DE1771480C - Aqueous explosives mixture - Google Patents

Description

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, erythritol are sensitized to ar lower amounts

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, but these are used

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 weiva man

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

Difficulties in processing, since sodium nitrate replaces itself at 15, so becomes the sensitive wedge

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; the sensitization

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

Impairs the blasting properties and cannot be shown in the ao.

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 as methylentetramine. 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 an excess or deficiency of the oxygen, the fUi

nation speed to. complete combustion is required and will be

The invention relates to the use of as the molecular weight of the Salts of an inorganic oxidizing acid and combustion required or released during the same

an acyclic nitrogen base in which no more than 35 oxygen divided by the molecular weight of the

2 hydrogen atoms on a basic nitrogen atom, calculated. A "sensitizer" is

are bound and which have up to 3 carbon atoms each a substance which, if it is present in small quantities (e.g.

may contain basic nitrogen atom, and / or some percent) added to an explosive

of a phenylamine which becomes at least one more positive, its sensitivity and initiating ability

Having an oxygen balance of about 150%, given a given temperature, increases considerably

if mixed with highly explosive explosives, as and vice versa when removing from the explosives

Sensitizers in a water-containing mixture of explosives increases the critical diameter of the mixture,

gene on the basis of an inorganic oxidizing The nitrogen bases used according to the invention

Salt, a fuel and water, which can be excluded from inorganic bases such as hydrazine

the use of the nitrates of tertiary amines in water but preferably aliphatic amines or phenyl

containing explosive mixtures, consisting of 5 bis amines, d. H. Compounds with a carbocyclic

15 percent by weight of water, 30 to 80 percent by weight of aromatic ring, to which at least one, preferred

percent ammonium nitrate, which contains up to 10 weight wise one or two primary amino group (s)

percent is (are) bound by alkali and / or alkaline earth nitrates. It can be secondary or tertiary

2 to 15 percent by weight of a bri- so amines can be used, but primary amines are

santen explosives with a detonation speed preferred because of the higher N to C ratio,

speed> 5000 m / sec., 2 to 10 percent by weight ter- bases, which are made up of the elements carbon, hydrogen

tiary amines or their nitrates, 5 to 25 weight and basic nitrogen, are preferred,

percent of ammonium perchlorates and / or other substituents may be present. Ge

■ B Bi * Jl _ ■■ M _t i Bk ■ * ^ ___. * .m__k ..B BBiB, Bh. Jb. ΛΛ Λ Λ B ^ B ₁

Alkali metals, It with the addition of swelling & saturated aliphatic «amines with up to 3 carbon

Agents and / or mutants containing 0.2 to 1 Oe * atoms are particularly preferred. The oxidizing «

weight percentage of the cesamtin mix, acid knows any suitable strong inorganic oxy

Monomethylamine nitrate would be a constituent acid, preferably a mineral acid,

gosienerAmmonsälpeter-Sprengstoffe In the German like nitric acid, nitrous acid, chloric acid odei Patent specification 581 $ 14 proposed and in the second «β üeerchlorslure, and should preferably be an oxygen ·

World War used «. ürbanskl, »Have a chemistry balance of at least + 10%. nitric acid

and Technology of Explosives *, Sd, 2, p. 465 bit 4M. is particularly preferred.

D Zt flt Hb d E Form for i The addition was made to reduce the solidification - examples of suitable lenslililating salts are

Punktee, in order to achieve a more homogeneous structure

Target. Containing in water * Sorengitoffmungenbe 'β' percnlorati salts aliphatic «amines, · such as mono-

the addition not recommended, also mentions ur · methylamine nitrate, «chforate and • Mdrehoratj ethylene«

b a η 1 k I all disadvantage the Hygroikoplzltlt. dlamindlperehlofat; Dimethylamine stepped; AthylamifH

In the clear patent specification 964 4 * 0, advocates and Proeviamlnltrat! Ouanidlnnl resigned

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 required amount of salt decreases, and ethylene diamine nitrate is particularly preferred because of its easy 5 when the water content is decreased and when the addability to explosive mixtures and the amount of other auxiliary sensitizers increases 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 bilating salts in amounts of about 10 to 50%. Each salt with other similar salts, the oxygen of which, according to its oxygen balance, forms the salt of the nitrogen balance more negative than -150 ° / _? is, for example, cyclohexyl base either part of the oxygen carrier or, more often, amine nitrate and diethylamine nitrate, can be used as part of the fuel. The resulting oxygen balance of the mixture is then more positive than -150 ° / ₀ . the salt of the nitrogen base sensitized explosives

The salts of the nitrogen bases can be added to the explosive mixture, if desired, in a 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 added to the neutralizing oxidizing acid. In addition, a fatty alcohol which is soluble in the mixture. This mixture is either separately dissolved in aqueous sulfate, d. H. a neutral salt of an acid ester of the Solution prepared and then with the remaining Be 10 sulfuric acid with a saturated aliphatic components of the explosive mixed, or it is of primary alcohol with 8 to 22, preferably 8 to On the spot in the presence of one or more of these 18 carbon atoms, adds. Preferably are Components manufactured. Thus the oxidizing sulfates of this kind can be salts of the alkali metals, especially of the Ingredient and fuel mixed with water, sodium and potassium, ammonium, ali, and the product is then neutralized by phatic amines with up to 5 carbon atoms Sieren one or more of the nitrogen bases with one or the amino alcohols with 2 to 6 carbon or more dei oxidizing acids obtained. atoms. Such preferred sulfates can be obtained by the *

It is an advantage of the water-containing explosives general formula mixtures according to the present invention that they q ^, q ^ ■> QgQ ^ do not require the usual metallic S. rengstoffsensibili- 30 " ² * sators, such as finely divided aluminum, or are shown in which M is one of the strong explosives mentioned, which fall into two categories, cations, e.g. Na ⁺ or K ⁺ , and η is a highly explosive explosives of the type of penta value from 7 to 21. Alkali salts of fatty alcohol erythritol tetranitrate, hexogen and Octogens (it is sulfates, especially sodium salts of monoesters, to be remembered that in German patent 35 sulfuric acid with an aliphatic alcohol with 1119 740 and British patent 882 555 8 to 14 carbon atoms, especially before pentaerythritol tetranitrate and hexogen are added as explosives Examples of suitable sulfates of fatty alcohols recommended with high detonation speed are sodium nonyl sulfate, Potassium lauryl sulfate, Am werden) or less strong, highly explosive Sensibili- monium lauryl sulfate, the methylamine salt of lauryls, such as trinitrotoluene and smokeless powder, 4 ° sulfate, the diethanolamine salt of lauryl sulfate, Na or mixtures thereof, z. B. Pentolite (pentaerythritol trium cetyl sulfate, ammonium cetyl sulfate, potassium cetyltf.tranitrate / 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 significantly lower 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 SSS, namely in an amount usually only 0.2 to 2 percent by weight and generally less than 8% of the weight of the total so 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, quantities must produce excessive foaming and must be sharply defined between the present invention, formulating and mixing the explosives, which divide on the sensitizing effects of one or more of the salts of Stick · SS described above without promoting the explosive properties The weight ratio between the fatty alcohol bases is based, but in addition high lutrophate and the salt of the sugar base are typically explosive sensitizers with a high detonation rate in the range from 1:10 to 1: 1000. preferably, speed should be contained in small amounts from 1:30 to 11 IK).

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

882 545 on the other hand, according to which certain explosions of an aqueous solution or pulpy dispersion

Mixtures of substances added by solid explosives from high levels, preferably to a hot one Detonation rate, such as pentaerythritol tetra · (50 to 80 "C),» neutral, essentially saturated

nitrite and hexogen, must be wllsiert, but with the solution of the oxidizing component before the addition

apart from small amounts of additives are included, the set of a thickening * or gelling agent, to

Because although there is a site of 8ückitoffbasen a · «1 beginning there is a reasonable large part

concludes "without there being recognized that the oxidizing salt is in solution. Bin Till de · Saht «

ü Silze it "this" group IQr crystallizes on its own but when the product cools down,

1 and can be effective sensitizers. M diS at room temperature 10 to 20 / d «of salt

unsolved, d. H. can be crystallized, while at 5 ° C up to 50% of the salt is crystallized, If necessary, auxiliary fuels and other additives, such as liquefaction additives, buffers, e.g. Fumaric acid, and sensitizing amounts of j * as-filled Hollow spheres can be added to the hot solution or to the cooled product in order to obtain the To influence characteristics of the mixture. The addition of the fatty alcohol sulfate to the hot solution before Cooling is particularly beneficial because salts of alcohol sulfates, especially the preferred sodium lauryl sulfate, tend to affect crystallization. Biliden especially from solutions of ammonium nitrate In this case, 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, the even inclusion is likely to be extremely small gas-filled Cavities, e.g. B. air bubbles, e.g. B. between 5 · 10 * and 5 -10- · cm in diameter, on the whole Attributing Mixture.

The other ingredients can be those normally conventionally used in hydrous explosives. Suitable mixtures therefore contain at least 20 percent by weight of inorganic oxidizing salt, such as ammonium, alkali, alkaline earth nitrates and / or perchlorates. At least 45 ° / ₀ of this component at room temperature are easily soluble in water, such as ammonium nitrate, so that desirably the aqueous phase is an elevating Liehe amount, eg. B. at room temperature 40 to 70 percent by weight, of oxidizing salt. Mixtures of inorganic oxidizing salts containing at least 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 provide essentially all of the fuel contribution, but it is often desirable to add a conventional auxiliary fuel provided that the fuel in question is chemically stable in the mixture during its manufacture and storage. Examples of auxiliary fuels are sulfur, carbonaceous fuels such as coal dust and other forms of finely divided coal, and solid carbonaceous natural products such as corn starch, ground wood, 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%. Apart from mixtures containing heavier metallic fuels such as ferro phosphorus and ferro silicon, the oxygen balance is preferably between -10 and + 10%.

The water content is generally at least 5 percent by weight and up to 50 percent by weight; It is preferably of 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 resin, usually in amounts of 0.1 to 5% of the total weight of the Mixture. The thickeners are normally incorporated before the auxiliary fuels or sensitizers. Galactans are preferably crosslinked with an oxidizing agent such as alkali bichrarnate either alone or in combination with a soluble antimony compound. The crosslinking agents are generally added shortly before packing in the case of packaged products and shortly before being poured into the well in the case of products which are pumped by tankers, but guar resin in combination with polyacrylic acid amide is often preferred for coherent yet pourable explosives .

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-! '. 74% aqueous Solution of monomethylamine nitrate ^ M MAN), alone or with ethylenediamine nitrate (ÄDAN), are

ao mixes, heated to 54 to 60 ° C and transferred to a mixing vessel, where premixed sodium nitrate (NN) and Guarh-rz are added. Mix 3 ¹ / "minutes is observed until thickened, then the fuel are mixed evenly in amounts shown in Tables I and II levels. 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 given in Table I were determined in cardboard tubes: (A) 7.5 cm diameter at room temperature, ie 24 ° C, except for mixture C, which was examined at 27 ° C. (B) 5 cm in diameter at the lower temperatures found in certain iron ore mines, namely 3 and 4 ° C, detonated with a conventional intermediate charge.

The detonation rates given in Table II were in cardboard tubes with a diameter of 12.5 cm which were initiated with standard 0.5 kg trinitrotoluene blocks.

Table I.

19.6
41.4
15th

0.25

19.6
43.4
15th

0.25

0.7 to 0.9 0.7 Wi 0.9 0.7 to 0.9

MMAN *)

ÄDAN *)

water

ON*)

NN *)

Aluminum*)

Stearic acid

money

Formamide

Guar resin,

Speed,

m / sec, A

Speed, m / sec. B ......

♦ 1 MMAN => monomethylamine filtrate,
ÄDAN = ethylene diamine nitrate.

AN = ammonium nitrate,
.. NN = sodium nitrate,

° ^a Al "= Reynold" 3XD pigment grade, coated with

3 weight percent stearic acid,

The amine nitrate knows because of the equal amount of monomethyl amlnperchlofte first «.

4650 3700

10

4500 3150

6.67 19.6 44.4 15

4400 4150

Ii i

480

table It

MMAN ·)

ÄBAN ·) .....

water

ON·)

ΝΝ ·)

oil

Sugar cane fiber

sulfur

Ferrophosphorus money

Micro-hollow ogel made of phenol * HCHO resin

Guar resin

Density, g / cm *

Speed, m / sec

·) See note to Table I.

D. B. P. O M. I. i 20th _ 45 15th 20th 30th 20.6 10 30th - 30th 15th . . IS IS IS • IS 15th 15th 8.8 33 35.2 22.2 22.2 31 35 28.8 IS IS 15th 15th IS IS 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 1.33 1.35 l, 3i 1.35 1.35 1.35 1.7 4900 4400 4000 • 000 4950 6300 5100

For comparison, mixtures are not produced 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 322S tn / 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 Vergleichsmessuagen also show higher sensitivity of the Aminnitratmisehungen with 4 * relatively small amounts of fuel (for example, only 2 ° / o aluminum, and 3 · / * coal) over previously known mixtures for example with more fuel (. 4 per ° / ₀ Aluminum and Money).

0.8 1.45 4350

Example 2

The amine nitrates listed in Table HI and half of the AN are added to the water and the mixture heated to 60-65 "C, whereupon the remainder of the AN, any NN and any sulfur, premixed with guar, added and mixed for 4 minutes. the crosslinking agent (0.01 * / · potassium bichromate than l * / * aqueous solution and potassium antimony tartarate 0,07Vt than 5 ^e / "aqueous solution) are mixed 30 seconds and the mixture is placed in a 230 cm * sive glass with 5 , 6 cm diameter, which stands on a cylindrical lead block (6.25 cm diameter, 10 cm height) 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

crowd

water

ON*)

NN *)

sulfur

Refined mineral oil

Guar resin

Density, g / cm ³

Oxygen office

Detonation temperature, ° C

• 1 See note on Table T.

MMAN *) -34 30

15 54.1

0.7

1.4

-0.4

1.5 ADAN *)
-26
29.8

15th
54.2

1.3

0.0

21

Monoethylamine nitrate -74 -74 20.2 24.6 10 15th 69.1 42.7 - 15th - 2 0.7 0.7 1.5 1.3 -1 -7 25th 25th

I 771

Table HI (continued)

Aminnitrate
Art.

Oxygen balance

crowd

water

ON·)

ΝΝ ·)

sulfur

Refineries «» Mineral Oil

Guar resin

Density, g / cm *

Oxygen bilflz

Detonation ^{temperature, 0} C ... *) See note on table t.

Trimethylamine nitrate -103 11th

15 71

1.3-0.6 21 aniline nitrate

-133 11th

15th 73

0.7 !.1 -0.8 25th

P'phenylenediamine nitrate -75 17.5

15th 66.7

0.75 1.3 -0.6 25th

Hydra2innUfat

+8 30th

10 48

1.42 +0.3 -1.5

Example 3

Aqueous AN solution with about 80% AN, solid AN and a 70 to 90% aqueous solution of MMAN, alone or with ADAN, are mixed and heated to 50 to 60 "C. Sodium lauryl sulfate (commercially available available as * DUPONOLME «) is intimately mixed in, premixed NN and guar resin are mixed in for 3 to 5 minutes until thickening occurs, then becomes the sulfur is mixed in well and crosslinking agents are added and mixed for a few minutes. Then the mixture is filled into polyethylene bags of 15 cm diameter and allowed to cool, to crystallize part of the AN.

Table IV

MMAN ·)

ÄDAN *)

water

ON·)

NN ·)

sulfur

Sodium lauryl sulfate

Guar resin

Speed, m / sec

*) See note to Table I.

30th

15th

36.75 |

15th

0.25 |

3000

30th

15th

37

15th

2800

30th

15th

36.5

15th

0.5

5700

15th

20th

15th

31.5

15th

0.5

4950

45

55

All mixtures have a density of 1.4 g / cm *, 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 and fatty alcohol mixture 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, excluding the use of the nitrate of tertiary amines in hydrous explosive mixtures, which are from 5 to 15 percent by weight Wesser, 30 to 80 percent by weight ammonium nitrate, which carries up to 10 percent by weight Alkali and / or alkaline earth nitrates can be replaced by 2 to 15 percent by weight of explosive explosives Substance with a detonation speed> 5000m / sec., 2 to 10 percent by weight tertiary « Amines or their nitrates, 5 to 25 percent by weight perchlorates of ammonium and / or cxie the alkali metals, optionally with the addition of swelling agents and / or emulsifiers which 0.2 to ί percent by weight of the total be able to make a mixture.