Conversion and Reactor Sizing

Conversion
Consider the general reaction
aA bB cC dD
We will choose A as our basis of calculation
b
c
d
A B C D
a
a
a

The basis of calculation is most always the limiting reactant.

The conversion of species A in a reaction is equal to the number of moles of A

reacted per mole of A fed.
N NA
batch reactor
X A A0
N A0
molesofA reacted
XA
molesofA fed
F F
flow reactor
X A A0 A
FA 0
For irreversible reactions, the maximum value of conversion, X, is that for complete
conversion, i.e. X=1.0.
For reversible reactions, the maximum value of conversion, X, is the equilibrium
conversion, i.e. X=Xe.
2

Batch Reactor Design Equations

X

N A0 N A
N A0

N A N A 0 N A 0 X N A 0 (1 X)
dN A
dX
N A0
dt
dt

dN A
rA V
dt

N A0

dX
rA V
dt

t=0
X=0

t N A0

differential form

For a constant-volume batch reactor, V=V0

dN A
rA V
dt

dX
rA V

integral form

The longer the reactants are

left in the reactor, the greater
will be the conversion.

1 dN A d ( N A / V0 ) dC A

rA
V0 dt
dt
dt

used for analyzing rate

data in a batch reactor
3

Design Equations for Flow Reactor

X

FA 0 FA
FA 0

FA FA 0 (1 X)

The entering molar flow rate of species A, FA0 (mol/s), is just the product of the entering
concentration, CA0 (mol/dm3), and the entering volumetric flow rate, v0 (dm3/s):
FA 0 C A 0 v 0
For liquid system, CA0 is commonly given in terms of molarity, for example,
CA0 = 2 mol/dm3
For gas system, CA0 can be calculated from the entering temperature and
pressure using the ideal gas law or some other gas law. For an ideal gas law
CA0

PA 0 y A 0 P0

RT0
RT0

FA 0 v 0 C A 0 v 0

y A 0 P0
RT0

yA0 = entering mole fraction of A (-)

P0 = entering total pressure (kPa)
PA0 = yA0P0 = entering partial pressure of A (kPa)
T0 = entering temperature (K)
R = ideal gas constant (=8.314 kPadm3/molK)

Example 2-1
A gas of pure A at 830 kPa enters a reactor with a volumetric flow rate, v0, of 2 dm3/s
at 500 K. Calculate the entering concentration of A, CA0, and the entering molar flow
rate, FA0.
Solution

CA0

y A 0 P0
(1)(830 kPa )

0.20 mol / dm 3
3
RT0
(8.314dm kPa / mol K )(500K )

FA 0 C A 0 v 0 (0.2mol / dm 3 )(2dm 3 / s) 0.4 mol / s

This feed rate (FA0 = 0.4 mol/s) is in the
range of that which is necessary to form
several million pounds of product per year.

CSTR Design Equations

F F
V A0 A
rA

FA FA 0 (1 X)

FA 0 FA 0 (1 X)
rA

FA 0 X
( rA ) exit

Because the reactor is perfectly mixed, the exit

composition from the reactor is identical to the
composition inside the reactor, and the rate of
reaction is evaluated at the exit conditions.

PFR Design Equations

dFA FA 0dX

FA FA 0 (1 X)
dFA FA 0dX

dFA
rA
dV

V=0
X=0

V FA 0

dX
rA

FA 0

dX
rA
dV

differential form

integral form

PBR Design Equations

differential form

integral form

FA 0

dX
rA '
dW

W FA 0

dX
rA '

used when analyzing reactors that

have a pressure drop along the length
of the reactor
used in the absence of pressure drop
7

Reactor Sizing

Given -rA as a function of conversion, -rA=f(X), one can size any type of
reactor. We do this by constructing a Levenspiel plot. Here we plot either
FA0/-rA or 1/-rA as a function of X.
For FA0/-rA vs. X, the volume of a CSTR and the volume of a PFR can be
represented as the shaded areas in the Levenspiel Plots shown below:

Consider the isothermal gas-phase isomerization

AB
We are going to the laboratory to determine the rate of chemical reaction as
function of the conversion of reactant A.
The laboratory measurement given in Table 2-1 show the chemical reaction rate
as a function of conversion. The temperature was 500 K, the total pressure was
830 kPa, and the initial charge to the reactor was pure A.

1/-rA as a
function of X

For all irreversible reactions of greater than zero order, as we approach complete
conversion where all the limiting reactant is used up, i.e., X=1, the reciprocal rate
approaches infinity as does the reactor volume, i.e.
A BC

AsX 1,  rA 0, thus , 

1
therefore V
rA

An infinite reactor volume is necessary to

reach complete conversion, X=1.0

For reversible reactions, the maximum conversion is the equilibrium conversion

Xe. At equilibrium, the reaction rate is zero. Therefore,
A BC

AsX X e ,  rA 0, thus , 

1
therefore V
rA

An infinite reactor volume would also be necessary to

reach the exact equilibrium conversion, X=X e.
10

To size a number of reactors for the reaction we have been considering, we will
use FA0 = 0.4 mol/s to add another row to the processed data shown in Table 2-2
to obtain Table 2-3.

FA0/-rA as a
function of X
0.4

11

Example 2-2
The reaction described by the data in Table 2-2
AB
is to be carried out in a CSTR. Species A enters the reactor at a molar flow rate of 0.4 mol/s.
(a)Using the data in either Table 2-2, Table 2-3, or Figure 2-1, calculate the volume necessary
to achieve 80% conversion in a CSTR.
(b)Shade the area in Figure 2-2 that would give the CSTR volume necessary to achieve 80%
conversion.
Solution
(a
)

rA

FA 0 X
( rA ) exit
20m 3 s / mol

X 0.8

V (0.4mol / s) (20 m 3 s / mol) (0.8) 6.4m 3

12

(b)

FA 0
X
rA

FA 0

rA

8
X 0.8

V (8m 3 ) (0.8) 6.4m 3

The CSTR volume necessary to achieve 80% conversion is 6.4 m3 when operated at 500 K,
830 kPa, and with an entering molar flow rate of A of 0.4 mol/s.
This volume corresponds to a reactor about 1.5 m in diameter and 3.6 m high.
Its a large CSTR, but this is a gas-phase reaction, and CSTRs are normally not used for
gas-phase reactions.

13

Example 2-3
The reaction described by the data in Table 2-1 and 2-2 is to be carried out in a PFR. The
entering molar flow rate of A is 0.4 mol/s.
(a)First, use one of the integration formulas given in Appendix A.4 to determine the PFR
reactor volume necessary to achieve 80% conversion.
(b)Next, shade the area in Figure 2-2 that would give the PFR volume necessary to achieve
80% conversion.
(c)Finally, make a qualitative sketch of the conversion X, and the rate of reaction, -rA, down
the length (volume) of the reactor.
Solution

(a
)

V FA 0

0.8

0.8 F dX
dX
A0

0
rA
rA

FA 0
4FA 0
2FA 0
4FA 0
FA 0
X

3 rA (X 0) rA (X 0.2) rA (X 0.4) rA (X 0.6) rA (X 0.8)

0 .2
(0.89 4(1.33) 2(2.05) 4(3.54) 8.0) m 3 2.165m 3
3
14

(b)

0 .8

FA 0dX
 Areaunder thecurve betweenX 0andX
rA

0 .8

For 80% conversion, the shaded area is roughly equal to 2.165 m3.
The PFR reactor volume necessary to achieve 80% conversion is 2.165 m3. This volume
could result from a bank of 100 PFRs that are each 0.1 m in diameter with a length of 2.8 m.

15

(c)
For X=0.2, we calculate the corresponding reactor
volume using Simpsons rule with X=0.1 and the
data in rows 1 and 4 in Table 2-3.

V FA 0

0.2

0.2 F dX
dX
A0

0
rA
rA

FA 0
4FA 0
FA 0
X

3 rA (X 0) rA (X 0.1) rA (X 0.2)

0.1
(0.89 4(1.08) 1.33) m 3 0.218m 3
3

16

Example 2-4
It is interesting to compare the volumes of a CSTR and a PFR required for the same
job. To make this comparison, we shall use the data in Figure 2-2 to learn which
reactor would require the smaller volume to achieve a conversion of 80%: a CSTR
or a PFR. The entering molar flow rate FA0 = 0.4 mol/s, and the feed conditions are
the same in both cases.
Solution

The CSTR volume was 6.4 m3 and the PFR volume was 2.165 m3. When we combine Figures
E2-2.1 and E2-3.1 on the same graph, we see that the crosshatched area above the curve is the
difference in the CSTR and PFR reactor volumes.
For isothermal reactions greater than zero order, the CSTR volume will usually be greater
than the PFR volume for the same conversion and reaction conditions (temperature, flow rate,
etc.)

17

We see that the reasons the isothermal CSTR volume is usually greater than
the PFR volume is that the CSTR is always operating at the lowest reaction
rate (e.g., -rA = 0.05 in Figure E2-4.1(b)).
The PFR on the other hand starts at high rate at the entrance and gradually
decreases to the exit rate, thereby requiring less volume because the volume is
inversely proportional to the rate.
However, for autocatalytic reactions, product-inhibited reactions, and
nonisothermal exothermic reactions, these trends will not always be the case.

18

Reactors in Series
For reactors in series, the conversion X is the total number of moles of A
that have reacted up to that point per mole of A fed to the first reactor.

Xi

Totalmole sofArea ctedupto po int i

MolesofA fedtoth efirstre actor

only be used when the feed stream

only enters the first reactor in the
series and there no side streams either
fed or withdrawn.

X1 at point i=1 is the conversion achieved in the PFR

X2 at point i=2 is the total conversion achieved in at this point in the PFR and the CSTR
X3 is the total conversion achieved by all three reactors
19

CSTR in Series

Reactor 1:
FA 0 FA1 rA1V1 0

FA1 FA 0 (1 X1 )

FA 0
X1
rA1

V1

Reactor 2:
FA1 FA 2 rA 2 V2 0

FA 2 FA 0 (1 X 2 )

F
V2 A 0 (X 2 X1 )
rA 2

20

Example 2-5
For the two CSTRs in series, 40% conversion is achieved in the first reactor. What is
the volume of each of the two reactors necessary to achieve 80% overall conversion
of the entering species A?

Solution

FA 0

V1
rA1
F
V2 A 0
rA 2

X1 (2.05m 3 )(0.4) 0.82 m 3

X1

(X 2 X1 ) (8.0 m 3 )(0.8 0.4) 3.2 m 3

X2

V V1 V2 0.82m 3 3.2m 3 4.02 m 3

The sum of the two CSTR reactor volumes (4.02 m3) in
series is less than the volume of one CSTR (6.4 m3) to
achieve the same conversion.

21

Consider approximating a PFR with a number of small, equal-volume CSTRs

of Vi in series (Figure 2.5). We want to compare the total volume of all the
CSTRs with the volume of one PFR for the same conversion.
From Figure 2-6, the total volume to achieve 80%
conversion for five CSTRs of equal volume in
series is roughly the same as the volume of a PFR.
As we make the volume of each CSTR smaller and
increases the numbers of CSTRs, the total volume
of the CSTRs in series and the volume of the PFR
will become identical.

We can model a PFR with a large number of CSTRs

in series.
This concept of using many CSTRs in series to model
a PFR will used later in a number of situations, such
as modeling catalyst decay in packed-bed reactors or
transient heat effects in PFRs.

22

PFR in Series

X2

V FA 0
0

X
X
dX
dX
dX
FA 0
FA 0
0
rA
rA X
rA
1

It is immaterial whether you place two plug-flow

reactors in series or have one continuous plugflow reactor; the total reactor volume required to
achieve the same conversion is identical.

23

Example 2-6
Using either the data in Table 2-3 or Figure 2-2, calculate the reactor volumes V1 and V2 for the
plug-flow sequence shown in Figure 2-7 when the intermediate conversion is 40% and the final
conversion is 80%. The entering molar flow rate is the same as in the previous example, 0.4 mol/s.
Solution

V1 FA 0

0.4

0.4 F dX
dX
A0

0
rA
rA

FA 0
4FA 0
FA 0
X

3 rA (X 0) rA (X 0.2) rA (X 0.4)

0.2
(0.89 4(1.33) 2.05) m 3 0.551m 3
3
0.8 dX
0.8 F dX
V2 FA 0
A0
0.4 r
0.4 r
A
A

V V1 V2 0.551m 3 1.614 m 3 2.165m 3

FA 0
4FA 0
FA 0
X

3 rA (X 0.4) rA (X 0.6) rA (X 0.8)

0.2
(2.05 4(3.54) 8.0) m 3 1.614 m 3
3

24

Combination of CSTRs and PFRs in Series

Reactor 1:
FA 0
X1
rA1

V1

Reactor 2:
F
V2 A 0 (X 2 X1 )
rA 2

Reactor 3:
X3

V3 FA 0
X2

dX
rA

25

Example 2-7
The isomerization of butane
nC4H10iC4H10
was carried out adiabatically in the liquid phase and the data in Table E2-7.1 were obtained.

It is real data for a real reaction carried out adiabatically, and the reactor scheme shown in
Figure E2-7.1 is used.
Calculate the volume of each of the reactors for an entering molar flow rate of n-butane of
50 kmol/hr.

26

Solution

For the first CSTR

FA 0
X1 (0.94 m 3 )(0.2) 0.188m 3
rA1

V1
For the PFR

0.6 F dX
dX
V2 FA 0
A0
0.2 r
0.2 r
A
A
0.6

FA 0
4FA 0
FA 0
X

3 rA (X 0.2) rA (X 0.4) rA (X 0.6)

0 .2
(0.94 4(0.85) 1.32) m 3 0.38m 3
3

For the second CSTR

F
V3 A 0 (X 3 X 2 ) (2.0 m 3 )(0.65 0.6) 0.1m 3
rA 3

27

If we look at Figure E7-2.2, the area under the curve

(PFR volume) between X = 0 and X = 0.2, we see that
the PFR area is greater than the rectangular area
corresponding to the CSTR volume, i.e., VPFR > VCSTR.
However, if we compare the areas under the curve
between X = 0.6 and X = 0.65, we see that the area
under the curve (PFR volume) is smaller than the
rectangular area corresponding to the CSTR volume,
i.e., VCSTR > VPFR. This result often occurs when the
reaction is carried out adiabatically.

Which reactor should go first to give the highest overall conversion?

It depends not only on the shape of the Levenspiel plots (FA0/-rA) vs. X,
but also on the relative reactor sizes.
VCSTR1 = 3 m3
VCSTR2 = 2 m3
VPFR = 1.2 m3
-rA = f(X, CA0, T, P)

finding the highest possible conversion X

data presented as rA as a function of X are useful
only in the design of full-scale reactors that are to be
operated at the identical conditions as the laboratory
experiments (temperature, pressure, initial reactant
concentrations)
28

Some Further Definitions

Consider the special case of the PFR design equation when
the volumetric flow rate is constant.
The space time, , is obtained by dividing reactor volume by the volumetric flow
rate entering the reactor:

V
v0

The space time is the time necessary to process one

reactor volume of fluid based on entrance conditions.
Consider the tubular reactor shown
in Figure 2-12, which is 20 m long
and 0.2 m3 in volume.

The dashed line in Figure 2-12 represents 0.2 m3 of fluid directly upstream of the
reactor. The time it takes for this fluid to enter the reactor completely is the space
time. It is also called the holding time or mean residence time.
v0 = 0.01 m3/s

V
0.2 m 3

20 s
v 0 0.01m 3 / s

taking 20 s for the fluid at point a to

move point b, which corresponds to
a space time of 20 s.

29

In the absence of dispersion, the

space time is equal to the mean
residence time in the reactor, tm.
This time is the average time the
molecules spend in the reactor.

A range of typical processing times in terms of the

space time (residence time) for industrial reactors
is shown in Table 2-4.

Table 2-5 shows space times

for six industrial reactions
and reactors.

30

The space velocity (SV), which is defined as

SV

v0
1
SV
V

The space velocity might be regarded at the first sight as the reciprocal of the space
time. However, there can be a difference in the two quantities definitions. For the
space time, the entering volumetric flow rate is measured at the entrance
conditions,
but for the space velocity, other conditions are often used.
The two space velocities commonly used in industry are the liquid-hourly and gashourly space velocities, LHSV and GHSV, respectively.
The entering volumetric flow rate, v0, in the LHSV is frequently measured as that
of a liquid feed rate at 60 F or 75 F, even though the feed to the reactor may be a
v 0 liquid
vapor at some higher temperature.
LHSV
V

The gas volumetric flow rate, v0, in the GHSV is normally measured at standard
temperature and pressure (STP). GHSV v 0 STP
V
31

Example 2-8
Consider the space time, , and space velocities for each of the reactors in Examples 2-2 and 2-3.
Solution
From example 2-2, the CSTR volume was 6.4 m3 and the corresponding space time
and space velocity are

V
6.4 m 3

3200s 0.89 h
3
v 0 0.002 m / s
SV

1
1

1.125h
0.89h

From example 2-3, the PFR volume was 2.165 m3 and the corresponding space time
and space velocity are

V
2.165m 3

1083s 0.30 h
3
v 0 0.002 m / s
SV

1
1

3.333h
0.30h

32

Levenspiel Plots in Terms of Concentration

FA 0 C A 0 v 0

F F
X A0 A
FA 0

FA C A v

dX

V FA 0

dX
rA

C v CA v
X A0 0
CA0 v0

v v0

CA0 CA
CA0

dC A
CA0

X=0, CA=CA0
X=X, CA=CA

V v0

CA 0

CA

dC A
rA

CA 0

CA

dC A
rA

a form of the design equation for constant volumetric

flow rate that may prove more useful in determining
the space time or reactor volume for reaction rates
that depend only on the concentration of one species.
The area under the curve gives the space time necessary
to reduce the concentration of A from CA0 to CA.

33

Example
For the irreversible gas-phase reaction:
A2B
the following correlation was determined from laboratory data (the initial concentration
of A is 0.2 g mol/L):

10 8
ForX 0.5, 
3.0 m 3 s / mol
rA

10 8
ForX 0.5, 
3.0  10(X 0.5) m 3 s / mol
rA
The volumetric flow rate is 5 m3/s.
a. Over what range of conversions are the plug-flow reactor and CSTR volumes identical?
b. What conversion will be achieved in a CSTR that has a volume of 90 L?
c. What plug-flow reactor volume is necessary to achieve 70% conversion?
d. What CSTR reactor volume is required if effluent from the plug-flow reactor in part (c) is fed
to a CSTR to raise the conversion to 90%?
e. If the reaction is carried out in a constant-pressure batch reactor in which pure A is fed to the
reactor, what length of time is necessary to achieve 40 % conversion?
f. Plot the rate of reaction and conversion as a function of PFR volume.
g. Critique the answers to this problem.

34

Solution

a.

Until the conversion (X) reaches 0.5, the reaction rate is independent of conversion
and the reactor volumes will be identical.

b.

FA 0 X C A 0 v 0 X

rA
rA
V
0.09m 3
13
X

10
C A 0 v 0 200 mol / m 3 5m 3 / s 3 108 m 3 s / mol
rA
35

c.

3
FA 0 X C A 0 v 0 X
mol
m3
8 m s
0.5 1.5 1011 m 3
V1

200 
5 3 10 
rA
rA
s
s
mol

8 m3 s
dX

V2 FA 0
v 0C A 0 10 
0.5 r
mol
A

0.7

0.7

0.5 (10X 2)dX

0.7
m3
mol 8 m 3 s
(5X 2 2X) 8 1010 m 3
5 200  3 10 
0.5
s
mol
m

V V1 V2 1.5 1011  8 1010 m 3 2.3 1011 m 3

36

d.

F
VCSTR A 0
rA

X 0.9

CA0 v0

rA

(0.9 0.7)

( 0 .9 0 .7 )
X 0.9

3
mol
m3
8 m s
200  3 5 [3 10 (0.9 0.5)](0.9 0.7) 10 
1.4 1011 m 3
m
s
mol

37

e.

dN A
rA V
dt
V V0 (1 X)

CA0

N A0
V0

N A N A 0 (1 X)

rA V N A 0

rA V0 (1 X) N A 0
t

dt C A 0

dX
dt

dX
dt

dX
rA (1 X)

1
C A 0 ln(1 X)
rA

m3 s
mol
t 3 10 
200  3 ln(1 0.4) 2.02 1010 s
mol
m
8

38

f.

Notice how the relation is linear

until the conversion exceeds 50%.
g.
The rate of reaction for this problem is extremely small, and the flow rate is quite large.
To obtain the desired conversion, it would require a reactor of geological proportions (a
CSTR or PFR approximately the size of the Los Angeles Basin), or as we saw in the case
of the batch reactor, a very long time.

39

Closure

In this section, we have shown that if you are given the rate of reaction as a
function of conversion, i.e., -rA=f(X), you will be able to size CSTRs and PFRs
and arrange the order of a given set of reactors to determine the best overall
conversion. After completing this section, the student should be able to
a. define the parameter conversion and rewrite the mole balances in terms of
conversion
b. show that by expressing rA as a function of conversion X a number of
reactors and reaction systems can be sized or a conversion calculated from
a given reactor size.
c. arrange reactors in series to achieve the maximum conversion for a given
Levenspiel plot.

40