H83RED Reactor

Design

Conversion
and
Reactor Sizing

Suchithra Thangalazhy Gopakumar

Autumn Semester 2015

Outline

Characterisation of reactor feed

Identification of Limiting reactant
Definition of the conversion
Conversion as a measurable design parameter
Design equations in terms of conversion
Levenspiel Plot
Levenspiel Plot as a reactor sizing tool
Sizing reactors in different configurations to
achieve a given conversion

Characterisation of the Reactor Feed

Limiting reactant is the one that get consumed faster in a
reaction
Excess reactant is the surplus amount of a reactant over
the stoichiometric amount required for the reaction to
complete.

+ +


  
= 
 

Characterisation of the Reactor Feed: Example

The gas phase reaction + 2 takes place inside a constant volume batch
reactor at isothermal conditions. Initially, the reactor contains 1.5 kmol of CO, 1 kmol of O2
and 1 kmol of CO2 and 0.5 kmol of N2 at a pressure 5 atm.
(a) Identify the limiting reactant
(b) Determine the excess amount of the other reactant.

Solution

For reactants calculate the

ratios
Values of the ratios
show

1.5
=
= 0.75

1.0
=
= 1.0

Therefore CO is the limiting

reactant

One mole of CO2 reacts with 0.5 moles of O2

Stoichiometric amount of O2
required

= 0.5 1.5 =0.75

 . 

=
= .

. 

Characterisation of the Reactor Feed

Stoichiometric coefficients

When we consider the reactions taking place inside a reactor,

the stoichiometric equation should be considered.
Consider following reaction

The stoichiometric equation is

Consider a chemical reaction as shown below

This can be rewritten in the form

-a, -b, c and d are called stoichiometric coefficients. Negative and

positive signs indicate the consumption and generation of
materials respectively.

Conversion
Conversion of species A is defined as the number of moles A that have
reacted per mole of A fed into the system:

XA

moles of A reacted
moles of A fed

(1)

XA(max)

= 1 for irreversible reaction

= XAeq for reversible reaction

In general, for reaction of any complexity we are able to follow conversion of any
substance via stoichiometry. For example, in case of the following reaction:
aA +

bB

cC

dD

every quantity could be put on a per mole A basis

A

b
c
B
C
a
a

d
+
D
a

Conversion of reactants correlates with product generation via stoichiometry

Conversion in a Batch Reactor

Batch reactors are operated for a given period of time. Consider a
general form of the reaction within a batch reactor as
[A]
At time t = 0 the amount of A (the limiting reactant) charged into the batch
reactor in NA0. After time t = t the amount of A remaining in the reactor is NA.
Amount of A reacted during the period t

[2]

The number of moles of A that remain in the reactor after a time t:

moles of A
reacted N A0 X

[3]

Conversion in a Batch Reactor

The design equation for the batch reactor is (in which reaction [A] takes
place)
=

Substituting equation [3] in [4]

=

[4]

=

The design equation in differential form in term of XA is

[5]

We call eq [5] the design equation for a batch reactor, because we

have written the mole balance in terms of conversion XA .

Conversion in a Batch Reactor

The design equation in differential form in term of XA is

Integration with the limits at reaction start: t = 0, X = 0

()

[6]

The design equation in integral form in term of XA is

()

[7]

Levenspiel* Plot
When we inspect the equations derived above, it is clear that we
have to carry out an integration of the form

It is clear from the rate law

that

The above integral can be estimated graphically if we know the values of

or for various values of conversion X.

The rate of reaction for various

conversions of a limiting reactant
can be measure in a series of
controlled experiments.
Curve that shows

against

conversion x is called the LEVENSPIEL

PLOT

Conversion
X

* Named after Octave Levenspiel, Oregon State University, who suggested this graphical method first

1.0

Levenspiel Plot as a Reactor Sizing Tool

Batch Systems Graphical analysis
Consider a batch reactor
=

At the start of the reaction (t=0)

Therefore

Levenspiel Plot

Area=

Nearer to the end of the

reaction

As a result lowest at

have higher value that at

Conversion
X

()

1.0

Levenspiel Plot as a Reactor Sizing Tool

When we consider a constant volume batch
reactor

and

= 1

[8]

1
=

=

[9]

Levenspiel Plot

Area=

()

Concentrati
on

Conversion: Example
A liquid phase reaction A + B C + D takes place in a constant volume Batch
Reactor. The initial concentration of A, the limiting reactant, is 7 mol dm-3. The
reaction is non-elementary so that rA= k CA with the specific rate constant k = 0.06
min-1. what is the conversion of A if the reactor has been operational for 30 minutes?

Solution
The reaction is

+ +

For a Batch reactor

Integrating gives

=

=
=

With =

Reason out how the concentration is

included
Reason out the limits
uses

=
=



=
=
=1


= 1
= 1

Therefore

= .

Conversion: Example
A liquid phase reaction A C + D takes place in a constant volume Batch Reactor. The initial
amount of A, the limiting reactant, fed to the reactor is 20 mol. The reaction is elementary so that
rA= k CA with the specific rate constant k = 0.06 min-1.
How long would it take to achieve 90% conversion?
How long would it take to achieve 99 % conversion?

Solution

The reaction is +

For a Batch reactor

Substituting for NA

=

()

=

= 0.06

With =
=

()

1
1

Therefore when XA
=0.9

=

1
1
2.3

min =
min
0.06
1 0.9
0.06

Therefore when XA
=0.99

=

1
1
2.3

min =
min
0.06
1 0.99
0.06

Fill the missing steps

Conversion in Flow Reactors

In batch reactors: X = f (t). In flow systems, reaction time increases
with increasing reactor volume, therefore X = f (V )
Conversion is defined as

[10]

Rearranging equation [10]

 




gives the molar rate at which

species A is reacting within the entire
system at steady state

[11]

Molar flowrate
Molar

of A leaving
= flowrate

the system
of A fed

Conversion in Flow Reactors

Flow Systems
The entering molar flow rate of species A, FAO (mol/s) is the product of the entering
concentration, CAO(mol/dm3) and the entering volumetric flow rate, v0 (dm3/s):

FA0 C A0 v0
Liquid phase
CAO is given in term of molarity.

Example:

CAO =2 mol/dm3

Gas phase
CAO and FAO can be calculated by the entering temperature and pressure using the
ideal gas law:

PA0V0 N A0 RT0

C A0

PA0 y A0 P0

RT0
RT0

FA0 v0C A0 v0

y A0 P0
RT0

where NA0= entering number of mole of A

yA0 = entering mole fraction of A
P0 = entering total pressure, e.g., kPa
PA0 = yA0 P0 = entering partial pressure of A, e.g., kPa
T0 = entering temperature, K
kPa.dm 3
R = ideal gas constant (e.g., R = 8.314 mol.K )

Conversion in Flow Reactors

Continuous Stirred Tank Reactor (CSTR)
Following equation was derived from mole
balance

[12]

For flow reactor systems, from equation

[11]
[11]

Substituting eq [11] in eq [12]

[13]

Since the exit composition from

the reactor is identical to the
composition inside the reactor
(perfect mixing), the rate of
reaction is evaluated at the exit
conditions.

Conversion in Flow Reactors

Plug Flow Reactor (PFR)
The mole balance applied to
PFR provided

[14]

[11]

Substituting eq [11] in eq [14]

[16]

[11]

Substituting eq [13] in eq
[18]

The mole balance applied to

PFR provided

Packed Bed Reactor (PBR)

[15]

[17]

Conversion: Example
A liquid phase reaction A C + D takes place in a Packed Bed Reactor. The
reaction is elementary so that rA= k CA with the specific rate constant k = 0.005 dm3
min-1 [kg(cat)]-1 . The expected conversion is 80%.
a. Find the mass of the catalyst as a function of the inlet flowrate.

Solution

The reaction is +

For a PBR

Substituting for NA

()

=
Therefore when XA
=0.8

=

= 0.005 ()

With =
=

()

1
1

0.005
1 0.8

= 

= 200 1.61

Fill the missing steps

Levenspiel Plot as a Reactor Sizing Tool

CSTR Graphical analysis

Rearranging the design equation

Levenspiel Plot

The area of the rectangle

shown in the figure gives

the ratio.

Area=

()

Conversion
X

1.0

Levenspiel Plot as a Reactor Sizing Tool

Tubular Flow Reactors
Plug Flow Reactor

Packed Bed Reactor

1
=

1
=

[16]

Levenspiel Plot

Area=

Area=

[17]

Levenspiel Plot

Conversion
X

()

1.0

Conversion
X

()

1.0

Levenspiel Plot as a Reactor Sizing Tool

Space Time and Space Velocity
The space time (the holding time or mean residence time) is the time
necessary to process one reactor volume of feed fluid based on entrance
conditions.
V
V the reactor volume

[18]
0 the volumetric flow rate entering the reactor
0
20 m

20 m
Reactor

Consider the tubular reactor, which is 20 m long and 0.2 m3 in volume. The dashed
line represents 0.2 m3 of fluid directly upstream of the reactor The time it takes for this
volume to enter the reactor completely is the space time. For instance, if the space
time is 5 min, it means that every 5 minutes one reactor volume of feed at specified
conditions is being treated by the reactor.

The space velocity (SV) is defined as:

SV

0
V

so

SV

[19]

SV and are not just the reciprocal parameters since they often refer to different
conditions: to the entrance conditions; SV might be referred to the conditions at
specific location in the reactor

Levenspiel Plot as a Reactor Sizing Tool

CSTR

F X
V A0
(rA ) exit

Design equations

[20]

Put the left-hand sides

in terms of space times

V FA 0
0

V
FA0 X

0 0 (rA ) exit

Divide both sides of the

equations by the entering
volumetric flow rate

1
rA

PFR

V FA0

0 0

C A0 X

( rA )exit

[22]

Area=/CA0=X

r
A

1
rA

dX
rA

[21]

dX
0 rA
X

dX
rA
0

C A0

[23]
X

dX
rA
0

Area = /CA0=

1
rA exit

XA

XA

Conversion: Summary
Mole Balance for Different Reactors
Reactor Type
Batch

Differential

N A0

Algebraic

dX
rAV
dt

Integral

t N A0

X A (t )

dX
rAV

FA 0 X
(rA ) exit
C X
A0
( rA )exit
V

CSTR

PFR

FA0 dX
rA
dV

V FA 0

C A0

X out

dX
rA

dX
rA

X in
X out

X in

PBR

FA0 dX
rA
dW

W FA 0

X out

X in

dX
rA

Levenspiel Plot as a Reactor Sizing Tool

Constant Density Systems
Since the reaction volume does not change in the reactor (q = q0), molar flux
of species A into the reactor:

FA0 0 C A0
Lets express conversion from the equation (13):

FA FA0 (1 X )

FA0 FA 0C A0 0C A C A0 C A

FA0
0C A0
C A0

In CSTR operated at steady-state

conditions, conversion does not change
through the reactor volume:

C A0 C A
X
C A0

FA 0 FA
FA 0

In PFR systems conversion changes

depending on location. The conversion at
specific point can be expressed via
differentiation:

dC A
dX
C A0

Levenspiel Plot as a Reactor Sizing Tool

Finding Space Time

CSTR

PFR
X

Design equations

C A0 X

( rA )exit

Replace conversion
using its relation with
concentrations

Design equations via

concentration term

C CA
A0
rA

1
rA

[26]

C A0 C A0 C

rA
C A0

Constant density
only

Area = = C A0 C A
r

dX
rA
0

C A0

[27]

1
dC A

C A0

rA
C A0
C A0
CA

[28]

C A0

CA

1
rA

dC A
rA

[29]

Constant density
only
C A0

Area = =

CA

CA(t)

CA0

CA

CA(t)

CA0

dC A
rA

CA

Reactor Sizing: Graphical Method

Methodology
If the rate of reaction is available as a function of conversion, -rA=f(X) (or in
some specific cases as a function of concentration, rA=f(CA)), or if it can be
generated by some intermediate calculation, one can size the reactor using
the set of design equations by determining reactor volume or space time.
Task: The laboratory measurements of reaction rate for the gas phase
reaction
A B + C
3 s)
gave
the
result
in mol/(dm
0.0 following
0.1
0.2 - rates
0.3 are0.4
0.5
0.6
0.7
0.8
0.9
X
-rA

0.0053

0.0052

0.0050

0.0045

0.0040

0.0033

0.0025

0.0018

0.00125

0.001

T = 422.2 K, total pressure = 1013 kPa, initial charge 50 % inerts, 50 % A.

Compare the volumes of CSTR and PFR required for the same conversion
of 60%, if the volumetric flow rate is 34.65 dm3/s.

Reactor Sizing: Graphical Method -Example

X

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

-rA

0.0053

0.0052

0.0050

0.0045

0.0040

0.0033

0.0025

0.0018

0.00125

0.001

1/rA

189

192

200

222

250

303

400

556

800

1000

Solutio
n

CSTR

600

FA 0 X
(rA ) exit

V
FA0

V
X

FA0 ( rA )exit

(0.6, 0)

1
rA

1
V
dm 3 s
X 400 0.6 240

FA0 rA
mol

400

The CSTR volume necessary to

achieve 60% conversion is:

200

is the area of rectangle with

vertices
(0, 0), (0, 400), (0.6,400), and

0.2

0.4
0.6
Conversion X

0.8

3
5 mol 240 dm s
1200 dm 3
V

mol
s

Reactor Sizing: Graphical Method -Example

X

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

-rA

0.0053

0.0052

0.0050

0.0045

0.0040

0.0033

0.0025

0.0018

0.00125

0.001

1/rA

189

192

200

222

250

303

400

556

800

1000

Solution (continuation)
V
PFR

FA 0

dX
0 rA

dX
X 1
4
1

0 rA 3 rA ( 0 ) rA ( 0.3 ) rA ( 0.6 )

0.6

numerical evaluation of integral

based on Simpson's One-Third
Rule
0 .3

[189 4 222 400]

3

600

1
rA
400

dm 3 s
148
mol

The PFR volume necessary to

achieve 60% conversion is:

200

A B

0.2

0.4
Conversion X

0.6

0.8

3
5 mol 148 dm s
740 dm 3
V

mol
s

Reactor Sizing: Graphical Method -Example

X

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

-rA

0.0053

0.0052

0.0050

0.0045

0.0040

0.0033

0.0025

0.0018

0.00125

0.001

1/rA

189

192

200

222

250

303

400

556

800

1000

A B

Solution (continuation)

Graphical Analysis
600

1
rA

Difference
between
CSTR and PFR

PFR

For isothermal reactions of

greater than zero order, the PFR
will always require a smaller
volume that the CSTR
to
achieve the same conversion

400

200

0.2

0.4
Conversion X

0.6

0.8

Reactor Sizing: Different Configurations

Reactor in Series
The same conversion may be reached in two stages, for example, one reactor will
provide conversion to 30% while second one will increase the conversion from 30%
to 60%:
Two CSTR
Two PFR
FA0
i =1

FA0

FA1
X1=0.3

V1

V1

i=2
-rA1

i=1
FA1
X1=0.3

-rA1

i=2
V2

FA2
V2

X2=0.6

FA2
X2=0.6

-rA2

-rA2

Conversion is defined in terms of location at a point downstream rather than with

respect to any single reactor
Xi =

Total moles of A reacted up to point i

Moles of A fed to the first reactor

Reactor Sizing: Different Configurations

Two CSTR
FA0

V = V1 + V2

i =1

F A0
X1
r A1
V 2 ?
V1

FA1
X1=0.3

V1

i=2
-rA1

FA2
V2

X2=0.6

-rA2

A mole balance on the second reactor:

In Out + Generation = 0
Reactor 2:

F A1 F A2 r A2 V2 0
F F A2
V2 A1
- r A2
F A1 F AO - F AO X 1
F A2 F AO - F AO X 2

(F
V2
V2
V2

- F AO X 1 )(F
- r A2
- F AO X 1 F AO X 2

- r A2
F (X 2 X 1 )
AO
- r A2
AO

AO

- F AO X 2 )

Reactor Sizing: Different Configurations

Two CSTR in series

Two PFR in series

X 1 dX X 2 dX
V V1 V2 FA0

r
0 A X 1 A

F
F
V V1 V2 A0 X 1 A0 X 2 X 1
rA1
rA 2
600

1
rA

600

CSTR 1

1
rA

CSTR 2

PFR 2

400

400

200

200

0.2

0.4

0.6

0.8

Conversion X

Volume of two CSTR in series smaller

than the volume of one CSTR

PFR 1

0.2

0.4

0.6

0.8

Conversion X

Volume of two PFR in series is

identical to that of one PFR

The difference between overall volume of two CSTR in series and two (or one)
PFR decreases

Reactor Sizing: Different Configurations

2) PFR-CSTR

1) CSTR-PFR

X1

2
FA0
dX
V V1 V2
X 1 FA0
rA1
rA
X1

600

1
rA

V V1 V2 FA0
0

600

CSTR

1
rA

PFR

400

400

200

200

0.2

0.4
Conversion X

0.6

0.8

dX
F
A0 X 2 X 1
rA rA2

CSTR

PFR

0.2

0.4

0.6

Conversion X

Reactor size can be optimised by the selection of number of stages, type of

reactors, and their combinations

0.8

Reactor Sizing: Different Configurations

3) PFR - CSTR - PFR

X =0

X1

600

V1
FA0

V2
X1

V1 FA0
0

dX
rA

F
V2 A0 X 2 X 1
rA2
X3

dX
rA
X2

V3 FA0

X2

V3

X3

CSTR

1
rA

PFR

400

200
V1 / FA0

V2 / FA0

X1

V3 / FA0

X2

Conversion X

X3

Reactor Sizing: Different Configurations

Sequencing of reactors
Question:
Which arrangement is the best?

Answer:
It depends on the:
a) Shape of the Levenspiel plots
b) Relative reactor sizes

For autocatalytic reactions:

CSTR is more efficient at low conversions,
PFR is more efficient at high conversions

Reactor Sizing: Different Configurations

Reactor Staging
Lets analyse multistage reactor system, say 5 stages of similar reactor:
1

FA0
rA

As we make the volume of each

CSTR smaller and increase the
number of CSTRs,

V5

V4

Total number of the CSTRs in series

Volume of the PFR

V3
V2

V1

A PFR can modelled as a

number of CSTR in series
0

X1

X2

X3

X4

X5

Reactor Sizing: Different Configurations -Example

Consider the reaction A B . It is carried out adiabatically in the liquid

phase and following data were obtained.
X

0.0

0.2

-rA (kmol/m3
39
53
h)
The reactor scheme is shown below

0.4

0.6

0.65

59

38

25

FA0
X1=0.2
V1

X2=0.6
V2

FA1

FA0
FAex
V3
X2=0.65

Calculate the volume of each of the reactors for an entering molar flowrate of
A of 50 kmol/h

Reactor Sizing: Different Configurations -Example

Solution

FA0
X1=0.2

X2=0.6
V2

V1

FA1

FA0

PFR 1

CSTR 1

FAex
V3
CSTR 2

For CSTR 1

For PFR 1

F
V1 A0 X 1
rA

X3=0.65

For CSTR 2
F
V3 A0 X 3 X 2
rA

FA0
dX
V2
rA
X1
X2

Molar flowrate of A FA0 50 mol / h

X

0.0

0.2

0.4

0.6

0.65

-rA (kmol/m3
h)
[FA0/-rA] (m3)

39

53

59

38

25

1.28

0.94

0.85

1.32

2.0

Reactor Sizing: Different Configurations -Example

FA0

0.0

0.2

-rA
(kmol/m3 h)

39

[FA0/-rA]
(m3)

1.28

0.4

53

0.6

59

0.94

0.65

38

0.85

25

1.32

2.0

X1=0.
2
FA1

V1
CSTR
1

V2
PFR 1

X2=0.
6
FA0
FAex
V3
CSTR
2

CSTR 1

X3=0.6
5

F
V1 A0 X 1 0.94 0.2 0.188 m3
rA

2.5

FA0
dX
rA
0.2
0.6

X
V2
3

1.5
1.32

1.28
1

PFR V2

FA0

FA0
FA0

r
A x 0.2
A x 0.4 A x 0.6

V2 0.38 m 3

0.94

0.85

CSTR 2

0.5

0
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

F
V3 A0 X 3 X 2 2.0 0.65 0.6 0.1m3
rA

Summary