CN108911025A - A kind of method for treating water removing micropollutants - Google Patents
A kind of method for treating water removing micropollutants Download PDFInfo
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- CN108911025A CN108911025A CN201810803964.8A CN201810803964A CN108911025A CN 108911025 A CN108911025 A CN 108911025A CN 201810803964 A CN201810803964 A CN 201810803964A CN 108911025 A CN108911025 A CN 108911025A
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- Prior art keywords
- micropollutants
- water body
- water
- permanganate
- treating water
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 238000000034 method Methods 0.000 title claims abstract description 46
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 84
- 150000003839 salts Chemical class 0.000 claims abstract description 28
- 238000011065 in-situ storage Methods 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 7
- 230000015556 catabolic process Effects 0.000 claims abstract description 6
- 238000006731 degradation reaction Methods 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 239000003814 drug Substances 0.000 claims description 9
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 9
- 229910052753 mercury Inorganic materials 0.000 claims description 9
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 claims description 8
- 229940079593 drug Drugs 0.000 claims description 8
- 239000011550 stock solution Substances 0.000 claims description 8
- 229940099596 manganese sulfate Drugs 0.000 claims description 7
- 235000007079 manganese sulphate Nutrition 0.000 claims description 7
- 239000011702 manganese sulphate Substances 0.000 claims description 7
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 7
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 241000195493 Cryptophyta Species 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000002158 endotoxin Substances 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 4
- 239000000575 pesticide Substances 0.000 claims description 4
- 239000003053 toxin Substances 0.000 claims description 4
- 231100000765 toxin Toxicity 0.000 claims description 4
- 229910000497 Amalgam Inorganic materials 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 230000005260 alpha ray Effects 0.000 claims description 3
- 238000011109 contamination Methods 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- 230000002085 persistent effect Effects 0.000 claims description 2
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- -1 hydroxyl radical free radical Chemical class 0.000 abstract description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052748 manganese Inorganic materials 0.000 abstract description 7
- 239000011572 manganese Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000006303 photolysis reaction Methods 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 239000012286 potassium permanganate Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000010453 quartz Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003344 environmental pollutant Substances 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- 239000003708 ampul Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 5
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical group Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 5
- 235000002867 manganese chloride Nutrition 0.000 description 5
- 239000011565 manganese chloride Substances 0.000 description 5
- 229940099607 manganese chloride Drugs 0.000 description 5
- 239000002957 persistent organic pollutant Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 239000003651 drinking water Substances 0.000 description 4
- 235000020188 drinking water Nutrition 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- 241000402754 Erythranthe moschata Species 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003556 anti-epileptic effect Effects 0.000 description 1
- 239000001961 anticonvulsive agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000820 nonprescription drug Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000003204 tranquilizing agent Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000000273 veterinary drug Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Landscapes
- 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)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The present invention provides a kind of method for treating water for removing micropollutants, include the following steps：1) manganous salt and permanganate are added into the water body containing micropollutants, stirs evenly, the manganous salt and permanganate react in-situ preparation manganese dioxide；2) ultraviolet light will be used through step 1) treated water body, stirring removes the micropollutants in water body；Wherein, the molar ratio of manganese dioxide and micropollutants in water body is 20-50:1.The present invention utilizes ultraviolet light photodissociation manganous salt and the generated in-situ manganese dioxide of permanganate, generate hydroxyl radical free radical and intermediate state Active manganese substance, so as to quickly remove the micropollutants in water body, this method can significantly improve the rate of individually manganese dioxide degradation micropollutants in situ, have many advantages, such as throwing amount is small, at low cost, easy to operate, removal efficiency is high, easily controllable, without secondary pollution.
Description
Technical field
The invention belongs to water-treatment technology field more particularly to a kind of method for treating water for removing micropollutants.
Background technique
With the rapid development of industrial or agricultural, a large amount of poisonous and harmful substances enter water body and water body are caused seriously to pollute, and water quality is not
It is disconnected to deteriorate.Research shows that the efficiency for removal micropollutants such as traditional water treatment technology such as coagulation, precipitating, filtering, disinfection
It is lower, therefore, under the threat that drinking water source is polluted by micropollutants, seek effective further treatment technique to strengthen
Except trace contaminant has important strategic importance.
At present mainly using harmful micro-content organism in the oxidizing process such as chlorine, ozone, hydrogen peroxide removal water body.Chlorine is to having
Machine object has certain oxidation, usually the pre-oxidation agent as water body processing, but gas chromatography in chlorine and water body
It is easy reaction and generates poisonous and hazardous chloro by-product, the application which greatly limits chlorine as pre-oxidation agent.The oxidation of ozone
Property is very strong, but its at high cost and easy reacts with organic matter to form the defect of bromate carcinogen and limits its application.Peroxide
Change hydrogen and can combine to form Fenton system and generate the hydroxyl radical free radical of strong oxidizing property with ferrous ion and removes organic micro-pollution
Object, but it is acid condition that the process, which needs to control, therefore the process requirement constantly regulate pH, so as to cause the operation process control
It makes complex.
Summary of the invention
In view of the above-mentioned drawbacks in the prior art, the main purpose of the present invention is to provide a kind of water for removing micropollutants
Processing method removes the organic pollutant in water removal using the generated in-situ manganese dioxide of UV activation, also without additional addition
Former agent or catalyst can efficiently go the micropollutants in water removal.
In order to achieve the above object, the present invention adopts the following technical scheme that：A kind of method for treating water removing micropollutants,
Include the following steps：
1) manganous salt and permanganate are added into the water body containing micropollutants, stirs evenly, the manganous salt
In-situ preparation manganese dioxide is reacted with permanganate；
2) ultraviolet light will be used through step 1) treated water body, stirring removes the micropollutants in water body；
Wherein, the molar ratio of manganese dioxide and micropollutants in water body is 20-50:1.
As a further preference, the permanganate is selected from potassium permanganate and sodium permanganate.
As a further preference, the manganous salt is selected from manganese chloride, manganese nitrate and manganese sulfate.
As a further preference, the permanganate or manganous salt are solid or the preparatory stock solution dissolved.
As a further preference, the light source of the ultraviolet light be light emitting diode (LED), low pressure mercury lamp, medium pressure mercury lamp,
High-pressure sodium lamp, amalgam ultraviolet lamp, halogen lamp, xenon lamp, blackout, vacuum UV lamp, X-ray, alpha ray, in gamma-rays or sunlight
Any one or combination.
As a further preference, the mode of the ultraviolet light is overflow-type, immersion or surface irradiation formula.
As a further preference, when the ultraviolet light is using the Single wavelength ultraviolet lamp fluorescent tube that wavelength is 254nm, institute
It is 40-200mJ cm with ultraviolet light intensity-2。
As a further preference, the pH value of the water body is 4-9.
As a further preference, the pH value of the water body is 7-8.
As a further preference, the micropollutants include that drug and personal care articles (PPCPs), persistence are organic
In object, Taste and odor compounds, algae toxin, endotoxin, pesticide, petroleum-type organic contamination or hardly degraded organic substance any one or it is more
Kind.
Above-mentioned method for treating water in processing water body containing micropollutants application also protection scope of the present invention it
It is interior.
The beneficial effects of the invention are as follows：Method for treating water of the invention adds bivalent manganese in the water body containing micropollutants
Salt and permanganate carry out UV Light to water body to generate manganese dioxide in situ；Wherein, ultraviolet light photodissociation is utilized
Manganous salt and the generated in-situ manganese dioxide of permanganate generate hydroxyl radical free radical and intermediate state Active manganese substance, thus
The micropollutants in water body can be quickly removed, this method can significantly improve independent manganese dioxide degradation micropollutants in situ
Rate, the present invention are not necessarily to expensive oxidant and catalyst, by combining cheap ultraviolet wave spectrum light source, it can be achieved that quickly
Remove micropollutants, it is small, at low cost, easy to operate with throwing amount, removal efficiency is high, easily controllable, without secondary pollution etc. all
More advantages.Meanwhile present method solves the defect that manganese dioxide itself is unable to the stable micropollutants of oxidation structure, strengthen simultaneously
The effect of independent ultraviolet light removal micropollutants.
Detailed description of the invention
Fig. 1 is removal effect figure of 1 method of the embodiment of the present invention to micropollutants in water.
Fig. 2 is removal effect figure of 2 method of the embodiment of the present invention to micropollutants in water.
Fig. 3 is removal effect figure of 3 method of the embodiment of the present invention to micropollutants in water.
Fig. 4 is removal effect figure of 4 method of the embodiment of the present invention to micropollutants in water.
Fig. 5 is removal effect figure of 5 method of the embodiment of the present invention to micropollutants in water.
Fig. 6 is 6 method of the embodiment of the present invention and control group to the drug in water --- acidum nalidixicum (NDA) is in pH 7.4
Removal effect figure.
Specific embodiment
The present invention solves existing generated in-situ titanium dioxide by providing a kind of method for treating water for removing micropollutants
The manganese micro quantity organic pollutant stable to aouatic structure is unable to oxidation removal and UV (ultraviolet light) photodissociation to most of micro- pollution
The limited problem of object removal efficiency.
In order to solve drawbacks described above, the main thought of the embodiment of the present invention is：
The embodiment of the present invention removes the method for treating water of micropollutants, includes the following steps：
1) oxidant is added into water body to be processed, the oxidant is that manganous salt and permanganate reaction are in situ raw
At manganese dioxide；
2) ultraviolet light will be used through step 1) treated water body, stirring ensures to remove by generating active specy
Micropollutants in water body；
Wherein, the molar ratio of manganese dioxide and micropollutants in water body is 20-50:1,.
Above-mentioned steps 1) in, manganous salt and permanganate react in-situ preparation manganese dioxide, and reaction equation is：
2MnO4 -+3Mn2++2H2O=5MnO2+4H+ (1)
The permanganic acid that above-mentioned permanganate can be potassium permanganate/sodium permanganate or combined solid or dissolve in advance
Salt stock solution.Above-mentioned manganous salt can be the solid of manganese chloride, manganese nitrate and manganese sulfate or combinations thereof or dissolve in advance
Stock solution.
Above-mentioned manganese dioxide can be the water-soluble manganese dioxide that generates after permanganate water process, or self-control two
Manganese oxide, manganous salt and potassium permanganate/sodium permanganate or combination are prepared according to above-mentioned reaction equation (1) proportion.
Above-mentioned steps 2) in, ultraviolet light use UV irradiation systems include ultraviolet lamp tube, UV intensity sensor and its
His appliance, the presence or absence of quartz socket tube is depending on light radiation mode, and reactor specific structure and specification are according to actual needs
Depending on.
The light source of ultraviolet lamp tube is light emitting diode (LED), low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, amalgam are ultraviolet
Lamp, halogen lamp, xenon lamp, blackout, vacuum UV lamp, X-ray, alpha ray, in gamma-rays or any one or combination of sunlight.
The arrangement principle of fluorescent tube is that each point in cylinder section is made to have the ultraviolet radiation intensity being substantially the same.Fluorescent tube quantity
It is determined according to practical fluorescent tube intensity, required uv dosage, processing water and operation cost.
Ultraviolet light dosage according to water quality, ultraviolet transmission rate, UV arc aging coefficient and with remove quartz socket tube knot
The factors such as the related cleaning way of dirt determine.
Ultraviolet light should carry out the irradiation intensity that preheating ensures to have stable before the use, and regularly clean or replace ultraviolet light
Source is to keep the requirement of uv dosage.
The mode of above-mentioned ultraviolet light uses overflow-type, immersion or surface irradiation formula.When use overflow-type and submergence
When formula, shell causes the quartz glass of ozone-ultraviolet beta radiation to manufacture with a kind of 200nm or less that can effectively absorb.The disinfection of single fluorescent tube
A fluorescent tube is set in device, fluorescent tube is located at the center of cylinder section, and the arrangement principle of fluorescent tube, is to make cylinder in the sterilizer of more fluorescent tubes
Each point has the ultraviolet radiation intensity being substantially the same in section.
Ultraviolet lamp tube may be arranged that with water flow parallelly distribute on, it may be arranged that making it as far as possible with water flow vertical distribution
It is evenly distributed, comes into full contact with ultraviolet light with water flow.
When using the Single wavelength ultraviolet lamp fluorescent tube that wavelength is 254nm, ultraviolet light intensity used is 40-200mJ cm-2Compare
Properly.
Theoretically, the oxidation rate of manganese dioxide can enhance under acid condition, and the degradation efficiency of micropollutants is higher；Light intensity
Bigger, the effect for removing pollutant is better.But it is generally neutrality in view of by the drinking water after advanced treating, therefore real to meet
Border needs to control pH as 7-8.If it is necessary, can adjust optimal pH range according to its characteristic and realize the fast of pollutant
Speed removal.Theoretically, temperature is higher, and the degradation efficiency of pollutant is higher.But in order to which the demand of gearing to actual circumstances controls temperature for 20-
40 DEG C of room temperature.Furthermore, it is possible to design different reactor configurations, dosages distribution according to water quality requirement and design specification, reach
Quickly go the purpose of micropollutants in water removal.
The micropollutants include drug and personal care articles (PPCPs), persistent organism, Taste and odor compounds, algae toxin,
Any one or more in endotoxin, pesticide, petroleum-type organic contamination or hardly degraded organic substance.PPCPs then includes various places
Side and non-prescription drugs (such as antibiotic, tranquillizer, antiepileptic), veterinary drug, natural and artificial hormone, various makeups
Product, synthetic musk, x-ray contrast agent etc..
Manganese dioxide is common product during potassium permanganate oxidation, itself also has certain oxidisability, can be with
Promote the compound of phenolic compound, aniline, fatty amine and heterocyclic that non-biodegradation reaction occurs.
Ultraviolet light is a kind of clean energy resource, is usually used in disinfection and oxidation technology.Meanwhile ultraviolet light is also commonly used for excitation oxygen
It is micro- in water body to effectively remove to generate the very strong hydroxyl radical free radical of oxidisability or other active materials in this process for agent
Pollutant.Ultraviolet radiation is a kind of effective means of excitation manganese dioxide generation active specy, is more advantageous to the micro- pollution of removal
Object object.
The embodiment of the present invention utilizes the method for treating water of the generated in-situ manganese dioxide removal organic matter of UV activation
Principle is that ultraviolet light can excite manganese dioxide to generate hydroxyl radical free radical and other Active manganese species.Hydroxyl radical free radical has very strong
Oxidisability, oxidation-reduction potential is up to 2.7V, as a kind of oxidant of non-selectivity, can aoxidize a variety of different forms
Organic micro-pollutants；And Active manganese species are a kind of selective oxidants in contrast, it can be with efficient oxidation spy
Determine the pollutant of functional group.The embodiment of the present invention takes full advantage of the manganese dioxide generated after permanganate oxidation processing, can
The micropollutants with rock-steady structure for making permanganate or manganese dioxide itself that can not degrade are degraded rapidly, and original position has been widened
The manganese dioxide of generation and has played ultraviolet and manganese dioxide combined disinfection concertedness in the application range of water treatment technology.
This method is suitable for the serial water body such as drinking water, surface water, underground water, sanitary sewage or industrial wastewater containing micropollutants,
Suitable for the water body after Potassium Permanganate Preoxidation, the water quality safety of water environment has been ensured by efficiently removing micropollutants.
The method for treating water of the embodiment of the present invention can be applied not only to the drinking water containing organic pollutant, surface water, underground water, life
The preoxidation process of sewage or industrial wastewater living, while it being equally applicable to the advanced treating of water body, therefore application easy to spread.
The present invention is further illustrated below in conjunction with Figure of description and specific embodiment, but embodiment is not to the present invention
It limits in any form.Unless stated otherwise, the present invention uses reagent, method and apparatus routinely try for the art
Agent, method and apparatus.
Unless stated otherwise, following embodiment agents useful for same and material are commercially available.
Embodiment 1
The embodiment of the present invention removes the method for treating water of micropollutants, includes the following steps：
1) manganous salt and permanganate are added in sequence into the water body containing micropollutants, is stirred evenly, divalent
Manganese salt and permanganate react generated in-situ manganese dioxide；
2) ultraviolet light will be used through step 1) treated water body, stirring removes the micropollutants in water body；
Wherein, the molar ratio of manganese dioxide and micropollutants in water body is 30:1.
The irradiation of ultraviolet light uses overflow-type, and ultraviolet source outer wall needs nested quartz ampoule to be protected.Ultraviolet lamp tube
Light source is light emitting diode (LED).
Wherein, the molar ratio of manganese dioxide and micropollutants in water body is 30:1.
Above-mentioned permanganate is potassium permanganate.
Above-mentioned manganous salt is manganese chloride.
Above-mentioned potassium permanganate or manganese chloride are the stock solution dissolved in advance.
The Single wavelength ultraviolet lamp fluorescent tube that above-mentioned ultraviolet light is 254nm using wavelength, irradiation time are 20 minutes.
Room temperature is maintained at 25 DEG C.
The pH value of water body is 7.
Above-mentioned micropollutants include pesticide organic pollutant.As shown in Figure 1, after the embodiment of the present invention is handled, water body
Micropollutants have apparent reduction.
Embodiment 2
The present embodiment is similar to Example 1, the difference is that：
The molar ratio of micropollutants is 50 in manganese dioxide and water body:1.
The Single wavelength ultraviolet lamp fluorescent tube that ultraviolet light is 254nm using wavelength, irradiation time are 30 minutes.
Light irradiation uses immersion, and ultraviolet source outer wall needs nested quartz ampoule to be protected.
The light source of ultraviolet lamp tube is vacuum UV lamp.
The pH value of water body is 8.
Room temperature is maintained at 25 DEG C.
Above-mentioned permanganate is sodium permanganate.
Above-mentioned manganous salt is manganese nitrate.
Above-mentioned sodium permanganate or manganese nitrate are solid.
Above-mentioned micropollutants include petroleum-type organic pollutant.As shown in Fig. 2, after the embodiment of the present invention is handled, water body
Micropollutants have apparent reduction.
Embodiment 3
The present embodiment is similar to Example 1, the difference is that：
The molar ratio of micropollutants is 20 in manganese dioxide and water body:1.
The Single wavelength ultraviolet lamp fluorescent tube that ultraviolet light is 254nm using wavelength, irradiation time are 25 minutes.
Light irradiation uses surface irradiation formula, and ultraviolet source outer wall needs nested quartz ampoule to be protected.
The light source of ultraviolet lamp tube is low pressure mercury lamp.
The pH value of water body is 9.
Room temperature is maintained at 25 DEG C.
Above-mentioned permanganate is potassium permanganate.
Above-mentioned manganous salt is manganese sulfate.
Above-mentioned potassium permanganate or manganese sulfate are the stock solution dissolved in advance.
Above-mentioned micropollutants include algae toxin, endotoxin etc..As shown in figure 3, after the embodiment of the present invention is handled, water body
Micropollutants have apparent reduction.
Embodiment 4
The present embodiment is similar to Example 1, the difference is that：
The molar ratio of micropollutants is 40 in manganese dioxide and water body:1.
The Single wavelength ultraviolet lamp fluorescent tube that ultraviolet light is 254nm using wavelength, irradiation time are 20 minutes.
Light irradiation uses surface irradiation formula, and ultraviolet source outer wall needs nested quartz ampoule to be protected.
The light source of ultraviolet lamp tube is low pressure mercury lamp.
The pH value of water body is 4.
Room temperature is maintained at 25 DEG C.
Above-mentioned permanganate is potassium permanganate and sodium permanganate.
Above-mentioned manganous salt is manganese sulfate and manganese chloride.
Above-mentioned permanganate or manganous salt are the stock solution dissolved in advance.
Above-mentioned micropollutants include the pollutants such as medicament residue.As shown in figure 4, after the embodiment of the present invention is handled, water body
Micropollutants have apparent reduction.
Embodiment 5
The present embodiment is similar to Example 1, the difference is that：
The molar ratio of micropollutants is 20 in manganese dioxide and water body:1.
The Single wavelength ultraviolet lamp fluorescent tube that ultraviolet light is 254nm using wavelength, irradiation time are 15 minutes.
Light irradiation uses surface irradiation formula, and ultraviolet source outer wall needs nested quartz ampoule to be protected.
The light source of ultraviolet lamp tube is low pressure mercury lamp.
The pH value of water body is 5.
Room temperature is maintained at 25 DEG C.
Above-mentioned permanganate is potassium permanganate and sodium permanganate.
Above-mentioned manganous salt is manganese sulfate and manganese nitrate.
Above-mentioned permanganate or manganous salt are the stock solution dissolved in advance.As shown in figure 5, through the embodiment of the present invention
After processing, the micropollutants of water body have apparent reduction.
Embodiment 6
Light irradiation uses surface irradiation formula, and ultraviolet source does not need nested quartz ampoule and is protected.To containing NDA drug
Pure water is handled, and pH condition is 7.4.Meanwhile two groups of control groups are set：Reaction solution is carried out respectively under the same conditions former
Position manganese dioxide dark treatment and ultraviolet photolysis, reaction time are 20 minutes.Generated in-situ manganese dioxide throwing amount is 100 μM,
The throwing amount of drug is 2 μM.
The method of the embodiment of the present invention is as shown in Fig. 6 to the removal effect of NDA in water, C and C0Respectively surveyed drug
Concentration and parent drugs concentration；In independent UV illumination, the removal rate of NDA only about 50% when 10min；Independent manganese dioxide into
(illumination is not added) when row oxidation, the removal rate of NDA is almost 0；And when UV illumination and generated in-situ manganese dioxide are combined,
The removal efficiency of NDA obviously increases, and only 10min can make NDA degrade substantially completely, and wherein pseudo first-order reaction rate constant is than independent
The first order reaction rate constant of UV illumination increases 4.66 times.
Technical solution in above-mentioned the embodiment of the present application, at least has the following technical effect that or advantage：
The method for treating water of the embodiment of the present invention adds manganous salt and permanganate in the water body containing micropollutants
To generate manganese dioxide in situ, while UV Light is carried out to water body；Wherein, ultraviolet light photodissociation manganous salt and height are utilized
The generated in-situ manganese dioxide of manganate generates hydroxyl radical free radical and intermediate state Active manganese substance, so as to quickly remove
Micropollutants in water body, this method can significantly improve the rate of individually manganese dioxide degradation micropollutants in situ, the present invention
Without expensive oxidant and catalyst, by combining cheap ultraviolet wave spectrum light source, it can be achieved that quickly removing micro- pollution
Object has many advantages, such as throwing amount is small, at low cost, easy to operate, removal efficiency is high, easily controllable, without secondary pollution.Together
When, present method solves the defects that manganese dioxide itself is unable to the stable micropollutants of oxidation structure, while enhancing independent purple
The effect of outer light removal micropollutants.
Above-described specific embodiment has carried out further the purpose of the present invention, technical scheme and beneficial effects
It is described in detail, it should be understood that being not limited to this hair the foregoing is merely a specific embodiment of the invention
Bright, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should be included in the present invention
Protection scope within.
Claims (10)
1. a kind of method for treating water for removing micropollutants, it is characterised in that：Include the following steps：
1) manganous salt and permanganate are added into the water body containing micropollutants, stirs evenly, the manganous salt and height
Mangaic acid reactant salt in-situ preparation manganese dioxide；
2) ultraviolet light will be used through step 1) treated water body, stirring removes the micropollutants in water body；
Wherein, the molar ratio of manganese dioxide and micropollutants in water body is 20-50:1.
2. removing the method for treating water of micropollutants according to claim 1, it is characterised in that：The permanganate is selected from height
Potassium manganate and sodium permanganate.
3. removing the method for treating water of micropollutants according to claim 1, it is characterised in that：The manganous salt is selected from chlorine
Change manganese, manganese nitrate and manganese sulfate.
4. removing the method for treating water of micropollutants according to claim 1, it is characterised in that：The permanganate or divalent
Manganese salt is solid or the preparatory stock solution dissolved.
5. removing the method for treating water of micropollutants according to claim 1, it is characterised in that：The light source of the ultraviolet light is
Light emitting diode, low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, amalgam ultraviolet lamp, halogen lamp, xenon lamp, blackout, vacuum UV lamp,
X-ray, alpha ray, in gamma-rays or any one or combination of sunlight.
6. removing the method for treating water of micropollutants according to claim 1, it is characterised in that：The side of the ultraviolet light
Formula is overflow-type, immersion or surface irradiation formula.
7. removing the method for treating water of micropollutants according to claim 1, it is characterised in that：The ultraviolet light uses
When wavelength is the Single wavelength ultraviolet lamp fluorescent tube of 254nm, ultraviolet light intensity used is 40-200mJ cm-2。
8. removing the method for treating water of micropollutants according to claim 1, it is characterised in that：The pH value of the water body is 4-
9。
9. removing the method for treating water of micropollutants according to claim 8, it is characterised in that：The pH value of the water body is 7-
8。
10. removing the method for treating water of micropollutants according to claim 1, it is characterised in that：The micropollutants include
Drug and personal care articles, persistent organism, Taste and odor compounds, algae toxin, endotoxin, pesticide, petroleum-type organic contamination or difficulty
Any one or more in degradation of organic substances.
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| CN110282693A (en) * | 2019-07-31 | 2019-09-27 | 上海应用技术大学 | A kind of method that ultraviolet/chlorine group technology removes Iopamidol in water removal |
| CN110668527A (en) * | 2019-08-01 | 2020-01-10 | 湖南大学 | Method for removing organic micropollutants in water by using ultraviolet light and ethylene diamine tetraacetic acid |
| CN113461104A (en) * | 2021-07-20 | 2021-10-01 | 杭州师范大学 | Ultraviolet light and potassium permanganate combined algae control method |
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Application publication date: 20181130 |