DE1771480B1 - Water-based explosives mixture - Google Patents

Description

1 2

The invention relates to hydrous explosives, whipped, dry ammonium nitrate explosives

also known as slurries. to improve by adding hydrazine mononitrate.

Water-containing explosives of high explosive power It is also known, alkylammonium nitrates

and detonation speed, as required for peak-water containing explosives to add through

services are required, contain an oxidizing 5 highly explosive explosive such as nitropenta

of the salt, mostly ammonium nitrate, are sensitized to lower amounts of erythritol

a fuel and an aqueous phase, which, if used, the high-explosive can use

is coherent, usually thickened or, thereby increasing safety (British pa-

is gelled. A highly explosive tentschrift 882 855, German patent specification 1119 740) serves to raise awareness.

Explosives, such as trinitrotoluene or smokeless powder, io Practically, the nitrates of diethanol

or a finely divided metal such as aluminum, minamine and triethanolamine are used, but these are

at least as part of the fuel to generate explosive power and salts for the behavior of these water-containing explosives

Increase sensitivity. Such explosives and substances are not required at all, because if one

metallic additives are expensive and cause the diethanolamine or triethanolamine nitrate through

Difficulty in processing, as it replaces sodium nitrate at 15, so will sensitivity

they are usually insoluble solids, which are not reduced, but actually increased. From it

are distributed in the explosives during manufacture, it follows that in these explosives only the nitropenta

must and during storage and use this verythritol acts as a sensitizer; raising awareness

must maintain division. Their deposition with alkylamine nitrates is described in these patents

adversely affects the blasting properties and cannot be shown in FIG.

Case of the use of high-explosive explosives as In the United States patent 3 318 740 was

Sensitizers become dangerous. beaten, hydrous explosives with the salt

It has now been found that such water-containing a certain nitrogen base to sensitize,

Explosives in whole or in part by certain namely the mononitrate and / or dinitrate of hexa-

liquid, soluble or easily dispersible solid salts 25 methylenetetramine. Are hexamethylenetetramine nitrates

a nitrogen base can be sensitized, but so the salts of

that at relatively low cost explosive nitrogen bases are clearly inferior sensitizers.

Mixtures of substances with a surprisingly high detonation The "oxidizing salt" and the "fuel" are

speed and explosiveness in a density range explosive components with positive or negative

receives up to 1.4 g / cm ^3. The explosive effect decreases the oxygen balance. The oxygen balance is the percentage

usually all other things being equal, with the details of excess or deficiency of the oxygen required for

nation speed to. complete combustion is required and will be

The invention relates to the use of an acyclic nitrogen base with no more than 35 oxygen divided by the molecular weight of 2 hydrogen atoms, as the molecular weight of an acyclic nitrogen base required for the complete salting of an inorganic oxidizing acid and combustion basic nitrogen atom of the substance concerned, calculated. A "sensitizer" is bound and which has up to 3 carbon atoms each a substance, which, if it can contain in small amounts (e.g. basic nitrogen atom, and / or a few percent) to an explosive, a phenylamine, at least one is more positive, the sensitivity and initiation ability of which have an oxygen balance of about 150 per cent, increases considerably at a certain temperature if in a mixture with highly explosive explosives, than and vice versa when removing from the explosives sensitizers in water-containing explosives mixture its critical diameter increases ,
The nitrogen bases used according to the invention, a salt, a fuel and water, with the exception of inorganic bases such as hydrazine, are the use of the nitrates of tertiary amines in water, but preferably aliphatic amines or phenyl-containing explosive mixtures, consisting of 5 to amines, ie compounds with a carbocyclic 15 percent by weight of water. 30 to 80 percent by weight aromatic ring to which at least one, preferably percent, ammonium nitrate, up to 10 percent by weight of one or two primary amino group (s) is (are) bound by alkali metal and / or alkaline earth metal nitrates. There can be secondary or tertiary sets, 2 to 15 percent by weight of a bri 50 amine can be used, but primary amines are santen explosives with a detonation speed of the higher N to C ratio preferred, speed> 5000 m / sec., 2 up to 10 percent by weight of bases consisting of the elements carbon, hydrogen, tertiary amines or their nitrates. 5 to 25 weight and basic nitrogen are preferred, percent perchlorates of ammonium and / or other substituents may be present. Ge-alkali metals, optionally with the addition of swelling-saturated aliphatic amines with up to 3 carbon agents and / or emulsifiers, which 0.2 to 1 ge atoms are particularly preferred. The oxidizing weight percent of the total mixture can make up. Acid can be any suitable strong inorganic oxy-

Monomethylamine nitrate would be a constituent acid, preferably a mineral acid, poured ammonium nitrate explosives in German such as nitric acid, nitrous acid, chloric acid or Patent 581 814 proposed and in the second 60 superchloric acid, and is preferably supposed to be an oxygen world war used, see Urbanski, »Have a chemistry balance of at least + 10%. nitric acid and Technology of Explosives, "Vol. 2, pp. 465-466. is particularly preferred.

The addition was made to reduce the solidification. Examples of suitable sensitizing salts are inorganic salts such as hydrazine nitrate, hydrazine dinitrate and aim. For explosive mixtures containing water, 65 perchlorate; Salts of aliphatic amines such as monoder Addition not recommended, also mentions original methylamine nitrate, chlorate and perchlorate; Ethylenbans ki is the disadvantage of hygroscopicity. diamine diperchlorate; Dimethylamine nitrate; Ethylamine

In the German patent specification 968 480, pre-nitrate and propylamine nitrate; Guanidine nitrate and

3 4

Urea nitrate and salts of the phenylamines, such as The total content of the explosives mixture of the aniline nitrate, chlorate and perchlorate, p-chloroaniline salt of the nitrogen base varies depending on the mixture nitrate, phenylenediamine dinitrate, as well as any mixture and can e.g. B. from 5 to 90 percent by weight, mix from these salts. Monomethylamine nitrate In general, the amount of salt required decreases, and ethylenediamine nitrate is particularly preferred because of its ease of 5 when the water content is decreased and when addability to explosive mixtures and which increases the amount of other auxiliary sensitizers, the blasting properties of the products. or if a weaker blasting mixture is desired. Some of these amine salts are self-detonating. The sensi explosives are preferably used. Mixtures of one or more of these-stabilizing salt in amounts of about 10 to 50 ° / _0th Depending on salts with other similar salts, the oxygen of which, according to its oxygen balance, forms the salt of the nitrogen balance is more negative than -150%, e.g. cyclohexyl base either part of the oxygen carrier or, amine nitrate and diethylamine nitrate, can be used more often, part of the fuel,
will. The resulting oxygen balance of the mixture is then more positive than -150%. the salt of the nitrogen base sensitized explosives

The salts of the nitrogen bases can be added to the explosive mixtures, if desired, even further in pure form, but will be improved, especially at low temperatures, preferably as a crude reaction mixture from the base and / or small charge diameters by is added to the neutralizing oxidizing acid. In addition, a fatty alcohol soluble in the mixture - this mixture is either prepared separately in aqueous sulfate, ie a neutral salt of an acidic ester of the solution and then mixed with the remaining sulfuric acid with a saturated aliphatic component of the explosive, or it is used on primary Alcohol with 8 to 22, preferably 8 to m , is added on the spot in the presence of one or more of these 18 carbon atoms. Components are preferably made. So the oxidizing such sulfates can be salts of the alkali metals, especially the constituent and the fuel mixed with water, sodium and potassium, ammonium, and the product is then neutralized by neutral phosphatic amines with up to 5 carbon atoms of one or more the nitrogen bases with one or the amino alcohols with 2 to 6 carbon or more of the oxidizing acids. atoms. Such preferred sulfates can by

It is a benefit of the hydrous explosives general formula

Mixtures according to the present invention that they _{rH iru} -> _{n <; n λ / Γ}

not the usual metallic explosives sensitive- 30

Sators need such as finely divided aluminum, or be shown, wherein M is one of the aforementioned strong explosives, which fall into two categories, cations, e.g. B. Na ⁺ or K ⁺ , means and η is a highly explosive explosives of the penta-value from 7 to 21. Alkali salts of fatty alcohol erythritol tetranitrate, hexogen and octogen (it is sulphates, especially sodium salts of monoesters, should be remembered that in German patent 35 sulfuric acid with an aliphatic alcohol with 1,119,740 and British patent 882 555 8 to 14 carbon atoms, are particularly before -Pentaerythritol tetranitrate and hexogen added as explosives. Examples of suitable sulfates of fatty alcohols with a high detonation rate are recommended sodium nonyl sulfate, potassium lauryl sulfate, or less strong, highly explosive sensibili- monium lauryl sulfate, the methylamine salt of lauryl sulfate, the powder of lauryl sulfate, such as trinitrotoluene Lauryl sulfate, sodium or mixtures thereof, e.g. B. Pentolite (pentaerythritol cetyl sulfate, ammonium cetyl sulfate, potassium cetyl tetranitrate / trinitrotoluene) and "Composition B" (hexosulfate, sodium oleyl sulfate and potassium oleyl sulfate. Wegen / trinitrotoluene). If, however, conventional solid due to their low cost and the explosive self-explosives of high detonation rate shear the resulting products, in addition to the salts of nitrogen bases proposed according to the invention as sensitizers 45 trium octyl sulfate, sodium decyl sulfate, sodium oleyl sulfate and especially sodium lauryl sulfate (they should be used in much smaller amounts of niche quality) are particularly preferred. Of the salts used, as they are recommended in the British patent of fatty alcohol sulfates, only small amounts, 882 555, namely in an amount usually only 0.2 to 2 percent by weight and generally less than 8% of the weight of the entire 50 common only 0.25 to 1 percent by weight, based on the explosives mixture, and in practice still considerably the total weight of the mixture. Larger less, e.g. B. less than 5%. In this regard, amounts must produce excessive foaming and compliman sharply between the present invention submitting the formulation and mixing of the explosive, which divide on the sensitizing effect of one or more of the above-described salts of stick-55 without favoring the explosive properties The weight ratio between the fatty alcohol bases is based, but in addition high sulfate and the salt of the nitrogen base are typically explosive sensitizers with a high detonation in the range from 1:10 to 1: 1000. preferably be contained in small amounts from 1:30 to 1: 150.

can, and the proposal of the British patent The fatty alcohol sulfate is usually in the form

882 555, on the other hand, according to which certain explosives are an aqueous solution or slurry-like dispersion

Mixtures of substances added by solid explosives from high levels, preferably to a hot one

Detonation speed, such as pentaerythritol tetra- (50 to 80 ⁰ C), "neutral", essentially saturated

nitrate and hexogen, are sensitized, however, dissolving the oxidizing component before adding

It also contains small amounts of additives that include a thickening or gelling agent. to

by definition, salts of nitrogen bases are at the beginning of a relatively large proportion

close, but without there being recognized that the oxidizing salt is in solution. Part of the salt

However, certain salts from this group crystallize on their own when the product cools,

cheap and effective sensitizers. so that at room temperature 10 to 20% of the salt

undissolved, ie can be crystallized, while at 5 ° C up to 50% of the salt is crystallized. Optionally, auxiliary fuels and other additives, such as liquefaction additives, buffers, e.g. B. fumaric acid, and sensitizing amounts of gas-filled hollow spheres can be added to the hot solution or to the cooled product in order to influence the characteristics of the mixture. The addition of the fatty alcohol sulfate to the hot solution before cooling is particularly advantageous since salts of the alcohol sulfates, particularly the preferred sodium lauryl sulfate, tend to affect the crystallization. In this case, especially from solutions of ammonium nitrate, smaller crystals of a shell-like or porous shape form when they cool down. The increased sensitivity to detonators and intermediate charges at low temperature is likely due to the uniform inclusion of extremely small gas-filled cavities, e.g. B. air bubbles, e.g. B. between 5 x 10 ~ ⁶ and 5 x 10 ~ ² cm in diameter, in the whole mixture.

The other ingredients can be those normally used in hydrous explosives in conventional Way to be used. Suitable mixtures therefore contain at least 20 percent by weight inorganic oxidizing salt, such as ammonium, alkali, alkaline earth nitrates and / or perchlorates. At least 45% of this component is easily soluble in water at room temperature, such as ammonium nitrate, so that desirably the aqueous phase contains a considerable amount, e.g. B. at room temperature 40 to 70 percent by weight, contains oxidizing salt. Mixtures of inorganic oxidizing salts containing at least Contain 50 percent by weight ammonium nitrate and at least 5 percent by weight sodium nitrate, are particularly preferred, and the pH is preferably adjusted to between 4 and 7.

The sensitizing salts of the nitrogen bases can make essentially all of the fuel contribution supply, but it is often desirable to add a conventional auxiliary fuel provided that the fuel in question in the mixture is chemically stable during its manufacture and storage. Examples of auxiliary fuels are sulfur, carbonaceous fuels such as pulverized coal and others Forms of finely divided coal and solid natural products containing carbon, such as corn starch, wood pulp, sugar, Nutshells and / or sugar cane waste. Examples of metallic auxiliary fuels are aluminum and / or Iron and / or alloys, such as aluminum-magnesium alloys, ferrosilicon and / or ferrophosphorus. The total amount of fuel is balanced so that the explosives mixture has an oxygen balance of -25 to + 10% has- apart from mixtures that Containing heavier metallic fuels, such as ferrophosphorus and ferrosilicon, the oxygen balance lies preferably between -10 and +10% ■

The water content is generally at least 5 percent by weight and up to 50 percent by weight; preferably it is on the order of about 10 to 30 percent by weight of the total Mixture. Conventional substances can be used to thicken or gel the aqueous phase, preferably Galactans, especially guar gum, usually in amounts of 0.1 to 5% of the total weight of the Mixture. The thickeners are usually used before the auxiliary fuels or sensitizers incorporated. Galactans are preferably treated with an oxidizing agent such as alkali dichromate either alone or in combination with a soluble antimony compound, crosslinked. The crosslinking agents are generally in the case of packaged products just before packaging and in the case of Products that are pumped by the tanker are added shortly before they are filled into the borehole. Guar resin in connection with polyacrylic acid amide is often used for coherent yet castable explosives preferred.

In the following examples, parts and percentages are by weight, unless otherwise is specified.

example 1

Aqueous ammonium nitrate solution (AN) with 80% AN, solid AN and a 70 to 74% aqueous solution of monomethylamine nitrate (MMAN), alone or with ethylene diamine nitrate (AEDAN), are mixed, heated to 54 to 60 ° C and placed in a mixing vessel transferred, where premixed sodium nitrate (NN) and guar resin are added. Mixing is carried out for 3 to ₂ minutes until thickening is observed, whereupon the fuels are mixed in uniformly in the amounts given in Tables I and II. Crosslinking agents are then added, the ingredients are mixed for several minutes and then filled into polyethylene bags.

The mixtures in Table I have densities of 1.1 to 1.2 g / cm ³ and can be detonated with a No. 3 detonator at a relatively low temperature (2 to 4 ° C.). The detonation velocities indicated in Table I were determined in the cardboard tubes: (A) 7.5 cm in diameter at room temperature, ie 24 ° C, except blend C, which was studied at 27 ⁰ C. (B) 5 cm in diameter at the lower temperatures found in certain iron ore mines, namely 3 and 4 ³ C, detonated with a conventional intermediate charge. The detonation rates given in Table II were determined in cardboard tubes 12.5 cm in diameter initiated with standard 0.5 kg trinitrotoluene blocks.

Table I.

60

MMAN *) 10 10 3.33

ADAN *) - - 6.67

Water 19.6 19.6 19.6

AN *) 41.4 43.4 44.4

NN *) 15 15 15

Aluminum *) 4 2 2

Stearic acid 0.25 0.25 0.25

Coal 4 4 3

Formamide 4 4 4

Guar resin 0.7 to 0.9 0.7 to 0.9 0.7 to 0.9

Speed,

m / sec. A 4650 4500 4400

Speed,

m / sec. B 3700 3150 4150

*) MMAN = monomethylamine nitrate.
ÄDAN = ethylene diamine nitrate.
AN = ammonium nitrate.
NN = sodium nitrate.

Al = Reynolds 3XD pigment grade, coated with 3 percent by weight stearic acid.

The amine nitrates can be obtained by d ^; The same amount of monomethylamine perchlorate must be replaced.

Table II

D. E. F. G H I. J 20th _ 45 15th 20th 30th 20.6 10 30th - 30th 15th - · - 15th 15th 15th 15th 15th 15th 8.8 33 35.2 22.2 22.2 31 35 28.8 15th 15th 15th 15th 15th 15th 19.3 1 2 - - - - - 2 -. - · - - - - 2 2 2 2 2 2 2.6 - - - - - - 19.3 2 - - - - 2 - 1 1 0.8 0.8 0.8 0.8 0.8 0.6 1.35 1.35 1.35 1.35 1.35 1.35 1.7 4900 4400 4000 6000 4950 6300 5100

MMAN *)

ÄDAN *)

water

AT*)

NN *)

oil

Sugar cane fiber

sulfur

Ferrophosphorus
money

Hollow microspheres made of phenol HCHO resin

Guar resin

Density, g / cm ³

Speed, m / sec

*) See note to Table I.

For comparison, mixtures are not prepared in accordance with the invention, but essentially like mixtures A and B, but with 10 parts of AN replacing the 10 parts of MMAN (total AN content therefore 51.4 and 53.4 parts, respectively). These detonate under condition (A) with only 4250 or 3225 m / sec. and under condition (B) with 3550 and 2550 m / sec., from which the higher sensitivity of the amine nitrate-containing explosive mixtures according to the invention results, especially at the relatively low temperatures in iron ore mines. The comparative measurements also show higher sensitivity of the amine nitrate mixtures with relatively small amounts of fuel (z. B. only 2 ° / ₀ aluminum and 3 ° / o carbon) z over previously known mixtures with more fuel (. B. 4% each aluminum and carbon ).

0.8
1.45 4350

Example 2

The specified in Table III amine nitrates and half of the AN can be added to the water and the mixture to 60 to 65 ⁰ C is heated, after which the rest of the AN, eventual sea level, and any sulfur, premixed with guar gum added and 4 minutes are mixed. The crosslinking agent (0.01 ° / o potassium bichromate than l% aqueous solution is ^e, and 0.07% potassium antimony tartarate than 5% 'ge aqueous solution) are mixed in 30 seconds and the mixture is, in a 230 cm ³ glass with prehensive 5 Cast 6 cm in diameter, which stands on a cylindrical lead block (6.25 cm diameter, 10 cm high). The mixture is detonated with a hexogen charge of 50 g. All mixtures detonate at the specified temperatures.

Table III

Amine nitrate

Art

Oxygen balance

lot

water

AT*)

NN *)

sulfur

Refined mineral oil

Guar resin

Density, g / cm ³

Oxygen balance

Detonation ^{temperature, 0} C ....
*) See note to Table I.

MMAN *) -34 30

15 54.1

ÄDAN *)
-26
29.8

15th

54.2

0.7

1.4

-0.4

1.5

1.3

0.0

21

Monoethyl
-74
24.6 amine nitrate
-74
20.2 15th 10 42.7 69.1 15th - 2 - 0.7 0.7 1.3 1.5 -7 -1 25th 25th 109546/287

Table III (continued)

Amine nitrate
Art

Oxygen balance

lot

water

AT*)

NN *)

sulfur

Refined mineral oil

Guar resin

Density, g / cm ³

Oxygen balance

Detonation ^{temperature, 0} C ...

*) See note to Table I.

Trimethylamine nitrate -105 13

15 71

1.3 -0.6 21 aniline nitrate

-133
11th

15th
73

0.7

1.1
-0.8
25th

p-phenylenediamine nitrate
-75
17.5

15th
66.7

0.75
1.3

-0.6

Hydrazine nitrate

+8 30th

10
48

1.42
+0.3
-1.5

Example 3

AN aqueous solution with about 80% AN, solid AN and a 70 to 90 ° / ₀ aqueous solution of MMAN, or aedan alone, are mixed and heated to 50 to 6O ⁰ C. Sodium lauryl sulfate (commercially available as "DUPONOL ME") is intimately mixed in, premixed NN and guar resin are mixed in for 3 to 5 minutes until thickening occurs, then the sulfur is mixed in well, and crosslinking agents are added and mixed for a few minutes. The mixture is then filled into polyethylene bags with a diameter of 15 cm and allowed to cool in order to crystallize some of the AN.

Table IV

MMAN *)

ÄDAN *)

water

AT*)

NN *)

sulfur

Sodium lauryl sulfate

Guar resin

Speed,
m / sec

*) See note on

T U V 30th 30th 30th 15th 15th 15th 36.75 37 36.5 15th 15th 15th 2 2 2 0.25 - 0.5 1 1 1 3000 2800 5700

45 15 20 15 31.5

15 so 2

0.5 1

4950

55

Table I.

All mixtures have a density of 1.4 g / cm ³ , and their detonation speeds are determined at 0.5 ^° C., with the exception of mixture W, which is tested ^{at 10 ° C.}

This comparison shows an improvement in the sensitivity of the amine nitrate / fatty alcohol sulfate mixtures at low temperatures compared to amine nitrate mixtures without fatty alcohol sulfates.

Claims (1)

Claim: Use of salts of an inorganic oxidizing acid and an acyclic nitrogen base, in which no more than 2 hydrogen atoms are bonded to a basic nitrogen atom and which can contain up to 3 carbon atoms per basic nitrogen atom, and / or one Phenylamines that have at least a more positive oxygen balance than about -150%, possibly in a mixture with highly explosive explosives, as sensitizers in water-containing ones Explosive mixtures based on an inorganic oxidizing salt, a fuel and water, with the exception of the use of the nitrates of tertiary amines in water-containing explosives mixtures, those of 5 to 15 percent by weight of water, 30 to 80 percent by weight of ammonium nitrate, up to 10 percent by weight can be replaced by alkali and / or alkaline earth nitrates, 2 to 15 percent by weight of a high explosive with a detonation rate > 5000 m / sec., 2 to 10 percent by weight of tertiary amines or their nitrates, 5 to 25 percent by weight Perchlorates of ammonium and / or alkali metals exist, optionally under Addition of swelling agents and / or emulsifiers, which are 0.2 to 1 percent by weight of the total mixture can make out.