Advanced Chemical Engineering Kinetics

(ChemE 7004)
Topic 5:
Steady-State Non-Isothermal Reactor Design

Prof. Wen-Yueh Yu ()
Catalysis and Surface Chemistry Lab
Department of Chemical Engineering
National Taiwan University
 Topic 5 | Page 01
Non-Isothermal Reactor:
An Example
Consider a non-isothermal reactor for a highly exothermal reaction
(A B) in an adiabatic liquid-phase plug-flow reactor (PFR). Find
the reactor volume required for a given conversion.

Mole Balance (Design equation)

Rate Law where

Stoichiometry
 Topic 5 | Page 02
Non-Isothermal Reactor:
An Example (contd)
Combination of rate law with stoichiometry

Combination with design equation

Energy Balance [for finding X(T) or V(T)],

e.g.,
 Topic 5 | Page 03
Energy Balance:
First Law of Thermodynamics
Energy Work done Energy from
accumulation by system mass flow out

Heat from Energy from

surroundings mass flow in

Work:
shaft work
(e.g., produced by stirrer in
flow work CSTR or turbine in PFR)
 Topic 5 | Page 04
Energy Balance:
First Law of Thermodynamics (contd)

For internal energy >> kinetic energy, potential energy

Enthalpy

or
 Topic 5 | Page 05
Energy Balance:
Examples of Equations
Adiabatic (Q = 0), no WS, and constant CP

Fi 0 Ci 00 Ci 0 y
i i0
FA0 C A00 C A0 y A0

CSTR with heat exchanger

U: overall heat-transfer coefficient

A: area

PFR with heat exchanger

 Topic 5 | Page 06
Energy Balance:
Heat of Reaction

steady state

Fi 0 Ci 00 Ci 0 y
i i0
FA0 C A00 C A0 y A0
 Topic 5 | Page 08
Energy Balance:
Enthalpies and Heat Capacity
 Topic 5 | Page 07
Heat of Reaction:
An Example
?

H oNH3 (298K) 11020 cal/mol

H oN 2 (298K) H oH 2 (298K) 0
H oRx (298K) 22040 cal/mol - N 2 reacted

C p 10.12 cal/mol - N 2 reacted

H Rx (423K) - 23.3 kcal/mol - N 2 reacted

- 7.8 kcal/mol - H 2 reacted
 Topic 5 | Page 09
Energy Balance:
A Brief Summary

steady state
 Topic 5 | Page 10
Adiabatic Operation -
Adiabatic Energy Balance

<<

Conversion based on energy balance (EB)

for adiabatic exothermic reaction
 Topic 5 | Page 11
Adiabatic Operation -
Adiabatic Tubular Reactor
Elementary reversible gas-phase reaction (see Table 8-2A)

Mole balance

Rate law

Arrhenius equation

Van't Hoff equation

Stoichiometry

Energy balance equation

Numerical method or ODE solver (Table 8-2B) or hand calculation (Example 8-3)
 Topic 5 | Page 12
Adiabatic Tubular Reactor:
Example 8.3
Liquid-phase isomerization of n-butane to i-butane
Set X = 0.2
 Topic 5 | Page 13
Adiabatic Tubular Reactor:
Example 8.3 (contd)
Liquid-phase isomerization of n-butane to i-butane
EBE AE VHE RL RL

Levenspiel plot

Reactor volume
(V)
Simpson's rule
 Topic 5 | Page 14
Adiabatic Tubular Reactor:
Example 8.3 (contd)
With ODE solver
 Topic 5 | Page 15
Adiabatic Operation:
Example 8.3 - PFR versus CSTR
Comparison of the reactor volume for CSTR and PFR for X = 0.4.
 Topic 5 | Page 16
Steady-State Tubular Reactor
With Heat Exchanger
c
m
Ta
FA0
T0 T

Variable Ta Variable Ta
Constant Ta Constant Ta Exothermic Exothermic
Exothermic Endothermic Counter-current Co-current
 Topic 5 | Page 17
Equilibrium Conversion (Xe)

Equilibrium conversion (Xe):

Highest conversion that can be achieved in reversible reactions.
Exothermic reactions:
KC Xe For first-order reaction

T T
at equilibrium
Endothermic reactions:
KC ~1
Xe

T T
 Topic 5 | Page 18
Equilibrium Conversion (Xe)
Adiabatically Exothermic Reactions

<<

X Energy
Equilibrium balance
T01 > T0
Energy
balance Xe (T01) < Xe (T01)
Xe
Tadiabatic (T01) >
Tadiabatic (T0)
T
T0 T01 TAdiabatic
 Topic 5 | Page 19
Equilibrium Conversion (Xe)
Adiabatically Exothermic Reactions: Example 8-6
The elementary solid-catalyzed liquid-phase reaction A B
 Adiabatically Exothermic Reactions Topic 5 | Page 20
Reactor Staging with Interstage Cooling
Increase Xe: (i) lower inlet temperature (slow kinetics); or
(ii) interstage cooling or heating (more investment)

(570, 0.9)
(700, 0.7)

(800, 0.4)
 Adiabatically Endothermic Reactions Topic 5 | Page 21
Reactor Staging with Interstage Heating
Exothermic reactions Endothermic reactions
X X
XEB XEB

T T

Why not isothermal:

the temperature control is
difficult or expensive.
Why not higher To:
T safe concerns.
Adiabatically Endothermic Reactions Topic 5 | Page 22
Optimum Feed Temperature
 Topic 5 | Page 23

CSTR with Heat Effects

and are negligible (or )

energy balance

mole balance
 Topic 5 | Page 24
CSTR with Heat Effects
(contd)

non-adiabatic operation
 Topic 5 | Page 25
Multiple Steady States
G(T) and R(T)

non-adiabatic operation

heat-generated term

heat-removed term

steady state = graphic intersection of G(T) and R(T)

 Topic 5 | Page 26
Heat-Removed Term

Vary entering temperature Vary Non-Adiabatic Parameter

slope =

increase T0
increase

?
 Topic 5 | Page 27
Heat-Generated Term

For 1st-order reaction

@ low T

@ high T
low E

increase
high E
 Topic 5 | Page 28
Ignition-Extinction Curve

graphic intersection of G(T) and R(T) = steady state operation

G(T): curve y (independent of entering temp.)

R(T): straight line a with T01 as entering temp.
b with T02 as entering temp.
Ts1: steady-state reactor temp. determined from T01
Ts2 and Ts3: steady-state reactor temp. determined
from T02
 Topic 5 | Page 29
Ignition-Extinction Curve
(contd)

Entering Stead-State
Temp. Reactor Temp.

a
b
c
d
e
f
 Topic 5 | Page 30
Ignition-Extinction Curve
(contd)
Ignition-Extinction Curve

T05: ignition temperature

T02: extinction temperature
 Topic 5 | Page 31
Ignition-Extinction Curve
(contd)
unstable

R(T), G(T)
T
stable

R(T), G(T)

T
 Topic 5 | Page 32
Ignition-Extinction Curve
(contd)

unsteady state: 5 and 8

upper steady state: 3-12
lower steady state: 2-10

[Note] just locally stable, not globally stable

 Topic 5 | Page 33
Runway Reactions in A CSTR

runaway
slope

At T*,
 Topic 5 | Page 34
Runway Reactions in A CSTR
(contd)

Irreversible reaction and C C(T) or zeroth order kinetics

 Topic 5 | Page 35
Runway Reactions in A CSTR
(contd)

If Trc > RT*2/E, transition to the upper steady state occur.

E/RT: typically 16-24

critical Trc: 15-30 oC
K: 300-500 K
 Topic 5 | Page 36
Runway Reactions in A CSTR
Stability Diagram

runaway