CHEMICAL

REACTION
ENGINEERING
CATALYTIC REACTIONS
(II)
RATE LAWS USING PSSH

◼ Pseudo-steady-state-hypothesis
◼ Each species adsorbed on the surface is a reactive
intermediate
◼ Net rate of formation of species i adsorbed on the surface is
zero:

◼ Applied when irreversible mechanisms are involved, or

when two are more steps are rate-limiting
 Example : isomerization of normal pentene to iso-
pentene
Mechanisms
:
Rate
limiting

The net rates of generation of N·S and I·S are:

TEMPERATURE DEPENDENCE OF THE
RATE LAW

◼ Since the adsorption of all species on the surface is

exothermic, the higher the temperature, the smaller the
adsorption equilibrium constant.
◼ For a surface-reaction-limited irreversible rxn A→B:

High
temperature

◼ For a surface-reaction-limited reversible rxn A→B:

High
temperature
 The principles for the design of the ideal reactors
remain valid.

HETEROGENEO The rate laws are usually more complicated.

US REACTORS
DESIGN 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.
Batch reactor:

Packed-bed reactor:

(Fluidized) CSTR reactor:

Steps for the design of a catalytic reactor:

• Deducing a rate law from the experimental
data
• Find mechanism
• Evaluate rate law parameters
• Design of a reactor
 The design of a heterogeneous reactor (Example)

A feed consisting of 30 % toluene, 45% hydrogen, and 25% inert.

Toluene is fed at 50 mol/min at 640 °C and 40 atm. A packed-bed and a
fluidized CSTR are required to be designed using the experimental data
presented in Table 10.5 on page 621.

Deducing a rate law from the experimental

data
Find the relationship between

rate of disappearance of partial pressure of all

toluene species
 Relationship with methane:
If the methane were adsorbed on the catalytic
surface:
However, this is not consistent with the experimental observation. Therefore, we assume that
methane is either very weakly absorbed or goes directly into the gas phase.

Relationship with benzene:

If the benzene were adsorbed on the catalytic
surface:
The experimental data support this formulae. Benzene is probably on the surface.

Relationship with
toluene:
The formulae supports the experimental observation.

(i.e., the rate increases with increasing partial pressure of toluene at low concentration of toluene. At high
concentration of toluene, the rate is independent of the toluene partial pressure.)
Relationship with Hydrogen:
The formulae supports the experimental observation.

(i.e., the rate increases linearly with the increasing hydrogen concentration,
which shows that hydrogen is either not adsorbed on the surface or it’s converge
of the surface is low)

Combining all these

equations:

is in qualitative agreement with the experimental

data.
 Steps for the design of a catalytic reactor:
• Deducing a rate law from the experimental
data
• Find mechanism
• Evaluate rate law parameters
• Design of a reactor
Find
mechanisms
Adsorption:

Surface
reaction:
Desorption:
Assuming the
surface reaction is
the rate-limiting if irreversible surface reaction
mechanism: (i.e. the value of KP is infinite)

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

results. These might be the correct mechanisms.
Steps for the design of a catalytic reactor:
• Deducing a rate law from the experimental
data
• Find mechanism
• Evaluate rate law parameters
 Linearize the rate equation

POLYMATH regression analysis

Using the least-square
analysis
 

Steps for the design of a catalytic reactor:

• Deducing a rate law from the experimental
data
• Find mechanism
• Evaluate rate law parameters
•
Mole balance Rate law Stoichiometry
(PBR)

We can obtain the conversion as a function of the catalyst weight.

Mole balance Rate law

(CSTR)

We can obtain the weight of catalyst required to achieve a specific conversion.

CHEMICAL VAPOR DEPOSITION
(CVD)
◼ This method can be applied to the formation of
microcircuits (electrically interconnected films).
◼ The mechanisms of CVD are very similar to those of
heterogeneous catalysis.
◼ The reactant(s) adsorbed on the surface and then react on the
surface to form a new surface.
◼ The difference: using fractional surface area coverage
The growth of germanium films by CVD
Mechanism
s
Gas-phase dissociation

Adsorption

Adsorption

Surface reaction

rate-
limiting

Deposition rate
(nm/s) Fraction of the surface covered by H
Surface specific reaction rate (nm/s)
Fraction on the surface occupied by GeCl2
Adsorption

Adsorption

Rate of deposition
Gas-phase dissociation
At
equilibrium
 CATALYST DEACTIVATION

◼ The loss of catalytic activity as the reaction take place on the

catalyst (i.e., Ct decreases). Refer to the book by Butt and
Petersen “Activation, deactivation and Poisoning of Catalysts”
(1988)
◼ The adjustment for the decay of the catalysts:
◼ the reactions are divided into two categories
◼ separable kinetics

◼ nonseparable kinetics
The activity of the catalyst at time a (t)
1.0
t:

0
t
The rate of catalyst decay is a function of time, temperature and
concentration

Decay law Specific decay

constant
CATALYST DEACTIVATION TYPES

◼The loss of catalytic activity

◼sintering (aging)

◼fouling (coking)

◼poisoning
SINTERING (AGING)
◼ A loss of active surface area resulting from the
prolonged exposure to high gas-phase temperatures.
◼ The active surface area is lost by
◼ crystal agglomeration and growth of the metals deposted on the support
◼ narrowing or closing of the pores inside the catalyst pellet
◼ surface recrystallization
◼ the formation or elimination of surface defects (active sites)

◼ Sintering is usually negligible at temperature below

40% of the melting temperature of the solid.
◼ Second-order decay:
Conversion with catalyst decay example

The first order isomerization is carried out isothermally in a batch reactor

on a catalyst that is decaying as a result of aging. Determine the
conversion as a function of time.

Mole balance Rate law Stoichiometr

(Batch) y
COKING (FOULING)

◼ Common to reactions involving hydrocarbons.

◼ A carbonaceous (coke) material being deposited on the surface of a catalyst.
◼ The amount of coke on the surface after a time t:

concentration of carbon on the surface

◼ Coking can be reduced by running at elevated pressure and hydrogen-rich
streams.
◼ Catalyst deactivated by coking can usually be regenerated by burning off the
carbon.
POISONING
◼ The poisoning molecules become irreversibly
chemisorbed to active sites, reducing the number of sites
available for the main reaction.
◼ The poisoning molecule

◼ a reactant
◼ a product
◼ impurity
CATALYST DECAY IN A FLUIDISED BED
EXAMPLE
A gas-phase cracking reaction:

is carried out in a fluidised CSTR reactor. The feed stream contains 80%
crude (A) and 20% inert I. The crude oil contains sulfur compounds
which poison the catalyst.
Assuming that the cracking reaction is first-order in the crude 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 modelled as a well-mixed CSTR, determine the reactant
concentration, activity, and conversion as a function of time.
Mole balance Rate law
(CSTR)

non-steady state

constant
volume
uniformly distributed
catalysts

Stoichimetry (P = P0, T = T0)

Combinin
g

CA = f (t, a)

The two equations are solved simultaneously.

REACTION SYSTEMS TO HANDLE THE
DECAYING OF CATALYSTS

◼ Slow decay
◼ deactivation by poisoning
◼ temperature - time trajectories

◼ Moderate decay
◼ significant catalyst decay
◼ moving - bed reactors

◼ Rapid decay
◼ e.g., coking in heavier petroleum fractions cracking
◼ straight-through transport reactors (STTR)
 TEMPERATURE - TIME TRAJECTORIES

◼ Steadily increasing the feed temperature to the reactor to increase the reaction rate.
◼ The reaction rate remains constant with time:

For first-order
reaction

How the temperature should be increased with

 the decay
law

Eliminating T

t = 0, a = 1
Eliminating
a
MOVING - BED REACTORS
◼ Because catalyst decays significantly, continual
regeneration and/or replacement of the catalyst is
required.
◼ The catalyst is coked continuously as it moves through
the reactor until it exits the reactor. (p. 650)
◼ Steady-state: the feed rates of the catalyst and the
reactants do not vary with time
[Flow rate in] - [flow rate out] + [rate of generation] = [rate of
accumulation]
We need relationship between W and t.

When the solid catalyst is moving through the bed at a rate Us (mass/unit
time), and the weight of a catalyst is W, the contact time between the catalyst
and the reactant gas is:
STRAIGHT-THROUGH TRANSPORT REACTORS
(STTR)

◼ The catalyst pellets and the reactant feed enter together

and transported very rapidly through the reactor. (p. 655)
◼ The bulk density is very small. The particles are often
carried through at the same velocity as the gas velocity.
◼ Also known as a “circulating fluidized bed” (CFB).
A mole balance over a differential reactor volume at steady-state:

We need relationship between z and t.

When the solid catalyst is travelling through the reactor at a velocity UP, and
the time when it reaches a height z is:
 THE ORDER OF DEACTIVATION
in a CSTR reactor, the mole balance gives:

If this is a first-order
decay:

t
If this is a second-order
decay:

t
 in a PBR reactor, the mole balance gives:

If this is a first-order
decay:

t
 REACTION ENGINEERING AND
MICROELECTRONICS DEVICE FABRICATION

◼ Surface reactions play important role in the manufacture of

microelectronic and photonic devices and recording materials.
◼ The manufacture of an integrated circuit requires the
fabrication of a network of pathways for electrons.
◼ The principal steps include
◼ depositing material on the surface of a substrate (e.g. CVD)
◼ changing the conductivity of regions of the surface
◼ removing unwanted material

◼ Example: page 663

ETCHING
◼ Wet etching
◼ liquids such as HF or KOH to dissolve the layered material
◼ manufacture of micromechanical devices
◼ Dry etching
◼ gas-phase reaction
◼ highly reactive species, usually plasma, impinge on the
surface either to react with the surface, erode the surface, or
both
◼ manufacture of optoelectronic devices