JP2002102671A - High pressure corrosion resistant reaction vessel, treatment apparatus, and method for corrosion resistant treatment of the apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an inexpensive high pressure corrosion resistant reaction vessel having excellent corrosion resistance in an environment of a high temperature and a high pressure and high strength, a treatment apparatus, and a method for the corrosion resistant treatment of the apparatus in which the corrosion resistance and durability of the coating layer of Ti or a Ti alloy are improved. SOLUTION: In the reaction vessel 1 which has a container main body 3 and a lid 4 and can shut up a material to be treated in it, coating layers 8a and 8b of a coating material are formed on the surface of a contact place with which the material in the vessel can be contacted, and a pressure adjusting means for adjusting the pressure of a clearance part 10 formed between the main body 3 and the coating layers 8a and 8b and the pressure of the vessel is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-pressure corrosion-resistant reaction vessel for treating a material to be treated using a liquid under supercritical or subcritical conditions as a reaction medium, a processing apparatus having the high-pressure corrosion-resistant reaction vessel, and a processing apparatus. The present invention relates to a corrosion-resistant treatment method.

[0002]

2. Description of the Related Art Reactors such as waste treatment equipment that operate in a high-temperature and high-pressure environment are susceptible to corrosion in a high-pressure vessel that actually performs decomposition treatment and the like. Is required. Examples of the material having high corrosion resistance include noble metals such as titanium, tantalum, and platinum.

[0003] Although the above-mentioned noble metal materials can obtain high corrosion resistance,
Since high-temperature strength cannot be sufficiently obtained, it has been difficult to form a high-pressure container from only a noble metal material and put the high-pressure container into practical use.

Therefore, a method has been proposed in which a high-strength stainless steel or nickel-based alloy is used as a pressure-resistant material for the container body, and a coating made of a highly corrosion-resistant material is formed as a coating on the container body. In addition, the high pressure vessel itself
A method has been proposed in which a highly corrosion-resistant material is used as a double container and an inner container of a double container.

For example, Japanese Patent Application Laid-Open No. 9-85075 discloses a high-pressure reaction method and a high-pressure reaction apparatus, and discloses a high-pressure reaction apparatus and a high-pressure reaction method using a double vessel. Japanese Patent Application Laid-Open No. 2000-189781 discloses a high-pressure processing apparatus, a method for supplying the high-pressure processing apparatus, and a method for protecting the high-pressure processing apparatus.
No. 7160 discloses a pressure vessel, a high-pressure test apparatus, and a high-pressure processing apparatus.

In the above-mentioned conventional high-pressure container comprising a double container, the pressure in the gap between the inner container and the outer container and the pressure in the inner container are adjusted, that is, a part of the inner container is connected to the gap. A method has been proposed in which the pressure is adjusted by doing so, and excessive pressure is not applied to the inner container.

[0007]

However, the above method has a problem in that the corrosive substance in the inner container penetrates into the gap by diffusion, thereby corroding the outer container.

Further, even when a coating made of a material having high corrosion resistance is formed on the inner surface of the container, it is necessary to replace the coating every several years. However, when used for a long time under high temperature and high pressure, the coating material is pressed against the container body and becomes tightly adhered or adhered, making it difficult to replace the coating material, shortening the product life, As a result, there have been problems such as an increase in product cost.

The present invention has been made to solve the above problems, and has excellent corrosion resistance and strength characteristics in a high-temperature and high-pressure environment, and a coating material formed inside a container can be periodically replaced. An object of the present invention is to obtain a high-pressure corrosion-resistant reaction vessel and a processing apparatus to which the high-pressure corrosion-resistant reaction vessel is applied.

In addition, Ti or Ti which is a high corrosion resistant material is used.
It is an object of the present invention to provide a method of treating a coating apparatus in which the coating layer made of an alloy has improved corrosion resistance and durability.

[0011]

Means for Solving the Problems As a result of various studies to achieve the above object, the present inventors have made a reaction vessel in which at least a part of a vessel body and a lid are covered with a metal or alloy having higher corrosion resistance, The present invention has been completed based on the idea that the adhesion between the container body and the coating material can be prevented by adjusting the pressure between the main body, the coating material and the gap, and the pressure inside the container body.

That is, the high-pressure corrosion-resistant reaction container of the present invention is a high-pressure corrosion-resistant reaction container having a container body and a lid, wherein the material to be treated can be hermetically sealed inside the container. A coating layer made of a coating material is formed on the surface of the contact portion which can be provided, and pressure adjusting means for adjusting the pressure in the gap formed between the container body and the coating layer and the pressure inside the container is provided. It is characterized by the following.

According to the present invention, since the pressure adjusting means is provided, the pressure in the gap between the container body and the covering material and the pressure in the container body can be adjusted to the same level, and the close contact between the container body and the covering material can be prevented. In addition, the replacement of the coating material can be easily performed periodically.

In the above-mentioned high-pressure corrosion-resistant reaction vessel, the pressure adjusting means is a pressure supply pipe having one end connected to the inside of the vessel and the other end connected to the gap.

In the present invention, since the pressure supply pipe is provided between the coating material (lining material) and the container main body from the inside of the reaction container through the outside of the container main body, the same pressure as the inside of the container is provided between the container main body and the coating material. By applying the pressure, the close contact between the container body and the covering material can be prevented. In addition, by forming a thin film of the high-pressure fluid between the container body and the coating material by adjusting the pressure by the pressure adjusting means, adhesion between the container body and the coating material can be prevented.

In the high-pressure corrosion-resistant reaction vessel, the pressure supply pipe may include one or both of a filter and an ion exchange resin. In this case, by providing one or both of the filter and the ion exchange resin in the pressure supply pipe, the corrosive reaction liquid is removed by the filter or the ion exchange resin, thereby preventing the corrosive reaction liquid from coming into contact with the container body. it can.

In the above high-pressure corrosion-resistant reaction vessel, the pressure supply pipe may include a cooler. In this case, heating of the pressure supply pipe can be prevented by providing the pressure supply pipe with a cooler.

The high-pressure corrosion-resistant reaction vessel according to the present invention comprises a container body and a lid, and is configured so that a material to be treated can be sealed inside the vessel. A coating layer made of a coating material is formed on the surface of the contact portion which can be formed, and an isolation layer made of an anti-adhesion material is provided between the container body and the coating layer.

According to the present invention, since an isolation layer made of an anti-adhesion material is provided between the coating material and the container body to prevent the adhesion between the container body and the coating material, the coating material can be easily replaced. .

In the high-pressure corrosion-resistant reaction vessel, the isolation layer may be an oxide layer formed by oxidizing the surface of the coating material. In this case, by performing an oxidation treatment on the surface of the coating material in the atmosphere or a high-temperature gas containing oxygen to form an isolation layer that is an oxide layer, adhesion between the container body and the coating material can be prevented.

In the above-mentioned high-pressure corrosion-resistant reaction vessel,
At least one of the container body and the lid is made of an alloy selected from carbon steel, stainless steel, a nickel (Ni) -based alloy, and a titanium (Ti) alloy.

Further, in the high-pressure corrosion-resistant reaction container, a metal packing may be provided at a contact portion between the container main body and the lid.

In the above-mentioned high-pressure corrosion-resistant reaction vessel, the coating material is made of Ti or an alloy containing Ti, and the contact portion with the packing is made of a high-strength material containing molybdenum (Mo), vanadium (V) or aluminum (Al). It is made of a titanium alloy.

In the present invention, by using Ti or an alloy containing Ti as a coating material and using a high-strength Ti alloy containing Mo, V or Al in a contact portion with the packing, deformation of the contact surface of the packing is prevented, Even when used repeatedly, leakage from the packing can be prevented.

In the above high-pressure corrosion-resistant reaction vessel, the coating material is made of Pt or an alloy containing Pt, and a contact portion with the packing is made of a high-strength Pt alloy containing rhodium (Rh) or iridium (Ir). It is characterized by.

In the present invention, Pt or an alloy containing Pt is used as a coating material, and Rh or Ir
By using a high-strength Pt alloy containing, deformation of a contact portion with the packing can be prevented, and leakage from the packing can be prevented even when repeatedly used.

In the above high-pressure corrosion-resistant reaction vessel, two or more metal packings are concentrically arranged at a fixed distance from each other at a contact portion between the vessel body and the lid, and a space between each packing is provided. It is characterized by having a leak detecting means for detecting a leak in response to a pressure change.

In the present invention, by providing the leak detecting means, even when a leak occurs in the packing portion, it can be immediately detected. Therefore, according to the processing apparatus provided with the high-pressure corrosion-resistant reaction vessel, the processing apparatus can be stopped based on the detection of the leak detection means, and the leakage of the reactant from the outer packing can be prevented. Can operate the processing device.

The leak detecting means may be composed of, for example, a conductive tube connected between each packing and a leak detector provided in the conductive tube and detecting a leak in response to a pressure change.

The processing apparatus of the present invention comprises a high-pressure corrosion-resistant reaction vessel for decomposing a material to be treated using high-temperature high-pressure water and an oxidizing agent under supercritical conditions as a reaction medium, and supplies the material to be treated into the high-pressure corrosion-resistant reaction vessel. Material supply means to be processed, a reaction medium supply means for supplying the reaction medium into the high-pressure corrosion-resistant reaction vessel, and a processing product discharge means for discharging the processing product generated by the decomposition treatment from the inside of the high-pressure corrosion-resistant reaction vessel. Wherein the high-pressure corrosion-resistant reaction vessel comprises a container body and a lid, and is configured to be able to seal the material to be treated inside the container, and to the surface of a contact portion where the material to be treated inside the container can come into contact. A coating layer made of a coating material is formed, and pressure adjusting means for adjusting a pressure in a gap formed between the container body and the coating layer and a pressure in the container is provided.

In the above processing apparatus, the reaction medium supply means includes a means for supplying high-temperature and high-pressure water, and a means for supplying an oxidizing agent, and the pressure adjustment means branches off from the means for supplying the high-pressure and high-pressure water. And a pressure supply pipe connected to a gap between the container body and the coating layer.

In the above processing apparatus, the reaction medium supply means includes means for supplying high-temperature and high-pressure water, and means for supplying oxygen gas as an oxidant. A pressure supply pipe is provided which branches off from a means for supplying gas and is connected to a gap between the container body and the coating material.

Further, in the above processing apparatus, the high-pressure corrosion-resistant reaction vessel may be the high-pressure corrosion-resistant reaction vessel according to any one of claims 1 to 7.

According to a further aspect of the present invention, there is provided a method for treating a corrosion-resistant coating of a processing apparatus, comprising: a coating layer coated on at least a part of a contact portion of the processing apparatus which is in contact with a material to be processed. The method according to claim 1, wherein the liquid material containing a noble metal is circulated in the processing apparatus when the coating layer is made of Ti or an alloy containing Ti.

In the present invention, the corrosion resistance of the coating layer formed at the contact portion that comes into contact with the material to be treated can be improved by flowing the liquid containing the noble metal through the treatment device. Examples of the contact portion include a container body, a lid, and an inner surface of a pipe constituting a liquid contact portion of the device.

In the present invention, the liquid containing the noble metal is circulated in the processing apparatus. However, the liquid may be filled inside the processing apparatus for a certain period of time. As the liquid containing a noble metal, for example, a solution or suspension of a compound containing a noble metal may be used.

[0037]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a high-pressure corrosion-resistant reaction vessel, a processing apparatus and a method for performing a corrosion-resistant treatment of a processing apparatus according to the present invention will be described.
This will be described with reference to FIGS.

First Embodiment (FIGS. 1 to 3) In this embodiment, a high-pressure corrosion-resistant reaction vessel will be described with reference to FIGS.

FIG. 1 is a schematic sectional view showing the structure of a high-pressure corrosion-resistant reaction vessel.

As shown in FIG. 1, a high-pressure corrosion-resistant reaction vessel 1
Is provided with a container body 3 having a heater 2 on the outer peripheral surface, and a lid 4 for the container body provided on the upper part of the container body 3, and a contact portion 5 between the container body 2 and the lid 4 is provided with a metal. A packing 6 is provided, and an outer peripheral side of the metal packing 6 is fastened by a holding bolt 7 to seal the inside of the high-pressure corrosion-resistant reaction vessel 1.

The container body 3 and the lid 4 are made of a Ni-based alloy, and the container body 3 which is a contact portion with which the material to be treated comes into contact.
And coating layers 8a and 8b made of a Ti alloy are formed on the inside of the cover 4 and on the bottom side of the lid 4, respectively.

The high-pressure corrosion-resistant reaction vessel 1 is connected to a pressure supply pipe 9 as pressure adjusting means. One end of the pressure supply pipe 9 is connected to the upper part of the lid 4 and communicates with the inside of the reaction vessel 1,
The other end of the pressure supply pipe 9 is connected to an upper position on the side surface of the reaction vessel 1 and communicates with the gap 10 between the reaction vessel 1 and the coating layer 8a so that pressure is supplied from the inside of the reaction vessel 1 to the gap 10. It has become. The pressure supply pipe 9 is provided with an ion exchange column 11 and a filter 12.

FIG. 2 shows a high-pressure corrosion-resistant reaction vessel 1 shown in FIG.
Is a high-pressure corrosion-resistant reaction vessel 13 in which cooling units 14a and 14b are provided before and after the ion exchange resin column 11 of the pressure supply pipe 9, respectively. The reaction vessel 13 includes the filter 1 shown in FIG.
2 was not installed.

FIG. 3 is a schematic cross-sectional view of a high-pressure corrosion-resistant reaction vessel 15 provided with a leak detecting means for detecting leakage of an object to be treated in the high-pressure corrosion-resistant reaction vessel 1. The description of the same parts as those of the high-pressure corrosion-resistant reaction vessel 1 shown in FIG. 1 is omitted.

As shown in FIG. 3, a metal packing 16a is provided on the contact portion 5 between the container body 3 and the lid 4 on the inner peripheral side and the outer peripheral side of the holding bolt 7 with reference to the position of the holding bolt 7. , 16b. That is, when the present reaction vessel 15 is viewed from above, the metal packings 16a and 16b are arranged concentrically with a certain distance therebetween. A supply pipe 17 is connected between the metal packings 16a and 16b, and a leak detector 18 responsive to a pressure change is connected to the supply pipe 17. The high-pressure corrosion-resistant reaction vessel 15 shown in FIG.
Are provided, but the number of packings is not limited to two, and two or more packings may be provided.

The high-pressure corrosion-resistant reaction vessel 1, 1 of this embodiment
In Nos. 3 and 15, the thermal expansion coefficient of the Ti alloy is about half that of the Ni-based alloy.
Tend to form a gap between However, during operation of the high-pressure corrosion-resistant reaction vessels 1, 13, and 15, the reaction vessels 1, 1 and 1
The insides of the coating layers 3 and 15 become high pressure, and the coating layer 8a is expanded by the pressure to be in a state where plastic deformation occurs. On the other hand, when the high-pressure corrosion-resistant reaction vessels 1, 13, 15 are cooled, the shrinkage of the vessel body 3 is larger than that of the coating layer 8a.
And the coating layer 8a are in close contact with each other, making it difficult to pull out the coating layer 8a.

According to the present embodiment, the reaction vessels 1, 13,
15, the pressure supply pipe 9 is provided between the coating layer 8 a and the container body 3 through the outside of the reaction vessels 1, 13, 15 from the inside, so that the reaction vessels 1, 1
By applying a pressure equal to the inside of the inside 3, 15, it is possible to prevent the coating layer 8 a from being pushed out toward the outside, that is, toward the container body 3. Therefore, adhesion between the container body 3 and the coating layer 8a can be prevented, and even if the coating layer 8a is deteriorated due to corrosion or the like, the coating material can be easily replaced to form a new coating layer.

According to the present embodiment, the reaction vessels 1 and
Even if the corrosive contents are diffused from the insides 13 and 15, the corrosive contents can be removed because the ion exchange column 11 and the filter 12 are provided in the pressure supply pipe 9. Therefore, it is possible to prevent the corrosive contents from coming into contact with the reaction vessels 1, 13, and 15, and to prevent the occurrence of corrosion in the reaction vessels 1, 13, and 15.

Further, as shown in FIG. 2, since the coolers 14a and 14b are provided before and after the ion exchange resin column 11, the ion exchange resin column 11 is heated by heat conduction, and deterioration due to heating can be prevented.

Further, by employing the structure of the reaction vessel 15 shown in FIG. 3, when leakage occurs around the metal packings 16a and 16b, the leakage can be immediately detected. Therefore, when the high-pressure corrosion-resistant reaction vessel 15 described in the present embodiment is applied to a processing apparatus, the processing apparatus can be stopped immediately based on the detection signal of the leak detector 18. Further, since the metal packings 16a and 16b are provided at the contact portion 5 between the container body 3 and the lid 4, external leakage of the reactant in the reaction container 15 is prevented, and as a result, safe operation can be performed.

In this embodiment, a high-pressure corrosion-resistant reaction vessel without the ion-exchange column 11, filter 12, and coolers 14a and 14b provided in the pressure supply pipe 9 may be used. It may be a reaction vessel. Further, the leak detector 18 shown in FIG.
May be provided as high-pressure corrosion-resistant reaction vessels provided in the high-pressure corrosion-resistant reaction vessels 1 and 13 shown in FIGS. 1 and 2, and are not limited to the configuration shown in the present embodiment.

Second Embodiment (FIG. 4) In this embodiment, a high-pressure corrosion-resistant reaction vessel different from the first embodiment will be described.

FIG. 4 is a schematic sectional view of a high-pressure corrosion-resistant reaction vessel.

As shown in FIG. 4, the high-pressure corrosion-resistant reaction vessel 1
Reference numeral 9 denotes a container main body 20 capable of withstanding pressure, and a container main body 20 installed on the upper part of the container main body 20 via a metal packing 21.
And a lid for use. The lid includes an inner lid 22 and an outer lid 24 connected to the upper part of the inner lid 22 via a bush 23.

A coating layer 25a made of a coating material is provided on the inside of the container body 20, the bottom surface of the inner lid 22, and the bush 23.
25b and 25c are formed, and the container body 20 is removed from the corrosive environment.
And the inner lid 22 is protected. Further, the container body 20
An insulating layer 26 made of a sheet of graphite wool is formed between the coating layer 25a and the coating layer 25a as an anti-adhesion material.

According to the present embodiment, the graphite wool sheet forming the isolation layer 26 serves as a cushioning material, and
This prevents adhesion between the coating layer 25 and the coating layer 25a, and enables the coating material to be easily replaced even when the coating layer 25a is deteriorated due to corrosion or the like, thereby forming a new coating layer. In the present embodiment, a graphite wool sheet is used as the anti-adhesion material, but the anti-adhesion material is not limited to this. For example, a case where a metal sheet or the like to which ceramic powder is applied may be applied. Further, the surface of the coating layers 25a, 25b, 25c is subjected to an oxidation treatment to form an oxide film, or the container body 20 and the coating layers 25a, 25c are formed.
By inserting a material capable of preventing adhesion between the container body 20 and the coating layers 25a, 25b, 25c.
Can be prevented.

Third Embodiment (FIG. 5) In the present embodiment, a study was made on an alloy material applied to a high-pressure corrosion-resistant reaction vessel. The configuration of the high-pressure corrosion-resistant reaction vessel is substantially the same as that of FIG. 4 shown in the second embodiment, and the description of the same portions will be omitted.

FIG. 5 is a schematic cross-sectional view of the high-pressure corrosion-resistant reaction vessel. As for the coating layer 25a at the contact portion between the vessel body 20 and the inner lid 22 shown in FIG. A high strength Ti-15Mo-5Zr-3Al alloy was used. Note that a Ni-based alloy is used as a material for the container body 20 and the lids 22, 24, and the coating layers 25a, 25b,
As for 25c, a Ti-0.2Pd alloy having high corrosion resistance was used.

Since a large compressive stress is applied to the contact surface between the metal packing 21 and the coating layer 25a at the contact portion between the container body 20 and the inner lid 22, Ti-0, which has high corrosion resistance but low high-temperature strength, has high corrosion resistance. The 2Pd alloy is apt to be deformed and difficult to use repeatedly.

Accordingly, by applying a Ti-15Mo-5Zr-3Al alloy having excellent high-temperature strength to the contact surface with the metal packing 21 to which a large compressive stress is applied as in the present embodiment, the deformation amount is small. Repeated use after open inspection is now possible.

Incidentally, a Ti-15Mo-5Zr-3Al alloy having high high-temperature strength may be applied to the whole of the coating layers 25a, 25b and 25c. Since the product form is limited and expensive, it is reasonable to apply the Ti alloy only to the contact surface with the metal packing 21. Also, Ti-6Al-4V alloys and the like are known as high-strength Ti alloys, but these are generally inferior in corrosion resistance to Ti-15Mo-5Zr-3Al alloys, so their use is restricted in highly corrosive environments. .

Further, when used in a highly corrosive environment, Pt is preferably used as the coating material. When Pt is applied as the coating material, it is effective to use a Pt-Rh alloy or a Pt-Ir alloy having high hardness on the contact surface with the metal packing 21.

Therefore, according to the present embodiment, the container body 2
0 and the lids 22 and 24 are coated with a coating material.
By coating the coating material on the bush 23 which may come into contact with the reactant, the corrosion resistance of the high-pressure corrosion-resistant reaction vessel 19 can be further improved.

Fourth Embodiment (FIGS. 6 and 7) In this embodiment, a liquid waste decomposition apparatus for decomposing liquid waste will be described as a specific example of a processing apparatus. The liquid waste decomposing apparatus is an apparatus for decomposing liquid waste using high-temperature and high-pressure water under supercritical or subcritical conditions as a reaction medium, and the configuration of the present liquid waste decomposing apparatus is schematically shown in FIG. .

As shown in FIG. 6, the liquid waste decomposing device 2
Reference numeral 7 denotes a high-pressure corrosion-resistant reaction vessel 28 for decomposing liquid waste as a material to be treated using high-temperature high-pressure water and an oxidizing agent under supercritical conditions as a reaction medium, and supplies the liquid waste into the high-pressure corrosion-resistant reaction vessel 28. Waste supply means 29, reaction medium supply means 30 for supplying the reaction medium into the high-pressure corrosion-resistant reaction vessel 28, and decomposition product for discharging the decomposition products generated by the decomposition treatment of the liquid waste from the high-pressure corrosion-resistance reaction vessel 28 And an object discharging means 31.

The high-pressure corrosion-resistant reaction container 28 includes a container body 33 having a heater 32 on the outer peripheral surface thereof, and a lid 34 for the container body 33 provided on the upper part of the container body 33. A coating layer 35 made of a coating material is formed on the bottom surface side of 34. The container body 33 and the lid 34 are made of a Ni-based alloy, and the covering material is made of a Ti alloy.

The contact portion between the container main body 33 and the lid 34 is connected via a metal packing 36 to the outer periphery of the metal packing 36 with fastening bolts 37 so that the inside of the reaction container 28 can be sealed. ing.

The waste supply means 29 includes a waste tank 38 for storing liquid waste, and a waste supply pipe 39 connected to the waste tank 38. A pump 40 and a check valve 41 for preventing backflow of the liquid waste are provided.

The reaction medium supply means 30 includes means 30a for supplying high-temperature and high-pressure water under supercritical (or subcritical) conditions, and means 30b for supplying an oxidizing agent.

The means 30a for supplying high-temperature and high-pressure water includes a pure water tank 42 for storing pure water, and a pure water supply pipe 43 connected to the pure water tank 42.
Is provided with a pure water pump 44, a check valve 45 for preventing backflow of the pure water, and a preheater 46 for heating the pure water. Further, a pure water supply pipe 43 branches off and is connected to a pressure supply pipe 47 as pressure supply means at a stage subsequent to the pure water pump 44. The pressure supply pipe 47 is connected to an upper position on the side surface of the reaction vessel 28. It is connected to a gap 48 between the reaction vessel 28 and the coating layer 35 a, so that the pressure inside the reaction vessel 28 is supplied to the gap 48 via a pressure supply pipe 47.

The means 30b for supplying an oxidizing agent is provided with an oxidizing agent tank 50 for storing an oxidizing agent such as a hydrogen peroxide solution.
And the pure water supply pipe 4 connected to the oxidant tank 50.
An oxidant supply pipe 51 connected to the fuel cell 3 and a pump 52 are provided.

The decomposition product discharging means 31 is provided with a discharge pipe 53 for discharging decomposition products from the high-pressure corrosion-resistant reaction vessel 28.
And a decomposition product storage tank 54 connected to the discharge pipe 53. The discharge pipe 53 is provided with a cooler 55 for cooling the decomposition products and a pressure holding valve 56.

In the high-pressure corrosion-resistant decomposition device 27 having the above configuration,
The water in the pure water tank 42 and the hydrogen peroxide solution in the oxidant tank 50 are pressurized by the pure water pumps 44 and 52 and passed through the preheater 46 to cause the high-pressure corrosion-resistant reaction vessel 2
8. The liquid waste in the waste tank 38 is pressurized by the waste supply pump 40 without heating,
It is transferred into the reaction vessel 28. On the other hand, the reaction product generated by the decomposition treatment of the liquid waste is discharged from the high-pressure corrosion-resistant reaction vessel 28 through the discharge pipe 53, cooled by the cooler 55, and collected in the decomposition product storage tank 54.

FIG. 7 is a schematic diagram showing the structure of a liquid waste decomposing apparatus obtained by improving the reaction medium supply means 30 of the liquid waste decomposing apparatus 27 shown in FIG. As a means 30b for supplying the oxidant of the supply means 30, a decomposition apparatus for supplying oxygen gas instead of an oxidant such as hydrogen peroxide solution. The description of the same parts as in FIG. 6 is omitted.

As shown in FIG. 7, the means 30b for supplying the oxidizing agent is such that oxygen gas is filled in the oxygen gas cylinder 57, the oxygen gas supply pipe 58 is connected to the oxygen gas cylinder 57, and the oxygen gas supply pipe 58 Is connected to a pure water supply pipe 43 in the preceding stage of the preheater 46. In addition, a compressor 59 is provided in the oxygen gas supply pipe 58, and the oxygen gas supply pipe 58
Are branched and a pressure supply pipe 60 is connected. further,
The pressure supply pipe 60 is connected to an upper position on the side surface of the reaction vessel 28, communicates with the gap 48 between the reaction vessel 28 and the coating layer 35 a, and supplies oxygen gas to the gap 48.

In the liquid waste decomposing apparatus having the above structure, first, pure water in the pure water tank 42 is pressurized by the pure water pump 44 and oxygen gas is pressurized by the compressor 59, so that the oxygen gas is dissolved in the pure water. After heating through the preheater 36, the mixture is supplied into the reaction vessel 28. Further, the liquid waste in the waste tank 38 is transferred into the reaction vessel 28 after being pressurized by the waste supply pump 40 without heating.
The decomposition products generated by the decomposition treatment in the reaction vessel 28 are cooled by the cooler 55 and then discharged to the decomposition product storage tank 54 through the pressure holding valve 56.

According to the present embodiment, as shown in FIG.
By branching the pure water supply pipe 43 and providing a pressure supply pipe 47 to supply pressure to the gap 48, the pressure in the gap 48 between the coating layer 35a and the container body 33 is equal to the pressure inside the reaction vessel 28. Since the close contact between the container body 33 and the coating layer 35b can be prevented, the coating material can be easily replaced even when the coating layer 35b is deteriorated due to corrosion or the like.

As shown in FIG. 7, when oxygen gas is used as the oxidizing agent, the oxygen gas supply pipe 58 is branched and a pressure supply pipe 60 is connected to the oxidation gas supply pipe 58 at a stage subsequent to the compressor 59. By doing so, oxygen gas can be supplied to the gap 48 between the container main body 33 and the coating layer 35b, so that the same effect as when pressure is supplied in the liquid waste decomposer 27 shown in FIG. 6 can be obtained.

Fifth Embodiment (FIG. 8) In this embodiment, a liquid waste decomposing apparatus having another embodiment will be described.

FIG. 8 is a schematic diagram of a liquid waste decomposition apparatus. The description of the same parts as those in FIG. 6 shown in the fourth embodiment will be omitted.

The liquid waste decomposition apparatus 61 shown in FIG. 8 is provided with a waste supply means 29, a reaction medium supply means 30, and a decomposition product discharge means 31 in a high-pressure corrosion-resistant reaction vessel 62.

The high-pressure corrosion-resistant reaction container 62 includes a container main body 63.
And lids 64 provided above and below the container body 63,
A coating layer 65 made of a coating material is formed inside the reaction vessel 62. The container body 63 and the lid 64 are made of a Ni-based alloy, and the coating layer 65 is made of a Ti alloy.

The pure water supply pipe 43 of the reaction medium supply means 30
The oxidant supply pipe 51 is integrated at the subsequent stage of each of the pumps 44 and 52 and connected to a heat exchanger 66. A pressure supply pipe 67 is connected to the subsequent stage of the heat exchanger 66, and the pressure supply pipe 67 is connected to a side surface of the reaction vessel 62 to supply a reaction medium to a gap between the vessel main body 63 and the coating layer 65. .

The reaction medium supply pipe 68 for introducing the reaction medium in the gap between the container body 63 and the coating layer 65 into the reaction vessel 62 is connected to the high-pressure corrosion-resistant reaction vessel 62. A pressurizing valve 69 is provided on the pipe 68, and the pressure in the gap is adjusted by adjusting the pressurizing valve 69.
2 is controlled slightly higher than inside.

The discharge pipe 53 of the decomposition product discharge means 31
Is connected to the heat exchanger 66 of the reaction medium supply means 30,
Heat exchange between the heat of the decomposition products and the reaction medium takes place.

Further, a pressure gauge 70 for measuring the pressure in the reaction vessel 62 and a pressure gauge 71 for measuring the pressure in the gap.
Are provided.

In the liquid waste decomposing apparatus 61 having the above configuration,
The water as the reaction medium is obtained by pressurizing the water in the pure water tank 42 and the oxidant in the oxidant tank 50 by the pure water pumps 44 and 52, and then heating the heat through the heat exchanger 66 to the container body. It is supplied into the reaction vessel 62 through a gap between the coating 63 and the coating layer 65. The liquid waste in the waste tank 38 is not heated, but is transferred into the reaction vessel 62 after being pressurized by the pump 40. The decomposition products generated in the reaction vessel 62 are cooled by the cooler 55 and then collected in the decomposition product storage tank 54 through the pressure holding valve 56.

According to the present embodiment, the reaction medium supply pipe 6
8, the pressure in the gap is controlled to be slightly higher than the inside of the reaction vessel 62, so that the coating layer 65 is formed.
Is subjected to compressive stress from outside, and the container body 63
In addition, the adhesion of the coating layer 65 is prevented, so that the coating material can be easily replaced even when the coating layer 65 is deteriorated due to corrosion or the like.

Further, according to the present embodiment, the pressure gauge 70,
71, the pressure in the reaction vessel 62 and the pressure in the gap between the vessel body 63 and the coating layer 65 are measured, and the pressure fluctuation in the gap is measured, whereby the coating layer 65 is damaged by corrosion or the like. Since it is possible to detect even when a through-hole is generated, maintenance and inspection of the covering material can be performed.

Sixth Embodiment (FIG. 9) In this embodiment, a description will be given of a corrosion-resistant treatment method of a liquid waste decomposition apparatus.

FIG. 9 is a schematic diagram showing the configuration of a liquid waste decomposition apparatus. The configuration of the liquid waste decomposer 72 is substantially the same as the high-pressure corrosion-resistant reaction vessel 27 shown in FIG. 6 of the fourth embodiment, and therefore the description of the configuration at the same location is omitted.

[0092] As shown in FIG.
At a position upstream of the first cooler 55, a circulation pipe 73 was provided, which branched off the discharge pipe 53 and connected to the oxidizing agent tank. A pump 74 is provided in the main circulation pipe 73 and palladium acetylacetonate containing about 1 ppm of Pd
Circulating at a temperature of ° C. for about 50 hours.

The liquid waste decomposing device 72 uses Ti as a covering material for the container body 33. It is known that when Ti is mixed with a small amount of 0.12 to 0.25 wt% of Pd as an alloy component, an oxide film is stabilized and corrosion resistance is improved. However, since Pd is expensive, even a small amount increases the price of the alloy. Therefore, as shown in FIG. 9, a discharge pipe 53 of the decomposition product discharge means 31 is branched to provide a circulation pipe 73, and Pd is provided in the circulation pipe 73.
By circulating a solution containing Pd, Pd is precipitated on the surface of the Ti alloy as the coating material, thereby improving the corrosion resistance of the coating material.

According to the present embodiment, by circulating palladium acetylacetonate containing about 1 ppm of Pd at a temperature of 150 ° C. for about 50 hours, the corrosion resistance of the coating material made of the Ti alloy is equal to that of the Ti—Pd alloy. Can be improved.

[0095]

As described above, according to the high-pressure corrosion-resistant reaction vessel and the processing apparatus to which the high-pressure corrosion-resistant reaction vessel of the present invention is applied, the processing apparatus has excellent corrosion resistance and strength characteristics even under a high-pressure and high-temperature environment. The reliability can be improved, and the covering layer and the container body are prevented from sticking to each other to facilitate the replacement of the covering material, and the covering material can be periodically replaced. As a result, the cost can be reduced.

Further, according to the corrosion-resistant treatment method of the treatment apparatus of the present invention, the corrosion resistance of the coating layer made of Ti or Ti alloy in the treatment apparatus can be improved, and a high-pressure corrosion-resistant reaction vessel having more excellent durability can be obtained. .

[Brief description of the drawings]

FIG. 1 is a schematic view showing a cross section of a high-pressure corrosion-resistant reaction vessel according to a first embodiment of the present invention.

FIG. 2 is a schematic view showing a cross section of a reaction vessel obtained by improving the high-pressure corrosion-resistant reaction vessel shown in FIG.

FIG. 3 is a schematic view showing a cross section of a high-pressure corrosion-resistant reaction vessel provided with a leak detecting means.

FIG. 4 is a schematic view showing a cross section of a high-pressure corrosion-resistant reaction vessel according to a second embodiment of the present invention.

FIG. 5 is a schematic view showing a cross section of a high-pressure corrosion-resistant reaction vessel according to a third embodiment of the present invention.

FIG. 6 is a schematic diagram illustrating a configuration of a liquid waste decomposition apparatus according to a fourth embodiment of the present invention.

FIG. 7 is a schematic diagram showing a configuration of a liquid waste decomposer in which a reaction medium supply means of the liquid waste decomposer is improved.

FIG. 8 is a schematic diagram of a liquid waste decomposition apparatus according to a fifth embodiment of the present invention.

FIG. 9 is a schematic diagram illustrating a configuration of a liquid waste decomposition apparatus according to a sixth embodiment of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... High pressure corrosion-resistant reaction vessel, 2 ... Heater, 3 ... Container body,
DESCRIPTION OF SYMBOLS 4 ... Lid, 5 ... Contact part, 6 ... Metal packing, 7 ... Holding bolt, 8a, 8b ... Coating layer, 9 ... Pressure supply pipe, 10 ... Gap, 11 ... Ion exchange column, 12 ... Filter, 13 ...
High pressure corrosion resistant reaction vessel, 14a, 14b ... cooler, 15 ...
High pressure corrosion resistant reaction vessel, 16a, 16b ... metal packing,
17 supply pipe, 18 leak detector, 19 high-pressure corrosion-resistant reaction vessel, 20 container body, 21 metal packing, 22
Inner lid, 23 ... bush, 24 ... outer lid, 25a, 25b,
25c ... Coating layer, 26 ... Separation layer, 27 ... Liquid waste decomposer, 28 ... High pressure corrosion resistant reaction vessel, 29 ... Waste supply means, 30 ... Reaction medium supply means, 31 ... Decomposition product discharge means, 32 ... Heater , 33 ... container body, 34 ... lid, 35
a, 35b: coating layer, 36: metal packing, 37: holding bolt, 38: waste tank, 39: waste supply pipe,
Reference numeral 40: waste supply pump 41: check valve 42: pure water tank 43: pure water supply pipe 44: pure water pump 45
... check valve, 46 ... preheater, 47 ... pressure supply pipe, 4
8 gap, 49 oxidizer, 50 oxidizer tank, 51
... Oxidant supply pipe, 52 ... Pump, 53 ... Discharge pipe, 5
4: Decomposition product storage tank, 55: Cooler, 56: Pressure holding valve, 57: Gas cylinder, 58: Oxygen gas supply pipe, 59
... Compressor, 60 ... Pressure supply pipe, 61 ... Liquid waste decomposer, 62 ... High pressure corrosion resistant reaction vessel, 63 ... Container body, 64 ... Lid, 65 ... Coating layer, 66 ... Heat exchanger, 67 ...
Pressure supply pipe, 68 ... Reaction medium supply pipe, 69 ... Pressure gauge,
70 pressure gauge for reaction vessel, 71 pressure gauge for gap, 72
Liquid waste decomposer, 73 ... Circulation piping, 74 ... Pump

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yoshie Akai 2-1 Ukishima-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture Inside the Toshiba Hamakawasaki Plant (72) Inventor Kazuya Yamada 2, Ukishima-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa No.1 F-term in Toshiba Hamakawasaki Plant (reference) 3J046 AA06 BC06 BD10 CA02 DA04 4K062 AA03 AA10 BA05 FA02

Claims (10)

[Claims] 1. A high-pressure corrosion-resistant reaction vessel comprising a container main body and a lid, wherein a material to be treated can be hermetically sealed inside the container. A high-pressure corrosion-resistant reaction vessel provided with a pressure-controlling means for controlling a pressure in a gap formed between the container body and the coating layer and a pressure in the container. . 2. The high-pressure corrosion-resistant reaction vessel according to claim 1, wherein the pressure adjusting means is a pressure supply pipe having one end connected to the inside of the vessel and the other end connected to the gap. 3. A high-pressure corrosion-resistant reaction vessel comprising a container body and a lid, wherein the material to be treated can be hermetically sealed inside the container. A high-pressure corrosion-resistant reaction vessel, wherein a coating layer is formed, and an isolation layer made of an anti-adhesion material is provided between the container body and the coating layer. 4. The container according to claim 1, wherein at least one of said container body and said lid is made of any one of carbon steel, stainless steel, nickel (Ni) based alloy and titanium (Ti) alloy. Item 4. A high-pressure corrosion-resistant reaction vessel according to any one of Items 1 to 3. 5. The coating material is made of Ti or an alloy containing Ti, and a contact portion with the packing is made of molybdenum (Mo), vanadium (V), or aluminum (A).
The high-pressure corrosion-resistant reaction vessel according to any one of claims 1 to 4, comprising a high-strength titanium alloy containing 1). 6. The coating material is made of Pt or an alloy containing Pt, and a contact portion with the packing is made of rhodium (R).
The high-pressure corrosion-resistant reaction vessel according to any one of claims 1 to 4, comprising a high-strength Pt alloy containing h) or iridium (Ir). 7. At least two metal packings are installed concentrically at a fixed distance from each other at a contact portion between the container body and the lid, and respond to pressure changes between the packings. The high-pressure corrosion-resistant reaction vessel according to any one of claims 1 to 6, further comprising a leak detecting means for detecting the leak. 8. A high-pressure corrosion-resistant reaction vessel for decomposing a material to be treated using a high-temperature high-pressure water and an oxidizing agent under supercritical conditions as a reaction medium, and a material to be treated for supplying the material to be treated into the high-pressure corrosion-resistant reaction container Means, a reaction medium supply means for supplying the reaction medium into the high-pressure corrosion-resistant reaction vessel, and a processing product discharge means for discharging the processing product generated by the decomposition treatment from the inside of the high-pressure corrosion-resistant reaction vessel. The high-pressure corrosion-resistant reaction vessel is provided with a vessel body and a lid, and is configured to be able to hermetically seal a material to be treated inside the vessel. A processing apparatus, comprising a layer, and pressure adjusting means for adjusting a pressure in a gap formed between the container body and the coating layer and a pressure in the container. 9. The reaction medium supply means includes a means for supplying high-temperature and high-pressure water and a means for supplying oxygen gas as an oxidant, and the pressure adjusting means includes a means for supplying an oxidant and oxygen gas. The processing apparatus according to claim 8, further comprising a pressure supply pipe branched from the container and connected to a gap between the container body and the coating layer. 10. A processing apparatus for performing a corrosion-resistant treatment of a coating layer made of a coating material coated on at least a part of a contact portion in contact with a material to be processed in the processing apparatus according to claim 8. In the corrosion-resistant treatment method, the coating layer may be Ti
Alternatively, in the case of a Ti-containing alloy, a liquid material containing a noble metal is circulated in the processing apparatus.