Unit 9

Elements of Heterogeneous
Catalysis
This lecture covers:
• Inorganic catalysis and their properties
• Derivation of rate laws for heterogeneous catalytic reactions
• Catalytic reactor design (X or W?)
• Catalyst deactivation and its rate laws
• Operational solutions to catalyst deactivation problems
Objectives – Be able to:
• Outline the steps in a catalytic reaction and use the concept of a rate-
limiting step to derive a rate law.

• Develop a rate law and linearize it to determine the rate-law parameters

from a set of gas-solid reaction rate data.

• Derive the design equation for a catalytic reactor.

• Calculate the conversion or catalyst weight for packed bed reactors.

• Describe the different types of catalyst deactivation.

• Outline the basic idea to design reactors to solve the catalyst deactivation
problems.

• Calculate the conversion or catalyst weight for moving bed reactors.

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 Catalyst Accelerates Rate of Reaction but
is not Consumed
• Early example of catalysts: wine, cheese and bread production.

• Berzelius (1835): definition of catalysis, catalyst, and catalytic force.

• Ostwald (1887): definition of order of a reaction.

• Langmuir (1915): quantitative theory of adsorption of gases on

surfaces.

• Taylor (1925): catalytically active sites on surfaces.

• Hinshelwood (1927): kinetic mechanism of reactions in

heterogeneous catalysis.

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 Catalyst
Commercial catalysts • Affects the rate of a reaction but
the process unchanged. Does
NOT affect the equilibrium.

• Changes a reaction rate by

promoting a different path for
the reaction.

Nanocatalysts • Affects both the yield and

selectivity.

• Widely used in energy

processing, bulk and fine
chemicals, food processing,
biology, and environmental area.

Highly catalytic surface High surface area

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Catalyst can Decrease the Activation Energy

• Provide an alternative mechanism

Ea(no catalyst)
involving a different transition state
Energy

and lower activation energy.

X, Y
Ea(with catalyst) • Change the operating temperature.
Z DG
• Influence the product distribution.
Reaction progress

Example

Ethylene hydrogenation CH 2 = CH 2 + H 2 ® CH 3CH 3

æ 43000 ö
Homogeneous: r = 10 expç -
27
÷ PH 2
è RT ø
æ 13000 ö
Catalytic: r = 2 ´10 27 expç - ÷ PH 2
è RT ø
At 600 K the ratio of catalytic to homogeneous rate is 1.44*1011
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 Catalytic Reactors
Heterogeneous reactions are encountered by the transport of materials and heat to and
away from the reaction sites. Thus the rate expression in general will incorporate mass/heat
transfer terms in addition to the usual chemical kinetics term (intrinsic reaction rate).

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 Catalytic Reaction on a Porous Catalyst

The overall rate of reaction is equal 1. Mass transfer through external boundary layer
to the rate of the slowest step in the 2. Diffusion into pores
mechanism – rate-determining 3. Adsorption
step. 4. Surface reaction
5. Desorption
6. Diffusion of products out of pores
P-8 This lecture 7. Mass transfer back to bulk fluid
 An Algorithm for Catalytic Reactor Design

Obtain data from

laboratory reactors

Synthesize rate Develop mechanism

law from data and rate-limiting step

Estimate rate law

Reactor design
parameters

• Postulate catalytic mechanisms

-adsorption, surface reaction, desorption
-one of which is usually rate-limiting
• Derive rate laws for the various mechanisms
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 Adsorption
A B
A + S Û A× S
B + S Û B×S
vacant and occupied sites

S represents an active site

(vacant site, with no atom, molecule, or complex adsorbed on it)

Site balance equation:

C t = C v + C A× S + C B × S

Postulated Models

For CO on metal, two models may be proposed:

1. Molecular or non-dissociated adsorption CO + S Û CO × S
2. Dissociated adsorption CO + 2 S Û C × S + O × S

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 Molecular Adsorption

CO + S Û CO × S
Elemental reaction:

rate of attachment = k A PCO Cv

rAD = k A PCO Cv - k - ACCO×S
rate of detachment = k - ACCO×S
kA adsorption
KA = equilibrium constant
k- A
æ C ö
rAD = k A çç PCO Cv - CO×S ÷÷
è KA ø
rAD = 0 at equilibrium
CO is the only material
K A PCO Ct adsorbed on the catalyst
CCO×S = CCO×S = K A PCO Cv
1 + K A PCO Ct = Cv + CCO×S
Langmuir Isotherm
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 Langmuir Isotherm

K P C PCO ¯ ® CCO×S » K ACt PCO

CCO×S = A CO t
1 + K A PCO PCO ­ ® CCO×S » Ct

CCO×S
æ mol ö
çç ÷÷
è g catalyst ø

linear

PCO (kPa)

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 More than one substance

• Same principles as single

A B
A + S Û A× S substance.
B + S Û B×S • Adsorption/desorption of A and
B are first order processes,
and both A and B are
adsorbed as molecules.

K A PACt
C A×S =
1 + K A PA + K B PB
All the things that
the catalyst binds to

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 Surface Reaction Models
1. Single site. only the site on which the reactant is adsorbed is
involved in the reaction.
A B
A× S Û B × S
æ C ö k surface reaction
rS = k S çç C A×S - B×S ÷÷; K S = S equilibrium
è KS ø k-S constant
2. Dual site. the absorbed reactant interacts with another site (either
unoccupied or occupied).
(1) react with a vacant site A× S + S Û B × S + S
A B æ C C ö
rS = k S çç C A×S Cv - B×S v ÷÷
è KS ø
(2) reaction between two adsorbed species

A B C D A× S + B × S Û C × S + D × S
æ C C ö
rS = k S çç C A×S C B×S - C ×S D×S ÷÷
è KS ø
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 (3) reaction of two species adsorbed on different types of sites S and S’

A B C D A × S + B × S ' Û C × S '+ D × S
æ C C ö
rS = k S çç C A×S C B×S ' - C ×S ' D×S ÷÷
è KS ø
e.g., Bi-metallic catalysts

Models 1 & 2 are referred to Langmuir-Hinshelwood Kinetics

- All reagents bind to catalyst, and bound form react.

3. Eley-Rideal: single site and non-adsorbed molecule. The

adsorbed molecule interacts with a molecule in the gas phase.

B
A C
A × S + B( g ) Û C × S
CC × S
rS = k S (C A×S PB - )
KS
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 Desorption

C×S Û C + S
æ PC ö k
rDC = k D çç CC ×S - C v ÷÷; K DC = D desorption
è K DC ø k- D equilibrium constant

• Desorption step for C is the reverse of the adsorption step for C:

1
rDC = -rADC ; K DC =
KC

rDC = k D (C C ×S - K C PC C v )

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 The Rate-Limiting Step

• At steady state, the overall rate of reaction –rA :

- rA = rAD = rS = rD

•Langmuir-Hinshelwood approach is usually applied

to determine catalytic and heterogeneous
mechanisms.

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 Synthesizing a Rate Law Algorithm:
Langmuir-Hinshelwood Approach

1. Assume a sequence of steps in the reaction.

2. Write rate laws for each step assuming all steps to be

reversible.

3. Postulate a rate-limiting step.

4. Use the rates of other steps to eliminate all coverage-

dependent terms.

5. Write a site balance.

6. If the derived rate law does not agree with experimental

data, return to (3).

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Example C6 H 5CH (CH 3 ) 2 Û C6 H 6 + C3 H 6
cumene benzene propylene

C Û B+P

Steps in a Langmuir-Hinshelwood kinetic mechanism

CC × S
• Adsorption C + S Û C×S rAD = k A ( PC Cv - )
KC

PP C B×S
• Surface C × S Û B × S + P(g ) rS = k S (CC ×S - )
reaction KS

• Desorption B×S Û B + S PB Cv
rD = k D (C B×S - )
K DB
= k D (C B×S - K B PB Cv )
Which step is rate-limiting???
Benzene adsorption
P-19 equilibrium constant
 The surface reaction is rate-limiting C Û B+P
k S << k A PP C B×S can’t be measured
- rC = rS = k S (CC ×S - ) and must be replaced
k S << k D KS

rAD CC × S
rate of adsorption : = (PC Cv - )@0
kA KC
rD
rate of desorption : = (C B×S -K B PB Cv ) @ 0
kD
site balance : Ct = C v + CC × S + C B × S

k S Ct K C (PC - PB PP / K P )
- rC = rS =
1 + K B PB + K C PC

K S KC
KP = Overall partial pressure
KB equilibrium constant

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 General Form for Langmuir-Hinshelwood Kinetics

More than 75% of all heterogeneous

C Û B+P reactions that are not diffusion-limited are
surface-reaction-limited.

k S Ct K C (PC - PB PP / K P )
- rC = rS =
1 + K B PB + K C PC

(kinetic factor)(driving - force group)

rate =
(adsorption group)

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 Temperature Dependence of the Rate Law

• The adsorption of all species on the surface is exothermic,

therefore the higher the temperature, the smaller the adsorption
equilibrium constant.

• For a surface-reaction-limited irreversible reaction A ® B

kPA High T
- rA = - rA @ kPA
1 + K A PA + K B PB

• For a surface-reaction-limited reversible reaction AÛ B

k ( PA - PB / K P ) High T æ PB ö
- rA = - rA @ k çç PA - ÷÷
1 + K A PA + K B PB è KP ø

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 An Algorithm for Catalytic Reactor Design

Obtain data from

laboratory reactors

Adsorption
Synthesize rate Develop mechanism
law from data and rate-limiting step Surface reaction
Desorption

More than 75% of all

Estimate rate law heterogeneous reactions are
Reactor design
parameters surface-reaction-limited.

(kinetic factor)(driving - force group)

rate =
(adsorption group)

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 Irreversible Surface-Reaction-Limited
Rate Laws

(kinetic factor)(driving - force group)

rate =
(adsorption group)

kPA
• Single site A× S ® B × S - rA =
1 + K A PA + K B PB

kPA
• Dual site A× S + S ® B × S + S - rA =
(1 + K A PA + K B PB )2
kPA PB
A× S + B × S ® C × S + S - rA =
(1 + K A PA + K B PB + K C PC )2
kPA PB
• Eley-Rideal A × S + B ( g ) ® C × S - rA =
1 + K A PA + K C PC
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 Heterogeneous Reactors Design

• The principles for the design of the ideal reactors remain valid.
• The rate laws are usually more complicated.
• The catalyst weight is used to substitute the reactor volume in
design equations.
• The catalytic or fluid-solid reactor design equations, r’A, are based
on catalyst mass.
dX
1. Batch reactor: N A0 = - rA 'W
dt
dX
2. Packed-bed reactor: FA 0 = - rA '
dW
FA0 X
3. Fluidized CSTR reactor: W=
- rA '
V × ri = W × ri ' = S × ri ' '
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 Steps for the Design of a Catalytic Reactor

1. Deducing a rate law from the experimental data.

2. Finding a mechanism consistent with

experimental observations.

3. Evaluating the rate law parameters.

4. Design of a reactor.

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 Example
Hydrogen and toluene are reacted over a solid mineral
catalyst containing catalyst (a crystalline silica-alumina) to
yield methane and benzene.

C6 H 5CH 3 + H 2 ® C6 H 6 + CH 4
T + H2 ® B + M
• A feed consisting of 30% of toluene, 45% of hydrogen,
and 25% of inert.
• Toluene is fed at 50 mol/min at 640 oC and 40 atm.
• A packed-bed reactor is required to be designed
using the experiments presented below.
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 Experimental Data

P-28
1. Deducing a Rate Law from the Experimental Data

T + H2 ® B + M
(kinetic factor)(driving - force group)
rate =
(adsorption group)

• Relationship with methane

Methane is either absorbed very weakly or goes directly into the gas
phase.

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 (kinetic factor)(driving - force group)
T + H2 ® B + M rate =
(adsorption group)

• Relationship with benzene

Benzene adsorbs on the catalytic surface…

1
- rT ' µ
1 + K B PB + × × ×

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 (kinetic factor)(driving - force group)
T + H2 ® B + M rate =
(adsorption group)

• Relationship with toluene

PT
- rT ' µ
1 + K T PT + × × ×
combine PT
- rT ' µ
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1 + K T PT + K B PB × × ×
 (kinetic factor)(driving - force group)
T + H2 ® B + M rate =
(adsorption group)

• Relationship with hydrogen

- rT ' µ PH 2

combine k ' PH 2 PT
- rT ' =
1 + K T PT + K B PB
It is in qualitative agreement with the experimental data.
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 Steps for the Design of a Catalytic Reactor
1.Deducing a rate law from the experimental data.
2.Finding a mechanism consistent with experimental
observations.
3.Evaluation of the rate law parameters.
4.Design of a reactor.

C6 H 5CH 3 + H 2 ® C6 H 6 + CH 4
T + H2 ® B + M

From the k ' PH 2 PT

experimental data - rT ' =
1 + K T PT + K B PB
k ' PA PB
• Eley-Rideal A × S + B ( g ) ® C × S - rA ' =
1 + K A PA + K C PC
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 2. Proposed Mechanism T + H2 ® B + M

æ CT ×S ö
Adsorption: T (g) + S Û T × S rAD ç
= k A ç Cv PT - ÷÷
è KT ø
Surface-
Surface reaction: H2 (g) + T × S Û B × S + M (g) reaction-limited
æ C P ö
rS = k S çç PH 2 CT ×S - B×S M ÷÷
è KS ø
Desorption: B × S Û B( g ) + S rD = k D (C B×S - K B PB Cv )

k ' PH 2 PT irreversible reaction k ' ( PH 2 PT - PB PM / K P )

- rT ' = KP ® ¥
- rT ' =
1 + K T PT + K B PB 1 + K T PT + K B PB

It has the same equation as that we obtained from the experimental

data. Correct mechanism!!!
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 Steps for the design of a catalytic reactor

3. Evaluate Rate 1. Deducing a rate law from the experimental data.

2. Finding a mechanism consistent with experimental
Law Parameters observations.
3. Evaluation of the rate law parameters.
4. Design of a reactor.

- rT ' =
k ' PH 2 PT T + H2 ® B + M
1 + K T PT + K B PB

linearize

PH 2 PT 1 K B PB K T PT
= + +
- rT ' k ' k' k'

8.7 ´10 -4 PH 2 PT
- rT ' =
1 + 1.04 PT + 1.39 PB
P-35
 Steps for the design of a catalytic reactor
1. Deducing a rate law from the experimental data.
2. Finding a mechanism consistent with experimental
4. Reactor Design observations.
3. Evaluation of the rate law parameters.
4. Design of a reactor.

1. Design equation: dX - rT '

=
dW FT 0

2. Rate law: 8.7 ´ 10 -4 PH 2 PT

- rT ' =
1 + 1.04 PT + 1.39 PB

3. Stoichiometry: PT , PH 2 , PB ® f ( X )

X = f (W )

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 Catalyst Deactivation

Time dependent decrease in catalyst activity due to the loss

of active surface area (Ct decreases).

Examples:
• Coke deposition (homogeneous site attack leading to
uniform deactivation)
• Structural modifications
- sintering
- pore mouth blocking
- vaporization of active materials
• Poisoning (preferential site attack)

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 k is Proportional to Ct
The surface reaction is rate-limiting C Û B+P
k S << k A PP C B×S can’t be measured
- rC = rS = k S (CC ×S - ) and must be replaced
k S << k D KS

rAD CC × S
rate of adsorption : = (PC Cv - )@0
kA KC
rD
rate of desorption : = (C B×S -K B PB Cv ) @ 0
kD
site balance : Ct = C v + CC × S + C B × S
k S Ct K C (PC - PB PP / K P ) k (PC - PB PP / K P )
- rC = rS = =
1 + K B PB + K C PC 1 + K B PB + K C PC
(kinetic factor)(driving - force group)
rate =
(adsorption group)
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Adjustment of Rate Laws for the Decay of the Catalysts

Separable kinetics
- rA ' = a (past history) ´ ( - rA ' ) (fresh catalyst)

The activity of the catalyst at time t: - rA ' (t )

a (t ) =
- rA ' (t = 0)

The rate of catalyst decay: 1.0

da a (t )
rd = - = f [ a (t )]k d (T ) h (C A , C B ,× × ×, C P )
dt
decay law specific decay constant 0 t

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 Types of Catalyst Deactivation
1. Sintering (aging)
waste space
t
t =0 t =t
Pore closure

2. Fouling or coking
t
t =0 t =t
Coking

3. Poisoning
A B A P P P
P

Progression of sites being poisoned

P-40
 Sintering (Aging)
• A loss of active surface area due to prolonged exposure to
high gas-phase temperatures.
• The active surface area is lost by:
- crystal agglomeration and growth of the metals deposited on the support.
- narrowing or blocking of the pores inside the catalyst pellet.
- surface recrystallization.
- the formation or elimination of surface defects (active sites).
• Sintering is usually negligible at temperatures below 40% of
the melting temperature of the solid.
• One of the most commonly used decay laws is second
order with respect to the present activity.

da 1
- = rd = k d a 2 a (t ) =
dt 1 + kd t é Ed æ 1 1 öù
k d = k d (T0 ) exp ê çç - ÷÷ ú
ëR è T0 T ø û
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 Coking or Fouling
• Common to reactions involving hydrocarbons.
• A carbonaceous (coke) material being deposited
on the surface of a catalyst.
• One common decay law

1
a=
1+ k 't m

• Coking can be deduced by running the reactions

at elevated pressure and hydrogen-rich streams.
• Catalyst deactivated by coking can usually be
regenerated by burning off the carbon.

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 Poisoning

• Poisoning molecules irreversibly chemisorbed

to active sites, reducing the number of sites
available for the reaction.

• The poisoning molecule (P) can be: reactant,

product, and impurity.

Poison in the feed (P)

da
rd = - = k d a (t )C P
dt

P-43
 Empirical Decay Rate Laws

P-44
 Example: Catalyst Decay in a Fluidized Bed
(Fogler P717)

The gas-phase cracking reaction: Gas oil (g) ® Products (g)

A® B+C
is carried in a fluidized CSTR reactor. The feed stream contains 80% gas oil
(A) and 20% inert I. The gas oil contains sulfur compounds, which poison the
catalyst.

Assuming that the cracking reaction is first-order with the respect to the gas
oil concentration. The rate of catalyst decay is first-order in the present
activity, and first-order in the reactant concentration.

Assuming that the bed can be modeled as a well-mixed CSTR, determine the
reactant concentration, activity, and conversion as a function of time (CA(t),
a(t) and X(t)).

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 1. Mole balance (CSTR)
dN A dC A
v0 C A 0 - vC A + rA 'W = v0 C A 0 - vC A + rAV = V
dt dt
2. Rate law - rA = a × - rA (t = 0) = a × kCA

3. Decay law da
rd = - = k d aC A
dt
4. Stoichiometry
1 + y A0
v = v0
1 + C A / CT 0
5. Combining

dC A C A 0 (1 + y A 0 ) /(1 + C A / CT 0 ) + atk
= - CA C A = f (t , a )
dt t t
C A = f (t ) da
- = k d aC A
X = f ' (t ) dt
P-46 a = f ' ' (t )
P-47 t (h)
 Overcoming Catalysts Decay
in Continuous Operations

To offset the decline in chemical reactivity

of decaying catalysts:

• Slow decay – Temperature-Time Trajectories

• Moderate decay – Moving-Bed Reactors

• Rapid decay – Straight-Through Transport

Reactors (Circulating Fluidized Bed Reactors)

Transport reactors

P-48
 Moving-Bed Reactor

Principle: co- or counter-current flow of reactant

and solid catalyst. Moving the catalyst to
compensate for the loss of activity over time.

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 Moving-Bed Reactor
Steady-state: the feed rates of the catalyst
and the reactants do not vary with time.

Material balance on A over DW:

FA W - FA W + DW + rA ' DW = 0

dX
FA 0 = - rA ' = a (t )[ - rA ' (t = 0)]
dW
da
- = kd a n
dt
Z r b Ac Z W dW
t= = = dt =
U r b AcU U s Us

X = f (W ) catalyst moving rate

(mass/time)
P-50
 Example: Moving-Bed Reactor

P-51
P-52
P-53
P-54
 Summary adsorption rAD = k A (C v PA - C A×S / K A )
surface rxn rS = k S (C A×S - C B ×S / K S )
• Scheme of surface reaction kinetics desorption rD = k D (C B ×S - K B PB C v )
site balance C t = C v + C A×S + C B ×S
A® B
Surface-reaction-limited
fluid reactants products
Ct k S K A ( PA - PB / K P )
- rA = rS =
external 1 + K A PA + K B PB
transport
General form for surface reaction kinetics
(kinetic factor)(driving - force group)
rate =
(adsorption group)
internal
diffusion
- rA ' (t )
Catalyst deactivation a (t ) =
- rA ' (t = 0)
Rate of reaction
adsorption desorption
- rA ' = a(t)
k ' (T ) fn(C A , C B ,..., C P )
rxn Decay law
solid sites da
- = p[ a (t )]k d (T ) g (C A , C B ,..., C P )
dt
Overcoming catalyst deactivation
transport reactors
P-55