Advanced Reaction Engineering

Non-Isothermal Reactor Design

Lecture -5

By Dr. Eng. Hundessa D. Demsash

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Energy Balance
Energy Balance, Rationale and Overview
Let’s calculate the volume necessary to achieve a
conversion, X, in a PFR for a first-order, exothermic and
adiabatic reaction.
The temperature profile might look something like this:
T k X

V V V
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Energy Balance, Rationale and Overview
Mole Balance:
dX  rA

dV FA0
 E  1 1 
Rate Law: rA  ki exp    C A
 R  T1 T 

Stoichiometry: C A  C A0 1  X 
 E  1 1 
ki exp   
dX  R  T1 T 
 C A 0 1  X 
Combine: dV FA0
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Energy Balance, Rationale and Overview

 E  1 1 
ki exp   
dX  R  T1 T 
 C A 0 1  X 
dV FA0

We cannot solve this equation because we don’t

have X either as a function of V or T.

We need another equation. That equation is:

The Energy Balance

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Mass Balance—Equation of Continuity

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Energy Balance
Reactor with no Spatial Variations

Reactor
Energy Balance
Reactor with no Spatial Variations
Q

Reactor

Rate of flow
of heat to the
system from
the
surroundings

Q
(J/s)
Energy Balance
Reactor with no Spatial Variations
Q W

Reactor

Rate of flow
Rate of work
of heat to the
system from - done by the
system on the
the
surroundings
surroundings

Q - W
(J/s) (J/s)
Energy Balance
Reactor with no Spatial Variations
Q W

Fin
Reactor
Ein

Rate of flow Rate of energy

Rate of work
of heat to the added to the
system from - done by the
system on the
+ system by
the mass flow into
surroundings
surroundings the system

Q - W + Fin Ein
(J/s) (J/s) (J/s)
Energy Balance
Reactor with no Spatial Variations
Q W

Fin Reactor Fout

Ein Eout

Rate of flow Rate of energy Rate of energy

Rate of work
of heat to the added to the leaving system
system from - done by the
system on the
+ system by - by mass flow
the mass flow into out of the
surroundings
surroundings the system system

Q W Fin Ein Fout Eout

- + -
(J/s) (J/s) (J/s) (J/s)
Energy Balance
Reactor with no Spatial Variations
Q W

Fin Fout
Reactor
Ein Eout

Rate of Rate of flow Rate of energy Rate of energy

Rate of work
accumulation of heat to the added to the leaving system
of energy = system from - done by the
system on the
+ system by - by mass flow
within the the mass flow into out of the
surroundings
system surroundings the system system
dEˆ sys
Q W Fin Ein Fout Eout
dt - + -
(J/s) = (J/s) (J/s) (J/s) (J/s)
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Energy Balance

Q
Fi in  Fi out
 
 e.g., FA 0    e.g., FA 
 
H i in  H i out

 e.g., H A 0   W S  e.g., H 
 A

Energy Balance on an open system: schematic.

dE system
  F E
Q  W
S i 0 i 0 in   Fi E i out  1
dt
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equation into a usable form.

1. Replace Ui by Ui=Hi-PVi
2. Express Hi in terms of heat capacities
3. Express Fi in terms of either conversion or rates
of reaction
4. Define ΔHRx
5. Define ΔCP
6. Manipulate so that the overall energy balance
is in terms of the User Friendly Equations.

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Intro to Heat Effects
Assumptions:
=0 =0
E i  U i  PE i  KEi Other energies small compared to internal
W  flow work  shaft work
~ ~  ~ m3 
flow work    Fi 0 P0 Vi 0   Fi PVi  V  
 mol 

Recall:
˜ i
H i  U i  PV 

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Intro to Heat Effects
Substituting for W&
& % % & dEsys
�Fi 0U i 0  �FU  �Fi 0 PV
i i Q  �
� 0 i0  �Fi PVi  WS �
� dt

Hi 0
6 44 7 4 48 6 4 7Hi 48
% % & & dEsys
�Fi 0 �
�U i 0  PV � �Fi �
0 i0 � �U i  PVi �
� Q  WS  dt

dEsys
�F i0 H i 0  �Fi H i  Q& W&S 
dt

Steady State: Q    F H  F H  0
 W
S i0 i0 i i
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Intro to Heat Effects

General Energy Balance :

   F H  F H 
 W dE system
Q S i0 i0 i i
dt

For Steady State Operation:

   F H  F H  0
 W
Q S i0 i0 i i

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Intro to Heat Effects

F i0 H i0  FA 0  i H i0

64D7H Rx48
�Fi H i  FA0 � i  ui X  H i  FA0 �i H i  FA0 X �ui H i

Q& W&S  FA0  �i  H i 0  H i   FA0 X DH Rx   0

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Intro to Heat Effects
For No Phase Changes
T
H i T   H TR 
0
i  TR
CPidT
Enthalpy of formation at temperature TR
Constant Heat Capacities
H i T   H i0 TR  CPi T  TR 

H i0  H i  CPi T  T0 

u H  u H  u C T  T 
i i i
0
i i Pi R

Heat of reaction at temperature T

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Enthalpies of change of
state
• Conversion of a substance from one state to another involves
heat input or output
• Heat is absorbed when breaking bonds
• Solid → liquid → gas
• Heat is released when making bonds
• Gas → liquid → solid
• Heat of fusion, vaporization etc. (formerly known as “latent”
heats – heat consumed with no change in T)
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 Intro to Heat Effects

u H  u H  u C T  T 
i i i
0
i i Pi R

ˆ  T  T 
DH R T   DHoR TR  DC 
P R

d ˆ c ˆ b ˆ
 i Pi
u ˆ
C  DCˆ
P 
a
C PD 
a
C PC 
a
C PB  ˆ
C PA

Substituting back into the Energy Balance

Q& W&S  FA0 X �

D H o
� R R  T   DCˆ  T  T  � F � C%  T  T   0
P R � A0 i Pi i0


Adiabatic (Q=0) and no Work (WS  0)
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Intro to Heat Effects

d c b
DH Rx  HD  HC  HB  HA
a a a

d c b
DC P  C PD  C PC  C PB  C PA
a a a

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 Intro to Heat Effects

Q& W&S  FA0  �i  H i 0  H i   FA0 X DH Rx   0

Substituting back into the Energy Balance

Q& W&S  FA0 X �

D H o
� R R  T   DCˆ  T  T  � F � C%  T  T   0
P R � A0 i Pi i0

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Adiabatic Energy Balance

Adiabatic (Q=0) and no Work (WS  0)

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Adiabatic Energy Balance

Adiabatic (Q=0) and no Work (WS  0)

T  T0 
 
X DH Ro  TR   DCˆ P  T  TR 
 T0 
X  DH R  T  
~ ~
T  i Pi
 C  X D Cˆ
P  i Pi
 C  X D ˆ
C P

This equation will be coupled with the

differential mole
balance

T0

X
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Example: Adiabatic PFR
A↔B
1) Mole Balance: dX   rA
dV FA 0

2) Rate Laws: � CB � �E �1 1 ��
rA   k �
CA  � k  k1 exp � �  � �
� k C � �R �T1 T �
�
DCP  0

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Example: Adiabatic PFR
A↔B
3) Stoichiometry:
C A  C A 0 1  X 

CB  CA0X
4) Energy Balance
 DH 0X X
T  T0 
 i CPi
First need to calculate the maximum conversion
which is at the adiabatic equilibrium conversion.
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Example: Adiabatic PFR
Example: Adiabatic PFR
A↔B  DH X0 X
T  T0 
iCPi
Xe Adiabatic equilibrium conversion
and temperature

T
KC
X eq 
1 KC 45
Example: Adiabatic PFR
We can now form a table. Set X, then calculate T, -V A,
and FA0/-rA, increment X, then plot FA0/-rA vs. X:

FA0/-rA

X 46
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