KR102726063B1 - Emulsion explosive composition for Priming of bulk explosives - Google Patents

Abstract

The present invention provides an emulsion explosive composition for use as a bulk explosive, which comprises an oxidizing agent aqueous solution of 88 to 98 wt%, an emulsifier of 0.1 to 6 wt%, fuel oil of 0.1 to 5 wt%, and PMB (Plastic Micro Balloon) of 0.1 to 1.0 wt%, wherein the oxidizing agent aqueous solution is composed of at least one selected from monomethyl amine nitrate (MMAN) and ethylene diamine dinitrate (EDDN), ammonium nitrate, sodium nitrate, calcium nitrate, and water, and wherein the manufactured emulsion particle size is in the range of 0.5 ㎛ to 2.0 ㎛.

Description

{Emulsion explosive composition for priming of bulk explosives}

The present invention relates to an emulsion explosive composition for use as a propellant for bulk explosives.

Pentolite, which is currently mainly used as a propellant for bulk explosives, is manufactured through a process of melting and mixing high explosives, TNT and PETN. Pentolite has the advantage of a very fast detonation velocity due to the high explosives used in its manufacture (PETN, TNT detonation velocity = 8,000 m/s or more). On the other hand, it has the disadvantage of being sensitive due to the characteristics of the high explosives used as a raw material, so it has the disadvantage of being able to accidentally explode due to the influence of the surrounding environment (shock, friction, static electricity). In addition, since Pentolite is a solid, it can be damaged by external impact, so care must be taken when handling the product.

TNT and PETN, which are components of Pentolite, have the problem of decomposition under certain conditions. TNT is decomposed under each condition such as alkaline hydrolysis, thermal decomposition, and biodegradation, and PETN is decomposed by reaction with metals and metabolic reactions of microorganisms or strains. If decomposition occurs in this way, the performance of Pentolite may deteriorate, or an accidental explosion may occur due to the decomposition reaction.

Another problem that can be mentioned is the melting point of Pentolite. That is, TNT, which is a component of Pentolite, has a melting point of approximately 80℃, but the site where blasting takes place can be very hot depending on the location, so Pentolite is generally prohibited from being used in high-temperature ground sites above 60℃.

Emulsion explosives have been introduced as a propellant that can solve the above-mentioned shortcomings of Pentolite. The above-mentioned propellant emulsion explosives have the advantages of being usable in high-temperature ground, being free from damage by impact, and not being accidentally detonated by the external environment, but have the disadvantage of low detonation velocity compared to solid propellants. Therefore, a method for improving the detonation velocity is required.

Republic of Korea Publication Patent No. 2008-0083920

The present invention has been devised to solve the above problems of the prior art.

The purpose of this invention is to provide a bulk explosive emulsion explosive composition that has the advantages of being usable in high-temperature ground, having no risk of damage due to impact, and preventing accidental detonation due to the external environment, as well as having excellent detonation velocity.

The present invention

Contains 88~98 wt% oxidizer aqueous solution, 0.1~6 wt% emulsifier, 0.1~5 wt% fuel oil, and 0.1~1.0 wt% PMB (Plastic Micro Balloon).

The above oxidizing agent aqueous solution is an oxidizing agent aqueous solution composed of at least one selected from monomethyl amine nitrate (MMAN) and ethylene diamine dinitrate (EDDN), ammonium nitrate, sodium nitrate, calcium nitrate, and water.

Provided is a bulk explosive emulsion explosive composition for use as a propellant, characterized in that the manufactured emulsion particle size is in the range of 0.5 ㎛ to 2.0 ㎛.

The emulsion explosive composition for bulk explosives of the present invention is an emulsion-based explosive having an emulsion particle size of 2㎛ or less, which provides an explosion velocity that can maximize the power of bulk explosives. In addition, it has the advantages of being usable in high-temperature reactive ground, having no risk of damage by impact, and not being accidentally detonated by the external environment.

Figure 1 is a graph showing the correlation between the particle size of the emulsion in the emulsion explosive and the explosion velocity when PMB is applied, as confirmed in Test Example 1.
Figure 2 is a graph showing the correlation between the particle size of the emulsion in the emulsion explosive and the explosion velocity when PMB is applied, as confirmed in Test Example 1.

The present invention is described in detail below.

The present invention comprises 88 to 98 wt% oxidizing agent aqueous solution, 0.1 to 6 wt% emulsifier, 0.1 to 5 wt% fuel oil, and 0.1 to 1.0 wt% PMB (Plastic Micro Balloon).

The above oxidizing agent aqueous solution is an oxidizing agent aqueous solution composed of at least one selected from monomethyl amine nitrate (MMAN) and ethylene diamine dinitrate (EDDN), ammonium nitrate, sodium nitrate, calcium nitrate, and water.

The present invention relates to a composition of an emulsion explosive for use as a bulk explosive, characterized in that the manufactured emulsion particle size is in the range of 0.5 ㎛ to 2.0 ㎛.

Conventional emulsion explosive compositions for explosives have the advantages of being usable in high-temperature ground, being free from concerns of damage by impact, and not being accidentally detonated by the external environment, compared to solid explosives (e.g., Pentolite), but have the disadvantage of having a low detonation velocity compared to solid explosives.

The present invention is characterized in that the explosive velocity is improved by controlling the emulsion particle size of the emulsion explosive to be 2 ㎛ or less.

The particle size of the above emulsion may be 0.5 ㎛ to 2 ㎛. When producing an emulsion with a particle size of less than 0.5 ㎛, the shear required in the production process is too high and therefore difficult to manage. When the particle size exceeds 2 ㎛, the explosion speed becomes slow, which is not desirable.

In one embodiment of the present invention, the emulsion explosive composition comprises 88 to 98 wt% of an oxidizer aqueous solution, 0.1 to 6 wt% of an emulsifier, 0.1 to 5 wt% of fuel oil, and 0.1 to 1 wt% of PMB based on the total weight of the composition.

If the composition ratio of the above oxidizing agent solution is out of the above range, an emulsion may not be formed, and if the amount is small, a problem of non-explosion may occur. If the composition ratio of the above emulsifier is out of the above range, an emulsion may not be formed or a problem of non-explosion may occur. If the composition ratio of the above fuel oil is out of the above range, an emulsion may not be formed or a problem of non-explosion may occur.

In one embodiment of the present invention, the oxidizing agent aqueous solution comprises 2 to 15 wt% of at least one selected from monomethyl amine nitrate (MMAN) and ethylene diamine dinitrate (EDDN), 65 to 94 wt% of ammonium nitrate, 2 to 15 wt% of sodium nitrate, 1 to 10 wt% of calcium nitrate, and 1 to 10 wt% of water, and at least one selected from MMAN and EDDN contained in the oxidizing agent aqueous solution is used so as to be included in an amount of 3 to 10 wt% of the total weight of the emulsion explosive composition.

In one embodiment of the present invention, the emulsifier may be at least one selected from the group consisting of SMO (sorbitan monoleate) and PIBSA (amine salt of polyisobutylenesuccinicanhydride), but is not limited to the above components.

In one embodiment of the present invention, the fuel oil may be at least one selected from the group consisting of wax, mineral oil, light oil, and liquid paraffin.

In one embodiment of the present invention, the PMB is used as a foam retainer. The foam retainer is a component that forms a space with a certain portion of air or other gases in the gunpowder and acts as a sensitizer. The PMB may be selected from a copolymer of vinyldiene chloride (VDC), methyl methacrylate (MMA), and acrylonitrile (ACN), or a polymer of ACN. Since the chemical resistance may be lowered when the ACN content in the copolymer is less than 50 wt%, it is preferable that the copolymer contains 50 wt% or more of ACN.

When the above PMB is less than 0.1 wt% or more than 1 wt%, the ballistic blast or detonation velocity may decrease and half-explosion may occur, so it is not preferable. When the above PMB is used as a foam retainer, it is also preferable to use a PMB having a specific gravity (d) of 0.02 to 0.1 g/cc and an average particle size of 20 to 100 μm to play the role of a hot spot (maintaining continuous explosion by adiabatic compression).

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are intended to explain the present invention more specifically, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Example 1.

An emulsion was prepared by emulsifying 93 wt% of a 100°C aqueous oxidizer solution consisting of 10 wt% MMAN, 70 wt% ammonium nitrate, 10 wt% sodium nitrate, 5 wt% calcium nitrate, and 5 wt% water; and 7 wt% of a 90°C fuel solution consisting of 3 wt% diesel fuel and 4 wt% emulsifier using an emulsifier. An emulsion explosive was prepared by mixing 99.8 wt% of the emulsion and 0.2 wt% of PMB (a copolymer of VDC, ACN, and MMA having 50% ACN, true specific gravity (d) = 0.02) using a mixer.

Example 2.

An emulsion was prepared by emulsifying 7 wt% of a 90°C fuel solution, which was a mixture of 93 wt% of an oxidizer aqueous solution having the same composition as in Example 1, 3 wt% of wax, and 4 wt% of an emulsifier, using an emulsifier. An emulsion explosive was prepared by mixing 99.8 wt% of the emulsion and 0.2 wt% of PMB using a mixer.

Example 3.

An emulsion was prepared with the same composition as in Example 1. 99.74 wt% of the emulsion and 0.26 wt% of PMB were added, and then mixed using a mixer to prepare an emulsion explosive.

Example 4.

An emulsion was prepared with the same composition as in Example 2 above. 99.74 wt% of the emulsion and 0.26 wt% of PMB were added, and then mixed using a mixer to prepare an emulsion explosive.

Example 5.

An emulsion was prepared by emulsifying 7 wt% of a 90°C fuel solution, which was a mixture of 93 wt% of an oxidizer aqueous solution having the same composition as Example 1, 3 wt% of liquid paraffin, and 4 wt% of an emulsifier, using an emulsifier. An emulsion explosive was prepared by mixing 99.7 wt% of the emulsion and 0.3 wt% of PMB using a mixer.

Example 6.

An emulsion was prepared by emulsifying 6 wt% of a 90°C fuel solution, which was a mixture of 94 wt% of an oxidizer solution having the same composition as Example 1, 3 wt% of liquid paraffin, and 3 wt% of an emulsifier, using an emulsifier. An emulsion explosive was prepared by mixing 99.7 wt% of the emulsion and 0.3 wt% of PMB using a mixer.

Example 7.

An emulsion was prepared by emulsifying 5.5 wt% of a 90°C fuel solution containing 94.5 wt% of an oxidizer solution having the same composition as Example 1, 3 wt% of liquid paraffin, and 2.5 wt% of an emulsifier using an emulsifier. 99.67 wt% of the emulsion and 0.33 wt% of PMB were added, and then mixed using a mixer to prepare an emulsion explosive.

Comparative example 1.

An emulsion was prepared with the same composition as in Example 1. 98.4 wt% of the emulsion and 1.6 wt% of GMB (3M, Glass Micro Bubble K-15) were added, and an emulsion explosive was prepared using a mixer.

Test Example 1: Evaluation of explosion velocity according to emulsion particle size

By controlling the emulsification speed and emulsification time of the emulsion of the above Example 1, emulsion explosives according to the particle size of the emulsion were manufactured, and the explosion speeds of the emulsion explosives according to the emulsion particle size were compared. The emulsion particle size was measured using a measuring device (Mastersizer), and the explosion speed was evaluated by performing a test under conditions confined in a Φ50 mm steel pipe. The emulsion explosive of Comparative Example 1 was manufactured using the same method, and the test was performed. The sizes of the manufactured emulsions are as shown in Table 1 below, and the results of the explosion speed test are shown in Figs. 1 and 2.

As shown in Fig. 1, when PMB was used, a similar explosion velocity was observed regardless of the emulsion particle size. On the other hand, as shown in Fig. 2, when GMB was used, the explosion velocity tended to decrease as the emulsion particle size increased. It can be confirmed that it is good to apply PMB in order to reduce the deviation according to the manufacturing conditions.

Test Example 2: Performance Evaluation of Emulsion Explosives

In order to compare the existing solid-type explosive, Pentolite, with the emulsion explosive of the present invention (prepared in Example 5), a comparative test was conducted under mine field conditions. That is, an explosion test was performed using Pentolite and the emulsion explosive of the present invention (prepared in Example 5) in a field using ANFO and HiMEX 75-120 as bulk explosives with a pore diameter of Φ89 mm, and the explosion velocity was measured. The results of the test using 150 g and 200 g of Pentolite, and 150 g, 200 g, 230 g, and 300 g of the emulsion explosive for explosive (prepared in Example 5) in the same field environment were as shown in Table 2 below.

Bulk products Types of explosives Full explosive
Dosage (g) Explosion velocity (m/s) Ave. Range ANFO Pentolite 150 3771 3667~3836 200 3429 2145~3868 Full-scale use
Emulsion explosive
(Manufacturing Example 5) 150 2801 2013~3588 200 3475 3470~3480 230 3383 2121~3902 300 3370 2072~3828 HiMEX 75-120 Pentolite 150 4893 4452~5334 200 5405 5092~5691 Full-scale use
Emulsion explosive
(Manufacturing Example 5) 150 5125 - 200 5247 5040~5485 230 5454 - 300 5159 4737~5424

From the results in Table 2 above, it was confirmed that the detonation velocity of bulk explosives was similar regardless of the type of propellant. These results mean that the emulsion explosive of the present invention, despite being an emulsion explosive, has no difference in performance compared to Pentolite, a solid-type propellant.

Test Example 3.

Emulsion explosives for explosives should be usable in both low-temperature and high-temperature environments, taking into account the usage environment. Therefore, the possibility of using the emulsion explosive of Example 7 in low-temperature and high-temperature environments was evaluated. In the case of a low-temperature environment, the test was conducted at -20℃, which is the low-temperature evaluation temperature for general explosives. In the case of a high-temperature environment, since no clear standard has been established, the test was conducted after storing it at a temperature of 100℃ for more than 2 hours, and then the change in performance was measured. The evaluation results are as shown in Table 3 below.

division condition Explosion velocity (m/s) Room temperature Φ50 mm confined 6,466 Room temperature Φ50 mm film 6,292 Low temperature (-20℃) 5,920 High temperature (100℃) 5,700

From the above test results, it was confirmed that the emulsion explosive for use as a propellant of the present invention provides an explosion velocity that can be used in both low-temperature and high-temperature environments.

Claims (5)

Contains 88~98 wt% oxidizer aqueous solution, 0.1~6 wt% emulsifier, 0.1~5 wt% fuel oil, and 0.1~1.0 wt% PMB (Plastic Micro Balloon).
The above oxidizing agent aqueous solution is an oxidizing agent aqueous solution composed of at least one selected from monomethyl amine nitrate (MMAN) and ethylene diamine dinitrate (EDDN), ammonium nitrate, sodium nitrate, calcium nitrate, and water.
The manufactured emulsion particle size ranges from 0.5 ㎛ to 2.0 ㎛.
An emulsion explosive composition for use as a bulk explosive, characterized in that it does not contain a solid oxidizer and has an average explosion velocity of 5,925 m/s or more. In the first paragraph,
An emulsion explosive composition for use as a bulk explosive, characterized in that MMAN or EDDN contained in the above-mentioned oxidizing agent aqueous solution is contained in an amount of 3 to 10 wt% based on the total weight of the emulsion explosive composition. In the first paragraph,
An emulsion explosive composition for use as a bulk explosive, characterized in that the above PMB is at least one selected from a copolymer of vinyldiene chloride (VDC), methyl methacrylate (MMA) and acrylonitrile (ACN) or a polymer of ACN. In the first paragraph,
An emulsion explosive composition for use as a propellant for bulk explosives, characterized in that the emulsifier is at least one selected from the group consisting of SMO (sorbitan monoleate) and PIBSA (amine salt of polyisobutylenesuccinicanhydride). In the first paragraph,
An emulsion explosive composition for use as a propellant for bulk explosives, characterized in that the fuel oil is at least one selected from the group consisting of wax, mineral oil, kerosene, and liquid paraffin.