WO2018062222A1 - Method and device for decomposing organic halogen compound - Google Patents

Abstract

[Problem] To provide a method and device for decomposing an organic halogen compound such that an organic halogen compound can be decomposed easily and safely under mild conditions, and the compound can be treated without a burning step, thereby contributing to CO₂ reduction. [Solution] An organic halogen compound-containing liquid such as PCBs or dioxin and an alkali metal hydroxide solution such as sodium hydroxide or potassium hydroxide are placed in an electrolytic reaction vessel and mixed. A high shear mixing device such as a disperser or a homogenizer is submerged in the mixed solution. A positive electrode such as platinum or iridium is disposed around the shear mixing device, and the shear mixing device is energized as a negative pole and the positive electrode as the positive pole to perform electrolysis. It is also preferable to perform an electrolysis reaction while applying ultrasonic vibrations to the electrolytic reaction vessel.

Description

Method and apparatus for decomposing organohalogen compounds

The present invention relates to a method for decomposing organic halogen compounds, and more particularly, to a method and apparatus for decomposing and removing harmful organic halogen compounds such as difficult-to-decompose PCBs and dioxins.

Organohalogen compounds have many harmful substances, and in particular, many substances that pollute the environment, such as polychlorinated biphenyls (PCBs), dioxins, and organic pesticides.
In particular, since PCB is a hardly decomposable harmful substance, it takes many years for detoxification treatment.

Currently recognized methods for the disposal of waste oil containing PCB include the high-temperature thermal decomposition method, dechlorination decomposition method, hydrothermal oxidation decomposition method, reductive thermal chemical decomposition method, and photolysis method. The plasma decomposition method and the supercritical method are known.
Among these, the dechlorination / decomposition method is considered desirable from the viewpoints that a large-sized and special apparatus is not necessary, that no harmful by-products are generated, and that by-products can be reused.

In such background technology, in the case of a high concentration, a metal sodium dispersion oil or an alkali metal organic compound or a Pd / C catalyst is used for hydrogen reduction in the dehalogenation decomposition method. It is difficult to make it 0.5 ppm or less, and the combustion method is mainly used.

JP2002-756 JP 2001-269673 A JP-A-8-66494 JP 2002-265391 A JP 2002-345991 Republished 2005-092448 (WO2005 / 092448)

As a method for detoxifying PCB and the like by a relatively simple operation means, a method for dehalogenating by adding metallic calcium to an alcohol solution such as PCB and mixing it has also been proposed. However, this method also has a problem that an organic solvent must be used. [Patent Document 4]

Also proposed is a method in which a PCB is mixed with a solvent such as water or acetonitrile, and the PCB is treated by electrolysis. This method is an excellent method capable of detoxifying PCB relatively easily, but has a problem that a special apparatus is required. [Patent Document 5]

The electrolysis method is characterized in that a hydrogen storage metal or an alloy thereof is used as a cathode, and a method of increasing electrolysis efficiency by using a diaphragm electrolytic layer and an ultrasonic generator and stirring has been proposed. This method is effective for high-concentration PCB, but less effective for low-concentration PCB. [Patent Document 6]

As described above, according to the conventional technology, it was not possible to dehalogenate / detoxify organic halogen compounds with high efficiency at normal temperature and pressure.

As a result of earnest research, the inventor of the present application succeeded in decomposing an organic halogen compound-containing liquid with high efficiency at normal pressure from normal temperature to relatively low temperature (100 ° C. or less) by the following constitutional invention.
That is, the present invention is an organic halogen compound decomposition method and apparatus according to the following [1] to [10].
[1] An organohalogen compound-containing liquid and an alkali metal hydroxide aqueous solution are put into an electrolytic reaction tank and mixed, and a conductive high-speed shearing type miniaturization mixing device such as a disperser or homogenizer is mixed in the mixed liquid. And an anode is disposed around the same fine-mixing device, the high-speed shearing-type fine-mixing device is used as a cathode, and the positive electrode is used as an anode for electrolysis and electrolysis. Method for decomposing halogen compounds.
[2] The organic halogen compound is one or more selected from organic fluorine compounds, organic chlorine compounds, organic bromine compounds, VOCs, PCBs, dioxins, or organic chlorine-based pesticides [ [1] A method for decomposing an organic halogen compound according to [1].
[3] The alkali metal hydroxide aqueous solution is one or more selected from a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution or a lithium hydroxide aqueous solution. [1] or [2] Of decomposition of organic halogen compounds.
[4] The high-speed shearing type micronizing / mixing device as a cathode is a conductive high-speed shearing type micronizing / mixing device such as a disperser, a homogenizer, a homomixer, a line mixer, or an emulsion generator [1] ] To [3]. The method for decomposing an organic halogen compound according to any one of [3].
[5] Any one of [1] to [4], wherein the positive electrode is a white metal such as platinum, iridium, osmium, or an alloy thereof, or a plated product or carbon thereof, which is an insoluble metal The method for decomposing an organic halogen compound according to claim 1.
[6] The method for decomposing an organic halogen compound according to any one of [1] to [5], wherein the electrolytic reaction is performed while applying ultrasonic vibration in the electrolytic reaction tank.
[7] An electrolytic reaction tank into which an organic halogen compound-containing liquid and an aqueous alkali metal hydroxide solution are charged, and a conductive high-speed shearing type micronizing / mixing device such as a disperser, line mixer, and homogenizer provided therein An organic halogen compound decomposition comprising: a positive electrode disposed in the periphery of the fine mixing device; and a power supply device energized with the fine mixing device as a cathode and the positive electrode as an anode. apparatus.
[8] The high-speed shearing type micronizing / mixing device as a cathode is a conductive high-speed shearing type micronizing / mixing device such as a disperser, a homogenizer, a homomixer, a line mixer, or an emulsion generator [7] ] The decomposition | disassembly apparatus of the organic halogen compound as described in any one of.
[9] Described in [7] or [8], wherein the positive electrode is a white metal such as platinum, iridium, or osmium which is an insoluble metal, or an alloy thereof, or a plated product or carbon thereof. Organic halogen compound decomposition equipment.
[10] The organohalogen compound decomposition apparatus according to any one of [7] to [9], wherein an ultrasonic oscillator is attached to the electrolytic reaction tank.

According to the present invention, an organic halogen compound-containing liquid such as PCB or dioxin can be decomposed with high efficiency at normal temperature to 100 ° C. and normal pressure.
According to the present invention, the high-speed shearing type refining / mixing device itself is used as a cathode, and an organic halogen compound such as PCB is refined by high-speed shearing, and at the same time, an alkali metal hydroxide (for example, alkali metal hydroxide generated by electrolysis) By greatly contacting and reacting Na), the reaction rate between the organic halogen compound and the alkali metal can be dramatically increased.
The present invention adopts an unprecedented idea of causing an electrolytic reaction while using a high-speed shearing-type micronizing / mixing device as a cathode to cause an electrolysis reaction while miniaturizing and mixing. Reacts under normal pressure and can operate safely with only electricity as the power source.
Since the decomposition reaction of the present invention is carried out in a large amount of aqueous solution and no dangerous material such as Na metal is used, there is no danger of fire or explosion.
Especially for low-concentration PCB-containing liquids, which has been difficult to achieve in the past, the reaction rate is dramatically increased by using the high-speed shearing type micronizing / mixing device as the cathode and making the electrode reaction while miniaturizing. Is done.
According to the present invention, organic chlorine compounds such as PCBs, dioxins, organic pesticides, VOCs, etc., organic fluorine compounds, and organic bromine compounds, which have been difficult to decompose in the past, are also from room temperature to 100 ° C. It became possible to process at normal pressure.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram of the decomposition apparatus of the organic halogen compound used in the Example of this invention, (a) A figure is a cross-sectional explanatory drawing, (b) A figure is an upper surface explanatory drawing. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram of the decomposition apparatus of the organic halogen compound used by a prior art example, (a) A figure is a cross-sectional explanatory drawing, (b) A figure is a top explanatory drawing It is a detailed structure figure of the principal part of the high-speed shearing type | mold refinement | mixing apparatus 3, (a) is a front view, (b) is a longitudinal cross-sectional view, (c) is a bottom view.

In carrying out the present invention, first, an organic halogen compound decomposition apparatus equipped with a high-speed shearing type fine-mixing apparatus as shown in FIG. 1 is prepared.
FIG. 1 is a schematic view of an organohalogen compound decomposition apparatus used in the embodiment of the present invention. FIG. 1 (a) is a cross-sectional explanatory view, and FIG. 1 (b) is a top explanatory view.
2A and 2B are schematic views of an organic halogen compound decomposition apparatus used in the conventional example. FIG. 2A is a cross-sectional explanatory view, and FIG. 2B is a top explanatory view.
FIG. 3 is a detailed structural diagram of the main part of the high-speed shearing type micronizing / mixing device 3, wherein (a) is a front view, (b) is a longitudinal sectional view, and (c) is a bottom view.
In the figure, 1 is an electrolytic reaction tank, 2 is a lid of an electrolytic reaction tank, 3 is a high-speed shearing type fine-mixing device, 30 is a cylinder (made of stainless steel), 30a is a slit, 31 is a rotor (made of stainless steel), 31a Is a rotor blade, 4 is a motor, 5 is an anode (insoluble metal electrode), 6 is an ultrasonic oscillator, 7 is a thermometer, 8 is a base, and 9 is a palladium (Pd) cathode metal plate.
The solution to be treated next (however, in the case of a solid, it cannot be treated, so it is finely pulverized and made into a colloidal form) is weighed and charged into the electrolytic reaction tank 1, and 2 to 20 times as much water is added. Alkali metal hydroxide (for example, sodium hydroxide, potassium hydroxide, lithium hydroxide) 2 to 20 times the halogen element equivalent of the organic halogen compound is added and mixed, and electrolysis is performed using the high-speed shearing type miniaturization mixing device 3 as a cathode. To do.
The rotational speed of the high-speed rotary shear type refinement mixer is 1,000 to 8,000 RPM, preferably 3,000 to 5,000 RPM, and the distance between the rotor and the stator is 0.5 to 5.0 mm, preferably 1.0. ~ 2.0 mm.
Note that the rotor blades 31a and the slits 30a are not arranged in parallel, and the rotor blades 31a are slightly inclined (around 10 °) (see FIG. 3), that is, the interval S2 is also provided to be inclined non-parallel to the slits 30a. It is preferable for increasing the shearing force for miniaturization and increasing the suction force of the mixed liquid from below.
Furthermore, it is also preferable to arrange a separate stirrer in the electrolytic reaction tank 1 to improve the convective mixing of the mixed liquid in the tank.

The detailed structure of the main part of the high-speed shearing type refinement mixing apparatus 3 is as shown in FIGS. 3 (a) to 3 (c).
That is, from a stainless steel cylinder 30 having a large number of slits 30a in the vertical direction, and a rotor 31 provided with a large number of stainless steel long blade-like rotor blades 31a rotatably and radially housed inside thereof. Become.
As shown in FIGS. 3B and 3C, a large number of rotor blades 31a extend radially downward from the upper center, and each rotor blade 31a has a small width at the bottom and a large width at the top. It is a right-angled triangular plate body, and the right-angled portion is arranged close to the upper part inside the cylinder 30.
There is a gap S1 between the outer wall surface of the rotor blade 31a facing the inner wall surface of the cylinder 30, and the mixture of the organic halogen compound-containing material and the alkali metal hydroxide aqueous solution is sucked from the lower center by the rotation of the many rotor blades 31a. And introduced into the gap S1.
The mixture that has entered the gap S1 is sheared and refined by high-speed rotation of the rotor blade 31a, and halogen ions (for example, Cl ions) and alkali metal ions (for example, Na ions) in the refined product are frequently generated in the electrolyte. To form an alkali metal halide (for example, NaCl), which is dehalogenated from the organic halogen compound.
In addition, the mixture of the organic halogen compound-containing material and the alkali metal hydroxide aqueous solution sucked from the lower center of the high-speed shearing type fine mixing device 3 and introduced into the gap S1 is sheared at high speed, It is led out from the slit 30 a and mixed while generating convection in the electrolytic reaction tank 1.
At this time, if an ultrasonic wave is applied by the ultrasonic oscillator 6, the efficiency increases.

In this electrolysis, the high-speed shearing type refinement mixing apparatus 3 serves as a cathode and is characterized in that an organic halogen compound-containing material, for example, a PCB-containing oil is electrolyzed simultaneously in an alkali metal aqueous solution while being sheared and refined.
When the PCB-containing oil is applied to the high-speed shearing type micronizing / mixing device 3, the hit ratio at which the Cl of PCB contained in the liquid hits the electrode is remarkably increased, and the electrolysis efficiency is improved.
When the PCB touches or approaches the negative electrode, Cl in the PCB receives electrons to become Cl- ions and desorbs from the PCB, and the generated Cl- ions combine with Na + ions in the aqueous sodium hydroxide solution to form NaCl (salt). ) And PCB is decomposed.

In addition, it is preferable to plate palladium (Pd) on the + electrode of the high-speed shearing type micronizing / mixing device 3 because the PCB decomposition rate is improved.

The mixing ratio of PCB and water has conventionally required 500 to 1,000 times as much water as emulsion of PCB by electrolysis, but in the present invention, it does not emulsify and electrolyze PCB and water. Since the electrolysis is performed while the PCB is refined by the high-speed shearing type refinement mixing apparatus which is a cathode without using an activator, the ratio of water can be drastically reduced (2 to 20 times). Moreover, since no activator was used, oil / water separation was easy after the reaction, opening the way for industrialization.
In addition, the water after oil-water separation can be recycled for the electrolytic treatment of the next PCB.

There are various types of high-speed shearing type miniaturization mixing equipment, but it is necessary to cause an electrolytic reaction at the same time as miniaturization, so it is made of conductive material such as stainless steel, and PCB is repeatedly miniaturized mixing equipment. It is preferable that the negative electrode rotor 3 (rotating blade 31a) has a high probability of being hit.
In that respect, “Disperser”, a high-speed rotary shearing type micronizing and mixing device, was successfully used as a negative electrode. Adopted as a negative electrode.

In order to assist in miniaturization, the entrance of the high-speed shearing type micronizing / mixing device 3 as shown in FIG. 1 is usually drawn up from below, sheared / miniaturized, and discharged from the top or side. If the ultrasonic transmitter 6 is installed near (outside) the lower part of the mixing apparatus, it is effective to promote the miniaturization and activation of the PCB. The frequency is preferably 20 to 1,000 KHz. (Mixed liquid may be scattered above 1,000KHz)

Another feature of the present invention is safety. Since it is operated under normal pressure at a low temperature of 100 ° C. or less, the present invention is an electrolysis of PCB using an alkali metal hydroxide aqueous solution as an electrolyte, and does not use dangerous chemicals. Just stop responding and it is completely safe against power outages.

For the positive electrode, platinum which is an insoluble metal or an alloy thereof, platinum plating or the like is preferably used. A carbon electrode is also suitable.
The present invention applies to all organic halogen compounds. Although there are considerable harmful compounds in organic fluorine compounds, they are sufficiently treated by this method.
Organic bromine compounds can also be treated. It can also be applied to the degradation of pesticides.

Next, the present invention will be specifically described based on examples.
[Example 1]
20 L of tap water and 100 g of sodium hydroxide were added to 1 L of transformer oil containing 60% (600,000 ppm) of PCB, and electrolysis was performed at 33 ° C. and normal pressure in the electrolytic cell 1 shown in FIG.
The detailed structure of the main part of the high-speed shearing type micronizing / mixing device 3 is as shown in FIGS. 3 (a) to 3 (c), and a stainless steel cylinder 30 having a large number of slits 30a in the vertical direction; The rotor 31 includes a plurality of long blade-like rotor blades 31a that are rotatably and radially housed inside.
As shown in FIGS. 3B and 3C, a large number of rotor blades 31a extend radially downward from the upper center, and each rotor blade 31a has a small width at the bottom and a large width at the top. It is a right-angled triangular plate body, and the right-angled portion is arranged close to the upper part inside the cylinder 30.
In the figure, the cylinder 3 has an outer diameter of 60 mm, an inner diameter of 54 mm, the slit has a width of 1 mm, and a length of 7 mm, the inner rotor 31 has an outer diameter of 52 mm, and the rotor blade 31a has a thickness of 4 mm.
The gap S1 between the inner wall surface of the cylinder 30 and the outer wall surface of the rotor blade 31a is 1 mm, and the interval S2 between the rotor blade 31a and the adjacent rotor blade 31a is 3 mm.

There is a gap S1 between the outer wall surface of the rotor blades 31a facing the inner wall surface of the cylinder 30, and a mixture of PCB and aqueous sodium hydroxide solution is sucked from the lower center and introduced into the gap S1 by the rotation of a large number of rotor blades 31a. Is done.
The mixture that has entered the gap S1 is sheared and refined by high-speed rotation of the rotor blades 31a, and Cl ions and Na ions in the refined product come into contact with each other in the electrolyte at a high frequency to be combined as NaCl. And dechlorinated from the PCB.
Note that the mixture of the PCB-containing material and the aqueous sodium hydroxide solution sucked from the lower center of the high-speed shearing type fine mixing device 3 and introduced into the gap S1 is sheared at a high speed, and then the outside of the longitudinal slits 3a. And mixed while generating convection in the electrolytic reaction tank 1.

Although electrolysis was initially performed at 48V and 50A, the initial voltage with a constant current of 50A gradually decreased to 26V and 50A after 2 hours.
The rotational speed of the rotor was 5,000 RPM.

The temperature gradually increased to 88 ° C. Since the temperature rose, the electricity was turned off after 2 hours for cooling. The next day, electrolysis was resumed at a liquid temperature of 35 ° C. The initial voltage after resumption was 57V and 50A, but the voltage gradually decreased to 27V and 50A, almost the same as the previous day.
After 3 hours in total, 20 g of sodium hydroxide was additionally charged and mixed, and electrolysis was terminated after 1 hour.
As a result of analysis, the PCB concentration was reduced from 60% to 0.6% (6,000 ppm) to 1/100, and the removal rate was 99%.

[Example 2]
20 L of water and 100 g of sodium hydroxide were added to 1 L of transformer oil containing 15% of PCB (150,000 ppm), and electrolysis was initially performed at 48 V, 50 A (constant current) in the electrolytic cell of FIG. The voltage gradually dropped to 27V and 50A after 2 hours.
The temperature was 28 ° C. at the beginning, but after 2 hours it reached 90 ° C., so 30 mL of water was added twice and the reaction was completed in 3 hours and 50 minutes. As a result of analysis, PCB was 1,800 ppm, and the removal rate was 98.2%. The rotational speed of the rotor was 5,000 RPM.

[Comparative Example 1] (Conventional method 1)
The high-speed shearing type micronizing / mixing apparatus shown in FIG. 2 was used. That is, instead of the cathode, it was used as a simple high-speed shearing type miniaturization mixing apparatus, a separately prepared palladium metal plate was used as the cathode 9, and the anode 5 was electrolyzed using a platinum-plated titanium plate as in FIG.
This method is a conventional method, and the electrolysis conditions were electrolysis of a mixture of 1 L of PCB containing 1% (10,000 ppm) of transformer oil 1 L, water 20 L, and sodium hydroxide 120 g at 49 V and 50 A, but the voltage gradually decreased to 26 V. , 50A. The electrolysis time was 8 hours, which is twice that in the case of the present example. As a result of analysis, PCB was 4,700 ppm, and the removal rate was 53%.

[Comparative Example 2] (Conventional method 2)
Transformer oil 5 L containing PCB 200 ppm, water 20 L, and sodium hydroxide 80 g were set in the electrolytic cell 1, and the electrolysis conditions started at 48 V and 50 A, which were almost the same as in Comparative Example 1, but the voltage dropped to the latter half 26 V and 50 A. . As a result of analysis after 8 hours, PCB was 120 ppm, and the removal rate remained at 40%.
Compared with the results of the embodiment of the present application, the removal rate is only about 50% despite doubling the processing time, demonstrating the superiority of the present invention.

[Example 3]
Water (20 L) and sodium hydroxide (200 g) were added to 1 kg of a 60% (600,000 ppm) PCB solution obtained by adding 400 g of mineral oil to 600 g of PCB, and electrolysis was performed using the apparatus shown in FIG.
Initially, it started with a voltage of 58V and a constant current of 50A, but after 3 hours it became a voltage of 26V and a current of 50A. The temperature was initially 31 ° C. and reached 77 ° C. at the end of 4 hours.
After 4 hours, the analysis showed that PCB 600,000 ppm dropped to 7,200 ppm, resulting in a removal rate of 98.8%.

[Example 4]
Up to 20 L of water is added to 1 kg of PCB 60% (600,000 ppm) solution obtained by adding 400 g of mineral oil to 600 g of PCB, but 120 g of lithium hydroxide (LiOH) is added instead of sodium hydroxide (corresponding to 200 g of NaOH). Electrolysis was performed using the apparatus shown in FIG. The reaction was almost the same, and the voltage was initially 59 V for a constant current of 50 A, but dropped to 26 V at the end of 4 hours. The temperature started at 28 ° C and reached 80 ° C at the end.
As a result of analysis, PCB 600,000 ppm was 6,000 ppm, and the removal rate was 99%. As a result, lithium hydroxide is slightly better, but it seems to have almost the same effect as sodium hydroxide.

[Example 5]
110 g of PCB 100% (1,000,000 ppm), 20 L of water, and 200 g of sodium hydroxide were placed in the electrolytic cell of FIG. 1 and electrolyzed at a constant current of 40 A and a voltage of 40 V. Since the PCB was 100% this time, the electrolysis time was doubled to 8 hours.
At a constant current of 40A, the voltage dropped from 40V to 20V and finished. The temperature started at 26 ° C and reached 67 ° C at the end. This is probably because the temperature rise of the electrolyte was small because the current was reduced to 40A.
As a result of PCB analysis, 1,000,000 ppm was initially reduced to 4,950 ppm, resulting in a removal rate of 99.5%.

[Example 6]
Agricultural chemicals: (containing 2.4% dimethylamine (2.4.D) of 2.4 dichlorophenoxy) (500 g), 20 L of water and 200 g of sodium hydroxide were placed in the electrolytic cell shown in FIG. 1, constant current 40 A, initial voltage 42 V Was electrolyzed. Since it was the first time for agrochemicals, it was 6 hours in operation. The voltage dropped to the removal and reached 20V, 40A at the end. The temperature started at 26 ° C and ended at 65 ° C.
Results of analysis 2.4. D was 0.3% and the removal rate was 99.4%. As a result, it was proved that the present invention is effective for the decomposition of agricultural chemicals and the like.

[Example 7]
500 g of PCB, 500 g of mineral oil, 15 L of water, and 200 g of sodium hydroxide were placed in the electrolytic cell of FIG. 1 and electrolyzed at a constant current of 40 A and an initial voltage of 40V. The temperature was initially 26 ° C, but increased to 68 ° C. After 4 hours, the voltage dropped to 20 V and the electrolysis process was completed. As a result of the analysis, it was 8,500 ppm, and the removal rate was 98.3%.
In this example, since the constant current was suppressed to 40 A, the removal rate was somewhat low, but the temperature rise could be avoided.

[Example 8]
PCB 500 g mineral oil 500 g, water 19 L, potassium hydroxide (KOH) 250 g were put in the electrolytic cell of FIG. 1 and were carried out at a constant current of 50 A and a voltage of 50 V (first), but gradually decreased to 20 V. The temperature was initially 26 ° C. and 72 ° C. at the end. As a result of the 4-hour post-reaction analysis, the initial PCB concentration of 500,000 ppm became 6,000 ppm after 4 hours, and the removal rate was 98.8%.
In this example, KOH is used instead of NaOH. As a result, it was demonstrated that any of NaOH, LiOH, and KOH can be applied to the present invention.

[Example 9]
The low-concentration PCB treatment is in a form where the PCB is hidden in the raw material oil, and the hit rate hitting the cathode is extremely reduced, which is a game with time. In the apparatus of FIG. 1 g and 1,000 g of mineral oil were added (PCB 100 ppm), 20 L of water and 150 g of sodium hydroxide were further added, and electrolysis was performed at a constant current of 50 A and a voltage of 50 V initially. The voltage gradually decreased from 50V to 30V. When the electrolysis time was analyzed after 10 hours of treatment, the analytical value was 0.8 ppm, which is one step closer to the Japanese standard values of 0 and 5 ppm.
Therefore, the remaining liquid of Example 9 was further treated for 2 hours under the same conditions for a total of 12 hours. The result was set to [Example 9 ′], and the result of analysis was 0.4 ppm (removal rate 99.6%), and the reference value of 0.5 ppm or less could be cleared.

Table 1 shows a summary of the nine examples and the two conventional examples.
Comparing the method of the present invention with the conventional method, the conventional method has a removal rate of about 50% over 8 hours. However, according to the method of the present invention, 98% of the high concentration PCB treatment is 98%. ~ 99% treatment was possible.
In particular, in the high-speed shearing type refinement mixing device 3, the oil containing PCB or the like is sheared and refined between the gaps S1 while repeatedly hitting the rotor blades 31a. The hit rate of the inclusion hitting the cathode is significantly improved.
Moreover, in this-invention Example, it is 2.4. Although D was treated, it can be applied to all decomposition removal of organic halogen compounds.

1: Electrolytic reaction tank 2: Electrolytic reaction tank lid 3: High-speed shearing type micronization mixing device 4: Motor 5: Insoluble anode 6: Ultrasonic generator 7: Thermometer 8: Pedestal 9: Pd cathode metal plate 30 : Cylinder 30a: slit 31; rotor 31a; rotor blade S1: gap between the inner wall surface of the cylinder 30 and the outer wall surface of the rotor blade 31a S2: distance between the rotor blade 31a and the adjacent rotor blade 31a

Claims (10)

In the electrolytic reaction tank, the organohalogen compound-containing liquid and the alkali metal hydroxide aqueous solution are added and mixed, and a conductive high-speed shearing type miniaturization mixing device such as a disperser or homogenizer is immersed in the mixed liquid. An organic halogen compound characterized in that a positive electrode is disposed around the same fine-mixing device, the high-speed shearing type fine-mixing device is used as a cathode, and the positive electrode is used as an anode for electrolysis and electrolysis. Disassembly method. 2. The organic halogen compound is one or more selected from organic fluorine compounds, organic chlorine compounds, organic bromine compounds, VOCs, PCBs, dioxins, and organic chlorine-based pesticides. Of decomposition of organic halogen compounds. 3. The organic halogen compound according to claim 1, wherein the alkali metal hydroxide aqueous solution is one or more selected from a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, and a lithium hydroxide aqueous solution. Disassembly method. The high-speed shearing type micronizing / mixing device used as a cathode is a conductive high-speed shearing type micronizing / mixing device such as a disperser, a homogenizer, a homomixer, a line mixer, or an emulsion generator. The decomposition | disassembly method of the organic halogen compound of any one of these. 5. The positive electrode according to claim 1, wherein the positive electrode is a white metal such as platinum, iridium, or osmium which is an insoluble metal, or an alloy thereof, a plated product thereof, or carbon. Of decomposition of organic halogen compounds. The method for decomposing an organic halogen compound according to any one of claims 1 to 5, wherein the electrolytic reaction is carried out while applying ultrasonic vibration in the electrolytic reaction tank. Electrolytic reaction tank into which an organohalogen compound-containing liquid and an alkali metal hydroxide aqueous solution are charged, a conductive high-speed shearing type refining and mixing device such as a disperser, a line mixer, a homogenizer, and the like An organic halogen compound decomposition apparatus comprising: a positive electrode disposed in the periphery of a chemical mixing device; and a power supply device that is energized with the fine mixing device as a cathode and the positive electrode as an anode. The high-speed shearing type micronizing / mixing device used as a cathode is a conductive high-speed shearing type micronizing / mixing device such as a disperser, a homogenizer, a homomixer, a line mixer, or an emulsion generator. Organic halogen compound decomposition equipment. The positive electrode is a white metal such as platinum, iridium, or osmium, which is an insoluble metal, or an alloy thereof, or a plated product thereof or carbon. Disassembly equipment. The organic halogen compound decomposition apparatus according to any one of claims 7 to 9, wherein an ultrasonic oscillator is attached to the electrolytic reaction tank.

Images