JPH0220599B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing an ammonium nitrate explosive with very little chargeability or a non-chargeable ammonium nitrate explosive. Ammonium nitrate explosives (hereinafter abbreviated as nitric oil) are widely used because they do not contain highly sensitive sensitizers, are safe in terms of manufacturing and handling, and are inexpensive. Generally, nitrate explosives are poured directly into the borehole of the object to be destroyed, or loaded into the borehole using a loading machine that uses compressed air. At this time, the nitrate explosive particles collide with the loading hose and the inner wall of the borehole due to friction. static electricity is generated. This static electricity accumulates on workers, loading hoses, boreholes, loading machines, and nitric oil explosive particles, and if these charges are discharged all at once, there is a danger of exploding the electric detonator, and furthermore, there is a risk of electric shock to the human body. The accumulation of static electricity is a major safety problem that cannot be ignored, as it can cause secondary disasters. Conventionally, as a countermeasure against static electricity, a metal container or a charging hose made of a good conductor was used, and these were completely connected to the battery. However, this measure does not allow the generated static electricity to
It attempts to prevent the build-up of charge in the borehole, loading hose, and loading machine, and does not take into account any possibility of charging the nitrate explosive particles. It has been difficult to eliminate accidental explosions when loading parent dies. A nitric oil explosive composition (Japanese Patent Publication No. 43-9678) is known that contains 0.5 to 4 parts by weight of water per 100 parts by weight of the explosive in order to reduce the charge on the nitric oil explosive particles. However, in order to prevent deterioration in explosive performance due to direct contact between ammonium nitrate (hereinafter abbreviated as ammonium nitrate) and water, this nitric oil explosive composition emulsifies water and fuel oil using a surfactant. The method involves forming an emulsion and mixing it with ammonium nitrate, which is complicated to manufacture because the emulsion must be formed, and the degree of non-static property is not perfect. Furthermore, if stored for a long period of time, the emulsion would break down, causing a decline in explosive performance. Furthermore, there was the inherent problem that the explosive performance was low because it contained water. In addition, after infiltrating fuel oil into ammonium nitrate, nitrate explosives are
A method for producing nitric oil explosives is also known (Japanese Patent Publication No. 12440/1983) in which 0.1 to 5 parts by weight of carbon black that has passed through a 150 mesh sieve is mixed with 100 parts by weight. Since the nitric oil explosive thus produced contains carbon black, the nitric oil explosive particles themselves become black, and even if the content is less than 1 part by weight, anything that comes into contact with the nitric oil explosive particles will
All of them turned black and caused manufacturing and handling problems. Furthermore, using the same manufacturing method, metal salts of higher fatty acids, in a range of 0.1 to 5 parts by weight per 100 parts by weight of explosives,
A method for producing nitric oil explosives containing one kind of substance selected from keacates and inorganic metal salts is also known (Japanese Patent Publication No. 43-837); Oil explosives had a problem with their non-static properties. The purpose of the present invention is to solve the problems of the conventional method for producing nitric oil explosives, to manufacture nitric oil explosives that are easy to manufacture, have excellent stability over time, and have significantly excellent non-static properties. It is about providing law. As a result of extensive research into various surfactants that are easily dispersed in fuel oil and do not react with ammonium nitrate, the present inventors have discovered a method for adding a specific surfactant and have completed the present invention. The present invention provides 0.07 to 100 parts by weight of nitric oil explosive.
0.6 parts by weight of the following general formula () and general formula ()
A low or non-chargeable nitric oil explosive (hereinafter simply referred to as This is a method for producing non-charged nitric oil explosives. General formula [RN ⁺ (CH ₃ ) ₃ ]Cl ^- ... () (In the formula, R represents an alkyl group having 4 to 18 carbon atoms)
Alkyltrimethylammonium chloride represented by general formula (In the formula, R represents an alkyl group having 4 to 18 carbon atoms)
Alkyldimethylbenzylammonium chloride represented by The ammonium nitrate used in the present invention is usually granular ammonium nitrate, and the conventionally used porous granular ammonium nitrate (bryl ammonium nitrate) is particularly preferred from the viewpoint of improving explosive performance. The fuel oil used in the present invention includes, for example, heavy oil, light oil, kerosene, petroleum mineral oil such as liquid hydrocarbon, whale oil,
Seed oil, coal tar, etc. In the present invention, in addition to the main components consisting of ammonium nitrate and fuel oil, additives such as pigments may be added to distinguish the explosive from other explosives. According to research conducted by the inventors of the present invention, the specific surfactant used in the present invention does not react with ammonium nitrate to generate ammonia gas, and is extremely effective in improving the non-static effect of nitric oil explosives that do not contain water. It is effective and its effects last for a long period of time. The surfactants used in the present invention are alkyltrimethylammonium chloride and alkyldimethylbenzylammonium chloride represented by the above general formulas () and (). chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, etc.
Further, the alkyldimethylbenzylammonium chloride is, for example, coconut dimethylbenzylammonium chloride. Further, the content of the surfactant used in the method for producing a non-charged nitric oil explosive of the present invention is as follows:
0.07 to 0.6 per 100 parts (based on weight, the same applies hereinafter)
Department. If the content is less than 0.07 parts, the non-static effect will be small, and even if it exceeds 0.6 parts, the non-static effect will not be significantly improved compared to 0.6 parts, so it is not economical. disadvantageous from this point of view. The uncharged nitric oil explosive consisting of the above components can be produced by the production method of the present invention, which involves uniformly dispersing one or more surfactants specified in the present invention in fuel oil, and then mixing this with ammonium nitrate. Therefore, it can be easily manufactured. The obtained non-charged nitric oil explosive can be used as it is by being loaded into the borehole of the object to be destroyed, or it can be loaded into an appropriate packaging material to form an explosive cartridge, which is then used by filling it into the borehole of the object to be destroyed. . The production method of the present invention as described above does not use water, so it does not require a step of emulsifying water into fuel oil. Unlike the conventional production method in which inorganic metal salts, etc. are mixed after infiltrating fuel oil into ammonium nitrate, a specific surfactant that is easily dispersed in fuel oil is dispersed in advance and then mixed with ammonium nitrate. Because of this method, the fuel oil permeates the ammonium nitrate and the surfactant is uniformly attached to the surface of the ammonium nitrate, and the resulting nitric oil explosive has much better non-static properties than conventional ones. It has the feature that the effect lasts for a long time. Next, the method for producing the non-chargeable nitric oil explosive of the present invention will be specifically explained with reference to Examples and Comparative Examples. Note that all parts in each example are based on weight. Example 1 A non-chargeable nitric oil explosive having the composition shown in Table 1 was manufactured as follows. First, 6 parts of octadecyltrimethylammonium chloride (Cateon AB, manufactured by Nippon Oil & Fats Co., Ltd.) was uniformly dispersed in 60 parts of No. 2 diesel oil by stirring for 10 minutes with a propeller-type stirrer, and then 940 parts of ordinary ammonium bryl nitrate ( (manufactured by Sumitomo Chemical Industries, Ltd.) and mixed well to obtain a non-chargeable nitric oil explosive. 500 g of this non-charged nitric oil explosive was placed in a polyethylene bag with a diameter of 190 mm and a length of 350 mm, and both ends of the bag were closed to form a medicine package, which was used to measure the charging voltage. The charging voltage was measured by rotating the medicine bag at a speed of 60 times per minute to generate static electricity, and then measuring the charging voltage on the outside of the bag using a collector-type electrostatic potential measuring device (manufactured by Kasuga Denki Co., Ltd., KS- 471 model) to find the relationship curve between the number of frictions and the charged voltage, and the results are shown in Figure 1 as curve E.
-1 is indicated by a solid line. In the figure, the number of frictions N is scaled on the horizontal axis, and the charging voltage E (KV) is scaled on the vertical axis. In addition,
The room temperature during the measurement was 9 to 12°C, and the humidity was 37 to 45%. In addition, 190 g of the above-mentioned non-charged nitric oil explosive was packed with an inner diameter of 35 mm.
A total of two cartridges were manufactured by placing the nitric oil explosive in an iron tube with a wall thickness of 3 mm and a length of 250 mm and having a specific gravity of 0.88. One of the two tubes was immediately used for detonation velocity measurements, and the remaining one was stored for two months before being used for detonation velocity measurements. Incidentally, the explosion velocity was measured by a conventional counter method. However, 50g of No. 2 Enoki dynamite was used as the detonator, and each measurement result was
Shown in the table. Examples 2 to 7 Non-chargeable nitric oil explosives were produced according to Example 1, except that the type or amount of surfactant added was changed as shown in Table 1. Each cartridge was obtained in the same manner as in Example 1 using this non-charged nitric oil explosive. Using this medicine package, the electrostatic voltage was measured in the same manner as in Example 1, and the results are shown in the curve E-
2, E-3, E-4, E-5, E-6 and E-
7 as a solid line. The detonation velocity was also measured using the same method as in Example 1, and the results are shown in Table 1. Comparative Example 1 A nitric oil explosive consisting only of ammonium nitrate and No. 2 light oil as shown in Table 2 was produced as follows. 940 parts of ordinary Bryl nitrate (manufactured by Sumitomo Chemical Industries, Ltd.) was added to 60 parts of No. 2 diesel oil and mixed well to obtain a nitric oil explosive. A cartridge was obtained in the same manner as in Example 1 using this nitric oil explosive. Using this medicine package, the charging voltage was measured in the same manner as in Example 1, and the results are shown in FIG. 1 by a broken line as curve C-1. The explosion velocity was also measured using the same method as in Example 1, and the results are shown in Table 2. Comparative Example 2 As shown in Table 2, a nitric oil explosive containing a care acid salt was produced as follows. Add 940 parts of ordinary Bryl ammonium nitrate (manufactured by Sumitomo Chemical Co., Ltd.) to 60 parts of No. ) were mixed to obtain a nitric oil explosive. A cartridge was obtained in the same manner as in Example 1 using this nitric oil explosive. Using this medicine package, the charging voltage was measured in the same manner as in Example 1, and the results are shown in FIG. 1 by a broken line as curve C-2. The explosion velocity was also measured using the same method as in Example 1, and the results are shown in Table 2. Comparative Example 3 As shown in Table 2, a nitric oil explosive containing a metal salt of a higher fatty acid was produced in the following manner. Add 940 parts of ordinary Bryl ammonium nitrate (manufactured by Sumitomo Chemical Co., Ltd.) to 60 parts of No. 2 diesel oil and mix well. After the No. 2 diesel oil has sufficiently penetrated into the Bryl ammonium nitrate, add zinc stearate (manufactured by Katayama Chemical Co., Ltd.). Mix 5 parts;
Obtained nitrate explosives. Example 1 using this nitric oil explosive
The medicine packet was obtained in a similar manner. Using this medicine package, the charging voltage was measured in the same manner as in Example 1, and the results are shown in FIG. 1 by a broken line as curve C-3. The explosion velocity was also measured using the same method as in Example 1, and the results are shown in Table 2. Comparative Example 4 A nitric oil explosive containing water as shown in Table 2 was manufactured as follows. First, 40 parts of water was added to 60 parts of No. 2 diesel oil, and then 1 part of a surfactant (Dispanol 86, manufactured by Nihon Yushi Co., Ltd.) was added as an emulsifier and stirred well to obtain an emulsion. 940 parts of Brillammonium nitrate (manufactured by Sumitomo Chemical Industries, Ltd.) was added and mixed well to obtain a nitric oil explosive. A cartridge was obtained in the same manner as in Example 1 using this nitric oil explosive. Using this medicine package, the charging voltage was measured in the same manner as in Example 1, and the results are shown in FIG. 1 by a broken line as curve C-4. The detonation velocity was also measured using the same method as in Example 1, and the results are shown in Table 2.

【table】

[Table] As is clear from the curves E-1 to E-7 (Examples 1 to 7), the non-static property of the non-chargeable nitric oil explosive obtained by the present invention in Fig. This shows significantly superior non-static properties compared to curve C-1 (Comparative Example 1), which shows the non-static properties of the conventional nitric oil explosive. Curve C-2 (Comparative Example 2) showing the non-static property of the nitric oil explosive containing silicate (magnesium silicate) and the non-static property of the nitric oil explosive containing the metal salt of higher fatty acid (zinc stearate) Curve C showing chargeability
-3 (Comparative Example 3) and curve C-4 (Comparative Example 4) showing the non-static property of a nitric oil explosive containing water. Furthermore, in Examples 1 and 2 using octadecyltrimethylammonium chloride, the non-static property clearly improved as the amount added increased. Furthermore, as shown in Table 1, the detonation velocity of the non-charged nitric oil explosive obtained by the present invention is
This is clearly higher than the detonation speed of the conventional nitric oil explosive containing water (Comparative Example 4) shown in the table. Furthermore, as shown in Table 1, there is almost no change over time in the detonation velocity of the non-charged nitric oil explosive obtained by the present invention, whereas the conventional nitric oil explosive containing water shown in Table 2 (comparison) Example 4) shows a tendency for the detonation velocity to decrease.

[Brief explanation of drawings]

FIG. 1 is a characteristic diagram showing the relationship between the number of frictions N and the charging voltage E, where the solid line shows the characteristics when using the non-chargeable nitric oil explosive obtained by the present invention, and the broken line shows the characteristics when using the conventional nitric oil explosive. The characteristics when using are shown below. The relationship between the curve in the figure and the example or comparative example is as follows. E-1: Example 1, E-2: Example 2, E-
3: Example 3, E-4: Example 4, E-5: Example 5, E-6: Example 6, E-7: Example 7, C
-1: Comparative example 1, C-2: Comparative example 2, C-3: Comparative example 3, C-4: Comparative example 4.

Claims (1)

[Scope of Claims] 1. 0.07 to 0.6 parts by weight of one or more surfactants represented by the following general formula () and general formula () are dispersed in fuel oil per 100 parts by weight of ammonium nitrate explosive. 1. A method for producing an ammonium nitrate oil explosive with low or non-electrification property, which comprises: mixing the fuel oil with ammonium nitrate. General formula [RN ⁺ (CH ₃ ) ₃ ]Cl ^- ... () (In the formula, R represents an alkyl group having 4 to 18 carbon atoms)
Alkyltrimethylammonium chloride represented by general formula (In the formula, R represents an alkyl group having 4 to 18 carbon atoms)
Alkyldimethylbenzylammonium chloride represented by