CEB2093

REACTION ENGINEERING II

FUNDAMENTAL OF
CATALYTIC TECHNOLOGIES
Content prepared by: Dr Mohd Hizami Mohd Yusoff Prof Ir Dr Suzana Yusup
Edited by: AP Dr Suriati Sufian

1
Topics:
• Adsorption
isotherms
• Catalysis: active
materials and
reactions
• Application of
catalyst for
industrial process:
current technology,
future direction and
needs

2
 Course Learning Outcomes
By the end of this chapter, students should be able to:
• Distinguish between physical adsorption and chemisorption
• Understand adsorption isotherms and derivation

3
 Adsorption Isotherms
“A relation between the amount of adsorbate adsorbed on a given
surface at constant temperature at different pressures”

4
 Adsorption
“The phenomenon of attracting and retaining the molecules of a gas or
a dissolved substance by the surface of a solid, resulting in their higher
concentration on the surface is called adsorption”

The substance which gets adsorbed is

called the adsorbate and the solid
substance which adsorbs is called the
adsorbent.

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Adsorption vs Absorption

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 ADSORPTION

Physical
Chemisorption
Adsorption

“The adsorbate molecules are held at the “Whenever a chemical combination takes place between the
surface of the adsorbent by weak van der adsorbent and the adsorbate the adsorption becomes very
Waals forces” strong. This type of adsorption caused by forces similar to
chemical bonds between the adsorbent and the adsorbate”

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 Physical vs Chemical Adsorption
Physical adsorption Chemisorption
The forces operating between adsorbate and The forces operating between adsorbate and
adsorbent are the weak van der Waals forces adsorbent are strong and similar to chemical bonds

The enthalpy of adsorption is low and ranges from 10 The enthalpy of adsorption is high and ranges from 40
to 40 kJ mol–1. to 400 kJ mol–1.
No activation energy is involved. Significant activation energy is involved.
Adsorption occurs more readily at low temperature Chemisorption occurs at relatively high temperature
and high pressure. and high pressure
It is reversible in nature. The gas is desorbed on It is irreversible in nature. Desorption also separates
increasing the temperature or decreasing the some amount of the compound formed.
pressure.
Multilayer formation is common. Monolayer formation occurs.

Example: Example:
Adsorption of nitrogen on carbon or alumina. Adsorption of hydrogen on active platinum sites on
any support 8
 9
Schematic representation of different adsorption processes
Adsorption Layers
• Figure (a) shows adsorption
with monolayer formation at
saturation point

• Figure (b) shows a situation

when several layers of
adsorbate molecules are
formed on the surface of the
adsorbent (multilayer
adsorption).

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 Heterogeneous Catalytic Reaction

Heterogeneous catalyst works in general term;

➢ Adsorption Mechanism

➢ Surface Reaction Mechanism

➢ Desorption Mechanism
 Heterogeneous Catalytic Reaction
Steps in Catalytic Reaction;
1. Mass transfer (diffusion) of the reactant(s)
A B (eg. Species A) from bulk fluid to the surface.
2. Diffusion of the reactant from the pore mouth
7
Very fast step

1 External Diffusion through the catalyst pores to the immediate

vicinity of the internal catalytic surface.
3. Adsorption of reactant A onto the catalyst
6 surface (active site).
2 Internal Diffusion 4. Reaction on the surface of the catalyst (eg; A
→ B)
5. Desorption of the products (eg. B) from the
Slowest step

surface
3 5
4 6. Diffusion of the products from the interior of
Catalytic the pellet to the pore mouth at the external
Surface A B surface
7. Mass transfer of the products from the
external pellet surface to the bulk fluid.
 Steps in a Catalytic Reaction

AB
Adsorption on Surface A + S  A •S
Surface Reaction
Single Site A •S  B•S
Dual Site A •S + S  B•S + S
Desorption from Surface B•S  B + S

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 Steps in a Catalytic Reaction

A+B C+D
Adsorption on Surface A + S  A •S
B + S  B•S
Surface Reaction Dual Site
A •S + B•S  C•S + D •S
A • S + B • S'  C • S + D • S'

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 Steps in a Catalytic Reaction

Surface Reaction Eley-Rideal

A • S + B(g )  C • S + D(g )

Desorption form Surface C•S  C + S

D •S  D + S

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Adsorption Mechanism
 Dissociative and non-dissociative adsorption
• Adsorption of a component may be non-dissociative or dissociative.

• In non-dissociative case, the molecule is adsorbed as a whole and it

may be called as molecular adsorption.

• In dissociative adsorption, the molecule such as of H2 is dissociated

into H-H form and adsorbed. Of course the dissociative case requires
2 sites for the adsorption.

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 Adsorption isotherms
Adsorption and heterogeneous reaction are closely related.

1) Langmuir type (single layer)

1-1) One component, non-dissociation
1-2) One component, dissociation
1-3) Two component, non-dissociation
2) BET type (one component, non-dissociation, multilayer)

Porosimetry for measuring the pore structure

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 Langmuir Isotherm Adsorption site
Described as S, s or *

1) Langmuir type (single layer)

Adsorbate
1-1) One component, non-dissociation
A A
kA
A+S↔
k
AS A A
-A
S S S S S S

CiS: surface concentration of sites occupied by

species i [mol-adsorbate/kg-adsorbent]
Adsorbent
Ct: total surface concentration of sites [mol/kg] CAS Cv Vacant or
unoccupied sites
Cv: surface concentration of vacant sites [mol/kg]

Pi: partial pressure of species i [Pa] Ct = Cv + CAS

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 Langmuir Isotherm
1) Langmuir type (single layer)
1-1) One component, non-dissociation

Adsorbate
kA
A+S↔
k
AS A A

-A

Adsorption rate equation A A

 C AS 
S S S S S S

radsorption = k A  PACv − 
 KA  Adsorbent
Adsorption isotherm CAS Cv Vacant or
unoccupied sites

K A PACt
C AS = How to derive??? Ct = Cv + CAS
1 + K A PA
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 Langmuir Isotherm
1) Langmuir type (single layer)
1-2) One component, dissociation
Adsorbate
kA
A1A2+2S ↔
k
A1S+A2S A1 A2

A1 A2
-A

Adsorption rate equation

A1 A2
 2 C A1S C A2 S 
radsorption = k A  PACv −  S S S S S S

 KA 
CAS = CA1S = CA2S Adsorbent
CA1S CA2S C Vacant or
Adsorption isotherm v unoccupied sites

( K A PA )1/ 2 Ct Ct = Cv + CA1S + CA2S

C AS = How to derive???
1 + 2( K A PA )1/ 2
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 Langmuir Isotherm

MODEL 1 MODEL 2
MOLECULAR DISSOCIATIVE ADSORPTION
(NONDISSOCIATED ADSORPTION) CO is adsorbed as C and O
CO is adsorbed as molecules CO

LANGMUIR ISOTHERM

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1) Langmuir type (single layer) Langmuir Isotherm
1-3) Two component, non-dissociation

A+S ↔
k
AS kA
-A
Adsorbate
A
A

B+S ↔ BS
kB B
B
k -B

Adsorption rate equation (q denotes A or B) A B

S S S S S S
 CqS 
radsorption = k q  Pq Cv − 
 K 
 q  Adsorbent
Adsorption isotherm Try to derive! CAS CBS C Vacant or
v unoccupied sites

K q PqCt Ct = Cv + CAS + CBS

CqS =
1 + K A PA + K B PB 31
 Langmuir Isotherm
• Langmuir adsorption isotherm
Cs BP
Strong adsorption kads>> kdes q = Cs → 1
case I q= = 0 C
C 1 + B0 P kads<< kdes C
Weak adsorption q = s = B0 P
Cs ( B0 PAB )1/2 C
q= =

Amount adsorbed
case II C 1 + ( B0 PAB )1/2
C B0 ,A PA
q A = s ,A = mono-layer
C 1 + B0 ,A PA + B0 ,B PB
Case III C B0 ,B PB
large B0 (strong adsorp.)
q B = s ,B = moderate B0
C 1 + B0 ,A PA + B0 ,B PB
small B0 (weak adsorp.)

Pressure

➢ Langmuir adsorption isotherm established a logic picture of adsorption process

➢ It fits many adsorption systems but not at all
➢ The assumptions made by Langmuir do not hold in all situation, that causing error
▪ Solid surface is heterogeneous thus the heat of adsorption is not a constant at different q
▪ Physisorption of gas molecules on a solid surface can be more than one layer
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 Adsorption On Solid Surface
• Five types of physisorption isotherms are found over all solids
I
• Type I is found for porous materials with small pores e.g. charcoal.
It is clearly Langmuir monolayer type, but the other 4 are not
II
• Type II for non-porous materials
amount adsorbed

III • Type III porous materials with cohesive force between adsorbate molecules
greater than the adhesive force between adsorbate molecules and adsorbent

IV

• Type IV staged adsorption (first monolayer then build up of additional layers)

• Type V porous materials with cohesive force between adsorbate molecules

1.0
and adsorbent being greater than that between adsorbate molecules
relative pres. P/P0
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 Adsorption On Solid Surface
• Summary of adsorption isotherms

Name Isotherm equation Application Note

Cs BP Chemisorption and Useful in analysis of

q= = 0
Langmuir C 1 + B0 P physisorption reaction mechanism

Chemisorption Chemisorption
Temkin q =c1ln(c2P)

Easy to fit adsorption

q = c1 p1/ C2 Chemisorption and
data
physisorption
Freundlich
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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 BET Isotherm

2) The Brunauer-Emmett-Teller
(BET) Theory

• An extension to Langmuir type

• Explain the physical adsorption of gas
molecules on a solid surface Assumptions
• Gas molecules physically adsorb on a solid in
• Use unreactive gas (Nitrogen) at 77 K layers infinitely.
• There is no interaction between each
(liquid nitrogen) adsorption layer,
• Langmuir theory can be applied to each
• Used to measure the surface area of solid layer.
or porous materials
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 Multilayer Adsorption

• As the relative pressure is increased,

more and more molecules adsorb on
the surface.
• A thin layer will eventually cover the
entire surface (dark red) in a single
or mono-layer.
• Additional molecules are then
adsorbed to form multilayer (red)
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 BET equation for calculating monolayer adsorption amount (vm)

x 1 c −1
= + x x = p/p0
v(1 − x) vm c vm c 0.05<p/p0<0.35

y c m x (Min 3 data points)

v = the amount of adsorbate on adsorbent at equilibrium [mol/kg] or [cm3/g] etc.

vm= the amount of adsorbate required to form one monolayer over the entire
adsorbent surface [mol/kg] or [cm3/g] etc.
c = system constant (function of kinetic constants and heats of adsorption) ≈100
p = partial pressure of adsorbate (subscript 0 denotes saturation)

From vm [cm3/g], we can calculate the surface area of adsorbent from the following idea:

Na = Avogadro constant (6.022 × 1023 mol−1)

m = mass of test powder (g)
22400 = molar volume at STP (mL)
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Example:

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Surface Reaction Mechanism
 The Surface Reaction Step

A + S  B.S
CA.S. CB.S

A B

Single site catalyst catalyst

41
 The Surface Reaction Step

A.S + S  B.S + S

CA.S. CB.S

S S
A B

Dual site catalyst catalyst

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 The Surface Reaction Step

A.S + B.S  C.S + D.S

CA.S. CB.S. CC.S CD.S.

A B C D

Dual site catalyst catalyst 43

 The Surface Reaction Step

A.S + B.S '  C.S '+ D.S

CA.S. CB.S’ CD.S C

C.S’

A B D C

Dual site catalyst catalyst

 The Surface Reaction Step

A.S + B( g )  C.S + D( g )

CA.S.
CC.S D
A C

catalyst catalyst

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 The Surface Reaction Step

Langmuir Hinshelwood
SINGLE SITE

langmuir hinshelwood
DUAL SITE

ELEY-RIDEAL

46
 The Surface Reaction Step
A gas phase component reacts with an adsorbed species,
i.e., a component reacts from the gas phase with an
adsorbed component. A•s + B(g) → C(g) + s

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Nanotechnology for Water Treatment and Purification by Anming Hu and Allen Apblett
 The Surface Reaction Step

Development of a typical kinetic rate equation

1. Assume a reaction mechanism. The mechanism may include single-site or dual-site

surface reactions and dissociated or non-dissociated adsorption steps
2. Assume the single rate determining step (rds)
3. Assume that all the other steps except the rate determining step are in equilibrium
(pseudoequilibrium)
4. Write down the adsorbed concentration variables in terms of measurable
concentrations
5. Write down the total site balance, eliminate the variable Cs (concentration of empty
sites), and simplify to get the required rate equation.
Desorption Mechanism
 Desorption

C.S  C + S
CC.S.
S
C C

Single site catalyst catalyst

The rate of desorption of C

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Catalysis: Active Materials
& reactions

51
 Elements finding application as catalytic phases, support or promoters.
Alkaline earth metal
Alkali metal

transition metal

52
C. H. Bartholomew et al., Fundamentals of Industrial Catalytic Processes 2nd ed., Wiley Interscience (2006).
Components of heterogeneous catalyst

53
C. H. Bartholomew et al., Fundamentals of Industrial Catalytic Processes 2nd ed., Wiley Interscience (2006).
 Active phases & its catalytic reaction

54
C. H. Bartholomew et al., Fundamentals of Industrial Catalytic Processes 2nd ed., Wiley Interscience (2006).
Catalysis: configuration of adsorbed molecule

Carbon monoxide on metal; proposed schemes

Linear Bridged Twin Dissociated

T. Kei, Catalytic Chemistry, Tokyo Kagaku Doujin (1981). 57

Catalysis: configuration of adsorbed molecule

Carbon monoxide
on metal;
observation by
infrared
spectroscopy

58
T. Kei, Catalytic Chemistry, Tokyo Kagaku Doujin (1981).
59
 Application of Catalyst for
Petrochemical Processes:
Current Technology, Future Direction
& Needs

3-1. Hydrotreating
3-2. Catalytic Cracking
3-3. Naphtha reforming
3-4. Future process
60
61
 3-1 Hydrotreating
1) Objectives
Removing nitrogen, sulfur, oxygen and metal compounds
S and metal; to prevent catalyst deactivation at downstream
S and N; to reduce fuel NOx and fuel SOx

2) Reactions

3) Catalyst
Ni-Mo/g-Al2O3
Co-Mo/g-Al2O3

4) Reactor
Fixed beds or trickle beds (350ºC, 100atm)
62
C. H. Bartholomew et al., Fundamentals of Industrial Catalytic Processes 2nd ed., Wiley Interscience (2006).
 3-1 Hydrotreating

Hydrogen

350ºC
Residuum

100atm

63
C. H. Bartholomew et al., Fundamentals of Industrial Catalytic Processes 2nd ed., Wiley Interscience (2006).
 3-1 Hydrotreating
Stepwise hydrodemetallization and hydrodesulfurization

HDS can be carried out here.

Metal deposit by demetallization

64
C. H. Bartholomew et al., Fundamentals of Industrial Catalytic Processes 2nd ed., Wiley Interscience (2006).
65
 3-1 Hydrotreating

66
C. H. Bartholomew et al., Fundamentals of Industrial Catalytic Processes 2nd ed., Wiley Interscience (2006).
67
 3-2. Catalytic cracking

1) Objectives
To obtain more light fractions (smaller carbon numbers)
Heavy gas oil (C20-C40, 350-500ºC) and vacuum residue (>C40, >550ºC) are
cracked to gasoline range hydrocarbons (C5-C10, 70-220ºC)

2) Reactions
Cracking, cyclization, isomerization, dealkylation etc.
(Next two slides)

3) Catalyst and reactor

- Basically, the catalyst is solid acids.
- SiO2/Al2O3(14wt%) in 1944, moving bed or fluidized bed
- SiO2/Al2O3(28wt%) in 1950, moving bed or fluidized bed
- Zeolite in 1962, higher activity than conventional SiO2/Al2O3, fluidized bed
Current process
- Rare earth exchanged Y-zeolites (60-70 mm, 5-20 wt% supported on SiO2/Al2O3), fluidized bed
(reactor: 490-565 ºC, 1-2.5 atm, contact time around 3 sec, regenerator: 575-760 ºC)
68
 3-2. Catalytic cracking

69
C. H. Bartholomew et al., Fundamentals of Industrial Catalytic Processes 2nd ed., Wiley Interscience (2006).
 3-2. Catalytic cracking

70
C. H. Bartholomew et al., Fundamentals of Industrial Catalytic Processes 2nd ed., Wiley Interscience (2006).
3-2. Catalytic cracking
Catalytic
Catalyst regeneration cracking
(coke burning) Residence time = 4-6 s
Temp.=510-550 ˚C

Since the catalyst is deactivated very fast, it is regenerated continuously.

71
C. H. Bartholomew et al., Fundamentals of Industrial Catalytic Processes 2nd ed., Wiley Interscience (2006).
 3-2. Catalytic cracking
The FCC process

1937 Fixed bed reactor 1942 Fluidized bed reactor 1960s Riser Reactor
(Houdry process) (1943 Moving bed reactor)
Acid treated clay 1944 14wt% Al2O3 type SiO2-Al2O3 1964 zeolite for FCC
1950 28wt% Al2O3 type SiO2-Al2O3 1986 ZSM-5

The fluidized bed reactor was replaced by the riser reactor after the mechanical strength and the activity of the catalyst
had been sufficiently improved.
From left to right: R. A. van Santen et al., “Catalysis: An Untegrated Approach,” Elsevier (1999). 72
Kunii & Levenspiel, “Fluidization Engineering,” Butterworth-Heinemann, Boston, (1991)
C. H. Bartholomew et al., Fundamentals of Industrial Catalytic Processes 2 nd ed., Wiley Interscience (2006).
 3-3. Naphtha reforming
1) Objectives
To improve gasoline quality (octane number)
Naphtha (alkanes and cycloalkanes of C5-C10) is converted to branched alkanes
and aromatics.

2) Reactions
Next slide

3) Catalyst
Dual functions; an acid function for isomerization (alumina) and a dehydrogenation function (metal)
Pt-X/g-Al2O3 -Cl- (X=Ge, Sn, Pb, Re or Ir)

4) Reactor (multi-stage adiabatic)

(1) Semi-regenerative
(2) Cyclic fully regenerative
(3) Continuously regenerative (moving bed)
Conditions: 500 ºC, 14-17 atm
Catalyst regeneration is required.
73
 3-3. Naphtha reforming

desirable

undesirable

74
C. H. Bartholomew et al., Fundamentals of Industrial Catalytic Processes 2nd ed., Wiley Interscience (2006).
 3-3. Naphtha reforming-
semi-regenerative process-

Multi-stage adiabatic reactors

75
C. H. Bartholomew et al., Fundamentals of Industrial Catalytic Processes 2nd ed., Wiley Interscience (2006).
3-3. Naphtha reforming
-composition profile

76
C. H. Bartholomew et al., Fundamentals of Industrial Catalytic Processes 2nd ed., Wiley Interscience (2006).
3-4 Future
Process

77
C. H. Bartholomew et al., Fundamentals of Industrial Catalytic Processes 2nd ed., Wiley Interscience (2006).
 Summary
Hydrotreating Catalytic cracking Naphtha reforming
To remove nitrogen, To obtain more light To improve
Purpose sulfur, oxygen and fractions gasoline quality
metal compounds (octane number)
Hydrodenitrification Cracking Dehydrogenation
Hydrodesulfurization Cyclization Isomerization
Reaction
Hydrodemetalization Isomerization
Dealkylation
Ni-Mo/g-Al2O3 SiO2-Al2O3 Pt-X/g−Al2O3 -Cl-
Catalyst Co-Mo/g-Al2O3 Zeolite (ZSM-5) (X=Ge, Sn, Pb, Re or
Ir)
Reactor Fixed bed Moving bed Fixed bed
and Trickle bed Fluidized bed Moving bed
process (350ºC, 100atm) (500ºC,14-17atm) 78