KR100919918B1 - Method and Apparatus for cleaning up material being polluted by PCBs - Google Patents

Abstract

The present invention relates to a method and apparatus for purifying pollutants containing polychlorinated biphenyls. The present invention relates to a method and apparatus for purifying polychlorinated biphenyls by improving a hydrogen donating mechanism for a dehalogenation reaction. The purpose is to provide.

Purification method according to the present invention for achieving the above object, to promote the reaction mechanism of the electron donor, iron, hydrogen donor selected from water, alcohol, ether, aliphatic hydrocarbons and mixtures thereof, and the hydrogen donor Mixing an additive, which is added in an amount of 0.1 to 20% by weight based on the content of iron as the electron donor, with a pollutant containing polychlorinated biphenyl; And heating the contaminants mixed with the electron donor, the hydrogen donor, and the additive to 100 to 600 ° C. to rapidly replace chlorine of the polychlorinated biphenyl with hydrogen.

Polychlorinated biphenyls, electron donors, hydrogen donors, additives, iron, nickel

Description

Method and apparatus for cleaning pollutants containing polychlorinated biphenyls {Method and Apparatus for cleaning up material being polluted by PCBs}

The present invention relates to a method and apparatus for purifying pollutants containing polychlorinated biphenyls, and more particularly, to contaminants such as soil, industrial by-products and wastes containing polychlorinated biphenyls in a high temperature reactor. The present invention relates to a method and an apparatus capable of effectively removing polychlorinated biphenyls by a rapid dehalogenation reaction.

Poly Chlorinated Biphenyls (PCBs) are compounds in which 2 to 10 of the 10 hydrogen atoms of the biphenyls linked by two benzene rings are substituted with chlorine atoms, which are insoluble in water and soluble in organic solvents. Good and stable to acids and alkalis, but long-lasting in soil and seawater, injuring the liver and skin when it enters the human body, banning its use and manufacture worldwide in 1976.

Until use and manufacture were prohibited, polychlorinated biphenyls were often used as industrial heat mediums, pigment solvents for carbonless copy paper, insulating oils for capacitors, and plasticizers for rubber for power cable coating. Therefore, the by-products and wastes of these industrial products, or the factory area where the products containing polychlorinated biphenyls are produced, or the soil where the wastes are discarded, are contaminated with polychlorinated biphenyls for a long time, causing serious environmental problems. Statistics show that 1 million tonnes of polychlorinated biphenyls have been released into the world worldwide, and 2 million tonnes have to be disposed of.

If the soil contaminated with polychlorinated biphenyl is left as it is, it will not only dissolve in rainwater and contaminate other soils, but will also accumulate in plants and animals, which will have a detrimental effect on humans, the end consumers of ecosystems. Therefore, the necessity of the purification of the soil contaminated with polychlorinated biphenyl has been greatly highlighted, which has been an important research subject in the industrial waste field.

One method for purifying soil contaminated with polychlorinated biphenyls is disclosed in Korean Patent No. 380549. This purification method is to install a reaction wall filled with a palladium (Pd) coated iron and soil and sandwiched between two layers of nonwoven fabric in a place where pollutants containing polychlorinated biphenyls pass. The polychlorinated biphenyls can be removed while passing through the reaction wall. However, this purification method has a limitation in the purification ability because the contaminant is purified only while passing through the reaction wall, there is a problem that the reaction rate is also considerably slower due to the reaction at room temperature.

Another method for purifying soil contaminated with polychlorinated biphenyls is disclosed in Korean Patent Laid-Open No. 2006-71565. This purification method is to prepare a disintegrant by mixing iron byproduct iron oxide and boron hydride in a ratio of 1: 1 to 1: 3, and then mixed the disintegrant to contaminated soil, add water, and leave it for a while. It is a method of removing biphenyl chloride. However, this method still has a problem that the purification rate is very slow because it should be left for at least 7 days.

On the other hand, a method of removing the toxicity through dehalogenation of all toxic halogenated aromatic compounds such as polychlorinated biphenyls (PCBs), polychlorinated phenols (PCP), dioxin (PCDD / PCDF) is Republic of Korea Patent No. 689683 Posted in This method comprises a halogenated aromatic compound with a reducing metal selected from the group consisting of lithium, potassium, sodium, magnesium, aluminum, zinc and iron in the presence of a hydrogen donor compound selected from the group consisting of water, alcohols, ethers, aliphatic hydrocarbons and mixtures thereof. In the method for dehalogenation through the reaction of, the dehalogenation reaction is configured to be carried out in the presence of at least one amine as a reaction accelerator.

According to this method, extreme toxicity can be eliminated by reacting a halogenated aromatic compound with a reducing metal which is an electron donor and water, an alcohol which is a hydrogen donor, and the like to dehalogenate. However, in order to prevent the metal surface is inactive because its surface is covered with an inhibitory layer containing halogenated hydrocarbons attached via metal halides and radical anions, such as iron, zinc, aluminum and magnesium. There was a problem that an additional surface activator such as amine must be added.

In order to solve this problem, the present invention newly improves the hydrogen donating mechanism for the dehalogenation reaction and thereby greatly improves the removal efficiency of polychlorinated biphenyls, thereby purifying pollutants containing polychlorinated biphenyls more quickly. The goal is to provide a way to make it work.

It is another object of the present invention to provide an optimal apparatus for implementing the above-described method for purifying contaminants containing polychlorinated biphenyls.

In order to achieve the above object, a method for purifying pollutants containing polychlorinated biphenyls according to the present invention includes an electron donor using iron, a hydrogen donor selected from water, alcohols, ethers, aliphatic hydrocarbons, and mixtures thereof; Mixing an additive, which is added in an amount of 0.1 to 20% by weight relative to the content of iron, which is the electron donor, with a pollutant containing polychlorinated biphenyls to promote the reaction mechanism of the hydrogen donor; And heating the contaminants mixed with the electron donor, the hydrogen donor, and the additive to 100 to 600 ° C. to rapidly replace chlorine of the polychlorinated biphenyl with hydrogen.

As the additive, one or two or more metals selected from the base metal group consisting of nickel, aluminum, copper, and zinc may be used, and one or two or more metals selected from the precious metal group consisting of gold, platinum, silver, rhodium, and tantalum. May be used, and a carbon material such as graphite or carbon black may be used.

In addition, when the contaminant containing polychlorinated biphenyl is soil, the mixing step may further include a pretreatment step of selecting coarse particles such as gravel from the soil previously contaminated with polychlorinated biphenyl. And, the step of replacing may further comprise the step of separating and discharging only the purified soil by precipitating the soil is complete the reaction for a certain time.

On the other hand, the apparatus for purifying pollutants containing polychlorinated biphenyls according to the present invention includes an electron donor using iron, a hydrogen donor selected from water, alcohols, ethers, aliphatic hydrocarbons, and mixtures thereof, and a reaction mechanism of the hydrogen donor. Reactor 10 for heating a contaminant containing polychlorinated biphenyl mixed with an additive that is added 0.1 to 20% by weight relative to the content of the electron donor iron to promote a temperature to a temperature of 100 ~ 600 ℃, from outside The first heat exchanger 20 for preheating the incoming water by the treated water discharged from the reaction tank 10 and the preheated water introduced from the first heat exchanger 20 are heated by high temperature steam. It consists of the 2nd heat exchanger 30 which flows into the reaction tank 10. As shown in FIG.

According to the method and apparatus for purifying contaminants containing polychlorinated biphenyls according to the present invention configured as described above, by using an additive which promotes the reaction mechanism of the hydrogen donor, the reaction rate of the dehalogenation of polychlorinated biphenyls is improved. Contaminants containing polychlorinated biphenyls can be purged in a short time. This allows for rapid recovery of pollutants. In addition, in the case of factory sites and land contaminated with polychlorinated biphenyls, it can be quickly restored and recycled for various purposes, and can prevent pollution spread of polychlorinated biphenyls through soil in advance.

Prior to describing the technical configuration of the present invention, the dehalogenation reaction of polychlorinated biphenyls will be briefly described. Polychlorinated biphenyls (PCBs) are halogenated aromatic compounds such as dioxins, and 2 to 10 of the 10 hydrogen atoms forming the two benzene rings of biphenyl are substituted with chlorine atoms, which are toxic by the chlorine atoms. Therefore, the removal of chlorine atoms through the dehalogenation reaction of polychlorinated biphenyls can eliminate the toxicity.

The dehalogenation reaction of polychlorinated biphenyls is achieved by mixing polychlorinated biphenyls with an electron donor with iron and a hydrogen donor of water, alcohols, ethers, aliphatic hydrocarbons, mixtures thereof, and the like. The dehalogenation reaction of such polychlorinated biphenyls will be described using zero valent iron and water.

First, Young's Iron serves to supply electrons through a reaction as shown in the following Formula (1).

^{Fe (s) -> Fe 2+} + 2e - (1)

Water serves to supply hydrogen ions to be finally substituted with chlorine through a reaction such as the following formulas (2) and (3).

_{H 2 O -> 1/2 H 2} + OH - (2)

H _2- > H ⁺ + H ⁺ (3)

The polychlorinated biphenyl is dehalogenated by reacting with ferrous iron and water through a reaction such as the following formula (4).

Fe (s) + R-nCl + nH + -> Fe 2n + + R-nH + nCl - (4)

Thus, electron donation reaction [formula (1)] by metals, hydrogen donation reaction [formula (2) and (3)] by water and the like, and dehalogenation reaction of polychlorinated biphenyls by electron and hydrogen donation Finally, the toxicity of the polychlorinated biphenyl is removed by the formula (4).

At this time, the dehalogenation reaction of the polychlorinated biphenyl may act as a rate-limiting step of the entire reaction because an inert layer is formed on the surface of metals that are electron donors and the rate of the electron donating reaction is lowered. Conventionally, the amine was added as a surface activator to prevent this, as described above. The problem of surface inactivation of the metal which is an electron donor can be solved to some extent by increasing the dehalogenation reaction temperature.

The inventors noted that during the hydrogen donation reaction, the formula (3) may be another rate-limiting step of the dehalogenation reaction of polychlorinated biphenyls. That is, under normal circumstances, since hydrogen gas (H ₂ ) is more stable than hydrogen ions (H ⁺ ), the production rate of hydrogen ions is lowered, and as a result, it is necessary to be donated for the dehalogenation reaction (Equation 4). The lack of hydrogen ions slows the dehalogenation reaction.

The present inventors have found a substance which acts as a kind of catalyst which promotes the hydrogen donation reaction [Formula 3] as a result of dozens of experiments, and chlorine of polychlorinated biphenyl is always added during the reaction by increasing the reaction temperature at the same time. More hydrogen ions were donated than equivalent ratios, thereby greatly improving the dehalogenation reaction rate. This constitutes the most characteristic technical configuration of the present invention.

As described above, the present invention is to allow the dehalogenation reaction to occur quickly by mixing the electron donor, the hydrogen donor and the additive to the contaminant containing polychlorinated biphenyl and raising the reaction temperature. The electron donor, hydrogen donor and additive according to the invention are described in detail.

First, as the electron donor, iron (Fe), which is the most economical among metals, is used. Iron may use zero valent iron or iron oxide which is a by-product of the iron making process. However, iron oxide is useful in recycling industrial wastes, but it is preferable to use zero iron for rapid dehalogenation because it has a lower electron donating ratio than zero iron.

As the hydrogen donor, one substance selected from water, alcohols, ethers, aliphatic hydrocarbons and mixtures thereof is used. These materials are readily available on the market and do not cause side reactions during the dehalogenation reaction. In addition, the hydrogen donor preferably supplies an equivalent ratio or more so as to supply sufficient hydrogen to substitute chlorine of the polychlorinated biphenyl.

As an additive for promoting the reaction mechanism of the hydrogen donor, one or more metals selected from the group of base metals consisting of nickel (Ni), aluminum (Al), copper (Cu), and zinc (Zn) are typically used. .

These additives increase the amount of hydrogen ions generated by acting as a catalyst in separating hydrogen gas (H ₂ ) into hydrogen ions (H ⁺ ) in the hydrogen donation reaction (Formula 3). The exact mechanism for the action of the additive has not yet been elucidated, but it is speculated that it promotes the separation of hydrogen gas, which has previously been achieved by electron donors such as iron.

Figure 1 is a graph showing the results of the dehalogenation reaction after using a small iron as an electron donor, using a water as a hydrogen donor, a small amount of nickel as an additive, demonstrating the excellent effect of the dehalogenation reaction according to the present invention Do it.

In more detail, Figure 1 is mixed with 9.5g of ferrous iron, 0.0095g of nickel (0.1% by weight of iron), and 150ml of water to 300g of soil, a pollutant containing polychlorinated biphenyl, and then heated to 300 ℃ in the reaction tank Then, it is a graph measuring the residual amount of polychlorinated biphenyl in the soil over time. According to this, it can be seen that the polychlorinated biphenyl, which had reached the initial 143 mg / kg, decreased below the soil tolerance of 12 mg / kg (12 ppm) before 60 minutes had elapsed. This is drastically shortened the reaction time compared to the dehalogenation reaction that took more than a week conventionally.

Table 1 shows the experimental results of the dehalogenation reaction carried out under the same experimental conditions as in FIG.

PCBs residual concentration in soil (mg / kg) PCBs Residual Concentration of Water (mg / L) Removal rate pH Before treatment 143 7.8 After 60 minutes 8.3 0.001 94.2% 7.5

As shown in Table 1, as a result of the dehalogenation reaction according to the present invention, the residual concentration of polychlorinated biphenyl in the soil was 8.3 mg / kg, lower than the legal soil tolerance of 12 mg / kg (12 ppm), and the water discharged after the reaction. The residual concentration of polychlorinated biphenyl contained in was extremely low at 0.001 mg / L. Therefore, the soil or water after the reaction can be used immediately without any treatment.

According to the present invention, the removal rate (chlorine substitution rate) of polychlorinated biphenyls in the dehalogenation reaction is related to the reaction temperature. That is, the higher the reaction temperature, the higher the oxidation rate of the electron donating reaction [formula (1)] of iron, and the higher the removal rate of polychlorinated biphenyl. Table 2 shows the removal rate of polychlorinated biphenyl after reacting for 60 minutes at each reaction temperature under the same experimental conditions as in FIG. 1 except for the reaction temperature.

Temperature (℃) PCBs residual concentration in soil (mg / kg) Removal rate Before treatment 143.287 50 117.937 17.7% 100 28.647 80.0% 200 21.063 85.3% 300 8.301 94.2% 500 6.100 95.7% 600 4.580 96.8%

According to the dehalogenation reaction of the present invention, as shown in Table 2, the removal rate of polychlorinated biphenyl was very low at 50 ° C, but the removal rate of polychlorinated biphenyl is 80% or more when water is 100 ° C or more, which is changed to steam. In order to achieve the productivity improvement through the rapid dehalogenation reaction, which is the object of the present invention, it is preferable to exhibit a removal rate of 80% or more based on the reaction time of 60 minutes. However, even if the reaction temperature is higher than 100 ℃, the removal rate continues to improve as the temperature is increased, but if the removal rate is lowered above 600 ℃, the cost of heating to above 600 ℃ by the normal steam heating method increases significantly. The efficiency is lowered. Therefore, it is preferable to control reaction temperature to 100-600 degreeC.

According to the present invention, the removal rate (chlorine substitution rate) of polychlorinated biphenyls in the dehalogenation reaction is also related to the content of the additive for iron used as the electron donor. That is, the higher the content of the additive, the higher the contribution to the separation action of hydrogen gas by iron, so that the dehalogenation reaction is promoted. Table 3 shows the removal rate of polychlorinated biphenyl after reacting for 30 minutes for each nickel content under the same experimental conditions as in FIG. 1 except for the nickel content.

division PCBs residual concentration in soil (mg / kg) Removal rate Before treatment 143.287 Fe (Ni 0.1 mass%) 20.102 86.0% Fe (Ni 5 mass%) 13.320 90.7% Fe (Ni 20 mass%) 9.216 93.6% Fe (Ni 25 mass%) 9.210 93.6%

As shown in Table 3, even if only 0.1 mass% of the nickel content as an additive was mixed, the removal rate of 86% was shown after 30 minutes of the dehalogenation reaction. In addition, the removal rate continued to increase as the content of nickel increased, but the removal rate was saturated to 93.6% at 20 and 25% by mass. In view of this, it is preferable to control the content of the additive to the content of the iron as the electron donor in the present invention to 0.1 to 20% by mass.

On the other hand, in addition to the base metal consisting of nickel, aluminum, copper, zinc, there are materials that can be used as an additive to promote hydrogen donation for the dehalogenation reaction. That is, the additive may use one or more metals selected from the group of noble metals consisting of gold (Au), platinum (Pt), silver (Ag), rhodium (Rh), tantalum (Ta), and graphite Carbon materials such as Graphite or Carbon black can also be used.

Table 4 shows the reaction for 60 minutes after mixing the nickel in the base metal, the platinum in the precious metal and the graphite in the carbon material at 0.5 mass%, respectively, under the same experimental conditions as in FIG. 1 except for the type of the additive. Then, the removal rate of polychlorinated biphenyl was measured.

division PCBs residual concentration in soil (mg / kg) Removal rate Before treatment 143.287 Fe (Ni 0.5 mass%) 7.370 94.9% Fe (Pt 0.5 mass%) 6.735 95.3% Fe (Graphite 0.5 mass%) 8.101 94.3%

As shown in Table 4, the removal rate of the high polychlorinated biphenyl was shown regardless of the type of the additive. Therefore, it can be seen that not only nonmetals, but also precious metals, carbon materials, and the like can be used as the additive according to the present invention. In addition, although the noble metal is a slight difference, the polychlorinated biphenyl removal rate is higher than that of the nonmetal. This is presumably because the noble metal is more stable than the base metal with little reactivity, and thus can perform a better role as a catalyst. On the other hand, since the carbon material is not a metal, it showed the lowest polychlorinated biphenyl removal rate.

Hereinafter, with reference to the accompanying drawings will be described in detail with respect to the method for purifying pollutants containing polychlorinated biphenyls and apparatus using the electron donor, hydrogen donor and additives according to the present invention. Since a representative example of the pollutant containing the polychlorinated biphenyl is soil, the following describes a method and apparatus for purification based on soil contaminated with polychlorinated biphenyl.

2 is a process flowchart showing a method for purifying soil among pollutants containing polychlorinated biphenyls according to the present invention. The purifying method of the present invention basically contains polychlorinated biphenyl as an electron donor in which iron is used, a hydrogen donor selected from water, alcohols, ethers, aliphatic hydrocarbons, and mixtures thereof, and an additive for promoting the reaction mechanism of the hydrogen donor. Mixing in the soil which is one pollutant (S20); It is composed of a step (S30) to rapidly replace the chlorine of the polychlorinated biphenyl with hydrogen by heating the soil mixed with the electron donor, hydrogen donor and additives to 100 ~ 600 ℃.

The mixing step (S20) is an electron donation reaction with iron [(1)], hydrogen donation reaction with water, alcohol, etc. [(2) and (3)] and dehalogenation reaction [(4)] This is the step of mixing the required reactants to take place in turn. This mixing step may be configured to be made by a stirring device installed inside the reaction tank, it may be configured to be carried out by a separate mixing device installed outside the reaction tank and then put the mixed soil into the reaction tank.

In addition, the mixing step (S20) may further include a pretreatment step (S10) for screening the coarse particles, such as gravel from the soil previously contaminated with polychlorinated biphenyls in order to increase the effect of the dehalogenation reaction. . In this pretreatment step (S10), polychlorinated biphenyl is mainly mixed with soil of fine particles such as soil, silt, and sand, so that coarse particles such as gravel are selected and After the cleaning process, it is used for other purposes.

The substitution step (S30) by heating the soil mixed in the step S10 to 100 ~ 600 ℃ to promote the dehalogenation reaction to quickly replace the chlorine of the polychlorinated biphenyls with hydrogen, thereby reducing the toxicity of the polychlorinated biphenyls Remove Increasing the reaction temperature increases the rate of the electron donating reaction of iron or the hydrogen gas separation action of the additive to improve the removal rate of the polychlorinated biphenyl as described above with reference to Table 2.

In addition, the substitution step (S30) may further include the step (S40) of separating and discharging only the purified soil by precipitating the soil is completed for a certain time. This separate discharge step (S40) is performed by precipitating the hydrogen donor and the purified soil for a predetermined time after completion of the step S30 in consideration of the fact that a hydrogen donor such as water is always added in a much larger amount than the equivalent ratio of chlorine of polychlorinated biphenyls. Separate. The purified soil can be used as it is for reforming work without any additional treatment.

Figure 3 shows the heating method of the apparatus for purifying pollutants containing polychlorinated biphenyls according to the present invention. In the purifying apparatus of the present invention, the reactor 10 in which the contaminant containing the electron donor, the hydrogen donor, the additive, and the polychlorinated biphenyl is introduced is the most essential component.

The reactor 10 is heated to a high reaction temperature of 200 ~ 600 ℃, in the present invention by applying an indirect heating method using the two heat exchangers (20,30) significantly reduced the energy cost. In more detail, this indirect heating method is a polychlorinated mixture of an electron donor in which iron is used, a hydrogen donor selected from water, alcohols, ethers, aliphatic hydrocarbons, and mixtures thereof, and additives for promoting the reaction mechanism of the hydrogen donor. A first heat exchanger for preheating the soil, which is a pollutant containing biphenyl, to a temperature of 100 to 600 ° C., and preheating the water flowing from the outside by the treated water discharged from the reaction tank 10 ( 20) and a second heat exchanger 30 which heats the preheated water flowing from the first heat exchanger 20 with high temperature steam and flows it into the reactor 10.

The case where the reaction tank 10 is heated to 300 degreeC by the said indirect heating system is demonstrated to an example. First, in the first heat exchanger 20, water (A) having a temperature of 25 ° C. supplied from the outside and high temperature treated water (D) having a temperature of 300 ° C. heated and discharged from the reactor 10 are introduced to exchange heat. As a result, the water (A) at 25 ° C is discharged as water (B, steam form) preheated to 200 ° C, and the high temperature treated water (D) is finally discharged to the discharged water (E) at 95 ° C.

In the second heat exchanger 30, water B preheated to 200 ° C. and steam F 350 ° C. supplied from an external steam device are introduced to exchange heat. As a result, the water B preheated to 200 ° C. is heated to 300 ° C. and introduced into the reaction tank 10 to heat it, and the 350 ° C. steam F is discharged to 300 ° C. steam G. The discharged steam G is supplied to the steam apparatus again and recycled.

According to the apparatus for purifying pollutants containing polychlorinated biphenyls according to the present invention configured as described above, energy costs can be greatly reduced by effectively utilizing the waste heat of the treated water discharged to the reaction tank 10.

Since the content described so far corresponds to an embodiment of the present invention, the technical idea of the present invention is not limited thereto. Further, the detailed description of the present invention describes a method for purifying the soil mainly contaminated with polychlorinated biphenyls, but is not limited thereto. Waste oil and hydraulic fluids containing polychlorinated biphenyls in addition to the soil are not limited thereto. It can also be applied to the purification of oils, transformer oils, chiller oils, filter dusts, ash, industrial residues, industrial by-products and industrial wastes.

1 is a graph showing the experimental results of the purification method according to the present invention.

2 is a process flow chart of the purification method according to the present invention.

3 is a view showing a purification device according to the present invention.

※ Explanation of code for main part of drawing ※

10: reactor 20: first heat exchanger

30: second heat exchanger

Claims (8)

0.1 to 20% by weight of the electron donor using iron, a hydrogen donor selected from water, an alcohol, an ether, an aliphatic hydrocarbon, and a mixture thereof, and iron, the electron donor, in order to promote the reaction mechanism of the hydrogen donor Mixing the additive with a contaminant containing polychlorinated biphenyls; Method of purifying pollutants containing polychlorinated biphenyl comprising the step of rapidly replacing the chlorine of the polychlorinated biphenyl with hydrogen by heating the contaminant mixed with the electron donor, the hydrogen donor and the additive to 100 ~ 600 ℃ . The method of claim 1, wherein the additive is one or two or more metals selected from the group of base metals consisting of nickel, aluminum, copper, and zinc. The method of claim 1, wherein the additive is one or two or more metals selected from the group of noble metals consisting of gold, platinum, silver, rhodium, and tantalum. The method of claim 1, wherein the additive is one or two selected from carbon materials of graphite or carbon black. delete The coarse particle according to any one of claims 1 to 4, wherein the mixing step is coarse particles such as gravel from soil contaminated with polychlorinated biphenyl before the mixing step, when the pollutant containing polychlorinated biphenyl is soil. A method for purifying pollutants containing polychlorinated biphenyls, further comprising a pretreatment step of sorting out. The method of claim 6, wherein the replacing step further comprises the step of precipitating the soil is completed for a predetermined time to separate the purified soil and to discharge the pollutants containing polychlorinated biphenyls. 0.1 to 20% by weight of the electron donor used with iron, hydrogen donor selected from water, alcohol, ether, aliphatic hydrocarbon, and mixtures thereof, and iron, the electron donor, to promote the reaction mechanism of the hydrogen donor A preheating agent 10 for heating contaminants containing polychlorinated biphenyl mixed with an additive to a temperature of 100 to 600 ° C., and pre-heated water introduced from the reaction tank 10 by treatment water discharged from the reaction tank 10. The first heat exchanger 20 and the second heat exchanger (30) for heating the preheated water flowing from the first heat exchanger 20 by the high temperature steam to enter the reactor 10, characterized in that Purifying apparatus for pollutants containing polychlorinated biphenyl.

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