Hazard Material

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Hazard Material
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Reference Essential Practices for Managing
Chemical Reactivity Hazards, by Robert W.
Johnson, Steven W.Rudy, and Stephen D. Unwin,
Center for Chemical Process Safetyof the
American Institute of Chemical Engineers? 3 Park
Avenue, New York, NY
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HAZMAT

• Hazardous Material ????????????
• ??????? ????????????????????????? ???????????
  ???????????????????

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????? ????????????????????????????????
?????????????????????????????????? ???? ??????
????????? ?????????????Chlorine bleach
Ammonia-based cleaner ?????
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..??????- ????????????????????????????
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Lesson learns from past - The 1976 runaway
reaction at Seveso, Italy that resulted in the
contamination of several square miles of land
with dioxin. - The 1984 methyl isocyanate
release in Bhopal, India that resulted in 2000
fatalities -The 2001 massive ammonium nitrate
explosion near Toulouse, France that led to 30
fatalities, 2500 injuries, damage to nearly a
third of the city of Toulouse, and the permanent
closing of the facility.
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Essential Practices for Managing Chemical
Reactivity Hazards, by Johnson et al., Center
for Chemical Process Safety of the AIChE
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Storage Incident Springfield, Massachusetts,
June 17, 1988 Rainwater leaked into a room where
hundreds of large cardboard drums of solid
swimming pool chemicals were stored. The
resulting explosion andfire set off a sprinkler
system, soaking the remaining drums and spreading
the fire. Explosions, fire, and chlorine releases
lasted three days. Over 25,000 people were
evacuated and 275 people went to the hospital
with skin burns and respiratory problems.
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Mixing Incident
Lodi, New Jersey, April 21, 1995An explosion
and fire at the Napp Technologies facility
resulted in five deaths as well as injuries,
public evacuations and serious damage both on and
off site. According to a joint EPA/OSHA
investigation report, water apparently leaked
into a blender where sodium hydrosulfite,
aluminum powder, potassium carbonate and
benzaldehyde were being mixed. Operators noticed
production of heat and the release of a
foul-smelling gas, indicating an unexpected
reaction taking place in the blender. The water
caused the sodium hydrosulfite in the blender to
decompose, generating heat, sulfur dioxide, and
additional water. The decomposition process, once
started, was self-sustaining. The reaction
generated sufficient heat to cause the aluminum
powder to react rapidly with the other
ingredients and generate more heat. During an
emergency operation to remove the contents of the
blender, the material ignited, resulting in the
severe consequence.
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Physical Processing IncidentHanover Township,
Pennsylvania, February 19, 1999 A process vessel
containing several hundred pounds of
hydroxylamine exploded at the Concept Sciences,
Inc., production facility near Allentown,
Pennsylvania. Employees were distilling an
aqueous solution of hydroxylamine and potassium
sulfate, the first commercial batch to be
processed at the companys new facility. After
the distillation process was shut down, the
hydroxylamine in the process tank and associated
piping explosively self-reacted, most likely due
to high concentration and temperature. Four
Concept Sciences employees and a manager of an
adjacent business were killed. Two employees and
four people in nearby buildings were injured. Six
firefighters and two security guards suffered
minor injuries during emergency response efforts.
The explosion caused extensive damage to the
production facility, significant damage to other
buildings in the Lehigh Valley Industrial Park,
and shattered windows in several nearby homes.
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Flixborough Incident England, 1974
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Intentional Chemistry IncidentColumbus, Ohio,
September 10, 1997 An explosion at a
Georgia-Pacific Resins, Inc. resins production
unit killed one worker and injured four others.
The vessel rupture explosion was caused by a
runaway reaction. As detailed in an EPA Chemical
Safety Case Study, the runaway was triggered
when, contrary to standard operating procedures,
all the raw materials and catalyst were charged
to the reactor at once, followed by the addition
of heat. Under the runaway conditions, the heat
generated exceeded the cooling capacity of the
system and the pressure generated could not be
vented through the emergency relief system,
causing the reactor to explode.
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Intentional Chemistry Incident Processing of
substances such that a chemical reaction is
intended to takeplace, and products are of a
different chemical composition than the
startingmaterials. Exothermic reactions !!!!!!
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What Can Go Wrong?- Wrong material of
construction used- Inadequate cleaning or
purging before introducing material into vessel
or reactor- Wrong material used or added -Too
much material added- Too little or no material
added- Materials added in wrong sequence-
Material added too rapidly- Material added too
slowly- Contaminated feed material- Excess
catalyst or promoter added- Insufficient or no
catalyst added
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What Can Go Wrong?- Wrong catalyst added
Catalyst addition delayed Heat-up delayed
Cooling/refrigeration lost Heat added Heating
lost Incoming material too cold Incoming
material too hot- Air leak under vacuum Heat
transfer fluid leak Insufficient or no
agitation Start of agitation delayed
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Type of Hazards

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Chemical/ Physical Properties
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Physical Properties(??????????????????)

• pH (???-????)
• Vapor pressure (?????????)
• Boiling point (????????)
• Vapor Density (?????????????)
• Specific gravity (??????????????)
• Water solubility (??????????????????)
• Expansion or Liquid-Gas ratios (??????????????????
  ????)

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pH
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14 7 1

• pH 12-14 ???????
• pH 1-2 ??????

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Vapor Pressure (VP)
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?????????????????
EDC
VCM
Chlorine
VP 7600 mmHg
VP 3877mmmHg
VP 60 mmHg
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Boiling point (BP)
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??????????????? BP ??? ??????? VP ???
H2O
VCM
HCl
Chlorine
BP -34.6 C
BP -13.88 C
BP 100 C
BP 50.55 C
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Vapor Density (VD)
VD of dry air 1
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Specific gravity (SG)
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?????????
SG of Water 1
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Water Solubility
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???????? (Flammability)
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Flash Point
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Flammability
Flammable (Explosive) Range
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0
100
LEL
UEL
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Expansion Ratio???????????????
CO2 ???? 7001
LPG 2701
Gasoline 371
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Engineers must be knowledgeable about- The way
toxicants enter biological organisms,- The way
toxicants are eliminated from biological
organisms,- The effects of toxicants on
biological organisms, - Methods to prevent or
reduce the entry of toxicants into biological
organisms,
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Preliminary ScreeningMethod for
ChemicalReactivity Hazards
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Reference R. W. Johnson, S. W. Rudy, S. D.
Unwin, Essential Practices for Managing Chemical
Reactivity Hazards, Center for Chemical Process
Safety of the American Institute of Chemical
Engineers, 3 Park Avenue, New York, NY 10016-5991
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Reference R. W. Johnson, S. W. Rudy, S. D.
Unwin, Essential Practices for Managing Chemical
Reactivity Hazards, Center for Chemical Process
Safety of the American Institute of Chemical
Engineers, 3 Park Avenue, New York, NY 10016-5991
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Chemical Reactivity Hazard Management- An
ongoing effort to protect employees, contractors,
customers, the public, environment, and property
against the potential consequences of chemical
reactivity incidents.- An explicit management
commitment to employees, the community, and other
stakeholders to manage chemical reactivity
hazards throughout the life of the facility.
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Chemical Reactivity Hazard Management 4 simples
principles- Inform- Implement- Communicate-
Verify Know, Do, Tell and Check
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Inform
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Inform- Know if you have the potential for
uncontrolled reaction(s) to take place within
your facility. Know how such reactions might be
initiated (e.g., heat, contamination, inadvertent
mixing, impact, friction, electrical short,
lightning). Know how to recognize when an
uncontrolled reaction is taking place. Know
what the consequences would be if such a reaction
took place (e.g., toxic gas release, fire,
explosion). Know what safeguards are (or need
to be) in place to prevent uncontrolled reactions
from taking place, including how to avoid them
altogether (inherently safer design/operations)
and how to control them within safe limits
(automatic controls, procedures, etc.). Know
how to respond properly if an uncontrolled
reaction takes place (including operator actions,
emergency response plans, community alerting
plans, etc.).
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Implement
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Implement Do all of the required action items
uncovered in reactive chemistry testing, hazard
analyses and lessons learned from previous
incident investigations. Do apply all basic
process management practices, such as management
of change (MOC), to accurately assess any
chemical reactivity hazards that might be
introduced into the process. Do investigate all
reactivity-related incidents and near misses.
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Communicate
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Communicate Tell all affected personnel of the
potential hazards involved with the operation
(including normal operating instructions,
emergency procedures, etc.). Tell all affected
personnel what to do (e.g., training, drills) to
avoid chemical reactivity hazards, recognize when
an uncontrolled chemical reaction is taking
place, and respond properly if an uncontrolled
reaction occurs. Tell customers, suppliers,
trade and technical associations of any relevant
information regarding the chemical reactivity
hazards posed by raw materials, intermediates and
products. Tell emergency responders and other
potentially affected persons, including
industrial and residential neighbors, what to
expect and how to respond to a chemical
reactivity incident if one occurs at your
facility.
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Verify
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Verify Check that all new information
concerning chemical reactivity hazards is
incorporated into current operational
practices. Check that all items from hazard
analyses, incident investigations and other
discovery processes have been properly
implemented and documented. Check that all
communications protocols are being used as
intended. Check that all key personnel,
including the facility manager, have a complete
understanding of the chemical reactivity hazards,
including scenarios, lines of defense and
emergency actions to mitigate the consequences of
an uncontrolled reaction.
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??????????? Toxicology

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??????????? Toxicology

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??????????? Toxicology

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????????????

• Acetaldehyde
• 2-Acetylaminofluorene
• Acryl amide
• Acrylonitrile
• Aldrin
• 4-Aminobiphenyl
• Aniline
• Anisidine
• Arsenic and compounds
• Arsine
• Asbestos
• Benzene
• Benzidine
• Beryllium
• 1,3-Butadiene
• tert-Butyl chromate
• Cadmium dust
• Cadmium fume
• Carbon black

• Chlorinated camphene
• Chlorodiphenyl(42 and 54chlorine)
• Chloroform
• bis-Chioromethyl ether
• Chloromethyl methyl ether
• beta-Chloroprene
• Chromic acid and chromates
• Coal tar pitch
• DDT
• 1 ,2-Dibromo-3-chloropropane
• p-Dichlorobenzene
• 3,3-Dich1orobenzidine (and its salts)
• Dichloroethyl ether
• Dieldrin
• Diglycidyl ether
• 4-Dimethylaminoazobenzene
• 1,1-Dimethylhydrazine
• Deimethyl sulfate
• Dinitrotoluene

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• 4-Nitrobiphenyl
• p-Nitrochlorobenzene
• 2-Nitropropane
• N-Nitrosodimethylamine
• Phenyl glycidyl ether
• Phenyl hydrazine
• beta-Propiolactone
• Propylene dichloride
• Propylene imine
• Propylene oxide
• Silica (crystalline)
• 1,1,2,2-Tetrachloroethane
• Tetrachloroethane
• Titanium dioside
• Toluene-2,4-diisocyanate
• o-Toluidine
• 1,1,2-Trichloroethane
• Trichloroethylene
• 1,2,3-Trichloropropane

• Di-sec octyl phthalate
• Dioxane
• Epichlorohydrin
• Ethyl acrylate
• Ethylene dibromide
• Ethylene dichloride
• Ethyleneimine
• Ethylene oxide
• Formaldehyde
• Heptachlo
• Hexachioroethane
• Hydrazine
• Methoxychlor
• Methyl bromide
• Methyl chloride
• Methylene chloride
• Methyl hydrazine
• Methyl iodide
• alpha-Naphthylamine

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Route of Entry????????????????????????

• Ingestion via mouth through stomach
• Inhalation via mouth or nose into lungs
• Injection via cuts into skin
• Dermal absorption through skin membrane

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• Inhalation, injection and dermal absorption
  generally result in the toxicant entering the
  blood stream unaltered.
• Toxicants entering through ingestion are
  frequently modified or excreted in the bile.

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Methods for Control

• Entry route Entry organ Method for
  Control
• Ingestion mouth or stomach
  Enforcement of rules on eating,
  drinking, and smoking
• Inhalation mouth or nose
  Ventilation, respirators, hoods, and
  other PPE
• Injection cuts in skin
  Proper protecting cloth
• Dermal skin
  Proper protecting cloth
• absorption

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Inhalation Protection??????????????????????
APR - Air Purified Respirator ???????????????????
HF-Respirator (Half Face) ????????????????
FF-Respirator (Full Face) ???????????????
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Inhalation Protection ??????????????????????
SAR Supplied Air Respirator 1. SCBA 2. Air
Line ????????????????
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Eye Protection???????????????
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Skin Protection?????????????????
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Ingestion Protection????????????????????????
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Toxicants are eliminated or rendered inactive by

• Excretion through the kidneys, liver, lungs, or
  others.
• Detoxication by changing the chemical into
  something less harmful by biotransformation.
• Injection via cuts into skin
• Storage in the fatty acid.

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Health Effects

• TLV-TWA ?????????????????????????????????? 8 ??
• ??????????????? (????????????)
• Threshold limit Values-Time Weighted Average
• TLV-STEL ???????????????????????????? 15 ????
• ??????????????? (?????????????)
• Threshold limit Values-Short Time Exposure limit
• TLV-C ???????????????????????????? ??????
  ???????????????
• Threshold limit Values-Ceiling
• IDLH ???????????????????????????????????????????
  
• Immediately Dangerous to Life or Health

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Lethal Dose
LD50 ???????????????????????????????
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