Reactive Hazards Webinar September 15, 2008
<ul><li>Reactive properties and physical conditions of a single chemical or mixture that have the potential to generate he...
CSB Reactive Hazard Investigation <ul><ul><li>167 incidents since 1980 </li></ul></ul><ul><ul><li>108 fatalities </li></ul...
Severe Reactive Chemical Incidents 4 12/13/94 Port Neal IA 6 5 2/19/99 Allentown PA 5 5 4/21/95 Lodi NJ 4 8 5/1/91   Sterl...
Severe Reactive Chemical Incidents 3 3/13/01 Augusta, GA 12 3 5/8/97   West Helena AR 11 3 5/27/94   Belpre OH 10 3 6/12/8...
Types of Reactive Hazards <ul><li>Reactive Materials </li></ul><ul><li>Reactive Interactions </li></ul>
Reactive Materials <ul><li>Unstable  – Has a tendency to break down over time or when exposed to certain conditions. </li>...
Reactive Materials <ul><li>Polymerizing  – Has the tendency to self-react to form larger molecules, while possibly generat...
Reactive Materials <ul><li>Pyrophoric  – Will ignite spontaneously when exposed to air. </li></ul>Photo from unknown origin
Reactive Materials <ul><li>Peroxide Former  – Has the tendency to slowly react with oxygen, such as when exposed to air, t...
Reactive Materials <ul><li>Water Reactive  – Will react violently with water or moisture.  Heat and flammable/toxic gases ...
Reactive Materials <ul><li>Oxidizer  – Will give up oxygen easily or readily oxidize other materials. </li></ul>
Reactive Interactions <ul><li>Intentional Reactions </li></ul><ul><li>GA Pacific Resins Columbus, OH </li></ul><ul><li>Rea...
Reactive Interactions <ul><li>Contamination </li></ul><ul><li>Pool Chemical Fire Springfield, MA  June 1989 </li></ul><ul>...
Reactive Interactions <ul><li>Conditions </li></ul><ul><li>Bartlo Packaging West Helena, AR May 8, 1997 </li></ul><ul><li>...
Reactive Interactions <ul><li>Unintentional Mixing </li></ul><ul><li>Confusion over common chemical name </li></ul><ul><li...
What Chemicals are most often involved in Reactive Incidents? Source: CSB CSB Investigation of Reactive Incidents 79 Other...
What Types of Reactions cause Reactive Incidents? Source: CSB CSB Investigation of Reactive Incidents 8 Other 4 Oxidation/...
Where Do Reactive Incidents Occur? Source: CSB CSB Investigation of Reactive Incidents Transfer   Equipment 5% Reactor 25%...
Where Do Reactive Incidents Occur? Source: CSB CSB Investigation of Reactive Incidents Nearly 30% Storage, Handling, Consu...
What are the Consequences of Reactive Incidents? Source: CSB CSB Investigation of Reactive Incidents 37% Toxic Gas Release...
Identifying Reactive Hazards Identifying Reactive Hazards
Identifying Reactive Hazards <ul><li>MSDSs </li></ul><ul><li>Literature </li></ul><ul><li>Computer tools </li></ul><ul><li...
MSDS Reactivity Information – 1 <ul><ul><li>MSDSs should have a “reactivity” or “stability and reactivity” section noting ...
MSDS Reactivity Information – 2 <ul><ul><li>May  include overview of gross incompatibilities </li></ul></ul><ul><ul><ul><l...
Literature – Data Compilations <ul><li>Urben, P.G. (ed.) 2006.  Bretherick’s Handbook of Reactive Chemical Hazards . Acade...
Literature – Control of Reactive Hazards <ul><li>CCPS, 2003.  “Essential Practices for   Managing Chemical Reactivity Haza...
Computerized References <ul><li>NOAA  Chemical Reactivity Worksheet (version 1.9.2 current) - interactions </li></ul><ul><...
Compatibility / Chemical Interaction  Charts -1 Determine cleaning solution contents, e.g., ammonia, then determine reacti...
Compatibility / Chemical Interaction  Charts -2 <ul><li>Interaction hazards may not be obvious!   </li></ul><ul><ul><li>Ma...
Compatibility / Chemical Interaction  Charts - 3 <ul><li>Charts are a good practice:   </li></ul><ul><ul><li>Display possi...
Compatibility / Chemical Interaction  Charts - 4 <ul><li>May require testing to develop </li></ul><ul><li>Don’t tell the w...
Compatibility / Chemical Interaction  Charts - 5 <ul><li>Charts require a long-term commitment to maintain as processes ch...
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Osha Reactives

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  • Osha Reactives

    1. 1. Reactive Hazards Webinar September 15, 2008
    2. 2. <ul><li>Reactive properties and physical conditions of a single chemical or mixture that have the potential to generate heat, energy, and gaseous by-products that have the potential to do harm. </li></ul>Reactive Hazard Definition from CSB
    3. 3. CSB Reactive Hazard Investigation <ul><ul><li>167 incidents since 1980 </li></ul></ul><ul><ul><li>108 fatalities </li></ul></ul><ul><ul><li>5 fatalities per year (average) </li></ul></ul><ul><ul><li>50 incidents with public impact </li></ul></ul>
    4. 4. Severe Reactive Chemical Incidents 4 12/13/94 Port Neal IA 6 5 2/19/99 Allentown PA 5 5 4/21/95 Lodi NJ 4 8 5/1/91 Sterlington LA 3 9 6/17/91 Charleston SC 2 17 7/5/90 Channelview TX 1 Fatalities Date Location
    5. 5. Severe Reactive Chemical Incidents 3 3/13/01 Augusta, GA 12 3 5/8/97 West Helena AR 11 3 5/27/94 Belpre OH 10 3 6/12/86 Barceloneta Puerto Rico 9 3 6/2/82 Gulfport MS 8 4 6/28/88 Auburn IN 7 Fatalities Date Location
    6. 6. Types of Reactive Hazards <ul><li>Reactive Materials </li></ul><ul><li>Reactive Interactions </li></ul>
    7. 7. Reactive Materials <ul><li>Unstable – Has a tendency to break down over time or when exposed to certain conditions. </li></ul>STABILITY
    8. 8. Reactive Materials <ul><li>Polymerizing – Has the tendency to self-react to form larger molecules, while possibly generating enough heat/gases to burst a container. </li></ul>Photo from BP Amoco Augusta GA 2001 Explosion
    9. 9. Reactive Materials <ul><li>Pyrophoric – Will ignite spontaneously when exposed to air. </li></ul>Photo from unknown origin
    10. 10. Reactive Materials <ul><li>Peroxide Former – Has the tendency to slowly react with oxygen, such as when exposed to air, to form unstable organic peroxides. </li></ul>Photo from Lawrence Berkley National Laboratory Website
    11. 11. Reactive Materials <ul><li>Water Reactive – Will react violently with water or moisture. Heat and flammable/toxic gases may be produced. </li></ul>
    12. 12. Reactive Materials <ul><li>Oxidizer – Will give up oxygen easily or readily oxidize other materials. </li></ul>
    13. 13. Reactive Interactions <ul><li>Intentional Reactions </li></ul><ul><li>GA Pacific Resins Columbus, OH </li></ul><ul><li>Reactor vessel rupture </li></ul><ul><li>All raw materials & catalysts charged at once </li></ul><ul><li>Runaway reaction </li></ul><ul><li>Exceeded relief system </li></ul><ul><li>Exceeded cooling capacity </li></ul>
    14. 14. Reactive Interactions <ul><li>Contamination </li></ul><ul><li>Pool Chemical Fire Springfield, MA June 1989 </li></ul><ul><li>Rainwater leaked into a room contaminating pool chemicals </li></ul><ul><li>Heat and chlorine released </li></ul>USFA Technical Report Series
    15. 15. Reactive Interactions <ul><li>Conditions </li></ul><ul><li>Bartlo Packaging West Helena, AR May 8, 1997 </li></ul><ul><li>Bulk storage & distribution center </li></ul><ul><li>Bulk sacks of pesticide stored too close to compressor discharge pipe </li></ul><ul><li>Decomposition released flammable vapor </li></ul>Rick McFarland, Arkansas Democrat-Gazette
    16. 16. Reactive Interactions <ul><li>Unintentional Mixing </li></ul><ul><li>Confusion over common chemical name </li></ul><ul><li>Truck of sodium hydrosulfide unloaded into ferrous sulfate tank </li></ul><ul><li>Hydrogen sulfide released </li></ul>Lisa Medendorp, The Chronicle Whitehall Leather Whitehall, MI June 4, 1999
    17. 17. What Chemicals are most often involved in Reactive Incidents? Source: CSB CSB Investigation of Reactive Incidents 79 Other 6 Hydrosulfite 6 Inorganic/metal 7 Hydrocarbon 8 Alcohol 10 Hypochlorite 12 Organic Peroxide 12 Base 14 Water 15 Monomer 20 Oxidizer 38 Acid No. of Incidents Chemical Class
    18. 18. What Types of Reactions cause Reactive Incidents? Source: CSB CSB Investigation of Reactive Incidents 8 Other 4 Oxidation/Reduction 5 Decomp by another reaction 6 Oxidation 10 Polymerization 10 Water Reactive 11 Acid/Base 26 Decomposition Percentage Reaction Type
    19. 19. Where Do Reactive Incidents Occur? Source: CSB CSB Investigation of Reactive Incidents Transfer Equipment 5% Reactor 25% Storage Equipment 22% Other Process Equipment 22% Separation Equipment 5% Unknown 8% Storage Drum 10% Waste Equipment 3%
    20. 20. Where Do Reactive Incidents Occur? Source: CSB CSB Investigation of Reactive Incidents Nearly 30% Storage, Handling, Consumer Sites 70% + Chemical Manufacturing Percent of Incidents Type of Facility
    21. 21. What are the Consequences of Reactive Incidents? Source: CSB CSB Investigation of Reactive Incidents 37% Toxic Gas Release 16% Fire/explosion and toxic release 5% Hazardous liquid spill 42% Fire/explosion Percent of Incidents Consequence
    22. 22. Identifying Reactive Hazards Identifying Reactive Hazards
    23. 23. Identifying Reactive Hazards <ul><li>MSDSs </li></ul><ul><li>Literature </li></ul><ul><li>Computer tools </li></ul><ul><li>Compatibility Charts </li></ul><ul><li>Testing </li></ul><ul><ul><li>Stability testing </li></ul></ul><ul><ul><li>Reactive Interaction Screening </li></ul></ul><ul><ul><li>Reaction calorimetry </li></ul></ul><ul><ul><li>Adiabatic calorimetry </li></ul></ul><ul><li>Multiple data sources are almost always needed! </li></ul>
    24. 24. MSDS Reactivity Information – 1 <ul><ul><li>MSDSs should have a “reactivity” or “stability and reactivity” section noting if materials are: </li></ul></ul><ul><ul><ul><li>Unstable (decomposing) </li></ul></ul></ul><ul><ul><ul><li>Self-reactive (polymerizing) </li></ul></ul></ul><ul><ul><ul><li>Pyrophoric </li></ul></ul></ul><ul><ul><ul><li>Peroxide formers </li></ul></ul></ul><ul><ul><ul><li>Oxidizers </li></ul></ul></ul><ul><ul><ul><li>Water reactive </li></ul></ul></ul>
    25. 25. MSDS Reactivity Information – 2 <ul><ul><li>May include overview of gross incompatibilities </li></ul></ul><ul><ul><ul><li>Oxidizers / Organic materials </li></ul></ul></ul><ul><ul><ul><li>Bases / Acids </li></ul></ul></ul><ul><ul><li>Heat sensitivity </li></ul></ul><ul><ul><li>Shock sensitivity </li></ul></ul><ul><ul><li>Level of detail in, and reliability of, MSDSs can vary greatly! </li></ul></ul><ul><ul><li>Don’t rely ONLY on MSDS reactivity data! </li></ul></ul>
    26. 26. Literature – Data Compilations <ul><li>Urben, P.G. (ed.) 2006. Bretherick’s Handbook of Reactive Chemical Hazards . Academic Press. </li></ul><ul><li>Lewis, R.J. 2004. Sax’s Dangerous Properties of Industrial Materials. Wiley-Interscience. </li></ul>
    27. 27. Literature – Control of Reactive Hazards <ul><li>CCPS, 2003. “Essential Practices for Managing Chemical Reactivity Hazards” , New York: AIChE. </li></ul><ul><li>(available for free download from http://info.knovel.com/ccps/ ) </li></ul><ul><li>HSE 2000. “Designing and Operating Safe Chemical Reaction Processes”. UK Health and Safety Executive </li></ul>
    28. 28. Computerized References <ul><li>NOAA Chemical Reactivity Worksheet (version 1.9.2 current) - interactions </li></ul><ul><ul><li>http://response.restoration.noaa.gov/ </li></ul></ul><ul><ul><li>Click on “responding to chemical spills”, then “The Chemical Reactivity Worksheet” </li></ul></ul><ul><li>ASTM “CHETAH” package can estimate reactive energy releases </li></ul><ul><ul><li>May require expert assistance </li></ul></ul>
    29. 29. Compatibility / Chemical Interaction Charts -1 Determine cleaning solution contents, e.g., ammonia, then determine reactions! Cleaning Solution REACTIVE Not Reactive Not Reactive Not Reactive Lube Oil REACTIVE REACTIVE REACTIVE Sulfuric Acid REACTIVE Not Reactive Water REACTIVE Acetic Anhydride Acetic Acid Cleaning Solution Lube Oil Sulfuric Acid Water Acetic Anhydride Acetic Acid Reaction Possible?
    30. 30. Compatibility / Chemical Interaction Charts -2 <ul><li>Interaction hazards may not be obvious! </li></ul><ul><ul><li>Materials may individually be stable, but violently reactive with each other </li></ul></ul><ul><ul><ul><li>sulfuric acid </li></ul></ul></ul><ul><ul><ul><li>caustic </li></ul></ul></ul>
    31. 31. Compatibility / Chemical Interaction Charts - 3 <ul><li>Charts are a good practice: </li></ul><ul><ul><li>Display possible interactions at a glance </li></ul></ul><ul><ul><li>Good guide for storage, mixing, disposal </li></ul></ul><ul><ul><li>May be able to develop using the free NOAA program, literature </li></ul></ul><ul><ul><li>Many employers will have at least a partial chart for reactive processes </li></ul></ul>
    32. 32. Compatibility / Chemical Interaction Charts - 4 <ul><li>May require testing to develop </li></ul><ul><li>Don’t tell the whole story: </li></ul><ul><ul><li>Will materials generate gases / high pressures? </li></ul></ul><ul><ul><li>Can an explosion occur? </li></ul></ul><ul><ul><li>Are products of reaction toxic? </li></ul></ul><ul><ul><li>Generally based on ambient conditions, not process temperatures and pressures </li></ul></ul>
    33. 33. Compatibility / Chemical Interaction Charts - 5 <ul><li>Charts require a long-term commitment to maintain as processes change over time </li></ul><ul><li>May not be comprehensive </li></ul><ul><li>May not address issues of contamination, complex mixtures, and materials of construction incompatibilities </li></ul>

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