EP0968985A1 - Cartridged energetic emulsion explosives - Google Patents
Cartridged energetic emulsion explosives Download PDFInfo
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- EP0968985A1 EP0968985A1 EP99401491A EP99401491A EP0968985A1 EP 0968985 A1 EP0968985 A1 EP 0968985A1 EP 99401491 A EP99401491 A EP 99401491A EP 99401491 A EP99401491 A EP 99401491A EP 0968985 A1 EP0968985 A1 EP 0968985A1
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B47/00—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase
- C06B47/14—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase comprising a solid component and an aqueous phase
- C06B47/145—Water in oil emulsion type explosives in which a carbonaceous fuel forms the continuous phase
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- the present invention is in the field general of industrial explosives for civil use.
- It relates to new explosive emulsions particularly suitable for slaughter hard rocks in quarries or on construction sites.
- Water-in-oil cartridge-type explosive emulsions are well known to those skilled in the art.
- emulsions Compared to the usual dynamites, which contain 25% to 45% nitroglycerin, emulsions aforementioned explosives offer safe use and very clearly improved manufacturing. In counterpart, they are much less powerful and release less explosion energy.
- a person skilled in the art has long been at the search for explosive emulsions of the aforementioned type, presenting both safety and sensitivity to initiation of cartridge-containing explosive emulsions known and the power of dynamites, namely a detonation speed close to 6000 m / s measured in diameter 80 mm confined, and a total energy measured under water greater than approximately 1100 cal / g.
- sensitizing molecules such as nitrate hydrazine and organic nitrates, especially amine nitrates such as methylamine nitrate, or well again reaction catalysts such as copper chloride, or even very oxidizing reagents such as chlorates or perchlorates.
- Patent application EP 598 115 describes for example energetic explosive emulsions based on nitrate ammonium containing an amine nitrate and / or nitrate hydrazine as a sensitizer.
- US Patent 4,371,408 describes explosive emulsions based on ammonium nitrate and sodium nitrate sensitized with an amine nitrate and containing CuCl 2 as a detonation catalyst.
- detonation velocity close to 6000 m / s measured in diameter 80 mm confined and a total energy measured under water greater than 1100 cal / g, which can even exceed 1200 cal / g, with a energy efficiency greater than 80%.
- the object of the present invention is therefore to new cartridge type explosive emulsions water-in-oil sensitized by a gas phase dispersed and comprising ammonium nitrate, sodium nitrate, water, fuel hydrocarbon, emulsifier and aluminum.
- the aforementioned weight contents are expressed by compared to the sensitized explosive emulsion and have to be understood limits included.
- the above-mentioned new explosive emulsions according to the invention are in particular devoid of chlorates and perchlorates, for example those of ammonium, of metals alkaline or alkaline earth, devoid of molecules sensitizers of the organic nitrates type, by example of alkylamine nitrates and nitrates alkanolamines, or hydrazine nitrates, for example example of hydrazine nitrate and methylhydrazine, free of metal catalysts such as copper chloride.
- chlorates and perchlorates for example those of ammonium, of metals alkaline or alkaline earth
- molecules sensitizers of the organic nitrates type by example of alkylamine nitrates and nitrates alkanolamines, or hydrazine nitrates, for example example of hydrazine nitrate and methylhydrazine, free of metal catalysts such as copper chloride.
- the hydrocarbon fuel can be a mixture of several hydrocarbon fuels and the emulsifier a mixture of several emulsifiers.
- the hydrocarbon fuel can be aliphatic, cycloaliphatic, aromatic, saturated or unsaturated.
- We may for example include toluene, xylenes, petrol, kerosene, fuel oil, paraffins, oils, especially paraffinic oils or naphthenics, fatty acids and their derivatives, waxes, and mixtures thereof, namely any mixture of at least minus two of the above compounds.
- the hydrocarbon fuel is chosen from the group consisting of oils, waxes, paraffins and their mixtures.
- the emulsifier can be any well known emulsifier skilled in the art promoting physical stability water-in-oil emulsions by lowering the interfacial tension between the 2 phases of the emulsion.
- the emulsifier is preferably chosen from the group consisting of polymeric emulsifiers which simultaneously comprise hydrophilic chains and hydrophobic chains, such as derivatives of polyisobutylene and succinic anhydride, amines, in particular those containing from 12 to 24 atoms of carbon, fatty acid esters such as monooleate sorbitan, sorbitan laurate, palmitate sorbitan and sorbitan stearate, alkylaryl sulfonates, and mixtures thereof.
- polymeric emulsifiers which simultaneously comprise hydrophilic chains and hydrophobic chains, such as derivatives of polyisobutylene and succinic anhydride, amines, in particular those containing from 12 to 24 atoms of carbon, fatty acid esters such as monooleate sorbitan, sorbitan laurate, palmitate sorbitan and sorbitan stearate, alkylaryl sulfonates, and mixtures thereof.
- Aluminum used in the context of this invention is finely divided, preferably powdery.
- Its particle size is generally between 0.1 ⁇ m and 250 ⁇ m, better still between 0.5 ⁇ m and 150 ⁇ m.
- the explosive emulsions according to the invention are sensitized by a dispersed gas phase, according to a method well known to those skilled in the art.
- nitrites such as nitrite sodium
- ammonium ions of ammonium nitrate cause in situ formation nitrogen.
- This reaction can be accelerated by temperature rise and / or by a urea, thiourea or thiocyanate type.
- the emulsions explosives according to the invention contain between 13% and 17% by volume of dispersed gas phase, better still between 14% and 16% by volume.
- the sum of the weight contents of ammonium nitrate and sodium nitrate is between 73% and 77%, better still between 74% and 76%.
- the content by weight in ammonium nitrate is between 61% and 67%, better still between 62% and 65%.
- the content water weight is between 4.5% and 6.5%, better still between 5% and 6%.
- the content aluminum weight is between 13% and 17%, better still between 13.5% and 16.5%, better still between 14% and 16%.
- the content by weight in emulsifier is between 1.5% and 4%, better still between 2% and 3.5%.
- the content weight in hydrocarbon fuel is between 0.7% and 4%, better still between 0.8% and 3%, better still between 1% and 2%.
- the density of explosive emulsions according to the invention is preferably between 1.26 and 1.40, better still between 1.28 and 1.37, their speed detonation measured in diameter 80 mm confined is between 5500 m / s and 6300 m / s, better still between 5750 m / s and 6300 m / s, and their total real energy, determined under water, is between 1100 cal / g and 1400 cal / g, better still between 1200 cal / g and 1400 cal / g.
- the explosive emulsions according to the invention can be obtained by analogy with any process already known obtaining water-in-oil explosive emulsions sensitized by a dispersed gas phase and comprising ammonium nitrate, sodium nitrate, water, a hydrocarbon fuel, an emulsifier and aluminum.
- the emulsifier may also not be incorporated into this hydrocarbon fuel stage.
- the emulsion may be obtained using a turbine and simultaneously homogenized for example using a pale clover.
- the 2 phases, and the emulsifier if it is not incorporated into the phase oily are pumped using metering pumps in supply lines for an foam concentrate.
- aluminum, microspheres and / or the chemical gas generator are from preferably incorporated into the emulsion by kneading, in the mixer used to make the emulsion, or in a planetary shaker.
- the adjuvants are preferably incorporated continuously, for example using auger, in a mixer in which also pours the water-in-oil emulsion into from the foam concentrate.
- the sensitized explosive emulsion thus prepared is then sealed, possibly after a first cooling, manually or automatic, in sheaths such as paper or plastic, using an installation of packaging well known to those skilled in the art.
- the cartridges obtained are then generally cooled, for example with cold water or air cold depending on the nature of the sheath, so as to stabilize the final emulsion obtained.
- the aqueous phase (a) and the fatty phase (b) are then introduced into a mixer, then we realize the emulsion using a turbine while homogenizing simultaneously mixing with a pale clover.
- the temperature self-maintains between 105 ° C and 110 ° C in the mixer.
- the mass of explosive emulsion that we introduce in each sheath is evidently deduced from the volume of the cartridge sought, the density of the emulsion explosive that is measured before the packaging and the addition of sodium nitrite, and the volume rate sought for gas phase (about 15%).
- the volume level of desired gas phase is reached and the chemical reaction of formation is then stopped of nitrogen by abruptly lowering the temperature of the emulsion, which is easily achieved by spraying cold water on the cartridges.
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Abstract
Description
La présente invention se situe dans le domaine général des explosifs industriels à usage civil.The present invention is in the field general of industrial explosives for civil use.
Elle a pour objet de nouvelles émulsions explosives encartouchées particulièrement adaptées pour l'abattage des roches dures en carrières ou sur chantiers.It relates to new explosive emulsions particularly suitable for slaughter hard rocks in quarries or on construction sites.
Les émulsions explosives encartouchées de type eau-dans-huile sont bien connues de l'homme du métier.Water-in-oil cartridge-type explosive emulsions are well known to those skilled in the art.
Elles comprennent comme constituants :
- une phase aqueuse discontinue sous forme de gouttelettes d'une solution aqueuse de sels oxydants inorganiques,
- une phase organique continue non miscible à l'eau dans laquelle les gouttelettes précitées sont dispersées,
- un émulsifiant formant une émulsion des gouttelettes aqueuses dans toute la phase organique continue,
- une phase gazeuse discontinue, uniformément dispersée dans l'émulsion, qui permet d'augmenter la sensibilité à l'amorçage de l'émulsion, chaque bulle de gaz dispersée jouant le rôle de point chaud.
- a discontinuous aqueous phase in the form of droplets of an aqueous solution of inorganic oxidizing salts,
- a continuous organic phase immiscible with water in which the aforementioned droplets are dispersed,
- an emulsifier forming an emulsion of the aqueous droplets throughout the continuous organic phase,
- a discontinuous gas phase, uniformly dispersed in the emulsion, which makes it possible to increase the sensitivity to priming of the emulsion, each dispersed gas bubble playing the role of hot spot.
Comparativement aux dynamites usuelles, qui contiennent 25% à 45% de nitroglycérine, les émulsions explosives précitées présentent une sécurité d'usage et de fabrication très nettement améliorée. En contrepartie, elles sont nettement moins puissantes et libèrent une énergie d'explosion moindre.Compared to the usual dynamites, which contain 25% to 45% nitroglycerin, emulsions aforementioned explosives offer safe use and very clearly improved manufacturing. In counterpart, they are much less powerful and release less explosion energy.
L'homme du métier est depuis fort longtemps à la recherche d'émulsions explosives de type précité, présentant à la fois la sécurité et la sensibilité à l'amorçage des émulsions explosives encartouchées connues et la puissance des dynamites, à savoir une vitesse de détonation voisine de 6000 m/s mesurée en diamètre 80 mm confiné, et une énergie totale mesurée sous eau supérieure à 1100 cal/g environ. A person skilled in the art has long been at the search for explosive emulsions of the aforementioned type, presenting both safety and sensitivity to initiation of cartridge-containing explosive emulsions known and the power of dynamites, namely a detonation speed close to 6000 m / s measured in diameter 80 mm confined, and a total energy measured under water greater than approximately 1100 cal / g.
Il est bien connu d'augmenter la densité des explosifs pour augmenter leur vitesse de détonation. Toutefois, dans le cas des émulsions explosives encartouchées sensibilisées par une phase gazeuse dispersée, une augmentation de la densité implique une diminution de la teneur volumique en phase gazeuse et donc une moindre sensibilité à l'amorçage.It is well known to increase the density of explosives to increase their detonation speed. However, in the case of explosive emulsions cartridges sensitized by a gas phase dispersed, an increase in density implies a decrease in the volume content in the gas phase and therefore less sensitivity to priming.
Il est possible de compenser cette moindre sensibilité en incorporant dans les compositions des molécules sensibilisatrices telles que le nitrate d'hydrazine et les nitrates organiques, notamment les nitrates d'amines comme le nitrate de méthylamine, ou bien encore des catalyseurs de réaction tels que le chlorure de cuivre, ou bien encore des comburants très réactifs tels que des chlorates ou perchlorates.It is possible to compensate for this lesser sensitivity by incorporating into the compositions sensitizing molecules such as nitrate hydrazine and organic nitrates, especially amine nitrates such as methylamine nitrate, or well again reaction catalysts such as copper chloride, or even very oxidizing reagents such as chlorates or perchlorates.
Toutefois, l'usage de telles molécules sensibilisatrices, catalyseurs, et/ou comburants réactifs entraíne un risque important d'accident pyrotechnique. En effet, les nitrates organiques, chlorates et perchlorates sont particulièrement dangereux à manipuler, le nitrate d'hydrazine est instable et les catalyseurs métalliques peuvent réagir avec le nitrate d'ammonium, sel oxydant inorganique en pratique toujours utilisé dans les compositions, seul ou en mélange avec d'autres sels oxydants.However, the use of such molecules sensitizers, catalysts, and / or oxidizers reagents involves a significant risk of accident pyrotechnic. Indeed, organic nitrates, chlorates and perchlorates are particularly dangerous to handle, hydrazine nitrate is unstable and metallic catalysts can react with ammonium nitrate, an inorganic oxidizing salt in practice always used in compositions, alone or mixed with other oxidizing salts.
La demande de brevet EP 598 115 décrit par exemple des émulsions explosives énergétiques à base de nitrate d'ammonium contenant un nitrate d'amine et/ou le nitrate d'hydrazine comme sensibilisant.Patent application EP 598 115 describes for example energetic explosive emulsions based on nitrate ammonium containing an amine nitrate and / or nitrate hydrazine as a sensitizer.
Le brevet US 4 371 408 décrit des émulsions explosives à base de nitrate d'ammonium et de nitrate de sodium sensibilisées par un nitrate d'amine et contenant du CuCl2 comme catalyseur de détonation.US Patent 4,371,408 describes explosive emulsions based on ammonium nitrate and sodium nitrate sensitized with an amine nitrate and containing CuCl 2 as a detonation catalyst.
Il est également connu d'incorporer de l'aluminium dans les émulsions explosives pour augmenter leur énergie. Toutefois, l'accroissement du taux d'aluminium est en pratique limité par le fait que le rendement énergétique, qui est le rapport entre l'énergie mesurée et l'énergie théorique calculée, diminue alors fortement.It is also known to incorporate aluminum in explosive emulsions to increase their energy. However, the increase in aluminum levels is in practice limited by the fact that the yield energy, which is the ratio between the energy measured and the calculated theoretical energy then decreases strongly.
De plus, il est connu que la vitesse de détonation diminue lorsque le taux d'aluminium augmente, du fait de la diminution du taux massique des produits gazeux dans les produits de décomposition.In addition, it is known that the detonation speed decreases when the aluminum level increases, due to the reduction in the mass rate of gaseous products in decomposition products.
Sur la base de cet enseignement et de ces constatations, il paraissait inconciliable, à l'homme du métier, d'obtenir des émulsions ayant toutes les propriétés et caractéristiques recherchées précitées.Based on this teaching and these findings, it seemed irreconcilable, to the man of the profession, to obtain emulsions having all the properties and characteristics sought above.
Ce préjugé a pourtant été vaincu.However, this prejudice has been overcome.
Il a été découvert, de façon particulièrement inattendue, qu'en associant le nitrate d'ammonium et le nitrate de sodium, à des teneurs pondérales bien particulières, en l'absence d'autres sels inorganiques, de molécules sensibilisatrices de type nitrates organiques ou nitrate d'hydrazine et de catalyseurs métalliques, et en sélectionnant de façon judicieuse la nature et la teneur pondérale des autres constituants, notamment la teneur en eau et en aluminium, on pouvait obtenir des émulsions explosives présentant la sensibilité à l'amorçage et la sécurité d'usage et de fabrication des émulsions explosives encartouchées classiques, tout en présentant les performances des dynamites usuelles, à savoir une vitesse de détonation voisine de 6000 m/s mesurée en diamètre 80 mm confiné et une énergie totale mesurée sous eau supérieure à 1100 cal/g, pouvant même dépasser 1200 cal/g, avec un rendement énergétique supérieur à 80%.It was discovered, particularly unexpected, that by combining ammonium nitrate and sodium nitrate, at good weight contents particular, in the absence of other inorganic salts, nitrates-like sensitizing molecules organic or hydrazine nitrate and catalysts metal, and by judiciously selecting the nature and weight content of the other constituents, especially the water and aluminum content, we could get explosive emulsions with the sensitivity to ignition and safety of use and manufacture of cartridge-filled explosive emulsions while presenting the performances of usual dynamites, i.e. detonation velocity close to 6000 m / s measured in diameter 80 mm confined and a total energy measured under water greater than 1100 cal / g, which can even exceed 1200 cal / g, with a energy efficiency greater than 80%.
La présente invention a donc pour objet de nouvelles émulsions explosives encartouchées de type eau-dans-huile sensibilisées par une phase gazeuse dispersée et comprenant du nitrate d'ammonium, du nitrate de sodium, de l'eau, un combustible hydrocarboné, un émulsifiant et de l'aluminium.The object of the present invention is therefore to new cartridge type explosive emulsions water-in-oil sensitized by a gas phase dispersed and comprising ammonium nitrate, sodium nitrate, water, fuel hydrocarbon, emulsifier and aluminum.
Ces nouvelles émulsions explosives sont caractérisées en ce que :
- la teneur pondérale en nitrate d'ammonium est comprise entre 60% et 70%,
- la teneur pondérale en nitrate de sodium est comprise entre 8% et 14%,
- la teneur pondérale en eau est comprise entre 4% et 7%,
- la teneur pondérale en combustible hydrocarboné est comprise entre 1% et 4%,
- la teneur pondérale en émulsifiant est comprise entre 0,5% et 4%,
- la teneur pondérale en aluminium est comprise entre 12% et 18%,
- la somme des teneurs pondérales en nitrate d'ammonium et en nitrate de sodium est comprise entre 70% et 80%,
- la somme des teneurs pondérales en nitrate d'ammonium, nitrate de sodium, eau, combustible hydrocarboné, émulsifiant et aluminium est comprise entre 95% et 100%, de préférence entre 98% et 100%, mieux encore entre 99% et 100%.
- the weight content of ammonium nitrate is between 60% and 70%,
- the weight content of sodium nitrate is between 8% and 14%,
- the water content by weight is between 4% and 7%,
- the weight content of hydrocarbon fuel is between 1% and 4%,
- the content by weight of emulsifier is between 0.5% and 4%,
- the aluminum content by weight is between 12% and 18%,
- the sum of the weight contents of ammonium nitrate and sodium nitrate is between 70% and 80%,
- the sum of the contents by weight of ammonium nitrate, sodium nitrate, water, hydrocarbon fuel, emulsifier and aluminum is between 95% and 100%, preferably between 98% and 100%, better still between 99% and 100%.
Les teneurs pondérales précitées sont exprimées par rapport à l'émulsion explosive sensibilisée et doivent être comprises limites incluses.The aforementioned weight contents are expressed by compared to the sensitized explosive emulsion and have to be understood limits included.
Les nouvelles émulsions explosives précitées selon l'invention sont notamment dépourvues de chlorates et perchlorates, par exemple ceux d'ammonium, de métaux alcalins ou alcalino-terreux, dépourvues de molécules sensibilisatrices de type nitrates organiques, par exemple de nitrates d'alkylamines et de nitrates d'alcanolamines, ou de type nitrates d'hydrazines, par exemple de nitrate d'hydrazine et de nitrate de méthylhydrazine, dépourvues de catalyseurs métalliques de réaction tel que le chlorure de cuivre.The above-mentioned new explosive emulsions according to the invention are in particular devoid of chlorates and perchlorates, for example those of ammonium, of metals alkaline or alkaline earth, devoid of molecules sensitizers of the organic nitrates type, by example of alkylamine nitrates and nitrates alkanolamines, or hydrazine nitrates, for example example of hydrazine nitrate and methylhydrazine, free of metal catalysts such as copper chloride.
Par ailleurs, le combustible hydrocarboné peut être un mélange de plusieurs combustibles hydrocarbonés et l'émulsifiant un mélange de plusieurs émulsifiants.Furthermore, the hydrocarbon fuel can be a mixture of several hydrocarbon fuels and the emulsifier a mixture of several emulsifiers.
Le combustible hydrocarboné peut être aliphatique, cycloaliphatique, aromatique, saturé ou insaturé. On peut citer par exemple le toluène, les xylènes, l'essence, le kérosène, le fuel, les paraffines, les huiles, notamment les huiles paraffiniques ou naphténiques, les acides gras et leurs dérivés, les cires, et leurs mélanges, à savoir tout mélange d'au moins deux des composés précités.The hydrocarbon fuel can be aliphatic, cycloaliphatic, aromatic, saturated or unsaturated. We may for example include toluene, xylenes, petrol, kerosene, fuel oil, paraffins, oils, especially paraffinic oils or naphthenics, fatty acids and their derivatives, waxes, and mixtures thereof, namely any mixture of at least minus two of the above compounds.
De façon préférée, le combustible hydrocarboné est choisi dans le groupe constitué par les huiles, les cires, les paraffines et leurs mélanges.Preferably, the hydrocarbon fuel is chosen from the group consisting of oils, waxes, paraffins and their mixtures.
L'émulsifiant peut être tout émulsifiant bien connu de l'homme du métier favorisant la stabilité physique des émulsions eau-dans-huile par abaissement de la tension interfaciale entre les 2 phases de l'émulsion.The emulsifier can be any well known emulsifier skilled in the art promoting physical stability water-in-oil emulsions by lowering the interfacial tension between the 2 phases of the emulsion.
L'émulsifiant est de préférence choisi dans le groupe constitué par les émulsifiants polymériques qui comportent simultanément des chaínes hydrophiles et des chaínes hydrophobes, tels que les dérivés du polyisobutylène et de l'anhydride succinique, les amines, notamment celles comportant de 12 à 24 atomes de carbone, les esters d'acides gras tels que le monooléate de sorbitan, le laurate de sorbitan, le palmitate de sorbitan et le stéarate de sorbitan, les alkylaryl sulfonates, et leurs mélanges.The emulsifier is preferably chosen from the group consisting of polymeric emulsifiers which simultaneously comprise hydrophilic chains and hydrophobic chains, such as derivatives of polyisobutylene and succinic anhydride, amines, in particular those containing from 12 to 24 atoms of carbon, fatty acid esters such as monooleate sorbitan, sorbitan laurate, palmitate sorbitan and sorbitan stearate, alkylaryl sulfonates, and mixtures thereof.
L'aluminium utilisé dans le cadre de la présente invention est finement divisé, de préférence pulvérulent. Aluminum used in the context of this invention is finely divided, preferably powdery.
Sa granulométrie est en général comprise entre 0,1µm et 250µm, mieux encore entre 0,5µm et 150µm.Its particle size is generally between 0.1µm and 250µm, better still between 0.5µm and 150µm.
Les émulsions explosives selon l'invention sont sensibilisées par une phase gazeuse dispersée, selon une méthode bien connue de l'homme de métier.The explosive emulsions according to the invention are sensitized by a dispersed gas phase, according to a method well known to those skilled in the art.
Parmi les procédés les plus connus d'incorporation d'une phase gazeuse à des explosifs en émulsions, on peut citer le mélange mécanique, le dégagement gazeux in situ au moyen d'agents chimiques, et l'incorporation d'une matière poreuse à alvéoles fermées, par exemple des microballons en verre ou en matière plastique, des perles de mousse en styrène, ou des cendres volantes. On peut aussi associer diverses méthodes, par exemple utiliser simultanément un agent chimique et des microsphères.Among the best known methods of incorporation from a gas phase to explosives in emulsions, we may include mechanical mixing, gas evolution in situ by means of chemical agents, and the incorporation porous material with closed cells, for example glass or plastic microballoons, styrene foam beads, or fly ash. We can also combine various methods, for example use a chemical agent and microspheres.
Selon la présente invention, on préfère utiliser le dégagement gazeux in situ au moyen d'agents chimiques, notamment l'utilisation de nitrites, comme le nitrite de sodium, qui, par réaction avec les ions ammonium du nitrate d'ammonium, provoquent la formation in situ d'azote. Cette réaction peut être accélérée par élévation de la température et/ou par un catalyseur de type urée, thiourée ou thiocyanate.According to the present invention, it is preferred to use the in situ gas evolution using chemical agents, including the use of nitrites, such as nitrite sodium, which, by reaction with ammonium ions of ammonium nitrate, cause in situ formation nitrogen. This reaction can be accelerated by temperature rise and / or by a urea, thiourea or thiocyanate type.
De façon particulièrement préférée, les émulsions explosives selon l'invention contiennent entre 13% et 17% en volumes de phase gazeuse dispersée, mieux encore entre 14% et 16% en volumes.Particularly preferably, the emulsions explosives according to the invention contain between 13% and 17% by volume of dispersed gas phase, better still between 14% and 16% by volume.
Selon une variante préférée de l'invention, la somme des teneurs pondérales en nitrate d'ammonium et en nitrate de sodium est comprise entre 73% et 77%, mieux encore entre 74% et 76%.According to a preferred variant of the invention, the sum of the weight contents of ammonium nitrate and sodium nitrate is between 73% and 77%, better still between 74% and 76%.
Selon une autre variante préférée, la teneur pondérale en nitrate d'ammonium est comprise entre 61% et 67%, mieux encore entre 62% et 65%. According to another preferred variant, the content by weight in ammonium nitrate is between 61% and 67%, better still between 62% and 65%.
Selon une autre variante préférée, la teneur pondérale en eau est comprise entre 4,5% et 6,5%, mieux encore entre 5% et 6%.According to another preferred variant, the content water weight is between 4.5% and 6.5%, better still between 5% and 6%.
Selon une autre variante préférée, la teneur pondérale en aluminium est comprise entre 13% et 17%, mieux encore entre 13,5% et 16,5%, mieux encore entre 14% et 16%.According to another preferred variant, the content aluminum weight is between 13% and 17%, better still between 13.5% and 16.5%, better still between 14% and 16%.
Selon une autre variante préférée, la teneur pondérale en émulsifiant est comprise entre 1,5% et 4%, mieux encore entre 2% et 3,5%.According to another preferred variant, the content by weight in emulsifier is between 1.5% and 4%, better still between 2% and 3.5%.
Selon une autre variante préférée, la teneur pondérale en combustible hydrocarboné est comprise entre 0,7% et 4%, mieux encore entre 0,8% et 3%, mieux encore entre 1% et 2%.According to another preferred variant, the content weight in hydrocarbon fuel is between 0.7% and 4%, better still between 0.8% and 3%, better still between 1% and 2%.
Par ailleurs, la densité des émulsions explosives selon l'invention est de préférence comprise entre 1,26 et 1,40, mieux encore entre 1,28 et 1,37, leur vitesse de détonation mesurée en diamètre 80 mm confiné est comprise entre 5500 m/s et 6300 m/s, mieux encore entre 5750 m/s et 6300 m/s, et leur énergie totale réelle, déterminée sous eau, est comprise entre 1100 cal/g et 1400 cal/g, mieux encore entre 1200 cal/g et 1400 cal/g.In addition, the density of explosive emulsions according to the invention is preferably between 1.26 and 1.40, better still between 1.28 and 1.37, their speed detonation measured in diameter 80 mm confined is between 5500 m / s and 6300 m / s, better still between 5750 m / s and 6300 m / s, and their total real energy, determined under water, is between 1100 cal / g and 1400 cal / g, better still between 1200 cal / g and 1400 cal / g.
Les émulsions explosives selon l'invention peuvent être obtenues par analogie avec tout procédé déjà connu d'obtention d'émulsions explosives de type eau-dans-huile sensibilisées par une phase gazeuse dispersée et comprenant du nitrate d'ammonium, du nitrate de sodium, de l'eau, un combustible hydrocarboné, un émulsifiant et de l'aluminium.The explosive emulsions according to the invention can be obtained by analogy with any process already known obtaining water-in-oil explosive emulsions sensitized by a dispersed gas phase and comprising ammonium nitrate, sodium nitrate, water, a hydrocarbon fuel, an emulsifier and aluminum.
On peut, par exemple, préparer dans un premier
temps :
L'émulsifiant peut aussi ne pas être incorporé à ce stade au combustible hydrocarboné.The emulsifier may also not be incorporated into this hydrocarbon fuel stage.
On réalise ensuite, dans un second temps, l'émulsion eau-dans-huile, soit en continu, soit en discontinu.Then, in a second step, the water-in-oil emulsion, either continuously or discontinuous.
Selon un procédé en discontinu, après incorporation dans un malaxeur des quantités nécessaires de phase aqueuse, de phase grasse, et d'émulsifiant si celui-ci n'a pas été intégré à la phase grasse, l'émulsion peut être obtenue à l'aide d'une turbine et simultanément homogénéisée par exemple à l'aide d'une pale trèfle.According to a batch process, after incorporation necessary quantities of phase in a mixer aqueous, fatty phase, and emulsifier if the latter has not been incorporated into the fatty phase, the emulsion may be obtained using a turbine and simultaneously homogenized for example using a pale clover.
Selon un procédé en continu, les 2 phases, et l'émulsifiant s'il n'est pas incorporé à la phase grasse, sont pompés à l'aide de pompes doseuses dans des conduits d'alimentation d'un émulseur.According to a continuous process, the 2 phases, and the emulsifier if it is not incorporated into the phase oily, are pumped using metering pumps in supply lines for an foam concentrate.
On réalise ensuite, dans un troisième temps, l'incorporation, dans l'émulsion obtenue, des divers adjuvants utilisés, à savoir l'aluminium, le générateur de gaz chimique et/ou les microsphères.We then realize, in a third step, the incorporation, in the emulsion obtained, of the various adjuvants used, namely aluminum, the generator chemical gas and / or microspheres.
Selon le procédé en discontinu, l'aluminium, les microsphères et/ou le générateur de gaz chimique sont de préférence incorporés à l'émulsion par malaxage, dans le malaxeur ayant servi à réaliser l'émulsion, ou dans un malaxeur à agitation planétaire. According to the batch process, aluminum, microspheres and / or the chemical gas generator are from preferably incorporated into the emulsion by kneading, in the mixer used to make the emulsion, or in a planetary shaker.
Selon le procédé en continu, les adjuvants sont de préférence incorporés en continu, par exemple à l'aide de vis sans fin, dans un mélangeur dans lequel se déverse également l'émulsion eau-dans-huile en provenance de l'émulseur.According to the continuous process, the adjuvants are preferably incorporated continuously, for example using auger, in a mixer in which also pours the water-in-oil emulsion into from the foam concentrate.
L'émulsion explosive sensibilisée ainsi préparée est ensuite encartouchée, éventuellement après un premier refroidissement, de façon manuelle ou automatique, dans des gaines par exemple en papier ou en matière plastique, à l'aide d'une installation d'encartouchage bien connue de l'homme du métier.The sensitized explosive emulsion thus prepared is then sealed, possibly after a first cooling, manually or automatic, in sheaths such as paper or plastic, using an installation of packaging well known to those skilled in the art.
Les cartouches obtenues sont ensuite généralement refroidies, par exemple par de l'eau froide ou de l'air froid selon la nature de la gaine, de façon à stabiliser l'émulsion finale obtenue.The cartridges obtained are then generally cooled, for example with cold water or air cold depending on the nature of the sheath, so as to stabilize the final emulsion obtained.
Les exemples non limitatifs suivants illustrent l'invention et les avantages qu'elle procure.The following nonlimiting examples illustrate the invention and the advantages it provides.
On a réalisé les émulsions explosives ayant la
composition pondérale suivante :
Dans une cuve munie d'un système de chauffage et d'un système d'agitation, on dissout, à une température comprise entre 100°C et 105°C, 74,3 parties en poids de nitrate d'ammonium, 13,8 parties en poids de nitrate de sodium et 0,04 partie en poids de thiourée dans 6,6 parties en poids d'eau.In a tank fitted with a heating system and of a stirring system, it is dissolved at a temperature between 100 ° C and 105 ° C, 74.3 parts by weight of ammonium nitrate, 13.8 parts by weight of nitrate of sodium and 0.04 parts by weight of thiourea in 6.6 parts by weight of water.
Dans une autre cuve également munie d'un système de chauffage et d'un système d'agitation, on homogénéise, à 95°C, un mélange de :
- 3,7 parties en poids d'émulsifiant constitué d'un mélange 40/60 en poids respectivement de monooléate de sorbitan et d'un polymère constitué de chaínes polyisobutylènes à terminaisons hydrophiles reliées par des fonctions anhydride succinique,
- 1,6 parties en poids de combustible hydrocarboné constitué d'un mélange 10/35/20/35 en poids respectivement d'une huile minérale naphténique de point éclair supérieur à 100°C, d'une paraffine solide de point de fusion supérieur à 50°C, d'une paraffine liquide de point éclair supérieur à 150°C et d'une cire microcristalline de point de fusion supérieur à 50°C.
- 3.7 parts by weight of emulsifier consisting of a 40/60 mixture by weight respectively of sorbitan monooleate and of a polymer consisting of polyisobutylene chains with hydrophilic endings linked by succinic anhydride functions,
- 1.6 parts by weight of hydrocarbon fuel consisting of a mixture 10/35/20/35 by weight respectively of a naphthenic mineral oil with a flash point above 100 ° C., of a solid paraffin with a melting point above 50 ° C, a liquid paraffin with a flash point higher than 150 ° C and a microcrystalline wax with a melting point higher than 50 ° C.
La phase aqueuse (a) et la phase grasse (b) sont ensuite introduites dans un malaxeur, puis on réalise l'émulsion à l'aide d'une turbine tout en homogénéisant simultanément le mélange à l'aide d'une pale trèfle. La température s'auto-entretient entre 105°C et 110°C dans le malaxeur. The aqueous phase (a) and the fatty phase (b) are then introduced into a mixer, then we realize the emulsion using a turbine while homogenizing simultaneously mixing with a pale clover. The temperature self-maintains between 105 ° C and 110 ° C in the mixer.
Après obtention d'une émulsion homogène et stable, on ajoute dans le malaxeur, tout en maintenant l'agitation et la température, 17,7 parties en poids d'aluminium en poudre de granulométrie 0-150µm (diamètre médian environ 80µm), puis, juste avant l'encartouchage, 0,09 partie en poids de nitrite de sodium.After obtaining a homogeneous emulsion and stable, add to the mixer, while maintaining agitation and temperature, 17.7 parts by weight aluminum powder with grain size 0-150µm (diameter median about 80µm), then, just before the cartridge filling, 0.09 parts by weight of sodium nitrite.
On encartouche ensuite l'émulsion explosive obtenue en (c), dont on maintient la température, dans des gaines en matière plastique que l'on clippe ensuite aux 2 extrémités, de façon à obtenir des cartouches approximativement cylindriques ayant par exemple une longueur d'environ 320 mm et un diamètre d'environ 80 mm.We then cartridge the explosive emulsion obtained in (c), the temperature of which is maintained, in plastic sleeves which are then clipped at both ends, so as to obtain cartridges approximately cylindrical having for example a length of about 320 mm and a diameter of about 80 mm.
La masse d'émulsion explosive que l'on introduit dans chaque gaine se déduit de façon évidente du volume de la cartouche recherchée, de la densité de l'émulsion explosive que l'on mesure avant l'encartouchage et l'addition de nitrite de sodium, et du taux volumique recherché de phase gazeuse (environ 15%).The mass of explosive emulsion that we introduce in each sheath is evidently deduced from the volume of the cartridge sought, the density of the emulsion explosive that is measured before the packaging and the addition of sodium nitrite, and the volume rate sought for gas phase (about 15%).
Lorsque l'émulsion explosive contenue dans la gaine occupe tout le volume offert par la cartouche, le taux volumique de phase gazeuse recherché est atteint et l'on stoppe alors la réaction chimique de formation d'azote en abaissant brusquement la température de l'émulsion, ce qui est facilement réalisé en pulvérisant de l'eau froide sur les cartouches.When the explosive emulsion contained in the sheath occupies all the volume offered by the cartridge, the volume level of desired gas phase is reached and the chemical reaction of formation is then stopped of nitrogen by abruptly lowering the temperature of the emulsion, which is easily achieved by spraying cold water on the cartridges.
On opère comme selon l'exemple 1, mais avec les différences suivantes :We operate as according to Example 1, but with the following differences:
On utilise 74,9 parties en poids de nitrate d'ammonium (au lieu de 74,3), 13,9 parties en poids de nitrate de sodium (au lieu de 13,8) et 6,7 parties en poids d'eau (au lieu de 6,6).74.9 parts by weight of nitrate are used ammonium (instead of 74.3), 13.9 parts by weight of sodium nitrate (instead of 13.8) and 6.7 parts in weight of water (instead of 6.6).
On utilise 3,2 parties en poids de l'émulsifiant (au lieu de 3,7) et 1,3 partie en poids du combustible hydrocarboné (au lieu de 1,6).3.2 parts by weight of the emulsifier are used (instead of 3.7) and 1.3 parts by weight of the fuel hydrocarbon (instead of 1.6).
Les caractéristiques physiques et détoniques des
émulsions explosives obtenues selon les méthodes
usuelles bien connues de l'homme du métier sont les
suivantes :
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SI9930259T SI0968985T1 (en) | 1998-07-03 | 1999-06-17 | Cartridged energetic emulsion explosives |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9808498A FR2780726B1 (en) | 1998-07-03 | 1998-07-03 | ENERGY CARTRIDGE EXPLOSIVE EMULSIONS |
| FR9808498 | 1998-07-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0968985A1 true EP0968985A1 (en) | 2000-01-05 |
| EP0968985B1 EP0968985B1 (en) | 2003-04-09 |
Family
ID=9528202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP99401491A Expired - Lifetime EP0968985B1 (en) | 1998-07-03 | 1999-06-17 | Cartridged energetic emulsion explosives |
Country Status (17)
| Country | Link |
|---|---|
| EP (1) | EP0968985B1 (en) |
| AT (1) | ATE236863T1 (en) |
| BG (1) | BG64046B1 (en) |
| CZ (1) | CZ294205B6 (en) |
| DE (1) | DE69906626T2 (en) |
| DK (1) | DK0968985T3 (en) |
| ES (1) | ES2196739T3 (en) |
| FR (1) | FR2780726B1 (en) |
| HU (1) | HU224307B1 (en) |
| NO (1) | NO311670B1 (en) |
| OA (1) | OA11073A (en) |
| PL (1) | PL189609B1 (en) |
| PT (1) | PT968985E (en) |
| RU (1) | RU2222519C2 (en) |
| SI (1) | SI0968985T1 (en) |
| SK (1) | SK285047B6 (en) |
| UA (1) | UA58528C2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110526791A (en) * | 2019-09-18 | 2019-12-03 | 北方爆破科技有限公司 | A kind of mixed explosive and preparation method thereof for fluidized bed |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CZ2017112A3 (en) * | 2017-03-01 | 2018-11-14 | Explosia A.S. | A powder circulation ammonium nitrate industrial explosive |
| AU2019207518B2 (en) | 2018-01-09 | 2024-03-21 | Dyno Nobel Asia Pacific Pty Limited | Explosive compositions for use in reactive ground and related methods |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2086364A (en) * | 1980-10-27 | 1982-05-12 | Atlas Powder Co | Emulsion explosives containing a reduced amount of water |
| EP0155800A1 (en) * | 1984-03-21 | 1985-09-25 | Imperial Chemical Industries Plc | Emulsion explosives composition |
| EP0159171A1 (en) * | 1984-04-05 | 1985-10-23 | Ireco Incorporated | Cast explosive composition |
| EP0256447A1 (en) * | 1986-08-11 | 1988-02-24 | Nippon Kayaku Kabushiki Kaisha | Method for explosive cladding |
| EP0292234A2 (en) * | 1987-05-20 | 1988-11-23 | Aeci Limited | Low water content emulsion |
| AU591976B2 (en) * | 1987-04-24 | 1989-12-21 | Norsk Hydro A.S | Emulsion explosive |
| US4976793A (en) * | 1990-06-12 | 1990-12-11 | Dantex Explosives (Proprietary) Limited | Explosive composition |
| EP0598115A1 (en) * | 1989-08-23 | 1994-05-25 | Nof Corporation | W/o emulsion explosive composition |
-
1998
- 1998-07-03 FR FR9808498A patent/FR2780726B1/en not_active Expired - Fee Related
-
1999
- 1999-06-17 SI SI9930259T patent/SI0968985T1/en unknown
- 1999-06-17 ES ES99401491T patent/ES2196739T3/en not_active Expired - Lifetime
- 1999-06-17 EP EP99401491A patent/EP0968985B1/en not_active Expired - Lifetime
- 1999-06-17 DE DE69906626T patent/DE69906626T2/en not_active Expired - Lifetime
- 1999-06-17 AT AT99401491T patent/ATE236863T1/en not_active IP Right Cessation
- 1999-06-17 DK DK99401491T patent/DK0968985T3/en active
- 1999-06-17 PT PT99401491T patent/PT968985E/en unknown
- 1999-07-01 BG BG103547A patent/BG64046B1/en unknown
- 1999-07-01 NO NO19993278A patent/NO311670B1/en not_active IP Right Cessation
- 1999-07-01 RU RU99113834/02A patent/RU2222519C2/en not_active IP Right Cessation
- 1999-07-01 PL PL99334147A patent/PL189609B1/en not_active IP Right Cessation
- 1999-07-02 HU HU9902263A patent/HU224307B1/en not_active IP Right Cessation
- 1999-07-02 UA UA99073778A patent/UA58528C2/en unknown
- 1999-07-02 CZ CZ19992408A patent/CZ294205B6/en not_active IP Right Cessation
- 1999-07-02 SK SK909-99A patent/SK285047B6/en not_active IP Right Cessation
- 1999-07-02 OA OA9900151A patent/OA11073A/en unknown
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2086364A (en) * | 1980-10-27 | 1982-05-12 | Atlas Powder Co | Emulsion explosives containing a reduced amount of water |
| EP0155800A1 (en) * | 1984-03-21 | 1985-09-25 | Imperial Chemical Industries Plc | Emulsion explosives composition |
| EP0159171A1 (en) * | 1984-04-05 | 1985-10-23 | Ireco Incorporated | Cast explosive composition |
| EP0256447A1 (en) * | 1986-08-11 | 1988-02-24 | Nippon Kayaku Kabushiki Kaisha | Method for explosive cladding |
| AU591976B2 (en) * | 1987-04-24 | 1989-12-21 | Norsk Hydro A.S | Emulsion explosive |
| EP0292234A2 (en) * | 1987-05-20 | 1988-11-23 | Aeci Limited | Low water content emulsion |
| EP0598115A1 (en) * | 1989-08-23 | 1994-05-25 | Nof Corporation | W/o emulsion explosive composition |
| US4976793A (en) * | 1990-06-12 | 1990-12-11 | Dantex Explosives (Proprietary) Limited | Explosive composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110526791A (en) * | 2019-09-18 | 2019-12-03 | 北方爆破科技有限公司 | A kind of mixed explosive and preparation method thereof for fluidized bed |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE236863T1 (en) | 2003-04-15 |
| SK90999A3 (en) | 2000-05-16 |
| OA11073A (en) | 2003-03-17 |
| NO993278L (en) | 2000-01-04 |
| FR2780726A1 (en) | 2000-01-07 |
| RU2222519C2 (en) | 2004-01-27 |
| HU9902263D0 (en) | 1999-08-30 |
| HUP9902263A2 (en) | 2001-12-28 |
| EP0968985B1 (en) | 2003-04-09 |
| CZ294205B6 (en) | 2004-10-13 |
| CZ9902408A3 (en) | 2000-10-11 |
| DE69906626D1 (en) | 2003-05-15 |
| DE69906626T2 (en) | 2004-02-05 |
| BG103547A (en) | 2000-01-31 |
| ES2196739T3 (en) | 2003-12-16 |
| NO311670B1 (en) | 2002-01-02 |
| BG64046B1 (en) | 2003-11-28 |
| FR2780726B1 (en) | 2000-08-25 |
| UA58528C2 (en) | 2003-08-15 |
| PL189609B1 (en) | 2005-08-31 |
| DK0968985T3 (en) | 2003-08-04 |
| HU224307B1 (en) | 2005-07-28 |
| SK285047B6 (en) | 2006-05-04 |
| HUP9902263A3 (en) | 2002-02-28 |
| NO993278D0 (en) | 1999-07-01 |
| PT968985E (en) | 2003-08-29 |
| SI0968985T1 (en) | 2003-10-31 |
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