CN101168455A - Method for catalytically degrading estrogen-like contaminant by simulating natural light - Google Patents
Method for catalytically degrading estrogen-like contaminant by simulating natural light Download PDFInfo
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- CN101168455A CN101168455A CNA2006101340167A CN200610134016A CN101168455A CN 101168455 A CN101168455 A CN 101168455A CN A2006101340167 A CNA2006101340167 A CN A2006101340167A CN 200610134016 A CN200610134016 A CN 200610134016A CN 101168455 A CN101168455 A CN 101168455A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention relates to a method for simulating natural photo-catalysis to degrade estrogen contaminant, which comprises adding catalyst into the water solution of estrogen contaminant of which the mass density is 10<SUP>-3</SUP>-10mg/L, and arranging the solution in an artificial climate chamber, keeping luminous intensity at 12000-15000Lux, using circulation radiation that radiates at 10-30Deg. C for 8-16h, keeps dark at 0-20Deg. C for 4-8h, and completing one circulation in 12-24h, at least processes one circulation. The catalyst is composed of A and B parts, wherein A part is bivalent or trivalent soluble ferric salt, B part is the soluble salt of alkali metal, the mass ratio of the A and B parts is 0.01-1, and the mass ratio between the catalyst and estrogen is 0.01-1. The invention has warm reaction, low cost, high degrade rate, non secondary pollution, and wide application for degrading estrogen contaminant with wide distribution and low density, therefore, the invention has wide industrial application outlook.
Description
Technical field
The present invention relates to the photodegradation removal method of oestrogenic hormon pollutent, the method for abiotic factor catalyzed degradation oestrogenic hormon pollutent under specifically a kind of simulating nature optical condition.
Background technology
After environmental estrogens (estrogen) is meant that a class exogenous compounds enters body, have processes such as synthetic, the release of disturbing normal secretion matter in the body, running, metabolism, combination, activate or inhibition endocrine system function, thereby destroy the material that it keeps organism stability and regulating and controlling effect.It disturbs the mankind or all too many levels of animal endocrine system and causes anomalous effect.
Environmental hormone is divided into natural estrogen, plant estrogen and fungoid oestrogenic hormon, the oestrogenic hormon of synthetic, environmental chemical pollutants.
The harm of environmental estrogens mainly contains: under extremely low concentration, just can cause biological and human body sex hormone secretion amount and actively descend, sperm quantity reduces, reproductive organ is unusual, and reproductive performance is reduced, offspring's health and surviving rate descend, the sickness rate of various cancers increases, some animals female phenomenons are serious.Secondly also can cause some neurotoxicities and immunotoxicity ((a) Ohko, Y.; Iuchi, K.-I.; Niwa, C.; Tatsuma, T.; Nakashima, T.; Iguchi, T.; Kubota, Y.; Fujishima, A.Environ.Sci.Technol.2002,36,4175. (b) Hanselman, T.A.; Graetz, D.A.; Wilke, A.C.Environ.Sci.Trchnol.2003,37,5471. (c) Casey, X.M.; Larsen, G.L.; Hakk, H.;
J.Environ.Sci.Technol.2003,37,2400. (d) Rosenfeldt, E.J.; Linden, K.G.Environ.Sci.Technol.2004,38,5476. (e) Science 2004,303,950. (f) Hess, R.A.; Bunick, D.; Lee; K.H.; Bahr, J.; Taylor, J.A.; Korach, K.S.; Lubahn, B.B.Nature 1997,390,509. (g) Science 1998,279,1631. (h) Spearow, J.L.; Doemeny, P.; Sera, R.; Leffler, R.; Barkley, M.Science 1999,285,1259., and therefore estrogenic environmental behaviour and Study on degradation have very important significance to strategy of sustainable development tool.
The pollution channel of environmental estrogens mainly contains:
(1) environmental hormone of synthetic much is the composition of agricultural chemicals, and they remain on the agricultural-food, by human directly edible; The herbage that contains environmental hormone is raiseeed with the mixed feed that adds hormone, fowl is edible, and meat, egg, the milk that contains environmental hormone is provided to the mankind.
(2) contain after the organism death of environmental hormone, decompose, enter soil, water body once more, enter human body by multiple channel through corruption.
(3) people use washing composition, sterilizing agent in daily life in a large number, and oral contraceptive, polluted-water.
(4) burn away the refuse and plastics, discharge multiple environmental hormones such as Dioxins.
(5) refuse that gives off of the factory of environmental hormone class material.
(6) human edible leguminous plants and some vegetables are taken in phytoestrogen, change the hormonal equilibrium of human body.
(7) environmental hormone is general fat-soluble good, is slightly soluble in water, carries out biology and concentrate in food chain, enters human body again, retains in fat, and concentration further increases.Mother can pass to children to environmental hormone by placenta or milk.
(8) plastics.Dihydroxyphenyl propane is the raw material of polycarbonate, Resins, epoxy, poly phenol oxygen, and infant article much is plastics, has the people to pour boiling water in the plastics feeding bottle of polycarbonate, and the content of dihydroxyphenyl propane is 3.1～5.5 μ g/L in the water.
The degradation method of environmental estrogens mainly contains photodegradation ((a) Ohko, Y. at present; Iuchi, K.-I.; Niwa, C.; Tatsuma, T.; Nakashima, T.; Iguchi, T.; Kubota, Y.; Fujishima, A.Environ.Sci.Technol.2002,36,4175. (b) Rosenfeldt E.J.﹠amp; Linden, K.G.Environ.Sci.Technol.2004,38,5476-5483. (c) Coleman, H.M., Eggins, B.R., Byrne, J.A., Palmer, F.L.﹠amp; King, E.Appl.Catal.B:Environ.2000,24,1-5.), biological degradation ((a) T.Tanaka, K.Yamada, T.Tonosaki, T.Konishi, H.Goto, M.Taniguchi, Water sci.Technol.2000,42,89-95. (b) .C.Layton, B.W.Gregory, J.R.Seward, T.W.Schultz, G.S.Sayler, Environ Sci.Technol.2000,34,3925-3931. (c) J.S.Vader, C.G.van Ginkel, F.Sperling, W.de Jong, J., deBoer, J.S.de Graaf, M.van der Most, Chemosphere 2000,41,1239-1243. (d) M.S.Colucci, H.Bork, E.Topp, J.Environ.Qual.2001,30,2070-2076. (e) M.S.Colucci, E.Topp, J.Environ.Qual.2001,30,2077-2080. (f) K.Fujii, S.Kikuchi, M.Satomi, N.Ushio-Sata, N.Morita, Appl.Environ.Microbiol.2002,68,2057-2060.), wherein photodegradation method mainly is to use semiconductor material TiO
2And material modified, employed light source great majority are UV-light, and directly utilize the report that has only minority ((a) Asahi, the R. of sunlight or visible light; Morikawa, T.; Ohwaki, T.; Aoki, K.; Taga, Y.Science 2001,293,269. (b) Khan, S.U.M.; Al-Shahry, M.; Ingler, W.B., Jr.Science 2002,297,2243. (c) Zhao, W.; Ma, W.H.; Chen, C.C.; Zhao, J.C.; Shuai, Z.G.J.Am.Chem.Soc.2004,126,4782.).The biological degradation estrogenic effect is better, but must collect pollutent, and this is operational difficulty in actual applications.In addition, also have the method for degrading estrogens such as ozone oxidation, charcoal absorption, UV-irradiation, these methods are the cost height not only, and weak effect.
Summary of the invention
In order to overcome the some shortcomings that exist in the above-mentioned degrading estrogen method, the object of the present invention is to provide a kind of catalytic activity height, treatment effect is good, the reaction conditions gentleness, processing cost is low, and the industrial applications prospect is big, can realize the estrogenic method of photocatalytic degradation of in-situ treatment.
For achieving the above object, the technical solution used in the present invention is:
A kind of method of catalytically degrading estrogen-like contaminant by simulating natural light,
At first in mass concentration 10
-3Add catalyzer in the estrogen-like contaminant aqueous solution of-10mg/L, the container that solution is housed is put into phytotron, be mimic natural light irradiation environment, keep the intensity of illumination of 12000-15000Lux; Be used in 10-30 ℃, 8-16 hour illumination, 0-20 ℃, 4-8 hour dark, 12-24 hour is a round-robin circulation radiation modality; Circulation primary or once more than;
Described catalyzer is made up of component A and B component, and component A is divalence or trivalent soluble ferric iron salt, and B component is alkali-metal soluble salt; The ratio of the amount of substance of component A, B component is 0.01～1; Catalyzer is 0.01～1 with the ratio of estrogenic amount of substance.
Described trivalent soluble ferric iron salt is iron trichloride, iron nitrate and/or ferric sulfate; Alkali-metal soluble salt is a nitrate, and these soluble salts are with NO
3 -, NO
2 -Be the active anion component; Catalyzer is preferably 0.5～1 with the ratio of estrogenic amount of substance.
The present invention has following advantage:
1. catalyst activity height, the reaction conditions gentleness.The present invention is in having the ground-in small test tube, adds the catalyzer of the salts solution composition of trivalent soluble ferric iron salt and nontransition metal, is oxygenant with the air, oestrogenic hormon can be degraded to carbonic acid gas, water and the small molecules carboxylic acid that some are nontoxic.This method is handled oestrogenic hormon solution can reach 100% degradation rate, measures estrogen activity by utilizing the special gene yeast method of human body, finds that estrogen activity reduces, and does not have secondary pollution in degradation process.
2. processing cost is low, and industrial prospect is big.Oxygenant and the catalyst levels used owing to the present invention are little, and cheaply be easy to get, treating processes is easy, but therefore catalytic oxidation of the present invention has the application prospect of industrial treatment estrogen-like contaminant, is applicable to the degraded of the estrogen-like contaminant wide, that concentration is low that distributes; This method is handled oestrogenic hormon waste water reaction mild condition, and is cheap, the degradation rate height.
3. environmental friendliness.Reaction system of the present invention is simple, and is convenient and practical, and catalyst reaction is active high, and is thorough to the removal of pollutent.Catalyzer can not cause secondary pollution to environment in used concentration range.
4. applied widely.The present invention is applicable to that oestrogenic hormon waste water and some about the processing of the waste water of oestrogenic hormon growth factory, comprise the natural oestrogenic hormon and the oestrogenic hormon of synthetic, and the processed estrogenic structural formula of common need is given an example as F:
17β-estradiol estriol 17α-ethynylestradiol
Embodiment
Give further instruction below by example to the present invention, certainly, the present invention is not limited only to following embodiment.
Embodiment 1
At first 40 ℃ of methods that adopt ultrasonic dissolution, the 17 β estradiol solution of preparation 5mg/L, again 15ml concentration is packed in the test tube of 20ml/L band grinding port plug for this solution, and in test tube, add catalyzer, cover lid, put into phytotron and carry out illumination, finish in the experiment in the controlled environment chamber, complete mimic physical environment, keep the intensity of illumination of 12000-15000Lux, adopt illumination in 16 hours, 8 hours dark, circulation in 24 hours, wherein temperature being set during light application time is 22 ℃, and it is 18 ℃ that temperature is set interlunation.Every day, sample detecting was done a series of control reaction simultaneously, and the clearance of reaction back 17 β estradiol sees Table 1.
The result of photocatalytic degradation 17 β estradiol under table 1 simulating natural condition
*: the degradation rate after 30 days is 100%; Mol% is catalyzer and estrogenic ratio.
Embodiment 2
According to the operation steps of the foregoing description 1, use FeCl
3/ NaNO
2Be catalyzer, under same condition, handle the trihydroxy-oestrin of 10mg/L, the results are shown in Table 2.
The result of photocatalytic degradation trihydroxy-oestrin under table 2 simulating natural condition
Mol% is catalyzer and estrogenic ratio.
Embodiment 3
According to the operation steps of the foregoing description 1, use FeCl
3/ NaNO
2Be catalyzer, under same condition, handle 17 α-lynoral of 4mg/L, the results are shown in Table 3.
The result of photocatalytic degradation 17 α-lynoral under table 3 simulating natural condition
Mol% is catalyzer and estrogenic ratio
Embodiment 4
According to the operation steps of the foregoing description 1, be with example 1 difference, use FeCl
3/ NaNO
2Be catalyzer, carry out illumination respectively when temperature is 10 ℃, 15 ℃, 25 ℃, 30 ℃, the black status temperature is 0 ℃, 10 ℃, 15 ℃, 20 ℃ and has also obtained good effect.
Embodiment 5
According to the operation steps of the foregoing description 4, be with example 4 differences, use FeCl
3/ NaNO
2Be catalyzer, change light application time into 8 hours, change 4 hours interlunation into, circulation in 12 hours has obtained and the same good effect of circulation in 24 hours.
Claims (4)
1. the method for a catalytically degrading estrogen-like contaminant by simulating natural light is characterized in that:
At first in mass concentration 10
-3Add catalyzer in the estrogen-like contaminant aqueous solution of-10mg/L, the container that solution is housed is put into phytotron, be mimic natural light irradiation environment, keep the intensity of illumination of 12000-15000Lux; Be used in 10-30 ℃, 8-16 hour illumination, 0-20 ℃, 4-8 hour dark, 12-24 hour is a round-robin circulation radiation modality; Circulation primary or once more than;
Described catalyzer is made up of component A and B component, and component A is divalence or trivalent soluble ferric iron salt, and B component is alkali-metal soluble salt; The ratio of the amount of substance of component A, B component is 0.01～1; Catalyzer is 0.01～1 with the ratio of estrogenic amount of substance.
2. according to the method for the described catalytically degrading estrogen-like contaminant by simulating natural light of claim 1, it is characterized in that: described trivalent soluble ferric iron salt is iron trichloride, iron nitrate and/or ferric sulfate.
3. according to the method for the described catalytically degrading estrogen-like contaminant by simulating natural light of claim 1, it is characterized in that: the described metal soluble salt of crying out is a nitrate, and these soluble salts are with NO
3 -, NO
2 -Be the active anion component.
4. according to the method for the described catalytically degrading estrogen-like contaminant by simulating natural light of claim 1, it is characterized in that: described catalyzer is 0.5～1 with the ratio of estrogenic amount of substance.
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| CN2006101340167A CN101168455B (en) | 2006-10-25 | 2006-10-25 | Method for catalytically degrading estrogen-like contaminant by simulating natural light |
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| CN2006101340167A CN101168455B (en) | 2006-10-25 | 2006-10-25 | Method for catalytically degrading estrogen-like contaminant by simulating natural light |
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| CN101168455A true CN101168455A (en) | 2008-04-30 |
| CN101168455B CN101168455B (en) | 2010-08-25 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103754981A (en) * | 2014-01-02 | 2014-04-30 | 上海大学 | Method for removing biotoxicity of estrogen in water body and electronic beam radiation water treatment device |
| TWI655600B (en) * | 2016-05-20 | 2019-04-01 | 古高爾控股有限公司 | Eel aquaculture system using ict |
| CN112958138A (en) * | 2021-03-05 | 2021-06-15 | 重庆科技学院 | Composite photocatalyst AgIn5S8/g-C3N4And preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1028508C (en) * | 1988-09-06 | 1995-05-24 | 厦门大学 | Process of photocatalysis treatment of waste water |
| CN1666815A (en) * | 2004-03-11 | 2005-09-14 | 曾庆琳 | Anatase type nanometer titanium dioxide with photcatalytst disinfecting ability |
-
2006
- 2006-10-25 CN CN2006101340167A patent/CN101168455B/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103754981A (en) * | 2014-01-02 | 2014-04-30 | 上海大学 | Method for removing biotoxicity of estrogen in water body and electronic beam radiation water treatment device |
| TWI655600B (en) * | 2016-05-20 | 2019-04-01 | 古高爾控股有限公司 | Eel aquaculture system using ict |
| CN112958138A (en) * | 2021-03-05 | 2021-06-15 | 重庆科技学院 | Composite photocatalyst AgIn5S8/g-C3N4And preparation method and application thereof |
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| CN101168455B (en) | 2010-08-25 |
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