CN1636882A - Irradiation method of degrading hexachlorobenzene in water - Google Patents

Irradiation method of degrading hexachlorobenzene in water Download PDF

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CN1636882A
CN1636882A CN200410065466.6A CN200410065466A CN1636882A CN 1636882 A CN1636882 A CN 1636882A CN 200410065466 A CN200410065466 A CN 200410065466A CN 1636882 A CN1636882 A CN 1636882A
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perchlorobenzene
irradiation
water body
water
utilizing
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CN1277755C (en
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郑正
顾春晖
杨光俊
周忻
王灿
袁守军
帖靖玺
江芳
郭照冰
唐登勇
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Nanjing University
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Abstract

The irradiation method of degrading hexachlorobenzene in water is one high efficiency energy saving water treating technology. High energy electron beam or gamma ray radiated during the decay of radioactive atom is utilized to treat water containing hexachlorobenzene for degrading hexachlorobenzene.

Description

Utilize the method for Perchlorobenzene in the irradiation-induced degradation water body
Technical field
The present invention relates to the method for Perchlorobenzene in a kind of water body of degrading, the method for specifically utilizing irradiation that the Perchlorobenzene in the water body is degraded.
Background technology
Calendar year 2001, by United Nations Environment Programme (UNEP) (UNEP) tissue, in the council of ministers of Sweden, signed the international law constraint treaty of 12 kinds of typical persistence organic compound of a control (POPs), China is one of signatory country.
United Nations Environment Programme (UNEP) (UNEP) carried out Global Environment Facility's project evaluation of relevant PTS in 2000, the expert is consistent to be thought to speak with simple word and defines the persistence Toxic, though these materials are enjoyed following general character really: organic (comprising that metal is organic) material; Slowly degraded in environment; Biology gathers; Has toxicity.
Perchlorobenzene is one of 12 kinds of listed POPs of above-mentioned pact, also is a kind of typical PTS.It is carcinogenic substance that Perchlorobenzene is confirmed to be, and human health and environment are all had serious harm, no matter still is listed on " Black List " of priority pollutants in the equal name of European Union in the U.S..Perchlorobenzene once generally was used for all types of industries production and pesticide producing, intermediate as organic synthesis, the sterilant and the wood preservative of seed are used for organic synthesis, can also be used to produce Pentachlorophenol, fluorocarbon and paper dipping,, the use of agricultural chemicals simultaneously makes Perchlorobenzene form pollution of area source.The approach that Perchlorobenzene enters environment comprises waste water, air and the stack gas of Incineration of waste generation and the release of flying dust that contains these products, thereby Perchlorobenzene is distributed widely in the environment.
The chemical property of Perchlorobenzene is stable, is difficult to biological degradation, and is lasting in environment.To mainly be present in the vapor phase after being discharged into atmosphere, degraded is slow (being estimated as 2 years with the transformation period of hydroxyl free radical reaction) extremely, and the whole world migration of long distance can take place.Wet deposition and the dry deposition Perchlorobenzene in can the physical removal atmosphere.After entering water body, Perchlorobenzene will obviously be assigned in bed mud and the suspended substance.It volatilizees very fast from water, and still the strong adsorption with bed mud causes its persistence very strong. and Perchlorobenzene biomagnification in the fish body enters food chain (the food market investigation is found can detect in the food).The mankind can be exposed to Perchlorobenzene by ambient air, contaminated tap water and food, polluted soil and occupational environment.
The standard value of Perchlorobenzene is for being no more than 0.01 μ g/L in The World Health Organization's suggestion tap water.China's Perchlorobenzene at present also has production, also is being used as chemical intermediate.
Owing at present time decades has been carried out in the research of 12 kinds of typical POPs both at home and abroad, we can be generalized to a lot of achievements in research in the research and improvement of other persistence Toxics modestly, but simultaneously, concrete material also needs concrete analysis.Chlorobenzene compound is compared with arene compounds, biodegradability reduces greatly, along with increasing of chlorine substituent, the activity of chlorobenzene compound reduces one by one, Perchlorobenzene is minimum, major cause is that high electronegative chlorine atom makes phenyl ring become a very difficult oxidized electrophobic ring, so Perchlorobenzene almost can not be biochemical.Have the scholar to find that the microorganism in the specific mud had certain removal effect to Perchlorobenzene, but it is subjected to environmental influence bigger.Perchlorobenzene is very insensitive to illumination, and what Degradation illumination does not almost have to Perchlorobenzene.Polystream, particularly Perchlorobenzene have very high thermostability, are difficult to destroyed.Moreover, when containing the urban solid garbage of Perchlorobenzene, burning disposal also can produce another kind of high toxicity pollution substance-Dioxins.This shows that the Perchlorobenzene chemical property is highly stable, handle very difficulty.Carry out big quantity research both at home and abroad for the degraded and the removal of Perchlorobenzene at present, but also do not had special ideal method.
In sum, for the Perchlorobenzene of one of generally acknowledged 12 kinds of POPs that seriously jeopardize human health and environment in the whole world and typical PTS, it is very urgent to research and develop a kind of comparatively ideal effective treating method.
Summary of the invention
The objective of the invention is the problem that exists at above-mentioned prior art, the method for the Perchlorobenzene in a kind of method degraded water body that utilizes irradiation is provided, is a kind of water technology of high-efficiency and energy-saving type.
Technical scheme of the present invention:
A kind of method of utilizing Perchlorobenzene in the irradiation-induced degradation water body, its gamma-rays that radiates when adopting high-power electron beam or radioactive atom decay is handled the water body that contains Perchlorobenzene, and the Perchlorobenzene in the water body is degraded.
Wherein irradiation source is a radionuclide 60Co or 137Cs, irradiation dose is high more simultaneously, and degradation rate is high more;
Wherein high-power electron beam is produced by high-energy electron accelerator;
Wherein water body is the tap water water body;
Higher pH value has promoter action to the irradiation effect.Under the identical situation of other condition, pH value is high more, and degradation rate is high more, and treatment effect is good more.
Wherein in the water body at CO 3 2-Concentration is higher to have promoter action to the irradiation effect.Under the identical situation of other condition, carbonate concentration is high more, and degradation rate is high more, and treatment effect is good more.
Along with more concerns are dropped into to persistence organic pollutant (POPs) and the staying quality poison material (PTS) that enters the difficult degradation in the environment in countries in the world, the new technology of developing a kind of toxic organic compound of degrading just becomes more and more urgent, is exactly to produce under these circumstances radiation application in the processing of this type of material.
The gamma-rays that radiates during the radioactive atom decay has great penetrating force, and industrial modal irradiation source is a radionuclide 60Co and 137Cs is used for the processing of water and mud.And the controllability of high-power electron beam is good, and speed of reaction is fast, and penetration power is strong, has realized industrial applications at home and abroad.There are some researches show that high-power electron beam and gamma-radiation there is no remarkable difference to the effect of compound in the water body.High-power electron beam and gamma-rays can both produce the similar activity intermediate, and major different is that the gamma-ray dosage release rate in cobalt source is relatively low.The research that utilizes radiotechnology that waste water is handled has been carried out the long period abroad, studies show that gamma-rays and electron beam to containing the waste water of heavy metal, and phenolic wastewater, cyanide wastewater, industry contain anthracene, the quinone waste water from dyestuff all has the good treatment effect.Relevant report is few both at home and abroad at present to be applied to the processing of tap water for gamma-rays and electron beam irradiation.
It is basic identical that high-power electron beam and gamma-rays enter the reaction that water body takes place, after high-power electron beam or gamma-rays enter water body, 10 -7With water molecules following reaction taking place in second generates various active substances:
Figure A20041006546600051
During the energy of the every absorption of the numeral in bracket 100eV, the quantity of the various free radicals that produce in the water.Table 1-1 has listed main active substances and the concentration under different irradiation doses thereof that produces in the irradiation.Irradiation is exactly that the moment and the water molecule reaction that utilize high-energy electron or gamma-rays to enter water body produce active free radical e Aq -, OH, H etc. handles waste water.These free radicals OH, H, e Aq -All be the high reactivity material, can be rapidly with water body in organism react, thereby reach the organic purpose of Degradation and Transformation.Because OH and e that reaction produces Aq -Quantity is suitable substantially, also can be reductive action so the removal of pollutent can be an oxygenizement, and this depends primarily on concentration, chemical structure and the condition of water quality of pollutent.OH is a typical oxidizing agents, its standard oxidation also original position up to 2.80V, be only second to fluorine (2.87V), it is the present known the strongest oxygenant that can in water treatment, use, it is as the intermediate product of reaction, can bring out the chain reaction of back, and in OH and the water most organic reaction velocity constants all 10 8~10 10M -1S -1Order of magnitude scope mainly is addition and proposes H-H reaction with the organism reaction.Addition mainly is and the organism that contains unsaturated link(age), as contains the organism of ethylene linkage and aromatic ring.Proposing H-H reaction mainly is and saturated fatty compounds of group and the reaction of many unsaturated compounds, as aldehydes and ketone organism.
The invention has the advantages that:
Carry out big quantity research both at home and abroad for the degraded and the removal of Perchlorobenzene at present, but also do not had special ideal method.And irradiation is the unique both high equal strong oxidizer and technology of strong reductant of being close to of generation concentration in aqueous systems simultaneously.
Compare with other traditional treatment method, irradiation technique has following advantage: the standard oxidation of the free radical OH that produces in the reaction also original position up to 2.80V, be only second to fluorine (2.87V), be the present known the strongest oxygenant that can in water treatment, use, and in OH and the water most organic reaction velocity constants all 10 8~10 10M -1S -1Order of magnitude scope [46]It can bring out the chain reaction of back as the intermediate product of reaction; OH does not have selectively direct and the pollutants in waste water reaction is degraded to carbonic acid gas, water and mineral salt with it, can not produce secondary pollution; Because it is a kind of physical chemical process, be easy to be controlled, handle needs to satisfy, even can degrade 10 -9M -1S -1The pollutent of level; It. both can be used as individual curing, can be complementary with other treating processes again,, satisfied processing requirements to reduce cost; The reaction conditions gentleness is a kind of water technology of high-efficiency and energy-saving type.Can reach clearance on 80% with the Perchlorobenzene in the method for the irradiation degraded water body.
Embodiment
Embodiment 1: the conventional water body that contains the Perchlorobenzene of 0.4mg/L, through 1.5MeV, the high-power electron beam that the high-energy electron accelerator of 50mA produces is under the irradiation dose of 2kGy, Perchlorobenzene can reach the degradation rate more than 80%, and degraded product does not contain other harmful chlorobenzene compound substantially.Higher pH value has promoter action to the irradiation effect, therefore, under the higher situation of pH value, can consider to reduce irradiation dose to reduce processing cost in water body.
Embodiment 2: when the irradiation dose among the embodiment 1 changes 10kGy into, can reach degradation rate more than 90% to Perchlorobenzene.But the irradiation cost significantly improves, and should look various places drinking water treatment requirement and choose irradiation dose.
Embodiment 3: it is 500 that the irradiation among the embodiment 1 adopts source strength, 000Ci 60The Co ray carries out irradiation, and other condition is constant, and degradation effect is constant substantially.
Embodiment 4: it is 500 that the irradiation among the embodiment 2 adopts source strength, 000Ci 60The Co ray carries out irradiation, and other condition is constant, and degradation effect is constant substantially
Embodiment 5: in embodiment 1 and the example 2, in the water body at CO 3 2-Under the concentration condition with higher, the irradiation effect is had promoter action, the irradiation dose of can suitably degrading.

Claims (6)

1, a kind of method of utilizing Perchlorobenzene in the irradiation-induced degradation water body, its gamma-rays that radiates when adopting high-power electron beam or radioactive atom decay is handled the water body that contains Perchlorobenzene, and the Perchlorobenzene in the water body is degraded.
2, the method for utilizing Perchlorobenzene in the irradiation-induced degradation water body according to claim 1, wherein irradiation source is a radionuclide 60Co or 137Cs.
3, the method for utilizing Perchlorobenzene in the irradiation-induced degradation water body according to claim 1, wherein high-power electron beam is produced by high-energy electron accelerator.
4, the method for utilizing Perchlorobenzene in the irradiation-induced degradation water body according to claim 1, wherein water body is the tap water water body.
5, the method for utilizing Perchlorobenzene in the irradiation-induced degradation water body according to claim 1, higher pH value has promoter action to the irradiation effect.
6, the method for utilizing Perchlorobenzene in the irradiation-induced degradation water body according to claim 1, wherein in the water body at CO 3 2-Concentration is higher to have promoter action to the irradiation effect.
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102219280A (en) * 2011-04-30 2011-10-19 南京大学 Method for removing high-concentration dimethyl phthalate through radiation
CN101746872B (en) * 2009-10-23 2012-11-07 湖北省农业科学院农产品加工与核农技术研究所 60Cogamma-ray irradiation for degrading five fish drugs of chloramphenicol, sulphadimidine, terramycin, oxolinic acid and furazolidone
CN103145213A (en) * 2013-03-20 2013-06-12 中国科学院高能物理研究所 Method for treating furaltadone-containing wastewater
CN107212111A (en) * 2017-06-21 2017-09-29 四川治生科技有限公司 The method that high energy X x ray irradiation x removes Pesticide Residues in Tea thing
CN109607792A (en) * 2019-02-20 2019-04-12 中广核达胜加速器技术有限公司 The anaerobic- anoxic- oxic biological denitrification phosphorous removal technique improved using electron beam irradiation
CN110372064A (en) * 2019-07-19 2019-10-25 常熟理工学院 A method of medical waste liquid is handled using electronic beam irradiation technology
CN110449453A (en) * 2019-09-19 2019-11-15 陈葆良 A kind of restorative procedure of organic material contaminated soil
CN111115745A (en) * 2019-11-21 2020-05-08 清华大学 Method for degrading organic pollutants in water by ionizing radiation

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101746872B (en) * 2009-10-23 2012-11-07 湖北省农业科学院农产品加工与核农技术研究所 60Cogamma-ray irradiation for degrading five fish drugs of chloramphenicol, sulphadimidine, terramycin, oxolinic acid and furazolidone
CN102219280A (en) * 2011-04-30 2011-10-19 南京大学 Method for removing high-concentration dimethyl phthalate through radiation
CN102219280B (en) * 2011-04-30 2013-08-07 南京大学 Method for removing high-concentration dimethyl phthalate through radiation
CN103145213A (en) * 2013-03-20 2013-06-12 中国科学院高能物理研究所 Method for treating furaltadone-containing wastewater
CN107212111A (en) * 2017-06-21 2017-09-29 四川治生科技有限公司 The method that high energy X x ray irradiation x removes Pesticide Residues in Tea thing
CN109607792A (en) * 2019-02-20 2019-04-12 中广核达胜加速器技术有限公司 The anaerobic- anoxic- oxic biological denitrification phosphorous removal technique improved using electron beam irradiation
CN110372064A (en) * 2019-07-19 2019-10-25 常熟理工学院 A method of medical waste liquid is handled using electronic beam irradiation technology
CN110372064B (en) * 2019-07-19 2022-01-28 常熟理工学院 Method for treating medical waste liquid by using electron beam irradiation technology
CN110449453A (en) * 2019-09-19 2019-11-15 陈葆良 A kind of restorative procedure of organic material contaminated soil
CN111115745A (en) * 2019-11-21 2020-05-08 清华大学 Method for degrading organic pollutants in water by ionizing radiation

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