CS205268B3 - Explosive mixture - Google Patents

Description

The present invention relates to the use of aqueous solutions of inorganic nitrates containing nonvolatile organic compounds of the type polyols, sugars or N-Mannich bases as one of the components of water-plasticized explosives.

From the preparation of 1,5-eniomethylene-3,7-dinitroso-1,3,5,7-tetraazacyclooctane by nitrosation cleavage of hexamethylenetetramine using a combination of nitric acid and alkali metal nitrite (Gries and H-rrow: Ber. 1888, 21, 2737) Duden and Scharff: Ann., 1895, 288, 218; Antos, Forman and Kristian: Chem. Rumors 1956, 10 162; French Pat. No. 1,580,636; Inorganic nitrate solutions containing some of the starting nitrite, formaldehyde, hexamethylenetetramine and sometimes even small amounts of organic polyol-type compounds (C ^-C)) are omitted as sources of nitrosating agent. or sugars (C 1 to C 2). Nitrite present is easily removable from wastes of this type but disposed of (Czechoslovak author 's certificates no. 85 888 and no.

196 707) or the use (Czechoslovak author's certificate no. 199 088) of organic fractions is very complicated.

Czechoslovak author's certificate No. 199 090 solves the treatment of wastes from the production of 1,5-endomethylene-3,7-dinitroso-1,3,5,7-tetraazacyclooctane so that after the removal of the present nitrite the free formaldehyde is converted into non-volatile substances of the type polyols (C1-C4), sugars (C1-Cy) and N-Mannich bases (hexamethylenetetramine and condensates corresponding to sugars). Said p-products of the formation reactions are individually applied as components of water-plasticized explosives, which can be documented in the case of hexamethylenetetramine, for example, by U.3. No. 3,962,001 (1976), in the case of polyols, by S. Africa 74 03, 305 (1975), U. S. 3,899,374 (1974) and Japan. Kokai 76 01, 616 (1976) and in the case of sugars, for example, U.S. Pat. No. 3,962,001 or Japan. Kokai 76, 67, 71, (1976).

The present invention solves the application of inorganic nitrate solutions containing polyols, sugars and / or N-Uanich bases and obtained by treatment of wastes from the production of 1,5-endomethylene-3,7-dinitroso-1,3,5,7-tetraazacyclooctane (U.S. Pat. No. 199 090) as one of the water-plasticized explosive components. Exploatable in this sense and mixtures of the above composition have not been described in the scientific or patent literature. It solves environmental issues in relation to the production of 1,5-endomethylene-3,7-dinitroso-1,3,5,7-tetraazacyclooctane by fully evaluating the waste from this production during rock disintegration.

He did

Treated wastes from the production of 1,5-endomethylene-3,7-dinitroso-1,3,5,7-tetraazacyclooctene (MSc. No. 199 090) were available, having a pH = 6.7, a density at · 20 ° C = 1,330 g.cm 3 _and composition by weight: 11,35% sodium nitrate, 16,66% calcium nitrate, 4,86% ammonium nitrate, 2,75% hexamethylenetetramine, 0,80% polyols (expressed as glucose) and 63.58% water. The polyols in said composition represent a mixture of polyols (C 1 -C 4) and sugars (C 1 -C 4), expressed as glucose. In 200 g of this mixture, to which 50 g of ethylene glycol was added, 6 g of a surfactant (here oleylacetyl polyglycol ether) and 6 g of guar meal were dispersed with vigorous stirring.

This mixture, together with 900 g of ammonium nitrate and 60 g of hexamethylenetetramine, was subjected to a five minute homogenization in a kneader. This resulted in a water-plasticized explosive with a composition (in percent by weight): 75.06% ammonium nitrate, 2.75% calcium nitrate,

1.87% sodium nitrate, 4.58% hexamethylenetetramine, 4.12% ethylene glycol, 0.13% polyols (expressed as glucose), 0.50% guar gum, 0.50% oleylacetyl polyglycol ether and 10.49% water. With a diameter of 90 mm and a charge density of 1.337 charge g.cm ^- ^ detonation velocity was 4.38 km.s ^- 'vetonační calculated and then the pressure was 6 GPa o2.

Example 2

Treated and thickened wastes from the production of 1,5-phendomethylene-3,7-Uinitroso-1,3,5,7-tetraazacyclooctane (according to the author's certificate No. 199 090) having a pH = 6.3, chemical consumption were available oxygen 40 g oxygen per kg and composition in mass for oceans: 38, ‘07% sodium nitrate, 8.12% calcium nitrate, 0.40% ammonium nitrate, 3.43 $ polyols (calculated as glucose) and 49.98% water.

Similar to Example 1, a water-plasticized explosive having a composition (by weight%) was prepared from this mixture with the addition of oleyl acetyl polyglycol ether, guar gum, ammonium nitrate and 1,3,5-trinitro-1,3,5-triazacyclohexane: 4 Sodium nitrate, 66.99% ammonium nitrate, 1.03% calcium nitrate, 8.30% ethylene glycol, 9.34% 1,3,5-trinitro-1,3,5-triazacyclohexane, 0.43 % polyols (calculated as glycose), 0.80% guar gum, 0.53% oleylacetyl polyglycol ether and 7.69% water. At a charge diameter of 90 mm and a charge density of 1,420 g.cm < -1 > it was detonating. speed 5.33 km.s ^- 1 and calculated detonation pressure 10.41 GPa. The proportion of treated wastes from the production of 1,5-endomethylene-3,7-dinitroso-1,3,5,7-tetraazacyclooctane in this explosive was 12.7% by weight.

Example 3

Treated wastes from the production of 1,5-endomethylene-3,7-dinitroso-1,3,5,7-tetraazacyclooctane (according to the author's certificate No. 199 090) were available, having a density of 1,280 g.cm at 20 ° C. ^- ^, chemical oxygen demand 25.05 grams of oxygen per 1 kg of the composition in wt. percentages: 23.86% sodium nitrate, 5.09% calcium nitrate, 0.25% ammonium nitrate, 2.15% polyols (expressed as glucose) and 68.65% water. 4.5 g of surfactant (oleylacetyl polyglycol ether) and 4.5 g of guar meal were dispersed in 150 g of this mixture with vigorous stirring. This mixture, together with 800 g of ammonium nitrate, 83 g of 1,8-dinitronaphthalene and 37 g of aluminum powder (atomic aluminum), was subjected to a five minute homogenization in a kneader.

Resulting explosive composition (% by weight): 74.12% ammonium nitrate, 3.31% sodium nitrate, 0.71% calcium nitrate, 7.68% 1,8-dinitronaphthalene, 3.42% atomic aluminum, 0 , 30% polyols (expressed as glucose), 0.42% guar gum, 0.51% oleylacetyl polyglycol ether and 9.53% water. With a diameter of 90 mm and a charge density of 1.518 charge g.cm ^- · ^ showed a mixture of said composition having a detonation velocity km.s 4.28 ^- 'and the calculated detonation pressure 7.18 GPa. Share of wastes from the production of 1,5-endomethylene-3,7-dinitroso-1,3,5,7-tetraazacyclooctane, treated according to MS. No. 199 090, in this mixture was 13.88 wt.

Example 4

Treated wastes from the production of 1,5-endomethylene-3,7-dinitroso-1,3,5,7-tetraazacyclooctane of the same composition as in Example 3 were available. A procedure, analogous to Examples 1, 2 and 3, produced an explosive (composition % by weight): 5.01% sodium nitrate, 68.35% ammonium nitrate, 1.07 calcium nitrate, 4.20% ethylene glycol, 3.62% PA-4 aluminum powder, 1.62% atomic aluminum, 0.45% polyols (expressed as glucose), 0.63% oleylacetyl polyglycol ether and 14.41% water. At a charge diameter of 90 mm.a and a charge density of 1> 570 g.cm 3, the detonation velocity was 4.44 km.s' and the detonation pressure was 7.99 GPa. The proportion of treated wastes from the production of 1,5-endomethylene-3,7-dinitroso-1,3,5,7-tetraazacyclooctane in this explosive is 21% by weight.

Example 5

Treated wastes from the production of 1,5-endomethylene-3,7-dinitroso-1,3,5,7-tetraazacyclooctane (according to the author's certificate No. 199 090), having a density of 1.58 g.cm ^{- were available.} chemical oxygen demand 67 g oxygen per kg and composition in mass percentages: 43.92% sodium nitrate, 3.12% calcium nitrate, 0.93% ammonium nitrate, 1.20% polyols (expressed as glucose) and 50.83% water. This mixture was a suspension at normal temperature, turning into a solution above 75 ° C. In an analogous manner to Examples 1, 2 and 3, an explosive having the following composition (in weight percent) was prepared: 57.19% ammonium nitrate, 10.0% sodium nitrate, 0.71% calcium nitrate, 9.57% urea 5.01% sublimed sulfur, 4.55% ethylene glycol, 0.27% polyols (expressed as glucose), 0.45 guar gum, 0.64% oleylacetyl polyglycol ether and 11.58% water.

At a charge diameter of 90 mm and a charge density of 1.474 g ^/ cm @ 2, the mixture of this type exhibited a detonation velocity of 4.32 km / s and a calculated detonation pressure of 7.10 GPa. The proportion of concentrated wastes from the production of 1,5-endomethylene-3,7-dinitroso-1,3,5,7-tetraazacyclooctane in this explosive was 22.7% by weight.

Example 6

From the treated wastes from the production of 1,5-endomethylene-3,7-dinitroso-1,3,5,7-tetraazacyclooctane of the same composition as in Example 5, an explosive (composition in percent by weight) was prepared: 54.99% ammonium nitrate, 10.37% sodium nitrate, 0.47% calcium nitrate, 20.53% 2,4,6-trinitrotoluene, 0.28% polyols (expressed as glucose), 0.54% guar gum, 0.54 % oleylacetylpolyglycol ether and 12.0% wasp. At a charge diameter of 90 mm and a charge density of 1.560 g.cm, the detonation velocity was 4.49 km / s and the calculated detonation pressure was 8.12 GPa. The proportion of treated wastes from the production of 1,5-enuomethylene-3,7-dinitroso-1,3,5,7-tetraazacyclooctane (according to the author's certificate No. 199 090) in the explosive was 23.6% by weight.

Claims (1)

OBJECT OF THE INVENTION A water-plasticized explosive mixture consisting of an oxidizing component, a fuel, a sensitizing component, a thickening component, and generally containing also rheological modifiers and Ss-dependent performance modifiers. Certificate No. 199 090, characterized in that it contains 0.70% to 15.0% by weight of the composition. % sodium nitrate and / or calcium nitrate, preferably 0.71 to 10.37 wt. % sodium and / or calcium nitrate resulting in aqueous solutions from mother liquor processing from the production of 1,5-endomethylene-3,7-dinitroso-1,3,5,7-tetraazacyclooctane; % ammonium nitrate, preferably 54.99 to 75.05 wt. % ammonium nitrate, 0.10 to 9.0 wt. % of polyols C8 to C18, preferably 0.13 to 8.30 wt. % C 3 -C 7 polyols, 3 to 7 wt. % of aluminum powder, preferably 3.42 to 5.24 wt. % of powdered aluminum, 4.58 to 9.57% oxidizing-capable additives such as urea, sulfur or hexamethylenetetramine, 7.68 to 20.54 wt. % of organic polynitro compounds such as dinitronaphthalene, trinitrotoluene or 1,3,5-trinitro-1,3,5-triazacyclohexane, 7 to 16 wt. % water, preferably 7.69 to 14.41 wt. % water, 0.42-0.80 wt. % thickening components such as guar meal and 0.50-0.64 wt. surfactants such as oleylacetyl polyglycol ether.