Chemical Reaction Engineering

Course Code: CHE 331

Course Cr. Hrs.: 4(3,1)
Course Instructor:
Dr. Muhammad Haris Hamayun
Assistant Professor,
Department of Chemical Engineering,
COMSATS University Islamabad, Lahore Campus.
Contact Email: mhhamayun@cuilahore.edu.pk
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 Course Contents

Kinetics of homogeneous reactions: rate of reaction, variables affecting the rate of

reaction, order of reaction, rate constant; searching for a mechanism of reaction,
activation energy and temperature dependency. Interpretation of batch reactor data for
single and multiple reactions. Integral method and differential method of analysis for
constant volume and variable volume batch reactors, search for a rate equation. Design
of homogeneous reactors, Batch, Mixed flow, Plug flow reactors, Comparison of single
reactor, multiple reactor systems in parallel/series. Temperature and pressure effects.
Adiabatic and non-adiabatic operations. Surface phenomenon and catalysis,
Heterogeneous reaction systems, rate equations for heterogeneous reactions, fluid
particle reactions, determination of rate controlling steps. Catalysis desorption
isotherms, kinetics of solid catalyzed reactions. Catalyst deactivation and regeneration.
Design of fluid-solid catalytic reactors.

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 Recommended Books

1) H. Scott Fogler, Elements of Chemical Reaction Engineering, 5th edition, Prentice

Hall, 2016.

2) Octave Levenspiel, Chemical Reaction Engineering, 3rd edition, Wiley India Pvt.
Limited, 2006.

3) Elsie Perkins, Chemical Reaction Engineering, WILLFORD Press, 2022.

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 CLOs and Mapping with PLOs

Understand • Describe the fundamentals of chemical reaction

(C2, PLO1) engineering.

Apply • Apply the fundamentals of chemical reaction

(C3, PLO1) engineering.

Analysis • Analyze the kinetic data using different methods of

(C4, PLO2) data analysis.

Design • Design isothermal and nonisothermal reactors (e.g.,

(C6, PLO3) Batch, CSTR, PFR, PBR etc.)

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 OBE in a Nutshell

◼ What do you want the students to have or able

to do? ◼ Knowledge, Skill, Affective

◼ How can you best help students achieve it?

◼ Student Centred Delivery

◼ How will you know what they have achieved it?

◼ Assessment

◼ How do you close the loop

◼ Plan, Do, Check, Act (PDCA)
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 Lecture # 1 – Today’s Course Coverage (CLO # 1)

• Introduction to Chemical Reaction Engineering

• Pillars of Chemical Reaction Engineering

• Let’s have a look at CRE in Industry

• How the Chemical Engineer is different from others?

• Applications of Chemical Reaction Engineering

• Chapter # 1: Mole Balance

• Chemical Specie and Chemical Identity
• Rate of Reaction
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 Introduction to Chemical Reaction Engineering

• Chemical reaction engineering (CRE) is one of two core courses that is unique to
chemical engineering and that separates the chemical engineer from other
engineering.

• CRE is the heart of chemical engineering.

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 How the Chemical Engineer is different from others?

1 Chemical kinetics is study of chemical reaction rates and reaction mechanisms.

The study of CRE combines the study of chemical kinetics with the reactors in which the reactions
2 occur.

3 Chemical kinetics and reactor design are at the heart of producing almost all industrial chemicals.

Primarily knowledge of chemical kinetics and reactor design that distinguishes the chemical engineer
4 from other engineers.

Selection of a reaction system that operates in the safest and most efficient manner can be the key to the
5 economic success or failure of a chemical plant.

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 Applications of Chemical Reaction Engineering

• Industrial processes, i.e., manufacturing of chemicals, pharmaceuticals, etc.

• Research and Development (R&D): Waste treatment, Micro-electronics, Nano-

particles and many more

• Department has a research group related to CRE, “Catalysis and reaction

Engineering Research Group”

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 Let’s have a look at CRE in Industry
Recycle
Recycles between these two operations are often incorporated to
improve conversion and yield.
Reaction
Batch A+B→C+D
CSTR
PFR
PBR
D1 (C) D2 (A, B)

Fresh B, XB

C1 C2
ROUT
XA
Fresh A, XA XB

B1 (A, B, D)
XC
XD
Reaction conditions Reactor Efficiency

Isothermal
B2 (D)

Adiabatic Separation
Catalytic
Single phase Separation can be performed by several types of operations
(distillation, extraction, crystallization, adsorption, etc.)
Multiple phase Product separation with Distillation being the far most used method 10
 Pillars of Chemical Reaction Engineering

CRE Algorithm:
Mole Balance + Rate Laws + Stoichiometry + Energy Balance + Combine Solution

Heat Effects
Isothermal Design

Stoichiometry
Rate Laws
Mole Balance
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 Pillars of Chemical Reaction Engineering

Be careful not to cut corners on any of the CRE building blocks while learning
this material! Otherwise, your algorithm will become unstable.

Heat Effects
Isothermal Design

Stoichiometry
Rate Laws

Mole Balance

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 Chapter # 1: Mole Balance

Objectives of this Chapter:

• Describe and define the rate of reaction (CLO # 1)
• Derive the general mole balance equation (CLO # 2)
• Apply the general mole balance equation to the four most common types of
industrial reactors (CLO # 2).
• Develop a preliminary form of the design equations of the most common industrial
reactors (CLO # 4):

• Batch Reactor (BR)

• Continuous-Stirred Tank Reactor (CSTR)
• Plug-Flow Reactor (PFR)
• Packed-Bed Reactor (PBR)
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 Chemical Species and 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.
Decomposition

• CH3CH3 → H2 + H2C=CH2

Combination
Three ways for a specie to lose its identity
• N2 + O2 → 2 NO

Isomerization

• C2H5CH=CH2 → CH2=C(CH3)2 14
 Rate of Reaction, – rA

• The reaction rate is the rate at which a species loses 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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 Rate of Reaction, – rA

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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 Basic Concept to keep in mind!!

• For reactants, the rate of disappearance is a positive (+) number.

• For products, the rate of disappearance is a negative (-) number because they are
being formed and not disappearing.

• For reactants, the rate of formation is a negative (-) number because they are
disappearing and not being formed.

• For products, the rate of formation is a positive (+) number.

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 Rate of Reaction, – rA

Example: A→B

• If species B is being formed at a rate of 0.2 moles per decimeter cubed per second,

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

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 Rate of Reaction, – rA

• 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/g.cat/s).

• NOTE: dCA/dt is not the rate of reaction

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 Rate of Reaction

Consider species j:

• r j is the rate of formation of species j per unit volume [e.g. mol/dm3s]

• r j is a function of concentration, temperature, pressure, and the type of catalyst (if
any)
• r j is independent of the type of reaction system (batch, plug flow, etc.).
• r j is an algebraic equation, not a differential equation
(e.g. -rA = kCA or -rA = kCA2)

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 Now Test yourself ?

Consider the reaction:

in which the rate of disappearance of A is 5 moles of A per dm3 per second at the
start of the reaction. At the start of the reaction:

• What is -rA?
• What is the rate of formation of B?
• What is the rate of formation of C?
• What is the rate of disappearance of C?
• What is the rate of formation of A, rA?
• What is -rB?
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 Now Test yourself ?

Rate of disappearance of A = -rA = 5 mole/dm3/s

Rate of disappearance of B = -rB = 10 mole/dm3/s

Rate of disappearance of C = -rC = -15 mole/dm3/s

Rate of formation of A = rA = -5 mole/dm3/s

Rate of formation of B = rB = -10 mole/dm3/s

Rate of formation of C = rC = 15 mole/dm3/s

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 General Mole Balance
System
Volume, V

Fj0 Gj Fj

 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  23
 General Mole Balance

Condition # 1: If spatially uniform, then

G j = r jV

Condition # 2: If NOT spatially uniform, then


V1
V2
r j1
rj 2
G j1 = rj1V1
G j 2 = rj 2 V2
 24
 General Mole Balance

n
G j =  rji Vi
i =1

Take limit
n
Gj =  rjiVi =  r dV
j
i=1 lim V → 0 n → 


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 General Mole Balance

System
Volume, V

FA0 GA FA

General Mole Balance on System Volume V

In − Out + Generation = Accumulation

dNA
FA 0 − FA +  rA dV =
dt
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 Today’s Course Coverage (CLO # 1, 2)

• Chapter # 1: Mole Balance

• General Mole Balance

• Types of Processes and Reactors

• Batch Reactor (BR)

• Continuous Stirred Tank Reactor (CSTR)

• Plug Flow Reactor (PFR)

• Packed Bed Reactor (PBR)

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 Types of Processes and Reactors

Batch
Continuous Processes
Processes

Batch Continuous stirred Tubular Packed Bed

Reactor tank reactor (CSTR) Reactor Reactor (PBR)

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Pictorial Representation of Batch Reactor

• Reactants are placed in the reactor, and the reaction is allowed

to proceed for some amount of time
• Closed system- no addition of reactants or removal of
products during the reaction
• Unsteady-state conditions- the composition changes with
time
• Ideal batch reactor- vessel is perfectly mixed
• Concentration and temperature are spatially constant, but
NOT constant in TIME

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 Batch Reactor (BR)

Characteristics Phases Applications Advantages Disadvantages

• Closed system • Gas, typical • Small scale • High • High
(No charge or for liquid production, conversion per operational
discharge during phase New process unit volume cost,
reaction), liquid reactions. development for one pass
phase. • Product
• Long reaction • Flexibility of quality varies
• Assumption: time, operation, easy batch to batch.
Constant density, Obtaining to clean
Well mixed kinetic data for
(Conc, T are reactor scaleup
spatially
uniform).

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 Mole Balance on Batch Reactor
dNA
FA0 − FA + ‫ ׬‬rA dV =
dt
FA0 = FA = 0
Well Mixed ‫ ׬‬rA dV = rA V
dNA
= rA V
dt
t = 0, NA = NA0
dNA t = t, NA = NA1
Integrating = dt
rA V
NA1 NA0
dNA dNA
t= න t= න
NA0 rA V NA1 −rA V
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Mole Balance on Batch Reactor

NA0
dNA
t= න
NA1 −rA V

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Continuous Stirred Tank Reactor (CSTR)

• Continuously add reactants and remove products (open

system)
• Inlet stream instantaneously mixes with bulk of reactor
volume
• Ideal batch reactor- assume perfect mixing occurs in vessel
• Temperature and concentration are uniform
throughout space
• Composition of the exit stream is the same as that
inside reactor (CA,outlet = CA, tank)
• Steady-state conditions- the reaction rate is the same at
every point and does not change with time

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 Continuous Stirred Tank Reactor (CSTR)

Characteristics Phases Applications Advantages Disadvantages

• Tank reactor • Typical for • Continuous • Good • Low

sufficiently liquid phase operation. temperature conversion per
well stirred i.e., reactions. • Processes with control unit volume
exit condition intense • Low operating
(C, T) = agitation. cost
reactor • Improve
conditions, selectivity by
steady state. temperature
and
concentration.
• Auto-
refrigeration

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 Mole Balance on CSTR
dNA
FA0 − FA + ‫ ׬‬rA dV =
dt

Steady State dNA

=0
dt

Well Mixed ‫ ׬‬rA dV = rA V

FA0 − FA + rA V = 0

FA0 − FA
V=
−rA

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Plug Flow Reactor (PFR)

• Also called a tubular reactor

• Cylindrical pipe with openings at both ends
• Steady movement of material down length of
reactor
• Reactants are consumed as they flow down the
length of the reactor
• Operated at steady state:
• No radial variation in temperature,
concentration, or reaction rate
• All fluid/gas elements have the same residence
time

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 Plug Flow Reactor (PFR)

Characteristics Phases Applications Advantages Disadvantages

• No radial • Typical for gas • Continuous • High • Poor

variations, phase operation conversion per temperature
concentration reactions. • Large scale unit volume control (hot
varies with production • Easy spot),
length down processes maintenance • Poor mixing.
the reactor • Fast reaction (No moving
parts)

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Mole Balance on Plug Flow Reactor

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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 Mole Balance on Plug Flow Reactor

Rearrange and take limit as ΔV→0

FA V + V − FA V
lim = rA
V →0 V
𝑓 𝑥 + ∆𝑥 − 𝑓(𝑥) 𝑑𝑓
lim [ ]=
∆𝑥→0 ∆𝑥 𝑑𝑥

dFA
= rA
dV
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 Mole Balance on Plug Flow Reactor
dNA
FA0 − FA + ‫ ׬‬rA dV =
dt

Steady State dNA

=0
dt

FA0 − FA + ‫ ׬‬rA dV = 0

dFA V = 0, FA = FA0
Integrating = rA
dV V = V1 , FA = FA1

FA1 FA0
dFA dFA
V1 = න V1 = න
FA0 rA FA1 −rA
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Mole Balance on Plug Flow Reactor

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 Plug Flow Reactor (PFR)

• Cylindrical shell, vertically oriented

• Often gravity-driven flow
• Heterogeneous reaction: fixed bed of catalyst inside
• Reactants enter top and flow through the packed bed of catalyst
• Concentration gradient of reactant and product down the length of the
reactor
• Reaction occurs on the surface of the catalyst pellets
• Reaction rate is based on the mass of the solid catalyst, W, not reactor
volume V

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 Packed Bed Reactor (PBR)

Characteristics Phases Applications Advantages Disadvantages

• Tubular • Gas/Solid • Heterogenous • High • Poor

reactor packed catalyst reactions conversion per temperature
with catalyst involving unit catalyst control (hot
catalyst • Mass, Low spot).
• Continuous operating • By passing and
operation (Labor) cost channeling.
• Shutdown and
cleaning may
be expensive.

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 Mole Balance on Packed Bed Reactor
′ dNA
FA0 − FA + r
‫ ׬‬A dW =
dt

Steady State dNA

=0
dt

FA0 − FA + ‫ ׬‬rA′ dW = 0

dFA W = 0, FA = FA0
Integrating = rA′
dW W = W, FA = FA

FA FA0
dFA dFA
W= න ′ W= න
r
FA0 A FA −rA′
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Summary of Reactors

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