Dehydration of Methanol to Dimethyl Ether by
Catalytic Distillation
Weizhu An, Karl T. Chuang* and Alan R. Sanger
Department of Chemical and Materials Engineering, University of Alberta, Edmonton, AB Canada T6G 2G6
D
imethyl ether (DME) is a key intermediate in methanol to
gasoline (MTG) and methanol to olen (MTO) processes (Chang
1983, 2000). DME has several properties that make it attractive
as a fuel or fuel additive for automobile engines (Fleisch et al., 1997;
Kikkawa and Aoki, 1998). The physical properties of DME are similar to
those of LPG. The weight-based heating value of DME is higher than
that of methanol. The gaseous volume-based heating value is higher
than that of methane. The cetane number is between 55 and 60, and
is higher than those of diesel fuels. Moreover, DME is non-toxic and
reacts quickly in the atmosphere to form CO2 and water. DME is an
ultra-clean alternative fuel that contains no sulfur or nitrogen (Fleisch
et al., 1997; Adachi et al., 2000; Muller et al., 2000). Presently, DME
is also used as feed for the synthesis of chemicals including acetic acid
and its esters and other chemicals, as a hydrogen source for fuel cells,
as a refrigerant, and as an aerosol propellant in the cosmetic industry
to replace environmentally harmful CFC propellants (Kikkawa and Aoki,
1998).
The potential use of DME as fuel for local power generation,
transportation and household gas requires the production of DME on a
large scale. Presently, the major process for the production of DME on
an industrial scale comprises dehydration of methanol using an acidic
dehydration catalyst in a xed bed reactor in the temperature range 523
to 673 K, followed by rectication of the product stream to recover high
purity DME (Bercic and Levec, 1993; Spivey, 1991).
Zeolites, silica/aluminas, alumina, metal phosphates and
sulfates, and ion exchange resins have been investigated as acidic
catalysts for alcohol dehydration. Among these solid acid catalysts,
ion exchange resins have the advantages that they require relative
low operation temperatures (303423 K) and show high selectivity
to DME (Spivey, 1991).
Direct synthesis of DME from synthesis gas, with co-production
of methanol, uses a physical combination of a methanol synthesis
catalyst, most commonly Cu, Zn and Al, or Cr catalyst, and a methanol
dehydration catalyst, such as -Al2O3 or other acidic catalysts (Haugaard
and Voss, 2001; Voss et al., 1999; Lewnard et al., 1990; Armbruster,
2000). However, the concentration of DME in the product stream
from a single reactor is not sufciently high for use as fuel grade DME,
and so further distillation of the liquid product is required to recover a
concentrated DME stream (Voss et al., 1999).
High purity DME, or a product mixture with a high DME
concentration, has higher commercial value than mixtures having a
low concentration of DME. Direct catalytic dehydration of methanol
* Author to whom correspondence may be addressed. E-mail address:
karlt.chuang@ualberta.ca
948
The kinetics of liquid catalytic dehydration of methanol
over an ion exchange resin (Amberlyst 35) has been
determined for the temperature range 343 to 403
K using a batch reactor. The experimental data
are described well by an Eley-Rideal type kinetic
expression, for which the surface reaction is the rate-
determining step. A catalytic distillation process for
methanol dehydration to dimethyl ether (DME) has
been modeled using the experimentally determined
kinetic data. The results were incorporated into the
rate-controlled reaction mode for RadFrac, a part of
the commercial simulation program Aspen Plus. It
was shown that synthesis of high purity DME can be
achieved using a single catalytic distillation column.
Thus there is signicant potential for reduction of
overall capital cost for a plant for methanol dehydra-
tion to DME when compared to conventional produc-
tion facilities that involve separate reaction and distil-
lation processes.
La cintique de la dshydratation catalytique liquide du
mthanol sur une rsine changeuse dions (Amberlyst
35) a t dtermine pour la gamme de tempratures
de 343-403 K laide dun racteur discontinu.
Les donnes exprimentales sont bien dcrites par
une expression cintique de type Eley-Rideal, pour
laquelle la raction de surface est ltape dterminant
la vitesse. Un procd de distillation catalytique pour
la dshydratation du mthanol en dimthylther
(DME) a t modlis laide de donnes de cintique
dtermines exprimentalement. Les rsultats ont t
introduits dans le modle de raction contrle par la
vitesse de RadFrac, qui fait partie du programme de
simulation commercial Aspen Plus. On montre que
la synthse du DME puret leve peut tre russie
avec une seule colonne de distillation catalytique.
Il a donc un potentiel signicatif pour la rduction
des cots globaux en capitaux pour une usine de
dshydratation de mthanol en DME, comparative-
ment des installations de production convention-
nelles, qui impliquent des procds de raction et de
distillation distincts.
Keywords: Dimethyl ether; catalytic distillation;
methanol dehydration to DME; ion exchange resin
catalyst; Eley-Rideal kinetics.
The Canadian Journal of Chemical Engineering, Volume 82, August 2004
to DME offers the prospect of a straightforward process for
production of DME. The foundations for this approach include
the availability of mature industrial processes for production
of methanol and known catalysts having high selectivity
for dehydration of methanol to DME. However, a separate
distillation apparatus is required to produce high purity DME
using present processes, which increases the overall capital and
operating costs.
Application of catalytic distillation (CD) methodology to
methanol dehydration offers advantages in operation, costs,
and quality of product when compared with conventional
processes (Nemphos and Hearn, 1997). The principles behind
application of CD are well established, and CD has been applied
successfully to several industrial processes, including production
of methyl acetate and synthesis of fuel ethers (Nemphos and
Hearn, 1997; Malone and Doherty, 2000; Taylor and Krishna,
2000). The catalytic reaction and separation processes typically
are performed in a single distillation column. The limitations
imposed by thermodynamic equilibrium of the reaction are
overcome by continuous removal of product from the reaction
zone. Combining reaction and separation processes within one
vessel reduces the overall capital cost compared with use of
separate vessels for each process.
A CD system for dehydration of methanol to DME described
by Nemphos and Hearn (1997) comprises contacting the stream
with a xed bed zeolite catalyst. However, ion exchanged resins
are preferred over acidic zeolites as catalysts for the methanol
to DME process because they require relative low operation
temperatures (303423 K) and show high selectivity to DME
(Spivey, 1991). In this paper we will describe the kinetics of
catalytic dehydration of methanol over the ion exchange resin
Amberlyst 35. Amberlyst 35 is preferred over the related resin
Amberlyst 15 because it has a higher tolerance to elevated
temperatures. The inhibition effects of reaction products such as
water on catalytic activity of acidic resin catalysts are alleviated
by separating them from the reaction zone in a CD column
(Aiouache and Goto, 2002a). The kinetic data then are used to
design and to model a CD process for production of DME. We
have determined the dependence of DME yield and purity on
several key design parameters, including operating pressure,
reux ratio, location of feed stage, total number of theoretical
stages, and catalyst loading. We will show that dehydration
of methanol to DME by catalytic distillation is more efcient
than conventional methanol dehydration processes, and that
Amberlyst 35 is superior to zeolites as catalyst in the CD process.
Synthesis of high purity DME can be achieved in a single CD
column, without the need for an additional separation unit,
resulting in signicantly reduced capital cost.
Experimental
Kinetics
Liquid phase catalytic dehydration of methanol was performed
in a 5 104 m3 stainless steel autoclave batch reactor
equipped with four-bladed Teon impellers. The stirrer speed
was 800 rpm in all experiments, at which speed the rate of
reaction was not inuenced by external mass transfer. Argon
was used as inert gas to purge the system and to provide an
initial reaction pressure of 0.82 MPa. To determine the effect
of concentration, o-xylene was used as inert solvent. For each
run, 4g catalyst and 120g solution were charged into the
reactor, which was then pressurized to 0.82 MPa and heated
to a selected temperature in the range 343403 K.
The Canadian Journal of Chemical Engineering, Volume 82, October 2004
Materials
A commercial cation ion exchange resin catalyst (DuPont,
Amberlyst 35 wet; Table 1) was dried and then used for the
kinetics experiments. Amberlyst series catalysts are divinyl
benzene/styrene copolymers with sulfonic acid functional
groups situated on the aromatic rings, which act as acidic
catalytic sites for the methanol dehydration reaction. The
catalyst was dried under vacuum at 358 to 363 K for 24 hours
to remove adsorbed water so as to determine the dry weight
before use. Methanol (Aldrich, 99.99%) and o-xylene (Aldrich,
anhydrous, 99%) were used as received.
Gas and Liquid Sample Analysis
An on-line GC equipped with a Porapak T column and TCD
(HP 5896 Series II) was used to analyze the gas phase and
liquid samples from reactors. A gas sampling port on the batch
reactor was connected to the GC using a short line heated with
heating tape to avoid condensation of sample vapours.
Catalytic Reactive Distillation Simulation
Experimentally determined reaction kinetic data were used to
develop the model for a CD process for methanol dehydration
to DME (Table 2). In this study RadFrac, the rigorous equilibrium
stage model that is a part of the commercial simulation package
Aspen Plus (version 10.10) (Aspen Technology Inc., 1999, and
Simulation Sciences Inc., 1994), was used to simulate the
catalytic distillation process. Vapour-liquid equilibrium was
reached at every stage of the column. In this simulation, the
operating pressure was specied via the condenser pressure,
and it was assumed that there was no pressure drop across the
column (Sneesby et al., 1997).
The catalyst was predominantly in contact with liquid,
and so the kinetic equation developed from our experimental
results was used with a user kinetics subroutine for the program
REAC-DIST to calculate the liquid phase generation rate for
each component at each stage in the reaction zone. The
location of the reaction zone within the column was selected
by determining the stage having a reaction temperature that
gives maximum product yield. The composition at the reaction
zone optimally comprised a high concentration of methanol to
ensure a high rate of production of DME.
Results and Discussion
Kinetics of Liquid Phase Catalytic Dehydration of
Methanol to DME
The kinetics of catalytic dehydration of methanol (Eq. 1) has
been studied extensively using either acidic oxide catalysts or
acidic ionic exchange resins other than Amberlyst 35. However,
Amberlyst 35 has advantages over alternative catalysts. Ion
exchanged resins have higher activity and required milder
operating conditions than zeolite catalysts (Table 3) (Nemphos
and Hearn, 1997). Amberlyst 35 is preferred because it has
better temperature tolerance than Amberlyst 15, for example.
To date, all alcohol dehydration mechanisms have been found
to follow Langmuir-Hinshelwood or Eley-Rideal kinetics. Both
the Langmuir-Hinshelwood (Gates and Johanson, 1969) and
Eley-Rideal (Kiviranta-Paakkonen et al., 1998) mechanisms have
been proposed to describe the dehydration of methanol over
acidic resin catalysts, and included the inhibiting effect of water.
It was unknown which mechanism would apply for reaction over
Amberlyst 35. Consequently, the two possible kinetic models
949
 Table 1. Physiochemical properties of Amberlyst 35.
methanol to DME over Amberlyst 35 (Eq. 1) was determined
using a batch slurry reactor in the temperature range of 343
Ionic form Hydrogen to 403 K and initial reaction pressure of 0.82 MPa. Adsorption
of the more polar components (alcohol and water) is much
Concentration of acid sites $ 5.2 eq/kg stronger than the adsorption of the less polar component
(ethers) (Linnekoski et al., 1997; Zhang and Datta, 1995), due to
Surface area 45,000 m2/kg
the signicant difference in dielectric constants (e.g. methanol:
33; DME: 5) (CRC Handbook of Chemistry and Physics, 2002
Average pore diameter 25 m
2003). Equations (2) and (3) can be rearranged by dividing both
Maximum operating temperature 413 K denominators and numerators by KM. The resulting terms
1 KC
and E E are both relatively very small when compared
Particle size 0.700 0.950 mm KM KM
with the other components of the denominator. Consequently,
Table 2. Optimum input parameters for Aspen Plus simulation of Equations (2) and (3) can be simplied to Equations (4) and
catalytic distillation of methanol to DME, low catalyst loading. (5) respectively.

Feed Stream CD Column 2

ksCM
rDME = 2
Temperature: 298 K Total stages: 30 KW (4)
Pressure: 0.9 MPa Rectication stages: 17 K CW + CM
M
Flow rate: 2.5 mol/s Reaction stages: 820
Feed composition: Stripping stages: 2130
Methanol: 100 mol% Feed stage: 8
DME: 0 Catalyst loading: 9.23 kg/stage 2
ksCM
rDME =
KW (5)
Water: 0 Column pressure: 0.9 MPa CW + CM
KM
Reux ratio: 9 (mol)

Distillate to feed ratio 0.5 To determine which model best describes the kinetics
of dehydration of methanol to DME, a series of experiments
1 of Kpatented was performed to examine the effects of methanol and water
Table 3. Comparison EC E CD conditions with this study.
concentration separately on the initial reaction rate. First, the
KM KM
Nemphos and initial methanol concentration was varied (5.3524.57M) for
anhydrous solutions in an inert solvent, o-xylene, to determine
This Study Hearn, 1997 the dependence of initial surface reaction rate on initial methanol
concentration in the absence of water. Second, the initial water
Catalyst Amberlyst 35 Zeolite
concentration was varied (03.56M) while keeping the initial
Catalyst Zone Temperature (K) 399411 623673 methanol concentration constant, to determine the effect of
water on reaction rate. DME and water were the only products
Column Pressure (MPa) 0.82 4.1 under these reaction conditions.

Effect of Methanol Concentration on Initial

have been evaluated for modeling reaction 1 over this catalyst.
Each of the Langmuir-Hinshelwood (Eq. 2) and Eley-Rideal
(Eq. 3) models is based on the surface reaction as the rate-
determining step, and incorporates the effect of competitive
chemisorption of water and methanol:
2CH3OH CH3OCH3 + H2O
2 2
ksK MCM
rDME =
(1+ KWCW + KMCM + KECE )2
2 Rideal model and not by the Langmuir-Hinshelwood model.
ksK MCM
rDME =
1+ KW CW + K MCM + K ECE
where ks is the surface reaction rate constant, and KM, KW and
KE, and CM, CW and CE are the adsorption equilibrium constants
and concentration of methanol, water, and DME, respectively.
The global kinetics of liquid phase catalytic dehydration of
Reaction Rate
The initial rate of formation of DME varied linearly with
initial methanol concentration (Fig. 1). Therefore, catalytic
dehydration of methanol over Amberlyst 35 in the absence of
water was rst order with respect to methanol concentration
over the range of initial methanol concentration. The results
(1) were consistent only with Equation (5). Equation (4) requires
that the initial reaction rate should be zero order with respect to
methanol in the absence of initial water, which is contradicted
(2) by the experimental data. Thus the initial rates for the present
process in the absence of water can be described by the Eley-
(3) The kinetic equation for dehydration of methanol to DME
over Amberlyst 35 in the absence of water reduces to:
rDME = ksCM (6)
where

950 The Canadian Journal of Chemical Engineering, Volume 82, October 2004
Figure 1. Effect of initial MeOH concentration on DME formation
rate. Figure 2. Arrhenius plot and ratio of adsorption equilibrium constants
of water and methanol as a function of temperature.

ks = k0 exp( Ea RT ) (7)

Linear regression of the Arrhenius plot for the initial reaction

rates (Fig. 2) gave values for k0 of 4.72 m3/kgcat.s and Ea of
51.7 kJ/mol

Effect of Water Concentration on Initial Reaction Rate

Water inhibits catalytic methanol dehydration to DME over
either acidic oxides or acidic ion exchange resins (Spivey,
1991; Xu et al., 1997). Desorption of water from acidic active
sites was identied as a component of the global reaction
kinetics (Tanabe et al., 1989). Water and methanol compete
for adsorption at catalytic active sites on the surface of acid
catalysts. Hence, there is an inverse relationship of reaction rate
and concentration of water in the reaction mixture.
Figure 3 shows the inhibiting effect of water by comparing
reaction proles for DME formation as a function of reaction time
at 393 K and 0.82MPa for reaction mixtures having different
initial concentrations of water. The non-linear regression curve Figure 3. Effect of initial water concentration on DME formation.
based on the E-R model (Eq. 5) tted the experimental results
very well (Fig. 4), thus supporting attribution of the Eley-Rideal
mechanism for methanol dehydration to DME over Amberlyst KW
35 under the present reaction conditions. The value for the = K exp(Q RT ) (10)
KM
surface reaction rate constant kS calculated from the non-
linear regression equation (Fig. 4) was 4.72 107m3/kgcat.
s at 393 K, which was in very good agreement with the value where K = KW 0 and Q = (HM HW) (Eq. 10). The linear
KM 0
we obtained from the initial rates for the set of experiments
conducted in the absence of water (5.6 107 m3/kgcat. regression of ln(KW/KM) versus 1/T (Fig. 2) gave the temperature
s). The temperature dependence of the ratio of adsorption dependence of the ratio of adsorption equilibrium constants of
equilibrium constants of water and methanol was derived water and methanol (Eq. 11).
from the dependence of adsorption constants, KW and KM on KW 11138
temperatures, van,t Hoff Equations (8) and (9): = exp 25.75 + (11)
KM T
KW = KW 0 exp( RT )
HW R (8)

The ratio of adsorption equilibrium constant of water to

K M = K M 0 exp( RT )
HM R (9) methanol was 13.3 at 393 K, calculated from Equation (8),
compared to 9.95 for the related acidic ionic exchange resins
Amberlyst 15 (Aiouache and Goto, 2002b) and Dowex 50 (Al-

The Canadian Journal of Chemical Engineering, Volume 82, October 2004 951
Figure 4. Effect of water concentration on initial formation rate of
DME at 393 K.
Jarallan et al., 1988) at that temperature. Thus water is more
strongly adsorped at acid sites of Amberlyst 35, and so will
have a stronger inhibiting effect on forward reaction 1.
Mass Transfer Resistance
The stirring speed for the mixture was set sufciently high that
external mass transfer was not a limiting factor.
The resin particle size was not varied in this study.
However, we have shown in a parallel study (Meng et al.,
2003) that varying the particle size of Amberlyst 35 in the
range 0.32 103 to 1.2 103 m had little effect on the
overall kinetics of hydration/dehydration and etherication
reactions of butene-water-butanol-ethanol-ETBE systems
under similar conditions. It is therefore anticipated that
internal mass transfer resistance will have little impact on the
kinetics of the present system.
Simulation of Catalytic Distillation Process for
Methanol Dehydration to DME
A catalytic distillation process for kinetics-controlled methanol
dehydration to DME has been modeled. The process for
reaction 1 is based on Equations (5), (7) and (11). The CD
column used for the simulation (Fig. 5) comprised three
sections: an upper rectication zone, a central reaction zone,
and a lower stripping zone. The total number of vapour/liquid
(V/L) stages, the number and location of the V/L stages for
the reaction zone, the location for feeding liquid methanol,
the column operating pressure, and the reux ratio were each
varied independently. The temperature at each stage was
determined by the other parameters.
For determination of the optimum size of the column,
and the optimum size and location reaction zone, the location
for liquid feed (pure methanol) was positioned just above the
reaction zone. The reaction zone was located in the middle
section of the CD column, where the concentration of reactant
had a maximum value due to the difference of volatilities
between methanol and DME, and the corresponding column
temperature range was suitable for the highest achievable
reaction rates. The positioning of the reaction zone within the
952
Figure 5. Schematics of the CD column for dehydration of methanol
to DME.
column was determined by comparing the relative volatilities
of reactant and product, and the corresponding temperature
within the zone. An optimized set of input specications for
ASPEN PLUS simulation of catalytic distillation of methanol to
DME was determined by sequentially varying the parameters
according to the following steps (Table 2).
Total Number of Vapour-Liquid Equilibrium Stages
A set of simulations was performed in which the total number
of stages was 15, 20 or 30, and the size of the reaction
zone was always 13 stages. A second set of simulations was
performed using the same total numbers of stages, in which
the corresponding size of the reaction zone was 6, 11 or
13 stages, to accommodate the limitations imposed by the
operating reaction temperature range of the catalyst. In each
case the feed location was positioned closely above the top
stage of the reaction zone. The purity of both products, DME
and water, was improved as the total number of stages was
increased, up to 30 stages, and the reaction zone was 13
stages (Fig. 6). There was no signicant further improvement
from use of a larger CD column or reaction zone. The purity
of the DME that was recoverable from the top condenser
was 98.4 mol% when using a 15-stage CD column with a 6-
stage reaction zone (condenser, stage 1; rectication, stages
24; reaction zone, stages 510; stripping, stages 1114; and
reboiler: stage 15). The purity of the DME and water products
The Canadian Journal of Chemical Engineering, Volume 82, October 2004
Figure 6. Dependence of DME purity on number of stages.

each was increased to almost 100 mol% when using a 30- Figure 7. Dependence of DME purity on location of methanol feed
stage CD column having a 13-stage reaction zone (condenser, stage.
stage 1; rectication, stages 27; reaction zone, stages 820;
stripping stages 2129; and reboiler, stage 30). Thus, it is
necessary to use the larger column to obtain substantially pure
DME as product.
Feed Stage
The optimum location for the feed was determined by varying
that location between stages 2 and 21 within the 13 stage
reaction zone (stages 820) (Fig. 7) . The concentration of
methanol in the reaction zone, and therefore the reaction rate
in the reaction zone, was maximized by feeding methanol
closely above the reaction stage, between stages 5 and 8.
When methanol was fed at the top of the reaction zone (stage
8), the column temperature was high enough to ensure a
high reaction rate and methanol was consumed to produce a
substantially pure product stream. In contrast, when methanol
was injected at a higher stage, some methanol was entrained in
the product stream and the purity of product DME decreased.
When methanol was injected at a lower stage, either within
or below the reaction zone, conversion of methanol was
compromised, and the purity of the DME product was again
Figure 8. Relationship between column pressure and column
reduced. Therefore the optimum position for methanol feed
temperature.
was at the top of the reaction zone.

Reaction Zone
The reaction zone comprised an alternating sequence of
catalyst beds and vapour-liquid equilibrium stages. The catalyst
bed at each reaction zone effectively acted as a small liquid-
phase reactor. The packed bed was designed to ensure that
the liquid reaction mixture made good contact with the
catalyst in each small reactor. Based on our kinetic data, the
total amount of catalyst required in the reactors is 120 kg for
a production scale of 1500 tons DME/year. The amount of
catalyst was an optimum value determined by considering
catalyst requirement and reux ratio.
Column Pressure
Operating pressure in a CD column strongly affects reaction
rates by changing the column temperature prole (Taylor and
Krishna, 2000). The dependence of reaction zone temperature
on column pressure in the range 0.7 to1.0 MPa is shown in
Figure 8, and the resulting dependence of purity of product
DME on pressure is shown in Figure 9. An operating pressure in
the range 0.9 to 1.0 MPa provided the optimum combination
of reaction rate and high purity of DME product.
Reux Ratio
Reux ratio inuences both reaction rate and separation
performance in CD columns (Subawalla and Fair, 1999). In
the present model, a higher reux ratio increased the reactant
methanol recycle across the reaction zone, thereby increasing the
local methanol concentration and so increased the driving force
for the reaction (Fig. 10). The residence time of methanol in the
reaction zone, and hence the required catalyst loading, was also
dependent on the reux ratio. It was found that high purity of
DME (99.997% as top liquid) can be achieved at a reux ratio
of 7 for catalyst loading of 150.3 kg, compared with 99.97%
purity at the higher reux ratio of 9 for the corresponding
catalyst loading of 120 kg. Consequently, the selection of reux
ratio, and corresponding catalyst amount, to be used in practical
applications of the CD process for methanol dehydration to DME
will be dictated by the compromise between required purity of

The Canadian Journal of Chemical Engineering, Volume 82, October 2004 953

Figure 9. Relationship of DME product purity to column pressure.
Figure 10. Dependence of DME product purity on reux ratio.
Figure 11. Proles of liquid composition and temperature within the
column.
product and economic considerations.
Figures 11 and 12 show proles for the compositions of
the liquid and vapour phases respectively within the CD column
when operated at the optimal conditions as determined from
the simulation (Table 2). DME is more volatile than either
954
Figure 12. Proles of vapour composition and temperature within
the column.
water or methanol, and was collected as the overhead product.
The least volatile component, water, was collected at the
bottom. Methanol, the intermediate component in terms of
boiling point, was retained inside the column and converted
to DME and water. Methanol dehydration to DME is a mildly
endothermic reaction. The DME concentration in the liquid
phase within the reaction zone was very low due to its high
volatility. Removal of DME as vapour from the reaction zone
overcame equilibrium limitations of reaction 1, and drove the
reaction to the right. The concentrations of methanol and water
in the rectication zone were each very low. Consequently,
substantially pure DME can be obtained using the present CD
process. Compared to the patented CD process based on zeolite
catalyst (Table 3) (Nemphos and Hearn, 1997), the advantages
found for the current CD process for DME production were
signicantly lower reaction zone temperatures and pressures.
The simulation also showed advantages to using a single CD
column and process to produce DME, when compared with
the conventional two-step approach having separate reaction
and distillation units, including reduced capital costs and
capability to produce very pure DME.
Conclusions
Kinetics of dehydration of methanol to DME over Amberlyst 35
as catalyst has been modeled using a Eley-Rideal mechanism
in which the surface reaction is the rate-determining step. The
reaction under anhydrous conditions is rst order in methanol.
Water inhibits the reaction. The activation energy over this
catalyst is 51.7 kJ/mol.
Acidic ion exchanged resin catalysts have higher activity than
zeolite catalysts, and operate under milder conditions. Amberlyst
35 is preferred as it has a higher temperature tolerance than
alternative resin catalysts, including Amberlyst 15.
A process using a catalytic distillation process for DME
production has been simulated, based on the experimental
kinetic data. High purity DME can be produced using a 30-
stage catalytic distillation column having a 13-stage reaction
zone, operating in the pressure range 0.9 to 1.0 MPa. Use of a
single CD column, instead of the separate reactor, distillation
and/or rectication units used in a conventional methanol to
DME process, offers economic advantages for production of
very pure DME.
The Canadian Journal of Chemical Engineering, Volume 82, October 2004
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Manuscript received July 22, 2003; revised manuscript received March

11, 2004; accepted for publication April 23, 2004.

The Canadian Journal of Chemical Engineering, Volume 82, October 2004 955