JP2002179490A - Producing method of powdery gunpowder composition and producing equipment thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for safely and inexpensively obtaining a crystalline explosive which is poorly sensitive and is pulverized using a convenient producing equipment and to provide a method for obtaining a powdery gunpowder composition which is excellent in dispersibility and combination property of the crystalline explosives and the component other than the crystalline explosives. SOLUTION: The liquid which dissolves or suspends the crystalline explosive of one kind or more, or the raw material of gunpowder composition which contains the crystalline explosive of one kind or more and polymer compound into an organic solvent is sprayed as fog by using inactive gas, etc., the solvent of 40-90 wt.% of used solvent is trapped from the raw material of explosive composition while the spray liquid passes through an injection pipe and, thereafter, the powdery explosive composition which is controlled so as to be particulate of desirable grain size is produced by allowing the powdery explosive to contact with an insoluble poor solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for producing a powdery explosive composition containing one or more crystalline explosives or one or more crystalline explosives and a polymer compound. is there. More specifically, a method for producing explosives such as powdered propellants, and a method and apparatus for producing powdered explosive compositions for use in the production of propellants and propellants as raw materials for molding them into desired shapes It is about.

[0002]

2. Description of the Related Art In recent years, explosives containing crystalline explosives have been used because of their high thermal stability. However, when using explosives containing this type of explosive, it is difficult to control the size of the explosive despite the fact that the size of the explosive greatly affects the combustion performance of the explosive. -In addition to the problem of high sensitivity to friction, when explosives containing crystalline explosives are manufactured by conventional methods, the dispersibility and bonding properties of the explosive composition materials in the manufactured explosives However, as a result, there were problems such as deterioration of physical properties and combustion performance of the explosive. 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 reducing the sensitivity by rounding the shape of the crystalline explosive have been studied. Techniques for increasing the dispersibility and binding properties of the explosive composition raw materials in the contained explosive have been desired and studied.

[0003] In the prior art, for example, in order to obtain a crystalline explosive having a desired particle size, a method is employed in which a raw material crystalline explosive is vigorously stirred and pulverized in a liquid such as water or an organic solvent. U.S. Pat. No. 4,065,529). However, the method involves a risk of explosion due to impact or the like, though the liquid is added. Alternatively,
A method of obtaining a crystalline explosive having a desired particle size by cooling or bringing a solution in which a crystalline explosive is dissolved in a soluble solvent into contact with a poor solvent and recrystallizing the same is disclosed (US Pat. No. 463).
No. 8065, U.S. Pat. No. 4,794,180). With this method, the risk of explosion due to impact etc. is low, but in order to obtain reproducible small particles, the selection of solvent type and temperature condition control during recrystallization must be very strict. In addition, it is often difficult to obtain spherical crystals having low sensitivity.

[0004] Further, among the same recrystallization methods, there has been disclosed that a crystalline explosive having a desired shape is obtained by recrystallizing the crystalline explosive 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 become large-scale in order to obtain an ultra-high pressure state. As described above, there is a problem of safety in the method of atomization by pulverization, a problem of difficulty in obtaining low-sensitivity crystals by the method of atomization by recrystallization, and a problem of simple equipment. When producing explosives containing explosives, the production method used up to now must be used, and therefore, there is a problem that the dispersibility and bonding properties of the explosive composition raw materials in the obtained explosive are poor. Was.

[0005] As a method for solving these problems, a solution in which a crystalline explosive is dissolved in a soluble solvent together with an additive having an affinity for a binder component of an explosive composition raw material is sprayed into a high-temperature atmosphere to spray the explosive. A method of obtaining a crystalline explosive of a particle size is disclosed (US Pat. No. 40923)
No. 83). Although the method is highly safe and the apparatus is simple, by using an additive having an affinity for the binder, it is possible to obtain an explosive with good dispersibility and binding properties between the explosive composition raw materials, After the spraying, the solvent is rapidly removed, and the surface of the generated crystalline explosive may become porous, and it is difficult to completely remove the solvent only by spraying. There is a danger that the explosive will aggregate and affect the combustion performance of the explosive using this explosive.

On the other hand, as another method for solving the problems of dispersibility and bonding, a crystalline explosive that is not dissolved or completely dissolved in an organic solvent is slurried in water together with other explosive composition raw materials. A method of obtaining a small-sized explosive composition having a desired shape by adding a polymer coagulant and a protective colloid to the mixture and granulating the mixture (Japanese Patent Application Laid-open No. Sho 61-1986).
37239). By using that method, it is possible to obtain an explosive composition with good dispersibility, but if the crystalline explosive is used without dissolving it, it is necessary to use a crystalline explosive that has been atomized to some extent in advance. Therefore, a separate step such as crushing and recrystallization of the crystalline explosive is necessary,
In addition, when the crystalline explosive was dissolved, the possibility of exposing the crystalline explosive to the surface of the explosive composition was high when mixed with water.

The explosive composition containing a crystalline explosive has been used as a method for solving such problems of operation safety, product particle size, shape stability, dispersibility of the explosive composition raw material in the explosive, and binding at a glance. A method for producing an explosive composition containing a crystalline explosive having a desired particle size and shape by spraying a solution obtained by dissolving raw materials in a solvent in which these are soluble using an ejector by steam is disclosed (JP-A-Hei. 1-331382
issue). Although the method is certainly superior in terms of handling safety and product quality as compared with the previous methods, the raw material solution of the explosive composition comes into contact with steam immediately after being ejected from the ejector, Components other than the crystalline explosive may be exfoliated from the crystalline explosive, and there is a risk that a highly sensitive crystalline explosive may be exposed.When an explosive is manufactured using this powder explosive composition as a raw material, the exposed crystalline explosive may be exposed. By dissolving with a solvent, there is also a risk that the particle size of the crystalline explosive becomes large or the dispersibility of the explosive composition in the explosive becomes poor.
Further, in order to obtain an explosive composition having a desired particle size and shape, there is a problem that control of steam pressure and temperature is difficult.

[0008]

SUMMARY OF THE INVENTION In order to solve all of the above-mentioned problems, the present invention provides a method and apparatus for obtaining a low-sensitivity, atomized crystalline explosive more safely and inexpensively by using a simple manufacturing facility. And a method and apparatus for obtaining a powder explosive composition having good dispersibility and binding property between a crystalline explosive and components other than the crystalline explosive.

[0009]

Means for Solving the Problems In order to solve the above problems, the present inventors have made intensive studies and as a result, have found that a solution or suspension of a powder composition raw material dissolved or suspended in an organic solvent is used. Spraying with a gas to form a mist, and while passing this sprayed liquid through an injection tube, at least one of heating and depressurization is performed to distill off 40 to 90 wt% of the organic solvent, and then contact with a poor solvent, The present inventors have found a method for producing a powdery explosive composition controlled to be spherical, and have accomplished the present invention. That is, the method for producing a powder explosive composition of the present invention comprises spraying a solution or suspension of the explosive composition raw material dissolved or suspended in an organic solvent with a gas, and passing the sprayed liquid through a chamber. And at least one of heating and depressurizing to remove 40 to 90% by weight of the organic solvent, and then contacting the organic solvent with a poor solvent. Further, the apparatus for producing a powder explosive composition of the present invention is an apparatus for producing a powder explosive composition, which comprises means for spraying a solution or suspension of a raw material for an explosive composition dissolved or suspended in an organic solvent. And a means for removing a part of the organic solvent from the sprayed liquid through a chamber, and a means for bringing the sprayed liquid from which a part of the organic solvent is distilled off into contact with a poor solvent. It is an apparatus for producing an explosive composition.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a raw material for an explosive composition may contain one or more crystalline explosives or one or more crystalline explosives and a polymer compound. The raw material for 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, ie, trimethylenetrinitramine (RDX), octogen, ie, cyclotetramethylenetetranitramine (HMX),
Pentaerythritol tetranitramine (PETN) and hexanitrohexaazaisowurtzitane (HNIW)
A nitramine compound such as

As the polymer compound, any compound may be used as long as it has a role of bonding a crystalline explosive and a raw material for an explosive composition other than the crystalline explosive. Examples of the polymer compound include cellulose acetate, Cellulose 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. Examples of the plasticizer include diethyl phthalate, dibutyl phthalate, dioctyl phthalate, butanetriol trinitrate (BTTN), acetate triethyl citrate, tributyl citrate (TBC), and 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 centralit, diphenylamine, 2-nitrodiphenylamine and the like can be used. As the anti-inflammatory agent, for example, potassium sulfate, potassium nitrate, and chlorite can be used. Further, the organic solvent in the present invention is a liquid that can be easily distilled off from a solution or suspension of the explosive composition raw material by performing at least one of heating and depressurization. Further, the organic solvent may contain moisture as long as it does not separate into two layers. In the present invention, decompression is often relatively efficient. When the boiling point of the organic solvent is lower than 15 ° C., the liquid is often not liquid at room temperature, and the solvent may evaporate before the explosive composition raw material is dissolved, and if the boiling point is higher than 160 ° C.,
Heating or reducing the pressure is not preferred because the organic solvent often cannot be easily distilled off from the solution or suspension of the explosive composition raw material. As the organic solvent, for example, acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, acetonitrile, nitroethane, and the like can be used, and acetone, methyl ethyl ketone, and ethyl acetate are preferably 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 nebulizer, and FIG. 3 shows a cross-flow 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 is at least one of components other than the crystalline explosive and the crystalline explosive in the explosive composition raw material. 10-95wt%
Refers to a liquid in a solid-liquid coexisting state in which the compound is dissolved in an organic solvent, the remaining crystalline explosive is not dissolved, and remains as a solid. In this suspension, if the amount of the crystalline explosive dissolved 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. When more than 95 wt% is dissolved,
It is not preferable because the possibility of changing the crystal structure of the explosive having a crystalline isomer increases. When a solution of a raw material for an explosive composition dissolved in an organic solvent is used as a liquid to be sprayed, it can often be performed relatively easily.

In FIG. 1, a sprayer (1) blows a solution or suspension of a raw material for an explosive composition supplied to a sample supply pipe (2) with a gas supplied to a gas supply pipe (3). Is a means for spraying a solution or suspension of a raw material for an explosive composition into a fine mist, and any one generally used as an atomizer can be used. Preferably, the spray pressure of the gas is from 0.1 MPa to 1.
The solution is preferably sprayed in the range of 0 MPa, and most preferably, the spray pressure of the gas is in the range of 0.2 MPa to 0.4 MPa. If the spray pressure is lower than 0.1 MPa, spraying cannot be performed or droplets after spraying may become large, which is not preferable. On the other hand, if the spray pressure exceeds 1.0 MPa, the spray speed increases and the spray distance of the droplets increases, and during this time, the solvent in the droplets may be excessively distilled off, which is not preferable.

The diameter of the gas spray port (5) is not limited as long as the gas spray pressure can keep the gas spray pressure 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 is good. 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. On the other hand, 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 spray 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 nebulizer (1) must be in the range of 0 to 90 degrees, and any number within this range. good. If it exceeds this range, the gas supplied from the gas supply pipe (3) flows into the sample supply pipe (2), and the solution or suspension is not sprayed. As the nebulizer (1), for example, a nebulizer can be used, and as the nebulizer, for example, a coaxial nebulizer or a cross-flow nebulizer can be used. FIG. 2 shows a coaxial nebulizer, and FIG. 3 shows a cross-flow nebulizer.

The solution or suspension of the raw material for the explosive composition supplied to the sample supply pipe (2) utilizes a negative pressure state in the sample supply pipe (2) generated by spraying gas from the gas spray port (5). And the solution may be supplied to the sample spraying port (4), or a solution for the explosive composition raw material may be prepared by providing a pressure pump in the sample supply tube (2) and pressurizing the inside of the sample supply tube (2). May be supplied to the sample spray port (4). 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).

As the gas to be supplied to the gas supply pipe (3), any gas may be used, and for example, compressed air, inert gas and the like can 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, a nitrogen gas, an argon gas, carbon dioxide, or the like can be used. In the present invention, the chamber (6) is an injection pipe for receiving the sprayed liquid. That is, the length of the chamber (6) is defined as the distance until the solution or suspension of the explosive composition raw material sprayed from the sample spray port (4) comes into contact with the poor solvent. A container provided for the purpose of distilling out the solvent therein from the solution or suspension of the explosive composition raw material and having a length sufficient to distill off 40 to 90% by weight of the solvent used. Any shape may be used, for example, a cylindrical shape may be used. Preferably, the solvent should have a length sufficient to distill off 50 to 70 wt% of the solvent used. Preferably, the length of the chamber (6) should be 100 mm to 500 m.
m.

When the amount of the solvent distilled off in the chamber (6) is less than 40% of the amount of the solvent used, the raw material for the explosive composition agglomerates and the particle size of the powdery explosive composition to be formed becomes large. It is not preferable because there is a possibility. On the other hand, 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 evaporate the solvent, and further for efficiently evaporating the solvent. The chamber (6) may be provided with a pressure reducing port (9) for reducing the pressure inside the chamber (6) and for connecting a pressure reducing pump. At this time, when the pressure in the chamber (6) is reduced to a range of 10 to 10000 Pa, the temperature in the chamber (6) is raised to a temperature of 100 ° C. or less, so that the solvent is reduced to 40 to 90 Pa.
wt% can be distilled off. Preferably, the pressure in the chamber (6) is reduced to a range of 100 to 7000 Pa. If the pressure in the chamber (6) is reduced to less than 10 Pa, the solvent is excessively distilled away, and the surface of the resulting powder explosive composition may become porous, which is not preferable. Further, when the pressure in the chamber (6) is reduced only to a pressure exceeding 10000 Pa, it is necessary to heat the inside of the injection tube to a temperature exceeding 100 degrees depending on the kind of the solvent. And the danger increases.

In order to completely remove the residual solvent contained in the powder explosive composition and to efficiently recover the powder explosive composition, the poor explosive composition in which the powder explosive composition is insoluble is used. Must be brought into contact with. As a method, a poor solvent supply port (10) for supplying a poor solvent can be provided in the chamber (6). Poor solvent supply port (10)
It is necessary to take 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 is distilled off from the solution or suspension. The poor solvent used can be any solvent as long as the explosive composition raw material is insoluble, for example,
Water, steam, heptane, hexane and the like can be used. If you do not use water or steam as a poor solvent,
Water-soluble compounds such as nitrate esters can be used as explosive composition raw materials. Specific examples of the compound soluble in water include nitroglycerin (NG), diethylene glycol dinitrate (DEGN), and the like.

The raw material for the explosive composition containing one or more crystalline explosives or one or more crystalline explosives and a polymer compound is
These materials are dissolved or suspended in a soluble organic solvent. At this time, in order to dissolve or suspend the explosive composition raw material in the organic solvent, the solution or suspension can be heated to a temperature not lower than room temperature and 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 sprayer (1) and sprayed with the gas supplied from the gas supply pipe (3). At this time, the solution or suspension of the explosive composition raw material supplied through the sample supply pipe (2) is sprayed in a mist form from the sample spray port (4). While the sprayed solution or suspension passes through the chamber (6), 40 to 90 wt% of the used solvent is distilled off, and solid components in the explosive composition are precipitated. The precipitated solid component is mixed with the poor solvent supplied from the poor solvent supply port (10),
Through the precipitation tank inlet (11), the powder explosive composition is collected in a precipitation tank (7) containing a poor solvent insoluble therein. 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 removing the organic solvent. When the boiling point of the poor solvent used was higher than the boiling point of the organic solvent, the remaining organic solvent was removed from the slurry suspension collected in the precipitation tank (7) under reduced pressure or normal pressure. 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. Then, the precipitation tank outlet (12)
After being taken out from the flask, a suction-filtering is performed to obtain a spherical powder explosive composition controlled to have a desired particle size.

In the present invention, since a liquid such as steam does not directly collide with the solution or suspension of the raw material for the explosive composition sprayed from the sample spray port (4), the explosives other than the crystalline explosives may be used. The components do not peel off. In addition, the organic solvent is distilled off in a spherical form without being crushed because the droplets are brought into contact with the poor solvent after a certain distance after spraying, and the poor solvent is not completely distilled off in the injection tube without the solvent being completely distilled off. Therefore, a powdery explosive composition having a porous surface cannot be obtained, and a powdery explosive composition having a spherical shape and a desired particle size without pores can be obtained. Furthermore, in the present invention, an explosive composition having a desired particle size can be obtained by controlling the gas spray pressure and the nozzle diameter. In addition, since the structure of the apparatus is simple, cleaning after use can be easily performed, and danger due to residual explosive in the apparatus can be eliminated.
In particular, when a suspension of the raw material for the explosive composition is used as the liquid to be supplied to the sample supply pipe (2), the crystalline isomer of the crystalline explosive after spraying changes because there is an undissolved crystalline explosive. Therefore, a spherical powder explosive composition having a desired crystal isomer can be obtained by using a desired crystal isomer as the crystalline explosive contained in the explosive composition raw material.

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.

[0024]

Example 1 Wet RDX (moisture 10%, average particle size 12
8.6 μm) was added to 20 ml of methyl ethyl ketone, and the mixture was heated to 70 ° C. and stirred to completely dissolve RDX. While maintaining this solution at 65 to 70 ° C., it was sprayed into a chamber (length: 150 mm) supplying steam using a coaxial nebulizer (spray port diameter: 0.1 mm). The RDX fine powder thus produced was added together with the steam to vigorously stirred water. The aqueous suspension of the RDX fine powder was stirred at 65 ° C. for 15 minutes under reduced pressure to remove the remaining methyl ethyl ketone. After the suspension was cooled to room temperature, it was filtered by suction. The obtained RDX fine powder was evaluated by the following test. Table 1 shows the test results. FIG. 4 shows a photograph of the raw material RDX, and 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 the raw material RDX. 4 and 5, it was found that the micronized RDX was spherical. Here, a measurement test of the particle size distribution will be described.

[0025]

[Measurement of Particle Size Distribution] About 1 to 3 ml of an about 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 dispersed by ultrasonic waves for 1 to 5 hours.
The particle size of the dispersed fine powder sample was measured according to the following measurement requirements. Equipment HELOS & CUVETTE made by JEOL Measurement principle Laser diffraction method (Franforfar diffraction theory) Light source He-Ne laser (632.8 nm / 5 mW) Detector 31-element ring-shaped multi-detector Disperser Stationary wet dispersion unit

[0026]

Example 2 Wet RDX (10% moisture, average particle size 27)
Micron) 26.2 g to 197 ml of methyl ethyl ketone
And 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) supplying steam using a coaxial nebulizer (spray port diameter 1.1 mm). The RDX fine powder thus produced was added to stirring water. The aqueous suspension of the RDX fine powder was stirred at 65 ° C. for 15 minutes under reduced pressure to remove the remaining methyl ethyl ketone. After the suspension was cooled to room temperature, it was filtered by suction. The obtained RDX fine powder was evaluated by the same test as in Example 1. Table 1 shows the test results.

[0027]

Example 3 197 g of methyl ethyl ketone was added to wet R
25.1 g of DX (10% moisture), 3.57 g of cellulose acetate butyrate, 1.2 g of nitrocellulose, 0.12 g of ethylcentralit, 2.26 g of acetyltriethyl citrate were added, and the solution was heated to 60 to 70 ° C. Then, each component was completely dissolved. 60-70 ° C
While maintaining the coaxial nebulizer (spray diameter 0.1 m)
m) and sprayed into a chamber (length 200 mm), and the resulting powdered explosive composition was added to stirring water. The aqueous suspension of the powdery explosive composition is placed under reduced pressure for 65 hours.
The mixture was stirred at 20 ° C. for 20 minutes to remove the remaining methyl ethyl ketone. After the suspension was cooled to room temperature, a white powdery explosive composition was obtained by suction filtration. The obtained powder explosive composition was evaluated by the same test as in Example 1 and the following test. Table 1 shows the test results. From Table 1,
It was found that the RDX surface of the obtained powder explosive composition was covered with components other than RDX than the powder explosive composition obtained in Comparative Example 1. Here, X-ray photoelectron spectroscopy will be described.

[0028]

[X-ray photoelectron spectroscopy] The sample is irradiated with X-rays, and the photoelectron spectrum emitted from the surface is measured. Measure the concentration. In this measurement, the photoelectron spectrum of carbon, oxygen and nitrogen derived from each component of the generated powder explosive composition surface is measured,
It was examined which of the components of the raw material for the explosive composition was present in a large amount on the surface of the generated powder explosive composition, and from the result, 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 explosive composition raw material other than RDX) / (carbon concentration of RDX). The greater the value of the RDX coverage,
It can be said that RDX on the surface is covered with other explosive composition raw materials. The test conditions are as follows. Apparatus ULVAC PHI ESCA5400 X-ray source Mg, Ka output 400 W (15 kV × 26.7 mA)

[0029]

Example 4 R wetted with 52.8 g of methyl ethyl ketone
DX (water 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 were added and the solution was warmed to 65 ° C.
Each component was completely dissolved. While maintaining this solution at 65 ° C., it was sprayed into a chamber (length 200 mm) supplying steam using a coaxial nebulizer (spray port diameter 0.1 mm). The resulting powdered explosive composition was added to vigorously stirred water. The suspension of the powder explosive composition and water was stirred at 65 ° C. for 20 minutes under reduced pressure to remove the remaining methyl ethyl ketone. After the suspension was cooled to room temperature, a white powdery explosive composition was obtained by suction filtration. The obtained powder explosive composition was evaluated by the same test as in Example 4. FIG. 6 shows a photograph of the obtained powder explosive composition, and Table 1 shows the results of each test.

[0030]

Example 5 The same operation as in Example 4 was carried out except that acetyltriethyl citrate was contacted with diethylene glycol dinitrate and the poor solvent to be contacted after passing through the chamber was changed from water to hexane. Thereby, a white powdery explosive composition was obtained. The obtained powder explosive composition was evaluated by the same test as in Example 4. Table 1 shows the test results. 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 High-purity silica 5μ C18 Column size 3.9 × 150mm Column temperature 40 degrees Mobile phase 50% acetonitrile aqueous solution Flow rate 0.8ml / min Detector UV detector Measurement wavelength range 210 nm to 600 nm

[0031]

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

[0032]

[Comparative Example 1] RD wet with 197 g of methyl ethyl ketone
25.1 g of X (moisture 10%), 3.57 g of cellulose acetate butyrate, 1.2 g of nitrocellulose, 0.12 g of ethylcentralit, 2.26 g of acetyltriethyl citrate are added, and the solution is heated to 60 to 70 ° C. Then, each component was completely dissolved. 60-70 ° C
The spray was then sprayed into the cyclone using an ejector, and immediately thereafter the spray was added to stirring water. This suspension was subjected to suction filtration to obtain a white powder explosive composition. The obtained explosive composition was prepared in Example 4.
Was evaluated by the same test as described above. Table 1 shows the test results.

[0033]

Comparative Example 2 R wetted with 52.8 g of methyl ethyl ketone
DX (water 50.5%) 14.26 g, cellulose acetate butyrate 0.95 g, nitrocellulose 0.3
g, ethyl centralit 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 maintaining this solution at 65 ° C., a white powder explosive composition was obtained using the same method as in Reference Example 1. The obtained explosive composition was evaluated by the same test as in Example 4. Table 1 shows the test results.

[0034]

[Table 1]

[0035]

By using the method according to the present invention,
A low-sensitivity spherical powder explosive composition having a desired average particle size can be obtained simply and at low cost. Further, when the method of the present invention is used, components other than the crystalline explosive in the obtained powder explosive composition do not peel off, so that the dispersibility and binding property of the powder explosive composition are reduced. It is possible to increase the physical properties and combustion performance of the explosive manufactured using the raw material.

[Brief description of the drawings]

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

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

FIG. 3 shows a cross-flow type nebulizer (partly in cross-section) 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 microns).

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

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

[Explanation of symbols]

 (1) Sprayer (2) Sample supply pipe (3) Gas supply pipe (4) Sample spray port (5) Gas spray port (6) Chamber (7) Precipitation tank (8) Heating device (9) Decompression port (10) ) Poor solvent supply port (11) Inlet of precipitation tank (12) Outlet of precipitation tank (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 passing the sprayed liquid through a chamber. 40-90 wt% of organic solvent
A method for producing a powdery explosive composition, comprising the steps of: 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 pressure is reduced as a method of distilling off the solvent. 4. The explosive composition raw material contains at least one kind of crystalline explosive, or at least one kind of crystalline explosive and a polymer compound.
The method according to claim 3. 5. A suspension in which the explosive composition raw material is mixed with an organic solvent as a liquid to be sprayed, at least one crystalline explosive is dissolved in the organic solvent in an amount of 10 to 95% by weight, and the other components are completely dissolved. The method according to claim 1, wherein a liquid is used. 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%.
Production method described in 1. 7. An organic solvent having a boiling point of 15 ° C. to 160 ° C.
7. The method of claim 1, wherein
The production method according to any one of the above. 8. The method according to claim 1, wherein 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 explosive composition raw material. The manufacturing method according to claim 7. 9. The production method according to claim 1, wherein spraying is performed using an inert gas. 10. The 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 spraying has a spraying port diameter of 0.01 mm.
The method according to any one of claims 1 to 10, wherein the process is performed at a distance of about 5 mm. 12. A liquid and a gas to be sprayed are respectively supplied by using tubes, and spraying is performed by setting an angle between the tubes to 0 ° to 90 °. The production method described in 1. 13. The method according to claim 1, wherein spraying is performed using a nebulizer. 14. A coaxial nebulizer or a cross-flow nebulizer is used.
Production method described in 1. 15. The liquid to be sprayed is heated to a temperature lower than the boiling point of the solvent used.
4. The production method according to any one of 4. 16. The method according to claim 1, wherein the length of the chamber through which the sprayed liquid is passed is set to 100 mm to 500 mm. 17. An apparatus for producing a powder explosive composition, comprising:
A means for spraying a solution or suspension of the explosive composition raw material dissolved or suspended in an organic solvent, a means for removing a part of the organic solvent from the sprayed liquid through a chamber, and a part of the organic solvent An apparatus for producing the powder explosive composition, comprising: a means for bringing the sprayed liquid from which the water has been distilled off into contact with a poor solvent. 18. The chamber for passing a spray liquid sprayed thereon has means for heating or reducing pressure.
3. The manufacturing apparatus according to claim 1. 19. The manufacturing apparatus according to claim 18, wherein the chamber has a means for reducing pressure. 20. The method according to claim 17, wherein the means for spraying the solution or the suspension has means for injecting a gas of 0.1 MPa to 1.0 MPa. apparatus. 21. The apparatus according to claim 17, wherein the means for spraying the solution or suspension has a spray port having a diameter of 0.01 mm to 5 mm. 22. A gas supply tube and a tube for supplying a liquid to be sprayed, wherein an angle between each tube is 0.
22. The manufacturing apparatus according to claim 17, wherein the angle is between 90 degrees and 90 degrees. 23. The manufacturing apparatus according to claim 17, wherein the means for spraying is a nebulizer. 24. A device for heating a liquid to be sprayed to a temperature lower than the boiling point of the solvent.
The manufacturing apparatus according to any one of the above. 25. The length of the chamber through which the spray liquid passes is 10
18. The distance between 0 mm and 500 mm.
25. The manufacturing apparatus according to claim 24.