Reactive Hazards Webinar September 15, 2008

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. Reactive Hazard Definition from CSB

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.

CSB Reactive Hazard Investigation 167 incidents since 1980 108 fatalities 5 fatalities per year (average) 50 incidents with public impact

167 incidents since 1980

108 fatalities

5 fatalities per year (average)

50 incidents with public impact

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

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

Types of Reactive Hazards Reactive Materials Reactive Interactions

Reactive Materials

Reactive Interactions

Reactive Materials Unstable – Has a tendency to break down over time or when exposed to certain conditions. STABILITY

Unstable – Has a tendency to break down over time or when exposed to certain conditions.

Reactive Materials Polymerizing – Has the tendency to self-react to form larger molecules, while possibly generating enough heat/gases to burst a container. Photo from BP Amoco Augusta GA 2001 Explosion

Polymerizing – Has the tendency to self-react to form larger molecules, while possibly generating enough heat/gases to burst a container.

Reactive Materials Pyrophoric – Will ignite spontaneously when exposed to air. Photo from unknown origin

Pyrophoric – Will ignite spontaneously when exposed to air.

Reactive Materials Peroxide Former – Has the tendency to slowly react with oxygen, such as when exposed to air, to form unstable organic peroxides. Photo from Lawrence Berkley National Laboratory Website

Peroxide Former – Has the tendency to slowly react with oxygen, such as when exposed to air, to form unstable organic peroxides.

Reactive Materials Water Reactive – Will react violently with water or moisture. Heat and flammable/toxic gases may be produced.

Water Reactive – Will react violently with water or moisture. Heat and flammable/toxic gases may be produced.

Reactive Materials Oxidizer – Will give up oxygen easily or readily oxidize other materials.

Oxidizer – Will give up oxygen easily or readily oxidize other materials.

Reactive Interactions Intentional Reactions GA Pacific Resins Columbus, OH Reactor vessel rupture All raw materials & catalysts charged at once Runaway reaction Exceeded relief system Exceeded cooling capacity

Intentional Reactions

GA Pacific Resins Columbus, OH

Reactor vessel rupture

All raw materials & catalysts charged at once

Runaway reaction

Exceeded relief system

Exceeded cooling capacity

Reactive Interactions Contamination Pool Chemical Fire Springfield, MA June 1989 Rainwater leaked into a room contaminating pool chemicals Heat and chlorine released USFA Technical Report Series

Contamination

Pool Chemical Fire Springfield, MA June 1989

Rainwater leaked into a room contaminating pool chemicals

Heat and chlorine released

Reactive Interactions Conditions Bartlo Packaging West Helena, AR May 8, 1997 Bulk storage & distribution center Bulk sacks of pesticide stored too close to compressor discharge pipe Decomposition released flammable vapor Rick McFarland, Arkansas Democrat-Gazette

Conditions

Bartlo Packaging West Helena, AR May 8, 1997

Bulk storage & distribution center

Bulk sacks of pesticide stored too close to compressor discharge pipe

Decomposition released flammable vapor

Reactive Interactions Unintentional Mixing Confusion over common chemical name Truck of sodium hydrosulfide unloaded into ferrous sulfate tank Hydrogen sulfide released Lisa Medendorp, The Chronicle Whitehall Leather Whitehall, MI June 4, 1999

Unintentional Mixing

Confusion over common chemical name

Truck of sodium hydrosulfide unloaded into ferrous sulfate tank

Hydrogen sulfide released

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

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

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%

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

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

Identifying Reactive Hazards Identifying Reactive Hazards

Identifying Reactive Hazards MSDSs Literature Computer tools Compatibility Charts Testing Stability testing Reactive Interaction Screening Reaction calorimetry Adiabatic calorimetry Multiple data sources are almost always needed!

MSDSs

Literature

Computer tools

Compatibility Charts

Testing

Stability testing

Reactive Interaction Screening

Reaction calorimetry

Adiabatic calorimetry

Multiple data sources are almost always needed!

MSDS Reactivity Information – 1 MSDSs should have a “reactivity” or “stability and reactivity” section noting if materials are: Unstable (decomposing) Self-reactive (polymerizing) Pyrophoric Peroxide formers Oxidizers Water reactive

MSDSs should have a “reactivity” or “stability and reactivity” section noting if materials are:

Unstable (decomposing)

Self-reactive (polymerizing)

Pyrophoric

Peroxide formers

Oxidizers

Water reactive

MSDS Reactivity Information – 2 May include overview of gross incompatibilities Oxidizers / Organic materials Bases / Acids Heat sensitivity Shock sensitivity Level of detail in, and reliability of, MSDSs can vary greatly! Don’t rely ONLY on MSDS reactivity data!

May include overview of gross incompatibilities

Oxidizers / Organic materials

Bases / Acids

Heat sensitivity

Shock sensitivity

Level of detail in, and reliability of, MSDSs can vary greatly!

Don’t rely ONLY on MSDS reactivity data!

Literature – Data Compilations Urben, P.G. (ed.) 2006. Bretherick’s Handbook of Reactive Chemical Hazards . Academic Press. Lewis, R.J. 2004. Sax’s Dangerous Properties of Industrial Materials. Wiley-Interscience.

Urben, P.G. (ed.) 2006. Bretherick’s Handbook of Reactive Chemical Hazards . Academic Press.

Lewis, R.J. 2004. Sax’s Dangerous Properties of Industrial Materials. Wiley-Interscience.

Literature – Control of Reactive Hazards CCPS, 2003. “Essential Practices for Managing Chemical Reactivity Hazards” , New York: AIChE. (available for free download from http://info.knovel.com/ccps/ ) HSE 2000. “Designing and Operating Safe Chemical Reaction Processes”. UK Health and Safety Executive

CCPS, 2003. “Essential Practices for Managing Chemical Reactivity Hazards” , New York: AIChE.

(available for free download from http://info.knovel.com/ccps/ )

HSE 2000. “Designing and Operating Safe Chemical Reaction Processes”. UK Health and Safety Executive

Computerized References NOAA Chemical Reactivity Worksheet (version 1.9.2 current) - interactions http://response.restoration.noaa.gov/ Click on “responding to chemical spills”, then “The Chemical Reactivity Worksheet” ASTM “CHETAH” package can estimate reactive energy releases May require expert assistance

NOAA Chemical Reactivity Worksheet (version 1.9.2 current) - interactions

http://response.restoration.noaa.gov/

Click on “responding to chemical spills”, then “The Chemical Reactivity Worksheet”

ASTM “CHETAH” package can estimate reactive energy releases

May require expert assistance

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?

Compatibility / Chemical Interaction Charts -2 Interaction hazards may not be obvious! Materials may individually be stable, but violently reactive with each other sulfuric acid caustic

Interaction hazards may not be obvious!

Materials may individually be stable, but violently reactive with each other

sulfuric acid

caustic

Compatibility / Chemical Interaction Charts - 3 Charts are a good practice: Display possible interactions at a glance Good guide for storage, mixing, disposal May be able to develop using the free NOAA program, literature Many employers will have at least a partial chart for reactive processes

Charts are a good practice:

Display possible interactions at a glance

Good guide for storage, mixing, disposal

May be able to develop using the free NOAA program, literature

Many employers will have at least a partial chart for reactive processes

Compatibility / Chemical Interaction Charts - 4 May require testing to develop Don’t tell the whole story: Will materials generate gases / high pressures? Can an explosion occur? Are products of reaction toxic? Generally based on ambient conditions, not process temperatures and pressures

May require testing to develop

Don’t tell the whole story:

Will materials generate gases / high pressures?

Can an explosion occur?

Are products of reaction toxic?

Generally based on ambient conditions, not process temperatures and pressures

Compatibility / Chemical Interaction Charts - 5 Charts require a long-term commitment to maintain as processes change over time May not be comprehensive May not address issues of contamination, complex mixtures, and materials of construction incompatibilities

Charts require a long-term commitment to maintain as processes change over time

May not be comprehensive

May not address issues of contamination, complex mixtures, and materials of construction incompatibilities