Professor Ashok Deshpande

Welcomes You All!

Probabilistic Risk Assessment for
Chemical Process Industry:
An Overview

Ashok Deshpande Ph. D.

Founding Chair: Berkeley Initiative in Soft computing (BISC) Special Interest
Group (SIG)-Environment Management Systems (EMS)
Guest faculty: University of California, Berkeley CA USA
Adjunct Professor :College of Engineering Pune (COEP), India
Former Deputy Director: National Environmental Engineering Research
Institute (NEERI) India
Professor Albert Einstein famously
suggested,
Without changing our patterns of
thought, we will not be able to solve
the problems we created with our
current patterns of thought.
 Professor Babitt visited University of
Roorkee and said
Industrialise OR Perish
Industrialise AND Perish

We must strike a balance between the two realities.

Therefore the need for sustainability development

 What is a Disaster?

Aster means a star in French, and

Disaster signifies an Unwanted star

-Natural Disaster :
Usually with severe consequences
-Man Made Disaster
 Origin of the Word Risk

The word "Risk" comes to us through French, Italian

and Latin, originating from the Greek word Rhiza in
reference to the Hazards of sailing around a cliff.
By 750 BC Bottomary was highly developed in Greece.
At that time all voyages were covered by bottomary
contracts with 10-25% Risk premiums, depending upon
the perceived riskiness of the venture.
Risk could be expressed as
-Qualitative
Risk due to
-Quantitative
Accidental releases
Continuous releases
 Preamble

Major industrial disaster during the last four decades

have brought to fore the adverse consequences of
industrial development with less concern on industrial
safety.

The Flixborough disaster ( 1974), the Bhopal Gas

Tragedy (1985), Mexico LPG disaster (1984), and
many such events have underlined the need for a -
priori Probabilistic Risk Assessment (PRA) to enable
industrial safety and social well being.

The developing countries have recognized the need

for PRA in their quest for sustainable development.
 Why Perform Risk Analysis ?

1. Planners / Engineers have a moral obligation to

design the safest possible system (with lowest
probability of system failure and minimal
consequences if the system does fail) within the given
set of engineering constraints

2. Information useful in comparative risk assessment

3. Government regulations
 What is Risk?

the likelihood of a specified undesired Serious consequence

x high likelihood =
event occurring within a specified period or
higher risk
in specified circumstances.

RISK = Likelihood x consequence

Likelihood

high

moderate

Minor consequence x
low likelihood = low

low risk
minor serious extensive
Consequence
 Tolerable Risk

Moral, Legal and financial responsibility to limit our risk

In some countries, the law mandates tolerable risk levels
Meeting OSHA requirements as minimum

Make plant as safe as

possible, disregard cost
Comply with regulation
as written, regardless Legal Moral
of cost or level of risk

Financial

Build the lowest cost plant and keep

operating budget as small as possible
Glossary of Terms
 Glossary of Terms

Acute

Severe but short duration. Acute health effects are

those that occur immediately after exposure to
hazardous chemicals
Acutely toxic Chemicals
Chemicals that can cause both severe short and long
term health effects after a single brief exposure
(short duration). These chemicals ( when ingested ,
inhaled or absorbed through skin ) can cause
damage to living tissues ,impairment of the central
nervous , system , severe illness , or, in extreme
cases death .
 Glossary of Terms

Hazard
Any situation that has the potential for causing
damage to life, property, and/or the environment.
Hazardous Chemical
Any chemical which is a physical injury or a health
hazard .
Hazardous Material
Any substance or material in a quantity or form which
may be harmful to humans, animals, crops, water
systems or other property when released into the
environment .
 Glossary of Terms

Hazardous materials include: explosives, gases

(compressed, liquefied or dissolved), flammable and
combustible liquids , flammable solids or substances ,
oxidizing substances poisonous and infectious
substances , radioactive materials and corrosives
Hazard Analysis
Includes the procedures for identify ing potential
sources of a hazardous material release from fixed
facilities or from transportation accidents: for
determining the susceptibility or vulnerability of a
geographical area to a hazardous material release and
for comparing hazards to determine which pose
greater or lesser risks to a community
 Glossary of Terms

Hazard Identification
Provides information on those facilities which have
extremely hazardous substances, what those
chemicals are, and quantity at each facility. Also
provides information on how the chemicals are stored
and weather they are used at high temperatures.

Immediately Dangerous to Life and Health ( IDLH)

The maximum level to which a healthy worker can be
exposed for 30 minutes and escape without
suffering irreversible health effects or escape
impairing symptoms . Used as a measure of the level
of concern .
 Glossary of Terms

Lethal
Causing or capable of causing death.
Lethal Concentration Low (LCLO)
The lowest concentration of a chemical at which some
test animals died following exposure by inhalation.
Lethal Dose (LDL)
The lowest dose of a chemical at which some test
animals died following the exposure.
Level of Concern
The concentration of an extremely hazardous
substance in the air above which there may be serious
immediate health effects to anyone exposed to it for
a short periods of time.
 Glossary of Terms

Median Lethal Concentration (LC50)

Concentration level at which 50 percent of the test
animals died when exposed to inhalation for a
specified time period.

Median Lethal Dose (LD50)

Dose at which 50 percent of the animals died. Dose
usually given in mg per kg of the body weight of the
test animal.
 Glossary of Terms

Risk
The probability that the damage to life, property, and
/or the environment will occur if a hazard manifests
itself.
Risk Analysis
Assessment of the probable damage that may be
caused to the community by a hazardous release.
Threshold Planning Quantity
A quantity designed for each chemical on the list of
extremely hazardous substances that triggers
notification by facilities of the State Emergency
Response Commission
 Glossary of Terms

Toxicity
The state or degree to which a substance is poisonous
and may chemically produce an injurious or deadly
effect upon introduction into a living organism.
Vulnerability Analysis
Assessment of elements in the community that are
susceptible to damage should a hazardous material
release occur, includes gathering information on the
extent of the vulnerable zone and condition that
influence the zone, private and public property that
might be damaged, and the environment that might be
affected.
 Glossary of Terms

Vulnerable Zone
An area over which the airborne concentration of a
chemical involved in an accidental release could reach
the level of concern.
Toxic Levels of Chlorine and Ammonia
There are certain limits which are frequently used in
deciding the safe distance from the source . These
are as follows :
 Glossary of Terms

IDLH
Immediately dangerous to life and health
concentration . this is usually defined as thirty
Minute exposure . it is used as a guide in the
industrial situation as a concentration from which
workers would not be able to safely escape if their
respiratory equipment failed .
 Glossary of Terms

Properties of Hazardous Materials

Dangerous Materials :
Chemicals that may , under specific circumstances,
cause injury to persons or damage to property
because of reactivity, instability , spontaneous
decomposition , flammability , or volatility .
Reactivity Hazard :
Reactivity ( instability ) hazard deals with the degree
of susceptibility of materials to release energy .
 Glossary of Terms

Reactive Materials :
Reactive materials are those which can enter into a
chemical reaction with other stable Or unstable
materials .
Unstable Materials :
Chemicals which in the pure state or as commercially
produced will vigorously polymerize , decompose or
condense or become self reactive and undergo
other violent chemical changes .
 Glossary of Terms

Stable Materials
Chemicals that normally have the capacity to resist
changes in their chemical composition , despite
exposure to air ,water and heat .
Explosives
Those substances, mixtures or compounds which are
capable of entering in to a combustion reaction so
rapidly and violently as to cause an explosion .
 Glossary of Terms

Corrosive Materials :
Corrosive materials include acids and alkalis which
react with the vessel in which they are stored
resulting in their destruction -may cause serious
burns and eye damage to personnel .
Toxic chemicals :
Those gases , liquids and solids which through their
chemical properties produce injurious or lethal
effects upon contact with body cells .
 Glossary of Terms

Oxidizing Materials :
Those chemicals which decompose readily under
certain conditions to yield oxygen . they may cause a
fire when in contact with combustible materials , may
react violently with water ,and when involved in fire
may react violently .
Flash point :
It is the lowest temperature of liquid at which its
vapour is given off in sufficient quantities so that the
vapour / air mixture above the surface will propagate
a flame away from the source of ignition through the
vapour / air mixture .
 Glossary of Terms

Fire point :
The lowest temperature at which a liquid evolves vapours fast
enough to support continuous combustion is called the fire
point.
Boiling point
The temperature at which the vapour pressure of the liquid is
equal to the atmospheric pressure at the surface is called
the boiling point.

Vapour Pressure
It is the pressure (usually expressed in mm of Hg) at any
given temperature of the vapour of the substance in
equilibrium with its liquid or solid form
 Glossary of Terms

Flammable (explosive) limits

The minimum/maximum concentration of vapour or
gas in air below/above which propagation of flame
does not occur on contact with a source of ignition
are called the flammable limits.
Ignition Temperature
Minimum temperature of a substance , whether solid,
liquid or gas required to ignite or cause self
sustained combustion independently of the heating or
heated element.
 Glossary of Terms

Flammable Liquid
Any liquid having a flash point below 100 degree F (
37.8 degree C) and having a vapour pressure not
exceeding 40 psia at 100 degree F.

Combustible Liquids
Liquids with flash points at or above 100 degree F.
Specific Gravity
It is the ration of the mass of a given volume of
material to the mass of equal volume of water at a
given temperature.
 Glossary of Terms

Threshold Limit Value- Short Term Exposure (TLV-

STEL)
It is the maximum concentration to which workers
can be exposed for a period up to 15 minutes
continuously without suffering from irritation,
irreversible tissue change or narcosis of sufficient
degree to increase accident proneness, impair self-
rescue, or materially reduce work efficiency,
provided that no more than four excursions per day
are permitted, with at least 60 minutes between
exposure periods, and provided that daily TLV-TWA
also is not exceeded.
 Glossary of Terms

Threshold Limit value (TLV)

It is the air- borne concentration of substances
representing conditions under which it is believed that
nearly all workers may be repeatedly exposed, day after
day, without adverse effect.
TLVTime Weighted Average (TLV-TWA)
This is defined as time weighted average concentration
for a normal 8 hour work day and a 40 hour work week, to
which all workers nearby may be repeatedly exposed , day
after day, without adverse effect.
TLV Ceiling (TLV-C)
It is the concentration that should not be exceeded even
instantaneously
 What is Mathematical Risk?

Risk is the product of probability of occurrence of an

undesired event (p) and the expected damage (d) due
to the occurrence of such an event and is
mathematically expressed as:

R = p* d

The damage could result into:

-fatalities
-economic losses etc.
 Other Definitions of Risk

The other possible definitions of risk are:

Rk= f *Dk
where k > 1 is a risk function which signifies the
importance of events with large damages.
Another approach to the interpretation of risk may be
developed by using a mathematical notation, such as risk
density Rj (Xj, t), which is the frequency of consequence
of an event Ej at any time t producing an ultimate damage
of consequence type j between Xj and Xj+ dxj per unit dxj.
The risk is considered-1 a density function because it has
units of (consequence) .

Rj ( Xj, t) = Rj ( xj t) dxj
xj
 Other Definitions of Risk

When the operation of a system leads to risks from

more than one consequence type, yet another type of
risk can be defined. Aggregated risk from event Ej, Rj
k (t), as measured from the consequence type k, is
the risk arising from event Ej due to all the possible
consequences. Aggregated risk may be written as:

Rj (k) (t) = aj (k) Rj (Xj, t) dXj ; aj (k) is
j 0 aggregation factor
 Why Perform Risk Analysis ?

1. Planners / Engineers have a moral obligation to

design the safest possible system (with lowest
probability of system failure and minimal
consequences if the system does fail) within the given
set of engineering constraints

2. Information useful in comparative risk assessment

3. Government regulations
 What is Hazard ?

Hazard signifies consequences (d) of an event.

While

Risk is the product of probability of occurrence of an

event (f )and the corresponding damage (d).
Safety is ( may be!) inversely proportional to
Risk

-Risk is expressed as fatality probability/year

Risk (Fatality Probability)/year =
f {p (occurrence of hazardous event)
x p (weather conditions)
x p (lethality factor ) x p (ignition
source) x number of persons
exposed} x p (hazardous event) }

In this training workshop, we will discuss PRA study

:only due to accidental release of hazardous
chemicals.
Conceptual Activities : Hazard Study
and Risk Analysis

Hazard Hazard
Identification Quantification

Hazard
Evaluation
 Risk Evaluation Risk Contour
Plot
Consequence (fatality probability) Mapping
Plan / Area Map
Analysis (D)

More Hazardous Hazard and operability

Process Information Units studies
Inventory Analysis
Identification of
Hazard Prone areas
P&I Risk Mitigation
Diagrams Fault Tree Analysis (f)
FEI and Measures DMP Report
Toxicity Index
Data collection on Less Hazardous Sensitivity Analysis
properties of Units
chemicals

Protective System Hazard

Analysis
Meteorological data

Check List
Population Approach
data

Failure Frequency
Past Accident Data
Analysis

Reliability Analysis
Failure Data

Probabilistic Risk Assessment at a Glance

Logical Sequence in Hazard and Risk
Analysis

qSafety Audit: Checklist & Rating

q Safety Review
-plot Plan, P & IDs Procedures
-applicable Codes & Standards
-schedule Interviews with specific
individuals
-request for records [e.g., Personal
injury, Hazardous incident reports,
pressure vessel inspection, prior
testing]
Suggest Action Plan
 Logical Sequence in Hazard and Risk Analysis

Relative Ranking
FETI / MOND Index
Preliminary Hazard Analysis
- A precursor to Hazard Analysis
Rapid Risk Assessment
MCA & Recommendations based on MCA
PRA / QRA / PSA -----
Mathematical Risk, Risk Mitigation
Measures, DMP / EPP
 Hazardous Installations (SEVESO
Directives) : Schedule 1
Group 1: Toxic Substances
Chemical Qty (t) Qty (t)
Notification Survey Reqd
Reqd
Phosgene 2 20
Chlorine 10 100
ACN 20 200
Hydrogen 20 200
Cyanide
Carbon disulfide 20 200
Sulfur dioxide 20 200
Bromine 40 400
Ammonia 100 1000
 Hazardous Installations (SEVESO Directives) : Schedule 1

Group 2: Substance of Extreme Toxicity

Toxic Liquid / Gas Lethal to man Con < 1 mg/l

Toxic Solids Lethal to man Con < 1 mg

Other than those which are and which will be

maintained at ambient temp & pressure (atm)
 Hazardous Installations

Group 3: Highly Reactive Substances

Chemical Qty (t) Qty (t)
Notification Reqd Survey Reqd

Hydrogen 2 20
Ethylene oxide 5 50
Propylene oxide 5 50
Organic peroxides 5 50
Nitrocellulose 5 500
compounds
Ammonium nitrate 500 5000
Sodium chlorate 500 5000
Liquid oxygen 1000 10000
 Hazardous Installations:

Group 4 Other Substances

Flammable gases 15 150

LPG / propane / butane & 30 300

mixture thereof
Flammable liquids above their 20 200
boiling point (at 1 bar) and pr >
1.4 bar including flammable
gases dissolved under pr.
20 200
Liquid flammable gas under
refrigeration which have 50 500
0
boiling point below 0 C at 1
bar
500 5000
com. fertiliser
500 5000
Plastic foam
 Safety Audits

1.Site level- Management System ,Specific tech

features, and Plant level Management System
Main Elements (5)
1.Identification of possible loss producing situation;
2.assessment of potential losses associated with
these risks;
3.selection of measures to minimize losses;
4.Implementation of measures within organization;
5.Monitoring of changes.
 Safety Audits

The Audit is conducted in a fairly formal way, using a

check list.
Activity standards for safety audits can be used as
the basis of a numerical rating scheme.
 Activity Standards for Safety Audits
Activity: Poor / Fair / Good / Excellent

A Organisation and administration

q statement of policy; responsibility assigned
q safe operation procedures (SOP)
q employee selection & placement
q emergency & disaster control plans
q direct management involved
B Industrial hazard control
q house-keeping storage of materials etc
q machine guarding
q general area guarding
q maintenance of equipment, hand tools, etc
q personal protective equipment adequate & use
 Activity Standards for Safety Audits
Activity: Poor / Fair / Good / Excellent

C Fire control & industrial hygiene

q chemical hazard control references
q flammable & explosive material control
q ventilation fumes, smoke and dust control
q skin contamination control
q fire control measures
q wash-trash collection, disposal air / water pollution
D Supervisory participation, motivation & Training
q line supervisor safety training
q indoctrination of new employees
q job hazard analysis
q training for specialised operations
 Activity Standards for Safety Audits
Activity: Poor / Fair / Good / Excellent

internal safe inspection

-safety promotion and publicity
-employee / supervisor safety contact / community

E Accident investigation, Statistics & report

q accident investigation by line personnel
q accident, cause, injury, location anlys & statistics
q investigation of property damage
q proper reporting of accident and contact with carrier
Note
q Management should try to implement recommendations of
the safety audit
Safety Audit & Hazard Identification
Techniques
Project Stage HI Techniques
All Stages Management & Safety system
audits
Checklists
Feedback from workforce
R&D Screening & testing for
chemicals (toxicity, instability,
explosiveness)
Reactions (explosive)
impurities; pilot plant
Pre-design Hazard Indices
Insurance assessments
Hazard Study (coarse scale)
 Safety Audit & Hazard Identification Techniques

Design Process design checks

Unit process /
operations
Plant equipments
Pressure systems
Instrument systems
HAZOP Study
Failure mode and
effect analysis
Failure Tree & Event
tree
Hazard analysis
Reliability assessments
Operational Task
analysis & operating
Instruments
 Safety Audit & Hazard Identification Techniques

Commissioning Checks against D, I, E, T

Non destructive testing /
condition Monitoring
Plant safety Audit

Operation Inspection, Testing, NDT,

Con. Monitoring, CO, Plant
US Legislation on Safety and Loss Prevention (Selected)
Year

1899 Rivers and Harbour Act

1908 Explosive Transportation Act
1909 Explosive Transportation Act (Rev 1)
1921 Explosive Transportation Act (Rev 2)
1936 Tank Vessels Act
1938 Natural Gas Act
1956 Federal Water Pollution Control Act
1958 Federal Aviation Act
1965 Solid Waste Disposal Act
Water Quality Act
1968 Natural Gas Pipeline Safety Act
1969 National Environmental Policy Act
1970 Clean Air Act
Dangerous Cargo Act
Fed. Environmental Pollution Control Act
Hazardous materials Transportation Act
Occupational Safety & Health Act
Resource Recovery Act
1972 Coastal Zone Management Act
Fed. Water Pollution Control Act / Noise Control Act
Parts and waterways Safety act
1974 Safe Drinking Water Act
1976 Toxic Substances Control Act
 Hazard Assessment
Acceptable Risk Problems
1. individual and average risk 5. max risk to public
2. death v/s injury 6. multiple formula
3. max risk to employees 7. engg feasibility
4. value of human life 8. allocation of resources
Value of Life Approaches
1. Future production
Value between 10000 100,000
2. Administrative decisions
Worker safety 15,000 20 m
Consumer safety 0 20 m
Medical care - up to 20,000
3. Consumer preference 00 000 (value of life)
4. Court awards 5. Life Insurance
Fire and Explosion Index
 Fire and Explosion Index
and Toxicity Index

The Fire and Explosion Index is intended as a tool to

determine the areas of greatest loss potential in a
particular process. The F & EI system is primarily
designed for any operation in which a flammable,
combustible or reactive material is stored, handled
or processed
In short the purpose of the F & EI system is to :
Quantify the expected damage of potential fire &
explosion incident in realistic terms; Identify
equipment that would be likely to contribute to the
creation or escalation of an incident; Communicate
the F & Explosion risk potential to management.
Past Accident Analysis
Why do we need Functional Safety?
Analysis Of 34 Incidents, based on 56 causes identified
20 %
Changes after
commissioning

44 %
Specifications

15%
Operations and
maintenance

6%
15%
Installations and
Design and
commissioning
implementations

Out of control
Why control systems go wrong and how to prevent failure?
(2nd edition, source: Health & Safety Executive HSE UK)
 Past Accident Analysis
Ammonia Plant, International Scenario

Desulphurizer Sec. Reformer

Primary Reformer Methanator
Syn. Gas Converter Ammonia Seperator
Storage Storage Vessel
Vessel Desulphurizer
29.3% 3%
Sec. Reformer
14%

Ammonia
Seperator
3% Primary Reformer
26%
Syn. Gas Converter
Methanator
22%
2%

Bullets in Mexico Disaster

Buncefield Petro Depot Fire in UK
Piper Alpha Aftermath
Flixborough Disaster
 Flixborough Disaster

On Saturday, June 1, 1974, an explosion occurred in

the Nypro UK works. The explosion was similar in
magnitude to one that would have resulted from 15 t
of TNT.
The factory was engaged in the production of cyclo
hexanone from cyclohexanol by means of an air
oxidation process in the presence of catalysts at
1550C and 125 psi pressure. The oxidation process
involved the use of a series of six reactors.
 Flixborough Disaster

The exothermic chemical reaction involved the

formation of cyclo hexyl hydro peroxide, which being
unstable is known to undergo ready decomposition to
cyclo hexanone and cyclo hexanol along with some
byproducts. The process involved a low conversion to
minimize build-up of side reaction products.
In the course of time, one of the reactors suffered
a maintenance problem and a decision was taken to
continue the process with five reactors in place of
six. This amounted to temporary changes in the
equipment configuration.
 Flixborough Disaster

Since the process chemistry involved the formation

of hydro peroxides and other side products, greater
care was necessary to ensure that the reaction
assembly was capable of withstanding the release of
energy from the exothermic process involved in the
air oxidation process used by the company. Such care
was not taken.
Whereas the total system should have been tested to
an operating pressure of 11.05 atm, the system was
actually checked for a pressure of 9 atmosphere
after readjustments in equipment configuration.
 Flixborough Disaster

Furthermore, in the readjusted configuration, the lack

of nitrogen purging in the process line may also be
significant because of the implication of a hydro
peroxide intermediate. Due to the excessive build-up
and release of energy during the reaction, the reactor
assembly gave way. The sudden release of pressure led
to an explosion.
Especially because the process chemistry involved the
formation of peroxides, it was all the more necessary to
test the system for its ability to meet the pressure
requirements. Unfortunately, such analysis were not
carried out and the result was the explosion leading to
the loss of life and the entire plant and damage to
environment.
Simplified plan and elevation of the
X 2529 X 2531
cyclohexane oxidation plant at Flixborough Disaster
Flixborough
Elevation on AA
H
S = Separator V = Valve NR
R = Reactor NR = Non 4 6
V
Return Valve
X = Mixer
H = Pipe hanger

S 2539 S 25309

Ground

N 8 inch pipe 20 inch pipe Ground

Scaffolding omitted
Plan
A
S 25309 S 2538

1 2 3 4 6

Feet 10 0 10 20 30
 F Effective
areas of
bellows A
PA

2e
Thrust PA

2L

Shear Force
F = PAe / L

Maximum
BM = PAe / L
Bending Moment
Sketch of pipe and bellows assembly Diagram
showing shear force and bending
moments in pipe
(Due to internal pressure only)
 Lessons learn from the Accident
Analysis?
Respect for domain expertise of all the
concerned.
Go for HAZOP study with utmost care.
 Allocating Safety Integrity Levels in
Practice
Risk Acceptability
ALARP
Risk shall be brought As Low As Reasonably Practicable;
Three risk zones: unacceptable, acceptable, negligible
assumes that we know where the acceptable limit is!
GAMAB
Any modification shall leave a system globally at least as
good ("Globalement Au Moins Aussi Bon") as it was allows
for redistribution of risks assumes current level is
already acceptable
MEM
Starts with lowest technological mortality rate in the
population (Minimum Endogenous Mortality)
a new system should not increase that mortality rate
 Reducing Risk

Inherent Process Risk

Likelihood

Unacceptable
Risk Region

Tolerable Risk
Region
Consequence
 Fuzzy numbers for risk acceptability
criteria (Experts Opinion)
Level of Presumption ()

Not Acceptable
Very Safe Safe Acceptable
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1

0 -10 -9 -8 -7 -6 -5 -4 -3 -2 -1 0
Interval of confidence (Fatality Probability)
Knowing Ignorance is Strength
Ignoring Knowledge is Sickness

Lao Tsu
Chinese philosopher, in Tao Te Ching, circa 600 BC