Chemical Process Safety

ChE 405: Process Design I

Reference:
Chapter 1, Daniel A Crowl, Joseph F. Louvar;
Chemical Process Safety: Fundamentals with
Applications (3rd edition) Prentice Hall, 2011

Department of Chemical Engineering

History of Ammonia Synthesis

Oct 13, 1908 : Haber astonished

the world by producing the first
practical and cost-effective
means of synthesizing ammonia,
now known as the Haber-Bosch
Process and had its greatest
impact on the production of
fertilizers

Fritz Haber
Impact of Haber-Bosch Ammonia
on World Population

Erisman et al., 2008

 History Chemical Weapon

PHOTO: The Canadian Press

April 22, 1915: The first use of WMDs (Cl gas) in human
history occurred, on a battlefield at Ypres, Belgium. Haber
developed early gas masks with absorbent filters and
masterminded the first chlorine attacks at Ypres, Belgium.
 Overview of Presentation

 Process Safety: what, how, where/when?

 Occupational vs Process safety

 How accidents occurs: Examples

 Bangladesh Scenario

 Exisitng rules and regulations

 Safety culture

 Process Safety Management System

 Chemical Process Industry

Processes that belong to chemical industry are

• Manufacturing of substances/materials on an
industrial scale from other materials
– by chemical processes
– by separation refining and purifying
The industry also includes gas and oil
industry and power generating plants
 Chemical/Process Industries in Bangladesh
(Public Sector)
• BCIC: Bangladesh Chemical Industries
Corporation
– Fertilizer factories: Urea , TSP, DAP
– Glass/ ceramics/ insulators/cement factories
– Paper mills
• BPC: Bangladesh Petroleum Corporation
– Crude oil refinery
• Petrobangla:
– Gas well drilling (?), gas processing and distribution
 Chemical/Process Industries in Bangladesh
(Private Sector)

• Urea Fertilizer factory: • Salt and sugar

KAFCO • Pulp and paper
• Gas drilling(?) and • Soap and detergents
processing: Gazprom, • Beauty products
Chevron, NIKO, • Food processing
ConocoPhillips, Santos
• Gas transmission
• Glass and ceramics • Basic Chemicals
• Cement factories • Pharmaceuticals
• Condensate refineries • Textiles and leather
 What is ‘Safety in Process Plants’?
• The word “safety” used to mean the older
strategy of accident prevention through the
use of hard hats, safety shoes, and a variety of
rules and regulations. The main emphasis was
on worker safety.
• Much more recently, “safety” has been
replaced by “loss prevention.” This term
includes hazard identification, technical
evaluation, and the design of new engineering
features to prevent loss.
 Process Safety vs Occupational Safety

Improvement of personal safety does not mean automatic

improvement in process safety
 Process Safety vs Occupational Safety
Process safety Occupational safety
• Focuses on prevention of • Primarily covers the
fires, explosions and management of personal
accidental chemical releases safety: creating working
in chemical process facilities conditions that prevent
or other facilities dealing injuries in general.
with hazardous materials • Examples: falls ,tips, slips
• Examples: Toxic release, crushing, electronics etc.
fire, explosion • Low consequences, High
• High consequences, Low frequency
frequency accidents
Improvement of personal safety does not mean automatic
improvement in process safety
BP Texas City Refinery Explosion 23 March,
2005
• Hydrocarbon vapor
cloud exploded at
the isomerization
process unit killing
15 workers and
injuring more than
170 others
• Miscommunication
and instrument
malfunctioned
 Why is Process Safety Important?

“Chemical plants are the safest of all manufacturing facilities.

However, the potential always exists for an accident of
catastrophic proportions.”(Source : Crowl and Louvar, 2002)
 Why is Process Safety Important? (cont’d)
• Immediate effects Bhopal, India (December
3, 1984)
– Fatalities within the  Immediate effects: Killed
boundary and 2000 civilians in adjacent
town and injured 20,000
surrounding
 Long term effects:
communities
 Soil and ground water
– Property damage pollution inside and
nearby area
• Long term effects  gas affected population
– Environment of 520,000.
 200,000 were below 15
– Future generation years of age, and 3,000
were pregnant women
Process Safety: Where to Apply ?
Process safety is applied to
• Storage of materials
• Transportation of materials on road, rail,
water and in air
• Manufacturing and refining of materials
Process safety is for all materials with
hazardous properties or under hazardous
conditions
 Process Safety: When to Apply?
Safety at All stages
• Design
• Construction and Commissioning
• Operation
• Shutdown
• Maintenance
• Transportation
The concept of inherently safer design starts from
Process development (R&D) and pre-design stage
 Safety Programs

• System
• Attitude
• Fundamentals
• Experience
• Time
• You
 Safety Programs cont’d

• A Good safety program identifies and

eliminates existing safety hazards
• An Outstanding safety program has
management system that prevent existence of
safety hazards
 Definitions

• Safety/loss prevention: the prevention of accidents

through the use of appropriate technologies to
identify the hazards of chemical plant and eliminate
them before an accident occurs.
• Hazard: a 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 and
injury.
 Types of Chemical Plant Accidents

Type of Probability Potential Potential

accidents of for for
occurrence fatalities economic
loss
Fire High Low Intermediate

Explosion Intermediate Intermediate High

Toxic Low High Low

release
Statistics
 Acceptable Risk & Public Perceptions

• We cannot eliminate risk entirely

• In a single Chemical Process plant the risk becomes too
high because of multiple exposure to several processes
• Modern site layout requires sufficient separation of
plants within site to minimize multiple exposure
• Public perception about hazards of chemicals can be
confusing and may not reflect the real situation
 Layers of Protection
Typical Layers of
Protection
exist in process
industries
 How Accident Occurs (cont’d)
SSAP The ‘Swiss cheese’ model of
2
organisational accidents

Some holes due Hazards

To active failures

Other holes due to

latent conditions
Losses
Successive layers of defences
Reason’s “Cheese Model”
James Reason, presentation to Eurocontrol 2004
Example of Disaster: Bhopal, India (December
3, 1984)

• Plant Location: Madhya Pradesh, central India; nearest

inhabitants were 1.5 miles away, but a shanty town grew
nearby.
• Produced Pesticides; owned by Union Carbide and
partially owned locally
• Intermediate compound methyl iso-cyanate (MIC):
reactive, toxic, volatile, flammable and vapor heavier
than air.
• MIC unit was not operating because of labor dispute
 Example of Disaster cont’d

• Accident:
– Storage tank containing large amount of MIC became
contaminated by water, heated by reaction; vapor traveled
through pressure relief system into a scrubber and flare system
that was not operating
– 25 tons toxic MIC vapor released, spread to the adjacent town
killing over 2000 civilians and injuring 20,000 more. No plant
workers were killed.
• Recommendation:
– Alternative reaction scheme or redesigning of the process with
reduced inventory of MIC (less than 20 pounds)
 Example: Bhopal Tragedy (Dec 3,1984)
 40 tons of
toxic MIC
vapor was
released
 Failure of
several
safety
system
 Inadequate
emergency
planning
and
community
awareness
 Major Incidents in Bangladesh
Date Location Release Consequence Short Description
Sep UFFL, NH3 2 killed, 17 Ammonia Control room
1974 Ghorashal injured explosion
June, UFFL, CO2/NH3 11 Fatalities, Explosion of high pressure
1991 Ghorashal 50 injured, CO2 stripper during the
Estimated startup, release CO2 and
property loss: NH3, Employee exposed to
US$ 60 M toxic gas and 7 died on spot

June Magurchhara NG Environmental Gas well blowout

2005 damage (Occidental)
Jan Tangratilla NG Environmental Gas well blowout (Niko)
2005 damage
October, Global Heavy Cl2 100 seriously Pipe failure due to rust and
2011 Chemicals, exposed to toxic Cl2 gas leaks to surrounding
Narayongonj gas area
22 Aug, DAP-1, NH3 50 hospitalized, 325 tons of ammonia
2016 Anawara, environmental release due to a drastic
Chittagong damage explosion of 500 MT
ammonia tank.
 Case-1: CO2 Stripper failure (UFFL, 1991)
Incident Description:
 On 20 June 1991, at 00:10 AM, Carbon
dioxide stripper exploded during start-
up.
 CO2 gas and liquid ammonia was
pumped into the high pressure
stripper. At the time of the explosion,
stripper pressure reached 160 kg/cm2.
 Two loud explosions occurred and a
large quantity of toxic gas was
released to the environment. Control
room power system failed. Stripper
main body fell out and was lifted up
30-35 ft. CO2 stripper after the
 11 fatalities and estimated property explosion
loss 62.5 million USD
 Case-1: Safety Issues

 Pre-start-up safety reviews were not

adequate
 Process Hazard Analysis was not performed
 Mechanical Integrity failure: defective
fabrication/welding of stripper column.
 Faulty facility layout and poor design of
control room
 Safety drill and procedures were not
followed
 Absence of emergency response planning
 Case-2: NH3 release (DAP-1, 2016)
Incident Description: Top

 At around 9:30 PM on 22 August 2016,

500MT anhydrous ammonia tank suddenly
exploded catastrophically and released 325
tons of anhydrous ammonia
 The tank was completely lifted from its base
and landed about 35 ft away from its base
 Fire fighters used water to contain the
release toxic gas
 250 people became sick and many were
required hospitalization
 Ammonia that diffused into water bodies
increased pH and had an adverse impact
on the overall aquatic ecosystem
Bottom
 Case-2: Safety Issues

 Failures of pressure relief system, alarm

system
 Process Hazard Analysis was not performed
 Mechanical Integrity failure: inspection and
certification
 No safety audit and inspection
 Absence of additional layer of protection
 Absence of emergency response planning
 Inadequate community planning and lack of
awareness of potential impact of NH3 release
 Case 3: Fire at Tampaco Foils Ltd

• On 10 September, 2016 early morning fire erupted after explosions

caused by gas leak and continue to burn for three days
• Chemicals stored on ground floor first including ethyl acetate and
other adhesives caused the quick spread of fire and sustain
• 35 died and 100 hospitalized
• Fire fighters used water / water spray to contain the fire
 Case-3: Safety Issues

• Unsafe chemical storage

• Lack of information about the stored
chemicals
• Lack of monitoring system
• Inadequate emergency response planning
 Global Scenario

Technology
development
Influenced by
major incident
1974-2016
 Bangladesh Scenario
Boiler Fire and
Boiler Explosion in Explosion in
Toxic Cl2 gas
Ammonia Magurchhar explosion and Chemical Tampaco
release in
control room a Gas oil fire in KTS Factory Foils Factory
Global Heavy
explosion, blowout factory Gazipur Gazipur
Chemicals ltd
UFFL (Occidental) (54 Fatalities) (6 fatalities) (34 fatalities)

1974 1997 2006 2011 Jan 2016 Sep 2016

1991 2005 2010 2014 Aug 2016

We
are
here
CO2 stripper Tagratilla Nimtoli fire Oil spill in DAP-1 500
explosion Gas oil Tragedy, Old Sundarban MT Tank
UFFL blowout Dhaka (1 fatality and Explosion
(11 fatality) (Niko) (124 fatalities) environmental and
damage) ammonia
release

Major incident due to chemical release and explosion (1974-2016)

 Challenges
 Could these incident have been prevented?
 Do we have any safety regulation and good
safety culture?
 Do we have any management system that is
needed to control process safety issues?
 Existing Rules and Regulations
• The Boiler Acts 1923
• Industrial rules and regulations 1961
• Bangladesh Standards and Testing Institution (BSTI)
Ordinance, 1985
• Bangladesh National Building Codes,1993
• The Environment Conservation Rules,1997
• Bangladesh Labour Act, 2006, amended in 2013
• The Chemical Weapons (Prohibition) Act, 2006 and
Enrolment Rules, 2010
• National Occupational Health and Safety Policy, 2013
 What do We Need?

Safety Regulations
Safety Education and Safety culture
Safety Management System
 • Inherently safer system
• Process Safety Management
 Inherent Safety Technique
• Depends on chemistry or physics to prevent accidents rather than
on control system, interlocks, redundancy, special operating
procedures
• It specially directed to process design features , for example:
– Minimize:
• reduce storage, hold-up, inventory of hazardous material
– Substitute:
• use chemicals with higher flash points, use water as heat transfer fluid
instead of oil
– Moderate:
• reduce process temperature & pressure, control room away from
operations
– Simplify:
• keep piping system neat and visible
 Process Safety Management System
Why do we need Process Safety Management (PSM) ?

 Prevent Catastrophic release of Highly Hazardous

Chemicals.
 Minimize consequences of such release to
employees and the community and the Environment
 14 Elements of PSM
Commit to Safety Management of Risk
 Employee Participation  Operating Procedures
 Training
Understanding hazard and risk  Contractors Safety
 Process Safety Information (PSI)  Pre-startup Safety Review
 Process Hazard Analysis (PHA)  Mechanical Integrity
 Hot Work Program
Learn from experience  Management of Change
 Incident investigation  Emergency Planning and
Response
 Compliance audit
 Trade Secrets
History: First Protest against WMDs

1900:First woman to get a

PhD in Chemistry
1901: Got married with
Haber
1915 : Committed suicide
in protest to her husband’s
work

Clara Immerwahr
 Case History 1: ( Washington DC, Manufacturing
Chemists’ association)

• Static Electricity :Tank car loading explosion

– Two plant operators were filling a tank car with
vinyl acetate. After few seconds the contents of
the tank exploded, one operator died from
fractured skull and body burns
– Caused by a static spark jumped from the steel
nozzle to the tank car
 Case History 2: ( Washington DC, Manufacturing
Chemists’ association)

• Chemical Reactivity
– Bottle of isopropyl ether; A chemist twisted the
cap of a bottle of isopropyl ether to open it. As the
cap broke loose, the bottle exploded. The man
died due to massive internal hemorrhage.
– Caused by rapid decomposition of peroxides,
which formed in the ether while the bottle sat in
storage.
 Case History 3: ( Washington DC, Manufacturing
Chemists’ association)

• System Design
– Ethylene oxide explosion: A process storage tank contained
6500 gal of ethylene oxide. It was accidentally contaminated
with ammonia. The tank ruptured and dispersed ethylene oxide
into the air. A vapor cloud was formed and immediately
exploded. One person was killed and nine were injured;
property losses $16.5 million
– Lack of design protection to prevent back up of ammonia into
the storage tank.
 Case History 4: ( Washington DC, Manufacturing
Chemists’ association)

• System Procedure
– Man working in a Vessel: two maintenance
workers were replacing part of a ribbon in a large
ribbon mixer. The main switch was left energized,
the mixer was stopped with one of three start-
stop buttons. The operator by mistake pushed one
of the start stop button , the mixer started and the
mechanic inside was killed.