Lec 12

DEPARTMENT OF CHEMICAL ENGINEERING
SAFETY IN CHEMICAL INDUSTRIES

Course Code: CLPE15
Number of Credits: 3
Lecture- 12
Dr. Kartikeya Shukla
Assistant Professor
Department of Chemical Engineering
NIT Trichy 1
Radiations hazards and its control
• Radiation refers to the process of emission, transmission,
reflection or absorption of energy.
• Electromagnetic.
• Electromagnetic radiation is special type doesn’t requires
medium.
– Ionizing : X-rays, γ rays, β particle, α particle
• Very high dose can cause death
• Moderate dose can cause tumor
– Non ionizing: UV rays, visible light, Radiowaves,
Television waves
• High exposure can heat up body tissues
Department of Chemical Engineering Safety In Chemical Industries 2

• Ionizing radiation:
– Nuclear
– Electronic: Cathode ray tube, electron guns
• Radioactive isotopes and stable isotopes.

• Radioactive isotopes tend to stabilize after giving off radiations.
• Half life
• 2He
4
• Alpha particle:
– Little penetration due to large size
– Not potential hazard if not ingested
– Helps in cancer treatment
– smoke detectors

• β particle
– (-)vely charged particle
– can penetrate deeper than alpha
– Cathode rays
– Electron accelerators
– Glass, plastic, aluminium, used for shielding purpose
– For low energy, iron, copper, are used

X-rays, γ rays
• Electromagnetic radiations analogous to light but short
wavelength
– Shortwave radiation contains higher amounts of energy
and longwave radiation contains a smaller amount of
energy.
– Therefore, the sun gives off shortwave radiation, as it is
extremely hot and has a lot of energy to give.
• Emitted from nuclei, electron transfer

• X-rays are called Roentgen rays
• X-rays are used in clinical purpose.
• γ rays can be followed by alpha or beta decay.

• Neutrons
• Not emitted spontaneously from radioactive nuclei
• Release depends on the interaction of α particle, γ particles
with nuclei of target materials
• Neutrons are neutral hence very high penetrating power.
• Too many protons in nucleus leads to emit positron.
• Too much energy in nucleus leads to emit γ rays.
• Too much mass in nucleus leads to emit alpha particle.

Radiation measurements
• Curie (Ci), Becquerel (Bq)
• 1 Curie=3.7×1010 nuclear disintegrations per second.
• Many laboratories perform less than 1mCi.
• Radiation depends on type, quantity, type and amount of
interaction with matter.
• The roentgen is a unit of measurement for the exposure of X-
rays and gamma rays, and is defined as the electric charge
freed by such radiation in a specified volume of air divided by
the mass of that air (coulomb per kilogram).
• 1 Roentgen=0.000258 coulomb/kg

• The radiation dose absorbed by a person (that is, the amount of
energy deposited in human tissue by radiation) is measured using
the conventional unit rad or the SI unit gray (Gy).
• The biological risk of exposure to radiation is measured using the

conventional unit rem or the SI unit sievert (Sv).
• When a person is exposed to radiation, energy is deposited in the

tissues of the body.
• The amount of energy deposited per unit of weight of human tissue

is called the absorbed dose.
• The rad, which stands for radiation absorbed dose

• To determine a person’s biological risk, scientists have
assigned a number to each type of ionizing radiation (alpha
and beta particles, gamma rays, and x-rays) depending on that
type’s ability to transfer energy to the cells of the body. This
number is known as the Quality Factor (Q).
• When a person is exposed to radiation, scientists can multiply
the dose in rad by the quality factor for the type of radiation
present and estimate a person’s biological risk in rems. Thus,
risk in rem = rad × Q.
• The rem has been replaced by the Sv. One Sv is equal to 100
rem.

Measuring radiation
• To maintain a cumulative record.
• To measure over short period the exposure of individual

carrying out a specific operations.
• To survey flux or radiation level in all parts of the facility.
• To monitor contamination of hands, feets, hair, skin.
• To establish legal protection for employers and employees.

Radiation instrumentation
• Film badges
• Photographic film
• Low cost, convenient size, capability of integrating dose for a
long time
• X-rays, β rays, γrays, neutron radiations.
• Don’t respond to α rays.
• Holder with small disks of different metal pieces.
• If neutrons are involved, additional film of Cd should be
taken.
• 7-10 days and returned to the service supplier.
• Emergency processing should also be done.
• Filters, absorption leadsSafety
toIndetermine
Chemical Industries
level of exposure. 12
Ionization chamber
• Provides a method of measurement based on the movement of
ions from one part of chamber to electric plate.
• Ions in a gas are reactive and may be chemically changed
while moving towards electrode.
• Total charge is not altered.
• Personal monitoring pocket ionization chamber like fountain
pen.
– Initially pen is charged to a known voltage.
– Change in the capacitance can be noted down.

Grieger Mueller Counter
• Countmeter
• Count rate meter
• Thin walled tube reacts with radiation to produce electronic

pulses that are amplified so that they can be heard through
speakers or earphones.
• Can pinpoint the radiation .
• Cannot determine their energies.

Scintillation counters
• Atom excited to higher electronic state.
• Loses energy and return to its lowest state by emitting
photons.
• For some substance the energy is lost by collisions.
• For some substances, energy is not degraded and light is
emitted under irradiation.
• Inorganic media such as ZnS, organic substances serve as
scintillating media and burst of light is detected, and
amplified.
• ZnS

Alpha detectors
• Except scintillating counters, others will not work for alpha.
• Very Thin plastic covered window permits alpha particle to

enter electric field.
• Electronic pulse amplified and indicated by meter.

Exposure to radiations
• Biological effects of radiation
– Genetic and cellular damage
• Terrestrial sources include uranium, actium,
thorium.
• Radon contribute largest to radioactivity to
natural background

• Body can repair damage from radiation upto a
level.
• At what point?
– Depends upon the ionization
– Direct
– Indirect
• Effects may be reversible or irreversible.

Decreasing order of sensitivity to
radiation
• Lymphocytes
• Granulocytes
• Basal cells
• Alveolar cells
• Bile ducts cells
• Cells or tubules of the kidneys
• Endothelial cells
• Connective tissue cells
• Muscle cells
• Bone cell
• Nerve cell
• Internal radiation exposure
• Certain isotopes tend to concentrate in most
vital organs.

Control of exposure to radiation
• No unnecessary exposure should be permitted.
• Risk of the exposure should be balanced against importance of
results to be obtained.
• Strong source require meticulous care
• Preplanning of a facility, careful selection and use of
equipment, SOP, adequate education and training of personnel.
• Every operation involving ionizing radiation should be
preplanned, if possible, rehearsed
– Time
– Distance
– Shielding

Time
• Exposure dose=rate×time
• Preplanned
• Distance:
• Radiation follows inverse square law (light
intensity)
• If radiation flux is 1 at a given distance, it will be
¼ at twice distance
– Mirrors, telescope.
Shielding or filters
• Any matter or mass placed between a radiation source or
beam and point of exposure will screen or decrease the
exposure
• Even air has some shielding effect.
• Lead or other heavy metals excellent shields for radiation,
but cost is high
• Concrete mixed with iron ore, heavy mineral is effective
• Frequently used approach is locate the machine, source in a
pit or depression underground
• Deep pools of water, if water doesn’t adversely affected by
water.

Course Code: CLPC22
Lecture- 13
Assistant Professor
NIT Trichy
• Location
• Site selection
• Plant layout
• Unit plot planning

• Processing units
• Maintenance shop
• Ware house
• Safety house
• SRP
• R&D
• Pilot plants
• Admin block
• Waste water treatment
• Boiler
• Elevated flare
• ETP
• R&D section
• Safety office
• Warehouse
• First degree Line of defense to prevent second
degree hazard. Engineering
– Direction of wind
– Providing adequate access ways
• Second line of defense
– Separating hazardous areas from areas occupied by
people
– Strategically locating fire fighting equipment.
• Third line of defense
– Hospital facilities
Tools and techniques of defense
• Natural tones
– Topography
– Direction of wind, adequate water
• Intelligence of man
– Separation
– Concentration of hazards and identification of
hazards
• Design and build physical facilities to combat
hazards.
Safety problems of site selection
• Toxic gases to residential area
• Flammable gases to ignition source
• Fog from cooling towers
• Two ways to combat these types
• Plant downwind from the community
• Waste stream
• High speed highways
• Community
• Adequate source of water
• Topography low land area for plant

Safety problems of plant layout
• Processing units most hazardous areas.
• Processing units should be removed from boundaries.
• Should be consolidated rather than scattered.
• Processing units and ignition sources.
• Processing units should be downwind from ignition sources
• Processing units and tanks area.
• Not too consolidated. Mutually hazardous. One unit operation and one shut
down
• Spacing of process units, remains a matter of good judgment
– Operating temperature
– Operating pressure
– Types of materials
– Quantities of materials
– Space required for fire fighting

• Administrative facilities at the periphery and isolated
from hazardous components.
– Sales
– Largest concentration of people
• One adverse factor
• Laboratories adjacent to administrative facilities (no direct
contact)
• Safety office should be located on the periphery on the plant
• Boiler, maintenance shop ignition source, upwind location.
• Warehouse nearby maintenance shop
• Tank truck traffic, downwind area is preferred (peripheral
locations).

• Waste water facilities downwind.
• Cooling towers (toxics) downwind
location from roadways.
• Elevated flare or burning pot upwind or
downwind?
• Sidewind?
• Storage vessels downwind in tank area
consolidated.
– Separation of tanks from each other
– Separation of tanks from other
facilities
– Area required to provide dikes
• Try out for a layout Road
connectivity
• Arrange heavily travelled roads
• Ground level pipe alleys.
• Overhead pipe alleys.
• Expansion loop
• Pipe allies and road crossing overhead clearance
• Pipe allies and liked areas
• Power in wires
• Power lines below ground
• Safety locations remote from hazardous locations but
not enough
• General pattern for location of safety showers
• We may not get always the way we want.
• Flammable mixtures may not be uphill from point of
ignition
Safety considerations in unit plot
planning
• Construction and operation cost along with the
safety.
• Compact unit, cost and safety

• Accessways to both sides of considerable
portion of processing equipment, firefighting,
fire breaks
• Gantry crane
• Cooling tower header
• Depressed area firewalls

Department of Chemical
Safety In Chemical Industries 41
Engineering
Engineering
• A roadway
• A gantry way
• Cooling water header beneath the gantry way
• A line of fractionating towers, heat exchangers,
accumulators, reflux drums. Depressed about eight
inches.
• The main pipe alley of the unit. If the unit includes fan
type air coolers, they can also be mounted.
• A rows of pumps
• A roadway
• Roadways flanking fire fighting
• Gantry crane
• Area required for gantry way provides space
• Cooling water header water facility
• Depressed area will retain spills
• Removal of pump while unit is operating

• Control house
• Periphery best view of the unit
• Upwind location
• Furnace sideways
• Compressors reasonable separation
• Compressor leaks downwind.
• Reactors hot ignition source
• Electrical unit below ground
• Fire hydrants close to hazardous spots
• Indoors units
• No prevailing winds
• Distance would have solved the purpose of low cost containment
• Physical barrier
• Separate compartment ignition and flammables
• Two doors
• High temperature, high pressure isolated
• Fire resistant walls

• Building of multiple floors
• Flammable liquids should not be uphill of ignition sources
• Flammable vapors heavy or light
• Concentration of hazards:
– Ventilating systems
– High capacity drainage
– Remotely operated handling devices
• After that also limit size of hazards

Chemical Process safety
• There are many reasons for explosions during
chemical processing
– Decomposition and runaway chemical reactions
are the most common
– Often these are either exothermic and/or gas
producing reactions that go out of control
– Can be avoided if reactions are understood and
reactive chemicals are identified.


Course Code: CLPC22
Lecture- 15
Assistant Professor
NIT Trichy
Chemical Process safety
• There are many reasons for explosions during
chemical processing
– Decomposition and runaway chemical reactions
are the most common
– Often these are either exothermic and/or gas
producing reactions that go out of control
– Can be avoided if reactions are understood and
reactive chemicals are identified.

Runaway Reaction
• In chemical engineering, runaway is a process by which an
exothermic reaction goes out of control, often resulting in an
explosion.
• Exothermic chemical reactions can lead to a thermal runaway if the
heat generation rate exceeds the heat removal rate.
• When the reaction rate increases due to an increase in temperature,

causing a further increase in temperature and hence a further increase
in the reaction rate.
• Thermal runaway may result from exothermic side reaction(s), and is
characterized by an exponential increase in the rate of heat
generation, temperature and pressure.
Thermal profile of exothermic
reaction

Initiating factors
• Incorrect charging and inadequate cooling are the most
important initiating factors for the runaway reactions followed
by unknown exotherm/ decomposition, impurities and
incorrect agitation/mixing resulting in hotspots.
• Incorrect charging
• Inadequate cooling

• Unknown exotherm/decompostion: In the manufacture of
tetrachloro-ethane excess chlorine was reacted with acetylene
at 100°C in the presence of ferric chloride catalyst. On one
occasion, the temperature of the mix dropped to 60 °C and an
explosion ruptured the bursting disc and also cracked the
reactor. It was suggested that monochloroacetylene had
decomposed, initiating the explosion.

• Impurity exotherm: An initiating mix of ether, butyl chloride,
cyclohexane and butyl bromide for the preparation of a
Grignard reagent was added to a reactor containing
magnesium. Cyclohexane was added and immediately vapours
emerged from the condenser vent and the bursting disc
ruptured. The investigation revealed that the cyclohexane
transfer line was wet and the Grignard reagent had reacted
with the water to produce hydrogen and ethane.

• Incorrect agitation: Monoethanolamine was added slowly with
stirring to 98% H2SO4 which was maintained at 110°C in a
glass-lined reactor. The monoethanolamine and H2SO4 were
immiscible. When the reaction was complete the mix was
cooled and isopropyl alcohol was added to precipitate the
product. On the day of the incident, the reactor was charged
with H2SO4 and then there was a shift change. The oncoming
shift did not realize that the stirrer had not been switched on
and proceeded to add the monoethanolamine. When they
realised the temperature was not rising and switched on the
stirrer. The two liquids were mixed causing an instantaneous
chemical reaction and explosion.

Fault tree

Case studies
• T2 Laboratories, Florida

Phenol-formaldehyde reactions
• Phenol-formaldehyde reactions are common industrial processes.
• The reaction of phenol or substituted phenol with an aldehyde, such
as formaldehyde, in the presence of an acidic or basic catalyst is
used to prepare phenolic resins.
• Phenolic resins are used in adhesives, coatings, and molding
compounds.
• Typically, phenol-formaldehyde reactions are highly exothermic.
Once a reaction is initiated, heat generated by the reaction increases
the reaction rate generating more heat. Because the reaction rate is
typically an exponential function of temperature, the rate of heat
generation will accelerate. Without intervention, a thermal runaway
will occur, producing a large amount of heat in a very short time.

• Once the reaction begins to accelerate, the pressure of the system
will typically increase suddenly due to gas production and/or the
vigorous evaporation of liquid.
• If the reaction continues to accelerate, the pressure buildup may
reach and exceed the ultimate strength of the reactor and cause it to
explode.
• The heat of reaction is removed by the evaporation of water or other
liquid from the process, condensation of the liquid in the overhead
condensation system, and return of the liquid to the reactor vessel.
• Emergency relief on the reactor is usually provided by rupture disks.
• For safety reasons, slow continuous or stepwise addition of
formaldehyde is preferred.

Chemical Reactivity Hazard
• A chemical reactivity hazard is a situation with the potential
for an uncontrolled chemical reaction that can result directly
or indirectly in serious harm to people, property, or the
environment.
• The resulting reaction may be violent, releasing heat, large
quantities of toxic, or flammable gases or solids.
• If the reaction is confined in a container, the pressure within
the container may increase resulting in an explosion.
• Common materials that we use routinely by themselves with
negligible hazard may react violently when mixed with other
common materials, or react violently when the temperature or
pressure is changed.
Components of intrinsic safety
• The basic parameters that have to be considered for assessing the chemical reaction systems
are
• Thermodynamics
• Reaction energy
• Adiabatic temperature and pressure rise
• Kinetics
• Activation energy
• Reaction rate
• Rate of heat generation
• Rate of pressure rise
• Time to maximum rate
• Physical
• Heat capacity
• Thermal conductivity
• In addition to the above parameters the safe limits of temperature, feed rate and concentration
have to be defined as a function of operating conditions.

Reaction Hazard
• Analysis indicates that incidents occur due to:
• Lack of proper understanding of the thermo-
chemistry and chemistry
• Inadequate engineering design for heat transfer
– Inadequate control systems and safety back-up
systems Including venting arrangements
• Inadequate operational procedures, including
training

Assessing Reaction Hazard
• Controlling an exothermic reaction depends on the interaction
among: the kinetics and reaction chemistry
– the plant equipment design
– the operating environment.
• Chemical process industry must consider the following factors

to better understand and address the potential hazards and
consequences of reactive systems:

• Thorough hazard assessment: The chemical &
process hazards and the consequences of
deviations must be thoroughly understood,
evaluated, and appropriately addressed
through preventive measures. Several layers of
safety systems, whether complementary or
redundant should be considered to enhance
reliability.

• Complete identification of reaction chemistry and
thermochemistry:
• For some exothermic reactions, the time to runaway is very short.
• Over-pressurization can occur when gas or vapor is produced as
a byproduct of the reaction or any decomposition reactions.
• The kinetics of the runaway reaction will be reaction specific and
may differ in various runaway situations.
• The characteristics of the particular reactions must be determined
experimentally.
• Experimental data should be used to define process boundaries in
terms of the pressure, temperature, concentration, and other
parameters as well as the consequences of operating outside of
these boundaries.
• Addition of raw materials: Frequently, the
reaction rate is controlled by the addition rate
of one reactant or the catalyst and should be
determined based on chemistry studies.
Process industries must pay attention to the
order of ingredients, the addition rates, under-
or over-charging, and loss of agitation.

• Emergency relief: Runaway reactions may lead to
the rapid generation of gas or vapor. Under
certain conditions, the vapor generation rate may
be large enough to cause the vapor-liquid mixture
to swell to the top of the vessel, resulting in two-
phase flow in the relief venting system. Relief
system capacity should be evaluated in
conjunction with the hazard analysis to ensure
that sizing is based on an appropriate worst case
scenario.
• Administrative controls: If administrative
controls, such as training and standard
operating procedures (SOP), are used as a
safeguard against process deviation and
accidental release, consideration must be given
to human factors to ensure reliability

• Chemical plants produce products using a
variety of complex reactive chemistries.
• It is essential that the behavior of these
reactions be well characterized prior to using
these chemicals in large commercial reactors.
• Calorimeter analysis is important to
understand both the desired reactions and also
undesired reactions.

Characterization using Calorimeters
• Important questions that must be asked for the characterization of

reactive chemicals:
• At what temperature does the reaction rate become large enough
• What is the maximum temperature increase
• What is the maximum pressure during the reaction.
• At what time and temperature does the maximum self-heat rate or
pressure rate occurs
• Are there any side reactions
• Can the heat generated by chemical reactions (desired or
undesired) exceed the capability of the vessel/process to remove
heat
Tools for evaluating thermal
explosion
– Thermal analysis Differential Scanning

Calorimeter (DSC),
– Thermo Gravimetric Analyzer (TGA),
– Differential Thermal Analyzer (DTA).

Steps to Reduce Reactive Hazards
• Facilities should take the following steps to prevent runaway

reactions: Modify processes to improve inherent safety.
• Minimize the potential for human error.
• Understand events that may lead to an overpressure and
eventually to vessel rupture.
• Use lessons learned.
• Evaluate Safe Operating Procedures.
• Evaluate the effectiveness of the emergency relief system.
• Evaluate employee training and oversight
• Through Inherent Safety
• Use a reaction pathway that uses less hazardous chemicals
• Use reaction pathway that is less energetic, slower or easier to control
• Use smaller inventories of reactive chemicals both in process and in
storage
• Reduce shipping of reactive chemicals – produce on site on demand.

• Design equipments or procedures to prevent an incident in the event
of a human error.
• Control reactor stoichiometry and charge mass so that in the event of
a runaway reaction the pressure rating of the vessel will not be
exceeded.

Course Code: CLPC22
Lecture- 16
Assistant Professor
NIT Trichy
Phenol-formaldehyde reactions
• Phenol-formaldehyde reactions are common industrial processes.
• The reaction of phenol or substituted phenol with an aldehyde, such
as formaldehyde, in the presence of an acidic or basic catalyst is
used to prepare phenolic resins.
• Phenolic resins are used in adhesives, coatings, and molding
compounds.
• Typically, phenol-formaldehyde reactions are highly exothermic.
Once a reaction is initiated, heat generated by the reaction increases
the reaction rate generating more heat.
• Because the reaction rate is typically an exponential function of
temperature, the rate of heat generation will accelerate. Without
intervention, a thermal runaway will occur, producing a large
amount of heat in a very short time.
• Once the reaction begins to accelerate, the pressure of the system
will typically increase suddenly due to gas production and/or the
vigorous evaporation of liquid.
• If the reaction continues to accelerate, the pressure buildup may
reach and exceed the ultimate strength of the reactor and cause it to
explode.
• The heat of reaction is removed by the evaporation of water or other
liquid from the process, condensation of the liquid in the overhead
condensation system, and return of the liquid to the reactor vessel.
• Emergency relief on the reactor is usually provided by rupture disks.
• For safety reasons, slow continuous or stepwise addition of
formaldehyde is preferred.

Chemical Reactivity Hazard
• A chemical reactivity hazard is a situation with the potential
for an uncontrolled chemical reaction that can result directly
or indirectly in serious harm to people, property, or the
environment.
• The resulting reaction may be violent, releasing heat, large
quantities of toxic, or flammable gases or solids.
• If the reaction is confined in a container, the pressure within
the container may increase resulting in an explosion.
• Common materials that we use routinely by themselves with
negligible hazard may react violently when mixed with other
common materials, or react violently when the temperature or
pressure is changed.
Components of intrinsic safety
• The basic parameters that have to be considered for assessing the chemical reaction systems
are
• Thermodynamics
• Reaction energy
• Adiabatic temperature and pressure rise
• Kinetics
• Activation energy
• Reaction rate
• Rate of heat generation
• Rate of pressure rise
• Time to maximum rate
• Physical
• Heat capacity
• Thermal conductivity
• In addition to the above parameters the safe limits of temperature, feed rate and concentration
have to be defined as a function of operating conditions.

Reaction Hazard
• Analysis indicates that incidents occur due to:
• Lack of proper understanding of the thermo-
chemistry and chemistry
• Inadequate engineering design for heat transfer
– Inadequate control systems and safety back-up
systems Including venting arrangements
• Inadequate operational procedures, including
training

Assessing Reaction Hazard
• Controlling an exothermic reaction depends on the interaction
among: the kinetics and reaction chemistry
– the plant equipment design
– the operating environment.
• Chemical process industry must consider the following factors

to better understand and address the potential hazards and
consequences of reactive systems

• Thorough hazard assessment: The chemical &
process hazards and the consequences of
deviations must be thoroughly understood,
evaluated, and appropriately addressed
through preventive measures. Several layers of
safety systems, whether complementary or
redundant should be considered to enhance
reliability.

• Complete identification of reaction chemistry and
thermochemistry:
• For some exothermic reactions, the time to runaway is very short.
• Over-pressurization can occur when gas or vapor is produced as
a byproduct of the reaction or any decomposition reactions.
• The kinetics of the runaway reaction will be reaction specific and
may differ in various runaway situations.
• The characteristics of the particular reactions must be determined
experimentally.
• Experimental data should be used to define process boundaries in
terms of the pressure, temperature, concentration, and other
parameters as well as the consequences of operating outside of
these boundaries.
• Addition of raw materials: Frequently, the
reaction rate is controlled by the addition rate
of one reactant or the catalyst and should be
determined based on chemistry studies.
Process industries must pay attention to the
order of ingredients, the addition rates, under-
or over-charging, and loss of agitation.

• Emergency relief: Runaway reactions may lead to
the rapid generation of gas or vapor. Under
certain conditions, the vapor generation rate may
be large enough to cause the vapor-liquid mixture
to swell to the top of the vessel, resulting in two-
phase flow in the relief venting system. Relief
system capacity should be evaluated in
conjunction with the hazard analysis to ensure
that sizing is based on an appropriate worst case
scenario.
Characterization using Calorimeters
• Important questions that must be asked for the characterization of

reactive chemicals:
• At what temperature does the reaction rate become large enough
• What is the maximum temperature increase
• What is the maximum pressure during the reaction.
• At what time and temperature does the maximum self-heat rate or
pressure rate occurs
• Are there any side reactions
• Can the heat generated by chemical reactions (desired or
undesired) exceed the capability of the vessel/process to remove
heat
Tools for evaluating thermal
explosion
– Thermal analysis Differential Scanning

Calorimeter (DSC),
– Thermo Gravimetric Analyzer (TGA),
– Differential Thermal Analyzer (DTA).

Steps to Reduce Reactive Hazards
• Facilities should take the following steps to prevent runaway

reactions: Modify processes to improve inherent safety.
• Minimize the potential for human error.
• Understand events that may lead to an overpressure and
eventually to vessel rupture.
• Use lessons learned.
• Evaluate Safe Operating Procedures.
• Evaluate the effectiveness of the emergency relief system.
• Evaluate employee training and oversight
• Through Inherent Safety
• Use a reaction pathway that uses less hazardous chemicals
• Use reaction pathway that is less energetic, slower or easier to control
• Use smaller inventories of reactive chemicals both in process and in
storage
• Reduce shipping of reactive chemicals – produce on site on demand.

• Design equipments or procedures to prevent an incident in the event of
a human error.
• Control reactor stoichiometry and charge mass so that in the event of a
runaway reaction the pressure rating of the vessel will not be exceeded.


Course Code: CLPC22
Lecture- 17
Assistant Professor
NIT Trichy
Hazards Identification
For each process in a chemical plant the
following questions must be asked:
1. What are the hazards?
2. What can go wrong and how?
3. What are the chances?
4. What are the consequences?
Hazard identification. The last three questions
are associated with risk assessment
• A risk assessment procedure that determines
probabilities is frequently called probabilistic
risk assessment (PRA), whereas a procedure
that determines probability and consequences
is called quantitative risk analysis (QRA).

Engineering
• Hazards identification and risk assessment
studies can be performed at any stage during
the initial design or ongoing operation of a
process.
• Hazard identification can be performed
independent of risk assessment. However, the
best result is obtained if they are done
together.

The hazard identification methods described in this chapter include the
following:
• Process hazards checklists: This is a list of items and possible problems
in the process that must be checked.
• Hazards surveys: This can be as simple as an inventory of hazardous
materials, or it can be as detailed as the Dow indexes. The Dow indexes
are a formal rating system, much like an income tax form, that provide
penalties for hazards and credits for safety equipment and procedures.
• Hazards and operability (HAZOP) studies: This approach allows the
mind to go free in a controlled environment. Various events are
suggested for a specific piece of equipment with the participants
determining whether and how the event could occur and whether the
event creates any form of risk.
• Safety review: An effective but less formal type of HAZOP study. The
results are highly dependent on the experience and synergism of the
group reviewing the process.

Process Hazards Checklists
• Check oil in engine.
• Check air pressure in tires.
• Check fluid level in radiator.
• Check air filter.
• Check headlights and taillights.
• Check exhaust system for leaks.
• Check fluid levels in brake system.
• Check gasoline level in tank.
Hazards Surveys

Hazards and Operability Studies
• The HAZOP procedure uses the following steps to complete an analysis:
• Begin with a detailed flow sheet. Break the flow sheet into a number of process units.
Thus the reactor area might be one unit, and the storage tank another. Select a unit for
study.
• Choose a study node (vessel, line, operating instruction).
• Describe the design intent of the study node. For example, vessel V-1 is designed to store
the benzene feedstock and provide it on demand to the reactor.
• Pick a process parameter: flow, level, temperature, pressure, concentration, pH, viscosity,
state (solid, liquid, or gas), agitation, volume, reaction, sample, component, start, stop,
stability, power, inert.
• Apply a guide word to the process parameter to suggest possible deviations. A list of
guide words is shown in. Some of the guide word process parameter combinations are
meaningless, as shown in Tables 10-4 and 10-5 for process lines and vessels.
• If the deviation is applicable, determine possible causes and note any protective systems.
• Evaluate the consequences of the deviation (if any). 8. Recommend action (what? by
whom? by when?) 9. Record all information.

Engineering
Engineering
Perform a HAZOP study on this unit to improve the safety of the process.
Use as study nodes the cooling coil (process parameters: flow and temperature) and the
stirrer (process parameter: agitation).
Engineering
Engineering
Engineering
Risk Assessment
• Risk assessment includes incident
identification and consequence analysis.
• Need?

• Review of Probability Theory
• Data are collected on the failure rate of a
particular hardware component. With adequate
data it can be shown that, on average, the
component fails after a certain period of time.
This is called the average failure rate and is
represented by p with units of faults/time.
• R is the reliability

• The failure density function is defined as the
derivative of the failure probability:

Interactions between Process Units

Engineering

Course Code: CLPC22
Lecture- 18
Assistant Professor
NIT Trichy
Hazards Identification
For each process in a chemical plant the
following questions must be asked:
1. What are the hazards?
2. What can go wrong and how?
3. What are the chances?
4. What are the consequences?
Hazard identification. The last three questions
are associated with risk assessment
• A risk assessment procedure that determines
probabilities is frequently called probabilistic
risk assessment (PRA), whereas a procedure
that determines probability and consequences
is called quantitative risk analysis (QRA).

Engineering
Engineering
Engineering
Perform a HAZOP study on this unit to improve the safety of the process.
Use as study nodes the cooling coil (process parameters: flow and temperature) and the
stirrer (process parameter: agitation).
Engineering
Engineering
Engineering
Risk Assessment
• Risk assessment includes incident identification and
consequence analysis.
• Review probability mathematics

• Describe two probabilistic methods (event trees and
fault trees)
• Describe the concepts of layer of protection analysis
(LOPA)
• Describe the relationship between quantitative risk
analysis (QRA) and LOPA.
particular hardware component.
• With adequate data it can be shown that, on
average, the component fails after a certain
period of time. This is called the average failure
rate and is represented by p with units of
faults/time.

• The failure density function is defined as the
derivative of the failure probability:
• The time interval between two failures of the

component is called the mean time between
failures (MTBF) and is given by the first
moment of the failure density function


Engineering
• For a system composed of two components A
and B


Course Code: CLPC22
Lecture- 19
Assistant Professor
NIT Trichy
Risk Assessment
• Risk assessment includes incident identification and
consequence analysis.
• Review probability mathematics

• Describe two probabilistic methods (event trees and
fault trees)
• Describe the concepts of layer of protection analysis
(LOPA)
• Describe the relationship between quantitative risk
analysis (QRA) and LOPA.
particular hardware component.
• With adequate data it can be shown that, on
average, the component fails after a certain
period of time. This is called the average failure
rate and is represented by p with units of
faults/time.

• The failure density function is defined as the derivative of the
failure probability:
• The time interval between two failures of the component is

called the mean time between failures (MTBF) and is given by
the first moment of the failure density function


Engineering
• For a system composed of two components A
and B

Event Trees
• The typical steps in an event tree analysis are:
• Identify an initiating event of interest
• Identify the safety functions designed to deal
with the initiating event
• Construct the event tree
• Describe the resulting accident event
sequences.

Engineering
• Four safety functions are identified:
– These are written across the top of the sheet.
– The first safety function is the high-temperature alarm.
– The second safety function is the operator noticing the
high reactor temperature during normal inspection.
– The third safety function is the operator reestablishing
the coolant flow by correcting the problem in time. The
final safety function is invoked by the operator
performing an emergency shutdown of the reactor.

Engineering
Fault Trees
• Fault trees originated in the aerospace industry and have
been used extensively by the nuclear power industry to
qualify and quantify the hazards and risks associated
with nuclear power plants.
• This approach is becoming more popular in the chemical
process industries, mostly as a result of the successful
experiences demonstrated by the nuclear industry.
• The approach starts with a well-defined accident, or top
event, and works backward toward the various
scenarios that can cause the accident

• Define precisely the top event. Events such as "high reactor
temperature" or "liquid level too high" are precise and
appropriate. Events such as "explosion of reactor" or "fire in
process" are too vague, whereas an event such as "leak in
valve' is too specific.
• Define the existing event. What conditions are sure to be
present when the top event occurs?
• Define the unallowed events. These are events that are unlikely
or are not under consideration at the present. This could include
wiring failures, lightning, tornadoes, and hurricanes.
• Define the physical bounds of the process. What components
are to be considered in the fault tree?
Engineering
• Consider again the alarm indicator and emergency shutdown
system of previous example. Draw a fault tree for this system.
• The first step is to define the problem.
• Top event: Damage to reactor as a result of overpressuring.
• Existing event: High process pressure.
• Unallowed events: Failure of mixer, electrical failures, wiring
failures, tornadoes, hurricanes, electrical storms.
• Physical bounds: The equipment shown in Figure 11-5.
• Equipment configuration: Solenoid valve open, reactor feed
flowing.
• Level of resolution: Equipment as shown in Figure 11-5.

Engineering

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DEPARTMENT OF CHEMICAL ENGINEERING

SAFETY IN CHEMICAL INDUSTRIES

Department of Chemical Engineering Safety In Chemical Industries 2

• Radioactive isotopes and stable isotopes.

Department of Chemical Engineering Safety In Chemical Industries 3

Department of Chemical Engineering Safety In Chemical Industries 4

• Emitted from nuclei, electron transfer

Department of Chemical Engineering Safety In Chemical Industries 5

Department of Chemical Engineering Safety In Chemical Industries 7

Department of Chemical Engineering Safety In Chemical Industries 8

• The biological risk of exposure to radiation is measured using the

• When a person is exposed to radiation, energy is deposited in the

• The amount of energy deposited per unit of weight of human tissue

• The rad, which stands for radiation absorbed dose

Department of Chemical Engineering Safety In Chemical Industries 10

• To measure over short period the exposure of individual

• To survey flux or radiation level in all parts of the facility.

• To monitor contamination of hands, feets, hair, skin.

• To establish legal protection for employers and employees.

Department of Chemical Engineering Safety In Chemical Industries 11

Department of Chemical Engineering Safety In Chemical Industries 14

• Thin walled tube reacts with radiation to produce electronic

• Can pinpoint the radiation .

• Cannot determine their energies.

Department of Chemical Engineering Safety In Chemical Industries 16

Department of Chemical Engineering Safety In Chemical Industries 18

• Very Thin plastic covered window permits alpha particle to

• Electronic pulse amplified and indicated by meter.

Department of Chemical Engineering Safety In Chemical Industries 19

Department of Chemical Engineering Safety In Chemical Industries 20

Department of Chemical Engineering Safety In Chemical Industries 21

Department of Chemical Engineering Safety In Chemical Industries 23

Department of Chemical Engineering Safety In Chemical Industries 24

SAFETY IN CHEMICAL INDUSTRIES

• Unit plot planning

Department of Chemical Engineering Safety In Chemical Industries 28

Department of Chemical Engineering Safety In Chemical Industries 32

Department of Chemical Engineering Safety In Chemical Industries 34

Department of Chemical Engineering Safety In Chemical Industries 35

Department of Chemical Engineering Safety In Chemical Industries 39

Department of Chemical Engineering Safety In Chemical Industries 40

Department of Chemical Engineering Safety In Chemical Industries 44

Department of Chemical Engineering Safety In Chemical Industries 45

Department of Chemical Engineering Safety In Chemical Industries 46

Department of Chemical Engineering Safety In Chemical Industries 47

SAFETY IN CHEMICAL INDUSTRIES

Department of Chemical Engineering Safety In Chemical Industries 49

• When the reaction rate increases due to an increase in temperature,

Department of Chemical Engineering Safety In Chemical Industries 51

Department of Chemical Engineering Safety In Chemical Industries 53

Department of Chemical Engineering Safety In Chemical Industries 54

Department of Chemical Engineering Safety In Chemical Industries 55

Department of Chemical Engineering Safety In Chemical Industries 56

Department of Chemical Engineering Safety In Chemical Industries 57

Department of Chemical Engineering Safety In Chemical Industries 58

Department of Chemical Engineering Safety In Chemical Industries 59

Department of Chemical Engineering Safety In Chemical Industries 60

Department of Chemical Engineering Safety In Chemical Industries 62

Department of Chemical Engineering Safety In Chemical Industries 63

• Chemical process industry must consider the following factors

Department of Chemical Engineering Safety In Chemical Industries 64

Department of Chemical Engineering Safety In Chemical Industries 65

Department of Chemical Engineering Safety In Chemical Industries 67

Department of Chemical Engineering Safety In Chemical Industries 69