Chemical Engineering Journal xxx (2017) xxxxxx

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Chemical Engineering Journal

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Direct synthesis of dimethyl ether from synthesis gas: Experimental

study and mathematical modeling
I.A. Kurzina a,, S.I. Reshetnikov b, N.I. Karakchieva a,c, L.N. Kurina a
a
Tomsk State University, 634050 Tomsk, pr. Lenina, 36, Russia
b
Boreskov Institute of Catalysis SB RAS, 630090 Novosibirsk, pr. Akad. Lavrenteva, 5, Russia
c
Siberian Research Institute of Agriculture and Peat, Branch of the Siberian Federal Research Center, Russian Academy of Sciences, 3, Gagarina St., Tomsk 634050, Russia

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Direct synthesis of dimethyl ether CO+H2

(DME) from syngas was studied.

Thermodynamic analysis of the
equilibrium mixtures was modeling. kat1

The variants loading of Cu-Zn-Al and 2
a c-Al2O3 catalysts was studied.

The effect of operating conditions on 1
DME yield was investigated.
kat2

The optimal reaction conditions were 2
determined.

DME, ets

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

Article history: Direct synthesis of dimethyl ether (DME) from syngas, was investigated over a CuO-ZnO-Al2O3 catalyst
Available online xxxx for methanol synthesis and a c-Al2O3 catalyst for a methanol dehydration. On the base of mathematical
modeling, thermodynamic analysis was carried out in a wide range of pressures (10100 bar) and tem-
Keywords: peratures (220280 C) for binary mixtures (H2 + CO) with an H2/CO = 16 M ratio. The influence of reac-
Direct synthesis of dimethyl ether tion conditions on the equilibrium content of components in the mixture was modelled. The effect of the
Syngas loading method of catalysts of the methanol synthesis and its dehydration (layerwise loading, mixing) in
Mathematical modeling
the DME synthesis in a single reaction step on the CO conversion and the yield of DME was experimen-
tally studied. It has been demonstrated that the layerwise combined loading with the intermediate mixed
layer of CuO-ZnO-Al2O3 catalysts of the methanol synthesis and the c-Al2O3 catalyst for the DME synthe-
sis (2:1:2, ratio parts, i.e. two parts of the catalyst of the methanol synthesis, one part of a mixture of the
catalysts and two parts of the catalyst of the methanol dehydration) allow to obtain the higher yield of
DME. The effect of operating conditions (pressure, temperature, ratio H2/CO, time on stream, and catalyst
stability) on the CO conversion and yield of DME was studied. The optimal conditions for loading variant
2:1:2 are: the pressure is 30 bar, the temperature is 280 C and the initial ratio of H2/CO is equal to 2. At
that, the CO conversion remains practically constant during 180 h reaction run.
2017 Published by Elsevier B.V.

1. Introduction

Dimethyl ether (DME) finds its wide application as raw materi-

als for the chemical industry, the solvent and refrigerant, in cos-
Corresponding author.
metic industry (aerosol propellant), but particular interest has
currently been aroused regarding its use as a clean and economical
E-mail address: kurzina99@mail.ru (I.A. Kurzina).

http://dx.doi.org/10.1016/j.cej.2017.04.132
1385-8947/ 2017 Published by Elsevier B.V.

Please cite this article in press as: I.A. Kurzina et al., Direct synthesis of dimethyl ether from synthesis gas: Experimental study and mathematical modeling,
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2 I.A. Kurzina et al. / Chemical Engineering Journal xxx (2017) xxxxxx
alternative fuel [15]. DME can be obtained from oil alternative
raw materials (coal, natural gas, and biomass) via synthesis gas
[610], but the most promising one is represented by natural gas
owing to its availability.
There are two strategies for the production of dimethyl ether
from synthesis gas. The first method includes a two-step process:
the synthesis of methanol on a metallic catalyst and then the dehy-
dration of methanol on an acid catalyst. In this case, the stage of
the methanol dehydration is considered as a separate step in the
conversion of methanol to DME [1115]. At present, much atten-
tion is paid to the development of another method an STD-
process (synthesis gas to dimethyl ether), which consists in the
obtainment of dimethyl ether in a single step using a bifunctional
catalyst [1620]. This method due to the lower thermodynamic
limitations allows the process to be carried out at higher tempera-
tures and lower pressures [21].
In the literature, considerable attention has been paid to the
search of optimal catalysts. For the process of the methanol syn-
thesis, catalytic systems Cu/Zn/Al/O and Cu/Zn/Cr/O are used. In
a number of papers, it has been demonstrated that the active phase
is represented by the copper in the dispersed state. The catalysts
are obtained by coprecipitation of zinc and chromium salts or by
dry mixing of oxides, by a solgel method. In order to enhance
the dispersity of copper particles and to increase the specific sur-
face, all kinds of promoters are also used, including such metallic
elements as Pd [22], Cr [23,24], Mn [25,26], Zr [2729], and Ca
[30].For the synthesis of dimethyl ether from methanol, the cata-
lysts of acid type are applied: aluminum oxide, combined
aluminum-silicon oxides, zeolites. For the effective progression of
the reaction, the presence of a high concentration of acid sites is
of great importance. The use of c-Al2O3 as a dehydration agent is
connected with the existence of several types of active Lewis cen-
ters of different intensities [3137]. Different modifications of cat-
alysts are possible for the increase of the surface acidity.
In the direct synthesis of the single-step DME synthesis from
the synthesis gas, bifunctional (hybrid) catalysts that possess two
types of active centers inherent in the methanol formation and
its dehydration are used. The interaction of two types of active cen-
ters influences the catalytic properties of bifunctional catalysts.
The catalysts are obtained by means of mixing the catalysts of
the methanol synthesis and its dehydration up to dimethyl ether,
by coprecipitation, by solgel, by impregnation and by the method
of physical mixing [23,25,32,37,38]. The ratio among the compo-
nents of bifunctional catalysts becomes significant and a determin-
ing factor in the increase of the activity. The study of the STD-
process has been aimed not only at a hybrid catalyst improving,
but at the effect of operating conditions as well.
The objective of the paper was a theoretical and experimental
study of the influence of reaction conditions (pressure, tempera-
ture, ratio H2/CO, time on stream) as well as the loading variants
of catalysts of the methanol synthesis and its dehydration (layer-
wise loading, mixing) on CO conversion and the dimethyl ether
yield in a direct synthesis of DME from syngas.
2. Experimental
2.1. Preparation of catalysts
The CuOZnOAl2O3 catalyst for the methanol synthesis was
prepared by decomposition at 623 K in air of the corresponding
mixed hydroxycarbonate with aurichalcite-like structure [39].
The hydroxycarbonate was precipitated from the 10% wt aqueous
solution of Cu2+ and Zn2+ nitrates by Na2CO3 solution at 70 C
and pH = 7, washed thoroughly by distilled water and dried
overnight under IR lamp and finally calcined at 350 C for 4 h
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Chem. Eng. J. (2017), http://dx.doi.org/10.1016/j.cej.2017.04.132
and granulated. The dry sample was crushed to a grain size of
0.250.5 mm. This 27 wt% ZnO/13 wt% CuO/60 wt% Al2O3 catalyst
(R-1) is similar to Katalco-58 which has been used in industry for
methanol production.
2.2. Characterization of catalysts
The composition of the catalyst samples was analyzed using an
Agilent 4100 atomic emission spectrometer of microwave plasma.
Sample specimens were decomposed in strong acid. 5 ml of nitric
acid was added to the sufficient amount of sample specimens.
The decomposition of sample specimens was conducted for a
day. The porous structure and the specific surface of the samples
were determined by BET using an automatic TriStar II 3020 ana-
lyzer of Micromeritics (USA). The value of the specific surface area
was determined from the data of nitrogen adsorption isotherms
observed at 76 K. The investigation of the samples by the method
of the temperature-programmed reduction was carried out using
a Chemisorb 2750 chemisorption analyzer in a flow of the 10% H2
mixture in argon.
2.3. Catalytic procedure
Gaseous hydrogen and carbon monoxides were used as compo-
nents of the initial reaction mixture. The catalyst with a particle
size in the range of 0.51.0 mm was used; 5.0 cm3 of the samples
was loaded. Before catalytic studies, the samples were being
reduced in a flow of hydrogen at 300 C for 35 h. The conditions
are as follows: P = 15 bar, T = 220-280 C, H2/CO = 0.52, contact
time 6 s. Gas chromatographic analysis of the product was carried
out on a Crystal 5000.2 gas chromatograph with two packed col-
umns: Porapak N for the analysis of DME(g), H2O(g), CH3OH(g);
and a carbon molecular sieve Activated charcoal for the analysis
of H2, CO, CH4, CO2.
3. Results and discussion
3.1. Thermodynamic study
In the course of the synthesis of dimethyl ether from H2, CO and
CO2 in a single reaction step, four basic reactions proceed: hydro-
genation of carbon monoxide, the reverse water-gas shift reaction,
the dimethyl ether (DME) formation, which proceeds as a result of
methanol (MeOH) dehydration and the reaction of carbon dioxide
hydrogenation. A scheme with the following reactions has been
considered [4042]:
Hydrogenation of CO:
CO 2H2 CH3 OH
1
DH 90:4 kJ=mol;DG 25:34 kJ=mol
Reversed water-gas shift reaction:
CO H2 O CO2 H2
2
DH 41:0 kJ=mol;DG 28:60 kJ=mol
Dehydration of methanol to DME:
2CH3 OH CH3 OCH3 H2 O
3
DH 23:5 kJ=mol;DG 16:55 kJ=mol
Hydrogenation of CO2:
CO2 3H2 CH3 OH H2 O
4
DH 49:5 kJ=mol;DG 3:30 kJ=mol
For studying the influence of the conditions of reactions perfor-
mance on the equilibrium concentration of methanol and dimethyl
ether, the calculations on determination of the mixture composi-
 I.A. Kurzina et al. / Chemical Engineering Journal xxx (2017) xxxxxx 3

tion when attaining the thermodynamic equilibrium were done for 100
different reaction conditions. When calculating the equilibrium H2/CO=1 CO conversion
composition in the methanol synthesis, reactions (1) and (2) were
taken into consideration; when determining the equilibrium con- 80
centration of dimethyl ether (DME), the reaction of dehydration
of methanol to DME was additionally taken into account (reaction YDME
60

Eq (%)
(3)). Reaction (4) was not taken into consideration as it was an
overall reaction of the two first reactions. The constants of the
equilibrium of reactions are presented by the following equations: 40 DME

f CH3OH f CO2 f H2 f CH32 O f H2O CO2

K1 ; K2 ; K3
2
f CO f H2 f CO f H2O 2
f CH3OH 20
The mathematical modeling was carried out in a wide range of MeOH
H2O
pressures (10100 bar) and temperatures (220-280 C) for binary 0
mixtures (H2 + CO) with a H2/CO = 16 M ratio. A calculation pro-
gram has been developed in Fortran. The method is the one estab- 0 20 40 60 80 100
lished in the literature for determining the equilibrium constants
from the standard values of formation of enthalpies and entropies
P (bar)
for the components of each individual reaction [43].
Fig. 2. CO conversion, dimethyl ether yield (YDME) and the equilibrium content of
The results of thermodynamic calculations are presented in components for DME synthesis vs. pressure. Reaction conditions: H2/CO = 1,
Figs. 13. The conversion of CO, XCO (%) and the yield of DME, YDME T = 280 C.
(%) and methanol YMeOH (%) are calculated by using the following
equations:
  50
nCO
X 1  100; 7
n0CO
Concentration (%)
2nDME
40
Y DME  100; 8
nCO nCO2 0
30 DME
nMeOH
Y MeOH  100; 9
nCO nCO2 0
20
where nCO and nDME are the molar flowrates of CO and DME in the
outlet stream and (nCO + nCO2)0 is the sum of CO or CO2 flowrates
in the feed. 10 MeOH
Fig. 1, demonstrates the equilibrium concentrations of metha-
nol and dimethyl ether depending on the ratio of the hydrogen
to the carbon monoxide. From these data it follows that the 0
maximum equilibrium concentration of methanol in the methanol
220 240 260 280
o
25 Temperature ( C)
Fig. 3. Methanol (MeOH) and dimethyl ether (DME) equilibrium concentration at
different temperatures. Reaction conditions: H2/CO = 1, P = 30 bar, T = 280 C.
20
Concentration (%)

DME
synthesis is attained when the ratio of the initial reagents is H2/
CO = 2, and that of dimethyl ether in the fusion reaction of DME
15 when H2/CO = 1. The obtained ratio of H2/CO = 2 agrees with
the stoichiometry of the brutto-reaction of methanol reaction pro-
ceeding (1). As to the reaction of dimethyl ether, the preferable
10 ratio of H2/CO must formally equal the value of 2 as the stoichiom-
MeOH etry of this reaction corresponds to the equation:

2CO 4H2 CH3 OCH3 H2 O 5

5
However, taking into account the fact that the resulted water
reacts with carbon monoxide according to reaction (2), then, virtu-
ally, the brutto reaction takes place:
0
0 2 4 6 3CO 3H2 CH3 OCH3 CO2 6

H2/CO Consequently, in order to obtain dimethyl ether, the CO:H2

mixture in the ratio of 1:1 is required. In the middle of the 90s,
Fig. 1. Dimethyl ether (DME) and methanol (MeOH) equilibrium concentration vs. the synthesis gas of the same composition was suggested for using
Reaction conditions: H2/CO. P = 30 bar, T = 280 C. in industrial production of dimethyl ether [44,45].

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4 I.A. Kurzina et al. / Chemical Engineering Journal xxx (2017) xxxxxx
The composition of the equilibrium mixture of the fusion reac-
tion of the dimethyl ether synthesis depending on the pressure for
H2/CO = 1 and temperature 280 C is presented in fig. 2. From the
obtained data it follows that independently of the pressure, for
the H2/CO = 1 mixture, there is virtually no water and methanol
observed; the reaction products are dimethyl ether and carbon
dioxide. When increasing the pressure, an increase in the CO con-
version and the DME equilibrium concentration is also observed. A
strong enough change occurs when increasing the pressure up to
30 bar. Thus, with the increase in the pressure from 10 to 30 bar,
the DME yield increases by 21%; and the increase in the pressure
from 30 to 50 bar leads to the yield increase only by 6%. This ten-
dency is observed at other temperatures as well. Consequently, the
pressure of 30 bar can be recommended for carrying out experi-
mental researches.
Fig. 3 shows the equilibrium concentration of dimethyl ether
and methanol depending on the temperature for the gas mixture
of the following composition: CO = 50%, H2 = 50%. From these data
it follows that when H2/CO = 1, the equilibrium content of
dimethyl ether and methanol in the considered temperature range
of 220280 C increases with the decrease in the temperature. The
equilibrium value of the DME concentration amounts to 4024%
vol., and that of methanol 266% vol.
Therefore, if to carry out the process in a single reactor compris-
ing two catalyst beds (layers) during the first one, to obtain
methanol (equilibrium content) using the catalyst of the methanol
synthesis, and then to feed the resulted gas mixture onto the cat-
alyst bed where its dehydration will proceed, then, based on the
equilibrium concentration of methanol, in case of its complete
dehydration during reaction (3) proceeding, theoretically the max-
imal concentration of DME equal approximately two times lower
then the equilibrium concentration of the methanol. In case of
simultaneous proceeding of the process over physical mixing of
catalysts, the equilibrium concentration of DME is several times
higher than that during two layerwise catalysts loading.
3.2. Effect of methods of catalyst loading
Let us consider the influence of loading of the catalysts on the
conversion of CO and the yield of dimethyl ether in the DME syn-
thesis in a single reaction step over the CuO-ZnO-Al2O3 catalyst for
the methanol synthesis and the c-Al2O3 catalyst for a methanol
dehydration. The catalysts were characterized. Textural and acidic
properties of c-alumina samples were characterized by XRD, BET
surface area analysis, powder X-ray diffraction, NH3 temperature-
programmed desorption, and N2 adsorption-desorption and
NH3-TPD techniques. Table 1 shows the physical properties and
the acidic function of the catalysts.
The analysis of several variants of catalyst loading into the reac-
tor was carried out experimentally. The total amount (5 cm3) of the
catalyst was taken as equal. The following variants of catalyst load-
ing have been considered:
1. The physical mixture of catalysts of the MeOH and DME synthe-
sis in equal parts.
2. Layerwise loading with different ratios of catalysts of the
methanol synthesis and its dehydration in DME in the ratio of
parts: 1:1 and 2:3;
Table 1
Properties of the catalysts.
Catalyst BET surface
(m2 g1)
CuO-ZnO-Al2O3 (R-1) 110
c-Al2O3 250
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Chem. Eng. J. (2017), http://dx.doi.org/10.1016/j.cej.2017.04.132
3. Combined loading 2:1:2, i.e. 2 parts of the catalyst of the metha-
nol synthesis, one part of a mixture of the catalyst of methanol
and DME synthesis and two parts of the catalyst of the DME
synthesis.
The methods of reactor loading of the catalysts are schemati-
cally shown in Fig. 4. Catalytic studies were carried out at
P = 3 bar, H2/CO = 2, T = 280 C and at contact time of 6 s. The
results are presented in Fig. 4.
In case of the physical mixture of catalysts R-1: c-Al2O3 = 1:1,
the CO conversion reaches 72% with the DME yield of 33%. During
layerwise loading in the ratio of R-1:c-Al2O3 = 1:1, the CO conver-
sion amounts to 36%, and the dimethyl ether yield 22%. The CO
conversion value of 30% is attained when loading a less content of
the catalyst of the DME synthesis, i.e. when the ratio is 2:3. The CO
conversion value of 30% is attained when loading a less content of
the catalyst of the menthol synthesis, i.e. when the ratio is 2:3.
With the increase of the share of the acid c-Al2O3 catalyst, the
CO2 concentration has a minimum value of 5% vol. with a 17% yield
of DME. The decrease in the DME yield can be explained by the fact
that the amount of the formed methanol has decreased when
reducing the catalysts amount. Consequently, the reaction under
these conditions (temperature, contact time) proceeds at a dis-
tance from the equilibrium (Fig. 5) as the reduction in the DME
yield is directly proportional to the reduction of the catalyst of
the methanol synthesis. A more preferable variant of loading in
the case under consideration is a combined one, 2:1:2. In spite of
the similar value of the DME yield, making up 34%, the CO conver-
sion in case of the 2:1:2 loading amounts approximately to 67%,
whereas in case of the physical mixture of 1:1 72%. However,
experimentally it was obtained, that in the last variant, at the reac-
tor outlet, we have virtually two times more methanol. Probably,
this is connected with the fact that the methanol formed in the
gas phase on catalysts granules is not completely transformed into
DME. In case of layerwise loading 2:1:2, the CO + H2 mixture
passes first through the layer of the catalyst of the methanol syn-
thesis; then, the unreacted gases and formed products pass
through the intermediate layer and further through c-Al2O3
where the formed methanol transforms into DME.
3.3. Effect of operating conditions
In the industrial production of methanol, dimethyl ether is
formed on the copper-zinc-aluminum catalyst as a by-product.
This is due to the presence in the catalyst of aluminum oxide which
has acid function (Table 1) for the transformation of methanol into
DME.
For the estimation of the contribution of aluminum oxide in the
DME formation, a blank experiment on the conversion of the
mixture of CO + H2 was performed on the R-1 catalyst before cat-
alytic studies. The CO conversion, when the mixture passes
through the layer of the catalyst, amounted to 17%, the DME yield
did not exceed 1%.
It is known that for catalysts of the methanol synthesis, there is
an initial evolutionary equilibration period. During this period, the
activity of the catalyst increases until a stable condition is attained.
The duration of the period of stabilization of the catalyst activity
depends on operating conditions (temperature, pressure, initial
feed composition) of the catalyst pretreatment and the composi-
Pore volume Average pore Acidity
(cm3 g1) diameter () mol NH3 g1
0.3 162 0.064
0.7 154 0.254
 I.A. Kurzina et al. / Chemical Engineering Journal xxx (2017) xxxxxx
Fig. 4. Variants of reactor loading of catalysts of methanol (dark marks) and dimethyl ether (light marks) synthesis.
100
Equilibrium
80 X CO
60
%
40 YDME
20 CO2
0
2:3 1:1 2:1:2 1:1 (mix)
Fig. 5. CO conversion, dimethyl ether yield (YDME) and CO2 conversion vs. variants
of catalyst loading presented in Fig. 4. Reaction conditions: H2/CO = 2, P = 30 bar,
T = 280 C. Experimental data (dotes) and calculated result (dash line).
tion of catalysts. Fig. 6 shows the initial period of stabilization of
the activity of layerwise (2:1:2 variant) loading of CuO-ZnO-
Al2O3 and c-Al2O3 catalysts. The results show that the catalyst
steady state is attained after the initial period of approximately
4 h. The activity and the selectivity of the catalysts remain constant
at least for the next 4 h. The time period during 8 h has been cho-
sen as a period of pretreatment of catalysts.
The effect of operating conditions (pressure, temperature, initial
ratio H2/CO, and catalyst stability) on the conversion of CO and the
yield of dimethyl ether was carried out experimentally for the
2:1:2 variant of catalyst loading (fig.5). Experimental results are
presented in figs. 610.
Fig. 7 shows the influence of pressure on the conversion of CO
and the yield of DME. The DME yield represents a parabolic depen-
dence, the maximum of which is attained at 30 bar and consist of
34%. The CO conversion increases along with the increase in the
pressure. The reagents concentrations at a pressure of 20 and
30 bar are close in values: the water content in the liquid phase
is 1215%, the methanol content is 8386%; nevertheless, the con-
version value is 13% greater at 30 bar. Despite the greater value of
the CO conversion, at 40 bar, the yield of DME amounts to 31%.
Please cite this article in press as: I.A. Kurzina et al., Direct synthesis of dimethyl ether from synthesis gas: Experimental study and mathematical modeling,
Chem. Eng. J. (2017), http://dx.doi.org/10.1016/j.cej.2017.04.132
5
100
80
XCO
60
40 YDME
20
0
1 2 3 4 5 6 7 8
Time on stream (hour)
Fig. 6. Initial evolution period of CO conversion and dimethyl ether yield (YDME) vs.
time on stream. Reaction conditions: H2/CO = 2, P = 30 bar, T = 280 C.
Another important parameter influencing the efficiency of the
reaction proceeding is temperature. When the temperature
increases, the equilibrium value of the DME concentration reduces
(fig. 3); however, its yield in the temperature range of 220280 C
increases due to the increase of the reaction rate. In the tempera-
ture range of 280300 C, while approaching to the equilibrium,
the reaction rate reduces and the DME yield reduces. Therefore,
in this case the optimal temperature of the direct synthesis is the
temperature approximately equal to 280 C (fig. 8).
The obtained results are in good agreement with the data of
paper [20]. The authors have established that for the H2/CO/CO2
molar ratio in the feed, 3/1.5/1, the optimal conditions for conduct-
ing the reaction of the direct synthesis of DME from CO and H2 on
the hybrid catalyst of CuOZnOAlO/NaHZSM5 are the tempera-
ture of 275 C and the pressure of 40 bar.
One more important parameter that influences the DME yield is
the initial ratio of H2/CO. The molar ratio of hydrogen and carbon
monoxide influences the product distribution. From the viewpoint
6 I.A. Kurzina et al. / Chemical Engineering Journal xxx (2017) xxxxxx

100 100
ium
Equilibr Equilibrium
X CO
80 80 X CO

60 60
%

%
40 40 YDME
YDME

20 20

0 0
10 20 30 40 50 0.5 1.0 1.5 2.0
Pressure (bar) H2/CO
Fig. 7. Effect of pressure on CO conversion and dimethyl ether yield (YDME). Fig. 9. Effect molar ratio H2/CO on CO conversion and dimethyl ether yield (YDME).
Reaction conditions: H2/CO = 2, T = 280 C. Experimental data (dotes) and calcu- Reaction conditions: P = 30 bar, T = 280 C. Experimental data (dotes) and calcu-
lated result (dash line). lated result (dash line).

100 E q u il 100
ibriu m

80 80
X CO XCO
60 60
%

YDME
40 40 YDME

20 20

0 0
220 240 260 280 300 0 30 60 90 120 150 180
o
Temperature ( C) Time (hour)
Fig. 8. Effect of temperature on CO conversion and dimethyl ether yield (YDME).
Reaction conditions: P = 30 bar, H2/CO = 2. Experimental data (dotes) and calculated Fig. 10. CO conversion and dimethyl ether yield (YDME) vs. time of reaction.
result (dash line). Reaction conditions: H2/CO = 2, P = 30 bar, T = 280 C.

of thermodynamics of simultaneously proceeding reactions (1)(3), 4. Conclusion

the optimal ratio is H2/CO = 1 (Fig. 1). However, depending on the
activity of catalysts of the methanol synthesis and its dehydration,
as well as their interaction in the mixture of catalysts or in the
composition of the bifunctional catalyst, the optimal ratio can be
different. Fig. 9 shows the influence of the initial molar ratio of
H2/CO on the CO conversion and the DME yield. On catalysts R-1
and c-Al2O3 when H2/CO = 0.5, the value of the CO conversion
equal to 13% and the DME yield equal to 2% are observed. With
the increase of the hydrogen content in the mixture, the DME yield
increases up to 34% during the conversion of 67% and reaches the
maximum when H2/CO = 2; apparently, the reaction of the metha-
nol synthesis prevails.
Fig. 10 shows the CO conversion and dimethyl ether yield
(YDME) vs. time of reaction. The results correspond to the following
reaction conditions: the catalysts loading - variant 2:1:2, H2/
CO = 2, P = 30 bar, T = 280 C. At that, the catalyst activity and
selectivity towards DME (stability) of catalyst remains practically
constant during 180 h reaction run.
On the basis of thermodynamic analysis, the study of the influ-
ence of reaction conditions (pressure, temperature, initial ratio H2/
CO) on the equilibrium content of components in the mixture dur-
ing the dimethyl ether synthesis from synthesis-gas was per-
formed. Theoretically, it has been found that the maximum
equilibrium concentration of DME is reached when H2/CO = 1,
which corresponds to the stoichiometry of brutto-reaction (6).
The increase of the CO conversion and the equilibrium concentra-
tion of DME was observed with the pressure increase. A sufficiently
strong change takes place when increasing the pressure up to 30
40 bar, which can be recommended for reaction run.
The effect of reaction conditions as well as the loading variants
of CuO-ZnO-Al2O3 catalysts for the methanol synthesis and its
dehydration (c-Al2O3) on the CO conversion and the dimethyl
ether yield in the direct synthesis of dimethyl ether from syngas
has been experimentally studied. It has been demonstrated
that the layerwise loading with the intermediate mixed layer of

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Please cite this article in press as: I.A. Kurzina et al., Direct synthesis of dimethyl ether from synthesis gas: Experimental study and mathematical modeling,
Chem. Eng. J. (2017), http://dx.doi.org/10.1016/j.cej.2017.04.132