WO2023106587A1 - Emulsion explosive composition for pre-explosives of bulk explosives - Google Patents

Abstract

The present invention provides an emulsion explosive composition for pre-explosives of bulk explosives, the emulsion explosive composition containing 88-98 wt% of an aqueous oxidizing agent solution, 0.1-6 wt% of an emulsifier, 0.1-5 wt% of a fuel oil, and 0.1-1.0 wt% of plastic micro balloons (PMBs), wherein the aqueous oxidizing agent solution is composed of: at least one selected from among monomethyl amine nitrate (MMAN) and ethylene diamine dinitrate (EDDN); ammonium nitrate; sodium nitrate; calcium nitrate; and water, and the particle size of the prepared emulsion is in the range of 0.5 μm to 2.0 μm.

Description

Emulsion explosive composition for pre-explosives of bulk explosives

The present invention relates to an emulsion explosive composition for pre-explosives of bulk explosives.

Currently, Pentolite, which is mainly used as a pre-explosive for bulk explosives, is manufactured through a process of melting and mixing TNT and PETN, which are high explosives. Pentolite has the advantage of very fast detonation speed due to the high explosive used in its manufacture (PETN, TNT detonation speed = 8,000 m/s or more). On the other hand, due to the characteristics of high explosives used as raw materials, sensitivity is sensitive, and it has the disadvantage that accidental explosions are possible due to the influence of the surrounding environment (impact, friction, static electricity). In addition, since Pentolite is solid, it can be damaged by external impact, so care must be taken when handling the product.

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

Another problem can be mentioned is the melting point of Pentolite. That is, TNT, a component of Pentolite, has a melting point of about 80℃, but the site where blasting takes place may be at a high temperature depending on the place, so Pentolite is generally prohibited from being used in high-temperature ground sites of 60℃ or higher.

Emulsion explosives have been introduced as pre-explosives that can overcome the above disadvantages of Pentolite. The emulsion explosive for full width has the advantage that it can be used in high-temperature ground, there is no fear of damage due to impact, and there is no accidental detonation caused by external environment, but the detonation speed is lower than that of solid-state explosives have Therefore, a method capable of improving the width speed is required.

As a prior patent related to the present invention, there is Korean Patent Publication No. 2008-0083920 ""water-in-oil type emulsion explosive" (published on September 19, 2008).

The present invention was made to solve the above problems of the prior art,

It is possible to use in high-temperature ground, there is no fear of damage by impact, and it has the advantage of not causing accidental detonation due to external environment, as well as providing an emulsion explosive composition for bulk explosives with excellent detonation speed. to be

the present invention

88 to 98 wt% oxidizing agent aqueous solution, 0.1 to 6 wt% emulsifier, 0.1 to 5 wt% fuel oil, 0.1 to 1.0 wt% PMB (Plastic Micro Balloon),

The 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 an emulsion "explosive" composition for bulk explosives, characterized in that the prepared emulsion particle size has a range of 0.5 μm to 2.0 μm.

The emulsion explosive composition for bulk explosives of the present invention is an emulsion-based explosive having an emulsion particle size of 2 μm or less, and provides a level of detonation speed capable of maximizing the power of the bulk explosive. In addition, it has the advantage that it can be used in high-temperature reactive ground, there is no fear of damage due to impact, and there is no accidental detonation caused by the external environment.

1 is a graph showing the correlation between the particle size of the emulsion and the detonation speed in the emulsion explosive when PMB is applied, which was 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 rate when PMB is applied, which was confirmed in Test Example 1.

Hereinafter, the present invention will be described in detail.

The present invention includes 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 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,

It relates to an "emulsion" composition for "explosives" of bulk explosives, characterized in that the prepared emulsion has a particle size in the range of 0.5 μm to 2.0 μm.

Compared to solid-state explosives (e.g., Pentolite), the conventional emulsion explosive composition for pre-explosives can be used in high-temperature ground, has no risk of damage due to impact, and does not cause accidental detonation due to external environments. Advantages However, it had the disadvantage of low detonation speed compared to solid-state explosives.

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

The particle size of the emulsion may be 0.5 μm to 2 μm. When preparing an emulsion with a particle size of less than 0.5 μm, management is difficult because the shear required in the manufacturing process is too high.

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

If the composition ratio of the aqueous oxidizing agent solution is out of the above range, an emulsion may not be formed, and if the amount is small, a problem of unexplosion may occur. If the composition ratio of the emulsifier is out of the above range, a problem in that an emulsion is not formed or exploded may occur. If the composition ratio of the fuel oil is out of the above range, an emulsion may not be formed or a problem may occur.

In one embodiment of the present invention, the aqueous oxidizing agent solution contains 2 to 15% by weight of one or more selected from monomethyl amine nitrate (MMAN) and ethylene diamine dinitrate (EDDN), 65 to 94% by weight of ammonium nitrate, It consists of 2 to 15% by weight of sodium nitrate, 1 to 10% by weight of calcium nitrate, and 1 to 10% by weight of water, and at least one selected from MMAN and EDDN contained in the aqueous oxidizing agent solution is 3 to 10% of the total weight of the emulsion explosive composition It is used so that the weight percent is included.

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 (amine salt of polyisobutylenesuccinicanhydride), etc., 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 holding agent. The bubble-preserving agent serves as a sensitizer as a component that forms a space with a certain portion of air or other gas in the gunpowder. The PMB may be a copolymer of vinyldiene chloride (VDC), methyl methacrylate (MMA) and acrylonitrile (ACN) or may be selected from polymers of ACN. If the content of ACN in the copolymer is 50% by weight or less, chemical resistance may be lowered, so the copolymer preferably contains 50% by weight or more of ACN.

When the amount of PMB is less than 0.1% by weight or more than 1% by weight, the ballistic gun or width speed is lowered and half-width may occur, which is not preferable. The PMB has a specific gravity (d) of 0.02 to 0.1 g / cc and an average particle size of 20 to 100 μm for the role of a hot spot (continuous explosion maintenance by adiabatic compression) when used as a bubble-retaining agent. can be used preferably.

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

Example 1.

93% by weight of an oxidizing agent aqueous solution at 100° C. composed of 10% by weight of MMAN, 70% by weight of ammonium nitrate, 10% by weight of sodium nitrate, 5% by weight of calcium nitrate, and 5% by weight of water; An emulsion was prepared by emulsifying 7 wt% of a 90° C. fuel solution composed of 3 wt% of light oil and 4 wt% of an emulsifier using an emulsifier. 99.8% by weight of the emulsion and 0.2% by weight of PMB (a copolymer of VDC, ACN and MMA with 50% ACN, true specific gravity (d) = 0.02) were mixed using a mixer to prepare an emulsion explosive.

Example 2.

An emulsion was prepared by emulsifying 7 wt% of a fuel solution at 90° C., a mixture composed of 93 wt% of an oxidizing agent 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% by weight of the emulsion and 0.2% by weight of PMB using a blender.

Example 3.

An emulsion was prepared with the same composition as in Example 1. After putting 99.74% by weight of the emulsion and 0.26% by weight of PMB, they were mixed using a blender to prepare an emulsion explosive.

Example 4.

An emulsion was prepared with the same composition as in Example 2. After putting 99.74% by weight of the emulsion and 0.26% by weight of PMB, they were mixed using a blender to prepare an emulsion explosive.

Example 5.

An emulsion was prepared by emulsifying 7 wt% of a fuel solution at 90° C., a mixture composed of 93 wt% of an oxidizing agent aqueous solution having the same composition as in Example 1, 3 wt% of liquid paraffin, and 4 wt% of an emulsifier, with an emulsifier. An emulsion explosive was prepared by mixing 99.7% by weight of the emulsion and 0.3% by weight of PMB using a blender.

Example 6.

An emulsion was prepared by emulsifying 6% by weight of a fuel solution at 90° C., a mixture of 94% by weight of an oxidizing agent aqueous solution having the same composition as in Example 1, 3% by weight of liquid paraffin, and 3% by weight of an emulsifier, using an emulsifier. An emulsion explosive was prepared by mixing 99.7% by weight of the emulsion and 0.3% by weight of PMB using a blender.

Example 7.

94.5% by weight of an oxidizing agent aqueous solution having the same composition as in Example 1; An emulsion was prepared by emulsifying 5.5 wt% of a fuel solution at 90° C. composed of 3 wt% of liquid paraffin and 2.5 wt% of an emulsifier using an emulsifier. After putting 99.67% by weight of the emulsion and 0.33% by weight of PMB, they were mixed using a blender to prepare an emulsion explosive.

Comparative Example 1.

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

Test Example 1: Explosion rate evaluation according to emulsion particle size

Emulsion explosives according to the particle size of the emulsion were prepared by adjusting the emulsification speed and emulsification time of the emulsion of Example 1, and the explosion speed of the emulsion explosives according to the emulsion particle size was 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 to a Φ50 mm steel pipe. In the same way, the emulsion explosive of Comparative Example 1 was prepared and tested. The size of the prepared emulsion is shown in Table 1 below, and the results of the explosion rate test are shown in FIGS. 1 and 2.

As shown in FIG. 1, when PMB was used, the explosion rate tended to be similar regardless of the emulsion particle size. On the other hand, as shown in FIG. 2, in the case of using GMB, the explosion rate tended to decrease as the particle size of the emulsion increased. It can be seen that it is better to apply PMB in order to reduce the variation according to manufacturing conditions.

division	Emulsion particle size (μm)	Average explosion velocity (m/s)
Example 1	0.74	6,108
	0.92	6,246
	1.07	5,925
	1.78	6,172
Comparative Example 1	0.74	6,338
	1.13	6,211
	1.54	5,917
	1.78	5,945

Test Example 2: Evaluation of Emulsion Explosives Performance Comparison tests were conducted under mine field conditions to compare Pentolite, a previously used solid-state explosive, and the emulsion explosive of the present invention (prepared in Example 5). That is, an explosion test was performed using Pentolite and the emulsion explosive of the present invention (prepared in Example 5) at a site using ANFO and HiMEX 75-120 as bulk explosives with a hole diameter of Φ89mm, and the explosion speed was measured. The test results using 150g, 200g, and 150g, 200g, 230g, and 300g of Pentolite emulsion explosives for explosives (prepared in Example 5) in the same field environment are shown in Table 2 below.

Bulk products	type of explosives	explosive charge Approximate amount (g)	Explosion speed (m/s)
			Ave.	Range
ANFO	Pentolite	150	3771	3667~3836
		200	3429	2145~3868
	for full explosive emulsion explosives (Example 5 Preparation)	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
	for full explosive emulsion explosives (Example 5 Preparation)	150	5125	-
		200	5247	5040~5485
		230	5454	-
		300	5159	4737~5424

From the results of Table 2, it was confirmed that the explosion speed of bulk explosives was similar regardless of the type of explosives. These results mean that the emulsion explosive of the present invention, despite being an emulsion explosive, has no performance difference compared to Pentolite, which is a solid form of explosive.

Test Example 3.

Emulsion explosives for pre-explosives must be usable in low-temperature and high-temperature environments in consideration of the use environment. Therefore, the possibility of using the low-temperature and high-temperature environment was evaluated using the emulsion explosive of Example 7. In the case of a low-temperature environment, the test was conducted at -20 ° C, which is the low-temperature evaluation temperature of general explosives. Changes were measured. The evaluation results were shown in Table 3 below.

division	condition	Explosion speed (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 pre-explosives of the present invention provides an explosion speed usable in both low-temperature and high-temperature environments.

Claims (5)

1. 88 to 98 wt% oxidizing agent aqueous solution, 0.1 to 6 wt% emulsifier, 0.1 to 5 wt% fuel oil, 0.1 to 1.0 wt% PMB (Plastic Micro Balloon),

   The 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 prepared emulsion particle size is in the range of 0.5㎛ to 2.0㎛.
2. According to claim 1,

   MMAN or EDDN contained in the oxidizing agent aqueous solution is included in an amount of 3 to 10% by weight relative to the total weight of the emulsion explosive composition.
3. According to claim 1,

   The PMB is a copolymer of vinyldiene chloride (VDC), methyl methacrylate (MMA) and acrylonitrile (ACN) or at least one selected from polymers of ACN.
4. According to claim 1,

   The emulsifier is at least one selected from the group consisting of SMO (Sorbitan monoleate) and PIBSA amine salt (Amine salt of polyisobutylenesuccinicanhydride).
5. According to claim 1,

   The fuel oil is at least one selected from the group consisting of wax, mineral oil, light oil, and liquid paraffin.

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