KR100522575B1 - Wastewater and wasteliquid disposal apparatus using supercritical water oxidation process - Google Patents

Abstract

The present invention relates to a wastewater and wastewater treatment apparatus using supercritical water oxidation method, and more particularly, to completely solve the problem of corrosion and salt precipitation by acid generated during the oxidative decomposition of wastewater and wastewater under supercritical pressure and temperature. It is an object of the present invention to provide a wastewater and waste liquid treatment apparatus using a supercritical water oxidation method configured to solve the problem.

In order to achieve the above object, the present invention is a wastewater and waste liquid treatment apparatus using a supercritical water oxidation method for oxidatively decomposing a reaction material mixed with an oxidant and a treatment material of wastewater and wastewater at a supercritical pressure and temperature, the reaction body The oxidation reaction ceramic tube (4) embedded in (2) is configured to pass through the supercritical pressure and the subcritical temperature reactant to be oxidatively decomposed, but the inlet flows into the water supply port (2-1) of the reaction body (2). The inlet portion of the oxidation-reaction ceramic tube 4 is made of subcritical temperature by water at a critical temperature, and the oxidation-reaction ceramic tube 4 is heated by the heater 3 external to the reaction body 2 to the supercritical temperature. ), The central portion of the c) constitutes a supercritical temperature, and the outlet portion of the oxidized reaction ceramic tube 4 forms a subcritical temperature by the neutralizing agent at room temperature flowing into the neutralizing agent supply port 2-2 of the reaction body 2. Supercritical Water Oxidation It is provided a waste water and waste water treatment apparatus using a.

Description

Wastewater and wastewater treatment system using supercritical water oxidation method {WASTEWATER AND WASTELIQUID DISPOSAL APPARATUS USING SUPERCRITICAL WATER OXIDATION PROCESS}

The present invention relates to a wastewater and wastewater treatment apparatus using a supercritical water oxidation method, and more particularly to completely solve the problem of corrosion and salt precipitation by acid in the process of oxidatively decomposing wastewater and wastewater under supercritical pressure and temperature. The present invention relates to a wastewater and waste liquid treatment apparatus using the supercritical water oxidation method.

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 of the hardly decomposable organic substances contained in various wastewaters and waste liquids is a decomposition method developed to decompose toxic organic compounds having high concentrations that are difficult to biodegrade but low concentrations to be destroyed 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 a 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. 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. Has not been solved and has not been commercialized.

Recently, research has been conducted to solve the problem of acid corrosion or fouling by applying a corrosion resistant material, but even if the inner wall of the reactor in which the oxidation reaction is made of a corrosion resistant metal still has corrosion, US Patent No. 5,461,648 , 5,527,471, 5,545,337, 5,545,337 is a technique for coating the inner wall of the reactor with a non-metal ceramic, etc., there is a problem in durability due to the non-uniformity of the coated ceramic.

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

First, as shown in FIG. 1, the reaction material (a mixture of the treatment material and the oxidant) is supplied to the internal ceramic tube 51, and water is injected into the external metal tube 50 while the supercritical water is supplied into the external ceramic tube 51. It is configured to prevent the phenomenon that the reaction material flowing in the inner ceramic tube is discharged to the outside through the injection hole while being injected into the interior of the inner ceramic tube through (52).

However, this reactor structure can solve the problem of corrosion by acid to some extent, there is a problem in the durability of the internal ceramic tube 51, such as cracks are generated around the injection port 52 by the supercritical pressure of water.

Then, as shown in FIG. 2, after supplying the oxidizing agent and the treatment material into the reactor 60, inducing the oxidation reaction in the supercritical water state to decompose the treatment material, and then controlling the salt water state to prevent salt precipitation. It is configured to.

This prior art is effective in preventing salt precipitation, but has a structural problem that can not be prepared at all against corrosion by acid.

As such, the supercritical water oxidation method is the only technology capable of completely oxidatively decomposing almost all organic matters, but it is an obstacle to practical use because no solution for corrosion and salt precipitation caused by the acid generated during the oxidation process is made.

SUMMARY OF THE INVENTION The present invention has been made to improve such a conventional problem, and supercritical water is configured to completely solve the problem of corrosion and salt precipitation by acid generated during the oxidative decomposition of wastewater and waste liquid under supercritical pressure and temperature. It is an object of the present invention to provide an apparatus for treating wastewater and waste liquid using an oxidation method.

In order to achieve the above object, the present invention provides a wastewater and waste liquid treatment apparatus using a supercritical water oxidation method for oxidatively decomposing a reaction material mixed with an oxidant and a treatment material of wastewater and wastewater at a supercritical pressure and temperature, and is embedded in a reaction body It is configured to oxidatively decompose by passing the reaction material of supercritical pressure and subcritical temperature through the oxidized reaction ceramic tube. When the water is heated to the supercritical temperature by the heater external to the reaction body, the central part of the oxidation reaction ceramic tube forms the supercritical temperature, and the neutralization of the oxidation reaction ceramic tube is carried out by the neutralizing agent at room temperature flowing into the neutralizing agent supply port of the reaction body. Wastewater and waste liquid treatment apparatus using supercritical water oxidation method characterized in that the outlet portion to achieve a subcritical temperature Will be provided.

And, in the present invention, the oxidation ceramic tube is composed of one or more pipes each having one flow path, or composed of one pipe having a plurality of flow paths, the upper packing for supporting the outlet portion of the oxidation reaction ceramic pipe Is provided to contact the outer peripheral surface of the oxidation reaction ceramic tube.

In addition, in the present invention, a neutralization chamber is provided on the outlet side of the oxidized reaction ceramic tube, and is configured to mix and neutralize the neutralizing agent injected through the injection port and the decomposed substance discharged from the oxidized reaction ceramic tube.

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

Figure 3 is a block diagram illustrating one embodiment of the present invention, Figure 4 is a cross-sectional view illustrating one embodiment of the reaction treatment unit of the present invention, Figure 5 is a decomposition illustrating an embodiment of the reaction treatment unit of the present invention. 6 is an exploded perspective view illustrating another embodiment of the reaction treatment unit in the present invention, and FIG. 7 is an exploded perspective view illustrating another embodiment of the reaction treatment unit in the present invention.

According to an embodiment of the present invention, as shown in Figure 3, the reactant supply unit 20 and the water supply unit for supplying the reaction material of the treatment material and the oxidant, such as waste water and waste liquid, respectively or mixed in a subcritical state, 29), a neutralizer supply unit 30, an oxidation and neutralization reaction unit 1, and a decomposing substance treatment unit 40.

Here, the reactant supply unit 20 is for transporting the treatment material and the oxidant stored in the reactant storage tank 21 at a supercritical pressure (221 bar or more) using the pressure pump 22, the second in the preheater 24 It is configured to supply through the reactant supply line 26 while heated to about 15-35% of the critical temperature.

However, when the reactant supply unit 20 generates a large amount of acid while oxidizing the treated material and the oxidant in a subcritical state, the reactant storage tank 21 may include the reactant storage tank 21 to prevent corrosion by the acid. The oxidant storage tank is separated and stored, and after passing through each of the pressure pump 22 and the preheater 24, it may be configured to be supplied through the reactant supply line 26.

In addition, the water supply unit 29 pumps the water stored in the water storage tank 27 using a pressure pump 23, and heats the water supply line 25 in a state in which the preheater 24 is heated to a predetermined temperature or more. It is configured to feed through.

In addition, the neutralizing agent supply unit 30 is to pressurize the neutralizing agent stored in the neutralizing agent storage tank 31 using the pressure pump 32, through the check valve 33 and the needle valve 35, the neutralizing agent supply line 36 It is configured to supply at room temperature through.

On the other hand, the reaction treatment unit 1 according to the present invention is a supercritical pressure and temperature of the reaction material which is a mixture of the processing material and the oxidant supplied through the reactant inlet 8-1 connected to the reactant supply line 26 After oxidizing and decomposing in a state, it is neutralized and discharged to the decomposer outlet 7-1.

More specifically, in the reaction treatment unit 1, as shown in Figs. 4 and 5, the cylindrical tubular reaction body 2 has a neutralizing agent supply port 2-2 and a water supply port at upper and lower ends of its outer circumferential surface, respectively. (2-1) is provided.

At this time, the neutralizing agent supply port (2-2) of the reaction body (2) is connected to the neutralizing agent supply line 33 to supply the neutralizing agent into the reaction body, the water supply port (2-1) is a water supply line (25) ) To supply water to the inside of the reaction body.

Here, the heater 3 provided to heat the inside of the reaction body 2 to the supercritical temperature is the outer circumferential surface of the reaction body 2 so as to be located between the water supply port 2-1 and the neutralizer supply port 2-2. It is configured to attach to.

The upper and lower packings 9 and 10 are fitted to the reaction body 2 so as to close the inside thereof, and the upper and lower packings 9 and 10 are equipped with upper parts respectively provided at their centers. The upper and lower ends of the oxidation reaction ceramic tube 4 are coupled to the sphere 18 and the lower mounting hole 17.

At this time, the oxidation reaction ceramic tube 4 is fixed while the upper and lower ends are inserted into the upper mounting hole 18 of the upper packing 9 and the lower mounting hole 17 of the lower packing 10, respectively. It is installed vertically in the center of the inside.

In particular, the lower mounting hole 17 is simply a circular hole to block the leakage while the oxidation reaction tube 4 is inserted in the interference fitting method, the upper mounting hole 18 is the oxidation reaction ceramic as shown in FIG. The upper end side of the tube 4 is fixed to each other, and a small gap injection port 18-1 is formed on the circumferential surface thereof so as to enable injection of the neutralizing agent.

In this way, the injection port 18-1 is configured to be in contact with the outer circumferential surface of the oxidation reaction ceramic tube 4 to maximize the cooling efficiency by bringing the neutralizing agent of the subcritical temperature into contact with the oxidation reaction ceramic tube as much as possible.

Also, the upper cap 5 is placed on the upper portion of the upper packing 9, or the upper cap 5 is placed on the lower portion of the lower packing 10. When screwing with the upper side of the outer circumferential surface or screwing the lower cap (6) with the lower side of the outer peripheral surface of the reaction body (2) the upper compression block (7) or lower compression block (8) is the upper packing (9) or lower The packing 10 is pressed, thereby keeping the upper and lower packings in close contact with the upper and lower end surfaces of the reaction bodies, respectively, to prevent leakage.

Here, the lower compression block (8) is provided with a reactant inlet (8-1) at the center side thereof is connected to the reactant supply line (26), the reaction material flowing through the reactant inlet is oxidized reaction It is configured to supply through the lower side of the mixing tube (4).

In addition, the upper compression block (7) is provided with a decomposition material discharge port (7-1) at the center side of the decomposition material discharged through the upper side of the oxidation reaction ceramic tube (4) to the decomposition material processing unit 40 side It is configured to discharge.

In particular, the upper compression block (7) is provided with a neutralization chamber (15) therein, the neutralization chamber (15), the decomposition material discharged through the upper side of the oxidation reaction ceramic tube (4), and the injection port (18-) The neutralizing agent injected through 1) is mixed with each other to neutralize each other, and then discharged through the discharge material outlet 7-1.

Then, the water supplied into the reaction body (2) through the water supply port (2-1) is heated to the supercritical temperature by the heater (3) while raising the inside of the reaction body in the state heated to the subcritical temperature, the heating It is to perform the heat medium function to transfer the self heat to the oxidation reaction ceramic tube (4).

Furthermore, the water supplied into the reaction body 2 through the water supply port 2-1 pushes up the neutralizing agent supplied into the reaction body through the neutralizing agent supply port 2-2 so that the neutralizing agent flows backward to the lower side of the reaction body. Will block.

On the other hand, when the operation of the reaction treatment unit 1 will be described in detail, the reaction material which is a mixture of the treatment material (wastewater and waste liquid) and the oxidant supplied at the state of the supercritical pressure and the subcritical temperature from the reactant supply unit 20 reacts. It is supplied to the reactant inlet 8-1 through the material supply line 25 and passes through the oxidation reaction ceramic tube 4.

At this time, the water supplied into the lower side of the reaction body (2) through the water supply port (2-1) is heated in the heater (3) above the supercritical temperature, the temperature of the water heated above the supercritical temperature is oxidized again As it is delivered into the reaction ceramic tube 4, the reactants passing through the tube are heated to reach a supercritical temperature.

As a result, the reactant introduced through the reactant inlet 8-1 leads to a rapid oxidation reaction in a supercritical state while passing through the intermediate portion of the oxidative reaction ceramic tube 4, thereby completely decomposing the treated material. Proceeds.

And, the neutralizing agent at room temperature supplied from the neutralizing agent supply line 36 is mixed into the upper side of the reaction body 2 through the neutralizing agent inlet (2-2) and mixed with the water of the supercritical temperature rising in the reaction body. Dilution is made.

At this time, the neutralizing agent supplied from the neutralizing agent storage tank 31 is a high concentration and is mixed with water of the supercritical temperature in the reaction body 2 to have a subcritical temperature and to be diluted to an appropriate concentration. The neutralizing agent diluted with is injected into the neutralization chamber 15 through the injection port 18-1 while cooling the outlet side of the oxidation reaction ceramic tube 4.

Here, the decomposition material decomposed by the oxidation reaction while passing through the oxidation reaction ceramic tube 4 is discharged through the upper side of the oxidation reaction ceramic tube 4 and mixed with the neutralizing agent of the neutralization chamber 15 to be neutralized.

Hereinafter will be described in detail the problem solving for the corrosion and salt precipitation of the acid in the reaction treatment unit (1) according to the present invention.

First, the reactant, which is a mixture of the treatment material (wastewater and waste solution) and the oxidant, passes through the oxidation reaction ceramic tube 4 and reaches a supercritical water state to cause a rapid oxidation reaction, thereby generating 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 ceramic tube 4, and is discharged into the neutralization chamber 15 through the upper side of the oxidation reaction ceramic tube. Immediately through the process of being discharged back to the decomposition material processing unit 40 neutralized by the neutralizing agent it is possible to completely solve the problem of corrosion by acid.

In addition, salt precipitation generated during the reaction of the reactants passing through the oxidized reaction ceramic tube 4 causes problems such as blocking or blocking the movement of fluid in the pipe while causing scaling on the inner wall of the oxidized reaction ceramic tube. This can minimize the amount of production or block production when controlling solubility with temperature.

In the present invention, when the oxidation reaction ceramic tube 4 through which the reactant passes is divided into approximately the lower end, the middle end, and the upper end, the lower end of the oxidation reaction ceramic tube does not generate salt precipitation while its solubility is gradually increased as the subcritical temperature. In the middle portion of the oxidized reaction ceramic tube, the solubility reaches a maximum as a supercritical temperature, and the salt is precipitated while rapidly decreasing.

At this time, in the present invention, the neutralizing agent at room temperature introduced into the reaction body (2) through the neutralizing agent supply port (2-2) and the water heated to the supercritical temperature while being risen in the reaction body are diluted at the subcritical temperature. Will produce a neutralizer.

The neutralizing agent of the subcritical temperature is cooled by contact with the upper end of the oxidation ceramic tube (4), thereby increasing the solubility as the upper end of the oxidation ceramic tube is lowered to the subcritical temperature, eventually stopping the oxidation ceramic tube Salt precipitation, which began to occur in the unit, reaches the upper end of the oxidation-reaction ceramic tube and is cooled to subcritical temperature, and is dissolved again with an increase in 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 the wastewater and the waste liquid by the oxidation reaction in the reaction treatment unit 1.

6 is an exploded perspective view illustrating another embodiment of the reaction treatment part of the present invention, in which a plurality of flow paths are formed in the oxidation reaction ceramic tube 4 having one body, thereby increasing the decomposition throughput of the treatment material. There is an advantage.

Fig. 7 is an exploded perspective view illustrating another embodiment of the reaction treatment section of the present invention, which is a method of increasing the decomposition productivity of a treated material by providing a plurality of oxidation reaction ceramic tubes 4 each having one flow path.

On the other hand, the decomposition material discharged through the decomposition material discharge port 7-1 is processed while passing through the decomposition material processing unit 40, the decomposition material processing unit 40 heat exchanges the neutralized decomposition material discharged from the reaction processing unit (1) After cooling to room temperature in the group 41, the filter in the line filter 43, and then the pressure regulator 42 to reduce the pressure to normal pressure.

And, the decomposition products converted to room temperature and atmospheric pressure is separated into gas and liquid through the gas-liquid separator 44, the gas is discharged to the atmosphere, the liquid is discharged to the stream, a portion of the liquid to the sampling tank 45 The collected and analyzed components of the decomposition material are reflected in the decomposition process of the treated material.

The present invention constituted as described above has the technical features to completely solve the problems of corrosion and salt precipitation by the acid generated during the oxidation reaction in the oxidation treatment of the treatment material in the supercritical water state.

As described above, specific embodiments have been described in the detailed description of the present invention, but various modifications may be made without departing from the scope of the present invention.

Therefore, the substantial scope of the present invention should not be limited by the above-described embodiment, but should be defined by the same structure as the claims as well as the claims described below.

The present invention configured as described above provides an effect that can completely solve the problems of corrosion and salt precipitation by acid generated in the process of oxidatively decomposing wastewater and waste liquid under supercritical pressure and temperature.

1 and 2 is a configuration diagram illustrating one conventional embodiment;

3 is a block diagram illustrating an embodiment of the present invention;

4 is a cross-sectional view illustrating one embodiment of a reaction treatment unit of the present invention;

5 is an exploded perspective view illustrating an embodiment of a reaction treatment unit of the present invention;

Figure 6 is an exploded perspective view illustrating another embodiment of the reaction treatment unit in the present invention,

Figure 7 is an exploded perspective view illustrating another embodiment of the reaction treatment unit in the present invention.

<Description of the symbols for the main parts of the drawings>

DESCRIPTION OF SYMBOLS 1 Reaction treatment part 20: Reactant supply part 29: Water supply part 30: Neutralizing agent supply part 40: Decomposition | disassembly material processing part

Claims (4)

In the wastewater and wastewater treatment apparatus using the supercritical water oxidation method, which oxidatively decomposes a reaction material mixed with an oxidant and a treatment material of wastewater and wastewater at supercritical pressure and temperature Oxidation reaction ceramic tube (4) embedded in the reaction body (2) is configured to pass through the reaction material of the supercritical pressure and subcritical temperature to be oxidatively decomposed, but flows into the water supply port (2-1) of the reaction body (2) The inlet portion of the oxidation-reaction ceramic tube 4 is subcritical temperature by the water of the subcritical temperature, and the water is heated to the supercritical temperature by the heater 3 external to the reaction body 2. The central portion of (4) forms a supercritical temperature, and the outlet portion of the oxidized reaction ceramic tube (4) forms a subcritical temperature by the neutralizing agent at room temperature introduced into the neutralizing agent supply port (2-2) of the reaction body (2). Waste water and waste liquid treatment apparatus using a supercritical water oxidation method. The method according to claim 1, The oxidation reaction ceramic tube (4) is composed of one or more tubes each having one flow path, wastewater and wastewater treatment apparatus using a supercritical water oxidation method, characterized in that composed of one tube having a plurality of flow paths. The method according to claim 1, The upper packing 9 for supporting the outlet of the oxidation ceramic tube 4 is a supercritical water oxidation method, characterized in that a plurality of injection holes (18-1) are provided to contact the outer peripheral surface of the oxidation reaction ceramic tube (4) Wastewater and wastewater treatment device used. The method according to claim 1, The neutralization chamber 15 is provided at the outlet side of the oxidation reaction ceramic tube 4 so as to neutralize the neutralizing agent injected through the injection port 18-1 and the decomposed substance discharged from the oxidation reaction ceramic tube 4. Wastewater and waste liquid treatment apparatus using a supercritical water oxidation method characterized in that the.