CH 6602 – Chemical Reaction Engineering I

Dr. P. Senthil Kumar

Associate Professor
Department of Chemical Engineering
 Unit II

Design for continuous reactors,

Stirred tank and Tubular flow reactor,

Recycle reactors

Combination of reactors

Size comparison of reactors.
 Types of Reactors (Mode of Operations)

1. Batch reactor
2. Steady-state flow or Continuous flow reactor (PFR and MFR)
3. Unsteady-state flow or Semi-batch reactor

Batch reactor
Continuous flow reactor

Semi-batch reactor
Material balance for an element of volume of reactor
Energy balance for an element of volume of reactor
Symbolic representation of a flow reactor system
 Relationship b/w CA and XA

Case (1). Constant density batch and flow reactor

To relate changes in B and R aA + bB → rR

Case 2: Changing density batch and flow systems with T and P
constant
Case 3: Batch and flow systems for gases in general
(with changing ρ, T and P)
 Design for continuous reactors
1. Mixed Flow Reactor (MFR) – homogeneous liquid phase reaction
2. Plug Flow Reactor (PFR) – homogeneous gas phase reaction
 Design for continuous reactors
1. Mixed Flow Reactor (MFR) – homogeneous liquid phase reaction
2. Plug Flow Reactor (PFR) – homogeneous gas phase reaction
Mixed Flow Reactor (MFR)
Advantages
1. Easy to maintain good temperature control with this reactor
2. Possible to operate the reactor under isothermal conditions even
when the heat of reaction is high
3. Low cost of construction
4. Provides long residential time due its large volume – CSTR runs at
optimum temperature for long reaction times.
Disadvantages
1. The conversion of reactant per unit volume of reactor is small
2. Not recommended for high pressure operations because of cost
considerations.
3. Not suitable for reactions with very high heat effects due to
availability of a low area of heat transfer per unit volume.
4. Low heat transfer coefficients
Plug Flow Reactor (PFR)
Advantages
1. Easy maintenance (no moving parts)
2. Highest conversion per unit volume of reactor
3. Suitable for high pressure reactions because of cost consideration.
4. High heat transfer coefficients

Disadvantages
1. Difficult to control temperature within the reactor
2. Hot spots can occur with the exothermic reaction
Space time (τ)
It is the time necessary to process one reactor volume of feed at
specified conditions.
unit is time units.
V
τ=
υo
Space velocity (s)
It is the number of reactor volumes of feed at specified conditions
which can be treated in unit time.
1 υ o (FAo / C Ao ) FAo
s= = = =
τ V V C Ao V
 Steady-state Mixed Flow Reactor (MFR/CSTR)

A material balance of A over the reactor as a whole is

Input of A(moles/ time) , FAo = FAo (1 − X Ao ) = FAo

Output of A(moles/ time), FA = FAo (1 − X A )
Disappearance of A by reaction = (−rA )V
Substitutethe terms
FAo = FAo (1 − X A ) + (−rA )V
FAo = FAo − FAo X A + (−rA )V
FAo X A = (−rA )V
V XA ∆X A
= =
FAo (−rA ) (−rA )
V CAo τ X ∆X A
. = = A =
FAo CAo CAo (−rA ) (−rA )
continue...
V C Ao X A C Ao − C A
τ= = =
υo (−rA ) (−rA )
These performance equations are used to det er min e the
size of reactor required to achieve a given conversion
Example:
Consider first order reaction i.e. − rA = kC A
C Ao − C A
τ=
(−rA )
C Ao − C A
τ=
kC A
C Ao − C A
τk =
CA
in terms of conversion
C Ao X A
τ=
(−rA )
C Ao X A
τ=
kC A
C Ao X A
τk =
C Ao (1 − X A )
XA
τk =
(1 − X A )
Damkohler number (Da)
It is a dimensionless number that helps us to make a quick estimate
of the conversion that can be achieved in flow reactor
For first order reaction in MFR with εA = 0
XA
τk =
(1 − X A )
τk
XA =
1 + τk
For first order reaction τk = Da
Da
XA =
(1 + D a )
Significance of Da
(i). A high value of Da indicates high conversion and
(ii). Low value of Da indicates low conversion
For D a ≤ 0.1, X A < 10%
For D a ≥ 10, X A > 90%
For change in volume reaction systems and first order kinetics
V = Vo (1 + ε A X A )
C Ao (1 − X A )
CA =
(1 + ε A X A )
C Ao X A
τ=
− rA
C Ao X A
τ=
kC A
C Ao X A
kτ =
 C Ao (1 − X A ) 
 (1 + ε X ) 
 A A 
X A (1 + ε A X A )
kτ = for any ε A
(1 − X A )
Steady-state Plug Flow Reactor
For any component A, the material balance (on mole basis) over a
differential element of volume dV is

Substitute the terms

FA = (FA + dFA ) + (−rA )dV
− dFA = (−rA ) V
− d[FAo (1 − X A )] = ( −rA )dV
FAo dX A = (−rA )dV
FAodX A = ( −rA )dV
Re arranging the above eqn, int egrate and apply the lim its
V dV X Af dX A
∫ = ∫
0 FAo 0 ( −rA )
V X Af dX A
= ∫
FAo 0 ( −rA )
X Af dX A
V= FAo ∫
0 ( −rA )
V τ X Af dX
= = ∫ A
FAo C Ao 0 ( −rA )

V VC Ao X Af dX
τ= = = C Ao ∫ A
, for any ε A
υo FAo 0 ( −rA )
For partially converted feed

For partially converted feed,

τ V X Af
dX A
= = ∫
C Ao FAo X Ai (−rA )

X Af
V dX A
τ= = C Ao ∫
υo X Ai ( −rA )

int erms of concentration

τ V 1 C Af dC A
= =− ∫
C Ao FAo C Ao C Ao (−rA )

C Af
V dC A
τ= =− ∫ for ε A = 0
υo C Ao ( −rA )
Integrated performance equations for plug flow

1. Cons tan t volume system and first order reaction

− rA = kC A = kC Ao (1 − X A )
X Af
dX A
τ = C Ao ∫
0 (−rA )
X Af
dX A
τ = C Ao ∫
0 kC Ao (1 − X A )
kτ = − ln(1 − X A )

The above eqn is the performance eqn for plug flow

for first order reaction
2. Change in volume system and first order reaction
V = Vo (1 − X A )
C Ao (1 − X A )
CA =
1+ εA XA
X Af
dX A
τ = C Ao ∫
0 (−rA )
X Af
dX A
τ = C Ao ∫
0  kC Ao (1 − X A ) 
 1+ ε X 
 A A 
X Af
(1 + ε A X A )dX A
kτ = ∫
0 (1 − X A )
Use substitution method to solve
kτ = −(1 + ε A ) ln(1 − X A ) − ε A X A

The above eqn is the int egrated performance eqn for

first order reaction for change in volume systems
Distinction b/w holding time (t ) and space time (τ) for flow reactors

Space time Holding time

Time required to process one Mean residence time of flowing
reactor volume of feed material in the reactor or

it may be defined as the average

time the flowing material spent in
the reactor

V
(i). For constant density/volume system τ = =t
υo

(ii). For change in volume system τ≠t for ε A ≠ 0

 Problems
1. In an isothermal batch reactor the conversion of a liquid reactant
A is 70% in 13 min. Find the space time and space velocity
necessary to effect this conversion in a plug flow reactor and in
a mixed flow reactor. Consider first order kinetics
2. A gaseous feed with CAo=100, CBo=200 and CIo=100 enters a
steady-flow reactor in which the isothermal gas phase reaction
A+3B→ 6R takes place. Determine CB, XB, XA at the exit of the
reactor if CA at exit is 40.
3. A homogeneous liquid phase reaction with the stoichiometry
and the kinetics A → S, -rA = kCA2 takes place with 50%
conversion in a MFR.
(i). Find the conversion if this reactor is replaced by another
MFR having volume 6 times that of the original reactor – all else
remains unchanged.
(ii). Find the conversion if the original reactor is replaced by a
PFR of the same size – all else remains unchanged.
4. Assuming a stoichiometry A → R for a first order gas phase
reaction, the size of a PFR for 99% conversion of pure A is
calculated to be 32 liters. In fact, however, the stoichiometry
of the reaction A → 3R. For this corrected stoichiometry, find
the required volume of a reactor.
5. The saponification reaction
NaOH + CH3COOC2H5 → CH3COONa + C2H5OH
follows second order kinetics. A laboratory well-stirred tank
reactor is charged with an aqueous solution containing NaOH
and ethyl acetate, both of 0.1 molar (mol/l). After 15 min, the
conversion of ethyl acetate is 18%.
For the initial charge containing NaOH and ethyl acetate in
equal concentration of 0.2 molar, what time is required to
obtain a conversion of 30 % in a commercial batch reactor?
6. A homogeneous gas reaction A → 3R proceeds with
-rA = 0.1 CA, mol/l.s at 200 oC
Find the space time required to achieve 80 % conversion of a
50% inerts feed to a PFR operating at 200 oC and 5 atm
pressure. The initial concentration of A is 0.0625 mol/l.
7. The liquid phase reaction:
k1
A + B⇔R +S
k2
with k1 = 7 l/mol.min and k2 = 3 l/mol.min is to take place in a
steady-state MFR (V = 120 liter). Two feed streams, one
containing 1.4 mol A/l and the other containing 0.8 mol B/l, are
to be fed in equal volumes into the reactor. 75% conversion of
the limiting component is desired. What should be the flow
rate of each stream assuming a constant density throughout?
8. A specific enzyme acts as catalyst in the fermentation of substrate
A . At a given enzyme concentration in the aqueous feed stream of
25 l/min, determine the size of PFR needed to achieve 95 %
conversion of reactant A (CAo = 2 mol/l). The kinetics and
stoichiometry of fermentation reaction are given by
0.10 C A
A enzyme
 → R , − rA = mol /(l. min)
1 + 0.5 C A
9. It is proposed to operate a batch reactor for converting A into
R. This is a liquid phase reaction with stoichiometry A→R.
How long must we react batch in order to drop the
concentration from CAo =1.3 mol/l to CAf = 0.30 mol/l? The rate
v/s concentration data are given below:
CA, mol/l 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 1.0 1.3 2.0
-rA, 0.1 0.3 0.5 0.6 0.5 0.25 0.10 0.06 0.05 0.045 0.042
mol/(l.min)
 Recycle Reactor
Recycle reactors are used in the following situations, if
1. The reaction is autocatalytic
2. It is necessary to maintain nearly isothermal operation of the
reactor
3. It is necessary to promote a certain selectivity.
 Volume of fluid returned to the reactor inlet
Re cycle ratio ( R ) =
Volume of fluid leaving the system

R = 0 ( Plug flow behavior )

R = ∞ (Mixed flow behavior )
The performance eqn for PFR (partially converted feed )
X A2
V dX A
'
= ∫ ( −r ) (1)
FAo X A1 A

 A in an unconverted 
'
FAo = (A in fresh feed ) +  
 recycle stream 
'
FAo = FAo + R FAo
= ( R + 1) FAo ( 2)
1 − C A1 / C Ao
X A1 = (3)
(1 + ε A C A1 / C Ao )
For cons tan t pressure (change in volume )
FA1 FAo + FA 3 FAo + R FAo (1 − X Af )
C A1 = = =
υ1 υo + R υf υo + R υo (1 + ε A X Af )
 1 + R (1 − X Af )   1 + R − R X Af 
= C Ao   = C Ao   ( 4)
1 + R (1 + ε A X Af 
) 1 + R + R ε A X Af 
C A1  1 + R − R X Af 
=
C Ao 1 + R + R ε A X Af 
Substitute this value in eqn (3)
 1 + R − R X Af 
1− 
1 + R + R ε A X Af 
X A1 =
 1 + R − R X Af 
1 + εA  
1 + R + R ε A X Af 
R (1 + ε A )X Af
X A1 =
(1 + ε A ) + R (1 + ε A )
 R 
X A1 =   X Af ( 5)
 R + 1
'
Substitute FAo and X A1 in eqn (1)
( X Af )
V dX A
= ∫
FAo ( R + 1)  R  ( −rA )
 X
 R +1  Af
 ( X Af )
V dX A
= ( R + 1) ∫ , for any ε A ( 6)
FAo  ( −rA )
 R  X Af
 R +1 
The above eqn is the desired performance eqn for recycle
reactors applicable for any kinetics, any value of ε A and
for X A = 0

Performance eqn in terms of concentration (ε A = 0)

(C Af )
C Ao V dC A
τ= = −( R + 1) ∫ , for ε A = 0
FAo  C Ao + RC Af  ( −rA )
 
 R +1 
 ( X Af )
V dX A
= ( R + 1) ∫ , for any ε A (1)
FAo  ( −rA )
 R  X Af
 R +1 
For R = 0, the above eqn (1) becomes
X Af
V dX A
= ∫ ( PFR eqn )
FAo 0 ( −rA )
For R = ∞, the above eqn (1) becomes
V X
= Af (MFR eqn )
FAo ( −rA )

For first order reaction (ε A = 0) the int egrated form of performance eqn is
kτ  C + RC Af 
= ln  Ao 
R +1  ( R + 1) C Af 
For sec ond order reaction, 2 A → Pr oducts (ε A = 0) the int egrated form of
performance eqn is
k τC Ao  C Ao (C Ao − C Af ) 
= 
R +1  Af Ao
C ( C + RC Af 
)
Autocatalytic Reactions
PFR versus MFR, No recycle
 Optimum Recycle Operations
( X Af )
V τ dX A
= = ( R + 1) ∫ , for any ε A (1)
FAo C Ao  R  ( −rA )
 X
 R +1  Af
The optimum recycle ratio is obtained by differentiating eqn (1) w .r .to
 d( V / FAo ) 
R and setting  =0
 dR 
This operation requires differentiating under an int egral sign
b (R)
F( R ) = ∫ f ( x, R ) dx ( 2)
a (R)

From the theorem of calculus is

dF b ( R ) ∂f ( x, R ) db da
= ∫ dx + f (b, R ) − f (a, R ) (3)
dR a ( R ) ∂R dr dR
For our case
d( τ / C Ao ) X Af
dX A R +1 dX Ai
=0= ∫ +0−
dR X Ai ( − rA ) ( −rA ) dR
X Ai

where
dX Ai X Af   R  
= Q X =   X Af 
 R + 1
Ai
dR ( R + 1) 2  
Combining and rearranging then gives for the optimum
X Af
dX A
∫ ( −r )
1 X Ai A
=
( −rA ) X ( X Af − X Ai )
Ai
 Examples of Autocatalytic Reactions

1. Fermentation reactions which involve the action of microorganism

on an organic feed.
2. Combustion of fuel gas occurring in an adiabatic manner with a
feed consisting of cool reactants to the system (autothermal
reactions)
3. Haloform reaction
4. Tin pest
5. Reaction of Permanganate with Oxalic acid
6. Vinegar syndrome
7. Binding of oxygen by hemoglobin
8. α- bromination of acetophenone with bromine
9. Spontaneous degradation of aspirin into salicylic acid and acetic
acid
Reactor Combinations for Autocatalytic Reactions
 Problems
1. A first-order liquid phase reaction resulting in 92%
conversion, is occurring in a MFR. It has been suggested that
a fraction of the product stream, without any additional
treatment, be recycled. If the feed rate remains unchanged,
how would this affect conversion?
2. At present conversion is 66.67% for the elementary secondary
liquid phase reaction 2A → 2R when operating in an
isothermal PFR with a recycle ratio of unity. Determine the
conversion if the recycle stream is shut off.
 Design of reactors for single reactions

Factors to be considered for the reactor selection

1. Type of reaction
2. Scale of production
3. Cost of equipment and operation
4. Stability and flexibility of operation
5. Equipment life
6. Time period over which product is to be manufactured
7. Ease of convertibility of equipment to modified operating conditions
or to new unit processes
8. Safety
 Size comparison of single reactors

Comparison of MFR and PFR

The rate eqn for n th order reaction is
− rA = kCnA
For MFR , the performance eqn is
C Ao X A C Ao X A
τm = =
− rA kCnA
C Ao (1 − X A )
put C A =
1 + εA XA
C Ao X A (1 + ε A X A )n
τm =
kCnAo (1 − X A )n
 CnAo V  X A (1 + ε A X A )n
τm .CnAo−1 =   =
 ....(1)
 FAo  m k (1 − X A )n
For PFR , the performanc e eqn is
X A dX
τp = C Ao ∫ A
0 ( −r )
A

XA dX A X A (1 + ε X ) n
τp = C Ao ∫ = C ∫
A A
dX A
Ao (1 − X A )
n Ao n n
0 kC A 0 kC

 C n
V  1 X A (1 + ε X ) n
τp CnAo−1 =  Ao  = ∫ A A
dX A ........( 2)
 FAo  p k 0 (1 − X A )
n

Eqn (1) / Eqn ( 2)

(τ.C )
n −1
Ao m (CnAo V / FAo )m (X A (1 + ε A X A )n /(1 − X A )n )
= n =
(τ.C )
n −1
Ao p (C Ao V / FAo )p X A (1 + ε X ) n
∫
A A
dX A
(3)

0 (1 − X A ) n

For cons tan t volume system , ε = 0, the above eqn int egrates to
(τ.C )
n −1
Ao m
=
[X A /(1 − X A ) n
]m , n ≠1
(τ.C )
n −1
Ao p  (1 − X A )n −1 − 1
 n −1 
 p
For first order reaction with ε A = 0, n = 1 and thus eqn ( 3) becomes
(τ.C )
n −1
=
τm [X A /(1 − X A )]m
=
(τ.C )
Ao m
( 4)
n −1
Ao p τp [− ln (1 − X A )]p
For sec ond order reaction and thus eqn ( 3) becomes
(τ.C ) = [X
n −1
/(1 − X ) ]
2

(τ.C ) [X
Ao m A A m
( 5)
A / (1 − X A )]p
n −1
Ao p
 Multiple-Reactor Systems
PFR in series and/or in parallel

For ' i' th reactor

Xi
Vi dX A
= ∫
Fo Xi −1 ( −rA )
For the N reactors in series
V N Vi V1 + V2 + .......... + VN
=∑ =
Fo i =1 Fo Fo
X1 XN
dX A X 2 dX A dX A
= ∫ + ∫ + ... + ∫
X0=0 ( −rA ) X1 ( − rA ) X N −1 ( −rA )
XN
dX A
= ∫
X 0 ( −rA )
 Equal sized MFR in series

Material balance for component A about vessel ' i' gives

τ i ( X i − X i −−11 )
=
Co − rAi
Consider n = 1 with ε = 0
τ i (1 − C i / Co ) − (1 − C i −1 / C o )
=
Co k Ci
C i −1 − C i
τi =
k Ci
C i −1
= 1 + k τi
Ci
For cons tan t volume system τ = t in all the equal − size reactors
of volume Vi
Co 1 C C C
= = o . 1 ... N −1 = (1 + k τ i ) N
CN 1 − XN C1 C 2 CN
Re arranging we find for the system as a whole
 1 
N  Co  N 
τ Nreactors = N.τ i =   − 1
k  C N  
 
for N → ∞, this eqn reduces to PFR eqn
1  Co 
τp = ln 
k C
Unequal-size CSTRs/Different-size CSTRs in series

We may write for component A in the first reactor

V1 Co − C1
τ1 = t = =
υ ( −r )1
1 ( −r )1
− =
τ1 C1 − C o
For ' i' th reactor
1 ( −r ) i
− =
τ i C i − C i −1
Determining the best system for a given conversion
 Maximization of Rectangles
1. construct a rec tan gle b / w the x − y axes and touching the
arbitrary curve at po int M( x, y )
2. The area of the rec tan gle then, A = xy
3. This area is max imized when dA = 0 = y .dx + x.dy
dy y
or − =
dx x
For n = 1 : equal − size reactors are best
For n > 1 : smaller reactor should come first
For n < 1 : l arg er reactor should come first
Reactors of different size in series
 CSTRs in parallel

X A1 = X A 2 ... = X An
− rA1 = −rA 2 ... = −rAn
V
Vi =
N
V = V1 + V2 + ... + Vn
V = N Vi
FAo
FAoi =
N

XA
V = FAo
( − rA )
 PFR in series

V N V V1 + V2 + .... + VN
=∑ i
=
FAo i =1 Fo Fo

XN
V X1 dX X2 dX dX XN dX
=∫ +∫ + ....+ ∫ = ∫
FAo 0 − r X1 − r XN−1 − r 0 − rA
 PFRs in parallel

V X 2 dX
For branch (1) = ∫ (Q V = V1 + V2 )
Fo1 0 −r

X3
V3 dX V V
For branch ( 2 ) = ∫ = 3
0 − r
Fo 2 Fo1 Fo 2
Fo = Fo1 + Fo 2
 Problems

1. The elementary liquid phase reaction A+B→R+S is carried out

in a PFR. For equimolar amounts of A and B (CAo=CBo= 0.9
mol/l), 94% conversion is achieved in it. If a CSTR, 10 times as
large as the PFR, were arranged in series with the existing
unit, which unit needs to be arranged first (in series) to
enhance the production rate?
2. The kinetics of the liquid phase decomposition of A is studied
in two MFR in series the second unit having twice the volume
of the first one. At steady-state with a feed containing 1 mol
A/l and mean residence time of 96 seconds in the first reactor,
the concentration of A in the first reactor is 0.5 mol/l and in
the second is 0.25 mol/l. Find the kinetic equation for the
decomposition of A.
3. A liquid reactant stream with CAo = 1 mol/l passes through two
MFR in series. The concentration of A in the exit stream from
the first reactor is 0.5 mol/l. Find the concentration of A in the
exit stream of the second order. The reaction A→R follows
second order kinetics and V2/V1 = 2.
4. An aqueous reactant stream with CAo = 4 mol/l passes through
a MFR followed by PFR. Find the concentration at the exit of
the PFR if the concentration of A in the MFR is 1 mol/l. The
reaction is second order with respect to A. The volume of the
PFR is three times that of MFR.
5. The elementary irreversible liquid phase reaction A+B→R+S
takes place in a PFR using equimolar amounts of A & B.
Conversion is 96% and CAo = CBo =1 mol/l. If MFR ten times as
large as PFR were placed in series with the existing reactor,
which reactor should come first and by what fraction could
production be increased for that set-up?
6. The elementary liquid phase reaction A+B→ Products with
–rA= 500 (l/mol.min) CA.CB, mol/(l.min) is carried out in an
experimental tubular reactor under the following conditions:
volume of reactor = 0.1 litre, volumetric flow rate = 0.05 l/min.
Concentrations of reactants in feed: CAo=CBo= 0.01 mol/l
(i). Find the fractional conversion of reactants that can be
obtained?
(ii). For the same conversion as in part (i), find the size of MFR
needed
(iii). Find the conversion that can be expected in a MFR which
is equal in size to the PFR.
7. The elementary irreversible reaction aqueous phase reaction
A+B→R+S is carried out isothermally. Equal volumetric flow
rates of two liquid streams are fed into a 4 liter mixing tank.
One stream contains A with CAo = 0.020 mol/l and the other
contains B with CBo = 1400 mol/l. The mixed stream is then
passed through a 16 liter PFR. It is found that some R is
formed in the mixing tank, its concentration is 0.002 mol/l.
Assume that the mixing tank acts as a MFR. Find the
concentration of R at the exit of the PFR and the fraction of
initial A that has been converted in the system.
 8. For the reaction data given in the following table, consider a
series arrangement of a MFR and a PFR. If the intermediate
conversion is 70% and the final conversion is 80%, which
reactor should be placed first to obtain the smaller total
volume (of reactors in series)? FAo = 0.083 mol/s.

XA 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.85

-rA 0.0053 0.0052 0.0050 0.0045 0.0040 0.0033 0.0025 0.0018 0.0012 0.001
(mol/l.s) 5