Reaction Engineering

CHEG 443
s5

Ch.2. Conversion and Reactor Sizing

1
Review

 Define the residence time or “Space Time”

 What is reaction conversion,
 Derive the design equations in terms of for the most
common types of reactors

2
Reactor Sizing
It is normal to calculate the size needed for a certain
reaction / process to achieve certain conversion

The size is an important factor and it implies $

The bigger the reactor gets, the higher the price

3
Levenspiel Plots
•Given as a function of conversion, ,
one can size any type of reactor by
constructing a Levenspiel plot.

•Here, we plot either or as a function Levenspiel Plot

of .

•Then, the plots can be used to solve 𝐹 𝐴𝑜

for the required volume of CSTR and −𝑟𝐴
PFR reactors, or the required batch
time in a constant-batch reactor.

𝑋
4
Reactor Sizing (Levenspiel Plot)
Show how Levenspiel (reciprocal rate) plots can be used to solve for the required
volume of CSTR and PFR reactors, or the required batch time in a constant-
volume batch reactor.

CSTR
Material Balance: 0=𝐹 𝐴𝑜 − 𝐹 𝐴 +𝑟 𝐴 𝑉 Levenspiel Plot

In terms of , sub.
0=𝐹 𝐴𝑜 𝑋 +𝑟 𝐴 𝑉 𝐹 𝐴𝑜
𝑉=
𝐹 𝐴𝑜 𝑋 −𝑟𝐴
−𝑟 𝐴

𝑉=
𝐹 𝐴𝑜
−𝑟𝐴 ( ) 𝑋 Area = Volume of CSTR

Experimental data
Function of , i.e.
𝑋
Note that the data of does not depends on the reactor!
5
Reactor Sizing (Levenspiel Plot)
Show how Levenspiel (reciprocal rate) plots can be used to solve for the required
volume of CSTR and PFR reactors, or the required batch time in a constant-batch
reactor.

PFR
𝑑𝐹𝐴 Levenspiel Plot
Material Balance: =𝑟 𝐴
𝑑𝑉
In terms of , sub.
𝑑𝑋 𝐹 𝐴𝑜
− 𝐹 𝐴𝑜 =𝑟 𝐴
𝑑𝑉 −𝑟𝐴
𝑋
𝑑𝑋
𝑉 = 𝐹 𝐴𝑜 ∫
0 −𝑟 𝐴
Area = Volume of PFR

( )
𝑋
𝑉 =∫
𝐹 𝐴𝑜
−𝑟 𝐴
𝑑𝑋 𝑋
0

6
Reactor Sizing (Levenspiel Plot)
Show how Levenspiel (reciprocal rate) plots can be used to solve for the required
volume of CSTR and PFR reactors, or the required batch time in a constant-batch
reactor.

Constant-Volume Batch Reactor

𝑑𝑁𝐴 Levenspiel Plot
Material Balance: =𝑟 𝐴 𝑉
𝑑𝑡
In terms of , sub.
𝑑𝑋 𝐶 𝐴𝑜
− 𝑁 𝐴𝑜 =𝑟 𝐴 𝑉
𝑑𝑡 −𝑟𝐴
𝑋
𝑁 𝐴𝑜 𝑑𝑋
𝑡= ∫
𝑉 0 −𝑟 𝐴
Area = Time of Batch

( )
𝑋
𝐶 𝐴𝑜
𝑡 =∫
−𝑟 𝐴
𝑑𝑋 𝑋
0

7
Reactors in Series

Now let’s suppose we have different existing reactors in the plant

We could arrange them to maximize our production/conversion
What order are the best orders?
• PFR  PFR
• CSTR  CSTR
• CSTR  PFR
• PFR  CSTR

The fun starts here!

8
CSTR in Series
Example
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?
0.0 0.1 0.2 0.4 0.6 0.7 0.8
0.89 1.09 1.33 2.05 3.54 5.06 8.0

𝐹 𝐴𝑜 𝐹 𝐴𝑜
𝑉=
−𝑟𝐴(
𝐹 𝐴𝑜
) 𝑋

𝑋=40 % 𝑉 1= ( 2.05 ) ( 0.4 )= 0.82 𝑚3 𝑋=80 %

𝑉 2= ( 8.0 ) ( 0.4 ) =3.2 𝑚3
𝑋=80 % 𝑉 𝑡𝑜𝑡𝑎𝑙= 𝑉 1 +𝑉 2= 4.02 𝑚3 𝑉 = ( 8.0 ) ( 0.8 ) = 6.4 𝑚

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 CSTR in Series
𝐹 𝐴𝑜
𝐹 𝐴𝑜

𝑋=40%
𝑋=80 %
𝑋=80 %
𝑉 = ( 8.0 ) ( 0.8 )= 6.4 𝑚3 𝑉 𝑡𝑜𝑡𝑎𝑙= 𝑉 1 +𝑉 2= 4.02 𝑚3

• Note that
– For 1 CSTR to get 80% Conversion  6.4 m3
– For the new arrangement (2 CSTR @ 40% and
80%) We need  4.02 m3 which is 30% less
 Is it worth ?!

10
CSTR in Series
consider a number of CSTRs in series
We see that we approach the
PFR reactor volume for a large
number of CSTRs in series

Similar to trapezoidal rule

(rectangles in this case)

𝐹 𝐴𝑜
−𝑟𝐴

𝑋
11
CSTR in Series

For CSTRs connected in series we

have:
𝐹 𝐴𝑜
𝑉 𝑖= ( 𝑋 𝑖 − 𝑋 𝑖− 1)
( −𝑟 𝐴 )𝑖

As the number of CSTRs increases:

 The volume of the CSTRs becomes
equivalent to that of PFR to achieve
the same conversion

PFR can be modeled as an infinite

number of CSTRs connected in series

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PFR in Series
• In the case of PFR, this is not that “amazing”
• Using multiple PFRs in series to achieve a desired conversion
results in the same volume as using a single PFR!
• Why?Mathematically:

𝑋=30 % 𝑋=60 % 𝑋=80 % 𝑋=80 %

( ) ( ) ( ) ( )
𝑋 =0.3 𝑋 =0.6 𝑋 =0.8 𝑋 =0.8
𝐹 𝐴𝑜 𝐹 𝐴𝑜 𝐹 𝐴𝑜 𝐹 𝐴𝑜
𝑉= ∫ −𝑟 𝐴
𝑑𝑋 + ∫
−𝑟
𝑑𝑋 + ∫
−𝑟
𝑑𝑋 𝑉= ∫ 𝑑𝑋
𝑋 =0 𝑋 =0 .3 𝐴 𝑋 =0 .6 𝐴
𝑋 =0 −𝑟 𝐴

( )
𝑋 =0.8
𝐹 𝐴𝑜
¿ ∫ −𝑟𝐴
𝑑𝑋 𝐹 𝐴𝑜 𝐹 𝐴𝑜
𝑋=0
−𝑟𝐴 −𝑟𝐴

𝑋 𝑋
13
 PFR in Series
Example Calculate the reactor volume for the plug flow reactor for the
final conversion is 80%. The entering molar flow is 0.4 mol/s.
0.0 0.1 0.2 0.4 0.6 0.7 0.8

0.89 1.08 1.33 2.05 3.54 5.06 8.0

( )
𝑋
𝐹 𝐴𝑜
𝑉 =∫ 𝑑𝑋 Trapezoidal rule
0 −𝑟 𝐴

0 0.89
0.1 1.08 0.1 0.985 0.0985
b2 0.2 1.33 0.1 1.205 0.1205
0.4 2.05 0.2 1.69 0.338
h
0.6 3.54 0.2 2.795 0.559
0.7 5.06 0.1 4.3 0.430
b1
Area of a trapezoid 0.8 8.0 0.1 6.53 0.653

1
A
2
b1  b2   h
∑ ¿𝟐.𝟐𝑚 3
14
Best vs. worst Arrangements
Exercise
Let’s design the reactor sizing that achieve a conversion of for the
following two cases:

𝐹 𝐴𝑜 Min. Volume Max. Volume

𝐹 𝐴𝑜
−𝑟𝐴 −𝑟𝐴

𝑋 𝑋 15
Combinations of CSTRs and PRFs in
Series
CSTR and PFR can be connected in series
The arrangement of the reactors in this case is of high
importance
For the case of two CSTRs and one PRF:

Option 1: CSTR-CSTR-PRF

Option 2: CSTR-PRF-CSTR

Option 3: PFR-CSTR-CSTR

16
Combinations of CSTRs and PRFs in
Series
Q. Does the order of two isothermal reactors (a plug flow reactor and a
continuous stirred tank reactor) in series affect the final conversion?

A. Yes, in general. For example: conversion higher for 2nd-order reaction if the
PFR is first.
But order does not matter for a first-order reaction of the form under
isothermal conditions. (Can you prove?)
𝐴 𝐵 𝑟 𝐴=− 𝑘 𝐶 𝐴
→

𝑪𝑨𝒐 𝑪𝑨𝒐 𝑪𝑨𝟏

𝑪𝑨𝟏 𝑪𝑨𝟐 𝑪𝑨𝟐

17
 Combinations of CSTRs and PRFs in Series
𝑪𝑨𝒐 𝑨
→
𝑩 𝒓 𝑨 =− 𝒌 𝑪 𝑨
𝑪𝑨𝒐 𝑪𝑨𝟏
𝑪𝑨𝟏 𝑪𝑨𝟐
CSTR PFR 𝑪𝑨𝟐
0= 𝐹 𝐴𝑜 − 𝐹 𝐴 1 +𝑟 𝐴 𝑉 𝐶𝑆𝑇𝑅 𝑑𝐹𝐴
0=𝑣𝐶 𝐴𝑜 −𝑣𝐶 𝐴 1 −𝑘 𝐶 𝐴 1 𝑉 𝐶𝑆𝑇𝑅 =𝑟 𝐴
𝑑𝑉
𝑣𝐶 𝐴𝑜 𝐶 𝐴𝑜 𝐶
𝐶 𝐴 1= =
𝐴1
𝑑𝐶𝐴
𝑣 +𝑘 𝑉 𝐶𝑆𝑇𝑅 1+𝑘 τ 𝐶𝑆𝑇𝑅 ∫ 𝐶 =−𝑘 τ 𝑃  𝐶 𝐴 1=𝐶 𝐴𝑜 𝑒− 𝑘 τ 𝑃

𝐴
PFR 𝐶𝐴0

𝑑𝐹𝐴
=𝑟 𝐴 CSTR
𝑑𝑉 0= 𝐹 𝐴 1 − 𝐹 𝐴 2+𝑟 𝐴 𝑉 𝐶𝑆𝑇𝑅
𝑑𝐶𝐴
𝑣 =− 𝑘 𝐶 𝐴 0=𝑣𝐶 𝐴 1 −𝑣𝐶 𝐴 2 −𝑘 𝐶 𝐴 2 𝑉 𝐶𝑆𝑇𝑅
𝑑𝑉 𝑣𝐶 𝐴 1 𝐶 𝐴1
𝐶𝐴2
𝑑𝐶𝐴 𝐶 𝐴2= =
𝑣+𝑘 𝑉 𝐶𝑆𝑇𝑅 1+𝑘 τ 𝐶𝑆𝑇𝑅
∫ 𝐶 =−𝑘 τ 𝑃  𝐶 𝐴2 =𝐶 𝐴1 𝑒−𝑘τ 𝑃

𝐶𝐴1
𝐴
𝐶 𝐴𝑜 −𝑘 τ 𝑃 𝐶𝐴𝑜 − 𝑘τ
𝐶 𝐴2=  𝑒 𝐶 𝐴2= 𝑒 𝑃

1+𝑘 τ 𝐶𝑆𝑇𝑅 1+𝑘 τ 𝐶𝑆𝑇𝑅

18
 Combinations of CSTRs and PRFs in
Series
Prove that conversion is higher for 2nd-order reaction if the PFR is first.

A 100-L CSTR is used for a reaction that follow a 2nd-order rate law:
where is the conversion and is the inlet concentration of the limiting
reactant. A conversion of 75% is achieved in the CSTR. A PFR of the
same volume is added in series to the CSTR to increase the
conversion. Should it be added before of after the CSTR? What is the
final conversion?
CSTR
𝐹 𝐴𝑜 𝑋 𝐹 𝐴𝑜 0.75 𝐹 𝐴𝑜 0.75 𝐹 𝐴𝑜
𝐶 𝐴𝑜 𝑉= ¿ 2¿ 2
−𝑟 𝐴 2
𝑘 𝐶 𝐴𝑜 ( 1− 𝑋 ) 𝑘 𝐶 2𝐴𝑜 ( 1− 0.75 )
𝑉 =100 𝐿 𝑉 =100 𝐿 𝑉𝑘 𝐶 2𝐴𝑜 0.75
 ¿ ¿ 12
𝑋=75 % 𝐹 𝐴𝑜 ( 1 − 0.75 ) 2

19
 Combinations of CSTRs and PRFs in
Series 𝑉
=∫
𝑑𝑋
𝑋2

𝐹 𝐴𝑜 0 .75
−𝑟𝐴
1 PFR downstream 𝑉𝑘 𝐶 2𝐴𝑜
𝐹 𝐴𝑜 
𝐶 𝐴𝑜 𝐹 𝐴𝑜
𝑉 =100 𝐿 1 1
𝑉 =100 𝐿 12= −
( 1 − 𝑋 2 ) ( 1 −0.75 )  𝑋 2=93.8 %
𝑋=75 %
𝑋1 𝑋1
2 PFR upstream 𝑉
=∫
𝑑𝑋
=∫
𝑑𝑋
𝐹 𝐴𝑜 0
− 𝑟 𝐴 0 𝑘 𝐶 2𝐴𝑜 (1 − 𝑋 )2
𝑋1
𝑉𝑘 𝐶 2𝐴𝑜 𝑑𝑋
𝐹 𝐴𝑜  =∫
𝐶 𝐴𝑜 𝑉 =100 𝐿 𝐹 𝐴𝑜 2
𝑋1 0 (1 − 𝑋 )
1
12= −1
( 1 − 𝑋 1)  𝑋 1=92.3 %
CSTR
𝑉 =100 𝐿 𝑉
=
𝑋 2− 𝑋 1
𝐹 𝐴𝑜 𝑘 𝐶 2𝐴𝑜 ( 1 − 𝑋 )2
𝑋2
𝑉𝑘 𝐶 2𝐴𝑜 𝑋 2 − 0.923
12=
𝐹 𝐴𝑜
= 2  𝑋 2=95.1 %
( 1− 𝑋 2 ) 20
Combinations of CSTRs and PRFs in
Series
System A System B
Exercise
Which is More Efficient? or
1. Which system is more efficient with
the intermediate conversion of (0.3)?

System B

2. Which system is most efficient with

the intermediate conversion of
(0.65)?
System A

3. Which system makes the best use of

the reactor volume (i.e., least “wasted”
volume)?
System B with intermediate
conversion of 0.3 21
Space Time vs. Space Velocity
Space time : The time necessary to process one reactor
volume of fluid based on the entrance
conditions
𝑽
𝝉=
𝒗

Space velocity : is the reciprocal of the space time

𝟏 𝒗
𝑺𝑽 = =
𝝉 𝑽

22
Class exercise (Problem 2-7)

23
Class exercise (Problem 2-7)

24
Class exercise (Problem 2-7)

25
26
Class exercise (Problem 2-7)

27
Class exercise (Problem 2-7)

28
Class exercise (Problem 2-7)

29
Class exercise (Problem 2-7)

30
Class exercise (Problem 2-7)

31
Class exercise (Problem 2-7)

0.08

0.08

32
Class exercise (Problem 2-7)

33
Class exercise (Problem 2-7)

34
 -rA VPFR
FA,0 X 1/(-rA) Area pieces
(mol/L.min) (L)
300 0 1 1 0 0
mol/min 0.2 1.67 0.5988024 0.15988024 47.9640719
0.4 5 0.2 0.07988024 71.9281437
0.45 5 0.2 0.01 74.9281437
0.5 5 0.2 0.01 77.9281437
0.6 5 0.2 0.02 83.9281437
0.8 1.25 0.8 0.1 113.928144
0.9 0.91 1.0989011 0.09494505 142.41166

35
 -rA VPFR
FA,0 X 1/(-rA) Area pieces
(mol/L.min) (L)
300 0 1 1 0 0
mol/min 0.2 1.67 0.5988024 0.15988024 47.9640719
0.4 5 0.2 0.07988024 71.9281437
0.45 5 0.2 0.01 74.9281437
0.5 5 0.2 0.01 77.9281437
0.6 5 0.2 0.02 83.9281437
0.8 1.25 0.8 0.1 113.928144
0.9 0.91 1.0989011 0.09494505 142.41166

-rA
The graph X(V) can be built by using the experimental data X(–r A) given in the statement of the problem and calculating
the several VPFR graphically by using the graph -1/rA(X), as we did in point (a) only for X=0.4. We will stop when volume
reaches 100 dm3.

The graph -rA(V) reports the rate at the exit of the PFR, and it can be built by using the values of X in the X(V) graph,
and obtaining –rA from the graph -1/rA(X). –rA can be finally drawn versus the V read in the X(V) graph.

36