CHE 611

Advanced Chemical Reaction

Engineering

Muhammad Rashid Usman, PhD

Institute of Chemical Engineering and Technology
University of the Punjab, Lahore 54590 1
Feb, 2016 [Link]@[Link]
Course contents (1.5 + 1.5 credit hours)
Homogeneous and heterogeneous reaction
rate expressions
Characterization of solid catalysts
General characteristics of heterogeneous
reactors. Simultaneous mass and heat
transports with chemical reaction in porous
catalysts
Analysis and design of gas-liquid reactors: Mechanically
agitated vessels, bubble columns, and packed columns
Non-catalytic reactors
Analysis and design of three phase reactors: Slurry reactors,
trickle bed reactors, and fluidized bed reactors 2
 Relevant books
 Froment, G.F.; Bischoff, K.B.; De Wilde, J. 2011. Chemical
reactor analysis and design. 3rd ed. John Wiley & Sons, Inc.
 Fogler, H.S. 2006. Elements of chemical reaction engineering.
4th ed. Prentice-Hall.
 Levenspiel, O. 1999. Chemical reaction engineering. 3rd ed.
Wiley & Sons, Inc., Singapore.
 Missen, R.W.; Mims, C.A.; Saville, B.A. 1999. Introduction to
chemical reaction engineering and kinetics. John Wiley &
Sons, Inc., New York.
 Carberry, J.J. Chemical and catalytic reaction engineering.
Dover Publications, Inc. New York
 Smith, J.M. 1981. Chemical engineering kinetics. 3rd ed.
McGraw-Hill Int. Book Co., Singapore.
 Hill, Jr., C.G.; Root, T.W. 2014. Introduction to chemical 3
nd
engineering kinetics and reactor design. 2 ed. Wiley.
 Course objectives (1.5 credit hours)
The objective of the part of my course is to develop the
understanding of heterogeneous catalytic (gas-solid)
reactions.
The course attendee will be encountered to the:
 Concepts of catalysts, catalytic kinetic rate
expressions, pore diffusion, and effectiveness factor
 Use of rate expressions in the designing of a chemical
reactor
 Concepts of one-dimensional and two-dimensional
pseudohomogeneous models

Student will learn how can a chemical engineer develop

a rate expression and design an industrial reactor 4
Ammonia synthesis

5
 Concept of
fuel refinery

6
Petrochemicals flowchart

7
 Catalysis and reaction engineering
Catalysis and reaction engineering tries to answer to the
following types of questions:

 What are the optimum operating conditions for a reaction

system to carry out one ore more desired reactions?
 What is the optimum reactor design, i.e., size, type,
energy considerations, and configuration of the reactor
system?
 Is there a need of a catalyst? If yes, how to develop and
design of an optimum industrial catalyst?
 What is the right reaction mechanism which will helpful
for developing the basic science as well as in the design
of a suitable catalyst?
8
Catalysis and reaction engineering

9
 Stoichiometric coefficient
For the reaction
aA  bB  cC  dD ν
a, b, c and d are the stoichiometric coefficients.
If Ai is the ith component of a reaction, then one can write

0  i Ai
By convention:
• A stoichiometric coefficient for a reactant is negative
• A stoichiometric coefficient for a product is positive
• A stoichiometric coefficient for an inert, solvent, or
catalyst is zero. 10
 Extent of a reaction

ξ ni  ni 0  i  
Fi  Fi 0  i   

ni  ni 0 change in moles of a species

 
i stoichiometric coefficient

Fi  Fi 0 change in molar flowrate of a species

  
i stoichiometric coefficient

ξ extent of a reaction in terms of change in moles

ξ′ extent of a reaction in terms of change in molar flowrate
νi stoichiometric coefficient of an ith species
11
 Conversion or fractional conversion
Ratio of change in moles of a reactant (usually limiting
reactant) to the moles of the reactant fed.

n A0  n A FA0  FA
For a reactant A: XA  
n A0 FA0

nA0 = initial moles of the reactant “A”, mol; nA = moles of “A” at

any time t (s), mol; FA0 = initial molar flowrate, mol·s−1, FA =
molar flowrate of A at any time t (s), mol·s−1.

For an irreversible and single (no side reaction) reaction, an

increase in the outlet conversion is an indication of higher rate
of the reaction
12
 Relationship between extent of a
reaction and fractional conversion [1]

For reactant A:
n A  n A0

A

n A  n A0 n A0  n A0  n A n A0 
       
A n A0  n A0 A 

n A0  n A
XA 
n A0

 n A0  X A n A0

   X A  
 
 A  A
13
 Selectivity
It is the ratio of moles of the one (usually desired)
product to the moles of another (usually undesired)
product.
A B
AC
moles of B formed
Selectivity of B 
moles of C formed
moles of C formed
Selectivity of C 
moles of B formed

The definition of selectivity may vary from source to source, so

be careful while taking the value from a literature source
14
 Yield
It is the ratio of moles of a certain product to the maximum
possible moles of that product which can be formed.
Or
It is the ratio of moles of a certain product to the moles consumed
of the limiting reactant.
Or
It is the ratio of moles of a certain product to the moles of the
limiting reactant fed.

The definition of yield may vary from source to source. The

definitions of yields defined above may be referred to as the
definition of selectivity in some reference.

15
 Limiting and excess reactant
 In a chemical reaction the reactant present in excess to that
required stoichiometrically is the excess reactant the other is
limiting reactant
 If the reactants are added in stoichiometric amounts, there is
no point using the concept of limiting or excess reactant
 The limiting or excess reactant is indicated by dividing the
number of moles of each reactant in the feed to the
corresponding stoichiometric amount (from a balanced
chemical equation) of the reactant. The reactant with the
lowest ratio is the limiting reactant and will be the first to be
fully consumed in the reaction, if the reaction goes to
completion
The choice of the limiting reactant is arbitrary and depends
on the cost (profit) considerations 16
 Limiting and excess reactant
Can you mention any example of an industrial
process and indicate the limiting reactant?
What are the reasons for the choice of a particular
limiting reactant in your example?

Combustion of a coal
required excess air

[Link]

17
 Rate of a chemical reaction [2]
The rate of consumption of a reactant species is defined as
the change in number of moles of the reactant species per
unit volume of the reaction mixture per unit time.
Negative sign
indicates that rate is 1 dnA Perfectly
decreasing with time (rA )    general
and required as dnA is V dt
negative for a reactant Volume of
reaction mixture
Not general
dC A Applicable when volume of the reaction mixture
( rA )   does not change during the course of reaction
dt It may be true for liquid phase reactions or for
constant density gas phase reactions

The volume of a gas also changes due to changes in operating

conditions (temperature and pressure) in addition to changes in
number of moles 18
 Rate of a chemical reaction
 The rate of a chemical reaction is usually based on the limiting
reactant
 On the similar basis, a rate may be defined for the formation of
a product species
 For the reaction:
aA  bB  cC  dD
or

(rA ) ( rB ) rC rD
  
a b c d

This minus sign is to show rate of consumption of a reactant

It has no mathematical importance, only a symbol 19
 Various definitions of rate of a
chemical reaction [3]
Based on unit volume
of the reaction mixture

Based on unit mass

in fluid-solid system

Based on unit surface of solid in fluid-solid

system or unit interfacial area in two fluid systems

Based on unit volume of solid

in fluid-solid system

Based on unit volume of reactor when different

from unit volume of the reaction mixture

8 20
 Various definitions of rate of a
chemical reaction [3]
Rates defined on various basis are interchangeable and
the following may be shown:

In our course we will use (‒rA) as the rate of

consumption of a limiting reactant A having the
SI unit of mol A·s‒1·g-kcat‒1
21
 Relative values of rates of reactions [3]

Rates of reactions vary in a wide range. Some reaction

are very fast and some reactions are extremely slow.

22
 Why are we interested in rate?
A higher rate of reaction means less processing time in a
batch reactor and smaller size of reactor vessel in a continuous
flow reactor (CSTR and plug flow reactor)
As the residence time is dependent upon the rate, the
knowledge of rate is required for the design of a reactor
(remember basic design equations for batch and flow reactors)
The question is then how can we find rate?
We need an expression (rate equation) that describes the rate
of a given reaction

Rate equation cannot be found reliably from the reaction

stoichiometry or by any other theoretical means and therefore
rate expressions are always to be empirical, i.e., to be
discovered through experiments. 23
 Types of reactions
Chemical reactions are either
Homogeneous (single phase) or
Heterogeneous (more than one phase is involved)

Catalytic or
Non-catalytic (or autocatalytic)
In a heterogeneous catalytic reaction, the catalyst should be present
in a separate (distinct) phase. For a reaction when a component
from the gas phase is absorbed in the liquid body and reacts in the
presence of a catalyst that is mixed (dissolved) in the liquid, the
term heterogeneous catalysis is not justified. This is a
heterogeneous system with homogenous catalysis.

Nearly 90% of all industrial reactions involve heterogeneous

catalysis, i.e., they are heterogeneous as well as catalytic 24
 Types of reactions
Hydrogenation of vegetable oils in the presence of Ni
(Raney nickel) catalyst is an example of heterogeneous
catalysis and that the solid reactant is a distinct phase
from the reacting components (liquid phase). Gas phase
dehydrogenation of ethyl benzene is another example of
heterogeneous catalysis.

Recall others! There are many.

We will go through the reaction engineering principles and
develop rate expressions based on gas-solid reactions mostly in a
tubular reactor of fixed bed of catalysts. The principles would
remain the same and may be employed for the other types of
25
reactor systems.
Industrial examples of heterogeneous catalysis [5]

26
Heterogeneous catalysis in refinery processing [5]

27
 Space time and space velocity
Space time (τ): It is the time needed to process one
reactor volume of feed measured at specified conditions
Space velocity (s): It is the number of reactor volumes
of feed at specified conditions treated in unit time. A
space velocity of 10 h‒1 means that ten reactor volumes
of the feed at specified conditions are processed in a
reactor per hour.
1
space time 
space veloicty

1 V volume of reactor 10 feed reactor volumes

  
s v0 feed volumetric flowrate 28
 Gas hourly space velocity (GHSV)

In chemical reaction engineering, space velocity

is sometimes reported in terms of gas hourly
space velocity, which is the ratio of volume per
time in hours of the gaseous feed to the volume
of the reactor.

volumetric flowrate of the gaseous feed in cubic meter per hour

GHSV 
volume of reactor in cubic meter

It has unit of h1. It is usually reported for volumes

measured at temperature of 25°C and pressure of 1.013 bar.
29
Weight hourly space velocity (WHSV)
The term is frequently used in heterogeneous
reactor technology and it is defined as the ratio
of mass of the feed per hour to the mass of the
catalyst. Its unit is h1.

mass of the feed per hour

WHSV 
mass of the catalyst

In the dehydrogenation of n-butane to 1-butene in an

experimental gas phase fixed bed reactor, the catalyst weight
in the reactor is 2.0 g, while the volumetric flowrate of the
pure n-butane is 0.5 mL/min. The inlet conditions are 1.013
bar and 25 °C. Find out the WHSV for the given conditions. 30
 Liquid hourly space velocity (LHSV)
It is defined as the ratio of the volume of the
liquid feed per hour to the volume of the reactor
or catalyst required. The volume of the liquid
feed is usually taken at 60°F. 60°F is not worth
mentioning as volume (density) of a liquid does
not appreciably change with small changes in
temperature. Again the unit is h1.

Volume of the liquid feed per hour

LHSV 
volume of the catalyst

31
 Space time and space velocity data
Residence times and space velocities of various
industrial reactors are given in Chapter 17, p.
592 of Couper et al. [4] and in Section 19, p. 19-
5 of Perry’s Chemical Engineers’ Handbook.
2008. 8th ed. McGraw-Hill.

These values are only guidelines and may not

used in the actual reactor design calculations.

A part of the data from Couper et al. [4] is given

in the next slide. 32
Space time and space velocity data [4]

33
 Possibility of a reaction
For a thermodynamically possible reaction means that a
catalyst works only for those reactions for which Gibbs
free energy of reaction ∆Grxn is less than zero, i.e., the
reactants have higher free energy than the products.

A useful criterion (although not exact) for knowing the

possibility of reaction occurrence is to know the
standard state Gibbs free energy of reaction, ∆Grxno. A
reaction, however, may not be feasible at the standard
conditions but may occur at the other conditions.
What is the reason for using ∆Grxno and not
∆Grxn? 34
 Possibility of a reaction [6]

Value of ∆Grxno Possibility of reaction occurrence

Reaction is possible with very high
< ‒10 kcal/mol (‒41.8 kJ/mol)
equilibrium conversions
0 to ‒10 kcal/mol (‒41.8 Reaction is possible with moderately
kJ/mol) high equilibrium conversions
Reaction is possible at the other
process operating conditions but
0 to 10 kcal/mol (41.8 kJ/mol)
usually with low equilibrium
conversions
Reaction may be possible at the other
process operating conditions and if
> 10 kcal/mol (41.8 kJ/mol)
possible occurs with generally very
low equilibrium conversions
35
 Catalyst
 A catalyst is a substance that modifies (accelerates or decelerates)
the rate of a chemical reaction without itself being used up.
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.
 A catalyst can only alter the rate of a chemical reaction and
cannot affect the thermodynamics associated with the reaction. It
is, therefore, 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.

36
 Examples of catalysts
Sulfuric acid, hydrofluoric acid, vanadium pentaoxide,
metal over alumina, and zeolites with and without
loading of metals are common examples of catalysts.
Structure of
[Link]

zeolite Y

SO2 conversion
[Link]
catalysts [Link]
Zeolite ZSM-5

[Link]
37
[Link] [Link]
Hydrotreating catalyst
 Variety of commercial catalysts [5]

Monolith

38
Variety of commercial catalysts

[Link]

39
 Ammonia synthesis
The reaction of ammonia synthesis from N2 and H2 is
favorable thermodynamically
In the absence of a catalyst it occurs at extremely low
pace. The activation energy, 238.5 kJ/mol [6],
associated with the homogenous reaction is quite high
The presence of a typical catalyst decreases the
activation energy of the rate controlling step (adsorption
of nitrogen) to only 50.2 kJ/mol [6]

N2 + 3H2 = 2NH3 The Nobel

Prize in
Chemistry 40
1918 [Link]
Catalytic reaction path for ammonia synthesis [6]

41
 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 (an important reforming reaction) as
well as for hydrogenation of toluene to methylcyclohexane (reverse
reaction). Only the conditions of operation has to be changed. At
higher pressures and lower temperatures Pt/Al2O3 catalyses
hydrogenation of toluene while at lower pressures and higher
temperatures it catalyses dehydrogenation.
This fact can be used to discover a catalyst for a reaction at mild
conditions which can be used for its counter reaction such as synthesis
of ammonia requires high pressures whereas its reversible reaction,
decomposition of ammonia is carried out at low pressures [6]. 42
 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, Rh/SiO2 are
examples of supported catalysts.
Are there any unsupported metal TEM image of Rh/SiO2 [7a]
catalysts? Raney catalyst!!!

Al2O3

Pt
43
TEM image of Pt/Al2O3
 Structured catalysts
A structured catalyst is a regular structure free of
randomness in reference to the reactor. It is unlike the
discrete catalyst particles such as in a conventional fixed
bed reactor. Bring to mind the random packing and
structured packing in a packed bed.

[Link]

44
[Link]
[Link]
 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,
silica, titania, and carbon.

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. 45
 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 46
Cracking catalyst Reforming catalyst catalyst
 Active sites or active centers [2]
“In a landmark contribution to catalytic theory, Taylor
suggested that a reaction is not catalyzed over the entire
solid surface but only at certain active sites or centers. He
visualized these sites as unsaturated atoms in the solids that
resulted from surface irregularities, dislocations, edges of
crystals, and cracks along grain boundaries. Other
investigators have taken exception to this definition,
pointing out that other properties of the solid surface are also
important. The active sites can also be thought of as places
where highly reactive intermediates (i.e., chemisorbed
species) are stabilized long enough to react. However, for
our purposes we will define an active site as a point on the
catalyst surface that can form strong chemical bonds with an
adsorbed atom or molecule.” 47
Schematic representation of a single crystal surface [7a]

48
 Turnover frequency (TOF) [2]
It is the number of molecules converted per unit time
per active site.

49
 Activity, selectivity, stability, and regenerability of
a catalyst
The selection of a suitable catalyst for a process usually
demands the knowledge regarding the

 Activity
 Selectivity
 Stability, and
 Regenerability

of a catalyst.

50
 Activity, selectivity, stability, and regenerability 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).
51
Selectivity of a catalyst

52
Activity, selectivity, stability, and regenerability 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.
53
Activity, selectivity, stability, and regenerability of
a catalyst

Richardson [6] suggests the order of

importance of the activity, selectivity, and
stability as:

Selectivity
Stability
Activity

54
 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.
 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
55
defects at nano-level can be detected.
 Characterization of catalysts
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 skeletal and particle
densities of the material.
 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.
56
 XRD patterns of a zeolite Y
Catalyst
Characterization
SEM image of a zeolite Y

N2-Adsorption-
Desorption for a γ-
alumina

Pore volume =

57
TEM image of Rh/SiO2
Source of many chemical engineering related
terms

Comprehensive Dictionary of
Chemical Engineering
(576 pages) 58
The dehydrogenation of methylcyclohexane (MCH)

59
 Importance of the dehydrogenation of
methylcyclohexane (MCH) reaction

 Dehydrogenation of methylcyclohexane is an important

reforming reaction
 Dehydrogenation of methylcyclohexane may be useful in
the conversion of naphthenic base heavy oils
 Dehydrogenation of methylcyclohexane is involved in the
hydrogen storage applications in the MTH
(methylcyclohexane-toluene-hydrogen) system
 Dehydrogenation of methylcyclohexane may be used as a
fuel to absorb energy in high speed air craft engines

60
 Requirements for the realization of MCH as
organic hydride

The dehydrogenation reaction is highly

endothermic and occurs at a high temperature

The minimum T of 306.9°C is required for 90%

equilibrium conversion at 2.0 bar with pure MCH as feed
Heat of reaction at 1 bar and 25°C is 205 kJ/mol

A highly active, selective, and stable catalyst is

required (Catalyst Development)

61
 Various commercial and In-house catalysts [7]

Median
Pore
Dispersio Method of BET pore
Catalyst Assay Supplier volume Reference
n type preparation (m2g1) diameter
(cm3/g)
(Å)
CAT-A 0.3 wt% Pt/Al2O3 Commercial Egg-shell     This study
CAT-B x wt% Pt/-Al2O3 Commercial Egg-shell     This study
CAT-C 1.0 wt% Pt/-Al2O3 Development Uniform Wet impregnation 208 0.58 69 This study
CAT-D 1.0 wt% Pt/-Al2O3 Development Uniform Wet impregnation 99.1 0.84 291.3 This study
CAT-E 20.0 wt% Ni/-Al2O3 Development Uniform Dry impregnation 208 0.58 69 This study
CAT-F 1.0 wt% Pt/-zeolite Development Uniform Ion exchange 509.8 0.38 33.3 This study
CAT-G 1.0 wt% Pt/-Al2O3 Commercial Uniform  302.3 0.51 67.2 Tsakiris [2007]
Alhumaidan [2008]
CAT-H 0.5 wt% Pt/-Al2O3 Commercial Egg-shell  124.6 0.35 110.3 Tsakiris [2007]
Alhumaidan [2008]
CAT-I 0.3 wt% Pt/-Al2O3 Development Uniform Wet impregnation 220 0.62 70 Alhumaidan [2008]
CAT-J 0.3 wt% Pd/-Al2O3 Development Uniform Wet impregnation 220 0.62 70 Alhumaidan [2008]
CAT-K 0.1 wt% Pt/-Al2O3 Commercial   172.7 0.58 131.4 Tsakiris [2007]
CAT-L 0.3 wt% Pt/-Al2O3 Development Uniform Wet impregnation 14.2 0.05 133 Tsakiris [2007]
CAT-M 1.0 wt% Pt/-Al2O3 Development Uniform Wet impregnation 14.3 0.05 127.7 Tsakiris [2007]

62
 Various commercial and in-house
dehydrogenation catalysts

Commercial Pt/alumina catalysts Ni/γ-alumina 1.0wt%Pt/γ-alumina

Commercial
Commercial γ- zeolite beta
alumina support support 63
1.0 wt% Pt/γ-Al2O3 catalyst
XRD

γ-alumina support

Pt/γ-alumina support

SEM TEM

Pt

64
 High pressure (upto 30 bar) experimental rig

Product
gas outlet HPLC Pump

Condenser
MCH feed
reservoir

Furnace

Liquid
Reactor tube product outlet

65
High pressure (upto 30 bar) experimental rig

66
 High pressure (upto 30 bar) experimental rig
Description Specification
Body material SS-316
Reactor tube length (cm) 66
Reactor bed length (cm) 55
Tube outside diameter (cm) 1.27
Tube inside diameter (cm) 1.02
Tube wall thickness (cm) 0.1245
Thermowell material Al2O3
Thermowell outside diameter (cm) 0.28800.3175
400

380

360
Temperature ( C)
o

Catalyst bed
340 length = 4 cm

320
Tw = 380 C
p = 1.013 bar
300 Wall Temperature
H2/MCH (molar) = 8.4
Temperature in the reactor
W/FA0 = 17.3 [Link]-cat/kmol
280
-4 -2 0 2 4 6 8 67
Axial position in the reactor (cm)
 Activity results [7]

p = 1 bar; Tw = 380 C; H2 to MCH (molar)= 8.4

0.3 wt% Pt/Al2O3 (CAT-A)
1.0 x wt% Pt/Al2O3 (CAT-B)
0.3 wt% Pd/-Al2O3 (CAT-J)
0.3 wt% Pt/-Al2O3 (CAT-I)
0.8
0.5 wt% Pt/-Al2O3 (CAT-H)
1.0 wt% Pt/-Al2O3 (CAT-G)
0.6 1.0 wt% Pt/-Al2O3 (CAT-C)
XA

0.4

0.2

0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

W/FA0 x 105 (s.g-cat/mol-MCH)

68
 Selectivity results [7]
p = 5 bar; Tw = 380 C; H2 to MCH (molar)= 8.4
x wt% Pt/Al2O3 ((CAT-B)
1.0
0.3 wt% Pd/-Al2O3 (CAT-J)
0.3 wt% Pt/-Al2O3 (CAT-I)
Total by-products selectvity (%)

0.5 wt% Pt/-Al2O3 (CAT-H)

0.8
1.0 wt% Pt/-Al2O3 (CAT-C)

0.6

0.4

0.2

0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

W/FA0 x 105 (s.g-cat/mol-MCH) 69

 Comparative activity and selectivity for in-house
development catalysts [7]

W/FA0 = 0.62  105 sg-cat/mol MCH, Tw = 360 C, p = 1.0 bar, H2 to MCH molar ratio = 1.0

MCH conversion By-product selectivity

Catalyst Assay
(%) (%)
CAT-C 1.0 wt% Pt/-Al2O3 92.0 0.63
CAT-D 1.0 wt% Pt/-Al2O3 91.0 0.10
CAT-E 20.0 wt% Ni/-Al2O3 31.0 7.87
CAT-F 1.0 wt% Pt/-zeolite 73.0 22.48

70
 Deactivation behavior of catalysts [7]

p = 1 bar; Tw = 380 C; Pure MCH; W/FA0 = 34.5 hkg-cat/kg

1.0 wt% Pt/-Al2O3 (CAT-M)

1.0
0.3 wt% Pt/-Al2O3 (CAT-L)
0.5 wt% Pt/-Al2O3 (CAT-H)

0.8 1.0 wt% Pt/-Al2O3 (CAT-G)

0.1 wt% Pt/-Al2O3 (CAT-K)
1.0 wt% Pt/-Al2O3 (CAT-C)
0.6 0.3 wt% Pt/-Al2O3 (CAT-I)
XA

1.0 wt% Pt/-Al2O3 (CAT-D)

1.0 wt% Pt/-Al2O3 (CAT-F)
0.4

0.2

0.0
0 50 100 150 200 250
td (h)
71
 Hydroisomerization of heavy naphtha
Isomerization is used to improve the octane
number of the n-paraffinic feeds by converting
them into iso-paraffins.
n-pentane has RON (research octane number) of
61.7 while isopentane has an octane rating of 92.3.

Hydrogen is added to the feed to avoid the

deposition of coke on the catalyst surface and
consumption of hydrogen is negligible. Due to
hydrogen presence in the feed, the process is
frequently called as hydroisomerization. 72
 Hydroisomerization of heavy naphtha

Benzene is toxic and therefore we do not want

benzene in a gasoline. If present in gasoline, the
spillage of gasoline and incomplete combustion of
gasoline in an engine may add benzene to the
atmosphere we breath in.

For a naphtha feed, how can we reduce the

concentration of benzene in a gasoline while
virtually keeping the same octane rating? By
isomerizating naphtha.
73
Hydroisomerization of heavy naphtha

74
Hydroisomerization of n-heptane

Isoms Cracks Others

2,2-Dimethylpentane n-Propane 1,2-Dimethylcyclopentane
2,4-Dimethylpentane n-Butane Methylcyclopentane
2,2,3-Trimethylbutane i-butane Ethylcyclopentane
3,3-Dimethylpentane n-Pentane Toluene
2-Methylhexane 2-Methylpentane 2-Methylheptane
2,3-Dimethylpentane 3-Methylpentane 3-Methylheptane
3-Methylhexane 2,2-Dimethylbutane 1,3-Dimethycyclohexane
3-Ethylpentane n-Hexane

75
Catalysts studied [8]

76
Concept of zeolite structures [7a]

Zeolite Y 77
 Activity
results [8]
p = 1.0 bar
H2/C7H16 molar ratio = 9:1

78
 Selectivity
results [8]
p = 1.0 bar
H2/C7H16 molar ratio = 9:1
Values in parentheses are
temperatures in degrees
Celsius

79
Hydrocracking of waste plastics [8a]

80
T = 375 oC, pH2,0 = 7.0 MPa, t = 60 min, Reactor volume = 27 mL
Steps involved in a heterogeneous catalytic gas-
solid reaction

81
 Steps involved in a heterogeneous catalytic gas-
solid reaction

1. Diffusion of reactant/s through external gas 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 gas phase.
82
 Intrinsic and global 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.

The intrinsic kinetics of a gas-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 surface83
 Common kinetic models

 The power law (PL) kinetics

 The Langmuir-Hinshelwood-Hougen-
Watson (LHHW) kinetics

 The Eley-Rideal (ER) kinetics

84
 The power law kinetics

The power law is an empirical kinetic

model and assumes homogenous gas-solid
reaction.

See the following article in favor of the power law.

Weller, S. (1956). Analysis of kinetic data
for heterogeneous reactions. AIChE J. 2,
59–62.
85
 The power law kinetics
For the reaction
aA  bB  cC  dD

According to the law of mass action, a rate equation can

be written as:
a b
(rA )  k  C A  CB

The sum of a and b is called overall order of the reaction.

Eq. 3 (from the law of mass action) seldom

represents the true rate of a reaction and in most of
the cases, rate equation has to be found empirically.
86
 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.

What are elementary and non-elementary reactions?

87
 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:
n
(rA )  k  C A 88
 The power law kinetics
As the reaction is a gas-phase chemical reaction:

n
(rA )  k  p A

The parameter k and n are the regression parameters to be

found (fitted) against the experimental data.

Rate constant k is described as a function of

temperature and usually represented by the Arrhenius
equation, the above equation will be used with
Arrhenius equation and additional parameters
(Arrhenius parameters) are also to be fitted. 89
 Arrhenius equation
Arrhenius equation is frequently applied to approximate
the temperature dependency of reaction rate and the rate
constant or velocity constant, k, is related to temperature,
T, by the following expression:

d ln k Ea
 2
dT RT
Ea

k  k0  e RT
[Link]

k0 = pre-exponential factor and has units similar to that of k

Ea = activation energy, J·mol–1 90
 Arrhenius equation
 Reactions having large value of Ea are more
temperature sensitive while with low value of Ea are
less temperature dependent
 Ea and k0 are called Arrhenius parameters. To estimate
the effect of temperature on the rate of a chemical
reaction, the values of Arrhenius parameters are to be
known, otherwise experimental data of rate vs
temperature can be used to calculate the parameters.
 Arrhenius equation may be written in terms of two rate
constants and two temperatures:

 k 2  Ea  1 1 
ln      
 k1  R  T1 T2  91
 Arrhenius plot
A plot of lnk vs 1/T will be straight line, the slope of
which is Ea/R. The SI unit of the slope is K. A large
slope of Arrhenius plot means large value of Ea and vice
versa.

92
 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 so as to minimize the
diffusion limitations (intrinsic kinetics). External diffusion
limitations are also required to be eliminated
For simplicity of calculations and more reliable results, attempts
are made to have an isothermal reactor. This may be done in PFR
by diluting the catalyst bed with inert particles. Gradientless
reactors may be required
Experiments are performed over a stable catalyst, otherwise the
effect of time is to be incorporated in the rate equation
Go to the laboratory to generate some experimental
93
reaction data or obtain from a reliable source
 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
Various rate equations based on various kinetic models,
e.g., the power law model, LHHW kinetics, and ER
kinetics are assumed. Each rate equation is fitted with
the experimental data and the kinetically and statistically
best-fit equation is the rate equation for the experimental
94
data.
 Developing a rate equation
Sum of squares of the errors (SSE) is the common
objective function to be minimized. F-value, residual
plot, t-values of the parameters, 95% confidence
intervals of the parameters, and correlation matrix of the
parameters are the common statistical tools required to
discriminate the rival models.
Both linear and non-linear regressions may be applied
Excel using the Solver tool, Polymath (available in a
CD with book of Elements of Chemical Reaction
Engineering, by H. S. Fogler, 3rd ed., Prentice-Hall,
1999), SigmaPlot, TableCurve 2D, and subroutines
made in FORTRAN and MATLAB may be used for the
regression of the data. 95
 Basic performance equations of flow
reactors
CSTR (100% backmixed PFR (one-dimensional pseudo-
reactor) system homogeneous reactor) system
W XA dX A
  (rA )
FA0 (  rA ) Fractional W 
conversion of A d  
 FA0 
Weight of catalyst,
Weight of catalyst, Initial molar flowrate of the
kg
kg limiting reactant, mol/s

Catalyst XA
W dX A
FA0
 
0
(rA )
96
Example 1: 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

97
 Example 1: Laboratory experimental data

(W/Fmch,0) Target
RUN Fmch,0 Fhyd,0 Fhyd,0/Fmch,0 W/Fmch,0 T Tave Tave Xave
No. ×10–5
mol/min mol/s — (g·s)/mol (g·s)/mol °C °C K —
1 0.25 2.74E-04 8.3774 61875.8 0.6187584 380 377.72 650.87 0.119
2 0.125 1.37E-04 8.3774 123752 1.2375168 380 378.93 652.08 0.2005
3 0.5 5.47E-04 8.3774 30937.9 0.3093792 380 374.53 647.68 0.032
4 0.25 2.74E-04 8.3774 61875.8 0.6187584 380 378.73 651.88 0.063
5 0.25 0 0 61875.8 0.6187584 380 369.46 642.61 0.3405
6 0.125 0 0 123752 1.2375168 380 373.54 646.69 0.4895
7 0.5 0 0 30937.9 0.3093792 380 366.11 639.26 0.2135
8 0.063 0 0 245539 2.4553906 380 376.28 649.43 0.644
9 0.25 0 0 61875.8 0.6187584 430 412.57 685.72 0.6145

10 0.125 0 0 123752 1.2375168 430 418.44 691.59 0.855

11 0.5 0 0 30937.9 0.3093792 430 407.61 680.76 0.3845
12 0.063 0 0 245539 2.4553906 430 423.87 697.02 0.9745

98
 Fitting of experimental data

Using the power law of the following form

n
(rA )  k  p A

99
Mole fractions in the vapor phase (reaction
mixture) at conversion XA

100
Regression in MS Excel Solver Tool

101
Regression in SigmaPlot Software

102
Regression in SigmaPlot Software

103
 Fitting of experimental data
Now assume the reversible reaction is also important, therefore,
reversible kinetics are also included which is mostly true when
high conversions are obtained during the experimentation.
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.
Repeat Example 1 using the power law form
shown above. Use SigmaPlot and compare the
104
results with Example 1.
Example 2: Fitting the experimental data in a PFR

The experimental data given in the next slide for

the dehydrogenation of methylcyclohexane
(MCH) is generated in a plug flow reactor (PFR)
under integral conditions. Using power law
kinetics for the irreversible reaction, fit the
experimental data and find out the kinetic
parameters.
dX A dX A ( rA )
 ( rA ) 
 W  dW FA0
d  
 FA0 
105
 Example 2: Laboratory experimental data
Twall Tave Tave p Fmch0 Fhyd0 Fhyd0/ W/Fmch0
ymch0 yhyd0 yimp0 Xmche %Xmch
(oC) (oC) (K) (bar) (mol/s) (mol/s) Fmch0 (s.g/gmol)
360.6 324.6 597.786 1.013 3.23E-05 2.72E-04 8.428431 62185.22 0.106 0.893 0.0011 0.992 93.676
360.6 321.7 594.864 1.013 6.46E-05 5.45E-04 8.428431 31092.61 0.106 0.893 0.0011 0.991 62.878
360.6 338.1 611.2 1.013 1.62E-05 1.36E-04 8.428431 124370.4 0.106 0.893 0.0011 0.997 98.349
360.6 328.3 601.457 2 3.23E-05 3.41E-05 1.053554 62185.22 0.485 0.5105 0.0049 0.972 87.802
360.6 323 596.121 2 6.46E-05 6.81E-05 1.053554 31092.61 0.485 0.5105 0.0049 0.959 50.802
340.49 312.4 585.571 1.013 3.23E-05 2.72E-04 8.428431 62185.22 0.106 0.893 0.0011 0.982 78.1895
340.5 307.7 580.814 1.013 3.23E-05 3.41E-05 1.053554 62185.22 0.485 0.5105 0.0049 0.983 79.211
360.6 341.5 614.6 2 1.62E-05 1.70E-05 1.053554 124370.4 0.485 0.5105 0.0049 0.989 97.699
360.6 322.5 595.614 1.013 3.23E-05 3.41E-05 1.053554 62185.22 0.485 0.5105 0.0049 0.994 90.57
360.6 337.2 610.329 1.013 1.62E-05 1.70E-05 1.053554 124370.4 0.485 0.5105 0.0049 0.998 99.217
380.44 342.4 615.5 1.013 3.23E-05 2.72E-04 8.428431 62185.22 0.106 0.893 0.0011 0.998 97.622
340.5 312 585.143 1.013 3.23E-05 2.72E-04 8.428431 62185.22 0.106 0.893 0.0011 0.981 78.37
340.5 308.2 581.386 1.013 3.23E-05 3.41E-05 1.053554 62185.22 0.485 0.5105 0.0049 0.983 77.549
360.6 320.1 593.214 1.013 6.46E-05 6.81E-05 1.053554 31092.61 0.485 0.5105 0.0049 0.993 55.609
340.5 307 580.121 1.013 3.23E-05 0 0 62185.22 0.99 0 0.01 0.985 77.653
360.6 318.6 591.793 1.013 6.46E-05 0 0 31092.61 0.99 0 0.01 0.994 54.001
360.6 322.2 595.321 1.013 3.23E-05 0 0 62185.22 0.99 0 0.01 0.995 87.951
360.6 336.4 609.507 1.013 1.62E-05 0 0 124370.4 0.99 0 0.01 0.998 98.507
380.44 339.8 612.979 1.013 3.23E-05 3.41E-05 1.053554 62185.22 0.485 0.5105 0.0049 0.998 97.371
380.44 339.5 612.614 1.013 3.23E-05 0 0 62185.22 0.99 0 0.01 0.999 96.204
340.69 317.1 590.271 1.013 1.62E-05 1.70E-05 1.053554 124370.4 0.485 0.5105 0.0049 0.9914 98.241
340.69 307.9 581.093 1.013 6.46E-05 6.81E-05 1.053554 31092.61 0.485 0.5105 0.0049 0.9828 44.015
319.76 290.1 563.279 1.013 6.46E-05 0 0 31092.61 0.99 0 0.01 0.9453 35.4
106
340.69 304.5 577.621 1.013 6.46E-05 0 0 31092.61 0.99 0 0.01 0.9817 44.3
Example 2: Fitting the experimental data in a
PFR

The regression with PFR requires differential

equation to be solved. Euler or 4th order RK
method can be used for this purpose. As
discussed before subroutines made in
FORTRAN and MATLAB may be used for the
regression of the data. Try in Excel using
Solver..

107
 Chemical reaction equilibrium constant

 Experimental equilibrium constant may be

found in the literature such as in a research
article or a handbook

 When experimental Ke is not available it may

be worked out in the laboratory

 Equilibrium constant can also be calculated

using the values of Gibbs free energies of
formation
108
 Chemical reaction equilibrium constant

 G  (T )
ln K e 
R T 
d ln K e H rxn

  G  (T )  dT R T 2
K e  exp 
 R T 
 
 K2  H rxn

1 1
ln      
G  (T )    Gi (T )  K1  R  T2 T1 

Gio is a property of pure component i in its standard state

at fixed pressure but depends on temperature
How can one calculate heat of reaction? 109
 Determination of equilibrium constant
(Using Gibbs free energies of formation)

When experimental equilibrium constant is not available,

one can find from the information of Gibbs free energy of
formation of each species. Please see references [10] and
[10a].
Equilibrium constant for the dehydrogenation of MCH to
toluene using the information of Gibbs free energies of
formation from Yaws [10].
14

12

10

8
lnKe

2 y = -25,652.70621017x + 47.15123250
R² = 0.99999451
0
0 0.0005 0.001 0.0015 0.002 0.0025
-2
1/T (K-1)
110
N.B.: Some people prefer to plot with 1000/T instead of 1/T
 Example: Calculations for equilibrium composition

Calculate the equilibrium composition of the reaction

dehydrogenation of methylcyclohexane carrying out at 5 bar
and 380 °C with 50 mol% H2 in the feed. The experimental
equilibrium constant is given below [11a].

How can we find experimental

equilibrium constant? 111
Calculations for equilibrium composition

3 3
pBe  ( pCe ) y Be  ( yCe ) 3
Ke   p
p Ae y Ae

112
 Calculations for equilibrium composition

3
 ( y B 0  X Ae  y A0 )   yC 0  3  X Ae  y A0 
      p 3
 1   1  3  X Ae  y A0 
 Ke  0
 ( y A0  X Ae  y A0 ) 
 
 1 

3
 ( y B 0  X Ae  y A0 )   yC 0  3  X Ae  y A0 
      p 3
 1   1  3  X Ae  y A0    217650 1 1 
 3600 exp      0
 ( y A0  X Ae  y A0 )   8.31434  T 650  
 
 1 

Put p in bar and T in K.

We need such a value of XAe that LHS equals

RHS, i.e., LHS becomes equal to zero. 113
Calculations for equilibrium composition
(MS Excel Solver application)
Equilibrium composition for MCH dehydrogenation

Ke = 16.25940041 bar3

yMCH0 = 1 mol/s

yH20 = 0 mol/s

yTol0 0

yN20 = 0

T= 300 C

T= 573.15 K

p= 10 bar

f(Xe) = -0.0000008987 =0
114
Xe = 0.21394081 Inputs
Class activity

115
Class activity

116
 Homework problem
Ethylbenzene is produced by the alkylation of benzene as
shown in the following simultaneous chemical reactions.
Workout the relationship for mole fraction of each species
involved in the reaction in terms of initial mole fractions.
Use XI and XII as the fractional conversions for the first and
the second chemical reactions, respectively.

II
117
 Homework problems
1.

2.

118
 Homework problems
Calculate the equilibrium composition of the reaction
dehydrogenation of cyclohexane to benzene carrying out at 10 bar
and 350 °C with 10 mol% H2 and 30 mol% N2 in the feed along
with cyclohexane.
Hint: Consider ideal gas conditions and avoid fugacity calculations.

119
Physical and chemical adsorption

120
Concept of multilayer adsorption

(a) Monolayer adsorption

(b) Multilayer adsorption

121
[Link]
 Dissociative and non-dissociative adsorption

Adsorption of a component may be non-dissociative or

dissociative. The previous case is for non-dissociative
adsorption.

In non-dissociative case, the molecule is adsorbed as a

whole and it may be called as molecular adsorption.
In dissociative adsorption, the molecule such as of H2 is
dissociated into H-H form and adsorbed. Of course the
dissociative case requires 2 sites for the adsorption.

Non-dissociative:

Dissociative: 122
 Activated and non-activated adsorption
For activated adsorption, rate of adsorption is dependent upon
temperature. It requires some activation energy before the
component is adsorbed. Chemisorption is usually activated
adsorption. Non-activated adsorption or ordinary adsorption does
not depend upon temperature therefore activation energy is zero.

123
[7a]
Langmuir-Hinshelwood-Hougen-Watson (LHHW)
kinetics
The Langmuir-Hinshelwood-Hougen-Watson (LHHW)
approach accounts for the surface concentrations of the species
taking part in the reaction.
Relating surface species to the observed species partial
pressures in the gas phase provides equations that can be fitted to
the kinetic data.
Based on the Langmuir adsorption isotherm, the approach was
first developed by Hinshelwood and therefore sometimes termed
as Langmuir-Hinshelwood kinetics. Hougen and Watson [1943]
developed a similar approach and popularize the Langmuir-
Hinshelwood kinetics.
The LHHW approach assumes that all active sites are
energetically uniform and, upon adsorption, adsorbed species do
not interact (except for surface reaction) with species already
adsorbed. 124
 Langmuir-Hinshelwood-Hougen-Watson (LHHW)
kinetics
Active sites have similar kinetic and thermodynamic
characteristics and the entropy and enthalpy of adsorption are
constant and not functions of the adsorbed amount.
The species adsorption restricts itself to only monolayer
coverage and the rate of adsorption is proportional to the
concentration of the active sites not occupied (empty) and the
partial pressure of the component in the gas phase.
[Link]

Langmuir Adsorption
Isotherm
125
Irving Langmuir
 Eley-Rideal kinetics
A gas phase component reacts with an adsorbed species,
i.e., a component reacts from the gas phase with an
adsorbed component.
A  s  B( g )  C ( g )  s

126
Nanotechnology for Water Treatment and Purification by Anming Hu and Allen Apblett
 Langmuir adsorption isotherm
For the adsorption of component A on a certain surface

Non-dissociative adsorption Dissociative adsorption

127
 Competitive adsorption
If more than one component competes for the adsorption:

128
 Development of a typical kinetic rate equation

Assume a reaction mechanism. The mechanism may

include single-site or dual-site surface reactions and
dissociated or non-dissociated adsorption steps
Assume the single rate determining step (rds)
Assume that all the other steps except the rate
determining step are in equilibrium (pseudoequilibrium)
Write down the adsorbed concentration variables in
terms of measurable concentrations
Write down the total site balance, eliminate the
variable Cs (concentration of empty sites), and simplify
to get the required rate equation.
129
 Development of kinetic rate equation based on
LHHW kinetics single-site mechanism
The surface reaction may be single-site or dual-site, i.e., a
single site or two sites may be involved:

Single-site

Dual-site
130
Development of kinetic rate equation based on LHHW
kinetics single-site mechanism: Step-II as RDS

 pB 
k  K A  p A  1  
 p A  Ke 
(rA ) 
1  K A  p A  K B  pB

131
 Development of kinetic rate equation based on
LHHW kinetics dual-site mechanism: Step-II as RDS

 pB 
k  K A  p A  1  
 pA  Ke 
( rA ) 
(1  K A  p A  K B  p B ) 2 132
 Class activity

Workout for the other possible rate equations based on the

mechanisms given earlier, i.e. develop rate equation when

 First step (adsorption of A) is the rate controlling step

for single-site mechanism

 Third step (desorption of B) is the rate controlling step

for dual-site mechanism

133
 Homework problem [2]

Workout the example given in Section 10.3 of the book

by Fogler [2]: Decomposition of cumene to form benzene
and propylene.

134
 Eley-Rideal kinetics

For the Eley-Rideal kinetic mechanism shown below,

workout the rate equation for the surface reaction rate
controlling.

135
 General rate equation
kineticterm potentialterm
(r ) 
adsorptionterm
For intrinsic kinetics, the kinetic term contains the reaction
velocity constant and may or may not contain adsorption
constants.
The potential term is the simple driving potential and for
an essentially irreversible reaction should be equal to unity.
The adsorption term contains the adsorption coefficients
and partial pressures of species and provides a means of
quantifying the competition among the species to occupy the
active centres. This is useful in the sense that it helps in
interpreting the effect of partial pressures of reaction species
and even inert and poisons on the rate of reaction. 136
 Successive dehydrogenations in
methylcyclohexane dehydrogenation

137
Development of kinetic rate equation based on
LHHW dual-site surface reaction for the
dehydrogenation of methylcyclohexane

138
 Development of kinetic rate equation based on
dual-site surface reaction for the dehydrogenation
of methylcyclohexane

139
Development of kinetic rate equation based on dual-site surface reaction for
the dehydrogenation of methylcyclohexane

140
Development of kinetic rate equation based on dual-site surface reaction for
the dehydrogenation of methylcyclohexane

141
Development of kinetic rate equation based on dual-site surface reaction for
the dehydrogenation of methylcyclohexane

142
Development of kinetic rate equation based on dual-site surface reaction for
the dehydrogenation of methylcyclohexane

143
Development of kinetic rate equation based on dual-site surface reaction for
the dehydrogenation of methylcyclohexane

144
Development of kinetic rate equation based on dual-site surface reaction for
the dehydrogenation of methylcyclohexane

145
 Homework problems

 For the mechanisms given on slide 130, work out the rate
equations by considering adsorption, surface reaction, and
desorption as the rate controlling step.
 For the Eley-Rideal mechanism,

C
workout the rate equation for the adsorption of A and desorption of
C.

146
 Homework problems
For the oxidation of nitric oxide to produce e, the
following Eley-Riedel mechanism is proposed. Derive
rate expression assuming surface reaction as rate
determining step.

147
 Homework problems
Modify the mechanisms given on slide 137 to single-site surface
reaction while neglecting hydrogen adsorption-desorption step,
develop kinetic rate equation based on LHHW kinetics when the
rate controlling step is:

• Adsorption of methylcyclohexane (Class activity)

• Single-site surface reaction for the loss of first hydrogen
• Single-site surface reaction for the loss of second hydrogen
• Single-site surface reaction for the loss of third hydrogen
• Desorption of toluene

See a few next slides. You may consult Chapter 10 of Fogler [2].
See also Chapter 2 of Froment et al. [11].
148
Class activity

149
 Discrimination among the rival models
Now we have a number of rate models developed based on
power law, LHHW, and Eley-Rideal. Each of the rate
equations developed is to be fitted against the experimental
data and the one which is the most appropriate kinetically
and statistically would be chosen as the best-fit rate
equation. “Initial rate” analysis may be used to get a clue of
the final form of the equation best suited to the experimental
data. Comparing the results to the literature findings and
microkinetic analysis may be carried for the final
discrimination and for observing the validity of the final rate
model. For more on discrimination among the rival models,
see Chapter 10 of Fogler [2], Chapter 2 of Froment et al. [11],
and Usman et al. [12].
150
Problem: Design of a fixed bed reactor

151
 Problem: Design of a fixed bed reactor

dX A
 (rA )
W 
d  
 FA0 

The software is an excellent source for

solving single and simultaneous
ordinary differential equations. 152
 Homework problems

Using POLYMATH software, find out the weight of

the catalyst for the problem described above, however,
use the rate equation as described in Usman et al. 2011
[13]. Solve the problem and see the difference for using
two different rate equations. What are your comments?
Example 10-3 of Fogler [2].

Instead of using POLYMATH software, you can prepare

an excel spreadsheet using Euler’s method or Runge-
Kutta method for finding the weight of the catalyst, etc.

153
 Diffusion and reaction for porous catalysts
Solid catalysts are usually porous structures in order to
have high surface area (m2) per unit gram. Due to the
porous nature, the inner surface is many times greater than
the outer particle surface. Now as the reactants have to
reach the inner surface through small pores, there may be
significant resistance to mass and heat diffusion (transfer).
Due to the reason, concentration and temperature profiles
may be developed across the particle, i.e., within the
particle.

For temperature distribution, if a reaction is exothermic,

higher temperatures are possible at the center of the
particle than at the outer surface and vice versa for an
154
endothermic reaction.
Concentration and temperature distributions
in a gas-solid catalytic reaction [14]

155
 Diffusion and reaction for porous catalysts:
Effectiveness factor
The rate (kinetics) of a chemical reaction are dependent on the
concentration of the reactant, say A, and temperature at any
point of the catalyst. Now as concentration and temperature
may vary from point to point so does the rate of the reaction.
Therefore, it is required to account for these variations
(diffusional resistances) to define the rate which represents the
particle as whole. It may be interpreted that the effectiveness of
the catalyst towards the rate of reaction varies within the
catalyst particle and this effectiveness has to be considered in
the final rate law. A factor known as effectiveness factor is
required.
Effectiveness factor is defined as the ratio of the observed or
overall rate of reaction to the intrinsic rate of reaction at the
outer surface of the particle where there are no diffusional
156
limitations.
 Diffusion and reaction for porous catalysts:
Effectiveness factor

(  rA ) obs

(  rA ) int
(rA )int is the rate of the reaction at the conditions
at the outside surface, i.e., cAS and Ts.

(rA ) obs is the rate of the reaction actually observed.

 is effectiveness factor
157
 Diffusion and reaction for porous catalysts:
Effectiveness factor

Satterfield [15] defines the effectiveness factor as

“the ratio of the actual reaction rate to that which

would occur if all of the surface throughout the
inside of the catalyst particle were exposed to
reactant of the same concentration and
temperature as that existing at the outside surface
of the particle”.

158
 Diffusion and reaction for porous catalysts:
Effectiveness factor
Consider, now, a spherical catalyst particle of radius R as shown in
the figure below:

cAs

Δr

159
 Diffusion and reaction for porous catalysts:
Effectiveness factor
Considering a thin spherical shell within the catalyst particle
and apply mass balance across the thin shell for the following
assumptions:

1) Porous particle is spherical;

2) Porous particle is isothermal
3) Reaction is A  Products (irreversible)
4) Kinetics are represented by (  rA )  k  c An
5) Steady-state conditions
6) Reactants are transported through diffusion and there is no
turbulence. The diffusion is described by Fick’s law with
mass diffusivity defined as effective diffusivity.
160
Diffusion and reaction for porous catalysts:
Effectiveness factor

161
Diffusion and reaction for porous catalysts:
Effectiveness factor

162
Diffusion and reaction for porous catalysts [15]

163
 Diffusion and reaction for porous catalysts:
Effectiveness factor

A modified Thiele modulus can be defined which is

based on observed values

R2  1 dn  1
   
Deff  Vc dt  c As
This modified Thiele modulus is related for various
values of heat generation function, β, and dimensionless
Arrhenius number to include the effect of temperature
while determining the effectiveness factor. One such
relationship (graph) is shown in the figure on the next
slide. 164
Diffusion and reaction for porous catalysts [15]

165
 Effective diffusivity
The effectiveness diffusivity can be calculated by the
following equation

1 1 1
 
Deff DKn,eff DA,eff

Where,

Deff effective mass diffusvity, m2/s

DA,eff ordinary or bulk effective mass diffusivity, m2/s
DKn ,eff effective Knudsen mass diffusvity, m2/s
166
 Knudsen diffusivity
“If the gas density is low, or if the pores are quite small,
or both, the molecules collide with the pore wall much
more frequently than with each other, This is known as
Knudsen flow or Knudsen diffusion. The molecules
hitting the wall are momentarily adsorbed and then given
off in random directions (diffusively reflected). The gas
flux is reduced by the wall resistance. Knudsen diffusion
is not observed in liquids.” [15]

167
[16]
 Knudsen diffusivity

The pore radius rp is for a round straight pore, the actual pore
geometry is complex and the therefore including the effect of
pore geometry, the following relationship can be written for
the effective Knudsen diffusivity [15]. 168
Effective Knudsen and ordinary diffusivities
Effectiveness Knudsen diffusivity

Effectiveness bulk diffusivity

169
 Bulk diffusion coefficient for gases at low pressure

Based on the Chapman-Enskog theory, the following

equation using ideal gas law for the determination of total
concentration “c” may be written [17]

Here, DAB is in cm2/s, σAB is Å, and p in atm.

The mass diffusivity DAB for binary mixtures of non-polar
gases is predictable within about 5% by kinetic theory. 170
Bulk diffusion coefficient for gases at low pressure

The parameters σAB and εAB could, in principle, be determined

directly from accurate measurement of DAB over a wide range of
temperatures.
Suitable data are not yet available for many gas pairs, one may
have to resort to using some other measurable property, such as
the viscosity of a binary mixture of A and B.
In the event that there are no such data, then we can estimate
them from the following combining rules for non-polar gas pairs.

Use of these combining rules enables us to predict values of

DAB within about 6% by use of viscosity data on the pure species
A and B, or within about 10% if the Lennard-Jones parameters for
A and B are estimated from boiling point data as discussed in
Chapter 1 of Bird et al. 2002 [17]. 171
Bulk diffusion coefficient for gases at low pressure

The Lennard-Jones parameters can be obtained from the

Appendix of the book [17] and in cases when not known can
be estimated as described in first chapter of the book [17]. To
avoid interpolation, a graphical relationship for collision
integral is given on the next slide.

A mathematical relationship by Neufeld is recommended for

computational (spreadsheet) work [18].

172
Bulk diffusion coefficient for mixture of gases and
gases at high pressure
The behavior of gases at high pressures (dense gases)
and of liquids is not well understood and difficult to
interpret to a mathematical evaluation. The following
approach can be used for estimating the mass diffusivity
of gases at high pressures. The method is very good for
gases at low pressures. At high pressures, due to the lack
of large number of experimental data, a comparison is
difficult to make.

For the diffusivity of gases at high pressure and mixture

of gases, see “Poling, B.E.; Prausnitz, J.H.; O’Connell,
J.P. 2000. The properties of gases and liquids. 5th ed.
McGraw-Hill” and Chapter 1 of the book by Bird et al.
[17]. 173
Class activity

174
Homework problem

152

175
Industrial batch
reactor

[p.124, 19] 176

 Various design of reactors

Based on the phases involved, reactors may

adopt various shapes and designs
depending upon the process requirements.

177
 Reactors for gas phase only [20]
If rate of the reaction is high, the reaction can be carried
out in small reaction spaces, e.g., in flames and arcs.
For slower reaction larger reaction space is required.

178
 Reactors for liquid phase only [20]

8 179
Gas-liquid reactors only [20]

180
Gas-liquid reactors [20]

181
Liquid-solid reactors [20]

182
 Gas-solid
reactors [20]

183
Gas-Liquid-solid reactors [20]

Think other designs.

184
You may have a novel idea.
 Design of a fixed bed reactor

A commonly used fixed bed reactor has the following

features:
The reactor is used for a fluid-solid contact though
gas-solid systems are more common.
The solid catalyst particles are arranged randomly in a
cylindrical shell or tube, where the solid particles
remain fixed with respect to each other as well with
respect to the reactor wall.

How will you define moving bed reactor and fluidized

bed reactor?
185
 Design of a fixed bed reactor

The gas or liquid flows from top to the bottom. The

flow in upward direction may loosen the bed giving rise
to attrition and fine particles may increase the pressure
drop and may possibly be fluidized.
Sulfuric acid production (SO2 oxidation), methanol
production, ammonia synthesis, manufacture of styrene
by the dehydrogenation of ethylbenzene are some of the
industrial examples that require a fixed bed reactor.
The catalytic bed may be arranged in a single shell,
single shells adjacent to one another (multibed), or
multitubular reactor.
186
 Design of a fixed bed reactor

The catalyst bed may be arranged in a multitubular

geometry in which a set of tubes are placed inside a shell.
This conforms to a shell and heat exchanger type
assembly. The catalyst may be packed inside or outside of
the tubes.
A radial flow reactor may also be used where pressure
drop is an issue.
The usual catalyst particle size ranges between 2-6 mm.
Various shapes of catalysts may be used. Spherical, solid
cylindrical, hollow cylindrical (Raschig ring type),
Lessing ring type, extrudates, etc., are the different kinds
of shapes of catalyst that may be employed.
187
Variety of catalysts: pressure drop [6]

188
 Design of a fixed bed reactor
 Thermodynamics of the reaction (heat of reaction and chemical
reaction equilibrium consideration)
 Reaction reversibility
 Kinetics (rate) of the given reaction
 Feed composition and product specifications
 Flow requirement
 Thermal energy requirement
 Bed arrangement
 Properties of catalytic particles and catalytic bed
 Catalyst weight (size of the reactor)
 Length to diameter ratio
 Pressure drop
 Temperature and composition distributions
 One or more of these requirements may be dependent on each189
other.
 Fixed bed reactors

[4]

[21]

[21a] 190
Types of fixed bed reactors [14]

191
Fixed bed reactor models [14]

192
Fixed bed reactor models [14]

193
Steady-state two-dimensional pseudo-
homogeneous model

194
 Steady-state two-dimensional pseudo-
homogeneous model

Mass balance:
Rate of mass in  Rate of mass out  Rate of mass generation
 Rate of mass consumption   Rate of accumulation of mass

Energy balance:
Rate of energyin  Rate of energyout  Rate of energy generation
 Rate of energy consumption   Rate of accumulation of energy

195
 Steady-state two-dimensional pseudo-
homogeneous model

Continuity equation (Constant Dea and Der):

Energy equation (Constant cp, Δhrxn and ker):

For the derivations, see class notes and book by Missen, Ref. 14.
196
 Peclet numbers
Peclet number for mass transfer
Mass trasnfer rate by convection
Peclet number 
Mass transfer rate by conduction

udp Gdp udp Gdp

Pea ,m   Per ,m  
Da   Da Dr   Dr

Peclet number for heat transfer

Heat trasnfer rate by convection
Peclet number 
Heat transfer rate by conduction

udp G cp  d p udp G  cp  d p

Pea ,h   Per ,h  
ka ka kr kr 197
Boundary conditions

198
 Overall heat transfer coefficients: hollow
cylinder
1 1 Ai  ln(r2 / r1 ) Ai Pipe wall
  
U i hi 2   k  L ho  Ao resistance
1 Ao Ao  ln(r2 / r1 ) 1
  
U o hi  Ai 2   k  L ho

Outside fluid r2
film resistance
r1

Inside fluid
film resistance 199
 Bed properties and Ergun equation for
pressure drop calculations
s B
Particle density   p  Bulk voidage   B  1 
(  s  v )  1 p
Bulk density   B   p  (1   p )  (1   B )

d p G
Particle Reynolds number  Re p 


Ergun equation

dp 150 G   (1   B ) 1.75  G 1   B
2 2
     3
2
dz   s  d v 2
B
3
  s  d v  B
200
Recommended correlations for fixed bed
reactors [21]

201
Recommended correlations for fixed bed
reactors [21]

202
Recommended correlations for fixed bed
reactors [21]

203
 Physical properties of mixtures
Average molecular weight:
M ave  y A  M A  yB  M B  yC  M C  yI  M I

Density (applicable at low pressure):

p  M ave

R T
Heat capacity:
c p  y A  c p, A (T )  y B  c p,B (T )  yC  c p,C (T )  y I  c p,I (T )

Transport properties such as mass diffusivity, thermal

conductivity, viscosity should not be taken as additive.
Recommended mixing rules should be applied for such
calculations. See Poling et al. [18] and Bird et al. [17] Chapters 1,
9, and 17. 204
 Steady-state one-dimensional pseudo-
homogeneous model with negligible axial
diffusion for adiabatic operation
Continuity equation:
dX A   Di2   B  (rA )

dz 4  FA0
dX A  B  ( rA )  M 0
or 
dz G  y A0
Energy equation (Constant cp and Δhrxn):
dT  B  (rA )  (hrxn )

dz G  cp
205
 Steady-state one-dimensional pseudo-
homogeneous model with negligible axial
diffusion for non-adiabatic operation
Energy equation (Constant cp and Δhrxn):

dT  B  (rA )  (hrxn ) 4 U i  (T  T f )
 
dz G  cp G  c p  Di

What would be the boundary

conditions for each case?

206
 Fixed bed: A few rules of thumb
1. Usually dp is chosen so that the ratio Di/dp > 10 to
avoid flow problems. A very small particle, on the
other hand, will cause excessive pressured drop.
2. In one of the criteria, the effect of axial dispersion
depends on the ratio of the length of the reactor to
the particle size. If the ratio is 100 or more, the
effect is usually negligible compared to convective
mass transfer.
3. Carman-Kozeny equation is suitable for fine
particles. Ergun equation works well for both
laminar and turbulent regions.

207
 Solution of partial differential equations

 Finite difference approach

 Finite element approach

Finite difference:
 Explicit methods
(Easy to put but beware of convergence and stability)
 Implicit methods
The Crank-Nicolson method

Finite element:
 Comsol Multiphysics (old name Femlab).
208
Problem

209
 Solution of one-dimensional pseudo-
homogeneous model
Euler’s method is employed for approximate solution of ordinary
differential equations with initial value problems.

y n 1  y n  h  f ( x n , y n )
h  xn1  xn
Take interval “h” as low as Euler (1707-1783)
possible. Take large number of
steps to avoid numerical
instability.
Runge-Kutta 4th order
method has better efficiency
than Euler’s method.
210
Assignment (Last date: 09-May-2016)
Total marks: 12.5

211
 Reading materials
R-1 Pages 2 and 3 of Hill and Root [1]
R-2 Pages 591 to 594 of Couper et al. [4]
R-3 Complete article by Usman et al. [7]
R-4 Complete article by Ding et al. [8a]
R-5 Pages 1 to 11 of Richardson [6]
R-6 Complete article by Usman et al. [8]
R-7 Chapter 10 of Fogler [2]
R-8 Complete article by Weller, 1956
R-9 Pages 129 to 147 of Satterfield [15]
R-10 Pages 512 to 517 and 523 to 531 of Missen et al. [14]

212
 References
[1] Hill, Jr., C.G.; Root, T.W. 2014. Introduction to chemical engineering kinetics
and reactor design. 2nd ed. Wiley.
[2] Fogler, H.S. 2006. Elements of chemical reaction engineering. 4th ed. Prentice
Hall PTR.
[3] Levenspiel, O. 1999. Chemical reaction engineering. 3rd ed. Wiley & Sons, Inc.,
Singapore.
[4] Couper, J.R.; Penney, W.R.; Fair, J.R.; Walas, S.M. 2012. Chemical Process
Equipment: Selection and Design. 3rd ed. Butterworh-Heinemann.
[5] Hagen, J. Industrial catalysis: A practical approach. Wiley-VCH. 2006.
[6] Richardson, J.T. 1989. Principles of catalyst development. Kluwer
Academics/Publishers.
[7a] Davis, M.E.; David, R.J. 2003. Fundamentals of chemical reaction engineering.
McGraw-Hill.
[7] Usman, M.R. 2011. Catalytic Dehydrogenation of Methylcyclohexane over
Monometallic Catalysts for On-board Hydrogen Storage, Production, and
Utilization. Energy Sources A 33, 22312238.
[8] Usman, M.R.; Alotaibi, F.M. 2015. Unified kinetics of n-heptane
hydroisomerization over various Pt/zeolite catalysts. Prog. React. Kinet. Mech.213
Accepted for publication.
 References
[8a] Ding, W.; Liang, J.; Anderson, L.L. 1997. Hydrocracking and
hydroisomerization of high-density polyethylene and waste plastic over zeolite and
silica-alumina-supported Ni and Ni-Mo sulfides. Energy & Fuels 11, 1219‒1224.
[9] Catalysis looks to the future. 1992. Panel on New Directions in Catalytic
Science and Technology, National Research Council, National Academy Press,
Washington, D.C.
[10] Yaws, C.L. 1999. Chemical properties handbook. McGraw-Hill.
[10a] Stull
[11a] Schildhauer,T.; Newson, E.; Muller, St. 2001. The equilibrium constant for
the methylcyclohexane dehydrogenation system. J. Cata. 198, 355 358.
[11] Froment, G.F., Bischoff, K.B., and De Wilde, J. 2011. Chemical reactor
analysis and design. 3rd ed. John Wiley & Sons, Inc.
[12] Usman, M.R.; Cresswell, D.L.; Garforth, A.A. 2012. Detailed Reaction
Kinetics for the Dehydrogenation of Methylcyclohexane over Pt Catalyst. Ind. Eng.
Chem. Res. 51, 158170.
[13] Usman, M.R.; Aslam, R.; Alotaibi, F. 2011. Hydrogen storage in a recyclable
organic hydride: Kinetic modeling of methylcyclohexane dehydrogenation over 1.0
214
wt% Pt/θ-alumina. Energy Sources, Part A 33, 2264‒2271.
 References
[14] Missen, R.W., Mims, C.A., and Saville, B.A. 1999. Introduction to chemical
reaction engineering and kinetics. John Wiley & Sons, Inc., New York.
[15] Satterfield, C.N.1970. Mass transfer in heterogeneous catalysis. MIT Press.
[16] Welty, J.R.; Wicks, C.E.; Wilson, R.E.; Rohrer, G.L. 2007. Fundamentals of
momentum, heat, and mass transfer, 5th ed., John Wiley & Sons, Inc.
[17] Bird, R.B. Stewart, W.E. Lightfoot, E.N. 2002. Transport phenomena. 2nd ed.
John Wiley & Sons, Inc. Singapore.
[18] Poling, B.E.; Prausnitz, J.H.; O’Connell, J.P. 2000. The properties of gases and
liquids. 5th ed. McGraw-Hill.
[19] Smith, J.M. 1981. Chemical engineering kinetics. 3rd ed. McGraw-Hill Int.
Book Co., Singapore.
[20] Brötz, W. 1965. Fundamentals of chemical reaction engineering. Addison-
Wesley Publishing Company, Inc., Reading.
[21] Rase, H.F. 1990. Fixed bed reactor design and diagnostics: Gas-phase
reactions, Butterworths, Boston.
[21a] Mann, U. 2009. Principles of Chemical Reactor Analysis and Design. 2nd
ed. John Wiley & Sons, Inc.
215