CN100551843C - A kind of method of catalysis wet-type oxidation degradation oestrogenic hormon pollutent - Google Patents
A kind of method of catalysis wet-type oxidation degradation oestrogenic hormon pollutent Download PDFInfo
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- CN100551843C CN100551843C CNB2006101340222A CN200610134022A CN100551843C CN 100551843 C CN100551843 C CN 100551843C CN B2006101340222 A CNB2006101340222 A CN B2006101340222A CN 200610134022 A CN200610134022 A CN 200610134022A CN 100551843 C CN100551843 C CN 100551843C
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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 present invention relates to a kind of method of catalysis wet-type oxidation degradation oestrogenic hormon pollutent, is 10 with mass concentration
-3The oestrogenic hormon pollutent aqueous solution of-10mg/L is packed in the autoclave, adds catalyzer, is oxygenant with oxygen or air, stirs and removes the oestrogenic hormon pollutent; Temperature of reaction is 90～180 ℃, and reaction pressure is 0.1～0.5MPa, and wherein oxygen partial pressure is 0.1～0.5MPa, and the reaction times is 1～8h.Catalyzer is made up of component A and B, and A is divalence or trivalent soluble ferric iron salt, and B is the alkali-soluble nitrite; The ratio of the amount of substance of A, B is 0.01～1; The ratio of the estrogenic amount of substance in catalyzer and the oestrogenic hormon solution is 0.01～1.This method is handled oestrogenic hormon waste water reaction mild condition, and cheap, the degradation rate height does not have secondary pollution, is applicable to the degraded of the estrogen-like contaminant wide, that concentration is low that distributes, and the industrial applications prospect is big.
Description
Technical field
The present invention relates to the processing of oestrogenic hormon pollutent, specifically a kind of method of catalysis wet-type oxidation degradation oestrogenic hormon pollutent.
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.; Wilkle, A.C.Environ.Sci.Technol.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 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., de Boer, 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 handled waste strength is smaller, and biological bacteria has certain selectivity, generally be difficult to find a kind of to all effective microbial strains of all oestrogenic hormon, the waste water that comes out for those hormone factories, oestrogenic hormon and concentration of intermediate products are big, are difficult to directly handle with biodegradable method.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 subject matter that more above-mentioned degrading estrogen waste water systems exist, 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, the industrial applications prospect is big, can handle the method for catalyzing oxidizing degrading oestrogenic hormon waste water of the oestrogenic hormon waste water of high density.
For achieving the above object, the technical solution used in the present invention is:
A kind of method of catalysis wet-type oxidation degradation oestrogenic hormon pollutent is with mass concentration 10
-3The oestrogenic hormon pollutent aqueous solution of-10mg/L is packed in the autoclave, adds catalyzer, is oxygenant with oxygen or air, magnetic agitation, oxidation removal oestrogenic hormon pollutent under heating condition; Temperature of reaction is 90～180 ℃, and reaction pressure is 0.1～0.5MPa, and wherein oxygen partial pressure is 0.1～0.5MPa, and the reaction times is 1～8h.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 that (these soluble salts are with NO for the alkali-soluble nitrite
2 --Be the active anion component); The ratio of the amount of substance of component A, B component is 0.01～1; The ratio of the estrogenic amount of substance in catalyzer and the oestrogenic hormon solution is 0.01～1.
Described trivalent soluble ferric iron salt is iron trichloride, iron nitrate and/or ferric sulfate etc.; The ratio of the estrogenic amount of substance in catalyzer and the oestrogenic hormon pollutent is 0.5～1; Temperature of reaction is preferably 130～160 ℃, is preferably 150 ℃; Reaction pressure is preferably 0.3～0.5MPa, and wherein oxygen partial pressure is preferably 0.3～0.5MPa; Reaction times is preferably 4～8h.
The present invention has following advantage:
1. catalyst activity height, the reaction conditions gentleness.The present invention is in having the stainless steel cauldron of liner, the catalyzer that adds the salts solution composition of divalence or trivalent soluble ferric iron salt and nontransition metal, with oxygen or air is oxygenant, 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 waste water can reach 100% degradation rate, and estrogen activity is reduced, and intermediate product does not have secondary pollution.
2. processing cost is low, and industrial prospect is big.Because used oxygenant and the catalyzer of the present invention cheaply is easy to get, and consumption is few, treating processes is easy, but therefore catalytic oxidation of the present invention has the application prospect of industrial treatment oestrogenic hormon waste water.
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 the processing of oestrogenic hormon waste water, and the processed organic pollutant structural formula of common need is exemplified below:
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 beta estradiol solution of preparation 5mg/L, be that the 17 beta estradiol solution of 5mg/L are packed in the little autoclave again with 20ml concentration, then in system, add catalyzer, sealing charges into oxygen with certain pressure or air at last, and warming while stirring is to assigned temperature, reacted 1～8 hour, reacted 17 beta estradiol clearances see Table 1.
Table 1 catalytic wet air oxidation is handled the result of 17 beta estradiol solution
| Catalyzer | Reaction total pressure (MPa) | Reaction oxygen partial pressure (MPa) | Temperature of reaction (℃) | Reaction times (h) | Clearance (%) |
| 50mol％FeCl 3/ 100mol％NaNO 2 | 0.5 | 0.5 | 90 | 4 | 47 |
| 50mol％FeCl 3/ 100mol％NaNO 2 | 0.5 | 0.5 | 120 | 4 | 70 |
| 50mol％FeCl 3/ 100mol％NaNO 2 | 0.5 | 0.5 | 150 | 4 | 99 |
| 50mol％FeCl 3/ 100mol％NaNO 2 | 0.5 | 0.5 | 180 | 4 | 99 |
| 1mol％FeCl 3 | 0.5 | 0.5 | 150 | 4 | 0 |
| 10mol％FeCl 3 | 0.5 | 0.5 | 150 | 4 | 65 |
| 20mol％FeCl 3 | 0.5 | 0.5 | 150 | 4 | 86 |
| 50mol％FeCl 3 | 0.5 | 0.5 | 150 | 4 | 97 |
| 50mol％FeCl 3/ 50mol％NaNO 2 | 0.5 | 0.5 | 150 | 4 | 99 |
| 50mol％FeCl 3/ 1mol％NaNO 2 | 0.5 | 0.5 | 150 | 4 | 98 |
| 50mol％FeCl 3/ 20mol％NaNO 2 | 0.5 | 0.5 | 150 | 4 | 98 |
| 50mol％FeCl 3/ 50mol％NaNO 2 | 0.5 | 0.5 | 150 | 1 | 53 |
| 50mol％FeCl 3/ 50mol％NaNO 2 | 0.5 | 0.5 | 150 | 2 | 88 |
| 50mol％FeCl 3/ 50mol％NaNO 2 | 0.5 | 0.5 | 150 | 8 | 99 |
| 50mol％FeCl 3/ 50mol％NaNO 2 | 0.1 | 0.1 | 150 | 4 | 70 |
| 50mol％FeCl 3/ 50mol％NaNO 2 | 0.5 | 0.3 | 150 | 4 | 94 |
| 50mol％FeCl 3/ 50mol％NaNO 2 | 0.5 | 0.5 | 150 | 4 | 99 |
| 10mol％Fe 2(SO 4) 3/ 10mol％NaNO 2 | 0.5 | 0.5 | 150 | 4 | 94.4 |
| 10mol％FeCl 2/ 10mol％NaNO 2 | 0.5 | 0.5 | 150 | 4 | 75.6 |
In the table: mol% is catalyzer and estrogenic ratio, and temperature of reaction is the outer oil bath temperature of reactor.
Embodiment 2
According to the operation steps of the foregoing description 1, use FeCl
3/ NaNO
2Being catalyzer, is 150 ℃ in temperature of reaction, and the reaction oxygen partial pressure is 0.5MPa, and the reaction times is to handle other oestrogenic hormon waste water (10mg/L or 5mg/L) under the condition of 4h, the results are shown in Table 2.
Table 2 catalytic wet air oxidation is handled the result of other oestrogenic hormon solution
| Oestrogenic hormon | Catalyzer | Reaction total pressure (MPa) | Reaction oxygen partial pressure (MPa) | Temperature of reaction (℃) | Reaction times (h) | Clearance (%) |
| Trihydroxy-oestrin | 50mol％FeCl 2/ 50mol％NaNO 2 | 0.5 | 0.5 | 150 | 4 | 99.2 |
| Ethinylestradiol | 50mol％FeCl 2/ 50mol％NaNO 2 | 0.5 | 0.5 | 150 | 4 | 86.2 |
In the table: mol% is catalyzer and estrogenic ratio, and temperature of reaction is the outer oil bath temperature of reactor.
Claims (5)
1, a kind of method of catalysis wet-type oxidation degradation oestrogenic hormon pollutent is characterized in that: with mass concentration 10
-3The oestrogenic hormon pollutent aqueous solution of-10mg/L is packed in the autoclave, adds catalyzer, is oxygenant with oxygen or air, magnetic agitation, oxidation removal oestrogenic hormon pollutent under heating condition; Temperature of reaction is 90～180 ℃, and reaction pressure is 0.1～0.5MPa, and wherein oxygen partial pressure is 0.1～0.5MPa, and the reaction times is 1～8h;
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 the alkali-soluble nitrite; The ratio of the amount of substance of component A, B component is 0.01～1; The ratio of the estrogenic amount of substance in catalyzer and the oestrogenic hormon solution is 0.01～1;
Described oestrogenic hormon is 17 beta estradiols, trihydroxy-oestrin or ethinylestradiol.
2, according to the method for the described catalysis wet-type oxidation degradation oestrogenic hormon of claim 1 pollutent, 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 catalysis wet-type oxidation degradation oestrogenic hormon of claim 1 pollutent, it is characterized in that: the ratio of the estrogenic amount of substance in described catalyzer and the oestrogenic hormon pollutent is 0.5～1.
4, according to the method for the described catalysis wet-type oxidation degradation oestrogenic hormon of claim 1 pollutent, it is characterized in that: described temperature of reaction is 130～160 ℃, and reaction pressure is 0.3～0.5MPa, and wherein oxygen partial pressure is 0.3～0.5MPa.
5, according to the method for the described catalysis wet-type oxidation degradation oestrogenic hormon of claim 1 pollutent, it is characterized in that: the described reaction times is 4～8h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1498861A (en) * | 2002-11-06 | 2004-05-26 | 中国科学院大连化学物理研究所 | Method for treating wastewater with high hydroxybenzene contained through catalyzing wet oxidation |
| CN1753837A (en) * | 2002-08-14 | 2006-03-29 | 梅迪斯坎两合公司 | Method and device for post-treating waste water from sewage plants |
| WO2006090780A1 (en) * | 2005-02-23 | 2006-08-31 | Kabushiki Kaisha Yakult Honsha | Estrogenic substance degradable microorganism and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1753837A (en) * | 2002-08-14 | 2006-03-29 | 梅迪斯坎两合公司 | Method and device for post-treating waste water from sewage plants |
| CN1498861A (en) * | 2002-11-06 | 2004-05-26 | 中国科学院大连化学物理研究所 | Method for treating wastewater with high hydroxybenzene contained through catalyzing wet oxidation |
| WO2006090780A1 (en) * | 2005-02-23 | 2006-08-31 | Kabushiki Kaisha Yakult Honsha | Estrogenic substance degradable microorganism and use thereof |
Non-Patent Citations (2)
| Title |
|---|
| 环境激素酞酸酯类化合物的净化技术进展. 张天永等.环境科学与技术，第28卷第1期. 2005 * |
| 环境雌激素及其降解途径. 刘先利等.环境科学与技术，第26卷第4期. 2003 * |
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