Hazards of Combustible Metals – Titanium
Hazards of Combustible Metals – Titanium
International Titanium Association
Kevin L. Kreitman EFO - Fire Chief, Redding CA Birmingham, UK May 2015
DISCLAIMER This presentation is for informational purposes only. In preparing and making this information available, the Author is not undertaking to render professional or other services for or on behalf of any person or entity. This presentation does not purport to address all the safety concerns. Anyone using or reviewing the presentation should rely on their own independent judgment, experience, circumstances and use extreme care and caution. Users are strongly recommended to review the latest edition of appropriate safety related materials for their location; National Fire Protection Association (NFPA) 484 Standard for Combustible Metals and referenced standards which maybe applicable; and their own National laws and standards for safety guidelines and regulations.
NIOSH Injury Report July 13, 2010
Incident Seven Career Firefighters Injured at a Titanium Metal Recycling Facility Fire Contributing Factors Unknown building contents Unrecognized presence of combustible metals Use of traditional fire suppression tactics Darkness NIOSH LODD Report Wisconsin, 12/29/09 Incident One Firefighter killed, and Eight Injured Contributing Factors Wet extinguishing agent applied to a combustible metal fire. Lack of hazardous materials awareness training. No documented site pre-plan. Insufficient scene size-up and risk assessment. Inadequate disposal/storage of materials. What Standards Do You Follow? What standards apply to your operations with regard to combustible metal operations and safety? Global Harmonized System (GHS) of Classification
Dust Explosion Hazards Work Group • Many organic materials, plastics and metals are explosible in dust form. • 281 incidents US 1980-2005 • 269 incidents Japan 1952-1995 • 159 incidents UK 1979-1988 • 72 incidents China 1981-2011 GHS Work on Combustible Dusts Sub-Committee • Workstream 3 – start discussion and develop an outline or work plan for guidance or a separate chapter in the GHS containing more detailed information on the conditions under which a dust explosion hazard could be encountered. GHS Work on Combustible Dusts Discussions • Substantial evidence that many, but not all, materials shipped present a serious hazard downstream. • CSB Study • Lack of a uniform, harmonized definition and criteria for explosible dust. • Commonalities exist that might be built upon to achieve a harmonized classification. GHS Work on Combustible Dusts Proposal • Chapter be developed, titled “Explosible Dusts” • Nano Materials • Commonalities exist that might be built upon to achieve a harmonized classification. GHS Work on Combustible Dusts Discussions • Substantial evidence that many, but not all, materials shipped present a serious hazard downstream. • CSB Study • Lack of a uniform, harmonized definition and criteria for explosible dust. • Commonalities exist that might be built upon to achieve a harmonized classification. Survey Responses GHS Definition • How should explosible dust be defined – by minimum particle size, or should definition vary for the type of dust? • Do you determine whether a dust is considered explosible by reference to published data, testing, safety data sheets (SDS’s) or other means? Please explain. Survey Responses GHS
Testing Is responsibility assigned (by law) for determining if a dust presents an explosion hazard? If so, must the person making the determination have any expertise or qualifications? Are there any prescribed tests to determine the explosibility of materials when dust form? Survey Responses GHS
Testing • Indicate what additional tests are conducted to determine the level of explosibility of a particular dust. If there are tests, are they generic or specific to the circumstances of the particular dust? Survey Responses GHS
Testing • Australia – ISO 6184 or equivalent, ASTM E 1515-93 or Kuhner 20L., IEC Standard 1241.2.1 and the equivalent Austrialian Standard. • Canada – No answer • China – Test of particle size and moisture content are conducted. Survey Responses GHS
Testing • Germany – 1518814034 1-4, EN 13821, EN 15188, EN 50281-2-1,VDI-guideline 2263 part 1. • Ireland – No test data provided • Netherlands – EN 14034 1-4, EN 13821, EN 15188, EN 50281-2-1, VDI-guideline 2263 part 1. • UK – BS EN 1382:2002, BS EN 14034-3. Survey Responses GHS
Testing • USA – ASTM E1226, ASTM E1515, ASTM E2019,. Survey Responses GHS
Standards • What standards or guides are used in your country to address explosible dust in any manner (definition, testing, hazard recognition, hazard assessment, hazard communication, mitigation methods, emergency response, investigation, etc.)? Indicate if they are used throughout your country, or in a portion (state, province, city, etc.) Survey Responses GHS
Standards • Australia/New Zealand – AS/NZS Standards are used throughout, AS/NZS 61241 series are local equivalents to the EN 61241 series. • Canada – Regulatory proposal to repeal and replace the Controlled Products Regulations to implement GHS of classification an labelling of Chemicals (GHS) in Canada, and to make consequential amendments to relate regulations. Survey Responses GHS
Standards • China – GB/T standards, in Chinese form. • Germany – Basis for all the European and German Laws, orders and regulations dealing with explosions prevention and protection are the European Atex-directives. • Ireland – no developed codes of practice or standards that deal with dust explosions. Would refer to European Standards. Survey Responses GHS
Standards • Netherlands – Directive 1999/92/EC 1999 minimum requirements for improving the safety and health protection of workers potentially at risk from explosive atmospheres. Directive 94/9/EC on the approximation of laws of the Member States concerning equipment and protective systems intended for use in potentially explosible atmospheres. Survey Responses GHS
Standards • South Africa – SANS 612421- 0:205/EC61424:10:2014 Electrical apparatus for us in the presence of a combustible dust. • UK – Standards described previously plus, EN 1127-1:2009, EN 1050:1996, EN 13463-1:2005, EN 14491:2006, EN 14460:2006, EN 14797:2006, EN 15089:2007, EN 13821:2002, EN 50281-2- 1:1998, EN 618:2002. Survey Responses GHS
Standards • USA – 29 CFR 1910.1200, 29 CFR 1910.272, 29 CFR 1910.94, 29 CFR 1910.22, 29 CFR 1910.176, 29 CFR 1910.269, 29 CFR 1910.132(a), 29 CFR 1910.307 for Class II dusts. • OSHA can enforce section 5(a)(1) of the OSHAct, if workers during inspection are found to be exposed to serious hazards, such as fire and explosion hazards and there a feasible means of abatement. • Industry consensus standards such as National Fire Protection Association (NFPA) standards may be used for potential abatement and establishing industry knowledge of the hazard. NFPA Standards
OSHA has used the following (but not limited to) NFPA Standards: • 61, 68, 69, 77, 499, 654, 664, • And 484 Standard for Combustible Metals U.S Standards - NFPA 484
Standard for Combustible Metals – Includes specific chapters on alkali metals, aluminum, magnesium, niobium, tantalum, titanium, zirconium and hafnium. – Also includes requirements for metals not listed above, that exhibit combustible metal characteristics capable of combustion or explosion. – Chapter on Recycling and Waste Management Facilities NFPA 484
U.S. References to NFPA 484 –NFPA 1 National Fire Code –International Fire Code (IFC) NFPA 484
Standard for Combustible Metals Current edition 2015 Chapter 1: Administration Chapter 4: Determination of the Combustibility or Explosibility of a Metal, Metal Powder, or Metal Dust Chapter 5: General Chapter 6: Fire Prevention, Fire Protection, and Emergency Response NFPA 484 Standard for Combustible Metals Current edition 2015 Chapter 7: Housekeeping Chapter 8: Control of Ignition Sources Chapter 9: Dust Collection Chapter 10: Performance-Based Design Option Chapter 16: Titanium Chapter 19: Recycling and Waste Management Facilities NFPA 484
Standard for Combustible Metals Chapter 16: Titanium General Provisions Facility Design Requirements Primary Metal Production Powder Production Processing and Handling Machining, Fabrication, Finishing, and Media Blasting Storage and Handling Fire and Explosion Prevention Other (Reserved) NFPA 484
Standard for Combustible Metals Chapter 6: Fire Prevention, Fire Protection, and Emergency Response Fire Prevention – Inspection and Maintenance – Control of Combustible Materials – Ordinary Combustible Storage – Removal of Combustible Metal Chips, Fines, Swarf, Paste, Powder, Dust, and Sweepings NFPA 484
• Standard for Combustible Metals Chapter 6: Fire Prevention, Fire Protection, and Emergency Response Fire Protection – Automatic Sprinkler Protection for Combustible Metals other than Alkali Metals – Sprinkler Protection of Alkali Metals – Extinguishing Agents and Application – Solvent-Wetted Powders NFPA 484
Standard for Combustible Metals Chapter 6: Fire Prevention, Fire Protection, and Emergency Response Emergency Response – Considerations – Emergency Preparedness NFPA 484
Standard for Combustible Metals Chapter 6: Fire Prevention, Fire Protection, and Emergency Response Emergency Preparedness – Notification – Emergency Preparedness Plan NFPA 484 Standard for Combustible Metals Chapter 16: Combustible Metal Recycling Facilities General Receiving Criteria Storage of Combustible Metals for Recycling Processing Emergency Preparedness Ignition Sources Waste Disposal Combustible Metal
Any metal composed of distinct particles or pieces, regardless of size, shape, or chemical composition that will burn. Chapter 4 covers determination of combustibility for metals. Determination of Combustibility & Explosivity - 484
Determination of Combustibility – UN Screening Test – Unbroken strip or powder train 250 mm long x 20 mm wide x 10 mm high Determination of Explosibility – ASTM E 1226, standard test method for explosibility of dust clouds. The ‘Rs’ of Dust Hazards
Recognition – GOOD Response – BAD Recovery – BAD Good Powder or BAD DUST
Powder is generally a product of a production operation and has value. Dust is the loss of powder from a production process. Dust that is lost from a production process is generally referred to as: FUGITIVE DUST. FUGITIVE DUST CAN KILL! Recognition of Fugitive Dust
Two simple elements of Recognition:
1. Is fugitive dust present?
2. Is the fugitive dust combustible? Fugitive Dust Explosion
To have a fire or explosion, dust has to be present and be combustible. It is easy to determine if a fugitive dust is present! How do you determine if the dust is ‘combustible’? TEST IT! Definition of Combustible Metal Dusts
Combustible Metal Dust – Any finely divided metal 420 µm (microns) or smaller in diameter (that is, material passing through a U.S. No. 40 standard sieve) that presents a fire or explosion hazard. Recognition
Three Conditions Required for a Fire: Five Conditions for a Dust Explosion
Fuel Oxygen
Confinement Dispersion
Ignition CSB Findings from Recent Dust Explosions in the U.S.
Findings
– Facilities did not fully comply with recognized guidelines and standards NFPA 484. – Many SDSs and product warnings do not adequately address dust explosion hazards. – Insurance and government inspectors did not recognize dust explosion hazards. – OSHA has limited regulations related to dust explosion hazards and has not adopted a comprehensive standard for the prevention and mitigation of dust explosions. CBS Recommendations from Recent Dust Explosions
Recommendations
– Train inspectors to recognize dust explosion hazards. – Incorporate dust explosion standards into local code requirements and federal regulations. – Create outreach programs to educate industries about dust explosion hazards. Control of Dust and Good Housekeeping Procedures are Key to Preventing Fires and Explosions Should a fire and/or explosion incident occur however, it is important to recognize the unusual hazards associated with titanium and other metals involved in fire to prevent further hazards and risks. Unusual Hazards of Combustible Metal Fires
Water when applied to burning combustible metals results in an increase in burning intensity and possible explosion, particularly if alkali metals are present.
Application of carbon dioxide has similar effects as water; the carbon dioxide adds to the intensity of the burning. Most combustible metals will ignite and burn in 100-percent carbon dioxide atmospheres. True Facts on Water Application on a Combustible Metals Fire Water applied to Titanium and non-alkali metals will disassociate to its base compounds of hydrogen and oxygen. Water applied to alkali metals, results in hydroxides and hydrogen immediately generated.
CO2 will disassociate to its base compounds. You are potentially adding the equivalent of .43 gallons of gasoline for every gallon of water applied to a combustible metals fire. Hydrogen Conversion Factor
One gallon of water weighs 8.34 lbs. Fraction of hydrogen = 11% Weight of hydrogen per gallon of water = .917 lbs Hydrogen has a heat value (BTU/lb) of about 2.8 times that of gasoline = 2.57 lbs/gallon. Gasoline has a density of 6 lbs per gallon or an equivalent of .428 gallons of gasoline applied per gallon of water. The Hydrogen Conversion Factor If you have complete disassociation of water on a combustible metals fire, you are potentially providing an additional energy component equivalent of:
– .43 gallons of gasoline per gallon of water – 100 gpm = 43 gallons of gasoline – 1000 gpm = 430 gallons of gasoline
This does not include the addition of the oxygen you are also providing to the fire. Would you consider ordering this hydrogen tanker to a fire scene and instructing your personnel to begin pumping hydrogen and oxygen on a fire? Videos – Slauson Avenue Titanium Fires – You Tu b e
http://www.youtube.com/watch?v=NDhnwLheoU4 Videos – Slauson Avenue Titanium Fires – You Tube http://www.youtube.com/watch?v=5ykseFxoWqA Unfortunately these incidents occur on a regular basis in the United States!
The Fire Service and some industries have been led to believe that if enough water is put on a combustible metals fire it can be extinguished!
When this doesn’t work, a comment like, “We were trying to accelerate the burning,” is usually made.
That comment is very accurate!
Application of water on combustible metals fires makes for great news photo opportunities. Unusual Hazards of Combustible Metal Fires Dusts, fines, and powders of combustible metals present an explosion hazard, especially if suspended or disturbed in confined spaces.
Dust, fines, and powders of titanium present extreme hazards; Static electric charges can ignite some dusts and powders of titanium. Unusual Hazards of Combustible Metal Fires Fires involving Titanium cannot be extinguished. Unless they are placed in an inert atmosphere of argon or helium, they can only be controlled. Use of Nitrogen is ineffective. Titanium powder– above 800oC (1470oF) burns readily and vigorously in atmospheres of pure nitrogen. Fires involving large quantities should be allowed to cool for at least 24 hours prior to being disturbed to prevent re-ignition. Fires will oxidize the metal. Safe Handling of Fires
A good size-up and identification of involved materials; physical state of the product, e.g. chips, powder, fines, dust, etc.; the quantity of product involved and/or potentially involved in the fire are extremely important factors for emergency responders. Obtain Safety Data Sheets for the involved products, and if available contact those familiar with the product and hazards. For fires at facilities: have someone with facility familiar with the hazards, establish and maintain direct contact with fire personnel throughout the incident. Safe Handling of Fires
Control Utilities and Process Hazards – Water Supply to the Structure – Power – Natural Gas/Propane – Industrial Gases, etc. Safe Handling of Fires
Fires beyond the incipient stage within structures can place responders at risk. Extreme caution should be taken prior to committing resources. If fires can be safely isolated, the best course of action is to allow them to burn out. Safe Handling of Fires
Uninvolved product and exposures in some cases can be protected by hose streams if adequate precautions are taken.
It is extremely important that care is taken to ensure runoff from the hose streams does not come in contact with burning and/or molten material. Safe Handling of Fires
If a fire is burning in a closed container, such as a dust collection system; and an adequate delivery system is available; with consideration taken for personnel safety, utilization of argon or helium may be effective in controlling the fire by placing an inert blanket over it.
Evaluation of explosion potential should also be considered. Safe Handling of Fires
Extreme caution needs to be taken for fires involving combustible metal powders, dusts, and fines.
Explosions are possible with these products, especially if product becomes airborne with an available ignition source.
Thin layers of dust maybe enough to produce an a flash fire hazard and/or explosive atmosphere for products under 420 µm (microns). Safe Handling of Fires
Water in contact with molten combustible metals will result in violent steam and hydrogen explosions and reactions. Large fires are impossible to extinguish. The best approach is to isolate material as much as possible, if it can be done safely. Protection of exposures with water streams can be considered, if adequate review is conducted and adequate drainage is present, to ensure contact of water with the burning material will not occur. Let the fire burn itself out naturally to minimize hazards to personnel and loss to exposures. Safe Handling of Fires
Use of Clean Agents on Class “D” fires HFC 227 ea, FK-5-1-12, HFC-125. Use Prohibited - on class “D” fires, NFPA 484 and 2001. Clean Agents will decompose between 900oF and 1500oF. Clean Agents are ineffective and may result in hazardous byproducts and exposures. Imperative Elements for the Prevention of a Dust Explosion
1. HOUSEKEEPING 2. HOUSEKEEPING 3. HOUSEKEEPING 4. HOUSEKEEPING The Majority of Combustible Metal Incidents Can be Avoided
Good housekeeping is a must. Control of Ignition sources. Adequate segregation of combustible metals. Recognition of dust hazards is a must. Not all dusts are problem dust. FUGITIVE Combustible Dust are DEADLY. Recovery Plans are an inadequate excuse for less than adequate implementation of Mitigation for known hazards. Use of water on fires is extremely hazardous and presents significant risks and dangers. Contact Information
Kevin L. Kreitman E-mail: [email protected] Phone: 1-530-921-1711