Post on 07-Feb-2018
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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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Automatic Sprinkler System
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Automatic Sprinkler System
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After…..
Automatic Sprinkler System
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Automatic Sprinkler System
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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Halogenated Compounds as Fire Suppression Agents
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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Halogenated Compounds as Fire Suppression Agents
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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• 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