Kinetics Modelling of 2Butene Metathesis Over Tungsten Oxide

Containing Mesoporous Silica Catalyst

Tazul I. Bhuiyan,1,2 Palani Arudra,1 Mohammad M. Hossain,1,2 Mohammad N. Akhtar,1 Abdullah M. Aitani,1
Raed H. Abudawoud3 and Sulaiman S. AlKhattaf1,2*
1. Center of Research Excellence in Petroleum Rening and Petrochemicals, King Fahd University of Petroleum & Minerals, Dhahran 31261,
Saudi Arabia
2. Department of Chemical Engineering, King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia
3. Research & Development Center, Saudi Aramco, Dhahran 31311, Saudi Arabia

This article reports the activity, reaction mechanism and reaction kinetics of 2butene metathesis over tungsten oxide containing mesoporous silica
(SBA15) catalyst. Physicochemical characterisation of the catalyst indicates that the dispersion and nature of tungsten oxide species on the catalyst
are mainly responsible for the metathesis activity. The ample availability of Brnsted acid sites created by tetrahedrally coordinated tungsten species
also enhances the metathesis reaction. The product analysis indicates that lower temperature favours the butene isomerisation, while higher
temperature is required for metathesis. The high temperature is also responsible for cracking reactions. A kinetics model is developed based on the
experimental observations and the possible reactions including isomerisation, metathesis and cracking. The model parameters are estimated by
tting the experimental data implemented in MATLAB. The estimated apparent activation energy of 2butene isomerisation reaction was found to
be the lowest (39.4 kJ/mol) among the competing reactions. The activation energy of cross metathesis of 2butene and 1butene, selfmetathesis of
1butene and 2butene cracking are 71.3, 176.9 and 73.1 kJ/mol, respectively. These results are consistent to the product selectivity and the proposed
reaction scheme, which suggests that the isomerisation of 2butene gives 1butene and it further reacts (cross metathesis) with 2butene to produce
propylene.

Keywords: metathesis, 2butene, propylene, tungsten on mesoporous material, kinetic modelling

INTRODUCTION be used in metathesis, the heterogeneous catalysts are preferred

due to their higher thermal stability, easy handling and possibility

T
he demand for propylene is increasing for the downstream
applications such as polypropylene, acrylonitrile, cumene,
oxoalchohols, propylene oxide, acrylic acid and isopropy-
lalcohol and polygas chemicals.[1] Current global propylene
demand is 73 million tons which is expected to riseup to
110 million tons by 2020. On the other hand, the projected global
production of propylene by 2020 stands at about 100 million tons
per year. Therefore, one can foresee a signicant decit in the
annual global propylene production in just after 10 years from now
if the current production remains similar. Conventionally, propyl-
ene is produced mostly by naphtha steam cracking and uid
catalytic cracking (FCC) units.[2] These conventional processes
cannot push further to increase the propylene production given
these processes have the priorities to produce ethylene and
transportation fuels.[3] Considering these facts, in recent years
several onpurpose propylene production technologies including
metathesis of butene have been investigated to meet the high
propylene demand.[2]
The metathesis reaction is an important organic transformation
that transforms less desired olens to higher value products
through C


C bonds rearrangement. For instance, in the presence


of a tungsten catalyst, metathesis of the C4 olens converts C4 into
more valuable propylene.[4,5] At present, the olens conversion
technology (OCT) process licensed by Lummus Technology is the
only commercial olen metathesis technology producing propyl-
ene for the petrochemical industry.[6] The key step in olen
metathesis is the intermediacy of metal carbene active species and
consequently the formation of unstable metallocyclobutane.
Although, both homogeneous and heterogeneous catalysts can
of reuse after regeneration.[7,8] In the open literature, supported
rhenium, molybdenum and tungsten oxides are considered as the
most promising candidates as metathesis catalysts.[9,10] Sang[11]
and Balcar[12] reported high activity and selectivity of alumina,
silicaalumina and mesoporous organised alumina supported
rhenium (Re) oxide catalysts under mild reaction conditions.
However, the activity of these catalyst are poor with low Re loading
(<10 wt %).[13] The deactivations rate of Re catalysts are also
fast.[14] The other major issue with Re based catalyst is the high
price of rhenium.[6] The molybdenum oxide based catalysts have
received much attention because of their relatively low price, and
comparable activity under mild reaction conditions.[1517] The
main limitation of molybdenum catalysis is that it requires a
comparatively high pure feed stream.[18] The tungsten based
catalysts shows good activity and selectivity for a longer period of
time. They are also resilient to frequent poisoning.[19] In addition,
continuous regeneration without negative effects on the catalyst
structure makes the tungsten based catalysts more attractive for
commercial use.[19] Usually the tungsten oxide catalysts require
a comparatively higher temperature (2505008C) to achieve
*Author to whom correspondence may be addressed.
Email address: skhattaf@kfupm.edu.sa
Can. J. Chem. Eng. 92:12711282, 2014
2014 Canadian Society for Chemical Engineering
DOI 10.1002/cjce.21976
Published online 25 February 2014 in Wiley Online Library
(wileyonlinelibrary.com).

VOLUME 92, JULY 2014 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 1271
appreciable activity. The catalytic activity of tungsten based
catalysts widely depend on the oxidation state of tungsten species,
the content of tungsten oxide, the properties of support and the
pretreatment condition.[2,5,19,20]
Regarding the support materials, galumina has been widely
used as catalyst supports because of their stability and reasonable
surface area. On the other hand, periodic mesoporous silicas (i.e.
MCM41, SBA15) having large pores (520 nm) with hexagonal
structure are more attractive due to their large channel diameter
and its thermal as well as hydrothermal stability.[21,22] The high
surface (6001200 m2 g
1) of these materials also makes them
interesting support material.[23,24] Direct tungsten incorporation
using a hydrothermal method has advantages over a conventional
impregnation method such as high tungsten species dispersibility
and the presence of more active tungsten species into the
support.[25,26]
Considering the great promise of tungstenbased catalysts, the
present research is focussed on the highly active and selective
tungsten oxide containing mesoporous silica (WO3SBA15) as
the catalyst for metathesis of 2butene to produce propylene. There
are two important aspects of this present research, which have not
been reported in the open literature:
(i) Metathesis of 2butene using only 2butene as a feed: the
advantage of the present approach is the use of much cheaper
butene ($775/ton) as a raw material than the conventional
metathesis of 2butene with higher value ethylene ($1200/
ton) to produce propylene ($1375/ton).[27,28] There are
several studies describing the production of propylene by 1
butene metathesis.[26,29,30] However, 1butene is expensive
as compared to 2butene because 1butene has a huge
demand as a monomer for the production of liner low density
polyethylene (LLDPE) and polybutene.[31] To the best of
our knowledge, there is no communication dealing with
the application of tungsten oxide containing mesoporous
silica (WO3SBA15) as a catalyst for 2butene metathesis
reaction. In this study, we also investigate the reaction
mechanism of 2butene metathesis considering a wide range
of temperature.
(ii) Investigate the kinetics of 2butene metathesis over tungsten
oxide containing mesoporous silica (WO3SBA15): In the
open literature, there are only a very limited number of
contributions considered for the kinetics of propylene
metathesis. For instance, Kapteijn et al.[32] and Spinicci
and Tofanari[33] investigated the kinetics of propylene
metathesis over rhenium oxide based catalyst support on
alumina. The apparent activation energy for metathesis of
propylene was 46.8 kJ/mol.[33] Cheng and Lo[7] developed a
density functional theory only considering ethylene and 2
butene metathesis reaction over WO3 catalysts. Li et al.[34]
investigated the inuence of Mo oxidation state for metathe-
sis of ethylene and 2butene over Mo/HBeta catalyst by
developing a DFT theory. Surprisingly, there is no work
reported in the open literature studying the kinetics
modelling of 2butene metathesis to produce propylene. On
the other hand, the kinetics study of this reaction is very
critical in determining the reactor/process design and
performance analysis. Keeping the above factors in mind,
the present work is focused on the development of kinetic
model(s) for the metathesis of 2butene over tungsten based
SBA15 catalyst. This is an attempt starting from an extensive
set of kinetic experiments using a laboratory scale xed bed
reactor. The ratecontrolling step of the heterogeneous
1272 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING
reaction model is dened by observing the reaction rates at a
different set of experimental conditions. The mechanism of
metathesis reaction was derived with the catalyst investigat-
ed along with the effect of temperature and spacetime.
Kinetic parameters are assessed using their physical signi-
cances and various statistical indicators.
EXPERIMENTAL
Materials
Pluronic123 (EO20PO70EO20), tetraethylorthosilicate (TEOS,
98%), sodium tungstate (NaWO4.2H2O), HCl were purchased
from SigmaAldrich, Chemie Gmbh Munich, Germany and used
without any further purication. 2butene with 99.9% purity (50%
cis2butene and 50% trans2butene) was purchased from Saudi
Industrial Gas Company, Dammam, Saudi Arabia.
Catalyst Synthesis
Hexagonally ordered mesoporous SBA15 was synthesised using
triblock copolymer P123 (EO20 PO70EO20) as the structure
directing agent and tetraethylorthosilicate (TEOS) as the silica
precursor. Synthesis of SBA15 was performed according to the
procedure reported in literature.[25,26] In a typical batch, 6 g of
Pluronic 123 was dissolved to 210 mL of 2 M HCl and stirred at 408C
to achieve a transparent solution. After 34 h, 12.8 g TEOS was
quickly added into the solution. Then, a calculated amount of
sodium tungstate solution was added to the solution and stirred at
958C for 3 days under hydrothermal conditions. The resultant
solution was stirred at 958C for 3 days. The solid products obtained
were recovered by ltration and dried at 808C overnight. The
template was removed by calcination in air at 5508C for 5 h.The
catalysts obtained in this way were identied as WO3SBA15(x),
where x represented the molar ratio of silica to tungsten (Si/W).
The molar ratio of the gel composition is SiO2: 0.033 WO3: 0.0167
P123: 5.82 HCl: 190 H20.
Catalyst Characterisation
The chemical composition of synthesised tungsten containing SBA
15 was determined by inductively coupled plasma atomic emission
spectroscopy (ICPAES), using Ultima 2 (Horiba scientic)
equipment.
The prepared catalysts were characterised by the Xray powder
diffraction (XRD) method, using a Rigaku Miniex II system using
nickel ltered CuKa radiation (l 0.154 nm) at a scanning rate of
18/min in the 2u range of 1.3508. The Xray tube was operated at
40 kV and 30 mA.
The textural properties of the samples were measured by
nitrogen adsorption measurements at 77 K using Quantachrome
AUTOSORB 1C adsorption analyser. Before adsorption measure-
ments, the solid samples (ca. 0.1 g) were degassed at 2208C under
vacuum nitrogen ow for 3 h. The nitrogen adsorption isotherms of
calcined materials were measured at liquid nitrogen temperature
(77 K). The surface areas and pore sizes were calculated by the
BrunauerEmmettTeller (BET) method and the BarrettJoyner
Halenda (BJH) method, respectively.
Raman spectra were recorded at room temperature on Horiba
Jobin Yvon in situ Raman, iHR 320 with synapse CCD detector(-
excitation line, 532.5 nm of an Ar ion laser; source power, 40
60 mW; resolution, 4 cm
1).
UV vis DR spectra were collected on a JASCO V670
spectrophotometer at 200 nm/min scan rate using BaSO4 as
reference.
VOLUME 92, JULY 2014
 The acidity of the synthesised material was analysed by pyridine
adsorption followed by FTIR study. The catalyst sample was nely
ground and pressed into a selfsupporting wafer. The wafers were
calcined under a vacuum at 4008C for 1 h, followed by exposure to
pyridine vapour. The adsorbed pyridine was desorbed at various
temperatures (1504508C). The thin wafer was placed in the FTIR
cell and the spectrum was recorded on a Nicolet FTIR spectrometer
(Magna 500 model). The difference between the spectra of pyridine
adsorbed on the samples and that of the reference was obtained by
subtraction. The amount of Brnsted acid sites (B) and Lewis acid
sites (L) were calculated using the following equation as reported
in literature[35]:
C pyridine on B sites 1:88 IAB R =W;
2 Selectivity
C pyridine on L sites 1:42 IAL R2 =W SC
where C is the concentration (mmol/g catalyst); IA(B, L) is the
integrated absorbance of B or L band (cm
1); R is the radius of
catalyst disk (cm) and W is the weight of disk (mg).
Kinetics Experiments
For this kinetics investigation, the metathesis reaction of 2butene
(1:1 mixture of trans2butene and cis2butene) was performed in
a xedbed tubular reactor (stainless steel tube grade 316 material,
0.312 inch ID  0.562 inch OD  8 inch length). A schematic
diagram of the reactor is shown in Figure 1. In a typical experiment,
the reactor was charged with 2 mL of catalyst previously sieved to a
particle size of 0.51.0 mm diameter. The catalyst sample was rst
activated in a nitrogen stream (99.9% purity) at 5508C for 1 h. The
metathesis reaction was carried out at different temperatures,
ranging from 3505508C, GHSV (gas hourly space velocity) of 900
2700 h
1 and atmospheric pressure. The quantitative analysis of
the reaction products was carried out on line using Varian GC with
FID (Varian 450GC), equipped with a CPAl2O3/Na2SO4 column
(50 m length  0.32 mm ID  df 5 mm). To check the reproduc-
ibility of the experimental results, a number of runs were
performed and typical errors were in the range of 1%.
The GC analysed data were further processed to calculate the
conversion and selectivity using the following equations according
to Liu et al.[36]:
Figure 1. Schematic diagram of the xed bed tubular reactor.
VOLUME 92, JULY 2014
Conversion of 2butene
moles of 2butene convertedW2C
4 =4
X 2C4  100% 1
moles 2butene fed
Yield
X2
C4  WC n =n
Yield; YC
n  100%
WC2 =2 WC
3 =3 WC4 =4
WC5 =5 WC6 =6
2
Yield; YC
n
n  100% 3
Conversion of 2butene; X 2
C4
In the formula, YC
n and SCn is the yield and selectivity of
alkene with carbon number n, and WC n is the mass percent of
alkene with different carbon number n.
RESULTS AND DISCUSSION
Physicochemical Properties of the Catalyst
The Xray diffraction patterns of the calcined SBA15, WO3SBA15
(30) samples are shown in Figure 2. Two diffraction peaks in
the region of 2u 1.528, which can be indexed to the [1 1 0] and
[2 0 0] diffractions characteristic of the p6mm hexagonal sym-
metry, were observed for the SBA15 samples, which is also
reported by Herrera et al.[37] In both cases, 100 reections were not
observed due to the limitation of the XRD instrument. There is no
signicant difference in the XRD patterns for the SBA15 samples
showing the retention of hexagonal symmetry after tungsten
incorporation in the framework. There were small peaks assigned
to the crystalline phase of WO3 as observed for WO3SBA15(30)
sample at high angle XRD. Table 1 summarises the textural
properties of the supports and catalysts calculated from nitrogen
adsorption studies.
Raman spectra of the support SBA15 and catalyst WO3SBA15
(30) are shown in Figure 3. For the catalyst WO3SBA15(30), three
peaks were observed at 267, 712 and 807 cm
1. These crystalline
WO3 peaks were assigned to the symmetric stretching mode of
W--O, bending mode of W--O and the deformation mode of
W--O--W, respectively.[29] The band at 970 cm
1 was associated to
the symmetric stretching mode of the terminal W


O bond of the


tetrahedrally coordinated tungsten oxide species, which suggested
as the active site of the WO3SBA15(30) catalyst.[26,38] It is obvious
that pure SBA15 do not have any peaks in these regions.
Diffuse reectance spectra of tungsten supported samples in the
region of 200600 nm are shown in Figure 4. The spectrum of
sodium tungstate presents a spinal structure at 230 nm which
mainly implies the presence of ligand to metal charge transfer
involving isolated transition metal sites and considered direct proof
of the framework tungsten oxide species in tetrahedral co
ordination.[39] For pure SBA15, there is no evidence of the band
(not in the gure). The sample tungsten incorporated into the
framework, WO3SBA15(30), shows a similar band at 230 nm can
be attributed to the presence of isolated [WO4]2
tetrahedral
species. The second band at 290 nm may be assigned to isolated
tungsten species or lowcondensed oligomeric tungsten oxide
species. For the sample bulk WO3, a broad band at 350400 nm is
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 1273
Figure 2. XRD of support SBA15 and WO3SBA15(30) catalyst at (A) low angle and (B) wide angle.

observed, implying that mainly extraframework bulk WO3
particles or clusters in the sample.[5,26]
Pyridine adsorption measured by IR spectroscopy was carried
out to evaluate the strength and types of acid sites present in the
tungsten impregnated and framework sample. Figure 5 shows
the FTIR spectra of support and the catalyst recorded after the
adsorption of pyridine and subsequent evacuation at 1508C and
2508C. The PyFTIR spectrum recorded after adsorption of
pyridine at room temperature on the pure SBA15 shows two
major peaks at 1595 and 1445 cm
1, ascribed to pyridine
coordinately bonded to weak surface Lewis acid sites. These peaks
disappeared after out gassing at 3508C. In the case of the WO3SBA
15(30) sample, two additional peaks at 1545 and 1635 cm
1 were
also observed due to protonated pyridine bonded to the surface of
Brnsted acid sites, indicating the presence of tungstenincorpo-
rated species.[38,40] The peak at 1485 cm
1 has been identied as
the combination of both Lewis and Brsted acid sites.[35] The
intensities of all of these bands were decreased after out gassing at
2508C. It can be concluded that the presence of Brnsted acid sites
in the tungsten containing SBA15 samples are related to the
presence of tetrahedrally coordinated tungsten oxide species.
Metathesis of 2Butene Over WO3SBA15(30) Catalyst
As mentioned in the experimental section, the metatheses of 2
butene experiments were conducted in a laboratory scale xed bed
reactor. In order to identify the possible products, the experiments
were conducted in a wide range of experimental conditions (T:
3505508C; space time: 824 s). The product analysis results
during the metathesis of 2butene over WO3SBA15(30) catalyst
are presented in Table 2. One can see that the main products of 2
butene metathesis are propylene, ethylene, pentene, hexene and 1
butene. However, remarkable differences observed both in 2
butene conversion and product yields at different temperature
levels. Therefore, it is very important to discuss the effects of
reaction temperature during the metathesis of 2butene over WO3
SBA15(30) catalyst.
Effects of Temperature
In order to study the inuence of reaction temperature the
experiments were conducted at different temperatures which
varied between 3508C and 5508C with a constant GHSV (900 h
1)
at atmospheric pressure. Figure 6 plots the 2butene conversion
and selectivity of different products as a different reaction
temperature. It is clear from the gure that the temperature has
signicant effects both on 2butene conversion and product
selectivity. This observation indicates that several reactions are
involved during this wide range temperature including isomer-
isation, primary cross metathesis, selfmetathesis, secondary cross
metathesis and cracking. As expected, 2butene conversion was
increasing with the increase of the reaction temperature. It is
instructive to concentrate rst on the temperature range below
4008C where the 2butene conversion was low (35.8%). In this
temperature range 1butene is the major product while the
formation of ethylene, propylene, 2pentene and 3hexene are
minimal. When the reaction temperature was raised from 4008C to
4508C, 2butene conversion was drastically increased from 35.8 to

Table 1. Physicochemical properties of synthesised catalysts

Surface Pore Brnsted Lewis

% of WO3 area diameter acid site acid site
Samples (ICPAES) (m2/g) (nm) (1508C) (1508C)

SBA15 833 4.4 0.0265 0.3818

WO3SBA15(30) 9.19 501 6.9 0.1086 0.3521
Lewis and Brnsted acid sites are calculated by FTIR pyridine sorption
(only at 1508C). Figure 3. Raman spectra of support SBA and catalyst WO3SBA15(30).

1274 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 92, JULY 2014

Figure 4. UVvis diffuse reectance spectra of Na2WO4.2H2O, WO3SBA15
(30) and bulk WO3.
72.4%, 1butene selectivity also dropped from 58 to 13.5 mol% and
the selectivity of the propylene and 2pentene increased to 41.3 and
25.9 mol%, respectively. At 4508C the other products such as
ethylene and 3hexene started to appear. One can speculate the
following reactions steps based on the observed shift of conversion
and product selectivity due to the change in the reaction
temperature from 4008C to 4508C:
2butene isomerisation:
2butene $ 1butene starts at  3508C
2 and 1butene cross metathesis:
2butene 1butene $ propylene 2pentene starts at  4508C
Figure 5. FTIR spectra of pyridine adsorbed on the sample recorded at
different temperature (a) SBA15 at 1508C, (b) SBA15 at 2508C, (c) WO3
SBA15(30) at 1508C, (d) WO3SBA15(30) at 2508C. B, Bronsted acidity; L,
Lewis acidity.
VOLUME 92, JULY 2014
Figure 6. 2Butene conversion and selectivity of product over WO3SBA15
(30) catalyst from 3508C to 5508C temperature at 24 s spacetime.
1butene selfmetathesis:
1butene $ ethylene 3hexene starts at  4508C
According to the above reactions, the molar ratio of propylene
and pentene should be 1:1. However, the product analysis shows
that propylene selectivity was 15% higher than that of 2pentene at
4508C. This shows the possibility of some secondary metathesis
reactions. In the temperature range between 4508C and 5008C both
the 2butene conversion and propylene and ethylene selectivity
proportionately increased while the selectivity of pentene and
hexene decreased with the increase of the reaction temperature
(Figure 6). When the reaction temperature was further increased
from 5008C to 5508C, 2butene conversions and selectivity of
propylene and ethylene were increased, but the selectivity of 2
pentene and 3hexene started to decrease. This is a clear indication
of 2pentene and 3hexene cracking, which are favourable at a
higher temperature in the presence of an acidic catalyst. Due to the
cracking of 2butene more propylene and ethylene were produced.
In order to determine the effects of cracking, the C3

/C5

and
C2

/C6

ratios are plotted at a different temperature (Figure 7). It
was noticed that, at 4508C C2



/C6




ratio was 1.02, which


increased to 1.69 and 2.74 at 5008C and 5508C, respectively. In the
same way, C3



/C5






ratio was 1.62 at 4508C, which increased to
1.89 and 2.36 at 5008C and 5508C. These increments of ratios with
temperature are the clear evidence of 2butene and 2pentene
cracking for the formation of ethylene and propylene at a higher
Figure 7. 2Butene conversion and selectivity of product over WO3SBA15
(30) catalyst from 3508C to 5508C temperature at 24 s spacetime.
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 1275
 Table 2. Product distribution (mol %) for metathesis reaction of 2butene at 3505508C and 8 to 24 s spacetime over WO3SBA15(30) catalyst

Temp (8C) C. time (s) Conv. 2C4

1C4


C3






2C5


C2


3C6

550 24 81.2 18.8 8.2 36.4 14.7 11.2 4.2

18 78.8 21.2 9.2 36.2 15.3 10.2 3.5
14 74.3 25.7 10.0 34.0 16.7 7.6 3.9
12 66.2 31.8 9.0 31.9 16.7 5.1 3.5
10 61.6 38.4 8.4 29.7 16.2 4.0 3.4
9 56.1 43.9 7.3 26.6 16.4 2.9 3.0
8.5 51.8 48.2 6.9 24.8 15.0 2.4 2.7
8.25 49.1 50.9 6.2 23.6 14.7 2.2 2.5
8 41.6 58.4 5.1 20.1 13.0 1.5 2.0
500 24 80.6 19.38 7.77 33.83 17.83 9.22 5.48
18 76.6 23.38 9.24 33.21 18.35 7.51 5.18
14 72.4 27.61 10.02 31.37 18.36 5.77 4.67
12 64.0 35.96 8.30 30.02 18.00 4.03 3.69
10 57.8 42.16 7.77 26.53 17.50 2.75 3.29
9 44.4 55.60 7.65 19.23 14.15 1.38 1.99
8.5 42.2 57.85 7.51 18.80 13.99 1.18 1.90
8.25 38.8 61.22 7.10 17.23 12.95 1.08 1.04
8 30.6 69.39 4.94 14.16 10.62 0.00 0.88
450 24 72.7 27.29 9.62 29.97 18.77 5.15 5.00
18 65.0 34.99 12.45 26.14 16.98 3.79 3.82
14 56.3 43.73 14.67 21.50 15.15 2.43 2.52
12 53.2 46.79 11.19 21.91 15.84 1.97 2.31
10 42.2 57.83 13.36 14.83 12.04 0.95 0.99
9 29.8 70.22 16.29 5.93 4.56 0.00 0.00
8.5 26.6 73.37 13.08 9.20 7.35 0.00 0.00
8.25 26.5 73.50 10.13 9.17 7.19 0.00 0.00
8 18.7 81.34 11.20 4.11 3.35 0.00 0.00
400 24 35.4 64.60 20.90 6.87 4.98 0.39 0.20
18 32.1 67.92 21.95 5.11 3.74 0.00 0.00
14 26.6 73.39 23.97 1.99 0.65 0.00 0.00
12 24.0 76.05 22.84 1.12 0.00 0.00 0.00
10 21.3 78.72 21.28 0.00 0.00 0.00 0.00
9 17.9 82.07 17.93 0.00 0.00 0.00 0.00
8.5 16.4 83.60 16.90 0.96 0.00 0.00 0.00
8.25 15.5 84.52 15.48 0.00 0.00 0.00 0.00
8 12.0 88.03 11.97 0.00 0.00 0.00 0.00
350 24 27.5 72.51 20.48 3.26 2.03 0.00 0.00
18 24.7 75.34 21.23 1.72 0.63 0.00 0.00
14 22.6 77.45 21.73 0.82 0.00 0.00 0.00
12 20.0 80.03 19.97 0.00 0.00 0.00 0.00
10 17.7 82.30 17.70 0.00 0.00 0.00 0.00
9 15.6 84.36 15.64 0.00 0.00 0.00 0.00
8.5 14.9 85.12 14.88 0.00 0.00 0.00 0.00
8.25 13.1 86.92 13.08 0.00 0.00 0.00 0.00
8 9.5 90.48 9.52 0.00 0.00 0.00 0.00

temperature. In summary, the isomerisation of 2butene to 1
butene takes place at a relatively lower temperature (3508C)
while the metathesis and cracking reactions occur at a higher
(>4008C) temperature.
Effect of SpaceTime
In order to study the effects of spacetime, the experiments were
conducted at various feed ow rates using the same amount of
catalyst. The spacetime were varied between 8 and 24 s. Figure 8
shows the products yield as a function of space time at 5508C and
atmospheric pressure. With the increasing of the space time (8
24 s), 2butene yield was decreased from 58.4 to 18.8 mol%.
However, propylene yield was increasing with the increase of
spacetime. The same trend was followed to other products. The
involvement of secondary metathesis and cracking of 2butene
could be explained with the comparison of C3



/C5





ratios at


different temperature and different spacetime, which are pre-



/C5

sented in Figure 9A. The ratio of C3





decreased more at 5508C


than 4508C with the decreasing of spacetime. From this trend, it is
assumed that spacetime inuenced cracking more than the
secondary metathesis reactions for the production of propylene.
The ratio of C2


/C6 at different spacetime and temperature is


presented in Figure 9B. The ratio of C2



/C6 decreased with the


decreasing of spacetime and there was no formation of ethylene
and 3hexene at 4508C at 9 s spacetime. From this result, it is
conrmed that selfmetathesis of 1butene for the production of
ethylene and 3hexene is highly inuenced by the spacetime.

1276 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 92, JULY 2014
Figure 8. Product distribution from 8 to 24 s spacetime over WO3SBA15
(30) catalyst at 5508C.
Catalytic Stability
The catalytic stability of WO3SBA15(30) catalyst was investigat-
ed at 5508C for 16 h of stream. The results are presented in
Figure 10. The conversion of 2butene, yield of propylene and
ethylene were initially 81.1%, 37.5 and 12.11 mol%, respectively.
After 16 h, the catalyst has almost the same metathesis activity
with 2butene conversion 80.2%, propylene yield 35.7 mol% and
ethylene yield 10.5 mol%, respectively. There was very little coke
formation after 16 h of operation. Furthermore, the opportunity of
pore blocking is low due to the large pore diameter of WO3SBA15
(30) catalyst.
Reaction Scheme
Based on the above discussion, during the metathesis of 2butene
over WO3SBA15(30) catalyst one can consider Scheme 1 for the
possible reaction pathways. In this scheme all the pentene isomers
Figure 9. Ratio of (A) propylene to 2pentene (B) ethylene to 3hexene over
WO3SBA15(30) catalyst from 8 to 24 s spacetime at 4508C and 5508C
temperature.
VOLUME 92, JULY 2014
Scheme 1. Possible reaction scheme of 2butene metathesis reaction along
with isomerisation and cracking reactions over WO3SBA15(30) catalyst.
lumped as C5



, while hexane isomers combined as C6





.


According to Scheme 1, the desired product, propylene is produced
via three alternative routes: (i) cross metathesis of 1butene and 2
butene, (ii) secondary metathesis of ethylene and 2butene and (iii)
by cracking of 2butene. From the carbene metal complex
formation of 2butene, it is predicted that 2butene does not
undergo selfmetathesis.[7,34,41] Due to the low concentration of
ethylene (by product) the secondary metathesis as a source of
propylene is considered to be negligible. Although the contribu-
tions of each of the pathways widely depend on the characteristics
of the catalysts material, it is important to recognise that the 1
butene required in cross metathesis via the isomerisation of 2
butene. On the other hand, 1butene also undergoes selfmetathesis
to form ethylene and 3hexene. An excessive isomerisation of 2
butene will promote the 1butene selfmetathesis. Therefore, a
balance of 2butene isomerisation is crucial to maximise propylene
production by cross metathesis and to minimise side products.
Aromatic compounds are not considered in the reaction scheme
due to its negligible amount.
Mass Transfer Limitations
The overall reaction rate for metathesis of 2butene over WO3SBA
15(30) catalyst involves diffusion, adsorption and intrinsic
reaction steps. In the context of the present study, the possibilities
of both the external and internal diffusions were examined by
evaluating the mass transfer limiting criterions using the
experimental data. The possibility of external mass transfer
(bulk uid to catalyst surface) limitations of the reactants and
products is assessed using the Sherwood number with Froesslings
dimensionless correlations evaluated at the experimental con-
ditions[42,43]:
essling correlation
Sh 2 0:6 Sc0:33 Re0:66 Fro 4
ShDAB
kc 5
dp

r 00 ABobs
C AB;b
C AB;s film DC film 6
kc
1  10
3 T 1:75 1=M A 1=M B 1=2
DAB 1=3 1=3
7
Patm SvA SvB 2
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 1277
 bulk 2butene concentration. The small values of DClm suggest
that in the context of the present study the external mass transfer
limitation is not signicant.
The inuence of intraparticle mass transfer (diffusion) is
examined by evaluating the WeiszPrater criterion.[42] According
to the WeiszPrater criterion the diffusion mass transfer can be
considered negligible if the following inequality satises:

r 00 ABobsrp R2p
C WP 1 9
Deff C AB;s

where,
r 0 ABobs is the observed reaction rate (mol/kg s), rP is the

Figure 10. Results of 2butene metathesis reaction over WO3SBA15(30)
catalyst at 16 h operation.
where, Sh, Sc and Re are Sherwood, Schmidt and Reynolds
numbers, respectively. kc is the external mass transfer coefcient
(m/s), subscript A is using for 2butene and B is using for nitrogen,
DAB molecular diffusivity of 2butene in carrier gas nitrogen (m2/
s), dp is the particle diameter (m),
r 00 ABobs is the observed
reaction rate (mol/m2 s), CAB,b is the bulk concentration of gaseous
reactant and CAB,s is the surface concentration of gaseous reactant
(mol/m3). The diffusivity for 2butene in nitrogen (DAB) is
estimated using the Fuller, Schettler and Giddings correlation
(Equation 7).[44] Frossling correlation is evaluated by considering
that the uid surrounding the particles is almost stagnant (highest
possible gas lm resistances). The observed reaction rate (mol/
m2 s) in the xed bed reactor can be expressed as:
particle density (kg/m3), Rp is the particle radius (m), Deff is the
effective diffusivity (m2/s) and CAB,s is the concentration of gaseous
reactant at the surface of solid particles (mol/m3). The effective
diffusivity (Deff) is estimated as[43]:
Deff 0:1DAB 10
The initial concentration of 2butene is considered as the
concentration of 2butene at the surface of the catalyst. This
ensures the evaluation of WeiszPrater criterion at conditions,
where the possibility of diffusion limitations is the highest. Table 4
reports the calculated WeiszPrater parameters and the other
variables used for this evaluation. It is clear for Table 4 that even in
the worst case scenarios the values of CWP was much smaller than 1
(one). Thus, the concentration gradient within the catalyst carrier
pellet is expected to be negligible. Thus, it can be concluded that in
the studied reaction conditions, the chemical reaction is the
limiting resistance for all the runs developed in the xed bed
reactor.

F A0 X A

r 00 ABobs  8
Sex W
where, FA0 is the molar ow rate of reactant 2butene, XA is the
conversion of 2butene and Sex is the external surface area per gram
of sample and W is the weight of the catalyst.
The calculated DClm (using Equation 6) values are listed in
Table 3. One can easily notice that at calculated values of DClm, at
various reaction conditions, are very small when compared to the
Kinetic Modelling
Model development
The mathematical models representing the rates of chemical
reactions are developed based on Scheme 1 which considers (i)
isomerisation of 2butene to 1butene (ii) cross metathesis of 2
butene and 1butene, (iii) selfmetathesis of 1butene and (iv)
cracking of 2butene. As previously discussed, all these reactions
are greatly inuenced by temperature and spacetime. In formula-

Table 3. Parameter used to calculate the effects of external mass transfer limitations

Temp. (8C) DAB (m2/s) kc (m/s) Spacetime (t), s r 00 AB obs (mmol/m2 s) CAB,b (mol/m3) DCfilm (mmol/m3)

350 3.7  10
5 0.12 24 98.3 43.0 0.80

400 4.2  10
5 0.14 24 122.8 43.0 0.87
450 4.8  10
5 0.16 24 256.2 43.0 1.60
500 5.4  10
5 0.18 24 284.3 43.0 1.58
550 6.1  10
5 0.20 24 287.8 43.0 1.43

Table 4. Parameter used to calculate the effects of internal mass transfer limitations

Temp. (8C) Deff (m2/s) Spacetime (t), s r 00 AB obs(mmol/kg s) CAB,s (mol/m3) CWP

6
350 3.7  10 24 3.34 43.0 5.7  10
4
400 4.2  10
6 24 4.18 43.0 6.2  10
4
450 4.8  10
6 24 8.71 43.0 1.1  10
3
500 5.4  10
6 24 9.67 43.0 1.1  10
3
550 6.1  10
6 24 9.79 43.0 1.0  10
3

1278 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 92, JULY 2014
tion of the kinetic model the following assumptions have been (average of all the temperatures) is introduced to reduce parameter
considered: interaction.
i. Isomerisation, cross metathesis and selfmetathesis reactions For the thermodynamic consistency of the reaction, the
are reversible while 2butene cracking is irreversible. temperature dependent equilibrium constants were formulated
ii. The pentene isomers are considered as 2pentene and the using Gibbs energy of formation of pure species:
hexene isomers as 3hexene. Isomerisation of 2butene to 1butene
iii. All parafn, isobutene and aromatic products are negligible.   
iv. Contribution of secondary metathesis in propylene produc- 9600 1 1
k1e 21:45 exp

19
tion is insignicant. R T T0
Based on these assumptions and using power law model, the rate
Cross metathesis of 2butene and 1butene
of disappearance/formation of each of the species involved in 2
butene metathesis can be expressed as follows:   
1200 1 1
Disappearance of 2butene: k2e 196:5 exp

20
R T T0
   
dCA 1 1

k1 CA
CB
k2 CA CB
CC CD
2k4 C24 Selfmetathesis of 1butene
dt0 k 1e k2e
11   
26100 1 1
k3e 181:8 exp

21
R T T0
Formation of 1butene:
   
dCB 1 1 Parameter estimation and kinetics evaluation
k 1 CA
C B
k 2 C A CB
CC C D
dt0 k1e k2e To estimate the parameters and evaluate the developed models, the
  12
1 temperature dependent specic reaction rate constants (Equa-

2k3 CB
2
CE CF
k3e tion 18) and temperature dependent equilibrium constants
(Equations 1921) were rst combined with the kinetics model
Formation of propylene: equations (Equations 1116). The concentrations of various
species were expressed in terms of mass fraction according
  Equation 17. The resulting differential equations were then
dCC 1
k 2 C C
A B
CC D 2k 4 CA
C 2
13 numerically solved in conjunction with a least square tting of
dt0 k2e
the experimental 2butene metathesis data to be obtained from the
xed bed reactor. In solving the differential equation MATLAB
Formation of 2pentene: ODE 45 subroutine (RungeKuttaGill method) was employed
  while the parameters were estimated using LSQCURVEFIT
dCD 1 subroutine (Modied Marquad method).
k2 CA CB
CC CD 14
dt0 k 2e In order to ensure reliable model parameter estimation, the
catalytic 2butene metathesis experiments were conducted at a
Formation of ethylene: wide range of reaction temperatures (3505508C) and various
  space times (824 s). In this fashion a total of 270 data points were
dCE 1 obtained and used in parameter estimation. Therefore, eight
k 3 CB
CE F k 4 CA
C 2
15
dt 0 k3e kinetics parameters were determined with a degree of freedom of
262 (degree of freedom No. of experimental data points
No. of
Formation of 3hexene: model parameters). The sufcient numbers of experimental data
  points obtained/used in parameter estimation provides reliability
dCF 1 of the model parameter.
k 3 C2

CE CF 16
dt0 B
k3e

The concentration of various species in Equation (11)

through (16) can be written in terms of mass fraction of (yi)
according to the following equation:

yi F TM
Ci 17
MWi q

The rate constants ki can be represented with the temperature

dependent form of the Arrhenius equation:
  
Ei 1 1
ki ki0 exp

18
R T T0

Figure 11. Comparison between experimental results and model

where, ki0 and Ei are the preexponential factor and activation predictions for 2butene conversion at the reaction temperature at 350 8C,
energy of the reaction i, respectively. T0, the centering temperature 4508C and 5508C.

VOLUME 92, JULY 2014 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 1279

Figure 12. Comparison between experimental results and model
predictions for propylene concentration at the reaction temperature at
3508C, 4508C and 5508C.
The following model evaluation criteria are considered:
(i) All the kinetics parameters (specic reaction rates and
activation energies) should be consistent with physical
principles.
(ii) Coefcient of determination (R2).
Figure 13. Arrhenius plots of different reactions rate constants obtained from power law model (A) isomerisation reaction, (B) cross metathesis of 1butene
an 2butene, (C) selfmetathesis of 1butene and (D) cracking of 2butene.
1280 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING
(iii) Lower SSR (sum of the squares of the residuals).
(iv) Lower crosscorrelation coefcient (g).
(v) Smaller individual condence intervals for the model
parameters.
Figures 11 and 12 show the comparison between the experi-
mental data and model predictions for the reaction scheme. We
observed in these plots that model predictions compared favour-
ably with the experimental data for the reactions at 3508C, 4508C
and 5508C. Some deviations due to high conversion are predicted at
5508C and 24 s space time. Several reactions are involved in the
reaction scheme to produce various products. During the long
range of space time the model predicted a higher conversion at a
higher temperature. Figure 13 shows the Arrhenius plots of various
specic reaction rate constants. The straight line with negative
slopes of all the Arrhenius plots (as shown in Figure 13) of the rate
constants conrms the thermodynamic consistency of the present
Power Law model.
Table 5 lists the estimated kinetics parameters for different
reaction paths displayed in Scheme 1. From Table 5, it is noticed
that the estimated activation energy of 2butene isomerisation
forming 1butene requires the least activation energy (39.4 kJ/
mol) as compared to the other competing reactions. The estimated
VOLUME 92, JULY 2014
 Table 5. Estimated values of the parameters, 95% condence intervals However, the probability of cross metathesis of 2butene and 1
and R2 butene is much higher than the selfmetathesis of 1butene.
4. The kinetics investigation shows that among the competing
Estimated 95% confidence reactions, isomerisation of 2butene to 1butene requires the
Parameter value interval R2
least amount of activation energy (39.4 kJ/mol) while the
k01  102 (m3/kg) 4.72 0.17 0.9727 activation energy for selfmetathesis of 1butene is the highest
E1 (kJ/mol) 39.4 1.92 (176.9 kJ/mol). The activation energy of cross metathesis of 2
k02  102 (m6/kg) 5.7 0.4 butene and 1butene, selfmetathesis of 1butene and 2butene
E2 (kJ/mol) 71.3 6.1 cracking are 71.3, 176.9 and 73.1 kJ/mol, respectively. These
k03  102 (m6/kg) 1.64 0.48 results are consistent to the proposed reaction mechanisms
E3 (kJ/mol) 176.9 36.8 and the product selectivity data, which suggests that the
k04  102 (m3/kg) 1.8 0.031 isomerisation of 2butene gives 1butene which further reacts
E4 (kJ/mol) 73.1 15.3 (cross metathesis) with 2butene to produce propylene.

NOMENCLATURE
activation energies for cross metathesis of 2butene and 1butene is
71.3 kJ/mol, cracking of 2butene is 73.1 kJ/mol. Unfortunately, in Ci concentration of species i in the fixed bed reactor (mmol/
the open literature the activation energies for butene metathesis cm3)
(either 1 and 2butene cross metathesis or 1butene self CI confidence limit
metathesis) are not available for comparison. The value of Ei apparent activation energy of the ith reaction (kJ/mol)
activation energy for selfmetathesis of 1butene found to the ki apparent rate constant for the ith reaction (1/s)
highest (176.5 kJ/mol). The high activation energy for 1butene ki0 preexponential factor for the ith reaction after reaction
selfmetathesis is consistent to the experimental low selectivity 3 parameterisation
hexene as shown in Figure 6 and Table 2. On the other hand, the MWi molecular weight of the species
low value of activation energy of 2butene isomerisation is also ri rate constant of the species
reasonable given that the product 1butene further reacts with 2 vo volumetric flow rate of the feed
butene (cross metathesis) to give propylene. Therefore, isomer- t the spacetime
isation of 2butene to 1butene is a prerequirement of cross yi mass fraction of species i in the reactor
metathesis. The high selectivity of propylene as seen in Figure 6 FTM total mass flow rate
and Table 2 conrms this explanation. One can argue that the Symbols
origin of propylene might be the cracking of 2butene. However, at
a low temperature (until 4008C) the selectivity of the other cracking A 2butene
products ethylene is negligible, while the selectivity of propylene is B 1butene
still high. This conrms the formation of propylene mainly via C propylene
cross metathesis of 2butene and 1butene. D 2pentene
E ethylene
F 3hexene
CONCLUSION
ACKNOWLEDGEMENT
The present investigation is to develop a kinetic model on 2butene
metathesis reaction over WO3SBA15 catalyst which leads to the The authors would like to acknowledge the support provided by
following conclusions: Saudi Aramco for funding project #CRP02252. The support from
the Ministry of Higher Education, Saudi Arabia, in establishment of
1. The synthesised WO3SBA15(30) catalyst has tetrahedral the Center of Research Excellence in Petroleum Rening &
tungsten oxide species as conrmed by Raman spectroscopy Petrochemicals at King Fahd University of Petroleum & Minerals
and UVvis DRS. The tetrahedral tungsten oxide species act as (KFUPM) is appreciated. The support of KFUPM is also highly
the active site for the metathesis reaction. Tungsten oxide appreciated.
effectively incorporated into the SBA15 framework and
highly dispersed into the lattice of the support as revealed
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