CHEE 321: Chemical Reaction Engineering

Module 1: Mole Balances, Conversion & Reactor Sizing

(Chapters 1 & 2, Fogler)
Module 1: Mole Balances, Conversion & Reactor Sizing

• Topics to be covered:
– Basic elements of reactor design, terminology/notation

– Development of general mole balance equation with

reaction
– Key characteristics and mole balance equations for common
industrial reactors (batch, CSTR, PFR, PBR)

– Reactor design for single-reaction systems

• Definition of conversion
• Levenspiel Plots
 Basic Elements of Reactor Design
• Reactor design usually involves the following:
– Knowledge of nature of reaction
• Catalytic or Non-Catalytic
• Homogeneous or Heterogeneous
• Reversible or Irreversible
– Selection of operating conditions
• Temperature, Pressure, Concentrations
• Type of catalyst (if applicable)
• Flow rates

– Selection of reactor type for a given application

– Estimation of reactor volume required to process given amount
(moles or molar rate) of raw material to desired amount of products
• How fast the reaction occurs (reaction rates) dictates how large the
reactor volume will be
 Our approach to reactor design
• Operation of most reactors are relatively complex
– Temperature is not uniform and/or constant
– Multiple reactions can occur
– Flow patterns are complex

• To gain an insight into basic concepts relevant to reactor

design, we will first consider simplified and/or ideal
reactor systems.

• Design of isothermal reactors involves solution of MOLE

BALANCE equation only
– In some cases, pressure drop must also be calculated

• Let us first familiarize ourselves with some common

terminology and notation that we will be using throughout
the course
Ethylene Æ Low Density Polyethylene Monomer
Feed

Initiator
Feed

- A multi-zone Autoclave is a vertical cylindrical

vessel with large L/D of 10-20. The reaction
mixture is intensely mixed by a stirrer shaft.

- Reactor is divided into separated reaction zones.

- Reactor (and each zone) is considered as well-

mixed CSTR in perfect mixing model approach.

- Imperfect mixing of initiator feed can occur due

to very fast initiator decomposition rate, despite
intense agitation
Reversible and Irreversible Reactions
Irreversible Reactions: Reactions that proceed uni-
directionally under the conditions of interest
CH4 + 2O2 Æ CO2+2H2O

Reversible Reactions: Reactions that proceed in both

forward and reverse directions under conditions of interest.
SO2 + 0.5 O2 ⇄ SO3

H2S⇄ H2 + 1/xSx

Thermodynamics tells us that all reactions are reversible.

However, in many cases the reactor is operated such that the
rate of the reverse reaction can be considered negligible.
Homogeneous & Heterogeneous Reactions
Homogeneous Reactions: reactions that occur in a
single-phase (gas or liquid)
NOx formation
NO (g) + 0.5 O2 (g) ↔ NO2 (g)
Ethylene Production
C2H6 (g) ↔ C2H4 (g) + H2 (g)

Heterogeneous Reactions: reactions that require the presence

of two distinct phases

Coal combustion
C (s) + O2 (g) ↔ CO2 (g)
SO3(for sulphuric acid production)
SO2 (g) + 1/2 O2 (g) ↔ SO3 (g) Vanadium catalyst (s)
 Material Balances: It all starts from here!
System with Rxn: use mole balances

Output Rate
Input Rate

Rate of INPUT – Rate of OUTPUT + Rate of GENERATION – Rate of CONSUMPTION

= Rate of ACCUMULATION

Note: Rates refer to molar rates (moles per unit time).

Before we get into the details of the mole balance equation, we must introduce
definition for reaction rate as well as associated notation.
Notation: Reaction Rate for Homogeneous Reactions

(– rA) = rate of consumption of species A (A is a reactant)

= moles of A consumed per unit volume per unit time
A+BÆC

(rA) = rate of formation of species A (A is a product)

DÆA

Units of (rA) or (– rA)

• moles per unit volume per unit time
• mol/L-s or kmol/m3-s
Notation: Reaction Rate for Heterogeneous Reactions

For a heterogeneous reaction, rate of consumption of species

A is denoted as (-rA')

Heterogeneous reactions of interest are primarily catalytic in

nature. Consequently, the rates are defined in term of mass of
catalyst present

Units of (-rA')
•mol per unit time per mass of catalyst
•mol/(g cat)-s or kmol/(kg cat)-h
 Reaction Rate and Rate Law
Reaction Rate
• Rate of reaction of a chemical species will depend on the local conditions
(concentration, temperature) in a chemical reactor

Rate Law
• Rate law is an algebraic equation (constitutive relationship) that relates reaction
rate to species concentrations.
• Rate law is independent of reactor type

(-rA) = k ·[concentration terms] Note: a more appropriate description

e.g. (-rA) = k CA or (-rA) = k CA2 of functionality should be in terms of
“activities” rather than concentration.
where, k is the rate coefficient [k=f(T)]

We’ll learn more about rate laws in Modules 2 and 4.

 General Mole Balance Equation (GMBE)

General mole balance equation is the foundation of reactor design.

Rate of INPUT – Rate of OUTPUT + Rate of GENERATION/CONSUMPTION =
Rate of ACCUMULATION

dN A
FA0 − FA + GA =
All terms
dt
with units FA
of mol/s
FA0
System volume V
GA = (rate of generation of A) · V
V
Need to integrate over
= ∫ rA dV ′ reactor volume, as reaction
conditions (T, CA ) may vary
If A is consumed, add a –ve sign with position
Common Reactor Types

• Batch Reactor

• Flow Reactors
– Continuous-Stirred Tank Reactor (CSTR)
– Plug Flow Reactor (PFR)
– Packed Bed Reactor (PBR)

• Other Reactor Types

– Semibatch Reactors
– Fluidized Bed Reactor, Trickle Bed Reactor, Membrane
Reactor, …
 Batch Reactor

Key Characteristics
• No inflow or outflow of material
• Unsteady-state operation (by definition)
• Mainly used to produce low-volume high-value
products (e.g., pharmaceuticals)
• Often used for product development
• Mainly (not exclusively) used for liquid-phase
reactions
• Charging (filling/heating the reactor) and clean-
out (emptying and cleaning) times can be large

For an ideal batch reactor, we assume no

spatial variation of concentration or temperature.
i.e.; lumped parameter system (well-mixed)
 General Mole Balance for an Batch Reactor
Input = Output = 0
V
dN A
= ∫ rA dV ′
dt
If well-mixed (no temperature or
concentration gradients in reactor):
differential form integral form
dN A dN A′
NA
= rAV ; t= ∫
dt rV
N A = N A0 at t = 0
N A0 A

Class exercise:
Derive concentration vs. t profiles for A and B for AÆB with rB=-rA=kCA
for a well-mixed constant-volume isothermal batch reactor.
At t=0, CA=CA0 and CB=0
 General Mole Balance for Ideal CSTR at Steady-State
FA0=v0CA0
CSTRs are also known as “back-
mix” reactors, as concentrations
in the outlet stream are the same
FA=vCA as concentrations in the reactor (a
consequence of being well-mixed)
NA=VCA

v0, v= volumetric flowrates (L/min, m3/s) of inlet and exit;

if at steady-state and constant density, v0 = v

Average residence or space time of fluid in vessel based on

inlet conditions τ = V/v0

Class exercise:
Derive expressions for concentration of A and B for AÆB with rB=-rA=kCA for
a well-mixed steady-state CSTR with inlet concentrations CA=CA0 and CB=0,
assuming no density change.
 General Mole Balance for Ideal CSTR at Steady-State
FA0=v0CA0
CSTRs are also known as “back-
mix” reactors, as concentrations
in the outlet stream are the same
FA=vCA as concentrations in the reactor (a
consequence of being well-mixed)
NA=VCA

v0, v= volumetric flowrates (L/min, m3/s) of inlet and exit;

if at steady-state and constant density, v0 = v

Average residence or space time of fluid in vessel based on

inlet conditions τ = V/v0

Class exercise:
Derive expressions for concentration of A and B for AÆB with rB=-rA=kCA for
a well-mixed steady-state CSTR with inlet concentrations CA=CA0 and CB=0,
assuming no density change.
 Class Problem

Calculating Reaction Rate in a CSTR

1.0 L/min of liquid containing A and B (CA0=0.10 mol/L, CB0=0.01 mol/L)
flow into a mixed flow reactor of volume 1.0 L. The materials in the reactor
interact (react) in a complex manner for which the stoichiometry is unknown.
The outlet stream from the reactor contains A, B and C at concentrations
of CA= 0.02 mol/L, CB=0.03 mol/L and CC=0.04 mol/L.

Find the rate of reactions of A, B and C at conditions of

the reactor.
 Plug Flow Reactor (PFR)

V
dN A
= FA0 − FA + ∫ rA dV ′
dt
Key Characteristics
• Generally a long cylindrical pipe with no moving parts (tubular reactor)
• Suitable for fast reactions (good heat removal), mainly used for gas phase
systems
• Concentrations vary along the length of the tube (axial direction)

For an ideal PFR, we assume:

- constant flowrate
- no variation of fluid velocity or species concentration in radial direction
We also generally assume reactor is operating at steady-state: i.e.; no variation in
properties with time at any position along reactor length
 General Mole Balance for Ideal PFR at Steady-State
integral form

dFA′
FA

Infinitesimally small V= ∫
control volume FA 0
rA
FA V ΔV FA V +ΔV

At steady state: FA V − FA V +ΔV + rA ΔV = 0 differential form

dFA
= rA ;
dV
FA = FA0 at V = 0

Class exercise:
Derive concentration profiles for A and B for AÆB with rB=-rA=kCA for a
isothermal PFR at steady-state, assuming constant volumetric flowrate.
At the reactor inlet, CA=CA0 and CB=0
 Packed Bed Reactor (PBR)

FA0 FA

Key Characteristics
• Can be thought of as PFR packed with solid particles, usually
some sort of catalyst material.
• Mainly used for gas phase catalytic reaction although examples for
liquid-phase reaction are also known.
• Pressure drop across the packed bed is an important consideration.
• This is the reactor type used in your integrated design project.
 Mole Balance for PBR
Let W = Weight of the packing
FA0 FA

Making the same assumptions as for a PFR:

- no variation of fluid velocity or species concentration in radial direction
- operating at steady-state

differential form integral form

dFA FA
dFA′
= rA′ ;
dW W= ∫ rA′
FA = FA0 at W = 0
FA 0

Same as PFR, but with rate (r ) specified per mass of

catalyst (instead of per unit volume) and using catalyst wt
(W) instead of V as the coordinate
 Summary - Design Equations of Ideal Reactors

Differential Algebraic Integral

Remarks
Equation Equation Equation
Conc. changes with time
dN j Nj
dN ′j
Batch = (rj )V but is uniform within the
(well-mixed) dt
t= ∫
N j0
(rj )V reactor. Reaction rate
varies with time.

Conc. inside reactor is

CSTR Fj 0 − Fj uniform. (rj) is constant.
(well-mixed V= Exit conc = conc inside
− ( rj ) reactor.
at steady-state)

PFR dF j
= rj dFj′
Fj
Concentration and hence
(steady-state flow;
well-mixed radially)
dV V= ∫ ( rj )
reaction rates vary
Fj 0 spatially (with length).
 Human Body as a System of Reactors
Food

Small Intestine
Mouth Large
Intestine
Stomach
What reactor type can we represent the various body parts with?

• We can often approximate behaviour of complex reactor

systems by considering combinations of these basic reactor
types (batch, PFR, CSTR)
• Next step (Fogler Ch 2):
¾Formulate design equations in terms of conversion
¾Apply to reactor sizing
 Approaches in modeling imperfect mixing in LDPE Autoclave Reactors
Flow of initiator and
side feed
Compartments model
V1
Each reaction zone is considered as a
Recycle
set of interconnected three CSTR’s.
flow

Flow from
V2
Recycle flow models the effect of
imperfect mixing in initiator
Monomer
previous zone injection point and backmixing in
the reaction space. The model
Feed
parameters are based on geometrical
V3 and flow dynamic of the industrial
system.
Initiator
Marini, L., Georgakis, C., AIChE J. 30, 401 (1984).
Feed
CSTR segment
Segments model

Feed Recycle to Each reaction zone is

previous zone considered as a CSTR
section followed by a plug
flow section. The plug flow is
Plug flow
considered as a series of
segment
CSTR’s in series due to
complex mathematical
difficulties. Recycle streams
show the effects of imperfect
mixing.

Recycle from
the next zone

Chan ,W., Gloor, P. E., & Hamielec, A. E.,

AIChE J. 39, 111 (19xx).
 Conversion (X) [Single Reaction System]
• Quantification of how far a reaction has progressed
Continuous (or Flow) Reactors Batch Reactors
mols of species-j reacted mols of species-j reacted
Xj = Xj =
mols of species-j fed mols of initial species-j
Fj 0 − Fj N j0 − N j
= =
Fj 0 N j0

• Defined in terms of limiting reactant

Reactants Æ Products aA + bB → cC + dD
b c d
Assume “A” is our limiting reactant A+ B → C+ D
a a a
 Design Equation in Terms of Conversion
(limiting reactant A)
IDEAL DIFFERENTIAL ALGEBRAIC INTEGRAL
REACTOR FORM FORM FORM

dX A′
XA

∫
dX A t = N A0
BATCH N A0 = (− rA )V
dt 0
− rAV

FA0 ( X A )
V=
CSTR (− rA )

dX A′
XA
dX A
PFR FA0
dV
= (− rA ) V = FA0 ∫
0
− rA
These equations can be used to size reactors
required to achieve a desired conversion for
a single-reaction system
Æ Levenspiel Plots (Fogler, Ch 2.4-2.5)

Octave Levenspiel
considered to be one of the
founders of Chemical Reaction
Engineering
 FA0
Basic idea: use plot of (− rA )
vs. X to calculate V

Plug Flow Reactor (PFR)

FA0 X PFR
FA0
(− rA ) VPFR = ∫
0
−rA
dX

X XPFR

Continuous Stirred Tank Reactor (CSTR)

FA0
FA0
(− rA ) VCSTR =[ ] ×[ X CSTR ]
(−rA )
Evaluated at X=XCSTR

X XCSTR
 Class Problem

The following reaction is to be carried out isothermally in a

continuous flow reactor operating at steady-state:

A→B

Compare the volumes of CSTR and PFR that are necessary to

consume 90% of A (i.e. CA=0.1 CA0). The entering molar and
volumetric flow rates are 5 mol/h and 0.5 L/h, respectively. The
reaction rate for the reaction follows a first-order rate law:
(-rA) = kCA where, k=0.0001 s-1
 For same conversion, is the CSTR volume
always higher than PFR volume ?

For most cases yes, provided that

rA decreases as X increases.
FA0
-rA See Fogler Section 2.4 (Ex. 2-2
to 2-4) for using Levenspiel plots
to size reactors (PFR vs. CSTR)

The real power of Levenspiel

plots is for reactor networks
(reactor in series)
 PFR in Series

FA0 FA1
FA2
X=0
X=X2
X=X1 FA3; X=X3

Let us compare two scenarios

(i) Single reactor achieving X3

FA0 (ii) 3 reactors in series achieving X3
-rA • How is the total volume of 3
reactors in series related to single
reactor ??

X
 CSTR in Series
See Fogler 2.5.1 Compare volume for the following 2 cases
FA0
(i) A single reactor achieving X3
X=0 (ii) 3 reactors in series achieving X3
FA1
X=X1 FA2 How is the total volume of 3 reactors in
FA3; X=X3 series related to single reactor ??
X=X2

If you could replace one of the

CSTRs with a PFR, which one would FA0
you choose to minimize the total -rA
volume of the reactor system

We can model a PFR as a series of

“n” equal volume CSTRs X
 Closing Thoughts on Levenspiel Plots

• Levenspiel Plots are useful means to illustrate the difference

between PFR and CSTR behavior
– If the rate law is given in terms of conversion (-rA) = f(X) or can be
generated/derived by intermediate calculations, one can size PFR,
CSTRs, and batch reactors.
– PFR can be modeled as many CSTR in series (strategy used in
UNISIM design software)

• Levenspiel plots are seldom used to design ‘real world’

reactors
– Restrictive conditions: no secondary side streams, single reaction
– Can only be used for scale-up if reaction conditions are kept identical: i.e.;
(-rA) varies with conversion identically in the full-size reactors as in the lab
 Class Problem
The following aqueous-phase reaction is carried out isothermally in both a
laboratory-scale reactor and an industrial-scale continuous stirred tank reactor:
A→B
The reaction rate follows a first-order rate law:
(-rA) = kCA where, k=0.1 min-1 at 50 oC

The operating conditions of the reactors are provided below

Industrial CSTR Lab CSTR

Feed concentration 10%A in solution 2% A in solution
Reactor volume 3600 L 63 mL
Volumetric flow rate 40 L/min 0.7 mL/min

The two reactors, vastly different in scale, and with different feed concentrations
yield similar conversion. Why?
 Time is of the Essence

• The extent of conversion of reactants in a chemical reactor

is related to the time the chemical species spend in the
reactor.

• Remember the definition: Average residence or space time

of fluid in vessel is τ = V/v0
– Space time is often used as a scaling parameter in reactor design

• Residence time is chosen to achieve desired conversion

(different for PFR and CSTR!), and can vary from a few
seconds to several hours, depending on the rate of reaction
– See Fogler Table 2.5
 Reaction Rates of Some Known Systems

Slow reaction Fast Reaction

(requires large residence time) (short residence time)