JPH1076282A - Method and apparatus for supercritical hydroxylation treatment of organic chlorine compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable the implementation of a supercritical hydroxylation treatment method by equipment of industrial scale by a method in which in the oxidative decomposition of an organic substance in the presence of water in conditions exceeding the critical temperature and pressure of water, a produced acid substance is neutralized with a potassium alkaline substance or a calcium alkaline substance. SOLUTION: Waste liquid containing an organic chlorine compound, which is fluid to be treated, is pressurized from the initial end of a reactor 1 and supplied through a line 6. In the line 6, pressurized air as an oxidizing agent from a line 13 is combined and mixed, and a potassium hydroxide aqueous solution for neutralization from a line 12 is combined and mixed. Fluid after heat recovery by a heat recovering apparatus 2 connected with a fluid discharge line 7 connected with the terminal end of the reactor 1 is sent to a pressure reducing apparatus 3 through a line 8 and sent further an alkali regenerating apparatus 4 through a line 9. The potassium hydroxide aqueous solution for neutralization is regenerated and recovered by the apparatus 4, pressurized at a prescribed pressure, introduced into the reactor 1 from the line 12, and circulated to be reused.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating an organic chlorine compound, and more particularly, to a method for completely decomposing a persistent chlorinated organic chlorinated compound or a harmful organic chlorinated compound waste, the treatment of which has recently become a problem. The present invention relates to a method and apparatus suitable for

[0002] In the present invention, the target organochlorine compounds include P, which is designated as a harmful substance in environmental standards.
Various organic chlorine compounds such as CBs, trichloroethylene and tetrachloroethylene are included.

[0003]

2. Description of the Related Art Conventionally, treatment of hardly decomposable waste, waste liquid, toxic waste and waste liquid has been generally performed by a combustion method. If present, insufficient combustion, that is, partial decomposition will be insufficient, and when chlorine compounds or the like are targeted, it is considered that highly toxic substances may be generated. Also, in many cases, the combustion method may spread the problem because the end product is diffused from the stack to the atmosphere. Conventionally, PCBs that have been used as various heat media or insulating oils have been banned from production and use after their toxicity has been confirmed and their disposal is required, but little progress has been made. It is said that this is because the reliability of complete decomposition of organochlorine compounds by the combustion method has not been sufficiently obtained.

[0004] From these, closed and complete decomposition treatment is required for hardly decomposable and harmful organic chlorine compounds, and the supercritical water oxidation (treatment) method has recently attracted attention as a candidate. ing.

The supercritical water oxidation method is disclosed in
As disclosed in Japanese Unexamined Patent Publication No.
This method decomposes organic matter into water and carbon dioxide by using water as a medium for a decomposition reaction at a temperature of 74 ° C. or more and 22 Mpa or more. In this reaction, thermal decomposition, hydrolysis, and oxidative decomposition proceed simultaneously. Very high reaction rates can be achieved.

[0006] The basic flow of the supercritical water oxidation method is as follows. A decomposition target is pressurized by a feed pump, mixed with supercritical water after treatment by an ejector, heated, and then introduced into a reactor maintained at supercritical conditions. In the above reactor, high pressure air from an air compressor is usually introduced to perform supercritical water oxidation. The supercritical water after the treatment is, for example, partly recirculated to the ejector, and the remaining part is rotated by a turbine to recover energy. Some conventional documents which disclose specific examples of decomposing organic substances under the supercritical condition will be described below.

[0007] In the above-mentioned Japanese Patent Publication No. 1-38532, the details of the reactor are not described, but it is possible to adopt a tubular, cylindrical or fluidized bed type reactor. Also, Japanese Patent Laid-Open No. 3-50
No. 0264 describes details of the reactor, and proposes a reactor of a Vessel type (vertical cylinder type) as a reactor type for an organic waste liquid containing an inorganic salt or generating an inorganic salt after the reaction. ing.

In general, when a waste liquid containing no inorganic salt or inorganic salt-forming substance is used, a tubular (pipe) reactor is suitable. When trying to decompose an organic chlorine compound, it contains chlorine, so if this is subjected to supercritical water oxidation treatment, hydrochloric acid will be generated, and if this hydrochloric acid is neutralized with sodium alkali to protect the reactor materials, etc. Produces NaCl. However, it is known that this NaCl does not usually dissolve in supercritical water. Therefore, if a substance containing high concentration of chlorine is oxidized and neutralized in a tubular reactor, it is blocked in a short time. Is a problem.

Several proposals have been made to solve such problems. For example, Japanese Patent Publication No. Hei 6-511190 discloses a method in which a flow rate at which inorganic salts can be discharged from a long elongated tubular reactor is secured. Suggests how to drive.
However, the adhesion of the inorganic salt generated by the reaction is very strong, and it is almost impossible to discharge the inorganic salt in a normal flow rate range. The publication also discloses methods such as the addition of a scale-suppressing component and the use of a scale-suppressing magnet, but the former does not describe specific additives, and the latter does not confirm its effectiveness. However, no suitable proposal has been made yet as a countermeasure against the clogging of the pipe due to the precipitation of inorganic salts.

Japanese Patent Application Laid-Open No. 7-275869 proposes a reactor having a double-tube type structure using a porous inner tube for supplying an object to be treated to an inner tube and supplying supercritical water to an outer tube. In addition to supercritical water oxidation in the inner tube of this reactor, precipitated inorganic salts can be discharged without adhering to the inner tube wall by supercritical water spouting from the outer tube toward the inner tube. It has been. However, in this method, not only is it difficult to supply uniform supercritical water over the entire area of the double-tube reactor, but also there is a major problem of an increase in energy consumption accompanying the production of supercritical water. It is difficult to do.

[0011] In addition to the above, various supercritical water oxidation treatment methods have been proposed (for example, JP-A-7-27).
No. 5,870, JP-A-7-275871, JP-A-7-275872, JP-A-7-313988, JP-A-8-38853, and the like. There is no.

On the other hand, according to the method disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 3-500264, in which the vessel type reaction vessel is installed vertically, it is possible to address the problem of inorganic salt precipitation. In other words, in this method, a supercritical zone is formed in the upper part of the vertical cylindrical reaction vessel, and a subcritical zone is formed in the lower part. This is dissolved in subcritical water in the zone and discharged. Since the vessel type reactor has such a vertical structure, two outputs (fluid discharge paths) from the reactor are provided, one of which is a processing fluid (supercritical water, excess oxygen) from the upper part of the reactor. , A mixture of carbon dioxide and nitrogen), and the other is a brine stream (aqueous solution containing an inorganic salt such as sodium chloride) discharged from the lower part of the reactor.

As described above, in the system using a vessel type reaction vessel, since supercritical water and inorganic salts can be separated in the reaction vessel, the adherent salt that precipitates in the supercritical region adheres to the inner wall of the vessel. This is extremely excellent in that the problem of blockage can be eliminated. However, since there are two outputs from the reaction vessel, subsequent heat recovery, cooling, and decompression steps are required for each, and this involves complexity and complexity in equipment configuration, control, and maintenance. There is difficulty.

[0014]

As described above, the supercritical water oxidation treatment can completely decompose hard-to-decompose toxic wastes and waste liquids in a closed system. Although attention is being paid to this method as an extremely effective method for treating chlorinated organic compounds, the method for oxidizing an organic chlorine compound has many technical problems as described above.
And, in order to carry out the supercritical water oxidation treatment method on an industrial scale, it is extremely important to realize large-scale treatment and continuous treatment. In particular, in order to effectively utilize the advantages of the treatment method,
Appropriate countermeasures against the above-mentioned problems, that is, generation of acid generated from the chemical structure of the object to be treated, neutralization of the acid, prevention of adhesion of salt generated by the neutralization to the inner wall of the container, or removal of adhered substance Finally, it is required to prevent the reaction vessel from being blocked by the deposits.

However, it is theoretically possible to industrially carry out the supercritical water oxidation treatment using a tubular (pipe-shaped) reaction vessel which is excellent in efficiency because the object to be treated which does not generate an acid can be used. There is a problem that is limited to
The method in which the above-described vessel-type reaction vessel is installed and used vertically is excellent in that salts generated by neutralization can be separated and removed in the reaction vessel, but the number of fluid discharge lines from the reaction vessel is two. Therefore, as compared with the case where a tubular reaction vessel having a single discharge line is used, there is a difficulty that the apparatus configuration, control and maintenance are complicated and complicated.

As described above, among the conventional documents that disclose the supercritical water oxidation treatment method, the acid generated in the reaction container of the supercritical water oxidation treatment or the object to be treated is brought into the reaction container. If there is a salt formed by neutralizing an acid to be neutralized with an alkaline substance, it is directly confirmed that this salt does not dissolve in supercritical water, and that the adhesion of the salt may cause problems such as clogging. In addition, although there are documents indirectly pointed out, these methods reduce the adhesion of the generated neutralized salt by taking measures for the structure of the apparatus (the structure of the vessel-type reaction vessel) or by moving at a high flow rate to suppress the adhesion. (Japanese Unexamined Patent Publication No. 6-511190), and there is no study on the magnitude of the adhesion due to the type of salt generated and its influence.

According to the present inventors, salts formed under the conditions of performing supercritical water oxidation treatment under the above-described conventional techniques are generally not dissolved in supercritical water and have an adhesive property. Although it is believed that the type of salt produced has an influence on the configuration, operation method, and control method of the above-described apparatus for supercritical water oxidation, intensive studies have been made.

In the course of the study, surprisingly, in the process of supercritical water oxidation of an organochlorine compound, sodium alkali, potassium alkali or calcium alkali, whose behavior was considered to have little difference as an alkali metal, was surprising. It has been found that there is a great difference in the degree of attachment to the reaction vessel with the product, and the present invention has been made based on such knowledge.

That is, an object of the present invention is to provide a treatment method effective for carrying out a supercritical hydroxylation treatment suitable for completely decomposing an organic chlorine compound on an industrial scale apparatus. And an apparatus.

Another object of the present invention is to provide a tubular reaction having a single fluid discharge path in a supercritical water oxidation treatment in which an acid generated when supercritical water oxidation of an organic chlorine compound needs to be neutralized. It is an object of the present invention to provide a processing method and an apparatus capable of using a container.

[0021]

The feature of the present invention to achieve the above object is described in each of the claims, and the method for supercritical water oxidation of an organochlorine compound according to claim 1 is provided. The invention of the present invention relates to a supercritical water oxidation method in which organic substances are oxidatively decomposed in the presence of water at a temperature exceeding the critical temperature and critical pressure of water. It is characterized by summing.

In the above, the potassium alkali or calcium alkali is preferably supplied in a state suitable for supply to the reaction vessel, for example, in the form of an aqueous solution.
It can be supplied alone or, if necessary, mixed with an organic substance or water to be treated. When a tubular reaction vessel is used, the mixing in the tube must be sufficiently large to allow the supercritical hydroxylation reaction to proceed smoothly. For example, the supply fluid is supplied from the beginning of the reaction vessel to the tube by a two-fluid nozzle. Or sufficient turbulence in the pipe (Reynolds number> 10,000 to 20,000)
In many cases, it is preferable to select the reaction vessel diameter so that

The supply amount of the alkali substance may be an amount necessary for neutralizing the generated acid substance, and is determined according to the amount of the acid generation substance contained in the organic substance to be decomposed.

According to the present invention, it is not always clear whether the formed potassium chloride or calcium chloride has high solubility or low adhesion, but potassium chloride or calcium chloride is formed by supercritical oxidation. It does not flow out of the system together with the other fluid and does not cause blockage due to adhesion to the wall surface of the reaction vessel. The passability of potassium chloride or calcium chloride through a supercritical water reactor is very good, and as described in detail below,
It has been confirmed that 10% of potassium chloride or calcium chloride can pass through in supercritical water at ℃.

The potassium alkali of the present invention includes:
Although not limited, potassium hydroxide or potassium carbonate is preferably used, but this does not exclude the use of an organic potassium compound.

The calcium alkaline substance is not limited, but calcium hydroxide or calcium carbonate is preferably used, but it does not exclude an organic calcium compound.

According to a fourth aspect of the present invention, a relatively expensive salt of potassium alkali is recovered from a product fluid obtained by the supercritical water oxidation treatment and the neutralization treatment, and the potassium alkali is regenerated. It is characterized by the following. As a method of regenerating potassium alkali from a salt of potassium alkali,
For example, an electrolysis method can be mentioned.

The invention of a supercritical water oxidation treatment apparatus according to claim 6 of the present application is directed to a tubular reactor in which the inside of a tube is maintained under supercritical conditions exceeding the critical temperature and critical pressure of water, and from the beginning of the tubular reactor. Water, oxidizing agent for supercritical water oxidation treatment and neutralization treatment,
A supply fluid inflow means for inflowing an organic substance and potassium alkali or calcium alkali, and a discharge means for discharging the fluid generated by the supercritical water oxidation treatment and the neutralization treatment, which is connected from the terminal end of the tubular reactor to a subsequent treatment means. Characterized in that it comprises:

According to this device invention, the above-described method invention can be suitably implemented.

In the above invention, the tubular reactor and a pipe connected to the tubular reactor may be a continuous pipe extending from the beginning of the tubular reactor to the end of the pipe. Or a bend in a circular or elliptical shape, and in particular, a bend in a circular or elliptical shape to extend the tubular reaction vessel and the subsequent connection pipe for fluid discharge. When the device is provided, it is excellent in that the installation volume of the device can be reduced.

The above-mentioned invention can completely decompose an organic chlorine compound in a closed system, so that it can be effectively used particularly for decomposition treatment of a hardly decomposable and harmful organic chlorine compound. As a specific organic chlorine compound as an object to be treated which can be effectively treated by applying the present invention, PCB specified as a harmful substance in environmental standards
Organic chlorine compounds such as s, trichloroethylene, tetrachloroethylene and waste agricultural chemicals can be mentioned.

Although the supercritical water oxidation reaction vessel of the present invention is a high-pressure gas target facility, either a tubular type vessel or a vessel type vessel can be used. It is used more effectively in a mold reaction vessel. In this case, the reaction temperature is generally 400 ° C. or higher,
The temperature is preferably about 600 to 650 ° C., and the reaction pressure is 22 to 50 MPa, preferably 22 to 25 MPa.
a is preferable. The reaction time is 1 to 10 minutes, preferably 1 to 2 minutes. As the oxidizing medium, it is possible to use a liquid phase oxidizing agent such as hydrogen peroxide in addition to air and oxygen gas.

Compared to the present invention, sodium chloride produced when a sodium alkali such as sodium hydroxide is used as a neutralizing agent has a solubility of 0.1% or less in supercritical water at 450 ° C. or higher. In addition, the adhesion of the precipitated sodium chloride to the metal is intense. Therefore, when supercritical water oxidation of an organic chlorine compound is performed in a tubular reaction vessel using sodium hydroxide as a neutralizing agent, the pressure in the reaction vessel gradually increases, and it is possible to prevent the reaction vessel from being eventually clogged. As described above, the present invention is extremely excellent in that the present invention can be carried out without causing blockage.

The present inventors are the first to clarify that the use of a potassium alkali or calcium alkali as a neutralizer has a great advantage in a supercritical water oxidation reaction.

[0035]

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows a flow sheet of an embodiment of the present invention.

In FIG. 1, reference numeral 1 denotes a reaction vessel, from which a waste liquid containing an organic chlorine compound as a fluid to be treated is pressurized to a predetermined pressure and supplied through a line (pipe) 6. In addition, air pressurized to a predetermined pressure, for example, as an oxidizing agent is merged and mixed into the line 6 from the line 13, and an aqueous solution of potassium hydroxide for neutralization is merged and mixed from the line 12. (No pressurizing means such as a high-pressure pump is shown).

Numeral 2 denotes a heat recovery device connected to a fluid discharge line 7 connected to the end of the reaction vessel 1. Fluid recovered by the heat is sent to a pressure reducing device 3 through a line 8 and further to a line 9 Is sent to the alkali regenerator 4 via In this example, the aqueous potassium hydroxide solution for neutralization is regenerated and recovered by the alkali regenerator 4 and pressurized to a predetermined pressure (pressurizing means is not shown). It is introduced and recycled for recycling.

Reference numeral 5 denotes a re-neutralizing unit. Hydrochloric acid contained in the fluid from which the potassium salt has been separated by the alkali regenerating unit 4 is treated in the re-neutralizing unit 5 through the line 10 and
It is discharged out of the system of the supercritical water oxidation apparatus.

The treatment in the supercritical water oxidation treatment apparatus constructed as described above will be described. In the reaction vessel 1, an organic chlorine compound, water, air and potassium alkali are supplied, and the critical temperature of water in the vessel, Conditions above the critical pressure (generally the temperature is 400 ° C. or higher, preferably 600 to 6
Around 50 ° C., the pressure is 22-50 MPa, preferably 22
-25 MPa), a supercritical water oxidation reaction is performed in the presence of water, and the supplied organic chlorine compound is completely decomposed. At the same time, the hydrochloric acid generated as a result of the reaction reacts with potassium hydroxide supplied (introduced) into the container and is neutralized. The above reaction is carried out for about 1 to 10 minutes, preferably for 1 to 2 minutes.

Since the potassium chloride produced as a result of the neutralization reaction has a permeability even in supercritical water at 600 to 650 ° C., the operation can be effectively performed even if a tubular reaction vessel is used as the reaction vessel.

The processing fluid after the completion of the oxidation reaction, that is, the reaction gas such as supercritical water, carbon dioxide, nitrogen, potassium chloride, etc. is discharged out of the reaction vessel 1 through the discharge line 7 directly connected to the outlet (terminal). The high-pressure supercritical fluid recovers heat in the heat recovery device 3 and is cooled to, for example, 100 ° C. or lower.

The heat recovery device 3 can be used as a heating source of supercritical water for heating (not shown), in addition to preheating an organic chlorine compound as a fluid to be treated. A double-pipe heat exchanger is preferably employed, but is not particularly limited.

As the pressure reducing device 4, an air-operated pressure reducing valve can be usually used, but is not particularly limited.

The processing fluid after cooling and depressurization is separated into processing gas and processing water by a gas-liquid separator (not shown), and the processing water is sent to the alkaline regenerating unit 4 through a line 9. The alkali regenerating apparatus 4 generally uses an electrolysis apparatus. Potassium chloride dissolved and contained in treated water is separated into hydrochloric acid and potassium hydroxide through an ion exchange membrane. It is circulated through 12 to the preceding reaction vessel. On the other hand, the hydrochloric acid leaving the alkali regenerating unit 4 is treated by the re-neutralizing unit 5 through the line 10 and discharged from the supercritical water oxidation unit through the line 11.

[0045]

Next, the present invention will be described in more detail by way of examples.

Example 1 This example was performed using a supercritical water oxidation bench scale apparatus (tubular reactor: inner diameter 4.5 mm × length 450 mm). The inorganic salt was adjusted to a predetermined concentration using sodium chloride, potassium chloride, and calcium chloride, and used for the test.

In the test procedure, first, pure water was supplied by a high-pressure pump while heating the reactor and the preheater. When the temperature in the reaction vessel reached a predetermined temperature, each salt solution was supplied by a high-pressure pump in the same manner as pure water. Water was supplied into the reactor. The pure water and each salt solution were not brought into contact with each other until they reached the reactor.

The treatment liquid is passed through a cooler and a decompressor at room temperature,
At normal pressure, the processing solution was sampled at predetermined time intervals, and then the ion concentration of each sample was measured. Factors governing inorganic salt solubility are mainly temperature,
Pressure, but in this example, the pressure is 25 MPa
And the temperature and salt concentration were varied as shown in Table 1 below.

The concentration at the inlet of the reactor was calculated from the flow rate of each solution and the salt concentration, assuming that the prepared salt solution and supercritical water were uniformly mixed.

[0050]

[Table 1]

In this test, if salts precipitate in supercritical water and adhere to the inner wall of the reactor, the salt concentration at the outlet decreases with respect to the reactor inlet. Then, the recovery rates of various ion concentrations of the collected sample solution were measured, and the solubility (or permeability) of the inorganic salt in supercritical water was examined. The ion concentration is measured by ion chromatography (manufactured by Nippon Dionex:
DX AQ) was used.

Prior to the test shown in Table 1, changes in the sodium ion concentration and the chloride ion concentration with time of the outlet treated water when a 1% aqueous sodium chloride solution was passed through a reactor at 350 ° C. were examined. 2 is shown.

As can be seen from FIG. 2, the ion concentration became constant in about 60 minutes, and the outlet concentration became almost equal to the inlet concentration (the sum of Na ions and Cl ions at the outlet of the reactor became almost 10,000 ppm). Therefore, in the case of sodium chloride, it was determined that there was a solubility of 1% or more in the reactor at 350 ° C. (or it could pass through the reaction vessel: the same applies hereinafter). The tests at the concentrations and temperatures of other salt solutions in Table 1 were performed in the same manner, and the results are shown in Table 2 below.

[0054]

[Table 2]

From the results in Table 2 above, sodium chloride was 4%.
If the temperature is not higher than 00 ° C., the solubility (permeability) is 10%. However, the solubility (permeability) is sharply reduced from around 450 ° C., and it does not dissolve (pass) even at 0.1% above 500 ° C. .

On the other hand, potassium chloride and calcium chloride exhibited a solubility (permeability) of 10% or more even at 600 ° C. or more.

These results indicate that the use of potassium alkali or calcium alkali is suitable as a neutralizing agent in the case of performing supercritical water oxidation of an organic chlorine compound.

Example 2 Trichlorethylene (TCE) was selected as the organochlorine compound, and the test was carried out using the same supercritical water oxidation bench scale apparatus as in Example 1 (tubular reactor: inner diameter 4.5 mm × length 450 mm). went.

In the test, the TCE stock solution was supplied to the reactor, and the TCE concentration at the reactor inlet was adjusted to about 1% by mixing with supercritical water immediately before the reactor. Supply T as oxidizing agent
Hydrogen peroxide was used in an amount sufficient to decompose CE. As the neutralizing agent, two kinds of aqueous solutions of sodium hydroxide and potassium hydroxide were used, and an amount sufficient to neutralize the entire amount of hydrochloric acid generated after decomposition of TCE was added. The reaction temperature was 600 ° C. and the pressure was 25 MPa.

As a result, when sodium chloride was used as the neutralizing agent, the pressure inside the reactor rapidly increased about 40 minutes after the start of the operation, and the operation had to be stopped.

On the other hand, when potassium hydroxide was used as the neutralizing agent, it was possible to operate for several hours while keeping the pressure in the reactor almost constant. After completion of the test, the treatment liquid was analyzed. As a result, it was confirmed that potassium ions and chloride ions had passed through in total as well as complete decomposition of TCE. This result indicates the effectiveness of potassium alkali as a neutralizing agent.

[0062]

As described above, according to the present invention in which a potassium alkali or calcium alkali is used as a neutralizing alkali agent, potassium chloride or calcium chloride produced by a supercritical water oxidation reaction and a neutralization treatment is used. For example, 6
Since it has the property of being able to pass through even in supercritical water at a temperature of 00 to 650 ° C. without being deposited or adhered, an extremely excellent effect is achieved in which supercritical water oxidation can be efficiently performed without incurring clogging of the apparatus.

Further, since such neutralized potassium chloride or calcium chloride has the above-mentioned permeability, even in the case of a tubular type reaction vessel which has conventionally been difficult to carry out continuously as a result of precipitation and adhesion of sodium salts, It becomes possible to carry out the supercritical water oxidation treatment, and there is an extremely great advantage that a tubular reaction vessel having a simple structure can be used as the reaction vessel.

In particular, when providing an industrial device capable of completely decomposing a hardly decomposable and harmful organic chlorine compound in a closed system, the configuration of the device is simple and the control or maintenance is easy. An excellent effect is obtained in that an apparatus using a tubular reaction vessel, which is also advantageous, can be employed.

If potassium chloride contained in the produced fluid is recovered by using an alkali regenerating device provided at the subsequent stage and is recycled as potassium alkali for neutralization, relatively expensive potassium alkali can be recovered. The economic disadvantages during use can be eliminated.

Therefore, it can be said that the supercritical water oxidation treatment method of the present invention is a technically and economically very advantageous method.

[Brief description of the drawings]

FIG. 1 shows a flow sheet according to an embodiment of the present invention.

FIG. 2 is a diagram showing the results in the examples, and shows the ion concentration of the NaCl solution at the outlet of the reaction vessel.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Reaction container, 2 ... Heat recovery device, 3 ... Decompression device, 4 ... Alkaline regeneration device, 5 ... Re-neutralization device.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Noriyuki Aki 1-4-9 Kawagishi, Toda City, Saitama Prefecture Inside Organo Research Institute (72) Inventor Hiroshi Suzugaki 1-4-9 Kawagishi, Toda City, Saitama Prefecture No. Organo Research Institute

Claims (7)

[Claims] 1. A supercritical water oxidation method for oxidatively decomposing an organic chlorine compound in the presence of water at a temperature exceeding the critical temperature and critical pressure of water. A supercritical water oxidation method for an organic chlorine compound, characterized by neutralizing with an organic solvent. 2. The method for supercritical water oxidation of an organic chlorine compound according to claim 1, wherein the potassium alkali is potassium hydroxide or potassium carbonate. 3. The method for supercritical water oxidation of an organic chlorine compound according to claim 1, wherein the calcium alkali is calcium hydroxide or calcium carbonate. 4. The organic method according to claim 1, wherein a potassium alkali salt is recovered from a product fluid obtained by performing the supercritical water oxidation treatment and the neutralization treatment, and the potassium alkali material is regenerated. Supercritical water oxidation of chlorine compounds. 5. The supercritical water oxidation method for an organic chlorine compound according to claim 4, wherein the method for regenerating the potassium alkali from the potassium alkali salt is an electrolysis method. 6. A tubular reactor in which the inside of the tube is maintained at supercritical conditions exceeding the critical temperature and pressure of water, and water for supercritical water oxidation and neutralization from the beginning of the tubular reactor. A supply fluid inflow means for introducing an oxidizing agent, an organochlorine compound and a potassium alkali or calcium alkali, and a downstream stage from the end of the tubular reactor for discharging the fluid generated by the supercritical water oxidation treatment and the neutralization treatment. 6. A supercritical water oxidation treatment apparatus for an organic chlorine compound used in the supercritical water oxidation method according to claim 1, further comprising a pipe connected to the processing means. 7. The tubular reactor according to claim 6, wherein the tubular reactor and a pipe connected to the tubular reactor are pipes continuous from a start end of the tubular reactor toward an end of the pipe, and the pipe is:
A supercritical water oxidation treatment apparatus for an organic chlorine compound, which is extended linearly or bent in a circular or elliptical shape.