Overview of Process Safety,
Green Engineering, and
Inherently Safer Design
Harry J. Toups LSU Department of Chemical Engineering with
significant material from SACHE 2003 Workshop presentation
entitled: Inherently Safer Design, by
Dennis Hendershot
Rohm and Haas Company
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Three Elements of Process Safety
Behavior
Process
Safety
Systems Process
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Process Safety Milestone Practices
Pre-1930s Identify who caused the loss
Behavior
and punish the guilty
Pre-1970s Find breakdown in, and fix
Process
man-machine interface
1970s, 80s Development of risk
Mgmt Systems
assessment techniques and
systematic approaches
1980s + Performance-, risk-based
Comprehensive
standards, regulations;
green and inherent designs
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Causes of Losses in Large Plant
Accidents
44
Process
Design
Accidents (%)
22
12 11
5 5
1
Mechanical Operator Unknown Process Natural Design Sabotage
Error Upsets Hazards and Arson
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Green chemistry and engineering
A Definition
The design, commercialization, and
use of chemical processes and
products, which are feasible and
economical while minimizing:
1) generation of pollution at the source,
and
2) risk to human health and the
environment.
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New paradigm for the environment
Traditional environmental approach
End of pipe waste treatment
Waste minimization an advance,
but we can go further
Green chemistry and engineering
Eliminate or dramatically reduce
hazards to the environment
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Many of us learned this as children
Dr. Suess
The Cat in the Hat
Comes Back
Once you get something dirty, the
only way to get it clean is to make
something else dirty.
The best way to keep the world clean is
to not get it dirty to begin with.
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Inherently Safer Design
A Definition
The design of chemical processes and
products with specific attention to
eliminating hazards from the
manufacturing process rather than
relying on the control of these hazards
Notice the common philosophy to
Green Engineering?
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New paradigm for safety
Traditional safety approach
Add on safety features
Prevent - alarms, safety interlocks,
procedures, training
Mitigate sprinkler systems, water
curtains, emergency response
systems and procedures
Inherently safer design
Eliminate or significantly reduce
process hazards
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Inherently safer design, green
chemistry, and green engineering
Inherently
Safer
Design
Green Chemistry
and Engineering
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Why are we interested in
inherently safer design?
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Flixborough, England (1974)
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Flixborough, England (1974)
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Henderson, Nevada, (1988)
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What is inherently safer design?
Inherent - existing in something as a
permanent and inseparable element...
safety built in, not added on
Eliminate or minimize hazards rather
than control hazards
More a philosophy and way of thinking
than a specific set of tools and methods
Applicable at all levels of design and
operation from conceptual design to plant
operations
Safer, not Safe
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Hazard
An inherent physical or chemical
characteristic that has the potential for
causing harm to people, the
environment, or property (CCPS, 1992).
Hazards are intrinsic to a material, or its
conditions of use.
Examples
Phosgene - toxic by inhalation
Acetone - flammable
High pressure steam - potential energy due
to pressure, high temperature
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To eliminate hazards:
Eliminate the material
Change the material
Change the conditions of use
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Chemical Process Safety
Strategies
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Inherent
Eliminate or reduce the hazard by
changing to a process or materials which
are non-hazardous or less hazardous
Integral to the product, process, or plant -
cannot be easily defeated or changed
without fundamentally altering the
process or plant design
EXAMPLE
Substituting water for a flammable solvent
(latex paints compared to oil base paints)
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Passive
Minimize hazard using process or
equipment design features which
reduce frequency or consequence
without the active functioning of
any device
EXAMPLE
Containment dike around a
hazardous material storage tank
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Active
Controls, safety interlocks, automatic shut down
systems
Multiple active elements
Sensor - detect hazardous condition
Logic device - decide what to do
Control element - implement action
Prevent incidents, or mitigate the consequences
of incidents
EXAMPLE
High level alarm in a tank shuts automatic feed
valve
Caution: Even protective systems can cause
incidents! (See Hendershot et al handouts)
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Procedural
Standard operating procedures,
safety rules and standard
procedures, emergency response
procedures, training
EXAMPLE
Confined space entry procedures
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Batch Chemical Reactor Example
Hazard of concern
Runaway reaction causing high
temperature and pressure and
potential reactor rupture
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Passive
Maximum adiabatic pressure for
reaction determined to be 150 psig
Run reaction in a 250 psig design
reactor
Hazard (pressure) still exists, but
passively contained by the
pressure vessel
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Active
Maximum adiabatic pressure for
100% reaction is 150 psig, reactor
design pressure is 50 psig
Gradually add limiting reactant with
temperature control to limit
potential energy from reaction
Use high temperature and pressure
interlocks to stop feed and apply
emergency cooling
Provide emergency relief system
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Procedural
Maximum adiabatic pressure for
100% reaction is 150 psig, reactor
design pressure is 50 psig
Gradually add limiting reactant with
temperature control to limit
potential energy from reaction
Train operator to observe
temperature, stop feeds and apply
cooling if temperature exceeds
critical operating limit
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Inherent
Develop chemistry which is not
exothermic, or mildly exothermic
Maximum adiabatic exotherm
temperature < boiling point of all
ingredients and onset temperature of
any decomposition or other
reactions
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Which strategy should we use?
Generally, in order of robustness
and reliability:
Inherent
Passive
Active
Procedural
But - there is a place and need for
ALL of these strategies in a
complete safety program
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Inherently Safer Design
Strategies
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Inherently Safer Design Strategies
Minimize
Moderate
Substitute
Simplify
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Minimize
Use small quantities of hazardous
substances or energy
Storage
Intermediate storage
Piping
Process equipment
Process Intensification
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Benefits
Reduced consequence of incident
(explosion, fire, toxic material
release)
Improved effectiveness and
feasibility of other protective
systems for example:
Secondary containment
Reactor dump or quench systems
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Semi-batch nitration process
Catalyst (usually
sulfuric acid) feed
or pre-charge
Organic Substrate and Nitric acid gradual
solvents pre-charge addition
Batch Reactor
~6000 gallons
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How can Process Intensification
be used in this reaction?
Mixing bringing reactants into
contact with each other
Mass transfer from aqueous
phase (nitric acid) to organic phase
(organic substrate)
Heat removal
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CSTR Nitration Process
Raw
Material
Feeds
Organic substrate
Catalyst
Nitric Acid
Reactor ~ 100 gallons
Product
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One step further:
Do this reaction in a pipe reactor?
Raw
Cooled continuous
Material
mixer/reactor
Feeds
Organic substrate
Catalyst
Nitric Acid
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Scale up
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Scale out
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On-demand phosgene generation
Continuous process to produce phosgene
Phosgene consumers are batch processes
No phosgene storage
Engineering challenges
Rapid startup and shutdown
Quality control
Instrumentation and dynamic process
control
Disposal of tail gas and inerts
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Moderate
Dilution
Refrigeration
Less severe processing conditions
Physical characteristics
Containment
Better described as passive rather
than inherent
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Dilution
Aqueous ammonia instead of
anhydrous
Aqueous HCl in place of anhydrous
HCl
Sulfuric acid in place of oleum
Wet benzoyl peroxide in place of dry
Dynamite instead of nitroglycerine
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0
Effect of dilution
0 5
Distance, Miles
Concentration, mole ppm 20,000
(B) - Release Scenario:
Centerline Ammonia
2 inch transfer pipe failure
10,000 Anhydrous
Ammonia
28%
Aqueous
Ammonia
0
0 Distance, Miles 1
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Less severe processing conditions
Ammonia manufacture
1930s - pressures up to 600 bar
1950s - typically 300-350 bar
1980s - plants operating at pressures
of 100-150 bar were being built
Result of understanding and
improving the process
Lower pressure plants are cheaper,
more efficient, as well as safer
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Substitute
Substitute a less hazardous
reaction chemistry
Replace a hazardous material with
a less hazardous alternative
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Substitute materials
Water based coatings and paints in
place of solvent based alternatives
Reduce fire hazard
Less toxic
Less odor
More environmentally friendly
Reduce hazards for end user and
also for the manufacturer
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Simplify
Eliminate unnecessary complexity
to reduce risk of human error
QUESTION ALL COMPLEXITY! Is it
really necessary?
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Simplify - eliminate equipment
Reactive distillation methyl acetate
process (Eastman Chemical)
Which is simpler?
Acetic Acid
Methanol
Catalyst
Methyl
Methyl Acetate
Acetate
Acetic Acid
Reactor Methanol
Recovery
Solvent
Recovery
Sulfuric
Splitter
Acid
Extractive
Distillaton
Water
Methanol
Reactor
Decanter Column
Extractor Impurity
Removal
Columns Heavies
Color
Column
Flash
Azeo Column
Column
Water
Heavies
Flash
Column
Water
Water
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Modified methyl acetate process
Fewer vessels
Fewer pumps
Fewer flanges
Fewer instruments
Fewer valves
Less piping
......
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But, it isnt simpler in every way
Reactive distillation column itself is
more complex
Multiple unit operations occur
within one vessel
More complex to design
More difficult to control and
operate
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Single, complex batch reactor
Large
Rupture
Disk
A
B
C Condenser
D
E
Distillate
Receiver
Steam
Refrigerated
Brine
Water Return
Water Supply
Condensate
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A sequence of simpler batch reactors
for the same process
A Large Rupture
B Disk
C
Refrigerated
Brine
Water Return
Water Supply
Condenser
E
Distillate
Receiver
Steam
Condensate
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Inherent safety conflicts
In the previous example
Each vessel is simpler
But
There are now three vessels, the
overall plant is more complex in some
ways
Compare to methyl acetate example
Need to understand specific hazards
for each situation to decide what is
best
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Conflicts and Tradeoffs
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Some problems
The properties of a technology which
make it hazardous may be the same as
the properties which make it useful:
Airplanes travel at 600 mph
Gasoline is flammable
Any replacement must have the ability to store
a large quantity of energy in a compact form
Chlorine is toxic
Control of the hazard is the critical issue
in safely getting the benefits of the
technology
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Multiple hazards
Everything has multiple hazards
Automobile travel
velocity (energy), flammable fuel,
exhaust gas toxicity, hot surfaces,
pressurized cooling system,
electricity......
Chemical process or product
acute toxicity, flammability,
corrosiveness, chronic toxicity,
various environmental impacts,
reactivity.......
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What does inherently safer mean?
Inherently safer is in the context of
one or more of the multiple hazards
There may be conflicts
Example - CFC refrigerants
low acute toxicity, not flammable
potential for environmental damage,
long term health impacts
Are they inherently safer than
alternatives such as propane
(flammable) or ammonia (flammable
and toxic)?
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Inherently safer hydrocarbon
based refrigerators?
Can we redesign the refrigeration
machine to minimize the quantity of
refrigerant sufficiently that we
could still regard it as inherently
safer?
Home refrigerators perhaps (<120
grams)
Industrial scale applications
probably not, need to rely on
passive, active, procedural risk
management strategies
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Multiple impacts
Different populations may perceive the
inherent safety of different technology
options differently
Example - chlorine handling - 1 ton
cylinders vs. a 90 ton rail car
A neighbor two miles away?
An operator who has to connect and
disconnect cylinders 90 times instead
of a rail car once?
Who is right?
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Inherently safer = safer
Air travel Automobile travel
several hundred people a few people
5 miles up on the ground
control in 3 dimensions control in 2 dimensions
600 mph 60 mph
thousands of gallons of a few gallons of fuel
fuel
passengers in a might even be a
pressure vessel convertible
......... .........
Automobile travel is inherently safer
But, what is the safest way to travel from
Washington to Los Angeles?
Why?
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At what level of design should
engineers consider inherently
safer design?
Selecting Technology? Plant Design?
Equipment Details? Operations?
Best answer? All levels!
Inherently safer design is not a meeting.
Inherently safer design is a way of
thinking, a way of approaching
technology design at every level of detail
part of the daily thought process.
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Questions a designer should ask
when he has identified a hazard
In this order
1. Can I eliminate this hazard?
2. If not, can I reduce the magnitude of the
hazard?
3. Do the alternatives identified in questions 1
and 2 increase the magnitude of any other
hazards, or create new hazards?
4. At this point, what technical and management
systems are required to manage the hazards
which inevitably will remain?
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The Future: Inherently safer design
Some hazardous materials and processes
can be eliminated or the hazards
dramatically reduced.
The useful characteristics of other
materials or processes make their
continued use essential to society for the
foreseeable future we will continue to
manage the risks.
E.g., Air travel
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Is It Worth the Effort?
Number of US workplace injuries/illnesses
Total Recordable Injury/Illness Rate
12 per 100 employees continues to drop
10
8
6
4 due to comprehensive safety strategies,
including Inherently Safer Design
2
0
1973 1983 1993 2003
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END OF
PRESENTATION
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