INHERENTLY SAFER DESIGN

Safety terminologies

† Accident: the occurrence of a sequence of

unwanted events that produced unintended
injury, death or property damage
† Hazard: a chemical or physical condition that
has the potential to cause damage to people,
environment or property
† Risk: a measure concerning both the likelihood
and magnitude of loss
† Safety or loss prevention: the prevention of
accidents through appropriate hazard
identification, risk assessment and control
strategies
Inherently safer design -
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
 Inherently safer design in the chemical
industry
† Trevor Kletz, ICI, UK (1977)
„ Jubilee Lecture to the UK Society of the
Chemical Industry
„ Reaction to Flixborough, England explosion
„ Named the concept
„ Developed a set of specific design principles for
the chemical industry
„ Later published - original paper referring to
“Inherently Safer Design”
† Kletz, T. A. “What You Don't Have, Can't
Leak.” Chemistry and Industry, 287-292,
6 May 1978.
Inherently Safer Design

†Inherent - “existing in something as a

permanent and inseparable element...”
†Eliminate or minimize hazards rather than
control hazards
†Safety based on physical and chemical
properties of the system, not “add-on”
safety devices and systems
†“Safer” – not “Safe”
In reality no design can be inherently safe,
however you can have an inherently safer
design
Why are we interested in
inherently safer design?
Flixborough, England (1974)

A large release of cyclohexane from a caprolactam plant

killed 28 workers, injured 36, and destroyed the plant.
 Bhopal, India, 1984

The worst disaster in the history of the chemical industry

occurred when water entered a storage tank containing
methyl isocyanate (MIC). The resulting reaction
generated heat and pressure, lifting the tank relief valve
and released highly toxic MIC vapors into the city.
 Pasadena, TX (1989)

•A leak of gas from a polyethylene plant formed a flammable vapor

cloud which ignited, causing 23 fatalities and hundreds of injuries,
and destroying the plant.
A subset of Green Engineering

Inherently
Safer
Design

Green Chemistry
and Engineering
 Hazard

† An inherent physical or chemical characteristic

that has the potential for causing harm to people,
the environment, or property.
† 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
To eliminate hazards:

† Eliminate the material

† Change the material
† Change the conditions of use
Chemical Process Safety Strategies

† Inherent
† Passive
† Active
† Procedural
Inherent

† Eliminate or reduce the hazard by changing the

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)
Passive

† Minimize hazard using process or

equipment design features which reduce
frequency or consequence without the
active functioning of any device
† EXAMPLE
„ Containment dike (a barrier) around a
hazardous material storage tank
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
Procedural

† Standard operating procedures,

safety rules and standard
procedures, emergency
response procedures, training
† EXAMPLE
„ Confined space entry procedures
Batch Chemical Reactor Example

† Hazard of concern – runaway reaction

causing high temperature and pressure
and potential reactor rupture

„ Example – Morton
International, Paterson,
NJ runaway reaction in
1998, injured 9 people
 Inherent

†Develop chemistry which is not exothermic,

or mildly exothermic
„Maximum adiabatic reactor temperature
< boiling point of all ingredients and onset
temperature of any decomposition or other
reactions, and no gaseous products are
generated by the reaction

„The reaction does not generate any pressure,

either from confined gas products or from boiling
of the reactor contents
VENT

REACTANT FEEDS

PI

COOLING

TI
 Passive

†Maximum adiabatic pressure for reaction

determined to be 150 psig
„From vapor pressure of reactor contents or
generation of gaseous products
†Run reaction in a 250 psig design reactor
†Hazard (pressure) still exists, but
passively contained by the pressure vessel
 VENT

REACTANT FEEDS

PRV

PI

TI

COOLING
 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
 RUPTURE DISK WITH DISCHARGE
VENT TO SAFE PLACE

REACTANT FEEDS

PA
H SAFETY SYSTEM
LOGIC ELEMENT
TA
H

COOLING
 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
 RUPTURE DISK WITH DISCHARGE
VENT TO SAFE PLACE

REACTANT FEEDS

PA
H

TA
H

COOLING
 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
Layers of Protection
COMMUNITY EMERGENCY REPSONSE

PLANT EMERGENCY REPSONSE

PHYSICAL PROTECTION (DIKES)

PHYSICAL PROTECTION (RELIEF DEVICES)

AUTOMATIC ACTION SIS OR ESD

CRITICAL ALARMS, OPERATOR

SUPERVISION, AND MANUAL INTERVENTION

BASIC CONTROLS, PROCESS ALARMS,

AND OPERATOR SUPERVISION

PROCESS
DESIGN
I

LAH
1

SIS – Safety Interlock System; ESD – Emergency Shutdown

Inherently Safer Design Strategies

† Minimize
† Moderate
† Substitute
† Simplify
 Strategy Examples

Substitute Replace material with a less hazardous

substance.

Minimize Use smaller quantities; eliminate unnecessary

equipment; reduce size of equipment or
volumes processed.

Moderate Use less hazardous conditions, a less hazardous

form of material or facilities which minimize the
impact of a release.

Simplify Design facilities which eliminate unnecessary

complexity and make operating errors less
likely.
Minimize

† Use small quantities of hazardous

substances or energy
„ Storage
„ Intermediate storage
„ Piping
„ Process equipment
† “Process Intensification”
• Continuous reactors (stirred tanks, loop reactors,
tubular reactors) in place of batch reactors
• Reduced inventory of raw materials and in-process
intermediates
• High efficiency heat exchangers

Example: A 50-liter loop polymerization reactor has a

capacity equal to that of a 5000-liter batch reactor
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
Opportunities for process intensification in
reactors

† Understand what controls chemical

reaction to design equipment to
optimize the reaction
„ Heat removal
„ Mass transfer
† Mixing
† Between phases/across surfaces
„ Chemical equilibrium
„ Molecular processes
Generic Nitration Reaction

H2SO4
Organic substrate (X-H) + HNO3 Solvent

Nitrated Product (X-NO2) + H2O

†Reaction is highly exothermic

†Usually 2 liquid phases – an aqueous/acid
phase and an organic/solvent phase
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
What controls the rate of this reaction?

†Mixing – bringing reactants into contact

with each other
†Mass transfer – from acid/aqueous phase
(nitric acid) to organic phase (organic
substrate)
†Heat removal
CSTR Nitration Process

Raw
Material
Feeds
Organic substrate
Catalyst
Nitric Acid

Reactor ~ 100 gallons

Product
Can you do this reaction in a
tubular reactor?

Raw
Cooled continuous
Material
mixer/reactor
Feeds
Organic substrate
Catalyst
Nitric Acid
Substitute

† Substitute a less hazardous reaction

chemistry
† Replace a hazardous material with a
less hazardous alternative
 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
Alternative chemistry using less hazardous materials

Acrylic esters were formerly manufactured using the

Reppe process, using acetylene, carbon monoxide, and
a nickel carbonyl catalyst. The newer propylene
oxidation process uses significantly less hazardous
materials
 Substitution - Refrigeration

† Many years ago (pre-1930)

„ Toxic, flammable refrigerants
† Ammonia, light hydrocarbons, sulfur dioxide
† Quantity – often several kilograms
† Inherently safer alternative (1930s)
„ CFCs
† Discovery of environmental problems (1980s)
„ “Green” alternatives include light hydrocarbons
„ Require re-design of home refrigerators to minimize
quantity of flammable hydrocarbon (currently as little as
120 grams of hydrocarbon refrigerant)
Moderate

†Dilution
†Refrigeration
†Less severe processing conditions
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
Effect of dilution

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
Impact of refrigeration
Monomethylamine Distance to
Storage ERPG-3 (500 ppm)
Temperature Concentration,
(°C) km
10 1.9
3 1.1
-6 0.6

The distance to an atmospheric concentration of

500 ppm of mono-methylamine in the event of the
failure of a 2-inch pipe is reduced from 1.9 miles
to 0.6 miles by reducing the temperature of the
monomethylamine from 10ºC to -6ºC
 The Emergency Response Planning Guideline (ERPG)

The ERPG-3 is the maximum airborne concentration

below which it is believed that nearly all individuals could
be exposed for up to 1 hour without experiencing or
developing life-threatening health effects.
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
 Simplify

† Eliminate unnecessary complexity to

reduce risk of human error
„ QUESTION ALL COMPLEXITY! Is it really
necessary?
Simplify - eliminate equipment

† Reactive distillation methyl acetate

process (Eastman Chemical)
† Which is simpler?
Acetic Acid
Methanol
Catalyst Methyl
Acetate
Methyl
Acetate
Acetic Acid

Reactor Methanol
Recovery
Solvent
Recovery
Sulfuric
Acid
Splitter
Extractive
Distillaton
Water Methanol

Reactor
Column
Decanter
Impurity
Extractor Removal
Columns Heavies
Color
Column

Flash
Azeo Column
Column Water

Heavies

Flash
Column

Water
Water
Modified methyl acetate process

† Fewer vessels
† Fewer pumps
† Fewer flanges
† Fewer instruments
† Fewer valves
† Less piping
† ......