CN106995251B - Method for removing estrogen pollutants in water body - Google Patents
Method for removing estrogen pollutants in water body Download PDFInfo
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- CN106995251B CN106995251B CN201710302128.7A CN201710302128A CN106995251B CN 106995251 B CN106995251 B CN 106995251B CN 201710302128 A CN201710302128 A CN 201710302128A CN 106995251 B CN106995251 B CN 106995251B
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- water body
- nitrate
- pollutants
- estrogen
- mixed gas
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 37
- 231100000719 pollutant Toxicity 0.000 title claims abstract description 36
- 229940011871 estrogen Drugs 0.000 title claims abstract description 29
- 239000000262 estrogen Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 16
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000007789 gas Substances 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 12
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 238000005286 illumination Methods 0.000 claims abstract description 6
- 230000001678 irradiating effect Effects 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 239000000356 contaminant Substances 0.000 claims description 4
- 230000001076 estrogenic effect Effects 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 abstract description 9
- 238000006731 degradation reaction Methods 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 230000015271 coagulation Effects 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229940088597 hormone Drugs 0.000 description 2
- 239000005556 hormone Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 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
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
-
- 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
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Abstract
The invention relates to a method for removing estrogen pollutants in a water body, which comprises the following steps: taking a water body containing estrogen pollutants, adding activated carbon into the water body, and introducing a mixed gas containing ozone and pure oxygen; filtering the treated water body, adding ferric salt and nitrate into the water body, and then irradiating for 10-15h at 30-40 ℃ under ultraviolet light, wherein the illumination intensity of the ultraviolet light is 20000-25000 Lux; filtering the treated water body, adding hydrated manganese dioxide, and stirring at the temperature of 20-35 ℃ under the condition that the pH value is 4-7 so as to degrade estrogen pollutants in the water body. The method has the advantages of mild reaction conditions, low cost and high pollutant degradation rate, and can effectively remove other colored impurities in the water body and improve the self-purification capacity of the water body.
Description
Technical Field
The invention relates to the field of environmental pollutant degradation, in particular to a method for removing estrogen pollutants in a water body.
Background
In the process of urbanization, as the sewage collection and treatment and the surface source pollution control system are imperfect, a large amount of pollutants enter urban landscape rivers, so that the dissolved oxygen in the rivers is consumed completely, and the water body is seriously polluted. Besides conventional pollutants, researches show that the concentration of the environmental hormone trace pollutants in the polluted urban rivers is very high and generally reaches the range of 600 ng/L-6000 ng/L, and the ecological safety level of the water body is 10ng/L, so that the control of the environmental hormone trace pollutants in the urban rivers becomes an urgent problem about the ecological safety of the water environment.
Especially, most of estrogen pollutants are fat-soluble organic matters, the chemical properties are stable, the degradation is mainly biological or photodegradation, but the degradation time is long, the degradation efficiency is low, and the degradation can be realized only by using a high-efficiency catalyst. The prior art for treating estrogen pollutants in water has high requirements on reaction conditions, low efficiency and high cost.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a method for removing estrogen pollutants in a water body, which has the advantages of mild reaction conditions, low cost and high pollutant degradation rate, and can effectively remove other colored impurities in the water body and improve the self-cleaning capacity of the water body.
The invention discloses a method for removing estrogen pollutants in a water body, which comprises the following steps:
(1) taking a water body containing estrogen pollutants, adding activated carbon into the water body, and introducing a mixed gas containing ozone and pure oxygen;
(2) filtering the water body treated in the step (1), adding ferric salt and nitrate into the water body, and then irradiating for 10-15h at 30-40 ℃ under ultraviolet light, wherein the illumination intensity of the ultraviolet light is 20000-25000 Lux;
(3) and (3) filtering the water body treated in the step (2), adding hydrated manganese dioxide into the water body, and stirring the mixture at the temperature of 20-35 ℃ under the condition that the pH value is 4-7 so as to degrade estrogen pollutants in the water body.
Further, in the step (1), the volume percentage of the ozone in the mixed gas is 5-10%, and the volume percentage of the pure oxygen is 90-95%.
Further, in the step (1), the pressure of the mixed gas is 0.1-0.3 MPa.
Further, in the step (1), the mixed gas is introduced for 1 to 10 hours.
Further, in the step (1), the temperature of the water body is 5-35 ℃.
Further, in the step (2), the iron salt is one or more of ferric nitrate, ferric chloride and ferric sulfate.
Further, in the step (2), the nitrate is one or more of ferric nitrate, cupric nitrate, magnesium nitrate, sodium nitrate and potassium nitrate.
Further, in the step (2), the molar ratio of the ferric salt to the nitrate is 0.1-0.5: 1.
Further, in the step (2), the mass ratio of the sum of the mass of the ferric salt and the nitrate to the water body is 1: 100-1000.
Further, in the step (3), the concentration of the hydrated manganese dioxide in the water body is 0.5 to 1. mu. mol/L.
The preparation method of hydrated manganese dioxide in the application is a method reported in the literature "preparation of hydrated manganese dioxide and coagulation characteristics thereof, water supply and drainage in China, 2006, 22 (15)".
By the scheme, the invention at least has the following advantages:
according to the invention, firstly, the strong oxidizing property of the mixed gas of ozone and pure oxygen is utilized, the dissolved oxygen concentration of the water body is greatly improved in a short time, and meanwhile, pollutants in the water are rapidly oxidized, and meanwhile, the activated carbon is added, so that colored substances and trace estrogen pollutants in the water body can be effectively adsorbed; secondly, under the action of a conventional catalyst, the sterilization and degradation effects of ultraviolet light are exerted, and estrogen pollutants are further removed; finally, hydrated manganese dioxide provides a highly effective degradation of estrogenic contaminants.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a preferred embodiment of the present invention and is described in detail below.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
(1) Taking 10kg of water containing estrogen pollutants, adding 100g of activated carbon into the water at 15 ℃, and simultaneously introducing mixed gas containing ozone and pure oxygen for 10h, wherein the volume percentage of ozone in the mixed gas is 5%, the volume percentage of pure oxygen is 95%, and the pressure of the mixed gas is 0.1 MPa.
(2) Filtering the water body treated in the step (1) by a PTFE filter membrane of 500nm, adding 50g of ferric chloride and 50g of sodium nitrate into the water body, and then irradiating the water body for 15 hours at 40 ℃ under ultraviolet light, wherein the illumination intensity of the ultraviolet light is 20000 Lux.
(3) And (3) filtering the water body treated in the step (2) by a PTFE (polytetrafluoroethylene) filter membrane of 200nm, adding hydrated manganese dioxide into the water body, and stirring the mixture at the temperature of 20 ℃ for 30min under the condition that the pH value is 7 so as to degrade estrogen pollutants in the water body. Among them, the method for producing hydrated manganese dioxide is described in "production of hydrated manganese dioxide and coagulation property thereof, water supply and drainage in china, 2006, 22 (15)". The concentration of hydrated manganese dioxide in the water body is 0.5 mu mol/L.
The water body before treatment and the water body after treatment are taken, and the estrogen pollutants in the water body are measured, and the result shows that the removal rate of the estrogen pollutants in the water body treated by the method of the invention reaches 88%.
Example 2
(1) Taking 10kg of water containing estrogen pollutants, adding 100g of activated carbon into the water at 25 ℃, and simultaneously introducing mixed gas containing ozone and pure oxygen for 1h, wherein the volume percentage of ozone in the mixed gas is 10%, the volume percentage of pure oxygen is 90%, and the pressure of the mixed gas is 0.3 MPa.
(2) Filtering the water body treated in the step (1) by a PTFE filter membrane with the diameter of 1 mu m, adding 40g of ferric sulfate and 70g of copper nitrate into the water body, and then irradiating the water body for 10 hours at the temperature of 30 ℃ under ultraviolet light, wherein the illumination intensity of the ultraviolet light is 25000 Lux.
(3) Filtering the water body treated in the step (2) by a PTFE filter membrane of 500nm, adding hydrated manganese dioxide, and stirring at 35 ℃ for 1h under the condition that the pH value is 4 so as to degrade estrogen pollutants in the water body. Among them, the method for producing hydrated manganese dioxide is described in "production of hydrated manganese dioxide and coagulation property thereof, water supply and drainage in china, 2006, 22 (15)". The concentration of hydrated manganese dioxide in the water body is 1 mu mol/L.
The water body before treatment and the water body after treatment are taken, and estrogen pollutants are detected in the water body, and the result shows that the removal rate of the estrogen pollutants in the water body treated by the method of the invention reaches 99%.
Example 3
(1) Taking 10kg of water containing estrogen pollutants, adding 200g of activated carbon into the water, and simultaneously introducing mixed gas containing ozone and pure oxygen for 6 hours, wherein the volume percentage of the ozone in the mixed gas is 3%, the volume percentage of the pure oxygen in the mixed gas is 97%, and the pressure of the mixed gas is 0.2 MPa.
(2) Filtering the water body treated in the step (1) by a PTFE filter membrane of 500nm, adding 10g of ferric chloride and 90g of sodium nitrate, and then irradiating for 12h at 35 ℃ under ultraviolet light, wherein the illumination intensity of the ultraviolet light is 22000 Lux.
(3) And (3) filtering the water body treated in the step (2) by a PTFE (polytetrafluoroethylene) filter membrane of 200nm, adding hydrated manganese dioxide into the water body, and stirring the mixture at the temperature of 18 ℃ for 30min under the condition that the pH value is 5 so as to degrade estrogen pollutants in the water body. Among them, the method for producing hydrated manganese dioxide is described in "production of hydrated manganese dioxide and coagulation property thereof, water supply and drainage in china, 2006, 22 (15)". The concentration of hydrated manganese dioxide in the water body is 0.8 mu mol/L.
The water body before treatment and the water body after treatment are taken, and the estrogen pollutants in the water body are measured, and the result shows that the removal rate of the estrogen pollutants in the water body treated by the method of the invention reaches 92 percent.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (4)
1. A method for removing estrogen pollutants in a water body is characterized by comprising the following steps:
(1) taking a water body containing estrogen pollutants, adding activated carbon into the water body, and introducing a mixed gas containing ozone and pure oxygen;
(2) filtering the water body treated in the step (1), adding ferric salt and nitrate into the water body, and then irradiating for 10-15h at 30-40 ℃ under ultraviolet light, wherein the illumination intensity of the ultraviolet light is 20000-25000 Lux; the ferric salt is one or more of ferric nitrate, ferric chloride and ferric sulfate; the nitrate is copper nitrate or sodium nitrate; the molar ratio of the ferric salt to the nitrate is 0.1-0.5: 1; the mass ratio of the sum of the mass of the ferric salt and the nitrate to the water body is 1: 100-1000;
(3) and (3) filtering the water body treated in the step (2), adding hydrated manganese dioxide into the water body, wherein the concentration of the hydrated manganese dioxide in the water body is 0.5-1 mu mol/L, and stirring the mixture at the temperature of 20-35 ℃ under the condition that the pH value is 4-7 so as to degrade estrogen pollutants in the water body.
2. The method for removing estrogen-like contaminants from water according to claim 1, wherein: in the step (1), the volume percentage of ozone in the mixed gas is 5-10%, and the volume percentage of pure oxygen is 90-95%.
3. The method for removing estrogen-like contaminants from water according to claim 1, wherein: in the step (1), the pressure of the mixed gas is 0.1-0.3 MPa.
4. The method for removing estrogen-like contaminants from water according to claim 1, wherein: in the step (1), the mixed gas is introduced for 1-10 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710302128.7A CN106995251B (en) | 2017-05-02 | 2017-05-02 | Method for removing estrogen pollutants in water body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710302128.7A CN106995251B (en) | 2017-05-02 | 2017-05-02 | Method for removing estrogen pollutants in water body |
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| Publication Number | Publication Date |
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| CN106995251A CN106995251A (en) | 2017-08-01 |
| CN106995251B true CN106995251B (en) | 2020-05-22 |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111707652B (en) * | 2020-06-24 | 2021-06-15 | 中国科学院南京地理与湖泊研究所 | Method for evaluating biodegradation potential of estrogen in water body based on three-dimensional fluorescence spectrum |
Citations (8)
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| JP2000042575A (en) * | 1998-08-04 | 2000-02-15 | Kurita Water Ind Ltd | Treatment of water containing endocrine disrupters |
| CN101168459A (en) * | 2006-10-25 | 2008-04-30 | 中国科学院大连化学物理研究所 | Catalysis wet-type oxidation degradation method for estrogen-like contaminant |
| WO2008052233A1 (en) * | 2006-10-30 | 2008-05-08 | Hans-Peter Bierbaumer | Method for the treatment of waste water |
| CN101219371A (en) * | 2007-01-08 | 2008-07-16 | 北京化工大学 | Photocatalysis oxidation treated high concentration organic trade waste |
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2017
- 2017-05-02 CN CN201710302128.7A patent/CN106995251B/en active Active
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