Chemical Reactivity Hazard Identification

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Chemical Reactivity Hazard Identification

• Scott Berger
• Center for Chemical Process Safety
• Presentation to DOE/EFCOG,
• March 9, 2005
• scotb_at_aiche.org
• 212-591-7237

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About CCPS

• Formed in 1985 as Chemical Engineering
  professions response to Bhopal incident and many
  others
• Organized within American Institute of Chemical
  Engineers
• More than 70 sponsor companies and organizations

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Mission of CCPS

• Eliminate catastrophic process safety incidents
  by
• Advancing state-of-the-art in process safety
  technology management practices
• Serving as a premier resource for PS information
• Fostering PS in engineering education
• Promoting PS as a key industry value

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CCPS is

• 3M
• ABB Lummus
• Abbott Laboratories
• ABS Group
• AcuTech
• Advantica
• Air Products Chemicals
• AIU Energy/Starr Tech
• AKZO Nobel Chemicals
• Albemarle
• Arch Chemicals
• ATOFINA Chemicals
• Baker Engineering
• Bayer Matl Science
• Buckman Laboratories
• BP
• Bristol-Myers Squibb
• Celanese Chemicals

ChevronTexaco Ciba ConocoPhillips Contra Cost
County Health Services CYTEC Degussa DNV Dow
Chemical DuPont Company Eastman Chemical Eastman
Kodak Eli Lilly ExxonMobil Fluor Enterprises FM
Global FMC Formosa Plastics GE Advanced Matl
Georgia Pacific Honeywell International Specialty
Products Intel ioMosaic JohnsonJohnson Johnson
Polymer KBR LanXess Lubrizol Lyondell Marsulex Me
rck Monsanto NOVA Occidental Olin Pioneer
PPG Primatech Reilly Industries Rhodia RRS Rohm
and Haas Sartomer Schering-Plough Shell SIS
Tech Solutions Solutia Sunoco Syncrude Canada
Syngenta TNO US Chemical Safety Board US
EPA/OEM Westinghouse Savannah River Company
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• Monthly Process Safety lessons for operators
• www.aiche.org/ccps/ safetybeacon.htm
• Its free!

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A World Without Reactive Chemistry
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A World Without Reactive Chemistry
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A World Without Reactive Chemistry
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A World Without Reactive Chemistry
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A World Without Reactive Chemistry
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A World Without Reactive Chemistry
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A World Without Reactive Chemistry
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A World Without Reactive Chemistry
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A World Without Reactive Chemistry
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A World Without Reactive Chemistry
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A World Without Reactive Chemistry
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Excuse me, Scott

• We dont run chemical reactions on DOE sites
• So we cant have any chemical reactivity issues,
  can we?

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Do you?

• Transport, store, dispense, or repackage chemical
  substances?
• Mix, blend, compound, heat, distill, extrude or
  otherwise process chemical substances?
• Cure, neutralize, acidify, or bleach chemical
  substances or using chemical substances?
• Carry out synthetic chemistry?

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If so

• You may have chemical reactivity hazards.
• Please postpone checking your voice mail

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At least one
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But first, a word fromour sponsors
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29 CFR 1910.1200Hazcom

• (g)(1) MSDS Chemical manufacturers and
  importers shall obtain or develop a material
  safety data sheet shall contain at least the
  following information
• (g)(2)(iii) The physical hazards of the hazardous
  chemical, including the potential for fire,
  explosion, and reactivity
• (h)(3) "Training." Employee training shall
  include at least
• (h)(3)(ii) The physical and health hazards of the
  chemicals in the work area
• (h)(3)(iii) The measures employees can take to
  protect themselves from these hazards, including
  specific procedures the employer has implemented
  to protect employees from exposure to hazardous
  chemicals, such as appropriate work practices,
  emergency procedures, and personal protective
  equipment

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29 CFR 1910.11940 CFR 68

• General duty clauses
• assure that all dangerous chemicals are stored
  and handled with an appropriate level of care.
• (To comply with the general duty clause)
• identify hazards that may result
• design, maintain, and operate a safe facility
• minimize the consequences of accidental releases
  which might occur

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Regulatory Problems

• Very loose interpretation of MSDS provision
• MSDSs vary greatly in quality and completeness
• Guidance re protective measures for reactivity
  not provided
• Reactivity hazards not explicit in PSM or RMP
• For guidance
• OSHA reactivity alliance
• http//www.osha.gov/SLTC/reactivechemicals/
• OSHA and EPA offer CCPS book Essential
  Practices as a resource.

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• www.AIChE.org/CCPS/Resources.htm

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We now return to our regularly scheduled
programming
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Do you have chemical reactivity hazards to
manage? Lets find out.From Essential
Practices for Managing Chemical Reactivity
Hazards, Figure 3.1
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Do you perform intentional chemistry?
1. Is Intentional Chemistry Performed?
Yes
Start
No
5. Is combustion in air the only chemistry
performed?
Yes
Next slide

• Synthetic reactions
• Neutralization
• Bleaching (oxidation)
• Decomposition
• Heat treatment
• Pickling
• (Above not a complete list)

Anticipate chemical reactivity hazards
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Pay particular attention if

• Certain functional groups present
• Heat of reaction gt 100 cal/g under reasonable,
  foreseeable conditions
• Even if reaction rate is slow
• By measurement or calculation
• Includes diluents
• Account for gas generation
• Absence of these factors doesnt mean no
  reactivity hazard

• Example groups
• Peroxides
• Acetylenics
• Nitroso cpds
• Nitrates
• Epoxides
• Azides
• Halogen oxides
• Alkenes

http//www.nj.gov/dep/enforcement/relprev/tcpa/t
cparulefinal.pdf
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Could you be performing unintentional chemistry?
No intentional chemistry other than combustion in
air
2. Mixing or combining Substances?
No

• Look for clues
• Heat, even just a little bit or only occasionally
• pH change
• Color change
• Curing / setting

3. Any other physical processing?

Yes
Yes
6. Is heat generated during mixing or processing?
No
Continue
No
Anticipate chemical reactivity hazards
Yes
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No chemistry, no physical processing, no heat
4. Any hazardous substances?
Any 7. pyrophoric? 8. peroxide former?
Yes
Yes
No

• Look at MSDS, then look at another
• Look at NFPA diamond
• Red-Reactivity
• 4 May detonate
• 3 Shock/heat sensitive
• 2 Other violent reaction
• 1 Unstable if heated
• White-Special
• Oxy Oxidizer
• W Water reactive

Any 9. water reactive? 10. oxidizer
Anticipate chemical reactivity hazards
Yes
No
Any 11. self reactive? (polymerize, decomp.)
Yes
Continue
No
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Storage

• Supplier should provide maximum storage
  temperature
• If not, store material at least 50 oF below the
  adiabatic onset temperature
• Also see
• NFPA 49 and 325 (instability)
• NFPA 430 (oxidizers)
• NFPA 432 (peroxide formers)
• NFPA 491 (incompatibility)

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No other hazards

• Prepare interaction matrix

12. Hazardous interactions?
No
Yes
Anticipate chemical reactivity hazards
Find out what cleaning solution contains, then
determine reactions
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Interaction resources

• NFPA 491
• NOAA worksheet http//response.restoration.noaa.g
  ov/chemaids/react.html
• Brethericks Handbook of Reactive Chemical Hazards

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Summary

• If you use chemicals, consider seriously the
  possibility of reactivity hazards
• The MSDS is your friend
• You need all the friends you can get
• Consult a second MSDS
• Check other resources
• Dennis Hendershot will discuss how to manage
  reactivity hazards

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Thank you!

• Any Questions?