Catalysis and catalytic reactors

 Catalysts
 Definitions
Catalyst: a substance that affects the rate of a reaction but emerges from the
process unchanged
Catalysis: the occurrence, study, and use of catalysts and catalytic processes
Homogeneous catalysis: catalyst is in solution with at least one of the
reactants

An example of homogeneous catalysis is the industrial 0x0 process for manufacturing nor
mal isobutylaldehyde. It has propylene, carbon monoxide, and hydrogen as the reactants a
nd a liquid-phase cobalt complex as the catalyst.
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

A heterogeneous catalytic reaction occurs at or very near the fluid-

solid interface
 Catalyst properties
Catalytic reaction occurs at the fluid-solid interface: large surface area
Catalyst type: porous, molecular sieves, monolithic, supported, unsupported
Because a catalytic reaction occurs at the fiuid-solid interface, a large
Interfacial area is almost always essential in attaining a significant
reaction rate. In many catalysts, this area is provided by an inner
porous structure {i.e.solid contains many tiny pores, and the surface of
these pores supplies the area needed for the high rate of reaction), The
area possessed by some porous material is surprisingly large. A typical
silica-alumina cracking catalyst has a pore volume of 0.6 cm3/g and
an average pore radius of 4 nm. The corresponding surface area is 3
00 m2/g.

Porous Catalyst
A catalyst that has a Large area resulting from pores is called a porous
catalyst. Examples of these include the Raney nickel used in the
Hydrogenation of vegetable and animal oils, the platinum-on-alumina
used in the reforming of petroleum naphthas to obtain higher octane
ratings, and the promoted iron used in ammonia synthesis
Molecular Sieve
Sometimes pores are so small that they will admit small molecules but
prevent large ones from entering. Materials with this type of pore are
called molecular sieves, and they may be derived from natural
substances such as certain clays and zeolites, or be totally synthetic,
such as some crystalline aluminosilicates.
 The pores can control the residence time of various molecules near
the catalytically active surface to a degree that essentially allows
only the desired molecules to react.
One example of the high selectivity of zeolite cataIysts is the formation
of xylene from toluene and methane. Here benzene and toluene enter th
rough the pore of the zeolite and react on the interior surface to form a
mixture of ortho. meta. And para xylenes. However, the size of the pore
mouth is such that only para-xylene can exit through the pore mouth as
meta and ortho xylene with their methyl group on the side cannot fit
through the pore mouth. There are interior sites that can isomerize
ortho and meta to para-xylene. Hence we have a very high selectivity
to form para-xylene
Chris Tran, Xiao-Qing Yang, Deyang Qua
Journal of Power Sources 195
Monolithic Catalyst
Not all catalysts need the extended surface provided by a porous
structure, however. Some are sufficiently active so that the effort
required to create or nonporous. a porous catalyst would be wasted.
For such situations one type of catalyst is the monolithic catalyst.
Monolithic catalysts are normally encountered in processes where
pressure drop and heat removal are major considerations.
 They can be porous (honeycomb) or nonporous.
 Platinum is a primary catalytic material in the monolith.
Supported 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.
 Examples of supported catalysts are the packed-bed catalytic
converter automobile,
 the platinum-on-alumina catalyst used in petroleum reforming, and
the vanadium pentoxide on silica used to oxidize sulfur dioxide in
manufacturing sulfuric acid. On the other hand, the platinum gauze
for ammonia oxidation, the promoted iron for ammonia synthesis, and
the silica-alumina dehydrogenation catalyst used in butadiene
manufacture typify unsupported catalysts.
Deactivation of the catalyst
Most catalysts do not maintain their activities at the same levels for
indefinite periods. They are subject to deactivation, which refers to th
e 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 structure;
 (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 carbonaceous
or other material on the entire surface. Deactivation may occur
very fast, as in the catalytic cracking of petroleum naphthas,
where coking on 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 automotive
exhaust catalysts, which gradually accumulate minute amounts of
lead even if unleaded gasoline is used because of residual lead in th
e
Physical adsorption and Chemisorption
For a catalytic reaction to occur, at least one and frequently all of the r
eactants 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. 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 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 that occur
between bonded atoms in molecules.
 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 adsorbed reactant
to be stretched. Making them easier to break.
• Catalyst deactivation: aging phenomenon, poisoning, fouling or coking
• Adsorption: physical adsorption & chemisorption

• Active site: a point on the catalyst surface that can form strong chemical bonds
with an adsorbed atom or molecule
• Turnover frequency (TOF): the number of molecules reacting per active site
per second at the conditions of the experiment
• Dispersion: the fraction of the metal atoms deposited that are on the surface
 Classification of catalysts
 Alkylation and dealkylation reactions

 Isomerization reactions
Normal paraffins to isoparaffins over Pt on Al2O3 (hydrogenation site + acid site)
 Hydrogenation and dehydrogenation reactions

 Oxidation reactions
 Hydration and dehydration reactions

Alumina, silica-alumina gels, clays, phosphoric acid, and phosphoric acid salts on inerts carriers

 Halogenation and dehalogenation reactions

Halogenation of hydrocarbon: supported copper and silver halide
Hydrochlorination: mercury copper or zinc halide
 Steps in a catalytic reaction
  Adsorption isotherms
Adsorption of A on a site S

Site balance

Total concentration of sites Molar concentration of vacant sites

Consider the adsorption of a gas onto the surface of a catalyst. Adsorption data are
frequently reported in the form of adsorption isotherms.
• Adsorption of CO on metal surfaces
CO adsorption as a molecular CO (molecular or nondissociated adsorption)
If, Carbon monoxide is adsorbed as oxygen and carbon atoms instead of molecular CO.
CO adsorption as oxygen and carbon atoms (dissociative adsorption)

• Rate of molecular adsorption

Elementary reaction

Independent of temperature Exponential increase with increasing temperature

Adsorption equilibrium constant

Because carbon monoxide is the only material adsorbed on the catalyst

At eq. rAD=0

Langmuir isotherm
• Rate of dissociative adsorption

Exponential increase with increasing temperature

Decrease with increasing temperature

At eq. rAD=0
 • When more than one substance is present

 Surface reaction

Rate of adsorption of A onto a solid surface

• Surface reaction model
 Single site

Surface reaction equilibrium constant = kS/k-S

 Dual site
 Reaction involving either single- or dual-site mechanism
: Langmuir-Hinshelwood kinetics

 Eley-Rideal
 Desorption

Desorption equilibrium constant

Adsorption equilibrium constant

 Rate-limiting step
Heterogeneous reaction at steady state
  Langmuir-Hinshelwood approach
① Each reaction step as molecular or atomic adsorption, and single- or dual site
reaction
② Rate law for the individual steps assuming all steps are reversible
③ Postulating RDS and the others for eliminating all coverage-dependent terms
*Uniform surface: surface activity toward adsorption, desorption, or surface reaction
is independent of coverage

Ex, adsorption-limited reaction Ex, surface-limited reaction

 Synthesizing a rate law, mechanism, and rate-limiting step
 Adsorption of cumene

 Surface reaction

Surface reaction
equilibrium constant

Propylene is not adsorbed on the surface

 Benzene desorption

Desorption is the reverse of the

adsorption

No accumulation of reacting species on the surface

 RDS: adsorption of cumene
Rate law of Adsorption

Need to express Cv and CC·S in terms of PC, PB, and PP

For steady-state operation

For adsorption-limited rxn, kA << kS and kD
 very small value of rS/kS and rD/kD, while relatively large value of rAD/kA

Rate law of surface reaction

For adsorption-limited reactions

Rate law of desorption

 for the reaction

Concentration of vacant site

Initial rate as a function of the partial pressure of cumene

Initially, no product
 RDS: surface reaction
Rate law of surface reaction

Initial rate

At low partial pressures of cumene

At high partial pressures of cumene
 RDS: Desorption of benzene
Rate law of desorption

KC: Cumene adsorption constant

For PP=PB=0
 Summary of the cumene decomposition

Consistent with the assumption that

surface reaction is RDS

For adsorbing inert in the feed

Adsorption of the inert is at equilibrium

The rate law for surface reaction control when an adsorbing inert is present
 Reforming catalysts

•Dual site mechanism

•Assume a rate-limiting step (surface reaction step)

•Find the expression for concentration of the adsorbed species

•Write a site balance

•Derive the rate law

•Compare with data

 Rate laws derived from the pseudo-steady state hypothesis
• Using PSSH rather than setting

• If more than two step is rate-limiting or if some of the steps are irreversible or if none of the
steps are rate-limiting
Ex, isomerization of n-pentene to iso-pentene by following mechanism
• Rate law for irreversible surface reaction

•Net rates of generation of N·S and I·S sites

 If surface reaction is rate-limiting

 Temperature dependence of the rate law

Surface-reaction-limited irreversible

As temperature increases, KA & KB decrease

(adsorption is exothermic)

For a reversible isomerization

 Heterogeneous data analysis for reactor design
• Developing an algebraic rate law consistent with experimental observations
• Analyzing the rate law in such a manner that the rate law parameters can readily be extracted
from the experimental data
• Finding a mechanism and rate-limiting step consistent with the experimental data
• Designing a catalytic reactor to achieve a specified conversion
 Deducing a rate law from the experimental data
Assume that the reaction is essentially irreversible

• Dependence on the product methane

If methane were adsorbed on the surface

However, from run 1 & 2:

methane is either very weakly adsorbed or goes directly into the gas phase

• Dependence on the product benzene

From run 3 & 4

• Dependence on toluene
From run 10 & 11 (at low concentrations of toluene)
From run 14 & 15 (at high concentrations of toluene)
• Dependence on hydrogen
From run 7, 8, 9
 Finding a mechanism consistent with experimental observations

Surface reaction-limited mechanism

Neglecting reverse reaction

 Evaluation of the rate law parameters
To obtain a linear relationship between measured variables

Regression using the equation

 Reactor design

Example 10-3 PBR design

The hydrodemethylation of toluene is to be carried out in a PBR. Plot the conversion, the pressure
ratio, y, and the partial pressures of toluene, hydrogen, and benzene as a function of catalyst
weight. The molar feed rate of toluene to the reactor is 50 mol/min, and the reactor is operated at
40 atm and 640oC. The feed consists of 30% toluene, 45% hydrogen, and 25% inerts. Hydrogen is
used in excess to help prevent coking. The pressure drop parameter, , is 9.8 x 10-5 kg-1. Also
determine the catalyst weight in a CSTR with a bulk density of 400 kg/m3 (0.4 g/cm3).
• Design equation

• Rate law

• Stoichiometry

Maximum catalyst weight

Fluidized CSTR catalyst weight necessary to achieve the same conversion
 Catalyst deactivation
Reaction over decaying catalysts
• Nonseparable kinetics

• Separable kinetics

Possible to study catalyst decay and reaction kinetics independently

Rate of catalyst decay For a first order decay

For a second order decay

Depending on the gas catalytic system being used and the reason or
mechanism for catalytic decay
 Types of catalyst deactivation
• Deactivation by sintering (aging)

Amount of sintering in terms of the active surface area

Example 10-5 Calculating conversion with catalyst decay in batch reactors
The first-order isomerization is being carried out isothermally in a batch reactor on a catlyst that
is decaying a result of aging. Derive an equation for conversion as a function of time

• Design equation

• Rate law

• Decay law

• Stoichiometry
• Combining
• Deactivation by coking or fouling

Amount of coke on the surface after a time t

Concentration of carbon on the surface (g/m2)

A & n: fouling parameter, function of the feed rate

Activity & amount of coke on the surface

or
• Deactivation by poisoning
 Poison in the feed

Dividing by Ct0 & letting f be the fraction of the total number of sites poisoned
 Packed-bed reactors

 Poisoning by either reactants or products

For separable deactivation kinetics

For first-order decay (n=1)

 Empirical decay laws
Example 10-6 Catalyst decay in a fluidized bed modeled as a CSTR
The gas-phase cracking reaction is carried out in a fluidized CSTR. The feed stream contains 80%
gas oil and 20% inert. The gas oil contains sulfur compounds. Which poison the catalyst. As a first
approximation we will assume that the cracking reaction is first order in the gas oil 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. The volumetric feed rate to the reactor is 5000 m3/h.
there are 50000 kg of catalyst in the reactor and the bulk density is 500 kg/m3
 Temperature-time trajectories
 Slow decay
 Constant conversion by increasing the feed temperature

For a first-order reaction

Neglecting any variations in concentration

 Moving-bed reactors
 Significant decaycontinual regeneration or replacement of the catalyst
 moving-bed and straight-through transport reactor

 Mole balance on reactant A over ΔW

Reaction rate at any time t

Combining activity equation with mole balance

Decay rate law

&
Contact time
combining with decay rate law

(Mass/time)
Example 10-7 Catalytic cracking in a moving-bed reactor
 Dimensionless decay time

Damkohler number for a second-order

reaction
Conversion in a moving bed where a
second-order reaction is taking place

• Heat effects in moving beds

Energy balance on the gas phase Wall surface area per mass of catalyst

Pipe diameter Bulk catalyst density

Energy balance on the solid catalyst External surface area of the catalyst pellet per
unit mass of catalyst bed

Catalyst loading Heat capacity of solid Pellet diameter

 Straight-through transport reactor (STTR)

 Very rapid deactivation

 production of gasoline from the cracking of heavier petroleum fractions
Mole balance on the reactant A

The time for catalyst pellet to reach a height z

Catalyst particle velocity

 Summary
 Types of adsorption: chemisorption, physical adsorption
 Langmuir isotherm

 Sequence of steps for the solid-catalyzed isomerization

 Rate of adsorption, surface reaction, and desorption

 If surface reaction is rate-limiting

 Catalyst deactivation
 Temperature-time trajectory
 Moving-bed reactor

 Straight-through transport reactor