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
4
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
time of atoms have spent in the reactor
Residence Time Distribution (RTD)
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 species
•easily detectable
•similar physical properties to those of the reacting mixture
•completely soluble in the mixture
•not 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 dN vC (t )dt
resulting to N o vC (t )dt
0
resulting to N o vC (t )dt
0
C (t )
Residence-time distribution function, E (t )
C (t )dt
0
Fraction of matrial leaving
the reactor that has resided t 2
E (t )dt
in the reactor for times t1
between t1 and t 2
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
t spending in reactor for
0 E (t )dt less than time t @ from F (t )
t 0 to t t Cumulative
distribution
Graph plotting function
F (t)
t (min)
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
2
(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
1
s (t t m ) 3 E (t )dt
3
3 0
2
Normalized RTD Function
To compare directly the flow performance inside reactors
of different sizes.
Example, CSTR:
1
E (t ) e t /
t
E () E (t ) e
where
Internal Age Distribution
To identify the reaction mixture condition in the reactor
Internal Age Distribution,
I(α )d α = Fraction of molecules inside the reactor that
have been inside the reactor between a time (α) and
(α+d α)
Example
From our experimental data of the exit tracer concentration from pulse trace test
t(min) : 0 1 2 3 4 5 6
C(mg/m3) : 0 0 0.1 0.2 0.3 0.1 0
→ → → →
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 Co
t
C (t ) Co e
C(t)
e t
E (t )
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
A→R
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).
30 30 Figure 1. (a) Tracer data
C (x10-6molcm-3)
C (x10-6molcm-3)
20 20 of the reactor before it
10 10 was first used. (b) Tracer
data of the reactor after it
0 0
was used for 2 years.
13 14 15 16 17 9 10 11 12 13
t (s) t (s)
(a) (b)
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
Apply the segregation model to an ideal PFR
Solve for X(t) for a first order reaction in a batch reactor. The
conversion-time relationship is
Calculate the mean conversion
LFR
For a Laminar flow reactor the RTD function is
The mean conversion is
The last integral is the exponential integral and can be
evaluated from Tabulated values
Fortunately, Hilder developed an approximate formula ( =Da).
CSTR
Mean Conversion of CSTR
Mean Conversion of Multiple
Reactions
For multiple reactions use an ODE solver to couple the mole
balance equations, dCi/dt=ri, with the segregation model
equations: d /dt=Ci(t)*E(t), where C i is the concentration of
i in the batch reactor at time t and is the concentration of i
after mixing the batch reactors at the exit.
Example:
The second order reaction
occurs in the liquid phase. The RTD function for the reactor in which it is to be carried
out is given by
E(t)=0 for 0 < t < 10
E(t) = 0.01 (t–10) for 10 < t < 20
E(t) = 0.01 (30–t) for 20 < t < 30
E(t) = 0 for t > 30
This RTD function is the same one we previously studied in these lectures. The
entering concentration is 2 molar and the specific reaction rate is 0.06 dm 3/mol•s.
(a) What is the conversion after 30 seconds in a batch reactor?
Solution
(b) What conversion would be achieved in a PFR with the same mean residence time?
Solution
(c) What conversion would be achieved in a CSTR with the same mean residence
time?
Solution
(d) What is the conversion predicted by the segregation model?
Solution
Continue Lec
Maximum Mixedness Model
Mixing occurs at the earliest possible moment.
Note E()=E(t)
E()d =Fraction of molecules that have a life expectancy between
+d and .
Modeling maximum mixedness as a plug flow reactor with side
entrances
Dividing by and taking the limit as goes to zero
Substitute
Differentiating the first term and recalling
We obtain
We need to integrate backwards from = (the entrance) to = 0
(the exit). In real systems we have some maximum value of (say
= 200 minutes) rather than = minutes.
Consequently we integrate backward from = 200. However,
because most ODE packages will not integrate backwards, we have
to use the transfer
z = T - to integrate forward
Thus,
In terms of conversion
The End
