymers of algae cells on the surface of the membrane are oxidized, the zero-valent iron is converted into ferric iron, the aggregation of the algae cells is promoted through the micro-flocculation effect, a loose filter cake layer is formed, the resistance of the filter cake layer is reduced, and the filtration flux is improved.
Thirdly, the invention utilizes the sieving function of the microfiltration membrane to intercept algae cells, thereby realizing the separation from the water phase and achieving the aim of removing algae.
The invention has the advantages that:
the invention loads the nano zero-valent iron on the surface of the polycarbonate membrane to activate the peroxymonosulfate, thereby realizing the interface catalytic oxidation in the process of filtering the algae-containing water. The main advantages of the invention are:
firstly, the process of membrane pollution is slowed down, and the filtration flux and the filtration efficiency of the filtered algae-containing water are improved;
compared with the traditional in-situ reaction preoxidation, the method greatly reduces the rupture rate of the algae cells, thereby better ensuring the water supply safety.
Drawings
FIG. 1 is an infrared spectrum of film I, film II, film III and film IV obtained by the present invention.
FIG. 2 is a photoelectron spectrum of film I and film IV in example 2.
FIG. 3 is a graph of flux versus filtration volume for membrane I and membrane IV filtered algae-containing water in example 4.
FIG. 4 shows the release rate of potassium ions from membrane I obtained in example 2 under in-situ oxidation conditions and membrane IV obtained in example 2 under interfacial catalysis conditions.
FIG. 5 shows the chloroform evolution potential of membrane I from example 2 under in-situ oxidation conditions and membrane IV from example 2 under interfacial catalysis conditions.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
The reagents used in the examples are commercially available without specific reference.
Example 1: the preparation of the micro-filtration membrane with the nano zero-valent iron load is completed according to the following steps
(1) Cleaning basement membranes
A commercially available Polycarbonate (PC) membrane with an average pore size of 0.4 μm was soaked in deionized water for 12 hours to give membrane I.
(2) Coating a polydopamine/polypropylene imine layer
Soaking the membrane I obtained in the step (1) in absolute ethyl alcohol for 5 minutes, then soaking the membrane I in the solution I, shaking the membrane I at a rotating speed of 50r/min for 12 hours, taking out the membrane I, and then washing the membrane I with deionized water for 5 minutes to obtain a membrane II.
The solution I in the step (2) is a mixed aqueous solution of dopamine hydrochloride and polyethyleneimine, and the pH value of the mixed solution is controlled to be 7 by using 10mM Tris-HCl buffer solution. The concentration of the dopamine hydrochloride is 1g/L, and the concentration of the polyethyleneimine is 1 g/L. The water used for preparing the solution is deionized water.
(3) Assembling the polyelectrolyte layer
Soaking the membrane II obtained in the step (2) in a polyacrylic acid aqueous solution for 5 minutes, and then washing with deionized water for 5 minutes; and further soaked in an aqueous solution of poly (diallyldimethylammonium chloride) for 5 minutes, followed by rinsing with deionized water for 5 minutes. This process was repeated 3 times and the final soaking was guaranteed to be aqueous polyacrylic acid. Thus, film III was obtained.
In the step (3), the concentration of the polyacrylic acid aqueous solution is 1g/L, 0.1M sodium chloride is mixed, and the pH value is adjusted to 3 by hydrochloric acid; the concentration of the aqueous solution of poly (diallyldimethylammonium chloride) was 1g/L, and the pH was adjusted to 3 with hydrochloric acid in the presence of 0.1M sodium chloride.
(4) Ion exchange
And (3) soaking the membrane III obtained in the step (3) in a ferrous sulfate solution for 15 minutes, then washing with deionized water for 5 minutes, dropwise adding a sodium borohydride aqueous solution onto the surface of the membrane until no new hydrogen bubbles are generated, and then washing with deionized water for 5 minutes. This process was repeated 1 time, thereby obtaining a film IV.
The concentration of the ferrous sulfate solution in the step (4) is 0.1M, and the pH is adjusted to 3 by hydrochloric acid. The concentration of the sodium borohydride solution is 0.1M, and the temperature is controlled at 1 ℃.
(5) Drying
And (5) placing the membrane IV obtained in the step (4) in a vacuum drying oven, and performing vacuum drying at 25 ℃ for 12h to obtain a membrane V for later use.
Example 2: the preparation of the micro-filtration membrane with the nano zero-valent iron load is completed according to the following steps
(1) Cleaning basement membranes
A commercially available Polycarbonate (PC) membrane with an average pore size of 0.4 μm was soaked in deionized water for 24 hours to give membrane I.
(2) Coating a polydopamine/polypropylene imine layer
Soaking the membrane I obtained in the step (1) in absolute ethyl alcohol for 15 minutes, soaking the membrane I in the solution I, shaking the membrane I at the rotating speed of 100r/min for 24 hours, taking out the membrane I, and washing the membrane I with deionized water for 10 minutes to obtain a membrane II.
The solution I in the step (2) is a mixed aqueous solution of dopamine hydrochloride and polyethyleneimine, and the pH value of the mixed solution is controlled to be 8 by using 50mM Tris-HCl buffer solution. The concentration of the dopamine hydrochloride is 5g/L, and the concentration of the polyethyleneimine is 10 g/L. The water used for preparing the solution is deionized water.
(3) Assembling the polyelectrolyte layer
Soaking the film II obtained in the step (2) in a polyacrylic acid aqueous solution for 10 minutes, and then washing with deionized water for 10 minutes; and then soaked in an aqueous solution of poly (diallyldimethylammonium chloride) for 10 minutes, followed by rinsing with deionized water for 10 minutes. This process was repeated 5 times and the final soaking was guaranteed to be aqueous polyacrylic acid. Thus, film III was obtained.
In the step (3), the concentration of the polyacrylic acid aqueous solution is 3g/L, 0.5M sodium chloride is mixed, and the pH value is adjusted to 4 by hydrochloric acid; the poly (diallyldimethylammonium chloride) solution was adjusted to a concentration of 3g/L in water, mixed with 0.5M sodium chloride, and adjusted to pH 4 with hydrochloric acid.
(4) Ion exchange
And (3) soaking the membrane III obtained in the step (3) in a ferrous sulfate solution for 30 minutes, then washing with deionized water for 10 minutes, dropwise adding a sodium borohydride aqueous solution onto the surface of the membrane until no new hydrogen bubbles are generated, and then washing with deionized water for 10 minutes. This process was repeated 3 times, thereby obtaining a film IV.
The concentration of the ferrous sulfate solution in the step (4) is 0.3M, and the pH is adjusted to 4 by hydrochloric acid. The concentration of the sodium borohydride solution is 0.3M, and the temperature is controlled at 3 ℃.
(5) Drying
And (5) placing the membrane IV obtained in the step (4) in a vacuum drying oven, and performing vacuum drying at 40 ℃ for 24h to obtain a membrane V for later use.
Example 3: the preparation of the micro-filtration membrane with the nano zero-valent iron load is completed according to the following steps
(1) Cleaning basement membranes
A commercially available Polycarbonate (PC) membrane having an average pore size of 0.4 μm was immersed in deionized water for 72 hours to obtain membrane I.
(2) Coating a polydopamine/polypropylene imine layer
Soaking the membrane I obtained in the step (1) in absolute ethyl alcohol for 30 minutes, then soaking the membrane I in the solution I, shaking the membrane I at a rotating speed of 200r/min for 48 hours, taking out the membrane I, and then washing the membrane I with deionized water for 20 minutes to obtain a membrane II.
The solution I in the step (2) is a mixed aqueous solution of dopamine hydrochloride and polyethyleneimine, and the pH value of the mixed solution is controlled to be 10 by using 100mM Tris-HCl buffer solution. The concentration of the dopamine hydrochloride is 10g/L, and the concentration of the polyethyleneimine is 15 g/L. The water used for preparing the solution is deionized water.
(3) Assembling the polyelectrolyte layer
Soaking the film II obtained in the step (2) in a polyacrylic acid aqueous solution for 20 minutes, and then washing with deionized water for 20 minutes; and then soaked in an aqueous solution of poly (diallyldimethylammonium chloride) for 20 minutes, followed by rinsing with deionized water for 20 minutes. This process was repeated 7 times and the final soaking was guaranteed to be aqueous polyacrylic acid. Thus, film III was obtained.
In the step (3), the concentration of the polyacrylic acid aqueous solution is 5g/L, 1M sodium chloride is mixed, and the pH is adjusted to 6 by hydrochloric acid; the concentration of the aqueous solution of poly (diallyldimethylammonium chloride) was 5g/L and the pH was adjusted to 6 with hydrochloric acid in the presence of 1M sodium chloride.
(4) Ion exchange
And (3) soaking the membrane III obtained in the step (3) in a ferrous sulfate solution for 60 minutes, then washing with deionized water for 20 minutes, dropwise adding a sodium borohydride aqueous solution to the surface of the membrane until no new hydrogen bubbles are generated, and then washing with deionized water for 20 minutes. This process was repeated 5 times, thereby obtaining a film IV.
The concentration of the ferrous sulfate solution in the step (4) is 0.5M, and the pH is adjusted to 6 by hydrochloric acid. The concentration of the sodium borohydride solution is 0.5M, and the temperature is controlled at 5 ℃.
(5) Drying
And (5) placing the membrane IV obtained in the step (4) in a vacuum drying oven, and performing vacuum drying at 70 ℃ for 48h to obtain a membrane V for later use.
Example 4: the filtering of algae-containing water by using the micro-filtration membrane loaded with nano zero-valent iron is completed according to the following steps:
(1) dosing
Adding 0.1mM potassium monopersulfate into algae-containing water to obtain algae solution I.
The chlorella solution with concentration of 1 × 10 is prepared from algae-containing water in laboratory6cell/Ml.
(2) Filtration
The membrane IV obtained in example 2 was used to filter the algal solution I, and a cross-flow filtration mode was used, with a cross-flow rate of 1L/min and a pressure of 0.5 bar.
The filtration of the algal solution I by an unmodified polycarbonate membrane under the same condition is taken as a reference, the flux of the membrane before and after modification changes with the filtration volume as shown in figure 3, and the reduction speed of the flux of the membrane after modification (membrane IV) is obviously lower than that of the original membrane (membrane I), which shows that the filtration membrane prepared by the method can effectively reduce the membrane pollution degree in the process of separating the algal from water.
The significance of the release rate of potassium ions and the trichloromethane formation potential is to evaluate the rupture of algae cells. The more the algae cells are broken, the more serious the dissolution of intracellular substances, wherein the leakage of intracellular potassium ions causes the increase of the concentration of potassium ions in the solution, which is shown as the increase of the release rate of the potassium ions; meanwhile, the release of macromolecular organic matters such as intracellular protein, polysaccharide and the like enables the concentration of the organic matters in the solution to rise, the precursor of the disinfection by-products to increase, and the generation potential of the trichloromethane is increased, so that the higher release rate of potassium ions and the generation potential of the trichloromethane represent that the damage degree of algae cells is also higher. As can be seen from FIGS. 4 and 5, when the persulfate concentration is the same, under the in-situ oxidation condition (i.e., adding ferrous sulfate to the algal solution, using Fe)2+The nanometer zero-valent iron on the surface of the film IV is replaced by the catalytic persulfate. The method specifically comprises the steps of taking ferrous sulfate as a catalyst, adding 0.2mM potassium monopersulfate as an oxidant, and filtering after adding and stirring uniformly. ) The release rate of potassium ions and the trichloromethane generation potential of the membrane I are far greater than those of a membrane IV under an interfacial catalysis condition (0-0.4 mM of potassium monopersulfate is directly added and uniformly stirred, and then filtration starts), which indicates that the nano zero-valent iron loaded on the surface of the membrane is taken as a catalyst, so that the damage of an oxidation process to algae cells can be effectively reduced, and series negative effects caused by release of intracellular substances are avoided.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A construction method of an interface catalytic oxidation film suitable for algae-laden water separation is characterized by comprising the following steps:
(1) cleaning a polycarbonate membrane to obtain a membrane I, soaking the membrane I in an organic solvent, then placing the membrane I in a mixed aqueous solution of dopamine hydrochloride and polyethyleneimine for continuous soaking, and washing the membrane I with water to obtain a membrane II after soaking;
(2) soaking the membrane II obtained in the step (1) in a polyacrylic acid aqueous solution, and then soaking in a poly (diallyl dimethyl ammonium chloride) aqueous solution; repeating the process, and ensuring that the finally used soaking solution is polyacrylic acid aqueous solution, thereby obtaining a membrane III;
(3) soaking the membrane III obtained in the step (2) in a ferrous ion solution, washing with water after soaking is finished, dropwise adding a sodium borohydride aqueous solution to the surface of the membrane until new hydrogen bubbles are not generated, and washing the surface of the membrane with water; this procedure was repeated to give membrane IV.
2. The construction method according to claim 1, characterized in that:
the concentration of the dopamine hydrochloride in the mixed aqueous solution of the dopamine hydrochloride and the polyethyleneimine in the step (1) is 1-10 g/L, and the concentration of the polyethyleneimine is 1-15 g/L.
3. The construction method according to claim 1, characterized in that:
the concentration of the polyacrylic acid aqueous solution in the step (2) is 1-5 g/L, 0.1-1M sodium chloride is mixed, and the pH value is 3-6; the concentration of the poly (diallyl dimethyl ammonium chloride) aqueous solution is 1-5 g/L, 0.1-1M sodium chloride is mixed, and the pH value is 3-6.
4. The construction method according to claim 1, characterized in that:
the ferrous ion solution in the step (3) is a ferrous sulfate solution, a ferrous chloride solution or a ferrous nitrate solution; the concentration of the ferrous ion solution is 0.1-0.5M, and the pH value is 3-6; the concentration of the sodium borohydride aqueous solution is 0.1-0.5M, and the temperature is controlled at 1-5 ℃.
5. The construction method according to any one of claims 1 to 4, characterized in that:
when the membrane I in the step (1) is soaked in a mixed aqueous solution of dopamine hydrochloride and polyethyleneimine, the oscillation speed is 50-200 r/min, and the oscillation time is 12-48 h;
the single soaking time of the membrane II in the polyacrylic acid aqueous solution or the poly (diallyl dimethyl ammonium chloride) aqueous solution in the step (2) is independently 5-20 minutes;
and (4) soaking the membrane III in the ferrous ion solution for 15-60 minutes.
6. The construction method according to claim 5, wherein:
controlling the pH value of the mixed aqueous solution of dopamine hydrochloride and polyethyleneimine to be 7-10 by using 1-100 mM Tris-HCl buffer solution during oscillation; the process in the step (2) is repeated for 1-7 times; and (4) repeating the process in the step (3) for 1-5 times.
7. An interfacial catalytic oxidation membrane suitable for algae-laden water separation, prepared by the method of any one of claims 1 to 6.
8. The application of the interface catalytic oxidation film in algae-laden water separation according to claim 7 is characterized by comprising the following specific steps:
adding peroxymonosulfate into algae-containing water to obtain algae solution; then, the obtained interface catalytic oxidation membrane is used for filtering the algae liquid.
9. The use of the interfacial catalytic oxidation membrane according to claim 8 for the separation of algae-laden water, wherein:
the concentration of the peroxymonosulfate is 0.05-0.5 mM, and the type of the peroxymonosulfate is sodium salt or potassium salt.
10. The use of the interfacial catalytic oxidation membrane according to claim 8 for the separation of algae-laden water, wherein:
the filtration adopts a cross-flow filtration mode, the cross-flow speed is 1-5L/min, and the pressure is 0.5-2 bar.
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