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:
PR
t tc
SE 0.6 P

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)
tc=corrosion allowance = 0.125 in.
 Reactor Cost
Pressure Vessel Material of Construction
gives metal
Mass of vessel = metal (VC+2VHead)
Vc = DL
VHead from tables that are based upon D

Cp= FMCv(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 Used in early stages of design
Kinetic model for a PFR
Custom-made models (UDF)
Kinetic Reactors - CSTR & PFR
Used to Size the Reactor
Used to determine the reactor dynamics
Reaction Kinetics

dC j C
rj k (T ) Ci i
dt i 1

EA
k (T ) ko exp( /)
RT
 PFR no backmixing
Used to Size the Reactor
Xk
dX
V Fko
0
rk

Space Time = Vol./Q

Outlet Conversion is used for flow sheet
mass and heat balances
 CSTR complete backmixing
Used to Size the Reactor

Fko X k
V
rk
Outlet Conversion is used for flow sheet
mass and heat balances
 Review : Catalytic Reactors Brief Introduction
Major Steps

B
Bulk FluidCAb

1. External 7 . Diffusion of
Diffusion products
Rate = kC(CAb from pore
CAS) mouth to
External Surface bulk
CAs
of Catalyst Pellet
6 . Diffusion of
2. Defined by an products
Effectiveness from interior to
Factor
Internal pore
Surface mouth
of Catalyst
3. Surface
Pellet
Adsorption A B
A + S <-> A.S 5. Surface Desorptio
Catalyst 4. Surface Reaction
B. S <-> B + S
Surface
 Catalytic Reactors
Various Mechanisms depending on rate limiting step
Surface Reaction Limiting
Surface Adsorption Limiting
Surface Desorption Limiting
Combinations
Langmuir-Hinschelwood Mechanism (SR Limiting)
H2 + C7H8 (T) CH4 + C6H6(B)

k pT p H 2
rT
1 1.39 p B 1.04 pT
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

k1k3C H 2O C E C S
rs
k1C S k 2 k3C H 2O
S= substrate (reactant)
E= Enzyme (catalyst)
 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

ai activity of component I
Gas Phase, ai = iyiP,
Vant Hoff eq.
i== fugacity coefficient of i
Liquid Phase, ai= i xi exp[Vi (P-Pis) /RT]

a Rr aSs Grxn
o
d ln K eq H rxn o
i = activity coefficient of i
Vi =Partial Molar Volume of i

K eq a a exp , 2
a A aB RT dT RT
Overview of CRE Aspects related to Process
Design

Le Chateliers
Principle
1. Levenspiel , O. (1999), Chemical Reaction Engineering, John Wiley and Sons , 3 rd ed.
 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 , 3rd ed.
 Feed Temperature, Hrxn

Adiabatic
Adiabatic
Cooling

Heat Balance over Reactor

Q = UA Tlm
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

dC j C
rj k (T ) Cii
dt i 1

EA
k (T ) ko exp
RT
 PFR no backmixing
Used to Size the Reactor
Xk
dX
V Fko
0
rk

Space Time = Vol./Q

Outlet Conversion is used for flow sheet
mass and heat balances
 CSTR complete backmixing
Used to Size the Reactor

Fko X k
V
rk
Outlet Conversion is used for flow sheet
mass and heat balances
 Unfavorable Equilibrium

Increasing Temperature Increases the Rate

Equilibrium Limits Conversion
Various Reactors, Various
Reactions X
dX
k

V Fko
rk
0

Fko X k
V
rk
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

Lowers Temp.

Exothermic Equilibria
 Inter-stage Cold Feed

Lowers Temp
Lowers Conversion

Exothermic Equilibria
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
CH2=CH2 + 3O22CO2 + 2H2O

CH2=CH2 + O2CH2-CH2(desired)
 Examples
Diethanolamine Synthesis

/ O\
CH 2 CH 2 NH 3 HOCH 2CH 2 NH 2
/ O\
CH 2 CH 2 HOCH 2CH 2 NH 2 ( HOCH 2CH 2 ) 2 NH (desired )
/ O\
CH 2 CH 2 ( HOCH 2CH 2 ) 2 NH ( HOCH 2CH 2 ) 3 N
 Examples
Butadiene Synthesis, C4H6, from Ethanol

C2 H 5OH C2 H 4 H 2O
C2 H 5OH CH 3CHO H 2
C2 H 4 CH 3CHO C4 H 6 H 2O
 Rate Selectivity
Parallel Reactions
A+BR (desired)
A+BS k D ( D U ) ( D U )
Rate Selectivity
SD/U rD
rU CA CB
kU
(D- U) >1 make CA as large as possible
(D U)>1 make CB as large as possible

(kD/kU)= (koD/koU)exp[-(EA-D-EA-U)/(RT)]
EA-D > EA-U T
EA-D < EA-U T
 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
1
CH 3CH 2OH ( g ) O2 CH 3CHO H 2O
2
5
CH 3CHO O2 2CO2 2 H 2O
2

(k2/k1)=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 ProMax
Kinetics Reactor type and
Must put in with Kinetics must match!!
Aspen Units Kinetics
Equilibrium constants Selectable units
Must put in in the form Equilibrium constants
lnK=A+B/T+CT+DT2