CHAPTER 6 - Industrial Catalysis:

Introduction & Applications

This section covers introduction to industrial catalysis and
various applications of catalysis in chemical
industries
(I. Chorkendorff, J.W. Niemantsverdriet. Concepts of Modern Catalysis
and
Kinetics. 2nd Edition, Wiley-VCH, 2007 &
Jens Hagen. Industrial Catalysis. 2nd Edition, Wiley-VCH,
2006)

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 I. INTRODUCTION

 In chemical industries, reaction must be controlled to get:

 high yield = high conversion and selectivity
 reasonably fast rate
 milder (T,P) conditions
those can be achieved by using appropriate catalysts
 Industrial catalysts have important characteristics:
 Ea < 170 kJ/mol; even lower for enzyme-catalyzed
reaction (i.e. 35 – 50 kJ/mol)
 specific or selective
 only need a relatively small amount of catalyst
 homogeneous & heterogeneous catalysts

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 I. INTRODUCTION

 Desirable (ideal) catalyst properties – read Hagen

section 1.2:
 selective
 stable (long lifetime) order of
 highly active – fast reaction rate
priority
 relatively cheap

and for a heterogeneous catalyst:

 high thermal conductivity
 gives uniform fluid flow and low pressure drop

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 II. SOLID CATALYSTS
 A solid (heterogeneous) catalyst normally consists of:
 active sites (phases) = speed up and direct desirable reaction(s)
 promoters = increase catalyst performance by physical (textural)
interaction or chemical (structural) interaction
 support = gives high surface area and increase active sites’
reactivity

https://cdn.comsol.com/wordpress/2015/02/Catalyst-particle.png
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 II. SOLID CATALYSTS

 Active sites (read Hagen 143 – 145) :

(a) redox catalysts : metal & metal oxides / sulfides as semiconductors
(b) acid/base catalysts (e.g. Al2O3/SiO2 & MgO/SiO2)

 Redox catalysts with metal active sites :

 active metal (normally transitional groups) atoms dispersed over the
surface of the support (read Hagen, section 5.3.3.1)
 can be monometallic or bimetallic (read Hagen, section 5.3.3.2)
 adsorb reactant molecules differently (some molecules are adsorbed
more strongly than others) – discuss about Volcano Plot (Hagen page
125 – 126)
 place where chemisorption (read Hagen, section 5.2.1) and surface
reactions occur
 can be temporarily or permanently deactivated (catalyst poisoning) –
read Hagen, section 5.5
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 J.W. Niemantsverdriet, The Concepts of Heterogeneous Catalysis, 2003

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 J. Hagen, Industrial Catalysis, 2006

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 J.W. Niemantsverdriet, The Concepts of Heterogeneous Catalysis, 2003

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 II. SOLID CATALYSTS
 Promoters = catalyst additives :
 promoters = increase catalyst activity but they are not catalytically
active
 4 types: physical (textural), chemical (structural), electronic,
catalyst-poison-resistant (read Hagen, section 5.4.3)

 added to catalysts in amounts of a few percent, or more up to 25%

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 II. SOLID CATALYSTS

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 II. SOLID CATALYSTS
 To choose a support (discuss Hagen page 180 – 183), these properties
must be considered:
 should be inert
 enough mechanical strength under reactor pressure
 stable on the reaction conditions (T,P) range
 can be regenerated if temporary poisoning occurs (read Hagen,
section 5.5)
 very high surface area
 porosity
 reasonable cost

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 II. SOLID CATALYSTS

 Examples of good support:

 -alumina
 silica
 alumina-silica (zeolites): natural & synthetic
 activated C

 Other supports:
 MgO – rather poor mechanical strength
 ZnO – poor stability as prone to reduction
 Cr2O3 – acid sites cause undesirable
reactions
 TiO2 – highly stable at high T, but expensive
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 III. INDUSTRIAL CATALYSTS

Hagen,
Section 5.5

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 IV. HOMOGENEOUS INDUSTRIAL CATALYSTS

 Organometallic (transition metal) complexes – compounds with

metal-C bonds – as homogeneous catalysts:
 reactivity comes from organic ligands – such as H, CO, alkenes
–
bound to the metal center (d orbitals)
 molecular transformations require a loose coordination of the
reactants to metal (central) atom and easy release of the products
from the coordination sphere
 therefore, extremely labile metal complexes are required which
have a vacant coordination site or at least one weakly bound ligand
 some key reactions in homogeneous catalysis is extensively
discussed in Hagen, section 2.1, i.e. coordination & exchange of
ligands, complex formation, acid-base (Bronsted & Lewis)
reactions, redox (oxidative addition and reductive elimination)
reactions, insertion & elimination reactions, reactions at
coordinated ligands
 16/18-electron rule and catalytic cycles of organometallic catalytic
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reactions are discussed page 18
in Hagen, CHAPTER 6 – INDUSTRIAL CATALYSIS
section 2.2
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 IV. HOMOGENEOUS INDUSTRIAL CATALYSTS

 Some industrial examples of homogeneous (transition metal)

catalysis are given in Hagen, section 3.2, which cover:
 Oxo synthesis: hydroformylation of propene with CO and H2.
Main products are 1-butanol and 2-ethylhexanol via intermediate
product butyraldehyde
 Acetic acid production by carbonylation of methanol with CO
 Wacker process: selective ethylene oxidation to form acetaldehyde
 Oxidation of cyclohexane producing cyclohexanone and
cyclohexanol
 Suzuki coupling: cross coupling between organoboronic acid and
halides, widely used in fine chemicals production
 Oligomerization of ethylene (SHOP – Shell Higher Olefin Process):
synthesize long-chain straight olefins (C4-C10, C12-C18, and C20+)
for detergents, plasticizers, and lubricants.
 Olefin polymerization in the manufacture of high molecular weight
polyolefins (polyethylene and polypropylene)
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 IV. HOMOGENEOUS INDUSTRIAL
CATALYSTS

 Other important examples of homogeneous industrial

catalysis are enzyme catalyzed reactions. 6 classes
of enzymes based on reaction types:
(1) oxidoreductase (oxidation-reduction reactions)
(2) transferases (transfer of chemical group from one
substrate to another or from one part of substrate
to another)
(3) hydrolases (hydrolysis reactions)
(4) lyases (elimination of groups from adjacent atoms
or
addition of groups to double bonds)
(5) isomerases (rearrangement of atoms in a
molecular
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page 23 CHAPTER 6 – INDUSTRIAL CATALYSIS
(6) ligases (formation of bonds to groups with
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 IV. HOMOGENEOUS INDUSTRIAL CATALYSTS

 Some industrial examples of enzyme catalysed

reactions are given in Hagen, section 4.3, which cover:
 Production of acrylamide from water addition to
acrylonitrile using nitrile hydratase enzyme.
Acrylamide is a base molecule for water-soluble polymers
used as flocculants, paper mill, surface coatings, etc.
 Synthesis of aspartame, a widely used artificial low-
calorie sweetener – 200 times as sweet as sucroce, using
thermolysin enzyme.

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 V. HETEROGENEOUS INDUSTRIAL CATALYSTS

 The use of heterogeneous industrial catalysts,

based on product types (refer to Chapter 8 & 9
Chorkendorff & Niemantsverdriet and Section
8.1 Hagen):
 Production of organic and inorganic chemicals
 Crude oil refinery & petrochemical industries

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 V. HETEROGENEOUS INDUSTRIAL CATALYSTS
• Examples of heterogeneous industrial catalysts, in
NH3/urea plant :
 Primary Reformer – Ni based

Top Section Bottom Section

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 V. HETEROGENEOUS INDUSTRIAL CATALYSTS
NH3 plant

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 V. HETEROGENEOUS INDUSTRIAL
CATALYSTS

• Examples of heterogeneous industrial catalysts,

in NH3/urea plant :
 Water Gas Shift Reactor – HTSC: Fe based, LTSC: Cu
based

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 V. HETEROGENEOUS INDUSTRIAL
CATALYSTS

• Examples of heterogeneous industrial catalysts,

in NH3/urea plant :
 Methanator – Ni based

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 V. HETEROGENEOUS INDUSTRIAL
CATALYSTS

• Examples of heterogeneous industrial catalysts,

in NH3/urea plant :
 NH3 Reactor – promoted Fe

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 V. HETEROGENEOUS INDUSTRIAL CATALYSTS

 The use of heterogeneous industrial catalysts,

based on production scales (Section 8.2 &
8.3 Hagen) :
 Bulk chemicals production
 Fine chemicals production

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 V. HETEROGENEOUS INDUSTRIAL CATALYSTS

 Other examples of heterogeneous industrial catalysts, for

bulk and fine chemicals :
 Hydrogenation reactions, eg in margarine production
 Methanol synthesis
 Selective oxidation of alkene, eg ethylene oxide,
acrolein, maleic anhydride and phthalic anhydride
production
 Olefin polymerization

 Catalytic hydrogenation in vitamin productions

 Oxidation process, eg citral production (an intermediate
for fragnances and vitamins A & E)
 Catalytic C-C linkage, eg ibuprofen (analgesic) production
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 DISCUSSION &
FURTHER SELF-STUDY

https://ww
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w.slideshare.net/GerardBHawkins/design-and-