Non-ideal Reactors: Residence Time Distribution (RTD)

Introduction:

The reactors treated thus far have been modeled as ideal reactors. In the real world,
however, we often observe reactor behavior very different from the ideal model equations.
In this section we learn how to diagnose and handle chemical reactors whose
performance deviates from the ideal. 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. By residence time we mean the time that a fluid element
(particle) spends within the boundaries of the reactor. We will first define all the functions
that are needed to characterize the flow pattern.

After studying this section, you should be able to describe the cumulative F(t) and external
age E(t) and residence-time distribution functions, and to recognize these functions for
PFR, CSTR, and laminar flow reactors. You should also be able to apply these functions
to calculate the conversion and concentrations exiting a reactor.

Non-ideal flow in a CSTR:

In an ideal CSTR, there is uniform reactant concentration throughout the vessel

In real (non-ideal) stirred tank:
• Relatively high reactant concentration at the feed entrance,
• Relatively low concentration in the stagnant regions, called dead zones (usually
corners and behind baffles)
Non-ideal flow in a PFR:

In an Ideal plug flow reactor, all reactant and product molecules at any given axial position
move at same rate in the direction of the bulk fluid flow.
In real plug flow reactor: fluid velocity profiles, turbulent mixing, and molecular diffusion
cause molecules to move with changing speeds and in different directions.

In a real, non-ideal packed-bed there may be sections in the packed bed that offer little
resistance to flow, and as a result a major portion of the fluid may channel through this
pathway. Consequently, the molecules following this pathway do not spend as much time
in the reactor as those flowing through the regions of high resistance to flow. There is
thus a distribution of times that molecules spend in the reactor in contact with the catalyst.

Residence Time Distribution (RTD):

In an ideal plug-flow reactor or an ideal batch reactor all the atoms of materials within the
reactor have been inside it for an identical length of time. The time the atoms have spent
in the reactor is called the residence time of the atoms in the reactor. In all other reactor
types, and NON-IDEAL reactors, the various atoms in the feed spend different times
inside the reactor; that is, there is a distribution of residence times of the material within
the reactor.
In the CSTR above, some atoms entering the reactor leave it almost immediately because
of bypassing. Some atoms remain in the reactor almost for a very long time because they
end up in the dead zone. Most of the atoms, however, leave the reactor after spending
some period of time - somewhere in the vicinity of the mean residence time.

Measurement of the RTD:

The RTD is determined experimentally by injecting an inert chemical, molecule, or atom,

called a tracer, into the reactor at some time t = 0 and then measuring the tracer
concentration, C, in the effluent stream as a function of time. In addition to being a
nonreactive species that is easily detectable, the tracer should have physical properties
similar to those of the reacting mixture and be completely soluble in the mixture. It also
should not adsorb on the walls or other surfaces in the reactor.

In a pulse input, an amount of tracer N0 is suddenly injected in one shot into the feed
stream in as short a time as possible. The outlet (effluent) concentration is then measured
as a function of time. Typical concentration–time curves at the inlet and outlet of an
arbitrary reactor are shown in the figure below:
The effluent concentration–time curve is referred to as the C curve in RTD analysis.

In non-ideal reactors different elements of fluid take different routes through the reactor
and thus may take different lengths of time to pass through the vessel. The distribution of
these times for the stream of fluid leaving the vessel is called the exit age distribution E(t),
or the residence time distribution RTD of fluid. E(t) has the units of time-1. E(t) is also
known as the Exit Age Density Function. RTD ≡ E(t) ≡ “residence time distribution”
function. E(t) is the function that describes in a quantitative manner how much time
different fluid elements have spent in the reactor.
For a pulse input, we define E(t) as:
u C (t )
E (t ) =
N0
where u is effluent volumetric flowrate. Since u and N0 are constants we see that
E (t ) a C (t )
which implies that the E curve is proportional to the concentration, C(t) – this implies that
the C(t) and E(t) have the same shape – they are not equal or identical, but have the
same shape!

The integral in the denominator is the area under the C curve.

Properties of E-curve:
1)
t2
æ Fraction of material leaving reactor that has ö
çç ÷÷ =
è been inside reactor for a time between t 1 and t 2 ø
ò E (t ) dt
t1

2)
We know that the fraction of all the material that has resided for a time t in the reactor between
time t =0 and t = ¥ is 1. This simply means that given a sufficiently long time, all the material will
leave the reactor, ie total fraction is 1.

3)
The fraction of material younger than age t1 is given by:
t1

ò E (t )dt
0

whereas the fraction of material older than t1 (shown as the shaded area in the figure
above), is given by:
¥ t1

ò E (t )dt = 1 - ò E (t )dt
t1 0

Example (from your Textbook!)

A sample of the tracer hytane at 320 K was injected as a pulse to a reactor, and the
effluent concentration was measured as a function of time, resulting in the data shown in
table below:

The measurements represent the exact concentrations at the times listed and not average
values between the various sampling tests.
a) Construct figures showing C(t) and E (t) as functions of time.
b) Determine both the fraction of material leaving the reactor that has spent between
3 and 6 min in the reactor and the fraction of material leaving that has spent
between 7.75 and 8.25 min in the reactor, and
c) Determine the fraction of material leaving the reactor that has spent 3 min or less
in the reactor.
Solution:

a) The C curve was done using both EXCEL and POLYMATH:

The C-curve was plotted using EXCEL and POLYMATH:

t C
0 0
Chart Title
1 1 12
2 5 10 C curve
3 8
4 10 8
C (g/m^3)

5 8 6
6 6
7 4 4
8 3 2
9 2.2
10 1.5 0
0 2 4 6 8 10 12 14 16
12 0.6
14 0 t (min)

POLYMATH

For E Curve:
C (t )
E (t ) = ¥

ò C (t )dt
o
 ¥
To determine ò C ( t )dt we need to determine the area under the curve. One could plot the
0

curve on a graph paper and dertermine the area under the curve by counting the number
of squares, one use use the 3 point or 5 point formula to determine area under a curve or
you simply use POLYMATH (this literally takes 1 second to do). POLYMATH gave an
area of 50.03 g.min/m3 using Simpsons Rule – the text book gave an area of 50.0
breaking the area into two regions and using the 3 point formula.

t C(t) E(t)
0 0 0.00 Chart Title
1 1 0.02 0,25
2 5 0.10
0,20
3 8 0.16
4 10 0.20
(min^-1)

0,15
5 8 0.16
0,10
6 6 0.12
7 4 0.08 0,05
8 3 0.06 0,00
9 2.2 0.04 0 2 4 6 8 10 12 14 16
10 1.5 0.03 t (min)
12 0.6 0.01
14 0 0.00

POLYMATH
b) To determine the fraction of material leaving the reactor that has spent between 3
and 6 min in the reactor we simply find the area underneath the E(t) vs t curve (ie
integrate) between the time 3 and 6 minutes. POLYMATH gave an answer of
0.513. This means that 51% of the material leaving the reactor spends between 3
and 6 minutes in the reactor.
To determine the fraction of material leaving that has spent between 7.75 and 8.25
min in the reactor we again find the area under the curve. POLYMATH gave an
answer of 0.030 ie 3% of the material leaving the reactor spends between 7.75
and 8.25 min in the reactor.
c) To determine the fraction of material leaving the reactor that has spent 3 min or
less in the reactor we integrate between time t = 0 and time t=3: POLYMATH gives
an answer of 0.19 (Textbook: 0.2). This means that 19% of material spends less
than 3 minutes in reactor. This also means that 1 – 0.19 = 0.81 or 81% of the
material spends more than 3 minutes in the reactor.