Introduction to

Inherently Safer Design

Prepared for Safety and Chemical
Engineering Education (SACHE) by:

Dennis C. Hendershot
Rohm and Haas Company, retired

American Institute of Chemical Engineers, 2006 1

Introduction to Inherently Safer Design

What is 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

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Introduction to Inherently Safer Design

Why Inherently Safer Design?

Flixborough, UK, 1974

Bhopal, India,
1984
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Pasadena, TX, 1989
Introduction to Inherently Safer Design

A subset of Green Engineering

Inherently
Safer
Design

Green Chemistry
and Engineering

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Introduction to Inherently Safer Design

History of inherently safer

design
Not really a new concept elimination of
hazards has a long history
Second half of 20th Century chemical
industry increased hazards from huge,
world scale petrochemical plants
Concern about cost and reliability of
traditional add on safety systems
Trevor Kletz ICI (1977) Is there a better
way?
Eliminate or dramatically reduce hazards
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Introduction to Inherently Safer Design

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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Introduction to Inherently Safer Design

To eliminate hazards:
Eliminatethe material
Change the material
Change the conditions of use

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Introduction to Inherently Safer Design

Chemical Process Safety

Strategies

Inherent
Passive
Active
Procedural

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Introduction to Inherently Safer Design

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)
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Introduction to Inherently Safer Design

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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Introduction to Inherently Safer Design

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
EXAMPLES
High level alarm in a tank shuts automatic feed
valve
A sprinkler system which extinguishes a fire 11
Introduction to Inherently Safer Design

Procedural
Standard operating procedures, safety
rules and standard procedures,
emergency response procedures,
training
EXAMPLE
Confined space entry procedures

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Introduction to Inherently Safer Design

Human Reliability
Available Response Probability of
Time (minutes) incorrect diagnosis
single control room
1 event
10 ~1.0
20 0.5
30 0.1
60 0.01
0.001
Source: Swain, A.D., Handbook of Human Reliability Analysis, August 1983,
NUREG/CR-1278-F, U.S. Nuclear Regulatory Commission 13
Introduction to Inherently Safer Design

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
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Introduction to Inherently Safer Design

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

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Introduction to Inherently Safer Design

Inherent
VENT

REACTANT FEEDS

PI

COOLING

TI

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Introduction to Inherently Safer Design

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
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Introduction to Inherently Safer Design

Passive
VENT

REACTANT FEEDS

PRV

PI

TI

COOLING

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Introduction to Inherently Safer Design

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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Introduction to Inherently Safer Design

Active
RUPTURE DISK WITH DISCHARGE
VENT TO SAFE PLACE

REACTANT FEEDS

PA
H SAFETY SYSTEM
LOGIC ELEMENT
TA
H

COOLING

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Introduction to Inherently Safer Design

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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Introduction to Inherently Safer Design

Procedural
RUPTURE DISK WITH DISCHARGE
VENT TO SAFE PLACE

REACTANT FEEDS

PA
H

TA
H

COOLING

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Introduction to Inherently Safer Design

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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Introduction to Inherently Safer Design

Layers of Protection
COMM UNITY EM ERGENCY REPSONSE

PLANT EM ERGENCY 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

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Introduction to Inherently Safer Design

Multiple Layers of Protection

Potential Incidents

Layers of Protection

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Actual Risk
Introduction to Inherently Safer Design

Degraded Layers of Protection

Potential Incidents

Layers of Protection
Degraded

Degraded

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Higher Actual Risk
Introduction to Inherently Safer Design

Inherently Safe Process

No additional layers of protection
needed
Probably not possible if you consider
ALL potential hazards
But, we can be Inherently Safer
PROCESS
DESIGN
I

LAH
1

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Introduction to Inherently Safer Design

Inherently Safer Process Risk

Potential Incidents

No Layers of Protection
Needed

Actual Risk 28
Introduction to Inherently Safer Design

Managing multiple hazards Process Option No. 1

Toxicity Explosion Fire ..

COMMUNITY EMERGENCY REPSONSE

PLANT EMERGENCY REPSONSE

PHYSICAL PROTECTION (DIKES)

PHYSICAL PROTECTION (RELIEF DEVICES) AUTOMATIC ACTION SIS OR ESD

AUTOMATIC ACTION SIS OR ESD

CRITICAL ALARMS, OPERATOR
SUPERVISION, AND MANUAL INTERVENTION
CRITICAL ALARMS, OPERATOR
PROCESS SUPERVISION, AND MANUAL INTERVENTION BASIC CONTROLS, PROCESS ALARMS,
DESIGN AND OPERATOR SUPERVISION
I BASIC CONTROLS, PROCESS ALARMS,
AND OPERATOR SUPERVISION
PROCESS
LAH
1 PROCESS DESIGN
DESIGN I
I

LAH
LAH
1 1

Hazard 2 Hazard 3 Hazard n

Hazard 1 - Passive, Passive, ????
Inherent Active, Active,
Procedures Procedures

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Introduction to Inherently Safer Design

Managing multiple hazards Process Option No. 2

Toxicity Explosion Fire ..

COMMUNITY EMERGENCY REPSONSE

PLANT EMERGENCY REPSONSE

PHYSICAL PROTECTION (DIKES)

AUTOMATIC ACTION SIS OR ESD PHYSICAL PROTECTION (RELIEF DEVICES)

CRITICAL ALARMS, OPERATOR AUTOMATIC ACTION SIS OR ESD

SUPERVISION, AND MANUAL INTERVENTION
BASIC CONTROLS, PROCESS ALARMS,
AND OPERATOR SUPERVISION
PROCESS
CRITICAL ALARMS, OPERATOR
SUPERVISION, AND MANUAL INTERVENTION
BASIC CONTROLS, PROCESS ALARMS, PROCESS
AND OPERATOR SUPERVISION DESIGN
I

DESIGN PROCESS
I DESIGN LAH
1
I

LAH
LAH
1 1

Hazard 3 Hazard 2 Hazard n

Passive, Passive, Hazard 1 - ????
Active, Active, Inherent
Procedures Procedures

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Inherently Safer Design
Strategies

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Introduction to Inherently Safer Design

Inherently Safer Design Strategies

Minimize
Moderate
Substitute
Simplify

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Introduction to Inherently Safer Design

Minimize
Use small quantities of hazardous
substances or energy
Storage
Intermediate storage
Piping
Process equipment
Process Intensification

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Introduction to Inherently Safer Design

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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Introduction to Inherently Safer Design

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
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Introduction to Inherently Safer Design

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
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Introduction to Inherently Safer Design

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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Introduction to Inherently Safer Design

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

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Introduction to Inherently Safer Design

CSTR Nitration Process

Raw
Material
Feeds
Organic substrate
Catalyst
Nitric Acid

Reactor ~ 100 gallons

Product
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Introduction to Inherently Safer Design

Can you do this reaction in a

tubular reactor?

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

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Introduction to Inherently Safer Design

Semi-Batch solution
polymerization
Solvent
Additives
Initial Monomer "Heel"
Monomer and
Initiator gradually
added to minimize
inventory of
Large (several
unreacted material
thousand gallons)
batch reactor

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Introduction to Inherently Safer Design

What controls this reaction

Contacting of monomer reactants and
polymerization initiators
Heat removal
Temperature control important for
molecular weight control

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Introduction to Inherently Safer Design

Tubular Reactor
Initiator Static mixer pipe reactor (several
inches diameter, several feet long,
cooling water jacket)

Monomer, solvent, additives

Product Storage Tank

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Introduction to Inherently Safer Design

Substitute
Replace a hazardous material with a less
hazardous alternative
Substitute a less hazardous reaction
chemistry

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Introduction to Inherently Safer Design

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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Introduction to Inherently Safer Design

Substitute Reaction Chemistry

Acrylic Esters
Reppe Process
Ni(CO )4
CH CH + CO + ROH CH 2 = CHCO2 R
HCl
Acetylene - flammable, reactive
Carbon monoxide - toxic, flammable
Nickel carbonyl - toxic, environmental hazard
(heavy metals), carcinogenic
Anhydrous HCl - toxic, corrosive
Product - a monomer with reactivity
(polymerization) hazards
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Introduction to Inherently Safer Design

Alternate chemistry
Propylene Oxidation Process
3 Catalyst
CH 2 = CHCH 3 + O2 CH 2 = CHCO2 H + H 2 O
2
H+
CH 2 = CHCO2 H + ROH CH 2 = CHCO2 R + H 2 O
Inherently safe?
No, but inherently safer. Hazards are primarily
flammability, corrosivity from sulfuric acid
catalyst for the esterification step, small
amounts of acrolein as a transient
intermediate in the oxidation step, reactivity
hazard for the monomer product. 47
Introduction to Inherently Safer Design

Moderate
Dilution
Refrigeration
Less severe processing conditions

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Introduction to Inherently Safer Design

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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 Conc
Ce
28%
Aqueous
Ammonia
Introduction to Inherently Safer Design
0
0 5
Effect of dilution
Distance, Miles

20,000
Concentration, mole ppm

(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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Introduction to Inherently Safer Design

Impact of refrigeration

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

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Introduction to Inherently Safer Design

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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Introduction to Inherently Safer Design

Simplify
Eliminate unnecessary complexity to
reduce risk of human error
QUESTION ALL COMPLEXITY! Is it really
necessary?

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Introduction to Inherently Safer Design

Simplify - eliminate equipment

Reactive distillation methyl acetate
process (Eastman Chemical)
Which is simpler?
Acetic Acid
Methanol Methyl
Catalyst Acetate
Methyl
Acetate Acetic Acid

Reactor Methanol
Recovery Sulfuric
Solvent
Recovery Acid

Splitter
Extractive Methanol
Distillaton
Water

Reactor
Column
Decanter
Impurity
Removal
Extractor
Columns Heavies

Color
Column

Flash
Column
Water
Azeo
Column

Heavies

Flash
Column
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Water
Water
Introduction to Inherently Safer Design

Modified methyl acetate

process
Fewer vessels
Fewer pumps
Fewer flanges
Fewer instruments
Fewer valves
Less piping
......
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Introduction to Inherently Safer Design

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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Introduction to Inherently Safer Design

Single, complex batch reactor

Large
Rupture
Disk

A
B
C Condenser
D
E
Distillate
Receiver

Steam
Refrigerated
Brine

Water Return

Water Supply

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Condensate
Introduction to Inherently Safer Design

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 58
Inherent Safety Considerations
through the Process Life Cycle

(Use manufacture of acrylate

esters as an example)

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Introduction to Inherently Safer Design

Research
Basic technology
Reppe process
Propylene oxidation followed by
esterification
Other alternatives
propane based
Others - ????

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Introduction to Inherently Safer Design

Process Development
Implementation of selected technology
Oxidation catalyst options
Temperature
Pressure
Selectivity
Impurities
Catalyst hazards
Esterification catalyst options
Sulfuric acid
Ion exchange resins or other immobilized acid
functionality catalysts

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Introduction to Inherently Safer Design

Preliminary Plant Design

Plant location
Plant site options
Plant layout on selected site
Consider
People
Property
Environmentally sensitive locations

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Introduction to Inherently Safer Design

Detailed Plant Design

Equipment size
Inventory of raw materials
Inventory of process intermediates
One large train vs. multiple smaller
trains
Specific equipment location

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Introduction to Inherently Safer Design

Detailed Equipment Design

Inventory of hazardous material in each
equipment item
Heat transfer media (temperature,
pressure, fluid)
Pipe size, length, construction (flanged,
welded, screwed pipe)

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Introduction to Inherently Safer Design

Operation
Userfriendly operating procedures
Management of change
Consider inherently safer options when
making modifications
Identify opportunities for improving
inherent safety based on operating
experience, improvements in technology
and knowledge

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Introduction to Inherently Safer Design

When to consider Inherent

Safety?
Start early in process research and
development
NEVER STOP looking for inherently
safer design and operating
improvements

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Introduction to Inherently Safer Design

Questions designers should ask

when they have identified a hazard
Ask, 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?
(If so, consider all hazards in selecting the best alternative.)
4. At this point, what technical and management
systems are required to manage the hazards which
inevitably will remain?
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Introduction to Inherently Safer Design

Inherently Safer Design and

Regulations
Contra Costa County, CA Industrial Safety Ordinance
(1999)
Requires evaluation of inherently safer technologies
Reviewed by enforcement agencies
Allows consideration of feasibility and economics
New Jersey Department of the Environment (2005)
Facilities covered by the New Jersey Toxic Catastrophe
Prevention Act (TCPA) must review the practicality of
adopting inherently safer technology as an approach to
reducing the potential impact of a terrorist attack
United States Federal requirements
Several chemical security bills which include requirements
for consideration of inherently safer design have been
introduced in Congress, but, as of June 2006 none of these
have been enacted.
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Introduction to Inherently Safer Design

Resources
Kletz,T. A., Process Plants - A
Handbook for Inherently Safer Design,
Taylor and Francis, London, 1998.
Inherently Safer Chemical Processes - A
Life Cycle Approach, American Institute
of Chemical Engineers, New York, 1996.
Note: A second edition is being written in 2006.

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Introduction to Inherently Safer Design

Resources
Guidelines for Engineering Design for
Process Safety, Chapter 2 Inherently
Safer Plants. American Institute of
Chemical Engineers, New York, 1993.
Guidelinesfor Design Solutions for Process
Equipment Failures, American Institute of
Chemical Engineers, New York, 1998.

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Introduction to Inherently Safer Design

Resources
INSIDEProject and INSET Toolkit,
Commission of the European
Community, 1997 - available for
download from:
http://www.aeat-safety-and-
risk.com/html/inset.html
Extensivejournal and conference
proceedings literature

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