Department of Mechanical Engineering

Even Semester
2013 2014

ME654: SAFETY IN CHEMICAL INDUSTRY

Chemical reaction
A Chemical reaction is a process that results in the conversion of
chemical substances.
The substance or substances initially involved in a chemical reaction are
called reactants.
These reactants are characterized by a chemical change and they yield
one or more products.
These products are generally different from the original reactants.
Chemical reactions may be of different nature depending on the type of
reactants, type of product desired, conditions and time of the reaction.

Chemical reaction
Type of reaction

Area of utility

Combination

To synthesize new compounds.

Decomposition

Breakdown of larger, unuseful compounds/

complexes into smaller useful compounds.

Substitution

Salt formation, New compounds formation

/ One small group in a molecule is replaced
by another small group.

Isomerization

A chemical compound undergoes a

structural rearrangement without any
change in the atomic composition.

Chemical reaction
Type of reaction

Area of utility

Esterification

A reaction between an organic acid and an

alcohol forming an ester and water.

Hydrolysis

A large molecule is split into two smaller

molecules in the presence of water.

Hydrogenation

Hydrogen is added across a double bond or

a triple bond.

Chemical reactors
Chemical reactors are vessels designed to contain chemical reactions.
The design of a chemical reactor where bulk drugs would be
synthesized on a commercial scale would depend on multiple aspects of
chemical engineering.
Reactors are designed based on features like mode of operation or
types of phases present or the geometry of reactors.
Batch or Continuous depending on the mode of operation.
Homogeneous or Heterogeneous depending upon the phases
present.

Chemical reactors
Depending upon the flow pattern and manner in which the phases make
contact with each other, chemical reactors may also be classified as,
Stirred Tank Reactor
Tubular Reactor
Packed Bed Reactor
Fluidized Bed Reactor

Batch Process
A process in which all the reactants are added together at the beginning of
the process and products removed at the termination of the reaction is called a batch
process. In this process, all the reagents are added at the commencement and no
addition or withdrawal is made while the reaction is progressing (Fig. 1). Batch
processes are suitable for small production and for processes where a range of
different products or grades is to be produced in the same equipment for example,
pigments, dye stuff and polymers.

Continuous Process
A process in which the reactants are fed to the reactor and the products or
byproducts are withdrawn in between while the reaction is still progressing (Fig. 2). For
example, Haber Process for the manufacture of Ammonia. Continuous production will
normally give lower production costs as compared to batch production, but it faces the
limitation of lacking the flexibility of batch production. Continuous reactors are usually
preferred for large scale production.

Semi Batch Process

Process that do not fit in the definition of batch or a semi-batch reactor is operated
with both continuous and batch inputs and outputs and are often referred to as semi
continuous or semi-batch.
In such semi-batch reactors, some of the reactants may be added or some of the
products withdrawn as the reaction proceeds.
A semi-continuous process can also be one which is interrupted periodically for
some specific purpose, for example, for the regeneration of catalyst, or for removal
of gas for example, a fermentor is loaded with a batch, which constantly produces
carbon dioxide, which has to be removed continuously.
Another example is chlorination of a liquid.

Catalytic Processes
Most of the chemical reactions either proceed in the presence of catalysts or increases
their yield in the presence of catalysts. A catalyst is a substance that, without itself
undergoing any permanent chemical change, increases the rate of a reaction. The rate
of a catalytic reaction is proportional to the amount of catalyst the contact with a fluid
phase reagents. This is proportional to the exposed area, efficiency of diffusion of
reagents in and products out, type of mixing. The assumption of perfect mixing cannot
be assumed. A catalytic reaction pathway is often multistep with intermediates that are
chemically bound to the catalyst. Since the chemical binding is also a chemical
reaction, it may affect the reaction kinetics. The behaviour of the catalyst is also a
consideration. Particularly in high temperature petrochemical processes, catalysts are
deactivated by sintering, coking and similar processes.

Homogeneous Reactions
Homogeneous reactions are those in which the reactants, products and any catalyst
used form one continuous phase; for example, gaseous or liquid. Homogeneous gas
phase reactors will always be operated continuously. Tubular (Pipe line) reactors are
normally used for homogeneous gas phase reactions; for example, in the thermal
cracking of petroleum, crude oil fractions to ethylene, and the thermal decomposition of
dichloroethane to vinyl chloride. Homogeneous liquid phase reactors may be batch or
continuous. Batch reactions of single or miscible liquids are almost invariably done in
stirred or pump around tanks. The agitation is needed to mix multiple feeds at the start
and to enhance heat exchange with cooling or heating media during the process.

Heterogeneous Reactions
In a heterogeneous reaction two or more phases exist and the overriding problems in
the reactor design is to promote mass transfer between the phases.
Liquid-Liquid
Liquid-Solid
Liquid-Solid-Gas
Solid-Solid
Gas-Solid
Gas-Liquid

Heterogeneous Reactions

Reactor Geometry
The reactors used for established processes are usually complex designs which have
been developed and evolved over a period of years to suit the requirements of the
process, and are unique designs. However, it is convenient to classify reactor designs
into the following broad categories.

Stirred Tank Reactors

Stirred tank agitated reactors consist of a tank fitted with a mechanical agitator and a
cooling jacket or coils. They are operated as batch reactors or continuous reactors.
Several reactors may be used in series.

Stirred Tank Reactors

The stirred tank reactor can be considered the basic chemical
reactor; modeling on a large scale the conventional laboratory flask.
They are used for homogeneous and heterogeneous liquid-liquid and
liquid-gas reactions and for reactions that involve freely suspended
solids, which are held in suspension by the agitation.
As the degree of agitation is under the designers control, stirred tank
reactors are particularly suitable for reactions where good mass
transfer or heat transfer is required.

Tubular Reactors
Tubular reactors are generally used for gaseous reactions, but are
also suitable for some liquid phase reactions.
If high heat transfer rates are required small diameter tubes are used
to increase the surface area to volume ratio.
Several tubes may be arranged in parallel, connected to a manifold
or fitted into a tube sheet in a similar arrangement to a shell and tube
heat exchangers.
For high temperature reactions the tubes may be arranged in a
furnace.

Packed Bed Reactors

There are two basic types of packed bed reactor; those in which the solid is a reactant
and those in which the solid is a catalyst. In chemical process industries, the
emphasize is mainly on the designing of catalytic reactors. Industrial packed bed
catalytic reactors range in size from small tubes, a few centimeters diameter to large
diameter packed beds. Packed-bed reactors are used for gas and gas-liquid reactions.
Heat-transfer rates in large diameter packed beds are poor therefore, where high heattransfer rates are required, fluidised beds should be considered.

Fluidised Bed Reactors

A fluidized-bed reactor is a combination of the two most common, packed-bed and
stirred tank, continuous flow reactors. It is very important to chemical engineering
because of its excellent heat and mass transfer characteristics. The essential features
of a fluidised bed reactor is that the solids are held in suspension by the upward flow of
the reacting fluid. This promotes high mass and heat transfer rates and good mixing.

Reactor Design
Fundamentals of Reactor Design
The design of a chemical reactor deals with multiple aspects of chemical
engineering. Chemical reactions, chemical energetics and equations/laws of
thermodynamics play an important role in the selection and design of chemical
reactors.

Reactor Design
The design of an industrial chemical reactor must satisfy the following requirements.
The chemical factors: The kinetics of the reaction. The design must provide sufficient
residence time for the desired reaction to proceed to the required degree of conversion.
The mass transfer factors: With hetereogeneous reactions, the reaction rate may be
controlled by the rates of diffusion of the reacting species, rather than the chemical
kinetics.
The heat transfer factors: The removal or addition of the heat of reaction.
The safety factors: The confinement of hazardous reactants and products and the
control of the reaction and the process conditions.
Economic factors: Minimum amount of money should be required to purchase and
operate.

Reactor Design
A general procedure for reactor design is outlined below:
Kinetic and thermodynamic data; Rate of reaction (Pressure, Temperature, Flow
rate, Catalytic Concentration)
Data on physical properties
Rate controlling mechanism (kinetic, mass or heat transfer)
Reactor type (based on experience with similar studies or from the laboratory and
pilot plant work)
Selection of optimum reaction conditions
Size of the reactor
Material of Construction
Preliminary mechanical design for the reactor including the vessel design, heat
transfer surfaces etc.
Design is optimized and validated
An approximate cost

Reactor Design Mathematical Models

A model of a reaction process is a set of data and equation that is believed to represent
the performance of a specific vessel configuration (mixed, plug flow, laminar,
dispersed, etc.).
Key process variables include:
Residence Time Distribution (RTD)
Volume
Temperature
Pressure
Concentrations of chemical
Heat transfer coefficients

Commonly used Chemical reactors

Reaction hazard evaluation and assessment

What is the Hazard?
When processing exothermic chemical reactions including thermally unstable
substances and mixtures, it should be remembered that the hazard comes from
PRESSURE generation.
Pressure can be generated in a closed vessel (or inadequately vented vessel) from:
Permanent gas generation e.g. generation of nitrogen, carbon dioxide, etc from the
desired process or an unexpected event.
Vapour pressure effects caused by heating, possibly arising from an exothermic
reaction or a process failure condition, thus raising a mixture above its boiling point.
Identification of pressure generation is critically important for vent sizing, the most
common basis of safety in the chemical industry, since the design calculations will
require different data input.

Reaction hazard evaluation and assessment

What is the impact of Scale-Up and why is it so Important?
Firstly, and most obviously, energy is consumed
in heating the REACTION MASS

To retain thermal equilibrium, energy is also consumed

in heating the REACTOR to an equilibrium temperature

Finally, once the outer walls of the vessel are above

the ambient temperature, heat is lost through
the walls to the SURROUNDINGS

Reaction hazard evaluation and assessment

Essentially, as the scale increases, the ability to remove excess heat by
heat loss to the vessel and its surroundings reduces, resulting in a much
higher proportion of the heat retained in the reaction mass.
Heat losses are 10 times higher in the lab scale vessel
Only 2% heat loss to the large scale vessel compared with 19% heat
loss to the small scale vessel
The effects of scale are real and very significant!
Classical laboratory reactor systems are inadequate in
providing this data as they typically have high heat losses. As a
consequence specialist equipment is required to simulate large scale
conditions.

Reaction hazard evaluation and assessment

Reaction hazards assessment comprises of a number of experimental and other
assessment procedures and tools which ultimately fit together to provide a basis of
safety for any chemical process.
This basis of safety is the implemented and documented system that is in place to
either prevent a process running out of control under normal and foreseeable
conditions or provide engineering solutions to control the consequences of run-away
process.

Reaction hazard evaluation and assessment

Process Lifecycle Activities

Chemical route selection

Process development and optimization
Pilot (small) scale production
Large scale production

Reaction hazard evaluation and assessment

Reaction hazard evaluation and assessment

Reaction hazard evaluation and assessment

CHEMICAL ROUTE SELECTION

Reaction hazard evaluation and assessment

Chemical route selection

Reaction hazard evaluation and assessment

PROCESS DEVELOPMENT AND OPTIMIZATION
DIFFERENTIAL SCANNING CALORIMETRY (DSC)
To determine the energy associated with the decomposition of a material or
mixture potentially to screen for explosive properties.
CARIUS (10 G) TUBE SCREENING TEST
The test is designed to provide a preliminary indication of the thermal
behaviour of a material. Exothermic, endothermic and gas generating events are
determined in a semiquantitative fashion. The test can be undertaken on a liquid, solid
or mixture.
ACCELERATING RATE CALORIMETRY (ARC)
The test is normally performed to determine the onset temperature of an
exothermic decomposition and the subsequent kinetics and magnitude of the contained
runaway.

Reaction hazard evaluation and assessment

HEAT FLOW CALORIMETRY (METTLER TOLEDO RC1 REACTION
CALORIMETER)
To determine the heat of reaction under isothermal or isoperibolic conditions
and identify the effect of changes in feed rates, temperatures and concentrations on
the "instantaneous" nature of a reaction system.
ADIABATIC PRESSURE DEWAR CALORIMETRY
To examine the stability of materials under adiabatic (zero heat loss)
conditions.

Reaction hazard evaluation and assessment

The following tests can be conducted in the calorimeter:
Specification of Maximum Safe Handling Temperatures
Collection of Time to Maximum Rate (TMR) Data
Vent Sizing Information Collection for Batch Processes
Vent Sizing Information Collection for Semi-Batch Processes
Tempering Test
Blowdown Test

Reaction hazard evaluation and assessment

Process development and optimization
Impact for which the BAM Fall hammer test is employed.
Friction for which the BAM Friction test is employed.
Burning for which the USA small scale-burning test is employed
Heating for which the DSC (or similar) thermal screening test is employed

Reaction hazard evaluation and assessment

PILOT (SMALL) SCALE PRODUCTION
Examine the existing thermochemical data for obvious hazards inherent in the
process.
Conduct a thorough hazard identification exercise to identify foreseeable (and
realistic) scenarios which may present an over pressurisation hazard.
Hazard and Operability (HAZOP) Studies, Check List Assessments, Informal
what if? Assessments, Failure Modes and Effects Analysis (FMEA), Fault
Tree Analysis

Reaction hazard evaluation and assessment

PILOT (SMALL) SCALE PRODUCTION
Identify the consequences of foreseeable deviations and define the worst case over
pressurisation scenario.
Once a short-list of hazardous scenarios is available, it is necessary to
conclusively ascertain whether the consequences of the scenarios are
hazardous or benign. The methods through which this can be done include:
Computational simulation
Estimation based on existing process safety data
Experimental simulation

Reaction hazard evaluation and assessment

PILOT (SMALL) SCALE PRODUCTION
Specify and implement safety measures to protect the vessel(s) from all
foreseeable scenarios which may present a risk of over pressurisation.
Once the consequences of all the worst case candidates have been
quantified, the final task is to specify which safety measures are required to
protect the reactor from the consequences or to validate if existing protection
measures and protocols are acceptable.
There are numerous options available including:
Process control
Design for containment
Reaction dumping / passive quenching
Reaction inhibition / active quenching
Emergency pressure relief (venting)

Reaction hazard evaluation and assessment

LARGE SCALE PRODUCTION
The procedure for safety evaluation of large scale production would generally follow the
lines of that detailed for pilot scale-up. The most important differences being:
The consequences of a deviation will be more dramatic due to the larger inventory.
This implies the need for a more rigorous and exhaustive hazard identification
exercise.
The variability of the plant is likely to be less than for the pilot plant. The need for
instrumented safety systems to comply with best practice will require assessment
of safety systems to international standards such as IEC 61508/11.