CN111087036A - Method for synchronously removing chlorite and emerging organic micropollutants in water by using ultraviolet light - Google Patents
Method for synchronously removing chlorite and emerging organic micropollutants in water by using ultraviolet light Download PDFInfo
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- CN111087036A CN111087036A CN201911381660.8A CN201911381660A CN111087036A CN 111087036 A CN111087036 A CN 111087036A CN 201911381660 A CN201911381660 A CN 201911381660A CN 111087036 A CN111087036 A CN 111087036A
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- China
- Prior art keywords
- chlorite
- water
- ultraviolet light
- chlorine dioxide
- micropollutants
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- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910001919 chlorite Inorganic materials 0.000 title claims abstract description 37
- 229910052619 chlorite group Inorganic materials 0.000 title claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 23
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000004155 Chlorine dioxide Substances 0.000 claims abstract description 16
- 235000019398 chlorine dioxide Nutrition 0.000 claims abstract description 16
- 238000004659 sterilization and disinfection Methods 0.000 claims abstract description 12
- 239000006227 byproduct Substances 0.000 claims abstract description 7
- 230000005855 radiation Effects 0.000 claims abstract description 7
- 239000003814 drug Substances 0.000 claims description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052753 mercury Inorganic materials 0.000 claims description 4
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 4
- 229960002218 sodium chlorite Drugs 0.000 claims description 4
- 229940079593 drug Drugs 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 claims description 3
- 239000000575 pesticide Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 239000003053 toxin Substances 0.000 claims description 3
- 231100000765 toxin Toxicity 0.000 claims description 3
- 108700012359 toxins Proteins 0.000 claims description 3
- WOHVONCNVLIHKY-UHFFFAOYSA-L [Ba+2].[O-]Cl=O.[O-]Cl=O Chemical compound [Ba+2].[O-]Cl=O.[O-]Cl=O WOHVONCNVLIHKY-UHFFFAOYSA-L 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- 230000002124 endocrine Effects 0.000 claims description 2
- 239000003205 fragrance Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- NWAPVVCSZCCZCU-UHFFFAOYSA-L magnesium;dichlorite Chemical compound [Mg+2].[O-]Cl=O.[O-]Cl=O NWAPVVCSZCCZCU-UHFFFAOYSA-L 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000003344 environmental pollutant Substances 0.000 abstract description 8
- 239000000460 chlorine Substances 0.000 abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000033558 biomineral tissue development Effects 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 230000001360 synchronised effect Effects 0.000 abstract 1
- 238000005286 illumination Methods 0.000 description 8
- 239000003651 drinking water Substances 0.000 description 6
- 235000020188 drinking water Nutrition 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- -1 hydroxyl free radical Chemical class 0.000 description 4
- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical compound C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 description 3
- 229960000623 carbamazepine Drugs 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- 206010063003 Endocrine toxicity Diseases 0.000 description 1
- 206010029350 Neurotoxicity Diseases 0.000 description 1
- 206010044221 Toxic encephalopathy Diseases 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000007059 acute toxicity Effects 0.000 description 1
- 231100000403 acute toxicity Toxicity 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000007665 chronic toxicity Effects 0.000 description 1
- 231100000160 chronic toxicity Toxicity 0.000 description 1
- 230000007673 developmental toxicity Effects 0.000 description 1
- 231100000415 developmental toxicity Toxicity 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 231100000049 endocrine disruptor Toxicity 0.000 description 1
- 231100000146 endocrine toxicity Toxicity 0.000 description 1
- 210000003743 erythrocyte Anatomy 0.000 description 1
- 208000007475 hemolytic anemia Diseases 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 208000005135 methemoglobinemia Diseases 0.000 description 1
- 231100000219 mutagenic Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 231100000228 neurotoxicity Toxicity 0.000 description 1
- 230000007135 neurotoxicity Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000007281 self degradation Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
-
- 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
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
Abstract
The invention belongs to the field of water treatment, and discloses a method for synchronously removing chlorite and emerging organic micropollutants in water by using ultraviolet light. The method specifically comprises the steps of utilizing main inorganic byproduct chlorite generated after chlorine dioxide preoxidation of water plants or chlorine dioxide disinfection of water from plants, and then generating a large amount of hydroxyl radicals, chlorine radicals and chlorine-oxygen radicals to attack micro-pollutants through ultraviolet radiation, so that synchronous degradation of the chlorite and the micro-pollutants is realized. The method has the advantages of simple operation, obvious effect and safe use, can synchronously remove chlorite and various new organic micro-pollutants in water, and can achieve mineralization to a certain degree.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a method for synchronously removing chlorite and new organic micropollutants in water by using ultraviolet light.
Background
In the production of drinking water, about 32.8% of water plants in China adopt chlorine dioxide for preoxidation or factory water disinfection. Although the disinfection by chlorine dioxide generates less organic disinfection byproducts than other disinfection modes, the disinfection by chlorine dioxide inevitably generates inorganic disinfection byproducts, and the main component is chlorite. Since chlorite can destroy red blood cells, resulting in methemoglobinemia and hemolytic anemia, and simultaneously, it produces developmental toxicity, endocrine toxicity and neurotoxicity to animal growth, the Chinese Ministry of health and the world health organization have made definite limit values for chlorite in drinking water, which needs to be less than 0.7 mg/L. The emerging organic micro-pollutants mainly comprise medicines and personal care products, endocrine disruptors, brominated flame retardants, pesticides, algal toxins, smelly substances and the like, wherein one part of the organic micro-pollutants is carcinogenic, teratogenic and mutagenic substances. Emerging organic micropollutants are detected in surface water, underground water and domestic drinking water all around the world, and although the concentration of the organic micropollutants is low in the residual concentration of water bodies and is not easy to generate acute toxicity, the potential possibility of chronic toxicity exists due to the continuous accumulation of food chains in the environment for a long time. It has also been reported that the distribution of different emerging organic contaminant residual contaminant types is detected at certain concentrations in certain tissues or body fluids of the human body.
At present, the water treatment process has extremely low removal efficiency on chlorite and emerging organic micropollutants. Therefore, the process for synchronously removing chlorite and new organic micropollutants in water is sought, the water quality is effectively improved, and the important significance is realized for people to drink safe, healthy and high-quality drinking water.
Disclosure of Invention
The invention aims to solve the problems of chlorite and various toxic and harmful emerging organic micro-pollutants commonly existing in drinking water in an efficient and quick manner, and provides a method for synchronously removing chlorite and emerging organic micro-pollutants in water by utilizing the synergistic effect of ultraviolet light and chlorite which is a harmful substance.
The technical scheme of the invention is to provide a method for synchronously removing chlorite and emerging organic micropollutants in water by using ultraviolet light, which is characterized by comprising the following specific steps: the main inorganic byproduct chlorite generated after chlorine dioxide preoxidation of water plants or chlorine dioxide disinfection of water from plants is utilized, and then ultraviolet radiation is carried out to synchronously remove the chlorite and emerging micropollutants in water.
Further, the chlorite is any one or a mixture of sodium chlorite, magnesium chlorite, barium chlorite and other salts.
Further, the micropollutants include drugs, dyes, personal care products, endocrine regulators, brominated flame retardants, pesticides, algal toxins, odorants, and the like.
Further, the main inorganic byproduct chlorite is generated after chlorine dioxide preoxidation of the water plant or chlorine dioxide disinfection of the water plant.
Further, the light source adopts any one or a combination of a plurality of low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure palace lamp, halogen lamp, vacuum ultraviolet lamp, ultraviolet light-emitting diode, UV-A, UV-B and UV-C.
Further, the initial pH value of the water is 2.0-11.0.
Further, the radiation mode is a surface irradiation type, an immersion type or an overflow type.
The principle of the invention is that chlorite in water generates hydroxyl free radical (HO), chlorine free radical (ClO), chlorine free radical (Cl) and oxygen free radical (O) under the condition of illumination-O.cndot.). The oxygen free radicals are generated by hypochlorous acid generated by chlorite illumination and chlorine dioxide illumination, the oxygen free radicals have poor stability and can quickly react with water to generate hydroxyl free radicals, the chlorine free radicals are generated by chlorite illumination and chlorine dioxide illumination generated by chlorite illumination, and the chlorine free radicals are generated by hypochlorite illumination generated by chlorite illumination.
ClO2 -→ClO·+O·-
ClO2 -→(ClO2 -)*
(ClO2 -)*+ClO2 -→ClO2(g)+ClO-
ClO-→Cl·+O·-
ClO2→ClO·+O·
O·+H2O→H2O2→2HO·
Compared with other advanced oxidation methods based on ultraviolet light, the method has the advantages that (1) chlorite exists after chlorine dioxide disinfection in a water plant, no additional medicament is needed, and the method has obvious advantage in cost performance; (2) the chlorite can generate a plurality of free radicals with strong oxidizability in the process of self degradation, and can synchronously degrade other organic micro-pollutants in water, thereby achieving the win-win effect.
Drawings
Fig. 1 is a graph showing the effect of ultraviolet radiation on chlorite removal.
Fig. 2 is a graph showing the effect of ultraviolet radiation of chlorite on the removal of carbamazepine in water.
Detailed Description
The present invention will be further described with reference to the accompanying drawings, but the embodiments of the present invention are not limited thereto.
Example 1:
the embodiment provides a method for synchronously removing chlorite and emerging organic micropollutants in water by using ultraviolet light. The method comprises the following specific steps: an aqueous solution containing micropollutants to be treated was prepared as a solution to be treated (pH 7.0), with a volume of 100mL, and an initial benzoic acid concentration of 1 μ M, (where M is mol/L, μ M is 10-6mol/L, mM is 10-3mol/L, the same applies below), a sodium chlorite concentration of 10 μ M (this concentration does not exceed the chlorite limit in the sanitary standard for drinking water (GB5749-2006), and UV light is appliedThe absorbance of chlorite is very high by light radiation, the chlorite is completely degraded within 30s, when the illumination time reaches 5min, the removal rate of carbamazepine can reach more than 80 percent, and the carbamazepine cannot be removed by ultraviolet alone and sodium chlorite alone.
Claims (7)
1. A method for synchronously removing chlorite and emerging organic micropollutants in water by ultraviolet light is characterized in that main inorganic byproduct chlorite generated after chlorine dioxide preoxidation of a water plant or chlorine dioxide disinfection of factory water is utilized, and then the chlorite and the emerging micropollutants in the water are synchronously removed by ultraviolet light radiation.
2. The method as claimed in claim 1, wherein the chlorite is any one or more of sodium chlorite, magnesium chlorite, barium chlorite and other salts.
3. The method of claim 1, wherein the micropollutants comprise any one or a mixture of drugs, dyes, personal care products, endocrine regulators, brominated flame retardants, pesticides, algal toxins, and odorants.
4. The method of claim 1, wherein the chlorite salt is derived from a main inorganic byproduct chlorite salt produced after pre-oxidation of waterworks chlorine dioxide or disinfection of waterworks chlorine dioxide.
5. The method according to claim 1, wherein the light source of the ultraviolet light is any one or a combination of a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure palace lamp, a halogen lamp, a vacuum ultraviolet lamp, an ultraviolet light emitting diode, UV-A, UV-B and UV-C.
6. The method of claim 1, wherein the initial pH of the water is 2.0 to 11.0.
7. The method of claim 1, wherein the irradiation mode is surface irradiation, immersion, or overflow.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911381660.8A CN111087036A (en) | 2019-12-27 | 2019-12-27 | Method for synchronously removing chlorite and emerging organic micropollutants in water by using ultraviolet light |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911381660.8A CN111087036A (en) | 2019-12-27 | 2019-12-27 | Method for synchronously removing chlorite and emerging organic micropollutants in water by using ultraviolet light |
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| Publication Number | Publication Date |
|---|---|
| CN111087036A true CN111087036A (en) | 2020-05-01 |
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|---|---|---|---|
| CN201911381660.8A Pending CN111087036A (en) | 2019-12-27 | 2019-12-27 | Method for synchronously removing chlorite and emerging organic micropollutants in water by using ultraviolet light |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111977866A (en) * | 2020-07-13 | 2020-11-24 | 中山大学 | Chlorine dioxide and ultraviolet and chlorine coupled water purification method |
| CN113060877A (en) * | 2021-03-30 | 2021-07-02 | 上海应用技术大学 | Method for removing Trimethoprim in water based on ultraviolet/sodium chlorite combined technology |
| CN114314736A (en) * | 2021-12-27 | 2022-04-12 | 四川大学 | Method for removing pollutants in water based on light irradiation/chlorotrimeric acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1552633A (en) * | 2003-05-26 | 2004-12-08 | 深圳市海川实业股份有限公司 | Running water ultraviolet technology pretreatment method |
| CN101372369A (en) * | 2008-09-26 | 2009-02-25 | 刘伟 | Ultraviolet catalytic sterilization and chlorination combined disinfection method for water |
| CN103523900A (en) * | 2013-10-24 | 2014-01-22 | 中山大学 | Method for removing micro-pollutants in water via combination of ultraviolet light and free chlorine |
| CN104944513A (en) * | 2015-06-26 | 2015-09-30 | 清华大学深圳研究生院 | Method for treating azo dye wastewater with ultraviolet light |
| CN106082390A (en) * | 2016-07-27 | 2016-11-09 | 中山大学 | A kind of method that ultraviolet light and the combination of free chlorine reduce water quality comprehensive toxicity |
-
2019
- 2019-12-27 CN CN201911381660.8A patent/CN111087036A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1552633A (en) * | 2003-05-26 | 2004-12-08 | 深圳市海川实业股份有限公司 | Running water ultraviolet technology pretreatment method |
| CN101372369A (en) * | 2008-09-26 | 2009-02-25 | 刘伟 | Ultraviolet catalytic sterilization and chlorination combined disinfection method for water |
| CN103523900A (en) * | 2013-10-24 | 2014-01-22 | 中山大学 | Method for removing micro-pollutants in water via combination of ultraviolet light and free chlorine |
| CN104944513A (en) * | 2015-06-26 | 2015-09-30 | 清华大学深圳研究生院 | Method for treating azo dye wastewater with ultraviolet light |
| CN106082390A (en) * | 2016-07-27 | 2016-11-09 | 中山大学 | A kind of method that ultraviolet light and the combination of free chlorine reduce water quality comprehensive toxicity |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111977866A (en) * | 2020-07-13 | 2020-11-24 | 中山大学 | Chlorine dioxide and ultraviolet and chlorine coupled water purification method |
| CN113060877A (en) * | 2021-03-30 | 2021-07-02 | 上海应用技术大学 | Method for removing Trimethoprim in water based on ultraviolet/sodium chlorite combined technology |
| CN114314736A (en) * | 2021-12-27 | 2022-04-12 | 四川大学 | Method for removing pollutants in water based on light irradiation/chlorotrimeric acid |
| CN114314736B (en) * | 2021-12-27 | 2023-08-25 | 四川大学 | Method for removing pollutants in water based on light irradiation/chlorocyanuric acid |
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