22/05/2017

Class Information
Course Instructor: Amenaghawon, N.A. andrew.amenaghawon@uniben.edu
Lecture Venue: 500L Class
Department of Chemical Engineering, University of Benin Second term 2016/2017: Tuesdays (12pm-1pm); Thursdays (11am-1pm)
Course Website: http://amenaghawon.com/view_courses.php?c=che562
Grading and Assessment:
• Continuous Assessment with a weight of 30% of final mark
CHEMICAL REACTION ENGINEERING IV • Class activities
• Quizzes
CHE 562 • Take home assignment
• Group presentation
• Closed book final exam with a weight of 70% of final mark
Recommended texts:
Engr. Dr. N.A. Amenaghawon • Levenspiel, O. (1999). Chemical Reaction Engineering, John Wiley & Sons, New York
• Fogler, H.S. (2006). Elements of Chemical Reaction Engineering, 4th Ed. Prentice Hall, NJ
BEng (Uni. Benin), MSc/DIC (Imperial College London), Ph.D (Uni. Benin) • Froment, G.F., Bischoff, K.B. and De Wilde, J. (2011). Chemical Reactor Analysis and
Design, 3rd Ed. John Wiley & Sons, Inc., New York.
MNSChE, MNSE, MNIM, R.Eng (COREN) • Smith, J.M. (1981). Chemical Engineering Kinetics, 3rd Ed. McGraw-Hill Inc., New York
• Chorkendorff, I. and Niemantsverdriet, J.W. (2003). Concepts of Modern Catalysis and
Department of Chemical Engineering, University of Benin, Benin City 1
Kinetics. Wiley 2

Class Information
Class Information Aim and Learning outcomes:
Aim:
Course Outline:
To provide students with an in-depth understanding of the
This course in chemical reaction engineering will focus theory of reaction systems catalysed by solids
on reaction systems that are catalysed by solids. It will Outcomes:
cover the following: At the end of taking this course, the student should be able to:
Introduction to heterogeneous reactions understand the theory of catalysis with particular focus on
heterogeneous fluid-solid catalytic reactions
Catalysts and catalysis
develop kinetic rate expressions for these types of reactions
Reactions catalysed by solids
determine rate controlling steps and use this information for
The packed bed catalytic reactor efficient reactor design
The course outline can be downloaded from the identify the optimum temperature progression for reactions in
staged adiabatic reactors and identify the best choice of reactor
course website in .doc format for a given reaction
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INTRODUCTION
In general, heterogeneous reactions are those that
involve more than one phase

These can include gas-liquid, liquid-liquid, liquid-solid,

gas-solid reactions to name some
INTRODUCTION TO
When a solid phase is involved, this can be a reactant
HETEROGENEOUS REACTIONS (e.g., combustion of a solid fuel) or a catalyst that is not
part of the stoichiometry of the reaction(s)
For the purpose of this course, we will consider gas-
solid, liquid-solid, or gas-liquid-solid reactions only,
where the solid phase is a catalyst, and the reactants
5 are in the gas or in the liquid (or both) 6

INTRODUCTION INTRODUCTION
The presence of phase boundaries in
For these systems there are two complicating
heterogeneous systems introduces the need
factors that must be accounted for beyond
to deal with physical processes (mass and
what is normally considered in homogeneous
energy transfer) between the bulk fluid and
systems
the solid catalyst
The rate equation

Physical processes affect reactor design in a

more intrinsic way for heterogeneous The contacting patterns for two-phase
reactions than for homogeneous ones systems
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INTRODUCTION
The Rate Equation
The basic difference between a
homogeneous reaction and a heterogeneous
reaction is the expression for the reaction
rate
Since more than one phase is present, the
movement of material from phase to phase
must be considered in the rate equation
Terms for mass transfer
Terms for chemical reaction
9 10
INTRODUCTION
The Rate Equation
Thus the rate expression in general will
incorporate mass transfer terms in addition to
the usual chemical kinetics term
These mass transfer terms are different in
type and numbers in the different kinds of
heterogeneous systems
No single rate expression has general
application

INTRODUCTION INTRODUCTION
The Rate Equation The Rate Equation
i. Diffusion of reactant(s) from the bulk phase to the catalyst
Contrary to what happens in a homogeneous external surface
reaction, reactants have to go through a ii. Diffusion of reactant(s) into the pores of the particle (porous
materials)
series of steps before the actual reaction
iii. Adsorption of reactant(s) onto the catalyst surface within the
occurs porous catalyst matrix
iv. Chemical reaction at the active sites within the catalyst
These steps are enumerated as follows: v. Desorption of product(s) from the catalyst surface within the
porous catalyst matrix
vi. Diffusion of product(s) through the pores to the catalyst
external surface
vii. Diffusion or convection of product(s) from the catalyst external
surface to the bulk phase
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INTRODUCTION INTRODUCTION
The Rate Equation-the journey The rate equation

Adsorption is
critical to
heterogeneous
reactions

13 14

INTRODUCTION INTRODUCTION
The rate equation The Rate Equation
Oxidation of carbon monoxide
At steady state, the rates of the individual
steps will be identical

Formulating and equating the rate

expressions for these steps can be a means
of developing an overall rate equation in
terms of the concentration of the bulk fluid

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Example 1 Solution

The combustion of a particle of carbon in air is The combustion process can be represented
represented as follows: practically as shown in the Figure

C + O2 
→ CO2

If the formation of CO can be neglected, how

many rate steps are involved?

Practical burning of carbon in air

17 18

Solution Solution

The combustion process can be represented

conceptually as shown in the Figure

From the conceptual model, we see that two/three steps

in series are involved:
Mass transfer of oxygen to the surface of the carbon
particle
Reaction at the surface of the particle
Mass transfer of CO2 from the reaction sites back to
A conceptual model of carbon burning in air the bulk gas phase
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Example 2 Solution

The air transport and uptake process in the

• Air is bubbled through a tank of liquid to be
tank can be represented practically as shown
utilised for the metabolic activity of an aerobic
in the Figure
microbe.

• How many rate steps are involved if the

aerobe is to produce metabolic products in
the tank?

Aerated tank with aerobes

21 22

Solution Solution

• In order to conceptually model the

transport process, we consider that
the required solute component (A
for instance) exists in the gas (air) • In order, for the microbe to get
phase access to A, it (A) needs to be
transported through the bulk liquid
• Also, we consider that the microbe phase to get to the microbe
can only take up the component if it
is mobilised to the liquid phase

• Component A has to be transported

from the gas phase to the liquid
phase 23 24
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Solution INTRODUCTION
The Rate Equation
To obtain an overall rate expression, rate equations
for each step should be appropriately combined

First write the individual rate steps on the same basis

(e.g unit surface of burning particle, unit volume of
• A has to undergo further transport to finally fermenter, unit mass of solid, etc)
get to the microbial cell
• The metabolic products formed will also need
to diffuse back into the bulk liquid phase
• In all, as much as 7 rate steps are possible
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INTRODUCTION INTRODUCTION
The Rate Equation The Rate Equation

If the acting rate steps are in series, then:

Next, put all the mass transfer and reaction steps

into the same rate form and then combine as
follows:
If the acting rate steps are parallel, then:

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INTRODUCTION INTRODUCTION
The Rate Equation The Rate Equation
For steps in series: For steps in series:
In general, if all the steps are linear in In combining rates, the concentration of
concentration, then it is easy to combine materials at intermediate conditions is usually
them not known
If any of the steps are nonlinear, then the
resulting overall rate expression will be These concentrations are typically eliminated
complex when combining rates

Therefore, you may try to bypass this

nonlinear step 29 30

Example 3 Solution

A solute component (A) in a liquid phase is to be The reaction is stoichiometrically represented as

contacted with a solid surface containing a reacting follows:
component (B). Reaction takes place when contact is A(l ) + B( s) 
→ P (l )
initiated between A and B at the solid surface to The transport process can be conceptually
produce a product P which is mobilised back into the represented as shown:
bulk liquid phase

a. Create a conceptual model of this L/S reaction

system
b. Derive an overall rate expression for the process
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Solution Solution

This reaction system is made up of two rate steps Step 2: Chemical reaction
• Mass transfer The stoichiometry indicates that the reaction is first
• Chemical reaction order wrt A
Hence, the overall rate expression will contain terms
The rate of reaction of A at the surface is given as
accounting for mass transfer as well as chemical reaction
(based on unit surface of B):
Step 1: Mass transfer
1 dN A
The rate of transfer (diffusion flux) of A from the bulk liquid −rA'' 2 = = k " C As
S dt
phase to the surface of the solid is given as (based on unit
surface of B):
1 dN A D ''
−rA'' 2 = k " C As
rA''1 = = (C As − C Al ) = kl (C As − C Al ) −rA1 = kl (C Al − C As )
S dt ∆x
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Solution Solution

Combining rate steps Combining rate steps

At steady state, the rate of transfer of A to the surface is Replacing CAs in either of the equations for steps 1 or 2 gives
equal to the rate of reaction of A at the surface (moreover, the the overall rate expression as follows:
steps are in series)
1
Hence: kl k " −rA''1 = − rA'' 2 = − rA'' = C
−rA''1 = −rA'' 2 = − rA'' = C Al 1 1 Al
kl + k " +
kl (C Al − C As ) = k " C As kl k "

Transforming the above equation in favour of CAs results in 1 1

(CAs is the concentration of an intermediate specie, so we −rA'' = C koverall =
1 1 Al −rA'' = koverall C Al 1 1
eliminate it): + +
kl k " kl k "
kl
C As = C Al The resistances are additive (steps in series)
kl + k " 35 36
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Solution Solution

Comments: The Figure shows how the concentration varies

1 between the bulk fluid phase and the catalyst
''
−r = koverall C Al koverall =
A 1 1
+ surface
kl k "

The resistances are additive (steps in series)

The addition of resistances to obtain on overall

resistance is permissible only when the rate is a
linear function of the driving force and when the
processes occur in series
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Class Activity 2
A solute component (A) in a liquid phase is to be
contacted with solid surface containing a reacting
component (B). Reaction takes place when contact is
initiated between A and B at the solid surface to
produce a product P which is mobilised back into the
bulk liquid phase. If the reaction step is second order
with respect to A
a. Create a conceptual model of this L/S reaction
system
b. Derive an overall rate expression for the process
INTRODUCTION
The Rate Equation
The overall rate expression is obtained by
combining rate equations for each step
Therefore, “the complexity of the analysis and design
of catalytic reactors resides on the combination of all
these steps, rather than in the design equation itself”
Down the road, we will study each of the steps
involved in the previous scheme

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INTRODUCTION
Contacting pattern for two phase system
The second complication encountered with
heterogeneous reaction systems has to do with the
selection and design of contactors for the two
phases involved
There are many options regarding how to contact
both phases
Each contacting pattern will require a unique
equation for its design
Design equations for ideal flow patterns may be
developed without too much difficulty
41
INTRODUCTION
Contacting pattern for two phase system
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INTRODUCTION
Contacting pattern for two phase system
However, when real flow deviates considerably from
the ideal, we may:
Develop models to mirror actual flow closely
Calculate performance with ideal patterns which
"bracket" actual flow
Fortunately, most real reactors for heterogeneous
systems can be satisfactorily approximated by one
of the five ideal flow patterns
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