KR102473077B1 - A non-vibration crushing agent composition ignited with gunpowder and a method of manufacturing the same - Google Patents

Abstract

The present invention relates to a microvibration crusher composition complexed with explosives and a manufacturing method. In order to increase the ignition reactivity, by selecting a composition with a low ignition point, the present invention is to solve the problem of applicability caused because the existing microvibration crusher has no choice but to use a separate ignition port as an ignition method, and also solve the low destructive power due to the low combustion speed, thereby improving the crushing efficiency. The microvibration crusher composition complexed with explosives according to the present invention contains, based on 100 wt% thereof, 27 to 40 wt% of an oxidizing agent, 10 to 20 wt% of a reducing agent, 30 to 50 wt% of a gas generating agent, 0.5 to 10 wt% of industrial nitrocellulose with a nitrogen content of less than 12.2 wt% and in a state melted in acetone as an auxiliary smoke and binder, and 1 to 30 wt% of basic copper carbonate (CuCO_3·Cu(OH)_2) as a power enhancer that functions as both an oxidizing agent and a gas generating agent.

Description

A non-vibration crushing agent composition ignited with gunpowder and a method of manufacturing the same}

The present invention relates to a micro-vibration crusher composition, and more particularly, to a micro-vibration crusher composition and manufacture of a micro-vibration crusher composition ignited with explosives that allow a thermite reaction to occur with thermal energy by the explosion of a small amount of explosives in a sealed hole It's about how.

This section provides background information related to the subject matter of this application and is not necessarily prior art.

There is a blasting method using gunpowder or explosives as a method of crushing bedrock during the construction of a civil structure (for example, a tunnel) or foundation work for the construction of a building. The blasting method using gunpowder or explosives is a method of drilling a plurality of blasting holes in the rock mass, loading gunpowder or explosives into the blasting holes, dispersing, and crushing the rock mass with the energy of exploding the gunpowder or explosives. Instead of having a large destructive power, there are many cases where it is difficult to use in places close to downtown areas and permits because of the large amount of noise and vibration caused by explosions and the scattering of debris.

Due to these problems, various microvibration crushing methods have been developed to crush bedrock without using gunpowder or explosives.

A typical microvibration crushing method is to charge a crushing agent in a blasting hole, spread (mese) it, and rapidly burn the crushing agent by ignition in a sealed state. It is to crush bedrock, etc.

Patent documents that can confirm the background technology of the microvibration crushing method include a Goldschmidt rocking device (Patent No. 10-0184541), a power shock cell for plasma rocking (Patent No. 10-0308081), and a reaction triggering device for rapid expansion mixture (Patent No. 10-0442551). ), plasma blasting method and device (patent 10-0323215), insensitive crushing composition with improved net width, ignition mechanism for low-energy ignition and a rocking device including them (patent 10-0922597), blasting method using an insensitive crushing composition (patent 10 -2062839), etc.

The prior art has the following problems.

First, since general microvibration crushers mainly use aluminum or magnesium with a high melting point and high calorific value as a heating agent, they have problems such as being difficult to ignite or unreacted substances remaining even when ignited.

As a method of igniting the micro-vibration crusher, there is a method of igniting the crushing composition by generating an electric arc by supplying high energy of several tens to hundreds of kilojoules (KJ) or more using high voltage and high power of several thousand volts to tens of thousands of volts. This method increases the risk of safety due to high voltage, equipment failure and misfire due to contact failure due to surge voltage through charging and discharging of large-capacity capacitors, inconvenience in handling equipment due to ultra-large equipment, and energy supply Due to electrical limitations, it is inevitable to dig only a few holes, so the efficiency is very low.

As another ignition method, it is a method of using an ignition port containing a composition capable of causing a high-temperature thermite reaction by electric energy in a tube shaped like a detonator used for detonation of explosives. Compared to the previous method, in that a general blaster can be used Convenient to use. However, it is difficult to artificially adjust the time lag of ignition, so it is impossible to apply it in a tunnel requiring multiple time lag blasting. Of course, it is possible to overcome this problem by using an ignition device including an electronic circuit board, but it is questionable whether a precise time difference of 1 ms is effective for a micro-vibration crusher that is expensive and burns only 1/10 of gunpowder. have.

Second, these microvibration crushing compositions have a very large particle size difference for each raw material, so they cannot achieve a uniform mixed composition size, resulting in partial oxygen deficiency, which is highly likely to stop the reaction or cause misfire. Methyl cellulose (MC), hydroxypropylmethyl cellulose (HPMC), carboxymethyl Through granulation using a binder such as cellulose (CMC), these problems were overcome and reactivity was improved. However, there is a limit to increasing the reactivity in many cases where the granulation is not sufficient or the particles are broken and changed into powder even with a small impact.

Third, even if the composition is granulated, the powdered material with a small particle size existing between the particles serves to lower the combustion rate. The burning speed of general microvibration crushers is 250 to 300 m/s, which is less than 1/10 of the explosive speed of 4,000 to 6,000 m/s of general explosives. When the blast speed is low, the bedrock is hard rock, or it is difficult to exert a sufficient destructive effect in tunnel blasting with a relatively large confining resistance.

Registered Patent No. 10-0184541 Registered Patent No. 10-0308081 Registered Patent No. 10-0442551 Registered Patent No. 10-0323215 Registered Patent No. 10-0922597

The present invention is to solve the above-mentioned problems, and to increase the ignition reactivity, a composition with a low ignition point is used as a binder and the particle size is uniformly formed, thereby providing a separate ignition port as an ignition method of the existing micro-vibration crusher. It is an object of the present invention to provide a microvibration crusher composition and manufacturing method that solves the problem of applicability and the problem of low destructive power due to low burning speed, that is, ignited with gunpowder.

The microvibration crusher composition complexed with explosives according to the present invention contains 27 to 40% by weight of an oxidizing agent, 10 to 20% by weight of a reducing agent, 30 to 50% by weight of a gas generating agent, and acetone as an auxiliary smoke and binder, based on 100% by weight of the total. 0.5 to 10% by weight of industrial nitrided cotton with a nitrogen content of less than 12.2% by weight and 1 to 30% by weight of basic copper carbonate (CuCO3 Cu(OH)2) as a power enhancer that functions as both an oxidizing agent and a gas generator. It is characterized by including.

According to the microvibration crusher composition ignited with explosives and the manufacturing method thereof according to the present invention, the possibility of ignition causing the thermite reaction is increased through the characteristics of industrial nitriding surface, and the combustion rate is increased by 50% or more compared to existing products, so crushing Efficiency can be greatly improved.

In addition, since the particles coated with the industrial nitriding screen are not easily broken due to the characteristics of the industrial nitriding screen and are not greatly affected by temperature change or transportation, the loss is small and the performance can be maintained for a long time.

In addition, the micro-vibration crusher according to the present invention is ignited not only by thermal energy from the explosion of gunpowder or explosives in a closed ball, but also by the detonator used for detonation of general gunpowder or explosives. Therefore, the micro-vibration crusher according to the present invention can be used without a separate ignition port, so it can be said to be superior to existing products in terms of applicability.

1 is a graph of the results of the explosion test of the present invention and a comparative example.
2 is a view showing a crusher to which a micro-vibration crusher composition complexed with explosives according to the present invention is applied.
3 and 4 are photographs showing the results of blasting experiments according to an embodiment of the present invention, respectively.

The microvibration crusher composition complexed with explosives according to the present invention contains 27 to 40% by weight of an oxidizing agent, 10 to 20% by weight of a reducing agent, and 30 to 50% by weight of a gas generating agent, acting as a softening agent and binder, based on 100% by weight of the total amount. 0.5 to 10% by weight of industrial nitriding cotton dissolved in a solvent of acetone (a state in which industrial nitriding cotton is melted using acetone as a solvent) (nitrogen content less than 12.2% by weight), basic carbonic acid serving as a power increasing agent 1 to 30% by weight of copper (CuCO3 Cu(OH)2) is mixed.

1. Oxidizers.

At least one of copper oxide, cupric oxide, manganese dioxide, ferric oxide, triferric oxide, zinc oxide, and silicon dioxide (if two or more are mixed, they can be freely mixed within the above mixing range), and less than 27% by weight is insufficient oxygen supply If the crushing efficiency cannot be satisfied and exceeds 40% by weight, it is difficult to satisfy the crushing efficiency due to the imbalance of the material.

2. Reducing agents.

At least one of aluminum, magnesium, and zirconium is used as the reducing agent (when two or more are mixed, they can be freely mixed within the above mixing range), and the ignition is easy and the heat value during combustion is high, so that the entire combustion reaction is accelerated, and the oxidation is high. It has a heat of reaction (130 - 400 kcal/mol). The mixing ratio of 10 to 20% by weight of the reducing agent is an optimal ratio for the above function.

3. Gas generators.

Magnesium sulfate, copper sulfate heptahydrate (CuSO4 5H2O), magnesium sulfate heptahydrate (MgSO4 7H2O), iron sulfate heptahydrate, zinc sulfate heptahydrate, sulfate monohydrate (H2SO4 H2O), barium hydroxide octahydrate (Ba(OH) 2 8H2O) or at least one of iron oxide hydrate, potassium alum dodecahydrate (AIK(SO4)2 12H20), sodium azide, sodium percarbonate, ammonium pentaborate, ammonium oxalate monohydrate ((NH4)2C2O4 H2O) (2 If more than one is mixed, it can be freely mixed within the above mixing range), and 30 to 50% by weight is the optimal mixing ratio for increasing the crushing efficiency by increasing the gas generation amount.

4. Supporting agents and binders.

The combustion and caking agent functions as a retardant for lowering the ignition temperature and a caking agent for granulating materials, and industrial nitrided cotton is preferably used in an amount of 0.5 to 10% by weight.

The background of the use of industrial nitrile screens will be described as follows.

Basically, it is known that the combustion rate of the microvibration crusher is less than 1/10 compared to the explosion speed of gunpowder or explosives, so that the explosion of gunpowder or explosives does not ignite the microvibration crusher well. That is, sufficient thermal energy must be accumulated to induce the thermite reaction of the crushing agent, but since the energy from gunpowder or explosive explosion is quickly dissipated, sufficient energy to generate the thermite reaction is not gathered. However, if a hole is made in bedrock or concrete and sealed sufficiently with full color, the energy from gunpowder or explosives may ignite the crushing agent in the hole and cause a thermite reaction. However, being able to ignite is different from being able to ignite 100% successfully. For 100% successful ignition, it is necessary to increase the reactivity of the crushing agent.

Sulfur has been typically used as a softening agent to increase the reactivity of the crushing agent. Sulfur lowers the ignition temperature to make the reaction easier. However, in several experiments, it is difficult to satisfy 100% of the ignition success rate with only sulfur, and when a lot of sulfur is added, problems arise not only in the performance of the crusher but also in the generation of toxic gases.

In order to solve this problem, in the present invention, industrial nitrided cotton (C ₂₄ H ₂₉ O ₉ (NO ₃ ) _11, nitrogen content less than 12.2% by weight) is selected as a key composition that increases the reactivity of the crusher to the extent that 100% successful ignition is possible did Industrial nitration cotton with a nitrogen content of less than 12.2% by weight is not classified as gunpowder. The ignition point of industrial nitriding screen is 160 to 170 degrees, which is lower than the ignition point of sulfur, which is 230 degrees, which can increase reactivity.

The industrial nitriding surface preferably has a nitrogen content of 11.5 to less than 12.2% by weight.

In addition, the purpose pursued by the present invention can be achieved only when industrial nitriding cotton is used as a binder rather than simply entering the mixture. To this end, it is possible to make particles of a certain size mixed with an oxidizing agent, reducing agent, gas generating agent, and power increasing agent by demonstrating the function of a binder through the process of melting industrial nitriding screen using a solvent and mixing it evenly using a mixer. .

The industrial nitrided cotton (nitrogen content less than 12.2% by weight) is used after being dissolved in a solvent. Acetone is mainly used as a solvent, and acetone in a capacity of 800 cc is appropriate for a weight of 150 g of industrial nitriding screen at room temperature. In the case of industrial nitriding cotton (nitrogen content less than 12.2% by weight), since it is used as a caking agent and a softening agent at the same time, it is mixed in a larger amount than the general caking agent mixing ratio of 0.1 to 0.5% by weight.

At this time, acetone gas used as a solvent may adversely affect the eyes and respiratory system when exposed to the human body. It is preferable to add a ventilation device to the cover of the mixer to discharge acetone gas generated during the mixing process to prevent contact with the human body. A pipe is connected to the outside of the cover, so when the valve is opened, the acetone gas is discharged far away from the human body through a ventilation device.

In addition, complete emission of acetone gas may be induced by injecting carbon dioxide or nitrogen. After mixing is completed, inject carbon dioxide or nitrogen into the cover through a ventilation device and a separate pipe connection passage, and the appropriate injection amount is about 2/3 of the mixer capacity.

Industrial nitriding screen (nitrogen content less than 12.2% by weight) with such a composition not only increases the possibility of ignition due to its low ignition point, but also particles coated with industrial nitriding screen (nitrogen content less than 12.2% by weight) dissolved in a solvent of acetone are shown in the table. 1 (particle size analysis result table), compared to existing products, the size is uniform and the particles of fine size are small, so the heat energy from gunpowder or explosives is well transmitted and the total area of the particles in contact is large, making it easier to ignite the thermite reaction. As a result of this, the combustion speed of the present invention is increased to 500 ~ 600m / s, which is twice the 250 ~ 300m / s of the existing product, as shown in FIG. In addition, particles coated with industrial nitrided cotton (nitrogen content less than 12.2% by weight) dissolved in acetone solvent are not easily broken and are not greatly affected by temperature change or transportation, so long-term performance can be maintained.

body number diameter
(mm) A B the present invention
micro-vibration crusher Residual amount (g) ratio Residual amount (g) ratio Residual amount (g) ratio No.10 2.000 14.02 2.35% 1.48 0.30% 89.21 18.18% No.20 0.850 282.97 47.38% 158.19 32.31% 279.74 57.00% No. 30 0.600 36.64 6.13% 23.5 4.80% 13.59 2.77% No.40 0.425 47.09 7.88% 26.82 5.48% 16.56 3.37% No. 50 0.300 30.56 5.12% 22.71 4.64% 11.22 2.29% Pan - 186 31.14% 256.88 52.47% 80.45 16.39% Total 597.28 100.00% 489.58 100.00% 490.77 100.00%

6. Power Boosters

The power enhancer is basic copper carbonate (CuCO3 Cu(OH)2).

Basic copper carbonate contains an oxidizing agent and a hydrate, which can increase thermal energy and gas pressure. However, since separate heat energy is required for the reaction to separate the oxidizing agent and the hydrate, it is not used as a composition for general micro-vibration crushers. However, the micro-vibration crusher according to the present invention can further increase the crushing force by causing the thermite reaction by the thermal energy of gunpowder (including gunpowder, explosives, and detonator) and at the same time separating the oxidizing agent and hydrate of basic copper carbonate. .

The mixing ratio of basic copper carbonate is 1 to 30% by weight to enable high gas pressure and sufficient oxygen supply, that is, when less than 1% by weight is mixed, it is difficult to see a significant increase in power, and when it exceeds 30% by weight The energy required for the reaction to separate CuO and H2O increases, and there is a risk that the possibility of ignition is lowered.

Basic copper carbonate [CuCO3 Cu(OH)2] can be seen in the form of 2CuO CO2 H2O, and since there are CuO that can act as an oxidizing agent and CO2 and H2O that can act as a gas generator, reducing agents (aluminum ( Al), etc.) and can be simply used as a crushing composition. Basic copper carbonate [CuCO3 Cu(OH)2] generates high heat as CuO reacts with aluminum, a reducing agent, to generate high heat.

3CuCO3·Cu(OH)2+4Al → 6Cu+3CO2+3H2O+2Al2O3 The gas volume is 174.37 l/kg and the calorific value is 698.97 kcal/kg.

A mixture of basic copper carbonate and aluminum can be stored for a long time without fear of deterioration (chemical stability).

Meanwhile, in the present invention, an antistatic agent may be further added as needed.

7. Antistatic agent.

Antistatic agents are used to reduce the risk of explosion due to static electricity when handling crushing agents. do.

The manufacturing method of the micro-vibration crusher composition complexed with explosives according to the present invention is as follows.

1. Mixing ingredients.

Add oxidizing agent, reducing agent, gas generating agent, industrial nitriding cotton (industrial nitriding cotton melted with acetone solvent) and basic copper carbonate to the mixer and mix them. First, oxidizing agent, reducing agent, gas generating agent and basic copper carbonate are mixed for 10 to 20 minutes, then industrial nitrided cotton dissolved in acetone solvent is introduced and mixing is performed for 20 to 30 minutes.

2. Acetone gas (vapour) capture/exhaust.

While materials are mixed through the entire process, acetone gas is collected through the cover of the mixer, and the acetone gas is discharged from the inside of the mixer by opening the ventilator (opening the valve of the ventilator).

In this process, an action of inducing acetone gas emission may be further included.

For example, by injecting carbon dioxide or nitrogen into the mixer, acetone gas is discharged.

2 shows an example for crushing using the micro-vibration crusher composition 1 complexed with explosives according to the present invention.

A crushing hole (2) is drilled in the rock mass, and the explosives (3) (gunpowder or explosives, detonator), the micro-vibration crushing agent composition (1) ignited with the explosives of the present invention, and the vehicle (4) are placed in the crushing hole (2). Install (fill).

As the vehicle 4, sand or the like can be used.

<Example 1>

In order to compare the crushing effect according to the amount of basic copper carbonate, it was confirmed whether the crushing agent was put into a steel pipe having a diameter of 20 mm and a length of 300 mm, and when thermal energy was applied.

division oxidizer reducing agent gas generator basicity
copper carbonate for industrial use
nitriding screen result Formulation 1-1 35 13 42 5 5 full width Formula 1-2 33 13 39 10 5 full width Formula 1-3 29 14 34 20 3 full width Formula 1-4 24 14 29 30 3 fire

As can be seen in FIG. 3, the experimental results according to the mixing ratio confirmed complete explosion when 5 to 20% by weight of basic copper carbonate was mixed, and it was confirmed as non-explosion when 30% by weight was mixed.

<Example 2>

In order to compare the crushing effect according to the amount of industrial nitriding screen, the crushing agent was put into a steel pipe with a diameter of 20 mm and a length of 300 mm, and when thermal energy was applied, whether or not the crushing effect was confirmed was confirmed.

division oxidizer reducing agent gas generator basicity
copper carbonate for industrial use
nitriding screen result Formula 2-1 33 13 44 9 One full width Formula 2-2 33 13 43 9 2 full width Formula 2-3 32 13 42 8 5 full width Formula 2-4 30 12 40 8 10 fire

As can be seen in FIG. 4, the experimental results according to the blending ratio confirmed full width when 1 to 5% by weight of industrial nitriding cotton was mixed, and it was confirmed as low width when 10% by weight was mixed.

1: Micro-vibration crusher composition complexed with explosives,
2: crushing hole, 3: gunpowder
4: vehicle,

Claims (6)

Based on the total 100% by weight, 27 to 40% by weight of oxidizing agent, 10 to 20% by weight of reducing agent, 30 to 50% by weight of gas generator, dissolved in a solvent of acetone as an auxiliary smoke and binder, industrial nitride screen with nitrogen content of less than 12.2% by weight 0.5 to 10% by weight, a micro-vibration crusher composition ignited with explosives, characterized in that it contains 1 to 30% by weight of basic copper carbonate (CuCO3 Cu(OH)2) as a power increasing agent that functions as both an oxidizing agent and a gas generating agent .
delete delete delete In the mixer, 27 to 40% by weight of oxidizing agent, 10 to 20% by weight of reducing agent, 30 to 50% by weight of gas generating agent, basic copper carbonate (CuCO3 Cu (OH) 2) a first step of adding 1 to 30% by weight and mixing;
A second step of adding and mixing 0.5 to 10% by weight of industrial nitriding cotton having a nitrogen content of less than 12.2% by weight and dissolved in a solvent of acetone as an auxiliary smoke and binder;
A method for producing a microvibration crusher composition ignited with gunpowder, characterized in that it comprises a third step of collecting acetone vapor generated in the mixer during the second step. The method according to claim 5, wherein the third step is to inject carbon dioxide or nitrogen into the mixer to induce discharge of the acetone vapor.

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