CN113522259B - 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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- CN113522259B CN113522259B CN202110784738.1A CN202110784738A CN113522259B CN 113522259 B CN113522259 B CN 113522259B CN 202110784738 A CN202110784738 A CN 202110784738A CN 113522259 B CN113522259 B CN 113522259B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 34
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 54
- 229910005887 NiSn Inorganic materials 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 26
- 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 20
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 239000000956 alloy Substances 0.000 claims abstract description 7
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 7
- 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 42
- 229910021641 deionized water Inorganic materials 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 34
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000001291 vacuum drying Methods 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
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000010992 reflux 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
- 239000000203 mixture Substances 0.000 claims description 9
- 241000080590 Niso Species 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
- 239000000047 product Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 230000001105 regulatory effect Effects 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
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- 229910021645 metal ion Inorganic materials 0.000 abstract description 18
- 239000002351 wastewater Substances 0.000 abstract description 6
- 239000010842 industrial wastewater Substances 0.000 abstract description 5
- 238000004065 wastewater treatment Methods 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 36
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 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
- 238000006731 degradation reaction Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 229920006318 anionic polymer Polymers 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 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
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000033116 oxidation-reduction process Effects 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 239000004065 semiconductor Substances 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
- 238000005286 illumination Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 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
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000006978 adaptation 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
- 238000013329 compounding Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 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
- 230000035945 sensitivity Effects 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 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
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- 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
- B01J35/33—Electric or magnetic properties
-
- 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
-
- 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
- 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
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- 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
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- 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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- 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
- B01J31/40—Regeneration or reactivation
- B01J31/4007—Regeneration or reactivation of catalysts containing polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
- B01J35/39—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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- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- 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
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
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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 ZnFe 2 O 4 The method comprises the steps of carrying out a first treatment on the surface of the Synthesis of porous TiO 2 @ZnFe 2 O 4 The method comprises the steps of carrying out a first treatment on the surface of the In porous TiO 2 @ZnFe 2 O 4 Is deposited with NiSn alloy to obtain NiSn/TiO 2 @ZnFe 2 O 4 A composite material; and 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 favorable for adsorbing 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 favorable for removing 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 in particular relates to a poly- (methacrylic acid-ethylene glycol diacrylate) @ NiSn/TiO 2 /FeZn 2 O 4 A water treatment agent and a preparation method thereof.
Background
The industrial wastewater has complex components and contains various metal ions, and belongs to wastewater difficult to treat. The existing treatment methods are many, and common metal ion treatment methods include precipitation method, oxidation-reduction method, solution extraction method, adsorption method, membrane separation method, ion exchange method and biological treatment method. The precipitation method needs to carry out sectional precipitation on different metal ions, has complex procedures, needs to add various medicaments, and has higher cost. The oxidation-reduction method needs oxidation-reduction, electrolytic reduction and the like, and then the treatment by the precipitation method is more complicated in technological process. The extraction method has the advantages of high energy consumption in the extraction process and the regeneration process. The adsorption method has high efficiency in removing metal ions, but has low regeneration efficiency. The membrane separation method has better treatment effect, but has higher treatment cost. Ion exchange methods are currently used, such as ion exchange resins, selective, complex to manufacture, high in cost, and high in regenerant consumption, and thus limited in application. The biological treatment method has a complex process flow.
The anionic polymer has a porous structure, and has certain application research in the field of metal ion treatment, but has the problems of poor selectivity, difficult recovery and the like. NiSn/TiO is coated by an anionic polymer poly- (methacrylic acid-ethylene glycol diacrylate) formed by crosslinking porous polyethylene glycol diacrylate with polymethacrylic acid 2 Composite porous semiconductor magnetic nano FeZn 2 O 4 Synthesis of Poly- (methacrylic acid-ethylene glycol diacrylate) @ NiSn/TiO by Material 2 /FeZn 2 O 4 The 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 and a method for preparing the same, which can effectively adsorb metal ions in industrial wastewater and reduce the metal ions into metal.
In order to solve the problems in the prior art, the invention provides a magnetic photocatalytic water treatment agent, which comprises 60 to 70 weight percent of poly- (methacrylic acid-ethylene glycol diacrylate) and 30 to 40 weight percent of NiSn/TiO 2 /ZnFe 2 O 4 Is compounded by coating the poly- (methacrylic acid-ethylene glycol diacrylate) on NiSn/TiO 2 /ZnFe 2 O 4 Is a surface of NiSn/TiO 2 /ZnFe 2 O 4 From TiO 2 @ZnFe 2 O 4 The surface is loaded with NiSn alloy; wherein the content of the NiSn alloy is NiSn/TiO 2 /ZnFe 2 O 4 3 to 5wt%; in the NiSn alloy, the molar ratio of Ni to Sn is 1 (0.42-2.4); the TiO 2 @ZnFe 2 O 4 Is porous TiO 2 Coated porous spherical nano ZnFe 2 O 4 Carrier of ZnFe 2 O 4 The content is the TiO 2 @ZnFe 2 O 4 25-75wt%.
The invention also provides a preparation method of the magnetic photocatalytic water treatment agent, which comprises the following steps:
(1) Zn (NO) 3 ) 2 ·6H 2 O、Fe(NO 3 ) 3 ·9H 2 O and C 6 H 8 O 7 ·H 2 After O is dissolved in deionized water, adding a surfactant PEG400, stirring until the O is dissolved, performing high-pressure hydrothermal reaction, washing, drying and roasting the obtained product, and obtaining porous spherical nano ZnFe 2 O 4 ；
(2) The porous spherical nano ZnFe 2 O 4 And surfactant PEG-400 are added into absolute ethanol solution of butyl titanate, a mixture of absolute ethanol, glacial acetic acid and deionized water is dropwise added under the stirring condition, the mixture is hydrolyzed to form sol, stirring is continued, standing is carried out for 2-3 days after gel is formed, vacuum drying is carried out at 80 ℃ for 8-10 hours, and the obtained powder is ground and then is empty at 500 DEG CRoasting for 3 hours to obtain porous TiO 2 @ZnFe 2 O 4 A nanosphere;
(3) The porous TiO 2 @ZnFe 2 O 4 Adding nanospheres into deionized water, and uniformly dispersing by ultrasonic waves to form TiO 2 @ZnFe 2 O 4 A dispersion; to the TiO 2 @ZnFe 2 O 4 0.1mol/L NiSO is added dropwise to the dispersion in an amount such that the molar ratio of Ni to Sn is 1 (0.42-2.4) 4 Solution and 0.1mol/L SnCl 2 The pH of the solution is regulated to 8.5-11 after the solution is uniformly dispersed by ultrasonic, and the solution is stirred, and is protected by inert gas, and the solution is prepared by KBH at 50 DEG C 4 The number of moles of (2) is n Ni And n Sn And 5 times of the total amount, dropwise adding KBH of 0.2-0.4mol/L 4 Reacting the solution for 5-6 hours, filtering, washing the filtrate with deionized water until no chloride ions and sulfate ions exist, and vacuum drying at 80 ℃ to obtain NiSn/TiO 2 @ZnFe 2 O 4 ；
(4) The NiSn/TiO is processed by 2 @ZnFe 2 O 4 Adding 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 reacting for 4 hours, heating to 95-97 ℃, refluxing for 1 hour, standing after the reaction is finished, removing supernatant, washing the product deionized water for 2-3 times, and vacuum drying at 80 ℃ to obtain a magnetic photocatalytic water treatment agent, wherein the magnetic photocatalytic water treatment agent is poly- (methacrylic acid-ethylene glycol diacrylate) @ NiSn/TiO 2 @ZnFe 2 O 4 A composite material.
Further, in the step (1) of the above preparation method, zn (NO 3 ) 2 ·6H 2 O、Fe(NO 3 ) 3 ·9H 2 O、C 6 H 8 O 7 ·H 2 The dosage ratio of O, deionized water, and surfactant PEG400 was 0.01mol:0.02mol:0.06mol:60mL:0.8mL.
Further, in the step (2) of the preparation method, porous spherical nano ZnFe 2 O 4 The dosage ratio of the surfactant PEG-400, butyl titanate, absolute ethyl alcohol, glacial acetic acid and deionized water(1.33～12)g:0.68mL:17mL:44mL:3.6mL:3.6mL。
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 dosage of the potassium persulfate is 1 to 2 percent of the total dosage 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-vinylimidazole) is beneficial to the adsorption of metal ions in wastewater on the surface of a water treatment agent, and meanwhile, the anionic polymer poly- (methacrylic acid-ethylene glycol diacrylate) has a large number of carboxylic acid functional groups with negative charges, and is combined with the metal ions in the wastewater through electrostatic action, so that the removal of various metal ions is facilitated, and the selectivity of the metal ions is good.
(2) ZnFe in water treatment agent 2 O 4 The high magnetism 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 pH less than or equal to 4, and carboxylate exists in molecular form, so that the water treatment agent has good regeneration capability and can be recycled.
(4)ZnFe 2 O 4 Is a semiconductor catalyst with higher photocatalytic activity and sensitivity to visible light, the band gap energy is 1.9eV, and the semiconductor catalyst is prepared from TiO 2 Compounding, reducing TiO 2 The band gap energy of the photo-generated electrons is improved, the transfer rate and the efficiency of the photo-generated electrons are improved, the probability of photo-generated electron-hole recombination is greatly reduced, and the synergistic effect of the photo-generated electrons and the NiSn is greatly improved 2 The 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 wastewater treatment flow, reduces the wastewater treatment cost, and is also beneficial to recycling the metal ions in the wastewater.
Drawings
FIG. 1 shows the property of the magnetic photocatalytic water treatment agent prepared in example 1 to Cr under ultraviolet light 6+ Degradation properties;
FIG. 2 is a schematic diagram of the process of example 1Cr in visible light of magnetic photocatalytic water treatment agent 6+ Degradation properties.
Detailed Description
The invention will be further illustrated with reference to specific examples, which are carried out on the basis of the technical solutions of the invention, it being understood that these examples are only intended to illustrate the invention and are not intended to limit the scope thereof.
Example 1:
(1) Porous spherical nano ZnFe 2 O 4 Is synthesized by (a)
2.975g (0.01 mol) of Zn (NO) 3 ) 2 ·6H 2 O, 8.081g (0.02 mol) Fe (NO) 3 ) 3 ·9H 2 Dissolving O and 12.608g (0.06 mol) citric acid in 60mL deionized water, adding 0.8mL PEG400, stirring for 30 min for dissolution, transferring the mixed solution into a 100mL stainless steel high-pressure reaction kettle, reacting at 180 ℃ for 12h, 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 in a vacuum oven at 80 ℃, and roasting in a muffle furnace at 500 ℃ for 3h to obtain porous spherical nano ZnFe 2 O 4 。
(2) Porous TiO 2 @ZnFe 2 O 4 Is synthesized by (a)
The sol-gel method is adopted. 17mL of butyl titanate is dissolved in 22mL of absolute ethyl alcohol, and 0.68mL of PEG-400 and 4g of porous nano ZnFe are added 2 O 4 Dropwise adding a mixture of 22mL of absolute ethyl alcohol, 3.6mL of glacial acetic acid and 3.6mL of deionized water under stirring, continuously stirring after hydrolysis to form sol, standing for 2-3 days after gel is formed, vacuum drying at 80 ℃ for 8-10 hours, grinding the obtained powder, and roasting in a muffle furnace at 500 ℃ for 3 hours to obtain ZnFe 2 O 4 Porous TiO in an amount of 50wt% 2 @ZnFe 2 O 4 A nanosphere.
(3)NiSn/TiO 2 @ZnFe 2 O 4 Preparation of composite materials
1) 1g of porous TiO 2 @ZnFe 2 O 4 Adding into 20mL deionized water, and dispersing with ultrasound to obtain TiO 2 @ZnFe 2 O 4 A dispersion;
2) NiSO is carried out 4 Dissolving with deionized water to form 0.1mol/L NiSO 4 A solution;
3) SnCl is added 2 Dissolving with deionized water to form 0.1mol/L SnCl 2 A solution;
4) 1.74mL of 0.1mol/L NiSO was measured 4 Solution and 1.74mL of 0.1mol/L SnCl 2 Mixing the solutions, dispersing by ultrasonic wave uniformly, and dripping into TiO 2 @ZnFe 2 O 4 In the dispersion;
5) Preparing 2mol/L ammonia water solution;
6) Dripping the prepared 2mol/L ammonia water solution into the dispersion liquid obtained in the step 4), and regulating the pH value to 8.5-11;
7) KBH of 4 Dissolving in deionized water to obtain KBH 4 KBH at a concentration of 0.2mol/L 4 A solution;
8) Stirring, inert gas shielding, and dripping 8.7mL KBH into the mixed suspension with the pH value of 8.5-11 in the step 6) at 50 DEG C 4 Reacting the solution for 5 to 6 hours;
9) Filtering after the reaction is finished, washing with deionized water until the filtrate is free of chloride ions and sulfate ions, and vacuum drying at 80 ℃ to obtain W NiSn ＝3％，n Ni :n Sn NiSn/TiO in a molar ratio of 1:1 2 @ZnFe 2 O 4 A composite material.
(4) Poly- (methacrylic acid-ethylene glycol diacrylate) @ NiSn/TiO 2 @ZnFe 2 O 4 Preparation of Water treatment agent
Firstly, weighing 5g of NiSn/TiO prepared in the step (1) 2 @ZnFe 2 O 4 The composite material was added to 100mL of deionized water and dispersed with stirring. 6.9g of ethylene glycol diacrylate and 0.15g of initiator potassium persulfate were added. Stirring and heating to about 60 ℃, reacting for 30 minutes, then adding 0.6g 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 with deionized water for 2-3 times, and vacuum drying at 80 ℃ to obtain the poly- (methacrylic acid-ethylene glycol diacrylate) with the poly- (methacrylic acid-ethylene glycol diacrylate) content of 60 percentAcid ester) @ NiSn/TiO 2 @ZnFe 2 O 4 Composite material water treatment agent.
Example 2
(1) Porous spherical nano ZnFe 2 O 4 Is synthesized by (a)
2.975g (0.01 mol) of Zn (NO) 3 ) 2 ·6H 2 O, 8.081g (0.02 mol) Fe (NO) 3 ) 3 ·9H 2 Dissolving O and 12.608g (0.06 mol) citric acid in 60mL deionized water, adding 0.8mL PEG400, stirring for 30 min for dissolution, transferring the mixed solution into a 100mL stainless steel high-pressure reaction kettle, reacting at 180 ℃ for 12h, 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 in a vacuum oven at 80 ℃, and roasting in a muffle furnace at 500 ℃ for 3h to obtain porous spherical nano ZnFe 2 O 4 。
(2) Porous TiO 2 @ZnFe 2 O 4 Is synthesized by (a)
The sol-gel method is adopted. 17mL of butyl titanate is dissolved in 22mL of absolute ethyl alcohol, and 0.68mL of PEG-400 and 1.72g of porous nano ZnFe are added 2 O 4 Dropwise adding a mixture of 22mL of absolute ethyl alcohol, 3.6mL of glacial acetic acid and 3.6mL of deionized water under stirring, continuously stirring after hydrolysis to form sol, standing for 2-3 days after gel is formed, vacuum drying at 80 ℃ for 8-10 hours, grinding the obtained powder, and roasting in a muffle furnace at 500 ℃ for 3 hours to obtain ZnFe 2 O 4 Porous TiO in an amount of 30% 2 @ZnFe 2 O 4 A nanosphere.
(3)NiSn/TiO 2 @ZnFe 2 O 4 Preparation of composite materials
1) 1g of porous TiO 2 @ZnFe 2 O 4 Adding into 20mL deionized water, and dispersing with ultrasound to obtain 50-100 mg/mL TiO 2 @ZnFe 2 O 4 A dispersion;
2) NiSO is carried out 4 Dissolving with deionized water to form 0.1mol/L solution;
3) SnCl is added 2 Dissolving with deionized water to form 0.1mol/L solution;
4) 1.74mL of 0.1mol/L was measuredNiSO 4 Solution and 1.74mL of 0.1mol/L SnCl 2 Mixing the solutions, dispersing by ultrasonic wave uniformly, and dripping into TiO 2 @ZnFe 2 O 4 In the dispersion;
5) Preparing 2mol/L ammonia water solution;
6) Dripping the prepared 2mol/L ammonia water solution into the dispersion liquid obtained in the step 4), and regulating the pH value to 8.5-11;
7) KBH of 4 Dissolving in deionized water to obtain KBH 4 KBH at a concentration of 0.2mol/L 4 A solution;
8) Stirring, inert gas shielding, and dripping 8.7mL KBH into the mixed suspension with the pH value of 8.5-11 in the step 6) at 50 DEG C 4 Reacting the solution for 5 to 6 hours;
9) Filtering after the reaction is finished, washing with deionized water until the filtrate is free of chloride ions and sulfate ions, and vacuum drying at 80 ℃ to obtain W NiSn ＝3％，n Ni :n Sn NiSn/TiO in a molar ratio of 1:1 2 @ZnFe 2 O 4 A composite material.
(4) Poly- (methacrylic acid-ethylene glycol diacrylate) @ NiSn/TiO 2 @ZnFe 2 O 4 Preparation of Water treatment agent
Firstly, weighing 5g of NiSn/TiO prepared in the step (1) 2 @ZnFe 2 O 4 The composite material was added to 100mL of deionized water and dispersed with stirring. 8.7g of ethylene glycol diacrylate and 0.15g of initiator potassium persulfate were added. Stirring and heating to about 60 ℃, reacting for 30 minutes, then adding 0.6g 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 with deionized water for 2-3 times, and vacuum drying at 80 ℃ to obtain the poly- (methacrylic acid-ethylene glycol diacrylate) @ NiSn/TiO with the poly- (methacrylic acid-ethylene glycol diacrylate) content of 65 percent 2 @ZnFe 2 O 4 Composite material water treatment agent.
Example 3
(1) Porous spherical nano ZnFe 2 O 4 Is synthesized by (a)
2.975g (0.01 mol) of Zn (NO) 3 ) 2 ·6H 2 O, 8.081g (0.02 mol) Fe (NO) 3 ) 3 ·9H 2 Dissolving O and 12.608g (0.06 mol) citric acid in 60mL deionized water, adding 0.8mL PEG400, stirring for 30 min for dissolution, transferring the mixed solution into a 100mL stainless steel high-pressure reaction kettle, reacting at 180 ℃ for 12h, 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 in a vacuum oven at 80 ℃, and roasting in a muffle furnace at 500 ℃ for 3h to obtain porous spherical nano ZnFe 2 O 4 。
(2) Porous TiO 2 @ZnFe 2 O 4 Is synthesized by (a)
The sol-gel method is adopted. 17mL of butyl titanate is dissolved in 22mL of absolute ethyl alcohol, and 0.68mL of PEG-400 and 9.33g of porous nano ZnFe are added 2 O 4 Dropwise adding a mixture of 22mL of absolute ethyl alcohol, 3.6mL of glacial acetic acid and 3.6mL of deionized water under stirring, continuously stirring after hydrolysis to form sol, standing for 2-3 days after gel is formed, vacuum drying at 80 ℃ for 8-10 hours, grinding the obtained powder, and roasting in a muffle furnace at 500 ℃ for 3 hours to obtain ZnFe 2 O 4 70% by weight porous TiO 2 @ZnFe 2 O 4 A nanosphere.
(3)NiSn/TiO 2 @ZnFe 2 O 4 Preparation of composite materials
1) 1g of porous TiO 2 @ZnFe 2 O 4 Adding into 20mL deionized water according to the use, and uniformly dispersing by ultrasonic to form 50-100 mg/mL TiO 2 @ZnFe 2 O 4 A dispersion;
2) NiSO is carried out 4 Dissolving with deionized water to form 0.1mol/L solution;
3) SnCl is added 2 Dissolving with deionized water to form 0.1mol/L solution;
4) 1.74mL of 0.1mol/L NiSO was measured 4 Solution and 1.74mL of 0.1mol/L SnCl 2 Mixing the solutions, dispersing by ultrasonic wave uniformly, and dripping into TiO 2 @ZnFe 2 O 4 In the dispersion;
5) Preparing 2mol/L ammonia water solution;
6) Dripping the prepared 2mol/L ammonia water solution into the dispersion liquid obtained in the step 4), and regulating the pH value to 8.5-11;
7) KBH of 4 Dissolving in deionized water to obtain KBH 4 KBH at a concentration of 0.2mol/L 4 A solution;
8) Stirring, inert gas shielding, and dripping 8.7mL KBH into the mixed suspension with the pH value of 8.5-11 in the step 6) at 50 DEG C 4 Reacting the solution for 5 to 6 hours;
9) Filtering after the reaction is finished, washing with deionized water until the filtrate is free of chloride ions and sulfate ions, and vacuum drying at 80 ℃ to obtain W NiSn ＝3％，n Ni :n Sn NiSn/TiO in a molar ratio of 1:1 2 @ZnFe 2 O 4 A composite material.
(4) Poly- (methacrylic acid-ethylene glycol diacrylate) @ NiSn/TiO 2 @ZnFe 2 O 4 Preparation of Water treatment agent
Firstly, weighing 5g of NiSn/TiO prepared in the step (1) 2 @ZnFe 2 O 4 The composite material was added to 100mL of deionized water and dispersed with stirring. 11.0g of ethylene glycol diacrylate and 0.15g of initiator potassium persulfate were added. Stirring and heating to about 60 ℃, reacting for 30 minutes, then adding 0.7g 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 with deionized water for 2-3 times, and vacuum drying at 80 ℃ to obtain the poly- (methacrylic acid-ethylene glycol diacrylate) @ NiSn/TiO with the poly- (methacrylic acid-ethylene glycol diacrylate) content of 70 percent 2 @ZnFe 2 O 4 Composite material water treatment agent.
1g/L of photocatalytic water treatment agent is added to 1mg/L of Cr 6+ In the solution, the pH value of the solution is adjusted to 4 by a pH meter. Stirring for 30 min under dark condition to perform dark adsorption before illumination to reach adsorption-desorption equilibrium. Continuous N-up during dark adsorption and illumination 2 Ensure no O in the system 2 . 100W mercury lamps and 300W xenon lamps are used as ultraviolet and visible light sources. Sampling every 5minq when irradiating with ultraviolet lamp, sampling every 15 minutes when irradiating with visible light, comparing the concentration change when no catalyst is added,and (5) calculating the degradation rate. The results are shown in FIGS. 1 and 2.
The results in FIGS. 1 and 2 show that Cr is present at about 25 minutes under UV irradiation 6+ The degradation rate of the catalyst reaches 100 percent, and Cr is contained in the catalyst under the condition of visible light for 90 minutes 6+ The degradation rate of the water treatment agent reaches 100 percent, which indicates that the prepared magnetic photocatalytic water treatment agent is specific to Cr 6+ Has better removal performance.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (5)
1. A magnetic photocatalytic water treatment agent is characterized by comprising 60-70wt% of poly- (methacrylic acid-ethylene glycol diacrylate) and 30-40wt% of NiSn/TiO 2 /ZnFe 2 O 4 Is compounded by coating the poly- (methacrylic acid-ethylene glycol diacrylate) on NiSn/TiO 2 /ZnFe 2 O 4 Is a surface of NiSn/TiO 2 /ZnFe 2 O 4 From TiO 2 @ZnFe 2 O 4 The surface is loaded with NiSn alloy; wherein the content of the NiSn alloy is NiSn/TiO 2 /ZnFe 2 O 4 3 to 5wt%; in the NiSn alloy, the molar ratio of Ni to Sn is 1 (0.42-2.4); the TiO 2 @ZnFe 2 O 4 Is porous TiO 2 Coated porous spherical nano ZnFe 2 O 4 Carrier of ZnFe 2 O 4 The content is the TiO 2 @ZnFe 2 O 4 25-75wt%.
2. A method for preparing the magnetic photocatalytic water treatment agent as set forth in claim 1, characterized by comprising the steps of:
(1) Zn (NO) 3 ) 2 ·6H 2 O、Fe(NO 3 ) 3 ·9H 2 O and C 6 H 8 O 7 ·H 2 O is dissolved in the deionized waterAdding surfactant PEG400 into the sub water, stirring until the mixture is dissolved, performing high-pressure hydrothermal reaction, washing, drying and roasting the obtained product, and obtaining porous spherical nano ZnFe 2 O 4 ；
(2) The porous spherical nano ZnFe 2 O 4 And adding surfactant PEG-400 into anhydrous ethanol solution of butyl titanate, dropwise adding a mixture of absolute 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 80deg.C for 8-10 hr, grinding the obtained powder, and air roasting at 500deg.C for 3 hr to obtain porous TiO 2 @ZnFe 2 O 4 A nanosphere;
(3) The porous TiO 2 @ZnFe 2 O 4 Adding nanospheres into deionized water, and uniformly dispersing by ultrasonic waves to form TiO 2 @ZnFe 2 O 4 A dispersion; to the TiO 2 @ZnFe 2 O 4 0.1mol/L NiSO is added dropwise to the dispersion in an amount such that the molar ratio of Ni to Sn is 1 (0.42-2.4) 4 Solution and 0.1mol/L SnCl 2 The pH of the solution is regulated to 8.5-11 after the solution is uniformly dispersed by ultrasonic, and the solution is stirred, and is protected by inert gas, and the solution is prepared by KBH at 50 DEG C 4 The number of moles of (2) is n Ni And n Sn And 5 times of the total amount, dropwise adding KBH of 0.2-0.4mol/L 4 Reacting the solution for 5-6 hours, filtering, washing the filtrate with deionized water until no chloride ions and sulfate ions exist, and vacuum drying at 80 ℃ to obtain NiSn/TiO 2 @ZnFe 2 O 4 ；
(4) The NiSn/TiO is processed by 2 @ZnFe 2 O 4 Adding 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 reacting for 4 hours, heating to 95-97 ℃, refluxing for 1 hour, standing after the reaction is finished, removing supernatant, washing the product deionized water for 2-3 times, and vacuum drying at 80 ℃ to obtain a magnetic photocatalytic water treatment agent, wherein the magnetic photocatalytic water treatment agent is poly- (methacrylic acid-ethylene glycol diacrylate) @ NiSn/TiO 2 @ZnFe 2 O 4 A composite material.
3. The method according to claim 2, wherein in step (1), zn (NO 3 ) 2 ·6H 2 O、Fe(NO 3 ) 3 ·9H 2 O、C 6 H 8 O 7 ·H 2 The dosage ratio of O, deionized water, and surfactant PEG400 was 0.01mol:0.02mol:0.06mol:60mL:0.8mL.
4. The method according to claim 2, wherein in step (2), porous spherical nano ZnFe 2 O 4 The dosage ratio of the surfactant PEG-400, the butyl titanate, the absolute ethyl alcohol, the glacial acetic acid and the deionized water (1.33-12) g is 0.68mL:17mL:44 mL:3.6mL.
5. The method according to claim 2, wherein in the step (4), the mass ratio of ethylene glycol diacrylate to methacrylic acid is (10 to 20): 1, the dosage of the potassium persulfate is 1 to 2 percent of the total dosage of the methacrylic acid and the ethylene glycol diacrylate.
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