6.

Catalytic Reactors

Reference(s):
Elements of Chemical Reaction Engineering
(Ch 10)

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Reading---
Reaction Engineering I
(LECTURE_7_Kinetics of Heterogeneous Catalytic Reactions )
---is recommended
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 Objectives
(1) define a catalyst and describe its properties.
(2) describe the steps in a catalytic reaction and apply the
concept of a rate-limiting step to derive a rate law,
(3) describe the different types of catalyst deactivation,
determine an equation for catalytic activity from concentration-
time data, define temperature-time trajectories to maintain a
constant reaction rate, and
(4) calculate the conversion or catalyst weight for packed (fixed)
beds, moving beds, well-mixed (CSTR) and straight-through
(STTR) fluid-bed reactors for both decaying and nondecaying
catalysts.

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Contents
6.1 Catalysts
6.2 Steps in a Catalytic Reaction
6.3. Algorithm for Determining Reaction Mechanism and
Rate-limiting Step
6.4. Design of Reactors for Gas-Solid Reactions
6.5. Catalyst Deactivation
6.6. Matching the reactor type with speed of catalyst decay
6.7. Summary

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 6.1 Catalysts
• A catalyst is a substance that affects the rate of a reaction
but emerges from the process unchanged.

• A catalyst usually changes a reaction rate by promoting a

different molecular path (“mechanism”) for the reaction

• Catalysis is the occurrence, study, and use of catalysts

and catalytic processes.

• Approximately one-third of the material gross national

product of the United States involves a catalytic process
somewhere between raw material and finished product
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 Cont’d

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 Cont’d
• Homogeneous catalysis concerns processes in which a
catalyst is in solution with at least one of the reactants.

• A heterogeneous catalytic process involves more than one

phase; usually the catalyst is a solid and the reactants and
products are in liquid or gaseous form.

• Simple and complete separation of the fluid product

• Thus, economically attractive, especially because
many catalysts are quite valuable and their reuse is
demanded.
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6.1.1. Catalyst Properties
• Because a catalytic reaction occurs at the fluid–solid interface,
a large interfacial area is almost always essential in attaining a
significant reaction rate.
• In many catalysts, this area is provided by an inner porous
structure (i.e., the solid contains many fine pores, and the
surface of these pores supplies the area needed for the high
rate of reaction)
• Example: Silica-alumina cracking catalyst :Ten grams of this
catalyst possess more surface area than a U.S. football field
(300 m2/g)
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 6.1.2. Catalyst types

A. Porous
B. Molecular sieves
C. Supported
D. Unsupported

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 Cont’d

(b) Schematic of reaction CH4

and C6H5CH3.

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6.2 Steps in a Catalytic Reaction

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 Cont’d

The overall
rate of
reaction is
limited by
the rate of
the
slowest
step in the
sequence
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 Cont’d

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 Cont’d

•Revise:
10.2.1 Adsorption Isotherms
10.2.2 Surface Reaction
10.2.3 Desorption
10.2.4 The Rate-Limiting Step
10.3 Synthesizing a Rate Law, Mechanism, and
Rate-Limiting Step

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6.3. Algorithm for Determining Reaction
Mechanism and Rate-limiting Step

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 Cont’d

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 Cont’d

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 Cont’d

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 Cont’d
Pseudo-SteadyState Hypothesis (PSSH)

• An alternative way to derive a catalytic rate law is to assume that each species
adsorbed on the surface is a reactive intermediate. Consequently, the net rate
of formation of species i adsorbed on the surface will be zero
• The PSSH is primarily used when more than one step is rate-limiting.

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 Cont’d

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Evaluation of the Rate-Law Parameters

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 Solution
non linear regression_for_chapter_6.xlsx

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 6.4 Design of Reactors for Gas-Solid
Reactions
• All the design equations for ideal catalytic or fluid-solid
reactors can be obtained from their homogeneous reactor
analogs merely by substituting the catalyst or solid weight,
W, for the reactor volume, V.

• The reactor volume is merely the catalyst weight W divided

by the bulk density of the catalyst ρb.

• In the catalytic or fluid-solid reactor design equations, r’A ,

based on catalyst mass, must of course be used.

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 Cont’d
• Batch Reactor design equation a
heterogeneous reaction:

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 Cont’d
• Packed-bed reactor design equation for
heterogeneous reaction:

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 Cont’d
• For the ideal CSTR, the design equation is

• and the equivalent equation for a catalytic or fluid-solid

reactor ("Fluidized" CSTR) (Figure 10-16) is

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 Example

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 Solution
1. Design equation:

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 Cont’d
2. Rate Law

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 Cont’d
3. Stoichiometry:

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 Cont’d

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 Cont’d
• The initial mole fraction of toluene is 0.3 (i.e., yTo = 0.3), so that the
initial partial pressure of toluene is
• PTO = (0.3)(40) = 12 atm

• The maximum catalyst weight we can have and not fall below 1 atm
is found from Equation (4-33) for an entering pressure of 40 atm.

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 Cont’d

•Consequently, we will set our final weight at

10,000kg and determine the conversion as a
function of catalyst weight up to this value.

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Read:
10.6 Chemical Vapor Deposition
10.8 Reaction Engineering in Microelectronic Device
Fabrication

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 Cont’d
Chemical vapor deposition

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6.5. Catalyst Deactivation
• One of the most insidious problems in catalysis is the loss of
catalytic activity that occurs as the reaction takes place on
the catalyst.

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 Cont’d
• The activity of the catalyst at time t, a(t),

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 Cont’d

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 Cont’d
• Reaction rate law accounting for catalyst activity

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 Cont’d
•Catalyst decay rate law

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6.5.1 Types of Catalyst Deactivation

There are three categories :

•Sintering or aging,
•Fouling or coking, and
•Poisoning.

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6.5.1.1.Deactivation by Sintering (Aging)
• Sintering, also referred to as aging, is the loss of catalytic activity due to a
loss of active surface area resulting from the prolonged exposure to high
gas-phase temperatures.
• The active surface area may be lost either
by crystal agglomeration and growth of the metals deposited on
the support or
 by narrowing or closing of the pores inside the catalyst pellet.
• A change in the surface structure may also result from either
surface recrystallization or
from the formation or elimination of surface defects (active
sites).

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 Cont’d

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 Cont’d
• Sintering: second order decay (Commonly used decay law ):

• Integrating

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 Cont’d
• The amount of sintering is usually measured in terms
of the active surface area of the catalyst Sa:

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 Cont’d
• The sintering decay constant follows the Arrhenius
equation

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Example 10-4 Calculating Conversion with
Catalyst Decay in Batch Reactors

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 Solution
•Algorithm

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 Cont’d
1 . Design equation:

2. Reaction rate law:

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 Cont’d
3. Decay law. For second-order decay by sintering:

4. Stoichiometry:

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 Cont’d
5. Combining

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 Cont’d

6. Solving for the conversion X at any time t

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 clear all
clc
close all
tspan=[0 500];
x0=0;
xd0=0;
[t X]=ode15s(@fun_aging, tspan, [x0 xd0])
plot (t,X(:,1),t,X(:,2));
xlabel ('time')
ylabel ('Conversion with and with out
decay')
legend ('x','xd')
function dXdt=fun_aging(t,X)
x=X(1);
xd=X(2);
%%%Constants
k=0.01;
kd=0.1;
%%%Differential equations
dxdt = k*(1-x);
dxddt= k*(1-xd)/(1+kd*t);
dXdt=[dxdt;dxddt]
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6.5.1.2. Deactivation by Coking or Fouling

• Results from a carbonaceous (coke) material being

deposited on the surface of a catalyst.
• is common to reactions involving hydrocarbons.

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 Cont’d

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 Cont’d
• The amount of coke on the surface after a time t has been
found to obey the following empirical relationship:

• where C, is the concentration of carbon on the surface and

• n and A are fouling parameters which can be functions of the feed
rate.

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 Cont’d
• Different functionalities between the activity and amount of
coke on the surface have been observed.
• One commonly used form is

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 Cont’d

•Other commonly used forms:

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6.5.1.2. Deactivation by Poisoning

• A poisoning molecules become irreversibly

chemisorbed to active sites, thereby reducing
the number of sites available for the main
reaction.
• The poisoning molecule, P, may be a reactant
and/or a product in the main reaction, or it may
be an impurity in the feed stream

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 Cont’d
• Poison in the Feed:
For the case of an impurity, P, in the feed stream, such as
sulfur, for example, in the reaction sequence

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 Cont’d

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 Cont’d
• Assume the rate of removal of the poison from the reactant
gas stream onto the catalyst sites is

where CPS is the concentration of poisoned sites and Ct0, is the

total number of sites initially available.

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 Cont’d
• Because every molecule that is adsorbed from the gas
phase onto a site is assumed to poison the site, this
rate is also equal to the rate of removal of sites from
the surface:

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 Cont’d
• Dividing through by Ct0 and letting f be the fraction
of the total number of sites that have been poisoned
yields

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 Cont’d

•The fraction of sites available for adsorption

(1 - f) is essentially the activity a(t).
• Consequently, Equation (I0-108) becomes

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Example 10-5 Catalyst Decay in a Fluidized Bed
Modeled as a CSTR

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 Cont’d

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6.6.Matching the reactor type with
speed of catalyst decay

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6.6.1 Temperature-Time Trajectories
• In many large-scale reactors, such as those used for
hydrotreating, and reaction systems where deactivation by
poisoning occurs, the catalyst decay is relatively slow.
• In these continuous-flow systems, constant conversion is
usually necessary in order that subsequent processing steps
(e.g., separation) are not upset.
• One way to maintain a constant conversion with a decaying
catalyst in a packed or fluidized bed is to increase the
reaction rate by steadily increasing the feed temperature to
the reactor.

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 Cont’d

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 Cont’d
• We are going to increase the feed temperature in such a
manner that the reaction rate remains constant with time:

• For a first-order reaction we have

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 Cont’d
• We will neglect any variations in concentration

• The goal is to find how the temperature should be

increased with time ( the Temperature-Time Trajectories )

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 Cont’d
• Substituting for k in terms of EA gives

• Solving for 1/ T yields

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 Cont’d
• The decay law is

• Substituting Equation (10-115) into (10-116) and rearranging yields

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 Cont’d

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 Cont’d
• Solving Equation (10-114) for a and substituting in (10-118)
gives

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Cont’d

•Equation (10-119) tells us how the

temperature of the catalytic reactor
should be increased with time in
order for the reaction rate to
remain unchanged with time.
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6.6.2. Moving-Bed Reactors
•Reaction systems with significant catalyst
decay require the continual regeneration
and/or replacement of the catalyst.

•Two types of reactors currently in commercial

use that accommodate production with
decaying catalysts are the moving-bed and
straight-through transport reactor.

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A schematic diagram of
a moving-bed reactor

Used for reactions

with moderate rate
of catalyst decay.

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 Cont’d

•The mole balance on reactant A over ΔW is

•

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Cont’d
• Dividing by ΔW, letting ΔW approach zero, and expressing
the flow rate in terms of conversion gives

• The rate of reaction at any time t is

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 Cont’d
• The decay rate law is

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 Cont’d
• We now need to relate the contact time to the weight of the catalyst.
• Consider a point z in the reactor, where the reactant gas has passed
concurrently through a catalyst weight W.
• Since the solid catalyst is moving through the bed at a rate Us(mass
per unit time), the time t that the catalyst has been in contact with
the gas when the catalyst reaches a point z is

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 Cont’d
• differentiate Equation (10- 122)

• combine it with the decay rate law

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 Cont’d
• The activity equation is combined with the mole balance
•The design equation for moving-bed
reactors

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Example 10–5 Catalytic Cracking in a Moving-Bed
Reactor

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Solution

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6.6.3.Straight-Through Transport Reactors

• This reactor is used for reaction systems in which the catalyst

deactivates very rapidly.
• In the STTR, the catalyst pellets and the reactant feed enter together
and are transported very rapidly through the reactor.
• The bulk density of the catalyst particle in the STTR is significantly
smaller than in moving-bed reactors, and often the particles are
carried through at the same velocity as the gas velocity.
• In some places the STTR is also referred to as a circulating fluidized
bed (CFB).

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 Cont’d
• A mole balance on the reactant A over the differential reactor
volume

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 Cont’d
• In term of conversion and catalyst activity

• For a catalyst particle traveling through the reactor with a velocity

Up, the time the catalyst pellet has been in the reactor when it
reaches a height z is just

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Cont’d
• Substituting for time t in terms of distance z [i.e., a(t) = a(z/Up)], the
mole balance now becomes

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Cont’d
• The molar flow rate, FAo,can be expressed in terms of the gas
velocity Ug, CAo,and Ac:

• Substituting for FAO, we have

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Example 10–6 Decay in a Straight-Through
Transport Reactor

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 SUMMARY

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• NB:
Project Will Be Part Of Final Exam
Typical Final Exam Problem
 Derive All the Equations
 Write A Matlab Script To Solve The Problem

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