JP2002361069A - Supercritical hydroreaction apparatus and vessel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a supercritical hydroreaction apparatus for subjecting liquid to be treated which contains an organic chlorine compound in particular to supercritical water treatment. SOLUTION: This apparatus is the supercritical hydroreaction apparatus which has a reactor 12 housing supercritical water, introduces the liquid to be treated which contains the organic chlorine compound into the reactor and subjects the liquid to oxidation decomposition by air. The apparatus has a temperature controller 32 for controlling the temperature in the reactor to a range from >=550 to <=650 deg.C by regulating the feed inflow rate, etc., of the liquid to be treated. The surface layers of the reactor walls are coated with composite corrosion resistant layers composed of titanium layers consisting of titanium or a titanium alloy and iridium oxide layers laminated on the titanium layers. The apparatus has a treating fluid flow passage in which the treating fluid flows and an aqueous alkaline solution flow passage which injects an aqueous alkaline solution into the treating fluid by confluence with the treating fluid flow passage and has a neutralizing and rapid cooling section 30 for subjecting the treating fluid to neutralizing and rapid cooling to <=450 deg.C by the aqueous alkaline solution. The wall surfaces in contact with the treating fluid of the neutralizing and rapid cooling section are coated with the composite corrosion resistant layers of the tantalum layers, titanium layers and iridium oxide layers successively disposed on the wall surfaces.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid to be treated,
The present invention relates to a supercritical water reactor for treating a liquid to be treated containing an organic chlorine compound such as CB with supercritical water.
The present invention relates to a supercritical water reactor optimal for supercritical water treatment for completely decomposing and rendering harmless.

[0002]

2. Description of the Related Art With increasing awareness of environmental issues,
As one of the application fields of the supercritical water reactor, attention has been paid to decomposition and detoxification of environmental pollutants. In other words, by supercritical water reaction utilizing the properties of the reaction medium of supercritical water,
Harmful hard-to-decompose organic substances that were difficult to decompose in the prior art, for example, PCB (polychlorinated biphenyl),
This is an attempt to decompose dioxins, organic chlorinated solvents, etc., and convert them to harmless products such as carbon dioxide, water, and inorganic salts.

[0003] Supercritical water refers to water that is in a supercritical state, that is, water that is beyond the critical point of water, and more specifically, has a critical temperature, that is, a temperature of 374.1 ° C or higher, and Of water under a critical pressure of 22.04 MPa or more. Supercritical water has a high ability to dissolve organic substances and can completely dissolve non-polar substances, which are abundant in organic compounds, but has a very low ability to dissolve inorganic substances such as metals and salts. The supercritical water can be mixed with a gas such as oxygen or nitrogen at an arbitrary ratio to form a single phase.

Referring to FIG. 8, a basic configuration of a conventional supercritical water reactor for treating a liquid to be treated containing an organic chlorine compound with supercritical water will be described. FIG. 8 is a flow sheet showing the configuration of a conventional supercritical water reactor. The supercritical water reactor 100 is a so-called modal process type device which is conventionally known as an optimal device for oxidative decomposition of organic chlorine-based hardly decomposable organic substances such as salts that precipitate during supercritical water treatment. There is provided a pressure-resistant closed vertical reactor 102 having a subcritical water area at the bottom, and a salt precipitated as a solid substance in supercritical water is settled and separated into a subcritical water area at the lower part of the reaction vessel. .

[0005] As shown in FIG. 8, a supercritical water area 104 in which supercritical water is retained is formed at an upper portion of the reactor 102, and a condition above a critical point of water, that is, a supercritical condition is maintained. I have. On the other hand, in the lower part of the reactor 102,
08 is formed via the virtual interface 106 with the supercritical water area 104 and retains subcritical water having a temperature lower than the critical temperature of water. At the upper part of the reactor 102, an inflow pipe 110 for flowing the liquid to be treated and the oxidizing agent to be subjected to the supercritical water treatment into the supercritical water zone 104 is connected. A liquid line 112 for supplying a liquid to be treated having an organochlorine compound to be treated by the supercritical water reaction and an air line 114 for supplying air as an oxidizing agent for oxidizing organic substances are merged into the inflow pipe 110. are doing. If necessary, a supercritical water line 115 for supplying supercritical water or make-up water for generating supercritical water to the supercritical water area may be connected to the inflow pipe 110.

A neutralizing agent line 116 for supplying an alkali neutralizing agent for neutralizing hydrochloric acid generated by the organic chlorine compound in the liquid to be treated is connected to the liquid line 112. In this example, the liquid to be treated and the neutralizing agent are usually supplied to the reactor 102 through the inflow pipe 110, and are atomized downward by the air as the oxidizing agent, so that the supercritical fluid in the reactor 102 It is sprayed into the water area 104. Organochlorine compounds in the sprayed liquid to be treated are instantaneously oxidized and decomposed in the supercritical water area 104. As a result of the supercritical water reaction, the chlorine of the organochlorine compound contained in the liquid to be treated is neutralized with the alkali neutralizer to form a salt, and shifts from the supercritical water area to the subcritical water area. A processing fluid line 118 is further connected to the upper part of the reactor 102, and the organic substance in the liquid to be processed is mainly converted into water and carbon dioxide by a supercritical water reaction, and the processing fluid from the supercritical water zone 104 together with the processing fluid. Exit through line 118.

On the other hand, a subcritical water line 120 and a subcritical drain line 122 are connected to a lower portion of the reactor 102.
The sub-critical water line 120 supplies sub-critical water to the sub-critical water area 108, and the sub-critical drain line 122 uses the sub-critical water in which the salt generated by the supercritical water reaction and the neutralization reaction is dissolved as waste water to drain the sub-critical water. Discharge from water area 108. Although not shown, the processing fluid line 118 and the subcritical drainage line 122 also include a pressure controller that maintains the pressure in the reactor 104 at a predetermined pressure, a cooler that lowers the temperature of the processing fluid and subcritical drainage to a predetermined temperature, A decompression device for reducing the pressure to a predetermined pressure, a gas-liquid separation device, and the like are provided.

[0008]

However, the following problems have been encountered when attempting to treat a liquid to be treated containing high-concentration PCB with supercritical water using the above-described conventional supercritical water treatment apparatus. First, as in the conventional case, the reaction temperature slightly exceeds the critical temperature of water (374.1 ° C.), that is, 450 ° C.
At temperatures in the range from 1 to 500 ° C., it was extremely difficult to reduce the PCB content of the processing solution to 3 ppb or less, which is allowed by the discharge standard. Conversely, it is expected that higher reaction temperatures will be required.

Second, there are two problems caused by the two-zone system in which a supercritical water area and a subcritical water area are formed in a reactor. One problem is that corrosion of the reactor wall, particularly near the boundary between the two regions, is remarkable. Normally, the neutralization reaction proceeds concurrently with the supercritical water reaction, so that no corrosion problem occurs. However, if the neutralization is incomplete, corrosion becomes a problem. In the conventional method, since a high-temperature supercritical water area and a low-temperature subcritical water area exist in the reactor, a severely corrosive area always exists, which is an obstacle to the practical use of PCB supercritical water treatment. Had become. Second, if the spraying of the liquid to be treated is not good in the conventional method, the PC
B and the like may not enter into the subcritical water area without being completely decomposed. In this case, because the temperature of the subcritical water area is low,
The undecomposed material mixed in the subcritical water area remains as it is without being decomposed, and is discharged as wastewater from the subcritical water area. Therefore, there is a problem that the PCB content in the subcritical wastewater exceeds the discharge standard.

Thirdly, when the concentration of organic chlorine in the liquid to be treated is high, as in the case of treating PCB, there are many unclear points in the mechanism of neutralization reaction and salt formation / separation. In such a case, there is a problem that it is actually difficult to completely neutralize hydrochloric acid generated from the organic chlorine of the PCB in the reactor as in the related art, and the reliability is poor.

Therefore, as an improvement of the neutralization treatment, a neutralization and quenching section is provided at the outlet or downstream of the reactor for injecting an alkaline aqueous solution into the treatment fluid and quenching and neutralizing the same. Attempts have been made to neutralize and quench the fluid. However, in this method, a large amount of hydrochloric acid generated by the supercritical water reaction is present in the reactor because the process fluid flows out of the reactor and enters the neutralization quenching section before neutralization. For this reason, nickel alloys such as Inconel 625, which have been conventionally used as a corrosion-resistant layer on the inner wall of a reactor, have a problem in that they are significantly corroded by hydrochloric acid and cannot be used. Further, even in the quenching neutralization section, there is a problem that the pipe is significantly corroded up to the point where the neutralization reaction between the alkaline aqueous solution and the processing fluid is completed, and it is difficult to use the nickel alloy for the pipe for a long time. .

Further, attempts have been made to employ a pressure balanced reactor in combination with a neutralization and quenching section. As shown in FIG. 9, the pressure-balanced reactor 130 is provided as an outer cylinder 131 formed as a pressure vessel and as an inner cylinder communicating with the outer cylinder 131, and contains supercritical water. It is formed as a double cylinder with a reaction cartridge 132 forming a reaction zone. From the inlet nozzle 133 connected to the inflow pipe 110 (see FIG. 8),
An oxygen-containing gas, such as air, as an oxidant is caused to flow into the reaction zone 134 in the reaction cartridge 132, and from the pressure-balancing gas inlet 135 to the annular portion 136 between the outer cylinder 131 and the reaction cartridge 132, For example, air is supplied as a pressure balancing gas. The pressure balancing gas is supplied from the pressure vessel 131 and the reaction cartridge 132.
From the annular portion 136 via the upper gap 137 to the reaction zone 1
34 and is consumed as part of the oxidant.

The reaction zone 134 in the reaction cartridge 132
Is oxidized and decomposed by oxygen in the supercritical water and flows out of the reactor outlet pipe 138. The neutralization and quenching section is located downstream of the reaction cartridge 132,
Is provided inside or outside. In the conventional pressure-balanced reactor, since there is almost no pressure difference between the inside and the outside, the reaction cartridge 132 can be formed as a non-pressure vessel with a small thickness, so that the reaction cartridge 132 can be made of an expensive corrosion-resistant metal, for example, a nickel alloy such as Inconel 625 or the like. There is an advantage that the cost is not increased even if it is formed with. In addition, the annular portion 136
Since the atmosphere is not a highly corrosive atmosphere, the outer cylinder 131 does not necessarily need to be formed of the same material as the reaction cartridge 132, and is usually formed of heat-resistant / pressure-resistant carbon steel or stainless steel. However, there is a problem that even a reaction cartridge formed of an expensive nickel alloy is significantly corroded by hydrochloric acid and must be replaced in a short time.

Therefore, an object of the present invention is to treat a liquid to be treated, in particular, a liquid to be treated containing a high concentration of PCB or the like, with supercritical water to reduce the concentration of PCB to 3 ppb or less which is permitted by the discharge standard. An object of the present invention is to provide a supercritical water treatment apparatus that reduces the PCB concentration of a liquid and that can operate stably for a long period of time.

[0015]

In order to achieve the above object, the present inventor has set forth the following object: (1) To increase the concentration of a liquid to be treated having a high organochlorine concentration, such as PCB, to a PCB concentration of 3 ppb, which is allowable on a discharge standard. Establishing a reaction temperature at which critical water treatment is possible;
(2) It was considered necessary to establish a reactor material that can be used under such temperature conditions and in a highly concentrated hydrochloric acid atmosphere.

Therefore, first, the relationship between the decomposition rate of PCB and the reaction temperature of the supercritical water reaction was investigated in order to reduce the PCB content in the processing fluid generated by the supercritical water treatment of PCB to 3 ppb or less. As a result, under the conditions of a reaction pressure of 23 MPa and a reaction time of 2 minutes or more and 4 minutes or less, when the reaction temperature is 500 ° C., the PCB concentration is 3 ppb or more, and it is not possible to satisfy the discharge standard of 3 ppb. It was found that the PCB concentration could be reduced to 3 ppb or less by setting the reaction temperature to 550 ° C. and 650 ° C. When the reaction temperature is 500 ° C., the PCB concentration is 3
It was also found that it could not be less than ppb.

That is, the reaction temperature is 550 ° C. or higher and 650 ° C.
By setting the temperature in the range of not more than ℃, oxidative decomposition of the liquid to be treated containing the organic chlorine-based compound composed of PCB or PCB-like compound by the supercritical water reaction so that the PCB concentration in the treatment fluid is 3 ppb or less. can do.
The PCB-like compound is a compound having a chemical structure substantially similar to that of PCB, and includes, for example, dioxins, chlorobenzene compounds, chlorophenols, and the like.

Next, in order to select a material having corrosion resistance to high-concentration hydrochloric acid at a temperature of 550 ° C. or more, reactors are made of various materials, and the PCB is actually treated with supercritical water to obtain a material. A corrosion test was performed to evaluate the corrosion resistance. By the way, for example, when a PCB having a purity of 100% from trichloride to pentachloride is treated with supercritical water, the concentration of the generated hydrochloric acid is about 10% to 15% by mass. Therefore, in the corrosion test, the hydrochloric acid concentration of the aqueous hydrochloric acid solution was set to 2
At 0% by mass, the corrosion rates of various materials were measured as follows.

First, autoclave-shaped reactors were prepared from the following materials, respectively, and an aqueous hydrochloric acid solution having a hydrochloric acid concentration of 20% by mass was accommodated in each of the reactors. Temperature to 500 ℃
The temperature was maintained from time to 600 hours and the corrosion rate of the vessel wall of each reactor was measured. The results are as shown in Table 1. In Table 1, the symbol "-" indicates that the weight per unit area of the reactor was increased by the generation of chloride. Accordingly, the corrosion rate indicated by a minus sign also means that corrosion is in progress.

[Table 1]

Next, from a temperature of 300 ° C. to 650 ° C.,
Except for 550 ° C., the experiment temperature was set in increments of 50 ° C. and the same corrosion experiment was performed. As a result, the corrosion experiment results shown in Table 1 and FIG. 10 were obtained. FIG. 10 is a graph of the numbers in Table 1. The materials used in the experiments were platinum (Pt), iridium (Ir), ruthenium (Ru), and rhodium (Rh) among the platinum group elements evaluated to have high corrosion resistance.
And titanium (Ti (ASTM grade 12)) and tantalum (T
a) and alumina oxide (Al ₂ O ₃ ).

Incidentally, it was found that rhodium (Rh) was easily dissolved in an aqueous hydrochloric acid solution having a hydrochloric acid concentration of 20% by mass, and it was found that it was not possible to prepare a reactor and perform an actual corrosion test. The test piece was immersed in a hydrochloric acid aqueous solution under the same conditions as above, and the corrosion resistance was evaluated. The results of the rhodium corrosion experiment are shown in Table 1 as a corrosion rate of 27 mm / y at 300 ° C. However, since rhodium is dissolved in an aqueous hydrochloric acid solution at 300 ° C., the dissolution rate is indicated as the corrosion rate. It was done.

By the way, in the actual supercritical water treatment, if the corrosion rate of the vessel wall of the reactor is less than 1 mm / year, the corrosion resistance is low and it can be evaluated that it is the most preferable corrosion resistant material as the material of the reactor. When the corrosion rate is 1 mm / year or more and less than 5 mm / year, the corrosion rate is corrosive within an allowable range and can be evaluated as a corrosion resistant material that can be used as a material for the reactor. However, when the corrosion rate exceeds 5 mm / year, the corrosion rate exceeds the allowable range, and cannot be evaluated as a corrosion-resistant material that can be used as a reactor material.

According to the above criterion for corrosion (corrosion resistance), based on the corrosion rate of the container wall obtained in the corrosion test, whether or not each material subjected to the corrosion test can be used in a reactor is evaluated as follows. did. Materials other than iridium, namely, titanium, tantalum (Ta), platinum (Pt), ruthenium (Ru), rhodium (Rh), and alumina oxide (A
corrosive l ₂ O _3), in particular temperature range, the corrosion rate was less than 1 mm / year over 5 mm / year, but falls within the allowable range, high corrosion rate at that temperature range, it is Cannot be adopted. For example, titanium, ruthenium, and rhodium have a low corrosion rate in a high-temperature region, but have a very high corrosion rate at a temperature of 400 ° C. or less, particularly at 300 ° C. Conversely, tantalum has a low corrosion rate in a temperature range of 400 ° C. or lower, but has a very high corrosion rate in a high temperature range of 400 ° C. or higher. In addition, although alumina oxide has a low corrosion rate in a high-temperature region, it cracks and cannot be used as a corrosion-resistant material for a reactor.

Furthermore, even among platinum group elements which are evaluated as having high corrosion resistance, platinum other than iridium, ruthenium (Ru) and rhodium (Rh) have poor corrosion resistance except in a specific temperature range. Only iridium has good corrosion resistance over the temperature range from room temperature to 650 ° C.

In the reactor, 550 to 65
Although it is desirable that the temperature is in a temperature range of 0 ° C., in actual operation, when the nozzle spraying is deteriorated, it is considered that a temperature of a part of the reactor, particularly the lower part, becomes 400 ° C. or less. It is necessary that the corrosion rate be within an allowable range. For example, if the reactor uses titanium,
In order for the corrosion resistance of titanium to work, it is necessary to keep the reactor always in a high temperature range, and a special temperature maintenance device is required. In this case, there is a problem that the equipment cost increases and the operation becomes complicated.

From the above experimental results, the present inventor found that 400
Consideration was given to combining titanium having good corrosion resistance in a temperature range of 400 ° C. or more with tantalum having good corrosion resistance in a temperature range of 400 ° C. or less. By the way, titanium and tantalum have a disadvantage that the temperature range in which corrosion resistance is good is extremely critically limited, and if the temperature of the reaction vessel deviates from the temperature range in which corrosion resistance is exhibited for some reason, corrosion proceeds significantly. On the other hand, iridium has good corrosion resistance over a temperature range from room temperature to 650 ° C., but has a problem that mechanical processing is difficult.

Therefore, the present inventor has proposed that instead of forming an iridium layer by mechanical processing such as lining, a chemical vapor deposition method (Chemical Vapor Deposition Process,
Hereafter, the idea was to grow an iridium oxide layer (IrO ₂ ) on a titanium layer or a tantalum layer by a CVD method. When the corrosion resistance of the iridium oxide layer was examined by the same experiment as described above, it was confirmed by the experiment that the iridium oxide layer had the same corrosion resistance as the iridium layer. The present inventor has repeatedly conducted experiments to grow an iridium oxide layer on a titanium layer or a tantalum layer by a CVD method, whereby a composite corrosion-resistant layer of a titanium layer and an iridium oxide layer, a tantalum layer and an iridium oxide It was confirmed that a composite corrosion-resistant layer with a layer or a composite corrosion-resistant layer of three layers of a tantalum layer, a titanium layer, and an iridium oxide layer could be formed.

Then, a film thickness of 2500 to 30 is formed on the titanium layer.
The inner wall surface of the reactor was covered with a Ti / IrO ₂ composite corrosion-resistant layer in which a 00 nm iridium oxide layer was laminated by a CVD method, and the same corrosion test as described above was performed. As a result of the corrosion experiment, the corrosion rate was the same as that of iridium in the range from room temperature to 650 ° C., and was, for example, less than plus 2 mm / year at 300 ° C. That is, the Ti / IrO ₂ composite corrosion-resistant layer is
The titanium layer exhibits sufficient corrosion resistance even at 400 ° C. or lower where the corrosion resistance is low, and has almost the same corrosion resistance as iridium in the range from room temperature to 650 ° C.

Further, the present inventor has found that when forming a corrosion resistant layer, rather than forming a corrosion resistant layer with a single corrosion resistant material, for example, an iridium layer, a plurality of corrosion resistant materials having slightly different corrosion resistance, for example, a titanium layer, It was considered that the formation of a composite corrosion-resistant layer composed of a metal and an iridium oxide layer exhibited more reliable corrosion resistance even under unexpected conditions. For example, in the case of pitting-like corrosion, even if pitting occurs in the iridium oxide layer, pitting corrosion rarely progresses to the underlying titanium layer.
In addition, even if an unexpected sudden temperature drop occurs in the reactor, if the titanium layer alone is used, the occurrence and progress of corrosion may be concerned. However, since the iridium oxide layer is provided on the surface layer, no corrosion occurs. Therefore, the present inventor has proposed that the reaction vessel wall, which is easily corroded, is coated with the above-mentioned composite corrosion-resistant layer so that the temperature of the reaction vessel wall is reduced from room temperature to 6
The present invention has been made so that supercritical water treatment of an organochlorine compound can be performed safely over a temperature range up to 50 ° C. and within an allowable limit of the corrosion rate, that is, for a long period of time.

In order to achieve the above object, based on the above-mentioned findings, the supercritical water reactor (hereinafter referred to as the first
Comprises a reactor containing supercritical water,
In a supercritical water reactor in which a liquid to be treated containing an organic chlorine compound is introduced into a reactor and oxidized and decomposed by an oxidizing agent, a temperature controller for controlling the temperature in the reactor to a range of 550 ° C or more and 650 ° C or less. The reactor wall in contact with the liquid to be treated in the reactor is coated with a composite corrosion-resistant layer of a titanium layer made of titanium or a titanium alloy provided on the wall and an iridium oxide layer laminated on the titanium layer. It is characterized by having.

In the present invention, at least the feed flow rate of the liquid to be treated, the feed flow rate of supercritical water, the feed flow rate of make-up water fed into the reactor for generating supercritical water, and the temperature of make-up water By adjusting any of them and setting the reaction temperature to a temperature in the range of 550 ° C. or more and 650 ° C. or less, when the organic chlorine compound is PCB or a PCB-like compound, the treatment liquid generated by oxidative decomposition of the liquid to be treated PCB concentration of 3ppb
It can be: In the present invention, the PCB-like compound is a compound having a chemical structure substantially similar to that of PCB, such as dioxins, chlorobenzene compounds, and chlorophenols. Further, in the present invention, since the wall surface of the reactor is covered with the specified composite corrosion resistant layer, even at the above-mentioned temperature, it is stable for a long time against the corrosive atmosphere due to the generated hydrochloric acid, and the organic chlorine compound such as PCB can be removed. The liquid to be treated can be treated. The thickness of the iridium oxide layer depends on the organochlorine compound to be treated and the concentration of hydrochloric acid in the reactor, but is practically 1500 nm or more.

In a preferred embodiment of the present invention, the reactor wall in contact with the liquid to be treated in the reactor has a tantalum layer made of tantalum or a tantalum alloy provided on the wall, and a titanium or tantalum layer provided on the tantalum layer. A titanium layer composed of a titanium alloy and an iridium oxide layer laminated on the titanium layer;
The layers are coated with a composite corrosion resistant layer. Accordingly, even when the iridium oxide layer is corroded and the titanium layer is corroded due to unexpected circumstances when the temperature of the reactor falls below 400 ° C., the corrosion resistance of the inner tantalum layer can be maintained. That is, it is based on a fail-safe concept required when handling extremely harmful substances such as PCBs. Also,
The temperature calculated based on the temperature distribution in the reactor is 400 ° C
The reactor wall in the region below is covered with a composite corrosion-resistant layer of a tantalum layer made of tantalum or a tantalum alloy provided on the wall and an iridium oxide layer laminated on the tantalum layer. Thereby, the corrosion resistance of the reactor can be further increased.

In the present invention, in order to coat with a composite corrosion-resistant layer, first, a titanium layer or a tantalum layer is coated on a reactor wall formed of a nickel alloy or the like by a known lining method.
Next, an iridium oxide layer is grown on the titanium layer or the tantalum layer by a CVD method. Further, a reactor is formed by processing a coated metal material in which a titanium layer or a tantalum layer is coated on a nickel alloy layer, and then an iridium oxide layer is grown on the titanium layer or the tantalum layer on the reactor wall by a CVD method. . In the present invention, the expression "coating the wall surface with the composite corrosion-resistant layer" includes an embodiment in which the reactor itself is formed of titanium or tantalum, and an iridium oxide layer is laminated on the inner wall surface.

The titanium and titanium alloy used in the present invention are specified by the JIS standard or the ASTM standard. For example, in the JIS standard, pure titanium is a titanium metal or a titanium alloy specified by one to three types of JIS. Are titanium alloys of JIS 11 to 13 specified as titanium-palladium alloys, and Ti-6Al as other titanium alloys.
-4V alloy and Ti-6Al-4VELI alloy.
According to the ASTM standard, pure titanium is ASTM Gra.
titanium metal and titanium alloy specified by de1 to Grade 4 are AST specified as titanium palladium alloy
M Grade 7 and Grade 11 are titanium alloys. Also, Grade 12 and the like can be applied according to the ASTM standard.

The tantalum and the tantalum alloy used in the present invention are specified by the JIS standard or the ASTM standard. In addition to pure tantalum, a tantalum-tungsten alloy or the like can be applied. In the first invention, the titanium layer or the titanium alloy layer and the tantalum layer or the tantalum alloy layer may be lined with the vessel wall of the reactor, or may be built up by welding. Further, it can be joined to the vessel wall of the reactor by HIP processing.

When the reactor is a pressure balanced reactor, the supercritical water reactor according to the present invention (hereinafter referred to as the second invention) comprises a reactor containing supercritical water, and comprises an organic chlorine reactor. A supercritical water reactor in which a liquid to be treated containing a compound is introduced into a reactor and oxidatively decomposed by an oxidizing agent is provided with a temperature controller for controlling the temperature in the reactor to a range of 550 ° C or more and 650 ° C or less. Wherein the reactor is a double cylinder comprising a pressure vessel and a reaction cartridge communicating with the pressure vessel, and supplies the liquid to be treated and the oxidizing agent into the reaction cartridge, and reacts with the pressure vessel. It is configured as a pressure-balanced reactor that supplies a pressure-balancing gas between the cartridge and the reaction cartridge to oxidize and decompose the liquid to be treated with the oxidizing gas in the reaction cartridge. A titanium layer formed is characterized in that it is formed of a composite corrosion-resistant material composed of iridium oxide layer laminated on both surfaces of the titanium layer.

[0037] In the second invention, the temperature control device is configured to control the flow rate of the liquid to be treated, the flow rate of the supercritical water, the flow rate of the make-up water fed to the reactor for generating the supercritical water, By adjusting at least one of the temperature of the makeup water and the temperature of the makeup water, the temperature in the reactor can be controlled in the range of 550 ° C. or more and 650 ° C. or less.

Alternatively, the reaction cartridge may be
A tantalum layer made of tantalum or a tantalum alloy, a titanium layer made of titanium or a titanium alloy provided on both surfaces of the tantalum layer, and a composite corrosion-resistant material formed of an iridium oxide layer stacked on both surfaces of the titanium layer good. Accordingly, even when the iridium oxide layer is corroded and the titanium layer is corroded due to unexpected circumstances when the temperature of the reactor falls below 400 ° C., the corrosion resistance of the inner tantalum layer can be maintained.

The third invention of the present invention is directed to a supercritical water reaction in which a reactor containing supercritical water is provided, and a liquid to be treated containing an organic chlorine compound is introduced into the reactor and oxidatively decomposed by an oxidizing agent. In the apparatus, the temperature in the reactor is set to 550 ° C. or higher and 65
A temperature control device for controlling the temperature within a range of 0 ° C. or lower is provided, and the reactor is a double cylinder comprising a pressure vessel and a reaction cartridge communicating with the pressure vessel, and reacts the liquid to be treated with the oxidizing agent. It is configured as a pressure-balanced reactor for supplying a pressure-balancing gas between the pressure vessel and the reaction cartridge, and oxidizing and decomposing the liquid to be treated in the reaction cartridge, through which the processing fluid flows. A neutralization method comprising a processing fluid flow path, and an alkaline aqueous solution flow path that joins the processing fluid flow path and injects an alkaline aqueous solution into the processing liquid, and neutralizes and quenches the processing fluid to 450 ° C. or less with the alkaline aqueous solution. A quenching unit is provided outside the reactor, and the flow path walls of the processing fluid flow path and the alkaline aqueous solution flow path are stacked on the tantalum layer made of tantalum or a tantalum alloy provided on the wall face and the tantalum layer It is coated with a composite corrosion resistant layer of iridium oxide layer. Further, the processing fluid flow path and the flow path wall surface of the alkaline aqueous solution flow path, a titanium layer made of titanium or a titanium alloy provided on the wall surface, and a tantalum layer made of tantalum or a tantalum alloy provided on the titanium layer,
You may make it cover with the composite corrosion-resistant layer with the iridium oxide layer laminated on the tantalum layer. Further, the neutralization and quenching section of the present invention may be used in combination with the first or second invention.

In a pressure balanced reactor, a neutralization quench may be provided in the annular portion between the pressure vessel of the reactor and the reaction cartridge. In the supercritical water apparatus according to the first and second aspects of the present invention, the reactor forms only a supercritical water area over the entire area of the reactor and does not form a subcritical water area.

[0041]

Embodiments of the present invention will be described below in detail with reference to the accompanying drawings. Embodiment 1 This embodiment is an example of an embodiment of the supercritical water reactor according to the first invention, and FIG. 1 is a flow sheet showing the configuration of the supercritical water reactor of this embodiment. 2 is a sectional view showing details of the reactor. The supercritical water reactor of the present embodiment is an apparatus for treating a liquid to be treated mainly containing PCB by a supercritical water reaction in the presence of supercritical water,
As shown in FIG. 1, as a reactor for performing a supercritical water reaction,
A vertical pressure-resistant closed type reactor 12 is provided, a processing fluid pipe 14 through which a processing fluid flows out from the reactor 12, a cooler 16 for sequentially cooling the processing fluid, and a pressure control valve for controlling the pressure in the reactor 12. And a gas-liquid separator 20 for gas-liquid separation of the processing fluid into gas and liquid.

The supercritical water reactor 10 includes, as a supply system for supplying the liquid to be subjected to the supercritical water reaction to the reactor 12, a liquid to be treated pump 24 whose discharge amount can be adjusted by inverter control or stroke control. , Air compressor 28
The liquid to be treated including the PCB is fed into the reactor 12 through the liquid pipe 22 to be treated, and air is supplied as an oxidizing agent through the air inlet pipe 26 and the liquid pipe 22 to be treated. It is fed into the reactor 12 together with the processing liquid. Although not shown, supercritical water or make-up water for generating supercritical water may be replenished to the reactor 12 if necessary, and a heater for heating the make-up water to a desired temperature may be provided. it can. Further, the supercritical water reactor 10 is provided with a neutralization quenching unit 30 in the processing fluid pipe 14 immediately after exiting the reactor 12, and an alkaline aqueous solution is injected into the processing fluid from the injection pipe 31 to raise the temperature of the processing fluid to 450 ° C.
The neutralization and rapid cooling is preferably performed at 350 ° C. or lower.

The supercritical water reactor 10 includes a temperature controller 32 for controlling the reaction temperature in the reactor 12 to, for example, 550 ° C. by adjusting the flow rate of the liquid to be treated. The temperature control device 32 has a thermometer 34 for measuring the temperature inside the reactor 12, and adjusts the discharge amount of the liquid to be treated pump 24 based on the temperature of the thermometer 34 to adjust the outlet temperature of the liquid to be treated. Thereby, the reaction temperature is controlled to a set temperature in the range of 550 ° C. or more and 650 ° C. or less. The configuration of the temperature control device 32 is not limited to this. For example, by adjusting the supply flow rate of supercritical water, or by adjusting the supply flow rate of makeup water for generating supercritical water, The reaction temperature in the reactor 12 can be controlled in the range of 550 ° C. or more and 650 ° C. or less by adjusting the feed temperature of the reactor.

As shown in FIG. 2, the reactor 12 is formed as a vertical cylindrical container 12a having a mechanical strength against the pressure during supercritical water treatment, for example, 23 MPa. The inner wall of the container 12a has a titanium layer 1 lined with the inner wall.
2b and the titanium layer 12b are covered with a composite corrosion-resistant layer of an iridium oxide layer 12c grown by a CVD method.

The growth process of the iridium oxide layer 12c by the CVD method is performed, for example, as follows. That is, after the titanium layer is degreased in advance with acetone, the titanium layer is oxidized in a steam stream at 700 ° C. to turn the titanium layer surface into titanium oxide. On the other hand, iridium chloride (IrCl ₃ ) was dissolved in amyl alcohol, put into a heating distillation apparatus equipped with a reflux device, and refluxed at a temperature of 90 ° C for 10 hours to obtain 3/4 of the iridium chloride chloride obtained. An iridium coating solution substituted with amyl alcohol is produced. This iridium coating solution is applied to the surface of titanium oxide, air-dried at room temperature, and then forcedly dried at 110 ° C. Then, under an atmosphere containing steam at 700 ° C., 10
Perform a thermal decomposition reaction treatment for a minute. This coating → drying → thermal decomposition reaction treatment was repeated 10 times to form a coating layer of iridium oxide having an apparent film thickness of 3000 nm.

The reactor 12 is connected to the liquid pipe 22 to be treated,
Inflow port 3 through which liquid to be treated and air flow into reactor 12
6 is provided on the upper side, and an outlet 38 connected to the processing fluid pipe 14 and allowing the processing fluid to flow out is provided on the side wall. Titanium layer 12b
Is formed of titanium or a titanium alloy. Instead of the titanium layer 12b, a laminated film of a titanium layer made of titanium or a titanium alloy and a tantalum layer made of tantalum or a tantalum alloy provided between the titanium layer and the container wall may be used.

As shown in FIG. 3, the neutralizing and quenching unit 30 joins the processing fluid flow path 40 through which the processing fluid flows and the injection pipe 31 to the processing fluid flow path 40 to inject the alkaline aqueous solution into the processing fluid. And an aqueous alkaline solution channel 42. In the present embodiment, the processing fluid flow path 40 and the alkaline aqueous solution flow path 42 join in a Y-shape, but may join at a right angle. The flow path walls of the processing fluid flow path 40 and the alkaline aqueous solution flow path 42 are respectively a tantalum pipe wall 44 formed of a tantalum alloy and a titanium pipe formed of titanium or a titanium alloy and provided on the inner periphery of the tantalum wall. A wall 46;
It is formed in a three-layer structure with an iridium oxide layer 47 grown on a titanium tube wall 46 by a CVD method. Note that a nickel alloy steel tube may be inserted into the outer periphery of the tantalum tube wall 44, and the nickel alloy steel tube may be used as the pressure structure.

To form the neutralization and quenching portion 30, first, a columnar body of a tantalum alloy is formed, and then the columnar body is drilled to form a tantalum tube wall 44 having a through passage.
Then, a molten solution of the titanium alloy is poured into the through passage of the tantalum tube wall 44, and is allowed to cool and solidify. Then, HIP processing is performed to ensure the joining between the tantalum alloy phase and the titanium alloy phase. Next, the titanium alloy phase is drilled to form a titanium tube wall 46 and a tantalum tube wall 44 provided outside the titanium tube wall 46. Subsequently, by growing the iridium oxide layer 47 on the titanium tube wall 46 by the CVD method, the processing fluid flow path 40 and the alkaline aqueous solution flow path 42 can be formed. As another manufacturing method, a columnar body of a tantalum alloy is formed, and then the cylinder is drilled to form a tantalum tube wall 44 having a through passage, and a titanium alloy is formed on the titanium tube wall 44 by a welding method or the like. A titanium wall 46 is provided by building up, and then an iridium oxide layer 47 is grown on the titanium tube wall 46 by a CVD method.

Alternatively, the processing fluid flow path 40 and the alkaline aqueous solution flow path 42 of the neutralization and quenching section 30 may be respectively provided with a tantalum tube wall made of pure tantalum or a tantalum alloy and a tantalum tube wall on the tantalum tube wall. And an iridium oxide layer grown by a conventional method. In order to manufacture the neutralization quenching part 30 of another method, for example, first, a cylinder of a tantalum alloy is formed, and then the cylinder is drilled to form a tantalum tube wall having a through passage. Next, an iridium oxide layer is grown on the wall surface of the tantalum tube by the CVD method.

In the present embodiment, by controlling the temperature in the reactor 12 to 600 ° C. by the temperature control device 32, the liquid to be treated including PCB is completely decomposed by the supercritical water treatment, and the PCB of the treatment liquid is decomposed. Can be suppressed to 3 ppb or less. In addition, the composite corrosion-resistant layer of the titanium alloy layer 12b and the iridium oxide layer 12c reliably functions as a corrosion-resistant layer of the reactor 12. Further, even if the temperature in the reactor 12 drops to 400 ° C. or less, the iridium oxide layer 12
Since c is present in the surface layer, the corrosion does not proceed. Since the neutralization and quenching section 30 is covered with the iridium oxide layer 44, corrosion does not proceed. Even if the iridium oxide layer 44 is corroded, in a normal state where the temperature is high, the titanium tube wall 44 maintains corrosion resistance, and conversely, in a state where the temperature unexpectedly drops to, for example, 400 ° C. or less, The titanium tube wall 44 is corroded, but the outer tantalum tube wall 46 maintains corrosion resistance.

Embodiment 2 This embodiment is an example of the embodiment of the supercritical water reactor according to the second invention, and FIG. 4 shows the configuration of the supercritical water reactor of this embodiment. 5 (a) is a cross-sectional view showing details of the reactor, and FIG. 5 (b) is a cross-sectional view taken along line II of FIG. 5 (a) showing the structure of the composite corrosion-resistant material forming the reaction cartridge. It is. 4 and 5, the same parts as those shown in FIGS. 1 to 3 are denoted by the same reference numerals, and description thereof will be omitted. Supercritical water reactor 5 of this embodiment
Numeral 0 is a supercritical water reactor equipped as a reactor with a pressure-balanced reactor composed of a pressure vessel and a reaction cartridge mutually communicating with the reaction vessel. As shown in FIG. 4 and FIG. The configuration of the reactor 52 and the
It has the same configuration as that of Embodiment 1 except that it is built in the inside and that air for pressure balance is fed into the reactor 52.

FIG. 5A shows a pressure-balance type reactor 52.
As shown in the figure, a pressure vessel 54 provided as an outer cylinder,
It is formed as a double cylinder with a reaction cartridge 56 provided as an inner cylinder in the pressure vessel 54, and an inside 58 of the reaction cartridge 56 is configured as a reaction zone for a supercritical water reaction. The pressure vessel 54 is formed as a thick, high-strength steel pressure-resistant cylindrical vessel in order to oppose the reaction pressure, and an annular portion 62 between the pressure vessel 54 and the reaction cartridge 56 is formed as described later. This is an air layer as a pressure balancing gas, not a corrosive atmosphere. On the other hand, as shown in FIG. 5 (b), the reaction cartridge 56 is a thin-walled bottomed cylindrical body 5 made of titanium or a titanium alloy.
6a, and an iridium oxide layer 56b grown by a CVD method on the inner surface (inside 58 side) of the closed bottomed cylindrical body. Reaction cartridge 5
6 and the bottom of the pressure vessel 54 are arranged in the pressure vessel 54 so as to have some gap between them.

An annular portion 62 communicating with the inside of the reaction cartridge 56 through a communication hole 60 is formed between the pressure vessel 54 and the reaction cartridge 56. The annular portion 62 communicates with the air flowing into the reaction cartridge 56 through the nozzle 64. Since air having the same pressure is introduced into the annular portion 62, there is almost no pressure difference between the inside and outside of the reaction cartridge 56, and the pressure between the annular portion 62 and the inside of the reaction cartridge 56 is balanced.
In other words, the pressure vessel 54 has a pressure during supercritical water treatment,
For example, the reaction cartridge 56 has a strength against 23 MPa, and functions as a corrosion-resistant partition wall that partitions the reaction zone by not receiving the internal pressure of the reactor 52.
The air is introduced into the annular portion 62 because the air is a non-corrosive fluid.

The reactor 52 includes a nozzle 64 that penetrates through the pressure vessel 54 and the reaction cartridge 56 and protrudes into the reaction cartridge 56, and a processing fluid from the reaction cartridge 56 to the outside of the reactor 52 through the annular portion 62. A processing fluid conduit 66 to flow out, a neutralizing and quenching portion 68 provided in the processing fluid conduit 66 in the annular portion 62, and an air inlet nozzle 70 for sending air as a pressure balancing gas into the annular portion 62 are provided. ing. The neutralizing and quenching section 68 has the same structure as the neutralizing and quenching section 30 of the first embodiment (see FIG. 3).
Is connected, and an alkaline aqueous solution is injected into the processing fluid, and 45
Neutralization and quenching are performed below 0 ° C. Nozzle 64
Is connected to the liquid pipe 22 to be processed (see FIG. 4), and the processing fluid conduit 66 is connected to the processing fluid pipe 14. Also,
The air inlet nozzle 70 is connected to an air inlet branch pipe 72 (see FIG. 4) branched from the air inlet pipe 26 to introduce air into the annular portion 62, and then through the communication hole 60 to the inside of the reaction cartridge 56. To make a part of the oxidizing agent.

In the present embodiment, similarly to the first embodiment, by controlling the temperature in the reactor 52, more precisely, the reaction cartridge 56 to, for example, 600 ° C. by the temperature control device 32, the processing target including the PCB is controlled. The solution is completely decomposed by supercritical water treatment to reduce the residual amount of PCB in the treatment solution to 3 ppb
It can be suppressed to the following. Further, since the temperature in the reactor 12 is controlled to 600 ° C., the reaction cartridge 56 formed of a titanium alloy and further coated with an iridium oxide layer reliably functions as a corrosion-resistant wall for securing a reaction region. The neutralization and quenching section 68 also functions in the same manner as in the first embodiment,
It has a similar effect.

Embodiment 3 This embodiment is an example of an embodiment of the supercritical water reactor according to the second invention, and FIG. 6A shows the details of the reactor of Embodiment 3 of the present invention. FIG. 6B is a cross-sectional view showing the structure of the composite corrosion-resistant material forming the outer cylinder of the reaction cartridge.
FIG. 6A is a cross-sectional view taken along a line II-II, and FIG. 6C is a cross-sectional view taken along a line II-II in FIG. 6A, illustrating a configuration of a composite corrosion-resistant material forming an inner cylinder of the reaction cartridge. . 6, the same parts and components as those in FIG. 5 are denoted by the same reference numerals, and description thereof is omitted. The supercritical water reactor of the present embodiment includes a reactor 76
Is different from the reactor 52 and has the same configuration as that of Embodiment 2 except that the reaction cartridge has an inner cylinder in the reaction cartridge.

The reactor 76 is, as shown in FIG.
A pressure-balanced reactor comprising a pressure vessel 54 and a reaction cartridge 80 mutually communicating with the pressure vessel 54. The reaction cartridge 80 is housed in the outer cylinder 82 and the outer cylinder 82, and is used for supercritical water reaction. And an inner cylinder 84 having a reaction zone therein. The outer cylinder 82 is a second embodiment.
As shown in FIG. 6B, similarly to the reaction cartridge 56 of FIG.
2a, and the inner surface of the cylindrical body 82a is formed by CVD.
It is covered with an iridium oxide layer 82b grown by the method. The inner cylinder 84 is formed as a bottomed cylindrical body 84a made of titanium or a titanium alloy having an open upper end and an inverted conical bottom, as shown in FIG. 6 (c).
Are covered with an iridium oxide layer 84b grown by the CVD method. Note that the inner cylinder 84 is not limited to this shape, as long as it can reverse the flow of the fluid ejected from the nozzle and moving downward, such as an umbrella having an inverted shape, as long as it can be directed upward. There are no restrictions on its shape.

The liquid to be treated flowing from the nozzle 64 is subjected to supercritical water treatment inside the inner cylinder 84, and flows as a treatment fluid into the annular portion 86 between the outer cylinder 82 and the inner cylinder 84 from the opening at the upper end. Then, it flows down the annular portion 86 to enter the bottom of the outer cylinder 82, and flows out to the processing fluid pipe 14 via the processing liquid conduit 88 connected to the bottom of the outer cylinder 82. The processing fluid conduit 88 in the pressure vessel 54 is provided with a neutralization and quenching section 90 having the same structure as the neutralization and quenching section 30 of the first embodiment (see FIG. 3). Inject the alkaline aqueous solution into the solution,
Neutralization and quenching are performed below 50 ° C. The air inlet nozzle 70 introduces air into the annular portion 62, and then flows the air into the reaction cartridge 80 from the upper end opening of the reaction cartridge 80 through the communication hole 60, thereby forming a part of the oxidizing agent. With the above configuration, the supercritical water reactor of the present embodiment also has the same effects as the second embodiment.

Embodiment 4 This embodiment is an example of an embodiment of the supercritical water reactor according to the second invention, and FIG. 7 is a sectional view showing details of the reactor. 7, the same parts and components as those in FIG. 6 are denoted by the same reference numerals, and description thereof will be omitted. The supercritical water reactor of the present embodiment is different from the supercritical water reactor of Embodiment 3 except that the neutralization and quenching section 92 is provided outside the reactor and the configuration of the reactor 94 is different in relation thereto. It has the same configuration. As shown in FIG. 7, the reactor 94 has the same configuration as the reactor 76 of Embodiment 3 except that a neutralizing and quenching unit 92 is provided outside the reactor. 8
2 is in contact with the bottom of the pressure vessel 54, and the processing fluid pipe 14 penetrates directly through the bottom of the pressure vessel 54 and communicates with the inside of the outer cylinder 82. The neutralization quenching section 92 is provided in the processing fluid pipe 14 so as to be in contact with the bottom of the pressure vessel 54. In the reactor 94 of the present embodiment, the installation of the neutralization quenching part 92 is easier than in the reactor 76 of the third embodiment. Note that, in the reactor 52 of the supercritical water reactor of the second embodiment, the bottom of the reaction cartridge 56 is disposed on the bottom of the pressure vessel 54, and the neutralization and quenching section 68 provided in the annular section 62 is replaced with the drawing. As shown in FIG. 7, a neutralization quenching section 92 may be provided so as to be in contact with the bottom of the pressure vessel 54.

[0060]

According to the present invention, by controlling the reaction temperature in the range of 550 ° C. or more and 650 ° C. or less, the liquid to be treated containing the organic chlorine compound can be rendered harmless by supercritical water treatment. For example, in the case of PCB or a PCB-like compound, the concentration of PCB in the processing fluid can be 3 ppb or less. Further, according to the present invention, by coating the reactor wall or the reaction cartridge with the specified composite corrosion resistant layer, or by forming the specified composite corrosion resistant material, the progress of corrosion of the reactor is suppressed, and the organochlorine compound is suppressed. , For example, PCB or P
A supercritical water reaction apparatus has been realized which can stably treat a liquid to be treated containing a CB-like compound with supercritical water to reduce the PCB concentration in the treatment fluid to 3 ppb or less over a long period of time.

[Brief description of the drawings]

FIG. 1 is a flow sheet showing a configuration of a supercritical water reactor of a first embodiment.

FIG. 2 is a cross-sectional view illustrating details of a reactor according to Embodiment 1.

FIG. 3 is a sectional view of a neutralization and quenching section.

FIG. 4 is a flow sheet showing a configuration of a supercritical water reactor of a second embodiment.

5 (a) is a cross-sectional view showing details of a reactor according to a second embodiment, and FIG. 5 (b) is a line in FIG. 5 (a) showing a configuration of a composite corrosion-resistant material forming a reaction cartridge. It is sectional drawing of II.

6 (a) is a cross-sectional view showing details of a reactor according to Embodiment 3; FIG. 6 (b) shows a configuration of a composite corrosion-resistant material forming an outer cylinder of a reaction cartridge; FIG. 6) is a cross-sectional view taken along line II, and FIG. 6C is a cross-sectional view taken along line II-II in FIG.
FIG.

FIG. 7 is a cross-sectional view illustrating details of a reactor according to a fourth embodiment.

FIG. 8 is a flow sheet showing a configuration of a conventional supercritical water reactor.

FIG. 9 is a cross-sectional view showing a configuration of a conventional pressure balanced reactor.

FIG. 10 is a graph showing the results of a corrosion experiment.

[Explanation of symbols]

Reference Signs List 10 supercritical water reactor of Embodiment 1 12 reactor 12a vertical cylindrical container 12b titanium alloy layer 12c iridium oxide layer 14 processing fluid pipe 16 cooler 18 pressure control valve 20 gas-liquid separator 22 liquid pipe to be treated 24 Liquid pump 26 to be treated 26 Air inlet tube 28 Air compressor 30 Neutralizing and quenching part 31 Injection tube 32 Temperature controller 34 Thermometer 36 Inlet 38 Outlet 40 Processing fluid channel 42 Alkaline aqueous solution channel 44 Tantalum tube wall 46 Titanium Tube wall 47 Iridium oxide layer 50 Supercritical water reactor of Embodiment 2 52 Reactor 54 Pressure vessel 56 Reaction cartridge 56a Thin-walled bottomed cylindrical body formed of titanium or a titanium alloy 56b Iridium oxide layer 58 Reaction cartridge Inside 60 Communication hole 62 Annular part 64 Nozzle 66 Processing fluid conduit 68 Neutralization quenching part 70 Air inlet nozzle 72 Air inlet branch pipe 76 Reactor of Embodiment 3 80 Reaction cartridge 82 Outer cylinder 82a Covered closed cylinder made of titanium or titanium alloy 82b Iridium oxide layer 84 Inner cylinder 84a Made of titanium or titanium alloy Cylinder with bottom 84b Iridium oxide layer 86 Annular part 88 Processing fluid conduit 90 Neutralization quenching part 92 Neutralization quenching part of Embodiment 4 94 Reactor of Embodiment 4 100 Conventional supercritical water reactor 102 Reactor 104 Supercritical water region 106 Virtual interface 108 Subcritical water region 110 Inflow pipe 112 Liquid line to be treated 114 Air line 115 Supercritical water line 116 Neutralizer line 118 Processing fluid line 120 Subcritical water line 122 Subcritical drainage line 130 Pressure Balance type reactor 131 Outer cylinder 132 Reaction cartridge 133 Inlet Le 134 feeding the reaction zone 135 the pressure balance gas inlet 136 annulus 137 upper gap 138 reactor effluent pipe

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B01J 19/00 B01J 19/00 B 301 301A 19/26 19/26 C07B 35/06 C07B 35/06 37 / 06 37/06 61/00 61/00 B C07C 25/18 C07C 25/18 (72) Inventor Tomoyuki Iwamori 1-2-8 Shinsuna, Koto-ku, Tokyo Organo Co., Ltd. (72) Inventor Takayuki Shimamune Tokyo 2-37-5 Minami-Otsuka, Toshima-ku, Tokyo Furuya Metal Co., Ltd. (72) Inventor Takanori Kojima 2-37-5, Minami-Otsuka, Toshima-ku, Tokyo F-Terminal Co., Ltd. F-term (reference) 2E191 BA13 BC01 BD11 4G075 AA37 BA05 BA06 BB05 CA02 CA05 CA62 CA65 CA66 DA01 DA18 EB01 EC01 FA12 FB02 FC09 4H006 AA05 AC13 AC26 BB31 BB49 BC10 BD81 BD83 BD84 BE10 BE30

Claims (10)

[Claims] 1. A supercritical water reactor comprising a reactor containing supercritical water, wherein a liquid to be treated containing an organic chlorine compound is introduced into the reactor and oxidatively decomposed by an oxidizing agent. A temperature control device for controlling a temperature in a range of 550 ° C. or more and 650 ° C. or less, wherein a reactor wall in contact with the liquid to be treated in the reactor has a titanium layer made of titanium or a titanium alloy provided on the wall, and a titanium layer A supercritical water reactor characterized by being coated with a composite corrosion-resistant layer with an iridium oxide layer laminated thereon. 2. A reactor wall in contact with a liquid to be treated in a reactor, comprising: a tantalum layer made of tantalum or a tantalum alloy provided on the wall; and a titanium layer made of titanium or a titanium alloy provided on the tantalum layer. The supercritical water reactor according to claim 1, wherein the supercritical water reactor is coated with three composite corrosion-resistant layers including an iridium oxide layer laminated on a titanium layer. 3. The reactor wall in a region where the temperature calculated based on the temperature distribution in the reactor is less than 400 ° C. is laminated on a tantalum layer made of tantalum or a tantalum alloy provided on the wall and on the tantalum layer The supercritical water reactor according to claim 1, wherein the supercritical water reactor is coated with a composite corrosion-resistant layer with the iridium oxide layer formed. 4. A supercritical water reactor comprising a reactor containing supercritical water, wherein a liquid to be treated containing an organic chlorine compound is introduced into the reactor and oxidatively decomposed by an oxidizing agent. A temperature control device for controlling a temperature in a range of 550 ° C. or more and 650 ° C. or less, wherein the reactor is a double cylinder of a pressure vessel and a reaction cartridge mutually communicating with the pressure vessel; , An oxidizing agent is supplied into the reaction cartridge, and a pressure-balancing gas is supplied between the pressure vessel and the reaction cartridge to constitute a pressure-balanced reactor for oxidatively decomposing the liquid to be treated in the reaction cartridge. At least the inner wall of the reaction cartridge is made of a composite corrosion-resistant material composed of a titanium layer made of titanium or a titanium alloy and an iridium oxide layer laminated on the titanium layer. Supercritical water reactor characterized. 5. The reaction cartridge according to claim 1, wherein at least an inner wall surface of the reaction cartridge comprises a tantalum layer made of tantalum or a tantalum alloy;
The super-corrosion material according to claim 4, wherein the composite material is formed of a composite corrosion-resistant material including a titanium layer formed of titanium or a titanium alloy provided on a tantalum layer, and an iridium oxide layer stacked on the titanium layer. Critical water reactor. 6. A supercritical water reactor comprising a reactor containing supercritical water, wherein a liquid to be treated containing an organic chlorine compound is introduced into the reactor and oxidatively decomposed by an oxidizing agent. A temperature control device for controlling a temperature in a range of 550 ° C. to 650 ° C .; a processing fluid flow path through which the processing fluid flows; and an alkaline aqueous solution flow path that joins the processing fluid flow path and injects the alkaline aqueous solution into the processing fluid. And treating the solution with an alkaline aqueous solution
A neutralization and quenching section for neutralizing and quenching to 50 ° C or less is provided outside the reactor, and the flow path wall of the processing fluid flow path and the alkaline aqueous solution flow path is made of tantalum or a tantalum alloy provided on the wall. A supercritical water reactor characterized by being coated with a composite corrosion-resistant layer of a layer and an iridium oxide layer laminated on a tantalum layer. 7. A supercritical water reactor comprising a reactor containing supercritical water, wherein a liquid to be treated containing an organic chlorine compound is introduced into the reactor and oxidatively decomposed by an oxidizing agent. A temperature control device for controlling a temperature in a range of 550 ° C. to 650 ° C .; a processing fluid flow path through which the processing fluid flows; and an alkaline aqueous solution flow path that joins the processing fluid flow path and injects the alkaline aqueous solution into the processing fluid. And treating the solution with an alkaline aqueous solution
A neutralization and quenching unit for neutralizing and quenching to 50 ° C. or less is provided outside the reactor, and the processing fluid flow path and the alkaline aqueous solution flow path wall face are formed of titanium or titanium alloy provided on the wall face. A supercritical water reactor characterized by being coated with a composite corrosion-resistant layer of a layer, a tantalum layer made of tantalum or a tantalum alloy provided on a titanium layer, and an iridium oxide layer stacked on the tantalum layer . 8. A supercritical water reactor comprising a reactor containing supercritical water, wherein a liquid to be treated containing an organic chlorine compound is introduced into the reactor and oxidatively decomposed by an oxidizing agent. A temperature control device for controlling a temperature in a range of 550 ° C. or more and 650 ° C. or less, wherein the reactor is a double cylinder of a pressure vessel and a reaction cartridge mutually communicating with the pressure vessel; An oxidizing agent is supplied into the reaction cartridge, and a pressure-balancing gas is supplied between the pressure vessel and the reaction cartridge to constitute a pressure-balanced reactor for oxidatively decomposing the liquid to be treated in the reaction cartridge. A processing fluid flow path through which the processing fluid flows, and an alkaline aqueous solution flow path that joins the processing fluid flow path and injects an alkaline aqueous solution into the processing fluid.
A neutralizing and quenching unit for neutralizing and quenching to 50 ° C or lower is provided in an annular portion between the pressure vessel of the reactor and the reaction cartridge. A supercritical water reactor characterized by being coated with a composite corrosion-resistant layer of a tantalum layer made of tantalum or a tantalum alloy provided on a tantalum layer and an iridium oxide layer laminated on the tantalum layer. 9. A supercritical water reactor comprising a reactor containing supercritical water, wherein a liquid to be treated containing an organic chlorine compound is introduced into the reactor and oxidatively decomposed by an oxidizing agent. A temperature control device for controlling a temperature in a range of 550 ° C. or more and 650 ° C. or less, wherein the reactor is a double cylinder of a pressure vessel and a reaction cartridge mutually communicating with the pressure vessel; An oxidizing agent is supplied into the reaction cartridge, and a pressure-balancing gas is supplied between the pressure vessel and the reaction cartridge to constitute a pressure-balanced reactor for oxidatively decomposing the liquid to be treated in the reaction cartridge. A processing fluid flow path through which the processing fluid flows, and an alkaline aqueous solution flow path that joins the processing fluid flow path and injects an alkaline aqueous solution into the processing fluid.
A neutralizing and quenching unit for neutralizing and quenching to 50 ° C or lower is provided in an annular portion between the pressure vessel of the reactor and the reaction cartridge. Is provided with a titanium layer made of titanium or a titanium alloy, a tantalum layer made of tantalum or a tantalum alloy provided on the titanium layer, and a composite corrosion-resistant layer of an iridium oxide layer stacked on the tantalum layer. A supercritical water reactor. 10. A container configured to contain a fluid containing an aqueous hydrochloric acid solution at a temperature of 700 ° C. or lower, or a reactor configured to react a reaction fluid containing an aqueous hydrochloric acid solution in a temperature range of 700 ° C. or less, A vessel wall in contact with the fluid or the reaction fluid of the vessel, a titanium layer made of titanium or a titanium alloy provided on the wall,
A container characterized by being coated with a composite corrosion-resistant layer with an iridium oxide layer laminated on a titanium layer.