Catalysis
Catalysis
Catalysis
applied chemistry
Catalysis
Pradeep Kumar
Department of Chemical engineering
UIET CSJM University Kanpur
1
Chemistry and Chemical engineering more
integarted to the society
Society:
Cleaner and safer processes
Well accepted and integrated processes
Industry:
Speed-up processes
Energy and cost effective processes
New catalysts and catalytic processes
New technologies
Academia:
New innovations
Deeper knowledge and understanding of phenomena
Control of phenomena
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Catalysis & Catalysts
catalytic
energy
reactant
product
reaction process
7
Action of Catalysts
Use of catalyst DOES NOT vary G & Keq of the reaction
Feasibility of reaction is solely determined by thermodynamics, which
is governed by the values of G & Keq, NOT by the catalysts.
Reaction thermodynamics provide the driving force for a rxn; the
presence of catalysts changes the way how driving force acts on
that process.
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Action of Catalysts
At 100C, G373=151 kJ/mol > 0
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Types of Catalysts
based on the its physical state
gas
liquid
Solid
based on the substances from which a catalyst is made
Inorganic (gases, metals, metal oxides, inorganic acids, bases etc.)
Organic (organic acids, enzymes etc.)
based on the ways catalysts work
Homogeneous - both catalyst and all reactants/products are in the same phase (gas or
liq)
Heterogeneous - reaction system involves multi-phase (catalysts + reactants/products)
based on the catalysts action
Acid-base catalysts
Enzymatic
Photocatalysis
Electrocatalysis, etc. 10
Advantages of Catalyst
Industrial applications
Almost all chemical industries employing catalysts
Petroleum, energy sector, fertiliser, pharmaceutical, fine chemicals
Advantages of catalytic processes
Achieving better process economics and productivity
Increase reaction rates - fast
Simplify the reaction steps - low investment cost
Carry out reaction under mild conditions (e.g. low T, P) - low energy
consumption
Reducing wastes
Improving selectivity toward desired products - less raw materials required, less
unwanted wastes
Replacing harmful/toxic materials with readily available ones
Having better control of process (safety, flexible etc.)
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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
Other applications
Catalysis and catalysts play one of the key roles in new technology development.
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Commercial Catalytic Processes
Haber-Bosch process
N2 + 3 H2 2 NH3
Fe/Ru catalysts, high pressure and temperature
Critical for fertilizer and nitric acid production
Fischer-Tropsch
n CO + 2n H2 (CH2)n + n H2O , syn gas to liquid fuels
Fe/Co catalysts
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Research in Catalysis
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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Catalytic Reaction Processes
Understanding catalytic reaction processes
A catalytic reaction can be operated in a batch manner
Reactants and catalysts are loaded together in reactor for a desired time /
desired conversion
Type of reactor is usually simple, basic requirements
Withstand required temperature & pressure
Some stirring to encourage mass and heat transfers
Provide sufficient heating or cooling
Catalytic reactions are commonly operated in a continuous manner
Reactants, which are usually in gas or liquid phase, are fed to reactor in steady
rate
Usually a target conversion is set for the reaction, based on this target
required quantities of catalyst is added
required heating or cooling is provided
required reactor dimension and characteristics are designed accordingly.
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Catalytic Reaction Processes
Reactants in continuous operation are mostly in gas phase or liquid phase
easy transportation
The heat & mass transfer rates in gas phase is much faster than those in
liquid
Catalysts are pre-loaded, when using a solid catalyst, or fed together with
reactants when catalyst & reactants are in the same phase and pre-mixed
It is common to use solid catalyst because of its easiness to separate
catalyst from unreacted reactants and products
With pre-loaded solid catalyst, there is no need to transport catalyst
which is then more economic and less attrition of solid catalyst (Catalysts
do not change before and after a reaction and can be used for number
cycles, months or years),
catalytic reactions are carried out with catalyst in a fixed-bed reactor
(fluidised-bed in case of regeneration being needed)
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Catalytic Reaction Processes
General requirements for a good catalyst
Activity - being able to promote the rate of desired reactions
Selective - being to promote only the rate of desired reaction and also
retard the undesired reactions
Note: The selectivity is sometime considered to be more important
than the activity and sometime it is more difficult to achieve
(e.g. selective oxidation of NO to NO2 in the presence of SO2)
Stability - a good catalyst should resist to deactivation, caused by
the presence of impurities in feed (e.g. lead in petrol poison TWC.
thermal deterioration, volatility and hydrolysis of active components
attrition due to mechanical movement or pressure shock
A solid catalyst should have reasonably large surface area needed for
reaction (active sites). This is usually achieved by making the solid
into a porous structure.
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Example Heterogeneous Catalytic Reaction Process
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Solid Catalysts
Some common solid support / carrier materials
Alumina Other supports
Inexpensive Active carbon (S.A. up to 1000 m2/g)
Surface area: 1 ~ 700 m2/g Titania (S.A. 10 ~ 50 m2/g)
Acidic Zirconia (S.A. 10 ~ 100 m2/g)
Silica Magnesia (S.A. 10 m2/g)
Inexpensive Lanthana (S.A. 10 m2/g)
Surface area: 100 ~ 800 m2/g Active site
Acidic
Zeolite
mixture of alumina and silica, porous pore
solid
often exchanged metal ion present
shape selective
acidic
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Solid Catalysts Support
Preparation of catalysts
Precipitation
Drying
To form non-soluble precipitate by desired & firing
reactions at certain pH and temperature precursor add acid/base precipitate filter & wash
solution with pH control or deposit the resulting
Adsorption & ion-exchange precipitation precipitate
Support
Cationic: S-OH+ + C+ SOC+ + H+
adsorbed
Amount
Anionic: S-OH- + A- SA- + OH-
Drying
I-exch. S-Na+ + Ni 2+ D S-Ni 2+ + Na+ Concentration
& firing
Support
Impregnation
Fill the pores of support with a metal salt
solution of sufficient concentration to give Drying
the correct loading. & firing
Soln. of metal Pore saturated
Dry mixing precursor pellets
Physically mixed, grind, and fired
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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
BET S.A.
Commonly used Pre-treatments 75
50
Reduction 25
if elemental metal is the active phase 0 0
0 10
500 600 700 800 900 Time / hours
Sulphidation Temperature C
if a metal sulphide is the active phase
Activation
Some catalysts require certain activation steps in order to receive the best performance.
Even when the oxide itself is the active phase it may be necessary to pre-treat the
catalyst prior to the reaction ActivityInduction period
Normal use
Typical catalyst life span dead
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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Adsorption On Solid Surface
Adsorption process
Adsorbent and adsorbate
Adsorbent (also called substrate) - The solid that provides surface for adsorption
high surface area with proper pore structure and size distribution is essential
good mechanical strength and thermal stability are necessary
Surface coverage, q
The solid surface may be completely or partially covered by adsorbed molecules
number of adsorption sites occupied
define q= q = 0~1
number of adsorption sites available
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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Catalysis & Catalysts
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 an 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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Catalysis & Catalysts
V3>V2
P4>P3
V2>V1
P3>P2
T1 V4>V3
Vol. adsorbed
Vol. adsorbed
T2 >T1 V1
Pressure
P2>P1
T3 >T2
P1
T4 >T3
T5 >T4
k Cs ( B0 PAB )1/2
Let. B0 ads q
k des C 1 ( B0 PAB )1/2
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Catalysis & Catalysts
Cs , A B0 ,A PA Cs ,B B0 ,B PB
rearrange it for q qA qB
C 1 B0 ,A PA B0 ,B PB C 1 B0 ,A PA B0 ,B PB
kads,A k
where B0 ,A and B0 ,B ads,B are adsorption coefficients of A & B.
kdes ,A kdes ,B
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Catalysis & Catalysts
case III
case II Cs , A B0 ,A PA
case I qA
C 1 B0 ,A PA B0 ,B PB
C BP Cs ( B0 PAB )1/2
q s 0 q C B0 ,B PB
C 1 B0 P C 1 ( B0 PAB )1/2 q B s ,B
C 1 B0 ,A PA B0 ,B PB
k ads k ads k k
B0 B0 B0 ,A ads,A and B0 ,B ads,B
k des k des kdes ,A kdes ,B
Adsorption Adsorption qA
Cs , A
B0 ,A PA
A, B both strong C B0 ,A PA B0 ,B PB
Strong kads>> kdes kads>> kdes C B0 ,B PB
q B s ,B
B0>>1 q C s 1 B0>>1 q
Cs
1 C B0 ,A PA B0 ,B PB
C C q A Cs ,A / C 1
Weak kads<< kdes kads<< kdes A strong, B weak PB
q B Cs ,B / C ( B0 ,B / B0 ,A )
Cs C PA
B0<<1 q B0 P B0<<1 q s ( B0 P)1/2 q A Cs ,A / C B0 ,A PA
C C A weak, B weak
q B Cs ,B / C B0 ,B PB 30
Catalysis & Catalysts
Amount adsorbed
C 1 ( B0 PAB )1/2
C B0 ,A PA
Case III q A s ,A mono-layer
C 1 B0 ,A PA B0 ,B PB
large B0 (strong adsorp.)
C B0 ,B PB
q B s ,B moderate B0
C 1 B0 ,A PA B0 ,B PB
small B0 (weak adsorp.)
Pressure
DH of ads
Langmuir
B0 P b1eQs / RT P Temkin
q qs
1 B0 P 1 b1eQs / RT P
q
where Qs is the heat of adsorption. When Qs is a linear function of qi. Qs=Q0-iS (Q0 is a
constant, i is the number and S represents the surface site),
1 1 [b1eQs / RT P RT 1 b1P
the overall coverage q q s dS dS ln
1 b P exp(- i
0 (1 b eQs / RT P i RT
0
1 1
When b1P >>1 and b1Pexp(-i/RT) <<1, we have q =c1ln(c2P), where c1 & c2 are constants
DH of ads
rads=kads(1-q)P rdes=kdesq Langmuir
Freundlich
B0 P b1eQi / RT P
q qi
1 B0 P 1 b1eQi / RT P q
where Qi is the heat of adsorption which is a function of qi. If there are Ni types of surface
sites, each can be expressed as Ni=aexp(-Q/Q0) (a and Q0 are constants), corresponding to a
fractional coverage qi, i qi Ni 0 [b1eQ / RT P / (1 b1eQ / RT P)] aeQ/Q0 dQ
the overall coverage q
iN
i 0
ae 0 dQ
Q/Q
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Catalysis & Catalysts
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Catalysis & Catalysts
P / P0 1 c -1
BET ( P / P0 ) Multilayer physisorption Useful in surface area
V ( 1 - P / P0 ) cVm cVm determination
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Catalysis & Catalysts
When both A is weakly adsorbed or the partial pressure of A is very low (B0,APA<<1),
ri kB0 ,A PA PB k' PA PB 2nd order reaction
When A is strongly adsorbed or the partial pressure of A is very high (B0,APA>>1)
kB0 ,A PA PB
ri kPB 1st order w.r.t. B
B0 ,A PA
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Catalysis & Catalysts
We then have ri k
(B0 ,AD PAD
1/ 2
P
k (B0 ,AD PAD PB
1/ 2
When both AD is weakly adsorbed or the partial pressure of AD is very low (B0,ADPAD<<1),
ri k (B0,AD PAD PB k' PAD
1/ 2 1/ 2
PB The reaction orders, 0.5 w.r.t. AD and 1 w.r.t. B
When A is strongly adsorbed or the partial pressure of A is very high (B0,APA>>1)
k (B0 ,AD PAD PB
1/ 2
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Catalysis & Catalysts
45
Catalysis & Catalysts
Dd d d
Cumulative curve Frequency curve
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Complex Reactions
d [A] [A]0
-k[A][-OH] -k[A] 2 or [A]
dt 1 kt[A]0
the conversion of B (-OH containing substance) at time t is
[A]0 - [A] kt[A]0
XB
[A]0 1 kt[A]0
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Complex Reactions
Initiation: H2 + O2 O2H + H
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Complex Reactions
Explosion Reactions
Type II Explosion: Thermal explosion
A rapid increase of the rate of exothermic reaction with temperature
Strictly speaking thermal explosion is not caused by multiple production of chain carriers
Must be exothermic reaction
Must be in a confined space and within short time
DH T r DH T r DH
A combination of chain-branching reaction with heat accumulation can occur
simultaneously
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Complex Reactions
Photochemical Reactions
Photochemical reaction
The reaction that is initiated by the absorption of light (photons)
Characterisation of photon absorption - quantum yield
A reactant molecule after absorbing a photon becomes excited. The excitation may lead
to product formation or may be lost (e.g. in form of heat emission)
The number of specific primary products (e.g. a radical, photon-excited molecule, or an ion)
formed by absorption of each photon, is called primary quantum yield,
The number of reactant molecules that react as a result of each photon absorbed is call
overall quantum yield, F
E.g. HI + hv H + I primary quantum yield =2 (one H and one I)
H + HI H2 + I
2I I2 overall quantum yield F =2 (two HI molecules reacted)
Note: Many chain reactions are initiated by photochemical reaction. Because of chain reaction
overall quantum yield can be very large, e.g. F = 104
The quantum yield of a photochemical reaction depends on the wavelength of light used
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Complex Reactions
Photochemical Reactions
Wave-length selectivity of photochemical reaction
A light with a specific wave length may only excite a specific type of molecule
Quantum yield of a photochemical rxn may vary with light (wave-length) used
Isotope separation (photochemical reaction Application)
Different isotope species - different mass - different frequencies required to match
their vibration-rotational energys
508 nm light
e.g. I36Cl + I37Cl I36Cl + I37Cl* (only 37Cl molecules are excited)
C6H5Br + I37Cl* C6H537Cl + IBr
Photosensitisation (photochemical reaction Application)
Reactant molecule A may not be activated in a photochemical reaction because it
does not absorb light, but A may be activated by the presence of another molecule
B which can be excited by absorbing light, then transfer some of its energy to A.
254 nm light
e.g. Hg + H2 Hg* + H2 (Hg is, but H2 is not excited by 254nm light)
Hg* + H2 Hg + 2H* & Hg* + H2 HgH + H*
CO H2
H* HCO HCHO + H*
2HCO HCHO + CO
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