Chapter III

Designing Single and

Multiple-Reactor System
 Introduction
 Chemical kinetics and reactor design are at the heart of
producing almost all industrial chemicals.
 It is primarily a knowledge of chemical kinetics and reactor
design that distinguishes the chemical engineer from other
engineers.
 For example, if a reaction system produced a large amount
of undesirable product, subsequent purification and
separation of the desired product could make the entire
process economically unfeasible.
 Reaction-separation system producing
both desired and undesired products.
Efficiency of a reactor system.

 The selection of a reaction system that operates in the safest

and most efficient manner can be the key to the economic
success or failure of a chemical plant.
The chemical kinetic principles, in addition to the production of
chemicals, can be applied in areas such as living systems, waste
treatment, and air and water pollution.
Some of the examples and problems used to illustrate the
principles of chemical reaction engineering are:
 the use of wetlands to remove toxic chemicals from rivers,
 increasing the octane number of gasoline,
 the production of anti freeze starting from ethane,
 the manufacture of computer chips,
 and the application of enzyme kinetics to improve an
artificial kidney.
 Definition of Ideal Reactor Types
 A reactor is an apparatus or a structure in which
chemical, biological, and physical processes
(reactions) proceed intentionally, purposefully, and in
a controlled manner.
 In ideal reactors, the transport and mixing processes
can be described mathematically exactly; this is in
contrast to real, technical, built or natural reactors
which must be modeled, but where the transport
processes are only approximately known.
 Ideal reactors are a theoretical proxy or concept which is
analyzed instead of the real-world system to be simulated.
 Ideal reactors have three ideal contacting/flow patterns

Batch flow Mixed flow Plug flow

Uniform composition Uniformly mixed, same Fluid passes through the

everywhere in the reactor, composition everywhere, reactor with no mixing of
but composition changes within the reactor and at earlier and later entering fluid,
with time the exit. and with no overtaking .
Mass/ Mole balance on reactors
Rate of generation of Rate of flow of “J” Rate of
Rate of flow of “J” “J” by chemical rxn accumulation of “J”
out of the system
into the system with in the system with in the system
moles/time
moles/time moles/time moles/time

d N
F Jo  G J  F J

dt
J

Where:
G  rJ dv
J System Volume

G J F
F Jo
J
 Reactor Types
Batch reactor:
–has neither inflow nor outflow of reactants & products during process
F F Jo J
0
therefore, the general mole balance on species “J” is
dN J
 r dv
dt J

If reaction is perfectly mixed there is no variation in the rate of reaction throughout

reaction volume
, then
rJ = constant
dN J
 rJ V
dt
Q1- Write the mole balance for a reactant “A” in terms of reactor volume,
concentration and rate of formation for both constant volume and
constant pressure where “B” is in excess amount for the reaction.
A+B→C
Constant-volume batch reactor : The reactor is perfectly mixed
so that the concentration of the reacting species is spatially
uniform. Because the volume is constant we can take V inside
the differential and write the mole balance in terms of the
concentration of A:

Constant-pressure batch reactor. To write

the mole balance for this reactor in terms
of concentration, we again use the fact
that
Continuous –flow reactors (Back mix reactor)
• It is very commonly used in industrial processing
• It is normally run at steady state, and is usually operated so as to be
quite well mixed
Features
– Steady state
– Well mixed: have no spatial variation in concentration, temperature, or
reaction rate throughout the vessel
• Temperature and Concentration are identical everywhere with in the
reactor and they are the same with the exit point as they are elsewhere in
the tank.
• Where mixing is non-ideal a well mixed model is inadequate and other
models shall be thought as an option.
The mole balance in CSTR
 r J dV 
d N
F Jo F J

dt
J

For steady state , For well mixed

d N J
0 r J
dV r J V
dt
Then,
V

F Jo  r J V 
,F J
0

F FJ Jo
r J Design equation for CSTR
V
Tubular reactor
• It consists of a cylindrical pipe and is normally operated at
– steady state
–Turbulent flow
–No radial variation in concentration, temperature …
–Concentration changes /varies continuously in axial direction
through the reactor (reactants are consumed down through
the length)
* Consequently reaction rate as a function of conc. For all but
zero order reactions will also vary axially
Design equation for the PFR is given from the general mole balance
as follows:
d N
F  r  F  ----- *
J
Jo
dVJ J
V
dt

** PFR can be assumed as a series of very small CSTRs, where it is given as:
Then in spatially uniform sub volume ∆V,

V
r J dV r J V, for tubular reactor at
steady state
dN J 0 , then equation * becomes,
dt

F J
( y)  F J
for ∆V ----- **
( y  y )  r J V 0
∆V = A . ∆y ----- substituting this in to eq. **

F J ( y y) F ( y)

y
J
r J
A
This term resemble the derivative of a function, taking the limit as
∆y approaches to zero, we obtain
dF J
A r J dF J
r J
dy → dV

** Remark: the extent of reaction achieved in a plug flow reactor

doesn’t depend on its shape it only depends on its total volume
Isothermal reactor design

•Previous days
–Laboratory data → Pilot plant study
•But because of cost nowadays full scale plants are designed from lab /bench
scale units called micro-plants
•Design structure for isothermal reactors
Design of Batch Reactors
•Assumption
–Liquid phase rxn (density change is negligible)
–No inflow and outflow during process
–Completely mixed
Then mole balance is given by

1  dN A   dC A 
  r A  
V  dt 
 →  dt  r A
 

Since “CA” is measurable than “NA”

Then for irreversible 2nd order reaction where “A” is consumed

 dC A 2
k C A
2A→B , dt

Substituting the rate equation in the mole balance equation

1  1 1 
 t

k  CA 
C Ao 
Time needed to reduce the reactant conc. From an initial conc. “C AO” to specified “CA” in a batch
reactor.
Isothermal reactor cont…

Total cycle time = tf + te + tc + t

tf = filling and agitation time
te = emptying time
tc = cleaning time
t = reaction time
 Isothermal reactor cont…
Determining K from batch data
 Isothermal reactor cont…
Design of CSTRs
The design equation of a CSTR is given by F A
F Ao  F Ao
X
dF A  , considering
dV r A

The design equation can be written as V  F X Ao

r A

***Which gives a given volume V necessary to achieve a conversion X

or in terms of space time,

 Isothermal reactor cont…
For first order irreversible reaction the rate is given by:
r A
k C A

Combining the mole balance and the rate law

Solving for the effluent conc. CA

C A0
C A 1 k


where, substituting this in the above equation

k
X
1  k
k
Where, is referred as Da= Damkohler Number
 Isothermal reactor cont…
• For first and second order irreversible reactions the Damkohler
Number is given by

D k D a
k C Ao
a

• Knowledge of Da number helps to understand the extent of

conversion that can be achieved by a given volume reactor.
–A value of Da = 0.1 or less will usually give less than 10% conversion
whereas
– A value of Da = 10 or greater will usually give greater than 90%
conversion
 Isothermal reactor cont…

CSTR in Series
A first order rxn with no volume change is assumed to be carried out in two
CSTRs placed in series

Source: H. Scott Fogler , 2004

• The effluent conc. of A from reactor 1is given by:
C A0
C A1 1 

 1 k1
 Isothermal reactor cont…

From a material balance on reactor 2:

V  F A1
 F A2
 (C 0 A1
 C A2
)
• Solving for CA2
2
r A2 k C 2 A2

C
C A2 1  A1  (1 
 C Ao

2k2  k )(1  k )
2 2 1 1

• For “n” equal size CSTRs connected in series and operating at the same
temperature

  
1 2 3
....  n and k k k
1 2 3
.... k n

Then, the concentration and conversions leaving the last reactor is given by:
 Isothermal reactor cont…
C  C X 1 
1
C  A0 A0

(1k )
n
(1k ) (1 Da)
An n n

Source: H. Scott Fogler , 2004

 Isothermal reactor cont…

• Reading assignment
–CSTR in Parallel
–Example 4.2 on (H. Scott Fogler , 2004)
 Isothermal reactor cont…

• Stoichiometry in Volume change with reaction

– Most batch, and liquid phase, and some gas phase systems are categorized under the
systems at which the reaction volume or the volumetric flow rate do not vary.
– In a gaseous reactions where the number of moles of the reactants is not equal to the
number of resulting products there a molar flow rate will be changing as the reaction
proceeds for a gas phase reaction at a constant pressure and temperature. (Because
equal number of moles occupy equal volume)
N2 + 3H2  2NH3
– Other variable volume case which rarely happen is where volume changes with time
in a batch reactor.
– When volume changes concentration expressed by conversion density variation will
be considered.
 Isothermal reactor cont…
Expressing volume change as a function of conversion
• State equation for a gaseous system at any time “t” is
PV=ZNTRT -------------------- a
Where: T = temperature, K
P = total pressure, atm (kPa; 1 atm = 101.3 Wa)
Z = compressibility factor
R = gas constant
• at time t=0 it is expressed as
P0V0=Z0NT0RT0 -------------- b
• Dividing equation “a” with “b”
------------ --------------c
 Isothermal reactor cont…

For a reaction of b c d
A B C D
a a a
The stochiometric table is given by

d c b
   1 
a a a
Where:
 Isothermal reactor cont…
The total number of moles at any given time after the reaction started is given by:
dividing this by NTO then,

N
But from this equation  is given by T
1  N Ao
X 1   y X
N To N To
Ao

  y Ao

Then equation “c” becomes

------------------------- d
•This could further be simplified for low variation in Z, P & T
 Isothermal reactor cont…

Tubular Reactors
• Gas-phase reactions are carried out primarily in tubular reactors.
– Assumption:
The integral form of the plug flow design equation is given by
X
dX
V F Ao 
0
 rA
substituting the rate law for second–order reaction
X
dX 1 X
V F Ao  2 , where, C A C A 0 1  X )
 ( then
0  kCA


2

V F 
(1X
X ) dX
2
 k C (1 X )
Ao 2
0
A0
 Isothermal reactor cont…
Solving for the integral


2

 v
(1 ) X

2
V 0
[ 2 (1   ) ln(1  X )  X  ]
kC A0
(1  X )


2
v (1 ) X

2
L 0
[ 2 (1   ) ln(1  X )  X  ]
kC A A0 C
(1  X )
 Isothermal reactor cont…

Parameters used to
construct the graph
•k= 5 m3/mol.s
•CA0= 0.02 mol/m3
•Ac = 1 m2
•Ʋo= 1 m3/s
***For a fixed reactor length and identical
rate law parameters the reaction that
has a decrease in the total number of
moles will have the highest
Source: H. Scott Fogler , 2004 conversion at fixed temperature and
pressure.
Reading Assignment: Pressure drop in reactors
 Size comparison of Single reactors

• Batch reactor
– Advantages
• small instrumentation cost
• flexibility of operation
– Disadvantage
• high labor and handling cost
• considerable shutdown time to empty clean out, and refill
• poorer quality control of the product
• Therefore, batch reactor is well suited to produce small amounts of material and to
produce many different products from one piece of equipment
• For large amount of chemical process handling continuous system is more economical
 Size comparison …

• Design equations
Batch CSTR PFR
1  dN A 

V  dt 

  r A
dF A
 r A
dF A
r A
dV dV
N  dX A  F F dX 
   r  r F A
r
A0 A A0
V  dt 
 A
V A A0
dV A

For =0
 Size comparison …

Comparison of Batch and PFR

**Time required for a given reaction to achieve a given conversion in a batch and PF
reactors is similar but in a batch reactor tf+te+tc must also be considered.

Batch PFR
For =0
 Size comparison …

Mixed (CSTR) Vs PFR

• The ratio of sizes of mixed and plug flow reactors will depend on
– the extent of reaction,
– the stoichiometry, and
– the form of the rate equation
• For a simple nth order rate law
The mixed flow equation is given by:
--------- d
Whereas the plug flow is given by
------------ e
 Size comparison …

Dividing eqn. “d” by “e”

For constant density,  = 0 this will be reduced to

or
 Size comparison

Source: H. Scott Fogler , 2004

 Size comparison …

If the same quantities of feed are used to the system the ordinate becomes the
volume ratio V
or space-time ratio
m
 m

V p
 p

1. 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;
consequently, a proper representation of the flow becomes very important in
this range of conversion.
3. Density variation during reaction affects design; however, it is normally of
secondary importance compared to the difference in flow type.
 Multiple reactor system
PFR in series and/or in parallel
• consider N plug flow reactors connected in series, and let X1, X2, . . ., XN, be the
fractional conversion of component A leaving reactor 1, 2, . . . , N. Then the design
equation for the ith reactor is given as:

Then for “N” PFRs in series

***Therefore, N PFRs in series gives the same conversion as a single PFR with the same
volume as that of the total volume of the PFRs in series
 Multiple reactor system

• If many PFR systems that are connected in parallel and the inlet and outlet
compositions are the same then V or  must be the same for each
parallel line. F A0

Eg: The reactor setup shown below consists of three plug flow reactors in two parallel
branches. Branch D has a reactor of volume 50 liters followed by a reactor of volume 30
liters. Branch E has a reactor of volume 40 liters. What fraction of the feed should go to
branch D?

Source: O. Levenspiel , 1999 Page 125 Two-thirds of the feed must be fed to branch D
 Multiple reactor system
Equal sized mixed flow reactors (CSTR) in series
• In PF, the concentration of reactant decreases progressively through the system; in CSTR,
the concentration drops immediately to a low value. Therefore, PFR is more efficient than
CSTR for reactions whose rates increase with reactant concentration.

• Consider a system of N mixed flow reactors connected in series. Though the concentration
is uniform in each reactor, there is, nevertheless, a change in concentration as fluid moves
from reactor to reactor.

Source: O. Levenspiel , 1999 Page 126

 Multiple reactor system

Assume Density changes will be assumed to be negligible then, =0

then  t
For first order reaction
• a material balance for component A in vessel “i” is given by

------------------------------- f

• Since, =0 equation “f” can be written as

or
 Multiple reactor system

• Since the space time,  (or mean residence time “t”) is the same in all the equal
sized reactors of volume “Vi” then,

--------------- g

Rearranging this

-----------------h
when N→ ∞ equation “h” reduces to the plug flow equation
 Multiple reactor system
Graphical Presentation

Source: O. Levenspiel , 1999 Page 126

Reading Assignment:
•CSTR of same volumes in series for second order reaction rates
•CSTR of different volumes in series