JP3342438B2 - Method and apparatus for treating PCB-containing electrical insulating oil - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a PCB containing
The present invention relates to a method and an apparatus for treating electrical insulating oil .

[0002]

2. Description of the Related Art When incinerating and treating halogenated organic compounds such as PCBs and dioxins, the surrounding environment may be adversely affected. For this reason, for example, a halogenated organic compound and a catalyst such as sodium carbonate in a slurry form are added to high-temperature and high-pressure water, and an oxidizing agent such as oxygen gas is supplied to the water to decompose the halogenated organic compound and render it harmless. There has been proposed a method of performing a chemical treatment (for example, see US Pat. No. 5,746,926).

[0003]

SUMMARY OF THE INVENTION However, PCB
If the electrical insulating oil containing is industrially treated by the above-described method, the treatment cost becomes very high,
It was difficult to put it to practical use.

[0004] In view of the above, the present invention is based on the PCB including
It is an object of the present invention to provide a method and an apparatus capable of reliably treating electric insulating oil at low cost industrially.

[0005]

SUMMARY OF THE INVENTION in order to solve the problems described above, the processing method of the PCB-containing electrical insulating oil according to the present invention is to supply oxygen to PCB-containing electrical insulating oil in water 30
A heat treatment is performed at a temperature of 0 to 350 ° C. to decompose oil and transfer PCB to the water.

In order to solve the above-mentioned problems, a method for treating a PCB-containing electrical insulating oil according to the present invention comprises supplying oxygen to PCB-containing electrical insulating oil in water , heating the PCB-containing electrical insulating oil at a temperature of 300 to 350 ° C. After decomposing the water and transferring the PCB to the water, the water and sodium carbonate are supplied with oxygen.
The PCB is supplied and heated at 350 to 400 ° C. to decompose the PCB.

[0007] In order to solve the above-mentioned problems, the apparatus for treating a PCB-containing electrical insulating oil according to the present invention supplies oxygen in water to the PCB-containing electrical insulating oil and heat-treats the PCB-containing electrical insulating oil at a temperature of 300 to 350 ° C to remove oil content. And an electrically insulating oil decomposing means for decomposing the PCB and transferring the PCB to the water.

[0008] In order to solve the above-mentioned problems, the apparatus for treating a PCB-containing electrical insulating oil according to the present invention is characterized in that the PCB-containing electrical insulating oil is heated at a temperature of 300 to 350 ° C. An oil separating means for decomposing the water and transferring the PCB to the water; and supplying oxygen from the water and sodium carbonate from the electric insulating oil decomposing means.
PCB decomposing means for decomposing the PCB by heat treatment at 350 to 400 ° C.

In the above-described apparatus for treating PCB-containing electric insulating oil , the electric insulating oil decomposition means supplies the PCB-containing electric insulating oil to the oil decomposition reaction vessel, the oil decomposition reaction vessel being capable of maintaining the inside at high temperature and high pressure. PCB-containing electricity
Insulating oil supply means, water supply means for supplying water to the oil decomposition reaction vessel, and the water supplied to the oil decomposition reaction vessel
And a combustion means for burning the PCB-containing electric insulating oil at a temperature of 300 to 350 ° C.

In the above-described apparatus for treating a PCB-containing electrical insulating oil , the combustion means includes an oxygen supply means for supplying oxygen into the reaction vessel, and an oil supply means for supplying oil to the reaction vessel. It is characterized by the following.

[0011] In the above-described apparatus for treating a PCB-containing electrical insulating oil , the oil supply means may include the PCB in the reaction vessel.
The PCB-containing electric insulating oil supplying means for supplying the electric insulating oil containing PCB .

In the above-described apparatus for treating electrical insulating oil containing PCB, the water sent from the oil decomposition reaction vessel is stored, and a part of the water is returned to the water supply means to be contained in the water. PCB to increase PCB concentration
It is characterized in that a concentration means is provided in the electric insulating oil decomposition means.

[0013] In the processing apparatus of the PCB-containing electrical insulating oil as described above, the PCB and PCB decomposition reactor can be maintained decomposition means an internal high temperature and high pressure state, containing PCB supplying water contained in the PCB decomposition reaction vessel PCB a water supply means, a sodium hydroxide supply means for supplying an aqueous solution of sodium hydroxide to the PCB decomposition reaction vessel, the
And a combustion means for burning the inside of the PCB decomposition reaction vessel at a temperature of 350 to 400 ° C.

In the above-described apparatus for treating a PCB-containing electrical insulating oil , the combustion means includes oxygen supply means for supplying oxygen to the reaction vessel, and oil supply means for supplying oil to the reaction vessel. It is characterized by the following.

[0015] In the above-described apparatus for treating a PCB-containing electrical insulating oil , the oil supply means may include the PCB in the reaction vessel.
Characterized in that it is a PCB-containing electrical insulating oil supply means for supplying containing electrical insulating oil.

In the above-described apparatus for treating an electrical insulating oil containing PCB , the sodium carbonate circulating means for separating sodium carbonate sent out together with water from the PCB decomposition reaction vessel from the water and returning the same to the inside of the PCB decomposition reaction vessel is provided with the PCC.
B disassembly means is provided.

[0017] In the processing apparatus of the PCB-containing electrical insulating oil as described above, through the ejector to the side wall lower side of the PCB decomposition reaction vessel was connected to the PCB-containing water supply means, those <br/> the PCB-containing water supply means And the ejector is connected with the sodium hydroxide supply means.

In the above-described apparatus for treating a PCB-containing electrical insulating oil , the PCB- containing water supply means is connected to the lower side of the side wall of the PCB decomposition reaction vessel via an ejector, and a large-diameter portion provided at a throttle portion of the ejector. And the oil supply means is connected to the oil supply means.

In the above-described apparatus for treating a PCB-containing electric insulating oil , the PCB- containing water supply means is connected to the lower side of the side wall of the PCB decomposition reaction vessel via an ejector, and the sodium carbonate circulating means has a sodium carbonate sending-out side. Is connected to the suction chamber of the ejector.

In the above-described apparatus for treating a PCB-containing electrical insulating oil , a water outlet is provided on a side wall of the PCB decomposition reaction vessel.

[0021]

DETAILED DESCRIPTION OF THE INVENTION PCB-containing electrical insulation according to the invention
An embodiment in which the oil treatment method and the treatment apparatus are applied to the treatment of electric insulating oil containing a low concentration of PCB will be described with reference to FIG. FIG. 1 is an overall schematic configuration diagram of the apparatus.

[Configuration] <Overall> As shown in FIG. 1, the PCB-containing electric insulating oil processing apparatus of the present embodiment comprises a low-concentration PCB-containing oil 1 and water 3
An oil cracking device 10 which is an electrically insulating oil cracking means for decomposing oil by heating at a temperature of 00 to 350 ° C. and transferring the PCB 2 to the water 3, and the water 3 and sodium carbonate 8 from the oil cracking device 10. Is a PCB decomposition means for decomposing PCB2 by heat-treating PCB2 at 350 to 400 ° C.
A disassembly device 20 is provided.

<Oil Cracking Device 10> The oil cracking device 10 includes an oil cracking reaction vessel 11 capable of maintaining the inside at high temperature and high pressure, and a
The PCB-containing oil tank 12a and the oil supply pump 12b that constitute the PCB-containing electric insulating oil supply means that supplies the oil 1, and the water storage tank 13a and the water supply that constitute the water supply means that supplies the water 3 to the oil decomposition reaction vessel 11. Pump 13b and the like, and the PCB-containing oil 1 supplied into the
Oxygen cylinder 14a and the like constituting an oxygen supply means for supplying oxygen 5 into the oil cracking reaction vessel 11 for burning at a temperature of 0 to 350 ° C, and oil supply for supplying combustion oil 4 into the oil cracking reaction vessel 11 Combustion oil tank 25 constituting means
a, a refueling pump 25b, etc.
Also serves as a thing. ) And a sodium hydroxide aqueous solution tank 23a and a supply pump 23b which constitute a pH adjusting means for supplying an aqueous solution of sodium hydroxide 6 into the oil cracking reaction vessel 11 to adjust the pH in the vessel 11 (PCB described later). The heat is exchanged between the water 3 from the water storage tank 13a supplied into the oil cracking reaction vessel 11 and the water 3 sent out from the oil cracking reaction vessel 11). The heat exchanger 16 and the oil cracking reaction vessel 1
1, the water 3 sent out via the heat exchanger 16 is temporarily stored and released under the atmospheric pressure, and a part of the water 3 is returned to the water storage tank 13 a to return the PCB in the water 3.
It is provided with a concentration tank 17a, a circulation pump 17b, and the like, which constitute a PCB concentration means for increasing the concentration of 2. In FIG. 1, reference numeral 19 denotes a supply header.

<PCB Decomposition Apparatus 20> The PCB decomposition apparatus 20 is composed of a PCB decomposition reaction vessel 21 capable of maintaining the inside at a high temperature and a high pressure, and the water 3 in the concentration tank 17a of the oil decomposition apparatus 10 by the PCB decomposition reaction vessel 21.
Feed pump 2 which is a means of supplying PCB- containing water to the inside
2 and the like, and an aqueous solution of sodium hydroxide 6 is supplied into the PCB decomposition reaction vessel 21 so that sodium carbonate 8 is present in the PCB decomposition reaction vessel 21. The pump 23b and the inside of the PCB decomposition reaction
Oxygen cylinder 14a, etc., which constitutes oxygen supply means for supplying oxygen 5 to the PCB decomposition reaction vessel 21 for burning at a temperature of 00 ° C. (also serves as the oil decomposition apparatus 10 described above) and PCB decomposition. Combustion oil tank 25a constituting oil supply means for supplying combustion oil 4 into reaction vessel 21
And oil supply pump 25b, etc., and cyclone separator 28 which constitutes sodium carbonate circulating means for separating sodium carbonate 8 sent out together with water 3 from PCB decomposition reaction vessel 21 from water 3 and returning the same to inside PCB decomposition reaction vessel 21 And the water 3 sent out from the PCB decomposition reaction vessel 21 through the cyclone separator 28 and the PCB decomposition reaction vessel 21
A heat exchanger 26 for exchanging heat with the water 3 from the concentration tank 17a of the oil cracking device 10 to be supplied to the inside;
A treatment water tank 27 is provided for storing the water 3 sent out from the decomposition reaction vessel 21 via the cyclone separator 28 and the heat exchanger 26 and opening the water 3 under atmospheric pressure. In FIG. 1, reference numeral 29 denotes a supply header.

[Operation / Effect] <Oil decomposition device 10> The water supply pump 13b is operated to operate the water 3 in the water storage tank 13a.
Is supplied into the oil cracking reaction vessel 11, and the inside of the vessel 11 is filled with the water 3, and then the oil supply pump 25b is operated to supply the combustion oil 4 from the combustion oil tank 25a into the oil cracking reaction vessel 11, and , Oxygen decomposition reaction vessel 1 from oxygen cylinder 14a
By supplying oxygen 5 into the oil decomposition reaction vessel 1
1 is burned in water to heat the internal temperature to 300 to 350 ° C. When the temperature in the oil cracking reaction vessel 11 reaches 300 to 350 ° C., the oil supply pump 25b is stopped to stop the supply of the combustion oil 4, and the oil supply pump 12b is operated to remove the PCB-containing oil 1 from the PCB-containing oil tank 12a. Oil decomposition reaction vessel 1
When supplied into the PCB 1, the oil contained in the PCB-containing oil 1 burns and decomposes to generate water 3 and carbon dioxide 7, while the PCB 2 moves to the water 3 without burning and decomposing.

At this time, the aqueous solution of sodium hydroxide 6 in the aqueous sodium hydroxide tank 23a is appropriately supplied into the oil decomposition reaction vessel 11 in order to suppress the pH of the water 3 from being lowered by the generated carbon dioxide 7. The pH of water 3 is kept near neutral.

Here, using an autoclave, 300
The decomposition rate of PCB and electrical insulating oil in water (containing dissolved sodium hydroxide and solid sodium carbonate (pH 8)) heated to ３380 ° C. is shown in FIG.
As can be seen from FIG. 2, the decomposition rate of the oil was 38
It is about 8 to 9 times faster at 380 ° C and about 3 times faster at 300 ° C compared to the decomposition rate at 0 ° C. Therefore, if the PCB-containing oil 1 is heat-treated at 300 to 350 ° C., the oil component can be burned and decomposed without decomposing the PCB 2. The reaction mechanism here is as shown below.

[Chemical Formula 1] C ₁₉ H ₃₄ + 27.5O ₂ ⇔19CO ₂ + 17H ₂ O (1) CO ₂ + H ₂ O⇔17H ₂ CO ₃ (2) H ₂ CO ₃ + NaOH⇔NaHCO ₃ + H ₂ O (3 )

FIG. 3 shows the pH and the proportion of carbonate ions in water at normal temperature. As can be seen from FIG.
Is near neutral, most of the CO ₂ is NaHCO ₃
And a very small portion is H ₂ CO ₃ .

Incidentally, the PCB-containing oil 1 is usually 1000 p
pm or less of PCB2 and electrical insulating oil ,
Generally, PCB2 is often 100 ppm or less. Therefore, if the PCB-containing oil 1 is treated as described above, the oil can be decomposed into CO ₂ and H ₂ O,
PCB 2 can be transferred to water 3.

The water 3 containing the PCB 2 and having the carbon dioxide 7 dissolved therein (300 to 350
(° C.) is passed through the heat exchanger 16 to heat the water 3 supplied from the water storage tank 13 a into the oil cracking reaction vessel 11 to make-up water, and then supplied to the concentration tank 17 to be supplied to the atmospheric pressure. Decompressed below and dissolved carbon dioxide 7
Is released to the atmosphere and the circulation pump 17
b, a part of the water 3 (about 100 ° C.) is stored in the water storage tank 13a.
And the concentration of the contained PCB is increased by being used again for the heat treatment of the PCB-containing oil 1.

<PCB Decomposition Apparatus 20> The water supply pump 22 is operated to supply the water 3 in the concentration tank 17a in which the concentration of the PCB 2 is increased into the PCB decomposition reaction vessel 21, and the inside of the vessel 21 is supplied with the water. After filling with 3, the fuel supply pump 25b is operated to supply the combustion oil 4 from the combustion oil tank 25a into the PCB decomposition reaction vessel 21 and to supply oxygen 5 from the oxygen cylinder 14a into the PCB decomposition reaction vessel 21. By this, the PCB decomposition reaction vessel 2
1 is heated to 350 to 400 ° C. (preferably 380 to 400 ° C.) while the inside is burned in water, and the supply pump 23 b is operated to activate the sodium hydroxide aqueous solution tank 23.
The aqueous solution of sodium hydroxide 6 in a is supplied into the PCB decomposition reaction vessel 21, and the inside of the vessel 21 is maintained at pH 8 to 12.

When sodium hydroxide 6 is added to the inside of the PCB decomposition reaction vessel 21 and heated to 350 to 400 ° C. (preferably 380 to 400 ° C.) while maintaining the pH at 8 to 12, the combustion oil 4 and oxygen 5 The carbon dioxide 7 generated as a result of the combustion reaction with the sodium hydroxide 6 reacts with the sodium hydroxide 6, and the sodium carbonate 8 is formed in the water 3 in the form of a slurry as solid particles and acts as a decomposition catalyst for the PCB 2,
2 decomposes into water, carbon dioxide and sodium chloride (salt) 9.

That is, in the PCB decomposition reaction vessel 21, the following reactions occur in addition to the above-described reaction mechanisms (1) to (3).

[Formula 2] NaHCO ₃ + NaOH⇔NaCO ₃ + H ₂ O (4) C ₁₂ H ₆ Cl ₄ + 12.5O ₂ + 2Na ₂ CO ₃ ⇔14CO ₂ + 3H ₂ O + 4NaCl (5)

[0036] Here, by setting the water 3 in the alkaline region of PH8～12 (preferably pH 10-12), as can be seen from FIG. 3 described above, CO ₂ is the most part Na ₂
It is present as CO ₃ , and a very small portion is present as NaHCO ₃ . As can be seen from FIG. 4, this Na ₂ CO ₃ rapidly decreases when its solubility in water is 350 ° C. or more, and therefore precipitates as an active solid in the form of slurry in water 3 at 350 ° C. or more. .

Therefore, the water 3 is heated to 350 to 400 ° C. (preferably 380 to 400 ° C.) while adding the sodium hydroxide 6 to the water 3 and keeping the pH at 8 to 12, that is, Na ₂ CO ₃ is present in the water 3. While heating to 350 to 400 ° C (preferably 380 to 400 ° C), PCB2
Is CO ₂ , H ₂ O, N by O ₂ and Na ₂ CO ₃
It is decomposed into aCl and becomes completely harmless.

The Na ₂ CO ₃ is produced and replenished by reacting the CO ₂ generated by the combustion of the combustion oil 4 and NaOH by making up NaOH in the PCB decomposition reaction vessel 21.

The water 3 (300 to 350 ° C.) thus treated, in which the salt 9 and the carbon dioxide 7 are dissolved and the sodium carbonate 8 is kept in a slurry state, is passed through the cyclone separator 28 from the inside of the PCB decomposition reaction vessel 21. Then, the sodium carbonate 8 is removed, and the water 3 supplied from the concentration tank 17a of the oil cracking device 10 into the PCB cracking reaction vessel 21 via the heat exchanger 26 is heated. The gas is supplied into the tank 27 and depressurized to the atmospheric pressure, and most of the dissolved carbon dioxide 7 is released into the atmosphere.

Therefore, even if the electrical insulating oil contains a low concentration of PCB2, the PCB2 and the electrical insulating oil can be efficiently decomposed, so that the detoxification process can be reliably performed at low cost industrially. .

In the present embodiment, the combustion oil 4 is supplied by using the combustion oil tank 25a, the oil supply pump 25b, or the like as the oil supply means. If the PCB-containing electric insulating oil supply means such as the oil-containing tank 12a and the oil supply pump 12b also serves as the oil supply means and supplies the PCB-containing oil 1 instead of the combustion oil 4, processing can be performed at lower cost. Can be.

In this embodiment, an aqueous solution of sodium hydroxide 6 is supplied into the oil decomposition reaction vessel 11 to adjust the inside of the vessel 11 to neutral (about pH 8). There is no particular problem even if the inside of the container 11 is in a neutral to weakly acidic region.
Need not be supplied into the oil decomposition reaction vessel 11.

Further, in the PCB disassembling apparatus 20, it is more preferable to use an ejector 39 as shown in FIG.

That is, as shown in FIG. 5, the distal end of the ejector 39 is connected to the lower side of the side wall of the PCB decomposition reaction vessel 21, and the base end of the ejector 39 is connected to the outlet of the water supply pump 22. Supply pump 23b connected via an exchanger 26 to supply an aqueous solution of sodium hydroxide 6
Of the heat exchanger 26 with the base end of the ejector 39
And an oil supply pump 1 that connects the outlet of sodium carbonate 8 of the cyclone separator 28 to the suction chamber of the ejector 39 and feeds the PCB-containing oil 1 and the combustion oil 4.
The outlets 2b and 25b are connected to the high-speed flow position of the enlarged diameter portion provided in the throttle portion of the ejector 39. In FIG. 5, reference numeral 14b denotes an oxygen supply nozzle.

Therefore, the water 3 supplied from the heat exchanger 26 and the aqueous solution of sodium hydroxide 6 supplied from the supply pump 23 b sent by the water supply pump 22 into the PCB decomposition reaction vessel 21 via the ejector 39 at a high speed. , The water 3 and the aqueous solution are uniformly mixed, and the shearing force accompanying the flow of the water 3 causes the oil pump 1
Since the oils 1 and 2 from 2b and 25b are mixed evenly with the water 3, the reaction is performed uniformly in the PCB decomposition reaction vessel 21 and partial heat generation and temperature rise in the vessel 21 are prevented. can do.

Further, the sodium carbonate 8 separated by the cyclone separator 28 is returned into the PCB decomposition reaction vessel 21 by the suction force of the ejector 39 caused by the flow of the water 3, so that the sodium carbonate 8 can be circulated. It is not necessary to provide a circulating pump, and the cost can be reduced.

Here, as shown in FIG. 5, by providing an outlet for water 3 or the like from the PCB decomposition reaction vessel 21 on the side wall of the vessel 21, oxygen 5 or dioxide not dissolved in the water 3 or the like can be obtained. Since the gas such as carbon 7 stays at the top of the container 21 (the level of the interface between the gaseous phase and the liquid phase is such that the dissolution rate of the staying gas in the liquid phase and the gas generation rate are balanced. ). It is possible to prevent these gases from flowing into the cyclone separator 28, the heat exchanger 26, and the like, and to suppress a decrease in heat transfer efficiency and operation efficiency.

In the present embodiment, the oil decomposer 1
0 and the PCB cracking device 20 are connected via a line, but the oil cracking device 10 and the PCB cracking device 20 may be individually and independently provided.

When only the oil in the PCB-containing oil 1 is to be treated, only the oil decomposer 10 may be used.

[0050]

EXAMPLES The following tests were conducted to confirm the effects of the method of treating electric insulating oil containing PCB and the treatment apparatus according to the present invention.

[0051] [Test Example 1] Based on the embodiments described above, and processing the electrical insulating oil to 50ppm containing PCB on a scale of 10ton / day. Note that sodium hydroxide was added during the decomposition treatment of the electric insulating oil. FIG. 6 shows various data at that time.

[0052] [Test Example 2] Based on the embodiments described above, and processing the electrical insulating oil to 50ppm containing PCB on a scale of 10ton / day. Incidentally, sodium hydroxide was not added during the decomposition treatment of the electric insulating oil. FIG. 7 shows various data at that time.

[0053] [Comparative Example] collectively without separating the decomposition process of the decomposition process and PCB oil of PCB-containing electrical insulating oil were conducted at the same time. FIG. 8 shows various data at that time.

As can be seen from FIGS. 6 to 8, the volume ratio is about 1/4 in the case of Test Example 1 and about 1/5 in the case of Test Example 2 as compared with the comparative example. Extremely high efficiency. Further, compared with the comparative example, the amount of sodium hydroxide used is about 1/5 in the case of Test Example 1 and about 1/70 in the case of Test Example 2, so that the chemical cost for the treatment is extremely low. Become. Therefore, it was confirmed that the treatment can be performed industrially at low cost.

[0055]

The method for treating a PCB-containing electric insulating oil according to the present invention comprises supplying the PCB-containing electric insulating oil with oxygen in water.
Heat treatment at a temperature of 300 to 350 ° C. to decompose the oil component and transfer the PCB to the water, so that only the oil component can be decomposed without burning the PCB,
The detoxification treatment can be reliably performed at low cost industrially.

In the method for treating a PCB-containing electrical insulating oil according to the present invention, the PCB-containing electrical insulating oil is supplied with oxygen in water and heat-treated at a temperature of 300 to 350 ° C. to decompose oil and to convert the PCB into the water. After the transfer, the water and the sodium carbonate are supplied with oxygen and heat-treated at 350 to 400 ° C. to decompose the PCB, so that the PCB and the electric insulating oil can be decomposed efficiently and industrially. In addition, the detoxification process can be reliably performed at low cost.

The apparatus for treating a PCB-containing electrical insulating oil according to the present invention supplies oxygen in the PCB-containing electrical insulating oil and heat-treats the PCB-containing electrical insulating oil at a temperature of 300 to 350 ° C. to decompose the oil component and to convert the PCB into the water. Since the apparatus is provided with the electrically insulating oil decomposing means for shifting, only the oil component can be decomposed without burning the PCB, and the detoxification can be reliably performed at low cost industrially.

The apparatus for treating a PCB-containing electrical insulating oil according to the present invention supplies oxygen to the PCB-containing electrical insulating oil and heat-treats the PCB-containing electrical insulating oil at a temperature of 300 to 350 ° C. to decompose the oil component and to convert the PCB into the water. An electrical insulating oil decomposing means to be transferred, and a PCB decomposing means for decomposing the PCB by supplying oxygen from the water and sodium carbonate from the electric insulating oil decomposing means and heating at 350 to 400 ° C. Therefore, the PCB and the electric insulating oil can be efficiently decomposed, and the detoxification process can be reliably performed at low cost industrially.

Further , an oil cracking reaction vessel in which the electric insulating oil cracking means can maintain the inside at a high temperature and high pressure state, and a PCB for supplying the PCB- containing electrical insulating oil to the oil cracking reaction vessel
Containing electrical insulating oil supply means, water supply means for supplying water to the oil cracking reaction vessel, and combustion for burning the PCB-containing electrical insulating oil supplied into the oil cracking reaction vessel at a temperature of 300 to 350 ° C. Therefore, it is possible to reliably transfer the PCB to the water side while completely decomposing the oil component.

Further , since the combustion means includes an oxygen supply means for supplying oxygen into the reaction vessel and an oil supply means for supplying oil into the reaction vessel, the combustion means includes PCBs even in water under a high pressure environment. The oil content of the electric insulating oil can be reliably burned.

[0061] Further, said PCB for supplying electrical insulating oil supply means to the PCB-containing electrical insulating oil into the reaction vessel
With the contained electric insulating oil supply means, the cost and efficiency of the treatment can be improved.

Further , there is provided a PCB enrichment means for storing the water sent from the oil cracking reaction vessel and for refluxing a part of the water to the water supply means to increase the concentration of PCB contained in the water. Since it is provided in the electric insulating oil decomposition means, it is possible to efficiently process PCB .

[0063] Also, the PCB decomposition reactor can be maintained at a high temperature and a high pressure state inside the PCB decomposing means, the electrical insulation
A PCB- containing water supply means for supplying the water from the rim oil decomposition means to the PCB decomposition reaction vessel, a sodium hydroxide supply means for supplying an aqueous solution of sodium hydroxide into the PCB decomposition reaction vessel, and the PCB decomposition reaction 35 in the container
Since a combustion means for burning at a temperature of 0 to 400 ° C. is provided, it is possible to reliably decompose the PCB transferred to the water side.

Further , since the combustion means includes an oxygen supply means for supplying oxygen to the reaction vessel and an oil supply means for supplying oil to the reaction vessel, the PCB can be used even in water under a high pressure environment. Decomposition processing can be performed reliably.

[0065] Further, the PCB-containing electrical supplies the oil supply means to the PCB-containing electrical insulating oil into the reaction vessel
With the insulating oil supply means, the cost and efficiency of the processing can be improved.

Further, sodium carbonate delivered together with water from the PCB decomposition reaction vessel is separated from the water and separated.
Since the sodium carbonate circulating means for returning to the inside of the PCB decomposition reaction vessel is provided in the above-mentioned PCB decomposition means, sodium carbonate can be used without waste, and the processing cost can be reduced.

Further, the PCB- containing water supply means is connected to the lower side of the side wall of the PCB decomposition reaction vessel via an ejector, and the sodium hydroxide supply means is connected between the PCB- containing water supply means and the ejector. If you do, PC
Since the B- containing water and the aqueous solution of sodium hydroxide can be uniformly mixed, it is possible to prevent partial heat generation and temperature rise in the PCB decomposition reaction vessel.

Further , if the PCB- containing water supply means is connected to the lower side of the side wall of the PCB decomposition reaction vessel via an ejector, and the oil supply means is connected to a large-diameter portion provided in a throttle portion of the ejector, Since oil can be uniformly mixed with PCB- containing water, it is possible to prevent partial heat generation and temperature rise in the PCB decomposition reaction vessel.

Further , the PCB- containing water supply means is connected to the lower side of the side wall of the PCB decomposition reaction vessel via an ejector, and the sodium carbonate sending / outlet side of the sodium carbonate circulating means is connected to the suction chamber of the ejector. The sodium carbonate separated by the sodium carbonate circulating means to the PCB
Since it can be supplied into the PCB decomposition reaction vessel together with the contained water, there is no need to provide a circulation pump or the like for circulating the separated sodium carbonate under a high-pressure environment in the sodium carbonate circulating means, and the cost of the apparatus can be reduced.

[0070] Further, by providing the water outlet on the side wall side of the PCB decomposition reaction vessel, the generated gases is such that the reservoir on top of the PCB decomposition reaction vessel, PCB decomposing reaction vessel together with the water From the outside, and a decrease in heat transfer efficiency and operation efficiency can be suppressed.

[Brief description of the drawings]

FIG. 1 is an overall schematic configuration diagram of an embodiment in a case where a treatment device for a PCB-containing electric insulating oil according to the present invention is applied to the treatment of an electric insulating oil containing a low concentration of PCB.

FIG. 2 is a graph showing decomposition rates of PCB and electric insulating oil .

FIG. 3 is a graph showing the pH in water and the proportion of carbonate ion species present.

FIG. 4 is a graph showing the solubility of sodium carbonate in water.

FIG. 5 is an enlarged enlarged view of a main part of another example of the embodiment in a case where the apparatus for treating a PCB-containing electrical insulating oil according to the present invention is applied to the treatment of an electrical insulating oil containing a low concentration of PCB.

FIG. 6 is a diagram showing various data of Test Example 1.

FIG. 7 is a diagram showing various data of Test Example 2.

FIG. 8 is a diagram showing various data of a comparative example.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 PCB containing oil 2 PCB 3 Water 4 Combustion oil 5 Oxygen 6 Sodium hydroxide 7 Carbon dioxide 8 Sodium carbonate 9 Sodium chloride (salt) 10 Oil cracking device 11 Oil cracking reaction vessel 12a PCB containing oil tank 12b Oil pump 13a Water storage tank 13b Water supply pump 14a Oxygen cylinder 14b Oxygen supply nozzle 16 Heat exchanger 17a Concentration tank 17b Circulation pump 19 Supply header 20 PCB decomposer 21 PCB decomposition reaction vessel 22 Water supply pump 23a Sodium hydroxide aqueous solution tank 23b Supply pump 25a Combustion oil tank 25b Oil supply pump 26 heat exchanger 27 treated water tank 28 cyclone separator 29 supply header 39 ejector

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI // C10N 40:16 C10N 40:16 (72) Inventor Toshiyuki Hatano 1-1-1, Akunouracho, Nagasaki-shi, Nagasaki Mitsubishi Heavy Industries, Ltd. Inside Nagasaki Shipyard (56) References JP-A-8-141107 (JP, A) JP-A-10-28951 (JP, A) JP-A-11-639 (JP, A) JP-A-2000-5594 (JP, A) JP-A-2000-116814 (JP, A) JP-A-11-90385 (JP, A) JP-A-11-319773 (JP, A) JP-A-11-197492 (JP, A) JP-A-10-156174 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) A62D 3/00 B01J 3/00 B01J 19/00 301 G10G 9/00 C10M 175/02

Claims (16)

(57) [Claims] 1. An oxygen- containing electrical insulating oil containing PCB is supplied in water.
A heat treatment at a temperature of 300 to 350 ° C. to decompose oil and transfer the PCB to the water. 2. A method of supplying oxygen containing PCB-containing electrical insulating oil in water.
After the heat treatment is performed at a temperature of 300 to 350 ° C. to decompose the oil component and transfer the PCB to the water, the water and the sodium carbonate are supplied with oxygen to perform a heat treatment at 350 to 400 ° C. P is characterized by disassembling the PCB
A method for treating CB-containing electrical insulating oil. 3. An oxygen- containing PCB-containing electrical insulating oil is supplied in water.
An apparatus for treating PCB-containing electrical insulating oil, comprising electrical insulating oil decomposing means for supplying oil and decomposing oil by heating at a temperature of 300 to 350 ° C. and transferring PCB to the water. 4. An oxygen- containing electrical insulating oil containing PCB is supplied in water.
And a heat treatment at a temperature of 300 to 350 ° C. to decompose oil and decompose the PCB and transfer the PCB to the water; and convert the water and sodium carbonate from the electric insulating oil decomposer into oxygen. A PCB decomposing means for decomposing the PCB by supplying it and heating at 350 to 400 ° C. to treat the PCB-containing electric insulating oil. 5. An oil cracking reaction vessel in which the electric insulating oil decomposition means can maintain the inside at a high temperature and high pressure state; a PCB-containing electric insulating oil supply means for supplying the PCB-containing electric insulating oil to the oil decomposition reaction vessel; Water supply means for supplying water to the oil cracking reaction vessel; and burning means for burning the PCB-containing electric insulating oil supplied into the oil cracking reaction vessel at a temperature of 300 to 350 ° C. The apparatus for treating a PCB-containing electrical insulating oil according to claim 3 or 4, wherein: 6. The apparatus according to claim 5, wherein the combustion means includes an oxygen supply means for supplying oxygen to the reaction vessel, and an oil supply means for supplying oil to the reaction vessel. Equipment for treating PCB-containing electrical insulating oil. 7. The method according to claim 7, wherein the oil supply means includes the P
The P-containing electrical insulating oil supply means for supplying CB-containing electrical insulating oil.
Processing equipment for CB-containing electrical insulating oil. 8. A method for storing the water sent from the oil cracking reaction vessel, and refluxing a part of the water to the water supply means to increase the concentration of PCB contained in the water.
The apparatus for treating PCB-containing electric insulating oil according to any one of claims 5 to 7, wherein a CB concentrating means is provided in the electric insulating oil decomposing means. 9. A PCB decomposition reaction vessel, wherein the PCB decomposition means can maintain the inside at high temperature and high pressure, a PCB-containing water supply means for supplying water containing PCB to the PCB decomposition reaction vessel, and the PCB decomposition reaction vessel 5. A sodium hydroxide supply means for supplying an aqueous solution of sodium hydroxide therein, and a combustion means for burning the inside of the PCB decomposition reaction vessel at a temperature of 350 to 400 ° C. Equipment for treating PCB-containing electrical insulating oil. 10. The apparatus according to claim 9, wherein said combustion means includes an oxygen supply means for supplying oxygen to said reaction vessel, and an oil supply means for supplying oil to said reaction vessel. Equipment for treating PCB-containing electrical insulating oil. 11. The P according to claim 10, wherein said oil supply means is a PCB-containing electrical insulating oil supply means for supplying said PCB-containing electrical insulating oil to said reaction vessel.
Processing equipment for CB-containing electrical insulating oil. 12. The sodium carbonate sent out together with water from the PCB decomposition reaction vessel is separated from the water and
The apparatus for treating a PCB-containing electrical insulating oil according to any one of claims 9 to 11, wherein a means for circulating sodium carbonate returning to the inside of the CB decomposition reaction vessel is provided in the PCB decomposition means. 13. The PCB-containing water supply means is connected via an ejector to a lower side of a side wall of the PCB decomposition reaction vessel, and the sodium hydroxide supply means is connected between the PCB-containing water supply means and the ejector. The apparatus for treating a PCB-containing electrical insulating oil according to any one of claims 9 to 12, wherein: 14. The method according to claim 14, wherein the PCB-containing water supply means is connected to a lower side of the side wall of the PCB decomposition reaction vessel via an ejector, and the oil supply means is connected to a large-diameter portion provided in a throttle portion of the ejector. 10. The method according to claim 10, wherein:
2. The apparatus for treating a PCB-containing electrical insulating oil according to claim 1. 15. The PCB-containing water supply means is connected to the lower side of the side wall of the PCB decomposition reaction vessel via an ejector, and the sodium carbonate sending / outlet side of the sodium carbonate circulating means is connected to a suction chamber of the ejector. The apparatus for treating a PCB-containing electrical insulating oil according to claim 12, wherein: 16. The apparatus for treating a PCB-containing electrical insulating oil according to claim 9, wherein a water outlet is provided on a side wall of the PCB decomposition reaction vessel.