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Chemical
Reactivity
Hazards:
2005 SACHE Faculty Workshop
Chemical
foresee
Reactivity
avoid
Hazards:
control
Introduction
Course Texts
Pretest
Key Concepts 1
Midterm Exam
Key Concepts 2
Open-Book Final
Extra-Credit Activities
Course
Texts
Texts
CCPS Safety Alert 2001.
Reactive Material Hazards: What You Need to Know.
New York: AIChE. 10 pages.
0
4 3
WW
OX
OX
Pretest
A1 Flammability
0
Toxicity
4 3 Instability
WW
OX
OX
Special Hazards
Pretest
C4H7NO
Pretest
CH3
C O + HCN
CH3
Pretest
CH3 OH
C
CH3 C N
Acetone Cyanohydrin
NFPA 49
Severe health hazard; combustible;
readily decomposes, producing
HCN; no special hazards;
reacts with acids, alkalis,
oxidizing materials,
reducing agents
2
3 1
Acetone Cyanohydrin
International Chemical Safety Card
Extremely toxic, Class IIIB combustible,
unstable at elevated temp,
decomposes in water
1
4 2
Acetone Cyanohydrin
WISER (http://wiser.nlm.nih.gov)
HIGHLY FLAMMABLE: Easily ignited by heat, sparks or flames
DO NOT GET WATER on spilled substance or inside containers
2
4 2
Acetone Cyanohydrin
DOT
Class 6.1 Poisonous material
Acetone Cyanohydrin
CHRIS
Acetone Cyanohydrin
CHRIS
Acetone Cyanohydrin
SIDS: Stability in Water
60
50
T (min)
40
30
20
10
0
4.5 5 5.5 6 6.5 7 7.5
pH
Acetone Cyanohydrin
Conclusions
Extremely toxic; must keep contained
and avoid all contact
Combustible; must avoid flame, ignition
Dissociates to produce highly toxic and
flammable gases; dissociation increases
with heat, moisture, alkalinity
Must prevent spills into drains, etc.
Must avoid incompatible materials
Key Concepts
Key Concepts
Summary
Flowchart
Source: Johnson et al. 2003
Incident
Inherently Environ-
Pollution Waste
Cleaner mental
Prevention Management
Processes Restoration
Processes
Recovery
Mitigation Prevention Safer
Accident
Inherently
Safe Operation
(with respect to Chemical Reactivity Hazards)
MINIMIZE
SUBSTITUTE
MODERATE
SIMPLIFY
Foresee, Avoid, Control
Reactivity
4.3 Incidents Management
Identify Chemical Practices/Program
Reactivity Hazards
Hazards 4.4
Test for Chemical IMPLEMENT; OPERATE FACILITY
NO
Reactivity
Sufficient
information to evaluate 4.8
hazard?
Communicate and Train on
Chemical Reactivity Hazards
YES
3 (continued)
If any components can decompose at the maximum
adiabatic reaction temperature, you will have to
under-stand the nature of this decomposition and
evaluate the need for safeguards including emergency
pressure relief systems.
Reaction Hazard Identification
4 (continued)
Again, if this is possible, you will have to understand
how these reactions will impact the need for safeguards,
including emergency pressure relief systems.
Understanding the stability of a mixture of components
may require laboratory testing.
Reaction Hazard Identification
10 (continued)
The location of the reactor temperature sensor relative
to the agitator, and to heating and cooling surfaces may
impact its ability to provide good information about the
actual average reactor temperature. These problems will
be more severe for very viscous systems, or if the
reaction mixture includes solids which can foul
temperature measurement devices or heat transfer
surfaces. Either a local high temperature or a local low
temperature could cause a problem. A high temperature,
for example, near a heating surface, could result in a
different chemical reaction or decomposition at the
higher temperature.
Reaction Hazard Identification
10 (continued)
A low temperature near a cooling coil could result in
slower reaction and a buildup of unreacted material,
increasing the potential chemical energy of reaction
available in the reactor. If this material is subsequently
reacted because of an increase in temperature or other
change in reactor conditions, there is a possibility of an
uncontrolled reaction due to the unexpectedly high
quantity of unreacted material available.
Reaction Hazard Identification
Scenario-based
Inadvertent Mixing Scenarios
CONDITIONS R, NR
SCENARIO 1 2 INFORMATION SOURCES; COMMENTS
NORMAL? or ?
1 Mix one liter of household ammonia Yes R Based on sodium hypochlorite solution
cleaner into four liters of household chlorine MSDS. Generates heat and toxic
bleach in an open bucket, with intention of vapors; can form explosive nitrogen
immediate use trichloride under certain conditions
2 Inadvertently pump up to 1400 kg of 38C No ? Compatibility information only known for
cyclohexane at 0.3 kg/s into closed, ambient conditions; no reaction with
temperature-controlled storage tank of cyclohexane expected, but may be hot
between 700 and 2800 kg of acrylic acid with enough to increase dimer formation and
200 ppm MEHQ inhibitor, maintained at 20C possibly initiate polymerization
1
Does the contact/mixing occur at ambient temperature, atmospheric pressure, 21% oxygen atmosphere, and
unconfined? (IF NOT, DO NOT ASSUME THAT PUBLISHED DATA FOR AMBIENT CONDITIONS APPLY)
2
R = Reactive (incompatible) under the stated scenario and conditions
NR = Non-reactive (compatible) under the stated scenario and conditions
? = Unknown; assume incompatible until further information is obtained
SCENARIO
2 Inadvertently pump up to 1400 kg of 38C
cyclohexane at 0.3 kg/s into closed,
2 Inadvertently pump up to 1400 kg of 38C
cyclohexane at 0.3 kg/s into closed,
temperature-controlled storage tank of
temperature-controlled
between 700 and 2800 kg of acrylic acid with
200 ppm MEHQ inhibitor, maintained at 20C
storage tank of
between 700 and 2800 kg of acrylic acid with
200 ppm MEHQ inhibitor, maintained at 20C
Inadvertent Mixing Scenarios
SCENARIO CONDITIONS
1
NORMAL?
GuideWord/ Severit
Cause Freq Consequences
Deviation On Off
AS WELL AS Connecting valve Containment rupture
Cyclohexane left open explosion
Added Fire
Toxic reaction products
release
Chemistry Hazard Analysis Scenarios
Guideword Deviation Consequences Comments/Actions
No No Catalyst C No reaction when Reactants A Develop kinetic and
added and B are mixed; if Catalyst C thermodynamic data on
is added after the entire charge this reaction
of Reactants A and B has been
completed, a rapid and violent
reaction can occur
More High Side reactions have been Investigate the
temperature; observed in similar systems behavior of the reaction
greater than above 70C, and may also at elevated temperature
70C occur with this chemistry
As well as Rust, as well The effect of contamination Determine the effect of
as normal with iron or rust is unknown iron/rust contamination
materials
Identify,
characterize
hazards
Normal Situation - Reactives
Reactive materials contained
Reactive interactions (incompatibilities) avoided
Intended reactions controlled
Chemical
Reactivity
Hazards
Potential Loss Event
Impacts
People
Property
Environment
Abnormal Situation - Reactives
Loss of containment
Reactive interaction (incompatibility)
Loss of reaction control
Chemical
se
Reactivity
au
Hazards
C
Deviation
Chemical Reactivity: Loss Events
Loss Event
Fire
Explosion
Release
Loss Events Associated with Reactivity
Hazards
Hazard Type Typical Uncontrolled Chemical Reaction Consequences
See
http://www.diers.net/diersweb/home.aspx for
schedule and information
DIERS Conference
Chemical
Reactivity
Hazards
Contact Information
Robert W. Johnson
Unwin Company
1920 Northwest Blvd, Suite 201
Columbus, OH 43212-1197 USA
(614) 486-2245
rjohnson@unwin-co.com
www.unwin-co.com