Integrated Safety Management at PNNL

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Integrated Safety Management at PNNL

• A Success Story of Handling
• Pyrophoric Reagents

Mikhail Alnajjar, Ph.D. Chemical Hygiene
Officer Patti Ammonet Lessons Learned/Operating
Experience Program Manager
Presented at EFCOG 2010 Safety Analysis
Workshop April 28, 2010
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Handling Pyrophoric Reagents

• Acknowledgement
• Jason Armstrong
• Cindy Caldwell
• Todd Haynie
• Tim Bays, John Linehan, Aaron Appel, Tim Hubler,
  Michael Bates, Andy Minister
• Neal Langerman

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Initiating event UCLA pyrophoric accident and
researcher death caused us to ask questions

• Could it happen in our lab are we vulnerable?
• Are our labs equipped to handle pyrophorics?
• Are researchers knowledgeable of correct
  protocols?
• Are existing systems and controls adequate for
  planning and performing work when pyrophorics are
  involved?
• Do we have adequate training for those working
  with pyrophorics?
• PNNLs dynamic process we addressed short-term
  actions and plan for long-term improvement efforts

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To be proactive toward prevention and
dissemination of information to staffA shared
goal between Workers Safety and Health and
Lessons Learned / OE Program where
Our actions
This collaborative effort proved to be very
effective and aligns well with Integrated Safety
Management (ISM) functions (to be
discussed in later slides)
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Pyrophoric Reagents

• Represent a unique class of reactants
• They participate in many different types of
  reactions
• They are very useful in organic synthesis
• They play an important role in industrial
  applications

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Handling Pyrophoric Reagents

• Definition
• According to Occupational Safety and Health
  Administration (OSHA) and National Fire
  Protection Association (NFPA)
• Pyrophorics as substances that will
  self-ignite in air at temperatures of 130F
  (54.4C) or less
• According to U.S. Department of Transportation
  (DOT)
• Pyrophorics as Substances (liquid or solid)
  that, even in small quantities and without an
  external ignition source, can ignite within five
  minutes after coming in contact with air

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Handling Pyrophoric Reagents

• Due to their Inherent Nature,
• Pyrophorics (gases, solids, and Liquids) Ignite
  Spontaneously upon exposure to air
• Therefore,
• Special precautions must be taken to ensure
  their safe handling and use

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Handling Pyrophoric Reagents

• Three Types of Pyrophorics
• 1) Gases (diborane, phosphine, arsine,
  silane)
• These are easiest class of Pyrophorics to handle
  because the gas can be connected directly to the
  application and use remotely.

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Handling Pyrophoric Reagents

• Three Types of Pyrophorics
• 2) Solids
• A) Finely divided metals (Fe, Mg, U)
• B) Alkali metals (Li, Na, K, Na-K Alloy)
• C) Metal hydrides (LiAlH4, KH, UH3)
• D) Others (Ni-carbonyl, Raney Ni, FeS, FeS2,
  K2S, etc)
• KO2 (superoxide) forming on the surface of the
  metal is shock-sensitive and can explode when
  handled or cut.

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Handling Pyrophoric Reagents

• Three Types of Pyrophorics
• 3) Liquids
• A) Pure liquids (diethylzinc, triethylborane,
  tributylphosphine, hydrazine hypergolic and
  used in rocket fuel an explosives)
• B) Solutions (alkyl metals such as
  Methyllithium, n-Butyllithium, t-Butyllithium)
• The alkyl metals are usually dissolved in
  pentane, hexane, diethyl ether, or THF

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Handling Pyrophoric Reagents

• Objectives
• A brief discussion on proper techniques for
  disposal
• A brief discussion on proper techniques for
  storage
• Illustrate best practices for handling this class
  of reagents
• Answer any questions you may have
• Overall goal to provide guidelines and general
  safety precautions to avoid serious or fatal
  injury.

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Handling Pyrophoric Reagents

• General Precautions
• Do not work alone (use the Buddy System)
• Safety glasses, fire-retardant coats gloves
  should be mandatory along with chemically-resistan
  t gloves when appropriate
• Wear Natural fiber clothing if possible.
  Synthetic materials tend to melt instead of
  charring when exposed to high heat.
• In case of emergency, use the safety shower or a
  fire blanket. Stop, drop, and roll may come
  handy at times
• Read the manufacturers MSDS and understand the
  technical information within or find
  experienced staff
• Work must be performed inside a (clean) Fume Hood
  with the sash down for protection from chemical
  splashes

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Handling Pyrophoric Reagents

• General Precautions
• The bottle should be secured to a stand with a
  clamp before use to prevent from tipping over
• Ensure that the assembly is purged and maintained
  under an inert atmosphere
• When extracting liquid pyrophoric from a reagent
  bottle, use a Luer-lock airtight glass syringe
  with a wide bore. Note Needle with gauge 18 or
  larger is preferred.
• Practice the experimental technique with
  non-hazardous materials to refine the technique
  and build confidence
• When Possible, use oxygen FREE gloveboxes

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Disposal of Pyrophoric Reagents---liquids and
Solids---

• Syringes, double-tipped needles, spatulas, and
  reaction assembly, should be rinsed with an inert
  solvent
• Excess reagents should be diluted with an inert
  solvent
• The rinsates are transferred to a flask under an
  inert atmosphere and cooled in a cooling bath
  (DMK/CO2)
• Start the neutralization by slowly adding
  isopropyl alcohol (IPA)
• Follow the addition of IPA with methanol (a
  stronger neutralization solvent)
• Finally, add copious amounts of water or dilute
  acid if needed to insure that neutralization is
  complete
• Dispose of the waste safely in accordance with
  requirements or organizations waste disposal
  process

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Storage of Pyrophoric Reagents

• Typically keep away from heat and ignition
  sources, flammable and combustible materials,
  oxidizers, air, and water/in case of water
  reactive Pyrophorics.
• Solids Are stored as suspensions or chunks in
  mineral oil or under an inert atmosphere of dry
  Nitrogen or Argon
• Liquids Are stored under an inert atmosphere of
  dry Nitrogen or Argon

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Handling Pyrophoric Reagents---Syringe
Transfer---

• Syringe Transfer Assembly Equipped with an Inert
  Gas Line and a Bubbler during Reagent Transfer

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Handling Pyrophoric Reagents---Syringe
Transfer---

• Syringe Transfer Assembly with Inert Gas Line
  (1), Bubbler (2), Secure Reagent Bottle (3), and
  Fire Resistant Gloves

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Handling Pyrophoric Reagents---Syringe
Transfer---

• Transfer Assembly in Fume Hood (1) Fire resistant
  pilot glove (2) Fire resistant lab coat (3)
  safety glasses with side shield.
• Note Sash has been lowered to reduce potential
  splash hazards.

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Handling Pyrophoric Reagents---Double-Tipped
Needle Transfer---

• Double-Tipped Needle Assembly Equipped with a
  Bubbler and Kept Under an Inert Atmosphere
  during Reagent Transfer

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Our actions align with ISM functions shared
commitment to integrated safety and prevention
Evaluating work planning process for improvements
to working with chemicals
Provide e-chemical process permits assess
chemical hazards to assure greater safety in the
workplace
Developed detailed pyrophoric protocols
Update train staff
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Prevention a shared goal between the CHO and
Lessons Learned / OE Program
Provide feedback and improvement

• Shared beyond PNNL
• Adopted as a new standard
• Invited to the American Chemical Society Workshop
• Shared with EFCOG
• Published in the Journal of Chemical Health
  Safety

• Issued PNNL lessons learned
• promoted discussion among researchers
• provided updated guidelines
• discussed in Lab safety councils

• Detailed pyrophoric guidelines
• updated Lab processes/procedures
• basis for new training
• updated LL and links

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Methods for the Safe Storage, Handling, and
Disposal of Pyrophoric Liquids and Solids in the
Laboratory

• Mikhail Alnajjar, Dave Quigley, Fred Simmons,
  Murty Kuntamukkula, David Freshwater, and Samuel
  Bigger
• e-mail ms.alnajjar_at_pnl.gov
• Published in the Journal of Chemical Health
  Safety
• (Publication)

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Handling Pyrophoric Reagents

• Thank you
• Questions???
• Comments!!!