ICH 3101: REACTOR DESIGN

Dr. William Wanasolo

(Chemical and Processing Engineering)

12/13/2021
 Introduction
• Chemical kinetics is the study of rates of
chemical reactions and factors that affect
these rates.
• Different factors affect chemical reaction
rates differently.
• These factors include temperature,
pressure, concentration,
catalyst/inhibitors, surface area and nature
or phase of reactants and products.
12/13/2021
• When all reactants, catalyst and products
are in the same physical state the reaction
is said to be homogeneous, otherwise it is
heterogeneous reaction.
• Chemical kinetics is one of the principle
concept behind reactor design.
• Chemical reactions can be very fast/slow
or no reaction at all.
• Most industrial reactions occur at rates
between these extremes.
12/13/2021
 Reaction Rates
•  In homogeneous systems the rate of
chemical reaction is defined based on unit
volume of reacting fluid.
• It is expressed as rate of disappearance of
reacting component or rate of formation
of a product. Consider the reaction:

12/13/2021
•  For species A, if NA is the number of
moles of A, then the rate of change in
number of moles of A is:

• The negative implies the number of

moles is decreasing with time.

12/13/2021
•  If V is the volume of fluid, then the rate
of reaction is given by:

12/13/2021
• For homogeneous systems the volume of
fluid and volume of reactor are identical.
• Therefore, the rate of reaction for
homogenous system is defined as the
change in moles of reactant or product
per unit time per unit volume of reactor.
• Usually rate of change of product is equal
to rate of change of reactant.
A+B = C+D

12/13/2021
• Therefore, the rate of change of a given
chemical species can be expressed as rate of
disappearance of reactant or rate of
formation of a product.
• Generally the rate of reaction is a function
of concentration, temperature, pressure
and the type of catalyst.
• However, it is independent of the type of
reactor.
• Explain how the above factors affect rate of
chemical reaction
12/13/2021
•  The rate of reaction is an algebraic
equation and not differential equation.
• It is used to relate the rate of reaction to
the concentration of reacting species and
temperature at which the reaction takes
place.
• Consider a hypothetical reaction
between species A and B:

12/13/2021
•  Species A and B are reactants while C and
D are products that form during reaction.
• The small letters are stoichiometric
coefficients. The rate of chemical reaction
with respect to species B is:

• Where V is volume of reaction vessel and

it is constant.

12/13/2021
 •  Equation (i) can be written as:

• If CB is the concentration of B then:

12/13/2021
•  And:

12/13/2021
•  Therefore, the rate of chemical reaction is
the rate of change of the concentration of
reacting species or product. Similarly:

12/13/2021
 Variation of Reaction Rate with
Concentration
•  The rate of reaction is proportional to
concentration raised to some power; which
can be zero, first or second order kinetics. For
zero order kinetics:

12/13/2021
• Rate of reaction is proportional to conc
raised to some power (n=0, 1, 2)
• n=0, zero order kinetics
• n=1, first order kinetics
• n=2 second order kinetics
• Show the steps from Equation (iii) to
Equation (iv)

12/13/2021
•  For first order:

12/13/2021
•  For second order kinetics:

• Equations (iii); (v) and (vii) are called rate

law equations.

12/13/2021
 Mole Balance
•  The general mole balance for species A in the
following reaction is:

12/13/2021
•  If:

12/13/2021
•  Then:

• OR:

• This is the general mole balance of the

species A
NB:
• From kinetics, the 1st order reaction rate is:

12/13/2021
Study Question:
a) The rate of reaction of a certain reactant is 10
mol/(dm3 s), if the reactor volume is 30 dm3,
what is the consumption
Solution:
b) Consumption is given by:
Consumption  reactor volume x rate of reaction
 rAV
 10 x30
 300 mol/s

12/13/2021
 Reactors
(Wed 14th Oct 2021)
• Reactors are vessels designed for chemical
reaction or physical change.
• The reactor designer aims at obtaining the
highest efficiency and yield; and least
energy and material of construction.
• There are two main types of structural
vessels used as reactors. These are tank
type and tubular type, based upon
structural design
12/13/2021
• Examples of tank type are: batch reactors;
continuous stirred tank reactor (CSTR) and
fixed bed reactor (FBR).
• Tubular type reactors have cylindrical
geometry and include plug flow reactors and
fluidized bed reactors.
• Reactors are also classified according to
mode of operation. This classification gives
batch and flow reactors.

12/13/2021
• Flow reactors include CSTR; PFR and FBR;
while batch reactors are batch and fixed bed
rectors
• Reactors can also be classified according to
function.
• This classification is commonly used in
process simulators used for reactor design
• Under this classification there is kinetic;
stoichiometric; equilibrium; and Gibbs
reactors.
12/13/2021
 Reactors by Function
• Most process simulators use the four types
of reactors classified according to function:
stoichiometric; kinetic for CSTR; kinetic for
PFR and equilibrium reactor models.
• The stoichiometric model permits the
specification of reactant conversion and
extent of reaction for one or more
reactions;

12/13/2021
• The kinetic model for CSTR is for
homogenous phase (vapor and liquid)
assuming perfect mixing;
• The kinetic model for tubular reactor (PFR)
for homogeneous phase (vapor and liquid)
assuming no back-mixing (dispersion); and
• The equilibrium reactor model for multiple
phase (vapor, liquid and solid), where
approach to equilibrium for individual
reactions can be specified.
12/13/2021
Study Question:
a) Explain the different ways in which reactors
can be classified

12/13/2021
 Stoichiometric Reactor
• Using the fractional conversion of key
reactant or the extent of reaction the
RSTOIC determines the flow rates of all the
species leaving the reactor.
• The RSTOIC also includes energy balance
and determines either the rate of heat
transfer to/fro the reactor, or the
temperature of the product stream.

12/13/2021
•  The fraction conversion, x (0 ), of a given
reactant is given by:

• Where Nin and Nout = moles of species, i,

entering and leaving the reactor,
respectively, are specified (or the extent of
reaction).
• Using this equation the flowrates for all
species leaving the reactor are determined.

12/13/2021
•  Consider the catalytic oxidation of ethanol.
• A very dilute stream containing ethanol
and oxygen is heated over a catalyst bed,
and ethanol is oxidized to acetaldehyde,
which is in turn oxidized to carbon dioxide:

12/13/2021
• The conversion of ethanol is
approximately 95% and the conversion of
acetaldehyde formed by the first reaction
is approximately 88%.
• The reaction can be simulated using a
stoichiometric reactor model.
• The specifications are as shown:

12/13/2021
12/13/2021
12/13/2021
 Equilibrium Reactors
• Most simulators provide two models for
chemical equilibrium reactions.
• In addition, simultaneous phase
equilibrium can also be requested.
• The first type is based on the use of
chemical equilibrium constants for
specified stoichiometric reactions.

12/13/2021
• The second model is based on the
minimization of Gibbs free energy and the
reactions are not specified but the possible
products are specified.
• The REQUIL reactor calculates chemical
equilibrium and phase equilibrium
involving vapor and liquid phases.
• Pure solid species may participate in the
reactions, but are not taken to be in phase
equilibrium.
12/13/2021
• It is also possible to specify an approach
to chemical equilibrium for one or more
of the reactions.
• REQUIL uses chemical equilibrium
constants for specific stoichiometric
reactions.
• It solves the mass-action equations for
chemical equilibrium.

12/13/2021
• Unlike the RGIBBS reactor that can have
any number of product streams, only one
liquid and one vapor streams are allowed
in the REQUIL reactor.
• Consider the hydro-dealkylation reactor
below.
• The conversion of toluene is 75% and the
conversion of bi-phenyl (including that
produced by the main reaction) is 2%.

12/13/2021
•  Adiabatic operation with a 5 psia pressure
drop across the reactor is also assumed.

• Forinstances where reactions that take place

are known, REQUIL is a better choice for
determining equilibrium conditions.

12/13/2021
12/13/2021
 Effluent Conditions REQUIL
Temperature (°F) 1.284.0
Flowrates  
Hydrogen 1,700.3
Methane 3,376.9
Benzene 381.3
Toluene 5.9
Biphenyl 11.5
Total 5,475.9

12/13/2021
 Gibbs Reactor
• The RGIBBS reactor computes multi-phase
chemical equilibrium involving a vapor
phase, multiple liquid phases and pure
solid phases.
• There is no need to specify the
stoichiometry for an independent set of
chemical reactions because RGIBBS
minimizes the Gibbs free energy subject to
mass balance constraints.
12/13/2021
• It is however, possible to specify
stoichiometry when is it desirable to
specify the approach of one or more
reactions to chemical equilibrium
• In the RGibbs model, any number of
product streams can be specified, since
RGIBBS can calculate phase equilibrium
for any number of product phases.
• Also, heat streams can be used.

12/13/2021
 Kinetic Reactors
• Steady state simulation programs contain at
least two kinetic reactor models: one for the
PFR and another for CSTR.
• Both models require the user to provide
rate equations for the chemical reactions.
• The model can be used for any of two
modes: Either to compute the reactor
volume for a specific conversion or to
compute the conversion for a specified
reactor volume.
12/13/2021
• A PFR model is a cylindrical reactor in which
conditions vary uni-dimensionally in the
axial direction and radial dispersion is
neglected.
• Consequently, there are no radial gradients
of temperature, composition, or pressure;
and mass transfer by diffusion does not
occur in the axial direction.
• Operation of the reactor can be adiabatic,
isothermal or non-adiabatic, non-
isothermal.
12/13/2021
• For the latter, heat transfer to or from
the reacting mixture occurs along the
length of the reactor.
• The RPLUG subroutine is a rigorous
one-dimensional plug flow model that
neglects radial dispersion.
• To use RPLUG, it is necessary to
specify kinetic rate expressions for
each of the chemical reactions.
12/13/2021
 Batch Reactor

12/13/2021
• This is a vertical cylinder fitted with stirrer
and having an external steam jacket for
heating/cooling purposes.
• It is a reactor in which the reactants and
catalyst are added in desired quantities,
the vessel is closed & the contents allowed
to react.
• The products are discharged and fresh
reactants (or new batches) are introduced.

12/13/2021
• Batch reactor is heated and cooled by use
of a steam jacket.
• In industry batch reactors are commonly
used for fermentation processes;
pharmaceuticals; soaps and detergents;
paints; foaming; etc.

12/13/2021
• Batch reactor operates under unsteady
state conditions because the composition
changes with time.
• However, at a given time of reaction the
composition is uniform throughout the
reactor.
• It is characterized by varying extent of
reaction with time and properties of
reaction mixture.

12/13/2021
 Advantages
The batch reactor has several advantages
• Simple in construction
• Easy to operate
• Flexibility of operation (e.g., can be used for
different products)
• Relatively low cost
• Requires less instrumentation and auxiliaries
• Can give higher conversion by allowing long
residence times for reactants
12/13/2021
 Disadvantages
• Higher labor costs per unit production
• Requires time to charge, startup and re-
charge (with cleaning if different products
are to be made)
• Poor quality control for different batches,
product quality may differ from batch to
batch
• Does not support large scale production.
12/13/2021
 Mole Balance

12/13/2021
•  For batch reactor:

• The general mole balance Equation (ix)

becomes:

• Since volume of reactor is constant, the mole

balance for batch reactor is:

12/13/2021
•  Separating and integrating:

• This equation gives the time required to

reduce the number of moles in a batch
reactor from NAO to NA.

12/13/2021
12/13/2021
 Example-1
•  Evaluate the time taken to reduce the
number of moles by a factor of 10 in a
batch reactor for the reaction

• Given that it is first order kinetics with

rate constant = 0.046 min-1

12/13/2021
•Solution
 
• Mole balance (Equation (ix))

12/13/2021
•  Rate law (first order kinetics):

• Substituting into (a) for rAV

12/13/2021
•  Separating and integrating

12/13/2021
•  But

12/13/2021
Study question
• What will be the time taken in the above
example if the reaction followed:
– Zero order kinetics
– Second order kinetics

12/13/2021
 Example-2
•  Evaluate the number of moles in example-1,
remaining after 2 min in a batch reactor with
initial number of moles of 4 moles

• Given that it is first order kinetics with rate

constant = 0.046 min-1

12/13/2021
 Solution
•  

12/13/2021
 Stoichiometry and Mole Balance
• Stoichiometry is the relationship between
initial amount of feed; amount reacted and
conversion.
• Conversion is the fraction of initial feed
that is reacted to form products.
• It is the moles of feed that react per unit
feed.

12/13/2021
• Percent conversion is conversion
multiplied by 100%.
• The basis for calculation of conversion is
the limiting reactant. If x is conversion,
then:

12/13/2021
•  

12/13/2021
•  Equation (xii) is the mole balance in
terms of conversion
• If V reactor volume; dividing through by
V:

12/13/2021
•  But:

12/13/2021
• Equation (xiii) is the stoichiometry of the
reaction
• At the beginning of reaction, the
conversion is zero; and after some time, t,
it is x.
• Similarly, the initial number of moles is NA0
and after time t, it is NA;

12/13/2021
•  Therefore, Equation (xii) can be written
as:

12/13/2021
•  Dividing Equation (xiv) by dt:

• But from mole balance:

12/13/2021
 •  Equation (xv) becomes:

12/13/2021
•  Equation (xvi) is the mole balance
equation in terms of conversion, x and
reaction time t.
• Separating and integrating Equation (xvi);

12/13/2021
•  OR:

• If reaction is first order;

12/13/2021
•  Combining stoichiometry; rate law and
mole balance, i.e., substitute rate law
and stoichiometry into mole balance:

12/13/2021
•  

12/13/2021
•  

• If the reaction is second order:

• The mole balance becomes:

12/13/2021
•  

12/13/2021
•  

• If reaction is zero order:

• The mole balance becomes:

12/13/2021
•  

12/13/2021
•Example:
 
• The elementary reaction

• Takes place in a batch reactor at constant

temperature of 500°C.
• Initially the concentrations of A and B are
equal.
• If CA0 = 0.2 mol/dm3 and k = 10 dm3/mol-s;
calculate the time taken to achieve a
conversion of 90%.
12/13/2021
•Solution
 
• For batch reactor; the volume is
constant.
• The reaction is second order
therefore;

12/13/2021
•  

• Since CA0 = CB0;

12/13/2021
•  The mole balance becomes:

12/13/2021
•  Integrating:

12/13/2021
•  

12/13/2021
NB:
• For irreversible reactions the maximum
value of conversion corresponds to a
complete reaction, i.e., x = 1.0; for
reversible reaction the maximum value
of conversion correspond to the
equilibrium conversion, i.e., x = xe.

12/13/2021