JP3354743B2 - How to handle unwanted ammunition - 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 disposing of unnecessary ammunition, such as artillery ammunition, bombs and torpedoes.

[0002]

2. Description of the Related Art Unnecessary munitions, such as artillery shells, bombs, torpedoes, etc., which have become unnecessary conventionally, are burned or exploded little by little after being subjected to some pretreatment such as cutting, crushing, etc.
Although the explosion method is used, explosives contained in this method are treated without being decomposed, so workers are always at risk of explosion, and there are also problems with noise and vibration. Was. Therefore, as a safer treatment method, a supercritical water oxidation method of oxidative decomposition in supercritical water, a hydrolysis method in an alkaline solution, and the like have been proposed. However, the supercritical water oxidation method can be processed in a short time, but requires an oxidizing agent. Therefore, there is a problem that the corrosion of the equipment material is a problem and the equipment is expensive such as lining the inner surface of the equipment with gold. Further, the alkali hydrolysis method has a disadvantage that the decomposition rate is slow and the capacity of the apparatus is large.

[0003] That is, it is known that explosives and explosives are gradually oxidized or hydrolyzed when heated in water to change into safer substances. However, in order to decompose at a practical rate, it was necessary to treat in supercritical water at a critical temperature or higher, or to add an oxidizing agent such as oxygen, hydrogen peroxide, ozone or an alkali. Moreover, in this supercritical water oxidation method, since it is processed at a temperature of 400 to 600 ° C., explosives,
Explosives and explosives could reach the self-decomposition temperature or higher, causing explosives and explosives to decompose rapidly and locally, causing an explosion. In addition, it was necessary to line up gold from the viewpoint of corrosion of equipment materials. Also, in the method using an oxidizing agent, a gold lining or the like is required from the viewpoint of corrosion, and the apparatus is expensive. Further, in the alkaline hydrolysis method, it is possible to treat in water at a temperature lower than the self-decomposition temperature of explosives and explosives, but the decomposition reaction rate is slow, and this is not a practical method.

[0004]

SUMMARY OF THE INVENTION The present inventors have proposed an explosive that has become unnecessary 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 has been confirmed that by heating to below the critical temperature of water, it is possible to decompose formic acid, acetic acid and other low-molecular-weight organic substances with little risk of explosion, and filed earlier (Japanese Patent Application No. 6-213702).
However, even with this method, explosives contained in shells, bombs, torpedoes, etc. are protected by shells,
It is impossible to process it as it is. SUMMARY OF THE INVENTION An object of the present invention is to provide a method for treating unnecessary ammunition, which can solve the above-mentioned disadvantages of the prior art and is safe and free from pollution problems such as noise and vibration.

[0005]

A first aspect of the present invention is a method for treating unnecessary ammunition, comprising the following steps (a) to (e). (A) Unnecessary ammunition from which the fuse was removed in advance in liquid nitrogen
A step of crushing after cooling to −150 ° C. or lower . (B) heating the crushed material in an alkali solution to which an alkali silicate or an alkali aluminate is added to a temperature lower than the critical temperature of the solution to reduce explosives in the crushed material with less risk of explosion; A step of hydrolyzing to low molecular organic matter. (C) a step of separating the reaction solution in the hydrolysis step into a crushed residue and a decomposition solution. (D) a step of subjecting the separated crushed and crushed residue to a burning treatment to remove the remaining explosive; And (e) detoxifying the decomposed liquid containing the low-molecular-weight organic substance with low danger of explosion separated in the hydrolysis step.

A second aspect of the present invention is a method for treating unnecessary ammunition, comprising the following steps (f) to (j). (F) Unnecessary ammunition with the fuse previously removed in liquid nitrogen
A step of crushing after cooling to −150 ° C. or lower . (G) a step of contacting the crushed material with an alkali solution to which an alkali silicate or an alkali aluminate is added at 50 to 100 ° C., and washing and separating explosives contained in the crushed material; (H) a step of subjecting the compressed and crushed residue obtained in the washing and separating step to a combustion treatment to remove the residual explosive; (I) a step of heating the solution containing explosives obtained in the washing and separation step to a temperature lower than the critical temperature of the solution and hydrolyzing the explosives in the solution to low-molecular-weight organic substances having a low risk of explosion. (J) detoxifying the decomposed liquid containing the low-molecular-weight organic substance having a low risk of explosion separated in the hydrolysis step.

According to the present invention, the shells protecting explosives are brittlely broken at a low temperature at which there is no danger of explosion, and the explosives and an alkali silicate such as sodium silicate or an alkali aluminate such as sodium aluminate are used. Is characterized in that the contact with an alkali solution such as sodium hydroxide to which is added.

The ammunition to be treated in the present invention includes explosives such as smokeless powder and black powder, nitro compounds such as TNT (trinitrotoluene), nitroamine compounds such as RDX (trimethylenetrinitroamine), and nitroglycerin. And other unnecessary ammunition such as gun shells, bombs, torpedoes, etc. in which explosives and explosives such as nitric acid ester compounds and mixtures thereof are held in metal shells.

As the alkaline solution used in the method of the present invention, an aqueous solution of a sodium salt or a potassium salt such as sodium hydroxide or potassium hydroxide is preferable. As the alkali silicate or alkali aluminate to be added as a reaction accelerator, sodium salts and potassium salts such as sodium silicate, potassium silicate, sodium aluminate and potassium aluminate are preferable. The addition amount of alkali silicate or alkali aluminate is 1% in the alkaline solution.
0 to 1000 ppm is preferable, and 50 is more preferable.
５００500 ppm. 10 ppm added
Above, the reaction promoting effect is large, and 1000 ppm
Until the effect of the addition is effective. In one example of a decomposition test in which the reaction was performed at 150 ° C. for 4 hours, a decomposition rate of twice or more of the decomposition rate in the case of no addition was obtained with the addition of 50 ppm, and the alkali silicate or the alkali aluminate 100 ppm,
In the former case, the addition of 200 ppm and 500 ppm 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 and 50 times in the case of 50 ppm addition. Since the decomposition rate is 1.27 times, and the improvement of the decomposition rate is not so large with the increase of the addition amount, the addition amount of these alkali salts is up to 100.
About 0 ppm is sufficient.

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 less likely 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 is increased and the reaction is more practical. Further, since the temperature of corrosion or explosive device not more than the critical temperature of the solution, a small risk of rapid decomposition of explosives, temperature critical <br/> temperature degrees or of an alkali solution, preferably not more than 350 ° C. It is good to do.

[0011]

As described above, explosives can be decomposed into organic substances with a low risk of explosion by heating in an alkali solution to which alkali silicate or alkali aluminate has been added. However, gunshots, bombs, torpedoes Explosives contained in unnecessary ammunition such as are protected inside a metal shell, and unless the shell is crushed by some method, the explosives cannot be brought into contact with the alkaline solution, Can not do it. When these metal shells are immersed in liquid nitrogen and squeezed at a high pressure in a state of being cooled to -190 ° C or lower, brittle fracture easily occurs and can be crushed. In this case, since the temperature at the time of squeezing is low and the liquid nitrogen is inert, there is no danger of explosive explosives even when squeezed at high pressure. Therefore, the unnecessary ammunition from which the fuse has been removed in advance can be immersed in liquid nitrogen , sufficiently cooled, and then crushed at a high pressure to break the shell. The cooling temperature is -1.
The cooling medium may be 50 ° C. or lower, and the cooling medium is not limited to liquid nitrogen, and any inactive substance such as liquid argon and liquid helium can be used. However, liquid nitrogen is most suitable from the viewpoint of cost and availability.

In the first aspect of the present invention, unnecessary ammunition whose shell is crushed in this manner is converted into an alkali silicate such as sodium silicate or sodium hydroxide to which an alkali aluminate such as sodium aluminate is added. The explosives in the pressed crushed product are heated to a temperature below the critical temperature of the solution with an alkaline solution to hydrolyze explosives in the crushed product into formic acid, acetic acid, and other low-molecular-weight organic substances with low risk of explosion. After completion of the decomposition of the explosives, the explosive is cooled to room temperature and separated into an alkali solution containing a low molecular weight organic substance as a decomposition product and a metal shell pressed and crushed residue.

The separated metal shell crushed and crushed residue can be subjected to post-treatment such as washing with water and incineration, and then discarded such as landfilling, or can be reused as valuable resources. On the other hand, alkaline solutions containing low-molecular-weight organic substances are subjected to detoxification treatment such as activated sludge treatment to meet wastewater standards,
It can be discharged to the outside of the system or subjected to treatment such as spray combustion.

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

The crushed residue of the shell after washing and separation of explosives is incinerated with a rotary kiln or the like in order to completely remove the explosives, and then landfilled in the same manner as in the first invention. Can be disposed of or reused as valuable resources. The explosives remaining in the crushed residue obtained by washing and separating the explosives are very small, and there is no danger of explosion due to incineration.

On the other hand, the separated washing waste liquid containing explosives is 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. By heating to a temperature lower than the temperature, explosives are hydrolyzed to formic acid, acetic acid and other low molecular organic substances having little risk of explosion using alkali silicate or alkali aluminate as a reaction accelerator. The alkali solution containing the low-molecular-weight organic substance may be subjected to detoxification treatment such as activated sludge treatment so as to conform to the wastewater standard, and then discharged outside the system, or subjected to treatment such as spray combustion.

In the process of the second invention, unnecessary ammunition containing explosives after crushing is heated only up to about 100 ° C. at the maximum. There is an advantage that energy consumption is smaller than in the case of the first invention in which the solution is heated to below the critical temperature in the solution.

[0018]

EXAMPLES The method of the present invention will be described more specifically with reference to the following examples. (Example 1) A processing test of a torpedo warhead was performed by the method of the present invention. Normally, torpedo warheads have an explosive charge and fuze inside an aluminum shell, but in processing tests we used a warhead without a fuze from the beginning. The weight of the warhead used was about 40kg, of which the weight of the explosive was about 30kg
Met. The explosive is HBX-3, the main components of which are TNT (trinitrotoluene), RDX (trimethylenetrinitroamine) and aluminum powder, and also contains wax and the like.

First, the warhead was immersed in a container containing 150 liters of liquid nitrogen for 20 minutes, cooled sufficiently, and then pressed and crushed by a tester for measuring the compressive strength of a metal test piece. The crushed pieces are collected, and 1/10 of the crushed pieces are put into a pressure vessel containing 100 liters of a sodium hydroxide solution having a pH of 11 to which sodium silicate is added to a concentration of 200 mg / liter, and stirred for 1 hour at room temperature. −
The aluminum powder contained in 3 was dissolved, and the generated hydrogen gas was released to the atmosphere. Next, sodium hydroxide was added so that the pH of the solution became 11, and the temperature was raised to 300 ° C. while stirring and stirring the vessel, and hydrolysis treatment was performed for 1 hour. During this time, check the pH of the solution periodically and check the pH
Was added so that was maintained in the range of 10-11.

One hour after the temperature reached 300 ° C., the solution was gradually cooled, and after the temperature of the solution reached room temperature, the contents were separated into a solution and a shell crushed 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 matter such as acetic acid is detected, and its concentration is about 120
It was 0 mg / liter. The biochemical oxygen demand (BOD) of the solution after decomposition was measured to be about 800 mg / liter, which is almost equivalent to the amount of oxygen that decomposes organic substances in the solution. It was also confirmed that this solution could be rendered harmless by activated sludge treatment.

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

After the washing of the crushed pieces was completed, the crushed pieces were separated into the crushed residue and the washing waste liquid. Residual HB for this crushed residue
When the amount of X-3 was measured, the residual amount was about 5 g, and 9
It was found that a cleaning efficiency of 9.8% or more was obtained. With such a residual amount, it can be incinerated using a rotary kiln or the like without danger of explosion.

On the other hand, the washing waste liquid was added with sodium hydroxide so as to have a pH of 11, then heated to 300 ° C. while stirring in a pressure vessel, and subjected to a hydrolysis treatment for 1 hour.
During this time, check the pH of the solution periodically to
Sodium hydroxide was added to keep it in the range of ~ 11. As described above, when the crushed residue and the washing waste liquid were separated and only the washed waste liquid was heated to 300 ° C., the heat amount of about 50 kcal could be saved as compared with the case where the crushed residue was heated together.

One hour after the temperature reached 300 ° C., the solution was gradually cooled. After the temperature of the solution 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, and low-molecular-weight organic substances such as formic acid and acetic acid were detected in the solution.
000 mg / liter. The biochemical oxygen demand (BOD) of the solution after decomposition was measured to be about 700 mg / liter, which is almost equivalent to the amount of oxygen that decomposes organic substances in the solution. It was also confirmed that this solution could be rendered harmless by activated sludge treatment.

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

[0026]

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

Claims (2)

(57) [Claims] 1. A method for treating unnecessary ammunition, comprising the following steps (a) to (e). (A) Unnecessary ammunition from which the fuse was removed in advance in liquid nitrogen
A step of crushing after cooling to −150 ° C. or lower . (B) heating the crushed material in an alkali solution to which an alkali silicate or an alkali aluminate is added to a temperature lower than the critical temperature of the solution to reduce explosives in the crushed material with less risk of explosion; A step of hydrolyzing to low molecular organic matter. (C) a step of separating the reaction solution in the hydrolysis step into a crushed residue and a decomposition solution. (D) a step of subjecting the separated crushed and crushed residue to a burning treatment to remove the remaining explosive; And (e) detoxifying the decomposed liquid containing the low-molecular-weight organic substance with low danger of explosion separated in the hydrolysis step. 2. A method for treating unnecessary ammunition, comprising the following steps (f) to (j). (F) Unnecessary ammunition with the fuse previously removed in liquid nitrogen
A step of crushing after cooling to −150 ° C. or lower . (G) a step of contacting the crushed material with an alkali solution to which an alkali silicate or an alkali aluminate is added at 50 to 100 ° C., and washing and separating explosives contained in the crushed material; (H) a step of subjecting the compressed and crushed residue obtained in the washing and separating step to a combustion treatment to remove the residual explosive; (I) a step of heating the solution containing explosives obtained in the washing and separation step to a temperature lower than the critical temperature of the solution and hydrolyzing the explosives in the solution to low-molecular-weight organic substances having a low risk of explosion. (J) detoxifying the decomposed liquid containing the low-molecular-weight organic substance having a low risk of explosion separated in the hydrolysis step.