CN103286125A - Method for removing hydrochloric ether contained in soil through chemical oxidation method - Google Patents
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- CN103286125A CN103286125A CN2013102702042A CN201310270204A CN103286125A CN 103286125 A CN103286125 A CN 103286125A CN 2013102702042 A CN2013102702042 A CN 2013102702042A CN 201310270204 A CN201310270204 A CN 201310270204A CN 103286125 A CN103286125 A CN 103286125A
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Abstract
The invention relates to a method for removing hydrochloric ether contained in soil in the restoring and treating process of hydrochloric ether contaminated soil, and belongs to the technical field of environment treatment. The method mainly removes certain hydrochloric ether contaminants which exist in the soil through the oxidation action of sodium persulfate (Na2S2O8). The method can be used for treating the hydrochloric ether contained in the soil by carrying out out-phase activation on an oxidizing agent by simultaneously adding ferroferric oxide powder under the condition of ensuring the existence of the sodium persulfate in a treatment process, thereby accelerating the chemical oxidation process and enhancing the treatment effect. The method disclosed by the invention is simple, easy to operate and outstanding in effect. According to the invention, the sodium persulfate as a green oxidizing agent is stable in chemical property and higher in oxidization capacity, the hydrochloric ether achieves high removal efficiency, and the removal rate of trichloroethylene in the soil achieves 99%. The method disclosed by the invention has the advantages of fast dechlorination on the hydrochloric ether contaminated soil, less destruction on a soil structure, no toxicity of products, convenience for subsequent utilization and low expense.
Description
[technical field]
The present invention relates to the soil remediation technical field, specifically, is the method that a kind of chemical oxidization method is removed chlorohydrocarbon in the contaminated soil.
[background technology]
Soil is in the center of natural environment, and it is bearing in the environment pollutant from each side.The chlorinated hydrocarbon organic matter is frequently detected in the contaminated site all over the world, major part has carcinogenesis or potential " three cause " (carcinogenic, teratogenesis, mutagenesis) harm, there are 10 kinds to be chlorinatedorganic in the highest 25 kinds of pollutants of verification and measurement ratio, common have a trichloro-ethylene, 1,1,1-trichloroethanes, tetrachloro-ethylene and chloroform etc.Soil is in a single day contaminated, and not only can directly influence ecological environment of soil but also can threaten groundwater quality, and one of underground water domestic water water source that to be China important.
In view of soil is subjected to popularity that chlorinated hydrocarbon pollutes and chlorinated hydrocarbon pollutant to the strong harmfulness of soil and groundwater environment, Chinese scholars has extensively been carried out control and the recovery technique of chlorinated hydrocarbon pollutant in the soil environment.The main method that chlorohydrocarbon in the soil is removed in research at present both at home and abroad comprises: gas phase extraction method, original position hot repair are multiple, biological restoration method and in-situ chemical oxidizing process (ISCO).
One, gas phase extraction method
The gaseous phase of soil extraction method is a kind of soil based technique for in-situ remediation that starts from the middle and later periods eighties 20th century, succeeded in developing in 1984 and patented power by U.S. Terra Vac company the earliest, be by injecting hole air to be injected in the soil, utilize vacuum equipment to pass through wellhole simultaneously, the volatile organic contaminant matter that contains in the soil is extracted out the face of land, and the gas of extraction need be collected and do post-processed.This method can be handled volatile organic contaminant (VOCs) and some semi-volatile organic matter (SVOCs).But in view of the complexity of soil environment, construct in earlier stage loaded down with trivial details to the destruction of soil and operation maintenance of gas phase extraction method makes it to be unsuitable on a small scale and the place of geological conditions complexity, also need further improve the wide usage of the method.
Two, the original position hot repair is multiple
The multiple cardinal principle of original position hot repair is the recovery by improving the temperature in soil and the groundwater environment and then improving pollutant.Hot repairing method has two tangible advantages: the one, can in underground environment, not introduce chemical reagent; The 2nd, can pass the porous media zone of variety classes and hypotonicity by heating.But only the original position hot repair is a pure physical process again, fundamentally do not remove harmful substance, just harmful substance is transferred to from liquid phase in gas phase or the solid phase and gone, rather than with thoroughly decomposition or degraded of target contaminant, so the control of simple physics can't fundamentally reach optimal removal effect, is difficult to satisfy the standard of soil.In heat treatment process, the rising of temperature can cause the variation of ecological environment of soil in the underground environment, and the processing follow-up to soil impacts.
Three, biological restoration method
Bioremediation technology mainly comprises plant and microorganism recovery technique.Phytoremediation technology since its to have a rehabilitation cost cheap and to advantages such as environment and soil texture disturbance are few, be used widely at present and approved, particularly pollute in the reparation at agricultural and natural soils and bringing into play important effect.But, the polluted soil phyto recovery technique is because repairing efficiency is long, it is bigger to take up room, also be subjected to the restriction of soil types, temperature, humidity and nutritional condition simultaneously, and phytoremediation technology is general only to have effect preferably to the top layer contaminated soil, relatively poor to the removal effect that is distributed in more profound pollutant in soil, so a technology not large-scale promotion utilization as yet.
The microbial degradation mechanism of chlorohydrocarbon is divided into aerobic degradation, anaerobism transforms and be total to metabolism etc.Biodegradable method effect is better, but specific aim is stronger, and degradation speed is slower.But the microorganism that this technology is chosen needs specifically to tame sometimes, and the toxicity of pollutant suppresses activation of microorganism sometimes, and microbial degradation also needs simultaneously the monitoring and the maintenance that continue.
Four, in-situ chemical oxidative treatment
The in-situ chemical oxidizing process refers under the situation of not mobile polluted soil or pollutant, and oxidant (commonly used is had Fenton reagent, potassium permanganate, an O
3And persulfate) imports under the face of land, make target contaminant degraded mineralising or change into land forming method than innocuous substance via oxidation.Because it makes pollutant remove by the degraded mode, and can eliminate or reduce pollutant toxicity the facilitation of the organic matter that is difficult for biological restoration (for example polycyclic aromatic hydrocarbon, Polychlorinated biphenyls etc.) degraded and degradation rate efficiently.But because the complexity of chemical composition of soil, all kinds of organic substances that comprise, inorganic mineral, reducing substances etc. can preferentially consume oxidant, simultaneous oxidation agent non-directiveness of migratory direction and scope in the soil under the face of land makes that directly to add oxidant separately relatively poor to the chlorohydrocarbon treatment effect.
Therefore need to seek a kind of to the respond well and stable removal method of chlorinated hydrocarbon organic matter removal in the soil.
[summary of the invention]
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of chemical oxidization method to remove the method for chlorohydrocarbon in the soil.
The objective of the invention is to be achieved through the following technical solutions:
A kind of chemical oxidization method is removed the method for chlorohydrocarbon in the soil, its concrete steps are: add ferroferric oxide powder in the chlorohydrocarbon contaminated soil, add sodium peroxydisulfate solution in the soil that adds ferroferric oxide powder and react, realize the repairing and treating of chlorohydrocarbon contaminated soil.
The described quality of tri-iron tetroxide that adds is for handling 1.25%～10% of soil gross mass; Be preferably 5%.
The described ferroferric oxide powder particle diameter that adds is 0.2～0.3mm.
The mol ratio of the described tri-iron tetroxide that adds and sodium peroxydisulfate is 1: 1.5～1: 3, is preferably 1: 2.
Mol ratio between the contained chlorohydrocarbon of the sodium peroxydisulfate of described adding and soil is 200: 1～800: 1, is preferably 500: 1.
Described reaction condition: utilize the solid-liquid mixing apparatus to stir, reaction temperature control is 20 ℃ in room temperature.
Described chlorohydrocarbon is modal pollutant in the chlorohydrocarbon contaminated soil: trichloro-ethylene and 1,1,1-trichloroethanes.
To being subjected to add ferroferric oxide powder in the chlorohydrocarbon contaminated soil, the sodium peroxydisulfate solution that added molar ratio with respect to chlorohydrocarbon and be 200: 1～800: 1 carries out oxidation reaction; Take a sample from soil in the different time periods, with the chlorohydrocarbon content of gas chromatograph for determination sample, find that the removal effect of chlorohydrocarbon is remarkable behind above-mentioned chemical oxidation reaction.
Described oxidant activation method: add the tri-iron tetroxide pressed powder and activate, the mol ratio of tri-iron tetroxide and sodium peroxydisulfate is best results in 1: 1.5～1: 3 scope;
Compared with prior art, good effect of the present invention is:
(1) operation is simple and effect is remarkable in the present invention;
(2) than carrying out under the condition, it is little to add the oxidizing agent solution volume, more repairs situation near actual contaminated site in low water and soil quality in the present invention;
(3) sodium peroxydisulfate is a kind of green oxidation agent, and product does not influence soil characteristic, produces the oxidant with higher oxidation-reduction potential as the activated back of oxidant, and is cheap;
(4) the sodium peroxydisulfate oxidation is selectively good, can avoid soil constitution to disturb in course of reaction, and preferential and chlorohydrocarbon carries out haptoreaction;
(5) the tri-iron tetroxide preparation is simple, cheap, and stable in properties is obvious to the sodium peroxydisulfate activation effect;
(6) molar ratio of the strong and tri-iron tetroxide of the sodium peroxydisulfate oxidability among the present invention was at 1.5: 1～3: 1 o'clock, and the clearance of trichloro-ethylene reaches 99%;
(7) course of reaction of the present invention is little to the destruction of structure of the soil itself, and the environment that is fit to is more, and the product avirulence is convenient to subsequent treatment, is widely used.
[specific embodiment]
Below provide a kind of chemical oxidization method of the present invention to remove the specific embodiment of the method for chlorohydrocarbon in the soil.
Embodiment 1
Be that the contaminated soil matrix of 100mg/kg (adds 50gFe in advance in the trichloro-ethylene pollution concentration
3O
4/ kg soil (dry weight)) in, adding 5L concentration is the Na of 127mM
2S
2O
8Solution fully mixes stirring, reaction temperature control simultaneously is at 20 ℃, 48 hours reaction time, carried out the soil sample extraction respectively at 1,3,6,9,12,24,48 hour, adopt gas chromatograph to analyze trichloro-ethylene concentration, the result reaches 99% through trichloro-ethylene clearance after 48 hours of PROCESS FOR TREATMENT of the present invention.
Embodiment 2
Be that the contaminated soil matrix of 100mg/kg (adds 100gFe in advance in the trichloro-ethylene pollution concentration
3O
4/ kg soil (dry weight)) in, adding 5L concentration is the Na of 127mM
2S
2O
8Solution fully mixes stirring, reaction temperature control simultaneously is at 20 ℃, 48 hours reaction time, carried out the soil sample extraction respectively at 1,3,6,9,12,24,48 hour, adopt gas chromatograph to analyze trichloro-ethylene concentration, the result reaches 99.9% through trichloro-ethylene clearance about 48 hours of PROCESS FOR TREATMENT of the present invention.
Embodiment 3
Be that the contaminated soil matrix of 100mg/kg (adds 50gFe in advance in the trichloro-ethylene pollution concentration
3O
4/ kg soil (dry weight)) in, adding 4L concentration is the Na of 254mM
2S
2O
8Solution fully mixes stirring, reaction temperature control simultaneously is at 20 ℃, 48 hours reaction time, the extraction of taking a sample at 1,3,6,9,12,24,48 hour respectively, adopt gas chromatograph to analyze trichloro-ethylene concentration, the result reaches 90% through trichloro-ethylene clearance about 48 hours of PROCESS FOR TREATMENT of the present invention.
Embodiment 4
Be that the contaminated soil matrix of 100mg/kg (adds 100gFe in advance in the trichloro-ethylene pollution concentration
3O
4/ kg soil (dry weight)) in, adding 4L concentration is the Na of 254mM
2S
2O
8Solution fully mixes stirring, reaction temperature control simultaneously is at 20 ℃, 48 hours reaction time, the extraction of taking a sample at 1,3,6,9,12,24,48 hour respectively, adopt gas chromatograph to analyze trichloro-ethylene concentration, the result reaches 99.2% through trichloro-ethylene clearance about 48 hours of PROCESS FOR TREATMENT of the present invention.
Embodiment 5
Be that the contaminated soil matrix of 100mg/kg (adds 50gFe in advance in 1,1,1-trichloroethanes pollution concentration
3O
4/ kg soil (dry weight)) in, adding 4L concentration is the Na of 254mM
2S
2O
8Solution fully mixes stirring, reaction temperature control simultaneously is at 20 ℃, 120 hours reaction time, the extraction of taking a sample at 3,6,12,24,48,72,120 hours respectively adopts gas chromatograph to analyze 1,1,1-trichloroethanes concentration, the result is through 1,1 of PROCESS FOR TREATMENT of the present invention, and 1-trichloroethanes clearance about 120 hours reaches 48%.
Embodiment 6
Be that the contaminated soil matrix of 100mg/kg (adds 100gFe in advance in 1,1,1-trichloroethanes pollution concentration
3O
4/ kg soil (dry weight)) in, adding 4L concentration is the Na of 254mM
2S
2O
8Solution fully mixes stirring, reaction temperature control simultaneously is at 20 ℃, 120 hours reaction time, the extraction of taking a sample at 3,6,12,24,48,72,120 hours respectively adopts gas chromatograph to analyze 1,1,1-trichloroethanes concentration, the result is through 1,1 of PROCESS FOR TREATMENT of the present invention, and 1-trichloroethanes clearance about 120 hours reaches 49%.
The above only is preferred embodiment of the present invention; should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some improvements and modifications, these improvements and modifications also should be considered within the scope of protection of the present invention.
Claims (7)
1. a chemical oxidization method is removed the method for chlorohydrocarbon in the soil, it is characterized in that, its concrete steps are: add ferroferric oxide powder in the chlorohydrocarbon contaminated soil, add sodium peroxydisulfate solution in the soil that adds ferroferric oxide powder and react, realize the repairing and treating of chlorohydrocarbon contaminated soil.
2. a kind of chemical oxidization method as claimed in claim 1 is removed the method for chlorohydrocarbon in the soil, it is characterized in that, the described quality of tri-iron tetroxide that adds is for handling 1.25%～10% of soil gross mass; Be preferably 5%.
3. a kind of chemical oxidization method as claimed in claim 1 is removed the method for chlorohydrocarbon in the soil, it is characterized in that the described ferroferric oxide powder particle diameter that adds is 0.2～0.3mm.
4. a kind of chemical oxidization method as claimed in claim 1 is removed the method for chlorohydrocarbon in the soil, it is characterized in that the mol ratio of the described tri-iron tetroxide that adds and sodium peroxydisulfate is 1: 1.5～1: 3, is preferably 1: 2.
5. a kind of chemical oxidization method as claimed in claim 1 is removed the method for chlorohydrocarbon in the soil, it is characterized in that the mol ratio between the contained chlorohydrocarbon of the sodium peroxydisulfate of described adding and contaminated soil is 200: 1～800: 1, is preferably 500: 1.
6. a kind of chemical oxidization method as claimed in claim 1 is removed the method for chlorohydrocarbon in the soil, and it is characterized in that described reaction condition: utilize the solid-liquid mixing apparatus to stir, reaction temperature is controlled at 20 ℃.
7. a kind of chemical oxidization method as claimed in claim 1 is removed the method for chlorohydrocarbon in the soil, it is characterized in that described chlorohydrocarbon is modal pollutant in the contaminated site: trichloro-ethylene and 1,1,1-trichloroethanes.
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Cited By (10)
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| CN103537481A (en) * | 2013-10-30 | 2014-01-29 | 江苏上田环境修复有限公司 | Preparation method of curing isolation impervious body for organic pollutants |
| CN103814720A (en) * | 2014-02-12 | 2014-05-28 | 江苏上田环境修复有限公司 | Method of lowering soil organic pollution for low-selenium tea garden and producing selenium-rich tea |
| CN104438302A (en) * | 2014-10-23 | 2015-03-25 | 江苏盖亚环境工程有限公司 | Method for restoring trichloro ethylene polluted soil |
| CN105414171A (en) * | 2016-01-06 | 2016-03-23 | 上田环境修复股份有限公司 | Horizontal permeable reactive plant barrier restoration system for restoring chlorohydrocarbon organic contaminated soil and treatment method thereof |
| CN106734164A (en) * | 2016-12-22 | 2017-05-31 | 常州大学 | A kind of microwave reinforced nanometer Fe3O4/Na2CO4The method for repairing PAEs contaminated soils |
| CN108213064A (en) * | 2017-12-05 | 2018-06-29 | 中国科学院南京土壤研究所 | A kind of medicament of in-situ immobilization high concentration polycyclic aromatic hydrocarbon pollution and its application |
| CN109794220A (en) * | 2019-01-31 | 2019-05-24 | 河北工业大学 | A method of utilizing organic compound in tailings glass soil |
| CN110436605A (en) * | 2019-08-06 | 2019-11-12 | 华东理工大学 | The method of chlorohydrocarbon in underground water of the iron plane flower activation sodium peroxydisulfate removal containing surfactant |
| CN114951260A (en) * | 2022-06-22 | 2022-08-30 | 昆明理工大学 | Method for restoring organic contaminated soil by using plants rich in polyphenol |
| CN115415305A (en) * | 2022-08-30 | 2022-12-02 | 成都理工大学 | Harmless treatment method for chlorinated organic compounds in soil |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103537481A (en) * | 2013-10-30 | 2014-01-29 | 江苏上田环境修复有限公司 | Preparation method of curing isolation impervious body for organic pollutants |
| CN103814720A (en) * | 2014-02-12 | 2014-05-28 | 江苏上田环境修复有限公司 | Method of lowering soil organic pollution for low-selenium tea garden and producing selenium-rich tea |
| CN103814720B (en) * | 2014-02-12 | 2016-01-06 | 上田环境修复股份有限公司 | A kind of low selenium tea place reduces soil organic contamination and produces the method for Se rich tea |
| CN104438302A (en) * | 2014-10-23 | 2015-03-25 | 江苏盖亚环境工程有限公司 | Method for restoring trichloro ethylene polluted soil |
| CN105414171B (en) * | 2016-01-06 | 2018-09-28 | 上田环境修复股份有限公司 | Reaction plant walls repair system and its processing method for contaminated soil remediation |
| CN105414171A (en) * | 2016-01-06 | 2016-03-23 | 上田环境修复股份有限公司 | Horizontal permeable reactive plant barrier restoration system for restoring chlorohydrocarbon organic contaminated soil and treatment method thereof |
| CN106734164A (en) * | 2016-12-22 | 2017-05-31 | 常州大学 | A kind of microwave reinforced nanometer Fe3O4/Na2CO4The method for repairing PAEs contaminated soils |
| CN108213064A (en) * | 2017-12-05 | 2018-06-29 | 中国科学院南京土壤研究所 | A kind of medicament of in-situ immobilization high concentration polycyclic aromatic hydrocarbon pollution and its application |
| CN109794220A (en) * | 2019-01-31 | 2019-05-24 | 河北工业大学 | A method of utilizing organic compound in tailings glass soil |
| CN109794220B (en) * | 2019-01-31 | 2022-03-22 | 河北工业大学 | Method for treating organic compounds in soil by using tailings |
| CN110436605A (en) * | 2019-08-06 | 2019-11-12 | 华东理工大学 | The method of chlorohydrocarbon in underground water of the iron plane flower activation sodium peroxydisulfate removal containing surfactant |
| CN110436605B (en) * | 2019-08-06 | 2022-03-22 | 华东理工大学 | Method for removing chlorinated hydrocarbons in underground water containing surfactant by activating sodium persulfate through iron shavings |
| CN114951260A (en) * | 2022-06-22 | 2022-08-30 | 昆明理工大学 | Method for restoring organic contaminated soil by using plants rich in polyphenol |
| CN115415305A (en) * | 2022-08-30 | 2022-12-02 | 成都理工大学 | Harmless treatment method for chlorinated organic compounds in soil |
| CN115415305B (en) * | 2022-08-30 | 2023-10-13 | 成都理工大学 | Harmless treatment method for chlorinated organic compounds in soil |
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Application publication date: 20130911 |