Learning unit 4: Isothermal reactor design

Reading: To complete this unit, please study chapter 4 in your prescribed textbook, Elements of
Chemical Reaction Engineering.

4.1 Introduction

This learning unit will bring the previous three chapters together to arrive at a logical structure for
the design of various types of reactors. The previous learning units discussed mole balances for the
different types of reactors, design equations, rate constants and concentration profiles. The
procedures for isothermal design of reactors using the knowledge you have gained from the other
learning units will be introduced in this learning unit. When using this structure, you should be able
to solve reaction engineering problems through reasoning, with due regard for the various
restrictions and conditions applicable to each equation. It is very dangerous simply to substitute
numbers into the formulas, as this could give rise to answers that may not be logical.

Before continuing with this learning unit, consult the mind map in Appendix A and identify any
concepts that you may be unsure of. Revise these concepts to ensure that you have a clear
understanding before going on to the rest of the learning unit.

4.2 Learning outcomes

At the end of this learning unit, you should be able to:

1. Calculate equilibrium conversion for the different type of reactors

2. Calculate the specific reaction rate constant needed for the design of a CSTR for a liquid
phase batch reactor
3. Design a CSTR from batch reactor data
4. Design a tubular reactor for a gas phase reaction

4.3 Design structure for isothermal reactors

Figure 4.1 gives a pathway for the design structure of isothermal reactors. If you understand the
pathway to the solution, you will avoid having to plug numbers into memorised equations, and you
will understand isothermal reactor design better.

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 Figure 4.1: Isothermal reaction design flowchart

Raili takes you through the flowsheet in her clip, Step by Step Approach to Solving Isothermal
Reactor Design Problems (8.28). View it at: https://youtu.be/3rBVlg5ugaY.

4.4 Scale-up of liquid phase batch reactor data for the design of a CSTR

The scale-up of laboratory experiments to pilot plant or full-scale plant is carried out by chemical
engineers. In order for scale-up to be successful, a thorough understanding of the chemical kinetics
and transport limitations is required. In this section we show you how to analyse a laboratory-scale
batch reactor in which a liquid phase reaction of known order is being carried out. After determining
the specific reaction rate, k, from a batch experiment, we use it in the design of a full-scale flow
(CSTR) reactor.

4.4.1 Batch operation

In modelling a batch reactor, we have assumed that there is no inflow or outflow of material and
that the reactor is well mixed. For most liquid phase reactions, the density change with reaction is
usually small and can be neglected (i.e., = ). For gas phases in which the batch reactor volume
remains constant, we also have = . Therefore, for a constant-volume ( = ) batch reactor,
the mole balance is:
1
=

2
We can then write this in terms of concentration:

Generally, when analysing laboratory experiments, it is most convenient to process the data in terms
of the measured variable. Because concentration is the measured variable for most liquid phase
reactions, the general mole balance equation applied to reactions in which there is no volume
change becomes:

− =−

Consider the reaction

2 →
which is irreversible and second order in A. The rate at which A is being consumed is given by the
rate law:

− =
Combining the rate law and the mole balance:

− =

At t = 0, = . For an isothermal reaction, we can integrate this equation to obtain the reactant
concentration at any time t:

1
− =

The time needed to reduce the reactant concentration in a batch reactor from an initial value to
some specified value for a second-order, isothermal liquid phase reaction is:
1 1 1
− =

In reality, the total cycle time in any batch operation is considerably longer than the reaction time,
tR, as one must account for the time necessary to fill (tf) and empty (te) the reactor together with the
time necessary to clean the reactor between batches, tc. In some cases, the reaction time calculated
may be only a small fraction of the total cycle time, tt.

= + + +

For example, consider a batch polymerisation process:

Table 4.1: Typical time for a batch polymerisation process (Fogler, 2013)
Activity Time (hr)
1. Charge the feed to the reactor and agitate, 1.5 – 3.0
2. Heat to reaction temperature, 1.0 – 2.0
3. Carry out reaction, Variable
4. Empty and clean reactor, 0.5 – 1.0

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 Total time excluding reaction 3.0 – 6.0

Batch polymerisation reaction times have been measured to vary between 5 and 60 hours.
Decreasing the reaction time in the case of a 60-hour reaction is a critical problem. As the reaction
time is reduced, it becomes increasingly important to use large pipelines and pumps to achieve rapid
transfers and to utilise efficient sequencing in order to minimise the cycle time.

In order to demonstrate the magnitude of batch reaction times, tR, for a given conversion of 90%,
with varying values of the specific reaction rate, k, consider the irreversible reaction:

→
which is carried out in a constant-volume batch reactor for a first- and a second-order reaction.

Following the flowsheet in Figure 4.1:

Table 4.2: Example to estimate reaction times

Mole balance
=−
Rate law First order − = Second order − =
Stoichiometry (V = V0)
= = (1 − )
Combining
= (1 − ) = (1 − )
Integrate 1 1
= =
1− (1 − )
X = 0.9 1 1 2.3 0.9 9
= = = =
1 − 0.9 (1 − 0.9)
= 10 then = 6.4 ℎ = 10 then = 2.5 ℎ

Example 4.1

1. A liquid phase reaction between cyclopentadiene (A) and benzoquinone (B) is conducted in an
isothermal batch reactor producing an adduct (C).

+ →
The reaction is first order with regard to each reactant. Determine the reactor volume required to
produce 175 mol C per hour if we know the following: Fractional conversion is 0.90, CA0 = CB0 = 0.15
mol/L, k = 9.92*10-3 L/mol.s at 25 °C, and the downtime between batches is 30 min.

We have CA0 = CB0 and our stoichiometry is the same for A and B.

Our rate expression thus reduces to:

− = = = (1 − )

=
(1 − )
1 1 0.9
= = = 1.68 ℎ
1− 9.92 × 10 × 0.15 0.1

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 ( + ) (1.68 + 0.5)175
= = = 2830
1 × 0.15 × 0.90
Work through example 4.1 in the prescribed textbook, Elements of Chemical Reaction Engineering.

The clip Isothermal Batch Reactor Part 1 (4.59) contains an additional example. View it at:
https://youtu.be/im6jNzr70KQ

Activity 4.1

A 200 dm3 constant volume batch reactor is pressurised to 20 atm with a mixture of 75% A
and 25% inert. The gas phase reaction → + is carried out isothermally at 227 °C.
a. Assuming that the ideal gas law is valid, how many moles of A are in the reactor
initially? What is the initial concentration of A? (Answer: = 0.366 )
b. If the reaction is first order, calculate the time to consume 99% of A, given that k =
0.1 min-1. (Answer: t = 46 min)
c. If the reaction is second order, calculate the time to consume 80% of A. k = 0.7
dm3/mol. min. Calculate the pressure at the end of the reaction. (Answer: t = 16 min
and P = 25.6 atm)

Please contact your lecturer or e-tutor should you have trouble in arriving at the same answer.

4.4.2 Design of CSTRs

In learning unit 2, the following design equation for a CSTR was derived:

=
(− )

This makes it possible to calculate the volume V necessary to achieve a conversion X. When the
volumetric flowrate does not change with reaction, (i.e. = ):
−
=
−
Or, expressed in terms of the space time:
−
= =
−
For a first-order irreversible reaction, the rate law is

− =
Combining the rate law and mole balance gives:
−
=

Solving for the concentration of A:

=
1+

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For this case, where there is no volume change during the course of the reaction, we can express the
concentrations in terms of conversion:

= (1 − )
Therefore:

=
1+
For a first-order reaction the product is often referred to as the reaction Damköhler number.

The Damköhler is a dimensionless number that can give a quick estimate of the degree of conversion
achieved in continuous-flow reactions. The Damköhler number is the ratio of the rate of reaction of
A to the rate of convective transport of A at the entrance to the reactor. For first- and second-order
irreversible reactions the Damköhler numbers are:
−
= = =

and

= =

respectively. Values of the Damköhler number, Da, indicate the conversion in continuous-flow
reactors. For example, a value of Da ≤ 0.1 will usually give less than 10% conversion and a value of
Da ≥ 10.0 will usually give a conversion greater than 90%.

LearnChemE discusses design of a CSTR using the Damköhler number (8.42) at the following link:
https://youtu.be/Eu4sx_mTttc.

Activity 4.2

1. For a CSTR, conversion increases with residence time, τ. Is the same true for a PFR?
2. The equation = is valid for a first-order reaction. Would it be valid for a second-order
reaction as well?
3. Calculate how much increase in volume we expect for a CSTR with a first-order, isothermal
reaction → when we want the conversion to be 95% instead of 80%. The concentration
of A in the stream is 3 mol/L.
4. The reaction + → 2 occurs in the liquid phase. It is thought that the reaction is first
order in A and zero order in B.
a. Write an expression for the rate of formation of A that would satisfy the statement
above.
b. If the reaction is performed in a CSTR, show that the relationship between residence
time, , and concentration of A in the exit stream from the CSTR, CA, is given by:

=1+

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CSTRs in series

A first-order reaction with no volume change ( = ) is to be carried out in two CSTRs placed in
series.

− −

Figure 4.2: Two CSTRs in series

The effluent concentration of A from reactor 1 is

=
1+
From a mole balance on reactor 2 we obtain:
− ( − )
= =
−
The concentration exiting the second reactor, :

= =
1+ (1 + )(1 + )

If instead of two CSTRs in series we have n equal-sized CSTRs connected in series ( = = ⋯ =

= ) operating at the same temperature ( = =⋯= = ), the concentration leaving the
last reactor would be

= =
(1 + ) (1 + )
The conversion for n reactor tanks in series is:
1
= 1−
(1 + )
A plot of the conversion as a function of the number of reactors in series for a first-order reaction is
shown in Figure 4.3 for various values of the Damköhler numbers.

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 Figure 4.3: Conversion as a function of the number of tanks in series for different Da numbers

From Figure 4.3 we see that for a 0.5 < Da < 1, conversion increases marginally once we have 4 or 5
CSTRs in series. The cost of adding more CSTRs in series would have to be economically viable in
attaining a significant conversion increase. For a Da 0.1, we notice that the conversion is increased
significantly through the addition of further CSTRs in series.

The rate of disappearance of A in the nth reactor is then calculated from:

− = =
(1 + )

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CSTRs in parallel

If reactors of equal size are placed in parallel and the feed is divided equally between them, then:

Figure 4.4: CSTRs in parallel

The balance over any reactor, i, gives the individual reactor volume.

=
−
Because the reactors are of equal size, operate at the same temperature, and have identical feed
rates, the conversion will be the same for each reaction:

= =⋯= =
and so the rate of reaction in each reactor will also be the same.

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The volume of each individual reactor, Vi, is related to the total volume, V, of all the reactors by:

For the total molar flow rate:

Thus:

=
−
or

= =
− −
This result shows that the conversion achieved in any one of the reactors in parallel is identical to
what would be achieved if the reactant were fed in one stream to one large reactor of volume V.

Study example 4.2 in the prescribed textbook, Elements of Chemical Reaction Engineering.

If you need some extra help in understanding CSTRs in a parallel arrangement, try watching the clip
CSTRs in a Parallel Arrangement (9.22), which you can access at: https://youtu.be/puJXBMtB4W4.

Activity 4.3

1. The design equations for a CSTR in series and in parallel in section 4.4.2 have been derived
for a first-order reaction. Re-derive these equations for a second-order reaction.
2. Sketch conversion as a function of the Damköhler number for a second-order reaction.
3. What can you say about conversion of CSTRs in series, in comparison to CSTRs in parallel?

4.5 Tubular reactors

Gas phase reactions are carried out primarily in tubular reactors where the flow is generally
turbulent. This is because mass transfer co-efficients are higher for turbulent flow. Assuming that
there are no dispersion and radial gradients in either temperature, velocity or concentration, then
the flow in the reactor can be modelled as plug-flow. The differential form of the design equation

=−

must be used when there is a pressure drop in the reactor or heat exchange between the PFR and
the surroundings. When there is no pressure drop or heat exchange, the integral form of the plug-
flow design equation is used:

=
−

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Substituting the rate law for the special case of a second-order reaction gives us:

Considering a constant-temperature and constant-pressure gas phase reaction, the concentration is

expressed as a function of conversion:
1−
=
1+
and then substituted into the design equation:

(1 + )
=
(1 − )

The entering concentration CA0 can be taken outside the integral sign, since it is not a function of
conversion. Because the reaction is carried out isothermally, the specific reaction rate constant, k, is
not a function of temperature and can also be taken outside the integral sign.

(1 + )
=
(1 − )

Simplifying mathematically, we find that

(1 + )
= 2 (1 + ) ln(1 − ) + +
1−

A plot of conversion along the volume of the reactor is shown for four different reactions and values
of ϵ in Figure 4.5 to illustrate the effects of volume change on reaction parameters.

Figure 4.5: Conversion as a function of distance along the reactor

From Figure 4.5 we can see that for identical rate-law parameters, the reaction that has a decrease
in the total number of moles (i.e. = −0.5) will have the highest conversion for a fixed reactor

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length. This relationship should be expected for fixed temperature and pressure because the
volumetric flow rate,

= (1 − 0.5 )
decreases with increasing conversion, and the reactant spends more time in the reactor than
reactants that produce no net change in the total number of moles (e.g., → and = 0).
Similarly, reactants that produce an increase in the total number of moles upon reaction (e.g., = 2)
will spend less time in the reactor than reactants of reactions for which s is zero or negative.

Study example 4.3 in the prescribed textbook, Elements of Chemical Reaction Engineering.

If you need some extra help in following the example in the textbook, try watching PFR Design
Example (6.12) at the following URL: https://youtu.be/Xv1tcwIQ1Jw.

4.6 Using Ca (liquid) and Fa (gas) in the mole balances and rate laws

Sometimes it is more convenient to work in terms of the number of moles (N A, NB) or molar
flowrates (FA, FB, etc.) rather than conversion. Examples of this are membrane reactors and multiple
reactions taking place in the gas phase where molar flowrates rather than conversion are preferred.
We will briefly discuss how we express concentrations in terms of the molar flowrates of the
reacting species rather than conversion, after which we will develop the algorithm using
concentrations (liquids) and molar flowrates (gas) as our dependent variables. The main difference is
that when conversion is used as the variable to relate one species concentration to another species
concentration, we need only write a mole balance on one species, which forms the basis of our
calculation. When molar flowrates and concentrations are used as variables, write a mole balance on
each species and then relate the mole balances to one another through the relative rates of
reaction. For

+ → +

this gives:

= = =
− − − −
Combining the reaction with the generic rate law

− =

This expression is used to develop the algorithms when Ci (liquids) and Fi (gases) are used as the
system variables.

CSTRs, PFRs and batch reactors

Liquid phase

Concentration is a favoured variable for liquid phase reactions in which there is no volume change.
Table 4.3, adapted from Fogler (2013), shows the mole balances for the different types of reactors
we have thus far discussed. These are valid for liquid phase reactions only.

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 Table 4.3: Mole balances for liquid phase reactions
Batch
= =
CSTR ( − ) ( − )
= =
− −( / )
PFR
= =

From Table 4.3 we would need to specify the parameter values for the system ( , , etc.) and for
the rate law (i.e., , , ) to solve the coupled ordinary differential equations for either a PFR or
batch reactor. For the CSTRs we would need to solve the coupled algebraic equations.

Gas phase

Table 4.4 gives the mole balances for gas phase reactions. In the case of the gas phase, the
concentrations in the rate laws need to be expressed in terms of the molar flowrates:

Recalling from learning unit 3:

= =

For an ideal case where Z = 1:

The total molar flowrate is given as the sum of the flowrates of the individual species:

when species A, B, C, D and I are the only ones present. Then

= + + + +
The molar flowrates for each species Fj are obtained from a mole balance on each species, as given
in Table 4.4:

Table 4.4: Mole balances for gas phase reactions + →

Batch CSTR PFR
−
= = =
−

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 −
= = =
−
−
= = =
−

Work through example 4.9 in the prescribed textbook, Elements of Chemical Reaction Engineering.

Activity 4.4

1. The elementary, liquid phase, irreversible reaction

+ →
is to be carried out in a flow reactor. Two reactors are available, an 800 dm3 PFR that
can only be operated at 300 K and a 200 dm3 CSTR that can be operated at 350 K.
The two feed streams to the reactor mix to form a single feed stream that is
equimolar in A and B, with a total volumetric flowrate of 10 dm3/min. Which of the
two reactors will give us the highest conversion?
Additional information:
At 300 K, = 0.07 / ∙
= 85000 / ∙
= =2 /
= = 0.5 × = 5 /
(Answer: CSTR: = 0.926, PFR: = 0.84)

2. Two CSTRs are available in series. The feed stream enters the first CSTR and has a
concentration of A = 1 mol/L. The concentration of A in the exit of the first reactor is
0.5 mol/L. Determine the concentration in the exit stream of the second reactor.
The reaction is second order with regard to A and = 2.
(Answer: = 0.25 / )
3. In an isothermal batch reactor, 70% of a liquid reactant is converted in 13 min.
Calculate the space time needed to achieve the same conversion in a PFR and in a
CSTR.
(Answer: = 13 and = 25 )

4.7 Sources consulted

1. Fogler, HS. (2013), Elements of Chemical Reaction Engineering: International Edition,

PEARSON, 4th Edition.

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