SKF 3223 CHEMICAL REACTION ENGINEERING

INTRODUCTION

Chemical reaction engineering (CRE) combine the study of chemical kinetics with the
reactor in which the reaction occurs.

CRE is needed in the development of new and improvement of existing technologies.

search for alternative processes to replace old ones
novel reactors (use of metallocene catalysts)
find routes to make a product from different feedstock
novel processes for synthesis-gas production
Hydrocarbon production from syn gas
Biodiesel production
reduce/eliminate unwanted byproducts
fuel-cells for automobiles
NOx reduction

CRE is perhaps the key course that differentiates Chem Eng from other engineers.

CHAPTER 1: MOLE BALANCES

Learning Outcome
Define the rate of chemical reaction
Apply the mole balance equations to a batch reactor, CSTR, PFR, and PBR
Describe two industrial reaction engineering systems

Topics outline

Introduction to basic elements of reactor design

Quick refresher of basic terminology/notation
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)

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
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Whats involved in reactor design ?

Heat
Transfer

Mass
Transfer

Fluid
Mechanics

REACTANT(S)

PRODUCT

REACTOR
(Ethylene)

(Ethane)

Thermodynamics

Reaction
Kinetics
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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

Homogeneous & Heterogeneous Reactions

Homogeneous Reactions: reactions that occur in a
single-phase (gas or liquid)
NOx formation

NO (g) + 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) SO2 (g)

Vanadium catalyst (s)

Reversible and Irreversible Reactions

Irreversible Reactions: Reactions that proceed unidirectionally 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 + O2
SO3
H2S
H2 + 1/xSx
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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]
e.g. (-rA) = k CA or (-rA) = k CA2
where, k is rate constant [k=f(T)]

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

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/s-g or kmol/hr-kg catalyst

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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
CA

10:00 am
12:00 pm
3:00 pm
5:00 pm

CAO

CA

50.0
50.0
50.0
50.0

10.0
10.0
10.0
10.0

Reactor operates at steady state,

neither CAO nor CA are changing with time
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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

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General Mole Balances

IN

+ GENERATION

OUT

= ACCUMULATION
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General Mole Balances (2)

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Batch Reactor

Key Characteristics
unsteady-state operation (by definition)
High conversion can be achieved
no spatial variation of concentration or temperature
mainly used for small scale operation
suitable for slow reactions
mainly (not exclusively) used for liquid-phase reaction
Long downtime for cleaning leads to periods of no production
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General Mole Balance for a Batch Reactor

For reaction A B

in differential form as

in integral form as

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Continuous Stirred Tank Reactor (CSTR)

FA0
FA

Key Characteristics
steady state operation
good mixing leads to uniform concentration
and temperature
mainly used for liquid phase reaction
suitable for viscous liquid
Lower conversion

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General Mole Balance for CSTR

For reaction A B

v C vC A FAo
V = 0 A0
(rA )

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Plug Flow Reactor (PFR)

Key Characteristics
Steady-state operation
Spatial variation but no temporal variation
suitable for fast reaction mainly used for gas phase
reaction
Good for studying rapid reactions
temperature control may be difficult
there are no moving parts

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General Mole Balance for PFR

For reaction A B

Differential Form

dFA
= (rA )
dV

Integral Form
FA

V=

FAO

dFA
(rA )

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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 liquidphase reaction are also known.
temperature control may be difficult
There are no moving parts
Catalyst difficult to replace
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Pressure drop across the packed bed is an important consideration

Mole Balance for PBR

Differential Form

dFA
= (rA' )
dW
W = Weight of the packing

Integral Form
FA

W=

FAO

dFA
(rA' )
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Summary - Design Equations of Ideal

Reactors
Differential
Equation

Batch

dN j
dt

dV
dFj

PBR

t=

dW

N jO

V=

dF j

Integral
Equation
Nj

= (r j )V

CSTR

PFR

Algebraic
Equation

dN j
(rj )V

F jo F j
(rj )

V=

F jO

'

= (r j )

No spatial variations,
steady state

No spatial variations,
steady state
Fj

= rj

Remarks

Fj

W=

dF j

Steady state

(rj )
dF j

'
F jO ( r j )

Steady state
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