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 ρmetal
– Mass of vessel = ρmetal (VC+2VHead)
• Vc = πDL
• 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

A B
Bulk Fluid CAb

1. External Diffusion 7 . Diffusion of products

Rate = kC(CAb – CAS) from pore mouth to
bulk

External Surface
CAs
of Catalyst Pellet
6 . Diffusion of products
2. Defined by an from interior to pore
Effectiveness Factor mouth
Internal Surface
of Catalyst Pellet
3. Surface Adsorption
A + S <-> A.S A B 5. Surface Desorption
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

k1k3CH 2OCE CS
rs  
k1CS  k2  k3CH 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 Chap’t. 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 Van’t Hoff eq.

aRr aSs   Grxn

o
  d ln K eq  H rxno
K eq  a a  exp  ,    2
a A aB  RT   dT  RT
– ai activity of component I
• Gas Phase, ai = φiyiP,
– φi== fugacity coefficient of i
• Liquid Phase, ai= γi xi exp[Vi (P-Pis) /RT]
– γi = activity coefficient of i
– Vi =Partial Molar Volume of i
Overview of CRE – Aspects related to Process Design

Le Chatelier’s Principle
1. Levenspiel , O. (1999), “Chemical Reaction Engineering”, John Wiley and Sons , 3rd 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, ΔHrxn

Adiabatic
Adiabatic
Cooling

Heat Balance over Reactor

Q = UA ΔTlm
Reactor with Heating or Cooling

Q = UA ΔT
 Kinetic Reactors - CSTR & PFR –
Temperature Effects
• Used to Size the Reactor
• Used to determine the reactor dynamics
• Reaction Kinetics

C
dC j
 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
 Unfavorable Equilibrium

• Increasing Temperature Increases the

Rate
• Equilibrium Limits Conversion
Various Reactors, Various
Reactions X k
dX
V  Fko 
0
 rk

Fko X k
V
 rk
Reactor with Heating or Cooling

Q = UA ΔT
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 Chap’t. 6.
• Reactors and bypass
• Reactor sequences
Reactor Design for Selective
Product Distribution
S,S&L Chapt. 7
 Overview
• Parallel Reactions
– A+BR (desired)
– AS
• Series Reactions
– ABC(desired)D
• Independent Reactions
– AB (desired)
– CD+E
• Series Parallel Reactions
– A+BC+D
– A+CE(desired)
• Mixing, Temperature and Pressure Effects
 Examples
• Ethylene Oxide Synthesis
• CH2=CH2 + 3O22CO2 + 2H2O

• CH2=CH2 + O2CH2-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+BR (desired)
– A+BS  k D  ( D U ) (  D  U )
• Rate Selectivity SD/U  rD
rU   CA CB
kU 
• (αD- αU) >1 make CA as large as possible
• (βD –βU)>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
– AB(desired)CD
• 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