KR20040057105A - Waste water oxidation apparatus and system thereof - Google Patents

Abstract

PURPOSE: An apparatus for oxidizing and decomposing waste solution is provided which is capable of treating waste solution containing organic matter using porous ceramic pipe and supercritical water oxidation, and a system for oxidizing and decomposing waste solution using the apparatus is provided. CONSTITUTION: The apparatus comprises a main body(11) on an upper part of a supercritical water inflow port(16) for flowing in supercritical water is formed, and on a lower part of which a neutralized water inflow port(17) for flowing in neutralized water is formed based on a supporting flange for separating an inner space of the main body into two spaces; a sealing plate(14) which is connected to an upper part of the main body, and on which a wastewater inflow port(13) for flowing in waste solution is formed; a nozzle plate(15) which is connected to a lower part of the main body, and on which nozzle(15a) is formed; and a ceramic pipe(12) which is connected with the wastewater inflow port and the nozzle by passing through the supporting flange, and on the side surface of which a plurality of micro-holes are formed, wherein the apparatus further comprises a discharge can(18) which is connected with the nozzle with being connected to the nozzle plate, and on which treated water discharge ports(19) for discharging treated water are formed.

Description

Wastewater Oxidative Decomposition Device and Wastewater Oxidative Decomposition System Using the Same {WASTE WATER OXIDATION APPARATUS AND SYSTEM THEREOF}

The present invention relates to an apparatus and system for treating waste liquid, and more particularly, to a waste liquid oxidative decomposition apparatus capable of treating waste liquid containing organic matter using a porous ceramic tube and supercritical water oxidation, and a waste liquid oxidative decomposition system using the same. It is about.

Representative by-products generated by industrialization include industrial wastewater and wastewater discharged from various industrial sites. The most widely used method for the treatment of industrial wastewater and wastewater is a biological treatment method, but the method is not suitable for the treatment of wastewater and wastewater containing high concentrations of organic matter, or especially hardly degradable organic matter or toxic organic matter. there was.

In order to solve the above problems, a lot of technical researches and developments have recently been conducted on the wastewater treatment technology by supercritical water oxidation. The supercritical water oxidation method is a method of adjusting the water itself with contaminants above a critical point of water (temperature 374 ° C., pressure 218 atm) and oxidizing contaminants in the presence of an oxygen source such as oxygen or air. Silver can decompose more than 99.99% of most organic contaminants within minutes. In this case, the main product is water vapor, carbon dioxide, etc., and the final aqueous solution mixture is harmless, so it can be discharged as it is without special aftertreatment.

The supercritical water oxidation technology described above is funded by universities and research institutes funded by government and military organizations such as the US Department of Energy (DOE), NASA, DOD, and the Army and Naval Research Institute. Technological developments have been carried out with a focus on the development of technologies for treating wastewater and waste generated from other military chemicals. The oldest company established to commercially apply these findings to industrial wastewater treatment is Modar Inc., which is known to sell the technology to ABB Lummus Crest, Organo of Japan. Modar Inc.'s technology is designed to coexist with supercritical and subcritical zones in a reactor, and to separate and dissolve solid components into subcritical zones and discharge them from the reactor (US Pat. Nos. 4,338,199, 4,543,190, 4,822,497, 5,106,513, and 5,190,560). The first commercialized facility for supercritical water oxidation technology was installed at Huntsman Corp., Texas, USA, which was installed by research at Eco Waste Technologies (EWT) and Texas State University, USA. In Japan, the first supercritical hydroxide test facility was built in February 1995 in the central research facility of Organo Corp. in Toda, Tokyo. Organo Corp.'s technology was developed by adopting Modar's technology (1 ton / day of processing capacity) of the United States. Especially, research and development focused on the decomposition of hardly degradable and toxic chloride organic compounds such as PCB, TCE and dioxin. (Japanese Patent Laid-Open No. 9-85075).

However, the supercritical water oxidation method described above has some problems as described below, and it has been a major problem to solve such problems efficiently.

First, the biggest problem is that the corrosion of the device is very high because the oxidation power is very strong. In other words, since expensive metal materials must be used to prevent such corrosion, a lot of equipment costs are required. To solve this problem, techniques have been developed to coat the inside of the reactor with corrosion resistant materials (US Pat. Nos. 5,461,648, 5,527,471, 5,545,337). Techniques for installing the outer wall with a low-cost metal have also been developed (US Pat. No. 5,591,415, Japanese Patent Laid-Open No. 9-085075, PCT Publication No. WO 9602471, WO 9218426). In addition, a technology has been developed to continuously and evenly inject noncorrosive water into the double pipe to prevent direct contact of corrosive substances on the wall surface (US Patent Nos. 5,670,040, 5,571,424, 5,571,423, and European Patent Publications). 708058). However, the above techniques are effective in preventing corrosion, but they are weak to solve the following problems, and above all, there is a problem of high cost.

Second, another problem is that in supercritical water, inorganic components precipitate and accumulate on the reactor wall. Organic matter is completely dissolved in the supercritical water, while inorganic matter is present in the salt state in the supercritical state or is produced during supercritical oxidation. Accumulated and precipitated solids foul the reactor internal walls, making long term operation of the reactor impossible. In order to solve the above problems, technologies for dissolving and discharging solids while maintaining the reactor in the supercritical and subcritical regions have been developed (US Pat. Nos. 4,338,199, 4,543,190, 4,822,497, 5,106,513, and 5,190,560). ), And also a technique for preventing the generation of scale on the wall as the particles flow (US Pat. No. 5,543,057, PCT Publication WO 9418128), etc., and a method of changing the reactor operating conditions (PCT Publication WO9519323, WO 9619415). ) Has been developed. However, the above-described techniques also have a problem that it is difficult to solve the problem that creates a high cost and a weak corrosion prevention.

The present invention is proposed to solve the above problems, by installing a porous ceramic tube that can be in direct contact with the waste water containing the oxidant through the supercritical water to form a supercritical water film on the inner surface of the device to prevent corrosion, minerals It is to provide a waste liquid oxidative decomposition device and waste drug oxidative decomposition system using the same that can effectively solve the problems of accumulation prevention and high cost prevention at the same time.

1 is a cross-sectional view briefly showing the structure of a waste liquid oxidative decomposition apparatus according to the present invention,

2 is a block diagram illustrating a waste liquid oxidative decomposition system using a waste liquid oxidative decomposition apparatus according to the present invention,

3 is an enlarged cross-sectional view showing the flow of supercritical water and wastewater containing an oxidant in a ceramic tube according to the present invention.

Explanation of symbols on the main parts of the drawings

1: supercritical reactor 11: body

12 ceramic tube 13 wastewater inlet

14: sealing plate 15a: nozzle

15: nozzle plate 16: supercritical water inlet

17: neutralized water inlet 18: outlet

19: treated water outlet 20: temperature measuring instrument

21: waste water storage tank 22, 32, 42, 52: high pressure injection pump

23: wastewater heater 24, 34: transfer pipe

31: supercritical water storage tank 33: supercritical water heater

41: neutralized water storage tank 51, 53: treated water evaporator

54: treated water storage tank

In order to achieve the above object, the waste liquid oxidative decomposition apparatus of the present invention has a supercritical water inlet through which a supercritical water is introduced based on a support flange separating the internal space into two, and a neutralized water inlet through which neutralized water is introduced into the lower part. A body formed; A sealing plate coupled to an upper end of the main body and having a wastewater inlet through which waste liquid is introduced; A nozzle plate coupled to a lower end of the main body and having a nozzle formed thereon; And a ceramic tube communicating with the wastewater inlet and the nozzle while passing through the support flange and having a plurality of micropores on a side thereof.

The waste liquid oxidative decomposition system using a waste liquid oxidative decomposition device may include a wastewater heater connected to a wastewater inlet of a wastewater oxidative decomposition device to heat wastewater introduced from the wastewater storage tank to the wastewater inlet; A supercritical water heater connected to the supercritical water inlet for heating supercritical water introduced from the supercritical water storage tank to the supercritical water inlet; A neutralized water storage tank connected to the neutralized water inlet; And a treated water evaporator connected to the treated water outlet.

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

1 is a cross-sectional view schematically showing the structure of the waste liquid oxidative decomposition apparatus according to the present invention, Figure 2 is a block diagram for explaining the oxidative decomposition process of the waste liquid using the waste liquid oxidative decomposition apparatus according to the present invention.

As can be seen from the figure, the apparatus of the present invention is a supercritical reactor 1, which comprises a main body 11 made of a highly corrosion-resistant alloy tube (SUS 316 and Hastelloy C alloy), and a ceramic at the center of the main body 11. It consists of a tube (12).

The main body 11 is divided into an upper main body pipe 11a and a lower main body pipe 11b, and a support flange 13 is disposed between the upper main body pipe 11a and the lower main body pipe 11b. The sealing plate 14 is coupled to the flange of the upper body tube 11a on the upper side of the main body tube 11a, and the nozzle plate 15 having the nozzle 15a is coupled to the lower side of the lower body tube 11b.

A supercritical water inlet 16 is formed above the upper main body pipe 11a, and a neutralized water inlet 17 is formed above the lower main body pipe 11b.

In the center of the main body 11, the ceramic tube 12 having a plurality of fine holes formed on the side thereof is supported at both ends by the sealing plate 14 and the nozzle plate 15 while being inserted into the support flange 13.

The support flange 13 is coupled to the upper flange of the lower body pipe 11b to spatially separate the upper body pipe 11a and the lower body pipe 11b, and the support flange 13 and the ceramic pipe 12 are By being tightly coupled, the supercritical water flowing into the supercritical water inlet 16 and the neutralized water flowing into the neutralizing water inlet 17 are not mixed with each other.

The discharge vessel 18 bolted to the lower side of the above-described nozzle plate 15 is formed with a treatment water discharge port 19 for discharging the treatment water on the lower side and the side.

The temperature measuring device 20 is installed outside the upper body pipe 11a, the lower body pipe 11b, and the discharge container 18 to measure the temperature in each space.

The supercritical reactor 1 configured as described above is included in a waste liquid oxidative decomposition system as shown in FIG. 2 to treat waste water and waste liquid.

The process is described in more detail with reference to Figures 1 and 2 as follows.

The supercritical reactor 1 has an internal condition in the upper main body pipe 11a in which the water pressure is maintained at 220 to 350 atm and the temperature at 400 to 600 ° C., for example, at the critical pressure of water 218 atm and the critical temperature of the water (374 ° C.) or more. A corresponding upper region; Internal conditions include a lower region corresponding to the lower body pipe (11b) having a pressure of 220 to 350 atm and a temperature of 25 to 200 ° C, for example, at least 218 atm and less than 374 ° C; And it can be divided into a discharge area corresponding to the discharge container 18 in which the treated water is discharged. Therefore, the upper region maintains the supercritical state, and the lower region and the discharge region maintain the subcritical state.

At the top of the upper region, a wastewater inlet 13 communicating with the ceramic tube 12 is provided on the sealing plate. The waste water containing the oxidant is temporarily stored in the waste water storage tank 21 and then raised to an operating pressure above the critical pressure (218 atm) of water through the high pressure injection pump 22, and then the temperature is 250 to 300 in the waste water heater 23. After being heated to < RTI ID = 0.0 > C, < / RTI > the wastewater inlet 13 is introduced into the apparatus of the present invention, ie the supercritical reactor 1.

The transfer pipe 24 from the wastewater heater 23 to the wastewater inlet 13 is thermally insulated to prevent heat from being released to the outside. The waste liquid containing organic matter may be waste water, sewage, sludge and organic waste liquid, and the like, and as the oxidizing agent, oxygen, air, gas containing oxygen, aqueous hydrogen peroxide solution or liquid containing ozone and oxygen may be used.

In addition, a supercritical inlet 14 through which the supercritical water flows is formed at the upper end of the cylindrical body 11a of the upper region. The supercritical water is temporarily stored in the supercritical water storage tank 31, and then The pump was boosted to a temperature far exceeding the critical pressure (218 atmospheres) of the pump 32 and then heated in a supercritical water heater 33 to a temperature of 550 to 600 ° C., and then through the supercritical water inlet 14. It is introduced into the upper region of the supercritical reactor (1).

The transfer pipe 34 from the supercritical water heater 33 to the supercritical reactor 1 is thermally insulated to prevent the heat from being released to the outside. Wastewater flowing into the upper zone is introduced below the supercritical temperature of water, but since the temperature of the incoming supercritical water is 550 to 600 ° C as described above, it does not affect the supercritical conditions for the supercritical reaction, but rather at the top of the upper zone. By preheating the waste water effectively, it can make efficient use of heat.

3 is an enlarged cross-sectional view showing the flow of supercritical water and wastewater containing an oxidant in a ceramic tube according to the present invention.

As shown in FIG. 3, a ceramic tube 12 is provided in the center of the main body 11 of the upper region maintained in the supercritical region.

The ceramic tube 12 is a porous tube in which minute holes are innumerable, and the supercritical water introduced from the supercritical water inlet 16 passes from the outside to the inside to allow the oxidant to be formed on the inner and inner surfaces of the ceramic tube 12. It will be able to effectively oxidize the waste water containing. At the same time, the fine holes drilled in the ceramic tube 12 allow the supercritical water to form a supercritical water film outside the ceramic tube 12 so that the ceramic tube 12 can pass through the waste water containing the oxidant. Even if there is a fine material, it is impossible to reach the body 11 to prevent corrosion of the body 11 and reactor fouling of the inorganic material.

In addition, the supercritical water film formed by the fine pores functions to effectively absorb the inorganic material present in the supercritical water in the salt state in the supercritical region to oxidize organic substances in the wastewater of the supercritical water.

In addition, the upper region of the ceramic tube 12 is a heat insulation treatment is surrounded by the main body 11 to prevent the discharge of heat to the outside of the reactor.

As described above, the wastewater having undergone the supercritical oxidation in the upper region moves to the lower region maintained in the subcritical state by gravity. The main body 11 of the lower region is provided with a neutralized water inlet 17 through which neutralized water at about 25 ° C. flows. As shown in FIG. 2, the neutralized water is temporarily stored in the neutralized water storage tank 41 and then raised to an operating pressure equal to or higher than the critical pressure (218 atm) of water through the high-pressure injection pump 42. Inflow to the lower region through (17).

In the lower region of the supercritical reactor 1 as in the upper region, the wastewater reacts efficiently with neutralized water in the inner and inner surfaces of the porous ceramic tube 12 to be converted into a harmless component and to the outside of the ceramic tube 12. The wastewater does not go out, but unlike the upper region, the inorganic components in the wastewater are present in the dissolved state in the water, not in the salt state, below the subcritical region.

Neutralized wastewater, that is, treated water, moves from the lower region to the discharge region maintained below the critical region by gravity, and its inlet is pointed as a nozzle (15a) to increase the flow rate of the treated water. .

The discharge area is an area that is maintained below the critical condition. Unlike the upper and lower areas, the discharge area is not provided with the ceramic tube 12 therein, and the treatment water discharge port 19 is provided at the side and the lower part.

The inorganic substance dissolved in the treated water is heavy and sinks, and thus is discharged to the lower treated water outlet 19, and then transferred to the treated water evaporator 51 to which cooling water is supplied, as shown in FIG. After some is pressurized by the high-pressure injection pump 52 and mixed with the neutralized water is injected into the lower region and circulated, some are discharged to the outside and some are sent to the analyzer for analysis. The treated water excluding the inorganic substance in the treated water is discharged to the side treated water outlet 19 and then transferred to the treated water evaporator 53 to which the cooling water is supplied, and then to the treated water storage tank 54 and then externally. Is discharged.

The outside of the main body 11 is provided with a plurality of temperature measuring device 20 to control and operate to achieve a suitable condition in the supercritical region, the subcritical region, the discharge region.

As described above, according to the present invention, the supercritical oxidation reaction between the main body and the organic material made of the corrosion-resistant alloy tube can be efficiently performed to prevent corrosion and high cost.

In addition, by forming the supercritical water film on the outside of the fine holes of the ceramic tube, it is possible to prevent the corrosion that was a problem in the process of the supercritical water treatment.

Furthermore, there is an effect that can be treated with high efficiency and high purity in the efficiency of wastewater treatment.

Claims (6)

A supercritical water inlet through which supercritical water is introduced based on a support flange separating the internal space into two and a neutralized water inlet through which neutralized water is introduced; A sealing plate coupled to an upper end of the main body and having a wastewater inlet through which waste liquid is introduced; A nozzle plate coupled to a lower end of the main body and having a nozzle formed thereon; A ceramic tube communicating with the wastewater inlet and the nozzle while passing through the support flange and having a plurality of micropores on the side thereof. Waste liquid oxidative decomposition apparatus comprising a. The waste liquid oxidative decomposition apparatus according to claim 1, further comprising a discharge container coupled to the nozzle plate and in communication with the nozzle, the discharge container having a treated water outlet configured to discharge the treated water. The apparatus of claim 1, wherein the supercritical water flowing into the supercritical water inlet is 550 to 600 ° C. The waste liquid oxidative decomposition apparatus according to claim 1, wherein the internal space between the sealing plate and the support flange into which the supercritical water flows is 220 to 350 atm and 400 to 600 ° C. The waste liquid oxidative decomposition apparatus according to claim 1 or 4, wherein the internal space between the support flange and the nozzle plate into which the neutralized water flows is 220 to 350 atm and 25 to 200 ° C. In a waste liquid oxidative decomposition system using a waste liquid oxidative decomposition device, A wastewater heater connected to the wastewater inlet of the wastewater oxidative decomposition apparatus to heat the wastewater flowing into the wastewater inlet from the wastewater storage tank; A supercritical water heater connected to the supercritical water inlet for heating supercritical water introduced from the supercritical water storage tank to the supercritical water inlet; A neutralized water storage tank connected to the neutralized water inlet; And Wastewater oxidative decomposition system comprising a treatment water evaporator connected to the treatment water outlet.