KR100778332B1 - Apparatus and method for chemical agent disposal by a 2-step process - Google Patents

Abstract

An apparatus and method for chemical agent disposal by a 2-step process is provided to treat a chemical agent safely and completely, by converting the chemical agent into a substance harmless to a human being. An apparatus for chemical agent disposal includes: a hydrolysis reactor(10) to hydrolyze or neutralize a chemical agent and to obtain a nontoxic substance; and a super critical water oxidation device to supply process water and oxygen. The super critical water oxidation device is constituted by an oxidation reactor(20), a main body including the oxidation reactor, and a heater inside, a pressure reducing set, a separator(33) to separate a product into a gas substance and a liquid substance; a heat exchanger(34) to cool the product, a filter to remove any particles in the product, and a treated water reservoir(36) to reserve treated water and to recycle it as process water.

Description

Apparatus and Method for Chemical Agent Disposal by a 2-step Process}

1 is a conceptual diagram schematically showing a two-step disposal process of a chemical agent according to the present invention.

2 is a view showing an embodiment of a supercritical water oxidizer which is a main component of a two-stage waste disposal apparatus of a chemical agent according to the present invention.

Figure 3 is a cross-sectional view showing an oxidation reactor of the supercritical water oxidizing apparatus of the main component of the present invention.

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

10: hydrolysis reactor

12: decomposition material supply

14: oxygen supply

14A: oxygen generator

14C: Oxygen Compressor

14 V: oxygen storage tank

16: process water supply

18: auxiliary fuel supply

12E, 14E, 16E, 18E: Heating Heat Exchanger

12F, 16F, 16F ', 18F: Particle Filter

12P, 16P, 16P ', 18P: High Pressure Pump

12V, 16V, 18V: reservoir

20: oxidation reactor

21: shell

22: inner tube

23: top cover

24: oxygen injector

25: Degradant Injector

26: lower cover

30: supercritical water oxidizer

31: oxidizer main body

32: decompression device

33: separator

34: cooling heat exchanger

35: particle filter

36: treated water reservoir

37: feed mixer

38: emissions mixer

The present invention relates to an apparatus and a method for the disposal of chemical agents, wherein the chemical agent is hydrolyzed or neutralized with water or caustic soda solution, and then oxidized in a supercritical state to be converted into a completely harmless substance and discharged. An apparatus and method for two-stage disposal of agents.

In general, chemical weapons designated as weapons of mass destruction must be disposed of completely in accordance with the Chemical Weapons Convention (CWC) so that they cannot be used again within a designated period of time. The key to achieving this is the safe and complete disposal of chemical agents, the most important substance of chemical weapons. However, most chemical agents are very deadly to humans, even with minor exposure to the atmosphere, and are very dangerous to handle and are toxic chemicals.

In the past, many countries deal with small amounts of chemical weapons by separating chemical agents from chemical weapons such as chemical coal, rockets, chemical mines, etc., and then incinerating them, neutralizing them with basic aqueous solutions or methylethanolamine, and then burying or incineration them. have. Russia, meanwhile, will neutralize chemical agents and solidify them to landfill, but this will not only require large landfills, but it will not be considered complete.

In addition, in the United States, in order to mass-produce stockpiles of chemical weapons, the chemicals are separated from chemical weapons, and then chemical incinerators and carcasses are incinerated directly in an incinerator. However, in the process of incineration of the chemical agent directly, the chemical agent leaks into the atmosphere or incompletely burned during the incineration operation, so that there is a problem that toxic substances may be released to the outside without being completely processed.

Therefore, in the future, the chemical weapons processing area to be established is expected to find and apply incineration alternative technology in accordance with the opposition from local residents. As an alternative to incineration, the U.S. has been selected as a candidate for neutralizing chemical agents and then oxidizing the neutralizing material into microcritical water or supercritical water.

In addition, the chemical agent must be thoroughly installed in order to protect the worker through the whole process before and after handling and treatment and to prevent the leakage of the chemical agent to the surrounding environment, such a device has a problem that becomes large. In addition, a plurality of activated carbon particle filters are used to remove harmful gases emitted during incineration. In this case, after a certain period of time, a new problem of treating waste activated carbon to which various harmful gases are adsorbed may occur.

As mentioned above, the technology to convert chemical agents into harmless materials through two-stage treatment has been developed as an incineration alternative technology that can supplement the shortcomings of waste disposal facilities by incineration and be newly applied according to the opposition of local residents.

In general, once a chemical agent is hydrolyzed with water or completely neutralized with a basic substance, the toxicity of the agent is dramatically reduced. Therefore, the resulting decomposition products are easy to handle even if the operator does not use or wear special equipment. However, decomposition products still contain substances regulated by the Chemical Weapons Convention (CWC), acidic substances such as halogens, and salts, which must be converted into completely harmless substances.

In other words, the conventional chemical agent treatment is proceeding by incineration of the chemical agent directly or by hydrolyzing the chemical agent and then solidifying the decomposition material and embedding it.

However, in the conventional chemical agent treatment method, when incineration of the chemical agent is directly incinerated due to inadvertent air leakage or incomplete combustion, the harmful gas may be present in a state where no toxic substances may be released to the outside of the human body and nature. There is a problem that is very harmful to the environment.

In addition, in the case where the neutralizing material is solidified and then landfilled after hydrolysis of the chemical agent, the neutralizing material contains an acidic substance such as a halogen group element and a salt, thereby causing a major cause of environmental pollution.

The present invention has been made in order to solve the above-mentioned conventional problems, and by treating the decomposition material formed by hydrolysis or neutralization of the chemical agent again to convert it into a harmless substance to the human body to safely and completely process the chemical agent It is an object of the present invention to provide a two-stage waste disposal apparatus and method for chemical agents.

Specifically, depending on the type of chemical agent, it is hydrolyzed or neutralized with water or caustic soda (NaOH) solution to completely remove the toxicity of the agent, and then the neutralized material is completely processed through supercritical water oxidation to remove water or carbon dioxide. It is to provide a two-stage waste disposal apparatus and method for the chemical agent that can be converted into.

In addition, the present invention is a two-step waste treatment apparatus of a chemical agent to prevent environmental pollution due to waste water by reusing as a hydrolysis solution or process water without releasing any water generated in the hydrolysis or supercritical water oxidation process to the outside And to provide a method.

In addition, the present invention is to minimize the corrosion of the external reactor is made thick to withstand the stress caused by the pressure difference while limiting the damage caused by the corrosion to the inner tube by the oxidation reaction in the inner tube of the double-walled oxidation reactor. It is an object of the present invention to provide an apparatus and method for two-step disposal of chemical agents.

The two-stage waste treatment apparatus of the chemical agent of the present invention for achieving the above object, by supplying water or caustic soda solution with the chemical agent to hydrolyze or neutralize the chemical agent to produce a decomposed substance to remove the toxicity of the chemical agent A hydrolysis reactor; It is characterized in that it comprises a supercritical water oxidizing apparatus for supplying the high temperature and high pressure process water and oxygen to the decomposition material produced in the hydrolysis reactor to supercritical oxidation.

In addition, according to the two-stage waste treatment apparatus of the chemical agent of the present invention, the supercritical water oxidizing apparatus comprises an oxidation reactor for completely oxidizing the decomposition material produced in the hydrolysis reactor using high temperature and high pressure process water and oxygen, An oxidizer main body installed inside the oxidizer and equipped with a heater, a decompression device for reducing the pressure of a product formed by oxidizing decomposition products in a supercritical water state by the oxidation reactor to atmospheric pressure, and a vapor phase of the product. It characterized in that it comprises a separation device for separating the substance and the liquid substance.

In addition, according to the two-stage waste treatment apparatus of the chemical agent of the present invention, the supercritical water oxidizing apparatus is installed in the upstream side of the depressurization apparatus and a cooling heat exchanger for rapidly cooling the product formed in the oxidation reactor, the cooling heat exchanger It is characterized in that it further comprises a particle filter installed on the front side of the group to remove the particulate matter contained in the product.

In addition, according to the two-stage waste treatment apparatus of the chemical agent of the present invention, the liquid substance from which the particulate matter is removed by the particle filter is discharged as it is through the separator or stored in the treated water storage tank and recycled into the process water. It is done.

In addition, the two-stage waste treatment apparatus of the chemical agent of the present invention, the decomposition material supply unit for providing a decomposition material produced in the hydrolysis reactor to the oxidation reactor of the supercritical water oxidizer; An oxygen supply unit for providing high temperature and high pressure oxygen to the oxidation reactor; The process water supply unit for supplying the process water of the high temperature and high pressure of the main reaction medium to the lower portion of the oxidation reactor, and provides the process water to the outlet side of the oxidation reactor for rapid cooling of the product.

In addition, according to the two-stage waste treatment apparatus of the chemical agent of the present invention, the oxidizer main body is installed at the inlet side of the oxidation reactor, the decomposition material supplied from the decomposition material supply unit and the oxygen supplied from the oxygen supply unit And an emission mixer installed at an outlet side of the oxidation reactor and cooling and neutralizing the product using process water or caustic soda solution.

In addition, the two-stage waste treatment apparatus of the chemical agent of the present invention, further comprises an auxiliary fuel supply for supplying auxiliary fuel of IPA (Isopropyl Alcohol) class to the oxidation reactor, the feed mixer is the auxiliary fuel It is characterized in that the auxiliary fuel supplied from the supply unit is also mixed and supplied together.

In addition, according to the two-stage waste treatment apparatus of the chemical agent of the present invention, the oxidation reactor is a cylindrical shell in which through holes penetrating up and down, and the inflow located in the through hole of the shell and containing the decomposition material The inner tube is formed at a height lower than that of the shell, the upper tube is coupled to the upper portion of the shell to block the upper end of the through hole, and is installed through the upper cover and is inside the inner tube. An oxygen injector for supplying oxygen to the oxygen injector, a decomposition material injector positioned inside the oxygen injector and protruding relative to the oxygen injector, and coupled to a lower portion of the shell to block a lower end of the through hole and communicate with the inner tube. A lowerkerer formed with a product supply hole for supplying water between the product discharge hole and the inner circumferential surface of the inner tube and the through hole and the outer circumferential surface of the inner tube. And, coupled to the lower end of the inner tube it is characterized in that it comprises a valve for Closed Open the resulting material discharge hole.

Further, according to the two-stage disposal device of the chemical agent of the present invention, the chemical agent is characterized in that it is one of a nerve agent, a nerve agent precursor and a blistering agent; The nerve agent is sarin (GB; O-Isopropyl Methylphosphonofluoridate) or VX, the nerve agent precursor is a binary agent such as DF (Methylphosphonicdifluoride) or OPA, the blistering agent is characterized in that mustard (HD).

Further, according to the two-stage waste treatment apparatus of the chemical agent of the present invention, the decomposition product of the chemical agent is characterized in that one of MPA (Methylphosphonic Acid) or TDG (Thiodiglycol); The decomposition product of the chemical agent is characterized in that it comprises an acid and a salt of a halogen group element.

In addition, the two-stage disposal method of the chemical agent of the present invention comprises: a toxic removal step of supplying water or caustic soda solution with the agent to hydrolyze or neutralize the chemical agent; It is characterized in that it comprises an oxidation step to oxidize the decomposition material by introducing the decomposition material produced in the step into the supercritical state of the reactor at a high temperature and high pressure and supply the process water and oxygen at a high temperature and high pressure.

In addition, the two-step waste treatment method of the chemical agent of the present invention, the post-treatment step of processing the product formed in the oxidation step to enable the external discharge and the discharge to separate and discharge the product after completion of the post-treatment as gas and liquid It further comprises a step.

In addition, according to the two-stage disposal method of the chemical agent of the present invention, the post-treatment step, the step of rapidly cooling the product, filtering the particulate matter contained in the product, and the supercritical pressure Characterized in that the step consisting of reducing the pressure to atmospheric pressure.

In addition, according to the two-stage disposal method of the chemical agent of the present invention, the toxic treatment step includes the step of further treating the primary decomposition material produced by neutralizing or hydrolyzing the chemical agent with a caustic soda solution. It is done.

In addition, according to the two-stage disposal method of the chemical agent of the present invention, the detoxification step causes the hydrolysis or neutralization reaction to proceed until the decomposition rate of the chemical agent reaches 99.99%, and the oxidation step is performed to It is characterized in that it is oxidized until the waste efficiency reaches 99.99% based on the total organic carbon or the treated material.

In addition, according to the two-stage waste disposal method of the chemical agent of the present invention, the internal reaction pressure of the reactor is 220 to 300 atm, the internal reaction temperature is characterized in that more than 374 ℃ 660 ℃.

In addition, according to the two-stage disposal method of the chemical agent of the present invention, the oxygen is characterized in that the pressurized to the internal reaction pressure of the reactor and then heated to a temperature of 400 ~ 500 ℃.

In addition, according to the two-stage disposal method of the chemical agent of the present invention, the decomposition material is characterized in that it is pressurized to the internal reaction pressure of the reactor and then heated to room temperature or 400 ℃ according to the type of decomposition material is supplied. .

In addition, according to the two-stage disposal method of the chemical agent of the present invention, the process water is characterized in that the pressurized supply to the internal reaction pressure of the reactor and heated to 400 ℃ to supply to the oxidation step.

In addition, according to the two-stage waste disposal method of the chemical agent of the present invention, in the oxidation step, further supplying the secondary fuel IPA to the reactor, the IPA is pressurized to the internal reaction pressure of the reactor, and then to 400 ℃ temperature It is characterized by supplying by heating.

According to the chemical agent waste treatment apparatus and method of the present invention described above, a hydrolysis reactor is used to hydrolyze or neutralize the chemical agent to generate a decomposed substance, which is oxidized in a supercritical oxidation reactor to the human body. It is made of harmless gases and liquids and discharged. In this case, a particle filter is used to remove salts or solid particles that may be generated in the oxidation reactor. That is, the particulate matter is filtered through the particle filter, and the pressure is reduced by using a decompression device and finally separated by gas / liquid separation through a separator to discharge the gaseous material and the liquid material. At this time, the sample is analyzed to determine the composition of the gas phase material and the treatment efficiency of the liquid material, and most of the gases discharged by treatment are nitrogen and carbon dioxide, which are harmless to the human body, and the liquid material is made of clean water.

On the other hand, the oxidation reactor may cause corrosion when treating the liquid waste containing the material consisting of a halogen group element. Therefore, in order to reduce the damage of the oxidation reactor due to corrosion, it comprises a plurality of pipes through which the reactant and the oxidant pass, and the reactants introduced into the reactor by the plurality of pipes are mixed at the top of the oxidation reactor and reacted instantly to oxidize. . The reactants (exhaust gas and liquid material) that have passed through the oxidation reactor are rapidly cooled in a cooling device.

In addition, the chemical agent to be treated in the present invention includes a blistering agent such as a nerve agent, a nerve agent precursor and mustard (HD), the nerve agent is VX or sarin (GB; O-Isopropyl Methylphosphonofluoridate), the mustard ( HD) is a sulfur mustard (Sulfurmustard; bis (2-chloroethyl) sulfide), and the nerve agent precursor consists of DF (Methylphosphonicdifluoride). In addition, the degradation agents of the nerve agent and mustard are MPA (Methylphosphonic acid) and TDG (Thiodiglycol), respectively. Etc.

Hereinafter, with reference to the accompanying drawings, a two-stage waste treatment apparatus and method of the chemical agent of the present invention will be described.

1 is a conceptual diagram schematically showing a two-stage disposal process of a chemical agent according to the present invention, Figure 2 is an embodiment of a supercritical water oxidizer which is a main component of the two-stage waste treatment apparatus of the chemical agent according to the present invention 3 is a cross-sectional view showing an oxidation reactor of a supercritical water oxidizer which is a main component of the present invention.

In the two-stage waste treatment apparatus of the chemical agent according to the present invention, a hydrolysis reactor for supplying water or a caustic soda solution together with the chemical agent to hydrolyze or neutralize the chemical agent to generate a decomposed substance which removes the toxicity of the chemical agent (10) )Wow; A supercritical water oxidizer (30) for supercritical oxidation by supplying high temperature and high pressure process water and oxygen to the decomposition material produced in the hydrolysis reactor (10); Decomposition material supply unit 12 for providing a decomposition material produced in the hydrolysis reactor 10 to the oxidation reactor 20 of the supercritical water oxidizer 30; An oxygen supply unit 14 for providing high temperature and high pressure oxygen to the oxidation reactor 20; Process water supply unit 16 for supplying the process water of the high temperature and high pressure, the main reaction medium to the lower portion of the oxidation reactor 20, and provides the process water to the outlet side of the oxidation reactor 20 for rapid cooling of the product material And an auxiliary fuel supply unit 18 for supplying auxiliary fuels of IPA (Isopropyl Alcohol) to the oxidation reactor 20.

The hydrolysis reactor 10 is a device for hydrolyzing or neutralizing a chemical agent, and since a commercial hydrolysis reactor is used, further description thereof will be omitted.

The supercritical water oxidizer 30, the oxidation reactor 20 for completely oxidizing the decomposition material generated in the hydrolysis reactor 10 by using the process water and oxygen of high temperature and high pressure, the oxidation reactor 20 is An oxidizer main body 31 installed therein and provided with a heater, a decompression device 32 for depressurizing a pressure of a generated material formed by oxidizing decomposition products in a supercritical water state by the oxidation reactor 20 to atmospheric pressure; Separator 33 for separating the product into a gaseous material and a liquid material, and a cooling heat exchanger 34 is installed on the upstream side of the decompression device 32 to rapidly cool the product formed in the oxidation reactor 20 ) And a particle filter 35 installed at the front side of the cooling heat exchanger 34 to remove particulate matter contained in the product material. At this time, the liquid material from which the particulate matter is removed by the particle filter 35 is discharged as it is through the separation device 33 or stored in the treated water storage tank 36 and recycled as process water.

Here, the reaction temperature in the inside of the oxidation reactor 20 is to be 374 ℃ to 660 ℃ or less, the reaction pressure is to be at least 220 atm and less than 300 atm so that the oxidation reaction in the supercritical state. If the reaction temperature and the reaction pressure of the oxidation reactor is less than the set time, the time required for the oxidation reaction is longer, and if the set time is more than the set time, the time required for the oxidation reaction can be shortened, but the thickness of the device increases, which is uneconomical. . In the actual experiment, the reaction temperature in the oxidation reactor 20 was set to 560 ° C., and the reaction pressure was set to 250 atm.

The oxidizer main body 31 is installed at the inlet side of the oxidation reactor 20, the decomposed material supplied from the decomposition material supply unit 12 and the oxygen supplied from the oxygen supply unit 14 and the auxiliary fuel supply unit ( 18, a feed mixer 37 for mixing IPA, which is an auxiliary fuel supplied from 18), and supplying it to the oxidation reactor 20 and an outlet side of the oxidation reactor 20 are installed using process water or caustic soda solution. An emission mixer 38 is further included to cool and neutralize the product.

On the other hand, the decomposition material supply unit 12, the storage tank (12V) for storing the decomposition material generated in the hydrolysis reactor 10, and a particle filter for removing particulate matter contained in the decomposition material from the storage tank (12V) 12F, a high pressure pump 12P for pressurizing the filtered liquid decomposition material to 250 atm, and a heating heat exchanger 12E for heating the fluid after heating the OPA to 400 ° C in the decomposition product, respectively. do. If the decomposition material is TDG or MPA, since there is a risk of thermal decomposition, it is preferable to supply the feed mixer 37 at room temperature without heating to be mixed with high temperature and high pressure oxygen.

The oxygen supply unit 14 includes an oxygen storage tank 14V for storing oxygen produced by the oxygen generator 14A, an oxygen compressor 14C for compressing oxygen from the oxygen storage tank 14V to 250 atm, and an oxygen compressor. And a heating heat exchanger 14E for heating the oxygen from 14C to a temperature of 400 to 500 ° C., depending on the type of decomposition material. On the other hand, the oxygen supply unit 14 is a device for supplying the oxidant required for the oxidation of the organic matter contained in the decomposition material to the feed mixer 37, the oxygen or hydrogen peroxide (H ₂ O ₂ ) is used. When liquid oxygen is used, it is sent to an air heated oxygen vaporizer to vaporize, and this oxygen vaporizer acts as an oxygen generator 14A. When overpressure occurs during operation of the oxygen compressor 14C, a portion of the overpressure is sent to the oxygen storage tank 14V using a pump (not shown) to adjust the pressure.

The process water supply unit 16 is a device for supplying water, which is the main reaction medium in the supercritical water oxidation reaction, to the lower portion of the oxidation reactor 20. The process water storage unit 16V and the storage tank 16V A particle filter 16F for removing foreign matters from the process water, a high pressure pump 16P for pressurizing and filtering the filtered process water to 250 atm, and a heating heat exchanger 16E for heating the process water to 400 ° C. do. In addition, the process water supply unit 16 supplies water used to rapidly cool the product generated in the oxidation reactor 20, and removes foreign substances of process water from the lower portion of the storage tank 16V. And a high pressure pump 16P 'for cooling the filtered process water to the discharge mixer 38.

The auxiliary fuel supply unit 18 includes a storage tank 18V for storing auxiliary fuel such as IPA, a particle filter 18F for removing particulate matter contained in the IPA from the storage tank 18V, and filtered. A high pressure pump 18P for pressurizing and feeding particulate matter to 250 atm and a heating heat exchanger 18E for heating IPA to 400 ° C are respectively provided.

The oxidation reactor 20 has a cylindrical shell 21 in which a through hole 21 'penetrates up and down, and is located inside the through hole 21' of the shell 21, and the decomposition material Oxidation reaction of the influent material is made and the inner tube 22 formed at a lower height than the shell 21 and the upper portion coupled to the upper portion of the shell 21 to block the upper end of the through hole 21 '. An oxygen injector 24 installed through the cover 23, the upper cover 23, and supplying oxygen into the inner tube 22, and positioned inside the oxygen injector 24 and the oxygen injector Decomposition material injector 25 that protrudes compared to (24), and the product material discharge hole is coupled to the lower portion of the shell 21 to block the lower end of the through hole (21 ') and communicate with the inner tube (22) And a water supply hole 26 "for supplying water between the inner tube 22 and the inner circumferential surface of the through hole 21 'and the outer circumferential surface of the inner tube 22. It comprises a lower cover 26 and a valve (not shown) coupled to the lower end of the inner tube 22 to open and close the product discharge hole 26 '.

Here, the shell 21 and the shell of the heat exchanger are formed of Hastelloy C-276 material, and the inner tube 22 is formed of a relatively inexpensive titanium grade II material. In addition, the feed line of the decomposition material supply unit 12 and the auxiliary fuel supply unit 18 is preferably formed of an Inconel 600 material.

On the other hand, chemical agents are nerve agents such as VX and sarin (GB), nerve agent precursors such as DF or OPA-type dualization agents and blisters such as mustard (HD). In addition, the decomposed substances due to the hydrolysis and neutralization of the chemical agent is MPA (Methylphosphonic Acid) in the case of neurological agents, TDG (Thiodiglycol) in the case of mustard, and may include acids and salts of halogenated elements.

In addition, the two-stage disposal method of the chemical agent of the present invention comprises: a toxic removal step of supplying water or caustic soda solution with the chemical agent to hydrolyze or neutralize the chemical agent; The oxidizing step and the discharged product formed in the oxidizing step are introduced into the reactor of the supercritical state at high temperature and high pressure and supply the process water and oxygen at high temperature and high pressure so that the decomposition material is oxidized. And a post-treatment step of treating the product as possible, and a discharge step of separating and discharging the finished material into a gas and a liquid.

Here, the post-treatment step comprises the step of rapidly cooling the product, filtering the particulate matter contained in the product, and reducing the supercritical pressure to atmospheric pressure. In addition, the toxic treatment step may include a step of further treating a primary decomposition material such as MPA, TDG, etc., produced by neutralizing or hydrolyzing a chemical agent, with a caustic soda solution. In addition, the detoxification step allows the hydrolysis or neutralization reaction to proceed until the decomposition rate of the chemical agent reaches 99.99%, and the oxidation step results in the disposal efficiency of the decomposition products being 99.99% based on the total organic carbon or the treated material. Allow oxidation to proceed until this is achieved.

According to the two-stage waste treatment apparatus and method of the chemical agent of the present invention, the chemical agent is converted into a material harmless to the human body through the two-stage treatment of the chemical agent.

The hydrolysis reactor 10 is filled with water or caustic soda solution according to the type of chemical agent that is the substance to be treated, and stirred while gradually injecting the chemical agent. Hydrolyze or neutralize the chemical agent at a certain temperature for a period of time, stabilize the degradant, and then analyze the concentration of the chemical agent to decompose until the hydrolysis efficiency reaches 99.99% or higher; It is sent to the decomposition reactor 10 for reprocessing. Meanwhile, when the hydrolysis efficiency satisfies 99.99% or more, the generated decomposition material is transferred to the decomposition material storage tank 12V and finally processed by the supercritical water oxidizer 30.

Types of chemical agents reported to the chemical weapons ban mechanism include nerve agents such as VX and sarin, and blister agents such as mustard, accounting for about 70% or more of the total amount, as well as industrial gases and dualization agents. Therefore, in the present invention, as an example of the chemical agent to be treated, the most current stockpile and sarin, which is a representative substance of nerve agents, HD is selected as a representative substance of the blistering agent, and in addition, DF and OPA are selected as a dualizing agent to select these substances. Allow complete disposal.

Looking at the hydrolysis or neutralization process of the agent in the hydrolysis reactor described above are as follows.

In the case of sarin, a representative neurological agent, neutralization with a caustic soda solution produces non-toxic organic salts, NaF, and water through a chemical reaction described in Chemical Formula 1 below.

In addition, in the case of mustard (HD), which is a blistering agent, hydrolysis with water produces TDG (Formula: (OHCH ₂ CH ₂ ) ₂ S) and HCl as shown in Chemical Formula 2 below.

When DF is hydrolyzed, a reaction occurs as shown in Chemical Formula 3 below, and finally, it is decomposed into MPA (Chemical Formula: CH ₃ P (O) (OH) ₂ ) and HF.

As described above, hydrolysis or neutralization of sarin (GB), mustard (HD) and DF with basic substances such as water or caustic soda almost eliminates the original toxicity of chemical agents. However, MPA and TDG, which are major degradation products, are also designated as regulated by the CWC, so these materials must be disposed of completely for reuse. Therefore, a final treatment process of the decomposed substance produced by hydrolysis or neutralization is required, and in the present invention, the decomposed substance is finally treated by a supercritical water oxidation (SCWO) method.

In addition, since decomposition of the chemical agent generates an acid of a halogen group such as HF and HCl as shown in Chemical Formulas 2 and 3, in order to prevent the reverse reaction by the generated acids and further promote decomposition, caustic soda is finally added. Further processing to inject allows for the inclusion of salts such as NaF.

As a result, the decomposition products generated in the hydrolysis or neutralization step are almost eliminated the toxicity of the chemical agent. Therefore, it is possible to work more safely in the step after hydrolysis or neutralization, and the decomposed material due to hydrolysis and neutralization is finally processed in the supercritical water oxidizer 30. In particular, in the supercritical water oxidizing apparatus 30, by oxidizing the decomposed substances that have been removed toxic, even if incomplete oxidation during the secondary treatment or the decomposed substances leak in the form of gas or liquid substances, they do not act deadly to the human body. Therefore, the secondary treatment work in the supercritical water oxidizer 30 can be proceeded more safely.

The supercritical water oxidizing apparatus 30 will be described in detail as follows.

Hydrolysates of sarin, DF, and HD, which are chemical agents addressed in the present invention, contain acids and salts, making them difficult to process in commercial supercritical water oxidizers. In general supercritical water oxidizers, most of the reactors are coil-type reactors, and experiments using alternative materials instead of actual chemical agents. However, the hydrolyzable substances of chemical agents that need to be dealt with in the actual process include alkali metals such as Na and salts thereof in addition to organic substances, which are the main decomposition substances, and acidic substances (HF, VX for GB or GD) during hydrolysis. Sulfuric acid, etc.) as well as various types of impurities. However, in the case of the coil type reactor, the diameter is small and the flow path is bent, so that a large amount of solid materials such as salts may have difficulty in avoiding plugging.

In order to overcome this problem, in the present invention, a vertical tubular reactor having a diameter of more than two times and a short length is used, and reaction conditions of a relatively high conversion rate are set. In addition, in the experiment subjects, hydrolysis conditions are established using actual chemical agents that are not substitutes for agents, and two-step treatment processes for chemical agents that can be applied by supercritical water treatment by simulating the composition of these decomposition products are established. I can do it.

2 is a conceptual diagram for explaining a supercritical water oxidizing apparatus according to the present invention, and an oxidation reactor 20, which is a main component of the apparatus, oxidizes a material to be treated in a supercritical state at a reaction temperature of 560 ° C and 250 atm. That is, the feed neutralizer (37) is pressurized to a neutralizing agent (or hydrolysis generating material; decomposition product), an oxidizing agent, and isopropyl alcohol (IPA), an auxiliary fuel, at a reaction temperature of 560 ° C and 250 atm, respectively. Injected into the oxidation reactor 20 through. The water, which is the reaction medium, is heated to 400 ° C. and pressurized to 250 atm, and injected through the water supply hole 26 ″ of the lower cover 26 provided at the bottom of the oxidation reactor 20 shown in FIG. 3. It is allowed to flow to the upper portion of the oxidation reactor 20. Therefore, the decomposition product and the oxidizing agent, auxiliary fuel and the reaction medium (water) is mixed in the upper portion of the oxidation reactor 20, where the organic material contained in the decomposition material and auxiliary fuel, etc. Is oxidized and decomposed.

The product material formed while passing through the oxidation reactor 20 and flowing out through the product material discharge hole 26 ′ is cooled in the cooling heat exchanger 34, and then reduced in pressure to atmospheric pressure by the pressure reducing valve 32. Thereafter, the gaseous substance and the liquid substance are separated through the separator 33, and the gaseous substance is discharged to the atmosphere and the liquid substance is stored in the treated water storage tank 36 and reused as the hydrolysis process water or the process water for oxidation. Discharge to the outside. The process of each sector is described in detail as follows.

The decomposer supply unit 12 is a device for supplying a decomposed substance produced by hydrolyzing or neutralizing a chemical agent, and supplies an aqueous solution of the decomposed substance to the feed mixer 37 provided in front of the oxidation reactor 20. The chemical agent hydrolyzate is stored in the storage tank (12V) to remove the solid impurities remaining in the particle filter 12, and pressurized to 250 atm by a high pressure pump (12P). Thereafter, TDG and MPA in the agent hydrolyzate are sent directly to the feed mixer 37 at room temperature, and OPA is heated to 400 ° C. in the heating heat exchanger 12E and then supplied to the feed mixer 37.

The oxygen supply unit 14 is an apparatus for supplying an oxidant used for oxidizing organic substances contained in a chemical agent decomposition product. The oxygen supply unit uses liquid oxygen or hydrogen peroxide as an oxidant. In the case of liquid oxygen, an oxygen vaporizer, that is, an air heating heat exchanger, that is, an oxygen generator ( Gaseous oxygen is produced by evaporation to 14A). The gaseous oxygen is pressurized to 250 atm in the oxygen compressor 14C, the flow rate is measured by a flow meter (not shown), sent to the heating heat exchanger 14E, heated, and then supplied to the feed mixer 37. The heating temperature of the gaseous oxygen is heated to 400 ℃ when the decomposition material is OPA, and to 500 ℃ for MPA and TDG. If overpressure occurs during operation of the oxygen compressor 14C, a portion of the pressurized oxygen is sent to the oxygen storage tank V by a pump (not shown) to adjust the pressure.

 The auxiliary fuel supply unit 18 is a device for supplying auxiliary fuel (isopropyl alcohol, IPA) used to raise the reaction temperature of the oxidation reactor 20 to the feed mixer 37 installed in front of the oxidation reactor 20. After removing the auxiliary fuel (IPA) stored in the auxiliary fuel storage tank (18V) to remove the solid impurities with the particle filter (18F) and pressurized to 250 atm by a high pressure pump (18P), 400 using the heating heat exchanger (18E) It is heated to ℃ and supplied to the feed mixer 37.

 The process water supply unit 16 supplies process water (water), which is a main reaction medium in the oxidation reactor 20, to the oxidation reactor 20 and process water (water) for quenching the product produced in the oxidation reactor 20. It is a device for supplying. The process water stored in the process water storage tank 16V is pressurized to 250 atm using a high pressure pump 16P while impurities are removed by the particle filter 16F, and heated to 400 ° C. using a heating heat exchanger 16E to oxidize the oxidation. Feed into the bottom of the reactor 20. Therefore, the process water is moved upward along the space between the inner tube 20 of the oxidation reactor 20 and the inner wall of the shell 21, and the decomposition material above the inner tube 22 of the oxidation reactor 20. And by admixing with auxiliary fuel and oxidizing agent, the organic material and the acid and salt of TDG, MPA, and halogen group element are oxidized to decompose into gaseous substances such as nitrogen and carbon dioxide and liquid substance mainly containing water.

On the other hand, OPA, TDG and MPA in the oxidation reactor 20 is operated at 560 ℃, 250 atm through the chemical reaction described in the following formula (4).

Here, OPA is a mixture of 71.7 wt% of isopropylalcohol and 28.3wt% of isopropylamine, so isopropyl alcohol {OPA (alcohol)} and isopropyl amine {OPA (amine)} in OPA It can be seen that this different type of oxidation reaction.

In addition, the auxiliary fuel IPA also serves to raise the reaction temperature in the oxidation reactor 20 by causing the oxidation reaction as follows.

In addition, the product material formed in the oxidation reactor 20 is mixed with the process water supplied from the process water supply unit 16 in the discharge mixer 38 and quenched at 250 ° C., and then cooled to room temperature by a cooling heat exchanger 34. To cool. Thereafter, while passing through the decompression device 32, the pressure is reduced to atmospheric pressure, that is, atmospheric pressure, and separated by the separator 33 into gaseous substances such as nitrogen, oxygen, carbon dioxide, and liquid substances mainly composed of water. The separated gaseous material is discharged to the atmosphere, and the liquid material is discharged as it is or stored in the treated water storage tank 36 and reused as process water used in a hydrolysis process or a supercritical water oxidizer. Here, the supercritical water oxidizer 30 is operated so that the destruction efficiency (DE) of various organic materials introduced into the oxidation reactor 20 is 99.99% or more.

The gaseous substances discharged from the supercritical water oxidizing apparatus 30 are completely harmless gases such as CO ₂ (carbon dioxide), N ₂ (nitrogen), O ₂ (oxygen), and water vapor, but are prepared for the generation of trace amounts of harmful gases. In addition to the discharge end of the material (not shown), a simple exhaust gas treatment device (not shown) such as a particle filter for gas may be provided. However, this exhaust gas treatment device is a safety device for the incomplete oxidation of organic matter and is not necessarily installed.

In addition, since the liquid substance discharged from the supercritical water oxidizer 30 has water as a main component, it is stored in the treated water storage tank 36 and then circulated to the hydrolysis reactor 10 to process water for hydrolysis of the chemical agent. It can be reused or used as process water or general water of the supercritical water oxidizer 30. This works very well in mountainous areas where there is a lack of water supply or where it is difficult to obtain water, and in certain areas such as military units or confined areas.

On the other hand, the oxidation process in the oxidizer main body 31 of the supercritical water oxidizer 30 will be described in detail.

The supercritical water oxidizer main body 31 has an oxidation reactor 20 which completely oxidizes the decomposition material generated in the hydrolysis reactor 10 by using high temperature and high pressure process water and oxygen, and is installed therein. The apparatus is provided with a heater (not shown), is installed at the inlet side of the oxidation reactor 20 by mixing the decomposition material supplied from the decomposition material supply unit 12 and the oxygen supplied from the oxygen supply unit 14 A feed mixer 37 for supplying the oxidation reactor 20 and an emission mixer 38 installed at the outlet side of the oxidation reactor 20 to cool and neutralize the product using process water or caustic soda solution are provided. It includes more.

In the oxidation reactor 20, a reaction chamber is formed in a vertical direction. An inner tube 22 of the oxidation reactor 20 serves as a reaction chamber. Into the reaction chamber, decomposition products generated by hydrolysis or neutralization of the chemical agent supplied from the decomposition material supply unit 12, oxidants, process water, etc. supplied from the oxygen supply unit 14 are introduced through the respective inflow lines. This results in decomposition and oxidation reactions.

In detail, each inflow process is carried out by the high pressure pump 12P in a state in which the decomposition material (decomposition rate of 99.99% or more) of the chemical agent completely decomposed in the first hydrolysis process is temporarily stored in the decomposition storage tank 36. After being mixed in the feed mixer 37 with the auxiliary fuel and the like, it is introduced into the oxidation reactor 20 by an injector (not shown). At this time, the decomposition material determined according to the chemical agent is introduced into the upper side of the oxidation reactor 20 without preheating or preheating. Of course, the decomposing material, the oxidizing agent, and the process water may be mixed at the upper side of the oxidation reactor 20 without mixing in the feed mixer 37.

On the other hand, the oxidation reactor 20 is for oxidizing the first stage treatment material (decomposition material) of the chemical agent or various inflow materials introduced into the oxidation reactor 20, formed at a high temperature of more than 374 ℃ and a high pressure of 220 atm or more In the supercritical state, the mixture is oxidized. At this time, in order to facilitate the reaction, a heater (not shown) may be provided around it.

The injector is intended to introduce influents including decomposition materials to the top of the oxidation reactor 20, and has a structure in which a triple triple hole is formed so that inflow materials required for supercritical water oxidation can pass therethrough. Of course, the oxygen injector 24 and the decomposer injector 25 may be configured separately so that each inflow material may be independently supplied into the oxidation reactor 20. On the other hand, when the calorific value of the decomposition material introduced into the oxidation reactor 20 is low, it is possible to inject auxiliary fuel such as IPA supplied from the auxiliary fuel supply unit 16 using one of the injectors.

In addition, the discharge mixer 38 provided in the lower portion of the oxidation reactor 20 serves to reprocess the product material discharged from the oxidation reactor 20. That is, the caustic soda solution or process water is circulated into the discharge mixer 38 to neutralize the acidic product and rapidly quench the temperature of the product. Subsequently, the product material is changed to room temperature and pressure while passing through the cooling heat exchanger 34 and the decompression device 32, and is separated and discharged into a gaseous material and a liquid material by the separator 33.

In this way, the supercritical water oxidizer 20 processes MPA, which is a hydrolyzate such as OPA, sarin (GB), and DF, and TDG, which is a hydrolyzate of mustard (HD). Meanwhile, particle filters 12F, 16F, and 18F respectively installed in the discharge material supply unit 12, the auxiliary fuel supply unit 16, and the process water supply unit 18 are included in the inflow material of the oxidation reactor 20. The removed solid particles are removed, and the particle filter 35 installed upstream of the cooling heat exchanger 34 removes the solid particles of the product which may be generated by the oxidation reaction in the oxidation reactor 20.

The cooling heat exchanger 34 is used to cool the product discharged from the oxidation reactor 20 and cools the gas and adsorbs water. In addition, since a plurality of pipes to which cooling water is supplied is provided, the product is cooled by the cooling water, and the temperature of the product is rapidly lowered to change to room temperature. Since the product material changed to the normal temperature is still in the supercritical state, the product is passed through the decompression device 32 to be decompressed to normal pressure so as to be a product in the normal state. Thereafter, the product is separated into a gaseous substance and a liquid substance by the separator 33, and the gaseous substance is discharged into the atmosphere, and the liquid substance is discharged as it is or temporarily stored in the treated water storage tank 36, and then the hydrolysis reactor 10 ) May be supplied to the process water supply unit 16.

The following describes specific experimental examples of the two-stage waste disposal apparatus and method of the chemical agent of the present invention.

In the experiment, the hydrolysis reactor 10 is filled with water or caustic soda solution according to the type of chemical agent, and the hydrolysis or neutralization is carried out while slowly injecting chemical agents such as sarin, mustard, and DF. After hydrolysis or neutralization for a period of time at a certain temperature, the degradation products are stabilized and the concentration of the chemical agent is analyzed. At this time, when the hydrolysis efficiency reaches 99.99% or more, the decomposed material is transferred to the decomposed material storage tank 12V of the supercritical water oxidizing apparatus 30 for final processing through the supercritical water oxidation reaction.

Experimental Example 1 Hydrolysis and Neutralization of Sarin (GB)

In order to convert sarin (O-Isopropyl Methylphosphonofluoridate, GB), which is a representative of nerve agents, into harmless substances, it was hydrolyzed and neutralized with caustic soda solution. The experiment was conducted by connecting a circulator to a jacketed small reactor and injecting 10 wt% of sarin into a 2.05 equivalent solution of caustic soda and changing the temperature (50 ° C, 70 ° C and 90 ° C) respectively. Constants were obtained. As the amount of caustic soda during hydrolysis and neutralization increases, NaF increases as well as the amount of salts generated, so to minimize this, caustic soda is used the minimum amount necessary for hydrolysis and neutralization.

As a result of hydrolyzing and neutralizing sarin in aqueous solution of caustic soda, as shown in Table 1, decomposition was promoted, and when hydrolyzed and neutralized at 90 ° C. for 60 minutes or more, it was found to decompose more than 99.99%.

Table 1 below shows the results of hydrolysis and neutralization experiments of sarin according to temperature and reaction time (degradation rate:%).

It is necessary to obtain the rate constant by applying the first-order rate equation and to apply the dependence of the rate constant on the temperature to the Arrhenius equation to achieve more than 99% of the hydrolysis efficiency of sarin at each temperature. As a result of predicting the reaction time required, the results shown in Table 2 were obtained.

On the other hand, in the actual process, it is preferable to dispose of sarin within the shortest time (12 hours). Referring to Table 2 below, the reaction conditions under which sarin decomposes 99.99% or more are at least 2 hours at 80 ° C or at least 1.2 hours at 90 ° C. It will react.

Table 2 below shows the reaction prediction time for achieving the hydrolysis efficiency (99.99% or more) of the sarin by reaction temperature.

Decomposition material of the hydrolysis and neutralization of sarin in the experiment was analyzed by gas chromatography-mass spectrometry (GC-MSD) and liquid chromatography (LCQ (IT)), isopropylmethyl phosphonate (Isopropylmethyl Phosphonate; iMPA).

Experimental Example 2 Hydrolysis of Mustard (HD)

Mustard (sulfur mustard, HD, bis 2-chloroethylsulfide), a representative substance of the blister agonist, was hydrolyzed with water. Since mustard (HD) is rapidly decomposed in water at high temperature (80-90 ° C), the reaction temperature is fixed at 90 ° C, and mustard (HD) must be considered in consideration of the reaction time, mustard (HD) concentration and the effect of caustic soda after hydrolysis. The disposal conditions of) were set.

The experiment was carried out by injecting 10-20 wt% of mustard (HD) into water at 90 ° C. in the same small reactor as in Experimental Example 1 for 1.5 hours or more, and then further reacting for 30 minutes with 2.01 equivalents of aqueous sodium hydroxide solution at room temperature. The decomposition rate of (HD) was 99.99%.

The hydrolyzate of mustard (HD) was quantitatively analyzed by gas chromatography-mass spectrometry (GC / MSD). As a result, 68 wt% TDG (Thiodiglycol), 8 wt% 1,2-Bis (2-hydroxyethylthio) ethane, and Bis- (2-hydroxyethylthioethyl) ether 24wt%.

Table 3 below shows the hydrolysis efficiency (%) of mustard (HD) according to the concentration at a temperature of 90 ° C.

On the other hand, in order to determine the effect of the hydrolysis according to the concentration of the mustard (HD) concentration (10, 15 and 20wt%) experiments with the results, it can be seen that after 1 hour to about 99.9% as shown in Table 3. However, even if the reaction time was increased to 2 hours or more, the decomposition efficiency did not increase much.

In addition, in order to prevent regeneration of mustard by reverse reaction by neutralizing hydrochloric acid (HCl) generated during hydrolysis, 2.1 equivalents of the initial mustard (HD) amount was injected at room temperature after the reaction, and the reaction results over time. As a result, the decomposition rate was achieved 99.99% in all concentration range within 1 hour.

Experimental Example 3 Hydrolysis of DF

After hydrolysis of DF (Methylphosphonicdifluoride), which is a binary agent, with water at a ratio of 1: 1.5 at 70-90 ° C. for 2 hours or more, the result of analysis by ion chromatography (IC) showed 45% water and methylphosphonic acid (MPA) 39 % And HF 16% were produced and no DF was detected.

Since hydrolyzate of DF contains a large amount of HF, which is a strong acid, it can corrode the post-treatment device when it is finally processed. Therefore, HF is removed to the maximum and organic MPA is dissolved in water as much as possible (maximum solubility: 32.3wt%) was judged economically. In addition, as a result of repeated distillation using the azeotropy point of water and HF in order to separate HF, the composition of the final treated material could be composed of about 32% MPA, about 1% HF and water.

An experiment was conducted to oxidize OPA, which is a decomposition material and a binary agent generated by hydrolysis of the chemical agent, using a supercritical water oxidizer, and the experimental results are as follows.

Experimental Example 4 Supercritical Water Oxidation of OPA

OPA, a binary agent, was oxidized in a supercritical water oxidizer. OPA and oxidizing agent were used for external diameter 1/8 "SUS 316 pipe and passed through preheater of 0.5 and 6 m length, respectively, and then mixed in feed mixer 37 installed at the inlet of oxidation reactor 20 to the oxidation reactor 20. The oxidation reactor 20 was made of an outer diameter of 18mm, an inner diameter of 9.5mm, and a length of 280mm, and was made of SUS 304. In addition, the product coming out of the outlet of the oxidation reactor 20 was formed in a double tube type. After rapid cooling in the cooling heat exchanger (35), the pressure was reduced by the decompression device (32), and separated into a gaseous substance and a liquid substance using the separator (33), and the liquid sample was collected in the cylinder. Was analyzed online in gas chromatography (GC) equipped with a thermal conductivity detector (TCD).

Experimental conditions are shown in Table 4 below, and the oxidizing agents were compared with efficiency using hydrogen peroxide and oxygen, respectively.

After experimenting with hydrogen peroxide in the initial concentration of 2.11 × 10 ^-3 to 1.43 × 10 ^-1 mol in the reactor and from 956 to 70,190ppm in the feed tank, the total organic carbon ( TOC) 99.97% was degraded.

In case of using oxygen, the OPA removal efficiency was 84.26 ~ 99.39%. If the high temperature and residence time were prolonged under the appropriate excess oxygen (50 ~ 150%) condition, the carbon monoxide production was minimized and the OPA removal efficiency was Higher. In addition, OPA was completely decomposed at 200% excess oxygen. On the other hand, the decomposition rate was higher when using hydrogen peroxide as the oxidant than when using oxygen.

Experimental Example 5 Degradation of TDG (Thiodiglycol)

In order to measure the decomposition efficiency of TDG with or without oxygen supply in supercritical water conditions, hydrolysis and oxidation experiments were performed as shown in Table 5 below. The oxidation reactor used an outer diameter of 31.7mm, an inner diameter of 10mm, a length of 0.3m, was made of Hastelloy C-276.

The oxidant was preheated above 550 ° C. and the TDG solution was mixed with the preheated oxidant to preclude the possibility of pyrolysis due to preheating. TDG and oxidant are mixed in the opposite direction to the cross type pipe made of Hastelloy C-276, and K-type thermocouple is installed on the top of the pipe to adjust the temperature just before the mixed fluid enters the oxidation reactor. Measured.

1) As a result of experiment by supplying deionized water without using any oxidizing agent, TDG produced strong odor due to hydrogen sulfide (H ₂ S) generated during hydrolysis. As a result of gas analysis, carbon monoxide (CO), methane (CH) ₄ ), carbon dioxide (CO ₂ ), ethylene (C ₂ H ₄ ), ethane (C ₂ H ₆ ), and the like were detected. In the liquid sample, sulfuric acid was detected by ion chromatography (IC), but the concentration was mostly lower than 1%, and the sulfur component was not converted well to sulfuric acid.

2) A supercritical water oxidation experiment was conducted under the conditions of Table 5 using the same apparatus as in 1) above. In order to determine the conversion rate according to the temperature and residence time, the reaction temperature was varied (400 ~ 500 ℃) and experimented at the initial concentration of 2.39 mmol and the excess oxygen 188%. The conversion rate increased with increasing temperature and residence time. More than 90% of cases.

Experimental Example 6 Supercritical Water Oxidation of MPA (Methylphosphonic Acid)

In order to oxidize MPA in supercritical water, the oxygen as the oxidant was 0-280 of the required oxygen demand, while the pressure was fixed at 25 MPa and the temperature, residence time, MPA concentration and oxygen concentration were changed, as in the conditions shown in Table 6 below. Supercritical oxidation was carried out using up to%.

The experiment was a continuous flow reactor, and both the flow path and the preheater of the liquid material were made of SUS 316. Hydrogen peroxide (H ₂ O ₂ ) and water as the oxidant is introduced into the oxidation reactor 20 through a separate pump and preheater, water is introduced from the lower end of the double-walled oxidation reactor 20 as shown in FIG. Moving to the upper end of 22, the oxidant (H ₂ O ₂ ) is introduced into the upper portion of the inner tube 22 is mixed with water in the inner tube (22). MPA was injected into the oxidation reactor 20 without heating to prevent pyrolysis. On the other hand, the product material exiting the outlet of the oxidation reactor 20 was rapidly cooled in the cooling heat exchanger (34), in order to remove the particles generated during the reaction using a particle filter 35 of 0.5㎛ diameter, after decompression The gaseous phase and the liquid phase were separated, and the gas was analyzed by gas chromatography (GC), the liquid was measured by TOC, and the reaction was performed by ion chromatography (IC).

The outside of the oxidation reactor 20, ie, the shell 21, was made in a vertical cylindrical shape having a wall thickness of 19 mm, an inner diameter of 38 mm, an outer diameter of 76 mm, and a height of 380 mm, and a Hastelloy-C 276 material was used. The inner tube (22) uses a 3/8 "SUS 316 tube, the MPA is the innermost 1/16" tube and the oxidant ((H ₂ O ₂ ) is the 1/8 "tube surrounding the MPA tube. The experiment was carried out through the inner tube 22. As a result, the maximum conversion rate was 99.3715% based on the TOC and 99.9988% based on the MPA, where the total flow rate was 10.55 g / min. , Feed ratio was MPA: oxidizing agent (H ₂ O ₂ ): water = 1.08: 2.85: 6.62, the residence time was 4.77 seconds (627 ℃) and 5.28 seconds (573 ℃) and 25% excess oxidant, respectively, depending on the temperature It was a case of using more than.

Therefore, the reaction temperature predicted the disposal rate of 99.99% or more according to the initial load of MPA with reference to the above experimental conditions, it can be seen that the MPA concentration is at least 627 ℃ at 1wt% and at least 573 ℃ at 10 wt%, respectively. .

Experimental Example 7 Supercritical Water Oxidation Using a Bench Scale Double Wall Reactor

On the other hand, as a result of the oxidation test of the TDG and MPA in Experimental Examples 5 and 6, corrosion of the oxidation reactor 20 was serious because of their high reactivity. Therefore, a bench-scale oxidation reactor 20 having a double wall was manufactured in a continuous flow experiment and tested on three kinds of materials to be treated.

The oxidation reactor 20 is a vertical reactor composed of a concentric double wall, as shown in FIG. 3, in which the shell 21 of the oxidation reactor (52 mm inner diameter, 102 mm outer diameter, about 1.3 L volume) has been used. The inner tube 22 (inner diameter 22 mm, outer diameter 25.4 mm, length 590 mm) manufactured by using a 276 material and made of titanium, etc., is inserted into the shell 21, and the inside of the inner pipe 22 is inserted therein. The oxidation reaction takes place at. At this time, the internal and external flow of the inner tube 22 is maintained at the same pressure, and the thermocouple is installed at four places such as the inlet and the middle portion of the inner tube 22 and the upper end of the inner tube 22 to oxidize. The temperature distribution of the reactor 20 was measured.

The decomposing material was heated to 550 ° C. or higher at the inlet of the oxidation reactor 20 before mixing with the process water, and the decomposing material was mixed with the heated oxidant without preheating to exclude the possibility of thermal decomposition due to preheating. .

The process water flowing into the lower portion of the oxidation reactor 20 is introduced into the internal space of the oxidation reactor 20 under supercritical conditions of 25 MPa and 400 ° C., and the two reactors surrounding the outside are oxidation reactors. (20) was heated. The decomposition material and the oxidant are introduced into the inner tube 22 from the top of the oxidation reactor 20, while the process water flows from the bottom of the oxidation reactor 20 to the top. At the upper end of the oxidation reactor 20, the flow direction of the process water is reversed, and the decomposition material and the oxidant introduced into the inner tube 22 are mixed and oxidized instantaneously, and the product generated by the oxidation of the decomposition material is an oxidation reactor ( 20) is discharged to the bottom.

This oxidation experiment was carried out at a pressure of 25 MPa with a temperature range of 500 to 660 캜 and a residence time of 11 to 15 seconds. As a result of the experiment, the conversion rate of OPA was 99.7% or more, based on TOC, in all cases, up to 99.99%, and the TOC was less than 3 ppm at the outlet of the oxidation reactor 20. As a result of observing the inner tube 22 after the experiment, there was almost no effect of corrosion even under high temperature and high concentration of severe oxidation condition. In order to confirm the protection role of the inner tube 22 against corrosion, oxidation experiments with a more corrosive TDG solution showed a conversion rate of more than 99.99%, and carbon monoxide (CO), sulfur dioxide (H ₂ S), and methane (CH _4). ) Was not measured and all of the sulfur dioxide (H ₂ S) in the discharge was recovered as sulfuric acid (H ₂ SO ₄ ).

In the case of MPA, which is expected to be the most corrosive among the decomposition products, the conversion rate was 99.99% or more, and carbon monoxide (CO), phosphorus pentoxide (P ₂ O ₅ ) and methane (CH ₄ ) were not measured and phosphorus pentoxide ( P ₂ O ₅ ) was all recovered with phosphoric acid (mP ₂ O ₅ nH ₂ O).

  In addition, after 100 hours of testing the corrosion state of the inner tube 22, the oxidation reactor 20 was dismantled and confirmed, but no damage, cracks, or pin holes occurred, and no deposits were found. As a result, the inner tube 22 was resistant to corrosion and no significant abnormality was found even after 300 hours of use.

Experimental Example 8 Oxidation of TDG Containing Acids and Salts

In the bench-scale double wall reactor used in Experimental Example 7, an experiment was performed to determine the effect of acid or salt contained in the TDG solution upon oxidation of supercritical water. That is, as a result of experiment by adding 1% hydrochloric acid (HCl) to the TDG solution under the same apparatus and conditions as in Experimental Example 7, no effect on TOC conversion and corrosion of the apparatus was found.

Therefore, regardless of the decomposition products depending on the type of chemical agent is converted into a gas and liquid substances harmless to the human body through supercritical oxidation reaction, and the chemical agent is disposed of through the two-step treatment regardless of the type of chemical agent It becomes possible.

In the above described exemplary embodiments of the present invention by way of example, the scope of the present invention is not limited to the specific embodiments as described above, the scope of the present invention by those skilled in the art to the claims It is possible to make appropriate changes within the stated categories.

As described above, according to the two-stage waste disposal apparatus and method of the chemical agent of the present invention, in order to safely treat the chemical agent such as the nerve agent or the bullous agent, in one step, hydrolysis or neutralization treatment according to the type of chemical agent It generates a decomposed substance that completely removes the toxicity of chemical agent, and in the second stage, the decomposed substance is finally processed in a supercritical water oxidizer and converted into a gaseous substance and a liquid substance which is harmless to the human body. It has the effect of completely treating chemical agents.

In addition, according to the two-stage waste treatment apparatus and method of the chemical agent of the present invention, by oxidizing the decomposition material of the chemical agent to remove the toxicity by hydrolysis, etc. in a supercritical state, air and wastewater than when treated by conventional incineration method It has the effect of minimizing environmental pollution caused by and working safely.

 In addition, according to the two-stage waste treatment apparatus and method of the chemical agent of the present invention, hydrolysis or neutralization in a chemical agent hydrolysis reactor, and the hardly decomposable substance containing the strong acid or salt generated at this time is oxidized in a supercritical water oxidizer. Since it can be treated as a completely harmless substance, there is an effect that can safely and economically treat hydrolyzable substances of chemical agents.

In addition, according to the two-stage waste treatment apparatus and method of the chemical agent of the present invention, the water finally treated in the supercritical water oxidation process is not discharged to the outside and reused as the hydrolysis process or the supercritical water oxidation process water. It is possible to prevent the environmental pollution caused by the wastewater generated in the country, and has a very beneficial effect in military units, mountainous areas and areas where supply of process water is insufficient.

In addition, according to the two-stage waste treatment apparatus and method of the chemical agent of the present invention, the occurrence of device corrosion generated when treating a highly reactive or acid-containing decomposition substance such as TDG and MPA in a supercritical water oxidizer is minimized. To this end, a vertical cylindrical oxidation reactor having a concentric double wall and an inner tube made of a commercially available titanium tube are inserted into the reactor so that the oxidation reaction occurs in the inner tube, thereby causing malfunction of the device due to corrosion. It is effective to prevent the occurrence of problems such as impurity generation and incomplete oxidation in the treatment of decomposition products.

In addition, according to the two-stage waste disposal apparatus and method of the chemical agent of the present invention, if corrosion occurs in the inner tube using the oxidation reactor for a certain time, it is replaced with a new tube, thereby protecting the expensive outer reactor and continuously using it. It can be effective. In this case, the inner tube serves as a consumable replacement reactor.

In addition, according to the two-stage waste disposal apparatus and method of the chemical agent of the present invention, the oxidation reaction occurs in the inner tube of the oxidation reactor, so as to limit the damage due to corrosion to the inner tube and to withstand the stress caused by the pressure difference. There is an effect that can minimize the corrosion of the external reactor is made thick.

In addition, according to the two-stage waste disposal apparatus and method of the chemical agent of the present invention, by using a commercially available conduit of stainless steel, Inconel, or titanium of low cost as the material of the inner tube that can cause corrosion, It is very effective in the case that it is difficult to use a commercial oxidation reactor due to the corrosion and the deposition of salt, as in the experiment.

Claims (25)

A hydrolysis reactor (10) for supplying a water or caustic soda solution with the chemical agent to hydrolyze or neutralize the chemical agent to produce decomposable substances from which the chemical agent is toxic; And a supercritical water oxidizer (30) for supplying process water and oxygen to the decomposed material produced in the hydrolysis reactor (10) to supercritically oxidize. The method of claim 1, The supercritical water oxidizer 30 includes an oxidation reactor 20 which completely oxidizes the decomposition material generated in the hydrolysis reactor 10 using process water and oxygen, and the oxidation reactor 20 is installed therein. And an oxidizer main body 31 provided with a heater, a decompression device 32 for reducing the pressure of a product material formed by oxidizing decomposition products in a supercritical water state by the oxidation reactor 20 to atmospheric pressure, and the product material And a separation device (33) for separating the gaseous material and liquid material. The method of claim 2, The supercritical water oxidizing apparatus 30 is provided on the upstream side of the depressurizing apparatus 32 to cool a heat exchanger 34 for cooling a product formed in the oxidation reactor 20, and the cooling heat exchanger 34. And a particle filter (35) installed at the front side of the product to remove particulate matter contained in the product. The method of claim 3, The second step of the chemical agent, characterized in that the liquid material from which the particulate matter is removed by the particle filter 35 is discharged as it is through the separator 33 or stored in the treated water storage tank 36 and then recycled as process water. Waste treatment device. The method of claim 2, Decomposition material supply unit 12 for providing a decomposition material produced in the hydrolysis reactor 10 to the oxidation reactor 20 of the supercritical water oxidizer 30; An oxygen supply unit 14 for providing oxygen to the oxidation reactor 20; The process water supply unit 16 for supplying the process water which is the main reaction medium to the lower portion of the oxidation reactor 20, and provides the process water to the outlet side of the oxidation reactor 20 for the cooling of the product material. Two-stage waste disposal apparatus of a chemical agent, characterized in that. The method of claim 5, The oxidation device main body 31 is installed at the inlet side of the oxidation reactor 20 to mix the decomposition material supplied from the decomposition material supply unit 12 and oxygen supplied from the oxygen supply unit 14 to the oxidation reactor. A feed mixer 37 for supplying to the feedstock, and an exhaust mixer 38 installed at an outlet side of the oxidation reactor 20 to cool and neutralize the product using process water or caustic soda solution. Two-stage waste disposal apparatus of a chemical agent, characterized in that. The method of claim 6. Further comprising a supplementary fuel supply unit 18 for supplying an auxiliary fuel made of IPA (Isopropyl Alcohol) to the oxidation reactor 20, the feed mixer 37 is supplied from the auxiliary fuel supply unit 18 Two-stage waste treatment apparatus of a chemical agent, characterized in that the auxiliary fuel is also mixed and supplied together. The method of claim 7, wherein The decomposition product supply unit 12, the process water supply unit 16 and the auxiliary fuel supply unit 18, the reservoir 12V (16V) (18V) and the reservoir 12V (16V) (18V) in which the substance is stored. Particle filters 12F, 16F, 18F for removing particulate matter from the fluid from the fluid, high pressure pumps 12P, 16P, 18P for pumping the filtered fluid, and a heating heat exchanger 12E for heating the fluid. And (16E) and (18E), respectively, wherein the two-stage waste treatment apparatus of the chemical agent is provided. The method of claim 5, The oxygen supply unit 14 includes an oxygen storage tank 14V for storing oxygen produced by the oxygen generator 14A, an oxygen compressor 14C for compressing oxygen from the oxygen storage tank 14V, and an oxygen compressor 14C. And a heating heat exchanger (14E) for heating the oxygen from). The method of claim 2, The oxidation reactor 20 has a cylindrical shell 21 in which a through hole 21 'penetrates up and down, and is located inside the through hole 21' of the shell 21, and the decomposition material Oxidation reaction of the influent material is made and the inner tube 22 formed at a lower height than the shell 21 and the upper portion coupled to the upper portion of the shell 21 to block the upper end of the through hole 21 '. An oxygen injector 24 installed through the cover 23, the upper cover 23, and supplying oxygen into the inner tube 22, and positioned inside the oxygen injector 24 and the oxygen injector Decomposition material injector 25 that protrudes compared to (24), and the product material discharge hole is coupled to the lower portion of the shell 21 to block the lower end of the through hole (21 ') and communicate with the inner tube (22) And a water supply hole 26 "for supplying water between the inner tube 22 and the inner circumferential surface of the through hole 21 'and the outer circumferential surface of the inner tube 22. A lower cover (26) and a valve coupled to a lower end of the inner tube (22) to open and close the product discharge hole (26 '). The method of claim 10, The shell 21 is a Hastelloy (Hastelloy) C-276 material, the inner tube (22) is a two-stage waste treatment apparatus of a chemical agent, characterized in that the titanium grade II material. The method according to any one of claims 1 to 11, Wherein said chemical agent is any one of a nerve agent, a nerve agent precursor, and a blistering agent. The method of claim 12, The nerve agent is sarin (GB; O-Isopropyl Methylphosphonofluoridate) or VX, The nerve agent precursor is a binary agent of methyl phosphonic difluoride (DF) or OPA, Wherein said blistering agent is mustard (HD). The method of claim 12, Decomposition material of the chemical agent, MPA (Methylphosphonic Acid or TDG (Thiodiglycol), characterized in that any one of the two-step waste treatment apparatus of the chemical agent. The method of claim 12, Decomposition material of the chemical agent, the two-stage waste treatment apparatus of the chemical agent, characterized in that it comprises an acid and salt of a halogen group element. A detoxification step of supplying water or caustic soda solution with the chemical agent to hydrolyze or neutralize the chemical agent; And a oxidizing step of introducing the decomposed material generated in the step into a supercritical reactor and supplying process water and oxygen to oxidize the decomposed material. The method of claim 16, The second step disposal of the chemical agent characterized in that it further comprises a post-treatment step of processing the product formed in the oxidation step to enable the external discharge and the discharge step of separating and discharging the finished material after the post-treatment into a gas and a liquid Treatment method. The method of claim 17, The post-treatment step includes the steps of rapidly cooling the product, filtering the particulate matter contained in the product, and depressurizing the supercritical pressure to normal pressure. Disposal Method. The method of claim 16, The toxic treatment step includes the step of further treating the primary decomposition product produced by neutralizing or hydrolyzing the chemical agent with a caustic soda solution.  The method according to any one of claims 16 to 19, The detoxification step allows the hydrolysis or neutralization reaction to proceed until the decomposition rate of the chemical agent reaches 99.99%, The oxidation step is a two-step waste treatment method of the chemical agent, characterized in that the oxidation until the disposal efficiency of the total organic carbon or treated material reaches 99.99%. The method of claim 20, The internal reaction pressure of the reactor is at least 220 atm and at most 300 atm, and the internal reaction temperature is at least 374 ° C and at most 660 ° C. The method of claim 20, Wherein the oxygen is pressurized to the internal reaction pressure of the reactor, according to the type of decomposition material is heated to a temperature of 400 ℃ ~ 500 ℃ characterized in that the two-stage disposal method of the chemical agent. The method of claim 20, The decomposition material is supplied by pressurizing to the internal reaction pressure of the reactor, and heated to room temperature or 400 ℃ according to the type of decomposition material and then supplied to the oxidation step, characterized in that the two-stage disposal method of the chemical agent. The method of claim 20, The process water is pressurized to the internal reaction pressure of the reactor and supplied, heated to 400 ℃ to supply to the oxidation step, characterized in that the two-stage disposal of chemical agents. The method of claim 20, Further supplying auxiliary fuel IPA to the reactor in the oxidation step, Wherein the IPA is pressurized to an internal reaction pressure of the reactor and then heated to 400 ° C. to supply the IPA.

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