CRE - II

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Dirac-Delta Function
■ The Dirac delta function is a linear function that maps every function to its value at zero.
It is used to model the density of an idealized point value as a function equal to zero
everywhere.
■ The two properties of this function which we need to know are
∞ Any integration with ∞
Area under the curve: 𝛿 𝑡−𝜏 =1 function results in the 𝛿 𝑡 − 𝜏 𝑓(𝑡) = 𝑓(𝜏)
0 function itself 0

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RTD in ideal Reactors
■ RTD in PFR and Batch Reactor
■ 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
■ Mathematically, this spike is represented by the Dirac delta function 𝐸 𝑡 = 𝛿(𝑡 − 𝜏)
■ The Dirac delta function has the following properties
RTD in ideal Reactors
■ Mean Residence Time set g(x) = t

■ Variance

All material spends exactly a time  in the reactor, so there is no variance

■ The cumulative distribution function F(t) is

■ RTD in Single CSTR

■ In an ideal CSTR the concentration of any substance in the effluent stream is identical to
the concentration throughout the reactor
RTD in ideal Reactors
■ Exit age distribution

■ Cumulative Distribution

■ Mean Residence Time

■ Variance

■ The standard deviation is the square root of the variance. For a CSTR, the standard
deviation of the residence time distribution is as large as the mean itself
RTD in LFR
■ For laminar flow in a tubular (i.e. cylindrical) reactor, the velocity profile is parabolic
with the fluid in the center of the tube spending the shortest time in the reactor

■ The Velocity profile can be given by

■ The time of passage for an element

RTD in LFR
■ Exit age Distribution can be given by

■ Minimum time fluid may spend in reactor

■ Complete RTD Function for Laminar Flow can be given as

■ Cumulative Distribution function

■ Mean residence time is just space time 𝑡𝑚 = 𝜏

PFR/CSTR in series RTD
■ Modeling real reactors as PFR and CSTR in series
■ In some stirred tank reactors, there is a highly agitated zone in the vicinity of the
impeller that can be modeled as a perfectly mixed CSTR
■ the reacting mixture may follow a somewhat tortuous path either before entering or
after leaving the perfectly mixed zone—or even both. This tortuous path may be
modeled as a plug-flow reactor
■ Thus the reactor may be modeled as a CSTR in series with a plug-flow reactor, and
the PFR may either precede or follow the CSTR
PFR/CSTR in SeRieS RTD…
■ For CSTR outlet concentration as function of time

■ This output will be delayed by a time p at the outlet of the plug-flow section of the
reactor system

■ If the reactor system with CSTR is preceded by the PFR will be treated. If the pulse of
tracer is introduced into the entrance of the plug-flow section, then the same pulse will
appear at the entrance of the perfectly mixed section τp seconds later, meaning that the
RTD of the reactor system will again be same
■ No matter where the CSTR occurs within the PFR/CSTR reactor sequence, the same
RTD results. What about conversion??
PFR/CSTR in SeRieS RTD…
■ The RTD is not a complete description of structure for a particular reactor or system of
reactors.
■ The RTD is unique for a particular or given reactor. However, the reactor or reaction
system is not unique for a particular RTD.
■ When analyzing nonideal reactors, the RTD alone is not sufficient to determine its
performance, and more information is needed.
■ In addition to the RTD, an adequate model of the nonideal reactor flow pattern and
knowledge of the quality of mixing or “degree of segregation” are both required to
characterize a reactor properly
CSTR
1
𝐸 𝑡 = 𝑒 −𝑡 𝜏
𝜏 ■ Perfect Operation – Base,
Exponential Decay in
concentration
■ Effective mean time = 

■ Bypassing – Part vb/v0 bypassing,

lesser material for reaction with
same reactor volume
■ Effective mean time  > b

■ Dead Volume – Reactor volume

occupied by dead zone
■ Effective Reactor volume
decreases  < b
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CSTR

■ Calculate and plot E(t) and F(t) for the ideal case (P) and then compare with the
measured RTD E(t) to see if the RTD suggests either bypassing (BP) or dead zones
(DV).

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Example -1
■ A large tank (860 liters) is used as a gas-liquid contactor. Gas bubbles up through the vessel
and out the top, liquid flows in at one part and out the other at 5 liters. To get an idea of the
flow pattern of liquid in this tank a pulse of tracer (150 gm) is injected at the liquid inlet
and measured at the outlet, as shown in Fig.
A. Is this a properly done experiment?
B. If so, find the liquid fraction in the vessel.
C. Determine the E curve for the liquid.
D. Qualitatively what do you think is happening in the vessel?

Levenspiel Example 11.2 13

Conversion in Non-ideal reactors
■ To evaluate reactor behavior in general we have to know four factors:
1. the kinetics of the reaction (CRE-1)
2. the RTD of fluid in the reactor
3. the earliness or lateness of fluid mixing in the reactor
4. whether the fluid is a micro or macro fluid
■ For a reactor processing a second-order reaction
– (a) the reactant starts at high concentration and reacts away rapidly because n > 1.
– (b) the fluid drops immediately to a low concentration.
■ Since the rate of reaction drops more rapidly than does the concentration you will end up with a
lower conversion.
Conversion in Non-ideal reactors
■ To Predict conversion in real reactor following models were proposed
■ Zero adjustable Parameter Model
– Segregation Model
– Maximum Mixedness Model
■ One Adjustable Parameter Model
– Tanks in series Model
– Dispersion Model
■ Two adjustable Parameter Model
– Real Reactors are modeled as combination of ideal reactors
■ For the zero adjustable parameter models, we do not need to make any intermediate
calculations; we use the E- and F-Curves directly to predict the conversion given the kinetic
parameters.
■ For the one-parameter models, we use the RTD to calculate mean residence time, tm, and
variance, 2, which we can then use
– to find the number of tanks in series necessary to accurately model a nonideal CSTR
– calculate the Peclet number, Pe, to find the conversion in a tubular flow reactor using the
dispersion model
Mixing-1
■ RTD tells us how long the various fluid elements have been in the reactor, but it does not tell us
anything about the exchange of matter between the fluid elements (i.e., the mixing)
■ Mixing of reacting species is one of the major factors controlling the behavior of chemical
reactors
■ First order reactions are independent of the concentration hence mixing is of no importance and
knowledge of the length of time each molecule spends in the reactor is all that is needed to predict
conversion. For first-order reactions conversion can be given as -
𝑑𝑋
= 𝑘(1 − 𝑋)
𝑑𝑡

■ For reactions other than first order, knowledge of the RTD is not sufficient to predict conversion.
For reactions other than first order, the degree of mixing of molecules must be known in addition
to how long each molecule spends in the reactor
■ The model needs to be developed which takes care of mixing which occur at 2 different levels –
– Micromixing
– Macromixing
Mixing-2
■ Macromixing produces a distribution of residence times without specifying how molecules of different
ages encounter one another in the reactor
■ Micromixing describes how molecules of different ages encounter one another in the reactor. There are
two extremes of micromixing:
1. all molecules of the same age group remain together as they travel through the reactor and are not
mixed with any other age until they exit the reactor (i.e., complete segregation);
2. molecules of different age groups are completely mixed at the molecular level as soon as they enter
the reactor (complete micromixing).
■ For a given state of macromixing (i.e., a given RTD), these two extremes of micromixing will give the
upper and lower limits on conversion in a nonideal reactor.
■ For single reactions with orders greater than one or less than zero, the segregation model will predict the
highest conversion.
■ For reaction orders between zero and one, the maximum mixedness model will predict the highest
conversion
Mixing-3
■ Define a globule as a fluid particle containing millions of molecules all of the same age.
■ A fluid in which the globules of a given age do not mix with other globules is called a macrofluid. A
macrofluid could be visualized as non-coalescent globules where all the molecules in a given globule
have the same age.
■ A fluid in which molecules are not constrained to remain in the globule and are free to move everywhere
is called a microfluid
■ There are two extremes of mixing of the macrofluid globules—early mixing and late mixing. The
extremes of late and early mixing are referred to as complete segregation and maximum mixedness,
respectively.

Macrofluid Microfluid
Zero Parameter Model
■ Segregation Model - The extremes of complete micromixing and complete segregation are the limits
of the micromixing of a reacting mixture
■ Consider a CSTR, in the segregated flow model, the flow through the reactor to consist of a
continuous series of globules

■ These globules retain their identity; that is, they do not interchange
material with other globules in the fluid during their period of residence,
i.e., they remain segregated.
■ Each globule spends a different amount of time in the reactor.
■ In essence, lumping all the molecules that have exactly the same
residence time in the reactor into the same globule.
■ The principles of reactor performance in the presence of completely
segregated mixing were first described by Danckwerts and Zwietering
 Feed In
Multi-tubular Reactor
t2
t3 t1

• Those Entering through center will have

shorter residence times

• Those Entering through corner will have

long residence time

X3
X1 X2

Product Out
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Maximum Mixedness Model
■ Completely Segregated flow are at minimum mixedness
■ The maximum mixedness occur when fluid is completely mixed radially (not longitudinally)
as soon as it enters the reactor.
■ The entering fluid is fed into the reactor through the side entrances in
such a manner that the RTD of the plug-flow reactor with side
entrances is identical to the RTD of the real reactor.
■ Let λ be the time it takes for the fluid to move from a particular point
to the end of the reactor. In other words, λ is the life expectancy of
the fluid in the reactor at that point
■ Moving down the reactor from left to right, the
life expectancy, λ,decreases and becomes zero at
the exit. At the left end of the reactor, λ
approaches infinity or the maximum residence
time if it is other than infinite
Maximum Mixedness Model
■ The volumetric flow at the outlet can be given as

■ Mole Balance -

For given RTD and reaction orders greater than one, the maximum
mixedness model gives the lower bound on conversion
Comparison of Model prediction
■ If Rate is represented by power law model

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Multiple reactions
■ When multiple reactions occur in reacting systems, it is best to work in concentrations,
moles, or molar flow rates rather than conversion

Segregation Model

Maximum Mixedness

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Segregation Model

■ Consider a PFR, the fluid flows down the reactor in plug flow, each exit stream corresponds to a
specific residence time in the reactor.
■ Batches of molecules are removed from the reactor at different locations along the reactor in such
a manner as to duplicate the RTD function, E(t).
■ The molecules removed near the entrance to the reactor correspond to those molecules having
short residence times in the reactor.
■ Physically, this effluent would correspond to the molecules that channel rapidly through the reactor.
The farther the molecules travel along the reactor before being removed, the longer their residence
time.
■ The points at which the various groups or batches of molecules are removed correspond to the
RTD function for the reactor.
SegRegaTion MoDel…

Sum it for all globules for mean conversion

First Order Reactions

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SegRegaTion MoDel…
Reactor RTD Function Mean Conversion
∞
Batch - 𝑋 =1− 𝑒 −𝑘𝑡 𝐸 𝑡 𝑑𝑡
0
𝐸 𝑡 = 𝛿(𝑡 − 𝜏) 𝑋 = 1− 𝑒 −𝑘𝜏 = 1 − 𝑒 −𝐷𝑎1
PFR
Dirac-Delta Function
1 𝑡 𝜏𝑘 𝐷𝑎1
CSTR 𝐸 𝑡 = 𝑒− 𝜏 𝑋= =
𝜏 1 + 𝜏𝑘 1 + 𝐷𝑎1
0, 𝑡<𝜏 2
Laminar FR 𝐸 𝑡 = 𝜏2
, 𝑡≥𝜏 2
2𝑡 3

■ Da is Damkohler number which relates the reaction time to residence time.

Example
■ Given that the Damkohler number values are – 0.1, 1, 2, 4, 10, find out the
conversion of first order reactions in PFR, CSTR and LFR using Segregation Model.

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Distributions in reactors

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One Parameter Model
■ A single parameter to account for the nonideality of our reactor.
■ This parameter is most always evaluated by analyzing the RTD determined from a tracer
test.
■ Examples of Two-parameter models for nonideal CSTRs include
– reactor dead volume, VD, where no reaction takes place,
– Volumetric flow rate with part of the fluid bypassing the reactor, vb, thereby exiting
unreacted.
■ Examples of one-parameter models for tubular reactors include
– the tanks-in-series model
– the dispersion model.
■ For the tanks-in-series model, the one parameter is the number of tanks, n, and for the
dispersion model, the one parameter is the dispersion coefficient, Da

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One Parameter Model
■ Consider ideal tubular reactors with usual assumptions
– fluid moves through the reactor in a piston-like flow (i.e., plug flow reactor), and every
atom spends an identical length of time in the reaction environment. Here, the velocity
profile is flat, and there is no axial mixing
■ In reality this is never the case and to compensate non ideality
– One approach involves modeling the non ideal tubular reactor as a series of
identically sized CSTRs.
– The other approach (the dispersion model) involves a modification of the ideal reactor
by imposing axial dispersion on plug flow.

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Tanks in series (TIS) Model
■ The TIS model is one parameter model
■ This model can be used whenever the dispersion model is used; and for not too large a
deviation from plug flow both models give identical results, for all practical purposes.
■ The dispersion model has the advantage in that all correlations for flow in real reactors
invariably use that model.
■ The tanks-in-series model is simple, can be used with any kinetics, and it can be extended
without too much difficulty to any arrangement of compartments, with or without recycle
■ Consider n tanks in series then define
𝑡
𝜃𝑖 = Dimensionless time based on Mean residence time per tank
𝑡𝑖
𝑡
𝜃= Dimensionless time based on Mean residence time in all tanks
𝑡
𝜃 = 𝑁𝜃𝑖

At any given time 𝐸 𝜃 = 𝑡𝐸(𝑡) Real System Model

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TankS in SeRieS (TiS) MoDel…
■ Consider N tanks in series, with steady flow of v m3/s
■ The first tank with volume V1 inject a pulse tracer at time t = 0
■ When the tracer is evenly distributed in tank1 the concentration becomes C0. Now consider
material balance for tracer at time t

Real System Model

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■ For the first reactor 𝐶1 = 𝐶0 𝑒 −𝑡 𝜏𝑖

𝑑𝐶2
■ For the second reactor 𝑉2
𝑑𝑡
= 𝑣𝐶1 − 𝑣𝐶2

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TankS in SeRieS (TiS) MoDel…
■ The RTD curve with Exit
■ When the number of the CSTRs are increased the system starts behaving more like the plug
flow reactor.

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Example
■ The first-order reaction A  B is carried out in a 10-cm-diameter tubular reactor 6.36 m
in length. The specific reaction rate is 0.25 min1. The results of a tracer test carried out
on this reactor are shown in Table

Calculate the conversion using (a) PFR, (b) the tanks-in-series model, and (c) a single CSTR.

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SiMPSon’S 1/3 Rule
3 points

Quadrature
Formula
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Dispersion Model
■ These models apply when there is deviation from plug flow behavior e.g. to turbulent
flow in pipes, laminar flow in very long tubes, flow in packed beds, shaft kilns, long
channels, screw conveyers, etc.
■ For laminar flow in short tubes or laminar flow of viscous materials these models may
not apply, and it may be that the parabolic velocity profile is the main cause of deviation
from plug flow. We treat this situation, called the pure convection model
■ What is dispersion?
– It is nothing but spread and suggests how the distribution is.
■ The dispersion coefficient D (m2/s) represents this spreading process. Thus
– large D means rapid spreading
– small D means slow spreading
– D = 0 means no spreading, hence plug flow

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Dispersion Model

■ A dimensionless group D/uL, characterizes the spread. This group can be evaluated by
recording the shape of the tracer curve as it passes the exit of the vessel using mean time
and variance

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Dispersion Model
■ A dimensionless group D/uL, characterizes the spread. This group can be evaluated by
recording the shape of the tracer curve as it passes the exit of the vessel using mean time
and variance

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Two Parameter Model
■ The premise for the two-parameter model is that we can use a combination of ideal reactors
to model the real reactor. Consider a packed bed reactor with channeling.

■ We can model the real reactor as two ideal PBRs in parallel, with the two parameters being
the volumetric flow rate that channels or by passes, vb, and the reactor dead volume, VD.
The real reactor volume is V = VD + VS with entering volumetric flow rate v0 = vb + vs.

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