REACTION KINETICE

AND REACTOR
DESIGN (CH-322)
By H. Scott Fogler 1
Fourth Edition
CHAPTER. 4
ISOTHERMAL
REACTOR DESIGN
By H. Scott Fogler 2
Fourth Edition
PART. 1
MOLE BALANCES IN
TERMS OF
CONVERSION
By H. Scott Fogler 3
Fourth Edition
4.1:
DESIGN STRUCTURE
FOR ISOTHERMAL
REACTORSBy H. Scott Fogler 4
Fourth Edition
4.1: DESIGN STRUCTURE FOR ISOTHERMAL REACTORS:
(USING ALGORITHM RATHER THAN MEMORIZING EQUATIONS)

Use of
Algorithm:

5
4.1: DESIGN STRUCTURE FOR ISOTHERMAL REACTORS:
(USING ALGORITHM RATHER THAN MEMORIZING EQUATIONS)

Use of
Algorithm:

6
4.1: DESIGN STRUCTURE FOR ISOTHERMAL REACTORS:
(USING ALGORITHM RATHER THAN MEMORIZING EQUATIONS)

Use of
Algorithm:

7
4.1: DESIGN STRUCTURE FOR ISOTHERMAL REACTORS:
(APPLICATION OF ALGORITHM TO SPECIFIC SITUATION)

Use of Algorithm:
To draw an algorithm to
calculate the PFR reactor
volume for First order gas
phase reaction
Algorithm layout will be ,

8
4.1: DESIGN STRUCTURE FOR ISOTHERMAL REACTORS:
(APPLICATION OF ALGORITHM TO SPECIFIC SITUATION)

1. Analytically (Appendix. A1) 3. Numerically (Appendix. A4)

2. Graphically (Chapter. 2) 4. Using Software

9
4.1: DESIGN STRUCTURE FOR ISOTHERMAL REACTORS:
(APPLICATION OF ALGORITHM TO SPECIFIC SITUATION)

Use of
Algorithm:

10
4.1: DESIGN STRUCTURE FOR ISOTHERMAL REACTORS:
(APPLICATION OF ALGORITHM TO SPECIFIC SITUATION)

Use of Algorithm:

11
4.1: DESIGN STRUCTURE FOR ISOTHERMAL REACTORS:
(APPLICATION OF ALGORITHM TO SPECIFIC SITUATION)

Use of Algorithm:

12
4.1: DESIGN STRUCTURE FOR ISOTHERMAL REACTORS:
(APPLICATION OF ALGORITHM TO SPECIFIC SITUATION)

Integrating the above equation for a constant temperature and pressure to find
the volume necessary to achieve a specified conversion (or calculate the
conversion that can be achieved in a specified reactor volume).

13
4.2:
SCALE-UP OF LIQUID
PHASE BATCH
REACTOR DATA TO
THE DESIGN OF A
CSTR By H. Scott Fogler 14
Fourth Edition
4.2.1:
BATCH OPERATION
By H. Scott Fogler 15
Fourth Edition
4.2.1: BATCH OPERATION:
In modelling a batch reactor, we have assumed that
there is no inflow or outflow of material and that the
reactor is well mixed.
For most liquid phase reactions, the density change
with reaction is usually small and can be neglected
(i.e: V = ).
For gas phase reactions in which the batch reactor
volume remains constant, we also have V = .
16
4.2.1: BATCH OPERATION:
(CALCULATING THE TIME NECESSARY TO ACHIEVE GIVEN
CONVERSION ‘X’ FOR AN IRREVERSIBLE SECOND-ORDER
REACTION)

17
4.2.1: BATCH OPERATION:
(CALCULATING THE TIME NECESSARY TO ACHIEVE GIVEN
CONVERSION ‘X’ FOR AN IRREVERSIBLE SECOND-ORDER
REACTION)

18
4.2.1: BATCH OPERATION:
(ALGORITHMS TO ESTIMATE REACTION TIMES FOR
BOTH FIRST ORDER AND SECOND ORDER
REACTIONS)

19
4.2.1: BATCH OPERATION:
(CALCULATING THE TIME NECESSARY TO ACHIEVE GIVEN
CONVERSION ‘X’ FOR AN IRREVERSIBLE SECOND-ORDER
REACTION)
This is the reaction time , for second
order, isothermal, constant-volume
batch reaction.
 Therefore the time necessary to achieve 90% of conversion for this case of
second order reaction would become,

20
4.2.1: BATCH OPERATION:
(ESTIMATING THE REACTION TIMES FOR FIRST ORDER REACTIONS)

This is the reaction time , for first

order, isothermal, constant-volume
batch reaction.

21
4.2.1: BATCH OPERATION:
(TOTAL CYCLE TIME, )
The total cycle time in any batch operation is considerably
longer than the reaction time, , as one must also account,
Time necessary to “Fill” ()
Time necessary to “Heat” ()
Time necessary to “Clean he reactor between batches” ()

22
4.2.1: BATCH OPERATION:
(FOR EXAMPLE, FOR BATCH POLYMERIZATION PROCESS)

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 STRATEGY FOR SOLVING NUMERICAL
 Problem Statement
 Sketch
 Identify
 Relative Theories
 Variables
 Knowns and Unknowns
 Inputs and Outputs
 Missing Information

 Assumptions and Approximation

 Specification
 Relative Material
 Use an Algorithm 26
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4.3:
DESIGN OF CSTR
By H. Scott Fogler 34
Fourth Edition
4.3: DESIGN OF CONTINUOUS STIRRED TANK REACTORS:

General Mole Balance for CSTR

Volume necessary to achieve

conversion ‘X’ in ‘CSTR’

Space time required to achieve

conversion ‘X’ in ‘CSTR’

This equation applies to a single CSTR or to the first

reactor of CSTRs connected in series. 35
4.3.1:
A SINGLE CSTR
By H. Scott Fogler 36
Fourth Edition
4.3.1: A SINGLE CSTR:
Stoichiometry:
Equation correlating conversion and concentration for
liquid phase reaction with no change in volume

Putting value of into rate equation

Rate Law:
First-order irreversible reaction in terms of concentration

−𝐫 𝐀 =𝐤 𝐂𝐀𝐎 (𝟏 − 𝐗 ) Rate Law:

First-order irreversible reaction in terms of conversion

General mole balance equation in terms of

space time 37
4.3.1: A SINGLE CSTR:
Space time required to reach concentration ‘X’

Rearranging

CSTR relationship between space time and conversion

for a first-order liquid-phase reaction

Relationship between
concentration and space time for
first-order, irreversible reaction

38
4.3.1: A SINGLE CSTR:
Relationship between concentration and space time for
first-order, irreversible reaction

For the first order reaction, the product is often referred to

as the reaction ‘Damkohler Number’, Da.
‘Da’ number is a dimensionless number that can give us
quick estimate of the degree of conversion that can be
achieved in continuous flow reactor.
‘Da’ number is the ratio of “the rate of reaction of ‘A’” to
“the rate of convective transport of ‘A’ at the entrance of the
reactor” 39
4.3.1: A SINGLE CSTR:
(DAMKOHLER NUMBER)

• Conversion in terms of ‘Da’ number for first

order liquid phase reaction.
40
• As for first order reaction ‘Da’=
4.3.1: A SINGLE CSTR:
(INFORMATION FROM DAMKOHLER NUMBER)

‘Da’ number for first order, irreversible ‘Da’ number for second order, irreversible
reactions reactions 41
4.3.2:
CSTR IN SERIES
By H. Scott Fogler 42
Fourth Edition
4.3.2: CSTR IN SERIES:
Considering a first
order reaction with no
change in volumetric
flow rate(V=) to be
carried out in two
CSTRs connected in
series.

43
 4.3.2: CSTR IN SERIES:

Exiting concentration from 2nd

CSTR for first-order liquid
phase reaction. 44
4.3.2: CSTR IN SERIES:

45
4.3.2: CSTR IN SERIES:

46
4.3.2: CSTR IN SERIES:

Equation for
rate of
disappearance of
‘A’ in ‘nth’
reactor
47
4.3.3:
CSTR IN PARALLEL
By H. Scott Fogler 48
Fourth Edition
4.3.3: CSTR IN PARALLEL:
 Considering a case in which equal-
sized reactors are placed in parallel
rather than in series.
 The feed is distributed equally among
each of the reactor.
 The balance on any reactor, say ‘i’,
gives the individual reactor volume as:

49
4.3.3: CSTR IN PARALLEL:

Constant Temp.

50
4.3.3: CSTR IN PARALLEL:

51
4.3.3: CSTR IN PARALLEL:

This result shows that conversion achieved in

any one of the reactor in parallel is identical
to what would be achieved if the reactants
were fed in one stream to one large reactor of
volume V.
52
4.3.4:
A SECOND ORDER
REACTION IN CSTR
By H. Scott Fogler 53
Fourth Edition
4.3.4: A SECOND ORDER REACTION IN CSTR:

54
4.3.4: A SECOND ORDER REACTION IN CSTR:

Munis sign. Must be

choosen in quadratic
equation because
‘X’can not be greater
than 1.

55
4.3.4: A SECOND ORDER REACTION IN CSTR:
A point to consider in
this diagram is from
conversion of 67% to
88%, there is a 10
fold rise in reactor
volume required.

CSTR normally operates under the condition of lowest value of the reactant concentration (i.e:
the exit concentration), and consequently the smallest value of rate of reaction.
56
EXAMPLE: 4.2

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4.4:
TUBULAR REACTORS
By H. Scott Fogler 63
Fourth Edition
LIQUID PHASE
SYSTEMS

64
4.4: TUBULAR REACTORS:
 Gas phase reactions are carried out primarily in tubular reactors where the
flow is generally turbulent.
 By assuming that there is no dispersion and there are no radial gradients in
either temperature, velocity, or concentration, we model the flow in the
reactor as plug flow.

65
4.4: TUBULAR REACTORS:
 The differential form of the PFR design equation,
 Must be used when there is a pressure drop in the
reactor or heat exchanger between the PFR and
the surroundings.

Considering an example of a second order reaction and

studing the reaction both for “liquid-phase” reaction and
“gas-phase” reaction.
66
 4.4: TUBULAR REACTORS:
(LIQUID PHASE SYSTEMS)

Combined PFR mole balance and Rate law

If the reaction is carried out in liquid phase, the

concentration of ‘A’ would become

Integrating the differential equation for PFR and taking ‘k’

outside the integral assuming it a constant due to constant
temperature (isothermal process)

Dividing this equation with volumetric flowrate to introduce ‘Da’ number into the expression

• Equation for PFR working under isothermal conditions,

for liquid-phase second order reaction.
• Obtained equation is in terms of ‘Da’ number, giving the
relationship of conversion with ‘Da’. 67
GAS PHASE
SYSTEMS

68
 4.4: TUBULAR REACTORS:
(GAS PHASE SYSTEMS)

Equations for dealing with gas phase concentrations

Volumetric flow rate for

gas phase systems

For constant temperature (T=) and constant pressure (P=) gas phase reactions, the concentration is
expressed as a function of conversion as:

Stoichiometry for gas

phase reactions
69
4.4: TUBULAR REACTORS:
(GAS PHASE SYSTEMS)

Combining rate law,

stoichiometry and
mole balances for
PFR, we get:

This is the volume required in case of PFR to

reach upto conversion ‘X’, with gas phase 2nd
order system, assuming temperature and
pressure constant

Assuming a constant and therefore can be taken outside the integral.

Similarly ‘k’ can be treated as a constant due to constant temperature and
likewise will be taken outside the integral
Integrated form of reactor volume equation
for PFR with integration completed using
70
Appendix A.1
APPENDIX A-1

71
APPENDIX A-1

72
APPENDIX A-1

73
APPENDIX A-1

74
4.4: TUBULAR REACTORS:
(GAS PHASE SYSTEMS)

A plot of conversion along the length (i.e:

volume) of the reactor is shown for four
different reactions, and values of ‘’ are
varied.

𝜺= 𝑦 𝐴𝑂 𝛿
𝑐 𝑑 𝑏
𝛿= + −1 −
𝑎 𝑎 𝑎 75
4.4: TUBULAR REACTORS:𝛿= 𝑐 + 𝑑 −1 − 𝑏
(GAS PHASE SYSTEMS) 𝑎 𝑎 𝑎
What does it mean by increasing or decreasing ….???
Case 1:
 When the number of moles of the product are more as compared to reactants
(as concluded from stoichiometric balanced chemical equation), will always
be positive.

Case 2:
 When the number of moles of the product are less as compared to reactants
(as concluded from stoichiometric balanced chemical equation), will always
be negative.
76
4.4: TUBULAR REACTORS:𝛿= 𝑐 + 𝑑 −1 − 𝑏
(GAS PHASE SYSTEMS) 𝑎 𝑎 𝑎
What does it mean if is zero….???
Case 3:
 When the number of moles of the product are equal to the number of moles of reactants (as
concluded from stoichiometric balanced chemical equation), will always be zero.

77
4.4: TUBULAR REACTORS:
(GAS PHASE SYSTEMS)
Effect of Change in number of moles in the gas phase on the
relationship between conversion and volume:
Volumetric flow rate for
gas phase systems

At constant temperature and pressure, this equation becomes:

Considering this equation for three set of systems:

1. Increasing number of moles
2. Decreasing number of moles
3. Number of moles remain unchanged 78
4.4: TUBULAR REACTORS:
(GAS PHASE SYSTEMS)

79
4.4: TUBULAR REACTORS:
(GAS PHASE SYSTEMS)

80
4.4: TUBULAR REACTORS:
(GAS PHASE SYSTEMS)

81
EXAMPLE: 4.3

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4.5:
PRESSURE DROP IN
REACTORS
By H. Scott Fogler 89
Fourth Edition
4.5: PRESSURE DROP IN REACTORS:

90
4.5.1:
PRESSURE DROP AND
RATE LAWS
By H. Scott Fogler 91
Fourth Edition
4.5.1: PRESSURE DROP AND RATE LAWS:
 For gas phase reactions the pressure drop may be very important.
 So focusing our attention on accounting for the pressure drop in the rate law.
 Since we know that the “Gas-phase concentration as a function of conversion” is given
as:

92
4.5.1: PRESSURE DROP AND RATE LAWS:

93
4.5.1: PRESSURE DROP AND RATE LAWS:

Rate of reaction in terms of

conversion and pressure drop for
second order reaction in PBR
As it is clear from the equation,
 The larger the pressure drop due to frictional losses, the smaller the value of ‘P’ and
smaller will be the reaction rate.

Combining rate of reaction with differential

form of mole balance for PBR and assuming 94
isothermal operation (T=)
 4.5.1: PRESSURE DROP AND RATE LAWS:
Dividing by

For isothermal operation (T=), the right

hand side is only the function of ‘Pressure’
and ‘Conversion’

function of ‘Pressure’ and ‘Conversion’

Now we need to relate pressure drop as a function of catalyst weight in order to

determine the conversion as a function of catalyst weight

Equation required of the form…!!! 95

4.5.2:
FLOW THROUGH
PACKED BED
By H. Scott Fogler 96
Fourth Edition
4.5.2: FLOW THROUGH PACKED BED:
 The majority of gas phase reactions are catalyzed by passing the reactant through a
packed bed of catalyst particles.

 The equation used most to calculate pressure drop in a packed porous bed is the “Ergun
Equation”.

 Term-1 is dominant for laminar flow, and Term-2 is dominant for turbulent flow.

97
 4.5.2: FLOW THROUGH PACKED BED:

Understanding about
the terminology…!!!

98
 4.5.2: FLOW THROUGH PACKED BED:

Understanding about the terminology…!!!

Superficial
velocity (or superficial flow veloci
ty), in engineering of multiphase
flows and flows in porous media, is
a hypothetical (artificial)
flow velocity calculated as if the
given phase or fluid were the only
one flowing or present in a given
cross sectional area.
99
4.5.2: FLOW THROUGH PACKED BED:

 In calculating the pressure drop using the Ergun Equation, the only parameter that varies
with pressure on the right-hand side of “Ergun Equation” is the gas density, .
 Because the reactor is operated at steady state, the total mass flow rate at any point down
the reactor, is equal to the entering mass flow rate, (i.e: equation of continuity).

Due to steady-state process, the entering mass flow

rate will always be equal to the mass flow rate at any
point within the reactor
100
 4.5.2: FLOW THROUGH PACKED BED:

Since equation for gas-phase volumetric

flow rate for flow reactors

Equation for gas-phase variable density Equation for gas-phase pressure drop with length
equation for flow reactors derived from through a packed bed of solid catalyst in terms of
variable volumetric flowrate variable density 101
 4.5.2: FLOW THROUGH PACKED BED:

Where is a constant that depends only on the

If properties of the packed bed and the entrance
conditions

Equation for Pressure drop with distance travelled into the

catalyst

 For tubular packed-bed reactors, we are more interested in catalyst weight rather than the
distance ‘z’ down the reactor.
Catalyst weight upto
a distance ‘z’ into the
reactor 102
4.5.2: FLOW THROUGH PACKED BED:

Equation for bulk density in terms of particle density and fraction of

solid mass of catalyst (excluding the porous region)

103
4.5.2: FLOW THROUGH PACKED BED:
(BULK DENSITY)

104
4.5.2: FLOW THROUGH PACKED BED:
𝑊 =( 1− 𝜑 ) 𝐴𝑐 𝑧 𝜌 𝑐

• Equation for pressure drop in terms of weight

‘W’ of catalyst rather than distance ‘z’ travelled
into the catalyst structure.
• This equation can be used for multiple reactions
and membrane reactors

Accumulating all the system relevant physical

If properties under a single constant

And
If
105
4.5.2: FLOW THROUGH PACKED BED:
This equation can be used when multiple reactions are occurring
or when there is pressure drop in a membrane reactor

 In case of only single reaction taking place in the system, we have:

Dividing this equation by

Putting in equation,

We get: Differential form of ‘Ergun

Equation’ for the pressure drop
in ‘Packed Beds’ 106
 4.5.2: FLOW THROUGH PACKED BED:
Differential form of ‘Ergun
Equation’ for the pressure drop
in ‘Packed Beds’

Where

Function of: Function of: 107

ANALYTICAL
SOLUTION
By H. Scott Fogler 108
Fourth Edition
ANALYTICAL SOLUTION:

109
 ANALYTICAL SOLUTION:

Note:
Be sure not to use this
equation if does not
equal to zero or the
reaction is not carried
out isothermally.
Equation for pressure drop for
gaseous system with can be
written in terms of reactor 110
length ‘z’,
4.5.4:
ANALYTICAL SOLUTION
FOR REACTION WITH
PRESSURE DROP
By H. Scott Fogler 111
Fourth Edition
4.5.4: ANALYTICAL SOLUTION FOR REACTION WITH PRESSURE DROP:
(STUDYING THE EFFECT OF PRESSURE DROP WITH WEIGHT OF CATALYST AND
RELATING PARAMETERS)
process
isothermal
Assuming

and

112
4.5.4: ANALYTICAL SOLUTION FOR REACTION WITH PRESSURE DROP:
It is clear from the graphical relations that:
 When there is a pressure drop in a reactor, the reactant concentrations and thus reaction
rate for reaction will always be smaller than the case with no pressure drop.
 As a result of smaller reaction rate, the conversion will be less with pressure drop than
without pressure drop.

113
 4.5.4: ANALYTICAL SOLUTION FOR REACTION WITH PRESSURE DROP:

Since
114
4.5.4: ANALYTICAL SOLUTION FOR REACTION WITH PRESSURE DROP:

115
4.5.4: ANALYTICAL SOLUTION FOR REACTION WITH PRESSURE DROP:

116
The void fraction is 45% 117
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WHAT IF PROBLEM FOR EXAMPLE 4.5

126
WHAT IF PROBLEM FOR EXAMPLE 4.5

127
SUMMARY
 In both laminar and turbulent flow, increasing the pressure, P0, decreases the pressure-drop
parameter
 Decreasing the particle diameter Dp increases the pressure-drop parameter for both laminar
and turbulent flow, but more so for the laminar where ~ 1/Dp2.
 The smaller the pressure-drop parameter, the smaller the pressure drop and thus the greater
the conversion.
 For laminar flow, the negative effects of reducing the particle size by a factor of 4 are
stronger than the effect of increasing pressure by a factor of 3.

128
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• Using Polymath / Matlab for evaluation of multiple Ordinary Differential Equations (ODE)

135
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4.5.5:
SPHERICAL PACKED
BED REACTORS
By H. Scott Fogler 137
Fourth Edition
4.5.5: SPHERICAL PACKED BED REACTORS:
 In a spherical reactor, the cross-
section varies as we move through
the reactor and is greater than in a
normal packed bed reactor.
 Consequently, the superficial mass
velocity ‘G’ will be smaller.

 Equation 4-22 shows that the

smaller the value of ‘G’, smaller
will be the pressure drop and thus a
greater conversion.

138
4.6:
SYNTHESIZING THE
DESIGN OF A CHEMICAL
PLANT By H. Scott Fogler 139
Fourth Edition
4.6: SYNTHESIZING THE DESIGN OF A CHEMICAL PLANT:
Profit = Value of
the products – Cost
of reactants –
Operating cost –
Separation costs.
 The operating costs
include such costs
as energy, labor,
overhead, and
depreciation of
equipment.
140