recent development in clean agent fire suppression · pdf file4 4 4 04/2009 4-dupont...

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-DuPont Confidential-

Recent Developments in Clean Fire Suppression Agents

Mark L. Robin, Ph.D.DuPont Chemicals & Fluoroproducts

NFPA Conference & ExpoJune 12, 2013Chicago, IL

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Learning Objectives

1. What Are Clean Agents?2. The History of Clean Agents3. The Halon Clean Agents4. Halon Replacements

Desired PropertiesCurrent Commercial Clean Agents

5. DuPont Clean Agent ProgramTotal Flood CandidateStreaming Candidates

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I. Clean Agents: What are they?

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What is a Clean Agent?NFPA 2001 Standard on Clean Agent Fire

Extinguishing Systems (2012 edition)

3.3.6 Clean Agent. Electrically nonconducting, volatile, or gaseous fire extinguishing agent that does not leave a residue upon evaporation

No residueNo cleanupNo downtime

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Which Fire Extinguishing Agents are NOT Clean? Water Foam Powder

ResidueCleanupDowntimeNon-fire damage to assets

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Comparison Testing of Preaction Sprinkler and FM-200® Systems

• In-cabinet fire• Clean Agent System

FM-200® system designed and installed in accordance with NFPA 2001

• Preaction Sprinkler SystemDesigned and installed in accordance with NFPA 13

• Detection/Alarm SystemsDesigned and installed in accordance with NFPA 72

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Clean Agent vs Sprinklers

In-cabinet fire

NFPA Compliant FM-200® and pre-action sprinkler systems

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Before…..

DuPont FM-200® Clean Agent System

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After…..

DuPont FM-200® Clean Agent System

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Automatic Sprinkler System

Before…..

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After…..


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After…..

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Suppression agent

Sprinkler Systems Clean Agent System Water Gas

Design Objective

Fire Control: Confine fire Control ceiling T

Fire Extinguishment

Design Objective Protect structure Protect contents Activation

Sprinkler head T 135 oF

Automatic activation following detection (air sampling, smoke detectors)

Fire size at activation

Can be 100's of kW Low as 0.1 kW with air aspirating detection system

Total Flooding

No. Water not three dimensional, will not fill entire enclosure

Yes. Agent distributed uniformly throughout enclosure

Cleanliness

No. Water damage, smoke damage

Yes. No residues to clean up following extinguishment

Comparison of Sprinkler and Clean Agent Systems

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Foam System Discharge

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Dry Chemical System Discharge

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II. History of Clean Agents

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The History of Clean Agent Fire Suppression

“Why should we look to the past in order to prepare for the future? Because there is

nowhere else to look.”

– James Burke

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Halogenated Compounds as Fire Suppression Agents

1870 to 1910• CCl4 extinguishers introduced• Handhelds• Fire Grenades

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Late 1920s : Methyl Bromide (CH3Br)• More effective than CCl4• British – aircraft applications• WWII - German military aircraft, marine

Late 1930s: Bromochloromethane (CH2BrCl)• German Luftwaffe• US Air Force in late 1940s

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Late 1940s US Army sought agent as effective as

CH3Br or CH2BrCl, but with lower toxicity Over 60 agents evaluated: Purdue University

Four selected for further studyHalon 1301 CF3Br Halon 1211 CF2BrClHalon 1202 CF2Br2Halon 2402 BrCF2CF2Br

Br reacts chemically with key flame species

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

Total flooding applications

Prefer a Gaseous Agent

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The Halon Era: 1960s to 1994Halon 1211: CF2BrCl

Portable applications

Prefer a Liquid Agent

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III. The Halons were near ideal…– What Happened?

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IV. Halon to be Phased Out- Now What?

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The Search for “Son of Halon” mid-1980s to Present

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The Search for Halon Replacements:Mid 1980s to today

AcademiaNMERI / CGET

Government/MilitaryNISTArmy, Navy, Air ForceFAA

IndustrialDuPontICIGreat Lakes Chemical Corporation3MAmerican PacificAnsul

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Chemical Agents Extinguish fire by interfering with the flame chemistry

React with and remove key flame species Chain carriers H, O and HO radicals removed Very efficient

Physical Agents Extinguish fire via physical mechanisms

Heat removal O2 dilution Separation of fuel and oxidant

Search for Halon Replacements

Fire Tetrahedron

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Chemical AgentsBromine or iodine containing molecules• Great Lakes Chemical Corporation

FM-100TM ; CF2HBr Performance = Halon 1301 ODP too high; toxicity too high

• ICI CF3CHFBr “Fluothane” Good performance Inhalation Anesthetic, ODP too high

• CF3I “Purple Haze” Good performance High toxicity Chemically reactive, corrosive High manufacturing cost

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Chemical Agents• Advanced Agent Working Group (AAWG)• Roots in CF3I working group• Goal: Halon 1301 replacement• North Slope Operators, U.S. military, EPA, NASA,

Kidde International, Kidde-Fenwal Combustion Research, QinetiQ, UK MOD, American Pacific Corporation, NMERI, NIST, 3M, Great Lakes, DuPont, HARC

Bromine-containing alkenes, alcohols, ethers, amines, carbonyl compounds, and aromatics

Selection: bromine-containing alkenes

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Chemical Agents• Advanced Agent Working Group (AAWG)• Bromine-containing alkenes

CF2BrCH=CH2CF2BrCF2CH=CH2CF3CH=CHBrCF3CBr=CH2CF2BrCF2CH=CH2CF3CF2CBr=CH2

“Tropodegradable” – short lifetime due to rxn with hydroxyl radical

Too reactive = high toxicityShort atmospheric lifetime = high toxicity

All too toxic for total flooding in occupied areas

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Physical Agents• Chlorine-containing Agents: Safety Hi-Tech

NAF-S-III: HCFC-22/HCFC-123/HCFC-124/d-limonene Nonzero ODP; slated for phaseout

• Perfluorocarbons: 3M C3F8 PFC-2-1-8 n-C4F10 PFC-3-1-10 Extremely long atmospheric life, extremely high GWP Permanent effect on climate change

• Ethers C-O linkage leads to more rapid rxn with HO

• Only true for -OCH2-, -OCHF-, -OCH2F, -OCH3 groups

• AminesRfNH2, RfR’f’NH, RfRfRfNDifficult synthesis; toxic

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Physical Agents• Inert Gases: Ansul

Inergen: N2/Ar/CO2

• Hydrofluorocarbons Great Lakes: CF3CHFCF3 FM-200®

DuPont: CF3H (FE-13TM); CF3CF2H (FE-25TM)

• Perfluoroketones: 3MCF3CF2C(O)CF(CF3)2 NovecTM 1230 ; NovecTM 649

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Why Fluorine?

VolatilityStabilityLow ToxicityFlame Suppression

-C-H - C-F

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V. Halon Replacements- Commercialized Agents

100s of Researchers1000s of Compounds Screened Later……..

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Commercialized Halon 1301 Replacements

• Hydrofluorocarbons (HFCs) HFC-227ea: DuPont FM-200® CF3CHFCF3 HFC-125: DuPont FE-25TM CF3CF2H HFC-23: DuPont 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/CO2 IG-55: ArgoniteTM Ar/N2

• Perfluorinated Ketones FK-5-1-12: NovecTM 1230 CF3CF2C(O)CF(CF3)2

Subject to Phase-out

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Commercialized Halon 1211 Replacements

• Hydrofluorocarbons (HFCs) HFC-236fa: DuPont FE-36TM CF3CH2CF3

• Hydrochlorofluorocarbons (HCFCs) Halotron® I: HCFC-123 + Ar + CF4

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Ideal Halon 1301 Replacement Halon 1301 HFCs Inert Gases PerfluoroketonesHigh weight efficiency XX X Gas at ambient temperature X X XLow chemical reactivity X X XElectrically nonconducting X X X XLow toxicity X X XLack of metabolism X X XLow agent cost X X XLow system cost X X XLow number agent cylinders X X XLow storage volume X X XLow system footprint X X XLow cylinder pressure rating X X XLow manifold pressure rating X X XLow negative pressures during discharge X X XLow positive pressures during discharge X X XSlow stratification X X XZero ODP (ozone depletion potential) X X XZero GWP (global warming potential) XVOC exempt (no contribution to smog) X X X

Comparison of Halon ReplacementsX = provides desired property

HFCs offer the best overall combination of the properties desirable in a Halon replacement

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Worldwide Clean Agent MarketNumber of Installed Systems

HFCs (70%)

Inert Gases (20%)

Other (10%)

HFCs are the most widely employed Halon 1301 alternatives

70% FM-200®

20% FE-25TM

10% NovecTM 1230

90% Inergen®

10% Argonite®

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VI. Recent Developments in Clean AgentsDuPont’s Clean Agent Program

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DuPont Clean Agent History• 1947 Halon 1301 identified (U.S. Army Engineering Development

Research Lab, DuPont, and Purdue Research Foundation)

• 1960s Halon 1301 - manufactured and marketed by DuPont

• 1995 DuPont launches FE-13™ (HFC-23)

• 1997 DuPont launches FE-36™ (HFC-236fa) for portable extinguishers

• 2001 DuPont launches HFC-227ea as FE-227™

• 2002 DuPont launches FE-25™ (HFC-125)

• 2008 DuPont acquires FC business of GLCC- FM-200® becomes DuPont trade name

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Goal: Discover and commercialize a range of new clean fire extinguishing agents to extend our current portfolio and

satisfy the safety, environmental and performancerequirements of clean agent users around the world

DuPont Clean Agent Program

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Clean Agent DevelopmentTotal Flooding Agents

• High mass efficiency• Chemically inert

• No reaction with water, common solvents• Long term storage stability

• High volatility• bp -70 to + 40 oC

• Electrically non-conducting• Low toxicity

• MDC < CS NOAEL• MDC < 4h LC50

• Cost effective

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Toxicological Requirements = BIG Challenge

Tox Requirements

• 4h LC50 > MDC• Cardiac NOAEL > MDC• Cardiac LOAEL > MDC

Much higher bar compared to refrigeration, foam blowing, propellant, & solvent tox requirements

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Toxicological TestingNo Qualitative Structure Activity Relationships

(QSAR) available for 4h LC50 or cardiac sensitization tests

Agent screening: 1h LC50• 200 - 300 g material = $$• $10,0000

4 h LC50 and Cardiac Sensitization Tests• 50 – 60 kg material = $$$$• $150,000 for tox tests

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Fire Suppression Testing Class B

Cup Burner TestingTotal Flood Tests

Class APlastic Rod TestTotal Flood Tests

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Total Flooding AgentsFire Suppression Testing

• Class B (liquid, gaseous) FuelsCup burner apparatus• Standardized apparatus (NFPA 2001/ISO 14520)

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235 mm

90 mm

535 mm

85 mm

fuel inletair/agent inlet

heater/TC

Cup Burner: Assembled View

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Total Flooding AgentsFire Suppression Testing

• Class A (solid) Fuels• UL 2166 Full-scale Tests

• Plastic Sheets (PMMA, ABS, PP)• Wood crib• 100 m3 enclosure; 50 kg per single test run

95% of clean agent applications

are Class A/Class C hazard protection

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DuPont-developed rod tests• Modification of cup burner apparatus• Plastic rod – special design• Laboratory scale : 300 g requirement• Excellent agreement with UL 2166 results

FM-200, FE-25, Novec 1230

Class A PerformanceLab Scale Method Developed

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Small Scale Total Flooding Tests

• 0.6 m3 Lexan test enclosure• Class B “pan” fire tests• Class A tests

plastic pieces (PMMA, PP, ABS)“mini wood crib”

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Toxicology• 4h LC50 > 231,000 ppm (> 23.1% v/v)• CS NOAEL = 100,000 ppm (10% v/v)• CS LOAEL = 125,000 ppm (12.5% v/v)

Fire Suppression• Class A MDC = 5.6% v/v• Class B MDC = 6.9% v/v a• Class C MDC = 6.3% v/v

Total Flooding Candidate

95% of applications

bp = 31 oC

a n-heptane

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Total Flooding Candidate• Stability

High thermal and chemical stabilityStable to water

• Material compatibilityCompatible with common metals, plastics, elastomers

• Environmental PropertiesODP = 0GWP < 20 (estimate; determination in

progress)

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Total Flooding Candidate• Inert gas solubility

• N2, Ar, CO2• Isotherms measured isotherms -10, 20, 50 oC

• Henry’s Law constants generated for -40 to 80 oC

• Thermodynamic and Transport Properties• PVT data• Fit to various equations of state

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Total Flooding Candidate

• Current Activity• Process scale-up to produce 1000 kg • Intermediate-scale fire testing• Additional material of construction

testing• GWP determination in progress

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Clean Agent DevelopmentStreaming Agents

• High mass efficiency• Chemically inert

• No reaction with water, common solvents• Long term storage stability

• Liquid or high bp gas• bp -10 to + 40 oC

• Electrically non-conducting• Toxicity

• Equal to or better than Halon 1211 or HCFC-123• Cost effective

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Portables Development Complex interaction of variables affecting

performance• Fill density• Superpressure level• Application rate• Agent droplet size• Agent quality (% mass in vapor)• Valve, nozzle, horn design• Operator technique

Design of Experiment (DOE) not applicable Brute force empirical approach to

optimization

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Portable Fire Extinguisher Design

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-DuPont Confidential-Source: NFPA 12B (1990)

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• Fill density = kg agent per volume of unit• As the fill density increases, a more rapid

decrease in the application rate and throw distance during discharge occurs

• As the fill density decreases, the application rate and throw remain more constant throughout the discharge

Portable Fire Extinguisher DesignFill Density

Low fill densities not economical; balance between economics and performance required

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Portables Development• No reliable small-scale test available

• Pan fire tests according to UL 711

• Wood crib tests according to UL 711

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Flow Visualization : PLIFConcentration, temperature, and velocity maps

Qualitative droplet size infoDischarge shapeDischarge throw

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Small droplet size:150 psig61 lb/ft3

1530 nozzle2 kg

“atomizing nozzle”

Droplets too small and light

– buoyed away from flame

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Large droplet size150 psig23 lb/ft3

2 kgH nozzle

Droplets too big- Poor fire

performance

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Sweet spot:150 psig43 lb/ft3H nozzle

2 kg

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Toxicology• 4h LC50 > 102,900 ppm (> 10.3% v/v)• CS NOAEL = 12,500 ppm (1.25 % v/v)• CS LOAEL = 25,000 ppm (2.5% v/v)

Fire Suppression• Class A MEC = 4.7% v/v• Class B MEC = 5.3% v/v a

Streaming Candidate 1bp = 31 oC

a n-heptane

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Toxicology• 4h LC50 = 120,000 ppm (12% v/v)• CS LOAEL = 25,000 ppm (2.5% v/v)

Fire Suppression• Class A MEC = 3.7% v/v• Class B MEC = 4.8 % v/v a

Streaming Candidate 2bp = 18 oC

a n-heptane

Efficiency on mass basis ~ Halon 1301

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Recent Developments in Clean Agents: Summary

• Total flooding: occupied areasDevelopment of a promising candidate based on toxicological testing and small-scale fire testing

• Suitable for use in normally occupied areas• Zero ODP• Low GWP• Low chemical reactivity

Further evaluation in progress

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Recent Developments in Clean Agents: Summary

• Streaming or Non-occupied AreasDevelopment of several promising candidates based on toxicological testing and small-scale fire testing• High mass efficiency; Candidate #2 close to Halon 1301 in

mass efficiency• Zero ODP• Low GWP• Low chemical reactivity

Further evaluation in progress

recent development in clean agent fire suppression · pdf file4 4 4 04/2009 4-dupont...

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