RU2203258C2 - Hydrogen-containing explosive composition and its modifications - Google Patents

Abstract

FIELD: hydrogen-containing explosive composition used for blasting operations by the method of deep-hole charges in mining industry. SUBSTANCE: according to modification 1, the hydrogen-containing explosive composition in mining industry contains 45-65% aqueous or water-glycoholic solution of inorganic oxidant (5 to -25 mas.%)<RDX, and/or octagen (95 to 75 mas.%), according to modification 2, the hydrogen-containing explosive composition contains 45 to 65% aqueous or water glycoholic solution of inorganic oxidant (9-17 mas. %) DX and/or octagen (58-68 mass percentage), ammonium nitrate (32-18 mass percentage). According to modification 3, the hydrogen containing explosive composition contains 45-65-% aqueous or water-glycoholic solution of inorganic oxidant (0.5-17 mas.%) X and/or octogen (4.5-66 mas.%) ammonium nitrate (91-81 mas.%), liquid oil product (0.1-5.2 mas.%). EFFECT: enhanced efficiency of hydrogen-containing explosive, safety in manufacture and use due to the reduction of its sensitivity to mechanical actions and reduction of electrization that is suitable for charging of dry and water-enroached rocks of any strength. 16 cl, 2 tbl

Description

 The invention relates to water-containing explosive compositions (VVS) used as industrial explosives (PVV) for blasting on the earth's surface using the method of borehole charges.

 The air force is widely used both in Russia (aquanite, aquanal) and abroad (hablastite in Germany, tovex in the USA, nitrex in Canada, etc.). They consist of two phases - liquid and solid. The liquid phase is an aqueous solution of an inorganic oxidizing agent or water-in-oil emulsions of water or oil. Explosive and non-explosive components are used as the solid phase (US Pat. No. 2147567 dated 04/12/99, 2118307 dated 07/31/97, 2076089 dated 08/30/94, 2092473 dated 08/29/95, US Pat. No. 3,235,425 dated 02/15/66).

 Bulk industrial explosives are most widely used in blasting operations on the earth's surface, especially in quarries of low power. The flowability of water-containing aircraft is determined by the viscosity and mass fraction of the liquid phase, and the working capacity and energy characteristics are determined by the solid phase. The most energy-intensive components of the solid phase are blasting explosives, such as TNT, RDX, HMX, etc. Blasting explosives - RDX and HMX are not used as individual industrial explosives due to their high sensitivity to mechanical stress, dusting, and environmental hazard of explosion products, poor drowning.

 It is known to use a water-containing aircraft, including at least 1 wt. % aqueous solution of nitrate with a concentration of at least 20 wt.% and blasting explosive - flaked or granulated TNT - the rest, for loading waterlogged wells in the winter (Pat. Russia 2117911 from 12.11.97), adopted by the authors as a prototype. The disadvantage of the prototype composition is the limited use (only waterlogged wells), limited temperature range of use, high harmfulness of explosion products due to the high negative balance of the air force determined by TNT (minus 74%).

 An object of the invention was to increase the effectiveness of a water-containing explosive composition by expanding the scope, increasing efficiency, improving operational properties, ensuring flowability, expanding the raw material base with an increase in the range of explosives.

The problem was solved by the creation of a loose water-containing aircraft and its variants:
- for waterlogged wells, for hard rocks and rocks of medium strength - option 1, containing a liquid phase based on an inorganic oxidizer and a blasting explosive, in which an aqueous or water-glycol solution of an inorganic oxidizer with a concentration of 45-65 wt.% is selected, as blasting explosive - RDX and / or HMX;
- for wet wells and wells with running water, for hard rocks and rocks of medium strength - option 2, containing a liquid phase based on an inorganic oxidizing agent and a blasting explosive, in which ammonium nitrate is additionally introduced, an aqueous or water-glycol solution is selected as the liquid phase inorganic oxidizing agent concentration of 45-65 wt.%, and as a blasting explosive - RDX and / or HMX;
- for dry and moistened wells, rocks of any strength - option 3, - containing a liquid phase based on an inorganic oxidizer and a blasting explosive, in which ammonium nitrate and a liquid oil product are additionally added, an aqueous or water-glycol solution of an inorganic oxidizing agent is selected as the liquid phase 45-65 wt.%, As a blasting explosive - RDX and / or HMX, while the components included in the Air Force (options 1, 2, 3) are taken in the following ratio, wt.% (See Table 1).

 In this case, ammonia, or calcium, or sodium nitrate, or a mixture thereof is selected as an inorganic oxidizer of the liquid phase. As ammonium nitrate (options 2, 3), porous or dense granular, or crystalline, or powder, or a mixture thereof is selected. In the composition of options 2 and 3, carbamide is additionally introduced in an amount of 2-10 wt.% Of the content of ammonium nitrate. As a liquid petroleum product for option 3, diesel fuel and / or mineral oils are selected. In the liquid phase of the air force for options 1, 2, 3, an additional 0.5-3.0 wt.% Surfactant is introduced. As a RDX in the composition of options 1, 2, 3, phlegmatized RDX is taken. As part of option 3, ammonium nitrate and liquid oil can be introduced in the form of explosives (ammonium nitrate - liquid oil) with an oxygen balance close to zero.

 To increase the effectiveness of the air force, the authors chose powdery Hegsogen and / or HMX as a blasting explosive, which belong to the class of nitramines: they practically have the same energy characteristics and elemental composition. RDX and HMX have a heat of explosion of 1.4 times, performance 1.4-1.6 times higher, and the oxygen balance is 3 times better than TNT, which is the main component of the prototype composition.

 The need to create three variants of the Air Force was caused by a significant dispersion of mining and geological conditions for blasting - rock strength, water cut wells. For hard rocks and medium-strength rocks in flooded conditions, it is recommended to use the air force of option 1 containing hexogen and / or octogen and a liquid phase; for hard rocks and medium-strength rocks for wells with running water, wet and dry - VVS option 2, containing RDX and / or HMX, liquid phase and ammonium nitrate; for rocks of any strength in dry and humid conditions - the air force of option 3, containing hexogen and / or octogen, a liquid phase, ammonium nitrate and liquid petroleum product. Moreover, for loading wells with a diameter of less than 100 mm, it is recommended to use porous ammonium nitrate or its mixture with dense granular (GOST 2-85); for loading holes - porous or a mixture thereof with a powder; for wells with running water and wet, crystalline or granular ammonium nitrate, or a mixture thereof.

 The choice of ingredients of the inventive free-flowing aqueous BC and its variants was determined by the following factors: 45-65% aqueous or water-glycolic inorganic oxidizer solution reduces the static electrization of RDX (HMX) by increasing the electrical conductivity of the powdery material, reduces sensitivity to mechanical stress, which allows carry out storage and transportation of the inventive air force and its variants and safe loading of dry and flooded wells. But at the same time, the solution acts as a wetting agent for fine powders of RDX and HMX, which leads to an increase in bulk density, a decrease in the surface tension at the water-RDX (HMX) -air interface, and determines the flooding of the inventive air force when charging flooded wells. The introduction of a hydrophilic water-soluble surfactant into the inorganic oxidizer solution accelerates the wetting and flooding of the inventive air force. The claimed amount of a solution of inorganic oxidizer provides flowability of the Air Force, prevents caking and freezing during storage, transportation and loading of wells. The inorganic oxidizing agent of the solution, having a positive oxygen balance, contributes to a more complete explosive conversion of RDX (HMX), which plays the role of a fuel, sensitizer, and energy-carrying component in this air force. The introduction of ammonium nitrate allows not only to reduce the sensitivity to mechanical stresses, the electrification of powdered RDX (HMX), but also to improve the oxygen balance of the proposed Air Force options 2 and 3. In the inventive air force containing a powerful detonation sensitizer, which is RDX (HMX), the parameters of the detonation wave determined mainly by the density of the sensitizer filling the intergranular space of a less reactive component - ammonium nitrate. Ammonium nitrate, being a phlegmatizer of sensitivity to mechanical stress and an antistatic agent in relation to RDX (HMX), decomposes in their detonation wave with a weak exothermic effect, i.e. possesses weakly expressed explosive properties and therefore is not a purely inert filler. The surface treatment of ammonium nitrate with liquid oil (oiling) accelerates the process and the completeness of the chemical conversion of ammonium nitrate due to a more dense oxidizer-fuel contact. As a liquid petroleum product, diesel fuel or mineral oils are used, which practically have the same elemental composition and thermodynamic characteristics. Mortar filling of BC based on a blasting explosive (RDX or HMX) does not lead to a significant expansion of the chemical reaction zone.

 When choosing the components of the inventive air force and its variants, the circumstance was also taken into account that hexogen (octogen), which is located at the State Reserve storage facilities, cannot be transported without its preliminary phlegmatization. Their disposal in industrial explosives is possible only at the places of their storage. Based on the technological capabilities of the storage buildings (the small cubic capacity of the buildings, the lack of powerful air handling units and the inability to install them), it was necessary to choose less toxic components than RDX and HMX, which belong to the 2nd group of toxicity. Water and water-glycol solutions of an inorganic oxidizing agent, ammonium nitrate, and liquid petroleum products belong to 3-4 toxicity groups (low-hazard substances). Therefore, the production of the inventive air force and its variants can be carried out on the technological areas of RDX and HMX storage bases. RDX and / or HMX are treated with an aqueous or water-glycol solution of an inorganic oxidizer until they are completely wetted (option 1), by mixing a completely moistened powder with ammonium nitrate (option 2), ammonium nitrate and liquid oil or oily ammonium nitrate (option 3) to form loose water-containing explosive composition. At the same time, in comparison with the original HGX (HMX), the sensitivity to mechanical stress and the ability to accumulate charges of static electricity are reduced. The air forces of options 2 and 3 can also be produced at specialized factories for the production of explosives by mixing the air force of option 1 with ammonium nitrate (option 2), oily ammonium nitrate or explosive composition ammonium nitrate - liquid petroleum product (option 3).

 As hexogen, hexogen stored at the base can be used, phlegmatized, for example, with ceresin, paraffin and other phlegmatized additives, which cannot be divided into its constituent parts. The method of its processing and use as a component of the inventive air force and its variants is similar to the above.

 To ensure the safety of blasting during the breaking of aggressive sulfide-containing ores, urea is additionally introduced in an amount of 2-10 wt.% Of the content of ammonium nitrate.

 With the selected components and their ratio, optimal conditions for the destruction and crushing of rocks are created. Reducing the brisant effect of RDX (HMX) due to the selected components and their ratio in the inventive air force and its variants prevents overcrushed rock in contact with the charge.

The inventive air force and its variants provide the main technical result - improving the safety of manufacture and use by reducing sensitivity to mechanical stress, increasing efficiency due to the selected blasting explosive, failure-free and safe action of the borehole charge, flowability provides the ability to charge dry and flooded wells with manual and mechanized methods adopted at the quarries, achieved environmental clean blasting. The inventive air force and its variants are used for breaking rocks of any strength and water cut in the temperature range plus or minus 50 ^o C; for their storage, transportation does not require the development of special transport containers. The inventive Air Force and its variants are made on Russian raw materials.

 Examples of the inventive air force and its variants are given in table. 2.

 As follows from the table. 2, sensitivity to shock (Ho = 500 mm,% adult = 0), friction (more than 400 MPa) ensures the safety of storage, transportation and use of the Air Force and its variants. The Air Force and its variants are operable in dry, wet, and flooded wells for breaking rocks of any strength. They retain flowability during the warranty period, have good flooding when loading waterlogged wells, and are safe when loading dry wells.

Claims (15)

1. A water-containing explosive composition comprising an inorganic oxidizer-based liquid phase and a blasting explosive, characterized in that it contains a 45-65% aqueous or water-glycolic inorganic oxidizer solution as a liquid phase based on an inorganic oxidant, and as blasting explosive - RDX and / or HMX in the following ratio of components, wt.%:
45-65% Aqueous or water-glycolic inorganic oxidizer solution - 5 - 25
RDX and / or HMX - 95 - 75
2. The composition according to claim 1, characterized in that it contains phlegmatized RDX.  3. The composition according to claim 1, characterized in that as an inorganic oxidizing agent it contains ammonia, or calcium, or sodium nitrate, or a mixture thereof in any ratio.  4. The composition according to p. 1 or 3, characterized in that the 45-65% aqueous or water-glycolic inorganic oxidizer solution contains 0.5-3 wt.% Surfactant. 5. A water-containing explosive composition, comprising a liquid phase based on an inorganic oxidizing agent and a blasting explosive, characterized in that it additionally contains ammonium nitrate; as a liquid phase based on an inorganic oxidizing agent, it contains a 45-65% aqueous or water-glycol solution inorganic oxidizing agent, and as a blasting explosive - hexogen and / or octogen in the following ratio of components, wt.%:
45-65% Aqueous or water-glycolic inorganic oxidizer solution - 9 - 17
RDX and / or HMX - 58 - 68
Ammonium nitrate - 32 - 18
6. The composition according to claim 5, characterized in that, as ammonium nitrate, it contains porous, or dense granular, or crystalline, or powdered ammonium nitrate, or a mixture thereof.  7. The composition according to claim 5, characterized in that it additionally contains urea in an amount of 2-10 wt.% From the content of ammonium nitrate.  8. The composition according to claim 5, characterized in that it contains phlegmatized hexogen.  9. The composition according to claim 5, characterized in that as an inorganic oxidizing agent it contains ammonia, or calcium, or sodium nitrate, or a mixture thereof in any ratio.  10. The composition according to claim 5 or 9, characterized in that a 45-65% aqueous or water-glycol solution of an inorganic oxidizing agent contains 0.5-3 wt.% Surfactant. 11. A water-containing explosive composition, comprising a liquid phase based on an inorganic oxidizer and a blasting explosive, characterized in that it further comprises ammonium nitrate and a liquid oil product, as a liquid phase based on an inorganic oxidizer, it contains 45-65% aqueous or aqueous -glycolic solution of an inorganic oxidizing agent, and as a blasting explosive - hexogen and / or octogen in the following ratio of components, wt.%:
45-65% Aqueous or water-glycolic inorganic oxidizer solution - 0.5 - 17
RDX and / or HMX - 4.5 - 66
Ammonium nitrate - 91 - 18
Liquid oil - 0.1 - 5.2
12. The composition according to claim 11, characterized in that as ammonium nitrate it contains porous, or dense granular, or crystalline, or powdered ammonium nitrate, or a mixture thereof.  13. The composition according to p. 11, characterized in that it additionally contains urea in an amount of 2-10 wt.% From the content of ammonium nitrate.  14. The composition according to claim 11, characterized in that it contains phlegmatized hexogen.  15. The composition according to p. 11, characterized in that as an inorganic oxidizing agent it contains ammonia, or calcium, or sodium nitrate, or a mixture thereof in any ratio.  16. The composition according to claim 11 or 15, characterized in that the 45-65% aqueous or water-glycolic inorganic oxidizer solution contains 0.5-3 wt.% Surfactant.  17. The composition according to claim 11, characterized in that it contains ammonium nitrate and liquid oil in the form of an explosive with an oxygen balance close to zero.  18. The composition according to p. 11 or 17, characterized in that as a liquid petroleum product it contains diesel fuel and / or mineral oils.

Images