Catalysis

Catalysts
• A catalyst is a substance that affects the rate of a reaction but emerges
from the process unchanged. A catalyst usually changes a reaction rate by
promoting a different molecular path ("mechanism") for the reaction.
• For example, gaseous hydrogen and oxygen are virtuaIly inerl at room
temperature, bur react rapidly when exposed to platinum.
• Catalysis is the occurrence, study, and use of catalysts and catalytic processes.
• The development and use of catalysts is a major part of the constant
search for new ways of increasing product yield and selectivity from
chemical reactions.
• Because a catalyst makes it possible to obtain an end product by a
different pathway with a Iower energy barrier. it can affect both the yield
and the selectivity.
• Normally when we talk about a catalyst, we mean one that speeds up a
reaction, although strictly speaking, a catalyst can either accelerate or
slow the formation of a particular product species.
• A catalyst changes only the rate of reaction; it does nor affect the equilibrium
 Gas

H› • 0,

kcxtinn i ”ncrdinzic
 Homogeneous catalysis
• concerns processes in which a catalyst is in solution with at least one of
the reactants. An example of homogeneous catalysis is the industrial 0x0
process for manufacturing normal isobutylaldehyde. It has propylene,
carbon monoxide, and hydrogen as the reactants and a liquid-phase
cobalt complex as the catalyst.
• Reactions carried out in supercritical fluids have been found to accelerate
the reactino rate greatly.' By manipulating the properties of the solvent in
which the reaction is taking place, interphase mass transfer limitations can
be eliminated.
A heterogeneous catalytic process involves more
than one phase:
• usually the catalyst is a solid and the reactants and products are in liquid
or gaseous form. Much of the benzene produced in this country today is
manufactured from the dehydrogenation of cyclohexane (obtained
from the distillation of crude petroleum) using platinum-on-alumina as
the catalyst.
• Sometimes the reacting mixture is in both the liquid and gaseous forms, as
in the hydro desulfurization of heavy petroleum fractions. Of these two
types of catalysis, heterogeneous catalysis is the more common type. The
simple and complete separation of the fluid product mixture from the
solid catalyst makes heterogeneous catalysis economically attractive,
especially because many catalysts are quire vaIuable and their reuse is
demanded.
 A Heterogeneous catalytic

• A heterogeneous catalytic reaction occurs at or

very near the fluid-solid interface.
• The principles that govern heterogeneous
catalytic reactions can be applied to both
catalytic and noncatalytic fluid-solid
reactions.
• The two other types of heterogeneous reactions
invoIve gas-Iiquid and gas-liquid-solid systems.
• Reactions between gases and Iiquids are
usually mass-transfer limited
 Catalyst Properties
• Because a catalytic reaction occurs at the fiuid-solid interface, a large
intercial area is almost always essential in attaining a significant reactian rate.
many catalysts, this area is provided by an inner porous structure {i.e., i solid
contains many tine pores, and the surface of these pores supplies the a
needed for the high rate of reaction).
• The area possessed by some porous materials is surprisingly large. A typical
silica-alumina cracking catalyst has a pc volume of 0.6 crn3/g and an
average pore radius of 4 nm. The corresponding surface area is 300 m2/g.
• A catalyst that has a Large area resulting from pores is called a poro catalyst.
• In some cases a catalyst consists of minute particles of an active material
dispersed over a less active substance called a support. The active material is
frequently a pure metal or metal alloy. Such catalysts are called supported
catalysts, as distinguished from unsupported catalysts. Catalysts can also
have small amounts of active ingredients added called promoters, which
increase their activity.
 Deactivation
Most catalysts do not maintain their activities at the same levels for indefinite
periods.
They are subject to deactivation, which refers to the decline in a catalyst's
activity as time progresses.
Catalyst deactivation may be caused by
1. aging phenomenon, such as a gradual change in surface crystal
struc- ture;
2. by poisoning, which is the irreversible deposition of a substance on the
active site; or
3. by fouling or coking, which is the deposit of carbon- aceous or
other material on the entire surface.

Deactivation may occur very fast, as in the catalytic cracking of petroleum naphthas,
where coking an the catalyst requires that the catalyst be removed after only a couple
of minutes in the reaction zone. In other processes poisoning might be very slow, as in
auto- motive exhausr catalysts, which gradually accumulate minute amounts of lead
even if unleaded gasoline is used because of residual lead in the gas station storage
tanks.
 Adsorption :
• For the moment, let us focus our attention on gas-phase reactions
catalyzed by solid surfaces. For a catalytic reaction to occur, at least one
and frequently all of the reactants must become attached to the
surface.
• This attachment is known as adsorption and takes place by two different
processes: physical adsorption and chemisorption. Physical adsorption is
similar to condensation.
• The process is exothermic, and the heat of adsorption is relatively small,
being on the order of 1 to 15 kcal/mol. The forces of attraction between
the gas molecules and the solid surface are weak. These van der Waals
forces consist of interaction between permanent dipoles, between a
permanent dipole and an induced dipole, and or between neutral atoms
and molecules.
• The amount of gas physically adsorbed decreases rapidly with increasing
temperature, and above its critical temperature only very small amounts
of a substance are physically adsorbed.
 Chemisorption
• The type of adsorption that affects the rate of a chemical reaction is
chemisorption. Here, the adsorbed atoms or molecules are held to
the surface by valence forces of the same type as those than occur
between bonded atoms in molecuIes. As a result the electronic
structure of the chemisorbed molecule is perturbed significantly,
causing it to be extremely reactive. Interaction with the catalyst
causes bonds of the adsorb reactant to be stretched. making them
easier to break.
• Like physical adsorption. chemisorption is an exothermic process,
but the heats of adsorption are generally of the same magnitude
as the heat of a chemical reaction (it.. 40 to 400 kJ/mol). If a
catalytic reaction involves chemisorption, it must be carried out
within the temperature rang whek chemisorption of the reactants
is appreciable
 Turnover frequency (TOR)
• In a landmark contribution to catalytic theory, Taylor suggested that a
reaction is not catalyzed over the entire solid surface but only at certain
active sites or centers. He visualized these sites as unsaturated atoms in
the solids that resulted from surface irregularities, dislocations, edges of
crystals. and cracks along grain boundaries. Other investigators have taken
exception to this definition, pointing out that other properties of the solid
surface are also important. The active sites can also be thought of as
places where highly reactive intermediates (i.e., chemisorbed species) are
stabilized long enough to react. This stabilization of a reactive
intermediate is key in the design of any catalyst. However, for our
purposes we wilI define an active site as a point on the catalyst surface
that can form strong chemical bonds with an adsorbed atom or molecule.
• One parameter used to quantify the activity of a catalyst is the turnover
frequency (TOR. f. It is the number of molecules reacting per active site
per second at the conditions of the experiment. Wen a metal catalyst such
as platinum is deposited on a support, the metal atoms are considered
active sites. The dispersion, D, of the catalyst is the fraction of the metal
atoms deposited that are on the surface.
uJ
Hydroqenatton
Turnover Frequency (mot ecutmfaRo •

IO

IO
O
n J9omari zo
C ycli zof ion
A1kone Hydroganoiyss,
lxomsrizoton, Cyclizotion
-q
IO

200 400 600

Temperotur e (K) 8OO
Hifiure J0•¥ R:in¿* t›f ‹urn‹›*'*‹ t"rc«nci«^ a« .s fun<ii‹›i› fcr Jit"f•rcni r»:›=‹ien•
an‹J tciapcra urcx. .1‹Jnptcd from C. A. Sort›‹›rj:ii. 7/irrru/«r /i‹/// /r› Air o‹-r
 Classification of Catalysts
1. Alkylation and Dealkylation Reactions
2. Isomerization Reactions
3. Hydrogenation and Dehydrogenation Reactions. The bonding strength
be- tween hydrogen and metal surfaces increases with an increase in
vacant d-orblt- als. Maximum catalytic activity will not be realized if the
bonding is too strong and the products are not readily desorbed from
the surface. Consequently, this maxjrnum in catalytic activity occurs
when there is approximately one vacant d-orbital per atom.
4. Oxidation Reactions. The transition group elements (group VIII) and
sub- group I are used extensively in oxidation reactions
5. Hydration and Dehydration Reactions. Hydration and dehydration
catalysts have a strong affinity for water.
6. HaIogenation and DehaIogenation Reactions. Usually, reactions of this
type take place readily without utilizing catalysts. However, when
selectivity of the desired product is low or it is necessary to run the
reaction at a lower temperature, the use of a catalyst is desirable
 C»Clt, AgCl. Pd

5. AI5yIatioo-<AaIkylnuon
4. Hy4sog«natios••dctiydrogcsazion
3. Oxidatian Cu. Ag, Ni, ¥jOj
 Steps in a Catalytic Reaction

Tx8LF. ! o-z STE,PS IN a CaTacwic Rzacnou

1. !*I•=* ‹ran»frr ‹difFurinn› nf ñx rcacuntlsj (c.g.. species ,If from the bulk éuid to th• cxtc
surface nf the ca‹atyét pellc!
1. DiPu.tion of Ie rcxcient fom the pore maul ‹hrough ‹he catalyst pore» Ie the
immedia vicinity of1ke internal caial¿tic surface
1. Adsorption ‹›f rcaciacl A ono the catalyst surface
J. Rcaciion o« th• surfacc of tkc catalyst (c.g., A By
5. Dcsorj¥tion of the products (c.g.. By fom the wrfwc
6. Di7usioe .of the p6oJwtl from ‹he in‹c6er of Ie pJfci la the pore mouth ai ihc utcmal

7. Mnss Lrazi.¥fcr of the products fom the external pellet surface ‹o 1c¥uIk Ruid
 lntarnal

Figure IO-6 $tcps in a heterogcneous catalytic reaction.

 The overall rate of reaction
• is equal ra the sate of the slowest step in the mechanism.
• When the diffusion steps (1,2,6, and 7 in Table 10-2) are very fast
compared with the reaction steps (3, 4. and S), the concentrations in
the immediate vicinity of the active sites are indistinguishable from
those in the bulk fluid. In this situation, the mass transpont or diffusion
steps do not affect the overall rate of the reaction.
• In other situations, if the reaction steps are very fast compared with the
diffusion steps, mass transport does affect the reaction rate.
• In systems where diffusion from the bulk gas or liquid to the catalyst
surface or to the mouths of catalyst pores affects the rate, changing the
flow conditions past the catalyst should change the overall reaction rate.
In porous catalysts, on the other hand, diffusion within the catalyst pores
may limit the rate of reaction. Under these circumstances, the overall rate
will be unaffected by external flow conditions even though diffusion
affects the overall reaction rate.
 Where Are We Heading?
• One of the tasks of a chemical reaction engineer is to analyze rate data and to
deveIop a rate law that can be used in reactor design.
• We will postulate catalytic mechanisms and then derive rate laws for the various
mechanisms. The mechanism will typically have an adsorption step, a surface
reaction step, and a desorption step, one of which is usually rate-limiting.
Suggesting mechanisms and rate-limiting steps is not the first thing we normally do
when presented with data. However, by deriving equations for different
mechanisms, we will observe the various forms of the rare law one can have in
heterogeneous catalysis.
• Knowing the different forms that catalytic rate equations can take, it will be easier to
view the trends in the data and deduce the appropriate rate law. This deduction is
usually what is done first in industry before a mechanism is proposed. Knowing the
form of the rate law, one can then numerically evaluate the rate law parameters and
postulate a reaction mechanism and rate-limiting step that is consistent with the
rate data. Finally, we use the rate law to design catalytic reactors.
• This procedure is shown in Figure 10-7. The dashed lines represent feedback to
obtain new data in specific regions le.g., concentrations, temperature) to
evaluate the rate law parameters more precisely or to differen- tiate between
reaction mechanisms.
 Spxh% gs

Reastor deslp1

Flgurg 10-7 Colleciing infomalioo for caialyiic reacior design.