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Distribution of Residence Times for Chemical ReactorsTopics1. Residence Time Distribution 2. RTD for Ideal Reactors 3. RTD to Diagnose Faulty Operation 4. Models to Calculate Exit Concentrations and Conversions A. Segregation Model 1. Segregation Model Applied to an Ideal PFR 2. Segregation Model Applied to an LFR 3. Segregation Model Applied to a CSTR 4. Mean Concentration for Multiple Reactions B. Maximum Mixedness Model 5. Comparing XMM and Xseg 6. RTD and Multiple Reactions1. 1. Residenc
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Distribution of Residence Times for Chemical Reactors
Topics
1. Residence Time Distribution 2. RTD for Ideal Reactors 3. RTD to Diagnose Faulty Operation
4. Models to Calculate Exit Concentrations and Conversions A. Segregation Model
1. Segregation Model Applied to an Ideal PFR 2. Segregation Model Applied to an LFR 3. Segregation Model Applied to a CSTR 4. Mean Concentration for Multiple Reactions
B. Maximum Mixedness Model 5. Comparing X MM and Xseg
6. RTD and Multiple Reactions
1. 1. Residence Time Distribution top
We shall use the RTD to characterize existing (i.e. real) reactors and then use it to predict exit conversions and concentrations when reactions occur in these reactors.
Inject a tracer and measure exit concentration, CT(t).
From the exit tracer concentration we can determine the following information:
A. RTD (Residence Time Distribution) Function (E(t))
= Fraction of molecules exiting the reactor that have spent a time between (t) and (t + dt) in the reactor.
B. The Cumulative Distribution Function F(t)
= Fraction of molecules exiting the reactor that have spent a time t or less in the reactor.
= Fraction of molecules that have spent a time t or greater in the reactor.
C. Definitions
1. Mean Residence Time
13.113.1 Mean Residence Time
13.113.1 Residence Time Distribution Analysis using COMSOL Multiphysics
2. Variance
3. Space Time - For no dispersion/diffusion and v = v0, the space time equals the mean residence time.
4. Internal Age Distribution, = Fraction of molecules inside the reactor that have
been inside the reactor between a time and .
5. Life Expectancy = Fraction of molecules inside the reactor with age that are
expected to leave the reactor in a time to .
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
We can obtain
-> -> -> ->
13.213.2 Calculate E(t), t and s2
13.213.2 Using the E(t) curves
2. 2. RTD for Ideal Reactors top
for Ideal Reactors
PFR- Inject a pulse at t=0
Dirac Delta Function
CSTR
Laminar (LFR)
13.313.3 Drawing the F(theta) curves for the above ideal reactors
13.413.4 Matching Reactors with Tracer Step Inputs
13.513.5 Matching Reactor Models with E(t)
3. 3. RTD to Diagnose Faulty Operation top
Experimentally injecting and measureing the tracer in a laminar flow reactor can be a difficult task, if not a nightmare. For example, if one uses tracer chemicals that are photo-activated as they enter the reactor, the analysis and interpretation of E(t) from the data becomes much more involved.
Diagnostics and Troubleshooting
The CSTR
Concentration
RTD Function
Cumulative Function
Space Time
a. Perfect Operation
b. Passing (BP)
c. Dead Volume
A summary for ideal CSTR mixing volume is shown in Figure 13-14
Tubular Reactor
A similar analysis to that for a CSTR can be carried out on a tubular reactor.
a. Perfect Operation of PFR (P)
b. PFR with Channeling (Bypassing, BP)
c. PFR with Dead Volume (DV)
A summary for PRF is shown in Figure 13-18
In addition to its use in diagnosis, the RTD can be used to predict conversion in existing reactors when a new reaction is tried in an old reactor. However, the RTD is not unique for a given system, and we need to develop models for the RTD to predict conversion.
Medicinal Uses of RTD 4. 4. Models to Calculate the Exit Concentrations and Conversions top
If using mathematical software to apply the models described below, you may need to fit C(t) and E(t) to a polynomial. The procedure for fitting C(t) and E(t) to a polynomial is identical to the techniques use to fitting concentration as a function of time described in Chapter 5.
Polymath regression analysis tutorial
Use combinations of ideal reactors to model real reactors that could also include: Zero parameter models
Segregation Model Maximum Mixedness Model
One parameter models
Tanks-in-Series Model Dispersion Model
Two parameter models
Bypassing Dead Space Recycle
4A. Segregation Model
Models the real reactor as a number of small batch reactors, each spending a different time in the reactor. All molecules that spend the same length of time in the reactor (i.e., that are of the same age) remain together in the same globule (i.e., batch reactor). Mixing of the different age groups occurs at the last possible moment at the reactor exit.
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 real reactor at different times will have a different conversion. (X1,X2,X3...)
But, the mean conversion for the segregation model is
4A.1 Segregation Model Applied To An Ideal PFR
Lets apply the segregation model to an ideal PFR and see if we get the same result for conversion as we did in Chapter 4.
Solve for X(t) for a first order reaction in a batch reactor.
For the batch reactor the conversion-time relationship is
Calculate the mean conversion
which is the same conversion one finds from a mole balance (Chapter 4)
Further Explanation of Mean Conversion in Segregation Model
4A.2 Segregation Model Applied to an 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).
Hilder, M.H. Trans. IchemE 59 p143(1979)
For large values of the Damkohler number then there is complete conversion along the streamlines off the center streamline so that the conversion is determined along the pipe axis.
4A.3 Segregation Model Applied to a CSTR
4A.4 Mean Concentration for Multiple Reactions
Solutions Using Software Packages
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.
13.613.6 Batch, PFR, CSTR, Segregation
4B Maximum Mixedness Model
Mixing occurs at the earliest possible moment.
Note E(l)=E(t)
E(l)dl =Fraction of molecules that have a life expectancy between l+dl and l.
Modeling maximum mixedness as a plug flow reactor with side entrances.
Dividing byDland taking the limit asDlgoes 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,
13.713.7 Maximum Mixedness Model
13.313.3 Calculate Xmm and Xseg 5. 5. Comparing Segregation and Maximum Mixedness Predictions top
For example, if the rate law is a power law model
From the product [(n)(n-1)], we see
If n > 1, then > 0 and Xseg > Xmm
If n < 0, then > 0 and Xseg > Xmm
If 0 > n < 1, then < 0 and Xseg < Xmm
6. 6. Multiple Reactions and RTD Data top
For multiple reactions use an ODE solver to couple the mole balance equations, dCi/dt=ri (where ri is the net rate of reaction), with the segregation model equations: dCi/dt=Ci(t)*E(t) as previously shown. For maximum mixedness:
To obtain solutions with an ODE solver, first fit E(t) to a polynomial or several polynomials.
Then let z = T - where T is the largest time in which E(t) is recorded. Proceed to solve the resulting equations.
Ideal Reactor Design EquationsResidence Time
theoretical mean residence time
reactor volume
reactor flow rate
Step input for completely mixed or continuously stirred tank reactor CSTR
concentration
initial concentration
time
theoretical mean detention time
Pulse Input for completely mixed or continuously stirred tank reactor CSTR
concentration
initial concentration
time
theoretical mean detention time
concentration at n tank in series
Plug Flor Reactor PFR
step input:when t < tR, C = 0when t >= tR, C = C0
pulse input:when t = tR, C = C0
when t < tR, C = 0when t > tR, C = 0
Where tR = theoretical mean residence timeV = reactor volume Q = reactor flow rate C = concentration at time C0 = initial concentrationCn = concentration at tank nt = timen = number of tanks
Models for Non ideal Reactors
Topics
1. One Parameter Models
2. Two Parameter Models
1. 1. One Parameter Models top
A. Tanks-In-Series
A real reactor will be modeled as a number of equally sized tanks-in-series. Each tank behaves as an ideal CSTR. The number of tanks necessary, n (our one parameter), is determined from the E(t) curve.
For n tanks in series, E(t) is
It can be shown that
In dimensionless form
Carrying out the integration for the n tanks-in-series E(t)
For a first order reaction
For reactions other than first order and for multiple reactions the sequential equations must be solved
B. Dispersion Model
The one parameter to be determined in the dispersion model is the dispersion coefficient, Da. The dispersion model is used most often for non-ideal tubular reactors. The dispersion coefficient can be found by a pulse tracer experiment.
After a very, very narrow pulse of tracer is injected, molecular diffusion (and eddy diffusion in turbulent flow) cause to pulse to widen as the tracer molecules diffuse randomly in all directions. The convective transport equation is:
Finding the Dispersion Coefficient
1) For laminar flow Taylor-Aris Dispersion, the molecules diffuse across radial
streamlines as well as axially to disperse the fluid.
2) To find Da for pipes in turbulent flow see Figure 14-6
3) To find Da for packed bed reactors see Figure 14-7
Using the RTD to find the Dispersion Coefficient.
Results of the tracer test can be used to determine Per from E(t). We need to
consider two sets of boundary conditions.
1. Closed-Closed Vessels
2. Open-Open Vessels
For a Closed-Closed Vessel
We note there is a discontinuity at the entering boundary in the tracer concentration.
Due to the discontinuity at boundary due to forward diffusion, Ct(O-)=Ct0>Ct(O+)
However, at the end of the reactor, Ct(L-)=Ct(L+)
Returning to the unsteady tracer balance
(1)
Let λ = z/L, and
Then in dimensionless form
For the closed-closed boundary condition the solution to the tracer balance at the exit (λ = 1) , at any time Θ, i.e., Ψ(1,Θ) gives
where
(2)
From page 530 of Froment and Bischoff Chemical Reactor Analysis, 2 nd Edition, John Wiley & Sons, 1966. Eigen Values αi are found from the equation
For Pe = 10 α1=1.5 α2=2.4 α3=4.8 α4=5.1 α5=7.9 α6=8.1
F
0 ≤ λ ≤ 1
Integrating Equation (3) using Equation (2) gives
(3)
We see from the equation for E(theta) that the exponential term dies out as the values of alpha i become large.
then tm and Per is found from the relationship:
Use RTD data to calculate tm, 2, and then Per (i.e. Da) and then use Da in calculating conversion.
For the solution to with the above boundary conditions we find
For an Open-Open Vessel
Dispersion occurs upstream, downstream and within the reactor.
Per>100, for long tubes, the solution at the exit is
Because of the dispersion the mean residence time is greater than the space time. The molecules can flow out of the reactor and then diffuse back in.
Use RTD data to calculate tm, 2, and then Per (i.e. Da) and then use Da in calculating conversion. It can be shown that at steady state, the open-open boundary conditions reduce to the Dankwerts Boundary Conditions.
14.114.1 Sketch of F curves
Dispersion with Reaction
For a First Order Reaction
Let Ψ = CA/CA0, λ = z/L , Pe = UL/Da , and Da = kτ. The dimensionless balance on the concentration of A in the reaction zone is
Danckwerts Boundary conditions
At λ = 0 then
At λ = 1, then
the solution is [See John B. Butt, Reaction Kinetics and Reactor Design, 2 nd Edition, page 378, Marcel Dekker, 2000.]
where
The Polymath program used to plot Ψ versus λ is given below
Polymath Program
Sketches of the dimensionless concentration profiles for different values of Peclet and Damköhler numbers are shown below
Note how Ψ(0+) changes as Pe and Da change.
The exit conversion is
The following figures given the Polymath solutions for y versus l for different values of Pe and Da
Open Open System
Upstream of the reaction zone the balance on A in dimensionless form is
For these boundary conditions
the solution is
Rearranging
A typical profile is
The following profiles were obtained from the Polymath Program given above. Here Ψ1 is the dimensionless concentration of A upstream of the reaction section where Da is greater than zero and Ψ is the dimensionless concentration of A in the reaction section.
Use RTD data to calculate tm, 2, and then Per (i.e. Da) and then use Da in calculating conversion.
2. 2. Two Parameter Models top
The goal is to model the real reactor with combinations of ideal reactors.
CSTR with Bypass and Dead Volume
Two parameters and , the fraction of volume that is well-mixed (alpha), and the fraction of the stream that is bypassed (beta).
Reactor Balance
We now find the parameters a and b from a tracer experiment. We will choose a step tracer input
The balance equations are:
14.114.1 Finding a two parameter model
OTHER SCHEME INCLUDED
Real Reactor Model of Reactor
Two parameters, and :
1. Use the tracer data to find and . 2. Then use the mole balances and the rate law to solve for CA1 and CA2.
Reactor 1:
(Eqn. A)
Rate Law:
for a first order reaction or
for a second order reaction
Reactor 2:
(Eqn. B)
Rate Law:
Solve Equations (A) and (B) to obtain CA1 as a function of , , k, , and CA0.
Overall Conversion