CN102807263A - Method for degrading 2,2-bis(p-chlorophenyl)-1,1,1-trichloroethane pesticide in water by photocatalysis - Google Patents
Method for degrading 2,2-bis(p-chlorophenyl)-1,1,1-trichloroethane pesticide in water by photocatalysis Download PDFInfo
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- CN102807263A CN102807263A CN2011103497525A CN201110349752A CN102807263A CN 102807263 A CN102807263 A CN 102807263A CN 2011103497525 A CN2011103497525 A CN 2011103497525A CN 201110349752 A CN201110349752 A CN 201110349752A CN 102807263 A CN102807263 A CN 102807263A
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- trichloroethane
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Abstract
The invention relates to a method for degrading 2,2-bis(p-chlorophenyl)-1,1,1-trichloroethane pesticide in water by photocatalysis, which is characterized in that a polyvinyl alcohol film carried with nanometer La2O3, Fe2O3 and NiO composite oxide is used as carrier catalyst, the carrier catalyst is put in a photocatalysis reactor containing aqueous solution to be processed; under the irradiation of ultraviolet light, the 2,2-bis(p-chlorophenyl)-1,1,1-trichloroethane pesticide in water can be quickly decomposed. The preparation method for the carrier catalyst comprises the following steps of: under continuous stirring, slowly adding polyvinyl alcohol powder of which the average molecular weight is 80000-90000 and the alcoholysis degree is 70-80% into distilled water, wherein the mass ratio of the polyvinyl alcohol to water is 1:(20-50); after the polyvinyl alcohol is fully swelled, raising temperature to 90 DEG C; under continuous stirring, adding La2O3, Fe2O3 and NiO powder dispersed by ultrasonic wave into the above mixed liquor; continuously stirring for 2-3 hours to form homogeneous colloidal solution; dipping cleaned ceramic matrix material into the solution for standing for 1-3 hours; after the cleaned ceramic matrix material is taken out, baking for 0.5-1.5 hours at the temperature of 180-230 DEG C to enable the surface of the ceramic matrix material to form a catalyst film of which the thickness is 50-200 naometers; and cooling to obtain the carrier catalyst. The method disclosed by the invention not only can be used for processing various types of waste water containing pyrethroid pesticide but also can be used for degrading the 2,2-bis(p-chlorophenyl)-1,1,1-trichloroethane pesticide in agricultural product aqueous extracts, such as grain, fruit, tea or Chinese herbal medicine.
Description
Technical field
The present invention relates to a kind of method of degrading pesticide, especially the method for biconjugate chloro-phenyl-trichloroethane agricultural chemicals in the photocatalytic degradation water belongs to catalysis technical field.
Background technology
Along with the development of agriculture industrialization, chemical pesticide is being brought into play more and more important effect in the production of agricultural-food such as China's grain, vegetables, fruit, tealeaves and medicinal material.But; Because people are to the characteristics of motion of agricultural chemicals in the nature biotechnology body; The acquisition of knowledge such as aspects such as pathways metabolism, degraded mode and residual savings is not enough, when the enjoyment chemical pesticide brings good harvest happy, has usually ignored its residual harm that brings.
Biconjugate chloro-phenyl-trichloroethane (Dichlorodiphenyltrichloroethane) is DDT (DDT), chemical formula (ClC again
6H
4)
2CH (CCl
3), be white crystal, water insoluble, be dissolved in kerosene, can be made into emulsion, be the effective insecticidal agent.Be that 20 th Century prevent agricultural pest, very big effect has been played in the disease harm that alleviates mosquitos and flies propagation such as malaria typhoid fever.DDT is reined in 1874 first by the diligent moral of Ou Tema to synthesize, and but is nineteen thirty-nine just to be realized out by Miller but this compound has the characteristic of sterilant effect.This product is almost all very effective to all insects.During the World War II, the use range of DDT has obtained expansion rapidly, and is exhibiting one's skill to the full aspect the treatment of diseases such as malaria, dysentery, has given treatment to a lot of life, but also has brought the raising the output of farm crop.But find DDT very difficult degradation in environment in the eighties of last century scientists sixties; And can in animal tallow, accumulate; Even in the blood of antarctic penguin, also detect DDT; The birds body includes DDT and can cause producing soft shelled egg and can not hatch, and therefore the bird of prey such as the U.S. national bird white-crowned sea eagle that especially are in the food chain climax almost become extinct.1962, U.S. scientist Lei Qieerkaxun suspected that in its works " silent spring " it is to cause the major cause of the bird of some food meat and ichthyophagy near extinction that DDT gets into food chain.Therefore DDT is prohibited by countries in the world gradually and is produced and use after the seventies.DDT can be in the medium-term and long-term accumulation of body fat; Be proved and can have upset biological hormone secretion; " epidemiology " magazine of calendar year 2001 is mentioned, and scientist has confirmed first that through 24 16 to 28 years old Mexico man's of selective examination blood sample the rising of DDT level can cause sperm number to reduce in the human body.In addition, the increase of neonatal premature labor and nascent body weight also has certain contact with DDT, and existing medical research has shown that also it is influential to the mankind's liver function and form, and tangible carcinogenic performance is arranged.
Set up a kind of method that can transform biconjugate chloro-phenyl-trichloroethane agricultural chemicals fast, not only help protecting environment, and can effectively handle the aqueous extract of many agricultural-food, for the standard of living that improves us provides safeguard.All more or less there are some defectives in the degradation method of at present common biconjugate chloro-phenyl-trichloroethane agricultural chemicals: (1) utilizes the microbiological deterioration selectivity ratios higher; But culture of strains bothers very much; Bacterial classification is very strict to the requirement of temperature when degraded; Higher degradation rate is only just arranged, the extensive relatively difficulty of utilizing under its best temperature; (2) utilize the ozone oxidation degraded to have broad spectrum, but also can destroy effective constituent simultaneously, therefore relatively be fit to Industrial Wastewater Treatment, the required time of degrading in addition is long, and the manufacturing expense of ozone is than higher.(3) utilize the mechanical ball milling dechlorination to be fit to solid powder substance, normally in argon atmosphere, CaO and pastille material are mixed ball milling in cylinder of steel; After more than ten hours, can remove the agricultural chemicals in the material basically, this method length consuming time; Expensive, applicable surface is narrow; (4) utilize the photocatalytic degradation technical prospect wide, this method utilizes the electronics-hole with redox ability that photocatalyst produces under action of ultraviolet light to target compound is effectively decomposed, and utilizes nano-TiO in the document mostly
2Aqeous suspension come the agricultural chemicals in the catalyzed degradation aqueous solution, the subject matter of existence has two, the one, catalytic material be difficult to be recycled even is produced secondary pollution thus, the 2nd, the degraded selectivity of single nano material is not high
Summary of the invention
The objective of the invention is to overcome the deficiency of technology in the past, the method for biconjugate chloro-phenyl-trichloroethane agricultural chemicals in the high efficiency photocatalytic degradation water of a kind of high selection is provided.Handle the aqueous solution contain biconjugate chloro-phenyl-trichloroethane agricultural chemicals in this way, characteristics such as have that degradation speed soon, does not destroy effective constituent, non-secondary pollution, catalyzer can use repeatedly and easy to operate.
The method of biconjugate chloro-phenyl-trichloroethane agricultural chemicals is with La in the photocatalytic degradation water of the present invention
2O
3, Fe
2O
3With the NiO nano composite oxide be catalyzer; With its immobilized in PVA (PVOH) FILM as carried catalyst; This carried catalyst is placed the photo catalysis reactor that fills the pending aqueous solution; Turn on agitator under UV-irradiation, can be decomposed the biconjugate chloro-phenyl-trichloroethane agricultural chemicals in the aqueous solution in 90 minutes.The preparation method of carried catalyst is: with molecular-weight average be 80000～90000, alcoholysis degree is that 70%～80% pva powder is slowly adding in the zero(ppm) water under constantly stirring; The mass ratio of Vilaterm alcohol and water is 1: 20～50; Be warmed up to 90 ℃ after the abundant swelling of Z 150PH; Under constantly stirring, the particle diameter that ultrasonic dispersing is crossed is the La of 20～40 nanometers
2O
3, Fe
2O
3Add in the above-mentioned mixed solution with the NiO powder, continue to stir 2～3 hours, form even colloidal solution.Constant temperature in the above-mentioned solution of cleaning of ceramic matrix material (can be different shape) immersion was left standstill 1～3 hour; Taking-up was toasted 0.5～1.5 hour under 180～230 ℃ of temperature; Making the ceramic matrix material surface form thickness is the catalyst film of 50～200 nanometers, promptly gets after the cooling.
The present invention has following distinguishing feature:
(1) the carried catalyst chemical property is stable, and acidproof, alkaline-resisting, heat-resisting, the life-span is long, can use repeatedly, can not cause secondary pollution;
(2) good to biconjugate chloro-phenyl-trichloroethane degradation of pesticide selectivity, generally can remove the biconjugate chloro-phenyl-trichloroethane agricultural chemicals 90% or more in the aqueous solution in 90 minutes at UV-irradiation, other effective constituents are almost not variation then;
(3) the inventive method both can be used for handling the various waste water that contain biconjugate chloro-phenyl-trichloroethane agricultural chemicals, the biconjugate chloro-phenyl-trichloroethane remains of pesticide in the agricultural-food aqueous extracts such as grain, fruit, tealeaves or herbal medicine that also can be used for degrading.
Embodiment
Embodiment 1
With molecular-weight average be 80000, alcoholysis degree is that 80% pva powder is slowly adding in the zero(ppm) water under constantly stirring; The mass ratio of Vilaterm alcohol and water is 1: 30; Be warmed up to 90 ℃ after the abundant swelling of Z 150PH; Under constantly stirring, the median size that ultrasonic dispersing is crossed is the La of 30 nanometers
2O
3, Fe
2O
3Add in the above-mentioned mixed solution with the NiO powder, continue to stir 2 hours, form even colloidal solution.Constant temperature in the above-mentioned solution of cleaning of ceramic matrix material (can be different shape) immersion was left standstill 2 hours; Taking-up was toasted 1 hour under 190 ℃ of temperature; Making the ceramic matrix material surface form thickness is the catalyst film of 50～200 nanometers, promptly gets carried catalyst behind the naturally cooling.
Use: this carried catalyst is placed photo catalysis reactor, and the aqueous solution that will contain biconjugate chloro-phenyl-trichloroethane injects wherein, turn on agitator under UV-irradiation, can make the biconjugate chloro-phenyl-trichloroethane degraded 93% in the aqueous solution in 50 minutes.
Embodiment 2
With molecular-weight average be 90000, alcoholysis degree is that 70% pva powder is slowly adding in the zero(ppm) water under constantly stirring; The mass ratio of Vilaterm alcohol and water is 1: 40; Be warmed up to 90 ℃ after the abundant swelling of Z 150PH; Under constantly stirring, the median size that ultrasonic dispersing is crossed is the La of 25 nanometers
2O
3, Fe
2O
3Add in the above-mentioned mixed solution with the NiO powder, continue to stir 3 hours, form even colloidal solution.Constant temperature in the above-mentioned solution of cleaning of ceramic matrix material (can be different shape) immersion was left standstill 1 hour; Taking-up was toasted 0.5 hour under 200 ℃ of temperature; Making the ceramic matrix material surface form thickness is the catalyst film of 50～200 nanometers, promptly gets carried catalyst behind the naturally cooling.
Use: this carried catalyst is placed photo catalysis reactor, and the aqueous solution that will contain biconjugate chloro-phenyl-trichloroethane injects wherein, turn on agitator under UV-irradiation, can make the biconjugate chloro-phenyl-trichloroethane degraded 92% in the aqueous solution in 60 minutes.
Embodiment 3
With molecular-weight average be 85000, alcoholysis degree is that 75% pva powder is slowly adding in the zero(ppm) water under constantly stirring; The mass ratio of Vilaterm alcohol and water is 1: 25; Be warmed up to 90 ℃ after the abundant swelling of Z 150PH; Under constantly stirring, the median size that ultrasonic dispersing is crossed is the La of 35 nanometers
2O
3, Fe
2O
3Add in the above-mentioned mixed solution with the NiO powder, continue to stir 2 hours, form even colloidal solution.Constant temperature in the above-mentioned solution of cleaning of ceramic matrix material (can be different shape) immersion was left standstill 3 hours; Taking-up was toasted 1.5 hours under 210 ℃ of temperature; Making the ceramic matrix material surface form thickness is the catalyst film of 50～200 nanometers, promptly gets carried catalyst behind the naturally cooling.
Use: this carried catalyst is placed photo catalysis reactor, and the aqueous solution that will contain biconjugate chloro-phenyl-trichloroethane injects wherein, turn on agitator under UV-irradiation, can make the biconjugate chloro-phenyl-trichloroethane degraded 95% in the aqueous solution in 80 minutes.
Embodiment 4
With molecular-weight average be 80000, alcoholysis degree is that 70% pva powder is slowly adding in the zero(ppm) water under constantly stirring; The mass ratio of Vilaterm alcohol and water is 1: 40; Be warmed up to 90 ℃ after the abundant swelling of Z 150PH; Under constantly stirring, the median size that ultrasonic dispersing is crossed is the La of 32 nanometers
2O
3, Fe
2O
3Add in the above-mentioned mixed solution with the NiO powder, continue to stir 3 hours, form even colloidal solution.Constant temperature in the above-mentioned solution of cleaning of ceramic matrix material (can be different shape) immersion was left standstill 1.5 hours; Taking-up was toasted 1 hour under 220 ℃ of temperature; Making the ceramic matrix material surface form thickness is the catalyst film of 50～200 nanometers, promptly gets carried catalyst behind the naturally cooling.
Use: this carried catalyst is placed photo catalysis reactor, and the aqueous solution that will contain biconjugate chloro-phenyl-trichloroethane injects wherein, turn on agitator under UV-irradiation, can make the biconjugate chloro-phenyl-trichloroethane degraded 93% in the aqueous solution in 60 minutes.
Embodiment 5
With molecular-weight average be 90000, alcoholysis degree is that 80% pva powder is slowly adding in the zero(ppm) water under constantly stirring; The mass ratio of Vilaterm alcohol and water is 1: 45; Be warmed up to 90 ℃ after the abundant swelling of Z 150PH; Under constantly stirring, the median size that ultrasonic dispersing is crossed is the La of 40 nanometers
2O
3, Fe
2O
3Add in the above-mentioned mixed solution with the NiO powder, continue to stir 3 hours, form even colloidal solution.Constant temperature in the above-mentioned solution of cleaning of ceramic matrix material (can be different shape) immersion was left standstill 2 hours; Taking-up was toasted 0.5 hour under 230 ℃ of temperature; Making the ceramic matrix material surface form thickness is the catalyst film of 50～200 nanometers, promptly gets carried catalyst behind the naturally cooling.
Use: this carried catalyst is placed photo catalysis reactor, and the aqueous solution that will contain biconjugate chloro-phenyl-trichloroethane injects wherein, turn on agitator under UV-irradiation, can make the biconjugate chloro-phenyl-trichloroethane degraded 92% in the aqueous solution in 70 minutes.
Claims (2)
1. the method for biconjugate chloro-phenyl-trichloroethane agricultural chemicals agricultural chemicals in the photocatalytic degradation water is characterized in that to be loaded with nanometer La
2O
3, Fe
2O
3With the PVA (PVOH) FILM of NiO composite oxides be carried catalyst, this carried catalyst is placed the photo catalysis reactor that fills the pending aqueous solution, under UV-irradiation, can the biconjugate chloro-phenyl-trichloroethane agricultural chemicals agricultural chemicals in the water be decomposed; The preparation method of carried catalyst is: with molecular-weight average be 80000～90000, alcoholysis degree is that 70%～80% pva powder is slowly adding in the zero(ppm) water under constantly stirring; The mass ratio of Vilaterm alcohol and water is 1: 20～50; Be warmed up to 90 ℃ after the abundant swelling of Z 150PH; Under constantly stirring, the La that ultrasonic dispersing is crossed
2O
3, Fe
2O
3Add in the above-mentioned mixed solution with the NiO powder, continue to stir 2～3 hours, form even colloidal solution; The ceramic matrix material of cleaning immersed constant temperature left standstill 1～3 hour in the above-mentioned solution, take out and under 180～230 ℃ of temperature, toasted 0.5～1.5 hour, making the ceramic matrix material surface form thickness is the catalyst film of 50～200 nanometers, promptly gets after the cooling.
2. the method for biconjugate chloro-phenyl-trichloroethane agricultural chemicals agricultural chemicals is characterized in that described La in the photocatalytic degradation water according to claim 1
2O
3, Fe
2O
3With the particle diameter of NiO powder be 20～40nm.
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| CN2011103497525A CN102807263B (en) | 2011-11-08 | 2011-11-08 | Method for degrading 2,2-bis(p-chlorophenyl)-1,1,1-trichloroethane pesticide in water by photocatalysis |
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|---|---|---|---|
| CN2011103497525A CN102807263B (en) | 2011-11-08 | 2011-11-08 | Method for degrading 2,2-bis(p-chlorophenyl)-1,1,1-trichloroethane pesticide in water by photocatalysis |
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| CN102807263A true CN102807263A (en) | 2012-12-05 |
| CN102807263B CN102807263B (en) | 2013-12-11 |
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| CN107744838A (en) * | 2017-10-16 | 2018-03-02 | 辽宁大学 | A kind of photochemical catalyst that catalytic activity is respectively provided with visible region and ultraviolet region and its preparation method and application |
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| CN107744838A (en) * | 2017-10-16 | 2018-03-02 | 辽宁大学 | A kind of photochemical catalyst that catalytic activity is respectively provided with visible region and ultraviolet region and its preparation method and application |
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| CN102807263B (en) | 2013-12-11 |
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