WO2011002118A1

WO2011002118A1 - Method for treating insulating oil containing pcbs

Info

Publication number: WO2011002118A1
Application number: PCT/KR2009/003605
Authority: WO
Inventors: 황성일; 현준목; 조종수; 김영선
Original assignee: (주)엠비즈텍씨앤씨
Priority date: 2009-07-01
Filing date: 2009-07-01
Publication date: 2011-01-06
Also published as: KR100970947B1

Abstract

The present invention relates to a method for treating insulating oil containing polychlorinated biphenyls (PCBs), comprising the steps of: A) dissociating chlorine from PCBs in insulating oil; and B) adsorbing the dissociated chlorine in step A) on a sorbent, wherein as the sorbent is a waste product such as shells including calcium (Ca) or calcium carbonate (CaCO3), the method is capable of recycling insulating oil into a resource in which PCBs are degraded by recycling environmental waste products and degrading and removing PCBs.

Description

Insulating oil treatment method including PCX

The present invention relates to an environmentally friendly method of removing PCBs contained in insulating oil of a waste transformer and recycling or recycling waste oil and shells, which are environmental wastes.

PolyChlorinated Biphenyls (PCBs) refer to compounds in which 2 to 10 of the 10 hydrogen atoms of biphenyl are linked with two benzene rings substituted with chlorine atoms.

This compound is insoluble in water, good in solubility in organic solvents, stable in acids and alkalis, low in volatility, high in viscosity, and very high in thermal resistance, so PCBs are used in insulating oils in transformers and accumulators or in heat exchangers. It has been used as a medium and widely used in industries such as paint, ink and pesticides.

However, since the PCBs are known to have serious adverse health and environmental impacts in the mid-1970s, much research has been made on the development of methods to effectively process PCBs that have already been produced and disposed of.

Conventional processes for treating PCBs mixed oils have generally been incinerated at high temperatures. However, since the incineration method has a problem of generating a large amount of dioxins and carbon dioxide and waste of resources due to incineration of waste oil, other treatment methods have been studied.

As a technique for processing such PCBs, a "chemical extraction decomposition method" has been introduced on Tokyo Electric Power Company's Internet website ("Decontamination Technology of PCBs", December 2, 1996). This method adds a solvent to the insulating oil containing PCBs, which activates chlorine in the PCBs to react with sodium hydroxide and convert it into biphenyl and a completely harmless salt. However, in this technique, the chemical extraction and decomposition method is not clear, and when the chemical reaction is only processed, there is a problem that the chemical conversion is not 100% possible and the remaining PCBs are not processed.

Korean Patent Application No. 10-1999-0018650 (Invention: Oxidative Decomposition Method of PCB) is a technology to decompose and remove PCBs including oil by water and carbon dioxide by oxidizing PCBs by using persulfate ion and ultraviolet ray. . However, in order to remove PCBs with a general content of less than about 0.1%, there was a problem of failing to recycle a large amount of waste insulating oil, which is a valuable resource of 99.9%.

Accordingly, an object of the present invention is to provide a treatment method for removing PCBs contained in waste insulating oil by using waste and treating waste insulating oil from which PCBs have been removed as a resource for recycling.

Insulating oil treatment method comprising a PCBs according to the present invention for achieving the above object is a step of desorbing the chlorine of the PCBs from the insulating oil containing PCBs (Polychlorinated Biphenyls); And a step B of adsorbing the chlorine desorbed in the step A to an adsorbent; It includes, the adsorbent is characterized in that the waste containing calcium (Ca) or calcium carbonate (CaCO ₃ ).

Here, the waste is another feature that is a shell.

In addition, the waste is characterized in that the pores are formed.

Here, the chlorine of the PCBs in step A is characterized in that the hydroxy group radicals generated by adding hydrogen peroxide and iron sulfate solution to the insulating oil is detached by the reaction of the PCBs.

Further, the hydroxy radical and the hydrocarbon compound of the insulating oil react to form a polyol.

Further step C after the step B to form a polyurethane from the polyol; It is characterized by another comprising a further.

Wherein the step C is a step C1 of dehydrating a mixture of the adsorbent and the polyol to which the chlorine is adsorbed after the step B; And a step C2 of adding a crosslinking agent to the mixture dehydrated in step C1; It is another feature to include a.

Wherein step C is a step C0 of separating the upper polyol mixture after leaving the mixture of the adsorbent and the polyol adsorbed chlorine for a predetermined time; C1 step of dehydrating the polyol mixture separated in step C0; And adding a crosslinking agent to the polyol mixture dehydrated in the step C1; It is another feature to include a.

Wherein step C is a C0 step of separating the polyol mixed precipitate of the lower layer after leaving the mixture of the adsorbent and the polyol adsorbed chlorine for a predetermined time; C1 step of dehydrating the polyol mixture precipitate separated in step C0; And a step C2 of adding a crosslinking agent to the lower precipitate layer dehydrated in the step C1; It is another feature to include a.

Furthermore, it is another feature that the color of the polyurethane formed after the C2 step can be selected by controlling the heating temperature or the dehydration time for the polyol mixed precipitate in the C1 step.

Insulating oil treatment method including the PCBs according to the present invention for achieving the above object is a hydroxyl group radical generated by adding hydrogen peroxide and iron sulfate solution to the insulating oil containing PCBs (Polychlorinated Biphenyls) react with the PCBs A step of desorbing the chlorine of the PCBs; And B step of adsorbing the chlorine desorbed in the A step to the adsorbent. The hydroxyl group radical reacts with the hydrocarbon compound of the insulating oil to form a polyol.

Wherein step C after the step B to form a polyurethane from the polyol; It is characterized by another comprising a further.

Insulating oil treatment method including PCBs according to the present invention uses environmental waste waste and hydroxy radicals to decompose and remove PCBs of harmful waste PCBs insulation oil so that the waste waste is recycled and harmful PCBs are recycled. Has the effect of removing the residue without residue.

In addition, since the hydroxyl radical reacts with the oil of the insulating oil from which the PCBs are decomposed to form a polyol, the waste insulating oil from which the PCBs are decomposed and removed can be recycled without waste.

Furthermore, since the polyol can be used to form a polyurethane, there is an advantage of recycling resources, and there is an advantage of forming a colored polyurethane according to the oxidation of the transparent polyurethane and iron sulfate.

1 is a flow chart schematically showing an insulating oil processing method including PCBs according to an embodiment of the present invention.

2 is a cross-sectional photograph of a shell showing a state before forming a porous structure in the shell in the insulating oil processing method including the PCBs according to an embodiment of the present invention.

3 is a cross-sectional photograph of a shell showing a porous structure formed on the shell in the insulating oil processing method including the PCBs according to an embodiment of the present invention.

S101: Step A

S102: Stage B

S201: C0 step

S202: C1 step

S203: C2 stage

Hereinafter, with reference to the accompanying drawings to be described in more detail with respect to the present invention will be described with reference to a preferred embodiment.

1 is a flow chart schematically showing an insulating oil treatment method including PCBs (hereinafter, simply referred to as PCBs) according to an embodiment of the present invention.

Referring to Figure 1 PCBs insulating oil treatment method according to an embodiment of the present invention is made to include a step A and B and may further comprise a step C.

And here, the PCBs insulating oil containing PCBs and paraffin hydrocarbons such as n-pentane (isopentane), isopentane (neo pentane) and naph such as cyclopentane (cyclopentane |), cyclohexane (cyclopentane) Refers to single or mixed oils of naphtene hydrocarbons.

In addition, in this specification, an adsorbent means the substance which adsorb | sucks a predetermined substance.

<Step A> (S101)

A step (S101) is a step of desorbing chlorine of the PCBs from the insulating oil containing the PCBs.

Here, there may be various ways to desorb chlorine in PCBs, but it is preferable to desorb chlorine using radicals, and it is produced by adding hydrogen peroxide (H ₂ O ₂ ) and iron sulfate solution (FeSO ₄ ) to insulating oil. It is more preferable that the hydroxy group radical and the PCBs contained in the insulating oil undergo radical reaction to desorb chlorine from the PCBs.

That is, the reaction tank is filled with insulating oil containing PCBs (hereinafter, simply referred to as PCBs insulating oil), and hydrogen peroxide (H ₂ O ₂ 35%) and iron sulfate (FeSO ₄ ) aqueous solution (20%) are added to the hydroxy radical. (OH) is generated.

Hydroxy radicals attack and desorb chlorine bound to the diphenyl ring of PCBs. Desorbed chlorine is either blown off with chlorine gas or left in insulating oil with chlorine ions.

Hydrogen peroxide (formula: 35% H ₂ O ₂ ) and iron sulfate (FeSO ₄ or Fe ₂ (SO ₄ ) ₃ ) aqueous solution (solid content 20%) are used as radical generators to dissolve or decompose each molecule of PCBs insulating oil. When a small amount is added to the PCBs insulating oil for 10 to 120 minutes, it generates a rapid exothermic reaction at room temperature. Here, the weight ratio of oil to hydrogen peroxide is preferably 1: 0.2 to 1: 2. And the weight ratio of the oil to the iron sulfate solution is 1: 0.2 to 1: 2.

At this time, iron ions circulate between Fe ₂ ⁺ and Fe ₃ ⁺ when the organic material is oxidized and decomposed. I.e., Fe ⁺ _2, which is a catalyst to catalyze the hydrogen peroxide generates a hydroxyl radical (and OH) and of hydrogen peroxide from the oxidized to the Fe ⁺ _3.

The generated (.OH) decomposes an organic substance to generate an organic radical (R.). Fe ₃ ⁺ by the organic radical is reduced back to Fe ⁺ _2. Organic radicals are oxidatively decomposed.

Here, if the Fe ⁺ ₃ by organic radicals are reduced to Fe ₂ ^+, the greater the concentration of Fe ₃ ^+. Therefore, if the Fe ₂ ⁺ is supplied further oxidation stops.

The hydroxy radical (.OH) generated by the reaction of hydrogen peroxide with iron sulfate is desorbed from the diphenyl ring of PCBs as outlined in Scheme 1, and the diphenyl ring is substituted with a hydroxyl group instead of chlorine.

In this way, the chlorine desorbed from the phenyl ring through the radical reaction is adsorbed to the adsorbent containing calcium or calcium carbonate in step B to be described later to become calcium chloride, and the chlorine component is removed from the oil.

On the other hand, hydroxy radicals desorb chlorine from PCBs as described above, but as shown schematically in Scheme 2, radical reactions to molecules of hydrocarbon oils in waste insulating oil form compounds such as polyols in which hydrogen is substituted with hydroxyl groups. Sometimes.

(Here, the number of substitution of H and OH is at least two.)

The polyol is formed by the reaction of hydroxy radicals and hydrocarbon oil as shown in Scheme 2 in step A (S101). This polyol formation reaction may occur while chlorine is adsorbed to the adsorbent in step B (S102), which will be described later. .

<Step B> (S102)

Next, in step S102, desorbed chlorine (chlorine ion) is adsorbed onto an adsorbent containing calcium (Ca) or calcium carbonate (CaCO ₃ ). In this case, it is preferable to use a porous waste containing calcium as the adsorbent. It is more preferable to use a shell as a porous waste containing calcium here.

Here, the porous waste containing calcium as an adsorbent for adsorbing chlorine for a while will be described.

Shells can be used as porous waste containing calcium. The shell is shell of shellfish, which is composed of tananium calcium and composed of an outer layer, an inner layer, and a myostracum layer. Its main component is calcium carbonate and is usually composed of about 1 to 4% amino acids (NH ₂ ).

In order to remove chlorine effectively by using such a shell, the following predetermined processing can be performed on the shell.

2 and 3 will be described with reference to the picture. 2 is a sectional view of a shell showing a state before forming a porous structure in the shell in the insulating oil processing method including the PCBs according to an embodiment of the present invention, Figure 3 includes a PCB according to an embodiment of the present invention Shell cross-section picture showing the porous structure formed on the shell in the insulating oil treatment method.

A shell is put in a sealed container to create an environment where oxygen is blocked. Here, the cross-sectional view of the shell before the predetermined processing is performed on the shell is as shown in FIG. And the shell is heat-treated at high temperature (for example 400-900 degrees Celsius). The heat treatment time is heated to about 1 hour to 12 hours. In this process, components such as amino acids are thermally decomposed to form a porous structure in the shell while expanding out of the gas state. Here, the porous structure formed on the shell is shown as a photograph shown in FIG.

In addition, carbon dioxide and oxygen are released from some of the main components of calcium carbonate and mixed with calcium, CaO, and CaCO ₃ to increase the adsorption reactivity of the adsorbent. During the heat treatment of the shell, a low oxygen environment is created in the container to prevent oxidation of the shell so that the porous structure of the shell does not collapse.

A shell having a porous structure, including calcium or calcium carbonate as described above, is used to remove chlorine desorbed from PCBs.

In order to adsorb chlorine desorbed in step A (S101), a shell, which is a waste, is adsorbed into the reaction tank. In addition, wet grinding is performed so that chlorine gas or chlorine ions can be smoothly adsorbed on the shell which is the adsorbent.

In order to adsorb chlorine desorbed during radical reaction, it is preferable to add an adsorbent containing calcium after adding hydrogen peroxide and iron sulfate solution. Calcium is alkaline and can neutralize the acid groups of hydrogen peroxide, which can interfere with the smooth production of radicals. Therefore, it is preferable to add the adsorbent containing calcium after a predetermined time passes after adding hydrogen peroxide and iron sulfate solution.

And an adsorbent containing calcium is added in a weight ratio of 1: 0.1 to 1: 1 with respect to PCBs insulating oil.

And, even though the adsorbent is not crushed, desorbed chlorine will be adsorbed to the adsorbent, but it is preferable to crush the adsorbent so that the desorbed chlorine can be adsorbed more smoothly. Grinding the adsorbent increases the specific surface area of the adsorbent, thus aiding in the smooth adsorption of desorbed chlorine and is not an obstacle in forming the polyurethane to be described later. The grinding of the adsorbent is preferably, for example, wet grinding to have a size of 30 μm or less by rotating at 300 to 3000 RPM with an injector for grinding for 5 to 30 minutes.

<C step> (S200)

Step C (S200) is a step of forming a polyurethane using waste insulating oil in which PCBs are decomposed and removed after step B102 and a polyol is formed. That is, after step B (S102) to form a polyurethane from the polyol.

The C step (S200) of forming the polyurethane is made to include the C1 step (S202) and the C2 step (S203), it may be made by further comprising a C0 step (S201) as necessary.

First, step C0 (S201) will be described.

In step C0 (S201), the PCBs are decomposed and removed after step B (S102), and the polyol mixture of the upper layer is left after leaving the waste insulating oil (ie, a mixture of chlorine-adsorbed adsorbent and polyol) having a polyol for a predetermined time. Separate step.

When the mixture of the chlorine adsorbent and the polyol is left for a predetermined time, layer separation occurs. In the upper part of the mixture there is a transparent liquid layer and in the lower part a sedimentary layer containing the precipitate appears.

In this case, in order to form a transparent polyurethane, the polyol mixture in the transparent liquid layer of the upper layer is separated, and steps C1 (S202) and C2 (S203), which will be described later, are described in the polyol mixture in the transparent liquid layer of the separated upper layer. Transparent polyurethane can be formed through.

On the other hand, the precipitated layer appearing in the lower layer is colored. Hydrogen peroxide and ferrous sulfate in this embodiment (FeSO ₄ or Fe ₂ (SO ₄₎ _3), using the aqueous solution process decomposing PCBs in the PCBs waste transformer oil, and while forming the polyol iron sulfate (FeSO ₄ or Fe ₂ (SO ₄₎ ₃ The yellow color of FeO is yellow due to the iron content of the aqueous solution.

Therefore, in the case of forming a colored polyurethane, the polyol sediment mixture in the sedimentation layer of the lower layer is separated, and steps C1 (S202) and C2 (S203) which will be described later on the separated polyol sediment mixture are performed. It is possible to form a colored polyurethane through.

Step C1 (S202) is a step of dehydrating the waste insulating oil (ie, a mixture of chlorine-adsorbed adsorbent and polyol) in which PCBs are decomposed and removed.

After the separation is subjected to a reduced pressure heating treatment for 1 to 24 hours at a temperature of 20 to 100 ℃ in an environment of vacuum 700 to 100 Torr. And in order to lower the water content, the adsorption treatment with activated carbon is dewatered to make the moisture content less than 0.05%.

In this case, when the transparent polyurethane is to be formed, the polyol mixture in the transparent liquid layer separated in the C0 step (S201) is dehydrated, and then a transparent polyurethane can be formed by adding a crosslinking agent in the C2 step (S203). .

In particular, when the colored polyurethane is to be formed, the color of the polyurethane may be determined according to a method of dehydrating the polyol precipitate mixture in the precipitate layer of the lower layer. That is, the color may be determined by adjusting the heating temperature or the dehydration time for the polyol mixed precipitate.

After dehydrating the polyol precipitated mixture at a temperature of 20 ° C. to 50 ° C. under a vacuum of 700 to 100 Torr for 5 hours or less, adsorbing moisture to the filter while passing the polyol precipitate to the activated carbon filter, the polyol precipitate Iron sulfate contained in the mixture is oxidized to iron oxide (FeO) to obtain a yellow iron oxide-calcium composite polyol and the like. The yellowish polyol precipitate mixture is a yellow iron oxide-calcium composite polyol dehydrated without color change.

When the polyol precipitant mixture is dehydrated for 5 hours or more in a vacuum environment of 100 to 700 Torr at a temperature of 80 ° C. to 100 ° C., the oxidation of iron sulfate proceeds further and the color changes from yellow to reddish brown. ₂ O ₃ )-can form calcium complex polyols.

Alternatively, when the polyol precipitate mixture is dehydrated at a high temperature of 120 ° C. to 200 ° C. for 3 hours or more in an environment of vacuum degree of 700 to 100 Torr, oxidation of iron sulfate is further progressed and black iron oxide (Fe ₃ O ₄ ) is black. )-Can form calcium complex polyols.

By adjusting the temperature and time in this way, the degree of oxidation of iron sulfate can be controlled (that is, the higher the temperature or the longer the dehydration time, the greater the oxidation of iron sulfate). The color of the polyol is determined. When the polyol is formed of polyurethane, the color of the polyol becomes the color of the polyurethane.

Step C2 (S203) is a step of adding a crosslinking agent to the mixture dehydrated in step C1 (S202).

MDI (methylene diphenyl diisocyanate), TDI (toluene diisocyanate), HMDI (hexamethylene diisocyanate), XDI (xylene diisocyanate), MXDI (m-xylene diisocyanate) as crosslinking agent in dehydrated polyol Any one of aromatic isocyanate or aliphatic isocyanate such as) is selected and added. It is preferable that the weight ratio of a polyol and a crosslinking agent is 1: 0.1-1: 1 here. The addition of the crosslinking agent forms a polyurethane from the polyol.

The color of the polyurethane formed in step C2 (S203) is determined according to the color of the polyol mixture dehydrated in step C1 (S2020).

A transparent polyurethane is formed by adding a crosslinking agent to the transparent polyol dehydrated in step C1 (S202).

Yellow polyurethane is formed by adding a crosslinking agent to the yellow iron oxide-calcium composite polyol dehydrated without color change in step C1 (S202). The reddish-brown polyurethane is formed by adding a crosslinking agent to the reddish-brown iron oxide (Fe ₂ O ₃ ) -calcium complex polyol formed during the dehydration process in step C1 (S202). In addition, a black polyurethane is formed by adding a crosslinking agent to the iron (Fe ₃ O ₄ ) -calcium complex polyol of black (BLACK) formed while being dehydrated in the step C1 (S202).

As described above, according to the present invention, chlorine is desorbed from the diphenyl ring, adsorbed to calcium, calcium chloride, and eventually included in the urethane polymer. A small amount of calcium chloride is a harmless substance to the human body and does not adversely affect the environment.

In addition, calcium chloride is only about 0.0002% (2ppm) to less than 0.1% of the total amount of the polymer does not significantly affect the polyurethane polymer properties.

Therefore, the residual of PCBs, which is an important issue when handling PCBs waste insulating oil, is not a problem. Thus, according to the embodiment of the present invention, PCBs in which chlorine is bonded to a ring in diphenyl in waste insulating oil are completely removed without the problem of PCBs remaining by chlorine desorbing and adsorption.

According to the insulating oil treatment method including the PCBs as described above, more specific embodiments and data of treating the PCBs insulating oil will be described.

Example 1 PCBs Removal

1000g of shells, which are environmental wastes, were placed in a ceramic sealed container and sealed, and heated at 817 ° C for 4 hours to process an adsorbent containing calcium.

In addition, 500 g of PCBs insulating oil collected from the waste transformer (containing 317 ppm of PCBs) was placed in a reactor. Subsequently, 500 g of hydrogen peroxide (35%) and an aqueous solution of iron sulfate (20% of solid content) were slowly added over 500 g for 30 minutes while stirring at a speed of RPM 200 to perform a substitution reaction.

500 g of calcium sorbent was then added to the reaction and wet milled with a blade infeller at a speed of RPM 1800. Then, 50g was sampled and the PCBs residual test was performed by the Korea Testing Institute.

PCBs residual test result: PCBs were found to be 317ppm → “not detected” and PCBs were completely removed (see Table 1).

Table 1

Test Items	unit	Result	Test Methods
PCBs	mg / L	Not detected	Waste Process Test Criteria: 2008 (Section 14C Act)

Example 1-1: Transparent Polyurethane Formation

The reaction product prepared in Example 1 was precipitated for 24 hours to obtain a transparent liquid phase of the upper layer, which was dehydrated for 6 hours at a temperature of 90 ° C. in a low vacuum environment of 100 to 700 Torr.

Next, 100 g of dehydrated polyol, 100 g of ethyl acetate (organic solvent), and 10 g of a crosslinking agent, TDI (NCO 13% / Songwon Industrial Product Name: CA75) 10g were mixed, and the polymerization reaction was carried out at a temperature of 40 ° C. for 2 hours under urethane to obtain a urethane. Prepolymers were formed.

Subsequently, 10 g of a tin (TIN) -based crosslinking accelerator (solid content 3% / Songwon Industrial Product Name: AT222R2) was added thereto, and then applied to an iron plate with a thickness of 50 μm, after 48 hours at room temperature, a transparent polyurethane cured coating film having a hardness of 4H was formed.

Example 1-2 Yellow Polyurethane Formation

The reactant prepared in Example 1 was precipitated to obtain a yellow liquid, which is a precipitate layer, and dehydrated in a low vacuum environment at a vacuum degree of 100 to 700 Torr for 12 hours at a temperature of 30 ° C., followed by finishing dehydration treatment using an activated carbon filter. To a water content of 0.05% or less.

After dehydration, 100 g of a yellow colored polyol and 10 g of TDI (NCO13% / Songwon Industrial Product Name: CA75) were mixed, and a urethane prepolymer was formed by polymerization for 1 hour at 30 ° C. under closed conditions, followed by tin (TIN). 5 g of a crosslinking accelerator (solid content 3% / Songwon Industrial Product Name: AT222R2) was mixed and dried at room temperature for 24 hours to obtain an elastic yellow elastomer (elastomer).

Example 1-3: Reddish-brown Polyurethane Formation

The reactant prepared in Example 1 was precipitated to obtain a yellow liquid, which is a precipitate layer, and dehydrated at a water content of 0.05% or less by dehydrating at 100 ° C to 700 Torr for 12 hours at a temperature of 90 ° C.

After dehydration, 100 g of reddish brown colored polyol and 10 g of TDI (NCO13% / Songwon Industrial Product Name: CA75) were mixed, and a urethane prepolymer was formed through polymerization for 1 hour at 30 ° C. under closed conditions, followed by tin (TIN). 5 g of a crosslinking accelerator (solid content 3% / Songwon Industrial Product Name: AT222R2) was mixed and dried at room temperature for 24 hours to obtain an elastic reddish brown elastomer.

The reactant prepared in Example 1 was precipitated to obtain a yellow liquid, which is a precipitate layer, and dehydrated in a vacuum of 100 to 700 Torr for 12 hours at a temperature of 180 ° C. to dehydrate to 0.05% or less of water content.

After dehydration, 100 g of black colored polyol and 10 g of TDI (NCO13% / Songwon Industrial Product Name: CA75) were mixed and polymerized at 30 ° C. for 1 hour in a sealed condition to form a urethane prepolymer, followed by tin-based crosslinking. 5 g of an accelerator (solid content 3% / Songwon Industrial product name: AT222R2) was mixed and dried at room temperature for 24 hours to obtain an elastic black elastomer.

Comparative Example 1: Residue of PCBs

1 kg of insulating oil (containing 317 ppm of PCBs) collected from the waste transformer is placed in the reactor, and 0.5 kg of hydrogen peroxide (35%) and 0.5 kg of aqueous solution of iron sulfate (solid content of 20%) are slowly mixed over 60 minutes while stirring at a speed of 200 rpm. The addition reaction was performed. Thereafter, 50g was sampled and the PCBs residual test was requested to the Korea Testing Institute.

PCBs Residual Test Result: PCBs were not completely removed from 317ppm to 92ppm (see Table 2).

TABLE 2

Test Items	unit	Result	Test Methods
PCBs	mg / L	92	Waste Process Test Criteria: 2008 (Section 14C Act)

As a result of comparing the test results of <Example 1> and <Comparative Example 1> according to the PCBs processing method according to the present invention it can be seen that the PCBs were removed without remaining.

And it can be seen that there is no PCBs remaining by adsorbing chlorine desorbed from PCBs using shells, which are environmental wastes.

0.5kg shells were placed in a ceramic sealed container and sealed, and heated at 817 ° C for 4 hours to process calcium adsorbent. In addition, 1 kg of PCBs insulating oil collected from the waste transformer (containing 317 ppm of PCBs) was placed in the reactor. Subsequently, the adsorbent was wet-pulverized with a blade infeller at a speed of RPM 1800, and 200 g of hydrogen peroxide was added thereto, followed by stirring for 30 minutes.

After that, 50g was sampled and the PCBs residual test was conducted by the Korea Testing Institute.

PCBs residual test result: PCBs increased from 317ppm to 426ppm (see Table 3).

TABLE 3

Test Items	unit	Result	Test Methods
PCBs	mg / L	426	Waste Process Test Criteria: 2008 (Section 14C Act)

As a result of not adding the iron sulfate solution, it can be seen that PCBs are not decomposed.

0.5 kg of shells were placed in a ceramic sealed container and sealed, and heated at 817 ° C. for 4 hours to process an adsorbent containing calcium. In addition, 1kg of PCBs insulating oil collected from the waste transformer (PCBs contained 317ppm) was put into the reactor and wet-pulverized the adsorbent with a blade infeller at a speed of RPM 1800, and 50g was sampled as follows. PCBs residual test was performed.

PCBs residual test result: PCBs increased from 317ppm to 385ppm (see Table 4).

Table 4

Test Items	unit	Result	Test Methods
PCBs	mg / L	385	Waste Process Test Criteria: 2008 (Section 14C Act)

As can be seen in Comparative Example 3, it can be seen that only the shells, which are environmental wastes, are decomposed and removed.

As described above, the insulating oil treatment method including the PCBs according to the present invention recycles waste wastes, which are environmental wastes, because the waste wastes and the hydroxyl radicals can be decomposed and removed so that PCBs of harmful waste PCBs insulation oils do not remain. Toxic PCBs can be removed.

In addition, since the hydroxy radicals react with the oil of the insulating oil in which the PCBs are decomposed to form a polyol, the waste insulating oil from which the PCBs are decomposed can be recycled.

Furthermore, since the polyol can be used to form a polyurethane, there is an advantage of resource recycling, and the colored polyurethane can be formed by oxidation of the transparent polyurethane and iron sulfate.

As described above, the detailed description of the present invention has been made by the embodiments with reference to the accompanying drawings, but since the above-described embodiments have only been described with reference to the preferred examples of the present invention, the present invention has been described above. It should not be understood to be limited only to the embodiments, and the scope of the present invention should be understood by the claims and equivalent concepts described below.

The present invention can be applied to the technical field of removing PCBs included in waste insulating oil and recycling or recycling waste oil and waste waste, which are environmental wastes.

Claims

A step of desorbing the chlorine of the PCBs in the insulating oil containing polychlorinated Biphenyls (PCBs); And

A step B of adsorbing the chlorine desorbed in the step A to an adsorbent; Including,

The adsorbent is characterized in that the waste containing calcium (Ca) or calcium carbonate (CaCO 3 )

Insulating oil treatment method including PCBs.
The method of claim 1,

The waste is characterized in that the shell (貝殼)

Insulating oil treatment method including PCBs.
The method according to claim 1 or 2,

The waste is characterized in that the pores are formed

Insulating oil treatment method including PCBs.
The method of claim 1,

The chlorine in the PCBs in step A

It is characterized in that the desorption by the reaction of the hydroxyl groups and the PCBs generated by the addition of hydrogen peroxide and iron sulfate solution to the insulating oil

Insulating oil treatment method including PCBs.
The method of claim 4, wherein

The hydroxy radical and the hydrocarbon compound of the insulating oil react to form a polyol

Insulating oil treatment method including PCBs.
A step in which the hydroxyl radical generated by adding hydrogen peroxide and iron sulfate solution to the insulating oil containing Polychlorinated Biphenyls (PCBs) reacts with the PCBs to desorb chlorine from the PCBs; And

And a step B of adsorbing the chlorine desorbed in the step A to an adsorbent.

The hydroxyl radical reacts with the hydrocarbon compound of the insulating oil to form a polyol

Insulating oil treatment method including PCBs.
The method according to claim 5 or 6,

C step of forming a polyurethane from the polyol after the step B; Characterized in that it further comprises

Insulating oil treatment method including PCBs.
The method of claim 7, wherein

Step C is

Dehydrating a mixture of the adsorbent to which the chlorine is adsorbed after the step B and the polyol; And

C2 step of adding a crosslinking agent to the mixture dehydrated in the C1 step; Characterized in that it comprises

Insulating oil treatment method including PCBs.
The method of claim 7, wherein

Step C is

C0 step of separating the polyol mixture of the upper layer after leaving the mixture of the adsorbent and the polyol adsorbed the chlorine for a predetermined time;

C1 step of dehydrating the polyol mixture separated in step C0; And

C2 step of adding a crosslinking agent to the polyol mixture dehydrated in the C1 step; Characterized in that it comprises

Insulating oil treatment method including PCBs.
The method of claim 7, wherein

Step C is

C0 step of separately separating the polyol mixture precipitate of the lower layer after the mixture of the adsorbent adsorbed with the chlorine and the polyol for a predetermined time;

C1 step of dehydrating the polyol mixture precipitate separated in step C0; And

A C2 step of adding a crosslinking agent to the lower precipitate layer dehydrated in the C1 step; Characterized in that it comprises

Insulating oil treatment method including PCBs.
The method of claim 10,

The color of the polyurethane formed after the step C2 can be selected by adjusting the heating temperature or dehydration time for the polyol mixture precipitate in the step C1.

Insulating oil treatment method including PCBs.