Chemical Reaction

Engineering

Dr. Rabya Aslam

Institute of Chemical Engineering and Technology
University of the Punjab, Lahore 54590 1
Dec, 2018 rabya.icet@pu.edu.pk
 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
 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.

3
 Course objectives

The objective of this course is to give the understanding

of designing of commonly used chemical reactors. This
course will provide in-depth knowledge of the
application of laws of thermodynamics and reaction
kinetics for the economical design of chemical reactors.

Students will learn how can a chemical engineer

develop a rate expression and design an
industrial reactor.

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 Course Learning Outcomes

 Explain chemical reaction engineering related

terminology
 Develop the rate equation with concentration and
time data using integral and differential methods.
 Derive the performance equations of ideal batch and
flow reactors to size the ideal reactors (homogeneous
and heterogeneous system).
 Evaluate the combination of reactors’ system to
minimize the volume.

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 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 = 𝑣 𝑜
𝑉
1 + 𝑘( )
𝑣𝑜
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 Size comparison of PFR and MFR

2. For PFR/Tubular reactor

Assumption: constant density first order reaction
𝑋𝐴
𝑉 𝑑𝑋𝐴
𝜏 = = 𝐶𝐴0 න
𝑣𝑜 0 𝑘𝐶𝐴0(1 − 𝑋𝐴)

𝑉 1
= − ln(1 − 𝑋𝐴)
𝑣𝑜 𝑘

𝑉
−𝑘(𝑣 )
𝑋𝐴 = 1 − 𝑒 0

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 Size comparison of PFR and MFR

Fractional conversion, XA

𝑉𝑚 𝑉𝑃
𝑘 𝑜𝑟 𝑘( )
𝑣0 𝑣0
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 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)

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 Comparison of PFR and CSTR for nth order reaction

Dividing 2 and 3

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Comparison of PFR and CSTR

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Comparison of PFR and CSTR

12
 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.
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Ratio of CSTR volume to PFR volume

14
 Assignment 03

Drive the following relation for first order system

Where α is the ratio of MFR to PFR volume.

Submit till 19th March 2019.

15
 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.
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 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.

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 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.

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 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
𝑋1 =
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 𝑓𝑒𝑑 𝑡𝑜 𝑓𝑖𝑟𝑠𝑡 𝑟𝑒𝑎𝑐𝑡𝑜𝑟
𝑡𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑢𝑝𝑡𝑜 𝑝𝑜𝑖𝑛𝑡 2
𝑋2 =
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 𝑓𝑒𝑑 𝑡𝑜 𝑓𝑖𝑟𝑠𝑡 𝑟𝑒𝑎𝑐𝑡𝑜𝑟
19
And so on.
 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.

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 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.
𝑉 𝑉 𝑉
= =
𝐹 𝐴 𝐹 𝐵 𝐹 𝑁 21
 Class Activity

𝑉 𝑉
N =
𝐹 𝐷 𝐹 𝐸

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

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 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

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 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,

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 Assignment

Derive the space time correlation for N-CSTRs in

series for a zero order reaction.

Submit till 19th March 2019

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Case 3: CSTR in series

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Case 3: CSTR in series

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 Case 3: CSTR in series
For second order reaction

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 Class activity

If instead of one reactor, two MFRs of same

volume are used;

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Class activity

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 Case 4: CSTR in parallel

For ith reactor

(1)

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. 31
 Case 5: 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.

32
 Case 5: CSTR of different volumes in series
A graphical procedure for finding the outlet composition from a series of
mixed flow reactors of various sizes for reactions with negligible density
change (Ɛ=0) has been presented by Jones (1951). All that is needed is an r
versus C curve for component A to represent the reaction rate at various
concentrations.
Let us illustrate the use of this method by considering three mixed flow
reactors in series with different volumes, feed rates, concentrations, space-
times and volumetric flow rates. we may write for component A in the first
reactor.

or

For ith reactor

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 Case 5: CSTR of different volumes in series
Plot the C versus (-rA) curve for
component A. To find the conditions in
the first reactor note that the inlet
concentration Co is known (point L),
C1, and (-r)1, correspond to a point on
the curve to be found (point M), and
that the slope of the line LM = MN/NL
= -(l/ 𝜏1) Hence, from Co draw a line of
slope -(l/ 𝜏1) until it cuts the rate curve;
this gives C1.
This procedure is then repeated as
many times as needed.

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 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.

35
Determining the Best System for a Given Conversion

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 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
37
best arrangement of units.
 Class Activity

CA2 = 0.25 mol/L

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 Class Activity

It is improved and expected activity

is approximately 1/20 of feed
stream.
39
Class Activity

CA2 = 0.1 mol/L

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 Class Activity

Vtotal, 1 = 305 dm3

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Vtotal,2= 262 dm3
 Class Activity

V = 364 dm3
Repeat the same problem for single CSTR and compare the result with
two CSTR is series?
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 Assignment 4
Solve following exercise problems from Chapter 6, Octave
Levenspiel, 3rd edition.

P6.4
P6.5

And exercise problem from Scott Fogler, 3rd edition

P2.3

Submit till 25th March 2019

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 Recycle Reactors
In certain situations, when one desires to promote
backmixing in PFR, it is found to be advantageous to
divide the product stream from the reactor and return a
portion of it to the entrance of the reactor.
The need for backmixing arises to
 enhance the reaction selectivity
 to moderate the thermal effects associated with the
reaction.
Recycle ratio may be defined as

44
 Recycle Reactors
The recycle ratio can be made to vary from zero to infinity. Reflection suggests
that as the recycle ratio is raised the behavior shifts from plug flow (R = 0) to
mixed flow (R = ∞). Thus, recycling provides a means for obtaining various
degrees of backmixing with a plug flow reactor.
Performance Equation for the recycle reactor:
Consider a recycle reactor with following nomenclature

For PFR,

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 Recycle Reactors
The flow entering the reactor includes both fresh feed and the recycle stream.
Measuring the flow split at point L, we then have

(1)

And conversion in terms of concentration for 𝝐 ≠0 can be written as follows:

(2) 46
 Recycle Reactors
Because the pressure is taken to be constant, the streams meeting at
point K may be added directly. This gives

Using eq (1)

Using FA0 = v0 CA0, we have

(3)

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 Recycle Reactors

Combining (2) and (3), we have XA1 in measurable variables

Thus performance equation for recycle reactor can be written as

When density changes are negligible, above equation can be written as

48
 Recycle Reactors

cv
cv

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Fig A: Representation of the performance equation for recycle reactors.
 Recycle Reactors
For the extremes of negligible and infinite recycle the system
approaches plug flow and mixed flow.

50
 Recycle Reactors

Fig b: The recycle extremes approach plug flow and mixed flow
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Comparison of performance of recycle and plug flow for
first-order reactions

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Comparison of performance of recycle and plug flow for
Recycle Reactors
second-order reactions

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 Class activity

XAf = 0.75

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For solution, pls see the lecture notes.
 Class activity

CAf = 2.3 mol/L

55
For solution, pls see the lecture notes.
 Recycle Reactors-MFR
Derive the performance equation for MFR reactor with Recycle

56
Recycle Reactors: Assignment

Submit till 2nd April 2019

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 Assignment 5
Solve following problem from Chapter 6, Octave
Levenspiel, 3rd edition.

P 6.20
P6.21

Submit till 2nd April 2019

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 Summary :Combination of reactors: Optimum size ratio of two
reactors
Important Points: Selection of reactors if intermediate
conversion is known.
The optimum size ratio for two mixed flow reactors in
series is found in general to be dependent on the kinetics of
the reaction and on the conversion level.

 For first-order reactions, equal-size reactors are best.

 For reaction orders n > 1, the smaller reactor should come
first followed by the larger reactor.
 For n < 1, the larger reactor should come first followed by
the smaller reactor.

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 Combination of reactors: Optimum size ratio of two reactors

If intermediate conversion is not known, method of maximization of

rectangles may be used.

The optimum size ratio of the two reactors is achieved where the
slope of the rate curve at M equals the diagonal NL. The best
value of M determines the intermediate conversion X1, as well as the
size of units needed.

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 Combination of reactors: Optimum size ratio of two reactors

If PFR and MFR are to be used as combination then optimum

conversion point or point at which rate is maximum should be taken
as intermediate point.

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 Packed bed reactors(PBR)

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

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 Packed bed reactors
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.

Packed bed reactor scheme

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 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

64
 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 )
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 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 )
66
Basic performance equations of heterogeneous flow
reactors (FBR)

CSTR (100% backmixed reactor) system

W XA
 Fractional
FA0 (rA ) conversion of A
Weight of catalyst,
kg

Initial molar flowrate of the

limiting reactant, mol/s

Catalyst

67
Basic performance equations of heterogeneous
flow reactors
CSTR system PFR system
Weight of catalyst,

dX A (rA )
kg
W XA
 
FA0 (rA ) Fractional dW FA0
conversion of A

Initial molar flowrate of the

limiting reactant, mol/s
XA
W dX A
Catalyst FA0
 
0
(rA )

68
 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.

69
 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.

70
 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 72

 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.

73
 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.
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 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]

75
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 76
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.

77
 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.

78
 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

79
 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).
80
Selectivity of a catalyst

81
 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.
82
 Selection of a catalyst

The order of importance of the activity,

selectivity, and stability as suggested by
scholars is as follows:

Selectivity
Stability
Activity

83
 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.

84
 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.
85
 Characterization
V 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.
86
 Catalyst Characterization
SEM image of a zeolite Y

XRD patterns of a zeolite Y

87
TEM image of Rh/SiO2
Steps involved in a heterogeneous catalytic fluid-
solid reaction

Fluid
(mainly
gas)

88
 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.
89
 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.

90
 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

91
Steps involved in a heterogeneous catalytic fluid-
solid reaction

Fluid
(mainly Important in
Intrinsic
gas) kinetics

92
Heterogeneous reactors

93
 Commonly used industrial heterogeneous
reactors: Introduction
1: Packed Bed Reactors (PBR) also known as Fixed Bed Reactors (FBR)

94
 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.

95
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

Gas/Liq/Solid phase reactor

96
Packed Bed Reactors: Types

97
 Packed Bed Reactors: Types
B

98
Packed Bed Reactors: Types

99
Packed Bed Reactors: Types

100
 Packed Bed Reactors: Types

101
Tubular reactor
 Packed Bed Reactors: Introduction

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

to 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.

102
 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
103
 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 104
 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 105
 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
106
 Packed Bed Reactors: Design
6. Volume of reactor

 2
Vreactor  H reactor Dcatalyst 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

107
 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
108
 Packed Bed Reactors: Design
7. Pressure Drop inside reactor

109
Packed Bed Reactors: Design

110
Packed Bed Reactors:
V Design

111
 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 f mixture

can be find as

112
Packed Bed Reactors: Design

Any Question??

113
 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.

114
 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 115
acceptable level.
 Fluidized bed reactors: Introduction

 Another application is coal gasification, which is

becoming increasingly important as industry switches
from imported petroleum and natural gas to coal as a
primary source of chemical raw material feedstocks and
energy.
 Orthophthalic anhydride is made by oxidation of
naphthalene in a fluidized bed of V2O5 deposited on
silica gel with a size range of 0.1–0.3mmwith a contact
time of 10–20 sec at 350–3808C. 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.
116
 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.

117
 Fluidized bed reactors: Introduction
Features of FBR Common Applications

118
 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.
119
 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.

120
 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.

121
 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

122
Fluidization: review

Regime of fluidization

123
 Fluidization: review

Regime of fluidization

124
 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 drop inside reactor 125
Fluidized bed reactor: Design steps
Initial molar flowrate of the
limiting reactant, mol/s

Catalyst

CSTR system
Weight of catalyst,
kg
W XA

FA0 (rA ) Fractional
conversion of A
126
 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

127
 Fluidized bed reactor: Design steps
6. Characterize the particle group

p
128
Fluidized bed reactor: Design steps

129
 Fluidized bed reactor: Design steps
7. Determination of minimum fluidization velocity

ρf =density of gas/ fluid

8-a. Determination of minimum bubbling conditions

130
 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

131
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

132
 Fluidized bed reactor: Design steps
11: Bed expansion ratio

Bed expansion ratio as a function of reduced flow rate and

particle size
133
 Fluidized bed reactor: Design steps
11: Bed expansion ratio

εmf can be determined using above equation

134
 Fluidized bed reactor: Design steps
12-a: Ratio of the bed levels

Lmb = length of bed at minimum bubbling conditions

Lmf = bed length at minimum fluidization point

12-b: ratio of maximum disturbed level to the average level

135
Fluidized bed reactor: Design steps

136
 Fluidized bed reactor: Design steps
12: Transport disengagement height, TDH

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

superficial linear velocity
137
 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 2 W = weight of catalyst
𝜌𝑝 (1 − 𝜀𝑚𝑏 ) 𝐷 r = ratio of maximum disturbed level
4
to the average level
Lv = length of vessel
𝐿𝑏 = 𝑟. 𝐿 TBH = disengagement height

𝐿𝑏 = 𝐿𝑏 + 𝑇𝐷𝐻

138
 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.

139
 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

140
 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

141
 Fluidized bed Reactors: Design

Ug = The linear velocity of carrier gas at 1 atm and 25 0C 142

Fluidized bed Reactors: Design

143
 Class Activity
Powdered coal of 100 micrometer 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

144
 Class Activity
Terminal falling velocity is

Find voidage

(1)

Particle velocity may be found using eq 14

(2)

145
 Class Activity
Where friction factor for solids is given as follows(using Yang correlation)

(3)

Simultaneously solving (1), (2), and (3)

Next step is to calculate Reynolds number

146
 Class Activity
Friction factor for turbulent region

147
 Assignment: Sizing a FBR

Submit the assignment till 3rd May 2019 both in

handwritten form.
Also make excel sheet for FBR sizing for the
same question and submit the hard copy of
148
excel sheet as well.