CN113877609B - Application of flower-shaped bismuth oxyiodide material and method for treating organic pollutants in water - Google Patents
Application of flower-shaped bismuth oxyiodide material and method for treating organic pollutants in water Download PDFInfo
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- CN113877609B CN113877609B CN202111196654.2A CN202111196654A CN113877609B CN 113877609 B CN113877609 B CN 113877609B CN 202111196654 A CN202111196654 A CN 202111196654A CN 113877609 B CN113877609 B CN 113877609B
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- bismuth oxyiodide
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- CBACFHTXHGHTMH-UHFFFAOYSA-N 2-piperidin-1-ylethyl 2-phenyl-2-piperidin-1-ylacetate;dihydrochloride Chemical compound Cl.Cl.C1CCCCN1C(C=1C=CC=CC=1)C(=O)OCCN1CCCCC1 CBACFHTXHGHTMH-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000000463 material Substances 0.000 title claims abstract description 85
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 31
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000010525 oxidative degradation reaction Methods 0.000 claims abstract description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 102
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 88
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical group [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 18
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 17
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 17
- 229910052740 iodine Inorganic materials 0.000 claims description 17
- 239000011630 iodine Substances 0.000 claims description 17
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 238000004729 solvothermal method Methods 0.000 claims description 10
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 claims description 5
- 229960004306 sulfadiazine Drugs 0.000 claims description 5
- 229960005404 sulfamethoxazole Drugs 0.000 claims description 5
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 claims description 5
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical group O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 4
- 229950000244 sulfanilic acid Drugs 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 20
- 238000007254 oxidation reaction Methods 0.000 abstract description 20
- 239000003054 catalyst Substances 0.000 abstract description 16
- 229940124530 sulfonamide Drugs 0.000 abstract description 11
- 150000003456 sulfonamides Chemical class 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 9
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000004021 humic acid Substances 0.000 abstract description 7
- 239000007800 oxidant agent Substances 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 6
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- 238000004064 recycling Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 4
- 231100000331 toxic Toxicity 0.000 abstract description 4
- 230000002588 toxic effect Effects 0.000 abstract description 4
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- 229910001411 inorganic cation Inorganic materials 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 42
- -1 bismuth oxyiodide-peracetic acid Chemical compound 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 17
- 230000015556 catabolic process Effects 0.000 description 13
- 238000006731 degradation reaction Methods 0.000 description 13
- 238000003760 magnetic stirring Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000005406 washing Methods 0.000 description 8
- 230000000593 degrading effect Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000356 contaminant Substances 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000002135 nanosheet Substances 0.000 description 5
- 235000013824 polyphenols Nutrition 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
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- 239000002086 nanomaterial Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 3
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
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- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- ZHRLVDHMIJDWSS-UHFFFAOYSA-N 4-fluoro-2-nitrophenol Chemical compound OC1=CC=C(F)C=C1[N+]([O-])=O ZHRLVDHMIJDWSS-UHFFFAOYSA-N 0.000 description 1
- RHMPLDJJXGPMEX-UHFFFAOYSA-N 4-fluorophenol Chemical compound OC1=CC=C(F)C=C1 RHMPLDJJXGPMEX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
- 229940123317 Sulfonamide antibiotic Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
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- 125000003277 amino group Chemical group 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
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- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229960002135 sulfadimidine Drugs 0.000 description 1
- ASWVTGNCAZCNNR-UHFFFAOYSA-N sulfamethazine Chemical compound CC1=CC(C)=NC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 ASWVTGNCAZCNNR-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B01J35/30—
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- 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
- C02F2101/345—Phenols
-
- 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
- C02F2101/40—Organic compounds containing sulfur
-
- 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
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention relates to the technical field of wastewater treatment, in particular to application of a flower-shaped bismuth oxyiodide material and a method for treating organic pollutants in water. The invention provides an application of a flower-shaped bismuth oxyiodide material as a catalyst for oxidative degradation of organic pollutants in water. The flower-shaped bismuth oxyiodide material is used as a catalyst to construct a novel oxidation system, and the method has the advantages of high organic pollutant removal efficiency, no generation of toxic byproducts, material recovery and recycling, no interference of inorganic anions and cations, humic acid and other substances on the removal rate, wide application pH range and the like. Experimental results show that the flower-shaped bismuth oxyiodide material is used as the catalyst, the peracetic acid is used as the oxidant, a novel oxidation system is constructed, and various organic pollutants such as phenolic substances and/or sulfonamides in the water body can be effectively degraded, so that the water body is purified.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to application of a flower-shaped bismuth oxyiodide material and a method for treating organic pollutants in water.
Background
As social productivity develops, more and more organic matters are used for industrial and agricultural production, and the emission and release of these organic matters pose many environmental problems. Many organic materials with wide application are difficult to degrade in the traditional biological treatment process, and if the organic materials are not properly disposed, the organic materials cause harm to public health and ecological environment. Advanced oxidation technology is generally used to carry out efficient and rapid oxidative degradation on the organic pollutants with high chemical stability. However, the practical application scenarios of the existing advanced oxidation systems are still limited, for example: the advanced oxidation system using hydrogen peroxide as an oxidant has weak oxidation capacity; and the persulfate-based advanced oxidation system can cause a large amount of sulfate ions to be discharged, thereby causing secondary pollution. Therefore, a new environment-friendly advanced oxidation system is urgently needed for the harmless treatment of organic pollutants.
Recently, researchers have used the common disinfectant peracetic acid in a high-level oxidation system, and the reduction product acetic acid of the peracetic acid has no toxic effect on the ecological environment and the human health, is a carbon source which most microorganisms can utilize, can promote the proliferation of the microorganisms in the subsequent biological treatment process, and can realize the thorough removal. However, there are fewer known types of catalysts having activating capabilities for this new type of oxidant. Most of the existing researches use transition metal ions and peracetic acid to construct homogeneous advanced oxidation systems, but the systems inevitably cause secondary pollution of the transition metal ions, and the applicable pH range is narrow; research reports that a heterogeneous advanced oxidation system can be constructed by using transition metal oxide and peracetic acid, but the problems of metal ion leakage and poor cycle stability cannot be solved. Meanwhile, when the existing peroxyacetic acid-based advanced oxidation system is used for degrading sulfonamides, nitrosation, nitration and coupling byproducts generated by oxidation of amino groups are commonly observed, and the byproducts still have high biological toxicity and environmental hazards. Therefore, there is still a lack of an environmentally friendly and economically efficient peroxyacetic acid activation technology.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an application of a flower-shaped bismuth oxyiodide material and a method for treating organic pollutants in water, wherein the flower-shaped bismuth oxyiodide material is used as a catalyst to construct a novel oxidation system, so that various organic pollutants in a water body can be effectively degraded.
The invention provides an application of a flower-shaped bismuth oxyiodide material as a catalyst for oxidative degradation of organic pollutants in water.
The invention also provides application of the flower-shaped bismuth oxyiodide material as a catalyst for oxidative degradation of phenolic substances and/or sulfonamides in water.
Preferably, the flower-like bismuth oxyiodide material is prepared according to the following method:
a) Stirring and mixing the ethylene glycol solution containing bismuth nitrate and the ethylene glycol solution containing iodine inorganic salt to obtain a flower-shaped bismuth oxyiodide material precursor;
the ethylene glycol solution containing bismuth nitrate and the ethylene glycol solution containing iodine inorganic salt have the same concentration and the same volume;
b) And carrying out solvothermal reaction on the flower-shaped bismuth oxyiodide material precursor to obtain the flower-shaped bismuth oxyiodide material.
Preferably, in step a), the bismuth-containing nitrate is bismuth nitrate pentahydrate;
the iodine-containing inorganic salt is potassium iodide;
the concentration of the ethylene glycol solution containing bismuth nitrate and the concentration of the ethylene glycol solution containing iodine inorganic salt are both 40-160 mu mol/L.
Preferably, in the step B), the temperature of the solvothermal reaction is 160-180 ℃ and the time is 12-24 h.
The invention also provides a method for treating organic pollutants in water, which comprises the following steps:
mixing the flower-shaped bismuth oxyiodide material, peracetic acid and the water containing organic pollutants, and performing oxidative degradation to obtain the treated water.
Preferably, the concentration of the organic pollutants in the water body containing the organic pollutants is 20-220 mu mol/L.
Preferably, the adding amount of the flower-shaped bismuth oxyiodide material in the water body containing the organic pollutants is 0.1-1 g/L.
Preferably, the adding amount of the peroxyacetic acid in the water body containing the organic pollutants is 200-1600 mu mol/L.
Preferably, the oxidative degradation is carried out under stirring;
the pH value of the oxidative degradation is 2-11.
The invention provides an application of a flower-shaped bismuth oxyiodide material as a catalyst for oxidative degradation of organic pollutants in water. The method uses the flower-shaped bismuth oxyiodide material as the catalyst to construct a novel oxidation system, and has the advantages of high organic pollutant removal efficiency, no generation of toxic byproducts, material recovery and recycling, no interference of inorganic anions and cations, humic acid and other substances on the removal rate, wide pH application range and the like. Experimental results show that the flower-shaped bismuth oxyiodide material is used as a catalyst, the peroxyacetic acid is used as an oxidant, a novel oxidation system is constructed, and various organic pollutants such as phenolic substances and/or sulfonamides in a water body can be effectively degraded, so that the water body is purified.
Drawings
FIG. 1 is a phase characterization of a flower-like bismuth oxyiodide material of example 1 of the present invention;
FIG. 2 is an SEM image of a flower-like bismuth oxyiodide material of example 1 of the present invention;
FIG. 3 is a TEM image of a flower-like bismuth oxyiodide material of example 1 of the present invention;
FIG. 4 is a graph showing the degradation kinetics of various concentrations of bisphenol A in a flower-like bismuth oxyiodide material-peracetic acid system;
FIG. 5 shows the removal rate of bisphenol A by activated peracetic acid in each cycle of the flower-shaped bismuth oxyiodide material within 5 min;
FIG. 6 is a graph showing the degradation kinetics of bisphenol A in a bismuth oxyiodide-peracetic acid system with different amounts of flower-like bismuth oxyiodide material added;
FIG. 7 is a graph showing the kinetics of degradation of bisphenol A in a bismuth oxyiodide-peracetic acid system with different amounts of peracetic acid added;
FIG. 8 is a graph of reaction rate constants and bisphenol A removal at different initial pH values;
FIG. 9 shows the reaction rate constants and bisphenol A removal rates for different water samples as reaction media;
FIG. 10 is a kinetic curve of a flower-like bismuth oxyiodide-peracetic acid system for degrading sulfanilic acid, sulfadiazine, sulfamethoxazole, and other substances;
FIG. 11 shows bisphenol A removal at the water outlet with different inlet flow rates.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The invention provides an application of a flower-shaped bismuth oxyiodide material as a catalyst for oxidative degradation of organic pollutants in water.
The flower-shaped bismuth oxyiodide material is used as a catalyst to construct a novel oxidation system, and the method has the advantages of high organic pollutant removal efficiency, no generation of toxic byproducts, material recovery and recycling, no interference of inorganic anions and cations, humic acid and other substances on the removal rate, wide application pH range and the like. Therefore, the application of the flower-shaped bismuth oxyiodide material as a catalyst for oxidative degradation of organic pollutants in water is claimed.
In certain embodiments of the invention, the organic contaminants comprise phenolics and/or sulfonamides.
In certain embodiments of the invention, the flower-like bismuth oxyiodide material is prepared according to the following method:
a) Stirring and mixing the ethylene glycol solution containing bismuth nitrate and the ethylene glycol solution containing iodine inorganic salt to obtain a flower-shaped bismuth oxyiodide material precursor;
the ethylene glycol solution containing bismuth nitrate and the ethylene glycol solution containing iodine inorganic salt have the same concentration and the same volume;
b) And carrying out solvothermal reaction on the flower-shaped bismuth oxyiodide material precursor to obtain the flower-shaped bismuth oxyiodide material.
The method comprises the steps of stirring and mixing the ethylene glycol solution containing bismuth nitrate and the ethylene glycol solution containing iodine inorganic salt to obtain a flower-shaped bismuth oxyiodide material precursor.
Preferably, the method comprises the following steps: under the condition of stirring, dropwise adding an ethylene glycol solution containing iodine inorganic salt into an ethylene glycol solution containing bismuth nitrate to obtain a flower-like bismuth oxyiodide material precursor.
In some embodiments of the invention, the stirring speed is 480 to 520r/min. In certain embodiments of the invention, the rotational speed of the agitation is 500r/min.
In certain embodiments of the invention, the dropping is at a rate of 15 to 25 drops/min. In certain embodiments of the invention, the instillation is at a rate of 20 drops/min.
In certain embodiments of the invention, the bismuth-containing nitrate salt is bismuth nitrate pentahydrate.
In certain embodiments of the present invention, the iodine containing inorganic salt is potassium iodide.
In certain embodiments of the invention, the ethylene glycol solution containing bismuth nitrate and the ethylene glycol solution containing iodine inorganic salt have the same concentration, ranging from 20 to 200. Mu. Mol/L. In certain embodiments, the concentration of the ethylene glycol solution containing bismuth nitrate salt and the concentration of the ethylene glycol solution containing iodine inorganic salt are both 40 to 160. Mu. Mol/L. In certain embodiments, the concentration of the ethylene glycol solution containing bismuth nitrate salt and the concentration of the ethylene glycol solution containing iodine inorganic salt are both 80 μmol/L.
In certain embodiments of the invention, the ethylene glycol solution containing bismuth nitrate salt and the ethylene glycol solution containing iodine inorganic salt have the same volume.
And after obtaining a flower-shaped bismuth oxyiodide material precursor, carrying out solvothermal reaction on the flower-shaped bismuth oxyiodide material precursor to obtain the flower-shaped bismuth oxyiodide material.
In certain embodiments of the present invention, the solvothermal reaction is carried out at a temperature of 160 to 180 ℃ for a period of 12 to 24 hours. In certain embodiments, the solvothermal reaction temperature is 160 ℃. In certain embodiments, the solvothermal reaction time is 12h.
In certain embodiments of the present invention, the solvothermal reaction further comprises: and (5) naturally cooling. In certain embodiments of the invention, cooling to room temperature is natural.
In some embodiments of the present invention, after the natural cooling, the method further comprises: centrifuging, washing and drying.
In certain embodiments of the present invention, the washing comprises:
sequentially washing with water and ethanol.
In certain embodiments of the present invention, the water wash employs deionized water. In certain embodiments, the number of water washes is 3. In certain embodiments, the ethanol is at a mass concentration of 50% to 100%. In certain embodiments, the ethanol is present at a mass concentration of 60%. In certain embodiments, the number of ethanol washes is 1.
In certain embodiments of the invention, the temperature of the drying is 65 to 75 ℃. In certain embodiments, the temperature of the drying is 70 ℃.
The flower-shaped bismuth oxyiodide material prepared by the invention is orange or orange red, has a flower-ball-shaped structure and is assembled by bismuth oxyiodide nanosheets, and the whole material is uniform and spherical.
In certain embodiments of the invention, the flower-like bismuth oxyiodide material has a particle size of 1 to 10 μm. In certain embodiments of the invention, the flower-like bismuth oxyiodide material has a particle size of 2 to 8 μm.
In certain embodiments of the present invention, the bismuth oxyiodide nanoplates have a thickness in the range of 5 to 25nm. In certain embodiments of the present invention, the bismuth oxyiodide nanosheets have a thickness of from 10 to 20nm. The main exposed crystal faces of the bismuth oxyiodide nanosheets are a [110] crystal face and a [001] crystal face.
The invention also provides a method for treating organic pollutants in water, which comprises the following steps:
mixing the flower-shaped bismuth oxyiodide material, peracetic acid and the water containing organic pollutants, and performing oxidative degradation to obtain the treated water.
Preferably, the method comprises the following steps:
a) Adding the flower-shaped bismuth oxyiodide material into a water body containing organic pollutants to obtain a mixed feed liquid;
b) And adding the peroxyacetic acid into the stirred mixed feed liquid for oxidative degradation.
The flower-shaped bismuth oxyiodide material adopted in the method for treating the organic pollutants in the water is the same as the flower-shaped bismuth oxyiodide material, and is not described again here.
In certain embodiments of the present invention, the water body containing organic contaminants comprises phenolics and/or sulfonamides. Specifically, the compound comprises at least one of bisphenol A, halogenated phenol, sulfanilic acid, sulfadiazine and sulfamethoxazole.
In some embodiments of the invention, the concentration of the organic pollutant in the water body containing the organic pollutant is 20-220 mu mol/L. In certain embodiments, the concentration of organic contaminants in the water containing organic contaminants is 5mg/L (21.9. Mu. Mol/L), 10mg/L (43.8. Mu. Mol/L), 20mg/L (87.6. Mu. Mol/L), or 50mg/L (219. Mu. Mol/L).
In some embodiments of the invention, the dosage of the flower-like bismuth oxyiodide material in the water body containing the organic pollutants is 0.1-1 g/L. In certain embodiments, the amount of flower-like bismuth oxyiodide material added to the organic contaminant-containing water is 0.1g/L, 0.2g/L, 0.4g/L, or 1g/L.
In some embodiments of the invention, the amount of the peroxyacetic acid added in the water body containing the organic pollutants is 200 to 1600 mu mol/L. In certain embodiments, the peroxyacetic acid is added to the organic contaminant-containing water in an amount of 200, 400, 800, or 1600 μmol/L.
In certain embodiments of the invention, the oxidative degradation has a pH of from 2 to 11. In certain embodiments, the oxidative degradation has a pH of 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11. In certain embodiments of the invention, the pH of the oxidative degradation may be adjusted by adding an acid, which may be sulfuric acid, or a base, which may be sodium hydroxide.
In some embodiments of the invention, the stirring speed of the mixed liquid is 480 to 520r/min.
In certain embodiments, the agitation rate of the mixed liquor is 500r/min.
In certain embodiments of the invention, the oxidative degradation is carried out under agitation. In certain embodiments of the invention, the rate of agitation is 480 to 520r/min. In certain embodiments, the rate of stirring is 500r/min.
In certain embodiments of the present invention, after the oxidative degradation, further comprising: centrifuging and washing the oxidatively degraded flower-shaped bismuth oxyiodide material. The flower-shaped bismuth oxyiodide material can be recycled. In certain embodiments, the washing may be with deionized water.
The source of the above-mentioned raw materials is not particularly limited, and the raw materials may be generally commercially available.
The invention adopts flower-shaped bismuth oxyiodide material as catalyst and peracetic acid as oxidant to construct a novel oxidation system, which can effectively degrade various organic pollutants in water body, thereby purifying the water body. Compared with the prior art, the invention has the following advantages:
(1) The secondary pollution of sulfate ions and transition metal ions can not be generated;
(2) Common phenolic organic pollutants can be efficiently degraded, the sulfonamide antibiotics can be effectively removed, and toxic coupling byproducts are not generated;
(3) The removal efficiency is less influenced by chloride ions, bicarbonate ions, humic acid and initial pH value;
(4) The flower-shaped bismuth oxyiodide material can be collected and recycled for a plurality of times.
In order to further illustrate the present invention, the following will describe the application of a flower-shaped bismuth oxyiodide material and the method for treating organic pollutants in water in detail with reference to the examples, but the application is not to be construed as limiting the scope of the present invention.
Example 1
Preparing a flower-shaped bismuth oxyiodide material:
in a 250mL beaker, 3.886g of bismuth nitrate pentahydrate was added, 100mL of ethylene glycol was added, and the mixture was dissolved with stirring to obtain an ethylene glycol solution of bismuth nitrate. And adding 1.328g of potassium iodide into another 250mL beaker, adding 100mL of ethylene glycol, and stirring for dissolving to obtain an ethylene glycol solution of potassium iodide. Under the continuous magnetic stirring of 500r/min, dropwise adding the ethylene glycol solution of potassium iodide into the ethylene glycol solution of bismuth nitrate by using a dropping funnel at the speed of 20 drops/min to obtain 200mL of transparent orange-red precursor solution;
and subpackaging the orange-red transparent precursor solution into a polytetrafluoroethylene reaction kettle inner container with the volume of 100mL, and accommodating 50mL of transparent precursor solution in each kettle. Sleeving a stainless steel kettle sleeve, placing the stainless steel kettle sleeve in an oven, heating to 160 ℃, carrying out solvent thermal reaction for 12 hours, then naturally cooling to room temperature, washing with deionized water for three times, washing with 60% ethanol for one time, and placing in a forced air drying oven at 70 ℃ for drying to obtain the flower-shaped bismuth oxyiodide material.
FIG. 1 is a phase diagram of a flower-like bismuth oxyiodide material of example 1 of the present invention. The X-ray standard diffraction spectrograms of the synthesized bismuth oxyiodide nano material and the bismuth oxyiodide can be well matched, and no obvious phase change occurs before and after the reaction, so that the bismuth oxyiodide nano material can keep good stability in the catalysis process.
Fig. 2 is an SEM image of the flower-like bismuth oxyiodide material of example 1 of the present invention. The synthesized bismuth oxyiodide nano material presents a uniform flower-ball-shaped microstructure, and the diameter of the bismuth oxyiodide nano material is about 2-8 mu m. The flower ball is formed by combining smaller bismuth oxyiodide nano-sheets.
FIG. 3 is a TEM image of a flower-like bismuth oxyiodide material of example 1 of the present invention. The thickness of the bismuth oxyiodide nano-sheet is about 10-20 nm, and two clear lattice fringes of a [110] crystal face and a [001] crystal face are presented.
Example 2
Removing bisphenol A in water by using a flower-shaped bismuth oxyiodide-peroxyacetic acid system:
the flower-like bismuth oxyiodide material obtained in example 1 was added to a solution to be treated with bisphenol a in an amount of 0.2g/L; under the magnetic stirring of 500r/min, peroxyacetic acid is added, the adding amount is 800 mu mol/L, and the oxidative degradation is carried out.
FIG. 4 is a graph showing the degradation kinetics of various concentrations of bisphenol A in a flower-shaped bismuth oxyiodide material-peracetic acid system. As can be seen from FIG. 4, within 2min, bisphenol A within 10mg/L (43.8. Mu. Mol/L) was completely removed, the removal rate of bisphenol A within 20mg/L (87.6. Mu. Mol/L) was 80%, and the removal rate of bisphenol A within 50mg/L (219. Mu. Mol/L) was about 60%.
Example 3
Recycling of flower-shaped bismuth oxyiodide material:
the flower-shaped bismuth oxyiodide material used in example 2 was recovered by centrifugation, washed with deionized water, and then 10mg/L of bisphenol A solution was added, and further peracetic acid was added under magnetic stirring at 500r/min in an amount of 800. Mu. Mol/L. And detecting the removal rate of the bisphenol A after 5min of reaction. And (3) repeatedly washing and recycling the flower-shaped bismuth oxyiodide material according to the scheme, and monitoring the removal rate of the bisphenol A after 5min until the catalytic capacity is reduced to the extent that the bisphenol A in the solution cannot be completely degraded due to catalyst loss. FIG. 5 shows the removal rate of bisphenol A by activated peracetic acid in 5min of each cycle of use of the flower-shaped bismuth oxyiodide material, and it can be seen from FIG. 5 that in the previous 5 cycles, the degradation rate of bisphenol A in 5 minutes can reach 100%, and in the previous 8 cycles, 80% degradation rate can be guaranteed, thus showing good stability.
Example 4
The application of removing bisphenol A in water under different bismuth oxyiodide dosage comprises the following steps:
the flower-shaped bismuth oxyiodide material of the embodiment 1 is added into a solution taking bisphenol A as a treatment object, and the adding amount is 0.1 to 1g/L; peroxyacetic acid is added under the magnetic stirring of 500r/min, and the adding amount is 800 mu mol/L. FIG. 6 is a graph showing the kinetics of degradation of bisphenol A in a bismuth oxyiodide-peracetic acid system with different amounts of flower-like bismuth oxyiodide material. As can be seen from FIG. 6, within 2min, when 5mg of flower-like bismuth oxyiodide material is added into each 50mL of reaction system, the removal rate of bisphenol A is only 50.3%; the addition of 50mg of flower-shaped bismuth oxyiodide material powder can improve the removal rate of the bisphenol A to 96.2%, and the reaction rate is in direct proportion to the addition amount of the flower-shaped bismuth oxyiodide material powder.
Example 5
Application of removing bisphenol A in water under different adding amounts of peroxyacetic acid:
the flower-like bismuth oxyiodide material of example 1 was added to a solution to be treated with bisphenol a in an amount of 0.2g/L; different amounts of peroxyacetic acid were added under magnetic stirring at 500r/min. FIG. 7 is a graph showing the kinetics of degradation of bisphenol A in a bismuth oxyiodide-peroxyacetic acid system with different amounts of peroxyacetic acid added. As can be seen from fig. 7, within 2min, different amounts of peracetic acid had little effect on the reaction rate and degradation efficiency, while an increase in the amount of peracetic acid would rather result in a slowing of the reaction rate to some extent, probably because an excess of oxidizing agent would cause damage to the structure and morphology of the catalyst. Therefore, in practical use, the amount of the oxidizing agent to be added needs to be controlled.
Example 6
The application of a flower-shaped bismuth oxyiodide-peracetic acid system in removing bisphenol A in water under different pH values:
the flower-like bismuth oxyiodide material of example 1 was added to a solution to be treated with bisphenol a in an amount of 0.2g/L; adjusting the initial pH value by using sulfuric acid and sodium hydroxide, and then adding peroxyacetic acid under the magnetic stirring of 500r/min, wherein the adding amount is 800 mu mol/L. FIG. 8 is a graph of reaction rate constants and bisphenol A removal at different initial pH values. As can be seen from fig. 8, when the initial pH value is 2 to 11 within 2min, the flower-like bismuth oxyiodide-peracetic acid system can effectively remove bisphenol a (the removal rate corresponding to pH value 2 is 22.31%, the removal rate corresponding to pH value 3 is 50.26%, the removal rate corresponding to pH value 4 is 65.94%, the removal rate corresponding to pH value 5 is 68.78%, the removal rate corresponding to pH value 6 is 66.92%, the removal rate corresponding to pH value 7 is 66.56%, the removal rate corresponding to pH value 8 is 73.51%, the removal rate corresponding to pH value 9 is 79.18%, the removal rate corresponding to pH value 10 is 87.65%, and the removal rate corresponding to pH value 11 is 93.41%), and particularly, the system shows a significant weak alkaline degradation capability improvement under the weak alkaline condition. Therefore, compared with the existing advanced oxidation system based on peroxyacetic acid, the floriform bismuth oxyiodide-peroxyacetic acid system constructed by the invention has a wide pH application range.
Example 7
The application of a flower-shaped bismuth oxyiodide-peracetic acid system to removing bisphenol A in water in the presence of chloride ions is as follows:
the flower-like bismuth oxyiodide material of example 1 was added to a solution to be treated with bisphenol a in an amount of 0.2g/L; after sodium chloride with different concentrations is added, peroxyacetic acid is added under the magnetic stirring of 500r/min, and the adding amount is 800 mu mol/L.
Experimental results show that the addition of 0.2-2 mu mol/L of chloride ions does not affect the capacity of a flower-like bismuth oxyiodide-peracetic acid system for removing bisphenol A, but has a certain promotion effect. Therefore, the bismuth oxyiodide-peracetic acid system constructed by the invention has stronger resistance to common chloride ion interference in the environment.
Example 8
The application of a flower-like bismuth oxyiodide-peracetic acid system in removing bisphenol A in water in the presence of bicarbonate ions:
the flower-like bismuth oxyiodide material of example 1 was added to a solution to be treated with bisphenol a in an amount of 0.2g/L; after sodium bicarbonate with different concentrations is added, peroxyacetic acid is added under the magnetic stirring of 500r/min, and the adding amount is 800 mu mol/L.
The experimental result shows that the addition of 0.2-2 mu mol/L bicarbonate ions can promote the bisphenol A removal capability of the flower-shaped bismuth oxyiodide-peroxyacetic acid system; when the bicarbonate ion concentration reaches 2. Mu. Mol/L, the reaction rate is increased by nearly 5 times. Therefore, the flower-like bismuth oxyiodide-peroxyacetic acid system constructed by the invention has stronger resistance to bicarbonate ion interference common in the environment.
Example 9
The application of a flower-like bismuth oxyiodide-peracetic acid system in removing bisphenol A in water in the presence of humic acid:
the flower-like bismuth oxyiodide material of example 1 was added to a solution to be treated with bisphenol a in an amount of 0.2g/L; after humic acid with different concentrations is added, peroxyacetic acid is added under the magnetic stirring of 500r/min, and the adding amount is 800 mu mol/L.
Experimental results show that the addition of 1-10 mg/L humic acid does not affect the bisphenol A removing capability of the flower-shaped bismuth oxyiodide-peracetic acid system, but has a certain promoting effect. Therefore, the flower-shaped bismuth oxyiodide-peracetic acid system constructed by the invention has stronger resistance to the interference of common soluble organic matters in the environment.
Example 10
The application of a flower-shaped bismuth oxyiodide-peracetic acid system in removing bisphenol A in an actual water source comprises the following steps:
for better explanationThe feasibility of the flower-shaped bismuth oxyiodide-peracetic acid system provided by the invention in the actual removal of pollutants respectively obtains a tap water sample of a fertilizer market and a water inlet sample and a water outlet sample of a sewage treatment plant of the fertilizer market through an open area. The obtained water sample was filtered through a 22 μm cellulose acetate membrane and then dissolved with 20mg/L bisphenol A as a treatment object. The flower-like bismuth oxyiodide material of example 1 was added to the above solution in an amount of 0.2g/L. Peroxyacetic acid is added under the magnetic stirring of 500r/min, and the adding amount is 800 mu mol/L. FIG. 9 shows the reaction rate constants and bisphenol A removal rates for different water samples as reaction media. As can be seen from FIG. 9, the rate constant of the reaction was only 29.7X 10 in deionized water -3 The removal rate within s-1,2min can only reach 90.7 percent; in tap water, the reaction rate constant can reach 59.6 multiplied by 10 -3 s -1 The removal rate within 2min reaches 93.1 percent; the reaction rate constants of the water inlet and the water outlet of a sewage treatment plant reach 93.3 and 107.87 multiplied by 10 respectively -3 s -1 And the removal rate in 2min also reaches 97.1 percent and 97.9 percent respectively. It can be seen that when water which is common in cities is used as a reaction medium, ions or organic matters which may exist in the water can promote the degradation and removal of organic pollutants by the flower-shaped bismuth oxyiodide-peracetic acid system constructed by the invention, and the removal efficiency of the organic pollutants can also be improved.
Example 11
The application of a flower-shaped bismuth oxyiodide-peracetic acid system in removing various halogenated phenols:
the flower-like bismuth oxyiodide material of example 1 was added to a solution to be treated with bisphenol a in an amount of 0.2g/L; peroxyacetic acid is added under the magnetic stirring of 500r/min, and the adding amount is 800 mu mol/L.
Tests prove that the flower-shaped bismuth oxyiodide-peracetic acid system constructed by the invention has better removal capability on various halogenated phenols: the kinetic constant of the system for degrading the 4-fluorophenol is 137 multiplied by 10 -3 min -1 Kinetic constants for degradation of 4-fluoro-2-nitro-phenol are 13X 10 -3 min -1 The kinetic constant for degrading 4-chlorophenol is 127 multiplied by 10 -3 min -1 Method for degrading 2,4,6-trichlorophenolKinetic constant of 12X 10 -3 min-1, kinetic constant for degrading tetrabromobisphenol A is 58 multiplied by 10 -3 min -1 。
Example 12
The application of a flower-shaped bismuth oxyiodide-peracetic acid system in removing various sulfonamides is as follows:
the flower-shaped bismuth oxyiodide material in the embodiment 1 is added into solutions taking different sulfonamides as treatment objects, and the adding amount is 0.2g/L; peroxyacetic acid is added under the magnetic stirring of 500r/min, and the adding amount is 800 mu mol/L. FIG. 10 is the kinetic curve of the flower-like bismuth oxyiodide-peracetic acid system for degrading sulfanilic acid, sulfadiazine, sulfamethoxazole and other substances. As can be seen from figure 10, the system can effectively degrade different sulfonamides, and particularly the removal rates of sulfamethoxazole, sulfamethazine and sulfadiazine which are commonly used sulfonamides reach 72.84%, 83.34% and 76.53% respectively. The flower-shaped bismuth oxyiodide-peroxyacetic acid system constructed by the invention has better removing capability on various sulfonamides.
Example 13
The application of removing bisphenol A by peroxyacetic acid oxidation for a long time is realized by constructing a continuous flow reactor by using flower-shaped bismuth oxyiodide:
the flower-like bismuth oxyiodide material powder of example 1 was supported on a cotton wool carrier, and a continuous degradation experiment was performed with bisphenol a as a treatment target. A peristaltic pump was used to continuously inject a mixed solution of peracetic acid and bisphenol A into the upflow reactor, wherein the concentration of peracetic acid was 800. Mu. Mol/L and the concentration of bisphenol A was 20mg/L. Tests prove that the flower-shaped bismuth oxyiodide-peracetic acid system constructed by the invention can remove bisphenol A for 48 hours in an upflow reactor, and the removal rate is kept stable. FIG. 11 shows bisphenol A removal at the water outlet with different inlet flow rates. As can be seen from FIG. 11, the removal rate of bisphenol A was substantially at or near 50% at various inlet flow rates, indicating that flower-like bismuth oxyiodide has a strong catalytic performance in this simple reactor. Therefore, the flower-like bismuth oxyiodide-peroxyacetic acid system constructed by the invention has a certain application prospect in the flow reaction.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A method for treating organic pollutants in water comprises the following steps:
mixing a flower-shaped bismuth oxyiodide material, peracetic acid and a water body containing organic pollutants, and then carrying out oxidative degradation to obtain a treated water body;
the organic pollutant is at least one of bisphenol A, halogenated phenol, sulfanilic acid, sulfadiazine and sulfamethoxazole.
2. The treatment method as claimed in claim 1, wherein the flower-like bismuth oxyiodide material is prepared according to the following method:
a) Stirring and mixing the ethylene glycol solution containing bismuth nitrate and the ethylene glycol solution containing iodine inorganic salt to obtain a flower-shaped bismuth oxyiodide material precursor;
the ethylene glycol solution containing bismuth nitrate and the ethylene glycol solution containing iodine inorganic salt have the same concentration and the same volume;
b) And carrying out solvothermal reaction on the flower-shaped bismuth oxyiodide material precursor to obtain the flower-shaped bismuth oxyiodide material.
3. The treatment process of claim 2 wherein in step a), the bismuth-containing nitrate salt is bismuth nitrate pentahydrate;
the iodine-containing inorganic salt is potassium iodide;
the concentration of the ethylene glycol solution containing bismuth nitrate and the concentration of the ethylene glycol solution containing iodine inorganic salt are both 40-160 mu mol/L.
4. The process according to claim 2, characterized in that in step B), the temperature of the solvothermal reaction is between 160 and 180 ℃ for 12 to 24 hours.
5. The treatment method according to claim 1, wherein the concentration of the organic pollutants in the water body containing the organic pollutants is 20-220 μmol/L.
6. The treatment method according to claim 1, wherein the addition amount of the flower-like bismuth oxyiodide material in the water body containing the organic pollutants is 0.1-1 g/L.
7. The treatment method according to claim 1, wherein the amount of the peroxyacetic acid added to the water body containing the organic pollutants is 200 to 1600 μmol/L.
8. The treatment process according to claim 1, characterized in that said oxidative degradation is carried out under stirring conditions;
the pH value of the oxidative degradation is 2-11.
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| CN101455973A (en) * | 2009-01-05 | 2009-06-17 | 清华大学 | Preparation method of photocatalyst for removing phenols incretion interferent in water |
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| CN111302395A (en) * | 2020-03-25 | 2020-06-19 | 长春大学 | Bismuth oxyiodide visible-light-driven photocatalyst and preparation method and application thereof |
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| CN101455973A (en) * | 2009-01-05 | 2009-06-17 | 清华大学 | Preparation method of photocatalyst for removing phenols incretion interferent in water |
| CN105565378A (en) * | 2015-12-11 | 2016-05-11 | 中国科学院兰州化学物理研究所 | BiOI mimetic enzyme material and application thereof |
| CN111302395A (en) * | 2020-03-25 | 2020-06-19 | 长春大学 | Bismuth oxyiodide visible-light-driven photocatalyst and preparation method and application thereof |
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