SOLID CATALYZED

REACTIONS
Prof. Anand Tiwari

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Heterogeneous Reactions
■ Rate equation for heterogeneous reactions
■ combining linear & non-linear rate expressions
■ the concept of rate controlling step, linearization of a non-linear rate equation
■ contacting patterns for two phase systems

Reaction Kinetics Effect of Mass

Rate law –rA =k 𝐶𝑟𝑛 Transfer

Reactor Design
and operation

Effect of Velocity distribution Heat Effects

(Flow pattern)
Heterogeneous Reactions
■ A reaction is heterogeneous if it requires the presence of at least two phases to proceed
at the rate that it does.
■ It is immaterial whether -
– the reaction takes place in one, two, or more phases;
– at an interface;
– whether the reactants and products are distributed among the phases
– are all contained within a single phase.
■ All that counts is that at least two phases are necessary for the reaction to proceed
■ For these systems there are two complicating factors that must be accounted for
– The complication of the rate expression,
– The complication of the contacting patterns for two-phase systems
■ Heterogeneous reactions are divided in two classes
– Uncatalyzed
– Catalyzed
Important Characteristics
■ Heterogeneous reactions are complicated by the fact that before substances in different
phases can react, they must migrate to at least the interface.
■ In addition to chemical affinity, certain physical factors which affect the rate of mass
transfer between phases also affect the overall rate of heterogeneous reaction. These
factors are as follows:
– Amount of interfacial surface, to which the rate may be proportional under some
conditions. Interfacial surface is created by grinding solids, or dispersion of fluids
with spray nozzles or agitators, or dispersion by percolation through beds of solid
particles.
– Rate of diffusion of fluids to and across the interfacial film, which is influenced
principally by the relative velocities of the two phases, the pressure of the gas
phase, and to a minor extent the temperature of the system, in addition to the
physical properties of the reactants and the geometry of the system.
– Rate of diffusion of the products away from the reaction zone, which is of
importance only with reversible reactions, unless the concentrations of the products
are sufficient to influence the diffusivities of the

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Heterogeneous Reaction
■ The complication of the rate expression –
– movement of component from one phase to another must be considered in rate
equation
– The rate expression incorporates mass transfer term
– These mass transfer terms are different depending on process
Example
■ Dilute A diffuses through a stagnant liquid film onto a plane surface consisting of B,
reacts there to produce R which diffuses back into the mainstream. Develop the
overall rate expression for the L/S reaction

Linear and Nonlinear Process

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Diffusion of A from Bulk to Surface

Irreversible reaction of A with B

At Steady State " "

𝑟𝐴1 = 𝑟𝐴2

■ This result shows that 1/kl, and 1/k" are additive resistances.
■ The addition of resistances to obtain on overall resistance is permissible only when the
rate is a linear function of the driving force and when the processes occur in series.

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Heterogeneous Reactions
■ The complication of contacting pattern of the phases – many ways that two phases can
be contacted, and for each the design equation will be unique.
■ Design equations for these ideal flow patterns may be developed without too much
difficulty. However, when real flow deviates considerably from these, we can do one of
two things:
■ We may develop models to mirror actual flow closely
■ we may calculate performance with ideal patterns which "bracket" actual flow
■ Most real reactors for heterogeneous systems can be satisfactorily approximated by one
of the five ideal flow patterns with exception like fluidized bed reactor
Contacting patterns
Catalysis
■ 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.
– Gaseous hydrogen and oxygen are virtually inert at room temperature, but react
rapidly when exposed to platinum.
– Important step is to pass over the activation energy barrier
■ A catalyst changes only the rate of a reaction; it does not affect the equilibrium
Catalysis
■ A heterogeneous catalytic reaction involves more than one phase; usually the catalyst is
a solid and the reactants and products are in liquid or gaseous form
■ The simple and complete separation of the fluid product mixture from the solid catalyst
makes heterogeneous catalysis economically attractive, because many catalysts are quite
valuable and their reuse is demanded.
■ 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 non-catalytic fluid–solid reactions.
■ The two other types of heterogeneous reactions involve gas–liquid and gas–liquid–solid
systems. Reactions between gases and liquids are usually mass-transfer limited
Catalyst Properties
■ Large surface area - because a catalytic reaction occurs at the fluid–solid interface,
large interfacial area is almost always essential in attaining a significant reaction
rate.
■ Easily separable - It should have distinct phase so that it can be separated when
change needed.
■ Good Thermal Strength – to avoid any changes in thermal properties or structure or
deactivation
■ Good Mechanical Strength – to avoid any wear or tear losses
Terms
■ 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 in an
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.

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 Steps in Heterogeneous Rxns
1. Mass transfer (diffusion) of the reactant(s)
(e.g., species A) from the bulk fluid to the
external surface of the catalyst pellet
2. Diffusion of the reactant from the pore
mouth through the catalyst pores to the
immediate vicinity of the internal catalytic
surface
3. Adsorption of reactant A onto the catalyst
surface
4. Reaction on the surface of the catalyst
(e.g., A  B)
5. Desorption of the products (e.g., B) from
the surface
6. Diffusion of the products from the interior
of the pellet to the pore mouth at the
external surface
7. Mass transfer of the products from the
external pellet surface to the bulk fluid

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■ There are many variations of the situation
■ Sometimes, two reactants are necessary for a reaction to occur, and both of these may
undergo the steps listed above.
■ Other reactions between two substances may have only one of them adsorbed.
■ What is needed is to treat individually the steps involved in heterogeneous catalytic reactions.
■ First only adsorption, surface reaction, and desorption (3, 4, 5) are considered
■ Assume that the diffusion steps (1, 2, 6, and 7) are very fast so that the overall reaction rate is
not affected by mass transfer in any fashion.
■ One of the tasks of a chemical reaction engineer is to analyze rate data and to develop a rate
law that can be used in reactor design.
■ Rate laws in heterogeneous catalysis seldom follow power-law models and hence are
inherently more difficult to formulate from the data.
■ To develop an in-depth understanding and insight as to how the rate laws are formed from
heterogeneous catalytic data, we are going to proceed a reverse approach is normally done in
industry when one is asked to develop a rate law.
■ 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

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■ By deriving equations for different mechanisms, one may find various forms of the rate
law 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 are consistent
with the rate data.
■ Finally, we use the rate law to design catalytic reactors.

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Step 1 – External Mass Transfer
■ Diffusion from the Bulk to the External Surface of the Catalyst
■ Let’s assume that the transport of A from the bulk fluid to the external surface of the
catalyst is the slowest step in the sequence.
■ Lump all the resistance to transfer from the bulk fluid to the surface in the mass-
transfer boundary layer surrounding the pellet.
■ In this step the reactant A, which is at a bulk concentration CAb must travel (diffuse)
through the boundary layer of thickness δ to the external surface of the pellet where
the concentration is CAs

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■ This rate of transfer will depend on various factors along with concentration gradient
■ Rate = kc(CAb – CAs)
■ kc is called mass transfer coefficient and is a function of hydrodynamic conditions
fluid velocity and particle diameter
■ This mass transfer is inversely proportional to the thickness of the boundary layer
and proportional to diffusion coefficient

■ At very high velocities the boundary layer thickness is so small that it offers no
resistance at all to diffuse
■ The resistance also decreases as the particle size is decreased
■ This mass transfer finally reaches a plateau where CAb = CAs

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Step 2 – Internal Diffusion
■ Consider that we are operating at a fluid velocity where external diffusion is no longer the
rate-limiting step and that internal diffusion is the slowest step.
■ In Step 2 the reactant A diffuses from the external pellet surface at a concentration CAs
into the pellet interior, where the concentration is CA.
■ As A diffuses into the interior of the pellet, it reacts with catalyst deposited on the sides
of the catalyst pellet’s pore walls.
■ For large pellets, it takes a long time for the reactant A to diffuse into the interior,
compared to the time that it takes for the reaction to occur on the interior pore surface.
■ Under these circumstances, the reactant is only consumed near the exterior surface of
the pellet and the catalyst near the center of the pellet is wasted catalyst.
■ On the other hand, for very small pellets it takes very little time to diffuse into and out of
the pellet interior and, as a result, internal diffusion no longer limits the rate of reaction.
■ When internal mass transfer no longer limits the rate of reaction, the rate law can be
expressed as - Rate = krCAs

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■ These steps (2 through 6) are not at all affected by flow conditions external to the
pellet.
■ So we are going to choose our pellet size and external fluid velocity such that neither
external diffusion nor internal diffusion is limiting

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Adsorption Isotherm
■ Chemisorption is usually a necessary part of a catalytic process
■ The letter S will represent an active site; alone, it will denote a vacant site, with no atom,
molecule, or complex adsorbed on it.
■ The combination of S with another letter (e.g., A.S) will mean that one unit of species A
will be chemically adsorbed on the site S.
■ The adsorption of A on a site S is represented by A + S  A.S
■ The total molar concentration of active sites per unit mass of catalyst is equal to the
number of active sites per unit mass divided by Avogadro’s number and will be labeled
Ct (mol/g-cat)
■ Similarly, The molar concentration of vacant sites, Cv (mol/g-cat)
■ In the absence of catalyst deactivation, we assume that the total concentration of active
sites, Ct, remains constant

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Adsorption Isotherm
■ Pi = partial pressure of species i in the gas phase, (atm or kPa)
■ Ci.S = surface concentration of sites occupied by species i, (mol/g-cat)

■ The total concentration of sites Ct = Cv + CA.S + CB.S

■ This is called site balance
■ Consider the adsorption of a non-reacting gas onto the surface of a catalyst.
■ Adsorption data are frequently reported in the form of adsorption isotherms.
■ Isotherms portray the amount of a gas adsorbed on a solid at different pressures at a
given temperature

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■ First, an adsorption mechanism is proposed, and then the isotherm obtained from the
mechanism is compared with the experimental data.
■ If the isotherm predicted by the model agrees with the experimental data, the model may
reasonably describe what is occurring physically in the real system.
■ If the predicted curve does not agree with the experimental data, the model fails to
match the physical situation and modification of the model may be needed.
■ Consider two types of adsorption:
– molecular or non-dissociative adsorption
– Dissociative adsorption

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■ In obtaining a rate law for the rate of adsorption, the reaction can be treated as an
elementary reaction.
■ The rate of attachment of the carbon monoxide molecules to the active site on the
surface is proportional to the number of collisions that these molecules make with a
surface active site per second.
■ In other words, a specific fraction of the molecules that strike the surface become
adsorbed.
■ The collision rate is, in turn, directly proportional to the carbon monoxide partial
pressure, PCO. Because carbon monoxide molecules adsorb only on vacant sites and not
on sites already occupied by other carbon monoxide molecules, the rate of attachment is
also directly proportional to the concentration of vacant sites, Pco.
■ Combining these two facts means that the rate of attachment of carbon monoxide
molecules to the surface is directly proportional to the product of the partial pressure of
CO and the concentration of vacant sites; that is,

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■ The net rate of adsorption is equal to the rate of molecular attachment to the
surface minus the rate of detachment from the surface.
■ If kA and k-A are the constants of proportionality for the attachment and detachment
processes

■ The ratio KA = kA/k-A is the adsorption equilibrium constant.

■ The adsorption rate constant, kA, for molecular adsorption is virtually independent of
temperature, while the desorption constant, k-A, increases exponentially with
increasing temperature.
■ Consequently, the equilibrium adsorption constant KA decreases exponentially with
increasing temperature
■ The site balance - Ct = Cv + CCO.S
■ At equilibrium, net rate of adsorption is zero  CCO.S = KACvPCO

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■ This equation thus gives the equilibrium concentration of carbon monoxide
adsorbed on the surface, CCO.S, as a function of the partial pressure of carbon
monoxide, and is an equation for the adsorption isotherm.
■ This particular type of isotherm equation is called a Langmuir isotherm
■ The Langmuir isotherm for the amount of CO adsorbed per unit mass of catalyst as
a function of the partial pressure of CO.
■ For the case of dissociative adsorption, the concentration of the atoms C and O
adsorbed per unit mass of catalyst.

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■ One method of checking whether a model (e.g., molecular adsorption versus
dissociative adsorption) predicts the behavior of the experimental data is to linearize
the model’s equation and then plot the indicated variables against one another.

■ The linearity of a plot of PCO/CCO.S as a function of PCO will determine if the data
conform to molecular adsorption, i.e., a Langmuir single-site isotherm

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■ Derive the isotherm for carbon monoxide disassociating into separate atoms as it
adsorbs on the surface

■ The rate of adsorption is proportional to the pressure of carbon monoxide in the

system because this rate is governed by the number of gaseous collisions with the
surface.
■ For a molecule to dissociate as it adsorbs, two adjacent vacant active sites are
required, rather than the single site needed when a substance adsorbs in its
molecular form.
■ The probability of two vacant sites occurring adjacent to one another is proportional
to the square of the concentration of vacant sites.
■ Hence the rate of adsorption is proportional to the product of the carbon monoxide
partial pressure and the square of the vacant-site concentration, 𝑃𝐶𝑂. 𝐶𝑣2

For desorption to occur, two occupied sites must be adjacent, meaning that
the rate of desorption is proportional to the product of the occupied-site concentration
C.S x O.S

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■ The Net rate of adsorption -

■ For dissociative adsorption, both kA and k-A increase exponentially with increasing
temperature, while the adsorption equilibrium constant KA decreases with
increasing temperature.

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■ Take inverse and multiply by

■ If dissociative adsorption is correct model this should give straight line

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■ In case of more than one substance getting adsorbed

■ When the adsorption of both A and B are first-order processes, the desorptions are also
first order, and both A and B are adsorbed as molecules.
■ The derivations of other Langmuir isotherms are relatively easy. In obtaining the
Langmuir isotherm equations, several aspects of the adsorption system were
presupposed in the derivations.
■ The most important of these, and the one that has been subject to the greatest doubt, is
that a uniform surface is assumed. In other words, any active site has the same
attraction for an impinging molecule as does any other active site.
■ Isotherms different from the Langmuir isotherm, such as the Freundlich isotherm, may
be derived based on various assumptions concerning the adsorption system, including
different types of nonuniform surfaces

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Surface reaction
■ The rate of adsorption of species A onto a solid surface

■ After a reactant has been adsorbed onto the surface, i.e.,

A · S, it is capable of reacting in a number of ways to form
the reaction product. Three of these ways are
■ Single site. The surface reaction may be a single-site mechanism in which only the site
on which the reactant is adsorbed is involved in the reaction. For example, an adsorbed
molecule of A may isomerize (or perhaps decompose) directly on the site to which it is
attached, such as

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■ Dual site. The surface reaction may be a dual-site mechanism in which the adsorbed
reactant interacts with another site (either unoccupied or occupied) to form the
product

First type dual site mechanism

Second type dual site mechanism

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Third type dual site mechanism

■ Reactions involving either single- or dual-site mechanisms, which were described

earlier, are sometimes referred to as following Langmuir– Hinshelwood kinetics

Eley–Rideal. A third mechanism is the reaction between an adsorbed molecule and a

molecule in the gas phase, such as the reaction of propylene and benzene

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Desorption
■ In each of the preceding cases, the products of the surface reaction adsorbed on
the surface are subsequently desorbed into the gas phase. For the desorption of a
species. The rate of adsorption of species A onto a solid surface

In addition, we see that the desorption equilibrium constant KDC is just the reciprocal of the
adsorption equilibrium constant for C, KC

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Pore diffusion resistance combined with
Surface Reaction
■ Single Cylindrical Pore, First-Order Reaction
■ First consider a single cylindrical pore of length L, with reactant A diffusing into the
pore, and reacting on the surface by a first-order reaction taking place at the walls
of the pore, and product diffusing out of the pore

The flow of materials into and out of any section of pore. At

steady state a material balance for reactant A for this elementary
section gives

Output - input + disappearance by reaction = 0

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Note that the first-order
chemical reaction is
expressed in terms of unit
surface area of the wall of the
catalyst pore; hence k" has
unit of length per time

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Hence for the cylindrical catalyst pore

Solution

By applying boundary conditions M1 and M2 can be evaluated

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Distribution and average
value of reactant
concentration within a
catalyst pore as a function
of the parameter mL

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■ This progressive drop in concentration on moving into the pore is be dependent on
the dimensionless quantity mL or MT called the Thiele modulus.
■ To measure how much the reaction rate is lowered because of the resistance to pore
diffusion, define the quantity 𝜉 called the effectiveness factor

In particular, for first-order reactions 𝜉 = CA/CAS because the rate is

proportional to the concentration. Evaluating the average rate in the pore

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 The effectiveness factor as a function of the
parameter mL or MT called the Thiele modulus

With this figure we can tell whether pore diffusion modifies the
rate of reaction, and inspection shows that this depends on
whether mL is large or small.
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■ For small mL, or mL < 0.4, we see that 𝜉 = 1, the concentration of reactant does not
drop appreciably within the pore; thus pore diffusion offers negligible resistance.
■ This can also be verified by noting that a small value for mL = 𝐿 𝑘 𝔇 L means either
a short pore, slow reaction, or rapid diffusion, all three factors tending to lower the
resistance to diffusion
■ For large mL, or mL > 4, we find that 𝜉 = 1/mL, the reactant concentration drops
rapidly to zero on moving into the pore, hence diffusion strongly influences the rate of
reaction. We call this the regime of strong pore resistance.

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Determining Controlling Resistances and
the Rate Equation
■ Interpretation of experiments becomes difficult when more than one resistance
affects the rate.
■ To avoid this problem we should like, with preliminary runs, to first find the limits of
operations where the various resistances become important.
■ This will allow us to select conditions of operations in which the resistances can be
studied separately.
■ Film Resistance - First of all, it is best to see whether film resistance of any kind (for
mass or heat transfer) need be considered.
■ Experiments can be devised to see whether the conversion changes at different gas
velocities but at identical weight-time. This is done by using different amounts of
catalyst in integral or differential reactors for identical values for weight-time, by
changing the spinning rate in basket reactors, or by changing the circulation rate in
recycle or batch reactors.

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■ If data are available we can calculate whether film resistance to mass transport is
important by comparing the observed first-order rate constant based on the volume
of particle with the mass transfer coefficient for that type of flow.

Or while Fluid Passing through packed bed

Thus to see whether film mass transfer resistance is important compare

If the two terms are of the same order of magnitude we may suspect that the
gas film resistance affects the rate. On the other hand, if kobsVp is much
smaller than kgSexp we may ignore the resistance to mass transport through
the film. 44
Pore Resistance
■ The effectiveness factor accounts for this resistance. Thus, based on unit mass of
catalyst we have

The existence of pore resistance can be determined by

1. Calculation if D is known.
2. Comparing rates for different pellet sizes.
3. Noting the drop in activation energy of the reaction with rise in
temperature, coupled with a possible change in reaction order

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Experimental methods for finding rates
■ Any type of reactor with known contacting pattern may be used to
explore the kinetics of catalytic reactions
■ The experimental strategy in studying catalytic kinetics usually
involves measuring the extent of conversion of fluid/gas passing in
steady flow through a batch of solids.
■ Any flow pattern can be used, as long as the pattern selected is
known; if it is not known then the kinetics cannot be found.
■ A batch reactor can also be used. In turn we discuss the following
experimental devices:
– Differential (flow) reactor
– Integral (plug flow) reactor
– Mixed flow reactor
– Batch reactor for both gas and solid

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■ Differential Reactor - We have a differential flow reactor when we choose to consider
the rate to be constant at all points within the reactor.
■ Since rates are concentration-dependent this assumption is usually reasonable only
for small conversions or for shallow small reactors.
■ But this is not necessarily so, e.g., for slow reactions where the reactor can be large,
or for zero-order kinetics where the composition change can be large.
■ For each run in a differential reactor the plug flow performance equation becomes

■ The average rate for each run is found. Thus each run gives directly a value for the
rate at the average concentration in the reactor, and a series of runs gives a set of
rate-concentration data which can then be analyzed for a rate equation.

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■ Integral Reactor - When the variation in reaction rate within a reactor is so large that
we choose to account for these variations in the method of analysis, then we have
an integral reactor.
■ Since rates are concentration-dependent, such large variations in rate may be
expected to occur when the composition of reactant fluid changes significantly in
passing through the reactor. We may follow one of two procedures in searching for a
rate equation.
– Integral Analysis
– Differential Analysis
■ Mixed Flow Reactor
■ Batch Reactor
■ In these the procedure to be followed is same as homogeneous reactor.

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■ What chemical reaction engineers need to be able to do:
– Developing an algebraic rate law consistent with experimental observations,
– Analyzing the rate law in such a manner that the rate-law parameters (e.g., k,
KA) can readily be determined 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

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■ Illustration - Hydrogen and toluene are reacted over a solid mineral catalyst
containing crystalline silica-alumina to form methane and benzene. The aim is to
design a packed-bed reactor and a fluidized CSTR to process a feed consisting of
30% toluene, 45% hydrogen, and 25% inert. Toluene is fed at a rate of 50 mol/min
at a temperature of 640C and a pressure of 40 atm (4052 kPa).
■ First determine the rate law from the differential reactor data given
– The rate of reaction of toluene as a function of the partial pressures of
hydrogen (H2), toluene (T), benzene (B), and methane (M).

■ Approximately 75% to 80% of all heterogeneous reaction mechanisms are surface-

reaction-limited rather than adsorption- or desorption-limited.
■ Analyze the reaction rate data available.

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■ What are the parameters on which the rate of reaction depends in case of
Heterogeneous reaction?
– Temperature
– Pressure
– Residence time (relative contact time between two phases)
– Relative velocity of the phases
– Particle Size

■ In this can the data is given only for rate and effect of partial pressure of component

■ This suggests that the effect of other parameters were already checked and
determined.

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52
Overall Rate expression and Mechanism

■ Propose a mechanism for the hydrodemethylation of toluene.

■ Assume that the reaction follows an Eley-Rideal mechanism where toluene is
adsorbed on the surface and then reacts with hydrogen in the gas phase to produce
benzene adsorbed on the surface and methane in the gas phase.
■ Benzene is then desorbed from the surface.
■ Because approximately 75% to 80% of all heterogeneous reaction mechanisms are
surface-reaction-limited rather than adsorption- or desorption-limited, begin by
assuming the reaction between adsorbed toluene and gaseous hydrogen to be
reaction-rate-limited.

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■ For surface limited reaction, replace CT.S and CB.S by measurable quantities
■ From the adsorption rate of toluene at equilibrium (not controlling) rAD = 0

Similarly
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From Site Balance

■ If you compare Run 3 and 5 it will be clear that reverse reaction is not happening
■ Which means the Thermodynamic Equilibrium constant is very large and term becomes
very small, which gives

In the original work on this reaction over 25 models were tested against
experimental data, and this was concluded

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Estimation of parameters
■ Next step is to determine how best the data is to evaluate the rate-law parameters, k, KT,
and KB
■ Invert the equation derived and estimate parameters using least-square or any other
method

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