Advanced Chemical Engineering Kinetics

(ChemE 7004)
Topic 7:
Distributions of Residence Times for Chemical Reactors

Prof. Wen-Yueh Yu ()
Catalysis and Surface Chemistry Lab
Department of Chemical Engineering
National Taiwan University
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Non-Ideal Flow Patterns

Ideal flow patterns:

Residence time of all molecules are identical
Perfectly mixed CSTRs & batch reactors
No radial diffusion in a PFR/PBR
CSTR
Non-ideal flow patterns:
A(g) + B(l) C(l)

dead zone

channeling

Liquid-Gas Reactor PBR

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Residence-Time Distribution (RTD)
Tracer

Tracer:
Inert. Injection Detection
Easy to track (colorful, radioactive).
Has physical properties similar to those of reactants (complete mixing).
No adsorption on the wall of reactor.
pulse injection and step injection.
C curve

Pulse injection

Step injection
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Residence-Time Distribution (RTD)
Pulse Injection

measured mass at outlet with residence time

between t and t + t

measured mass fraction at outlet with

residence time between t and t + t

residence-time distribution function

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Residence-Time Distribution (RTD)
Pulse Injection (contd)

Sum of mass fraction = 1

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Residence-Time Distribution (RTD)
Pulse Injection: An Example
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Residence-Time Distribution (RTD)
Pulse Injection: An Example (contd)
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Residence-Time Distribution (RTD)
Pulse Injection: An Example (contd)

0.51 0.3
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Difficulties in Pulse Injection

Hard to achieve "perfect pulse

The integration of tail region is difficult

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Cumulative Distribution Function

Cumulative Distribution Function

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Residence-Time Distribution (RTD)
Step Injection
Advantage:
Easier operation than that of
pulse injection.
No need to know the total
amount.

Disadvantage:
Maintain constant C0
Data differentiation
Need a large amount of tracer
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Mean Residence Time (tm) and
Other Moments

Mean residence time

For a constant volumetric flow, tm = (prove it yourself)

Variance

The "spread" of the distribution; the greater the value of

this moment is, the greater a distributions spread will be.

Skewness

The extent that a distribution is skewed in one direction or

another in reference to the mean.
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Normalized Residence-Time Distribution Function

The purpose of creating this normalized distribution function is that the flow
performance inside reactors of different sizes can be compared directly.
Take CSTR as example,
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RTD in Ideal Reactors
Plug-Flow Reactors
All the atoms leaving such reactors have spent precisely the same amount of time
within the reactors.
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RTD in Ideal Reactors
Single CSTR
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RTD in Ideal Reactors
Single CSTR (contd)

Ideal CSTR Ideal PFR

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Residence-Time Distribution (RTD)
Ideal vs. Non-ideal

Nearly ideal PFR Non-ideal PBR

Nearly ideal CSTR Non-ideal CSTR

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Diagnostics and Troubleshooting
CSTR: Perfect Operation (P)
For CSTR with pulse tracer
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Diagnostics and Troubleshooting
CSTR: Bypassing (BP)

The analysis of a bypass to the CSTR may be elucidated by observing the

output to a step tracer input to the real reactor.
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Diagnostics and Troubleshooting
CSTR: Dead Volume (DV)
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Diagnostics and Troubleshooting
CSTR: Summary

BP

DV
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Diagnostics and Troubleshooting
PFR: Perfect Operation (P) and Bypassing (BP)
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Diagnostics and Troubleshooting
PFR: Dead Volume (DV) and Summary
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Residence Time Distribution
Laminar Flow Reactor

Molecules near the center spend a shorter time in the reactor than
those close to the wall.

where
Umax: the centerline velocity,
Uavg: the average velocity through the tube; the volumetric flow rate
divided by the cross-sectional area.
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Residence Time Distribution
Laminar Flow Reactor
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Residence Time Distribution
Laminar Flow Reactor (contd)
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Residence Time Distribution
Laminar Flow Reactor (contd)
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Residence Time Distribution
CSTR and PFR in Series

No matter where the CSTR occurs within the PFR/CSTR reactor

sequence, the same RTD results! But not same conversion!
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CSTR and PFR in Series -
Example 13-3

The RTD is not a complete description of structure for a particular

reactor or system of reactors.
When analyzing non-ideal reactors, the RTD alone is not sufficient
to determine its performance, and more information is needed.