Introduction to Chemical

Process Safety
Instructor: Dr. Tamaghna Chakraborti
Ph. No. : +91 9892770980
Outline
• Need for safety
• Safety technology
• Accident and Loss Statistics
• Nature of the accident process
• Inherent safety
• Four significant disasters
Need for safety
• Bulk of economic growth a result of technological advances
• Leads to technologically advanced processes in the industry
• In chemical industry, technologically advanced process  higher
pressure, more reactive chemicals and exotic chemistry
• More complex processes require advanced safety technologies
• From an industrialist’s viewpoint safety a constraint on the growth of
industry
• Why?  As it requires money to make processes safe
• An extremely naive viewpoint
Need for safety (2)
• To invest in safety is to invest in yourself, your near and dear ones,
your community and in humanity
• Better be safe than sorry!!
Safety technology
• In the current industrial scenario safety = production in importance
• Scientific discipline that requires highly technical and complex
theories
• Example :
• Hydrodynamic models representing two-phase flow through vessel relief
• Dispersion models representing spread of toxic vapor through a plant
• Mathematical techniques to determine the probability of failure
• Use of appropriate technologies for providing information for safety
decisions
Safety, Hazard and Risk
• Safety : the prevention of accidents through the use of appropriate
technologies to identify the hazards of a chemical plant and eliminate
them before an accident occurs.
• Hazard : the chemical or physical condition that has the potential to
cause damage to people, property or the environment.
• Risk : a measure of human injury, environmental damage or economic
loss in terms of both the incident likelihood and the magnitude of loss
or injury.
Hazards in a chemical plant
• Usual mechanical hazards that cause worker injury from tripping,
falling and moving equipment
• Chemical hazards : Fire and explosion hazards, Reactivity hazards,
Toxic hazards
• Contrary to perception, chemical plants safest of all manufacturing
facilities
• Accidents usually do not occur but there are devastating consequences if they
do
Good and outstanding safety programs
• Good safety program : Identifies and eliminates existing safety
hazards
• Outstanding safety program : Has management systems that prevent
the existence of safety hazards
Accident and loss statistics
• Accident and loss statistics : A measure of the effectiveness of safety
programs
• Statistics must be used carefully.
• According to a popular proverb, there are three kinds of lies
• Lies
• Damn lies
• Statistics
• Only averages and do not reflect the potential of single accidents
causing loss of catastrophic proportions
Accident and loss statistics (Cont’d)
• Three systems will be considered in the syllabus
1. OSHA incidence rate
2. Fatal accident rate (FAR)
3. Fatality rate or deaths/person/year
• Report the number of accidents and/or fatalities for a fixed number of
workers during a specified period.
OSHA incidence rate
• OSHA  Occupational Safety & Health Administration of the US
government
• Based on cases per 100 worker years
• 1 worker year = 2000 hrs (50 work weeks/year * 40 hrs/week)
• OSHA incidence rate hence based on 200,000 hours of worker
exposure to a hazard
OSHA incidence rate (based on injuries or illness) =
(Number of injuries/illness * 200,000) / (Total hours worked by all
employees during the period covered)
Fatal accident rate (FAR)
• Mostly used by the British chemical industry
• Reports the number of fatalities based on 1000 employees working
for their entire lifetime in the same set-up
• Lifetime of work = 50 years
• Total hrs = 1000 workers * 50 years/worker * 2000 hours/yr
= 100,000,000 (10^8) hours
FAR = Number of fatalities * 10^8 / (Total hours worked by all
employees during period covered)
Fatality rate
• Final statistic: Fatality rate or deaths/person/year
• Independent of the number of hours actually worked (which is a
measure of the amount of risk taken)
• Useful for performing calculations when the number of exposed hours
is poorly defined (for example, accident statistics due to striking of
lightning)
Fatality rate = (Number of fatalities per year)/( Total number of people
in the applicable population)
Problem
If twice as many people used motorcycles for the same average amount
of time each, what will happen to (a) the OSHA incidence rate, (b) FAR,
(c) the fatality rate and (d) the total number of fatalities?
Solution
• OSHA incidence rate  remain the same. Injuries/deaths double but
number of exposed hours double as well.
• FAR  remain the same. Same reason as above
• Fatality rate  double. Fatality rate does not depend on number of
exposed hours
• Total number of fatalities  double.
Acceptable risk
• Risk cannot be eliminated entirely
• But has to be reduced to minimal levels
• Concept of acceptable risk
• Acceptable risk  Risk similar to or less than that during normal day to day
operations
• Objective of the engineer  Minimize risk within the economic constraint of
the process
• Even with low risk levels, general public has to be convinced with great
difficulty
• Has to do with the involuntary nature of the risk taken
Nature of the accident process
• Chemical plant accidents follow typical patterns
• Most common accidents in the chemical plant:
• Fires and explosions
• Fires
• Vapor cloud explosions
• Toxic release
The accident process
• Initiation  the event that starts the accident
• Propagation  the event or series of events that maintain or expand
the accident
• Termination  the event or events that stop the accident or
diminishes it in size
Example
• The following accident report has been filed.
Failure of a threaded one and half inch drain connection on a rich oil line at
the base of an observer tower in a large (1.35 MCF/D) gas producing plant
allowed the release of rich oil and gas at 850 psi and -40 degrees F. The
resulting vapor cloud probably ignited from the ignition system of engine
driven recompressors. The 75 ft high and 10 ft diameter absorber tower
eventually collapsed across the pipe rack and on two exchanger trains.
Breaking pipes added more fuel to fire. Severe flame impingement on an
11,000-horsepower gas turbine-driven compressor, waste heat recovery and
super-heater train resulted in its near total destruction
Identify the initiation, propagation and termination steps.
Solution
• Initiation  Failure of threaded one and half inch connection

• Propagation Release of rich oil and gas, formation of vapor cloud,

ignition of vapor cloud by recompressors, collapse of absorber tower
across pipe rack

• Termination  Consumption of all combustible materials

Few definitions
• Accident: The occurrence of a sequence of events that produce unintended injury,
death or property damage. “Accident” refers to the event, not the result of the event.
• Hazard: A chemical or physical condition that has the potential for causing damage to
people, property or the environment.
• Incident: The loss of containment of material or energy; not all events propagate into an
incident; not all incidents propagate into an accident
• Consequence: A measure of the expected effects of the results of an incident
• Likelihood: A measure of the expected probability or frequency of occurrence of an
event. This may be expressed as a frequency, a probability of occurrence during some
time interval or a conditional probability.
• Risk: A measure of the human injury, environmental damage or economic loss in terms
of both the incident likelihood and the magnitude of loss/injury.
Inherent safety
• Relies on chemistry and physics to
make a plant safe instead of relying
on control systems, interlocks,
redundancy and special operating
procedures to prevent accidents.
• Advantages of an inherently safe
plant
• Error tolerance
• Cost effectiveness
• Process safety depends on multiple
layers of protection
Inherent safety (Cont’d)
• Inherent safety best implemented at early stages of process
development
• Maximum freedom in the plant and process specifications
• Inherent safety aptly described by 4 ‘golden’ words
• Minimize  Smaller vessels, less storage inventory, reduction of hold-up
• Substitute mechanical pump seals vs. packing, welded pipes vs. flanged, less
toxic and less volatile solvents, use water as heat transfer fluid instead of hot oil
• Moderate reduce process temperatures and pressures, operate at conditions
where reactor runaway is not possible, refrigerate storage vessels
• Simplify  design plants for easy and safe maintenance, design control panels
that are easier to comprehend, keep piping systems neat and visually easy to
follow
Review of major accidents in the chemical
industry
1. Flixborough, England
• Explosion at a chemical plant close to the village of Flixborough, North
Lincolnshire, England
• Occurrence: Saturday, June 1st, 1974.
• Casualty: 28 dead, 36 wounded
• Casualties could have been higher had the disaster occurred on a
weekday
• Led to public outcry over process plant safety
• Health and Safety at Work Act as well as a more systematic approach
to process safety
Cause of the Accident
Cause of the accident
• Reactor 5 leaking
• Water hose stream was directed
to cool the crack and quench the
cyclohexane leak
• Water contained nitrates which
encouraged stress corrosion
• Reactor 5 removed for
maintenance and a bypass line
constructed to connect reactors 4
and 6
Cause cont’d
• No stress analysis performed on the by-pass line
• On day of accident, the bypass line jack-knifed due to thermal stresses
• Crack in the pipeline
• Release of 40,000 lbs of cyclohexane into the congested space in the
reactors
• Flammable vapor cloud exploded within two minutes
Lessons learnt
• Three root causes:
1. Use of cooling water with nitrates to quench reactors. Technical causes
2. Installing a by-pass line without performing a stress analysis.
3. Critical man-power shortage  Absence of mechanical engineering Management
failure
personnel
• Lessons:
1. Proper hazard study to be performed before any modifications made to the
plant
2. Presence of proper personnel on the site.
Bhopal, India
• The world’s WORST industrial disaster in terms of fatalities
and second-most tragic moment in the history of disasters
after Chernobyl
• Immediate casualties: 3500+
• 15,000+ deaths over the next several days
• Occurred due to the release of toxic gas as a result of failure
of safety features
• A result of acute negligence on behalf of plant management
• Resulted in several acts and regulations both in India and
abroad
Cause of the Accident
Cause of the Accident
• Water accidentally introduced into the MIC
storage tank.
• Violent exothermic reaction of water with
methyl iso-cyanate
• Caused the temperature and pressure in the
storage tank to shoot up
• Refrigeration system turned off due to COST
CONCERNS
• Scrubber with brine solution not working
• Flare system for burning the gas off in case of
emergency leak under repair
• Result: 40 tons of methyl isocyanate gas leaked
into the atmosphere (Source)
• Carried by wind towards the shantytown
developed nearby (Dispersion)
• The gas being heavier than air settled down on
the ground causing severe casualties
Lessons learnt
• NEVER COMPROMISE ON SAFETY ISSUES
• Safety audits a must for every chemical plant
• Bhopal not a result of lack of safety features
• Three safety features in place
• Neglected due to cost cutting and sheer negligence
• Also properly trained workers to handle emergency situations like
pressure build-up and runaway reactions
Seveso, Italy
• Occurred in Meda, a small town about 15 miles north of Milan
• Named after Seveso, the community most affected
• Date of occurrence : July 10th , 1976
• Resulted in the highest known exposure to TCDD
• 2,3,7,8-tetrachlorodibenzo-p-dioxin  The most potent toxin known to
humans
• Gave rise to numerous scientific studies and standardized industrial
safety regulations
• Introduced laws known as Seveso II Directive
 Cause of the accident

1,2,4,5-tetrachlorobenzene TCDD
2,4,5-trichlorophenol

• Plant used to make 2,4,5-trichlorophenol from 1,2,4,5-tetrachlorobenzene as

intermediate for hexachlorophene
• At higher temperature, conversion to side product TCDD.
• Temperature for the primary reaction : 158 °C
 Cause of the accident

1,2,4,5-tetrachlorobenzene TCDD
2,4,5-trichlorophenol

• Plant used to make 2,4,5-trichlorophenol from 1,2,4,5-tetrachlorobenzene as

intermediate for hexachlorophene
• At higher temperature, conversion to side product TCDD.
• Temperature for the primary reaction : 158 °C
• Temperature of the side reaction : observed experimentally to be 230 °C
Cause (Cont’d)
• Reaction temperature above those achievable using the available plant
utilities
• Use exhaust steam pipe from on-site electricity generation plant
• Exhaust steam normally at 12 bar and 190 °C
• No steam temperature reading available to plant operators
• Plant shutdown on day of accident
• No load on power plant, so steam temperature ↑ to 300 °C
• Result : Runaway side reaction to produce TCDD at 180 °C with increase in
reactor pressure
• 2 kgs of TCDD released to the atmosphere which further contaminated the
soil after heavy rain
Lessons learnt
• Inlet conditions of different processes independent of other processes
• Different processes should operate independent of each other as far as
possible
• Application of proper containment systems to contain toxic
substances like scrubbers, flares and others.
• Initiation step would not have occur if proper hazard evaluation
procedures performed
Pasadena, Texas
• Occurred in Philips 66 Company’s Houston Chemical Complex facility
in Pasadena on October 23rd, 1989.
• Blast which measured 3.5 on the Richter scale
• Casualty: 23 killed, 314 injured
Causes
• Produced polyethylene in plug-flow mode
• Reaction : Condensation polymerization
• Reactant : 95% ethylene dissolved in
isobutene
• Extremely flammable mixture
• Product polyethylene removed from reactor
via a settling leg
• Plugging of the settling leg by polyethylene
• Must be periodically cleaned
Causes
• Cleaning procedure
1. Close DEMCO valve
2. Apply lock-out device
3. Remove pneumatic connections
4. Remove leg for cleaning
• Wrong connection of pneumatic pipes
• Lock-out device removed
• On day of accident, DEMCO valve was in open
position releasing combustible vapor
• Explosion due to unknown ignition source
Lessons
• Several safety norms and regulations violated.
• A complex cleaning procedure amenable to mistakes
• FOLLOW SAFETY REGULATIONS TO THE BOOK
• Plant operations must be simplified
• Applicable to even laboratories
• Simple plant operations such that anyone can do it without much
effort
Conclusions
• Learning about plant safety a MUST from all aspects
• MUST ATTEND ALL THE LECTURES OF THIS COURSE