Chemical Storage: Myths vs' Reality

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Chemical StorageMyths vs. Reality

• Dave Quigley, Ph.D.
• BW Y-12
• March 5, 2008

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Why Is Chemical Storage Important?

• Mixing incompatible materials involved in a
  simple spill may cause fires, explosions,
  releases toxic or flammable gases, or other upset
  condition
• Improper storage may cause an upset condition
  without any spill
• During an upset condition, improper storage can
  make a bad situation very much worse
• Important for product quality

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Why is Chemical Storage So Difficult?

• Regulations
• Lots of Them
• 25-50 regulatory documents that define storage
  conditions
• OSHA, ANSI, NFPA, CGA, etc.
• Organized by Chemical Type
• Compressed gases, flammable liquids, oxidizers,
  organic peroxides, etc.
• Some substance specific standards
• Different Goals Behind Regulations
• OSHA, NFPA, building/fire code

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Why is Chemical Storage So Difficult? (cont.)

• Chemicals
• Lots of Them
• Several million known
• Each May Have Multiple Hazards
• Nitric acid Corrosive acid, oxidizer, toxic
• Form Counts
• Metal powders vs. metal ingots
• The World of Gray
• Little in chemistry is black or white
• Nomenclature

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Questions

• Simple Questions to Demonstrate Difficulties
• Can acids and bases be stored together?

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Questions (cont.)

• Which chemical will develop additional hazards
  upon prolonged storage?
• Chloroform
• Isopropanol
• 1M BF3 in Diethyl Ether

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Questions (cont.)

• Where is the incompatibility?
• 2,2,6-Trimethylbicyclo3.1.1hept-2-ene
• 1,1-(2,2,2-trichloroethylidene)bis4-chlorobenzen
  e
• Sodium Dichloroisocyanurate
• ?????????????????????????????????

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Questions (cont.)

• Whos the bad actor?
• Sodium Dichloroisocyanurate (swimming pool
  chlorinator/oxidizer)
• Calcium Hypochlorite (bleach/oxidizer)
• Sulfuric Acid (acid and, in some cases, oxidizer)
• Perchloric Acid (acid and oxidizer)

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HELP!!!
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Methods Available

• Compatibility Listings by Chemical Class
• Manufacturers Storage Schemes

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Compatibility Listings

• Examples
• US Coast Guard Cargo Compatibility Chart
• USEPA Method 600 Compatibility Chart
• NOAA Chemical Reactivity Worksheet

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Compatibility Listings (cont.)

• Problems Using This Method
• Chemicals with more than one hazard class
• Not all hazards listed on charts
• Not all chemicals in a hazard classification are
  compatible
• Leads to inconsistent applications between work
  areas
• Jargon causes charts to be confusing

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Manufacturers Storage Schemes

• Not consistent between manufacturers

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Manufacturers Storage Schemes (cont.)

• Incompatibilities exist within the systems
• Systems may appear the same, but are not
• Systems limited to chemicals sold by manufacturer

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But Wait, Theres More!

• Regulatory and common sense considerations not
  present in these or other schemes
• Facility limits
• Storage compatible with location
• Heating requirements

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Example 1
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Example 2
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Example 3
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Example 4
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Basics of Chemical Storage

• Know the Requirements
• Some experts not very knowledgeable
• DOE Chemical Management Handbook, Vol. 3,
  Consolidated Chemical Users Safety and Health
  Requirements
• Understand Your Facility Limits

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Basics of Chemical Storage (cont.)

• Secure Chemical Storage Areas
• Keeps untrained and dangerous people out
• Essential for accurate inventories
• Maintain control of different chemical types
• Drug precursors
• Controlled substances
• Recognize Time-Sensitive Chemicals
• Signage
• Develop Storage Strategy

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Storage Strategy

• First Classify all chemical present
• Include process to classify new chemicals
• Obtain help for making classifications
• Chemist would be useful
• Hazard classifications indicate storage area
  requirements
• Need to understand the intent of regulations to
  solve contradictions
• Help required for chemicals with multiple hazards

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Storage Strategy (cont.)

• Second Determine Appropriate Storage Areas
• Size
• Easy for small inventories, difficulty increases
  with inventory size
• Chemical types and building will help define
  storage area size
• Avoid cramped areas

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Storage Strategy (cont.)

• Second Determine Appropriate Storage Areas
  (cont.)
• Compatibility
• Temperature controlled
• Shelving material
• Sprinklered vs. nonsprinklered areas
• Compatibility of adjacent containers

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Storage Strategy (cont.)

• Second Determine Appropriate Storage Areas
  (cont.)
• Ventilation
• Special requirements for toxic gases or other
  chemicals over de-minimus quantities
• Minimum air exchanges required
• Air return required near floor
• Air recirculation may be prohibited
• Negative pressure might be needed

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Storage Strategy (cont.)

• Second Determine Appropriate Storage Areas
  (cont.)
• Other Considerations
• Anchored shelves
• Illumination
• Spill containment
• Room for refrigerators, storage cabinets, glove
  boxes, etc.
• Other requirements if dispensing is allowed

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Storage Strategy (cont.)

• Third Determine Compatibility Scheme
• Classify all chemicals according to the scheme
• Develop compatibility scheme based upon chemical
  hazards and classify chemicals present according
  to the scheme
• Complications increase with inventory size
• Not all chemicals in a compatibility group will
  compatible
• Sort by compatibility group and look for
  incompatibilities present

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Storage Strategy (cont.)

• Fourth Publish Chemical Compatibility
  Classifications
• Publish in easy-to-find location
• Do not provide workers with the option to figure
  it out for themselves
• Leads to errors
• Dictate compatibility groupings?
• Required to maintain control over the inventory?

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Credits

• Lydia Boada-Clista, Office of Logistic Management
• David Freshwater, NA 41
• J. C. Laul
• Dave Quigley, Y-12
• Janeen Robertson, LLNL
• Fred Simmons, WSR
• Helena Whyte, LANL
• Manuscript published in J. Chem. Hlth Safety

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Storage Strategy (cont.)

• Fifth Develop a Time-Sensitive Chemical Program
• See DOE Chemical Safety home page for three
  articles on how this is done
• 6 elements
• Identification Tracking
• Storage Inspection periods
• Defining safe Managing unsafe
• chemicals

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Storage Strategy (cont.)

• Sixth Feedback
• Important to measure programs health
• Stop problems before they become insurmountable
• Getting feedback also gets backing by users

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Disclaimer

• This work of authorship and those incorporated
  herein were prepared by Contractor as accounts of
  work sponsored by an agency of the United States
  Government. Neither the United States Government
  nor any agency thereof, nor Contractor, nor any
  of their employees, makes any warranty, express
  or implied, or assumes any legal liability or
  responsibility for the accuracy, completeness,
  use made, or usefulness of any information,
  apparatus, product, or process disclosed, or
  represents that its use would not infringe
  privately owned rights. Reference herein to any
  specific commercial product, process, or service
  by trade name, trademark, manufacturer, or
  otherwise, does not necessarily constitute or
  imply its endorsement, recommendation, or
  favoring by the United States Government or any
  agency or Contractor thereof. The views and
  opinions of authors expressed herein do not
  necessarily state or reflect those of the United
  States Government or any agency or Contractor
  thereof.