JP3274280B2 - High pressure reaction vessel equipment - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-pressure reactor suitable for use in a process for decomposing harmful organic substances with water mainly under supercritical conditions.

[0002]

2. Description of the Related Art Conventionally, regarding the decomposition treatment of organic substances, the decomposition treatment by microorganisms has been generally carried out by taking human waste treatment as a typical example. However, the large amount of sludge generated due to the treatment is problematic. As a result, a method for reducing this was studied. The typical method is 200-3
A method called a wet oxidation method in which air or oxygen is forcibly sent as an oxidizing agent under a hot water condition of about 100 ° C. and about 100 atm to cause oxidative decomposition,
This method has no particular problem in the case of general organic substances such as night soil, but it has been said that there is a problem in the level of decomposition when applied to wastewater containing harmful organic substances such as PCB.

In order to further improve such a problem relating to the degree of decomposition, supercritical water (temperature 374) is used.
Supercritical water oxidation, in which an oxidizing agent is allowed to act at a temperature and pressure of 220 ° C. or more to cause decomposition, has recently attracted attention and has been actively researched and developed. There is a technique disclosed in Japanese Patent Publication No. 4225 (Japanese Patent Publication No. 1-38532).

That is, water under supercritical conditions can dissolve organic substances which are difficult to dissolve under normal pressure due to the change in polarization characteristics (thus, it becomes an excellent solvent), and water When an oxidizing agent such as oxygen or aqueous hydrogen peroxide coexists, these are also uniformly dispersed, and oxidative heat (combustion) of the organic substance occurs, and the decomposition reaction proceeds without additional input of combustion energy.

The degree of the decomposition is said to be, for example, 99.99% or more in the case of PCB, which is close to complete decomposition,
In addition, since the reaction conditions are milder than combustion, they do not cause the generation of secondary harmful substances such as dioxin, and the treatment of harmful organic substances has become a problem. Processing technology. As shown in FIG. 17, the basic flow is that an organic substance-containing fluid (water), which is an object to be processed, is sent from a tank 14 through a shut-off valve 15 to a high-pressure pump 16 through a check valve 17 under pressure. An oxidant fluid (for example, hydrogen peroxide solution) is sent from the tank 21 via the shut-off valve 22 to the pressurized pump 23 via the check valve 24 under pressure.
These merge into the preheater 52 where the heater 55
Thus, heating is performed to reach 374 ° C. or more, which is the supercritical condition of water. Thus, the mixed fluid entering the high-pressure reactor 53 heats up due to the oxidation reaction of the organic matter, and during this time, the organic matter is mainly decomposed into water and carbon dioxide gas. These decomposed products are then cooled by the cooler 54 and enter the gas-liquid separator 28, where they are separated into gas and liquid, and the gas is released from the pressure reducing valve 29 through the shut-off valve 30 to the atmosphere, while the liquid is discharged to the atmosphere. The gas is discharged from the pressure reducing valve 31 through the closing valve 32, and a series of processing is completed.

[0006]

However, as to the conventional supercritical water oxidation treatment technology, although the basic flow (process) is disclosed as described above, most of the high-pressure reaction vessel apparatus which forms the center of the flow is disclosed. The fact is not disclosed. In view of the above situation, an object of the present invention is to provide a high-pressure reactor suitable for efficiently performing a decomposition treatment of an organic substance mainly with water under supercritical conditions.

[0007]

According to the present invention, a cylindrical container body 2 is hermetically covered with lid members 3 and 4, and a high-pressure chamber 1A is provided therein.
Is a high-pressure reaction vessel device 1 which employs the following technical means to achieve the above object. That is, in the present invention according to claim 1, one end portion 7a of the flow path forming member 7 that forms the inner / outer flow paths 11 and 12 in the high-pressure chamber 1A is fixed to one cover member 4, and the flow path is formed. The other end 7b of the passage forming member 7 is a free end, and forms a mixing passage 8 which connects the inner / outer passages 11 and 12 in cooperation with the other cover member 3 facing the other end. The lid member 4 on the side where the passage forming member 7 is fixed is connected to first pressure supply means A for supplying a first fluid 14A to one of the inner and outer flow paths 11 and 12 by pressurization. The cover member 3 on the side of the flow path 8 is connected to a second pressure supply means B for supplying the second fluid 21A to the mixing flow path 8 under pressure, and further fixes the flow path forming member 7. An outlet 13 for a fluid mixture flowing through the other of the inner and outer flow paths 11 and 12 through the mixing flow path 8 is formed in the side lid member 4. And it is characterized in that it is.

In the present invention according to claim 2, the high-pressure chamber 1
Flow path forming member 7 that forms inner and outer flow paths 11 and 12 in A
Is fixed to one lid member 4 and the other end 7b of the flow path forming member 7 is a free end and cooperates with the other opposing lid member 3 to form inner and outer flow paths. A mixing channel 8 connecting the channels 11 and 12 is formed.
The first pressure supply means A for supplying the first fluid 14A to the outer flow path 11 under pressure is connected to the lid member 4 on the side where the pressure is fixed. Second pressurizing and supplying means B for pressurizing and supplying the second fluid 21A to the mixing channel 8 is connected to the lid member 4 on the side where the channel forming member 7 is fixed. Inner channel 1 via channel 8
The first gas-liquid separation means C is connected to the outflow hole 13 of the fluid mixture flowing through the second flow path 2, and further through a pipe 64 drawn upward from the upper part of the inner flow path 12. And the second gas-liquid separation means D is connected.

According to a third aspect of the present invention, the first fluid 14A is an organic-containing fluid, and the second fluid 21A is an oxygen-containing fluid. Claim 4
According to the present invention, the first fluid 14A is water, and the second fluid 21A is an organic fluid. According to a fifth aspect of the present invention, in the second aspect of the present invention, the first gas-liquid separating unit C and / or the second gas-liquid separating unit D are provided with a flow rate adjusting unit 60. It is assumed that.

[0010] In the present invention according to claim 6, according to claim 4 of the present invention.
And the third fluid 35A is pressurized and mixed into the mixing channel 8 together with the second fluid 21A in
The third fluid 35A is an oxygen-containing fluid. In the present invention according to claim 7, the first fluid 14A and the second fluid 21A or the first to third fluids 14A are provided.
Along with A, 21A, and 35A, a fourth fluid 39A can be pressurized and supplied to the mixing channel 8 to be mixed, and the fourth fluid 39A is an alkaline aqueous solution.

The present invention according to claim 8 is characterized in that a heat insulating member 25 is provided on the inner surface of the container body 2. According to the ninth aspect of the present invention, the flow path forming member 7 has a cylindrical shape made of a heat-resistant material,
The inside of the cylinder is an inner passage 12 extending in the axial direction, and the outside of the cylinder is an annular outer passage 11.

According to a tenth aspect of the present invention, the cylindrical flow path forming member 7 is characterized in that the corrosion resistant layer 7A is applied to the mixing flow path 8 side on the inner surface and / or the outer surface. Things. In the present invention according to claim 11, the cylindrical flow path forming member 7 has at least two portions 7 in the axial direction.
It is characterized in that it is divided into c and 7d and can be joined and separated freely.

In the twelfth aspect of the present invention, the cylindrical flow path forming member 7 has axial fins 44, 4 on its inner and outer surfaces.
4A, 45, 45A, 46, 46A, 47, and 47A are provided. Claim 13
According to the present invention, the flow path forming member 7 is a plurality of straight tubular heat transfer tubes 48, 48A, and the first fluid 14A is guided to the mixing flow path 8 with the second fluid 21A through the inside of the tubes. It is characterized by having been made.

According to the present invention, the inner flow path 12 is connected to the reaction section 12 A and the heat exchange section 12 through the throttle section 73.
B are formed separately in the longitudinal direction of the flow path, and the opening of the conduit 64 in the second gas-liquid separation means D is positioned above the heat exchange section 12B. It is. The present invention according to claim 15 is characterized in that the reaction section 12A is provided with a liner 107A as a removable corrosion-resistant layer.

According to the present invention, heat is exchanged with the first fluid 14A through the pipe 28A of the first gas-liquid separation means C and / or the pipe 65 of the second gas-liquid separation means D. Heat exchangers 77 and / or 78 are provided. According to the seventeenth aspect of the present invention, there is provided the main line 18A of the first pressurizing supply means A and the sub line 18B branched from the main line 18A.
A heat exchanger 77 is provided over the pipe 65 of the gas-liquid separation means D, and the discharge port of the sub-pipe 18B is
It is characterized in that it is positioned in the middle part of the outer channel 11.

According to the present invention, the main line 18A and / or the sub line 18B of the first pressurizing / supplying means A are provided.
In addition, a throttle means 79 for controlling the flow rate is provided. In the present invention according to claim 19,
A heater 80 is provided in the outer channel 11.

According to the twentieth aspect of the present invention, the sub-line 18
The discharge port of B is characterized in that it is located in the heat exchange portion 12B of the inner flow path 12 and near the inner wall of the flow path forming member 7. In the present invention according to claim 21, the liquid separated by the second gas-liquid separation means D is supplied to the first pressure supply means A.
Conduit 83 that recirculates to the suction side of supply pump 16 at
It is characterized by having.

[0018]

The basic operation of the high-pressure reactor 1 according to the present invention will be described, for example, assuming that an aqueous solution of a harmful organic substance is subjected to oxidative decomposition under supercritical water conditions. In FIG. 1, a first fluid 14A, which is water containing a harmful organic substance, is pressurized and supplied from a tank 14 to an outer channel 11 in a high-pressure chamber 1A via a first pressurizing supply unit A.

That is, the harmful organic substance-containing fluid 14A is pressurized and supplied from the tank 14 via the shut-off valve 15 by the feed pump 16 to the header section 9 from the check valve 17 through the pipe line 18. The water is heated by a preheater 19 provided in the passage 18 so as to reach a supercritical condition of water (374 ° C.), and the pressure is set by a pressure reducing valve described later so as to maintain the supercritical condition of water (220 atm). And flows into the high-pressure chamber 1A.

The harmful organic substance-containing fluid 14A that has flowed into the high-pressure chamber 1A rises in the outer flow path 11 and reverses in the mixing flow path 8. On the other hand, the second fluid 21A, which is an oxygen-containing fluid necessary for causing an oxidation reaction under supercritical water conditions, is supplied from the opening 20 of the upper lid member 3 to the second pressure supply means B, that is, the closing valve 22 from the tank 21. The pressure is supplied to the mixing channel 8 through the check valve 24 by the feed pump 23 via the feed pump 23 to be mixed.

The harmful organic substances are oxidized and decomposed under the supercritical water condition by the mixing of the oxidizing agent and flow down the inner flow path 12 of the flow path forming member 7, and during this time, the fluid rising in the outer flow path 11 and the flow path forming liquid are formed. The heat exchange is performed via the member 7 (therefore, once the exothermic reaction has occurred, the heating by the preheater 19 is not essential, so the power supply and the like are stopped).

The fluid mixture oxidatively decomposed and cooled in the high-pressure reaction chamber 1A flows out of the outlet hole 13 of the lower cover 4 and is further cooled by the cooler 27 to reach the gas-liquid separator 28, where the gas The gas (main component is carbon dioxide) is separated into a liquid (main component is water).
The liquid is discharged to the storage tank 33 via the pressure reducing valve 31 and the closing valve 32, and the processing of the target organic-containing fluid is completed.

[0023]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described below with reference to the drawings. In FIG. 1 showing a first embodiment of the present invention, a high-pressure reaction vessel device 1 is provided with a lid member through seal members 5 and 6 at upper and lower openings of a container body 2 formed in a cylindrical shape, preferably a cylindrical shape. (The upper lid 3 and the lower lid 4) form an airtight high-pressure chamber 1A.

In the embodiment, a flow path forming member 7 for forming the inner and outer flow paths 11 and 12 in the high-pressure chamber 1A is provided with one end 7a fixed to the lower lid 4, and the other end 7b is connected to a free end. In cooperation with the upper lid 3, which is the other opposing lid member, a mixing flow path 8 that connects the axially long inner flow path 12 and the annular outer flow path 11 is formed. The flow path forming member 7 is formed of a heat-resistant material such as Inconel in a cylindrical shape, but the free end side near the mixing flow path 8 becomes a high-temperature reaction field accompanied by generation of a strong acid. A corrosion-resistant layer (including a film) on its inner surface and / or outer surface by thermal spraying or lining of ceramics such as silicon carbide
It is desirable to apply A. In this case, it is recommended that the corrosion-resistant layer be configured as a tubular liner so as to be detachable, since it is expected that the portion will be severely damaged.

A first fluid 14A is applied to one of the inner and outer flow paths 11 and 12 on the lid member on the side to which the flow path forming member 7 is fixed, in the embodiment, the lower lid 4, and to the outer flow path 11 in the embodiment. The first pressure supply means A for supplying pressure is connected. In the embodiment, an annular header 9 is formed on the lower lid 4, and the header 9 and the outer flow path 11 are communicated with each other through a plurality of through holes 10 formed at equal intervals in the circumferential direction. One pipeline 18 is connected.

Further, the first conduit 18 has a first tank 14 for an aqueous solution 14A containing, for example, a harmful organic substance as a first fluid, a shutoff valve 15, a feed pump 16 exemplified by a high-pressure pump, and a check valve. The valves 17 are arranged in series in that order, and the water is placed under supercritical conditions (374 ° C.) when the system is started.
A preheater 19 for heating up to the vicinity is provided.

On the other hand, the upper lid 3 is placed under supercritical water conditions (temperature 3
Second pressurizing and supplying means B capable of pressurizing and supplying a second fluid 21A, for example, an oxygen-containing fluid, necessary for inducing an oxidation reaction at 74 ° C. or higher and a pressure of 220 atm or higher to the mixing channel 8
Is connected. In the embodiment, the second conduit 20A is connected to the through hole 20 formed in the upper lid 3, and the second conduit 20A has a second tank 21 for the second fluid 21A.
A shut-off valve 22, a feed pump 23 exemplified by a high-pressure pump, and a check valve 24 are arranged in series in that order.

Here, an example of the oxygen-containing fluid is hydrogen peroxide solution. When the second fluid is a gas such as air or oxygen, the second tank 21 becomes a cylinder. It is also possible to use a second pressurizing / supplying means for temporarily accumulating the pressure in the accumulator from a cylinder by a booster pump, reducing the pressure by a pressure reducing valve, and then supplying the pressure. The lower lid 4 communicates with the inner flow path 12 and has an outlet 13 for a fluid mixture flowing down the inner flow path 12. The outlet 13 is connected to a first gas-liquid separation means C. ing.

In the embodiment, a third conduit 28A is connected to the outflow hole 13, and a cooler 27 and a gas-liquid separator 28 are arranged in series in the third conduit 28A. First
-The two branch pipes 28B and 28C are connected and the gas is the first
The pressure is reduced by the pressure reducing valve 29 provided in the branch pipe 28B and the closing valve 3
The liquid is released to the atmosphere from 0, and discharged to the storage tank 33 via the pressure reducing valve 31 and the closing valve 32 provided in the second branch pipe 28C.

Next, the operation of the first embodiment shown in FIG. 1 will be described assuming that an aqueous solution of harmful organic substances is subjected to oxidative decomposition under supercritical water conditions. First fluid 14
The harmful organic substance-containing fluid A is supplied from the first tank 14 to the check valve 17 by the feed pump 16 via the shut-off valve 15.
The pressure is supplied to the header section 9 via a pipe 18 through a pipe 18, and when the system is started, the preheater 19 provided in the pipe 18 heats the water so as to reach a supercritical condition (374 ° C.) of water, and the pressure is reduced. The pressure is set by the valves 29 and 31 to maintain the supercritical condition of water, that is, 220 atm, and flows into the high-pressure chamber 1A.

The first fluid 14A containing harmful organic substances which has flowed into the high-pressure chamber 1A rises in the outer flow path 11 and reverses in the mixing flow path 8. On the other hand, an oxygen-containing fluid 21A necessary for causing an oxidation reaction under supercritical water conditions is supplied from a through hole 20 of an upper lid 20 to a mixing flow path 8 through a shut-off valve 22 from a second tank 21 through a feed pump. 23 pressurizes and mixes through a check valve 24.

The harmful organic substances are oxidized and decomposed under supercritical water conditions (at a temperature of 374 ° C. or higher and a pressure of 220 atm or higher) due to the mixing of the oxidizing agent, and flow down the inner flow path 12 while moving up the outer flow path 11. Heat exchange is performed with the first fluid 14A via the flow path forming member 7 (therefore, once an exothermic reaction has occurred, heating by the preheater 19 is not essential).

Further, since the container body 2 generates heat in the internal high-pressure chamber 1A as described above, it is desirable to insulate the container body 2 from the viewpoint of ensuring the strength of the container body 2 and also from the viewpoint of effective use of energy. It is more preferable to use an external heat insulation system as the heat insulation means. However, the heat insulation member 25 is provided inside the container body 2 and further, the inside of the upper lid 3 which is significantly affected by the exothermic reaction due to the supply of the oxidant is provided. The internal heat insulation system in which the heat insulating material 26 is provided is advantageous in terms of efficiency. Here, as the heat insulating materials 25 and 26, oxides such as alumina, nitrides such as silicon nitride, and carbides such as silicon carbide can be used.

The fluid mixture oxidized and decomposed and cooled in the high pressure chamber 1A flows out of the outlet hole 13 of the lower cover 4 while being cooled in the process of flowing down the inner flow path 12, and is further cooled by the cooler 27. The gas reaches a gas-liquid separator 28, where it is separated into a gas (main component is carbon dioxide) and a liquid (main component is water), and the gas is depressurized by a pressure reducing valve 29 and released to the atmosphere from a shutoff valve 30, The liquid is discharged to the storage tank 33 via the pressure reducing valve 31 and the closing valve 32, and the processing of the target organic substance-containing fluid is completed.

In the above described example, the outer flow path 1
The function of the high-pressure reactor device 1 according to the present invention has been described in which the first fluid flowing into the mixing vessel 1 is an organic-containing fluid, and the second fluid flowing from the upper lid 3 into the mixing channel 8 is an oxygen-containing fluid. The present invention can also be applied to a case where the decomposition reaction under the conditions is utilized as hydrolysis by water instead of oxidation reaction. In this case, the first fluid is water and the second fluid is an organic fluid (for example, chlorofluorocarbon).

FIG. 2 shows a second embodiment of the present invention, in which the decomposition of the organic fluid is carried out under supercritical water conditions and using an oxidizing agent, and in particular, is stored. This is a high-pressure reaction vessel device 1 preferable for treating high-concentration harmful organic substances. Parts common to the first embodiment are denoted by common reference numerals, and differences will be mainly described below. That is, the first fluid 14A exemplified by water related to generation of supercritical conditions
Is supplied from the tank 14 through the check valve 17 to the outer flow path 11 of the flow path forming member 7 of the high-pressure chamber 1A via the check valve 17 via the shut-off valve 15, and then rises in the outer flow path 11 to mix the flow path. Reach 8. Here, the harmful organic substance to be processed is the above-described second fluid 21A as the third fluid 35A from the third tank 35 via the shut-off valve 36 and the feed pump 37 via the check valve 38. The mixture is pressurized and supplied to the mixing channel 8 together with the oxygen-containing fluid.

Under a steady condition, however, the organic substance and the oxidizing agent are uniformly dispersed in the water solvent that has reached the supercritical water condition to cause an oxidation reaction. Is cooled in the process of flowing down. Note that the configuration of this figure in which mixing is performed in the same part has a good dispersibility of the mixture because the water solvent has already reached the supercritical condition, and since only the water rises in the outer flow path 11, even in heat exchange, Further, it is preferable from the viewpoint of the corrosion resistance of the container body 2. In view of the fact that corrosion does not pose a problem, the preheater 19 for preheating water can be formed by an internal heat method using a sheath heater in the first conduit 18.

When the organic fluid to be treated contains chlorine, such as PCB, for example, hydrochloric acid is generated by an oxidative decomposition reaction. To neutralize the hydrochloric acid, an alkali solution (as an example, caustic soda) is added. In FIG. 2, this is supplied as a fourth fluid 39A from the fourth tank 39 via the shut-off valve 40 via the shut-off valve 40 via the check valve 42 to the mixing channel 8 by pressurization and mixing. ing.

The gas-liquid separation of the mixed fluid is described in the first section.
As in the embodiment, when the amount of the mixed fluid is large, a preheater such as a pre-heater or a sheath heater is provided in the pipeline of the second to fourth fluids (not shown) to supply the second to fourth fluids, although not particularly shown. It is desirable to individually preheat and then pressurize and supply the mixture to the mixing channel 8. FIG. 3 shows a third embodiment of the present invention. In the second embodiment described with reference to FIG.
8. The difference is that an external auxiliary heat exchanger 43 is provided in the third conduit 28A, and other configurations and operations are common to those of the second embodiment.

The third embodiment can function effectively when heat exchange in the high-pressure chamber 1A is insufficient. FIGS. 4 to 7 show the fourth to seventh embodiments of the present invention, respectively. In the second embodiment described above with reference to FIG. The parts common to the second embodiment are denoted by the same reference numerals, the description of the common configuration and operation is omitted, and the differences will be described below.

First, in the fourth embodiment shown in FIG. 4, the cylindrical flow path forming member 7 is divided in the axial direction into an upper portion 7c and a lower portion 7d which can be joined and separated by a flange joining means 7e. It is. In the fourth embodiment, as described above, in the reaction chamber 1A, the oxidative decomposition reaction is exothermic and the environmental conditions are severe due to the generation of a strong acid such as hydrochloric acid, and the flow path forming member 7 is severely damaged. In order to make it easy to replace as a consumable, the upper part 7c for the oxidative decomposition reaction and the lower part 7d for the cooling heat exchange are divided into two parts so that they can be joined and separated.

In the fourth embodiment, the inner surface and / or the outer surface of the upper portion 7c can be formed of a corrosion-resistant material such as alumina, or can be sprayed or lined with the corrosion-resistant material. The number of divisions may be two or more. The fifth embodiment shown in FIG. 5 is an extension of the fourth embodiment, and includes fins 44, 44A, 45, 45A,
46, 46A, 47 and 47A are provided to promote heat exchange inside and outside.

The sixth embodiment shown in FIG. 6 is an example in which the flow path forming member 7 is not cylindrical but has straight tubular heat transfer tubes 48, 48A provided in the through holes 10, 10 of the lower lid 4. This is an example in which the first fluid 14A passes through the inside and is guided to the mixing flow path 8 with the second fluid 21. In this case, the heat transfer tubes 48 and 48A are arranged equally on the circumference. Is desirable.

The seventh embodiment of FIG. 7 is an example in which the heat transfer tube is formed in a spiral shape, and although one tube functions, as shown, a plurality of tubes 49, 49A are equally divided in the axial direction on the circumference. It is desirable to arrange at pitch. FIG. 8 shows an eighth embodiment of the present invention. The liquid 33A after gas-liquid separation, which has been diluted in the second embodiment described above with reference to FIG. In the eighth embodiment, the efficiency of the system can be further improved in combination with the excellent thermal efficiency of the high-pressure reaction vessel device 1, and particularly, the water This is effective when a small amount of a second fluid containing a second harmful organic substance to be decomposed is mixed and treated as one fluid.

The above-described third to eighth embodiments can be applied to the first embodiment. The vertical direction of the container body 2 may be reversed, or the container body 2 may be It may be a so-called horizontal type installed. Further, the container body 2
The cover members 3 and 4 for airtightly covering at least one of them may be openable and closable from the viewpoint of maintenance and the like.
The container body 2 may be configured as a bottomed cylinder.

FIGS. 9 to 16 show ninth to nineteenth embodiments of the present invention, respectively.
In the sixteenth embodiment, a second gas-liquid separation for further gas-liquid separation of a gas component generated in the reaction section 12A at the upper free end of the inner flow path 12 separately from the first gas-liquid separation means C described above. The point that the means D is provided is different from the above-described first to eighth embodiments in the configuration and operation, and since other basic configurations are common, common parts are denoted by common reference numerals. The differences will be mainly described.

FIGS. 9 and 10 both correspond to FIG. 1. The flow path forming member 7 has an inner flow path 12 formed by a flange 12C provided on the inner peripheral side of the member 7.
2A and the heat exchange portion 12B are formed separately in the longitudinal direction of the flow path, and a liner 107A as a corrosion-resistant layer is detachably provided on the flange 12C. The first gas-liquid separation means C includes a throttle 60 in the third conduit 28A and the cooler 2.
An on-off valve 62, which is provided in series on the upstream side of the pipe 7 and is controlled to open and close by a signal of a liquid level gauge 61 provided in the gas-liquid separator 28, is provided in the second branch pipe 28C.

The second gas-liquid separation means D has a tendency that gas components generated mainly from carbon dioxide by the oxidation reaction of the organic substance-containing fluid in the reaction section 12A tend to move upward in the reaction section in terms of buoyancy. Is provided as a response. That is, in the ninth embodiment shown in FIG.
A communication pipe 64 is connected to the through-hole 63 through the liner 107A and opened at the lower end of the reaction section 12A.
A pipe 65 is connected, and a cooler 66 and a gas-liquid separator 67 are arranged in series in the fourth pipe 65. Further, the gas-liquid separator 67 has a first / second branch pipe 67B. , 67C
The gas is decompressed by the pressure reducing valve 68 provided in the first branch pipe 67B and released to the atmosphere from the shut-off valve 69, while the liquid accompanying the gas component is opened and closed by the second branch pipe 67C. The liquid is discharged to the storage tank 71 via the valve 70.

Here, the opening / closing valve 70 is a pressure reducing valve that is opened / closed in conjunction with a signal from a liquid level gauge 72 provided in the gas-liquid separator 67. In the ninth embodiment shown in FIG. 9, similar to the first embodiment described with reference to FIG.
Harmful organic substance containing fluid (first fluid 14A)
When it is supplied to 1, it rises and reverses in the mixing channel 8, while
The oxygen-containing fluid necessary for inducing an oxidation reaction under supercritical water conditions is supplied under pressure from the second pressurized supply means B, whereby harmful organic substances are oxidized and decomposed under supercritical water conditions while flowing into the internal stream. When flowing out of the outflow hole 13 while being cooled in the course of flowing down the passage 12, the first gas-liquid separation means C treats it as described above.

In the ninth embodiment, of the components produced by the reaction in the reaction section 12A, the gaseous component is
While flowing down the second heat exchange section 12B, it reverses and rises as shown by the arrow in FIG. 9, flows upward through the heat exchange section 12B, flows into the opening of the conduit 64, flows out of the through hole 63, and flows out of the cooler 66. To reach a gas-liquid separator 67 where it is separated into a gas (main component is carbon dioxide) and an accompanying liquid (main component is water), and the gas is reduced in pressure by a pressure reducing valve 68 to a closing valve 69. Is released to the atmosphere, and the liquid is discharged to a storage tank 71 via a pressure reducing valve 70 linked with a liquid level gauge 72.

The throttle 60 in the ninth embodiment has the function of controlling the flow to the gas-liquid separation means.
It can also be provided in the conduit 65 of the gas-liquid separation means D. In the ninth embodiment, when the decomposition reaction under the same supercritical water condition is used not as an oxidation reaction but as hydrolysis with water, the first fluid is water, and the second fluid is an organic fluid (fluorocarbon). Including).

FIG. 10 shows a tenth embodiment of the present invention. In particular, the reaction section 12A and the heat exchange section 12B are clearly separated by providing a throttle section 73, and the gas from the heat exchange section 12B is separated. Components that smoothly flow out to the second gas-liquid separation means D are denoted by common reference numerals, and portions common to the first and ninth embodiments described above with reference to FIGS. The differences will be mainly described.

In FIG. 10, the flow path forming member 7 has a throttle section 73 and a staying section 74 formed in the inner flow path 12 thereof.
The gas component generated in the reaction section 12A is prevented from moving to the reaction section 12A by the presence of the throttle section 73, and reaches the stagnation section 74. The opening of the conduit 64 faces the retaining portion 74, and a bellows 74 a is provided at the upper end of the conduit 64, and the bellows 74 a is housed in a concave portion 75 formed in the upper lid 3, and the through hole 63 is formed in the concave portion 75. Are in communication. The concave portion 75 is hermetically closed by a lid 76, and the bellows 74a blocks leakage flow through the through hole in the upper lid 3 of the conduit 64 and absorbs axial expansion and contraction.

FIG. 11 shows an eleventh embodiment of the present invention, in which a heat exchanger 77 is provided in place of the cooler 66 shown in FIG.
The first fluid 14A of the pressurized supply means A is preheated, whereby the efficiency of the entire system is further improved. The means for exchanging heat with the first fluid is as follows.
A heat exchanger 78 may be provided between the pressurizing supply means A and the first gas-liquid separation means C, and the heat exchangers 77 and 78 may be provided.
Can be provided for either one or both.

The eleventh embodiment shown in FIG. 11 is the same as the tenth embodiment described with reference to FIG.
Portions common to the embodiment are denoted by common reference numerals. FIG.
Is a twelfth embodiment of the present invention, which corresponds to the second embodiment described above with reference to FIG. 2. The flow path forming member 7 has a throttle 73 and a stagnant portion 74 formed therein. The first gas-liquid separating device C is different from the second embodiment in that the throttle 60 is provided, the second gas-liquid separating device D is provided, and the heat exchanger 77 is provided. -Since the operation is common to the second embodiment, the common parts are indicated by common symbols.

FIG. 13 shows a thirteenth embodiment of the present invention, in which a line 18 in the first pressurizing / supplying means A is branched into a main line 18A and a sub line 18B downstream of the check valve 17, The main conduit 18A communicates with the header 9 while the sub conduit 18B is passed through the heat exchanger 77 and then introduced into the intermediate portion of the outer flow passage 11 to improve the heat exchange efficiency in the heat exchange section 12B. Is common to the second embodiment referring to FIG. 2 and the twelfth embodiment referring to FIG. 12, the common parts are indicated by common symbols.

FIG. 14 shows a fourteenth embodiment of the present invention, which is different from FIG. 13 in that a throttle 79 is provided in the main conduit 18A described above with reference to FIG. Different from the thirteenth embodiment, other configurations
Since the operation is common, common parts are indicated by common symbols.
In the fourteenth embodiment, the flow rate can be controlled by the throttle 79, and the throttle 79 can also be provided in the sub-line 18B.

Further, the temperature state in the mixing channel 8 can be controlled by the sheath heater 80, and the first
When the fluid 14A is water, it can be said to be a preferable configuration in that the fluid 14A can be installed without any problem such as corrosion resistance. FIG. 15 shows a fifteenth embodiment of the present invention.
In the twelfth embodiment described above with reference to the above, the sub-line 18B is branched downstream of the check valve 17 to provide an on-off valve 81 in the sub-line 18B, and the discharge port 118B of the sub-line 18B is provided. To the heat exchange portion 12B of the inner flow path 12.
And the first fluid 14 on the inner wall of the flow path forming member 7.
A according to the fifteenth embodiment, the fixing of the deposit (salt) generated during the decomposition reaction and the neutralization to the inner wall of the flow path forming member 7 is performed according to the fifteenth embodiment. It can be prevented by passing water from the discharge port 118B by opening as needed, and the other configuration is common to the configuration and operation shown in FIG. 12, so common parts are denoted by common reference numerals.

FIG. 16 shows a sixteenth embodiment of the present invention. In each of the embodiments shown in FIGS. 14 and 15, the liquid separated by the gas-liquid separator 67 of the second gas-liquid separating means D is stored. A return line 83 is provided on the suction side of the supply pump 16 for the first fluid 14A from the tank 71 via the on-off valve 82 to further enhance the thermal efficiency of the system. Other configurations and operations are shown in FIGS. Therefore, common parts are indicated by common symbols.

In the first to sixteenth embodiments, the respective embodiments can be combined with each other. As the reaction conditions, not only supercritical water conditions but also high-temperature and high-pressure water conditions other than supercritical conditions are selected. It goes without saying that you get it.

[0061]

As described in detail above, the present invention provides a high-pressure reaction vessel apparatus for decomposing organic substances under supercritical water which is excellent in energy efficiency, and furthermore, a water solvent which enhances pressure resistance and corrosion resistance of the high-pressure reaction vessel. , A structure related to the supply of organic substances, oxidizing agents, etc., and a structure related to the promotion of the heat exchange function, and a high-pressure reactor excellent in treating gas (main component carbon dioxide) generated in the decomposition of organic substances under high-temperature and high-pressure water. To provide a structure for preventing the heat exchange function from being hindered by the deposit (salt) generated in the process of neutralizing the decomposition product, thereby promoting the industrial use of organic decomposition under supercritical water. As far as possible, this can be said to be extremely significant in meeting the social demands for reducing harmful organic substances.

[Brief description of the drawings]

FIG. 1 is an overall configuration diagram showing a first embodiment of the present invention.

FIG. 2 is an overall configuration diagram showing a second embodiment of the present invention.

FIG. 3 is an overall configuration diagram showing a third embodiment of the present invention.

FIG. 4 is an overall configuration diagram showing a fourth embodiment of the present invention.

FIG. 5A is an overall configuration diagram showing a fifth embodiment of the present invention, and FIG. 5B is a sectional view of a main part EE thereof.

FIG. 6 is an overall configuration diagram showing a sixth embodiment of the present invention.

FIG. 7 is an overall configuration diagram showing a seventh embodiment of the present invention.

FIG. 8 is an overall configuration diagram showing an eighth embodiment of the present invention.

FIG. 9 is an overall configuration diagram showing a ninth embodiment of the present invention.

FIG. 10 is an overall configuration diagram showing a tenth embodiment of the present invention.

FIG. 11 is an overall configuration diagram showing an eleventh embodiment of the present invention.

FIG. 12 is an overall configuration diagram showing a twelfth embodiment of the present invention.

FIG. 13 is an overall configuration diagram showing a thirteenth embodiment of the present invention.

FIG. 14 is an overall configuration diagram showing a fourteenth embodiment of the present invention.

FIG. 15 is an overall configuration diagram showing a fifteenth embodiment of the present invention.

FIG. 16 is an overall configuration diagram showing a sixteenth embodiment of the present invention.

FIG. 17 is an overall configuration diagram showing a conventional example.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 High-pressure reaction container apparatus 1A Reaction chamber (high-pressure chamber) 2 Container main body 3 Upper lid member 4 Lower lid member 7 Flow path forming member 8 Mixing flow path 11 Outer flow path 12 Inner flow path 13 Outflow hole A First pressure supply means B First 2 Pressurized supply means C First gas-liquid separation means D Second gas-liquid separation means

────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C02F 1/74 101 C02F 1/74 101 ZAB ZAB (72) Inventor Taku Aogata 1-5-5 Takatsudai, Nishi-ku, Kobe-shi, Hyogo Prefecture No. Kobe Steel, Ltd.Kobe Research Institute (72) Inventor Satoshi Furuta 1-5-5 Takatsukadai, Nishi-ku, Kobe City, Hyogo Prefecture Kobe Steel Co., Ltd.Kobe Research Institute (56) References Special Kaihei 6-225926 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B01J 3/00-3/04 B01J 19/00 C02F 1/74

Claims (22)

(57) [Claims] 1. A cylindrical container body (2) is covered with a lid member (3).
A high-pressure reaction vessel device (1) in which a high-pressure chamber (1A) is formed inside by airtightly covering in (4), wherein an inner / outer flow path (11) (12) is formed in the high-pressure chamber (1A). ) Is formed by fixing one end (7a) of a flow path forming member (7) to one of the lid members (4).
The other end (7b) is a free end and forms a mixing flow path (8) which communicates with the inner / outer flow paths (11) and (12) in cooperation with the other opposing lid member (3). The cover member (4) on the side to which the flow path forming member (7) is fixed has
The first fluid (14) is supplied to one of the outer flow paths (11) and (12).
A first pressurizing supply means (A) for pressurizing and supplying A) is connected, and the lid member (3) on the side of the mixing channel (8) has a second fluid with respect to the mixing channel (8). The second pressure supply means (B) for pressurizing and supplying (21A) is connected, and the lid member (4) on which the flow path forming member (7) is fixed is further provided with the mixing flow path (8). ), Through which an outlet (13) for a fluid mixture flowing through the other of the inner and outer flow paths (11) and (12) is formed. 2. A cylindrical container body (2) is covered with a lid member (3).
A high-pressure reaction vessel device (1) in which a high-pressure chamber (1A) is formed inside by airtightly covering in (4), wherein an inner / outer flow path (11) (12) is formed in the high-pressure chamber (1A). ) Is formed by fixing one end (7a) of the flow path forming member (7) to the one lid member (4).
The other end (7b) is a free end and forms a mixing flow path (8) which communicates with the inner / outer flow paths (11) and (12) in cooperation with the other opposing lid member (3). A first pressurizing supply means for pressurizing and supplying the first fluid (14A) to the outer flow path (11) on the lid member (4) on the side to which the flow path forming member (7) is fixed; (A) is connected, and a second pressurized supply of the second fluid (21A) to the mixing channel (8) is supplied to the lid member (3) on the mixing channel (8) side. The means (B) is connected, and the lid member (4) to which the flow path forming member (7) is fixed has a fluid flowing through the internal flow path (12) via the mixing flow path (8). Outlet for mixture (1
3) is formed, the first gas-liquid separation means (C) is connected to the outflow hole (13), and a pipe (64) drawn upward from the upper part of the inner flow path (12) is formed. A high-pressure reaction vessel device, wherein a second gas-liquid separation means (D) is connected via the second gas-liquid separation means (D). 3. The high-pressure reactor device according to claim 1, wherein the first fluid (14A) is an organic-containing fluid, and the second fluid (21A) is an oxygen-containing fluid. 4. The high-pressure reactor apparatus according to claim 1, wherein the first fluid (14A) is water, and the second fluid (21A) is an organic fluid. 5. A flow rate adjusting means (60) for said first gas-liquid separation means (C) and / or second gas-liquid separation means (D).
The high-pressure reaction vessel device according to claim 2, further comprising: 6. The third fluid (35A) is pressurized and supplied to the mixing channel (8) together with the second fluid (21A), and the third fluid (35A) is mixed with oxygen. The high-pressure reaction vessel device according to claim 4, wherein the high-pressure reaction vessel device is a contained fluid. 7. The first fluid (14A) and the second fluid (2)
1A) or first to third fluids (14A) (21A)
(35A) and the fourth mixing channel (8).
The high-pressure reaction vessel according to any one of claims 3 to 4, wherein the fluid (39A) is pressurized and supplied so as to be mixed, and the fourth fluid (39A) is an aqueous alkaline solution. apparatus. 8. A heat insulating member (25) is provided on an inner surface of the container body (2).
A high-pressure reaction vessel device according to any one of claims 7 to 13. 9. The flow path forming member (7) has a cylindrical shape made of a heat-resistant material, is installed on the axis of the container body (2), and has an inner flow path (axial) extending inside the cylinder in the axial direction. The high-pressure reaction vessel device according to any one of claims 1 to 8, wherein the outside of the cylinder is an annular outer flow path (11). 10. The cylindrical flow path forming member (7), wherein a corrosion resistant layer (7A) is applied to the mixing flow path (8) side on the inner surface and / or outer surface thereof. Items 1 to 9
Item 14. The high-pressure reactor device according to any one of the above items. 11. The cylindrical flow path forming member (7) is divided into at least two portions (7c) and (7d) in the axial direction and can be joined and separated.
11. The high-pressure reaction vessel device according to any one of 10 above. 12. The cylindrical flow path forming member (7) has axial fins (44) (44A) (45) on its inner and outer surfaces.
The high-pressure reaction vessel device according to any one of claims 1 to 11, wherein (45A), (46), (46A), (47), and (47A) are provided. 13. The flow path forming member (7) is a plurality of straight tubular heat transfer tubes (48) (48A) through which the first fluid (14A) and the second fluid (21A) communicate with each other. The high-pressure reaction vessel device according to any one of claims 1 to 6, wherein the high-pressure reaction vessel device is guided to the mixing channel (8). 14. The flow path forming member (7) is a heat transfer tube (49) (49A) extending spirally in the axial direction,
The said 1st fluid (14A) is guide | induced to the mixing flow path (8) with a 2nd fluid (21A) through the inside, The any one of Claim 1 or 6-8 characterized by the above-mentioned. High pressure reaction vessel equipment. 15. The throttle (73) wherein the inner channel (12) is a throttle (73).
The reaction section (12A) and the heat exchange section (12B) are formed separately in the longitudinal direction of the flow path through the opening, and the opening of the pipe (64) in the second gas-liquid separation means (D) is The high-pressure reaction vessel device according to claim 2 or 5, wherein the high-pressure reaction vessel device is located at an upper portion of the heat exchange section (12B). 16. The high-pressure reactor apparatus according to claim 15, wherein the reaction section (12A) is provided with a liner (107A) as a removable corrosion-resistant layer. 17. A heat exchanger with a first fluid (14A) is connected to a pipe (28A) of the first gas-liquid separation means (C) and / or a pipe (65) of the second gas-liquid separation means (D). The high-pressure reactor according to any one of claims 2, 5, 15, and 16, further comprising a heat exchanger (77) and / or (78) for performing exchange. 18. The main line (1) of the first pressure supply means (A).
8A) and a branch line (18B) branched therefrom, and the heat exchanger (77) extends between the branch line (18B) and the line (65) of the second gas-liquid separation means (D). ) Is provided, and the discharge port of the sub-channel (18B) is positioned at an intermediate portion of the outer flow path (11). 2. The high-pressure reactor device according to claim 1. 19. The main line (1) of the first pressure supply means (A).
The high-pressure reactor device according to claim 18, characterized in that a throttle means (79) for controlling the flow rate is provided in 8A) and / or the auxiliary conduit (18B). 20. A heater according to claim 1, wherein a heater is provided in the outer channel.
20. A high-pressure reaction vessel device according to any one of 5 to 19. 21. The discharge port of the sub-channel (18B) is located in the heat exchange part (12B) of the inner channel (12) and near the inner wall of the channel forming member (7). 20. The high-pressure reaction vessel device according to claim 18, wherein: 22. The liquid separated by the second gas-liquid separation means (D) is supplied to a supply pump (1) in the first pressure supply means (A).
22. The high-pressure reactor device according to claim 2, further comprising a reflux pipe (83) on the suction side of (6).