CN111977866A - Chlorine dioxide and ultraviolet and chlorine coupled water purification method - Google Patents
Chlorine dioxide and ultraviolet and chlorine coupled water purification method Download PDFInfo
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- CN111977866A CN111977866A CN202010669146.0A CN202010669146A CN111977866A CN 111977866 A CN111977866 A CN 111977866A CN 202010669146 A CN202010669146 A CN 202010669146A CN 111977866 A CN111977866 A CN 111977866A
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- chlorine
- ultraviolet
- treatment
- chlorine dioxide
- water
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- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 title claims abstract description 188
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 239000004155 Chlorine dioxide Substances 0.000 title claims abstract description 94
- 235000019398 chlorine dioxide Nutrition 0.000 title claims abstract description 94
- 239000000460 chlorine Substances 0.000 title claims abstract description 90
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 89
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 82
- 238000000746 purification Methods 0.000 title claims abstract description 59
- 238000011282 treatment Methods 0.000 claims abstract description 96
- 238000004659 sterilization and disinfection Methods 0.000 claims abstract description 47
- 229910001919 chlorite Inorganic materials 0.000 claims abstract description 25
- 229910052619 chlorite group Inorganic materials 0.000 claims abstract description 25
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000008878 coupling Effects 0.000 claims abstract description 9
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 10
- 229910052753 mercury Inorganic materials 0.000 claims description 10
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 8
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- 230000001954 sterilising effect Effects 0.000 claims description 8
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- 239000002253 acid Substances 0.000 claims description 2
- 238000011276 addition treatment Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 38
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- 231100000719 pollutant Toxicity 0.000 abstract description 8
- 230000002195 synergetic effect Effects 0.000 abstract description 2
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- 230000000052 comparative effect Effects 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 11
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
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- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 5
- 239000011550 stock solution Substances 0.000 description 5
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- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
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- SMZHKGXSEAGRTI-UHFFFAOYSA-N 1,1,1-trichloropropan-2-one Chemical compound CC(=O)C(Cl)(Cl)Cl SMZHKGXSEAGRTI-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- HEMJJKBWTPKOJG-UHFFFAOYSA-N Gemfibrozil Chemical compound CC1=CC=C(C)C(OCCCC(C)(C)C(O)=O)=C1 HEMJJKBWTPKOJG-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
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- CMWTZPSULFXXJA-UHFFFAOYSA-N Naproxen Natural products C1=C(C(C)C(O)=O)C=CC2=CC(OC)=CC=C21 CMWTZPSULFXXJA-UHFFFAOYSA-N 0.000 description 2
- 239000004100 Oxytetracycline Substances 0.000 description 2
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 2
- RNFNDJAIBTYOQL-UHFFFAOYSA-N chloral hydrate Chemical compound OC(O)C(Cl)(Cl)Cl RNFNDJAIBTYOQL-UHFFFAOYSA-N 0.000 description 2
- 229960002327 chloral hydrate Drugs 0.000 description 2
- 229960003405 ciprofloxacin Drugs 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- DCOPUUMXTXDBNB-UHFFFAOYSA-N diclofenac Chemical compound OC(=O)CC1=CC=CC=C1NC1=C(Cl)C=CC=C1Cl DCOPUUMXTXDBNB-UHFFFAOYSA-N 0.000 description 2
- 229960001259 diclofenac Drugs 0.000 description 2
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- 239000007789 gas Substances 0.000 description 2
- 229960003627 gemfibrozil Drugs 0.000 description 2
- DGAIEPBNLOQYER-UHFFFAOYSA-N iopromide Chemical compound COCC(=O)NC1=C(I)C(C(=O)NCC(O)CO)=C(I)C(C(=O)N(C)CC(O)CO)=C1I DGAIEPBNLOQYER-UHFFFAOYSA-N 0.000 description 2
- 229960002603 iopromide Drugs 0.000 description 2
- 229960002009 naproxen Drugs 0.000 description 2
- CMWTZPSULFXXJA-VIFPVBQESA-N naproxen Chemical compound C1=C([C@H](C)C(O)=O)C=CC2=CC(OC)=CC=C21 CMWTZPSULFXXJA-VIFPVBQESA-N 0.000 description 2
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 description 2
- 229960001180 norfloxacin Drugs 0.000 description 2
- IWVCMVBTMGNXQD-PXOLEDIWSA-N oxytetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3[C@H](O)[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-PXOLEDIWSA-N 0.000 description 2
- 229960000625 oxytetracycline Drugs 0.000 description 2
- 235000019366 oxytetracycline Nutrition 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
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- 229960005224 roxithromycin Drugs 0.000 description 2
- XOXHILFPRYWFOD-UHFFFAOYSA-N sulfachloropyridazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=CC=C(Cl)N=N1 XOXHILFPRYWFOD-UHFFFAOYSA-N 0.000 description 2
- 229950008831 sulfachlorpyridazine Drugs 0.000 description 2
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 2
- 229960004306 sulfadiazine Drugs 0.000 description 2
- 229960002135 sulfadimidine Drugs 0.000 description 2
- ASWVTGNCAZCNNR-UHFFFAOYSA-N sulfamethazine Chemical compound CC1=CC(C)=NC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 ASWVTGNCAZCNNR-UHFFFAOYSA-N 0.000 description 2
- 229960005404 sulfamethoxazole Drugs 0.000 description 2
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 2
- IWVCMVBTMGNXQD-UHFFFAOYSA-N terramycin dehydrate Natural products C1=CC=C2C(O)(C)C3C(O)C4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-UHFFFAOYSA-N 0.000 description 2
- 229960000278 theophylline Drugs 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229960003500 triclosan Drugs 0.000 description 2
- IEDVJHCEMCRBQM-UHFFFAOYSA-N trimethoprim Chemical compound COC1=C(OC)C(OC)=CC(CC=2C(=NC(N)=NC=2)N)=C1 IEDVJHCEMCRBQM-UHFFFAOYSA-N 0.000 description 2
- 229960001082 trimethoprim Drugs 0.000 description 2
- NWQWQKUXRJYXFH-UHFFFAOYSA-N 2,2-Dichloroacetaldehyde Chemical compound ClC(Cl)C=O NWQWQKUXRJYXFH-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- STZZWJCGRKXEFF-UHFFFAOYSA-N Dichloroacetonitrile Chemical compound ClC(Cl)C#N STZZWJCGRKXEFF-UHFFFAOYSA-N 0.000 description 1
- MDNWOSOZYLHTCG-UHFFFAOYSA-N Dichlorophen Chemical compound OC1=CC=C(Cl)C=C1CC1=CC(Cl)=CC=C1O MDNWOSOZYLHTCG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FMWLUWPQPKEARP-UHFFFAOYSA-N bromodichloromethane Chemical compound ClC(Cl)Br FMWLUWPQPKEARP-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000005779 cell damage Effects 0.000 description 1
- 208000037887 cell injury Diseases 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- LFHISGNCFUNFFM-UHFFFAOYSA-N chloropicrin Chemical compound [O-][N+](=O)C(Cl)(Cl)Cl LFHISGNCFUNFFM-UHFFFAOYSA-N 0.000 description 1
- 238000011278 co-treatment Methods 0.000 description 1
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- 230000000593 degrading effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000004989 dicarbonyl group Chemical group 0.000 description 1
- 229960003887 dichlorophen Drugs 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- -1 permanganate Chemical compound 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
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Images
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
- C02F1/001—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
- C02F1/30—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
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
-
- 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
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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)
- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a water purification method by coupling chlorine dioxide with ultraviolet and chlorine, belonging to the technical field of drinking water treatment and comprising two treatment methods: (1) carrying out oxidation treatment on chlorine dioxide, ultraviolet and chlorine in sequence, and then carrying out conventional water treatment; (2) firstly, chlorine dioxide treatment is carried out, and after the conventional treatment process, ultraviolet and chlorine treatment is used as advanced treatment; when the concentration of the soluble organic matters in the water is less than 3mg/L, the effective concentration of the added chlorine dioxide is 0.2-0.5 mg/L; when the concentration of the soluble organic matters in the water is not less than 3mg/L, the effective concentration of the added chlorine dioxide is 0.5-1.0 mg/L; the treatment time of chlorine dioxide is 2-30 minutes. The method removes the pollutants difficult to degrade by the synergistic action of chlorine dioxide, ultraviolet and chlorine, can greatly reduce the generation amount of chlorite and halogenated disinfection byproducts, reduce the concentration of residues, and improve the water supply safety.
Description
Technical Field
The invention belongs to the technical field of drinking water treatment, and particularly relates to a water purification method by coupling chlorine dioxide with ultraviolet and chlorine.
Background
The micro-polluted water source contains a large amount of soluble organic matters and exists in trace amount of nondegradable pollutants with complex components (such as persistent organic matters, algal toxins and smelly substances, medicines and personal care products, pesticides and the like). However, the conventional water treatment process has limited treatment capacity on micro-polluted water sources by coagulation, precipitation, filtration and disinfection, is difficult to completely remove trace pollutants which are difficult to degrade, can generate a large amount of disinfection byproducts, and is not beneficial to the water supply safety of drinking water.
At present, the water plant is usually used for treating micro-polluted water sources by adopting a pre-oxidation strengthening technology, and the commonly used pre-oxidation technology comprises chlorination, chlorine dioxide, permanganate, ozone and the like. However, these highly toxic by-products from pre-oxidation and reaction with water-soluble organics adversely affect water quality. For example, liquid chlorine pre-oxidation produces chlorinated disinfection byproducts such as trichloromethane and chloroacetic acid; chlorine dioxide preoxidation to produce chlorite; the manganese ions are overproof and have chromaticity problems due to permanganate; ozone pre-oxidation presents bromate problems. Meanwhile, the single pre-oxidation technology is difficult to ensure the complete removal of the composite difficultly-degradable pollutants in the micro-polluted water.
The ultraviolet/chlorine advanced oxidation technology is a novel advanced oxidation technology, synergistically degrades various micro pollutants by generating strong oxidizing hydroxyl radicals (HO), chlorine radicals (Cl) and chlorine oxygen radicals (ClO), has sterilization capability, and is an effective means for removing the micro pollutants. At present, researches on high-efficiency degradation of drugs and personal care products by ultraviolet/chlorine advanced oxidation technology are widely reported, and the effect of the researches is similar to or superior to that of ultraviolet/hydrogen peroxide advanced oxidation. However, the soluble organic matters contained in the actual slightly polluted water obviously consume free radicals, the capacity of ultraviolet/chlorine advanced oxidation for degrading pollutants is weakened, and the free radicals react with the soluble organic matters in the water to generate highly toxic dicarbonyl products to cause cell damage. And ultraviolet/chlorine advanced oxidation technology promotes the generation of disinfection byproducts such as trichloromethane and the like. These problems limit the application of uv/chlorine advanced oxidation technology to practical drinking water treatment.
Chinese patent application CN101774711A (a method for reducing chlorite as a disinfection by-product of drinking water) discloses a method for using chlorine dioxide for pre-oxidation and sodium hypochlorite for disinfection, which comprises the following steps: the method comprises the steps of pre-oxidizing raw water by using chlorine dioxide gas, adjusting the pH value by adding lime, adding a coagulant, performing coagulation, precipitation and filtration to remove turbidity, and adding a sodium hypochlorite solution for disinfection. The object of this published patent is to reduce the amount of chlorite produced, but it is still difficult to effectively reduce the amount of chlorite in drinking water due to the addition of sodium hypochlorite. In the chinese patent application CN104370402A (method for removing trace organic pollutants in reclaimed water), the synergistic effect of pretreatment, ozone preoxidation, and ultraviolet enhancement treatment is adopted, so that the efficient removal of trace organic pollutants in reclaimed water can be realized, the action capacity is significantly greater than the treatment effect of any one or two of them, and at the same time, a good treatment effect can be achieved under the conditions of low ozone addition amount and low ultraviolet lamp output power, and the operation cost is low. However, the ozone pre-oxidation technology has the problem of bromate introduction, so that the treatment effect is poor. In the chinese patent application CN103342411A (a method for regulating water quality of raw water transportation pipeline by using chlorine dioxide and chlorine combined oxidation), chlorine dioxide and chlorine are added into the raw water pipeline at a ratio of 1:3-5 simultaneously, and the raw water pipeline is kept for two days under the condition that the concentration of chlorine dioxide is 0.5-1.5mg/L, but this method will leave a large amount of chlorides such as chlorite and the like in the raw water.
Therefore, a new water purification method is needed to solve the deficiencies of the prior art.
Disclosure of Invention
The invention aims to solve the technical problems of more disinfection byproducts, high residue concentration and the like in the drinking water purification technology in the prior art.
In order to solve the technical problem, the invention discloses a water purification method by coupling chlorine dioxide with ultraviolet and chlorine, when the concentration of soluble organic matters in raw water is less than 3mg/L, the effective concentration of the added chlorine dioxide is 0.2-0.5 mg/L; when the concentration of soluble organic matters in raw water is not less than 3mg/L, the effective concentration of added chlorine dioxide is 0.5-1.0 mg/L; the treatment time of chlorine dioxide is 2-30 minutes.
Furthermore, in the water purification process, chlorine dioxide is added into raw water for treatment, and then coagulation, precipitation, filtration and disinfection are sequentially carried out.
Further, after the chlorine dioxide addition treatment is completed, before coagulation, ultraviolet and chlorine treatments are performed.
Further, after filtration and before sterilization, ultraviolet and chlorine oxidation treatment and sterilization treatment may be performed. In this case, the ultraviolet and chlorine treatments correspond to the deep treatment.
After the coupling treatment of chlorine dioxide, ultraviolet rays and chlorine is completed, the purified water needs to be subjected to final disinfection treatment, wherein the disinfection is conventional disinfection treatment, and is an important one-step conventional operation for converting the purified water into drinking water in a water treatment plant.
Further, when the chlorine dioxide treatment is carried out, the added chlorine dioxide is chlorine dioxide aqueous solution; the aqueous chlorine dioxide solution is prepared by reacting chlorite and acid.
Further, the method of ultraviolet and chlorine treatment is a combination of ultraviolet irradiation and chlorine treatment. Namely, chlorine is added for treatment at the same time of ultraviolet irradiation.
Further, the time for the UV and chlorine treatment is 5 to 30 minutes.
Furthermore, in the ultraviolet irradiation, the ultraviolet light source is an ultraviolet low-pressure mercury lamp, an ultraviolet medium-pressure mercury lamp or an LED ultraviolet lamp, and the ultraviolet irradiation dose is 50-150mJ/cm2(ii) a The ultraviolet irradiation mode includes an immersion type, an overflow type or a surface irradiation type.
Furthermore, the ultraviolet wavelength of the ultraviolet low-pressure mercury lamp is 185nm and/or 254nm, and the ultraviolet wavelength of the LED ultraviolet lamp is 265nm, 280nm and/or 300 nm. The ultraviolet light of the ultraviolet medium-pressure mercury lamp has multiple wavelengths, no specific wavelength is output, and the wavelength range of the ultraviolet light is 300-600 nm.
Furthermore, in the chlorine oxidation treatment, chlorine is hypochlorite or liquid chlorine, and the effective concentration of the added chlorine is 1-10 mg/L.
In the invention, chlorine and organic pollutants are subjected to chlorination, oxidation and other reactions, so that the molecular structure of the organic matters is changed fundamentally, and the removal effect of the organic pollutants is enhanced.
The chlorine dioxide can oxidize soluble organic matters in water, and the organic matters react with phenol, amine, aniline groups and the like in the organic matters to change the structure of the soluble organic matters, and the reaction activities of the organic matters, chlorine and other reaction active substances are different.
The generation of a byproduct chlorite is reduced by reducing the dosage of chlorine dioxide, a part of chlorite is consumed in the ultraviolet and chlorine treatment process, the concentration of chlorite is further reduced, namely, the effect of oxidizing and removing organic pollutants by chlorine dioxide is limited, if the single chlorine dioxide technology is used for achieving the same pollutant removal effect as the ultraviolet and chlorine treatment, the higher effective concentration of chlorine dioxide is needed, and the chlorine dioxide is coupled with the ultraviolet and chlorine, so that the organic pollutants can be effectively removed by means of the ultraviolet and chlorine under the lower effective concentration of chlorine dioxide, and at the moment, the generation of the byproduct chlorite of the organic matters oxidized by the chlorine dioxide can be reduced; additionally the chlorite formed is also consumed in the uv and chlorine system and the overall chlorite concentration is further reduced.
Compared with the prior art, the water purification method based on the coupling of chlorine dioxide, ultraviolet and chlorine has the following advantages:
(1) the removal effect of the refractory organic pollutants is improved through various oxidation ways;
(2) by combining chlorine dioxide treatment with ultraviolet and chlorine treatment, the structure and properties of soluble organic matters in water are changed, and the content of final halogenated disinfection byproducts is controlled;
(3) by reducing the input amount of chlorine dioxide, the generation amount of chlorite is reduced, the concentration of chlorite byproducts is effectively controlled, chlorite can be consumed in an ultraviolet and chlorine system, and the total chlorite concentration is further reduced;
(4) the water purification method is easy to realize in a drinking water plant, has simple operation management and is convenient for technical upgrading and reconstruction of a conventional water plant.
Description of the drawings:
FIG. 1: flow chart of water purification method by coupling chlorine dioxide with ultraviolet and chlorine in example 1.
FIG. 2: example 4 is a flow chart of a water purification method by coupling chlorine dioxide with ultraviolet and chlorine.
FIG. 3: concentration of halogenated disinfection by-products in water before post-chlorination.
FIG. 4: and (4) performing post-chlorination treatment on the water for 2 hours to obtain the concentration of halogenated disinfection byproducts.
FIG. 5: the method has the advantages of single use of chlorine dioxide and purification treatment effect on different organic matters during water purification by adopting the method.
FIG. 6: the tendency of uv and chlorine reaction times to affect the chlorite concentration in water after treatment with chlorine dioxide at various concentrations.
Detailed Description
The technical solution of the present invention will be described in detail by the following specific examples.
Fig. 1 and 2 show two different water purification process flows, respectively, in fig. 1, chlorine dioxide is firstly added into raw water for oxidation, then ultraviolet and chlorine treatment is carried out, and then coagulation, precipitation, filtration and conventional disinfection treatment are carried out; in fig. 2, chlorine dioxide is first added to raw water to perform oxidation, then coagulation, precipitation and filtration are performed, then ultraviolet and chlorine oxidation treatment is performed, and finally conventional disinfection treatment is performed. Both methods can be used to treat raw water.
First, a chlorine dioxide stock solution was prepared according to the method of the American publicStandard methods for Water and wastewater detection promulgated by the Council of sanitation (WALTER W G.Standard methods for the Examination of Water and Water (11th ed.) [ J].American Journal of Public Health&the national Health,1961,51(6): 940-: first 10g of NaClO2Dissolving in 500mL of water to prepare a sodium chlorite aqueous solution; simultaneously dissolving 2mL of concentrated sulfuric acid with the mass fraction of 98% in 18mL of water to prepare H2SO4A solution; then H is introduced2SO4Slowly adding the solution into a sodium chlorite aqueous solution, dissolving chlorine dioxide gas generated after reaction in water to form a chlorine dioxide aqueous solution, namely a chlorine dioxide stock solution, calibrating the concentration of the stock solution before use, and then calculating the amount of the chlorine dioxide stock solution required to be added in a reaction system according to the effective concentration of chlorine dioxide. In practical application, according to the amount of water required to be purified, a proper amount of chlorine dioxide stock solution is prepared for later use according to the dosage ratio of the sodium chlorite to the sulfuric acid.
Example 1
The concentration of soluble organic matters in raw water is 2.5mg/L, 17 trace organic pollutants are respectively detected to be estrone, sulfamethazine, sulfachlorpyridazine, sulfamethoxazole, oxytetracycline, diclofenac, sulfadiazine, triclosan, gemfibrozil, roxithromycin, theophylline, butylthiodiphenylamine, naproxen, trimethoprim, norfloxacin, ciprofloxacin and iopromide, and the concentration level of the raw water is 500 ng/L.
The water purification method of fig. 1 is adopted: (1) adding chlorine dioxide into raw water, measuring the effective concentration of the added chlorine dioxide to be 0.5mg/L by using a residual chlorine machine, treating for 30 minutes, then carrying out ultraviolet and chlorine oxidation treatment for 5 minutes, wherein in the ultraviolet and chlorine oxidation treatment, a low-pressure mercury lamp with an ultraviolet light source of 254nm wavelength is adopted for surface irradiation, and the ultraviolet irradiation dose is 81mJ/cm2Chlorine-oxidizing treatment is carried out by using liquid chlorine, and the effective concentration of the added chlorine is measured by using a chlorine residual machine to be 5 mg/L. (2) Coagulating, precipitating, filtering and sterilizing.
Examples 2 to 3
The raw water to be treated is the same as in example 1, and the steps of the water purification method are the same as in example 1, except that specific process parameters in the processes of treatment with chlorine dioxide and treatment with ultraviolet and chlorine oxidation are provided in table 1.
Example 4
The raw water to be treated was the same as in example 1, and the water purification method shown in FIG. 2 was used: (1) adding chlorine dioxide into water, measuring the effective concentration of the added chlorine dioxide to be 0.5mg/L by using a residual chlorine machine, and treating for 5 minutes; (2) coagulating, precipitating and filtering; (3) in the ultraviolet and chlorine oxidation treatment, an LED ultraviolet lamp with an ultraviolet light source of 280nm wavelength is adopted for overcurrent irradiation, and the ultraviolet irradiation dose is 100mJ/cm2Carrying out chlorine oxidation treatment by using sodium hypochlorite, measuring the effective concentration of added chlorine to be 2mg/L by using a residual chlorine machine, and carrying out ultraviolet and chlorine oxidation treatment for 20 minutes; (4) and (6) sterilizing. Specific process parameters during treatment with chlorine dioxide and uv and chlorine treatment are shown in table 1.
Comparative examples 1 to 2
In order to verify the water purification effect of the chlorine dioxide treatment and the ultraviolet and chlorine treatment processes in the method when the concentration of the soluble organic matters in the raw water is less than 3mg/L, comparative examples 1-2 are provided, wherein the steps of the water purification method of comparative example 1 are the same as those of example 1, the steps of the water purification method of comparative example 2 are the same as those of example 4, and the specific process parameters are shown in Table 1.
TABLE 1 concrete Process parameters of the Water purification method in examples 1 to 3 and comparative examples 1 to 2
Example 5
The concentration of soluble organic matters in raw water is 4mg/L, and 17 trace organic pollutants in the raw water are detected to be estrone, sulfamethazine, sulfachlorpyridazine, sulfamethoxazole, oxytetracycline, diclofenac, sulfadiazine, triclosan, gemfibrozil, roxithromycin, theophylline, butylthiodiphenylamine, naproxen, trimethoprim, norfloxacin, ciprofloxacin and iopromide. The respective concentration levels were 500 ng/L.
The water purification method of fig. 1 is adopted: (1) adding chlorine dioxide into raw water, measuring the effective concentration of the added chlorine dioxide to be 1mg/L by using a residual chlorine machine, treating for 30 minutes, and then carrying out ultraviolet and chlorine oxidation treatment for 5 minutes, wherein in the ultraviolet and chlorine oxidation treatment, a low-pressure mercury lamp with an ultraviolet light source of 185nm wavelength is adopted for surface irradiation, and the ultraviolet irradiation dose is 81mJ/cm2Chlorine-oxidizing treatment is carried out by using liquid chlorine, and the effective concentration of the added chlorine is measured by using a chlorine residual machine to be 5 mg/L. (2) Coagulating, precipitating, filtering and sterilizing.
Examples 6 to 7
The raw water to be treated was the same as in example 5, and the procedure of the water purification method was the same as in example 4, except that specific process parameters in the treatment with chlorine dioxide and the ultraviolet and chlorine oxidation treatment were used in the water purification method, and the corresponding specific process parameters are shown in table 1.
Example 8
The raw water to be treated was the same as in example 5, and the water purification method shown in FIG. 2 was used: (1) adding chlorine dioxide into raw water, measuring the effective concentration of the added chlorine dioxide to be 0.8mg/L by using a residual chlorine machine, and treating for 5 minutes; (2) coagulating, precipitating and filtering; (3) in the ultraviolet and chlorine oxidation treatment, a low-pressure mercury lamp with an ultraviolet source of 185nm wavelength is adopted for surface irradiation, and the ultraviolet dose is 110mJ/cm2Carrying out chlorine oxidation treatment by using sodium hypochlorite, measuring the effective concentration of added chlorine to be 1mg/L by using a residual chlorine machine, and carrying out ultraviolet and chlorine oxidation treatment for 1 minute; (4) and (6) sterilizing. The specific process parameters during the treatment with chlorine dioxide and the treatment with uv and chlorine oxidation are shown in table 1.
Comparative examples 3 to 4
In order to verify the water purification effect of the chlorine dioxide treatment and the ultraviolet and chlorine oxidation treatment processes in the method when the concentration of the soluble organic matters in the water is not less than 3mg/L, comparative examples 3-4 are provided, wherein the steps of the water purification method of comparative example 3 are the same as those of example 5, the steps of the water purification method of comparative example 4 are the same as those of example 8, and the specific process parameters are shown in Table 1.
TABLE 2 concrete process parameters of the water purification method in examples-8 and comparative examples 3-4
The water purification effect test data in the above examples and comparative examples are shown in table 3.
TABLE 3 Water purification Effect data of the Water purification method in the above examples and comparative examples
As can be seen from Table 3, when the water purification method of the present invention is used for water treatment, the average removal rate of organic substances is significantly higher than that of the water treatment method of the comparative example, and the concentrations of chlorite and halogenated disinfection byproducts are significantly lower than that of the comparative example, which indicates that the water purification method of the present invention has good water treatment effect.
In the water purification method of the present invention, the halogenated disinfection byproducts mainly include chloroform, dichlorobromomethane, chloral hydrate, trichloroacetone, dichlorophen, dichloroacetaldehyde, dichloroacetonitrile, trichloronitromethane, etc., wherein chloroform, chloral hydrate and trichloroacetone are the main halogenated disinfection byproducts, and therefore, only the contents of the three main halogenated disinfection byproducts are given in table 3. Meanwhile, the concentrations of the halogenated disinfection byproducts in the purified water after 30 minutes of treatment (i.e., before post-chlorination) and 2 hours of post-chlorination by the water purification method are also shown in table 3, and after 2 hours of post-chlorination, the concentration of the halogenated disinfection byproducts in the water is measured after the water purification method is completed and 30 minutes later, liquid chlorine with the chlorine effective concentration of 10mg/L is added into the water, and the post-chlorination treatment is carried out for 2 hours.
To demonstrate that the water purification method of the present invention can effectively suppress the production of halogenated disinfection byproducts, the control example of example 1 was set up, namely: the difference from example 1 is only that the effective concentration of chlorine dioxide added was 0mg/L, 0.2mg/L, and the concentration of halogenated disinfection by-products in the purified water after 30 minutes of treatment (i.e., before post-chlorination) was measured, as shown in FIG. 3; meanwhile, after the above-mentioned water purification method was completed, 30 minutes later, liquid chlorine having an effective chlorine concentration of 10mg/L was added to the water, and after the post-chlorination treatment was carried out for 2 hours, the concentration of the halogenated disinfection by-products in the water was measured, as shown in FIG. 4.
The liquid chlorine is continuously added after the water purification is finished, in order to simulate that some precursor substances of halogenated disinfection byproducts in water can also react with residual chlorine in the water to generate disinfection byproducts when water discharged from a water plant enters a pipe network of a user for a certain time, and the experimental design can determine the generation potential of the halogenated disinfection byproducts in the water treated by the method, namely the concentration of all the generated halogenated disinfection byproducts.
Combining the concentrations of halogenated disinfection byproducts before post-chlorination and after post-chlorination for 2h in table 3, and as can be seen in fig. 3 and 4, the concentration of halogenated disinfection byproducts in water increases significantly after post-chlorination for 2 h; particularly, as for fig. 3 and 4, after the water purification method of the invention is adopted to complete water purification treatment for 30 minutes, the concentration of halogenated disinfection byproducts in water is below 35 mug/L, and after the post-chlorination treatment is carried out for 2 hours, the concentration of the halogenated disinfection byproducts is greatly improved, particularly, the content of trichloromethane reaches more than 65 mug/L and almost reaches 2 times of the original concentration, which indicates that after the water purification treatment is carried out for 30 minutes by adopting the method of the invention, partial disinfection byproduct precursor substances are not completely reacted, and the post-chlorination completely converts the partial precursor substances into the halogenated disinfection byproducts.
Meanwhile, referring to fig. 3 and 4, respectively, the experimental groups of chlorine dioxide were added at the concentrations of halogenated disinfection byproducts at different chlorine dioxide effective concentrations, that is, when the chlorine dioxide concentrations were 0.2mg/L and 0.5mg/L, respectively, the concentrations of the halogenated disinfection byproducts were lower than the experimental groups without chlorine dioxide as a whole, which demonstrates that the water purification method of the present invention effectively suppresses the generation of the halogenated disinfection byproducts.
In order to prove that the water purification method by coupling chlorine dioxide with ultraviolet and chlorine has good water purification effect, the comparison example of the embodiment 1 is provided, namely: compared with the example 1, the difference is only that 0.5mg/L chlorine dioxide is used for pure water treatment. As shown in FIG. 5, the water purification effect of the method of example 1 using 0.5mg/L chlorine dioxide alone is shown, and the results show that: after the chlorine dioxide, ultraviolet rays and chlorine are adopted for treatment, the removal effect of 17 medicines in raw water is higher than that of raw water treated by the chlorine dioxide alone, the removal rate of the 17 organic matters is higher than 50%, and the removal rate of 13 medicines is higher than 85%. Several organic substances in group ii were difficult to degrade when treated with chlorine dioxide alone, but the concentration was significantly reduced after co-treatment of chlorine dioxide with uv and chlorine.
To investigate the tendency of chlorine dioxide dosage, uv and chlorine treatment time to affect the chlorite concentration in water during the chlorine dioxide treatment, a control example of example 1 was set up, namely: compared with example 1, the difference is only that the effective concentration of the added chlorine dioxide is 0.2mg/L, as shown in figure 6, the ultraviolet dose is gradually increased along with the prolonging of the ultraviolet and chlorine treatment time, and it can be seen that, because the chlorite is mainly a disinfection by-product generated in the process of the chlorine dioxide treatment, when the adding amount of the chlorine dioxide is 0.5mg/L, the concentration of the chlorite in the water is obviously higher than that of the chlorine dioxide, which is 0.2 mg/L; the chlorite concentration in the water gradually decreased with increasing uv and chlorine treatment time, indicating that the uv and chlorine treatment effectively decreased the concentration of the disinfection by-product chlorite in the water.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, so any modifications, equivalents, improvements and the like made within the spirit of the present invention should be included in the scope of the present invention.
Claims (10)
1. A chlorine dioxide and ultraviolet and chlorine coupling water purification method is characterized in that: when the concentration of soluble organic matters in raw water is less than 3mg/L, the effective concentration of added chlorine dioxide is 0.2-0.5 mg/L; when the concentration of soluble organic matters in raw water is not less than 3mg/L, the effective concentration of added chlorine dioxide is 0.5-1.0 mg/L; the treatment time of chlorine dioxide is 2-30 minutes.
2. The water purification method of claim 1, wherein: in the water purification process, chlorine dioxide is added into raw water for treatment, and then coagulation, precipitation, filtration and disinfection are sequentially carried out.
3. The water purification method of claim 2, wherein: after the chlorine dioxide addition treatment is completed, the ultraviolet and chlorine treatments are performed before coagulation.
4. The water purification method of claim 2, wherein: after filtration, uv and chlorine treatments were performed before sterilization.
5. The water purification method of claim 1, wherein: when the chlorine dioxide treatment is carried out, the added chlorine dioxide is a chlorine dioxide aqueous solution; the aqueous chlorine dioxide solution is prepared by reacting chlorite and acid.
6. The water purification method of claim 3 or 4, wherein: the method of ultraviolet and chlorine treatment is the combination of ultraviolet irradiation and chlorine treatment.
7. The water purification method of claim 6, wherein: the time of the ultraviolet and chlorine treatment is 5-30 minutes.
8. The water purification method of claim 6, wherein: in the ultraviolet irradiation, the ultraviolet light source is an ultraviolet low-pressure mercury lamp, an ultraviolet medium-pressure mercury lamp or an LED ultraviolet lamp, and the ultraviolet irradiation dose is 50-150mJ/cm2(ii) a The mode of ultraviolet irradiation includesImmersion, overflow or surface irradiation.
9. The water purification method of claim 8, wherein: the ultraviolet wavelength of the ultraviolet low-pressure mercury lamp is 185nm and/or 254nm, and the ultraviolet wavelength of the LED ultraviolet lamp is 265nm, 280nm and/or 300 nm.
10. The water purification method of claim 6, wherein: in the chlorine treatment, chlorine is hypochlorite or liquid chlorine, and the effective concentration of the added chlorine is 1-10 mg/L.
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