JP3513226B2 - How to handle explosives and explosives - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for safely treating unnecessary explosives and explosives.

[0002]

2. Description of the Related Art Conventionally, unnecessary explosives and explosives are burned in small amounts and treated by an explosive combustion method. However, in this method, workers are constantly exposed to danger and noise. There was also a problem of vibration. Therefore, as a method for solving these problems, a supercritical water oxidation method of oxidative decomposition in supercritical water and an alkali hydrolysis method of causing hydrolysis in an alkaline solution have been proposed. Although the supercritical water oxidation method can be processed in a short time, it requires an oxidizing agent, so that there is a problem in that the equipment is expensive due to corrosion of the equipment material and gold lining of the inner surface of the equipment. Further, the alkali hydrolysis method has a drawback that the decomposition rate is slow and the apparatus has a large capacity.

[0003]

As described above, it is known that explosives and explosives are gradually oxidized or hydrolyzed when heated in water and converted into safer substances. However, in order to decompose it at a practical rate, it was necessary to treat it in supercritical water at a critical temperature or higher, or to add an oxidizing agent such as oxygen, hydrogen peroxide, or ozone, or an alkali.
Moreover, since this supercritical water oxidation process is carried out at a temperature of 400 to 600 ° C., it becomes higher than the self-decomposition temperature of explosives and explosives, and explosives and explosives may locally decompose rapidly and cause an explosion accident. It was necessary to line gold with respect to the corrosion of equipment materials. In addition, the method using an oxidizing agent also requires a gold lining or the like from the viewpoint of corrosion, and the apparatus is expensive. In addition, the alkaline hydrolysis method can be carried out in water at a temperature lower than the self-decomposition temperature of explosives and explosives, but the decomposition reaction rate is slow, which is not a practical method.

Further, in the conventional explosive treatment, an unpopular small island or a spacious and spacious space is selected, which has a large explosive force (destructive force) and an explosive sound, and there is also a fear of misfire, which does not affect human resources at all. However, due to space and legal regulations, there is a limit to the amount of explosives that can be processed, and explosives work requires a high level of technical capability. Is currently not implemented. The present invention is capable of preventing the corrosion of the equipment materials by improving the problems of the prior art as described above, and preventing the explosives and explosives from being rapidly decomposed. It aims to provide a method for treating explosives and explosives that does not cause pollution problems.

[0005]

According to the present invention, a powdered explosive or explosive is hydrolyzed by heating it to a temperature below the critical temperature of the solution in an alkaline solution containing an alkali silicate salt or an aluminate aluminate salt as a reaction accelerator. A method of treating explosives and explosives characterized by decomposing, heating explosives and hydrolyzing the explosives in an alkaline solution whose pH is appropriately adjusted at a critical temperature or lower to hydrolyze, and then burning. It is a method of treating explosives and explosives.

The explosives and explosives to which the present invention is applicable include smokeless explosives, explosives such as black explosives, nitro compounds such as TNT (trinitrotoluene), nitramine compounds such as RDX (trimethylenetrinitroamine), and nitro compounds. Explosives containing nitrate ester compounds such as glycerin and the like, or a mixture thereof. The first and second methods of the present invention use these explosives and explosives as waste explosives such as those that are no longer needed or that are generated as defective products in the manufacturing process,
Explosives are hydrolyzed in an alkaline solution, characterized by adding an alkali silicate salt or an aluminate aluminate salt as a reaction accelerator, and heating the solution to a temperature below the critical temperature for hydrolysis. I am trying. Third of the present invention
The method is characterized by heating explosives and explosives in an alkaline solution whose pH is properly adjusted below the critical temperature to hydrolyze intermediate products that have no danger of explosion, and then burning the intermediate products. I am trying.

The alkaline solution used in the first and second methods of the present invention is preferably an aqueous solution of sodium salt or potassium salt such as sodium hydroxide or potassium hydroxide. As the alkali silicate salt or alkali aluminate salt added as a reaction accelerator, sodium salts such as sodium silicate, potassium silicate, sodium aluminate and potassium aluminate, and potassium salts are preferable. The amount of alkali silicate or alkali aluminate added is preferably 10 to 1000 ppm, more preferably 50 to 500 ppm, in the alkaline solution. If the addition amount is 10 ppm or more, the reaction promoting effect is large, and
The effect of addition is effective up to 000 ppm. 1
In one example of the decomposition test in which the reaction was performed at 50 ° C. for 4 hours, 50 p
When pm is added, a decomposition rate more than twice that obtained when no pm is added is obtained, and alkali silicate or alkali aluminate 1
In the case of the addition of 00 ppm, 200 ppm, and 500 ppm, the former case and in the case of addition of 50 ppm, respectively, 1.11
2 times, 1.23 times and 1.28 times, respectively 5 in the latter case
1.08 times, 1.21 times, and 1.
The decomposition rate is 27 times, and the improvement rate of the decomposition rate with respect to the increase of the addition amount is not so large, so that the addition amount of these alkali salts is about 1000 ppm at maximum.

The pH of the alkaline solution is preferably in the range of 10-12. When the pH is 10 or more, the hydrolysis reaction is fast, and when the pH is 12 or less, the problem of corrosion of the apparatus is unlikely to occur. The temperature of the hydrolysis reaction is preferably 150 ° C. or higher, and when the temperature is 150 ° C. or higher, the reaction rate becomes faster, which is more practical. Further, if the temperature is below the critical temperature of the solution, there is little risk of corrosion of the equipment and rapid decomposition of explosives and explosives, so the temperature is below the critical temperature of the alkaline solution (about 374 ° C in the case of alkaline aqueous solution), preferably Is 35
The temperature is preferably 0 ° C or lower.

Preferred embodiments of the first and second methods of the present invention include the following (1) to (3). (1) The concentration of the silicic acid alkali salt or aluminate alkali salt is 10 to 1000 ppm in the alkaline solution.
And is hydrolyzed in an alkaline solution whose pH is adjusted to 10 to 12. (2) The hydrolysis temperature is 150 to 350 ° C. (3) The concentration of the silicic acid alkali salt or aluminate alkali salt is 10 to 1000 ppm in the alkaline solution.
Then, it is heated to a temperature of 150 to 350 ° C. in an alkaline solution whose pH is adjusted to 10 to 12 to cause hydrolysis.

The alkaline solution used in the third method of the present invention may be the same as the alkaline solution used in the first method. The third method of the present invention is to disperse or dissolve explosives and explosives in an alkaline solution, and then to heat and hydrolyze and burn them at a critical temperature or lower to prevent corrosion of equipment materials, and to prevent explosives and explosives. It aims to prevent explosive decomposition of chemicals and to process explosives safely.

[0011]

[Action]

(Operations of the first and second methods): Explosives and explosives are slowly decomposed by simply heating them in water, and it is necessary to hydrolyze them by adding an alkali or oxidatively decompose them by adding an oxidizing agent. . In supercritical water at 600 ° C and 370 atm, 98 to 99.99% of explosives and explosives decompose in the presence of excess hydrogen peroxide in a reaction time of several seconds to several minutes, but when the temperature and pressure decrease The reaction rate decreases, for example, 200 ° C, 1
At 5 atm, a reaction time of several tens to several hundreds of hours is required to decompose 99% or more. On the other hand, almost the same reaction time is required for hydrolysis in an alkaline solution. On the other hand, in an alkaline solution containing silicate alkali salt or aluminate salt, silicate alkali salt or aluminate salt acts as a catalyst, so no alkali silicate salt or aluminate salt is added at the same temperature and pressure. The reaction time is only a fraction of the reaction time in alkaline solutions, and even at a reaction temperature below the autolysis temperature of explosives and explosives, explosives and explosives are decomposed within a reaction time of several minutes to several tens of hours. It becomes possible to do. Further, since the reaction temperature and pressure are below the critical temperature and critical pressure of water and no oxidizing agent is required, there is an advantage that a material such as stainless steel used for general pressure vessels can be used. .

(Operation of the third method): The complete decomposition of explosives and explosives in water or an alkaline solution is as described in the operations of the first and second methods, but the hydrolysis in the alkaline solution is performed. When the reaction time is short in the decomposition, intermediate products with low explosion risk such as toluene and aldehydes are produced. Although it cannot be disposed of as such, in the second method of the present invention, these intermediate products are produced by short-time hydrolysis in an alkaline solution, and by burning these intermediate products, explosive powder, It enables the safe handling of explosives. That is, the first and second methods of the present invention completely hydrolyze and process explosives and explosives by hydrolysis, whereas the third method of the present invention is a short-time hydrolysis treatment and combustion method. Is used in combination to process explosives and explosives.

[0013]

EXAMPLES The method of the present invention will be described in more detail with reference to the following examples.

(Example 1) TNT (trinitrotoluene) was selected as a representative of explosives and explosives, and the method of the present invention, an oxidative decomposition method using an oxidizing agent for comparison, an alkali silicate salt or an alkaline aluminate was selected. A decomposition test was carried out by three types of treatment methods, that is, an alkaline hydrolysis method without using a salt. For each treatment method, the test solution having the composition shown in Table 1 was placed in a small pressure vessel, and the temperature was 200 ° C, 250 ° C, 300 ° C.
And 400 ° C. in four stages of temperature conditions. All pressures were performed under saturated pressure. In addition,
In the method of the present invention and the alkaline hydrolysis method, the pH decreases as the reaction progresses, so sodium hydroxide was replenished successively to maintain the pH at about 11. The progress of the reaction is
The reaction solution was sampled at predetermined time intervals under each reaction condition, and the residual amount of TNT and the amount of nitrate ion produced were analyzed by high performance liquid chromatography and ion chromatography.

[0015]

[Table 1]

Table 2 shows the reaction time until a decomposition rate of 99% or more was obtained under each test condition. From the results of Table 2, according to the method of the present invention, the progress of the reaction is fast even at a temperature below the critical temperature, and it is 99% or more in the time required for about 1/4 as compared with the alkali hydrolysis method in which sodium silicate is not added. It can be seen that the decomposition rate can be obtained. In addition, the method of the present invention has no risk of explosion, and there is little risk of corrosion of the device because no oxidizing agent is required. Similar results were obtained with a nitro compound such as trinitroanisole, a nitroamine compound such as trimethylenetrinitroamine, a nitrate ester compound such as nitroglycerin, or a mixture thereof in addition to TNT.

[0017]

[Table 2]

(Example 2) Table 3 shows an example in which the third method of the present invention was applied to the decomposition of TNT. As a comparative example, the treatment temperature and the reaction time until a decomposition rate of 99% or more are obtained when TNT is treated by an oxidative decomposition method using hydrogen peroxide as an oxidizing agent and a hydrolysis method using only an alkali (sodium hydroxide) solution. It is also shown in Table 3. Both the third method of the present invention and the hydrolysis method using only the alkaline solution of the comparative example have a pH of 10
The treatment efficiency is poor below, and alkali corrosion may occur at pH 12 or above. Therefore, it is preferable to adjust the pH within the range of 10-12.
I went in 1. In addition, in the comparative example using hydrogen peroxide as an oxidizing agent in the comparative example, the addition amount of hydrogen peroxide was TNT of CO ₂ , H.
_The amount was 10 times the amount required to oxidize to ₂ O and NO ₃ .

[0019]

[Table 3]

In the test, a small pressure vessel is used to heat the test solution in the pressure vessel, the test solution is taken out every time, and the test solution is analyzed by high performance liquid chromatography and ion chromatography.
The amount of residual NT, the amount of nitrate ions produced, and the amount of intermediate products were analyzed.

As can be seen from these results, according to the third method of the present invention, it is possible to decompose the TNT explosive into an intermediate product having a low explosion risk within 5 hours at a temperature of 200 ° C. or higher even at a temperature below the critical temperature. Since the produced intermediate product is burned and decomposed into CO ₂ , NOx, and H ₂ O, the treatment time can be shortened as compared with other methods.

Although only TNT has been described in this example, other nitro compounds, nitramine compounds, nitric acid ester compounds alone or in a mixture thereof may be used.
It was confirmed that almost the same effect was obtained.

[0023]

According to the method of the present invention, unnecessary explosives, explosives, or explosives or explosives generated as defective products in the manufacturing process can be treated by the oxidative decomposition method or alkali hydrolysis at a temperature higher than the supercritical temperature of the prior art. There is no problem of rapid reaction or corrosion due to high reaction temperature in the decomposition method, and in a relatively short time,
It can be safely processed.

─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-54-143771 (JP, A) JP-A-50-97574 (JP, A) JP-A-9-500058 (JP, A) JP-A-5- 504379 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) B09B 3/00 A62D 3/00 C06B 21/00-49/00

Claims (3)

(57) [Claims] 1. A powder of explosives and explosives as a reaction accelerator, silicic acid.
Sodium hydroxide and / or alkali salt added
A method for treating explosives and explosives, which comprises heating in an aqueous solution of potassium hydroxide to a temperature not higher than the critical temperature of the solution for hydrolysis. 2. Explosives and explosives, characterized in that they are hydrolyzed by heating explosives or explosives in an alkaline solution containing an alkali aluminate salt as a reaction accelerator at a temperature below the critical temperature of the solution. Processing method. 3. The processing method according to claim 1 or 2.
And containing the reaction accelerator and having a pH of 10 to 12
In an alkaline aqueous solution adjusted to
The explosive and explosive using the method of heating below the critical temperature of
A method of treating explosives and explosives , which comprises hydrolyzing the compounds and then further burning them.