JP2004161522A - Method for treating gunpowder and explosive - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for treating a gunpowder or an explosive whereby the treatment can be safely and efficiently carried out without causing pollution. <P>SOLUTION: A gunpowder or an explosive is impregnated with an organic solvent to produce a pasty substance. The pasty substance is mixed with a liquid to form slurry or a solution. The gunpowder or explosive contained in the slurry or solution is subjected to a wet oxidation treatment. <P>COPYRIGHT: (C)2004,JPO

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for treating explosives and explosives, and more particularly to a method for treating explosives and explosives that can be performed safely without causing pollution.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, when disposing of a propellant, a propellant, or the like, which is a kind of explosive or explosives, a method of dumping and disposing of the propellant and the propellant (hereinafter, referred to as waste propellant) into the sea. However, as the problem of marine pollution has become more serious in recent years, land-based treatment methods such as explosion and incineration have been implemented.In particular, smokeless explosives, including waste propellants, are generally incinerated. And other processing methods have been implemented. However, since the waste propellant is processed in a state where it is not decomposed, noise, odor, or vibration is generated at the time of combustion, and when burning the waste propellant, dust, nitrogen oxides, or dioxin In some cases, causing air pollution.
As a method for solving the above-mentioned problems, a method has been proposed in which explosives and explosives are hydrolyzed by heating to a temperature lower than the critical temperature of the solution in an alkali solution to which an alkali silicate is added as a reaction accelerator. (For example, see Patent Document 1).
[0003]
[Patent Document 1]
JP-A-8-59383
[Problems to be solved by the invention]
However, in the above treatment method, the explosives and explosives contained in the solution are not subjected to any pretreatment, and the explosives and explosives to be disposed of are directly mixed with the solution, and the solution is hydrolyzed. The explosives and explosives had to be finely divided before mixing, and a hydrolysis treatment had to be carried out without fail.
[0005]
The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a method for treating explosives and explosives that can be carried out safely and efficiently without causing pollution.
[0006]
[Means for Solving the Problems]
In order to solve the above-mentioned problem, the invention according to claim 1 provides a method for treating explosives, explosives by decomposing explosives by performing a wet oxidation treatment on explosives, explosives, etc. A paste-like substance by impregnating the paste-like substance with an organic solvent, mixing a liquid with the paste-like substance to form a slurry or a solution, and subjecting explosives and explosives contained in the slurry or the solution to wet oxidation treatment. And
According to this explosive and explosives processing method, first, after explosives and explosives are impregnated with an organic solvent to produce a paste-like substance, a liquid is mixed with the paste-like substance to form a slurry or a solution, Thereafter, the explosives and explosives contained in the slurry or solution are subjected to wet oxidation treatment.
It should be noted that, during the production of the paste-like substance and / or the formation of the slurry or the solution, heating at a temperature equal to or lower than the combustion temperature of the explosive or explosive causes the respective production. Speed can be increased.
[0007]
The invention described in claim 2 is characterized in that before the slurry or the solution is subjected to wet oxidation treatment, a hydrothermal reaction is generated in the slurry or the solution to hydrolyze the explosive and explosives.
According to this method for treating explosives and explosives, before the slurry or solution is subjected to wet oxidation treatment, a hydrothermal reaction is generated in the slurry or solution, and the explosives and explosives are hydrolyzed. In this case, the hydrothermal reaction indicates a hydrothermal reaction performed at a subcritical temperature or a temperature below the subcritical temperature.
[0008]
The invention according to claim 3 is a method for treating explosives and explosives by generating a hydrothermal reaction in a solution containing explosives and explosives to hydrolyze the explosives and explosives. Impregnating a solvent to form a paste-like substance, mixing a liquid with the paste-like substance to form a slurry or a solution, generating a hydrothermal reaction in the slurry or the solution, and hydrolyzing the explosive and explosives. It is characterized by: According to the method for treating explosives and explosives, first, an explosive or explosive is impregnated with an organic solvent to produce a paste-like substance, and then a liquid is mixed with the paste-like substance to form a slurry or a solution. The explosives and explosives contained in the slurry or solution are subjected to a hydrothermal reaction. In this case, the hydrothermal reaction indicates a hydrothermal reaction performed at a subcritical temperature or a temperature below the subcritical temperature.
It should be noted that, during the production of the paste-like substance and / or the formation of the slurry or the solution, heating at a temperature equal to or lower than the combustion temperature of the explosive or explosive causes the respective production. Speed can be increased.
[0009]
The invention described in claim 4 is characterized in that the liquid is an alkaline aqueous solution, and the slurry or the solution is an alkaline solution.
According to the method for treating explosives and explosives, the liquid is an alkaline aqueous solution, and the slurry or solution is an alkaline solution.
[0010]
The invention described in claim 5 is characterized in that the oxidation-reduction potential of the alkaline solution is adjusted to a low potential.
According to this method for treating explosives and explosives, the oxidation-reduction potential of an alkaline solution is adjusted to a low potential.
[0011]
The invention described in claim 6 is characterized in that the explosives and explosives are roughly crushed before the paste-like substance is generated.
According to the method for treating explosives and explosives, the explosives and explosives are roughly crushed into a desired shape before the paste-like substance is generated.
[0012]
The invention described in claim 7 is characterized in that the explosives and explosives are smokeless explosives.
According to the method for treating explosives and explosives, smokeless explosives are employed as the explosives and explosives.
The smokeless explosive means a propellant and a propellant such as a single base, a double base, and a triple base. The present invention does not limit the types and number of components of the smokeless powder.
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the method for treating explosives and explosives of the present invention will be described in detail.
[0014]
(1st Embodiment)
The explosives and explosives targeted in the present invention include smokeless explosives, black explosives, or explosives mainly containing perchlorate and the like, and nitro compounds, nitroamine compounds, nitrate compounds, nitrates, chlorates, Examples include explosives containing perchlorate as a main component, or a mixture of the above compounds, and in particular, in the following embodiments, double-based propulsion composed of nitrobenzene and nitrocellulose as waste propellants. The explanation is made using drugs.
[0015]
First, a paste-like substance is generated by impregnating an organic solvent with a waste propellant such as an explosive or explosive. Usually, explosives and explosives are formed as solids including molding materials such as rubber and resin in addition to the raw materials such as the explosives and explosives. . The subdivision of the solid is performed by a crushing method such as low-temperature crushing or crushing by a mill or a water jet. The coarsely crushed material finely divided to a particle size of about 2 mm by crushing is impregnated with an organic solvent, and further kneaded to produce a paste-like substance. As the organic solvent, acetone and alcohols are preferably used. The time for impregnating the coarsely crushed product with the organic solvent depends on the type and amount of the waste propellant, and is tens of minutes to several hours. In this embodiment, the time is about 10 minutes. In addition, in order to reduce the time for impregnation with the organic solvent, it is also possible to heat the explosive or explosive at or below the ignition ignition temperature.
[0016]
Next, a liquid is mixed with the paste-like substance to form a slurry or a solution (hereinafter, described as a slurry). As a liquid to be mixed, an alkali solution is adopted, and in the present embodiment, a description will be made using a sodium hydroxide solution. As the alkali solution, a solution which is particularly easily dissolved in water is selected. In addition to sodium hydroxide, for example, a water-soluble alkali salt such as potassium hydroxide or sodium phosphate can be selected. The oxidation-reduction potential is previously adjusted to a low potential by appropriately adjusting the concentration of the alkali solution to 0.1% or more. Further, in order to accelerate the formation of the slurry, it is possible to heat the explosives and explosives at the ignition temperature or lower.
[0017]
As described above, by mixing the paste-like substance with the alkaline solution to form a slurry, explosives and explosives contained in the slurry can be made into non-explosives in a short time because the particles are fine, since the particles are fine. Become. Further, since the oxidation-reduction potential is adjusted to a low potential in advance, it is possible to more efficiently de-explode. As a result, as will be described later, when the slurry is subjected to the wet oxidation treatment, the wet oxidation treatment can be safely performed. In addition, since the paste-like substance is obtained by impregnating the waste propellant with an organic solvent, the amount of the organic solvent is sufficient to be impregnated, and when the waste propellant is completely dissolved by the organic solvent. In this case, the amount of the organic solvent used can be reduced, and the amount of the organic solvent used can be reduced. Further, before performing the wet catalytic oxidation treatment described below, the organic solvent can be recovered and reused.
[0018]
Next, a wet catalytic oxidation treatment (wet oxidation treatment) was performed on the slurry. As the conditions for wet catalytic oxidation, the above-mentioned slurry was heated at a temperature of 180 to 200 ° C. for 10 to 60 minutes. As the catalyst, titanium, granular or pellet-shaped titania, and alumina, on which a noble metal such as ruthenium or palladium is supported, further, platinum, zeolite, volcanic ash, etc. can be used. Was used.
[0019]
Here, before and after the wet catalytic oxidation treatment of the slurry, the COD (Chemical Oxygen Demand) value, which is an index of the organic matter content, was compared. The COD value of chromium before the wet catalytic oxidation treatment was about 6000 ppm, whereas the COD value after the treatment was about 100 ppm. The COD value of manganese before the wet catalytic oxidation treatment was about 2400 ppm, whereas the COD value after the treatment was about 30 ppm.
[0020]
Therefore, it can be seen that the performance of the waste propellant is reduced because the organic matter is reduced by performing the wet catalytic oxidation treatment. That is, the waste propellant is impregnated with an organic solvent to form a paste-like substance, the paste-like substance is mixed with an alkaline solution to form a slurry, and the waste propellant is made non-explosive, and the waste propellant is disposed of by wet oxidation. By combining the propellant with non-explosive, it becomes possible to decompose waste propellant efficiently and safely without performing hydrolytic treatment by hydrothermal reaction.
[0021]
In addition, in order to reduce the load of the above-mentioned wet catalyst oxidation treatment, hydrolysis treatment by a hydrothermal reaction may be further performed as a pretreatment of the wet catalyst oxidation treatment. In other words, depending on the type and amount of waste propellant used, slurrying of waste propellant and wet catalytic oxidation treatment alone can make it non-explosive, but the efficiency is poor and the decomposition treatment time is long. Therefore, hydrolysis treatment by a hydrothermal reaction can be appropriately performed as appropriate. In this case, before the hydrolysis treatment, the waste propellant is subjected to a first treatment step of performing a thermal decomposition treatment at a temperature lower than the thermal decomposition temperature of the waste propellant, and after the first treatment step, a hydrothermal treatment is further performed. A second treatment step of generating a reaction and hydrolyzing may be performed.
[0022]
(Second embodiment)
In the second embodiment of the present invention, in the first embodiment, after the slurry is formed, the slurry is subjected to a wet oxidation treatment. The method is characterized in that a contained alkaline solution is formed, and the solution is subjected to hydrolysis treatment (hydrothermal treatment) by a hydrothermal reaction.
[0023]
First, similarly to the first embodiment, after the waste propellant is crushed to form a coarsely crushed material, the coarsely crushed material is impregnated with an organic solvent to form a paste-like substance, and the paste-like substance is treated with an alkali. The solutions were mixed to form a solution of spent propellant. Thereafter, the waste propellant solution was subjected to hydrothermal treatment.
[0024]
FIG. 1 shows generation characteristics of SS (suspended matter) during hydrothermal treatment of waste propellant. The conditions of the hydrothermal treatment were as follows: 20 ml of an aqueous solution of sodium hydroxide having a normality of 1/10 was used as an absorbing solution, and 0.4 g of a double base propellant was impregnated with acetone to form a paste-like substance. To form a mixed solution. The gas phase was argon gas. Under these conditions, heating was performed for 30 minutes under four temperature conditions of 150 ° C., 200 ° C., 250 ° C., and 300 ° C.
[0025]
From FIG. 1, it can be seen that the higher the heating temperature is, the lower the generation rate of the organic SS component is. In particular, when the heating temperature is 250 ° C., the generation rate of SS is a value lower than 1%. That is, by setting the heating temperature to 250 ° C., a decomposition rate of 99% or more can be obtained in 30 minutes required for hydrothermal treatment. The slightly remaining SS is a carbide, and the property as a propellant has already disappeared, so that there is no danger of explosion.
[0026]
FIG. 2 shows the generation characteristics of the SS component during the hydrothermal treatment of the waste propellant. The conditions of the hydrothermal treatment are almost the same as the generation characteristics of the SS component shown in FIG. 1, but in FIG. 2, the temperature is set at 150 ° C., 200 ° C., 250 ° C., and 300 ° C. for 60 minutes. Heating was performed.
[0027]
From FIG. 2, it can be seen that, as in FIG. 1, as the heating temperature increases, the generation rate of the organic SS component decreases. In particular, when the heating temperature is 200 ° C., the generation rate of SS is lower than 1%. That is, by setting the heating temperature to 200 ° C., a decomposition rate of 99% or more can be obtained in 60 minutes required for hydrothermal treatment. The slightly remaining SS is a carbide, and the property as a propellant has already disappeared, so that there is no danger of explosion.
[0028]
1 and 2, the waste propellant is made non-explosive at the time of forming the solution of the waste propellant, and the treatment temperature is in the range of 150 to 300 ° C. and the treatment time is 30 to 60 minutes. By performing the hydrothermal treatment, the properties of the waste propellant can be eliminated.
[0029]
FIG. 3 shows the oxidation-reduction potential of the waste propellant during hydrothermal treatment. The conditions of the hydrothermal treatment are the same as those in FIG. 1. Under these conditions, heating was performed at 150 ° C., 200 ° C., 250 ° C., and 300 ° C. for 30 minutes. Point A in the figure indicates the oxidation-reduction potential before the hydrothermal treatment.
[0030]
From FIG. 3, it can be seen that at point A in the figure, the oxidation-reduction potential is low since it is before the hydrothermal treatment, indicating a reducibility. However, it can be seen that the oxidation-reduction potential increases when the hydrothermal treatment is performed. However, when the heating temperature is set high, the oxidation-reduction potential decreases, and the alkaline solution exhibits reducibility. In other words, it indicates that the waste propellant is more efficiently decomposed and lost in the alkaline solution.
[0031]
FIG. 4 shows the oxidation-reduction potential of the waste propellant during hydrothermal treatment. The conditions of the hydrothermal treatment are the same as those in FIG. 2. Under these conditions, heating was performed at 150 ° C., 200 ° C., 250 ° C. and 300 ° C. for 60 minutes for 60 minutes. Point B in the figure indicates the oxidation-reduction potential before the hydrothermal treatment.
[0032]
From FIG. 4, at point B in the figure, the oxidation-reduction potential is low because it is before the hydrothermal treatment, indicating a reducibility. However, it can be seen that the oxidation-reduction potential increases when the hydrothermal treatment is performed. Also, as in FIG. 3, when the heating temperature is set high, the oxidation-reduction potential decreases, and the alkali solution exhibits a reducing property. In other words, it indicates that the waste propellant is more efficiently decomposed and lost in the alkaline solution.
[0033]
3 and 4, the hydrothermal treatment of the waste propellant in the condition that the treatment temperature is in the range of 150 to 300 ° C. and the treatment time is 30 to 60 minutes is performed by setting the heating temperature higher. Decomposition can be performed efficiently. Considering the oxidation-reduction potential before hydrothermal treatment, the concentration of the alkali solution is appropriately adjusted to 0.1% or more, and the oxidation-reduction potential is adjusted to a low potential in advance, so that hydrolysis can be performed more efficiently. Becomes possible.
[0034]
In the above embodiment, only the hydrolysis treatment was performed on the waste propellant, but before the hydrolysis treatment, the waste propellant was subjected to the thermal decomposition treatment at a temperature lower than the thermal decomposition temperature of the waste propellant. After the first processing step, a second processing step of generating a subcritical hydrothermal reaction and performing a hydrolysis treatment may be performed.
[0035]
For example, FIG. 5 shows the transition of the processing temperature and pressure with respect to the time of the decomposition processing of the waste propellant. As the conditions for the decomposition treatment, 20 ml of an aqueous solution of sodium hydroxide having a normality of 1/10 was used as an absorbing solution, and 2.0 g of a double base propellant was impregnated with acetone to form a paste-like substance. To form a mixed solution. Under these conditions, first, thermal decomposition of waste propellant was performed. The heating rate was set to 5 minutes, and heating was performed for 30 minutes under five temperature conditions of 150, 160, 170, 180, and 190 ° C. After the thermal decomposition, the temperature was continuously raised to a subcritical temperature of 230 ° C. to carry out the hydrolysis.
[0036]
According to FIG. 5, the pressure value gradually rises as the temperature rises to the set temperature of the thermal decomposition process. When the treatment time exceeds 25 minutes, the pressure value is stabilized together with the temperature, and further, after the thermal decomposition treatment, as the temperature is raised to the set temperature of the hydrolysis treatment, the pressure value rises slowly and enters the stabilization. . As described above, the fluctuation tendency of the pressure value is constant when the temperature setting range during the thermal decomposition treatment is between 150 ° C and 190 ° C. Therefore, a sudden increase in pressure, which is usually a concern during the treatment of waste propellants, is suppressed, and when forming a solution of waste propellants, in addition to making the propellants non-explosive, safety It is possible to carry out the treatment of the waste propellant.
[0037]
It should be noted that the present invention is not limited to the above embodiment, and various changes can be made without departing from the spirit of the present invention.
[0038]
For example, in the above embodiment, as the waste propellant, a double base propellant composed of nitrobenzene and nitrocellulose was employed, but even if a composite propellant that can be impregnated with an organic solvent was employed, The same operation and effect as those of the above-described embodiment can be obtained.
[0039]
【The invention's effect】
As described above, according to the invention described in claim 1, after an explosive or explosive is impregnated with an organic solvent to produce a paste-like substance, a slurry or solution is mixed by mixing a liquid with the paste-like substance. After being formed, the explosives and explosives contained in the slurry or the solution are subjected to wet oxidation treatment, so that the explosives and explosives can be processed safely without causing pollution.
[0040]
According to the invention described in claim 2, before the slurry or the solution is subjected to the wet oxidation treatment, a hydrothermal reaction is generated in the slurry or the solution, and explosives and explosives are hydrolyzed, thereby causing pollution. In addition, it is possible to safely and reliably carry out the processing of explosives and explosives.
[0041]
According to the invention described in claim 3, after the explosives and explosives are impregnated with the organic solvent to generate a paste-like substance, a liquid is mixed with the paste-like substance to form a slurry or a solution. Alternatively, the explosives and explosives contained in the solution are subjected to hydrothermal treatment, so that the explosives and explosives can be safely processed without causing pollution.
[0042]
According to the invention described in claim 4, since the liquid is an alkaline aqueous solution and the slurry or the solution is an alkaline solution, the processing of explosives and explosives can be performed safely without causing pollution. It can be implemented.
[0043]
According to the fifth aspect of the present invention, since the oxidation-reduction potential of the alkaline solution is adjusted to a low potential, it is possible to efficiently perform non-explosive conversion.
[0044]
According to the invention described in claim 6, since explosives and explosives are roughly crushed before the paste-like substance is generated, it is possible to efficiently de-explosive.
[0045]
According to the invention described in claim 7, smokeless explosives are employed as the explosives and explosives, so that explosives to be disposed of, especially double-base propellants, do not cause pollution. , And can be safely processed.
[Brief description of the drawings]
FIG. 1 is a diagram showing a relationship between a heating temperature and a SS generation characteristic (heating time of 30 minutes) during hydrothermal treatment of waste propellant in a second embodiment of the method for treating explosives and explosives of the present invention. .
FIG. 2 is a diagram showing the relationship between the heating temperature and the SS generation characteristics (heating time of 60 minutes) during hydrothermal treatment of waste propellant in the second embodiment of the method for treating explosives and explosives of the present invention. .
FIG. 3 is a diagram showing a relationship between a heating temperature and an oxidation-reduction potential (heating time of 30 minutes) during hydrothermal treatment of waste propellant in the second embodiment of the method for treating explosives and explosives of the present invention.
FIG. 4 is a diagram showing a relationship between a heating temperature and an oxidation-reduction potential (heating time of 60 minutes) during hydrothermal treatment of waste propellant in the second embodiment of the method for treating explosives and explosives of the present invention.
FIG. 5 is a diagram showing the relationship between the processing time, the heating temperature, and the pressure during the thermal decomposition and hydrolysis of waste propellants in the second alternative embodiment of the method for treating explosives and explosives of the present invention. .

Claims (7)

Explosives, the explosives are subjected to a wet oxidation treatment, and the explosives, explosives for decomposing explosives, a method for treating explosives,
The explosive, explosives are impregnated with an organic solvent to produce a paste-like substance,
Mixing a liquid with the paste-like substance to form a slurry or a solution,
A method for treating explosives and explosives, wherein explosives and explosives contained in the slurry or solution are subjected to wet oxidation treatment. 2. The method for treating explosives and explosives according to claim 1, wherein a hydrothermal reaction is generated in the slurry or solution to hydrolyze the explosives and explosives before the slurry or solution is subjected to wet oxidation treatment. . Explosives, generating a hydrothermal reaction in a solution containing explosives, the explosives, explosives for hydrolyzing explosives, in the method of treating explosives,
The explosive, explosives are impregnated with an organic solvent to produce a paste-like substance,
Mixing a liquid with the paste-like substance to form a slurry or a solution,
A method for treating explosives and explosives, comprising generating a hydrothermal reaction in the slurry or solution to hydrolyze the explosives and explosives. The liquid is an alkaline aqueous solution,
4. The method for treating explosives and explosives according to claim 1, wherein the slurry or the solution is an alkaline solution. The method for treating explosives and explosives according to claim 4, wherein the redox potential of the alkaline solution is adjusted to a low potential. The method for treating explosives and explosives according to claim 1, wherein the explosives and explosives are roughly crushed before the paste-like substance is generated. The method for treating explosives and explosives according to any one of claims 1 to 6, wherein the explosives and explosives are smokeless explosives.

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