WO1998050324A1 - Reduzierung von schadgasen in gasgemischen aus pyrotechnischen reaktionen - Google Patents
Reduzierung von schadgasen in gasgemischen aus pyrotechnischen reaktionen Download PDFInfo
- Publication number
- WO1998050324A1 WO1998050324A1 PCT/EP1998/002562 EP9802562W WO9850324A1 WO 1998050324 A1 WO1998050324 A1 WO 1998050324A1 EP 9802562 W EP9802562 W EP 9802562W WO 9850324 A1 WO9850324 A1 WO 9850324A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- urea
- pyrotechnic
- nitrogen
- gas
- concentration
- Prior art date
Links
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
-
- 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
- C06B23/02—Compositions characterised by non-explosive or non-thermic constituents for neutralising poisonous gases from explosives produced during blasting
Definitions
- the present invention relates to the reduction of harmful gases in gas mixtures from pyrotechnic reactions
- An airbag system consists of the basic components of the impact bag, gas generator and trigger device, which, if necessary, initiates an electrical ignition in the gas generator if a predetermined trigger threshold is exceeded.This produces a gas within a very short time (approx. 40 ms, depending on the airbag module) an airbag flows in, which spreads between the vehicle occupant and the point of impact
- a gas mixture propellant, propellant
- NaJS sodium azide
- LD 50 value of 27 mg / kg potassium cyanide
- cyanide potassium cyanide
- Suitable alternative substances are organic, nitrogen-rich compounds that achieve similarly good performance values (gas yield, pressure curve, etc.) as sodium azide.
- 5-aminotetrazole is suitable as an environmentally compatible alternative fuel. The result was a blowing agent made of 5- Aminotetrazole, oxidizing agents and additives called SINCO
- alternative solid fuels such as 5-aminotetrazole are burned up, not only the non-toxic working gases nitrogen, carbon dioxide and water vapor, but also parts of the toxic gases carbon monoxide, nitrogen monoxide and nitrogen dioxide are produced
- the object of the present invention was therefore to achieve a minimization of the harmful gas concentrations when using the alternative solid fuels
- the NO formation (all types) is generally favored at higher temperatures and longer dwell times of the gases or exhaust gases in the high-temperature range.
- the processes for nitrogen oxide reduction known to date in the prior art are mainly based on a lowering of the combustion temperature Cooling of the exhaust gases prevented
- the low combustion temperatures have the disadvantage that they increase the CO formation. Uneven combustion processes can lead to the strong formation of both harmful gases. Local or short-term overheating causes NO formation and local or short-term supercooling causes CO formation
- the object on which the invention is based was achieved by introducing substances into the flow path of the working gas, for example by coating components of the gas generator.
- the introduced substance is evaporated by the heat of combustion, which causes the harmful gases to be converted into nontoxic compounds in a homogeneous gas phase reaction
- the airbag module can be heated up to 105 ° C. It must be ensured that the additive does not liquefy in such a case and escapes from the airbag module. Therefore, only substances with a melting point> 105 ° C can be used.
- a gas generator should be fully operational over the entire lifespan of a car (up to 15 years).
- the introduced substance should reduce nitrogen oxides in a homogeneous gas phase reaction.
- the tests were carried out in an apparatus which enables the measurement of the concentration curves of nitrogen monoxide and nitrogen dioxide over time in a reaction vessel with a volume of 60 l.
- FIG. 1 The process flow diagram of the experimental apparatus is shown in FIG. 1. It can be divided into the following system parts:
- the experimental apparatus essentially consists of the plastic set reactor and the nitrogen oxide analyzer. At the beginning of each experiment, nitrogen monoxide is metered into the reactor, which partially converts with the atmospheric oxygen into nitrogen dioxide after an equilibrium reaction. The temperature in the reactor is 45 ° C. in all experiments. After about 10 minutes, when the nitrogen dioxide concentration hardly changes, the respective substance is evaporated in the container. By regularly recording the values for nitrogen dioxide or Nitrogen monoxide concentration, the concentration curves can be determined, which allow statements about the effectiveness of the respective substance
- Plastic was chosen as the material for the reactor in order to avoid reactions that can occur on a metallic wall.
- the plastic container used is not very temperature-resistant.Therefore, the temperature in the container should not exceed 45 ° C, so that no deformation of the container wall occurs the reactor has an evaporator and a fan heater
- the evaporator essentially consists of a heating plate that can be continuously heated to 350 ° C, on which the test substances can be heated to sublimation or boiling temperature in a glass dish.
- the fan heater is used to set a desired temperature and to intensive mixing of the reaction mixture The mixing is necessary in order to ensure the same reactant concentrations and temperatures throughout the reactor.
- the temperature in the reactor can be set and readjusted manually
- the temperature in the container must be adjusted due to the heat loss via the wall, the heat supply via the heating plate and the endothermic or exothermic reactions taking place in the reactor.
- the temperature is measured using a thermocouple connected to a voltmeter
- a chemiluminescence device is used, to which the bypass pump, the silica gel drying cartridge and the ozone destroyer / pump unit are connected.
- the reactor and the chemiluminescence device built a microfiber filter
- the nitrogen monoxide is supplied with the help of a gas bag, which, once filled, is connected to the three-way valve.
- the calibration gas nitrogen with 80 ppm nitrogen monoxide
- the gas should therefore flow into the analyzer without pressure Flowing out approx. 50% or 0.6 1 / min of the required amount of gas via a T-piece with an excess line.
- the excess is led into a fume cupboard.
- the excess line has a length of more than 2 m in order to avoid mixing the calibration gas with the atmospheric air
- a flow meter is attached to the line in order to be able to control the specified value for the volume flow. Only pipes with a smooth surface and made of inert material such as PTFE, glass or steel were used as gas lines
- thermocouple is connected to the voltmeter and the cables from the fume cupboard and filter must be set with the three-way cocks on the container cover, which must be set so that the container is closed.
- the calibration can be carried out As soon as the temperature in the reactor has reached 45 ° C, 1 nitrogen monoxide is metered into the container via a gas bag on the three-way valve Same Weight reaction partly in nitrogen dioxide implemented As soon as the nitrogen monoxide is in the reactor, the measurement of the time is started
- the first measured value is recorded after about 30 seconds and the second after about 5 minutes.
- the preheating time that was determined before the measurement determines a point in time at which the evaporator is switched on, so that the substance evaporates after about 10 minutes begins At this time, the plastic container is in a state in which the nitrogen dioxide concentration changes only slowly
- a measured value is read from the chemiluminescence device and entered in the measurement protocol.
- the time intervals between the measurement points after the boiling point has been reached depend on the course of the reaction that results with a specific substance.
- the measurement values are recorded over a period of 25 - 30 minutes carried out During the entire measurement, the temperature in the reactor must be constantly checked and, if necessary, readjusted by hand using a dimmer
- the plastic container After completing the measurement, the plastic container must be opened outdoors and ventilated for at least 15 minutes. Then the hoses, filter, container and three-way cock are thoroughly cleaned and dried
- Table 2 shows an overview of the tests carried out with the additives.
- Table 3 Overview of nitrogen dioxide reduction by ferrocene in the gas phase
- the combustion gases of a gas generator contain not only nitrogen oxides, but also carbon monoxide. For this reason, 3 measurements with a substance amount of 0.03 g ferrocene and the same test conditions as in the previous tests were additionally carried out with carbon monoxide gas in order to identify possible effects of carbon monoxide on the results.
- the ratio CO to NO 2 in the combustion gases of a gas generator is about 10 to 1. This concentration ratio was set in the reactor.
- the CO gas content was measured using Dräger tubes (relative standard deviation: ⁇ 10 to 15%). The results show that the nitrogen monoxide and nitrogen dioxide concentration curve does not change with carbon monoxide gas.
- Table 4 compares the values for nitrogen dioxide reduction with and without carbon monoxide.
- a GC analysis was also carried out to identify the gaseous products.
- 100 mg of ferrocene were stored in a headspace glass for two hours at 80 ° C. in order to convert part of the ferrocene into the gas phase
- Glasses 3 ml of a NO / NO 2 mixture added 2 ml of gas from the headspace glass were analyzed in a gas chromatograph. It was found that cyclopentadiene is also in the gas phase in addition to the ferrocene and air components.
- the course of the nitrogen oxide concentrations was investigated in an experiment with 0.1 g of 1,1'-diacetylferrocene.
- the concentrations change as expected until the substance evaporates.
- the nitrogen monoxide values decrease due to the oxidation and the nitrogen dioxide values increase shortly after the start of the The evaporation process increases the nitrogen monoxide concentration by 23 ppm in 233 s - initially stronger, then becoming weaker -
- the nitrogen dioxide concentration also drops by 26 ppm. Then the normal NO / NO 2 equilibrium is restored
- the nitrogen dioxide concentration drops almost linearly in 25 s from 253 ppm to 225 ppm due to titanocene pentasulfide in the gas phase.
- the nitrogen monoxide concentration increases in the same way from 269 ppm to 298 ppm.
- the normal concentration courses result, i.e. Decrease in nitrogen monoxide due to oxidation and consequently an increase in nitrogen dioxide.
- Table 7 Overview of the increase and decrease in the concentrations of NO and NO
- Table 8 Overview of the increase and decrease in the concentrations of NO and NO 2
- the nitrogen dioxide When using 0.4 g of urea, the nitrogen dioxide is broken down significantly more than when 0.1 g of urea is added. In the first 300 s after the start of the evaporation process, the nitrogen dioxide concentration decreases relatively quickly. The values then decrease further with decreasing speed. At the end of the measurement, a drop in the nitrogen dioxide concentration can still be determined. Overall, the nitrogen dioxide is reduced by 111 ppm in 20 minutes. Table 10 shows all the results obtained with 0.4 g of urea.
- ammonia (NH 3 ) is produced, which is known as a reducing agent for nitrogen oxide reduction. It can be assumed that the nitrogen dioxide decomposition takes place through a homogeneous gas phase reaction of ammonia with nitrogen dioxide. The reduction of NO 2 with NH 3 can be described by the following gross reaction equations:
- the reaction products of this selective reduction are nitrogen (N 2 ) and water vapor in the main reactions.
- the undesirable dinitrogen monoxide (N 2 O) from the side reaction does not seem to form to a substantial extent.
- Nitrogen monoxide is inert compared to nitrogen dioxide. This could be the reason why the nitrogen monoxide is not reduced with ammonia at a temperature of 45 ° C. Influence of N-formylurea on nitrogen oxide concentrations:
- the nitrogen dioxide concentration begins to drop relatively slowly from the time 750 s to the time 1230 s.
- the concentration is reduced from 162 ppm by 12 ppm to 150 ppm. After that, the values remain almost constant. There are no noticeable changes in the nitrogen monoxide concentration curve.
- Table 12 summarizes all the results which were achieved in the 3 experiments with 0.1 g of N-formylurea.
- N-formylurea When N-formylurea is heated above the melting point, ammonia is presumably formed. The homogeneous gas phase reactions that result from this are the same as stated for urea. N-formylurea has a higher molar mass than urea because of the formyl group N-formylurea less ammonia than with urea This explains the poorer values for nitrogen dioxide reduction compared to the tests with urea
- N, N'-dimethylurea When N, N'-dimethylurea is heated above the melting point, ammonia is likely to form, which reduces part of the nitrogen dioxide by means of homogeneous gas-phase reactions. If one compares the results with those obtained in the tests with urea, it is clear that the effect of Use of N, N'-dimethylurea is worse, except for the experiments with 0.1 g of substance.
- the worse values for nitrogen dioxide degradation depend, as with N-formylurea, with the higher molar mass and thus the smaller amount of ammonia that is produced when heated. together
- the better values when comparing the tests with 0.1 g substance amount may result from a positive influence of the two methyl groups. This can also be the reason that the values for nitrogen dioxide degradation compared to the tests with N-formylurea are higher Influence of N y'-dimethylurea on the nitrogen oxide concentrations:
- Table 26 Overview of the increase and decrease in the concentrations of NO and NO 2
- Table 27 Overview of the increase and decrease in the concentrations of NO and NO 2
- Table 28 Overview of the increase and decrease in the concentrations of NO and NO 2
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Biomedical Technology (AREA)
- Combustion & Propulsion (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
- Exhaust Gas After Treatment (AREA)
- Treating Waste Gases (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Air Bags (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR9808712-6A BR9808712A (pt) | 1997-05-02 | 1998-04-30 | Redução de gases poluentes em misturas de gás resultantes de reações pirotécnicas |
JP54770698A JP2001525782A (ja) | 1997-05-02 | 1998-04-30 | 火工品反応からの気体混合物中の有害ガスの減少 |
EP98922789A EP0979219A1 (de) | 1997-05-02 | 1998-04-30 | Reduzierung von schadgasen in gasgemischen aus pyrotechnischen reaktionen |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19718553 | 1997-05-02 | ||
DE19718553.3 | 1997-05-02 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998050324A1 true WO1998050324A1 (de) | 1998-11-12 |
Family
ID=7828413
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1998/002562 WO1998050324A1 (de) | 1997-05-02 | 1998-04-30 | Reduzierung von schadgasen in gasgemischen aus pyrotechnischen reaktionen |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0979219A1 (de) |
JP (1) | JP2001525782A (de) |
CN (1) | CN1253538A (de) |
BR (1) | BR9808712A (de) |
DE (1) | DE19819623A1 (de) |
WO (1) | WO1998050324A1 (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2871797A1 (fr) * | 2004-06-18 | 2005-12-23 | Trw Airbag Sys Gmbh | Composition pyrotechnique |
CN116510225A (zh) * | 2023-05-31 | 2023-08-01 | 上海应用技术大学 | 一种抑烟型环保泡沫灭火剂及制备方法 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999054270A1 (fr) | 1998-04-20 | 1999-10-28 | Daicel Chemical Industries, Ltd. | PROCEDE DE REDUCTION DE NO¿x? |
RU2250800C2 (ru) * | 1999-09-30 | 2005-04-27 | Тно Принс Мауритс Лаборатори | Способ генерирования газов, предпочтительно азота, с низкой температурой и газогенератор для его осуществления |
JP2002302010A (ja) | 2001-04-04 | 2002-10-15 | Daicel Chem Ind Ltd | ハイブリッドインフレータの窒素酸化物の低減法 |
CN102179027B (zh) * | 2010-09-16 | 2012-06-27 | 陕西坚瑞消防股份有限公司 | 一种二茂铁类灭火组合物 |
CN109721446B (zh) * | 2019-03-17 | 2021-07-13 | 程爱宝 | 一种微烟火药复配组合物及其应用 |
PL442263A1 (pl) * | 2022-09-12 | 2024-03-18 | Sieć Badawcza Łukasiewicz - Instytut Przemysłu Organicznego | Stałe heterogeniczne paliwo rakietowe o obniżonej emisyjności chlorowodoru w produktach spalania |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3404531A (en) * | 1966-07-18 | 1968-10-08 | United Aircraft Corp | Method and compositions for producing condensable combustion products |
EP0509763A1 (de) * | 1991-04-15 | 1992-10-21 | Automotive Systems Laboratory Inc. | Verfahren zur Kontrolle der Menge von Stickoxiden im generierten Gas für Airbags |
EP0586060A2 (de) * | 1992-08-24 | 1994-03-09 | Morton International, Inc. | Gaserzeugende Körper ausgestattet mit aufgepresster Verbrennungsinhibitorschicht |
WO1996013405A1 (en) * | 1994-10-31 | 1996-05-09 | Automotive Systems Laboratory, Inc. | Coated fabric for use with nonazide gas generants |
DE19505568A1 (de) * | 1995-02-18 | 1996-08-22 | Dynamit Nobel Ag | Gaserzeugende Mischungen |
WO1997029927A2 (en) * | 1996-02-14 | 1997-08-21 | Automotive Systems Laboratory, Inc. | Nonazide gas generating compositions |
WO1998006682A2 (en) * | 1996-08-12 | 1998-02-19 | Automotive Systems Laboratory, Inc. | Selective non-catalytic reduction (sncr) of toxic gaseous effluents in airbag inflators |
-
1998
- 1998-04-30 EP EP98922789A patent/EP0979219A1/de not_active Withdrawn
- 1998-04-30 CN CN98804448.XA patent/CN1253538A/zh active Pending
- 1998-04-30 BR BR9808712-6A patent/BR9808712A/pt unknown
- 1998-04-30 JP JP54770698A patent/JP2001525782A/ja not_active Withdrawn
- 1998-04-30 WO PCT/EP1998/002562 patent/WO1998050324A1/de not_active Application Discontinuation
- 1998-05-04 DE DE19819623A patent/DE19819623A1/de not_active Withdrawn
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3404531A (en) * | 1966-07-18 | 1968-10-08 | United Aircraft Corp | Method and compositions for producing condensable combustion products |
EP0509763A1 (de) * | 1991-04-15 | 1992-10-21 | Automotive Systems Laboratory Inc. | Verfahren zur Kontrolle der Menge von Stickoxiden im generierten Gas für Airbags |
EP0586060A2 (de) * | 1992-08-24 | 1994-03-09 | Morton International, Inc. | Gaserzeugende Körper ausgestattet mit aufgepresster Verbrennungsinhibitorschicht |
WO1996013405A1 (en) * | 1994-10-31 | 1996-05-09 | Automotive Systems Laboratory, Inc. | Coated fabric for use with nonazide gas generants |
DE19505568A1 (de) * | 1995-02-18 | 1996-08-22 | Dynamit Nobel Ag | Gaserzeugende Mischungen |
WO1997029927A2 (en) * | 1996-02-14 | 1997-08-21 | Automotive Systems Laboratory, Inc. | Nonazide gas generating compositions |
WO1998006682A2 (en) * | 1996-08-12 | 1998-02-19 | Automotive Systems Laboratory, Inc. | Selective non-catalytic reduction (sncr) of toxic gaseous effluents in airbag inflators |
Non-Patent Citations (2)
Title |
---|
CHEMICAL ABSTRACTS, vol. 125, no. 18, 28 October 1996, Columbus, Ohio, US; abstract no. 225916c, R.A. PESCE-RODRIGUEZ ET AL.: "Clean burning low flame temperature solid gun propellants" page 278; XP000661198 * |
J. ENERG. MATER., vol. 14, no. 3&4, 1996, pages 173 - 191 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2871797A1 (fr) * | 2004-06-18 | 2005-12-23 | Trw Airbag Sys Gmbh | Composition pyrotechnique |
CN116510225A (zh) * | 2023-05-31 | 2023-08-01 | 上海应用技术大学 | 一种抑烟型环保泡沫灭火剂及制备方法 |
Also Published As
Publication number | Publication date |
---|---|
BR9808712A (pt) | 2000-07-11 |
EP0979219A1 (de) | 2000-02-16 |
CN1253538A (zh) | 2000-05-17 |
JP2001525782A (ja) | 2001-12-11 |
DE19819623A1 (de) | 1998-11-05 |
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