Reactor Design

S,S&L Chapter 7
Terry A. Ring
ChE
Reactor Types
Ideal
PFR
CSTR
Real
Unique design geometries and therefore RTD
Multiphase
Various regimes of momentum, mass and
heat transfer
Reactor Cost
Reactor is
PRF
Pressure vessel
CSTR
Storage tank with mixer
Pressure vessel
Hydrostatic head gives the pressure to design for
Reactor Cost
PFR
Reactor Volume (various L and D) from reactor
kinetics
hoop-stress formula for wall thickness:


t= vessel wall thickness, in.
P= design pressure difference between inside and outside of
vessel, psig
R= inside radius of steel vessel, in.
S= maximum allowable stress for the steel.
E= joint efficiency (0.9)
t
c
=corrosion allowance = 0.125 in.
c
t
P SE
PR
t +

=
6 . 0
Reactor Cost
Pressure Vessel Material of Construction
gives
metal

Mass of vessel =
metal
(V
C
+2V
Head
)
V
c
= DL
V
Head
from tables that are based upon D

C
p
= F
M
C
v
(W)
Reactors in Process Simulators
Stoichiometric Model
Specify reactant conversion and extents of
reaction for one or more reactions
Two Models for multiple phases in
chemical equilibrium
Kinetic model for a CSTR
Kinetic model for a PFR
Custom-made models (UDF)

Used in early stages of design
Kinetic Reactors - CSTR & PFR
Used to Size the Reactor
Used to determine the reactor dynamics
Reaction Kinetics




/) exp( ) (
) (
1
RT
E
k T k
C T k
dt
dC
r
A
o
C
i
i
j
j
i

=
= =
[
=
o
PFR no backmixing
Used to Size the Reactor



Space Time = Vol./Q
Outlet Conversion is used for flow sheet
mass and heat balances
}

=
k
X
k
ko
r
dX
F V
0
CSTR complete backmixing
Used to Size the Reactor



Outlet Conversion is used for flow sheet
mass and heat balances
k
k ko
r
X F
V

=
Review : Catalytic Reactors Brief Introduction
Major Steps
A B
A
Bulk Fluid
External Surface
of Catalyst Pellet
Catalyst
Surface
Internal Surface
of Catalyst Pellet
C
Ab
C
As

2. Defined by an
Effectiveness Factor

1. External Diffusion
Rate = k
C
(C
Ab
C
AS
)


3. Surface Adsorption
A + S <-> A.S

4. Surface Reaction
5. Surface Desorption
B. S <-> B + S
6 . Diffusion of products
from interior to pore
mouth
B
7 . Diffusion of products
from pore mouth to
bulk
Catalytic Reactors
Various Mechanisms depending on rate limiting step
Surface Reaction Limiting
Surface Adsorption Limiting
Surface Desorption Limiting
Combinations
Langmuir-Hinschelwood Mechanism (SR Limiting)
H
2
+ C
7
H
8
(T) CH
4
+ C
6
H
6
(B)



T B
H T
T
p p
p p k
r
04 . 1 39 . 1 1
2
+ +
=
Catalytic Reactors Implications on design
1. What effects do the particle diameter and the fluid velocity above the catalyst
surface play?
2. What is the effect of particle diameter on pore diffusion ?
3. How the surface adsorption and surface desorption influence the rate law?
4. Whether the surface reaction occurs by a single-site/dual site / reaction
between adsorbed molecule and molecular gas?
5. How does the reaction heat generated get dissipated by reactor design?


Enzyme Catalysis
Enzyme Kinetics



S= substrate (reactant)
E= Enzyme (catalyst)
O H S
S E O H
s
C k k C k
C C C k k
r
2
2
3 2 1
3 1
+ +
=
Problems
Managing Heat effects
Optimization
Make the most product from the least reactant
Optimization of Desired Product
Reaction Networks
Maximize yield,
moles of product formed per mole of reactant consumed
Maximize Selectivity
Number of moles of desired product formed per mole of
undesirable product formed
Maximum Attainable Region see discussion in Chapt. 7.
Reactors (pfrs &cstrs in series) and bypass
Reactor sequences
Which come first
Managing Heat Effects
Reaction Run Away
Exothermic
Reaction Dies
Endothermic

Preventing Explosions
Preventing Stalling
Temperature Effects
On Equilibrium
On Kinetics
Equilibrium Reactor-
Temperature Effects
Single Equilibrium
aA +bB rR + sS



a
i
activity of component I
Gas Phase, a
i
=
i
y
i
P,

i=
= fugacity coefficient of i
Liquid Phase, a
i
=
i
x
i
exp[V
i
(P-P
i
s
)

/RT]

i
= activity coefficient of i
V
i
=Partial Molar Volume of i
2
ln
, exp
RT
H
dT
K d
RT
G
a a
a a
K
o
rxn
eq
o
rxn
a
B
a
A
s
S
r
R
eq
A
=
|
|
.
|

\
|
(

A
= =
Vant Hoff eq.
Overview of CRE Aspects related to Process Design
1. Levenspiel , O. (1999), Chemical Reaction Engineering, John Wiley and Sons , 3
rd
ed.
Le Chateliers Principle
Unfavorable Equilibrium
Increasing Temperature Increases the
Rate
Equilibrium Limits Conversion
Overview of CRE Aspects related to Process Design
1. Levenspiel , O. (1999), Chemical Reaction Engineering, John Wiley and Sons , 3
rd
ed.
Feed Temperature, H
rxn
Heat Balance over Reactor
Cooling
Adiabatic
Adiabatic
Q = UA T
lm
Reactor with Heating or Cooling
Q = UA T

Kinetic Reactors - CSTR & PFR
Temperature Effects
Used to Size the Reactor
Used to determine the reactor dynamics
Reaction Kinetics




(

=
= =
[
=
RT
E
k T k
C T k
dt
dC
r
A
o
C
i
i
j
j
i
exp ) (
) (
1
o
PFR no backmixing
Used to Size the Reactor



Space Time = Vol./Q
Outlet Conversion is used for flow sheet
mass and heat balances
}

=
k
X
k
ko
r
dX
F V
0
CSTR complete backmixing
Used to Size the Reactor



Outlet Conversion is used for flow sheet
mass and heat balances
k
k ko
r
X F
V

=
Unfavorable Equilibrium
Increasing Temperature Increases the
Rate
Equilibrium Limits Conversion
Various Reactors, Various
Reactions
}

=
k
X
k
ko
r
dX
F V
0
k
k ko
r
X F
V

=
Reactor with Heating or Cooling
Q = UA T

Temperature Profiles in a
Reactor
Exothermic Reaction
Recycle
Best Temperature Path
Optimum Inlet Temperature
Exothermic Rxn
Managing Heat Effects
Reaction Run Away
Exothermic
Reaction Dies
Endothermic

Preventing Explosions
Preventing Stalling
Inter-stage Cooler
Exothermic Equilibria
Lowers Temp.
Inter-stage Cold Feed
Exothermic Equilibria
Lowers Temp
Lowers Conversion
Optimization of Desired Product
Reaction Networks
Maximize yield,
moles of product formed per mole of reactant consumed
Maximize Selectivity
Number of moles of desired product formed per mole of
undesirable product formed
Maximum Attainable Region see discussion in Chapt. 6.
Reactors and bypass
Reactor sequences
Reactor Design for Selective
Product Distribution
S,S&L Chapt. 7
Overview
Parallel Reactions
A+BR (desired)
AS
Series Reactions
ABC(desired)D
Independent Reactions
AB (desired)
CD+E
Series Parallel Reactions
A+BC+D
A+CE(desired)
Mixing, Temperature and Pressure Effects
Examples
Ethylene Oxide Synthesis
CH
2
=CH
2
+ 3O
2
2CO
2
+ 2H
2
O


CH
2
=CH
2
+ O
2
CH
2
-CH
2
(desired)

O
Examples
Diethanolamine Synthesis


N CH HOCH NH CH HOCH CH CH
O
desired NH CH HOCH NH CH HOCH CH CH
O
NH CH HOCH NH CH CH
O
3 2 2 2 2 2 2 2
\ /
2 2 2 2 2 2 2 2
\ /
2 2 2 3 2 2
\ /
) ( ) (
) ( ) (
+
+
+
Examples
Butadiene Synthesis, C
4
H
6
,

from Ethanol

O H H C CHO CH H C
H CHO CH OH H C
O H H C OH H C
2 6 4 3 4 2
2 3 5 2
2 4 2 5 2
+ +
+
+
Rate Selectivity
Parallel Reactions
A+BR (desired)
A+BS
Rate Selectivity

(
D
-
U
) >1 make C
A
as large as possible
(
D

U
)>1 make C
B
as large as possible

(k
D
/k
U
)= (k
oD
/k
oU
)exp[-(E
A-D
-E
A-U
)/(RT)]
E
A-D
> E
A-U
Tl
E
A-D
< E
A-U
T



) ( ) (
A
U
D
r
r
D/U
D
U
D
C
k
k
S
U D U
B
C
| | o o
(

= =
Reactor Design to Maximize
Desired Product for Parallel Rxns.
Maximize Desired Product
Series Reactions
AB(desired)CD
Plug Flow Reactor
Optimum Time in Reactor

Fractional Yield
O H CO O CHO CH
O H CHO CH O g OH CH CH
2 2 2 3
2 3 2 2 3
2 2
2
5
2
1
) (
+ +
+ +
(k
2
/k
1
)=f(T)
Real Reaction Systems
More complicated than either
Series Reactions
Parallel Reactions
Effects of equilibrium must be considered
Confounding heat effects
All have Reactor Design Implications
Engineering Tricks
Reactor types
Multiple Reactors
Mixtures of Reactors
Bypass
Recycle after Separation
Split Feed Points/ Multiple Feed Points
Diluents
Temperature Management with interstage
Cooling/Heating

A few words about simulators
Aspen
Kinetics
Must put in with
Aspen Units
Equilibrium constants
Must put in in the form
lnK=A+B/T+CT+DT
2

ProMax
Reactor type and
Kinetics must match!!
Kinetics
Selectable units
Equilibrium constants