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Distributions of

Residence Times for


Chemical Reactors
Chapter 4
BKF3472

Objectives

Define a residence time distribution RTD [E(t), F(t)] and the


mean residence time.

Determine E(t) form tracer data.

Write the RTD functions (E(t), F(t), I(t)) for ideal CSTRs, PFRs,
and laminar flow reactors.

Predict conversions from RTD data using the segregation and


maximum mixedness models.

Predict effluent concentrations for multiple reactions using the


segregation and maximum mixedness models.

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.
3

1.

Dead Zone 2. Short Circuiting

Topics to cover

General characteristics

Measurement of the RTD

Characteristics of the RTD

RTD in Ideal Reactor

Reactor modeling with the RTD

Zero parameter models

RTD and multiple reactions

General Characteristics

Analyze non ideal reactor system

3 concepts to describe non-ideal reactor

Residence Time Distribution


Mixing quality
Model used to describe the system

Residence Time Distribution


(RTD)

Residence time

Residence Time Distribution (RTD)

time of atoms have spent in the reactor

Characteristic of the mixing that occurs in the chemical


reactor. i.e. plug flow and thoroughly-mixed flow show
different RTD

RTD purposes

To diagnose problems of reactors in operation


To predict conversion or effluent concentrations in
existing/available reactors when a new reaction is used

RTD determination via

Inject tracer, colored or radioactive material,


Time tracer have spent I the reactor is recorded

2 method of injection

Pulse input
Step input

Tracer:
non-reactive
easily

detectable

similar

physical properties to those of the reacting mixture

completely
not

species

soluble in the mixture

adsorb on the walls/other surfaces in the reactor

colored

and radioactive materials are most common types of


8

tracers

Measurements of the
RTD

Pulse Input

N C (t )vt
Integrating of
resulting to

dN vC (t )dt

N o vC (t )dt
0

N o vC (t )dt

resulting to

E (t )
Residence-time distribution function,

C (t )

C (t )dt
0

Fraction of matrial leaving


the reactor that has resided

t2

between t1 and t 2

in the reactor for times

E (t )dt

t1

See example 13-1!

Step Input

Drawbacks
Difficult to maintain a constant tracer
concentration in the feed
Large error
expensive

Characteristics of the
RTD

E(t) - exit age distribution function

Characteristics

Integral relationship
Mean Residence Time
Variance
Skewness
Normalized RTD function
Internal Age Distribution

Integral Relationship
fraction of effluent

spending in reactor for


0 E (t )dt less than time t @ from F (t )

t 0 to t t

Graph plotting

F (t)

t (min)

Cumulative
distribution
function

Mean Residence Time tm

when v=v0 and in the absence of dispersion effect, =tm


(proof is at pg 880-881 4th edition and only for closed
system). = space time
Give the average time the effluent molecules spent in the
reactor
Commonly used in analysis. Identified also as first moment

t m tE (t )dt
0

Variance

Also known as square of standard deviation


To indicate the spread of the distribution. The
magnitude measures how spread is the data.
Commonly use in analysis
Also identified as the 2nd moment

(t tm) 2 E (t )dt
0

Skewness

To measure the extent that a distribution is


skewed to one direction or another in reference to
the mean.
Also identified as Third-moment

s
3

3
2

(t t m ) 3 E (t )dt

Normalized RTD Function

To compare directly the flow performance inside reactors


of different sizes.
Example, CSTR:

1 t /
E (t ) e

E () E (t ) e

t
where

Internal Age Distribution

To identify the reaction mixture condition in the reactor


Internal Age Distribution,
I( )d = Fraction of molecules inside the reactor that
have been inside the reactor between a time () and
(+d )

Example
From our experimental data of the exit tracer concentration from pulse trace test
t(min)

C(mg/m3)

0.1

0.2

0.3

0.1

RTD in Ideal Reactor (Pulse Inj.)


RTD for Ideal PFR
PFR- Inject a pulse at t=0

Dirac Delta Function

F(t)

RTD in Ideal Reactor (Pulse Inj.)


Ideal CSTR

C (t ) Co e

Co

C(t)

e t
E (t )

F (t ) 1 e

RTD for Diagnose


Faulty Operation

(Ideal CSTR)

Model as PFR with recycle and some dispersion

Modelling Using
Ideal RTD

Perfect Operation

Passing (BP)

Dead Volume

Tubular Reactor
Perfect Operation
of PFR (P)

PFR with Channeling


(Bypassing, BP)

PFR with Dead


Volume (DV)

Diagnose the problem


occurred the plug flow reactor.
A liquid fluid reacts according to
AR
as the reactant A flows through a 60m3 plug flow reactor with the flow rate of
1m3 s-1 at the initial concentration of 0.05 mol L-1. The reaction is zero order with
the rate constant of 0.045 mol L-1 min-1. The tracer test was performed before
the plug flow reactor was first used and after it was used for 2 years. The
results are shown in Figure 1(a) and Figure 1(b).
Figure 1. (a) Tracer data
of the reactor before it
was first used. (b) Tracer
data of the reactor after it
was used for 2 years.

Model to Calculate the


Exit Concentrations and
Conversions

Combination of Ideal and Real Reactor involves:

Zero Parameter Model


Segregation model
Maximum Mixedness Model

One Parameter Models


Tanks-in series model
Dispersion model

Two Parameter Models


Bypassing
Dead Space
Recycling

Segregation Model

Mixing of the globules of different ages occurs here


Little batch reactors (globules) inside a CSTR.
X3>X2>X1

Mixing occurs at the latest possible moment. Each little batch reactor (globule) exiting

the mean conversion for the segregation model is

PFR

Detail description of segregation


A B
ApplythesegregationmodeltoanidealPFR
SolveforX(t)forafirstorderreactioninabatchreactor.The
conversion-timerelationshipis

Calculatethemeanconversion

LFR
ForaLaminarflowreactortheRTDfunctionis

Themeanconversionis

Thelastintegralistheexponential integralandcanbe
evaluatedfromTabulatedvalues

Fortunately, Hilder developed an approximate formula (

=Da).

CSTR
Mean Conversion of CSTR

Mean Conversion of Multiple


Reactions

FormultiplereactionsuseanODEsolvertocouplethemole
balanceequations,dCi/dt=ri,withthesegregationmodel
equations:d/dt=Ci(t)*E(t),whereCiistheconcentrationof
iinthebatchreactorattimetandistheconcentrationofi
aftermixingthebatchreactorsattheexit.

Example:
Thesecondorderreaction

occursintheliquidphase.TheRTDfunctionforthereactorinwhichitistobecarried
outisgivenby
E(t)=0for0<t<10
E(t)=0.01(t10)for10<t<20
E(t)=0.01(30t)for20<t<30
E(t)=0fort>30

ThisRTDfunctionisthesameonewepreviouslystudiedintheselectures.The
enteringconcentrationis2molarandthespecificreactionrateis0.06dm 3/mols.
(a)Whatistheconversionafter30secondsinabatchreactor?
Solution
(b)WhatconversionwouldbeachievedinaPFRwiththesamemeanresidencetime?
Solution
(c)WhatconversionwouldbeachievedinaCSTRwiththesamemeanresidencetime?
Solution
(d)Whatistheconversionpredictedbythesegregationmodel?
Solution
Continue Lec

Maximum Mixedness Model


Mixingoccursattheearliestpossiblemoment.

NoteE()=E(t)

E()d=Fractionofmoleculesthathavealifeexpectancybetween
+dand.

Modelingmaximummixednessasaplugflowreactorwithside
entrances

Dividing by and taking the limit as goes to zero


Substitute

Differentiating the first term and recalling

We obtain

Weneedtointegratebackwardsfrom=(theentrance)to=0
(theexit).Inrealsystemswehavesomemaximumvalueof(say
=200minutes)ratherthan=minutes.
Consequentlyweintegratebackwardfrom=200.However,
becausemostODEpackageswillnotintegratebackwards,wehave
tousethetransfer
z=T-tointegrateforward
Thus,

Intermsofconversion

The End

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