Chemical Engineering Science 55 (2000) 5907}5917

Interpretation of residence time distribution data

A. D. Martin*
North West Water Ltd, Dawson House, Liverpool Road, Warrington WA5 3LW, UK
Received 26 November 1998; received in revised form 15 November 1999; accepted 27 March 2000
Abstract
`Tracera or Residence time distribution (RTD) studies are commonly exploited as a means of developing an understanding of the
`mixinga status of vessels of various types. The e!ort involved in the setting up of such plant studies can be considerable and the
execution of the experiment its self is often a test of endurance. In the past full interpretation of the results has not been easy and as
a consequence super"cial treatments have been employed. This paper presents an alternative method for interpreting RTD data,
which is relatively easy to use and addresses some of the weaknesses of more conventional methods. An extention to the `tanks in
seriesa concept is presented (ETIS) and united with the `reactor networka formulation. The suitability and appropriateness of the
model is discussed and compared with the `closeda dispersion model 2000 Published by Elsevier Science Ltd. All rights reserved.
Keywords: Residence time; Tanks in series; `Closeda system; Networks; Comparison; Case studies
1. Introduction
Diagnosis of the operational ills and the characterisa-
tion of new equipment at both pilot and full scale are
common activities in the process industries. An impor-
tant component in the diagnosis or characterisation pro-
cess is an understanding of the vessel hydrodynamics,
which at a global or `black boxa level may be gained
from the interpretation of the vessel residence time distri-
bution (RTD). One of the many drivers for the character-
isation arises from the need to simulate process responses
to unusual operating conditions. Many reactor models
encoded within dynamic simulation packages such as
STOAT'` GPSX'` and SPEEDUP'` are capable of
using information regarding the RTD of the vessel under
consideration to improve the "delity of the model. Typi-
cally these models employ parameters such as the Peclet
number (Pe), the dispersion number (N
"
) or the number
of tanks in series (n
2
) in conjunction with the mean
residence time (
0
) to describe deviations from the ideal
continuous stirred tank reactor (CSTR) or the plug-#ow
reactor (PFR). The reactor models avoid the necessity of
employing complex computational #uid dynamics by
restricting their consideration to a single characteristic
* Now at: Environmental Technology Centre, Department of Chem-
ical Engineering, OMIST, Manchester M60 1QD, UK. Tel.: #44-161-
200-4340.
E-mail address: Alaistair.martin@OMIST.ac.uk (A. D. Martin).
length. These models are consequently one dimensional
in form.
2. One-dimensional models
There have been many models of this type designed to
interpret deviations from the two ideal extremes. The
entire family of models may be said to describe dispersed
plug-#ow reactors (DPFR). The magnitude of the disper-
sion as quanti"ed by N
"
increases from zero in the PFR
to in"nity in the CSTR. The `opena and `closeda disper-
sion models fall into this family as does the tanks in series
(TIS) model.
The **open++ dispersion model considers the axial
motion of a #uid element to be made up of two compo-
nents:
1. The convective component arising from the bulk
motion of the #uid.
2. The di!usive component arising from the random
motion of the element in response to the decay of
turbulent eddies.
This concept is expressed mathematically by the con-
ventional `di!usion with bulk #owa equation (Eq. (1)).
cC
c0
"

D
u
c`C
cz`
!
cC
cz
, (1)
0009-2509/00/$- see front matter 2000 Published by Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 0 0 ) 0 0 1 0 8 - 1
where the dimensionless group
D
u
"N
"
"
1
Pe
(2)
and
0"
t

0
"
Q
0
t
<
0
"
ut

(3)
The `opena boundary conditions from which this model
draws its name de"ne the #ow condition at the reactor
inlet and outlet. The `opena condition is physically
achieved when the #ow is undisturbed at the inlet and the
outlet. In 1957 Levenspiel and Smith published the ana-
lytical solution to Eq. (1) for the `opena boundary condi-
tions (Levenspiel & Smith, 1957). This solution is shown
in Eq. (4).
E(0)"
C
C
B
"
1
2
Pe
0
e

.C'F'
`
"F

(4)
Where C
B
is the concentration that would have been
obtained had the `dyea been evenly dispersed through-
out the vessel under study.
With mean and variance
0M
"
"1#
2
Pe
, (5)
o`
"
"
2
Pe
#
8
Pe`
, (6)
It can be seen that the mean of this distribution is
a function of the dispersion and at high dispersion (low
Pe) the mean is substantially '1. This result appears to
be inconsistent with the mass balance but may be ex-
plained by the di!usion of `dyea upstream of the injec-
tion point. Thus, the pulse injected at the inlet is not the
same as the pulse which would have been measured at
the inlet. Casual observation of the inlet to and exit from
a high-dispersion reactor would also con#ict with the
assumed `opena boundary conditions. The rigorous
mathematical de"nition of the `opena boundary condi-
tions makes this model more di$cult to use than the
tanks in series formulation as the user is often left in some
doubt as to the degree to which the `opena condition is
achieved in the system under investigation.
The **closed++ dispersion model treats the system in
exactly the same fashion as the `opena dispersion model.
Eq. (1) is solved with the `closeda boundary conditions.
The `closeda boundary conditions relate to the physical
situation in which the #ow approaches the inlet to the
reactor in idealised plug #ow (Pe"R), transforms to
dispersed #ow within the reactor and returns to idealised
plug #ow at the exit. This situation is very closely ap-
proximated in many real reactors even those which are
themselves low dispersion devices. Thomas and McKee
(1944) published the analytical solution with `closeda
boundary conditions in 1944. Their solution, published
in a dimensional form, is reproduced here in non-dimen-
sional form (Eq. (7)) to maintain consistency with Leven-
spiel and Smith's `opena solution (Eq. (4)). Yagi and
Miyauchi reproduced the Thomas and McKee solution
in 1953 with an alternative condensation of the terms
(Yagi & Miyauchi, 1953).
E(0)"
C
C
B
"2
L`

L
Pe:
L
e.C`

F'?
`
L >'`

Pe(:`
L
#1)#4
:
L
cos

Pe
2
:
L

#sin

Pe
2
:
L

, (7)
where :
L
is given by the positive roots of Eq. (8).
tan

Pe
2
:
L

"
2:
L
(:`
L
!1)
. (8)
Levenspeil (1972) published expressions for the mean and
variance of the `closeda system RTD though did not
report the analytical solution for the RTD itself. Leven-
spiel's mean and variance can be shown to be equal to
those of Eq. (7) thus con"rming their association. These
results are shown below Eq. (9) for the mean,
0M
!
"4
L`
L
K
L
Pe`(:
L
#1)`
L`
L
K
L
Pe(:
L
#1)
"1 (9)
and Eq. (10) for the variance.
o`
!
"32
L`
L
K
L
Pe`(:
L
#1)`
L"
L
K
L
Pe(:
L
#1)
!1
"
2
Pe
1!
(1!e.C)
Pe
, (10)
where K
L
is given by Eq. (11)
K
L
"
2Pe:
L
Pe(:`
L
#1)#4
. (11)
Satisfactory enumeration of Eq. (7) becomes increasingly
di$cult at higher values of Pe. This di$culty derives
from the relative magnitudes of the early terms in the
series with respect to the later terms and the "nal sum.
When 0"0 the series itself is non-convergent with suc-
cessive terms oscillating as the following.
lim
L"
(S
L
)"2(!1)'L'e.C`. (12)
At a practical upper limit of Pe"33 a conventional
double precision summation will yield a residual of less
than 0.00005 at 0"0.001 but will require some 300 terms
to achieve this.
5908 A. D. Martin / Chemical Engineering Science 55 (2000) 5907}5917
Fig. 1. Exit age distributions of the tanks in series model for 1 and
2 tanks in series.
Fig. 2. Comparison of the tanks in series model with the closed disper-
sion model with a common variance of 0.5.
The tanks in series model seeks to describe the #ow in
a reactor system by considering it to be discretised into of
a strand of equal-sized hypothetical CSTRs. Each hypo-
thetical CSTR is independent of those preceding or fol-
lowing it. The number of tanks in series n
2
describes the
dispersion with n
2
"1 representing in"nite dispersion
and being equivalent to Pe"0. Integration of a simple
dynamic mass balance around the strand of reactors
readily yields the system RTD (Eq. (13)). Eq. (13) is also
the de"nition of the Erlang distribution.
E(0)"
C
C
B
"
nL2
2
(n
2
!1)!
0'L2'eL2F. (13)
With mean and variance
0M
2
"1, (14)
o`
2
"
1
n
2
. (15)
Conceptually, the development of this model is easy to
follow. It also has the advantage that the precise de"ni-
tion of the inlet and exit boundary conditions is not
required. Similarly concerns regarding the method of
`dyea injection and measurement do not arise. Phys-
ically, this model is at its best when the number of tanks
in series is low and concerns over the appropriateness of
either `opena or `closeda boundary conditions are at
their height. This model however has a signi"cant draw-
back when n
2
is small due to the integer constraint.
Fig. 1 shows that the E curve for n
2
"1 di!ers very
signi"cantly from that resulting from n
2
"2. Many real
CSTRs exhibit RTDs which lie in this range and are
therefore only characterised very approximately by the
tanks in series model. Frequently in the interpretation of
RTD data n
2
has been related to Pe or N
"
via the
variances of the RTDs (Eqs. (10) and (15)). This is tanta-
mount to assuming that the tanks in series model and the
`closeda dispersion model are equivalent. Elgeti (1996)
develops an alternative relationship between the two
RTD forms by following the progress of an arbitrary
reaction and expanding the dispersion equation in
Taylor series. This analysis leads to the following equiva-
lence relationship for Pe:
Pe"2(n
2
!1). (16)
Kramers and Alberda (1953) also proposed this equiva-
lence. Fig. 2 shows quite clearly that for the variance
equivalence, n
2
"2 and Pe"2.557, respectively,
the RTDs are quite di!erent. A plot generated for the
`Kramers, Alberda and Elgetia equivalence shows very
similar behaviour though the co-location of the peaks is
slightly poorer than illustrated in Fig. 2. The `closeda
dispersion model exhibits a considerably higher peak
value than the tanks in series model. This di!erence
reaches a maximum at n
2
"2, Pe"2.557. The `closeda
dispersion model can also be seen to exhibit a region with
a positive second derivative at 0(1 which is absent from
the tanks in series model. At values of n
2
'15,
Pe'28.97 the di!erence between the two maxima is less
than 5% and is likely to be di$cult to resolve experi-
mentally. Thus for practical purposes the two models are
su$ciently similar to be regarded as the same. The tanks
in series and `closeda dispersion models however di!er
signi"cantly from the `opena dispersion model under the
same conditions.
3. Extended tanks in series
If the tanks in series model is merely regarded as
a residence time distribution function, whose form de-
pends solely on the value of the parameter n
2
, and is
freed from the arti"cial need to have a physical manifes-
tation, it becomes possible to address the quantisation
issue arising in the analysis of high-dispersion systems.
Simply introducing the concept of a non-integer number
of hypothetical tanks in series will achieve the desired
result. The exit age distribution or E curve of the
A. D. Martin / Chemical Engineering Science 55 (2000) 5907}5917 5909
Fig. 3. Thread and knot concept for the tractor network model.
extended tanks in series (ETIS) model is given by a subset
of the gamma distribution family (Eq. (17)).
E(0)"
nL2
2
I(n
2
)
0L2eL2F. (17)
When n
2
is integer it is identically equal to the Erlang
distribution (Eq. (11)). As with the Erlang distribution the
mean and variance are given by Eqs. (14) and (15). The
ETIS model removes the problem of quantisation which
occurs as n
2
tends to 1 in the tanks in series model.
4. Reactor network structure
The models described in the previous sections are all
one dimensional in their nature and are consequently
unable to describe gross structure in the #ow within
a reactor. To describe such large scale structures in the
#ow pattern it is necessary to introduce appropriate
large-scale structure to the model. Many model struc-
tures have been proposed to describe a range of physical
#ow con"gurations (Levenspeil, 1972; Monteith
& Stephenson, 1981; Smith, Elliot & James, 1993). To
date the fundamental building blocks or `threadsa of
these reactor networks have been limited to either ideal
CSTRs or ideal PFRs. Algebraic expressions for the
C and E curves of some of the simple con"gurations have
been derived (Levenspeil, 1972; Monteith & Stephenson,
1981). The technique for generating the model RTD for
the majority and the more complex networks involves
the numerical integration of the dynamic CSTR mass
balance Eq. (18) (Smith et al., 1993).
dC
dt
"
(C
G
!C)

(18)
Clearly to describe real DPFRs using simple CSTR or
PFR building blocks requires large numbers of the fun-
damental unit and the numerical integration of reactor
network models becomes inordinately cumbersome as
the extent of the network grows. The use of the CSTR as
the basic building block also constrains the network
description to integer values of n
2
. Employing the ETIS
model to characterise the basic building block signi"-
cantly reduces the complexity of network required whilst
simultaneously relaxing the integer n
2
constraint. To-
gether these advantages dramatically improve the tracta-
bility of the data analysis problem. The reactor network
structure is developed further in the following sections to
facilitate the description of `reala vessels exhibiting com-
plex composite dispersion behaviour with bypassing and
stagnant zones.
The network dexnition: The reactor network structure is
constructed from two component types.
1. Threads,
2. Knots.
These components serve to de"ne the volume elements
of the reactor and their connectivity, respectively. The
`threadsa receive #ow from an up stream or source
`knota and discharge to a down stream or sink `knota.
The characteristics of the `threadsa are de"ned by the
#ow through the thread its hypothetical volume and exit
age distribution (Q, <, E). The `knotsa receive #ows from
source `threadsa and distribute the summed #ow to the
sink `threadsa and are de"ned as zero-volume blender
splitters. The `knotsa are characterised by a single-#ow
split fraction parameter ( f
Q
). A number of assumptions
are implicit in this basic de"nition of the network.
1. Individual `threadsa are assumed to be fully seg-
regated from each other.
2. The exit age distribution of an individual `threada is
given by the convolution of the composite E curve
passed by the source `knota.
3. The composite E curve passed at any `knota is given
by the linear #ow weighted sum of the E curves of the
contributing `threadsa.
4. There is no dispersion through `knotsa.
Assumptions 1 and 4 are likely to be the most conten-
tious, particularly when considering reaction kinetics in
conjunction with the RTD. They are however critical to
the formulation of a manageable problem. Clearly within
the context of assumption 4 the choice of model for the
characterisation of dispersion is restricted to the `closeda
dispersion model, the TIS model and the ETIS model.
Despite the reservations expressed above the ETIS model
is used to illustrate the concept of the network.
Fig. 3 shows a network of three `threadsa connected
together in to two #ow paths or `strandsa by three
`knotsa. This type of network is a common result of
interpreting the RTD of a large shallow packed bed
reactor. This type of network di!ers from those employed
by previous authors (Levenspeil, 1972; Monteith
& Stephenson, 1981; Smith et al., 1993) in that all
`threadsa accommodate dispersed #ow.
5. Experimental data interpretation
Data Gathering. There are four general types of experi-
mental protocol for the conduct of `dye tracera
5910 A. D. Martin / Chemical Engineering Science 55 (2000) 5907}5917
experiments. The classical experimental technique in-
volves the injection of a Dirac function pulse of `dyea
followed by the measurement of its concentration as it
emerges in the outlet stream over an extended period of
time. This method produces a readily interpretable result
and maximises the potential for resolving the detailed
structure of the experimental exit age distribution.
A common alternative technique employs a `stepa input.
This technique generates the reactor F curve, which may
be di!erentiated to yield the E curve. Direct di!erenti-
ation of experimental data results in the ampli"cation of
noise arising from sampling and analytical methods.
Curve "tting to the integrated form or F curve may also
lead to poorer estimates of the parameters. This arises
because detailed features are less distinctive on the
F curve than on the E curve. A third experimental proto-
col involves the injection of a `blocka input. This method
is considerably inferior to the two previous methods. The
experimental exit age distribution obtained from this
technique is a hybrid lying between the classical E and
F curves. The duration of the `blocka tends to produce
a broad peak and damp out the detailed structure, which
would have been revealed by a function pulse input.
A "nal technique involves the analysis of a natural ran-
dom signal in the input stream. This technique has the
advantage of not altering the process stream but su!ers
from the same disadvantages as the `blocka input tech-
nique. The AWWA guide (Teefy, 1996) o!ers advice on
the conduct of `dye tracera tests in water and waste-
water treatment plants particularly with respect to the
selection of suitable `dyesa.
Data processing. Historically the interpretation of
experimental RTD data has been rather super"cial
(Tomlinson & Chambers, 1979). Often this interpretation
has been limited to extraction of the mean and variance
of the data set (Eqs. (19) and (20)).

C
tM
C
"
C
L
t
L
At
L
C
L
At
L
, (19)
o`
C

C
L
t`
L
At
L
C
L
At
L
!tM`
C
. (20)
The sequential nature of the data gathering guarantees
the collection of biased data sets. So whilst for randomly
gathered data fairly modest sample sizes are su$cient to
obtain good estimates of the population mean and vari-
ance this is not the case for RTD data. It can be seen that
Eq. (19) is acutely `tail sensitivea, thus early truncation of
the data set leads to serious under estimation of the
population mean or achieved mean residence time. To
overcome this problem protracted measurement periods
are usually prescribed. Typical measurement periods are
chosen to be of the order of 3}5 times the mean residence
time with the need for longer periods coinciding with
highly disperse systems. Furthermore tM
F
is an estimate of
the mean of the RTD. It is therefore only an estimate of
the mean residence time when the `closeda dispersion,
TIS or ETIS models are appropriate.
The estimates obtained from Eqs. (19) and (20) have
often been related to the dispersion number (N
"
) or the
number of tanks in series (n
2
) via Eqs. (10) and (15) with
little regard to the overall shape of the RTD. A number of
additional empirical relationships have also been de"ned
to characterise the dispersion in reactors:
p
&
"
t
"
tM
, (21)
I
+
"
t
""
t
"
, (22)
I

"1!
t
K
tM
. (23)
Smith et al. (1993) examined these indices and found
them to be mutually inconsistent when used to describe
their data. These indices may be consistently related to
the variance of the RTD only in circumstances when the
distribution is symmetrical, i.e. very low dispersion or
plug #ow. This situation rarely coincides with the occa-
sions when the departure from plug #ow is important.
6. Selected case studies
The ETIS model has been used in the following case
studies to provide the quanti"cation of the dispersion
within an individual `threada. This has been done be-
cause of the ease of application and despite concerns
regarding strict validity at intermediate values of Pe. The
curve-"tting process has been conducted on Microsoft
EXCEL 97 using the built in SOLVER and mathemat-
ical functions. The built in functions were also supple-
mented with visual basic for applications (VBA) code
developed by the author.
Simulated very large CSTR. The reactor under study
consisted of a nominal 1500 m` cuboid vessel with
a multi-ported inlet manifold located at the bottom of the
vessel and an outlet weir located on the opposite wall.
Fig. 4 shows a schematic elevation of the vessel which
was nominally 19.5 m in the axial direction by 19.5 m
wide by 4 m deep. The inlet manifold directed the feed
#ow across the #oor of the reactor underneath a grid of
aeration equipment. The process feed rate was
0.0523 m`/s. The reactor was simulated using a commer-
cial CFD package and an `experimentala RTD
generated using a particle tracing technique. Several ap-
proximations were made in the construction of the CFD
model of this reactor:
1. The vessel was assumed to be semi-in"nite (normal to
the direction of #ow).
2. The feed manifold was modelled by a continuous
axially pointing slot at the foot of the feed wall.
A. D. Martin / Chemical Engineering Science 55 (2000) 5907}5917 5911
Fig. 4. Schematic vertical section through the simulated very large
CSTR.
Fig. 5. Early period exit age distribution for the simulated very large
CSTR showing contributions from the component threads.
Fig. 6. Complete exit age distribution for the simulated very large
CSTR.
Fig. 7. Reactor network to model the exit age distribution of the
simulated very large CSTR.
3. A 300 mm wide #ow section with `periodica boundary
conditions was assumed to be su$ciently large to
model the expected #ow structure.
Preliminary inspection of the early period results
(Fig. 5) shows clearly a delay of approximately 20 min
before a signi"cant concentration of `dyea is found in the
exit. The delay is followed by a steady increase to a max-
imum at approximately 100 min elapsed time. These gen-
eral characteristics suggest a candidate framework
capable of describing the exit age distribution and
E curve. Additional threads are added to the network by
analysis of the residual after attempting to "t the model
to the data. The analysis of the residual must be under-
taken with some care as the degrees of freedom are
successively reduced with the addition of each new
thread. Equally, the inherent noise in the data arising
from measurement errors must be considered. The solid
line in Figs. 5 and 6 presents the E curve generated as
a result of this process. The broken lines show the #ow
weighted E curves of the individual threads. Fig. 7 illus-
trates the "nal network structure synthesised to describe
the data.
The theoretical hydraulic residence time of this vessel
T
0
is 484 min and the mean of the "tted residence time
distribution
0
is found to be 509 min. The estimate of

0
obtained from the `experimentala data set tMis found
to be 476 min. The data set from which this estimate is
made extends to 1620 min or 3.4 residence times. The "ve
`threada model proposed in Fig. 7 satisfactorily describes
the `experimentala data. The dominant #ow strand
consists of a plug-#ow `threada and a large CSTR
`threada. Together these account for the vast majority of
the vessel volume. Two small additional `threadsa are
required to describe the small by-pass #ow around the
large CSTR volume. The "fth `threada describes the
`deada volume. This technique is unable to order con-
secutive `threadsa. However, with knowledge of the reac-
tor geometry a considered assignment may be made. In
this instance the plug #ow section is placed "rst and its
characteristics are attributed to the region de"ned by the
decaying feed `jeta underneath the aeration grid. From
Fig. 7 it can be seen that `threadsa 1 and 4 are very
similar in character. This suggests that thread 4 is a por-
tion of the feed `jeta which by-passes the well-mixed
region. This may be considered to be a portion of the
#uid that travels the full length of the reactor underneath
the aeration grid and then ascends the end wall to the exit
weir. Such a #ow strand would have failed to interact
with the air bubbles in the reactor and would therefore
remain un-converted. A similar argument may be ad-
vanced to describe `threada 3. Together `threadsa 3 and
5 represent 5% of the #ow through the vessel. Thus,
based on the above argument this reactor would be
unlikely to achieve greater than 95% conversion.
The mean of the `experimentala data tM is remarkably
close to the value of T
0
. This situation is di$cult to
5912 A. D. Martin / Chemical Engineering Science 55 (2000) 5907}5917
Fig. 8. Schematic vertical section through the packed bed reactor.
Fig. 9. Exit age distribution for the packed bed reactor.
Fig. 10. Reactor network to model the exit age distribution of the
packed bed reactor.
support given the truncation of the data set at 3.4 resi-
dence times. Integration of the complex model E curve
over 1620 min (3.4 residence times) reveals an expected
98% `dyea recovery. It also provides an estimate of the
mean based on a truncated portion of the E curve. This
estimate is found to be 473 min which is in close agree-
ment with tM. On the basis of these consistency checks
509 min estimated from the consideration of the whole of
the "tted distribution is likely to be reliable. Practically,
neither
0
'T
0
nor negative dead volume fraction
(`threada 5) can be supported and may be indicative of an
error in either the #ow or volume speci"cation of the
model region. Such errors may arise from the numerical
handling of symmetrical or periodic boundary condi-
tions. The CFD model also predicts a signi"cant fraction
of the vessel to exhibit an occluded volume exceeding
5%. This is attributed to the presence of bubbles. The
expected e!ect is to reduce the value of
0
relative to
T
0
since the reactor network interpretation of the bubble
cloud is as dead volume. Hence the expected dead vol-
ume fraction is of the order of 5% rather than the !5%
estimated by the network model analysis.
Packed bed reactor. Fig. 8 shows a schematic vertical
section through this reactor, which consists of a 5 m by
5 m by 4.150 m deep cuboid vessel with 2.2 m depth of
bouyant granular packing operated in up #ow. The feed
enters the lower distribution chamber, then passes up
through the packed bed and hold down plate into an
upper collection chamber before discharging from the
reactor via wall mounted weirs. A second reactant is
introduced into the base of the packed bed and #ows in
co-current mode through the packing. The dumped
packing has a void volume fraction of approximately
55%.
Visual inspection of the experimental data (Fig. 9)
shows a delay in the detection of the `dyea in the outlet
stream and a substantial tail on the RTD. This suggests
that the reactor requires a minimum three `threada
model for characterisation. This model is shown in
Fig. 10. The reactor con"guration however suggests that
a four `threada model may be more suitable from a phys-
ical standpoint. Both models were constructed to ascer-
tain the improvement in "delity between a two `threada
model and a three `threada model. The overall improve-
ment was found to be insigni"cant with respect to the "t
to the experimental data. However, comparison of the
characteristics of the individual threads o!ered further
insights into the possible structure of the operating bed.
The low-dispersion `threada,1 in each model, was un-
changed between the 3 and 4 `threada models but the
high dispersion `threada of the 3 `threada model split
into 2 CSTR `threadsa in the 4 `threada model. It may be
inferred that the low dispersion `threada 1 models the
region in the reactor that is occupied by the packed bed.
However, the void volume of the packed depth is consis-
tently underestimated by approximately 20%. The
volume estimates of the high-dispersion regions are
equivalently high. The description of the high-dispersion
region by the 4 `threada model is particularly interesting
since the over estimate of the volume is con"ned to
a single `threada. The placement of the `knota between
`threadsa 2 and 3 coincides with the operating volume of
the upper collection chamber. By elimination the over
estimated `threada is assigned to the lower distribution
volume. The relative under and over estimates of the
volumes in this part of the reactor may be attributed to
2 causes:
1. Failure of the model to adequately describe the condi-
tions at the interface between the distribution volume
and the packed region.
2. Interaction between the lower portion of the packed
bed and the distribution volume such that a propor-
tion of the bed is disturbed.
The reactor network model assumes that there is no
dispersion through `knotsa which is likely to be valid
A. D. Martin / Chemical Engineering Science 55 (2000) 5907}5917 5913
Fig. 11. Schematic plan of the internally recirculating CSTR.
Fig. 12. Exit age distribution for the internally recirculating CSTR.
Fig. 13. Reactor network to model the exit age distribution of the
internally recirculating CSTR.
within the reactor if either the feed or discharge `threadsa
exhibit low dispersion. Whilst this assumption is imper-
fect at Pe"17 the error introduced is insu$cient to
describe the phenomenon observed in the analysis. The
corollary of this is that the placement of the model
`knota does not coincide with the expected physical
boundary between the packed bed and the distribution
volume. This was con"rmed by the observation of in-
stabilities at the interface between the packed bed and the
lower distribution volume. Particles occupying the lower
300 mm of the packing were observed shearing o! the
bed and temporally dispersing in the distribution vol-
ume. Thus both the 3 and 4 thread models have identi"ed
the stable packed bed only as a low-dispersion region.
Since the objective of this study was to characterise the
active portion of the reactor, the 3 `threada model is
adequate.
Internally recirculating CSTR. This reactor consists
of a 12 m wide by 3.1 m deep oval channel with a
centre line length of 236 m and an operating volume of
approximately 8200 m`. Fig. 11 shows a plan view sche-
matic of the vessel. The feed is introduced through the
outer perimeter wall and the discharge exits via the
interior perimeter wall approximately
`
of a lap down
stream of the feed position. Clockwise internal circula-
tion is mechanically induced by a system of surface
paddles.
The experimental procedure involved the injection of
a delta function pulse into the feed followed by a long tail.
This is indicated in Fig. 12 by the closed circles. The long
tail arises from the entrapment of `dyea in an external
recycle. Entrapped `dyea passes through a number of
external unit operations before returning to the feed. The
original delta function input is very heavily damped and
the intermittent peaks observed in this trace cannot be
attributed to this source. It is more probable that these
peaks arise as a result of random #ushing of residual
`dyea from the reactor inlet chamber where the original
injection was made.
The experimental output trace, open circles in Fig. 12,
shows two distinct patterns of behaviour. The early peri-
od behaviour extending from 0"0.0}0.6 shows clear
periodicity with decaying amplitude. The late period
behaviour extending from0"0.6 onward shows approx-
imate exponential decay. Based on the form of the input
trace and the observed response the experimental data
was modelled in two parts.
1. The response to the delta function input was modelled
in detail by the network shown in Fig. 13.
2. The response to the long tail was modelled solely on
the aggregated system behaviour, i.e. an exponentially
decaying RTD.
A calculation method for this type of reactor network
model is described by Battaglia et al. with reference to
land "ll leachate (Battaglia, Fox and Pohland, 1993). The
high dispersion of the Battaglia et al. system required
fewer than 10 terms of their series solution to achieve
a satisfactory result. In this work the development fol-
lowed a route equivalent to Battaglia et al. with the series
summation being implemented in (VBA). The recycle was
opened out and the circulating #ow considered to be
made up of a number of parallel `threadsa. Each `threada
was considered to represent the fraction of #uid entering
the reactor and completing a constant fraction of a lap
plus an integer number (s) of additional laps before exit-
ing. The general concept is illustrated in Fig. 14 together
with the recurrence relationships for the `threada para-
meter values. The numerical subscripts in Fig. 14 relate
to the parameters in Fig. 13. The total number of parallel
5914 A. D. Martin / Chemical Engineering Science 55 (2000) 5907}5917
Fig. 14. Numerical equivalent network for the evaluation of the inter-
nally recirculating CSTR model.
threads considered (c) was determined by a precision
criterion given by Eq. (24).
c"1#Int

log
"
(p)
log
"

1!

`
#
`

, (24)
where the numerical subscripts refer to the `threada
numbers in Fig. 13.
Analysis of the experimental data resolved the peri-
odicity in the early period to be 11.55 min (0.061
0
).
However the expected "rst peak at 4.75 min (0"0.025) is
almost completely absent from the experimental data.
The "rst strong peak is detected at 16.3 min (0"0.086).
This result has two possible explanations.
1. The sampling frequency at the outlet was insu$ciently
high to resolve the peak.
2. The dispersion normal to the direction of #ow was
incomplete.
A simple test to check the possible sample frequency
explanation indicates that at least two samples would
have been gathered which contained signi"cant concen-
trations of `dyea. This test indicates that the samples
collected at 4 and 6 min (0"0.0211 and 0.0316) are those
a!ected and the expected concentration of `dyea is likely
to be double that observed in any of the samples prior to
the "rst signi"cant peak. Whilst this test is not conclusive
the result suggests that incomplete normal dispersion is
the more likely explanation. Based upon these deduc-
tions the derived reactor network structure and para-
meter values are given in Fig. 13. The aggregated or late
period behaviour of this model is as expected equivalent
to a CSTR (n
2
"1) with a mean residence time of

0
"190 minutes. The convolution of the long tail of the
input trace with the CSTR characteristics describes the
late period behaviour of the experimental RTD very
satisfactorily.
7. Discussion
Suitability of ETIS model. From a theoretical stand-
point the ETIS model may be criticised because of its
lack of rigour with respect to the inlet and exit boundary
conditions. It is however this lack of rigour which makes
the model easy to use particularly in circumstances of
high dispersion. The extension of the classical tanks in
series model into the continuous (ETIS) form also con-
tributes to the ease of use since it becomes possible to use
simple optimisation algorithms for the interpretation of
experimental data. The ETIS model also eliminates the
quantisation e!ects observed in the tanks in series model
at low n
2
. The elimination of these e!ects is a signi"cant
advantage since it is at low n
2
or Pe that the tanks in
series analogy is at its most useful. To achieve an equiva-
lent removal of quantisation using the tanks in series
model requires the addition of further `threadsa to the
network with independent residence times.
Hitherto, the absence of a solution to the `closeda
dispersion model has been widely accepted. This solution
was however published by Thomas and McKee in 1944.
The rigorous handling of the inlet and outlet boundary
conditions is a signi"cant bene"t relative to the ETIS
model and unlike the `opena dispersion model does not
add to the di$culty of use. The series solution presented
in their paper is however numerically intensive in use and
becomes practically non-convergent at low values of
0 and high values of Pe. Frequently in the past the tanks
in series model has been assumed equivalent to the
`closeda dispersion model. The equivalence has been
established by equating the respective variances (Eqs. (10)
and (15)). This assumption has been shown to be false
except under the condition n
2
"1 and Pe"0. Practic-
ally however the di!erences become small enough for the
distributions to be regarded as the same when n
2
'15
and Pe'28.97. The di!erences between the two distri-
butions are such that, for a chosen variance or equivalent
pair of n
2
and Pe values, the reactor design based upon
the ETIS model yields a slightly larger volume than that
based on the `closeda dispersion model. This arises from
the more `peakya nature of the `closeda dispersion
model RTD. The `closeda dispersion model predicts that
signi"cantly more material is discharged from the reactor
with an exit age between 0.25
0
and
0
.
The ETIS model as applied in the three case studies
has provided very satisfactory "ts to the experimental
data. There are few areas in which the application of the
more numerically intensive `closeda dispersion model
would practically bene"t the interpretation of the data.
Thread 3 of the simulated very large CSTR may describe
the data better if the `closeda dispersion model were
used. This `threada, though, accounts for less than 3% of
the reactor throughput and the value of n
2
(22) is toward
the upper end of the range in which the ETIS
and `closeda dispersion models di!er signi"cantly.
A. D. Martin / Chemical Engineering Science 55 (2000) 5907}5917 5915
Application of the `closeda dispersion model to `threada
1 of the packed bed reactor network may improve the "t
to the experimental data in the region 0.2(0(0.3 and
0"0.75. However, as can be seen from Fig. 9 the scope
for improvement is small.
Dispersion at knots. A basic assumption of the reactor
network structure is that there is no dispersion through
the `knotsa. This assumption is completely consistent
with the application of the `closeda dispersion model to
characterise the interconnecting `threadsa. Such a high
level of consistency cannot be claimed for the use of the
ETIS due to the lack of rigour in the de"nition of the inlet
and outlet boundary conditions. The implied assump-
tions for the tanks in series model relate to the inlet and
outlet of a CSTR and would indeed be consistent with
the no dispersion through the `knotsa assumption. The
same implicit assumption is made in the ETIS model but
is conceptually di$cult when n
2
is not an integer.
The extent of dispersion through the `knotsa is only
likely to be signi"cant where both source and sink
`threadsa are themselves characterised by high disper-
sion. The qualitative e!ect of removing the central `knota
joining 2 CSTR `threadsa is shown in Fig. 2. By analogy
with the previous discussion regarding the suitability of
the ETIS model for the characterisation of individual
`threadsa it may be deduced that the no dispersion
through `knotsa assumption holds within experimental
accuracy when n
2
'15 and Pe'28.97 in the more plug
#ow `threada. Quantitative assessment of the breakdown
of the no dispersion through the `knotsa assumption is
not reported here but might be approached via consid-
eration of the Kurtosis of the RTDs.
Ordering. Using the simple conservative `dyea -tracing
methods reported here it is not possible to order the
`threadsa in a reactor network without additional struc-
tural information. To make progress with respect to
ordering of model elements in the absence of structural
information it is essential to employ a non-conservative
`dyea -tracer method with a second-order decay process.
The application of such techniques will not be discussed
here.
8. Conclusions
The ETIS model in conjunction with the reactor net-
work structure has been shown to be a versatile method
of describing the characteristics of a small but diverse
group of reactors. The ETIS model has been compared
with the conventional tanks in series approach and has
been found to be superior due to the elimination of the
quantisation which is inherent in the latter approach.
The ETIS model has also been compared with the
Thomas and McKee `closeda solution to the dispersion
model. The `closeda dispersion model has been shown to
di!er signi"cantly from the ETIS model in the range
0(Pe(28.97 and 1(n
2
(15. The `closeda disper-
sion model is also found to have the advantage of
rigorously de"ned inlet and exit boundary conditions.
Combination of the ETIS model with the reactor net-
work structure permits a considerable increase in the
versatility of networks with out the concomitant increase
in numerical intensity which characterises networks of
CSTRs.
Notation
C dimensionless concentration Dimensionless
D eddy di!usion coe$cient L` t
E(0) exit age distribution function Dimensionless
e base of natural logarithms
(2.718...)
Dimensionless
f #ow fraction Dimensionless
I `mixinga index Dimensionless
characteristic length L
N
"
dispersion number Dimensionless
n
2
number of tanks in series Dimensionless
p precision Dimensionless
Pe peclet number Dimensionless
Q liquid feed rate L` t
S a term in the series solution
of the closed dispersion
model
Dimensionless
mean residence time t
T Hydraulic mean residence
time
t
t elapsed time t
tM mean of the residence time
distribution
t
u velocity L t
< volume L`
v volume fraction Dimensionless
z axial displacement L
Greek letters
I gamma function
p E$ciency
3.14159
2
G strand dimensionless
residence time
dimensionless time Dimensionless
0M mean of the dimensionless
RTD
Dimensionless
o` variance of the dimensionless
RTD
Dimensionless
Subscripts
10 pertaining to the recovery of
10% of the injected `dyea
5916 A. D. Martin / Chemical Engineering Science 55 (2000) 5907}5917
90 pertaining to the recovery of
90% of the injected `dyea
c `closeda dispersion model
e experimental
H hydraulic
i inlet
M merril
m modal
o `opena dispersion model
R whole reactor
s thread index
sc short circuiting
pertaining to the TIS and ETIS
models
Acknowledgements
The author would like to acknowledge the assistance
of the following colleagues who contributed their experi-
mental data for the case studies. Ms. Laura Burrows,
Experimental data from the internally recirculating
CSTR. Mrs. Barbara Gray, Experimental data from the
packed bed reactor. Mr. Tony Robinson, Calculation of
the simulated RTD for the Large CSTR.
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