KR100787173B1 - Oxidation reactor using metal - Google Patents

Abstract

An oxidation reactor is provided to improve reaction efficiency and reduce a cost for controlling temperature and pressure to a supercritical state and a cost for injecting an oxidizer by filling a metal catalyst in a reactor for performing an oxidation reaction. An oxidation reactor includes: a mouth member(380) through which oxidation reaction objects flow into the oxidation reaction tube; an oxidation reaction tube(340) for oxidizing and decomposing the oxidation reaction objects that have flown into the oxidation reaction tube through the mouth member; and a heater(330) for varying a temperature of the oxidation reaction tube, wherein metal or metal alloy is filled in the oxidation reaction tube. The metal or metal alloy includes at least one metal selected from Fe, Ni, Cr, Mn, Cu, Mo, Zr, and Ti. The mouth member includes a body part(378) and a plurality of supply pipes(380a,380b). The oxidation reactor additionally includes: a reaction body(320) into which water and a neutralizing agent are supplied to vary a temperature of the oxidation reaction tube; and a neutralization chamber(370a) disposed at an exit side of the oxidation reaction tube to mix and neutralize a neutralizing agent that has flown into the neutralization chamber through the reaction body and a decomposed material discharged from the oxidation reaction tube.

Description

Oxidation reactor using metals {OXIDATION REACTOR USING METAL}

1 is a view showing a conventional oxidation reactor.

2 is a view showing another conventional oxidation reactor.

3 is a cross-sectional view showing an oxidation reactor according to an embodiment of the present invention.

4 is an exploded perspective view showing an oxidation reactor according to an embodiment of the present invention.

5 is an exploded perspective view showing a part of an oxidation reactor according to another embodiment of the present invention.

6 is an exploded perspective view showing a part of an oxidation reactor according to another embodiment of the present invention.

7 is a perspective view showing a mouse member according to an embodiment of the present invention.

8 is an exploded perspective view showing a mouse member according to another embodiment of the present invention.

Figure 9 (a) is a graph showing the decomposition efficiency of 2-chlorophenol using a stainless steel 316 metal according to an embodiment of the present invention.

Figure 9 (b) is a graph showing the decomposition efficiency of 2-chlorophenol using Inconel 625 metal according to an embodiment of the present invention.

Figure 10 (a) is a graph showing the decomposition efficiency of 2-chlorophenol using Monel K-500 metal according to an embodiment of the present invention.

Figure 10 (b) is a graph showing the decomposition efficiency of 2-chlorophenol using Hastelloy C-276 metal according to an embodiment of the present invention.

Figure 11 (a) is a graph showing the decomposition efficiency of 2-chlorophenol using titanium Gr2 metal according to an embodiment of the present invention.

11 (b) is a graph showing the decomposition efficiency of 2-chlorophenol using a zirconium 702 metal according to an embodiment of the present invention.

The present invention relates to an oxidation reactor, and more particularly, to an oxidation reactor having a plurality of supply pipes capable of supplying a treatment material and an oxidant separately, to prevent corrosion by acid at the inlet of the oxidation reactor.

Today, the hardly decomposable organic substances contained in various wastewaters and waste liquids generated by industrial development are decomposed and treated through biological decomposition, chemical oxidation, activated carbon adsorption, high temperature oxidation, wet oxidation, incineration, and the like.

However, as the toxicity of organic matter contained in waste water and waste liquids increases, new chemicals that are difficult to decompose have emerged, and thus, decomposition treatment methods and environmentally friendly processes with increased decomposition efficiency have been actively studied.

In particular, the wet oxidation method among the decomposition methods of the hardly decomposable organic matter contained in various wastewaters and waste liquids is a decomposition method developed to decompose toxic organic compounds having high concentration that is difficult to biodegrade but low concentration to be degraded by incineration.

However, in the wet oxidation method, the liquid phase oxidation reaction proceeds at a relatively high temperature (200 ° C.) and pressure (150 bar). Since the reaction time proceeds for about 1 to 2 hours, a large volume of high pressure reactor is required and incomplete. As oxidation occurs, reaction by-products are generated, and reprocessing is required again to completely decompose the reaction by-products.

In addition, since the incineration process decomposes the organic material at a high temperature, excessive processing costs are required, and there is a problem of emitting by-products harmful to the human body such as NOx, SOx, and dioxin.

The decomposition method developed to improve the problems of the wet oxidation method and the incineration method is a supercritical water oxidation method. The supercritical water oxidation method is used for supercritical water at a temperature of 374 ° C. (Tc) and 221 bar (Pc). Oxidative decomposition of waste water and waste liquid.

At this time, the supercritical water oxidation method is performed under operating conditions of a somewhat higher temperature and pressure than the wet oxidation method, but in the supercritical water state, organic matter and oxidizing agent are completely mixed so that there is no restriction on the material transfer necessary for the oxidation reaction, thereby high reaction. Being able to maintain the rate has the advantage that the waste water and waste liquid is completely decomposed into water and carbon dioxide, oxygen, nitrogen, etc., do not generate reaction by-products.

Moreover, it is known that in the supercritical water oxidation method, when the operation is performed at a temperature of about 400 to 500 ° C., oxidative decomposition of 99.99% or more occurs in a few minutes.

As such, the supercritical water oxidation method has a condition that the oxidation reaction rate is significantly increased by supplying abundant oxidizing agent and is evaluated as an optimal treatment method capable of completely decomposing hardly degradable toxic organic compounds.

However, despite the above-mentioned advantages, the supercritical water oxidation method is particularly resistant to acid corrosion, fouling and clogging due to precipitation of dissolved solids contained in wastewater and waste liquids. The problem has not been solved and has not been commercialized.

Recently, research has been conducted to solve the problem of acid corrosion and fouling by applying a corrosion resistant material, but corrosion is still generated even when the inner wall of the reactor in which the oxidation reaction occurs is made of a corrosion resistant metal. In addition, US Pat. Nos. 5,461,648, 5,527,471, and 5,545,337 disclose a technique of coating the inner wall of the reactor with a ceramic, such as a non-metal material, but there is a problem in durability due to the nonuniformity of the coated ceramic.

In addition, various techniques have been developed to solve problems related to acid corrosion and salt precipitation in the decomposition process of wastewater and waste liquid by oxidation, but here, for example, the conventional techniques as shown in FIGS. Introduce the problem.

First, as shown in FIG. 1, the reactant (a mixture of the treatment material and the oxidant) is supplied to the internal ceramic tube 102, and the water is supplied to the internal ceramic tube 102 while supplying water in a supercritical water state into the external metal tube 100. It is configured to prevent the phenomenon that the reaction material flowing in the internal ceramic tube 102 to the outside through the injection hole while being injected into the interior of the internal ceramic tube 102 through the injection hole 104 of the).

However, such a reactor structure can solve the problem of corrosion by acid to some extent, but there is a problem in the durability of the internal ceramic tube 102 such that cracks are generated around the injection hole 104 by the supercritical pressure of water.

In addition, the oxidation reactor shown in FIG. 2 supplies an oxidizing agent and a treatment material into the reactor 200, induces an oxidation reaction in a supercritical water state, decomposes the treatment material, and controls salt precipitation by controlling to a subcritical water state. It is configured to prevent. However, there is a problem that corrosion occurs at the supercritical and subcritical interface.

Although this prior art is effective in preventing salt precipitation, there is a structural problem that cannot be prepared for corrosion by acid generated by supplying an oxidizing agent and a treating material through a single pipe.

In addition, there is a problem that a lot of money is put into raising the prior art operating conditions as described above in the supercritical state.

An object of the present invention is to place a metal catalyst inside the reactor where the oxidation reaction takes place to increase the reaction efficiency and at the same time to reduce the cost of controlling the temperature and pressure in the supercritical state and the cost of the oxidant input To provide.

In order to achieve the above object, an oxidation reactor according to an embodiment of the present invention includes a mouse member for introducing the target materials of the oxidation reaction; An oxidation reaction tube for oxidatively decomposing target substances introduced through the mouse member; And it includes a heater for changing the temperature of the oxidation reaction tube, characterized in that the metal or metal alloy is filled in the oxidation reaction tube.

In addition, since the oxidation reactor according to the preferred embodiment of the present invention includes a mouse member capable of supplying a treatment material and an oxidant separately, corrosion by acid in the introduction portion of the oxidation reactor can be prevented.

The present inventors have found that the efficiency of the oxidation reaction can be increased only by adding the metal or the metal alloy to the oxidation reaction region, thereby completing the present invention.

This is because the pure metal components constituting the metal specimens are transformed into metal oxides by oxidation reaction to act as catalysts or fall off as metal ions to act as homogeneous catalysts. When only the metal is added, it is possible to reduce the cost of using the catalyst in terms of the fact that the metal can be automatically converted into the metal oxide or fall into the metal ion by the subcritical water and supercritical water oxidation reaction, and thus can act as a catalyst. It can be mitigated, resulting in lower operating costs.

The metal or metal alloy located inside the oxidation reaction tube according to the present invention is not particularly limited, but preferably includes at least one metal selected from iron, nickel, chromium, manganese, copper, molybdenum, zirconium, and titanium. Formation of the metal or metal alloy is also not particularly limited, and may have various forms such as spherical or plate-like.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

3 is a cross-sectional view showing an oxidation reactor according to an embodiment of the present invention. 4 is an exploded perspective view showing an oxidation reactor according to an embodiment of the present invention.

3 and 4, the oxidation reactor according to the present invention includes a reaction body 320, a neutralizer supply part 320b, a heater 330, an oxidation reaction tube 340, a metal specimen 410, and a mouse member 380. ).

The oxidation reactor oxidizes and decomposes the target material of the oxidation reaction, that is, the waste water, the waste liquid, and the oxidizing agent supplied through the mouse member 380 at a predetermined pressure and temperature, and then neutralizes it to the decomposition product outlet 370b. It is configured to discharge.

More specifically, in the oxidation reactor, as shown in FIGS. 3 and 4, the cylindrical tubular reaction body 320 is provided with a neutralizer supply part 320b and a water supply part 320a at upper and lower ends of the outer circumferential surface, respectively. have.

At this time, the neutralizer supply unit 320b of the reaction body 320 supplies the neutralizer to the inside of the reaction body 320, and the water supply unit 320a supplies water to the inside of the reaction body 320.

Here, the heater 330 provided to heat the inside of the reaction body 320 is configured to be attached to the outer circumferential surface of the reaction body 320 to be located between the water supply part 320a and the neutralizer supply part 320b.

According to an embodiment of the present invention, the inside of the reaction body 320 may be heated to a supercritical temperature by the heater 330.

Then, the upper and lower packings 390 and 400 are respectively inserted into the reaction body 320 so as to close the inside thereof, and the upper and lower packings 390 and 400 are respectively formed at the center thereof. The upper and lower ends of the oxidation reaction tube 340 are coupled to the mounting holes 390a and 400a.

At this time, the oxidation reaction tube 340 is fixed while the upper and lower ends are inserted into the upper mounting hole 390a of the upper packing 390 and the lower mounting hole 400a of the lower packing 400, respectively, of the reaction body 320. It is installed vertically in the inner center. Here, the oxidation tube 340 may be made of a metal or ceramic, such as stainless steel, Hastelloy C, Monel, Inconel, titanium or zirconium.

In particular, the lower mounting hole (400a) is simply inserted into the oxidation reaction tube 340 by interference fit as a circular hole to block the leakage, the upper mounting hole (390a) as shown in Figure 4 oxidation reaction tube (340) At the same time, the upper end side of the c) is fixed to the circumferential surface, and a small gap injection port 390b is formed to enable injection of the neutralizing agent through the same.

As such, the configuration in which the injection port 390b is in contact with the outer circumferential surface of the oxidation reaction tube 340 is to maximize the cooling efficiency by bringing the neutralizing agent of the subcritical temperature into contact with the oxidation reaction tube 340 as much as possible.

In addition, the upper cap 350 is placed on the upper portion of the upper packing 390, or the upper cap 350 in the state of placing the mouse member 380 in the lower portion of the lower packing 400, the reaction body 320 When screwing the upper peripheral side of the outer surface or screwing the lower cap 360 with the lower side of the outer peripheral surface of the reaction body 320, the upper compression block 370 or the mouse member 380 is the upper packing 390 or lower packing ( 400 is pressed, whereby the upper packing 390 and the lower packing 400 are in close contact with the upper and lower end surfaces of the reaction body, respectively, to prevent leakage.

Here, the mouse member 380 includes a body portion 378 and a plurality of supply pipes 380a and 380b. The plurality of supply pipes 380a and 380b penetrate the other surface from one surface of the body portion 378 and are spaced apart at predetermined intervals.

The treatment material and the oxidant are passed through the respective feed pipes 380a and 380b without mixing. Subsequently, the treatment material and the oxidant that have passed through the mouse member 380 are mixed in the oxidation reaction tube 340 to generate a reaction. Therefore, in the introduction part of the conventional oxidation reactor, it is possible to alleviate the corrosion phenomenon of the tube generated by mixing the treatment material and the oxidant into one tube. Thus, the life of the oxidation reactor can be extended.

In addition, the metal catalyst 410 is positioned inside the oxidation reaction tube 340, and the treatment material and the oxidant that enter the ceramic tube are decomposed with high reaction efficiency by the catalytic action. In this case, the ceramic catalyst 420 having a plurality of pores may be inserted into a portion where the lower portion of the ceramic tube and the separator 380c are connected to fix the metal catalyst inside the ceramic tube.

The upper compression block 370 is provided with a decomposition material discharge port 370b at the center side thereof and is configured to discharge the decomposition material discharged through the upper side of the oxidation reaction tube 340 to the outside.

In particular, the upper compression block 370 is provided with a neutralization chamber 370a therein, the neutralization chamber 370a in the decomposition material discharged through the upper side of the oxidation reaction tube 340, and the injection hole 390b The neutralizing agent injected through the mixture is neutralized by mixing with each other and then discharged through the decomposition product discharge port 370b.

Then, the water supplied into the reaction body 320 through the water supply unit 320a is heated to the supercritical temperature by the heater 330 while raising the inside of the reaction body 320 while being heated to the subcritical temperature. It performs a heating medium function to transfer the heated self heat to the oxidation reaction tube (340).

Furthermore, the water supplied into the reaction body 320 through the water supply part 320a pushes up the neutralizing agent supplied into the reaction body 320 through the neutralizing agent supply part 320b so that the neutralizing agent flows back to the lower side in the reaction body 320. Block the phenomenon.

Hereinafter, the operation of the oxidation reactor according to an embodiment of the present invention will be described in detail.

The treatment material (waste water and waste liquid) and the oxidant are supplied to the supply pipes 380a and 380b of the mouse member 380 and pass through the oxidation reaction tube 340.

At this time, the water supplied into the lower side of the reaction body 320 through the water supply unit 320a is heated in the heater 330 above the subcritical or supercritical temperature, and then heated above the subcritical or supercritical temperature. As the temperature of the water is transferred into the oxidation reaction tube 340, the reactant passing through the tube is heated to reach a subcritical or supercritical temperature.

As a result, the treatment material and the oxidant introduced through the supply pipes 380a and 380b cause a rapid oxidation reaction in the subcritical or supercritical state while passing through the intermediate portion of the oxidation reaction tube 340, thereby Complete decomposition proceeds.

In addition, the neutralizing agent at room temperature is supplied into the upper side of the reaction body 320 through the neutralizing agent inlet 320b and mixed with water of the subcritical or supercritical temperature rising in the reaction body 320 to be diluted. .

At this time, the neutralizing agent is mixed with water of a subcritical or supercritical temperature in the reaction body 320 as a high concentration, and is diluted to an appropriate concentration while having a predetermined temperature, for example, a subcritical temperature, and an appropriate concentration and a predetermined temperature. The neutralizing agent diluted with is injected into the neutralization chamber 370a through the injection hole 390b while cooling the outlet side of the oxidation reaction tube 340.

Here, the decomposition material decomposed by the oxidation reaction while passing through the oxidation reaction tube 340 is discharged through the upper side of the oxidation reaction tube 340 and mixed with the neutralizing agent of the neutralization chamber 370a to be neutralized.

Hereinafter, the problem of corrosion and salt precipitation of the acid in the oxidation reactor according to the present invention will be described in detail.

The treatment material (waste water and waste liquid) and the oxidant are supplied to the oxidation reaction tube 340 in a separated state through the supply pipes 380a and 380b of the mouse member 380, respectively. Here, since the treatment material and the oxidant are not mixed before entering the oxidation tube 340, the oxidation reaction does not occur, and thus, corrosion by acid does not occur at the inlet of the oxidation reactor.

Subsequently, the treatment material (waste water and waste liquid) and the oxidant are mixed in the oxidation reaction tube 340, and pass through the metal catalyst 410 located in the oxidation reaction tube 340 to reach a supercritical state and cause a rapid oxidation reaction. This creates a large amount of acid.

However, in the present invention, a large amount of acid generated by the oxidation reaction does not cause corrosion in the process of passing through the oxidation reaction tube 340 and is discharged into the neutralization chamber 370a through the upper side of the oxidation reaction tube 340. Therefore, it is possible to solve the problem of corrosion by acid.

In addition, salt precipitation generated in the course of the reaction material passing through the oxidation reaction tube 340 causes problems such as blocking or blocking fluid movement in the tube while causing scaling on the inner wall of the oxidation reaction tube 340. However, this can minimize the amount of production or block production when controlling solubility with temperature.

In an embodiment of the present invention, when the oxidation reaction tube 340 through which the reactant passes is divided into approximately the lower end, the middle end, and the upper end, the solubility is gradually increased as the subcritical temperature at the lower end of the oxidation reaction tube 340. Salt does not occur, and in the middle portion of the oxidation reaction tube 340, the solubility reaches a maximum as a supercritical temperature, and the salt rapidly precipitates while rapidly decreasing.

At this time, the neutralizing agent at room temperature introduced into the reaction body 320 through the neutralizing agent supply unit 320b and the water heated to the supercritical temperature while being raised in the reaction body 320 are mixed to generate a diluted neutralizing agent having a subcritical temperature. Done.

The neutralizing agent of the subcritical temperature is cooled while contacting the upper end of the oxidation reaction tube 340, thereby increasing the solubility as the upper end of the oxidation reaction tube 340 is lowered to the subcritical temperature, and eventually the oxidation reaction tube 340 Salt precipitation, which began to occur in the middle portion of the c), reaches an upper end of the oxidation reaction tube 340 and cools to a subcritical temperature, and is dissolved again with an increase in the neutralizer solubility to prevent or minimize the formation of salt precipitation.

As a result, in the present invention, it is possible to completely solve the problem of corrosion and salt precipitation of acid caused in the decomposition process of wastewater and waste liquid by oxidation reaction in the oxidation reactor.

5 is an exploded perspective view illustrating a part of an oxidation reactor according to another embodiment of the present invention, in which a plurality of flow paths may be formed in an oxidation reaction tube 340 formed of a single body to increase the throughput of decomposition of a treated material. There is an advantage.

6 is an exploded perspective view showing a part of an oxidation reactor according to another embodiment of the present invention, which is a method of increasing the decomposition productivity of a treated material by installing a plurality of oxidation reaction tubes 340 each having one flow path.

7 is a perspective view showing a mouse member according to an embodiment of the present invention.

Referring to FIG. 7, the mouse member 380 of the present invention includes a body portion 378 and a plurality of supply pipes 380a and 380b spaced apart from one surface of the body portion 378 at predetermined intervals penetrating the other surface. do.

Although the body portion 378 is shown in a disc shape in FIG. 7, the shape of the body portion 378 can be any shape for coupling to an oxidation reactor.

A groove of a predetermined depth may be formed in a portion of the body portion 378. Here, the supply pipes 380a and 380b inserted through one surface of the body portion 378 penetrate the bottom surface of the groove, and the oxidation reaction tube 340 is disposed along the outer circumference of the groove.

Body portion 378 may be made of stainless steel, Hastelloy C, Monel, Inconel, Titanium or Zirconium.

The separator 380c may be disposed inside the groove, and the separator 380c separates the space inside the groove so that the treatment material and the oxidant passed through the supply pipes 380a and 380b are not mixed. It is assisted to be supplied to the oxidation reaction tube (340).

Since one surface of the separator 380c may react with a reactant mixed with a treatment material and an oxidant, corrosion may occur, and the separator 380c may be made of ceramic, titanium, or zirconium, which is highly resistant to corrosion.

According to one embodiment of the present invention, a groove is not formed in the body portion 378 of the mouse member 380, and the supply pipes 380a and 380b inserted through one surface of the body portion 378 are the body portion 378. It can be configured to penetrate the other surface of the). Accordingly, the treatment material and the oxidant passing through the supply pipes 380a and 380b are directly supplied into the oxidation reaction pipe 340.

According to another embodiment of the present invention, the mouse member 380 may be configured to include three or more supply pipes and a separator separating the region inside the groove corresponding to the number of supply pipes. When the supply pipe is composed of three or more, the chemicals to assist the oxidation reaction in addition to the treatment material and the oxidant may be supplied into the oxidation reaction tube 340 through the respective supply pipes without being mixed.

8 is an exploded perspective view showing a mouse member according to another embodiment of the present invention.

Referring to FIG. 8, the second body portion 378b includes a plurality of circulation paths 384 and 386 connected to ends of the respective supply pipes 380a and 380b inserted through one surface of the second body portion 378b. Is formed. In addition, the plurality of communication paths 384A, 386A, 384B, 386B, 384C connected to the plurality of circulation paths 384 and 386 are connected to the first body part 378a, and penetrate the other surface of the first body part 378a. 386C, 384D, 386D, 384E and 386E).

In the plurality of circulation paths 384 and 386, the treatment material and the oxidant that have passed through the respective supply pipes 380a and 380b are introduced. Since each circulation path 384 and 386 is connected to the end of one supply pipe, the treatment material and the oxidant passing through the respective supply pipes 380a and 380b are not mixed and circulate in the circulation paths 384 and 386.

Although FIG. 8 illustrates that two circulation paths 384 and 386 are formed, the number of circulation paths may be added corresponding to the number of supply pipes.

Communication paths (384A, 386A, 384B, 386B, 384C, 386C, 384D, 386D, 384E, and 386E) are formed inside the body portion 378, and specific positions (384a, 384b, 384c, 384d, 384e, 386a, 386b, 386c, 386d, and 386e) to the circuits 384 and 386. Treatment materials and oxidants circulating in the circulation furnaces 384 and 386 can be supplied to the oxidation reaction tube 340 through the communication passages 384A, 386A, 384B, 386B, 384C, 386C, 384D, 386D, 384E and 386E. have.

A plurality of grooves having a predetermined depth may be formed in a portion of the body portion 378a of the mouse member 380 according to the present invention. Here, communication paths 384A, 384B, 384C, 384D, 384E, 386A, 386B, 386C, 386D and 386E connected to the circulation paths 384 and 386 penetrate the bottoms of the grooves. In addition, the formation position of the grooves corresponds to the positions of the plurality of flow paths of the oxidation reaction tube 340 described with reference to FIGS. 5 and 6.

Separators 382a, 382b, 382c, 382d, and 382e are disposed inside each groove to separate the region inside the groove. Accordingly, the treatment material and the oxidant discharged from the communication paths 384A, 386A, 384B, 386B, 384C, 386C, 384D, 386D, 384E, and 386E penetrating the bottom of the grooves are not mixed, and the oxidation reaction tube 340 ) Can be supplied.

Example

Supercritical water and subcritical water oxidation reaction was carried out by adding 100% of stoichiometric ratio H ₂ O ₂ to 1000ppm 2-chlorophenol, which is a model wastewater, without the addition of metal. , 400.degree. C.), the decomposition efficiency was 95.92%, and decomposition efficiency in the subcritical water oxidation reaction (reaction conditions: 220 atm, 360 ° C.) was 94.43%.

Since the six metals shown in Table 1, respectively, after the addition of the supercritical water and subcritical water oxidation reaction under the same conditions are shown in Figures 9 to 11.

Example 1 Stainless steel C Cr Fe Mn Mo P Si S Ni 0.08 17 66.35 2 1.5 0.045 One 0.03 12 Example 2 Inconel Al C Cr Co Fe Mn Mo Nb Si Ti Ni 0.4 0.1 22 One 5 0.5 9 3.7 0.5 0.4 57.4 Example 3 Monel Ni Fe Mn Al Ti Cu Si S 66.5 2.0 1.50 2.7 10.5 30.0 0.5 0.010 Example 4 Hastelloy C Co Cr Fe Mn Mo Ni P S Si Tu V 0.02 2.5 15.5 5.54 One 16 55.2 0.03 0.03 0.08 3.75 0.35 Example 5 Titanium C Cr Fe H N O Ti 0.1 0.015 0.2 0.015 0.03 0.25 99.41 Example 6 Zirconium C H Hf N Zr 0.05 0.005 4.5 0.025 95.42

9 to 14, the efficiency of the reaction involving the addition of metal in the subcritical water and supercritical water oxidation reactions was confirmed to show an efficiency increase of 1 to 3% compared to the reaction without adding metal. The increase in decomposition efficiency in the coefficient oxidation reaction was found to be larger than that in the supercritical water oxidation reaction.

In addition, it was confirmed that the metal elements constituting the alloy, such as iron, nickel, chromium, manganese, copper, molybdenum, zirconium and titanium, participated in improving the reaction efficiency.

Preferred embodiments of the present invention described above are disclosed for purposes of illustration, and those skilled in the art having various ordinary knowledge of the present invention may make various modifications, changes, and additions within the spirit and scope of the present invention. Additions should be considered to be within the scope of the following claims.

In the oxidation reactor of the present invention, a plurality of metal specimens having a predetermined shape are located inside the reaction zone, and the metal oxide produced by the oxidation reaction and the metal ions produced by the corrosion reaction act as catalysts to improve the reaction efficiency. At the same time it can have a high decomposition efficiency while relaxing the reaction conditions.

Claims (10)

A mouse member for introducing substances to be oxidized; An oxidation reaction tube for oxidatively decomposing target substances introduced through the mouse member; And Including a heater for changing the temperature of the oxidation reaction tube, An oxidation reactor, characterized in that the metal or metal alloy is filled in the oxidation reaction tube. The oxidation reactor of claim 1, wherein the metal or metal alloy comprises at least one metal selected from iron, nickel, chromium, manganese, copper, molybdenum, zirconium, and titanium. The method of claim 1, wherein the mouse member, Body portion; And And a plurality of supply pipes spaced apart from one surface of the body portion at predetermined intervals penetrating the other surface. The oxidation reactor according to claim 1, wherein the oxidation reactor further comprises a reaction body for supplying water and a neutralizing agent to change the temperature of the oxidation reaction tube. The oxidation reactor according to claim 4, wherein the water introduced through the reaction body is heated to a subcritical or supercritical temperature through the heater to change the temperature of the oxidation reaction tube. The oxidation reactor of claim 4, wherein a groove having a predetermined depth is formed in a portion of the body portion, and supply pipes inserted through one surface of the body portion penetrate a bottom surface of the groove. The oxidation reactor according to claim 1, wherein the oxidation reaction tube is composed of one or more tubes each having one flow path or one tube having a plurality of flow paths. The body portion of the mouse member, A plurality of circulation paths formed at a predetermined depth in the body part and connected to ends of respective supply pipes inserted through one surface of the body part; And Oxidation reactor, characterized in that connected to the circulation paths, a plurality of communication passages penetrating the other surface of the body portion is formed. The oxidation reactor according to claim 1, wherein the oxidation reaction tube is made of metal or ceramic. The method of claim 1, wherein the oxidation reactor, And an neutralization chamber disposed at an outlet side of the oxidation reaction tube and mixing and neutralizing the neutralizing agent introduced through the reaction body and the decomposition material discharged from the oxidation reaction tube.

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