CN113522259A - Magnetic photocatalytic water treatment agent and preparation method thereof - Google Patents
Magnetic photocatalytic water treatment agent and preparation method thereof Download PDFInfo
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- CN113522259A CN113522259A CN202110784738.1A CN202110784738A CN113522259A CN 113522259 A CN113522259 A CN 113522259A CN 202110784738 A CN202110784738 A CN 202110784738A CN 113522259 A CN113522259 A CN 113522259A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 33
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 98
- 229910001308 Zinc ferrite Inorganic materials 0.000 claims abstract description 75
- 229910005887 NiSn Inorganic materials 0.000 claims abstract description 43
- WIDLHXITRIUHNO-UHFFFAOYSA-N 2-methylprop-2-enoic acid;2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound CC(=C)C(O)=O.C=CC(=O)OCCOC(=O)C=C WIDLHXITRIUHNO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 7
- 239000000956 alloy Substances 0.000 claims abstract description 7
- NNGHIEIYUJKFQS-UHFFFAOYSA-L hydroxy(oxo)iron;zinc Chemical compound [Zn].O[Fe]=O.O[Fe]=O NNGHIEIYUJKFQS-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- 239000008367 deionised water Substances 0.000 claims description 43
- 229910021641 deionized water Inorganic materials 0.000 claims description 43
- 238000003756 stirring Methods 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 18
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 7
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- 239000002077 nanosphere Substances 0.000 claims description 7
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 claims description 7
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 241000080590 Niso Species 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 2
- -1 grinding Substances 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 18
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 239000002351 wastewater Substances 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 239000010842 industrial wastewater Substances 0.000 abstract description 5
- 230000009471 action Effects 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 38
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229920006318 anionic polymer Polymers 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000011651 chromium Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910000599 Cr alloy Inorganic materials 0.000 description 2
- 239000000788 chromium alloy Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
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- 239000000463 material Substances 0.000 description 2
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- 239000010865 sewage Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- YUYVOPQBMGKAHH-UHFFFAOYSA-N C(=C)C=1NC=CN1.C(=C)C1=C(C=CC=C1)C=C.C=CC1=CC=CC=C1 Chemical compound C(=C)C=1NC=CN1.C(=C)C1=C(C=CC=C1)C=C.C=CC1=CC=CC=C1 YUYVOPQBMGKAHH-UHFFFAOYSA-N 0.000 description 1
- 229910005885 NiSn2 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012492 regenerant Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- 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
- B01J35/33—Electric or magnetic properties
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- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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- B01J31/40—Regeneration or reactivation
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- B01J35/39—Photocatalytic properties
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- 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
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/70—Treatment of water, waste water, or sewage by reduction
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- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention belongs to the technical field of industrial wastewater treatment, and discloses a magnetic photocatalytic water treatment agent and a preparation method thereof. The preparation method comprises the following steps: preparation of porous spherical nano ZnFe2O4(ii) a Synthetic porous TiO2@ZnFe2O4(ii) a In porous TiO2@ZnFe2O4The surface of the NiSn alloy is deposited to obtain NiSn/TiO2@ZnFe2O4A composite material; and then coating poly- (methacrylic acid-ethylene glycol diacrylate) to obtain the magnetic photocatalytic water treatment agent. The magnetic photocatalytic water treatment agent prepared by the invention has a porous structure, is beneficial to adsorption of metal ions in wastewater on the surface of the water treatment agent, is combined with the metal ions in the wastewater through electrostatic action, is beneficial to removal of various metal ions, and has good selectivity on the metal ions.
Description
Technical Field
The invention belongs to the technical field of industrial wastewater treatment, relates to a magnetic photocatalytic water treatment agent and a preparation method thereof, and particularly relates to poly- (methacrylic acid-ethylene glycol diacrylate) @ NiSn/TiO2/FeZn2O4A water treatment agent and a preparation method thereof.
Background
The industrial wastewater has complex components and contains various metal ions, and belongs to wastewater which is difficult to treat. At present, a plurality of treatment methods are available, and the commonly used metal ion treatment methods comprise a precipitation method, a redox method, a solution extraction method, an adsorption method, a membrane separation method, an ion exchange method and a biological treatment method. Among them, the precipitation method requires fractional precipitation of different metal ions, which is complicated in process, requires addition of various reagents, and is high in cost. The redox method requires first redox, electrolytic reduction and the like, then treatment by a precipitation method, and the process flow is more complicated. The extraction method has large energy consumption in the extraction process and the regeneration process of the solvent. The adsorption method has high efficiency of removing metal ions, but has low regeneration efficiency. The membrane separation method has good treatment effect but high treatment cost. The ion exchange method uses selective ion exchange resin and zeolite, and the latter has complicated manufacture, high cost and great regenerant consumption, so that its application is limited. The process flow of the biological treatment method is relatively complicated.
The anionic polymer has a porous structure, has certain application and research in the field of metal ion treatment, but has the problems of poor selectivity, difficult recovery and the like. Poly (methacrylic acid-ethylene glycol diacrylate) cross-linked porous polyethylene glycol diacrylate (PMPEG-PDDA) to form anionic polymer poly- (methacrylic acid-ethylene glycol diacrylate) coated NiSn/TiO2Composite porous semiconductor magnetic nano FeZn2O4Material synthesis poly- (methacrylic acid-ethylene glycol diacrylate) @ NiSn/TiO2/FeZn2O4The research and application of the water treatment agent are not reported.
Disclosure of Invention
In view of the above, the present invention aims to provide a magnetic photocatalytic water treatment agent capable of effectively adsorbing metal ions in industrial wastewater and reducing the metal ions to metal, and a preparation method thereof.
In order to solve the problems in the prior art, the invention provides a magnetic photocatalytic water treatment agent which comprises 60-70 wt% of poly- (methacrylic acid-ethylene glycol diacrylate) and 30-40 wt% of NiSn/TiO2/FeZn2O4The poly- (methacrylic acid-ethylene glycol diacrylate) is coated on NiSn/TiO2/FeZn2O4The surface of said NiSn/TiO2/FeZn2O4From TiO2@ZnFe2O4The surface is loaded with NiSn alloy; wherein the content of NiSn alloy is NiSn/TiO2/FeZn2O43-5 wt% of (A); in the NiSn alloy, the molar ratio of Ni to Sn is 1 (0.42-2.4); the TiO is2@ZnFe2O4Is porous TiO2Coating porous spherical nano ZnFe2O4Carrier of ZnFe2O4In an amount of said TiO2@ZnFe2O425-75 wt% of (B).
The invention also provides a preparation method of the magnetic photocatalytic water treatment agent, which comprises the following steps:
(1) adding Zn (NO)3)2·6H2O、Fe(NO3)3·9H2O and C6H8O7·H2Dissolving O in deionized water, adding surfactant PEG400, stirring to dissolve, performing high-pressure hydrothermal reaction, washing, drying, and calcining to obtain porous spherical nano ZnFe2O4；
(2) The porous spherical nano ZnFe2O4Adding surfactant PEG-400 into anhydrous ethanol solution of butyl titanate, dropwise adding mixture of anhydrous ethanol, glacial acetic acid and deionized water under stirring, hydrolyzing to form sol, stirring, standing for 2-3 days after gel is formed, vacuum drying at 80 deg.C for 8-10 hr to obtain powder, grinding, and air roasting at 500 deg.C for 3 hr to obtain porous TiO2@ZnFe2O4Nanospheres;
(3) subjecting the porous TiO to a reaction2@ZnFe2O4Adding the nanospheres into deionized water, and performing ultrasonic dispersion uniformly to form TiO2@ZnFe2O4A dispersion liquid; to the TiO2@ZnFe2O40.1mol/L NiSO is added into the dispersion liquid according to the molar ratio of Ni to Sn of 1 (0.42-2.4)4Solution and 0.1mol/L SnCl2Ultrasonic dispersing the solution uniformly, adjusting pH to 8.5-11, stirring, protecting with inert gas, and reacting at 50 deg.C according to KBH4Is nNiAnd nSn5 times of the total amount of the components, 0.2 to 0.4mol/L of KBH is added dropwise4Reacting the solution for 5-6 hours, filtering, washing with deionized water until filtrate is free of chloride ions and sulfate ions, and drying at 80 ℃ in vacuum to obtain NiSn/TiO2@ZnFe2O4；
(4) Mixing the NiSn/TiO2@ZnFe2O4Adding the mixture into deionized water, stirring and dispersing, adding ethylene glycol diacrylate and an initiator potassium persulfate, stirring and heating to about 60 ℃, reacting for 30 minutes, then adding methacrylic acid, stirring and refluxing at about 80 ℃ for 4 hours, heating to 95-97 ℃, refluxing for 1 hour, standing after the reaction is finished, removing supernatant, washing the product with deionized water for 2-3 timesThen, vacuum drying is carried out at the temperature of 80 ℃ to obtain the magnetic photocatalytic water treatment agent, wherein the magnetic photocatalytic water treatment agent is poly- (methacrylic acid-ethylene glycol diacrylate) @ NiSn/TiO2@ZnFe2O4A composite material.
Further, in the step (1) of the above production method, Zn (NO)3)2·6H2O、Fe(NO3)3·9H2O、C6H8O7·H2The dosage ratio of O, deionized water and the surfactant PEG400 is 0.01 moL/0.02 moL/0.06 moL/80 mL/0.8 mL.
Further, in the step (2) of the preparation method, porous spherical nano ZnFe2O4The dosage ratio of the surfactant PEG-400 to the butyl titanate to the absolute ethyl alcohol to the glacial acetic acid to the deionized water (1.33-12) g is 0.68mL to 17mL to 44mL to 3.6 mL.
Further, in the step (4) of the preparation method, the mass ratio of the ethylene glycol diacrylate to the methacrylic acid is (10-20): 1, the using amount of the potassium persulfate is 1-2% of the total using amount of the methacrylic acid and the ethylene glycol diacrylate.
Compared with the prior art, the magnetic photocatalytic water treatment agent provided by the invention has the following beneficial effects:
(1) the porous structure of the anionic polymer poly- (styrene-divinylbenzene-vinyl imidazole) is favorable for the adsorption of metal ions in wastewater on the surface of a water treatment agent, and meanwhile, a large number of carboxylic acid functional groups with negative charges are arranged in the anionic polymer poly- (methacrylic acid-ethylene glycol diacrylate) and are combined with the metal ions in the wastewater through electrostatic action, so that the removal of various metal ions is facilitated, and the selectivity to the metal ions is good.
(2) ZnFe in water treatment agent2O4The catalyst has higher magnetism, which is beneficial to the recovery of the catalyst.
(3) The water treatment agent is very sensitive to pH, and is soaked in a solution with the pH being less than or equal to 4, and carboxylate exists in a molecular form, so that the water treatment agent has good regeneration capacity and can be recycled.
(4)ZnFe2O4Is a photocatalyst with high photocatalytic activity and good visual effectPhotosensitive semiconductor catalyst having a band gap energy of 1.9eV with TiO2Compounding, TiO reduction2The band gap energy of the material can improve the transmission rate and efficiency of photoproduction electrons, greatly reduce the probability of photoproduction electron-hole recombination, and greatly improve the TiO with the synergistic effect of NiSn2The catalytic performance of the catalyst can effectively reduce the adsorbed metal ions into metal, and the treatment efficiency is improved. The method can be used for treating industrial wastewater containing various metal ions, greatly optimizes the sewage treatment process, reduces the sewage treatment cost, and is also beneficial to recycling the metal ions in the wastewater.
Drawings
FIG. 1 shows the treatment of Cr with the magnetic photocatalytic water treatment agent prepared in example 1 under ultraviolet light6+Degradation performance;
FIG. 2 shows the treatment of Cr with the magnetic photocatalytic water treatment agent prepared in example 1 under visible light6+And (4) degradation performance.
Detailed Description
The present invention will be further illustrated by the following specific examples, which are carried out on the premise of the technical scheme of the present invention, and it should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention.
Example 1:
(1) porous spherical nano ZnFe2O4Synthesis of (2)
2.975g (0.01mol) of Zn (NO)3)2·6H2O, 8.081g (0.02mol) Fe (NO)3)3·9H2Dissolving O and 12.608g (0.06mol) citric acid in 60mL deionized water, adding 0.8mL PEG400, stirring for 30 minutes for dissolution, transferring the mixed solution into a 100mL stainless steel high-pressure reaction kettle, reacting at 180 ℃ for 12 hours, naturally cooling the high-pressure reaction kettle to room temperature after the reaction is finished, washing the obtained product with distilled water and absolute ethyl alcohol for 3 times respectively, drying at 80 ℃ in a vacuum oven, and roasting at 500 ℃ in a muffle furnace for 3 hours to obtain the porous spherical nano ZnFe2O4。
(2) Porous TiO2@ZnFe2O4Synthesis of (2)
A sol-gel method is adopted. 17mL of butyl titanate was dissolved in 22mL of absolute ethanol,0.68mL of PEG-400 and 4g of porous nano ZnFe are added2O4Dropwise adding a mixture of 22mL of absolute ethyl alcohol, 3.6mL of glacial acetic acid and 3.6mL of deionized water under stirring, hydrolyzing to form sol, continuously stirring, standing for 2-3 days after gel is formed, vacuum drying at 80 ℃ for 8-10 hours to obtain powder, grinding the powder, and roasting in a muffle furnace at 500 ℃ for 3 hours to obtain ZnFe2O4Porous TiO in an amount of 50 wt%2@ZnFe2O4Nanospheres.
(3)NiSn/TiO2@ZnFe2O4Preparation of composite materials
1) 1g of porous TiO2@ZnFe2O4Adding into 20mL deionized water, and dispersing uniformly by ultrasonic to form TiO2@ZnFe2O4A dispersion liquid;
2) mixing NiSO4Dissolving with deionized water to form 0.1mol/L NiSO4A solution;
3) SnCl2Dissolving with deionized water to form 0.1mol/L SnCl2A solution;
4) 1.74mL of 0.1mol/L NiSO was measured4Solution and 1.74mL of 0.1mol/L SnCl2Mixing the solution, dispersing the solution uniformly by ultrasonic wave, and then dripping the solution into TiO2@ZnFe2O4In the dispersion liquid;
5) preparing 2mol/L ammonia water solution;
6) dropwise adding the prepared 2mol/L ammonia water solution into the dispersion liquid obtained in the step 4), and adjusting the pH value to 8.5-11;
7) reacting KBH4Dissolving in deionized water to prepare KBH4KBH concentration of 0.2mol/L4A solution;
8) stirring, under the protection of inert gas, and dropwise adding 8.7mL of KBH into the mixed suspension with the pH value of 8.5-11 in the step 6) at 50 DEG C4Reacting the solution for 5 to 6 hours;
9) filtering after the reaction is finished, washing with deionized water until filtrate is free of chloride ions and sulfate ions, and drying in vacuum at 80 ℃ to obtain WNiSn＝3％，nNi:nSnNiSn/TiO with molar ratio of 1:12@ZnFe2O4A composite material.
(4) Poly- (methacrylic acid-ethylene glycol diacrylate) @ NiSn/TiO2@ZnFe2O4Preparation of water treatment agent
Firstly weighing 5g of NiSn/TiO prepared in the step (1)2@ZnFe2O4The composite material was added to 100mL of deionized water and dispersed with stirring. 6.9g of ethylene glycol diacrylate and 0.15g of the initiator potassium persulfate were added. Stirring and heating to about 60 ℃, reacting for 30 minutes, then adding 0.6g of methacrylic acid, stirring and refluxing at about 80 ℃ for reacting for 4 hours, heating to 95-97 ℃, and refluxing for 1 hour. After the reaction is finished, standing, removing supernatant, washing for 2-3 times by deionized water, and vacuum drying the product at 80 ℃ to obtain poly- (methacrylic acid-ethylene glycol diacrylate) @ NiSn/TiO with 60% of poly- (methacrylic acid-ethylene glycol diacrylate)2@ZnFe2O4A composite water treatment agent.
Example 2
(1) Porous spherical nano ZnFe2O4Synthesis of (2)
2.975g (0.01mol) of Zn (NO)3)2·6H2O, 8.081g (0.02mol) Fe (NO)3)3·9H2Dissolving O and 12.608g (0.06mol) citric acid in 60mL deionized water, adding 0.8mL PEG400, stirring for 30 minutes for dissolution, transferring the mixed solution into a 100mL stainless steel high-pressure reaction kettle, reacting at 180 ℃ for 12 hours, naturally cooling the high-pressure reaction kettle to room temperature after the reaction is finished, washing the obtained product with distilled water and absolute ethyl alcohol for 3 times respectively, drying at 80 ℃ in a vacuum oven, and roasting at 500 ℃ in a muffle furnace for 3 hours to obtain the porous spherical nano ZnFe2O4。
(2) Porous TiO2@ZnFe2O4Synthesis of (2)
A sol-gel method is adopted. Dissolving 17mL of butyl titanate in 22mL of absolute ethanol, adding 0.68mL of PEG-400 and 1.72g of porous nano ZnFe2O4Adding dropwise a mixture of 22mL of anhydrous ethanol, 3.6mL of glacial acetic acid and 3.6mL of deionized water under stirring, hydrolyzing to form sol, stirring, standing for 2-3 days after gel is formed, vacuum drying at 80 deg.C for 8-10 hr to obtain powder, grindingRoasting in a muffle furnace at 500 ℃ for 3 hours to obtain ZnFe2O4Porous TiO in an amount of 30%2@ZnFe2O4Nanospheres.
(3)NiSn/TiO2@ZnFe2O4Preparation of composite materials
1) 1g of porous TiO2@ZnFe2O4Adding into 20mL deionized water, and uniformly dispersing by ultrasonic to form 50-100 mg/mL TiO2@ZnFe2O4A dispersion liquid;
2) mixing NiSO4Dissolving with deionized water to form 0.1mol/L solution;
3) SnCl2Dissolving with deionized water to form 0.1mol/L solution;
4) 1.74mL of 0.1mol/L NiSO was measured4Solution and 1.74mL of 0.1mol/L SnCl2Mixing the solution, dispersing the solution uniformly by ultrasonic wave, and then dripping the solution into TiO2@ZnFe2O4In the dispersion liquid;
5) preparing 2mol/L ammonia water solution;
6) dropwise adding the prepared 2mol/L ammonia water solution into the dispersion liquid obtained in the step 4), and adjusting the pH value to 8.5-11;
7) reacting KBH4Dissolving in deionized water to prepare KBH4KBH concentration of 0.2mol/L4A solution;
8) stirring, under the protection of inert gas, and dropwise adding 8.7mL of KBH into the mixed suspension with the pH value of 8.5-11 in the step 6) at 50 DEG C4Reacting the solution for 5 to 6 hours;
9) filtering after the reaction is finished, washing with deionized water until filtrate is free of chloride ions and sulfate ions, and drying in vacuum at 80 ℃ to obtain WNiSn＝3％，nNi:nSnNiSn/TiO with molar ratio of 1:12@ZnFe2O4A composite material.
(4) Poly- (methacrylic acid-ethylene glycol diacrylate) @ NiSn/TiO2@ZnFe2O4Preparation of water treatment agent
Firstly weighing 5g of NiSn/TiO prepared in the step (1)2@ZnFe2O4The composite material was added to 100mL of deionized water and dispersed with stirring. 8.7g of ethylene glycol diacrylate and 0.15g of the initiator potassium persulfate were added. Stirring and heating to about 60 ℃, reacting for 30 minutes, then adding 0.6g of methacrylic acid, stirring and refluxing at about 80 ℃ for reacting for 4 hours, heating to 95-97 ℃, and refluxing for 1 hour. After the reaction is finished, standing, removing supernatant, washing for 2-3 times by deionized water, and vacuum drying the product at 80 ℃ to obtain poly- (methacrylic acid-ethylene glycol diacrylate) @ NiSn/TiO with 65% of poly- (methacrylic acid-ethylene glycol diacrylate)2@ZnFe2O4A composite water treatment agent.
Example 3
(1) Porous spherical nano ZnFe2O4Synthesis of (2)
2.975g (0.01mol) of Zn (NO)3)2·6H2O, 8.081g (0.02mol) Fe (NO)3)3·9H2Dissolving O and 12.608g (0.06mol) citric acid in 60mL deionized water, adding 0.8mL PEG400, stirring for 30 minutes for dissolution, transferring the mixed solution into a 100mL stainless steel high-pressure reaction kettle, reacting at 180 ℃ for 12 hours, naturally cooling the high-pressure reaction kettle to room temperature after the reaction is finished, washing the obtained product with distilled water and absolute ethyl alcohol for 3 times respectively, drying at 80 ℃ in a vacuum oven, and roasting at 500 ℃ in a muffle furnace for 3 hours to obtain the porous spherical nano ZnFe2O4。
(2) Porous TiO2@ZnFe2O4Synthesis of (2)
A sol-gel method is adopted. Dissolving 17mL of butyl titanate in 22mL of absolute ethanol, adding 0.68mL of PEG-400 and 9.33g of porous nano ZnFe2O4Dropwise adding a mixture of 22mL of absolute ethyl alcohol, 3.6mL of glacial acetic acid and 3.6mL of deionized water under stirring, hydrolyzing to form sol, continuously stirring, standing for 2-3 days after gel is formed, vacuum drying at 80 ℃ for 8-10 hours to obtain powder, grinding the powder, and roasting in a muffle furnace at 500 ℃ for 3 hours to obtain ZnFe2O4Porous TiO in an amount of 70%2@ZnFe2O4Nanospheres.
(3)NiSn/TiO2@ZnFe2O4Preparation of composite materials
1) 1g of porous TiO2@ZnFe2O4Adding the mixture into 20mL of deionized water according to the proportion, and uniformly dispersing by ultrasonic to form 50-100 mg/mL TiO2@ZnFe2O4A dispersion liquid;
2) mixing NiSO4Dissolving with deionized water to form 0.1mol/L solution;
3) SnCl2Dissolving with deionized water to form 0.1mol/L solution;
4) 1.74mL of 0.1mol/L NiSO was measured4Solution and 1.74mL of 0.1mol/L SnCl2Mixing the solution, dispersing the solution uniformly by ultrasonic wave, and then dripping the solution into TiO2@ZnFe2O4In the dispersion liquid;
5) preparing 2mol/L ammonia water solution;
6) dropwise adding the prepared 2mol/L ammonia water solution into the dispersion liquid obtained in the step 4), and adjusting the pH value to 8.5-11;
7) reacting KBH4Dissolving in deionized water to prepare KBH4KBH concentration of 0.2mol/L4A solution;
8) stirring, under the protection of inert gas, and dropwise adding 8.7mL of KBH into the mixed suspension with the pH value of 8.5-11 in the step 6) at 50 DEG C4Reacting the solution for 5 to 6 hours;
9) filtering after the reaction is finished, washing with deionized water until filtrate is free of chloride ions and sulfate ions, and drying in vacuum at 80 ℃ to obtain WNiSn＝3％，nNi:nSnNiSn/TiO with molar ratio of 1:12@ZnFe2O4A composite material.
(4) Poly- (methacrylic acid-ethylene glycol diacrylate) @ NiSn/TiO2@ZnFe2O4Preparation of water treatment agent
Firstly weighing 5g of NiSn/TiO prepared in the step (1)2@ZnFe2O4The composite material was added to 100mL of deionized water and dispersed with stirring. 11.0g of ethylene glycol diacrylate and 0.15g of the initiator potassium persulfate were added. Stirring and heating to about 60 ℃, reacting for 30 minutes, then adding 0.7g of methacrylic acid, stirring and refluxing at about 80 ℃ for reacting for 4 hours, heating to 95-97 ℃, and refluxing for 1 hour. After the reaction is finishedStanding, removing supernatant, washing with deionized water for 2-3 times, and vacuum drying at 80 deg.C to obtain poly- (methacrylic acid-ethylene glycol diacrylate) @ NiSn/TiO with poly- (methacrylic acid-ethylene glycol diacrylate) content of 70%2@ZnFe2O4A composite water treatment agent.
Adding 1g/L of photocatalytic water treatment agent into 1mg/L of Cr6+In the solution, the pH value of the solution is adjusted to 4 by a pH meter. Before illumination, stirring for 30 minutes in the dark for dark adsorption to achieve adsorption-desorption balance. Continuously introducing N during dark adsorption and illumination2Ensure no O in the system2. A100W mercury lamp and a 300W xenon lamp are used as ultraviolet and visible light sources. Sampling is carried out once every 5minq when the ultraviolet lamp irradiates, sampling is carried out once every 15 minutes when the visible light irradiates, the concentration change when the catalyst is not added is compared, and the degradation rate is calculated. The results are shown in FIGS. 1 and 2.
The results of FIGS. 1 and 2 show that Cr is present in the UV light for about 25 minutes6+The degradation rate of the chromium-free chromium alloy reaches 100 percent, and the chromium-free chromium alloy is obtained in 90 minutes under the visible light condition6+The degradation rate reaches 100 percent, which indicates that the prepared magnetic photocatalytic water treatment agent is applied to Cr6+Has better removal performance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (5)
1. The magnetic photocatalytic water treatment agent is characterized by comprising 60-70 wt% of poly- (methacrylic acid-ethylene glycol diacrylate) and 30-40 wt% of NiSn/TiO2/FeZn2O4The poly- (methacrylic acid-ethylene glycol diacrylate) is coated on NiSn/TiO2/FeZn2O4The surface of said NiSn/TiO2/FeZn2O4From TiO2@ZnFe2O4The surface is loaded with NiSn alloy; wherein the content of NiSn alloy is NiSn/TiO2/FeZn2O43-5 wt% of (A); in the NiSn alloy, the molar ratio of Ni to Sn is 1 (0.42-2.4); the TiO is2@ZnFe2O4Is porous TiO2Coating porous spherical nano ZnFe2O4Carrier of ZnFe2O4In an amount of said TiO2@ZnFe2O425-75 wt% of (B).
2. A method for preparing the magnetic photocatalytic water treatment agent according to claim 1, characterized by comprising the steps of:
(1) adding Zn (NO)3)2·6H2O、Fe(NO3)3·9H2O and C6H8O7·H2Dissolving O in deionized water, adding surfactant PEG400, stirring to dissolve, performing high-pressure hydrothermal reaction, washing, drying, and calcining to obtain porous spherical nano ZnFe2O4；
(2) The porous spherical nano ZnFe2O4Adding surfactant PEG-400 into anhydrous ethanol solution of butyl titanate, dropwise adding mixture of anhydrous ethanol, glacial acetic acid and deionized water under stirring, hydrolyzing to form sol, stirring, standing for 2-3 days after gel is formed, vacuum drying at 80 deg.C for 8-10 hr to obtain powder, grinding, and air roasting at 500 deg.C for 3 hr to obtain porous TiO2@ZnFe2O4Nanospheres;
(3) subjecting the porous TiO to a reaction2@ZnFe2O4Adding the nanospheres into deionized water, and performing ultrasonic dispersion uniformly to form TiO2@ZnFe2O4A dispersion liquid; to the TiO2@ZnFe2O40.1mol/L NiSO is added into the dispersion liquid according to the molar ratio of Ni to Sn of 1 (0.42-2.4)4Solution and 0.1mol/L SnCl2Ultrasonic dispersing the solution uniformly, adjusting pH to 8.5-11, stirring, protecting with inert gas, and reacting at 50 deg.C according to KBH4Is nNiAnd nSn5 times of the total amount of the components, 0.2 to 0.4mol/L of KBH is added dropwise4Reacting the solution for 5 to 6 hours, filtering,washing with deionized water until filtrate contains no chloride ion or sulfate ion, and vacuum drying at 80 deg.C to obtain NiSn/TiO2@ZnFe2O4；
(4) Mixing the NiSn/TiO2@ZnFe2O4Adding the mixture into deionized water, stirring and dispersing, adding ethylene glycol diacrylate and an initiator potassium persulfate, stirring and heating to about 60 ℃, reacting for 30 minutes, then adding methacrylic acid, stirring and refluxing at about 80 ℃ for 4 hours, heating to 95-97 ℃, refluxing for 1 hour, standing after the reaction is finished, removing supernatant, washing the product with deionized water for 2-3 times, and drying in vacuum at 80 ℃ to obtain the magnetic photocatalytic water treatment agent, wherein the magnetic photocatalytic water treatment agent is poly- (methacrylic acid-ethylene glycol diacrylate) @ NiSn/TiO2@ZnFe2O4A composite material.
3. The method according to claim 2, wherein in the step (1), Zn (NO)3)2·6H2O、Fe(NO3)3·9H2O、C6H8O7·H2The dosage ratio of O, deionized water and the surfactant PEG400 is 0.01 moL/0.02 moL/0.06 moL/80 mL/0.8 mL.
4. The preparation method according to claim 2, wherein in the step (2), the porous spherical nano ZnFe is used2O4The dosage ratio of the surfactant PEG-400 to the butyl titanate to the absolute ethyl alcohol to the glacial acetic acid to the deionized water (0.1237-0.2105) g is 0.68mL to 17mL to 44mL to 3.6 mL.
5. The preparation method according to claim 2, wherein in the step (4), the mass ratio of the ethylene glycol diacrylate to the methacrylic acid is (10-20): 1, the using amount of the potassium persulfate is 1-2% of the total using amount of the methacrylic acid and the ethylene glycol diacrylate.
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