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Chemical Industry
ca. $2 bn annual sale of catalysts
ca. $200 bn annual sale of the chemicals that are related products
90% of chemical industry has catalysis-related processes
Catalysts contributes ca. 2% of total investment in a chemical process
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CH4003 Lecture Notes 11 (Erzeng Xue)
What is Catalysis
Catalysis
Catalysis is an action by catalyst which takes part in a chemical reaction process and
can alter the rate of reactions, and yet itself will return to its original form without
being consumed or destroyed at the end of the reactions
(This is one of many definitions)
Action of Catalysts
Catalysis action - Reaction kinetics and
mechanism
Catalyst action leads to the rate of a reaction to change.
This is realised by changing the course of reaction (compared to non-catalytic reaction)
Forming complex with reactants/products, controlling the rate of elementary
uncatalytic steps
in the process. This is evidenced by the facts that
catalytic
The reaction activation energy is altered
energy
reactant
The intermediates formed are different from
those formed in non-catalytic reaction produc
The rates of reactions are altered (both reaction processt
desired and undesired ones)
Reactions proceed under less demanding conditions
Allow reactions occur under a milder conditions, e.g. at lower temperatures for those
heat sensitive materials
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CH4003 Lecture Notes 11 (Erzeng Xue)
Action of Catalysts
It is important to remember that the use of catalyst DOES NOT vary DG & Keq
values of the reaction concerned, it merely change the PACE of the process
Whether a reaction can proceed or not and to what extent a reaction can proceed
is solely determined by the reaction thermodynamics, which is governed by the
values of DG & Keq, NOT by the presence of catalysts.
In another word, the reaction thermodynamics provide the driving force for a rxn;
the presence of catalysts changes the way how driving force acts on that process.
e.g CH4(g) + CO2(g) = 2CO(g) + 2H2(g) DG373=151 kJ/mol (100 C)
DG973 =-16 kJ/mol (700 C)
At 100C, DG373=151 kJ/mol > 0. There is no thermodynamic driving force, the reaction
wont proceed with or without a catalyst
At 700C, DG373= -16 kJ/mol < 0. The thermodynamic driving force is there. However,
simply putting CH4 and CO2 together in a reactor does not mean they will react. Without
a proper catalyst heating the mixture in reactor results no conversion of CH4 and CO2 at
all. When Pt/ZrO2 or Ni/Al2O3 is present in the reactor at the same temperature,
equilibrium conversion can be achieved (<100%). 4
CH4003 Lecture Notes 11 (Erzeng Xue)
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CH4003 Lecture Notes 11 (Erzeng Xue)
Applications of Catalysis
Industrial applications
Almost all chemical industries have one or more steps
employing catalysts
Petroleum, energy sector, fertiliser, pharmaceutical, fine chemicals
Applications of Catalysis
Environmental applications
Pollution controls in combination with industrial processes
Pre-treatment - reduce the amount waste/change the composition of emissions
Post-treatments - once formed, reduce and convert emissions
Using alternative materials
Pollution reduction
gas - converting harmful gases to non-harmful ones
liquid - de-pollution, de-odder, de-colour etc
solid - landfill, factory wastes
And many more
Other applications
Catalysis and catalysts play one of the key roles in new technology development.
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CH4003 Lecture Notes 11 (Erzeng Xue)
Research in Catalysis
Research in catalysis involve a multi-discipline approach
Reaction kinetics and mechanism
Reaction paths, intermediate formation & action, interpretation of results obtained under
various conditions, generalising reaction types & schemes, predict catalyst performance
Catalyst development
Material synthesis, structure properties, catalyst stability, compatibility
Analysis techniques
Detection limits in terms of dimension of time & size and under extreme conditions (T, P)
and accuracy of measurements, microscopic techniques, sample preparation techniques
Reaction modelling
Elementary reactions and rates, quantum mechanics/chemistry, physical chemistry
Reactor modelling
Mathematical interpretation and representation, the numerical method, micro-kinetics,
structure and efficiency of heat and mass transfer in relation to reactor design
Catalytic process
Heat and mass transfers, energy balance and efficiency of process
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CH4003 Lecture Notes 12 (Erzeng Xue)
Solid Catalysts
Catalyst composition
Active phase
Where the reaction occurs (mostly metal/metal oxide)
Promoter
Textual promoter (e.g. Al - Fe for NH3 production) Catalyst
Electric or Structural modifier
Support
Poison resistant promoters
Support / carrier
Increase mechanical strength
Increase surface area (98% surface area is supplied within the porous structure)
may or may not be catalytically active
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CH4003 Lecture Notes 12 (Erzeng Xue)
Solid Catalysts
Some common solid support / carrier
materials Other supports
Active carbon (S.A. up to 1000 m2/g)
Alumina Titania (S.A. 10 ~ 50 m2/g)
Inexpensive Zirconia (S.A. 10 ~ 100 m2/g)
Surface area: 1 ~ 700 m2/g Magnesia (S.A. 10 m2/g)
Acidic
Lanthana (S.A. 10 m2/g)
Silica
Active site
Inexpensive
Surface area: 100 ~ 800 m2/g
Acidic
pore
Zeolite porous
solid
mixture of alumina and silica,
often exchanged metal ion present
shape selective
acidic
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CH4003 Lecture Notes 12 (Erzeng Xue)
Preparation of catalysts
Precipitation
Drying
To form non-soluble precipitate by & firing
desired reactions at certain pH and precursor add acid/base precipitate filter & wash
or deposit the resulting
temperature solution with pH control
precipitation precipitate
Adsorption & ion-exchange Support
adsorbed
Amount
Cationic: S-OH+ + C+ SOC+ + H+
Anionic: S-OH- + A- SA- + OH-
Drying
& firing
I-exch. S-Na+ + Ni 2+ D S-Ni 2+ + Na+ Concentration
Support
Impregnation
Fill the pores of support with a metal salt
solution of sufficient concentration to Drying
give the correct loading. & firing
Soln. of metal Pore saturated
Dry mixing precursor pellets
Solid Catalysts
Preparation of catalysts
Catalysts need to be calcined (fired) in order to decompose the precursor and to
received desired thermal stability. The effects of calcination temperature and time
are shown in the figures on the right. 40
100
BET S.A.
75
50
Reduction 25
0 0
if elemental metal is the active phase 0 10
500 600 700 800 900 Time / hours
Sulphidation Temperature C
dead
Typical catalyst life span
Can be many years or a few mins.
Time 16
CH4003 Lecture Notes 13 (Erzeng Xue)
Physisorption Chemisorption
force van de Waal chemcal bond
number of adsorbed layers multi only one layer
adsorption heat low (10-40 kJ/mol) high ( > 40 kJ/mol)
selectivity low high
temperature to occur low high
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CH4003 Lecture Notes 13 (Erzeng Xue)
Surface coverage, q
The solid surface may be completely or partially covered by adsorbed molecules
number of adsorption sites occupied
define q = number of adsorption sites available q = 0~1
Adsorption heat
Adsorption is usually exothermic (in special cases dissociated adsorption can be
endothermic)
The heat of chemisorption is in the same order of magnitude of reaction heat;
the heat of physisorption is in the same order of magnitude of condensation heat.
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CH4003 Lecture Notes 13 (Erzeng Xue)
Usually adsorption is only applied for a process dealing with small capacity
The operation is usually batch type and required regeneration of saturated adsorbent
Common adsorbents: molecular sieve, active carbon, silica gel, activated alumina.
Physisorption is a useful technique for determining the surface area, the pore
shape, pore sizes and size distribution of porous solid materials (BET surface area)
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