KR101464878B1 - Remediation system for Multi-contaminated soils combining Chemical Oxidation and Soil Flushing and Electrokinetic Separation and Remediation method using the same - Google Patents

Abstract

An aspect of the present invention provides a remediation system for complexly contaminated soil using a combined chemical oxidation and soil flushing method by electrokinetic remediation that increases the remediation efficiency of complexly contaminated soil as a treatment region is formed by hydrogen peroxide inserted into one side of a soil cell from an anode cell to induce the oxidation and decomposition of oil contaminants and the oil contaminants are oxidized and decomposed by being flushed and adsorbed by an anionic surface active agent inserted into the other side of the soil cell from a cathode cell to be moved into the treatment region. The remediation system for complexly contaminated soil using a combined chemical oxidation and soil flushing method by electrokinetic remediation according to an embodiment of the present invention comprises: a soil cell complexly contaminated by oil contaminants and heavy metal contaminants; an anode cell having an anode inserted into one side of the soil cell; a cathode cell having a cathode inserted into the other side of the soil cell to be separated from the anode by a certain distance; a hydrogen peroxide supply cell connected to the anode cell to supply hydrogen peroxide to one side of the soil cell; a first anionic surface active agent supply cell connected to the cathode cell to supply a first anionic surface active agent to the other side of the soil cell; and a power supply device for flushing and adsorbing oil contaminants via electric ion movement using the first anionic surface active agent to be moved from the cathode to the treatment region while simultaneously forming the treatment region, which is defined by the flowing distance of hydrogen peroxide, so that oil contaminants can be oxidized and decomposed as hydrogen peroxide is moved from the anode to the cathode via electroosmosis by supplying power to the anode and the cathode.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a purification system for a contaminated soil which combines a chemical oxidation method with a soil cleaning method and a purification method using the same.

The present invention relates to a purification system for a combined contaminated soil that combines a chemical oxidation method with a soil cleaning method in a coin technique and a purification method using the same. More particularly, the present invention relates to a purification system using a hydrogen peroxide injected from a cathode cell to a soil cell, The anion surfactant injected from the cathode cell into the soil cell side while the induced treatment area is formed, the oil contaminant is washed and adsorbed to the treatment area to oxidize and decompose the oil contaminant, thereby improving the purification efficiency of the contaminated soil And to a purification method using the same. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a purification system for a complex contaminated soil, which comprises a chemical oxidation method and a soil cleaning method.

As a result of the rapid increase of oil consumption due to industrialization and the development of various kinds of organic synthetic materials and their usage is continuously increased, these materials are used in natural environments due to accidents and deliberate discharge in the course of production, And has caused serious environmental pollution. Accordingly, there has been a great demand for development of a technique for recovering contaminated soil. Conventional methods for purifying contaminated soil include chemical oxidation, soil cleaning, and electrochemical purification.

The chemical oxidation method is a method of artificially introducing an oxidizing agent such as hydrogen peroxide into the soil to completely remove the contaminants by water and carbon dioxide. Recently, it is very popular because of its short treatment time and high treatment efficiency. However, oxidizing agent must be supplied to the soil to contact with pollutants for oxidation, but the hydraulic conductivity of the clay soil is too low to inject or contact the chemical oxidizing agent.

Soil cleansing method is a technique of extracting and disposing pollutants adsorbed on the soil by injecting water containing additive for enhancing solubility of water or pollutants into the soil pores through the gutters. The washing solution flowing through the injection wells passes through the contaminated area under the soil, increases the solubility of the contaminants adsorbed on the soil soil, desorbs them from the soil particles, and purges the soil in the contaminated area by pumping it through the extraction well. The soil washing method has a disadvantage in that it is less economical than other processes due to the high cleaning agent cost in treating insecticide, volatile organic compound, and semi-volatile organic compound. In addition, in the case of low permeability soil, the treatment efficiency is lowered because it is restricted by the movement of the washing solution. In addition, there is a possibility of secondary contamination due to a cleaning solution such as a surfactant, In particular, it may lead to the spread of pollutants to saturated areas.

Electrophoresis technology is a method in which electrodes are installed in a soil and electric current is applied to induce electrical, chemical, and hydraulic conduction phenomenon to remove contaminants by moving the fluid in the soil, Can effectively remove contaminants from soil and groundwater by the combined effect of electro-osmosis and ion transport.

One aspect of the present invention is to provide an anion surfactant which is injected by electric ion transfer from a cathode cell to a soil cell side while forming a treatment region in which oxidative decomposition of oil contaminants is induced by hydrogen peroxide injected into one side of a soil cell in a cathode cell, And a method of purifying a complex contaminated soil by combining a chemical oxidation method and a soil cleaning method to improve a purification efficiency of a complex contaminated soil by causing oil pollutants to oxidize and decompose by moving the oil pollutants to the treatment area And to provide a purification method.

Another aspect of the present invention is to suppress the introduction of OH- ions into the cathode cell caused by electrolysis using an organic acid having a large OH-buffering capacity in the cathode cell, thereby reducing the cleaning efficiency due to precipitation of heavy metal ions by hydroxide precipitation near the cathode cell The present invention is to provide a purification system for a complex contaminated soil that combines a chemical oxidation method and a soil washing method with a coin technique capable of preventing the contamination of the soil.

Another aspect of the present invention is to provide a purification system for a complex contaminated soil which combines a chemical oxidation method and a soil cleaning method with a coin technique that allows the hydrogen peroxide to be stably decomposed by further injecting an anionic surfactant into the anode cell, and a purification method using the same .

A purification system for a combined contaminated soil, which combines a chemical oxidation method and a soil washing method in a coin technique according to an embodiment of the present invention, comprises a soil cell complexly contaminated with oil contaminants and heavy metal contaminants, an anode having a positive electrode inserted into one side of the soil cell A cathode cell having a negative electrode inserted into the other side of the soil cell so as to be spaced apart from the positive electrode by a predetermined distance; a hydrogen peroxide supply cell connected to the anode cell to provide hydrogen peroxide to one side of the soil cell; A first anion surfactant supply cell connected to the cathode cell to provide a first anionic surfactant to the anode side and a cathode side electrode to supply electricity to the positive electrode and the negative electrode so that the hydrogen peroxide moves from the positive electrode toward the negative electrode by electroosmosis, A treatment area defined by the flow distance at which hydrogen peroxide is moved so as to induce degradation, and It characterized in that it comprises a; power supply which causes an electric ions move to the first anionic surfactant to the cleaning by suction of oil contaminants move to the treatment area on the negative electrode.

Further, the present invention is characterized by further comprising a pH buffer supply cell for providing a pH buffer for neutralizing OH ^- ions on the other side of the soil cell.

Further, the treatment area is characterized by being adjusted to a range of 40 to 60% of the interval between the negative electrode and the positive electrode.

And a second anionic surfactant supply cell connected to the anode cell to provide a second anionic surfactant to one side of the soil cell.

The anode cell and the cathode cell each include a vertical anode cell and a vertical cathode cell.

Each of the anode cell and the cathode cell includes a horizontal anode cell and a horizontal cathode cell.

In addition, the first and second anionic surfactants are characterized by comprising sodium dodecyl sulfate.

Further, the pH buffer solution is characterized by containing organic acid and / or nitric acid, sulfuric acid, and hydrochloric acid composed of at least one of nitric acid, citric acid, hydroxycarboxylic acid and succinic acid.

Also, the oil contaminants are characterized by comprising TPH contaminants.

In another aspect of the present invention, there is provided a system for purifying a complex contaminated soil, which comprises a chemical oxidation method and a soil washing method in combination with a coin technique according to an embodiment of the present invention. The system includes a soil cell complexly contaminated with oil pollutants and heavy metal contaminants, A negative electrode cell having a negative electrode inserted into the other side of the soil cell so as to be spaced apart from the positive electrode by a predetermined distance; a hydrogen peroxide supply cell connected to the positive electrode to supply hydrogen peroxide to one side of the soil cell; An anionic surfactant supply cell connected to the cathode cell to provide a first sodium dodecyl sulfate to the other side of the soil cell; and a second sodium dodecyl sulfate at one side of the soil cell connected to the anode cell, A pH buffer supply cell for supplying an organic acid to the other side of the soil cell; And the negative electrode is supplied with electric power to move the hydrogen peroxide from the positive electrode toward the negative electrode by electroosmosis to form a treatment region defined by the flow distance in which the hydrogen peroxide is moved so that the oxidative decomposition of the oil contaminant is oxidized and decomposed, And a power supply unit for causing the sodium dodecyl sulfate to clean and adsorb the oil contaminants and to move the electrode from the cathode electrode to the treatment area.

A method of purifying a composite contaminated soil, which is a combination of a chemical oxidation method and a soil washing method, in a coin technique according to an embodiment of the present invention includes the steps of inserting a positive electrode and a negative electrode into contaminated soil that is contaminated with oil pollutants and heavy metal pollutants, A step of injecting hydrogen peroxide and an anionic surfactant into the negative electrode; and a step of applying power to the positive electrode and the negative electrode to cause the hydrogen peroxide to move over the predetermined range from the positive electrode by electroosmosis to react with the iron in the soil, Forming a treatment region defined as a region where oxidative decomposition of oil pollutants is formed and simultaneously causing the anionic surfactant to adsorb and adsorb oil contaminants by electroion migration to move from the negative electrode to the treatment region and oxidative decomposition by hydroxyl radicals; And do.

A method for purifying a complex contaminated soil, which comprises combining a chemical oxidation method and a soil cleaning method in a coin technique according to another embodiment of the present invention, comprises the steps of: inserting a positive electrode and a negative electrode in contaminated soil that is contaminated with oil pollutants and heavy metal pollutants; A step of injecting hydrogen peroxide and an anionic surfactant and a pH buffer solution into the negative electrode side; and a step of applying a power source to the positive electrode and the negative electrode to cause hydrogen peroxide to move over a predetermined range from the positive electrode, The anion surfactant cleanses and adsorbs the oil contaminants by electroion migration and moves from the negative electrode to the treatment region and is oxidatively decomposed by the hydroxyl radicals while forming a treatment region defined as a region where the oil contaminants are oxidatively decomposed by the radicals ≪ / RTI > The features.

A method of purifying a complex contaminated soil, which combines a chemical oxidation method and a soil cleaning method in a coin technique according to another embodiment of the present invention, comprises the steps of: inserting a positive electrode and a negative electrode into contaminated soil contaminated with oil pollutants and heavy metal pollutants; A step of injecting hydrogen peroxide and an anionic surfactant and an anionic surfactant and a pH buffer into the negative electrode side; and applying power to the positive electrode and the negative electrode to move the hydrogen peroxide over the predetermined range by electroosmosis, The anion surfactant cleans and adsorbs the oil contaminants by electroion migration and moves to the treatment region from the negative electrode to form a treatment region defined by the hydroxyl radicals To be oxidatively decomposed by The method comprising the steps of:

Therefore, the purification system of the contaminated soil, which combines the chemical oxidation method and the soil cleaning method in the coin technique according to the embodiment of the present invention, and the purification method using the same, is characterized in that oxidative decomposition of oil pollutants by hydrogen peroxide injected from the anode cell to one side of the soil cell The anion surfactant injected from the cathode cell into the soil cell side while the induced treatment area is formed, the oil contaminant is washed and adsorbed to the treatment area to oxidize and decompose the oil contaminant, thereby improving the purification efficiency of the contaminated soil .

In addition, the purification system of the complex contaminated soil, which combines the chemical oxidation method and the soil cleaning method, with the coin technique according to the embodiment of the present invention is characterized in that the flow of hydrogen peroxide is reversed in order to flow the hydrogen peroxide over the whole soil It is possible to solve the problem of changing the polarities of the positive electrode and the negative electrode so as to induce them.

In addition, a purification system for a complex contaminated soil in which a chemical oxidation method and a soil cleaning method are combined with a coin technique according to an embodiment of the present invention, and a purification method using the same, are produced by electrolysis using an organic acid having OH- OH < / RTI > ions into the cathode cell, thereby preventing reduction of the purification efficiency of heavy metals due to hydroxide precipitation in the vicinity of the cathode cell.

In addition, a purification system for a complex contaminated soil in which a chemical oxidation method and a soil cleaning method are combined with a coin technique according to an embodiment of the present invention, and a purification method using the same, further include an anionic surfactant additionally injected into the anode cell to stably decompose the hydrogen peroxide .

In addition, the purification system for the contaminated soil, which combines the chemical oxidation method and the soil cleaning method in the coin technique according to the embodiment of the present invention, and the purification method using the same, comprises a horizontal anode cell and a horizontal cathode cell, It can be applied not only to a wide pollution space of the soil, but also to the effect that the pollution can be easily removed from the polluted space of the soil where the excavation is not possible, such as the lower part of the building.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view showing a purification system for a combined contaminated soil in which a chemical oxidation method and a soil washing method are combined with a coin technique according to an embodiment of the present invention. FIG.
FIG. 2 is a view showing a process of purifying oil contaminants in a system for cleaning contaminated contaminated soil by combining the chemical oxidation method and the soil washing method in the coin technique shown in FIG. 1;
FIG. 3 is a view illustrating a process of purifying heavy metal contaminants in a complex contaminated soil purification system combining the chemical oxidation method and the soil washing method in the coin technique shown in FIG. 1.
FIG. 4 is a view showing a method of purifying a complex contaminated soil by combining a chemical oxidation method and a soil washing method with a coin technique according to an embodiment of the present invention.
FIG. 5 is a view showing a purification system of a complex contaminated soil in which a chemical oxidation method and a soil cleaning method are combined with a coin technique according to another embodiment of the present invention.
FIG. 6 is a view showing a purification system of a complex contaminated soil, which is a combination of a chemical oxidation method and a soil washing method in a coin technique according to another embodiment of the present invention.
FIG. 7 is a view illustrating a system for purifying a complex contaminated soil by combining a chemical oxidation method and a soil washing method with a coin technique according to another embodiment of the present invention.
FIG. 8 is a view showing a purification system for a contaminated soil in which a chemical oxidation method and a soil cleaning method are combined with a coin technique according to another embodiment of the present invention.
9 is a graph showing the increase in hydrogen peroxide stability and the enlargement of the treatment area according to an embodiment of the present invention.
10 is a graph showing an increase in processing efficiency of the TPH according to the embodiment of the present invention.
11 is a graph showing an increase in treatment efficiency of a heavy metal (zinc) according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

FIG. 1 is a view showing a system for cleaning a contaminated soil, which is a combination of a chemical oxidation method and a soil washing method, according to an embodiment of the present invention. FIG. 2 is a schematic view showing a chemical oxidation method and a soil washing method FIG. 3 is a view showing a process of purifying oil contaminants in a combined contaminated soil purification system. FIG. 3 is a view showing a state in which heavy metal contaminants are purified in a purification system of a combined contaminated soil, which is a combination of a chemical oxidation method and a soil- Fig.

As shown in FIGS. 1 to 3, a cleaning system 10a for a combined contaminated soil, which combines a chemical oxidation method and a soil washing method in a coin technique according to an embodiment of the present invention, A cathode cell 200 having a cathode 100 inserted into one side of the soil cell 100 and a cathode electrode 200 inserted into the other side of the soil cell 100 so as to be spaced apart from the anode 210 by a predetermined distance, A hydrogen peroxide supply cell 400 connected to the anode cell 200 to provide hydrogen peroxide 410 to one side of the soil cell 100 and a hydrogen peroxide supply cell 400 connected to the anode cell 200 to supply the hydrogen peroxide 410 to one side of the soil cell 100, An anion surfactant supply cell 500 connected to the cathode cell 300 to supply the anion surfactant 510 to the anode electrode 210 and the anode electrode 310 and a hydrogen peroxide 410 Is moved from the positive electrode 210 toward the negative electrode 310, The treatment zone is defined as a flow distance at which the hydrogen peroxide 410 is moved so as to induce oxidative decomposition of the anion surfactant 510. At the same time, the anionic surfactant 510 cleanses and adsorbs the oil contaminants by the electro- 310 to a treatment zone (treatment zone).

The soil cell 100 is filled with soil contaminated with oil pollutants and heavy metal contaminants. Here, oil pollutants may include substances contaminated with TPH (total petroleum hydrocarbon), and heavy metal contaminants may include substances contaminated with arsenic, lead, copper, and cadmium.

A positive electrode 210 to which a positive voltage is applied is formed in the positive electrode cell 200 and an electrolyte solution is filled to cover the positive electrode 210. In addition, the anode cell 200 may include a first circulation pump 220 for keeping the concentration of the electrolyte filled therein constant.

A negative electrode 310 to which a negative voltage is applied is formed in the negative electrode cell 300 and an electrolyte solution is filled to surround the negative electrode 310. In addition, the cathode cell 300 may include a second circulation pump 320 for keeping the concentration of the electrolyte filled therein constant.

Here, the anode cell 200 and the cathode cell 300 may include a vertical anode cell 200 and a vertical cathode cell 300, respectively.

As the electrodes 210 and 310, conductors such as graphite, stainless steel, and titanium which are chemically inert and have conductivity can be used. On the other hand, in the positive electrode 210, an electrode coated with platinum, iridium, iron, or the like, which promotes the decomposition and consumption of the hydrogen peroxide 410 provided in the hydrogen peroxide supply cell 400 to be described later, is not used.

Each of the soil cell 100, the cathode cell 300 and the anode cell 200 is separated and connected to each other by a porous diaphragm 110 which is easily permeable to the solution, It is possible to prevent the cell 300 and the anode cell 200 from being introduced into the cell.

The hydrogen peroxide supply cell 400 is connected to the anode cell 200. The hydrogen peroxide supply cell 400 supplies a hydrogen peroxide solution 410 to the anode cell 200 to provide a treatment zone in which direct oxidation and decomposition of TPH contaminants present in the soil cell 100 is induced by hydroxyl radicals, .

That is, in the purification system 10a of the combined contaminated soil in which the chemical oxidation method and the soil washing method are combined with the coin technique according to the embodiment of the present invention, a treatment zone in which TPH contaminants are treated is formed. The treatment zone supplies power to the positive electrode 210 and the negative electrode 310 so that the hydrogen peroxide 410 is moved from the positive electrode 210 toward the negative electrode 310 by electroosmosis so that hydrogen peroxide 410) is moved.

An anion surfactant supply cell 500 is connected to the cathode cell 300. The anion surfactant supply cell 500 supplies the anion surfactant 510 to the cathode cell 300 to clean and adsorb the TPH contaminants present in the soil to thereby remove the treatment zone ).

The anionic surfactant 510 injected from the cathode cell 300 is present as a monomer in the solution but when the concentration of the anionic surfactant 510 exceeds the critical micelle concentration CMC, By the emulsifying action of these micelles, the surface tension of TPH contaminants and heavy metal contaminants adsorbed on the soil can be reduced to separate them from the soil, and the solubility can be increased to increase the removal efficiency.

As a result, the anionic surfactant 510 injected from the cathode cell 300 efficiently removes TPH contaminants by washing adsorption and electrophoresis, and at the same time, heavy metal contaminants can be efficiently removed by emulsification.

The anionic surfactant 510 may be selected from sodium dodecyl sulfate (SDS), sodium dodecyl benzene sulfonate (SDBS), preferably sodium dodecyl sulfate 510, Can be selected.

The electrolyte supply cell 700 can separately supply an electrolyte solution to the anode cell 200 and the cathode cell 300. The electrolytic solution supplied from the electrolyte supply cell 700 can maintain a constant head, Can be prevented. Here, examples of the electrolyte include NaCl, KH ₂ PO ₄ , MgSO _4, and the like.

An electrolyte recovery cell 800 is configured to measure the drainage amount of the electrolyte solution transferred from the positive electrode 210 to the negative electrode 310 by electroosmosis.

The power supply device 600 supplies power to the positive electrode 210 and the negative electrode 310, and can supply not only a direct current power source but also a pulsed power source.

Pulsed copper electrochemical technology is a technology to purify soil contaminated with TPH contaminants and heavy metal contaminants by generating various physical and electrochemical effects with instant pulse power instead of DC power. It is applicable to clay soil which was difficult to clean up pollution can do.

The power supply 600 supplies power to the positive electrode 210 and the negative electrode 310 so that the hydrogen peroxide 410 is moved from the positive electrode 210 toward the negative electrode 310 by electroosmosis, The anion surfactant 510 cleans and adsorbs the TPH contaminants by electroion migration to form a treatment zone in the treatment area (for example, Treatment zone.

As a result, the cleaning system 10a of the combined contaminated soil, in which the chemical oxidation method and the soil washing method are combined with the coin technique according to the embodiment of the present invention, is constructed such that one side and the other side of the soil cell 100, which is contaminated with TPH contaminants and heavy metal contaminants, The positive electrode 210 and the negative electrode 310 are inserted into the anode cell 200 and the cathode cell 300 respectively and the power supply device 600 is connected to supply electric power to cause electric osmosis. The hydrogen peroxide 410 and the electrolyte are injected into the hydrogen peroxide supply cell 400 and the electrolyte supply cell 700 connected to the cathode cell 200 and the anode cell 200, The anionic surfactant 510 is injected into the anion surfactant supply cell 500 connected to the anode cell 300 and injected to the other side of the soil cell 100 through the cathode cell 300.

The hydrogen peroxide 410 thus injected moves from the positive electrode 210 to the negative electrode 310 by electroosmosis, oxidizes and decomposes the TPH contaminants present therebetween, and flows into the treatment zone. The anion surfactant (510) moves from the negative electrode (310) to a treatment zone, thereby allowing the TPH contaminant present therein to be cleaned and adsorbed.

FIG. 4 is a view showing a method of purifying a complex contaminated soil by combining a chemical oxidation method and a soil washing method with a coin technique according to an embodiment of the present invention.

As shown in FIG. 4, a method of purifying a complex contaminated soil, which combines a chemical oxidation method and a soil cleaning method with a coin technique according to an embodiment of the present invention, is a method of cleaning a composite soil contaminated with oil pollutants and heavy metal contaminants, (Step S20) of injecting hydrogen peroxide into the positive electrode and injecting an anionic surfactant into the negative electrode, and applying power to the positive electrode and the negative electrode to move the hydrogen peroxide over the predetermined range in the positive electrode An anionic surfactant cleans and adsorbs TPH contaminants by electroion migration while forming a treatment region defined by the oxidative decomposition of TPH contaminants by the hydroxide radicals generated by the reaction with iron in the soil, And oxidized and decomposed by a hydroxyl radical (S3 0). ≪ / RTI >

Next, referring to FIGS. 1 to 4, the operation of the purification system for a complex contaminated soil, in which the chemical oxidation method and the soil cleaning method are combined with the coin technique according to one embodiment of the present invention, will be described in detail.

The combined contaminated soil purification system 10a that combines the chemical oxidation method and the soil washing method with the coin technique according to an embodiment of the present invention is a system in which TPH contaminants and heavy metal contaminants are present in the complexed soil cell 100, The hydrogen peroxide 410 and the anionic surfactant 510 are injected into the soil cell 100 and the anode 210 and the anode 310 are inserted into the soil cell 100 to supply electric power to the hydrogen peroxide 410, The anionic surfactant 510 moves from the negative electrode 310 toward the positive electrode 210. At the same time,

At this time, the hydrogen peroxide 410 has a treatment zone in a region adjacent to the positive electrode 210 defined by the flow distance at which the hydrogen peroxide 410 is moved so as to induce oxidative decomposition of TPH contaminants in the positive electrode 210, In this treatment zone, the TPH contaminant on the other side of the soil cell 100 which has undergone the oxidative decomposition of the TPH contaminant on one side of the soil cell 100 by the hydrogen peroxide 410 is treated in the treatment area zone to oxidize and decompose.

That is, the hydrogen peroxide 410 reacts with a metal salt such as iron (Fe ²⁺ ) existing in the soil cell 100 when it moves into the contaminated soil cell 100, thereby generating a hydroxyl radical by causing a Fenton oxidation reaction .

Thus, the Fenton oxidation reaction is one of the advanced oxidation processes for oxidizing and decomposing TPH contaminants, and the TPH contaminants are decomposed by hydroxyl radicals formed by the reaction of hydrogen peroxide (410) and the metal salt. In the actual soil treatment, since metal salts such as iron are present as minerals in the soil, the fentan oxidation reaction occurs without supplying metal salts such as iron separately.

The hydroxyl radicals (.OH) produced by the Fenton oxidation reaction have a strong oxidizing power and decompose and decompose TPH contaminants and react with heavy metal contaminants to change into harmless compounds.

As the hydrogen peroxide 410 is continuously injected into one side of the soil cell 100 while supplying power to the electrodes 210 and 310 as described above, hydroxide radicals are generated through the reaction as described above, and a predetermined region defined as a treatment zone The TPH contaminants are oxidatively decomposed in the range. At the same time, when the anionic surfactant 510 is continuously injected into the other side of the soil cell 100 while supplying power to the electrodes 210 and 310, the TPH contaminants are cleaned and moved to a treatment zone, So that it can be disassembled.

As a result, the cleaning system 10a of the combined contaminated soil, in which the chemical oxidation method and the soil cleaning method are combined with the coin technique according to an embodiment of the present invention, improves the mobility of the hydrogen peroxide 410 using electroosmosis, A treatment zone in which a radical reacts with TPH contaminants distributed in the soil cell 100 to form a treatment zone and an anionic surfactant 510 cleanses and adsorbs TPH contaminants by electrophoresis to form a negative electrode 310 ) To the treatment zone (treatment zone).

Electroosmosis is a phenomenon in which the surface of the soil is negatively charged. Therefore, when a current is applied to the electrodes due to the densification of the ions due to the attraction, the positive ions move from the positive electrode 210 toward the negative electrode 310 in the same direction It is a phenomenon of water flow. The electroosmosis phenomenon causes the hydrogen peroxide 410 to move toward the cathode electrode 310 by the flow of water so that the contaminants are oxidatively decomposed in the soil.

The oxidative decomposition of contaminants in the soil cell 100 is actively promoted at one side of the soil cell 100 which is the injection part where the hydrogen peroxide 410 is injected, that is, the anode 210, so that the contaminant removal efficiency is high, The anion surfactant 510 is injected into the portion where the hydrogen peroxide 410 is not injected so that the anionic surfactant 510 cleans the TPH contaminant and adsorbs the TPH contaminant Treatment zone so that it can be oxidatively decomposed by hydroxyl radicals.

As a result, on the negative electrode 310 where the pollutant removal rate has been lowered before, the detergent of the anionic surfactant 510 is removed by the oxidative decomposition action through the movement to the treatment zone by the electro- 100). ≪ / RTI > Here, the concentration of the hydrogen peroxide 410 for the formation of the treatment zone may be determined in consideration of the moisture content of the soil cell 100, the contaminant concentration and other organic matter contents, and the treatment zone And the distance between the cathode electrode 310 and the anode electrode 210 is controlled to be in the range of 40 to 60%, thereby achieving a more efficient and uniform purification efficiency in the whole area of the soil cell 100.

Another embodiment of the present invention will be described with reference to Fig. The same reference numerals are assigned to the same components as those of the above-described embodiment, and a description thereof will be omitted. FIG. 5 is a view showing a purification system of a complex contaminated soil in which a chemical oxidation method and a soil cleaning method are combined with a coin technique according to another embodiment of the present invention.

As shown in FIG. 5, the system 10b for cleaning a complex contaminated soil, which combines the chemical oxidation method and the soil washing method in the coin technique according to another embodiment of the present invention, comprises a soil pollution- A positive electrode 200 having a positive electrode 210 inserted into one side of the soil cell 100 and a negative electrode 310 inserted into the other side of the soil cell 100 so as to be separated from the positive electrode 210 by a predetermined distance, A hydrogen peroxide supply cell 400 connected to the anode cell 200 to provide hydrogen peroxide 410 to one side of the soil cell 100 and a hydrogen peroxide supply cell 400 connected to the other side of the soil cell 100, An anionic surfactant supply cell 500 connected to the cathode cell 300 to provide the activator 510 and a pH buffer 510 'for neutralizing OH ^- ions on the other side of the soil cell 100 A pH buffer liquid supply cell 500 'for supplying power to the positive electrode 210 and the negative electrode 310, A treatment zone defined as a flow distance in which the hydrogen peroxide 410 is moved so that the hydrogen peroxide 410 is moved from the anode 210 to the anode 310 by the electric osmosis to induce oxidative decomposition of oil pollutants, And an electric power supply device 600 for allowing the anionic surfactant 510 to clean and adsorb the oil contaminants and to move from the negative electrode 310 to the treatment zone by the movement of the electric ion .

On the other side of the soil cell 100, OH ^- ions generated by electrolysis in the cathode electrode 310 during the purification treatment of heavy metal contaminants are moved in the vicinity of the cathode electrode 310 due to electrical migration due to electrical attraction and diffusion due to the concentration difference In the cleaning system 10a for a combined contaminated soil in which the chemical oxidation method and the soil washing method are combined with the coin technique according to another embodiment of the present invention, ) To inject the pH buffer (510 ') so that the inflow of such OH ^- ions can be suppressed.

Here, the pH buffer solution 510 'injected from the pH buffer supply cell 500' may include an organic acid 510 'made of at least one of acetic acid, citric acid, hydroxycarboxylic acid, and succinic acid.

It goes without saying that any one of nitric acid, sulfuric acid, and hydrochloric acid may be added to the organic acid 510 'in the pH buffer solution 510' injected from the pH buffer supply cell 500 '.

Therefore, the cleaning system 10b of the combined contaminated soil, which combines the chemical oxidation method and the soil washing method in the coin technique according to another embodiment of the present invention, further includes a pH buffer supply cell 500 'to remove not only oil contaminants but also heavy metal contaminants Thereby enabling efficient purification treatment.

Another embodiment of the present invention will be described with reference to Fig. The same reference numerals are assigned to the same components as those of the above-described embodiment, and a description thereof will be omitted. FIG. 6 is a view showing a purification system of a complex contaminated soil, which is a combination of a chemical oxidation method and a soil washing method in a coin technique according to another embodiment of the present invention.

As shown in FIG. 6, the system 10c for cleaning a complex contaminated soil, which combines a chemical oxidation method and a soil washing method in a coin technique according to another embodiment of the present invention, comprises a soil cell A negative electrode 310 inserted into the other side of the soil cell 100 so as to be spaced apart from the positive electrode 210 by a predetermined distance; A hydrogen peroxide supply cell 400 connected to the anode cell 200 to provide hydrogen peroxide 410 to one side of the soil cell 100 and a hydrogen peroxide supply cell 400 connected to the other side of the soil cell 100, An anion surfactant supply cell 500 connected to the cathode cell 300 to provide a surfactant 510 and an anion surfactant supply cell 500 connected to the anode cell 200 to improve the stability of the hydrogen peroxide 410, A stabilizer supply cell 400 'provided on one side of the positive electrode 210, A treatment that is defined as a flow distance in which hydrogen peroxide 410 is moved so that the hydrogen peroxide is moved from the anode 210 to the anode 310 by the electric osmosis by supplying power to the cathode 310, And a power supply device 600 for forming a treatment zone and moving the anion surfactant 510 to move from the negative electrode to the treatment zone by washing and adsorbing the oil contaminant by the movement of the electric ion .

The stabilizer supply cell 400 'is connected to the anode cell 200 to increase the stability of the hydrogen peroxide 410 to provide an anionic surfactant 410' to one side of the soil cell 100, And a second anionic surfactant supply cell 400 'that delays the decomposition rate.

That is, the stabilizer supply cell 400 'may include a second anion surfactant supply cell 400' that prevents the hydrogen peroxide 410 from being abruptly decomposed into hydroxyl radicals having a short lifetime by the Fenton oxidation reaction .

This second anionic surfactant 410 'may be selected from sodium dodecyl sulfate (SDS), sodium dodecylbenzenesulfonate (SDBS), and preferably sodium dodecyl sulfate 410' .

Specifically, the hydrogen peroxide 410 introduced into the soil cell 100 is reacted with a metal salt of the soil to produce a hydroxide radical and a metal oxide, wherein the metal oxide is sodium dodecylsulfate 410 ' To form a complex.

Thus, the complex formed from the metal oxide and the sodium dodecylsulfate (410 ') acts as a stabilizer to delay the decomposition rate of the hydrogen peroxide, so that even when a small amount of the hydrogen peroxide 410 is treated, Effect can be achieved.

Therefore, the cleaning system 10c of the combined contaminated soil, in which the chemical oxidation method and the soil cleaning method are combined with the coin technique according to another embodiment of the present invention, And the process of treating the oil pollutants in the treatment zone is stabilized through the improvement of the stability of the hydrogen peroxide 410 and the effect of decomposing the oil pollutants is maintained for a longer period of time.

Another embodiment of the present invention will be described with reference to Fig. The same reference numerals are assigned to the same components as those of the above-described embodiment, and a description thereof will be omitted. FIG. 7 is a view illustrating a system for purifying a complex contaminated soil by combining a chemical oxidation method and a soil washing method with a coin technique according to another embodiment of the present invention.

As shown in FIG. 7, the system 10d for cleaning a complex contaminated soil, which combines a chemical oxidation method and a soil washing method in a coin technique according to another embodiment of the present invention, A negative electrode 310 inserted into the other side of the soil cell 100 so as to be spaced apart from the positive electrode 210 by a predetermined distance; A hydrogen peroxide supply cell 400 connected to the anode cell 200 to provide hydrogen peroxide 410 to one side of the soil cell 100 and a hydrogen peroxide supply cell 400 connected to the other side of the soil cell 100. [ A first anionic surfactant supply cell 500 connected to the cathode cell 300 to provide a first anionic surfactant 510 and a second anionic surfactant 410 'to one side of the soil cell 100 A second anionic surfactant supply cell 400 'connected to the anode cell 200 to form a soil cell A pH buffer liquid supply cell 500 'for supplying a pH buffer solution 510' for neutralizing OH ^- ions on the other side of the electrodes 100 and 100 and a pH buffer liquid supply cell 500 'for supplying electricity to both the positive electrode 210 and the negative electrode 310, A treatment zone is defined as a flow distance in which the hydrogen peroxide 410 is moved from the positive electrode toward the negative electrode to induce oxidative decomposition of the oil contaminant, And a power supply unit 600 for allowing the monoanionic surfactant 510 to sweep and adsorb oil contaminants to move from a negative electrode to a treatment zone.

In the coin technique according to another embodiment of the present invention, the complex contaminated soil purification system 10d, which combines the chemical oxidation method and the soil cleaning method, comprises the second anion surfactant supply cell 400 'and the pH buffer supply cell 500' Thereby improving the stability of the hydrogen peroxide 410 while stabilizing not only the oil pollutants but also the heavy metal contaminants more efficiently, and stabilizing the treatment process of the oil pollutants in the treatment zone.

Another embodiment of the present invention will be described with reference to Fig. The same reference numerals are assigned to the same components as those of the above-described embodiment, and a description thereof will be omitted. FIG. 8 is a view showing a purification system for a contaminated soil in which a chemical oxidation method and a soil cleaning method are combined with a coin technique according to another embodiment of the present invention.

As shown in FIG. 8, the system 10e for cleaning a complex contaminated soil, which combines a chemical oxidation method and a soil cleaning method in a coin technique according to another embodiment of the present invention, A negative electrode 310 inserted into the other side of the soil cell 100 so as to be spaced apart from the positive electrode 210 by a predetermined distance; A hydrogen peroxide supply cell 400 connected to the anode cell 200 to provide hydrogen peroxide 410 to one side of the soil cell 100 and a hydrogen peroxide supply cell 400 connected to the other side of the soil cell 100. [ A first anionic surfactant supply cell 500 connected to the cathode cell 300 to provide a first anionic surfactant 510 and a second anionic surfactant 410 'to one side of the soil cell 100 A second anionic surfactant supply cell 400 'connected to the anode cell 200 to form a soil cell A pH buffer liquid supply cell 500 'for supplying a pH buffer solution 510' for neutralizing OH ^- ions on the other side of the electrodes 100 and 100 and a pH buffer liquid supply cell 500 'for supplying electricity to both the positive electrode 210 and the negative electrode 310, A treatment zone is defined as a flow distance in which the hydrogen peroxide 410 is moved from the positive electrode toward the negative electrode to induce oxidative decomposition of the oil contaminant, And a power supply unit (not shown) for allowing the monoanionic surfactant 510 to move the pollutant to the treatment zone by washing and adsorbing the pollutant, and the positive electrode cell 200 and the negative electrode Each of the cells 300 includes a horizontal anode cell 200 and a horizontal cathode cell 300.

Although the anode cell 200 and the cathode cell 300 are formed as the horizontal anode cell 200 and the horizontal cathode cell 300 respectively and the electrode cells 200 and 300 are minimized in number, So that it is possible to easily remove contaminants from the contaminated space of the soil cell 100, which can not be excavated such as a lower part of the building.

Example

1. Increase of hydrogen peroxide stability and enlargement of treatment area (experimental period 240 hours, see FIG. 9)

Comparative Example A: anode: 7% hydrogen peroxide supply, cathode: non-ionized water supply

Example A: Positive electrode: 7% hydrogen peroxide + 20 mM SDS (anionic surfactant) supply, negative electrode: non-ionized water supply

2. TPH (Experimental period 240 hours, see Fig. 10)

COMPARATIVE EXAMPLE 1 Positive electrode: no hydrogen peroxide supply, negative electrode: non-ionized water supply

Comparative Example 2: anode: 7% hydrogen peroxide supply, cathode: non-ionized water supply

Example 1 Positive electrode: 7% hydrogen peroxide supply, negative electrode: 20 mM SDS (anionic surfactant) supply

Example 2 Positive electrode: 7% hydrogen peroxide + 20 mM SDS (anionic surfactant) supplied, negative electrode: 20 mM SDS (anionic surfactant) supplied

3. Increase in treatment efficiency of heavy metals (zinc) (see FIG. 11)

Comparative Example 3: anode: 7% hydrogen peroxide supply, cathode: non-ionized water supply

Example 3: anode: 7% hydrogen peroxide supply, cathode: 20 mM SDS (anionic surfactant) supply

Example 4 Anode: 7% Hydrogen peroxide + 20 mM SDS (anionic surfactant) supplied, Cathode: 20 mM SDS (anionic surfactant) supplied

Example 5: anode; 7% hydrogen peroxide + 20 mM SDS (anionic surfactant) supply, cathode: 20 mM SDS (anionic surfactant), 20 mM citric acid

4. Results

A 30 cm reactor was charged with soil contaminated with 500 mg of THP contaminant and 1000 mg of Zn per 1 kg of soil and sodium dodecyl sulfate was injected into the anode cell 200 and the hydrogen peroxide solution and the cathode cell 300 respectively. At this time, an anionic surfactant (SDS) was added as an electrolyte to the hydrogen peroxide solution. Then, a direct current was applied to the positive electrode 210 and the negative electrode 310 to cause an electroosmosis phenomenon.

As a result, a fluid flow from the positive electrode 210 to the negative electrode 310 was observed. After 7 days, samples were collected from the anode electrode 210 to the cathode electrode 310 at intervals of 5 cm, and the amount of THP contaminants remaining in the soil was analyzed by HPLC (high performance liquid chromatography).

After the completion of the experiment, the soil was collected by distillation and dried, and 1 g of the sample was taken in 10 ml of methanol and stirred for 24 hours. When the supernatant of the liquid phase was injected into the HPLC analyzer, And the concentration of phenanthrene is obtained by converting the area into the concentration.

As can be seen from FIGS. 9 to 11, in the case of Comparative Example 1 in which no hydrogen peroxide was injected into the anode cell 200, THP contaminants tend to be adsorbed on the soil even if fluid flow due to electroosmosis occurs Therefore, the cleaning efficiency was low and the cleaning efficiency was low.

In the case of Comparative Example 2 in which hydrogen peroxide was injected into the anode cell 200 but no sodium dodecyl sulfate was injected into the cathode cell 300, the hydrogen peroxide was difficult to migrate. In the treatment zone, , No decomposition occurred at all, showing very low removal efficiency.

In contrast, in Examples 1 to 5 where sodium dodecyl sulfate was injected into the cathode cell 300 while hydrogen peroxide was injected into the anode cell 200, all of them showed high contaminant removal rates.

For example, in the case of the first embodiment 1, 0.2 to 0.5 million remained in the treatment zone and 0.5 to 0.6 in the non-treatment zone in the positive electrode 210, indicating that even pollutants were decomposed and removed over the entire area . At this time, when the sodium dodecyl sulfate is injected into the anode cell 200, the stability of the hydrogen peroxide greatly increases and the treatment zone is enlarged.

As can be seen from FIG. 11, in Examples 3 to 5 as compared with Comparative Example 3, the removal rate of Zn contaminants is generally improved. In particular, in Example 5 in which citric acid was added, the Zn contaminants tended to migrate throughout the whole area.

As a result, in the first to fifth embodiments, sodium dodecyl sulfate is injected into the cathode cell 300 while injecting hydrogen peroxide into the anode cell 200. In the first to third embodiments, the treatment zone and the non-treatment zone The THP contaminants were greatly reduced, and in particular, Example 5 shows a remarkably high purification efficiency in the treatment of heavy metal contaminants.

As described above, the purification system of the complex contaminated soil, which combines the chemical oxidation method and the soil cleaning method in the coin technique according to the embodiment of the present invention, and the purification method using the same, is characterized in that the hydrogen peroxide injected to the one side of the soil cell in the anode cell oxidizes The treatment efficiency of the complex contaminated soil is improved by allowing the oil pollutants to be washed and adsorbed by the anionic surfactant injected from the cathode cell to the soil cell side while forming the treatment region in which the decomposition is induced, And the like, as a basic technical idea. Therefore, many modifications may be made by those skilled in the art without departing from the scope of the present invention.

10a ~ 10e ... Purification system of complex polluted soil 100 .. Soil cell
200 ... anode cell 210 ... anode
300 ... cathode cell 310 ... cathode
400 ... hydrogen peroxide supply cell 500 ... anion surfactant supply cell
600 ... power supply

Claims (13)

TPH contaminated soil and heavy contaminated soil cells;
A positive electrode cell having a positive electrode inserted into one side of the soil cell;
A cathode cell having a negative electrode inserted on the other side of the soil cell so as to be spaced apart from the positive electrode by a predetermined distance;
A hydrogen peroxide supply cell connected to the anode cell to supply hydrogen peroxide to one side of the soil cell;
A first anionic surfactant supply cell connected to the cathode cell to provide a first anionic surfactant on the other side of the soil cell;
A treatment region defined by a flow distance in which the hydrogen peroxide moves from the positive electrode to the negative electrode by electroosmosis by supplying power to the positive electrode and the negative electrode, and the first anionic surfactant is adsorbed to the TPH And a power supply device that cleans and adsorbs contaminants to be moved from the negative electrode to the treatment area,
The hydrogen peroxide reacts with the metal salt present in the soil cell when it moves into the soil cell complexed with the TPH contaminant and the heavy metal contaminant to generate the hydroxyl radical by causing the Fenton oxidation reaction,
The first anionic surfactant cleanses and adsorbs the TPH contaminant at the portion where the hydrogen peroxide is not injected and moves to the treatment region so that the TPH contaminant is oxidatively decomposed by the hydroxyl radical,
Wherein the treatment area is adjusted to a range of 40 to 60% of a distance between the positive electrode and the negative electrode, wherein the treatment area is chemically combined with a chemical oxidation method and a soil washing method. The method according to claim 1,
Further comprising a pH buffer supply cell for providing a pH buffer solution for neutralizing OH ^- ions from the other side of the soil cell, wherein the pH buffer solution supply cell comprises a chemical oxidation method and a soil washing method. delete The method according to claim 1,
And a second anion surfactant supply cell connected to the anode cell to provide a second anionic surfactant to one side of the soil cell, wherein the coin technique comprises the steps of: Purification system. The method according to claim 1,
Wherein the anode cell and the cathode cell each include a vertical anode cell and a vertical cathode cell, wherein the chemical oxidation method and the soil cleaning method are combined with each other. The method according to claim 1,
Wherein the anode cell and the cathode cell each include a horizontal anode cell and a horizontal cathode cell, wherein the chemical oxidation method and the soil cleaning method are combined with each other. 5. The method of claim 4,
Wherein the first and second anionic surfactants comprise sodium dodecyl sulfate. 6. The system of claim 1, wherein the first and second anionic surfactants comprise sodium dodecyl sulfate. 3. The method of claim 2,
Wherein the pH buffer solution comprises an organic acid composed of at least one of nitric acid, citric acid, hydrochloric acid, and succinic acid, and a chemical oxidation method and a soil cleaning method. delete TPH contaminated soil and heavy contaminated soil cells;
A positive electrode cell having a positive electrode inserted into one side of the soil cell;
A cathode cell having a negative electrode inserted on the other side of the soil cell so as to be spaced apart from the positive electrode by a predetermined distance;
A hydrogen peroxide supply cell connected to the anode cell to supply hydrogen peroxide to one side of the soil cell;
An anionic surfactant supply cell connected to the cathode cell to provide first sodium dodecyl sulfate to the other side of the soil cell;
A stabilizer supply cell connected to the anode cell to provide a second sodium dodecyl sulfate at one side of the soil cell to lower the consumption rate of the hydrogen peroxide;
A pH buffer supply cell for supplying an organic acid to the other side of the soil cell;
Wherein a treatment region is defined by a flow distance at which the hydrogen peroxide is moved from the anode to the cathode by electroosmosis by supplying power to the anode and the cathode, and at the same time, the first sodium dodecyl sulfate And a power supply device for cleaning and adsorbing the TPH contaminants to move the electrode from the negative electrode to the treatment area,
The hydrogen peroxide reacts with the metal salt present in the soil cell when it moves into the soil cell complexed with the TPH contaminant and the heavy metal contaminant to generate the hydroxyl radical by causing the Fenton oxidation reaction,
Wherein the first sodium dodecyl sulfate cleanses and adsorbs the TPH contaminant at the portion where the hydrogen peroxide is not injected and moves to the treatment region so that the TPH contaminant is oxidatively decomposed by the hydroxyl radical,
Wherein the treatment area is adjusted to a range of 40 to 60% of a distance between the positive electrode and the negative electrode, wherein the treatment area is chemically combined with a chemical oxidation method and a soil washing method. Inserting a positive electrode and a negative electrode into contaminated soil contaminated with TPH contaminants and heavy metal contaminants;
Injecting hydrogen peroxide into the positive electrode and injecting an anionic surfactant into the negative electrode,
Wherein the TPH contaminant is oxidized and decomposed by hydroxyl radicals produced by reacting the hydrogen peroxide with the iron in the soil while the hydrogen peroxide is moved over a predetermined range by electroosmosis by applying power to the positive electrode and the negative electrode, And simultaneously causing the anionic surfactant to cleanse and adsorb the TPH contaminants by electroion migration to move from the negative electrode to the treatment area and to be oxidatively decomposed by the hydroxyl radicals A method of purifying a complex contaminated soil by combining a chemical oxidation method and a soil cleaning method with a coin technique,
Wherein the treatment area is adjusted to a range of 40 to 60% of a distance between the positive electrode and the negative electrode, wherein the treatment area is combined with a chemical oxidation method and a soil washing method. Inserting a positive electrode and a negative electrode into contaminated soil contaminated with TPH contaminants and heavy metal contaminants;
Injecting hydrogen peroxide into the positive electrode, injecting an anionic surfactant and a pH buffer into the negative electrode,
Wherein the TPH contaminant is oxidized and decomposed by hydroxyl radicals produced by reacting the hydrogen peroxide with the iron in the soil while the hydrogen peroxide is moved over a predetermined range by electroosmosis by applying power to the positive electrode and the negative electrode, And simultaneously causing the anionic surfactant to cleanse and adsorb the TPH contaminants by electroion migration to move from the negative electrode to the treatment area and to be oxidatively decomposed by the hydroxyl radicals A method of purifying a complex contaminated soil by combining a chemical oxidation method and a soil cleaning method with a coin technique,
Wherein the treatment area is adjusted to a range of 40 to 60% of a distance between the positive electrode and the negative electrode, wherein the treatment area is combined with a chemical oxidation method and a soil washing method. Inserting a positive electrode and a negative electrode into contaminated soil contaminated with TPH contaminants and heavy metal contaminants;
Injecting hydrogen peroxide and an anionic surfactant into the positive electrode, injecting an anionic surfactant and a pH buffer into the negative electrode,
Wherein the TPH contaminant is oxidized and decomposed by hydroxyl radicals produced by reacting the hydrogen peroxide with the iron in the soil while the hydrogen peroxide is moved over a predetermined range by electroosmosis by applying power to the positive electrode and the negative electrode, And simultaneously causing the anionic surfactant to cleanse and adsorb the TPH contaminants by electroion migration to move from the negative electrode to the treatment area and to be oxidatively decomposed by the hydroxyl radicals A method of purifying a complex contaminated soil by combining a chemical oxidation method and a soil cleaning method with a coin technique,
Wherein the treatment area is adjusted to a range of 40 to 60% of a distance between the positive electrode and the negative electrode, wherein the treatment area is combined with a chemical oxidation method and a soil washing method.

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