CN114853146B - Water treatment agent and water treatment method for magnetic recyclable pyrite catalyst - Google Patents
Water treatment agent and water treatment method for magnetic recyclable pyrite catalyst Download PDFInfo
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- CN114853146B CN114853146B CN202210440635.8A CN202210440635A CN114853146B CN 114853146 B CN114853146 B CN 114853146B CN 202210440635 A CN202210440635 A CN 202210440635A CN 114853146 B CN114853146 B CN 114853146B
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- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052683 pyrite Inorganic materials 0.000 title claims abstract description 59
- 239000011028 pyrite Substances 0.000 title claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 20
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 12
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 235000013878 L-cysteine Nutrition 0.000 claims description 6
- 239000004201 L-cysteine Substances 0.000 claims description 6
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000004729 solvothermal method Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910052952 pyrrhotite Inorganic materials 0.000 claims 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 abstract description 46
- 235000006408 oxalic acid Nutrition 0.000 abstract description 14
- 239000003344 environmental pollutant Substances 0.000 abstract description 12
- 231100000719 pollutant Toxicity 0.000 abstract description 12
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 description 27
- 238000006731 degradation reaction Methods 0.000 description 27
- 229960000282 metronidazole Drugs 0.000 description 23
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 description 23
- 239000000243 solution Substances 0.000 description 18
- 238000002474 experimental method Methods 0.000 description 16
- 238000002835 absorbance Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 238000005070 sampling Methods 0.000 description 6
- 230000000593 degrading effect Effects 0.000 description 5
- 239000002957 persistent organic pollutant Substances 0.000 description 5
- 230000003213 activating effect Effects 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 4
- 229940043267 rhodamine b Drugs 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000004098 Tetracycline Substances 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229960001381 glipizide Drugs 0.000 description 2
- ZJJXGWJIGJFDTL-UHFFFAOYSA-N glipizide Chemical compound C1=NC(C)=CN=C1C(=O)NCCC1=CC=C(S(=O)(=O)NC(=O)NC2CCCCC2)C=C1 ZJJXGWJIGJFDTL-UHFFFAOYSA-N 0.000 description 2
- 229910052598 goethite Inorganic materials 0.000 description 2
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229960002180 tetracycline Drugs 0.000 description 2
- 229930101283 tetracycline Natural products 0.000 description 2
- 235000019364 tetracycline Nutrition 0.000 description 2
- 229960004989 tetracycline hydrochloride Drugs 0.000 description 2
- 150000003522 tetracyclines Chemical class 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- BOVGTQGAOIONJV-BETUJISGSA-N 1-[(3ar,6as)-3,3a,4,5,6,6a-hexahydro-1h-cyclopenta[c]pyrrol-2-yl]-3-(4-methylphenyl)sulfonylurea Chemical compound C1=CC(C)=CC=C1S(=O)(=O)NC(=O)NN1C[C@H]2CCC[C@H]2C1 BOVGTQGAOIONJV-BETUJISGSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 231100000049 endocrine disruptor Toxicity 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 229960000346 gliclazide Drugs 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- -1 iron ion Chemical class 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
- C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a water treatment agent and a water treatment method of a magnetic recyclable pyrite catalyst, comprising pyrite and oxalic acid dihydrate, and the invention has the beneficial effects that: the water treatment agent containing the magnetic recyclable pyrite can effectively activate oxalic acid under the assistance of visible light, and has the advantages of high reaction rate and wide pH application range; the method is suitable for removing various pollutants in water, so that the method has wide application prospect, and in addition, the pyrite serving as a catalyst can be magnetically recycled, and is an environment-friendly catalyst.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a water treatment agent and a water treatment method of a magnetic recyclable pyrite catalyst.
Background
In recent years, due to the rapid development of the chemical industry, the discharged wastewater contains a large amount of organic chemicals, such as dyes, antibiotics, phenols, endocrine disruptors and other refractory organic pollutants, and the organic matters have high toxicity and bioaccumulation property, and can generate toxic effects on ecological food chains even under low concentration, however, the traditional water treatment process of combining physics and chemistry with biology cannot effectively degrade the organic pollutants, and the organic pollutants are potentially harmful to ecological environment and human health after being discharged into water.
The advanced oxidation technology has remarkable effect of treating toxic and harmful refractory organic pollutants, thorough reaction and environmental friendliness, and has wide application potential in the aspect of environmental pollution treatment. Advanced oxidation technology based on oxalic acid activation is a novel water treatment technology which is rapidly developed in recent years, and is widely focused due to the characteristics of high-efficiency treatment of refractory organic matters and small environmental pollution. From Oxalic Acid (OA) and ferric ion (Fe) 3+ ) Fe formed 3+ The OA complex can generate a large amount of oxidation active substances under the illumination condition, and Fe 3+ The photocatalytic degradation properties of the OA complexes have also proved to be stronger than those of the Fenton system. Wherein Fe is 3+ Can be rapidly carried out at room temperature, has mild reaction conditions and does not need external energy, thereby showing great superiority in the field of environmental purification. However, the transition metal ions are unfavorable for recycling, and secondary pollution and biotoxicity can be caused, so that the wide application of the transition metal ions is limited.
Disclosure of Invention
The invention aims to solve the technical problem of providing a water treatment agent and a water treatment method of a magnetic recyclable pyrite catalyst, so as to overcome the defects in the prior art.
The technical scheme for solving the technical problems is as follows: a magnetically recoverable catalyst for treating the water containing the catalyst of gavite includes gavite and oxalic acid dihydrate.
The beneficial effects of the invention are as follows: the water treatment agent containing the magnetic recyclable pyrite can effectively activate oxalic acid under the assistance of visible light, and has the advantages of high reaction rate and wide pH application range; the method is suitable for removing various pollutants in water, so that the method has wide application prospect, and in addition, the pyrite serving as a catalyst can be magnetically recycled, and is an environment-friendly catalyst.
On the basis of the technical scheme, the invention can be improved as follows.
Further, the method for preparing the pyrite by the solvothermal method comprises the following steps:
step 1: sequentially adding ferrous sulfate heptahydrate and L-cysteine into a mixed solution of ethylene glycol and water, and uniformly stirring and mixing to form a mixed solution;
step 2: transferring the mixed solution into a hydrothermal reaction kettle, and sealing the hydrothermal reaction kettle by using a stainless steel cylinder sleeve;
step 3: placing the stainless steel cylinder sleeve in a blast drying box for hydrothermal reaction;
step 4: after the reaction is finished and the hydrothermal reaction kettle is cooled to room temperature, carrying out solid-liquid separation on the reaction product to extract solid substances;
step 5: and (3) washing the solid substance with carbon disulfide and ethanol for one time and three times respectively to obtain the pyrite.
Further, the mass ratio of the pyrite to the oxalic acid dihydrate is 1:3.15 to 9.45.
Further, the molar ratio of ferrous sulfate heptahydrate to L-cysteine in step 1 was 1:1.
Further, in the step 1, the volume ratio of the glycol to the water is 1:3.
Further, the temperature of the hydrothermal reaction in the step 3 is 180 ℃, and the hydrothermal time is 12 hours.
A water treatment method uses a water treatment agent of a magnetic recoverable type pyrite catalyst to treat water under illumination conditions.
Further, the water treatment agent is added in an amount such that the concentration of the pyrite in the water body is 0.01 to 0.1g/L and the concentration of the oxalic acid dihydrate in the water body is 0.063 to 0.189 g/L.
Further, the optimal duration of the water body treatment is 10 to 60 minutes.
Further, the optimal time for treating the water body is 60 minutes.
Drawings
FIG. 1 is a schematic view of the recovery of the pyrite from solution by magnets;
FIG. 2 is a graph showing the degradation effect of the water treatment agent and other water treatment agents of the present invention on metronidazole solution;
FIG. 3 is a graph showing the catalytic degradation effect of the water treatment agent of the present invention on different organic pollutants;
fig. 4 is a graph showing the experimental effect of catalytic degradation cycle of activated oxalic acid to degrade metronidazole by using the pyrite of example 1 under the assistance of visible light;
fig. 5 is a graph showing the catalytic degradation effect of gliclazide on visible light assisted activation of oxalic acid to degrade metronidazole at different pH conditions.
Detailed Description
The principles and features of the present invention are described below with reference to the drawings, the examples are illustrated for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.
As shown in fig. 1 to 5, the water treatment agent of the magnetic recoverable type pyrite catalyst of embodiment 1 of the present invention includes pyrite and oxalic acid dihydrate.
The method for preparing the pyrite by the solvothermal method comprises the following steps:
step 1: sequentially adding ferrous sulfate heptahydrate and L-cysteine into a mixed solution of ethylene glycol and water, and uniformly stirring and mixing to form a mixed solution;
step 2: transferring the mixed solution into a hydrothermal reaction kettle, and sealing the hydrothermal reaction kettle by using a stainless steel cylinder sleeve;
step 3: placing the stainless steel cylinder sleeve in a blast drying box for hydrothermal reaction;
step 4: after the reaction is finished and the hydrothermal reaction kettle is cooled to room temperature, carrying out solid-liquid separation on the reaction product to extract solid substances;
step 5: and (3) washing the solid substance with carbon disulfide and ethanol for one time and three times respectively to obtain the pyrite.
The mass ratio of the glipizide to the oxalic acid dihydrate is 1:3.15 to 9.45.
The molar ratio of ferrous sulfate heptahydrate to L-cysteine in step 1 was 1:1.
In the step 1, the volume ratio of the glycol to the water is 1:3.
The temperature of the hydrothermal reaction in the step 3 is 180 ℃, and the hydrothermal time is 12 hours.
Experiment one: under the condition of stirring, toAdding 0.02g/L of pyrite into a metronidazole solution with the initial concentration of 10mg/L and the volume of 100mL, and continuously stirring for 30min to uniformly disperse the pyrite serving as a catalyst; adding 0.126g/L oxalic acid dihydrate into the above solution, and placing in visible light (wavelength 420nm, light intensity 55mW cm) -2 ) Sampling at intervals, and measuring the absorbance value of metronidazole after centrifugal separation; and finally, calculating the degradation rate of the degradation system on the target pollutant by using the relation between the absorbance value and the concentration equation. After 60min, the degradation rate of metronidazole was 99.3%. The solution of metronidazole is degraded by replacing the pyrite with hematite, goethite, magnetite and pyrite which is not exposed to visible light under the same operating conditions, and the degradation rates are respectively 32.6%, 87.4%, 82.7% and 9.2%.
Experiment II: adding 0.02g/L of pyrite into a metronidazole solution with the initial concentration of 10mg/L and the volume of 100mL under the stirring condition, and continuously stirring for 30min to uniformly disperse the pyrite serving as a catalyst; adding oxalic acid dihydrate with an amount of 0.063g/L into the above solution, and placing in visible light (wavelength 420nm, light intensity 55mW cm) -2 ) Sampling at intervals, and measuring the absorbance value of metronidazole after centrifugal separation; and finally, calculating the degradation rate of the degradation system on the target pollutant by using the relation between the absorbance value and the concentration equation. After 60min, the degradation rate of metronidazole was 90.0%.
Experiment III: adding 0.02g/L of pyrite into a rhodamine B solution with the initial concentration of 10mg/L and the volume of 100mL under the stirring condition, and continuously stirring for 30min to uniformly disperse the pyrite serving as a catalyst; adding 0.126g/L oxalic acid dihydrate into the above solution, and placing in visible light (wavelength 420nm, light intensity 55mW cm) -2 ) Sampling at intervals, and measuring the absorbance value of rhodamine B after centrifugal separation; and finally, calculating the degradation rate of the degradation system on the target pollutant by using the relation between the absorbance value and the concentration equation.
Experiment IV: adding 0.02g/L of pyrite to a hexavalent chromium solution having an initial concentration of 10mg/L and a volume of 100mL under stirring, and maintainingStirring for 30min to uniformly disperse the pyrite serving as the catalyst; adding 0.126g/L oxalic acid dihydrate into the above solution, and placing in visible light (wavelength 420nm, light intensity 55mW cm) -2 ) Sampling at intervals, and measuring the absorbance value of hexavalent chromium after centrifugal separation; and finally, calculating the degradation rate of the degradation system on the target pollutant by using the relation between the absorbance value and the concentration equation.
Experiment five: adding 0.02g/L of pyrite into a tetracycline solution with the initial concentration of 10mg/L and the volume of 100mL under the stirring condition, and continuously stirring for 30min to uniformly disperse the pyrite serving as a catalyst; adding 0.126g/L oxalic acid dihydrate into the above solution, and placing in visible light (wavelength 420nm, light intensity 55mW cm) -2 ) Sampling at intervals, and measuring the absorbance value of the tetracycline after centrifugal separation; and finally, calculating the degradation rate of the degradation system on the target pollutant by using the relation between the absorbance value and the concentration equation.
Experiment six: adding 0.02g/L of pyrite into an acidic red solution with an initial concentration of 10mg/L and a volume of 100mL under the stirring condition, and continuously stirring for 30min to uniformly disperse the pyrite serving as a catalyst; adding 0.126g/L oxalic acid dihydrate into the above solution, and placing in visible light (wavelength 420nm, light intensity 55mW cm) -2 ) Sampling at intervals, and measuring the absorbance value of acid red after centrifugal separation; and finally, calculating the degradation rate of the degradation system on the target pollutant by using the relation between the absorbance value and the concentration equation.
Experiment seven: and (3) activating oxalic acid to degrade metronidazole under the visible light condition by using the obtained colloidal pyrite in the experiment I.
Experiment eight: in the experiment that the obtained gum pyrite activates oxalic acid under the visible light condition to degrade the metronidazole under different pH conditions, the adding amount of the gum pyrite, the adding amount of the oxalic acid, the initial concentration of the metronidazole is 10mg/L, and the degradation effect of the metronidazole solution after 60min reaches more than 88.5%.
In conclusion, the magnetic recyclable pyrite prepared by the invention has a wide applicable pH range in a system for degrading antibiotic pollutant metronidazole under the assistance of visible light.
Fig. 1 is a schematic view of the recovery of the pyrite from the solution by means of magnets. As can be seen from fig. 1, the gavite has strong ferromagnetism, which means that the gavite can be recycled through magnetic recovery.
Fig. 2 is a graph showing the effect of activated oxalic acid on degrading metronidazole with the help of visible light and without exposing the goethite to visible light in example 1. As shown in figure 2, the degradation effect of the magnetic gum pyrite for activating the oxalic acid on the metronidazole under the visible light is better than that of other iron-based catalysts of other types under the same condition, so that the magnetic recoverable catalyst gum pyrite material prepared by the method has strong capability of catalyzing and degrading the antibiotic pollutant metronidazole.
Fig. 3 shows the effect of the experiment seven on the cyclic experiment of degrading metronidazole by activating oxalic acid under the condition of visible light on the glipizide in the experiment one, and the cyclic period is 60min. From fig. 3, the degradation performance of the metronidazole is not obviously reduced in five times of catalyst cycle experiments, which shows that the catalyst has better catalytic activation stability. The catalyst can be recycled through magnetic recovery and centrifugation, and the problems of iron ion dissolution and narrow pH application range in a homogeneous oxalic acid activation system are well solved.
Fig. 4 is a graph showing the catalytic degradation effect of activated oxalic acid on rhodamine B, hexavalent chromium, tetracycline hydrochloride and acid red in experiments three to six under visible light. As can be seen from the graph in FIG. 4, the removal efficiency of the reaction system for rhodamine B, hexavalent chromium, tetracycline hydrochloride and acid red with the volume of 100mL and the concentration of 10mg/L in 60min is almost 100%, which indicates that the prepared magnetic recoverable pyrite has excellent catalytic degradation effect on various pollutants, and the magnetic recoverable pyrite has higher application potential in the field of treatment of actual industrial wastewater.
Fig. 5 is a graph showing the catalytic degradation effect of magnetic gum pyrite in experiment eight on the degradation of metronidazole solution under different pH conditions by activating oxalic acid under visible light. As shown in FIG. 5, the catalytic reaction system is carried out for 60min, and the degradation rate of the metronidazole is more than 85%.
In conclusion, the pH range applicable to a system for degrading metronidazole by using the prepared magnetically recyclable pyrite is larger, so that the pyrite water treatment agent material prepared by the invention has larger application potential in the aspect of anti-biological pollutant treatment of different pH values.
Example 2 of the present invention a water treatment method,
the water treatment agent of magnetically recoverable pyrite in example 1 was used under light conditions.
The input amount of the water treatment agent is the dosage that the concentration of the pyrite in the water body is 0.01 to 0.1g/L, and the concentration of the oxalic acid dihydrate in the water body is 0.063 to 0.189 g/L.
The optimal duration of the water body treatment is 10 to 60 minutes.
The optimal time for treating the water body is 60min.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (9)
1. A magnetic recyclable type water treatment agent for a pyrite catalyst, which is characterized by comprising pyrite and oxalic acid dihydrate;
the method for preparing the pyrite by the solvothermal method comprises the following steps:
step 1: sequentially adding ferrous sulfate heptahydrate and L-cysteine into a mixed solution of ethylene glycol and water, and uniformly stirring and mixing to form a mixed solution;
step 2: transferring the mixed solution into a hydrothermal reaction kettle, and sealing the hydrothermal reaction kettle by using a stainless steel cylinder sleeve;
step 3: placing the stainless steel cylinder sleeve in a blast drying box for hydrothermal reaction;
step 4: after the reaction is finished and the hydrothermal reaction kettle is cooled to room temperature, carrying out solid-liquid separation on the reaction product to extract solid substances;
step 5: and (3) washing the solid substance with carbon disulfide and ethanol for one time and three times respectively to obtain the pyrite.
2. The magnetically recoverable pyrite catalyst water treatment agent according to claim 1, wherein the mass ratio of the pyrite to the oxalic acid dihydrate is 1:3.15 to 9.45.
3. The magnetically recoverable gum pyrite catalyst water treatment agent according to claim 1, wherein the molar ratio of ferrous sulfate heptahydrate to L-cysteine in step 1 is 1:1.
4. The magnetically recyclable colloidal pyrite catalyst water treatment agent according to claim 1, wherein the volume ratio of glycol to water in the step 1 is 1:3.
5. The water treatment agent for the magnetic recyclable pyrite catalyst according to claim 1, wherein the hydrothermal reaction in the step 3 is performed at 180 ℃ for 12 hours.
6. A water treatment method, characterized in that a water body is treated under illumination conditions by using the water treatment agent of the magnetic recoverable pyrite catalyst according to any one of claims 1 to 5.
7. The method according to claim 6, wherein the water treatment agent is added in an amount such that the concentration of the pyrrhotite in the water body is 0.01 to 0.1g/L and the concentration of the oxalic acid dihydrate in the water body is 0.063 to 0.189 g/L.
8. A water treatment method according to claim 7, wherein the optimal length of time for treating the body of water is between 10 and 60 minutes.
9. A water treatment method according to claim 8, wherein the optimal duration of the treatment of the body of water is 60 minutes.
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