Catalytic Reactor Design - Fourth Year Dr.Ali .N.

Khalaf

University of Basrah
College of Engineering
Chemical Engineering Department
Fourth Year
Second Semester

Catalytic Reactor Design

Part One:
Heterogeneous processes; Catalysis and adsorption; Classification and
preparation of catalysts; Promoters and inhibitors, Rate equations of fluid-
solid catalytic reactions; Hougen-Watson and power law models;
Procurement and analysis of kinetic data;
Part Two:
Reaction and diffusion in porous catalysts; Isothermal and non-isothermal
effectiveness factors; Effect of intra-phase transport,effect of external mass
transfer,; Global reaction rate.
Part Three:
Design of catalytic reactors: Isothermal and adiabatic fixed bed reactors.
Part Four:
Kinetics of catalyst Poisoning, Kinetics of catalyst deactivation and
regeneration.

1 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

Part One:
• Heterogeneous processes; Catalysis and adsorption.
• Classification and preparation of catalysts; Promoters
and inhibitors.
• Rate equations of fluid-solid catalytic reactions.
• The Langmuir-Hinshelwood-Hougen-Watson (LHHW)
and power law models.
• Analyzing Data from Laboratory Reactors, analysis of
kinetic data.

2 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

1- Catalysts and Catalysis:

A Catalyst is a substance that affects the rate of chemical reaction but emerges from
the process unchanged. Normally when we talk about a catalyst, we mean one that
speed 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 a
reaction; it does not affect the equilibrium.A number of catalysts both homogeneous
and heterogeneous are employed in the industry. Sulfuric acid, hydrofluoric acid,
vanadium pentaoxide, platinum over alumina, and zeolites with and without loading
of metals or oxides are common examples
Catalysis is the occurrence, study, and use of catalysts and catalytic processes.
Reactions are not catalyzed over the entire surface but only at certain active sites or
centers that result from unsaturated atoms in the surface.
Figure 1 shows some of commercial catalyst .

Figure 1: some of commercial catalyst .

An Active Site is a point on the surface that can form strong chemical bonds with an
adsorbed atom or molecule.
To make a catalytic process commercially viable, the number of sites per unit reactor
volume should be such that the rate of product formation is on the order of 1
mol/L·hour .

3 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
A solid catalyst consists of mainly three components :
1. Catalytic agent
2. Support /carrier
3. Promoters and Inhibitors
1.1- Catalytic Agent:
These are the catalytically active component in the catalyst. These components
generate the active sites that participate in the chemical reaction. Activity of any
catalyst is proportional to the concentration of these active sites.
Catalytic agents may be broadly divided in the following categories:
i. Metallic conductors ( e.g Fe, Pt, Ag, etc.)
ii. Semiconductors (e.g. NiO, ZnO,etc.)
iii. Insulators (e.g. Al2O3, SiO2,MgO etc.)

Metallic conductors: The metals that have strong electronic interaction with the
adsorbates are included in this category. The metals are used in various catalytic
reactions such as methanol synthesis, oxidation , hydrogenation and dehydrogenation
processes.

Examples of metal catalysts :

Cu for water gas shift reaction and methanol synthesis ; Ag for oxidation of ethylene
to ethylene oxide, Au for oxidation of methanol to formaldehyde; Fe for ammonia
synthesis; Pd and Pt for hydrogenation of olefins, dienes, aniline or nitriles as well as
dehydrogenation of alkanes, alcohols, cyclohexanes, cyclohexanols etc.

Semiconductors :
The oxides and sulfides of transition metals that have catalytic activity are included in
this category. Similar to conducting metals, they are also capable of electronic
interaction with adsorbed species and catalyze the same type of reactions

Common transition oxides and sulfides such as CuO, AgO, NiO CoO, Fe 2O3 , MnO,
Cr2O3, FeS, V2O5 show conductivity. These materials participate in catalytic reactions
and reaction occurs through acceptation or donation of electrons between the reactant
material and catalysts. Few applications of semiconductor catalysts are : CuO for
oxidation of nitric oxides, NiO for dehydrogenation of alkanes, MnO 2 for oxidation
of alcohols, and V2O5 for oxidation of hydrocarbons.

4 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

1.2-Support or Carrier:
Support or carrier provides large surface area for dispersion of small amount of
catalytically active agent. This is particularly important when expensive metals, such
as platinum, ruthenium, palladium or silver are used as the active agent. Supports
give the catalysts its physical form, texture, mechanical resistance and certain activity
particularly for bifunctional catalysts. Area of the support can range from 1 - 1000
m2/gm. Common supports are alumina, silica, silica-alumina, molecular sieves etc.
The surface area of α - alumina is in the range 1-10 m2/gm whereas the surface area
for γ or η - alumina can be in the range 100 – 300 m2/gm.
1.3-Promoters :
Promoters are generally defined as substances added during preparation of catalysts
that improve the activity or selectivity or stabilize the catalytic agents. The promoter
is present in a small amount and by itself has little or no activity
Negative promoters or inhibitors:
Inhibitors act opposite to promoters. When added in small amounts, these can reduce
catalyst activity, selectivity or stability. Inhibitor is particularly useful for reducing
the activity of a catalyst for undesirable side reactions. In oxidation of ethylene,
ethylene dichloride is added to inhibit CO2 formation thus acting as an inhibitor.
• In the case of metal catalysts, the metal is generally dispersed onto a high area oxide
such as alumina.
• Metal oxides also can be dispersed on a second carrier oxide such as vanadium
supported on titanium, or it can be made into a high-area oxide.
• These carrier oxides can have surface areas ranging from 0.05m2/g to greater than
100 m2/g.
• The carrier oxides generally are pressed into shapes or extruded into pellets.
• The following shapes are frequently used in applications: Table 1 lists some of the
important commercial catalysts and their uses.

– 20–100 μm diameter spheres for fluidized-bed reactors

– 0.3–0.7 cm diameter spheres for fixed-bed reactors
– 0.3–1.3 cm diameter cylinders with a length-to-diameter ratio of 3–4
– Up to 2.5 cm diameter hollow cylinders or rings.

5 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
Table1: Industrial reactions over heterogeneous catalysts.

A catalytic reaction involves physical–chemical phenomena of adsorption and

desorption besides chemical reaction. As shown in Figure 2, the energy barrier or
activation energy of a catalytic reaction is lower than the activation energy of a non-
catalytic reaction due to the adsorption and desorption phenomena.

The adsorption in a catalytic reaction is an exothermic phenomenon. However, either

the adsorption of molecules at the surface or desorption from the surface occurs under
different strengths, decreasing the degree of freedom that facilitates the reaction.

The energy of activation of a catalytic reaction is, therefore, lower than the energy
barrier. Thus, it is necessary to determine the adsorption and desorption rates in a
catalytic process. Thermodynamically, we do explain the adsorption phenomenon of
a fluid at the surface from the Gibbs free energy. It should be spontaneous and, thus,
∆Gads <0.

6 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

Fig.2: Comparison of a catalytic and a noncatalytic reaction

potential energy changes during the reaction path.

1.2- Catalytical Reaction Steps:

As shown in figure 3,Molecules enter the reactor with uniform concentrations CAo
and leave with mixing- concentrations CAout. In between, they undergo the following
steps:
1. Mass transfer across a film resistance from the bulk gas phase to the external
surface of the porous catalyst.
2. Transport of the reactants into the catalyst particle by diffusion through the pores.
3. Adsorption of reactant molecules onto the internal surface of the catalyst.
4. Reaction between adsorbed components on the catalytic surface.
5. Desorption of product molecules from the surface to the pores.
6. Diffusion of product molecules out of the pores to the external surface of the pellet.
7. Mass transfer of the products across a film resistance into the bulk gas phase.

7 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

Fig.3: Steps in a Catalytic Reaction

Fig.4 Different size scales in a packed bed catalytic reactor.

8 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

Fig.5: Mass transfer and reaction steps for a catalyst pellet.

In a heterogeneous reaction sequence, mass transfer of reactants first takes place from
the bulk fluid to the external surface of the pellet. The reactants then diffuse from the
external surface into and through the pores within the pellet, with reaction taking
place only on the catalytic surface of the pores. A schematic representation of this
process is shown in Figures 4 and 5.

1.3-Catalytic Reactions Mechanism and Rate Equations:

For irreversible gas phase reaction, A(g) ⇌ B(g) global rate for catalyst particles is
expressed in terms of temperature and concentration of A in bulk gas stream which
can be measured or specified directly. Global rates of catalytic reactions are usually
expressed per unit mass of catalyst.

1.3.1-Langmuir-Hinshelwood –Hougen-Watson(LHHW) model :

The Langmuir-Hinshelwood-Hougen-Watson (LHHW) approach accounts for the
surface concentrations of the species taking part in the reaction.
Relating surface species to the observed species partial pressures in the gas phase
provides equations that can be fitted to the kinetic data.
Based on the Langmuir adsorption isotherm, the approach was first developed by
Hinshelwood and therefore sometimes termed as Langmuir-Hinshelwood kinetics.
Hougen and Watson [1943] developed a similar approach and popularize the
Langmuir-Hinshelwood kinetics.

• The LHHW approach assumes that all active sites are energetically uniform and,
upon adsorption, adsorbed species do not interact with species already adsorbed.

9 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
• Active sites have similar kinetic and thermodynamic characteristics and the
entropy and enthalpy of adsorption are constant and not functions of the
adsorbed amount.
• The species adsorption restricts itself to only monolayer coverage and the rate of
adsorption is proportional to the concentration of the active sites not occupied
(empty) and the partial pressure of the component in the gas phase.
• Rate derived by this method takes into account the adsorption-desorption process
occurring over the surface along with the surface reaction.
• Rate equation derived can be extrapolated more accurately to concentrations
lying beyond the experimentally measured values.

The rate equation derived from mechanistic model that simulates the actual surface
phenomenon during the process is preferred for reactions involving solid catalysts.
The Langmuir-Hinshelwood–Hougen-Watson(LHHW) approach is one of the most
commonly used way of deriving rate expressions for fluid solid catalytic reactions.
The advantages of this method are that :
During this method of derivation of rate expression, all the physical transport steps
like mass transfer from bulk phase to catalyst surface or diffusion of reactants from
pore mouth to interior pore (intraparticle diffusion) are excluded. Thus, it is assumed
that the external and internal mass transport processes are very rapid relative to the
chemical rate process occurring on or within the catalyst particle.
The chemical rate depends on as shown in figure 6:

(1) chemisorption steps

(2) surface reaction steps
(3) desorption steps
This simple kinetic model assumes isothermal condition about and within catalyst
that is temperature gradient is zero.

Fig. 6: The Langmuir-Hinshelwood-Hougen-Watson (LHHW)

10 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
In LHHW model development, the rate equation is first derived in terms of surface
concentration of adsorbed species and vacant sites. Then, these surface
concentrations are related to the fluid or bulk concentration that is directly
measurable.

1.3.1.1-Adsorption Step:
Types of adsorption:

1-Physical adsorption (Physisorption)

2-Chemical adsorption (Chemisorption)

11 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

Because chemisorption is usually a necessary part of a catalytic process, we shall

discuss it before treating catalytic reaction rates. The Jetter 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 adsorbed on the site S. Species A can be an atom, molecule, or
some other atomic combination, depending on the circumstances. Consequently, the
adsorption of A on a site S is represented by
A(g) + 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/gcat). The molar concentration of vacant sites, CV, is the number of
vacant sites per unit mass of catalyst divided by Avogadro's number. In the absence
of catalyst deactivation, we assume that the total concentration of active sites remains
constant. Some further definitions include, as shown in figure 7.
12 Chemical Engineering Department- University of Basrah
Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
Pi = partial pressure of species i in the gas phase, (atm or kPa)
Cis = surface concentration of sites occupied by species i, (mol\g cat)

Fig.7: schematic representation of adsorption phenomena.

Rate of adsorption = rate of attachment – rate of detachment

rate of attachment of a molecules to the surface is directly proportional to the
product of the partial pressure of A and the concentration of a vacant sites.

The rate of detachment of molecules from the surface can be a first-order process;
that is, the detachment from the surface is usually directly proportional to the
concentradon of sites occupied by the adsorbed molecules
𝑟𝐴𝐷 = 𝑘𝐴 𝑃𝐴 𝐶𝑉 − 𝑘 ′𝐴 𝐶𝐴𝑆 .........……………………………………….. (1)
In terms of the adsorption equilibrium constant KA where
𝑘𝐴
𝐾𝐴 =
𝑘 ′𝐴
 C 
rAD = k A  PA Cv − A S  --------------------------------------..(2)
 KA 

13 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
1.3.1.2-Surface Reaction Step:
After the molecule is adsorbed onto the surface, it can react by a few different
mechanisms:

1. Singe site mechanism: Only the site to which the reactant is absorbed is involved
in the reaction

…..(3)

Where
𝑘𝑆
𝐾𝑆 = ′
𝑘𝑆
2. Dual site mechanism: Adsorbed reactant interacts with another vacant site to form
the product

A·S + S ⇌ S + B·S

9(3)
……….(4)

3. Eley-Rideal mechanism: reaction between adsorbed reactant and a molecule in

the gas phase

A·S + B(g) ⇌ C·S

…………………….(5)

14 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

1.3.1.3-Desorption Step:
Products are desorbed into the bulk gas phase

……(6)

Where :
𝑘𝐷
𝐾𝐷 =
𝑘′𝐷

1.4-Derive a Rate Law for Catalytic Rractions:

• Postulate catalytic mechanism, and then derive the rate law for that mechanism
• Assume pseudo-steady state hypothesis (rate of adsorption = rate of surface
reaction = rate of desorption)
- No accumulation of species on the surface or near interface
- Each species adsorbed on the surface is a reactive intermediate
- Net rate of formation of species i adsorbed on the surface is 0, ri·S=0
• One step is usually rate-limiting
- If the rate-limiting step could be sped up, the entire rxn would be faster
- Although reactions involve all 7 steps , only adsorption, surface reaction, or
desorption will be rate limiting
• The surface reaction step is rate limiting ~70% of the time!
Steps to derive the rate law
✓ Select among types of adsorption, surface reaction, and desorption
✓ Write rate laws for each individual step, assuming all are reversible
✓ Postulate which step is rate limiting
✓ Use non-rate-limiting steps to eliminate the surface concentration terms that
cannot be measured
The reaction equation have the general form:

(𝑲𝒊𝒏𝒆𝒕𝒊𝒄 𝑻𝒆𝒓𝒎) ∗ (𝑷𝒐𝒕𝒆𝒏𝒕𝒊𝒂𝒍 𝑻𝒆𝒓𝒎)

−𝒓𝑨 =
(𝑨𝒅𝒔𝒐𝒓𝒑𝒕𝒊𝒐𝒏 𝑻𝒆𝒓𝒎)𝒏
We need to select one of these 3 reactions as the rate limiting step, then derive the
corresponding rate equation, and see if this rate equation matches experimental data.
Which step is the most logical to start with?
a) Adsorption
b) Surface reaction
c) Desorption
d) None of the above
e) Any of these would be “logical” - they all have equal probability of being the
rate limiting step

15 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

Derive the rate equation for when the surface reaction is rate limiting
(true ~70% of the time)
For Dual site mechanism:

Or Singe site mechanism:

CA·S, Cv, and CB·S need to be expressed in terms of measurable

quantities.
• For surface reaction-limited mechanisms, kS is small and kA and kD are
relatively large
• Therefore rAD/kA and rD/kD are very small, and can be approximated as equal to
zero .
Use this relationship to eliminate CA·S and CB·S from their respective rate equations
and the site balance to eliminate CV

16 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

Use rD/kD =0 & rD equation to solve for CB·S

Use site balance to solve for CV:

Make substitutions for CA·S & CB·S, solve for Cv

Substitute CA·S, CB·S, &Cv in one of the following equations:

17 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

……….(7)

This is the rate equation in terms of measurable species and rate constants for
the surface reaction control .

Now derive the rate equation for when adsorption is rate limiting

Concentration of vacant and occupied sites must be eliminated from the rate equation
If adsorption is rate limiting, kS>>kAD, so rS/kS can be approximated as 0. Then

……………………………………………….(8)

Need to put CB·S in measureable terms

If adsorption is rate limiting, kD>>kAD, so in the desorption equation , rD/kD can be

approximated as 0. Then:

……………………………………….(9)

Subsitute equations(7 and 8)in equation (9) and solve for Cv using the site balance
equation

18 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

………………………………(10)

Substitute Cv into the expression for CB·S:

…………………………. ……..(11)

Substitute CB·S into CA·S:

……………………………… (12)

Use these eqs.(11and 12) to replace CA·S & Cv in rAD:

………(13)

19 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
This is the rate equation in terms of measurable species and rate constants for
the adsorption control .

For the reaction A+B ⇌ C+D

Let the reaction follows the mechanism given below ;

Among the various steps described, the slowest step controls the overall rate of
reaction and the other remaining steps are assumed to be at near equilibrium
conditions. This approach greatly simplifies the overall rate expression, reducing the
number of rate constants and equilibrium constants to be determined from
experimental data. Further each step in this method is assumed to be elementary and
the number of sites is conserved in each step.

20 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
Therefore, the controlling step can be either of the following:
(1) Surface reaction
(2) Adsorption
(3) Desorption

Now total concentration of active sites on surface, Ct , will be the summation

concentrations of all sites on which either ractants or products are adsorbed and the
concentration of vacant sites.
𝑪𝒕 = 𝑪𝑽 + 𝑪𝑨𝑺 + 𝑪𝑩𝑺 + 𝑪𝑪𝑺 + 𝑪𝑫𝑺

Case 1 : Rate is surface reaction controlling

The surface reaction is the slowest step and is the rate controlling. According to the
mechanism, surface reaction occurs between adsorbed A and adsorbed B producing
adsorbed C & adsorbed D.

…………….. (14)

Now, since all the other steps are considered to be in equilibrium, therefore
concentration of adsorbed species can be obtained as follows.
For adsorption steps and desorption steps :

21 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

Substituting all these value in equation (14)

………………………….. (15)

Now ,
𝑪𝒕 = 𝑪𝑽 + 𝑪𝑨𝑺 + 𝑪𝑩𝑺 + 𝑪𝑪𝑺 + 𝑪𝑫𝑺
𝑪𝒕 = 𝑪𝑽 + 𝑲𝑨 𝑪𝑨 𝑪𝑽 + 𝑲𝑩 𝑪𝑩 𝑪𝑽 + 𝑲𝑪 𝑪𝑪 𝑪𝑽 + 𝑲𝑫 𝑪𝑫 𝑪𝑽
𝑪𝒕
𝑪𝑽 = … … … … … … … … … … . (16)
𝟏 + 𝑲𝑨 𝑪𝑨 + 𝑲𝑩 𝑪𝑩 + 𝑲𝑪 𝑪𝑪 + 𝑲𝑫 𝑪𝑫

……………………….. (17)

Substituting (16) &(17) in equation (15),

22 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

…………….(18)

The above rate expression can also be derived in terms of bulk partial pressure.

Case 2: Rate is adsorption control

(a) Adsorption of A controlling:

Let adsorption of A be the slowest step so that adsorption of B, surface reaction and
desorption of C are at equilibrium.
Adsorption of A is given as

…………………………. (19)

23 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

…………….(20)

Substituting equation (20) in equation (19) gives

…………………………. (21)

Now
𝑪𝒕 = 𝑪𝑽 + 𝑪𝑨𝑺 + 𝑪𝑩𝑺 + 𝑪𝑪𝑺 + 𝑪𝑫𝑺

𝑲𝑪 𝑲𝑫 𝑪𝑪 𝑪𝑫 𝑪𝑽
𝑪𝒕 = 𝑪𝑽 + . + 𝑲𝑩 𝑪𝑩 𝑪𝑽 + 𝑲𝑪 𝑪𝑪 𝑪𝑽 + 𝑲𝑫 𝑪𝑫 𝑪𝑽
𝑲𝑺 𝑲𝑩 𝑪𝑩

𝑲𝑪 𝑲𝑫 𝑪𝑪 𝑪𝑫
𝑪𝒕 = 𝑪𝑽 [𝟏 + .( ) + 𝑲𝑩 𝑪𝑩 + 𝑲𝑪 𝑪𝑪 + 𝑲𝑫 𝑪𝑫 ]
𝑲𝑺 𝑲𝑩 𝑪𝑩

𝑪𝒕 …………………….(22)
𝑪𝑽 = 𝑲 𝑲 𝑪 𝑪
𝟏+ 𝑪 𝑫 .( 𝑪 𝑫 )+𝑲𝑩 𝑪𝑩 +𝑲𝑪 𝑪𝑪 +𝑲𝑫 𝑪𝑫
𝑲𝑺 𝑲𝑩 𝑪𝑩

Substituting value of 𝑪𝑽 from equation(22) in equation (21) gives

𝑪 𝑪
𝑪𝑨 −[ 𝑪 𝑫 ]
𝑲𝑪𝑩 …………………(23)
𝒓𝑨 = 𝒌𝒂 𝑪𝒕 𝑲 𝑪 𝑪
𝟏+ 𝑨 .( 𝑪 𝑫 )+𝑲𝑩 𝑪𝑩 +𝑲𝑪 𝑪𝑪 +𝑲𝑫 𝑪𝑫
𝑲 𝑪𝑩

24 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
Similarly expression when desorption of product is the rate controlling step can be
derived.
For desorption of C controlling the whole reaction, the rate expression can be
derived as:

……………………(24)

Guidelines for finding Mechanisms from experimental observation:

• More than 70% of heterogeneous reaction mechanisms are surface reaction

limited
• If a species appears in the numerator of the rate law, it is probably a
reactant
• If a species appears in the denominator of the rate law, it is probably
adsorbed in the surface

Example 1:
We now propose a mechanism for the hydrodemethylation of toluene. We assume
that 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% of' heterogeneous
reaction mechanisms are surface-reaction limited rather than adsorption or
desorption-limited, we begin by mechanisms are assuming the reaction between
adsorkd toluene and gaseous hydrogen to be surface-reaction-rate-limited.
Symbolically, this mechanism and associated rate laws for each elementary step are.

25 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
For surface-reaction-limited mechanisms,

we see that we need to replace CT·S and CB .S in the above equation by quantities that
we can measure.For surface-reaction-limited mechanisms, we use the adsorption rate
to obtain C T·S

and we use the desorptinn rate Equation to obtainC BS:

Substituting Equations for 𝐶𝑇.𝑆 𝑎𝑛𝑑 𝐶𝐵.𝑆 into the site balance equation and
rearranging, we obtain

Next, substitute for C BS and CTS and then substitute for CV in surface reaction
equation to obtain the rate law for the case of surface-reaction control:

1.5-Eley Rideal Model:

Apart from power law and Langmuir-Hinshelwood models, other kinetic models are
also used to fit the data. Eley Rideal model depicts the reaction mechanism in which
one reactant species (say A) is adsorbed while the second reactant species (say B) is
not adsorbed on the catalyst surface. The reaction then occurs when the passing gas

26 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
molecules of B in gas phase directly reacts with the adsorbed species A. The
schematic representation is shown in Fig. 8.

Fig. 8: Eley Rideal mechanism for reaction of adsorbed A with

gas phase B producing product AB

1- Assuming that step 2, the reaction between adsorbed A and gas phase B is
irreversible and the rate determining step, then the rate of reaction can be written
as(the reaction is not irrevesibile)
………………………………(25)

For Adsorption Step

27 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

………………...(26)

………………..(27)

Fig.9: Langmuir adsorption isotherm.

Substituting value of CAS from equation(27) in equation (25)

𝒌𝑪𝒕 𝑲𝑨 𝑪𝑨 𝑪𝑩 …………………(28)
𝒓𝑺 = 𝒌𝑪𝑨𝑺 𝑪𝑩 =
𝟏+𝑲𝑨 𝑪𝑨

2-If the products are chemisorbed then the reaction may become reversible as shown
below(the reaction is reversibile)

………………………..(29)

28 Chemical Engineering Department- University of Basrah

 Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

Ct
𝑪𝒕
𝑪𝑽 =
𝟏 + 𝑲𝑨 𝑪𝑨 + 𝑲𝑷 𝑪𝑷

𝑲𝑨 𝑪𝑨 𝑪𝒕
𝑪𝑨𝑺 = 𝑲𝑨 𝑪𝑨 𝑪𝑽 =
𝟏 + 𝑲𝑨 𝑪𝑨 + 𝑲𝑷 𝑪𝑷
𝑲𝑷 𝑪𝑷 𝑪𝒕
𝑪𝑷𝑺 = 𝑲𝑷 𝑪𝑷 𝑪𝑽 =
𝟏 + 𝑲𝑨 𝑪𝑨 + 𝑲𝑷 𝑪𝑷
Substituting CAS and CPS in rate expression gives:
𝑲𝑷 𝑪𝑷
𝒌𝑪𝒕 (𝑲𝑨 𝑪𝑨 𝑪𝑩 − )
𝒓𝑺 = 𝒌𝑪𝑨𝑺 𝑪𝑩 − 𝒌𝒃 𝑪𝑷𝑺 = 𝑲 … … … … … … . . (𝟑𝟎)
𝟏 + 𝑲𝑨 𝑪𝑨 + 𝑲𝑷 𝑪𝑷

1.6-Analyzing Data from Laboratory Reactors:

The objectives of analyzing data include :

• Determining catalyst activity, selectivity and stability .

• Determining the effect of important process variables such as temperature, pressure,
reactant concentrations.
• Finding a rate equation .

1.6.1- Integral Analysis of Rate Data:

In this method a series of run are made in a packed bed at a fixed initial
concentrations CA0 and a fixed temperature while varying the catalyst mass W and/or
initial molar flow rate FA0 to generate a range of W/FA0 values at different
conversions XA. A rate equation is then selected for testing using the design equation
for packed bed reactor.

First simpler rate equations such as zero order, first order, second order irreversible
are tried. Mechanistic reaction models can also be tested. The W/F A0 and the right
hand integral in the design equation are evaluated numerically and plotted to test for
linearity (Fig.10). Linearity of the plot is used as criterion for judging if the selected
rate equation is a useful model for the data i.e consistent with the data. If not then
another rate equation may be tried.

29 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

Fig.10. Typical plot of W/FA0 vs integral value for linearity test in integral analysis of rate data.

1.6.2-Initial Rate Analysis:

Initial rate analysis for a reaction may be done to understand the mechanism of a
reaction. Initial rate is defined as the rate at zero conversion. It is obtained by
extrapolation of the rate vs conversion data to zero conversion. For higher accuracy,
the conversion data are collected at very low conversion region. In this method, the
dependence of initial rate data on partial pressure or total pressure of the reactant is
studied.

The rate expression derived from Langmuir Hinshelwood model when surface
reaction is controlling is.

Now at zero conversion all the product concentration will tend to zero, hence
putting CC =0 & CD =0, the rate expression simplifies to

Where ri is the initial rate. Now, if a equimolal initial concentration of CA and CB is

used then CA=CB .
Then assuming ideal gas mixture, CA=PA\RT : where PA is the partial pressure of A.
Similarly CB=PB\RT : where PB is the partial pressure of B.
Now since it is an equimolal mixture, then at initial condition PA= PB=0,5Pt ,
where Pt is the total pressure.

30 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
Or CA= CB=0.5Pt\RT
Then substituting CA and CB in equation [3] becomes

………………………………(31)

On plotting initial rate ri as a function of total pressure pt , a typical curve as shown

in Fig 11 is obtained. Hence if kinetic data for a reaction give similar plot then it can
be deduced that the reaction is surface reaction controlled.

When adsorption of A is controlling the dependence of initial rate on total pressure

can be derived in similar way as
…………………………….(32)

For this mechanism a typical plot of initial rate ri as a function of total pressure p t is
shown in Fig 11. When reaction data satisfy this plot then the reaction is said to be
adsorption A controlling. In similar way other models can be tested for fitting.
However, it should be noted that though the initial rate analysis is simple and can
reduce the number of rate expressions to be tested against the experimental but
cannot substitute a differential or integral analysis. It should be used as only as
preliminary kinetic analysis method.

31 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

Fig. 11. Typical plot for initial rate vs total pressure for reactions 𝐴 + 𝐵 ⇌ 𝐶 + 𝐷 when equimolal
mixture of A and B is used. A) surface reaction controlling B) adsorption of A controlling

Figure 12 shows the general types of initial rate expressions.

Fig.12: General types of initial rate expressions

32 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
1.6.3-Linear and Nonlinear Regression of Rate Data:
For a Langmuir –Hinshelwood type rate equation:

the value of rate law parameters k, KA, KB cannot be analyzed as simply as in power
law kinetics. The rate law parameters can be determined by linear least square or
nonlinear least square method. In linear least square method, the above LH rate
equation can be linearized by dividing throughout by pA and pB and inverting it as
shown below:

………………………… (33)

The parameters can be estimated by multiple regression technique using the

following equation for N experimental runs. For the ith run :
………………………… (34)

The best values of the parameters a0, a1 and a2 are found by solving following three
equations

The above LH rate equation can also be solved by non-linear regression analysis.
Usually linearized least square analysis is used to obtain the initial estimates of the
rate parameters and used in non-linear regression. In non linear analysis the rate law
parameters are first estimated to calculate the rate of reaction ‘rc’. Then the values of
rate law parameters that will minimize the sum of the squares of difference of the
measured reaction rate rm and the calculated reaction rate rc , that is the sum of (rm-
rc)2 for all data points, are searched. If there are N experiments with K number of
parameter values to be determined then the function to be minimized is given by:

……………………….. (35)

33 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
Here rim and ric are the measured and calculated reaction rate for ‘i’th run
respectively. The parameter values giving the minimum of the sum of squares, σ2, can
be searched by various optimization techniques using software packages.

Example 2:
The rate law for the ydrogenation (H) of ethylene (E) to form ethane (A)
H2 + C2H4 → C2H6 over a cobalt-molybdenum catalyst is:

Suggest a mechanism and rate-limiting step consistent with the rate law and then
derive the rate law.
Solution:

Because neither H2 or C2H6 are not in the denominator of the rate law they are either
not adsorbed or weakly adsorbed. Assume H2 in the gas phase reacts with C2H6
adsorbed on the surface and ethane goes directly into the gas phase. Then check to
see if this mechanism agrees with the rate law
Eley Rideal Model

Assume surface reaction

34 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
𝑃𝐸 𝑃𝐻
−𝑟𝐴 = 𝑘 [ ]
1+𝐾𝐸 𝑃𝐸

Example 3:
t-Butyl alcohol (TBA) is an important octane enhancer that is used to replace lead
additives in . TBA was produced by the liquid-phase hydration (W) of isobutene (I)
over an Amberlyst-15 catalyst. The system is normally a multiphase mixture of
hydrocarbon, water, and solid catalysts. However, the use of cosolvents or excess
TBA can achieve reasonable miscibility.
The reaction mechanism is believed to be

Derive a rate law assuming:

(a) The surface reaction is rate-limiting.
(b) The adsorption of isobutene is limiting.
(c) The reaction follows Eley-Rideal kinetics

and the surface reaction is limiting.

(d) Isobutene (I) and water (W) are adsorbed on different sites

TBA is not on the surface, and the surface reaction is rate-limiting.

e) What generalization can you make by comparing the rate laws derived in
parts (a) through (d)?

35 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
Solution:

(a)

36 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
(b) Adsorption of isobutene limited

(c)

37 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

(d)

Example(4):
The dehydration of n-butyl alcohol (butanol) over an alumina-silica catalyst. The data
in Figure were obtained at 750°F in a modified differential reactor. The feed
consisted of pure butanol.
(a) Suggest a mechanism and rate-controlling step that are consistent with the
experimental data.
(b) Evaluate the rate law parameters.

38 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
(c) At the point where the initial rate is a maximum, what is the fraction of vacant
sites? What is the fraction of occupied sites by both A and B?
(d) What generalizations can you make from studying this problem?
(e) Write a question that requires critical thinking and then explain why your question
requires critical thinking.

Initial reaction rate as function of initial partial pressure of butanol.

Solution:
(a)

39 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

(b)

40 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

41 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
(C)

Example 5:
The experimental data for the gas-phase, catalytic, irreversible reaction A + B→C is
given in the table. Suggest a rate law & mechanism consistent with the data.
Approach: Use graphs to show how -rA varies with Pi when Pj and Pk are held
constant.

42 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
Solution:

We need to use these graphs to determine whether A, B, & C are in the numerator,
denominator, or both.

43 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

The rate law suggested for the experimental data given for the gas-phase, catalytic,
irreversible reaction A + B→C is:

Suggest a mechanism for this rate law.

PA and PC are in the denominator. A (reactant) and C (product) must be adsorbed on
the surface, but B is not adsorbed on the surface:

Surface reaction step: B is not adsorbed on the surface, so B must be in the gas phase
when it reacts with A adsorbed on the surface.
The overall reaction is irreversible, so this step is likely irreversible

Postulate that the surface reaction is the rate limiting step since that is true the
majority of the time. Check if that is consistent with the observed kinetics

44 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

Example 6:
Methyl ethyl ketone (MEK) is an important industrial solvent that can be produced
from the dehydrogenation of butan-2-ol (Bu) over a zinc oxide catalyst A → B+C
Bu → MEK + H2
The following data giving the reaction rate for MEK were obtained in a differential
reactor at 490°C.

a- Suggest a reaction mechanism and rate-limiting step consistent with the

rate law. [Hint: Some species might be weakly adsorbed.]
45 Chemical Engineering Department- University of Basrah
Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

If the limiting step is 2(irreversible surface reaction) and the others at Pseudo Steady
State (steps 1,3,and 4).

46 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

b- First we need to calculate the rate constants involved in the equation for –rA in part
(a). We can rearrange the equation to give the following

47 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
Thus from the slope and intercept data:

Homework Problems:
1-The reaction A + B → C is speculated to occur with adsorption of A and C on one
type of site; independent adsorption of B on a second type of site; and the surface
reaction between adsorbed A and adsorbed B is the rate limiting step.
a) Determine the fraction of vacant sites?
b) Determine the fractions of adsorbed species.?
c) Determine the reaction rate expression according to the described mechanism?
d) Qualitatively sketch the dependence of the reaction rate on PA, PB, PC (i.e., One
sketch for each, with other partial pressures held constant) ?

2-The formation of propanol on a catalytic surface is believed to proceed by the

following mechanism

Suggest a rate-limiting step and derive a rate law.

Answer:

48 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
3- The irreversible, gas-phase, solid-catalyzed reaction A+B→C is carried out in a
differential reactor.
(a) Determine a mechanism and rate-limiting step consistent with the following
data:

(b) Evaluate all rate law parameters.

(c) Where would you take additional data points?
(d) Discuss what you learned from this problem.

4- Given the following reaction rate expression and the following data

5-The reaction A2 + B2 → C is speculated to occur with adsorption of A and B on the

same site. If no product adsorption takes place, and both A and B dissociate upon
adsorption and the surface
reaction between adsorbed A and adsorbed B is the rate limiting step.
a) Determine the fraction of vacant active sites?
b) Determine the fractions of adsorbed species.?
c) Determine the reaction rate expression according to the described mechanism?
d) Qualitatively sketch the rate versus the partial pressure of A2, B2 and C.

49 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
6-Given the following reaction rate expression and the following data

7- The reaction A2 + B → C is speculated to occur with adsorption of A and C on one

type of site; independent adsorption of B on a second type of site; If A dissociates
upon adsorption and the surface reaction between adsorbed A and adsorbed B is the
rate limiting step.
a) Determine the fraction of vacant active sites?
b) Determine the fractions of adsorbed species.?
c) Determine the reaction rate expression according to the described mechanism?

8-Given the following reaction rate expression and the following data

50 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

Part Two:
• Reaction and diffusion in porous catalysts.
• Isothermal and non-isothermal effectiveness factors.
• Effect of intra-phase transport.
• Effect of external mass transfer.
• Global reaction rate.

51 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

2-Internal Diffusion Phenomena:

Catalysts contain active sites which are located inside the pores. Therefore, molecules
must first diffuse into the pores. until reaching the sites before reaction.

The internal molecular diffusion inside pores can be the limiting step and therefore it
is unwanted. Basically, there are three forms of diffusions occurring in the pores of
the catalyst:
1. Molecular (bulk) diffusion: may occur in big pore diameters (1–10μm) where the
mean free path of the molecules is small compared to the pore diameter.
The calculation of binary molecular diffusion coefficients in gases has been the
subject of much research. Two relationships that are widely used are the Chapman–
Enskog formula and the Fuller formula. The Chapman–Enskog formula is

………………………. ……..(1)

2. Knudsen diffusion: exists in middle pore diameters (10–1.000 Å) where the mass
transport happens by collision between the molecules and the wall.
However, as the pores become smaller, collisions between the molecules and the pore
walls become significant for gas-phase systems. The collisions between the diffusing
molecules and the wall gives rise to Knudsen diffusion. The Knudsen diffusion
coefficient, in m2/s, in a straight round pore can be calculated from the formula:

………………………………….. (2)

Where dp is the pore diameter in m, T is the temperature in kelvin, and the molar
mass of the diffusion species, M, is in kg/kmol or g/mol. The Knudsen diffusion
coefficient varies with the pore diameter, which implies that a range of diffusion
coefficients applies to a catalyst with a significant pore size distribution.

52 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
3. Configuration diffusion: exists in pores where the diameter of molecules is of the
same order of the pore diameter.

For a binary system, it has been shown that the pore diffusion coefficient can be
expressed as a function of the two quantities using the following relationship:

……….. ……(3)

……………….(4)

It would not be fruitful to describe diffusion within each and every one of the
tortuous pathways individually; consequently, we define an Effective Diffusion (De)
so as to describe the average diffusion taking place at any position r in the pellet. An
equation that relates De to either the bulk or the Knudsen diffusivity is

……………………………. ……..(5)

53 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

Diffusion of molecules in porous catalysts is highly dependent on the dimensions of

the pore network. Figure 13 shows typical values of the gas-phase diffusivity as a
function of pore size.

Figure 13:Influance of pore size on the gas-phase diffusivity.

2.1-Effectiveness Factor η:
In a porous catalyst, the internal surface area within the pores constitutes the effective
surface on which the active metals are deposited. Hence, for reaction to occur, the
reactants need to travel through the pores to reach the active sites. If there is any
resistance in diffusion of the reactants through the pores, then both the activity and
selectivity of the process is affected. In the absence of any internal mass transfer
resistance within the pores the concentration of reactants can be assumed to uniform
and equal to the surface concentration. Hence, the rate of reaction will also be
uniform across the catalyst pellet and equal to the rate evaluated at surface

54 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
conditions. However, in the presence of diffusional resistance, concentration of
reactants gradually decreases from the surface towards the center of the catalyst
pellet, resulting in a concentration gradient. When this concentration gradient is large
enough, significant variation in reaction rate occurs within the pellet. The average
rate within pellet will be less than the rate corresponding to the surface concentration.
As pellet size decreases, the effect of intrapellet transport becomes less significant.

Rate of reaction for the whole catalyst pellets at any time is defined with respect to
outer surface conditions in term of effectiveness factor η as :

………………. (6)

Actual rate of whole pellet rp takes intrapellet mass transfer effects if any into
account.

2.1.1-Effectiveness Factor at Isothermal Conditions :

We now perform a steady-state mole balance on species A as it enters, leaves, and
reacts in a spherical shell of inner radius r and outer radius r + ∆r of the pellet (Figure
14). Note that even though A is diffusing inward toward the center of the pellet, the
convention of our shell balance dictates that the flux is in the direction of increasing
r. We choose the flux of A to be positive in the direction of increasing r (i.e., the
outward direction). Because A is actually diffusing inward, the flux of A will have
some negative value, such as - 10 mol/m2 .s, indicating that the flux is actually in the
direction of decreasing r

Fig.14: Shell balance on a catalyst pellet.

55 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
For an irreversible first order reaction A→B, at isothermal for a spherical catalyst
pellet of radius ‘Rs’, mass balance over a spherical shell volume of thickness ΔR at
steady state will be :
(Rate of diffusion of reactant into element) – (Rate of diffusion of reactant out of
element) = Rate of disappearance of reactant within element due to reaction

𝒎𝒐𝒍
Rate of reaction per unit mass of catalyst ( ) =k1C
𝒌𝒈𝒄𝒂𝒕 .𝒔𝒆𝒄
𝒎𝒐𝒍
Rate of reaction per unit volume of catalyst (
𝒎𝟑 𝒄𝒂𝒕 .𝒔𝒆𝒄
) = k1Cρp
𝒌𝒈
Where ρp is the density of pellet ( ).
𝒎𝟑
𝒎𝟑 𝒎 𝒎𝟐
The units of k1 is (
𝒌𝒈.𝒔𝒆𝒄
) = 𝒌 (𝒔𝒆𝒄) ∗ 𝑺𝒂 (𝒌𝒈 )
𝒎𝟐
Where 𝑺𝒂 ( ) is the is the total active area inside the porous pellet per gram of
𝒌𝒈
pellet.
Then the mass balance equation over the element of thickness ΔR can be written as :

If limit is taken as ΔR→0 and assuming that effective diffusivity is independent of

concentration of reactant the above equation can be written

………………………………(7)

…………………………(8)

……………………….. (9)
Solving the differential equation (7) with boundary conditions (8) and (9) following
relation is obtained

……………………….. (10)

910

……………………… (11)

56 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
The (ϕs ) is called Thiele Modulus for spherical pellet. Equation (10) gives the
concentration profile of A in the pellet.

This concentration profile is used to evaluate the rate of reaction rP for the whole
pellet. Calculating the diffusion rate of reactant into pellet at position Rs per unit mass
of catalyst pellet.
……………………. (12)

Substituting the value of mp in equation (12)

…………………(13)

Or
…….(14)

substituting in equation (14), following relation for η can be obtained for isothermal
conditions.

………………………….(15)

Where for spherical pellets of radius rs, for a first-order reaction is given as ϕs

……………………………(16)

k1 is rate constant, ρp is pellet density; De is effective diffusivity

Hence, to calculate Thiele modulus, both effective diffusivity De and rate constant k1
need to be known. Fig 15 shows the typical plot of η vs φs.The Concentration profile
in a spherical catalyst pellet in is shown in fig 16.

57 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

Fig. 15. Typical plot effectiveness factor η as function of Thiele modulus φs

For large values of ϕ the

Thiele modulus, internal
diffusion limit the rate of
reaction

Fig. 16: Concentration profile in a spherical catalyst pellet.

The magnitude of the effectiveness factor (ranging from 0 to 1) indicates the relative
importance of diffusion and reaction limitations. The effectiveness factor is defined
as
𝑹𝑨𝒑 = 𝜼 𝑹𝑨𝒔

The resulting expression for the effectiveness factor for first order reaction is:

58 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
𝟏 𝟏 𝟏
𝜂 = ( − )
∅𝒔 𝐭𝐚𝐧𝐡(𝟑∅𝒔 ) 𝟑∅𝒔

𝟏 ……………………….(17)
1- 𝑾𝒉𝒆𝒏 𝝋𝒔 ≤ 𝟑 , 𝜼 → 𝟏
As the figure shows, for small values of φs η→1 . Equation (16) shows that small
values of φs are obtained when the :
1. Pellets are small
2. Diffusivity is large
3. Reaction is intrinsically slow ( catalysts of low activity).

𝟏 ……………………….(18)
2- 𝑾𝒉𝒆𝒏 𝝓 ≥ 𝟓), 𝜼 = 𝝋𝒔
as For such large φs, intra-particle diffusion has a large effect on the rate. At this
condition, diffusion into the pellet is relatively slow and reaction occurs before the
reactant has diffused far into the pellet.

When η→1 , rate for the whole pellet is the same as the rate at surface concentration
Cs and the entire catalyst surface is fully active.

When η<<1 , the concentration within pellets drops from Cs to nearly zero in a
narrow region near rs. At this condition, only the surface near the outer periphery of
the pellet is effective and the catalyst surface in the central portion of the pellet is not
utilized. This situation can be caused by large particles, low De or high k 1; that is
very active catalysts.

Hence, low effectiveness factors are more likely with very active catalysts. More
active the catalyst, the more is the possibility that intrapellet diffusion resistance will
reduce global rate.

As noted in Equation 16, the Thiele modulus for spherical pellet is defined as:

𝟏 𝒎 𝒎𝟐 𝒌𝒈
Where 𝒌𝑽 (𝒔𝒆𝒄) = 𝒌𝟏 𝝆𝑷 = 𝒌(
𝒔𝒆𝒄
) ∗ 𝑺𝒂 (
𝒌𝒈
) ∗ 𝝆𝑷 (
𝒎𝟑
)

In the analysis of other shapes using an approximate one-dimensional analysis, a

generalized Thiele modulus has been proposed. The characteristic length (Lc) for
the catalyst particle is defined as the total particle volume divided by the external
surface area through which diffusion occurs. Thus, we can define a generalized
Thiele modulus as

59 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

………………….(19)

With this new definition of the Thiele modulus, the solution must also change, and
the three new equations for the effectiveness factor are:

For each of the three geometries (plane wall, infinite cylinder, and sphere) considered
thus far, the generalized Thiele modulus becomes, respectively

…………….(20)

• Effectiveness Factors for Non-First-Order Reactions:

The results presented thus far pertain to first-order reactions. As noted earlier, an
interesting result for the first-order case is that the effectiveness factor does not
depend on the value of the surface concentration, but only on the temperature.
Effectiveness factors can also be derived for other types of kinetics, and we start by
considering a reaction of order n; thus, let us consider a rate equation of the form

The general equation for irreversible reactions second order or higher can be
estimated from the formula:

𝒏+𝟏 𝒌 𝑽 ∗𝑪𝑨𝑺 𝒏−𝟏

∅𝒔 = 𝑳√( ) ………………………….(21)
𝟐 𝑫𝒆

The value of the Thiele modulus includes the surface concentration, which in turn
means that the effectiveness factor depends on the surface concentration of reactant.
In this case, the mole balance equation becomes a nonlinear differential equation and
requires a numerical solution.

60 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
For first order reversible reaction A↔B the Thiel modulus is given by

𝑹 𝟏 𝒌𝟏 (𝑲+𝟏) 𝒌𝟏
∅𝒔 = √ ( ) ∶ 𝑲= ………………..(22)
𝟑 𝑫 𝒆 𝑲 𝒌𝟐

It can be seen that ∅𝑠 for reversible reactions is greater than for irreversible reactions
, so the effectiveness factor (η ) for reversible reactions is less than η for irreversible
reactions.
The rate of reaction for for reversible reactions is given by
𝑟𝑝 = 𝑘𝑅 (𝐶𝐴 − 𝐶𝐴.𝑒𝑞𝑢 )
Where:
𝑘1 (𝐾 + 1)
𝑘𝑅 =
𝐾
𝒌𝟏 𝑪𝑩,𝒆𝒒 𝑪𝑨𝒐 ∗ 𝒙𝒆 𝒙𝒆
𝑲= =( )= =
𝒌𝟐 𝑪𝑨,𝒆𝒒 𝑪𝑨𝒐 (𝟏 − 𝒙𝒆 ) 𝟏 − 𝒙𝒆

2.3-Estimation of Diffusion- and Reaction-Limited Regimes:

It is instructive to compare this actual pellet production rate to the rate in the absence
of diffusional resistance. If the diffusion were arbitrarily fast, the concentration
everywhere in the pellet would be equal to the surface concentration, corresponding
to the limit ϕ=0 then η→1.

The pellet rate for this limiting case is simply

…………………………(23)

For η near unity, the entire volume of the pellet is reacting at the same high rate
because the reactant is able to diffuse quickly through the pellet.

For η near zero, the pellet reacts at a low rate. The reactant is unable to penetrate
significantly into the interior of the pellet and the reaction rate is small in a large
portion of the pellet volume.The pellet's diffusional resistance is large and this
resistance lowers the overall reaction rate.

As the particle diameter becomes very small, the Thiele modulus decreases, so that
the effectiveness factor approaches 1 and the reaction is surface-reaction-limited. On
the other hand, when the Thiele modulus is large, the internal effectiveness factor is
small and the reaction is diffusion-limited within the pellet (see figure 17).

61 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

Fig.17: Effectiveness factor for different reaction orders and catalyst shapes.

2.3.1-Significance of Intrapellet Diffusion:

The Weisz–Prater criterion uses measured values of the rate of reaction, (rAobs), to
determine if internal diffusion is limiting the reaction.

62 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

……………….(24)

This criterion can be approximately used for most catalytic kinetics though it is
derived for a 1st order reaction . There are no diffusion limitations(the internal
diffusion may be neglected) and consequently no concentration gradient exists
within the pellet.

……………………………..(25)

However, there is a diffusion limitations (the internal diffusion is very strong)

and consequently there is a concentration gradient within the pellet

…………………………….(26)

The summary of the Weisz–Prater criterion dictates that

Example 1:
Dehydrogenation of hydrocarbon (mol.wt = 58) at atmospheric pressure was carried
out over chromia-alumina catalysts at 530 0C. The reaction follows a first order
kinetics with rate constant of 0.94 cm3 /s. g cat. The spherical catalysts are of 30 mm
diameter and average pore radius is 11 nm. Pellets have porosity of 0.35 and density
of 1 gm/cm3. Assume Knudsen diffusivity to be dominant. Predict an effectiveness
factor for the catalysts. Use parallel pore model with a tortuosity factor of 3.0
Solution:

63 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

Example 2:
The first-order, irreversible reaction (A→B) takes place in a 0.3 cm radius spherical
catalyst pellet at T = 450 K.At 0.7 atm partial pressure of A, the pellet’s production
rate is 2.5 ×10−5 mol/(gm. sec).
Determine the production rate at the same temperature in a 0.15 cm radius spherical
pellet.The pellet density is ρp = 0.85 g/cm3. The effective diffusivity of A in the pellet
is De = 0.007 cm2/sec.
Solution:
𝑟𝐴𝑝 = 𝜂 𝑟𝐴𝑠
𝑟𝐴 = 𝜂 𝑘 𝐶𝐴 𝑠
1 1 1
𝜂= ( − )
∅𝑠 tanh(3∅𝑠 ) 3∅𝑠

The surface concentration and pellet production rates are given by

64 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
𝑃𝐴 0.7 𝑎𝑡𝑚 −5
𝑘𝑚𝑜𝑙 −5
𝑚𝑜𝑙
𝐶𝐴𝑆 = = = 1.9 ∗ 10 = 1.9 ∗ 10
𝑅𝑇 𝑚3 𝑎𝑡𝑚 𝑚3 𝑐𝑚3
0.082 ∗ 450 𝐾
𝑘𝑚𝑜𝑙. 𝐾

rA= 2.5 ×10−5 mol/(gm. sec)* 0.85 g/cm3 =2.125 mol\ cm3.sec

1 1 1
𝑟𝐴 = ( − ) ∗ 𝑘 𝐶𝐴 𝑠
∅𝑠 𝑡𝑎𝑛ℎ(3∅𝑠 ) 3∅𝑠
𝑚𝑜𝑙 1 1 1 −5
𝑚𝑜𝑙
2.125 = ( − ) ∗ 𝑘 ∗ 1.9 ∗ 10
𝑐𝑚3 . 𝑠𝑒𝑐 ∅𝑠 𝑡𝑎𝑛ℎ(3∅𝑠 ) 3∅𝑠 𝑐𝑚3
1
𝑘 = 2.61
𝑠𝑒𝑐
1
0.3 𝑐𝑚 2.61 𝑠𝑒𝑐
∅𝑠 = √ = 1.93
3 𝑐𝑚2
0.007
𝑠𝑒𝑐
1 1 1 1 1 1
𝜂 = ∅ (tanh(3∅ ) − 3∅ ) = 1.93 (𝑡𝑎𝑛ℎ(3∗1.93) − 3∗1.93) =0.38
𝑠 𝑠 𝑠

The smaller pellet is half the radius of the larger pellet, so the Thiele modulus is half
as large or ∅𝑠 = 0.964, which gives 𝜂 = 0.685.
𝑚𝑜𝑙
The production rate is therefore :𝑟𝐴 = 0.685 ∗ 2.6 ∗ 1.9 ∗ 10−5 = 3.38 ∗ 10−5 3
𝑐𝑚 𝑠𝑒𝑐

We see that decreasing the pellet size increases the production rate by almost 60%.
Notice that this type of increase is possible only when the pellet is in the diffusion-
limitted regime.

Example 3:
The rate constant for the first-order cracking of cumene on a silica-alumina catalyst
was measured to be 0.80 cm3\(s.gcat) in a laboratory reactor: Is the observed rate
constant the true rate constant or is there influence of pore diffusion?
Additional data:
𝑔𝑚 −3
𝑐𝑚2
𝑹 = 0.25 𝑐𝑚 ∶ 𝜌𝑝 = 1.2 3 ∶ 𝐷𝑒 = 1.0 ∗ 10
𝑐𝑚 𝑠𝑒𝑐

Solution:
the Thiele modulus is defined in terms of the characteristic length of a pellet:

65 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

𝟏 𝟏 𝟏
𝜼= ( − )
∅𝒔 𝐭𝐚𝐧𝐡(𝟑∅𝒔 ) 𝟑∅𝒔

𝟏 𝟏 𝟏
𝜼= ( − )
𝟐. 𝟗√𝒌 𝒕𝒂𝒏𝒉(𝟑 ∗ 𝟐. 𝟗√𝒌) 𝟑 ∗ 𝟐. 𝟗√𝒌

𝒄𝒎𝟑
𝒌 = 𝟎. 𝟖𝟎
𝒔𝒆𝒄. 𝒈𝒎𝒄𝒂𝒕
𝜼 = 𝟎. 𝟏𝟓

Since 𝜂 is small, there is a great influence of pore diffusion on the observed rate.
Or we can use the Weisz–Prater criterion

Example 4:
A rate of 105 mole/hr m3 cat is observed for a gas concentration of Aof 20 mole/m3.
The catalyst particle diameter is 2.4 mm.
Let us assume effective diffusivity is 5x10-5 m2/hr.Is there a strong pore diffusion
resistance?
Solution:
𝒓𝑨𝒑 = 𝜼 𝒓𝑨𝒔
𝒓𝑨 = 𝜼 𝒌 𝑪𝑨 𝒔
𝒓𝑨 𝟏𝟎𝟓
𝜼𝒌= = = 𝟓𝟎𝟎𝟎 𝒉𝒓−𝟏
𝑪𝑨 𝒔 𝟐𝟎
Since 𝜼 depends on k, we used a trial and error solution. We expect 𝜼 to be small. Let
us assume some value, say 0.01.

5000 5000
𝒌= = = 5 ∗ 105
𝜂 0.01
𝑹 𝒌𝑽 𝟐. 𝟒 ∗ 𝟏𝟎−𝟑 𝟓 ∗ 𝟏𝟎𝟓
∅𝒔 = √ = √ = 𝟒𝟎
𝟑 𝑫𝒆 𝟔 𝟓 ∗ 𝟏𝟎−𝟓

𝟏 𝟏 𝟏
𝜼= ( − ) = 𝟎. 𝟎𝟐𝟓
∅𝒔 𝐭𝐚𝐧𝐡(𝟑∅𝒔 ) 𝟑∅𝒔

66 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

Since 𝜼 = 0.0627 and ∅𝒔 > 𝟓 the internal diffusion is very strong :

Or we can use the Weisz–Prater criterion

Example 5:
The experimental data below is for first order reaction carried out in spinning basket
reactor. If the internal diffusion is important, find the effectiveness factor for each
spherical pellet.
Dp cm rA mol/gm.hr
0.6 0.09
0.3 0.162

The internal diffusion control when

ϕs ≥5 and η = 1/ϕs

𝑟𝐴1 = 𝜂1 𝑘 𝐶𝐴 𝑠1 for pellet 1

𝑟𝐴 2 = 𝜂2 𝑘 𝐶𝐴 𝑠2 for pellet 2
𝑟𝐴1 𝜂1
=
𝑟𝐴 2 𝜂2

0.09 𝜂1
=
0.162 𝜂2

𝜂1 = 0.556 𝜂2

∅𝒔𝟏 𝑅𝑝1
=
∅𝒔 2 𝑅𝑝2

0.6
∅𝒔𝟏
= 2 =2
∅𝒔 2 0.3
2
∅𝒔𝟏 = 2∅𝒔𝟐

η = 1/ϕs The internal diffusion control

67 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
1 1
=2
𝜂1 𝜂2
1
Assume 𝜂2 = 0.3 then 𝜂1 = 0.1668 then ∅𝒔𝟏 = = 5.99
𝜂1
From equation ( ) ∅𝒔𝟐 = 2.996 then 𝜂2 = 0.336
1
𝜂1 = 0.1858 ∅𝒔𝟏 = = 5.39
𝜂1
1
∅𝒔𝟐 = 2.69 𝜂2 = 0.37 then 𝜂1 = 0.205 then ∅𝒔𝟏 = = 4.878
𝜂1
1
∅𝒔𝟐 = 2.439 𝑡ℎ𝑒𝑛 𝜂2 = 0.41 → 𝜂1 = 0.227 → ∅𝒔𝟏 = = 4.386 → ∅𝒔𝟐 =
𝜂1
1
2.193 → 𝜂2 = 0.45 → 𝜂1 = 0.253 → ∅𝒔𝟏 = = 3.944 → ∅𝒔𝟐 = 1.972 → 𝜂2 =
𝜂1
0.506 → 𝜂1 = 0.281 → ∅𝒔𝟏 = 3.55 → ∅𝒔𝟐 = 1.774 → 𝜂2 = 0.56
and we continue calculation until 𝜂2 become constant .

2.4-Significance of External Mass Transfer:

For first order reactions we can use an overall effectiveness factor to help us analyze
diffusion, flow, and reaction in packed beds. We now consider a situation where
external and internal resistance to mass transfer to and within the pellet are of the
same order of magnitude (Figure 18). At steady state, the transport of the reactants
from the bulk fluid to the external surface of the catalyst is equal to the net rate of
reaction of the reactant within and the pellet.

Fig.18: Mass transfer and reaction steps.

The observed rate is also equal to the rate at which reactant "A" is transferred from
the bulk fluid to the external surface ("es") of the porous catalyst pellet.The rate of
mass transfer(MA) from the bulk fluid to the external surface is.

𝑴𝑨 = 𝒌𝒎 𝒂𝒆𝒔 (𝑪𝑨 𝒃 − 𝑪𝑨 𝒔 ) …………………………….(27)

𝑚
where km ( ) is the external mass transfer coefficient.
𝑠𝑒𝑐

68 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
𝑚2
and aes ( ) is the external "geometric" pellet area per unit mass of pellet (for a
𝑘𝑔
sphere, the external area = 4πR2).
𝟔
𝒂𝒆𝒔 = …………………………………….(28)
𝝆𝒄𝒂𝒕 ∗𝒅𝒑

𝑹𝑨𝒑 = 𝜼 𝑹𝑨𝒔

For a first-order reaction in a spherical catalyst.

𝟏 𝟏 𝟏
𝑹𝑨𝒑 = [ − ] 𝒌 𝑪𝑨𝒔
∅𝒔 𝒕𝒂𝒏𝒉(𝟑∅𝒔 ) 𝟑∅𝒔

At equilibrium 𝑅𝐴𝑝 = 𝑀𝐴 : then ………………………………(29)

………………………………(30)

Now substitute this expression for CA,es into either of the above expressions for –rA,obs
(a little quicker with the second one) and rearrange to get our final goal!
……………………………….(31)

Where

………………………………(32)

where Ω, The Overall Effectiveness Factor, is the ratio between the observed rate
and the rate that would be obtained if all active sites in the pellet were exposed to A
at concentration CA,bulk.

You should know the following limiting behavior:

Since ,
𝒎𝟑 𝒎 𝒎𝟐
k1 is (
𝒌𝒈.𝒔𝒆𝒄
) = 𝒌 (𝒔𝒆𝒄) ∗ 𝑺𝒂 (𝒌𝒈 )

Then

69 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

𝟏
𝑹𝑨𝒑 = [ 𝟏 𝒌𝟏 ] 𝒌𝟏 𝑪𝑨 𝒃 ………………………….(33)
+
𝜼 𝒌𝒎 𝒂𝒆𝒔

Or
𝟏
𝑹𝑨𝒑 = [ 𝟏 𝟏 ] 𝑪𝑨 𝒃 ………………………….(34)
+
𝜼 𝒌𝟏 𝒌𝒎 𝒂𝒆𝒔

𝟏
Resistance due to Internal Diffusion
𝜼 𝒌𝟏
𝟏
Resistance due to External Mass Transfer
𝒌𝒎 𝒂𝒆𝒔

𝜴 Overall Effectiveness Factor

𝟏 ……………………….. (35)
𝜴 = [𝟏 𝒌𝟏 ]
+
𝜼 𝒌𝒎 𝒂𝒆𝒔

1-External mass transfer control:

𝒌𝒎 𝒂𝒆𝒔 ≫ 𝜼 𝒌𝟏

𝒌𝒎 𝒂𝒆𝒔
𝜴→
𝒌𝟏

2-Negligible external mass transfer resistance

𝒌𝒎 𝒂𝒆𝒔 ≪ 𝜼 𝒌𝟏
𝜴→𝜼
𝑹𝑨𝒑 = 𝜼 𝒌𝟏 𝑪𝑨 𝒃
𝑪𝑨 𝒔 = 𝑪𝑨 𝒃

3- With negligible external and internal mass transfer resistance, Ω ≥ η ≥ 1, all active
sites inside the pellet are exposed to CA,b, and we have "kinetic control":

𝑹𝑨𝒑 = 𝒌𝟏 𝑪𝑨 𝒃

70 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
2.4.1-Mears’ Criterion for External Mass Transfer:
The Mears criterion, like the Weisz–Prater criterion, uses the measured rate of
reaction, , (kmol/kg cat.sec) to learn if mass transfer from the bulk gas phase to the
catalyst surface can be neglected. Mears proposed that when

..………………………………..(36)

external mass transfer effects can be neglected.

The mass transfer coefficient for single spheres is calculated from the Frössling
correlation:
𝒌𝒎 𝒅𝒑 𝟏 𝟏
𝑺𝒉 = = 𝟐 + 𝟎. 𝟔 ∗ (𝑹 ) 𝟐 ∗ (𝑺 ) 𝟑 ………………………….(37)
𝑫𝑨𝑩 𝒆 𝑪
𝒌𝒎 𝒅𝒑 𝝆 ∗ 𝒅𝒑 ∗ 𝒖 𝟏 𝝂 𝟏
𝑺𝒉 = = 𝟐 + 𝟎. 𝟔 ∗ ( )𝟐 ∗ ( )𝟑
𝑫𝑨𝑩 𝝁 𝑫𝑨𝑩
The Sherwood and Schmidt numbers are, respectively,

In this gas-phase catalytic reaction example, and for most liquids, the Schmidt
number is sufficiently large that the number 2 in Equation (37) is negligible with
respect to the second term when the Reynolds number is greater than 25. As a result,
Equation (37) gives
𝟏 𝟏
𝑫𝑨𝑩 𝒅𝒑 ∗ 𝒖 𝟐 𝝂 𝟐
𝒌𝒎 = 𝟎. 𝟔 ( )( ) ( )
𝒅𝒑 𝝂 𝑫𝑨𝑩
𝟐 𝟏
𝑫𝑨𝑩 𝟑 𝒖𝟐
𝒌𝒎 = 𝟎. 𝟔 ( 𝟏 )∗( 𝟏 )
𝝂𝟔 𝒅𝒑 𝟐

𝒌𝒎 = 𝟎. 𝟔 ∗ (𝑻𝒆𝒓𝒎 𝟏) ∗ (𝑻𝒆𝒓𝒎 𝟐) ………………………….(38)

71 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
Term 1 is a function of the physical properties DAB and 𝝂 , which depend on
temperature and pressure only. The diffusivity always increases with increasing
temperature for both gas and liquid systems. However, the kinematic viscosity 𝝂
increases with temperature (𝝂 ∝ T3/2) for gases and decreases exponentially with
temperature for liquids. Term 2 is a function of flow conditions and particle size.
Consequently, to increase km and thus the overall rate of reaction per unit surface
area, one may either decrease the particle size or increase the velocity of the fluid
flowing past the particle. For this particular case of flow past a single sphere, we see
that if the velocity is doubled, the mass transfer coefficient and consequently the rate
of reaction is increased by a factor of (U2 /U1 )0.5 = 20.5 = 1.41 or 41%

Figure 19 shows the variation in reaction rate with Term 2 in Equation (38), the ratio
of velocity to particle size. At low velocities the mass transfer boundary layer
thickness is large and diffusion limits the reaction. As the velocity past the sphere is
increased, the boundary layer thickness decreases, and the mass transfer across the
boundary layer no longer limits the rate of reaction. One also notes that for a given
velocity, reaction-limiting conditions can be achieved by using very small particles.
However, the smaller the particle size, the greater the pressure drop in a packed bed.

When one is obtaining reaction rate data in the laboratory, one must operate at
sufficiently high velocities or sufficiently small particle sizes to ensure that the
reaction is not mass transfer–limited.

Increasing the gas-phase velocity and decreasing the particle size will increase the
overall rate of reaction for reactions that are externally mass transfer–limited.

Fig. 19: Regions of mass transfer–limited and reaction–limited reactions.

72 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

2.5-Internal and External Heat and Mass Transfer:

To quickly estimate the importance of external mass-transfer limitations, the
magnitude of the change in concentration across the boundary layer can be calculated
from the observed rate and the mass-transfer coefficient:
𝒓𝑨 = 𝒌𝒎 𝒂𝒆𝒔 (𝑪𝑨 𝒃 − 𝑪𝑨 𝒔 ) ……………………………(39)

The effects of heat transfer are completely analogous to those of mass transfer. The
heat flux, q, across the stagnant boundary layer is related to the difference in
temperature and the heat-transfer coefficient, h according to:

𝒒 = 𝒉(𝑻𝒃 − 𝑻𝒔 ) …………………………...(40)

Steady state requires that the heat flux is equivalent to the heat generated (or
consumed) by reaction:

𝒓𝑨 ∗ ∆𝑯𝒓 = 𝒉(𝑻𝒃 − 𝑻𝒔 ) ……………………………..(41)

𝒓𝑨 ∗∆𝑯𝒓
= 𝑻𝒃 − 𝑻𝒔 = ∆𝑻 ………………………….(42)
𝒉

where ∆Hr is the heat of reaction per mole of A converted. To estimate the influence
of heat-transfer limitations on the observed rate, the change in temperature across the
film is found by evaluating the observed rate of heat generated (or consumed) and the
heat-transfer coefficient (obtained from J factor correlations, similar to the case of
mass-transfer coefficients):

Equation (42) can also be used to find the maximum temperature change across the
film. Using Equation (39) to eliminate the observed rate, the resulting equation
relates the concentration change across the film to the temperature change:

𝒌𝒎 𝒂𝒆𝒔 (𝑪𝑨 𝒃 − 𝑪𝑨 𝒔 )∗∆𝑯𝒓 ………………………………(43)

= 𝑻𝒃 − 𝑻𝒔 = ∆𝑻
𝒉
The maximum temperature change across the film will occur when CAS approaches
zero, which corresponds to the maximum observable rate. Solving Equation (43) for
∆Tmax with CAS = 0 gives the following expression:

𝒌𝒎 𝒂𝒆𝒔 ∗ ∆𝑯𝒓 ∗ 𝑪𝑨 𝒃 ………………………………(44)

∆𝑻𝒎𝒂𝒙 =
𝒉

that can always be calculated for a reaction, independent of an experiment. If both

external heat and mass transfer are expected to affect the observed reaction rate, the
balances must be solved simultaneously.

The relationship between temperature and concentration is:

73 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
∆𝑯𝒓 ∗𝑫𝒆 ………………………………(45)
𝑻 = 𝑻𝒔 + [ ] (𝑪𝑨 𝒔 − 𝑪𝑨 𝒃 )
𝒌𝒆

Where 𝑘𝑒 is the effective thermal conductivity of the fluid-solid system,

The above equation is called the Prater Relation. From this relationship, the
adiabatic temperature rise in a catalyst pellet can be calculated. The maximum
temperature is reached when the reactant is completely converted in the pellet, that is,
CA = 0:
∆𝑯𝒓 ∗ 𝑫𝒆 …………………………………(46)
𝑻𝒎𝒂𝒙 − 𝑻𝒔 = ∗ 𝑪𝑨 𝒔
𝒌𝒆

--------------------------------------------------------------------------------

Homework Problems:
1- A first order irreversible catalytic reaction A → P is carried out at isothermal
conditions, in absence of all external transport effects, in a stirred basket reactor on
two different size catalyst pellets. The pellets are spherical. The catalyst activity and
pore structure of the pellets are identical. Therefore the kinetic rate constant and
effective diffusivity are identical in pellets of both sizes. The temperature, pressure
and bulk reactant concentration are identical in both runs. The following data are
obtained.

Pellet Diameter(cm) Observed Rate x 105

(mol/cm3cat.s)
Run 1 1.0 3.0
Run 2 0.1 15.0

a) Estimate the Thiele modulus(𝜃𝑆 ) and effectiveness factor  for each particle. Are
internal diffusion effects pronounced in each pellet size?
b)What pellet diameter is needed to completely eliminate internal diffusion resistance
at the temperature of these experiments (i.e.   1).

2- The first-order reaction A→B was carried out over two different-sized pellets. The
pellets were contained in spinning basket reactor that was operated at sufficiently
high rotation speeds so the external mass transfer resistance was negligible. The

74 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
results of two experiment runs made under identical conditions are as given in Table
below
(a) Estimate the Thiele modulus and effectiveness factor for each pellet.
(b) How small should the pellet be made to virtually eliminate all internal diffusion
resistance?

3- The rate of isomerization of n-butane on a silica-alumna spherical catalyst

measured at 5 atm and 50oC, in a laboratory reactor with high turbulence in the gas
phase surrounding the catalyst pellet is given below. Turbulence ensures that the
external diffusion resistances are negligible. Kinetic studies indicate that the rate is
first order and irreversible. The effective diffusivity is 0.08 cm2/sec at the reaction
conditions, and the density of the catalyst pellet is 1 g/cm3 regardless of the size. The
measured rates when pure n-butane surrounds the catalyst are as follows:
Particle diameter 1/16 1/8 ¼ 3/8 1
(in)

Rate mol/sec/g of 4.88 x 10-4 4.85 x 10-4 4.01 x 10-4 3.54 x 10-4 1 x 10-5
catalyst

From the above data, determine the intrinsic first order rate constant in the absence of
intraparticle diffusion. Also predict the rate if the particle size is 1.5 inch. It may be
assumed that effectiveness factor (𝜂) is inverse of Thiele modulus (𝜃𝑆 ) (i.e. 𝜂 = 1/𝜃𝑆 )
when 𝜃𝑆 ≥3.

4- The irreversible, first-order reaction of gaseous A → B occurs in spherical catalyst

pellets with a radius of 2 mm. For this problem, the molecular diffusivity of A is 1.2
X 10-1 cm2 s- 1 and the Knudsen diffusivity is 9 * 10- 3cm2 s-1. The intrinsic first-order
rate constant determined from detailed laboratory measurements was found to be 5.0
s-1. The concentration of A in the surrounding gas is 0.0 I mol L-1. Assume the
porosity and the tortuosity of the pellets are 0.5 and 4, respectively.
(a) Determine the Thiele modulus for the catalyst pellets.
(b) Find a value for the internal effectiveness factor.
(c) For an external mass-transfer coefficient of 32s-1 (based on the external area of the
pellets), determine the concentration of A at the surface of the catalyst pellets.

5-The importance of diffusion in catalyst pellets can often be determined by

measuring the effect of pellet size on the observed reaction rate. In this exercise,

75 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
consider an irreversible first-order reaction occurring in catalyst pellets where the
surface concentration of reactant A is CAS = 0.15 M.

Data:

(a) Calculate the intrinsic rate constant and the effective diffusivity.
(b) Estimate the effectiveness factor and the anticipated rate of reaction (robs) for a
finite cylindrical catalyst pellet of dimensions 0.6 cm x 0.6 cm (diameter = length).

6- Ercan et al. studied the alkylation of ethylbenzene, EB, with light olefins (ethylene
and propylene) over a commercial zeolite Y catalyst in a fixed-bed reactor with
recycle.. The solid-catalyzed liquid-phase reaction was carried out in excess
ethylbenzene at 25 bar and 190°C.
Assume the reaction is pseudo-first-order with respect to olefin. The porosity of the
catalyst was 0.5, the tortuosity was 5.0, and the density was 1000 kg m-3. The
observed rate (robsJ and rate constant (kobs) were measured for two different catalyst
pellet sizes. Relevant results are given below:

(a) Determine whether or not external and internal mass transfer limitations are
significant for each case. Assume the diffusivity of olefins in ethylbenzene is DAB =
1.9 * 10-4 cm2S-l.
(b) Calculate the Thiele modulus, (𝜃𝑆 ) , and the internal effectiveness factor), for
each case.
(c) Determine the overall effectiveness factor for each case.

7- The production rate of a heterogeneously, first-order reaction in a 0.75cm diameter

spherical pellet is RAp = 3.25*105 mol/cm3.s when the catalyst is exposed to pure,
gaseous A at a pressure of 1 atm and a temperature of 525 K. This reaction's
activation energy is E= 18 600 cal/mol. Further, the effective diffusivity of A in the
pellet is DA= 0:009 cm2/s at 525 K and that diffusion is in the regime of Knudsen
floow. The bulk fluid and the external surface concentrations can be assumed the
same. Find the production rate if the catalyst is changed to a cylindrical pellet that is
0.5 cm in diameter and 1.0 cm in length, and the temperature is increased to 600 K.

76 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
8- A gas-phase hydrogenation reaction was studied using a catalyst fine enough to
avoid any effect of pore diffusion. The rate equation is:

a- For the following gas compositions, sketch the concentration gradients for A,
H2, and B for the case where the reaction is rapid enough to make PAave 10%
less than PA. Assume DA = 1\4DH2

b. Estimate the effectiveness factors for the two cases.

9-For the 1st order reaction A → B which takes place over a spherical catalyst
particle:The maximum temperature rise over the catalyst is equal to 90 oF.
The effective diffusivity De = 5*10 6 ft2/sec
The effective thermal conductivity ke =0.25 Btu/hr.ft. oF
The heat of reaction is ∆HR = -5000 Btu/mole
What is the concentration of component A on the surface of the catalyst particle?

10-For the 2nd order reaction A → B which takes place over a spherical catalyst
particle:
The maximum temperature rise over the catalyst is equal to 100 oF.
The effective diffusivity De = 5*10 6 ft2/sec
The effective thermal conductivity ke =0.25 Btu/hr.ft. oF
The heat of reaction is ∆HR = -5000 Btu/mole
a) What is the concentration of component A on the surface of the catalyst particle?
b) What is the rate of mass transfer if the bulk concentration is 2*C As and the mass
transfer coefficient for the binary system is 1 cm/sec

11- Consider a porous catalyst pellet with a diameter of 6 mm. The porosity of the
pellet is 0.55, the tortuosity factor is 4.0, the internal surface area is 200 m2/g, and the
pellet density is 2.0 g/cm3. The following first-order reaction occurs in the pellet at a
temperature of 475 K: A → B where (−rA) = kCA
The rate constant at the reaction temperature has a value of 0.1 s−1. The molecular
weight of A and B is 16 g/mol. The bulk diffusion coefficient of A in the reacting
mixture is 5 × 10−5 m2/s. Determine the value of the effectiveness factor in the
pellet.

77 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

Part Three:
• Design of catalytic reactors.
• Isothermal and adiabatic fixed bed reactors.

78 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

3.1-Fixed-bed Reactors Design:

Reactions on solid catalysts are often carried out in tubes or pipes packed with
spherical, cylindrical, or ring-shaped catalyst particles. For exothermic reactions,
small-diameter tubes are used to permit nearly isothermal operation and prevent a
temperature runaway. For small-scale operation, a cooling jacket can be placed
around each pipe. But for large production, hundreds or thousands of tubes
containing catalyst are mounted in a heat exchanger, with coolant circulated on the
shell side. The design is more complicated than for homogeneous reactions, since
there are radial as well as axial temperature gradients in the tubes, and there may also
be significant concentration and temperature gradients near the surface of the
individual particles.

In the chemical industry fixed-bed reactors are the standard type of reactors for
heterogeneously catalyzed gas phase reactions (two phase reactors). Multiple layers
of these screens constitute the catalyst bed that are used in commercial processes for
the oxidation or synthesis.
Applications of fixed bed reactor can be described in table 2.

Table 2 : Main fixed-tube reactor processes.

Fixed-bed reactors can be operated under adiabatic or nonadiabatic conditions that

depend of temperature change. Because of the necessity of removing or adding heat,
it may not be possible to use a single large-diameter tube packed with catalyst. In this
event the reactor may be built up of a number of tubes encased in a single body to
prevent excessive temperatures. There are types of fixed-bed reactors as shown in
figures 20and 21.

79 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

Figure 20 : Packed bed reactor types.

Fig. 21 : Multitube Fixed bed reactor for

exothermic and endothermic reactions.

80 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
Consider an isothermal catalytic reaction in a PBR where there is no pressure drop
and the catalyst pellets are uniformly packed & spherical. The kinetics are 1st
order, and k, all physical parameters, and the inlet conditions (pure A in feed,
A→ products) are given. Derive an equation for XA, taking into account the
diffusion to and within each catalyst particle, but ignore diffusion down the length of
the reactor.

The design equation for packed bed reactor is

𝑑𝑊 𝑥 𝑑𝑥 …………………………….(1)
∫𝐹 = ∫0
𝐴𝑜 𝑟𝐴 𝑝

𝟏
𝑹𝑨𝒑 = [ ] 𝑪𝑨 𝒃
𝟏 𝟏
+
𝜼 𝒌𝟏 𝒌𝒎 𝒂𝒆𝒔
𝟏
Resistance due to Internal Diffusion
𝜼 𝒌𝟏

𝟏
Resistance due to External Mass Transfer
𝒌𝒎 𝒂𝒆𝒔

𝑑𝑊 𝑥 𝑑𝑥
∫𝐹 = ∫0 ……………………………………(2)
𝐴𝑜 𝟏
[ 𝟏 𝟏 ]𝑪𝑨 𝒃
+
( 𝜼 𝒌𝟏 𝒌𝒎𝒂𝒆𝒔 )
𝑪𝑨 𝒃 = 𝐶𝐴𝑜 (1 − 𝑥)

𝟏 𝟏 𝟏
𝜼= ( − )
∅𝒔 𝐭𝐚𝐧𝐡(𝟑∅𝒔 ) 𝟑∅𝒔

𝑹 𝒌𝑽
∅𝒔 = √
𝟑 𝑫𝒆

Case 1: First order reaction ,both external and internal resistance are
important.

∅𝒔 is independent on conversion x , also the effectivnees factor. Then

81 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

1
𝑅𝐴𝑝 = [ ] 𝑘1 𝐶𝐴 𝑏
1 𝑘1
+
𝜂 𝑘𝑚 𝑎𝑒𝑠

1
𝜴=[ ]
1 𝑘1
+
𝜂 𝑘𝑚 𝑎𝑒𝑠
𝑥 𝑥
𝑑𝑊 𝑑𝑥 𝑑𝑥
∫ =∫ ( )=∫
𝐹𝐴 𝑜 0 𝜴𝒌𝟏 𝑪𝑨 𝒃 0 𝜴𝒌𝟏 𝐶𝐴𝑜 (1 − 𝑥)

𝑥
𝑑𝑊 1 𝑑𝑥
∫ = ∫
𝐹𝐴 𝑜 𝜴𝒌𝟏 𝐶𝐴𝑜 0 1 − 𝑥

𝑾 −𝟏
= 𝐥𝐧(𝟏 − 𝒙)
𝑭𝑨 𝒐 𝜴𝒌𝟏 𝑪𝑨𝒐

The weight of Catalyst is:

− 𝑭𝑨 𝒐
𝑾= 𝐥𝐧(𝟏 − 𝒙)
𝜴𝒌𝟏 𝑪𝑨𝒐
0r to find the conversion from

𝑾∗𝜴𝒌𝟏 𝑪𝑨𝒐
−
𝑭𝑨 𝒐
𝒙=𝟏−𝒆
Since :
𝑾 = 𝝆𝒄𝒂𝒕 ∗ 𝑽𝒄𝒂𝒕
𝑾 = 𝝆𝒄𝒂𝒕 ∗ 𝑽𝑹𝑬𝑨𝑪𝑻𝑶𝑹 (𝟏 − 𝒆)
𝑾 = 𝝆𝒄𝒂𝒕 (𝟏 − 𝒆) ∗ 𝑨𝒄 ∗ 𝒁 … … … … … … … … … … … . . (3)
And
𝑭𝑨 𝒐 = 𝑪𝑨𝒐 ∗ 𝑨𝒄 ∗ 𝒖 and 𝝆𝒃𝒆𝒅 = 𝝆𝒄𝒂𝒕 (𝟏 − 𝒆)
Where:

e = porosity of bed (void fraction).

𝜌𝑏𝑒𝑑 : bed density (kg/m3 bed)
Ac: Cross section area of reactor or tube (m2).
Z: reactor length (m).
u : gas velocity (m/sec).
𝐹𝐴 𝑜 : molar flow rate (mole/sec).
Then:

82 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

−𝝆𝒄𝒂𝒕 (𝟏−𝒆)∗𝑨𝒄 ∗𝒁∗𝜴𝒌𝟏 𝑪𝑨𝒐

𝒙=𝟏− 𝒆 𝑪𝑨𝒐 ∗𝑨𝒄 ∗𝒖
−𝝆𝒃𝒆𝒅∗𝒁∗𝜴𝒌𝟏
𝒙=𝟏−𝒆 𝒖

𝒁 𝑽(𝑹𝒆𝒂𝒄𝒕𝒐𝒓 𝑽𝒐𝒍𝒖𝒎𝒆) 𝒎𝟑
= = = 𝝉(𝑹𝒆𝒔𝒊𝒅𝒂𝒏𝒕 𝑻𝒊𝒎𝒆)
𝒖 𝑸𝒐 (𝑽𝒐𝒍𝒖𝒎𝒆𝒕𝒓𝒊𝒄 𝑭𝒍𝒐𝒘 𝒓𝒂𝒕𝒆 𝒎𝟑
𝒔𝒆𝒄
−𝝆𝒃𝒆𝒅 ∗ 𝜴𝒌𝟏 ∗𝝉
𝒙=𝟏−𝑒
Define:
𝒌∗ = 𝝆𝒃𝒆𝒅 ∗ 𝜴𝒌𝟏
∗
𝒙 = 𝟏 − 𝒆−𝒌 𝝉
∗
𝑪𝑨 = 𝑪𝑨𝒐 𝒆−𝒌 𝝉
Case 2: First order reaction , external mass transfer control.

𝟏
𝑹𝑨𝒑 = [ ] 𝒌𝟏 𝑪𝑨 𝒃
𝟏 𝒌𝟏
+
𝜼 𝒌𝒎 𝒂𝒆𝒔

𝒌𝒎 𝒂𝒆𝒔 ≫ 𝜼 𝒌𝟏

Then
𝑹𝑨𝒑 = 𝒌𝒎 𝒂𝒆𝒔 𝑪𝑨 𝒃

𝒙 𝒙
𝒅𝑾 𝒅𝒙 𝟏 𝒅𝒙
∫ =∫ ( )= ∫
𝑭𝑨 𝒐 𝟎 𝒌𝒎 𝒂𝒆𝒔 𝑪𝑨 𝒃 𝒌𝒎 𝒂𝒆𝒔 ∗ 𝑪𝑨𝒐 𝟎 (𝟏 − 𝒙)

The weight of Catalyst is:

− 𝑭𝑨 𝒐
𝑾= 𝐥𝐧(𝟏 − 𝒙)
𝒌𝒎 𝒂𝒆𝒔 ∗ 𝑪𝑨𝒐

𝑭𝑨 𝒐 𝟏
𝑾= 𝐥𝐧
𝒌𝒎 𝒂𝒆𝒔 ∗ 𝑪𝑨𝒐 𝟏 − 𝒙

0r to find the conversion from

𝒌 𝒂 ∗𝑪 ∗𝑾
− 𝒎 𝒆𝒔 𝑨𝒐
𝑭𝑨 𝒐
𝒙=𝟏−𝒆
83 Chemical Engineering Department- University of Basrah
Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
−𝝆𝒃𝒆𝒅∗𝒁∗𝒌𝒎𝒂𝒆𝒔
𝒙=𝟏− 𝒆 𝒖

𝒙 = 𝟏 − 𝒆−𝒌𝒎𝒂𝒆𝒔 ∗𝝉∗𝝆𝒃𝒆𝒅
𝑪𝑨 = 𝑪𝑨𝒐 𝒆−𝒌𝒎 𝒂𝒆𝒔 ∗𝝉∗𝝆𝒃𝒆𝒅
aes: external surface area of catalyst per catalyst mass.
𝟔 𝒎𝟐
𝒂𝒆𝒔 = ( )
𝝆𝒄𝒂𝒕 ∗ 𝒅𝒑 𝒌𝒈

Case 3: First order reaction , internal diffusion control.

𝟏
𝑹𝑨𝒑 = [ ] 𝒌𝟏 𝑪𝑨 𝒃
𝟏 𝒌𝟏
+
𝜼 𝒌𝒎 𝒂𝒆𝒔

𝒌𝒎 𝒂𝒆𝒔 ≪ 𝜼 𝒌𝟏
𝜴→𝜼
𝑹𝑨𝒑 = 𝜼 𝒌𝟏 𝑪𝑨 𝒃

𝒙 𝒙
𝒅𝑾 𝒅𝒙 𝟏 𝒅𝒙
∫ =∫ ( )= ∫
𝑭𝑨 𝒐 𝟎 𝜼 𝒌𝟏 𝑪𝑨 𝒃 𝜼 𝒌𝟏 𝑪𝑨 𝒐 𝟎 (𝟏 − 𝒙)

𝜼 𝒂𝒏𝒅 ∅𝒔 𝒂𝒓𝒆 𝒏𝒐𝒕 𝒇𝒖𝒏𝒄𝒕𝒊𝒐𝒏 𝒐𝒇 𝒙

𝟏 𝟏 𝟏
𝜼= ( − )
∅𝒔 𝐭𝐚𝐧𝐡(𝟑∅𝒔 ) 𝟑∅𝒔
𝑹 𝒌𝑽
∅𝒔 = √
𝟑 𝑫𝒆
The weight of Catalyst is:
− 𝑭𝑨 𝒐
𝑾= 𝐥𝐧(𝟏 − 𝒙)
𝜼 𝒌𝟏 𝑪𝑨 𝒐
𝑭𝑨 𝒐 𝟏
𝑾= 𝒍𝒏
𝜼 𝒌𝟏 𝑪𝑨 𝒐 𝟏 − 𝒙

0r to find the conversion from

𝑾∗𝜼 𝒌𝟏 𝑪𝑨 𝒐
− 𝑭𝑨 𝒐
𝒙=𝟏−𝒆
𝒙 = 𝟏 − 𝒆− 𝝆𝒃𝒆𝒅 ∗𝜼 𝒌𝟏∗𝝉
𝑪𝑨 = 𝑪𝑨𝒐 𝒆− 𝝆𝒃𝒆𝒅 ∗𝜼 𝒌𝟏 ∗𝝉
84 Chemical Engineering Department- University of Basrah
Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
The concentration and conversion profiles down a reactor of length Z for all cases
are shown in Figure 22.

Fig. 22: Axial concentration (a) and conversion (b) profiles in a packed bed.

Example 1:
The decomposition of hydrazine over a packed bed of alumina-supported iridium
catalyst is of interest . In a proposed study, a 2% hydrazine in 98% helium mixture is
to be passed over a packed bed of cylindrical particles 0.25 cm in diameter and 0.5
cm in length at a gas-phase velocity of 15 m/s and a temperature of 750 K. The
kinematic viscosity of helium at this temperature is 4.5 10 -4 m2 /s. The hydrazine
decomposition reaction is believed to be externally mass transfer–limited under these
conditions. If the packed bed is 0.05 m in length, what conversion can be expected?
Assume isothermal operation.

Solution:
𝒙 = 𝟏 − 𝒆−𝒌𝒎𝒂𝒆𝒔 ∗𝝉∗𝝆𝒃𝒆𝒅
𝑪𝑨 = 𝑪𝑨𝒐 𝒆−𝒌𝒎 𝒂𝒆𝒔 ∗𝝉∗𝝆𝒃𝒆𝒅
Calculate the mass transfer coefficient km

85 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

𝒌𝒎 𝒅𝒑 𝝆 ∗ 𝒅𝒑 ∗ 𝒖 𝟏 𝝂 𝟏
= 𝟐 + 𝟎. 𝟔 ∗ ( )𝟐 ∗ ( )𝟑
𝑫𝑨𝑩 𝝁 𝑫𝑨𝑩
𝒌𝒎 𝒅𝒑 𝟏 𝟏
= 𝟐 + 𝟎. 𝟔 ∗ ( 𝟏𝟐𝟎. 𝟑 ) ∗ (𝟏. 𝟑) 𝟑 = 𝟗. 𝟐𝟑
𝟐
𝑫𝑨𝑩

𝟗. 𝟐𝟑 ∗ 𝟑. 𝟒𝟕 ∗ 𝟏𝟎−𝟒 𝒎
𝒌𝒎 = = 𝟎. 𝟖𝟖𝟕
𝟑. 𝟔𝟏 ∗ 𝟏𝟎−𝟑 𝒔𝒆𝒄
𝒁 𝟎. 𝟎𝟓
𝝉= = = 𝟎. 𝟎𝟎𝟑𝟑 𝒔𝒆𝒄
𝒖 𝟏𝟓
𝟔
𝒂𝒆𝒔 =
𝝆𝒄𝒂𝒕 ∗ 𝒅𝒑
𝟔
− 𝒌𝒎 ∗ ∗𝝉∗(𝟏−𝒆)𝝆𝒄𝒂𝒕
𝝆𝒄𝒂𝒕 ∗𝒅𝒑
𝒙 = 𝟏 − 𝒆−𝒌𝒎 𝒂𝒆𝒔 ∗𝝉∗𝝆𝒃𝒆𝒅 = 𝟏 − 𝒆
−𝟔∗𝒌𝒎 ∗𝝉∗(𝟏−𝒆)
𝒙=𝟏− 𝒆 𝒅𝒑

𝒙 = 𝟏 − 𝟎. 𝟏𝟕 = 𝟎. 𝟖𝟑

3.2-Second Order Reaction in PBR:

The rate of mass transfer(MA) from the bulk fluid to the external surface is.
𝑀𝐴 = 𝑘𝑚 𝑎𝑒𝑠 (𝐶𝐴 𝑏 − 𝐶𝐴 𝑠 )
The rate of reaction is given by:
𝒓𝑨 = 𝜼 𝒌𝟐 𝑪𝑨𝑺 𝟐

At equilibrium 𝑀𝐴 = 𝒓𝑨 then
𝒌𝒎 𝒂𝒆𝒔 (𝑪𝑨 𝒃 − 𝑪𝑨 𝒔 ) = 𝜼 𝒌𝟐 𝑪𝑨𝑺 𝟐

𝒌𝒎 𝒂𝒆𝒔 𝒌𝒎 𝒂𝒆𝒔
𝑪𝑨𝑺 𝟐 + ( ) 𝑪𝑨𝑺 − ( ) 𝑪𝑨𝒃 = 𝟎
𝜼 𝒌𝟐 𝜼 𝒌𝟐

𝒌𝒎 𝒂𝒆𝒔 𝒌𝒎 𝒂𝒆𝒔 𝟐 𝒌 𝒂
−( ) + √( ) + 𝟒 ( 𝒎 𝒆𝒔 ) 𝑪𝑨𝒃
𝜼 𝒌𝟐 𝜼 𝒌𝟐 𝜼 𝒌𝟐
𝑪𝑨𝑺 =
𝟐
86 Chemical Engineering Department- University of Basrah
Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
The general equation for irreversible reactions second order or higher can be
estimated from the formula:
𝒏 + 𝟏 𝒌 𝑽 ∗ 𝑪𝑨𝑺 𝒏−𝟏
∅𝒔 = 𝑳√( )
𝟐 𝑫𝒆
For second order reaction(n=2) and for spherical pellet L=R\3
𝒏 + 𝟏 𝒌 𝑽 ∗ 𝑪𝑨𝑺 𝒏−𝟏
∅𝒔 = 𝑳√( )
𝟐 𝑫𝒆
𝑹 𝟑 𝒌 𝟐 𝑪𝑨𝑺
∅𝒔 = √( )
𝟑 𝟐 𝑫𝒆
For second order reaction and for large values of the Thiele modulus, the
effectiveness factor is calculated by two methods:
𝟏
(a) 𝜼=
∅𝒔
𝟏
𝟐 𝟐 𝟑
(b) 𝜼= ( ) ∗
𝒏+𝟏 ∅𝒔

Consequently, for reaction orders greater than 1 , the effectiveness factor decreases
with increasing concentration at the external pellet surface (function of conversion).
The preceding discussion of effectiveness factors is valid only far isothermal
conditions. Note that the Thiele Modulus will be a function of position.
For simple design procedure we use method (a).

Case 1: internal diffusion control. 𝑪𝑨𝒃 = 𝑪𝑨𝑺

𝒓𝑨𝒑 = 𝜼𝒌𝟐 𝑪𝑨𝒃 𝟐

𝑥 𝑥 𝑥
𝑑𝑊 𝑑𝑥 𝑑𝑥 1 𝑑𝑥
∫ =∫ =∫ = ∫
𝐹𝐴 𝑜 0 𝑟𝐴 𝑝 0 𝜼 𝒌𝟐 𝑪𝑨𝒃
𝟐
𝑘2 𝐶𝐴𝑜 2 0 (1 − 𝑥)2 𝜂
𝑥
𝑑𝑊 1 𝑑𝑥
∫ = ∫
𝐹𝐴 𝑜 𝑘2 𝐶𝐴𝑜 2 0 (1 − 𝑥)2 1
𝜑𝑠
𝑥
𝑑𝑊 1 𝜑𝑠
∫ = ∫ ( ) 𝑑𝑥
𝐹𝐴 𝑜 𝑘2 𝐶𝐴𝑜 2 0 (1 − 𝑥)2

𝑹 𝟑 𝒌 𝟐 𝑪𝑨𝑺 𝑹 𝟑 𝒌 𝑪
∅𝒔 = √( ) = √( ) 𝟐 𝑨𝒃
𝟑 𝟐 𝑫𝒆 𝟑 𝟐 𝑫𝒆
𝑹 𝟑 𝒌 𝟐 𝑪𝑨𝒃
√
𝑑𝑊 1 𝑥
𝟑 (𝟐) 𝑫𝒆
∫ = ∫ 𝑑𝑥
𝐹𝐴 𝑜 𝑘2 𝐶𝐴𝑜 2 0 (1 − 𝑥)2
( )
87 Chemical Engineering Department- University of Basrah
Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
Define
𝑹 𝟑 𝒌𝟐
𝒄= √ ∗
𝟑 𝟐 𝑫𝒆
𝒅𝑾 𝒄 𝒙
𝑪𝑨𝒃 𝟎.𝟓
∫ = (∫ 𝒅𝒙)
𝑭𝑨 𝒐 𝒌𝟐 𝑪𝑨𝒐 𝟐 𝟎 (𝟏 − 𝒙)𝟐

𝒅𝑾 𝑪𝑨𝒐 𝟎.𝟓 ∗ 𝒄 𝒙
(𝟏 − 𝒙) 𝟎.𝟓
∫ = (∫ 𝒅𝒙)
𝑭𝑨 𝒐 𝒌𝟐 𝑪𝑨𝒐 𝟐 𝟎 (𝟏 − 𝒙)
𝟐

𝒅𝑾 𝑪𝑨𝒐 𝟎.𝟓 ∗ 𝒄 𝒙
𝟏
∫ = ( ∫ 𝒅𝒙)
𝑭𝑨 𝒐 𝒌𝟐 𝑪𝑨𝒐 𝟐 𝟎 (𝟏 − 𝒙)
𝟏.𝟓

The integration could be calculated numericaly or analyticaly

The integral value =𝟑(𝟏 − 𝒙𝟎.𝟓 )

𝒅𝑾 𝑪𝑨𝒐 𝟎.𝟓 ∗𝒄
∫𝑭 = ∗ 𝟑(𝟏 − 𝒙𝟎.𝟓 )
𝑨𝒐 𝒌𝟐 𝑪𝑨𝒐 𝟐

𝟑 𝒄 ∗ 𝑭𝑨 𝒐
𝑾= (√𝒙 − 𝟏)
𝒌𝟐 𝑪𝑨𝒐 𝟏.𝟓
Note:
𝟑 𝒄∗𝑭𝑨 𝒐
The units of ( 𝟏.𝟓 ) is kgcat
𝒌𝟐 𝑪𝑨𝒐
𝑾 = 𝝆𝒄𝒂𝒕 (𝟏 − 𝒆) ∗ 𝑨𝒄 ∗ 𝒁

Case 2: mass transfer control:

From equation 2

𝒌𝒎 𝒂𝒆𝒔 𝒌𝒎 𝒂𝒆𝒔 𝟐 𝒌 𝒂
−( √
)+ ( ) + 𝟒 ( 𝒎 𝒆𝒔 ) 𝑪𝑨𝒃
𝜼 𝒌𝟐 𝜼 𝒌𝟐 𝜼 𝒌𝟐
𝑪𝑨𝑺 =
𝟐
𝟐
𝟐
𝒌𝒎 𝒂𝒆𝒔 𝒌 𝒂 𝒌 𝒂
−( ) + √( 𝒎 𝒆𝒔 ) + 𝟒 ( 𝒎 𝒆𝒔 ) 𝑪𝑨𝒃
𝜼 𝒌𝟐 𝜼 𝒌𝟐 𝜼 𝒌𝟐
𝑪𝑨𝑺 𝟐 =
𝟐

( )

88 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

𝒌𝒎 𝒂𝒆𝒔 𝟐 𝒌𝒎 𝒂𝒆𝒔 𝒌𝒎 𝒂𝒆𝒔 √ 𝒌𝒎 𝒂𝒆𝒔 𝟐 𝒌 𝒂

( ) + 2( ) 𝑪𝑨𝒃 − ( ) + 𝟒 ( 𝒎 𝒆𝒔 ) 𝑪𝑨𝒃
𝜼 𝒌𝟐 𝜼 𝒌𝟐 𝜼 𝒌𝟐 𝜼 𝒌𝟐 𝜼 𝒌𝟐
𝑪𝑨𝑺 𝟐 =
2
CAs ≈ 0 in most mass transfer-limited reactions
Then

𝒌𝒎 𝒂𝒆𝒔 𝟐 𝒌𝒎 𝒂𝒆𝒔 𝒌𝒎 𝒂𝒆𝒔 𝒌𝒎 𝒂𝒆𝒔 𝟐 𝒌𝒎 𝒂𝒆𝒔

( ) + 2( ) 𝑪𝑨𝒃 = √( ) + 𝟒( ) 𝑪𝑨𝒃
𝜼 𝒌𝟐 𝜼 𝒌𝟐 𝜼 𝒌𝟐 𝜼 𝒌𝟐 𝜼 𝒌𝟐

𝒌𝒎 𝒂𝒆𝒔 𝒌𝒎 𝒂𝒆𝒔 𝟐 𝒌𝒎 𝒂𝒆𝒔

+ 2𝑪𝑨𝒃 = √( ) +𝟒( ) 𝑪𝑨𝒃
𝜼 𝒌𝟐 𝜼 𝒌𝟐 𝜼 𝒌𝟐

𝟐
√(𝒌𝒎 𝒂𝒆𝒔 ) + 𝟒 (𝒌𝒎 𝒂𝒆𝒔 ) 𝑪𝑨𝒃 − 𝒌𝒎 𝒂𝒆𝒔
𝜼 𝒌𝟐 𝜼 𝒌𝟐 𝜼 𝒌𝟐
𝑪𝑨𝒃 =
𝟐

𝑹 𝟑 𝒌 𝟐 𝑪𝑨𝑺 𝑹 𝟑 𝒌 𝟐 𝑪𝑨𝒃
∅𝒔 = √( ) = √( )
𝟑 𝟐 𝑫𝒆 𝟑 𝟐 𝑫𝒆
𝟏
𝜼=
∅𝒔
𝑪𝑨𝒃 = 𝑪𝑨𝒐 (𝟏 − 𝒙)

The above equations solved by trial and error to𝑪𝑨𝒃 , ∅𝒔 ,and 𝜼 at different x

X ∅𝒔 𝜼
0
0.1
0.2

X final

Example 2:
Design a packed bed reactor in which the second order reaction A → B + 2C is being
conducted under internal diffusional limiting conditions and the exit conversion is
0.8. The fluid is being pumped into the reactor at a superficial velocity of u = 4 m/sec.
The reaction is being conducted at temperature T = 260°C = 533K and at inlet
pressure of P = 4.94 atm.
𝑘𝑔 𝑘𝑔
De=2.667 *10 -8 m2 / sec: 𝜌𝑐𝑎𝑡 = 2000 3 : 𝑑𝑝 = 0.4 𝑐𝑚 𝜌𝑔𝑎𝑠 = 1.9 3
𝑚 𝑚

89 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
𝑚6 𝑚𝑜𝑙
𝑘 = 50 :𝐹𝐴𝑜 = 1 𝐷𝐶 = 1 𝑚
𝑔𝑚𝑐𝑎𝑡 .𝑚𝑜𝑙.𝑠𝑒𝑐 𝑠𝑒𝑐
Solution:

𝑭𝑨 = 𝑭𝑨𝒐 (𝟏 − 𝒙)
𝑭𝑩 = 𝑭𝑨𝒐 𝒙
𝑭𝑪 = 𝟐𝑭𝑨𝒐 𝒙
𝑭𝑻 = 𝑭𝑨𝒐 (𝟏 + 𝒙)

𝑭𝑨 𝑭𝑨𝒐 (𝟏−𝒙) 𝟏−𝒙

𝑪𝑨 = = = 𝑪𝑨𝒐
𝝂 𝝂𝒐 (𝟏+𝝐𝒙) 𝟏+𝝐𝒙
𝝐=𝟑−𝟏=𝟐
𝟏−𝒙
𝑪𝑨 = 𝑪𝑨𝒐
𝟏 + 𝟐𝒙

𝟒. 𝟗𝟒 𝒂𝒕𝒎. 𝒌𝒎𝒐𝒍. 𝑲 𝒌𝒎𝒐𝒍 𝒎𝒐𝒍

𝑪𝑨𝒐 = = 𝟎. 𝟏𝟑𝟑𝟎𝟐 = 𝟏𝟑𝟑. 𝟎𝟐
𝟎. 𝟎𝟖𝟐𝒎𝟑 . 𝒂𝒕𝒎 ∗ 𝟓𝟑𝟑𝑲 𝒎𝟑 𝒎𝟑

𝑹 𝟑 𝒌 𝟐 𝑪𝑨𝑺 𝑹 𝟑 𝒌 𝟐 𝑪𝑨𝒔
∅𝒔 = √( ) = √( )
𝟑 𝟐 𝑫𝒆 𝟑 𝟐 𝑫𝒆

𝟎. 𝟒 ∗ 𝟏𝟎−𝟐 (𝒎) 𝟑 ∗ 𝟓𝟎𝒎𝟔 . 𝒔𝒆𝒄 ∗ 𝒎𝒐𝒍 ∗ 𝟐𝟎𝟎𝟎𝒌𝒈𝒄𝒂𝒕 ∗ 𝑪𝑨𝒔

∅𝒔 = √
𝟐∗𝟑 𝟐 ∗ 𝟏 ∗ 𝟏𝟎−𝟑 𝒌𝒈𝒄𝒂𝒕. 𝒎𝒐𝒍. 𝒔𝒆𝒄 ∗ 𝟐. 𝟔𝟔𝟕 ∗ 𝟏𝟎−𝟖 𝒎𝟐 𝒎𝟑 ∗ 𝒎𝟑

∅𝒔 = 𝟓. 𝟎 ∗ 𝟏𝟎𝟓 𝑪𝑨𝒔 𝟎.𝟓

𝟏
𝜼= = 𝟐. 𝟎 ∗ 𝟏𝟎−𝟓 𝑪𝑨𝒔 −𝟎.𝟓
∅𝒔

When internal diffusion control. 𝑪𝑨𝒃 = 𝑪𝑨𝑺

𝟏
Then 𝜼 = = 𝟐. 𝟎 ∗ 𝟏𝟎−𝟓 𝑪𝑨𝒃 −𝟎.𝟓
∅𝒔

−𝟓 −𝟎.𝟓 𝟏 − 𝒙 −𝟎,𝟓
𝜼 = 𝟐. 𝟎 ∗ 𝟏𝟎 𝑪𝑨𝒐 ∗( )
𝟏 + 𝟐𝒙

−𝟔
𝟏 − 𝒙 −𝟎,𝟓
𝜼 = 𝟏. 𝟕𝟑𝟒 ∗ 𝟏𝟎 ∗( )
𝟏 + 𝟐𝒙
At inlet x=0 then 𝜼 = 𝟏. 𝟕𝟑𝟒 ∗ 𝟏𝟎−𝟔

At outlet x=0.8 then 𝜼 = 𝟔. 𝟐𝟓 ∗ 𝟏𝟎−𝟔

The internal diffusion is very strong and can not be neglected

90 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

𝒓𝑨𝒑 = 𝜼𝒌𝟐 𝑪𝑨𝒃 𝟐

𝑥
𝑑𝑊 𝑑𝑥
∫ =∫
𝐹𝐴 𝑜 0 𝑟𝐴 𝑝

𝑥 𝑥
𝑑𝑥 1 𝑑𝑥
∫ = 2∫
0 𝜼 𝒌𝟐 𝑪𝑨𝒃 𝟐 𝑘2 𝐶𝐴𝑜 0 𝟏 − 𝒙 −𝟎,𝟓
(1 − 𝑥)2 𝟏. 𝟕𝟑𝟒 ∗ 𝟏𝟎−𝟔 ∗(
𝟏 + 𝟐𝒙 )
𝑥
𝑑𝑊 𝑔𝑚𝑐𝑎𝑡 . 𝑚𝑜𝑙. 𝑠𝑒𝑐 ∗ 𝑚6 𝑑𝑥
∫ = ∫
𝐹𝐴 𝑜 50𝑚6 ∗ (𝟏𝟑𝟑. 𝟎𝟐)2 𝑚𝑜𝑙2 ∗ 𝟏. 𝟕𝟑𝟒 ∗ 𝟏𝟎−𝟔 0 𝟏 − 𝒙 −𝟎,𝟓
(1 − 𝑥)2 (𝟏 + 𝟐𝒙 )

0,5
0.8 (
1 − 𝑥
1 ∗ 𝑚𝑜𝑙 ∗ 𝑔𝑚𝑐𝑎𝑡 . 𝑚𝑜𝑙. 𝑠𝑒𝑐 ∗ 𝑚6 )
𝑊= ∫ ( 1 + 2𝑥 ) 𝑑𝑥
𝑠𝑒𝑐 ∗ 50𝑚6 ∗ (133.02)2 𝑚𝑜𝑙 2 ∗ 1.734 ∗ 10−6 𝑜 (1 − 𝑥 )2

1 − 𝑥 0,5
0.8 (1 + 2𝑥 )
𝑊 = 0.652 ∫ 𝑑𝑥
𝑜 (1 − 𝑥 )2

𝑾 = 𝟎. 𝟔𝟓𝟐(𝒈𝒎𝒄𝒂𝒕 ) ∗ 𝑰𝒏𝒕𝒆𝒈𝒓𝒂𝒍 𝑽𝒂𝒍𝒖𝒆

𝑾 = 𝝆𝒄𝒂𝒕 (𝟏 − 𝒆) ∗ 𝑨𝒄 ∗ 𝒁

Then find the reactor length Z.

--------------------------------------------------------------------------------
Homework Problems:
1-A first-order, gas-phase reaction A→2B is performed in a PBR at 400 K and 10
atm. Feed rate is 5 mol/s containing 20% A and the rest inerts. The PBR is packed
with 8 mm-diameter spherical porous particles.
The intrinsic reaction rate is given as: rA= 3.75 CA mol/kg(cat).sec. Bulk density of
the catalyst is 2.3kg/liter. The diffusivity is 0.1 cm2/s.
a. What is the value of the internal effectiveness factor? What does it signify?
b. How much catalyst (kg) is required to obtain a conversion of 75% in the reactor?
c- what is the percentage of internal and external resistances.

91 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
2-Ethylene oxide (EO) is a major commodity chemical, with a production of about 3
million tons/a in the US (1997). (At 1997 price levels for ethylene oxide this
orresponds to a market value of about $4 billion!) Major uses for EO are antifreeze
(30%), polyester (30%), and surfactants and solvents (~ 10% each).
Your consulting company MeMyself&OthersInc. has taken on a new assignment to
design a fixed-bed reactor for EO production via the catalytic reaction of ethylene
with oxygen (C2H4+ 0.5 O2→EO), using a secret (but silver-based) catalyst.

The reactor is operated isothermally at 260°C, and ethylene is fed at a rate of 200
mol/h at an inlet pressure of 10 atm. A stoichiometricamount of oxygen is added
through an air feed. The reactor is a multitubularreactor with 1000 parallel tubes,
each with an inner diameter of 1.5”(38.1 mm). The tubes are filled with catalyst
particles (diameter = 0.25”(6.35 mm), particle density ρcat= 120 lb/ft3 = 1922 kg/m3),
resulting in a bed void fraction of ε= 0.45.
The kinetics have been determined as: –r’C2H4= k’PC2H41\3PO22/3[mol/(lb cat .h)]
with a rate coefficient at 260oC of k’= 4 mol/(atm.lb . cat h).

How much catalyst is needed to achieve 60% ethylene conversion? (For simplicity,
assume that the properties of the reaction mixtures are at this temperature always
identical to those of air.)

3- The use of a differential reactor to study the formation of methane from hydrogen
and carbon monoxide over a nickel catalyst gave the following rate of formation of
methane:

Suggest a mechanism and rate-limiting step that is consistent with the experimental
observation for the reaction:
It is desired to produce 20 tons/day of CH4. Calculate the catalyst weights necessary
to achieve 80% conversion in a fixed bed reactor. The feed consists of 75% H2 and
25% CO at a temperature of 500°F and a pressure of 10 atm. Assume both molecular
and atomic hydrogen are adsorbed on the surface.

4- The following second order liquid-phase catalytic reaction is conducted in an

isothermal fixed-bed reactor:A → B r = kCA2
The intrinsic rate constant is 16 L\mol . s. The feed is 0.8 L\s of a solution of A with
the concentration of A at 4 mol\L. Spherical catalyst pellets of radius 0.12cm are used
to pack the reactor. The catalyst has a pellet density of 0.88 g\cm3, and the reactor
bed density is 0.5 g\cm3. The effective diffusivity of A inside the catalyst pellet is
3.14 *10-3 cm2\s. You wish to achieve 99.9% conversion of A.

(a) First neglect both diffusional resistance and mass transfer resistance. What is the
mass of catalyst required to achieve the desired conversion?

92 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
(b) Next consider diffusional resistance but neglect mass transfer resistance. What are
the Thiele modulus and effectiveness factor at the entrance of the reactor? What are
the Thiele modulus and effectiveness factor at the exit of the reactor? Given these
two effectiveness factors, compute an upper bound and a lower bound on the mass of
catalyst required to achieve the desired conversion.
(c) Next consider both diffusional resistance and mass transfer resistance. Assume
that we have estimated the mass transfer coef®cient to be km= 0.35cm\s.
Find the effectiveness factor at the entrance of the reactor. Find the effectiveness
factor at the exit of the reactor.
Given these two effectiveness factors, compute an upper bound and a lower bound
on the mass of catalyst required to achieve the desired conversion.
(d) Compare your answers to parts (a)to(c). Discuss whether diffusion and/or mass
transfer limitations are important in this packed bed reactor.

5- A first order heterogeneous reaction: A → C is performed catalytically in a packed

bed reactor working at steady state using porous spherical catalyst particle with
iameter of 0.15 cm. The diameter of the reactor is 60 cm, the catalyst density is 2.3
gm/cm3. The bed voidage is 0.3 and the porosity of the catalyst particle is 0.4. The
volumetric flow rate to the reactor is 50000 cm3/sec and the reaction rate constant is
10 (cm3/gm cat. sec),and diffusion coefficient inside the pellet is 0.5 cm2/sec. The
inlet concentration of A into the reactor is 8.5*10-2 mole/cm3. Assume isothermal
operation and negligible dispersion. Calculate:
a) Thiele modulus.
b) The effectiveness factor.
c) The amount of the catalyst required for 85% conversion.

6-A first order reaction A→ B Where –rA =kCA mol/(gm. cat. sec.) is performed
catalytically in a packed bed reactor working at steady state using non porous
spherical catalyst particles with radius of 0.075 cm. The diameter of the reactor is 35
cm. The density of the catalyst is 2.2 gm/cm3 and the bed voidage is 0.28. The
reaction rate constant is 0.15 (cm3)/(gm cat. sec.). The volumetric flow rate to the
reactor is 20000 cm3/sec and the external mass transfer coefficient is 0.08 cm/sec.
Assume isothermal operation and negligible dispersion. Calculate:
a) The total length of the reactor required for 65% conversion of A.
b) The amount of the catalyst needed for 95% conversion of A.
c) The conversion if the length of the reactor is 1 m.

7-A first order reaction: A → C is performed catalytically in a packed bed reactor

working at steady state using porous spherical catalyst particle with diameter of 0.15
cm.The diameter of the reactor is 120 cm, the catalyst density is 2.0 gm/cm3. The bed
voidage is 0.3 and the porosity of the catalyst particle is 0.4. The volumetric flow rate
to the reactor is 20000 cm3/sec and the reaction rate constant is 1 (cm3/gm cat. sec),
and diffusion coefficient inside the pellet is 2 cm2/sec. The inlet concentration of A

93 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
into the reactor is 1.5*10-3 mole/cm3. Assume isothermal operation and negligible
dispersion.Calculate:
a) Thiele modulus.
b) The effectiveness factor.
c) The length of the reactor required for 65% conversion.
d) The amount of the catalyst needed for 85% conversion

8- We want to build a packed bed reactor filled with 1.2-cm porous catalyst particles
(density = 2000 kg/m3, De = 2 x 10-6 m3/m cat. s) to treat 1 m3/s of feed gas (1/3 A,
1/3 B, 1/3 inert) at 336 C and 1 atm to 80% conversion of A. Experiments with fine
catalyst particles which are free from diffusional resistance show that

How much catalyst must we use?

9-In aqueous solution, and in contact with the right catalyst, reactant A is converted
to product R by the elementary reaction A→R. Find the mass of catalyst needed in a
packed bed reactor for 90% conversion of 10 4mol A/hr of feed having CAo= 103
mol/m3. For this reaction k"' = 8 x 10-4m3/m3 bed. s and k"' = 2 m3/m3 bed. s
Additional data:
Diameter of porous catalyst pellets= 6 mm
Effective diffusion coefficient of A in the pellet = 4 * 104 m3/m cat. s
Voidage of packed bed = 0.5
Bulk density of packed bed = 2000 kg/m3 of bed

10-A packed bed reactor converts A to R by a first-order catalytic reaction, A→R.

With 9mm pellets the reactor operates in the strong pore diffusion resistance regime
and gives 63.2% conversion. If these pellets were re-placed by 18 mm pellets (to
reduce pressure drop) how would this affect the conversion?

94 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

Part Four:
• Kinetics of catalyst Poisoning.
• Kinetics of catalyst deactivation and regeneration.

95 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

4.1-Catalyst Deactivation:
Activity of catalysts normally decreases with time. The life of any catalyst generally
depends on type of reactions as well as reaction conditions. For example, catalysts for
catalytic cracking lose much of their activity within seconds due to carbon deposition
on the surface while promoted iron catalysts used in ammonia synthesis have a
lifetime of years. For any catalytic process, the life of catalyst is a major economic
factor. To regenerate or replace deactivated catalysts, the process needs to be
shutdown and consequently production is disrupted. Subsequent separation and
regeneration of catalysts also involve time and cost. Therefore, deactivation of
catalysts increases the cost of production significantly. Hence, any catalytic process
will be economically viable only if regenerations are required infrequently and can be
done inexpensively. A catalyst can be deactivated in three ways.

I. Poisoning
II. Fouling
III. Sintering or phase transformation

I. Poisoning
Poisoning basically involve chemisorption of reactants or products or feed impurities
on the active sites of the catalyst surface, thereby decreasing the number of active
sites available for catalytic reactions. Since poisoning involves chemisorptions, it is
known as chemical deactivation. This process can be reversible or irreversible.
Compound of sulphur and other materials are frequently chemisorbed on nickel,
copper and Pt catalysts. In reversible poisoning, the strength of adsorption bond is not
great and activity is regained when the poison is removed from the feed. When the
adsorbed material is tightly held on the active sites, poisoning is irreversible and
permanent.

II. Fouling
Rapid deactivation can be caused by physical deposition of substance on the active
sites of catalysts. Carbon deposition on catalysts used in petroleum industry falls in
this category. Carbon covers the active site of the catalysts and may also partially
plug the pore entrance. This type of deactivation is partially reversible and
regeneration can be done by burning in air.

III. Sintering or phase transformation

Because of local high temperature, support of catalysts or catalyst itself may undergo
structural modification or sintering causing a reduction in specific surface area or
change in chemical nature of catalytic agent so that it becomes catalytically inactive.
Hence, poisoning and fouling are dependent on concentration of reactant or product
or impurities. On the other hand, sintering and phase transformation may be assumed
96 Chemical Engineering Department- University of Basrah
Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
to be independent of fluid phase composition. This is also therefore known as
independent deactivation. Figure 23 shows the major types of deactivation.

Figure 23 : the major types of deactivation inhetrogenous catalysis.

Steps to reduce deactivation: Following steps can be taken to reduce the possibility
of deactivation of catalysts :

a. Removal of poison material form feed

b. Use of hydrogen which reduces coking
c. Removal of hot spot by proper design of reactor /process control to prevent any
thermal deactivation.

4.2-Mechanism of Catalysts Deactivation:

The deactivation of catalysts can occur by different mechanism as explained below :

1. Parallel deactivation

Reactant (A) produces a side product (P) which can deposit on the surface thereby
deactivating it. Deposition depends on reactant concentration.

97 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

2. Series deactivation :
Reaction product (R) can decompose or react further to produce material (P) that
deposits and deactivates the surface. In this case, deposition depends on product
concentration.

3. Side-by-side deactivation:
In this mechanism, impurity in feed (P) deposits on the surface deactivating it.
Deposition depends on concentration of impurities in the feed.

4. Independent deactivation :
This catalyst decay involves structural modification or sintering of catalyst surface
caused by exposure of catalysts to extreme conditions such as high temperature. This
decay is dependent on time that the catalyst spends in high temperature conditions
and is independent of the materials in the fluid.

4.3-Deactivation kinetics :
Activity of catalysts pellet at any time is defined as

………………….(1)

Reaction rate can be considered as function of temperature, reactant concentration

and present activity of the catalysts pellet. Therefore for n th order reaction, rate can be
written as
……………………….(2)

Similarly, deactivation rate can be considered as function of temperature,

concentration of substance that deactivates the catalyst (which can be reactant,
98 Chemical Engineering Department- University of Basrah
Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
product or impurities) and present activity of the catalyst pellet. Hence, deactivation
rate can be given as,

……………………………...(3)

i = A (reactant), R (product) , P(3rd substance)

Here d is called order of deactivation, kd is deactivation rate constant and n΄ is the
concentration dependency.
Deactivation rate for different types.

99 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
4.3.1-Deactivation Kinetics for Sintering:
Most commonly used decay law for sintering is second order with respect to
present activity.

…………………………...(4)

The kd is the sintering decay constant. Integration with a=1 at time t=0 gives

……………………………(5)

Activity can be measured in terms of amount of sintering. If the total active surface
area of the catalyst is Sao at t = 0 and Sa at any time t, then activity can be written as

………………………......(6)

From equation (5) and (6),we obtain

…………………………..(7)

The sintering decay constant kd is given as:

…………………………….(8)

Ed is the decay activation energy. For reforming of heptanes on Pt /Al 2O3 value of Ed
is in the order of 70 kcal/mol.

4.3.2-Deactivation Kinetics for Coking or Fouling:

Various empirical relations are available for calculation of amount of coke deposited
on catalyst surface after a time t.
………………………..…(9)

Cc is the concentration of carbon on the surface in g/m2. The ‘n’ and ‘A’ are fouling
parameter functions of feed rate. Representative value of A and n for cracking of light
gas oil is 0.47 and 0.5 respectively when ‘t’ is in minute.
The activity can be related to amount of coke deposited on the surface by following
relation :
…………………………(10)

Substituting value of Cc from relation (9), in term of process time, activity can be
expressed as shown below.

100 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

…………………..(11)

Or

Other dimensionless fouling correlations are also developed by several groups.

4.3.3-Deactivation Kinetics for Poisoning:

For petroleum feed containing trace impurities such as sulfur, the poisoning reaction
can be written as P+S→PS
The rate of deactivation is given as
…………………….……….(12)

The Cp is the concentration of poison in feed. The ‘m’ and ‘q’ are respective orders.
The rate of removal of poison from the reactant by catalyst sites is proportional to the
number of sites that are not poisoned (Cto - Cps) and concentration of poisons in the
gas phase, Cp. The Cps is the concentration of poisoned sites and Cto is the total
number of fresh sites initially available. Then rate of removal of poison is equal to
rate of formation of poisoned site and is given as

…………………………(13)

Dividing throughout by Cto and if ‘f’ is the fraction of the total number of the sites
that have been poisoned then equation (13) can be written as

……………………………………...(14)

The fraction of sites available for adsorption (1-f) is essentially the activity a (t). Then
equation (14) becomes
…………………………(15)

101 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

4.4-Determination of Deactivation Kinetic Parameters:

Case 1 : Consider a reaction in a mixed reactor under constant flow condition. Let
independent deactivation occur. Assume both the main reaction and deactivation
reaction to be first order with respect to activity ‘a’. Then,

…………………………(16)

Integrating equation (16) gives

……………………………(17)

.…………………………...(18)

Substituting expression for rate from equation (6)

102 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

…………………………….(19)

……………………(20)

τw is called the weight time similar to space-time τ . CA and ‘a’ vary with time
Substituting,

in equation (20)

…………………..(21)

Fig. 24. Plot to determine the rate constant and the deactivation rate constant for a reaction over
deactivating catalyst. ( For mixed reactor, constant flow and independent deactivation)

103 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
Case II : Consider a reaction in a mixed reactor under changing flow condition so
that concentration is constant. Let parallel deactivation occur. Assume the main
reaction to be nth order and the deactivation reaction to be of first order in activity
‘a’.

……………………………(22)

Since concentration is constant,

………………….(23)

For first order activity , d =1

104 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
Then substituting ‘a’in equation (23)
…………(24)

……………….(25)

Fig. 25 . Plot to determine rate constant and deactivation rate constant for a reaction over
deactivating catalysts for mixed reactor, changing flow condition and parallel deactivation

Example 1:
We plan to run an isomerization of A → R in isothermal packed bed reactor ( pure A
feed, FA, = 5 kmol\hr, W = 1ton catalyst, P = 3 atm, T = 730 K). The catalyst
deactivates so we plan to make 120 day runs, then regenerate the catalyst.
(a) Plot conversion and activity versus time for the run
(b) find x for the 120 day run
The rate of reaction with CA in mol/m3 is described by

and the rate of deactivation is given by

105 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

Solution:
In general for parts (a), (b), (c), and (d) we can write

or on rearranging

Let us now replace the activity term in the rate of reaction.

106 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

evaluating XA at various values of t gives the top most curve shown in Fig. 26.

𝟏𝟎𝟎 ∗ (𝟏 − 𝟖. 𝟑𝟏𝟐𝟓 ∗ 𝟏𝟎−𝟑 𝒕)

𝒙=
𝟏 + 𝟏𝟎𝟎 ∗ (𝟏 − 𝟖. 𝟑𝟏𝟐𝟓 ∗ 𝟏𝟎−𝟑 𝒕)

𝟏𝟎𝟎 ∗ 𝒆−𝟎.𝟎𝟓 𝒕
𝒙=
𝟏 + 𝟏𝟎𝟎 ∗ 𝒆−𝟎.𝟎𝟓 𝒕

𝟏𝟎𝟎
𝒙 = 𝟏 + 𝟑. 𝟑𝟐𝟓 𝒕
𝟏𝟎𝟎
𝟏+
𝟏 + 𝟑. 𝟑𝟐𝟓 𝒕

107 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf
𝟏
𝟏𝟎𝟎 ∗
𝒙= √𝟏 + 𝟏𝟑𝟑𝟑𝒕
𝟏
𝟏 + 𝟏𝟎𝟎 ∗
√𝟏 + 𝟏𝟑𝟑𝟑𝒕

From Fig. 26 we find by graphical integration that for the 120-day period, XA.start=
0.99, XA,end, = 0.20 for

It also clearly shows how different is the progress of the reaction with the different
orders of deactivation.

Fig. 26: Decrease in conversion as a function of time for various

deactivation orders.

108 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

Homework Problems:
1-Under conditions of strong pore diffusion the reaction A → R proceeds at 700°C on
a slowly deactivating catalyst by a first-order rate

Deactivation is caused by strong absorption of unavoidable and irremovable trace

impurities in the feed, giving third-order deactivation kinetics, or

We plan to feed a packed bed reactor (W = 10 kg) with v = 100 liters\min of fresh A
at 8 atm and 700°C until the catalyst activity drops to 10% of the fresh catalyst, then
regenerate the catalyst and repeat the cycle,
(a) What is the run time for this operation?
(b) What is the mean conversion for the run?

2-At 730K the isomerization of A → R (rearrangement of atoms in the molecule)

proceeds on a slowly deactivating catalyst with a second-order rate

Since reactant and product molecules are similar in structure, deactivation is caused
by both A and R. With diffusional effects absent, the rate of deactivation is found to
be

We plan to operate a packed bed reactor containing W = 1 ton of catalyst for 12 days
using a steady feed of pure A, FAo = 5 kmol\hr at 730 K and 3 atm (CAo = 0.05
mol\liter).
(a) First evaluate -da/dt, 𝝉, and then the general expression for 1 - XA.
(b) What is the conversion at the start of the run?
(c) What is the conversion at the end of the run?
(d) What is the average conversion over the 12-day run?

109 Chemical Engineering Department- University of Basrah

Catalytic Reactor Design - Fourth Year Dr.Ali .N.Khalaf

Relevant books:
1-Fogler, H.S. 1999. Elements of chemical reaction engineering. 3rd ed. Prentice-
Hall.
2- Levenspiel, O. 1999. Chemical reaction engineering. 3rd ed. Wiley & Sons, Inc.,
3-Froment, G.F.; Bischoff, K.B.; De Wilde, J. 2011. Chemical reactor analysis and
design. 3rd ed. John Wiley & Sons, Inc.
4-Missen, R.W.; Mims, C.A.; Saville, B.A. 1999. Introduction to chemical reaction
engineering and kinetics. John Wiley & Sons, Inc., New York.
5-Carberry, J.J. Chemical and catalytic reaction engineering.
6-Smith, J.M. 1981. Chemical engineering kinetics. 3rd ed. McGraw-Hill Int. Book
Co., Singapore.
7-Hill, Jr., C.G. 1977. Introduction to chemical engineering kinetics and reactor
design. John Wiley & Sons.

This is not the end.

It is not even the beginning of the end.
But it is, perhaps, the end of the beginning.
Winston Churchill
November 10, 1942

110 Chemical Engineering Department- University of Basrah