EP0666248B1 - Gas generating mixture - Google Patents

Gas generating mixture Download PDF

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Publication number
EP0666248B1
EP0666248B1 EP94119383A EP94119383A EP0666248B1 EP 0666248 B1 EP0666248 B1 EP 0666248B1 EP 94119383 A EP94119383 A EP 94119383A EP 94119383 A EP94119383 A EP 94119383A EP 0666248 B1 EP0666248 B1 EP 0666248B1
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EP
European Patent Office
Prior art keywords
catalyst
mixture according
mixture
carrier
metal
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Expired - Lifetime
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EP94119383A
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German (de)
French (fr)
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EP0666248A1 (en
Inventor
Klaus Martin Dr. Bucerius
Helmut Schmid
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/007—Ballistic modifiers, burning rate catalysts, burning rate depressing agents, e.g. for gas generating
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
    • C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids

Definitions

  • the invention relates to a gas-generating mixture of a fuel, an oxidizer and a catalyst.
  • Gas-generating mixtures of the aforementioned type - also called gas generator sets - are characterized in that they enable a high gas yield (> 14 mol / kg) during combustion. They are used for rocket and barrel weapon drives as well as for inflatable restraint (airbag) and rescue systems. In the civil sector in particular, thermal-mechanical insensitivity and non-toxicity of the starting mixtures, but also a lack of toxicity in the resulting gases are required. Many systems in use do not meet these requirements, or meet them only very inadequately.
  • the invention has for its object to lower the combustion temperature and increase the rate of combustion in a mixture of the structure mentioned in the introduction.
  • the oxidizer is Cu (NO 3 ) 2 * 3Cu (OH) 2 and the catalyst consists of a metal or a metal alloy on a support.
  • the oxidizer provided according to the invention results in sustained and rapid combustion.
  • the maximum pressure is reached within milliseconds, with the gas temperature remaining below harmful limits.
  • Hitherto necessary slag formers, which in known systems for binding pollutants, e.g. Alkali oxides, required, can be omitted in the mixture according to the invention, so that a higher gas yield can be achieved.
  • the catalyst which is also used according to the invention is primarily used to reduce harmful gas (CO and NO), the term "catalyst" in the broader sense here denoting an active reaction component which can be implemented itself and has a reaction-guiding and / or reaction-accelerating effect.
  • the carrier serves to present the main component with a large specific surface and a defined grain size distribution. Another property of the carrier is to develop a cooling effect through physical and / or chemical processes - in a special phase of the reaction, that goes beyond a pure capacitive cooling effect.
  • the carrier can also act as a promoter of the main component. Not only the metal catalyst, but also the oxidizer are thermally and mechanically stable and in particular also not hygroscopic.
  • the catalyst is preferably a pyrophoric metal or such a metal alloy on a support which remains as a solid after the combustion.
  • This can be a silicate, preferably a layered or framework silicate.
  • N-rich and C-poor fuels include the well-known fuels TAGN (triaminoguanidine nitrate), NIGU (nitroguanidine), NTO (3-nitro-1,2,3-triazol-5-one) and the GZT (diguanidinium-5,5 '), which is characterized by a particularly high nitrogen content. -azotetrazolate) (DE 4 108 225).
  • TAGN, NIGU, NTO, but in particular GZT are preferably used in the mixture according to the invention when used for rescue and restraint systems.
  • a preferred mixture consists of GZT and Cu (NO 3 ) 2 * 3Cu (OH) 2 with a balanced oxygen balance and up to 30% by mass of the catalyst.
  • the mixture can contain Fe 2 O 3 as the coolant, the oxidative properties of which can additionally be used in the reaction mixture (DE 41 33 655, EP 0 536 525).
  • a mixture consisting of GZT, pyrophoric Ag on a layer or framework silicate support as catalyst and Cu (NO 3 ) 2 * 3Cu (OH) 2 as oxidizer in a ratio of 22.05: 20.0: 57.95 mass% manufactured.
  • This formulation is investigated experimentally in the ballistic bomb with regard to its ignition and combustion behavior.
  • a pressure curve diagram according to the system is obtained. The diagram shows that the mixture has good ignition and combustion properties.
  • the combustion temperature can be determined very precisely by thermodynamic calculation. It is 2345 K. With the same GZT fuel and a balanced oxygen balance, other oxidizers deliver higher combustion temperatures. For example, they are 2501 K for KNO 3 , 2850 K for NH 4 NO 3 and 3248 K for K Cl O 3 .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Die Erfindung betrifft eine gaserzeugende Mischung aus einem Brennstoff, einem Oxidator und einem Katalysator.The invention relates to a gas-generating mixture of a fuel, an oxidizer and a catalyst.

Gaserzeugende Mischungen der vorgenannten Art - auch Gasgeneratorsätze genannt - zeichnen sich dadurch aus, daß sie bei Verbrennung eine hohe Gasausbeute (> 14 mol/kg) ermöglichen. Sie werden für Raketen- und Rohrwaffenantriebe sowie für aufblasbare Rückhalte- (Airbag) und Rettungssysteme verwendet. Besonders im zivilen Bereich werden thermisch-mechanische Unempfindlichkeit und Ungiftigkeit der Ausgangsmischungen, aber auch fehlende Toxizität bei den entstehenden Gasen gefordert. Viele im Einsatz befindlichen Systeme erfüllen diese Forderungen nicht oder nur sehr unzulänglich.Gas-generating mixtures of the aforementioned type - also called gas generator sets - are characterized in that they enable a high gas yield (> 14 mol / kg) during combustion. They are used for rocket and barrel weapon drives as well as for inflatable restraint (airbag) and rescue systems. In the civil sector in particular, thermal-mechanical insensitivity and non-toxicity of the starting mixtures, but also a lack of toxicity in the resulting gases are required. Many systems in use do not meet these requirements, or meet them only very inadequately.

Die Reaktion dieser Brennstoffe mit den bisher eingesetzten Katalysatoren und Oxidatoren zeigen eine unbefriedigende Gaszusammensetzung und/oder ein ungenügendes Abbrandverhalten. Hinzu kommt, daß viele Reaktionsmischungen eine so hohe Verbrennungstemperatur besitzen, daß - bei Airbag-Anwendungen - die thermisch empfindlichen Sackmaterialien geschädigt werden.The reaction of these fuels with the previously used catalysts and oxidizers shows an unsatisfactory gas composition and / or inadequate combustion behavior. Add to that many Reaction mixtures have such a high combustion temperature that - in airbag applications - the thermally sensitive sack materials are damaged.

Der Erfindung liegt die Aufgabe zugrunde, bei einer Mischung des eingangs genannten Aufbaus, die Verbrennungstemperatur abzusenken und die Abbrandgeschwindigkeit zu erhöhen.The invention has for its object to lower the combustion temperature and increase the rate of combustion in a mixture of the structure mentioned in the introduction.

Diese an sich konträren Anforderungen werden erfindungsgemäß dadurch erfüllt, daß der Oxidator Cu(NO3)2*3Cu(OH)2 ist und der Katalysator aus einem Metall oder einer Metallegierung auf einem Träger besteht .According to the invention, these contradictory requirements are met in that the oxidizer is Cu (NO 3 ) 2 * 3Cu (OH) 2 and the catalyst consists of a metal or a metal alloy on a support.

Durch den erfindungsgemäß vorgesehenen Oxidator ergibt sich eine halte und schnelle Verbrennung. Der Maximaldruck wird innerhalb Millisekunden erreicht, wobei die Gastemperatur unterhalb schädlicher Grenzen bleibt. Bisher notwendige Schlackenbildner, die bei bekannten Systemen zur Bindung von Schadstoffen, z.B. Alkalioxiden, benötigt werden, können bei der erfindungsgemäßen Mischung entfallen, so daß eine höhere Gasausbeute erzielbar ist.The oxidizer provided according to the invention results in sustained and rapid combustion. The maximum pressure is reached within milliseconds, with the gas temperature remaining below harmful limits. Hitherto necessary slag formers, which in known systems for binding pollutants, e.g. Alkali oxides, required, can be omitted in the mixture according to the invention, so that a higher gas yield can be achieved.

Der weiterhin erfindungsgemäß eingesetzte Katalysator dient vornehmlich der Schadgasreduzierung (CO und NO), wobei hier der Begriff "Katalysator" im erweiterten Sinn einen aktiven Reaktionsbestandteil bezeichnet, der selbst umgesetzt werden kann und reaktionslenkend und/oder reaktionsbeschleunigend wirkt. Der Träger dient dazu, die Hauptkomponente mit einer großen spezifischen Oberfläche und einer definierten Korngrößenverteilung vorzulegen. Eine weitere Eigenschaft des Trägers besteht darin, durch physikalische und/oder chemische Prozesse - in einer speziellen Phase der Reaktion - eine Kühlwirkung zu entfalten, die über eine reine kapazitive Kühlwirkung hinausgeht. Der Träger kann ferner als Promotor der Hauptkomponente wirken. Nicht nur der Metallkatalysator, sondern auch der Oxidator sind thermisch und mechanisch stabil und insbesondere auch nicht hygroskopisch.The catalyst which is also used according to the invention is primarily used to reduce harmful gas (CO and NO), the term "catalyst" in the broader sense here denoting an active reaction component which can be implemented itself and has a reaction-guiding and / or reaction-accelerating effect. The carrier serves to present the main component with a large specific surface and a defined grain size distribution. Another property of the carrier is to develop a cooling effect through physical and / or chemical processes - in a special phase of the reaction, that goes beyond a pure capacitive cooling effect. The carrier can also act as a promoter of the main component. Not only the metal catalyst, but also the oxidizer are thermally and mechanically stable and in particular also not hygroscopic.

Der Katalysator ist vorzugsweise ein pyrophores Metall oder eine solche Metallegierung auf einem Träger, der nach dem Abbrand als Feststoff verbleibt. Es kann sich hierbei um ein Silikat, vorzugsweise ein Schicht- oder Gerüstsilikat, handeln.The catalyst is preferably a pyrophoric metal or such a metal alloy on a support which remains as a solid after the combustion. This can be a silicate, preferably a layered or framework silicate.

Als Metall hat sich insbesondere Ag hervorragend bewährt. Bei insbesondere zivilen Anwendungen werden ungiftige Ausgangsverbindungen und ungiftige Reaktionsprodukte gefordert. Diese Forderungen werden von N-reichen und C-armen Brennstoffen erfüllt. Hierzu zählen die bekannten Brennstoffe TAGN (Triaminoguanidinnitrat), NIGU (Nitroguanidin), NTO (3-Nitro-1,2,3-triazol-5-on) und das sich durch einen besonders hohen Stickstoffgehalt auszeichnende GZT (Diguanidinium-5,5'-azotetrazolat) (DE 4 108 225). Es werden deshalb im Rahmen der erfindungsgemäßen Mischung bei Verwendung für Rettungs- und Rückhaltsysteme vorzugsweise TAGN, NIGU, NTO, insbesondere aber GZT eingesetzt.Ag, in particular, has proven to be an excellent metal. In civil applications in particular, non-toxic starting compounds and non-toxic reaction products are required. These requirements are met by N-rich and C-poor fuels. These include the well-known fuels TAGN (triaminoguanidine nitrate), NIGU (nitroguanidine), NTO (3-nitro-1,2,3-triazol-5-one) and the GZT (diguanidinium-5,5 '), which is characterized by a particularly high nitrogen content. -azotetrazolate) (DE 4 108 225). For this reason, TAGN, NIGU, NTO, but in particular GZT, are preferably used in the mixture according to the invention when used for rescue and restraint systems.

Eine bevorzugte Mischung besteht aus GZT und Cu(NO3)2*3Cu(OH)2 mit ausgeglichener Sauerstoffbilanz und bis zu 30 Mass.-% des Katalysators.A preferred mixture consists of GZT and Cu (NO 3 ) 2 * 3Cu (OH) 2 with a balanced oxygen balance and up to 30% by mass of the catalyst.

Die Mischung kann als Kühlmittel Fe2O3 enthalten, dessen oxidative Eigenschaften in der Reaktionsmischung zusätzlich genutzt werden können (DE 41 33 655, EP 0 536 525).The mixture can contain Fe 2 O 3 as the coolant, the oxidative properties of which can additionally be used in the reaction mixture (DE 41 33 655, EP 0 536 525).

Beispielexample

Es wird eine Mischung bestehend aus GZT, pyrophorem Ag auf einem Schicht- oder Gerüstsilikatträger als Katalysator und Cu(NO3)2*3Cu(OH)2 als Oxidator im Verhältnis 22,05 : 20,0 : 57,95 Mass.-% hergestellt. Diese Formulierung wird bezüglich ihres Anzünd- und Verbrennungsverhaltens experimentell in der ballistischen Bombe untersucht. Dabei wird ein Druckverlaufsdiagramm gemäß Anlage erhalten. Das Diagramm zeigt, daß die Mischung gute Anzünd- und Verbrennungseigenschaften besitzt. Bei einer Ladedichte von 0,1 g/cm3 liegt der maximale Druck im Bereich von 250 bar (25MPa), der nach etwa 21 ms erreicht wird (t(pmax) = 21 ms). Die Druckanstiegszeit zwischen 30 bis 80 % des Maximaldrucks beträgt t30-80 = 4,35 ms.A mixture consisting of GZT, pyrophoric Ag on a layer or framework silicate support as catalyst and Cu (NO 3 ) 2 * 3Cu (OH) 2 as oxidizer in a ratio of 22.05: 20.0: 57.95 mass% manufactured. This formulation is investigated experimentally in the ballistic bomb with regard to its ignition and combustion behavior. A pressure curve diagram according to the system is obtained. The diagram shows that the mixture has good ignition and combustion properties. With a loading density of 0.1 g / cm 3 , the maximum pressure is in the range of 250 bar (25MPa), which is reached after about 21 ms (t (pmax) = 21 ms). The pressure rise time between 30 to 80% of the maximum pressure is t 30-80 = 4.35 ms.

Die Verbrennungstemperatur läßt sich sehr exakt durch thermodynamische Berechnung ermitteln. Sie liegt bei 2345 K. Bei gleichem Brennstoff GZT und ausgeglichener Sauerstoffbilanz liefern andere Oxidatoren höhere Verbrennungstemperaturen. Beispielsweise liegen sie bei KNO3 bei 2501 K, bei N H4 NO3 bei 2850 K und bei K Cl O3 bei 3248 K.The combustion temperature can be determined very precisely by thermodynamic calculation. It is 2345 K. With the same GZT fuel and a balanced oxygen balance, other oxidizers deliver higher combustion temperatures. For example, they are 2501 K for KNO 3 , 2850 K for NH 4 NO 3 and 3248 K for K Cl O 3 .

Claims (8)

  1. A gas generating mixture of a fuel, an oxidant and a catalyst, characterized in that the oxidant is Cu(NO3)2*3Cu(OH)2 and the catalyst consists of a metal or a metal alloy on a carrier.
  2. A mixture according to claim 1, characterized in that the catalyst is a pyrophoric metal or a pyrophoric metal alloy on a carrier.
  3. A mixture according to claim 1 or 2, characterized in that a silicate, especially a layer or skeleton silicate serves as the carrier for the metal catalyst.
  4. A mixture according to claim 3, characterized in that pyrophoric Ag on a layer or skeleton silicate carrier serves as the catalyst.
  5. A mixture according to any of claims 1 to 4, characterized in that TAGN (triaminoguanidine nitrate), NIGU (nitroguanidine), NTO (3-nitro-1,2,3-triazol-5-one) or GZT (diguanidinium-5,5'-azotetrazolate) serves as the fuel.
  6. A mixture according to any of claims 1 to 5, consisting of a mixture of GZT and Cu(NO3)2*3Cu(OH)2 with equalised oxygen balance and up to 30% by mass of the catalyst.
  7. A mixture according to any of claims 1 to 6, characterized in that the catalyst has a mean grain size < 10 µm.
  8. A mixture according to any of claims 1 to 7, characterized in that it includes Fe2O3 as a coolant.
EP94119383A 1994-01-18 1994-12-08 Gas generating mixture Expired - Lifetime EP0666248B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4401214 1994-01-18
DE4401214A DE4401214C1 (en) 1994-01-18 1994-01-18 Gas-generating mixture

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EP0666248A1 EP0666248A1 (en) 1995-08-09
EP0666248B1 true EP0666248B1 (en) 1996-10-23

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EP0666248A1 (en) 1995-08-09
DE4401214C1 (en) 1995-03-02
DE59400902D1 (en) 1996-11-28
US5542999A (en) 1996-08-06

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