CN103626277B - Be applicable to the Ex-situ remediation method of chloronitrobenzene class polluted underground water - Google Patents
Be applicable to the Ex-situ remediation method of chloronitrobenzene class polluted underground water Download PDFInfo
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- CN103626277B CN103626277B CN201310419885.4A CN201310419885A CN103626277B CN 103626277 B CN103626277 B CN 103626277B CN 201310419885 A CN201310419885 A CN 201310419885A CN 103626277 B CN103626277 B CN 103626277B
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Abstract
The invention discloses a kind of Ex-situ remediation method being applicable to chloronitrobenzene class polluted underground water.The method is: sewage first filters removal mechanical impurity, then adds reduced iron powder stirring reaction, and add-on is the 30-40% of COD content, and Zero-valent Iron deoxygenization chlorination oil of mirbane generates ferrous ion Fe
2+and aniline; After reduction reaction 3-5 days, add FeSO
47H
2o, addition is 30% of COD content, is stirred to miscible; Be the hydrogen peroxide (H of 30% again by mass concentration
2o
2) to be progressively added in reaction soln by the 3-5 dosage doubly of COD content and to carry out oxidizing reaction, ferrous ion is oxidized to ferric ion; Ca (OH) is added by the amount of the 0.1-0.2% of sewage solution quality after oxidizing reaction terminates
2displace ferric ion, and regulate pH to 6-9; Last filtering separation removes throw out.Zero-valent Iron reduction treatment method and Fenton reagent oxidizing treatment are combined by the present invention, and obvious to the repairing effect of chloronitrobenzene class polluted underground water, pollutants removal rate is high.
Description
Technical field
The invention belongs to polluted underground water repairing and treating technical field, relate to a kind of Ex-situ remediation method being applicable to chloronitrobenzene class polluted underground water.
Background technology
Chloro monoitrotoluenes is widely used in national defence, printing and dyeing, plastics, agricultural chemicals and medicine industry, the whole world enters chloro nitrotoluene in environment every year more than 100t, very large harm is caused to ecotope, this compounds multiple is classified as priority pollutants by Environmental Protection Agency, and in strict control water body, chloro nitrotoluene content has realistic meaning.Chloro monoitrotoluenes phenyl ring electronic cloud is intensive, is difficult to provide electronics, and it is more difficult that logical snperoxiaized method removes chloronitrobenzene compounds.Such as, and oxidation chloronitrobenzene may produce more hazardous and noxious substances, picolinic acid.Therefore, remove chloro nitrotoluene by the method for reduction to receive much concern.
The pollutent using the zero-valent metal of reductibility to remove in water body is a kind of new pollutant control technology grown up recent years.Reduced iron powder is the most frequently used reducing metal, other zinc, aluminium, nickel, calcium, magnesium etc. in addition.Because reduced iron powder is cheap and easy to get and harmless, and technique is simple, cost is low, has greatly promoted the application of zero-valent metal reduction technique in process water pollutant.
Due in chloronitrobenzene class polluted underground water mostly with petroleum hydrocarbon class pollutant, and Zero-valent Iron Fe
0limited to the degradation capability of total petroleum hydrocarbon compounds, therefore, directly with reduced iron powder process chloronitrobenzene class polluted underground water limited efficiency.
Fenton reagent (ferrous ion and hydrogen peroxide, wherein hydrogen peroxide and hydrogen peroxide are a kind of strong oxidizers) has been widely used in commercial synthesis and water treatment procedure.When decomposing in water body, hydrogen peroxide can produce multiple free radical and active substance, can effective decomposing organic matter (see formula 1).
Formula 1:Fe
2++ H
2o
2→ Fe
3++ OH
-+ OH
Fenton reagent treatment of Nitrobenzene class waste water is utilized to have been reported, if but containing chloronitrobenzene pollutant in waste water, directly just more difficult by Fenton reagent oxide treatment.
Summary of the invention
The object of the invention is to: overcome the deficiencies in the prior art, there is provided a kind of repairing effect to chloronitrobenzene class polluted underground water Zero-valent Iron reduction treatment method and Fenton reagent oxidizing treatment are combined obvious, the Ex-situ remediation method of what pollutants removal rate was high be applicable to chloronitrobenzene class polluted underground water.
Design of the present invention is as follows: (one) utilizes Zero-valent Iron (Fe
0) deoxygenization chlorination oil of mirbane generation ferrous ion (Fe
2+) and toxicity is lower, the aniline that is easy to oxidation removal; (2) Fenton reagent in acid condition, is utilized to be oxidized aniline and Hydrocarbons; Zero-valent Iron and ferrous ion are all the catalyzer of hydrogen peroxide, and the two all can activate the OH that hydrogen peroxide produces strong oxidizing property, thus fast degradation organism aniline and total petroleum hydrocarbon; (3) Ca (OH) is added in the reaction soln after oxidation
2, adjust ph is to weakly alkaline, and under alkaline environment, ferric ion rapidly and Ca (OH)
2there is ion-exchange and generate yellow Fe (OH)
3precipitation, then effectively removes the iron ion in solution by filtering separation.
The technical solution used in the present invention is as follows:
Be applicable to an Ex-situ remediation method for chloronitrobenzene class polluted underground water, order is carried out as follows:
(1) sewage first filters removal mechanical impurity; (2) add reduced iron powder stirring reaction, add-on is the 30-40% of COD content, reaction times 3-5 days, and Zero-valent Iron deoxygenization chlorination oil of mirbane generates ferrous ion (Fe
2+) and aniline; (3) first FeSO is added
47H
2o, addition is 30% of COD content, is stirred to miscible; Be the hydrogen peroxide (H of 30% again by mass concentration
2o
2) to be progressively added in reaction soln by the 2-3 dosage doubly of COD content and to carry out oxidizing reaction (reaction times is about 1 day), ferrous ion is oxidized to ferric ion; (4), after oxidizing reaction terminates, Ca (OH) is added by the amount of the 0.1-0.2% of sewage solution quality
2displace ferric ion, and regulate pH to 6-9; (5) filtering separation removes throw out.
Beneficial effect of the present invention:
The present invention utilizes Zero-valent Iron (Fe
0) deoxygenization chlorination oil of mirbane generation ferrous ion (Fe
2+) and toxicity is lower, the aniline that is easy to oxidation removal.Zero-valent Iron and ferrous ion are all the catalyzer of hydrogen peroxide, and the two all can activate the OH that hydrogen peroxide produces strong oxidizing property, thus fast degradation organism aniline and total petroleum hydrocarbon.
Zero-valent Iron reduction treatment method and Fenton reagent oxidizing treatment are combined by the present invention, and obvious to the repairing effect of chloronitrobenzene class polluted underground water, pollutants removal rate is high.
Embodiment
Below in conjunction with embodiment, the present invention is further detailed explanation.
Embodiment 1
A kind of Ex-situ remediation method lab scale test being applicable to chloronitrobenzene class polluted underground water of the present invention
One, experimental technique
1, experiment material
Chloro monoitrotoluenes and Hydrocarbons polluted underground water take from place, Shengsi.In sewage, 4-Chloro-2-Nitrobenzene and total petroleum hydrocarbon concentration are respectively 21 and 7.3mgL
-1, COD content is 3620mgL
-1.
Reduced iron powder (the Fe adopted in experimentation
0), hydrogen peroxide (H
2o
2, 30%), iron vitriol (FeSO
47H
2and calcium hydroxide (Ca (OH) O)
2) be analytical pure.
2, experimental implementation
Sewage first filters with 45nm millipore filtration before the experiment, and initial pH is determined as 3.In 1L reaction soln, add 30% of 1g(COD content) Fe
0, react after 5 days, add 1gFeSO
47H
230% of O(COD content), be stirred to miscible, configuration 8g(7mL, 30%; 2.2 times of COD content) H
2o
2and be progressively added in reaction soln, the reaction times is 1 day, and reacted solution ph is 2.2.Reaction terminates rear interpolation Ca (OH)
2(0.1% of sewage solution quality) regulates pH to 6.83.Reaction terminates rear filtering separation, gets supernatant liquor.
Two, experimental result
1, Fe
0deoxygenization chlorination nitrotoluene
In acid condition, Fe
0effectively can generate aniline by deoxygenization chlorination nitrotoluene.After Fe3+ reduction in sewage the concentration of 4-Chloro-2-Nitrobenzene by initial 21mgL
-1degraded is to 0.065mgL
-1, degradation rate is more than 99%.Fe
0ferrous ion (Fe is reduced into from black
2+) be then oxidized to again yellow ferric ion.
In addition, Fe
0limited to the degradation capability of total petroleum hydrocarbon compounds.
2, Fenton oxidation
In acid condition, the oxidable aniline of Fenton reagent and Hydrocarbons.Aniline residual in sewage after Fenton oxidation and Hydrocarbons are all lower than 0.003mgL
-1, the pH of reaction solution is down to 2.2 by initial 3.Also produce with bubble in oxidising process, this is because reacting to each other between hydroxyl radical free radical and hydroxyl radical free radical generates oxygen and hydrogen ion.
3, pH regulator and ferric hydroxide precipitate
After reaction, the iron concentration of solution exceeds standard, and solution ph is 2.2, has exceeded underground water pH and has limited.Therefore, in order to reduce iron concentration and the restriction meeting underground water pH, in the reaction soln after oxidation, with the addition of Ca (OH)
2.Under alkaline environment, ferric ion rapidly and Ca (OH)
2there is ion-exchange and generate yellow Fe (OH)
3precipitation.Add Ca (OH)
2after pH value of solution meet the restriction of underground water pH, and effectively remove the iron ion in solution by filtering separation.
Embodiment 2
1, experiment material
Chloro monoitrotoluenes and Hydrocarbons polluted underground water take from place, Shanghai.In sewage, 4-chloro-2-methyl phenol and total petroleum hydrocarbon concentration are respectively 34 and 12mgL
-1, COD content is 3950mgL
-1.
Reduced iron powder (the Fe adopted in experimentation
0), hydrogen peroxide (H
2o
2, 30%), iron vitriol (FeSO
47H
2and calcium hydroxide (Ca (OH) O)
2) be analytical pure.
2, experimental implementation
Sewage first filters with 45nm millipore filtration before the experiment, and initial pH is determined as 3.2.In 1L reaction soln, add 40% of 1.5g(COD content) Fe
0, react after 3 days, add 1.2gFeSO
47H
230% of O(COD content), be stirred to miscible, configuration 12g(10.5mL, 30%; 3 times of COD content) H
2o
2and be progressively added in reaction soln, the reaction times, reacted solution ph was 2.1 for more than 1 day.Reaction terminates rear interpolation Ca (OH)
2(0.15% of sewage solution quality) regulates pH to 7.3.Reaction terminates rear filtering separation, gets supernatant liquor.
Two, experimental result
1, Fe
0deoxygenization chlorination nitrotoluene
In acid condition, Fe
0effectively can generate aniline by deoxygenization chlorination nitrotoluene.After Fe3+ reduction in sewage the concentration of 4-Chloro-2-Nitrobenzene by initial 34mgL
-1degraded is to 0.079mgL
-1, degradation rate is more than 99%.Fe
0ferrous ion (Fe is reduced into from black
2+) be then oxidized to again yellow ferric ion.
In addition, Fe
0limited to the degradation capability of total petroleum hydrocarbon compounds.
2, Fenton oxidation
In acid condition, the oxidable aniline of Fenton reagent and Hydrocarbons.Aniline residual in sewage after Fenton oxidation and Hydrocarbons are all lower than 0.002mgL
-1, the pH of reaction solution is down to 2.1 by initial 3.2.Also produce with bubble in oxidising process, this is because reacting to each other between hydroxyl radical free radical and hydroxyl radical free radical generates oxygen and hydrogen ion.
3, pH regulator and ferric hydroxide precipitate
After reaction, the iron concentration of solution exceeds standard, and solution ph is 2.1, has exceeded underground water pH and has limited.Therefore, in order to reduce iron concentration and the restriction meeting underground water pH, in the reaction soln after oxidation, with the addition of Ca (OH)
2.Under alkaline environment, ferric ion rapidly and Ca (OH)
2there is ion-exchange and generate yellow Fe (OH)
3precipitation.Add Ca (OH)
2after pH value of solution meet the restriction of underground water pH, and effectively remove the iron ion in solution by filtering separation.
Embodiment 3
1, experiment material
Chloro monoitrotoluenes and Hydrocarbons polluted underground water take from place, Shanghai.In sewage, chloro-2 nitrobenzyl alcohols of 5-and total petroleum hydrocarbon concentration are respectively 26 and 10mgL
-1, COD content is 3790mgL
-1.
Reduced iron powder (the Fe adopted in experimentation
0), hydrogen peroxide (H
2o
2, 30%), iron vitriol (FeSO
47H
2and calcium hydroxide (Ca (OH) O)
2) be analytical pure.
2, experimental implementation
Sewage first filters with 45nm millipore filtration before the experiment, and initial pH is determined as 3.5.In 1L reaction soln, add 35% of 1.3g(COD content) Fe
0, react after 4 days, add 30% of 1.1g(COD content) and FeSO
47H
2o, is stirred to miscible, configuration 8g(7mL, 30%; 2 times of COD content) H
2o
2and be progressively added in reaction soln, in about 1 day reaction times, reacted solution ph is 2.4.Reaction terminates rear interpolation Ca (OH)
2(0.2% of sewage solution quality) regulates pH to 8.5.Reaction terminates rear filtering separation, gets supernatant liquor.
Two, experimental result
1, Fe
0deoxygenization chlorination nitrotoluene
In acid condition, Fe
0effectively can generate aniline by deoxygenization chlorination nitrotoluene.After Fe3+ reduction in sewage the concentration of 4-Chloro-2-Nitrobenzene by initial 26mgL
-1degraded is to 0.067mgL
-1, degradation rate is more than 99%.Fe
0ferrous ion (Fe is reduced into from black
2+) be then oxidized to again yellow ferric ion.
In addition, Fe
0limited to the degradation capability of total petroleum hydrocarbon compounds.
2, Fenton oxidation
In acid condition, the oxidable aniline of Fenton reagent and Hydrocarbons.Aniline residual in sewage after Fenton oxidation and Hydrocarbons are all lower than 0.003mgL
-1, the pH of reaction solution is down to 2.4 by initial 3.5.Also produce with bubble in oxidising process, this is because reacting to each other between hydroxyl radical free radical and hydroxyl radical free radical generates oxygen and hydrogen ion.
3, pH regulator and ferric hydroxide precipitate
After reaction, the iron concentration of solution exceeds standard, and solution ph is 2.4, has exceeded underground water pH and has limited.Therefore, in order to reduce iron concentration and the restriction meeting underground water pH, in the reaction soln after oxidation, with the addition of Ca (OH)
2.Under alkaline environment, ferric ion rapidly and Ca (OH)
2there is ion-exchange and generate yellow Fe (OH)
3precipitation.Add Ca (OH)
2after pH value of solution meet the restriction of underground water pH, and effectively remove the iron ion in solution by filtering separation.
Claims (2)
1. be applicable to an Ex-situ remediation method for chloronitrobenzene class polluted underground water, it is characterized in that, order is carried out as follows:
(1) in sewage, 4-Chloro-2-Nitrobenzene and total petroleum hydrocarbon concentration are respectively 21mgL
-1and 7.3mgL
-1, COD content is 3620mgL
-1, sewage first carries out filtration with 45nm millipore filtration and removes mechanical impurity, and after filtering, pH is 3;
(2) add reduced iron powder stirring reaction, add-on is the 30-40% of COD content, reaction times 3-5 days, and Zero-valent Iron deoxygenization chlorination oil of mirbane generates ferrous ion Fe
2+and aniline;
(3) first FeSO is added
47H
2o, addition is 30% of COD content, is stirred to miscible; Be the hydrogen peroxide H of 30% again by mass concentration
2o
2progressively be added in reaction soln by the 2-3 amount doubly of COD content and carry out oxidizing reaction, ferrous ion is oxidized to ferric ion, and the reaction times is 1 day, and reacted solution ph is 2.2;
(4), after oxidizing reaction terminates, Ca (OH) is added by the amount of the 0.1-0.2% of sewage solution quality
2displace ferric ion, and regulate pH to 6-9;
(5) filtering separation removes throw out.
2. be applicable to the Ex-situ remediation method of chloronitrobenzene class polluted underground water as claimed in claim 1, it is characterized in that, in step (two), the add-on of reduced iron powder is 30% of COD content.
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|---|---|---|---|---|
| CN104591426B (en) * | 2014-12-15 | 2016-07-06 | 南京理工大学 | Zero-valent Iron reduction-Fenton oxidation integrated reacting device and the method utilizing its process nitro-aromatic compound waste water |
| CN104591368A (en) * | 2015-01-26 | 2015-05-06 | 大连理工大学 | Iron-coal ash-kaolin filler and method for reductively converting nitro-aromatic waste water |
| CN104944637A (en) * | 2015-06-09 | 2015-09-30 | 复旦大学 | Method for treating nitrobenzene waste liquid through iron scrap reduction by Fenton method |
| CN108356070B (en) * | 2018-04-28 | 2020-11-06 | 东南大学 | Method for degrading chlorofluorobenzene pollution in soil |
| CN114259984A (en) * | 2021-11-11 | 2022-04-01 | 上海市环境科学研究院 | Alkali modified charcoal-loaded zero-valent iron composite material and preparation method and application thereof |
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|---|---|---|---|---|
| EP0378888A1 (en) * | 1986-12-29 | 1990-07-25 | E.I. Du Pont De Nemours And Company | Destruction of nitrophenols |
| CN1907888A (en) * | 2006-06-30 | 2007-02-07 | 河北万圣环保科技集团有限公司 | Process method for waste water containing nitrobenzene and aniline |
| CN101597116A (en) * | 2009-04-27 | 2009-12-09 | 江苏隆昌化工有限公司 | A kind of 2,5-dichloronitrobenzene waste water treatment process |
| CN102627352A (en) * | 2012-04-17 | 2012-08-08 | 北京师范大学 | Method for catalytically reducing chloronitrobenzene waste water by using straw carbon |
-
2013
- 2013-09-13 CN CN201310419885.4A patent/CN103626277B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0378888A1 (en) * | 1986-12-29 | 1990-07-25 | E.I. Du Pont De Nemours And Company | Destruction of nitrophenols |
| CN1907888A (en) * | 2006-06-30 | 2007-02-07 | 河北万圣环保科技集团有限公司 | Process method for waste water containing nitrobenzene and aniline |
| CN101597116A (en) * | 2009-04-27 | 2009-12-09 | 江苏隆昌化工有限公司 | A kind of 2,5-dichloronitrobenzene waste water treatment process |
| CN102627352A (en) * | 2012-04-17 | 2012-08-08 | 北京师范大学 | Method for catalytically reducing chloronitrobenzene waste water by using straw carbon |
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