EP0084766A1 - Continuous process for the production of sirupeous explosive compositions that can be cartridged on a cutting machine, and products so obtained - Google Patents

Continuous process for the production of sirupeous explosive compositions that can be cartridged on a cutting machine, and products so obtained Download PDF

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Publication number
EP0084766A1
EP0084766A1 EP82870005A EP82870005A EP0084766A1 EP 0084766 A1 EP0084766 A1 EP 0084766A1 EP 82870005 A EP82870005 A EP 82870005A EP 82870005 A EP82870005 A EP 82870005A EP 0084766 A1 EP0084766 A1 EP 0084766A1
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EP
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Prior art keywords
explosive
composition
cutting machine
hardening agent
premix
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EP82870005A
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German (de)
French (fr)
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EP0084766B1 (en
Inventor
Lucien Waterlot
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PRB NOBEL EXPLOSIFS
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PRB NOBEL EXPLOSIFS
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Priority to DE8282870005T priority Critical patent/DE3267724D1/en
Priority to AT82870005T priority patent/ATE16794T1/en
Priority to EP82870005A priority patent/EP0084766B1/en
Priority to AU10320/83A priority patent/AU556444B2/en
Priority to IN18/DEL/83A priority patent/IN159851B/en
Priority to JP58012081A priority patent/JPS58208192A/en
Publication of EP0084766A1 publication Critical patent/EP0084766A1/en
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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
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying

Definitions

  • the present invention relates to improvements made to the continuous manufacturing and packaging of syrupy explosive compositions, having the property of solidifying rapidly, without sticking, so as to be sufficiently rigid and coherent to allow packaging in a paper case on a packaging machine. '' cutting type packing.
  • syrupy explosives have appeared on the market (also called “boullies” or “slurry”) in which the detonation support is provided by the redox reaction which takes place after ignition, between a prepared oxidizing solution hot, mineral or organic salts dissolved in water and a reducing premix consisting of solid combustible materials, mainly aluminum of different types, excluding any traditional explosive material proper.
  • a prepared oxidizing solution hot, mineral or organic salts dissolved in water and a reducing premix consisting of solid combustible materials, mainly aluminum of different types, excluding any traditional explosive material proper.
  • Such explosives are described in particular in United States patent 3,121,036 and in Belgian patent 575,043.
  • the sensitivity is mainly due to the presence of aluminum of the "paint" type while a complementary sensitivity is ensured as a function of the density of the gas microbubbles resulting from a chemical reaction within the mass. ; a more or less rubbery plastic texture is imparted to the explosive by gelation, by means of a crosslinking agent, of the guar gums present in the formula.
  • compositions lies in an increase in safety during manufacture, during storage, transport and use, while the methods of implementation offer a more extensive diversification than for conventional explosives.
  • this type of composition has a double defect.
  • the detonation capacity and the ability to transmit from one cartridge to another require increasingly fine sensitizers, and this at increasing rates; on the other hand, the plastic consistency of the cartridges makes them compressible, which in blast holes, may lead to the detonation being stopped under the effect of the compression waves which propagate in front of the detonation front.
  • the sensitivity could be increased so as to already ensure detonation for cartridge diameters less than 20 mm; an important additional advantage is due to the fact that certain explosives of this species can have a solid texture, instead of having a plastic consistency, which allows them to better resist the effects of the compression waves described above; the efficiency is all the greater as the manufacture is carried out from a solution rich in ammonium nitrate, that is to say at a higher crystallization point.
  • the disadvantage which the generally improved explosive porridge presents is a great difficulty of conditioning: the viscosity of some of them is such as the usual means (machines of the chub-pack type or barrels of extrusion) are not suitable.
  • a conventional sealing of the product cooled in tanks as it is carried out for traditional explosives (dynamites for example) from an extrusion screw or a cutting machine of the Rollex type offers the double disadvantage of being a discontinuous process and of completely desensitizing the explosive.
  • the cooled product is in the form of a solid mass, however powdery and brittle, too inconsistent to be easily cartoned. This is particularly the case for the composition described in US Patent 4,033,264 which describes the product obtained as a friable gelled explosive composition.
  • the present invention therefore aims to improve syrupy explosive compositions and to offer a process for their preparation which makes it possible to obtain explosives with a final solid texture allowing solidification which makes the product rigid but nevertheless sufficiently coherent for packaging in a case. paper on a cartoning machine of the cutting type is facilitated.
  • the aim is to obtain a product which solidifies rapidly without however sticking.
  • the invention relates to a continuous process for the production of cartridge-like syrupy compositions, characterized in that an oxidizing solution prepared hot, known per se, containing mineral or organic salts dissolved in water, and a premix are mixed.
  • reducing agent consisting of solid fuels based on combustible metals and a hardening agent introduced in solid form, prior to the final solidification of the composition, the mixture then being cartridge-filled using a cutting machine, preferably a cartoner Rollex type.
  • said mixture undergoes rapid and immediate cooling at the outlet of the device for mixing the oxidizing solution and the reducing premix.
  • Cartridges prepared using this composition and according to the above method are surprisingly characterized by aptitude characteristics of 6 cm in air in the case of the invention.
  • composition of the invention is no longer compressible, no "channel effect" is observed, as is the case for the composition described in Belgian patent 698,434 in which setting or hardening of the composition is ensured by metal salts.
  • the hardening agent necessary for extrudability is of the carboxymethylcellulose type; its content according to the invention, expressed as a percentage by weight relative to the final formula of the explosive composition is advantageously between 1 and 3%, preferably between 1.5 and 2.5% and very particularly advantageously is from around 2%.
  • Carboxymethylcellulose is a well known product in the porridge explosives industry; it is often cited as a fuel and thickener; this is the case in DE-A patents 1,813,173; 2,826,589 and 2,643,499, in patents FR-A 1,550,925 and 1,244,201 or also in patent US-E 26,115, US-A 3,235,425 and 3,524,777; certain particular properties have been found and claimed for it, such as for example to obtain better crosslinking (US-A patents 3,344,004 and 3,251,781) or better water resistance as well as longer storage (GB patent- A 1.238.818) or even improved stability (patent FR-A 2.006.804); in all these cases, it is an integral part of the oxidizing solution: it is associated with the aqueous phase either directly or in premix with glycol (GB-A 2 013 173 patent).
  • the carboxymethylcellulose acts as a hardening agent, essential for cloudability on a cartridge-type cutting machine, provided that it is incorporated, necessarily, in the solid part of the composition (that is to say with the reducing premix); it is therefore not, as in the aforementioned documents, a simple thickening (which would only have effects on the greater or lesser viscosity of the product), neither a crosslinking action (which would make the dough too plastic for the intended purpose), nor an improved water resistance or stability action.
  • the action of the hardening agent can be enhanced by the presence of a crosslinking agent based on chromium or antimony which acts on guar gum when the latter is present.
  • syrupy explosive compositions are well known to those skilled in the art and the invention extends to the compositions of the state of the art having the characteristic of the invention of containing a hardening agent in the solid combustible premix. . It appeared that the presence in the solution of a crystal regulator of the family of methyl naphthalene sulfonates sodium gives particularly favorable results.
  • a solution at 80 ° C. is prepared containing: and on the other hand, a premix containing:
  • the mixing in the proportion 87 parts by weight of solution and 13 parts by weight of premix is carried out by simple passage in a slurry mixer from where it is carried, either by gravity or by pumping, on the conveyor belt of the machine Rollex, cooled by water and air, and conveyed under the knife of the machine, in the form of a carpet ready for cutting, at the temperature of about 40 to 45 ° C, that is to say sufficiently cooled and coherent to be stuffed.
  • Each cut is individually molded in a paper case which, once closed, ensures and maintains the shape of the cartridge thus obtained.
  • the density of the explosive which conditions the weight of the cartridges, can, if necessary, be adjusted by bringing to the mixer at the same time as the solution and the premix of Example 1, 0 to 0.8 parts by weight of NO 2 Na in solution 75/25; the explosive preferably with 0.4 part by weight of N0 2 Na, packed in 30 mm / 200 g gives, without confinement, an aptitude in air of 6 cm and a detonation speed of 3800 to 4100 m / s per priming with a detonator at 440 mg of hexogen, at a density of 1.10-1.15.
  • Example 1 determines whether the atomized aluminum is replaced by silicon we obtain, at density 1.10:
  • the explosive power of Example 1 determined with a lead block is 400 cc, that is to say equivalent to that of a very good quality dynamite.
  • the process remains compatible with all the formulas based on the solution of Example 1 in which the content of combustible metal in the premix varies from 0 to 8 parts by weight. This will be illustrated in the following two examples giving the characteristics of the two extreme formulas.
  • the effect of the self-crosslinking guar added to the premix can be reinforced by 0.5 part by weight of a crosslinking agent based on chromium or antimony.
  • Example 2 To 86 parts by weight of the solution of Example 1, 14 parts by weight of a premix consisting of: The rest of the operations take place as in Examples 1 to 4. The product has excellent anti-sticking properties and can be easily implemented on a cartoning machine.
  • the hardening agent of the carboxymethylcellulose type can also be combined with the polyacrylamide.
  • Example 1 87 parts by weight of the solution of Example 1 are mixed with 13 parts by weight of the following premix: The characteristics of the products are the same as for Example 1.
  • Example 1 The solution of Example 1 is replaced by the following solution: The rest of the operations are carried out as in the previous examples and the results obtained are similar.

Abstract

1. Continuous process for the production of sirupeous compositions which can be put in cartridges, characterised in that an oxidising solution, which is prepared hot, of usual composition and containing inorganic or organic salts dissolved in water, is mixed with a reducing premix consisting of solid fuels based on metal fuels and of a hardener introduced in solid form of the carboxymethylcellulose type, prior to the final solidification of the composition, the mixture then being put in cartridges using a cutting machine.

Description

La présente invention concerne des perfectionnements apportés à la fabrication et au conditionnement en continu de compositions explosives sirupeuses, ayant la propriété de se solidifier rapidement, sans coller, de manière à être suffisamment rigides et cohérentes pour permettre un conditionnement en étui papier sur une machine d'encartouchage du type à découpe.The present invention relates to improvements made to the continuous manufacturing and packaging of syrupy explosive compositions, having the property of solidifying rapidly, without sticking, so as to be sufficiently rigid and coherent to allow packaging in a paper case on a packaging machine. '' cutting type packing.

Depuis quelques années sont apparus sur le marché des explosifs sirupeux (appelés aussi "boullies" ou "slurry") dans lesquels le support de détonation est assuré par la réaction oxydo-réductrice qui se déroule après la mise à feu, entre une solution oxydante préparée à chaud, de sels minéraux ou organiques dissous dans l'eau et un prémélange réducteur constitué de matières combustibles solides, principalement de l'aluminium de différents types, à l'exclusion detoute matière explosive traditionnelle proprement dite. De tels explosifs sont notamment décrits dans le brevet des Etats-Unis d'Amérique 3.121.036 et dans le brevet belge 575.043.In recent years, syrupy explosives have appeared on the market (also called "boullies" or "slurry") in which the detonation support is provided by the redox reaction which takes place after ignition, between a prepared oxidizing solution hot, mineral or organic salts dissolved in water and a reducing premix consisting of solid combustible materials, mainly aluminum of different types, excluding any traditional explosive material proper. Such explosives are described in particular in United States patent 3,121,036 and in Belgian patent 575,043.

Dans ce genre de composition, la sensibilité est principalement due à la présence d'aluminium du type "peinture" tandis qu'une sensibilité complémentaire est assurée en fonction de la densité des microbulles de gaz issues d'une réaction chimique au sein de la masse; une texture plastique plus ou moins caoutchouteuse est conférée à l'explosif par gélification, au moyen d'un agent de réticulation, des gommes de guar présentes dans la formule.In this type of composition, the sensitivity is mainly due to the presence of aluminum of the "paint" type while a complementary sensitivity is ensured as a function of the density of the gas microbubbles resulting from a chemical reaction within the mass. ; a more or less rubbery plastic texture is imparted to the explosive by gelation, by means of a crosslinking agent, of the guar gums present in the formula.

L'intérêt de ces compositions réside dans un accroissement de la sécurité au cours de la fabrication,pendant l'emmagasinage, le transport et l'emploi, tandis que les méthodes de mise en oeuvre offrent une diversification plus étendue que pour les explosifs classiques.The advantage of these compositions lies in an increase in safety during manufacture, during storage, transport and use, while the methods of implementation offer a more extensive diversification than for conventional explosives.

En petits diamètres (c'est-à-dire de 20 à 40 mm), ce type de compositions présente un double défaut. D'une part, au fur et à mesure que le diamètre est réduit, la capacité de détonation et l'aptitude à la transmission d'une cartouche à l'autre exigent des sensibilisants de plus en plus fins, et ceci à des taux de plus en plus élevés; d'autre part, la consistance plastique des cartouches les rend compressibles, ce qui en trous de mine, risque de conduire à l'arrêt de la détonation sous l'effet des ondes de compression qui se propagent en avant du front de détonation.In small diameters (that is to say from 20 to 40 mm), this type of composition has a double defect. On the one hand, as the diameter is reduced, the detonation capacity and the ability to transmit from one cartridge to another require increasingly fine sensitizers, and this at increasing rates; on the other hand, the plastic consistency of the cartridges makes them compressible, which in blast holes, may lead to the detonation being stopped under the effect of the compression waves which propagate in front of the detonation front.

Ainsi de nombreuses modifications ont été apportées à ces formules durant ces dernières années; parmi celles-ci, une modification particulièrement intéressante a consisté à améliorer la sensibilité de l'amorçage par l'introduction dans la composition d'un modificateur de cristaux. Lors du refroidissement de la bouillie, ce dernier règle la cristallisation des sels en empêchant la formation de cristaux trop gros, au profit de micro-cristaux favorables à la détonation.Many modifications have been made to these formulas in recent years; among these, a particularly interesting modification consisted in improving the sensitivity of the priming by the introduction into the composition of a crystal modifier. When the slurry cools, the latter regulates the crystallization of the salts by preventing the formation of excessively large crystals, in favor of micro-crystals favorable to detonation.

De cette façon, sans devoir passer à des teneurs trop élevées en aluminium sensibilisateur, la sensibilité a pu être accrue de manière à assurer déjà la détonation pour des diamètres de cartouches inférieures à 20 mm; un avantage supplémentaire important est dû au fait que certains explô- sifs de cette espèce peuvent présenter une texture solide, au lieu d'avoir une consistance plastique, ce qui leur permet de mieux résister aux effets des ondes de compression décrits plus haut; l'efficacité est d'autant plus grande que la fabrication se fait à partir d'une solution riche en nitrate d'ammonium, c'est-à-dire à point de cristallisation plus élevé.In this way, without having to switch to too high levels of sensitizing aluminum, the sensitivity could be increased so as to already ensure detonation for cartridge diameters less than 20 mm; an important additional advantage is due to the fact that certain explosives of this species can have a solid texture, instead of having a plastic consistency, which allows them to better resist the effects of the compression waves described above; the efficiency is all the greater as the manufacture is carried out from a solution rich in ammonium nitrate, that is to say at a higher crystallization point.

L'inconvénient que présentent d'une manière générale les bouillies explosives ainsi améliorées réside dans une grande difficulté de conditionnement : la viscosité de certaines d'entre elles est telle que les moyens habituels (les machines du type chub-pack ou les canons d'extrusion) ne conviennent pas. D'autre part, un encartouchage classique du produit refroidi en cuve tel qu'il est réalisé pour les explosifs traditionnels (dynamites par exemple) à partir d'une vis d'extrusion ou d'une machine à découpe du type Rollex, offre le double désavantage d'être un procédé discontinu et.de désensibiliser complètement l'explosif. A ce moment d'ailleurs, le produit refroidi se présente sous forme d'une masse solide mais cependant poudreuse et friable, trop peu cohérente pour être encartouchée facilement. C'est le cas notamment de la composition décrite dans le brevetlfméricain 4,033,264 qui décrit le produit obtenu comme une composition explosive gélifiée friable.The disadvantage which the generally improved explosive porridge presents is a great difficulty of conditioning: the viscosity of some of them is such as the usual means (machines of the chub-pack type or barrels of extrusion) are not suitable. On the other hand, a conventional sealing of the product cooled in tanks as it is carried out for traditional explosives (dynamites for example) from an extrusion screw or a cutting machine of the Rollex type, offers the double disadvantage of being a discontinuous process and of completely desensitizing the explosive. At this moreover, the cooled product is in the form of a solid mass, however powdery and brittle, too inconsistent to be easily cartoned. This is particularly the case for the composition described in US Patent 4,033,264 which describes the product obtained as a friable gelled explosive composition.

La présente invention vise par conséquent à améliorer des compositions explosives sirupeuses et à offrir un procédé pour leur préparation qui permette d'obtenir des explosifs à texture solide finale permettant une solidification qui rend le produit rigide mais cependant suffisamment cohérent pour qu'un conditionnement en étui papier sur une machine d'encartouchage du type à découpe soit facilité.The present invention therefore aims to improve syrupy explosive compositions and to offer a process for their preparation which makes it possible to obtain explosives with a final solid texture allowing solidification which makes the product rigid but nevertheless sufficiently coherent for packaging in a case. paper on a cartoning machine of the cutting type is facilitated.

Selon un aspect complémentaire de l'invention, on vise à obtenir un produit qui se solidifie rapidement sans cependant coller.According to a complementary aspect of the invention, the aim is to obtain a product which solidifies rapidly without however sticking.

Par le procédé de l'invention, il devient possible d'obtenir des cartouches du type de celles utilisées pour la dynamite, au départ d'un explosif sirupeux sans difficulté de conditionnement due à la friabilité du produit.By the method of the invention, it becomes possible to obtain cartridges of the type of those used for dynamite, starting from a syrupy explosive without difficulty in packaging due to the friability of the product.

En conséquence, l'invention porte sur un procédé continu de production de compositions sirupeuses encartouchées caractérisé en ce qu'on mélange une solution oxydante préparée à chaud, connue en soi, contenant des sels minéraux ou organiques dissous dans l'eau, et un prémélange réducteur constitué de combustibles solides à base de métaux combustibles et d'un agent durcissant introduit sous forme solide, préalablement à la solidification finale de la composition, le mélange étant ensuite encartouché à l'aide d'une machine à découpe, de préférence une encartoucheuse de type Rollex.Consequently, the invention relates to a continuous process for the production of cartridge-like syrupy compositions, characterized in that an oxidizing solution prepared hot, known per se, containing mineral or organic salts dissolved in water, and a premix are mixed. reducing agent consisting of solid fuels based on combustible metals and a hardening agent introduced in solid form, prior to the final solidification of the composition, the mixture then being cartridge-filled using a cutting machine, preferably a cartoner Rollex type.

Avantageusement, ledit mélange subit un refroidissement rapide et immédiat à la sortie du dispositif de mélange de la solution oxydante et du prémélange réducteur.Advantageously, said mixture undergoes rapid and immediate cooling at the outlet of the device for mixing the oxidizing solution and the reducing premix.

Il est apparu que cette addition de l'agent durcissant permet d'obtenir par refroidissement, la composition explosive sous forme durcie et liée, c'est-à-dire cohérente et ne présentant aucun caractère de friabilité.It appeared that this addition of the hardening agent makes it possible to obtain, by cooling, the explosive composition in hardened and bonded form, that is to say coherent and having no friability character.

Des cartouches préparées à l'aide de cette composition et selon le procédé ci-avant se caractérisent de manière surprenante par des caractéristiques d'aptitude de 6 cm dans l'air dans le cas de l'invention.Cartridges prepared using this composition and according to the above method are surprisingly characterized by aptitude characteristics of 6 cm in air in the case of the invention.

De plus, du fait que la composition de l'invention n'est plus compressible, on n'observe pas de "channel effect" comme c'est la cas pour la composition décrite dans le brevet belge 698.434 dans laquelle une prise ou durcissement de la composition est assuré par des sels métalliques.In addition, since the composition of the invention is no longer compressible, no "channel effect" is observed, as is the case for the composition described in Belgian patent 698,434 in which setting or hardening of the composition is ensured by metal salts.

L'agent durcissant nécessaire à la boudinabilité est du type carboxyméthylcellulose; sa teneur selon l'invention, exprimée en pourcentage en poids par rapport à la formule finale de la composition explosive est avantageusement comprise entre 1 et 3 %, de préférence entre 1,5 et 2,5 % et tout particulièrement avantageusement est de l'ordre de 2 %.The hardening agent necessary for extrudability is of the carboxymethylcellulose type; its content according to the invention, expressed as a percentage by weight relative to the final formula of the explosive composition is advantageously between 1 and 3%, preferably between 1.5 and 2.5% and very particularly advantageously is from around 2%.

La carboxyméthylcellulose est un produit bien connu de l'industrie des explosifs en bouillies; elle est citée souvent comme combustible et épaississant; c'est le cas dans les brevets DE-A 1.813.173; 2.826.589 et 2.643.499, dans les brevets FR-A 1.550.925 et 1.244.201 ou encore dans le brevets US-E 26.115, US-A 3.235.425 et 3.524.777; certaines propriétés particulières lui ont été trouvées et revendiquées, comme par exemple pour obtenir une meilleure réticulation (brevets US-A 3.344.004 et 3.251.781) ou une meilleure résistance à l'eau ainsi qu'un plus long stockage (brevet GB-A 1.238.818) ou encore une stabilité améliorée (brevet FR-A 2.006.804); dans tous ces cas, elle fait partie intégrante de la solution oxydante : elle est associée à la phase aqueuse soit directement,soit en prémélange avec du glycol (brevet GB-A 2 013 173).Carboxymethylcellulose is a well known product in the porridge explosives industry; it is often cited as a fuel and thickener; this is the case in DE-A patents 1,813,173; 2,826,589 and 2,643,499, in patents FR-A 1,550,925 and 1,244,201 or also in patent US-E 26,115, US-A 3,235,425 and 3,524,777; certain particular properties have been found and claimed for it, such as for example to obtain better crosslinking (US-A patents 3,344,004 and 3,251,781) or better water resistance as well as longer storage (GB patent- A 1.238.818) or even improved stability (patent FR-A 2.006.804); in all these cases, it is an integral part of the oxidizing solution: it is associated with the aqueous phase either directly or in premix with glycol (GB-A 2 013 173 patent).

La présente invention met en évidence un autre aspect particulier du produit : il a été trouvé que le carboxyméthylcellulose agit comme agent durcissant, indispensable à laboudinabilité sur une machine à encartoucher du type à découpe, pour autant qu'elle soit incorporée, obligatoirement, à la partie solide de la composition (c'est-à-dire au prémélange réducteur); il ne s'agit donc pas comme dans les documents précités d'un simple épaississement (qui n'aurait d'effets que sur la plus ou moins grande viscosité du produit), ni d'une action de réticulation (qui rendrait la pâte trop plastique pour le but recherché), ni d'une action de résistance à l'eau améliorée ou sur la stabilité.The present invention highlights another particular aspect of the product: it has been found that the carboxymethylcellulose acts as a hardening agent, essential for cloudability on a cartridge-type cutting machine, provided that it is incorporated, necessarily, in the solid part of the composition (that is to say with the reducing premix); it is therefore not, as in the aforementioned documents, a simple thickening (which would only have effects on the greater or lesser viscosity of the product), neither a crosslinking action (which would make the dough too plastic for the intended purpose), nor an improved water resistance or stability action.

A cet égard, il est apparu au contraire que la rigidité et la cohésion au moment de l'encartouchage étaient maximales lorsque la solution ne contenait pas les gommes de guat que l'on utilise habituellement, celles-ci de par leur nature assurant en effet toujours une certaine plasticité au produit final au détriment de sa rigidité. Les gommes de guar ne sont donc à utiliser dans les compositions de l'invention que lorsqu'un compromis entre plasticité et rigidité est recherché; dans le cas normal où l'on veut obtenir une rigidité et une cohésion maximales, la gomme de guar fait partie intégrante du prémélange solide et doit être du type autoréticulant.In this regard, it appeared on the contrary that the rigidity and cohesion at the time of the cartridge filling were maximum when the solution did not contain the guat gums that are usually used, these by their nature ensuring indeed always a certain plasticity to the final product at the expense of its rigidity. Guar gums are therefore only to be used in the compositions of the invention when a compromise between plasticity and rigidity is sought; in the normal case where it is desired to obtain maximum rigidity and cohesion, the guar gum is an integral part of the solid premix and must be of the self-crosslinking type.

Afin d'éviter que les compositions explosives obtenues ne présentent une consistance collante, il est apparu que l'addition d'un agent anti-collant du type du talc permet de faciliter la mise en oeuvre des compositions de l'invention sur les machines d'encartouchage.In order to prevent the explosive compositions obtained from exhibiting a sticky consistency, it appeared that the addition of an anti-sticking agent of the talc type makes it possible to facilitate the use of the compositions of the invention on machines for '' packaging.

Il est d'autre part apparu que l'action de l'agent durcissant peut être renforcée par la présence d'un agent réticulant à base de chrome ou d'antimoine qui agit sur la gomme de guar lorsque celle-ci est présente.It has also appeared that the action of the hardening agent can be enhanced by the presence of a crosslinking agent based on chromium or antimony which acts on guar gum when the latter is present.

Il est apparu que des résultats particulièrement satisfaisants permettant sans difficulté la transposition à l'encartouchage sur une machine du type Rollex peuvent être obtenus par ce procédé lorsque la composition subit un refroidissement rapide et immédiat à la sortie du dispositif de mélange de la solution oxydante et du prémélange réducteur.It appeared that particularly satisfactory results allowing without difficulty the transposition to cartridge filling on a machine of the Rollex type can be obtained by this process when the composition undergoes rapid and immediate cooling at the outlet of the device for mixing the oxidizing solution and of the reducing premix.

La préparation des compositions explosives sirupeuses est bien connue de l'homme de l'art et l'invention s'étend aux compositions de l'état de la technique présentant la caractéristique de l'invention de contenir un agent durcissant dans le prémélange combustible solide. Il est apparu que la présence dans la solution d'un régulateur de cristaux de la famille des méthyl-naphtalène-sulfonates sodiques donne des résultats particulièrement favorables.The preparation of syrupy explosive compositions is well known to those skilled in the art and the invention extends to the compositions of the state of the art having the characteristic of the invention of containing a hardening agent in the solid combustible premix. . It appeared that the presence in the solution of a crystal regulator of the family of methyl naphthalene sulfonates sodium gives particularly favorable results.

Egalement la présence dans la solution, en plus des sels oxydants, de 5 à 10 % d'urée confère d'excellentes caractéristiques explosives aux compositions obtenues.Also the presence in the solution, in addition to the oxidizing salts, of 5 to 10% of urea gives excellent explosive characteristics to the compositions obtained.

Dans le cas où l'on souhaite obtenir une texture rigide fibreuse de la composition, il est apparu intéressant d'ajouter à l'agent durcissant du type carboxyméthylcellulose, de la polyacrylamide.In the case where it is desired to obtain a rigid fibrous texture of the composition, it has appeared advantageous to add to the hardening agent of the carboxymethylcellulose type, polyacrylamide.

L'invention sera décrite plus en détail à titre d'illustration sans caractère limitatif à l'aide des exemples qui suivent.The invention will be described in more detail by way of illustration without limitation, using the following examples.

Exemple 1Example 1

D'une part, on prépare une solution à 80°C contenant :

Figure imgb0001
et d'autre part, un prémélange contenant :
Figure imgb0002
Le mélange dans la proportion 87 parties en poids de solution et 13 parties en poids de prémélange se réalise par simple passage dans un mélangeur à bouillie d'où il est porté, soit par gravité, soit par pompage, sur la courroie transporteuse de la machine Rollex, refroidie par eau et par air, et acheminé sous le couteau de la machine, sous la forme d'un tapis prêt à la découpe, à la température d'environ 40 à 45°C, c'est-à-dire suffisamment refroidi et cohérent pour être encartouché. Chaque découpe est moulée individuellement dans un étui en papier qui, une fois fermé, assure et maintient la forme de la cartouche ainsi obtenue. La densité de l'explosif, conditionnant le poids des cartouches peut s'il le faut, être réglée en amenant au mélangeur en même temps que la solution et le prémélange de l'exemple 1, 0 à 0,8 parties en poids de NO2Na en solution 75/25; l'explosif préférentiellement avec 0,4 partie en poids de N02Na, encartouché en 30 mm/200 g donne, sans confinement, une aptitude dans l'air de 6 cm et une vitesse de détonation de 3800 à 4100 m/s par amorçage au détonateur à 440 mg d'hexogène, à la densité de 1,10-1,15. Si l'aluminium atomisé est remplacé par du silicium on obtient, à la densité 1,10 :
Figure imgb0003
La puissance de l'explosif de l'exemple 1 déterminé au bloc de plomb est de 400 cc, c'èst-à-dire équivalente à celle d'une dynamite de très bonne qualité. Le procédé reste compatible avec toutes les formules basées sur la solution de l'exemple 1 dans laquelle la teneur en métal combustible du prémélange varie de 0 à 8 parties en poids. Ceci sera illustré dans les deux exemples qui suivent donnant les caractéristiques des deux formules extrêmes.On the one hand, a solution at 80 ° C. is prepared containing:
Figure imgb0001
 and on the other hand, a premix containing:
Figure imgb0002
 The mixing in the proportion 87 parts by weight of solution and 13 parts by weight of premix is carried out by simple passage in a slurry mixer from where it is carried, either by gravity or by pumping, on the conveyor belt of the machine Rollex, cooled by water and air, and conveyed under the knife of the machine, in the form of a carpet ready for cutting, at the temperature of about 40 to 45 ° C, that is to say sufficiently cooled and coherent to be stuffed. Each cut is individually molded in a paper case which, once closed, ensures and maintains the shape of the cartridge thus obtained. The density of the explosive, which conditions the weight of the cartridges, can, if necessary, be adjusted by bringing to the mixer at the same time as the solution and the premix of Example 1, 0 to 0.8 parts by weight of NO 2 Na in solution 75/25; the explosive preferably with 0.4 part by weight of N0 2 Na, packed in 30 mm / 200 g gives, without confinement, an aptitude in air of 6 cm and a detonation speed of 3800 to 4100 m / s per priming with a detonator at 440 mg of hexogen, at a density of 1.10-1.15. If the atomized aluminum is replaced by silicon we obtain, at density 1.10:
Figure imgb0003
 The explosive power of Example 1 determined with a lead block is 400 cc, that is to say equivalent to that of a very good quality dynamite. The process remains compatible with all the formulas based on the solution of Example 1 in which the content of combustible metal in the premix varies from 0 to 8 parts by weight. This will be illustrated in the following two examples giving the characteristics of the two extreme formulas.

Exemple 2Example 2

Composition à 89,5 % solution et 10,5 % de prémélange ne contenant pas de métal combustible (sauf l'Al sensibilisant) :

Figure imgb0004
Composition with 89.5% solution and 10.5% of premix containing no combustible metal (except the sensitizing Al):
Figure imgb0004

Exemple 3Example 3

Composition à 81,5 % solution et 18,5 % de prémélange contenant 8 parties de métal combustible (Al), en plus de l'Al sensibilisant; à la densité 1,15 :

Figure imgb0005
Composition with 81.5% solution and 18.5% of premix containing 8 parts of combustible metal (Al), in addition to the sensitizing Al; at density 1.15:
Figure imgb0005

Exemple 4Example 4

Dans des explosifs analogues à ceux des exemples précédents l'effet de la guar autoréticulante ajoutée au prémélange peut être renforcé par 0,5 partie en poids d'un agent réticulant à base de chrome ou d'antimoine.In explosives similar to those of the previous examples, the effect of the self-crosslinking guar added to the premix can be reinforced by 0.5 part by weight of a crosslinking agent based on chromium or antimony.

Exemple 5Example 5

A 86 parties en poids de la solution de l'exemple 1, on ajoute 14 parties en poids d'un prémélange constitué de :

Figure imgb0006
La suite des opérations se déroule comme pour les exemples 1 à 4. Le produit présente d'excellentes propriétés anti- collantes et se met en oeuvre facilement sur une machine d'encartouchage.To 86 parts by weight of the solution of Example 1, 14 parts by weight of a premix consisting of:
Figure imgb0006
 The rest of the operations take place as in Examples 1 to 4. The product has excellent anti-sticking properties and can be easily implemented on a cartoning machine.

Exemple 6Example 6

Dans le cas où une texture rigide fibreuse est souhaitée, l'agent durcissant de type carboxyméthylcellulose peut être également associé à la polyacrylamide.In the case where a rigid fibrous texture is desired, the hardening agent of the carboxymethylcellulose type can also be combined with the polyacrylamide.

On mélange dans ce cas 87 parties en poids de la solution de l'exemple 1 avec 13 parties en poids du prémélange suivant :

Figure imgb0007
Les caractéristiques des produits sont les mêmes que pour l'exemple 1.In this case, 87 parts by weight of the solution of Example 1 are mixed with 13 parts by weight of the following premix:
Figure imgb0007
 The characteristics of the products are the same as for Example 1.

Exemple 7Example 7

On substitue à la solution de l'exemple 1, la solution suivante :

Figure imgb0008
La suite des opérations s'effectue comme dans les exemples précédents et les résultats obtenus sont analogues.The solution of Example 1 is replaced by the following solution:
Figure imgb0008
 The rest of the operations are carried out as in the previous examples and the results obtained are similar.

Claims (13)

l.Procédé continu de production de compositions sirupeuses en- cartouchéescaractérisé en ce qu'on mélange une solution oxydante préparée à chaud connue en soi, contenant des sels minéraux ou organiques dissous dans l'eau, et un prémélange réducteur constitué de combustibles solides à base de métaux combustibles et d'un agent durcissant introduit sous forme solide, préalablement à la solidification finale de la composition, le mélange étant ensuite encartouché à l'aide d'une machine à découpe.1. Continuous process for the production of syrupy compositions in cartridges, characterized in that an oxidizing solution prepared hot known per se, containing mineral or organic salts dissolved in water, and a reducing premix consisting of solid fuels based of combustible metals and of a hardening agent introduced in solid form, prior to the final solidification of the composition, the mixture then being stuffed using a cutting machine. 2.Procédé selon la revendication 1 caractérisé en ce que ladite machine à découpe est une encartoucheuse de type Rollex.2. Method according to claim 1 characterized in that said cutting machine is a Rollex-type cartridge sealer. 3.Procédé selon la revendication 1 ou 2 caractérisé en ce que ledit mélange subit un refroidissement rapide et immédiat à la sortie du dispositif de mélange de la solution oxydante et du prémélange réducteur.3. Method according to claim 1 or 2 characterized in that said mixture undergoes rapid and immediate cooling at the outlet of the device for mixing the oxidizing solution and the reducing premix. 4.Procédé selon l'une quelconque des revendications 1 à 3 caractérisé en ce que l'agent durcissant mis en oeuvre sous forme solide dans le prémélange réducteur est du type carboxyméthylcellulose.4. Method according to any one of claims 1 to 3 characterized in that the hardening agent used in solid form in the reducing premix is of the carboxymethylcellulose type. 5.Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que la teneur en agent durcissant, exprimée en pourcentage en poids par rapport à la formule finale de la composition explosive est comprise entre 1 et 3%, de préférence entre 1,5 et 2,5 % et tout particulièrement est de l'ordre de 2%.5. Method according to any one of claims 1 to 4, characterized in that the content of hardening agent, expressed as a percentage by weight relative to the final formula of the explosive composition is between 1 and 3%, preferably between 1.5 and 2.5% and more particularly is of the order of 2%. 6.Procédé selon l'une quelconque des revendications 1 à 5 caractérisé en ce qu'on incorpore au mélange un agent anti-collant.6. Method according to any one of claims 1 to 5 characterized in that an anti-sticking agent is incorporated into the mixture. 7.Procédé selon la revendication 6 caractérisé en ce que l'agent anti-collant incorporé est le talc.7. Method according to claim 6 characterized in that the anti-sticking agent incorporated is talc. 8.Procédé selon l'une quelconque des revendications 1 à 7 caractérisé en ce que l'action de l'agent durcissant est renforcée par l'addition d'un agent réticulant à base de chrome ou d'antimoine.8. Process according to any one of Claims 1 to 7, characterized in that the action of the hardening agent is reinforced by the addition of a crosslinking agent based on chromium or antimony. 9.Procédé selon l'une quelconque des revendications 1 à 8 caractérisé en ce que les métaux combustibles ajoutés sont l'aluminium et/ou le silicium.9. Method according to any one of claims 1 to 8 characterized in that the combustible metals added are aluminum and / or silicon. 10. Procédé selon l'une quelconque des revendications 1 à 9 caractérisé en ce que dans la solution oxydante a été ajouté un régulateur de cristaux de la famille des méthyl-naphtalène-sulfonates sodiques.10. Method according to any one of claims 1 to 9 characterized in that in the oxidizing solution has been added a crystal regulator of the family of methyl naphthalene sulfonates sodium. 11. Procédé selon l'une quelconque des revendications 1 à 10 caractérisé en ce que dans la solution oxydante, on a ajouté 5 à 10% d'urée.11. Method according to any one of claims 1 to 10 characterized in that in the oxidizing solution, 5 to 10% of urea was added. 12. Procédé selon l'une quelconque des revendications 1 à 11 caractérisé en ce que la densité finale de l'explosif est réglée par O à 0,8% en poids de N02Na en solution 75/25.12. Method according to any one of claims 1 to 11 characterized in that the final density of the explosive is adjusted by O to 0.8% by weight of N0 2 Na in 75/25 solution. 13. Cartouches de compositions sirupeuses explosives obtenues par le procédé d'une quelconque des revendications 1 à 12.13. Cartridges of explosive syrupy compositions obtained by the process of any one of claims 1 to 12.
EP82870005A 1982-01-26 1982-01-26 Continuous process for the production of sirupeous explosive compositions that can be cartridged on a cutting machine, and products so obtained Expired EP0084766B1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
DE8282870005T DE3267724D1 (en) 1982-01-26 1982-01-26 Continuous process for the production of sirupeous explosive compositions that can be cartridged on a cutting machine, and products so obtained
AT82870005T ATE16794T1 (en) 1982-01-26 1982-01-26 CONTINUOUS PROCESS FOR THE MANUFACTURE OF SYRUP EXPLOSIVES WHICH CAN BE LOADED IN CARTRIDGE CASES BY MACHINE AND PRODUCTS OBTAINED IN THIS WAY.
EP82870005A EP0084766B1 (en) 1982-01-26 1982-01-26 Continuous process for the production of sirupeous explosive compositions that can be cartridged on a cutting machine, and products so obtained
AU10320/83A AU556444B2 (en) 1982-01-26 1983-01-12 Production of syrupy explosive compositions
IN18/DEL/83A IN159851B (en) 1982-01-26 1983-01-12
JP58012081A JPS58208192A (en) 1982-01-26 1983-01-26 Manufacture of syrup-like explosive composition and cartridge

Applications Claiming Priority (1)

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EP82870005A EP0084766B1 (en) 1982-01-26 1982-01-26 Continuous process for the production of sirupeous explosive compositions that can be cartridged on a cutting machine, and products so obtained

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EP0084766A1 true EP0084766A1 (en) 1983-08-03
EP0084766B1 EP0084766B1 (en) 1985-12-04

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Publication number Priority date Publication date Assignee Title
EP0251606A2 (en) * 1986-06-21 1988-01-07 Freeman Chemicals Limited Polymers Division Protection of dangerous substances
EP0366274A1 (en) * 1988-10-14 1990-05-02 Dyno Nobel Inc. Emulsion explosive manufacturing method
EP0622346A1 (en) * 1993-04-20 1994-11-02 Union Espanola De Explosivos S.A. Explosive composition suitable for cartridging in paper and its method of manufacture

Families Citing this family (1)

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Publication number Priority date Publication date Assignee Title
NO160770C (en) * 1986-10-03 1989-05-31 Dyno Industrier As PROCEDURE AND DEVICE FOR PATTERNING OF ADHESIVE EXPLOSIVES.

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US3344004A (en) * 1966-02-11 1967-09-26 Hercules Inc Explosive gel composition cross-linked with a hydroxy compound
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Publication number Priority date Publication date Assignee Title
EP0251606A2 (en) * 1986-06-21 1988-01-07 Freeman Chemicals Limited Polymers Division Protection of dangerous substances
EP0251606A3 (en) * 1986-06-21 1990-10-17 Freeman Chemicals Limited Polymers Division Protection of dangerous substances
EP0366274A1 (en) * 1988-10-14 1990-05-02 Dyno Nobel Inc. Emulsion explosive manufacturing method
EP0622346A1 (en) * 1993-04-20 1994-11-02 Union Espanola De Explosivos S.A. Explosive composition suitable for cartridging in paper and its method of manufacture
ES2081744A1 (en) * 1993-04-20 1996-03-01 Espanola Explosivos Explosive composition suitable for cartridging in paper and its method of manufacture.

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AU1032083A (en) 1983-08-04
DE3267724D1 (en) 1986-01-16
EP0084766B1 (en) 1985-12-04
IN159851B (en) 1987-06-13
JPS58208192A (en) 1983-12-03
ATE16794T1 (en) 1985-12-15

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