UNRI Chemical Engineering Department

Steady State NonIsothermal Reactor Design

Edy Saputra (PhD)
UNRI Chemical Engineering Department Rationale

• All reactions always accompanied by heat effect: exothermic

reactions vs. endothermic reactions
• Unless heat transfer system is carefully designed, reaction mass
temperature tend to change
• Design of heat transfer system itself requires the understanding of
this heat effect
• Energy balance is also needed, together with performance equations
derived from mass balance
UNRI Chemical Engineering Department Objectives

• Describe the algorithm for CSTRs, PFRs, and PBRs that are not operated
isothermally.
• Size adiabatic and nonadiabatic CSTRs, PFRs, and PBRs.
• Use reactor staging to obtain high conversions for highly exothermic reversible
reactions.
• Carry out an analysis to determine the Multiple Steady States (MSS) in a CSTR
along with the ignition and extinction temperatures.
• Analyze multiple reactions carried out in CSTRs, PFRs, and PBRs which are not
operated isothermally in order to determine the concentrations and temperature
as a function of position (PFR/PBR) and operating variables
 Why Do We Need Energy Balance ?
UNRI Chemical Engineering Department

The reaction A  B conversion is 70 %, Calculate the volume reactor. The reaction is exothermic and the
reactor is operate adiabatically. As a result the temperature will increase with conversion down the length of
the reactor
 Why Do We Need Energy Balance ?
UNRI Chemical Engineering Department

L X
dX
V  FAo 
0
 rA

L=0 L=L  Ea  1  1 
X=0 X = XL k 2  k1  exp     
T 
T = T0 T = Tx  R  T1  

We need to relate X and T  Energy Balance Equation

 General Form of Energy Balance
UNRI Chemical Engineering Department

Rate of flow Rate of work Rate of energy Rate of energy Rate of

of heat to the done by the added to the leaving the accumulation
system from
– system on + system by – system by = of the energy
the the mass flow into mass flow out within the
surrounding surroundings the system of the system system

W s

Fin Ein Control Volume Fout Eout

Q

dEˆ
Q  W  Fin Ein  Fout Eout 
dt
UNRI Chemical Engineering Department General Form of Energy Balance (for multi component system)

W s
F1 , E1
F1 , E1
F2 , E2
F2 , E2
...
...
Fn , En Q Fn , En

n n
dEˆ
Q  W  F E
i 1
i i in  F E
i 1
i i out 
dt

Next, we will evaluate the “W” and “E” terms

UNRI Chemical Engineering Department

Understanding Work and Energy

Terms in the EB equation
UNRI Chemical Engineering Department Evaluation of the Work (W) term
W s
F1 , E1
F1 , E1
F2 , E2
F2 , E2
...
...
Fn , En Q Fn , En

In a chemically reacting systems, there are usually two types of work that need
to be accounted for – (i) Shaft Work (e.g. work done by impellers in a CSTR
and batch reactor) and (ii) Flow Work
Rate of flow work is rate of work to
W  W s  Rate of Flow Work get mass into and out of the system

n n
Rate of Flow Work    F PVˆ
i 1
i i in   F PVˆ
i 1
i i
out
UNRI Chemical Engineering Department Evaluation of the E term
W s
F1 , E1
F1 , E1
F2 , E2
F2 , E2
...
...
Fn , En Q Fn , En

u 2i Energy Ei is the sum of internal, kinetic, potential

Ei  U i   g z  ... and any other type of energies.
2

For a majority of reactors, only internal energy is important

 Ei  U i
UNRI Chemical Engineering Department General Form of Energy Balance (for multi component system)

W s
F1 , E1
F1 , E1
F2 , E2
F2 , E2
...
...
Fn , En Q Fn , En

n n
dEˆ
Q  W  F E
i 1
i i in  F E
i 1
i i out 
dt
 Energy Balance Equation in terms of Enthalpy
dEˆ
UNRI Chemical Engineering Department
n n
Q  W  F E
i 1
i i in  F Ei 1
i i out 
dt
Substituting appropriate values of Ei and Rate of Work
n n n n
dEˆ
Q  W s   F PV
i 1
i i in   F PV
i 1
i i out  FU
i 1
i i in  FU
i 1
i i out 
dt

Now, H  U  PV

We now have, Energy Balance Equation in terms of Enthalpy

n n
dEˆ
Q  W s  F H
i 1
i i in  FH
i 1
i i out 
dt

Next, we will focus on the enthalpy terms

UNRI Chemical Engineering Department Here’s what we’ll do with Enthalpy terms

• Express Hi in terms of Enthalpy of Formation (Hio )

and Heat Capacity (Cpi)
• Express Fi in terms of conversion (for single
reaction) or rates of reaction
• Define Heat of Reaction (HRxn)
• Define  Cp
 Enthalpy Relationships: Single Reaction System
FA0 , H A0 FA , H A
UNRI Chemical Engineering Department

FB 0 , H B 0 T0 b c d T FB , H B
A B  C  D
... a a a ...
FI 0 , H I 0 FI , H I

If A is the limiting reactant

n
FA  FA0 (1  X )
n
In  H i0 Fi 0 Out  H F
i 1
i i
b
i 1
FB  FA0 ( B  X)
H A0 FA 0 H A FA a
c
H B 0 FB 0 H B FB FC  FA0 ( C  X )
a
H C 0 FC 0 H C FC d
Fd  FA0 ( D  X)
H D 0 FD 0 H D FD a
H I 0 FI 0 H I FI FI  FA0 ( I )  FI 0

Fi in terms of FA0 and X

from stoichiometry
UNRI Chemical Engineering Department Enthalpy Relationships: Single Reaction System
n n

F
i 1
i0 H i 0 (T0 )   F H (T )
i 1
i i

 FA0 {[ H A0 (T0 )  H A (T )]   B [ H B 0 (T0 )  H B (T )]

  C [ H C 0 (T0 )  H C (T )]   D [ H D 0 (T0 )  H D (T )]   I [ H I 0 (T0 )  H I (T )]}

d c b
[ H D (T )  H C (T )  H B (T )  H A (T )]FA0  X
a a a
HRxn

n n
 n 
 Fi0 H i0 (T0 )   Fi H i (T )  FA 0  i  [ H i0 (T0 )  H i (T )]  FA0  X  [ H Rxn ] 
i 1 i 1  i 1 
 Expressing Hi(T) in terms of Hio and Cpi
n n
 n 
  A 0  i    FA0  X  [ H Rxn ] 
UNRI Chemical Engineering Department
Fi0 H i0 (T0 )  Fi H i (T )  F [ H i0 (T0 )  H i (T )]
i 1 i 1  i 1 

Enthalpy at any given temperature is related to enthalpy at a reference

temperature and heat capacity
T
H i (T )  H io (Tref )  C
T Tref
pi dT

H io (Tref )  Heat of formation of species " i" at Tref For no phase change

Hi is available from
Chemical Engg handbook
T0
Therefore, H i 0 (T0 )  H i (T )   Cpi dT
T

T0

  H (T0 )  H i (T )   i  Cpi dT
n
And, i i0
i 1 T
UNRI Chemical Engineering Department Heat of Reaction (HRxn)
n n
 n 
 Fi0 H i0 (T0 )   Fi H i (T )  FA 0  i  [ H i0 (T0 )  H i (T )]  FA0  X  [ H Rxn ] 
i 1 i 1  i 1 

Heat of reaction is defined as:

d c b
H Rxn (T )  [ H D (T )  H C (T )  H B (T )  H A (T )]
a a a

Enthalpy at any given temperature is:

T
H i (T )  H io (Tref )  C
T Tref
pi dT


T
H Rxn (T )  H Rxn (Tref )   Cp dT
o
T Tref

d c b
where, Cp  a CpD  a CpC  a CpB  Cp A
 Energy Balance Equation in terms of Conversion

n
Q  W s  FA0   i  C pi  (T  Ti 0 )  FA0  X  H Rx (TR )  Cˆ p  T  TR   0
UNRI Chemical Engineering Department
o

i 1

For adiabatic reactions: Q  0

When work is negligible: W s 0

The energy balance at steady state becomes:

 
n
 FA0   i  Cpi  (T  Ti0 )  FA0  X  HoRx (TR )  Ĉp  T  TR   0
~
i 1

After rearrangement: n
~
 i pi  (T  Ti0 )
  C
i 1
X
 
H oRx (TR )  Ĉ p 
 T  TR 

This is the X=X(T) we’ve been looking for!

UNRI Chemical Engineering Department

Application: Heat Transfer (Q)

to/from Reactors
UNRI Chemical Engineering Department Application to Adiabatic CSTR Design
Case A: Sizing: X specified, calculate V (and T)
UNRI Chemical Engineering Department Application to Adiabatic CSTR Design
Case A: Sizing: X specified, calculate V (and T)

Performance equation: FA0  X

V
 rA
E  1 1 
Kinetics:  rA  k  CA k  k1  exp  a    
R  T1 T 

Stoichiometry: C A  C A0  (1  X)
n
~
FA0  X  i  C pi  (T  Ti 0 )
Combine: V X 
 
i 1

k  C A0  (1  X)  H (TR )  Cˆ p  T  TR 
o
Rx

Solve the energy balance for T

Calculate k
Calculate V using combining equation
 Application to Adiabatic CSTR Design
Case B (Rating): V specified, calculate X (and T)
UNRI Chemical Engineering Department

Performance equation: FA0  X

V
 rA
E  1 1 
Kinetics:  rA  k  CA k  k1  exp  a    
R  T1 T 

Stoichiometry: C A  C A0  (1  X)
n
~
FA0  X mb  i  C pi  (T  Ti 0 )
Combine: V X eb 
 
i 1

k  C A0  (1  X mb )  H (TR )  Cˆ p  T  TR 
o
Rx

Find X & T that satisfy BOTH the material balance and energy balance,
viz. plot Xmb vs T and Xeb vs T in the same graph: the intersection is the solution
 Application to Adiabatic CSTR Design
Problem: P85A
UNRI Chemical Engineering Department

The elementary irreversible organic liquid-phase reaction:

A+BC
is carried out adiabatically in a CSTR. An equal molar feed in A
and B enters at 27oC, and the volumetric flow rate is 2 L/s.

(a) Calculate the CSTR volume necessary to achieve 85%

conversion
(b) Calculate the conversion that can be achieved in one 500 L
CSTR and in two 250 L CSTRs in series