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Journal of Natural Gas Chemistry 15(2006)93-99

Article

Effect of Reaction Temperature and Pressure on the Metathesis

Reaction between Ethene and 2-Butene to Propene
on the W03/A1203-HY Catalyst
Shengjun Huang1i2,Shenglin Liu', Wenjie Xinl, Sujuan Xiel, Qingxia Wang', Longya Xu1>*
1. Laboratory of Natural Gas and Applied Catalyszs, Chznese Academy of Sciences, Dalian 116023, Chzna;
2. Graduate School of Chznese Academy

0s Sciences,

Bezjing 200049, China

[ Manuscript received January 20, 2006; revised March 7, 2006 ]

Abstract: Effect of reaction temperature and pressure on the metathesis reaction between ethene and
2-butene to propene was studied on the W03Iy-Al203-HY catalyst. The activity is found to increase with
elevated temperature and reaches a plateau at 150-240 "C. After that, the activity undergoes a remarkable
decrement at too high temperature. The effect of temperature is elucidated by the oxidation state of
tungsten species. The evaluation results also indicate that the stability is dependent on this reaction
parameter. Medium pressure (0.5-0.8 MPa) is favorable for stability, while atmospheric pressure or too
high pressure (>1.0 MPa) deteriorates the stability. For explanation, UV Vis, FT-IR, 02-TP0, and TG
techniques are used t o characterize the spent catalysts.
Key words: metathesis; tungsten oxide catalyst; temperature; pressure; ethene; 2-butene; propene

1. Introduction
Olefin metathesis is one of the very few fundamentally novel organic reactions discovered in the last
40 years. Recently, Prof. Y. Chauvin, Schrock, and
Grubbs have been honored with the 2005 Nobel Prize
in chemistry on account of their prominent work on,
"The development of the metathesis method in organic synthesis". It opens up many new routes for
the production of important chemicals. The metathesis between ethene and 2-butene is interesting to the
industry for the increment of propene output and utilization of surplus Cq feed. ABB Lummus Global and
IFP now offer this process for license as olefin conversion technology (OCT) [I] and Meta-4 process [a],
respectively, to produce more propene. The OCT
process has been commercialized and will be inte-

grated in more steam crackers. The catalyst used

is WO3/SiO2 and the typical reaction condition are
>260 "C and 30-35 bar [l]. However, the detailed
description of this catalyst and the process are rarely
reported.
According t o the literature, the most successful heterogeneous catalysts for the metathesis reaction of simple alkenes are supported rhenium, molybdenum, and tungsten oxide catalysts. It is well
demonstrated that rhenium oxide catalysts, especially
Re207/A1203, are active at room temperature [3],
however, the activities of catalysts with low loading
(<lo wt%Re) are poor [4]. The supported tungsten
oxide catalysts have great potential in application because of their low sensitivity to the impurity in the
feed. However, the disadvantages of the conventional
supported tungsten oxide catalysts are high tempera-

* Corresponding author. Tel: +86-411-84379279; Fax: f86-411-84693292; E-mail: lyxu@dicp.ac.cn.

Financial support by National Natural Science Foundation of China (No. 20303019) and National 973 Project of China (No.
2003CB615802).

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Shengjun Huang et al./ Journal of Natural Gas Chemistry VoJ. 15 No. 2 2006

ture and relatively lower activity than their rhenium

and molybdenum counterparts. As the metathesis
between ethene and 2-butene to propene is slightly
exothermic (25 "C, -1.7 kJ/mol). the application of
an active tungsten oxide catalyst at lower temperature
is thermodynamically feasible. Recently. the tungsten
oxide supported on 30wt%A1203-70wt%HY exhibited
a high activity for the metathesis between ethene and
2-butene at 180 "C [5]. which has been attributed to
its Bronsted acidity and abundance of tetrahedrally
or octahedrally coordinated surface tungsten oxide
species. So far, the effect of reaction conditions on
the catalytic performance of this new catalyst has not
been investigated.
In this paper, the effect of most governing factors,
i.e., reaction temperatures and pressure. on the catalytic performance of W03/30wt%A120~-7Owt%HY
have been studied. The results indicate that medium
temperature (-180 "C) and pressure (0.5-0.8 MPa) is
favorable for the catalytic performance of a catalyst.
which gives some useful information for the potential application of this or further modified catalysts.
In addition, UV Vis, FT-IR. TG. and 02-TPO techniques are used to characterize the spent catalysts for
a better understanding of the effect of these parameters.

middle position of the catalyst bed at the outside of

the steel reactor to measure the temperature of the
electric furnace. which was taken as the reaction temperature. After the catalyst was pretreated in situ
at 500 "C for 1 h under high purity Nz (0.1 MPa, 30
mljmin). it was cooled to the reaction temperature
in flowing N2. The catalyst was then used for the
metathesis reaction between ethene and 2-butene to
propene. The reaction products have been analyzed
by a gas chromatograph with an FID detector. The 2butene conversion and propene selectivity have been
calculated as follows:

rn=i

[C71n. [l-C:ln. . . . , the molar percent of each component in effluent gas. [C7Im, [l-C;lmr . . . , the weight
percent of each component in effluent gas.
In the experiments for the metathesis on the
lOW/A1203-zHY catalysts, the ethene conversion increased synchronously with that of 2-butene, thus 2butene conversion was used as the catalytic activity.
2.2 Characterization of catalysts

2. Experimental
2.1 Catalyst preparation and its evaluation

The A1203-HY support was prepared by extruding a mixture of -y-A1203 powder and HY zeolite
(WenZhou Zeolite Manufacture of China, Si/A12=10.
Na20<0.2 wt%) at 70%:30% weight percent into
strips, with a diameter of about 2 mm. The drawn extrudate was left a t room temperature for a few hours
and placed in an oven at 120 "C for 12 h. Subsequently, the dried extrudate was calcined a t 500 "C for
2 h and then ground into a 16-32 mesh. Catalysts
containing 10 weight percent tungsten were prepared
by impregnating the y-Al203-HY support with ammonium metatungstate solution according to the incipient wetness method. The impregnated samples
were dried at 120 "C for 5 h. and then calcined at
600 "C for 2 h. These prepared catalysts were denoted as 10W/A1203-70HY.
The catalysts were tested in a fixed-bed flow microreactor of 10 mm inner diameter. and 3 g of catalyst with a n average particle size of 0.56-1.3 mm was
loaded. An EU-2 type thermocouple was fixed in the

UV-Vis spectra were recorded with a JASCO

500 spectrophotometer equipped with a diffuse
reflectance attachment. The samples were studied
in the form of 12-mm-diameter, 2-mm-thick pellets
prepared as self-supporting waters. The spectra were
recorded under air-exposed conditions in the range
200-800 nm and the scan speed was 120 nm/min.
For the FT-IR (Bruker Equinox 55) spectroscopic
studies. self-supported wafers were pressed from the
powders with a thickness of 10-15 mg/cm2. The
wafers were composed of a catalyst and a KBr power
a t weight ratio of 4%:96%. The spectra were registered a t room temperature.
T G profiles were recorded on a Perkin-Elmer TG
1700 instrument. T h e catalyst loading was about
0.01 g and the flow rate of N2 was 30 ml/min.
The catalyst was heated from 50 to 1000 "C in a
20%02/N2 stream at a heating rate of 10 "C/min.
02-TPO was performed after the catalyst had undergone times on stream when the 2-butene was down
to about 50%. The spent catalysts were flushed with
10%02/He mixture a t room temperature for about 10
minutes and then the temperature was raised from 30

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Journal of Natural Gas Chemistry Vol. 15 No. 2 2006

to 950 "C with a rate of 10 "C/min. The mass intensities for 44 (COz) and 28 (CO) were recorded. For
simplification, the amount of CO has been added to
that of C02.

lies between 150-180 "C.

100

3. Results

3.1 The effect of reaction temperature on the

metathesis reaction

The metathesis of simple linear olefins is not accompanied by significant structural changes. Therefore, the reaction is almost a thermally neutral process
and the variation of temperature has a negligible
influence in view of the thermodynamics aspect. The
effect of reaction temperature on activity is shown in
Figure 1. The initial activity of the 10W/A1203-70HY
catalysts depends remarkably on the reaction temperature. When the temperature is 60 "C, the 2-butene
conversion is extremely low. With the increment of
reaction temperature, the activity increased almost
linearly. At 120 "C, the 2-butene conversion could be
obviously improved to 66%. As shown in Figure 1,
the 2-butene conversion is still far from the thermodynamic equilibrium value when the reaction temperature is below 120 "C. In the higher temperature region of 150 - 240 'C, the 2-butene conversion reaches a
plateau of 84%, which approaches the thermodynamic
equilibrium value of 437%. However, too high reaction temperature will result in a remarkable decrease
in initial activity. The profile of activity as the function of reaction temperature is an inversed 'U' type.
The stabilities of lOW/A1203-70HY catalysts are also
influenced by reaction temperature. As shown in Figure 2, under low reaction temperature (<120 "C) 2butene conversion decreases mildly with the extended
time on the stream. This suggests that lower activity should not be caused by the break-in phenomenon, which is occasionally reported on W 0 ~ / S i 0 2
catalysts [6]. With higher reaction temperature, catalysts exhibit better stability. Especially at 180 "C,
catalysts possess about an eight-hour stabilized time
during which the 2-butene conversion is above 80%.
A further increase in reaction temperature will lead to
shorter stabilizing time and quick deactivation. For
example, the 2-butene conversion decreases from 80%
to 20% within four hours under 240 "C. From the
above results, it can be concluded that the catalytic
performances of the 10W/A1203-70HY catalysts are
obviously influenced by reaction temperature. The
favorable temperature range for activity and stability

50

100

150
200
250
Temperature ("C)

300

350

Figure 1. Effect of reaction temperature on the activity of 10W/A1203-70HY catalyst

(1)2-Butene conversion, (2) Thermodynamic equilibrium value
Reaction conditions: p=O.l MPa, c2H4/2-CdH8=2.5-3.0,
WHSV=0.83 h-', TOS=l h
(Line (2) is the thermodynamic equilibrium value of 2-butene
conversion. The calculation condition is p=O.1 MPa, C2H4/2C4Hgd.0)

loo

2
00

10

12

Time-on-stream (h)

Figure 2. Stability of lOW/A1203-70HY at different temperatures

(1) 90 "C, (2) 120 "C, (3) 150 "C, (4) 180 "C, (5) 210 "C,
( 6 ) 240 "C, (7) 300 "C
Evaluation conditions: n(ethene): n(2-butene)=2.5-3.0,
p=O.l MPa, WHSV=0.83 h-l

3.2 Effect of reaction pressure on the catalytic

performances of 10W/A1203-70HY catalysts
Taking into account the fact that the diffusion
of molecules is important in metathesis, especially in
the gaseous phase, the reaction pressure will modify
the reaction kinetics under these conditions and will
therefore influence the outcome of the reaction. The

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Shengjun Huang et al./ Journal of Natural Gas Chemistry Vol. 15 No. 2 2006

effect of pressure on the metathesis reaction between

ethene and 2-butene was studied within a pressure
range of 0.1 and 2.0 MPa. As the metathesis between
ethene and 2-butene to propene is an equimolecular
process, the reaction pressure should not influence
the metathesis activity in view of thermodynamics
aspects. The difference shown in Figure 3 is because
of the varied molecular ratio between ethene and 2butene, which is not a constant value practically and
the higher value is proved to promote the 2-butene
conversion.
95

10

20

30
40
Time-on-stream (h)

50

60

Figure 3. Influence of reaction pressure on the 2butene conversion as the function of time
(1) 0.1 MPa, (2) 0.5 MPa. (3) 0.8 AlPa. (4) 1.0 MPa,
( 5 ) 2.0 MPa
Evaluation conditions: temperature 180 "C, WHSV=0.83 h-' ,
n(ethene)/n(2-butene)=2.5-3.5

The progress of this equimolecular reaction may

be influenced by the pressure on account of the possible oligomerization and polymerization side reactions.
As shown in Figure 3, the high activity decreases
quickly with the extended reaction time and falls to
50% in 17 h under atmospheric pressure. It is very
interesting t o note that the stability of the catalysts
is improved with increased pressure. For example, the
time with 2-butene higher than 80% is about 54 h for
0.5 MPa and 50 h for 0.8 MPa respectively. However, with higher pressure, the stability undergoes remarkable decrement again. As for 1.0 MPa pressure,
the 80% 2-butene conversion can be operated for only
about 17 h. The deteriorating effect of pressure on
stability becomes severe a t 2.0 MPa. under which the
2-butene conversion decreases to 70% after 12 h time
on stream. This indicates a quick deactivation behavior in W O S / S ~ O ZM003/&03,
,
and Mo03/A1203HP catalysts under high pressure [7-91.

3.3 The UV Vis spectra of spent 10W/A120370HY catalysts at different temperatures

In order to obtain an acceptable activity, much

higher reaction temperatures have to be used for
WO3/Ai203 because of the poor reducibility, than
those used for MoO3/A1203 and Re207/A1203.
Therefore, the reaction temperature may be related to
the reducibility of 10W/A1203-70HY catalysts. The
introduction of reductive feed will cause the immediate reduction of metal oxide species, as popularly observed, for other olefin metathesis catalysts system.
Therefore, at a lower reaction temperature (<120 "C)
it may be difficult to reduce the supported tungsten
oxide species by alkenes feed. The color of the unloaded catalysts after reaction also gives some hints.
The catalysts under 60 "C are colored violet red,
whereas catalysts under 180 and 240 "C are colored
brown. According to the literature [lo], there exist a
number of colored tungsten oxides: W 0 3 (green yellow), p-WO2.88 (blue), y-WO2.77 (purple red), 6-WO2
(brown). Therefore, the variation of color of spent
catalysts suggests a different reduction of tungsten
species by alkene feeds.
UV Vis spectra give some information about the
state of tungsten species on different spent catalysts.
As reported before, the fresh lOW/A1203-70HY catalyst just exhibits two adsorption peaks centered at 210
and 250 nm, whereas no obvious adsorption bands exist in the higher wavelength range [S]. After one hour
in the stream of ethene and 2-butene, the UV Vis
spectra undergo some variations depending on the reaction temperature. As shown in Figure 4, the spent
catalyst obtained a t 60 "C almost preserves the bands
a t 210 and 250 nm, and exhibits two obvious new
bands centered a t 320, 380 nm and two minor small
bands centered at 460 and 570 nm respectively. When
the temperature is elevated to 120 "C, 210, 250, and
320 nm bands decrease, whereas, the ones at 380 and
460 nm increase. Remarkable variations of spectra
appear for catalysts a t higher reaction temperature
of 180 and 240 "C. As shown in Figure 4, the bands
in the 260-400 nm range shift t o a higher wavelength
with the maximum adsorption at about 430, 500, and
650 nm, respectively. At the same time, the intensity
of the bands in the 400-700 nm range predominates
the bands in the 210-260 nm. After a one-hour time
on stream under 300"C, the spectrum of the spent catalyst is totally transformed. The bands in the 200700 nm range become broad and flat, accompanied
with sharply decreased intensity in the 200-350 and

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Journal of Natural Gas Chemistry Vol. 15 No. 2 2006

3.4 Characterization of spent 10W/A120370HY catalysts under different pressure

400-550 nm range.
0.8

200

300

400

500
600
Wavelength (nm)

700

800

960

Figure 4. UV Vis spectra of 10W/A1203-70HY catalysts after one hour reaction time at
different reaction temperatures
(1) 60 "C, (2) 120 "C, ( 3 ) 180 "C, (4) 240 "C, ( 5 ) 300 "C

In the case of the molybdenum species it has been

reported that the adsorption band between 400 and
800 nm is because of the reduced Mo ions such as
Mo4+ and Mo5+ [ll].As supported W 0 3 and Moo3
catalysts are comparable in chemistry, it is reasonable
to attribute the adsorption between 400 and 800 nm
to the reduced species such as W4+ and W5+. The
bands between 260 and 400 nm are tentatively attributed to the W species charged between 1 5 and
+6. Therefore, the variation of UV Vis spectra indirectly reflects the oxidation number state of tungsten
species under different reaction temperatures.
In case of the catalysts under extremely low temperature (e.g. 60 "C), the tungsten oxide species are
slightly reduced, probably in the intermediate state
between +5 and +6, and their amounts are also relatively low. With a moderately elevated reaction temperature (<120 "C), most of the tungsten species are
still kept in the intermediate state, but with the increment in abundance. With further increased reaction temperature (-180 "C), more tungsten species
are reduced and most of them are in +4 or +5 state,
whereas the tungsten species in intermediate state decrease remarkably. However, with too high reaction
temperature, the amount of tungsten oxide species in
+6 oxidation state and the W4+ and W5+ species all
undergo remarkable decrement. As a result, the tungsten species must be reduced to the lower oxidation
number state than +4, although the precise state is
unknown at present.

The occurrence of oligomerization and polymerization on the acid centers of the carrier can lead
to the formation of nondesorbed carbonaceous compound and block the active sites. The FT-IR and
02-TPO are employed to characterize the spent catalysts under different reaction pressures. It should
be noted that the samples are obtained when the 2butene conversion is below 50%.
FT-IR is frequently employed to investigate the
nature of nondesorbed products formed during hydrocarbon transformation over zeolite catalysts. As
shown in Figure 5, all spent catalysts display a band
a t about 2850, 2920, and 2960 cm-l, which becomes
stronger with an increase in pressure. According to
the literature 1121, bands corresponding to alkanic
species appear at about 2958, 2926, 2872, and 2856
cm-l, which are attributed to CH stretching mode.
The band at about 1460 cm-' is typical of branched
alkanes [131.

-..,
1500

2000

2500

3000

3500

4000

Wavenumber (cm-' )

Figure 5. FT-IR spectra of deactivated catalysts

(1) 0.1 MPa, (2) 0.5 MPa, (3) 0.8 MPa, (4) 1.0 MPa,
(5) 2.0 MPa

02-TPO also can give some information about

the nature of carbonaceous compounds on spent catalysts. The T P O profiles of various spent catalysts
with 2-butene below 50% are shown in Figure 6.
The T P O profile of spent 10W/A1203-70HY catalysts under 0.1 MPa consist overlapping peaks a t 460
and 570 "C. With increased pressure, the peak a t
about 400 "C becomes distinct, whereas the peak at

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Shengjun Huang et al./ Journal of Natural Gas Chemistry Vol. 15 No. 2 2006

570 "C becomes sharp. Sachtler et al. [14]. take these

kinds of T P O profiles typical of a bifunctional catalyst and assign the first peak at lower temperature to
the coke oxidation catalyzed by metal and the broad
one a t higher temperature to coke oxidation from the
cover acid sites. For the present stage, it is hard to
assign each peak to the definite coke type on this recently developed catalyst. However, from the comparison of FT-IR spectra and 02-TPO profiles, it can be
concluded that the difference in the coke type and its
location is not as remarkable as that in the stability
of catalysts.

100

200

300

400

500

600

700

800

900

1000

Temperature ( % )

Figure 6. The 0 2 - T P O profiles of spent low/

A1203-70HY catalysts under different reaction pressure
(1) 0.1 MPa. (2) 0 5 MPa, ( 3 ) 0.8 hIPa, (4)1.0 hlPa,
(5) 2.0 hlPa

4. Discussion

4.1 Discussion for the effect of reaction temperature

Although the definite oxidation number of active tungsten sites is still ambiguous, the active sites
are conventionally considered to be in reduced state.
Tungsten species with oxidation number of +4 lead to
the highest metathesis activity on W03/A1203 [15]
and SiO2 supported organotungsten complexes [16].
Choung et al. [17],have also proposed that some intermediate nonstoichiometric tungsten oxides are most
active for the propene metathesis. The previous results also revealed that the most active tungsten oxide
catalysts are also accompanied with adsorption bands
of +4. +5, especially intermediate state between 1 5

and +6 [5].
From the UV Vis spectra of spent catalysts, it
is still premature to conclude the precise oxidation
state of active species on W03/A120~-70HYcatalyst.
However, it really reveals that the reaction temperatures influence the state and amount of tungsten
species, leading to the remarkable different metathesis activity. With a favorable temperature range of
150-180 "C, abundant amount of W4+, W5+, and W
species in intermediate states between +5 and f 6 ,
lead to high metathesis activities. Too high reaction
temperatures cause the deep reduction of W species
and result in the quick deactivation of catalysts as
reported for other catalyst systems [l8,19].
The appearance of a maximum for the activity as
a function of the reaction temperature is a common
phenomena for the metathesis of propene over various
supported WO3 catalysts [20]. This is also explained
by a special criterion, between heat of adsorption of
alkene and activation energy for the metathesis, or a
reversible variation in the number of active sites taking place when poisons or assumed fragments of the
reaction are adsorbed or desorbed [21]. At low temperature, the catalyst is subject to the inhibition of
side products, which can be eased a t elevated temperature [all. However, the raised temperature also
binds the decrement of active sites [21] with possible
severe side reactions.
4.2 Discussion for the effect of reaction pressure
The FT-IR and 02-TPO results have revealed
that the nature and location of a carbonaceous compound is basically similar for all spent lOW/Al20370HY catalysts. Then, one possible reason may be
that the accumulating rate of these deposited carbonaceous compounds is different. TG gives the total
weight loss of these spent catalysts. As shown in Table 1, the total weight loss is 12.7 wt%, 14.9 wt%,
16.1 wt%, 18.1 wt%, and 23.0 wt% respectively, with
which the reaction time is 17, 76, 74, 36, and 23 h. As
the weight loss in the 50-150 "C range is attributed
to water, adsorbed alkenes feed, and some volatile
products, the weight loss in the 150-1000 "C should
be caused by deposited carbonaceous compound and
the value is 9.6 wt%, 12.6 wt%, 14.4 wt%, 16.2 wt%,
and 21.1 wt% respectively. For the most favorable
0.5-0.8 MPa pressure, the weight loss caused by the
carbonaceous compound is about 12.6 wt%-14.4 wt%
with 76 or 74 h reaction time. As a comparison, the

Journal of Natural Gas Chemistry VoJ. 15 No. 2 2006

weight loss of spent catalysts is 16.2 wt% and 21.1

wt%, whereas the reaction time is only 36 and 23 h.
For the present, the detailed kinetics of coking on
1OW/A12 03- 70HY catalyst under different pressure
is still unknown. Nevertheless, the rough comparison
can indicate that the accumulating rate of carbonaceous compound under 0.5-0.8 MPa is relatively low.
Table 1. The weight loss of spent 10W/A120370HY catalysts under different pressure

Reaction

Total weight

time (h)

loss (%)

0.1 MPa

17

12.7

3.1

0.5 MPa
0.8 MPa

76
74

2.3
1.7

1.0 MPa

36

2.0 MPa

23

14.9
16.1
18.1
23.0

9.6
12.6
14.4

1.9
1.9

21.1

Pressure

Weight loss (%)

I
I1

99

high pressures (>0.8 MPa) are not favorable to maintain 2-butence conversions. For 180 "C, the suitable
pressure is in the 0.5-0.8 MPa range. The characterization results of spent catalysts suggest that the accumulation of nondesorbed carbonaceous compound
under this pressure range is relatively slow. These results can give some useful information for the practical
application of WOs/Al203-HY and further modified
catalysts.

16.2

I: 50-150 "C, 11: 150-1000 "C.

It is still ambiguous why the stability under

atmospheric pressure is rather poor despite the
oligomerization and polymerization side reactions are
unfavorable under this low pressure. According to
the literature [3], other possible routes for deactivation include (I) reduction of central metal atom below
its optimum oxidation state; (11) an intrinsic reductive elimination of metallacyclobutane intermediate.
For example, the reduction of the active centers by 2pentene was proposed by Milanovic for the metathesis
of 2-pentene on the CoO.M003/A1203 catalysts [22].
This also indicates multi-routes for the deactivation
of WO3/Al203-70HY catalysts besides conventional
coking. More efforts should be made in the deactivation of this newly found catalyst and related work is
under way.
5. Conclusions
In summary, the reaction temperature and pressure are key parameters for the catalytic performance of W03/A1203-HY. At low reaction temperature (<120 "C), the possible inhibition of side products and the low amount of reduced tungsten species
lead to extremely poor catalytic performance. Higher
reaction temperature (150-180 "C) will promote the
formation of potentially active W4+, W5+, and intermediate states between $5 and +6, which can achieve
high 2-butene conversion of 85% and approach the
thermodynamic equilibrium of reaction conditions.
However, too high temperature (>240 "C) will lead
t o the quick deactivation of catalysts. The stability of the WOs/Al203-70HY catalyst is remarkably
influenced by pressure. Too low (0.1 MPa) and too

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