EP0968985B1 - Emulsions explosives encartouchées énergétiques - Google Patents
Emulsions explosives encartouchées énergétiques Download PDFInfo
- Publication number
- EP0968985B1 EP0968985B1 EP99401491A EP99401491A EP0968985B1 EP 0968985 B1 EP0968985 B1 EP 0968985B1 EP 99401491 A EP99401491 A EP 99401491A EP 99401491 A EP99401491 A EP 99401491A EP 0968985 B1 EP0968985 B1 EP 0968985B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- nitrate
- water
- weight
- emulsifier
- explosive emulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- 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
Definitions
- the present invention is in the field general industrial explosives for civil use.
- In-line explosive emulsions of the water-in-oil type are well known to those skilled in the art.
- the emulsions explosives mentioned above have a safety of use and significantly improved manufacturing. In counterpart, they are clearly less powerful and release less explosion energy.
- sensitizing molecules such as nitrate hydrazine and organic nitrates, including amine nitrates such as methylamine nitrate, or well again reaction catalysts such as the copper chloride, or else very oxidizers reagents such as chlorates or perchlorates.
- Patent application EP 598 115 describes for example explosive energy emulsions based on nitrate ammonium containing amine nitrate and / or nitrate hydrazine as a sensitizer.
- No. 4,371,408 discloses ammonium nitrate and sodium nitrate explosive emulsions sensitized with an amine nitrate and containing CuCl 2 as a detonation catalyst.
- the present invention therefore aims to new explosive emulsions encapsulated type water-in-oil sensitized by a gaseous phase dispersed and comprising ammonium nitrate, sodium nitrate, water, a fuel hydrocarbon, an emulsifier and aluminum.
- weight contents are expressed by compared to the sensitized explosive emulsion and must be understood limits included.
- the new explosive emulsions mentioned above according to the invention are in particular free of chlorates and perchlorates, for example those of ammonium, metals alkaline or alkaline earth metals, lacking molecules sensitizers of the organic nitrate type, by example of nitrates of alkylamines and nitrates alkanolamines, or nitrates of hydrazines, by example of hydrazine nitrate and nitrate methylhydrazine, free of metal catalysts reaction such as copper chloride.
- chlorates and perchlorates for example those of ammonium, metals alkaline or alkaline earth metals, lacking molecules sensitizers of the organic nitrate type, by example of nitrates of alkylamines and nitrates alkanolamines, or nitrates of hydrazines, by example of hydrazine nitrate and nitrate methylhydrazine, free of metal catalysts reaction
- 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.
- the hydrocarbon fuel is selected from the group consisting of oils, waxes, paraffins and mixtures thereof.
- the emulsifier can be any well-known emulsifier of the skilled person promoting physical stability water-in-oil emulsions by lowering the interfacial tension between the two phases of the emulsion.
- the emulsifier is preferably chosen from group consisting of polymeric emulsifiers that simultaneously contain hydrophilic chains and hydrophobic chains, such as polyisobutylene and succinic anhydride, the amines, especially those having from 12 to 24 carbon atoms carbon, esters of fatty acids such as monooleate of sorbitan, sorbitan laurate, palmitate sorbitan and sorbitan stearate, alkylaryl sulfonates, and mixtures thereof.
- polymeric emulsifiers that simultaneously contain hydrophilic chains and hydrophobic chains, such as polyisobutylene and succinic anhydride, the amines, especially those having from 12 to 24 carbon atoms carbon, esters of fatty acids such as monooleate of 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 powder.
- Its particle size is generally between 0.1 ⁇ m and 250 ⁇ m, more preferably 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.
- the gaseous release in situ by means of chemical agents, including the use of nitrites, such as nitrite sodium, which, by reaction with the ammonium ions of the ammonium nitrate, cause in situ formation nitrogen.
- nitrites such as nitrite sodium
- This reaction can be accelerated by raising of the temperature and / or by a catalyst of 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 ammonium nitrate and sodium nitrate is between 73% and 77%, better still between 74% and 76%.
- the content weight in ammonium nitrate is between 61% and 67%, better still between 62% and 65%.
- the content weight in water is between 4.5% and 6.5%, better still between 5% and 6%.
- the content weight in aluminum is between 13% and 17%, better still between 13.5% and 16.5%, better still between 14% and 16%.
- the content weight of emulsifier is between 1.5% and 4%, better still between 2% and 3.5%.
- the content weight of 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 of 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 actual total energy, determined under water, is between 1100 cal / g and 1400 cal / g, more preferably between 1200 cal / g and 1400 cal / g.
- the explosive emulsions according to the invention can be obtained by analogy with any known process for obtaining explosive emulsions of water-in-oil type 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 stage with hydrocarbon fuel.
- the emulsion can be obtained using a turbine and simultaneously homogenized for example using a clover blade.
- the two phases, and the emulsifier if it is not incorporated in the phase fat are pumped by means of metering pumps into feed ducts of an emulsifier.
- aluminum, microspheres and / or the chemical gas generator are preferably incorporated into the emulsion by kneading, in the mixer used to produce the emulsion, or in a planetary agitator mixer.
- the adjuvants are preferably incorporated continuously, for example using endless screw, in a mixer in which also discharges the water-in-oil emulsion from the emulsifier.
- the sensitized explosive emulsion thus prepared is then sintered, possibly after a first cooling, manually or automatic, in ducts for example of paper or plastic material, using an installation encartouchage well known to those skilled in the art.
- the cartridges obtained are then generally cooled, for example by cold water or air 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 realized the emulsion using a turbine while homogenizing simultaneously mixing with a clover blade.
- 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 the desired cartridge, the density of the emulsion explosive that is measured before the encartouchage and the addition of sodium nitrite, and the volume ratio gas phase (about 15%).
- the desired gas phase volume is achieved and we then stop the formation chemical reaction nitrogen by suddenly lowering the temperature of the emulsion, which is easily achieved by spraying cold water on the cartridges.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Colloid Chemistry (AREA)
- Air Bags (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
- Cosmetics (AREA)
- General Preparation And Processing Of Foods (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Disintegrating Or Milling (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Description
- 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.
- 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 0,5% et 5%,
- la teneur pondérale en émulsifiant est comprise entre 0,5% et 5%,
- 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%.
- 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.
Claims (10)
- Emulsion explosive encartouchée de type eau-dans-huile sensibilisée par une phase gazeuse dispersée, comprenant du nitrate d'ammonium, du nitrate de sodium, de l'eau, un combustible hydrocarboné, un émulsifiant et de l'aluminium, caractérisée 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 0,5% et 5%,la teneur pondérale en émulsifiant est comprise entre 0,5% et 5%,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%.
- Emulsion explosive selon la revendication 1, caractérisée en ce que la teneur pondérale en eau est comprise entre 5% et 6%.
- Emulsion explosive selon la revendication 1 ou 2, caractérisée en ce que la teneur pondérale en aluminium est comprise entre 13,5% et 16,5%.
- Emulsion explosive selon la revendication 1, caractérisée en ce que la somme des teneurs pondérales en nitrate d'ammonium et en nitrate de sodium est comprise entre 73% et 77%.
- Emulsion explosive selon la revendication 1, caractérisée en ce que sa densité est comprise entre 1,26 et 1,40.
- Emulsion explosive selon la revendication 1, caractérisée en ce que sa vitesse de détonation, mesurée en diamètre 80 mm confiné, est comprise entre 5500 m/s et 6300 m/s.
- Emulsion explosive selon la revendication 1, caractérisée en ce que son énergie totale réelle, déterminée sous eau, est comprise entre 1100 cal/g et 1400 cal/g.
- Emulsion explosive selon la revendication 1, caractérisée en ce que sa teneur volumique en phase gazeuse dispersée est comprise entre 13% et 17%.
- Emulsion explosive selon la revendication 1, caractérisée en ce que le combustible hydrocarboné est choisi dans le groupe constitué par les huiles, les cires, les paraffines et leurs mélanges.
- Emulsion explosive selon la revendication 1, caractérisée en ce que l'émulsifiant est choisi dans le groupe constitué par les amines, les esters d'acides gras, les alkylaryl sulfonates, les polymères comportant simultanément des chaínes hydrophiles et des chaínes hydrophobes, et leurs mélanges.
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 |
---|---|---|---|
FR9808498 | 1998-07-03 | ||
FR9808498A FR2780726B1 (fr) | 1998-07-03 | 1998-07-03 | Emulsions explosives encartouchees energetiques |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0968985A1 EP0968985A1 (fr) | 2000-01-05 |
EP0968985B1 true EP0968985B1 (fr) | 2003-04-09 |
Family
ID=9528202
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99401491A Expired - Lifetime EP0968985B1 (fr) | 1998-07-03 | 1999-06-17 | Emulsions explosives encartouchées énergétiques |
Country Status (17)
Country | Link |
---|---|
EP (1) | EP0968985B1 (fr) |
AT (1) | ATE236863T1 (fr) |
BG (1) | BG64046B1 (fr) |
CZ (1) | CZ294205B6 (fr) |
DE (1) | DE69906626T2 (fr) |
DK (1) | DK0968985T3 (fr) |
ES (1) | ES2196739T3 (fr) |
FR (1) | FR2780726B1 (fr) |
HU (1) | HU224307B1 (fr) |
NO (1) | NO311670B1 (fr) |
OA (1) | OA11073A (fr) |
PL (1) | PL189609B1 (fr) |
PT (1) | PT968985E (fr) |
RU (1) | RU2222519C2 (fr) |
SI (1) | SI0968985T1 (fr) |
SK (1) | SK285047B6 (fr) |
UA (1) | UA58528C2 (fr) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CZ307535B6 (cs) * | 2017-03-01 | 2018-11-14 | Explosia A.S. | Sypká koloběhovaná amonledková průmyslová trhavina |
CN111699166A (zh) | 2018-01-09 | 2020-09-22 | 戴诺诺贝尔亚太股份有限公司 | 用于反应性土壤中的炸药组合物和相关方法 |
CN110526791A (zh) * | 2019-09-18 | 2019-12-03 | 北方爆破科技有限公司 | 一种用于流化床的混装炸药及其制备方法 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4383873A (en) * | 1980-10-27 | 1983-05-17 | Atlas Powder Company | Sensitive low water emulsion explosive compositions |
GB2156799B (en) * | 1984-03-21 | 1987-12-16 | Ici Plc | Emulsion explosive |
CA1220943A (fr) * | 1984-04-05 | 1987-04-28 | Harvey A. Jessop, (Deceased) | Agent de sautage coule |
US4844321A (en) * | 1986-08-11 | 1989-07-04 | Nippon Kayaku Kabushiki Kaisha | Method for explosive cladding |
AU591976B2 (en) * | 1987-04-24 | 1989-12-21 | Norsk Hydro A.S | Emulsion explosive |
ZW5188A1 (en) * | 1987-05-20 | 1989-09-27 | Aeci Ltd | Explosive |
CA2065848C (fr) * | 1989-08-23 | 1999-12-14 | Akio Torii | Emulsion eau-huile detonante |
US4976793A (en) * | 1990-06-12 | 1990-12-11 | Dantex Explosives (Proprietary) Limited | Explosive composition |
-
1998
- 1998-07-03 FR FR9808498A patent/FR2780726B1/fr not_active Expired - Fee Related
-
1999
- 1999-06-17 PT PT99401491T patent/PT968985E/pt unknown
- 1999-06-17 AT AT99401491T patent/ATE236863T1/de not_active IP Right Cessation
- 1999-06-17 EP EP99401491A patent/EP0968985B1/fr not_active Expired - Lifetime
- 1999-06-17 SI SI9930259T patent/SI0968985T1/xx unknown
- 1999-06-17 ES ES99401491T patent/ES2196739T3/es not_active Expired - Lifetime
- 1999-06-17 DE DE69906626T patent/DE69906626T2/de not_active Expired - Lifetime
- 1999-06-17 DK DK99401491T patent/DK0968985T3/da active
- 1999-07-01 NO NO19993278A patent/NO311670B1/no not_active IP Right Cessation
- 1999-07-01 RU RU99113834/02A patent/RU2222519C2/ru not_active IP Right Cessation
- 1999-07-01 PL PL99334147A patent/PL189609B1/pl not_active IP Right Cessation
- 1999-07-01 BG BG103547A patent/BG64046B1/bg unknown
- 1999-07-02 SK SK909-99A patent/SK285047B6/sk not_active IP Right Cessation
- 1999-07-02 UA UA99073778A patent/UA58528C2/uk unknown
- 1999-07-02 CZ CZ19992408A patent/CZ294205B6/cs not_active IP Right Cessation
- 1999-07-02 HU HU9902263A patent/HU224307B1/hu not_active IP Right Cessation
- 1999-07-02 OA OA9900151A patent/OA11073A/fr unknown
Also Published As
Publication number | Publication date |
---|---|
CZ294205B6 (cs) | 2004-10-13 |
RU2222519C2 (ru) | 2004-01-27 |
HUP9902263A2 (hu) | 2001-12-28 |
NO993278D0 (no) | 1999-07-01 |
PL189609B1 (pl) | 2005-08-31 |
BG103547A (en) | 2000-01-31 |
FR2780726A1 (fr) | 2000-01-07 |
UA58528C2 (uk) | 2003-08-15 |
PT968985E (pt) | 2003-08-29 |
SK90999A3 (en) | 2000-05-16 |
DE69906626T2 (de) | 2004-02-05 |
ATE236863T1 (de) | 2003-04-15 |
HU224307B1 (hu) | 2005-07-28 |
OA11073A (en) | 2003-03-17 |
DE69906626D1 (de) | 2003-05-15 |
SI0968985T1 (en) | 2003-10-31 |
HUP9902263A3 (en) | 2002-02-28 |
CZ9902408A3 (cs) | 2000-10-11 |
NO311670B1 (no) | 2002-01-02 |
EP0968985A1 (fr) | 2000-01-05 |
SK285047B6 (sk) | 2006-05-04 |
FR2780726B1 (fr) | 2000-08-25 |
HU9902263D0 (en) | 1999-08-30 |
NO993278L (no) | 2000-01-04 |
ES2196739T3 (es) | 2003-12-16 |
BG64046B1 (bg) | 2003-11-28 |
DK0968985T3 (da) | 2003-08-04 |
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