CN1613784A - Method for light catalytic degrading carbamate pesticide in water - Google Patents
Method for light catalytic degrading carbamate pesticide in water Download PDFInfo
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- CN1613784A CN1613784A CN 200410067604 CN200410067604A CN1613784A CN 1613784 A CN1613784 A CN 1613784A CN 200410067604 CN200410067604 CN 200410067604 CN 200410067604 A CN200410067604 A CN 200410067604A CN 1613784 A CN1613784 A CN 1613784A
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- titanium dioxide
- carbamate
- photocatalytic degradation
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Abstract
A method for photo-catalytic degrading carbamate agricultural pesticide in water is carried out by fixing carrying TiO2 on ceramic slice with porous structure, putting the slice as catalyst slice into photo-catalytic reactor, degrading carbamate agricultural pesticide in water under ultraviolet irradiation, ultrasonic dispersing the superfine TiO2 powder in distilled water to form TiO2 suspensoid, immersing acidified and silanized porous ceramic slice in suspensoid for 2 hrs, baking at 110deg.C in oven for 1 hr, roasting at 600-7002deg.C for 6-8 hrs, and cooling to temperature in drier. Its advantages include low cost, fast speed and no pollution.
Description
Technical field
What the present invention relates to is a kind of method that is used for the degrading pesticide of environmental technology field, specifically is the method for carbamate chemicals for agriculture in a kind of photocatalytic degradation water.
Background technology
Along with the increase year by year of pesticide species and turnout, the trade effluent that agricultural chemicals produces in process of production also not only increases, and is a great problem of present wastewater treatment, also is one of reason that causes the drinking water source deterioration.Carbamate chemicals for agriculture accounts for pesticide species one big class, its trade effluent generally adopts chemical treatment or biochemical treatment at present, these treatment processs often must drop into other chemicals and destroy poisonous waste water, or build huge biochemical treatment apparatus, therefore these methods expend a large amount of manpowers, financial resources, material resources, and what have causes shortcomings such as secondary pollution, process cost height.Nanosecond science and technology have obtained widespread use in recent years, solve the waste water that produces in the pesticide producing process with nanotechnology and handle for the three wastes new approach is provided, and also will make environmental protection industry bring new hope and opportunity.Utilize the principle of titanium dioxide catalyze and degrade organic pollutants to be: it is right to produce electronics-hole with N-type semiconductor TiO2 nanoparticle under action of ultraviolet light, and this hole will be adsorbed on the OH of semiconductor surface to capturing the organic electronics of particle surface
-And H
2O carries out oxidation, generates the OH free radical with strong oxidizing property, is used for the oxidative degradation organism.The organism direct oxidation that itself also can be adsorbed on semiconductor surface is simultaneously decomposed, and to the semi-conductor aqueous systems oxygen that exposes to the sun, accelerates organic degradation speed, makes much to be difficult to biodegradable material mineralising.
Find by prior art documents, " Photocatalytic degradationof 3,4-xylyl N-methylcarbamate (MPMC) and other carbamate pesticides inaqueous TiO that people such as Robledo deliver on " Journal of MolecularCatalysis A:Chemical " 144 (1999) 425-430
2Suspensions ", this article is mentioned and is utilized TiO
2Aqeous suspension comes catalyzed degradation 3,4-dimethyl N-methyl carbamate agricultural chemicals, and with MPMC, MIPC, MTMC, XMC, five kinds of degradation of pesticides of MCC are inorganics CO
2, NO
3 -, NH
4 +Owing to utilize TiO
2Aqeous suspension, catalytic material TiO
2Be difficult to recycle, the cost recovery height is easy to generate secondary pollution; In addition on the one hand, TiO surface energy in aqeous suspension is easy to generate cohesion, and phenomenon such as pesticide granules reunion greatly, and catalytic activity can be passed in time and is reduced to inactivation.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, the method of carbamate chemicals for agriculture in a kind of photocatalytic degradation water is provided, makes that it has that degradation speed is fast, non-secondary pollution, catalyzer are easy to get, cheaply, recyclable use repeatedly, working cost is low, equipment is simple, the characteristics of less investment.
The present invention is achieved by the following technical solutions, and the present invention is with titanium dioxide TiO
2Be catalyzer, it is immobilized on the ceramic sheet with vesicular structure, the aperture is between (100-300) , this ceramic sheet is inserted in the photo catalysis reactor as the catalyzer thin slice, make catalytic laminate vertical with UV-light, under (15-500) W UV-light irradiation (30-300) minute to water in carbamate chemicals for agriculture degrade, start simultaneously to stir and make reaction solution even, can make between degradation of pesticide in the water (40-100) %.This catalyzer preparation of sections method is: with the superfine titanic oxide ultra-sonic dispersion in distilled water, form the suspension of titanium dioxide, the porous ceramics piece then caproic acidization, silanization handled immersed in the suspension about 2 hours, baking is after 1 hour in 110 ℃ of baking ovens, through (600-700) ℃ high-temperature roasting (6-8) hour, put into loft drier and be cooled to room temperature promptly.
Carbamate chemicals for agriculture comprises carbofuran, carbosulfan, benfuracarb, fenobucarb, isoprocarb, Propoxur, methomyl, UC-51762, alanycarb, fenothiocarb Aphox, ABG-6215, carbaryl, triaxamate, meta-tolyl-N-methylcarbamate (MTMC), thiobencarb, molinate in the degradable water of the present invention.
Used titanium dioxide is that anatase titanium dioxide is main powder body material, and the particle size range of this powder is (5-200) nm, and the optimum grain-diameter scope is (10-100) nm.
The material of used immobilized thing is a porous ceramics, and its aperture is between (100-300) , and its structural formula is with formula M e
xC
yRepresent, comprise SiC, B
4C, TiC, WC, ZrC, Cr
3C
2
The present invention is with titanium dioxide TiO
2Be catalyzer, it is immobilized on the ceramic sheet with vesicular structure, this thin slice is inserted in the photo catalysis reactor, under the irradiation of UV-light to water in carbamate chemicals for agriculture degrade, this thin slice catalyzer shows catalytic activity preferably, chemical property is stable, has acid-and base-resisting, heat, is difficult for oxidation, the characteristics of strong adhesion, good permeability.Utilize that carbamate chemicals for agriculture comprises carbofuran, carbosulfan, benfuracarb, fenobucarb, isoprocarb, Propoxur, methomyl, UC-51762, alanycarb, fenothiocarb Aphox, ABG-6215, triaxamate, meta-tolyl-N-methylcarbamate (MTMC), thiobencarb, molinate in this thin slice catalyzer degradable water, this method is handled waste water and is had that degradation speed is fast, non-secondary pollution, catalyzer are easy to get, cheaply, recyclable use repeatedly, working cost is low, equipment is simple, the characteristics of less investment.
Embodiment
The invention will be further described below in conjunction with specific examples.
Experimental example 1.
With the 4g median size is that ultrafine titania ultra-sonic dispersion about 100nm is in 100ml distilled water, form the suspension of titanium dioxide, the porous ceramics piece (300 * 100mm) that caproic acidization, silanization were handled then, its aperture is about 300 , it was immersed in tio_2 suspension about 2 hours, baking through 600 ℃ of high-temperature roastings 8 hours, was put into loft drier and is cooled to room temperature and promptly gets the catalyzer thin slice after 1 hour in 110 ℃ of baking ovens.This thin slice is inserted in the photo catalysis reactor, makes catalytic laminate vertical, start to stir and make reaction solution even with UV-light, the irradiation under the 75W UV-light 120 minutes to water in methomyl degrade, can make 'Miduowei ' agricultural chemical degraded 86% in the water.
Experimental example 2.
With the 4g median size is that ultrafine titania ultra-sonic dispersion about 100nm is in 100ml distilled water, form the suspension of titanium dioxide, the porous ceramics piece (300 * 100mm) that caproic acidization, silanization were handled then, its aperture is about 100 , it was immersed in tio_2 suspension about 1 hour, baking through 700 ℃ of high-temperature roastings 6 hours, was put into loft drier and is cooled to room temperature and promptly gets the catalyzer thin slice after 1 hour in 110 ℃ of baking ovens.This thin slice is inserted in the photo catalysis reactor, makes catalytic laminate vertical, start to stir and make reaction solution even with UV-light, the irradiation under the 100W UV-light 120 minutes to water in carbofuran degrade, can make carbofuran degradation of pesticide 95% in the water.
Experimental example 3.
With the 4g median size is that ultrafine titania ultra-sonic dispersion about 50nm is in 100ml distilled water, form the suspension of titanium dioxide, the porous ceramics piece (300 * 100mm) that caproic acidization, silanization were handled then, its aperture is about 200 , it was immersed in tio_2 suspension about 2 hours, baking through 650 ℃ of high-temperature roastings 6 hours, was put into loft drier and is cooled to room temperature and promptly gets the catalyzer thin slice after 1 hour in 110 ℃ of baking ovens.This thin slice is inserted in the photo catalysis reactor, makes catalytic laminate vertical, start to stir and make reaction solution even with UV-light, the irradiation under the 100W UV-light 180 minutes to water in fenobucarb degrade, can make agricultural chemicals fenobucarb degraded 92% in the water.
Experimental example 4.
With the 4g median size is that ultrafine titania ultra-sonic dispersion about 30nm is in 100ml distilled water, form the suspension of titanium dioxide, the porous ceramics piece (300 * 100mm) that caproic acidization, silanization were handled then, its aperture is about 150 , it was immersed in tio_2 suspension about 3 hours, baking through 600 ℃ of high-temperature roastings 6 hours, was put into loft drier and is cooled to room temperature and promptly gets the catalyzer thin slice after 1 hour in 110 ℃ of baking ovens.This thin slice is inserted in the photo catalysis reactor, makes catalytic laminate vertical, start to stir and make reaction solution even with UV-light, the irradiation under the 150W UV-light 120 minutes to water in carbaryl degrade, can make carbaryl degradation of pesticide 98% in the water.
Claims (5)
1. the method for carbamate chemicals for agriculture in the photocatalytic degradation water, it is characterized in that, with titanium dioxide TiO2 is catalyzer, it is immobilized on the ceramic sheet with vesicular structure, this ceramic sheet is inserted in the photo catalysis reactor as the catalyzer thin slice, under the irradiation of UV-light with water in carbamate pesticide degrade, this catalyzer preparation of sections method is: with ultrafine titania through ultra-sonic dispersion in distilled water, form the suspension of titanium dioxide, then with acidifying, porous ceramics piece that silanization was handled immersed in the suspension 2 hours, baking is after 1 hour in 110 ℃ of baking ovens, through 600-700 ℃ high-temperature roasting 6-8 hour, put into loft drier and be cooled to room temperature promptly.
2. the method for carbamate chemicals for agriculture is characterized in that in the photocatalytic degradation water according to claim 1, and used titanium dioxide is the powder body material of anatase titanium dioxide, and the particle size range of this powder is 5-200nm.
3. according to the method for carbamate chemicals for agriculture in the photocatalytic degradation water of claim 2, it is characterized in that used titanium dioxide is the powder body material of anatase titanium dioxide, the particle diameter of this powder further is 10-100nm.
4. according to the method for carbamate chemicals for agriculture in the photocatalytic degradation water of claim 1, it is characterized in that the material of used immobilized thing is a porous ceramics, its aperture is between 100-300 , and its structural formula is represented with formula M exCy, comprises SiC, B
4C, TiC, WC, ZrC, Cr
3C
2
5. according to the method for carbamate chemicals for agriculture in the photocatalytic degradation water of claim 1, it is characterized in that, carbamate chemicals for agriculture in the degrading waste water, comprise carbofuran, carbosulfan, benfuracarb, fenobucarb, isoprocarb, Propoxur, methomyl, UC-51762, alanycarb, fenothiocarb Aphox, ABG-6215,, carbaryl, triaxamate, meta-tolyl-N-methylcarbamate (MTMC), thiobencarb, molinate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100676044A CN1312050C (en) | 2004-10-28 | 2004-10-28 | Method for light catalytic degrading carbamate pesticide in water |
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|---|---|---|---|
| CNB2004100676044A CN1312050C (en) | 2004-10-28 | 2004-10-28 | Method for light catalytic degrading carbamate pesticide in water |
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| CN1613784A true CN1613784A (en) | 2005-05-11 |
| CN1312050C CN1312050C (en) | 2007-04-25 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102442711A (en) * | 2010-09-30 | 2012-05-09 | 北京联合大学生物化学工程学院 | Method for degrading carbamate pesticide in water through photocatalysis |
| CN104353477A (en) * | 2014-11-26 | 2015-02-18 | 济源职业技术学院 | P-n heterojunction type visible light catalyst B4C/TiO2 and preparation method thereof |
| CN106036375A (en) * | 2016-06-12 | 2016-10-26 | 中国农业大学 | Method for degrading carbamate pesticide |
| CN106070303A (en) * | 2016-06-01 | 2016-11-09 | 刘园 | A kind of compositions preventing and treating celery septoria disease and preparation method thereof |
| CN106754588A (en) * | 2017-03-30 | 2017-05-31 | 湖南农业大学 | Salt tolerant arprocarb agricultural chemicals efficient degrading bacterial strain and its application |
| CN106966556A (en) * | 2017-05-24 | 2017-07-21 | 广西碧清源环保科技有限公司 | The technique that a kind of film process UC-51762 produces waste water |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1405122A (en) * | 2001-08-20 | 2003-03-26 | 张彦青 | Water-cleaning ceramic ring and its production method |
| CN1197662C (en) * | 2001-09-24 | 2005-04-20 | 中国科学院理化技术研究所 | Method of forming metal composite titanium dioxide nano particle film on ceramic surface |
| CN1421396A (en) * | 2001-11-28 | 2003-06-04 | 中国科学院广州能源研究所 | Method of eliminating organic pollutant in photocatalytic fluidized bed |
| CN1187294C (en) * | 2002-02-01 | 2005-02-02 | 武汉大学 | Prepn of nanometer TiO2 antiseptic ceramic |
| CN1468937A (en) * | 2002-07-18 | 2004-01-21 | 青岛海洋大学 | Residual pesticide degrading agent |
| CN1206015C (en) * | 2003-03-11 | 2005-06-15 | 武汉理工大学 | Method for preparing porous ceramic material with titanium dioxide optical catalytic nano-coating for purifying air and water |
| CN1228138C (en) * | 2003-08-29 | 2005-11-23 | 哈尔滨工业大学 | Modified titanium dioxide immobilization method for degrading organic pollutant in water |
-
2004
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102442711A (en) * | 2010-09-30 | 2012-05-09 | 北京联合大学生物化学工程学院 | Method for degrading carbamate pesticide in water through photocatalysis |
| CN102442711B (en) * | 2010-09-30 | 2013-04-24 | 北京联合大学生物化学工程学院 | Method for degrading carbamate pesticide in water through photocatalysis |
| CN104353477A (en) * | 2014-11-26 | 2015-02-18 | 济源职业技术学院 | P-n heterojunction type visible light catalyst B4C/TiO2 and preparation method thereof |
| CN104353477B (en) * | 2014-11-26 | 2016-06-22 | 济源职业技术学院 | A kind of p-n heterojunction type visible light catalyst B4C/TiO2And preparation method thereof |
| CN106070303A (en) * | 2016-06-01 | 2016-11-09 | 刘园 | A kind of compositions preventing and treating celery septoria disease and preparation method thereof |
| CN106036375A (en) * | 2016-06-12 | 2016-10-26 | 中国农业大学 | Method for degrading carbamate pesticide |
| CN106754588A (en) * | 2017-03-30 | 2017-05-31 | 湖南农业大学 | Salt tolerant arprocarb agricultural chemicals efficient degrading bacterial strain and its application |
| CN106966556A (en) * | 2017-05-24 | 2017-07-21 | 广西碧清源环保科技有限公司 | The technique that a kind of film process UC-51762 produces waste water |
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|---|---|
| CN1312050C (en) | 2007-04-25 |
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