Influence of the catalyst composition in the oxidative dehydrogenation of 1-butene over BiVxMo1-x oxide catalysts

Article abstract of DOI:10.1016/j.apcata.2014.10.063

BiV_xMo_1-x oxide catalysts with varying compositions were investigated in the oxidative dehydrogenation (ODH) of 1-butene to 1,3-butadiene (BD). Notably, incorporation of vanadium in the Bi-Mo oxide significantly enhanced the catalytic performance in the ODH of 1-butene. Among the tested catalysts, the BiV_0.6Mo_0.4 oxide catalyst exhibited superior oxygen mobility in temperature-programmed re-oxidation experiments, revealed the facile desorption of adsorbed BD species in the temperature-programmed desorption of 1-butene, and displayed the highest performance (72.2% conversion of 1-butene and 64.0% yield in BD) in the ODH of 1-butene. Moreover, the performance of the tested catalysts decreased in the following order BiV_0.6Mo_0.4 > BiV_0.4Mo_0.6 > BiV_0.8Mo_0.2 > BiV_0.2Mo_0.8 > BiMo > BiV. In addition, the BiV_0.6Mo_0.4 oxide catalyst displayed stable performance over 85 h and its excellent catalytic ability makes it economically viable.

Full text of DOI:10.1016/j.apcata.2014.10.063

Accepted Manuscript
Title: Influence of the catalyst composition in the oxidative
dehydrogenation of 1-butene over BiV Mo
oxide catalysts
x
1−x
Author: Jung-Hyun Park Chae-Ho Shin
PII:
S0926-860X(15)00068-X
DOI:
Reference:
http://dx.doi.org/doi:10.1016/j.apcata.2014.10.063
APCATA 15233
To appear in:
Applied Catalysis A: General
Received date:
Revised date:
Accepted date:
28-5-2014
26-8-2014
5-10-2014
Please cite this article as: J.-H. Park, C.-H. Shin, Influence of the catalyst composition
in the oxidative dehydrogenation of 1-butene over BiV Mo oxide catalysts, Applied
x
1−x
Catalysis A, General (2015), http://dx.doi.org/10.1016/j.apcata.2014.10.063
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Influence of the catalyst composition in the oxidative
dehydrogenation of 1-butene over BiV Mo oxide catalysts
x
1-x
†
Jung-Hyun Park, Chae-Ho Shin
Department of Chemical Engineering, Chungbuk National University, 361-763 Cheongju,
Korea
Highlights
1
Page 1 of 33

►
►
►
Effect of cata ly st com pos it io n on B iV M o1-x ox id e cata ly st was in vest ig ated.
x
The cata ly st com pos it io n affects rem arkab ly the convers io n and se le ct iv it y.
B iV M o
0.4
cata ly st shows an
exce lle nt act iv it y for ox id at iv e
0
.6
dehydrogenat io n.
►Y ie ld in 1 ,3 -butad ie ne is corre la ted w it h the oxygen m ob ilit y.
†
To whom correspondence should be addressed.
E-mail: chshin@chungbuk.ac.kr
Abstract
x
BiV Mo1-x oxide catalysts with varying compositions were investigated in the oxidative
dehydrogenation (ODH) of 1-butene to 1,3-butadiene (BD). Notably, incorporation of
vanadium in the Bi-Mo oxide significantly enhanced the catalytic performance in the ODH
of 1-butene. Among the tested catalysts, the BiV0.6Mo0.4 oxide catalyst exhibited superior
oxygen mobility in temperature-programmed re-oxidation experiments, revealed the facile
desorption of adsorbed BD species in the temperature-programmed desorption of 1-butene,
2
Page 2 of 33

and displayed the highest performance (72.2% conversion of 1-butene and 64.0% yield in
BD) in the ODH of 1-butene. Moreover, the performance of the tested catalysts decreased
in the following order BiV0.6Mo0.4 > BiV0.4Mo0.6 > BiV0.8Mo0.2 > BiV0.2Mo0.8 > BiMo >
BiV. In addition, the BiV0.6Mo0.4 oxide catalyst displayed stable performance over 85 h and
its excellent catalytic ability makes it economically viable.
Keywords
x
BiV Mo1-x oxide catalyst
Catalyst composition
1,3-butadiene
Temperature-programmed re-oxidation
Oxygen mobility
3
Page 3 of 33

1
. Introduction
1
,3-butadiene (BD) constitutes an important raw material for the production of
compounds such as styrene butadiene rubber (SBR), poly-butadiene rubber (BR), and
acrylonitrile-butadiene-styrene resin (ABS) [1]. Over 98% of the global BD supply is
produced by extracting C4 raffinates from naphtha cracking. However, the generated
BD supply from this process does not satisfy the demands of the petrochemical market.
Therefore, alternative methods are required for the efficient production of BD. Of the
available alternatives, the oxidative dehydrogenation (ODH) of n-butenes has received
significant attention, because this reaction can produce BD in a high yield [2,3]. Various
metal oxide catalysts such as manganese oxide molecular sieves [4], K-doped
x 2 3
VO /Al O [5], ferrite catalysts [6,7], and pure bismuth-molybdate catalysts or bismuth-
molybdate based multicomponent oxide catalysts [8-17] have been tested in the ODH of
n-butenes. Among these catalysts, bismuth-molybdate-based catalysts have been studied
intensively. In particular, multicomponent oxide catalysts composed of various
transition metals and non-metals have been widely investigated in an attempt to
improve the low catalytic performance of pure bismuth-molybdate catalysts [8-17]. In
previous works, we compared the catalytic performance of multicomponent Bi-Fe-
Me(x)-Mo oxide catalysts prepared by the addition of different transition metals.
Notably, BiFe0.65Ni0.05Mo oxide exhibited the best catalytic performance in the ODH of
9 3 1
1-butene [11]. Jung et al. reported that Co Fe Bi Mo12O51 showed the highest oxygen
mobility and the best catalytic performance in the ODH of n-butenes [13].
Vanadium oxide is an effective catalyst or promoter of selective oxidation to
4
Page 4 of 33

yield acrolein from propylene and from n-butenes to butadiene [18-21]. Rossi et al. [22]
reported the catalytic performance of a scheelite-structured catalyst containing
vanadium in the ODH of 1-butene. Notably, the cationic vacancy of the catalysts
facilitated allylic oxidation and lattice oxygen diffusion. Ueda et al. [23] reported that in
the oxidation of propylene, the catalytic performance of Bi1-x/3
V1-xMo
x 4
O with a
5+
6+
scheelite-like structure increased upon substitution of V ions with Mo ions, without
any concomitant changes in the selectivity towards acrolein.
The ODH of n-butenes occurs via three major elementary steps according to the
Mars-van Krevelen (MvK) mechanism [24]. First, the alkene is adsorbed on the
catalyst surface and is activated by the abstraction of the α hydrogen to the double
bond to produce an allylic intermediate. Next, the catalyst’ oxygen is inserted into the
activated allylic intermediate and the intermediate reacts via the lattice oxygen to form
the desired products. Finally, the reduced catalyst is oxidized by a supply of gaseous
oxygen. The oxygen mobility of the catalyst is critical to the catalytic activity in ODH
reactions, and many researchers have measured this property using various analytical
tools such as temperature programmed re-oxidation [9-11,25], temperature-
18
16
programmed desorption of O
2
[26,27], and O/ O isotopic exchange measurements
[28], etc. In previous works, we performed temperature programmed re-oxidation
measurements to determine the oxygen mobility of certain catalysts and found that
catalysts with high oxygen mobility exhibited superior performance in the ODH of 1-
butene [9-11].
x
Here, the catalytic performance of BiV Mo1-x oxide catalysts with different
V/Mo molar ratios (x = 0-1.00; Bi to V/Mo molar ratio was set at 1.0), prepared by co-
5
Page 5 of 33

x
precipitation, were evaluated in the ODH of 1-butene to BD. BiV Mo1-x oxide catalysts
were characterized using X-ray diffraction (XRD), N sorption, Raman spectroscopy,
2
Inductively coupled plasma atomic emission spectroscopy (ICP-AES), 1-butene
temperature-programmed desorption (1-butene TPD) and temperature-programmed re-
oxidation (TPRO).
2
. Experimental
2.1. Catalyst preparation
A series of BiV
x
Mo1-x oxide catalysts (x = 0.0-1.0) was prepared by co-
∙5H O, Junsei, 98%), ammonium
O, Junsei, 99%), and ammonium metavanadate
3
, Sigma-aldrich, 99%) were used as received without further purification.
precipitation. Bismuth nitrate (Bi(NO
heptamolybdate ((NH Mo
NH VO
3
)
3
2
4
)
6
7 2
O24∙4H
(
4
Mixed metal oxide samples were prepared according to the following procedure:
bismuth nitrate was dissolved in deionized water acidified with 10% nitric acid.
Ammonium metavanadate and ammonium heptamolybdate were dissolved in deionized
o
water at 70 C, respectively. To prepare the mixed metal solution, the vanadium- and
bismuth-containing solutions were added to the molybdenum-containing solution with
o
vigorous stirring at 70 C and the pH of the mixed metal solution was adjusted to 8
using NH
4
OH (Samchun, 28-30 vol%). The resulting solution was vigorously stirred at
6
Page 6 of 33

o
7
0 C for 1 h and was then filtered and washed several times with deionized water. The
o
o
solid product was dried at 100 C for 12 h and calcined at 550 C for 2 h under a flow of
air.
2.2. Characterization
x
The crystalline structures of the BiV Mo1-x oxide catalysts were recorded on an
X-ray diffractometer (Bruker D5005) using CuK radiation (30 kV and 50 mA) with a
o
-1
x
scan rate of 1.2 min . The XRD phases of the BiV Mo1-x oxide catalysts were
identified by their characteristic diffraction peaks using JCPDS files. The surface areas
o
and pore volumes of the catalysts were determined by N
2
adsorption at -196 C using a
Micromeritics ASAP 2020. Prior to the measurement, 0.5g of the sample was degassed
o
at 250 C for 4 h. The surface area was determined using the Brunauer-Emmett-Teller
o
(BET) equation in the range of P/P = 0.05-0.20 and the total pore volume was
measured at P/P = 0.99.
o
Elemental analysis was carried out using inductively coupled plasma atomic
emission spectroscopy (ICP-AES, Jarrell-Ash Polyscan 61E) in combination with a
Perkin-Elmer 5000 atomic absorption spectrophotometer. Scanning electron microscopy
(SEM) images of the catalysts were acquired on a Hitachi S-2500C scanning electron
microscope at an acceleration voltage of 5 kV. Raman spectra were recorded on a
Bruker Optic GMBH FRA 106/S with an Nd:YAG laser (300 mW, 500 scans).
Temperature-programmed re-oxidation (TPRO) was performed in a U-shaped
7
Page 7 of 33

quartz reactor, and 0.15 g of the catalyst was used for each measurement in order to
elucidate the oxygen mobility. Prior to the analysis, the catalysts were pretreated at 420
o
3
-1
C for 1 h with a mixture of 50% H
room temperature (RT) under the same atmosphere. In this step, the catalysts would be
reduced by the H -Ar flow. To confirm the degree of oxygen consumption by the
oxidation reaction occurring on the reduced sites of the catalysts, a flow of 5% O in N
20 cm min ) was utilized in the reactor and the catalyst was subsequently heated to
2
in Ar (100 cm min ) and were then cooled to
2
2
2
3
-1
(
o
o
-1
6
2
00 C from RT at a heating rate of 10 C min . The mass signal of m/z = 32 (∙O ) in the
outlet gas was measured by mass spectroscopy (MS, Pfeiffer vacuum QMS 200).
2
O -pulse experiments were performed using the same apparatus as that used for
TPRO in order to measure the quantity of oxygen consumed during catalyst re-
o
oxidation. Prior to the analysis, 0.15 g samples were reacted at 420 C for 1 h under the
3
-1
specified reaction conditions and were flushed for 1 h with a 30 cm min Ar flow. To
measure the oxygen consumption of the reduced catalyst sites, 71.0 mol of O
2
with an
3
Ar carrier (2 cm sample loop) was introduced into the catalyst bed every 5 min and
2
pulse experiments were repeated 8 times. The mass signal of m/z = 32 (∙O ) in the outlet
gas was measured using the same MS analyzer as that in the TPRO experiments.
In order to elucidate the adsorption-desorption behavior of 1-butene,
temperature-programmed desorption of 1-butene (1-butene TPD) was carried out using
a similar apparatus to that in the TPRO measurements. Prior to the analysis, the
o
3
-1
catalysts were pretreated at 200 C for 1 h with Ar (30 cm min ) and then cooled to RT.
3
-1
4 8
The catalyst was then treated at RT for 0.5 h with 1-C H (20 cm min ). Following the
3
-1
adsorption of 1-butene at RT, the sample was purged under a flow of Ar (30 cm ∙min )
8
Page 8 of 33

o
o
-1
for 0.5 h. TPD was performed from 50 to 800 C at a heating rate of 10 C min . The
mass signals of m/z = 18 (·H O), 44 (·CO ), and 54 (·C ) were detected using the
same MS analyzer as that used in the TPRO experiments.
2
2
4 6
H
2.3. Catalytic testing
The ODH of 1-butene was carried out at ambient pressure with 0.5 g of the
catalyst in a continuous flow fixed-bed reactor. Prior to the reaction, all catalysts were
o
3
-1
o
pretreated at 500 C for 2 h with a flow of N
2
(50 cm min ) and were cooled to 420 C
/air/steam =
/3.75/5 with a total flow rate of 78 cm min . Steam was sufficiently vaporized by
passage through an evaporator. The products were analyzed by an on-line gas
chromatograph (Varian 3800) with an Al /KCl column (FID detector) for
hydrocarbons and a Porapak Q packed column (TCD detector) for CO and CO . The
production of CO was negligible under the reaction conditions. Cracking products such
as CH , C , and C were minor or negligible. The conversion, selectivity and yield
in BD were calculated following previously reported procedures [29].
under the same atmosphere. The feed composition was fixed at 1-C
4 8
H
3
-1
1
2 3
O
2
4
2
H
6
3 8
H
3
. Results and discussion
3.1. Characterization of catalysts
9
Page 9 of 33

x
Fig. 1 shows the XRD patterns of the BiV Mo1-x oxide catalysts prepared with
different V/Mo molar ratios. Generally, BiMo oxide is composed of three phases, -
Bi
Bi
2
2
Mo
3
O
O
12, -Bi
2
Mo
2
O
9
, and -Bi
2
Mo
1
O
6
2 2 9
Mo O
. -Bi partially decomposed to -
Mo
3
12 and -Bi
2
Mo
O
1 6
due to the calcination temperature [9,30]. BiMo oxide with
o
Bi/Mo = 1.0 calcined at 550 C contained two mixed phases, namely, -Bi
2
1 6
Mo O , and

-Bi
2
Mo
2
O
9
. The BiV oxide catalyst showed the typical BiVO
4
phase. The BiV Mo1-x
x
oxide catalysts exhibited different phases according to their composition. Catalysts with
high vanadium contents (BiV0.8Mo0.2, BiV0.6Mo0.4, and BiV0.4Mo0.6), displayed
Bi0.93Mo0.21
V
0.79
O
4
and Bi0.93Mo0.37
V
0.63
O
4
with a minor phase of -Bi
respectively, while the catalyst with a low vanadium content (BiV0.2Mo0.8) crystallized
primarily in the -Bi
Mo phase (Table 1). The relative intensities of the constituent
phases in the BiV Mo1-x oxide catalysts were also different depending on the molar ratio
of V/Mo. In addition, the diffraction patterns of the BiV Mo1-x oxide catalysts shifted to
a higher angle with decreasing Mo contents. Since the radii of V cations (0.068 nm)
2 1 6
Mo O ,
2
1 6
O
x
x
5+
6+
5+
are smaller than those of Mo cations (0.073 nm), V cations can be inserted into the
BiMo oxide catalyst [31], which leads to the formation of solid solution phases.
The BET surface areas and the total pore volumes of the BiV
x
Mo1-x oxide
catalysts are listed in Table 1. The BET surface areas of the BiV Mo1-x oxide catalysts
x
2
-1
were smaller than those of the pure BiMo oxide catalysts (3.9 m g ), but, larger than
2
-1
that of the BiV oxide catalyst (0.9 m g ). The BET surface areas of the BiV
x
Mo1-x
oxide catalysts showed no significant changes upon variation of the vanadium content
2
-1
(
2.6-4.6 m g ). The atomic ratios of the metal components are also summarized in
1
0
Page 10 of 33

Table 1. The catalyst composition was calculated as the molar ratio of each metal
component with respect to that of Bi. The catalyst molar ratios determined by ICP-AES
analysis were nearly consistent with the molar ratio of the mother solution, and were in
relatively good agreement with the theoretical values, suggesting that the BiV
x
Mo1-x
oxide catalysts were successfully prepared.
Fig. 2 shows the SEM images of the BiV
x
Mo1-x oxide catalysts with varying
Mo1-x oxide catalysts
compositions. The morphology and particle size of the BiV
x
greatly depended on the composition. BiMo oxide exhibited nanostructures with
diameters ranging between 100 and 200 nm. BiV0.2Mo0.8, BiV0.4Mo0.6, and BiV0.6Mo0.4
oxide catalysts showed somewhat different particle shapes as compared to the BiMo
x
oxide catalyst (Fig. 2(b-d)). In addition, the particle sizes of the BiV Mo1-x oxide
catalysts were larger than that of the BiMo oxide catalyst. The particle sizes of the
vanadium-rich catalysts (BiV0.8Mo0.2, and BiV) were significantly greater than those of
other catalysts (≈10 m), and the morphology of the catalysts was nearly spherical and
consisted of small microspheres. A similar observation was reported previously [32].
Raman spectroscopy can provide structural information and is a sensitive
method for the investigation of local structure and electronic properties of various
x
samples. Fig. 3 shows the Raman spectra of the BiV Mo1-x oxide catalysts with different
V/Mo molar ratios. Vibrational bands of the BiV oxide catalyst were observed at 212,
-1
3
25, 367, and 828 cm . These bands corresponded to the typical vibrational bands of
-1
4
BiVO [33,34]. The band at 828 cm was assigned to the symmetric V-O stretching
-1
mode, while the peaks at 325 and 367 cm were assigned to the asymmetric and
-1
4
symmetric bending vibration of the VO tetrahedron. The band at 212 cm represented
1
1
Page 11 of 33

the external vibrations [34,35]. The vibrational bands of the BiMo oxide catalyst were
-1
observed around 284, 293, 354, 404, 715, 780, 807, and 852 cm , corresponding to the
typical vibrational bands of -Bi Mo [36,37]. For catalysts with high vanadium
contents (BiV0.8Mo0.2, BiV0.6Mo0.4, and BiV0.4Mo0.6), the mixed oxides showed similar
2
1 6
O
-1
Raman spectra. The vibrational bands at 336, 817, 880, and 883 cm were assigned to
the Bi-V-Mo mixed phase. The peak shift was speculated to be related to the catalyst
composition. In addition, vibrational bands related to -Bi
all BiV Mo1-x oxide catalysts. For the catalyst with a low vanadium content
BiV0.2Mo0.8), the spectrum was very similar to that of the BiMo oxide catalyst. Overall,
the Raman results were in good agreement with the XRD results.
2 1 6
Mo O were also observed in
x
(
3.2. Catalytic testing
Fig. 4 shows the catalytic performance of the BiV
ODH of 1-butene to BD after an 8 h reaction, plotted as a function of the vanadium
content. For all catalysts, BD and CO constituted the main products and small amounts
of cracking products, such as CH , and C were also observed. All catalysts showed
x
Mo1-x oxide catalysts in the
2
4
2 6
H
stable catalytic performance over 8 h on stream (Fig. S1 in the supplementary data).
Notably, the catalyst composition had a significant influence on the catalytic
performance of the BiV
BD were maximized at a vanadium content of x = 0.6. The selectivity toward BD
increased, whereas the selectivity towards CO decreased with respect to the vanadium
x
Mo1-x oxide catalysts. The conversion of 1-butene and yield in
2
1
2
Page 12 of 33

content and showed a reverse volcano-shaped curve with respect to the vanadium
content. The conversion of 1-butene and the yield in BD with the BiV0.6Mo0.4 oxide
catalyst were 72.2% and 64.0%, respectively. The catalytic performance of the catalysts
in the ODH of 1-butene decreased in the following order: BiV0.6Mo0.4 > BiV0.4Mo0.6
>
BiV0.8Mo0.2 > BiV0.2Mo0.8 > BiMo > BiV. Table S1 lists the catalytic performance of the
reported catalysts in the ODH reaction. The catalytic performance of the catalysts used
in this study was slightly lower than those reported previously. Further studies are
required in order to improve the catalytic performance of BiVMo oxide catalytic
systems.
3.3. TPRO
x
In order to elucidate the oxygen mobility of the BiV Mo1-x oxide catalysts,
TPRO analysis was performed with the reduced catalysts, as shown in Fig. 5 (A). It is
well known that the oxygen mobility of the catalysts is important in the ODH of butenes.
The peak temperatures observed during TPRO runs reflect the oxygen mobility of the
catalysts, in that lower desorption peak temperatures reveal a higher oxygen mobility
[9,40,41]. For the BiV
x
Mo1-x oxide catalysts, several oxidation peaks were observed for
o
each catalyst. The first peak in the 150-250 C range was a sharp and asymmetric peak.
o
The other peaks appeared in the 280-500 C range and were related to the oxidation of
the partially reduced bismuth and molybdenum species [42]. The first peak was shifted
to lower temperatures with increasing vanadium content, and the minimum value was
1
3
Page 13 of 33

observed with the BiV0.6Mo0.4 oxide catalyst. The peak position sequence of the other
catalyst was in the following order: BiV0.6Mo0.4 < BiV0.4Mo0.6 < BiV0.8Mo0.2
<
BiV0.2Mo0.8 < BiMo < BiV. This was in good agreement with the catalytic performance
of the catalysts.
Fig. 5 (B) shows the correlation between the yield in BD and the oxygen
mobility of the BiV
x
Mo1-x oxide catalysts. The yield in BD increased with lower TPRO
temperatures. The BiV0.6Mo0.4 catalyst showed the lowest TPRO peak temperature (181
o
o
C), while the BiV oxide catalyst showed the highest TPRO peak temperature (254 C).
The BiV0.6Mo0.4 oxide catalyst, which showed the lowest TPRO peak temperature,
exhibited the best catalytic performance among the catalysts. As such, high catalytic
performance can be attributed to the oxygen mobility of the catalyst. In order to
measure the quantity of oxygen consumed, O
2
-pulse experiments were carried out and
the results are shown in Table 1. In the O -pulse experiments, the introduced oxygen
2
was completely consumed during the 3 pulses and subsequently, distinct changes were
not observed (Fig. S2), indicating that the reduced catalyst was completely re-oxidized.
The consumed oxygen was related to the oxygen migration to the catalyst surface or
2 2
lattice and was calculated by integrating the detected O peak during the O -pulse
experiments. The total quantity of consumed oxygen on BiV0.6Mo0.4 oxide was much
larger than that on the other catalysts (Table 1). The oxygen consumption decreased in
the following order: BiV0.6Mo0.4 > BiV0.4Mo0.6 > BiV0.8Mo0.2 > BiV0.2Mo0.8 > BiMo >
BiV, and was in good agreement with the catalytic performance; however, there was no
2
direct correlation between the quantity of consumed O and BD selectivity.
1
4
Page 14 of 33

3.4. TPD of 1-butene
TPD analysis was performed to investigate the desorption characteristics of 1-
butene over the BiV Mo1-x oxide catalysts. The TPD patterns of 1-butene are shown in
Fig. 6 and 7, where the response of m/z = 54 (·C ) was plotted as a functions of
desorption temperature. BD (·C ) is the product of 1-butene with lattice or surface
x
4
H
6
4
H
6
oxygen in the BiV
x
4 8
Mo1-x oxide catalysts. The TPD profiles of m/z = 56 (·C H )
o
gradually decreased with increasing desorption temperature until 450 C. Above this
2 2
temperature, no desorption of 1-butene was observed. Furthermore, H O and CO , the
products of 1-butene with non-selective oxygen at the combustion sites, were
o
completely desorbed above 500 C (Fig. 6). The TPD profiles of all BiV
x
Mo1-x oxide
catalysts revealed a broad and asymmetric peak. The peak temperature showed a
diminishing trend with respect to the vanadium content, indicating that the desorption of
BD was influenced by the vanadium content. In addition, the quantity of desorbed BD
increased with increasing vanadium content, and showed a maximum value at x = 0.6 in
BiV
x
Mo1-x oxide.
Fig. 7(B) depicts the correlation between the catalytic performance and the
quantity of desorbed BD and desorption temperature. The quantity of BD obtained via
integration of the TPD profile exhibited a volcano-shaped curve with respect to the
vanadium content, and the BiV0.6Mo0.4 oxide catalyst yielded the largest quantity of BD
as compared to the other catalysts, indicating that the BiV0.6Mo0.4 oxide catalyst had
more lattice/surface oxygen or adsorption sites. Also, the desorption temperature of BD
resulted in a reverse-volcano shaped curve with respect to the vanadium content, and the
1
5
Page 15 of 33

BiV0.6Mo0.4 oxide catalyst presented the lowest desorption temperature, indicating that
the BD adsorbed on the BiV0.6Mo0.4 oxide catalyst was more easily desorbed as
compared to on the other catalysts. From the TPD analysis, it can be concluded that the
catalytic performance was closely related to the quantity of lattice/surface oxygen,
adsorption sites, and facile desorption of BD.
Fig. 3S shows the MS signals in the reaction over the BiV0.6Mo0.4 oxide catalyst
in the absence of an oxygen feed. All other reaction parameters were fixed as the
standard reaction conditions. Under the O
(m/z = 56) slightly decreased at the beginning of reaction and subsequently
exhibited a constant value. The MS signals of ∙CO (m/z = 44) and ∙C (m/z = 54)
2
-free reaction conditions, the MS signal of
4 8
∙C H
2
4 6
H
gradually decreased as a function of time and finally reached zero after 35 min. This
indicates that the BiV0.6Mo0.4 oxide catalyst consumed lattice oxygen during the
reaction in the absence of an oxygen feed, which is in good agreement with the MvK
mechanism and is been generally accepted in the ODH of butenes [10,26,40]. Therefore,
the peak area of the BD signal reflects the quantity of lattice oxygen, which can be
4 8
calculated by integrating the peak area. The reduced catalyst upon reaction with 1-C H
can be re-oxidized via a supply of gas phase oxygen. Facile reduction-oxidation cycles
are critical in enhancing the catalytic performance.
3.5. Long-term stability test
To assess the stability of the catalyst, a long-term stability test of the BiV0.6Mo0.4
1
6
Page 16 of 33

oxide catalyst was carried out and the results are shown in Fig. 8. Conversion of 1-
butene was maintained throughout the reaction. The selectivity towards BD gradually
2
increased and the selectivity towards CO decreased over 30 h. After 30 h, the
selectivities towards the products were maintained. The conversion of 1-butene and the
yield in BD after 85 h were 72.5%, and 64.0%, respectively. The BiV0.6Mo0.4 oxide
catalyst showed suitable catalytic performance and stability, rendering it economically
viable.
4
. Conclusions
BiV
prepared and their performance in the ODH of 1-butene to BD was evaluated. The
formation of the BiV Mo1-x oxide catalysts was confirmed via XRD and ICP analysis.
The catalytic performance in the ODH reaction of 1-butene depended on the catalyst
composition. The oxygen mobility of the BiV Mo1-x oxide catalysts was related to their
x
Mo1-x oxide catalysts with various vanadium contents (x = 0-1.0) were
x
x
catalytic performance. The BiV0.6Mo0.4 oxide catalyst, which gave the best catalytic
performance, showed the lowest TPRO temperature. The BiV0.6Mo0.4 oxide catalyst
displayed the highest catalytic performance and stability during long-term stability tests.
Acknowledgement
1
7
Page 17 of 33

This work was financially supported by the Industrial Strategic technology development
program (2014-10042591) funded by the Ministry of Trade, industry & Energy (MOTIE,
Korea).
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2
0
Page 20 of 33

Graphical Abstract
Influence of the catalyst composition in the oxidative dehydrogenation
of 1-butene over BiV Mo oxide catalysts
x
1-x
Jung-Hyun Park, Chae-Ho Shin*
Department of Chemical Engineering, Chungbuk National University,Chungbuk 361-763,
Korea
2
Conversion of 1-butene and selectivity to 1,3-butadiene and CO with respect to V/Mo molar ratios
2
2
Page 21 of 33

*
Corresponding author. Tel.: +82-43-261-2376; fax: 82-43-269-2370.
E-mail address: chshin@chungbuk.ac.kr (C.-H. Shin).
2
3
Page 22 of 33

Figure captions
x
Fig. 1 XRD patterns of BiV Mo1-x oxide catalysts: (a) BiMo, (b) x = 0.2, (c) 0.4, (d) 0.6,
(e) 0.8, and (f) BiV.
x
Fig. 2 SEM images of BiV Mo1-x oxide catalysts: (a) BiMo, (b) x = 0.2, (c) 0.4, (d) 0.6,
(e) 0.8, and (f) BiV.
x
Fig. 3 Raman spectra of BiV Mo1-x oxide catalysts: (a) BiMo, (b) x = 0.2, (c) 0.4, (d)
0.6, (e) 0.8, and (f) BiV.
Fig. 4 Catalytic activity over BiV
x
Mo1-x oxide catalyst in the ODH after an 8 h reaction.
o
Reaction conditions: 0.5 g catalyst, T = 420 C, 1-C
4
H
8
/air/H
2
O = 1/3.75/5 and total
3
-1
flow rate of 78 cm min .
x
Fig. 5 (A) TPRO profiles of reduced BiV Mo1-x oxide catalysts and (B) correlation
curve between the yield in BD and the TPRO peak temperature: (a) BiMo, (b) x = 0.2,
c) 0.4, (d) 0.6, (e) 0.8, and (f) BiV.
(
Fig. 6 MS signals of 1-butene TPD of BiV0.4Mo0.6 oxide catalyst.
2
4
Page 23 of 33

Fig. 7 (A) 1-Butene-TPD profiles of BiV
curve between the peak area, temperature, and catalyst composition: (a) BiMo, (b) x =
.2, (c) 0.4, (d) 0.6, (e) 0.8, and (f) BiV.
x
Mo1-x oxide catalysts and (B) correlation
0
Fig. 8 Long-term stability test over BiV0.6Mo0.4 oxide catalyst in the ODH: (a)
conversion and yield in BD and (b) selectivity towards BD and CO
2
.
2
5
Page 24 of 33

Table
Table 1 physicochemical property of the BiV Mo1‒x oxide catalysts and their catalytic performance
x
c
Catalytic performance
b
SBET
Oxygen
Composition (mol)
Catalyst
XRD phase
Conv. Selectivity (wt.%) Yield
2
-1
a
(
m g )
quantity (mol)
Bi
V
-
Mo
0.85
0.69
0.55
0.40
0.12
-
(%)
BD
7.0
CO2
90.1
79.0
9.0
(wt.%)
BiMo
3.9
4.6
2.4
2.5
2.6
0.9
-Bi Mo O , -Bi Mo O
103.3
131.2
1.00
2.0
5.6
0.1
0.9
2
1
6
2
2
9
BiV Mo
-Bi Mo O , -Bi Mo O
1.00 0.19
1.00 0.45
1.00 0.58
1.00 0.78
1.00 0.91
16.5
89.1
88.6
41.0
7.7
0
.2
0.8
0.6
0.4
0.2
2
1
6
2
2
9
BiV Mo
Bi0.88Mo0.37V0.63O , -Bi Mo O 194.5
65.3
72.2
23.2
0.6
58.2
64.0
9.5
0
.4
4
2
1
6
BiV Mo
Bi0.93Mo0.21V0.79O , -Bi Mo O 225.3
9.9
0
.6
4
2
1
6
BiV Mo
Bi0.93Mo0.21V0.79O , -Bi Mo O 163.4
55.3
90.1
0
.8
4
2
1
6
BiV
BiVO4
94.5
0.0
a
Determined by O -pulse experiments.
2
b
c
Determined from ICP-AES.
o
The conversion and selectivity were obtained after an 8 h ODH reaction. Reaction conditions: 0.5 g catalyst, T = 420 C,
3
-1
1
‒C H /air/H O = 1/3.75/5 and total flow rate = 78 cm min .
4 8 2
1
Page 25 of 33

Fig. 1
2
Page 26 of 33

Fig. 2
3
Page 27 of 33

Fig. 3
4
Page 28 of 33

Fig. 4
5
Page 29 of 33