Selective Production of Propylene and 1-Butene from Ethylene by Catalytic Cascade Reactions

Article abstract of DOI:10.1021/acscatal.8b00663

In this study, we report that ethylene can be simultaneously and selectively converted into propylene and 1-butene through one-pot catalytic cascade reactions. In a single-continuous-flow reactor and under identical mild conditions (60 °C, 3 MPa), without the use of cocatalyst, ethylene was first dimerized/isomerized over Ni-AlKIT-6 catalysts to form butenes, which reacted then with the excess of ethylene over ReO_x/Al₂O₃ to produce propylene and 1-butene with more than 86% total selectivity. The selectivity for 1-butene was 97.4% in the C4 fraction. The initial ethylene conversion was 73% and stabilized at 35% after 4 h on stream, with around 45% selectivity in propylene and 42% selectivity in 1-butene.

Full text of DOI:10.1021/acscatal.8b00663

Subscriber access provided by UNIV OF DURHAM
Selective production of propylene and 1-butene
from ethylene by catalytic cascade reactions
Rémi Beucher, Radu Dorin Andrei, Claudia Cammarano,
Anne Galarneau, François Fajula, and Vasile Hulea
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.8b00663 • Publication Date (Web): 22 Mar 2018
Downloaded from http://pubs.acs.org on March 22, 2018
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a service to the research community to expedite the dissemination
of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in
full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully
peer reviewed, but should not be considered the official version of record. They are citable by the
Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore,
the “Just Accepted” Web site may not include all articles that will be published in the journal. After
a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web
site and published as an ASAP article. Note that technical editing may introduce minor changes
to the manuscript text and/or graphics which could affect content, and all legal disclaimers and
ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or
consequences arising from the use of information contained in these “Just Accepted” manuscripts.
is published by the American Chemical Society. 1155 Sixteenth Street N.W.,
Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the
course of their duties.

Page 1 of 16
ACS Catalysis
1
2
3
4
5
6
Selective Production of Propylene and 1-Butene from Ethylene by
Catalytic Cascade Reactions
7
8
9
Rémi Beucher, Radu Dorin Andrei, Claudia Cammarano, Anne Galarneau, François Fajula,
Vasile Hulea*
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Institut Charles Gerhardt Montpellier, UMR 5253, CNRS-ENSCM-Univ Montpellier,
Matériaux Avancés pour la Catalyse et la Santé, 240 avenue du Professeur Emile Jeanbrau,
CS 60297, 34296 Montpellier Cedex 5, France
*Corresponding author: vasile.hulea@enscm.fr
TOC graphic
CH3
H2C
CH3
S = 90%
H3C
H2C
2
CH3
CH3
CH2
ReOx/Al2O3
H C
5
2
60 °C, 3 MPa
H2C
Catalytic cascade reactions
ABSTRACT: In this study we report that ethylene can be simultaneously and selectively
converted into propylene and 1-butene through one-pot catalytic cascade reactions. In a single
continuous flow reactor, and under identical mild conditions (60 °C, 3 MPa), without the use
of co-catalyst, ethylene was first dimerized/isomerized over Ni-AlKIT-6 catalysts to form
butenes, which reacted then with the excess of ethylene over ReOx/Al2O3 to produce
propylene and 1-butene with more than 86% total selectivity. The selectivity for 1-butene was
97.4% in the C4 fraction. The initial ethylene conversion was 73% and stabilized at 35% after
4 h on stream, with around 45% selectivity in propylene and 42% selectivity in 1-butene.
KEYWORDS: heterogeneous catalysis, oligomerization, metathesis, ethylene, propylene, 1-
butene
1
ACS Paragon Plus Environment

ACS Catalysis
Page 2 of 16
1
2
3
4
5
6
7
8
9
With stricter environmental regulation and depletion of fossil feedstock, renewable resources
attracted increased interest in recent research. Various new bio-based molecules were
proposed for replacing the platform chemicals based on crude oil, but there are not yet well
established processes for producing these chemicals at large scale.1-3 As a result, in the short
to mid-term, a much larger impact might be expected from the production of bio-based
molecules with a structure identical to today’s bulk chemicals. Among them, ethylene is one
of the most promising bio-based chemicals, mainly because its high-volume production by
bioethanol dehydration became economically feasible. Additionally, ethylene is a key
intermediate for producing other major platform molecules like 1-butene and propylene.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
The dimerization of ethylene to 1-butene is a well-known reaction. The commercial processes
use organic solvents and homogeneous catalysts.4,5 The challenge is to obtain 1-butene in
greener dimerization processes based on heterogeneous catalysis. Among the main solid
catalysts studied, namely immobilized complexes on polymers and oxides,6-8 metal organic
frameworks (MOFs) materials9-12 and nickel supported on inorganic porous materials, the
latter are the most promising.13 First, they are very robust and efficient catalysts for ethylene
dimerization/oligomerization at temperatures lower than 150 °C.14-16 Moreover, unlike other
catalysts, no activator or co-catalyst is required in this case. Despite these advantages, the
main drawback associated with this method is that among the C4 isomers, 2-butenes
predominate to 1-butene.
Propylene can be also produced from ethylene via well-establish technology, i.e. cross-
metathesis with 2-butene.17-19 This reaction is activated by Re, Mo and W-based catalysts and
needs an equimolecular ethylene-butenes proportion. The high growth rate in the demand for
propylene during the past decade and the need to develop sustainable feedstocks stimulated
the interest for the conversion of ethylene to propylene without any addition of other
2
ACS Paragon Plus Environment

Page 3 of 16
ACS Catalysis
1
2
3
4
5
6
hydrocarbons. Two methods, based on acid catalysts (at high temperature) and
multifunctional heterogeneous catalysts (at lower temperature) are investigated.
7
8
9
The conversion of ethylene to propylene (ETP) at temperatures higher than 450 °C is
catalyzed by zeolites and SAPOs.20-22 The negative aspect of the acid microporous catalysts in
this process are their severe deactivation with time on stream and the low selectivity to
propylene.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
On the other hand, some multifunctional catalysts and strategies have been recently proposed
for producing propylene in ETP processes through successive dimerization/metathesis
reactions using only ethylene as a raw-material. Iwamoto,23 Seidel-Morgenstern24 and
Hinrichsen25 groups reported that Ni-MCM-41 and Ni-MCM-48 catalysts prepared by
"template ion exchange" catalyzed the conversion of ethylene to propylene at temperature
higher than 350 °C. Basset and co-workers26 reported the direct transformation of ethylene to
propylene over tungsten hydride supported on γ-alumina at 150 °C. Li et al.27 reported that a
dual site bimetallic catalyst, NiSO4/Re2O7/γ-Al2O3, catalyzed the direct conversion of
ethylene to propylene at 50 °C, in a reactor operated in pulse mode. A multicomponent
catalyst, namely NiO/Re2O7/B2O3-Al2O3 was also able to activate the ETP reaction at 80 °C.28
Conditions of reaction for these studies and the main experimental results will be summarized
below.
More recently, we have reported an original method for converting ethylene to propylene
involving cascade oligomerization/isomerization/metathesis reactions over two robust, air
stable, and highly active heterogeneous catalysts.29,30 In a single flow reactor and under
identical conditions, ethylene was selectively dimerized/isomerized over Ni-AlSBA-15 or Ni-
AlSiO2 catalysts to form 2-butenes, which then reacted then with the excess of ethylene over
Mo-based catalysts to produce propylene (Scheme 1).
3
ACS Paragon Plus Environment

ACS Catalysis
Page 4 of 16
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Scheme 1. Conversion of ethylene to propylene in a cascade process
At 80 °C and 3 MPa, the average conversion of ethylene was 40% leading to specific
activities up to 48 mmol of propylene per gram of catalyst per hour, with a selectivity of 90%
for propylene and butenes, but with a majority of 2-butenes (20% 1-C4 and 80% 2-C4).
Herein we report on a new very efficient heterogeneous catalytic system associating Ni-
AlKIT-6 and ReOx/γ-Al2O3, which is able to transform selectively ethylene into propylene
and 1-butene. KIT-6 is an ideal support combining high surface area and large interconnected
mesopores with homogeneous mesopore size distribution, which is key parameter for high
mass transfer properties.31,32 ReOx/γ-Al2O3 is a well-known metathesis catalyst able to work at
low temperature.18,33
The dimerization/isomerization catalyst, Ni-AlKIT-6, was prepared by grafting a KIT-6 silica
support (prepared according to our previous work34) with sodium aluminate (NaAlO2),
+
followed by cation exchange, first with NH4 then with Ni2+. The exchanged sample was dried
and then calcined for 5 h at 550 °C. Ni-AlKIT-6 had a Si/Al ratio of 7.0 and a Ni content of
+
1.9 wt%. The corresponding Ni/Al ratio is 0.2, indicating a partial exchange level of NH4
ions with Ni2+. As a consequence, Ni-AlKIT-6 contains both Ni2+ and Brønsted-type acidic
sites. The metathesis catalyst, ReOx/γ-Al2O3 was prepared by incipient wetness impregnation
using an aqueous solution of NH4ReO4 and a commercial γ-Al2O3. It contains 4.0 wt% Re (0.5
Re per nm2), corresponding to a ReO4 loading of 5.4 wt%. After impregnation and drying, the
catalyst was calcined in air at 550 °C for 8 h.
4
ACS Paragon Plus Environment

Page 5 of 16
ACS Catalysis
1
2
3
4
5
6
The composition of the catalysts and their main textural characteristics are summarized in
Table 1. Both catalysts have pores larger than 7 nm.
7
8
9
Table 1. Composition and texture of the catalysts
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Catalyst
Si/Al
Mea
wt%
1.9
DP
VP
SBET
m2 g-1
390
mol mol-1
nm
7.0
13.5
mL g-1
0.71
0.73
Ni-AlKIT-6
7.0
-
4.0
260
ReOx/γ-Al2O3
a Me = Ni or Re, BdB average pore diameter (DP), total pore volume (VP), BET specific surface area (SBET
)
Nitrogen adsorption-desorption isotherm (Figure 1) of Ni-AlKIT-6 is of type IV, with a sharp
capillary condensation step, characteristic of high-quality material with homogeneous
mesopores. As previously reported,14,15 the large mesopores are very beneficial to the free
diffusion of heavier oligomers/products inside the pore system, which results in a lower
deactivation rate and higher activity in comparison to microporous materials as zeolites.
ReOx/γ-Al2O3 exhibits mesopores with a large pore size distribution centered at 13 nm and a
high surface area for alumina materials.
Figure 1. Nitrogen physisorption isotherms at -196 °C of (a) Ni-AlKIT-6 and (b) ReOx/γ-
Al2O3 catalysts
5
ACS Paragon Plus Environment

ACS Catalysis
Page 6 of 16
1
2
3
4
Small-angle XRD pattern of Ni-AlKIT-6 (Figure S1) indicated the long range ordering of the
5
6
mesopores and the bicontinous cubic Ia3d symmetry characteristic of KIT-6 topology.35
7
8
27
ReOx/γ-Al2O3 was amorphous to XRD, confirming the absence of crystalline ReOx. The Al
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
MAS NMR spectrum (Figure S2) confirmed the insertion of aluminum atoms as tetrahedrons
in the silica network of KIT-6. Raman spectrum of the ReOx/Al2O3 catalyst (Figure S3)
indicated the presence of isolated ReO4 species.36,37 TPR analysis of the Re-based catalyst
revealed two peaks at 365 and 420 °C (Figure S4), which are assigned to reduction of Re7+
surface ions interacting with the support.38 These peaks indicate that there are two different
Re7+ species, although Raman spectroscopy detected only one monomeric tetrahedral species.
The reduction signal at 365 °C is attributed to the isolated ReO4 species, while that at 420 °C
indicates the presence of small and vibrationally undetected oligomeric rhenium oxo-surface
species.39
Before to perform the cascade reactions, the oligomerization reaction has been separately
studied on Ni-AlKIT-6 catalyst. The ethylene oligomerization was performed in a stainless
steel fixed bed reactor (i.d. 5 mm) using 0.2 g of Ni-based catalyst (0.15–0.25 mm sieve
fraction). At 60 °C and 3 MPa, with a gas feed consisting of ethylene and nitrogen (5/1
vol/vol, 20 mL min-1, WHSV = 7.5 h-1), the reaction products were butenes (80%), hexenes
(19%) and octenes (< 1%). In the C4 fraction, the only detected molecules were 1- and 2-
butene. During 4 h on stream the molar ratio 1-C4/2-C4 varied from 35/65 to 47/53. The
ethylene conversion decreased progressively from 47 to 27% (at 4 h on stream) and 16% (at
18 h on stream). The typical composition of C6 fraction was: 5% 1-C6, 40% 2-C6, 25% 3-C6,
25% 3-methyl-1-C5 and 5% 3-methyl-1-C5.
To produce propylene from ethylene oligomerization-metathesis reactions, according to
Scheme 1, two consecutive catalyst beds consisting of Ni-AlKIT-6 (0.2 g) and ReOx/γ-Al2O3
(0.5 g) were placed in the same reactor. Thus, the metathesis catalyst is in excess compared to
6
ACS Paragon Plus Environment

Page 7 of 16
ACS Catalysis
1
2
3
4
5
6
7
8
9
the oligomerization catalyst. The reaction was conducted at 60 °C, 3 MPa and with a gas flow
rate of 20 mL min-1 (ethylene/nitrogen : 5/1 vol/vol). The low temperature limits the
formation of high molecular weight oligomers in the oligomerization step, and increases the
conversion in the metathesis step. Figure 2 shows a typical chromatogram obtained during the
reaction. The major products were propylene and butenes (selectivity up to 86%). Some
pentenes and hexenes were also detected in low concentration (selectivity of 10-12%). The
presence of small amount of C5 olefins indicate that ReOx/γ-Al2O3 catalyzes also some
metathesis reactions involving C6 olefins.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Figure 2. Typical chromatogram for ethylene conversion; all products are unsaturated
hydrocarbons
The selectivity for 1-butene in the C4 fraction was remarkably high : 97.4% 1-C4, 1.9% 2-cis-
C4 and 0.7% 2-trans-C4. This value exceeds the selectivities previously obtained with various
solid catalysts (Table 2). It is comparable to the highest ethylene dimerization selectivity ever
obtained over MOF catalysts, in the presence of co-catalyst, recently reported by Metzer et
al.12
7
ACS Paragon Plus Environment

ACS Catalysis
Page 8 of 16
1
2
3
4
Table 2. 1-Butene selectivity in ethylene dimerization over selected catalystsa
5
6
Catalyst
Me, wt%
T, °C P, MPa 1-C4 selectivity, % Ref
7
8
9
Ni-MCM-41
Cr-Co-C
Ni-MOFb
5.0
-15
80
25
25
60
3.0
3.1
3.0
5.0
3.0
93
40
13.0 (Co), 5.0 (Cr)
93.6
95
41
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
10.0
9
Ni-MOFc
1.0
96.2
97.4
12
Ni-AlKIT-6 + ReOx/γ-Al2O3
a 1-butene (%mol) among butenes; b co-catalyst Et2AlCl ; c co-catalyst MAO
1.9 (Ni), 4 (Re)
This study
From a quantitative point of view, the process was also very efficient. The initial conversion
of ethylene reached 73% and decreased progressively to stabilize around 35% after 4 h on
stream (Figure 3).
100
80
60
40
20
0
0
1
2
3
4
Time on stream, h
Figure 3. Ethylene conversion (□), propylene (○) and 1-butene (∆) selectivity (%mol) as a
function of time at 60 °C.
Deactivation is a systematic well-known drawback for the metathesis catalysts, most probably
due to the poisoning of the active centers by strongly adsorbed products. The initial selectivity
in propylene and 1-butene were 60 and 30 mol%. These values vary with the time on stream
(TOS), to stabilize at 45 and 42 mol%, respectively, after 4 h of reaction (Figure 3). The
decrease of propylene and the increase of 1-butene are consistent with the oligomerization
8
ACS Paragon Plus Environment

Page 9 of 16
ACS Catalysis
1
2
3
4
5
6
7
8
9
step results: 2-butene, responsible for propylene formation by metathesis, decreases from 65
to 53%, while 1-butene increases from 35 to 47%. The turnover frequency (TOF) values
varied from 503 to 235 molC2H4 molNi-1 h-1, and the turnover number (TON = TOF x TOS)
after 4 h of reaction was more than 1200.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
The direct conversion of ethylene into propylene, without addition of other hydrocarbons, has
been investigated over various catalytic systems. The specific activity in propylene and 1-
butene obtained in the present study is compared with those reported in literature (Table 3).
The specific activity in propylene and 1-butene are among the highest achieved in such a
process. In addition, this process is the only one leading to almost pure 1-butene (more than
97% in the C4 fraction).
Table 3. Direct conversion of ethylene into propylene with multifunctional catalysts
Catalysts
T, °C P,
MPa
C2 conv.,a
%
C3,a
1-C4,a
mmolC4
gcatal-1 h-1
2.8d
0.1 e
0.1d
Ref
mmolC3
gcatal-1 h-1
3.1
Ni-MCM-41
400
400
350
150
50
0.1
0.1
0.1
0.1
0.1
0.1
3.0
3.0
3.0
68
23
Ni-AlMCM-41
75
1.1
24
Ni-MCM-48
48
40-10b
0.8
25
W-H/ γ-Al2O3
9.6-2b
12.6
2.8
0.2e
4.5d
26
NiSO4/Re2O7/γ-Al2O3
Pd/Re2O7/B2O3-Al2O3
Ni-AlSBA-15 + MoO3–SiO2–Al2O3
Ni-AlSiO2 + MoOx/(Al)SiO2
60
27
80
22
traces
10.0e
5.1e
28
80
40
48.0
28.0
29
80
41
73-35c
30
This study
Ni-AlKIT-6 + ReOx/γ-Al2O3
60
26.0-9.3c 13.0-8.7c,f
a
c
the highest values in each study; b 0.1-30 h on stream; 0.3-4 h on stream (only ReOx/γ-Al2O3 was considered
as catalyst for this evaluation); d 1-butene represents about 30% among the C4 isomers; e 1-butene represents
about 20% among the C4 isomers; f 1-butene represents > 97% among the C4 isomers
Accordingly to previous studies,15,16,29,30 the present catalytic behavior can be explained as
follow. Two ethylene molecules coordinated to a nickel ion on Ni-AlKIT-6 react to form 1-
butene, some of them migrates to an acid sites to isomerize into cis/trans-2-butene. Over the
9
ACS Paragon Plus Environment

ACS Catalysis
Page 10 of 16
1
2
3
4
5
6
7
8
9
second catalyst, ReOx/γ-Al2O3, the cross-metathesis between the excess of ethylene and
butenes occurs (according to Scheme 1). The couple ethylene/(cis/trans-2-butene) gives
propylene (Eq. 1), while ethylene/1-butene gives a symmetrical reaction leading to 1-butene
and ethylene (Eq. 2, Scheme 2).
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
CH3
Eq. 1
Eq. 2
H3C
H2C
H2C
2
CH3
CH3
CH2
CH3
+
H2C
H2C
H2C
CH3
CH3
H2C
CH3
+
H3C
H3C
Eq. 3
Eq. 4
CH3
CH2=CH2
CH3
H2C
2
CH3
H2C
H3C
Eq. 5
Eq. 6
+
H2C
CH3
CH3
CH3
H3C
CH3
CH3
CH3
H3C
+
+
H3C
H2C
H2C
CH3
Scheme 2. The main metathesis reaction pathways
The high selectivity in propylene and 1-butene is also due to the metathesis reactions between
the C6 oligomers and ethylene (Eq. 3-5). The contribution of the metathesis reaction between
1-butene and 2-butenes, leading to propylene and 2-pentene, can be also considered (Eq. 6).
In summary, we propose for the first time a catalytic method allowing the one-pot synthesis of
both propylene and 1-butene from ethylene. This method is based on the use of two robust
and highly active heterogeneous catalysts featuring large mesopores for a better transport of
products, which are able to activate the reactions at 60 °C. No co-catalyst is required. The
preliminary results reported here are very promising in terms of global selectivity to C3 and 1-
C4 olefins (more than 86%) and yield (26 mmolC3 gcatal h-1 and 15 mmol1-C4 gcatal h-1 at the
-1
-1
beginning of the process).
10
ACS Paragon Plus Environment

Page 11 of 16
ACS Catalysis
1
2
3
4
5
6
ASSOCIATED CONTENT
Supporting Information
7
8
9
The following file is available free of charge on the ACS Publications website at DOI: xxxxx
Experimental details and results of the synthesis, characterization and behavior of the
catalysts (PDF)
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
AUTHOR INFORMATION
Corresponding Author
*E-mail: vasile.hulea@enscm.fr.
ORICID
Vasile Hulea: 0000-0003-2652-5174
Notes
The authors declare no competing financial interest.
ACKNOWLEDGEMENTS
The authors thank Dr. E. Petit and Mr. P. Gaveau for Raman and NMR measurements.
REFERENCES
(1) Climent, M. J.; Corma, A.; Iborra, S. Converting Carbohydrates to Bulk Chemicals and
Fine Chemicals over Heterogeneous Catalysts. Green Chem. 2011, 13, 520-540.
(2) Rosatella, A. A.; Simeonov, S. P.; Frade, R. F. M.; Afonso, C. A. M. 5-
Hydroxymethylfurfural (HMF) as a Building Block Platform: Biological Properties, Synthesis
and Synthetic Applications . Green Chem. 2011, 4, 754-793.
(3) Gallezot, P. Conversion of Biomass to Selected Chemical Products. Chem. Soc. Rev. 2012,
41, 1538-1558.
(4) Al-Ali AlMa'adeed, M.; Krupa, I. Eds. Polyolefin Compounds and Materials,
Fundamentals and Industrial Applications, Springer: Heidelberg, 2016
(5) McGuinness, D. S. Olefin Oligomerization via Metallacycles: Dimerization,
Trimerization, Tetramerization, and Beyond. Chem. Rev. 2011, 111, 2321-2341.
(6) Rossetto, E.; Nicola, B. P.; de Souza, R. F.; Bernardo-Gusmao, K.; Pergher, S. B. C.
Heterogeneous Complexes of Nickel MCM-41 with β-Diimine Ligands: Applications in
Olefin Oligomerization. J. Catal. 2015, 323, 45-54.
11
ACS Paragon Plus Environment

ACS Catalysis
Page 12 of 16
1
2
3
4
5
6
(7) Scholz, J.; Hager, V.; Wang, X; Kohler, F. T. U.; Sternberg, M.; Haumann, M.; Szesni, N.;
Meyer, K.; Wasserscheid, P. Ethylene to 2-Butene in a Continuous Gas Phase Reaction using
SILP-Type Cationic Nickel Catalysts. ChemCatChem 2014, 6, 162-169.
7
8
9
(8) Kohler, F. T. U.; Gärtner, K.; Hager, V.; Haumann, M.; Sternberg, M.; Wang, X.; Szesni,
N.; Meyer, K.; Wasserscheid, P. Dimerization of Ethene in a Fluidized Bed Reactor using Ni-
Based Supported Ionic Liquid Phase (SILP) Catalysts . Catal. Sci. Technol. 2014, 4, 936-947.
(9) Canivet, J.; Aguado, S.; Schuurman, Y.; Farrusseng, D. MOF-Supported Selective
Ethylene Dimerization Single-Site Catalysts through One-Pot Postsynthetic Modification.
J. Am. Chem. Soc. 2013, 135, 4195-4198.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(10) Liu, B.; Jie, S.; Bu, Z.; Li, B. G. Postsynthetic Modification of Mixed-Linker Metal -
Organic Frameworks for Ethylene Oligomerization. RSC Adv. 2014, 4, 62343–62346.
(11) Madrahimov, S. T.; Gallagher, J. R.; Zhang, G.; Meinhart, Z.; Garibay, S. J.; Delferro,
M.; Miller, J. T. T.; Farha, O. K.; Hupp, J. T.; Nguyen, S. B. Gas-Phase Dimerization of
Ethylene under Mild Conditions Catalyzed by MOF Materials (bpy)NiII Complexes.
ACS Catal. 2015, 5, 6713-3718.
(12) Metzger, E. D.; Brozek, C. K.; Comito, R. J.; Dinca, M. Selective Dimerization of
Ethylene to 1-Butene with a Porous Catalyst. ACS Cent. Sci. 2016, 2, 148-153.
(13) Hulea, V. Towards Platform Chemicals from Bio-Based Ethylene: Heterogeneous
Catalysts and Processes. ACS Catal. 2018, DOI: 10.1021/acscatal.7b04294
(14) Finiels, A.; Fajula, F.; Hulea, V. Nickel-Based Solid Catalysts for Ethylene
Oligomerization – A Review. Catal. Sci. Technol. 2014, 4, 2412-2426.
(15) Andrei, R. D.; Popa, M. I.; Fajula, F.; Hulea, V. Heterogeneous Oligomerization of
Ethylene over Highly Active and Stable Ni-AlSBA-15 Mesoporous Catalysts. J. Catal. 2015,
323, 76-84.
(16) Hulea,V.; Fajula, F. Ni-exchanged AlMCM-41 – An Efficient Bi-functional Catalyst for
the Ethylene Oligomerization. J. Catal. 2004, 225, 213-222.
(17) Mol, J. C. Industrial Applications of Olefin Metathesis . Mol. Catal. A: Chem. 2004, 213,
39-45.
(18) Lwin, S.; Wachs, I. E. Olefin Metathesis by Supported Metal Oxide Catalysts. ACS
Catal. 2014, 4, 2505-2520.
12
ACS Paragon Plus Environment

Page 13 of 16
ACS Catalysis
1
2
3
4
5
6
(19) Gholampour, N.; Yusubov, M.; Verpoort, F. Investigation of the Preparation and
Catalytic Activity of Supported Mo, W, and Re Oxides as Heterogeneous Catalysts in Olefin
Metathesis. Catal. Rev. 2016, 58, 113-156.
7
8
9
(20) Lin, B.; Zhang, Q.; Wang, Y. Catalytic Conversion of Ethylene to Propylene and Butenes
over H-ZSM-5. Ind. Eng. Chem. Res. 2009, 48, 10788-10795.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(21) Zhou, H.; Wang, Y.; Wei, F.; Wang, D.; Wang, Z. Kinetics of the Reactions of the Light
Alkenes over SAPO-34. Appl. Catal. A 2008, 348, 135-141.
(22) Oikawa, H.; Shibata, Y.; Inazu, K.; Iwase, Y.; Murai, K.; Hyodo, S.; Kobayashi, G.;
Baba, T. Highly Selective Conversion of Ethene to Propene over SAPO-34 as a Solid Acid
Catalyst. Appl. Catal. A 2006, 312, 181-185.
(23) Iwamoto, M.; Kosugi, Y. Highly Selective Conversion of Ethylene to Propene and
Butenes on Butenes on Nickel Ion-Loaded Mesoporous Silica Catalysts. J. Phys. Chem. C
2006, 111, 13-15.
(24) Perea, L. A.; Wolff, T.; Veit, P.; Hilfert, L.; Edelmann, F. T.; Hamel, C.; Seidel-
Morgenstern, A. Alumino-Mesostructured Ni Catalyst for the Direct Conversion of Ethene to
Propene. J. Catal. 2013, 305, 154-168.
(25) Frey, A.; Hinrichsen, O. Comparison of Differently Synthesis Ni(Al)MCM-48 Catalysts
in the Ethene to Propene Reaction. Microporous Mesoporous Mater. 2012, 164, 164-171.
(26) Taoufik, M.; Le Roux, E.; Thivolle-Cazat, J.; Basset, J. M. Direct Transformation of
Ethylene into Propylene Catalyzed by a Tungsten Hydride Supported on Alumina:
Trifunctional Single-Site Catalysis. Angew. Chem., Int. Ed. 2007, 46, 7202-7205.
(27) Li, L.; Palcheva, R. D.; Jens, K. J. Conversion of Ethene to Propene by a Dual Function
NiSO4/Re2O7/γ-Al2O3 Catalyst. Top. Catal. 2013, 56, 783-788.
(28) Buluchevskii, E. A.; Mikhailova, M. S.; Lavrenov, A. V. One-Stage Synthesis of
Propylene from Ethylene using Pd-Re2O7/B2O3-Al2O3 Catalyst. Chem. Sustainable Dev.
2013, 21, 47-51.
(29) Andrei, R. D.; Popa, M. I.; Fajula, F.; Cammarano, C.; Al Khudhair, A.; Bouchmella, K.;
Mutin, P. H.; Hulea, V. Ethylene to Propylene by One-Pot Catalytic Cascade Reactions. ACS
Catal. 2015, 5, 2774-2777.
(30) Andrei, R. D.; Popa, M. I.; Cammarano, C.; Hulea, V. Nickel and Molybdenum
Containing Mesoporous Catalysts for Ethylene Oligomerization and Metathesis. New J.
Chem. 2016, 40, 4146-4152.
13
ACS Paragon Plus Environment

ACS Catalysis
Page 14 of 16
1
2
3
4
5
6
(31) Boulaoued, A.; Fechete, I.; Donnio, B., Bernard, M.; Turek, P., Garin, F. Mo/KIT-6,
Fe/KIT-6 and Mo-Fe/KIT-6 as New Types of Heterogeneous Catalysts for the Conversion of
MCP. Microporous Mesoporous Mater. 2012, 155, 131-142.
7
8
9
(32) Hu, B.; Liu, H.; Tao, K.; Xiong, C.; Zhou, S. Highly Active Doped Mesoporous KIT-6
Catalysts for Metathesis 1-Butene and Ethene to Propene: The Influence of Neighboring
Environment of W Species. J. Phys. Chem. C 2013, 117, 26385-26395.
(33) Lwin, S.; Wachs, I. E. Reaction Mechanism and Kinetics of Olefin Metathesis by
Supported ReOx/Al2O3 Catalysts. ACS Catal. 2016, 6, 272-278.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(34) Calin, N.; Galarneau, A.; Cacciaguera, T.; Denoyed, R.; Fajula, F. Epoxy-Functionalized
Large-Pore SBA-15 and KIT-6 as Affinity Chromatography Supports. C.R. Chim. 2010, 13,
199-206.
(35) Kleitz, F.; Choi, S. H.; Ryoo, R. Cubic Ia3d Large Mesoporous Silica: Synthesis and
Replication to Platinum Nanowires, Carbon Nanorods and Carbon Nanotubes. Chem.
Commun. 2003, 2136-2137.
(36) Edreva-Kardjieva, R.M.; Vuurman, M.A.; Mol, J.C. On the Structure of the Oxide form
of Re2O7/Al2O3 and Re2O7/MgO Catalysts. J. Mol. Catal. 1992, 76, 297-305.
(37) Vorakitkanvasin, S.; Phongsawat, W.; Suriye, K.; Praserthdam, P.; Panpranot, J. In situ-
DRIFTS Study: Influence of Surface Acidity of Rhenium-Based Catalysts in the Metathesis
of Various Olefins for Propylene Production. RSC Adv. 2017, 7, 38659-38665.
(38) Arnoldy, P.; van Oeres, E. M.; Bruinsma, O. S. L.; de Beer, V. H. J.; Mouijn, J. A.
Temperature-Programmed reduction of Al2O3-, SiO2-, and Carbon-Supported Re2O7 Catalysts.
J. Catal. 1985, 93, 231-245.
(39) Daniell, W.; Weingand, T.; Knözinger, H. Redox Properties of Re2O7/Al2O3 as
Investigated by FTIR Spectroscopy of Adsorbed CO. J. Mol. Catal. A: Chem. 2003, 204-205,
519-526.
(40) Agirrezabal-Telleria, I.; Iglesias, E. Stabilization of Active, Selective, and Regenerable
Ni-Based Dimerization Catalysts by Condensation of Ethene Withnordered Mesopores. J.
Catal. 2017, 352, 505-514.
(41) Xu, Z.; Chada, J. P.; Xu, L.; Zhao, D.; Rosenfeld, D. C.; Rogers, J. L.; Hermans, I.;
Mavrikakis, M.; Hubert, G. W. Ethylene Dimerization and Oligomerization to 1-Butene and
14
ACS Paragon Plus Environment

Page 15 of 16
ACS Catalysis
1
2
3
4
Higher Olefins with Chromium-Promoted Cobalt on Carbon Catalyst. ACS Catal. 2018, 8,
5
6
2488−2497.
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
15
ACS Paragon Plus Environment

ACS Catalysis
Page 16 of 16
1
2
3
4
Graphic for manuscript
5
6
7
8
9
CH3
H2C
H3C
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
CH3
S = 90%
H2C
2
CH3
CH3
CH2
ReOx/Al2O3
H C
5
2
60 °C, 3 MPa
H2C
Catalytic cascade reactions
ACS Paragon Plus Environment