Lecture 1

Advanced Reactor Design

(M. Sc.)
Dr. Usama Al-Rawi

Catalysts
Scope:
• Catalyst & Catalysis??
• Limited to gas phase reactions catalyzed by solids
• Mechanism & rate laws
• Interpretation of data – estimation of rate law parameters
• Physical properties of catalysts – estimation
• Catalytic reactors
• Design of Fixed bed reactor

What is a catalyst??
• Alters the rate of reaction
• Highly selective
• Does it participate in the reaction??
• How does it change the rate?? – Offers an alternate path with
low E.
• Does it affect HR, GR, and Eq. constant??
• Does it affect yield & selectivity??
• Does it initiate a reaction??

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 Lecture 1

Every catalytic reaction is a sequence of elementary steps, in which

reactant molecules bind to the catalyst, where they react, after which the
product detaches from the catalyst, liberating the latter for the next cycle

Potential energy diagram of a heterogeneous catalytic reaction, with

gaseous reactants and products and a solid catalyst. Note that the
uncatalyzed reaction has to overcome a substantial energy barrier,
whereas the barriers in the catalytic route are much lower.

Example: Boundary compared the homogeneous versus catalytic rates of

ethylene hydrogenation.
Homogeneous:
 43000 
r  1027 exp   pH
 RT  2

Catalytic:
 13000 
r  2 x1027 exp   pH 2
 RT 
At 600 K the ratio of catalytic to homogeneous rate is 1.44x1011

Examples of using catalysts

• Ammonia synthesis – Promoted iron
• SO2 oxidation – Vanadium Pentaoxide
• Cracking – Silica, alumina
• Dehydrogenation – Platinum, Molybdenum

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 Lecture 1

Classification:
• Homogenous catalysis
• Heterogeneous catalysis
Catalysts are generally used to:
• Speedup reactions
• Change the operating temperature level
• Influence the product distribution
Promoter: is an additive which has no catalytic properties of its own but
enhances the activity of a catalyst
Promoter results in:
• Increase of available surface area
• Stabilization against crystal growth and sintering
• Improvement of mechanical strength
Examples: Alumina, Asbestos

Carrier: principally serve as a framework on which catalyst is deposited -

no catalytic properties of its own
Carrier results in:
• Highly porous nature - increase of available surface
area
• Improve stability
• Improves the heat transfer characteristics
Examples: Alumina, Asbestos, Carborundum, Iron oxide, Manganese,
Activated carbon, Zinc oxide

Accelerator: are substances which can be added to a reacting system to

maintain the activity of a catalyst by nullifying the effects of poisons.

Poisons: substances which reduce the activity of a catalyst. They are not
deliberately added but are unavoidably deposited during the reaction.

Examples: Sulfur, Lead, Metal ions such as Hg, Pd, Bi, Sn, Cu, Fe etc.

Inhibitor: substances added to the catalyst during its manufacture to

reduce its activity.

Coking/Fouling: deposition of carbonaceous material on the surface of

the catalyst - Common to reactions involving hydrocarbons
Activity: of a catalyst depends on the texture and electronic structure.

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 Lecture 1

Activity of a catalyst can be explained by:

• Active centers on the surface of the catalyst
• Geometry of surface
• Electronic structure
• Formation of surface intermediates
• Efficiency of a catalyst depends on : Activity, Selectivity and
Life.

Active site: is a point on the catalyst surface that can form strong
chemical bonds with an adsorbed atom/molecule. These sites are
unsaturated atoms in the solid resulting from:
• Surface irregularities
• Dislocations
• Edges of crystals
• Cracks along grain boundaries

Classification of Catalysts According to Catalyst types

� Porous
� Molecular sieves
� Monolithic
� Supported
� Unsupported

Porous Catalysts
• A catalyst that has a large area resulting from pores. Raney nickel --
hydrogenation of vegetable and animal oils.
• A catalytic reaction occurs at the fluid-solid interface. A large
interfacial area can be helpful or even essential in attaining a significant
reaction rate.
• In many catalysts, this area is provided by a porous structure; the solid
contains many fine pores, and the surface of these pores supplies the area
needed for the high rate of reaction. The area possessed by some porous
materials is surprisingly large.
• A typical silica-alumina cracking catalyst: a pore volume of 0.6 cm3/g
average pore radius of 4 nm surface area is 300 m2/g

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 Lecture 1

Summery

• 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.
• The development and use of catalysts is a major part of the constant
search for new ways of increasing product yield and selectivity from
chemical reactions. Because a catalyst makes it possible to obtain an end
product by a different pathway (e.g. a lower energy barrier), it can affect
both the yield and the selectivity.
• Normally when we talk about a catalyst, we mean one that speeds up
a reaction, although strictly speaking, a catalyst can either accelerate or
slow the formation of a particular product species.
• A catalyst changes only the rate of a reaction; it does not affect the
equilibrium.

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 Lecture 2

Mechanism of Heterogeneous Catalysis:

1. Bulk Diffusion of reacting molecules to the surface of the catalyst
2. Pore Diffusion of reacting molecules into the interior pores of the
catalyst
3. Adsorption of reactants (chemisorption) on the surface of the catalyst
4. Reaction on the surface of the catalyst between adsorbed molecules
5. Desorption of products
6. Pore Diffusion of product molecules to the surface of the catalyst
7. Bulk Diffusion of product molecules

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 Lecture 2

We Focus on…
� Adsoroption
� Surface Reaction
� Desorption

Pore and film resistances in a catalyst particle

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 Lecture 2

Rate-Determining Step (rds)

In a kinetics scheme involving more than one step, it may be that one
change occurs much faster or much slower than the others (as determined
by relative magnitudes of rate constants).
In such a case, the overall rate, may be determined almost entirely by the
slowest step, called the rate-determining step (rds).
The rate of the rds is infinitesimal when compared to the rates of other
steps.
Alternately the rates of other steps are infinite compared to the rate of rds.

Bulk Diffusion:
• Diffusion controlled reactions are usually fast
• Design of reactors – design of mass transfer
equipment
• Increase in mass velocity increases the rate
• High L/D ratio reactors (narrow) are favored
Pore Diffusion:
• Pore diffusion controlled reactions are few
• Design of reactors – most complicated
• Approaches bulk diffusion if the pore size is large
• Approaches Knudsen diffusion if the pore size is
small.
• No effect of temperature or mass velocity
• Low L/D ratio reactors (wide) may be used with
consequent reduction in pressure drop

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 Lecture 2

Chemisorption:
• Chemisorption controlled reactions are usually fast
• Rate increases rapidly with increase in temp.
• Permits the use of wide reactors
Surface reaction:
• 70% of the reactions which are not controlled by
diffusion falls under this case
• Rate increases rapidly with increase in temp.
• Permits the use of wide reactors
Desorption:
• Desorption of a product could also be rate controlling
in a few cases
Complexities:
• Theoretically more than one step can be rate
controlling
• Too many possible mechanisms
• Experimental data is normally fitted to any single rate
controlling step, which is then called the most
plausible mechanism

Detailed Mechanism
Adsorption

Adsorption

Physical adsorption is similar to condensation. The process is

exothermic, and the heat of adsorption is relatively small, being on the
order of 1 to 15 kcal/g mol.
Chemisorption: adsorbed atoms or molecules are held to the surface by
valence forces of the same type as those that occur between bonded atoms
in molecules. The electronic structure of the chemisorbed molecule is
perturbed significantly, causing it to be extremely reactive.

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 Lecture 2

Chemisorption

Chemisorption is an exothermic process, but the heats of adsorption are

generally of the same magnitude as the heat of a chemical reaction (i.e.,
10 to 100 kcal/g mol).
It must be carried out within the temperature range where
chemisorption of the reactants is appreciable.

More on Adsorption
Taylor suggested that a reaction is not catalyzed over the entire solid
surface but only at certain active sites or centers.
active site : as a point on the catalyst surface that can form strong
chemical bonds with an adsorbed atom or molecule.
Turnover frequency, N : is the number of molecules reacting per active
site per second at the conditions of the experiment.
Dispersion, D : of the catalyst is the fraction of the metal atoms deposited
that are on the surface.

Adsorption Convention
The adsorption of A on a site S is represented by:

Ct (mol/g • cat) : Total molar concentration of active sites per unit mass
of catalyst
Cv : The molar concentration of vacant sites
Pi : Partial pressure of species i in the gas phase, atm

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 Lecture 2

Ci • S : Surface concentration of sites occupied by species i (mol/g • cat) ,

for instance i = A , B, C …

Adsorption Isotherms
Isotherms : isotherms portray the amount of a gas adsorbed on a solid at
different pressures but at one temperature.
Postulate adsorption models, then see which one(s) fit(s) the data

Example: CO Adsorption
1. Molecular / nondissociated adsorption:
CO is adsorbed as molecules on nickel, CO

2. Dissociated adsorption:
Carbon monoxide is adsorbed as oxygen and carbon atoms instead
of molecules, on iron

CO Adsorption

Molecular Adsorption
• Consider molecular adsorption first

• The goal is to obtain a rate law for the rate of adsorption

• Rate law for adsorption takes the form of elementary reactions
The rate of attachment is proportional to the number of collisions that
these molecules make with the surface per second and the rate of collision
is proportional to the carbon monoxide partial pressure, PCO

rate of attachment = kAPCOCv

rate of detachment = k-ACCO • S

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 Lecture 2

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

kA for molecular adsorption is virtually independent of temperature the

desorption constant k-A increases exponentially with increasing
temperature and equilibrium adsorption constant KA decreases
exponentially with increasing temperature.

Site Balance

Site Balance:

C t = Cv + CA • S + CB • S

Consider : when more than one substance is present, how to derive the
adsorption isotherm ?

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 Lecture 2

The adsorption isotherm of A in the presence of adsorbent B is given by

the relationship:

• Both A and B are first-order processes

• The desorption’s are also first-order
• Both A and B are adsorbed as molecules
Dissociative Adsorption

Molecular adsorption: the rate of adsorption here is proportional to the

pressure of carbon monoxide.
For dissociative adsorption: two adjacent vacant active sites are
required rather than the single site needed when a substance adsorbs in its
molecular form. The probability of two vacant sites occurring adjacent to
one another is proportional to the square of the concentration of vacant
sites. The rate of adsorption is proportional to the product of the carbon
monoxide partial pressure and the square of the vacant-site concentration,
PcoC2v

For dissociative adsorption both kA and k-A increases exponentially with

increasing temperature while KA decreases with increasing temperature.

At equilibrium, rAD = 0, and

For CC • S = CO • S

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 Lecture 2

Surface Reaction
1. Langmuir-Hinshelwood Single Site Mechanism

2. L-H Dual Site Mechanism

The adsorbed reactant interacts with another site (either unoccupied or
occupied) to form the product.
2.1 adsorbed A may react with an adjacent vacant site to yield a vacant
site and a site on which the product is adsorbed:

2.2 The reaction between two adsorbed species:

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 Lecture 2

2.3 the reaction of two species adsorbed on different types of sites S and
S’:

3. Eley-Rideal Mechanism
The reaction between an adsorbed molecule and a molecule in the gas
phase.

Desorption

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 Lecture 2

Summery
When heterogeneous reactions are carried out at steady state, the rates of
each of the three reaction steps in series (adsorption, surface reaction, and
desorption) are equal to one another:
-r’A = rAD = rS = rD
One particular step in the series is usually found to be rate-limiting or
rate-controlling.
If we could make this particular step go faster, the entire reaction would
proceed at an accelerated rate.

Synthesizing a rate law – Algorithm (Langmuir-Hinshelwood

Approach)

1. Assume a sequence of steps

2. Write rate laws for each step assuming all steps to be
reversible
3. Assume a rate limiting step
4. Equate the rate of rds to the overall rate
5. The rates of other steps are equated to zero
(equilibrium)
6. Using the rates of other steps eliminate all coverage
dependent terms
7. If the derived rate law does not agree with expt., goto
(3).

*Approach is similar to non-elementary reactions.

*In the case of non-elementary reactions there is only
one rate law for a given mechanism.
*But in the case of solid catalyzed gas phase reactions,
there could be many (equal to the number of steps)
rate laws for a given mechanism.
*In a given mechanism, even after assuming each of
the steps as rds, and none of them satisfy the
experimental data, start with a new mechanism and
repeat

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 Lecture 3

Reactor Design of catalyst Gas Solid Reaction

General Mass Balance Equation:

Rate of input = rate of output + accumulation
+ rate of disappearance

FA = (FA + dFA )+ 0 + (-r`A) dW

- dF = (-r` ) dW
A A

  dFA / dW   r `A

FA0 dxA = (-r`A) dW

General design equation for a FBR:

xA

W / FA0   dxA / rA

0

Definition of rate of reaction:

Moles of A disappeared 1 dN A
r `A  
(unit time)(unit Weight ) W dt

When the rate is expressed in terms of catalyst weight, mass transfer

effects between the catalyst and the bulk fluid & also within the catalyst
are ignored. Such mass transfer aspects could be important in some cases.

Fixed Bed Reactor – Integral form

W/F
A0

xA

W / FA0   dxA / rA

0
1 /-rA

xA

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 Lecture 3

Fixed Bed Reactor – differential form

dFA / dW  rA FA0 dx A / dW  rA

-rA
FA -rA xA

W W/FA0
Example 6.3 page 268
Ex: The hydromethylation of Toluene:
C6 H 5CH 3  H 2 C6 H 6  CH 4
catalyst

To design a tubular (packed-bed) and CSTR (Fluidized-bed) reactors, to

produce 10mol Benzene per min from a feed consisting of 20%T, 40%H2
and 40% inerts at 600oC and 10 atm.
The following data to find the rate law from the differential reactor
Run RT*1010mol/g.s PT PH2 PCH4 PB
Set A
1 71 1 1 1 0
2 71.3 1 1 4 0
Set B
3 41.6 1 1 0 1
4 19.7 1 1 0 4
5 42 1 1 1 1
6 17.1 1 1 0 5
Set C
7 71.8 1 1 0 0
8 142 1 2 0 0
9 284 1 4 0 0
Set D
10 47 0.5 1 0 0
11 71.3 1 1 0 0
12 117 5 1 0 0
13 127 10 1 0 0
14 131 15 1 0 0
15 133 20 1 0 0
16 41.8 1 1 1 1
RT is a function of PT, PH2, PB and PCH4

H.W. : Problem 6.6, 6.7, 6.10, 6.11, 6.12, 6.13, 6.15

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 Lecture 4

Catalyst decay
Catalytic deactivation adds another level of complexity to sorting out the
reaction rate law parameters and pathways. In addition we need to make
adjustments for the decay of the catalysts in the design of catalytic
reactors. This adjustment is usually made by a quantitative specification
of the catalyst's activity, a(i). In analyzing reactions over decaying
catalysts we divide the reactions into two categories: separable kinetics
and non separable kinetics. In separable kinetics, we separate the rate law
and activity:

Separable kinetics: rA  a( Past history ) * rA ( fresh catalyst )

When the kinetics and activity are separable, it is possible to study

catalyst decay and reaction kinetics independently. However,
nonseparability,

Nonseparable kinetics: rA  rA  Past history, Fresh catalyst 

Must be accounted for by assuming the existence of a nonideal surface or

describing deactivation by a mechanism composed of several elementary
steps

Types of Catalyst Deactivation

Separable Kinetics: rA (t )  a (t )  rA ( fresh catalyst ) 

Types of Decay

1.) Sintering da
  kD a 2
dt
1
2.) Coking a
1  Bt n
da
3.) Poisoning   kD a n f Ci 
dt

4.) Slow Decay Temperature-Time Trajectories

5.) Moderate Decay Moving Bed
6.) Rapid Decay straight-through transport reactor (STTR)

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 Lecture 4

Derivation of rate law for sintering

Deactivation by sintering may in some cases be a function of the main
stream gas concentration. Although other forms of the sintering decay
rate laws exist, one of the most commonly used decay laws is second
order with respect to the present activity:
da
  kD a 2
dt
Integrating, with a = 1 at time t = 0, yields
1
a(t ) 
1  kd t
The amount of sintering is usually measured in terms of the active surface
area of the catalyst Sa:

Sa 0
Sa 
1  kd t
The sintering decay constant, kd, follows the Arrhenius equation
E  1 1 
kd  kd (T0 ) exp  d   
 R  T0 T  

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 Lecture 4

The general properties and characterization of catalysts and methods of

measuring them
Properties Measurement Methods

1-Composition of chemical elements Standard chemical analysis

X-ray fluorescence
Emission spectrometry
Atomic adsorption
Flame spectrometry
Neutronic activation

2. Nature and structure of the catalytic chemical X-ray diffraction

species Electron diffraction
Nuclear magnetic resonance (NMR)
Electron paramagnetic resonance (EPR)
Infrared and Raman spectroscopy
Visible and ultraviolet spectroscopy
Magnetic methods
Thermogravimetric analysis
Differential thermal analysis
Mösshauer spectroscopy

3.The texture of the catalyst: BET methods

Porosimetry
Texture of the support (porosity, specific
surface, pore distribution) Chemisorption
X-ray diffraction
Electron microscopy
Scanning electron microscopy
State of the dispersed active agents. Magnetic methods
Chemical methods
Electron microprobe analyzer

4. The quality of the active surface Chemisorption kinetics

. Flash desorption
Heats of adsorption
Color doping
EPR, infrared spectroscopy

5. Electronic properties EPR

Conductivity, semi-conductivity
Electron extraction work functions

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 Lecture 5

Residence Time Distribution for Chemical Reactor

SCOPE:
• Design of non-ideal reactors
• Identify the possible deviations
• Measurement of RTD

• Quality of mixing
• Models for mixing
• Calculating the exit conversion in practical reactors

Practical reactor performance deviates from that of ideal reactor’s :

• Packed bed reactor – Channeling
• CSTR & Batch – Dead Zones, Bypass
• PFR – deviation from plug flow – dispersion
• Deviation in residence times of molecules
• the longitudinal mixing caused by vortices and turbulence
• Failure of impellers /mixing devices

How to design the Practical reactor ??

What design equation to use ??

Approach: (1) Design ideal reactor

(2) Account/correct for deviations

Deviations
In an ideal CSTR, the reactant concentration is uniform throughout the
vessel, while in a real stirred tank, the reactant concentration is relatively
high at the point where the feed enters and low in the stagnant regions
that develop in corners and behind baffles.
In an ideal plug flow reactor, all reactant and product molecules at
any given axial position move at the same rate in the direction of the bulk
fluid flow. However, in a real plug flow reactor, fluid velocity profiles,
turbulent mixing, and molecular diffusion cause molecules to move with
changing speeds and in different directions.
The deviations from ideal reactor conditions pose several problems
in the design and analysis of reactors.

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 Lecture 5

Possible Deviations from ideality:

Short Circuiting or By-Pass – Reactant flows into the tank through the inlet and then
directly goes out through the outlet without reacting if the inlet and outlet are close by
or if there exists an easy route between the two.

1. Dead Zone 2. Short Circuiting

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 Lecture 5

Three concepts are generally used to describe the deviations from

ideality:
• the distribution of residence times (RTD)
• the quality of mixing
• the model used to describe the system

These concepts are regarded as characteristics of Mixing.

Analysis of non-ideal reactors is carried out in three levels:

First Level:
• Model the reactors as ideal and account or correct for the
deviations

Second Level:
• Use of macro-mixing information (RTD)

Third Level:
• Use of micro-mixing information – models for fluid flow
behavior
RTD Function: Use of (RTD) in the analysis of non-ideal reactor
performance
In any reactor there is a distribution of residence times
• RTD effects the performance of the reactor
• RTD is a characteristic of the mixing

Measurement of RTD

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 Lecture 5

RTD is measured experimentally by injecting an inert material called

tracer at t=0 and measuring its concentration at the exit as a function of
time.
Injection & Detection points should be very close to the reactor

ASSUMPTIONS
1. Constant flow rate u(l/min) and fluid density ρ(g/l).
2. Only one flowing phase.
3. Closed system input and output by bulk flow only (i.e., no diffusion
across the system boundaries).
4. Flat velocity profiles at the inlet and outlet.
5. Linearity with respect to the tracer analysis, that is, the magnitude of
the response at the outlet is directly proportional to the amount of tracer
injected.
6. The tracer is completely conserved within the system and is identical to
the process fluid in its flow and mixing behavior.

Desirable characteristics of the tracer:

• non-reactive species
• easily detectable
• should have physical properties similar to that of the reacting
mixture
• completely soluble in the mixture
• should not adsorb on the walls
• Its molecular diffusivity should be low and should be conserved
• colored and radioactive materials are the most widely used tracers

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 Lecture 5

Types of tracer inputs:

• Pulse input
• Step input
• Ramp input
• Sinusoidal input

Pulse & Step inputs are most common

Pulse input of tracer

In Pulse input N0 moles of tracer is injected in one shot and the effluent
concentration is measured the amount of material that has spent an
amount of time between t and t+t in the reactor:
N = C(t) v t

The fraction of material that has spent an amount of time between t and
t+t in the reactor:

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 Lecture 5

dN  C (t )vdt

N 0   vC (t )dt
0

N
For pulse input E (t )t 
N0
C (t )
E (t )  
 0
C (t )dt

 E (t )dt  1
0

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 Lecture 5

t1

 E (t )dt  Fraction
0
having a residence time  t1

 E (t )dt  Fraction
t1
having a residence time  t1

The age of an element is defined as the time elapsed since it entered the
system

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 Lecture 5


h
 C (t )dt  2 C
0
0  Cn  2(C1  C2  .......  Cn1 

Disadvantages of pulse input

• injection must be done in a very short time
• when the c-curve has a long tail, the analysis can give rise to
inaccuracies
• amount of tracer used should be known
• however, require very small amount of tracer compared to step
input

Step input of tracer

In step input the conc. of tracer is kept at this level till the outlet conc.
equals the inlet conc.
t
Cout  C0  E (t )dt
0

For step input:

d  C (t ) 
E (t )   
dt  C0  step
Disadvantages of Step input:
• Difficult to maintain a constant tracer conc.
• RTD fn requires differentiation – can lead to errors
• large amount of tracer is required
• need not know the amount of tracer used

Characteristics of the RTD:

• E(t) is called the exit age distribution function or RTD function
• describes the amount of time molecules have spent in the reactor

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 Lecture 5

Cumulative age distribution function F(t):

t
F (t )   E (t )dt
0

1  F (t )   E (t )dt
t

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 Lecture 5

Relationship between the E and F curves

Cumulative age distribution function F(t): Washout function W(t) = 1 - F(t):

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 Lecture 5

E and F Curves with bypassing

E and F Curves with Dead space

Moments of RTD:


1
S   (t  t
3
)3 E (t )dt
 3/2
0
m

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 Lecture 5

If the distribution curve is only known at a number of discrete time

values, ti, then the mean residence time is given by:

Variance:
• represents the square of the distribution spread and has the units of
(time)2
• the greater the value of this moment, the greater the spread of the
RTD
• useful for matching experimental curves to one family of
theoretical curves

Skewness:
• the magnitude of this moment measures the extent that the
distribution is skewed in one direction or other in reference to the
mean

Space time vs. Mean residence time:


V
 tm   tE (t )dt
v0 0

The Space time and Mean residence time would be equal if the following
two conditions are satisfied:
• No density change
• No backmixing

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 Lecture 5

In practical reactors the above two may not be valid and hence there will
be a difference between them.

Normalized RTD function E() :

E ( )   E (t )
  t /

1   E (t )dt
0

1   E ( )d
0

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 Lecture 6

RTD in ideal reactors:

RTD for ideal PFR:
The RTDs in plug-flow reactors and ideal batch reactors are the simplest
to consider. All the atoms leaving such reactors have spent precisely the
same amount of time within the reactors. The distribution function in
such a case is a spike of infinite height and zero width, whose area is
equal to 1: the spike occurs at t = Vlvo = , or  = 1. Mathematically, this
spike is represented by the Dirac delta function:

E (t )   (t   )

 (t )  0 when t  0

 (t )   when t  0
 

  (t )dt  1
 
 g (t ) (t   )dt  g ( )
 
tm   tE (t )dt   t (t   )dt  
0 
 
 2   (t  tm )2 E (t )dt   (t  t m ) 2  (t   )dt  0
0 

RTD for ideal CSTR:

Material balance on tracer

in – out = accumulation

0 – υC = VdC/dt  C(t) = C0 e-t/

C (t ) C0 e  t / e  t /
E (t )    E ( )  e 
 

 C (t )dt  C e
 t /
0 dt
0 0

 
tm   tE (t )dt   te
 t /
/  dt  
0 

 
(t   )2
   (t  tm ) E (t )dt 
2 2
 et / dt   2
0 


1
 Lecture 6

Tanks in series (TIS) Model:

Material balance on the I reactor for tracer:

V1 dC1/dt = -v C1  C1 = C0 exp(-t/1)

Material balance on the II reactor for tracer:

V2 dC2/dt = v C1 – v C2  dC2/dt + C2/2 = C0exp(-t/2) 2

C0t C0t 2 t / i
C2  et / 2 Similarly C3  2 e
2 2 i

C3 (t ) t 2  t / i
E3 (t )   3e

2 i
 C (t )dt
0
3

2
 Lecture 6

For n equal sized CSTRs:

t n 1
E (t )  e t / i
(n  1)! in

Total  = n  = t/ n = t/

i i
t n 1
n(n ) n 1
E (t )   E ()  n i et / i  e n
(n  1)! in
(n  1)!

As the number becomes large,

the behavior of the system
approaches that of PFR

We can calculate the dimensionless variance 2

2 
   2   (  1)2 E ( )d
2

 0
  
   2 E ( )d  2  E ( )d   E ( )d
0 0 0
 
n(n ) n 1
nn
  2
e n d  2  1    n1e n d  1
0
(n  1)! (n  1)! 0

n n  (n  1)!  1 1
  n  2   1  2 n(n  1)  1 
(n  1)!  n  n n

The number of tanks n = 1/2 = 2/2

If the reaction is I order:

1
x  1
(1  k i ) n

3
 Lecture 6

RTD for PFR-CSTR series:

For a pulse tracer input into CSTR the output would be : C(t) = C0e-t/s
Then the outlet would be delayed by a time p at the outlet of the PFR.
RTD for the system would be:

E (t )  0 t   p

e (t  P )/ s
E (t )  t  p
s

If the pulse of tracer is introduced into the PFR, then the same pulse will
appear at the entrance of the CSTR p seconds later. So the RTD for PFR-
CSTR also would be similar to CSTR-PFR.

Though RTD is same for both, performance is different

Remarks:
• RTD is unique for a particular reactor
• The reactor system need not be unique for a given RTD
• RTD alone may not be sufficient to analyze the performance of
non-ideal reactors
• Along with RTD, a model for the flow behavior is required

4
 Lecture 7

Laminar Flow Reactor (LFR)

Before proceeding to show how the RTD can be used to estimate
conversion in a reactor, we shall derive E(t) for a laminar flow reactor.
For laminar flow in tubular reactor, the velocity profile is parabolic, with
the fluid in the center of the tube spending the shortest time in the reactor.
A schematic diagram of the fluid movement after a time t is shown in
Figure 13-8. The figure at the left shows how far down the reactor each
concentric fluid element has traveled after a time t.

Figure 13-8 Schematic diagram of Fluid elements in a laminar flow

reactor.

The velocity profile in a pipe of outer radius R is

  r 2    r  2  20   r 2 
U  U max 1      2U avg 1      1     13  55
  R     R    R   R  
2

where Umax is the centerline velocity and Uavg is the average velocity
through the tube. Uavg is just the volumetric flow rate divided by the
cross sectional area.

The time of passage of an element of fluid at a radius r is

 
L  R2 L  1 
t (r )  
U (r ) 0  2 1   r R 2  
  

t (r )  13  56
2 1   r R  
2

 
The fraction of total fluid between r and (r+dr) is d / 0
d U (r )2 r dr
 13  57
0 0

The fraction of fluid between r and (r + dr) that has a flow rate between v
and (v + d v) spends a time between t and (t + dt) in the reactor is
   
2

    2
 2  rdr
2r dr 4
dt  2  
2 R  1  r R 2    R  1   r R 2  
2


    
And then substitute for t using equation (13-56) to yield

1
 Lecture 7

4t 2
dt  r dr 13  58
 R2
Combining equations 13-57 and 13-58 we now have the fraction of fluid
spending between time t and t+dt in the reactor
d L  2 r dr  L  2   R 2 2
      dt  dt
0 t  0  t  0  4t 2 2t 3
The minimum time the fluid may spend in the reactor is
L L   R2  V 
t   2 
 
U max 2U avg   R  20 2

Consequently, the complete RTD function for a laminar flow reactor is

 
0 t
2
E (t )   2 13  59
 t

 2t 3 2

The cumulative distribution function for t   2 is

t
2 2 1
t
2
F (t )  
 2t2
3
dt 
2 2 t 3
dt  1 
4t 2
13  60

The mean residence time tm is

  
2 1 2  1
tm   tE (t )dt 
 2 2 2 t 2
dt 
2  t   
  2
The result was shown previously to be true for any reactor. The mean
residence time is just the space time .
The dimensionless form of the RTD function is

0   0.5

E ( )   1 13  61
 2 3   0.5

2
 Lecture 7

Reactor modeling with RTD

I. Zero parameter models: (Micro-mixing models)

(a) Segregation model
(b) Maximum mixedness model

II. One parameter models: (Macro-mixing models)

(a) Tanks-in-series model
(b) Dispersion model

III. Two parameter models:

Segregation model (Dankwerts & Zwietering, 1958)

Characteristics:
• Flow is visualized in the form of globules
• Each globule consists of molecules belonging to the same
residence time
• Different globules have different Res. Times
• No interaction/mixing between different globules

3
 Lecture 7

4
 Lecture 7

Mean conversion of globules spending between t and t+dt in the reactor =

(Conversion achieved after spending a time t in the reactor) *
(Fraction of globules that spend between t and t+dt in the reactor)
_
d x  x(t ) E (t )dt

_ 
x   x(t ) E (t )dt
0

Mean conversion in a PFR using Segregation model:

Example: A  R, I order, Constant density

x(t )  1  e  kt for I Order

_  
x   (1  e ) E (t )dt  1   e  kt E (t )dt
 kt

0 0 Mean conversion predicted by

Segregation model matches
_ 
with ideal PFR
x  1   e kt (t   )dt  1  e k
0

Mean conversion in a CSTR using Segregation model:

Example: A  R, I order, Constant density

_  
x  1   e E (t )dt   e kt et / dt / 
 kt

0 0

Mean conversion predicted by

_
k Segregation model matches
x
1  k with ideal CSTR

5
 Lecture 7

Mean conversion in a practical reactor using Segregation model:

Example: A  R, I order, Constant density
_  
x   x(t ) E (t )dt  1   e kt E (t )dt
0 0

• conduct tracer experiment on the practical reactor

• measure C(t) and evaluate E(t)
• plot and evaluate mean conversion

The Dispersion Model:

• The Dispersion Model is used to describe non-ideal PFR

• Axial dispersion is taken into consideration
• Analogous to Fick’s law of diffusion superimposed on the
flow

Da = Diffusivity coefficient; U = superficial velocity;

L = Characteristic length

Backmixing or dispersion is used to represent the combined action of all

phenomena, namely molecular diffusion, turbulent mixing, and non-
uniform velocities, which give rise to a distribution of residence times in
the reactor.

6
 Lecture 7

If the reactor is an ideal plug flow, the tracer pulse traverses through the
reactor without distortion and emerges to give the characteristic ideal
plug flow response. If diffusion occurs, the tracer spreads away from the
center of the original pulse in both the upstream and downstream
directions.

Closed vessel Dispersion Model:

2 2 2
2
  2
(1  e  Per )
t m Per Per

4qe Pe / 2
1 x 
(1  q) 2 e qPe / 2  (1  q) 2 e  qPe / 2

q  1 4 Da / Pe

n-1
D = Damkohler number = k C 
a 0

7
 Lecture 7

8
 Lecture 7

9
 Lecture 7

The x-axis, labeled ‘‘macromixing’’ measures the breadth of the

residence time distribution. It is zero for piston flow, fairly broad for the
exponential distribution of a stirred tank, and broader yet for situations
involving bypassing or stagnancy.
The y-axis is micromixing, which varies from none to complete.
Micromixing effects are unimportant for piston flow and have maximum
importance for stirred tank reactors.
Well-designed reactors will usually fall in the normal region
bounded by the three apexes, which correspond to piston flow, a perfectly
mixed CSTR, and a completely segregated CSTR.

Without even measuring the RTD, limits on the performance of

most real reactors can be determined by calculating the performance at
the three apexes of the normal region.
The calculations require knowledge only of the rate constants and
the mean residence time.
When the residence time distribution is known, the uncertainty
about reactor performance is greatly reduced.
A real system must lie somewhere along a vertical line in Normal
Region.
The upper point on this line corresponds to maximum mixedness
and usually provides one bound limit on reactor performance.
Whether it is an upper or lower bound depends on the reaction
mechanism.
The lower point on the line corresponds to complete segregation
and provides the opposite bound on reactor performance.

11