Chemical Engineering Science 54 (1999) 10291043

Steady-state multiplicities in reactive distillation columns

for the production of fuel ethers MTBE and TAME:
theoretical analysis and experimental verication
Klaus-Dieter Mohl*, Achim Kienle, Ernst-Dieter Gilles, Patrick Rapmund',
Kai Sundmacher', Ulrich Homann'
Institut fu r Systemdynamik und Regelungstechnik, Universita t Stuttgart, Pfaenwaldring 9, 70550 Stuttgart, Germany
'Institut fu r Chemische Verfahrenstechnik, Technische Universita t Clausthal, Leibnizstr. 17, 38678 Clausthal, Germany
Received 18 May 1998; accepted 4 November 1998
Abstract
In this contribution, the nonlinear dynamic behaviour of reactive distillation columns for the production of MTBE and TAME is
studied. The focus is on steady-state multiplicity and a rigorous bifurcation analysis of pilot plant reactive distillation columns for
both processes is presented. The dierent sources and physical causes for the existence of multiple steady-states in MTBE and TAME
synthesis are discussed. Further, a rigorous experimental verication of steady-state multiplicity in a pilot plant reactive distillation
column for the production of TAME is presented. Finally, some remarks on the implications of multiple steady-states on column
operation are made. 1999 Elsevier Science Ltd. All rights reserved.
Keywords: Reactive distillation; Fuel ethers (MTBE and TAME); Nonlinear dynamics; Numerical analysis, Multiple steady-states;
Experimental verication
1. Introduction
Due to clean air legislation (Hall, 1992) the production
of fuel ethers like methyl tert-butyl ether (MTBE) and
tert-amyl methyl ether (TAME) received a lot of atten-
tion in recent times. In particular, the production of fuel
ethers by reactive distillation gained an enormous eco-
nomic importance. The economic importance of these
processes gives rise to a need for a better understanding
of their complex dynamic behaviour. Recently, the atten-
tion of researchers was attracted by the intricate nonlin-
ear dynamic behaviour of reactive distillation columns
for the production of fuel ethers.
In particular, for MTBE synthesis several theoretical
studies indicate the existence of multiple steady-states.
Nijhuis et al. (1993) and Jacobs and Krishna (1993) found
multiple solutions varying the feed location. Hauan et al.
(1995) gave a mechanistic explanation for the multiple
*Corresponding author. Fax: 0049 711 685 6371.
E-mail address: mohl@isr.uni-stuttgart.de (K.-D. Mohl)
steady-states found. Schrans et al., (1996) further re-
ported the existence of self-sustained oscillations for the
same column conguration using a dynamic model ac-
counting for tray hydraulics. Gu ttinger and Morari
(1997) presented a reactive R/R-analysis using trans-
formed composition variables introduced by Ung and
Doherty (1995). They also studied how the existence of
multiplicities depends on model assumptions like con-
stant molar overow or choice of input variables. Mohl
et al. (1997a) considered two dierent process congura-
tions and studied the process behaviour in terms of
operating parameters rather than design parameters like
feed location and therefore discussed implications of mul-
tiple steady-states for process operation.
For the TAME synthesis the experimental work of
Bravo et al. (1993) indicates the existence of multiple
steady-states in a pilot plant catalytic distillation column.
In theoretical studies, Mohl et al. (1997a) found multiple
steady-states for operating conditions similar to those in
Bravo et al. (1993). But a comprehensive physical ex-
planation for the steady-state multiplicities observed
for TAME synthesis as well as a rigorous experimental
0009-2509/99/$ see front matter 1999 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 9 8 ) 0 0 3 2 7 - 3
verication of this phenomenon for reactive distillation
columns in general are, to our knowledge, still missing.
The aim of the present paper is to bridge this gap.
The paper is organized in the following way: rst some
preliminaries like the column conguration, the model
formulation considered and the model validation using
experimental data from pilot plant columns are present-
ed. Then the steady-state behaviour of the considered
reactive distillation columns for the production of MTBE
and TAME is discussed. For TAME synthesis the rst
experimental evidence for the existence of steady-state
multiplicity in a reactive distillation column is given. In
this context, some remarks on the choice of input vari-
ables and the implications of the observed multiple
steady-states for process operation are given. Finally,
a physical explanation for multiple steady-states found
for TAME synthesis is established.
2. Preliminaries
The ethers MTBE and TAME are produced according
to the generalized reaction scheme (Eq. (1)) where an iso-
olen (IO), reacts with methanol (MeOH) to form terti-
ary ethers like MTBE and TAME in a reversible,
exothermic reaction:
methanol # iso-olen A tert. ether.
(isobutylene/isoamylene) (MTBE/TAME).
(1)
The reactions are catalyzed by strong acid ion-exchange
resins and are usually carried out in the presence of inert
components. The inert components result from upstream
processing, where the iso-olen is produced along with
other hydrocarbon components in a steamcracker or a
FCC-unit. For MTBE synthesis the iso-olen is isobuty-
lene (IB) and for TAME synthesis the iso-olen are two
isoamylenes, the isomers 2-methyl-1-butene (2M1B) and
2-methyl-2-butene (2M2B). 1-butene and n-pentane are
assumed to represent inert components for the MTBE-
and TAME-synthesis, respectively.
2.1 Column conguration and experimental set-up
For the production of ethers via reactive distillation
dierent process congurations with regard to the feed-
ing strategy, catalyst technology and catalyst location
were introduced (Sundmacher, 1995). In this paper the
conguration shown in Fig. 1 is studied. In Fig. 1 the
column set-up is depicted for the TAME column, for
MTBE the setup is almost identical. This conguration
was introduced by Homann and coworkers for MTBE
(Flato and Homann, 1992; Sundmacher and Homann,
1996) and TAME (Homann et al. 1997) synthesis and is
realized at the Institut fu r Chemische Verfahrenstechnik
(ICVT), Technische Universita t Clausthal as two pilot
plant xed-bed columns, one for MTBE and one for
TAME synthesis. The columns have an inner diameter of
76 and 55 mm for TAME and MTBE, respectively. They
were designed for a maximum operating pressure of
12 bar and a maximum operating temperature of 400 K.
Two packings, each with a height of 500 mm, were instal-
led a catalytic packing in the upper section and a non-
catalytic packing in the lower section. All parts of the
column are isolated by a 50 mm layer of mineral wool to
minimize the thermal losses. The ion-exchange rings
(8;8 mm) in the upper column section were manufac-
tured by precipitation polymerization of a sulphonic acid
ion-exchange resin (divinylbenzene-styrene copolymer)
inside the structure of porous glass rings (Kunz and
Homann, 1995). The packings in the lower column
section contain porous glass rings without any ion-ex-
change material on it. They served for the non-reactive
separation of the products MTBE and TAME, respec-
tively, from the reaction mixture. Some properties of the
inert and catalytic glass rings are listed in Table 1.
In Fig. 1 also the column measuring and control devi-
ces are depicted. All process data (temperatures, pres-
sures, ow rates, liquid levels) were visualized and stored
by a monitoring system which enables the operator to
decide if steady-state is attained.
The pressure at the top of the column was controlled
by the condensing rate. The amount of condensate de-
pends on the ow rate and the temperature of the cooling
water. During the experiments, a constant ow rate was
circulated by the pump P1 and the water temperature
was varied by the ow rate of the introduced fresh cool-
ing water. The reux ratio was calculated from the ow
rates (Pelton turbines FIR 1 and FIR 2) before and
behind the distillate withdrawal. The distillate rate was
adjusted by the valve V1. The temperatures of the reux
ow and the feed ow were monitored by the thermo-
resistors TIRC 1.1 and TIRC 1.3. The temperatures were
controlled by heating devices to be 1 K below their
boiling temperatures. For the control of the liquid level in
the reboiler vessel the bottom product stream was ad-
justed by the valve V3. To keep the reboiler heating
devices from becoming dry, a minimum liquid level is
necessary. The mass uxes of feed and distillate were
gravimetrically controlled. The feed is premixed and in-
troduced in the middle of the column, below the catalytic
section. Oscillations from the feed piston pump were
damped by a membrane system connected to the feed
tube. Vapour and liquid phase samples were drawn from
the top (TV, TL), from the middle (MV, ML) and from
the bottom of the column (BV, BL). The locations can be
seen from Fig. 1. The samples were stored in an oven and
were subsequently analysed by a gas chromatographic
capillary system.
Thus, the column conguration studied here diers in
some points from the conguration mainly studied in the
1030 K.-D. Mohl et al. /Chemical Engineering Science 54 (1999) 10291043
Fig. 1. Conguration of pilot plant columns for TAME production.
Table 1
Some properties of the 8;8 mm inert and catalytic rings used in this work
Property Unit Inert rings Catalytic rings
Eective diameter, d
C
"6/S
T
m 5.2 5.2
Voidage of packing (1
1
) Dimensionless 0.47 0.47
Specic packing surface, S
T
m`/m` 567 567
porosity, Dimensionless 0.55 0.39
Ion-exchange capacity, q in dry state meq(H>) /g 0.0 1.2
Acid group concentration, c
*
per ring volume eq(H>) /l 0.0 0.9
Inner column diameter d
G
"0.076 m.
literature, (e.g. Nijhuis et al. 1993). The columns have
a single feed in the middle of the column, the feed at the
top in Fig. 1 is not used. Also dierent input variables are
used. At the top the reux ratio R and at the bottom the
heating rate Q (instead of the molar bottoms ow rate B)
are the input parameters of the column. Consequently,
the input parameters R and Q are used to study the
process behaviour instead of feed location or other de-
sign variables.
2.2 Process model and model validation
An equilibrium stage model is used. To account
for deviations from vapourliquid equilibrium (VLE),
K.-D. Mohl et al. /Chemical Engineering Science 54 (1999) 10291043 1031
Murphree point eciencies are employed. They are esti-
mated from experimental data for dierent operating
conditions. The values are 0.8 and 0.7 for MTBE and
TAME, respectively. According to Sundmacher and Ho-
mann (1996), 12 stages are used, ve for each column
section and two for reboiler and condenser. In contrast to
Mohl, et al. (1997a) a total reboiler is used.
For the MTBE process the VLE is calculated using
UNIQUAC with the binary interaction parameters from
Rehnger and Homann (1990). For the TAME process
the VLE is calculated using the Wilson model because
the UNIQUAC model incorrectly predicts a miscibility
gap. Experimental liquidliquid equilibrium and azeo-
tropic data indicate that for the relevant mixtures a phase
split only occurs for subcooled liquid. Because subcool-
ing of the reux and the feed is controlled to 1 K, no
phase split occurs and VLE is best described by the
Wilson model. The Wilson interaction parameters for the
TAME system are tted to experimental data from
(DDBST, 1993) and to predictions with UNIFAC where
experimental data were not available.
Further, heat losses along the column are taken into
account using constant heat transfer coecients, which
have been tted to experimental column data. This is
necessary despite the fact that the columns are isolated
by a 50 mm layer of mineral wool, because of the small
diameter of the columns and the fact that the columns are
built from steel.
The reactions for MTBE and TAME synthesis can be
modeled using the generalized rate expression (cf. Eq. (2)):

r"k()

a
'
a
`''
!
1
K
?
a
'''''"'
a`
`''

. (2)
In case of the TAME synthesis, the isoamylenes 2M1B
and 2M2B are lumped (Oost and Homann 1995). The
rate constants of Eq. (2) for MTBE and TAME are taken
from Rehnger and Homann (1990) and Oost and Hof-
fmann (1995) respectively. According to Rehnger and
Homann (1990) and Oost and Homann (1995) the
liquid-phase activities a
G
in Eq. (2) are calculated using
UNIQUAC and the corresponding binary interaction
parameters provided there. Note that besides the similar-
ities of the reactions the rate for MTBE is about one
order of magnitude larger than the rate for TAME (cf.
Fig. 2).
The model was validated using experimental data from
the columns at the ICVT, TU Clausthal. In the upper
plots of Fig. 3 the temperature proles along the column
height are shown, in the lower plots the concentrations
for the 12 stages of the column are plotted in the phase
diagrams. The C4- and C5-components (i.e. the iso-ole-
ns and the inert components) for MTBE and TAME,
respectively, are lumped. The experimental data for
MTBE (part a) of Fig. 3 are taken from Thiel (1997),
those for TAME (part b) of Fig. 3 from Rapmund (1998).
Fig. 2. Normalized mikrokinetic reaction rate (r
,
"r/) of MTBE and
TAME at sulphonic acid ion exchange resins ("333.15 K and x
#RFCP
+0).
As Fig. 3 shows, even with the simple model used here,
a good qualitative agreement of experimental and theo-
retical data is obtained. Hence, this process model is
suitable for the process analysis and the dynamic simula-
tion presented in the subsequent sections.
2.3 Steady-state behaviour of the processes
The analysis of the process behaviour was performed
using the continuation methods implemented in the
simulation tool DIVA (Holl et al. 1988; Kro ner et al.,
1990; Helget et al. 1994, Mohl et al. 1997b). The con-
tinuation methods (Kienle et al. 1995b) permit the e-
cient calculation of parameter-dependent solution
branches. Information on the stability of the calculated
solutions is obtained by calculating the corresponding
eigenvalues.
The steady-state behaviour of the MTBE and TAME
processes was studied in terms of the input parameters
reux ratio R and heating rate Q. For dierent constant
values of the reux ratio R, the heating rate Q was used as
continuation parameter. Though the processes are very
similar with regard to reaction kinetics, topology of the
residue curves and the conguration, the process
behaviour is completely dierent. In part a of the plots in
Figs. 4 and 5 the concentration of the desired product
MTBE and TAME in the bottoms respectively is plotted
vs. the continuation parameter Q for the dierent reux
ratios. The circle depicts the operation boundary of total
reboil.
1032 K.-D. Mohl et al. /Chemical Engineering Science 54 (1999) 10291043
Fig. 3. Comparison of experimental results (, location of composition measurements can be found in Fig. 1) and simulation results(, denotes tray
compositions) for MTBE (a) and TAME (b).
For the MTBE synthesis Fig. 4a gives some informa-
tion relevant for process design and operation. There is
a distinct maximum in the product composition over the
heating rate and even for small reux ratios high product
concentrations of MTBE can be achieved. Further, for
a reux ratio of R"15 there is a small range of heating
rates, where multiple solutions occur. The range of input
parameters for which multiple steady-states occur is de-
picted as the grey area in the (R, Q)-plane (cf. Fig. 4b).
As Fig. 5a shows the maximum product composition
for TAME synthesis is obtained at total reboil and alike
MTBE, for small reux ratios high product concentra-
tions may be obtained. But for TAME already at reux
ratios as small as R"3 multiple steady-states are pre-
dicted. This is also illustrated by Fig. 5b where the
multiplicity region is depicted as the grey area in the
(R, Q)-plane.
Further analysis shows that the multiple solutions
occur under dierent reaction regimes for MTBE and
TAME. As was shown by Jacobs and Krishna (1993) for
the MTBE synthesis the multiplicities occur under reac-
tion equilibrium conditions, whereas for the TAME syn-
thesis the column is operated in the kinetic regime of the
reaction (Mohl et al. 1997a). This is easily understood
from the slower reaction rate of the TAME synthesis
(cf. Fig. 2).
Although for both processes the multiplicity region
over the heating rate is increasing with increasing reux
ratio, for MTBE multiple steady-states occur only in
a small range of heating rates. For a given heating rate,
within the multiplicity region, they may occur over very
wide range of reux ratios though. This complies with
similar results of Nijhuis et al. (1993) for a conguration,
where reux ratio R and molar bottoms ow rate B are
used as input parameters (R/B-conguration).
According to Gu ttinger and Morari (1997) the multi-
plicity in Nijhuis et al. (1993), Jacobs and Krishna (1993),
Hauan et al. (1995) and Schrans et al. (1996) for the
R/B-conguration are rather academic because they
can be avoided using dierent (more common) input
parameters like the bottoms mass ow rate. In contrast,
the multiplicities studied here may be found in real op-
eration because reux ratio and heating rate are com-
monly used input parameters, which can be directly
adjusted at the real plant. However, an experimental veri-
cation of steady-state multiplicity for the MTBE process
is dicult due to the small size of the multiplicity region
with regard to the heating rate. This means that the
heating rate would have to be adjusted very accurately to
attain an experimental verication. Moreover, the small
size of the multiplicity region in terms of the heating rate
implies that the existence of multiple steady-states for the
MTBE process under these operating conditions is of
minor importance for practical process operation.
In contrast to MTBE for TAME synthesis the
multiplicity region is much larger, thus an experimental
verication of steady-state multiplicity for the reactive
distillation columns under consideration is possible for
the TAME process and will be presented in the next
section.
K.-D. Mohl et al. /Chemical Engineering Science 54 (1999) 10291043 1033
Fig. 4. MTBE process at p"11 bar, "1.0 and "0.3: (a) bifurca-
tion diagram for dierent reux ratios R, denotes total reboil; (b)
multiplicity region.
3. Experimental verication
3.1 Determination of operating conditions
In an iterative procedure of theoretical and experi-
mental work suitable operation conditions were deter-
mined. A rst attempt to verify the existence of multiple
steady-states showed that besides a sucient size of the
multiplicity region, uid dynamic stability of the column
was critical. Therefore, the feed stream was reduced to the
smallest possible value with reproducible constant ow
rate. Further, the continuation methods were used to
study the inuence of dierent operating parameters,
namely pressure p and feed composition and on size
and location of the multiplicity region. From these re-
sults operating conditions were chosen, which ensure
both a stable uid dynamic operation of the column and
Fig. 5. TAME process at p"2 bar, "1.0 and "0.3: (a) bifurcation
diagram for dierent reux ratios R, denotes total reboil; (b) multipli-
city region.
a multiplicity region large enough for reproducable ex-
perimental results (Mohl et al. 1998). In particular, the
operating conditions are: pressure p"2.5 bar; feed ow
rate F
K
"0.96 kg/h; feed conditions "0.8 and "0.3
and the reux ratio R"15. The bifurcation diagram for
these operating conditions is presented in Fig. 6a. It
shows that multiple steady-states are predicted in the
range of the heating rate Q from 0.25 to 0.45 kW. The
analysis shows that the upper and lower solution
branches are stable, while the intermediate branch is
unstable. For the experiments one value of the heating
rate (depicted as the vertical line in Fig. 6a) within
the multiplicity range was chosen for the reboiler
duty. The three steady-states obtained for Q"340 kW
as well as the corresponding temperature proles are
shown in Fig. 6. As can be seen from Fig. 6a though the
steady-states dier only slightly with regard to the
product concentration, they can easily be distinguished
1034 K.-D. Mohl et al. /Chemical Engineering Science 54 (1999) 10291043
Fig. 6. (a) Bifurcation diagram for TAME process (, stable solution);
(!!, unstable solution); (b) temperature proles for the steady states
(1)(3) at Q"340 W.
from their characteristic temperature proles shown in
Fig. 6b.
3.2 First experimental runs
For all the experimental runs presented here, the above
specied operating conditions were applied. In start-up
the column was heated up, at total reux conditions and
without feed supply. After reaching a stationary temper-
ature prole, the feed was introduced and the product
streams were withdrawn.
In the rst runs F2 and F5 dierent initial mixtures
(with and without TAME) in the reboiler, led to almost
identical column temperature proles which coincide
with the predicted steady-state (1).
Thus, a suitable startup procedure for reaching the
second stable steady-state (3) was needed. Using dynamic
simulation the experimental nding in runs F2 and F5,
i.e. the startup to steady-state (1) were reproduced with
the model introduced in section (2.2). Then a suitable
startup procedure for obtaining the steady-state (3) was
derived by dynamic simulation (Mohl et al., 1998). By
starting up the column with a low boiling mixture, i.e.
close to the azeotropic composition of methanol and
n-pentane, steady-state (3) was conrmed experimentally
in runs F6 and F7. In Fig. 7 the measured temperatures
along the column are depicted.
Fig. 7. Experimental steady-state temperature proles in packed react-
ive distillation column for TAME-production (low steady state
"solution(3); high steady state "solution (1)).
Note that all these proles were obtained for identical
operating conditions. The dierences of temperatures
between steady-states (1) and (3) are signicant. At the
top of the column nearly the same temperatures were
observed in all experiments. The temperature dierences
between the two steady-states are increasing towards the
stripping section of the column and in the reboiler. This
behaviour is in good qualitative agreement with the
simulated results. Quantitative dierences are due to the
fact that the applied model is quite simple. In particular,
neglecting the side reactions becomes important for the
substoichiometrical feed mixture ("0.8), because under
these feed conditions the dimerization of the IA becomes
important. This explanation is supported by the fact that
the temperature level in the experiments is higher than
that in the simulations, which can be explained by the
high boiling points of the di-isoamylenes. More detailed
information on the applied operating conditions and the
experimental results are listed in Table 2.
3.3 Transition between steady-states
The experiments were extended by investigating the
transition between the steady-states (3) and (1), runs F7
and F8 in Table 2, respectively. The rst experiments
demonstrated that the steady-state (1) with the higher
TAME concentration in the reboiler can be realized
easier. Therefore, the transition was started from the
steady-state (3) with low product concentration in the
reboiler (run F7, cf. Fig. 8). Then at t"860 min a block
pulse injection of pure TAMEto the feed was carried out.
The temperature near the feed point (TIR 5) increased
after a delay of 12 min, inuenced by the high liquid
hold-up of the porous catalyst packing. In the lower part
of the stripping section a temperature increase up to
K.-D. Mohl et al. /Chemical Engineering Science 54 (1999) 10291043 1035
Table 2
Experimental results for reactive distillation of TAME; operating conditions: p"2.5 bar; Q"0.34 kW; "0.8; "0.3; R"15
Run F
K
(kg/h) D
K
(kg/h) x
`''
T x
'^`' "
TIR 3 [C] TIR 8 [C]
F2 0.96 0.34 0.22 0.18 65.5 68.7
F5 0.98 0.38 0.23 0.22 65.0 67.8
F6 0.97 0.40 0.24 0.10 59.0 62.7
F7 0.98 0.37 0.27 0.12 63.3 63.2
F8 0.97 0.37 0.25 0.26 66.4 68.6
Dimensionless.
Fig. 8. Transient behaviour between runs F7 and F8. Above: TAME block pulse injection to feed, below: response of temperatures TIR5 and TIR10.
379 K was observed (TIR 10). Due to the pulse injection,
the operating pressure dropped for a time. This was
compensated by the controller loop with a delay only
and therefore some temperatures decreased during
transition, too. At t"920 min the feed composition
was set to the initial conditions of "0.8 and "0.3,
at t"1000 min the system stabilized and after t"
1360 min it came to a new steady-state, which corres-
ponds to the steady-state (1).
An analysis of the process behaviour, where the vol-
umentric reux
O
is used as continuation parameter for
dierent values of the heating rate Q shows, that multi-
plicities also occur for other input parameters. Note, that
the
O
/Q-conguration is the most frequently used con-
guration in industry for distillation control.
The results presented in this section illustrate clearly
the implications of multiple steady-states for process
operation. First it shows, that process startup in the
region of multiple steady-states is not a trivial task,
because it may be dicult to reach the desired steady-
state, like it was the case for steady-state (3) in the
experiments. Second, the transition between the stable
steady-states (1) and (3) shows, how temporary distur-
bances in the operating conditions may cause a transition
to an undesired steady-state of the process. Further the
results demonstrate that a close cooperation between
theoretical and experimental work was a necessary pre-
requisite for the successful experimental verication of
multiple steady-states.
4. Physical explanation for multiple steady-states
It is a well-known fact that for both individual unit
operations combined in reactive distillation processes
multiple steady-states can occur. For reactors two main
sources causing multiplicities can be identied. The
multiplicities can be either caused by heat eects or by
kinetic instabilities (see e.g. Razon and Schmitz (1987).
and references therein). For distillation columns three
dierent types of multiplicites are known, see e.g. Kienle,
et al. (1995) and references therein. Multiple steady-states
1036 K.-D. Mohl et al. /Chemical Engineering Science 54 (1999) 10291043
in distillation columns can occur due to the dependence
of the molar volume or the heat of vaporization on
composition for special choices of the input variables or
due to a special topology of the residue curves for azeo-
tropic mixtures. Thus, in principle, steady-state multipli-
city in reactive distillation columns can be caused by
every single one of these mechanisms, by any combina-
tion of these mechanisms or by some mechanisms arising
from the interaction of reaction and separation.
The mechanism for reactors, inducing multiplicities
due to heat eects can be discarded for reactive distilla-
tion, because in distillation temperature is in general
determined by the boiling point of the mixture.
The three mechanisms that may induce multiple
steady-states in distillation can be excluded for the
TAME synthesis in particular, because for the TAME
process considered here multiplicities cannot be due to
the concentration dependence of the molar volume or the
heat of vaporization, because reux ratio and heating
rate are used as inputs (Jacobsen and Skogestad, 1991).
Finally, multiple steady-states are not caused by the
azeotropes of the mixture, because the necessary condi-
tion, i.e. two neighbouring saddles is not satised (Be-
kiaris et al., 1993).
This indicates that multiple steady-states for the
TAME process are due to kinetic instabilities. This hy-
pothesis is supported by Fig. 9, where the steady-state
solution branches for the operating conditions of the
experiments and dierent amounts of active sites are
depicted. The plot shows that as the number of active
sites is increased and the process is getting closer to
reaction equilibrium the range of heating rates for which
multiple solutions are obtained decreases and nally
vanishes.
To study kinetic instabilities in more detail an isother-
mal CSTR is considered. For the heterogeneously
catalyzed TAME synthesis the Damko hler number (Eq.
(3)) is dened according to Rehnger and Homann
(1990) :

Da"
r
"
N
'
>
nR
`'' $

, (3)
where r
"
is the reaction rate at zero conversion, N
'
>
the
number of active sites and nR
`'' $
is the molar feed of
methanol.
Fig. 10 (right plot) shows that in an isothermal CSTR
multiple solutions of the methanol conversion are ob-
tained for the TAME synthesis. This is not surprising,
because it is a well-known fact that kinetic expressions
like the one in Eq. (2), i.e. self-inhibiting kinetics with
regard to one of the reactants, may cause multiple solu-
tions, e.g. Matsuura and Kato (1967). For the TAME
synthesis methanol acts as self-inhibiting reactant due to
the preferred adsorption to the active sites of the catalyst
(Oost and Homann 1995). For the isothermal CSTR
Fig. 9. Bifurcation diagram for the TAME process with dierent num-
bers of active sites: N
&
>
(); N
&
>
;10 (!!); N
&
>
;0.1 (!) !).
with a single reaction, explicit stability criteria can be
derived from an eigenvalue analysis. These stability cri-
teria are given in Appendix A.
To show that the multiplicity found for the reactive
distillation column do have the same source as the multi-
plicity found for the isothermal CSTR, i.e. kinetic
instabilities, the smallest possible column was studied.
That is a one-stage column (cf. Fig. 11) consisting
of a partial reboiler, where the reaction takes place,
and a total condenser. Comparison of the model equa-
tions for the one-stage column and the CSTR shows
that the equations become identical for heating rates or
vapour ows equal to zero and for very high reux ratios.
The only dierence remaining is that for the one-stage
column temperature is not constant. Temperature
changes due to the boiling point condition according
to changes of the composition for a given operating
pressure.
In the following, the process behaviour for reactive
distillation columns with dierent numbers of stages is
analysed: starting from the one-stage column and
heading towards the model of the pilot plant column
having 12 stages. The operating conditions for all col-
umns were as for the experimental verication. Namely,
pressure is set to p"2.5 bar, reux ratio to R"15,
heating rate Q"0.34 kW and the amount of IA among
the C5-components to "0.3.
K.-D. Mohl et al. /Chemical Engineering Science 54 (1999) 10291043 1037
Fig. 10. Methanol conversion vs. Damko hler number in an isothermal CSTR at "0.45 and "333.15 K for dierent values of : Left plot for
MTBE synthesis (according to Rehnger and Homann, 1990), right plot for TAME synthesis.
Fig. 11. One-stage column with partial reboiler and total condenser.
Critical boundaries of the process behaviour are very
sensitive to changes of the input parameters of the process.
Therefore, the results of the process analysis is presented in
terms of two parameters, i.e. feed composition and
Damko hler number Da. The critical boundary in this
case is the location of limit points in the (, Da)-plane,
separating the region of one unique and stable steady-
state solution from the multiplicity region, where three
steady-state solutions (one unstable and two stable) exist.
Fig. 12. Multiplicity region for TAME synthesis in the (,Da)-para-
meter plane for the CSTR (
$
"328 K,
!120
"335 K) and the one-
stage column (p"2.5 bar).
First, a comparison of the multiplicity region of the
CSTR and the one-stage column is given in Fig. 12.
While feed temperatures for CSTR and one-stage
1038 K.-D. Mohl et al. /Chemical Engineering Science 54 (1999) 10291043
Fig. 13. Multiplicity regions for TAME reactive distillation columns with dierent number of stages ( denotes the operating point of the
experiments).
K.-D. Mohl et al. /Chemical Engineering Science 54 (1999) 10291043 1039
column are identical, the temperature of CSTR is set to
the average value of the temperatures obtained in the
one-stage-column along the dashed curve in Fig. 12. It
shows that the shape of the multiplicity regions is very
similar, but the size diers. The dierences in size are
mainly due to the changes of the reaction temperature of
the one-stage-column according to the changes of the
boiling point of the reaction mixture. If the temperature
dependence of the reaction kinetic is neglected and a con-
stant temperature is used instead, the multiplicity regions
hardly dier. Thus, the dierence between CSTR and
one-stage-column due to the nite vapour stream and
the reux are of minor importance for the dierent sizes
of the multiplicity regions.
To accomplish a transfer from the one-stage column
to the model of the reactive distillation column having 12
stages, models of reactive distillation columns with dier-
ent number of stages were considered, in particular col-
umns with 4 and 8 stages. For all the columns a total
reboiler and a total condenser was used and the remain-
ing stages were split half in catalytic and half in inert
stages. Note that the column size is not changed, only the
number of stages used to model the column is increased.
Thus the number of active sites N
&
>
remains constant for
all models of the column, but with the number of stages
the eect of separation is increased.
The four plots in Fig. 13 show a steady transition of
size and shape of the multiplicity region with increasing
number of stages. This conrms that the multiple steady-
states observed in the experiments, denoted by a dot in
Fig. 13d, do have the same physical source as those in the
isothermal CSTR, i.e. kinetic instabilities. Further and
even more important from a process operation point of
view, is the fact that Fig. 13 illustrates clearly that the
multiplicity region and thus the possibility of obtaining
multiple steady-states in a reactive distillation is growing
with increasing separation by increasing the number of
stages. For example, for the 12-stage column multiple
steady-states may occur up to values of +1.6, which
corresponds to a feed mixture with 60% excess of
MeOH. Also the multiplicity region moves to higher
values of the Damko hler number, which is equivalent to
smaller feed ow rates.
At this point a comparison of the TAME process and
the MTBE process is of interest. According to Jacobs and
Krishna (1993) multiplicity for the MTBE process is not
eected by an increase in the amount of catalyst inside
the column. This means that the multiplicity reported by
Jacobs and Krishna (1993) occurs under reaction equilib-
rium and is not caused by kinetic instabilities. However,
Rehnger and Homann (1990) reported multiple
steady-states in an isothermal CSTR for the MTBE syn-
thesis, cf. left plot in Fig. 10. Hence, for suitable design
and operating parameters (dierent from Jacobs and
Krishna, 1993) kinetic instabilities can be also found for
the MTBE process (Mohl, et al., 1997a).
5. Conclusions
The rst rigorous experimental verication for the
existence of multiple steady-states in a reactive distilla-
tion column for the production of TAME was presented.
It was demonstrated that only the combination of theor-
etical and experimental studies enabled the experimental
verication. Steady-state multiplicity occurs when reux
ratio R and heating rate Q are chosen as the input
variables. Note that these parameters can be adjusted in
a real-plant condition as well.
The implications of steady-state multiplicity for pro-
cess operation were demonstrated by the development of
a start-up procedure, its experimental verication and by
the transition between steady-states in the experiments
due to changes of the feed conditions. The presented
results illustrated that column start-up to the desired
steady-state may be dicult and temporary changes in
any of the operating parameters, like heating rate, feed
composition may drive the column to an undesired
steady-state.
A detailed analysis shows that multiple steady-states
for the TAME process are caused by kinetic instabilities.
Further it is shown that the multiplicity region in para-
meters space grows due to simultaneous separation. It is
nally concluded that similar kinetic instabilities can
occur for the MTBE process.
Ackowledgements
The authors express their thanks to the Bundesminis-
terium fu r Bildung, Wissenschaft, Forschung und Tech-
nologie for sponsoring this work within the research
project Nichtlineare Dynamik bei chemischen Prozes-
sen Teil B: Reaktivdestillation (Sponsoring ID 03
D 0013 B).
Appendix
Stability criteria for an isothermal CSTR
In the remainder stability criteria are derived from an
eigenvalue analysis of an isothermal CSTR and a single
reaction. It is shown that these eigenvalues are always
real. Hence, in contrast to the well-known non-iso-
thermal case, Hopf bifurcations are not possible in the
isothermal case of a single reaction. Hopf bifurcations
correspond to the bifurcation of a branch of periodic
solutions from a branch of steady-state solutions. In-
stead, it is shown that real bifurcations are possible
corresponding to the occurrence of multiple steady-
states. Critical conditions for the occurrence of multiple
steady-states are discussed.
1040 K.-D. Mohl et al. /Chemical Engineering Science 54 (1999) 10291043
Assuming
E a single reaction with rate r,
E constant pressure and temperature,
E constant mixture volume inside the reactor,
the model equations of the CSTR follow from the mater-
ial balances
dn
dt
"nR
GL
!nR #
,A

I
rN
&
>
, (A.1)
d(nx
G
)
dt
"nR
GL
x
G GL
!nR x
G
#
G
rN
&
>
, i"1(1) N
A
!1.
(A.2)
It should be noted that inert components like 1-butene
for MTBE synthesis and n-pentane for TAME synthesis
are also included in this model for
G
"0. Since the
etherication reactions are heterogeneously catalyzed
the turnover of the reaction is not proportional to the
volume of the reaction vessel but to the number of
active sites N
&
>
available.
Substitution of Eq. (A.1) into Eq. (A.2) yields
n
dx
G
dt
"nR
GL
(x
G GL
!x
G
)#

G
!x
G
,A

rN
&
>
,
i"1(1) N
A
!1. (A.3)
Remark. Assuming constant mixture volume inside the
reactor the total material balance (A.1) represents an
algebraic relation for the ow nR in the outlet of the
reactor. Since nR has been eliminated from the component
material balances the total material balance can be ne-
glected for the following considerations.
The corresponding eigenvalues are obtained from
a linearization around some steady-state according to
[det+df
V
!nI,"0] (A.4)
where f is the right hand vector in Eq. (A.3) and df
V
is the
corresponding Jacobian of f w.r.t. x. I is the identity.
Dierentiation of the right hand side in Eq. (A.3) yields
det+!nR
GL
I!
,A

I
rN
&
>
I.
#

!x
,A

I

dr
dx
'
N
&
>
!nI

"0 (A.5)
which is equivalent to

!nR
GL
!
,A

I
rN
&
>
!n

,A
det

I!

!x ,A
I

dr
dx
'
N
&
>
nR
GL
#,A
I

I
rN
&
>
#n

"0. (A.6)
This equation can be simplied using the identity det
+I!ab',"1!a'b for column vectors a, b (e.g. Munro
and Patel 1982, p. 362). Thus, Eq. (A.6) can be written as

!nR
GL
!
,A

I
rN
&
>
!n

,A`
;

!nR
GL
!
,A

I
rN
&
>
!n
#

!x
,A

'

dr
dx
N
&
>

"0, (A.7)
and the eigenvalues are readily obtained as

`
2
,A`
"!
nR
GL
#,A
I

I
rN
&
>
n
, (A.8)

,A
"!
nR
GL
#,A
I

I
rN
&
>
#(!x,A
I

I
)'

dr
dx
N
&
>
n
.
(A.9)
Hence, we conclude:
E All eigenvalues are real. Hopf bifurcations leading to
oscillatory behaviour are therefore not possible.
E According to the steady-state material balances the
rst N
A
!2 eigenvalues in Eq. (A.8) are always nega-
tive and therefore stable.
E Instead, the eigenvalue with the number N
A
!1 in Eq.
(A.9) can be either stable or unstable depending on the
functional expression for the reaction rate r and the
values of the operating parameters. In particular, this
eigenvalue can move from the left to the right half
plane or vice versa upon variations of the operating
conditions leading to real bifurcations and multiple
steady-states. It is a well-known fact that these so-
called kinetic multiplicities can occur for reactions
with autocatalysis or self-inhibition (Matsuura and
Kato 1967) like the etherication processes considered
in this paper. The critical boundary for multiplicity is
readily derived from Eq. (A.9) by substituting the cor-
responding rate expression. However, we will not carry
out this program here in detail.
Notation
a
G
liquid-phase activity of component i, dimen-
sionless
B molar bottoms ow rate, mol/s
D
K
distillate mass ow rate, kg/h
Da Damko hler number (Eq. (3)), dimensionless
F
K
feed mass ow rate, kg/h
K.-D. Mohl et al. /Chemical Engineering Science 54 (1999) 10291043 1041
df
V
Jacobian of f with respect to x
f right-hand vector (Eq. (A.4))
H column height, m
I identity matrix
k reaction rate constant, mol/(s eq(H>))
K
^
chemical equilibrium constant, dimensionless

O
volumetric reux, ml/s
n molar hold-up, mol
nR molar ow rate, mol/s
N
'
>
number of active sites, eq(H>)
N

number of components, dimensionless

p operating pressure, bar
Q heating rate, kW
r reaction rate, mol/(s eq(H>))
r
"
reaction rate at zero conversion,
mol/(s eq(H>))
R reux ratio, ("/D), dimensionless
t time, s
temperature, K
x state vector, dimensionless
x
'
liquid mole fraction of component i dimen-
sionless
Greek letters
ratio of reactants in the feed, ("x
`''
/x
''
),
dimensionless
ratio of reactive hydrocarbons in the feed,
("x
''
/x
''
#x
'"''
) dimensionless
porosity, dimensionless
eigenvalues, dimensionless

'
stoichiometric coecient of component i,
dimensionless
Superscripts and Subscripts
F related to the feed
B related to bottoms product
related to top product
related to liquid phase
in inlet
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