EP2717972B1 - Method for controlling and/or preventing a fire in a vehicle air-conditioning system - Google Patents

Method for controlling and/or preventing a fire in a vehicle air-conditioning system Download PDF

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Publication number
EP2717972B1
EP2717972B1 EP12725424.1A EP12725424A EP2717972B1 EP 2717972 B1 EP2717972 B1 EP 2717972B1 EP 12725424 A EP12725424 A EP 12725424A EP 2717972 B1 EP2717972 B1 EP 2717972B1
Authority
EP
European Patent Office
Prior art keywords
extinguishant
calcium
fire
containing compound
gel
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.)
Not-in-force
Application number
EP12725424.1A
Other languages
German (de)
French (fr)
Other versions
EP2717972A1 (en
Inventor
Thomas Woehrle
Stephan Leuthner
Rainer Kern
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Robert Bosch GmbH
Samsung SDI Co Ltd
Original Assignee
Robert Bosch GmbH
Samsung SDI Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Robert Bosch GmbH, Samsung SDI Co Ltd filed Critical Robert Bosch GmbH
Publication of EP2717972A1 publication Critical patent/EP2717972A1/en
Application granted granted Critical
Publication of EP2717972B1 publication Critical patent/EP2717972B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62C—FIRE-FIGHTING
    • A62C3/00—Fire prevention, containment or extinguishing specially adapted for particular objects or places
    • A62C3/07—Fire prevention, containment or extinguishing specially adapted for particular objects or places in vehicles, e.g. in road vehicles
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0028—Liquid extinguishing substances
    • A62D1/0035—Aqueous solutions

Definitions

  • the present invention relates to a method for controlling and / or preventing a fire of an air conditioning system in vehicles.
  • DE 10 2009 035 908 A1 describes the use of an extinguishing agent to combat and / or prevent the firing of lithium ion secondary batteries.
  • the extinguishing agent contains a calcium compound and gelling extender additive.
  • the method for controlling and / or preventing a fire of an air conditioning system in vehicles which contains 2,3,3,3-tetrafluoroprop-1-ene as a refrigerant, is characterized in that at least the refrigerant-containing components of the air conditioner (and optionally resulting fire products) are contacted with an extinguishing agent containing an aqueous solution or suspension of a calcium-containing compound and a gelling extinguishing additive, wherein a weight fraction of the yellowing extinguisher additive per volume of the extinguishing agent is in the range of 0.1 to 3.0%. w / v is located.
  • the invention is based on the finding that a combination of a calcium-containing additive (in the form of calcium ions) and a generally polymeric gelling agent is capable of binding hydrogen fluoride formed in the event of a fire.
  • a weight proportion of the gel-forming extinguishing agent additive per volume of the extinguishing agent is in the range of 0.1 to 3.0% w / v, in particular 0.2 to 2.0% w / v, particularly preferably 0.1 to 1.0% w / v. v (weight per volume).
  • the maximum weight percentage of the gel should ensure that salting out of the calcium content by the gel is avoided.
  • the presence of the gel as an additive in the extinguishing agent composition according to the invention has the advantage over pure water that, in principle, a higher cooling capacity is brought about by a considerably reduced rate of evaporation of the water. At the same time, the gel film on the burned material ensures the completion of oxygen.
  • a proportion by weight of the calcium-containing compound per volume of the extinguishing agent is in the range from 1 to 40% w / v, in particular 10 to 30% w / v, particularly preferably 20% w / v.
  • the process basically all water-resistant calcium-containing compounds are suitable.
  • the calcium-containing compound is an inorganic salt, in particular calcium chloride (CaCl 2 ).
  • a further aspect of the invention relates to the use of the extinguishing agent described above, which contains an aqueous solution or suspension of a calcium-containing compound and a gelling extinguishing additive, for controlling and / or preventing a fire of an air conditioning system in vehicles, 2,3,3, Contains 3-tetrafluoroprop-1-ene as a refrigerant, wherein a weight proportion of the yellowing extinguishing agent additive per volume of the extinguishing agent in the range of 0.1 to 3.0% w / v.
  • the extinguishing agent can be used only at the place of use or already premixed.
  • Suitable dispensers and gel delivery devices are well known in the art.
  • a structurant water-absorbing polymers can be used.
  • examples include the product of Evonik available under the trade name Firesorb and the product of BASF available under the trade name Prevento.

Landscapes

  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Fire-Extinguishing Compositions (AREA)

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Bekämpfung und/oder Vorbeugung eines Brandes einer Klimaanlage in Fahrzeugen.The present invention relates to a method for controlling and / or preventing a fire of an air conditioning system in vehicles.

Stand der TechnikState of the art

Die meisten Neufahrzeuge weisen mittlerweile eine Klimaanlage auf, die häufig einen mit einem Kältemittel gefüllten Wärmeaustauscher umfasst. Herkömmliche Kältemittel stehen jedoch in Verdacht, klimaschädigend zu sein, und es gibt daher konkrete Bestrebungen für bestimmte Fahrzeugtypen einen europaweiten Standard für ein neues Kältemittel einzuführen. Das in diesem Zuge favorisierte Kältemittel 2,3,3,3-Tetrafluorprop-1-en (auch als R1234yf bezeichnet) ist laut Herstellerangaben signifikant klimafreundlicher. Ein Nachteil dieses Kältemittels ist jedoch seine Brennbarkeit. Zwar gilt R1234yf als nicht hoch entzündlich, jedoch ist es dennoch entflammbar. Bei einem Brand kann nach Herstellerangaben Fluorwasserstoff (HF) entstehen, eine äußerst toxische und hochkorrosive Verbindung.Most new vehicles now have an air conditioning system, which often includes a heat exchanger filled with a refrigerant. However, conventional refrigerants are suspected of harming the climate, and there are therefore concrete efforts to introduce a Europe-wide standard for a new refrigerant for certain vehicle types. The preferred refrigerant 2,3,3,3-tetrafluoroprop-1-ene (also referred to as R1234yf) is significantly more climate-friendly according to the manufacturer. A disadvantage of this refrigerant, however, is its flammability. Although R1234yf is not highly flammable, it is still flammable. In case of fire, according to the manufacturer, hydrogen fluoride (HF) can be formed, a highly toxic and highly corrosive compound.

Gängige Löschmittel, wie Wasser oder Kohlendioxid, sind nicht geeignet, Fluorwasserstoff zu binden oder zu neutralisieren.Common extinguishing agents, such as water or carbon dioxide, are not suitable for binding or neutralizing hydrogen fluoride.

DE 10 2009 035 908 A1 beschreibt den Einsatz eines Löschmittels zur Bekämpfung und/oder Vorbeugung eines Brandes von Lithiumionen-Sekundärbatterien. Das Löschmittel enthält eine Kalziumverbindung und gelbildendes Löschmitteladditiv. DE 10 2009 035 908 A1 describes the use of an extinguishing agent to combat and / or prevent the firing of lithium ion secondary batteries. The extinguishing agent contains a calcium compound and gelling extender additive.

Offenbarung der ErfindungDisclosure of the invention

Ein oder mehrere der geschilderten Probleme des Standes der Technik können mit Hilfe des erfindungsgemäßen Verfahrens behoben oder zumindest gemindert werden. Das Verfahren zur Bekämpfung und/oder Vorbeugung eines Brandes einer Klimaanlage in Fahrzeugen, die 2,3,3,3-Tetrafluorprop-1-en als Kältemittel enthält, zeichnet sich dadurch aus, dass zumindest die das Kältemittel enthaltenden Bestandteile der Klimaanlage (und gegebenenfalls daraus entstehende Brandprodukte) mit einem Löschmittel in Kontakt gebracht werden, welches eine wässrige Lösung oder Suspension einer Kalzium-haltigen Verbindung und eines gelbildenden Löschmitteladditivs enthält, wobei ein Gewichtsanteil des gelbindenden Löschmitteladditivs pro Volumen des Löschmittels im Bereich von 0,1 bis 3,0 % w/v liegt.One or more of the problems of the prior art described can be eliminated or at least mitigated with the aid of the method according to the invention. The method for controlling and / or preventing a fire of an air conditioning system in vehicles, which contains 2,3,3,3-tetrafluoroprop-1-ene as a refrigerant, is characterized in that at least the refrigerant-containing components of the air conditioner (and optionally resulting fire products) are contacted with an extinguishing agent containing an aqueous solution or suspension of a calcium-containing compound and a gelling extinguishing additive, wherein a weight fraction of the yellowing extinguisher additive per volume of the extinguishing agent is in the range of 0.1 to 3.0%. w / v is located.

Der Erfindung liegt die Erkenntnis zugrunde, dass eine Kombination eines Kalziumhaltigen Additivs (in Form von Kalziumionen) und eines in der Regel polymeren Gelbildners in der Lage ist, im Falle eines Brandes entstehenden Fluorwasserstoff zu binden.The invention is based on the finding that a combination of a calcium-containing additive (in the form of calcium ions) and a generally polymeric gelling agent is capable of binding hydrogen fluoride formed in the event of a fire.

Ein Gewichtsanteil des gelbildenden Löschmitteladditivs pro Volumen des Löschmittels im Bereich von 0,1 bis 3,0 % w/v liegt, insbesondere 0,2 bis 2,0 % w/v, besonders bevorzugt 0,1 bis 1,0 % w/v (weight per volume, also Gewicht pro Volumen). Der maximale Gewichtsanteil des Gels soll sicherstellen, dass ein Aussalzen des Kalziumgehaltes durch das Gel vermieden wird. Die Anwesenheit des Gels als Additiv in der erfindungsgemäßen Löschmittelzusammensetzung hat gegenüber reinem Wasser den Vorteil, dass prinzipiell eine höhere Kühlleistung durch eine erheblich reduzierte Verdunstungsgeschwindigkeit des Wassers bewirkt wird. Gleichzeitig sorgt der Gelfilm auf dem Brandgut für Sauerstoffabschluss. Weiterhin ist bevorzugt, wenn ein Gewichtsanteil der kalziumhaltigen Verbindung pro Volumen des Löschmittels im Bereich von 1 bis 40 % w/v, insbesondere 10 bis 30 % w/v, besonders bevorzugt bei 20 % w/v liegt.A weight proportion of the gel-forming extinguishing agent additive per volume of the extinguishing agent is in the range of 0.1 to 3.0% w / v, in particular 0.2 to 2.0% w / v, particularly preferably 0.1 to 1.0% w / v. v (weight per volume). The maximum weight percentage of the gel should ensure that salting out of the calcium content by the gel is avoided. The presence of the gel as an additive in the extinguishing agent composition according to the invention has the advantage over pure water that, in principle, a higher cooling capacity is brought about by a considerably reduced rate of evaporation of the water. At the same time, the gel film on the burned material ensures the completion of oxygen. It is further preferred if a proportion by weight of the calcium-containing compound per volume of the extinguishing agent is in the range from 1 to 40% w / v, in particular 10 to 30% w / v, particularly preferably 20% w / v.

Für das Verfahren sind grundsätzlich alle wasserbeständigen Kalzium-haltigen Verbindungen geeignet. Besonders bevorzugt ist für die Kalzium-haltige Verbindung jedoch ein anorganisches Salz, wie insbesondere Kalziumchlorid (CaCl2).For the process basically all water-resistant calcium-containing compounds are suitable. However, particularly preferred for the calcium-containing compound is an inorganic salt, in particular calcium chloride (CaCl 2 ).

Ein weiterer Aspekt der Erfindung betrifft die Verwendung des zuvor beschriebenen Löschmittels, welches eine wässrige Lösung oder Suspension einer Kalzium-haltigen Verbindung und eines gelbildenden Löschmitteladditivs enthält, zur Bekämpfung und/oder Vorbeugung eines Brandes einer Klimaanlage in Fahrzeugen, die 2,3,3,3-Tetrafluorprop-1-en als Kältemittel enthält, wobei ein Gewichtsanteil des gelbindenden Löschmitteladditivs pro Volumen des Löschmittels im Bereich von 0,1 bis 3,0 % w/v liegt.A further aspect of the invention relates to the use of the extinguishing agent described above, which contains an aqueous solution or suspension of a calcium-containing compound and a gelling extinguishing additive, for controlling and / or preventing a fire of an air conditioning system in vehicles, 2,3,3, Contains 3-tetrafluoroprop-1-ene as a refrigerant, wherein a weight proportion of the yellowing extinguishing agent additive per volume of the extinguishing agent in the range of 0.1 to 3.0% w / v.

Das Löschmittel kann erst am Einsatzort oder bereits vorgemischt zur Anwendung kommen. Geeignete Dosierer und Vorrichtungen zur Gelabgabe sind aus dem Stand der Technik hinreichend bekannt.The extinguishing agent can be used only at the place of use or already premixed. Suitable dispensers and gel delivery devices are well known in the art.

Als Gebildner können Wasser absorbierende Polymere Einsatz finden. Beispiele umfassen das unter dem Handelsnamen Firesorb erhältliche Produkt der Firma Evonik sowie das unter dem Handelsnamen Prevento erhältliche Produkt der Firma BASF.As a structurant water-absorbing polymers can be used. Examples include the product of Evonik available under the trade name Firesorb and the product of BASF available under the trade name Prevento.

Ausführungsbeispielembodiment

500 ml 2,3,3,3-Tetrafluorprop-1-en (HFO-1234yf der Firma Honeywell) werden in einer Glaswanne entzündet und anschließend gelöscht mit

  1. a) reinem Wasser
  2. b) einer wässrig basierten Gellösung von 10 % Kalziumchlorid (w/v) und 1 % Prevento (w/v).
500 ml of 2,3,3,3-tetrafluoroprop-1-ene (HFO-1234yf from Honeywell) are ignited in a glass pan and then quenched with
  1. a) pure water
  2. b) an aqueous based gel solution of 10% calcium chloride (w / v) and 1% Prevento (w / v).

Im Vergleichsversuch a) konnte der Brand gelöscht werden, jedoch wurde im Löschwasser Fluorid nachgewiesen. Bei Einsatz des erfindungsgemäßen Löschmittels gemäß Versuch b) konnte der Brand zum einen schneller gelöscht werden und zum anderen ließ sich im Löschwasser kein freies Fluorid mehr nachweisen. Beim Brand entstehender Fluorwasserstoff wurde als schwer löslicher Niederschlag in Form von Kalziumfluorid (CaF2) abgebunden.In comparison experiment a) the fire could be extinguished, but fluoride was detected in the extinguishing water. When using the extinguishing agent according to the invention according to experiment b) the fire could be extinguished faster and, secondly, no free fluoride could be detected in the extinguishing water. Hydrogen fluoride formed on burning was bound as a sparingly soluble precipitate in the form of calcium fluoride (CaF 2 ).

Analoge Ergebnisse ließen sich mit dem Gelbildner Firesorb erzielen.Analogous results could be achieved with the gel former Firesorb.

Claims (8)

  1. Method for controlling and/or preventing a fire in a vehicle air-conditioning system containing 2,3,3,3-tetrafluoro-1-propene as refrigerant, characterized in that at least the constituents of the air-conditioning system which contain the refrigerant are brought into contact with an extinguishant which contains an aqueous solution or suspension of a calcium-containing compound and of a gel-forming extinguishant additive, wherein a weight fraction of gel-forming extinguishant additive per volume of extinguishant is in the range from 0.1 to 3.0% w/v.
  2. Method according to Claim 1 wherein a weight fraction of gel-forming extinguishant additive per volume of extinguishant is in the range from 0.2 to 2.0% w/v.
  3. Method according to either preceding claim wherein a weight fraction of calcium-containing compound per volume of extinguishant is in the range from 1% to 40% w/v.
  4. Method according to any preceding claim wherein the calcium-containing compound is an inorganic salt.
  5. Method according to Claim 4 wherein the calcium-containing compound is calcium chloride.
  6. Use of an extinguishant which contains an aqueous solution or suspension of a calcium-containing compound and of a gel-forming extinguishant additive, for controlling and/or preventing a fire in a vehicle air-conditioning system containing 2,3,3,3-tetrafluoro-1-propene as refrigerant, wherein a weight fraction of gel-forming extinguishant additive per volume of extinguishant is in the range from 0.1 to 3.0% w/v.
  7. Use according to Claim 6 wherein a weight fraction of calcium-containing compound per volume of extinguishant is in the range from 1% to 40% w/v.
  8. Use according to either of Claims 6 and 7 wherein the calcium-containing compound is an inorganic salt.
EP12725424.1A 2011-06-09 2012-06-04 Method for controlling and/or preventing a fire in a vehicle air-conditioning system Not-in-force EP2717972B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011077312A DE102011077312A1 (en) 2011-06-09 2011-06-09 Method for controlling and / or preventing a fire of an air conditioning system in vehicles
PCT/EP2012/060458 WO2012168165A1 (en) 2011-06-09 2012-06-04 Method for controlling and/or preventing a fire in a vehicle air-conditioning system

Publications (2)

Publication Number Publication Date
EP2717972A1 EP2717972A1 (en) 2014-04-16
EP2717972B1 true EP2717972B1 (en) 2019-01-16

Family

ID=46208050

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12725424.1A Not-in-force EP2717972B1 (en) 2011-06-09 2012-06-04 Method for controlling and/or preventing a fire in a vehicle air-conditioning system

Country Status (6)

Country Link
US (1) US20140174767A1 (en)
EP (1) EP2717972B1 (en)
CN (1) CN103619420A (en)
DE (1) DE102011077312A1 (en)
ES (1) ES2720153T3 (en)
WO (1) WO2012168165A1 (en)

Family Cites Families (12)

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Publication number Priority date Publication date Assignee Title
GB354726A (en) * 1930-05-12 1931-08-12 Jens Orten Boving Improvements in reversible refrigerating apparatus employing a solid absorbent or an adsorbent
US2311374A (en) * 1938-11-01 1943-02-16 American District Telegraph Co Automatic fire control system for ventilating or air conditioning systems
US4033740A (en) * 1976-02-23 1977-07-05 Gershon Meckler Associates Combined environmental control and fire protection system
US4405347A (en) * 1982-01-11 1983-09-20 Multiform Desiccants, Inc. Adsorbent unit for mounting in the upper portion of a refrigerant receiver
ZA943048B (en) * 1993-05-04 1995-01-30 Programme 3 Patent Holdings High temperature storage battery
DE4411281B4 (en) * 1994-03-31 2004-07-22 Daimlerchrysler Ag Motor vehicle with an air conditioner
US6300378B1 (en) * 1996-09-27 2001-10-09 University Of New Mexico Tropodegradable bromine-containing halocarbon additives to decrease flammability of refrigerants foam blowing agents solvents aerosol propellants and sterilants
WO2002085460A1 (en) * 2001-04-20 2002-10-31 Kohjin Co., Ltd. Fire-extinguishing agent, water for fire extinguishing, and method of fire extinguishing
CN1765434A (en) * 2005-04-26 2006-05-03 昆明泰康集团有限公司 Multifunctional cold aerosol fire extinguishing agent and its preparation method
US7708903B2 (en) * 2005-11-01 2010-05-04 E.I. Du Pont De Nemours And Company Compositions comprising fluoroolefins and uses thereof
DE102008001707A1 (en) * 2008-05-09 2009-11-12 Robert Bosch Gmbh Energy converter or energy storage device comprises one or multiple energy converters or energy storage units for example, fuel cell or battery unit
DE102009035908A1 (en) * 2009-08-03 2011-02-10 Robert Bosch Gmbh Method for controlling and / or preventing a fire of lithium-ion cells and lithium-ion polymer cells

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
ES2720153T3 (en) 2019-07-18
EP2717972A1 (en) 2014-04-16
WO2012168165A1 (en) 2012-12-13
US20140174767A1 (en) 2014-06-26
CN103619420A (en) 2014-03-05
DE102011077312A1 (en) 2012-12-13

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