UNIVERSITY OF TRIPOLI

FACULTY OF ENGINEERING
CHEMICAL ENGINEERING DEPARTMENT

PAPER TITLE:
Distributions Of Residence Times for
Chemical Reactors

Prepared by:
E,benshebil
F. shaku

Under The Supervision Of

Dr.Hadi Alakarmi

Fall 2020
 ABSTRACT

In the core of Chemical Engineering is the reactor design that includes most of all
scientific disciplines. The reactor,in general, are treated ideally: mixed and plug-flow
patterns. Unfortunately, it is observed in the real world a very different behavior from
that expected. Thus, to characterize nonideal reactors is used, among others, residence
time distribution function E(t), mean residence time tm and cumulative distribution
function F(t).

The aim of this paper illustrated issue of reactors make to deviation from ideality And
methods to describe the nonideal reactor such: RTD distribution residence time and
function E(t), cumulative distribution function F(t)…

In addition, How to use the residence time data and function to make predication of
conversion & exit concentration by using two model (segregation model, maximum
mixedness model).

In finally, we compare between Ideal reactors & models the part of conversion.

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INTRODUCTION:
The Chemical Reaction Engineering (CRE) that includes in its scope the design of
reactors uses information, knowledge and experience from areas such as
thermodynamics, mass transfer, chemical kinetic, fluid mechanics, heat transfer and
economic analysis. [1]

In general, the modeling processes involved in CRE establishes idealized systems, with
assumptions of perfect mixing in the CSTR (Continuous Stirred Tank Reactor), slug flow
in PFR (Plug Flow Reactor) and uniform composition in the case of Batch Reactors.
However, in spite of the simplified mathematical treatment, many of cited assumptions
lead to real reactor behavior itself far from ideal, mainly with the capacity and products
distribution with significant

Deviation from the two ideal flow patterns can be caused by channeling of fluid, by
passing of fluid, or by creation of stagnant regions (dead Zone) in the vessel as shown
Figure (1).[2].

Figure (1) : Nonideal flow patterns which may exist in process equipment.

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Overall, three interrelated factors make up the contacting or flow pattern to account
deviations from idealities mentioned:

1.The RTD or residence time distribution of material which is flowing through the vessel.

2.The state of aggregation of the flowing material, its tendency to clump and for a group
of molecules to move about together.

3.The earliness and lateness of mixing of material in the vessel.

Light was placed just in the first statement. Thus, the residence-time distribution (RTD)
is a characteristic of the mixing that occurs inside the chemical reactor [1].

The RTD is one of the important parameters that can provide information on the
characteristics or hydrodynamics of the process plant or reactor. the RTD, which was first
developed by danckwerts (1953) have been widely utilized to diagnose possible system
malfunctions, such as bypassing, leakage, blockage, channeling, fouling and back mixing,
as well as to help estimate the quality of mixing. radiotracers technique uses a radioactive
source and scintillation detectors to accurately detect plant production anomalies (iaea,
2001; iaea, 2008). [1]

MEASUREMENT OF THE RTD

The RTD is determined experimentally by injecting an inert specie, called tracer, into the
reactor at some time and then measuring the tracer concentration, c, in the effluent stream
over time

The tracer must be a nonreactive specie, easily detectable and should have physical
properties close to the reacting mixture, in other words, it should be soluble in the system.
in addition, among others, the tracer’s behavior must reflect the material flowing through
the reactor.

There are, mainly, two used methods of tracer’s injection called pulse input and step
input

In a pulse input, tracer is, suddenly, injected in one shot into the feed stream, entering the
reactor in as short a time as possible. since the step input consider a constant rate of tracer
addition from an initial time, t = 0 before it, there is no tracer been added to the feed. the

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outlet concentration is measured over time, in both methods showed figure (2). in order to
become more understandable

The disadvantage of pulse input are 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.

In step input advantage are: the positive step is usually easy to carry out experimentally
than the pulse test , alse the total amount of tracer in the feed over the period of test does
not have to be known as it does in the pulse test .

The disadvantage of step input are:It is difficult to maintain a constant tracer

concentration in the feed , obtaining the RTD from step test involves differentiation of
the data and present more serious drawback to the technique since differentiation of data
can lead to large errors , large amount of tracer required for this test if the tracer is very
expensive a pulse test is better . [2]

Figure (2): RTD measurement

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THEORY:
Danckwerts introduced the concept of `fluid element', meaning a small volume of fluid
where

continuous properties, such as concentration, can still be defined. The RTD function,
external residence time distribution, E(t), measures the time that the various fractions of
`fluid element' reside in the reactor (macromixing); it gives no information about the
mixing details at a molecular level (micromixing). The expressions of the RTD functions
can be derived for the ideal reactors, as well as for any association of PFR and CSTR
elements.

The E(t) function of a real reactor can be obtained experimentally using stimulus-
response techniques, by well-known methods of tracer injection.

If an impulse of tracer is injected at the inlet, and its outlet concentration C(t) is measured
as function of time, the experimental RTD function, E(t), is obtained from the expression

Ct (t)
E ( t )= ∞ (1)
∫ C t ( t ) dt
0

1- Segregation model

EXIT CONVERSION
RTD + MODEL +KINETIC DATA =
EXIT CONCENTRATION

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To determine the mean conversion in the effluent stream we must average the
conversions of all of the various globules [3]

meancoversion

[ of those globules
spending between = ¿
timet∧t +dt
¿ the reactor
]
Then
d X́ = X(t) * E(t)dt

d X́
=X ( t ) E(t )
dt

Summing over all globules. then mean conversion is

∞

X́ = ∫ X ( t ) E (t ) dt
0

Consider the following first-order reaction :

For batch reactor we have

For constant volume and with NA = NA0 (1-X).

dX
NA0 dt = - rA V = k CAV = k NA =k NA0 (1 – X)
dX
=k ( 1−X )
dt
Solve for X(t) we have
X(t) = 1 – e-kt

Mean conversion for a first-order reaction :

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 ∞ ∞

X́ = ∫ X ( t ) E (t ) dt = ∫ ( 1 – e−kt ) E ( t ) dt
0 0
∞ ∞

= ∫ E ( t ) dt -∫ e−kt E ( t ) dt
0 0

X́ = 1- ∫ e
−kt
E ( t ) dt
0

2- Maximum mixedness model

In a reactor with a segregated fluid, mixing between panicles of fluid does not
occurs until the fluid leaves the reactor. The reactor exit is, of course, he largest latest
possible point that mixing can occur, and any effect of mixing is postpond until after all
reaction has taken place as shown in Figure. We can also think of completely segregated
flow as being in a state of minimum mixedness. We now want to consider the other
extreme, that of maximum rnixedness consistent with a given residence-time distribution.
We return again to the plug-flow reactor with side entrances. only this time the fluid
enters the reactor along its length (Figure3). As soon as the fluid enters the reactor, it is
completely mixed radially (but not longitudinally) with the other fluid already in 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.

Figure (3): Mixing at the earliest possible point

The globules at the far left of correspond to the molecules that spend a long time in the
reactor while those at the far right correspond to the molecules that channel through the
reactor. In the reactor with side entrances, mixing occurs at the earliest possible moment
consistent with the RTD. Thus the effect of mixing occurs as early as possible throughout
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the reactor, and this situation is termed the condition of maximum mixedness The
approach to calculating conversion for a reactor in a condition of maximum rnixedness
will now be developed. In a reactor with side entrances, let ʎ be the time it takes for the
fluid to move from a particular point to the end of the reactor. ln other words, A is the life
expectancy of the fluid in the reactor that point[3]

Figure (4):Modeling maximum by a plug flow reactor with side entrance

Moving down the reactor from left to right, ʎ decreases and becomes zero at the exit. At
the left end of the reactor. ʎ approaches infinity or the maximum residence time if it is
other than infinite.
Consider the fluid that enters the reactor through the sides of volume ΔV in Figure . The
fluid that enters here will have a life expectancy between ʎ and ʎ+dʎ. The fraction of
fluid that will have this life expectancy between the product of the total volumetric flow
rate. υ0 and the fraction of the total that has life expectancy between ʎ and ʎ+dʎ. is E(ʎ) d
ʎ. That is the volumetric rate of fluid entering through the sides of volume ΔV is υ0 E(ʎ)
Ah. Δ ʎ

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The volumetric flow rate at h. ui, is the flow rate that entered at bAk. plus what entered
through the sides vo E(h)M, i.e.,

v ʎ = v ʎ +d ʎ + v0E(ʎ)Δ ʎ

Rearranging and taking the limit as Δ ʎ→ 0

vʎ
= - v 0 E(ʎ)
dʎ

The volumetric Row rate vo at the entrance to the reactor (X= 0) is zero because the fluid
only enters through the sides along the length.
Integrating equation with limits vʎ = 0 at ʎ = ∞ and v ʎ = v ʎ at ʎ = ʎ, we obtain
∞

v ʎ = v0 ∫ E ( ʎ ) d ʎ = v0 [ 1 – F( ʎ ¿ ¿
0

The volume of fluid with a life expectancy between ʎ and ʎ+dʎ. is

ΔV = υ0 [ 1 – F( ʎ ¿ ¿ Δʎ

The rate of generation of the substance A in this volume is

rA ΔV = rA υ0 [ 1 – F( ʎ ¿ ¿ Δʎ

we now carry out a mole balance on substance A between ʎ and ʎ+dʎ

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[ at ʎ¿+ dʎ ] + [ through¿ side ]- [ Out ] +[ generation
at ʎ by reaction ]
=0

υ0 [ 1 – F( ʎ ¿ ¿ CA│ʎ+dʎ + v0 CA0 E(ʎ)Δ ʎ - υ0 [ 1 – F( ʎ ¿ ¿ CA│ʎ

+ rA υ0 [ 1 – F( ʎ ¿ ¿ Δʎ = 0

d {[1 – F(ʎ )]C A(ʎ )}

E(ʎ) CA0+ dʎ
+ rA [ 1 – F( ʎ ¿ ¿= 0

Taking the derivative of the term in brackets

dCA
CA0 E(ʎ) + [ 1 – F( ʎ ¿ ¿ dʎ
- CA E(ʎ) + rA [ 1 – F( ʎ ¿ ¿= 0

Or

We can rewrite equation in terms of conversion as

dX E (ʎ )
-CA0 d ʎ = rA + CA0 [1 – F( ʎ )]
Or
dX rA E(ʎ )
= + (X )
dʎ CA 0 [1 – F (ʎ )]

CASE STUDY:
A sample of the tracer was injected as a pulse to batch reactor,which carried out
irreversible first order (k= 0.1min^-1) in liquid phase , and the effluent concentration was
measured as a function of time, resulting in the data shown in Table

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 T(min) 0 5 10 15 20 25 30 35 40
C(gm/L 0 3 5 5 4 2 1 0.2 0
)

Solution:
We want to compare the conversion In Ideal CSTR.PFR,& Segregsion model

First step find E(t) , Ca

T C E(t) e− KtE(t) t*E(t)

0 0 0 0 0

5 3 0.03 0.0182 0.15

10 5 0.05 0.0182 0.5

15 5 0.05 0.0112 0.75

20 4 0.04 0.0054 0.8

25 2 0.02 0.00164 0.5

30 1 0.010 0.0004 0.3

35 0.2 0.002 6.04E-5 0.07

40 0 0 0 0

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40 40

∫ C ( t ) dt = ∫ C ( t ) dt
0 0

5
= 3 (0+ 4*3+2*5+2*5+2*4+4*2+2*1+4*0.2+0)
= 101.3 (g*min/m3)
C(t) C (t)
40
=
E(t) = 101.3
∫ C ( t ) dt
0

t 0 5 10 15 20 25 30 35 40
C 0 3 5 5 4 2 1 0.2 0
E(t) 0 0.03 0.05 0.05 0.04 0.02 0.01 0.00 0
2

Step 2:For PFR

Mole balance

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 dX −ra
=
dV Fao

Rate law

-ra=Kca

Stoichiometry

Ca= Cao*(1-X)

Combining

dX KCao∗(1− X)
=
dV vo∗Cao

Rearrangement
V
X=1- e vo∗K =1−e−1.513=0.779

Step 3: For CSTR

Mole balance

Fao∗X
V=
−ra

Rate law

- ra=Kca

Stoichiometry

Ca= Cao*(1-X)

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Combining

vo∗Cao∗X
V=
K∗Cao∗(1−X )

Rearrangement

τ∗K 0.1∗15.13
X= = =0.602
1+ τ∗K 1+0.1∗15.13

Step 4 : For Segregation Model

∞
−kt
X =1-∫ ( e )∗E ( t ) dt =1−0.288= 0.712
0

Results:
Reactor Conversion

Ideal PFR 0.779

Ideal CSTR 0.602

Segregation Model 0.712

Conclusions
 From results show in table the prediction conversion based on residence time is between
PFR & CSTR which the performance of reactor is nearest the PFR than CSTR.

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Recommendation:
 Chapter 13 is shown the principles of how to deal with nonideal reactors but Not
description of detailed of models
 In Chapter 14 more detailed on models.

Reference:
1. https://www.researchgate.net/publication/308797261_residence_time_distribution_rtd_in
_operating_plant_a_review/link/5ac6d5ee0f7e9bcd519326e9/download.
2. Levenspiel, Octave. Chemical reaction engineering. John Wiley & Sons, 1999.
3. Westmoreland, P. R. "ELEMENTS OF CHEMICAL REACTION ENGINEERING: by
H. Scott Fogler." Chemical Engineering Education 27, no. 4 (1993): 161-167.

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