Chemical Reaction

Engineering - II
CHE-S402
Instructor : Dr. Brishti Mitra
([email protected])
Introduction
• Any chemical industrial process can be characterized in terms of three major
components – pre-reaction, reaction, post-reaction

• The first and last components usually comprise of physical operations (mixing,
vaporization, absorption, adsorption, distillation, extraction etc)
• The middle component comprise of the actual chemical reaction that leads to the
formation of the desired chemical product
• The reaction can be of any type, single or multiple, involving more than one phase
and can be performed in reactors of various designs
BM-CHE-S402-Chemical Reaction Engineering - II, UIET, CSJM University, Kanpur
• There are two courses on Chemical Reaction Engineering in our syllabus –
Chemical Reaction Engineering- I (CHE-S304)
Chemical Reaction Engineering – II (CHE-S402)
In the first course (CHE-S304), all the basic aspects of reaction engineering was covered, such as
reaction kinetics, how to find a rate law based on laboratory experimental data, design of ideal
reactors, effect of kinetics on reactor design, how heat transfer affects reactor design and finally
study of non-ideal reactors
The ultimate objective of the study of reaction engineering is the design of chemical reactors

Reaction Pressure
kinetics effects

Reactor Design
Heat transfer Non-ideal
effects flow patterns

https://nptel.ac.in/courses/103/101/103101008

In this course, development of reaction rates and reactor design were all done for homogeneous systems
BM-CHE-S402-Chemical Reaction Engineering - II, UIET, CSJM University, Kanpur
In the second course, CHE-S402, we build on the basics learnt in the first course, and will deal
primarily with heterogeneous systems

• Reactions involving more than one phase are termed as heterogenous.

Such reactions may be either catalytic or non-catalytic
• In a catalytic reaction, the catalyst is usually in the solid phase and the reactants and products
may be gases or liquids
- Example: production of benzene (gas) from cyclohexane (gas) using a Pt-Al2O3 catalyst (solid)

(Catalytic reactions can also be homogeneous when the catalyst, reactants and products are all
in one phase)

• In a non-catalytic heterogenous reaction, the reactants or products are present in more then
one phase
3
- Example: 𝑍𝑛𝑆 𝑠 + 𝑂2 𝑔 → 𝑍𝑛𝑂 𝑠 + 𝑆𝑂2 𝑔
2
𝐶𝑎𝐶𝑂3 𝑠 → 𝐶𝑎𝑂 𝑠 + 𝐶𝑂2 𝑔

[Unlike a steady state operation of gas-solid catalytic reactors, non-catalytic gas-solid reactions are
intrinsically dynamic] BM-CHE-S402-Chemical Reaction Engineering - II, UIET, CSJM University, Kanpur
• Heterogenous systems have two complicating factors that must be accounted
for –
(a) the complication of the rate expression
(b) the complication of the contacting patterns of the multiphase systems

• The phase boundaries inherent in the heterogenous systems require that

(1) transport processes (mass and heat transfer) as well as
(2) intrinsic reaction rate must be accounted for in reactor design

Mass transfer
effects

Reaction Pressure
kinetics effects

Reactor Design
Heat transfer Non-ideal
effects flow patterns
https://nptel.ac.in/courses/103/101/103101008

BM-CHE-S402-Chemical Reaction Engineering - II, UIET, CSJM University, Kanpur

• For a gas-solid reaction, the different steps involved are -
movement of the gaseous reactant from the bulk to the O2 Cb
solid surface through the gas film, reaction at the solid
surface, the reverse movement of the gaseous product
from the solid to the bulk gas through the gas film Cs
C
• The rate of reaction is thus influenced by both mass
transfer and reaction kinetics CO2

For eg., 𝐶 + 𝑂2 → 𝐶𝑂2

Three steps involved are : i) mass transfer of O2 from bulk to the surface
ii) reaction at C surface
iii) diffusion of CO2 from the surface to the bulk
The resistance of mass transfer in the gas film results in the concentration on solid surface
(Cs) being lower than the bulk concentration (Cb)
As the surface concentration (Cs) is difficult to determine, the global rate is determined in
terms of the bulk concentration (Cb)

BM-CHE-S402-Chemical Reaction Engineering - II, UIET, CSJM University, Kanpur

Let us consider a gas phase catalytic reaction on a non-porous solid catalyst: 𝑨 𝒈 →𝑩 𝒈
Rate of transport of A from bulk gas phase to the solid catalyst surface, 𝒓𝒑 = 𝒌𝒎 𝒂𝒎 𝑪𝒃 − 𝑪𝒔
(km = mass transfer coefficient, am = external area per unit mass of catalyst)
Rate of reaction at the catalyst surface, 𝒓𝑹 = 𝒌𝑪𝒔 (k = reaction rate constant per unit mass of catalyst)
At steady state the two rates are equal.
Therefore, 𝒌𝒎 𝒂𝒎 𝑪𝒃 − 𝑪𝒔 = 𝒌𝑪𝒔
G -S system
As 𝑪𝒔 < 𝑪𝒃 , mass transfer resistance reduces the rate of reaction
Cb ~ Cs
or, 𝒌𝒎 𝒂𝒎 𝑪𝒃 − 𝒌𝒎 𝒂𝒎 𝑪𝒔 = 𝒌𝑪𝒔

𝒌𝒎 𝒂𝒎
or, 𝑪𝒔 = 𝒌 𝑪𝒃
𝒎 𝒂𝒎 +𝒌

𝒌𝒌𝒎 𝒂𝒎 Cb
or, 𝐫𝐞𝐚𝐜𝐭𝐢𝐨𝐧 𝐫𝐚𝐭𝐞 , 𝒓 = 𝑪
𝒌𝒎 𝒂𝒎 +𝒌 𝒃
This is the global rate, r.
Cs
𝟏 Also called overall rate or
or, 𝒓=𝟏 𝟏 𝑪𝒃 observed rate or measured Cs = 0
+
𝒌 𝒌𝒎 𝒂𝒎
rate

𝑪𝒃
𝒓= The effects of reaction and mass transfer are additive as seen in the resistance term in the denominator
𝛴𝒓𝒆𝒔𝒊𝒔𝒕𝒂𝒏𝒄𝒆𝒔
BM-CHE-S402-Chemical Reaction Engineering - II, UIET, CSJM University, Kanpur
 Other multiphase systems
G - L system (bubble) G - L - S system (slurry)

CALi
CAg CALi CAg
CAgi CAs
CAgi CAL CAL CAL
CA = f(r)

Chemical Reaction Engineering, O. Levenspiel

BM-CHE-S402-Chemical Reaction Engineering - II, UIET, CSJM University, Kanpur
• To get an overall rate expression, the individual steps are written first (they are equivalent forms) and then
the overall rate determined after eliminating the unknown terms

• The rate of reaction are often expressed in the following ways:

1 𝑑𝑁𝐴 𝑚𝑜𝑙 𝑜𝑓 𝐴 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑚𝑜𝑙𝑠 𝑟𝑒𝑎𝑐𝑡𝑒𝑑
Based on total reactor volume −𝑟𝐴 = − 𝑉 = , 𝑚3 𝑟𝑒𝑎𝑐𝑡𝑜𝑟.𝑠
𝑟 𝑑𝑡 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑜𝑟 𝑡𝑖𝑚𝑒

1 𝑑𝑁𝐴 𝑚𝑜𝑙 𝑜𝑓 𝐴 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑚𝑜𝑙𝑠 𝑟𝑒𝑎𝑐𝑡𝑒𝑑

Based on weight of catalyst pellets −𝑟𝐴′ = − 𝑊 𝑑𝑡
= 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡 𝑡𝑖𝑚𝑒
, 𝑘𝑔 𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡.𝑠

1 𝑑𝑁𝐴 𝑚𝑜𝑙 𝑜𝑓 𝐴 𝑟𝑒𝑎𝑐𝑡𝑒𝑑

Based on catalyst surface area −𝑟𝐴′′ = − 𝑆 =
𝑑𝑡 𝑖𝑛𝑡𝑒𝑟𝑓𝑎𝑐𝑖𝑎𝑙 𝑠𝑢𝑟𝑓𝑎𝑐𝑒 𝑎𝑟𝑒𝑎 𝑜𝑓 𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡 𝑡𝑖𝑚𝑒

𝑚𝑜𝑙𝑠 𝑟𝑒𝑎𝑐𝑡𝑒𝑑
𝑚2 𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡 𝑠𝑢𝑟𝑓𝑎𝑐𝑒.𝑠
𝑚𝑜𝑙 𝑜𝑓 𝐴 𝑟𝑒𝑎𝑐𝑡𝑒𝑑
= −𝑟𝐴 𝑉𝑟 = −𝑟𝐴′ 𝑊 = −𝑟𝐴′′ 𝑆
𝑡𝑖𝑚𝑒

If the steps are in series (as discussed), 𝑟𝑜𝑣𝑒𝑟𝑎𝑙𝑙 = 𝑟1 = 𝑟2 = 𝑟3

If the steps are in parallel, 𝑟𝑜𝑣𝑒𝑟𝑎𝑙𝑙 = 𝑟1 + 𝑟2 + 𝑟3

BM-CHE-S402-Chemical Reaction Engineering - II, UIET, CSJM University, Kanpur

• Now going back to the overall (global) rate determined earlier
𝟏
𝒓=𝟏 𝟏 𝑪𝒃
+
𝒌 𝒌𝒎 𝒂𝒎

The mass transfer resistance term mentioned above is known as the external
mass transfer resistance or external diffusion resistance
• As the catalytic reaction takes place at the fluid-solid interface, a large
interfacial area is required for a significant reaction rate
• This area is often provided by the inner porous structure of the solid catalyst
• The reaction takes place inside the pores of a porous catalyst instead of the
external catalyst surface (which has limited surface area)
• As the reactant has to be transported from the mouth of the catalyst pores
on the external surface to the catalytic surface in the pore,
there is another diffusional resistance involved
• This resistance is called the internal mass transfer
resistance or internal diffusion resistance
• The overall reaction rate of a heterogenous reaction will be
influenced by the external and/or internal diffusion
resistance and/or the kinetic resistance
• The largest resistance or the slowest step would be the rate
controlling step of the reaction
BM-CHE-S402-Chemical Reaction Engineering - II, UIET, CSJM University, Kanpur
• Apart from mass transfer resistances, heat transfer resistances also have an effect on the overall
reaction rate of an heterogenous reaction
• For an exothermic reaction taking place in the inner pores of a solid catalyst, the temperature at
the inner pores may be higher than that at the pellet surface
Example: Oxidation of SO2 with air is carried out using a Pt catalyst. Bulk temperature is 465oC.
Actual temperature on the catalyst surface is 15oC above, i.e., 480oC. The rate calculated at this
temperature is 31% higher than the rate calculated at the bulk temperature.
• High temperature in the pores is caused by exothermic reaction along with heat transfer
resistance
• Rate of reaction will be higher in the pores due to increased temperature, but mass transfer
resistance leads to lower reactant concentration inside the pores, resulting in decreased
reaction rate
• The global rate gives a balance of the two effects
• For an exothermic reaction the diffusion and thermal resistances have an opposite effect on the
rate

BM-CHE-S402-Chemical Reaction Engineering - II, UIET, CSJM University, Kanpur

Syllabus
• Introduction to heterogenous processes
• Catalysis – definition and general characteristics
• Adsorption – physical and chemical adsorption; adsorption isotherms
• Solid catalyst – preparation and characterization
• Rate equations for fluid-solid reactions (kinetic models) – Langmuir- Hinshelwood, Eley-Ridel
models
• Heterogenous Data Analysis
• Internal Transport Processes – Reaction and Diffusion in porous catalysts
• External Transport Processes in heterogenous reactions
• Deactivation
• Fluid-particle reaction kinetics (non-catalytic)
• Fluid-fluid reaction kinetics

BM-CHE-S402-Chemical Reaction Engineering - II, UIET, CSJM University, Kanpur

 Recommended Books
▪ Chemical Engineering Kinetics, J. M. Smith, 3rd Edition, Mc Graw Hill International Edition
▪ Elements of Chemical Reaction Engineering, H.S. Fogler, 4th Edition, Prentice Hall India
▪ Chemical Reaction Engineering, O. Levenspiel, 3rd Edition, Wiley and Sons

Relevant NPTEL courses

▪ Chemical Reaction Engineering II, Prof. Ganesh Vishwanathan, IIT Bombay
(https://nptel.ac.in/courses/103/101/103101141/)
▪ Chemical Reaction Engineering 2 (Heterogenous Reactors), Prof. K. Krishnaiah, IIT Madras
(https://nptel.ac.in/courses/103/106/103106117/)
▪ Chemical Reaction Engineering , Prof. Jayant M Modak, IISc Bangalore
(https://nptel.ac.in/courses/103/108/103108097/)
▪ Chemical Reaction Engineering II, Prof. A.K.Suresh, Prof. G. Vishwanathan, Prof. S. M. Mahajani, IIT Bombay
(https://nptel.ac.in/courses/103/101/103101008/)
▪ Catalyst Science and Technology, Dr. Mahuya De, IIT Guwahati
(https://nptel.ac.in/courses/103/103/103103026/)
▪ Heterogenous Catalysis and Catalytic Processes, Prof. K. K. Pant, IIT Delhi
(https://nptel.ac.in/courses/103/102/103102012/)

BM-CHE-S402-Chemical Reaction Engineering - II, UIET, CSJM University, Kanpur