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 length. These models are consequently one dimensional

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
STOAT2+ GPSX2+ and SPEEDUP2+ 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 ) in conjunction with the mean
2
residence time (¹ ) to describe deviations from the ideal
0
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-
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)).

 
200-4340.
*C D *C *C
" ! , (1)
E-mail address: Alaistair.martin@OMIST.ac.uk (A. D. Martin). *h u¸ *z *z

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
5908 A. D. Martin / Chemical Engineering Science 55 (2000) 5907}5917

where the dimensionless group boundary conditions in 1944. Their solution, published
in a dimensional form, is reproduced here in non-dimen-
D 1
"N " (2) sional form (Eq. (7)) to maintain consistency with Leven-
u¸ " Pe spiel and Smith's `opena solution (Eq. (4)). Yagi and
and Miyauchi reproduced the Thomas and McKee solution
in 1953 with an alternative condensation of the terms
t Q t ut (Yagi & Miyauchi, 1953).
h" " 0 " (3)
¹ < ¸
0 0


C L Pea e.C+\F?L >, Pe
E(h)" "2 L a cos a
The `opena boundary conditions from which this model C Pe(a#1)#4 L 2 L
draws its name de"ne the #ow condition at the reactor B L L


inlet and outlet. The `opena condition is physically Pe
#sin a , (7)
achieved when the #ow is undisturbed at the inlet and the 2 L
outlet. In 1957 Levenspiel and Smith published the ana-
where a is given by the positive roots of Eq. (8).
lytical solution to Eq. (1) for the `opena boundary condi- L


tions (Levenspiel & Smith, 1957). This solution is shown Pe 2a
in Eq. (4). tan a " L . (8)
2 L (a!1)
L

  

C 1 Pe \ .C\F Levenspeil (1972) published expressions for the mean and
E(h)" " e F
C 2 ph (4) variance of the `closeda system RTD though did not
B report the analytical solution for the RTD itself. Leven-
Where C is the concentration that would have been spiel's mean and variance can be shown to be equal to
B
obtained had the `dyea been evenly dispersed through- those of Eq. (7) thus con"rming their association. These
out the vessel under study. results are shown below Eq. (9) for the mean,
With mean and variance
K
2 L L
hM "1# , (5) L Pe(a #1)
 Pe hM "4 L "1 (9)
! K
L L
2 8 L Pe(a #1)
p " # , (6) L
 Pe Pe
and Eq. (10) for the variance.
It can be seen that the mean of this distribution is
K
a function of the dispersion and at high dispersion (low L L
Pe) the mean is substantially '1. This result appears to L Pe(a #1)
p "32 L !1
be inconsistent with the mass balance but may be ex- ! K
L L
plained by the di!usion of `dyea upstream of the injec- L Pe(a #1)
L
tion point. Thus, the pulse injected at the inlet is not the

 
same as the pulse which would have been measured at 2 (1!e\.C)
" 1! , (10)
the inlet. Casual observation of the inlet to and exit from Pe Pe
a high-dispersion reactor would also con#ict with the where K is given by Eq. (11)
assumed `opena boundary conditions. The rigorous L
mathematical de"nition of the `opena boundary condi- 2Pea
K " L . (11)
tions makes this model more di$cult to use than the L Pe(a#1)#4
tanks in series formulation as the user is often left in some L
doubt as to the degree to which the `opena condition is Satisfactory enumeration of Eq. (7) becomes increasingly
achieved in the system under investigation. di$cult at higher values of Pe. This di$culty derives
The **closed++ dispersion model treats the system in from the relative magnitudes of the early terms in the
exactly the same fashion as the `opena dispersion model. series with respect to the later terms and the "nal sum.
Eq. (1) is solved with the `closeda boundary conditions. When h"0 the series itself is non-convergent with suc-
The `closeda boundary conditions relate to the physical cessive terms oscillating as the following.
situation in which the #ow approaches the inlet to the
reactor in idealised plug #ow (Pe"R), transforms to lim (S )"2(!1)L\e.C. (12)
L
dispersed #ow within the reactor and returns to idealised L
plug #ow at the exit. This situation is very closely ap- At a practical upper limit of Pe"33 a conventional
proximated in many real reactors even those which are double precision summation will yield a residual of less
themselves low dispersion devices. Thomas and McKee than 0.00005 at h"0.001 but will require some 300 terms
(1944) published the analytical solution with `closeda to achieve this.
 A. D. Martin / Chemical Engineering Science 55 (2000) 5907}5917
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 describes the
2
dispersion with n "1 representing in"nite dispersion
2
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.
C nL2
E(h)" " 2 hL2 \e\L2 F. (13)
C (n !1)!
B 2
With mean and variance
hM "1, (14)
2 dispersion model can also be seen to exhibit a region with
1 a positive second derivative at h(1 which is absent from
p " . (15)
2 n
2 Pe'28.97 the di!erence between the two maxima is less
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 is small due to the integer constraint.
2
Fig. 1 shows that the E curve for n "1 di!ers very
2
signi"cantly from that resulting from n "2. Many real
2
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 has been related to Pe or N via the
2 "
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
Fig. 1. Exit age distributions of the tanks in series model for 1 and
2 tanks in series.
5909
reaction and expanding the dispersion equation in
Taylor series. This analysis leads to the following equiva-
lence relationship for Pe:
Pe"2(n !1). (16)
2
Kramers and Alberda (1953) also proposed this equiva-
lence. Fig. 2 shows quite clearly that for the variance
equivalence, n "2 and Pe"2.557, respectively,
2
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, Pe"2.557. The `closeda
2
the tanks in series model. At values of n '15,
2
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 , and is
2
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
Fig. 2. Comparison of the tanks in series model with the closed disper-
sion model with a common variance of 0.5.
5910 A. D. Martin / Chemical Engineering Science 55 (2000) 5907}5917

extended tanks in series (ETIS) model is given by a subset These components serve to de"ne the volume elements
of the gamma distribution family (Eq. (17)). of the reactor and their connectivity, respectively. The
`threadsa receive #ow from an up stream or source
nL2
E(h)" 2 hL2 \e\L2 F. (17) `knota and discharge to a down stream or sink `knota.
!(n )
2 The characteristics of the `threadsa are de"ned by the
When n is integer it is identically equal to the Erlang #ow through the thread its hypothetical volume and exit
2 age distribution (Q, <, E). The `knotsa receive #ows from
distribution (Eq. (11)). As with the Erlang distribution the
mean and variance are given by Eqs. (14) and (15). The source `threadsa and distribute the summed #ow to the
ETIS model removes the problem of quantisation which sink `threadsa and are de"ned as zero-volume blender
occurs as n tends to 1 in the tanks in series model. splitters. The `knotsa are characterised by a single-#ow
2 split fraction parameter ( f ). A number of assumptions
Q
are implicit in this basic de"nition of the network.
4. Reactor network structure 1. Individual `threadsa are assumed to be fully seg-
regated from each other.
The models described in the previous sections are all 2. The exit age distribution of an individual `threada is
one dimensional in their nature and are consequently given by the convolution of the composite E curve
unable to describe gross structure in the #ow within passed by the source `knota.
a reactor. To describe such large scale structures in the 3. The composite E curve passed at any `knota is given
#ow pattern it is necessary to introduce appropriate by the linear #ow weighted sum of the E curves of the
large-scale structure to the model. Many model struc- contributing `threadsa.
tures have been proposed to describe a range of physical 4. There is no dispersion through `knotsa.
#ow con"gurations (Levenspeil, 1972; Monteith
& Stephenson, 1981; Smith, Elliot & James, 1993). To Assumptions 1 and 4 are likely to be the most conten-
date the fundamental building blocks or `threadsa of tious, particularly when considering reaction kinetics in
these reactor networks have been limited to either ideal conjunction with the RTD. They are however critical to
CSTRs or ideal PFRs. Algebraic expressions for the the formulation of a manageable problem. Clearly within
C and E curves of some of the simple con"gurations have the context of assumption 4 the choice of model for the
been derived (Levenspeil, 1972; Monteith & Stephenson, characterisation of dispersion is restricted to the `closeda
1981). The technique for generating the model RTD for dispersion model, the TIS model and the ETIS model.
the majority and the more complex networks involves Despite the reservations expressed above the ETIS model
the numerical integration of the dynamic CSTR mass is used to illustrate the concept of the network.
balance Eq. (18) (Smith et al., 1993). Fig. 3 shows a network of three `threadsa connected
together in to two #ow paths or `strandsa by three
dC (C !C) `knotsa. This type of network is a common result of
" G (18)
dt ¹ interpreting the RTD of a large shallow packed bed
reactor. This type of network di!ers from those employed
Clearly to describe real DPFRs using simple CSTR or
by previous authors (Levenspeil, 1972; Monteith
PFR building blocks requires large numbers of the fun-
& Stephenson, 1981; Smith et al., 1993) in that all
damental unit and the numerical integration of reactor
`threadsa accommodate dispersed #ow.
network models becomes inordinately cumbersome as
the extent of the network grows. The use of the CSTR as
5. Experimental data interpretation
the basic building block also constrains the network
description to integer values of n . Employing the ETIS
2 Data Gathering. There are four general types of experi-
model to characterise the basic building block signi"-
mental protocol for the conduct of `dye tracera
cantly reduces the complexity of network required whilst
simultaneously relaxing the integer n constraint. To-
2
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. Fig. 3. Thread and knot concept for the tractor network model.
 A. D. Martin / Chemical Engineering Science 55 (2000) 5907}5917 5911

experiments. The classical experimental technique in- the mean residence time when the `closeda dispersion,
volves the injection of a Dirac d function pulse of `dyea TIS or ETIS models are appropriate.
followed by the measurement of its concentration as it The estimates obtained from Eqs. (19) and (20) have
emerges in the outlet stream over an extended period of often been related to the dispersion number (N ) or the
"
time. This method produces a readily interpretable result number of tanks in series (n ) via Eqs. (10) and (15) with
2
and maximises the potential for resolving the detailed little regard to the overall shape of the RTD. A number of
structure of the experimental exit age distribution. additional empirical relationships have also been de"ned
A common alternative technique employs a `stepa input. to characterise the dispersion in reactors:
This technique generates the reactor F curve, which may
t
be di!erentiated to yield the E curve. Direct di!erenti- g "  , (21)
& tM
ation of experimental data results in the ampli"cation of
noise arising from sampling and analytical methods. t
Curve "tting to the integrated form or F curve may also I "  , (22)
+ t
lead to poorer estimates of the parameters. This arises 
because detailed features are less distinctive on the t
I "1! K . (23)
F curve than on the E curve. A third experimental proto-  tM
col involves the injection of a `blocka input. This method
Smith et al. (1993) examined these indices and found
is considerably inferior to the two previous methods. The
them to be mutually inconsistent when used to describe
experimental exit age distribution obtained from this
their data. These indices may be consistently related to
technique is a hybrid lying between the classical E and
the variance of the RTD only in circumstances when the
F curves. The duration of the `blocka tends to produce
distribution is symmetrical, i.e. very low dispersion or
a broad peak and damp out the detailed structure, which
plug #ow. This situation rarely coincides with the occa-
would have been revealed by a d function pulse input.
sions when the departure from plug #ow is important.
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
6. Selected case studies
from the same disadvantages as the `blocka input tech-
nique. The AWWA guide (Teefy, 1996) o!ers advice on
The ETIS model has been used in the following case
the conduct of `dye tracera tests in water and waste-
studies to provide the quanti"cation of the dispersion
water treatment plants particularly with respect to the
within an individual `threada. This has been done be-
selection of suitable `dyesa.
cause of the ease of application and despite concerns
Data processing. Historically the interpretation of
regarding strict validity at intermediate values of Pe. The
experimental RTD data has been rather super"cial
curve-"tting process has been conducted on Microsoft
(Tomlinson & Chambers, 1979). Often this interpretation
EXCEL 97威 using the built in SOLVER and mathemat-
has been limited to extraction of the mean and variance
ical functions. The built in functions were also supple-
of the data set (Eqs. (19) and (20)).
mented with visual basic for applications (VBA) code
C t *t developed by the author.
¹
tM " L L L, (19)
C C C *t Simulated very large CSTR. The reactor under study
L L consisted of a nominal 1500 m cuboid vessel with
C t*t a multi-ported inlet manifold located at the bottom of the
p
L L L !tM . (20)
C C *t C vessel and an outlet weir located on the opposite wall.
L L
Fig. 4 shows a schematic elevation of the vessel which
The sequential nature of the data gathering guarantees
was nominally 19.5 m in the axial direction by 19.5 m
the collection of biased data sets. So whilst for randomly
wide by 4 m deep. The inlet manifold directed the feed
gathered data fairly modest sample sizes are su$cient to
#ow across the #oor of the reactor underneath a grid of
obtain good estimates of the population mean and vari-
aeration equipment. The process feed rate was
ance this is not the case for RTD data. It can be seen that
0.0523 m/s. The reactor was simulated using a commer-
Eq. (19) is acutely `tail sensitivea, thus early truncation of
cial CFD package and an `experimentala RTD
the data set leads to serious under estimation of the
generated using a particle tracing technique. Several ap-
population mean or achieved mean residence time. To
proximations were made in the construction of the CFD
overcome this problem protracted measurement periods
model of this reactor:
are usually prescribed. Typical measurement periods are
chosen to be of the order of 3}5 times the mean residence 1. The vessel was assumed to be semi-in"nite (normal to
time with the need for longer periods coinciding with the direction of #ow).
highly disperse systems. Furthermore tM is an estimate of 2. The feed manifold was modelled by a continuous
F
the mean of the RTD. It is therefore only an estimate of axially pointing slot at the foot of the feed wall.
5912 A. D. Martin / Chemical Engineering Science 55 (2000) 5907}5917

Fig. 4. Schematic vertical section through 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 is 484 min and the mean of the "tted residence time
0
distribution ¹ is found to be 509 min. The estimate of
0
¹ obtained from the `experimentala data set tM is found
0
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
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.
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 . This situation is di$cult to
0
 A. D. Martin / Chemical Engineering Science 55 (2000) 5907}5917 5913

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, Fig. 8. Schematic vertical section through the packed bed reactor.
neither ¹ 'T nor negative dead volume fraction
0 0
(`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 ¹ relative to
0
T since the reactor network interpretation of the bubble
0
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 Fig. 9. Exit age distribution for the packed bed reactor.
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 Fig. 10. Reactor network to model the exit age distribution of the
55%. packed bed reactor.
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 volume estimates of the high-dispersion regions are
that the reactor requires a minimum three `threada equivalently high. The description of the high-dispersion
model for characterisation. This model is shown in region by the 4 `threada model is particularly interesting
Fig. 10. The reactor con"guration however suggests that since the over estimate of the volume is con"ned to
a four `threada model may be more suitable from a phys- a single `threada. The placement of the `knota between
ical standpoint. Both models were constructed to ascer- `threadsa 2 and 3 coincides with the operating volume of
tain the improvement in "delity between a two `threada the upper collection chamber. By elimination the over
model and a three `threada model. The overall improve- estimated `threada is assigned to the lower distribution
ment was found to be insigni"cant with respect to the "t volume. The relative under and over estimates of the
to the experimental data. However, comparison of the volumes in this part of the reactor may be attributed to
characteristics of the individual threads o!ered further 2 causes:
insights into the possible structure of the operating bed.
1. Failure of the model to adequately describe the condi-
The low-dispersion `threada,1 in each model, was un-
tions at the interface between the distribution volume
changed between the 3 and 4 `threada models but the
and the packed region.
high dispersion `threada of the 3 `threada model split
2. Interaction between the lower portion of the packed
into 2 CSTR `threadsa in the 4 `threada model. It may be
bed and the distribution volume such that a propor-
inferred that the low dispersion `threada 1 models the
tion of the bed is disturbed.
region in the reactor that is occupied by the packed bed.
However, the void volume of the packed depth is consis- The reactor network model assumes that there is no
tently underestimated by approximately 20%. The dispersion through `knotsa which is likely to be valid
5914 A. D. Martin / Chemical Engineering Science 55 (2000) 5907}5917

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 Fig. 12. Exit age distribution for the internally recirculating CSTR.
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 Fig. 13. Reactor network to model the exit age distribution of the
paddles. internally recirculating CSTR.
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 imate exponential decay. Based on the form of the input
recycle. Entrapped `dyea passes through a number of trace and the observed response the experimental data
external unit operations before returning to the feed. The was modelled in two parts.
original delta function input is very heavily damped and
1. The response to the delta function input was modelled
the intermittent peaks observed in this trace cannot be
in detail by the network shown in Fig. 13.
attributed to this source. It is more probable that these
2. The response to the long tail was modelled solely on
peaks arise as a result of random #ushing of residual
the aggregated system behaviour, i.e. an exponentially
`dyea from the reactor inlet chamber where the original
decaying RTD.
injection was made.
The experimental output trace, open circles in Fig. 12, A calculation method for this type of reactor network
shows two distinct patterns of behaviour. The early peri- model is described by Battaglia et al. with reference to
od behaviour extending from h"0.0}0.6 shows clear land "ll leachate (Battaglia, Fox and Pohland, 1993). The
periodicity with decaying amplitude. The late period high dispersion of the Battaglia et al. system required
behaviour extending from h"0.6 onward shows approx- 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
Fig. 11. Schematic plan of the internally recirculating CSTR. to the parameters in Fig. 13. The total number of parallel
 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 (u) was determined by a precision
criterion given by Eq. (24).
 
log (p)



u"1#Int ¹ #¹ , (24)
log 1!   The rigorous handling of the inlet and outlet boundary
 ¹
0 conditions is a signi"cant bene"t relative to the ETIS
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 (0.061¹ ).
0
However the expected "rst peak at 4.75 min (h"0.025) is
almost completely absent from the experimental data.
The "rst strong peak is detected at 16.3 min (h"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 (h"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 "1) with a mean residence time of
2
¹ "190 minutes. The convolution of the long tail of the
0
input trace with the CSTR characteristics describes the
late period behaviour of the experimental RTD very
satisfactorily.
5915
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 . The elimination of these e!ects is a signi"cant
2
advantage since it is at low n or Pe that the tanks in
2
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.
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
h 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 "1 and Pe"0. Practic-
2
ally however the di!erences become small enough for the
distributions to be regarded as the same when n '15
2
and Pe'28.97. The di!erences between the two distri-
butions are such that, for a chosen variance or equivalent
pair of n and Pe values, the reactor design based upon
2
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 ¹ and ¹ .
0 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 (22) is toward
2
the upper end of the range in which the ETIS
and `closeda dispersion models di!er signi"cantly.
5916 A. D. Martin / Chemical Engineering Science 55 (2000) 5907}5917

Application of the `closeda dispersion model to `threada sion model is also found to have the advantage of
1 of the packed bed reactor network may improve the "t rigorously de"ned inlet and exit boundary conditions.
to the experimental data in the region 0.2(h(0.3 and Combination of the ETIS model with the reactor net-
h"0.75. However, as can be seen from Fig. 9 the scope work structure permits a considerable increase in the
for improvement is small. versatility of networks with out the concomitant increase
Dispersion at knots. A basic assumption of the reactor in numerical intensity which characterises networks of
network structure is that there is no dispersion through CSTRs.
the `knotsa. This assumption is completely consistent
with the application of the `closeda dispersion model to
characterise the interconnecting `threadsa. Such a high Notation
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 C dimensionless concentration Dimensionless
and outlet boundary conditions. The implied assump- D eddy di!usion coe$cient L t\
tions for the tanks in series model relate to the inlet and E(h) exit age distribution function Dimensionless
outlet of a CSTR and would indeed be consistent with e base of natural logarithms Dimensionless
the no dispersion through the `knotsa assumption. The (2.718...)
same implicit assumption is made in the ETIS model but f #ow fraction Dimensionless
is conceptually di$cult when n is not an integer. I `mixinga index Dimensionless
2
The extent of dispersion through the `knotsa is only ¸ characteristic length L
likely to be signi"cant where both source and sink N dispersion number Dimensionless
`threadsa are themselves characterised by high disper- "
n number of tanks in series Dimensionless
sion. The qualitative e!ect of removing the central `knota 2
p precision Dimensionless
joining 2 CSTR `threadsa is shown in Fig. 2. By analogy Pe peclet number Dimensionless
with the previous discussion regarding the suitability of Q liquid feed rate L t\
the ETIS model for the characterisation of individual S a term in the series solution Dimensionless
`threadsa it may be deduced that the no dispersion of the closed dispersion
through `knotsa assumption holds within experimental model
accuracy when n '15 and Pe'28.97 in the more plug mean residence time t
2 ¹
#ow `threada. Quantitative assessment of the breakdown T Hydraulic mean residence t
of the no dispersion through the `knotsa assumption is time
not reported here but might be approached via consid- t elapsed time t
eration of the Kurtosis of the RTDs. tM mean of the residence time t
Ordering. Using the simple conservative `dyea -tracing distribution
methods reported here it is not possible to order the u velocity L t\
`threadsa in a reactor network without additional struc- < volume L
tural information. To make progress with respect to v volume fraction Dimensionless
ordering of model elements in the absence of structural z axial displacement L
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 Greek letters
here.
! gamma function
8. Conclusions g E$ciency
p 3.141592
The ETIS model in conjunction with the reactor net- # strand dimensionless
work structure has been shown to be a versatile method residence time
of describing the characteristics of a small but diverse h dimensionless time Dimensionless
group of reactors. The ETIS model has been compared hM mean of the dimensionless Dimensionless
with the conventional tanks in series approach and has RTD
been found to be superior due to the elimination of the p variance of the dimensionless Dimensionless
quantisation which is inherent in the latter approach. RTD
The ETIS model has also been compared with the
Thomas and McKee `closeda solution to the dispersion Subscripts
model. The `closeda dispersion model has been shown to
di!er signi"cantly from the ETIS model in the range 10 pertaining to the recovery of
0(Pe(28.97 and 1(n (15. The `closeda disper- 10% of the injected `dyea
2
 A. D. Martin / Chemical Engineering Science 55 (2000) 5907}5917 5917

90 pertaining to the recovery of References

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H hydraulic Elgeti, K. (1996). A new equation for correlating a pipe #ow reactor
i inlet with a cascade of mixed reactors. Chemical Engineering Science,
M merril 51(23), 5077}5080.
m modal Kramers, H., & Alberda, G. (1953). Frequency response analysis of
o `opena dispersion model continuous #ow systems. Chemical Engineering Science, 2, 173}181.
Levenspeil O. (1972). Chemical reaction engineering, (2nd ed), ISBN
R whole reactor 0-471-5306-6 New York: Wiley.
s thread index Levenspeil, O., & Smith, W. K. (1957). Notes on the di!usion-type
sc short circuiting model for the longitudinal mixing of #uids in #ow. Chemical Engin-
¹ pertaining to the TIS and ETIS eering Science, 6, 227}233.
models Monteith H. D., & Stephenson J. P. (1981). Mixing e$ciencies in
full-scale anaerobic digesters by tracer methods. Journal WPCF
53(1).
Smith, L. C., Elliot, D. J., & James, A. (1993). Characterisation of mixing
patterns in an anaerobic digester by means of tracer curve analysis.
Eccological Modelling, 69, 267}285.
Acknowledgements
Teefy S. (1996). Tracer studies in water treatment facilities: A protocol and
case studies. ISBN 0-89867-857-9. AWWA Research Foundation
The author would like to acknowledge the assistance and American Water Works Association.
of the following colleagues who contributed their experi- Thomas, H. A., & McKee, J. E. (1944). Longitudinal mixing in aeration
mental data for the case studies. Ms. Laura Burrows, tanks. Sewage Works Journal, 16(1), 42}55.
Tomlinson E. J., & Chambers B. (1979). The e!ect of longitudinal
Experimental data from the internally recirculating
mixing on the settleability of activated sludge. TR122 WRc July
CSTR. Mrs. Barbara Gray, Experimental data from the 1979.
packed bed reactor. Mr. Tony Robinson, Calculation of Yagi, S., & Miyauchi, T. (1953). On the residence time curves of the
the simulated RTD for the Large CSTR. continuous reactors. Chemical Engineering (Tokyo), 17(10), 382}386.