Chemistry of Dimethyl Ether: Catalytic Synthesis of 1,3-Butadiene

Article abstract of DOI:10.1134/S096554411808011X

Catalytic synthesis of 1,3-butadiene from dimethyl ether (DME) has been carried out for the first time. It has been established that 1,3-butadiene forms via three possible routes of reactions between DME conversion products: by reaction of propylene with

Full text of DOI:10.1134/S096554411808011X

ISSN 0965-5441, Petroleum Chemistry, 2018, Vol. 58, No. 8, pp. 613–621. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © S.N. Khadzhiev, A.L. Maksimov, V.F. Tret’yakov, R.M. Talyshinskii, A.M. Ilolov, 2018, published in Neftekhimiya, 2018, Vol. 58, No. 4.
Chemistry of Dimethyl Ether: Catalytic Synthesis of 1,3-Butadiene
S. N. Khadzhieva, †, A. L. Maksimova, V. F. Tret’yakova, R. M. Talyshinskiia, *, and A. M. Ilolova
aTopchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, 119991 Russia
*e-mail: talyshinsky@list.ru
Received February 2, 2018
Abstract⎯Catalytic synthesis of 1,3-butadiene from dimethyl ether (DME) has been carried out for the first
time. It has been established that 1,3-butadiene forms via three possible routes of reactions between DME
conversion products: by reaction of propylene with formaldehyde according to the Prins condensation mech-
anism, by DME isomerization of to ethanol followed by its conversion to 1,3-butadiene through acetalde-
hyde, and by dehydrogenation of butylenes.
Keywords: catalysis, DME, 1,3-butadiene, mechanism, Prins condensation, formaldehyde, acetaldehyde,
propylene, ethylene, butylenes, renewable raw materials
DOI: 10.1134/S096554411808011X
lite catalyst was demonstrated by us in [17]. The possi-
bility of formation of significant amounts of ethanol
upon the conversion of DME over the 10%
WO3/HZSM-5 catalyst in the presence of small
amounts of oxygen was also established in [18].
To date, the use of alternative to oil carbon-con-
taining raw materials (natural and associated refinery
gas, coal, biomass, household waste and other carbon-
containing raw materials) is expanding significantly in
the production of motor fuel components and initial
monomers for organic synthesis. In many cases, an
intermediate agent, and, in some cases, the final prod-
uct of the processing of alternative carbon-containing
raw materials via gasification stage to obtain synthesis
gas is DME [1–3]. All monomers for organic and pet-
rochemical synthesis obtained in industry from petro-
leum feedstock can be synthesized from it. In particu-
lar, synthesis of light olefins (ethylene, propylene,
butylenes [4–7]) is possible on the basis of DME, as
well as synthesis of liquid synthetic hydrocarbons
(HCs) [8, 9], including aromatic ones, for subsequent
petrochemical synthesis [10, 11], production of hydro-
gen [12–14] and other value-added products.
However, there is no information in the literature
on the direct synthesis from DME of diene hydrocar-
bons, in particular, 1,3-butadiene which is the most
important starting monomer in the production of syn-
thetic rubbers of general and special purposes, syn-
thetic resins, adipodinitrile, sebacic acid, etc. [15].
In this paper, the direct synthesis of 1,3-butadiene
from DME has been carried out for the first time,
which expands the prospects for the use of alternative
carbon-containing raw materials. Considering that
DME is an inter-class isomer of ethyl alcohol, the
studies were focused on the conversion of DME over a
catalyst for the synthesis of 1,3-butadiene from ethyl
alcohol [16]. The principal possibility of inter-class
isomerization of DME to ethanol over a modified zeo-
EXPERIMENTAL
The synthesis of K2O–ZnO/γ-Al2O3, the classical
catalyst for the preparation of 1,3-butadiene from eth-
anol (product name, TsAK-16 [16]), was carried out
by impregnation of γ-alumina pre-calcined at 873 K
and shaped into sausages with a size of 2 to 6 mm with
solutions of zinc, aluminum and potassium nitrates.
The impregnation was carried out at 353 K for 1 h, fol-
lowed by stages of drying the samples at 393 K (16 h),
stepwise calcination at 473, 573, 693 K (for 2 h) and
activation of the precursor in a quartz reactor for 5 h by
alternating streams of hydrogen, nitrogen and air at
773 K.
The acid properties of the catalyst surface were
determined by the temperature-programmed desorp-
tion (TPD) of ammonia (Table 1). The total surface
acidity of the samples was evaluated on the assump-
tion of single-site adsorption of ammonia by the num-
ber of chemisorbed molecules, desorption of which
was practically completed upon the rise of the tem-
perature in the column with the catalyst to 673–693 K.
The total number of acid sites: NΣ (units/m2) was
calculated from the values of the area under desorp-
tion curves by the formula:
6.02×1023 Tmax
∑
i
(1)
NΣ =
,
†
22400SspG
Deceased.
613

614
KHADZHIEV et al.
Table 1. Comparison of the surface acidity properties for the support and the catalyst, calculated from ammonia thermal
desorption spectra. The initial NH3 adsorption temperature is within the range of 323–338 K, the programmed heating rate
is 10–20°C/min, the NH3 dosage is within the range 0.1–0.5 mmol
Temperature
Acidity corresponding to
T
maxi
ΣNi × 1019
units/m2
T
maxi
Samples
of carrier and catalyst
No
N1
N2
N3
T
max1
T
max2
T
max3
5 × 1018
6.4 × 1018 8.6 × 1018
1
2
γ-Al2O3
403–418
393–400
473–538
453–506
553–673
530–548
2.0
1.8
6.5 × 1018 6.3 × 1018 5.2 × 1018
K2O–ZnО/γ-Al2O3
where: 6.02 × 1023 is Avogadro’s number; Ssp is the
specific surface area of catalyst samples (m2/g); G is
nal normalization method providing adequate results
at equal response of the detector used in the instru-
ment to all components of the mixture. This equality
was achieved in the case of GC by using FID to ana-
lyze mixtures with a relatively similar chemical struc-
ture (for example, hydrocarbon fractions, aldehydes,
and ethers).
the catalyst charge (g);
is the total area of
T
maxi
∑
peaks on the thermal desorption curve (mm2), which
is proportional to the desorbed volume (V) of gaseous
ammonia (mL). The number of moles of desorbed
ammonia was calculated as V/22400, where 22400
(mL) is ≈ the volume of one mole of NH3.
The DME conversion was calculated by the for-
mula
When calculating and interpreting the results of
measurements, we were guided by the recommenda-
tions given in [19].
Physicochemical properties of the catalysts were
studied by the methods of IR spectroscopy (Perkin-
Elmer spectrophotometer in the 4000–400 cm−1
region), X-ray diffraction analysis (Dron-3 instru-
ment with Cu anode and Ni filter), and scanning elec-
tron microscopy (SEM).
Ci − CDME
∑
Conv =
× 100%,
Ci
∑
where ΣCi is the sum of molar concentrations of all gas
mixture components and CDME is the DME molar
concentration in the system after the reaction.
The yield of the ith product with respect to DME
decomposed was calculated by the formula:
The comparison of acidity properties of the sam-
ples listed in Table 1 shows the total acidity of alumina
to be two to three– times that of the catalyst sample for
1,3-butadiene synthesis (rows 1 and 2 in Table 1). For
alumina, the highest concentration of strong acid sites
is observed, the number of which is sharply reduced
when zinc and potassium are applied, and they are
probably involved in the formation of the catalyst for
1,3-butadiene synthesis.
The heterogeneous catalytic conversion of DME
was studied in a flow-through system with automatic
temperature and flow control in the temperature range
of 423–693 K, DME space velocity (GHSV) = 100–
400 h−1, nitrogen : feedstock molar ratio = 1–10 : 1, at
a catalyst charge in a quartz reactor of 5–10 mL.
The gas streams (DME, its conversion products,
and nitrogen) were fed through rotameters by means
of needle valves. Liquid reactants were fed with peri-
staltic pumps.
The schematic of the unit for catalyst testing and
studying the DME conversion features is given in [20].
Ci
Yi =
×100%.
Ci − CDME
∑
The yield of the product on a converted DME basis
was determined as
conv ×Yi
Y =
%.
100
Since the theoretical yield of 1,3-butadiene with
respect to converted DME, as in the case of ethanol, is
58.7%, the selectivity of DME conversion to 1,3-buta-
Yi
58.7
diene is determined by the ratio
.
× 100%
S =
The rates of change in the concentrations of sub-
stances were calculated by the following formulas:
GHSV
−1 is the DME feed space veloc-
W0 =
DME , s
3600
ity expressed in reciprocal seconds, L/(L s),
W0conv
−1 is the DME conversion rate.
WDME
=
, s
100
The DME conversion and the yield and composi-
tion of the products were determined chromatograph-
ically with Kristall-Lyuks gas chromatographs using
absolute calibration of the components, identified by a
flame ionization detector (FID) or a thermal conduc-
tivity detector (TCD), on Porapak Q-packed columns
of a 3 m length and by gas chromatography–mass
RESULTS AND DISCUSSION
The features of DME conversion were studied at a
10 : 1 dilution with nitrogen, a temperature of 623–
693 K, a DME gas hourly space velocity of GHSV =
100–190 h−1 (W0 = 0.0278–0.0528 s−1), a contact time
spectrometry. The control was carried out by the inter- for the total gas stream (DME with nitrogen) in the
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range of 1.7–3.3 s, and a space time of the catalyst with
%
45
40
35
30
25
20
15
10
5
DME from 19 to 36 s.
Sel
Taking into account rapid catalyst coking, its time
on stream was 10 min. Then, regeneration was carried
out for the same time.
Conv
Preliminarily, experiments were carried out on the
effect of linear flow rate in the reactor on the feedstock
conversion and the selectivity for 1,3-butadiene
(Fig. 1). The selectivity was evaluated as the yield of
1,3-butadiene relative to the theoretically attainable
one in terms of converted DME. The linear flow rate
was varied by changing the catalyst charge (10, 20,
0
0.3
0.6
1.2
30 cm3) at a constant DME feed rate of GHSVDME
=
Linear velocity, cm/s
200 h−1 and a nitrogen : DME dilution of 7 : 1. The
reaction temperature was maintained in the range of
663–683 K. The results obtained show the absence of
the effect of external diffusion on the feedstock con-
version of and the selectivity of DME conversion to
1,3-butadiene under the specified reaction conditions.
Fig. 1. Effect of DME linear velocity on the performance
of 1,3-butadiene synthesis.
with the catalyst TsAK-16 at temperatures of 653, 673,
and 693 K.
The results of study [20] on the kinetics of ethanol
conversion over TsAK-16 catalyst showed that there
were no significant changes by comminution of cata-
lyst granules from 2–3 to 0.5 mm, a fact that suggest
the absence of intradiffusional constraints and, hence,
occurrence of the reaction in the kinetic region, pre-
dicting a similar situation for DME.
Table 2 shows, as an example, material balance and
the most significant reaction products for one of the
experiments.
From the data obtained (Tables 2–5 and Fig. 2–4) it
follows that the final products of DME conversion reac-
tion are most likely methane, CO, hydrogen, and coke-
tar substances. The remaining products are intermediates
formed as a result of a set of consecutive–parallel reac-
tions. Notice a high yield of ethanol and, especially, its
growth with an increase in the reaction temperature. For
1,3-butadiene with increasing temperature, the maxi-
mum of its yield shifts toward smaller values of the space
The formation of significant amounts of 1,3-buta-
diene, diethyl ether, С2–С4 olefins, CO, and methane
was observed. Notice an unusual ratio of the yield of
ethylene, propylene, and butylenes. The yield of pro-
pylene is much lower than that of ethylene and buty-
lenes. For acid-catalyzed DME conversion reactions,
the yields of ethylene and propylene are commensura-
ble, and for pyrolysis of gasoline, for example, the
highest yield is for ethylene, then propylene, and fur-
ther butylenes. The ratio observed in our experiments
is possible in the case when propylene undergoes more
intensive conversion in the subsequent reactions in
comparison with ethylene and butylenes.
Tables 3–5 list the main results obtained for three
temperatures and three space velocities (100, 150, and
190 h−1) (runs 1–9), and chromatographic data on the
concentrations of substances participating in the pro-
cess, calculated in molar amounts of the converted
DME. The experiments were carried with a catalyst
charge of 10 mL.
Table 2. Material balance of DME conversion at 673 K and
a DME gas space velocity of GHSV = 150 h−1 (catalyst,
TsAK-16; nitrogen : DME = 10 : 1; gaseous DME volume
rate: W0 = 150/3600 = 0.0417 s−1 (L/(L s)). 10.46 g of DME
were taken for the study. The space time for DME is 24 s,
and the space time of the entire gaseous stream with the cat-
alyst is 2.2 s
Obtained
Substance
g
wt %
Dimethyl ether
6.33
0.02
1
60.5
0.17
9.56
0.48
7.28
1.14
5.44
3.31
4.22
0.19
0.02
0.62
8.00
100.00
Acetaldehyde
1,3-Butadiene
Ethanol
Ethylene
Propylene
0.05
0.76
0.12
0.57
0.34
0.44
0.01
0.002
0.06
0.83
10.46
Butylenes
Diethyl ether
СО + methane
Formaldehyde
Hydrogen
The molar amounts of hydrogen and water pro-
duced were determined by calculation from the stoi-
chiometric ratios of the main final routes, based on the
values of the observed molar concentrations of acetal-
dehyde; butadiene; and total CO with methane, buta-
diene, ethylene, propylene, butylenes, and DEE.
Water
Unidentified + coke + losses
Total
Figures 2–4 depict the dependences of the DME
conversion parameters on the contact time of DME
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KHADZHIEV et al.
Table 3. Effect of temperature at a space velocity GHSVDME of 100 h−1 on the concentration of reaction products in the
output stream, mol % (catalyst, TsAK-16; nitrogen : DME = 10 : 1; volume rate for gaseous DME: W0 = 100/3600 =
0.0278 s−1 (L/(L s)), The space time for DME is 36 s, and the space time for the entire gaseous stream with the catalyst is 3.3 s)
Run No.
1
2
3
Т = 653 K
Т = 673 K
Т = 693 K
substance
100 h−1
yield, mol %,
with respect to DME
yield, mol %,
with respect to DME
yield, mol %,
with respect to DME
fed
converted
fed
converted
fed
converted
Acetaldehyde
1,3-Butadiene
Ethanol
Ethylene
Propylene
~
8.5
2.0
4.4
~
~
19.3
4.5
10.0
~
~
9.6
13.0
9.42
~
~
20.0
27.1
19.58
~
~
10.4
8.5
10.1
~
~
19.4
15.9
18.9
~
Butylenes
~
~
~
~
2.0
3.7
Diethyl ether
СО + methane
Formaldehyde
Unidentified + coke + losses
Total
~
~
~
~
3.0
9.2
0.20
10.1
53.5
5.6
18.7
0.15
10.25
44.0
42.56
0.34
23.3
100.0
9.3
0.25
6.43
48.0
19.4
0.52
13.4
100.0
17.2
0.37
18.93
100.0
Conversion
44.0
48.0
53.5
Table 4. Effect of temperature at a space velocity GHSVDME of 150 h−1 on the concentration of products in the output
stream, mol % (catalyst, TsAK-16; nitrogen : DME = 10 : 1; volume rate for gaseous DME: W0 = 150/3600 = 0.0417 s−1
(L/(L s)). Space time for DME is 24 s, space time for the entire gaseous stream with the catalyst is 2.2 s)
Run No.
4
5
6
Т = 653 K
Т = 673 K
Т = 693 K
substance
150 h−1
yield, mol %,
with respect to DME
yield, mol %,
with respect to DME
yield, mol %,
with respect to DME
fed
converted
fed
converted
fed
converted
Acetaldehyde
1,3-Butadiene
Ethanol
Ethylene
Propylene
0.15
6.8
2.0
11.4
1.0
0.44
20.0
5.9
33.5
2.9
0.2
7.6
0.5
10.75
1.3
0.5
20.2
1.3
28.3
3.4
0.18
8.4
0.18
10.3
1.4
0.42
19.5
0.42
24.0
3.2
Butylenes
3.0
1.55
2.1
0.10
5.9
34.0
8.8
4.6
6.1
0.29
17.3
100.0
3.8
1.5
7.35
0.15
4.85
38.0
10.0
3.9
19.3
0.40
12.7
100.0
4.0
1.5
12.7
0.08
4.26
43.0
9.3
3.5
29.64
0.19
9.9
Diethyl ether
СО + methane
Formaldehyde
Unidentified + coke + losses
Total
100.0
Conversion
34.0
38.0
43.0
time, indicating its intensive transformation in the subse-
quent secondary reactions.
The conversion of DME over the TsAK-16 catalyst
under the conditions studied is accompanied by strong
coking and, therefore, the product composition was
analyzed and compared after 10 min of the catalyst on
stream. Special experiments on weighing the catalyst
samples before and after the reaction cycle (1 h)
showed that in the range of temperatures considered, a
The yield of acetaldehyde and formaldehyde is sig-
nificantly lower in comparison with the main interme-
diate products, which may be due to both low rate of
their formation and their intensive consumption in
subsequent reactions.
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Table 5. Effect of temperature at a space velocity GHSVDME of 190 h−1 on the concentration of the products in the output
stream, mol % (catalyst, TsAK-16; nitrogen : DME = 10 : 1; DME gas space velocity: W0 = 190/3600 = 0.0528 s−1 (L/(L s)).
Space time with respect to DME fed is 19 s, space time of the entire gaseous stream with the catalyst is 1.7 s
Run No.
7
8
9
Т = 653 K
Т = 673 K
Т = 693 K
substance
190 h−1
yield, mol %,
with respect to DME
yield, mol %,
with respect to DME
yield, mol %,
with respect to DME
fed
converted
fed
0.1
6.4
1.0
9.7
1.0
4.2
0.8
converted
fed
converted
Acetaldehyde
1,3-Butadiene
Ethanol
Ethylene
Propylene
0.07
5.8
2.5
11.6
0.7
3.3
0.23
19.3
8.3
38.77
2.3
0.29
18.3
2.86
27.79
2.86
12.0
0.09
7.2
0.07
8.2
1.2
4.5
0.23
18.9
0.18
21.7
3.15
Butylenes
11.0
4.0
11.8
1.3
Diethyl ether
СО + methane
Formaldehyde
Unidentified + coke + losses
Total
1.2
2.2
0.5
2.1
7.0
7.35
0.12
4.33
21.0
11.9
0.06
3.54
31.34
0.16
9.32
100.0
0.08
2.65
30.0
0.27
8.83
100.0
0.34
12.37
100.0
35.0
38.0
Conversion
30.0
35.0
38.0
maximum of coke (coke-tar substances) deposition is mation is 1,3-butadiene. In this case, it can be pro-
observed in the range of space time of ca. 25 s with
respect to DME (Fig. 5).
duced via the Prins condensation from propylene and
formaldehyde.
With increasing temperature, the yield of coke is
significantly reduced, which indicates its formation
from products whose yield also decreases with increas-
ing temperature.
When comparing the behavior of the yield of the
products with that of the coke yield, it is seen that over
TsAK-16 catalyst, in particular, there is a correlation
with the yield of formaldehyde.
For example, TsAK-16 catalyst exhibit maxima of
formaldehyde yield in the range of contact times cor-
responding to the maximum in coke formation
(Fig. 6). The dependence of formaldehyde yield on
the contact time in this case changed symbatically to
coke formation. As can be seen from the data
obtained, this trend occurs both at low and high tem-
peratures, and at low temperatures the yield of both
formaldehyde and coke is much higher.
Below are given the observed dependences of the
selectivity of the yield of possible intermediates in
1,3-butadiene formation by different mechanisms
(acetaldehyde, formaldehyde, and butylenes) of the
final products on the conversion (Fig. 7). Product
selectivity varies significantly with conversion, and
selectivity for aldehydes and butenes is significantly
reduced with a decrease in DME conversion, which
more likely indicates that they are primary prod-
ucts, and the selectivity for methane + carbon mon-
oxide decreases with decreasing DME conversion,
which is usually observed for the final products.
50
Conversion
40
CO + CH4
These facts indirectly indicate a possible effect of
formaldehyde or its conversion products on the coking
of the TsAK-16 catalyst surface.
30
20
10
Ethylene
1,3-butadiene
When the reaction temperature over TsAK-16
decreases to 573 K, the products contain 3-butenol-1
and oxane-4 in amounts commensurate with unbal-
ance in carbon. At the same time, DME conversion
over TsAK-16 does not exceed 30–40%. Perhaps these
products, the formation of which involves formalde-
hyde, lead to the formation of coke-tar substances at
low temperatures.
Ethanol
25
30
35
40
20
Space time for DME, τ, s
Fig. 2. Effect of the contact time on the yield of products
(on converted DME basis) and DME conversion over the
TsAK-16 catalyst at 653 K and 10 : 1 DME dilution with
nitrogen.
Another product that can be synthesized with the
participation of formaldehyde and leads to coke for-
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KHADZHIEV et al.
0.25
0.20
0.15
0.10
0.05
Conversion
50
40
30
20
10
CO + CH4
Formaldehyde
Ethylene
1,3-butadiene
Ethanol
Acetaldehyde
25
30
35
20
25
30
35
20
Space time for DME, τ, s
Space time for DME, τ, s
Fig. 3. Effect of the contact time over TsAK-16 catalyst on the yield of products (on converted DME basis) and DME conversion
at 673 K and 10 : 1 DME dilution with nitrogen.
Taking into account all the data obtained on the tions occurring in the system can generally be repre-
heterogeneous catalytic DME conversion, the reac- sented by the following scheme:
Route 1
−H2
+
−H2O
OH
−H2O
+
−H2O
+H2
O
O
−H2O
−H2O
Route 2a
OH
O
+
−H2
−H2O
O
−H2O
O
Route 2b
O
OH
−H2
−CH4
Route 3
+
−H2O
OH
CH2O
Possible scheme of chemical transformations of dimethyl ether over the TsAK-16 catalyst in the range of 423–673 K.
Conversion
50
40
Ethanol
30
Ethylene
20
1,3-butadiene
10
CO + CH4
25
30
35
40
20
Space time for DME, τ, s
Fig. 4. Effect of the contact time on the yield of products (on converted DME basis) and DME conversion at 693 K and 10 : 1 DME
dilution with nitrogen over TsAK-16 catalyst.
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CHEMISTRY OF DIMETHYL ETHER
619
10
8
653 K
673 K
693 K
6
4
2
25
30
35
40
20
Space time for DME, τ, s
Fig. 5. Effect of DME contact time (TsAK-16 catalyst) on the yield of coke at different temperatures.
423 K
0.25
0.20
673 K
0.15
0.10
0.05
K2O–ZnO/γ-Al2O3
25
30
35
20
Space time for DME, τ, s
Fig. 6. Effect of the contact time on the yield of formaldehyde over the TsAK-16 catalyst at a 10 : 1 molar DME dilution with
nitrogen at different temperatures.
The formation of 1,3-butadiene is possible via three observed patterns in the experiment with relative root-
routes:
mean-square deviations between the observed and
calculated rates of no more than 15% for byproducts
and no more than 5% for gross conversion of DME
and for the rate of 1,3-butadiene formation.
Figure 8 shows the experimental and calculated
dependences of the rate of DME conversion to propyl-
ene and 1,3-butadiene on the concentration of DME
in the reaction zone.
There is a good correlation between the rates of
propylene and 1,3-butadiene formation, which con-
firms the possible course of the reaction by the Prins
condensation mechanism.
⎯by the dehydrogenation of butylenes formed in
appreciable amounts by dimerization of ethylene or
directly in the conversion of diethyl ether, an interme-
diate in the reaction (routes 1a and 1b);
⎯from acetaldehyde by analogy with the mecha-
nism observed in the ethanol to 1,3-butadiene conver-
sion reaction. The formation of acetaldehyde occurs
via isomerization of DME to ethanol and its dehydro-
genation to acetaldehyde (route 2a) or via the forma-
tion of ethylene oxide, as evidenced by the presence of
C2H4O microimpurity in the gas phase (route 2b);
This also follows from the fact of the propylene
lower content in the reaction products, in comparison
with ethylene and butylene, which is most likely due to
its rapid consumption in the reaction of 1,3-butadiene
synthesis.
Mechanism of the Prins condensation (interaction
of formaldehyde with propylene) was studied in [21],
and the formation of 1,3-butadiene in significant
amounts was observed.
⎯from formaldehyde and its subsequent Prins
condensation with propylene (route 3).
On the basis of the experimental regularities, we
have considered an approximate stoichiometric basis
of the final routes in the process of converting DME to
1,3-butadiene for the given scheme, and developed a
semi-empirical kinetic model based on the selection of
DME, ethanol, 1,3-butadiene, ethylene , propylene,
carbon monoxide and DEE as 7 key substances for
seven stoichiometric basis routes. The obtained
The scheme of 1,3-butadiene formation from pro-
semiempirical kinetic model adequately describes the pylene by the Prins condensation mechanism is given
PETROLEUM CHEMISTRY Vol. 58 No. 8 2018

620
KHADZHIEV et al.
60
Butylenes
50
40
30
20
10
Ethylene
25
20
15
10
5
Methane + CO
Propylene
1,3-butadiene
CH3CHO
Diethyl ether
CH2O
40
60
80
0
20
40
60
0
20
Conversion, mol %
Conversion, mol %
Fig. 7. Dependence of the selectivity of DME conversion to some products on its conversion (control parameter of the conversion
is the volume feed rate of DME at a given temperature of 663 K).
below [21]. It can be seen that 3-butenol-1 is produced decomposition products), dehydration of which leads
in the reaction of propylene and formaldehyde (DME to the synthesis of 1,3-butadiene:
CH3
Isomerization
−H2O
H2C
HO
H3C
CH2O +
CH2
CH2
CH2
+CH2O
+CH2O
+CH2O
−H2O
O
H3C
O
HO
O
O
The formation of propylene during the DME con-
version process can be explained by the rapid interac-
tion of the methanol formed with ethylene, which in
the end creates favorable conditions for the realization
of the Prins condensation mechanism.
Wi, s–1
0.004
At the same time, according to the data given in
[21] for the zeolite catalysts tested, the Prins conden-
sation of formaldehyde with propylene under the con-
ditions considered does not result in the formation of
acetaldehyde and butylenes. Over the TsAK-16
catalys, their yield is significant and they can partici-
pate in the synthesis of 1,3-butadiene from DME.
1,3-butadiene
0.003
0.002
0.001
CONCLUSIONS
Propylene
Direct synthesis of 1,3-butadiene from DME was
carried out for the first time. The maximum yield of
1,3-butadiene with respect to converted DME using a
catalyst based on a ZnO/γ-Al2O3 composition in the
653–693 K temperature range at DME gas hourly
space velocities of 100–190 h−1 and a 10 : 1 molar dilu-
tion of the feedstock with nitrogen reaches 20 mol %
at 30–50% feedstock conversion.
0.060 0.070 CDME
DME mole fraction in the contact
gas (chromatography)
0.050
Fig. 8. Dependences of the rates of DME conversion to
By studying the trends in the catalytic conversion
of DME, it was also shown that 1,3-butadiene can
propylene and 1,3-butadiene on DME concentration in
−1
the reaction zone at 673 K and GHSV = 100–190 h
.
PETROLEUM CHEMISTRY
Vol. 58
No. 8
2018

CHEMISTRY OF DIMETHYL ETHER
621
6. K. Hemelsoet, J. van der Mynsbrugge, K. De Wispe-
form via three routes. The most probable route is the
formation of 1,3-butadiene from propylene and form-
aldehyde produced upon DME conversion followed
by their Prins condensation.
Part of 1,3-butadiene is probably formed via acetal-
dehyde by analogy with the mechanism observed in
the reaction of ethanol conversion to 1,3-butadiene.
In this case, acetaldehyde is produced by the isomeri-
zation of DME to ethanol and its dehydrogenation to
acetaldehyde. In addition, 1,3-butadiene can be
formed via the dehydrogenation of butylenes formed
by ethylene dimerization or directly in the conversion
of diethyl ether formed as an intermediate.
It is likely that the route associated with the dehy-
drogenation of butylenes makes a significant contribu-
tion to the synthesis of 1,3-butadiene from dimethyl
ether.
The data obtained show that 1,3-butadiene can be
synthesized from almost any carbonaceous raw mate-
rial (fossil, biomass, technogenic) via the steps of gas-
ification and dimethyl ether synthesis, thereby and
expanding the scope of DME use as a multipurpose
feedstock for petrochemical processes.
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PETROLEUM CHEMISTRY Vol. 58 No. 8 2018