JPH08297000A - Treating method for unnecessary explosive and the like - Google Patents

Abstract

PURPOSE: To obtain a method for safely treating unnecessary explosive and the like such as bullet and shell, bomb or torpedo which becomes unnecessary. CONSTITUTION: A bullet shell for protecting gunpowder or the like is cooled by liquid nitrogen, press crushed at a low temperature having no fear of explosion, brittle broken, the crushed material is retained as it is or press broken residue is removed, then it is heated in alkaline solution of sodium hydroxide added with alkali silicate such as sodium silicate or alkali amide such as sodium aluminate to hydrolyze the gunpowder or the like. Thus, unnecessary explosive or the like such as bullet and shell, bomb or torpedo which becomes unnecessary can be safely treated without exploding riskiness without public pollution due to noise or vibration.

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 ammunition such as unnecessary ammunition, bombs, torpedoes and the like.

[0002]

2. Description of the Related Art Conventionally, unnecessary ammunition such as unnecessary ammunition, bombs, torpedoes, etc. is burned or burned in small amounts as it is, or after some pretreatment such as cutting or crushing.
Although it is processed by the explosive method, in this method explosives contained are processed without being decomposed, so workers are always exposed to the danger of explosion, and there are also problems of noise and vibration. It was Therefore, as a safer treatment method, a supercritical water oxidation method of oxidizing and decomposing in supercritical water, a hydrolysis method in an alkaline solution, and the like have been proposed. However, 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 apparatus is expensive due to corrosion of the apparatus material and gold lining of the inner surface of the apparatus. Further, the alkali hydrolysis method has a drawback that the decomposition rate is slow and the apparatus has a large capacity.

That is, it is known that when explosives and explosives are heated in water, they are gradually oxidized or hydrolyzed to change 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, in this supercritical water oxidation method, since explosives are treated at a temperature of 400 to 600 ° C.,
There is a risk that explosives and explosives may decompose rapidly locally to cause an explosion accident when the temperature exceeds the self-decomposition temperature of explosives, and gold is lined to prevent 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.

[0004]

DISCLOSURE OF THE INVENTION The inventors of the present invention have used unnecessary explosives in an alkali solution such as sodium hydroxide to which an alkali silicate such as sodium silicate or an alkali aluminate such as sodium aluminate is added. It was confirmed that by heating below the critical temperature of water, even formic acid, acetic acid and other low molecular weight organic substances with less risk of explosion can be decomposed, and the application was filed earlier (Japanese Patent Application No. 6-213702).
However, even with this method, the explosives contained in the shells, bombs, torpedoes, etc. are protected by shells,
It is impossible to process it as it is. SUMMARY OF THE INVENTION The present invention is intended to provide a method for treating unnecessary ammunition which is safe and has no pollution problem such as noise and vibration by improving the above-mentioned problems of the prior art.

[0005]

A first aspect of the present invention is a method for treating unnecessary ammunition characterized by comprising the following steps (a) to (e). (A) A step of crushing after crushing unnecessary ammunition from which the fuze has been removed in liquid nitrogen sufficiently. (B) This crushed crushed product is heated to a temperature below the critical temperature of the solution in an alkaline solution to which an alkali silicate or alkali aluminate has been added, so that there is little risk of explosives in the crushed crushed product. The process of decomposing to organic matter. (C) A step of separating the reaction liquid of the decomposition step into a crushing residue and a decomposition liquid. (D) A step of burning the separated crushed residue to remove residual explosive. (E) A step of detoxifying the decomposed solution containing an organic substance having a low risk of explosion separated in the decomposition step.

A second aspect of the present invention is a method for treating unnecessary ammunition, which comprises the following steps (f) to (j). (F) A step of sufficiently crushing unnecessary ammunition from which the fuze has been removed in liquid nitrogen and then crushing by crushing. (G) A step of bringing the pressed crushed product into contact with an alkali solution containing an alkali silicate or an alkali aluminate at 50 to 100 ° C., and washing and separating explosives contained in the pressed crushed product. (H) A step of burning the compressed crushed residue obtained in the washing and separating step to remove residual explosive. (I) A step of heating the solution containing explosives obtained in the washing / separating step to a temperature equal to or lower than the critical temperature of the solution to decompose the explosives in the solution into organic substances having less risk of explosion. (J) A step of detoxifying the decomposition liquid containing an organic substance having a low risk of explosion separated in the decomposition step.

According to the present invention, the shell which protects the explosives is brittlely broken at a low temperature where there is no danger of explosion, and the explosives and the alkali silicate such as sodium silicate or the alkali aluminate such as sodium aluminate. It is characterized in that it facilitates contact with an alkaline solution such as sodium hydroxide added with.

The ammunition to be treated in the present invention includes smokeless explosives, explosives such as black explosives, nitro compounds such as TNT (trinitrotoluene), nitroamine compounds such as RDX (trimethylenetrinitroamine), and nitroglycerin. It is unnecessary ammunition such as ammunition, bombs, torpedoes, etc., in which a nitric ester compound, etc., and a mixture thereof, explosives, and explosives held in a metal shell.

The alkaline solution used in the method 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 addition amount of alkali silicate or alkali aluminate is 1 in the alkaline solution.
0 to 1000 ppm is preferable, more preferably 50
To be about 500 ppm. Addition amount is 10ppm
Above, the reaction acceleration effect is large, and 1000 ppm
Up to, the effect of addition is effective. In one example of a decomposition test in which the reaction was carried out at 150 ° C. for 4 hours, a decomposition rate of at least twice the decomposition rate in the case of no addition was obtained by adding 50 ppm, and 100 ppm of a silicic acid alkali salt or an aluminate alkali salt,
In the case of the addition of 200 ppm and 500 ppm, the former case is 1.11 times, 1.23 times and 1.28 times respectively in the case of 50 ppm addition, and the latter case is 1.08 times, 1.21 times in the case of 50 ppm addition, respectively. The decomposition rate is 1.27 times, and the degree of improvement in the decomposition rate with respect to the increase in the added amount is not large, so the maximum addition amount of these alkali salts is 100.
About 0 ppm is sufficient.

The pH of the alkaline solution is preferably in the range of 10-12. If the pH is 10 or more, the hydrolysis reaction is fast, and if 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 preferably 350 ° C. or lower.

[0011]

[Function] As described above, explosives can be decomposed into organic substances with a low risk of explosion by heating in an alkaline solution containing an alkali silicate or an alkali aluminate. The explosives contained in unnecessary ammunition such as is protected inside the metal shell, and unless the shell is crushed by some method, the explosives cannot be brought into contact with the alkaline solution, resulting in hydrolysis. Can not do it. When these metallic shells are immersed in liquid nitrogen and squeezed under high pressure in a state of being cooled to −190 ° C. or less, brittle fracture can be easily caused to crush. In this case, since the temperature at the time of compression is low and the liquid nitrogen is inactive, there is no danger of explosives exploding even when compressed at high pressure. Therefore, the shell can be destroyed by immersing the unnecessary ammunition from which the fuze has been removed in advance in the liquid ground, cooling it sufficiently, and then squeezing it at high pressure. The cooling temperature is -1
The cooling medium is not limited to liquid nitrogen, and any inert substance such as liquid argon or liquid helium can be used as long as it is 50 ° C. or lower. However, liquid nitrogen is most suitable because of its price and availability.

In the first aspect of the present invention, the unnecessary ammunition whose shell is crushed in this way is treated with sodium silicate or other alkali silicate or sodium aluminate or other alkali aluminate to add sodium hydroxide or the like. The mixture is heated to a temperature not higher than the critical temperature of the solution with an alkaline solution to hydrolyze the explosives contained in the crushed crushed product to formic acid, acetic acid and other low molecular weight organic substances with less risk of explosion. After the explosives are decomposed, the explosives are cooled to room temperature and separated into an alkaline solution containing a decomposition product, a low molecular weight organic compound, and a metal shell crush residue.

The separated metal shell crushing residue can be subjected to post-treatments such as water washing and incineration, and then can be disposed of as landfill or reused as a valuable resource. On the other hand, the alkaline solution containing low molecular weight organic matter is subjected to detoxification treatment such as activated sludge treatment so as to meet the drainage standard,
It can be discharged to the outside of the system or treated such as spray combustion.

In the second aspect of the present invention, unnecessary ammunition whose shell is crushed as described above is treated with an alkali silicate such as sodium silicate at 50 to 100 ° C. or an alkali aluminate such as sodium aluminate. It is contacted with an alkaline solution such as sodium hydroxide to which is added, and explosives contained in this crushed material are washed and separated. As a method of contacting the crushed ammunition with the alkaline solution, a method of immersing the crushed ammunition in the alkaline solution, spraying the crushed ammunition with the alkaline solution, or spraying it can be used. During washing separation, most of the explosives are dissolved, but some are separated in a form dispersed in an alkaline solution.

In order to completely remove the residual explosives from the crushed and crushed residue of the shell after washing and separating the explosives, after incineration with a rotary kiln or the like, landfilling is performed in the same manner as in the case of the first invention. Can be disposed of or reused as valuables. In addition, since the explosives remaining in the crushing residue obtained by washing and separating the explosives are in very small amounts, there is no risk of these exploding due to incineration.

On the other hand, the cleaning waste liquid containing the separated explosives is an alkaline solution such as sodium hydroxide to which an alkaline silicate such as sodium silicate or an alkaline aluminate such as sodium aluminate is added, and the criticality of the solution. By heating to a temperature lower than the temperature, the explosives are hydrolyzed to formic acid, acetic acid and other low molecular weight organic substances which are less likely to explode by using alkali silicate or alkali aluminate as a reaction accelerator. The alkaline solution containing the low molecular weight organic matter can be subjected to detoxification treatment such as activated sludge treatment so as to meet the drainage standard, and then discharged to the outside of the system, or subjected to treatment such as spray combustion.

In the process of the second invention, unnecessary ammunition containing crushed explosives can be heated up to about 100 ° C. at maximum, so that the crushed ammunition remains as it is. There is an advantage that the energy consumption is small as compared with the case of the first invention in which the temperature is heated below the critical temperature in a solution.

[0018]

EXAMPLES The method of the present invention will be described in more detail with reference to the following examples. Example 1 A torpedo warhead treatment test was conducted by the method of the present invention. Usually, a torpedo warhead contains an explosive and a fuze inside an aluminum shell, but in the treatment test, a warhead without a fuze was used from the beginning. The used warhead weighs about 40 kg, of which the explosive charge weighs about 30 kg.
Met. The explosive is HBX-3, the main components of which are TNT (trinitrotoluene), RDX (trimethylenetrinitroamine) and aluminum powder, and in addition, wax and the like are contained.

First, the warhead was immersed in a container containing 150 liters of liquid nitrogen for 20 minutes, sufficiently cooled, and then pressed and crushed by pressing with a tester for measuring the compressive strength of a metal test piece. The crushed pieces were collected, and 1/10 of the crushed pieces were put into a pressure vessel containing 100 liters of a sodium hydroxide solution having a pH of 11 to which sodium silicate was added so as to have a concentration of 200 mg / liter, and stirred at room temperature for 1 hour to prepare HBX. −
The aluminum powder contained in No. 3 was melted and the generated hydrogen gas was released into the atmosphere. Next, sodium hydroxide was added so that the pH of the solution became 11, then the container was sealed and the temperature was raised to 300 ° C. with stirring, and a hydrolysis treatment was carried out for 1 hour. During this period, periodically check the pH of the solution and
Sodium hydroxide was added so that was maintained in the range of 10-11.

One hour after reaching 300 ° C., the solution was gradually cooled to room temperature, and then the contents were separated into a solution and a shell crushing residue, taken out and analyzed. As a result, both TNT and RDX in the solution and the shell crushing residue were completely decomposed below the detection limit, and formic acid,
Low-molecular organic substances such as acetic acid are detected, and the concentration is about 120.
It was 0 mg / liter. In addition, the biochemical oxygen demand (BOD) of the solution after decomposition was measured to be about 800 mg / liter, which is almost the same as the amount of oxygen for decomposing organic matter in the solution. It was also confirmed that the solution in (1) could be rendered harmless by treatment with activated sludge.

(Example 2) The same warhead used in Example 1 was cooled in the same manner as in Example 1 and 1/10 of the crushed pieces crushed by compression was added with sodium silicate to a concentration of 200 mg / liter. PH to be adjusted to 80 ° C.
It is put in a container containing 100 liters of sodium hydroxide solution of 11, and stirred at room temperature for 3 hours to wash and separate HBX-3 adhering to the crushed pieces and dissolve aluminum powder contained in HBX-3. The generated hydrogen gas was released into the atmosphere.

After the washing of the crushed pieces was completed, the crushed pieces were separated into a crushed residue and a washing waste liquid. Residual HB for this crushing residue
When the amount of X-3 was measured, the residual amount was about 5 g.
It was found that a cleaning efficiency of 9.8% or more can be obtained. If the residual amount is around this level, it can be incinerated using a rotary kiln or the like without risk of explosion.

On the other hand, the washing waste liquid was added with sodium hydroxide so as to have a pH of 11, and then heated to 300 ° C. with stirring in a pressure vessel and hydrolyzed for 1 hour.
During this period, the pH of the solution is checked regularly to ensure that the pH is 10
Sodium hydroxide was added so that it was kept in the range of -11. In this way, when the crushing residue and the washing waste liquid were separated and only the cleaning waste liquid was heated to 300 ° C., it was possible to save about 50 kcal of heat as compared with the case where the crushing residue was also heated together.

One hour after reaching 300 ° C., the solution was gradually cooled, and after the solution temperature reached room temperature, the contents were taken out and analyzed. As a result, both TNT and RDX in the solution were completely decomposed below the detection limit, low-molecular organic substances such as formic acid and acetic acid were detected in the solution, and the concentration was about 1
It was 000 mg / liter. Also, the biochemical oxygen demand (BOD) of the solution after decomposition was measured to be about 700 mg / liter, which is almost the same as the amount of oxygen for decomposing organic matter in the solution. It was also confirmed that the solution in (1) could be rendered harmless by treatment with activated sludge.

From the results of these examples, it was confirmed that the method of the present invention can treat the warhead of a torpedo safely and without pollution.

[0026]

According to the method of the present invention, unnecessary ammunition such as unnecessary ammunition, bombs, torpedoes, etc. can be safely treated without danger of explosion and pollution due to noise and vibration. You can

Claims (2)

[Claims] 1. A method for treating unnecessary ammunition, comprising the following steps (a) to (e): (A) A step of crushing after crushing unnecessary ammunition from which the fuze has been removed in liquid nitrogen sufficiently. (B) This crushed crushed product is heated to a temperature below the critical temperature of the solution in an alkaline solution to which an alkali silicate or alkali aluminate has been added, so that there is little risk of explosives in the crushed crushed product. The process of decomposing to organic matter. (C) A step of separating the reaction liquid of the decomposition step into a crushing residue and a decomposition liquid. (D) A step of burning the separated crushed residue to remove residual explosive. (E) A step of detoxifying the decomposed solution containing an organic substance having a low risk of explosion separated in the decomposition step. 2. A method for treating unnecessary ammunition, comprising the following steps (f) to (j): (F) A step of sufficiently crushing unnecessary ammunition from which the fuze has been removed in liquid nitrogen and then crushing by crushing. (G) A step of bringing the pressed crushed product into contact with an alkali solution containing an alkali silicate or an alkali aluminate at 50 to 100 ° C., and washing and separating explosives contained in the pressed crushed product. (H) A step of burning the compressed crushed residue obtained in the washing and separating step to remove residual explosive. (I) A step of heating the solution containing explosives obtained in the washing / separating step to a temperature equal to or lower than the critical temperature of the solution to decompose the explosives in the solution into organic substances having less risk of explosion. (J) A step of detoxifying the decomposition liquid containing an organic substance having a low risk of explosion separated in the decomposition step.