KR20030087121A - Emulsion expolsive with improved power - Google Patents

Abstract

PURPOSE: Provided are high strength emulsion explosives having improved explosion and impact resistance compared with conventional emulsion explosives by using plastic micro balloon(PMB) instead of glass micro balloon(GMB) as a sensitizer and sodium perchlorate(NaClO4) as an oxidizer. CONSTITUTION: The water in oil type emulsion explosives enough to explode granite comprise 80-90wt.% of oxidizing solution, 0.1-5wt.% of fuel solution, 0.1-5wt.% of emulsifier, 0.1-1.0wt.% of plastic micro balloon(PMB), and 5-15wt.% of aluminum. The PMB, having 0.04-0.1g/cc of specific gravity, 20-100micrometer of particle size and 0.2-10micrometer of thickness, contains vinyl diene chloride(VDC) including more than 50wt.% of acrylonitrile(ACN), the copolymer of methyl meta acrylate(MMA) and ACN, or the polymer of ACN. The oxidizing solution consists of water and ammonium nitrate, sodium nitrate, sodium chlorate, sodium perchlorate, monomethyl amine nitrate and hydrazine nitrate. The fuel solution is one or more of wax, mineral oil and gasoline. The aluminum is selected from the types of sphere, flake, foil and a mixture of thereof.

Description

Powerful emulsion explosives {EMULSION EXPOLSIVE WITH IMPROVED POWER}

The present invention relates to an emulsion explosive used in the open-air and tunnel blasting site, in order to maximize the power of using an organic preservative PMB (Plastic Micro Balloon) instead of an inorganic preservative GMB (Glass Micro Balloon) in the emulsion explosives and at the same time an oxidizing agent The present invention relates to an emulsion explosive applying sodium perchlorate so that the metal content (energy-enhancing substance), which is the most heat-containing oxygen, can be used a lot.

Bubble preservatives are materials that form a space in the gunpowder with air or other gas.Sensitizer that generates high heat by adiabatic compression when explosives explode and keeps explosives stable. Do it. In other words, the emulsion that emulsifies the oxidant solution composed of ammonium nitrate, sodium nitrate, water, etc. and the fuel solution composed of wax, mineral oil, etc. with emulsifier has no primer detonation. do. There are two ways to add bubbles to the emulsion explosive. One is to add a pre-made spherical bubble support agent and the other is to add a substance that generates gas by chemically reacting. Typical examples of the former are GMB and Perlite. However, these materials make no contribution to the explosive energy of explosives when the inert silicon oxide (SnO2) explodes as a main component.

On the other hand, PMB can contribute to the explosion energy by generating CO2, H2O when the explosives explode as the main component of the organic material consisting of carbon, hydrogen, oxygen, nitrogen. In addition, oxidizing agents currently used in emulsion explosives include ammonium nitrate (NH4NO3) and sodium nitrate (NaNO3), and their oxygen balance (weight of oxygen generated per unit weight of oxidant) is +0.2 and +0.471, respectively. The content of aluminum, which is less than 0.523 and can be added to these combinations, is up to 5% by weight. However, the combination of ammonium nitrate and sodium perchlorate allows up to 5% by weight or more of aluminum.

The reason why the strength of emulsion explosives should be strengthened is that because the rock structure of Korea is composed of granite, which is stronger than other countries, the explosive power of granite is needed to effectively break it. Currently, only gelatin dynamite is suitable for this. to be. In the emulsion explosive of the present invention, by adding PMB as a bubble support agent and sodium perchlorate as an oxidizing agent, aluminum was added in an amount of 5% by weight or more to increase ballistic ball envelopment force and speed.

Conventionally, in order to increase the power of the emulsion explosives, there is a method of adding a large amount of frill draft and aluminum to the emulsion explosive, and a method of adding aluminum at least 10% by weight while sacrificing the oxygen balance of the emulsion explosive at -5.0 (0 is optimal). The method of adding large amounts of frill draft and aluminum to emulsion explosives is a product of ICI's MAGNUM, which increases the ball throwing power to some extent, but decreases the speed of detonation and contains the frill draft, so that it absorbs moisture and melts when it comes into contact with the atmosphere. . The method of injecting more than 10% by weight of aluminum while sacrificing the oxygen equilibrium of emulsion explosive at -5.0 is called EMULSTAR of NOBEL EXPLOSIVES FRANCE, which also has a slight increase in ballistic attack force, but also decreases the speed of explosion. The disadvantage is that since the oxygen balance is -5.0, hydrogen gas is generated during the explosion, which causes a lot of secondary combustion.

The present invention has been made in view of the above problems, using PMB instead of GMB, which is a conventional foam support agent, by adding sodium perchlorate as an oxidizing agent to increase the content of aluminum by more than 5% by weight to increase the ballistic ball throwing force and explosion speed At the same time, it provides an emulsion explosive that can be used to crush strong domestic granite, such as gelatin dynamite.

In order to achieve the above object, the present invention provides 80 to 90% by weight of oxidizing agent solution, 0.1 to 5% by weight of fuel solution, 0.1 to 5% by weight of emulsifier, 0.1 to 1.0% by weight of organic microspheres, and 5 to 15% by weight of aluminum. Including;

The organic microspheres may be copolymers of vinyldiene chloride (VDC), acrylonitrile (ACN), methyl methacrylate (MMA) or acrylonitrile (ACN) containing 50% by weight or more of acrylonitrile (ACN). As polymers, specific gravity 0.04-0.1 g / cc, thickness 0.2-0.4 micron; And the aqueous oxidant solution is water-in-oil emulsion explosive, characterized in that containing 5 to 15% by weight of sodium perchlorate relative to the aqueous solution.

The aqueous oxidant solution is composed of ammonium nitrate, sodium nitrate, sodium chlorate, sodium perchlorate, monomethylamine nitrate, hydrazine nitrate, water, and the like. It is preferable to include.

The fuel solution is at least one selected from the group consisting of wax, mineral oil, light oil and the like. As the emulsifier, SMO (Sorbitan monoleate), PIBSAamine salt (Amine salt of Polyisobutylene succinicanhydride) and the like can be used conventionally, there is no particular limitation.

In the organic microspheres, the microspheres are required to be polymerized into monomers having excellent chemical resistance. For such excellent chemical resistance, vinyl diene chloride (VDC), acrylonitrile (ACN), a copolymer of methyl methacrylate (MMA), or a homopolymer of acrylonitrile (ACN) may be used. In a copolymer, it is preferable to contain 50 weight% or more of acrylonitrile. When the content of acrylonitrile is 50% or less in the copolymer, the chemical resistance becomes low and the above object cannot be achieved. It is also preferred that the thickness of the foamed PMB is 0.2 to 0.4 microns. When the thickness of the shell is low, the storage stability may be lowered, and when the thickness of the shell is exceeded, it may be unbalanced. This enhanced power emulsion explosive PMB serves as a hot spot when used as a bubble support agent, and more preferably has a specific gravity of 0.04-0.1 g / cc. In addition, the amount of the microspheres may preferably contain 0.1 to 1.0% by weight in the emulsion explosive, and if less than 0.1 or more than 1.0% by weight, ballistic balls or speed drops may be reduced, and half width may occur.

Aluminum may be used in the emulsion explosive and the aluminum may be selected from the group consisting of atomized type, scaled type, foil type and mixtures thereof. In addition, such aluminum may be anodized alone or both anodized and wax coated. It is preferable to use 5-15% by weight of such aluminum.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples. The following Examples are only described to facilitate the practice of the present invention, and are not described to limit the invention.

EXAMPLE

Example 1

90% SMO emulsifier at 90 ° C in 91.2% by weight of oxidant solution at 90 ° C containing 5% by weight of sodium perchlorate, ammonium nitrate, sodium nitrate, water, etc. and 2% by weight of fuel solution at 90 ° C made of wax, mineral oil, etc. 5% by weight of spherical (Atomized type) aluminum and PMB2 (copolymer of VDC, ACN, MMA with 50% by weight of ACN) having a specific gravity of 0.04 and a thickness of 0.2 μm. Putting the weight percent by mixing with a mixer to prepare an emulsion explosive.

Example 2

8 weight% of oxidizing agent solution at 90 ° C. containing 8 weight% of sodium perchlorate, ammonium nitrate, sodium nitrate, water, etc., and 1.7 weight of SMO emulsifier at 90 ° C. in 2 weight% of fuel solution at 90 ° C. which is made of wax, mineral oil, etc. Emulsifier was added to the emulsifier, and then 8% by weight of spherical (Atomized type) aluminum and PMB2 (copolymer of VDC, ACN, MMA having 50% by weight of ACN with a specific gravity of 0.04 and a thickness of 0.2 μm) 1 The weight percent was added and mixed with a mixer to prepare an emulsion explosive.

Example 3

83.7 weight% of oxidizing agent solution at 90 ° C. containing 12 weight% of sodium perchlorate, ammonium nitrate, sodium nitrate, water, etc., and 1.7 weight% of SMO emulsifying agent at 90 ° C. at 90 ° C. fuel solution 2 composed of wax, mineral oil, etc. To emulsify with an emulsifier, 12% by weight of spherical (Atomized type) aluminum and 0.6% by weight of PMB3 (according to 0.04 in specific gravity with ACN polymer and 0.2 μm in thickness) were added and mixed with a mixer to prepare an emulsion explosive. .

Example 4

90% of the SMO emulsifier at 90 ° C in 80.7% by weight of an oxidizing agent solution at 90 ° C. containing 15% by weight of sodium perchlorate and ammonium nitrate, sodium nitrate, water, etc. 15% by weight of spherical (Atomized type) aluminum and PMB2 (copolymer of VDC, ACN, MMA with 50% by weight of ACN) having a specific gravity of 0.04 and a thickness of 0.2 µm. Putting the weight% mixed by a mixer to prepare an emulsion explosive.

Example 5

PIBSAamine emulsifier at 90 ° C in 87.7% by weight of an oxidant solution at 90 ° C containing 8% by weight of sodium perchlorate, ammonium nitrate, sodium nitrate, water and the like, and 2% by weight of fuel solution at 90 ° C made of wax, mineral oil, etc. Emulsified by emulsifier with 1.7% by weight, 8% by weight of spherical (Atomized type) aluminum and 0.6% by weight of PMB3 (0.04 in specific gravity with ACN polymer, 0.2㎛ thick) were mixed in an emulsion Explosives were prepared.

Example 6

8 weight% of oxidizing agent solution at 90 ° C. containing 8 weight% of sodium perchlorate, ammonium nitrate, sodium nitrate, water, etc. and 1.7 weight of SMO emulsifier at 90 ° C. in 2 weight% of fuel solution at 90 ° C. which is made of wax, mineral oil, etc. 8% by weight of foil type aluminum and PMB2 (copolymer of VDC, ACN, MMA having 50% by weight of ACN) with a specific gravity of 0.04 and a thickness of 0.2㎛ 0.6 wt% was added and mixed with a mixer to prepare an emulsion explosive.

Example 7

8 weight% of oxidizing agent solution at 90 ° C. containing 8 weight% of sodium perchlorate, ammonium nitrate, sodium nitrate, water, etc. and 1.7 weight of SMO emulsifier at 90 ° C. in 2 weight% of fuel solution at 90 ° C. which is made of wax, mineral oil, etc. Emulsifier was added to the emulsifier, and 8% by weight of flaky type aluminum and PMB4 (copolymer of VDC, ACN and MMA having 50% by weight of ACN) with a specific gravity of 0.1 and a thickness of 0.3㎛. 0.6 wt% was added and mixed with a mixer to prepare an emulsion explosive.

Example 8

8 weight% of oxidizing agent solution at 90 ° C. containing 8 weight% of sodium perchlorate, ammonium nitrate, sodium nitrate, water, etc. and 1.7 weight of SMO emulsifier at 90 ° C. in 2 weight% of fuel solution at 90 ° C. which is made of wax, mineral oil, etc. Emulsifier was added to the emulsifier, and 8% by weight of spherical (Atomized type) aluminum and 0.6% by weight of PMB5 (0.1% of specific gravity of ACN and 0.3 µm in thickness) were mixed with a mixer to form an emulsion explosive. Prepared.

Example 9

8 weight% of oxidizing agent solution at 90 ° C. containing 8 weight% of sodium perchlorate, ammonium nitrate, sodium nitrate, water, etc. and 1.7 weight of SMO emulsifier at 90 ° C. in 2 weight% of fuel solution at 90 ° C. which is made of wax, mineral oil, etc. 8% by weight of spherical (Atomized type) aluminum and PMB6 (copolymer of VDC, ACN, MMA with 50% by weight of ACN) having a specific gravity of 0.2 and a thickness of 0.5 µm. The weight percent was added and mixed with a mixer to prepare an emulsion explosive.

Example 10

8 weight% of oxidizing agent solution at 90 ° C. containing 8 weight% of sodium perchlorate, ammonium nitrate, sodium nitrate, water, etc. and 1.7 weight of SMO emulsifier at 90 ° C. in 2 weight% of fuel solution at 90 ° C. which is made of wax, mineral oil, etc. 8% by weight of spherical (Atomized type) aluminum and PMB1 (copolymer of VDC, ACN, MMA with 40% by weight of ACN) having a specific gravity of 0.02 and a thickness of 0.1㎛ 0.6 The weight percent was added and mixed with a mixer to prepare an emulsion explosive.

Example 11

90% of the SMO emulsifier at 90 ° C with 89.21% by weight of an aqueous oxidant solution at 90 ° C containing 8% by weight of sodium perchlorate, ammonium nitrate, sodium nitrate, water and the like, and 2% by weight of the fuel solution at 90 ° C made of wax, mineral oil, etc. Emulsified by emulsifier with%, spherical (Atomized type) 7% by weight of aluminum and PMB2 (copolymer of VDC, ACN, MMA with 50% by weight of ACN with a specific gravity of 0.04 and a thickness of 0.2㎛) 0.09 The weight percent was added and mixed with a mixer to prepare an emulsion explosive.

Example 12

88% oxidant solution at 90 ° C. containing 8% by weight of sodium perchlorate, ammonium nitrate, sodium nitrate, water, etc., and 1.7% SMO emulsifier at 90 ° C. in 2% by weight of 90 ° C. fuel solution consisting of wax, mineral oil, etc. Emulsified by emulsifier with%, followed by 7% by weight of spherical (Atomized type) aluminum and PMB2 (copolymer of VDC, ACN, MMA with 50% by weight of ACN with true specific gravity of 0.04 and thickness of 0.2㎛) 1.1 The weight percent was added and mixed with a mixer to prepare an emulsion explosive.

On the other hand, the results of testing the performance and long-term storage stability of the emulsion explosives prepared by the method according to Examples 1 to 12 listed above are shown in detail in Table 1.

※ Note)

PMB1 = Copolymer of VDC, ACN, MMA with 40% by weight of ACN, with specific gravity of 0.02 and thickness of 0.1㎛.

PMB2 = Copolymer of VDC, ACN, MMA with 50% by weight of ACN, with specific gravity of 0.04 and thickness of 0.2㎛.

PMB3 = ACN polymer with a specific gravity of 0.04 and a thickness of 0.2 µm.

PMB4 = Copolymer of VDC, ACN, MMA with 50% by weight of ACN, with specific gravity of 0.1 and thickness of 0.3㎛.

A polymer of PMB5 = ACN having a specific gravity of 0.1 and a thickness of 0.3 µm.

PMB6 = Copolymer of VDC, ACN, MMA with 50% by weight of ACN, with specific gravity of 0.2 and thickness of 0.5㎛.

As shown in Examples 1 to 8, 5 to 15% by weight of sodium perchlorate, 0.1 to 1.0% by weight of PMB having 0.04 to 0.1 (shell thickness = 0.2 to 0.3 µm) in true specific gravity, Atomized, Flaked and Foil Grade aluminum The composition containing 5-15% by weight is approximately 140 ~ 155% and 5700 ~ 5900m / sec, respectively, and the impact resistance is about 140 ~ 155%. The impact resistance is below 40cm and the long-term storage stability is maintained for more than 1 year. have. However, as shown in Example 9, emulsion explosives using PMB having a specific gravity of 0.2 (Shell thickness = 0.2 μm) are not detonated by primers, and PMB having a specific gravity of 0.02 (shell thickness = 0.1 μm) as shown in Example 10. The long-term storage stability is less than 6 months and the impact resistance is 60cm, which results in lack of performance and stability. In addition, emulsion explosives using 0.09% by weight of PMB having 0.04 (shell thickness = 0.2 μm) in specific gravity as shown in Example 11 had half widths generated by the primer, and in Example 12, PMB having 0.04 (shell thickness = 0.2 μm) in specific gravity Emulsion explosives used 1.1% by weight can be seen that the power is reduced.

On the other hand, MAGNUM of ICI has 140 to 150% of ballistic balls and 5200 to 5400m / sec of explosion speed, which is about 3% lower than that of the present invention, and about 9% of the ball speed drops. And the EMULSTAR of NOBEL EXPLOSIVES FRANCE is 135 ~ 145% ballistic ball and 5400 ~ 5600m / sec speed is about 7% less than the product of the present invention, the ball is about 7%, the speed of about 5% drop.

For reference, the power of gelatin dynamite is 155 to 165% of the ballistic balls and 5700 to 5900 m / sec of the detonation rate, which is about 7% higher than that of the present invention, and the detonation rate is about the same.

As described above, the products of the present invention are summarized in comparison with MAGNUM, EMULSTAR, and gelatin dynamite.

Vinyl diene chloride (VDC), acrylonitrile (ACN), methyl methacrylate (MMA) containing 5 to 15% by weight of sodium perchlorate and 50% by weight of acrylonitrile (ACN) to the oxidizing agent as described above. The effect of the present invention containing 0.2 wt.

Strong granite requires a strong explosive, such as gelatin dynamite, but there is no emulsion explosive to match the dynamite power. However, to reach the level of dynamite, ICI and NOBEL EXPLOSIVES FRANCE have developed and sold products called MAGNUM and EMULSTAR, but this also falls far short of dynamite.

However, the emulsion explosives of the present invention improved the power by about 3 to 10% over MAGNUM and EMULSTAR, and developed only about 7% less than the bombardment force.

Blasting tests with this product resulted in a blasting result almost similar to that of gelatin dynamite.

Claims (2)

Oxidizing agent solution 80-90% by weight, fuel solution 0.1-5% by weight, emulsifier 0.1-5% by weight, organic microspheres 0.1-1.0% by weight and aluminum 5-15% by weight, The organic microspheres may be copolymers of vinyldiene chloride (VDC), acrylonitrile (ACN), methyl methacrylate (MMA) or acrylonitrile (ACN) containing 50% by weight or more of acrylonitrile (ACN). Polymer of which has a specific gravity of 0.04-0.1 g / cc and a thickness of 0.2-0.4 micron; And The aqueous oxidant solution is water-in-oil emulsion explosive, characterized in that containing 5 to 15% by weight of sodium perchlorate relative to the aqueous solution. The method of claim 1, wherein the aluminum is selected from the group consisting of spherical (Atomized type), scaled (Flaked type), foil type (Foil type) and mixtures thereof, the surface is anodized alone or oxidized Water-in-oil emulsion explosives, characterized in that the coating and wax coating.