CN103288200A - Method for removing hydrochloric ether contained in underground water and soil mud system through chemical reduction - Google Patents
Method for removing hydrochloric ether contained in underground water and soil mud system through chemical reduction Download PDFInfo
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Abstract
The invention relates to a method for removing hydrochloric ether contained in underground water and a soil mud system through chemical reduction, and belongs to the technical field of environmental management. The method mainly removes certain hydrochloric ether contaminants which exist in the underground water and the soil mud system through the reduction action of ZVI (Zero-Valent Iron). The method achieves the purpose of hydrochloric ether treatment by adding the zero-valent iron to the mud system which contains the hydrochloric ether contaminants in a treatment process. The method disclosed by the invention is simple, effective and outstanding in treatment effect. According to the invention, the zero-valent iron is rich in source, low in cost and higher in reducing capacity, and the hydrochloric ether can be fast dechlorinated and degraded and achieves high removal efficiency, for instance, the removal ratio of 1,1,1-trichloroethane can achieve 99.5%. The method disclosed by the invention can be used for simultaneously treating the hydrochloric ether contained in the underground water and the soil mud system and is less influenced by temperature and pH on reaction process and wide in application range.
Description
[technical field]
The present invention relates to the environmental improvement technical field, specifically, is the method that hydrochloric ether in underground water and the soil mud system is removed in a kind of chemical reduction.
[background technology]
Underground water is important drinking water source, has irreplaceable effect to supporting the sustainable development of socio-economy, also is important environmental element simultaneously, directly influences and changes state of ecological environment.Soil is in the central position of physical environment, be the basis of agriculture production and the important component part of people's living environment key element, soil is in a single day contaminated, not only can directly influence the live and work environment of people in this soil scope, but also can threaten groundwater quality.What therefore, underground water and soil pollution were repaired is significant.
In the numerous pollutions that cause underground water and soil, organic contamination is a class the most common and that be difficult to administer most, becomes the research focus of scientific circles gradually.Wherein, and 1 (1,1,1-TCA), trieline (TCE) and zellon chlorinated hydrocarbon organism such as (PCE), frequently detected in the underground water of contaminated site and the soil all over the world.This class chlorinated solvent density usually than water big, water-soluble little, be difficult for degraded and remove, major part has potential " three cause " (carcinogenic, teratogenesis, mutagenesis) harm, wherein the overwhelming majority has been classified as the poisonous and harmful organic pollutants of preferential control by various countries.It easily to underground movement, thereby has increased underground water and the contaminated degree of soil owing to weigh than water, and it is very difficult to make improvement repair.In addition, the solubleness of hydrochloric ether is lower, be difficult to by biological degradation, and migration distance is big, so in the waterbearing stratum, can have several years to the centuries, this just make the underground water that contains hydrochloric ether administer with soil pollution and common Pollution control technology to compare difficulty bigger.The hydrochloric ether Pollution abatement has become focus and the difficult point problem in global underground water and soil research field in underground water and the soil.
In view of underground water and edatope are subjected to the popularity that hydrochloric ether pollutes, Chinese scholars has extensively been carried out chlorinated hydrocarbon pollutes in the groundwater environment control and recovery technique research, in nearest 20 years, and hydrochloric ether pollution remediation technology showed increased.The hydrochloric ether pollution remediation technology mainly contains three major types such as physics control techniques, microorganism recovery technique, chemical treatment method in underground water and the soil.
Utilizing the physical process control techniques to administer hydrochloric ether is simple, an effective treating processes, but only be a pure physical process, fundamentally do not remove objectionable impurities, just objectionable impurities 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.
The microorganism recovery technique refers to utilize microorganism under certain envrionment conditions, the very slow DeR that maybe can not take place takes place under natural condition originally for promotion or reinforcement can fast and effeciently carry out, thereby toxic pollutant is changed into the treatment technology of non-toxic substance.But because groundwater pollutant complicated component in the actually operating can not be single source of pollution, therefore how taming and cultivate the microorganism that meets specific polluted-water improvement also is a problem of needing solution badly.
Handle hydrochloric ether common chemical treatment process and mainly contain chemical oxidization method and chemical reduction method.In recent years, because the in-situ chemical oxidation style is to the high efficiency of toxic Pollutant Treatment with to the promoter action of biological restoration, thereby be subjected to people's extensive concern.At present, in-situ chemical oxidation oxygenant commonly used has potassium permanganate, hydrogen peroxide and Fenton reagent, persulphate and ozone.Yet deficiencies such as in-situ chemical oxidation style ubiquity use cost height and application conditions harshness.
Since the eighties in 20th century, developed country's study of groundwater pollution has turned to organic contamination from inorganic pollution, the reduction technique of Zero-valent Iron also grows up gradually, mainly be that reductive action by Zero-valent Iron is chlorion with the chlorine element reduction in organic hydrochloric ether, to reach the purpose of nontoxic or low toxicity.This technology has advantages such as cost is low, easy to operate, and the industrial waste that comes from mostly of the iron filings that use of experiment, has the meaning of the treatment of wastes with processes of wastes against one another for environment protection; In addition, abundant iron ore is rich in China, the raw material abundance, and the price material benefit, therefore, the Zero-valent Iron treatment technology has vast potential for future development.
Permeability response wall technology (PRB) is an important application of Zero-valent Iron reduction technique, can carry out reduction dechlorination to the hydrochloric ether in the underground water effectively.With respect to traditional methods such as extraction processing, it has can handle multiple pollutent, cost performance simultaneously relatively than advantages such as height.But in actual applications, because the groundwater environment condition is comparatively complicated, can form the layer of metal oxide film on the surface of Zero-valent Iron, has stoped metal and organic pollutant to carry out transfer transport, even the blocking medium hole, thereby the removal efficient of hydrochloric ether is descended gradually.
Though it is more to hydrochloric ether Processing Technology in the underground water both at home and abroad, but it is less for the research that the hydrochloric ether that is present in simultaneously in underground water and the soil is administered simultaneously, therefore, the treatment technology of studying hydrochloric ether in underground water and the soil mud system simultaneously has certain practical significance.
[summary of the invention]
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of chemical reduction to remove the method for hydrochloric ether in underground water and the soil mud system.
The objective of the invention is to be achieved through the following technical solutions:
The method of hydrochloric ether in underground water and the soil mud system is removed in a kind of chemical reduction, its concrete steps are: after making that by mechanical stirring the mud that contains chlorinated hydrocarbon contaminants mixes, add Zero-valent Iron in the mud system and react, realize the repairing and treating of hydrochloric ether polluted underground water and soil.
Mass ratio in the Zero-valent Iron of described adding and the contaminated soil between the contained hydrochloric ether is 100: 1～1600: 1, and particle diameter is 0.125～0.180mm.
Described Zero-valent Iron is iron powder.
The concentration of described hydrochloric ether in mud system is 100～500mg/kg soil; Soil ratio in the mud system is 5: 1.
Described reaction conditions is: the control temperature of reaction is at 15 ℃～30 ℃, and reaction pH is 6～7, and reaction process is carried out sufficient mechanical stirring.
Described hydrochloric ether is modal pollutent in the contaminated site: 1, trieline and zellon.
Add Zero-valent Iron in the mud system that contains chlorinated hydrocarbon contaminants and carry out reduction reaction, in the extraction of from mud system, taking a sample of different time periods, and with the content of hydrochloric ether in the gas chromatograph for determination sample, find that the removal effect of hydrochloric ether is remarkable after above-mentioned chemical reduction reaction.
Compared with prior art, positively effect of the present invention is:
(1) operation is simple in the present invention, and obvious processing effect can be handled the hydrochloric ether in underground water and the soil simultaneously;
(2) abundant iron ore is rich in China, raw material abundance, price material benefit;
(3) the present invention uses mechanical stirring, and in reaction process, water and soil can fully mix, and Zero-valent Iron also can fully contact with hydrochloric ether, thereby reaches best treatment effect;
(4) influenced by the temperature of mud system and pH less for reaction process of the present invention, and little to the destruction of structure of the soil itself, and the environment that is fit to is more, is widely used;
(5) Zero-valent Iron reducing power of the present invention is strong, and the mass ratio in Zero-valent Iron and the contaminated soil between the contained hydrochloric ether is 100: 1～1600: 1 o'clock, and the clearance of hydrochloric ether can reach more than 99.5%;
(6) the present invention not only can repair underground water and the soil that hydrochloric ether pollutes effectively simultaneously, and for the contamination with chlorinated organics of other easy volatilies very high processing efficiency is arranged also, and removable pollutant kind is various.
[embodiment]
Below provide a kind of chemical reduction of the present invention to remove the embodiment of hydrochloric ether method in underground water and the soil mud system.
Embodiment 1
1,1,1-trichloroethane pollution concentration is (guaranteeing that soil ratio is 5: 1) in the matrix of 100mg/kg contaminated soil, add 50g Zero-valent Iron (every kg soil (dry weight)), carry out slowly also sufficient mechanical stirring, the pH that controls mud system simultaneously is 7, temperature of reaction is 20 ℃, and the reaction times is 24 hours, respectively 2,4,6,8,10,12,16,20, the extraction of taking a sample in 24 hours, adopt gas chromatograph to analyze 1, the concentration of 1,1-trichloroethane, the result is through 1 of art breading of the present invention, the clearance of 1,1-trichloroethane about 24 hours reaches 99.5%.
Embodiment 2
1,1,1-trichloroethane pollution concentration is (guaranteeing that soil ratio is 5: 1) in the matrix of 100mg/kg contaminated soil, add 200g Zero-valent Iron (every kg soil (dry weight)), carry out slowly also sufficient mechanical stirring, the pH that controls mud system simultaneously is 7, temperature of reaction is 20 ℃, and the reaction times is 24 hours, respectively 2,4,6,8,10,12,16,20, the extraction of taking a sample in 24 hours, adopt gas chromatograph to analyze 1, the concentration of 1,1-trichloroethane, the result is through 1 of art breading of the present invention, the clearance of 1,1-trichloroethane about 12 hours reaches 99.9%.
Embodiment 3
1,1,1-trichloroethane pollution concentration is (guaranteeing that soil ratio is 5: 1) in the matrix of 500mg/kg contaminated soil, add 50g Zero-valent Iron (every kg soil (dry weight)), carry out slowly also sufficient mechanical stirring, the pH that controls mud system simultaneously is 7, temperature of reaction is 20 ℃, and the reaction times is 24 hours, respectively 2,4,6,8,10,12,16,20, the extraction of taking a sample in 24 hours, adopt gas chromatograph to analyze 1, the concentration of 1,1-trichloroethane, the result is through 1 of art breading of the present invention, the clearance of 1,1-trichloroethane about 24 hours reaches 99.5%.
Embodiment 4
1,1,1-trichloroethane pollution concentration is (guaranteeing that soil ratio is 5: 1) in the matrix of 100mg/kg contaminated soil, add 50g Zero-valent Iron (every kg soil (dry weight)), carry out slowly also sufficient mechanical stirring, the pH that controls mud system simultaneously is 7, temperature of reaction is 30 ℃, and the reaction times is 24 hours, respectively 2,4,6,8,10,12,16,20, the extraction of taking a sample in 24 hours, adopt gas chromatograph to analyze 1, the concentration of 1,1-trichloroethane, the result is through 1 of art breading of the present invention, the clearance of 1,1-trichloroethane about 24 hours reaches 99.5%.
Embodiment 5
1,1,1-trichloroethane pollution concentration is (guaranteeing that soil ratio is 5: 1) in the matrix of 100mg/kg contaminated soil, add 50g Zero-valent Iron (every kg soil (dry weight)), carry out slowly also sufficient mechanical stirring, the pH that controls mud system simultaneously is 6, temperature of reaction is 20 ℃, and the reaction times is 24 hours, respectively 2,4,6,8,10,12,16,20, the extraction of taking a sample in 24 hours, adopt gas chromatograph to analyze 1, the concentration of 1,1-trichloroethane, the result is through 1 of art breading of the present invention, the clearance of 1,1-trichloroethane about 8 hours reaches 99.9%.
Embodiment 6
Be in the matrix of 100mg/kg contaminated soil (guaranteeing that soil ratio is 5: 1) in the trieline pollution concentration, add 50g Zero-valent Iron (every kg soil (dry weight)), carry out slowly also sufficient mechanical stirring, the pH that controls mud system simultaneously is 7, temperature of reaction is 20 ℃, reaction times is 24 hours, the extraction of taking a sample at 2,4,6,8,10,12,16,20,24 hours respectively, adopt gas chromatograph to analyze the concentration of trieline, the result reaches 95% through the clearance of trieline about 24 hours of art breading of the present invention.
Embodiment 7
Be in the matrix of 100mg/kg contaminated soil (guaranteeing that soil ratio is 5: 1) in the trieline pollution concentration, add 200g Zero-valent Iron (every kg soil (dry weight)), carry out slowly also sufficient mechanical stirring, the pH that controls mud system simultaneously is 7, temperature of reaction is 20 ℃, reaction times is 24 hours, the extraction of taking a sample at 2,4,6,8,10,12,16,20,24 hours respectively, adopt gas chromatograph to analyze the concentration of trieline, the result reaches 99.5% through the clearance of trieline about 24 hours of art breading of the present invention.
Embodiment 8
Be in the matrix of 100mg/kg contaminated soil (guaranteeing that soil ratio is 5: 1) in the zellon pollution concentration, add 50g Zero-valent Iron (every kg soil (dry weight)), carry out slowly also sufficient mechanical stirring, the pH that controls mud system simultaneously is 7, temperature of reaction is 20 ℃, reaction times is 24 hours, the extraction of taking a sample at 2,4,6,8,10,12,16,20,24 hours respectively, adopt gas chromatograph to analyze the concentration of zellon, the result reaches 90% through the clearance of zellon about 24 hours of art breading of the present invention.
Method of the present invention is in treating processes, guarantees under the condition of Zero-valent Iron existence the hydrochloric ether in underground water and the soil mud system to be handled; The superiority of present method is: operation is simple for this method, and obvious processing effect can be handled the hydrochloric ether in underground water and the soil simultaneously; The Zero-valent Iron source is abundant, and low price has stronger reducing power; The removal efficient height of hydrochloric ether, the clearance of 1 reaches 99.5%; It is less that reaction process is influenced by the temperature of mud system and pH, and adaptability is strong, is widely used.
The above only is preferred implementation 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 (6)
1. the method for hydrochloric ether in underground water and the soil mud system is removed in a chemical reduction, it is characterized in that, its concrete steps are: after making that by mechanical stirring the mud that contains chlorinated hydrocarbon contaminants mixes, add Zero-valent Iron in the mud system and react, realize the repairing and treating of hydrochloric ether polluted underground water and soil.
2. the method for hydrochloric ether in underground water and the soil mud system is removed in a kind of chemical reduction as claimed in claim 1, it is characterized in that, mass ratio in the Zero-valent Iron of described adding and the contaminated soil between the contained hydrochloric ether is 100: 1～1600: 1, and particle diameter is 0.125～0.180mm.
3. the method for hydrochloric ether in underground water and the soil mud system is removed in a kind of chemical reduction as claimed in claim 1, it is characterized in that described Zero-valent Iron is iron powder.
4. the method for hydrochloric ether in underground water and the soil mud system is removed in a kind of chemical reduction as claimed in claim 1, it is characterized in that the concentration of described hydrochloric ether in mud system is 100～500mg/kg soil; Soil ratio in the mud system is 5: 1.
5. the method for hydrochloric ether in underground water and the soil mud system is removed in a kind of chemical reduction as claimed in claim 1, it is characterized in that, described reaction, its reaction conditions is: the control temperature of reaction is at 15 ℃～30 ℃, reaction pH is 6～7, and reaction process is carried out sufficient mechanical stirring.
6. the method for hydrochloric ether in underground water and the soil mud system is removed in a kind of chemical reduction as claimed in claim 1, it is characterized in that described hydrochloric ether is modal pollutent in the contaminated site: 1, trieline and zellon.
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| CN106492714A (en) * | 2016-10-28 | 2017-03-15 | 华中科技大学 | The preparation and application of calcium alginate coated Nanoscale Iron microsphere |
| CN107321782A (en) * | 2016-04-29 | 2017-11-07 | 上海市环境科学研究院 | A kind of method that EDTA complexings ferrous ion activation calper calcium peroxide removes soil petrochina hydrocarbon |
| CN107790488A (en) * | 2017-06-06 | 2018-03-13 | 大连理工大学 | The method of chlorohydrocarbon and recycling in degraded soil |
| CN110372083A (en) * | 2019-06-20 | 2019-10-25 | 华东理工大学 | The method that nano zero valence iron strengthens chlorohydrocarbon in underground water of SODIUM PERCARBONATE/Fe (II) system removal containing surfactant |
| 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 |
| CN110526377A (en) * | 2019-09-02 | 2019-12-03 | 北京高能时代环境技术股份有限公司 | A method of repairing chloro-carbon solvent polluted underground water |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111777158A (en) * | 2020-07-14 | 2020-10-16 | 清华大学深圳国际研究生院 | Method for reducing and degrading brominated flame retardant in liquid phase and soil |
| CN111892151A (en) * | 2020-07-16 | 2020-11-06 | 天津大学 | Method for degrading chlorohydrocarbon by using natural polyphenol-reduced iron powder composite agent |
| CN111892152A (en) * | 2020-07-16 | 2020-11-06 | 天津大学 | Method for degrading chlorohydrocarbon by activating persulfate through natural polyphenol-reduced iron powder |
| CN112429830A (en) * | 2020-10-28 | 2021-03-02 | 暨南大学 | In-situ constructed bone charcoal catalysis Fe (OH)2Environmental remediation method for removing chlorinated hydrocarbon |
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Application publication date: 20130911 |