Ethenolysis of C5+ Alkenes as a Method for Synthesis of Propylene

Article abstract of DOI:10.1134/S1070427217120011

A thermodynamic analysis of the interaction of ethylene with C5+ alkene in the case of occurrence in the system of metathesis and positional isomerization reactions was performed. The reaction of 1-hexene and 1-heptene with ethylene on the catalysts Re₂O₇/SO₄^2–- ZrO₂–Al₂O₃ and Re₂O₇/B₂O₃–Al₂O₃ was studied. Thermodynamic calculations demonstrated that the main reaction product was propylene. Tests performed indicated that, in ethenolysis of 1-hexene in an excess of ethylene, there occurred its full transformation, wherein the content of propylene in the reaction products was 75 wt% for the Re₂O₇/SO₄^2–/ ZrO₂–Al₂O₃ catalyst and 73 wt% for Re₂O₇/B₂O₃–Al₂O₂. The ethenolysis of 1-heptene also occurred with high formation selectivity of propylene but is accompanied by a substantial yield of C9+ alkene byproducts.

Full text of DOI:10.1134/S1070427217120011

ISSN 1070-4272, Russian Journal of Applied Chemistry, 2017, Vol. 90, No. 12, pp. 1893−1899. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © E.A. Buluchevskii, L.F. Saifullina, A.V. Lavrenov, T.R. Karpova, N.A. Glazov, 2017, published in Zhurnal Prikladnoi Khimii, 2017,
Vol. 90, No. 11, pp. 1560−1566.
CATALYSIS
Ethenolysis of C5+ Alkenes as a Method
for Synthesis of Propylene
E. A. Buluchevskiia,b,*, L. F. Saifullinaa, A. V. Lavrenova, T. R. Karpovaa, and N. A. Glazovb
a Institute of Hydrocarbons Processing, Siberian Branch, Russian Academy of Sciences,
ul. Neftezavodskaya 54, Omsk, 644040 Russia
b Omsk F.M. Dostoevsky State University, ul. Neftezavodskaya 11, Omsk, 644053 Russia
*e-mail: bulu@ihcp.ru
Received November 7, 2017
Abstract—Thermodynamic calculations demonstrated that, when any C5+ alkene is subjected to ethenolysis in
an excess of ethylene on a catalyst providing the occurrence of a metathesis and positional isomerization, the
main reaction product is propylene. The results of the calculations were confirmed experimentally for the cases
of ethenolysis of hexene-1 and heptene-1 on Re2O7/SO42–/ZrO2–Al2O3 and Re2O7/B2O3–Al2O3 catalysts.
DOI: 10.1134/S1070427217120011
At present, the main technology used to obtain
propylene is by pyrolysis of naphtha or other light
hydrocarbon materials, in which propylene is formed
as one of by-products [1–3]. The demand for propylene
substantially exceeds the amount produced in the course
of pyrolysis. Among the promising sources of propylene
are, together with the processes of deep catalytic cracking
and dehydrogenation of propane, the techniques based
on the reaction of metathesis of alkenes and, primarily,
butenes.
occurrence of the reactions of metathesis and positional
isomerization on bifunctional catalysts has been long
known [12]. This approach is used most frequently for
synthesis of ω-olefins on catalysts having varied level
of acid properties: Re2O7/Al2O3 [13–15], WO3/SiO2
[16–19], MoО3/Al2O3 [20, 21], NiMoO4/SiO2 [22],
MoO3/MCM-41 [23, 24], MoO3/MCM-48 [24], MoO3/
SBA-15 [24].
The goal of our study was to demonstrate the
possibility of obtaining propylene in high yield via
interaction between ethylene and C5+ alkene on a
bifunctional catalyst that simultaneously contains active
metathesis centers and acid centers. For example, in the
case of a joint conversion of ethylene and pentene-1 on
metathesis catalysts possessing an acid function, the
process must occur by the following Scheme 1.
Some of these technologies have been industrially
implemented, e.g., the OCT process (Olefins Conversion
Technology), by Lummus Technology Inc. [4], and the
Meta-4 process of the French Institute of Petroleum [5].
If these processes are combined with the dimerization of
ethylene, it becomes possible to obtain propylene with
only ethylene as raw material. This technique has been
tested by Lyondell Petrochemical Co.
According to this scheme, pentene-1 is isomerized at
low temperatures (approximately up to 250°C) into cis-
and trans-pentenes-2 more stable at a given temperature,
which undergo ethenolysis to give propylene and
butane-2. Butene-1 is also isomerized into butenes-2,
which enter into the reaction of metathesis with ethylene
to give propylene.
Examples of using C5+ alkenes as raw materials for
industrial synthesis of propylene are unknown. This issue
has also been poorly analyzed in the literature; there
have been only a set of publications concerned with the
ethenolysis of pentene-2 on rhenium-containing catalysts,
in which it was shown that the yield of propylene is
strongly affected by the acidity of a support.
The main goals of our study were to make a
thermodynamic analysis of the interaction of ethylene
with C5+ alkene in the case of occurrence in the system
of metathesis and positional isomerization reactions and
Meanwhile, the concept of a targeted synthesis of
various alkenes from other alkenes via a simultaneous
1893

1894
BULUCHEVSKII et al.
Scheme 1.
The chemical composition of the samples obtained was
determined by atomic-emission spectroscopy with induc-
tively coupled plasma (VARIAN 710-ES spectrometer).
The texture characteristics of the finished catalysts (Ssp,
specific surface area; Vpor, pore volume; Sav, average pore
diameter) were found by analysis of nitrogen adsorption-
desorption isotherms at 77.4 K (Sorpomatic 1900). The
value of Ssp was estimated by the BET method from the
adsorption isotherm at relative pressures in the range 0.05–
0.30. The value of Vpor was determined from the adsorbed
amount of nitrogen at P/P0 = 0.990. The average pore
diameter was calculated by the equation Dav = 4Vpor/Ssp.
Data on the actual content of metal oxides and the texture
characteristics of the catalysts are listed in the table.
experimentally examine the reaction of hexene-1 and
heptene-1 with ethylene on the catalysts Re2O7/SO42––
ZrO2–Al2O3 and Re2O7/B2O3–Al2O3.
EXPERIMENTAL
The SO42––ZrO2–Al2O3 (SZA) support was produced
by mixing of sulfated zirconium dioxide hydrate with
a prescribed amount of pseudoboehmite (Industrial
Catalysts ZAO, Ryazan). Zirconium dioxide hydrate was
prepared via its precipitation from a solution of zirconium
oxynitrate with aqueous ammonia (final precipitation pH
10). The resulting precipitate was washed with distilled
water and treated with a 16% solution of sulfuric acid,
taken in an amount providing the ZrO2/H2SO4 = 9 : 1 mass
ratio. After the mixing, the support was dried at 120°C
and calcined at 650°C. The content of aluminum oxide
in the support was 40 wt %.
Propylene was synthesized from C5+ hydrocarbons
in a flow-through reactor with fixed catalyst bed. A
catalyst sample was charged into the reactor as a fraction
with grain size of 0.2–0.5 mm and activated, before
beginning the tests, in a flow of dry air at 500°C for 1 h.
The synthesis of propylene from C5+ hydrocarbons was
performed at a temperature of 60°C, pressure of 0.1 MPa,
and mass raw material delivery rate of 2.0 h–1.
A borate-containing aluminum oxide support (BA)
was produced by mixing a solution of orthoboric acid
(chemically pure) with a pseudoboehmite paste at an
Al2O3/B2O3 mass ratio of 4. Then, drying at 120°C and
calcination at 550°C were performed. The content of
boron oxide in the finished support was 20 wt %.
We used as the raw material for the process individual
hexene-1 and heptene-1 and mixtures of these with eth-
ylene (all of chemically pure grade), taken in various
ratios. The conversion products were analyzed in the
on-line mode with a Tsvet 800 gas chromatograph with
flame-ionization detector and HP-PONA capillary col-
umn (19091S-001). Chromatograms were recorded and
Re2O7 was deposited by impregnating the support
with a solution of HReO4, with the subsequent stages of
drying at 120°C and calcination at 500°C. The calculated
amount of Re2O7 in the catalyst was constant and equal
to 2.0 wt %.
Chemical composition and texture characteristics of the catalysts
Content, wt %
Sample
Texture characteristics
Re2O7
Re/BA (Re2O7/B2O3–Al2O3) 2.1 ± 0.2
Re/SZA-40
Al2O3
B2O3
SO42–
–
Ssp, m2 g–1
Vpor, cm3 g–1
Dav, nm
23.4 ± 0.3
212
0.40
7.6
(Re2O7/SO42–/ZrO2–Al2O3)
1.9 ± 0.1
45.7 ± 1.0
–
6.4 ± 0.1
138
0.27
7.7
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 90 No. 12 2017

ETHENOLYSIS OF C5+ ALKENES
1895
processed with Tsvet-Analitik software. The quantitative
composition of the ethylene conversion products was
determined via normalization of the peak areas of the
corresponding groups of hydrocarbons to 100%.
function was made with consideration for the possible
occurrence in the system of the reactions of ethenolysis
of C4–C7 alkenes and positional isomerization of C5+
alkenes. To simplify the calculation, we disregarded the
possibility of occurrence of the reactions of metathesis of
C4+ alkenes because the effect of these on the composition
of products may only be significant at high concentrations
of C5+ alkenes, when the equilibrium concentrations of
propylene in the system are close to zero.
The degree of ethylene conversion (X), product
formation selectivity (S), and product yields (Y) were
calculated in an ordinary way from the composition of
process products.
RESULTS AND DISCUSSION
The equilibrium concentrations of the products
formed in the interaction of ethylene with hexene-1
and heptene-1 were calculated by solving the system of
equations (1–6) for the example of heptene-1.
Thermodynamic analysis of the process. Athermo-
dynamic analysis of the process of ethenolysis of
heptene-1 and hexene-1 on catalysts possessing an acid
where [C2]–[C7] are the equilibrium total (for all the
position isomers) concentrations of C2–C7 alkenes;
K1–K4, equilibrium constants of the formal reactions
СnH2n + C2H4 → Cn–1H2n–2 + C3H6 for butane-1,
pentene-1, hexene-1, and heptene-1, respectively; and
Ki, equilibrium constants for the reactions of positional
isomerization of C4+ alkenes.
heptene-1 mass fraction in the mixture of raw materials
of about 55%, is 64 wt %, which is rather close to the
thermodynamic yield of propylene in ethenolysis of a
mixture of butenes. Under these conditions, the equi-
librium mixture also contains about 17 wt % butenes.
Heavier alkenes are only present in trace amounts. If the
mass fraction of hexene or heptene in the starting mix-
tures does not exceed 0.2, propylene is nearly the only
product formed in the ethenolysis of pentene-1. The total
share of other products does not exceed 2–3%. Thus, we
demonstrated that it is thermodynamically possible to
produce propylene by ethenolysis of C5+ hydrocarbons
with high selectivity.
The results of calculations, shown in Fig. 1, dem-
onstrated that close equilibrium contents of propylene
are observed in the mixture in the cases of ethenolysis
of hexene-1 and heptene-1 for the same initial ratios
between the components. The maximum fraction of pro-
pylene in the reaction mixture, provided at a hexene-1/
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 90 No. 12 2017

1896
BULUCHEVSKII et al.
W, wt %
W, wt %
(b)
(a)
ω, %
ω, %
Fig. 1. Dependence of the equilibrium compositions of products formed in isomerization and ethenolysis of (a) hexene-1 and (b) heptene-1
on the composition of the starting reaction mixture. (W) Content of a reaction product, (ω) mass fraction of hexene-1 or heptene-1 in the
starting mixture. (1) Ethylene, (2) propylene, (3) butenes, (4) pentenes, (5) hexenes, (6) heptenes.
X, %
(a)
(b)
W, wt %
τ, min
C2
C3 C4
C5 C6
C7
C8 C9+
Fig. 2. (a) Variation of the conversion X of hexene-1 on (1) Re/SZA and (2) Re/BA catalysts with time τ and (b) composition W of the
reaction products after 10 min of the process.
Experimental study of the conversion of hydrocarbon
mixtures on Re2O7/SO42–/ZrO2–Al2O3 and Re2O7/
B2O3–Al2O3 catalysts. A study of the conversion of
pure ethylene on Re2O7/SO42–/ZrO2–Al2O3 (Re/SZA)
and Re2O7/B2O3–Al2O3 (Re/BA) catalysts at 60°C
demonstrated that these systems exhibit a low activity
in the conversion of ethylene. The degrees of conversion
are 6 and 1.2%, respectively.
and 34% for the catalyst based on sulfated zirconium
oxide. For the Re/BA system, the mixture of products
also contains 9% butenes and 3% pentenes, with higher
molecular alkenes present in trace amounts. For Re/SZA,
the total fraction of C4–C7 hydrocarbons does not exceed
15%, with C8+ alkenes constituting more than 50% of
the products.
To evaluate the catalytic properties of the systems under
study in the reaction of metathesis, we performed their tests
in the conversion of hexene-1 and heptene-1 (Figs. 2 and
3). It can be seen from these data that the systems under
study exhibit a low activity in the reactions of conversion
of hexene-1 and heptene-1. This is, in all probability, due
to their close contents and close states of rhenium. A large
degree of conversion (>90%) is observed for both catalysts
The observed conversion of ethylene is due to its
oligomerization on acid centers of the catalysts, with
further conversion of the oligomerization products in
metathesis reactions. The main reaction products of the
ethylene conversion are propylene, butenes, and C5+
alkenes. The selectivity of propylene formation is 86% for
the catalyst based on a boron-containing aluminum oxide
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 90 No. 12 2017

ETHENOLYSIS OF C5+ ALKENES
1897
(a)
W, wt %
(b)
X, %
C2
C3 C4
C5 C6
C7
C8 C9+
τ, min
Fig. 3. (a) Variation of the conversion X of heptene-1 on (1) Re/SZA and (2) Re/BA catalysts with time τ and (b) composition W of the
reaction products after 10 min of the process.
W, wt %
W, wt %
(b)
(a)
C3
C4
C5
C7
C8
C9+
C3
C4
C5
C7
C8
C9+
Fig. 4. Composition W of products formed in the conversion of the ethylene/hexene-1 mixture on (a) RE/SZAcatalyst at hexene-1 content
of (1) 40 and (2) 76 wt % and (b) Re/BA catalyst at hexene-1 content of (1) 50 and (2) 80 wt % after 10 min of the process.
in the initial period of their operation. After the first hour
in service, their activity decreases.
slower rate, and the oligomerization of the starting hexene
is substantially more intense, compared with that on the
Re/SZA catalyst. In the case of conversion of heptene-1,
this tendency is more clearly pronounced (Fig. 3b).
The compositions of the products formed in conversion
of hexene-1 strongly differ for both catalysts (Fig. 2b).
The system based on Re/SZA is characterized by the
bimodal distribution of conversion products, typical
of the metathesis of olefins. At the same time, mostly
products with molar mass exceeding that of the starting
alkene are mostly formed for the Re/BA catalysts. The
observed situation may point to the significant difference
between the rates of positional isomerization of alkenes
on the catalysts under study. In the presence of the Re/
SZAcatalyst, the reaction of isomerization of the position
of a double bond in hexene-1 is fast. The nonterminal
alkenes formed in the process enter into the reaction of
metathesis to give hydrocarbons with a shorter and longer
chain than that of the starting hydrocarbons. β-Olefins are
formed on a borate-containing catalyst at a substantially
The Re/BA and Re/SZA catalysts were tested in the
course of metathesis of hexene-1 with ethylene. It was
demonstrated that propylene is, indeed, the main process
product (Fig. 4). With increasing reaction duration, the
content of propylene in the reaction products decreases
from 75–78 to 25–37%. This is due to the deactivation
of active metathesis centers, associated with the
accumulation on the catalyst surface of C9+ hydrocarbons
formed as a result of side reactions of oligomerization
and metathesis.
When a mixture of ethylene with heptene-1 is used
as a raw material, the composition of the products
substantially changes. A high yield of propylene is
also observed for both systems. As also in the case of
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 90 No. 12 2017

1898
W, wt %
BULUCHEVSKII et al.
W, wt %
(b)
(a)
C3
C4
C5
C7
C8
C9+
C3
C4
C5
C7
C8
C9+
Fig. 5. Composition W of products formed in the conversion of the ethylene/heptene-1 mixture on (a) RE/SZA catalyst at heptene-1
content of (1) 40 and (2) 76 wt % and (b) Re/BA catalyst at heptene-1 content of (1) 50 and (2) 80 wt % after 10 min of the process.
hexene-1, this yield steadily grows with increasing
concentration of ethylene in raw materials on both the
catalysts under study. However, the products also contain
substantial amounts of C9+ alkenes. This tendency is
more pronounced for the Re/SZA catalyst. The content
of heaыvy hydrocarbons in the products formed in the
conversion of ethylene–heptene-1 mixture is about
30 wt % even at the initial content of a heavy hydrocarbon
in the raw material of less than 50 wt %. In all probability,
a capillary condensation of high-boiling heptene occurs
within pores of catalysts, with the result that the process
is complicated by diffusion factors, and the contribution
of oligomerization to the composition of the products
becomes more significant (Fig. 5).
SO42–/ZrO2–Al2O3), but is accompanied by a substantial
yield of by-products, C9+ alkenes.
REFERENCES
1. Paushkin, Ya.M., Adel’son, S.V., and Vishnyakova, T.P.,
Tekhnologiya neftekhimicheskogo sinteza (Technology
of Petrochemical Synthesis), Moscow: Khimiya, 1973,
part 1.
2. RF Patent 2 263 132 (2005).
3. RF Patent 2 348 678 (2009).
4. Mol, J.C., J. Mol. Catal., A, 2004, vol. 213, pp. 39–45.
5. FR Patent 2 608 595 (1988).
6. Phongsawat, W., Netiworaruksa, B., Suriye, K., et al.,
Catal. Lett., 2012, vol. 142, pp. 1141–1149.
7. Phongsawat, W., Netivorruksa, B., Suriye, K., et al., J. Nat.
Gas Chem., 2012, vol. 21, no. 1, pp. 83–90.
CONCLUSIONS
8. Phongsawat, W., Netivorruksa, B., Suriye, K., et al., J. Nat.
Gas Chem., 2012, vol. 21, no.. 2, pp. 158–164.
(1) Thermodynamic calculations demonstrated that,
when the reactions of positional isomerization and
metathesis occur in ethylene/C5+ alkene systems with
an excess of ethylene, the main conversion product is
propylene, irrespective of the chain length and position
of the double bond in the C5+ alkene.
9. Phongsawat, W., Netiworaruksa, B., Suriye, K., et al.,
Catal. Lett., 2012, vol. 142, no. 9, pp. 1141–1149.
10. Vorakitkanvasin, S., Kunjara Na Ayudhy, S., Suriye, K.,
et al., Appl. Catal., A, 2016, vol. 517, pp. 39–46.
11. Phongsawat, W., Netiworaruksa, B., Suriye, K., et al.,
(2) The tests performed in the study indicate that, in
ethenolysis of hexene-1 in an excess of ethylene, there
occurs its full transformation: the content of propylene
in the reaction products is 75 wt % for the Re2O7/SO42–/
ZrO2–Al2O3 catalyst and 73 wt % for Re2O7/B2O3–Al2O3.
J. Ind. Eng. Chem., 2014, vol. 20, pp. 145–152.
12. Fel’dblyum, V.Sh., Dimerizatsiya i disproportsionirovanie
olefinov (Dimerization and Disproportionation of Olefins),
Moscow: Khimiya, 1978.
13. Kustov, L.M., Furman, D.B., and Barkova, A.P., Catal.
Lett., 2016, vol. 146, pp. 1033–1039.
(3) It was shown that the ethenolysis of heptene-1
also occurs with high formation selectivity of propylene
(78 wt % for Re2O7/B2O3–Al2O3 and 50 wt % for Re2O7/
14. Aguado, J., Escola, J.M., Castro, M.C., et al., Appl. Catal.,
A, 2005, vol. 284, pp. 47–57.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 90 No. 12 2017

ETHENOLYSIS OF C5+ ALKENES
1899
15. Spronk, R. and Mol, J.C., Appl. Catal., 1991, vol. 70, no. 1,
20. Behr, A., Schu, U., Bauer, K., et al., Appl. Catal., A, 2009,
pp. 295–306.
vol. 357, pp. 34–41.
16. Lokhat, D., Starzak, M., and Stelmachowski, M.L., Appl.
Catal., A, 2008, vol. 351, pp. 137–147.
21. Aguado, J., Escola, J.M., and Castro, M.C., Stud. Surf. Sci.
Catal., 2005, vol. 156, pp. 835–842.
17. Schalkwyk, C., Spamer, A., Moodley, D.J., et al., Appl.
Catal., A, 2003, vol. 255, pp. 121–131.
22. Zavoianu, R., Dias, A.P.V.S., Pavel, O.D., et al., Catal.
Commun., 2005, vol. 6, pp. 321–327.
18. Spamer, A., Dube, T.I., Moodley, D.J., et al., Appl. Catal.,
A, 2003, vol. 255, pp. 133–142.
23. Balcar, H., Topka, P., Zilkova, N., et al., Stud. Surf. Sci.
Catal., 2005, vol. 156, pp. 795–802.
19. Schalkwyk, C., Spamer, A., Moodley, D.J., et al. Appl.
Catal., A, 2003, vol. 255, pp. 143–152.
24. Topka, P., Balcar, H., Rathousky, J., et al., Microporous
Mesoporous Mater., 2006, vol. 96, pp. 44–54.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 90 No. 12 2017