DE2159382A1 - Gel for explosive slurries and process for their preparation - Google Patents

Description

"HOMSEN - TlEDTKE - BüHLING

TEL. (Mil) S3 M11 TELEX: S-24 3OS U) (Mt

E3G212

PATENTANWÄLTE MflnchM: Frankfurt / M .:

Dipl.-Chem. Dr. D. Thomsen Dipl.-Ing. W. Weinkwiff

Dipl.-Ing. H. Ttedtke (Fuchthohl 71)

Dipl.-Chem. G. Buehling
Dipl.-Ing. R. Kinne
Dipl.-Chem. Dr. U. Eggera

8000 Munich 2

K «lsei ^ Ludwlg-Platze3O. November 1971

Imperial Chemical Industries Limited London (Great Britain)

Gel for explosive slurries and process for their preparation

The invention relates to thickened aqueous gels for Ekplosivaufschlangen, the production of such gels Punch exploratory preparations from such gels. These Gels are also generally applicable as binding and thickening agents.

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Explosive masses consisting of an oxygen-releasing salt, e.g. ammonium nitrate, a Solvents or media for this Saiz ₉ a thickener and a fuel are known "This hate is called usually ExplosivaufSchlammungsmassen or general explosive slurries «The consistency Such explosive sludge can become wet from highly viscous, almost plastic, extrudable to less viscous, almost liquid mixtures, that can be pumped or poured.

Exploitation reports of the type described usually contain materials and fuels that are widely known as essential components to increase performance * such as finely divided light metal, finely divided coal. It is beneficial in some cases to add a self-exploding fuel ingredient such as granular (QfT, FETK, or smokeless powder) to the hater to increase sensitivity and / or performance so that detonation and propagation are assured . Very different hates of this Irt are known.

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The greatest technical interest the hydrous Explosivaufschlämmungen in which most of the liquid carrier or are "dispersing agent for the solid components from water bestehtο While these hydrous Explosivaufschlämmungen many advantages have as a" B _e an economical method of production as well as an economic consumption and reduced At the moment of danger, however, the solid and liquid components tend to separate, both in the case of packaged explosives and explosives that are introduced directly into the borehole Components that could dissolve Hasse and thus lead to a false detonation ο To solve the problems of water attack and water penetration, the manufacturers of water-containing explosive slurries have a wide variety of Ve Thickeners are used as essential components of the slurries to "bind the components together to form a coherent gel that resists attack by excess water, so that the difficulties mentioned are overcome *

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A range of thickeners and / or gelling agents are known to be present in aqueous explosive slurries either alone or in Link bits to other agents by various means. Success have been used 'So are macromolecular compounds with neighboring cis-'. Hydroxyl groups are commonly used, and these are advantageously used with such crosslinking agents crosslinked to the cis-Ifydroxylgruppen bindο The most widely used thickener of this type are the galactomannans, in particular Guar gum, and these have been crosslinked with, for example, sodium dichromate, potassium dichromate, zinc chromate or potassium antimonate «These explosive slurries but have not fully proven themselves because they tend to syneresis when stored, especially when it is elevated Temperature and for explosive masses with calcium nitrate.

It is the aim of the present invention to provide a gel create j that is suitable for the thickening of aqueous explosive slurries and at increased Temperature is stable even in the presence of calcium nitrate «,

It has now been found that improved aqueous gels for explosive slurries with certain

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ice-bydroxylated compounds are thickened * can be generated in that the thickener with an oxide, acid or salt of ToIIiIr (VI) is networked. So can gels with a tough, rubbery Consistency can be easily produced «,

According to the invention, an aqueous gel which is suitable for an explosive slurry is an aqueous solution of a macromolecular compound with adjacent cis-hydroxyl groups as a thickening agent, this compound being linked with an acid τοη part (VI) or an acid produced from this oxide 'or a salt of this acid linked as macromolecular thickener may be moderately a Galaktomannangumml, a Glukomaaaangiiami, a Glukoxylgalaktangummi or Xylogalaktan »rubber, such as guar gum, Locustbohnengusimi, tara gum, Ile8mannangummi, Taraatindgummi or _Λ

Fsyllium seed gum, telluric acid, tellurium oxide or an alkali metal salt of taluric acid are advantageous as crosslinking agents. ZoB. Sodium tellurate, used »

When used in an explosive slurry, the gel can advantageously be at least one inorganic contain oxygen-releasing salt.

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A preferred aqueous gel for explosive slurries contains at least 15 to 83 parts by weight an inorganic oxygen-releasing salt, 10 to 30 parts of water and 0.2 to 10 Weight point of a crosslinked ice-hydroxylated one macromolecular thickener, in which the crosslinking agent in an amount of 1 to 30% by weight based on the thickener used became. .

The inorganic oxygen-releasing salt can expediently. be a nitrate or Ferchlorat _f of ammonia, sodium, potassium, barium or calcium or a mixture of two or more of these compounds "The gels of the invention have a high $ oleranz to electrolytes and can be used in saturated solutions of each of these salts or mixtures thereof formed will"

The exploitive slurries according to the invention contain the described gel with the inorganic one oxygen-releasing salt mixed with a sensitizing fuel. Preferably does the fuel 5 to 55% by weight of the explosive mass from ο

A water-soluble or water-insoluble, explosive or non-explosive combustible

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material are used * All insoluble fuels are advantageous partially ohenfSrmiges light metal or metalloid into consideration, a _or B. finely divided

Aluminum or. Aluminum alloy, silicon, ferrosilicon, ferrophosphorus, particulate organic Explosives, sulfur or carbonaceous

Substances under consideration ο

Suitable particulate organic explosives that can be used in the Hassen are for example THiD, EETN, Cyclotrimethylene trinltramine (BSKC, Mass B (mixture of THT and RItS) ₉ pentolite (mixture of PETK and TKT), smokeless powder, nitrocellulose, nitro starch and mixtures this·

Suitable soluble fuels are u »b. Glycol, diethylene glycol, dioxane, methyl cellosolve, methyl carbitol, sucrose, urea or thiourea o No compounds with cis-hydroxyl groups (soB ₀ glycerine) should preferably be used as monomeric soluble fuels, since such compounds could react with the crosslinking agent.

The masses can also be modifiers, e.g. middle to adjust the density, contained So it is generally advantageous if one of a mass, which do not have a self-explodable sensitizer

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included, a gas generator, ζ «.Β. Sodium nitrite, admixed.

The invention also relates to a method jfeur Preparation of an aqueous gel for explosive slurries, after which a macromolecular Thickening compound containing adjacent cis -hydroxyl groups dissolved in water with a Oxide of tellurium (VI) or an acid derived from this oxide or a salt of this acid is networked.

In an expedient Aueführungeform is the macromolecular compound in a non-dissolving liquid medium, ZOB "Oiathylenglykol dispersed and then a solution of the crosslinking agent in water, which optionally also contains dissolved inorganic oxygen-releasing salt, added _o Eb is also possible, the macromolecular compound and to disperse the crosslinking agent in a non-dissolving liquid medium and to mix the dispersion with water or an aqueous solution of the oxygen-releasing salt. A few hours after the thickening agent and the crosslinking agent have been dissolved in water, the crosslinking is complete and the solution is converted into a rubber-like gel.

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The crosslinking agent can be thickened as such Gel mass is added or formed in the course of mixing, in the latter case the tellurium in the form of a compound in the lower valence Oxidation condition as well as a quarrying agent for transfer of the! fellurs to the desired high quality Hate's state of oxidation admitted. So the hater can connect with Tellurium (IV) as well Hydrogen peroxide, chromium oxide or a Alkali metal dichromate, peroxide or permanganate be added so that a crosslinking agent with Tellurium (VI) is produced.

The networking is faster if the solution is somewhat acidic, so that ea is beneficial when the slurry is acidified "

The watery gels and explosives? Invention have a far better shelf life at elevated temperature and prolonged storage. They are stable at pH values from below 4 to over 1Ö and are very water-resistant

The invention is illustrated below by means of examples explained in more detail, all parts and percentages given being based on weight.

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Examples 1 to 4

Hall examples represent aqueous gels with different cross-linked! Guar gum.

In preparing these examples, four solutions were used with different amounts of telluric acid prepared, and dispersions of guar gum in dirnethylene glycol were added to these solutions At first a fast was formed. After several hours, however, gel formation occurred, so that Gels of different stiffness were obtained «as can be seen from Table 1«

Table 1

Example % Guar-Gu & ■% Telluric acid pH properties of gel no ο in gel in gel

1 5.0 1.5 5.3 Rubbery, no
deformable. 2
3 5.0
2.0 0.15
0.06 5.8
6.4 Guifflttiartigj, deformation
under dead weight »
Easily networked 2.0 0.02 6.7 Very easy
networked.

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Examples 5 to 9

These examples represent aqueous gel bases with dissolved inorganic oxidizing salt The compositions can be found in Table 2 »In the presentation of the gels, the ammonium nitrate, Calcium nitrate, water and the tellurium compound are mixed together, whereupon the pH value by adding saltpetre solution to 4.5 to 6.0, the normal pH value for explosive slurries, was discontinued. Then the guar guu was added in the form of a dispersion in diethylene glycol »

After standing for 12 hours at 50 ⁰ C a gel gutomiartiges each originated * dasmindestens for 3 months remained stable in storage at 5O ° C.

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Table 2

example
ffr. 5 . - 6th - 7 ■ - 8th 1 - 15th 9 Composition
(Parts) - - - 5.4 . · Ammonium nitrate 1600 5.9 1600 5.4 1600 4.8 1600 1600 Calcium nitrate 800 800 Examples 800 10 to 800 800 Guar-GuiB 40 40 40 40 40 Dietary glycol 50 50 50 50 50 water 800 800 600 800 800 Telluric acid 1 1 1 - - Ifodium tellurate - - Tellurium oxide 1 PH value 5.5

These examples represent Eacplosivaufschlamungen with the compositions and properties to be taken from Table 3. During the production of the cash registers, a mixture that contained the oxygen-releasing salts, the water and the guar gum (which was previously dispersed in the ethylene glycol) was added to one pH value of 5.0 acidified with acetic acid, ^{heated to 50 0} C and about 3 hours at this tem-

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temperature held until the guar gum was completely dissolved. An aqueous solution or suspension of the tellurium compound was then added, after which a mixture of powdered aluminum and the sensitizing fuel was added to the Hasse o In Example 12, the Hasse was sensitized by gassing with sodium nitrite, which was added last to the Hasse. After 12 hours, a cross-linked, rubber-like gel was formed, which was very storage-stable and water-resistant. After storage for 6 Honate at 50 ⁰ C in the no syneresis Explosivmas sen could be observed. The minimum initial explosive quantity and the detonation speed were measured for samples which were ignited in wrought iron pipes with a wall thickness of 6 mm.

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Tabel

Example ffr. 10 11 12th 13th Additional statement .Aan? N1 vtani entered 42.4 53.0 42.3 32 _f 4 Üatriium nitrate 3.3 5.0 3.3 3.3 Calcium nitrate 27.4 - 27.4 27.4 Diatbylenglorkol 8.0 1.2 8.0 8.0 ****** 8.3 15.0 8.3 8.3 Gwtr-Gu » 0.6 0.8 0.6 0.6 lluMiniuea deaf 7.5 5-0 10.0 5.0 A1n.1nlii «pulTer ' , · *
2.5

PIEIH

Hatriuenitrite Teliuric Acid Tellurium © jyd flatriustellurate

Eifenechaften Density (ftg / c ³ )

minimum initial quantity of fuel (Drilling 0 5 cm)

■ minimal initial amount of aprengate (Bohr 0 12.5 approx) Detonation agew. (ke / eec) 0 5cm

0 12.5 approx

20.0

0.10

0.012 0.012

1.35

1.40

0.012

1.10

Vr.6 3g

Detona-Fentolit gate

25.0

0.012

1.50

220g pt

Fentolite Pentollt

3.5

5.5

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Example 14

The composition of this cash register was the same as in Example 10, with the difference that one instead the telluric acid used 0.01 part of tellurium (IV) oxide and after mixing in all the components according to Example 10 to the power of 0.007 parts of potassium permanganate to oxidize tellurium (IV) oxide to tellurium (VI) oxide admitted. The properties of the explosive mass were identical to those according to Example 10

Example 15

Bs was worked as in Example 14, with the Deviation that as an oxidizing agent 0.007 parts Sodium dichromate were used · The properties are identical to those of Example 10

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Claims (1)

- 16 claims 1. Gel suitable for explosive slurry «that as Thickener contains an aqueous solution of a crosslinked macromolecular compound with adjacent eiB hydroxyl groups, thereby characterized in that an oxide of tellurium (VI) or one of this oxide is used as the crosslinking agent derived acid or a bale of this acid is chosen. 2ο Gel according to claim 1, characterized in that a galact omannan gum, a glucomannan gum, a glucoxylgalactan gum or a xylogalactan gum is selected as the macromolecular thickening agent. 3 »gel according to claim 2, characterized in that as macromolecular thickening agent guar gum, locust bean gum, tara gum, xlsemannan gum, Tamarind Gum or Fsylllum Seed Gum is chosen. 4. Gel according to one of claims 1 to 3 *, characterized in that tellurium oxide as the crosslinking agent Telluric acid or an alkali metal salt of telluric acid is selected. - 17 - 209827/1011 5. Gel according to claim 4, characterized in that as Crosslinking agent sodium tellurate is chosen 6ο gel according to one of claims 1 to: 5, characterized in that the gel contains 15 to 83 * * parts by weight of at least one inorganic oxygen-releasing salt, 10 to 30 parts by weight of water and 0.2 to 10 parts by weight of a crosslinked ois-hydrosylated macromolecular thickener, in which the crosslinking agent is used in amounts of 1 to 30% by weight based on the colloid. 7 · Gel according to claim 6, characterized * that as an inorganic oxygen-releasing salt Mitrat or ferchium of ammonia, sodium, potassium, Barium, magnesium or calcium or a mixture of two or more such compounds are selected will. 8 · Aqueous explosive slurry, characterized in that it contains an oil according to claim 1 ι. * {Inorganic oxygen- releasing »SaM WtA« inen Sensitizing fuel contains ^ ^ 209827/101 1 Exploaivsehlwuaung according to claim 10, characterized characterized, the ει derFuel 5 to 55 wt # that makes up expiosiYmass Explosive insulation according to claim 8 or 9t characterized in that the fuel used is a light metal or metalloid, particulate organic explosive, sulfur or as a fuel carbon-containing substance or a mixture of «wet or more of these fuels is selected. 11. Explpaivauf slurry according to claim 8 or 9 » characterized in that aluminum, aluminum alloy, silicon, ferrosilicon, perrophosphorus,! DSf, PETH, cyclotrimethylene trinitramine, Hasse B, fentolite, smokeless powder, nitrocellulose, Hitrostarke, Glycol, Oiäthylenglykol, Dioxan, Methjlcellosolve, Methylcarbitol, Sucrose, Urea, thiourea, or a mixture of two or more of these fuels are selected. 12. Exploit sludge according to one of the claims 8 to 11, characterized in that it contains a means of adjusting the density only. 1? · Exploitive slurry according to claim 12, characterized in gek «m *« is worth that as a means but attitude - 19 - 209827/1011 ~ «IQ - the density of sodium nitrite is chosen ο Method of making an aqueous gel for an explosive slurry, characterized in that that a macromolecular thickening compound which contains adjacent cis-hydroxyl groups and dissolved in water, hit an oxide of tellurium (VI) or an acid derived from this oxide or a salt of this acid is crosslinked. 15 «, method according to claim 14, characterized in that that the macromolecular compound is dispersed in a non-dissolving liquid medium, and that the dispersion obtained is added to an aqueous solution of the crosslinking agent o 16. The method according to claim 15, characterized in that that the dispersion of the macromolecular compound of an aqueous solution of the crosslinking agent f as well as an inorganic oxygen-releasing agent Salt is added. 17. The method according to claim 14, characterized in that that the macromolecular compound and the crosslinking agent in a non-solvent liquid Hedium are dispersed, and the water or an aqueous solution of an inorganic oxygen * - 20 -209827/1011 dispensing salt is added «. 18ο method according to any one of claims 15 to ^20,: characterized in that is chosen as the liquid medium niehtlosendes Dläthylenglykol " 19. The method according to any one of claims 14 to 18, characterized in that the crosslinking agent in situ in the hatred during their intermingling is formed by a tellurium compound with the tellurium in a low oxidation state as well as an oxidizing agent for converting the tellurium into the desired high-quality oxidizing state to be added » 20 _{o The} method according to claim 19, characterized in that a compound containing tellurium (IV) and a Qaydierungsmittei of hydrogen peroxide, chromium oxide or an alkali metal dichroate, peroxide or permanganate are added to the mass, so that a crosslinking agent, the tellurium (VI) contains, arises., "Method according to one of claims 14 to 20, characterized “that the hatred is acidified to accelerate networking - 21 ~ 209827/101 1 22. Aqueous gel for one is characterized by that it ^ eine® method according to any claims 14 to 21 eggs produced "