CN107515254A - A kind of method of phthalic acid ester content in reduction water - Google Patents
A kind of method of phthalic acid ester content in reduction water Download PDFInfo
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- CN107515254A CN107515254A CN201610423579.1A CN201610423579A CN107515254A CN 107515254 A CN107515254 A CN 107515254A CN 201610423579 A CN201610423579 A CN 201610423579A CN 107515254 A CN107515254 A CN 107515254A
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- water
- phthalic acid
- content
- acid ester
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 102
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 title claims abstract description 82
- -1 phthalic acid ester Chemical class 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 47
- 230000009467 reduction Effects 0.000 title description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 39
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 21
- 241000370738 Chlorion Species 0.000 claims abstract description 15
- 230000005855 radiation Effects 0.000 claims abstract description 8
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical group [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 13
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 13
- 235000019394 potassium persulphate Nutrition 0.000 claims description 9
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 239000001103 potassium chloride Substances 0.000 claims description 5
- 235000011164 potassium chloride Nutrition 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 26
- 239000007788 liquid Substances 0.000 description 26
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 22
- 150000002148 esters Chemical class 0.000 description 22
- 230000000694 effects Effects 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 5
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
- 239000002537 cosmetic Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 239000002352 surface water Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000003651 drinking water Substances 0.000 description 3
- 235000020188 drinking water Nutrition 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 150000003022 phthalic acids Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000003918 potentiometric titration Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- GFLJTEHFZZNCTR-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC(=O)C=C GFLJTEHFZZNCTR-UHFFFAOYSA-N 0.000 description 1
- 206010006187 Breast cancer Diseases 0.000 description 1
- 208000026310 Breast neoplasm Diseases 0.000 description 1
- OKJADYKTJJGKDX-UHFFFAOYSA-N Butyl pentanoate Chemical compound CCCCOC(=O)CCCC OKJADYKTJJGKDX-UHFFFAOYSA-N 0.000 description 1
- 201000009030 Carcinoma Diseases 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- 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 description 1
- 241001465754 Metazoa Species 0.000 description 1
- GFTGHOJGGLNVMC-UHFFFAOYSA-N N=NC=NN.N=NC=NN.C(C=1C(C(=O)O)=CC=CC1)(=O)O Chemical compound N=NC=NN.N=NC=NN.C(C=1C(C(=O)O)=CC=CC1)(=O)O GFTGHOJGGLNVMC-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940126678 chinese medicines Drugs 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920002457 flexible plastic Polymers 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 239000008266 hair spray Substances 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001850 reproductive effect Effects 0.000 description 1
- 210000004994 reproductive system Anatomy 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 210000000582 semen Anatomy 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000019100 sperm motility Effects 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 210000001550 testis Anatomy 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- 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
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
-
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/027—Liquid chromatography
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- Toxicology (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Medicinal Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Cosmetics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to water treatment field, discloses a kind of method for reducing phthalic acid ester content in water, and this method includes：When the mol ratio of the content of chlorion and the content of phthalic acid ester is more than 100 in accessing pending water, persulfate is added into the accessing pending water, then ultraviolet light radiation；When the mol ratio of the content of chlorion and the content of phthalic acid ester is less than 100 in accessing pending water, chloride and persulfate are added into the accessing pending water, then ultraviolet light radiation；Wherein, the concentration of the phthalic acid ester in the accessing pending water is less than 5 × 10‑6mol/L.The method of the invention can make the requirement that the content of phthalic acid ester in water reaches China's water environment quality standard (GB3838 2002).
Description
Technical field
The present invention relates to water treatment field, in particular it relates to a kind of method for reducing phthalic acid ester content in water.
Background technology
Phthalic acid ester (PAEs), also known as phthalate ester.When it is used as plasticiser, generally referred to as phthalic acid
The ester formed with the alcohol of 4-15 carbon.Phthalic acid ester is mainly used in the production of pvc material, and it can make polyvinyl chloride
Flexible plastic cement is changed into from hard plastic glue.In addition, phthalic acid ester is also widely used in manufacture toy, packaging for foodstuff material
Material, medical blood bag and sebific duct, vinyl flooring and wallpaper, cleaning agent, lubricating oil, personal-care supplies (such as nail polish, hair sprays
Agent, perfumed soap and shampoo) etc. hundreds of products.Therefore, as the use of plastic products, phthalic acid ester easily pass through diffusion
And enter environment, especially into natural water body.
Research shows that phthalic acid ester is a kind of common incretion interferent, is played in human body and animal body
The effect of similar female hormone, it can reduce man semen amount and sperm quantity, Sperm Motility is low, paramophia, sternly
The meeting of weight causes carcinoma of testis, is to cause man's reproductive problems " arch-criminal ".In cosmetics, the O-phthalic in nail polish
Acid and esters content highest, the fragrance ingredient of many cosmetics also contain the material.This material in cosmetics can pass through women
Respiratory system and skin enter in vivo, if the such cosmetics of excessive use, can increase the probability that women suffers from breast cancer, can also endanger
Reproductive system of the evil to the boy baby of their following fertilities.According to China's water environment quality standard (GB3838-2002), for
Centralized Drinking Water surface water water head site, the limit value of phthalic acid two (2- ethylhexyls) ester are 0.008mg/L, adjacent benzene
The limit value of dibutyl carboxylic acid is 0.003mg/L.
Domestic and international researcher carried out some researchs to the processing method of phthalate plasticiser in water, including inhaled
Attached, filtering, flocculation, oxidation etc., also disclose that several patents technology, but be difficult to phthalic ester concentration in water being down to mesh
Mark below limit value.Such as：CN1935776A is disclosed a kind of adsorbs the diethyl phthalate in water using macroreticular resin
Method, deal with objects and exist for the waste water containing hundreds of mg/L diethyl phthalates, water outlet diethyl phthalate concentration
1mg/L or so.Although this method treatment effeciency is higher, the recovery of diethyl phthalate can be achieved, water outlet needs to enter
Municipal sewage system is further processed.CN101665298A is disclosed one kind and gone using strong-base anion-exchange resin
Except the method for phthalic acid ester in water body, aqueous concentration phthalic acid ester also can only achieve the level in 0.1mg/L or so.
CN101186719A then discloses a kind of composite function resin class processing O-phthalic using micro-porous area rich in strong acid group
The method of acid esters polluted-water, when phthalic ester concentration of intaking is in 0.5mg/L, aqueous concentration can reach 0.008mg/
L or so, illustrate that this method has preferable removal effect to low concentration phthalic acid ester in water, but still not up to China's surface water
Environmental quality standards.CN101314504A is disclosed a kind of filtered successively with Wire-wound filter core, microporous barrier, resin and activated carbon and made a return journey
The device of phthalate organic matters in water removal, is mainly directed towards the processing of municipal water supply, but fails to provide specific processing
Effect.CN101700923A disclose it is a kind of using PDDA to the phthalic acid diformazan in water body
The method that ester carries out flocculation treatment, when the concentration of repefral in raw water is in 0.1-2mg/L, flocculant dosage
When several times of repefral amount are to tens times, the clearance of repefral can reach more than 60%,
Although the relatively simple economy of this method, water outlet still needs to process again.Oxidation processes research for phthalic acid ester,
CN1508080A, CN201458878U and CN103316902A individually disclose the processing side based on ozone and Fenton reagent
Method, but common technology is not significantly improved, also fail to provide specific treatment effect.It is it can be seen that adjacent for low concentration in water
The removal of phthalic acid ester, still need to provide more efficiently processing scheme, to meet water standard, reduce phthalic acid ester
Environmental risk.
In recent years, there is researcher to utilize ultraviolet excitation peroxide, produce the hydroxyl radical free radical with strong oxidizing property, come
The persistent organic pollutants gone in water removal, the processing to phthalic acid ester also have it is involved (B.Xu, N.Y.Gao,
H.F.Cheng,etc.,Oxidative degradation of dimethyl phthalate(DMP)by UV/
H2O2process,J.Hazard.Mater.162(2009)954-959).More there is researcher's discovery, high-concentration chlorine ion can be one
Determine in degree improve sulphuric acid free radical high-level oxidation technology degradation of dye effect (R.X.Yuan, S.N.Ramjaun,
Z.H.Wang,etc.,Effects of chloride ion on degradation of Acid Orange 7by
sulfate radical-based advanced oxidation process:Implications for formation
Of chlorinated aromatic compounds, J.Hazard.Mater.196 (2011) 173-179), but do not grind still
The person of studying carefully has found and proposes that low-level chlorinated ion strengthens ultraviolet light/persulfate coupling high-level oxidation technology degraded phthalic acid ester
Characteristic.
The content of the invention
The invention aims to overcome prior art to reduce the effect of the content of phthalic acid ester in water not reaching
The problem of China's water environment quality standard, and a kind of new method for reducing phthalic acid ester content in water is provided.
To achieve these goals, the present invention provides a kind of method for reducing phthalic acid ester content in water, wherein, should
Method includes：
When the mol ratio of the content of chlorion and the content of phthalic acid ester is more than 100 in accessing pending water, to institute
State and persulfate is added in accessing pending water, then ultraviolet light radiation；
When the mol ratio of the content of chlorion and the content of phthalic acid ester is less than 100 in accessing pending water, to described
Chloride and persulfate are added in accessing pending water, then ultraviolet light radiation；
Wherein, the concentration of the phthalic acid ester in the accessing pending water is less than 5 × 10-6mol/L。
The content of phthalic acid ester in water can be effectively reduced using the method for the invention, makes phthalic acid in water
The content of ester reaches China's water environment quality standard (GB3838-2002) and to centralized Drinking Water surface water
It is required that (content of phthalic acid ester is less than 0.003mg/L).
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
The invention provides a kind of method for reducing phthalic acid ester content in water, this method includes：
When the mol ratio of the content of chlorion and the content of phthalic acid ester is more than 100 in accessing pending water, to institute
State and persulfate is added in accessing pending water, then ultraviolet light radiation；
When the mol ratio of the content of chlorion and the content of phthalic acid ester is less than 100 in accessing pending water, to described
Chloride and persulfate are added in accessing pending water, then ultraviolet light radiation；
Wherein, the concentration of the phthalic acid ester in the accessing pending water is less than 5 × 10-6mol/L。
The present invention has preferable treatment effect to low concentration phthalic acid ester in accessing pending water, under preferable case, institute
The concentration for stating the phthalic acid ester in accessing pending water is 1 × 10-6-2.5×10-6mol/L。
In the present invention, using ultraviolet excitation persulfate, the potentiometric titrations with strong oxidizing property are produced, to degrade
Phthalic acid ester in water.In the present invention, to the dosage of the persulfate, there is no particular limitation, can be that this area is normal
The selection of rule.But in order to more effectively reduce the content of the phthalic acid ester in water, under preferable case, the persulfuric acid
The dosage of salt makes the concentration of the persulfate in the accessing pending water be 1 × 10-3-1×10-2mol/L。
In the present invention, there is no particular limitation for the selection to the persulfate, can be the conventional selection in this area, example
Such as, the persulfate can be at least one of sodium peroxydisulfate, potassium peroxydisulfate and ammonium persulfate.
In the present invention, the chlorion that the chloride is formed in accessing pending water can strengthen the oxidation of potentiometric titrations
Effect, so as to promote the degraded to phthalic acid ester.In the present invention, to the dosage of the chloride, there is no particular limitation,
Can be the conventional selection in this area, still, in order that the content of the phthalic acid ester in accessing pending water effectively reduces, preferably
In the case of, the dosage of the chloride makes rubbing for the content of the chlorion in the accessing pending water and the content of phthalic acid ester
Your ratio is more than 100, more preferably 100-200, more preferably 120-200.
In the present invention, there is no particular limitation for the selection to the chloride, can be the conventional selection in this area, example
Such as, the chloride can be sodium chloride and/or potassium chloride.The present invention is not particularly limited to the source of the chloride,
Can be pure chloride, or the existing various materials containing chloride, such as the running water containing chloride.
In the present invention, to the condition of the ultraviolet light, there is no particular limitation, can be the conventional selection in this area.But
It is that, in order to strengthen the degradation effect of phthalic acid ester, under preferable case, the wavelength of the ultraviolet light is 200-280nm；It is described
The dosage of ultraviolet light is 80-640mJ/cm2.It is further preferred that the wavelength of the ultraviolet light is 210-260nm；It is described ultraviolet
The dosage of light is 160-320mJ/cm2。
In the present invention, to the feed postition of the chloride and the persulfate, there is no particular limitation, can be this
The conventional mode in field, under preferable case, the mode of the chloride and the persulfate is added into the accessing pending water
The chloride is added into the accessing pending water for elder generation, adds the persulfate.
The present invention will be described in detail by way of examples below.
The phthalic acid ester used in following examples and comparative example is purchased from Sigma-Aldrich, to go
Ionized water dissolving is configured to concentration as 1.0 × 10-4Mol/L solution；Chloride (sodium chloride and potassium chloride) is purchased from Chinese medicines group
Chemical reagent Co., Ltd, solution of the concentration as 0.01mol/L is configured to using deionized water dissolving；Persulfate (sodium peroxydisulfate
And potassium peroxydisulfate) Chemical Reagent Co., Ltd., Sinopharm Group is purchased from, concentration is configured to as 0.1mol/L's using deionized water dissolving
Solution.
Phthalic acid ester after being analyzed and processed in following examples and comparative example using liquid chromatogram in solution it is dense
Degree.Condition determination：The reverse posts of C18 (4.6mm × 150mm, the average grain diameter of filler particles is 5 μm)；Mobile phase is first alcohol and water
(volume ratio 80：20)；Flow velocity is 0.6mL/min；Sample size is 50 μ L.
Embodiment 1
The embodiment is used to illustrate the method for reducing repefral content in water.
A diameter of 60mm glass culture dish is taken, it is molten to add repefral solution, sodium chloride thereto
Liquid, sodium peroxydisulfate solution and appropriate deionized water, 10mL repefrals concentration is made into as 1.0 × 10-6mol/L、
Chlorine ion concentration is 2.0 × 10-4Mol/L, sodium peroxydisulfate concentration are 1.0 × 10-3Mol/L solution.Stone is capped on culture dish
After English lid, culture dish is put into ultraviolet parallel apparatus for photoreaction.The flashboard of reaction unit is opened, 254nm ultraviolet light is hung down
Directly it is irradiated on culture dish.When ultraviolet light dosage is 160mJ/cm2When, flashboard is closed, takes out culture dish.Take molten in culture dish
Liquid, repefral concentration in solution is measured as 1.0 × 10 using liquid chromatogram-8mol/L(0.0019mg/L)。
Embodiment 2
The embodiment is used to illustrate the method for reducing diethyl phthalate content in water.
A diameter of 60mm glass culture dish is taken, it is molten to add diethyl phthalate solution, potassium chloride thereto
Liquid, potassium persulfate solution and appropriate deionized water, 10mL diethyl phthalates concentration is made into as 2.0 × 10-6mol/L、
Chlorine ion concentration is 2.5 × 10-4Mol/L, potassium peroxydisulfate concentration are 2.0 × 10-3Mol/L solution.Stone is capped on culture dish
After English lid, culture dish is put into ultraviolet parallel apparatus for photoreaction.The flashboard of reaction unit is opened, 260nm ultraviolet light is hung down
Directly it is irradiated on culture dish.When ultraviolet light dosage is 320mJ/cm2When, flashboard is closed, takes out culture dish.Take molten in culture dish
Liquid, diethyl phthalate concentration in solution is measured as 1.1 × 10 using liquid chromatogram-9mol/L(0.00024mg/L)。
Embodiment 3
The embodiment is used to illustrate the method for reducing diethyl phthalate content in water.
A diameter of 60mm glass culture dish is taken, it is molten to add diethyl phthalate solution, potassium chloride thereto
Liquid, potassium persulfate solution and appropriate deionized water, 10mL diethyl phthalates concentration is made into as 2.5 × 10-6mol/L、
Chlorine ion concentration is 3.0 × 10-4Mol/L, potassium peroxydisulfate concentration are 1.0 × 10-2Mol/L solution.Stone is capped on culture dish
After English lid, culture dish is put into ultraviolet parallel apparatus for photoreaction.The flashboard of reaction unit is opened, 210nm ultraviolet light is hung down
Directly it is irradiated on culture dish.When ultraviolet light dosage is 160mJ/cm2When, flashboard is closed, takes out culture dish.Take molten in culture dish
Liquid, diethyl phthalate concentration in solution is measured as 9.0 × 10 using liquid chromatogram-9mol/L(0.002mg/L)。
Embodiment 4
The embodiment is used to illustrate the method for reducing dibutyl phthalate content in water.
A diameter of 60mm glass culture dish is taken, it is molten to add dibutyl phthalate solution, sodium chloride thereto
Liquid, ammonium persulfate solution and appropriate deionized water, 10mL dibutyl phthalates concentration is made into as 5.0 × 10-6mol/L、
Chlorine ion concentration is 6.0 × 10-4Mol/L, ammonium persulfate concentrations are 8.0 × 10-3Mol/L solution.Stone is capped on culture dish
After English lid, culture dish is put into ultraviolet parallel apparatus for photoreaction.The flashboard of reaction unit is opened, 280nm ultraviolet light is hung down
Directly it is irradiated on culture dish.When ultraviolet light dosage is 640mJ/cm2When, flashboard is closed, takes out culture dish.Take molten in culture dish
Liquid, dibutyl phthalate concentration in solution is measured as 1.0 × 10 using liquid chromatogram-8mol/L(0.0028mg/L)。
Embodiment 5
The embodiment is used to illustrate the method for reducing phthalic acid two (2- ethylhexyls) ester content in water.
A diameter of 60mm glass culture dish is taken, adds phthalic acid two (2- ethylhexyls) ester, chlorine thereto
Change sodium solution, sodium peroxydisulfate solution and appropriate deionized water, be made into 10mL phthalic acids two (2- ethylhexyls) ester concentration
For 3.0 × 10-6Mol/L, chlorine ion concentration are 4.5 × 10-4Mol/L, sodium peroxydisulfate concentration are 4.0 × 10-3Mol/L solution.
After being capped quartz cover on culture dish, culture dish is put into ultraviolet parallel apparatus for photoreaction.The flashboard of reaction unit is opened, is made
230nm ultraviolet light vertical irradiation is on culture dish.When ultraviolet light dosage is 320mJ/cm2When, flashboard is closed, takes out culture
Ware.The solution in culture dish is taken, phthalic acid two (2- ethylhexyls) ester concentration in solution is measured as 7.5 using liquid chromatogram
×10-9mol/L(0.0029mg/L)。
Embodiment 6
The embodiment is used to illustrate the method for reducing dibutyl phthalate content in water.
A diameter of 60mm glass culture dish is taken, adds dibutyl phthalate solution, sodium peroxydisulfate thereto
(chlorine ion concentration is 1.5 × 10 by solution and appropriate running water A-3Mol/L), being made into 10mL dibutyl phthalate concentration is
1.0×10-6Mol/L, chlorine ion concentration are 1.5 × 10-3Mol/L, sodium peroxydisulfate concentration are 2.0 × 10-3Mol/L solution.
After being capped quartz cover on culture dish, culture dish is put into ultraviolet parallel apparatus for photoreaction.The flashboard of reaction unit is opened, is made
254nm ultraviolet light vertical irradiation is on culture dish.When ultraviolet light dosage is 320mJ/cm2When, flashboard is closed, takes out culture
Ware.The solution in culture dish is taken, dibutyl phthalate concentration in solution is measured as 8.4 × 10 using liquid chromatogram-9mol/L
(0.0023mg/L)。
Embodiment 7
The embodiment is used to illustrate the method for reducing phthalic acid two (2- ethylhexyls) ester solution content in water.
A diameter of 60mm glass culture dish is taken, it is molten to add phthalic acid two (2- ethylhexyls) ester thereto
(chlorine ion concentration is 2.4 × 10 by liquid, 0.36mL Klorvess Liquids, potassium persulfate solution and appropriate running water B-4Mol/L), match somebody with somebody
It is 4.0 × 10 into 10mL phthalic acids two (2- ethylhexyls) ester concentration-6Mol/L, chlorine ion concentration are 6.0 × 10-4mol/
L, potassium peroxydisulfate concentration is 6.0 × 10-3Mol/L solution.After being capped quartz cover on culture dish, culture dish is put into ultraviolet flat
In row apparatus for photoreaction.The flashboard of reaction unit is opened, makes 230nm ultraviolet light vertical irradiation to culture dish.Work as ultraviolet light
Dosage is 160mJ/cm2When, flashboard is closed, takes out culture dish.The solution in culture dish is taken, is measured with liquid chromatogram in solution
Phthalic acid two (2- ethylhexyls) ester concentration is 5.3 × 10-9mol/L(0.0021mg/L)。
Comparative example 1
The treatment effect when comparative example is used to illustrate to be not added with chloride.
The content of diethyl phthalate in water is reduced according to the method for embodiment 2, unlike, in processing procedure not
Klorvess Liquid is added, is comprised the following steps that：
A diameter of 60mm glass culture dish is taken, adds diethyl phthalate solution, potassium peroxydisulfate thereto
Solution and appropriate deionized water, 10mL diethyl phthalates concentration is made into as 2.0 × 10-6Mol/L, potassium peroxydisulfate concentration
For 2.0 × 10-3Mol/L solution.After being capped quartz cover on culture dish, culture dish is put into ultraviolet parallel apparatus for photoreaction
In.The flashboard of reaction unit is opened, makes 260nm ultraviolet light vertical irradiation to culture dish.When ultraviolet light dosage is 320mJ/
cm2When, flashboard is closed, takes out culture dish.The solution in culture dish is taken, the phthalic acid two in solution is measured with liquid chromatogram
Ethyl ester concentration is 1.5 × 10-8mol/L(0.0033mg/L)。
Comparative example 2
The comparative example is used to illustrate that the dosage of chloride does not make the content and phthalic acid of the chlorion in accessing pending water
The treatment effect when mol ratio of the content of ester is more than 100.
The content of dibutyl phthalate in water is reduced according to the method for embodiment 4, unlike, sodium chloride solution
Dosage makes the concentration for the Chlorine in Solution ion being made into be 2.0 × 10-4Mol/L, i.e. the content of chlorion and adjacent benzene in accessing pending water
The mol ratio of the content of dicarboxylic acid esters is less than 100, comprises the following steps that：
A diameter of 60mm glass culture dish is taken, it is molten to add dibutyl phthalate solution, sodium chloride thereto
Liquid, ammonium persulfate solution and appropriate deionized water, 10mL dibutyl phthalates concentration is made into as 5.0 × 10-6mol/L、
Chlorine ion concentration is 2.0 × 10-4Mol/L, ammonium persulfate concentrations are 8.0 × 10-3Mol/L solution.Stone is capped on culture dish
After English lid, culture dish is put into ultraviolet parallel apparatus for photoreaction.The flashboard of reaction unit is opened, 280nm ultraviolet light is hung down
Directly it is irradiated on culture dish.When ultraviolet light dosage is 640mJ/cm2When, flashboard is closed, takes out culture dish.Take molten in culture dish
Liquid, dibutyl phthalate concentration in solution is measured as 3.0 × 10 using liquid chromatogram-8mol/L(0.0084mg/L)。
Comparative example 3
The comparative example is used to illustrate that the dosage of chloride does not make the content and phthalic acid of the chlorion in accessing pending water
The treatment effect when mol ratio of the content of ester is more than 100.
The content of phthalic acid two (2- ethylhexyls) ester in water is reduced according to the method for embodiment 7, unlike, no
Klorvess Liquid is added, and the concentration of Chlorine in Solution ion that running water B dosage makes to be made into is 2.4 × 10-4Mol/L, i.e. treat
Handle the mol ratio of the content of chlorion and the content of phthalic acid ester in water and be less than 100, comprise the following steps that：
A diameter of 60mm glass culture dish is taken, it is molten to add phthalic acid two (2- ethylhexyls) ester thereto
(chlorine ion concentration is 2.4 × 10 by liquid, potassium persulfate solution and appropriate running water B-4Mol/L), it is made into 10mL phthalic acids
Two (2- ethylhexyls) ester concentrations are 4.0 × 10-6Mol/L, chlorine ion concentration are about 2.4 × 10-4Mol/L, potassium peroxydisulfate concentration
For 6.0 × 10-3Mol/L solution.After being capped quartz cover on culture dish, culture dish is put into ultraviolet parallel apparatus for photoreaction
In.The flashboard of reaction unit is opened, makes 230nm ultraviolet light vertical irradiation to culture dish.When ultraviolet light dosage is 160mJ/
cm2When, flashboard is closed, takes out culture dish.The solution in culture dish is taken, the phthalic acid two in solution is measured with liquid chromatogram
(2- ethylhexyls) ester concentration is 1.2 × 10-8mol/L(0.0047mg/L)。
The method of the invention can make containing for phthalic acid ester in water it can be seen from above example and comparative example
Amount is reduced to below 0.003mg/L, complies with China's water environment quality standard (GB3838-2002) and to centralization
The requirement of Drinking Water surface water.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
- A kind of 1. method for reducing phthalic acid ester content in water, it is characterised in that this method includes：When the mol ratio of the content of chlorion and the content of phthalic acid ester is more than 100 in accessing pending water, treated to described Persulfate is added in processing water, then ultraviolet light radiation；When the mol ratio of the content of chlorion and the content of phthalic acid ester is less than 100 in accessing pending water, wait to locate to described Manage and chloride and persulfate are added in water, then ultraviolet light radiation；Wherein, the concentration of the phthalic acid ester in the accessing pending water is less than 5 × 10-6mol/L。
- 2. according to the method for claim 1, wherein, the concentration of the phthalic acid ester in the accessing pending water is 1 × 10-6-2.5×10-6mol/L。
- 3. method according to claim 1 or 2, wherein, the dosage of the chloride make chlorine in the accessing pending water from The mol ratio of the content of son and the content of phthalic acid ester is more than 100.
- 4. according to the method for claim 3, wherein, the dosage of the chloride makes the chlorion in the accessing pending water The mol ratio of content and the content of phthalic acid ester is 100-200, preferably 120-200.
- 5. method according to claim 1 or 2, wherein, the dosage of the persulfate makes the mistake in the accessing pending water The concentration of sulfate is 1 × 10-3-1×10-2mol/L。
- 6. method according to claim 1 or 2, wherein, the chloride is sodium chloride and/or potassium chloride.
- 7. method according to claim 1 or 2, wherein, the persulfate is sodium peroxydisulfate, potassium peroxydisulfate and persulfuric acid At least one of ammonium.
- 8. method according to claim 1 or 2, wherein, the wavelength of the ultraviolet light is 200-280nm；The ultraviolet light Dosage be 80-640mJ/cm2。
- 9. according to the method for claim 8, wherein, the wavelength of the ultraviolet light is 210-260nm；The use of the ultraviolet light Measure as 160-320mJ/cm2。
- 10. method according to claim 1 or 2, wherein, the chloride and the mistake are added into the accessing pending water The mode of sulfate adds the persulfate first to add the chloride into the accessing pending water.
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