CN113024006A - Advanced oxidation method for degrading steroid estrogen in sewage - Google Patents
Advanced oxidation method for degrading steroid estrogen in sewage Download PDFInfo
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- CN113024006A CN113024006A CN202110396245.0A CN202110396245A CN113024006A CN 113024006 A CN113024006 A CN 113024006A CN 202110396245 A CN202110396245 A CN 202110396245A CN 113024006 A CN113024006 A CN 113024006A
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- 229940011871 estrogen Drugs 0.000 title claims abstract description 95
- 150000003431 steroids Chemical class 0.000 title claims abstract description 84
- 239000010865 sewage Substances 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 38
- 230000003647 oxidation Effects 0.000 title claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 19
- 230000000593 degrading effect Effects 0.000 title claims abstract description 18
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- 239000007800 oxidant agent Substances 0.000 claims abstract description 14
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- 238000003756 stirring Methods 0.000 claims abstract description 4
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- 239000011550 stock solution Substances 0.000 claims description 34
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 31
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims description 15
- 229960000583 acetic acid Drugs 0.000 claims description 13
- DNXHEGUUPJUMQT-CBZIJGRNSA-N Estrone Chemical compound OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 DNXHEGUUPJUMQT-CBZIJGRNSA-N 0.000 claims description 11
- BFPYWIDHMRZLRN-SLHNCBLASA-N Ethinyl estradiol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 BFPYWIDHMRZLRN-SLHNCBLASA-N 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001514 detection method Methods 0.000 claims description 10
- PROQIPRRNZUXQM-ZXXIGWHRSA-N estriol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H]([C@H](O)C4)O)[C@@H]4[C@@H]3CCC2=C1 PROQIPRRNZUXQM-ZXXIGWHRSA-N 0.000 claims description 10
- PROQIPRRNZUXQM-UHFFFAOYSA-N (16alpha,17betaOH)-Estra-1,3,5(10)-triene-3,16,17-triol Natural products OC1=CC=C2C3CCC(C)(C(C(O)C4)O)C4C3CCC2=C1 PROQIPRRNZUXQM-UHFFFAOYSA-N 0.000 claims description 9
- VOXZDWNPVJITMN-ZBRFXRBCSA-N 17β-estradiol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3CCC2=C1 VOXZDWNPVJITMN-ZBRFXRBCSA-N 0.000 claims description 9
- 229960001348 estriol Drugs 0.000 claims description 9
- 238000005189 flocculation Methods 0.000 claims description 9
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- 239000012362 glacial acetic acid Substances 0.000 claims description 8
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229940079593 drug Drugs 0.000 claims description 6
- 239000003814 drug Substances 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
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- 239000007790 solid phase Substances 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
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- DNXHEGUUPJUMQT-UHFFFAOYSA-N (+)-estrone Natural products OC1=CC=C2C3CCC(C)(C(CC4)=O)C4C3CCC2=C1 DNXHEGUUPJUMQT-UHFFFAOYSA-N 0.000 description 7
- 229960003399 estrone Drugs 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- BFPYWIDHMRZLRN-UHFFFAOYSA-N 17alpha-ethynyl estradiol Natural products OC1=CC=C2C3CCC(C)(C(CC4)(O)C#C)C4C3CCC2=C1 BFPYWIDHMRZLRN-UHFFFAOYSA-N 0.000 description 5
- 229960005309 estradiol Drugs 0.000 description 5
- 229930182833 estradiol Natural products 0.000 description 5
- 229960002568 ethinylestradiol Drugs 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000001076 estrogenic effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 101000882584 Homo sapiens Estrogen receptor Proteins 0.000 description 2
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003687 estradiol congener Substances 0.000 description 2
- 230000003637 steroidlike Effects 0.000 description 2
- 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 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 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
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
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- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 230000002124 endocrine Effects 0.000 description 1
- 231100000507 endocrine disrupting Toxicity 0.000 description 1
- 210000000750 endocrine system Anatomy 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000036737 immune function Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 239000002114 nanocomposite Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 210000000653 nervous system Anatomy 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
- 238000006552 photochemical reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
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- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
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Images
Classifications
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/305—Endocrine disruptive agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
-
- 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
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Physical Water Treatments (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses an advanced oxidation method for degrading steroid estrogen in sewage, which specifically comprises the following steps: pre-treating sewage to control suspended solid below 10 mg/L; determining the concentration of steroid estrogen in the wastewater; adding a strong oxidant into sewage containing steroid estrogen in a targeted manner, and uniformly stirring; then, placing the sewage under an ultraviolet light source for irradiation treatment; after the sewage containing steroid estrogen is treated by the method, the degradation rate of the steroid estrogen and the removal rate of the estrogen activity of the sewage can reach more than 90 percent, and the sewage is less influenced by the pH value of the sewage, has less byproduct generation, is easy to upgrade and modify in the prior art, and the like, and has better application prospect in secondary biochemical tail water deep purification and surface water body treatment polluted by the steroid estrogen.
Description
Technical Field
The invention relates to the technical field of treatment of steroid estrogen in sewage, in particular to a high-grade oxidation method for degrading steroid estrogen in sewage.
Background
Steroid Estrogens (SEs) are a kind of micro refractory organic substances with high endocrine disrupting toxicity, common steroid estrogens in water are mainly classified into natural estrogens and synthetic estrogens, the natural estrogens mainly include estrone (E1), 17 beta-estradiol (E2) and estriol (E3), and the synthetic estrogens mainly include 17 alpha-ethinyl estradiol (EE2), which are generally derived from animal and human excreta and the discharge of pharmaceutical industry. In recent years, with the development of detection technologies, the estrogen-like substances are frequently detected in natural water bodies, the concentration of the estrogen-like substances is different from several ng/L to several hundred ng/L, and the estrogen-like substances are often enriched in sediment of the water bodies and released into the water environment when the environment changes, so that the concentration of the steroid estrogen in the water environment is remarkably increased. Steroid estrogens in water, even at very low concentrations (ng/L), can have adverse effects on the proliferation and growth of organisms, the endocrine and nervous systems, and immune functions.
The sewage treatment plant is an important place for receiving and treating domestic sewage and industrial wastewater, and because of lack of corresponding discharge standards, the traditional sewage treatment plant cannot specifically and efficiently remove steroid estrogen in the sewage, and multiple studies show that the concentration level of the steroid estrogen in secondary biochemical tail water of the sewage treatment plant in various regions of China often exceeds related water quality safety standards, so that the sewage treatment plant becomes an important approach for the source of the steroid estrogen in the water environment, and therefore, the steroid estrogen in the sewage gradually becomes a type of refractory organic micropollutants which should be preferentially controlled in the processes of sewage deep treatment and reclaimed water safe utilization.
At present, ultraviolet-based advanced oxidation technologies are often used for treating steroid estrogens in sewage, such as ultraviolet/hydrogen peroxide, ultraviolet/persulfate, ultraviolet/chlorine and other advanced oxidation processes due to the characteristic of good oxidation effect, but the technologies usually consume a large amount of energy, are greatly influenced by water quality and may generate large secondary pollution problems, thereby limiting the application of the technologies in practice.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an advanced oxidation method for degrading steroid estrogen in sewage.
The technical scheme of the invention is as follows: a high-grade oxidation method for degrading steroid estrogen in sewage specifically comprises the following steps:
s1: pretreatment of
Pre-treating sewage to control suspended solid below 10 mg/L;
s2: sampling detection
Measuring the concentration of steroid estrogen in the sewage by adopting a solid-phase extraction-liquid chromatography-mass spectrometry combined detection method; the method specifically comprises the following steps:
s2-1: solid phase extraction of steroid estrogens
1) Activating a CNWHLB solid phase extraction column by using 2 column tubes of methanol/ethyl acetate (1:9, V/V) and methanol in sequence; 2) balancing a CNWHLB solid phase extraction column by using 2 column pipes of pure water; 3) enriching and purifying 3mL of water sample by a CNWHLB solid phase extraction column; 4) washing the CNWHLB solid phase extraction column with 1 column tube methanol/water (1: 9); 5) eluting steroid estrogen with 10mL of methanol/ethyl acetate (1:9, V/V), blowing the eluent with nitrogen, diluting to constant volume with 1mL of methanol/water (9:1), storing in a refrigerator at-20 deg.C, and testing;
s2-2: detecting steroid estrogen liquid chromatography-mass spectrometry;
s3: peroxyacetic acid dosing
Adding a strong oxidant into sewage containing steroid estrogen in a targeted manner, and uniformly stirring;
s4: irradiation treatment
And (4) placing the sewage treated by the S3 under an ultraviolet light source for irradiation treatment.
Further, the specific steps of the sewage pretreatment in S1 are: the sewage is sequentially subjected to drug flocculation precipitation treatment, sand filtration treatment and carbon filtration treatment.
Furthermore, the drug flocculation precipitation treatment specifically adopts a magnetic flocculation precipitation method.
Further, S2 the steroid estrogens include, but are not limited to, one or more of estrone (E1), 17 β -estradiol (E2), estriol (E3), and 17 α -ethinyl estradiol (EE 2).
Further, the strong oxidizer of S3 adopts a first peroxyacetic acid stock solution; the first peroxyacetic acid stock solution is prepared by mixing glacial acetic acid and hydrogen peroxide according to the volume ratio of 1:1 and standing for 24 hours at the low temperature of 4-6 ℃; the prepared first peroxyacetic acid stock solution has strong absorption capacity on ultraviolet light, can generate hydroxyl free radicals and a series of free radicals taking carbon as the center after being excited by the ultraviolet light, and can be used as an oxidant in an advanced oxidation process.
Furthermore, the ratio of the addition amount of the first peroxyacetic acid stock solution to the content of steroid estrogen in water is 50-200: 1.
Further, the strong oxidant adopts a second peroxyacetic acid stock solution; the second peroxyacetic acid stock solution is prepared from glacial acetic acid, hydrogen peroxide, acetic acid and ammonium persulfate according to a ratio of 2:2:1:0.2, ultrasonically dispersing for 4-8 hours at the low temperature of 4-6 ℃, and then standing for 12-15 hours at the temperature of 2-4 ℃ to prepare the nano-composite material.
Further, the ratio of the content of steroid estrogen in the added water of the second peroxyacetic acid stock solution is 30-110: 1.
Further, the ultraviolet light source of S4 is any ultraviolet lamp capable of emitting ultraviolet light, wherein the wavelength of the ultraviolet light is 250-258 nm.
Further, the dose of the ultraviolet irradiation is 7500-30000J/m2(ii) a Wherein, the ultraviolet irradiation dose is the ultraviolet light intensity multiplied by the irradiation time.
Compared with the prior art, the invention has the beneficial effects that:
1. the degradation rate of steroid estrogen in the sewage treated by the method of the invention reaches more than 90 percent, and the estrogen activity in the water treated by the method of the invention is obviously reduced, and the degradation rate can reach more than 94 percent compared with the degradation rate before treatment;
2. the treatment effect of the method is slightly influenced by the pH of the sewage, and the degradation rate of steroid estrogen in the water can reach more than 90 percent in the range of the pH of the sewage being 5.22-9.28;
3. the method has simple integral process; the sewage treatment plant is easy to reform on the basis of the original process of the existing sewage treatment plant, can disinfect sewage while degrading pollutants, and is easier to apply to actual engineering.
Drawings
FIG. 1 is a graph showing the effect of UV light and peracetic acid in the present invention on the degradation of steroid estrogens in sewage;
FIG. 2 is a graph of the effect of UV/peracetic acid on degradation of steroid estrogens in sewage and an equation fitting the degradation kinetics in accordance with the present invention;
FIG. 3 is a graph showing the effect of different initial pH on UV/peracetic acid degradation of steroid estrogens in wastewater in accordance with the present invention.
Detailed Description
For a further understanding of the present invention, reference will now be made in detail to the present invention by way of examples, which are illustrated in the accompanying drawings.
Example 1: a high-grade oxidation method for degrading steroid estrogen in sewage specifically comprises the following steps:
s1: pretreatment of
Pretreating the sewage by adopting a conventional sewage pretreatment mode to control the suspended solid to be 10 mg/L;
s2: sampling detection
Measuring the concentration of steroid estrogen in the sewage by adopting a solid-phase extraction-liquid chromatography-mass spectrometry combined detection method; the method specifically comprises the following steps:
s2-1: solid phase extraction of steroid estrogens
1) Activating a CNWHLB solid phase extraction column by using 2 column tubes of methanol/ethyl acetate (1:9, V/V) and methanol in sequence; 2) balancing a CNWHLB solid phase extraction column by using 2 column pipes of pure water; 3) enriching and purifying 3mL of water sample by a CNWHLB solid phase extraction column; 4) washing the CNWHLB solid phase extraction column with 1 column tube methanol/water (1: 9); 5) eluting steroid estrogen with 10mL of methanol/ethyl acetate (1:9, V/V), blowing the eluent with nitrogen, diluting to constant volume with 1mL of methanol/water (9:1), storing in a refrigerator at-20 deg.C, and testing;
s2-2: four steroid estrogen liquid chromatography-mass spectrometry detection methods of estrone (E1), 17 beta-estradiol (E2), estriol (E3) and 17 alpha-ethinyl estradiol (EE 2):
liquid phase gradient elution method:
mass spectrometric detection parameters
S3: peroxyacetic acid dosing
Adding a strong oxidant into the pretreated sewage to enable the ratio of the concentration of the strong oxidant to the total concentration of steroid estrogen in the sewage to be 150: 1; wherein the strong oxidant adopts a first peroxyacetic acid stock solution; the first peroxyacetic acid stock solution is prepared by mixing glacial acetic acid and hydrogen peroxide according to the volume ratio of 1:1 and standing for 24 hours at the low temperature of 4-6 ℃;
s4: irradiation treatment
Then the sewage enters a photoreactor provided with a stirring device, the stirrer is started, and an ultraviolet lamp is started simultaneously to carry out photochemical reaction; wherein the ultraviolet wavelength of the ultraviolet lamp is 254 nm; the ultraviolet irradiation dose is 7500-30000J/m2(ii) a Ultraviolet irradiation dose is equal to ultraviolet intensity multiplied by irradiation time;
samples were taken from the wastewater at 1, 2, 5, 10, 15, 20 and 30min of treatment, and the reaction was stopped by immediately adding an excess of sodium thiosulfate, and then the residual steroid estrogen in the water was measured by a solid phase extraction-liquid chromatography mass spectrometry method. The time t is plotted on the abscissa, the steroid estrogen concentration (C)/the initial steroid estrogen concentration (C0) is plotted on the ordinate, and t is plotted on the abscissa, and ln (C/C0) is plotted on the ordinate to fit the degradation kinetics of steroid estrogen, and the experimental results are shown in fig. 2.
It should be noted that: in this example, two additional comparative examples were provided, one of which was treated without peracetic acid, and the other was not treated by uv irradiation, and the other steps were the same as those of the examples in steps S1, S2, S3, and S4, and the experimental results are shown in fig. 1.
As can be seen from fig. 1 and fig. 2, in this example, after 30min of reaction, the first peracetic acid stock solution alone was used to treat the wastewater, and the degradation rates of the four steroid estrogens were less than 40%, and for the wastewater treated by ultraviolet irradiation alone, the degradation rate of the estrone was more than 95%, and the degradation rates of the other three steroid estrogens were less than 40%. In comparison, the ultraviolet/first peroxyacetic acid storage solution is adopted to treat the sewage, so that the degradation of the four steroid estrogens in the sewage can be obviously improved, the degradation rate of the four steroid estrogens in the sewage can reach more than 90% after 30min of treatment, and the degradation kinetics follow a first-order kinetic equation.
Example 2: to investigate the effect of different first peroxyacetic acid stock solution dosages on the degradation of steroid estrogens in wastewater, the four steroid estrogens examined in this example were estrone, estradiol, estriol, and ethinyl estradiol;
the difference from example 1 is: the amount of the first peroxyacetic acid stock solution added was changed so that the ratio of the concentration of the first peroxyacetic acid stock solution to the total concentration of steroid estrogen in the wastewater was 50:1, 100:1, 150:1 and 200:1, and the other operation steps were the same as in example 1; the removal rate of each group of steroid estrogens after 30min of treatment was calculated.
With increasing amounts of the first peroxyacetic acid stock solution, the degradation rates of all three other steroidal estrogens increased with increasing amounts of the first peroxyacetic acid stock solution, except that there was no significant change in the degradation rate of estrone after 30 minutes.
Example 3: the influence of the initial pH of the wastewater on the degradation of the steroid estrogens is studied, and the four steroid estrogens examined in this example are estrone, estradiol, estriol and ethinyl estradiol;
the difference from example 1 is: adjusting the initial pH of the sewage by using hydrochloric acid and a sodium hydroxide solution to ensure that the initial pH of the sewage is 5.22, 6.01 and 9.28 respectively, and performing the other operation steps as in example 1; the removal rate of each group of steroid estrogens after 30min of treatment was calculated and the results are shown in figure 3.
As can be seen from FIG. 3, in this example, the initial pH of the wastewater is in the range of 5.22-9.28, and after the wastewater is treated with the UV/first peroxyacetic acid stock solution for 30min, the degradation of the four steroid estrogens in the wastewater is not significantly affected, which indicates that the method of the present invention is more suitable for wastewater treatment with large pH fluctuation.
Example 4: the removal effect of the method on the estrogen effect in the sewage is verified, and the four steroid estrogens used in the embodiment are estrone, estradiol, estriol and ethinyl estradiol;
respectively taking sewage water samples before and after 30min treatment by using the ultraviolet/first peroxyacetic acid stock solution, adjusting the pH of the water samples to 7 by using hydrochloric acid and sodium hydroxide solution, and detecting the estrogen activity of the water samples before and after treatment by using a recombinant human estrogen receptor (h-ER) gene yeast detection kit; the removal rate of the estrogen activity in the sewage can reach more than 94% by experiments, which shows that the method for treating the sewage containing the steroid estrogen can effectively reduce the estrogen activity of the water body and does not generate byproducts with high estrogen activity.
Example 5: the procedure was essentially the same as in example 1, except that the secondary tail water from a sewage plant, containing chloride ions at a concentration of 0.5mM-5mM, alkalinity at 0.5mM-3mM, and nitrate at a concentration of 0.2mM-2mM, was used as the subject, and the four steroidal estrogens examined in this example were estrone, estradiol, estriol, and ethinyl estradiol;
in this example, after the treatment with the uv/first peroxyacetic acid stock solution, the degradation rate of steroid estrogen in the wastewater can reach more than 90%, which indicates that some coexisting substrates in the actual wastewater have less influence on the treatment of steroid estrogen by the method of the present invention.
Example 6: the operation steps are basically the same as example 1 by taking surface water as a research object, wherein the concentration range of humic acid in the water is 2mg/L-30mg/L, and the four steroid estrogens examined in the example are estrone, estradiol, estriol and ethinyl estradiol;
in this example, after the treatment with the uv/first peroxyacetic acid stock solution, the degradation rate of steroid estrogen in surface water can reach more than 90%, which indicates that the coexisting matrix in surface water has less influence on the treatment of steroid estrogen by the method of the present invention.
Example 7: the difference from example 1 is: s1 the specific steps of the sewage pretreatment are as follows: the sewage is subjected to drug flocculation precipitation treatment, sand filtration treatment and carbon filtration treatment in sequence; wherein, the drug flocculation precipitation treatment specifically adopts a magnetic flocculation precipitation method. Wherein, the flocculating agent adopts commercial modified polyaluminium chloride.
Example 8: the difference from example 1 is: the strong oxidant adopts a second peroxyacetic acid stock solution; the second peroxyacetic acid stock solution is prepared from glacial acetic acid, hydrogen peroxide, acetic acid and ammonium persulfate according to a ratio of 2:2:1: mixing at a volume ratio of 0.2, ultrasonically dispersing at a low temperature of 4 ℃ for 4h, and standing at a temperature of 2 ℃ for 12 h.
Wherein the ratio of the adding amount of the second peroxyacetic acid stock solution to the content of steroid estrogen in the water is 30: 1.
Example 9: the difference from example 1 is: the strong oxidant adopts a second peroxyacetic acid stock solution; the second peroxyacetic acid stock solution is prepared from glacial acetic acid, hydrogen peroxide, acetic acid and ammonium persulfate according to a ratio of 2:2:1: mixing at a volume ratio of 0.2, ultrasonically dispersing at 5 deg.C for 6 hr, and standing at 3 deg.C for 14 hr.
Wherein the ratio of the steroid estrogen content in the second peroxyacetic acid stock solution in the added water is 60:1
Example 10: the difference from example 1 is: the strong oxidant adopts a second peroxyacetic acid stock solution; the second peroxyacetic acid stock solution is prepared from glacial acetic acid, hydrogen peroxide, acetic acid and ammonium persulfate according to a ratio of 2:2:1: mixing at a volume ratio of 0.2, ultrasonically dispersing at 6 deg.C for 8 hr, and standing at 4 deg.C for 15 hr.
Wherein the ratio of the steroid estrogen content in the added water of the second peroxyacetic acid stock solution is 110: 1.
Example 11: the difference from example 1 is: the ultraviolet wavelength of the ultraviolet lamp is 250 nm; the ultraviolet irradiation dose is 7500J/m2(ii) a Wherein, the ultraviolet irradiation dose is the ultraviolet light intensity multiplied by the irradiation time.
Example 12: the difference from example 1 is: the ultraviolet wavelength of the ultraviolet lamp is 258 nm; ultraviolet radiationThe dose is 30000J/m2(ii) a Wherein, the ultraviolet irradiation dose is the ultraviolet light intensity multiplied by the irradiation time.
Claims (10)
1. A high-grade oxidation method for degrading steroid estrogen in sewage is characterized by comprising the following steps:
s1: pretreatment of
Pre-treating sewage to control suspended solid below 10 mg/L;
s2: sampling detection
Measuring the concentration of steroid estrogen in the sewage by adopting a solid-phase extraction-liquid chromatography-mass spectrometry combined detection method; the method specifically comprises the following steps:
s2-1: solid phase extraction of steroid estrogens
1) Activating a CNWHLB solid phase extraction column by using 2 column tubes of methanol/ethyl acetate (1:9, V/V) and methanol in sequence; 2) balancing a CNWHLB solid phase extraction column by using 2 column pipes of pure water; 3) enriching and purifying 3mL of water sample by a CNWHLB solid phase extraction column; 4) washing the CNWHLB solid phase extraction column with 1 column tube methanol/water (1: 9); 5) eluting steroid estrogen with 10mL of methanol/ethyl acetate (1:9, V/V), blowing the eluent with nitrogen, diluting to constant volume with 1mL of methanol/water (9:1), storing in a refrigerator at-20 deg.C, and testing;
s2-2: detecting steroid estrogen liquid chromatography-mass spectrometry;
s3: peroxyacetic acid dosing
Adding a strong oxidant into sewage containing steroid estrogen in a targeted manner, and uniformly stirring;
s4: irradiation treatment
And (4) placing the sewage treated by the S3 under an ultraviolet light source for irradiation treatment.
2. The advanced oxidation method for degrading steroid estrogens in sewage as claimed in claim 1, wherein the specific steps of pretreatment of sewage S1 are: the sewage is sequentially subjected to drug flocculation precipitation treatment, sand filtration treatment and carbon filtration treatment.
3. The advanced oxidation method for degrading steroid estrogens in sewage as claimed in claim 2, wherein said drug flocculation precipitation treatment is magnetic flocculation precipitation.
4. The advanced oxidation method for degrading steroid estrogens in sewage of claim 1, wherein S2 said steroid estrogens include but are not limited to one or more of estrone (E1), 17 β -estradiol (E2), estriol (E3), and 17 α -ethinyl estradiol (EE 2).
5. The advanced oxidation method for degrading steroid estrogen in sewage according to claim 1, wherein the strong oxidant of S3 is first peroxyacetic acid stock solution; the first peroxyacetic acid stock solution is prepared by mixing glacial acetic acid and hydrogen peroxide according to the volume ratio of 1:1 and standing for 24 hours at the low temperature of 4-6 ℃.
6. The advanced oxidation method for degrading steroid estrogens in sewage as claimed in claim 5, wherein the ratio of the dosage of said first peroxyacetic acid stock solution to the steroid estrogens content in water is 50-200: 1.
7. The advanced oxidation method for degrading steroid estrogen in sewage according to claim 1, wherein the strong oxidant is a second peroxyacetic acid stock solution; the second peroxyacetic acid stock solution is prepared by mixing glacial acetic acid, hydrogen peroxide, acetic acid and ammonium persulfate according to the volume ratio of 2:2:1:0.2, performing ultrasonic dispersion for 4-8 hours at the low temperature of 4-6 ℃, and then standing for 12-15 hours at the temperature of 2-4 ℃.
8. The advanced oxidation method for degrading steroid estrogens in sewage as claimed in claim 5, wherein the ratio of the dosage of the second peroxyacetic acid stock solution to the steroid estrogens content in water is 30-110: 1.
9. The advanced oxidation method for degrading steroid estrogens in sewage as claimed in claim 1, wherein the ultraviolet light source of S4 is any ultraviolet lamp capable of emitting ultraviolet light, wherein the wavelength of the ultraviolet light is 250-258 nm.
10. The advanced oxidation method for degrading steroid estrogens in sewage as claimed in claim 9, wherein said ultraviolet radiation dose is 7500-30000J/m2。
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