JPS5815468B2 - Water-in-oil emulsion explosive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-in-oil emulsion explosive composition that contains water-soluble glycinonitrile nitrate as a novel sensitizing agent and has excellent low-temperature detonability and safety. be.

In general, a water-in-oil type (hereinafter abbreviated as W2O type) emulsion explosive composition is a dispersion of a continuous phase of fuel oil/wax, water, an inorganic oxide salt, and an aqueous solution in which flammable substances are dissolved as necessary. A W10 type emulsion composition consisting of a phase and an emulsifier contains microscopic hollow spheres as a temporary specific gravity adjuster, and a sensitizing agent is added when higher explosive reactivity and detonator detonation properties are required. is used.

There are various types of sensitizing agents that have been conventionally used for the above purposes, such as:
Highly sensitive sensitizers such as nitroglycerin (N/G), TNT, trimethylene trinitramine (RDX), solid sensitizers such as fine aluminum powder, monomethylamine mononitrate (MMAN), ethylene glycol mono There were water-soluble sensitizers such as nitrate, and poorly water-soluble sensitizers such as nitroparaffin.

Among these conventional sensitizers, N/G, TNT, RDX, etc. are explosives, and they are very problematic in terms of safety during manufacture and handling, and are also expensive, so they are not economical. There was a problem.

Further, the fine aluminum powder used as a sensitizing agent is very expensive and requires particular care in handling during production.

Among nitroparaffins, nitromethane is mainly used, but it is expensive and poorly soluble in water, so in order to mix it uniformly into a hydrous explosive composition, it is necessary to form a gel using a gelling agent for nitromethane. It was necessary to take manufacturing measures such as making the

Water-soluble sensitizers such as monomethylamine mononitrate are relatively inexpensive, and since they are used after being dissolved in water, they are highly safe and easy to manufacture; The problems were that the amount was high (generally around 20%) and that the low-temperature detonability was poor.

As a result of intensive research to eliminate the drawbacks of conventional sensitizing agents as described above, the present invention uses a new water-soluble glycinonitrile nitrate as a sensitizing agent. Moreover, it was possible to obtain a W10 type emulsion explosive composition having excellent low-temperature detonation properties and detonation properties.

That is, the W10 type emulsion explosive composition of the present invention comprises a dispersed phase containing ammonium nitrate or ammonium nitrate and other inorganic oxide salts and water, a continuous phase of fuel oil/wax, an emulsifier, and a temporary specific gravity adjuster. The W10 emulsion explosive composition is characterized in that the dispersed phase contains glycinonitrile nitrate as a novel sensitizing agent.

Glycinonitrile nitrate (hereinafter referred to as GN) used in the present invention
(abbreviated as N) is produced by reacting glycinonitrile with nitric acid, or by neutralizing glycinonitrile sulfate with (N) hydroxide, and then reacting the separated and extracted glycinonitrile with nitric acid. Easy to manufacture.

This GNN is a water-soluble crystal, is non-explosive, easy to handle, and has excellent safety.

The amount of GNN to be blended in the W10 type emulsion explosive composition can be arbitrarily determined depending on the performance of the target W10 type emulsion explosive composition, but is usually 1 to 40% (by weight, the same applies hereinafter), preferably 5%. ~20%, but
Even if it is less than 5%, it has detonator detonation properties and low temperature detonation properties.

The components other than GNN of the W10 type emulsion explosive composition of the present invention are conventionally commonly used components, and specifically, are as follows.

That is, ammonium nitrate or ammonium nitrate and other inorganic oxide salts are usually used in an amount of 40 to 90%.

Examples of other inorganic oxide salts used with ammonium nitrate include nitrates such as sodium nitrate and calcium nitrate, chlorates such as sodium chlorate, and perchlorates such as sodium perchlorate.

Water is usually used in an amount of 5 to 25%, preferably 8 to 15%.

Among fuel oils and waxes, fuel oils include hydrocarbons such as paraffinic hydrocarbons, olefinic, naphthenic, or aromatic saturated or unsaturated hydrocarbons, petroleum, refined mineral oil, liquid paraffin, etc. Hydrocarbon derivatives such as nitrohydrocarbons and the like.

Examples of waxes include microcrystalline wax derived from petroleum.

Paraffin wax and the like, mineral waxes such as montan wax and osikerite, animal waxes such as spermaceti wax, and insect waxes such as beeswax.

The amount of these fuel oils and waxes is usually 1 to 10%.
used.

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

For example, (1) sorbitan fatty acid esters, such as sorbitan monolaurate, sorbitan monooleate, sorbitan monopalmitate, sorbitan monostearate, rubitan sesquioleate, sorbitan dioleate, and sorbitan trioleate; (2) fatty acids; Q
Monoglyceride or diglyceride, i.e., stearic acid monoglyceride, etc., (3) Polyoxyethylene sorbitan fatty acid ester, i.e., polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan, monostearate, etc., (4) Oxazoline derivative, (5) imidacillin derivatives, (6) phosphoric acid esters, (7) alkali metal salts or alkaline earth metal salts of fatty acids, (8) primary, secondary or tertiary amines, or
secondary, secondary or tertiary amine nitrates or acetates, and these are usually used in an amount of 0.1 to 5%.

As the temporary specific gravity adjuster, micro hollow spheres, chemical foaming agents, surfactants, etc. are used.

Microscopic hollow spheres include glass, silica, phenolic resin, etc., and these are usually used in an amount of 1 to 7%.Chemical blowing agents include those used in combination with sodium nitrite and thiourea, and N-N'-di There are organic substances such as nitrosopentamethylenetetramine, and these are usually used in an amount of 0.01 to 3%.

In addition, when it is necessary to adjust the oxygen balance etc. in the composition, flammable substances include ethylene glycol, formamide, sugars, gums, urea, aluminum powder, coal powder, sulfur powder, etc., and these are usually ~20% used.

The W10 type emulsion explosive composition of the present invention can be obtained, for example, by the following manufacturing method.

That is, all or part of an organic oxide salt such as ammonium nitrate and glycinoni)lyl nitrate were heated at 50 to 90°C.
A W10 type emulsion composition is prepared by mixing and stirring an aqueous solution dissolved in water and a mixed melt obtained by mixing an emulsifier and fuel oil/waxes at 50 to 90°C, and further adding to the W10 type emulsion composition, A W10 type emulsion explosive composition is obtained by mixing fine hollow spheres as a temporary specific gravity adjuster.

When mixing chemical blowing agents without using micro hollow spheres,
It is added before or after forming the W10 emulsion composition and foamed to obtain a W10 emulsion explosive composition.

The W10 type emulsion explosive composition of the present invention obtained in this manner has sufficient detonator detonation properties in a small diameter and open state due to the sharpening effect of GNN, and has particularly excellent detonation properties at low temperatures. be.

Next, the method for producing GNN will be specifically explained using reference examples, and the performance effects of the W10 type emulsion explosive composition of the present invention will be specifically explained using comparative examples and examples.

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

The performance of the W10 type emulsion explosive composition obtained on each side was evaluated by a performance test consisting of a low-temperature detonation test and a detonation velocity measurement.

A sample of the W10 type emulsion explosive composition used in this performance test was placed in a polyethylene tube with a diameter of 25 mm.
It was used as a medicine package filled with 200 g of type 0 emulsion explosive composition.

The low-temperature detonation test was carried out by heating a sample into which a probe for measuring detonation velocity was inserted to a predetermined temperature in a thermostat, detonating it in an open state on sand with a No. 6 detonator, and simultaneously measuring the detonation velocity with a digital counter. The lowest temperature at which detonation could occur and the detonation speed at that temperature were determined.

Furthermore, the detonation velocity at 20° C. was determined by the detonation velocity measurement method described above.

Reference Example [Manufacture of GNN] 210 parts of commercially available glycinonitrile sulfate was dissolved in 210 parts of water, and while stirring, 200 parts of 40% sodium hydroxide was gradually added dropwise to react.

After the completion of the reaction, the by-product sodium sulfate crystals were separated and removed by filtration under reduced pressure, etc., and an approximately 70% glycinonitrile aqueous solution 160%
I got the department.

70% of 80 parts of the obtained glycinonitrile aqueous solution
It was reacted with 90 parts of nitric acid.

The obtained product was evaporated to dryness to obtain colorless GNN crystals.

Comparative Example 1 A water-in-oil emulsion explosive composition having the formulation shown in Table 1 was manufactured by the following method.

That is, an aqueous solution at about 85°C prepared by dissolving 394 parts of ammonium nitrate in 55.5 parts of water, 8 parts of sorbitan sesquioleate, and 16 parts of microcrystalline wax.
．． A W10 type emulsion composition was obtained by mixing and stirring with a mixture of 5 parts at about 85° C. using a stirrer.

Furthermore, a W10 type emulsion explosive composition was obtained by mixing 26 parts of glass micro hollow spheres as a temporary specific gravity adjuster into the W10 type emulsion composition.

The performance test results of the obtained W10 type emulsion explosive composition were as shown in Table 1.

Comparative Example 2 A W10 type emulsion explosive composition having the formulation shown in Table 1 was manufactured according to the manufacturing method of Comparative Example 1.

The performance test results of the obtained W10 type emulsion explosive composition were as shown in Table 1.

Comparative Example 3 A W10 type emulsion explosive composition having the formulation shown in Table 1 was manufactured by the following method.

That is, an aqueous solution at about 85°C prepared by dissolving 317.5 parts of ammonium nitrate, 56.5 parts of sodium nitrate, and 25 parts of monomethylamine mononitrate in 50 parts of water, 9 parts of sorbitan sesquioleate, and 17 parts of microcrystalline wax. A W10 type emulsion composition was obtained by mixing and stirring the mixture with a mixed melt at about 85° C. using a stirrer.

Next, a W10 type emulsion explosive composition was obtained by mixing 25 parts of glass micro hollow spheres as a temporary specific gravity adjuster into the obtained W10 type emulsion composition.

The performance test results of the obtained W10 type emulsion explosive composition were as shown in Table 1.

Comparative Example 4 A W10 type emulsion explosive composition having the formulation shown in Table 1 was manufactured according to the manufacturing method of Comparative Example 3.

The performance test results of the obtained W10 type emulsion explosive composition were as shown in Table 1.

Example 1 Using the GNN obtained in Reference Example, a W10 type emulsion explosive composition of the present invention was manufactured in the following manner with the formulation shown in Table 1.

That is, 3785 parts ammonium nitrate and GNN2
An aqueous solution at about 85°C obtained by dissolving 5 parts of sorbitan sesquioleate in 50 parts of water and a mixed melt at about 85°C obtained by dissolving 6.5 parts of sorbitan sesquioleate and 15 parts of microcrystalline wax are mixed using a stirrer. By stirring, a W10 type emulsion composition was obtained.

Next, by mixing 25 parts of glass micro hollow spheres as a temporary specific gravity adjuster into the W10 type emulsion composition, W1
A type 0 emulsion explosive composition was obtained.

The performance test results of the obtained W10 type emulsion explosive composition were as shown in Table 1.

Examples 2 to 16 W10 type emulsion explosive compositions of the present invention were manufactured according to the manufacturing method of Example 1 using the formulations shown in Table 1.

The performance test results of the obtained W10 type emulsion explosive composition were as shown in Table 1.

As shown above, the W10 type emulsion explosive compositions containing no sensitizer shown in Comparative Examples 1 and 2 detonated with a detonator even when the temperature was lowered to 0° C., but did not detonate at even lower temperatures.

G as a sensitizing agent in this W10 type Emuljoy explosive composition.
When 5% NN was added, the explosion occurred even when the temperature was lowered to -20°C, as shown in Examples 1 and 2, and furthermore, Example 3
As shown in Figures 1 to 16, as the amount of GNN added increased, the detonation sensitivity at low temperatures improved.

Furthermore, as shown in Comparative Examples 3 and 4, W10 type emulsion explosive compositions using conventionally known monomethylamine mononitrate as a sensitizing agent had 10% It detonated even when the temperature was lowered to 10°C, and when it was mixed at 10%, it detonated even when the temperature was lowered to 20°C.

However, as shown in Examples 1 to 13, when using GNN, C
When the W10 emulsion explosive composition contained 5% GNN, it detonated even when the temperature was lowered to -20°C, and
%, it detonated even when the temperature was lowered to -30°C.

Therefore, monomethylamine mononitrate and GN
When compared with N at the same content, it was found that GNN has better low-temperature detonation properties.

Furthermore, even when the types of emulsifiers and fuel oils/waxes were changed, the performance was not particularly affected.

As described above, the W10 type emulsion explosive composition of the present invention was shown to exhibit sufficient detonator detonation properties, and was particularly excellent in low-temperature detonation properties.

Claims (1)

[Claims] 1 A dispersed phase containing ammonium nitrate or ammonium nitrate and other inorganic oxide salts and water, fuel oil,
A water-in-oil emulsion explosive composition comprising a continuous phase of waxes, an emulsifier, and a temporary specific gravity adjuster, characterized in that the dispersed phase contains glycinonitrile nitrate as a sensitizing agent. Water-in-oil emulsion explosive composition.