Olefin Synthesis from Dimethyl Ether in the Presence of a Hydrothermally Treated Mg–HZSM-5/Al2O3 Catalyst: Effect of Reaction Conditions on the Product Composition and Ratio

Article abstract of DOI:10.1134/S0965544117100115

Systematic studies of olefin synthesis from dimethyl ether (DME) in the presence of a hydrothermally treated HZSM-5 zeolite catalyst modified with magnesium have been conducted. Dependences of DME conversion, product yield and selectivity, and lower olefin ratio on space time in the temperature range of 320–360°C have been analyzed. The type of the resulting products has been determined, and assumptions about the reaction chemistry have been made to reveal the role of methylation and hydrogen-transfer reactions in the products formation.

Full text of DOI:10.1134/S0965544117100115

ISSN 0965-5441, Petroleum Chemistry, 2017, Vol. 57, No. 12, pp. 1043–1051. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © M.V. Magomedova, E.G. Peresypkina, I.A. Davydov, S.N. Khadzhiev, 2017, published in Neftekhimiya, 2017, Vol. 57, No. 6, pp. 663–671.
Olefin Synthesis from Dimethyl Ether in the Presence
of a Hydrothermally Treated Mg–HZSM-5/Al2O3 Catalyst:
Effect of Reaction Conditions
on the Product Composition and Ratio
M. V. Magomedova, E. G. Peresypkina*, I. A. Davydov, and S. N. Khadzhiev
Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, Russia
*e-mail: peresypkina_eg@ips.ac.ru
Received September 12, 2017
Abstract—Systematic studies of olefin synthesis from dimethyl ether (DME) in the presence of a hydrother-
mally treated HZSM-5 zeolite catalyst modified with magnesium have been conducted. Dependences of
DME conversion, product yield and selectivity, and lower olefin ratio on space time in the temperature range
of 320–360°C have been analyzed. The type of the resulting products has been determined, and assumptions
about the reaction chemistry have been made to reveal the role of methylation and hydrogen-transfer reac-
tions in the products formation.
Keywords: olefin synthesis, dimethyl ether, HZSM-5 zeolite, chemistry, kinetics
DOI: 10.1134/S0965544117100115
To date, olefin synthesis from methanol and/or
dimethyl ether (DME) has been extensively studied:
various theories on the reaction and formation of the
first C–C bond mechanism have been put forward
[1–3]; the secondary reactions of the С2–С4 olefins
conversion—the methylation of ethylene, propylene,
n-butene, pentene [4–8], and aromatic compounds
with methanol [5, 9, 10] and the methylation of olefins
with DME [11, 12]—have been studied; routes for the
transition states of isomerization, cracking, and
hydrogen transfer formation have been proposed [13–
16]; the kinetics has been studied in detail [17–20].
However, since the 2000s, close attention has been
paid to the study of olefin synthesis using DME as a
feedstock produced directly from synthesis gas [11,
22–28]. According to experiments of the cited
authors, the main products are С2–С4 olefins, higher
С5–С8 olefins, С1–С8 alkanes, and aromatic com-
pounds. The methanol formation as a by-product is
attributed with the DME reversible hydration reaction
[29] or the DME chemisorption on a zeolite surface to
form methanol and methoxy groups [27].
Almost all of the reported in literature research
results was received using fresh zeolite catalysts sam-
ples and do not take into account the possibility of sig-
nificantly changing their properties under commercial
operation conditions. In a number of studies over
HZSM-5-based catalysts [30–32], it was shown that,
under olefin synthesis conditions, these catalysts quite
rapidly lose their initial activity and selectivity; the
zeolite deactivation is associated with a change in
acidity caused by the blocking of the active sites by the
coke. These results show that studies should be con-
ducted in the presence of catalyst samples exhibiting
properties that are similar to those expected in a long-
term commercial use, i.e., artificially aged samples.
Most of the authors assume that the first stage is
methanol dehydration to DME; this reaction occurs at
a significantly higher rate than the rate of olefin pro-
duction steps and has a high enthalpy of −184 kcal/kg
(methanol) [21]. In this aspect, all other products,
except for DME, are formed during secondary reac-
tions. This concept has given rise to the development
of methanol-to-olefins (MTO) technologies wich
include two reactors—one is for methanol conversion
to DME by dehydration, and the second one to olefins
synthesis. This principle has been implemented in the
following commercial processes using HZSM-5 zeo-
lites: the MTP technology (Lurgi, Germany) and the
DTP technology (Japan Gasoline Company and Mit-
subishi Chemical, Japan).
A well-known method of catalyst aging is a high-
temperature steam treatment. A review of the litera-
ture shows that extensive studies of zeolite dealumina-
tion via steam treatment are mostly focused on
1043

1044
MAGOMEDOVA et al.
changes in the structural and acidic properties of the 1 : 1. To heat the feed, the upper part of the reactor
material [33–35]. However, studies of the reaction space was filled with a quartz.
chemical aspects in the presence of a steam-treated
A mixture of DME (amount, 99.99 wt %; manu-
catalyst have not been reported.
facturer, Akzo Nobel, the Netherlands) with nitrogen
was used as a feedstock in the experiments. The DME
In this context, analysis of the reaction conditions
concentration in the mixture with nitrogen was 10–13
effect on the product composition and ratio in the
vol %.
presence of a hydrothermal treated catalyst is relevant
In olefin synthesis, space time per DME carbon
was varied in a range of 0.2–3.2 gcat h/gC to provide the
DME conversion in a range of 20–95%.
for the industrial process of olefin synthesis from
DME; this study is focused on the problem.
Reaction product selectivity and yield were calcu-
lated without taking into account the resulting water
according to the equations
EXPERIMENTAL
A magnesium-containing catalyst was synthesized
at the pilot factory using a ZSM-5 type zeolite with a
SiO2/Al2O3 ratio of 37, which is supplied in the ammo-
nium form (Angarsk catalyst and organic synthesis
plant). The zeolite was mixed with an alumina suspen-
sion with an Al2O3 content of 23 wt % in terms of dry
residue (Promyshlennye Katalizatory); after that,
extrudates were formed (Al2O3 content in the finished
catalyst of 33–34 wt %) and calcined at 500°C for 4 h.
To introduce a required amount of magnesium
(1.0 wt %), the prepared pellets were impregnated
with an aqueous solution of magnesium nitrate at
room temperature for 24 h and then dried at 110°C and
calcined at 500°C for 4 h. The steam treatment of the
catalyst was conducted at 500°C for 6 h (stabilization)
using the equipment and procedure described in [25].
After high-temperature steam treatment, the crystal-
line phase content in the zeolite structure remained
almost unchanged (Table 1). The observed changes in
the structural and acidic properties of the catalyst are
consistent with the literature data [36, 37].
nCi
Si =
Yi =
, mol %
nCi…n
∑
nCi
nDME(feed)
, mol%,
where nCi is the moles number of carbon-containing
compound i, mol/h; i…n is the carbon-containing
products; and nDME(feed) is the number of DME moles,
mol/h.
Analysis of reaction products was conducted using
a Kristallyuks-4000M on-line gas chromatograph
equipped with a flame ionization detector and a ther-
mal conductivity detector. The composition of С1–С7
hydrocarbons, methanol, and DME was determined
on a 27.5 m × 0.32 mm × 10 μm capillary column with
a CP-Poraplot Q phase. Nitrogen was determined on
a 3.0 m × 4 mm × 3 mm packed column with a Pora-
pak Q phase. Analysis was conducted using tempera-
ture programming of 90–250°C and helium as a car-
rier gas. The chromatograms were processed using the
NetChromWin software.
The mechanisms of olefin synthesis from DME
were studied on a laboratory unit in the flow mode in
the temperature range of 320–360°C at atmospheric
pressure. The reactor was a quartz tube with an inter-
nal diameter of 10 mm; it was equipped with a central
well for a movable thermocouple with a diameter
of 4 mm to measure the temperature directly in the
catalyst bed. The reactor was heated using an electric
furnace; temperature in the furnace was set using a
TRM-210 regulator (Russia). The catalyst charge was
0.5–1.0 g (0.4–0.63 mm fraction). Before loading into
the thermal comfort zone of the reactor, a catalyst
sample was mixed with quartz in a volume ratio of
RESULTS AND DISCUSSION
Effect of Temperature and Space Time
Data on the DME conversion in a temperature
range of 320–360°C at a space time of 0.2–3.2 gcat
h/gC in the presence of a stabilized Mg–HZSM-
5/Al2O3 catalyst sample are shown in Fig. 1. An
increase in temperature leads to a significant increase
in the conversion rate of DME. The initial section of
the “conversion–space time” dependence is linear;
this behavior is most probably attributed to the first
order with respect to DME concentration in the equa-
tion for DME consumption rate.
Dependences of the product yield on the contact
time at temperatures of 320 and 360°C are shown in
Figs. 2, 4, and 5. It is evident that the stabilized Mg–
HZSM-5/Al2O3 catalyst sample provides a high meth-
anol content in the products; the dependence of meth-
anol yield on space time has an extremum (Fig. 2,
Table 1. X-ray diffraction analysis of the crystalline
phase content in the zeolite component
Catalyst
Crystallinity, %
Mg–HZSM-5/Al2O3
93
92
Steamed Mg–HZSM-5/Al2O3
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OLEFIN SYNTHESIS FROM DIMETHYL ETHER
1045
35
100
90
80
70
60
50
40
30
20
10
30
25
20
15
10
5
0
1
2
3
Contact time, gcat h/gC
T = 320°C T = 340°C T = 360°C
0
1
2
3
Contact time, gcat h/gC
T = 320°C T = 360°C
Fig. 1. The DME conversion vs space time for a stabilized
Mg–HZSM-5/Al O catalyst.
2
3
Fig. 2. The methanol yield (solid line) and propylene yield
(dashed line) VS contact time at the different tempera-
tures.
solid line). An increase in temperature leads to a shift
of the extremum toward shorter space times. It should
be noted that the highest methanol yield is 27–32 mol
%; this value is significantly higher than the equilib-
rium yield (Fig. 3, dash-and-dot line) calculated on
the assumption that DME is converted to olefins and
water and the resulting water is involved in the hydra-
tion of the remaining (unreacted) DME.
An increase in temperature from 320 to 360°C
leads to a change in the behavior of formation of С1–
С4 alkanes and С5–С7 hydrocarbons. The behavior of
the curves corresponds to the apparent dependences
for the final products at the low temperature and for
The propylene yield exhibits an extreme behavior
similar to that of methanol (Fig. 2, dashed line); as in
the case of methanol, the temperature increasing leads
to a shift of the propylene yield maximum to the
shorter space times.
35
30
25
20
15
10
5
The dependences of the ethylene, butenes, C1–C4
alkanes, and С5–С7 hydrocarbons yields exhibit quite
a different behavior (Figs. 4, 5). It is evident that, with
an increase in the space time, the ethylene and butenes
yield increases monotonically, while the yield of С1–
С4 alkanes and С5–С7 hydrocarbons increases nonlin-
early (Fig. 5).
The formation of С1–С4 alkanes and С5–С7
hydrocarbons, which are secondary products, as in
catalytic cracking [38], largely occurs involving hydro-
gen transfer reactions:
Alkene + Alkene → Alkane + Diene;
Alkene + Alkene → Cycloalkane;
0
20
40
60
80
100
DME conversion, %
Diene + Alkene → Alkane + Arene;
ΣDiene → Arene +Н2;
Fig. 3. The methanol yield VS DME conversion at Т =
320°C. The solid line denotes the experimental data; the
dash-and-dot line stands for the calculated equilibrium.
Cycloalkane + Alkene → Alkane + Arene.
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MAGOMEDOVA et al.
35
35
30
25
20
15
10
5
30
25
20
15
10
5
0
1
2
3
0
1
2
3
Space time, gcat h/gC
Space time, gcat h/gC
T = 320°C T = 360°C
T = 320°C T = 360°C
Fig. 4. The ethylene yield (solid line) and butenes yield
(dashed line) VS contact time at the different tempera-
tures.
Fig. 5. The C –C alkanes yield (dashed line) and C –C
7
1
4
5
hydrocarbons yield (solid line) VS contact time at the dif-
ferent temperatures.
the intermediate products at the higher temperature;
this relationship is most pronounced for butenes and
С5–С7 hydrocarbons.
The nonmonotonic propylene yield behavior was
supposed in [28] to be due to the high reactivity one in
oligomerization–cracking reactions with ethylene and
butenes producing. However, this assumption explains
neither the observed correlation of the propylene and
methanol yields nor the extremum absence in the
curve of the butene yield, although the butenes crack-
ing occurs more vigorously than propylene.
Note that the behavior of the ethylene yield varies
only slightly with increasing temperature; this is seems
seems to the lower reactivity of ethylene in comparison
with other hydrocarbons, wich was reported also in
[27, 28].
The data obtained by measuring the product yield
as a function of space time lead to the following con-
clusions: both methanol and propylene are intermedi-
ate products of the reaction; С1–С4 alkanes are final
products; and ethylene, butenes, and С5–С7 hydro-
carbons change their behavior with temperature and
can be either final (at T = 320–340°C) or intermediate
products (at T > 360°C).
The apparent dependences for the product yield
are consistent with the results [29] describing a kinetic
model and dependences of the product mole fractions
of the products on space time at temperatures of 325–
400°C in the presence of an HZSM-5 zeolite with a
high silica ratio (SiО2/Al2О3 = 280) for the initial cat-
alyst activity conditions—at zero time on stream.
Analysis of our data reveals features that have not
been previously observed in similar studies of oxygen-
ate conversion, in particular, the maximum yield of
methanol and propylene (in mole fractions) as a func-
tion of space time.
To reveal the product formation sequence (pri-
mary/secondary), dependences of product selectivity
via DME conversion at the different temperatures
were plotted (Figs. 6–8) and values corresponding to
DME zero conversion were determined.
Perez-Uriarte et al. [29] attribute the methanol for-
mation with the DME hydration reaction in the sys-
The data show that the methanol selectivity as a
tem; however, our calculations based on the amount of function of DME conversion linearly decreases and
water in the system give significantly lower equilib- hardly depends on the reaction temperature (Fig. 6a).
rium methanol yields. It seems, there is another path- Extrapolation of the line to the zero DME conversion
way of methanol formation which leads to the value gives a methanol selectivity of about 75–78 mol %.
observed yield; which is not associated with DME This finding suggests that methanol is a primary prod-
hydration reaction.
uct of the reaction.
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OLEFIN SYNTHESIS FROM DIMETHYL ETHER
(а) (b)
1047
80
70
60
50
40
30
20
10
35
30
25
20
15
10
5
0
20
40
DME conversion, %
T = 320°C T = 360°C
60
80
100
0
20
40
DME conversion, %
T = 320°C T = 360°C
60
80
100
Fig. 6. The selectivity of methanol (a) and propylene (b) formation VS DME conversion at the different temperatures.
(а)
(b)
35
30
25
20
15
10
5
35
30
25
20
15
10
5
0
20
40
DME conversion, %
T = 320°C T = 360°C
60
80
100
0
20
40
DME conversion, %
T = 320°C T = 360°C
60
80
100
Fig. 7. The selectivity of butenes (a) and ethylene (b) formation VS DME conversion at the different temperatures.
Along with methanol, the primary products with a
nonzero selectivity at a zero space time undoubtedly
include propylene, butenes, and С5–С7 hydrocarbons
(Figs. 6b, 7a, 8) with apparent molar selectivities of
75–78, 11–13, and 4–5 mol %, respectively. Ethylene
is a primary product at the low reaction temperature
This result is inconsistent with the literature con-
cepts of ethylene as the main primary product of oxy-
genate conversion. Propylene was identified as a pri-
mary product only in [27] in IR spectroscopy studies
in a temperature range of 200–250°C. Most probably,
ethylene is the main primary product only in the case
of methanol conversion and the mechanism details of
and a secondary product at the high temperature the methanol and DME conversion to olefins differ.
(Fig. 7b). Unlike selectivities for other reaction prod-
It is noteworthy that in a DME conversion range
ucts, the ethylene selectivity decreases with increasing
above 70–75%, the selectivity for propylene passes
temperature; this finding is an unexpected result.
С1‒С4 alkanes undoubtedly are secondary products of
the reaction.
through a maximum (Fig. 6b) and the selectivity for
butenes and С1–С4 alkanes abruptly increases
(Figs. 7a, 8). This behavior is most likely due to both
PETROLEUM CHEMISTRY Vol. 57 No. 12 2017

1048
MAGOMEDOVA et al.
3.0
35
30
25
20
15
10
5
2.5
2.0
1.5
1.0
0.5
0
20
40
DME conversion, %
T = 320°C T = 360°C
60
80
100
0
20
40
DME conversion, %
T = 320°C T = 360°C
60
80
100
Fig. 8. The selectivity of C –C alkanes (dashed line) and
Fig. 9. The С Н /С Н (dashed line) and С Н /С Н
8
1
4
2
4
3
6
2
4
4
C –C hydrocarbons (solid line) production VS DME
(solid line) ratio VS DME conversion at the different tem-
peratures.
5
7
conversion at the different temperatures.
the contribution of propylene methylation with meth-
anol to form butenes and hydrogen transfer reactions.
This assumption is supported by an increase in the
selectivity for С1–С4 and С5–С7 hydrocarbons pro-
duction with increasing DME conversion. The selec-
tivity for С5–С7 hydrocarbons, similar to that of eth-
ylene, decreases production with increasing reaction
temperature, while the С1–С4 alkane selectivity does
not (Fig. 8).
ylene/propylene and ethylene/butenes molar ratios
suggests that, at high DME conversion, the composi-
tion of the resulting products is significantly affected
by the propylene methylation reaction. As a conse-
quence, the propylene yield decreases and the butene
yield increases.
This conclusion is confirmed by the behavior of the
propylene/butenes mole ratio on DME conversion
(Fig. 10). At high DME conversion, where secondary
reactions occur, the ones ratio is decrease owing to the
propylene consumption during methylation reaction
with butenes production.
The ratio of the net rates (taking account of the for-
mation and consumption) for the key products can be
determined more clearly by analyzing the molar ratios
of the product yield. Dependences of the eth-
ylene/propylene and ethylene/butenes yield molar
ratio on DME conversion are shown in Fig. 9. With an
increase in the reaction temperature, at an identical
DME conversion, the ethylene/propylene ratio sig-
nificantly decreases. Extrapolation of line to the zero
DME conversion suggests that, at a high temperature
(360°C), ethylene is most probably a product of sec-
ondary reactions. In the range of high DME conver-
sion, where the contribution of secondary reactions is
significant, the ethylene/propylene ratio abruptly
increases; this fact indicates an intensification of the
secondary reactions of propylene conversion.
The dependences shown in Fig. 10 exhibit an
almost constant propylene/butenes ratio with an
increase in the DME conversion to 70–75%, i.e., until
the onset of secondary reactions. At a low DME con-
version, the total amount of ethylene and butenes in
the products is 1 mol per mole of propylene (Fig. 9);
with an increase the temperature, at an identical DME
conversion, the С3Н6/(С2Н4+С4Н8) ratio increases,
although the С3Н6/С4Н8 ratio decreases under the
same conditions. In this case, the result is attributed to
a significant increase in the propylene/ethylene ratio
with increasing temperature. In general, the data show
that, to achieve a high propylene yield, DME conver-
sion should be run at high temperatures and a mini-
mum contribution of methylation reactions.
Similarly, at an identical DME conversion, the
ethylene/butenes molar ratio also decreases with
increasing reaction temperature (Fig. 9). However, in
the high DME conversion range, it exhibits a plateau during DME conversion is clearly revealed by analysis
or slightly decreases. Joint analysis of the eth- of the ratio between isohydrocarbons and normal
The competition of various reactions that occur
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OLEFIN SYNTHESIS FROM DIMETHYL ETHER
1.2
1049
3.0
2.5
2.0
1.5
1.0
0.5
1.0
0.20
0.15
0.10
0.05
0
20
40
60
80
100
DME conversion, %
T = 320°C T = 360°C
0
20
40
DME conversion, %
T = 320°C T = 360°C
60
80
100
Fig. 11. The isobutenes and n-butenes ratio VS DME con-
version at the different temperatures (dashed line denotes
the thermodynamically equilibrium value).
Fig. 10. The С Н /С Н (solid line) and С Н /(С Н +
3
6
4
8
3
6
2
4
С Н ) (dashed line) ratio VS DME conversion at the dif-
4
8
ferent temperatures.
ficient high despite the fact that the rate of butenes for-
mation is considerably higher than that of alkanes.
hydrocarbons in C4 olefin and alkane fractions
(Figs. 11, 12).
It is evident that the iso-/n-C4H8 ratio (Fig. 11)
does not depend on the temperature; at a DME con-
version up to 70–75%, it is 0.17–0.18; this value is far
from the thermodynamically probable value of 0.97–
1.08 for the studied temperature range. In the DME
conversion range above 75%, the ratio significantly
decreases owing to the occurrence of secondary reac-
tions.
At high DME conversion rates, the trans-/cis-
butenes ratio abruptly increases and exceeds the ther-
modynamically equilibrium values; this feature is
characteristic of hydrocarbon conversion in the pres-
ence of zeolite catalysts by the carbocation mecha-
16
14
12
10
8
The ratio of С4 isolalkane and n-alkane hydrocar-
bons is up to 9–11; this value is significantly higher
than the thermodynamic equilibrium of 0.94–1.05
(Fig. 12). The dependence exhibits a nonmonotonic
behavior and increases with the increasing tempera-
ture despite the thermodynamic equilibrium suggests
the inverse relationship.
Most probably, isobutene, along with other
butenes, is a primary product; it is involved in a rapid
hydrogen transfer reaction with the predominant for-
mation of isobutane. The isomerization rate of butenes
is significantly higher than that of butanes; this feature
is responsible for the thermodynamically nonequilib-
rium content of isobutane in the reaction products.
This hypothesis is also confirmed by data on the trans-/
cis-butenes ratio in the reaction products (Fig. 13).
This ratio is fairly close to thermodynamic equilib-
rium; it increases with increasing temperature and
approaches a thermodynamic value of 1.3. Thus, it can
be assumed that the butenes isomerization rate is suf-
6
4
2
0
20
40
60
80
100
DME conversion, %
T = 320°C T = 360°C
Fig. 12. The isobutanes and n-butanes ratio VS DME con-
version at the different temperatures (dashed line denotes
the thermodynamically equilibrium value).
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MAGOMEDOVA et al.
ACKNOWLEDGMENTS
2.0
1.5
1.0
0.5
This work was carried out in the TIPS RAS
with support of Russian Science Foundation (project
no. 17-73-30046).
REFERENCES
1. U. Olsbye, S. Svelle, M. Bjorgen, et al., Angew. Chem.
Int. Ed. 51, 5810 (2012).
2. M. W. Erichsen, S. Svelle, and U. Olsby, J. Catal. 298,
94 (2013).
3. D. Lesthaege, J. van der Mynsbrugge, M. Vandichel,
et al., Chem. Catal. Chem. 3, 208 (2011).
4. S. Svelle, P. O. Ronning, and S. Kolboe, J. Catal. 224,
115 (2004).
5. X. Sun, S. Mueller, H. Shi, et al., J. Catal. 314, 21
(2014).
0
20
40
DME conversion, %
T = 320°C T = 360°C
60
80
100
6. S. Svelle, P. O. Ronning, U. Olsbye, and S. Kolboe,
J. Catal. 234, 385 (2005).
7. S. Svelle, S. Kolboe, O. Swang, and U. Olsbye, J. Phys.
Chem. B 109, 12874 (2005).
8. S. Svelle, M. Visur, U. Olsbye, and M. Bjorgen, Top.
Catal. 54, 897 (2011).
Fig. 13. The trans- and cis-butenes ratio VS DME conver-
sion at the different temperatures (dashed line denotes the
thermodynamically equilibrium value).
9. X. Sun, S. Mueller, Y. Liu, et al., J. Catal. 317, 185
(2014).
10. S. Rabiu and S. Al-Khattaf, Ind. Eng. Chem. Res. 47,
39 (2008).
nism, which is most likely to occur in secondary reac-
tions involving DME.
11. I. M. Hill, S. A. Hashimi, and A. Bhan, J. Catal. 285,
115 (2012).
12. I. M. Hill, A. Malek, and A. Bhan, ACS Catal. 3, 1992
Thus, to summarize the data derived in this study,
it can be stated that DME conversion over hydrother-
mal treated Mg–HZSM-5/Al2O3 catalyst provides a
high methanol yield; the numerical values of the yield
pass through a maximum with an increase in the space
(2013).
13. D. A. Simonetti, R. T. Carr, and E. Iglesia, J. Catal.
285, 19 (2012).
14. M. Boronat, P. Viruela, and A. A. Corma, J. Phys.
Chem. A 102, 9863 (1998).
time. A similar relationship is observed for the propyl- 15. D. A. Simonetti, J. H. Ahn, and E. Iglesia, Chem.
Catal. Chem. 3, 704 (2011).
ene yield.
16. M. Boronat, P. Viruela, and A. Corma, J. Phys. Chem.
B 103, 7809 (1999).
It has been found that the primary products of
17. A. T. Aguayo, D. Mier, A. G. Gayubo, et al., Ind. Eng.
DME conversion in the presence of this catalyst are
methanol, propylene, butenes, and С5–С7 hydrocar-
bons. Ethylene is a primary product at a low reaction
temperature and, most probably, a secondary product
at a high temperature.
Chem. Res. 49, 12371 (2010).
18. P. Kumar, J. W. Thybaut, S. Svelle, et al., Ind. Eng.
Chem. Res. 52, 1491 (2013).
19. H. A. Zaidi and K. K. Pant, Korean J. Chem. Eng. 27,
1404 (2010).
20. X. Huang, H. Li, W.-D. Xiao, and D. Chen, Chem.
The selectivity of products varies diversely with
temperature increasing. The selectivity of methanol
and С1–С4 alkanes formation does not depend
on temperature, while the selectivity of ethylene and
С5–С7 hydrocarbons decreases with increasing ones.
At the same time, the selectivity of propylene and
butenes production increases with increasing tem-
perature. The composition of С2–С4 olefins formed at
a high DME conversion significantly depends on the
secondary reactions intensity—methylation and
hydrogen transfer—determined by the temperature
and the space time.
Eng. J. 299, 263 (2016).
21. C. D. Chang and A. J. Silvestri, J. Catal. 47, 249 (1977).
22. A. S. Al-Dughaither, PhD Dissertation (The University
of Western Ontario, 2014).
23. T. S. Zhao, T. Takemoto, and N. Tsubaki, Catal. Com-
mun. 7, 647 (2006).
24. T. I. Goriyanova, E. N. Biryukova, N. V. Kole-
snichenko, and S. N. Khadzhiev, Pet. Chem. 51, 169
(2011).
25. S. N. Khadzhiev, N. V. Kolesnichenko, E. N. Khivrich,
et al., Pet. Chem. 53, 225 (2013).
26. T. I. Batova, E. N. Khivrich, G. N. Shirobokova, et al.,
Pet. Chem. 53, 383 (2013).
PETROLEUM CHEMISTRY
Vol. 57
No. 12
2017

OLEFIN SYNTHESIS FROM DIMETHYL ETHER
1051
27. H. Yamazaki, H. Shima, H. Imai, T. Yokoi, T. Tatsumi, 34. L. H. Ong, M. Domok, R. Olindo, et al., Microporous
J. N. Kondo, J. Phys. Chem. C, 24091 (2012).
Mesoporous Mater. 164, 9 (2012).
35. S. M. T. Almutairi, B. Mezari, E. A. Pidko, et al., J.
28. P. Perez-Uriarte, A. Ateka, M. Gamero, et al., Ind.
Catal. 307, 194 (2013).
Eng. Chem. Res. 55, 6569 (2016).
36. S. M. Campbell, D. M. Bibby, J. M. Coddington, et al.,
29. P. Perez-Uriarte, A. Ateka, A. T. Aguayo, et al., Chem.
J. Catal. 161, 338 (1996).
Eng. J. 302, 801 (2016).
37. S. Zhang, Y. Gong, L. Zhang, et al., Fuel Process.
30. A. Sardesai, T. Tartamella, and S. Lee, Pet. Sci. Tech-
Technol. 129, 130 (2015).
nol. 17, 273 (1999).
38. S. N. Khadzhiev, Catalytic Cracking: Refinery Engi-
neer’s Handbook, Ed. by G. A. Lastovkin, E. D. Rad-
chenko, and M. G. Rudin (Khimiya, Leningrad, 1986)
[in Russian].
31. A. S. Al-Dughaither and H. Lasa, Fuel 138, 52 (2014).
32. P. Perez-Uriarte, M. Gamero, A. Ateka, et al., Ind.
Eng. Chem. Res. 55, 1513 (2016).
33. A. G. Vlessidisa, L. Nalbandianb, and N. P. Evmiri-
Translated by M. Timoshinina
disa, Microporous Mesoporous Mater. 47, 369 (2001).
PETROLEUM CHEMISTRY Vol. 57 No. 12 2017