CN104307869A - Method for intensively removing hexachloro-cyclohexane soprocide and dichlorodiphenyl trichloroethane in soil by zero-valent iron - Google Patents

Method for intensively removing hexachloro-cyclohexane soprocide and dichlorodiphenyl trichloroethane in soil by zero-valent iron Download PDF

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CN104307869A
CN104307869A CN201410592288.6A CN201410592288A CN104307869A CN 104307869 A CN104307869 A CN 104307869A CN 201410592288 A CN201410592288 A CN 201410592288A CN 104307869 A CN104307869 A CN 104307869A
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soil
zero
valent iron
bhc
ddt
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万金忠
林玉锁
张胜田
龙涛
周艳
李群
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Nanjing Institute of Environmental Sciences MEP
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Nanjing Institute of Environmental Sciences MEP
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Abstract

The invention relates to a method for intensively removing hexachloro-cyclohexane soprocide and dichlorodiphenyl trichloroethane in soil by zero-valent iron. The method comprises the following steps: immersing reduced iron powder into a copper solution to prepare a micron Fe/Cu duplex metal material, so that the load amount of Cu is 1%; sequentially adding duplex metal and triton X-100 into the soil according to the adding amounts of 5% and 0.1%; adjusting the initial pH value of the soil to 4-5 and adjusting the water content rate of the soil to 25%-30%; and isolating oxygen and piling to react for a certain time so as to degrade and remove hexachloro-cyclohexane soprocide and dichlorodiphenyl trichloroethane in the soil. The method does not need to use complicated equipment, is simple to operate and environment-friendly; the method has economical cost and has no secondary pollution; and the method has a relatively good application prospect in the remediation of the soil polluted by low-medium concentration hexachloro-cyclohexane soprocide and dichlorodiphenyl trichloroethane.

Description

The method of BHC and DDT in soil is removed in a kind of Zero-valent Iron strengthening
Technical field
The invention belongs to the method removing organic residue in soil, particularly relate to the method that BHC and DDT in soil are removed in the strengthening of a kind of Zero-valent Iron.
Background technology
In developed areas such as China major part provinces and cities, particularly Jiangsu Province, organo-chlorine pesticide BHC and DDT etc. are once a large amount of to be produced and uses, and causes serious environmental pollution.As in more than 30 year in the past, the production of Chinese DDT reaches 400,000 tons, is 22% of Gross World Product.Only the former powder yield of China's BHC in 1980 is just up to 28.64 ten thousand tons.In recent years, along with honouring an agreement and the fast development of urbanization process of Convention of Stockholm, these BHC and DDT manufacturing enterprise are closed successively, but leave over lower a series of place soil contamination problem.
Decompose because BHC and DDT physicochemical property are very stable, difficult, persistence is strong, enter to hold for a long time after in soil to stay and to be formed health by water, air and food chain in soil and threaten.BHC and DDT have very large toxicity (carcinogenicity, neurotoxicity, endocrine disrupting etc.).Physician finds, has the residue of BHC and DDT in the blood of modern, brain, liver and fat, also has impact, and have obvious carcinogenic performance to the liver function of the mankind and form.Found out that BHC and DDT cause the reproduction of the biology of birds fish to poison, physiological abnormalities even becomes extinct, the heavy damage ecosystem simultaneously.Therefore the control carried out BHC and gesarex polluted place soil is badly in need of.
At present domestic/in the world for the not effective especially technology of reparation of organochlorine pesticide pollution place soil.Generally speaking, for the improvement in organic contamination place, mainly contain the methods such as air-extraction, burning method, curing/stabilizing, thermal desorption, drip washing, chemical treatment at present.Air lift is an in-situ soil remediation technology utilizing physical method to remove volatile organic contaminant in unsaturated soil.But for the organo-chlorine pesticide of half volatile, air lift is difficult to obtain desirable effect.Burning is foreign applications hot-fixing comparatively early, and its principle is the vaporization at high temperature utilizing 870 ~ 1200 DEG C and the organic pollution burnt in soil.Incineration technology is a kind of comparatively original, extensive place Treatment process, and may cause secondary pollution, the application of the burning method of Abroad in Recent Years has a declining tendency.Solidification/stable normally utilizes the material such as cement, flyash and soil to mix mutually and embed by pollutant, make it in graininess or large bulk existence, and then make pollutant be in metastable state.Solidifying/stablizing is a kind of technology being applicable to in-situ immobilization, in high concentration organic contamination and organic-combined pollution site remediation, have some to apply.But the method needs the long-term monitoring after repairing, and along with the change of space enrironment, pollutant may discharge again, thus there is potential environmental risk.Thermal desorption refers to by direct or indirect heat exchange, contaminated soil is heated to enough temperature (150 ~ 540 DEG C), makes the process that organic pollution volatilizees or is separated.Thermal desorption technology can process volatility or half volatile pollutants in soil, less to the destruction of soil.But want desorption OCPs soil entirety need be heated to more than the boiling point of pollutant, the energy consumed is higher, and volatile pollutants is revealed and may be caused secondary pollution.
Zero-valent Iron reduction, as a kind of green, economic recovery technique, obtains extensive investigation and application in the waste water/underwater prevention of organochlorine and heavy metal pollution.The electronation of Zero-valent Iron reduction dechlorination technology employing Fe removes the chlorine element in chlorinatedorganic, and make it become chlorion, many chlorine organics become parent hydro carbons, to reach nontoxic or the object of low toxicity.Around Zero-valent Iron to all kinds of nitro or organo-chlorine pollutant, comprise the deoxidization, degradation of the hardly degraded organic substance contaminated soils such as chlorinated organic solvent (as trichlorine/tetrachloro-ethylene TCE/PCE), herbicide (Atrazine, chlopyrifos), ammonium nitrate explosive (ring Sanya trinitramine), all have more research to report.Research about Zero-valent Iron rehabilitating soil is also relatively less, and mainly for nitrobenzene and Polychlorinated biphenyls (PCBs), there is not been reported in the process of polluting for Organochlorine Pesticides In Soil.Meanwhile, current also only have a small amount of report around ZVI reparation OCPs contaminated soil in the world, needs to be studied.
For BHC and this kind of difficult degradation organo-chlorine pesticide of DDT, the effect of tradition zero-valent iron technology can be subject to the restriction of two aspects: one is that BHC and DDT belong to typical hydrophobic organic compound, water-soluble extremely low, which has limited contaminant molecule to contact with zeroth order is ironing surface, be unfavorable for the carrying out of reduction dechlorination reaction in soil; Two is BHC and DDT Stability Analysis of Structures, and common iron powder limited activity, be difficult to its fast degradation.
Summary of the invention
1, the technical problem that will solve is invented
The object of the invention is the soil pollution caused for BHC and DDT, the method that BHC and DDT in soil are removed in the strengthening of a kind of Zero-valent Iron is proposed, adopt surfactant strengthening Zero-valent Iron bimetallic to come BHC and DDT in deoxidization, degradation soil, the difficult degradation organo-chlorine pesticides such as BHC in soil and DDT can be removed quickly and efficiently.
2, technical scheme
Inventive principle: surfactant is as good solubilizer, join in soil and significantly can promote that insoluble organic in soil (as BHC and DDT etc.) dissolves in aqueous phase, improve pollutant to contact with zeroth order is ironing surface, thus improve the degradation rate of pollutant.In addition, to Zero-valent Iron area load second metal, as Cu, Ni, Pd etc., namely build Zero-valent Iron bimetallic system, the catalytic degradation activity of Zero-valent Iron can be significantly improved.Build strengthening Zero-valent Iron reduction system from above two aspects, realize the rapidly and efficiently degraded of the organo-chlorine pesticide such as BHC and DDT in soil.
Object of the present invention is achieved through the following technical solutions:
A method for BHC and DDT in soil is removed in Zero-valent Iron strengthening, the steps include:
(1) in closed container, it is in the dilute sulfuric acid of 0.5mol/L that Zero-valent Iron is immersed into concentration by the solid-to-liquid ratio of 1:10, after surface oxide layer is removed in pickling, being immersed into copper concentration by identical solid-to-liquid ratio is again in the copper chloride solution of 2g/L, mix and blend 10min, copper ion is replaced Zero-valent Iron surface, clear water rinses surface removal iron ion and chlorion, obtains the micron Fe/Cu bimetallic material prepared;
(2) and primary dcreening operation process broken to contaminated soil, and sampling analysis measures the initial concentration of water content, pH value and BHC and DDT;
(3) add the micron Fe/Cu bimetallic material prepared according to step (1) to soil, adopt mixing plant fully to be mixed with Fe/Cu by soil;
(4) continue to add surfactant triton x-100 in soil, and supplementing water, make the moisture content of final soil control, 30%, again to stir;
(5) adopt weight percent concentration to be that 1% dilute sulfuric acid or 0.2mol/L acetic acid regulate soil mass pH value 4.5-5, rear oxygen barrier is banked up;
(6) sample to the soil of process after 7-10d, analysis pH and BHC, DDT level change;
(7) if soil pH value is elevated to more than 7 in process, adopt sulfuric acid or acetic acid that soil pH value is adjusted back to 5.
The above-mentioned method stated, is improved to further: Zero-valent Iron is powdery or graininess, and particle size is 10-200 order.Zero-valent Iron bimetallic is Fe/Cu, and the mass fraction that in bimetallic, Cu accounts for Fe is for being 1%.Further improvement project, when the bimetallic dosage of Fe/Cu is to account for soil dry basic weight calculated mass percentage for 5%.
Improved plan: the dosage of surfactant triton x-100 is to account for soil dry basic weight calculated mass percentage for 0.1%.
3, beneficial effect
Compared with prior art, tool of the present invention has the following advantages:
1) conventional oxidation or Zero-valent Iron reduction technique undesirable for the treatment effect of the difficult degradation such as BHC and DDT organochlorine, method of the present invention can realize the rapidly and efficiently degraded of BHC in soil and DDT.
2) method of the present invention is based on Zero-valent Iron reduction reaction, and reaction condition is gentle, and reagent is easy to be easy to get, economical, green non-secondary pollution.
3) equipment needed for method of the present invention is simple, without the need to setting up complex appts, easy to operation, only several medicament need be mixed, run without the need to professional.
Accompanying drawing explanation
Fig. 1 is the effect contrast figure that the present invention and traditional Zero-valent Iron (pickling iron powder) process α-BHC in soil;
Fig. 2 is the effect contrast figure that the present invention and traditional Zero-valent Iron (pickling iron powder) process γ-BHC in soil;
Fig. 3 is that the present invention and traditional Zero-valent Iron (pickling iron powder) process p, p in soil ' effect contrast figure of-DDT.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1: to the process of BHC contaminated soil
The method that this example adopts invention to propose processes BHC Polluted Soil in the discarded insecticide factory in Jiangsu place.The initial concentration that in soil, the initial concentration of α-BHC and γ-BHC is respectively is 3.6mg/kg and 10.1mg/kg.Take commercially available 100 order reduced iron powder 15g, after adopting the sulfuric acid washing of 0.5mol/L, iron powder being immersed into 150mL, Cu concentration is in the copper chloride solution of 2g/L, fully mixes, obtained Fe/Cu bimetallic material.Take 300g BHC Polluted Soil in 1L plastic bottle, add the 15g Fe/Cu bimetallic prepared, stir and evenly mix.Add the TX-100 that 50ml concentration is 10mmol/L (mass concentration 0.647%) again, and supplementing water 40ml.Final soil moisture content, about 25%, stirs.Glacial acetic acid is adopted to regulate soil pH to be 4.5.Seal, cultivate in the constant incubator of 25 DEG C.Sample respectively in 0d, 5d, 15d, 25d, 35d, 45d and 55d, analyze soil pH value and BHC content.When finding 30d in process, soil pH is close to 7, adopts acetic acid to pull back to about 5.0.After 55d process, the degradation rate of α-BHC and γ-BHC is respectively 100% and 89.7%.And common Zero-valent Iron (pickling iron powder) degradation rate to α-BHC and γ-BHC is respectively 59.8% and 54.8%.
Embodiment 2; To the process of gesarex polluted soil
The method that this example adopts invention to propose processes gesarex polluted soil in the discarded insecticide factory in Jiangsu place.In soil main target pollutant p, p '-DDT initial concentration be 19.0mg/kg.Take commercially available 100 order reduced iron powder 15g, after adopting the sulfuric acid washing of 0.5mol/L, iron powder being immersed into 150mL, Cu concentration is in the copper chloride solution of 2g/L, fully mixes, obtained Fe/Cu bimetallic material.Take 300 gesarex polluted soil in 1L plastic bottle, add the 15g Fe/Cu bimetallic prepared, stir and evenly mix.Add the TX-100 that 50ml concentration is 10mmol/L (mass concentration 0.647%) again, and supplementing water 40ml.Final soil moisture content, about 25%, stirs.Glacial acetic acid is adopted to regulate soil pH to be 4.5.Seal, cultivate in the constant incubator of 25 DEG C.Sample respectively in 0d, 5d, 15d, 25d, 35d, 45d and 55d, analyze soil pH value and DDT level.When pH is close to 7 in process, acetic acid is adopted to pull back to about 5.0.After 55d process, p, p ' degradation rate of-DDT reaches 73.1%, and common Zero-valent Iron (pickling iron powder) is only 24.7%.

Claims (5)

1. a method for BHC and DDT in soil is removed in Zero-valent Iron strengthening, the steps include:
(1) in closed container, it is in the dilute sulfuric acid of 0.5mol/L that Zero-valent Iron is immersed into concentration by the solid-to-liquid ratio of 1:10, after surface oxide layer is removed in pickling, being immersed into copper concentration by identical solid-to-liquid ratio is again in the copper chloride solution of 2g/L, mix and blend 10min, copper ion is replaced Zero-valent Iron surface, clear water rinses surface removal iron ion and chlorion, obtains the micron Fe/Cu bimetallic material prepared;
(2) and primary dcreening operation process broken to contaminated soil, and sampling analysis measures the initial concentration of water content, pH value and BHC and DDT;
(3) add the micron Fe/Cu bimetallic material prepared according to step (1) to soil, adopt mixing plant fully to be mixed with Fe/Cu by soil;
(4) continue to add surfactant triton x-100 in soil, and supplementing water, make the moisture content of final soil control, 30%, again to stir;
(5) adopt weight percent concentration to be that 1% dilute sulfuric acid or 0.2mol/L acetic acid regulate soil mass pH value 4.5-5, rear oxygen barrier is banked up;
(6) sample to the soil of process after 7-10d, analysis pH and BHC, DDT level change;
(7) if soil pH value is elevated to more than 7 in process, adopt sulfuric acid or acetic acid that soil pH value is adjusted back to 5.
2. method according to claim 1, is characterized by: Zero-valent Iron is powdery or graininess, and particle size is 10-200 order.
3. according to claim 1 or claim 2, it is characterized by: Zero-valent Iron bimetallic is Fe/Cu, the mass fraction that in bimetallic, Cu accounts for Fe is for being 1%.
4. according to claim 1 or claim 2, it is characterized by: the bimetallic dosage of Fe/Cu is to account for soil dry basic weight calculated mass percentage for 5%.
5. according to claim 1 or claim 2, it is characterized by: the dosage of surfactant triton x-100 is to account for soil dry basic weight calculated mass percentage for 0.1%.
CN201410592288.6A 2014-10-29 2014-10-29 Method for intensively removing hexachloro-cyclohexane soprocide and dichlorodiphenyl trichloroethane in soil by zero-valent iron Pending CN104307869A (en)

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CN105583224A (en) * 2016-03-11 2016-05-18 沈阳大学 Method for performing in-situ remediation on DDTs (dichlorodiphenyltrichloroethane)-contaminated ageing farmland soil by utilizing dried blood
CN107200392A (en) * 2017-07-31 2017-09-26 山东大学 A kind of sulfide modifier Fe Cu bimetallic materials, preparation method and the method for removing chromate waste water
CN107265665A (en) * 2017-08-04 2017-10-20 南京大学 It is a kind of for infiltration type reaction wall composite of the chloride pollution amelioration containing nitro-aromatic of underground water and preparation method thereof
CN110711770A (en) * 2019-11-20 2020-01-21 中国科学院南京土壤研究所 Method for removing organochlorine compounds in soil through enhanced advanced oxidation and cooperative electrokinetic remediation of surface ion active agent
CN111250527A (en) * 2020-01-15 2020-06-09 中国科学院南京土壤研究所 Method for removing persistent organic pollutants in soil through Triton X-100 enhanced advanced oxidation in cooperation with electrokinetic remediation
CN111266572A (en) * 2020-03-20 2020-06-12 中国科学院过程工程研究所 Iron-copper bimetal load ferrous sulfide composite material, preparation method and application thereof

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CN104692475A (en) * 2015-02-11 2015-06-10 中国科学院合肥物质科学研究院 Method for rapidly degrading DDT through acid-assisted flaky micro/nanostructure zero-valent iron
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CN105583224A (en) * 2016-03-11 2016-05-18 沈阳大学 Method for performing in-situ remediation on DDTs (dichlorodiphenyltrichloroethane)-contaminated ageing farmland soil by utilizing dried blood
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CN107200392A (en) * 2017-07-31 2017-09-26 山东大学 A kind of sulfide modifier Fe Cu bimetallic materials, preparation method and the method for removing chromate waste water
CN107265665A (en) * 2017-08-04 2017-10-20 南京大学 It is a kind of for infiltration type reaction wall composite of the chloride pollution amelioration containing nitro-aromatic of underground water and preparation method thereof
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CN110711770A (en) * 2019-11-20 2020-01-21 中国科学院南京土壤研究所 Method for removing organochlorine compounds in soil through enhanced advanced oxidation and cooperative electrokinetic remediation of surface ion active agent
CN110711770B (en) * 2019-11-20 2021-10-01 中国科学院南京土壤研究所 Method for removing organochlorine compounds in soil through enhanced advanced oxidation and cooperative electrokinetic remediation of surface ion active agent
CN111250527A (en) * 2020-01-15 2020-06-09 中国科学院南京土壤研究所 Method for removing persistent organic pollutants in soil through Triton X-100 enhanced advanced oxidation in cooperation with electrokinetic remediation
CN111250527B (en) * 2020-01-15 2021-09-14 中国科学院南京土壤研究所 Method for removing persistent organic pollutants in soil through Triton X-100 enhanced advanced oxidation in cooperation with electrokinetic remediation
CN111266572A (en) * 2020-03-20 2020-06-12 中国科学院过程工程研究所 Iron-copper bimetal load ferrous sulfide composite material, preparation method and application thereof
CN111266572B (en) * 2020-03-20 2021-04-09 中国科学院过程工程研究所 Iron-copper bimetal load ferrous sulfide composite material, preparation method and application thereof

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