KR100756558B1 - Chemical Agent Treatment System and Treatment Method - Google Patents

Abstract

The present invention relates to a chemical agent processing apparatus, wherein the chemical agent processing apparatus includes a hydrolysis reactor for hydrolyzing or neutralizing a chemical agent; And in-liquid incinerator which incinerates the decomposition material produced by the hydrolysis reactor in-liquid exhaust type to safely and completely dispose of the chemical agent.

Description

Chemical Agent Treatment Apparatus and Treatment Method {APPARATUS AND METHOD FOR DESTRUCTION OF CHEMICAL WARFARE AGENTS}

1 is a conceptual diagram schematically showing a chemical agent treatment process according to an embodiment of the present invention,

2 is a conceptual diagram schematically showing a chemical agent processing apparatus according to an embodiment of the present invention;

3 is a graph showing sarin (GB) hydrolysis rate with temperature and time,

4A is a graph showing the hydrolysis rate of HD according to the concentration and time of HD,

Figure 4b is a graph showing the hydrolysis rate of HD in accordance with the HD concentration and time in the state of caustic soda solution injected into the HD solution,

5 is a graph showing the concentration of sulfur compounds with time depending on whether or not the caustic soda solution is injected into the fluidized bed heat exchanger shown in FIG.

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

10; Hydrolysis reactor 30; Submerged incinerator

31; Incinerator body 35; burner

36; Injector 37; Quencher

50; Post-processing device 51; Venturi scrubber

52; Absorption tower 54; Fluidized bed heat exchanger

60; Chimney 61; Demister

90; Wastewater solidification phase 91; Wastewater evaporator

92; dryer

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chemical agent treatment apparatus and a treatment method, and more particularly, to a chemical agent treatment apparatus and a treatment method for incineration of hydrolyzed substances into harmless substances in a liquid exhaust type incinerator after hydrolysis of the chemical agent significantly removes toxicity. will be.

Chemical weapons, weapons of mass destruction, must be disposed of completely in accordance with the Chemical Weapons Convention (CWC) so that they cannot be reused within a designated period. The key to achieving this is to safely and completely dispose of the agent, the most important substance of chemical weapons. Agents are toxic chemicals that are extremely dangerous to handle and are extremely deadly to humans even with trace amounts of atmospheric exposure.

In the treatment of small amounts of chemical weapons, many countries in the world have separated their agents from coal, rockets, land mines, etc., and incinerated them, neutralized them with basic aqueous solutions or methylethanolamine, and then buried or incinerated them. In the United States, the technology has been used to safely remove chemical agents from chemical weapons and then directly incinerate the agents and carcasses. However, when incineration of chemical agents directly, not only the chemical agents are left untreated by incomplete combustion, but also toxic substances may be released to the outside during incineration.

For this reason, a safety device for preventing air leakage of an agent that is very harmful to the human body during the handling process should be separately installed, but there is a problem that such a stabilizer is huge. In addition, when using a plurality of activated carbon filter to remove the harmful gas discharged during incineration, there is a problem that the waste activated carbon absorbed various gases must be treated.

Meanwhile, Russia, the world's largest chemical weapons state, is planning to reclaim its landfills by neutralizing and neutralizing its agents. Once the agent is hydrolyzed with water or neutralized with a basic substance, the degradation product can dramatically reduce the toxicity of the agent, making it easier to handle without the operator using special equipment. However, since decomposition products still contain List 2 substances regulated by the CWC, halogens or acids and large amounts of salts, these substances must also be converted completely into harmless substances.

As described above, the treatment of the agent proceeds by direct incineration or by embedding the material produced during hydrolysis. However, when incinerated directly, as described above, not only the chemical agent may be left untreated due to incomplete combustion, but also toxic substances may be released to the outside during incineration, and the hydrolyzate-producing decomposition material may In this case, the decomposition material contains halogen or acid and a large amount of salt, which is the main cause of environmental pollution.

The present invention has been made in view of the above-described point, and an object of the present invention is to provide a chemical agent treatment apparatus and a treatment method capable of safely and completely treating a chemical agent.

It is another object of the present invention to provide a chemical agent treatment apparatus and a treatment method which can prevent the environmental pollution inherently by not discharge the chemical agent treatment wastewater to the outside.

Chemical agent processing apparatus according to the present invention for achieving the above object is a hydrolysis reactor for hydrolyzing or neutralizing the chemical agent; And a liquid exhaust type incinerator for incineration the decomposition products produced by the hydrolysis reactor in the liquid exhaust type.

According to an embodiment of the present invention, the submersible incinerator is an incinerator body provided with a chamber into which the decomposition material flows; A combustor provided in the incinerator body to incinerate the decomposition material introduced into the chamber; And a quencher in which water through which the exhaust gas of the decomposition material incinerated by the combustor passes is stored. Some of the exhaust gas is absorbed into the water of the quencher, and the remaining exhaust gas is discharged.

It may include a post-treatment device for purifying the exhaust gas discharged from the quencher, the post-treatment device comprises a venturi scrubber for removing the solid particles of the discharged exhaust gas; An absorption tower for absorbing the exhaust gas passing through the venturi scrubber into water; And a fluidized bed heat exchanger for cooling the exhaust gas passing through the absorption tower to absorb the exhaust gas into water.

The fluidized bed heat exchanger includes a plurality of pipes through which cooling water passes, and exhaust gas passing through the absorption tower is cooled by the plurality of pipes. The induction layer heat exchanger stores water for absorbing exhaust gas cooled by the plurality of pipes, and caustic soda solution may be circulated in the water.

On the other hand, the above-described chemical agent treatment apparatus is a chimney for discharging the exhaust gas passing through the fluidized bed heat exchanger to the outside, and wastewater for solidifying the wastewater absorbed by the flue gas generated by the submerged incinerator and the after-treatment device It may include a solidifier.

The chimney includes a demister for removing water vapor from the exhaust gas passing through the fluidized bed heat exchanger, and the wastewater solidifying unit comprises: a wastewater evaporator for evaporating and concentrating wastewater absorbing the exhaust gas; And a dryer for drying and solidifying the wastewater evaporated and concentrated by the wastewater evaporator.

The chemical agent includes a neuroagent, a neuroagent precursor and sulfur mustard, the neuroagent is GB (isopropyl methylphosphonofluoridate), and the precursor is made of DF (methylphosphonic difluoride). The degradant includes MPA, TDG, and OPA.

On the other hand, the above object is to a) hydrolyzing or neutralizing the chemical agent; And b) it can be achieved by a chemical agent treatment method comprising the step of incineration of the decomposition material produced by step a) in liquid exhaust.

According to an embodiment of the present invention, the step a), hydrolysis proceeds until the decomposition rate of the chemical agent reaches 99.99%, the step b) is the destruction and removal efficiency of the decomposition material (Destruction and Removal efficiency) Incinerator was incinerated until the efficiency (DRE) reached 99.99%.

In addition, the step a) may include the step of neutralizing the decomposition product produced by hydrolyzing the DF to a caustic soda solution.

On the other hand, the above-described chemical agent treatment method, c) comprises the step of purifying the exhaust gas generated by step b), the step c) is the step of c1) absorbing a portion of the exhaust gas in water; c2) cooling the portion of the off-gas not absorbed by the water in step c1) to absorb the water; And c3) removing moisture from the exhaust gas which is not absorbed in water in step c2). Wherein c2), the step of cooling the exhaust gas; Absorbing the cooled exhaust gas into water; And circulating a caustic soda solution in water absorbing the cooled exhaust gas.

In addition, the above-described chemical agent treatment method may include d) solidifying the water absorbing the exhaust gas of the steps c1) to c3), the step d), repeatedly evaporating the water absorbed the exhaust gas To form sludge; And solidifying the sludge by drying.

Hereinafter, with reference to the accompanying drawings will be described in detail with respect to the chemical agent processing apparatus and processing method according to an embodiment of the present invention.

1 and 2, the chemical agent processing apparatus according to an embodiment of the present invention, the hydrolysis reactor 10, submerged incinerator 30, after-treatment device 50, chimney ( 60), wastewater storage tank 70, and wastewater solidifier 90.

The hydrolysis reactor 10 is for hydrolyzing or neutralizing a chemical agent, and filling the commercial hydrolysis reactor 10 with water or caustic soda solution according to the type of chemical agent to be treated, and slowly injecting the chemical agent. Stir while. After hydrolysis or neutralization at a certain temperature for a certain period of time, the decomposition products are stabilized, and the concentration of the agent is analyzed. When the hydrolysis rate reaches 99.99% or more, the materials generated during decomposition are pumped to the decomposition material storage tank 12 to be incinerated. Incinerate. If the hydrolysis rate does not reach 99.99% or more, the chemical agent is transferred to the hydrolysis reactor 10 to hydrolyze or neutralize.

The types of agents reported to the chemical weapons ban are about 70% of the total amount of nerve agents such as VX, sarin, and blisters such as sulfur mustard, and industrial gases and dual agents. Therefore, in this embodiment, as an example of the chemical agent to be treated, is currently the largest stockpile and representative of the neurological agent (isopropyl methylphosphonofluoridate, GB) and the representative of the blistering agent Sulfur mustard, (((bis- (2- chloroethyl) sulfide, HD)) and binary chemical agent, DF (methylphosphonic difluide), a raw material of sarin synthesis, was selected and two-stage treatment (hydrolysis or neutralization and Submerged incineration) was implemented. Looking at the hydrolysis or neutralization process in the hydrolysis reactor 10 of the above-described chemical agent is as follows.

When sarin (GB) is hydrolyzed with an aqueous NaOH solution, non-toxic organic salts, NaF, and water are produced as shown in Chemical Formula 1.

C ₄ H ₁₀ FO ₂ P (GB) + 2NaOH-> C ₄ O ₁₀ O ₃ PNa + NaF + H ₂ O

Sulfur mustard (HD) hydrolyzes with water to produce thiodiglycol (TDG) and HCl, as shown in formula (2).

(ClCH ₂ CH ₂ ) ₂ S (HD) + H ₂ O-> (OHCH ₂ CH ₂ ) ₂ S + HCl

When DF is hydrolyzed by water, it is decomposed into methylphosphonic acid (MPA) and HF as shown in Chemical Formula 3.

CHP ₃ (O) F ₂ (DF) + H ₂ O-> CH ₃ P (O) (OH) ₂ + HF

 Hydrolyzing or neutralizing sarin (GB), sulfur mustard (HD) and DF with basic substances such as water or caustic soda almost eliminates the original toxicity of chemical agents, but MPA and TDG, the major hydrolysis products, As specified, these materials must also be disposed of completely so that they cannot be reused. Therefore, there is a need for a process for treating decomposed substances produced by hydrolysis or neutralization. Degradants also include salts such as NaF and acids such as HCl and HF, respectively.

Such decomposition products are ultimately processed by a Submerged Quench Incinerator. As such, the decomposition products generated in the hydrolysis or neutralization step by the hydrolysis reactor 10 are almost eliminated the toxicity of the chemical agent. Therefore, it is possible to work more safely at the stage after hydrolysis or neutralization. In particular, by incineration of the reduced decomposed substances by primarily treating the toxic in the liquid incineration incinerator 30 described later, even if incomplete combustion occurs in the liquid incineration incinerator 30 or the decomposition products leak in the form of gas to the human body It's not fatal. Therefore, the incineration in the liquid exhaust type incinerator 30 can be carried out more safely. Hereinafter, the liquid exhaust type incinerator 30 will be described.

The submersible incinerator 30 is operated to achieve at least 99.99% of the destruction and removal efficiency (DRE) of organic matter, and the exhaust gas generated at this time is stored in water at the lower portion of the incinerator. Some of them are dissolved in the waste water by contact, and some of them pass through the aftertreatment device 50 to satisfy the air emission standard and then discharged to the outside through the chimney 60. On the other hand, all the wastewater generated in the liquid incinerator 30 and the after-treatment device 50 is collected in the wastewater storage tank 70 and then neutralized, and the wastewater is concentrated in the wastewater evaporative concentrator 91 and finally dried. ), Remove moisture, dry and collect pneumonia. The waste salt is sent to a general waste treatment plant once a certain amount is collected. As such, the apparatus for treating chemical agents according to one embodiment of the present invention is to discharge the waste water freely.

The submersible incinerator 30 includes an incinerator body 31, a combustor 35 provided on an upper portion of the incinerator body 31, two injectors 36 disposed on both sides of the combustor 35, It includes a quencher (37, provided in the lower portion of the incinerator body 31).

The incinerator body 31 is composed of a plurality of stages and is easy to assemble and disassemble. The incinerator body 31 has a chamber 32 formed in a vertical direction, and the chamber 32 has a decomposition material storage tank 12. Decomposition material moved from) is introduced by the injector 36. Looking at the inflow process in more detail, the hydrolysis rate is completed up to 99.99% and the decomposed material stored in the decomposer storage tank 12 is stored in the feed tank 33 by a pump (not shown), the feed pump 34 It is introduced into the chamber 32 through the injector 36 by the.

The combustor 35 is for burning the decomposition material introduced into the chamber 32, a device such as a vortex burner may be used. In the case of using the vortex burner, the molten metal salt is moved to the wall with good mixing effect and strong centrifugal force and flows to the bottom of the incinerator body 31 by gravity to be easily recovered from the quencher 37.

The injector 36 is to introduce the decomposition material into the incinerator body 31, two air atomizers and the like can be used. If the calorific value of the decomposition material is low, either of the two injectors 36 may be used to inject auxiliary fuel.

The quencher 37 serves to primarily process the exhaust gas generated by the combustion of decomposition products from the incinerator body 31. Water is stored in the quencher 37, and downcomer 38 and down weir 39 are provided. The hot exhaust gas discharged after incineration of decomposition products flows into the water stored in the quencher 37 through the downcomer 38, and the exhaust gas introduced into the water is downcomer 38 and weir in the form of gas / liquid mixture. To rise between 39). At this time, part of the exhaust gas is dissolved in the water and absorbed. In addition, the molten salt generated in the incinerator body 31 falls to the lower portion of the quencher 37 by water flowing along the inclined surface of the downcomer 38.

This exhaust gas is partially absorbed by the quencher 37 and then moved to the aftertreatment device 50. As described above, MPA and TDG, which are decomposition products of sarin (GB), sulfur mustard (HD), and precursor DF, may be incinerated by the liquid exhaust type incineration. However, water neutralized with caustic soda may be used for the quencher 37.

The aftertreatment apparatus 50 is for purifying exhaust gas not absorbed by the quencher 37, and includes a venturi scrubber 51, an absorption tower 52, and a fluidized bed heat exchanger 54.

The venturi scrubber 51 removes relatively large solid particles of exhaust gas not absorbed by the quencher 37.

The absorption tower 52 is to absorb the exhaust gas passing through the venturi scrubber 51 into water, and supplies water to a passage through which the exhaust gas passes to absorb a portion of the exhaust gas into the water. Water in which exhaust gas is absorbed is recovered to the absorption tower wastewater tank 53.

The fluidized bed heat exchanger 54 is for cooling the exhaust gas passing through the absorption tower 52 and for absorbing it in water, and a plurality of pipes 55 to which cooling water is supplied are provided. The exhaust gas cooled by the plurality of pipes 55 is condensed and absorbed into the water inside the fluidized bed heat exchanger 54. The partial condensation of moisture in the flue gas makes it possible to remove the flue gas more effectively. The water in which the exhaust gas is absorbed is recovered to the heat exchanger wastewater tank 56. The exhaust gas passing through the fluidized bed heat exchanger 54 is cooled by the cooling water so that the temperature of the exhaust gas is drastically reduced. The exhaust gas passing through the fluidized bed heat exchanger 54 is moved to the chimney 60 by the fan 57.

The chimney 60 is for discharging the exhaust gas to the outside, a demister made of a four-stage plastic mesh is embedded. The exhaust gas passing through the aftertreatment device 50 contains water, and this water is removed by the demister 61. In addition, the demister 61 may remove fine particles of the exhaust gas, and is particularly effective for removing phosphorous components. The condensed water removed by the chimney 60 is collected in the chimney waste water tank 62.

The wastewater storage tank 70 is for collecting the wastewater collected in the quencher 37, absorption tower wastewater tank 53, heat exchanger wastewater tank 56, and chimney wastewater tank 62, 37) and the respective wastewater tanks 53, 56 and 62. The wastewater collected in the wastewater storage tank 70 contains a strong acid such as fluorine (F), phosphorus (P) or hydrogen chloride (HCl) generated when incineration of HD hydrolyzate contained in the sarin wastewater. Therefore, when the wastewater is discharged to the outside, it will cause eutrophication to SOHO or river water and should be thoroughly treated in accordance with environmental regulations and wastewater discharge standards. Therefore, a wastewater solidifier 90 is needed to solidify such wastewater.

The wastewater solidifier 90 is for solidifying the wastewater of the wastewater storage tank 70, and includes a wastewater evaporator 91 and a dryer 92.

The wastewater evaporation concentrator 91 repeatedly distills and concentrates the wastewater of the wastewater storage tank 70, thereby making the wastewater into a sludge form.

The dryer 92 is for drying and solidifying the sludge-type wastewater in order to collect the wastewater in the form of a solid salt, and a drum dryer or a spray dryer may be used. By treating the wastewater by solidifying the wastewater by the wastewater evaporation concentrator 91 and the dryer 92 in this manner, it is possible to prevent the wastewater from being directly discharged to the outside, thereby minimizing the pollution of the environment.

Hereinafter will be described in detail a chemical agent treatment method according to an embodiment of the present invention.

First, the hydrolysis reactor 10 is filled with water or caustic soda solution depending on the reactants, and stirred while slowly injecting a chemical agent such as sarin (GB), sulfur mustard (HD) or DF to hydrolyze or neutralize. After hydrolysis or neutralization at a certain temperature for a certain period of time, the decomposition products are stabilized and the concentration of the chemical agent is analyzed. When the hydrolysis rate reaches 99.99% or more, the decomposition products generated during decomposition are pumped into the decomposition material storage tank 12 (not shown). Transfer to).

Decomposition material transferred to the decomposition product storage tank 12 is transferred to the feed tank 33 is introduced into the chamber 32 of the incinerator body 31 through the injector 36 by the feed pump 34. The decomposition products introduced into the chamber 32 are incinerated by the combustor 35, and the exhaust gas after incineration is absorbed into the water stored in the quencher 37 through the downcomer 38 of the quencher 37. In more detail, the exhaust gas rises between the downcomer 38 and the weir 39 after entering the stored water through the downcomer 38. At this time, the exhaust gas introduced into the water rises between the downcomer 38 and the weir 39 in the form of gas / liquid mixture. At this time, part of the exhaust gas is dissolved in the water and absorbed. In addition, the molten salt generated in the incinerator body 31 falls to the lower portion of the quencher 37 by water flowing along the inclined surface of the downcomer 38. Meanwhile, water stored in the quencher 37 may be water neutralized with caustic soda. The water stored in the quencher 37 is transferred to the wastewater storage tank 70.

Flue gas not absorbed by the water in the quencher 37 is moved to the venturi scrubber 51 to remove relatively large solid particles. Exhaust gas not removed in the venturi scrubber 51 is moved to the absorption tower 52 and absorbed by the sprayed water. The water in which the exhaust gas is absorbed is recovered in the absorption tower wastewater tank 53, and the water recovered in the absorption tower wastewater tank 53 is collected in the wastewater storage tank 70.

Water passing through the absorption tower 53 is introduced into the fluidized bed heat exchanger (54). The water flowing into the fluidized bed heat exchanger 54 is cooled and condensed by a plurality of pipes 55 through which cooling water is circulated, and the condensed exhaust gas is efficiently absorbed by the water, which is the circulating water of the fluidized bed heat exchanger 54. do. At this time, caustic soda may be circulated in the circulating water of the fluidized bed heat exchanger 54 to reduce sulfur compounds from the exhaust gas.

The exhaust gas passing through the fluidized bed heat exchanger 54 is moved to the chimney 60 by the fan 57 to remove the fine particles of the moisture and the exhaust gas by the demister 61. In particular, the phosphorus component is efficiently removed. The condensation water removed by the demister 61 is collected in the chimney waste water tank 62 and collected in the waste water storage tank 70.

The wastewater collected in the wastewater storage tank 70 is sent to the wastewater evaporator 91, and repeatedly distilled by the wastewater evaporator 91 to form sludge. The sludge wastewater is again solidified in the form of a solid salt by the dryer 92.

Hereinafter, experimental examples for hydrolysis or neutralization of chemical agents and incineration of decomposition products will be described.

Experimental Example 1 Hydrolysis of Sarin (GB)

Sarin (isopropyl phosphonofluoridate, GB), a representative substance of neurological agents, was hydrolyzed with caustic soda solution to convert to harmless substance. The experiment was conducted by connecting a circulator to a jacketed small reactor, injecting 10 wt% of sarin into a 2.05 equivalent aqueous solution of caustic soda, and changing the temperature (50, 70, and 90 ° C), respectively. Obtained. When the amount of caustic soda is increased during hydrolysis, not only NaF increases but also the amount of salts generated increases the amount of caustic soda to minimize the amount of caustic soda.

As a result of GB hydrolysis experiment in aqueous NaOH solution, the degradation was accelerated when the temperature was increased as shown in Table 1 and FIG. 3, and more than 99.99% of the sarin was decomposed when hydrolyzed at 90 ° C. for 60 minutes or more. Table 1 below shows the results of hydrolysis experiment (hydrolysis rate:%) of sarin according to temperature and reaction time.

The experimental results were obtained by applying the first rate equation to find the rate constant and substituting the dependence of the temperature constant for temperature on the Arrhenius equation for good linearity. As a result of predicting the reaction time required to achieve more than% is shown in Table 2. In the actual process, it is preferable to dispose the agent within the shortest time (1 to 2 hours). Therefore, the reaction conditions under which the agent decomposes at least 99.99% are most preferably reacted at 80 ° C for 2 hours and at 90 ° C for 1.2 hours or more. The product was analyzed by gas chromatography-mass spectrometry (GC-MSD) and liquid chromatography (LCQ (IT)) and isopropylmethyl phosphonate (iMPA). Table 2 shows the reaction prediction time required to achieve the hydrolysis rate (more than 99.99%) of sarin by reaction temperature.

Experimental Example 2 Hydrolysis of Sulfur Mustard HD

HD was hydrolyzed with water to convert sulfur mustard (HD, bis 2-chloroethylsulfide), a representative substance of blister, into a harmless substance. Since HD is rapidly decomposed by water at high temperature (80-90 ° C.), the reaction temperature was fixed at 90 ° C., and HD waste conditions were set by analyzing reaction time, HD concentration, and the effect of caustic soda after hydrolysis. The experiment was connected to the same small reactor as in Experimental Example 1, and 10-20 wt% of HD was injected into 90 ° C water, followed by reaction for 1.5 hours or more, followed by additional reaction for 30 minutes with 2.01 equivalents of aqueous solution of caustic soda at room temperature. The final degradation product was quantitatively analyzed by gas chromatography-mass spectrometry ((GC / MS (SIM)), which showed 68 wt% Thiodiglycol (TDG), 1,2-Bis (2-hydroxyethylthio) ethane, 8wt% and Bis- (2-hydroxy ethylthioethyl) ether was 24wt% Table 3 shows the hydrolysis rate (%) of sulfur mustard (HD) with concentration at 90 ° C.

Sulfur mustard (HD) has very low solubility in water, so when it is put into water, it is separated into the lower layer, so it is important to increase the solubility in water to promote hydrolysis. In order to determine the hydrolysis effect depending on the concentration, sulfur mustard (HD) concentration (10, 15 and 20 wt%) was tested and the result was degraded to about 99.9% as shown in Table 3 and FIG. 4 (a) after 1 hour. Increasing the reaction time over 2 hours did not significantly increase the decomposition rate. In addition, in order to prevent the generation of sulfur mustard (HD) by the reverse reaction by neutralizing the HCl generated during the hydrolysis, after the reaction of the caustic soda solution at room temperature after 2.1 equivalents of the initial HD amount after analyzing the reaction results over time 1 Within 9 hours, 99.99% was achieved within all concentration ranges. Sulfur mustard (HD) decomposition rate was influenced not only by temperature but also by stirrer type and stirring speed. Therefore, the rotating rod used in the experiment was a small size (3 cm), but by improving the stirring method will be able to further reduce the decomposition time of sulfur mustard (HD).

Experimental Example 3 Hydrolysis of DF

Methylphosphonic difluoride (DF) is a precursor of sarin (GB) and together with OPA (a mixture of isopropyl alcohol and isopropyl amine), it forms a binary chemical weapon. In order to completely destroy the DF, DF was hydrolyzed at 70-90 ° C. for 2 hours or more with water at a ratio of 1: 1.5, and analyzed by ion chromatography (IC), 45% of water, methylphosphonic acid (MPA), 39% and 16% HF was produced and no DF was detected. Since the decomposition product contains a large amount of HF, a strong acid, in case of incineration, it may corrode the incinerator fire wall and exhaust gas treatment device. Therefore, HF is removed to the maximum while organic MPA is dissolved in water as much as possible (solubility: 32.3wt %) Incineration was considered economically.

In order to achieve this, HF was recovered by incineration using the azeotropy point of water and HF, and the optimum composition of the incinerator was composed of about 32% MPA, about 1% HF and water, and the remaining mixture of MPA and HF was incinerated. The final composition of the in-liquid incineration test solution according to the experimental example is I. The analysis consisted of 32.14 wt% MPA, 1.02 wt% HF and water.

(Experimental example 4): incineration of DF hydrolysis solution (1)

MPA (generated upon hydrolysis of sarin and DF) and TDG (generated upon hydrolysis of HD) among the major degradation products generated during hydrolysis in Experimental Examples 1 to 3 are CWC regulated substances and should be disposed of completely. Hydrolysis of nervous system agents such as VX, sarin, and DF commonly produces MPA. In particular, sarin and DF hydrolyzate contain hydrofluoric acid along with MPA, which is the most difficult to incinerate. Was incinerated.

The composition of the incineration solution was composed of MPA 26.4 ~ 32.1 wt%, HF 0.8 ~ 1.02wt%, the remainder of water, pH 2.0∼2.9, calorific value less than about 1,000 kcal / kg. When the mixture was incinerated at a weight ratio of 1.2 to 1.5, and the incineration temperature was incinerated at 900 to 1100 ℃, the DRE was achieved at 99.99% or more. At this time, the emission standards (CO, SOx, NOx, and HF) of the main generated gases were met. Smoke occurred.

(Experimental example 5): incineration after neutralization of DF hydrolysis solution with caustic soda (2)

The caustic soda solution was circulated through the incinerator rear end facility to remove the white smoke discharged in Experimental Example 4, but it was most effective to neutralize the incineration solution with caustic soda solution before incineration. Therefore, the neutralization effect of each concentration of caustic soda solution was tested to find the maximum input ratio of neutralizing agent, and the neutralization was well up to 40wt% (10 mol NaOH solution). . When precipitation occurs in the waste liquid, the nozzle hole of the injector 36 can be closed, neutralized with 40 wt% caustic soda solution, and incinerated, resulting in drastically removing white smoke while achieving DRE 99.99%. White smoke was produced by P ₂ O ₅ generated by thermal decomposition of MPA, a phosphorus compound at high temperature, in contact with water. PO ₄ ^-3 was measured by IC and the concentrations before and after neutralization were quantitatively compared. DRE and flue gas analysis results according to Experimental Examples 4 and 5 are shown in Table 4, respectively. Table 4 shows a comparison of organic material destruction efficiency (DRE) and chimney emissions.

Here, A is an unneutralized sample (DF hydrolysis solution) of Example 4, and B is a neutralizing sample of Example 5 (neutralizing the DF hydrolysis solution with 40wt% caustic soda). DRE is based on total hydrocarbons, and HF and PO ₄ ^-3 concentrations were collected by gas into the collection bottle and analyzed by IC after the experiment.

Experimental Example 6 Incineration of TDG

According to Experiment 2, 10 wt% of TDG, which is a major substance produced during HD hydrolysis, was dissolved in water and incinerated. The TDG solution was mixed with acetone at a ratio of 1: 1 and incinerated at an incineration temperature of 800-1,010 ° C. at 3 to 4 kg / hr. As a result, DRE was more than 99.99% but a large amount of sulfur compound (SOx) was generated (up to 240 ppm). Since TDG contains sulfur, various methods were tested to reduce SOx to less than 1/2 of the current standard of 100 ppm (incineration capacity below 200 Kg / hour), and the caustic soda solution was circulated in the fluidized bed heat exchanger (54). Was most effective at removing SOx. As a result of injecting 10 mol of caustic soda solution 50CC into the circulation tank of the fluidized bed heat exchanger 54, as shown in FIG. 5, the concentration of SOx in the exhaust gas was lowered to 100 ppm or less. Therefore, if the pH concentration controller is installed in the circulation tank and the pH is kept constant with the caustic soda solution, the concentration of SOx in the exhaust gas can be adjusted to the desired concentration.

In addition, as in Example 2, HCl, NaCl and TDG solution were added to the TDG solution to determine the effects of salt upon incineration by adding caustic soda solution to the decomposition material to prevent reverse reaction and increase hydrolysis efficiency after hydrolysis of HD. Incineration by mixing NaOH up to 1 wt% did not limit the incineration or reduce the DRE.

Experimental Example 7 OPA Incineration

OPA is a 72:28 mixture (weight ratio) of isopropyl alcohol and isopropyl amine, which is a CWC regulated agent that produces sarin when mixed with DF and must be disposed of completely. OPA is stored in a polyethylene container, and after removing the contents after drilling, the incineration solution contains a large amount of washing water as the storage container is thoroughly washed with water during the disposal process. The concentration of the waste liquid generated at this time was 70% water, 28% isopropyl alcohol and 2% isopropylamine. The calorific value was lowered by incineration at 900 ~ 1100 ℃ with injection fuel of 6.4 ~ 9.4Kg / hr and the DRE was more than 99.99%, and the NOx concentration, which is the main pollutant, was below the emission standard.

Experimental Example 8 Wastewater Treatment and Pulmonary Salt Production

The quencher circulating water and the flue-gas cleaning water discharged from the incineration process are acidified and must be discharged after the final treatment according to the wastewater discharge limit.

According to the above embodiment, after incineration of various waste fluids at 6-9 Kg / hr for 3-4 hours, the main pollutant was analyzed based on the quencher where the wastewater is most generated. Table 5 shows Quencher wastewater properties (example) after 3.5 hours incineration at 6 Kg / h.

The acceptance criteria are those specified in Article 8 of the Water Environment Preservation Act and Article 8 of the Enforcement Rule of the Act, MPA 1 is a hydrolysis solution of DF, and MPA 2 is a sample neutralized with MPA 1 with caustic soda solution.

Among the wastewaters from incineration wastewater, the regulated substances are, in particular, MPA wastewater that exceeds the fluoride and total phosphorus emission limits. Therefore, the quencher wastewater was chemically treated with 10 mol NaOH solution, the treated wastewater was evaporated and concentrated, dried in a dryer, and the waste salt was collected in a collection tank.

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 can be changed as appropriate within the scope described.

According to the present invention as described above, the chemical agent is first hydrolyzed or neutralized to treat the chemical agent first to reduce the toxicity, and thereafter, the decomposition material produced by the hydrolysis by the liquid exhaust incineration is secondary. By treating with, the chemical agent can be treated more safely and completely.

In addition, the exhaust gas discharged from the liquid exhaust type incinerator is purified by the venturi scrubber, the absorption tower, the fluidized bed heat exchanger, and the chimney's demister in order to completely purify the exhaust gas discharged to the outside.

In particular, the exhaust gas can be purified more efficiently by cooling the exhaust gas by condensing and absorbing it in water after condensing.

In addition, by adding a caustic soda solution to the water circulating water of the fluidized bed heat exchanger, it is possible to minimize the environmental pollution by reducing the emissions of sulfur compounds.

On the other hand, by solidifying and treating the wastewater treated with the chemical agent, it is possible to block the discharge of the wastewater to the outside. Therefore, it is possible to minimize environmental pollution by wastewater.

In other words, the two-stage treatment technology can easily hydrolyze the agent in the reactor by improving the existing techniques and methods, and it is possible to completely treat the hardly decomposable substances containing salts such as the decomposed substances generated by the liquid exhaust incinerator. This technology is the safest, most economical and most feasible technology for treating agent regardless of facility size.

Claims (28)

Hydrolysis reactors that hydrolyze or neutralize chemical agents; And Chemical treatment apparatus characterized in that it comprises a liquid incineration incinerator for incineration of the decomposition material produced by the hydrolysis reactor in the liquid exhaust. The incineration type incinerator of claim 1, wherein An incinerator body having a chamber into which the decomposition material flows; A combustor provided in the incinerator body to incinerate the decomposition material introduced into the chamber; And And a quencher storing water through which exhaust gas of the decomposition material incinerated by the combustor passes. The method of claim 2, Part of the exhaust gas is absorbed in the water of the quencher, the remaining exhaust gas is characterized in that the exhaust agent treatment apparatus. The method of claim 3, And a post-treatment device for purifying exhaust gas discharged from the quencher. According to claim 4, The post-processing device, A venturi scrubber for removing solid particles of the discharged exhaust gas; An absorption tower for absorbing the exhaust gas passing through the venturi scrubber into water; And And a fluidized bed heat exchanger for cooling the exhaust gas passing through the absorption tower to absorb the exhaust gas into water. The method of claim 5, The fluidized bed heat exchanger includes a plurality of pipes through which cooling water passes, And the exhaust gas passing through the absorption tower by the plurality of pipes is cooled. The method of claim 6, The induction layer heat exchanger is a chemical agent processing apparatus characterized in that the water for absorbing the exhaust gas cooled by the plurality of pipes is stored, the caustic soda solution is circulated in the water. The method of claim 5, And a chimney for discharging the exhaust gas passing through the fluidized bed heat exchanger to the outside. The method of claim 8, And the chimney comprises a demister for removing water vapor from the exhaust gas passing through the fluidized bed heat exchanger. The method of claim 4, wherein And a wastewater solidifying device for solidifying the wastewater absorbing the flue gas generated by the submerged incinerator and the aftertreatment device. The wastewater solidifying apparatus of claim 10, A wastewater evaporator for evaporating and concentrating the wastewater absorbing the exhaust gas; And And a dryer for drying and solidifying the wastewater evaporated and concentrated by the wastewater evaporator. The method according to any one of claims 1 to 11, Wherein the chemical agent comprises a neuroagent, a neuroagent precursor and sulfur mustard. The method of claim 12, The nerve agent is sarin (GB, isopropyl methylphosphonofluoridate), The precursor is a chemical agent processing apparatus, characterized in that DF (methylphosphonic difluoride). The method according to any one of claims 1 to 11, wherein the decomposition material, A chemical agent processing apparatus comprising MPA, TDG, and OPA. a) hydrolyzing or neutralizing a chemical agent; And b) a chemical agent treatment method comprising the incineration of the decomposition product produced by step a) in liquid exhaust. The method of claim 15, The step a) is a chemical agent treatment method, characterized in that to hydrolyze the chemical agent until the hydrolysis rate reaches 99.99%. The method of claim 15, Wherein said chemical agent comprises a nerve agent, a nerve agent precursor and sulfur mustard. The method of claim 17, The nerve agent is sarin (GB, isopropyl methylphosphonofluoridate), The precursor is a chemical agent treatment method, characterized in that DF (methylphosphonic difluoride). The method of claim 18, wherein b), Incinerating the decomposed substance produced by the hydrolysis until the destruction and removal efficiency (DRE) of the decomposing substance reaches 99.99%. The method of claim 19, wherein the decomposition material, A chemical agent treatment method comprising MPA, TDG, and OPA. The method of claim 18, wherein step a) And neutralizing the resulting decomposition product by hydrolyzing the DF with a caustic soda solution. The method of claim 15, c) purifying the exhaust gas produced by step b). The method of claim 22, wherein step c) c1) absorbing a portion of the exhaust gas into water; c2) cooling the portion of the off-gas not absorbed by the water in step c1) to absorb the water; And c3) removing water from exhaust gas not absorbed by water in step c2). The method of claim 23, wherein step c2), Cooling the exhaust gas; Absorbing the cooled exhaust gas into water; And And circulating a caustic soda solution in the water absorbing the cooled flue-gas. The method of claim 23, wherein d) solidifying the water absorbing the exhaust gas of the steps c1) to c3). The method of claim 25, wherein step d) Repeatedly evaporating the water absorbing the exhaust gas to form sludge; And And drying the sludge to solidify the sludge. Hydrolysis reactors that hydrolyze or neutralize chemical agents; A liquid exhaust type incinerator for incineration of the decomposition products produced by the hydrolysis reactor with liquid exhaust type; And And a post-treatment device for purifying exhaust gas discharged from the submerged incinerator. a) hydrolyzing or neutralizing a chemical agent; b) incineration of the decomposition products produced in step a); c) purifying the flue gas produced by step b); And d) solidifying the water absorbing the flue-gas generated by the steps b) and c).

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