CHEMICAL REACTION

ENGINEERING I
2018/2019 session

CHE 416
Course lecturers:
Dr. Ayeni O.A, Dr. Alagbe E.E & Dr.
Sanni S.E.
(contact: samuel.sanni@covenantuniversity.du.ng)
 CHEMICAL KINETICS AND REACTOR
DESIGN:
• Motivation for understanding chemical kinetics and
reaction design:
• This is what makes us chemical engineers – the
reactor is the central feature of most chemical
processes.
• Even if separation costs dominate, the reactor often
determines the separation costs.
• Chemical reactions are ubiquitous in nature and
industry.

2
 COURSE OUTLINE:CHE416
• IDEAL REACTORS
• ASSUMPTIONS (IDEAL VS. REAL)
• MATERIAL BALANCE / PERFORMANCE OR
DESIGN EQUATIONS
• COMPARISON OF IDEAL REACTORS
• NONISOTHERMAL OPERATION
• ENERGY BALANCE EQUATION
• APPLICATION TO DESIGN
 OUTLINE:CHE416 CONTD.
• REAL VERSUS IDEAL REACTORS
• SOURCE OF DEVIATIONS
• RESIDENCE TIME DSTRIBUTION
• RTD FUNCTIONS
• CONVERSIONS- First-Third ORDER RXNS
• REACTOR MODELS
REQUIREMENTS FOR PASSING THIS
COURSE
• ATTENTIVENESS IN SCLASS

• TAKING AND READING NOTES/ RELEVANT

TEXTS

• PROBLEM SOLVING (PBL; INTERNET AND

UNIVERSITY SITES)

• ATTENTION TO TUTORIALS
Some useful texts
1. Chemical reaction engineering by
Levenspiel O.
2. Elements of Chemical reaction engineering
by Fogler S.
3. Chemical reactor analysis and design by
Froment and Bishoff
4. Fundamentals of chemical reaction
engineering by Holland, C.D. and Anthony,
R.G.
5. Chemical Kinetics & Reaction Dynamics by
 Reaction Engineering

Mole Balance Rate Laws Stoichiometry

These topics build upon one another

 Heat Effects

Isothermal Design

Stoichiometry

Rate Laws

Mole Balance
 Chemical Identity & Process
• A chemically reacted species is one with
transformed chemical identity.

• By identity, we mean, the kind, number,

and atomic configuration of the species of
interest.
• A process simply refers to a network of
activities leading to the transformation of
reactant species
 WHY IDEAL REACTORS?
• Mixing: 100% in BR and CSTR; 0% in
axial direction for PFR
1. Ideal reactors: simple in design with
well defined fluid flow patterns
2. Complex real reactors can be examined
in terms of ideal reactors
3. For new designs, ideal reactors help
determine type of mixing for improved
results
 WHY IDEAL REACTORS? Contd.
• There’s much to gain from a study of ideal reactors.
• Sizing of reactor systems.
• INSIGHT into:
• the operation of real reactors
• Effect of parameters such as temp., press.
volume flow etc. on results
• They bring to bear, important factors to control
• Hence powerful models for chemical reaction
systems

12
 WHAT ARE IDEAL REACTOR
MODELS
• Based on assumptions about mixing
patterns within REACTORS
• One of the assumptions represent the
best way of contacting the reactants
• Easy to treat mathematically
• Insights obtained are significant in
knowing the type of mixing in real
reactors, important design parameters,
better control
 Ideal reactor types:
1.Batch Reactor (BR) 100%
mixing

2.Continuously(operated)
Stirred Tank Reactor (CFSTR)

3.Plug Flow Reactor (PFR) 14

 Batch Reactor (BR)
• operates in a discontinuous way(wrt
time)
• reactants and any other substances
(catalyst, solvent etc.) are loaded into the
reactor at beginning
• Contents subjected to perfect mixing
(and left to react) for a certain period.
• The resultant mixture is then discharged.
15
Batch reactor: homogenous reaction
mixture

16
 Batch Reactor (BR)2
• operates in unsteady mode with respect
to time at any position
• Composition at any point in reactor
changes continuously w.r.t time
• 1st order reaction: CA=CA0e-kt
• operates in steady mode w.r.t space. No
variation from point to point because of
perfect mixing at any point in time
 CHANGES IN A Batch Reactor
• reactants are consumed and products
formed with reaction
• -the composition of mixture changes
continuously[reactants decrease and
products increase)
• at any given time there is no variation in
composition at different points in the
reactor because of perfect mixing inside
the reactor 19
CA VS t,
 CA VS t,p Fig
• 1

21
Q2
The gas-phase reaction
A B+C
is carried out isothermally in a 20-dm3 constant-volume batch reactor. Twenty moles of pure A is initially placed in the reactor. The reactor is
well mixed
(a) If the reaction is first order with a specific rate constant of 0.865 min-1
calculate the time necessary to reduce the number of moles of A in the reactor to 0.2 mol.
(Ans.: t = 5.3 min)
(b) If the reaction is second order with a specific rate constant of 2 dm3/ mol.min, calculate the time necessary to consume 19.0 mol of A.
(c) If the temperature is 127"C, what is the initial total pressure?
What is the final total pressure assuming the reaction goes to completion?
Q3 Repeat Q2 assuming the reaction is in a constant-pressure batch reactor
Q4
The irreversible gas-phase nonelementary reaction
A+2B - - - -> C
is to be carried out isothermally in a constant-pressure batch reaction. The feed is at a temperature of 2270C, a pressure of 1013 kPa,
and its composition is 33.3% A and 66.7% B. Laboratory data taken under identical conditions are as follows:
-rA(mol/dm3.s)x103 0.0l 0.005 0.002 0.001

-xA 0.0 0.2 0.4 0.6

Calculate :
•The volume of the reaction mixture at xA=0
•The time required to attain 60% conversion
•The volume of the reaction mixture at xA=0.60
 Advantages/Disadvantages of BR
• is simple,
• needs little supporting equipment,
• high flexibility-high conversions
through high reaction time as
desired
• ideal for small-scale experiments
(kinetics studies).
 Advantages/Disadvantages of BR2
• single unit may be used for the
manufacture of relatively small
amounts of different material (drugs,
dyes, cosmetic articles)
• not a dedicated unit
• Disadvantages -idle periods (for
loading, unloading, cleaning, heating
etc).
 Design equation of BR
• Obtained from the law of conservation of
matter.
• Written for any component in the system
[ reactant, product, inert]
• Usually in terms of limiting reactant ,A
• Control volume is the whole volume of
reactor because of uniform conditions within
it
• element of volume= Control volume
 Control volume/element of
volume
• Reactions occur in a localized region of space
• Control volume or element of volume is
any region of space that has a finite volume
with boundaries that clearly separate the region
from the rest of the universe.
• real or abstract , macro sized
• Chosen according to the dictates of the
analysis that we are undertaking
26
 Law of conservation of mass

• a
 Balance after t>0
• Rate in=0 no inflow after charging
• Rate out=0 no outflow after charging
• Rate of disappearance by reaction=V(-rA)
• V(-rA)= vol x [mol/vol-time]=mol/time

• Rate of accumulation=dNA/dt

• t=reaction time
• V= volume of the reaction mixture
 Substituting in equation:
0 -0 - V(-rA) = -NA0dXA/dt
Integrating between from t=0, XA=0

X Ae
t X Ae
dX A

dX A
 dt  N  t  NA0
0
A0
0
V( rA ) 0
V( rA )
For constant volume reaction mixture
X Ae
dX A
t  CA 0 
0
( rA )

•equation gives time required for a desired level of conversion

•Integral evaluated by methods discussed 29
 Evaluating the integral
 d CA
X Ae CA CA 0
dX A d CA
t  CA 0 
0
(  rA )
 CA 0 
CA 0
 
(  rA )CA 0 C A (  rA )
CA  CA 0 (1  xA )
 d C A  C A 0 d xA
 d C A / C A 0  d xA

30
 Reaction time, t, is the performance
measure for a Batch Reactor
• Integral =area under the curve of 1/(-rA )
vs. XA.
• It may be evaluated:
1.Analytically
2.Graphically
3.Numerically( minimum of 5 points
considered sufficient)
31
f(x)
Graphical

1
2
3

a=0 x=(a+b)/2 b=XAe 32

 NUMERICAL integration : Simpson’s
1/3 rule
• Divide area into even number of equal–size
strips of width h
• Area=(h/3)x[ENDS + 4 x ODDS + 2 x EVENSS]
For 4 equal size strips
• Area=(h/3) x [(f0 + f4) +4(f1 + f3)+2f2 ]
• h=(b-a)/4
• Applicable for even number of strips
• Limitations exist for this calculation
33
Variable volume reaction mixture-constant
pressure reactor for gas phase
reaction

Substituting in the batch reactor design equation

t
 CONTINUOUS STIRRED TANK REACTOR
(CSTR)
• feed mixture continuously enters and the outlet
mixture is continuously withdrawn. Hence
• ‘Continuous’ refers to the inflow and outflow of
materials. Hence Continuous flow stirred tank
reactor is a better name CFSTR
• CSTR also misses the essence of the idealization
completely
• ideality arises from assumption that the reactor is
perfectly mixed and hence homogeneous. Hence:
• Continuous perfectly mixed reactor(=CPMR) is an
even better name
• used alone or as part of a battery of CSTRs
35
CSTR: Homogeneous reaction mixture,
constant inflow & outflow
Steady inflow

Steady outflow

36
 REACTORS IN SERIES

9/1/2018
38
 CSTR contd2.
• mixing so perfect that concentration and
temperature are spatially uniform within
whole of reactor and
• correspond to those of the exit stream;
• operates in a steady mode w.r.t. time
–at all times, Ci is same at any point
• operates in a steady mode w.r.t. Space
–Ci is same at all points at any t
40
Design equation: CSTR
element of volume= whole reactor. Why?-
whole reactor forms a homogeneous
mixture
• Rate in=FA0
• Rate out=FAe
• Rate of disappearance by reaction = V(-rA)
• Rate of accumulation = 0 (steady state)
• FA0 - FAe- V(-rA)=0
 CSTR contd.
•reactants continuously fed into the reactor
•products continuously drawn from reactor
• *
•Also called vat,
•backmix reactor,
•Mixed-flow reactor
•100% back mixing reactor

43
 Term In Square Brackets
=area of the rectangle: 1/(-rAe) By
X
• Rearranging to obtain the space
Ae time,

CA0/-rAe

CA0/-rA

xA xAe 44
45
VCSTR=[FA0/(-rA)] x XAe
 Space time and space velocity
• τ = time required to process one reactor volume of feed
measured at specified conditions, usually feed conditions
• τ = V/vo = (reactor volume)/(volumetric feed rate
• =space time
• Space velocity=1/space time
• But feed and reaction mixture may be in different phases.
• gas hourly Space velocity=GHSV=
• = [volume of gaseous feed per hour]=/[volume of reactor]
• liquid hourly Space velocity=LHSV=
• =[volume of liquid feed per hour]/[volume of reactor]
• feed may enter as a liquid but react as a vapour -important
to state conditions 47
 APPLICATION OF CSTR.
For continuous production
• WHEN INTENSE MIXING IS REQUIRED
• CAN BE USED ALONE OR AS part OF BATTERY of
CSTRs
• EASY TO MAINTAIN GOOD TEMPERATURE
CONTROL-perfect mixing
• CONVERSION OF REACTANT PER VOLUME IS
LOWEST OF THE FLOW REACTORS- large volume is
required
• USED FOR MOST LIQUID PHASE REACTIONS
48
Plug/Piston/ slug flow reactor [PFR]
Continuous Tubular Reactors (CTRs).
Plug flow Tubular Reactors (PFTR)

• FLUID flows orderly through the reactor

• No element of fluid mixes with or Overtakes
any other element ahead or Behind.
• There may Be Lateral Mixing,
• No diffusion along the flow path
• (0% of backmixing).
49
50
 Plug flow Tubular Reactors (PFTR)
• CONTINUOUS OPERATION
• reactants continuously fed into the reactor
• products continuously drawn from reactor
• operates in a steady mode wrt. time
• [at all times, Ci is same at a given point]
• Spatial variation in composition and
temperature from entrance to exit of
reactor
 PFR or PFTR or CTRs
• Variation in composition and temperature
along the length of reactor
• The PFR model works well for many fluids:
liquids, gases, and slurries.
• turbulent flow and axial diffusion cause a
degree of mixing in the axial direction in real
reactors
• PFR model is appropriate when these effects
are sufficiently small that they can be ignored.
53
Design equation2
 DESIGN EQUATION: PFR
• element of volume is a section of tube of
volume ∆V, small enough for the rate of
reaction within it to be considered uniform.
• Rate in (moles / time) =FA
• Rate out (moles / time) = FA + ∆ FA
• Rate of disappearance by reaction = ∆ V(-rA)
• Rate of accumulation =0 (steady state)
• Substituting in balance equation
55
FA-(FA+∆FA)-(-rA)∆V=0. Simplifying yields
• -∆FA=(-rA)∆V
• ∆FA/∆V=-(-rA)=rA
• As ∆V→0, equation becomes
• dFA/dV =(rA) or dV= dFA/(rA)
• Differentiating FA = FA0(1- XA ) w.r.t V,
• dV =FA0 [dXA/(-rA)]

56
From : FA= FA0(1- XA)

Separating variables

and integrating to give volume of reactor

Space time
 Applications of PFR
• Large-scale reactions
• Homogeneous or heterogeneous reactions
• Continuous production
• Most gas phase reactions
• Relatively Easy to maintain(no moving parts)
• Highest conversion per volume
• Difficult to control temperature within the
reactor, hence hot spots for exothermic rxns
• As one long tube or as a tube bank 58
 Actual residence time and space time
• THE actual time a fluid element resides in
the reactor will be equal to the space time
only if:
1. There is no change in the number of moles
during the reaction
2. There is no change in temperature along the
reactor
3. There is no change in pressure
Because: υ= vo(1+XAεA) [T /T0][P 0 /P]
 Actual residence time: PFR
If the time to traverse an element of volume of
reactor dV at constant and pressure, is dtr
• then
• From differential form of the design equation

• Substituting for dV from above,

•

• tr=Actual residence time of fluid in reactor, 60

 Actual residence time: PFR contd.
Summing up over the whole length of the reactor- by integrating

Q
The vapor-phase cracking of acetone to ketene and methane: CH3OCH3 → CH2O+ CH4
is first-order with respect to acetone and the specific reaction rate can be expressed by:
k=exp (45.45-45222/T) ; where k is in reciprocal seconds and T is in Kelvin.
In this design, it is desired to feed 3.5 g mol/min of acetone to a tubular reactor that is operated isothermally.
The feed of pure acetone enters at 2000 K and a pressure of 165 kPa. Assuming the same constant pressure
and temperature throughout the reactor, determine for 45 % conversion of the acetone
a) the space time ,
b) space velocity and
c) the actual residence time
d) Explain any difference between the space tie and the actual residence time
 PFR VS CSTR
• In a PFR, each and every molecule spends the same
amount of time in the reactor
• that period is equal to the residence time
• the concentration in each parcel of fluid entering the
reactor drops by the same amount.
• In contrast, in a CSTR there is no single amount of time
that each small parcel of fluid spends in the reactor.
• perfect mixing: some parcels may spend a long time
mixing around inside the CSTR
• others may, by chance, reach the exit in a relatively short
time. Since all these parcels are mixed together to result
in a single outlet concentration, an average value of
residence concentration results
62
 Some comments about the ideal reactors
• Comparison can be made from the Levenspiel plots
• For the plots shown VCSTR > VPFR Why?
Comparison: CSTR vs. PFR

64
CSTR IN SERIES VS. SINGLE CSTR
V SINGLE CSTR >V TWO CSTR in series

Why?

FA0
1/-rA2

XA2
FA2
1/-rA1
V1 XA1
V2
FA1

65
PFR IN SERIES VS. SINGLE PFR
V SINGLE PFR =V TWO PFR in series
Order of Sequencing Reactors in series
•Performance depends on intermediate conversion

67
• As the number of equal-size CSTR in series is
increased
• the performance approaches that of a single PFR
of the same total volume

68
cost of using several smaller reactors, which will be
greater than the cost of a single larger reactor.

Hence: there may be some economic trade-offs

between reactor size and cost.

 “Practice questions from “Elements of Chemical

Reaction Engineering by Scott Fogler”

69
 Reaction Rate
• 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)

NOTE: dCA/dt is not the rate of reaction

 Reaction Rate
• rj is the rate of formation of species j per
unit volume [e.g. mol/dm3*s]

• rj is a function of concentration,
temperature, pressure, and the type of
catalyst (if any)
 Reaction Rate
• rj is the rate of formation of species j per unit
volume [e.g. mol/dm3/s]
• rj is a function of concentration, temperature,
pressure, and the type of catalyst (if any)

• rj is independent of the type of reaction system

(batch reactor, plug flow reactor, etc.)
 Reaction Rate
• rj is the rate of formation of species j per
unit volume [e.g. mol/dm3/s]
• rj is a function of concentration,
temperature, pressure, and the type of
catalyst (if any)
• rj is independent of the type of reaction
system (batch, plug flow, etc.)

• rj is an algebraic equation, not a

differential equation
General Mole Balance
Batch Reactor Mole Balance
 CSTR
Mole Balance
Plug Flow Reactor
Plug Flow Reactor Mole Balance
PFR:

FA dFA
The integral form is: V
FA 0 rA

This is the volume necessary to reduce the entering molar flow rate (mol/s) from FA0 to the
exit molar flow rate of FA.
 Packed Bed Reactor
Mole Balance
PBR

FA0 FA   rdW  dNdt

A
A

FAdFA
The integral form to find the catalyst weight is: W
FA 0 rA
Reactor Mole Balance Summary