CN106830280A - The method for treating water of instability halogenated disinfection by-products in a kind of utilization persulfate in-situ control swimming-pool water - Google Patents
The method for treating water of instability halogenated disinfection by-products in a kind of utilization persulfate in-situ control swimming-pool water Download PDFInfo
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- CN106830280A CN106830280A CN201710050811.6A CN201710050811A CN106830280A CN 106830280 A CN106830280 A CN 106830280A CN 201710050811 A CN201710050811 A CN 201710050811A CN 106830280 A CN106830280 A CN 106830280A
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- persulfate
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- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 title claims abstract description 109
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 238000004659 sterilization and disinfection Methods 0.000 title claims abstract description 77
- 239000006227 byproduct Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 46
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 38
- 230000009182 swimming Effects 0.000 claims abstract description 53
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 36
- 125000005385 peroxodisulfate group Chemical group 0.000 claims description 29
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 23
- 239000003513 alkali Substances 0.000 claims description 22
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 17
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 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 1
- 239000011259 mixed solution Substances 0.000 claims 1
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical group OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- 230000000269 nucleophilic effect Effects 0.000 abstract description 11
- 230000007062 hydrolysis Effects 0.000 abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 8
- 238000001784 detoxification Methods 0.000 abstract description 7
- 239000000645 desinfectant Substances 0.000 abstract description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000000460 chlorine Substances 0.000 abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 abstract description 3
- 239000003651 drinking water Substances 0.000 abstract description 3
- 235000020188 drinking water Nutrition 0.000 abstract description 3
- 239000000126 substance Substances 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- -1 compound salt Chemical class 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 4
- 150000004053 quinones Chemical class 0.000 description 4
- RENMDAKOXSCIGH-UHFFFAOYSA-N Chloroacetonitrile Chemical compound ClCC#N RENMDAKOXSCIGH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000003869 acetamides Chemical class 0.000 description 3
- VXIVSQZSERGHQP-UHFFFAOYSA-N chloroacetamide Chemical compound NC(=O)CCl VXIVSQZSERGHQP-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229930182851 human metabolite Natural products 0.000 description 3
- 239000012038 nucleophile Substances 0.000 description 3
- 210000004243 sweat Anatomy 0.000 description 3
- 210000002700 urine Anatomy 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 239000012434 nucleophilic reagent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 1
- 239000012425 OXONE® Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 231100000190 chronic cytotoxicity Toxicity 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- LFINSDKRYHNMRB-UHFFFAOYSA-N diazanium;oxido sulfate Chemical compound [NH4+].[NH4+].[O-]OS([O-])(=O)=O LFINSDKRYHNMRB-UHFFFAOYSA-N 0.000 description 1
- YMGGAHMANIOXGP-UHFFFAOYSA-L disodium;oxido sulfate Chemical compound [Na+].[Na+].[O-]OS([O-])(=O)=O YMGGAHMANIOXGP-UHFFFAOYSA-L 0.000 description 1
- 231100000025 genetic toxicology Toxicity 0.000 description 1
- 230000001738 genotoxic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- HJKYXKSLRZKNSI-UHFFFAOYSA-I pentapotassium;hydrogen sulfate;oxido sulfate;sulfuric acid Chemical compound [K+].[K+].[K+].[K+].[K+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-] HJKYXKSLRZKNSI-UHFFFAOYSA-I 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- HDMGAZBPFLDBCX-UHFFFAOYSA-N potassium;sulfooxy hydrogen sulfate Chemical compound [K+].OS(=O)(=O)OOS(O)(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000002699 waste material 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
- C02F1/72—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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/42—Nature of the water, waste water, sewage or sludge to be treated from bathing facilities, e.g. swimming pools
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)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
一种利用过硫酸盐原位控制游泳池中非稳定性卤代消毒副产物的水处理方法，它涉及水处理方法。本发明解决了游泳池水液氯消毒过程中易形成非稳定性卤代消毒副产物的问题。本发明的水处理方法：在游泳池水中投加液氯进行消毒处理时，同时投加过硫酸盐溶液，保持搅拌，利用过硫酸盐的亲核水解作用对非稳定性卤代消毒副产物进行分解脱毒，即完成。本发明具有以下优点：过硫酸盐具有极强的亲核能力，能够快速分解非稳定性卤代消毒副产物，且不消耗液氯，可以与液氯共存，实现游泳池水中非稳定性卤代消毒副产物的原位高效转化脱毒；过硫酸盐已被国家正式列入饮用水消毒剂产品目录，能够在游泳池水处理中进行应用；操作简单方便、处理成本低。
A water treatment method for controlling non-stable halogenated disinfection by-products in a swimming pool in situ by utilizing persulfate, which relates to a water treatment method. The invention solves the problem that non-stable halogenated disinfection by-products are easily formed during chlorine disinfection of swimming pool water. The water treatment method of the present invention: when adding liquid chlorine to the swimming pool water for disinfection treatment, add persulfate solution at the same time, keep stirring, and use the nucleophilic hydrolysis of persulfate to decompose the non-stable halogenated disinfection by-products Detoxification is complete. The invention has the following advantages: persulfate has strong nucleophilic ability, can rapidly decompose the non-stable halogenated disinfection by-products, does not consume liquid chlorine, can coexist with liquid chlorine, and realizes non-stable halogenated disinfection in swimming pool water In-situ efficient conversion and detoxification of by-products; persulfate has been officially included in the catalog of drinking water disinfectants by the country, and can be applied in swimming pool water treatment; simple and convenient operation, low treatment cost.
Description
技术领域technical field
本发明涉及一种水处理方法，具体涉及一种控制游泳池水中非稳定性卤代消毒副产物的水处理方法。The invention relates to a water treatment method, in particular to a water treatment method for controlling non-stable halogenated disinfection by-products in swimming pool water.
背景技术Background technique
游泳池水中包括个人护理用品的化学成分、人体的代谢物(汗液、尿液、皮屑、头发等)等各种各样有机物。液氯作为广谱杀菌消毒剂，能够作用于细菌表面并穿透细胞膜进入菌体内，使菌体蛋白氧化导致细菌死亡，并且具有余氯的持续消毒作用，被广泛用于游泳池水消毒，但易产生卤代消毒副产物，尤其一些非稳定性卤代消毒副产物，如：卤代醌(HBQs)、卤乙腈(HANs)、卤代乙酰胺(HAcAms)等，这些新发现且还未被纳入国家相应管理规定的消毒副产物对人体所产生的危害远大于三卤甲烷(THMs)和卤乙酸(HAAs)等已被纳入规定的消毒副产物，虽然其平均浓度约为三卤甲烷的几分之一到几十分之一，但它们的慢性细胞毒性和急性遗传毒性是三卤甲烷的数百至数千倍，造成游泳池水的水质安全，对皮肤、眼睛以及呼吸系统产生危害。Swimming pool water includes chemical components of personal care products, human metabolites (sweat, urine, dander, hair, etc.) and various organic substances. As a broad-spectrum bactericidal disinfectant, liquid chlorine can act on the surface of bacteria and penetrate the cell membrane into the bacteria, oxidize the bacteria protein and cause the death of bacteria, and has the continuous disinfection effect of residual chlorine. It is widely used in swimming pool water disinfection, but it is easy to Produce halogenated disinfection by-products, especially some non-stable halogenated disinfection by-products, such as: haloquinones (HBQs), haloacetonitriles (HANs), haloacetamides (HAcAms), etc. These new findings have not yet been included The disinfection by-products regulated by the corresponding national regulations are far more harmful to the human body than trihalomethanes (THMs) and haloacetic acids (HAAs), which have been included in the regulations, although their average concentration is about a fraction of that of trihalomethanes. However, their chronic cytotoxicity and acute genotoxicity are hundreds to thousands of times higher than that of trihalomethanes, causing the safety of swimming pool water and causing harm to the skin, eyes and respiratory system.
游泳池水中消毒副产物的控制方法主要有控制前体物的进入和对已形成的副产物进行氧化去除。专利CN101475245A公开了一种游泳池水质消毒方法，利用过硫酸盐或单过硫酸氢盐经过钴离子催化方式产生的硫酸自由基杀灭游泳池水中的细菌和藻类生物，同时降解人体排泄的尿素和氨类废物。文献“一种新型过氧化物消毒剂在游泳池水消毒中的应用”利用单过硫酸氢钾溶于水后产生新生态氧、活性氧自由基(过氧化氢自由基、羟基自由基等)对游泳池水进行消毒处理。The control methods of disinfection by-products in swimming pool water mainly include controlling the entry of precursors and oxidative removal of formed by-products. Patent CN101475245A discloses a swimming pool water disinfection method, which uses persulfate or monoperhydrogensulfate to catalyze sulfuric acid free radicals produced by cobalt ions to kill bacteria and algae in swimming pool water, and simultaneously degrades urea and ammonia excreted by the human body waste. The document "Application of a New Peroxide Disinfectant in Swimming Pool Water Disinfection" uses potassium monopersulfate dissolved in water to generate new ecological oxygen and active oxygen free radicals (hydrogen peroxide free radicals, hydroxyl free radicals, etc.) Swimming pool water is disinfected.
非稳定性卤代消毒副产物(如：卤代醌、卤乙腈、卤代乙酰胺)具有分子中与卤素相连的碳原子易受到亲核试剂进攻的特点，易发生亲核水解进行脱毒。利用亲核水解特性对液氯消毒过程中产生的卤代消毒副产物进行控制，常见的亲核试剂有甲醇、过氧化氢等，但由于这些亲核试剂易造成水体的二次污染或液氯的大量消耗，因而难以进行应用。Unstable halogenated disinfection by-products (such as: halogenated quinones, halogenated acetonitriles, halogenated acetamides) have the characteristics that the carbon atoms connected to halogens in the molecule are easily attacked by nucleophiles, and are prone to nucleophilic hydrolysis for detoxification. Use the nucleophilic hydrolysis characteristics to control the halogenated disinfection by-products produced in the liquid chlorine disinfection process. Common nucleophilic reagents include methanol and hydrogen peroxide, but these nucleophilic reagents are likely to cause secondary pollution of water bodies or liquid chlorine A large amount of consumption, so it is difficult to apply.
目前还没有利用有机物的亲核水解特性进行原位控制卤代消毒副产物的研究报道。At present, there is no research report on the in situ control of halogenated disinfection by-products by utilizing the nucleophilic hydrolysis properties of organic matter.
发明内容Contents of the invention
本发明的目的是提供一种利用过硫酸盐原位控制游泳池水中非稳定性卤代消毒副产物的水处理方法，解决游泳池水液氯消毒过程中易形成非稳定性卤代消毒副产物的问题。The purpose of the present invention is to provide a water treatment method using persulfate in situ to control non-stable halogenated disinfection by-products in swimming pool water to solve the problem that non-stable halogenated disinfection by-products are easily formed during chlorine disinfection of swimming pool water .
本发明的一种利用过硫酸盐原位控制游泳池水中非稳定性卤代消毒副产物的水处理方法是通过以下步骤实现的：在游泳池水中投加液氯进行消毒处理时，同时投加过硫酸盐溶液，保持搅拌状态，即完成所述利用过硫酸盐原位控制游泳池水中卤代消毒副产物的水处理方法，其中，过硫酸盐的浓度为0.5～100mg/L。A kind of water treatment method of using persulfate in situ to control non-stable halogenated disinfection by-products in swimming pool water of the present invention is realized through the following steps: when adding liquid chlorine in swimming pool water for disinfection treatment, add persulfuric acid at the same time The saline solution is kept in a stirring state, that is, the water treatment method of using persulfate to control halogenated disinfection by-products in swimming pool water in situ is completed, wherein the concentration of persulfate is 0.5-100 mg/L.
本发明的一种利用过硫酸盐原位控制游泳池水中非稳定性卤代消毒副产物的水处理方法中所述过硫酸盐为过一硫酸盐、过二硫酸盐中的一种或两种按任意比混合的混合物，其中过一硫酸盐为过一硫酸钾、过一硫酸钠中的一种或两种按任意比混合的混合物，过二硫酸盐为过二硫酸钾、过二硫酸钠中的一种或两种按任意比混合的混合物。In a water treatment method of the present invention for in-situ control of non-stable halogenated disinfection by-products in swimming pool water, the persulfate is one or both of permonosulfate and peroxodisulfate. The mixture mixed in any ratio, wherein the persulfate is one of potassium persulfate and sodium persulfate or a mixture of two mixed in any ratio, and the peroxodisulfate is potassium peroxodisulfate and sodium peroxodisulfate One or two mixtures in any ratio.
本发明的一种利用过硫酸盐原位控制游泳池水中非稳定性卤代消毒副产物的水处理方法中所述过硫酸盐由过硫酸盐和碱的复合盐代替，其中过硫酸盐和碱的摩尔比为1:1～10，碱的加入能调节水处理体系的pH值在6～9，有利于过硫酸盐电离；其中，过硫酸盐为过一硫酸盐和/或过二硫酸盐，碱为氢氧化钾、氢氧化钠、氢氧化钙、碳酸钠、碳酸钾、碳酸氢钠、碳酸氢钾中的一种或其中几种按任意比混合的混合物；过一硫酸盐为过一硫酸钾、过一硫酸钠中的一种或两种按任意比混合的混合物，过二硫酸盐为过二硫酸钾、过二硫酸钠中的一种或两种按任意比混合的混合物。In a water treatment method of the present invention that utilizes persulfate in situ to control non-stable halogenated disinfection by-products in swimming pool water, the persulfate is replaced by a compound salt of persulfate and alkali, wherein the composition of persulfate and alkali is The molar ratio is 1:1-10, and the addition of alkali can adjust the pH value of the water treatment system at 6-9, which is conducive to the ionization of persulfate; wherein, persulfate is permonosulfate and/or peroxodisulfate, Alkali is one of potassium hydroxide, sodium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate or a mixture of several of them in any ratio; persulfate is persulfuric acid Potassium and sodium persulfate or a mixture of two in any ratio, and peroxodisulfate is a mixture of potassium and sodium persulfate or two in any ratio.
本发明一种利用过硫酸盐原位控制游泳池水中非稳定性卤代消毒副产物的水处理方法的原理：液氯对游泳池水进行消毒处理时，会与水中存在的大量个人护理用品的化学成分和人体的代谢物(汗液、尿液)等各种各样有机物发生反应形成非稳定性卤代消毒副产物(如：卤代醌、卤乙腈、卤代乙酰胺)，非稳定性卤代消毒副产物分子中与卤素相连的碳原子易受到亲核试剂过硫酸盐的进攻，能够快速发生亲核水解、脱毒，实现非稳定性卤代消毒副产物的原位控制。也就是说，非稳定性卤代消毒副产物一经形成就会快速与水中存在的过硫酸盐发生亲核水解作用被分解脱毒。The principle of the present invention is a water treatment method using persulfate in situ to control non-stable halogenated disinfection by-products in swimming pool water: when liquid chlorine disinfects swimming pool water, it will interact with chemical components of a large number of personal care products existing in the water React with various organic substances such as human metabolites (sweat, urine) to form unstable halogenated disinfection by-products (such as: halogenated quinones, halogenated acetonitriles, halogenated acetamides), unstable halogenated disinfection The carbon atom connected to the halogen in the by-product molecule is vulnerable to the attack of the nucleophile persulfate, which can quickly undergo nucleophilic hydrolysis and detoxification, and realize the in-situ control of the non-stable halogenated disinfection by-products. That is to say, once the non-stable halogenated disinfection by-products are formed, they will quickly undergo nucleophilic hydrolysis with the persulfate present in the water and be decomposed and detoxified.
本发明的一种利用过硫酸盐原位控制游泳池水中非稳定性卤代消毒副产物的水处理方法具有以下优点：(1)过硫酸盐已被国家正式列入饮用水消毒剂产品目录，能够在游泳池水处理中进行应用；(2)过硫酸盐具有极强的亲核能力，能够快速分解非稳定性卤代消毒副产物；(3)过硫酸盐不消耗液氯，能够与液氯共存；(4)可以实现非稳定性卤代消毒副产物的原位高效转化脱毒。(5)操作简单方便、不需要额外增加设备、处理成本低。A kind of water treatment method utilizing persulfate in situ to control non-stable halogenated disinfection by-products in swimming pool water of the present invention has the following advantages: (1) persulfate has been officially included in the catalog of drinking water disinfectant products by the country, and can It is applied in swimming pool water treatment; (2) persulfate has strong nucleophilic ability and can quickly decompose the unstable halogenated disinfection by-products; (3) persulfate does not consume liquid chlorine and can coexist with liquid chlorine (4) The in-situ efficient conversion and detoxification of non-stable halogenated disinfection by-products can be realized. (5) The operation is simple and convenient, no additional equipment is required, and the processing cost is low.
附图说明Description of drawings
图1是实施例中利用过硫酸盐原位控制游泳池水中非稳定性卤代消毒副产物的去除效果图；其中，□表示液氯消毒过程中形成的氯代醌，○表示液氯消毒过程中形成的氯代乙腈，△表示液氯消毒过程中形成的氯代乙酰胺。Fig. 1 is the removal effect figure of using persulfate in situ to control the non-stable halogenated disinfection by-products in swimming pool water in the embodiment; wherein, □ represents the chlorinated quinone formed in the liquid chlorine disinfection process, and ○ represents the liquid chlorine disinfection process Chloroacetonitrile formed, △ represents chloroacetamide formed during liquid chlorine disinfection.
具体实施方式detailed description
本发明技术方案不局限于以下所列举具体实施方式，还包括各具体实施方式间的任意组合。The technical solution of the present invention is not limited to the specific embodiments listed below, but also includes any combination of the specific embodiments.
具体实施方式一：本实施方式为一种利用过硫酸盐原位控制游泳池水中非稳定性卤代消毒副产物的水处理方法，其是通过以下步骤实现的：在游泳池水中投加液氯进行消毒处理时，同时投加过硫酸盐溶液，保持搅拌状态，即完成所述利用过硫酸盐原位控制游泳池水中卤代消毒副产物的水处理方法，其中，过硫酸盐的浓度为0.5～100mg/L。Specific Embodiment 1: This embodiment is a water treatment method using persulfate in situ to control non-stable halogenated disinfection by-products in swimming pool water, which is realized by the following steps: adding liquid chlorine to swimming pool water for disinfection During treatment, add persulfate solution at the same time, keep stirring, and complete the water treatment method of using persulfate in situ to control halogenated disinfection by-products in swimming pool water, wherein the concentration of persulfate is 0.5-100mg/ L.
本发明一种利用过硫酸盐原位控制游泳池水中非稳定性卤代消毒副产物的水处理方法的原理：液氯对游泳池水进行消毒处理时，会与水中存在的大量个人护理用品的化学成分和人体的代谢物(汗液、尿液)等各种各样有机物发生反应形成非稳定性卤代消毒副产物(如：卤代醌、卤乙腈、卤代乙酰胺)，非稳定性卤代消毒副产物分子中与卤素相连的碳原子易受到亲核试剂过硫酸盐的进攻，能够快速发生亲核水解、脱毒，实现非稳定性卤代消毒副产物的原位控制。也就是说，非稳定性卤代消毒副产物一经形成就会快速与水中存在的过硫酸盐发生亲核水解作用被分解脱毒。The principle of the present invention is a water treatment method using persulfate in situ to control non-stable halogenated disinfection by-products in swimming pool water: when liquid chlorine disinfects swimming pool water, it will interact with chemical components of a large number of personal care products in the water React with various organic substances such as human metabolites (sweat, urine) to form unstable halogenated disinfection by-products (such as: halogenated quinones, halogenated acetonitriles, halogenated acetamides), unstable halogenated disinfection The carbon atom connected to the halogen in the by-product molecule is vulnerable to the attack of the nucleophile persulfate, which can quickly undergo nucleophilic hydrolysis and detoxification, and realize the in-situ control of the non-stable halogenated disinfection by-products. That is to say, once the non-stable halogenated disinfection by-products are formed, they will quickly undergo nucleophilic hydrolysis with the persulfate present in the water and be decomposed and detoxified.
本发明的一种利用过硫酸盐原位控制游泳池水中非稳定性卤代消毒副产物的水处理方法具有以下优点：(1)过硫酸盐已被国家正式列入饮用水消毒剂产品目录，能够在游泳池水处理中进行应用；(2)过硫酸盐具有极强的亲核能力，能够快速分解非稳定性卤代消毒副产物；(3)过硫酸盐不消耗液氯，能够与液氯共存；(4)可以实现非稳定性卤代消毒副产物的原位高效转化脱毒。(5)操作简单方便、不需要额外增加设备、处理成本低。A kind of water treatment method that utilizes persulfate in situ to control non-stable halogenated disinfection by-products in swimming pool water of the present invention has the following advantages: (1) persulfate has been officially included in the catalog of drinking water disinfectant products by the country, and can It is applied in swimming pool water treatment; (2) persulfate has strong nucleophilic ability and can quickly decompose the unstable halogenated disinfection by-products; (3) persulfate does not consume liquid chlorine and can coexist with liquid chlorine (4) The in-situ efficient conversion and detoxification of non-stable halogenated disinfection by-products can be realized. (5) The operation is simple and convenient, no additional equipment is required, and the processing cost is low.
具体实施方式二：本实施方式与具体实施方式一不同的是：所述的待处理水中的过硫酸盐浓度为1～90mg/L。其它与具体实施方式一相同。Embodiment 2: This embodiment differs from Embodiment 1 in that: the persulfate concentration in the water to be treated is 1-90 mg/L. Others are the same as in the first embodiment.
具体实施方式三：本实施方式与具体实施方式一或二不同的是：所述的待处理水中的过硫酸盐浓度为2～80mg/L。其它与具体实施方式一或二相同。Embodiment 3: This embodiment differs from Embodiment 1 or Embodiment 2 in that: the persulfate concentration in the water to be treated is 2-80 mg/L. Others are the same as in the first or second embodiment.
具体实施方式四：本实施方式与具体实施方式一至三之一不同的是：所述的待处理水中的过硫酸盐浓度为3～70mg/L。其它与具体实施方式一至三之一相同。Embodiment 4: This embodiment differs from Embodiments 1 to 3 in that: the persulfate concentration in the water to be treated is 3-70 mg/L. Others are the same as those in the first to third specific embodiments.
具体实施方式五：本实施方式与具体实施方式一至四之一不同的是：所述的待处理水中的过硫酸盐浓度为4～60mg/L。其它与具体实施方式一至四之一相同。Embodiment 5: This embodiment differs from Embodiment 1 to Embodiment 4 in that: the persulfate concentration in the water to be treated is 4-60 mg/L. Others are the same as one of the specific embodiments 1 to 4.
具体实施方式六：本实施方式与具体实施方式一至五之一不同的是：所述的待处理水中的过硫酸盐浓度为5～50mg/L。其它与具体实施方式一至五之一相同。Embodiment 6: This embodiment differs from Embodiment 1 to Embodiment 5 in that: the persulfate concentration in the water to be treated is 5-50 mg/L. Others are the same as one of the specific embodiments 1 to 5.
具体实施方式七：本实施方式与具体实施方式一至六之一不同的是：所述的待处理水中的过硫酸盐浓度为10～40mg/L。其它与具体实施方式一至六之一相同。Embodiment 7: This embodiment differs from Embodiment 1 to Embodiment 6 in that: the persulfate concentration in the water to be treated is 10-40 mg/L. Others are the same as one of the specific embodiments 1 to 6.
具体实施方式八：本实施方式与具体实施方式一至七之一不同的是：所述的待处理水中的过硫酸盐浓度为15～30mg/L。其它与具体实施方式一至七之一相同。Embodiment 8: This embodiment differs from Embodiments 1 to 7 in that: the persulfate concentration in the water to be treated is 15-30 mg/L. Others are the same as one of the specific embodiments 1 to 7.
具体实施方式九：本实施方式与具体实施方式一至八之一不同的是：所述的待处理水中的过硫酸盐浓度为20mg/L。其它与具体实施方式一至八之一相同。Embodiment 9: This embodiment differs from Embodiment 1 to Embodiment 8 in that: the persulfate concentration in the water to be treated is 20 mg/L. Others are the same as one of the specific embodiments 1 to 8.
具体实施方式十：本实施方式与具体实施方式一至九之一不同的是：过硫酸盐为过一硫酸盐和/或过二硫酸盐。其它步骤及参数与具体实施方式一至九之一相同。Embodiment 10: This embodiment is different from Embodiment 1 to Embodiment 9 in that: the persulfate is permonosulfate and/or peroxodisulfate. Other steps and parameters are the same as one of the specific embodiments 1 to 9.
本实施方式中过硫酸盐为过一硫酸盐和过二硫酸盐的混合物时，两者以任意比混合。其中过一硫酸盐为过一硫酸钾、过一硫酸钠中的一种或两种按任意比混合的混合物，过二硫酸盐为过二硫酸钾、过二硫酸钠中的一种或两种按任意比混合的混合物。In the present embodiment, when the persulfate is a mixture of peroxomonosulfate and peroxodisulfate, both are mixed in an arbitrary ratio. Wherein the permonosulfate is potassium persulfate and sodium persulfate or a mixture of two mixed in any ratio, peroxodisulfate is one or both of potassium peroxodisulfate and sodium peroxodisulfate A mixture mixed in any ratio.
具体实施方式十一：本实施方式与具体实施方式一至十之一不同的是过硫酸盐为过一硫酸盐，其中过一硫酸盐为过一硫酸钾、过一硫酸钠中的一种或两种的混合物。其它步骤及参数与具体实施方式一至十之一相同。Embodiment 11: The difference between this embodiment and Embodiment 1 to 10 is that persulfate is persulfate, wherein persulfate is one or both of potassium persulfate and sodium persulfate. mixture of species. Other steps and parameters are the same as those in Embodiments 1 to 11.
本实施方式中过一硫酸盐为混合物时，以任意比混合。In the present embodiment, when the peroxymonosulfate is a mixture, it is mixed in an arbitrary ratio.
具体实施方式十二：本实施方式与具体实施方式一至十一之一不同的是过硫酸盐为过二硫酸盐，其中过二硫酸盐为过二硫酸钾、过二硫酸钠中的一种或两种的混合物。其它步骤及参数与具体实施方式一至十一之一相同。Embodiment 12: The difference between this embodiment and Embodiment 1 to Eleven is that the persulfate is peroxodisulfate, wherein the peroxodisulfate is one of potassium peroxodisulfate, sodium peroxodisulfate or A mixture of the two. Other steps and parameters are the same as those in Embodiments 1 to 11.
本实施方式中过二硫酸盐为混合物时，以任意比混合。In this embodiment, when peroxodisulfate is a mixture, it mixes in arbitrary ratios.
具体实施方式十三：本实施方式与具体实施方式一至十二之一不同的是过硫酸盐为过一硫酸盐和过二硫酸盐，其中过一硫酸盐为过一硫酸钾、过一硫酸钠中的一种或两种的混合物，过二硫酸盐为过二硫酸钾、过二硫酸钠中的一种或两种的混合物。其它步骤及参数与具体实施方式一至十二之一相同。Specific embodiment thirteen: The difference between this embodiment and one of specific embodiments 1 to 12 is that persulfate is persulfate and peroxodisulfate, wherein persulfate is potassium persulfate and sodium persulfate One or a mixture of two, the peroxodisulfate is one or a mixture of potassium peroxodisulfate and sodium peroxodisulfate. Other steps and parameters are the same as those in Embodiments 1 to 12.
本实施方式中过一硫酸盐和过二硫酸盐间以任意比混合，过一硫酸盐为混合物时，以任意比混合，过二硫酸盐为混合物时，以任意比混合。In the present embodiment, the permonosulfate and the peroxodisulfate are mixed in an arbitrary ratio, and when the peroxymonosulfate is a mixture, the mixture is mixed in an arbitrary ratio, and when the peroxodisulfate is a mixture, the mixture is mixed in an arbitrary ratio.
具体实施方式十四：本实施方式与具体实施方式一至十三不同的是过硫酸盐由过硫酸盐和碱的复合盐代替，其中过硫酸盐和碱的摩尔比为1:1～10，其中，过硫酸盐为过一硫酸盐和/或过二硫酸盐，碱为氢氧化钾、氢氧化钠、氢氧化钙、碳酸钠、碳酸钾、碳酸氢钠、碳碳酸氢钾中的一种或其中几种的混合物。其它步骤及参数与具体实施方式一至十三之一相同。Embodiment 14: The difference between this embodiment and Embodiments 1 to 13 is that the persulfate is replaced by a compound salt of persulfate and alkali, wherein the molar ratio of persulfate and alkali is 1:1-10, wherein , the persulfate is persulfate and/or peroxodisulfate, and the alkali is one of potassium hydroxide, sodium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate or A mixture of several of them. Other steps and parameters are the same as those in Embodiments 1 to 13.
本实施方式中过硫酸盐为过一硫酸盐和过二硫酸盐时，以任意比混合。碱为其中几种的混合物时，以任意比混合。In the present embodiment, when the persulfate is a peroxomonosulfate and a peroxodisulfate, they are mixed in an arbitrary ratio. When the base is a mixture of several of them, it is mixed in any ratio.
本实施方式中碱的加入能调节水处理体系的pH值在6～9，有利于过硫酸盐电离，使得诱发卤代消毒副产物分解能力增强。The addition of alkali in this embodiment can adjust the pH value of the water treatment system to 6-9, which is beneficial to the ionization of persulfate and enhances the ability to induce decomposition of halogenated disinfection by-products.
本实施方式中过硫酸盐和碱的摩尔比优选为1:3～8，最佳的是1:5。In this embodiment, the molar ratio of persulfate to alkali is preferably 1:3-8, most preferably 1:5.
具体实施方式十五：本实施方式与具体实施方式一至十四不同的是过硫酸盐由过一硫酸盐和碱的复合盐代替，其中过一硫酸盐和碱的摩尔比为1:1～10，其中过一硫酸盐为过一硫酸钾、过一硫酸钠和过一硫酸氨中的一种或几种的混合物。其它步骤及参数与具体实施方式一至十四之一相同。Embodiment 15: The difference between this embodiment and Embodiments 1 to 14 is that persulfate is replaced by a compound salt of persulfate and alkali, wherein the molar ratio of persulfate and alkali is 1:1-10 , wherein the persulfate is one or a mixture of potassium persulfate, sodium persulfate and ammonium persulfate. Other steps and parameters are the same as those in Embodiments 1 to 14.
本实施方式中过一硫酸盐为其中几种的混合物时，以任意比混合。In the present embodiment, when the peroxymonosulfate is a mixture of some of them, it is mixed in an arbitrary ratio.
本实施方式中过一硫酸盐和碱的摩尔比优选为1:3～8，最佳的是1:5。In this embodiment, the molar ratio of persulfate to alkali is preferably 1:3-8, and the most preferable is 1:5.
具体实施方式十六：本实施方式与具体实施方式一至十五不同的是过硫酸盐由过二硫酸盐和碱的复合盐代替，其中过硫酸盐和碱的摩尔比为1:1～10，其中过二硫酸盐为过二硫酸钾、过二硫酸钠和过二硫酸氨中的一种或几种的混合物。其它步骤及参数与具体实施方式一至十五之一相同。Specific Embodiment Sixteen: The difference between this embodiment and Embodiments 1 to 15 is that persulfate is replaced by a compound salt of persulfate and alkali, wherein the molar ratio of persulfate and alkali is 1:1-10, Wherein the peroxodisulfate is one or a mixture of potassium peroxodisulfate, sodium peroxodisulfate and ammonium peroxodisulfate. Other steps and parameters are the same as those in Embodiments 1 to 15.
本实施方式中过二硫酸盐为混合物时，以任意比混合。In this embodiment, when peroxodisulfate is a mixture, it mixes in arbitrary ratios.
本实施方式中过二硫酸盐和碱的摩尔比优选为1:3～8，最佳的是1:5。In this embodiment, the molar ratio of peroxodisulfate to alkali is preferably 1:3-8, most preferably 1:5.
具体实施方式十七：本实施方式与具体实施方式一至十六不同的是过硫酸盐由过一硫酸盐、过二硫酸盐和碱的复合盐代替，其中过一硫酸盐和过二硫酸盐总摩尔量与碱的摩尔量比值为1:1～10，其中过一硫酸盐为过一硫酸钾、过一硫酸钠和过一硫酸氨中的一种或几种的混合物，过二硫酸盐为过二硫酸钾、过二硫酸钠和过二硫酸氨中的一种或几种的混合物。Specific embodiment seventeen: The difference between this embodiment and specific embodiments one to sixteen is that the persulfate is replaced by a compound salt of persulfate, peroxodisulfate and alkali, wherein persulfate and peroxodisulfate are combined The ratio of the molar weight to the alkali is 1:1 to 10, wherein the peroxomonosulfate is a mixture of one or more of potassium peroxosulfate, sodium peroxomonosulfate and ammonium peroxomonosulfate, and the peroxodisulfate is One or a mixture of potassium peroxodisulfate, sodium peroxodisulfate and ammonium peroxodisulfate.
本实施方式中过一硫酸盐为其中几种的混合物时，以任意比混合。本实施方式中过二硫酸盐为混合物时，以任意比混合。In the present embodiment, when the peroxymonosulfate is a mixture of some of them, it is mixed in an arbitrary ratio. In this embodiment, when peroxodisulfate is a mixture, it mixes in arbitrary ratios.
本实施方式中过一硫酸盐和过二硫酸盐总摩尔量与碱的摩尔量比值优选为1:3～8，最佳的是1:5。In this embodiment, the ratio of the total molar weight of peroxomonosulfate and peroxodisulfate to the molar weight of alkali is preferably 1:3-8, and the best is 1:5.
通过以下实施例验证本发明的有益效果：Verify the beneficial effects of the present invention through the following examples:
本实施例的一种利用过硫酸盐原位控制游泳池水中非稳定性卤代消毒副产物的水处理方法，其是通过以下步骤实现的：在游泳池水中投加液氯进行消毒处理时，同时投加过一硫酸钾溶液，保持搅拌，即完成所述利用过硫酸盐原位控制压舱水中卤代消毒副产物的水处理方法，其中，过一硫酸钾浓度为20mg/L。A kind of water treatment method of using persulfate in situ to control non-stable halogenated disinfection by-products in swimming pool water in this embodiment is realized through the following steps: when adding liquid chlorine to swimming pool water for disinfection treatment, simultaneously throw Add potassium persulfate solution and keep stirring to complete the water treatment method of using persulfate in situ to control halogenated disinfection by-products in ballast water, wherein the concentration of potassium persulfate is 20 mg/L.
本实施例的利用过硫酸盐原位控制游泳池水中非稳定性卤代消毒副产物的效果见图1。由图1可知，在液氯消毒过程中，随着反应时间的进行氯代醌(□)、氯代乙腈(○)、氯代乙酰胺(△)逐渐生成，反应60min时，氯代醌的浓度达到3.3μg/L、卤乙腈的累积浓度达到2.1μg/L、卤代乙酰胺的累积浓度达到3μg/L；利用本实施例的方式在液氯消毒的过程中同时投加过一硫酸钾溶液，几乎检测不到氯代醌、氯代乙腈、氯代乙酰胺的生成。The effect of using persulfate in situ to control non-stable halogenated disinfection by-products in swimming pool water in this embodiment is shown in FIG. 1 . It can be seen from Figure 1 that during the liquid chlorine disinfection process, chloranil (□), chloroacetonitrile (○), and chloroacetamide (△) are gradually formed as the reaction time progresses. The concentration reaches 3.3 μg/L, the cumulative concentration of haloacetonitrile reaches 2.1 μg/L, and the cumulative concentration of haloacetamide reaches 3 μg/L; use the method of this embodiment to add potassium persulfate at the same time in the process of liquid chlorine disinfection solution, the formation of chloranil, chloroacetonitrile, and chloroacetamide was almost undetectable.
由此可见，本实施例的利用过硫酸盐原位控制游泳池水中非稳定性卤代消毒副产物的水处理方法具有比较突出的优势。It can be seen that the water treatment method of this embodiment using persulfate in situ to control non-stable halogenated disinfection by-products in swimming pool water has relatively prominent advantages.
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