Chapter 13 Summary Notes

9/24/13
Chapter 13 Summary Notes
13. DISTRIBUTION REACTORS*

Topics
1. 2. 3. 4.
OF
RESIDENCE TIMES
FOR
CHEMICAL
Residence Time Distribution RTD for Ideal Reactors RTD to Diagnose Faulty Operation 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 Reactions
1. Residence Time Distribution

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).
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From the exit tracer concentration we can determine the following information:
A. RTD (Residence Time Distribution) Function (E(t))
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= 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
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13.1 Mean Residence Time 13.1 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, inside the reactor between a time
= Fraction of molecules inside the reactor that have been and .
5. Life Expectancy leave the reactor in a time
= Fraction of molecules inside the reactor with age to .
that are expected to
From our experimental data of the exit tracer concentration from pulse trace test
t(min)
:01 2 3 4 5 6
C(mg/m3):000.10.20.30.10 We can obtain
->
->
->
->
13.2 Calculate E(t), t and s2 13.2 Using the E(t) curves
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2. RTD for Ideal Reactors

for Ideal Reactors PFR- Inject a pulse at t=0
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Dirac Delta Function
CSTR
Laminar (LFR)
13.3 Drawing the F(theta) curves for the above ideal reactors 13.4 Matching Reactors with Tracer Step Inputs 13.5 Matching Reactor Models with E(t)
3. RTD to Diagnose Faulty Operation
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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
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The CSTR Concentration
RTD Function
Cumulative Function
Space Time a. Perfect Operation
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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)
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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. Models to Calculate the Exit Concentrations and Conversions
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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
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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.
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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.
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4A.3 Segregation Model Applied to a CSTR
4A.4 Mean Concentration for Multiple Reactions
Solutions Using Software Packages

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For multiple reactions use an ODE solver to couple the mole balance equations, dCi/dt=ri, with the segregation model equations: d reactor at time t and /dt=Ci(t)*E(t), where C i is the concentration of i in the batch is the concentration of i after mixing the batch reactors at the exit.
13.6 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.
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Dividing byDland taking the limit asDlgoes to zero. Substitute
Differentiating the first term and recalling we obtain.
We need to integrate backwards from have some maximum value of (say
(the entrance) to
= 0 (the exit). In real systems we minutes. Consequently we
= 200 minutes) rather than
integrate backward from = 200. However, because most ODE packages will not integrate backwards, we have to use the transfer z =T Thus to integrate forward
In terms of conversion,
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13.7 Maximum Mixedness Model
13.3 Calculate Xmm and Xseg
5. Comparing Segregation and Maximum Mixedness Predictions
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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. Multiple Reactions and RTD Data
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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:
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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.
Object Assessment of Chapter 13
* All chapter references are for the 4th Edition of the text Elements of Chemical Reaction
Engineering . top
Fogler & G urmen 2 0 0 8 U nivers ity of M ic higan
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9/24/13