6.

1 Multiple - Reactor Systems

Single CSTR Reactor
 Since the fluid inside the vessel is uniformly
mixed (and hence elements of fluid are
uniformly distributed), all fluid elements
have equal probability of leaving the vessel
in the output stream at any time.

As a consequence of the output stream has

the same properties as the fluid inside the
vessel and the obtained conversion is low.
 Q
Reactant

FA,0 ; FV,0
(-rA) =(-rA)exit
(-XA) =(XA)exit
(-rA); XA; CA
(CA) =(CA)exit
Q

Product, FA; FV,f

Figure: - Mixed Flow Reactor

Multiple - Reactor
In minimizing the negative factors of a
single system reactors, sometimes it
may be desirable to use a series of
reactor, with the exit stream from the
first serving as the feed to the second,
and so on.
Some of the advantages of multiple reactor
system are to
enhance the conversion

enhance the yield and selectivity

control the heat effect in the reaction.
Generally, we can have two types of multiple reactors:
• Plug flow reactors connected
in series

and or in parallel.

• Continuous stirred tank reactor (CSTR),

connected
in series
6.1Design of plug Flow Reactors (PFR) in series
Used:
to boost the selectivity of multiple
reactions,
Used for high pressure reactions,
Used for high heat of reactions etc.
CA,0 CA,1 CA,2 CA,N-1 CA,N
XA,0 XA,1 XA,2 XA,N-1 XA,N

Let
X A,1, X A,2 ,.... X A, N 1, X A, N

be the conversion of components A

or for the N reactors in series, we obtain the equation

leaving the reactor 1, 2, .................................. N.
Based on the material balance of the feed rate of A to the
first reactor using PFR design equation, we find for the nth
of multiple plug flow reactors, which are
X A,n
Vn dX A
 
FA,0 X A,n -1 ( rA )
 X A,1 X A,2 X A,n X N dX
VT dX A dX A dX A A
     .....    ...  
FA,0 X (rA ) X (rA ) X (rA ) X ( rA )
A,0 A,,1 A,n -1 N -1

VT N V V  V2      Vn     VN
 ∑ n  1 (5.20)
FA,0 FA,0 FA,0
n 1

Thus N plug flow reactors connected in series

with total volume VT gives the same conversion as
a single plug flow reactor of volume V
6.1.1Plug flow reactors connected in parallel
or parallel - series

Such connection could be efficient,

if the space time in each reactor is
the same, i.e.,
V
F 
FV , f

To achieve this condition, we can treat the whole

system as a single plug flow reactor of volume
equal to the total volume of the individual units. if
the feed is distributed in such a manner that the
fluid streams which meet in the connection have
the same composition
6.2 Design of Continuous stirred tank reactors (CSTR) in
series One of the disadvantages of a single
continuous stirred tank reactor is that
 the reactant in the reactor is all at
the exit concentration level, i.e., very
low reaction rate
Cognizant to this low reaction rate
results, X
A  V
 low conversion,
(-r ) F
A A,0
 large holding time and

 large reactor volume.

To produce a higher conversion in a smaller
reactor volume a number of CSTR should be
installed.
A series (cascade) reactors
enables a fraction of the reaction to proceed in
each reactor, so that each reactor handles a
fraction of conversion as well as heat
liberated/absorbed.
Series reactors are normally arranged to flow
automatically under gravity by having the
reactors installed at progressively lower levels as
shown in the following Figure.
Feed

Product
To design a cascade reactors,
Normally required size of reactors for specified conversion
Additionally we have to get answers to the
following questions

• How many reactors should be in the

si tor

series?
De ac
gn
Re

• What would be the volume of each?

•
si ss

Do the reactants should be fed to the

De oce
gn

first only or distributed over more

Pr

than one reactor?

a s ed on
e r s b - concentration,
e a n s w h as
Th t io n s uc - temperature and
c o nd i
t he - required conversion
 Design consideration, if the conditions are not so
forced, it is preferred to
(1) have a minimum number of reactors and
in equal size reactors arrangements.

(2) Different size reactors may be employed,

if the heat dissipation is a problem.

Changing the size of the first reactor

would change the heat generation in it
and this might be used to overcome
heat transfer problems in the initial
stages.
The heat generation could then be
increased in the later reactors where
heat removal is lesser of the
6.2.1 Design of equal size CSTRs in series
Tank reactors are usually employed for liquid
reaction and in most cases, it is assumed that the
density of the reaction is constant.
Consider a system of N tank reactors connected in
series as shown in the following Figure

CA,1 CA,2 CA,n-1 CA,n CA,N-1 CA,N

Even though in each mixed reactor, the
concentration is uniform, there is nevertheless a
change in concentration as fluid moves reactor to
reactor C - C
  A,0 A
F (-r )
A
Using the CSTR design equation we can write for
each reactor

C - C  (-r )
A,0 A,1 A,1 F,1
C - C  (-r )
A,1 A,2 A,2 F,2
 (5.21.1)

C - C  (-r )
A,n-1 A,n A,n F, n

Assuming the first - order reaction for the condition that
T, m = constant equation (5.21.1) becomes

C - C k C 
A,0 A,1 1 A,1 F,1
C - C k C 
A,1 A,2 2 A,2 F,2 (5.21.2)


C - C  knC 
A,n-1 A,n A,n F, n


Separating the equation for each reactor, we get

• For the first reactor
C A,0
C A,1 
1  k1 F,1 (5.22.1)
For the second reactor C A,1
C A,2 
1  k 2 F,2 (5.22.2)
SubstitutingC A,1 from equation (5.22.1) to equation (5.22.2) yields
C A,0
C A,2  (5.22.3)
(1  k1 F,1 )(1  k 2 F,2 )

Applying the same rule, we can get for n-reactor

C A,0
C A,n  (5.22.4)
(1  k1 F,1 )(1  k 2 F,2 )     (1  k n F, n )

Taking the basis, volumetric flow rate and eventually the

space time, residence time and the temperature are being
the constants, then the equation (5.22.4) becomes,

C A,0
C A,n 
(1  k F ) n (5.22.5)
 

n
1 


C 


  1 A,0 

 -1


F, n k C 
 


A  

 
 

In such type of cascade reactor, concentration,

reaction rate and conversion are changed in every
reactor in a form of discrete as shown in the
following Figure.

Conversion of any reactor in a cascade can be

defined as

C A,0 - C A,n C A,n

X A,n  1- (5.23.1)
C A,0 C A,0
CA,0
CA,1

CA,2
CA CA,3

V1 V2 V3 VR

XA XA,3
XA,2
XA,1

V1 V2 V3 VR
Substituting equation (5.22.5) to equation (5.23.1) gives
CA,n
1
X A,n  1 -
X A,n  1- CA,0
(5.23.2)
(1  k F ) n C A,0
C A,n 
(1  k F ) n
Recalling the space time
VR C A,0 X A
F  
FV ,0 (-rA )
And we can use this equation for n, number of reactors, we have
VR,n X A,n - X A,n 1
 F ,n   C A,0
FV ,0 (-rA )

N X A,n - X A,n 1 C A,0X A,n

 F ,cascade    F ,n  C A,0  
n 1 (-rA ) (-rA )
As the number of reactors approach infinite, thenX A,n  0
and then the space time will be
X A,n X A dX
 F ,cascade  C A,0   C A,0  A (5.24)
(-rA ) 0 (-rA )
Equation (5.24 is analogy to the design equation of plug
flow reactors. This shows when a number of mixed
reactors are increased to infinite the conversion approach to
that of the plug flow reactor
General conclusion would be
i) WhenVR cascade = Constant and N  , then,
XA, cascade  X
A,PFR
i.e., conversion in cascade reactor is going to be equal
to conversion in PFR
When X A = constant and N  , then,
VR, cascade  VR,PFR
XA XA.3
XA.2
XA.2 X A0
XA.1 PFR
X A,2

X A,1

V1 V2 V3 V
As always,
the reactor design is to find the size of
the reactor for the specified conversion

Hence,
Main parameters required in Designing
CSTRs in series
Obtaining concentration/conversion

Obtaining volume of the reactor

A)Obtaining concentration/conversion
Knowing: V ; FV,0; CA,0
As for an illustration, we can take three identical
volumes of reactors as shown in the following Figure

FA,0

CA,3
V1 CA, 1
V2 CA V3
,2

Figure : Three continuous stirred tank reactors in series.

For the density constant, at steady - state, the volumetric
flow rate, the temperature are constants.
Assuming - reactor volume, V
- molar flow rate and FV,0
- initial concentration CA,0 are known,
 (-rA ) F  C A,0 - C A, 1
or for each series reactors the general equation would be

(-rA ) F  C A,n -1 - C A,n

or
1
(-rA )  ( C A,n -1 - C A,n )
F

1
(-rA )  ( C A,n -1 - C A,n ) (5.25)
F

For inlet concentration C A,n-1 = known, the rate

equation in steady - state mixed flow reactor is a function
of only the exit concentration and the equation (5.25) is
reduced to
 1
(-rA )  A n -1 - C A,n (5.26)
F

Equation (5.26), which we call it an operating line

We construct a graph of the rate of reaction

versus reactant concentration which gives

1 FA,0
Slope  tan  -  -
F VC A,0
 1 FV,0 FA,0
Slope  tan  - - -
F V VC A,0

-rA

CA,2 CA,1 CA,0 CA

Figure 5.24 Graphical method to find the exit
concentration of each reactors using (-rA )  f(CA )
 The exit concentration of any series reactors can be
found by using the following steps.
Step 1 Locate the initial concentration known, C A,0 on the
abscissa (point in Figure 5.24)

Step 2 Draw a straight line from C A,0 with a slope of

1 FA,0
-  - until it cuts the - rA versus concentration curve
F VC A,0
Step 3 Draw a perpendicular line until it cuts the C A abscissa
This point is the required exit concentration of the first reactor C A,1
1
Step 4 Draw a straight line from C A,1 with a slope of
F
The intersection of this line with the reaction curve,
establishes the exit concentration
C A,2 of the second reactor.
Step 5 Similar construction can be drawn for the third,
fourth etc reactors
Obtaining exit conversion: knowing CA,0; FA,0; V
Modifying the equation (5.25) gives
1
(-rA )  ( C A,n -1 - C A,n )
F
C A,0
(-rA )  ( X A,n - X A, n -1)
F
Using the same manner as above, equation (5.25) can be
rearranged

C A,0
(-rA )  A n -1  X A,n (5.27)
F

C A,0 C A,0FA,0 FA,0

Slope  tan    (5.28)
F VC A,0 V
 (-rA)

FA,0
Slope  tan 
V

  
XA,1 XA,2 XA,3 XA
Figure : Graphical method to find the required conversion for each reactor
using (-rA )  f(X A )
B. Obtaining volume of the reactor knowing
In such operation, CA,0; CA,f
initial CA,0 and
final concentration CA,f should be known.
For identical series of reactors to ascertain the
volume,
one must attempt on a trial and error basis.
Consider the two identical volumes of reactors in series as
shown in the following Figure

CA,0 CA,1 CA,2

V1 V2
Here C A,0 and C A,2 are known, and C A,1 is unknown
As starting, we write operating line equation,
1
(-rA )  ( C A,n -1 - C A,n )
F

1
(-rA )  A n -1 - C A,n
F
and
1 FV,0
Slope  tan  -  -
F V

Since the reactors are of identical volume

which, therefore, leads to have the same
slope
Procedure
Plot the rA versus C A
 where the points C A,0 and C A,2 are known
 From the point we draw a parallel line, to
find the value of R1

 But the position of R1 has to be adjusted to

make C A, 0 R1 and C A,1 R2 parallel because
these line must have the same slope if the
tanks are of equal size.
 -rA

R1

CA, 2 C A, 1 C A, 0 C A

1 FV,0
Slope  tan  -  -
F V
Figure : Graphical method to find the volume of equal
sized two mixed reactors
6.3.2.2 Design of different size CSTR in series

V1 V2
V3
Due to the nature of the reactants, which involves the
mixing behavior, heat effect, conversion ability etc, there
is a need to set up a reactor of different size. In designing
of a different size CSTR, there is also a need to evaluate
the following considerations
• To find the outlet concentration/conversion from a
given reactor system

•To find the best set up to achieve a given conversion

A) Finding the outlet concentration / conversion
in a given system knowing C A,0 V , V , V
1 2 3
The best method to find the outlet composition in various
sizes of a reactor, is graphical method using rA versus C A
F F C
V ,0 V , f  0 A,0 V1, V2, V3 known
Taking material balance design equation
we may write for the first reactor as

V1 C A,0 - C A -1
t   F,1  
FV,0 (-rA,1)

Rearranging gives
1 FV,0 (-rA,1)
  - 
 F,1 V1 C A,1 - C A,0
Similarly for the nth-reactor we may derive

1 FV,0 (-rA,n )
  - 
 F, n Vn C A,n - C A,n -1
or
1
 (C A,n - C A,n -1)  (-rA,n )
 F, n
or 1 1
(-rA,n )  C A,n -1 - C A,n
 F, n  F, n

(-rA,n )  An 1 - 1 C A,n
F, n

by plotting rA
versus C
A we can find for each reactor,
1
different slope of -
 F,n
( rA ) ( rA )1
Slope 
C A,1  C A,0

( rA ) 2
Slope 
C A,2  C A,1

CA.3 CA.2 CA,1 CA,0 CA

Figure 5.30 Graphical methods to find out the

concentration of different size of reactors
B) Determination of the best set up
Our target always is to have a total minimum size of the
reactors connected in series for a specified conversion.
Graphical method to determination of the best set up
Consider two set up models of reactors having small and
big size of reactors. The question arises for the specified
outcome conversion that whether there is a size advantage,
simply by having two alternative setups as shown in the
Figure

XA,1 XA,2 XA,1 XA,2

Figure : Different set up connection

 A general concept to get total minimum size in
SCTR in series on different size reactor is depend
on :

 the kinetics of the reaction and

 on the intermediate conversion level.

 Kinetics :based on the order of reaction

it is recommended to use

smaller reactor at first for the

reaction orders n>0.
larger reactor comes first for the
reaction orders n<0.
 Intermediate conversion
Taking design equation

V XA

FA ,0 (- rA )

Let us consider two reactors connected in series with

different intermediate conversion

Arrangement # 1
Intermediate
XA,1 and XA,2 conversion
XA,3 > XA,1
Arrangement # 2 Final conversion
XA,3 and XA,4 XA,2 = XA,4
 V   V
Area  F ,2  2 Area  F ,2  2
C F C F
A,0 A,0 A,0 A,0
P Q
1 P Q
(r ) 1
A (r )
A S R

S R

XA,1 XA,2 XA,3 XA,4

  V
F,1 V Area  F,1  1
Area   1 C F
C F A,0 A,0
A,0 A,0
Figure 5.30 Different set up with intermediate conversion
One can see from the above Figure that the intermediate
conversion changes (which depends on the size of the
reactor) so does
(A) the size ratio of the units (represented by the
two shaded areas)

(B) as well as the total volume of the reactors

required
Taking the objectives of the topic of total size volume of
the reactor is as small as possible i.e.,

total shaded area is minimized, when the

rectangle PQRS is as large as possible
This leads us to the problem of choosing the
intermediate conversion XA,1 and XA,3 (point R on
the curve) so as to minimize the area of the
rectangle.
Maximization of Rectangles.
In Fig. construct a rectangle between the x-y
axes and touching the arbitrary curve at point
M(x, y). The area of the rectangle is then
A =xy
This area is maximized when dA =ydx + xdy =0
or when
 dy  xy
dx
this condition means that the area is maximized
when M is at that point where the slope of the
curve equals the slope of the diagonal NL of the
rectangle.
6.2.3 Design of different types of reactors in series
Each reactor has advantage and disadvantage for
certain process.
Combining reactors might bring
 size reduction,

 increasing yield,

 achieving high conversion, and

 sink the heat effect etc.

General consideration #1
Considering the design equations of plug flow and
perfectly mixed reactor and the geometrical nature of the
reactors, one can observe the size of reactor in plug flow
is much smaller than CSTR
 X A,f
Design equation for PFR V dX A
  = Area (1)
FA,0 X A,,0 ( rA )
V X A, f - X A,0
Design equation for CSTR = Area (1+2)
FA,0 (-rA )
1
( rA )
2

XA,0 X A, f XA
Figure: smaller size in Plug flow over CSTR
General consideration #2
 The rate – conversion curve
s
t i (Kinetics) is a useful method to
c
ne
Ki determine which reactor comes
first to give a total smaller volume
for specified conversion
Mainly focus on
Order of reaction and

 Type of reaction
6.2.3.1 Kinetics method to determine which
reactor comes first using the rate
conversion curve
Let us see reactors of different sizes arranged in
series. Figure shows reactors arranged mixed
followed by a plug flow and then again in turn
with the mixed one.

V2 XA,2
V1 XA,1 XA,3
V3
 V3
1 Area 
FA,0
( rA ) V1
Area 
FA,0

V2
Area 
FA,0

XA,0 X A, 1 X A, 2 X A, 3
Figure 5.32 Graphical representations for reactors in series.
The design equations for the three reactors are
V X A,1 - X A,0
First - Reactor, CSTR, 1 
FA,0 (-rA,1)

Second - Reactor, PFR, X A,2

V2 dX A
 
FA,0 X A,,1 ( rA,2 )
Third - Reactor, CSTR V3 X A,3 - X A,2

FA,0 (-rA,3 )
Representing this way, it allows us to predict
the overall conversion or
the intermediate conversion and
the optimum size for the process.
Best arrangement can be arrived at by examining the rate
conversion curve.
 If the rate conversion curve rises monotonously (n>0)
the ordering of units should be
n>1
Plug flow followed by small CSTR and large
CSTR respectively V3
1 Area 
FA,0
( rA ) V1
Area 
FA,0

V2
Area 
FA,0

XA,0 XA,1 XA,2 XA,3

Figure 5.32 Graphical representations for reactors in series.
0<n<1
the reverse ordering namely large CSTR to be
followed by small CSTR and lastly by PFR can
be implemented.
1
( rA )

Large CSTR

small CSTR PFR

XA,0 XA,1 XA,2 XA,3

n<0
For a negative order, or any other form where
the rate has a maximum or minimum, the best
set up is a CSTR followed by a plug flow
reactor.

CSTR

PFR

XA,0 XA,1 XA,2 XA

The effect of type of reaction
e.g. Autocatalytic reaction

1
( rA ) 1
( rA )

XA XA
Figure 5.34 Typical rate concentration curve for
an autocatalytic reaction
In Autocatalytic reaction the rate - conversion
curve is a useful method to determine which
reactor is superior (i.e., which reactor requires a
smaller volume for specified conversion)

This depends on the magnitude of

conversion
Generally:
 at low conversion the mixed reactor
is suitable than PFR

 at high conversion PFR is more

suitable than CSTR
Low conversion CSTR is much better
F A, 0 X A, 1 X A, 2

1
( rA )

CSTR

Plug flow

XA,0 X A,1 X A,2 XA

Figure 5.33 CSTR followed by a plug flow reactor
High conversion PFR is much better
XA,1 XA,2

PFR
1
( rA )
CSTR

XA
XA,0 X A,1 X A,2
Exercise 6.1 The demirazation reaction,
2A  R

is carried out in the liquid phase under isothermal

conditions in the presence of inert solvent at 353
K. The equilibrium constant at this temperature is
a large positive number so that the reaction can
be considered irreversible. The reaction rate
constant, k equals to 2x10-3 m3 / mol . s and the
reaction is second order with respect to A, whose
feed concentration is 1000 mol / m3 and FV,0 = 0.5
m3 /s . Calculate the volume of two equal reactors
connected in series to obtain an overall
conversion of 75%.
Exercise 6.2 The isothermal decomposition
reaction
A 3B
is carried out in the flow reactors. The laboratory
measurements of the chemical reaction rate as a
function of conversion are given in the following
table
XA 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.85
(-rA) .0053 .0052 .005 .0045 .04 .003 .0025 .0018 .0013 .001

where , (-rA) is in mol x 10 3

dm 3 . s
The temperature was 422 K, the total pressure
1.01x103K Pa, and the initial charges were
The temperature was 422 K, the total pressure
1.01x103K Pa, and the initial charges were
consisting of an equimolar mixture of A and inert.
The gas mixture enters the reactor with a flow
rateof 6 dm3 / s.
8.309kPa.dm 3
The ideal gas constant is R =
mol.K
Using graphical method:

(a) Calculate the volume necessary to achieve

80% in one CSTR.
(b) Calculate the total volume to two CSTRs
necessary to achieve 80% conversion
when intermediate conversion is 40%.
(c) Calculate the volume necessary to achieve
80% conversion in one PFR.
(d) Calculate the total volume of two PFR's
necessity to achieve 80% conversion if
intermediate conversion is 40%.

(e) Calculate the individual reactor volume as

well as the total reactor volume for a
sequence of CSTR and PFR in series when
the intermediate conversion is 40%.

(f) Calculate the individual reactor volume as

well as the total reactor volume for a
sequence of a PFR and a CSTR in series
when the intermediate conversion is
40%.
6.3 Comparisons of Ideal Reactors
 Generally the Choice of a reactor for
a particular reaction is difficult

The Chemical Engineer is always asked about

 how we choose the right type of reactor
for the desired production / reaction / ?.

To answer the question we have to look into

different factors affecting the choice of reactor
such as:
•The reaction type

•Operating temperature
 •Planned scaled of production

•Cost of equipment and operation

• Working safety, stability and

flexibility

•Equipment life expectancy

• Easiness of convertibility of the

equipment
  No net formula is available to select the
reactor,
 we can only use our technical judgment
and the affordability of the process
:
mber

including the economic factor.

One of the technical comparison is based

Re m e

on the performance of ideal reactors

When we said performance we mean:
 determining the size of reactor for
a specified throughput or rate of
production or conversion,
 Fraction of unreacted
 Yield
 Selectivity
Comparison is distinguished for :
 single reaction, and
 multiple-reactions in a form of
parallel and series forms
6.3.1Reactor comparisons for Single
Reaction
 Single reactions are reactions whose
progress can be described and followed
adequately by using only one
 rate expression coupled with the
necessary stoichiometric and
equilibrium expressions.
 For such reactions product
distribution is fixed;
 hence,
the important factor in comparing
designs is the reactor size
Before we compare the size of reactors,
let us mention the batch reactor briefly.
 The batch reactor has the advantage
of small instrumentation cost and
flexibility of operation (may be shut
down easily and quickly).
It has the disadvantage
 of high labor and handling cost, often
considerable down time to empty, clean
out, and refill, and
 poorer quality control of the product.
Hence we may generalize to state that the
batch reactor is well suited to
produce small amounts of material
and to produce many different
products from one piece of
equipment.

On the other hand, for the chemical

treatment of materials in large
amounts the continuous process is
nearly always found to be more
economical
6.3.1.1 BR and CSTR
A performance comparison is made in
terms of
 the size of vessel required in each
case to achieve
 the same rate of production Pr
 the same fractional conversion
and
 The same reaction condition at
the same temperature and
constant-density systems,
Consider a first – order reaction type
A  .....  cC  .....
in which A is the limiting reactant
Definition of rate of production
A  .....  cC  .....

Batch process
n 
 mol


Pr  C 



(C)  

t 
 h 

C

Flow process
Pr  FC

 mol
(C) 

 h 
For a BR, the rate of production of C, may be
rewritten as, with XA,2 = XA and XA,l = 0,

n  n X  C X V
Pr  C  C A,0 A  C A,0 A BR
(C) t tr t (1  a)t r
C d
Where : a = td / tr , down time

From design equation of batch reactor we have,

XA
dX A
t r  C A,0 0 ( - rA )
For a CSTR, in steady-state operation at a
flow rate FV,0 , the rate of production of C is
the molar rate of flow of C, that is

Pr  F  C F  F  C X  (r )V
(C) C C V ,0 V ,0 C A,0 A C A CS

The ratio of the vessel sizes for the same P(C) (and
XA,) may be determined by equaling

Pr(C),BR = Pr(C),CS
and substituting for tr we get:

X
A
(1  a)  dX (r )
V A A
BR  0
V X (r )
CS A A

The ratio for any kinetics depends on,

XA and the

form of (-r ), (kinetics)

i) If size of vessel is a major consideration,
the advantage is
- to the CSTR for high values of a
(down time)
-to the BR for high conversion

2)for given XA and a, (kinetics solution)

 the ratio decreases as order of reaction
increases, and i.e smaller size in BR

 also that, at low conversion, it

approaches 1 + a, independent of order.
Exercise 6.3 P 403 Missen
Compare F for a CSTR and tr for a BR for the
same XA, and interpret the comparison
graphically.
6.3.1.2 Comparison of BR and PFR
1)with respect to time
Regarding reactor sizes, a comparison of the
following equations for a given duty and for ε = 0
X A dX CA
BR A dC A
tr  C A,0  - 
0 ( - rA ) C A,0 ( - rA )

PF R V F X A dX
A - 1 C A dC
A
   
F A,0 C A,0 0 ( - rA ) C A,0 C ( - rA )
A,0

V X A dX C A dC
F   C A,0  A - A

FV,0 0 ( - rA ) C A,0 ( - rA )
 shows that an element of fluid
reacts for the same length of time in
the batch and in the plug flow
Recalling equation for constant density
F 
VR
and
V F 
Fv,0 R v,0 F
dV  F d
R v,0 F
For plug flow reactor
X
A, f dX
 C  A
0 (rA)
F A,0

X
A
C  dX (r )
t A,0 A A
r, BR  0  1
 X
F , PFR C A
 dX (r )
A,0 A A
0
The above equation shows us,
for an isothermal first-order reaction
taking place in a constant-volume BR but
at varying density in a PFR,

t 
r,BR F ,PFR

the times are equal

Note that this is not the case
for other orders of reaction
2)with respect to sizes
 Using analogy comparison of vessel size
of BR and CSTR
For the same rate of production at the same
conversion comparison of vessel sizes gives
X
A
(1  a)  dX (r )
V A A
BR  0
V V X (r )
BR 1  a at constant  and T CS A A

V
PFR
 For a big production we must correct
the size requirement estimate to
account for the down-time between
batches.
 For a small production the same
volume of these reactors is needed to
do a given job.
6.3.1.3 Comparison of CSTR and
PFR
For a given duty the ratio of sizes of mixed
and plug flow reactors will depend on

the form of the rate equation.

the conversion of reaction, and

the stoichiometry,
A) The form of the rate equation.
THE l / rA PLOT
General
From the curve of plots of r versus (CA,0 - CA) for r
= kCn for several values of the order n
 It is obvious that r is a monotonically
decreasing function of CA,0 – CA if n > 0,
 a horizontal line if n = 0, and
 increases with CA,0 – CA if n < 0.
The l/r plots obviously have reversed slopes.
 Note that 1 /r goes to infinity as CA 0
for any kinetics because reaction rates
must go to zero when reactants have been
consumed.
 This is equivalent to saying that the
kinetics of all reactions must become
positive order in the limit of any reactant
disappearing
THE l / rA PLOT

 There is a graphical construction that

shows the difference of sizes in different
types and combinations of chemical
reactors

We write the mass balance equations as

C A,0 - CA 1
 F ,CS   (C A,0 - CA )
(-rA) (-rA)
and
CA 1
 F , PF -  dC A
C A,0 ( - rA )
 The size in a CSTR is the area under the
rectangle of width (CA,0 - CA) and height
l/r(CA),
 while the size in a PFR is the area
under the curve l/r(CA) from CA,0 to CA.
Sizes Comparison looking to the above
Fig.
 This construction also shows why the CSTR
becomes much less efficient (requires much
larger volume) at high conversions.
 The l/r curve increases rapidly as CA 0,
and therefore the size in a CSTR becomes
very large compared to the size of PFR.
 Large CSTR rectangle if 1 /r is a
monotonically increasing function of
CA,0 - CA (r monotonically decreasing),
n>0
 Areas are equal for
n = 0, and
 Smaller area for
n < 0.
 Thus it is evident that a PFR is
always the reactor of choice
(smaller V) for greater than zero-
order kinetics in an isothermal
reactor.
 The CSTR may still be favored for
n > 0 for cost reasons as long as
the conversion is not too high, but
the isothermal PFR is much
superior at high conversions
whenever n > 0.
  Analogy we compare for “normal” kinetics
the sizes of a CSTR and a PFR required to
achieve the same conversion.
Considering the design equation for both reactors
we have F X
V  A,0 A
CS (r )
A
X
and A
V F  dX (r )
PFR A,0 A A
0
V X (r )
Thus CS  A A
V X (a)
PFR A
 dX A (rA)
0
Let us make the comparison for the large class of
reactions approximated by the simple nth-order
rate law

where n varies anywhere from zero to three.

For mixed flow

whereas for plug flow

Dividing we find that

(a)

With constant density, or ε = 0, this expression

integrates to

(b)

or
Equations (a) and (b) are displayed in the
following graph to provide a quick comparison of
the performance of plug flow with mixed flow
reactors

 The ordinate becomes the volume ratio

VCS/VPFR or space-time ratio

 if the same quantities of identical feed

are used:CA,0 and flow rate FV,0, the
ordinate of this figure gives directly the
volume ratio required for any specified
conversion.
 n=3

Cn
 

 V F 



A,0 A,0 CS



n  n=2
C V F
 



A,0 A,0  PF

n=1

n=0.5

0 1 - XA 1.0
The above Figure shows the following:
1. For any particular duty and for all positive
reaction orders the mixed reactor is
always larger than the plug flow reactor.
 The ratio of volumes increases with
reaction order.
2. When conversion is small, the reactor
performance is only slightly affected by
flow type. The performance ratio
increases very rapidly at high conversion;

3. Density variation during reaction affects

design; however, it is normally of
secondary importance compared to the
Application of design equation similar to
eq. (a) and (b) V X (r )
CS  A A
V X
PFR A
 dX A (rA)
First – order reaction 0

V X kC (1  X )
CS  A A,0 A
V X
PFR A  

  A  kC A,0(1  X A)
dX 


0
X
 A
(1  X ) ln1 (1  X )
 

A  A 
Second – order reaction V X (r )
CS  A A
V X
PFR A
 dX A (rA)
0
V X kC 2 (1  X )2
CS  A A,0 A
V X
PFR A  
2 2
dX
  A 

kC (1  X )
A,0 A
0
 1
1 X
A
Table : VCS / VPFR for different n

XA

VCS / VPFR

- for small conversion insignificant

when we use CSTR or PFR.
- for higher conversions significant
when we use CSTR or PFR.
Exercise 6.4 Missen p405

Calculate the ratio of the volumes of a CSTR and a

PFR (VCS / VPFR) required to achieve, for a given
feed rate in each reactor, a fractional conversion
(XA) of (i) 0.5 and (ii) 0.99 for the reactant A,
if the liquid-phase reaction A -> products is

(a)first-order,
(b)second-order with respect to A. and
(c)What conclusions can be drawn?

Assume the PFR operates isothermally at the

same T as that in the CSTR.
B) Comparison with respect to conversion
The reaction is assumed to take place at constant
density and temperature
Let us take nth - order of reaction
nA  B (r )  k C n
A A
C
A 1 - X
C A
A,0
The values for a PFR are also valid for a BR for the
conditions stated,
with reaction time for no down-time (a = 0), as

t 
r,BR F ,PFR
For batch reactor, dC A (r )  k C n
A A
rA 
After integration,
dt

 n  1  n  1 
1 C


 - C 
  - kt
n  1 A 


A,0 


 

or,

C 1- n - C 1 n  (n  1) kt
A A,0 n # 1

 The order n cannot be found explicitly from

the equation, so a trial-and-error solution
must be made
CA as a function of time becomes
11 - n

n - 1 

C (t)  1  ( n - 1 )kC
 
C  t 
A A,0 


A,0




C 11 - n
A 

n - 1 
(a)
1  ( n - 1 )kC
 


t 

C  A,0 

A,0  

reaction conditions are normalized by means of a

dimensionless reaction number MA,n defined in the eq.
n 1
M  kC t
A,n A,0
MA,n :- Dimensionless Reaction Number
which normalized reaction conditions
where t is the reaction time in BR and  / t the
F
space / residence time in a PFR.
n 1 n 1
M  kC  M  kC t
A,n A,0 F A,n A,0
or substituting to (a)

C 1

A  1 (n 1)M
 1n

 (a)
C

 A,n 

A,0  
C
A 1 - X
C A
or conversion A,0
1
1n
 
X 1 - 1 (n 1)M
 
(b)
A 


A,n 


C 1
A  1 (n 1)M 1n




C 
 A


C
A,0 A 1 - X
C A
A,0
Fig. CA /CA,0 for various orders of reaction in a BR
or PPR as a function of M
Design equation for CSTR
F X (r )V
V  A,0 A X  A
A F
(r ) A,0
A
n kC n (1 - X ) n
kC V A,0 A V
X A A 
F C F
A,0 A,0 V ,0

X  kC n1 (1 - X )n
A A,0 A F

X  M (1 - X )n
A A,n A
Concentration ratio for CSTR C
A 1 - X
C A
A,0
C
A  1 - M (1 - X )n
C A,n A
A,0

n
C C







A  1 - M A 



(b)


C A,n C 




A,0
 

A,0 




n
C





 C
M A




 A  1  0
A,n C 



C
A,0
 



 A,0
C
A  1 - M (1 - X )n
C A,n A
A,0
 C
A  1 - M (1 - X )n
C A,n A
A,0

Fig. CA /CA,0 for various orders of reaction in a

CSTR as a function of M
Table CA /CA,0 for various orders of reaction in a
PFR /BR and CSTR as a function of order of rxn
1 C
C TR A  1 - M (1 - X )n
A  1 (n 1)M 1n
R

CS C
 
A,n A
/B

 
C 
 A

 A,0
R

A,0
PF
 1 C
C A  1 - M (1 - X )n
A  1 (n 1)M 1n
 
A
C




A

 C A,n
A,0 A,0
CSTR
PFR or BR

 the values of CA/CA,0 for a CSTR are higher

than those for a BR or PFR (except for n =
0, where they are the same)
Comparison using CA/CA,0 vs MA,n from the above
Fig. and Table
 the values of CA/CA,0 for a CSTR are
higher than those for a BR or PFR
(except for n = 0, where they are
the same)
Thus C
X 1 - A
A C
A,0
 Higher conversion is obtained in
PFR /BR than in CSTR
Thus
 The size of CSTR is higher than for
PFR /BR for similar conversion and
reaction condition
 XA

The Table confirms that for the

same order and MA,n the best
Table : Comparison with respect to conversion

performance is always
obtained in a PFR,
6.3.2 Reactor comparisons for Multiple
Reaction’s

Reactor comparisons can be seen

for:
 Product distribution
 Boosting selectivity of
the desired product

 Optimum temperature
for minimum size of
6.3.2.1 Boosting selectivity of the desired product
for Multiple Reaction’s
Consider the parallel reactions,
k
A 1 B
 desired  product (r )
B
k
A 2 C
 
 unwanted  product (r )
C
The selectivity ratio for the reaction becomes
r
S  rC
C
B
Recalling the differential equation for BR
n
dC
B  kC 1
dC n dt 1 A
C  k C 2
dt 2 A
Then the selectivity ratio becomes

r dC k
S  rC  C  2 C n -n (a)
C dC k A 2 1
B B 1

 Our target therefore, would be to keep

the selectivity ratio in equation (a)
as small as possible.

 Here CA, is the only factor which we

can adjust and control (k1, k2, n1,
and n2, are all constant for a specific
6.3.2.1.1 The concentration of the
reactant (characteristics of the
reactor)
r a l l y
G e ne
based on the characteristics of the reactor

 for low concentration, we use CSTR

 for higher concentration we use PFR

and BR
To keep concentration of the reactant
as low as possible through out the
reaction, C
X 1 - A
A C
A,0
 we have to maintain the conversion
as high as possible

 or we have to increase the inert

(dilute) in the feed

 or to decrease the pressure when

we are working in the gas phase
system.
If we want to keep the reactant concentration
high through out the reaction,
 we have to use adverse effect to the
above,
 namely maintain low conversion,
 remove inert from the feed
 or increase the pressure in gas system.

Effect of concentration of A to Maximize the

desired product
Maximize the desired product using equation (a)
means we have to keep SC as low as possible
r dC k
S  rC  C  2 C n -n
C dC k A 2 1
B B 1
1. n  n
1 2
i.e. the desired reaction is of higher order than
the unwanted reaction
dC k k
S  C  2C n - n  2 1
C dC k A 2 1 k C n2n1
B 1 1 A

To keep the selectivity ratio, SC low

 we need higher reactant
concentration and this is done in
plug flow or batch reactor which
means a smaller size of a reactor
2. n  n
1 2
i.e. the desired reaction is of lower order
than the unwanted reaction
dC k
S  C  2C n - n
C dC k A 2 1
B 1
A lower reactant concentration favors to form
minimum selectivity ratio. This is achieved in a
CSTR which gives an effect of a large reactor size.
There is a conflicting demand of, in
t e one side to keep that ratio small and
N o
on the other a big size of reactor
In such case, analysis of economic
justification is essential.
3. n  n
1 2
i.e. the two reactions are of the same order
dC k
S  C  2
C dC k
B 1
 The product distribution here is
fixed and unaffected by the type
of reactor used.
This equation can vary only by
changing the temperature of the
te

reaction and or by using a catalyst.

No
6.4.2.1.2 The condition of the reaction (k-Temperat
Consider reactions,
k
A 1 B
 desired  product (r )
B
k
A 2 C
 
 unwanted  product (r )
C
For the same order of reaction, n n
1 2
dCB k1 dC A (E - E ) / RT
SB   B  1 e 2 1
dCC k2 dC A
C 2
A general statement :
 a high temperature favors the reaction
of higher activation energies;
 a low temperature favors the reaction
of lower activation energies.
Applying the above statement, the desired
product is favored
if E1 > E2 using high T
if E1 < E2 using low T
 Similarly Consecutive reactions 1 2
A  P  C
where P is desired and C is unwanted product having
the same order of reaction. The production of P can be
written k2
CP  k1  k2 - k1
  
C A,0  k2 
the production of P is increased if k1 / k2 is increased,

if E1 > E2 we use high T

if E < E we use low T
6.3.2.2 Optimum temperature for
minimum size of reactor
 Our target in multiple reactions is to have
higher selectivity to the desired product
with a minimum size of a reactor.
The minimum size (volume)
ole

will be achieved if the

ba m m

reaction rate is maximum at

ce

all position in the reactor.

lan
Fro

 The optimum temperature

s will be chosen to establish
hu a maximum rate at any
T
conversion level.
It is, therefore, essential to investigate
optimum temperature we have to look the
relation of
kinetics (reaction order),

activation energy,

reactor size and

 temperature.
Considering Reactor size and temperature
For the flow process the reactor size will be
V
represented by space time F 
FV,0
Optimum temperature
 In such a case an alternative solution
such as an intermediate temperature
should be found by using analytical
method or by search procedures.

Alternative solution
i) parallel reactions
E1
A P desired product
E2
AC undesired product

where (E1< E2), P desired product and C

unwanted product
The optimum temperature for the
maximum desirable product is obtained
when E2
T  R
 
ln A2 F 
E2
- 1
  E1 
From the equation
Lowest temperature and high  F rate gives higher
selectivity for desire product

a) If  F is of no concern, use the lowest

allowable temperature and with larger
space time to favor the production P.
This is best carried out in mixed
reactor, CSTR.
 b) when a temperature progression is
permitted to carry out in PFR, for a
given,  F still it is better to use a rising
temperature progression than the best
i.e isothermal optimum.
High temperature and  F low
these conflicting factors can be reduced
by using an economic balance to use
the appropriate temperature and size of
a reactor
ii) For the consecutive reaction
E1 E2
A  P  C
where (E1< E2), P is desired product and C is
unwanted product
 a) when  F is no concern use the
R lowest allowable temperature
T
C S with the proper reactor size,  F to
se
U maximize the desired product P
b) If a temperature progression is
permitted to use PFR, then a
falling temperature progression is
better than to use isothermal
operation
Generally, for the series reaction, high
intermediate product is obtained by using PFR,
and the end product is obtained by increasing
temperature, which leads to increase both k1 and
k.