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FTLecture SLides

The document outlines the course content for Chemical Reaction Engineering (CHE356) taught by Dr. Rabya Aslam, covering topics such as kinetics of homogeneous and heterogeneous reactions, reactor design, and comparison of different reactor types. It includes details on methods for analyzing reactor data, designing batch and flow reactors, and the effects of temperature and pressure on reactions. Recommended textbooks and assignments for practical applications are also provided.

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0% found this document useful (0 votes)
3 views

FTLecture SLides

The document outlines the course content for Chemical Reaction Engineering (CHE356) taught by Dr. Rabya Aslam, covering topics such as kinetics of homogeneous and heterogeneous reactions, reactor design, and comparison of different reactor types. It includes details on methods for analyzing reactor data, designing batch and flow reactors, and the effects of temperature and pressure on reactions. Recommended textbooks and assignments for practical applications are also provided.

Uploaded by

Saliha Nawab
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
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Chemical Reaction

Engineering-CHE356

Dr. Rabya Aslam


Institute of Chemical Engineering and Technology
University of the Punjab, Lahore 54590
rabya.icet@pu.edu.pk 1
Course contents

 Introduction to chemical reaction engineering


 Kinetics of homogeneous reactions
 Interpretation of reactor data for single and multiple reactions.
Integral method and differential method of analysis for constant
volume and variable volume batch reactors.
 Design of homogeneous reactors: Batch, Mixed flow, Plug flow
reactors, Comparison of single reactor, multiple reactor systems in
parallel/series.
 Design of heterogeneous reactors: Rate equations for
heterogeneous reactions. Catalyst deactivation and regeneration.
Design of fixed bed and fluidized bed catalytic reactors.

2
Course contents
Kinetics of homogeneous reactions: Rate of reaction, variables affecting
the rate of reaction, order of reaction, rate constant; searching for a
mechanism of reaction, activation energy and temperature dependency,
Interpretation of batch reactor data for single and multiple reactions.
Integral method and differential method of analysis for constant volume
and variable volume batch reactors. Search for a rate equation.

Design of homogeneous reactors: Batch, Mixed flow, Plug flow reactors,


Comparison of single reactor, multiple reactor systems in parallel/series.
Temperature and pressure effects, Adiabatic and non-adiabatic operations.

Design of heterogeneous reactors: Surface phenomenon and catalysis,


adsorption/desorption isotherms, Heterogeneous reaction systems, Rate
equations for heterogeneous reactions, Determination of rate controlling
steps. Kinetics of solid catalyzed reactions. Catalyst deactivation and
regeneration. Design of fixed bed and fluidized bed catalytic reactors.

3
Recommended books
 Levenspiel, O. 1999. Chemical reaction engineering. 3rd ed. Wiley
& Sons, Inc., Singapore.
 Fogler, H.S. 2006. Elements of chemical reaction engineering. 4th
ed. Prentice-Hall.
 Froment, G.F.; Bischoff, K.B.; De Wilde, J. 2011. Chemical
reactor analysis and design. 3rd ed. John Wiley & Sons, Inc.
 Missen, R.W.; Mims, C.A.; Saville, B.A. 1999. Introduction to
chemical reaction engineering and kinetics. John Wiley & Sons,
Inc., New York.
 Smith, J.M. 1981. Chemical engineering kinetics. 3rd ed. McGraw-
Hill Int. Book Co., Singapore.

4
Size comparison of PFR and MFR
Comparison of CSTR and PFR for
 Conversion
 Reactor Volume
 Selectivity for a particular reaction
1. For CSTR/MFR
Assumption: constant density first order reaction
𝑉 𝑋𝐴
𝜏= =
𝑣𝑜 𝑘(1 − 𝑋𝐴)

𝑉
𝑘( )
𝑋𝐴 = 𝑣𝑜
𝑉
1 + 𝑘( )
𝑣𝑜
5
Size comparison of PFR and MFR

2. For PFR/Tubular reactor


Assumption: constant density first order reaction
𝑉 𝑑𝑋𝐴
𝜏 = = 𝐶𝐴0
𝑣𝑜 𝑘𝐶𝐴0(1 − 𝑋𝐴)

𝑉 1
= − ln(1 − 𝑋𝐴)
𝑣𝑜 𝑘

( )
𝑋𝐴 = 1 − 𝑒

6
Size comparison of PFR and MFR

𝑉𝑚 𝑉𝑃
𝑘 𝑜𝑟 𝑘( )
𝑣0 𝑣0
7
Comparison of PFR and CSTR for nth order reaction

For a given duty the ratio of sizes of mixed and plug flow reactors will
depend on the extent of reaction, the stoichiometry, and the form of
the rate equation.

For MFR:

(1)

For PFR:

(2)

8
Comparison of PFR and CSTR for nth order reaction

Dividing 2 and 3

9
Comparison of PFR and CSTR

10
Comparison of PFR and CSTR

11
Comparison of PFR and CSTR

 For any particular duty and for all positive reaction orders the
mixed reactor is always larger than the plug flow reactor. The
ratio of volumes increases with reaction order.
 When conversion is small, the reactor performance is only
slightly affected by flow type (CSTR/PFR).
 The performance ratio increases very rapidly at high
conversion; consequently, a proper representation of the flow
becomes very important at high conversion.
 For zero order reaction, reactor size is independent of the
reactor type.
 Density variation during reaction affects design; however, it
is normally of secondary importance compared to the
difference in flow type.
12
Ratio of CSTR volume to PFR volume

13
Home Assignment

Drive the following relation for first order system

Where α is the ratio of MFR to PFR volume.

14
Combination of reactors: For a single reaction
There are many ways of processing a fluid: in a single
batch or flow reactor, in a chain of reactors possibly with
inter-stage feed injection or heating, in a reactor with
recycle of the product stream using various feed ratios and
conditions, and so on.
Which scheme should we use?
With the wide choice of systems available and with the
many factors to be considered, no neat formula can be
expected to give the optimum setup. Experience,
Engineering judgment, and a sound knowledge of the
characteristics of the various reactor systems are all
needed in selecting a reasonably good design.
15
Combination of reactors: For a single reaction
Single reactions are those reactions whose progress can be
described and followed adequately by using only one rate
expression coupled with the necessary stoichiometric and
equilibrium expressions. For such reactions product
distribution is fixed; hence, the important factor in
comparing designs is the reactor size.
Any combination may be employed. For example
1. PFR in series or in parallel
2. CSTR in series or in parallel
3. PFR followed by CSTR in series
4. CSTR followed by PFR in series etc.

16
Multiple Reactor Systems: Reactors in series
 Many times reactors are connected in series so that the exit
stream of one reactor is the feed stream for another reactor.
 When this arrangement is used it is often possible to speed
calculations by defining conversion in terms of location at a
point downstream rather than with respect to any single
reactor. That is, the conversion X is the total number of moles
of A that have reacted up to that point per mole of A fed to the
first reactor. However, this definition can only be used
provided that there are no side streams withdrawn and the feed
stream enters only the first reactor in the series.

17
Multiple Reactor Systems: Reactors in series
 As an example, the relationships between conversion
and molar flow rates for the reactor sequence shown in
following Figure are given by the following equations:

PFR and CSTR in series


Where
𝑡𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑢𝑝𝑡𝑜 𝑝𝑜𝑖𝑛𝑡 1
𝑋 =
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 𝑓𝑒𝑑 𝑡𝑜 𝑓𝑖𝑟𝑠𝑡 𝑟𝑒𝑎𝑐𝑡𝑜𝑟
𝑡𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑢𝑝𝑡𝑜 𝑝𝑜𝑖𝑛𝑡 2
𝑋 =
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 𝑓𝑒𝑑 𝑡𝑜 𝑓𝑖𝑟𝑠𝑡 𝑟𝑒𝑎𝑐𝑡𝑜𝑟

And so on. 18
Case 1: PFR in series
Consider N plug flow reactors connected in series, and let XI, X,, . . . , X,
be the fractional conversion of component A leaving reactor 1, 2, . . . , N.
Applying the material balance on the feed rate of A to the first reactor, we
have
CA0 CA1 CAN
1 2 … N
XA0 XA1 XAN
FA0 FA1 FAN

Hence, N plug flow reactors in


series with a total volume V
gives the same conversion as a
single plug flow reactor of
volume V.

19
Case 2: PFR in parallel
Consider N plug flow reactors connected in parallel.
A
1

B
2



N

For the optimum hook up of plug flow reactors connected in parallel,


we can treat the whole system as a single plug flow reactor of volume
equal to the total volume of the individual units if the feed is distributed
in such a manner that fluid streams that meet have the same
composition. Thus, for reactors in parallel V/F or 𝝉 must be the same
for each parallel line. Any other way of feeding is less efficient.

= = 20
Class Activity

𝑉 𝑉
N =
𝐹 𝐹

two-thirds of the feed must be fed to branch D.

21
Case 3: CSTR in series

Consider N equal volume CSTRs connected in series.

Although the concentration is uniform in each reactor, there is a change in


concentration as fluid moves from reactor to reactor.
Assumptions:
1. Equal volume reactors
2. Expansion factor is zero
3. First order kinetics

22
Case 3: CSTR in series

Since the space-time (or mean residence time t) is the same in all the equal size
reactors of volume Vi. Thus,

23
Home Assignment

Derive the space time correlation for N-CSTRs in


series for a zero order reaction.

24
Case 3: CSTR in series

25
Case 3: CSTR in series

First Order System:

26
Case 3: CSTR in series

First Order System:

27
Case 3: CSTR in series

The Damköhler
numbers are
dimensionless
numbers used in
chemical
engineering to
relate the
chemical reaction
timescale to the
transport
phenomena rate
occurring in a
system. It is
named after
German chemist
Gerhard
28
Damköhler.
Case 3: CSTR in series
For second order reaction

29
Class activity

30
Class activity

1: kCA0t=90

2: When N=2
kCA0t=90 X2 = 180
3
1 3: at kCA0t =180
move to N=2 line
4
4: and find 1-XA

0.027

31
Class activity

32
Home Assignment for Practice

Solve following exercise problems from Chapter 6,


Octave Levenspiel, 3rd edition.

P 6.1 to 6.3

33
Case 4: CSTR in parallel

For ith reactor

Where
𝑉
𝑉𝑖 =
𝑁
𝐹𝐴0
𝐹𝐴0𝑖 =
𝑁
Putting in (1), we have

𝐹𝐴0. 𝑋
𝑉=
−𝑟𝐴
The conversion in any one reactor in parallel is identical to what would
be achieved if the reactant was fed to one large reactor of volume V. 34
Case 4: CSTR of different volumes in series

For arbitrary kinetics in mixed flow reactors of different size, two types
of questions may be asked:
1. how to find the outlet conversion from a given reactor system, and
2. how to find the best setup to achieve a given conversion.
For this purpose, graphical method is always easy to use in which only
an -rA versus C curve for component A to represent the reaction rate at
various concentrations is needed.

35
Case 5: CSTR of different volumes in series

36
Determining the Best System for a Given Conversion

Suppose we want to find the minimum size of two mixed flow


reactors in series to achieve a specified conversion of feed which
reacts with arbitrary but known kinetics.

For 1st reactor,

Best arrangement will be one for which


total volume will be minimum for required
For the 2nd reactor conversion.

37
Determining the Best System for a Given Conversion

38
Different reactors in series: best arrangement

Whatever may be the kinetics and the reactor system, an


examination of the l/(-rA) vs. CA curve is a good way to find the
39
best arrangement of units.
Different
Different
reactors
reactors
in in
series:
series:
best
Class
arrangement
activity
Calculate the total reactor volumes for the following scheme

The reaction data is as follows and molar flow rate is 2mol/s

40
Different
Different reactors
reactors in
in series:
series: Class
Class activity
activity

41
Levenspiel plot for CSTR/PFR/CSTR sequence.
Different reactors in series: Class activity

250

250*0.4 = 100 dm3

100 dm3

42
Different reactors in series: Class activity

∆𝑥
𝑓 𝑥 𝑑𝑥 = 𝑓 𝑥1 + 4(𝑓 𝑥 + 𝑓(𝑥2) 43
3
Different reactors in series: Class activity
Reactor 3: CSTR

100

44
Different reactors in series: Assignment

45
Selection of right type of reactor

46
Approach to reactor selection

 Identify number of phases present at reaction


conditions
 Identify stoichiometry, number of reactions,
energy requirements
 Identify mechanism (if possible) and active
intermediates
 Decide on the purpose of reactor selection
 Whether the reactor is for collection of
kinetic data or it’s a commercial reactor?

47
Rules worth remembering
Rule1: For single reaction
To minimize the reactor volume, keep the concentration as high as
possible for a reactant whose order is n > 0. For components where
n < 0 keep the concentration low.
Rule2: For reaction in series
In consecutive reactions, production of intermediate is always more
favored in a PFR than in a CSTR.

(a) Plug flow (no intermixing) gives the most of all the intermediates.(b) Intermixing
48
depresses the formation of all intermediates.
Rules worth remembering
Rule3: For parallel reaction

1. low CA favors the reaction of lowest order


2. high CA favors the reaction of highest order
3. If the desired reaction is of intermediate order then some
intermediate CA will give the best product distribution.
4. For reactions all of the same order the product distribution is not
affected by the concentration level.

49
Summary: Isothermal Design of Flow reactors: Class Activity

Designing a Plug Flow Reactor (PFR) and a Continuous


Stirred -Tank Reactor for the production of Dimethyl Ether
from dehydration of methanol.
Reaction Kinetics is based on volume of reactor

It’s a gas phase reaction


and the reaction mixture is
composed of 2.0 moles of
methanol and products, 1 of
dimethyl ether and 1 mole
of water

50
Design of PFR
The following assumptions were made for the development of
design/performance equations for the production of dimethyl
ether.
 The reactor operates at steady state
 The reaction takes place in the gaseous phase with
constant density.
 Pressure drop along the reactor is negligible (The vessel is
empty and refractory lined)

51
Design of PFR
1: The performance equation is

2: Reactor Volume (VR) for Plug Flow Reactor

52
Design of PFR
3: Reactor Length
Assume L/D ratio and use following equation

𝜋𝐷
𝑉 = 𝐴. 𝐿 = 𝐿
4

4: Diameter of reactor
Using value of length, calculate diameter of reactor from assumed
value of L/D

L/D=x Assumption

53
Design of PFR
5: Space Time

54
Design of CSTR

V X A

FA0  rA

Assumption

55
Design of
Design of PFR
CSTR

56
Design of CSTR
Stirrer Design
Usually, a clearance is allowed between the stirrer blade and
the reactor side

57
Summary: Isothermal Design of Flow reactors: Class Activity

Designing an isothermal Plug Flow Reactor (PFR) and a Continuous Stirred -Tank
Reactor for the production of Dimethyl Ether from dehydration of methanol at 533K
and 10bar.

Reaction Kinetics is based on volume of reactor


It’s a gas phase reaction and the
reaction mixture is composed of
2.0 moles of methanol and
products, 1 of dimethyl ether
and 1 mole of water, provided
rate data is based on reactor
volume.

58
Summary: Isothermal Design of Flow reactors: Class Activity

T 290 oC
P 1000 kPa
R 8.314 m3.Pa/mol/K
E 7.50E+04 j/mol
ko 1.0E+08 kmol/m3/s
k 5.40E+00 kmol/m3/s
CA0 0.23 kmol/m3
Fao 1.53 kmol/s
X 0.9 -
Expansion factor 0 -

Reactor operates isothermally


59
Summary: Isothermal Design of Flow reactors: Class Activity

60
Simulation with HYSYS

61
62
Pressure Drop in an Empty-Tube PFR
For a PFR without catalyst, pressure drop is calculated using the Darcy-Weisbach
equation

ΔP = Pressure drop (Pa)


f = Friction factor (depends on Reynolds number)
L = Length of reactor (m)
D = Diameter of reactor (m)
ρ = Density of the gas (kg/m³)
v = Gas velocity (m/s)

63
Pressure Drop in an Empty-Tube PFR
For a PFR without catalyst, pressure drop is calculated using the Darcy-Weisbach
equation

ΔP = Pressure drop (Pa)


f = Friction factor (depends on Reynolds number)
L = Length of reactor (m)
D = Diameter of reactor (m)
ρ = Density of the gas (kg/m³)
v = Gas velocity (m/s)

64
Pressure Drop in an Empty-Tube PFR

65
Pressure Drop in an Empty-Tube PFR

For turbulent flow, the Blasius equation estimates the friction factor:

Alternatively, the Haaland equation can be used, which applies to both transition and
turbulent regimes:

Where ϵ is the pipe roughness

For laminar flow, following eq is used to estimate the friction factor:

66
Design of Heterogeneous
reactors

67
Packed Bed Reactors: Introduction
 Packed Bed Reactors (PBR)
also known as Fixed Bed
Reactors (FBR) are often
used for catalytic processes
 PBR consists of a cylindrical
shell with convex heads,
most are vertical and allow
reactants to flow by gravity.
 A catalyst bed is placed
inside the reactor.

68
Packed Bed Reactors: Introduction

 Shell (vertical or
horizontal)
 Liquid distributor
 Packing support
 Packing hold down grid
Catalyst/packing
 Gas inlet
 Gas outlet
 Liquid inlet
 Liquid outlet

69
Packed Bed Reactors: Types

70
Packed Bed Reactors: Types
B

71
Packed Bed Reactors: Types

72
Packed Bed Reactors: Types

73
Packed Bed Reactors: Types

74
Tubular reactor
Packed Bed Reactors: Introduction

 When designing a PBR, active life of the catalyst must be


taken into consideration. This will affect the length of
catalyst bed may be used and how long the reactor may
be run before the catalyst needs to be regenerated.

 Catalyst are mostly in the form of pallets, granular with


diameters ranging from 1 to 5 mm. they can be loaded to
reactors in various ways: single bed, in tubes, multiple
beds etc.

 Selection of catalyst depends on reactants and products.

75
Packed Bed Reactors: Introduction
Advantages:
 Higher conversion per unit mass of catalyst than other
catalytic reactors
 Low operating cost
 Continuous operation
 No moving parts to wear out
 Catalyst stays in the reactor
 Reaction mixture/catalyst separation is easy
 Effective at high temperatures and pressures
Disadvantages:
 Undesired heat gradients
 Poor temperature control
 Difficult to clean
 Undesirable side reactions
76
Packed bed reactors: Design Equation

Packing/catalyst XA
W dX A
FA0
 
0
(rA )

77
Packed bed reactors
The principal difference between reactor design calculations
involving homogeneous reactions and those involving fluid-solid
heterogeneous reactions or packing is that for the latter, the reaction
rate is based on mass of solid catalyst or packing, W, rather than on
reactor volume, V.

Packed bed reactor scheme


Like a plug flow reactor, in packed reactor, the composition of the fluid
varies from point to point along a flow path; consequently, the material
balance for a reaction component must be made for a differential
element of weight dW. 78
Packed bed reactors

Input of A = FA
output of A = FA + dFA
Consumption of A by reaction = (-rA’) dW

moles of A reacting
= . mass of cat./packing
time (mass of cat. or packing)
moles of A reacting
=
time

Also
dFA  d FA0 (1  X A )    FA0 dX A
Inserting all values in general mole balance equation, we have

FA  FA  FA0 dX A  ( rA )dW  0
79
Packed bed reactors
On rearrangement, we get performance equation of a packed bed
flow reactor
dX A ( rA )

dW FA0

dX A ( rA ) dX A
  ( rA )
dW FA0  W 
d  
 FA0 
For the reactor as a whole the expression must be integrated. Where (–rA) is dependent on
the concentration or conversion of materials.
XA
W dX A
FA0
 0
(rA )
80
Basic performance equations of heterogeneous flow reactors

PFR system

dX A
 ( rA )
Fractional W 
conversion of A d  
 FA0 
Weight of catalyst,
Initial molar flowrate of the
kg
limiting reactant, mol/s

Catalyst XA
W dX A
FA0
 
0
(rA )
81
Class Activity
100 kmol/h pure methylcyclohexane enters the packed
bed dehydrogenation reactor that contains 2.0 mm
spherical alumina particles. The reactor operates
isothermally at 350°C and 2 bar pressure. Calculate the
weight of the catalyst for a conversion of 96%. Rate data
is provided as follows:
XA/- 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

(-rA)
9.6 8.8 8.4 8.0 7.1 6.7 6.0 5.4 4.8 4.0 3.4
(mol/kgcat.h)

82
Class Activity

(-rA)
(mol/
XA/- 1/(-rA)
kgcat.
s)
0 9.6 0.10
0.1 8.8 0.11
0.2 8.4 0.12
0.3 8.0 0.13
0.4 7.1 0.14
0.5 6.7 0.15
0.6 6.0 0.17
0.7 5.4 0.18
𝑊 ℎ 1 1
0.8 4.8 0.21 = +
𝐹𝐴0 2 −𝑟𝐴 −𝑟𝐴
0.9 4.0 0.25 .
1 3.4 0.29
𝑊 = 100 ∗0.48*(0.1+0.27)=17.76kg of catalyst

83
Catalyst
A catalyst is a substance that modifies (accelerates or
decelerates) the rate of a chemical reaction without itself
being used up.

 Although catalyst may accelerate or decelerate the rate


of reaction, however, the term catalyst is usually
employed when the objective is to increase the rate of
the desired reaction.
 The term inhibitor is used when the rate of the desired
reaction is required to decrease.

84
Catalyst
 A catalyst can only alter the rate of a chemical reaction
and cannot affect the thermodynamics associated with
the reaction. It cannot affect equilibrium compositions
and energy changes per mole of the reaction.

 For a thermodynamically possible reaction, a catalyst


modifies the path of the reaction and lowers the
activation energy. This results in increasing the rate of
the corresponding reaction.

85
Examples of catalysts
vanadium pentaoxide, metal over alumina, and zeolites, acids
such as H2SO4, alkalies such as NaOH, KOH are common
examples of catalysts.
Catalytic reactions: Example
The reaction of ammonia synthesis from N2 and H2 is favorable
thermodynamically.
 In the absence of a catalyst it occurs at extremely slow speed.
The activation energy, 238.5 kJ/mol associated with the
homogenous reaction is quite high.
 The presence of a typical catalyst decreases the activation
energy of the rate controlling step to only 50.2 kJ/mol

Fe3O4-based iron catalysts 87


Principles of catalysis
 As the equilibrium constant is a ratio of forward rate to the reverse
rate constants, increasing forward rate of reaction also increases the
rate of the reverse reaction (as equilibrium constant is to be
unaffected).

 Principally, the same catalyst is used for forward reaction and


reverse reaction. Pt/Al2O3 is a good catalyst for dehydrogenation of
methylcyclohexane to toluene as well as for hydrogenation of
toluene to methylcyclohexane (reverse reaction). Only the
operating conditions has to be changed. At higher pressures and
lower temperatures Pt/Al2O3 catalyzes hydrogenation of toluene
while at lower pressures and higher temperatures it catalyzes
dehydrogenation.

88
Catalyst support or catalyst carrier
Catalyst support provides surface to the active component
of a catalyst. A support is usually a high surface area
porous material on which the active component is
dispersed and that the support, itself, may be active or
inert. A support gives strength, shape, and size to a
catalyst. Examples of catalyst supports are alumina, and
silica.
In 1.0wt% Pt over alumina, Pt metal is the active
component dispersed over the alumina support.

The same active component when dispersed or supported


on a different support may greatly change the activity,
selectivity, regenerability, and life of the catalyst.
89
Supported catalysts
Usually an active component is dispersed over a relatively inactive
or less active material which usually has a high surface area.
Pt/Al2O3, Ni-W/Al2O3 are examples of supported catalysts.

TEM image of Rh/SiO2 [7a]

90
TEM image of Pt/Al2O3
Bifunctional catalyst
 It catalyzes two types of catalytic transformations
 Pt metal loaded on an acid support such as silica-
alumina or zeolite is a bifunctional catalyst
 The Pt metal cares for the dehydrogenation and
hydrogenation reactions while acid support facilitates
cracking and isomerization reactions
 A catalytic cracking process requires only an acidic
catalyst such as zeolite while hydrocracking process
requires a bifunctional catalyst such as Pt/zeolite
catalyst or Ni-W/silica-alumina catalyst.

Zeolite Pt/Al2O3 Pt/zeolite


Hydrocracking 91
Cracking catalyst Reforming catalyst catalyst
Active sites or active centers
Active site are the point on the catalyst surface that can form strong chemical bonds
with an adsorbed atom or molecule.”

In a catalytic theory, Taylor suggested that a reaction is not


catalyzed over the entire solid surface but only at certain
active sites or centers.

92
Important terminologies
Turnover number (TON): In catalysis, the term turnover
number is defined as the amount of substrate converted per
the amount of catalyst used.

Turnover frequency (TOF): It is the number of molecules


converted per unit time per active site. TOF characterize the
activity of a catalyst.
The larger the TOF, the more active the catalyst.

Turnover time: it is the inverse of TOF and defined as the


time required to form a product molecule.

93
Selection of a catalyst
The selection of a suitable catalyst for a process usually
demands the knowledge of the following parameters of
a catalyst.
 Activity
 Selectivity
 Stability, and
 Regenerability

94
Selection of a catalyst
Activity: Activity of a catalyst controls the extent of a
chemical reaction involved and describes the
effectiveness of a catalyst towards the rate of the
chemical reaction and conversion of the reactant. It has
no concern with the product distribution (selectivity).

Selectivity: Selectivity refers to the efficacy of a


catalyst towards producing the desired product. For both
the parallel and consecutive reactions, the selectivity is
important and a catalyst is required to produce the
desired product in greater amounts (increased
selectivity).
95
Selectivity of a catalyst

96
Selection of a catalyst
Stability: For a catalyst, it refers to the life of the
catalyst. If the activity and selectivity of a catalytic
system remains unchanged during the course of a
given period of time, under the same conditions of
temperature, pressure, and space time, the catalyst
gives the same product composition for the same
feed composition, the catalyst is said to have stable
characteristics for that period of time.
Regenerability: It refers the ability of a catalyst to
be reactivated to more or less to its original
conditions.
97
Selection of a catalyst
The order of importance of the activity,
selectivity, and stability as suggested by
scholars is as follows:

Selectivity
Stability
Activity

98
Characterization of catalysts
XRD: Stands for x-ray diffraction. It is commonly used for
phase identification and to observe bulk crystal structure.
Diffraction lines widen as crystallite size decreases. A broader
peak may show distortion and less degree of crystallinity. It
helps to make sure the presence of the desired material.

SEM: Stands for scanning electron microscopy. It is used to


see the topography of the catalyst surface. It gives an
information regarding surface features such as surface
irregularities and particle shape, size, and distribution. Lower
resolutions compared to TEM.

99
Characterization of catalysts
TEM: Stands for transmission electron microscopy. Electrons
have to be passed or transmitted through the sample. Sample
should be very thin and very high resolutions are obtained.
Atomic arrangement in crystals and crystalline defects at nano-
level can be detected.

N2-BET surface area: Surface area of catalytic materials is


measured by N2 adsorption using BET isotherm. Pore size and
pore volume of the pores present within the catalyst are also
measured.

Porosimetry: Helium or mercury intrusion porosimetry can be


used to measure the pore size, pore volume, and particle
densities of the material.
100
Characterization of catalysts
Elemental composition: Atomic absorption spectroscopy
(AAS), Inductively coupled plasma (ICP) spectroscopy,
Energy dispersive X-ray (EDX) analysis with SEM can be
used for the elemental identification and composition.

Temperature programmed techniques: Py-TPD (Pyridine-


temperature programmed desorption) or NH3-TPD is used to
measure the acidity of a catalyst. Other temperature
programmed techniques such as TPR (temperature
programmed reduction), TPO (temperature programmed
oxidation), TGA (thermogravimetric analysis), and DTA
(differential thermal analysis) are also used for various other
purposes.
101
Catalyst Characterization
SEM image of a zeolite Y

XRD patterns of a zeolite Y

102
TEM image of Rh/SiO2
Steps involved in a heterogeneous catalytic
fluid-solid reaction
Fluid
(mainly
gas)

103
Steps involved in a heterogeneous catalytic
fluid-solid reaction
1. Diffusion of reactant/s through external fluid film to
the catalyst surface.
2. Diffusion through pores of the catalysts.
3. Adsorption of the reactants on the surface of the
catalyst (within the pores).
4. Surface chemical reaction on the catalytic surface.
5. Desorption of the reaction products from the catalyst
surface.
6. Diffusion of the reaction products through the pores
back to the external surface.
7. Diffusion of the products into the fluid phase.
104
Global and Intrinsic rates of reaction
 When mass transfer resistances are also considered in
the development of a rate equation, the rate of the
corresponding chemical reaction is known as global
rate.
 When the external and internal diffusions are removed
or highly reduced, the rate of a gas-solid reaction is
based only on the intrinsic kinetics.

105
Intrinsic rates of reaction
The intrinsic kinetics of a fluid-solid reaction involves
only the following three steps as outlined in the previous
slide.
 Adsorption of the reactants on the surface of the
catalyst (within the pores)
 Surface chemical reaction on the catalytic surface
 Desorption of the reaction products from the catalyst
surface

106
Steps involved in a heterogeneous catalytic fluid-solid reaction

Fluid
(mainly Important in
gas) Intrinsic
kinetics

107
Common kinetic models for heterogeneous reactions

1. The power law (PL) kinetics

2. The Langmuir-Hinshelwood kinetics

3. The Eley-Rideal (ER) kinetics

108
The power law kinetics
The power law is an empirical kinetic model and
assumes homogenous fluid-solid reaction.
For the reaction
aA  bB  cC  dD
a rate equation can be written as:

( rA )  k  C Aa  C Bb
The sum of a and b is called overall order of the reaction.

The rate equation written based on law of mass action


rarely represents the true rate of a reaction and in most of
the cases, rate equation has to be found experimentally.
109
The power law kinetics
For the power law, the empirical rate equation my be of the type

n1 n2
( rA )  k  C A  CB

Where, sum of n1 and n2 is called the overall order of the


reaction and may be denoted as n.

n1 and n2 are not necessarily be equal to a and b in the above


equation. It happens rarely when reaction is elementary in
nature.

110
The power law kinetics
For the dehydrogenation of methylcyclohexane to toluene

A  B  3C
Assuming irreversible reaction (for the forward reaction
only), the power law rate equation may be written as:

( rA )  k CA
n
111
The power law kinetics
As the reaction is a gas-phase chemical reaction:

(  rA )  k  p n
A

The parameter k and n are the regression parameters to be


fitted against the experimental data.

Rate constant k is described as a function of temperature


and usually represented by the Arrhenius equation.
Ea

k  k0  e RT
112
Developing a rate equation
 Experimental data is required where experiments may
be carried out in a batch reactor, semi-batch reactor,
CSTR, or a tubular reactor system.

 Data can be obtained under differential or integral


conditions.
 A small enough particle size is used to minimize the
diffusion limitations (for intrinsic kinetics).

113
Developing a rate equation
 For simplicity of calculations and more reliable results,
attempts are made to have an isothermal reactor.

 Experiments are performed over a stable catalyst,


otherwise the effect of time is to be incorporated in the
rate equation

Experimental reaction data is generated in the


laboratory or obtained from a reliable source to
develop rate equation.

114
Developing a rate equation
The experimental data is fitted against the
appropriate rate model.
The basic performance equation as that of a batch
reactor, CSTR, or PFR is required.

 The solution of the performance equation requires a


rate expression.
 A rate equation is assumed and the experimental data
is fitted to obtain the model parameters.

115
Example : Fitting the experimental data in a CSTR

The experimental data given below for the


dehydrogenation of methylcyclohexane (MCH)
is generated in a catalytic continuous stirred tank
reactor (CSTR) under integral conditions. Using
power law kinetics for the irreversible reaction,
fit the experimental data and find out the kinetic
parameters.

W XA W
 XA  (rA )
FA0 (rA ) FA0
116
Fitting of experimental data
Using the power law of the following form

n
( rA )  k  p A

What to do next to find n


and k?

117
Mole fractions in the vapor phase (reaction
mixture) at conversion XA

118
Fitting of experimental data

( rA )  1.661  p A
0.942

Can you do it assuming reversible


reaction? 119
kinetics data from a Mixed Flow Reactor
 Measure reaction data at different input values such
as reactant flow rate, concentration and for various
conversion.
 Calculate reaction rate for each data point.
FA0 . X A  mol 
(  rA )   
W  s  g  catalyst 
 For convenience, nth order rate expression can be
tested and kinetic parameters can be evaluated.
n
( rA )  k  p A Slope

log( rA )  log k  n log p A


intercept

120
Rate equation from experimental data for a
reversible reaction

A  B  3C
Including reversibility, the following power law form may be used
with the experimental data:
n
 pB  p 3

(rA )  k   pA  C

 Ke 
Where, Ke is reaction equilibrium constant. Only rate equation is
changed, the rest of the procedure of fitting the data is the same 121
Fitting the experimental data in a PFR
Using power law kinetics for the irreversible
reaction, we have following performance
equation.

dX A dX A ( rA )
 ( rA ) 
 W  dW FA0
d  
 FA0 
The regression with PFR requires differential equation to be
solved. Euler or 4th order RK method can be used for this
purpose.

122
Curve Fitting and Regression Analysis

The regression analysis is systematic approach to find coefficients


(parameters) of a function that are believed to properly represent a set
of experimental data and to perform statistical analyses to confirm (or
deny) that the function gives a good fit to the data.

Without the additional statistical analysis, just finding the parameters


of some function is called curve fitting.

Curve fitting, while useful in certain circumstances, is not as powerful


as regression analysis.

123
Important Statistical Parameters for regression
analysis
Sum of squares of errors:
The SSE can be used as a gauge of the fitted curve's accuracy. Lesser the value of
SSE better will be the fitted parameters.
N 2

SSE   X
I 1
obs  X mod 

coefficient of determination:
R2 is the coefficient of determination, the most common measure of how well a
regression model describes the data. The closer R2 is to one, the better the
independent variables predict the dependent variable.
𝑆𝑆𝐸
𝑅 =1−
𝑆𝑆𝑀
Where SSM is sum of square of deviations from mean value.

𝑆𝑆𝑀 = 𝑥 , − 𝑥̅

And
𝑥 ,
𝑥̅ =
𝑁
124
Where xexp is the experimental value, N is the number of data points and i represents the ith value.
Important Statistical Parameters for regression analysis

F-Value
This transform compares two equations from the same family to determine if the
higher order provides a statistical improvement in fit. It may also be used to compare
the two model for the same data to decide which one is better. Higher the F-value,
better will be the model.

SSM  SSE
MSR m 1
F  value  
MSE SSE
N m
N =no of data point (experimental)
m = number of constants (parameters) in the equation

125
Class Activity: Use of Solver

126
Class Activity: Use of Solver

Step 1: Use solver to find the parameters of each equation


Step 2: Perform regression analysis (SSE, R2, F-value) to discriminate the
models)

127
Packed Bed Reactors: Design
XA
Steps involved in designing of fixed W dX A
bed reactors:
1. Reaction steps and mechanism FA0
 
0
(rA )
information
2. Rate equation information
Packing/catalyst
3. Determination of weight of the
catalyst for specific conversion
4. Determination of volume of fixed
bed
5. Determination of height and
diameter of bed
6. Determination of volume of
Reactor
7. Determination of Pressure Drop
inside reactor 128
Packed Bed Reactors: Design
3. Determination of weight of the catalyst for specific conversion

XA
dX A
W  FA0 . 
0
(rA )

4. Determination of volume of fixed bed


W
Vcatalyst 
 B ,catalyst
where
W  weight of catalyst
 B ,catalyst  bulk density of catalyst
Vcatalyst  volume of catalyst 129
Packed Bed Reactors: Design
4. Determination of volume of fixed bed (contd..)
Vcatalyst
Vcatalyst bed 
(1  bed )
where
bed  bed porosity
Vcatalyst bed  volume of catalyst bed
5. Height and diameter of bed
To find the height and diameter of the reactor, height and diameter of catalyst
bed is required
Vcatalyst bed
H catalyst bed  As rule of thumb,initial
 2 guess ma be
Dcatalyst bed H/D =2.5
4
130
Packed Bed Reactors: Design
6. Volume of reactor

 2
V reactor  H reactor D catalyst bed
4
Where height of reactor is height of bed plus clearance height which is normally taken
15% of the height of bed. Thus

H reactor  1 . 15 H bed

131
Packed Bed Reactors: Design
7. Pressure Drop inside reactor
In liquid-phase reactions, the concentration of reactants is
insignificantly affected by relatively large changes in the total
pressure. Consequently, the effect of pressure drop on the rate of
reaction is ignored for liquid phase reactions. However, in gas-phase
reactions, the concentration of the reacting species is proportional to
the total pressure;, proper accounting for the effects of pressure drop
on the reaction system can be a key factor in the success or failure of
the reactor operation. This fact is especially true in reactors packed
with solid catalyst. Here the channels are so small that pressure drop
can limit the throughput and conversion for gas-phase reactions.

The equation used to calculate pressure drop in a


packed porous bed is the Ergun equation
132
Packed Bed Reactors: Design
7. Pressure Drop inside reactor

133
Packed Bed Reactors: Design

134
Packed Bed Reactors: Design

135
Packed Bed Reactors: Design
Using equation of density as function of pressure and
temperature, Ergun equation may be written as follows

If more than one reactants are involved, viscosity of mixture


can be estimated as

136
Packed Bed Reactors: Design

Any Question??

137
Fluidized bed reactors: Introduction

 The term “Fluidized bed reactors” is restricted


here to equipment in which finely divided solids
in suspension interact with gases.

 Solids fluidized by liquids are called slurries.


Three phase fluidized mixtures occur in some
coal liquefaction and petroleum treating
processes.

138
Fluidized bed reactors: Introduction
 Fluidized-bed reactors are used in many
industries when heterogeneous reactions
take place involving solids and gases.
 From the standpoint of daily capacity, the
greatest application of fluidized bed
catalysis is to the cracking of petroleum
fractions into the gasoline range. In this
process the catalyst deactivates in a few
minutes, so that advantage is taken of the
mobility of fluidized catalyst to transport it
continuously between reaction and
regeneration zones in order to maintain its
activity; some catalyst also must be bled off
continuously to maintain permanent
poisons such as heavy metal deposits at an 139
acceptable level.
Fluidized bed reactors: Introduction
 Orthophthalic anhydride is made by oxidation of
naphthalene in a fluidized bed of V2O5 deposited on
silica gel with a size range of 0.1–0.3mm with a contact
time of 10–20 sec at 350–3800C. Heat of reaction is
removed by generation of steam in embedded coils. No
continuous regeneration of catalyst is needed.
Acrylonitrile and ethylene dichloride also are made under
conditions without the need for catalyst regeneration.

 Coal gasification is also major application area.

140
Fluidized bed reactors: Introduction

Fluidization catalysis may be conducted to


take advantage of the substantial degree of
uniformity of temperature and composition
and high rates of heat transfer to embedded
surfaces.

141
Fluidized bed reactors: Introduction
Features of FBR Common Applications

142
Fluidized bed reactors
Compared to a fixed bed reactor following advantages may be
achieved in fluidized bed reactor
 Larger fluid-solid contact area is possible
 higher rates of heat and mass transfer.
 As particle size is usually smaller there is a less resistance to
internal diffusion.
 Removal and addition of solid particles are easier therefore a
fluidized bed reactor is preferred over a fixed bed reactor where a
catalyst requires frequent regeneration.
Some disadvantages are as follows
 the catalyst particle may be reduced due to attrition.
 The flow of solids and fluid are in cocurrent and therefore
advantages of countercurrent are not possible to obtain. Fine
particles may be conveyed which may result in the loss of solids
and there is a need for a separator downstream to recover the
solids.
143
Fluidization: review

A process in which solid particles are suspended in a gas or liquid and the
solid particles behave like a fluid.

Chocking Velocity:
Although the phenomena are not clear-cut, partial settling out of solids from
the gas stream may develop below certain linear velocities of the gas called
choking velocities.
Above choking velocities, the process is called dilute phase transport and,
below, dense phase transport.

Minimum Fluidization:
As the flow of fluid through a bed of solid particles increases, it eventually
reaches a condition at which the particles are lifted out of permanent contact
with each other. The onset of that condition minimum fluidization.

144
Fluidization: review
Beyond the minimum fluidization point the solid–fluid mass exhibits
flow characteristics of ordinary fluids such as definite viscosity and
flow through lines under the influence of hydrostatic head difference.
The rapid movement of particles at immersed surfaces results in
improved rates of heat transfer. Moreover, although heat transfer rate
between particles and fluid is only moderate, 1–4 Btu/(hr)(sqft)(0F),
the amount of surface is so great, 10,000–150,000 sqft/cuft, that
temperature equilibration between phases is attained within a
distance of a few particle diameters.

Uniformity of temperature, rapid mass transfer, and rapid mixing of


solids account for the great utility of fluidized beds in process
applications.

145
Fluidization: review
Characteristics of Fluidization:

Fluidization depends primarily on the sizes and densities of the


particles, but also on their roughness and the temperature,
pressure, and humidity of the gas. Among the properties of
particles most conducive to smooth fluidization are the following
1. rounded and smooth shape
2. in the range of 50-1000 micrometer diameter
3. a broad spectrum of particle sizes, with ratios of largest to
smallest sizes in the range of 10 to 25.
4. enough toughness to resist attrition

146
Regime of fluidization
Fluidization: review

147
Fluidization: review

Regime of fluidization

148
Fluidized Bed Reactors: Design

Steps involved in designing of fixed bed reactors:


1. Reaction steps and mechanism information
2. Rate equation
3. Determination of weight of the catalyst for specific
conversion
4. Determination of surface average diameter of solid/catalyst
particles
5. Determination of terminal falling velocity
6. Characterize the particles
7. Determination of minimum fluidization velocity
8. Determination of minimum bubbling conditions
9. Determination of bed expansion
10-13. Determination of vessel dimensions (Diameter and
Length)
14. Determination of Pressure inside reactor 149
Fluidized bed reactor: Design steps
Initial molar flowrate of the
limiting reactant, mol/s

Catalyst

CSTR system
Weight of catalyst,
W X A kg
 Fractional
F A0 (  rA ) conversion of A

150
Fluidized bed reactor: Design steps
4. Determination of surface average particle diameter (ds) of solid/catalyst particles

5. Determination of terminal falling velocity

d= diameter of particle for particular fraction


X = wt. fraction of particles
G= gravitational acceleration
µ= viscosity of gas
ρP = true density of particles
ρ =density of gas

151
Fluidized bed reactor: Design steps
6. Characterize the particle group

152
Fluidized bed reactor: Design steps

153
Fluidized bed reactor: Design steps
7. Determination of minimum fluidization velocity

ρf =density of gas/ fluid

8-a. Determination of minimum bubbling conditions

154
Fluidized bed reactor: Design steps
The change of bed level with increasing gas
rate is represented in Fig a. The height remains
constant until the condition of minimum
fluidization is reached, and the pressure drop
tends to level off. Then the bed continues to
expand smoothly until some of the gas
begins to disengage from the
homogeneous dense phase and forms
bubbles. The point of onset of bubbling
corresponds to a local maximum in level
which then collapses and attains a
minimum. With increasing gas rate, the
bed again continues to expand until
entrainment develops and no distinct bed
level exists.
8-b. voidage at minimum bubbling conditions
Voidage at minimum bubbling is correlated by an
equation of Cheremisinoff and Cheremisinoff

155
Fig a.
Fluidized bed reactor: Design steps
9. Determination of operating velocity

Entrainment of the smallest particles cannot be avoided, but an appreciable multiple of


the minimum fluidizing velocity can be used for operation; say the ratio is 5.

Where uf = fluid operating velocity

156
Fluidized bed reactor: Design steps
10: Bed expansion ratio

εmf can be determined using above equation

Eq b is obtained by replacing following equation in eq.a

157
Fluidized bed reactor: Design steps
12-a: Ratio of the bed levels (r=Lmb/Lmf) = ratio of maximum disturbed
level

r=

Lmb = length of bed at minimum bubbling conditions


Lmf = bed length at minimum fluidization point

At high gas velocities the bed level fluctuates. The ratio of maximum disturbed level to
the average level is correlated in terms of Gf and Gmf.

m’ coefficient as a function of particle diameter can be


calculated from graph .
158
Fluidized bed reactor: Design steps

159
Fluidized bed reactor: Design steps
12: Transport disengagement height, TDH

Transport disengagement height, TDH, as a function of vessel diameter and superficial


linear velocity
160
Fluidized bed reactor: Design steps
13: Dimensions of vessel

4𝑄 D = diameter of vessel
𝐷= Q = volumetric flow rate
𝜋𝑢𝑓 uf = operating velocity of fluid
L=height of minimum bubbling bed
𝑊 Lb = bed height
𝐿= 𝜋 W = weight of catalyst
𝜌 (1 − 𝜀 ) 𝐷 r = ratio of maximum disturbed level
4
to the average level
Lv = length of vessel
𝐿 = 𝑟. 𝐿 TBH = disengagement height

𝐿 = 𝐿𝑏 + 𝑇𝐷𝐻

161
Fluidized bed Reactors: Design
14: Pressure drop

The pressure drop in simultaneous flow of gas and solid particles is


made up of contributions from each of the phases. When the
particles do not interact significantly, as in dilute transport, the
overall pressure drop is represented by

for vertical transport; in horizontal transport only the two frictional


terms will be present.

162
Fluidized bed Reactors: Design
14: Pressure drop
The friction factor fg for gas is given by following equation for
Laminar flow

for turbulent flow, it is given by following equation

163
Fluidized bed Reactors: Design
For the solid friction factor fs, many equations of varying complexity have been
proposed, of which some important ones are listed in following table

164
Fluidized bed Reactors: Design

Ug = The linear velocity of carrier gas at 1 atm and 25 0C 165


Fluidized bed Reactors: Design

166
Class Activity: Sizing a FBR

167
Class Activity: Sizing a FBR

ut= 0.39 m/s

168
Class Activity: Sizing a FBR
b) With dp = 84.5 micrometer and density difference of 1699
kg/m3, the material appears to be in Group A

169
Class Activity: Sizing a FBR

d)

170
Class Activity: Sizing a FBR

171
Class Activity: Sizing a FBR

R=1.22

172
Class Activity: Sizing a FBR

173
Class Activity: Sizing a FBR
Fluctuations in level

174
Class Activity: Sizing a FBR

4𝑄
𝐷=
𝜋𝑢𝑓

4 ∗ 0.3
𝐷= = 3.54𝑚
𝜋 ∗ 0.0305

175
Class Activity: Sizing a FBR
At uf=0.0305m/s=3.1 cm/s and vessel diameter of 354 cm
At uf=3.1 cm/s , the abscissa is off the plot, but a rough extrapolation and
interpolation indicates about 1.5m for TDH.

𝑇𝐷𝐻 = 0.43 ∗ 𝑑𝑡
𝑇𝐷𝐻 𝑇𝐷𝐻 = 0.43 ∗ 3.54𝑚
= 0.43
𝑑𝑡
𝑇𝐷𝐻 = 1.5𝑚

176
Class Activity: Sizing a FBR

𝑊
𝐿= 𝜋
𝜌 (1 − 𝜀 ) 𝐷
4

177
Class Activity
Powdered coal of 100 mm dia and 1.28 specific gravity is transported vertically
through a 1-in. smooth line at the rate of 15 g/ sec. The carrying gas in nitrogen
at 1 atm and 250C at a linear velocity of 6.1 m/sec. The density of the gas is 1.14
kg/m3 and its viscosity is 1.7x(10-5)N /sec/m2. Find pressure gradient ∆P/L

178
Class Activity

179
Class Activity
Terminal falling velocity is

Find voidage

(1)

180

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