CN1183758A - Gas-generating mixtures - Google Patents

Gas-generating mixtures Download PDF

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Publication number
CN1183758A
CN1183758A CN96193147A CN96193147A CN1183758A CN 1183758 A CN1183758 A CN 1183758A CN 96193147 A CN96193147 A CN 96193147A CN 96193147 A CN96193147 A CN 96193147A CN 1183758 A CN1183758 A CN 1183758A
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Prior art keywords
nitrate
amino
mixture
medicament
tetrazolium
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CN96193147A
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K·雷德克尔
W·维乌特尔
U·布赖
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Dynamit Nobel GmbH Explosivstoff und Systemtechnik
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Dynamit Nobel GmbH Explosivstoff und Systemtechnik
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B43/00—Compositions characterised by explosive or thermic constituents not provided for in groups C06B25/00 - C06B41/00
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Air Bags (AREA)
  • Catalysts (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
  • Treating Waste Gases (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The present invention concerns propellants for gas-generators containing (as the nitrogen-containing compound, i.e. fuel) at least one compound from the group comprising tetrazoles, triazoles, triazines, cyanic acid, urea, derivatives or salts thereof; (as oxidants) compounds from the group comprising peroxides, nitrates, chlorates or perchlorates; combustion moderators capable by heterogeneous or homogeneous catalysis of influencing the combustion process and velocity thereof; and, optionally, additives capable of reducing the proportion of toxic gases.

Description

Produce the mixture of gas
Much more more and more producer gas generator for example is used for lifesaving in Motor vehicles.The mixture that gas takes place contains sodiumazide usually.Sodiumazide itself is poisonous, and easy and heavy metal such as copper and plumbous generation extremely danger and the very active compound of reacting.Therefore in making raw material, gas charge mix (gas charge mixture) process and it processing and quality control in to take special measure.Owing to this reason, handle sodiumazide, for example replacing damaged producer gas generator or also bringing special problem when ruining the vehicles disappearing.Also to guarantee to prevent improper use.
Is no lack of the effort of adopting other material to replace sodiumazide now.The common ground of suggestion of promising replacement sodiumazide be that they all contain the organic carbon compound, and also contain organic nitrogen compound usually.EP 0 519 485 describes and adopts tetrazolium or one or more terazole derivatives, or adopting one or more cyanic acid derivatives and its salt, one or more triazines and pyrrolotriazine derivatives adopt urea and salt thereof, the derivative of these compounds and salt, above-claimed cpd also can exist with form of mixtures.Can adopt the nitrate of ammonium, sodium, potassium, magnesium, calcium and iron and/or the superoxide of zinc, calcium, strontium or magnesium as oxygenant.Also can add gas takes place for other component, refrigerant, reductive agent, catalyzer and/or pore former.
That EP 0 438 851 has described is nontoxic, the fireworks composition of non-azide, and it is applicable to the combustion prod that manufacturing is nontoxic basically, comprises a kind of gas, with filling accident buffering pad (accidentcushion).Said composition comprises by at least a mixture that hydrogenous tetrazolium or triazole compounds, at least a oxygen containing oxygenant and at least a metal oxide that is selected from cobalt oxide, nickel oxide, chromic oxide, aluminum oxide and boron oxide are formed in molecule.In combustion processes, produce an a kind of nontoxic substantially gaseous mixture and filtrable solid matter.For example adopt amino tetrazole and the oxygenant that wherein except nitrate, also can contain perchlorate.
Similarly prescription is disclosed in the European patent EP 0 372 733: adopt tetrazolium and triazole with as the ammoniumper chlorate of oxygenant and the mixture of base metal nitrate, and be added with a kind of additive and burn with control.
PCT application WO 94/01381 has described be used for airbag a kind of by organic nitro-compound with contain the gas generating agent that the oxygen halate is formed.For example can be regarded as alkaline metal chlorate, bromate and high hydracid compound as containing the oxygen halate.As regulating oxide compound, muriate, carbonate, the vitriol that the incendiary catalyzer proposes periodictable 4-6 family especially.
React so that in the air bag expansion process of the vehicles in above-mentioned gas charging (gas charge), except toxicological harmless working gas such as nitrogen, carbonic acid gas and hydrogen, also may there be a certain proportion of toxic gas, for example carbon monoxide or oxynitride.Consider the peak load situation for these gases, stipulated its ultimate value, for example the peak concentration of working position (MAC).There is a kind of thermodynamics and kinetics relation in their formation, with regard to the situation of carbon monoxide, for example is Bao Shi balance (Boudouard equilibrium) control.In addition, the fact shows, contains nitrogen and carbon compound and produce the high CO ratio of mixture generation of hanging down the NOx ratio in combustion processes, and vice versa.These equilibrated are set up relevant with temperature and pressure.As everyone knows, the composition of reactant gases can not adopt physical measure to realize separately to forming the abundant effective influence of non-toxic products process, for example with pressure and/or temperature control reaction.
Some currently known methods is a purpose with these components that reduce reaction gas on the document.For example balance is moved towards the opposite direction that forms carbon monoxide by in the gas charging, adding alkaline slag former formation carbonate.Oxynitride changes into nitrate or nitrite simultaneously.
But these measures also have shortcoming, since slag ratio height, the obvious variation of gas recovery ratio.In addition, slag must separate from gaseous component by filtration or other with holding back system's high cost, and working gas just can be used for for example charging into airbag then.
Use no chlorine system and can cause forming the gas of nitrogenfree oxide, but that the cost of doing like this is a gas recovery ratio is less.Its reason is, for making the Bao Shi balance to CO 2Direction shifts, and that must use excessive formation slag contains oxygen reagent.Therefore proposed a kind of mixed system, wherein the reaction of describing is in the past undertaken by the oxygenant that replaces forming slag with pressurized air.But this scheme has the high shortcoming of system weight and must control and additional pressurized air.
Press United States Patent (USP) 3,910,595, for improving yield, the gas that will generate in reaction guiding is by the Venturi nozzle, and the air that can suck surrounding environment like this helps to make air bag inflation.But the air that must consider surrounding environment like this can strong cooling hot gas.Particularly when ambient temperature is low, produce VOLUME LOSS, when airbag is expanded, must be supplied by the fireworks mixture.In the vehicle interior poisonous reaction gas ratio that raises, can not fully reduce thus by dilution.
The invention provides nontoxic, azide free mixture, it makes gas by burning.This system gas mixture can be used in particular on the safety features, for example is used for automobile and aircraft in the airbag system airbag is expanded.But they also are applicable to by the bag that is positioned at weight below is expanded and promote weight, or are used to discharge fire fighting powder, or are used for other and need fast formation gas to carry out the measure of work.
Mixture of the present invention contains
A) be selected from tetrazolium, triazole, triazine, cyanic acid, urea, their derivative or at least a compound of salt as nitrogenous compound (fuel);
B) as at least three kinds of compounds that are selected from superoxide, nitrate, oxymuriate or perchlorate of oxygenant;
C) burning negative catalyst (combustion moderator), it can be by heterogeneous or catalysis in a homogeneous system influence burning and speed thereof; And randomly
D) additive, they can reduce the ratio of toxic gas.
Mixture of the present invention is nontoxic, handles easily on the contrary mutually with the mixture that contains triazo-compound.Therefore they are in the manufacturing of raw material and mixture, and their shaping, storage or when destroying required security costs less.
The nitrogenous compound that uses by the present invention is such compound, and they mainly form CO in its heat/chemical reaction when mixing with oxygenant 2, N 2, O 2And H 2O, but do not generate gas such as the CO or the NOx of insalubrity concentration.
Preferably a kind of or some kinds of terazole derivatives that chemical formula is following of the nitrogenous compound that mixture of the present invention contains (fuel),
Figure A9619314700081
Wherein, R 1And R 2Or R 3Can be identical or different, but be R 2Be exactly R 3Exist, and they represent hydrogen, hydroxyl, amino, carboxyl, C 1-7-alkyl, C 2-7-thiazolinyl, C 1-16-alkylamino, aryl optional are replaced by one or several substituting groups, and these substituting groups can be identical or different amino, nitro, the C of being selected from 1-C 4Alkyl or aryl amino, wherein aryl is optional is substituted, or the sodium of above-mentioned terazole derivatives-, potassium-and Guanidinium salt.
In these compounds:
R 1Particularly represent hydrogen, amino, hydroxyl, carboxyl, methyl, ethyl, propyl group or sec.-propyl, butyl, isobutyl-or the tertiary butyl, n-pentyl, n-hexyl or n-heptyl, methylamino, ethylamino, dimethylamino, n-heptyl amino, n-octyl amino or positive decyl amino, tetrazyl, phenyl amino, phenyl, nitrophenyl or aminophenyl; With
R 2Or R 3Particularly represent hydrogen, methyl or ethyl, phenyl, nitrophenyl or aminophenyl.Particularly preferred compound is a terazole derivatives 5-amino tetrazole, lithium-, sodium-, potassium-, zinc-, magnesium-, strontium-or the 5-amino tetrazole thing of calcium, 5-amino tetrazole nitrate,-vitriol,-perchlorate and similar compound, 1-(4-aminophenyl)-tetrazolium, 1-(4-nitrophenyl)-tetrazolium, 1-methyl-5-dimethyl-amino tetrazole, 1-methyl-5-methylamino tetrazolium, 1-methyl tetrazolium, 1-phenyl-5-aminotetrazole, 1-phenyl-5-hydroxyl-tetrazolium, the 1-phenyltetrazole, 2-ethyl-5-amino tetrazole, 2-methyl-5-amino tetrazole, 2-methyl-5-carboxyl tetrazolium, 2-methyl-5-methylamino tetrazolium, 2-methyl tetrazolium, the 2-phenyltetrazole, 5-(right-tolyl)-tetrazolium, 5-diallyl amino tetrazole, 5-dimethylamino tetrazolium, 5-ethylamino tetrazolium, 5-hydroxyl tetrazolium, 5-methyl tetrazolium, 5-methylamino tetrazolium, the positive decyl amino tetrazole of 5-, 5-n-heptyl amino tetrazole, 5-n-octyl amino tetrazole, the 5-phenyltetrazole, 5-phenyl amino tetrazolium or two-(aminoguanidine)-azotetrazole and two Guanidinium 5,5 '-the azotetrazole thing, and 5,5 '-two tetrazoliums and its salt, 5,5 '-two-1H-tetrazolium ammonium compound for example.
In the mixture, contain 1 as pyrrolotriazine derivatives, 3, the 5-triazine, contain 1 as triazole derivative, 2,4-triazole-5-ketone, 3-nitro-1,2,4-triazole-5-ketone, as the cyanic acid derivative, contain Zassol, tricyanic acid, cyanurate, tricyanic acid acid amides (pyramine), the 1-dicyanodiamide, the dicyan sodium amide, the amino disodium of cyanogen, guanylurea nitrate, guanylurea vitriol, contain biuret as urea derivatives, guanidine, nitroguanidine, guanidine nitrate, aminoguanidine, aminoguanidine nitrate, thiocarbamide, triaminoguanidine nitrate, aminoguanidin carbonate, azodicarbonamide, the tetrazene, Urea,amino-nitrate, and urethanum, uride such as malonylurea and its derivative.
Adopt the 5-amino tetrazole as particularly preferred component.In mixture, the preferable amount ratio of this component is 10-40% (weight).As the 5-Aminotetrazole derivatives, adopt its salt, wherein the element that allowed by toxicology of the acid hydrogen atom on the 5-amino tetrazole such as calcium, magnesium or zinc replace with the form of salt.But also can adopting wherein, positively charged ion is the compound of ammonium, Guanidinium and its aminoderivative.
Adopt following compound as oxygenant among the present invention:
-basic metal and alkaline earth metal peroxide, zinc superoxide, and the peroxydisulfate of above-mentioned element and ammonium;
-ammonium nitrate, basic metal and alkine earth metal nitrate, particularly lithium nitrate, SODIUMNITRATE or saltpetre, and strontium nitrate;
-basic metal or alkaline-earth metal or ammonium contain the oxyhalogenation compound, preferred especially potassium perchlorate or ammoniumper chlorate.
Oxygenant can use individually or use with form of mixtures.For the oxynitride ratio is reduced in reaction mixture as far as possible, advantageously, in oxidant mixture the nitrate ratio keep the least possible, because of some nitrate can thermolysis.
Preferred oxygenant combination is to be to be made up of at 1: 2: 10 zinc peroxide, potassium perchlorate and at least a nitrate, particularly SODIUMNITRATE or strontium nitrate with ratio of mixture, and total share is about 60% (weight) in producing gaseous mixture.During burning, chlorine-containing compound is reacted into harmless sodium chloride/potassium chloride.Can consider also that as perchlorate independent ammoniumper chlorate or it and other contain the mixture of oxyhalogenation thing, but must prevent excessive, in order to avoid produce corrosive hydrochloric acid.If the employing ammoniumper chlorate, it is particularly advantageous having zn cpds simultaneously, because can avoid forming the danger of hydrochloric acid like this.Sodium-and the compound of potassium can be excessive, because these compounds and reactant gases reaction produce harmless carbonate.Partly or entirely base metal nitrate can cause the obvious minimizing of slag amount with the strontium nitrate replacement.
In mixture, nitrogenous compound is to the ratio of oxygenant, the ratio of tetrazolium and triazole and oxygenant for example, and balance like this makes and produce excess of oxygen when the reinforced mixture burns of gas.Excess of oxygen makes CO/CO 2Balance moves to the carbonic acid gas direction.
As the burning negative catalyst, can adopt can be by heterogeneous or catalysis in a homogeneous system influence burning or the material of combustionvelocity or their mixture.Negative catalyst by heterogeneous catalysis effect disturbance reponse is metal, metal oxide and/or metal carbonate and/or metallic sulfide.Particularly can adopt boron, silicon, copper, iron, titanium, zinc or molybdenum as metal.Also available lime carbonate.Can use the mixture of these negative catalyst equally.
With the negative catalyst of the form disturbance reponse of catalysis in a homogeneous system, for example be sulphur, boron, silicon or ferrocene and its derivative.These negative catalyst flash to gas phase owing to the temperature that occurs and can directly react with the form participation of own or subsequent products in reaction.The ratio of these materials can account for maximum about 8% in mixture.
In addition, mixture of the present invention also can contain the aerogenesis additive, and they can reduce the ratio of obnoxious flavour, as oxynitride and/or carbon monoxide.In the gaseous mixture of making, the ratio of these obnoxious flavoures depends on following factor:
The stoichiometric composition of-mixture,
The temperature and pressure of-reaction,
-additive to the reaction or post-reacted influence, and
The structure of-the producer that reacts therein.
Though at closed system, in for example withstand voltage bullet, the gaseous mixture that is easier to reach near the calculation of thermodynamics value is formed, this no longer can realize under the operational condition of producer reality, because can't reach balance in lasting several milliseconds reaction.Therefore, by the present invention, can rise material that katalysis is suitable for be incorporated in the mixture or the zone of outflow gas in.But burning negative catalyst and metal oxide containing precious metals in this application of aforementioned.Also can adopt precious metal such as palladium, ruthenium, rhenium, platinum or rhodium in addition, they utilize the excessive oxygen in the reactant gases to transform carbon monoxide in subsequent reactions.A preferred application form is, additive is coated onto that pottery is gone up or with their galvanic deposit to wire netting as carrier.According to said method, particularly can be reduced in the ratio of carbon monoxide in the gaseous mixture.
To reducing the NOx ratio, also adopt other material, their chemical property is particularly to oxynitride, and for example nitrogen peroxide changes into nitrate or nitrite has katalysis.In principle, all more or less the strong basicity reactive material all be suitable for.Comprise nontoxic element such as basic metal and alkali earth metal at this, the oxide compound of zinc, oxyhydroxide or carbonate, and the mixture of these compounds.When using these compounds, mainly form the nitrate or the nitrite of these elements.In addition, urea, guanidine and their derivative, band NH 2The compound of base is amido sulfonic acid for example, amido complex compound etc., and acid amides also is applicable to and NO 2Reaction.Particularly preferred embodiment is that the spout at producer adds superoxide.Here special tool advantage is except by the aforesaid reaction nitrogen oxides reduction, also to generate oxygen and be used for follow-up and catalyzed reaction carbon monoxide.
Additive of the present invention can be separately or is directly added together in system gas reinforced, or is added on the exit passageway of producer.When being used on the generator exports passage, additive can use with the form of compactness aptly, as tablet, pill or particulate form.The highest 10% (weight) that is approximately of additive capacity that in reinforced, adds.When being used for exit passageway, the amount of additive can account for 75% reinforced (weight) of gas.
Surprisingly, the minimizing of CO content reaches by the following method: a part of fuel is by salt, and particularly the calcium of amino tetrazole, magnesium or zinc salt, particularly corresponding salt of 5-amino tetrazole or urea derivatives are formed.In the case as long as add two kinds of oxygenants just enough.
Also can add other additive for influencing speed of response and temperature.These additives can be for example boron or metal powder, for example titanium, aluminium, zirconium, iron, copper, molybdenum and their stable hydride.Their ratios in additive can be at the order of magnitude of 5% (weight).
Gas of the present invention adds the manufacturing of material mixture to carry out with currently known methods.For example, each component carried out dry blending, sieve, synthesize several parts, tablet forming.For example obtain loose material, by the particle shape and the whole combustionvelocity of adjustable size of loose material with broken and each fragment that sieves.Loose material can be made in a large number, and has the active part of Different Dynamic by mixing and adapt to aflame various specific requirement.Also can adopt the premixture that has 2 or 3 components to improve security and improve mixing resultant at this.A kind of mixture of forming by oxygenant and additive can it with make before nitrogenous compound contacts.
Also can be by the aqueous component of kneading, granulation subsequently for example with sieve, press strip and similar approach make mixture.Can adopt binding agent at this, water glass for example, " inorganic rubber " (nitrile phosphorus chloride phosphornitrilchlorid) or also can adopt the organic binder bond of low ratio is as acrylic resin, PTFE, guar gum.Because applied component is not only nontoxic but also not active especially, and can only could react at enclosed space by means of the special ignition tool, thereby there is no need to take special safety precaution.
The loose material that obtains like this can directly use.Loose material contacts with producer and wearing and tearing can cause the change of combustioncharacteristics, and owing to its burn intensively causes danger, for avoiding this, can be with the loose material top coat.This can be coated with one deck by the outside and coat with lacquer and realize, and optional band promotes the additive of lighting to promote to light.Can consider oxygenant as the additive that helps to light, as zinc peroxide, perchlorate and metal powder, as titanium and zirconium.Coating can for example be undertaken by the evaporation of solvent with cylinder by the solvent-laden coating-forming agent of spraying.
For special Application Areas, porous grain pattern thing can be joined in the particle.The formation of this vesicular structure thing can make by usual way, for example also with The suitable solvent they are dissolved out subsequently by the salt that adds solubility, or but by adding thermolysis material for example bicarbonate of ammonia, Bing Tongersuosuan, whipping agent, superoxide or Diisopropyl azodicarboxylate, they are finished by heating with in the method that the sad temperature of high temperature is removed again in subsequent handling then.Its characteristic depends on adding quantity, granular size and distribution.The reinforced reinforced occasion of gas that for example need can be applicable to strong evolution reaction of such gas.
The reinforced available common method of lighting of the gas of making is as required finished.Wherein, importantly, do not have other poisonous reactive gas species and after reaction, from lighter for ignition, emit.
It is insensitive for security feature that gas adds material mixture, for example to friction-, impact-, effect of impact and under normal pressure, to flammable or all insensitive due to flame to cerium/iron spark combustibility.But in closed system, through suitably igniting it with regard to burn intensively.This has just improved the security in making and handling.
Mixture of the present invention for example can be used in the producer gas generator of Motor vehicles, is safe for common electric ignition system.
With opposite based on the reinforced producer of trinitride, slag charge filtration procedure that can costliness is not because contain poisonous component in the slag.It mainly is made up of the carbonate of sodium and potassium and muriate and considerably less nitrate/nitrite and zinc oxide.Therefore the discharge of these nontoxic components only is subjected to the restriction of dust discharging limit value.
Following examples are further explained the present invention, but are not limited.
Will by reinforced each the concrete component of gas of the present invention with given weight ratio in plastic containers centrifugal rolling mixing tank homogenizing 30 minutes.With the mixture compressing tablet, be pressed into the sheet that diameter is 6mm subsequently.As a burning mixt and by electrically heated iron wire it is reacted by means of 0.2g boron/saltpetre (25: 75 weight quota) in the withstand voltage bullet of 25ml stainless steel in the sample of 3.5g tablet forming.Out-of-phase diagram by the reaction of piezoelectricity determinator record.Generate combustion gases in thermopositive reaction, it is mainly by H 2O, CO 2, N 2And O 2Form and satisfy the toxicology requirement of regulation.
The gas that illustrates in example adds material mixture and for example carry out relevant Study on Combustion Characteristics in the test set of being made up of combustion chamber, airflow redirector and filtration chamber under the condition of certain physical structure.The gas-phase reaction product collection and characterizes (main ingredient: H in 60 volume containers 2O, CO 2, N 2And O 2).
Form (weight %)
Example number ????1 ????2 ????3 ????4 ????5
5-amino tetrazole SODIUMNITRATE potassium perchlorate zinc oxide zinc peroxide graphite ????33.1 ????52.3 ????10.1 ????4.0 ????---- ????0.5 ????33.1 ????52.3 ????10.1 ????3.0 ????1.0 ????0.5 ????34.0 ????61.5 ????---- ????1.0 ????3.0 ????0.5 ????33.1 ????52.3 ????10.1 ????---- ????4.0 ????0.5 ????34.2 ????64.8 ????---- ????---- ????---- ????1.0
Example Heat of explosion (kJ/g) Friction susceptibility (N) Bump susceptibility (J)
????1 ????2 ????3 ????4 ????5 ????3.61 ????3.69 ????3.70 ????3.82 ????3.82 ????＞360 ????＞360 ????＞360 ????＞360 ????＞360 ????10 ????10 ????10 ????7.5 ????10
Measurement result in the withstand voltage bullet of trajectory (ballistic pressure bomb)
Example Pressure maximum value (crust) Time difference 1)40-60%P maximum (millisecond) Cold air 2)(1/g) CO(ppm)
??1 ??2 ??3 ??4 ??5 ????715 ????707 ????729 ????660 ????730 ????6.7 ????5.9 ????6.1 ????6.5 ????6.7 ??0.41 ??0.38 ??0.41 ??0.40 ??0.41 ??1800 ??1100 ??2000 ??1800 ??3300
1Peak pressure 40 and 60% between reaction times, represent with millisecond
2After being cooled to room temperature, measure
Embodiment 1 describes the reaction of the binary mixture of 5-amino tetrazole (5-ATZ) and oxygenant.The composition of reactant gases show the sealing withstand voltage bullet in the burning after, the content of CO is 1800ppm in reactant gases.The zinc peroxide that only adds 1% (weight) in example 2 makes us promptly surprisingly that CO content obviously is reduced to 1100ppm under other same test parameter.The change that the mixture of example 3 to 5 is formed causes worse result.
Form (weight %)
Example number ??6(＝1) ????7 ????8 ????9
5-amino tetrazole SODIUMNITRATE potassium perchlorate Zn (5-ATZ) 2????Ca(5-ATZ) 2????Mg(5-ATZ) 2Zinc oxide graphite ????33.1 ????52.3 ????10.1 ????---- ????---- ????---- ????4.0 ????0.5 ????25.4 ????52.7 ????10.2 ????11.2 ????---- ????---- ????---- ????0.5 ????16.6 ????52.7 ????10.2 ????---- ????20.0 ????---- ????---- ????0.5 ????10.7 ????52.7 ????10.2 ????---- ????---- ????25.9 ????---- ????0.5
Example Heat of explosion (kJ/g) Friction susceptibility (N) Bump susceptibility (J)
??6(＝1) ??7 ??8 ??9 ????3.61 ????3.64 ????3.46 ????2.74 ????＞360 ????＞360 ????＞360 ????＞360 ????10 ????10 ????15 ????20
Test result in the withstand voltage bullet of trajectory
Example Pressure maximum value (crust) Time difference 1)40-60%P maximum (millisecond) Cold air 2)(l/g) CO(ppm)
????6(＝1) ????7 ????8 ????9 ????715 ????662 ????602 ????81 ????6.7 ????6.8 ????6.6 ????39.2 ??0.41 ??0.39 ??0.40 ??0.33 ????1800 ????250 ????140 ????100
Test result in 60 liters of test tanks
Example CO-reduces 3)(％) Peak pressure 4)(crust)
?6(＝1) ?7 ?8 ?9 ????0 ????10 ????40 ????95 ????2.2 ????2.1 ????1.7 ??＜1.5
1)Peak pressure 40 and 60% between reaction times, represent with millisecond
2)After being cooled to room temperature, measure
3)Result based on example 1 or example 6 test tanks
4)Filling quality 40g
Example 6 to 9 shows, add the zinc of 5-amino tetrazole-, calcium-and magnesium salts (Me (5ATZ) 2) advantageous effect is in the composition of gaseous mixture.Find that the CO ratio has tangible minimizing.Speed of response is also influenced.
Form (weight %)
Example number ????10 ????11 ????12 ????13
5-amino tetrazole Guanidinium nitrate SODIUMNITRATE strontium nitrate graphite ????33.0 ????8.3 ????58.2 ????---- ????0.5 ????31.6 ????8.0 ????39.0 ????20.9 ????0.5 ????30.8 ????7.8 ????27.1 ????33.8 ????0.5 ????28.9 ????7.3 ????---- ????63.3 ????0.5
Example Heat of explosion (kJ/g) Friction susceptibility (N) Bump susceptibility (J) The residue quality 3)(g)
????10 ????11 ????12 ????13 ????4.06 ????3.90 ????3.61 ????3.41 ????＞360 ????＞360 ????＞360 ????＞360 ????20 ????15 ????20 ????15 ????1.5 ????1.2 ????1.0 ????0.8
Test result in the withstand voltage bullet of trajectory
Example Pressure maximum value (crust) Time difference 1)40-60%P maximum (millisecond) Cold air 2)(l/g)
?10 ?11 ?12 ?13 ????779 ????767 ????723 ????620 ????6.1 ????7.0 ????7.3 ????8.6 ????0.46 ????0.41 ????0.42 ????0.39
1)Peak pressure 40 and 60% between reaction times, represent with millisecond
2)After being cooled to room temperature, measure
3)The solid masses of 30g gas reinforced burning back in the 60l test tank in the test producer
The ratio that example 10 to 13 is different from as the SODIUMNITRATE/strontium nitrate of oxygenant.The quality of the slag that generates in jar reduces along with the increase of strontium nitrate component.This means, in the strainer of producer, add strontium nitrate-after reaction-the improved filterableness of slag.Make simultaneously that the CO ratio is subjected to favorable influence in the reactant gases.

Claims (24)

1. be used for the medicament of the generation gas of producer gas generator, comprise nitrogenous compound, it is characterized in that it contains:
A) as at least a compound that is selected from tetrazolium, triazole, triazine, cyanic acid, urea and derivative thereof or its salt of nitrogenous compound (fuel);
B) as at least three kinds of compounds that are selected from superoxide, nitrate, oxymuriate or perchlorate of oxygenant;
C) burning negative catalyst, it can be by heterogeneous or catalysis in a homogeneous system influence burning and speed thereof; And randomly
D) additive, it can reduce the ratio of toxic gas.
2. by the medicament of the generation gas of claim 1, it is characterized in that, act as a fuel (nitrogenous compound) it contain the terazole derivatives of one or more following formulas, Wherein, R 1And R 2Or R 3Can be identical or different, but be R 2Be exactly R 3Exist, they represent hydrogen, hydroxyl, amino, carboxyl, C 1-7-alkyl, C 2-7-thiazolinyl, C 1-10-alkylamino, aryl, they are chosen wantonly and are replaced by one or several substituting groups, and these substituting groups can be identical or different, and be selected from amino, nitro, C 1-4-alkyl or aryl amino, wherein aryl is optional is substituted, or the sodium of above-mentioned terazole derivatives-, potassium-and Guanidinium salt.
3. press the medicament of the generation gas of claim 2, it is characterized in that
R 1Particularly represent hydrogen, amino, hydroxyl, carboxyl, methyl, ethyl, propyl group or sec.-propyl, butyl, isobutyl-or the tertiary butyl, n-pentyl, n-hexyl or n-heptyl, methylamino, ethylamino, dimethylamino, n-heptyl amino, n-octyl amino or positive decyl amino, tetrazyl, phenyl amino, phenyl, nitrophenyl or aminophenyl;
R 2And R 3Particularly represent hydrogen, methyl or ethyl, phenyl, nitrophenyl or aminophenyl.
4. press the medicament of the generation gas of one of claim 1 to 3, it is characterized in that, nitrogenous compound is selected from terazole derivatives, particularly be selected from the 5-amino tetrazole, lithium-, sodium-, potassium-, zinc-, magnesium-, strontium-or the 5-amino tetrazole thing of calcium, 5-amino tetrazole nitrate,-vitriol,-perchlorate and similar compound, 1-(4-aminophenyl)-tetrazolium, 1-(4-nitrophenyl)-tetrazolium, 1-methyl-5-dimethyl-amino tetrazole, 1-methyl-5-methylamino tetrazolium, 1-methyl tetrazolium, 1-phenyl-5-aminotetrazole, 1-phenyl-5-hydroxyl-tetrazolium, the 1-phenyltetrazole, 2-ethyl-5-amino tetrazole, 2-methyl-5-amino tetrazole, 2-methyl-5-carboxyl tetrazolium, 2-methyl-5-methylamino tetrazolium, 2-methyl tetrazolium, the 2-phenyltetrazole, 5-(right-tolyl)-tetrazolium, 5-diallyl amino tetrazole, 5-dimethylamino tetrazolium, 5-ethylamino tetrazolium, 5-hydroxyl tetrazolium, 5-methyl tetrazolium, 5-methylamino tetrazolium, the positive decyl amino tetrazole of 5-, 5-n-heptyl amino tetrazole, 5-n-octyl amino tetrazole, the 5-phenyltetrazole, 5-phenyl amino tetrazolium or two-(aminoguanidine)-azotetrazole and 5,5 '-azotetrazole two Guanidinium salt, and 5,5 '-two tetrazoliums and its salt, as 5,5 '-two-1H-tetrazolium ammonium compound.
5. press the medicament of the generation gas of claim 1 to 4, it is characterized in that, comprise 1 as pyrrolotriazine derivatives, 3, the 5-triazine, comprise 1 as triazole derivative, 2,4-triazole-5-ketone, 3-nitro-1,2,4-triazole-5-ketone, include Zassol as the cyanic acid derivative, tricyanic acid, cyanurate, tricyanic acid acid amides (pyramine), the 1-dicyanodiamide, the dicyan sodium amide, the amino disodium of cyanogen, guanylurea nitrate, guanylurea vitriol, contain biuret as urea derivatives, guanidine, nitroguanidine, guanidine nitrate, aminoguanidine, aminoguanidine nitrate, thiocarbamide, triaminoguanidine nitrate, aminoguanidin carbonate, azodicarbonamide, the tetrazene, Urea,amino-nitrate, and urethanum, uride such as malonylurea and their derivative.
6. press the medicament of the generation gas of claim 1 to 5, it is characterized in that, contain following compound as oxygenant:
-basic metal and alkaline earth metal peroxide, zinc superoxide, and the peroxydisulfate of above-mentioned element and ammonium, or the mixture of these compounds;
-ammonium nitrate, basic metal and alkine earth metal nitrate, particularly lithium nitrate, SODIUMNITRATE or saltpetre, and the mixture of strontium nitrate or these compounds;
-basic metal or alkaline-earth metal or ammonium contain oxyhalogenation thing, particularly potassium perchlorate or ammoniumper chlorate or the mixture of these compounds.
7. produce the medicament of gas by one of claim 1 to 6, it is characterized in that, contain the mixture of forming by zinc peroxide, potassium perchlorate or at least a nitrate, particularly SODIUMNITRATE or strontium nitrate as oxygenant.
8. press the medicament of the generation gas of one of claim 1 to 7, it is characterized in that the ratio of mixture of each oxygenant is 1: 2: 10 in the aerogenesis mixture, total content is 60% (weight).
9. press the medicament of the generation gas of one of claim 1 to 8, it is characterized in that nitrogenous compound is accounted like this to the ratio of mixture of oxygenant in mixture, promptly after the aerogenesis mixture burns, generate excess of oxygen.
10. press the medicament of the generation gas of one of claim 1 to 9, it is characterized in that, contain such material or its mixture as the burning buffer reagent, they can be by heterogeneous or catalysis in a homogeneous system influence burning and speed thereof, and wherein the ratio of these materials in mixture is the highest is about 8%.
11. press the medicament of the generation gas of one of claim 1 to 10, it is characterized in that, contain metal, metal oxide and/or metal carbonate and/or metallic sulfide as the burning negative catalyst, mixture with these burning negative catalyst wherein particularly adopts boron, silicon, copper, iron, titanium, zinc or molybdenum as metal.
12. press the medicament of the generation gas of one of claim 1 to 11, it is characterized in that, contain sulphur, ferrocene and its derivative as the burning negative catalyst.
13. the medicament by the generation gas of one of claim 1 to 12 is characterized in that, contain can reduce obnoxious flavour oxynitride and/or carbon monoxide material as additive.
14. press the medicament of the generation gas of one of claim 1 to 13, it is characterized in that, contain following material as additive :-burning negative catalyst, precious metal such as palladium, ruthenium, rhenium, platinum or rhodium, or the oxide compound of these precious metals, and the mixture of these compounds, or-material of alkali reaction, the for example oxide compound of basic metal and alkaline-earth metal, zinc, oxyhydroxide or carbonate, and the mixture of these compounds, or-urea, guanidine and derivative thereof, the amino compound of band is the mixture of thionamic acid, amido complex compound, acid amides and these compounds for example.
15. press the medicament of the generation gas of one of claim 1 to 14, it is characterized in that the additive capacity that (charge) adds in reinforced is about 10% (weight) and is up to 75% (weight) in exit passageway, all reinforced based on gas.
16. be used for the medicament of the generation gas of producer gas generator, comprise nitrogenous compound, it is characterized in that containing:
A) as the calcium of the amino tetrazole and the salt, particularly amino tetrazole of nitrogenous compound (fuel)-, magnesium-or the combination, particularly 5-amino tetrazole of zinc salt and combination of corresponding 5-aminotetrazole salt;
B) be selected from superoxide, nitrate, oxymuriate or perchlorate as oxygenant; At least two kinds of compounds of SODIUMNITRATE and potassium perchlorate particularly, and
C) burning negative catalyst, it can be by heterogeneous or catalysis in a homogeneous system influence burning and speed, particularly zinc oxide and zinc carbonate and lime carbonate.
Comprise nitrogenous compound 17. be used for the mixture of the generation gas of producer gas generator, it is characterized in that, contain:
A) as the urea of nitrogenous compound (fuel), its salt, its derivative and their salt, particularly biuret, guanidine, nitroguanidine, Guanidinium nitrate, aminoguanidine, aminoguanidine nitrate, thiocarbamide, triaminoguanidine nitrate, aminoguanidin carbonate, azodicarbonamide, guanylurea nitrate, guanylurea vitriol, the tetrazene and/or Urea,amino-nitrate and urethanum, uride are as clinging to than acid regurgitation and their derivative;
B) as at least two kinds of compounds that are selected from superoxide, nitrate, oxymuriate or perchlorate, particularly SODIUMNITRATE and potassium perchlorate of oxygenant, and
C) burning negative catalyst, they can be by heterogeneous or catalysis in a homogeneous system influence burning and speed, particularly zinc oxide, zinc carbonate and lime carbonate.
18. press the medicament of the generation gas of claim 16 or 17, it is characterized in that oxygenant is by claim 6 definition, and the burning negative catalyst defines by one of claim 10 to 12.
19. the medicament by the generation gas that is used for producer gas generator of one of aforesaid claim is characterized in that, mixes with other additive with nitrogenous compound (fuel) and oxygenant, burning negative catalyst with when optional, and with mixture homogenization.
20. the method by claim 19 is characterized in that, the medicament that produces gas is squeezed auxiliary agent in use, for example squeezes under the condition of graphite, moly-sulfide, tetrafluoroethylene, talcum powder, Zinic stearas or boron nitride.
21. the method by claim 20 is characterized in that, with the stampings coating.
22. the method by one of claim 19 to 21 is characterized in that, makes the stampings of certain porosity for the control combustionvelocity.
23. contain the life-saving system of medicament of the generation gas of one of claim 1 to 18.
24. the medicament of the generation gas of one of claim 1 to 18 is made the application of gas.
CN96193147A 1995-02-18 1996-02-13 Gas-generating mixtures Pending CN1183758A (en)

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CA2211579A1 (en) 1996-08-29

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