Chemical Reaction Engineering Lectures

University of Soran

College of Engineering

Chemical Engineering Department

1 Dr. Arkan Jasim Hadi

Fourth Year
Textbook:
1. Fogler H.S., Elements of Chemical Reaction Engineering, Prentice Hall of India
References:
1. Levenspiel O., Chemical Reaction Engineering, John Wiley
3. Smith J.M., Chemical Engineering Kinectics, McGraw Hill
4. Hill C.G., An Introduction to Chemical Engineering Kinetics & Reactor Design

2 Dr. Arkan Jasim Hadi

 Lecture 1

Chemical Reaction Engineering (CRE) is the field

that studies the rates and mechanisms of chemical
reactions and the design of the reactors in which they
take place.
Chemical reaction engineering is at the heart of
virtually every chemical process. It separates the
chemical engineer from other engineers

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 Lecture 1 – Thursday 1/10/2013
 Introduction

 Definitions

 General Mole Balance Equation

 Batch (BR)
 Continuously Stirred Tank Reactor (CSTR)
 Plug Flow Reactor (PFR)
 Packed Bed Reactor (PBR)

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 Chemical Identity
 A chemical species is said to have reacted when it
has lost its chemical identity.
 The identity of a chemical species is determined by
the kind, number, and configuration of that species’
atoms.
 There are three ways for a species to loose its
identity:

1. Decomposition CH3CH3  H2 + H2C=CH2

2. Combination N2 + O2  2 NO
3. Isomerization C2H5CH=CH2  CH2=C(CH3)2

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 1.1 Reaction Rate

 The reaction rate is the rate at which a species

looses its chemical identity per unit volume.

 The rate of a reaction (mol/dm3/s) can be

expressed as either:
 The rate of Disappearance of reactant: -rA
or as
 The rate of Formation (Generation) of product: rP

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 Reaction Rate

Consider the isomerization

AB
rA = the rate of formation of species A per unit
volume
-rA = the rate of a disappearance of species A
per unit volume
rB = the rate of formation of species B per unit
volume

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 Reaction Rate
EXAMPLE: AB
If Species B is being formed at a rate of
0.2 moles per decimeter cubed per second, i.e.,
rB = 0.2 mole/dm3/s

Then A is disappearing at the same rate:

-rA= 0.2 mole/dm3/s
The rate of formation (generation of A) is:
rA= -0.2 mole/dm3/s

For a catalytic reaction we refer to –rA’ , which is the rate of

disappearance of species A on a per mass of catalyst basis.
(mol/gcat/s)
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Types of reactors:

In chemical engineering, chemical reactors are vessels designed to contain chemical reactions.
The design of a chemical reactor deals with multiple aspects of chemical engineering.
Designers ensure that the reaction proceeds with the highest efficiency towards the desired
output product, producing the highest yield of product while requiring the least amount of
money to purchase and operate. Normal operating expenses include energy input, energy
removal, raw material costs, labor, etc.

There are a couple main basic vessel types:

A tank
A pipe or tubular reactor (laminar flow reactor (LFR))

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Types of reactors:
There are four main basic models used to estimate the most important process variables of
different chemical reactors:
Batch ReactorU
Continuous Stirred-Tank Reactor (CSTR)
Plug Flow Reactor (PFR)
Packed Bed Reactor (PBR)

Key process variables include

Residence time (τ) , Volume (V) , Temperature (T) , Pressure (P) , Concentrations of chemical
species (C1, C2, C3, ... Cn) ,Heat transfer coefficients (h, U)

Chemical reactions occurring in a reactor may be exothermic, meaning giving off heat, or
endothermic, meaning absorbing heat. A chemical reactor vessel may have a cooling or heating
jacket or cooling or heating coils (tubes) wrapped around the outside of its vessel wall to cool
down or heat up the contents.

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1.2 General Mole Balances

 To perform a mole balance on any system, the system

boundaries must first be specified. The volume enclosed by
these boundaries will be referred to as the system volume. We
shall perform a mole balance on speciesj in a system volume,
where species j represents the particular chemical species of
interest, such as water or NaOH

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 Building Block 1:
General Mole Balances
 Molar Flow  Molar Flow   Molar Rate   Molar Rate 
 Rate of    Rate of   Generation    Accumulation
       
 Species j in   Species j out  of Species j  of Species j 
dN j
Fj 0  Fj  Gj 
dt
 mole   mole   mole   mole 
          
 time   time   time   time 
where Nj represents the number of moles of species j in the system at time t.
If all the system variables (e.g., temperature, catalytic activity, concentration of the
chemical species) are spatially uniform throughout the system volume, the rate of
generation of species j , Gj, is just the product of the reaction volume, K and the
rate of formation of species j , rj.
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 Building Block 1:
General Mole Balances
If spatially uniform:
G j  r jV


Suppose now that the rate of formation of species j for the
reaction varies with the position in the system volume. That is, it
has a value rj1 at locatiion 1, which is surrounded by a small
volume, ∆V1 , , within which the rate is uniform similarly, the
reaction rate has a value rj2 at location 2 and an associated
volume, ∆V2.
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 Building Block 1:
General Mole Balances

n
G j   rji Vi
i 1
Take limit
n

Gj   rjiVi   r dV
j
14 Dr. Arkan Jasim Hadi i1 lim V  0 n  
 Building Block 1:
General Mole Balances
System
Volume, V

FA0 GA FA

General Mole Balance on System Volume V

In  Out  Generation  Accumulation

dN A
FA0  FA   r dV
A 
dt
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 Batch Reactor - Mole Balances
Batch
A batch reactor has neither inflow nor
outflow of reactants or products while
the reaction is being carried out; FA0 =
FA =0
dN A
FA0  FA   rA dV 
dt
FA0  FA  0
If the reaction mixture is
perfectly mixed so that there is
no variation in the rate of
 r dV
A  rAV
reaction throughout the reactor
volume, we can take rA out of
the integral and write the mole
balance in the form dN A
 rAV
16 Dr. Arkan Jasim Hadi dt
 Batch Reactor - Mole Balances
dN A
Integrating dt 
rAV
t  0 N A  N A0
when
t  t NA  NA

NA
dN A
t 
N A0
 rAV

Time necessary to reduce the number of moles of A from NA0 to NA.

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 Batch Reactor - Mole Balances
NA
dN A
t 
N A0
 rAV

NA

18 Dr. Arkan Jasim Hadi t

 Batch Reactor - Mole Balances
Figure 1-3 shows different type of batch
reactors used for gas phase reactions.
Reactor A is constant volume (variable –
pressure).
Reactor B is constant pressure (variable –
volume).
At time t=0, the reactant are injected into the reactor and the reaction is initiated.
The different forms the mole balance will take for each type of reactor, consider the
following examples, in which the gas-phase, decomposition of dimethyl ether is
taking place to form methane, hydrogen, and carbon monoxide:

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 Batch Reactor - Mole Balances
Example 1-2 Constant Volume or Constant Pressure: Does It Make a Difference?
Write the mole balance for dimethyl ether in terms of the reactor volume, concentration, and
rate of formation of dimethyl ether for both a constant-pressure and a constant-volume batch
reactor.
Solution
To reduce the number of subscripts, we write the reaction symbolically as

where A is dimethyl ether, M is methane, H is hydrogen, and C is carbon monoxide.

For both batch reactors, the mole balance on A is

In writing the mole balance for dimethyl ether for a batch reactor, the only
assumption made is that there are no spatial variations in rA

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 Batch Reactor - Mole Balances
Constant-volume batch reactor. The reactor is perfectly mixed so that the concentration of
the reacting species is spatially uniform. Because the volume is constant we can take V inside the
differential and write the mole balance in terms of the concentration of A:
𝑁
1 𝑑𝑁𝐴 𝑑( 𝐴 ) 𝑑𝐶𝐴
𝑉
= = = 𝑟𝐴
𝑉 𝑑𝑡 𝑑𝑡 𝑑𝑡

Constant-pressure batch reactor. To write the mole balance for this reactor in terms of concentration,
we again use the fact that

The difference between equations (El-2.1) and (El-2.3) for the two different types of reactors is apparent.

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 1.4 Continuous-Flow Reactors
1.4.1 Continuous-Stirred Tank Reactor (CSTR) - Mole Balances
A type of reactor used very commonly in industrial processing is a stirred tank
operated continuously

CSTR

• It is referred to as the continuous-stirred tank reactor (CSTR) or backmix reactor:

• The CSTR is normally run at steady state and is usually operated so as to be quite well
mixed.
• As a result of the latter quality, the CSTR is generally modeled as having no spatial variations
in concentration, temperature, or reaction rate throughout the vessel.
• Since the temperature and concentration are identical everywhere within the reaction vessel,
they are the same at the exit point as they are elsewhere in the tank.
• Thus the temperature and concentration in the exit stream are modeled as being the same as
those inside the reactor.
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 CSTR - Mole Balances
When the general mole balance equation
dNA
FA 0  FA   rA dV 
dt

is applied to a CSTR operated at steady state (i.e., dNA

conditions do not change with time),
Steady State 0
dt
Well Mixed means: no spatial
variations in the rate of reaction  r dV  r V
A A

FA 0  FA
FA0  FA  rAV  0 V
rA
CSTR volume necessary to reduce the molar flow rate from FA0 to FA.
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1.4.2Tubular Reactor or Plug Flow Reactor (PFR) - Mole Balances

In addition to the CSTR and

batch reactors, another type of
reactor commonly used in
industry is the tubular reactor
l: It consists of a cylindrical
pipe and is normally operated
at steady state, as is the CSTR.
For the purposes of the
material presented here, we
consider systems in which the
flow is highly turbulent and the
flow field may be modeled by
that of plug flow.
That is, there is no radial variation in concentration and the reactor is
referred to as a plug-flow reactor (PFR)
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 Plug Flow Reactor - Mole Balances
• In the tubular reactor, the reactants are continually consumed as
they flow down the length of the reactor.
• In modeling the tubular reactor, we assume that the
concentration varies continuously in the axial direction through
the reactor.
• Consequently, the reaction rate, which is a function of
concentration for all but zero-order reactions, will also vary
axially.
To develop the PFR design equation we shall divide (conceptually)
the reactor into a number of subvolumes so that within each
subvolume ∆V, the reaction rate may be considered spatially uniform
(Figure 1-5). We now focus our attention on the subvolume that is
located a distance y from the entrance of the reactor.

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 Plug Flow Reactor - Mole Balances
V

FA FA


V V  V
 

 In   Out  Generation
at V   at V  V   in V 0
     
FA V  FA V  V  rA V 0
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 Plug Flow Reactor - Mole Balances
Rearrange and take limit as ΔV0

FA V  V  FA V
lim  rA
V  0 V

dFA
 rA
dV

This is the volume necessary to reduce the entering molar

flow rate (mol/s) from FA0 to the exit molar flow rate of FA.
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
Dr. Arkan Jasim Hadi
 Plug Flow Reactor - Mole Balances
PFR

dN A
FA0  FA   rA dV 
dt
dN A
Steady State 0
dt

FA0  FA   rAdV  0
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 Alternative Derivation
Plug Flow Reactor - Mole Balances
Differientiate with respect to V

0
dFA
 rA
dFA
 rA
dV dV
FA
dFA
The integral form is: V   rA
 FA 0

This is the volume necessary to reduce the

entering molar flow rate (mol/s) from FA0 to the
exit molar flow rate of FA.
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1.4.3Packed Bed Reactor (PBR)- Mole Balances
The principal difference between reactor design calculations involving
homogeneous reactions and those involving fluid-solid heterogeneous
reactions is that for the latter, the reaction rate is based on mass of
solid catalyst, W, rather than on reactor volume, V For a fluid-solid
heterogeneous system, the rate of reaction of a substance A is defined
as

The mass of solid I s used because the amount of the catalyst is what
is important to the rate of reaction, The reactor volume that contains
the catalyst is of secondary significance.

the derivation of the design equation for a packed-bed catalytic

reactor will be carried out in a manner analogous to the development
of the tubular design equation.

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 Packed Bed Reactor - Mole Balances
To accomplish this derivation, we simply replace the volume coordinate in PFR with
the catalyst weight coordinate W (Figure 1-7)
W
PBR
FA FA

W W  W
 
The generalized mole balance on species A over catalyst weight AW
results in the equation

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 Packed Bed Reactor - Mole Balances
which are, as expected, the same dimension of the molar flow rate FA. After dividing
by ∆W and taking the limit as ∆W 0, we arrive at the differential form of the mole
balance for a packed-bed reactor:

VVhen pressure drop through the reactor (see Section 4.4) and catalyst decay (see
Section 10.7) are neglected, the integral form of the packed-catalyst-bed design
equation can be used to calculate the catalyst weight.

The integral form to find the catalyst weight is:

FA
dFA
W 
FA 0
rA

PBR catalyst weight necessary to reduce the entering molar flow

rate FA0 Jasim
Dr. Arkan to molar
Hadi flow rate FA.
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 Example 1-3 How Large Is It?

The first-order reaction

is carried out in a tubular reactor in which the volumetric flow rate, u , is constant.
Derive an equation relating the reactor volume to the entering and exiting
concentrations of A, the rate constant k , and the volumetric flow rate ʋ. Determine the
reactor volume necessary to reduce the exiting concentration to 10% of the entering
concentration when the volumetric flow rate is 10 dm3/min (i.e., liters/min) and the
specific reaction rate, k , is 0.23 min-1 .

Solution
For a tubular reactor, the mole balance on species A (j = A) was shown to be

For a first-order reaction, the rate law (discussed in Chapter 3) is

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 Reactor Mole Balances Summary
The GMBE applied to the four major reactor types
(and the general reaction AB)
Reactor Differential Algebraic Integral
NA
NA
dN A
Batch dN A
 rAV t  rAV
dt N A0
t
CSTR FA 0  FA
V
rA FA
FA
dFA dFA
PFR
dV
 rA V 
FA 0
drA
V

FA FA
dFA dFA
PBR

 rA W  rA
36 Dr. Arkan Jasim Hadi dW FA 0
W
 End of Lecture 1

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