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Fuel Processing Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / f u p r o c

Experimental study of improved two step synthesis for DME production

Yingying Zhu, Shurong Wang ⁎, Xiaolan Ge, Qian Liu, Zhongyang Luo, Kefa Cen
State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, China

a r t i c l e i n f o a b s t r a c t

Article history: Dimethyl ether (DME) has received growing attention due to its potential use as a multi-purpose fuel. A new
Received 25 August 2008 technical route of improved two step synthesis is proposed for DME production, which is composed of
Received in revised form 24 February 2009 methanol synthesis and methanol dehydration in a fixed-bed reactor. The influences of the operating
Accepted 4 May 2009
conditions including reaction pressure, temperature, H2/CO mole ratio in the syngas and space velocity on CO
Available online xxxx
conversion, selectivity and yield of DME are investigated. CO conversion and DME yield both increase
Keywords:
monotonically with the pressure increase. The optimal reaction temperatures for the synthesis and
Dimethyl ether dehydration of methanol are different. CO conversion increases at first and keeps constant when the H2/CO
Improved two step mole ratio is above 2. DME yield increases obviously and then decreases gradually with the space velocity
Synthesis increase. The optimal conditions are obtained to maximize the CO conversion and DME selectivity. The
Catalyst stability reaction temperatures of the top and bottom stage are in the range of 270–280 °C and 235–245 °C,
respectively. The optimal ratio of H2/CO is above 2, and the space velocity is in the range of 1000–1300 h− 1.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction DME synthesis with a higher ratio of dehydration catalyst [15].

During the past few years, dimethyl ether (DME) has received
growing attention due to its potential use as a multi-purpose fuel. It
can be obtained from natural gas, coal, waste products and biomass
[1]. DME can be used as a clean high-efficiency compression ignition
fuel with reduced NOx, SOx, and PM emissions [2]. It has similar
properties with propane and butane, which is potential for substitut-
ing LPG [3]. In addition, DME is an important chemical that can be
used as an aerosol propellant to replace chlorofluorocarbons due to its
environmentally benign characteristics. Generally, two methods are
mainly adopted for DME production from syngas. One is a two step
reaction process comprising methanol synthesis and dehydration, and
the other is the single step reaction to synthesize DME directly.
For two step reaction, mild operating condition and high
selectivity of DME can be easily achieved, and the purification of the
products is much easier than single reaction step. For the methanol
synthesis, CuO–ZnO–Al2O3 catalyst is widely used; however, it suffers
from the inferiority caused by the thermal sintering of Cu occurring at
the reaction temperature beyond 300 °C [4]. Other metal elements
such as Pd [5,6], Cr [7–9], Mn [10–12], and Zr [13,14] are impregnated
as metal components or promoter, which can improve the perfor-
mance of catalysts on methanol synthesis. For the methanol
dehydration, the widely used catalysts are the solid acids, such as γ-
Al2O3, ZSM-5, HY zeolites and silica–alumina. The optimum mass ratio
of methanol synthesis catalyst to dehydration catalyst was in the
range of 1–2, and the catalyst deactivation would be observed during
⁎ Corresponding author. Tel.: +86 571 87952801; fax: +86 571 87951616.
E-mail address: srwang@zju.edu.cn (S. Wang).
However, for the two step reaction, a long series of complicated
process results in high investment, and the conversion of syngas is low
due to the severe limitation of thermodynamics existing in the
methanol synthesis from syngas [16].
The single step reaction is performed over a hybrid catalyst. The
thermodynamic limitation existing in the methanol synthesis is mitigated,
due to the methanol continuous removal in the subsequent methanol
dehydration on solid acid catalyst [17,18]. The single step reaction leads to a
high CO conversion. Besides that, the investment is relatively lower than
the two step reaction. The catalyst preparation methods, such as physical
mixing, coprecipitation, impregnation, coprecipitate sedimentation and
sol–gel impregnation, have important effects on the CO conversion and
DME selectivity [19–23]. Moradi et al. [19] prepared nine hybrid catalysts
and found that the physical mixing catalysts showed better performance.
Ge et al. [22] reported that coprecipitate sedimentation was the best
preparation method for single step synthesis of DME. The hybrid catalysts
have two kinds of active sites corresponding to methanol formation and
dehydration, respectively. The contact of two kinds of active sites affects
the catalytic properties of hybrid catalysts [22,24]. And the deactivation
rate of the catalysts is accelerated due to the synergy effect. Aguayo et al.
[25] proved that water presence in the catalyst system could depress the
deactivation according to the effective coke deposition; however, it also
decreased the activity of acid function. Ereña et al. [26] studied the effect of
reaction conditions on coke deposition and found that coke deactivated
the metallic function. Luan et al. [27] pointed out that the redox cycle was
an effective method for the in-situ regeneration of deactivated catalysts in
the single step synthesis over the hybrid catalyst CuO–ZnO–Al2O3/γ-
Al2O3–HZSM-5. The effects of the operating conditions on CO conversion
and DME selectivity have been investigated by many researchers. Ereña

0378-3820/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2009.05.001

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Table 1 gas was monitored on-line by a Gas Chromatograph (Agilent 6820).

Physical properties of the catalyst. The analysis system is composed of one six-port value, three packed
Catalyst Surface area (m2/g) Pore volume (ul/g) Average pore diameter (Å) columns (one precolumn, DBWax and Molecular sieve column), and
CuO/ZnO/ 79 180 100 TCD and FID both as detectors. The column temperature was initially
Al2O3 kept at 50 °C for 3 min, and then elevated to 170 °C at a heating rate of
15 °C/min, and finally kept at 170 °C for 10 min. Helium was used as
the carrier gas at a flow rate of 30 ml/min.
et al. [28] found that on a CuO–ZnO–Al2O3/NaHZSM-5 hybrid catalyst, CO CO conversion, the selectivity of DME in oxygenates, selectivity of
conversion was total at 275 °C and 40 bar, with a DME selectivity of 80% DME, selectivity of CO2 and yield of DME were defined as follows:
and a DME yield of 78%. Ereña et al. [29] also proposed that a maximum CO
conversion was obtained when the H2/CO mole ratio was 2, while the Nin yCO;in − Nout yCO;out
DME selectivity and yield reached a maximum when H2/CO was 6. Moradi XCO = × 100 ð1Þ
Nin yCO;in
et al. [30] investigated the effects of syngas composition and space velocity
on the single step synthesis of DME in a slurry reactor, and reported that 2yDME;out
SDME in O = × 100 ð2Þ
feed composition had the dominant effect. 2yDME;out + yMOH;out
In this present study, a new technical route of improved two step
synthesis is proposed for DME production. A two-stage catalyst
2Nout yDME;out
system, which is composed of methanol synthesis and dehydration SDME = × 100 ð3Þ
Nin yCO;in − Nout yCO;out
catalyst respectively, is set up in a fixed-bed reactor. The reaction
temperatures for the two-stage catalyst system are set separately, so
as to improve the corresponding catalyst performance. A series of Nout yCO2; out
experimental researches were carried out at various operating SCO2 = × 100 ð4Þ
Nin yCO;in − Nout yCO;out
conditions to study the synthesis behavior and catalyst stability.
2Nout yDME
2. Experimental YDME = × 100 ð5Þ
Nin yCO

2.1. Characterization of the catalysts

3. Results and discussion

The two-stage catalytic system is composed of CuO–ZnO–Al2O3 as

the methanol synthesis catalyst and HZSM-5 as the methanol
dehydration catalyst.
A GENESIS-4000 X-ray energy dispersion spectroscopy was used to
identify the components of the catalysts. The mole ratio of CuO/ZnO/
Al2O3 is 66/23.7/10.3. For HZSM-5, the mole ratio of SiO2/Al2O3 is 20.
The surface area and pore size were measured by nitrogen adsorption
at − 196 °C after heat pretreatment under vacuum at 350 °C for 3 h.
Physical specifications of the catalysts including BET area, pore
volume, and average pore diameter are listed in Table 1.
The strength and distribution of acid sites were tested by NH3-TPD.
The HZSM-5 catalyst with an amount of 0.2 g was initially flushed with
a nitrogen flow at 500 °C for 5 h, subsequently cooled to 50 °C and then
saturated with NH3 for 30 min. After that the sample was heated from
50 °C to 500 °C at a heating rate of 10 °C/min. Fig. 1 shows the NH3-
TPD profiles of HZSM-5. It is shown that two peaks are in the range of
50–500 °C. The first peak appearing at 120 °C is generally attributed to
the weak acid sites of HZSM-5, while the second peak appearing at
350 °C is attributed to the strong acid sites. The total acid amount is
0.986 mmol NH3/g.
The improved two step synthesis of DME consists of three reaction
steps: methanol synthesis, methanol dehydration and water gas shift
reaction. The reaction formulae are listed as followings:
CO þ 2H2 ↔CH3 OH ð6Þ
2CH3 OH↔CH3 OCH3 þ H2 O ð7Þ
H2 O þ CO↔CO2 þ H2 ð8Þ
3.1. Effect of reaction pressure
The influence of reaction pressure on catalytic activity is shown in
Fig. 3. CO conversion and DME yield both increase monotonically with
pressure increase, due to the gas volume decrease during DME production.
This is in agreement with the result obtained by Song et al. [20].
Fig. 3 also shows that the selectivity of DME in oxygenates and the
selectivity of DME both increase obviously first and then keep
increasing slightly above the pressure of 5 MPa. With the increase of
pressure, the methanol dehydration reaction is liable to approach to
the equilibrium [31].

2.2. Reaction system

For DME synthesis, both catalysts were crushed and sieved to get a
particle size distribution in the range of 0.15–0.18 mm. The schematic
diagram of the reactor system is shown in Fig. 2. The CuO–ZnO–Al2O3 and
HZSM-5 catalysts are stacked in a fixed-bed reactor whose inner diameter
is 6 mm and length is 400 mm. The mass ratio of CuO–ZnO–Al2O3 and
HZSM-5 was selected as 2, and CuO–ZnO–Al2O3 was on the top of HZSM-5.
The catalyst of CuO–ZnO–Al2O3 was reduced in a N2 flow containing 5% H2.
The temperature was increased at a heating rate close to 1 °C/min from
ambient to 280 °C and then kept at 280 °C for 10 h.
During the experimental process, the feed gas was preheated and
introduced into the fixed-bed reactor. The temperatures of the reactor
were measured by two thermocouples which were inserted in the
center of the two catalyst beds for methanol synthesis and dehydra-
tion, respectively. The outlet gas was heated to avoid condensation of
liquid products until it entered the gas chromatograph. The effluent Fig. 1. The NH3-TPD profiles of HZSM-5.

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Fig. 2. Schematic diagram of improved two step synthesis reactor for DME production.

3.2. Effect of reaction temperatures
3.2.1. Effect of the top stage temperature
Generally, the catalyst suffers from the deactivation caused by the
thermal sintering of Cu occurring at the reaction temperature beyond
300 °C. The top stage temperature was then selected in the range of
234–300 °C. As shown in Fig. 4, CO conversion and DME yield arrives a
maximum of 70% and 58% at the temperature of 280 °C and 270 °C,
respectively. It indicates that the activity of methanol synthesis
catalyst increases first, and then decreases with the temperature
increase, due to the thermodynamic restrictions of the complicated
exothermal reaction.
Furthermore, the selectivity of DME increases slowly initially and
then decreases rapidly after 260 °C, while the selectivity of CO2 shows

Fig. 3. Effect of the reaction pressure on catalytic activity. (H2/CO = 2, top stage Fig. 4. Effect of the top stage temperature on catalytic activity. (H2/CO = 2,
temperature = 268 °C, bottom stage temperature = 236 °C, space velocity = 1800 h− 1). pressure = 6 MPa, bottom stage temperature = 235 °C, space velocity = 1800 h− 1).

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Fig. 5. Effect of the bottom stage temperature on catalytic activity. (H2/CO = 2, Fig. 6. Effect of H2/CO mole ratio on catalytic activity. (Pressure = 8 MPa, top stage
pressure = 6 MPa, top stage temperature = 268 °C, space velocity = 1800 h− 1). temperature = 300 °C, bottom stage temperature = 236 °C, space velocity = 1800 h− 1).

the reverse trend. With the top stage temperature increase, the 3.3. Effect of H2/CO mole ratio
selectivity of methanol in methanol synthesis reaction decreases
gradually and hydrocracking reactions are favored, which means that The effect of H2/CO mole ratio in feed gas is shown in Fig. 6. CO
more by-products like CO2 are formed, resulting in lower selectivity of conversion and DME yield increase at first and then keep constant
DME. when the H2/CO mole ratio is above 2. The methanol synthesis is
favored by the H2-rich syngas at a H2/CO mole ratio of 2. Besides that,
a low H2/CO mole ratio will easily cause coking on the catalyst,
3.2.2. Effect of the bottom stage temperature resulting in the catalyst deactivation.
The effect of bottom stage temperature is shown in Fig. 5. It indicates The selectivity of DME is rather lower when the H2/CO mole ratio
that the activity of methanol dehydration catalyst increases first and then is less than 1. This is because more by-products like CO2 and
decreases. However, the influence of the bottom stage temperature is hydrocarbons are easily formed. Along with the increase of H2/CO
slighter than that of the top stage temperature. It can be concluded that mole ratio (1 b H2/CO b 1.5), the selectivity of DME increases while the
the optimum bottom stage temperature lies in the range of 235–245 °C. selectivity of CO2 decreases. When H2/CO mole ratio is above 1.5, the
Based on the analyses above, the optimal temperatures of the top selectivity of DME and CO2 keep constant. It is consistent with the
stage and bottom stage are different. Table 2 shows the experimental single step synthesis of DME [24]. H2/CO mole ratio has less influence
results under two-stage and single-stage temperature control. For on the selectivity of DME in oxygenates. However, in Zhou et al.'s
two-stage temperature control, the temperature of the top stage was opinion [32], the H2/CO mole ratio could not be too large, because the
kept at 268 °C, while the bottom at 236 °C, both of which were dehydration catalyst showed a more rapid deactivation rate when H2/
controlled at the optimum. For single-stage temperature control the CO mole ratio was above 2.
temperature of both the top and bottom stages was kept at 268 °C.
Experimental researches were carried out under the same other 3.4. Effect of the space velocity
reaction conditions, in which the mole ratio of H2/CO was 2, the
reaction pressure was 6 MPa and the space velocity was 1800 h− 1. As shown in Fig. 7, CO conversion decreases from 98.4% to 30.2%
Under two-stage temperature control, CO conversion, selectivity of with the increase of the space velocity from 600 h− 1 to 3000 h− 1.
DME in oxygenates, selectivity of DME, and yield of DME are all higher
than those under single-stage temperature control. Ge et al. [22]
pointed out that CO conversion could achieve 89.4% and DME
selectivity was 87.2% on their single step reactor. It seems that CO
conversion in the single step reaction is higher than the improved two
step synthesis obtained due to the thermodynamic equilibrium.
However, DME selectivity is relatively lower. This is because that
CuO–ZnO–Al2O3 catalyst is located separately on the top of HZSM-5 in
the improved two step process. And H2O formed in the methanol
dehydration reaction would not contact with CuO–ZnO–Al2O3 catalyst
enough, therefore, less CO2 formed. Thus the improved two step
synthesis is beneficial to obtain higher selectivity of DME.

Table 2
Experimental results under two-stage and single-stage temperature control.

Temperature (°C) CO Selectivity Selectivity DME

Top stage Bottom stage conversion of DME in of DME yield
(%) oxygenates (%) (%)
(%)
268 268 54.2 93.6 85.8 46.5
Fig. 7. Effect of the space velocity on catalytic activity. (H2/CO = 2, pressure = 8 MPa,
268 236 66.3 96.4 89.6 56.7
top stage temperature = 300 °C, bottom stage temperature = 236 °C).

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Fig. 8. Operation test on catalyst stability.
Initially DME yield increases obviously with the space velocity, due to
the corresponding feed rate increase. With the continuous increase of
space velocity, the residence time becomes shortened, and thus DME
yield decreases gradually. The maximum DME yield can be achieved at
a space velocity of 1000 h− 1.
The selectivity of DME increases sharply first and then slowly with
the space velocity increase, while the selectivity of CO2 decreases
monotonically. When the space velocity is small, longer residence time
in the reactor will favor the hydrocracking reactions, and more by-
products like methane are formed. Therefore, high space velocity will
benefit DME selectivity. And the selectivity of DME in oxygenates
decreases with the increase of space velocity because that methanol
dehydration cannot proceed completely in the case of high space
velocity. The optimum space velocity lies in the range of 1000–1300 h− 1.
3.5. Catalyst stability
A long term test lasting for 100 h was operated at the following
conditions: the reaction pressure was 8 MPa, H2/CO mole ratio was 2,
the top stage temperature was 268 °C, the bottom stage temperature
was 236 °C, and the space velocity was 1800 h− 1. Fig. 8 shows that no
apparent decline in catalyst activity took place.
4. Conclusion
A new technical route of improved two step synthesis for DME
production is proposed in this paper. The effects of the operating
conditions, such as the reaction pressure, the reaction temperature,
H2/CO mole ratio and the space velocity, were investigated to obtain
the optimal CO conversion, selectivity and yield of DME. CO
conversion and DME yield both increase monotonically with the
pressure increase. The optimal reaction temperatures for the synthesis
and dehydration of methanol are different. The optimal reaction
temperatures of the top and bottom stage are in the range of 270–
280 °C and 235–245 °C, respectively. CO conversion increases at first
and keeps constant when the H2/CO mole ratio is above 2. Meanwhile,
the selectivity of DME keeps constant when H2/CO mole ratio is above
1.5. DME yield increases obviously and then decreases gradually with
the space velocity increase. Both methanol synthesis catalyst and
methanol dehydration catalyst had good stability over a 100 h period
operation.
Acknowledgments
The authors appreciate financial support granted from the National
Natural Science Foundation (50676085 and 90610035) and the
Please cite this article as: Y. Zhu, et al., Experimental study of improved two step synthesis for DME production, Fuel Processing Technology
(2009), doi:10.1016/j.fuproc.2009.05.001
5
National Basic Research Program of China (2007CB210200). Also
great appreciate the support from the International Science and
Technology Cooperation Programme (2009DFA61050).
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