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Clean Agent Fire Protection Clean Agent Fire Protection with Hydrofluorocarbonswith Hydrofluorocarbons

Mark L. Robin, Kenneth V. Blanchard and Souvik GhoshDuPont Fluoroproducts

Presented at:

Fire India 2009Mumbai, India

September 7, 2009

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Halogenated Compounds as Fire Suppression Agents

Early 1900sCCl4 extinguishers introduced

Late 1920s : Methyl Bromide (CH3Br)More effective than CCl4British – aircraft applicationsWWII - German military aircraft, marine

Late 1930s: Bromochloromethane (CH2BrCl)German LuftwaffeUS Air Force in late 1940s

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Halogenated Compounds as Fire Suppression Agents

Late 1940sUS Army sought agent as effective as

CH3Br or CH2BrCl, but with lower toxicityOver 60 agents evaluatedFour selected for further study

Halon 1301 CF3Br Halon 1211 CF2BrClHalon 1202 CF2Br2Halon 2402 BrCF2CF2Br

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The Halon Era: 1960s to 1994Halon 1301: CF3Br

Total flooding applications

Halon 1211: CF2BrClPortable, local applications

“Clean Agents”No corrosive or abrasive residues left

following extinguishment

Water, foam, powder – secondary damage due to agent can exceed damage due to fire

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Automatic Sprinkler System DischargeAutomatic Sprinkler System Discharge

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Foam System DischargeFoam System Discharge

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Dry Chemical System DischargeDry Chemical System Discharge

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Halon 1301/Halon 1211: “Clean Agents”

Clean Agents

No corrosive or abrasive residuesNo damage to sensitive/expensive assets

No cleanup required after dischargeNo business interruption

Source: Alinenan ROI Report, January 2004.

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Downtime Impact for Various Downtime Impact for Various Business ApplicationsBusiness Applications

Business Application Estimated Outage Cost per Minute, US$

Supply Chain Management $11,000

Electronic Commerce $10,000

Customer Service Center $3,700

ATM $3,500

Financial Management $1,500

Messaging $1,000

Infrastructure $700Source: Alinenan ROI Report, January 2004.

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The Halon Era: 1960s to 1994What made the Halons “Ideal Fire

Extinguishing Agents” ???CleanEfficient fire suppressionChemically inert• Storage stable• Non-reactive chemically

Electrically non-conductingLow ToxicityLow Cost

A unique combination of properties

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The Halon Era: 1960s to 1994Halon 1301/Halon 1211 Applications

Electronics facilitiesComputer roomsCommunications equipment roomsOil & gas industry

● pipeline pumping stations● offshore platforms

Shipboard machinery spacesMuseumsLibraries

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Ozone Depletion

Source: U.S. EPA

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Properties of the Ideal Halon ReplacementProperties of the Ideal Halon Replacement• Clean • Efficient fire suppression• Chemically inert

Long term storage stabilityNo chemical reactions with water, fuels, assets

• Electrically non-conducting• Low toxicity• Zero ODP• Zero GWP• Reasonable manufacturing cost

No replacement has been found which satisfies ALL of the above requirements

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Halon 1301 ReplacementsHalon 1301 Replacements• Hydrofluorocarbons (HFCs)

HFC-227ea: FM-200® CF3CHFCF3HFC-125: FE-25TM CF3CF2HHFC-23: FE-13TM CF3H

• Hydrochlorofluorocarbons (HCFCs)HCFC Blend A: NAF-S-III

• HCFC-22/HCFC-123/HCFC-124/d-limonene• Inert Gases

IG-541: InergenTM Ar/N2/CO2IG-55: ArgoniteTM Ar/N2

• Perfluorinated KetonesFK-5-1-12: NovecTM 1230 CF3CF2CCF(CF3)2

O

HCFCs Subject to Phaseout

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Halogenated Agents: Extinguishing Mechanism

• Primarily via physical mechanism of heat removal

Reduces flame temperature below that required to maintain combustion

Efficient mechanism – extinguishing concentrations typically 4 to 12% v/v

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Inert Gas Agents: Extinguishing Mechanism

• Flame extinguishment via O2 dilution

Slows combustion reaction rate to point where reaction can no longer sustain itself

Inefficient mechanism- extinguishing concentrations typically 40 to 70% v/v

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AGENT PERFORMANCE: Inert Gases & HFCsAGENT PERFORMANCE: Inert Gases & HFCsAgent Quantity for Protection of 100 m3 Volume

Class A Hazard Class B Hazard a

Agent Agent required,

% v/v

Agent required,

kg

Agent required,

% v/v

7.0 54.8

72.440.0

8.7

43.9

Agent required,

kg

HFC-227ea 69.4

IG-541 81.9

a Heptane

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Comparison of Inert Gas and Comparison of Inert Gas and Halogenated SystemsHalogenated Systems

Inert Gas Agents• Cannot be compressed to

liquid – stored as high pressure gas

• Require high pressure cylinders, piping

• Require large number of cylinders – large footprint

• Cost increases more rapidly with increasing system size

Halogenated Agents• Stored as liquid• Large mass of agent can

be stored in small volume• Standard cylinders,

piping• Small number of

cylinders required – small footprint

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Halocarbon vs Inert Gas System: Halocarbon vs Inert Gas System: 1000 m1000 m33 Enclosure, Class A HazardEnclosure, Class A Hazard

Agent Design Conc., %

v/v

Agent, kg

7.0 548

72440.0

No. Cylinders

HFC-227ea 2

IG-541 (300 bar) 22

HFCHFC--227ea227ea

IG-541

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Agent Efficiency: Requirements for Total Flooding Agents

Low boiling point• Desire gaseous agent to completely and rapidly flood

the protected enclosure, including obstructed areas• Allows for larger area coverage, higher maximum ceiling height,

lower storage and operation temperatures • Example: Halon 1301 vs Halon 1211 – Halon 1301 better suited

as total flooding agent

Low mass of agent required for extinguishment• Agent pricing is on a weight basis (kg), not volume

Low vapor density of air/agent mixture• Lower vapor density = longer hold times

Low system cost

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Halon 1301 Replacements:Halon 1301 Replacements:Chemical/Physical PropertiesChemical/Physical Properties

Halon 1301 HFCs Inert Gases F-Ketones

Physical State a Gas Gas

HFC-227ea -16 oCHFC-125 - 48 oCHFC-23 - 82 oC

Very Low

Gas Liquid

Boiling point - 58 oC IG-541 - 196 oCIG-55 -190 oC

NovecTM

1230:47 oC

Chemical Reactivity Very Low Very Low High

a At room temperature (25 oC)

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Agent EfficiencyProperty FM-200® NovecTM 1230 a

Boiling Point -16 oC 47 oC

Kg to protect 1000 m3, Class A 548 610

Maximum Area Coverage

239 m2

(2576 ft2)95 m2

(1024 ft2)

Maximum Ceiling Height

4.9 m(16 ft)

4.3 m(14 ft)

Container Storage Temperature b

0 to 54 oC(32 to 130 oF)

16 to 27 oC(60 to 80 oF)

Vapor Density of Agent/Air Mixture

1.75 kg/m3

(0.109 lb/ft3)1.94 kg/m3

(0.121 lb/ft3)a Sapphire Design Manual, Ansulb Engineered system protecting multiple hazards

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Halon Replacements: Halon Replacements: Chemical/Physical PropertiesChemical/Physical Properties

Fundamental Differences• Physical State

Halons/HCFCs/HFCs/Inert Gases: Gases at room temperatureC6 Perfluoroketone: Liquid at room temperature

• Chemical ReactivityHalons/HCFCs/HFCs/Inert Gases: Chemically unreactivePerfluoroketones: Chemically reactive – water, alcohols

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Halon Replacements and Halon Replacements and Chemical ReactivityChemical Reactivity

Low Chemical Reactivity Required –Chemical Reactivity Impacts:

Performance/LeakageHandling Human ExposureCleanlinessEnvironmental Impact

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Potential Consequences of Potential Consequences of Chemical ReactivityChemical Reactivity

System Performance CompromisedSystem Performance CompromisedAgent reacted is not available for suppression

“Contact with water or solvents either polar or hydrocarbon could render Novec 1230 fluid ineffective” a

Systems in place 10-20 years● Systems must remain leak-free throughout this period● Chemical reactions producing even small amounts of

corrosive products could lead to corrosion and eventual leakage of agent, compromising the effectiveness and safety of the system

aSapphire Installation Manual, 5/15/2003

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Potential Consequences of Potential Consequences of Chemical ReactivityChemical Reactivity

•• Special Handling ProceduresSpecial Handling Procedures• Example: vent driers, nitrogen purges required to

prevent contact of NovecTM 1230 with moist air a

•• Human Exposure ImplicationsHuman Exposure Implications• NovecTM 1230 hydrolyzed when crossing lung-air

interface to produce HFC-227ea and F-propionic acid b

a 3M: Sapphire Installation Manual, 5/15/2003b 3M Technical Brief, Novec 1230 Fire Protection Fluid Safety Assessment, 2004

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Potential Consequences of Potential Consequences of Chemical ReactivityChemical Reactivity

•• Atmospheric Impact ImplicationsAtmospheric Impact Implications• Example: Atmospheric hydrolysis of NovecTM 1230

not considered in evaluation of GWP • The extent of atmospheric hydrolysis, e.g., on

atmospheric aerosols, could render GWP of perfluoroketones similar to that of HFCs

•• Cleanliness ImplicationsCleanliness Implications• Detrimental chemical reaction with enclosure,

enclosure contents

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NovecNovecTMTM 1230 Discharge on Plastic Cladding1230 Discharge on Plastic Cladding

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Toxicological Profile of HFCsToxicological Profile of HFCs

• Hydrofluorocarbons • Toxicology well-characterized for a large number of HFCs• More toxicological studies have been performed on FM-200®

than any other clean agent • FM-200® approved for use in metered-dose inhalers• FM-200® not metabolized

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Environmental RegulationsEnvironmental Regulations• Montreal Protocol

• Related to ozone depleting substancesHFCs all zero ODP, so not subject to Montreal Protocol

• Kyoto ProtocolRelated to greenhouse gases (GHGs)HFCs are one type of GHGKyoto Protocol concerned with emission reductions

• No limits or banning of HFCs in fire suppression applications

• F-Gas RegulationsSimilar to Kyoto ProtocolNo limits or banning of HFCs in fire suppression applications

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Impact of Emissions of HFCs from Fire Impact of Emissions of HFCs from Fire Suppression ApplicationsSuppression Applications

• Impact of all HFC emissions < 3% of total impact of all GHG emissions

• Impact of HFC emissions from fire fighting< 1% of total impact of all HFC emissions, hence….

• Impact of HFC emissions from fire fighting < 0.03% of total impact of all GHG emissions

Fire suppression systems regarded as essentially non-emissive

Source: HEEP, US EPA 2009

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US EPA Position on HFCsUS EPA Position on HFCs“EPA does not anticipate any change to its acceptability listing of HFCs in fire suppression applications. The availability of Halon substitutes such as HFCs have been key in achieving the significant progress made to date and will continue to be important in eliminating the use of halons in the U.S. and globally.”a

The new U.S. EPA Supercomputing Center employs FM-200® for fire protection

On January 2, 2009, the U.S. EPA announced the approval of several HFC-containing blends as acceptable substitutes under SNAP for HCFC-22 in numerous refrigeration applications b

aEPA letter to Chemtura b Fed. Reg. 74(1), p. 23 (1/2/2009)

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Overall Comparison of Halon ReplacementsOverall Comparison of Halon Replacements

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Worldwide Clean Agent MarketNumber of Installed Systems

HFCs are the most widely employed Halon 1301 alternatives

HFCs (70%)

Inert Gases (20%)

Other (10%)

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Clean Agent Market: Installed SystemsClean Agent Market: Installed Systems

90.0%

7.0%3.0%

90.0%

9.0%1.0%

FM-200

HFC-125 7%

HFC-227ea 90%

Other 3%

IG-541 90%

IG-55 9%

Other 1%

HFCs Inert Gases

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HFC Clean Agents: Global Acceptability

• HFC-227ea (FM-200®) is the most widely employed Halon 1301 alternative worldwide

• > 300,000 systems installed• Internationally accepted standards • Approved by numerous international bodies

• SNAP (U.S. EPA)• Underwriters Laboratories • Factory Mutual• NFPA, ISO, numerous national standards• U.S. Department of Defense• IMO, US Coast Guard• U.S. FAA• LPC, VdS

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HFC Clean Agent Installations: Global Acceptability

• Afghanistan, Algeria, Argentina, Australia• Bahrain, Bermuda, Belgium, Brazil• Canada, Chile, Colombia, Congo, Czech Republic, China• Dominican Republic• Egypt• France• Gabon, Germany, Greece, Guam, Gibraltar• Hong Kong, Hungary• India, Indonesia, Iran, Iraq, Italy, Israel• Jamaica, Japan, Jordan• Kuwait• Lebanon• Malaysia, Mexico• Netherlands, New Zealand, Norway, North Korea

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HFC Clean Agent Installations: Global Acceptability

• Panama, Pakistan, Peru, Poland, Philippines, Portugal, Puerto Rico

• Qatar• Romania, Russia• Saudi Arabia, Singapore, Slovokia, S. Africa, S. Korea,

Spain, Sweden• Taiwan, Thailand, Trinidad, Tobago, Turkey• Ukraine, United Arab Emirates, UK, USA, Uruguay• Venezuela

• Over a decade of experience with HFC clean agent systems has demonstrated their safety and performance

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HFC Clean Agents: Applications• Telecommunications facilities• Computer rooms/Data centers• Museums, Libraries• Hospitals, Medical Facilities/Equipment• Clean rooms• Engine compartments/nacelles• Petrochemical facilities• Grain elevators• Oil rig platforms• Floating roof tanks• Aircraft• Motorsports

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FM-200® Applications:Museums and Cultural Landmarks• American Museum of Natural History• Smithsonian Institute – Star Spangled Banner• Library of Congress – 1st draft of Declaration of

Independence• Eiffel Tower• Alexandria Library, Egypt• National Museum of Prehistory, Taiwan• Field Museum, Chicago• Aristoteles University Rare Book Collection, Greece• Royal Thai Family Silk Museum, Thailand

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FM-200® Applications:Airports and Satellite Installations

• North American DEW Line Radar Installation• Dusseldorf Int’l Airport• Madrid Int’l Airport• Charles DeGaulle Airport• Newark Int’l Airport• San Francisco Int’l Airport• New Bangkok Int’l Airport• Dubai Int’l Airport

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FM-200® Applications:Data/Control Centers

• U.S. EPA Supercomputing Center• Caesar’s Palace, Las Vegas• Harrah’s Casino• MGM Casino, Las Vegas• Cox Communications

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HFC Clean Agents: Applications Military Aircraft, Ships, Vehicles

• Engine Nacelles – US DOD• FE-25TM (HFC-125) accepted as the best replacement for

Halon 1301 in engine nacelle protectionF/A-18 E/F, V-22, H-60 helicopter, UH-1Y, AH-1Z and

F22 aircraft

• FM-200® (HFC-227ea)• MLRS and M2/M3 Bradley fighting vehicle• LPD-17 amphibious transport ship• CVN-76 aircraft carrier• Stryker crew compartment• Lewis and Clark T-AKE-1 Combat Logistics Force Ship• LCU-2000 series watercraft

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Industry Leader Acceptance of Industry Leader Acceptance of HFC Fire Extinguishing AgentsHFC Fire Extinguishing Agents

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Industry Partners Offering Industry Partners Offering HFC Fire Extinguishing AgentsHFC Fire Extinguishing Agents

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HFCs in Fire Suppression: Conclusion• HFCs are the most widely employed Halon

replacements worldwide• Best combination of effectiveness, cleanliness, low

chemical reactivity, toxicity, environmental impact and cost of Halon replacement agents

• Globally accepted• Mature technology – 17 year history• Excellent safety history• Excellent performance history