DE1301750B - Weather explosive with improved deflagration behavior - Google Patents

Description

1 2

In recent years, the usual components, such as insbesichen, have been used in place of the hash Ammonium nitrate weather explosives with special cooking oil, contains and apart from an alkali salt additive especially for the safety class nitrate and possibly ammonium chloride as further sen II and III increasingly weather explosives inverse component such an amount of an ammit so-called inverse salt pair introduced, d. H. 5 monium salt of an organic one- or two-basi explosives, the mixtures of potassium or Na- see acid with up to 4 carbon atoms that the trium nitrate and ammonium chloride in addition to about 9 to an oxygen balance of about -2 to + 5%, preferably 12 ° / o contains explosive oil as a sensitizer. At - 1 to 4-3%. Suitable ammonium salts Detonation sets the alkali nitrate with the Am- are z. B. ammonium formate, ammonium rhodanide, monchloride as if it were made from alkali chloride in the form of ammonium acetate, ammonium glycolate, ammonium and ammonium nitrate, which would then consist of oxalate with or without water of crystallization and amknown detonative decay is assigned to: monium malonate.

These ammonium salts can be used as the sole salt

2 KNO ₃ + 2 NH ₄ Cl = 2 KCl + 2 N ₂ + 4 H ₂ O + O ₂ pair components are used, more advantageous-

15 but also as an additive to an alkali nitrate

The release of energy takes place in such a way that by the ammonium chloride salt pair, namely when primary detonation of the blasting oil the detonative the ammonium salts consume so much oxygen, Salt pair reaction is stimulated; for this it is necessary that, when used alone, the oxygen balance sufficient containment of the explosives which would be too degraded.

relatively sluggish conversion of the salt pair forced ²⁰ The binary and ternary salt according to the invention is; When exposed, only the blasting oil detonates in such a way that, as a mixture, it can be varied within wide limits whether it would be distributed in an inert salt bed. and it is thus possible to use explosives at any

The high level of safety of the salt pair explosives has made it desirable to establish an oxygen balance at their three reasons: detonation no free hydrochloric acid occurs.

Firstly, the conversion of the salt pair requires ² 5. Of course, one can also use mixtures that have a longer time component than ammonium nitrate as such;

distributed and thus the energy density of the shock wave

humiliated. Second, the practically molecularly complete conversion of the nitrates can only be achieved in a dispersed manner resulting alkali chloride is better than mechanical 3 ° if at least 1 mole of Amnisch per mole of nitrate Mixed in salt is able to very quickly monchloride is present, the organic can Absorb heat and therefore have a cooling effect. Ammonium salts partly also in a smaller MoI third But the implementation of the salt pair runs at proportion to be used, provided their oxygen deficiency Inclusion - as mentioned - only if necessary ensures the complete conversion of the nitrates, from a fraction, d. that is, the explosion temperature 35 The rest of the structure of the inventive explosive And the released energy will be crucial substances largely corresponds to that of the known lowered when cartridges of a borehole through the salt pair weather explosives. As a sensitizing, Detonation of the previous charge exposed highly explosive components one uses explosive oils, should be. This latter behavior of the salt d. H. essentially nitroglycerin and nitroglycol Paar weather explosives are documented in a 4 ° or a mixture of the two. To achieve the outstanding Edge security when testing in the desired water resistance can swellable high der Weather track. polymers, e.g. B. guar flour, carboxymethyl cellulose

In the case of the previously usual weather explosives with, inter alia. can be added. The well-known influence of the inverted salt pair one has to have in general grain distribution in the salt pair explosives Alkali nitrate and ammonium chloride in the stoichiometric ratio also in the explosives according to the invention Used 1: 1. In this mixture, account must be taken of, d. i.e., the grain size of the ratio if the result is a considerable excess of oxygen, the individual components must be sufficiently fine and shot at detonation, d. i.e. the oxygen balance is coordinated with one another, is despite the frequent addition of The explosives according to the invention surpass

swellable high-polymer carbohydrates to the 5 ° thanks to the better utilization of the oxygen significantly positive increase in water resistance. Performance of the previously common salt pair explosives.

These salt-pair weather explosives are good-looking, nonetheless they meet all the test conditions that

lent their deflagration resistance not fully satisfactory- are prescribed for weather explosives (cf. Begend. When testing according to Audibert-Del moods for testing mining explosives They only show a nozzle diameter above 5 mm, decree of the Minister for Economics and Transport no more deflagration. of the state of North Rhine-Westphalia on the examination

It has already been proposed to reduce the amount of oxygen in explosives for the approval of the sale of the salt pair explosives by the mining of February 19, 1959). In particular, it remains to be assumed that more than 1 mol of the salt pair character is introduced per mole of alkali nitrate, even in the absence of ammonium-ammonium chloride. Such a procedure has received ⁶⁰ chloride; z. B. KNO ₃ - (NHJ ₂ C ₂ O _4, however, have the disadvantage that with complete conversion only in the inclusion, but not exposed. The free hydrochloric acid occurs. Practical tests have shown that edge security remains Edge security not resistance is so high that it is given in the test under the strictest test conditions. According to Audibert-Delm as (Nobel-Hefte, 1963,

A weather explosive has now been found with improved ⁶ 5 p. 118 ff.) Even with the use of the smallest nozzle set deflagration behavior, high performance and a diameter of 1.5 mm no deflagration-sensitive edge security, which show on the basis of salts with exchangeable ions is constructed, there are also known explosive mixtures,

which in addition to a main proportion of around 50% ammonium nitrate, ammonoxalate and ammonium chloride and a Contain alkali nitrate, but these explosives are not to be addressed as salt pair explosives and do not have their advantages due to their high ammonium nitrate content. In particular, their edge security is not comparable with those of the salt pair explosives.

The use of stearic acid or its salts, i.e. acids of the fatty acid series with at least 10 carbon atoms, for the hydrophobization of explosives is from the German patent 1092 357 known. However, these explosives do not prove deflagration-proof when tested Audibert — Delmas up.

Examples of the explosives according to the invention are shown in the table below Mixtures called, in which also the blasting data of the mixtures and their behavior are specified under the official test conditions.

Example 1 relates to a class III weather explosive in the currently customary composition. As can be seen from this, the explosive mixtures according to the invention have the same properties as the comparable ones previously known a higher performance, which resulted in a considerable increase in the lead block bulge, the compression and the detonation speed expresses, and one so far not achieved deflagration resistance.

example

I 3 I.

Composition in ° / o

Explosive oil (nitroglycerin to nitro-

glycol 60:40)

Guar flour

KNO ₃

NaNO ₃

NH ₄ Cl

(NHJ ₂ C ₂ O ₄ -H ₂ O

NH ₄ COOH

NH ₄ CNS

Oxygen balance in%

Compression according to Käst

Lead block bulge

Transmission in the coal-cement pipe 2: 1

Detonation speed ...

Water resistance after storage for 5 hours under H ₂ O ...

Weather security

(according to official test specification KZ = no ignition)

Coal dust safety

(according to official test specification KZ = no ignition)

Deflagration security

According to Audibert-Delmas, safe with nozzle diameter

without additive according to the invention

2.0 58

31

+ 6.9

1.45 90

8 to 1500

concentration camp

concentration camp

5mm 8.5
1.5
52

+ 1.9

1.48
100

until 10
1640

concentration camp
1.5 mm

9.2
1.8
52

27
10

+2.0

1.55
110

10 to 15
1700

concentration camp

concentration camp

1.5 mm

9.3
1.9

30.3

4.5

+3.7

1.56 110

10 to 12 1680

concentration camp

concentration camp

1.5 mm

9.0 2.0

57

30.3

1.7

+4.7

1.54 115

10 to 15 1675

KZ KZ

1.5 mm

While the comparative explosive (Example 1) only showed no deflagration phenomena at a nozzle width of 5 mm shows more, the explosives according to the invention are already at one nozzle diameter of 1.5 mm deflagration-proof, i.e. with the smallest possible nozzle diameter, the method from Audibert — Delmas can be used.

Claims (4)

Patent claims: 1. Weather explosive with improved deflagration behavior based on salts with exchangeable Ions and other common constituents, such as in particular explosive oil, thereby characterized in that, in addition to an alkali nitrate and optionally ammonium chloride, as a further inverse component contains such an amount of an ammonium salt of an organic acid with up to 4 carbon atoms that the oxygen balance is approximately −2 to + 5%, preferably −1 to + 3%. 2. Weather explosive according to claim 1, characterized in that it is used as the ammonium salt an organic acid containing ammonium formate. 3. Weather explosive according to claim 1, characterized in that it is used as the ammonium salt an organic acid containing ammonium oxalate. 4. Weather explosive according to claims 1 to 3, characterized in that it is mixtures of ammonium salts of organic acids with up to 4 carbon atoms.