Ch.

10 Catalysis and Catalytic Reactors Chemical Reaction Engineering 2023

Chapter 10 Catalysis and Catalytic Reactors

※ Catalyst

A substrate that affects the rate of a reaction but emerges from the process unchanged.
．a different mechanism with lower activated energy
．affect both the yield and selectivity
．only change the rate of a reaction, not affect the equilibrium.

※ Homogeneous catalytic reaction

A catalyst is in solution with at least one of the reactants.

* Oxo process

※ Heterogeneous catalytic reaction (This chapter only discuss “hetero. catalytic rxn”. )
．It involves more than one phase.
．Usually the catalyst is a solid and the reactants and products are in liquid or gaseous form.
．Easily separation, economically attractive.
* Dehydrogenation of cyclohexane

Catalytic reactions occur at fluid-solid interfaces → mass-transfer limited → large interfacial area
Inner porous structure can provide larger fluid-solid interfacial area.

※ Classification of catalysis

．Alkylation and Dealkylation reactions ．Isomerization reactions

AlCl3, AgCl, Pd AlCl3, Pt/Al2O3, zeolite

．Hydrogenation and Dehydrogenation reactions ．Oxidation reactions

Co, Pt, Cr2O3, Ni Cu, Ag, Ni, V2O5

．Hydration and Dehydration reactions ．Halogenation and Dehalogenation reactions

Al2O3, MgO CuCl2, AgCl, Pd

10-1
Ch.10 Catalysis and Catalytic Reactors Chemical Reaction Engineering 2023

※ Type of Catalysts

◎ Porous catalyst

A catalyst has a large area resulting from pores.

．Porous metal ．Metallic foam

* Raney Nickel (Al-50wt%Ni (-68.5at%Ni) alloy power)

Used in hydrogenation of vegetable or animal oils.

as-casting microstructure of Al-Ni alloy

Al removal by the leaching reaction
2Al + 2NaOH + 6H2O2 → 2Na[Al(OH)2] + 3H2

◎ Monolithic catalyst
．High active catalyst without a large surface area.
．Pressure drop and heat removal are major consideration.
．Pt is a primarily catalytic material.
* porous (honeycomb)

* nonporous (wire gauze)

Used to oxidize pollutants of exhaust in automotive catalytic converter.

10-2
Ch.10 Catalysis and Catalytic Reactors Chemical Reaction Engineering 2023

◎ Molecular sieves
Materials with very small pores which admit small molecules
but prevent larger ones from entering.

* Zeolite

．Natural minerals or synthetic materials

．Crystalline aluminosilicates Mx/n [(AlO2)x (SiO2)y] · z H2O (D5R)
．Units: AlO4 and SiO4 tetrahedrons
．High selectivity

* Faujasite-type zeolite (D6R)

∙Reactant selectivity
∙Restricted transition-state selectivity
∙Product selectivity

◎ Supported catalyst and unsupported catalyst

Supported catalyst consists of minute particles of an active material dispersed over a
non-catalytic substrate, called support, which principally serves as a framework on
which catalyst is deposited.

．Highly porous nature - increase available surface area and activity

．Improve stability
．Improves the heat transfer characteristics
Supported catalyst : Pt/Al2O3 V2O5/SiO2

Unsupported catalyst: Pt gauze

10-3
Ch.10 Catalysis and Catalytic Reactors Chemical Reaction Engineering 2023

※ Catalysis and Activity

Activity
．Involved with active centers on the surface of the catalyst, geometry of surface, electronic
structure and formation of surface intermediates.

Activity site
．A reaction is not catalyzed over the entire solid surface but only at certain active sites.
．A point on the catalyst surface can form strong chemical bonds
with an adsorbed atom/molecule.
．Active sites or centers are the unsaturated atoms in the solids
that resulted from surface irregularity, dislocation, edges of
crystal and crack along grain boundaries.

Turnover frequency (TOF)

．Number of molecules reacting per active site per second at the specific condition.

Promoter
．An additive has no catalytic properties of its own but enhances the activity of a catalyst.
．A small amount of promoter addition will cause a steep rise in activity to a sharp maximum.

Inhibitor
．Added to the catalyst during its manufacture to reduce its activity.

Adsorbent
．Solid material that can adsorb gas molecules.

Adsorbate
．Gas that already has been adsorbed

※ Rate law for heterogeneous catalysis

．Power law Ignore the problems w.r.t. adsorption and surface reaction

．Langmuir-Hinshelwood approach (chemical adsorption)

Mechanism: adsorption
surface reaction one of which is rate-limiting
desorption

※ Rate of reaction

10-4
Ch.10 Catalysis and Catalytic Reactors Chemical Reaction Engineering 2023

※ Catalyst Deactivation

Aging
．Gradual change in surface structure of active materials.
．Sintering that the crystal agglomeration and growth of the metal atoms on the support.
．Narrowing or closing of the pores inside the catalyst pellet.
．Surface re-crystallization or the formation or elimination of surface defects.
．Sintering can be reduced by keeping the temperature below 0.4 times the metal’s MP.

Coking
．Deposition of carbonaceous material on entire surface.
．Catalysts deactivated by coking can usually be regenerated
by burning off the carbon. (See Ch.11 Shrinking core model)

Poisoning
．Poisoning molecules become irreversible chemisorbed to active
sites of a catalyst, therefore reducing the number of sites available.
．Poisoning molecules may be a reactant, or a product or an impurity.
．When poisoning occurs in PBR, the deactivation process can move through PBR
as a wave front.

10-5
Ch.10 Catalysis and Catalytic Reactors Chemical Reaction Engineering 2023

※ Mass transport steps in a catalytic reaction

1. External diffusion of the reactant
2. Intraparticle diffusion of reactant within the catalyst pores
3. Adsorption of the reactants
4. Chemical reaction on the surface of catalyst. (Ch.10)
5. Desorption of the products
6. Intraparticle diffusion within the catalyst pores
7. External diffusion

(Ch.11)

(Ch.12)

(Ch.10)

．External diffusion is in series with chemical steps.

．Internal diffusion occurs simultaneously with the chemical reaction.
．As the heterogeneously catalyzed reaction involves sequential steps, at steady state rate of
these steps must be the same.
．If the rate constant of one of these steps is markedly smaller than the other, the overall rate
is determined by this step, called the rate determining step.

◎ External diffusion (Ch.11)

◎ Internal diffusion (Ch.12)

Large pellets the reactant is consumed near the exterior surface of the pellet.
Small pellets internal diffusion no longer limits the rate of reaction.

10-6
Ch.10 Catalysis and Catalytic Reactors Chemical Reaction Engineering 2023

※ Adsorption
Adsorption is the process of interaction between the molecules of
a gaseous or liquid phase with the surface of a solid.

◎ Physical adsorption
．Weak undirected interactions due to Van der Waals forces.
．Epot minimum is at distance (d > 0.3nm) larger than a chemical bond.
．The adsorption heat (ΔHads) is small. (similar to ΔHcondensation)
．No energetic barrier, always not activated.
．Determine porosity and surface area of heterogeneous catalysts.

◎ Chemical adsorption Non-activated

．Formation of a true chemical bond.
．Strong directed interaction involving a substantial
rearrangement of electron density.
．Epot minimum is at chemical bond distance.
．The adsorption heat (ΔHads) is big. (as to ΔHreaction)
．Chemical adsorption can be activated.
．Physical adsorption reduces the energetic barrier to overcome. Activated
Adsorption isotherm

10-7
Ch.10 Catalysis and Catalytic Reactors Chemical Reaction Engineering 2023

Physical adsorption Chemical adsorption

van der Waal’s force Valance force
Non-specific Specific
Non-dissociative Often dissociative
Non-activated Often activated
Exothermic, but small Exothermic and large
ΔH≒-1~-15kcal/mol ΔH≒-10~-100kcal/mol
All solid/ all gases Active site/ reactive gas
Multi-layer Monolayer
Low temperature High temperature
High reversibility Low reversibility
Rapid rate Slow rate
BET model Langmuir-Hinshelwood model

10-8
Ch.10 Catalysis and Catalytic Reactors Chemical Reaction Engineering 2023

Adsorption isotherm

Macropore ( d > 50nm )

‧Reversible
‧Multilayer adsorption at high P/P0
‧If the knee of the isotherm is sharp, the uptake
at point B- beginning of the middle almost linear
section-corresponding to the monolayer volume.

Mesopore ( 2nm < d < 50nm )

‧Non-reversible
‧To calculate mesopore size distribution and volume
computational procedures have been developed.
‧The shape of the hysteresis loop depends on the
mesopore structure.

Micropore ( d < 2nm )

‧Reversible
‧Steep increase of Vads at low P/P0
‧The micropores are filled with N2 and the volume
corresponding to the horizontal plateau is a
measure of the micropore volume.

10-9
Ch.10 Catalysis and Catalytic Reactors Chemical Reaction Engineering 2023

Porosity
※ He-Hg method
‧ He gas :
Small molecule and weak molecular force, so all void
can be occupied by He.
The chamber was evacuated, and then a known quantity of helium
is admitted. From the gas laws and measurements of the
temperature and pressure, we can determine the volume occupied
by the helium (VHe)

‧ Hg :
High surface tension.
The chamber is filled with mercury at atmospheric pressure.
Since the mercury will not penetrate the pores of most catalysts
at atmospheric pressure, the mercury will occupy only the volume
exterior to the pellets (VHg).

(void volume per gram)

Porosity,

Pore size distribution

◎ Hg intrusion porosimetry

Because of high surface tension, the Hg penetration method is used to determine the pore
size distribution of larger pores, i.e., those with radii larger than about 10 nm. The
relationship between pore size and applied pressure, P, is as follows:

Experimental set-up
‧Hg intrusion porosimetry ‧Volumetric adsorption measurement
Pressure range: vacuum ~ 400MPa

N2 at 77K
Ar at 87K
CO2 at 273K

10-10
Ch.10 Catalysis and Catalytic Reactors Chemical Reaction Engineering 2023

10-11
Ch.10 Catalysis and Catalytic Reactors Chemical Reaction Engineering 2023

◎ N2 desorption method

．To determine the distribution of pores with diameters of < 20 nm.

．The porous material is exposed to high pressures of N2 (near the saturation vapor pressure)
and the void space is assumed to be filled with condensed N2. The pressure is lowered in
increments to obtain a desorption isotherm.
．The vapor pressure of a liquid in a capillary depends on the radius of curvature ( < 20nm).
．The smaller the pore radius, the lower the vapor pressure.
Kelvin equation

BJH pore size model

◎ BET method (Brunauer, Emmett and Teller, 1938)

An extension of the Langmuir theory, which is a theory for monolayer molecular

adsorption, to multilayer adsorption with the following hypotheses:
．Gas molecules physically adsorb on a solid in layers infinitely.
．There is no interaction between each adsorption layer.
．The Langmuir theory can be applied to each layer.

10-12
Ch.10 Catalysis and Catalytic Reactors Chemical Reaction Engineering 2023

※ Langmuir adsorption
In 1916, Langmuir proposed a model isotherm for gases adsorbed to solids.
It is a semi-empirical isotherm derived from a proposed kinetic mechanism, which is
based on four assumptions
．The entire active site is energetically uniform.
．Monolayer adsorption
．No interaction between adsorbed molecules.
．Each adsorbed molecules has the same structure and is localized.

◎ Adsorption with an atom or a molecule (non-dissociative adsorption)

S : activity site
k : adsorption constant
k’ : desorption constant
K : adsorption equilibrium constant
(Note: k are different based on conc. and θ)

．Coverage the fraction covered by adsorbed molecules

Site balance: Vads : volume of gas adsorbed

Vmax : max. monolayer volume

．Concentration ．Coverage

10-13
Ch.10 Catalysis and Catalytic Reactors Chemical Reaction Engineering 2023

◎ Adsorption with one dissociative molecule

※ Reaction determined by surface reaction

． ．

(PSSH) (PSSH)

◎ Bimolecular adsorption

※ Reaction determined by surface reaction

(Eley-Rideal kinetics)

10-14
Ch.10 Catalysis and Catalytic Reactors Chemical Reaction Engineering 2023

※ CO adsorption
* Molecular adsorption (nondissociated) * Atomic adsorption (dissociated)

．Consider (nondissociated adsorption)

．Consider (dissociated adsorption)

◎ Bimolecular adsorption
* Competitive adsorption * Noncompetitive adsorption

10-15
Ch.10 Catalysis and Catalytic Reactors Chemical Reaction Engineering 2023

※ Catalytic reaction mechanism

．Adsorption on surface

．Surface reaction

Single site

Dual site

．Desorption from surface

．Adsorption on surface

．Surface reaction

Dual site (Langmuir-Hinshelwood kinetics)

Single site (Eley-Rideal kinetics)

．Desorption

10-16
Ch.10 Catalysis and Catalytic Reactors Chemical Reaction Engineering 2023

◎ Langmuir-Hinshelwood kinetic mechanism

adsorption

surface rxn

desorption

．In the three steps, one of which is rate-limiting. Exp. data

．When heterogeneous reactions are carried out at steady-state,
the rates of the three steps in series are equal to one another.
At steady-state

※ If adsorption is rate-limiting

10-17
Ch.10 Catalysis and Catalytic Reactors Chemical Reaction Engineering 2023

※ If surface reaction is rate-limiting

※ If desorption is rate-limiting

10-18
Ch.10 Catalysis and Catalytic Reactors Chemical Reaction Engineering 2023

※ Relationship of rate-limiting step and rate law

adsorption

surface rxn

desorption

．If adsorption is rate-limiting,

>> the absorbed reactant (PA) is not present in the denominator.

．If surface rxn is rate-limiting,

>> the absorbed species (PA and PB) are present in the denominator and

the unabsorbed species (PP) is not present in the denominator.

．If desorption is rate-limiting,

>> the absorbed product (PB) is not present in the denominator.

※ If the irreversible surface reaction is rate-determining step in the catalytic reaction

partial pressure of reactants

k PP
i j
 rA  number of involved active sites in one reaction
(1+  K i Pi ) n
i
reactant and product adsorbed on the active site

10-19
Ch.10 Catalysis and Catalytic Reactors Chemical Reaction Engineering 2023

※ Rate laws derived from RDS (surface reaction is rate-limiting)

※ Rate laws derived from PSSH

If two or more steps are rate-limiting, if some of the steps are irreversible, or if none of the
steps are rate-limiting.

(RDS)

10-20
Ch.10 Catalysis and Catalytic Reactors Chemical Reaction Engineering 2023

※ Chemical vapor deposition (CVD)

CVD mechanism is similar to heterogeneous catalysis.

◎ Germanium deposition

Gas-phase dissociation
Adsorption
Adsorption
Surface reaction (RDS)

◎ Silicon deposition

Gas-phase dissociation
Adsorption
Surface reaction (RDS)

10-21
Ch.10 Catalysis and Catalytic Reactors Chemical Reaction Engineering 2023

◎ Catalyst Deactivation

Catalyst activity

: fresh catalyst

: catalyst that has been used for a time, t

．Rate of disappearance of reactant A on a catalyst accounting for catalyst activity

Separable kinetics
．Rate of catalyst decay

Where is some function of the activity, and kd is the specific decay constant.

◎ Aging - commonly considered to be 2nd order

◎ Coking

◎ Poisoning

※ Conversion with catalyst decay in a batch reactor

( lst -order)

10-22
Ch.10 Catalysis and Catalytic Reactors Chemical Reaction Engineering 2023

※ Response to catalyst deactivation

．Slow decay
- Temperature-time trajectory
To maintain a constant conversion (reaction rate) with a decay catalyst
increasing the feed temperature or decreasing the feed flow rate

．Moderate decay ．Rapid decay

- Using moving-bed reactors - Using straight-through transport reactors catalyst
regeneration (STTR)

※ Catalytic cracking in a moving-bed reactor

The reaction rate is 2nd order, the catalyst decay rate is 1st order and
the catalyst moving rate is US (mass/time).

10-23