Lecture #3

Chemical Reaction Engineering

Youn-Woo Lee
School of Chemical and Biological Engineering
Seoul National University
155-741, 599 Gwanangro, Gwanak-gu, Seoul, Korea  ywlee@snu.ac.kr  http://sfpl.snu.ac.kr
 第2章
Conversion
and Reactor Sizing

Reaction Engineering 1

反應工學 I

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개요. 제1장에서는 반응이 일어나는 영역(반응기)에서 일반 몰수지식
(GMBE)을 유도하였고 이를 4가지 이상적인 반응기에 적용하여 각 반응기에 대
하여 설계방정식을 유도하였다. 제2장에서는 어떻게 이런 반응기들의 크기를 구
하고 개념적으로 어떻게 배열하는지 보여줄 것이다. 이번 단원에서는
 전화율(X)을 정의하고,
 4종류의 이상적인 반응기의 설계방정식들을 전화율 X의 항으로 다시 쓰며,
 일단 반응속도와 전화율 사이의 관계가 주어진 경우(즉, -rA=f(x))에 Levenspiel
Plot을 그려보고,
 Levenspiel plot으로 부터 반응기의 크기를 구해보고,
 어떻게 CSTR과 PFR의 크기를 비교하는지 보여주고,
 어떻게 반응기들을 직렬로 최적 배열하는지 보여 줄 것이다.

더욱이, 반응속도와 전화율 사이의 관계가 주어진 경우에, CSTR과 PFR의 크기를
구할 수 있고 직렬로 배열된 반응기들의 총괄전화율과 각각의 반응기 부피들을
계산할 수 있을 것이다.
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Follow the Reaction Design Algorithm

Follow the Yellow Brick Road

Isothermal Reaction
Design Algorithm
 Objectives

After completing Chapter 2, reader will be able to:

편리한 전화율 사용!
왜 전화율을
사용하려고 하는가?
X=0.5일 때 반응기크기?

 Define conversion. X=0.9일 때 반응시간은?

 Write the mole balances in terms of conversion

for a batch reactor, CSTR, PFR, and PBR.
 Size reactors either alone or in series once given
the molar flow rate of A, and the rate of reaction,
- rA, as a function of conversion, X.

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 2.1 Definition of Conversion
Consider the general equation

aA  bB  cC  dD (2-1)
Choose A as our basis of calculation
(The basis of calculation is most always the limiting reactant )

b c d
A B  C D (2-2)
a a a
Questions
- How can we quantify how far a reaction has progressed ?
- How many moles of C are formed for every mole A consumed ?

The convenient way to answer these question is to define conversion.

mole of A reacted
X
mole of A fed
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 2.2 Batch Design Equations
In most batch reactors,
the longer a reactant is in the reactor, the more reactant is converted to
product the reactant is exhausted. Consequently, in batch system, the
conversion X is a function of reaction time the reactants spend in the
reactor.

If NA0 is the number of moles of A initially in the reactor, then the total
number of moles of A that have reached after a time t is [NA0 X]
 mole of A mole of A  moles of A reacted 
consumed    fed    mole of A fed 
     
 mole of A
(2-3)
consumed   N A0   X 
 

The number of moles of A that remain in the reactor after a time t, NA, can be
express in terms of NA0 and X:
moles of A  moles of A   moles of A that 
 in reactor    initially fed to    have been consumed  (2-4)
     
 at time t  reactor at t  0 by chemical reaction
N A   N A0   N A0 X 
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 The mole balance on species A for a batch system
2.2 Batch Design Equations
dN A
 rAV (1-5)
dt
The number of moles of A in the reactor after a conversion X

N A  N A0  N A0 X  N A0 (1  X ) (2-4)

In term of conversion by differentiating equation

dN A dX
 0  N A0
dt dt
The design equation for a batch reactor in differential form is

dX
The differential form
for a batch reactor
N A0  rAV (2-5)
dt
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 2.2 Batch Design Equations

The design equation for a batch reactor in differential form

dN A
 rAV (2-5)
dt

Write the mole balances

in terms of conversion

회분식반응기의
설계방정식 dX
N A0  rAV (2-6)
dt

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 2.2 Batch Design Equations

The design equation for a batch reactor in differential form

dN A
 rAV
dt
Constant volume, V=V0

1 dN A 1 dN A d  N A / V0  dC A
    rA
V dt V0 dt dt dt

dC A
rA  (2-7)
dt
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 2.2 Batch Design Equations

The design equation for a batch reactor in differential form

dN A dX
 rAV (2-5) N A0  rAV (2-6)
dt dt

The differential forms of the batch reactor mole balances, Eqs

(2-5) and (2-6), are often used
in the interpretation of reaction rate data (Chapter 7)
and for reactors with heat effects (Chapter 11-13), respectively.

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 2.2 Batch Design Equations

 Batch reactors are frequently used in industry for

both gas-phase and liquid-phase reactions.

 The lab bomb calorimeter reactor is widely used for

obtaining reaction rate data.

 Liquid-phase reactions are frequently carried out in

batch reactors when small-scale production is desired
or operating difficulties rule out the use of continuous
flow systems.

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For constant-volume batch reactor, V=V0

1 dN A d N A / V0  dC A
    rA CA 
NA
V0 dt dt dt V0

For the most common batch reactors where volume is not

predetermined function of time, the time necessary to achieve a
conversion X is

X t  dX
The integral form
t  N A0  (2-7)
for a batch reactor 0  rAV

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 2.3 Design Equations for Flow Reactors

If FA0 is the molar flow rate of species A fed to a system at

steady state, the molar rate at which species A is reacting
within the entire system will be FA0X.

FA0  X   moles of A fed moles of A reacted


time moles of A fed

FA0  X   moles of A reacted

time

FA0 FA

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 2.3 Design Equations for Flow Reactors

The molar flow rate

 molar flow rate  molar rate at which   molar flow rate 

 at which A is    consumed    at which A 
     
 fed to the system  within the system  leaves the system
FA0   FA0 X   FA 

Rearranging gives

FA  FA0 1  X  (2-8)

FA0 FA
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2.3.1 CSTR or Backmix Reactor
FA0
- The design equation for a CSTR
FA0  FA FA
V (2-11)
 rA A
b
a
B 
c
a
d
C D
a

- conversion of flow system

FA0  FA  FA0 X (2-12)

- Combining (2-12) with (2-11)

FA0 X
V design equation
 rA exit (2-13)
for a CSTR

Equation to determine the CSTR volume necessary to achieve a specified

conversion X. Since the exit composition from the reactor is identical to the
composition inside the reactor, the rate of reaction is evaluated at the exit condition.
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2.3.2 Tubular Flow Reactor (PFR)
FA0 FA
- General mole balance equation
dF A
   rA (1-12)
dV
- conversion of flow system

FA  FA0  FA0 X (2-12)

- The differential form of the design equation

dX
FA0   rA (2-15)
dV
- Volume to achieve a specified conversion X

X dX
V  FA0  (2-16)
0  rA
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2.3.3 Packed-Bed Reactor (PBR)
FA0 FA

- General mole balance equation

dF A
 r A' (1-15)
dW
- conversion of flow system
FA  FA0  FA0 X

- The differential form of the design equation with P 0

dX (2-17)
FA0   rA'
dW
-The catalyst weight W to achieve a specified conversion X with P=0

X dX
W  FA0  (2-18)
0  rA'
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 Summary of Design Equation
X t  dX
t  N A0  Design equation
NA0 0  rAV for a batch reactor

FA0 FA0 X
V Design equation
 rA exit for a CSTR
FA

X dX
FA0 FA V  FA0  Design equation
0  rA for a PFR

X dX Design equation
FA0 FA W  FA0  for a PBR
0  rA'
공통점?
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 Summary of Design Equation
Reaction time
X t  dX
t  N A0  ~ NA0
0  rAV
~X
~ 1/rAV
FA0 FA0 X
V
 rA exit
FA
Reactor volume
X dX (Catalyst weight)
FA0 FA V  FA0 
0  rA
~ FA0
~X
X dX
FA0 FA W  FA0  ~ 1/rA’
0  rA'
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Follow the Reaction Design Algorithm

Follow the Yellow Brick Road

Isothermal Reaction
Design Algorithm
 2.4 Applications of the design equation
for continuous-flow reactor
The rate of disappear of A, -rA, is almost always a function of the
concentrations of the various species present. When a single reaction
is occurring, each of the concentrations can be expressed as a
function of the conversion x; consequently, -rA, can be expressed as
a function of X.

X dX
FA0 FA V  FA0 
0  rA

For a first-order reaction :  r A  kC A  kC A 0 1  X 

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How to use the raw data of chemical reaction rate?

Consider the isothermal gas-phase isomerization

A B
The laboratory measurements give
the chemical reaction rate as a function of conversion.
(at T=500K, 8.2atm)
0.5
raw data
Greatest rate
0.4

-rA (mol/m3s)
0.3
Smallest rate
0.2

0.1

0.0
0.0 0.2 0.4 0.6 0.8 1.0

Conversion, X
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 Levenspiel Plot

- rate data convert reciprocal rates, 1/- rA

- plot of 1/- rA as a function of X

30 
25
Small rate

1/-rA (m3s/mol)
20

15
Greatest rate
10

0
0.0 0.2 0.4 0.6 0.8 1.0

Conversion, X

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 Levenspiel Plot

- plot of [FA/- rA] as a function of [X]

12

10
Table 2-3
8

FA/-rA (m )
3
6

0
0.0 0.2 0.4 0.6 0.8 1.0

Conversion

Fig. 2-2 Seoul National University

 Reactor Size
• Given –rA as a function of conversion.
• Constructing a Levenspiel plot.
FA0 1
• Here we plot either  rA
or as a function of X.
 rA

F A0
For vs. X, the volume of a CSTR and the volume of a PFR
 rA
can be represented as the shaded areas in the Levenspiel plots.
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 Example 2-1 Sizing a CSTR
The reaction described by the data in Table 2-3 (below)
A B
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 Table 2-3, or Fig. 2-1, calculate the volume
necessary to achieve 80% conversion in a CSTR.
(b) Shade the area in Fig. 2-2 that would give the CSTR volume
necessary to achieve 80% conversion.

Table 2-3
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 Example 2-1 Sizing a CSTR
Calculate the volume necessary to achieve 80% conversion in a CSTR
FA0=0.4 mol/s

FA 0 X mol m3  s
(a) V   ( 0 .4 )(0.8)(20 )  6.4m 3  6400l
 rA exit s mol
3.6m

FA

(b) 1.5m
12

10

FA/-rA (m )
3
6
VCSTR
4 = 8 x 0.8
EXIT 2
= 6.4 m3
In CSTR, C, T, P, and X of the effluent
stream are identical to that of the fluid 0
0.0 0.2 0.4 0.6 0.8 1.0
within the reactor, because perfect mixing is
Conversion
assumed. Seoul National University
 Example 2-1 Sizing a CSTR
The volume necessary to achieve 80% conversion in a CSTR is 6.4m3.

FA0=0.4 mol/s FA0=0.4 mol/s

3.6m
2.01m

FA FA

1.5m 2.01m

It’s a large CSTR, but this is a gas-phase reaction, and CSTRs are
normally not used for gas-phase reaction, and CSTRs are used
primarily for liquid-phase reactions.
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 Example 2-2 Sizing a PFR
Calculate the volume necessary to achieve 80% conversion in a PFR.
We shall use the five point quadrature formula (A-23) in Appendix A.4.
FA0  0 . 4 mol / s

X  0.8
FA0 dX
V 
0  rA
X  FA0 4 FA0 2 FA0 4 FA0 FA 0 
      
3   rA ( X  0)  rA ( X  0.2)  rA ( X  0.4)  rA ( X  0.6)  rA ( X  0.8) 
 0.2   0.2 
0.89  4(1.33)  2(2.05)  4(3.54)  (8.00) m  
3 3 3
 (32.47 m )  2.165m
 3   3 

V = 2.165 m3
= 2165 dm3

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 Example 2-2 Sizing a PFR
Calculate the volume necessary to achieve 80% conversion in a PFR

Graphic Method 12

X  0.8 10 FA0 FA
FA0
V 0  rA
dX
8

FA0/-rA (m )
3
= area under the curve 6
between X=0 and X=0.8
4

= 2165 dm3 (2.165 m3)

2
VPFR=2.165 m3
(see appropriate shaded 0
area in Fig. E2-3.1) 0.0 0.2 0.4 0.6 0.8 1.0

Conversion
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Example 2-2 Sizing a PFR
Sketch the profile of –rA and X down the length of the reactor.
A0 F A F
Solution
As we proceed down the reactor and more and more of reactant is
consumed, the concentration of reactant decreases, as does the
rate of disappearance of A. However, the conversion increases as
more and more reactant is converted to product.
Simpson’s rule (Appendix A.4 Eq. A-21)
X=0.2, X=0.1
X  0.2 X  FA 0 4 FA0 FA 0 

dX
V  FA0     
0  rA 3   rA ( X  0)  rA ( X  0.1)  rA ( X  0.2) 
 0.1  3 0.1
  0.89  4(1.08)  1.33 m  (6.54m 3 )  0.218m 3  218dm 3
 3  3
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Example 2-2 Sizing a PFR
Sketch the profile of –rA and X down the length of the reactor.
FA0 FA
Solution
Simpson’s rule (Appendix A.4 Eq. A-21)
X=0.4, X=0.2

X  0.4 X  FA 0 4 FA 0 FA 0 

dX
V  FA 0     
0  rA 3   rA ( X  0)  rA ( X  0.2)  rA ( X  0.4) 
 0.2  3 0.2
 0.89  4(1.33)  2.05 m  (8.26m 3 )  0.551m 3  551dm 3
 3  3

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 Example 2-2 Sizing a PFR
Sketch the profile of –rA and X down the length of the reactor.
FA0 FA
Solution
Simpson’s rule (Appendix A.4 Eq. A-21)
X=0.6, X=0.3

X  0.6 X  FA 0 4 FA 0 FA 0 

dX
V  FA 0     
0  rA 3   rA ( X  0)  rA ( X  0.3)  rA ( X  0.6) 
 0.3  3 0.3
 0.89  4(1.625)  3.54 m  (10.93m 3 )  1.093m 3  1093dm 3
 3  3

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 Example 2-2 Sizing a PFR
Sketch the profile of –rA and X down the length of the reactor.
FA0 FA
Solution
Simpson’s rule (Appendix A.4 Eq. A-21)
X=0.8, X=0.4

X  0.8 X  FA 0 4 FA 0 FA0 

dX
V  FA 0     
0  rA 3   rA ( X  0)  rA ( X  0.4)  rA ( X  0.8) 
 0.4  3 0.4
 0.89  4(2.05)  8.0 m  (17.09m 3 )  2.279m 3  2279dm 3
 3  3

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Example 2-2 Sizing a PFR

Sketch the profile of –rA and X down the length of the reactor.

X 0 0.2 0.4 0.6 0.8

-rA (mol/m3·s) 0.45 0.30 0.195 0.113 0.05

V (dm3) 0 218 551 1093 2279

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Example 2-2 Sizing a PFR

Sketch the profile of –rA and X down the length of the reactor.
V=1093 L V=2165 L
X=0.6 X=0.8

1.0

V=551 L
0.8
X=0.4

0.6

X 0.4
V=218 L
X=0.2 0.2

0.0

0 500 1000 1500 2000 2500

3
V (dm )

반응기를 따라 내려감에 따라서 전화율은 증가한다.

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Example 2-2 Sizing a PFR

Sketch the profile of –rA and X down the length of the reactor.
0.5

0.4

0.3
-rA
0.2
(mol/m3s)
0.1

0.0
0.0 0.5
0.2 1.0
0.4 1.5
0.6 2.0
0.8 2.5
1.0

X 3)
V (m
반응기를 따라 내려감에 따라서 전화율은 증가하는 한편 반응속도 rA는 감소한다.
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 Example 2-3 Comparing CSTR and PFR Sizes
Calculate the volume necessary to achieve 80% conversion
in a CSTR and a PFR
FA0

FA0  0 .4 mol / s FA0 FA

FA
12

V=2.2 m3 V=6.4 m3
10

8
FA/-rA (m )
3

6
For isothermal reaction of
greater than zero order, the
4
PFR will always require a
2 smaller volume than the CSTR
0
to achieve.
0.0 0.2 0.4 0.6 0.8 1.0

Conversion
0차보다 더 큰 차수의 등온반응의 경우에, 동일한 전화율과 동일한 반응조건들(온도, 유량 등)에 대해서
CSTR 부피가 PFR 부피보다 일반적으로 더 크다. Seoul National University
 Example 2-3 Comparing CSTR and PFR Sizes

V=2.2 dm3
The isothermal CSTR volume is
FA0 FA usually greater than the PFR
volume is that the CSTR is
0.5 always operating at the lowest
reaction rate (-rA=0.05).
0.4
The PFR start at the higher rate
at the entrance and gradually
0.3 decreases to the exit rate,
thereby requiring less volume
-rA because the volume is inversely
0.2 proportional to the rate.
FA0

0.1

0.0 FA
0.0 0.2 0.4 0.6 0.8 1.0
V=6.4 dm3
X Seoul National University
 Lecture #4

Chemical Reaction Engineering

Youn-Woo Lee
School of Chemical and Biological Engineering
Seoul National University
155-741, 599 Gwanangro, Gwanak-gu, Seoul, Korea  ywlee@snu.ac.kr  http://sfpl.snu.ac.kr
Follow the Reaction Design Algorithm

Follow the Yellow Brick Road

Isothermal Reaction
Design Algorithm
 2.5 Reactors in series
Define conversion
The conversion X defined as the “total number of moles” of A that
have reacted up to that point per mole of A fed to the “first” reactor.
(assumption : no side stream withdrawn and the feed stream enters
only the first reactor in the series)

total moles of A reacted up to point i

Xi 
moles of A fed to first reactor
PFR-CSTR-PFR in series
X1
X=0 FA1
FA0 V1
X2
FA2 X3
V2 FA3
V3

The relationships between conversion and molar flow rate

FA1 = FA0 - FA0 X1

FA2 = FA0 - FA0 X2
FA3 = FA0 - FA0 X3

total moles of A reacted up to point 2 similar definitions

where X2  exist for X1 and X3
moles of A fed to first reactor
 X1 dX
Reactor 1: V1  F A 0 
0  rA
Reactor 3 :
dX
X3
V3  FA0 
X=0
X1 X2  r
FA1 A
FA0 V1
X2
FA2 X3
V2 FA3
-rA
V3

Reactor 2 : -rA2 -rA

in  out  gen.  0
FA1  FA 2  rA 2V2  0

FA1 = FA0 - FA0 X1 -rA2 is evaluated

F ( X 2  X 1) at X2 for the CSTR
FA2 = FA0 - FA0 X2 V2  A0
In this series
 rA 2 arrangement
FA3 = FA0 - FA0 X3
 Four different schemes of reactors in series
FA0

Two CSTRs in series X1=0.4

FAe
X2=0.8

Two PFRs in series FA0

X1=0.4
FAe
X2=0.8

FA0 X1=0.5
a PFR and CSTR in series
FAe
X2=0.8

FA0
FAe
a CSTR and PFR in series X1=0.5 X2=0.8
 2.5.1 Two CSTRs in series
FA0

X1=0.4
FAe
X2=0.8
-rA1

-rA2

 1 
Reactor 1 V1  F A 0   X 1 (2-21)
  rA1 

FA0 ( X 2  X 1 )
Reactor 2 V2  (2-24)
 rA 2
 Example 2-5: Two CSTRs in Series
FA0
What is the volume of each of
X1=0.4
two CSTR reactors? FAe
X2=0.8

XA 0.0 0.1 0.2 0.4 0.6 0.7 0.8

[FAo/-rA] (m3) 0.89 1.09 1.33 2.05 3.54 5.06 8.0

Reactor 1

[FAo/-rA]x=0.4=2.05 m3
V1=([FAo/-rA]x=0.4)(X1-X0)=(2.05)(0.4-0)=0.82 m3

Reactor 2

[FAo/-rA]x=0.8=8.0 m3
V1=([FAo/-rA]x=0.8)(X2-X1)=(8.0)(0.8-0.4)=3.2 m3
 Example 2-4: Two CSTRs in Series

Therefore, V1 + V2 = 0.82 + 3.2 = 4.02 m3

What is the reactor volume to achieve 80% conversion in a

single CSTR?

[FAo/-rA]x=0.8 = 8.0 m3
V1 = ([FAo/-rA]x=0.8) (X1-X0)
= (8.0)(0.8-0) = 6.4 m3

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 (X=0.8)
Example 2-4 One CSTR vs Two CSTRs
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 (X=0.8)
12
FA0
10

X1=0.4
8
FAO/-rA 3.20 m3 FAe
3
[m ]
6
X2=0.8
4
V1 = 0.82 m3
0.82 m3
2
V1 = 3.2 m3
0 Vtotal = 4.02 m3
0.0 0.2 0.4 0.6 0.8 1.0

Conversion, X

FA0
12

10

8
FAO/-rA
6
X=0.8
[m3]
6.4 m3
4
FA
2

0 Vtotal = 6.4 m3
0.0 0.2 0.4 0.6 0.8 1.0

Conversion, X
 Approximating a PFR
Approximating a PFR with a number of small, equal-volume CSTRs of Vi in series

1 2 3 4 5

1 2 3 4 5

Then, compare the volume of all the CSTRs with the volume
of one plug-flow reactor for the same conversion, say 80%
We can model a PFR as a number of CSTRs in series

1 2 3 4 5 1 2 3 4 5

Modeling of a PFR with a large number of CSTRs in series.

V5
80

60 V4
FA0
 rA 40
V3
V2
20 V1

.35 .53 .65 .74 .8

X
As we make the volume of each CSTR smaller and increase the number of
CSTRs, the total volume of the CSTRs and the PFR will become identical!
 2.5.2 Two PFRs in series

FA0 FA1
X1=0.4 FAe
X2=0.8

X1 dX
Reactor 1 V1  F A 0 
0  rA

X2 dX
Reactor 2 V2  FA0 
X1  rA

X2 X1 X2
  
dX dX dX
V total  F A0  F A0  F A0
0  rA 0  rA X1  rA
 Two PFRs in Series

X1 X2 X2
0 X 0
FA0 FA0 FA0
VTotal= V1 + V2= dX + dX =
-rA 1
-rA -rA

12

10

8
FAO/-rA
3 6
[m ]
4

2
V2
V1
0
0.0 0.2 0.4 0.6 0.8 1.0

Conversion, X
 Sizing PFR in Series
What is the volume of each of two reactors?
Molar flow rate of A is 0.4 mol/s FA0
X1=0.4
FAe
X2=0.8
XA 0.0 0.1 0.2 0.4 0.6 0.7 0.8
[FAo/-rA] (m3) 0.89 1.09 1.33 2.05 3.54 5.06 8.0

Reactor 1
By applying Simpson’s rule in Appendix A.4 (Text page 60),

V1= ( 3 ) [0.89+4(1.33)+2.05] =0.551 m =551 dm

0.2 3 3

Reactor 2

By applying Simpson’s rule in Appendix A.4 (Text page 60),

V2= ( 3 ) [2.05+4(3.54)+8.0] =1.614 m =1614 dm

0.2 3 3

Therefore, V1 + V2=0.551 m3 + 1.614 m3=2.165 m3 < 4.02 m3 (Two CSTR in Series)

2.5.3 Combination of CSTR and PFR in Series

An industrial example of reactors in series

for using dimerization of propylene into isohexane

CH3
2 CH3-CH=CH2 CH3C=CH-CH2 -CH3

FA0
X=0 FA1
X1
FA2 FA3
V1 X2 X3

V2 V3
2.5.3 Combination of CSTR and PFR in Series
FA0
CSTR 1 X=0 FA1
X1
FA0 ( X 1  X 0 )
V1  FA2 FA3
 r A1 0 V1 X2 X3

CSTR 2 V2 V3
12

F A0 ( X 2  X 1 )
V2  10
 rA 2
8

PFR FAO/-rA
3 6
[m ]
X3 F A0
V3  
4
dX
X2  rA 2
V3
V2
V1
0
0.0 0.2 0.4 0.6 0.8 1.0

Conversion, X
Dimersol G unit (Two –CSTR and one PFR in series)
Institute Français du Petrόle Process

Dimerization propylene into isohexanes

Plug-flow reactor for Dimersol™ process

The finishing reactor (“the snake”) to comply with LPG specification

in the USA (less than 5% olefins)
 Description of Dimersol Process

The Dimersol process is used to dimerize light olefins such as

ethylene, propylene and butylene.

The process typically begins with the pretreatment of the propane

/propylene or butane/butene feed prior to entering the reactor
section of the process. Pretreatment can include the use of
molecular sieve dryers, sand filters, etc. to remove water and/or
H2S. Water in the feed stream can deactivate the catalysts used in
the Dimersol process.

After drying the feed is combined with a liquid nickel

carboxylate/ethyl aluminum dichloride (EADC) catalyst prior to
entering the first of a series of three reactors.
 Description of Dimersol Process

The first two are continuous stirred tank reactors and the third is a
plug-flow tubular reactor.

The reactor feed is converted to the process product, dimate,

primarily in the first reactor, and additional conversion is achieved
in the last two reactors. The final reactor effluent consists of
dimate product, unreacted C3/C4s, and liquid catalyst.

Immediately following the last reactor, the liquid catalyst is

removed from the reactor effluent by treating the reactor effluent
with caustic, subsequent water washing, and filtering to remove
solids.
 Description of Dimersol Process

Spent caustic residuals are typically reused or reclaimed on- or

off-site, and as a result, do not constitute solid wastes.

After filtering, the product stream enters a "Dimersol stabilizer," a

distillation unit that removes unreacted LPG from the dimate
product. In some cases, the product stream is also further treated
by drying.

LPG from the stabilizer overhead is typically sent to another unit

of the refinery for further processing. The dimate product from the
bottom of the stabilizer is sent to storage or product blending.
 LC 1252 catalyst

Application : C3 or C4 Olefins Dimerization (Dimersol®)

Type : nickel carboxylate/ethyl aluminum dichloride (EADC)
Shape : Liquid Catalyst

LC 1252 catalyst is used in the Dimersol process licensed by Axens.

High octane value motor gasoline is obtained from olefinic C3 cuts

from FCCs or steam crackers.

Oligomerization of C3 or C4 olefins produces, with high selectivity,

hexenes, heptenes and higher olefins up to dodecenes
 Dimersol G Process
25 plants, 3,000,000MT/year

C3H6 (l)  [C3H6]2 Ho298=-89.1 kJ/mol (-21.30 kcal/mol)

C3 67%
C3= 33%

LPG
Unreacted C3=

5% max.
T=57oC
propylene
P=17bar
in propane
X1=0.7 X2=0.9 (US LPG
X3=0.97 specification
as a fuel)

NaOH Dimersol stabilizer

NH3

Isohexane
bp=60oC
 Weak acid process for producing dinitrotoluene
EP 0 903 336 A2, AIR PRODUCTS 1998

Dinitrotoluene is an important intermediate in producing toluenediisocyanate based polyurethanes.

 TNT Production Plant
EP 0 903 336 A2, AIR PRODUCTS 1998

TNT plant in Hiroshima, Japan

 Isothermal vs. Adiabatic

12 2.5

10
Isothermal 2.0
Adiabatic
8
1.5
FAO/-rA FA0/-rA
3 6
[m ] 3
(m )
1.0
4

0.5
2

0 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

Conversion, X Conversion, X
Example 2-5: An Adiabatic Liquid-Phase Isomerization

Calculate the volume of Isomerization of butane

each of the three reactors
n-C4H10 i-C4H10
for an entering molar flow
rate n-butane of 50 kmol/hr.
X 0.0 0.2 0.4 0.6 0.65
-rA (kmol/m3-h) 39 53 59 38 25

FA0 FA1
X=0 FA2
X1=0.2
X2=0.6

V1 V2 FA3
rA1 X3=0.65
V3
rA3
Example 2-5
FAo = 50 kmol/h
X 0.0 0.2 0.4 0.6 0.65
-rA (kmol/m3-h) 39 53 59 38 25
[FAo/-rA](m3) 1.28 0.94 0.85 1.32 2.0
(a) CSTR 1 (X1=0.2)
F A0 ( X 1  X 0 ) F A0
V1   X 1  ( 0 . 94 m 3 )( 0 . 2 )  0 . 188 m 3
 r A1 0  r A1

(b) PFR (X2=0.6)

0 . 6
F A0  X  F A0 F A0 F 
V2   
0 .2 
  rA 

 dX  
3   r A X  0 . 2
 4
 rA X  0 .4
 A0
 rA

X  0 .6 

0 .2
 0 . 94  4 ( 0 . 85 )  1 . 32   0 . 38 m 3
3
(c) CSTR 2 (X3=0.65)
F A0
V3  ( X 3  X 2 )  ( 2 m 3 )( 0 . 65  0 . 6 )  0 . 1m 3
 rA3
Example 2-5

2.5

2.0

1.5
FA0/-rA
3
(m )
1.0
V3=0.1 m3

V1 =
0.5 V2 =0.38 m3
0.188 m3
0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

Conversion, X
 Comparing CSTR and PFR Sizes
12 FA0  0 .4 mol / s 12

10 10

FA0
8 8
FA/-rA (m )

FA/-rA (m )
3

3
>
6 6

4
FA
FA0 FA 4

2 2

0
V=6.4 dm3 V=2.2 dm3 0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0

Conversion Conversion

For isothermal reaction of greater than zero order, the PFR will always require a smaller volume than the CSTR to achieve.

2.5 2.5

2.0 2.0

FA0/-rA
(m )
3
1.5

1.0

0.5
FA0

FA
< FA0 FA
FA0/-rA
(m )
3
1.5

1.0

0.5

0.0 V=0.188 m3 V=0.207 m3 0.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

Conversion, X Conversion, X

For adabatic reaction, the CSTR may require a smaller volume than the PFR to achieve.
 Which reactor should go first
to give the highest overall conversion?
Which arrangement is best? “It depends.”
FA0

X1 그때 그때
FAe
X2
달라요

FA0
X1
FAe
X2

FA0 X1

FAe
X2
FA0
FAe
X1 X2
 An Adiabatic Liquid-Phase Isomerization

FA0 FA0 X1 =0.4

X1=0.4 FAe FAe

X2 =0.65 X2 =0.65
2.5 2.5

2.0 2.0

1.5 1.5
FA0/-rA FA0/-rA
3 3
(m ) (m )
1.0 1.0

0.5 0.5

0.0 0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

Conversion, X Conversion, X

Best arrangement Worst arrangement

Laboratory and Full-scale operating conditions must be identical.

-If we know the molar flow rate to the reactor and the reaction rate as a function
of conversion, then we can calculate the reactor volume necessary to achieve a
specific conversion.

-However, the rate does not depend on conversion alone. It is also affected by the
initial concentrations of the reactants, the temperature, and the pressure.

-Consequently, the experimental data obtained in the laboratory are useful only in
the design of full-scale reactors that are to be operated at the same conditions as
the laboratory experiments (T, P, CA0).

-This conditional relationship is generally true; i.e., to use laboratory data

directly for sizing reactors, the laboratory and full-scale operating conditions
must be identical.

-Usually, such circumstances are seldom encountered and we must revert to the
methods described in Chapter 3 to obtain –rA as a function of X.
Seoul National University
 To size flow reactor, only need -rA=ƒ(X),

It is important to understand that

if the rate of reaction is available or can be obtained solely as a

function of conversion, -rA=ƒ(X), or

if it can be generated by some intermediate calculations,

one can design a variety of reactor or a combination of reactors.

In Chapter 3, we show how we obtain the relationship between

reaction rate and conversion from rate law and reaction
stoichiometry.

Seoul National University

 2.6. Space time
Space-time :
The time necessary to process one reactor volume of fluid based on
entrance conditions. Also called the holding time or mean residence time.

 time required to process one 

 
  time 
V
    reactor volume of feed measured
v0  
 at specified condition 

A space-time of 2 min means that every 2 min one reactor volume of

feed at specified condition is being treated by the reactor.

V FA0 X dX X dX

v0
 
v0 0  rA
 C A0 
0 r
A
 Space time
The time necessary to process one reactor volume of fluid based on
entrance conditions. Also called the holding time or mean residence time.
a b
20m 20m

Consider the tubular reactor, which is 20m 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 fluid to enter the reactor completely is the space time.
For example, if the volumetric flow rate were 0.01 m3/s, it would take the
upstream volume shown by the dash lines a time 

V 0 .2 m 3
   20 s
0 3
0 . 01 m / s
To enter the reactor. It take 20s for the fluid at point “a” to move point “b”
 Space time

In the absence of dispersion, which is discussed in

Chapter 14, 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.
 Table 2-4 Typical Space time for industrial reactor

Reactor type  Production capacity

Batch 15 min ~ 20 h Few kg/day ~ 100,000 tons/year

CSTR 10 min ~ 4 h 10 ~ 3,000,000 tons/year

Tubular 0.5 s ~ 1 h 50 ~ 5,000,000 tons/year

Table 2-5 shows space times for six industrial reactions and reactors. (page 67)
 Space velocity
Definition of Space-velocity

 number of reactor volumes of 

SV 
v0 1 
 

   feed at specified condition which   time 1  
V 
 can be treated in unit volume 

• A space-velocity of 5 hr-1 means that five reactor volumes of feed at specified

condition are being fed into the reactor per hour.

• Difference in the definitions of SV and 

- space time : the entering volumetric flow rate is measured at the entrance condition
- space velocity : other conditions are often used
 LHSV and GHSV

• LHSV ( liquid hourly space velocity)

- v0 is frequently measured as that of a liquid at 60 or
75 0F, even though the feed to the reactor may be a
vapor at some higher temperature.

• GHSV ( gas hourly space velocity)

- v0 is normally measured at standard temperature and
pressure (STP).
v0 liquid v0
LHSV  GHSV  STP
V V
 Example 2-6 Reactor Space Times and Space Velocity

Calculate the space time and space velocity for each of the
reactors in Examples 2-2 and 2-3

From Examples 2-2,

v0=0.002 m3/s, Volume of CSTR=6.4m3
V 6 .4 m 3 1 1
   3200 s  0 . 89 h ; SV    1 . 125 h 1
0 3
0 . 002 m / s  0 . 89 h

From Examples 2-3,

v0=0.002 m3/s, Volume of PFR=2.165m3
V 2 . 165 m 3 1 1
   1083 s  0 . 30 h ; SV    3 . 3 h 1
0 3
0 . 002 m / s  0 . 30 h
 To summarized these last examples….

In the design of reactors that are to be operated at conditions (e.g.,

temperature and initial concentration) identical to those at which
the reaction rate data were obtained, we can size (determine the
reactor volume) both CSTRs and PFRs alone or in various
combinations.

In principle, it may be possible to scale up a laboratory-bench or

pilot-plant reaction system solely from knowledge of –rA as a
function of X or CA.

However, for most reactor systems in industry, a scale-up process

cannot be achieved in this manner because knowledge of –rA
solely as a function of X is seldom, if ever, available under
identical conditions.
Seoul National University
 To summarized these last examples….

In Chapter 3, we shall see how we can obtain -rA=ƒ(X) from

information obtained either in the laboratory or from the literature.
This relationship will be developed in a two-step process.

In Step 1, we will find the rate law that gives the rate as a function
of concentration and in Step 2, we will find the concentrations as a
function of conversion. Combining Step 1 and 2 in Chapter 3, we
obtain -rA=ƒ(X).

Seoul National University

 Homework #3

1. P2-5C
2. P2-7B
3. P2-10B
4. P2-13A

Due date: one week