JP2002165898A - Decomposition treatment equipment for organic halogen compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide decomposition treatment equipment for organic halogen compounds which is capable of suppressing the degradation in treatment ability when a large amount of the organic halogen compounds are treated. SOLUTION: The organic halogen compounds and a decomposition treating agent of the following (a) or (b) are continuously introduced into a reaction section 13 and are continuously discharged outside after making reaction by coming into contact with each other in the reaction section 13. The atmosphere temperature of the reaction section 13 is so set as to be higher in the upper part than in the lower part by external heaters 17a and 17b or an internal heater 18. The decomposition treating agent is preferably preheated by a preheater 19 and is then introduced into the reaction section 13. (a) The decomposition treating agent which contains >=50 wt.% magnesium oxide. (b) The decomposition treating agent which contains the magnesium oxide anti the calcium oxide and in which the content in total thereof is >=50 wt.% and [calcium oxide/(magnesium oxide + calcium oxide)] (molar ratio) is <=0.67.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic halogen compound decomposing apparatus for decomposing organic halogen compounds such as fluorocarbons, halons and sulfur hexafluoride.

[0002]

2. Description of the Related Art Organic halogen compounds are widely used in industry, and some of them have been pointed out as having serious effects on the global environment and have been regarded as problematic. For example, fluorocarbons, halons, and sulfur hexafluoride exhibit a high global warming potential and are known to cause global warming as a greenhouse gas. Fluorocarbons and halons are also known as ozone depleting substances. Therefore, there is an urgent need to develop a technique for decomposing used organic halogen compounds in parallel with restricting the use and production of these organic halogen compounds.

[0003] The inventors of the present invention disclose patent 27958.
No. 37 and Japanese Patent Application Laid-Open No. 10-225618 propose an apparatus for decomposing organic halogen compounds. This decomposition treatment apparatus utilizes a vertical lime calcination furnace, and can introduce an organic halogen compound into the furnace from an introduction portion, and a decomposition treatment agent made of limestone or dolomite is arranged in the furnace. It has become. Then, the organic halogen compound can be decomposed by contacting the decomposition agent with the organic halogen compound at a temperature of 800 to 1400 ° C. in a furnace.

[0004]

However, in the case of the above-mentioned disassembly processing apparatus, there is a possibility that the processing capacity is greatly reduced when the processing amount becomes large. This significant reduction in throughput is caused by the following reasons.

When a decomposition treatment agent made of limestone is used in the above decomposition treatment apparatus, when the decomposition treatment agent and the organic halogen compound come into contact with each other at a high temperature, calcium oxide and organic halogen compound generated when the limestone is heated are heated. Reacts with to produce calcium halide. This calcium halide has a relatively low melting point, and can be melted at a furnace temperature (800 to 1400 ° C.) during the decomposition treatment of the organic halogen compound. If the decomposing agent is aggregated by the melted calcium halide, the decomposing agent cannot perform its function sufficiently, and the processing capacity of the decomposing device decreases. While the amount of treatment is small, there is no particular problem because the amount of generated calcium halide is small,
When the processing amount increases, the amount of generated calcium halide also increases, and the decomposition treatment agent tends to be agglomerated. For this reason, when the processing amount is large, the processing capacity is significantly reduced. By the way, the organic halogen compound is Freon 12
In the case of the above, it has been confirmed that when about 0.1 nmol of Freon 12 reacts with nmol of calcium oxide, the decomposition treatment agent becomes lumpy. When the decomposition treatment agent is made of dolomite, not only calcium oxide but also magnesium oxide is simultaneously generated by heating. Magnesium halide produced by the reaction between magnesium oxide and an organic halogen compound also has a relatively low melting point like the above-mentioned calcium halide, and may cause agglomeration of the decomposition treatment agent.

The present invention has been made by focusing on the problems existing in the prior art as described above. An object of the present invention is to provide an organic halogen compound decomposition treatment apparatus capable of suppressing a decrease in processing capacity when treating a large amount of an organic halogen compound.

[0007]

In order to achieve the above object, the invention according to claim 1 comprises a reaction section in which an organic halogen compound reacts with a decomposition agent, and the reaction section has an organic compound. A halogen compound and a decomposition treatment agent are continuously introduced, and an organic halogen compound decomposition treatment apparatus configured to continuously discharge the organic halogen compound and the decomposition treatment agent after the reaction from the reaction unit, An apparatus for decomposing an organic halogen compound, wherein the decomposition agent is the following (a) or (b). (A) A decomposition treating agent containing 50% by weight or more of magnesium oxide. (B) containing magnesium oxide and calcium oxide,
Its content is 50% by weight or more in total,
The point is that [calcium oxide / (magnesium oxide + calcium oxide)] (molar ratio) is 0.67 or less.

According to a second aspect of the present invention, in the apparatus for decomposing an organic halogen compound according to the first aspect, the temperature of the atmosphere in the reaction section is higher on the upstream side than on the downstream side of the decomposition agent. Is set to be higher.

According to a third aspect of the present invention, there is provided the apparatus for decomposing an organic halogen compound according to the first or second aspect, further comprising a preheating means for preheating the decomposing agent, and the decomposition preheated by the preheating means. The gist is that the treatment agent is introduced into the reaction section.

[0010]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS (First Embodiment) Hereinafter, a first embodiment of the present invention will be described in detail with reference to the drawings.

FIG. 1 is a diagram showing an apparatus for decomposing an organic halogen compound in this embodiment. The decomposition treatment apparatus 11 shown in FIG. 1 includes a first storage chamber 12 for storing a decomposition treatment agent, a reaction section 13 where a reaction between the organic halogen compound and the decomposition treatment agent takes place, And a second storage chamber 14 for collecting and storing the decomposition treatment agent.

The first storage chamber 12 and the second storage chamber 14 are vertically arranged side by side and connected by a conduit 15. An intermediate portion of the conduit 15 is covered by a housing 16, and the reaction portion 13 is constituted by a portion of the conduit 15 covered by the housing 16. And the decomposition treatment agent,
From the first storage room 12 to the second storage room 1 via the reaction unit 13
4 is continuously transferred.

Inside the housing 16, a pair of upper and lower external heaters 17a, 1a for heating the inside of the conduit 15 from the outside is provided.
7b is provided. In addition, an internal heater 18 that heats the inside of the conduit 15 from the inside is disposed in an upper portion of the conduit 15. Furthermore, the first storage chamber 12 has
A preheater 19 is provided as a preheating means for heating the decomposition treatment agent in the storage chamber 12 of the first embodiment.

In the second storage chamber 14, a gas supply pipe 20 is provided.
Is connected. The gas supply pipe 20 is branched into two on the upstream side, and one end is connected to a supply section 21 for an organic halogen compound, and the other end is connected to a supply section 22 for a carrier gas. Then, the organic halogen compound is continuously introduced into the second storage chamber 14 via the gas supply pipe 20 as a mixed gas with the carrier gas, and is transferred to the first storage chamber 12 via the reaction unit 13. It has become. A gas discharge pipe 23 is connected to the first storage chamber 12, and the exhaust gas transferred to the first storage chamber 12 via the reaction unit 13 is continuously discharged to the outside via the gas discharge pipe 23. It has become.

The decomposition treatment apparatus 11 is provided with a control unit 24, which controls the speed at which the organic halogen compound and the decomposition treatment agent are introduced into the reaction unit 13 and the speed at which the organic halogen compound and the decomposition treatment agent are discharged from the reaction unit 13. In addition, the temperatures of the upper and lower outer heaters 17a and 17b, the inner heater 18, and the preheater 19 are controlled independently.

Examples of the organic halogen compound include fluorocarbons, halons, and sulfur hexafluoride.
As the fluorocarbons, fluorocarbons 11, 12, 113, 11
4,115 specific CFCs and other CF
Halons such as C, HCFC, HFC, and PFC include Halon 1211, 1301, and 4022, as well as other BCFCs, BFCs, and HBFCs. These organic halogen compounds may be used alone or in combination of two or more. The concentration of the organic halogen compound in the mixed gas introduced into the second storage chamber 14 is 10 v
ol% or more is preferable, and 30 vol% or more is more preferable. If the concentration is less than 10 vol%, the processing efficiency is undesirably reduced.

Next, the decomposition treatment agent used in the decomposition treatment apparatus 11 will be described. In the present embodiment, magnesium oxide is contained in an amount of 50% by weight or more, preferably 7% by weight or more.
A decomposition treatment agent containing 5% by weight or more is used. If the content of magnesium oxide is less than 50% by weight, the amount of the decomposition treatment per unit weight of the decomposition treatment agent becomes small, which is not suitable.

The components other than magnesium oxide contained in the decomposition agent are not particularly limited, and may be, for example, clay minerals, silica, shirasu, volcanic ash, coal ash, diatomaceous earth, glass powder, slag, and the like.

The shape of the decomposition treatment agent is preferably granular from the viewpoint of air permeability and contact efficiency. The particle size is not particularly limited, but is preferably 1 to 8 mm, and 2 to 5 mm
Is more preferred. If the particle size is less than 1 mm, the pressure loss becomes too large, which is not preferable.

This decomposing agent is manufactured as follows. First, water is added to a powdery composition containing at least one of magnesium oxide and a compound that produces magnesium oxide by firing, and then using a mixing device such as a ball mill, a kneader, a crusher, a muller, and a wet stirrer. Mix. Extrusion granulator, bread granulator,
The desired decomposition treatment agent can be obtained by granulating using a granulating device such as a stirring granulator or a tableting machine. However, when a compound that generates magnesium oxide upon firing is contained in the composition, it is necessary to fire somewhere in the process or at the time of use. In addition, the method of mixing and granulation is not limited to the method using each apparatus mentioned above.

Examples of the compound which forms magnesium oxide upon firing include magnesium hydroxide, magnesium carbonate, basic magnesium carbonate, magnesium acetate, magnesium nitrate, and the like. These may be used alone or in combination of two or more. You may.

When a compound that produces magnesium oxide upon firing is contained in the composition, the firing temperature is 1200.
It is preferred that the temperature be lower than ° C. If the temperature is 1200 ° C. or higher, magnesium oxide having low reactivity with the organic halogen compound and its decomposition product is generated, which is not preferable.

The following method is also possible as a method for producing the decomposition treatment agent. That is, a decomposition treatment agent may be formed by crushing a granular composition containing at least one of magnesium oxide and a compound that generates magnesium oxide upon firing to obtain a granular composition. However, when a compound that generates magnesium oxide upon firing is contained in the composition, it is necessary to fire somewhere in the process or at the time of use.

Next, the operation of the disassembly processing apparatus 11 configured as described above will be described. When the organic halogen compound is decomposed by the decomposition apparatus 11, first, the heating unit such as the external heaters 17a and 17b is operated to heat the reaction unit 13, and in this state, the mixed gas containing the organic halogen compound and The introduction of the decomposition treatment agent into the reaction section 13 is started.

At this time, the ambient temperature of the reaction section 13 is 80
0-1400 degreeC is preferable. If the temperature is lower than 800 ° C., the processing capacity decreases. On the other hand, if the temperature exceeds 1400 ° C., the reactivity of magnesium oxide with an organic halogen compound decreases, which is not preferable.

More preferably, the atmosphere temperature of the reaction section 13 is different between the upper portion, which is the upstream side of the decomposition treatment agent, and the lower portion, which is the downstream side, and it is desirable that the upper portion has a higher temperature than the lower portion. This temperature gradient is caused by the upper and lower external heaters 17.
Achieved mainly by adjusting the temperature of a, 17b or by activating the internal heater 18.

In the following, the chemicals which proceed when Freon 12 (CCl ₂ F ₂ ), Halon 1301 (CF ₃ Br) and sulfur hexafluoride (SF ₆ ) come into contact with the above-mentioned decomposition treatment agent in the reaction section 13 respectively. The reaction equation is shown below. (A) CCl ₂ F ₂ + 2MgO → aMgCl ₂ + aMgF ₂ + (2-2
a) MgClF + CO ₂ (where 0 <a <1) (B) CF ₃ Br + 2MgO → aMgF ₂ + (a-1) MgBr ₂ +
(3-2a) MgBrF + CO ₂ (where 1 <a <3/2) (C) SF ₆ + 4MgO → 3MgF ₂ + MgSO _{4 Since} these reactions occur under the catalytic action of magnesium oxide, water, methane, etc. Does not require a hydrogen source.

The melting points of magnesium chloride, magnesium fluoride and magnesium bromide produced by the above-mentioned reactions (A) to (C) are 714 ° C., 1248 ° C. and 711 ° C., respectively.
° C. These usually melt at a temperature of 800 to 1400 ° C., but no melting was observed in the present embodiment. Therefore, the decomposition treatment agent can maintain a granular shape without being aggregated, and can continue the reaction with the organic halogen compound. Therefore, the magnesium oxide in the decomposition treatment agent can react (quantitatively) with the organic halogen compound in substantially the same amount. That is, when 2 nmol of magnesium oxide is contained in the decomposing agent, about n mol of Freon 12 can be decomposed by this decomposing agent. In the case of nmol and sulfur hexafluoride, about 0.5 nmol can be decomposed.

The reason why the decomposition treatment agent does not form a lump is considered to be that a part of magnesium chloride returns to magnesium oxide according to the following formula [Nikka Kagaku, 74 , 46 (1)
971)]. Magnesium fluoride and bromide are expected to return to magnesium oxide in the same manner.

[0030]

Embedded image According to the embodiment described in detail above, the following effects are exhibited.

By using a decomposition treatment agent containing 50% by weight or more of magnesium oxide, the decomposition treatment agent can be prevented from agglomerating, and its function can be exerted continuously. That is, it is possible to suppress a decrease in processing capacity when a large amount of an organic halogen compound is treated,
The organic halogen compound can be efficiently and almost quantitatively decomposed. Further, by setting the content of magnesium oxide to 75% by weight or more, the above effect can be further improved.

The decomposing agent is continuously introduced into the reaction section 13 and is continuously discharged after coming into contact with the organic halogen compound. Therefore, even if the decomposing agent does not continuously exhibit its decomposing ability. Even so, there is no possibility that the processing capacity of the decomposition processing apparatus 11 itself is reduced.

An upper portion, which is upstream of the decomposition agent,
By setting the temperature of the atmosphere in the reaction section 13 different from that of the lower portion on the downstream side, and by setting the temperature of the upper portion to be higher than that of the lower portion, generation of by-products can be suppressed. For example, the amount of Freon 116 by-produced during the decomposition treatment of Halon 1301 can be suppressed.

A pair of upper and lower external heaters 17a, 17b
Can be controlled independently by the control unit 24, so that by adjusting the temperature settings of both heaters 17a and 17b, the ambient temperature in the upper part of the reaction unit 13 can be easily set higher than that in the lower part. .

Since the internal heater 18 is disposed in the upper portion of the conduit 15, the ambient temperature of the upper portion of the reaction section 13 can be easily set higher than that of the lower portion by operating the internal heater 18. it can.

By providing the preheater 19,
Since the decomposition treatment agent heated in advance can be introduced into the reaction section 13, it is easier to set the ambient temperature at the upper portion of the reaction section 13 higher than at the lower portion.

The decomposing agent absorbs the acid gas by-produced by the decomposition of the organic halogen compound immediately at the same time as the decomposition, so that no acid gas is substantially generated during the decomposition treatment of the organic halogen compound. Therefore, there is no possibility that the reaction section 13 is corroded by the acid gas. Therefore, the reaction section 13 can be made of not only alumina, quartz, ceramic, and the like having excellent durability and heat resistance to an acid gas, but also an iron-based alloy such as Hastelloy or Inconel.

Since the organic halogen compound and the decomposition treating agent come into contact with each other in the reaction section 13 in countercurrent, the two can be uniformly reacted, and the processing efficiency of the organic halogen compound can be improved.

The ambient temperature of the reaction section 13 is set to 800 to 1
By setting the temperature to 400 ° C., it is possible to suppress a decrease in the reactivity between the organic halogen compound and magnesium oxide, and to improve the decomposition treatment ability.

(Second Embodiment) Next, a second embodiment of the present invention will be described focusing on differences from the first embodiment.

In the present embodiment, a decomposition agent containing magnesium oxide and calcium oxide is used. The total amount of magnesium oxide and calcium oxide contained in the decomposition treatment agent is 50% by weight or more, preferably 7% by weight.
5% by weight or more. If the content is less than 50% by weight, the amount of decomposition treatment per unit weight of the decomposition treatment agent becomes small, which is not suitable.

The magnesium oxide and the calcium oxide contained in the decomposition treatment agent have a molar ratio of [calcium oxide / (magnesium oxide + calcium oxide)] of 0.6.
7 or less. When this value exceeds 0.67, the decomposition treatment agent is melted into a lump when it is brought into contact with an organic halogen compound at a temperature of 800 to 1400 ° C., and the decomposition treatment performance is reduced.

The components other than magnesium oxide and calcium oxide contained in the decomposition treatment agent are not particularly limited, and may be, for example, clay mineral, silica, shirasu, volcanic ash, or the like as in the case of the decomposition treatment agent in the first embodiment. Coal ash, diatomaceous earth, glass powder, slag and the like may be used.

This decomposing agent comprises a composition containing at least one of magnesium oxide and a compound that forms magnesium oxide when calcined, and a composition containing calcium oxide and at least one compound that forms calcium oxide when calcined. It is manufactured using. In the case of a powdery composition, it is prepared by adding water, mixing and granulating in the same manner as in the case of the decomposition treatment agent in the first embodiment. In the case of a lump-shaped composition, it is prepared by crushing into a granular form. However, when a compound that generates magnesium oxide or calcium oxide upon firing is contained in the composition, firing must be performed somewhere in the process or at the time of use.

As the compound that produces magnesium oxide upon firing, the same compounds as those described in the first embodiment are used. Compounds that generate calcium oxide upon firing include calcium hydroxide,
Calcium carbonate, calcium acetate and the like can be mentioned. These may be used alone or in combination of two or more.

The following is a reaction formula of a chemical reaction that proceeds when Freon 12, Halon 1301 and sulfur hexafluoride come into contact with the above-mentioned decomposition treating agent in the reaction section 13, respectively. In the following reaction formula, M represents Mg or Ca. (D) CCl ₂ F ₂ + 2MO → aMCl ₂ + aMF ₂ + (2-2a) MClF + CO ₂ (where 0 <a <1) (E) CF ₃ Br + 2MO → aMF ₂ + (a-1) MBr ₂ + (3- 2a) MBrF + CO ₂ (where 1 <a <3/2) (F) SF ₆ + 4MO → 3MF ₂ + MSO _{4 Since} these reactions occur under the catalytic action of magnesium oxide and calcium oxide, water, methane, etc. Does not require a hydrogen source.

The melting points of calcium chloride, calcium fluoride and calcium bromide produced by the above-mentioned reactions (D) to (F) are 772 ° C., 1403 ° C. and 730 ° C., respectively. It is known that when these coexist with calcium oxide, they melt even at a temperature below the melting point. For example, calcium chloride is 700 when coexisting with calcium oxide.
It has been confirmed that it melts even at ℃. For this reason, 8
When an organic halogen compound is brought into contact with a decomposition treatment agent at a temperature of 00 to 1400 ° C., it is expected that the decomposition treatment agent will be aggregated due to these molten compounds. In particular, when a predetermined amount or more of the organic halogen compound is reacted, for example, about 0.1 n
This agglomeration is considered to be significant when more than one mole of Freon 12 is reacted.

However, the amount of magnesium oxide and calcium oxide contained in the decomposition treatment agent was changed to [calcium oxide /
(Magnesium oxide + calcium oxide)] is set to be equal to or less than 0.67 in molar ratio, whereby the decomposition treatment agent can be prevented from being aggregated due to melting. Therefore, magnesium oxide and calcium oxide in the decomposition treatment agent can react (quantitatively) with the organic halogen compound in substantially the same amount. That is, when 2 nmol in total of magnesium oxide and calcium oxide is contained in the decomposition agent, about nmol of Freon 12 can be decomposed by this decomposition agent, and similarly, halon 13
In the case of 01, about nmol can be decomposed, and in the case of sulfur hexafluoride, about 0.5 nmol can be decomposed.

According to the above-described embodiment, the following effects can be obtained. The amount of decomposition treatment per unit weight of the decomposition treatment agent can be improved by adjusting the total amount of magnesium oxide and calcium oxide contained in the decomposition treatment agent to 50% by weight or more. Further, by setting the content to 75% by weight or more, the decomposition treatment amount per unit weight of the decomposition treatment agent can be further improved.

The magnesium oxide and the calcium oxide contained in the decomposition agent have a value of [calcium oxide / (magnesium oxide + calcium oxide)] of 0.6 in molar ratio.
7 or less. For this reason, 800-1
When brought into contact with an organic halogen compound at a temperature of 400 ° C., it is possible to prevent the decomposition treatment agent from being aggregated due to melting, and to exhibit its function continuously. Therefore, the organic halogen compound can be almost quantitatively decomposed.

(Third Embodiment) Next, a third embodiment of the present invention will be described focusing on differences from the second embodiment.

In the present embodiment, a decomposition agent is produced using dolomite which generates magnesium oxide and calcium oxide by firing. In particular, a decomposition treatment agent formed by calcining a lumpy composition containing dolomite and crushing it into granules is preferable because it can be produced at low cost.

Dolomite is a complex carbonate represented by Mg _(1-x) Ca _x CO ₃ (where 0 <x <1), and mainly contains magnesium oxide and calcium oxide obtained by calcining dolomite. What is called light dolomite. When dolomite is heated to about 800 ° C., magnesium carbonate is thermally decomposed to produce magnesium oxide, and when heated to about 900 ° C., calcium carbonate is thermally decomposed to produce calcium oxide.

The firing temperature for firing the composition containing dolomite is preferably from 900 to 1200 ° C. If the calcination temperature is lower than 900 ° C., thermal decomposition of calcium carbonate in the dolomite does not sufficiently occur, and if it exceeds 1200 ° C., magnesium oxide having low reactivity with the organic halogen compound and its decomposition product is generated. Therefore, it is not preferable.

[0055]

Next, the embodiment will be described more specifically with reference to examples. (Example 1) In Example 1, the decomposition apparatus 11 was used under the following conditions.

(1. Temperature Setting of Heating Device) The temperature of the upper external heater 17a is set to 1200 ° C., and the temperature of the lower external heater 17a is set to 1200 ° C.
The temperature of b was set to 600 ° C., and the internal heater 18 and the preheater 19 were not used. At this time, the atmosphere temperature in the upper part of the reaction part 13 was 800 ° C., and the atmosphere temperature in the lower part of the reaction part 13 was 700 ° C.

(2. Decomposition agent) Lightly calcined dolomite prepared to a particle size of 2 to 4 mm [manufactured by Ueda Lime Mfg. Co., Ltd., calcination temperature 1000 ° C., CaO content 63.0% by weight, MgO
31.5% by weight] was used as a decomposition treatment agent.
The introduction rate of the decomposition treatment agent was 15 kg / hour.

(3. Organic halogen compound) Halon 130
A mixed gas of 1 and air was used. The introduction rate of Halon 1301 was 25 l / min, and the introduction rate of air was 25 l / min.

(4. Measurement of Undecomposed Organic Halogen Compounds and By-products) The exhaust gas discharged to the outside from the gas discharge pipe 23 was treated with a 0.5N sodium hydroxide aqueous solution (absorbent) 2.
After passing through 00 ml, the concentration of undecomposed halon 1301 contained in the exhaust gas was measured.
It was 1 ppm (99.9998% in terms of decomposition rate). The concentration of Freon 116, a by-product, is 5.3.
ppm. On the other hand, when the fluorine content and the bromine content in the absorbing solution were measured, none was detected.

The concentration of halon 1301 in the exhaust gas is as follows:
It was measured by gas chromatography. The measurement conditions are shown below. Apparatus: Model 263-70 manufactured by Hitachi, column packing material: 1 m Chromosolve 102, column temperature: 50 ° C.
N ₂ flow rate: 40 ml / min, inlet temperature: 180 ° C., detector temperature: 200 ° C., detector: ECD.

The concentration of Freon 116 was also measured by gas chromatography. The measurement conditions are shown below. apparatus:
Model 15A, Shimadzu Corporation, column filler: 2 m Polapack Q, column temperature: 70 ° C., N ₂ flow rate: 30 ml / min,
Inlet temperature: 200 ° C, detector temperature: 250 ° C, detector: FID.

The fluorine content and the bromine content in the absorbing solution were measured by ion chromatography after 100 ml of the absorbing solution was steam-distilled and the volume was increased to 250 ml. The measurement conditions are shown below. Equipment: DX- manufactured by Nippon Dionex
100, column: AS4A-SC, eluent: 1.8 mM
Na ₂ CO ₃ /1.7 mM NaHCO ₃ , pump flow rate:
1.5 ml / min.

(Embodiment 2) In Embodiment 1, an internal heater 18 is used in addition to the external heaters 17a and 17b. Otherwise, the same operation as in Example 1 was performed to decompose Halon 1301. At this time, the temperature of the atmosphere above the reaction section 13 was 870 ° C.
The lower ambient temperature was 780 ° C.

The concentration of halon 1301 contained in the exhaust gas is 0.21 ppm (99.99999 in terms of decomposition rate).
% Or more), and the concentration of Freon 116 was 1.8 ppm. On the other hand, fluorine and bromine were not detected in the absorbing solution.

(Embodiment 3) In Embodiment 1, the internal heater 18 and the pre-heater 19 are used in addition to the external heaters 17a and 17b. Otherwise, the same operation as in Example 1 was performed to decompose Halon 1301. At this time, the atmosphere temperature above the reaction section 13 is 9
The temperature of the atmosphere at the lower portion of the reaction section 13 was 800 ° C.

The concentration of halon 1301 contained in the exhaust gas is 0.05 ppm (99.9999 in terms of decomposition rate).
% Or more), and the concentration of Freon 116 was 1.0 ppm. On the other hand, fluorine and bromine were not detected in the absorbing solution.

Embodiment 4 (1. Setting of Temperature of Heating Apparatus) In Embodiment 1, the internal heater 18 was changed to use both the external heaters 17a and 17b. At this time, the atmosphere temperature in the upper part of the reaction part 13 was 870 ° C., and the atmosphere temperature in the lower part of the reaction part 13 was 7
80 ° C.

(2. Decomposition agent) Magnesium hydroxide 2
Add 100 liters of water to 00 kg, mix and mix with a disk pelleter (F-5 type, manufactured by Fuji Paudal Company) with a diameter of 3 mm.
And then dried at 110 ° C. for 5 hours to obtain a cylindrical molded product having a diameter of 3 mm. Then, the formed body was fired at 1000 ° C. for 1 hour and further sieved to prepare 121 kg of a decomposition treatment agent having a particle size of 2 to 4 mm.

(3. Organic Halogen Compound) A mixed gas of sulfur hexafluoride and air was used. The introduction rate of sulfur hexafluoride was 12.8 l / min, and the introduction rate of air was 12.8 l / min.

(4. Measurement of undecomposed organic halogen compound)
The concentration of undecomposed sulfur hexafluoride contained in the exhaust gas is 0.1.
It was 02 ppm (at least 99.9999% in terms of decomposition rate). On the other hand, no fluorine was detected in the absorbing solution.

Incidentally, the concentration of sulfur hexafluoride in the exhaust gas was measured by gas chromatography. The measurement conditions are shown below. Equipment: Hitachi 263-70, column: 3m
Polapack Q, column temperature: 50 ° C., N ₂ flow rate: 40
ml / min, inlet temperature: 180 ° C, detector temperature: 200
° C, detector: ECD.

(Embodiment 5) (1. Temperature setting of heating device) In Embodiment 1, the internal heater 18 was used in addition to the external heaters 17a and 17b. At this time, the temperature of the atmosphere above the reaction section 13 was 870 ° C., and the temperature of the atmosphere below the reaction section 13 was 7 ° C.
80 ° C.

(2. Decomposition agent) Calcium hydroxide 56
110 liters of water was added to and mixed with 80.6 kg of magnesium hydroxide and 80.6 kg of magnesium hydroxide, and molded, dried and calcined in the same manner as in Example 4 to prepare 86 kg of a decomposition treating agent.

(3. Organic halogen compound) Halon 240
A mixed gas of 2 and air was used. Halon 2402 is heated and vaporized for use, and the introduction rate of Halon 2402 is 0.1
93 kg / min, and the air introduction speed was 40 l / min.

(4. Measurement of undecomposed organic halogen compound and measurement of by-products) Undecomposed halon 2 contained in exhaust gas
The concentration of 402 was 0.03 ppm (9 in terms of decomposition rate).
9.9999%), the concentration of Freon 116 is 1.5p
pm. On the other hand, fluorine and bromine were not detected in the absorbing solution.

The concentration of Halon 2402 in the exhaust gas is as follows:
It was measured by gas chromatography. The measurement conditions are shown below. Equipment: Hitachi 263-70 type, column: 1
Chromosolve 102, column temperature: 120 ° C., N ₂
Flow rate: 50 ml / min, inlet temperature: 180 ° C, detector temperature: 200 ° C, detector: ECD.

(Example 6) In Example 3, the organic halogen compound was changed to Freon 134a. In addition, the introduction speed of Freon 134a was set at 24.9 liter / min, and the introduction speed of air was set at 24.9 liter / min. Otherwise, the procedure was the same as in Example 3.

The undecomposed Freon 134 contained in the exhaust gas
The concentration of a was 0.15 ppm (99.
9999% or more). On the other hand, no fluorine was detected in the absorbing solution.

The concentration of Freon 134a in the exhaust gas is as follows:
It was measured by gas chromatography. The measurement conditions are shown below. Equipment: Shimadzu Corporation Model 15A, Column: 2
Polapack Q, column temperature: 120 ° C., N ₂ flow rate:
30 ml / min, inlet temperature: 200 ° C, detector temperature: 2
00 ° C, detector: FID.

Next, the technical ideas that can be grasped from the above embodiment will be described below. -The organic halogen compound and the decomposition treatment agent are contacted in a countercurrent in the reaction section.
The apparatus for decomposing an organic halogen compound according to any one of the above. With such a configuration, the organic halogen compound and the decomposition treating agent are uniformly contacted, so that the processing efficiency of the organic halogen compound can be improved.

The ambient temperature of the reaction section is 800 to 140
The apparatus for decomposing an organic halogen compound according to any one of claims 1 to 3, wherein the apparatus is set to 0 ° C. With such a configuration, it is possible to suppress a decrease in the reactivity between the organic halogen compound and magnesium oxide, and to improve the decomposition treatment ability.

[0082]

Since the present invention is configured as described above, it has the following effects. According to the first aspect of the present invention, it is possible to suppress a decrease in processing capacity when a large amount of an organic halogen compound is treated.

According to the invention described in claim 2, according to claim 1
In addition to the effects of the invention described in (1), the generation of by-products such as Freon 116 can be suppressed. According to the third aspect of the invention, in addition to the effects of the first or second aspect, the reaction is performed such that the temperature of the decomposition treatment agent on the upstream side is higher than the temperature on the downstream side. It is possible to easily set the ambient temperature of the section.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an apparatus for decomposing an organic halogen compound.

[Explanation of symbols]

Reference numeral 11 denotes an organic halogen compound decomposition treatment apparatus, 13 denotes a reaction section, and 19 denotes a preheating heater as preheating means.

Continuation of the front page (71) Applicant 391016842 Gifu Prefecture 2-1-1, Yabuta-minami, Gifu-shi, Gifu (74) One agent above 100068755 Patent Attorney Hironori Onda (72) Inventor Yoshimasa Akatsuka Midori, Nagoya-shi, Aichi Chubu Electric Power Co., Inc. (72) Inventor Akihiro Takeuchi 20-1 Kitakanyama, Odaka-cho, Midori-ku, Nagoya City, Aichi Prefecture Chubu Electric Power Co., Inc. Inside the Technical Research Institute (72) Inventor Hiroshi Tsunoda 673-1, Kurihara, Tarui-cho, Fuwa-gun, Gifu Prefecture 4232 Ueda Lime-Machi, Inc. (72) Inventor Tatsuo Murakami 4232 Akasaka-cho, Ogaki-shi, Gifu Prefecture Incorporated (72) Inventor Shigeru Aito 4232 Akasaka-cho, Ogaki-shi, Gifu Ueda-Lime Manufacturing Co., Ltd. F-term (reference) 2E191 BA01 BA12 BB00 BC01 BD12 BD13 4G075 AA03 AA37 AA62 A A63 BA05 BA06 BD14 BD23 CA02 CA54 CA57 CA66 DA02 DA18 EA01 EA07 EB01 4H006 AA02 AC13 AC26 BA06 BA30

Claims (3)

[Claims] 1. A reaction section for reacting an organic halogen compound and a decomposition treatment agent, wherein the organic halogen compound and the decomposition treatment agent are continuously introduced into the reaction section. An organic halogen compound decomposition treatment apparatus configured to continuously discharge the decomposition treatment agent from the reaction section, wherein the decomposition treatment agent is the following (a) or (b): Halogen compound decomposition processing equipment. (A) A decomposition treating agent containing 50% by weight or more of magnesium oxide. (B) containing magnesium oxide and calcium oxide,
Its content is 50% by weight or more in total,
A decomposition treatment agent having a [calcium oxide / (magnesium oxide + calcium oxide)] (molar ratio) of 0.67 or less. 2. The method according to claim 1, wherein the temperature of the atmosphere in the reaction section is set to be higher on the upstream side than on the downstream side of the decomposition treatment agent.
3. The decomposition treatment apparatus for an organic halogen compound according to claim 1. 3. A preheating means for preheating the decomposition treatment agent,
The decomposition treatment apparatus for an organic halogen compound according to claim 1 or 2, wherein the decomposition treatment agent preheated by the preheating means is introduced into the reaction section.