Reactor Design 1

CHE3044F :
Reactor Design 1
Klaus Mller
Department of Chemical Engineering
University of Cape Town
March 8, 2012
Contents
1 Mole (or mass) balances 5
1.1 Chemical Reaction Engineering . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.1.1 Generic ow diagram of a chemical process . . . . . . . . . . . . . . . 6
1.1.2 What do we need to know . . . . . . . . . . . . . . . . . . . . . . . . 8
1.1.3 Industrial processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.1.4 The Chemical Feed stocks . . . . . . . . . . . . . . . . . . . . . . . . 10
1.2 Rate of a reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
1.2.1 Dening when a chemical reaction takes place . . . . . . . . . . . . . 12
1.2.2 Dening the rate of reaction . . . . . . . . . . . . . . . . . . . . . . . 13
1.2.3 The volume in the reaction rate and its relationship to the mass of the
reacting system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
1.2.4 The rate equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
1.3 The general mole balance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1.4 Mole balance for batch reactors . . . . . . . . . . . . . . . . . . . . . . . . . 16
1.5 Mole balance for continuous stirred tank reactor (CSTR) . . . . . . . . . . . . 18
1.6 Mole balance for a homogeneous plug ow reactor (PFR) . . . . . . . . . . . 19
1.7 Mole balance for a heterogeneous xed bed reactor (FBR) . . . . . . . . . . . 22
1.8 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2 Reactor sizing for single reactions using conversion 24
3 Properties and denitions of the reaction rate equation (reaction rate law) (Fogler
chapter 3) 47
4 Reaction stoichiometry and the reaction rate law (Fogler chapter 3) 60
5 Isothermal reactor design for single reactions (Fogler chapter 4) 78
6 Isothermal reactor design for multiple reactions (Fogler chapter 6) 79
7 Collection and data analysis (Fogler chapter 5) 80
7.1 Algorithm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
7.1.1 Limitations on data collected . . . . . . . . . . . . . . . . . . . . . . . 81
7.1.2 Postulate a rate law . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
7.1.2.1 Homogeneous reactions : . . . . . . . . . . . . . . . . . . . 82
1
CONTENTS CONTENTS
7.1.2.2 Heterogeneous reactions (those with a catalyst): . . . . . . . 82
7.1.3 Choose the same reactor type that matches the data collected . . . . 82
7.1.4 Write the rate equation in terms of the data that has been collected . 83
7.1.5 Make simplications based on good chemical reaction engineering principles 83
7.1.6 Dierential analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
7.1.7 Integral analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
7.1.8 Goodness of t and variance in model parameters . . . . . . . . . . . . 85
7.2 batch reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
7.2.1 Method of excess . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
7.2.2 Example : Dierential method . . . . . . . . . . . . . . . . . . . . . . 86
7.2.3 Example : Integral method . . . . . . . . . . . . . . . . . . . . . . . . 91
7.2.3.1 The standard (linearised) analyses . . . . . . . . . . . . . . . 91
7.2.3.2 Example 5.2 (Fogler) . . . . . . . . . . . . . . . . . . . . . 93
7.2.4 Example : Non-linear regression . . . . . . . . . . . . . . . . . . . . . 94
7.3 Method of initial rates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
7.3.1 Example (Fogler 5-4) . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
7.4 Method of half lives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
7.5 Dierential reactors (including CSTR and recycle reactors) . . . . . . . . . . . 99
7.5.1 Mole balances : CSTR (and recycle reactor with rapid recycle) . . . . 100
7.5.2 Mole balances : Tubular and packed bed systems . . . . . . . . . . . . 101
7.5.3 Example : Fogler 5-5 . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
8 Developing rate laws from reaction mechanisms and reaction pathways 107
9 Bio-reactor engineering mechanisms 108
10 Bio-reactor design 109
11 Analysis of reactor ow patterns on reactor performance (Fogler chapter 13) 110
2
List of Figures
1.1 Generic ow diagram of a process. (adapted from Schmidt, 2005) . . . . . . 6
1.2 Phthalic anhydride process. (Fogler, 2006) . . . . . . . . . . . . . . . . . . . 6
1.3 The face of chemical reaction engineering. (Fogler, 2006) . . . . . . . . . . . 7
1.4 The multidisciplinary nature of chemical reaction engineering. (Schmidt, 2005) 8
1.5 The reaction rate in a reactor. . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.6 General mole balance. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1.7 Batch reactor. (Fogler, 2006) . . . . . . . . . . . . . . . . . . . . . . . . . . 16
1.8 Change of moles with time in a batch reactor. . . . . . . . . . . . . . . . . . 17
1.9 Continuous stirred tank reactor, abbreviated as CSTR. . . . . . . . . . . . . . 18
1.10 Diagrams of typical plug ow reactors commonly known as PFRs. . . . . . . 19
1.11 The PFR mole balance. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
1.12 Arbitrary shaped PFR. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
1.13 Molar ow rate proles across the PFR. . . . . . . . . . . . . . . . . . . . . 21
1.14 Tubular xed bed reactor. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
7.1 Cubic and polynomial t to the data. . . . . . . . . . . . . . . . . . . . . . . 89
7.2 Comparing the linear data t with the non-linear data t. The green line repre-
sents the non-linear t. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
7.3 Batch reactor integral analysis linear plots for zero, rst and second order kinetics
using concentrations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
7.4 Standard regression plot for the second order reaction. . . . . . . . . . . . . 94
7.5 Predicted and experimental data when using the non-linear leasts squares method
applied to concentration data. . . . . . . . . . . . . . . . . . . . . . . . . . . 96
7.6 Data for example (Fogler5-4). . . . . . . . . . . . . . . . . . . . . . . . . . . 97
7.7 Linearised initial rate plot for the dissolution process. . . . . . . . . . . . . . 98
7.8 Half-life analysis plot. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
7.9 Dierential reactor operation : concepts. . . . . . . . . . . . . . . . . . . . . 100
7.10 Regression plot for the r
CO
dependence on P
CO
. . . . . . . . . . . . . . . . 104
7.11 Plotting the r
CO
dependence on P
H
2
. . . . . . . . . . . . . . . . . . . . . . . 104
7.12 The prediction of the reaction rate when regressing for all the rate law constants.106
7.13 The prediction of the reaction rate when regressing for k, K
H
2
in the rate law. . 106
3
List of Tables
1.1 Summary of reactor mole balances. . . . . . . . . . . . . . . . . . . . . . . . 23
7.1 Reaction rate as a function of concentration using cubic spline and polynomial
tting. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
7.2 Experimental reaction data for the conversion of CO to CH
4
. . . . . . . . . . 102
7.3 Processed reaction data. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
4
Chapter 1
Mole (or mass) balances
5
1.1. CHEMICAL REACTION ENGINEERINGCHAPTER 1. MOLE (OR MASS) BALANCES
1.1 Chemical Reaction Engineering
1.1.1 Generic ow diagram of a chemical process
Figure 1.1: Generic ow diagram of a process. (adapted from Schmidt, 2005)
Figure 1.2: Phthalic anhydride process. (Fogler, 2006)
Reactors are the key unit operation on plant. A plant is typically designed around a reactor.
The operation of the reactor determines the operability and performance of the plant. See
Figs 1.1 and 1.2.
Almost all the worlds commodities and essential items are made using a reactive process.
The reactors can be as simple as a long hollow tube or a complex reaction vessel many
10s of meters tall with many reactions occurring in multiple phases and with the aid of a
catalyst.
It is their knowledge of chemical reaction engineering that makes chemical engineers unique
Reactors come in all shapes and sizes and arise in many interesting places, see Fig 1.3
6
Figure 1.3: The face of chemical reaction engineering. (Fogler, 2006)
7
1.1.2 What do we need to know
Some facts about practicing chemical engineers
Single reactions never happen. Reactors are complex unit operations with many simultane-
ous chemical reactions occuring in multiple phases. The engineer needs to know enough
about the reactions, the ow patterns in the vessel, the interaction of heat and mass
transfer in order to assemble the basic understanding of the reactor operation.
The kinetic rate equation almost never exists. Rate equations must be estimated, approx-
imated from reaction engineering fundamental knowledge and from experimental or plant
data. The rate equation indicates how fast a reaction proceeds and thus determines both
the size, productivity and selectivity of the reacctor.
Industrial processes are often severely limited by heat and mass transfer. The engineer
must know how to integrate these into the reactor design to yield its actual performance.
Reactor design typically proceeds according to a well dened path
Bench Scale reactor (batch, continuous) pilot plant operating plant
Very few engineers will have the honour of following this process. Practicing engineers will most
likely encounter and old reactor that has been modied many times which the engineer must
now operate in such a way to double the through-put, improve selectivity and reduce the waste.
Alternatively, reactor has failed and the engineer must understand the reasons of failure and
re-commission the reactor to operate better without failing.
The typical tasks are
Maintain and operate a process,
Fix a problem,
Increase the capacity or selectivity at minimum cost.
The task must be solved as quickly as possible,for there are many more tasks that need doing.
Often, gaining a deeper understanding is often not possible due to the presssure of other more
pressing tasks. Besides being competent at back of the envelope calculations and having a
good intuitive feel for reaction engineering, the engineer also needs to be able to build quick
practical models of the reaction process by integrating all the other engineering disciplines, see
Fig 1.4.
Figure 1.4: The multidisciplinary nature of chemical reaction engineering. (Schmidt, 2005)
8
This course is the rst course of two in reaction engineering and will aim to develop good
reactor engineering skills for optimal homogeneous, isothermal reactor design by combining the
knowledge of
kinetic models and their structure,
elementary reactor design equations,
various type of reactors and conguration of multiple reactor sequences,
multiple reactions and nature of the reactions,
experimental data to determine the rate equation.
There will essentially be two types of problems
1. The ones that can be solved in 3 lines often without a calculator. These will build good
reaction engineering intuition;
2. The ones that require more rigorous calculation and in many cases a computer. These
are the design type problems that will exercise the procedural skills and study the what
if scenarios.
1.1.3 Industrial processes
The following table shows the interesting contrasts between the large volume producers and
high value chemicals produced by the pharmaceutical companies.
(Schmidt, 2005)
9
1.1.4 The Chemical Feed stocks
The following tables shows the usage of chemicals in the USA in 1994. This ranking of these
chemicals isn constantly changing. It provides an interesting incetive for the development of
alternative processes.
(Schmidt, 2005)
This is in contrast to the prices of chemicals shown in the following table. Note the low value
of the crude oil in contrast to solvents and more so pharmaceuticals (see insulin).
10
11
1.2. RATE OF A REACTION CHAPTER 1. MOLE (OR MASS) BALANCES
(Schmidt, 2005)
1.2 Rate of a reaction
1.2.1 Dening when a chemical reaction takes place
Chemical species are dened by the type, the number and arrangement of the atoms. For
example isomers dier only by the arrangement of the chemical species
These, isomers, although they have the same type and number of atoms, the dierent arrange-
ment of the atoms results in these molecules having dierent physical properties and are thus
chemically distinct from each other.
A chemical reaction has taken place when one of more of the chemical species in the system
of study are transformed by an innitesimal amount into (an)other chemical species.
This transformation can be one of the following
Change the arrangement of the atoms :
double bond isomerisation :
skeletal isomerisation :
Decomposition :
12
disproportionation :
Addition :
and many more other types of reactions (see organic chemistry hand book!)
Often it is simpler to work with letters such as A, B, C, D for chemical species. Thus the
reaction of methanol to dimethyl-ether and water written as
2CH
3
OH CH
3
OCH
3
+ H
2
O
can be written as
2A D + W
or
A
1
2
D +
1
2
W (1.1)
1.2.2 Dening the rate of reaction
Consider that A is reacting in the vessel in Fig 1.5. r
A
represents the consumption of A at
some position in the reactor vessel and it is dened as follows.
Figure 1.5: The reaction rate in a reactor.
Denition of reaction rate : The number of moles of A that are being reacted (consumed or
produced) per unit volume per unit time [mol .m
3
.s
1
].
13
Denition of r
A
: r
A
represents the rate of formation of species A. Thus r
A
represents the
rate of consumption of A. Thus r
A
is positive for a product and negative for a reactant.
Reaction stoichiometry : In reaction 1.1, the consumption of one mole of A will yield 0.5 moles
of D and 0.5 moles of W. For example if the rate of consumption of A is -5 mol .m
3
.s
1
then r
A
= 5 or r
A
= 5 and r
D
= 2.5 and r
W
= 2.5. Similarly the rate equations for A,
D and W are related by the reaction stoichiometry: r
A
= 2r
D
= 2r
W
=
r
D
1
/2
=
r
W
1
/2
.
It is good practice to decide on a convention and stick to it. This course will work with the
denition of r
A
as given above.
1.2.3 The volume in the reaction rate and its relationship to the mass of
the reacting system.
Homogeneous reactors well mixed : When the vessel is well mixed such that the concentra-
tion of A is equal trhough the reacting vessel, the volume represented by the m
3
term
refers to the vessel volume. In gas phase systems the actual volume of the vessel is used.
In liquid phase systems, if the vessel is not completely lled, the liquid volume is used.
Homogeneous reactors with concentration gradient : When the species concentrations vary
throughout the reactor volume, the volume refered to in the rate equation is that of a
dierential element in which it can be assumed that the concentration is uniform for all
species (i.e. well mixed).
Heterogeneous reactors : In these reactors the reaction takes place on a catalyst surface (or
a solid surface or within the catalyst pores). The volume refered to in the rate equation is
then the volume of the catalyst. Since the density of a catalyst is constant, it is easy to
convert the rate equation into a mass basis using the catalyst density and then the rate
equation is dened as moles of A reacting per mass of catalyst per time [mol .kg
1
.s
1
] and
is denoted as r
A
. (Note that the activity per unit surface area can similarly be converted
into a mass basis by using the catalyst properties which dene the surface area to mass
ratio.
Multi-phase reactions : If the reaction contains a vapour and a liquid phase, then there will be
a rate equation for each phase, r
vap
A
and r
l i q
A
and the volume refered to will be the vapour
phase volume and the liquid phase volume respectively. Similarly, for more phase including
solids and catalysts.
1.2.4 The rate equation
The rate equation
r
A
= f uncti on(C
i
, T, P, C
catal yst
)
is a function of the concentration (activities) of all or some of the chemical species in the reacting
system, or the temperature and pressure of the system and the properties of the catalyst. The
rate equation is an algebraic expression dening how the reaction rate varies with the chemical
and physical properties of the reacting system.
NOTE : The rate equation is independent of the reactor in which the reaction is being
carried out in.
14
1.3. THE GENERAL MOLE BALANCE CHAPTER 1. MOLE (OR MASS) BALANCES
Examples of possible rate equations for the reaction
A Pr oducts
Linear variation of reaction rate with concentration : r
A
= kC
A
Quadratic variation of the reaction rate with concentration : r
A
= kC
2
A
Saturation of the reaction rate : r
A
=
k
1
C
A
(1 + k
2
C
A
)
2
NOTE : Although r
A
=
dC
A
dt
is true from the denition of the units of the reaction rate, this
equation is actually the design equation for a constant volume batch reactor, which will be
developed later in this course. It is not the denition of the rate equation.
1.3 The general mole balance
Consider a mole balance of species j in a arbritary shaped reaction vessel (or control volume) in
Fig 1.6. , For example in the reaction
A pr oducts
A would represent j . It is not necessary the know what the other products are at this stage.
Also species j can be a reactant of a product (i.e. sometimes products are fed to the reactor
as a result of recycle)
Figure 1.6: General mole balance.
The mole balance then can be written as
IN OUT + Gener ati on = Accumul ati on
_
_
rate of ow
of j INTO
the system
[mol .s
1
]
_
_
rate of ow
of j OUT of
the system
[mol .s
1
]
_
_
+
_
_
rate of generation
of j by chemical
reaction in the system
[mol .s
1
]
_
_
=
_
_
rate of accumulation
of j within
the system
[mol .s
1
]
_
_
15
1.4. MOLE BALANCE FOR BATCH REACTORS CHAPTER 1. MOLE (OR MASS) BALANCES
and in symbols this is
F
j,0
F
j
+ G
j
=
dN
j
dt
(1.2)
where N
j
is the total number of moles of j in the system. G
j
represents the total transformation
of j that has occurred when passing through this reaction vessel. G
j
can be related to the
reaction rate for two special cases
1. When the concentration of all species is constant throughout the entire system volume
: Then the reaction rate r
j
is the same throught the whole reaction vessel and G
j
= r
j
V
where V is the volume of the vessel. The general mole balance, equa 1.2 then becomes
F
j,0
F
j
+ r
j
V =
dN
j
dt
(1.3)
2. When the concentration of all species varies throughout the reaction volume : Then the
reaction rate will be dierent at all locations. Dividing the system volume into dierential
elements (see Fig 1.6), V
i
and assuming that the concentration of all species is constant
in each dierential element, means that the reaction rate is constant on each dierential
element. Thus the rate of generation of species j in each element is given by r
j,i
V
i
. The
rate of generation of species j in the system is thus the sum of all the dierential elements
: G
j
= r
j,1
V
1
+r
j,2
V
2
+r
j,3
V
3
=
M
i =1
r
j,i
V
j
. In the dierential limit, as V 0 and
M then G
j
=
_
V
r
j
dV . The general mole balance in this case becomes
F
j,0
F
j
+
V
_
r
j
dV =
dN
j
dt
(1.4)
Equation 1.4 is the GENERAL DESIGN EQUATION for chemical reaction engineering. When
used on its own, it is applicable to all ISOTHERMAL reaction systems. For NON-ISOTHERMAL
reaction systems an ENERGY BALANCE will also be needed in order to solve equation 1.4.
1.4 Mole balance for batch reactors
Figure 1.7: Batch reactor. (Fogler, 2006)
16
1.4. MOLE BALANCE FOR BATCH REACTORS CHAPTER 1. MOLE (OR MASS) BALANCES
Fig 1.7(A) shows a schematic diagram of a industrial batch reactor. Its a vessel with a lid so
that it can be opened for cleaning. It has ports for adding and removing chemicals. It almost
always has a stirrer (agitator) and they are almost always used for liquid phase operations. There
are coils or a jacket around the outside of the vessel for heating and cooling. Some vessels have
coils internally, others use evaporation cooling or direct steam heating. The vessel is always
raised o the ground.
Fig 1.7(B) shows the text book schematic of a batch reactor as a vessel lled with liquid and a
stirrer to provide perfect mixing, such that the concentration o all species in the reactor are
the same everywhere in the vessel. The reactor volume is that of the reactive mixture, in this
case the liquid volume and NOT the volume of the vessel.
A batch reactor is operated by lling the vessel with the required reactants. The reactor is
then heated to the desired reaction temperature and the reaction is allowed to proceed for a
predetermined amount of time, called the reaction time. During this time there is no ow into
or out of the reactor. An the end of the the reaction time the mixture is removed (pumped...)
out of the vessel. The reactor is then cleaned and the cycle starts again with fresh reactants.
Since there is no ow into or out of the vessel, the general mole balance on species j becomes
V
_
r
j
dV =
dN
j
dt
Assuming that the system is well mixed, the reaction rate equation will be the same through
the whole vessel, thus the design equation is
dN
j
dt
= r
j
V (1.5)
Notice that the general equation, equa 1.5 is based on the number of moles in the vessel and
not the concentration. More on this later.
For a reaction A B the number of moles of A decrease with time while the number of moles
of B increase with time, as shown in Fig 1.8.
Figure 1.8: Change of moles with time in a batch reactor.
17
1.5. MOLE BALANCE FOR CONTINUOUS STIRRED TANK REACTOR (CSTR) CHAPTER 1. MOLE (OR MASS) BALANCES
The time t
1
that is required to consume (N
A0
N
A
) moles can be obtained by integrating equa
1.5:
t
1
=
_
N
A1
N
A0
dN
A
r
A
V
(1.6)
where N
A0
are the number of moles at the start of the reaction, t = 0 and N
A1
are the number
fo moles of A that are remaining after a reaction time of t
1
.
1.5 Mole balance for continuous stirred tank reactor (CSTR)
(A) (B)
Figure 1.9: Continuous stirred tank reactor, abbreviated as CSTR.
Fig 1.9(A) shows a schematic diagram of a continuous stirred tank reactor (CSTR). These
reactors always have a stirrer or some form of vigorous agitation to ensure that the composition
of all species is uniform throughout the reaction system. They also have a heating/cooling jacket
of coils to control the temperature in the vessel. They can be closed vessels or open vessels.
They can be lled to capacity or have partially lled with or without two phase operation.
These reactors are most often used for liquid applications involving poorly miscible streams
and/or solids. They are also used for systems which require the additiion of another phase e.g.
like bubbling a reactive gas through a liquid reactant.
Fig 1.9(B) shows the diagramatic way in which a CSTR is represented for calculation purposes.
The mole balance for species j across this vessel is
F
j,0
F
j
+
V
_
r
j
dV =
dN
j
dt
If the reactor is operated at steady state, the there is no variation with time of all species on
the reactor, thus,
dN
j
dt
= 0 and the mole balance becomes;
F
j,0
F
j
+
V
_
r
j
dV = 0
18
1.6. MOLE BALANCE FOR A HOMOGENEOUS PLUG FLOW REACTOR (PFR) CHAPTER 1. MOLE (OR MASS) BALANCES
In addition, since there are no spatial variations in the concentrations as the contents of the
vessel is well mixed, the reaction rate, r
j
is constant throughout the whole vessel, which means
that
_
V
r
j
dV = r
j
V and the mole balance then becomes;
F
j,0
F
j
+ r
j
V = 0 (1.7)
V =
F
j 0
F
j
r
j
This is the nal design equation for the CSTR. It is important to note that the concentration
of the species in the reactor have the same concentration as the species leaving the reactor
in the exit ow.
1.6 Mole balance for a homogeneous plug ow reactor (PFR)
Figure 1.10: Diagrams of typical plug ow reactors commonly known as PFRs.
A plug ow reactor, Fig 1.10 is basically an empty tube through which a reactive uid ows. The
reactive streams are mixed at the reactor inlet. The reactor can be heated or cooled depending
on the reaction requirements by using a jacket, by making steam on the outside of the tubes
or coils in the vessel. The important aspect of these reactors is that they are extremely long
in relation to their diameter, as it is best to have turbulent ow. This is to promote plug ow.
Plug ow is dened as ow in which there is no axial mixing (no mixing along the length) by
good radial mixing (mixing perpendicular to the ow). This means that all the species that enter
the reactor spend exactly the same amount of time in the vessel. Species interact only radially
and not axially. Plug ow reactor can be mounted inside furnaces for very high temperature
operation.
19
Figure 1.11: The PFR mole balance.
In developing the general mole balance for a PFR, consider the schematic in Fig 1.11. The
general mole balance can be applied to the whole reaction vessel, thus for species j it is
F
j,0
F
j
+
V
_
r
j
dV =
dN
j
dt
Since the species concentrations (or molar ow rates) are not constant, it is not possible to
simplify the integral expression. Furthermore, when more than one reaction is taking place,
the reaction rate term, r
j
does not only depend on species j but can also depend on the other
species in the reaction vessel, preventing the integration from being carried out. Thus in this
case the general mole balance in this form is not particularly useful. Assuming steady state
makes
dN
j
dt
= 0. Then dierentiating with respect to the reactor volume yields
dF
j,0
dV

dF
j
dV
+ r
j
= 0
and since the feed does not depend on the reactor volume, thus
dF
j,0
dV
= 0 and thus
dF
j
dV
= r
j
(1.8)
which is the general mole balance for a PFR. Note that this is a dierential equation.
The reactor mole balance can be obtained in a more intuitive way by considering a dierential
element, in which it can be assumed that the species concentrations are constant and thus the
reaction rate is also constant. The dierential mole balance over the dierential element is then
_
_
molar ow rate
of species j
IN at V
[mol .s
1
]
_
_
molar ow rate
of species j
OUT at V + V
[mol .s
1
]
_
_
+
_
_
Molar rate of
generation of
species j in V
[mol .s
1
]
_
_
=
_
_
rate of accumulation
of species j
within V
[mol .s
1
]
_
_
which in symbols, for a reactor at steady state becomes
F
j
|
V
F
j
|
V +V
+ r
j
V = 0
Dividing through by V and re-arranging yields
F
j
|
V +V
F
j
|
V
V
= r
j
20
Since the ow rate us a function of V in the sense that F = f (V ) the term
F
j
|
V +V
F
j
|
V
V
represents an approximation to the dereivative of F with respect to V . In the limit as V
the PFR mole balance becomes
dF
j
dV
= r
j
as before.
IMPORTANT NOTE : for plug ow conditions, the shape of the reactor does not matter
and is arbitrary (in the derivation volume was used with no mention of the shape of the
vessel). Thus Fig 1.12 could also have been used for the derivation of the mole balance. This
is no longer true once other factors are accounted for, on in particular is pressure drop, which
depends on the velocity, which would vary with cross-setional area.
Figure 1.12: Arbitrary shaped PFR.
Consider again the reaction A B but this time in a PFR. The molar ow rate proles across
the reactor as shown in Fig 1.13. These are similar to the batch reactor, except that volume
has replaced time.
Figure 1.13: Molar ow rate proles across the PFR.
The design equation for this reaction is
dF
A
dV
= r
A
(1.9)
21
1.7. MOLE BALANCE FOR A HETEROGENEOUS FIXED BED REACTOR (FBR) CHAPTER 1. MOLE (OR MASS) BALANCES
To determine the volume of reactor required to achieve the exit ow rates F
A1
and F
B1
in Fig
1.13 can be obtained by integrating equation 1.9 from the beginning of the reactor where V = 0
and F
A
F
A0
until V
1
where F
A
= F
A1
;
_
V
1
0
dV = V
1
=
_
F
A1
F
A0
dF
A
r
A
1.7 Mole balance for a heterogeneous xed bed reactor (FBR)
(a) (b)
Figure 1.14: Tubular xed bed reactor.
Fig 1.14(a) shows a xed bed reactor with the catalyst packed in the tubes and coolant owing
around it (sometimes steam is made in this way). This conguration is used if the reaction is very
exothermic (produces a lot of heat) and/or the reactants or products are heat sensitive and/or
the catalyst deactivates at higher temperatures and/or the catalyst selectivity deteriorates and
it is crucial to keep the reactor as close to isothermal operation as possible. For other reactions
where the exothermicity can be tolerated or the reaction is near thermo-neutral, the vessel can
simply be packed with catalyst particles as a uniform bed.
The particle size and the bed diameter are key design parameters. The isothermal vessels are
typically long and thin with a relatively small vessel : particle diameter ratios (20-40). Adiabatic
vessels are typically short and squat with large vessel : particle diameter ratios (>>100). Mass
and heat transfer in the catalyst particle to/from the active site becomes more dicult as the
particle size increases. In contrast, the pressure drop across the bed increases as the particle
size decreases. These opposing eects need to be optimised during the reactor design phase.
The interplay of heat and mass transfer in catalytic reactions is a leads to exciting reaction
systems. More of this will be the topic of reactor design 2.
In this rst level mole balance, it will be assumed that heat and mass can be neglected and that
pressure drop can be ignored and that the ow in the vessel is perfect plug ow. The reaction
rate is thus based on the catalyst mass (or catalyst volume), since it is the catalyst that is
responsible for the reaction that is taking place. (Vessel volume and catalyst volume can easily
be used or converted to, through the density of the catalyst particles). Thus the reaction rate
22
1.8. SUMMARY CHAPTER 1. MOLE (OR MASS) BALANCES
is dened as
r
A
= [(mol Ar eacted).s
1
.g
1
catal yst
]
Fig 1.14(b) shows the dierential element used in the mole balance;
F
j
|
W
F
j
|
W+W
+ r
j
W = 0
Dividing through by V and re-arranging yields
F
j
|
W+W
F
j
|
W
W
= r
j
Since the ow rate us a function of W in the sense that F = f (W) the term
F
j
|
W+W
F
j
|
W
W
represents an approximation to the dereivative of F with respect to W. In the limit as W
the PFR mole balance becomes
dF
j
dW
= r
j
(1.10)
and the catalyst weight required to achieve a exit oe rate of F
A
is given by
W =
_
F
A
F
A0
dF
A
r
A
1.8 Summary
Table shows summary of all the mole balances carried out in this chapter.
Table 1.1: Summary of reactor mole balances.
reactor Comment Mole balance
dierential algebraic integral
Batch no spatial variation
dN
A
dt
= r
A
V t =
_
N
A
N
A0
dN
A
r
A
V
CSTR no spatial variation, steady state - V =
F
A0
F
A
r
A
PFR steady state
dF
A
dV
= r
A
V =
_
F
A
F
A0
dF
A
r
A
FBR steady state
dF
A
dW
= r
A
W =
_
F
A
F
A0
dF
A
r
A
(Fogler, 2006)
These represent the denite equations of the reactor design 1 course and for that matter all
reaction engineering design problems can be solved using these equations. The rest of this
course is on the application of these equations to specic problems.
23
Chapter 2
Reactor sizing for single reactions using
conversion
24
Chapter 3
Properties and denitions of the reaction
rate equation (reaction rate law) (Fogler
chapter 3)
47
Chapter 4
Reaction stoichiometry and the reaction
rate law (Fogler chapter 3)
60
Chapter 5
Isothermal reactor design for single
reactions (Fogler chapter 4)
78
Chapter 6
Isothermal reactor design for multiple
reactions (Fogler chapter 6)
79
Chapter 7
Collection and data analysis (Fogler
chapter 5)
80
7.1. ALGORITHM CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5)
This chapter develops some of the techniques that are used to obtain rate laws for chemical re-
actions, which are then ultimately used in the design of a pilot plant and ultimately a commercial
unit. THE KNOWLEDGE AND TOOLS GAINED HERE ARE EXTREMELY IMPORTANT.
The purpose of this chapter is to develop the following knowledge
1. To be able to estimate the reaction rate constant, the reaction order and other constants
in the rate law from appropriately collected experimental data.
2. To be able to study experimental data and decide how it should be analysed
3. To be able to develop the appropriate reactor design equation and rate law that will
describe the experimental data
4. To be able to formulate the design equation in the appropriate form such that it is suitable
for regression with experimental data to determine the rate law parameters
5. To be able to formulate the objective function and use appropriate computer code to carry
out the non-linear regression
6. To be able to select the best model based on good statistical methods.
7.1 Algorithm
The following steps are general and apply to all the examples and reactor types that follow.
7.1.1 Limitations on data collected
The following are guidelines when collecting data or looking at data to be analysed
1. Make every eort to ensure that the data is collected under isothermal and isobaric con-
ditions
2. Make sure that the data are collected at steady state and that the MASS BALANCE IS
OBEYED.
3. Make every eort to ensure that the data collected is free of transport limitations such as
lm resistance, pore diusion. (see later chapters)
4. Make every eort to ensure that the idealisations of the assumed reactor type are obeyed.
For example, if a plug ow reactor is assumed, the reactor conguration choosen must
behave like a plug ow reactor or else the estimated rate constant will depend on the
shape of the reactor and CANNOT BE USED FOR SCALE-UP. For example in a two
phase batch reactor (gas bubbles in the liquid), it is necessary that the stirring is fast
enough such that the bubbles are small enough to ensure that there are no mass transfer
limitations.
5. Make every eort to ensure that there are no unexpected concentration and temperature
gradients. For example, in a ow reaction bomb (CSTR) in which a combustion reaction
is taking place, gfeat care needs to be taken to ensure that the mixing (stirring) is fas
enough to ensure that there are NO temoperature and concentration gradients in the
vessel. The same applies to fast liquid phase reactions in a batch reactor, the stirring
must be fast enough to ensure complete mixing at all times during the reaction.
81
6. There are ways to analyse non-isothermal and non-isobaric data, but it is considerably
more dicult to get estimates of the kinetic constants that are reliable. It is also beyond
thre scope of this course. Similarly, non-ideal reactor behaviour can be accounted for, but
this also leads to less accurate estimations of the rate constants.
7.1.2 Postulate a rate law
The design and development of rate laws is the topic of the next section (Fogler!!!!). In many
cases the rate law needs to be developed in conjunction with the data analysis and experimental
observations.
Good places to start
7.1.2.1 Homogeneous reactions :
mono-molecular : r
A
= kC
n
A
= k
A
(7.1)
bi-molecular : r
A
= kC
A
C
B
= k
A
P
B
(7.2)
reversible : r
A
= k
_
C
A
C
B
C
C
C
D
K
e
_
(7.3)
In particular for reversible reactions it is important that the rate law is able to describe the
chemical equilibrium of the reaction(s) i.e. for reaction 7.3 the equilibrium limit is
K
e
=
C
Ce
C
De
C
Ae
C
Be
where the C
i e
are the equilibrium concentrations when r
A
= 0, and obtained from thermody-
namics.
7.1.2.2 Heterogeneous reactions (those with a catalyst):
Langmiur-Hinshilwood (LH) : r
A
=
kP
A
1 + K
A
P
A
(7.4)
LH-reversible : r
A
=
k
_
P
A
P
B
K
e
_
1 + K
A
P
A
+ K
B
P
B
(7.5)
Also here the rate law must obey the thermodynamic limitations of the reaction thermodynamics.
7.1.3 Choose the same reactor type that matches the data collected
Batch reactor :
r
A
=
1
V
d(N
A
)
dt
=
dC
A
dt
=
dC
A
dt
=
1
RT
dP
A
dt
(7.6)
PFR :
r
A
=
dF
A
dV
= F
A0
dX
A
dV
(7.7)
CSTR :
r
A
=
F
A0
F
A
V
=
F
A0
V
X
A
(7.8)
82
7.1.4 Write the rate equation in terms of the data that has been collected
e.g. P
A
vs t, N
A
vs t, X
A
vs W etc.
7.1.5 Make simplications based on good chemical reaction engineering
principles
Some typical examples are;
1. Reactants in excess : This means that for example that when the concentration of B
exceeds the concentration of A by more that a factor of 100, then the second order
reaction r
A
= kC
A
C
B
can be approximated by r
A
= k
A
where k
= kC
B
. NOTE that
in this csae the rate constant k
is a function of the concentration of B (C

B
). NOTE also
that this rate law cannot be used for conditions in which the concentration of B is of the
same order of magnitude as A. For situations like this new experimental data will have to
be collected.
2. Reactants are dilute in a reaction mixture : If for example the mole fractions of A, B in a
reacting mixture are less than 1%, then any volume expansion, pressure change, ow rate
change, due to the change the number of moles, can be neglected (i.e. = 0). Similarly
for liquid phase reactions.
3. Fast reactions can be assumed to be at chemical equilibrium, which simplies the rate
equations.
7.1.6 Dierential analysis
This method of analysis takes the approach that the data will be in the form
REACTION RATE vs RATE LAW
r
A
=
_
dC
A
dt
,
dF
A
dV
,
dP
A
dt
,
F
A0
V
X
A
, etc
_
vs kC
A
C
B
(7.9)
In a CSTR, the data automatically comes in this form i.e. r
A
=
F
A0
V
X
A
. However, for
all other reactors this provides an approximation to the data collected. All other reactors will
collect primarily C vs t or F vs V data which has to be converted into rate data by numerical
dierentiation. Numerical dierentiation increases the scatter (error) in the data and leads
to poor data analysis and this method is not recommended, although its use will be quickly
demonsrated as is done in Fogler.
Often, data is collected in what is known as a dierential reactor, in which the feed entering is
already partially converted (i.e. X
i n
> 0) and products leaving only increase the conversion by
a few percent (i.e. X
out
= X
i n
+ 0.05), then the reactor can be treated similarly to a CSTR,
viz. r
A
= F
A0
X
i n
X
out
V
.
In all cases the data analysis normally follows the following approach:
r
A
= kC
A
C
B
(7.10)
83
taking logs on both sides:
l n(r
A
) = l n
_
dC
A
dt
_
= l n(k) + l n(C
A
) + l n(C
B
) (7.11)
which is a linear equation in (l n(k), , ) which can then be found by linear regression. This is
a good approach when the reaction order are unknown and are needed to be estimated, since
the equation is linear in the reaction orders. NOTE : this methods uses log weighting of the
data, and this will have slightly dierent answers than the direct non-linear regression, which
can be formulated as :
mi n [f (k, , )] =
n
i =1
_
r
A,i
kC
A,i
C
B,i
2
0
where r
A,i
represents the measured data data at each experimental value i of the concentrations
C
A,i
, C
B,i
in the reaction system when a total number of n experiments have been carried out.
The objective function f (k, , ) must be minimised by adjusting k, , until the least squared
error is as close to zero as possible (using excels solver or scilabs lsqrsolve).
7.1.7 Integral analysis
This analysis is more applicable to standard reactors which generate data in the form:
C
A
, F
A
, P
A
, X
A
vs t, V, W, ,
W
F
A0
(7.12)
In all these cases the design equation must be integrated. Note that integration is a smoothing
process and reduces the errors in the estimated rate constants as opposed to the dierential
method. For the simple
th
order reaction r
A
= kC
A
in a liquid phase batch reactor this yields:
C
A
= C
A0
exp(kt) = 1 (7.13)
C
(1)
A
= k(1 )t + C
(1)
A0
(7.14)
For the rst equation ( = 1) the linear plot l n(C
A
) vs t will yield rate constant from the slope.
However, for the second equation, the linear plot of C
(1)
A
vs t will require an estimate of .
Thus the linear regression requires repeated guesses of , which is silly. Thus this type of data
can only be analysed using non-linear analysis except in some special cases. (typically when the
reaction order is given, linearisation is often possible).
Non-linear regression in this case yields:
mi n [f (k, )] =
n
i =1
_
C
(1)
A,i
+ k(1 )t
i
C
(1)
A0
_
2
0 (7.15)
or in terms of the measured variable, C
A
it is
mi n [f (k, )] =
n
i =1
_
_
C
A,i

_
k(1 )t
i
C
(1)
A0
_
1
1
_
_
2
0 (7.16)
There are many situations where integration is not possible. For example, consider the second
order non-equi-molar reaction with the rate law : r
A
= kC
A
C
B
. Writing in terms of conversions
84
for a constant ow rate system yields, the PFR design equation is:
F
A0
dX
A
dV
= kC
+
A0
(1 X
A
)
_
C
B0
C
A0
X
A
_
(7.17)
V
F
A0
kC
+
A0
=
X
A
_
0
1
(1 X
A
)
_
C
B0
C
A0
X
A
_
dX
A
(7.18)
which can be formulated as an objective function
mi n [f (k, , )] =
n
i =1
_
_
V
F
A0,i
kC
+
A0

X
A,i
_
0
1
(1 X
A
)
_
C
B0
C
A0
X
A
_
dX
A
_
_
2
0 (7.19)
where the dierent conversion are obtained by varying the ow rate (this is the most common
way, changing V is the other way). In this formulation the integral must be evaluated each time
for each value of X
A,i
. All this is not a problem on a computer. (NOTE, that if C
A0
= C
B0
then it is no longer possible to distinguish from . The advantage of this approach is that
it is general, requires no guessing of , and has no limitations of these values either. The
disadvantage is that it needs some computer code to be written!
It is possible to have multiple reactions with multiple rate constants, where integration using an
ODE solver is needed each time is also easily done on a computer.
7.1.8 Goodness of t and variance in model parameters
The goodness of t can be obtained in two ways
(i) A correlation coecient can be obtained between the experimental and the predicted data
e.g plotting (r
A
)
exp
versus (r
A
)
model
and estimating the mean and variance.
(ii) looking at the least squares error :
_
n
i =1
_
(r
A
)
exp
(r
A
)
model
2
n m
where n is he number
of data points and m is the number of estimated parameters (3 in the case shown here)
The variance in the model parameters can be obtained by studying the Jacobian matrix of the
objective function : J
i ,j
=
_
f (p)
j
p
i
_
where p is the vector p = [k, , ] and f (p) is evaluated
at each data point j , and thus J is a m n matrix. Then the variance in the parameters p is
given by
p
i
= p
i

i ,i
;
i ,i
=
_
f (p)
_
_
J
T
J
_
1
_
i ,i
n m
(7.20)
where
_
_
J
T
J
_
1
_
i ,i
refers to the diagonals of the matrix. When
i ,i
0.2p
i
then the parameter
is a poor estimated and the model is most likely over parameterised and that means that there
are most likely too many model parameters or there is not sucient data.
85
7.2. BATCH REACTORS CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5)
7.2 batch reactors
7.2.1 Method of excess
The idea of this method is to reduce the dependence of the rate law on multiple concentrations
into one concentration. This method is particularlygood for getting rst estimates of the reaction
order with respect to the key component. For example, the reaction :
A + B pr oducts
with the rate law
r
A
= kC
A
C
B
(7.21)
is dicult to analyse when both , are unknown. The idea then is to carry out the reation in
two ways (i) Using excess B such that C
B
= C
B0
and does not change signicantly during the
reaction. Then
r
A
= kC
A
C
B
= kC
B0
C
A
= k
A
(7.22)
which can then be used to nd .
(ii) Using excess A such that C
A
= C
A0
and remains eectively constant during the reaction,
similarly
r
A
= kC
A
C
B
= kC
A0
C
B
= k
B
(7.23)
which can be used to nd .
(iii) Once , have been found, then normal concentration data can be analysed for k.
7.2.2 Example : Dierential method
(Fogler, ex 5.1, p260)
The reaction of triphenyl methyl chloride (A) with methanol(B) viz
(C
6
H
5
)
3
CCl + CH
3
OH (C
6
H
5
)
3
COCl + HCl
A + B C + D
is carried out in a batch reactor in a solution of benzene and pyridine at 25C. HCl reacts with
the pyridine, which then precipitates making the reaction irreversible. The concentration time
data is collected
time (min) 0 50 100 150 200 250 300
Concentration of A, C
A
[mmol.L
1
] 50 38 30.6 25.6 22.2 19.5 17.4
The initial concentration of methanol was 500 mmol.L
1
.
1. determine the reaction order with respect to triphenyl-methyl-chloride
2. the reaction order of methanol was given as 1, determine the reaction rate constant
SOLUTION
PART 1
Looking at the data
the time vector is given by : [t] = [t
1
t
2
t
3
...t
n
]
the concentration vector is given by : [C
A
] = [C
A,1
C
A,2
C
A,3
...C
A,n
]
86
where n is the number of data points. This also means that you cannot estimate more than n
model parameters.
Proposed rate law : r
A
= kC
A
C
B
now, C
B0
= 10C
A0
thus the it may be assumed that C
B
= C
B0
constant over the range of
the data collected (well, not really that constant, by the change is less than 5%)
Then r
A
= k
A
where k
= kC
B0
Mole balance :
dN
A
dt
= r
A
V
stoichiometry : N
A
= N
B
= N
C
= N
D
Since this is dilute liquid phase system, the density (volume) of the system is constant, thus the
design equation becomes;
dC
A
dt
= k
A
(7.24)
dierential analysis then requires;
l n
_
dC
A
dt
_
i
= l n(k
) + l n(C
A,i
) (7.25)
where the i values run over all data points. Thus it is necessary to nd the reaction rate as a
function of time.
The best way to do this is to t a cubic-spline to the data
//fit a cubic-spline to the data
d = splin(tt,Ca);
function Cat=spln(t)
Cat=interp(t,tt,Ca,d)
endfunction
Cas=interp(t,tt,Ca,d) //spline interpolated values
and then to dierentiate the cubic-spline
//get the gradient
ttt=tt;ttt(n)=ttt(n)-0.1; //takingcare of the last point
dCa_dt_s=diag(numdiff(spln,ttt));
disp(-dCa/dt=+string(-dCa_dt_s))
. This yields the following data in table 7.1.
An alternative is to t a polynomial to the data. This is done as follows;
The error between each data point and the polynomial is given by
i
= C
A,i
(a
1
+ a
2
t + a
3
t
2
+ a
4
t
3
+ a
5
t
4
...) (7.26)
which can be vectorised as follows since it is a linear operation with basis sets
i
= C
A,i
[p]
i
[a]
T
(7.27)
[p]
i
= [1 t
i
t
2
i
t
3
i
t
4
i
...] [a] = [a
1
a
2
a
3
a
4
a
5
] (7.28)
Here the vectot [p] represents the basis sets. Note that these can be any set of independent
functions e.g. [p] = [1 t si n(t) exp(t) t
3
]. This can be expanded for every data point n :
_
3
.
.
.
n
_
_
=
_
_
c
A,1
C
A,2
C
A,3
.
.
.
C
A,n
_
_
1 1 1 1 1
t
1
t
2

t
2
1
t
2
2
.
.
.
.
.
.
t
3
1
.
.
.
.
.
.
t
n
1
t
n
n
_
_
_
_
a
1
a
2
a
3
.
.
.
a
m
_
_
= [] = [C
A
] [p][a]
T
0 (7.29)
87
Note that m is the number of parameters [a] which in this case is 5. Note also that m n
for a meaningful solution. When m = n then the solution is unique, one parameter for every
equation. However, as with most data, n > m and the solution will never be exactly zero, rather
the objective function needs to be minimized, thus
mi n = []
T
[] (7.30)
Matlabs and Scilabs backslash operator (\) does exactly that (i.e. the overdetermined system,
Ax = b yields the least squares solution x = A\b). Applying this concept here yields the
parameters of the polynomial that ts the C
A
vs t data;
[a]
T
= [p]\[C
A
] = [50 0.2978 1.34E 03 3.485E 06 3.67E 09]
The code that does this is and the data is given in the table.
//polynomial fit to the data using a non-linear leasts squares
solver (the long way)
function f=polfit(a,n)
tx=[ones(1:n); tt; tt^2; tt^3; tt^4]; //define the
vector of polynomial basis sets
f=Ca-tx*a //calculate the error at each point
endfunction
a0=[1 1 1 1 1]; //initial guess
a=lsqrsolve(a0,polfit,n) //solve the non-linear problem
disp(a_cubic=[+string(a)+]) //display
tx=[ones(1:nt); t; t^2; t^3; t^4];
Cap=tx*a; //calculate the polynomial fitted values
function f=CaPol(t) //define a function in terms of t
tx=[ones(1:n) t t^2 t^3 t^4]; //changes since t is a
column vector
f=tx*a //the value of Ca
endfunction
//polynomial regression using linear leasts squares (the short
but abstract way)
txx=[ones(1:n); tt; tt^2; tt^3; tt^4];
aa=txx\Ca
disp(a_poly=[+string(a)+])
Table 7.1: Reaction rate as a function of concentration using cubic spline and polynomial tting.
C
A
50 38 30.6 25.6 22.2 19.5 17.4
_
dC
A
dt
_
spl i ne
0.303 0.185 0.119 0.0814 0.0590 0.0485 0.0351
_
dC
A
dt
_
pol y
0.298 0.188 0.119 0.0801 0.0603 0.0485 .0334
The tted data is shown in Fig 7.1.
88
15
20
25
30
35
40
45
50
0 50 100 150 200 250 300
time; t [s]
c
o
n
c
e
n
t
r
a
t
i
o
n
;
C
A
[
m
m
o
l
:
L
1
]
Figure 7.1: Cubic and polynomial t to the data.
The linear regression using equa 7.25 is
//linear regression for the rate constant and reaction order
//using cubic spline data
aa_s=regress(log(Ca),log(-dCa_dt_s)); //such that
log(-dCa_dt)=aa(1)+aa(2)*log(Ca)
kr=exp(aa_s(1))
alpha=aa_s(2)
disp(k=+string(kr)+ alpha=+string(alpha));
//using polynomial data
aa_p=regress(log(Ca),log(-dCa_dt_p)); //such that
log(-dCa_dt)=aa(1)+aa(2)*log(Ca)
kr=exp(aa_p(1))
alpha=aa_p(2)
disp(k=+string(kr)+ alpha=+string(alpha));
Linear regression of the spline t data this data yields :
l n(k) = 9.116; k
= 0.0001099 L.mmol
1
.min
1
and = 2.035 and l sqr Er r r or = 0.0136
Linear regression of the poly t data this data yields :
l n(k) = 9.116; k
= 0.0001046 L.mmol
1
.min
1
Direct non-linear regression of the cubic spline data uses this equation
mi n f (k
, ) =
n
i =1
_
_
dC
A
dt
_
i
k
A,i
_
and the following code
89
//direct non-linear regression
function f=EE(b,n)
k=b(1);alpha=b(2)
f=-dCa_dt_s-k*(Ca^alpha)
endfunction
b0=[1 1];
b=lsqrsolve(b0,EE,n)
disp(k=+string(b(1))+ alpha=+string(b(2)));
this data yields :
k
= 0.0001467 L.mmol
1
.min
1
So why are these values dierent :
Figure 7.2 shows the two dierent plots which eectively represent the two dierent methods.
10
10
10
-2
-1
0
10 10
1 2
C
A
[mmol:L
1
]
d
C
A
d
t
[
m
m
o
l
:
L
1
:
m
i
n
1
]
(a) linear-t
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
15 20 25 30 35 40 45 50
C
A
[mmol:L
1
]
d
C
A
d
t
[
m
m
o
l
:
L
1
:
m
i
n
1
]
(b) non-linear-t
Figure 7.2: Comparing the linear data t with the non-linear data t. The green line represents
the non-linear t.
The linear regression transforms the data into a log-log scale. This means that the error for
the small values of the concentrations and small rates are weighted much more heavily than the
values at the large concentrations. However, typically, small concentrations are more dicult
to measure and thus also have the largest experimental error. This error is magnied by the
log-log scaling. The non-linear tting, on the other hand, leaves the data in its original for and
weights all errors on this basis.
Figure 7.2(a) shows the log-log plot is not able to distinguish between the dierent regressions.
On the other hand Fig 7.2(b) shows that the non-linear regression (green) shows a superior t to
the rate data at high concentrations. The non-linear tting thus provides a more representative
set of rate constants. This deviation is more pronounced in the rate constant.
PART 2
Since = 1 then the true rate constant k can eb calculated:
k =
k
C
B0
= 2.92E 7 [L.mol
1
.min
1
]
2
Thus the rate law is given by
r
A
= 0.292C
2
A
C
B
[mol.L
1
.s
1
]
90
It is possible to t for all 3 parameters k if the concentration of B can be found from the
concentration of A. (normally B should also be measured). This would give an idea of the errors
made in assuming that the concentration of B is constant. From the reaction stoichiometry
C
A
= C
A0
(1 X); X = 1
C
A
C
A0
C
B
= C
B0
C
A0
X = C
B0
C
A0
+ C
A
Then the rate law becomes
r
A
= kC
A
(C
B0
C
A0
+ C
A
)
which can be used for dirrect non-linear regression or linear regression using the log-log approach
non-linear
mi n f (k, , ) =
n
i =1
_
(r
A,i
) kC
A,i
(C
B0
C
A0
+ C
A,i
)
_
2
which can be solved by a non-linear leasts squares, Scilabs lsqrsolve
[k, , ] = [180, 2.13, 2.37] with l sqr Er r r or = 0.00712.
This has the smallest error of them all. Interesting, WHY
Linear log-log:
l n(r
A
)
i
= l n(k) + l n(C
A,i
) + l n(C
B0
C
A0
+ C
A,i
)
l n(r
A
) = p a
p =
_
_
1 l n(C
A
) l n(C
B0
C
A0
+ C
A,i
)
1
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
1
.
.
.
.
.
.
_
_
a =
l n(k)
which can be solved by the backslash (a = p\l n(r

A
)).
[k, , ] = [9.44E13, 2.47, 6.93] with l sqr Er r r or = 0.067.
This solution has failed. This is due to the linear dependence of the two concentration columns.
7.2.3 Example : Integral method
Contrary to what Fogler says, this is not a trial and error method. When the reaction orders are
known, then there are many standard rate laws for which the design equations can be integrated
and a appropriate regression can be carried out. If not, then they simply become partr of the
regression procedure.
7.2.3.1 The standard (linearised) analyses
For the reaction A pr oducts it is always useful to test the data with the standard cases,
or make a standard plot. Assuming a constant volume batch reactor, the following analyses
can be used for zero, rst, second and nth order reactions. Fig 7.3 shows these plots on a
concentration basis for a batch reactor.
91
Zero order reaction
C
A
= C
A0
kt
slope = k
WARNING
There is no natural limit
on the smallest value of C
A
it can go negative
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
time; t [s]
c
o
n
c
e
n
t
r
a
t
i
o
n
;
C
A
[
m
o
l
:
m
3
]
rst order reaction
log
C
A
C
A0
= kt
slope = k
-4.0
-3.5
-3.0
-2.5
-2.0
-1.5
-1.0
-0.5
0.0
0.5
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
time; t [s]
l
o
g
C
A
C
A
0
o
r
l
o
g
(
1
X
)
2nd order reaction; kC
2
A
1
C
A
= kt +
1
C
A0
slope = k
R
x
n

o
r
d
e
r

<

2
R
x
n

o
r
d
e
r

>

2
1.0
1.5
2.0
2.5
3.0
3.5
4.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
time; t [s]
1
C
A
2nd order reaction; kC
A
C
B
log
C
A
C
B0
C
A0
+ C
A
= k(C
B0
C
A0
)t + log
C
A0
C
B0
slope = k(C
A0
C
B0
)
-5.0
-4.5
-4.0
-3.5
-3.0
-2.5
-2.0
-1.5
-1.0
-0.5
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
time; t [s]
l
o
g
C
A
C
B
0
C
A
0
+
C
A
Figure 7.3: Batch reactor integral analysis linear plots for zero, rst and second order kinetics
using concentrations.
Zero order reaction :
dC
A
dt
= k; C
A
= C
A0
kt; X =
k
C
A0
t (7.31)
So plotting C
A
vs t is a linear plot with an intercept C
A0
and slope k, as shown in Fig
7.3. (or plotting X vs t has a slope of
k
C
A0
. Note that it is not necessary to know the
initial concentration C
A0
when making the C
A
vs t plot, since this given my the intercept.
First order reaction :
dC
A
dt
= kC
A
;
C
A
C
A0
= exp(kt); 1 X = exp(kt) (7.32)
linearisation yields
l n
_
C
A
C
A0
_
= kt; l n(1 X) = kt (7.33)
So when plotting l n
_
C
A
C
A0
_
vs t the slope of the line is k, as shown in Fig 7.3 (similarly
for plotting of l n(1 X) vs t) Note that re-arrangement to
l n(C
A
) = l n(C
A0
) kt (7.34)
92
and plotting l n(C
A
) vs t also does not require knowledge of the intial concentration.
Furthermore, the reaction rate does not depend on the concentration, and thus it is not
important to keep the initial concentration constant during experimentation.
Second order reaction :
dC
A
dt
= kC
2
A
;
dX
dt
= kC
A0
(1 X)
2
Also for C
A0
= C
B0
(7.35)
dC
A
dt
= kC
A
C
B
= kC
A
(C
B0
C
A0
+ C
A
);
dX
dt
= kC
A0
(1 X)
_
C
B0
C
A0
X
_
(7.36)
and their integrated forms re-arranged into linear equations for C
A0
= C
B0
:
1
C
A
= kt +
1
C
A0
plot :
1
C
A
vs t slope : k intercept :
1
C
A0
(7.37)
X
1 X
= kC
A0
t plot :
X
1 X
vs t slope: kC
A0
(7.38)
And for C
A0
= C
B0
:
l n
_
C
A
C
B0
C
A0
+ C
A
_
= k(C
B0
C
A0
)t + l n
_
C
A0
C
B0
_
(7.39)
plot : l n
_
C
A
C
B0
C
A0
+ C
A
_
vs t slope : k(C
B0
C
A0
) intercept : ln
_
C
A0
C
B0
_
(7.40)
l n
_
_
_
_
C
A0
C
B0
X 1
X 1
_
_
_
_
= k(C
B0
C
A0
)t (7.41)
plot : l n
_
_
_
_
C
A0
C
B0
X 1
X 1
_
_
_
_
vs t slope : k(C
B0
C
A0
) (7.42)
Some of these standard plots are made in Fig 7.3. In all cases, except for
1
C
A
= kt +
1
C
A0
it is necessary to know the concentrations of A and B at the start of the reaction.
q
th
order reaction :
dC
A
dt
= kC
q
A
;
dX
dt
= kC
q1
A0
(1 X)
q
(7.43)
1
C
q1
A
= k(1 q)t +
1
C
q1
A0
;
1 (1 X)
q1
(1 x)
q1
= k(1 q)t (7.44)
In these linearised equations it is necessary to know the reaction order q. (see Fig 7.3)
7.2.3.2 Example 5.2 (Fogler)
Continuation of example 5.1 : The purpose now is to regress the concentration data directly
without nding the reaction rate. Thus, assuming that teh reaction is second order;
dC
A
dt
= k
C
2
A
;
1
C
A
= k
t +
1
C
A0
(7.45)
93
Regression can be done by noting that the integrated equation is related to y = a + bx when
y =
1
C
A
and x = t. The the solution of this equation by for example Scilabs regress routine,
yields b = k
and a =
1
C
A0
. The value obtained for a provides a check on the validity of the
model, since C
A0
is already known. So k
= 0.0001248 and C
A0
= 49.7. So the model ts
the data well as shown in Fig 7.4..
0.010
0.015
0.020
0.025
0.030
0.035
0.040
0.045
0.050
0.055
0.060
0 50 100 150 200 250 300 350
time; t [min]
1
C
A
[
L
:
m
o
l
1
]
Figure 7.4: Standard regression plot for the second order reaction.
7.2.4 Example : Non-linear regression
Non-linear regression requires the development of a objective function which is then used in a
non-linear leasts squares solver (Scilabs lsqrsolve is a particularly good one, EBE-matlab does
not have such routines and the nextbest bet is EXCEL!!!)
Continuation of Foglers example 5-1:
Noting that k
and are to be found and that the data is given in the form C
exp
A,i
vs t
i
, it
therefore makes sense to integrate a general -order rate equation and its integrated form.;
dC
A
dt
= k
A
; C
model
A
=
_
C
1
A0
(1 )kt
1
1
(7.46)
This is the batch reactor design equation and will from now on be called the model. Now the
purpose of this method is to minimise the error between the experimental concentrations and
the model predicted concentrations, thus this will form the objective function;
mi n f (k
, ) =
n
i =1
i
=
T
(7.47)
94
7.3. METHOD OF INITIAL RATES CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5)
where n is the number of experimental data points and
i
is the error between the experimental
and model concentrations;
i
= C
exp
A,i
C
model
A,i
(7.48)
i
= C
exp
A,i

_
C
1
A0
(1 )kt
i
1
1
(7.49)
where is a vector of values,one for each data point collected
=
_

1

2
. . . . . .
n
(7.50)
The solution proceeds by developing a function that calculates the
i
values at each data point
and then call the scilab routine lsqrsolve to carry out the least squares minimisation. The scilab
function is
function f=model1(x,n)
kr=x(1);alpha=x(2); //x is a vector of two parameters
f=Ca-(Ca(1)^(1-alpha)-(1-alpha)*kr*tt)^(1/(1-alpha))
endfunction
The calling of the least squares solver then has hte code
//call the least squares solver
x0=[0.0001 2]; //initial guess
x=lsqrsolve(x0,model1,n)
kr=x(1);alpha=x(2);
disp(kr=+string(kr)+ alpha=+string(alpha))
Cam=(Ca(1)^(1-alpha)-(1-alpha)*kr*t)^(1/(1-alpha)) //model predicted val-
ues
The model parameters obtained are :
k
= 0.000111 = 2.037
And the quality of the fata t can be seen in Fig 7.5.
It is possible to use the same code to regress with = 2. When this is done then k
= 0.000126
similar to those obtained before. The values of k
are summarised here:

method k

dierential : Linear regression of the spline t 0.1109 2.035
dierential : Linear regression of the poly t 0.1046 2.048
dierential : non-linear regression 0.1467 1.95
Integral 0.1248 2.000
non-linear regression C
A
0.111 2.037
non-linear regression 0.126 2.000
7.3 Method of initial rates
The idea here is to study the reaction at very short reactions times, or more precisely, at small
conversions (say < 5% change in conversion over the reaction period). This avoids complications
from any possible reversible reaction steps, deactivation as a result of by-products forming,
etc. These experiments are carried out a various inlet concentrations (C
A0
) and/or various
conversions at the inlet. Then the reaction rate at these conditions is estimated from data
collected over a very small conversion range. Possible sequences might be
95
15
20
25
30
35
40
45
50
55
0 50 100 150 200 250 300
time; t [min]
C
A
[
m
o
l
:
L
1
]
Figure 7.5: Predicted and experimental data when using the non-linear leasts squares method
applied to concentration data.
C
A0
20 10 5 2 1
C
A
19 9.5 4.75 1.9 0.95
t 10 15 12 10 8
Which yields the reaction rate
C
A
t
=
C
A0
C
A
t
at the concentration
C
A0
+ C
A
2
from which
the law parameters can be obtained. Or possibly
X
i n
0.1 0.2 0.3 0.4 0.5
X
out
0.11 0.21 0.31 0.41 0.51
F
A0
10 15 20 25 30
From which the reaction rate can be obtained from a dierential reactor balance (see later)
Limitations of this method
1. Real reactions undergo deactivation. If deactivation is fast (FCC) then this method fails
since it becomes impossible to esrimate the initial reaction rate without the inuence of
the deactivation.
2. Real reactors operate at very high conversions, contrary to the very low conversions used
here. High conversions almost always produce side products which can inuence the
reaction kinetics, especially at high conversions, which are the conditions used under normal
operation. These methods fail to analyse such reaction systems
7.3.1 Example (Fogler 5-4)
The dissolution kinetics Calcium-Magnesium-carbonate within HCl has been measured and is
shown in the graphs below. The data in the tables have been extracted from the graphs. The
reaction is
4HCl + CaMg(CO
3
)
2
Mg
2+
+ Ca
2+
4Cl
+ 2CO
2
+ 2H
2
O (7.51)
96
Determine the reaction order with respect to HCl ?
DATA:
Run1, 4N HCl
C
HCl
4.0000 3.9993 3.9986 3.9980 3.9968
time [min] 0 2 4 6 8
Run2, 1N HCl
C
HCl
1 0.9996 0.9991 0.9986 0.9980
time [min] 0 2 4 6 8
Figure 7.6: Data for example (Fogler5-4).
SOLUTION
Assume a rate law with reaction order q :
r
HCl
= kC
q
HCl
(7.52)
This is a batch reactor, so the design equation for a constant volume system is
dC
HCl
dt
= kC
q
HCl
(7.53)
Linearising:
l n
_
dC
HCl
dt
_
= l n(k) + ql n(C
HCl
) (7.54)
Thus need to estimate the reaction rate at t = 0 in each case. This can be done with a forward
dierence formula since the data is equally spaced;
dC
CCl
dt
=
3C
t=0
HCl
+ 4C
t=2
HCl
C
t=4
HCl
2t
; t = 2 (7.55)
which yields
C
HCl ,0
[mol.L
1
] 1 4 2 0.1 0.5
dC
HCl
dt
[mol.L
1
.min
1
] 1.74E-4 3.50E-4 2.49E-4 0.66E-4 1.36E-4
Regressing these to get the reaction order: q = 0.45 and Fig 7.7 shows that the model ts the
data well.
97
7.4. METHOD OF HALF LIVES CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5)
10
10
10
-5
-4
-3
10 10 10
-1 0 1
d
C
A
d
t
0
[
m
o
l
:
L
1
:
m
i
n
1
]
Figure 7.7: Linearised initial rate plot for the dissolution process.
7.4 Method of half lives
The half life of a reaction is the time it takes to reduce the conversion (concentration) by half
the initial value. Thus a irreversible reaction, A pr oducts with a q
th
order rate law in a
batch reactor the design equation is;
r
A
= kC
q
A

dC
A
dt
= kC
q
A
(7.56)
Integration yields the reaction time to reach the concentration C
A
;
t =
1
k(q 1)
_
1
C
q1
A
1
C
q1
A0
_
=
1
kC
q1
A0
(q 1)
_
_
C
A0
C
A
_
q1
1
_
(7.57)
Using the half-life concept : t = t
1/2
then C
A
=
1
2
C
A0
, thus
t
1/2
=
2
q1
1
k(q 1)
_
1
C
q1
A0
_
(7.58)
or using a general concept, the n
th
life time, such that t = t
1/n
when C
A
=
1
n
C
A0
yields
t
1/n
=
n
q1
1
k(q 1)
_
1
C
q1
A0
_
(7.59)
Linearising this equation
l n(t
1/2
) = l n
_
2
q1
1
k(q 1)
_
+ (1 q)l n(C
A
)
The slope of the plot is (1 q) from which the reaction order can be obtained as shown in Fig
7.8.
98
7.5. DIFFERENTIAL REACTORS (INCLUDING CSTR AND RECYCLE REACTORS) CHAPTER 7. COLLECTION AND DATA ANALYSIS (FOGLER CHAPTER 5)
Figure 7.8: Half-life analysis plot.
7.5 Dierential reactors (including CSTR and recycle reac-
tors)
The idea of these kinds of reactors is to directly calculate the reaction rate and not have to
dierentiate the concentration-time data. This reduces the error. These reactors also operate
with no pressure drop and isothermally as a result of the reaction zone and conversion being
small. There are essentially 2 types of dierential reactors :
Fixed bed (plug ow) : In these reactors the conversion in the reactive zone is small. The
feed enters the reactor at various degrees of conversion which is achieved by dilution with
product species. In this way the reaction rate can be estimated at dierent conversions.
The ow rate of reactants to the reactor remains largely unchanged.
CSTRs and recycle reactors : The CSTR delivers the reaction rate at any concentration di-
rectly from the measured variables. The conversion is changed by changing the feed rate
and not the feed conversion as is needed for the xed bed reactor. A recycle reactor (no
separation of the products must take place) can be assumed to have the same analysis as
a CSTR when the recycle ratio is greater than 20, which translates into a conversion per
pass of <5%.
These type of experiments are not generally carried out in Batch type reactors, since it is dicult
to precisely dene the conditions at t = 0. These ideas can be viewed in Fig 7.9.
99
Figure 7.9: Dierential reactor operation : concepts.
7.5.1 Mole balances : CSTR (and recycle reactor with rapid recycle)
r
A
[mol.L
1
.s
1
] =
F
A0
F
A
V
=
F
A0
V
X =

0
C
A0
V
X =
C
A0
X (7.60)
r
A
[mol.kg
1
.s
1
] =
F
A0
F
A
W
=
F
A0
W
X = (WHSV )C
A0
(7.61)
So CSTRs yield the reaction rate directly at any concentration or conversion of the reactants
or products (even for multiple reactions). This is the ideal reactor conguration to use for the
development of rate laws. However, it is very dicult to achieve good CSTR operation, and
great care must be taken to ensure that the mixing is adequate such that the CSTR assumptions
are valid. The variation in reaction rate is obtained by changing the volume (V, W), the ow
rate (F
A0
) or more precisely the , WHSV .
Fig 7.9 shows the concepts of how a recycle system relates to a real integral reactor. Essentially
the catalytic zone (reactive zone) represents a slice of the normal reactor. When this reactor
section of the reactor is placed within a recycle loop in which the recycle ow rate exceeds 20
times the feed ow rate, the reactor feed will no longer be pure feed, by will be mixed with
products of the reaction and will thus enter partially converted. The high ow rates through the
reactor section ensure that (i) the conversion is low <5% (ii) the lm mass transfer limitations
are negligible. It thus provides a ideal reactor for studying the rate law of reactions.
100
7.5.2 Mole balances : Tubular and packed bed systems
Fig 7.9 also shows that the dierential reactor is also a slice of the full scale reactor. However,
in this reactor the feed must be pre-mixed with products to yield feeds that reproduce the
conversion prole of the full-scale reactor. For complex reactions this proves to be impossible.
In practice for complex reaction systems, the experimental system operates with two reactors
in series, the rst one large enough to generate the conversion desired to be used in the second
dierential reactor. These systems are not popular for the study of complex chemical reaction
system kinetics.
The mole balances are best viewed through the rst order approximation to the PBR design
equation, thus;
F
A
|
Z
F
A
|
Z+Z
r
A
W = 0;
dF
A
dW
=
0
dC
A
dW
= r
A
; F
A0
dX
dW
= r
A
(7.62)
Now making a rst order approximation of the dierential to yield the average reaction rate
within the dierential interval W is
r
A
=
F
A,out
F
A,i n
W
=
0
C
A,out
C
A,i n
W
= F
A0
X
out
X
i n
W
(7.63)
Here the conditions F
A0
and C
A0
are reserved for the ow rate and concentration of the un-
converted feed and correspond to X = 0. The reaction rate so evaluated represents, to a
rst approximation the reaction rate at the middle of the W interval, i.e. at
F
A,out
+ F
A,i n
2
;
C
A,out
+ C
A,i n
2
,
X
out
+ X
i n
2
. It is not the reaction rate at the inlet to the dierential reactor as
proposed by Fogler, i.e. draw a parallel with the trapazoidal integration where the integration
uses the average value between the end points of the interval if the integration step.
7.5.3 Example : Fogler 5-5
The formation of methane from carbon monoxide(A) and hydrogen(B)
CO + 3H
2
CH
4
+ H
2
O
A + 3B C + 2D
is being studied at 260C in a dierential reactor where the concentration of methane leaving
the reactor is measured.
(a) From the data supplied determine the conversion for each experiment and the partial pres-
sures of CO and H
2
at the inlet and outlet of the reactor. Determine also the average
reaction rate of CO across the reactor.
(b) The reaction rate equation is proportional to the partial pressure of CO with the function
f (CO) and proportional to the partial pressure of H
2
with the function g(H
2
);
r
CO
= f (CO) g(H
2
)
Determine the reaction order with respect to P
CO
by assuming the rate equation;
r
CO
= k
1
P
a
CO
101
(c) Show that the data suggests a rate law for the hydrogen dependence of
r
CO
=
k
2
P
b
1
H
2
1 + K
H
2
P
b
2
H
2
(d) By combining the two rate laws, yields the overall rate equation
r
CO
=
kP
CO
P
b
1
H
2
1 + K
H
2
P
b
2
H
2
Regress this equation for the constants k, b
1
, b
2
, K
H
2
.
DATA:
Table 7.2: Experimental reaction data for the conversion of CO to CH
4
.
Run P
CO
[atm] P
H
2
[atm] C
CH
4
[mol.L
1
]10
4
1 1 1 1.73
2 1.18 1 4.40
3 4.08 1 10.0
4 1 0.1 1.65
5 1 0.5 2.47
6 1 4.0 1.75
The exit volumetric ow rate was maintained at 300 [L.min
1
]. The catalyst bed contained
10 g of catalyst. P
CO
and P
H
2
were measured at the reactor inlet and C
CH
4
was measured at the
reactor exit.
SOLUTION
(a)
Looking at the data
(i) There are 2 sets of data, runs 1-3 are at constant P
H
2
and runs 1,4-6 are at constant P
CO
.
Thus the CO and H
2
dependence can be analysed separately
(ii) The data required will require a stoichiometric table to relate all the quantities to each other.
Make the usual assumptions : ideal gases, isothermal reactor, ...
Design equation for the reaction rate of CO is
r
CO
= F
A0
X
out
W
f (P
CO
) g(P
H
2
)
Thus it will be necessary to determine the conversion,X, the molar ow rate of CO, F
A0
and
the average partial pressures of CO and H
2
across the reactor.
Stoichiometric table gives
A B C D
in F
A0
F
B0
0 0
out F
A0
(1 X) F
A0
_
F
B0
F
A0
3X
_
F
A0
X 2F
A0
X
total F
0
= F
A0
(1 + ) F
T
= F
A0
(1 + X) =
F
B0
F
A0
=
P
B0
P
A0
102
From the data, the methane concentration gives the reaction rate, and since the exit volume
ow rate () is given, the molar ow rate of methane can be calculated from
F
C
= C
CH
4
= F
A0
X
The conversion can be obtained by looking at the methane concentration
C
CH
4
=
F
C
F
T
P
RT
=
X
1 + X
C
T
Re-arrangement gives the conversion
X =
C
CH
4
(1 + )
C
CH
4
+ C
T
Note that the total presssure P and thus the total concentration, C
T
is not constant since,
P = P
A0
+P
B0
and varies from run to run. Thus F
A0
can be obtained from the above equation.
The partial pressures of CO and H
2
at the reactor exit are given by
P
A
=
1 X
1 + X
(P
A0
+ P
B0
); P
B
=
3X
1 + X
(P
A0
P
B0
)
and the reaction rate of CO can be obtained from the above equation. Making a new table 7.3.
Table 7.3: Processed reaction data.
Run P
A,i n
P
B,i n
P C
T
X F
A0
P
A,out
P
B,out
r
CO
P
A,ave
P
B,ave
1 1.00 1.00 1.000 2.00 0.0457 0.0075 6.88 0.996 0.981 0.0052 0.998 0.990
2 1.18 1.00 0.847 2.18 0.0498 0.0161 8.16 1.171 0.951 0.0132 1.175 0.975
3 4.08 1.00 0.245 5.08 0.116 0.0106 28.2 4.071 0.877 0.0300 4.075 0.938
4 1.00 0.10 0.100 1.10 0.0251 0.0071 6.90 0.999 0.079 0.0049 0.999 0.089
5 1.00 0.50 0.500 1.50 0.0342 0.0107 6.90 0.996 0.471 0.0074 0.998 0.485
6 1.00 4.00 4.000 5.00 0.114 0.0076 6.86 0.993 3.983 0.0052 0.996 3.99
P
A
is relatively constant, however the biggest variation (still not much) is in P
B
across the
reactor even when P
B0
is a constant, since 3 moles of B required for every mole of A that reacts
away.
(b)
Regression for k
1
, a :
l n (r
CO
) = l n(k
1
) + a l n(P
CO
)
thus k
1
= 0.00745 and a = 1.03. Fig 7.10 shows that the data scatter is large and too few
points!!
103
10
10
10
-3
-2
-1
10 10 10
-1 0 1
P
CO
[atm]
l
n
(
r
C
O
)
[
m
o
l
:
L
1
:
m
i
n
1
]
Figure 7.10: Regression plot for the r
CO
dependence on P
CO
.
(c)
Looking at the second table and the rate law
r
CO
=
k
2
P
b
1
H
2
1 + K
H
2
P
b
2
H
2
and making a plot of the data, Fig 7.11.
0.0045
0.0050
0.0055
0.0060
0.0065
0.0070
0.0075
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
P
H
2
[atm]
l
n
(
r
C
O
)
[
m
o
l
:
L
1
:
m
i
n
1
]
Figure 7.11: Plotting the r
CO
dependence on P
H
2
.
(i) plotting the data shows that at low P the rate is low,it then increase as P
H
2
increases, goes
through a maximum and then decreases again.
104
(ii) At low P
H
2
: then 1 K
H
2
P
b
2
H
2
and the rate law reduces to : r
CO
= k
2
P
b
1
H
2
. Thus as
P
H
2
increases, so does the reaction rate.
(ii) At high P
H
2
: then 1 K
H
2
P
b
2
H
2
and the rate law reduces to r
CO
=
k
2
K
H
2
P
b
1
b
2
H
2
. If b
1
b
2
< 0
then increasing the pressure will decrease the reaction rate.
The data is rather few, but the trend of the rate law obeys the rate data at least conceptually.
(d)
Regressing all the data,use a non-linear regression for all the constants
mi n obj (k, b
1
, b
2
, K
H
2
) =
6
i =1
_
r
CO,i

kP
CO,i
P
b
1
H
2
,i
1 + K
H
2
P
b
2
H
2
,i
_
In Scilab this looks like this
//least squares regression for all the parameters
function f=model(p,n)
k=p(1);b1=p(2);b2=p(3);Kh2=p(4);
//b1=0.5;b2=1;
f=rate-k*Paa.*Pbb^b1./(1+Kh2*Pbb^b2)
endfunction
And calling the least squares solver with an initial guess
p0=[0.02 0.5 1 1];
[p v info]=lsqrsolve(p0,model,n)
disp(info,info);
disp(norm(v),lsqrE);
disp(p,p)
k=p(1);b1=p(2);b2=p(3);Kh2=p(4);
rate_m=k*Paa.*Pbb^b1./(1+Kh2*Pbb^b2) //predict the reaction rate from
parameters
The parameters are p = [k
2
, b
1
, b
2
, K
H
2
] = [0.01135, 0.33, 1.115, 0.510] with a LSQRerror of
0.0050 and a variance of = [0.79, 26, 46, 106] i.e p = p . The t of the model to the
reaction rate is shown inFig 7.12. It can be seen that the reaction rate at constant P
H
2
is not
was well predicted as the variation with P
H
2
. This is already noted in the scatter when tting
for the reaction order of CO. Furthermore the variance in the model parameters is very high,
in fact the model parameters are useless, since the variance exeeds the parameter value.
The rate law then is
r
CO
=
0.01135P
CO
P
0.33
H
2
1 + 0.510P
1.115
H
2
Also the reaction orders are non-integer values, which from mechanistic considerations is not
realistic. Typically reaction orders are [0, 0.5, 1, 1.5, ...]
With this in mind and the fact that there are too many parameters for such few data, rounding
the orders of the reactions o to the nearest accepable value, yields
r
CO
=
kP
CO
P
0.5
H
2
1 + K
H
2
P
H
2
Now regressing again yields k = 0.0287 and K
H
2
= 2.90 with a LSQRerror of 0.0050 and a
variance = [0.0484, 3.79] which is still very high, but at least better then before. Fig 7.13
shows the t of the reaction rate.
105
0.000
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
P
H
2
[atm]
r
C
O
[
m
o
l
:
L
1
:
m
i
n
1
]
Figure 7.12: The prediction of the reaction rate when regressing for all the rate law constants.
0.000
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
P
H
2
[atm]
r
C
O
[
m
o
l
:
L
1
:
m
i
n
1
]
Figure 7.13: The prediction of the reaction rate when regressing for k, K
H
2
in the rate law.
This yields the nal rate law
r
CO
=
0.0189P
CO
P
0.5
H
2
1 + 1.48P
H
2
The rate law is OK, just there are too few data points ot make these values reliable. Note, that
the LSQRerror does not change much between the last 2 rate laws. There are not enough data
points to accurately evaluate the reaction orders.
The Scilab code FoglerEx5-5.sce does all the calculations.
106
Chapter 8
Developing rate laws from reaction
mechanisms and reaction pathways
107
Chapter 9
Bio-reactor engineering mechanisms
108
Chapter 10
Bio-reactor design
109
Chapter 11
Analysis of reactor ow patterns on
reactor performance (Fogler chapter 13)
110

Reactor Design 1

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Reactor Design 1

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CHE3044F :

is a function of the concentration of B (C

which can be solved by the backslash (a = p\l n(r

are summarised here:

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