Synthesis of lower olefins from dimethyl ether in the presence of zeolite catalysts modified with rhodium compounds

Article abstract of DOI:10.1134/S0965544111010105

The catalytic properties of zeolite catalysts modified with rhodium compounds in the synthesis of olefins from dimethyl ether (DME) and methanol (MeOH) have been studied. The optimum concentration of rhodium in the composition of a zeolite catalyst has been determined. It has been shown that one of the possible precursors of ethylene in the conversion of DME is ethanol, which, under reaction conditions, can be formed through both the DME isomerization and methanol homologation stages.

Full text of DOI:10.1134/S0965544111010105

ISSN 0965ꢀ5441, Petroleum Chemistry, 2011, Vol. 51, No. 1, pp. 55–60. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © N.V. Kolesnichenko, T.I. Goryainova, E.N. Biryukova, O.V. Yashina, S.N. Khadzhiev, 2011, published in Neftekhimiya, 2011, Vol. 51, No. 1, pp. 56–61.
Synthesis of Lower Olefins from Dimethyl Ether in the Presence
of Zeolite Catalysts Modified with Rhodium Compounds
N. V. Kolesnichenko, T. I. Goryainova, E. N. Biryukova, O. V. Yashina, and S. N. Khadzhiev
Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, Russia
eꢀmail: nvk@ips.ac.ru
Received August 27, 2010
Abstract—The catalytic properties of zeolite catalysts modified with rhodium compounds in the synthesis of
olefins from dimethyl ether (DME) and methanol (MeOH) have been studied. The optimum concentration
of rhodium in the composition of a zeolite catalyst has been determined. It has been shown that one of the
possible precursors of ethylene in the conversion of DME is ethanol, which, under reaction conditions, can
be formed through both the DME isomerization and methanol homologation stages.
DOI: 10.1134/S0965544111010105
The production of lower olefins is of a large scale
and is constantly increasing [1]. The processes of therꢀ
mal pyrolysis and catalytic cracking of hydrocarbon
feedstock remain the basic methods to obtain ethylene
and propylene. The rates of growth in the consumpꢀ
tion of these useful chemicals are far ahead of the scale
of their production, thereby entailing the search for
another, cheaper, and more available hydrocarbon
feedstock. This raw material is natural gas; its producꢀ
tion and largeꢀscale use are forecast for a long period.
А
B
Syngas
methanol
C
DME
olefins
Scheme 1. Production of С –С olefins from natural gas
2
3
via methanol and/or DME.
Route A implies the production of olefins from
syngas via methanol in one stage in the presence of
ZSMꢀ5. This method of direct conversion of methaꢀ
nol to olefins was developed by a number of compaꢀ
nies (Mobil Oil Corporation, UOP, etc.) for over 30
years and commercialized [8].
The most known and explored method for obtainꢀ
ing chemicals from natural gas is their production via
a preliminary conversion of natural gas to syngas
The same period was marked by the appearance of
a more efficient process that employs a highly selective
HꢀSAPOꢀ34 catalyst at the stage of synthesis of olefins
from methanol. Being developed by UOP and Norsk
Hydro [4, 8–12], this process is focused on the proꢀ
duction of ethylene and propylene; in addition, it is
intended to utilize byꢀproducts, including butenes, as
a fuel for heat power plants. The yield of С2–С3 olefins
is 75–90 wt %.
(
СО/Н2). The methaneꢀderived syngas can be subseꢀ
quently converted into olefins, which are the most
important feedstock of the petrochemical industry.
This conversion is carried out either in one stage
(using the Fischer–Tropsch process) or via an interꢀ
mediate production of methanol or dimethyl ether
(DME).
Route B includes the stage of DME synthesis from
methanol by the dehydration of СН3ОН with the subꢀ
sequent conversion of a mixture of methanol, DME,
and Н2О to olefins; it is being developed by the Lurgi
Co. in cooperation with some other German compaꢀ
nies (MG Technologies AG) [6, 7, 13–16]. The proꢀ
cess is aimed to obtaining propylene on a ZSMꢀ5ꢀ
based catalyst. The Lurgi process gives the possibility
to process more than 99% methanol, of which 70% is
consumed to produce propylene, 26% makes gasoline,
and 4% acts as a heat transfer agent. The Lurgi process
has been patented in a number of countries [7, 13, 14],
and a demonstration unit is in operation [6].
Iron catalysts, which are the most active and selecꢀ
tive in the Fischer–Tropsch synthesis of olefins, proꢀ
duce lower olefins (С2–С4) with a yield of at most 27%
[2]. Unlike the Fischer–Tropsch process, the proꢀ
cesses of syngas conversion to lower olefins via methaꢀ
nol and/or DME give the possibility to obtain
ethylene and/or propylene with yields at a level of 75–
90% [3–7].
Several routes to obtain С2–С3 olefins from natural
gas via methanol and/or DME are under development
(Scheme 1).
55

56
KOLESNICHENKO et al.
Further development of the synthesis of lower oleꢀ good catalysts for methanol homologation, and anaꢀ
fins from natural gas can even more significantly lyzed certain features of olefin synthesis from DME.
increase the advantages of this method in comparison
with the traditional technique. For example, at
present, great interest is aroused by the version of proꢀ
EXPERIMENTAL
duction of С2–С3 olefins that involves a direct syntheꢀ
sis of DME from syngas (route C), which is being
developed by the JGC Corp. (Japan) [17], by the Chiꢀ
nese group [4], and in our studies [18, 19]. In [4, 17],
natural gas is converted at the first stage to syngas (a
mixture of СО/Н2) using steam or autothermal
reforming. At the second stage, syngas is converted to
a mixture of СН3ОН, DME, and Н2О (at a temperaꢀ
Dimethyl ether with a purity of 99.8% (manufacꢀ
tured by the OAO NAK Azot, Novomoskovsk, Russia)
was used as a feedstock. In the reaction of formation of
lower olefins from DME, we studied catalyst samples
based on zeolite ZSMꢀ5, or, more precisely, its domesꢀ
tic analog highꢀsilica zeolite TsVM with a SiO2/Al2O3
mole ratio of 30 (which, produced by ZAO Nizhegorꢀ
odskie sorbenty, contains no more than 0.11 wt %
sodium oxide). To obtain the hydrogen form of the
zeolite (HZSMꢀ5) with a preset residual sodium oxide
content, we used a double cation exchange of Na+ in a
1 N ammonium nitrate solution with subsequent dryꢀ
ture of 210–300 С and a pressure of 4–150 atm) in the
°
presence of a bifunctional catalyst that comprises the
“metal” component, i.e., a methanol synthesis cataꢀ
lyst (CuO–ZnO/Al2O3 or ZnO–Cr2O3/Al2O3), and the
“acid” component, i.e., an alcohol dehydration site
(aluminum oxide or zeolite), thus in one stage comꢀ
bining the production of methanol and its dehydration
to DME. The resulting СН3OH/DME/H2О mixture,
without separation into individual components, is
placed into an olefin synthesis reactor, where at a temꢀ
ing and calcining at 500 С for 4 h.
°
Zeoliteꢀcontaining catalysts were prepared via
mixing the HZSMꢀ5 zeolite with an alumina slurry
(with 18 wt % dry Al2O3 produced by ZAO Nizhegorꢀ
odskie sorbenty) as a binding agent and the subsequent
shaping of granular extrudates (the Al2O3 content of
the resulting catalyst was 33–34 wt %). After that, the
extrudates were successively dried in air and in a drying
perature of 380–550 С and a pressure of 1–6 atm, in
°
the presence of HꢀSAPOꢀ34, a hydrocarbon product
is obtained from which the ethylene and propylene
fractions are isolated and the remaining components
are used as a heat transfer agent for thermal power
plants. Lower olefins are produced with a high yield
(86%) and high selectivity (80–90%), with ethylene
and propylene making about 80% of the hydrocarbon
product.
oven and calcined at 500 С for 4 h. To introduce active
°
metals into the zeolites, we used the ion exchange of
the zeolites with an aqueous solution of a metal salt
(La, Zr) followed by mixing with the binding agent
(
Al2O3) or the impregnation of the resulting zeolite–
binder extrudates with an aqueous solution of a macꢀ
romolecular metal (Rh) complex.
The experiments were carried out using a laboraꢀ
tory setup employing a flowꢀtype microreactor. The
feedstock was DME (or methanol), and the DME and
methanol diluent was helium. A 0.5ꢀg (1.0 ml) charge
of the catalyst (a fraction of 0.4–0.63 mm) was placed
in a quartz flow reactor. After that, the catalyst was
However, with a decreasing content of methyl alcoꢀ
hol and an increasing amount of DME in the original
feedstock, the yield of olefins decreases. This is due to
the properties of the selected catalyst: the microporous
SAPOꢀ34 material, which proved to be the best cataꢀ
lyst for the synthesis of olefins from methanol, is not so
effective in the reaction with DME and is rapidly
deactivated because of heavy coking.
activated in a flow of helium at 400
reactant feed space velocity (500–5000 h–1), temperaꢀ
ture (240–340 ), and pressure (~1 atm) were set.
°
С. The desired
°С
Unlike the cited authors [4, 17], in [18, 19] we synꢀ
thesized olefins from DME that barely contained
methanol, and its conversion was carried out over a
catalyst based on highꢀsilica pentasil, which is an anaꢀ
logue of HꢀZSMꢀ5, modified with La and Zr. This was
possible owing to the development of both a singleꢀ
step syngasꢀtoꢀDME process [20] and an efficient catꢀ
alyst for the conversion of DME to olefins. The selecꢀ
tivity for С2–С4 olefins was up to 80% with a DME
conversion of ~80%.
Liquid products were condensed in a receiver; the gas
flow, using a dosing cock, was supplied to a chromatoꢀ
graph for analysis. The reaction gas stream of DME
conversion is a mixture of С1–С6 hydrocarbons; the
main method of their analysis is gas–liquid chromaꢀ
tography (GLC).
The gas mixtures were analyzed on a Kristallyuks
4000M chromatograph with a flame ionization detecꢀ
tor. The dimensions of the capillary column were
27.5 m
×
0.32 mm
×
10 m; the nonpolar CPꢀporaꢀ
μ
The key factor of high selectivity for the yield of PLOT Q phase was used as an adsorbent; this phase
olefins from CO and Н2 via DME is the rate and direcꢀ proved to be fairly efficient in separation of the basic
tion of formation of the single C–C bond from the groups of the products (DME, СН3ОН
O bond. Most researchers assume that the primary carbons). The temperature was programmed from 80
product in this process is ethanol and/or methyl ethyl to 150 C at a heating rate of 30 C/min; helium was
, С1–С6 hydroꢀ
C
⎯
°
°
ether [21–27]. In this work, in order to improve the used as a carrier gas (a flow rate of 30 ml/min). The
properties of catalysts, we studied the effect of their resulting chromatograms were processed using the
modification with rhodium compounds, which are NetChromWin software.
PETROLEUM CHEMISTRY Vol. 51
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SYNTHESIS OF LOWER OLEFINS FROM DIMETHYL ETHER
57
Table 1. Effect of rhodium concentration in an Rh/HZSM/Al2O3 zeolite catalyst on its catalytic properties in the conversion of
DME to olefins
Product composition
,
wt %
C5=
Rh concentration in Converꢀ
C2=
C3=
C4=
ΣC=2 C=4
–
the catalyst
,
wt %
sion, %
CH4
Σ
C2+
0.05
0.1
99.6
99.9
99.5
0.8
0.2
0.9
19.9
24.3
21.4
18.3
19.4
20.3
7.9
6.3
7.1
3.5
2.7
3.0
50.4
47.1
48.2
46.1
50.0
48.8
0.2
–1
Note: T = 340°C, P = 0.1 MPa; feed mixture: 10% DME + He;v = 2000 h
.
0
Table 2. Effect of the nature of a rhodium compound on the catalytic properties of a zeolite catalyst
Product composition, wt %
Rh introducꢀ
tion mode
Converꢀ
sion, %
T, C
°
C2=
C3=
C4=
C5=
ΣC=2
–
C4=
CH4
Σ
C2+
from RhCl3
from AcAc
from PEI
320
340
320
340
320
340
79.1
99.7
97.2
99.6
87.4
99.9
1.3
1.2
1.6
1.6
0.4
0.2
29.2
18.6
24.5
10.9
28.2
24.3
27.2
11.4
14.3
7.4
14.6
10.1
15.2
8.7
3.8
5.4
6.1
3.4
0.9
2.7
23.9
71.0
40.1
54.0
27.0
75.2
50.0
53.3
38.3
68.0
23.5
47.1
35.4
19.4
11.6
6.3
–1
Note: P = 0.1 MPa; feed mixture: 10% DME + He; v = 2000 h ; an Rh (0.1%)–HZSM/Al O catalyst; AcAc is acetylacetonate; PEI is
0
2 3
polyethyleneimine.
RESULTS AND DISCUSSION
(Table 2). The highest selectivity for С2–С4 olefins
(50.0–75.2 wt %) was obtained on the sample modiꢀ
fied with the rhodium macromolecular (polyethyleneꢀ
imine) complex.
The initial HꢀZSMꢀ5 zeolite was modified with a
rhodium complex and tested in the conversion of
DME to olefins. First, we studied the effect of rhodꢀ
ium concentration in the zeolite catalyst on its cataꢀ
lytic properties (Table 1). The data in Table 1 show that
under these conditions, the reaction occurs with
almost total conversion of DME; an increase in the
concentration of rhodium from 0.05 to 0.1 wt % leads
to an increase in the selectivity for ethylene and propyꢀ
lene by 4.4 and 1.1 wt %, respectively; the further
increase in the rhodium loading is accompanied by a
decrease in the ethylene selectivity and an insignifiꢀ
cant increase in the propylene selectivity. The best
results were obtained for rhodium loading of 0.1 wt %.
To study the direction of formation of a primary
C–C bond from a C–O bond in the conversion of
DME to olefins, the rhodiumꢀcontaining catalyst was
tested under the “methanol homologation condiꢀ
tions” at 240 С and atmospheric pressure (Table 3).
°
The DME conversion is fairly low in this case; signifiꢀ
cant amounts of methanol and up to 8.2 wt % ethanol
were found in the product, as well as a large number of
alkanes. A rise in the reaction temperature to 270 С
°
leads to an appreciable increase in the selectivity for
ethylene and propylene and to a decrease in the
The effect of the nature of a rhodium compound on
the catalytic properties of a zeolite catalyst was studied amount of ethanol and methanol, with the decline in
Table 3. Conversion of DME on an Rh (0.1)/HZSM/Al2O3 catalyst
Product composition, wt %
Converꢀ
T, °C
C2=
C3=
C4=
C5=
sion, %
CH4
Σ
C2+
MeOH
EtOH
240
270
8.6
1.0
1.5
5.8
16.9
29.2
0.1
0.1
–
24.1
7.1
43.9
35.2
8.2
2.8
20.4
22.0
2.3
–1
Note: P = 0.1 MPa; feed mixture: 10% DME + He; v = 2000 h
.
0
PETROLEUM CHEMISTRY Vol. 51
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58
KOLESNICHENKO et al.
of DME is much lower than that on RhꢀHZSM/Al2O3
35
30
25
20
15
10
5
(Table 3); the conversion of methanol in an atmoꢀ
sphere of CO and Н2 on the LaꢀZrꢀRhꢀHZSM/Al2O3
catalyst, unlike the RhꢀHZSM/Al2O3 catalyst, occurs
with the formation of trace amounts of ethanol. The
occurrence of the DME conversion reaction in a flow
of syngas instead of helium leads to an insignificant
increase in the conversion of DME and an increase in
the total selectivity for C2=
increase for propylene.
–
C=4 olefins with a higher
0
500
1500
2500
3500
4500
5500
–1
Space velocity of the DME + He mixture, h
The appreciably lower yield of ethanol on LaꢀZrꢀ
RhꢀHZSM/Al2O3 can be explained by a higher activity
of the catalyst in the synthesis of olefins. The increase
in the selectivity for olefins in the DME conversion in
an atmosphere of CO and Н2 suggests that, along with
the isomerization of DME, a competitive reaction of
DME dehydration to methanol takes place, and ethaꢀ
nol can also be formed via its homologation reaction.
Dependence of the MeOH/EtOH ratio on the space
velocity of the feed gas mixture on Rh/HZSM/Al O (
270°C; original mixture: 10% DME + He).
T
3
=
2
the yield of ethanol being more considerable. The
methanol/ethanol ratio varies from 5.4 to 12.6.
Based on the above results, we can assume that the
formation of lower olefins follows Scheme 2, which
implies ethanol is produced mostly via the isomerizaꢀ
tion of DME.
The study of the effect of space velocity on the
methanol/ethanol ratio showed that an increase in the
space velocity is accompanied by an increase in the
MeOH/EtOH weight ratio, thereby suggesting that
methanol is an intermediate product in the formation
of ethanol (figure).
2CH OH
3
–H O
2
+H O
2
To verify this assumption, we carried the homoloꢀ
gation of methanol on an Rh/HZSM/Al2O3 catalyst.
Table 4 shows that methanol homologation occurs at
an extremely low rate under these conditions. The
amount of ethanol in the product of methanol converꢀ
sion at a low temperature is significantly lower than
that of the product of DME conversion under the
same conditions (Table 3).
CO/H
2
CH3OCH3
isomerization
…
C2H5OH
C2H4
Scheme 2. Formation of ethylene from DME or methanol.
An increase in the temperature to 340 С sharply
°
enhances the selectivity for the formation of olefins
from DME on rhodiumꢀmodified samples (Table 6).
For example, an increase in the temperature from 270
to 340°C leads to an increase in the DME conversion
over the Rh/HZSMꢀ5/Al2O3 catalyst from 20.4 to
Based on these data, we can conclude that ethanol
is most probably formed mainly through the isomerꢀ
ization of DME; that is, the reaction of methanol
homologation to ethanol is much more difficult than
the isomerization of DME to ethanol.
100 wt %; the selectivity for ΣC=2 C4= olefins remains
–
almost unchanged. By contrast, the DME conversion
on La/Zr/Rh/HZSM/Al2O3 increases only up to 73%
and the selectivity for C=2 C=4 olefins increases from
–
The conversion of DME and MeOH was studied
under the “homologation conditions” on a LaꢀZrꢀ
HZSM/Al2O3 catalyst modified with the rhodium
macrocomplex. Table 5 shows that the selectivity for
ethanol on LaꢀZrꢀRhꢀHZSM/Al2O3 in the conversion
Table 4. Conversion of MeOH on an Rh(0.1)/HZSM/Al2O3 catalyst
Product composition, wt %
Converꢀ
sion, %
T, °C
C2=
C3=
C4=
C5=
CH4
Σ
C2+
2.1
DME
EtOH
240
270
9.4
1.2
2.7
8.2
2.8
–
–
–
90.6
21.3
0.6
4.0
78.3
11.9
16.3
0.4
37.9
–1
Note: P = 0.1 MPa; original mixture: 10% MeOH + 30% CO + 60% H ; v = 2000 h
.
2
0
PETROLEUM CHEMISTRY Vol. 51
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SYNTHESIS OF LOWER OLEFINS FROM DIMETHYL ETHER
Table 5. Conversion of DME and MeOH on LaꢀZrꢀRh(0.1)/HZSM/Al2O3
59
Product composition, wt %
Converꢀ
sion, %
Feed mixture
DME + Не
T, C
°
C2=
C3=
C4=
C5=
CH4
SC2+
MeOH EtOH DME
240
270
0.5
1.7
45.0
55.4
0.6
0.9
0.4
1.3
1.3
0.9
0.6
4.6
7.1
–
tr.
8.8
13.9
14.2
30.8
–
–
28.4
39.2
0.3
1.2
–
–
–
0.2
0.6
–
–
–
0.8
1.3
tr.
tr.
3.8
3.4
79.0
57.1
–
–
56.9
41.6
–
1.5
tr.
tr.
1.2
1.3
–
–
98.7
98.7
–
MeOH + CO + H2 240
270
DME
+
СО + H2
240
270
1.9
–
–
–
–1
P
= 0.1 MPa,
v
= 2000 h
.
0
Table 6. Conversion of DME and MeOH in conditions of olefin synthesis
Product composition, wt %
C2+
Converꢀ
sion, %
Catalyst
Feed mixture
C=2 C=3 C=4 C=5
ΣC=2 C=4
–
CH4
Σ
Rh/HZSM/Al2O3
DME (10%) + He
DME (10%) + He
99.9 0.2 24.3 19.4 6.3 2.7 47.1
70.0 2.5 26.0 44.4 6.4 3.6 17.1
73.0 0.2 30.4 37.9 18.7 0.8 12.0
50.0
76.8
87.0
57.3
90.1
LaꢀZr/HZSM/Al2O3
LaꢀZrꢀRh/HZSM/Al2O3 DME (10%) + He
MeOH (10%) + CO (30%) + H2 (60%) 100
2.4 28.1 22.2 7.0
–
40.3
DME (10%) + CO (30%) + H2 (60%)
96.0 0.5 32.0 48.0 10.1 0.9 8.5
–1
Note: (T = 340°C, P = 0.1 MPa, v = 2000 h ).
0
Table 7. Parameters of the synthesis of lower olefins from DME and methanol according to data of the different companies
Process
Parameters
Topchiev Inst.,
Russ. Acad. Sci.
company
1
company
2
company 3
Catalyst
SAPOꢀ34
500
SAPOꢀ34
450
ZSMꢀ5
450
LaꢀZrꢀRh/HZSMꢀ5
Temperature
,
°
C
340
1.0
Pressure, atm
Feedstock
.
1.5
1.0
1.0
:
DME/methanol, vol
0, h–1
%
50/50
3000
97
50/50
2000
100
50/50
–
100/0
2000
96
v
DME/methanol conversion, %
Product composition %:
ethylene
98
33
47
9
40
34
8
4
32
propylene
68
1.5
1.5
25
48
butylene
10
methane
1.5
9.5
–
0.5
9.5
C2–C5 alkanes
–
Selectivity for C2–C4 olefins
olefins, %
89
87
82
82
74
72
90
87
Yield of olefins, %
Catalyst onꢀstream time, h
1–2
1–2
700
700
PETROLEUM CHEMISTRY Vol. 51
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2011

60
KOLESNICHENKO et al.
4. G. Cai, Z. Liu, R. Shi, et al., Appl. Catal. A: Gen. 125
,
39.7 to 87 wt %. In the case of methanol, the selectivity
for olefins is 57.3 wt % with a conversion of 100%.
Thus, the introduction of rhodium into
La/Zr/HZSM/Al2O3 leads to an insignificant increase
in the activity in the conversion of DME and to a conꢀ
siderable increase in the selectivity for C=2 C4= olefins
–
29 (1995).
5. G. Ror, R. Ganea, D. Ivanessu, et al., AU Patent
No. 768633 (2000).
6. Hydrocarbon Process. 82, 128 (2003).
7. M. Hask, U. Koss, R. Konig, et al., US Patent
No. 7015369 (2006).
(an increment of more than 10 wt %). Simultaneously,
a redistribution of the composition of resulting olefins
toward an increase in the yield of ethylene and butyꢀ
lenes and a decrease in the yield of propylene takes
place. These data show that it is, in principle, possible
to vary the composition of resulting olefins over a fairly
wide range. The occurrence of the DME conversion
reaction in a syngas instead of a helium stream leads to
a sharp increase in the conversion and to a change in
the composition of olefins in the direction of increasꢀ
ing propylene with an almost unchanged total yield of
8. M. Stoker, Microporous Mesoporous Mater. 29, 3
(1999).
9. B. V. Vora, T. L. Marker, and H. R. Nielsen, US Patent
No. 5714662 (1998).
10. B. V. Vora, P. R. Pujado, L. W. Miller, et al., Stud. Surf.
Sci. Catal., 136, 537 (2001).
11. Eur. Chem. News 79, 30 (2003).
12. ICIS Chem. Bus. 1, 27 (2006).
13. P. Konig, M. Rothaemel, H.ꢀD. Holtmann, and
U. Koss, DE Patent No. 10,027,159 (2001).
14. M. Hack, U. Koss, P. Konig, et al., RU Patent
No. 2266885 (2004).
15. M. Scheidtr, F. Schmidt, G. Bugfels, et al., EP Patent
No. 0448000.
C2=
–
C=4 olefins at a level of 87–90 wt %.
Table 7 collates our data with the published data
obtained at main engineering centers that have
designed their own processes.
16. C. Higman, P. Konig, F.ꢀW. Moller, et al., DE Patent
No.19723363 (1972).
17. M. Inomata, A. Higashi, Y. Makino, and Y. Mashiko,
US Patent No. 6852897 (2002).
18. E. N. Biryukova, T. I. Goryainova, R. V. Kulumbegov,
The technology and the catalyst designed by the
Topchiev Institute make it possible to synthesize lower
olefins from DME with the same high yield as in the
commercialized “methanol” processes and, moreover,
at a lower temperature and using a more stable cataꢀ
lyst.
In summary, the direct production of DME from
syngas and its subsequent conversion to C=2 C4= oleꢀ
–
et al., Neftekhimiya 51 (2011) [Pet. Chem. 51 (2011)].
19. N. V. Kolesnichenko, O. V. Yashina, N. A. Markova,
et al., Neftekhimiya 49, 45 (2009) [Pet. Chem. 49, 42
(2009)].
20. A. Ya. Rozovskii, G. I. Lin, and V. S. Sobolevskii, RU
Patent No. 2218988 (2003).
21. van den Berg, J.P., Wolthuizen, J.P., van Hooff, J.H.C.,
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lite Conference (Naples), Heyden, London. 649
(1980).
22. C. Lo, C. A. Giurumescu, R. Radhakrishnan, and
B. L. Trout, Mol. Phys. 102, 281 (2004).
23. S. R. Blaszkowski and R. A. Van Santen, J. Am. Chem.
fins on rhodiumꢀcontaining zeolite catalysts provide a
high feedstock conversion and a high selectivity for
olefins (up to 90 wt %), opens an opportunity for varyꢀ
ing the composition of olefins according to the manuꢀ
facturing requirements, and significantly simplifies
the process technology.
Soc. 118, 5152 (1996).
24. S. R. Blaszkowski and R. A. Van Santen, J. Am. Chem.
Soc. 119, 5020 (1997).
25. N. Tajima, T. Tsuneda, F. Toyama, and K. Hirao, J. Am.
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PETROLEUM CHEMISTRY Vol. 51
No. 1
2011