1.

1 Catalysts

1.2 Steps in Heterogeneous

Catalytic Reactions

1.3 Rate Limiting Steps

1.4 Temperature Dependence

of Catalytic Reaction Rates

1.5 Langmuir-Hinshelwood
Kinetic

1.6 Designing Catalytic

Reactors

1.7 Deactivation of Catalyst

CHE505: REACTION ENGINEERING II 1

THE PACKED BED REACTOR

Most used as industrial reactor

Typically a tank or tube filled with catalyst pellets with

reactants entering at one end and products leaving at the
other.

The fluid flows in the

void space around the
pellets and reacts on
and in the pellets.

Figure: Packed bed

reactors, which may be
a single bed, many
tubes, or a single tube
filled with catalyst
pellets.

Multitube reactors allow efficient heat transfer for exothemic or

endothemic reactions 2
 Assume no mixing  The fluid in a packed bed reactor flows
from one end of the reactor to the other

Mass balance:

 Single reaction  Multiple reaction

dC j dC j
u  jr Reaction u   ij ri
dz rate dz i

Average velocity of the fluid Kinematic velocity

flowing around the catalyst
particles

3
 Total
reactor volume Volume Volume
occupied by the occupied by the
fluid catalyst

Volume occupied
by the fluid

Void fraction or the fraction of

the reactor volume occupied by
the fluid

4
THE SLURRY REACTOR & FLUIDIZED BED REACTOR

The fluid and the catalyst are stirred instead of having the
catalyst fixed in a bed.

Fluid is a liquid, we call this a slurry reactor.

Catalyst pellets or powder is held in a tank through which

catalyst flows.
 The stirring must obviously be fast enough to mix the fluid
and particles
To keep the particles from settling out, catalyst particle
sizes in a slurry reactor must be sufficiently small.

If the catalyst phase is another liquid that is stirred to

maintain high interfacial area for reaction at the interface,
we call the reactor an emulsion reactor

5
Fluid is a gas:

It is difficult to stir solid particles and gas mechanically

 But this can be simply accomplished by using very small
particles and flowing the gas such that the particles are
lifted and gas and particles swirl around the reactor.
 We call this reactor a Fluidized bed

The moving fluid in these reactors is frequently well mixed

within the reactor; so the mass balance on reactant species A
is that of a CSTR

The reactor residence time is now:

6
Slurry reactor (left) for liquid solid reactions and fluidized bed reactor
(right) for well-mixed gas-solid reactions.. The slurry reactor is
generally mixed and is described by the CSTR model, while the
fluidized bed is described by the PFTR or CSTR models

7
RISER REACTOR

Figure show a riser reactor in which the catalyst is carried

with the reactants and separated and returned to the
reactor.

In this reactor the flow velocity is so high that

the solids are entrained in the flowing fluid
and move with nearly the same velocity as the
fluid.

The solids are then separated from the effluent

gases at the top of the reactor by a cyclone,
and the solids are returned to the reactor.

The flow profile of this reactor is incompletely

mixed, and in the limit there is no mixing at
all to yield the PFTR.

8
The flow profile of this reactor is incompletely
mixed, and in the limit there is no mixing at
all to yield the PFTR.

Thus the riser reactor behaves identically to

the packed bed reactor (a PFTR) with suitable
modification of the definition of τ

9
SURFACE AND ENZYME REACTION RATES

ASSUMPTION??

 The catalyst is in a solid phase with the reactants and

products in a gas or liquid phase.

 All reaction occurs on the surface of the catalyst (there is

no reaction in the fluid phase).

The surface reaction rate has the units of moles per unit area of
catalyst per unit time, which we will call r”.

Pseudohomogeneous
rate
(moles/volume time) surface area of catalyst per
volume of reactor 10
SURFACE AND ENZYME REACTION RATES

A PACKED BED REACTOR

 filled with pellets with surface area Sgρc, per unit volume
of pellet (units of cm-i, for example)

 Sg :surface area per unit weight of catalyst (area per gram

is a common set of units)

 ρc : density of a catalyst pellet

surface area of the catalyst Volume of Fraction occupied

based on pellet volume reactor by the catalyst.

11
SURFACE AND ENZYME REACTION RATES

A PACKED BED REACTOR

 The pellet is usually porous, and there is fluid (void space)

both between catalyst pellets and within pellets

 SPACE TIME, τ

volume of fluid in a reactor


volumetric flow rate passes through t he reactor

HOMOGENEOUS REACTOR HETEROGENEOUS REACTOR

V volume of reactor V
    
0 inlet volu metric flow rate 0
12
 1.1 Catalysts

1.2 Steps in Heterogeneous

Catalytic Reactions

1.3 Rate Limiting Steps

1.4 Temperature Dependence

of Catalytic Reaction Rates

1.5 Langmuir-Hinshelwood
Kinetic

1.6 Designing Catalytic

Reactors

1.7 Deactivation of Catalyst

CHE505: REACTION ENGINEERING II 13

So far, we have assumed that the
activity of the catalyst remains constant
throughout the catalyst’s life.
Ct = total
concentration
of active sites

Unfortunately, this
is not the case in
most industrially
significant catalytic
dCt / dt = 0
reactions!!

Catalyst
Deactivation
14
• Defined as the loss of catalytic activity that occurs as
the reaction takes place on the catalyst.

• Major problem faced by most industries when

conducting catalytic reactions.

• Known to strongly affect the conversion, hence as a

result, affect the performance of the reactor itself.

• Catalysts have only a limited lifetime. Some lose their

activity after a few minutes, others last for more
than ten years.

• The maintenance of catalyst activity for as long as

possible is of major economic importance in industry.

15
In catalyst deactivation, the most important quantity that
need to be described is the activity of the catalyst, a(t):

?
• Naturally, the activity of catalyst is going to change
(decrease) with time

• A typical curve of the activity

as a function of time is:

Fogler (4th Ed.)-Elements of Chemical Reaction Engineering, Copyright 

2006 Pearson Education, Inc. 16
• Catalyst deactivation is the result of number of
unwanted chemical and physical changes.

• Decline in activity is due to:

- Blocking of the catalytically active sites
- Loss of catalytically active sites due to chemical,
thermal or mechanical processes.

17
TYPES OF CATALYST DEACTIVATION

• The decaying of catalyst activity can traditionally

happens through 3 ways:

Types of Catalyst Deactivation

Poisoning
18
• Loss of catalytic activity due to a loss of active surface area (due to
prolonged exposure to high gas-phase temperatures).

• The active surface area may be lost by:

– Crystal agglomeration and growth of the metals deposited on the
support.

– Loss of activity by narrowing or closing of the pores inside the

catalyst pellet.

Fogler (4th Ed.)-Elements of Chemical Reaction Engineering, Copyright  2006 19 .com

www. Chemical Engineering Guy
Pearson Education, Inc.
 This mechanism of decay is common to reactions
involving hydrocarbon.

It results from a carbonaceous (coke) material from

fluid phase being deposited on the surface of a catalyst,
causing activity loss due to blocking of sites and/or
pores.

Fogler (4th Ed.)-Elements of Chemical Reaction Engineering, Copyright  2006 Pearson www. Chemical Engineering Guy .com
Education, Inc.
20
When the catalyst is already Fouled or coked, the
material is normally called “spent catalyst”

Fresh catalysts Spent Catalysts

21
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The amount of coke deposited on the surface after a time t has
been found to obey the following empirical relationship
(Voorhies, 1945):

Cc  At n

Cc is the n is the fouling

concentration of parameter, value
carbon on the typically  0.5
surface (g/m2)
A is the fouling parameter,
which is a function of
feedstock and reactor type

Coke deposited can be measured using TGA, DTA or by

monitoring the evolution of CO2 and H2O.

Fogler (4th Ed.)-Elements of Chemical Reaction Engineering, Copyright  2006 Pearson 22

Education, Inc.
 Poisoning molecules become irreversibly chemisorbed to active
sites.
This reduce the number of sites available for the main reaction.

The poisoning molecule, P may be a reactant or a product in

the main reaction, but normally is the impurities in the feed
stream.

www. Chemical Engineering Guy .com, www.n-u.co.jp 23

Petroleum feed stocks contain trace impurities such as:
sulfur, lead, and other components which are too
costly to remove.

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25
Decline on catalyst’s activity
with time

Sintering/Aging
phenomena
Loss of catalytic activity
due to loss of active
surface area (due to
prolonged exposure to
high T).

Poisoning
irreversible chemisorption
of substances on the
active sites.

Fouling/coking
carbonaceous deposition
on active catalytic sites.
26
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 REFER TEXTBOOK:

Fogler, H.S. (2006). Elements of Chemical

Reaction Engineering, 4th Edition, New
Jersey: Prentice Hall

(pp.710)

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