Ind. Eng. Chem. Res.

1993,32, 2767-2774

2767

Multiple Steady States during Reactive Distillation of

Methyl tert-Butyl Ether
S.A. Nijhuist
Chemical Engineering Department, University of Amterdam, Nieuwe Achtergracht 166,
The Netherlands

1018 WV Amsterdam,

F,P. J. M. Kerkhof and A. N. S. Mak'

Comprimo Engineers & Contractors, P.O.Box 58026, 1040 HA Amsterdam, The Netherlands
This paper presents results of computer simulations of the synthesis of methyl tert-butyl ether
(MTBE) in a fixed-bed reactor and in a reactive distillation column. These calculations clearly
showed the advantages of MTBE synthesis in a catalytic distillation tower. Furthermore, the
computer simulations showed that multiple steady states may occur in the reactive distillation
column during MTBE synthesis in a broad range of operating conditions. An analysis of some
sensitivity studies is presented.
1. Introduction
Gasoline lead phase-out has stimulated the production
of ethers like MTBE (methyl tert-butyl ether), TAME
(tert-amyl methyl ether), and others (e.g., Short, 1986;
Unzelman, 1989). Blended in the gasoline pool, these socalled octane boosters increase the octane number of
gasoline and decrease carbon monoxide emissions. At
present, the world MTBE production capacity is sharply
increasing and it is expected that in 1993 17 X 106 tons will
be produced worldwide, which is almost twice as much as
the 1990 MTBE production capacity.
The most commonly used production for MTBE is based
on the liquid-phase chemical reaction between methanol
and isobutene in a fixed-bed reactor. The above-mentioned reaction is acid catalyzed, and the majority of the
production processes use a strong-acid ion-exchange resin
as a catalyst. The catalytic reaction
CH,OH
methanol

+ (CH,),C=CH,
isobutene

H+

(CH,)COCH,
MTBE

between methanol and isobutene to MTBE has the

following characteristics:
1. The reaction is exothermic (A",= -37.7 kJ/mol)
and the maximum conversion is determined by a thermodynamic equilibrium value.
2. The reaction is selective to isobutene; i.e., other
butenes are not converted and almost no byproducts are
formed.
3. The vapor-liquid equilibrium behaves nonideally;
i.e., relatively large activity coefficients can be obtained.
Liquid-phase separations, however, do not occur.
In a conventional MTBE production process (e.g.,
Ancillotti et al., 19871, methanol, a mixture of butenes,
and a cooled recycle stream are fed to a fixed-bed reactor
consisting of a strong-acid ion-exchange resin. The net
product stream of this reactor consists of unconverted
methanol and isobutene, MTBE, and the inert other
butenes which are separated by distillation and extraction.
The isobutene from the distillation column and the
methanol from the extraction column are recycled to the

* To whom correspondence should be addressed.

+ Present address: University of Twente,Faculty of Chemical

Technology,P.O. Box 217,7500 AE Enschede,The Netherlands.

reactor feed stream. In a catalytic distillation unit both

the chemical reaction and distillation occur simultaneously
in a packed or tray column (see Figure 1). This combination offers potential advantages over the above-mentioned fixed-bed and subsequent distillation system,
including the following: use of the heat of reaction for
product separation; a relatively easy controllable temperature profile in the catalytic section, i.e., no cooling
required and no occurrence of hot spots; lower operating
costs due to higher obtainable conversions (see, e.g,
Kerkhof et al., 1991), because thermodynamic equilibrium
limitations are avoided due to in situ product separation;
lower capital cost due to less equipment.
At present some commercial catalytic distillation processes are operated using a distillation tower packed with
bales of glass wool in which the catalyst is embedded
(Lander et tal., 1983). Other kinds of packing, like acid
resins embedded in structured packing (DeGarmo et al.,
1992) can also be used as a suitable material.
Reactive distillation is the subject of an increasing
number of theoretical and experimental studies. The
following applications of this new unit operation can also
be considered hydrolysis reactions (e.g., deesterifications),
heterogeneous catalytic systems (e.g., etherification, alkylation), and metathesis reactions.
The combination of reaction and distillation in a single
process step may be hampered by a number of complex
interactions. Simulation studies may help to determine
the influence of feed locations, the reflux ratio, and the
amount of catalyst on the overall conversion and product
purities and to optimize column performance. In the
following, results will be presented of computer simulations
of MTBE synthesis in a fixed bed and in a reactive
distillation column.
2. Simulation Basis
2.1. Feed Specifications and Physical Properties.
The simulations of the catalytic distillation column (CDC)
and the fixed-bed reactor (FBR) were executed using the
commercially available flowsheeting package ASPEN
PLUS licensed by ASPEN TECH (ASPEN, 1988).
As a basis for the simulations of the catalytic distillation
column (CDC) and the fixed-bed reactor (FBR), it will be
assumed that 197 mol/s (500 000 metric tons/year) MTBE
is produced. Furthermore, it will be assumed that the

0SSS-5SS5/93/2632-2767~04.00/00 1993 American Chemical Society

2768 Ind. Eng. Chem. Res., Vol. 32, No. 11, 1993
Table I. Feed and Operating Conditions (Design Cases)
Used for the Computer Simulations of the Catalytic
Distillation Column (see Figure 1) and the Fixed-Bed
Reactor (FBR)
CDC
FBR
feed
methanol
methanol
quantity
(liq)
C 4 O (vap)
(liq)
C4 (liq)
units
Fi
206
549
206
549
mol/s
T
320
350
343/353
343/353 K
P
11
11
50
50
bar
feed stage
10
9/10/11b
W
6400
6400
kg
R,
7
B
197
mol/s
a

35.6% isobutene, balance n-butene. Split: 30-30-40.

Table 11. Coefficients Which Can Be Used To Calculate

the Binary UNIQUAC (Reid et aL, 1977) Interaction
Parameters 7u = exp(Au/T) (from Rehfinger et ab, 1991)
Ai?
value
Ai?
value
A12
35.38 K
A23
-52.20 K
A13
88.04 K
A31
-468.76 K
A21
-706.34 K
A32
24.63 K
MeOH = 1; isobutene = 2; MTBE = 3.

reactor feed streams consist of a slight stoichiometricexcess

of pure methanol and a binary mixture of isobutene (35.6
mol 5%) and 1-butene. This butene mixture can be
regarded as a simplification of a FCC butene stream
assuming that the C i s like trans-2-butene, cis-2-butene,
and butanes do not significantly change the physical and
chemical behavior of the isobutene and 1-butene mixture.
This also implies that the methanol, isobutene, 1-butene
mixture can be regarded as a pseudobinary system. In
Table I a summary is presented of the input variables, i.e.,
amount of catalyst, feed streams, temperature, pressure,
and feed stage, which were provided to the program
package.
As mentioned in section 1,a liquid mixture of butenes,
methanol, and MTBE behaves strongly nonideally (see,
e.g., Alm and Ciprian (1980) and Colombo (1983)). As a
result of this nonideality, a minimum boiling azeotrope
occurs for the binary methanol/MTBE and the pseudobinary methanollbutenes system. The azeotropic compositions also depend on the system pressure.
For the description of liquid-phase and gas-liquid
interactions, the UNIQUAC (Reid et al., 1977) method
was used while gas-phase interactions were modeled using
the well-known Redlich-Kwong equations (property set
Sysop 11of the ASPEN PLUS program package). In Table
I1 the UNIQUAC parameters are presented which were
used by Rehfinger and Hoffmann (1990) to describe the
kinetics of the MTBE reaction (see section 2.2). These
kinetics were used in our simulations, and it will be obvious
that we applied, therefore, the same interaction model as
the above-mentioned authors. General thermodynamic
data were obtained from the DIPPR data bank (ASPEN,
1988).
2.2. Reaction Kinetics and Diffusion Limitations.
During the computer simulations, the reaction kinetics of
the liquid-phase reaction between methanol and isobutene
dissolved in 1-butene, presented by Rehfinger and Hoffmann (1990) were applied:

where r represents the reaction rate per unit catalyst mass,

q is the amount of acid groups on the resin per unit mass
(4.9 equiv/kg), and a is the activity of a component.

Table 111. Thermodynamic Equilibrium Constant K. and

Reaction Rate Constant k. as a Function of Temperature T
k, = 3.67 X 10l2 e-lllloITmol/@equiv)
K, = 284 exp[f(T)I

($- $)+ c2 log( i)+

f(T) = c1

c3(T - To) c , ( p

c,(P- 2';)

- T:) +

+ c,(P- Tt)

To = 298.15 K
~1

= -1493K; ~2 = -77.4; ~3 = 0.508K-l;

~4 = -0.913 X 1 W P ,cs =
1.11X 10-BK4; cg -0.628 X IO%-'

In Table I11 the temperature dependencies of the

reaction rate constant k, and the thermodynamic equilibrium constant K, are presented.
In section 1it was stated that the acid-catalyzed reaction
between methanol and isobutene is selective and that
almost no byproducts are formed. This is only valid if
mass-transfer rates are determined by the reaction rate
itself. If the rate of methanol transfer inside the pores of
the particles to the acid sites of the resin is the ratedetermining step, large MTBE formation rates can be
obtained but the byproduct diisobutene will also be formed.
If the transfer rate of isobutene is rate limiting, low reaction
rates will be obtained. Rehfinger and Hoffmann (1990)
defined two parameters 4 and 4~ which determine the
influence of diffusion limitations on the effective reaction
rate:

(3)
In eqs 2 and 3 d, is the particle diameter, p, is the density
of the of catalyst particles, ct is the total concentration of
e ~effective
~
diffusion coefficient of
the liquid, D e ~is the
methanol inside the pores of the particles, and Deois the
limiting diffusion coefficient of methanol in isobutene. It
should be noted that the effective diffusion coefficient
depends on liquid composition and pore sizes as was shown
by Rehfinger and Hoffmann (1990). If in eqs 2 and 3 the
value of 4 < 0.5 and the value of 4~ > 0.001, the reaction
rate will not be limited by particle diffusion.
2.3. Simulationof the Fixed-BedReactor. Assuming
plug flow, a mass balance of the reactants over a differential
slice of the reactor results in

ax,

(4)

where L is the reactor length, r is the reaction rate per unit

of catalyst mass, W is the catalyst weight and Fi is the
molar feed rate of component i. With eq 4 the conversion
Xi of reactant i can be calculated as a function of the
distance z from the reactor inlet if this reactor is operated
isothermally. If a heat balance is applied to a differential
slice of the reactor, one obtains

where U denotes the overall heat-transfer coefficient, A

is the heat-transfer area, T is the temperature in the
reactor, and T , is the reactor wall temperature.
If in eq 5 the heat-transfer term UA(T - T,) is
considered, the following equalities are valid in case the
reactor is operated:

Ind. Eng. Chem. Res., Vol. 32, No. 11, 1993 2769
isothermally

aTia(ziL)= o

countercurrently cooled

d(F C T
aziL

= AU(T - T,) (6)

where F,and C, denote the coolant flow and heat capacity,

respectively.
Assuming plug flow and countercurrent separate flow
of coolant and reactants, the concentration and temperature profile in the reactor can be obtained if eqs 4-6 are
solved simultaneously using the appropriate reaction
kinetics.
2.4. Simulationof the Catalytic Distillation Tower.
In order to calculate the concentration profile, reaction
rates, and the temperature profile in the CDC column, it
was assumed that the column consisted of 17 equilibrium
stages. A schematic representation of the column used
for the simulations is plotted in Figure 1. Figure 1shows
the following three sections of the catalytic distillation
unit: a rectification zone in the top section, stages 1-3; a
reactive distillation zone in the middle section, stages 4-11;
a stripping zone in the bottom, stages 12-17 (including
reboiler).
The simulations of the CDC were performed using the
RADFRAC block with user-supplied reaction kinetics.
This program block solves the following set of equations
(Venkataraman et al. 1990) associated to any stage j in
the distillation column:

methanol

2
3
4

-+

methanol
-

Cpix

13
14
15
16

Figure 1. Schematic representation of the configuration of the CDC

used during the computer simulations. The stage numbers in this
figure refer to the rectification zone, stages 1-3; reactive distillation
zone, stages 4-11; and stripping zone, stages 12-17.

component material balances

1-00 I

virjwj3 = 0 (7)
where Lj denotes the molar liquid flow rate, Gj is the molar
gas flow rate, Jj is the amount of catalyst on stage j (W
= 0 outside reactive section of the column) and vi is the
stoichiometric coefficient of component i;
phase equilibrium equations
I

0.00

0.00

0.20

0.40

0.60

0.80

1.00

where Kij denotes the phase equilibrium ratio of component i at stage j ;

enthalpy balances

Figure 2. Isobutene conversion X plotted against dimensionless

length z/L at two different temperatures in an isothermally operated
fixed-bed reactor. The lines in this figure were calculated by the
ASPEN PLUS program package using the RPLUG block with user
supplied kinetics (eq 1). The reactor operating and feed conditions
used for the simulations are presented in Table I.

estimated and calculated values of the unknown physical

quantities had a value lower than 10-4.
where Jij and H G j denote the enthalpy of the liquid and
gas mixture on stage j , respectively. The elemental
reference state is used for the calibration of the enthalpies
of the mixtures, and thus the heat generated by the
chemical reaction does not appear in eq 9.
Equations 7-9 are equal to the basic equations used for
the calculation of the temperature and concentration
profile in a distillation column except for the fifth term
in eq 7, which is a consumption/production term resembling the chemical reaction occurring on stage j . The set
of equations represented in eqs 7-9 combined with eq 1,
the reaction rate equation, are solved iteratively by the
ASPEN PLUS program package. During our calculations,
convergence was assumed if the relative error between

3. Fixed Bed Reactor Simulation Results

In Figure 2 the isobutene conversion X is plotted against

the dimensionless reactor length zJL at two different
temperatures T. The lines in Figure 2 were calculated by
the ASPEN PLUS program package assuming isothermal
operation of a FBR and using the RPLUG block with
user-supplied kinetics (eq 1). The reactor operating and
feed conditions are represented in Table I. A reactor
operating pressure of 50 bar is used in order to stay below
the boiling point of the reaction mixture at any condition.
Figure 2 clearly shows that, in a fixed-bed reactor, the
isobutene conversion X is limited by its thermodynamic

2770 Ind. Eng. Chem. Res., Vol. 32, No. 11, 1993

1.00

[mrnol/s kg]

X
0.75

0.50

CASE A

I '

4, C A S E B

0.25

0.0ot " ' I " " I ' ' ' " "
0 1 2 3 4 5 6 7 8 9 1011121314151617
0.00

0.00

b.20

b.10

b.38

0.40

0.5b

4b8

0.00

~~

49-

0.20

b.40

b.68

8.8b

2
-

1.W

L
Figure 3. (a, top) Isobutene conversion X and reaction rate r againat
dimensionlees reactor length z/L. The lines in this f i e were
calculated by the ASPEN PLUS program package using the RPLUG
block with user supplied kinetics (eq 1). The reactor operating and
feed conditions used for the simulations are represented in Table I.
Furthermore, it was assumed for the calculations of the abovementioned profies that the reactor was countercurrently cooled with
cooling water (cooling water flow 10 kmol/s, UA = 600 kW/K). (b,
bottom) Reactor temperature and cooling water temperature profile
against z/L. The lines in this figure correspond to the case described
in the caption of part a.

equilibrium value. Furthermore, Figure 2 shows that this

equilibrium value decreases with increasing values of the
reactor temperature T.
In Figure 3a the isobutene conversionX and the reaction
rater are plotted against zlL in the case where the reactor
is cooled countercurrently. The lines in Figure 3a were
calculated by the ASPEN PLUS program package using
the RPLUG block with user-supplied kinetics (eq l),and
the operating data are presented in Table I and in the
caption of Figure 3a. In Figure 3b the corresponding
profiles of the reactor temperature and the cooling medium
temperature are presented. Figure 3 shows that in a
countercurrently cooled reactor hot spots may occur which
result in a relatively low value of the isobutene conversion
and in a decrease of the selectivity of the reaction (see
section 2.3). In practice, therefore, MTBE reactors are
operated with a recycle flow causing smooth temperature
and reaction rate profiles. However, the obtainable
isobutene conversion value in a recycle reactor is limited.
Clearly, the above-mentioned simulation results show the
benefits of the use of a catalytic distillation column for
the synthesis of MTBE, i.e., high obtainable conversions
and smooth operation.
4. Catalytic Distillation Column Simulation
Rasults
As mentioned in section 1, the intention of this study
was to investigate the influence of reflux ratio, catalyst

STAGE NUMBER

Figure 4. Isobutene conversion X as a function of location of

methanol feed stage. The solid line in this f i e refers to the highconversion case (case A). The dashed line in thie f i e refera to the
low-conversion case (case B). Both cases were obtained with equal
feed conditions but with different initial Conditions (seesection 4.1).
The dots in this figure refer to the design case (see Figures 6 and 6
andTable1). BothlinesinthiefiiewerecalculatedwiththeASPEN
PLUS program package and usingeq 1as a user-supplied production/
consumption term on an equilibrium stage.

weight, and location of the methanol feed stream upon

the column operating temperture and isobutene conversion. The location of the butene feed stream at the bottom
trays is determined by ita relatively low volatility.
The followinginitial values were supplied to the ASPEN
PLUSprogram package: composition bottom stage, X ~
= 0.95 and X M ~ O H= 0.05; bottom temperature 420 K; top
temperature 350 K. The compositions of the intermediate
stages are set by the program and are equal to the
composition of the bottom stage. The temperatures of
the intermediate stages are calculated by the program by
linear interpolation between the top stage and the bottom
stage. With these initial values, the program starts the
iteration procedure and proceeds until convergence (see
section 2.4) is obtained.
4.1. Influence of Methanol Feed Stage Location.
When the influence of the location of the methanol feed
stage on isobutene conversion was investigated, no convergence was obtained using the above-mentioned initial
values if methanol was fed to stage 10. Therefore, we
decided to use the following iterative procedure. First
the column temperature and concentration profile were
calculated with the methanol feed point located at stage
1. Then the values obtained from this simulation were
used as initial values for the calculations with the methanol
feed point located at stage 2 using the same operating and
feed conditions as in the previous simulation. The
concentration and temperature profile thus obtained were
used for the simulation with the methanol feed point at
stage 3 and so on until stage 10. This procedure will be
referred toas case A. Avery interestingresult wasobtained
when the above-mentioned procedure was reversed, i.e.,
the column concentration and temperature profile were
calculated with the methanol feed located at stage 17which
were then used to calculate the concentration and column
profile with the methanol feed at stage 16 and so on. With
this procedure, steady-state concentration and temperature profiles totally different from the profiles of case A
were found. These steady-state profiles will, therefore,
be referred to as case B.
The resulting isobutene conversions obtained by the
above-mentioned procedures are plotted as a function of
the methanol feed location in Figure 4. Figure 4 shows
that, a t least, two steady states can exist in a CDC column,
i.e., a high-conversion steady state (case A, solid line) and
a low-conversion steady state (case B, dashed line).

Ind. Eng. Chem. Res., Vol. 32, No. 11, 1993 2771

m methsnol 0I-butene

MTBE

0n-butene

1.00

methanol

0I-butene

0n-butene

MTBE

1.00

0.75

0.75

0.50

0.50

0.25

0.25

0.00

0.00

0 1 2 3 4 5 6 7 8 9 1011121314151617

1 2 3 4 5 6 7 8 9 1011121314151617

STAGE NUMBER

STAGE NUMBER

T
K

440
420
400

400

STAGENUMBER

380
360

340' " ' ' ' ' ' ' '

' '
"
0 1 2 3 4 5 6 7 8 91011121314151617
I

'

'

STAGE NUMBER

340' I ' '

"
"
'
'
'
0 1 2 3 4 5 6 7 8 91011121314151617
I

'

'

'

STAGE NUMBER

Figure 5. (a, top) Mole fractions of the different components in the

catalytic distillation column against the columnstage number. Each
bar pattern in this figure represents a calculated value of the mole
fraction x of a component at steady state, and refers to design case
A (see Table I for operating conditions). (b,bottom) temperature
Tand reaction rate r in the catalytic distillation column corresponding
to the tray compositions represented in part a.

Figure 6. (a, top) Mole fractions of the different components in the

catalytic distillation columnagainst the columnstage number. Each
bar pattern in this figure represents a calculated value of the mole
fraction x of a component at steady state, and refers to case B (see
Table I for operating conditions). (b, bottom) Temperature T and
reaction rate r in the catalytic distillation column correspondingto
the tray compositions represented in part a.

Furthermore, by following the arrows, it can be obtained

from Figure 4 that by varying the methanol feed location
(with very small nondiscrete steps) hysteresis occurs; i.e.,
case A disappears and only case B is obtained if the feed
location is lowered to below stage 11 while the opposite
happens if the feed location is heighten to above stage 9.
Again it should be noted that both cases were obtained
using the feed and operating conditions presented in Table
I.
Also note that the isobutene conversion X in Figure 4
is practically equal to the MTBE mole fraction in the
column bottom product since there is a negligible amount
of MTBE present in the top of the column. In Figure 5a
the composition of the liquid on each tray resulting from
the simulation of the reactive distillation between methanol and isobutene is plotted. The values of the mole
fractions x of the four different components in the liquid
phase presented in this figure refer to the high-conversion
case (case A) and were calculated with the methanol feed
located at stage 10. Figure 5a shows that the major part
of the top and the reactive section of the column consists
of n-butene and that the bottom part consists of MTBE.
In Figure 5b the temperature profile and the reaction rate
in the CDC column are plotted, which correspond with
the concentration profile presented in Figure 5a. This
figure shows that the temperature of the reactive zone has
a relatively low value which results in a relatively large
obtainable equilibrium conversion value of isobutene.
Furthermore, it can be seen in Figure 5b that the values
of the reaction rate in the reaction section are always
positive. In Figure 6, the low-conversion (case B) con-

centration, temperature, and reaction rate profiles are

plotted. Figure 6a shows that in this case the major part
of the reaction zone consists of methanol and MTBE. As
a consequence, the temperature of the reaction section in
the column is much higher compared to case A (Figure 5a)
and as a result lower equilibrium conversion values are
obtained (Figure 4). Figure 6a also shows that no
separation of methanol and MTBE occurs in the bottom
section.
4.2. Influence of Reflux Ratio. The influence of the
reflux ratio R, upon the isobutene conversion X in the
CDC column was determined by varying this ratio in the
domain 0.2 IRr I10. For each value of R, the steadystate column concentration and temperature profiles were
calculated using, as initial values, the concentration and
temperature profiles of case A and case B, respectively.
In Figure 7 the overall isobutene conversion X is plotted
against the reflux ratio Rp Figure 7 shows that both the
high-conversion case (case A indicated by the solid line)
and a low-conversion case (case B indicated by a dashed
line) still occur in a large range of Rr values. For case A
the conversion to isobutene is large and practically
independent of the reflux ratio, provided R , exceeds a
minimum value 4. If R, < 4 only case B was obtained. For
the low-conversion case, Figure 7 shows that X first
increases and then decreases with increasing values of R,.
In Figure 8, concentration, temperature, and reaction
rate profiles in the CDC column are presented, which were
obtained with a value of R, = 10 and which refer to case
B. Figure 8a showsthat in spite of the low overallisobutene
conversionvalue which was obtained in the column, MTBE

2772 Ind. Eng. Chem. Res., Vol. 32, No. 11, 1993
100

CASE A

75

50

25

0 '

'

0.0

I "

"

2.5

'

'

"

'

"

5.0

'

"

'

'

7.5

'
10.0

0.25

CASE B

ti

o . o o " " " " " " ' " ' ' ' " ' ' ' ' ~
0

R,

methanol

0isobutene

MTBE

0n-bulene

0.40
0.20
0.00
0 1 2 3 4 5 6 7 8 9 1011121314151617
STAGE NUMBER

T
K

380

360
340

10

10' kg

Figure 7. Isobutene conversion X as a function of reflux ratio R,.

The solid line in this figure refers to the high-conversion case, case
A, and the dashed line in this figure refers to the low-conversioncase,
case B. The lines in this figure were calculated by the ASPEN PLUS
program package using the RADFRAC block option with usersupplied production terms (eq 1)on catalyst containing equilibrium
stages. Other operating and feed conditions used during the
simulation are presented in Table I. The dots in this figure refer to
the design cases A and B (see Figures 5 and 6) which were taken as
a start of the parameter sensitivity study.

Figure 9. Isobutene conversion X as a function of total amount of

catalyst Win the column. The solid line in this figure refers to the
high-conversioncase, case A, and the dashed line in this figure refers
to the low-conversion case, case B. Both lines in this figure were
calculated with the methanol feed at stage 10. The dots in this figure
refer to the design cases A and B (see Figures 5 and 6) which were
taken as a start of the parameter sensitivity study.

4.3. Influenceof Amount of Catalyst. The influence

of the amount of catalyst Won the trays in the CDC column
upon isobutene conversion was determined using a procedure similar to that described in section 4.2.
In Figure 9 X is plotted as a function of the total catalyst
weight Win the CDC. Figure 9 shows that starting from
the base case (W = 6400 kg), increasing the amount of
catalyst does have a small effect on the conversion of both
case A (solid line) and case B (dashed line). If one follows
the arrows in the direction of decreasing values of W, the
conversion of case B first increases until W = 800 kg after
which the conversion decreases until a zero conversion at
W = 0. Figure 9 also shows that multiplicity starts to
occur at W 700 kg. This rules out that multiplicities are
a result from vapor-liquid nonidealities alone.
It should be noted that if the value of W is relatively
low (<4000 kg), large reaction rates per kilogram of catalyst
are obtained because the chemical reaction is far from
equilibrium. These large reaction rates can only be
obtained if the reaction is not limited by particle diffusion,
in other words if 4 < 0.5 (eq 2) and $A > 0.001 (eq 3). Using
eqs 2 and 3, we found that if the CDC column contained
6400 kg (case A, Figure 5 ) of catalyst (800 kg/tray), the
maximum particle diameter was calculated to be 280pmin
order to avoid particle diffusion limitations and thus the
formation of byproducb. This is already a relatively small
diameter considering that a commercially available ionexchange resin has particle diameters ranging from 100 to
1200 pm. The maximum value of the particle diameter
in a CDC containing 1500 kg of catalyst was calculated to
be 75 pm.
The dashed line in Figure 9, which refers to case B,
shows that X decreases if the amount of catalyst in the
column is increased. This phenomenon is due to the fact
that a small amount of catalyst causes low decomposition
rates of MTBE and thus higher conversion values. In
general, the influence of the amount of catalyst in the
column is almost negligible if W > 2000 kg and if particle
diffusion limitations are not considered.

1
0 1 2 3 4 5 6 7 8 9 1011121314151617

STAGE NUMBER

Figure 8. (a, top) Mole fractions of the different components in the

catalytic distillation column against the column stage number. Each
bar pattern in this figure represents a calculated value of the mole
fraction r of a component at steady stateand refers to case B. During
the calculations a reflux ratio value of 10 was assumed, keeping the
other design conditions constant (see Table I). (b, bottom) Temperature 5" and reaction rate r in the catalytic distillation column.
The lines in this figure refer to case B at a reflux ratio value of 10.

is present in substantial amounb on the upper trays. This

low-conversion value is caused by the relatively large
temperature of the bottom trays which causes the formed
MTBE to decompose. This can also be seen in Figure ab,
which shows that the positive area of the reaction rate
curve almost equals the negative (decomposition) area.
The net result is an almost zero conversion.

5. Discussion

The results of the simulations show that, for identical

column feed flows, reflux ratios, and catalyst weights, two
different steady states can exist during reactive distillation
of MTBE, i.e., a high (caseA) and a low (case B) conversion
state. Furthermore, it was shown in the previous section

Ind. Eng. Chem. Res., Vol. 32, No. 11, 1993 2773
T
K

420

415

410

405

0.00

0.25

0.50

0.75
4

1.00
m

Figure 10. Gas-liquid equilibrium of the methanoVMTBE mixture

as a function of temperature T a t a pressure of 11bar. The lines in
this f i e are calculated using the UNIQUAC group contribution
method (see Table 11) for liquid-phase activities and the Antoine
formula for vapor pressures.
Table IV. Operating Conditions and Feed and Product
Flow Compositions of Case A and Case B, Calculated Using
the Feed and Operating Conditions Presented in Table I
case A
case B
'cold state"
'hot state"
property
top bottom top bottom units
0.04 0.00
0.02 0.56
X W H
0.01 0.00
0.25 0.00
xm
XbslgE
~*but.o.

T
product flows
Q (duties)

X
T (range in reactive zone)
T (mean in reactive zone)
K. (at mean 27
Lo(reflux flow)

0.00
0.95
348
366
49.7

0.98
0.02
424
197
35.1

98.5
350-357
352
24.4
2.6

0.00 0.41
0.73
349
478
64.1

0.03
406
197
53.7

41.4
354-391
375
9.9
3.3

K
moUs

MW
%

K
K
km0VS

that the occurrence of either case depends on the initial

state of the column and that by changing operating
conditions it is possible to jump from one state to another.
In Table IV, operating conditions and feed and product
flow compositions of case A and case B are presented,
which were calculated using the feed and operating
conditions presented in Table I. Table IV shows that in
case A relatively large values of the isobutene conversion
X (and thus the MTBE bottom mole fraction XMTBE) are
obtained and that the temperature of the reactive section
is relatively low. Case B in Table IV shows the opposite
characteristics, Le., relatively low conversion and high
temperatures in the reactive zone. Table IV also shows
that the equilibrium constant Ka drops 40% due to a
temperature increase of 23 "C.
Possible phenomena responsible for the multiple steady
states can be the nonideality of the liquid mixtures or the
presence of a chemical equilibrium reaction in the column.
In Figure 10the T-x-y diagram of the methanol/MTBE
system is presented. Figure 10clearly shows the methanol/
~ = 0.57.
E
The case B column
MTBE azeotrope at X
concentration profile presented in Figure 6a shows that,
indeed, the column bottom section operates at this
azeotropic composition. However, from the dashed line
(case B) in Figure 4 it can be seen that by increasing the
location of the methanol feed tray, the conversion X and
thus the bottom MTBE mole fraction increases to values

far beyond the azeotropic methanol/MTBE composition.

This means that the above-mentioned azeotrope is not an
explanation for the existence of multiple steady states in
a CDC.
Figure 9 shows that, for both case A and case B, the
isobutene conversion X becomes almost independent of
the catalyst weight W, if the amount of catalyst exceeds
a minimum value. This means that the CDC operates
close to chemical equilibrium for both cases and that the
multiple steady states are not caused by the presence of
a chemical reaction, i.e., kinetic limitations.
A much better explanation of the existence of multiple
steady states is that this phenomenon is caused by a
combination of physical separation and the presence of a
exothermic chemical equilibrium reaction inside the
column. This can be seen from Figures 4-6. Figure 5
shows that, at the high-conversion state, butenes are
present throughout the column resulting in relatively low
temperatures on the reactive stages. Figure 6 shows that,
a t the low-conversion state, methanol and MTBE are
present on the reactive stages resulting in relatively high
temperatures on these stages.
As the reaction of methanol and isobutene to MTBE is
exothermic and conversion is limited by thermodynamic
equilibrium, high temperatures on the reactive stages will
lead to low Ka values (see Table IV) and thus to lowconversion values whereas low temperatures will result in
high values of X which explains the occurrence of a lowconversion state and a high-conversion state.
Figure 4 can also be explained by the above-mentioned
assumption, i.e., that the exothermicity of the reaction is
responsible for the existence of multiple steady states. If
the arrows on the solid line (case A) are followed, it can
be seen that if methanol is fed below stage 11, the last
reactive stage, conversion drops immediately. The reason
for this jump is that methanol displaces the butenes in the
column bottom section, causing a temperature increase.
The opposite effect is encountered for case B when the
location of the methanol feed stage is moved upward. Now
the butenes start to displace the methanol in the column
bottom section, thereby lowering the temperature and
increasing conversion. The jump to case A is made when
all the methanol in the bottom of the column is replaced
by butenes. A further understanding of the multiple
steady states during reactive distillation of MTBE might
be obtained if so-called residue curves (see, e.g., Barbosa
and Doherty (1988))are made.
A final remark has to be made about the values of the
reflux and reboiler duties presented in Table IV. It may
be expected that the difference between these two duties
will be equal to the sum of the heat released by the chemical
reaction and the heat of vaporization of the butene feed
as this is completely vaporized. For this reason, it may
also be expected that for the high-conversion case A the
reflux duty will be larger than that for case B as in case
A muchmore heat will be released by the chemical reaction.
As can be seen in Table IV the opposite is true; Le., case
B has larger reflux duties than case A. This can be
explained if the stoichiometry of the chemical reaction is
considered. As 1mol of methanol and 1mol of isobutene
form 1 mol of MTBE, lower conversion values on the
reactive stages will lead to larger vapor flows inside the
column (bottom molar flow rate was fixed during the
simulations). This means that reflux and reboiler duties
can be larger at low isobutene conversions although less
heat is generated by the chemical reaction compared to
the high-conversion case.

2774 Ind. Eng. Chem. Res., Vol. 32, No. 11, 1993

6. Conclusions

Calculations of the concentration profiles and the

temperature profile at reactive distillation of MTBE
showed that at least two types of steady states may occur:
a high isobutene conversion state with a relatively low
temperature in the reactive section; a low isobutene
conversion state with a relatively high temperature in the
reactive section.
At the high-conversion state the isobutene conversion
X increases with increasing amounts of catalyst in the
column until a limiting value is reached and is independent
of the reflux ratio R, provided R, > 4.
At the low-conversion state the isobutene conversion X
decreases with increasing amounts of catalyst and initially
increases and then decreases with increasing values of R,.
The existence of the two steady states can be explained
by the simultaneous occurrence of physical equilibrium
of a multiphase mixture and an exothermic chemical
equilibrium reaction in the catalytic distillation column.
The simulations show that it might be feasible to install
more than one methanol feed location on a CDC in order
to avoid or to overcome an unwanted steady state caused
by, e.g., column misoperation.

Acknowledgment
The authors would like to thank Prof. R. Krishna for
his valuable advice.
Nomenclature
ai = liquid-phase activity of component i
A = heat-transfer area, m2
B = product flow rate at the bottom of the column, mol/s
ci = liquid concentration of component i, mol/m3
ct = total liquid concentration, mol/m3
C, = heat capacity, J/(mol K)
E, = activation energy, J/mol
d, = particle diameter, m
De,MeOH = effective binary diffusion coefficient of methanol
inside the pores of the resin, m2/s
Deo = effective limiting diffusion coefficient of methanol in
isobutene, m2/s
Fi = molar flow rate of component i, mol/s
F, = molar flow rate of coolant, m o b
Gj = molar gas flow rate from stage j , mol/s
H = enthalpy, J/mol
AH, = reaction enthalpy, J/mol
k = first-order reaction rate constant, m3/(s kg of catalyst)
k, = reaction rate constant, mol/@equiv)
K = phase equilibrium ratio
K, = thermodynamic equilibrium constant
L = reactor length, m
Lj = molar liquid flow rate from stage j , m o b
q = moles of acid groups per unit mass of ion-exchangeresin,
equiv/kg
Q = duty, W
r = reaction rate, mol/(s kg)
R = gas constant, J/(mol K)
R, = reflux ratio
T = temperature, K
T, = reactor wall temperature, K
T,= critical temperature, K

U = heat-transfer coefficient, W/(m2 K)

W = catalyst weight, kg
= mole fraction of component i in the liquid phase
X = isobutene conversion
yi = mole fraction of component i in the gas phase
z = axial distance from reactor inlet, m
xi

Greek Letters

v = stoichiometric coefficient
pp =

density of the catalyst, kg/m3

9 = dimensionless parameter defined in eq 2
$A = dimensionless parameter defined in eq 3
Subscripts

G = gas phase
i = component number
IB = isobutene
j = stage number
L = liquid phase
MeOH = methanol
MTBE = methyl tert-butyl ether

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Received for review November 20, 1992
Revised manuscript received July 12, 1993
Accepted July 27, 1993.
Abstract published in Advance ACS Abstracts, October 1,
1993.
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