Ethylene to Propylene by One-Pot Catalytic Cascade Reactions

Article abstract of DOI:10.1021/acscatal.5b00383

An original method for converting ethylene to propylene involving cascade oligomerization/isomerization/metathesis reactions over two robust and highly active heterogeneous catalysts is investigated. In a single flow reactor and under identical conditions, ethylene was first selectively dimerized/isomerized over Ni-AlSBA-15 catalyst to form 2-butenes, which reacted then with the excess of ethylene over MoO₃-SiO₂-Al₂O₃ to produce propylene. At 80 °C and 3 MPa, specific activities up to 48 mmol of propylene per gram of catalyst per hour were obtained. (Chemical Equation Presented).

Full text of DOI:10.1021/acscatal.5b00383

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Letter
Ethylene to propylene by one-pot catalytic cascade reactions
Radu Dorin Andrei, Marcel Ionel Popa, François Fajula, Claudia Cammarano,
Atheer Al Khudhair, Karim Bouchmella, P. Hubert Mutin, and Vasile Hulea
ACS Catal., Just Accepted Manuscript • Publication Date (Web): 27 Mar 2015
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ACS Catalysis
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Ethylene to Propylene by One-Pot Catalytic Cascade Reactions
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Radu Dorin Andrei , Marcel Ionel Popa , François Fajula , Claudia Cammarano , Atheer Al Khud-
,2
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hair , Karim Bouchmella , P. Hubert Mutin , Vasile Hulea *
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Institut Charles Gerhardt Montpellier, UMR 5253, CNRS-UM2-ENSCM-UM1, 8 rue de l’Ecole Normale, 34296 Montpel-
lier Cedex 5, France
2
Faculty of Chemical Engineering and Environment Protection, Technical University of Iasi, 71 D. Mangeron Ave., 700050,
Iasi, Romania
KEYWORDS: tandem catalysis, heterogeneous catalysis, oligomerization, metathesis, Al-SBA-15, non-hydrolytic sol-gel.
ABSTRACT: An original method for converting ethylene to propylene involving cascade oligomeriza-
tion/isomerization/metathesis reactions over two robust and highly active heterogeneous catalysts is investigated. In a single flow
reactor and under identical conditions, ethylene was first selectively dimerized/isomerized over Ni-AlSBA-15 catalyst to form 2-
butenes, which reacted then with the excess of ethylene over MoO –SiO –Al O to produce propylene. At 80 °C and 3 MPa, specif-
3
2
2
3
ic activities up to 48 mmol of propylene per gram of catalyst per hour were obtained.
Discovered in 1955, olefin metathesis has become one of
the most important reactions for producing various chemicals
Several works have been reported on the direct conversion
of ethylene to propylene in a continuous, 1-pot process, while
avoiding the use of homogeneous catalysts. Thus, the direct
1-4
in both petrochemistry and organic synthesis areas. In 1964,
8
conversion of ethylene to propylene over zeolites or SAPO
9
the first process involving metathesis (Triolefin process) was
developed by Phillips Petroleum for converting propylene into
catalysts at temperatures higher than 400 °C has been ex-
plored, but these catalysts showed a severe deactivation with
5
highly demanded ethylene and 2-butene. Metathesis is a
10
reversible reaction, and as the demand for polymer-grade
propylene grew after the 1970s, metathesis was used in the
Olefin Conversion Technology (OCT®) licensed by ABB
Lumnus to produce propylene by conversion of an equimolar
mixture of ethylene and butene over a supported W catalyst.
Since then, a number of technologies based on OCT® and W,
Re and Mo-based catalysts have been developed by other
companies, such as BASF & Atofina, Mitsui Chemicals, BP
time on stream. Iwamoto and co-workers and more recently
Seidel-Morgenstern et al.
11,12
13
and Hinrichsen et al. reported
that nickel-loaded mesoporous materials catalyzed the conver-
sion of ethylene to propylene, but only at temperatures higher
than 350 °C. The catalytic tests were carried out at very low
-
1
-1
reactant feed rate (0.1-0.2 LC2H4
h gcatal ) and the yield of
1
4
propylene was about 30%. Basset and co-workers reported
the direct transformation of ethylene to propylene over tung-
sten hydride supported on γ-alumina. At 150 °C and at a vol-
4,6
Chemical, Sinopec & Shanghai Petrochemical Processes.
-
1
ume hourly space velocity of 260 h , the selectivity to propyl-
ene was higher than 95%, but the ethylene conversion dropped
rapidly from 40% to 10% over the first hours on stream.
A higher growth rate in the demand for propylene compared
to ethylene during the last decade and the need to develop
sustainable feedstocks stimulated the interest for the conver-
sion of ethylene to propylene without any addition of other
hydrocarbons. Ethylene is usually produced from crude oil
derivatives (via steam thermal cracking), but alternative meth-
ods involving natural gas (via zeolite-catalyzed methanol-to-
olefin process) or bio-ethanol conversion into ethylene, are
very promising also. Several catalytic systems and strategies
were proposed for the propylene production using only eth-
ylene as a raw-material. Lyondell Petrochemical Co. devel-
oped in the 1980s a two-step process for the production of
propylene, using the ethylene from ethane-cracking technolo-
gy. First, using a homogeneous nickel catalyst, part of the
ethylene is dimerized to 2-butene, which is reacted in a second
15
Recently, Li et al. reported that a dual site bimetallic cata-
lyst, NiSO /Re O /γ-Al O , prepared by co-impregnation,
catalyzed the direct conversion of ethylene to propylene under
4
2
7
2
3
-1
mild reaction conditions (50°C, 1 atm, GHSV of 2,682 h ).
The two catalyst functions worked independently for dimeri-
zation (NiSO ) and metathesis (Re O ). However, the yield for
4
2
7
propylene was lower than 30%, and the catalytic system rapid-
ly deactivated.
Rather than using a single, multifunctional catalyst, an op-
tion could be to use two (or more) distinct heterogeneous
catalysts in a single reactor. This would offer increased control
and allow using robust existing catalysts. However, there is no
example of such a tandem catalysis coupling ethylene dimeri-
zation, butene isomerization, and metathesis to produce pro-
pylene, although several tandem reactions involving metathe-
step with the rest of the ethylene over a W/SiO catalyst to
2
4
7
produce propylene. Pillai et al. reported the 2-step conver-
sion of ethylene to propylene in a batch reactor by sequential
use of homogeneous catalysts, Ni(acac) -Et Al Cl as a dimer-
16
2
3
2
3
sis have been described.
ization-isomerization catalyst, and WCl -Et Al Cl as a me-
6
3
2
3
tathesis catalyst.
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During the last decade, our institute has been working ex- MoO –SiO –Al O had a Si/Al ratio of 14.4, and a Mo content
3
2
2
3
2
+
2
of 6.5 wt% (0.75 Mo per nm ), corresponding to a MoO load-
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tensively for developing highly active and selective Ni -based
ordered mesoporous catalysts (Ni-AlMCM-41, Ni-AlMCM-
3
ing of 9.7 wt%. Both catalysts were mesoporous (Figure 1),
with high specific surface areas and large mesopores. Large
pore sizes are needed for ethylene oligomerization: mi-
croporous catalysts such as Ni-exchanged zeolites rapidly
deactivate due to the blocking of micropores by heavy prod-
ucts.
1
7-20
48, and Ni-AlSBA-15) for the ethylene oligomerization . In
particular, Ni-AlSBA-15 catalysts exhibited outstanding
productivity and stability in the ethylene conversion to C4-
C10 olefins (up to 175 g of oligomers per g of catalyst per
hour at 150 °C and 3.5 MPa). By choosing the reaction mode
and parameters, the conversion of ethylene could be selective-
ly directed to butenes or larger olefins.
2
0
In parallel we have been developing in our institute an inno-
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vative non-hydrolytic sol–gel route for preparing mesopo-
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rous mixed oxides catalysts. The MoO –SiO –Al O mixed
2
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2
2
3
oxides prepared by this route exhibited high specific surface
areas, large disordered mesopores, and highly dispersed sur-
face molybdenum species. They were found to be highly ac-
tive and selective catalysts in the self-metathesis of propylene
23,24
at low temperature.
In this context, the objective of this study was to investigate
the conversion in a single flow reactor of ethylene to propyl-
ene under mild conditions, using two robust inorganic hetero-
geneous catalysts (Ni-AlSBA-15 and MoO –SiO –Al O )
3
2
2
3
through tandem dimerization, isomerization, and metathesis
reactions (Scheme 1). Note that both catalysts are stable in air,
and that no special precautions are needed for their storage and
handling.
Figure 1. Nitrogen physisorption isotherms of Ni-AlSBA-15 and
MoO –SiO –Al O catalysts.
3
2
2
3
CH
3
CH3
Ni-AlSBA-15
Ni-AlSBA-15
2
H
2
C CH
2
The XRD pattern of Ni-AlSBA15 and of the starting SBA-
15 material were similar (Figure S1), indicating that the long
range ordering of the pores was maintained after alumination
H C
3
H
2
C
20
and ion exchange. On the other hand, Mo-Si-Al was amor-
phous to XRD, confirming the absence of crystalline MoO3,
while the sorption isotherm ruled out any long range ordering
CH
3
CH3
MoO -SiO -Al O
3
3
2
2
+
H C CH
2
2 H C
2
2
H C
3
24
of the mesoporosity.
20
Scheme 1. Reaction sequence: ethylene dimerization, bu-
tene isomerization and cross-metathesis.
In a recent study, we showed that Ni-AlSBA-15 was a
highly active and stable catalyst for the ethylene oligomeriza-
tion carried out in flow mode, under various conditions: T =
The dimerization/isomerization catalyst, Ni-AlSBA-15, was
prepared by grafting a SBA-15 silica support with sodium
aluminate (NaAlO ), followed by cation exchange, first with
5
(
0-150°C, p = 1.0-4.0 MPa, and mass hourly space velocity
-1
WHSV) = 10-17.5 h . Butenes, hexenes and octenes were the
2
major products. The reaction conditions had a decisive influ-
ence on the ethylene conversion and the oligomer distribution.
The increase of temperature, residence time and pressure
resulted in an increase of the ethylene conversion, a decrease
of the selectivity to butenes, and an increase of the double
bond isomerization within the butene fraction. MoO –SiO –
+
2+
NH4 then with Ni . The exchanged sample was dried and
2
0
then calcined for 5 h at 550°C. The metathesis catalyst,
MoO –SiO –Al O , was prepared by a one-step non-hydrolytic
3
2
2
3
sol-gel method involving the reaction of chloride precursors
(MoCl , SiCl , AlCl ) with diisopropyl ether at 110 °C in an
autoclave. The gel was dried by evaporation and calcined at
5
4
3
3
2
Al O mixed oxides were found highly active in the metathesis
3
23
2
5
main textural characteristics are summarized in Table 1.
00 °C for 5 h. The composition of the catalysts and their
25
of propene as well as in the metathesis of ethylene and bu-
23
-1 -1
tene at 40 °C, with specific activities of about 45 mmol g h
for a catalyst with a Si/Al ratio of ≈14 and a Mo loading of
12.5 wt%.
a
Table 1. Composition and texture of the catalysts
Catalyst
Si/Al
Me
DP
VP
SBET
2
m /g
In order to produce propylene from ethylene (according to
Scheme 1), two consecutive catalyst beds consisting of Ni-
mol/mol wt%
nm mL/g
7.6 0.75
8.1 1.12
Ni-AlSBA-15
7.0
2.6
6.5
450
540
AlSBA-15 and MoO –SiO –Al O , respectively, were placed
3 2 2 3
in the reactor. Based on previous results obtained in the oli-
gomerization and metathesis reactions and preliminary exper-
iments, the following parameters were chosen for conducting
the oligomerization-metathesis reactions: T = 80 °C, p = 3.0
MoO -SiO -Al O
3
14.4
3
2
2
a
Me = Ni or Mo, BJH average pore diameter (D ), total pore
P
volume (V ), specific surface area (SBET)
P
-
1
MPa and flow rate = 33 mL min of pure ethylene. WHSV
-1
Ni-AlSBA-15 had a Si/Al ratio of 7.0 and a Ni content of
2.6 wt%. The corresponding Ni/Al ratio is 0.25, indicating an
-
was 16.5 h for the oligomerization catalyst (0.15 g) and 5 h
1
+
exchange level of NH4 ions with Ni of about 50%. As a
2+
for the metathesis catalyst (0.50 g). A moderate conversion of
ethylene is favorable, because it limits the formation of higher
consequence of this partial exchange level, Ni-AlSBA-15
contains Bronsted-type acidic sites, as AlSBA-15 materials.
20
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oligomers in the oligomerization step, and increases the con-
version in the metathesis step.
Considering the total number of Mo atoms in the catalyst, a
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specific activity of 51.3 mmol gcatal
-1
h
mmolC3 mmolMo h (4.6 mol molMo min ).
corresponds to 277
-1
C3
-
1
-1
Figure 2 shows typical chromatograms obtained with one
catalyst (Ni-AlSBA-15) and two catalysts (Ni-AlSBA-15 and
MoO –SiO –Al O ). Over Ni-AlSBA-15, butenes were the
C3
The mechanism of the ethylene oligomerization using
metal-based homogeneous catalysts involves the insertion of
3
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2
3
26,27
major products, but small amount of C6 and C8 olefins were
also formed. In the C4 fraction, the only detected molecules
were the three n-butene isomers: 1-C4, trans- and cis-2-C4.
Both ethylene conversion (28±1%) and oligomer distribution
did not change during 6 h on stream. In the presence of the
two catalysts, beside C4, C6 and C8 olefins, propylene, pen-
tenes and heptenes were also formed.
ethylene into an initial metal-alkyl or a metal-hydrogen
28
bond. A cocatalyst is required for generating the metal-active
species. Such a growth mechanism seems unlikely for the
oligomerization of ethylene catalyzed by nickel ions dispersed
on inorganic supports because neither metal-alkyl nor metal
hydride species are initially formed on these materials in the
absence of a cocatalyst.
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40
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70
60
5
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0
4
30
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0
50
100
150
200
250
300
Time on stream, min
Figure 2. Typical chromatograms for ethylene oligomerization
over Ni-AlSBA-15 (A) and oligomerization-metathesis over Ni-
AlSBA-15 + MoO –SiO –Al O (B); Conditions: 80 °C, 3.0 MPa
Figure 3. Selectivity to propylene (o), butenes (ꢀ) and productivi-
ty in propylene (+) vs. time on stream. Conditions: 80 °C, 3.0
MPa of ethylene.
3
2
2
3
of ethylene.
29,30
In two interesting studies published in the 80s, it has
Under the present reaction conditions the major olefins were
propylene and butenes (> 90%). The selectivity to C5, C6 and
C7+ olefins was 4-5%, 3-4% and 1-2%, respectively. The
presence of C5 and C7 olefins indicate that MoO –SiO –Al O
3
+
been shown that it was possible to produce supported Ni ions
+
on zeolites and SiO . These dispersed Ni ions can reversibly
2
2-
bind ligands (L) such as C H , C H , or surface oxide ions O
s
2
4
3
6
+
leading to various Ni(L)n species. The oligomerization mech-
3
2
2
was also able to catalyze metathesis reactions involving ole-
fins higher than C4.
anism involves a metallacyclopentane intermediate resulting
+
from a concerted coupling of two olefin molecules on each Ni
center. Such a mechanism has also been suggested for the
The selectivity profiles to C3 and C4 as a function of time
on stream are given in Figure 3. The initial selectivity to pro-
pylene reached 70% but decreased progressively to 46% at 5 h
on stream. The selectivity to butenes increased from 22% to
3
ethylene dimerization over phosphine-Ni complexes. In a
1
32
previous study we showed that during the treatment at tem-
peratures higher than 500 °C under a dry atmosphere, the
2+
initial Ni ions in Ni-MCM-41 and Ni-Y catalysts were dehy-
4
8%. Note that the conversion of ethylene was quasi-constant
+
drated and reduced to Ni ions. Based on these data, we pro-
at 40±2% throughout the reaction period. These results indi-
cate that the activity of the metathesis catalyst diminished with
time on stream, while the oligomerization catalyst maintained
its activity during the catalytic test. Deactivation is a rather
systematic drawback for metathesis catalysts, due mostly to
the poisoning of the active centers by strongly adsorbed reac-
tion products. In our system the low reaction temperature may
contribute to the deactivation process by preventing fast prod-
uct desorption. Further studies will be needed to determine
optimal conditions allowing to avoid, or at least minimize,
such a limitation.
pose for the ethylene dimerization step the mechanism shown
in Scheme 2, where two molecules of coordinated ethylene at
a nickel ion react by oxidative coupling to form a metallacy-
clopentane intermediate, which then forms 1-butene by β-
33
hydride transfer.
When the desorbed 1-butene migrates to an acid site, it is
easily converted to internal double-bond olefin, as shown in a
simplified manner in Scheme 2. Note that double-bond shift in
alkenes is an extremely facile reaction, exhibiting turnover
7
-1
34
frequencies up to 10 s in heterogeneous acid catalysis.
35
The specific activity of the catalysts for the C3 formation (in
Hartmann et al. showed that the isomerization of 1-butene to
cis-2-butene and trans-2-butene can be efficiently catalyzed
by Al-MCM-41 materials.
-
mmolC3 gcatal h ) was also reported in Figure 3. Although it
1
-1
-
1
-1
h with the time on
decreased from 51.3 to 33.7 mmol g
stream, these values are remarkably high. Indeed, they are
close to the values reported for Mo-Si-Al non-hydrolytic sol-
gel catalysts with similar compositions, previously used for
The cross-metathesis of ethylene and 2-butenes over the
MoO –SiO –Al O catalyst most likely involves the initial
3
2
2
3
6
formation of carbene species (Mo=CHR, R = H or alkyl),
followed by the formation of metallacyclobutane intermedi-
36,37
ates, as proposed in Chauvin’s reaction mechanism.
25
the self-metathesis of propylene to ethylene and butenes or in
23
the metathesis of ethylene and trans-2 butene to propylene.
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Scheme 2. Proposed mechanism for the conversion of ethylene to propylene (O = O surface oxide ions).
S
In summary, we have proposed an original cascade catalytic
method allowing the one-pot continuous synthesis of propyl-
ene from ethylene. This method is based on the use of two
robust and highly active heterogeneous catalysts developed in
our institute. The preliminary results reported here are promis-
ing in terms of catalyst productivity and selectivity to C3-C4
olefins, but additional work is needed to optimize conditions
in order to improve catalyst lifetime and selectivity to propyl-
ene.
(13)
Mesoporous Mater. 2012, 164, 164-171.
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ASSOCIATED CONTENT
Lallemand, M.; Finiels, A.; Fajula, F.; Hulea, V.
Supporting Information. Experimental details of the synthesis
and characterization of the catalysts.
(20) Andrei, R. D.; Popa, M. I.; Fajula, F.; Hulea, V.
J. Catal. 2015, 323, 76-84.
This material is available free of charge via the Internet at
http://pubs.acs.org.
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AUTHOR INFORMATION
Catal., A 2013, 451, 192-206.
(23)
Corresponding Author
Bouchmella, K.; Mutin, P. H.; Stoyanova, M.;
Poleunis, C.; Eloy, P.; Rodemerck, U.; Gaigneaux, E. M.; Debecker,
D. P. J. Catal. 2013, 301, 233-241.
*E-mail: vasile.hulea@enscm.fr
(
24)
Debecker, D. P.; Bouchmella, K.; Poleunis, C.;
Eloy, P.; Bertrand, P.; Gaigneaux, E. M.; Mutin, P. H. Chem. Mater.
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Graphic for manuscript
H
O
Mo
CH2
C H
0
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0
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0
2
C H
2 4
+
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Ni (O
s
)
n
Si
Al
Mo
Mo
+
+
H
Ni (O
s
)
n-
2
Ni (O
s
)
n-
2
+
Ni (O
s
)
n-
2
O
C H
3
6
Si
Al
Mo
H
C H
2
4
Dimerization Ni-AlSBA-15
Isomerization Ni-AlSBA-15 Metathesis MoO -SiO -Al O
( )
3 3
2 2
( )
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