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 in Module 1 (Lectures 2-7):

– Introduction to basic elements of reactor design
– Quick refresher of basic terminology/notation
• Homogeneous and heterogeneous reactions
• Reversible and irreversible reaction
– Definition/notation of reaction rate.
– Development of general mole balance equation
– Common reactor types
• Key characteristics
• Mole balance equations for common industrial reactors (batch and
continuous)
– Introduction to the concept of reactant conversion
– Reactor design of single-reaction systems
• Definition of conversion
• Levenspiel Plots
– Introduction of space time and residence time and few other concepts
 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 does the reaction occurs (reaction rates) dictates how large the
reactor volume will be

• Design of isothermal reactors involves solution of MOLE

BALANCE equation only
– In some cases, pressure drop must also be calculated
 Our approach to reactor design

• Operations 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.

• Let us first familiarize ourselves with some common

terminologies and notations that we will be using
throughout the course
Terminologies and Definitions
Homogeneous & Heterogeneous Reactions
Homogeneous Reactions: reactions that occur in a
single-phase (gas or liquid)
NOx formation Aside:
NO (g) + 0.5 O2 (g)  NO2 (g) What is the precise
definition of a phase?
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)  SO2 (g) Vanadium catalyst (s)
Reversible and Irreversible Reactions
Irreversible Reactions: Reactions that proceed uni-
directionally under the conditions of interest

CH4 + 2O2 ⇄ 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
 Form of Mole Balance Equation

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

= moles of A consumed per unit volume per unit time
(rA) = rate of formation of species A

Note: “minus” sign denotes consumption or disappearance.

Units of (rA) or (– rA)

• moles per unit volume per unit time
• mol/L-s or kmol/m3-s

Question: Can we use (rA) to describe reaction rate of species that is

actually being consumed in during a reaction ??
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 (why ?)

Units of (-rA')
•mol per unit time per mass of catalyst
•mol/s-g or kmol/hr-kg catalyst
 Rate of reaction has units of dCA/dt.
Does the relationship: (-rA) = dCA/dt always hold true?
Let us consider the following example of a flow reactor and
evaluate if dCA/dt is equal to (-rA).

Ethylene Oxide

CAO CAO CA
10:00 am 50.0 10.0
CA 12:00 pm 50.0 10.0
3:00 pm 50.0 10.0
5:00 pm 50.0 10.0

Reactor operates at steady state,

neither CAO nor CA are changing with time
 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 via a constant (?) that depends on temperature.
• 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 rate constant [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 =
Rate of ACCUMULATION

dN A
FAO - FA + GA =
dt
FA
FAO
Control Volume = V
GA = (rate of formation of A) · V
= (rA)·V
Could you write the GMBE in terms of consumption and NOT generation
of a species ?
Common Reactor Types

• Batch Reactor

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

• Other Reactor Types

– Fluidized Bed Reactor
– Trickle Bed Reactor
 Batch Reactor

Key Characteristics
• unsteady-state operation (by definition)
• no spatial variation of concentration or temperature, i.e.
lumped parameter system (well-mixed)
• mainly used for small scale operation
• suitable for slow reactions
• mainly (not exclusively) used for liquid-phase reaction
• charge-in/clean-up times can be large
 General Mole Balance for a Batch Reactor

Reaction: A  Products

General Mole Balance Equation (GMBE) for Batch Reactor

may be written
in differential form as

in integral form as
 Plug Flow Reactor (PFR)

Key Characteristics
• Steady-state operation
• Spatial variation in axial direction but not in radial
direction + no temporal variation, i.e. distributed system
• suitable for fast reaction mainly used for gas phase
reaction
• temperature control may be difficult
• there are no moving parts
 General Mole Balance for PFR

Reaction: A  Products

Differential Form Integral Form

FA
dFA dFA
dV
= (rA ) V= 
FAO
(rA )
 Continuous Stirred Tank Reactor (CSTR)

FA0

FA

• steady state operation

• used in series
• no spatial variation of concentration or temperature,
i.e. lumped parameter system (well-mixed)
• mainly used for liquid phase reaction
• suitable for viscous liquid
CSTRs are also known as back-mix reactor

Picture Source: http://www-micrbiol.sci.kun.nl/galleries/two.html

 General Mole Balance for CSTR
FA0

FA
Reaction: A  Products

General Mole Balance Equation (GMBE) for a CSTR is of algebraic form

FAo - FA
V=
- ( rA )
Picture Source: http://www-micrbiol.sci.kun.nl/galleries/two.html
 Packed Bed Reactor (PBR)

FA0 FA

Key Characteristics
• Similar to PFR. Can be thought of as PFR packed with solid
particles, which are almost always catalysts.
• Steady-state operation
• Spatial variation but no temporal variation
• Mainly used for gas phase catalytic reaction although examples
for liquid-phase reaction are also known.
• temperature control may be difficult
• There are no moving parts
• Pressure drop across the packed bed is an important consideration
 Mole Balance for PBR

FA0 FA

Reaction: A  Products

Differential Form Integral Form

FA
dFA dFA
dW
= (rA' ) W= 
FAO
(rA' )
W = Weight of the packing
 Summary - Design Equations of Ideal Reactors

Differential Algebraic Integral

Remarks
Equation Equation Equation
dN j Nj Conc. changes with time
= (rj )V dN j
Batch dt t=  (rj )V
but is uniform within the
N jO reactor. Reaction rate
varies with time.

Conc. inside reactor is

F jo - F j uniform. (rj) is constant.
CSTR V= Exit conc = conc inside
- (rj ) reactor.

Fj
dF j Concentration and hence
PFR dF j
= rj
V= 
F jO
(rj )
reaction rates vary
spatially.
dV
 Class Problem #1

• Calculating Reaction Rate in a CSTR

1.0 L/min of liquid containing A and B (CAO=0.10 mol/L, CBO=0.01 mol/L)
flow into a mixed flow reactor of volume VR=1.0 L. The materials in the
reactor interact (react) in a complex manner for which the stoichiometery is
unknown.
The outlet stream from the reactor contains A, B and C at concentrations
of CAf = 0.02 mol/L, CBf=0.03 mol/L and CCf=0.04 mol/L.

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

the reactor.
 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?
Single-Reaction Systems
 Conversion (X)
• Quantification of how far a reaction has progressed

Moles of species " i" reacted

X=
Moles of species " i" fed

• Batch Reactors
N IO - N I
X=
N IO

• Continuous (or Flow) Reactors

FIO - FI
X =
FIO
 Further Discussions on Conversion

• Limiting reactant..

• Maximum conversion for irreversible reactions

• Maximum conversion for reversible reactions

Notes to be provided in the class.

 Design Equation in Terms of Conversion

REACTOR DIFFERENETIAL ALGEBRAIC INTEGRAL

FORM FORM FORM

X
dX
BATCH N AO
dX
= (-rA )V t = N AO 
dt 0
- rAV

FAO ( X )
V=
CSTR (-rA ) Exit

X
dX dX
PFR FAO = (- rA ) V = FAO 
dV 0
- rA
 Levenspiel Plots:
Illustration of Reactor Sizing for
Single-Reaction Systems
 Octave Levenspiel

(PhD 1952): Octave Levenspiel also obtained an MS from

Oregon State and served as a faculty member for 25 years
until he retired in 1991. He published over 100 papers and
proceedings, two of which have been listed as "Citation
Classics." He was awarded 1977 American Institute of
Chemical Engineers W.K. Lewis Award, the 1979 R.H.
Wilhelm Award, and the 2003 Founders Award and Gold
Medal, the highest honor given by the society. In 2000 he
was inducted into the National Academy of Engineering. He
also received two honorary doctorates , one from France.

He is considered to be one of the founders of

Chemical Reaction Engineering.

SOURCE: http://engr.oregonstate.edu/oregonstater/fame/1998/che/octavelevenspiel.html
 Levenspiel Plots
Plug Flow Reactor (PFR)
FA0 x = xPFR
FA0
(-rA ) VPFR = 
x =0
- rA
dX

X XPFR

Continuous Stirred Tank Reactor (CSTR)

FA0 FA0
(-rA ) VCSTR =[ ] [ X CSTR ]
(-rA )
Evaluated at X=XCSTR

X XPFR
 Class Problem #2

The following reaction is to be carried out isothermally in a

continuous flow reactor:

AB

Compare the volumes of CSTR and PFR that are necessary to

consume 90% of A (i.e. CA=0.1 CAO). 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
[Assume the volumetric flow rate is constant.]
For same conversion, is the CSTR volume
always higher than PFR volume ?

FAO
-rA

X
For a given conversion, can the CSTR
volume be equal to PFR volume?

FAO
-rA

X
Reactors in Series
 PFR in Series

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

Let us compare two scenarios

(i) Single reactor achieving X3

FAO (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
Compare volume for the following 2
cases
FAO
(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

FAO
-rA

Can we model 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

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

reactors
– the conditions (P, T, and reactant concentration) must be identical to that in
the laboratory experiments.

• If the rate law is given in terms of conversion (-rA) = g(X) or can be

generated/derived by intermediate calculations, one can size PFR, CSTRs,
and batch reactors.
Space Time & Residence Time
 Class Problem #3
The following aqueous-phase reaction are carried out isothermally in a laboratory-
scale and an industrial-scale continuous stirred tank reactors:
AB
The reaction rate for the reaction 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 Essence

• The extent of conversion of reactants in a chemical reactor

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

• Two types of time-parameters are commonly used in

chemical reaction engineering
– space time
– residence time

• Space time is often used as a scaling parameter in reactor

design
Space Time & Residence Time - Definitions
Space Time () : Time required to process 1 =
V
reactor volume of fluid at inlet vo
conditions

Space Velocity: SV =
v
V
•LHSV - Liquid Hourly Space Velocity
•GHSV - Gas Hourly Space Velocity

Actual Residence Time: The time actually spent by fluid inside the
reactor.
 Illustration of difference between
space time () and residence time (tres)
The Pop Corn Example

Under what practical conditions do we expect space time = residence time ?

 Reaction Rates of Some Known Systems

Slow reaction Fast Reaction

(requires large residence time) (short residence time)
 Relative Rates of Reaction

For a reaction given below:

aA + bB  cC + dD

How is (-rA) related to (-rB), (rC) and (rD) ?