JP2003212684A - Method of manufacturing powdery explosive composition and apparatus for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of more safely and inexpensively obtaining crystalline explosives atomized with low sensitivity by using a simple manufacturing facility and to provide a method of obtaining a powdery explosive composition having good dispersibility and bondability of the crystalline explosives and the components exclusive of the crystalline explosives. <P>SOLUTION: A liquid prepared by dissolving or suspending explosive composition raw materials containing ≥1 kind of the crystalline explosives or ≥1 kind of the crystalline explosives and polymeric compound into an organic solvent is sprayed in a mist form using inert gas, etc., and while this sprayed liquid passes an injection pipe, the solvent of 40 to 90 wt.% of the used solvent is distilled away from the explosive composition raw materials and thereafter the powdery explosive raw materials are brought into contact with a poor solvent in which the powdery explosive composition is insoluble, by which the powdery explosive composition controlled to a spherical form of a desired grain size is manufactured. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention mainly relates to a method and an apparatus for producing a powdered explosive composition containing at least one crystalline explosive or at least one crystalline explosive and a polymer compound. is there. Specifically, a method for producing explosives such as powdered propellant, and a method and apparatus for producing powdered explosive composition used as a raw material for molding these into a desired shape in the production of propellant and propellant. It is about.

[0002]

2. Description of the Related Art In recent years, explosives containing a crystalline explosive have been used due to their high thermal stability. However, when using explosives containing this crystalline explosive, it is difficult to control the particle size, even though the particle size of the crystalline explosive greatly affects the combustion performance of the explosive.・ In addition to problems such as high sensitivity to friction, dispersibility and bondability between the raw materials of the explosive composition in the manufactured explosive when the explosive containing the crystalline explosive is manufactured by the conventional method. However, as a result, there was a problem that the physical properties and combustion performance of the explosive deteriorated. Therefore, in order to solve these problems, a method of controlling the particle size of the crystalline explosive to a desired size and a method of rounding the shape of the crystalline explosive to reduce the sensitivity are investigated, and the crystalline explosive is Techniques for improving dispersibility and bonding between the raw materials of the explosive composition in the explosive contained therein have been desired and studied.

In the prior art, for example, in order to obtain a crystalline explosive having a desired particle size, the raw crystalline explosive was vigorously stirred and pulverized in a liquid such as water or an organic solvent ( U.S. Pat. No. 4065529). However, even though the method added liquid, there was a risk of explosion due to impact or the like. Alternatively,
A method of obtaining a crystalline explosive having a desired particle size by recrystallization by cooling a solution of a crystalline explosive in a soluble solvent or contacting with a poor solvent is disclosed (US Pat. No. 463).
8065, U.S. Pat. No. 4,794,180). Although the risk of explosion due to impact is low when using this method, in order to obtain reproducible small particles, the selection of solvent type and temperature control during recrystallization must be very strict. In addition, it was often difficult to obtain spherical crystals having low sensitivity.

Further, among the same recrystallization methods, there is disclosed that a crystalline explosive having a desired shape is obtained by recrystallizing the crystalline explosive by using a supercritical fluid as a solvent (US Pat. No. 5,389,263). But the method is
There was a possibility that the equipment would be large-scale in order to obtain the ultra-high pressure state. As described above, the atomization method by pulverization has a safety problem, the atomization method by recrystallization has a problem that it is difficult to obtain a low-sensitivity crystal, and there is a problem that the apparatus is simple and the crystallinity When manufacturing explosives containing explosives, the manufacturing methods that have been used up to now must be used, and therefore there is a problem that the dispersibility and bondability between the explosive composition raw materials in the obtained explosive are poor. It was

As a method for solving these problems, a solution having a crystalline explosive dissolved in a soluble solvent together with an additive having an affinity with the binder component of the raw material for the explosive composition is sprayed in a high temperature atmosphere to obtain a desired shape. A method of obtaining a crystalline explosive of particle size is disclosed (US Pat. No. 40923)
No. 83). The method is highly safe and the device is simple, and by using an additive having affinity with the binder, it is possible to obtain a good explosive having dispersibility and bonding between the raw materials of the explosive composition, Since the solvent is rapidly removed after spraying, the surface of the generated crystalline explosive may become porous, and it is difficult to completely distill off the solvent only by spraying. There is a risk that the sex explosives may aggregate and affect the combustion performance of explosives using the explosives.

On the other hand, as another method for solving the problems of dispersibility and binding property, a crystalline explosive which is not dissolved or is completely dissolved in an organic solvent is slurried in water together with other raw materials for the explosive composition, There is disclosed a method for obtaining a small particle explosive composition having a desired shape by adding a polymer flocculant and a protective colloid agent to the above and granulating (JP-A-61-161).
37239). By using that method, it is possible to obtain a highly explosive composition that has good dispersibility.However, if a crystalline explosive is used without being dissolved, it must be prepared in advance by using a crystalline explosive that has been atomized to some extent. Therefore, a separate process such as crushing and recrystallization of crystalline explosive is required.
Moreover, when the crystalline explosive was dissolved, when mixed with water, there was a high possibility that the crystalline explosive was exposed on the surface of the explosive composition.

An explosive composition containing a crystalline explosive is used as a method for solving all of the problems such as safety of operation, product particle size, shape stability, dispersibility of raw materials of explosive composition in explosive, and binding property. Disclosed is a method for producing an explosive composition containing a crystalline explosive having a desired particle size and shape by spraying a solution prepared by dissolving the raw materials in a solvent in which these are soluble, using an ejector (Japanese Patent Laid-Open No. Hei 10 (1999) -29242). 1-313382
issue). The method is certainly superior in terms of handling safety and product quality compared to the conventional methods, but since the explosive composition raw material solution comes into contact with steam immediately after being ejected from the ejector, The components other than the crystalline explosive are peeled off from the crystalline explosive, and there is a risk of exposing the highly sensitive crystalline explosive, and when the powdered explosive composition is used as a raw material to produce the explosive, the exposed crystalline explosive is Dissolving in a solvent may increase the particle size of the crystalline explosive and may deteriorate the dispersibility of the explosive composition in the explosive.
Further, there is a problem that it is difficult to control the pressure and temperature of steam in order to obtain a powder composition having a desired particle size and shape.

[0008]

SUMMARY OF THE INVENTION In order to solve all of the above problems, the present invention uses a simple manufacturing facility to obtain a safe and inexpensive method for obtaining a crystalline explosive that is atomized with low sensitivity, more safely and at a lower cost. And a method and an apparatus for obtaining a powdered explosive composition which has good dispersibility and bonding of the crystalline explosive and components other than the crystalline explosive.

[0009]

In order to solve the above problems, the inventors of the present invention have conducted extensive studies and as a result have found that a solution or suspension of a raw material for an explosive composition dissolved or suspended in an organic solvent is used. After spraying with a gas to atomize and spraying this spray liquid through at least one of heating and depressurizing to distill off 40 to 90 wt% of the organic solvent, contact with a poor solvent, The present invention has been accomplished by finding a method for producing a powdery explosive composition controlled to be spherical.

That is, in the method for producing a powdered explosive composition of the present invention, a solution or suspension of a raw material for an explosive composition dissolved or suspended in an organic solvent is sprayed with a gas, and the sprayed spray liquid is chambered. The method for producing a powdered explosive composition is characterized in that 40 to 90 wt% of an organic solvent is distilled off by performing at least one of heating and depressurization while passing the solution through, and then contacting with a poor solvent. Further, the manufacturing apparatus for powdered explosive composition of the present invention is a manufacturing apparatus for powdered explosive composition,
Means for spraying a solution or suspension of a raw material for an explosive composition dissolved or suspended in an organic solvent, means for distilling a part of the sprayed spray liquid through a chamber, and part of the organic solvent An apparatus for producing the powdered explosive composition, comprising a means for bringing the spray liquid, which has been distilled off, into contact with a poor solvent.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the raw material of the explosive composition may contain one or more crystalline explosives or one or more crystalline explosives and a polymer compound. The raw material of the explosive composition may be a composition containing a plasticizer, a stabilizer, a flame retardant, a thickener, a combustion catalyst and the like.
Examples of the crystalline explosive include hexogen or trimethylenetrinitramine (RDX), octogen or cyclotetramethylenetetranitramine (HMX),
Pentaerythritol tetranitramine (PETN) and hexanitrohexaazaisourtitanium (HNIW)
Nitramine compounds such as

As the polymer compound, any compound having a role of adhering the crystalline explosive and the raw material of the explosive composition other than the crystalline explosive may be used, for example, cellulose acetate, Cellulose-based polymers such as cellulose acetate butyrate and nitrocellulose, and thermoplastic polymers such as polyethylene, polystyrene and polyamide, as well as polyazidomethylmethyloxetane (AMMO), polybisazidomethyloxetane (BAMO) and poly-3- Thermoplastic azide polymers such as nitratomethyl-3-methyloxetane (NIMO) can be used. The plasticizer includes, for example, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, butanetriol trinitrate (BTTN), acetate triethyl citrate, tributyl citrate (TBC), nitroglycerin (N
G), diethylene glycol dinitrate (DEG
N), butyl nitratoethyl nitramine (BuNEN
A), bis (2,2-dinitropropyl) acetal (B
A mixture of DNPA) and bis (2,2-dinitropropyl) formal (BDNPF) can be used.

As the stabilizer, for example, ethyl centrallite, diphenylamine, 2-nitrodiphenylamine or the like can be used. As the anti-inflammatory agent, for example, potassium sulfate, potassium nitrate, or ice salt can be used. Further, the organic solvent in the present invention is a liquid which can be easily distilled off from the solution or suspension of the raw material for the explosive composition by performing at least one of heating and depressurization. Further, the organic solvent may contain water as long as it does not separate into two layers. In the present invention, depressurization is often relatively efficient. If the boiling point of the organic solvent is lower than 15 ° C, it is often not a liquid at room temperature, and the solvent may evaporate before the raw material of the explosive composition is dissolved, and if the boiling point is higher than 160 ° C,
It is not preferable because the organic solvent cannot often be easily distilled off from the solution or suspension of the raw material for the explosive composition by heating or depressurizing. As the organic solvent, for example, acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, acetonitrile, nitroethane or the like can be used, and preferably acetone, methyl ethyl ketone or ethyl acetate is used.

The present invention will be described below with reference to the drawings.
FIG. 1 is a schematic diagram of an apparatus for carrying out the present invention.
FIG. 2 shows a coaxial type nebulizer, and FIG. 3 shows a cross flow type nebulizer. In the present invention, the solution refers to a liquid in which the explosive composition raw material is completely dissolved in an organic solvent, and the suspension means at least one of the components other than the crystalline explosive and the crystalline explosive of the explosive composition raw material. 10-95 wt%
Is dissolved in an organic solvent, the remaining crystalline explosive is not dissolved, and a liquid in a solid-liquid coexisting state exists as a solid. In this suspension, if the dissolved amount of the crystalline explosive is less than 10 wt%, the sample spray port (4) may be clogged during spraying, which is not preferable. The sample is a liquid to be sprayed. Also, when more than 95 wt% is dissolved,
This is not preferable because the crystal structure of the explosive having a crystal isomer is likely to change. When a solution of the raw material of the explosive composition dissolved in an organic solvent is used as the liquid to be sprayed, it can often be carried out relatively easily.

In FIG. 1, the atomizer (1) means that the solution or suspension of the raw material for the explosive composition supplied to the sample supply pipe (2) is blown off by the gas supplied to the gas supply pipe (3). Therefore, any means commonly used as a sprayer can be used as a means for spraying a solution or suspension of a raw material for an explosive composition into a fine mist. The gas spray pressure is preferably 0.1 MPa to 1.
The solution is preferably sprayed in the range of 0 MPa, and most preferably the gas spray pressure is in the range of 0.2 MPa to 0.4 MPa. If the spray pressure is lower than 0.1 MPa, spraying may not be possible, or the droplets after spraying may become large, which is not preferable. Further, if the spraying pressure exceeds 1.0 MPa, the spraying speed increases and the spraying distance of the droplets becomes long, so that the solvent in the droplets may be distilled off too much during that time, which is not preferable.

The diameter of the gas spray port (5) is not limited as long as the gas spray pressure can be maintained in the range of 0.1 MPa to 1.0 MPa. The diameter of the sample spray port (4) is preferably in the range of 0.01 mm to 5 mm, and most preferably the diameter of the sample spray port (4) is in the range of 0.05 mm to 3.5 mm. It should be If the diameter of the sample spray port (4) is smaller than 0.01 mm, the sample spray port (4) may be clogged during spraying, which is not preferable. If the diameter of the sample spray port (4) is larger than 5 mm, the amount of the spray liquid is too large, and the explosive composition may aggregate after spraying, which is not preferable.

The angle between the sample supply pipe (2) and the gas supply pipe (3) in the atomizer (1) must be in the range of 0 to 90 degrees, and any number within this range is possible. good. Beyond this range, the gas supplied from the gas supply pipe (3) flows into the sample supply pipe (2) and the solution or suspension is no longer sprayed. As the sprayer (1), for example, a nebulizer can be used, and as the nebulizer, for example, a coaxial type nebulizer or a cross flow type nebulizer can be used. FIG. 2 shows a coaxial type nebulizer, and FIG. 3 shows a cross flow type nebulizer.

The solution or suspension of the raw material of the explosive composition supplied to the sample supply pipe (2) utilizes the negative pressure state in the sample supply pipe (2) generated by the gas spray from the gas spray port (5). May be supplied to the sample spray port (4), or alternatively, the sample supply pipe (2) may be provided with a pump for pressurization to pressurize the inside of the sample supply pipe (2) to give a solution of the raw material for the explosive composition. May be supplied to the sample spray port (4). Further, the sample supply pipe (2) can be heated to a temperature lower than the boiling point of the solvent used in order to prevent the explosive composition raw material from unnecessarily depositing in the sample supply pipe (2).

Any gas may be used as the gas to be supplied to the gas supply pipe (3), for example, compressed air, inert gas, or the like may be used. In particular, since an organic solvent is used, it is preferable to use an inert gas in consideration of safety and the like. For example, nitrogen gas, argon gas, carbon dioxide or the like can be used.

In the present invention, the chamber (6) is
It is an injection tube that receives the atomized liquid. That is, the chamber (6) is defined as the distance until the solution or suspension of the raw material of the explosive composition sprayed from the sample spray port (4) comes into contact with the poor solvent, and the spray droplets are in between. It is a container provided for the purpose of distilling the solvent therein from the solution or suspension of the raw material for the explosive composition, and 40 to 90 w
Any shape may be used as long as it has a length sufficient to remove t% by distillation, and for example, a cylindrical shape can be used. It is preferable that the solvent has a length sufficient to distill off 50 to 70 wt% of the solvent used, and preferably the length of the chamber (6) is
It may be in the range of 100 mm to 500 mm.

In the chamber (6), when the amount of the solvent distilled off is less than 40% of the amount of the solvent used, the raw materials of the explosive composition agglomerate with each other, and the particle size of the powdery explosive composition produced increases. There is a possibility that it is not preferable. Further, if the amount of the solvent distilled off exceeds 90% of the amount of the solvent used, the surface of the resulting explosive composition may become porous, which is not preferable. Further, the chamber (6) can be provided with a heating device (8) for heating the inside of the chamber (6) to distill off the solvent, and further to distill off the solvent efficiently. A pressure reducing port (9) for connecting a pressure reducing pump may be provided for reducing the pressure in the chamber (6). At this time, when the pressure inside the chamber (6) is reduced to a range of 10 to 10,000 Pa, the temperature inside the chamber (6) is heated to a temperature of 100 ° C. or less, and the solvent is heated to 40 to 90 Pa.
wt% can be distilled off. Preferably, the pressure inside the chamber (6) is reduced to 100 to 7,000 Pa. When the pressure inside the chamber (6) is reduced to less than 10 Pa, the solvent is distilled off too much, and the surface of the powdery explosive composition produced may become porous, which is not preferable. Further, when the chamber (6) is depressurized only to a pressure exceeding 10,000 Pa, it is necessary to heat the inside of the injection pipe to a temperature exceeding 100 ° C. depending on the type of solvent, so that the generated powdered explosive composition is heated. Risk increases.

Further, the powdery explosive composition is a poor solvent in which the powdery explosive composition is insoluble in order to completely remove the residual solvent contained therein and to efficiently recover the powdery explosive composition. Must be in contact with. As a method, the chamber (6) can be provided with a poor solvent supply port (10) for supplying a poor solvent. Poor solvent supply port (10)
Is required to be at a sufficient distance from the sample spray port (4) so that the explosive composition comes into contact with the poor solvent after 40 to 90 wt% of the solvent used has been distilled from the solution or suspension. The poor solvent used may be any solvent as long as the explosive composition raw material is an insoluble solvent, for example,
Water, steam, heptane, hexane or the like can be used.

When water or steam is not used as the poor solvent, a water-soluble compound such as nitrate can be used as the raw material for the explosive composition. Specific examples of the water-soluble compound include nitroglycerin (NG) and diethylene glycol dinitrate (DEGN).

A raw material for an explosive composition containing one or more crystalline explosives or one or more crystalline explosives and a polymer compound,
These raw materials are dissolved or suspended in a soluble organic solvent. At this time, in order to dissolve or suspend the raw material for the explosive composition in the organic solvent, the solution or suspension can be heated to room temperature or higher and to a temperature not exceeding the boiling point of the organic solvent. The solution or suspension thus obtained is passed through the sample supply pipe (2) of the atomizer (1) and atomized by the gas supplied from the gas supply pipe (3). At this time, the solution or suspension of the raw material for the explosive composition supplied through the sample supply pipe (2) is atomized from the sample spray port (4). While the sprayed solution or suspension passes through the chamber (6), 40 to 90 wt% of the solvent used is distilled off, and the solid component in the explosive composition is precipitated. The precipitated solid component is mixed with the poor solvent supplied from the poor solvent supply port (10),
The powdery explosive composition is collected through a deposition tank inlet (11) into a precipitation tank (7) containing a poor solvent in which it is insoluble. At this time, the poor solvent in the precipitation tank (7) may be stirred by the stirrer (13). The chamber (6) can be provided with a heating device (8) and a decompression port (9) for efficiently distilling off the organic solvent. When the boiling point of the poor solvent used is higher than the boiling point of the organic solvent, the residual organic solvent is removed from the slurry suspension collected in the precipitation tank (7). When the boiling point of the poor solvent is lower than the boiling point of the organic solvent, the remaining organic solvent may not be removed. After that, the precipitation tank outlet (12)
After being taken out of the container, suction filtration is performed to obtain a spherical powdery explosive composition having a desired particle size.

In the present invention, a liquid such as vapor is not directly collided with the solution or suspension of the raw material of the explosive composition sprayed from the sample spray port (4), so that the crystalline explosives other than the crystalline explosives can be used. The components do not peel off. In addition, since the liquid is brought into contact with the poor solvent at a certain distance after spraying, the organic solvent is distilled off in a spherical shape without being crushed, and the solvent is not completely distilled off in the injection pipe. Since the powdery explosive composition having a porous surface is not obtained, a powdery explosive composition having a spherical surface and no pores having a desired particle size can be obtained. Furthermore, in the present invention, by controlling the gas spray pressure and the nozzle diameter, an explosive composition having a desired particle size can be obtained. In addition, since the structure of the device is simple, it is possible to easily perform cleaning after use, and it is possible to eliminate the danger of residual explosive in the device.
In particular, when a suspension of the raw material of the explosive composition is used as the liquid to be supplied to the sample supply pipe (2), there is an undissolved crystalline explosive, so that the crystal isomer of the crystalline explosive after spraying changes. Therefore, if the crystalline explosive contained in the raw material of the explosive composition has the desired crystalline isomer, a spherical powdery explosive composition having the desired crystalline isomer can be obtained.

Hereinafter, the present invention will be described in more detail with reference to Examples and the like, but the present invention is not limited to these Examples and the like.

[0027]

Example 1 Wet RDX (water content 10%, average particle size 12
8.6 μm) (1.9 g) was added to 20 ml of methyl ethyl ketone, and the mixture was heated to 70 ° C. and stirred to completely dissolve RDX. While keeping this solution at 65 to 70 ° C., it was sprayed into a chamber (length 150 mm) to which steam was being supplied using a coaxial nebulizer (spray port diameter 0.1 mm). The RDX fine powder thus produced was added to water with vigorous stirring with steam. The aqueous suspension of RDX fine powder was stirred under reduced pressure at 65 ° C. for 15 minutes to remove the residual methyl ethyl ketone. The suspension was cooled to room temperature and then suction filtered. The obtained RDX fine powder was evaluated by the following tests. The test results are shown in Table 1. A photograph of the raw material RDX is shown in FIG.
A photograph of the fine powder is shown in FIG. From Table 1, the obtained RDX
It was found that the particle size of the fine powder was smaller than that of the raw material RDX. Further, it was found from FIGS. 4 and 5 that the finely divided RDX was spherical.

Here, the measurement test of the particle size distribution will be described.

[0029]

[Measurement of Particle Size Distribution] About 1 to 3 ml of a 1% aqueous solution of a surfactant (dispersion medium) is prepared, and about 0.03 g of the sample is added thereto, and the sample is ultrasonically dispersed for 1 to 5 hours.
The dispersed fine powder sample was subjected to particle size measurement according to the following measurement conditions. Device JEOL HELOS & CUVETTE Measurement principle Laser diffraction method (Franforfer diffraction theory) Light source He-Ne laser (632.8 nm / 5 mW) Detector 31-element ring-shaped multi-detector disperser Static wet dispersion unit

[0030]

Example 2 Wet RDX (water content 10%, average particle size 27
26.2 g of micron) 197 ml of methyl ethyl ketone
In addition, the mixture was stirred while heating to 60 to 70 ° C. to completely dissolve RDX. While maintaining this solution at 60 to 70 ° C., it was sprayed into a chamber (length 150 mm) to which steam was being supplied using a coaxial nebulizer (spray port diameter 1.1 mm). The RDX fine powder thus produced was added to stirring water. An aqueous suspension of RDX fine powder was stirred under reduced pressure at 65 ° C. for 15 minutes to remove residual methyl ethyl ketone. The suspension was cooled to room temperature and then suction filtered. The RDX fine powder thus obtained was evaluated by the same test as in Example 1. The results of each test are shown in Table 1.

[0031]

Example 3 To 197 g of methyl ethyl ketone, wet R
DX (water content 10%) 25.1 g, cellulose acetate butyrate 3.57 g, nitrocellulose 1.2 g, ethyl centralite 0.12 g, acetyltriethyl citrate 2.26 g were added, and the solution was heated to 60 to 70 ° C. Then, each component was completely dissolved. This solution at 60-70 ° C
While keeping at, keep the coaxial nebulizer (spray diameter 0.1m
m) was used to spray into a chamber (length 200 mm) and the resulting powdered explosive composition was added to the stirring water. An aqueous suspension of this powdered explosive composition was added under reduced pressure to 65
The mixture was stirred at 0 ° C for 20 minutes to remove the residual methyl ethyl ketone. After the suspension was cooled to room temperature, a white powdery explosive composition was obtained by suction filtration. The powdery explosive composition obtained was evaluated by the same test as in Example 1 and the test shown below. The results of each test are shown in Table 1. From Table 1,
It was found that the obtained powdered explosive composition had the RDX surface covered with components other than RDX as compared with the powdered explosive composition obtained in Comparative Example 1.

Now, the X-ray photoelectron spectroscopy analysis will be described.

[0033]

[X-ray photoelectron spectroscopic analysis] By irradiating the sample with X-rays and measuring the photoelectron spectrum emitted from the surface, the atoms and their chemical states present on the sample surface from the peak position, and the surface atom from the area intensity of the spectrum are measured. Measure the concentration. In this measurement, the photoelectron spectrum of carbon, oxygen, and nitrogen derived from each component of the powdery explosive composition surface produced was measured,
It was examined which of the components of the raw material for the explosive composition was present on the surface of the powdery explosive composition produced, and from the results, it was determined how much the RDX was covered. Table 1
Shows the coverage of RDX. The coverage was determined by (carbon concentration derived from raw material of explosive composition other than RDX) / (carbon concentration of RDX). The larger the value of RDX coverage,
It can be said that the RDX on the surface is covered with other raw materials for the explosive composition. The test conditions are as follows. Equipment ULVAC PHI ESCA5400 X-ray source Mg, Ka output 400 W (15 kV × 26.7 mA)

[0034]

Example 4 R moistened with 52.8 g of methyl ethyl ketone
DX (water content 50.5%) 14.26 g, cellulose acetate butyrate 0.95 g, nitrocellulose 0.3
15 g, 0.032 g of ethyl centralite, 0.6 g of tributyl citrate are added, the solution is heated to 65 ° C.,
Each component was completely dissolved. While keeping this solution at 65 ° C., it was sprayed into a chamber (200 mm in length) supplying steam by using a coaxial nebulizer (spraying hole diameter: 0.1 mm). The resulting powdered explosive composition was added to vigorously stirred water. The powdered explosive composition and a suspension of water were stirred under reduced pressure at 65 ° C. for 20 minutes to remove residual methyl ethyl ketone. After the suspension was cooled to room temperature, a white powdery explosive composition was obtained by suction filtration. The obtained powdered explosive composition was evaluated by the same test as in Example 4. A photograph of the powdery explosive composition obtained is shown in FIG. 6, and the test results are shown in Table 1.

[0035]

Example 5 In the procedure of Example 4, the same procedure as in Example 4 is performed, except that acetyltriethyl citrate is changed to diethylene glycol dinitrate and the poor solvent to be contacted after passing through the chamber is changed from water to hexane. As a result, a white powdery explosive composition was obtained. The obtained powdered explosive composition was evaluated by the same test as in Example 4. The results of each test are shown in Table 1. Further, the presence of diethylene glycol dinitrate in the product was confirmed by measuring the product by three-dimensional high performance liquid chromatography. The test conditions are as follows. Equipment Waters 991J Photodiode Array Detector Column Waters μ Bondasphere Column packing material High-purity silica 5μ C18 Column size 3.9 × 150 mm Column temperature 40 degrees Mobile phase 50% Acetonitrile aqueous solution flow rate 0.8 ml / min Detector UV detector Measurement wavelength range 210nm-600nm

[0036]

Example 6 To 197 g of methyl ethyl ketone was added 3.57 g of cellulose acetate butyrate, 1.2 g of nitrocellulose, 0.12 g of ethyl centrallite, and 2.26 g of acetyltriethyl citrate, and this solution was added to 5 g.
HNIW which was dissolved by heating to 0-60 ℃
(Water content 10%) 25.1g was added, and added HNIW 8
A suspension in which 0% was dissolved was prepared. 50 ~ this suspension
While maintaining the temperature at 60 ° C., the powdery explosive composition was sprayed into a chamber (200 mm in length) using a coaxial nebulizer (spraying hole diameter: 0.1 mm), and the resulting powdered explosive composition was added to stirring water. The powdery explosive composition in water was stirred under reduced pressure at 50 ° C. for 20 minutes to remove the residual methyl ethyl ketone. After the suspension was cooled to room temperature, a white powdery explosive composition was obtained by suction filtration. The obtained powdered explosive composition was evaluated by the same test as in Example 4. The results of each test are shown in Table 1.

[0037]

Comparative Example 1 RD moistened with 197 g of methyl ethyl ketone
X (water content 10%) 25.1 g, cellulose acetate butyrate 3.57 g, nitrocellulose 1.2 g, ethyl centralite 0.12 g, and acetyl triethyl citrate 2.26 g were added, and the solution was heated to 60 to 70 ° C. Then, each component was completely dissolved. This solution at 60-70 ° C
The spray was sprayed into the cyclone using an ejector and immediately thereafter the spray was added to the stirring water. The suspension was suction-filtered to obtain a white powdery explosive composition. The resulting explosive composition was used in Example 4
It evaluated by the same test as. The results of each test are shown in Table 1.

[0038]

Comparative Example 2 R moistened with 52.8 g of methyl ethyl ketone
DX (water content 50.5%) 14.26 g, cellulose acetate butyrate 0.95 g, nitrocellulose 0.3
g, ethyl central lite 0.03 g, and tributyl citrate 0.6 g were added, and the solution was heated to 65 ° C. to completely dissolve each component. While keeping this solution at 65 ° C., a white powdery explosive composition was obtained in the same manner as in Reference Example 1. The obtained explosive composition was evaluated by the same test as in Example 4. The results of each test are shown in Table 1.

[0039]

[Table 1]

[0040]

By using the method according to the present invention,
A low-sensitivity spherical powdery explosive composition having a desired average particle diameter can be easily obtained at low cost. Further, when the method of the present invention is used, the components other than the crystalline explosive are not peeled off from the crystalline explosive in the obtained powdered explosive composition, so that the dispersibility and binding property of the powdered explosive composition are improved. Therefore, it is possible to improve the physical properties and the combustion performance of the explosive powder manufactured by using this as a raw material.

[Brief description of drawings]

FIG. 1 is a schematic diagram of an apparatus for carrying out the present invention.

FIG. 2 shows a cross-sectional view of a coaxial nebulizer as an example of a sprayer used in the present invention.

FIG. 3 shows a diagram (a part of which is a cross-sectional view) of a cross flow type nebulizer as an example of a sprayer used in the present invention.

FIG. 4 is an electron micrograph of raw material RDX (average particle size 150 μm).

5 shows an electron micrograph of fine powder RDX obtained in Example 1. FIG.

FIG. 6 shows an electron micrograph of the powdered explosive composition obtained in Example 4.

[Explanation of symbols]

(1) Atomizer (2) Sample supply tube (3) Gas supply pipe (4) Sample spray port (5) Gas spray port (6) Chamber (7) Deposition tank (8) Heating device (9) Decompression port (10) Poor solvent supply port (11) Deposition tank inlet (12) Deposition tank outlet (13) Stirrer

Claims (25)

[Claims] 1. A solution or suspension of an explosive composition raw material dissolved or suspended in an organic solvent is sprayed with a gas, and at least one of heating and depressurization is performed while the sprayed spray solution is passed through a chamber. 40 to 90 wt% of organic solvent
A method for producing a powdery explosive composition, which comprises contacting a poor solvent after distilling off. 2. The method according to claim 1, wherein a solution of the raw material for the explosive composition dissolved in an organic solvent is used as the liquid to be sprayed. 3. The method according to claim 1, wherein the method for distilling off the solvent comprises reducing the pressure. 4. The raw material of the explosive composition, comprising at least one crystalline explosive, or at least one crystalline explosive and a polymer compound.
The manufacturing method according to claim 3. 5. A suspension in which a raw material for an explosive composition is mixed with an organic solvent as a liquid to be sprayed, and at least one crystalline explosive is dissolved in the organic solvent in an amount of 10 to 95 wt% and other components are completely dissolved. A liquid is used, The manufacturing method in any one of Claim 1 thru | or 4 characterized by the above-mentioned. 6. The method according to claim 5, wherein at least one crystalline explosive is dissolved in an organic solvent in an amount of 50 to 70 wt%.
The manufacturing method described in. 7. The boiling point of the organic solvent is 15 ° C. to 160 ° C.
7. The method according to claim 1 to 6, characterized in that
The manufacturing method according to any one of 1. 8. At least one of acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, acetonitrile, and nitroethane is used as a solvent for dissolving the raw material for the explosive composition. The manufacturing method according to claim 7. 9. The manufacturing method according to claim 1, wherein the spraying is performed using an inert gas. 10. The manufacturing method according to claim 1, wherein the pressure of the gas for spraying the solution or suspension is 0.1 MPa to 1.0 MPa. 11. The spray has a diameter of a spray port of 0.01 mm.
The method according to any one of claims 1 to 10, wherein the manufacturing method is performed in a range of from 5 mm to 5 mm. 12. The liquid and gas to be sprayed are respectively supplied by using pipes, and the spraying is performed by setting the angle between the pipes to be 0 ° to 90 °. The manufacturing method described in. 13. The manufacturing method according to claim 1, wherein spraying is performed using a nebulizer. 14. A coaxial type nebulizer or a cross flow type nebulizer is used.
The manufacturing method described in. 15. The method according to claim 1, wherein the liquid to be sprayed is heated to a temperature below the boiling point of the solvent used.
4. The method according to any one of 4 above. 16. The manufacturing method according to claim 1, wherein the chamber through which the sprayed spray liquid is passed is set to have a length of 100 mm to 500 mm. 17. An apparatus for producing a powdered explosive composition, comprising:
Means for spraying a solution or suspension of a raw material for an explosive composition dissolved or suspended in an organic solvent, means for distilling a part of the sprayed spray liquid through a chamber, and part of the organic solvent An apparatus for producing the powdered explosive composition, comprising a means for bringing the spray liquid, which has been distilled off, into contact with a poor solvent. 18. The chamber for passing the atomized spray liquid comprises a heating or depressurizing means.
The manufacturing apparatus according to. 19. The manufacturing apparatus according to claim 18, wherein the chamber has a pressure reducing means. 20. The manufacturing method according to claim 17, wherein the means for spraying the solution or suspension has a means for injecting a gas of 0.1 MPa to 1.0 MPa. apparatus. 21. The manufacturing apparatus according to claim 17, wherein the means for spraying the solution or the suspension has a spray port having a diameter of 0.01 mm to 5 mm. 22. A pipe for supplying gas and a pipe for supplying liquid to be sprayed are provided, and an angle formed by each pipe is 0.
The manufacturing apparatus according to any one of claims 17 to 21, wherein the manufacturing apparatus has a degree of 90 degrees. 23. The manufacturing apparatus according to claim 17, wherein the spraying means is a nebulizer. 24. The method according to claim 17, further comprising means for heating the liquid to be sprayed to a temperature lower than the boiling point of the solvent.
The manufacturing apparatus according to any one of 1. 25. The length of the chamber through which the spray liquid passes is 10
The length is 0 mm to 500 mm.
25. The manufacturing apparatus according to claim 24.