Chemical Reactor Design

Y
Youn-Woo
W L Lee
School of Chemical and Biological Engineering
Seoul National University
y
155-741, 599 Gwanangro, Gwanak-gu, Seoul, Korea  [email protected]  http://sfpl.snu.ac.kr
 第2章
Conversion
and Reactor Sizing
g

Chemical Reactor Design

化學反應裝置設計

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 Objectives

After completing Chapter 2,

2 reader will be able to:

 Define conversion.
 Write the mole balances in terms of conversion
for a batch reactor, CSTR, PFR, and PBR.
 Size
Si reactors either
i h alone
l or in
i series
i once given
i
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)
(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
Q
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.

l off A reacted
mole d
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.
exhausted Consequently,
Consequently in batch system,
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 t    initially t    have consumedd  (2-4)
 i reactor i iti ll fed
f d to h b
been
 at time t  reactor at t  0 by chemical reaction
N A   N A0   N A0 X 
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 2.2 Batch Design Equations
The mole balance on species A for a batch system

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
Th design
The d i equation
ti for
f a batch
b t h reactor
t ini differential
diff ti l form
f is
i

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)
(2-5)
dt

Write the mole balances

in terms of conversion

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
d V0 dt
d d
dt d
dt

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

The design
g equation
q 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
i the
in th interpretation
i t t ti off reaction
ti ratet data
d t (Chapter
(Ch t 5)
and for reactors with heat effects (Chapter 9), 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
constant-volume
volume batch reactor,
reactor VV=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 
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  (2-10)

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)
(1-12)
dV
- conversion of flow system

FA  FA0  FA0 X

- The differential form of the design equation

dX
FA0   rA (2 15)
(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
y
FA  FA0  FA0 X

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

dX
FA0   rA' (2-17)
dW
-The
Th catalyst
l weight
i h W to achieve
hi a specified
ifi d conversion i h P=0
i 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 f a batch
for b h reactor

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

X dX
FA0 FA V  FA0  Design
D i equation
ti
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
y weight)
g )
FA0 FA V  FA0 
0  rA
~ FA0
~X
X dX
FA0 FA W  FA0  ~ 1/rA’
0  rA'
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 2.4 Applications of the design equation
for continuous
continuous-flow
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,
consequently -rrA, 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
h chemical
h i l reaction
i rate as a function
f i off conversion.
i
(at T=500K, 8.2atm)
0.5
raw data
d t
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

- ratee data
d convert
co ve reciprocal
ec p oc rates,
es, 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

C
Conversion
i

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 2-2 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 00.4
4 mol/s
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
CSTR.
(b) Shade the area in Fig. 2-2 that would give the CSTR volume
necessary to achieve
hi 80% conversion.
i

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

FA 0 X moll 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

m3)
FA/-rA (m
6
VCSTR
4 = 8 x 0.8
EXIT 2
= 6.4 m3
In CSTR, C, T, P, and X of the effluent
0
stream are identical to that of the fluid
fl id 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 2-2 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 gasgas-phase
phase reaction,
reaction and CSTRs are used
primarily for liquid-phase reactions.
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 Example 2-3 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  FA 0 4 FA 0 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   (32.47 m )  2.165m
3 3 3
 3   3 

165 m3
V = 22.165
= 2165 dm3

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 Example 2-3 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
Fig. E2-3.1)
E2-3 1) 00
0.0 02
0.2 04
0.4 06
0.6 08
0.8 10
1.0

Conversion
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Example 2-3 Sizing a PFR
Sketch the profile of –rA and X down the length of the reactor.
A0 F A F
Solution
S l ti
As we proceed down the reactor and more and more of reactant is
consumed the concentration of reactant decreases,
consumed, decreases as does the
rate of disappearance of A. However, the conversion increases as
more and more reactant is converted to product.
p
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 2-3 Sizing a PFR
Sketch the profile of –rA and X down the length of the reactor.
FA0 FA
S l ti
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 2-3 Sizing a PFR
Sketch the profile of –rA and X down the length of the reactor.
FA0 FA
S l ti
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 2-3 Sizing a PFR
Sketch the profile of –rA and X down the length of the reactor.
FA0 FA
S l ti
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 2-3 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
8 551
55 1093
093 2279
9

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Example 2-3 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
V 218 L
X=0.2 0.2

00
0.0

0 500 1000 1500 2000 2500

3
V (dm )

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Example 2-3 Sizing a PFR

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

04
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

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 Example 2-4 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
ll volume
l th the
than th CSTR
0
to achieve.
0.0 0.2 0.4 0.6 0.8 1.0

Conversion

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 Example 2-4 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 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 inverselyy
0.2 proportional to the rate.
FA0

0.1

00
0.0 FA
0.0 0.2 0.4 0.6 0.8 1.0
V=6.4 dm3
X Seoul National University
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
conversion, then we can calculate the reactor volume necessary to achieve a
specific conversion.

-However,
H the
h rate ddoes not ddepend
d on conversion
i alone.
l It
I iis also
l affected
ff d by
b the
h
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
y experiments
p (T,
( , P,, CA0)).

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

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

-Usually,
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.
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 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
b generated
t d by
b some intermediate
i t di t calculations,
l l ti

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

reactors

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

reaction rate and conversion from rate law and reaction
stoichiometry.

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 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
l l as a function
f ti off X is
i seldom,
ld if ever, available
il bl under
d
identical conditions.
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 To summarized these last examples….

In Chapter 3,3 wee shall see how

ho wee can obtain -rrA=ƒ(X)
ƒ(X) from
information obtained either in the laboratory or from the literature.
This relationship will be developed in a two
two-step
step process.

In Step 1,
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).

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