Journal of Industrial and Engineering Chemistry 53 (2017) 119–126

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Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

Metathesis of 2-pentene over Mo and W supported mesoporous

molecular sieves MCM-41 and SBA-15


Mohamed Ali Ibrahima , Muhammad Naseem Akhtara , Ji
rí Cejka a,b
, Erica Montanaric ,
b
b a,
Hynek Balcar , Martin Kubu , Sulaiman S. Al-Khattaf *
a
Center of Research Excellence in Petroleum Refining and Petrochemicals, King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia
b
J. Heyrovsky Institute of Physical Chemistry, Academy of Sciences of Czech Republic
c
Eni s.p.a., Research & Technological Innovation, Physical Chemistry Dept., Via F. Maritano 26,I-20097 San Donato Milanese, Italy

A R T I C L E I N F O A B S T R A C T

Article history:
Received 15 December 2016 Molybdenum and tungsten oxides were supported on silica, MCM-22, MCM-41 and SBA-15. XRD and N2
Received in revised form 29 March 2017 adsorption–desorption revealed that architecture and textural character of supports were preserved. The
Accepted 4 April 2017 catalysts were investigated in transformation of 2-pentene at different reaction temperatures. MoO3/
Available online 15 April 2017 MCM-22 exhibited highest conversions with isomerization and cracking as major reactions. MoO2(acac)2,
MoO3 and WO3 supported on MCM-41 and SBA-15 showed metathesis reaction of 2-C5= producing
Keywords: propylene, C4= and C6+=as major products. Catalysts based on MCM-41 exhibited higher activity and
Metathesis stability than SBA-15. Addition of ethylene to 2-C5= increased selectivity to propylene due to metathesis
MCM-41
of ethylene with 2-pentene.
SBA-15
© 2017 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
2-Pentene
Molybdenum oxide reserved.

Introduction used for olefin metathesis are based on molybdenum, tungsten,

C5 olefins are produced as by-products from FCC unit and steam
cracking unit and mainly used as a gasoline additive and also as a
raw material for some organic productions. Refiners have to meet
increasingly stringent specifications for cleaner gasoline by
removing C5 olefins, which have a little value as gasoline blending
stock due to their high volatility. Because of that low-value C5
olefins could be converted to more valuable products (propylene
and ethylene) via olefin cracking or metathesis, which can be
integrated with a Fluid Catalytic Cracking (FCC) unit or a naphtha
steam cracker [1,2].
Olefin metathesis represents an important reaction in the
upgrading of less valuable olefins into desired ones. This reversible
reaction between two olefins breaks double bonds of starting
olefins and forms new olefin products [3,4]. Heterogeneous
catalysts are commonly used in olefin metathesis due to the
advantages of simple and cheap catalyst recovery and regenera-
tion, also a wide range of pressures and temperatures can be used
to reach high catalyst stability. The best heterogeneous catalysts
* Corresponding author.
E-mail address: skhattaf@kfupm.edu.sa (S.S. Al-Khattaf).
and rhenium oxides supported on silica or alumina [5–9].
Rhenium oxide catalysts supported on silica–alumina or alumina
show very high selectivity and activity at temperature below 100
C
[7,10–12]. Negative features of these catalysts include fast deactiva-
tion and their price [13]. Tungsten and molybdenum oxide-based
catalysts remain the most attractive for commercial use due to their
high activity, low cost, long online life time, resistance to poisons and
regeneration without affecting the catalyst structure [9,14]. In
comparison with Re catalysts they usually operate at higher
temperatures (100–500
C). The activity of these catalysts depends
on metal species oxidation state [9,14,15], metal oxide loading,
pretreatment conditions [16], and the support properties [14,17,18].
The perfect dispersal of metal oxide phase on the surface of support is
critical [19,20], bulk oxide particles as well as MOx surface aggregates
do not contribute to the catalytic activity.
Conventional silica [17,21,22], mesoporous silica [9], g-Al2O3
[23], and HY zeolite-g-alumina [24–26] represent well-known and
frequently used supports for Mo and W oxide catalysts. The
successful synthesis of mesoporous molecular sieves has opened a
new research area [27]. The rapid development of new synthetic
pathways delivered numerous structures of different architecture
and pore size. Hexagonal MCM-41 with pore diameter 3–4 nm and
SBA-15 with 6–11 nm are the most frequently used materials
having large BET areas (up to 1000 m3/g), high void volumes (up to

http://dx.doi.org/10.1016/j.jiec.2017.04.012
1226-086X/© 2017 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
120 M.A. Ibrahim et al. / Journal of Industrial and Engineering Chemistry 53 (2017) 119–126
1 cm3/g) and narrow pore size distributions in mesopore region
with potential applications for sorption and catalysis [28–34]. They
have been used also as supports for advanced metathesis catalysts
[35,36].
Ookoshi & Onaka [37] reported Hexagonal Mesoporous Silica
(HMS) support for molybdenum-based olefin metathesis catalyst.
This catalyst exhibited superior catalytic activity in the metathesis
of 1-octene compared to MoO3 supported on conventional porous
silica and MoO3 on alumina. A similar enhancing effect on the
catalyst activity was observed for MoO3 supported on MCM-41,
MCM-48 and SBA-15 [9,15,36]. In metathesis of neat 1-octene,
7 times higher activity was observed for MoO3/MCM-41 in
comparison with MoO3/silica (conventional) and 75% conversion
to 7-tetradecene was achieved at 40
C (6 wt.% Mo loading, 6 h,
batch reactor). The dispersion of MoO3 on the surface was followed
by Raman spectroscopy and 6 wt.% loading was found optimal for
both dispersion and catalyst activity [9]. The application of
MoO2(acac)2 and MoO2(gly)2 (where acac and gly stand for
acetylacetonate and glycolate, respectively) as precursors for
molybdenum oxide catalysts brought a further increase in the
catalyst activity. A better dispersal of Mo oxide species was
achieved on the surface after calcination [15].
The increasing demands for propylene and availability of
advanced metathesis catalysts turned the attention of both
academic and applied research laboratories to the utilization of
metathesis reaction in light olefin processing.
Bhuiyan et al. [38] reported the metathesis of 2-butene using
WO3 supported SBA-15 and MCM-41 catalysts in a fixed-bed
reactor. The WO3-MCM-41 exhibited the highest propylene yield of
39 mol%. Hahn et al. [39,40] described the effect of Brønsted acidity
of supported MoOX species on the propene formation and
selectivity from metathesis of ethylene and 2-butene. Amakawa
et al. [41] studied propylene metathesis to produce ethylene and 2-
butenes over various types of MoOx/SBA-15 at 324 K.
In contrast to the reports concerning butene upgrading, there is
a little knowledge on the metathesis of pentene, especially over
Mo- and W-based catalysts. The only report describes 2-pentene
and ethylene metathesis using Re2O7/SiO2-Al2O3 [11]. Therefore,
we focused on the self- and cross-metathesis of pentenes.
The objective of this study is the investigation of advanced
catalysts prepared by supporting molybdenum and tungsten
oxides on two-dimensional zeolite MCM-22 and mesoporous
molecular sieves (MCM-41 and SBA-15) in metathesis of 2-pentene
and cross metathesis of 2-pentene and ethylene with a special
attention on the influence of reaction conditions on the catalyst
activity and selectivity to the individual products.
Experimental
Materials
Ammonium metatungstate [(NH4)6H2W12O40xH2O], molybde-
num oxide, molybdenum dioxide bis (acetylacetonate) and SiO2
nano powder were purchased from Sigma–Aldrich and used
without any further purification. 2-pentene was also purchased
from Sigma–Aldrich and was further treated with molecular sieves
4A to reduce the moisture. Ethylene gas (99.95% purity) was
purchased from Abdullah Hashim Gas Co. Saudi Arabia and was
passed through RGF-250-400 column of molecular sieves and
Oxiclear DGP-250 R1 from LabClear Inc. USA to remove the
moisture and oxygen.
Support synthesis
Mesoporous support MCM-41 was synthesized by homoge-
neous precipitation method described in a detail elsewhere [42].
Hexadecyltrimethyl ammonium bromide (CTABr, Aldrich) was
used as a template and sodium silicate (Aldrich) as a silicon source;
pH of the synthesis mixture was controlled by the addition of ethyl
acetate. The molar composition of the reaction mixture was
Na2SiO3:CTABr:H2O:ethyl acetate = 1:0.33:644:1.87.
Purely siliceous SBA-15 mesoporous molecular sieve was
synthesized according to the literature [9] using a triblock
copolymer Pluronic P123 (EO20PO70EO20; BASF) as a structure-
directing agent. Tetraethoxysilane (TEOS; 98%, Aldrich) was used
as a silica source, yielding a synthesis batch of molar ratio TEOS:
HCl:P123:H2O = 1:6.2:0.017:197. The mixture was stirred at 35
C
for 2 min and subsequently aged for 24 h at 35
C and 48 h at 95
C.
The resulting solid was recovered by filtration, extensively washed
with distilled water and ethanol, and dried at 95
C overnight.
MCM-22 (NH4+ form) was prepared according to Ref. [43] using
Ludox LS-30 (Aldrich), sodium aluminate (50–55% Al2O3, 40–45%
Na2O, Riedel-de-Haen), 50% solution of sodium hydroxide
(Aldrich) and hexamethyleneimine (HMI) as a structure-directing
agent with the following reactant ratios: Si/Al = 15, OH/Si = 0.09,
HMI/Si = 0.33 and H2O/Si = 27. The synthesis gel was loaded into
0.5 L Teflon-lined reactor and the hydrothermal synthesis was
carried out at 143
C for 4 days under agitation (400 rpm) and
autogenous pressure (5 bars). Solids were isolated by filtration,
washed with water and dried at 60
C. The product MCM-22P was
calcined under nitrogen at 482
C for 3 h followed by calcination
under air at 540
C for 8 h with a heating ramp 1
C/min. Ion-
exchange to NH4+-form was performed by four-fold treatment with
1 M NH4NO3 solution for 3 h.
Catalyst synthesis
Several catalysts were synthesized by supporting molybdenum
and tungsten oxide on conventional silica, mesoporous silica SBA-
15, MCM-41 and MCM-22 zeolite using thermal spreading and wet
impregnation procedures.
The molybdenum oxide catalysts were prepared via thermal
spreading method. Calcined supports (conventional silica, molec-
ular sieves, MCM-22 zeolite) were carefully mixed with MoO2(a-
cac)2 or MoO3 by hand-grinding. Then, the physical mixtures were
thermally treated at 500
C for 8 h in a temperature-programmed
furnace (ramp 1
C/min). Loading of 6 wt.% of Mo was chosen for all
our catalysts prepared based on the previous reports [9,15].
The tungsten oxide/mesoporous molecular sieve catalysts were
prepared via wet impregnation method according to the Ref. [38].
Calcined molecular sieves were carefully mixed with water solution
of ammonium metatungstate [(NH4)6H2W12O40xH2O] in weight
ratios corresponding to catalyst loadings of 6.0 wt.% of W. Then, the
mixtures were dried at 80
C for 12 h and calcined at 550
C for 5 h in a
temperature-programmed furnace (ramp 1
C/min).
Catalyst characterization
X-ray powder diffraction (XRD) data were obtained on a Bruker
AXS D8 Advance diffractometer with a graphite monochromator
and a Vantec-1 position sensitive detector using Cu Ka radiation
(at 40 kV and 30 mA) in Bragg–Brentano geometry. Nitrogen
adsorption/desorption isotherms were measured on a Micro-
meritics ASAP 2020 at liquid nitrogen temperature (196
C) to
determine the BET area and pore volume. Prior to the sorption
measurements, all samples were degassed on a Micromeritics
Flow-Prep060 instrument under helium at 110
C for 6 h.
Transition electron microscopy (TEM) images were obtained
on TEM JEOL JEM-3010 operating at 200 kV equipped with an
Oxford EDS system (Link ISIS). The catalyst powder was
embedded in resin and thin slices, about 30 nm thick, were
obtained by ultramicrotomy.
 M.A. Ibrahim et al. / Journal of Industrial and Engineering Chemistry 53 (2017) 119–126
The Mo and W contents in catalysts were checked by ICP-OES
(Thermo Scientific iCAP 7000 Series). The samples were mineral-
ized using a mixture of HCl, HNO3 and HF in a microwave oven.
Catalysts evaluation
The metathesis reaction of 2-pentene (mixture of trans-2-
pentene & cis-2-pentene) was performed in a tubular fixed-bed
reactor (5.16 mm ID  9.53 mm OD  200 mm length). The reactor
was charged with 0.5 ml of catalyst having particle size of 0.5–
1.0 mm. The catalyst was activated first in a nitrogen stream at
550
C for 1 h. The flow rates of 2-pentene and N2 were maintained
at 0.05 ml/min and 10 ml/min, respectively, during the reaction.
The metathesis reaction was performed at 200 to 500
C
temperature, for 5–12 h of time-on-stream (TOS) at atmospheric
pressure. Reaction products were analyzed using an on-line Agilent
GC equipped with FID detectors using GS-Gaspro and Innowax
columns.
The metathesis of 2-pentene and ethylene was carried out
following the same procedure except that feed was a mixture of 2-
C5= and C2= with a molar ratio of 1:1.
The conversion of 2-pentene and the selectivity of products
were calculated using following Eqs. (1) & (2):
Conversion of 2C¼
5 ¼ 100
Amount of 2C¼ ¼
5 in feed  amount of 2C5 in product

Amount of 2C¼ 5 in feed
Selectivity of product i ð%Þ ¼ 100
Amount of product i
 conventional silica, mesoporous molecular sieves (SBA-15 and
Sum of amounts of all products
Results and discussion
Catalyst characterization
All catalysts and supports were characterized by X-ray powder
diffraction (XRD). Diffraction patterns proved that (i) the structure
of the supports is preserved in the catalysts, (ii) the catalysts do not
contain crystalline MoO3 and WO3. Fig. 1 shows X-ray powder
diffraction patterns of catalyst MoO3/MCM-22 and of parent MCM-
Intensity, a.u.
5 10
Fig. 1. XRD patterns of catalyst MoO3/MCM-22 and of its parent support.
121
22. Both XRD patterns are practically identical and no diffraction
lines of MoO3 crystallites in catalysts (at 2u = 12.7
, 23.3
, 25.7
and
27.3
[9,44]) were observed. It suggests a good dispersion of MoOx
species on the surface, which is a prerequisite for a catalyst good
activity in metathesis [9]. Similarly, the agreement between XRD
patterns of mesoporous sieve based catalysts and corresponding
supports MCM-41 and SBA-15 indicates a preservation of sieves
architecture, Fig. 2. The absence of MoO3 and WO3 signals
(2u = 23.1
, 23.6
, and 24.4
[45]) was observed in the region 10–
30
(not shown in Fig. 2).
TEM images of catalysts MoO3/MCM-22, MoO2(acac)2/MCM-41,
and MoO2 (acac)2/SBA-15 (Supplementary data, Figs. S1–S3) do not
show any molybdenum oxide particles evidencing the conclusion of
a high dispersion of MoOx on the surface. This is in line with our
previous findings [9] showing that for both SBA-15 and MCM-
41 supports molybdenum oxide microcrystals appeared at loadings
higher than 8 wt.% of Mo. It is generally accepted that the precursors
for catalytically active species in metathesis are isolated MoO4
species on the surface [35,41]. The difference in the activity between
SBA-15 and MCM-41 based catalysts may be explained by different
amounts of these isolated species in individual catalysts [9].
Textural parameters determined from N2 isotherms show a
decrease in SBET values after the modification of the parent support
with Mo or W oxides (for details see Refs. [9,15]). Only a small
reduction in pore size was observed while the mesoporous
character of all catalysts based on mesoporous molecular sieves
was preserved, for details see Table 1.
ð1Þ
Metathesis experiments
A systematic study of metathesis reactions of 2-pentene was
performed over molybdenum and tungsten oxide supported on
MCM-41) and MCM-22 zeolite. 2-pentene can undergo different
ð2Þ
reactions as presented in Scheme 1 including
i) isomerization (both double bond shift and skeletal) to produce
1-C5= (1-pentene), 2-Me-2-C4= (2-methyl-2-butene), 2-Me-1-
C4= (2-methyl-1-butene) and 3-Me-1-C4= (3-methyl-1-butene)
isomers.
ii) cracking reaction to produce C2= (ethylene) and C3= (propyl-
ene), which can further undergo oligomerization/aromatiza-
tion to produce higher olefins or aromatics.
iii) self-metathesis (i.e. with another molecule of 2-C5=) to produce
2-C4= (2-butene) and 3-C6= (3-hexene).
M o O 3 /M C M - 2 2
M C M -2 2
15 20 25 30 35 40
2 T h e ta , °
122 M.A. Ibrahim et al. / Journal of Industrial and Engineering Chemistry 53 (2017) 119–126

1 a) 22 b)

In te n s it y , a .u .

b
c´
c
b´
d a´
0 1 2 3 4 5 6 7 8 9 1 2 3 4 5 6 7 8 9
2 T h e ta , °
Fig. 2. XRD patterns for catalysts on SBA-15 (1) and MCM-41 (2). Parent SBA-15 (a), WO3/SBA-15 (b), MoO2(acac)2/SBA-15 (c), MoO3/SBA-15 (d), parent MCM-41 (a’), WO3/
MCM-41 (b’), MoO2(acac)2/MCM-41 (c’).

iv) cross-metathesis with any other molecule of olefin present in

Table 1 the reaction mixture (Scheme 1).
Sorption characteristics of the supports and catalysts determined from nitrogen
adsorption isotherms.

Nr. Catalysts SBET (m2/g) d (nm) VTOT (cm3/g) Sext (m2/g) Metathesis of 2-pentene
1 SiO2 69 – 0.16 53 The results of metathesis of 2-pentene at 500
C under
2 MoO3/SiO2 43 – 0.05 38 atmospheric pressure over different catalysts are presented in
3 MoO2(acac)2/SiO2 49 – 0.06 40 Table 2 and Fig. 3. The MoO3/MCM-22 exhibited the highest
4 MCM-22 455 – 0.59 116
conversion of 2-C5= (78.7%) whereas with MoO3/SiO2 the lowest
5 MoO3/MCM-22 423 – 0.38 114
6 MCM-41 1040 3.9 0.86 46 conversion was achieved (8.3%). The product distribution revealed
7 MoO2(acac)2/MCM-41 1006 3.7 0.79 46 that molybdenum oxide supported on conventional silica cata-
8 SBA-15 877 6.4 1.07 51 lyzed only isomerization reaction of 2-pentene mainly to 1-
9 MoO2(acac)2/SBA-15 733 5.7 0.98 59 pentene. MoO3/MCM-22 catalyzed 2-pentene isomerization,
10 MoO3/SBA-15 719 5.5 0.88 42
metathesis and cracking reactions resulting in the highest amounts
11 WO3/SBA15 639 5.1 0.86 42
12 WO3/MCM-41 614 3.5 0.36 20 of ethylene and propylene produced as compared to other
catalysts. The close inspection of butene isomers revealed the
SBET = BET area (BET method, p/p0 = 0.05–0.20).
VTOT = total pore volume at p/p0 = 0.95. maximum amount of i-butene (8.1%) as compared to other
Sext = external area from as plot (reference sample Davisil663XWP, 82 m2/g). catalysts. The self-metathesis of 2-pentene produced 2-butene
d = average pore diameter (NLDFT, N2 on oxides at 350
C, cylindrical pores). (trans and cis 7.0%) which underwent double-bond isomerization
to 1-C4= (2.5%) and skeletal isomerization to isobutene (8.1%).
Similarly linear and branched isomers of hexene were observed

Higher olefins;
Aromatics
Ol

C3=+1-C4=+
Ar

ig o

2-C4=+3-C6=
om

2-Me-3-C5=
me
a ti

riz
za

ati

sis
tio

Meta
3-Me
on

he
n

=
at

C2=+C3= C5
et
-1-C4
thesis

2-
M

Cra
Other olefins ckin
g sis
athe C3=+3-C7=
=

= Met =
2-C5 1-C5
Me

n
io M
tat

at e
riz 2-M tathe
hes

2-Me-1-C4
Meta

e e-2 sis
om
is

Is -C
4=
thesis

2-C4=+2-Me-2-C5=
1-C5=+ 3-Me-1-C4=+
2-Me-2-C4=+ 2-Me-1-C4=
=

C3=+3-Me-3-C6=
1-C4=+3-Me-2-C5=

Scheme 1. Different possible reactions during conversion of 2-C5=.

 M.A. Ibrahim et al. / Journal of Industrial and Engineering Chemistry 53 (2017) 119–126 123

Table 2
Product distribution (mol%) during metathesis reaction of 2-pentene at 500
C under atmospheric pressure after time of stream of 2 h over different catalysts.

Catalysts MoO3/ SiO2 MoO2(acac)2/ SiO2 MoO3/ MCM-22 MoO3/ SBA-15 MoO2(acac)2/ SBA-15 MoO2(acac)2/ MCM-41 WO3/ SBA-15 WO3/ MCM-41
2-C5= Conversion 8.3 10.8 78.7 39.1 41.5 50.0 56.5 67.9
C1 0.0 0.0 0.0 0.5 0.0 0.3 0.0 0.0
C2 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
C 2= 0.0 0.0 6.7 0.8 0.8 1.0 1.1 1.4
C3 0.0 0.0 1.4 0.0 0.0 0.0 0.0 0.0
C 3= 0.0 0.0 14.7 5.0 5.2 7.6 8.9 12.7
i-C4 0.0 0.0 1.2 0.0 0.0 0.0 0.0 0.0
n-C4 0.0 0.0 0.8 0.0 0.0 0.0 0.0 0.0
1-C4= 0.0 0.0 2.5 3.8 3.6 4.7 5.6 6.2
t-2-C4= 0.0 0.0 4.2 4.5 4.3 6.0 6.9 8.6
i-C4= 0.0 0.0 8.1 0.0 0.0 0.0 0.8 0.9
c-2-C4= 0.0 0.0 2.8 3.2 3.2 4.3 5.1 6.4
i-C5 0.0 0.0 1.5 0.0 0.0 0.0 0.0 0.0
n-C5 0.0 0.0 2.5 0.3 0.0 0.4 0.0 0.0
3-Me-1-C4= 0.0 0.0 1.7 0.0 0.0 0.0 0.0 0.0
1-C5= 7.1 9.2 2.3 9.2 11.4 8.9 5.8 5.7
t-2-C5= 62.4 60.3 7.8 40.1 37.2 32.4 27.8 18.9
c-2-C5= 29.3 28.8 13.5 20.8 21.2 17.5 15.8 13.3
2-Me-2-C4= 1.2 1.7 20.9 1.7 3.1 1.6 2.6 6.6
C 6= 0.0 0.0 3.7 6.4 7.1 8.8 11.6 12.8
C 7= 0.0 0.0 1.8 2.5 2.6 4.4 5.0 5.2
C 8= 0.0 0.0 0.6 0.8 0.3 1.6 1.8 1.3
C 9= 0.0 0.0 0.3 0.0 0.0 0.3 0.5 0.0
C10= 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Aromatics 0.0 0.0 1.0 0.3 0.0 0.2 1.0 0.0

due to double-bond shift reaction and skeletal isomerization,
respectively, catalyzed by Brønsted acid sites of zeolite support. It
also resulted in the formation of C4 and C5 paraffins due to
hydrogen transfer reactions. In contrast to catalysts supported on
SiO2, the isomerization of 2-pentene led to high amounts of 2-
methyl-2-butene (20.9%) as a result of skeletal isomerization
induced by Brønsted acid sites of zeolite support.
Catalysts based on mesoporous molecular sieves initiated
metathesis reaction of 2-pentene as a dominant reaction.
Propylene, C4 olefins and C6+= were observed as major products.
The self-metathesis of 2-pentene resulted in the formation of 2-
butene and 3-hexene, whereas cross-metathesis between 2-
pentene and 1-pentene (produced from isomerization of 2-C5=)
resulted in the formation of propylene and 3-heptene. The product
distribution revealed that among C4 olefins, only 2-butene (cis and
trans) and 1-butene were present while i-butene was absent.
Therefore, it can be concluded that catalysts based on mesoporous
molecular sieves are active in double bond isomerization to
produce linear isomers of olefins but they do not catalyze skeletal
isomerization.
2-pentene conversion increased in the following order of
catalysts used MoO3/SBA-15 < MoO2(acac)2/SBA-15 < MoO2(a-
cac)2/MCM-41 < WO3/SBA-15 < WO3/MCM-41 at 500
C and atmo-
spheric pressure. Over both Mo and W oxides supported on MCM-
41 higher conversions were reached than over catalysts based on
SBA-15 in spite of larger pore diameter of SBA-15, which was
supposed to favor the diffusion of substrate and reaction products.
A similar trend has been reported by Topka et al. [9] in metathesis
of 1-octene. MoO3/MCM-41 exhibited higher metathesis activity
for 1-octene as compared to that of MoO3/SBA-15 because of
different dispersal of active phase over the supports. Due to higher
specific surface area of MCM-41 mononuclear Mo(¼O)2( O)2
species (responsible for the high metathesis activity [35,41])
appeared in considerably higher amounts. Similar observation was

90
MoO3
80 /MCM-22
WO3
70 /MCM-41
MoO2(acac)2 WO3
2-C5" Conversion (%)

60
/MCM-41 /SBA-15

50 MoO3 MoO2(acac)2
/SBA-15 /SBA-15
40

30

20 MoO2(acac)2
MoO3
/SiO2
10 /SiO2

0
I II III IV V VI VII VIII

Catalysts
Fig. 3. Conversion of 2-pentene over various catalysts at 500
C and one atmospheric pressure.
124 M.A. Ibrahim et al. / Journal of Industrial and Engineering Chemistry 53 (2017) 119–126

MoO3/MCM-22 MoO2/SBA-15 MoO2/MCM-41

WO3/SBA15 WO3/MCM-41
80

75

70
2-C5" Conversion (%)

65

60

55

50

45

40

35

30
0 100 200 300 400 500 600 700 800
Time (Minutes)
Fig. 4. Conversion of 2-pentene as a function of time over various catalysts at 500
C and one atmospheric pressure.

reported in metathesis of 2-butene over WO3/SBA-15 and WO3/
MCM-41 [38]: WO3/MCM-41 exhibited higher metathesis activity
than that of WO3/SBA-15. The higher activity of WO3/MCM-41 was
explained based on the well-dispersed WO3 species over MCM-
41 as compared to that of SBA-15. A slightly higher conversion for
catalyst prepared from mononuclear organometallic precursor
MoO2(acac)2 in comparison with that prepared from crystalline
MoO3 may also be connected with a higher amount of mononu-
clear Mo(¼O)2(O)2 species [15].
Effect of the reaction temperature
Metathesis of 2-pentene over MoO3/MCM-22, MoO3/SBA-15,
MoO2(acac)2/MCM-41, WO3/SBA-15, and WO3/MCM-41 was car-
ried out at different reaction temperatures ranging from 200 to
500
C. The compositions of the grouped products are given in
Table S1 (Supplementary data).
All catalysts exhibited only C5= isomerization activity at low
temperatures, i.e. MoO3/MCM-22 up to 300
C, MoO2(acac)2/MCM-
41 up to 250
C, MoO3/SBA-15 up to 300
C, WO3/MCM-41 up to
350
C, and WO3/SBA-15 C5= up to 400
C. In contrast, products of
metathesis and cracking reactions were observed at higher
temperatures.
For MoO3/MCM-22 products of metathesis, isomerization and
cracking reactions (ethylene, propylene, butenes, C6+=, paraffins
and aromatics) were observed in the temperature interval 350–
500
C and their amounts increased with increasing temperature.
MoO3/SBA-15, MoO2(acac)2/MCM-41, WO3/SBA-15 and WO3/
MCM-41 produced propylene butenes, and C6+= [indicating self-
metathesis between two molecules of 2-pentene and cross-
metathesis between 2-pentene and 1-pentene molecules] starting
at 300, 300, 450 and 400
C, respectively. The amount of these
products further increased till 500
C.
The changes in product distribution with temperature clearly
indicated that Mo oxide supported catalysts exhibited metathesis
activity at lower reaction temperatures than WO3 supported
catalysts, which is in accordance with literature data [46]. Also
MCM-41 based catalysts exhibited onset of metathesis at lower
temperature than those based on SBA-15.

Table 3
Selectivity (mol%) of products during metathesis reaction of 2-pentene with ethylene at 500
C over different catalysts.

MoO3/MCM-22 MoO2(acac)2/SBA-15 MoO2(acac)2/MCM-41 WO3/SBA-15 WO3/MCM-41

2-C5=:C2 =
Ratio 1:0 1:1 1:0 1:1 1:0 1:1 1:0 1:1 1:0 1:1
Conversion of 2-C5= 78.7 77.9 41.5 42.3 50.0 51.0 56.5 57.2 67.9 68.5
Conversion of C2= – 5.6 – 18.6 – 20.4 – 28.0 – 49.6
C1 0.0 0.0 0.0 0.0 0.6 0.0 0.0 0.0 0.0 0.0
C2 0.0 0.6 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
C2= 8.5 – 1.9 – 2.0 – 2.0 – 2.1 –
C3 1.8 1.3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
C3= 18.7 24.5 12.5 34.2 15.2 36.6 15.8 40.3 18.7 47.0
i-C4 1.5 1.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
n-C4 1.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
1-C4= 3.2 3.9 8.7 16.1 9.4 14.8 9.9 18.6 9.1 12.5
t-2-C4= 5.3 5.6 10.3 9.8 12.0 11.0 12.2 10.9 12.7 13.6
i-C4= 10.3 10.8 0.0 0.0 0.0 0.0 1.4 0.0 1.3 1.7
c-2-C4= 3.6 4.3 7.7 7.5 8.6 8.4 9.0 8.0 9.4 10.3
i-C5 1.9 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
n-C5 3.2 2.0 0.0 0.0 0.8 0.0 0.0 0.0 0.0 0.0
3-Me-1-C4= 2.2 3.1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
1-C5= 2.9 4.7 27.4 22.3 17.8 17.8 10.3 11.4 8.5 5.1
2-Me-2-C4= 26.6 33.4 7.5 3.0 3.2 3.1 4.6 3.3 9.7 4.6
C6+= 8.0 4.7 24.0 7.1 30.1 8.4 33.5 7.5 28.4 5.2
Aromatics 1.3 0.0 0.0 0.0 0.4 0.0 1.2 0.0 0.0 0.0
 M.A. Ibrahim et al. / Journal of Industrial and Engineering Chemistry 53 (2017) 119–126 125

Catalyst stability only 23.14 mg C/g. It evidences a higher extent of coke formation
Metathesis of 2-pentene over MoO3/MCM-22, MoO2(acac)2/ for MCM-22 based catalyst, which may result in a faster loss of its
SBA-15, MoO2(acac)2/MCM-41, WO3/SBA-15, and WO3/MCM- catalyst activity.
41 was carried out at 500
C for 720 min to study the catalyst
stability (Fig. 4). 2-pentene conversion over MCM-41 based Effect of addition of ethylene as feed with 2-pentene
catalysts (i.e. MoO2(acac)2/MCM-41 and WO3/MCM-41) was quite Metathesis reaction of ethylene with 2-pentene produces
stable decreasing about 3 rel.% over 720 min. The catalysts based propylene and 1-butene as shown below in Eq. (3).
on SBA-15 (i.e. MoO2(acac)2/SBA-15 and WO3/SBA-15) exhibited a
higher decrease in the 2-pentene conversion (12 rel.% over (3)
MoO2(acac)2/SBA-15 and 16 rel.% over WO3/SBA-15) after
720 min. The steepest drop in conversion was observed over
MoO3/MCM-22 (about 20 rel.% in the first 500 min). In this case it
The effect of the addition of ethylene on the metathesis reaction
was observed that amounts of C5= isomers (3-Me-1-C4=, 1-C5=, and
of 2-pentene over different catalysts was investigated at the
2-Me-2-C4=) in product gradually increased with time while the
reaction temperature 500
C, GHSV 1200 h1, the molar ratio of 2-
amounts of all other products (among them metathesis ones)
pentene to ethylene 1:1 (Table 3 and Fig. 5).
decreased (see Table S2). It indicates that metathesis centers
For MoO2(acac)2/SBA-15, MoO2(acac)2/MCM-41, WO3/SBA-
underwent progressive deactivation but acid centers responsible
15 and WO3/MCM-41, selectivity to propylene and 1-butene
for isomerization were preserved.
strongly increased (more than two times) when ethylene was
We have also analyzed coke amount (in terms of total carbon
added as a co-feed to 2-pentene. Whereas the selectivity of C6+=
amount) in two spent catalysts MoO3/MCM-22 and WO3/MCM-41.
products dropped to the fraction of the original value. This change
In the former case 101.73 mg C/g was found but in the latter case

Fig. 5. Selectivity of propylene (A) and C6+= (B) over various catalysts under ethylene as co-feed with 2-pentene at 500
C and atmospheric pressure.
126 M.A. Ibrahim et al. / Journal of Industrial and Engineering Chemistry 53 (2017) 119–126
in product distribution evidences that cross-metathesis between
ethylene and 2-pentene is the major reaction producing propylene
and 1-butene. The presence of 5–8% of C6+= (at 2-C5=:C2= 1:1 ratio)
indicated that self-metathesis of 2-pentene took place in small
extent. It was noted that tungsten based catalysts i.e. WO3/SBA-
15 and WO3/MCM-41 exhibited higher conversion of 2-C5= and a
higher conversion of ethylene for 2-C5=:C2= ratio 1:1 as compared
to those of molybdenum based catalysts. The selectivity to
propylene increased in the order MoO2(acac)2/SBA-15 < MoO2(a-
cac)2/MCM-41 < WO3/SBA-15 < WO3/MCM-41.
In the case of MoO3/MCM-22, propylene selectivity increased
only moderately for 2-C5=:C2= ratio 1:1 together with a moderate
drop in selectivity of C6+=. This observation clearly indicates that
cross-metathesis with ethylene proceeded in very small extent
which is in accord with the previous finding that MoO3/MCM-
22 causes cracking as the major reaction.
Our study shows that transformation of 2-pentene over
investigated catalysts is a complex reaction and the population
of individual products depends on the reaction conditions and
catalyst performance. Recent studies showed the crucial effect of
catalyst acidity (both Brønsted and Lewis) on their activity in olefin
metathesis [40]. On the other hand, the acid centers initiate
isomerization and cracking reactions leading sometimes to the
unwanted products. Changing Al/Si ratio in new zeolite supports
may give a possibility to tune the acidity of catalysts and to design
catalysts of required activities and selectivities.
Conclusions
The conclusions of this study can be summarized as below:
2-pentene can be effectively transformed to propylene, butenes
and C6+= over Mo and W oxides catalysts under conditions suitable
for industrial applications. The activity and selectivity of men-
tioned catalysts was found to depend strongly on used supports.
 Catalysts having molybdenum and tungsten oxides supported on
mesoporous molecular sieves (MCM-41 and SBA-15) exhibited
metathesis of 2-pentene as a strongly prevailing reaction.
Catalysts based on MCM-41 exhibited higher activity and
stability as compared to that of SBA-15.
 Catalysts having molybdenum oxide supported on conventional
silica exhibited only 2-pentene isomerization in low conversions.
 Catalysts having molybdenum oxide supported on MCM-
22 exhibited mainly isomerization and cracking reactions at
the highest 2 pentene conversions.
 The addition of ethylene in the feed resulted in increased
selectivity of propylene due to cross-metathesis reaction
between ethylene and 2-pentene (for Mo and W oxide catalyst
supported on MCM-41 and SBA-15).
Acknowledgments
The authors would like to acknowledge the support provided by
King Abdulaziz City for Science and Technology (KACST) through
the Science & Technology Unit at King Fahd University of Petroleum
& Minerals (KFUPM) for funding this work through project No. 14-
PET89-04. as part of the National Science, Technology and
Innovation Plan.
The authors also acknowledge the support from the Ministry of
Higher Education, Saudi Arabia, in the establishment of the Center
of Research Excellence in Petroleum Refining & Petrochemicals at
King Fahd University of Petroleum & Minerals (KFUPM). The
support of KFUPM is also highly appreciated.

H.B. and M.K. acknowledge the Czech Science Foundation
J.C.,
for support (P106/12/0189).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.jiec.2017.04.012.
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