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Department of Chemical Engineering

IIT Madras

Introduction to Catalysis

R. Vinu
4th Feb. 2015

Department of Chemical Engineering

IIT Madras

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Modak, J. M. Chemical Reaction Engineering Course Lectures, 2005, Indian Institute of Science, Bangalore

Department of Chemical Engineering

IIT Madras

Department of Chemical Engineering

IIT Madras

Potential Energy Surface (PES) of catalytic and


non-catalytic reaction

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Schmidt, L. D. The engineering of chemical reactions, Oxford University Press, 2005, New York

Department of Chemical Engineering

IIT Madras

Energy diagram for CO oxidation on Pt catalyst

Non-catalytic route

Transition
state

All energies in kJ/mol


Davis, M. E.; Davis, R. J. Fundamentals of Chemical Reaction Engineering, McGraw Hill, 2003

Department of Chemical Engineering

IIT Madras

Some commercial processes and the


catalysts used

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Schmidt, L. D. The engineering of chemical reactions, Oxford University Press, 2005, New York

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IIT Madras

Terms you should know


Homogeneous vs heterogeneous catalysis
Active Site, Support
Turnover frequency/number

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IIT Madras

Homogeneous catalytic cycle - example


The Monsanto Process

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IIT Madras

Homogeneous catalytic cycle - example

Photocatalytic water gas


shift reaction

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Ziessel, R. Angew. Chem. Int. Ed. 1991, 30, 844-847.

Department of Chemical Engineering

IIT Madras

Heterogeneous catalysts

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Modak, J. M. Chemical Reaction Engineering Course Lectures, 2005, Indian Institute of Science, Bangalore

Department of Chemical Engineering

IIT Madras

NH3-O and NH3-OH activation on Pt(100) surface

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Van Santen R. A. Molecular Catalytic Kinetics Concepts, Wiley-VCH, 2010

Department of Chemical Engineering

IIT Madras

Energy in kJ/mol

Direct NH3 activation vs NH3 activation with


adsorbed O on Pt(111)

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Van Santen R. A. Molecular Catalytic Kinetics Concepts, Wiley-VCH, 2010

Department of Chemical Engineering

IIT Madras

Multiscale Outlook

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Department of Chemical Engineering

IIT Madras

Key Steps

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Modak, J. M. Chemical Reaction Engineering Course Lectures, 2005, Indian Institute of Science, Bangalore

Department of Chemical Engineering

IIT Madras

Types of heterogeneous catalysts


Monoliths

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Fu-Zhen, Z.; Guang-Hong, Z.; Peng-Hui, Z.; Xiao, Y.; Sheng-Fu, J. Chin. J. Catal. 2011, 32, 821-826.

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IIT Madras

Wire Gauze

Wires made of Pt or Pt-Rh


E.g. High temp. oxidation of ammonia and hydrocarbons
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Department of Chemical Engineering

IIT Madras

Molecular sieves

http://www.refiningonline.com/engelhardkb/crep/TCR4_35.htm
http://www.sciencephoto.com/media/4937/view, accessed on 7 th Feb. 2013

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Davis, M. E.; Davis, R. J. Fundamentals of Chemical Reaction Engineering, McGraw Hill, 2003

Department of Chemical Engineering

IIT Madras

Correlation between pore size of molecular sieves and


diameter of various molecules

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Department of Chemical Engineering

IIT Madras

Pore size distribution of zeolite compared to amorphous


silica

Davis, M. E.; Davis, R. J. Fundamentals of Chemical Reaction Engineering, McGraw Hill, 2003

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http://training.fcps.org/tt6/Kindergarten/teddyb/Preschool%20Printables%20-%20Activity%20Page%20-%20Fairy%20Tales%20%20Goldilocks%20and%20The%20Three%20Bears%20Sizing%20(c)_files/3bears_sizingc.gif, access on 7th Feb. 2013

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IIT Madras

Pore size Not too large Not too small But just exact

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Department of Chemical Engineering

IIT Madras

Temperature corresponding to a specific rate

Sabatier Principle

The interaction
between a
substrate and a
catalyst should be
just right

Heat of formation of metal formate

Volcano plot for the decomposition of formic acid on transition metals


http://en.wikipedia.org/wiki/File:Volcano_plot.png, accessed on 7th Feb. 2013

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Department of Chemical Engineering

IIT Madras

Doped vs Impregnated catalysts

1 at.% Pd-doped-CeO2

1 at.% Ag-impregnatedTiO2
Ce4+
Pd2+
O2-

Oxide ion
Vacancy

200 nm

Ag clusters
on TiO2

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Department of Chemical Engineering

IIT Madras

Characterization of a catalyst pellet/particle

What are the various measures/methods?


Single crystal / powder XRD

Temperature programmed
desorption (TPD)

X ray Photoelectron
Spectroscopy (XPS)

Ultraviolet Spectroscopy

FT-IR/Raman

Photoluminescence

Nuclear Magnetic Resonance Porosimetry (BET, BJH)


Electron microscopy

Thermogravimetric analysis

X ray Fluorescence (XFS)

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IIT Madras

Pre-exponential factors for selected unimolecular surface


reactions

2Hads H2,g on transition


metal surfaces

Davis, M. E.; Davis, R. J. Fundamentals of Chemical Reaction Engineering, McGraw Hill, 2003

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IIT Madras

Measures of reaction rates

Levenspiel, O. Chemical Reaction Engineering,

3rd

Ed. John Wiley and Sons, Singapore.

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IIT Madras

Catalytic batch reactor configurations

Levenspiel, O. Chemical Reaction Engineering, 3rd Ed. John Wiley


and Sons, Singapore.

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Department of Chemical Engineering

IIT Madras

Cranberry basket type CSTR

Levenspiel, O. Chemical Reaction Engineering,

3rd

Ed. John Wiley and Sons, Singapore.

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IIT Madras

Circulating fluidized bed reactor

Levenspiel, O. Chemical Reaction Engineering,

3rd

Ed. John Wiley and Sons, Singapore.

28

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IIT Madras

Concentration and temperature profiles

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Department of Chemical Engineering

IIT Madras

Rate limiting steps

Levenspiel, O. Chemical Reaction Engineering,

3rd

Ed. John Wiley and Sons, Singapore.

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Department of Chemical Engineering

IIT Madras

Who are the key players/top catalyst companies?


Haldor Topsoe Denmark
UOP USA
Axens France
Johnson Matthey UK
CRI/Criterion Shell USA
Sd-Chemie Germany
Albemarle USA
Grace Davison UK
BASF Germany
Exxon Mobil - USA
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Department of Chemical Engineering

IIT Madras

What next?

Surface
reaction
kinetics

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