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Jun 05, 2013

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Reactor

Attribution Non-Commercial (BY-NC)

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Reactor

Attribution Non-Commercial (BY-NC)

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Deviation of real reactors from ideal reactors Residence time distribution (E) Cumulative residence time distribution (F) Pulse and step experiments E and F for ideal and real reactors

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Ideal reactors present two well-defined and opposite flow patterns: PFR: 0% backmixing

Each element of fluid translates with the same rate in the axial direction without overtaking or mixing with other elements ahead or behind (plug flow). Therefore each element of fluid spends the same time inside a ideal PFR. Composition and temperature are the same in each differential cylindrical element of volume dV, but they change along the axial direction.

The mixing is complete and instantaneous. Composition and temperature are homogeneous in the whole reactor.

2

Ex: stagnant regions and by-pass phenomena in a real stirred vessel

[A]0 By-pass [A]0 [A]

Ideal CSTR

real CSTR

[A]f

[A]f=[A]

stagnant regions

Ideal PFR real PFR

r

If we know precisely how every element of fluid moves within the vessel, then we should be able to predict the behaviour of a vessel as a reactor. This approach is impractical, but fortunately not necessary. We just need to know the residence time distribution (elements of fluid taking different routes through the reactor may take different lengths of time to pass through the vessel). This information can be determined easily and directly by stimulus-response experiments.

4

The distribution of the residence time for the stream leaving the vessel is called exit age distribution E (or residence time distribution). E(t)dt = fraction of exit stream that spends a time between t and (t+dt) in the reactor. The area below the curve E, which represents the fraction of exit fluid younger than t, is called cumulative residence time distribution F .

F (t ) = E (t )dt

0

t1

dF (t ) = E (t ) dt

E

0

t1

E(t) is normalized:

E (t )dt = 1

0

Pulse-Methode

A pulse of a nonreactive tracer is instantaneously introduced into the fluid entering the vessel and the concentration of the tracer leaving the vessel is recorded versus time. After normalisation of the area under the curve, we obtain the function residence time distribution E(t). 6

The concentration readings in the table represent the response to a pulse input into a vessel which is to be used as a chemical reactor. Tabulate and plot the exit age distribution E(t).

Time (min) 0 5 10 15 20 25 30 35 Cpulse (mg/liter)

Cpulse (mg/liter)

6 5 4 3 2 1 0 0 10 20 30 40

0 3 5 5 4 2 1 0

Time (min)

7

Solution: to find E, the concentration reading must each be divided by the total area under the curve Cpulse vs time t , giving:

6

Cpulse (mg/liter)

E(t)=C(t)/AREA=C(t)/100

5 4 3 2 1 0 0 5 10 15 20

AREA

Time (min) 0 5 10 15 20 25 30 35

Cpulse (mg/liter) 0 3 5 5 4 2 1 0

25

30

35

Time (min)

0.02 0.01 0

E (min-1)

0.04

Time (min)

Step experiment

At time t=0 we switch from ordinary fluid to a fluid with a nonreactive tracer of concentration Cmax and measure the outlet tracer Cstep versus time. This dimensionless form of the Cstep curve is the function cumulative residence time distribution F(t).

9

Pulse-method E(t) Step-method F(t)

Ideal and real reactors E(t) CSTR F(t)

11

Compartment models

The compartments model is an arrangement of ideal reactors (CSTR and/or PFR) distributed in series and/or in parallel.

General form: IN several lines with 1 n cells; every cell can be a CSTR or a PFR. OUT

By comparing the E curve for the real vessel with the theoretical curves for various compartment models, it is possible to find which model best fits the real vessel (modelling of real reactors with ideal reactors). Important examples: CSTR in series (cascade of CSTR) CSTR/PFR in parallel

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Cascade of CSTR

The cascade of CSTR is an arrangement of n ideal CSTR in series.

Problem: theoretically in a tubular reactor the fluid should move as a piston (0% of backmixing). However a certain degree of backmixing exists in every real tubular reactors. How to determine it? Solution: with respect to the fluodinamic, a cascade of ideal CSTR behaves between the two extreme cases of the ideal reactors CSTR (100% backmixing) and PFR (0% backmixing). Therefore a cascade of ideal CSTR can help us to determine the degree of backmixing and thus to model a real tubular reactor.

The number n of reactors in series correlates with the degree of backmixing in a real tubular reactor. 13

PFR 1 F(t)

1 2 4

32

0,5

1,5

2 t/

The curve distribution of the residence time F(t) of the real tubular reactor can be easily obtained by the step-experiment method and then compared with the theoretical one for a cascade of n ideal CSTR.

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The cascade of continuous stirred tank reactors has also an important role in industrial praxis because this configuration bypasses the principal disadvantage of a stirred tank (the reaction takes place on the low level concentration at the exit of the reactor, requiring a reactor with a large volume). It is possible to play with two different parameters: the number and the volumes of reactors in series. Additionally, a reactant can be added stepwise in every reactor composing the cascade if its concentration has to be kept low.

15

Problem: degree of by-pass in a real continuous stirred reactor. Solution: configuration CSTR/PFR in parallel: in the main line there is a ideal CSTR, in the second one an ideal PFR. The PFR in parallel and external to the CSTR can be thought to represent the internal bypass that occurs in a real CSTR.

16

Vocabulary

Backmixing Cascade of CSTR Compartment model Cumulative residence time distribution Exit age distribution Laminar flow Modelling of real reactors Normalization Parabolic profile of velocity Plug flow Pulse experiment Real reactors Residence time distribution Stagnant regions Step experiment Stimulus-response experiments Tracer substance vollstndige Rckvermischung KIK Kaskade Mehrparametriges Modell Verweilzeitsummenkurve Alterverteilung am Reaktorausgang Laminare Strmung Modellierung realer Reaktoren Normalisierung Parabelfrmiges Geschwindigkeitsprofil Pfropfenstrmung Stomarkierungsexperiment Reale Reaktoren Verweilzeitverteilung Totzonen Sprungmarkierungsexperiment Reiz-Reaktion Experiment 17 Tracersubstanz

Books

Octave Levenspiel Chemical Reaction Engineering, third edition, Wiley (1999). Chapter 11-12.

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