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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

PR
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
rj

dC j
dt

k (T ) Ci i
i 1

EA
k (T ) ko exp(
/)
RT

PFR no backmixing
Used to Size the Reactor
Xk

dX
V Fko
rk
0

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

Bulk FluidCAb
1. External
Diffusion
Rate = kC(CAb
CAS)
External Surface
CAs
of Catalyst Pellet
2. Defined by an
Effectiveness
Factor
Internal
Surface
of Catalyst
3. Surface
Pellet
Adsorption
A + S <-> A.S
Catalyst
Surface

7 . Diffusion of
products
from pore
mouth to
bulk
6 . Diffusion of
products
from interior to
pore
mouth

A B
5. Surface Desorptio
4. Surface Reaction
B. S <-> B + S

Catalytic Reactors
Various Mechanisms depending on rate limiting step
Surface Reaction Limiting
Surface Adsorption Limiting
Surface Desorption Limiting
Combinations

Langmuir-Hinschelwood Mechanism
H2 + C7H8 (T) CH4 + C6H6(B)

rT

k pT p H 2
1 1.39 p B 1.04 pT

(SR Limiting)

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
rs

k1k3C H 2O C E C S
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 ReactorTemperature 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]

o
Grxn

a Rr aSs
K eq a a exp
,
a A aB
RT
i = activity coefficient of i
Vi =Partial Molar Volume of i

o
d ln K eq H rxn


2
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

Cooling

Heat Balance over Reactor

Q = UA Tlm

Adiabatic

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
rj

dC j
dt

k (T ) Cii

EA
k (T ) ko exp
RT

i 1

PFR no backmixing
Used to Size the Reactor
Xk

dX
V Fko
rk
0

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
V Fko
rk
k

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
O

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

Rate Selectivity

SD/U

rD
rU

k D ( D U ) ( D U )

CB
CA
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
EA-D < EA-U

T
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
Kinetics
Must put in with
Aspen Units

Equilibrium constants
Must put in in the form
lnK=A+B/T+CT+DT2

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

Equilibrium constants