Chemical Process Safety

Chapter 11: Hazard Identification

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 Learning Objectives – Chapter 11

• Define terms related to hazard identification and risk

assessment.
• Describe the hazard identification and risk
assessment procedure.
• Identify the various methods available for hazard
identification / evaluation and risk assessment.
• Describe several commonly used methods for
hazard identification / evaluation.

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 Introduction
Why? To identify hazards so that they can be
eliminated or controlled.
How? Using a number of available
procedures.

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 Procedure in Simple Terms
1. What are the hazards?
2. What can go wrong and how?
3. How bad could if be?
4. How often could it happen?
5. What is the risk?
6. How do we control and manage this risk?

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Hazards
Identification

Hazards
Evaluation

Major Steps in Procedure

Risk
Analysis

Risk
Assessment
Non-scenario methods: Depends on the experience of
the review team.

Checklist analysis: A written list of items or

procedural steps to check and validate.
Safety review: A committee review that identifies plant
conditions or operating procedures that could lead to
an incident.
Inherent safety review: Identifies hazards to find ways
to eliminate or reduce hazards. Often incorporated
with checklist reviews, what-if, or HAZOP methods.
Preliminary hazard analysis: A list of hazards, causes,
major effects and corrective/preventive measures.
Relative ranking: Calculates a number that is a
relative indication of the hazard/risk.

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Scenario-Based Methods: Use predictive and analytical
methods to define the incident scenarios.

*Hazard and Operability (HAZOP) study: A careful

review of a process to identify deviations from the
design or operational intent that can lead to undesired
consequences.
*Fault Tree Analysis (FTA): A deductive technique that
focuses on one particular incident or main system
failure and determines the causes of the incident.
*Event Tree analysis (ET): Determines all the possible
outcomes following the success or failure of protective
systems.
Failure Modes and Effects Analysis (FMEA): Tabulates
failure modes of equipment and their effects on a
system or process.
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Scenario-Based Methods: Use predictive and analytical
methods to define the incident scenarios.

What-if analysis: A brainstorming approach to ask

questions or voice concerns about possible undesired
events.
What-if /checklist analysis: Combines what-if analysis
with a checklist.
Cause –Consequence Analysis (CCA) and bow-tie
analysis: A blend of the fault tree end event tree
methods.
Quantitative Risk Analysis (QRA): A very rigorous
approach using source models, dispersion models,
and effect models to calculate risk estimates for every
possible scenario.
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Scenario-Based Methods: Use predictive and analytical
methods to define the incident scenarios.

*Layer of protection analysis (LOPA): A simplified

form of quantitative risk analysis using order-of-
magnitude categories for initiating event frequency,
consequence severity, and likelihood of failure of
independent protection layers (IPL). LOPA
determines the adequacy of safeguards in the
context of hazard evaluations.

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 SAFE PROCESS DEVELOPMENT

Synthetic Desktop Discovery Automated Pilot plant Scale up Industrial production.

organic screening, research and laboratory studies and design Debottlenecking.
chemistry databases, multiple reactors. Optimization of
ideas calculations experiments Process mature processes.
optimization Retrofits.

CHEMICAL PROCES S LIFE CYCLE

Desktop Micro and Automated Kinetics, Adiabatic HAZOP, Design reappraisal,

mini scale Calorimeters modelling, calorimeters HAZAN, relief systems, dump and
studies simulation quench tanks
reactors and reactors HAZID
Objective is to move from the earliest phases of research and development through to
full scale production in a confident, safe and cost effective manner

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Process Example Hazard Typical Hazard Evaluation or Risk
Phase Identification/Evaluation Objectives Analysis Method
Research -Identify chemical reactions or Inherent safety review
and chemical incompatibilities that Relative ranking
development could cause runaway reactions, Preliminary hazard analysis
fires, explosions, or toxic gas
releases.
-Identify process safety data needs
for future analysis.
Conceptual -Select process technology based Inherent safety What-if
design on inherent safety. review What-
-Identify other opportunities for Checklist analysis if/checklist
inherent safety. Relative ranking Inherent
-Compare the hazards between Preliminary safety review
potential plant sites. hazard analysis LOPA
Pilot plant -Identify ways for hazardous Checklist analysis FMEA
materials to be released to the Preliminary Fault tree
environment. hazard analysis Event tree
-Identify ways a catalyst can be What-if Cause–
deactivated. What-if/checklist consequence
-Identify potentially hazardous HAZOP analysis
operator interfaces. LOPA
Bow-tie
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Process Example Hazard Typical Hazard Evaluation or
Phase Identification/Evaluation Objectives Risk Analysis Method
Detailed -Identify ways for a flammable mixture Inherent safety FMEA
engineering to form inside process equipment. review Fault tree
-Identify how a reportable spill might Checklist Event tree
occur. analysis Cause–
-Identify which process control Preliminary consequence
malfunctions will cause runaway hazard analysis
reactions. analysis QRA
-Identify ways to reduce hazardous What-if LOPA
material inventories. What- Bow-tie
-Evaluate whether designed if/checklist
safeguards are adequate to control HAZOP
process risks to required levels.
Construction -Identify error likely situations in the Safety review
and startup startup and operating procedures. Checklist analysis
-Verify that all issues from previous What-if
hazard evaluations were resolved What-if/checklist
satisfactorily and that no new issues
were introduced.
-Identify hazards that adjacent units
may create for construction and
maintenance workers. 12
Process Example Hazard Typical Hazard Evaluation or
Phase Identification/Evaluation Objectives Risk Analysis Method
Routine -Identify hazards associated with Inherent FMEA
operation operating procedures. safety review Fault tree
-Identify ways an overpressure Safety review Event tree
transient might occur. Checklist Cause–
-Update previous hazard evaluations to analysis consequence
account for operational experience. What-if analysis
-Identify hazards associated with out- What- QRA
of-service equipment. if/checklist LOPA
-Ensure that maintenance is done on HAZOP
time and safely. Bow-tie
Process -Identify whether changing the
modificatio feedstock composition will create any All methods
n or plant new hazards or worsen existing ones.
expansion -Identify hazards associated with new
equipment.
Decommis -Identify how demolition work will affect Safety What-if
sioning adjacent units. review What-if/checklist
-Identify any fire, explosion, or toxic Checklist
hazards associated with any residues analysis
left in the unit after shutdown.
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Process Phase Example Hazard Typical Hazard Evaluation or
Identification/Evaluation Objectives Risk Analysis Method
Incident As required. What-if Event tree
investigation HAZOP Cause–
FMEA consequence
Fault tree analysis
Bow-tie QRA

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 Factors that Influence the Selection of a Method

1. Motivation for the study, i.e. regulatory

requirements, company policy.
2. Type of results needed, i.e. list of hazards,
potential accident situations.
3. Type of information available to perform the study,
i.e. availability, quality and current status of
information.
4. Characteristics of the analysis problem, i.e. type of
process, complexity, nature of hazards.
5. Perceived risks associated with the process, i.e.
amount and nature of the risks.
6. Resource availability, i.e. availability of
knowledgeable personnel, target completion date,
financial resources. 15
 Checklists - 1

Checklists are a list of things to consider.

Can never be complete.
Not effective for procedures.
Are useful in preliminary design.
 Checklists - 2
CHECKLIST 10 - 1000 items
preliminary • general layout Fig. 11-2
stage • buildings
• process
• piping Further study required
• equipment Does not apply
• venting
• instruments & electrical Completed
• safety equipment
• raw materials Details
• handling equipment
• extreme weather
• toxic, flammable
• proper containers
• labelling containers
• bad spills
• storage / distribution
Fig. 11-2
in book
(much
longer)
 Relative Ranking Methods

Provide a unitless number representing the

relative hazard.

Examples:
Dow Fire and Explosion Index (F&EI)
Dow Chemical Exposure Index (CEI)

(Limited to flammable and toxic materials)

Dow Fire and Explosion Index
• The fire and Explosion Risk Analysis System is a step by step
objective evaluation of the realistic fire, explosion, and reactivity
potential of process equipment and its contents.
•Operates like an income tax form.
• Penalties for unsafe situations
•Credits for control and mitigation
• Produces a number - the bigger the number the greater the
hazard.
• Only considers flammable materials
• Not completely effective for procedures.
• Need greater than 1000 gallons of material
• Most sensitive to material quantity.
 Basic Procedures

•Select Process •Calculate Loss Control

•Find Hazard Factor Credit
•Calculate Index Factors
•Conduct Risk Analysis •Calculate Actual MPPD
•Calculate Base MPPD •Determine Maximum
(Maximum probable priority Probable Days Outage and
damage) Business Interruption
•Audits
 F&EI
This is the first page of
the F&EI form.
You need the complete
booklet (available from
AICHE) to use this.
The book provides
reference information.
 Dow Chemical
Exposure Index (CEI)
• Considers toxic materials only.
• Includes simple source and dispersion models.
• Not effective for procedures.
•Evaluates neighboring community risk

Dow Criteria: If sum of F&EI and CEI > 128, then

more detailed hazard review procedure required.

See Example 11-1 in textbook

 CEI
This is the first page of
the CEI form.
You need the complete
booklet (available from
AICHE) to use this.
The book provides
reference information.
Methodology
Material Factor
Material Reactivity
Material Temperature Adjustment
(for Process T>140oF)
Elements of the Index
Elements of the Index
 CEI Methodology
The Chemical Exposure Index (CEI) provides a simple method of rating the relative
acute health hazard potential to people in neighboring plants or communities from
possible chemical release incidents. Absolute measures of risk are very difficult to
determine, but the CEI system will provide a method of ranking one hazard relative to
another. It is NOT intended to define a particular design as safe or unsafe.
The CEI is used:

· For conducting an initial Process Hazard Analysis (PHA).

· In the Distribution Ranking Index (DRI) calculations.

· By all locations in their review process which provides the opportunity to make
recommendations for eliminating, reducing or mitigating releases.

· In Emergency Response Planning

 CEI Procedure
1. To develop a Chemical Exposure Index (CEI), the following items are used:
a. An accurate plot plan of the plant and the surrounding area.
b. A simplified process flow sheet showing containment vessels, major piping and chemical inventories.
c. Physical and chemical properties of the material being investigated, as well as the ERPG/EEPG
values.
2. Identify on the process flow sheet any process piping or equipment that could
contribute to a significant release of an acutely toxic chemical.

3. Determine the Chemical Exposure Index and the Hazard Distances.

4. Fill out CEI Summary Sheet.

 CEI Procedure

Similar treatment is provided in the software for liquid and 2-f release
CEI Procedure
CEI Procedure
 Hazard and Operability Studies
(HAZOP)

• Can identify hazards due to fixed equipment and

procedures.
• Is a huge effort.
• Provides a controlled mechanism to consider the
things that can go wrong.
• Customized for each company.
• Improves process performance, quality, etc.

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 Hazard and Operability Studies (HAZOP)

• HAZOP review done by a team of 5 to 10 people.

• Team leader must be trained.
• Procedure can generate 1000s of combinations.
• Need a method to keep track of issues considered.
• Need a management system to track action items.
• Procedure can take several months.
• Max. activity: about 2/3 meetings per week, 2-3
hours.

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 HAZOP Definitions
Node: A location on a process diagram at which process
parameters are investigated for deviations. Node
examples are:
A pipeline transferring material between two units
A specific tank or vessel
Design intent: Defines how the system is expected to
operate at the nodes. It provides a point of reference for
developing deviations.
Parameter: A characteristic of the process that describes
it physically, chemically, or in terms of what is
happening:
Specific parameters: flow, temperature, pressure, etc.
General parameters: addition, reaction, maintenance,
relief, etc.
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 HAZOP Definitions
Guidewords: See Table.
Deviations: These irregularities are discovered by
systematically applying the guidewords to each
parameter at each node (e.g., more + temperature =
higher temperature).
Causes: The reasons why deviations may occur. Causes
can be equipment failure, human error, or external
events.
Consequences: Documented as impacts resulting from
the loss event.

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 HAZOP Definitions
Recommendations: Suggested actions to prevent or
mitigate the consequence of deviations, or to obtain
further information.
Safeguards: The systems in place that reduce the
probability of the deviation occurring or mitigate the
severity of the consequences.

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 HAZOP Guidewords

No Other than
More Sooner than Batch
Less Later than
As Well as Where else
Part of
Reverse

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 HAZOP Guidewords
Guide Meaning Comments
words
no, not, The complete No part of the design intention is
none negation of the achieved, but nothing else happens.
intention

more, Quantitative Applies to quantities such as flow rate

higher, increase and temperature and to activities such
greater as heating and reaction.

less, lower Quantitative Applies to quantities such as flow rate

decrease and temperature and to activities such
as heating and reaction.
as well as Qualitative All the design and operating intentions
increase are achieved along with some
additional activity, such as
contamination of process streams.
part of Qualitative Only some of the design intentions are
decrease achieved; some are not. 44
Guide Meaning Comments
words
reverse The logical Most applicable to activities such as
opposite flow or chemical reaction. Also
applicable to substances—for
example, poison instead of antidote.

other than Complete No part of the original intention is

substitution achieved; the original intention is
replaced by something else.

sooner than Too early or in the Applies to process steps or actions.

wrong order

later than Too late or in the Applies to process steps or actions.

wrong order

where else In additional Applies to process locations, or

locations locations in operating procedures.
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 HAZOP Process Parameters
Temperature Start
Pressure Stop
Flow Power
Level Component
Concentration
Agitation
Reaction
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 Guideword / Parameter Combinations

Some combinations of guidewords and process

parameters do not make sense for specific equipment
pieces.
Examples: No temperature
Reverse temperature
No viscosity
Reverse pressure

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HAZOP Guide Words
HAZOP Process
HAZOP Process- 1
HAZOP Process- 2
HAZOP Process- 3
HAZOP Process- 4
 HAZOP Procedure - 1
1. Begin with a detailed flow sheet.
2. Divide flow sheet into sections, i.e. reactor, storage.
3. Choose a study node, i.e. line, vessel, pump,
operating instruction.
4. Describe its design intent.
5. Select a process parameter.
6. Apply a guide word to the process parameter.
7. If the deviation is applicable, determine possible
causes.
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 HAZOP Procedure - 2
8. Evaluate consequences of the deviation.
9. Recommend action:
what? who? when?
10. Record all information.
11. Repeat 5 to 10 for a new guide word.
12. Repeat 4 to 11 for a new process parameter.
13. Repeat 2 to 12 for a new study node.
14. Repeat 1 to 13 for a new flow sheet section.

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HAZOP Procedure - 3
HAZOP Example

Coffee grounds

Coffee filter
Water
Coffee
container
Power
Study Nodes

Select water as a study node.

Apply process parameter of flow.
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 HAZOP Example - 2
Param. Dev. Cause Consequence Action

Flow No 1. No water No coffee Check water

2. Plugged spout “ Clean spout
3. No power “ Check power
4. Basket plugged “ Clean basket
More Too much water Pot overflows Check level
Less Not enough water Pot not filled Check level

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HAZOP Exothermic Reaction
Example 11-2

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 HAZOP Summary
Advantages: Meets regulatory requirements
Plant operates better
Less down time
Product quality improved
Employees are happier
Disadvantages: Time, people and effort
Information management problem

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 Safety Review
INFORMAL REVIEW
- small changes to existing process responsible individual +
- laboratory & bench scale process (external) safety reviewer
Example 11 - 1

FORMAL REVIEW
- new process prepare initial safety report,
- substantial changes to existing process committee review,
- update review required inspection of process
implementation of recommendations
MISCELLENEOUS
- What if ? - applied to specific equipment pieces
- Human error analysis - useful for control panel layout
- Failure mode, effect & criticality analysis (FMECA) - list of failure modes
 Safety Review

Phosgene
TLV-TWA 0.1 ppm
Safety Review
 Safety Review
• A flow indicator provides a visual indication of the flow. This
is a simple bubbler.
• A relief system composed of a glass U-tube filled with liquid
is added with an outlet to the scrubber.
• The trap catches any liquid phosgene that may come from the
tank.
• Single scrubber is replaced by two bubblers with caustic and
ammonium hydroxide to absorb any phosgene or HCl vapor.
• Vacuum is added to reduce the boiling point temperature.
• A pail of caustic is added (the phosgene cylinder would be
dumped into this pail in the event of a cylinder or valve leak;
the caustic would absorb the phosgene).
 Safety Review Report
INTRODUCTION - summary
- process overview
- chemical reactions
- engineering data
RAW MATERIALS & PRODUCTS associated (minimization) hazards

EQUIPMENT SETUP configuration, technical specifications

PROCEDURES - normal procedures
- safety procedures emergency shutdown
fail safe
major releases
- waste disposal
- clean-up
SAFETY CHECKLIST operator
MSDS

Experienced committee required

Report easy to apply

End of Chapter 11

Questions?

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