CN102807263B - 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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- CN102807263B CN102807263B CN2011103497525A CN201110349752A CN102807263B CN 102807263 B CN102807263 B CN 102807263B CN 2011103497525 A CN2011103497525 A CN 2011103497525A CN 201110349752 A CN201110349752 A CN 201110349752A CN 102807263 B CN102807263 B CN 102807263B
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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 photocatalytic degradation water, belong 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 the agricultural-food such as China's grain, vegetables, fruit, tealeaves and medicinal material.But, due to people to agricultural chemicals the characteristics of motion in the nature biotechnology body, the acquisition of knowledge of aspects such as pathways metabolism, degraded mode and residual savings is inadequate, when the enjoyment chemical pesticide brings good harvest happy, has usually ignored its residual harm brought.
Biconjugate chloro-phenyl-trichloroethane (Dichlorodiphenyltrichloroethane) is again dichlorodiphenyl trichloroethane (DDT), chemical formula (ClC
6h
4)
2cH (CCl
3), be white crystal, water insoluble, be dissolved in kerosene, can be made into emulsion, be effective sterilant.Be that 20 th Century prevent agricultural pest, alleviate the fly-borne disease harm of the mosquito such as malaria typhoid fever and play a significant role.DDT is strangled in 1874 first and is synthesized by the diligent moral of Ou Tema, but this compound has the characteristic of sterilant effect, is but nineteen thirty-nine just by Miller, to be realized out.This product is almost all very effective to all insects.During World War II, the use range of DDT has obtained rapidly expansion, and is exhibiting one's skill to the full aspect the treatment of the diseases such as malaria, dysentery, has given treatment to a lot of life, but also has brought the volume increase of farm crop.But find dichlorodiphenyl trichloroethane 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 dichlorodiphenyl trichloroethane, the birds body includes dichlorodiphenyl trichloroethane and can cause producing soft shelled egg and can not hatch, and especially therefore the bird of prey in the food chain climax almost becomes extinct as U.S. national bird white-crowned sea eagle.1962, American scientist Lei Qieerkaxun suspected that in its works " silent spring " it is to cause the bird of some food meat and ichthyophagy to approach the major cause of becoming extinct that DDT enters food chain.Therefore from the seventies, dichlorodiphenyl trichloroethane is prohibited and is produced and use by countries in the world gradually.DDT can accumulate for a long time in body fat, be proved and can have upset biological hormone secretion, " epidemiology " magazine of calendar year 2001 is mentioned, and scientist, by 24 16 to 28 years old Mexico man's of selective examination blood sample, has confirmed that in human body, the rising of DDT level can cause sperm number to reduce first.In addition, the increase of neonatal premature labor and nascent body weight also has certain contact with DDT, and existing medical research has also shown that it is influential to the mankind's liver function and form, and obvious carcinogenic performance is arranged.
Set up a kind of method of energy rapid conversion biconjugate chloro-phenyl-trichloroethane agricultural chemicals, not only be conducive to protection of the environment, and can effectively process the aqueous extract of many agricultural-food, for the standard of living that improves us provides safeguard.All more or less there are some defects in the degradation method of at present common biconjugate chloro-phenyl-trichloroethane agricultural chemicals: (1) utilizes the microbiological deterioration selectivity ratios higher, but the cultivation of bacterial classification bothers very much, when degraded, bacterial classification is very strict to the requirement of temperature, only at it, at best temperature, higher degradation rate is just arranged, extensive utilize more difficult; (2) utilize the ozone oxidation degraded to have broad spectrum, but also can destroy effective constituent simultaneously, therefore relatively be applicable to Industrial Wastewater Treatment, the required time of degrading in addition is long, and the manufacturing expense of ozone is higher.(3) utilize the mechanical ball milling dechlorination to be applicable to solid powder substance, normally in argon atmosphere by CaO together with the pastille mixing of materials, ball milling in cylinder of steel, after more than ten hour, can substantially remove the agricultural chemicals in material, this method length consuming time, somewhat expensive, applicable surface is narrow; (4) utilize Photocatalyst to have a extensive future, the electronics-hole with redox ability that this method utilizes photocatalyst to produce under action of ultraviolet light, to target compound is effectively decomposed, utilizes nano-TiO mostly in document
2aqeous suspension carry out 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 and to be produced even thus secondary pollution, 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 conventional art, the method for biconjugate chloro-phenyl-trichloroethane agricultural chemicals in the high efficiency photocatalytic degradation water of a kind of high selection is provided.Process in this way the aqueous solution containing biconjugate chloro-phenyl-trichloroethane agricultural chemicals, but there is degradation speed, soon, do not destroy effective constituent, non-secondary pollution, catalyzer Reusability and the characteristics such as easy to operate.
In photocatalytic degradation water of the present invention, the method for biconjugate chloro-phenyl-trichloroethane agricultural chemicals is with La
2o
3, Fe
2o
3with the NiO nano composite oxide be catalyzer, using its immobilized in PVA (PVOH) FILM as carried catalyst, this carried catalyst is placed in to the photo catalysis reactor that fills the pending aqueous solution, turn on agitator, under UV-irradiation, the biconjugate chloro-phenyl-trichloroethane agricultural chemicals in the aqueous solution can be decomposed in 90 minutes.The preparation method of carried catalyst is: during the pva powder that molecular-weight average is 80000～90000, alcoholysis degree is 70%～80% is slowly added to distilled water under constantly stirring, the mass ratio of polyethylene alcohol and water is 1: 20～50, be warmed up to 90 ℃ after the abundant swelling of polyvinyl alcohol, under constantly stirring, the La that the particle diameter that ultrasonic wave was disperseed is 20～40 nanometers
2o
3, Fe
2o
3add in above-mentioned mixed solution with the NiO powder, continue to stir 2～3 hours, form even colloidal solution.Clean ceramic matrix material (can be different shape) is immersed in above-mentioned solution to constant temperature standing 1～3 hour, taking-up is toasted 0.5～1.5 hour at 180～230 ℃ of temperature, make ceramic matrix material surface form the catalyst film that thickness is 50～200 nanometers, cooling after and get final product.
The present invention has following distinguishing feature:
(1) carried catalyst stable chemical nature, acidproof, alkaline-resisting, heat-resisting, the life-span is long, can Reusability, can not cause secondary pollution;
(2) good to biconjugate chloro-phenyl-trichloroethane degradation of pesticide selectivity, the general biconjugate chloro-phenyl-trichloroethane agricultural chemicals 90% or more in UV-irradiation can be removed the aqueous solution in 90 minutes, other effective constituents are almost not variation;
(3) the inventive method both can be used for processing the various waste water containing 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
During the pva powder that molecular-weight average is 80000, alcoholysis degree is 80% is slowly added to distilled water under constantly stirring, the mass ratio of polyethylene alcohol and water is 1: 30, be warmed up to 90 ℃ after the abundant swelling of polyvinyl alcohol, under constantly stirring, the La that the median size that ultrasonic wave was disperseed is 30 nanometers
2o
3, Fe
2o
3add in above-mentioned mixed solution with the NiO powder, continue to stir 2 hours, form even colloidal solution.Clean ceramic matrix material (can be different shape) is immersed in above-mentioned solution to constant temperature standing 2 hours, taking-up is toasted 1 hour at 190 ℃ of temperature, make the ceramic matrix material surface form the catalyst film that thickness is 50～200 nanometers, obtain carried catalyst after naturally cooling.
Application: this carried catalyst is placed in to 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
During the pva powder that molecular-weight average is 90000, alcoholysis degree is 70% is slowly added to distilled water under constantly stirring, the mass ratio of polyethylene alcohol and water is 1: 40, be warmed up to 90 ℃ after the abundant swelling of polyvinyl alcohol, under constantly stirring, the La that the median size that ultrasonic wave was disperseed is 25 nanometers
2o
3, Fe
2o
3add in above-mentioned mixed solution with the NiO powder, continue to stir 3 hours, form even colloidal solution.Clean ceramic matrix material (can be different shape) is immersed in above-mentioned solution to constant temperature standing 1 hour, taking-up is toasted 0.5 hour at 200 ℃ of temperature, make the ceramic matrix material surface form the catalyst film that thickness is 50～200 nanometers, obtain carried catalyst after naturally cooling.
Application: this carried catalyst is placed in to 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
During the pva powder that molecular-weight average is 85000, alcoholysis degree is 75% is slowly added to distilled water under constantly stirring, the mass ratio of polyethylene alcohol and water is 1: 25, be warmed up to 90 ℃ after the abundant swelling of polyvinyl alcohol, under constantly stirring, the La that the median size that ultrasonic wave was disperseed is 35 nanometers
2o
3, Fe
2o
3add in above-mentioned mixed solution with the NiO powder, continue to stir 2 hours, form even colloidal solution.Clean ceramic matrix material (can be different shape) is immersed in above-mentioned solution to constant temperature standing 3 hours, taking-up is toasted 1.5 hours at 210 ℃ of temperature, make the ceramic matrix material surface form the catalyst film that thickness is 50～200 nanometers, obtain carried catalyst after naturally cooling.
Application: this carried catalyst is placed in to 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
During the pva powder that molecular-weight average is 80000, alcoholysis degree is 70% is slowly added to distilled water under constantly stirring, the mass ratio of polyethylene alcohol and water is 1: 40, be warmed up to 90 ℃ after the abundant swelling of polyvinyl alcohol, under constantly stirring, the La that the median size that ultrasonic wave was disperseed is 32 nanometers
2o
3, Fe
2o
3add in above-mentioned mixed solution with the NiO powder, continue to stir 3 hours, form even colloidal solution.Clean ceramic matrix material (can be different shape) is immersed in above-mentioned solution to constant temperature standing 1.5 hours, taking-up is toasted 1 hour at 220 ℃ of temperature, make the ceramic matrix material surface form the catalyst film that thickness is 50～200 nanometers, obtain carried catalyst after naturally cooling.
Application: this carried catalyst is placed in to 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
During the pva powder that molecular-weight average is 90000, alcoholysis degree is 80% is slowly added to distilled water under constantly stirring, the mass ratio of polyethylene alcohol and water is 1: 45, be warmed up to 90 ℃ after the abundant swelling of polyvinyl alcohol, under constantly stirring, the La that the median size that ultrasonic wave was disperseed is 40 nanometers
2o
3, Fe
2o
3add in above-mentioned mixed solution with the NiO powder, continue to stir 3 hours, form even colloidal solution.Clean ceramic matrix material (can be different shape) is immersed in above-mentioned solution to constant temperature standing 2 hours, taking-up is toasted 0.5 hour at 230 ℃ of temperature, make the ceramic matrix material surface form the catalyst film that thickness is 50～200 nanometers, obtain carried catalyst after naturally cooling.
Application: this carried catalyst is placed in to 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 in a photocatalytic degradation water, is characterized in that being 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 in to the photo catalysis reactor that fills the pending aqueous solution, under UV-irradiation, the biconjugate chloro-phenyl-trichloroethane agricultural chemicals in water can be decomposed; The preparation method of carried catalyst is: during the pva powder that molecular-weight average is 80000～90000, alcoholysis degree is 70%～80% is slowly added to distilled water under constantly stirring, the mass ratio of polyethylene alcohol and water is 1:20～50, be warmed up to 90 ℃ after the abundant swelling of polyvinyl alcohol, under constantly stirring, the La that ultrasonic wave was disperseed
2o
3, Fe
2o
3add in above-mentioned mixed solution with the NiO powder, continue to stir 2～3 hours, form even colloidal solution; Clean ceramic matrix material is immersed in above-mentioned solution to constant temperature standing 1～3 hour, takes out and toast 0.5～1.5 hour at 180～230 ℃ of temperature, make the ceramic matrix material surface form the catalyst film that thickness is 50～200 nanometers, cooling after and get final product.
2. the method for biconjugate chloro-phenyl-trichloroethane agricultural chemicals in photocatalytic degradation water according to claim 1, is characterized in that described La
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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| CN102807263B true CN102807263B (en) | 2013-12-11 |
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| CN103349111A (en) * | 2013-07-23 | 2013-10-16 | 华南农业大学 | Method for reducing imidacloprid residue in tea drinks |
| CN103926358A (en) * | 2014-03-17 | 2014-07-16 | 湖南工程学院 | Method for simulating transformation mechanism of reactive oxygen species acting on aromatic pesticides in water environment |
| 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 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004323459A (en) * | 2003-04-28 | 2004-11-18 | Toshiba Corp | Method for decomposing organic halogen compound |
| WO2008148363A2 (en) * | 2007-06-07 | 2008-12-11 | Rokospol A.S. | An agent for surface finishing of objects and strustures by a coating layer with a photocatalytic and self-cleaning effect and respective manufacturing process |
| CN101400374A (en) * | 2006-03-14 | 2009-04-01 | 3M创新有限公司 | Photocatalytic substrate with biocidal coating |
| CN101780952A (en) * | 2010-03-26 | 2010-07-21 | 上海交通大学 | Method for preparing loading functional oxide porous carbon |
| CN101966459A (en) * | 2010-09-03 | 2011-02-09 | 天津工业大学 | Hydroxyl nickel (iron)-oxide photocatalyst with visible light response and preparation method thereof |
| CN102120631A (en) * | 2010-12-07 | 2011-07-13 | 北京联合大学生物化学工程学院 | Photocatalytic degradation method of pyrethroid pesticide in water |
-
2011
- 2011-11-08 CN CN2011103497525A patent/CN102807263B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004323459A (en) * | 2003-04-28 | 2004-11-18 | Toshiba Corp | Method for decomposing organic halogen compound |
| CN101400374A (en) * | 2006-03-14 | 2009-04-01 | 3M创新有限公司 | Photocatalytic substrate with biocidal coating |
| WO2008148363A2 (en) * | 2007-06-07 | 2008-12-11 | Rokospol A.S. | An agent for surface finishing of objects and strustures by a coating layer with a photocatalytic and self-cleaning effect and respective manufacturing process |
| CN101780952A (en) * | 2010-03-26 | 2010-07-21 | 上海交通大学 | Method for preparing loading functional oxide porous carbon |
| CN101966459A (en) * | 2010-09-03 | 2011-02-09 | 天津工业大学 | Hydroxyl nickel (iron)-oxide photocatalyst with visible light response and preparation method thereof |
| CN102120631A (en) * | 2010-12-07 | 2011-07-13 | 北京联合大学生物化学工程学院 | Photocatalytic degradation method of pyrethroid pesticide in water |
Non-Patent Citations (8)
| Title |
|---|
| Chitsan Lin et al.Photocatalytic oxidation of toxic organohalides with TiO2/UV: The effects of humic substances and organic mixtures.《CHEMOSPHERE》.2006,第66卷(第10期),第1872-1877页. |
| Photocatalytic oxidation of toxic organohalides with TiO2/UV: The effects of humic substances and organic mixtures;Chitsan Lin et al;《CHEMOSPHERE》;20061107;第66卷(第10期);第1872-1877页 * |
| 农药光催化降解研究进展;陈小军等;《农药光催化降解研究进展》;20060630;第45卷(第6期);第381-384页 * |
| 朱静等.镧镍复合氧化物催化剂及其光催化活性的研究.《工业催化》.2006,第14卷(第3期),摘要，第49页1.2光催化降解反应体系，第50页2.1.2 TEM、2.2.1 催化剂用量对降解甲基橙的影响，图2、图4. |
| 王仲民等.纳米TiO2薄膜光催化性能的研究进展.《桂林电子工业学院学报》.2004,第24卷(第4期),第14页引言. |
| 纳米TiO2薄膜光催化性能的研究进展;王仲民等;《桂林电子工业学院学报》;20040831;第24卷(第4期);第14页引言 * |
| 镧镍复合氧化物催化剂及其光催化活性的研究;朱静等;《工业催化》;20060331;第14卷(第3期);摘要，第49页1.2光催化降解反应体系，第50页2.1.2 TEM、2.2.1 催化剂用量对降解甲基橙的影响，图2、图4 * |
| 陈小军等.农药光催化降解研究进展.《农药光催化降解研究进展》.2006,第45卷(第6期),第381-384页. |
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