JPS636518B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to slurry explosive compositions. More specifically, a slurry explosive composition containing an inorganic oxide salt component, a flammable component, and water as main components, glycerin, and a monocarboxylic acid consisting of an aliphatic monocarboxylic acid having 16 to 18 carbon atoms or tryptophan. A glycerin ester obtained by esterifying by a normal dehydration reaction and then reacting with a compound containing a hydroxyl group or an amino group selected from malic acid, citric acid, and glutamic acid and having two or more carboxyl groups. The present invention relates to a slurry explosive composition comprising: In recent years, so-called slurry explosive compositions have attracted attention as industrial explosive compositions, in which an inorganic oxide salt component and a combustible component are dispersed in water in the form of a slurry, and a viscosity agent and a sensitizing agent are added thereto. It has become like that. This product can be manufactured relatively cheaply,
It is extremely safe and the gas produced after explosion is cleaner than that of dynamite. Moreover, because of its high specific gravity, it can be secretly loaded into boreholes underwater, and has many features such as higher detonation velocity and explosive power than ammonium nitrate fuel oil explosives. However, inorganic oxide salt components, combustible components, water,
Traditional slurry explosives consisting of thickeners and sensitizers have had many drawbacks. That is, in conventional slurry explosives, as time passes, the inorganic oxide salt component in the slurry explosives crystallizes and gradually settles and separates. Along with this, combustible components and sensitizers also settle and separate, making it difficult to pump slurry explosives, reducing explosive power, and, in extreme cases, causing failures. In addition, conventional slurry explosives require a sensitizing agent, which is expensive and
It also had drawbacks such as decomposition reactions occurring during product storage. Therefore, various proposals have been made to produce slurry explosives that are stable for a long period of time and do not use sensitizers. For example, as shown in JP-A-50-89514 and JP-A-51-1616, polyoxyethylene fatty acid ester, polyoxyethylene alkyl ether, sorbitan monofatty acid ester, polyoxyethylene A method has been proposed in which a slurry explosive contains a large amount of fine air by using ethylene sorbitan monofatty acid ester, thereby eliminating the use of a sensitizer in the slurry explosive.
This method does not use a sensitizing agent, is relatively inexpensive, has high specific gravity, and has detonating properties.
A relatively stable slurry explosive is obtained. However, although some improvements have been observed in this method, it is still not sufficient. That is, since slurry explosives are often used underwater, they are required to have satisfactory durability, but they are not satisfactory in this respect. In addition, in these methods, in order to obtain a composition with a practical viscosity of slurry explosive, that is, 10 to 1000 poise, it is necessary to add a thickening agent, and in terms of long-term stability, However, it is not completely satisfactory. The present invention was achieved as a result of intensive research aimed at obtaining a slurry explosive composition that eliminates the above-mentioned defects without impairing the characteristics of conventional slurry explosives. That is, glycerin and an aliphatic monocarboxylic acid having 16 to 18 carbon atoms or a monocarboxylic acid consisting of tryptophan are added to a slurry explosive composition containing an inorganic oxide salt component, a combustible material component, and water as main components. After esterification by dehydration reaction, blending a glycerin ester obtained by reacting a compound containing a hydroxyl group or an amino group selected from malic acid, citric acid, and glutamic acid and having two or more carboxyl groups. To provide a slurry explosive composition that contains a large amount of fine air, has good water resistance, is economically stable, has high specific gravity, and has detonator detonation properties without adding a viscosity agent or a sensitizing agent. It is. The inorganic oxidizing acid salt component in the present invention is, for example, a salt such as an ammonium, alkali metal, or alkaline earth metal salt of an inorganic oxidizing acid such as nitric acid, chloric acid, hypochlorous acid, or perchloric acid. For, ammonium salt,
Sodium nitrate is often used. Practically speaking, the blending ratio of the inorganic oxide salt component is preferably 50 to 80% by weight of the slurry explosive. The combustible components are carbon powder, sulfur, sugar, dinitrotoluene, urea, nitroparaffin, liquid paraffin, and fuel oil such as light oil, and the blending ratio is 1 to 20% by weight of the slurry explosive, preferably 1 to 15% by weight. Weight%. The amount of water added is 18 to 53% by weight, preferably 13 to 43% by weight. Next, glycerin esters include caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linoleic acid, glycine, alanine, leucine, phenylalanine, tyrosine, histidine, tryptophan, etc. Monocarboxylic acids, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, malic acid, aspartic acid, glutamic acid, etc. Examples include glycerin esters of compounds having two or more carboxyl groups, such as tricarboxylic acids such as dicarboxylic acid, citric acid, oxalsuccinic acid, tricarballylic acid, and benzenetricarboxylic acid. 16~
After esterifying 18 aliphatic monocarboxylic acids or a monocarboxylic acid consisting of tryptophan by a normal dehydration reaction, it contains a hydroxyl group or an amino group selected from malic acid, citric acid, and glutamic acid, and 2 Glycerin esters obtained by reacting the above compounds having carboxyl groups are preferred. The glycerin ester in the present invention may be synthesized by first esterifying glycerin and the above-mentioned monocarboxylic acid by a normal dehydration reaction, and then adding the above-mentioned compound having two or more carboxyl groups. , a monocarboxylic acid, and a compound having two or more carboxyl groups may be simultaneously charged for synthesis. The amount of glycerin ester added in the present invention is 0.1 to 5.0% by weight based on the slurry explosive, but considering economic efficiency and long-term safety, it is 0.5% by weight.
The preferred addition range is 3.0% by weight. The present invention provides a good slurry explosive having a high specific gravity and sufficient detonator detonator by simply blending the above-mentioned composition, that is, an inorganic oxide salt component, a combustible component, water, and the above-mentioned glycerin ester. Because of the
Sensitizers such as nitrates of nitrogen bases (eg, monomethylamine nitrate, ethylenediamine nitrate) are not necessarily required, but may be used to improve potency. The present invention also uses water-soluble polysaccharide derivatives such as thickeners such as carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, guar gum, locust bean gum, and carboxymethyl starch, polyvinyl alcohol, polyethylene oxide, polyacrylate, and polysaccharide. Although it is not necessary to blend a water-soluble polymeric substance such as acrylamide, there is no restriction on blending these thickening agents. Furthermore, there is no restriction in any way that a known gelling enhancer such as borax may be blended together with the thickening agent. Although the reason why the explosive composition of the present invention is stable for a long period of time is not clear, the glycerin ester of the present invention has excellent dispersing power and has an effect of preventing precipitation of insoluble matter. Excellent emulsification power and emulsion stability. It is crosslinked by a compound having two or more carboxyl groups, and a network structure is formed in the slurry explosive composition. It is thought that it exerts the following effects. Next, the present invention will be explained with reference to examples, but the present invention is not limited to these examples. (All formulations shown in the examples indicate weight %.) Example 1 In a reactor equipped with a stirrer, a thermometer, a cooling dehydration tube, and a nitrogen introduction tube, 1 mole of glycerin [92 g],
1 mole of palmitic acid [256 g] and 1% para-toluenesulfonic acid [4.1 g] as a catalyst were added to 120
℃, melt the above raw materials, start stirring while introducing nitrogen, and esterify by dehydration reaction at a temperature of 230℃, then add 0.5 mol [67 g] of malic acid and dehydrate for 3 hours. After the reaction was completed, the mixture was cooled to room temperature to obtain a brown viscous substance. This product is glycerin ester No. A shown in Table 1. Glycerin esters Nos. B to V were also produced in the same manner as described above using the blending ratios shown in Table 1. Next, a slurry explosive composition having the composition (wt%) shown in Table 2 was prepared at 70°C. And the table-
After preparation as shown in No. 3, the sample was left at room temperature and the economical change in viscosity was measured. (A rotating cylindrical viscometer was used to measure the viscosity at 25°C.) The results are shown in Table 2 and Table 2.
Shown in 3. As is clear from Tables 1, 2, and 3, the slurry explosive composition (Experiment No. 23, 24) cannot be put to practical use because the inorganic oxide salt component crystallizes in a short period of time. Next, water resistance tests and explosive performance tests [JIS-K4810 (35mmφ
The results are shown in Table 4. In addition, the water resistance test was conducted using 1 g of the slurry explosive composition.
The slurry explosive composition was placed in a 100 ml beaker, 100 ml of distilled water was added thereto, and the slurry explosive composition was left to stand for one day, and the presence or absence of swelling of the slurry explosive composition was visually determined. As is clear from Table 4, in the long-term stability test (Table 3), the inorganic oxide salt component (ammonium nitrate) and the combustible component (n
- paraffin) and water-based slurry explosive compositions (Experiment Nos. 25 and 26) had poor water resistance;
It is impossible to put it into practical use. However, slurry explosive compositions (Experiments Nos. 1 to 22) in which the glycerin ester of the present invention was blended into a system consisting of an inorganic oxide salt component, a flammable component, and water were stable for a long period of time and had good water resistance. Therefore, it can be confirmed that it can be used as an explosive. Example 2 A slurry explosive composition having the composition (wt%) shown in Table-5 was prepared, and malic acid ester of sorbitan monooleate and glycerin monooleate (Table-1
A performance comparison test was conducted with glycerin ester No. E). The results are shown in Table-5. Note that the preparation and measurement methods are based on Example 1. As is clear from Table 5, malic acid ester of glycerin monooleate is significantly superior to sorbitan monooleate, and is effective against a wide range of inorganic oxide salts and combustible materials. You can check it. Additionally, a slurry explosive composition containing sorbitan monooleate (Experiment No. 30) and a slurry explosive composition containing a thickening agent (guar gum) (Experiment No. 30) were prepared.
61-62) or a slurry explosive composition prepared by adding a thickening agent and sorbitan monooleate (Experiment No. 63-62)
It can be confirmed that long-term stability and water resistance are improved by adding malic acid ester of glycerin monooleate to 66). (Experiment No. 57,
58, 67-72) Example 3 A slurry explosive composition having the composition (wt%) shown in Table 6 was prepared and the explosive performance was tested. The results are shown in Table-6. The aluminum powder used in this test was a 300 mesh pass powder covered with an oxide film. Results in Table 6 and Table 4, such as Experiment No. 5, 7,
When compared to 13 and 15 mag, its effectiveness as an explosive has not improved significantly. From this result, it can be confirmed that a sensitizing agent is not necessarily required in the slurry explosive composition containing the glycerin ester of the present invention.

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Claims (1)

[Claims] 1 Glycerin and a monocarboxylic acid consisting of an aliphatic monocarboxylic acid having 16 to 18 carbon atoms or tryptophan are added to a slurry explosive composition mainly composed of an inorganic oxide salt component, a combustible material component, and water by normal dehydration. After esterification by reaction, blending a glycerin ester obtained by reacting a compound containing a hydroxyl group or an amino group selected from malic acid, citric acid, and glutamic acid and having two or more carboxyl groups. Characteristic slurry explosive compositions.