JPS5815467B2 - Water-in-oil emulsion explosive composition - Google Patents

Description

Detailed Description of the Invention The present invention is a water-in-oil type (hereinafter abbreviated as W2O type) emulsion explosive composition that does not contain a sensitizing agent and contains an emulsion stabilizer, which improves detonation sensitivity at small diameters and low temperatures. This invention relates to a W10 type emulsion explosive composition with excellent stability over time.

Conventionally, we have developed products that contain small hollow spheres or microbubbles, do not contain sensitizers, and have small diameters (direct breakage 12.5 mm to 31.3 ut).
), a W10 type emuljoy explosive composition is known in which the detonation sensitivity does not decrease over a long period of time with a No. 6 or No. 8 detonator.

For example, US Pat. No. 4,110,134 contains ammonium, alkali metal, or alkaline earth metal perchlorate as a component of an inorganic oxide salt, micro hollow spheres as a temporary specific gravity adjuster, and 6 even after 2 years in the case of a 12.5 mm paper cartridge (temporary specific gravity 1-15)
It is recorded that the bomb exploded completely with the detonator.

Further, in US Pat. No. 4,149,916, a perchlorate of ammonium, alkali metal, or alkaline earth metal is contained as a component of an inorganic oxide salt, microbubbles are contained as a temporary specific gravity adjusting agent, and the diameter is 31. 1 for a 3 mg paper tube or polyethylene tube (temporary specific gravity 0.94)
It is stated that even after seven months have passed (temporary specific gravity 1.07), the bomb will be completely detonated by a No. 8 detonator (explosive temperature 32.2°C).

Further, in US Pat. No. 4,149,917, it does not contain ammonium, alkali metal or alkaline earth metal perchlorate as a component of the inorganic oxide salt, but contains microbubbles as a temporary specific gravity adjusting agent, and contains microbubbles with a diameter of 31 mm. In the case of a 3-inch paper cartridge or polyethylene cartridge (temporary specific gravity 0.95), the explosive temperature reaches 21 until it explodes completely with a No. 6 detonator after two months have elapsed.
．． It is stated that the bomb will be completely detonated using a No. 8 detonator after 8 months (explosive temperature: 21.1°C).

U.S. Pat. No. 4,110,134, U.S. Pat. No. 414, supra.
No. 9916, W10 emulsion explosive compositions containing a relatively sensitive class of ammonium, alkali metal or alkaline earth metal perchlorate as a component of an inorganic oxide salt are It is stated that the stability of detonation sensitivity over time is good.

However, perchlorates of ammonium, alkali metals, or alkaline earth metals have lower solubility in water than ammonium nitrate, and their own detonation sensitivity is high, so there is a high risk of explosion due to friction or impact during manufacturing.

There were also problems such as toxic chlorine gas or chlorine compound gas mixed into the gas produced after the explosion.

However, if it does not contain ammonium, alkali metal or alkaline earth metal perchlorates, U.S. Pat.
As described in the specification of No. 134, the detonation sensitivity is greatly reduced.

By the way, according to US Pat. No. 4,149,917,
W10 emulsion explosive compositions containing microbubbles without ammonium, alkali metal, or alkaline earth metal perchlorates can be completely destroyed after eight months without the use of a No. 8 detonator, which is more powerful than a No. 6 detonator. Don't explode.

Therefore, from these facts, W1 that does not contain ammonium, alkali metal or alkaline earth metal perchlorate
Type 0 emulsion explosive compositions had a problem in that the stability over time of detonation sensitivity was inferior to those containing them.

The present invention was obtained as a result of intensive research to solve the above-mentioned problem, namely, the poor stability of detonation sensitivity over time.

The object of the present invention is to contain no ammonium, alkali metal or alkaline earth metal perchlorates;
It is an object of the present invention to provide a W10 type emulsion explosive composition which has excellent stability of detonation sensitivity over time by containing an emulsion stabilizer.

In addition, by containing ammonium, alkali metal or alkaline earth metal perchlorate as a component of the W10 type emulsion explosive composition of the present invention and adding an emulsion stabilizer, it is possible to It is possible to provide a W10 emulsion explosive composition which has better stability over time in detonation sensitivity than a W10 emulsion explosive composition containing an earth metal perchlorate.

That is, the W10 type emulsion explosive composition of the present invention is (a)
a dispersed phase of an oxidizing agent aqueous solution consisting of ammonium nitrate or ammonium nitrate and other inorganic oxide salts and (b) water;
(c) Emulsifier (in the continuous phase of fuel oil/wax) and
e) W10 type emulsion consisting of an emulsion stabilizer that is a fine powder with an average particle size of 1.0μ or less and insoluble or poorly soluble in water and oil; and (f) W10 type emulsion containing microscopic hollow spheres or microbubbles. An emulsion explosive composition.

The aqueous oxidizing agent solution of the W10 type emulsion explosive composition of the present invention contains ammonium nitrate as a main component and contains other inorganic oxidizing acid salts as necessary.

Here, other inorganic oxide salts include, for example, sodium nitrate,
Alkali metal or alkaline earth metal nitrates such as calcium nitrate, and ammonium, alkali metal or alkaline earth metal chlorates or perchlorates such as sodium chlorate, ammonium perchlorate, sodium perchlorate, etc. It's salt.

These inorganic oxidized acid salts may be used alone or as a mixture of two or more.

The amount of ammonium nitrate is generally 40% to 8% of the total.
0% (on a weight basis, the same applies hereinafter), and if necessary, other inorganic oxide salts may be contained in an amount of 30% or less of the total inorganic oxide salts containing ammonium nitrate.

Fuel oils and waxes are hydrocarbons, such as paraffinic hydrocarbons, olefinic hydrocarbons, nandene hydrocarbons, aromatic hydrocarbons, saturated or unsaturated hydrocarbons,
Petroleum, refined mineral oils, lubricants, liquid paraffin, etc. and hydrocarbon derivatives, such as nitrohydrocarbons.

Waxes include unrefined microcrystalline wax derived from petroleum, purified microcrystalline wax, paraffin wax, mineral waxes such as montan wax and osikerite, animal waxes such as whale wax, and mixed waxes such as honey. Rowe et al.

These fuel oils and waxes may be used alone or as a mixture of two or more.

The blending amount of fuel oil and waxes is generally 1.5% to 10%.
It is.

The emulsifier is not particularly limited, and includes all conventionally known emulsifiers that form a W10 type emulsion.

For example, sorbitan fatty acid esters, i.e. sorbitan monolaurate, sorbitan monooleate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan dioleate, norbitan trioleate, mono- or diglycerides of fatty acids, i.e. stearin. Acid monoglycerides, etc., polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, etc., oxazoline derivatives, imidacillin derivatives, phosphoric acid esters, alkali metal salts or alkaline earth metals of fatty acids salts, primary, secondary and tertiary amines or nitrates or acetates of primary, secondary and tertiary amines.

These emulsifiers may be used alone or as a mixture of two or more.

The amount of emulsifier added is generally 0.5% to 5%.

The emulsion stabilizer used in the present invention has an average particle size of 1.0μ
It is a fine powder that is insoluble or sparingly soluble in water and oil.

If the average particle size of the emulsion stabilizer exceeds 1.0μ, it is usually W1.
Since the particle size is larger than the particle size of the dispersed phase obtained in the type 0 emulsion explosive composition, the effect of the emulsion stabilizer cannot be obtained considering the effects of the emulsion stabilizer described later.

The average particle size of this emulsion stabilizer should be as fine as possible considering its effects, but it is usually 0.005 μm.
~0.5μ.

Further, the dispersion directionality of the emulsion stabilizer is preferably such that it easily migrates to the continuous phase side or to the interface between the dispersed phase and the continuous phase.

Examples of such emulsion stabilizers include higher fatty acid alkali metal salts or alkaline earth metal salts such as zinc stearate, zinc myristate, aluminum stearate, and magnesium myristate, carbon black, anhydrous silica, iron oxide (black, red or yellow), titanium dioxide, talc, kaolin, zinc white, etc.

These emulsion stabilizers may be used alone or as a mixture of two or more.

The blending amount of the emulsion stabilizer is generally o, oi% to 10%, preferably 0.05% to 5%.

Further, the temporary specific gravity of the W10 type emulsion explosive composition of the present invention is adjusted to 0.80 to L35 (preferably 1.00 to 1.15) using a temporary specific gravity adjusting material.

The temporary specific gravity adjusting agent is a micro hollow sphere or a micro bubble, and the micro hollow sphere is, for example, glass, alumina, shale, shirasu, silica sand, volcanic rock, sodium silicate, borax,
Inorganic microscopic hollow spheres obtained from pearlite, obsidian, etc.
Carbonaceous micro hollow spheres obtained from pitch, coal, etc., synthetic resin micro hollow spheres obtained from phenolic resin, polyvinylidene chloride, epoxy resin, urea resin, etc., and these micro hollow spheres are of one or two types. Used as a mixture of more than one species.

The content of the micro hollow spheres is generally 1% to 10%.

Microbubbles include, for example, microbubbles obtained by foaming containing a chemical blowing agent, or microbubbles obtained by mechanically blowing air or other gas during or after the formation of a W10 emulsion. It is.

Chemical blowing agents include, for example, inorganic chemical blowing agents such as alkali metal boron hydrides, those using a combination of sodium nitrite and urea, or N-N'-dinitron pentamethylenetetramine, azodicarboxylic acid amide, azo These include organic chemical blowing agents such as bisisobutyronitrile.

These chemical blowing agents may be used alone or as a mixture of two or more.

The amount of chemical blowing agent added is generally 0.01% to 2%.

The W10 type emulsion explosive composition of the present invention as described above is characterized by containing the above-mentioned emulsion stabilizer, and the effects of the emulsion stabilizer are thought to be as follows. .

That is, by dispersing the emulsion stabilizer fine powder toward the continuous phase side of the W10 emulsion or toward the interface between the continuous phase and the dispersed phase, the fine powder of the emulsion stabilizer is physically dispersed toward the continuous phase or the interface between the continuous phase and the dispersed phase. In order to strengthen this, it has the effect of suppressing the transition phenomenon from aggregation of the dispersed phase to coalescence and separation, which is the main cause of W10 emulsion failure, and as a result, the morphology of the W10 emulsion becomes stable for a long period of time. It is thought that the effect of improving the stability over time of the detonation sensitivity of the W10 type emulsion explosive composition of the present invention can be obtained.

The method for producing the W10 type emulsion explosive composition of the present invention is, for example, as follows.

That is, an oxidizing agent aqueous solution is obtained by dissolving ammonium nitrate or a mixture of ammonium nitrate and other inorganic oxidizing acid salts in water at about 80°C to 90°C.

On the other hand, a mixture of a combustible agent and an emulsion stabilizer (hereinafter abbreviated as a combustible mixture) is obtained by dissolving and mixing an emulsifier, fuel oil/waxes, and an emulsion stabilizer at 80°C to 90°C.

Next, first put the combustible mixture into a heat-retainable container with a certain volume, and mix and stir for about 5 minutes at about 160 rpm using a commonly used propeller blade stirrer while gradually adding the oxidizing agent aqueous solution. A W10 type emulsion at ℃ is obtained.

Next, a W10 type emulsion explosive composition is obtained by mixing micro hollow spheres or a chemical blowing agent into the W10 type emulsion using a vertical kneading machine at about 30 rpm.

In addition, when containing microbubbles made of gas such as air instead of microbubbles made of micro hollow spheres or a chemical blowing agent, the composition of the W10 emulsion explosive can be changed by stirring while blowing gas such as air into the W10 emulsion. get something

Next, the W10 type emulsion explosive composition of the present invention will be specifically explained using Examples and Comparative Examples.

Note that all parts and percentages in each example are based on weight.

Example 1 A W10 type emulsion explosive composition having the formulation shown in Table 1 was manufactured as follows.

First, 3766 parts of ammonium nitrate and 227 parts of sodium nitrate were added to 544.5 parts of water and dissolved by heating to obtain an oxidizing agent aqueous solution at about 85°C.

On the other hand, a mixture of 84.5 parts of sorbitan monooleate and 169.5 parts of unrefined microcrystalline wax was heated and dissolved to obtain a combustible agent solution at about 85°C.

Next, 15 parts of carbon black having an average particle size of 0.03 μm was uniformly dispersed as an emulsion stabilizer in this combustible agent solution to obtain a combustible agent mixture.

First, put the combustible agent mixture in a heat-insulating container, then gradually add the oxidizing agent aqueous solution and mix and stir for 5 minutes at about 1600 rpm using a propeller blade stirrer.
A W10 type emulsion at about 80°C was obtained.

Next, 193.5 parts of glass micro hollow spheres having an average particle size of 75 μm were mixed into the W10 emulsion using a vertical kneading machine at about 3 Orpm to obtain a W10 emulsion explosive composition.

This W10 type emulsion explosive composition has a diameter of 25 mm.
The tablets were molded to have a length of about 180 mm and a dosage of 100 gr, and were packaged in Vizcose processed paper and subjected to various performance tests.

Performance tests include (a) measurement of provisional specific gravity one day after production;
b) After conducting a forced deterioration storage test in which the sample cartridge was kept at 60°C for 24 hours, then at -15°C for 24 hours, and this temperature cycle was repeated as one cycle, Determine the number of temperature cycles that can cause a complete explosion when performing an explosion test at -5℃, and calculate the number of temperature cycles at room temperature (15℃).
Estimated as the number of months of storage for complete explosion in storage at 0 to 30°C (estimated based on experimental confirmation that the 1 part degree cycle corresponds to approximately 1 month in storage at room temperature).

), and (c) provisional specific gravity measurements during the detonation test described in (b) above were conducted.

The results were as shown in Table 1.

Examples 2 to 9 W10 type emulsion explosive compositions having the formulations shown in Table 1 were manufactured according to Example 1.

Sample cartridges were prepared from this W10 type emulsion explosive composition in the same manner as described in Example 1, and performance tests were conducted on the same items.

The results are as shown in Table 1.

In addition, in Example 6, a chemical blowing agent (N-N'
- dinitrosopentamethylenetetramine) was decomposed and foamed to adjust the tentative specific gravity, and the same performance tests as in Example 1 were conducted.

Examples 10 to 11 W10 type emulsion explosive compositions having the formulation shown in Table 1 were manufactured by the following method.

That is, first, a W10 type emulsion was obtained according to Example 1.

Next, while blowing air through a thin nozzle into the W10 emulsion, use a propeller blade stirrer to mix the mixture for about 1 hour.
Mixing and stirring was performed for 2 minutes at 600 rpm to introduce microbubbles of air, thereby obtaining a W10 type emulsion explosive composition with a required tentative specific gravity.

Sample cartridges were prepared from this W10 type emulsion explosive composition in the same manner as described in Example 1, and performance tests were conducted on the same items.

The results are shown in Table 1.

Examples 1 to 5 W10 type emulsion explosive compositions having the formulations shown in Table 2 were manufactured according to Example 1.

A sample cartridge was prepared from this W10 type emulsion explosive composition in the same manner as described in Example 1, and performance tests were conducted on the same items.

The results are shown in Table 2.

Comparative Example 6 A W10 type emulsion explosive composition having the composition shown in Table 2 was produced according to Examples 10-11.

A sample cartridge was prepared from this W10 type emulsion explosive composition in the same manner as described in Example 1, and performance tests were conducted on the same items.

The results are shown in Table 2.

Next, the results of each example and the results of each comparative example will be compared and explained.

In the case of W10 type emulsion explosive compositions (Comparative Examples 1 and 2) that do not contain fine powder as an emulsion stabilizer and inorganic perchlorate of the present invention, complete detonation is possible at -5°C using a No. 6 detonator. The storage periods were 22 months and 20 months, respectively, but the average particle size defined by the present invention was 1. W10 emulsion explosive compositions (Examples 1.2 and 5) containing carbon black with an average particle size of 0.03μ and 0.2μ as an emulsion stabilizer having a particle size of θμ or less, anhydrous silica with an average particle size of 0.7μ In the case of a W10 type emulsion explosive composition (Example 3) containing zinc stearate and a W10 type emulsion explosive composition (Example 4) containing zinc stearate having an average particle size of 0.3μ, a No. 6 detonator was used to The storage periods for complete explosion at 5℃ are 32 months, 30 months, and 3 months, respectively.
They were 1 month, 29 months, and 29 months.

In addition, in the case of a W10 type emulsion explosive composition (Comparative Example 5) in which the fine powder as an emulsion stabilizer of the present invention was not blended, but sodium perchlorate was blended as an inorganic oxide salt, a No. 6 detonator was used. The storage period for complete detonation at -5°C was longer than that without perchlorate (29 months), but the emulsion stabilizer with an average particle size of 1.0μ or less as specified in the present invention In the case of the W10 type emulsion explosive composition (Example 9) containing carbon black with an average particle size of 0.03μ, the storage period for complete detonation at -5°C using a No. 6 detonator is 38 months. there were.

In the case of a W10 type emulsion explosive composition (Comparative Example 6) containing microbubbles without blending the emulsion stabilizer of the present invention, inorganic perchlorate, and glass micro hollow spheres as a temporary specific gravity adjuster, No. 6 The storage period for complete detonation at -5°C using a detonator was 16 months, but carbon black with an average particle size of 0.03μ was blended as an emulsion stabilizer with an average particle size specified by the present invention. In the case of the W10 emulsion explosive composition (Example io) and the W10 emulsion explosive composition containing anhydrous silica with an average particle size of 0.7 μm (Example 11), the composition was heated at 15°C using a No. 6 detonator. The storage periods for complete detonation were 28 months and 27 months, respectively.

Average particle size defined in the present invention 1. Emulsion stabilizers having θμ or more, i.e. 2.0μ carbon black and 3.0μ
In the case of W10 type emulsion explosive compositions containing anhydrous silica (Comparative Examples 3 and 4), the storage periods for complete detonation at -5°C using a No. 6 detonator were 21 months and 1 month, respectively.
It was 9 months.

An emulsion stabilizer having an average particle size of 1.0μ or less as specified in the present invention is added at the compounding point, but no inorganic perchlorate is added, and a chemical blowing agent (N・N'-dinitrone penetra) is used as a temporary specific gravity adjuster. W containing microbubbles due to tametelenetetramine)
In the case of Type 10 emulsion explosive composition (Example 6),
The number of months it could be stored for complete detonation using a No. 6 detonator at -5°C was 28 months.

In the case of a W10 type emulsion explosive composition (Example 7.8) in which a mixture of purified microcrystalline wax and lubricating oil or liquid paraffin was used instead of the unrefined microcrystalline wax of Example 1, a No. 6 detonator was used. The storage periods for complete explosion at -5℃ were 31 months and 29 months, respectively.

As explained above based on each Example and each Comparative Example, the W10 type emulsion explosive composition of the present invention has greatly improved stability over time of detonation sensitivity.

Claims (1)

[Claims] 1. (a) A dispersed phase of an oxidizing agent aqueous solution consisting of (a) ammonium nitrate or ammonium nitrate and other inorganic oxidizing acid salts and (0) water, (c) a continuous phase of fuel oil and waxes) an emulsifier, and (e) an average particle size. A water-in-oil emulsion explosive composition comprising a water-in-oil emulsion consisting of an emulsion stabilizer that is a fine powder of 0μ or less and insoluble or sparingly soluble in water and oil, containing microscopic hollow spheres or microbubbles. thing.