Catal Surv Asia (2016) 20:23–33
DOI 10.1007/s10563-015-9201-7
Oxidative Dehydrogenation of n-Butenes to 1,3-Butadiene
over Bismuth Molybdate and Ferrite Catalysts: A Review
Eunpyo Hong1 • Jung-Hyun Park2 • Chae-Ho Shin1
Published online: 2 November 2015
 Springer Science+Business Media New York 2015
Abstract 1,3-Butadiene, an important raw material for a
variety of chemical products, can be produced via the
oxidative dehydrogenation (ODH) of n-butenes over mul-
ticomponent oxide catalysts based on bismuth molybdates
and ferrites. In this review, the basic concept, reaction
mechanism, and catalysts typically used in an ODH reac-
tion are discussed.
Keywords Oxidative dehydrogenation  n-Butenes  1,3-
Butadiene  Bismuth molybdates  Ferrites
1 Introduction
1,3-Butadiene (BD) is an important raw material used in
the manufacturing of chemical products such as SBR
(styrene-butadiene rubber), polybutadiene (PB), styrene-
butadiene latex, acrylonitrile–butadiene–styrene (ABS)
resins, adiponitrile, and nitrile rubber. Among the listed
examples, the most significant use of BD is for the pro-
duction of synthetic rubbers. The production of SBR and
& Chae-Ho Shin
chshin@chungbuk.ac.kr
Eunpyo Hong
love_blueangel@hanmail.net
Jung-Hyun Park
wonga1@nate.com
1
Department of Chemical Engineering, Chungbuk National
University, Chungbuk, Cheongju 28644, Republic of Korea
2
Division of Physical Science and Engineering, KAUST
Catalysis Center (KCC), King Abdullah University of
Science and Technology (KAUST),
4700, Thuwal 23955-6900, Saudi Arabia
PB rubbers accounts for over 50 % of the total BD demand
[1]. While SBR is most commonly used in tires, it is also
used for adhesives, sealants, coatings, and other rubber
articles such as shoe soles. Meanwhile, PB rubber is a high
resistance material, which is usually used for tires and as an
additive to improve the mechanical strength of polymers,
such as ABS. Owing to its versatility, the global demand
for BD has been increasing consistently every year.
In order to satisfy the increasing demand for BD, the
industrial production of BD has been attempted via three
major routes [1]: (a) steam cracking of paraffinic hydro-
carbons (naphtha and other heavy hydrocarbons), (b) cat-
alytic dehydrogenation of n-butane and n-butene (the
Houdry process), and (c) oxidative dehydrogenation
(ODH) of n-butene. Currently, over 98 % of the global
BD supply is produced by extracting C4 raffinates from
naphtha cracking [2]. Steam cracking is the main method
used in the production of light olefins such as ethylene
and propylene, both of which are basic materials from the
petrochemical industries [3, 4]. In this process, BD is
produced as one of the co-products of the ethylene pro-
duction process. However, steam cracking is the most
energy-consuming process in the chemical industry
because the reaction is highly endothermic, and it
requires additional energy to activate the reactant. The
energy cost of the steam cracking process accounts for
approximately 70 % of the total operation costs in
naphtha olefin plants. In addition, this process evolves
approximately 180–200 million tons of CO2 globally [5,
6], and the deposition of coke formed by the pyrolysis of
hydrocarbons at high temperature is also a major concern.
Hence, from both environmental and economic perspec-
tives, a more efficient BD production process is required
in order to reduce overall CO2 emission and energy
consumption.
123
24
Catalytic dehydrogenation (direct dehydrogenation),
which has a relatively low production cost and is eco-
friendly compared to steam cracking, is one of the alter-
native processes used in the production of BD. A catalytic
dehydrogenation reaction is an unselective reaction on
metal surfaces and acid sites, which consecutively trans-
forms heavy paraffins into mono-, di-, and triolefins on the
same active sites [7]. In this reaction, alkene (or alkane)
decomposes into olefin and H2 molecule as shown below.
C4 H8 ! C4 H6 + H2 ðDHr ¼ 109:7 kJ/mol)
There are several commercial catalytic dehydrogenation
processes, including Catofin, UOP Oleflex, and Linde-
BASF. However, these catalytic processes have obvious
limitations [7, 8]:
(I) Thermodynamic restrictions on conversion and
selectivity.
(II) Side reactions such as thermal cracking.
(III) The necessity to supply heat owing to the strong
endothermic reaction.
(IV) The rapid formation of coke.
(V) Irreversible deactivation of catalyst owing to the
severe reaction conditions.
Various solutions have been proposed to overcome these
limitations. In particular, the ODH reaction has had
renewed interest in recent years, owing to the possibility
that olefins can be efficiently produced with high selec-
tivity and yield [9, 10]. In addition, the production of BD
by the ODH process does not suffer from the same prob-
lems affecting naphtha cracking and direct dehydrogena-
tion [11]. In this review, we have chosen to concentrate on
the ODH process as an effective means of producing BD.
The basic concept and reaction mechanism of the ODH
Table 1 Gas phase selective oxidation processes and the related industrial reactions [17]
Type of reaction
Allylic oxidation
Oxidative dehydrogenation
Electrophilic insertion of an oxygen atom
Acetoxylation
Oxychlorination
Ammonia oxidation
Synthesis of anhydrides
123
E. Hong et al.
reaction, in addition to the catalysts used, are discussed in
detail.
2 Basic Concept of Oxidative Dehydrogenation
The oxidation process can be divided into two main groups,
one of which is selective oxidation (partial oxidation) that
includes the ammoxidation and ODH processes. Unfortu-
ð1Þ nately, this selective oxidation route is not thermodynam-
ically favorable compared to the formation of CO and CO2
from total oxidation reactions (unselective oxidation),
which is the second type of oxidation process [12–14]. The
selective oxidation process has the potential to generate a
diverse range of valuable petrochemical intermediates,
though it must be facilitated by the use of effective cata-
lysts. About 50 % of chemical products and over 80 % of
monomers have been synthesized by selective heteroge-
neous catalytic oxidation [15]. The gas phase selective
oxidation processes for hydrocarbons and the related
industrial reactions are summarized in Table 1.
Among these selective oxidation processes, ODH is a
promising means of producing chemical intermediates,
including BD. An ODH reaction basically takes place in
the presence of oxygen, which leads to an exothermic
reaction that produces BD. As such, it avoids the thermo-
dynamic limitations of an endothermic reaction. As shown
in Eq. 2, butene and oxygen are reacted over a catalyst to
form BD and water via an ODH process.
C4 H8 + 1/2O2 ! C4 H6 + H2 O (DHr ¼  132:1kJ/mol)
ð2Þ
ODH can be performed at relatively low temperatures
(300–550 C) compared to direct dehydrogenation without
Example
Propylene to acrolein or acrylic acid
Isobutene to methacrolein or methacrylic acid
Butenes to butadiene and isopentenes to isoprenes
Methanol to formaldehyde
Isobutyric acid to methacrylic acid
Epoxidation of ethylene to ethylene oxide with O2
Direct synthesis of phenol from benzene with N2O
Synthesis of vinylacetate from ethylene and acetic acid
Synthesis of 1,2-dichloroethane from ethylene and HCl in the presence of O2
Propylene to acrylonitrile
Isobutene to methacrylonitrile
a-Methylstyrene to adiponitrile
n-Butane to maleic anhydride
o-Xylene to phthalic anhydride
Oxidative Dehydrogenation of n-Butenes to 1,3-Butadiene over Bismuth Molybdate and Ferrite… 25

the formation of coke and cracking products because the

reaction is irreversible and exothermic. The exothermic
reaction at low reaction temperatures leads to a substantial
energy saving. Furthermore, coke deposition is easily elim-
inated owing to the presence of oxygen. However, the ODH
reaction still presents some challenging problems as the
selectivity for a desired or undesired product is strongly
influenced by the reaction conditions used. The major by-
products are trans and cis-2-butene by isomerization reaction
of 1-butene which is considered as reactants in the ODH
reaction of butenes, and CO and CO2 by oxidation, and minor
by-products are CH4, C2H4, C2H6, C3H6 and C3H8 by
cracking of C4 compounds, and iso-C4H8 by skeletal iso-
merization of n-butenes. These by-products could be sepa-
rated by catalytic extractive distillation which is operating in
commercial process. By-products as aldehydes or acidic
compounds are not detected in our operating conditions by
relatively high reaction temperatures. Especially, the olefin
Fig. 1 Schematic view of the oxidative dehydrogenation cycle
and diolefin products are easily oxidized to CO and CO2 at
following the MvK mechanism
the temperatures that are required for the activation of the
reactant. In these undesired pathways, lattice, adsorbed, and
gas phase oxygen can be inserted into butene (or butane) to
form combustion products as shown in Eqs. 3 and 4 [16]:
C4 H8 + 6O2 ! 4CO2 + 4H2 O (DHr ¼  2540:8 kJ/mol)
ð3Þ

C4 H8 + 4O2 ! 4CO + 4H2 O (DHr ¼  1409:0 kJ/mol)

Fig. 2 Electron transfer in the ODH reaction leading to oxidation
ð4Þ processes

Owing to the aforementioned limitations, it is difficult to

use the ODH reaction for commercial processes. However,
extensive studies have been conducted to improve the
selectivity and yield of BD at mild reaction conditions, in
(iii)
order to allow the ODH process to compete with the current
steam cracking technology, as a means of providing a
stable supply of BD to the global chemical market.
3 Mechanism of Oxidative Dehydrogenation
The selective oxidation of alkenes with high selectivity
could potentially occur via the Mars and van Krevelen
(MvK) mechanism [18, 19]. Figure 1 shows the oxidation–
reduction cycle during a catalytic reaction that follows the
MvK mechanism, which contains three fundamental steps
[20–22]:
(i) Chemisorption of alkenes on the catalyst surface
through the abstraction of the a-hydrogen to
produce activated allylic intermediates.
(ii) The activated intermediates react with the lat-
tice oxygen coming from the catalyst, and
subsequently produce the desired product (BD).
Thus, the M1 cation is reduced at this point.
The active site and the cation (M1) are re-oxidized
by the migration of a lattice oxygen from another
site (M2). The lattice oxygen migrates from the
catalyst bulk to the surface of the active site.
Finally, the remaining oxygen vacancies are
recovered by the supplied gaseous oxygen. When
the reduced catalyst surface is replenished by the
gas phase oxygen, the surface is enriched with the
O- and O2- oxygen species [23], as shown in
Fig. 2. It has been reported that different oxygen
species exist in metal oxide catalysts, such as O2-,
O22-, O-, and O2- [24, 25]. The electrophilic
O2-, O22-, and O- species are responsible for the
unselective oxidation (total oxidation) of the
reactant, leading to a combustion reaction and
products such as CO2 and CO; while the nucle-
ophilic lattice O2- species is associated with
selective oxidation, generating the desired BD
product [25].

123
26
It is well known that the rate-determining step in the
ODH reaction varies with respect to reaction temperatures
[26–28]. The rate-determining steps at temperatures below
350 C are the re-oxidation [28] of the catalyst and the
desorption of products from the catalyst surface [26]. This
is because the mobility of the lattice oxygen is insufficient
for re-oxidation under this temperature threshold
(\350 C), while the abstraction of the a-hydrogen from
the hydrocarbon reactant (i.e., to form the allylic interme-
diate) determines the rate of reaction at temperatures above
350 C [27, 29]. The ODH reactions are usually carried out
in the temperature range of 400–500 C. Thus, the a-hy-
drogen abstraction step has a significant role on the overall
catalyst performance.
In the ODH reaction, the reaction feedstock is composed
of butene (as a reactant), air (as the O2 source), and steam.
Steam is commonly used in the ODH reaction as a diluent,
oxidant, coke remover, and heat sink [30, 31]. In addition,
Jung et al. [32, 33] have demonstrated that steam plays a
role in decreasing contact time and suppressing the total
oxidation of n-butene during reaction.
As mentioned previously (i.e., the MvK mechanism),
the lattice oxygen and oxygen vacancy have crucial roles at
the surface of heterogeneous metal oxide catalysts because
they are closely related to the oxidation–reduction cycle
involved in the production of BD. The lattice oxygen in the
metal oxide catalyst is considered as a more versatile and
selective oxidizing agent than the gaseous oxygen species
[34]. A transition metal containing lattice oxygen and
oxygen vacancy has multiple oxidation states that keep its
catalytic property constant during the redox cycle.
Although the metal component in metal oxide catalysts
does not directly take part in the ODH reaction, its intrinsic
characteristic critically influences the bonded oxygen spe-
cies (metal–oxygen bond) [35]. Therefore, the effect of
oxygen properties (mobility and capacity) on catalyst per-
formance depends on the metallic component of the indi-
vidual catalyst. In particular, bismuth molybdates and
ferrites are the most widely used catalysts for producing
BD using the ODH reaction. Therefore, the variables and
issues affecting these catalysts are discussed in the next
section, along with a brief mention of other types of
catalysts.
4 Oxidative Dehydrogenation Catalysts
The catalysts used in the ODH reaction are mainly
unsupported metal oxides containing two or more transi-
tion metal components. Amongst them, bismuth molybdate
catalysts have been extensively studied, and the co-pre-
cipitation method is usually used for synthesizing bismuth
molybdates with different Bi/Mo molar ratios. Beale and
123
E. Hong et al.
Sankar [36] reported that bismuth molybdates, synthesized
via the hydrothermal route, showed higher specific surface
area (a: 8.2–8.9, b: 9.8–10.1, and c 2.9 m2/g) than particles
obtained from the conventional co-precipitation method.
However, many studies [35, 37–39] have revealed that the
specific surface area is not directly related to catalyst
performance. Bismuth molybdate catalysts show good
catalytic performance for the ODH reaction of butene in
the Bi/Mo range of 2/1–2/3. In this range, the catalysts are
classified into three distinct forms: the a-Bi2Mo3O12, b-
Bi2Mo2O9, and c-Bi2MoO6 phases. It is well known that
the activities of these bismuth molybdate catalysts usually
diminish in the following order: c [ b [ a, owing to the
diffusion coefficient of the lattice oxygen [40] and the
adsorption ability of butene molecules [41]. Although this
order of catalytic activity is generally accepted, other
results have also been reported: b & c [ a [42] and
a & b [ c [43]. In addition, some researchers [33, 44]
have reported that b-Bi2Mo2O9 is thermally unstable and
decomposes into a-Bi2Mo3O12 and c-Bi2MoO6 in the
temperature range of 400–550 C. This range includes the
most typically used ODH reaction temperatures, as shown
in Table 2. Mixed catalyst phases have also been investi-
gated to promote the synergetic effect between different
phases such as the b ? c [45] and a ? c [46] phases. For
example, the a ? c phase shows much higher catalytic
activities than pure bismuth molybdates. This is because c-
Bi2MoO6 has a higher oxygen mobility than a-Bi2Mo3O12,
but the a phase has much more adsorption sites for n-
butene [46, 47].
The catalytic performance of bismuth molybdate is crit-
ically dependent on its surface composition [45], in which
the bismuth (Bi) and molybdenum (Mo) components are
responsible for the rate-determining a-hydrogen abstraction
step and the selective oxygen insertion, respectively [48].
The lattice oxygen also has a crucial role in the ODH reac-
tion because of its reaction pathway that follows the MvK
mechanism (see Sect. 3). Keulks [49] has demonstrated that
both the lattice oxygen on the surface layer, as well as the
oxygen on the subsurface layer participate in the ODH
reaction. Therefore, oxygen mobility is a very important
factor in determining the movement of the oxygen species
among the bulk, surface, and gaseous systems.
There are various parameters influencing the oxygen
mobility of bismuth molybdate catalysts in the ODH
reaction, and these factors are summarized in Table 2.
Oxygen mobility refers to the ability to fill the oxygen
vacancy via other lattice oxygen sites and gaseous mole-
cules. Therefore, a catalyst with a high oxygen mobility
typically shows excellent catalytic activity. The other fac-
tor influencing catalyst performance is the oxygen capacity,
which indicates the amount of oxygen (i.e., in the catalyst)
involved in the reaction.
Oxidative Dehydrogenation of n-Butenes to 1,3-Butadiene over Bismuth Molybdate and Ferrite… 27

Ref.

[50]

[51]

[33]

[44]

[45]

[46]
X & 66, Y & 60 at 440 C with c

32 mol % c phase (not indicated)

X & 66, S & 90 with 90 wt% c
S & 90, Y & 46 at pH 3 (after

X = 81.8, S = 82.8, Y = 67.7

S & 90, Y & 46 calcined at
Activity (%)b (reaction time)

with c phase (after 48 h)

X = 39.8, S = 72.6 with

phase (not indicated)

475 C (after 6 h)

phase (after 48 h)
12 h)
Table 2 Bismuth molybdate catalysts with pure phases (a, b, c) used in the production of 1,3-butadiene via the oxidative dehydrogenation process

Oxygen mobility, oxygen capacity

Oxygen mobility, oxygen capacity

Synergetic effect

Synergetic effect
Oxygen mobility

Oxygen mobility

Fig. 3 TPRO profiles of BiFe0.65NixMo oxide catalyst with different

Propertya

Ni composition: a x = 0, b 0.05, c 0.10, d 0.15, and e 0.20 [37]

Oxygen mobility and capacity are readily characterized

Calcination temperature (425–675 C)

by the temperature-programmed re-oxidation (TPRO)

Reaction temperature and steam ratio

measurement [44, 50, 51]. In order to analyze the oxygen

mobility, the conversion of 1-butene to BD is carried out in
the absence of oxygen feed prior to a TPRO experiment.
From the TPRO measurement, two kinds of oxidation
X conversion of n-butene, S selectivity for 1,3-butadiene, Y yield for 1,3-butadiene

peaks were usually observed as shown in Fig. 3. In Fig. 3,

b ? c mixed phase

a ? c mixed phase
Reaction pH (1–7)

Crystalline phase

the first peak in the 100–250 C range is from oxidation of

Experimental

the partially reduced bismuth oxide [37]. At this point, the

peak position indicates that the temperature at which the
variables

oxygen vacancy is recovered is closely related to the

oxygen mobility during the re-oxidation step. A lower peak
temperature reflects a higher oxygen mobility of the cata-
temperature (C)

lyst. Meanwhile, the oxygen capacity can be computed via

the peak area obtained during a TPRO measurement, or it
Reaction

320–420

can be directly measured by integrating the peak area

380-460

obtained from the ODH reaction of 1-butene in the absence

420

420

420

420

Parameters influencing catalyst performance

of oxygen feed. The oxygen mobility of metal oxide cat-

alysts can also be measured using various analytical tools
a-Bi2Mo3O12, b-Bi2Mo2O9, c-Bi2MoO6

such as 18O/16O isotope exchange [24, 52], H2-tempera-

ture-programmed reduction (TPR) [53], O2-temperature-
programmed desorption (TPD) [24, 54], and X-ray photo-
electron spectroscopy measurements [39, 55]. Although
a-Bi2Mo3O12, c-Bi2MoO6

a-Bi2Mo3O12, c-Bi2MoO6
b-Bi2Mo2O9, c-Bi2MoO6

there are multiple variables influencing catalyst perfor-

mance, most of them affect the oxygen mobility and
capacity. The correlation between catalyst activity and
oxygen properties have been established previously, as
c-Bi2MoO6

c-Bi2MoO6

shown in Table 2 and Fig. 4. For example, Jung et al. [44]

Catalyst

have synthesized bismuth molybdates with different crys-

talline phases (a, b, and c) as an experimental variable, and
b
a

123
28
Fig. 4 Correlation between catalyst performance and oxygen properties (mobility and apacity): a, b in [44]. c in [50], and d in [51]
these different phases led to an observed difference in
oxygen mobility. Evidently, catalyst activity increases with
respect to an increasing oxygen mobility as shown in
Fig. 4a, b. In other cases [50, 51], catalyst performance is
also associated with oxygen capacity (TPRO peak area), as
well as oxygen mobility (TPRO peak temperature) as
shown in Fig. 4c, d.
In order to surpass the catalytic performance of pure
bismuth molybdates (a, b, and c phases), multicomponent
bismuth molybdate catalysts, with additional metal com-
ponents apart from bismuth and molybdenum, have been
widely studied (Table 3). Different metal components have
been used for the Bi-Mo-Metal oxide system, such as V
[2], La [53], Zr [35], and Fe [56]; with these Bi-Mo-Metal
oxide catalysts exhibiting higher catalytic activity than
pure bismuth molybdate catalysts. It is well known that an
appropriate amount of added metal (as a promoter)
improves the catalyst performance through the enhance-
ment of redox property, oxygen mobility, and other func-
tionalities [53, 57, 58]. Although oxygen properties also
play a crucial role in multicomponent bismuth molybdates,
the catalytic performance of a multicomponent system is
associated with more complicated parameters, such as
123
E. Hong et al.
adsorption ability, surface acidity, and the formation of
metal molybdates (Table 3; Fig. 5).
Other multicomponent systems are commonly com-
posed of four essential components: divalent metal (MII),
trivalent metal (MIII), bismuth, and molybdenum. It could
be expressed in the general form of MIIa MIIb BicModOe [38].
In this multicomponent structure, active bismuth molyb-
date phases are located at the catalyst surface, whereas the
divalent and trivalent metal molybdates disproportionately
exist in the catalyst bulk as supports. Jung et al. proposed a
representative particle model of the Co–Fe–Bi–Mo–O
catalyst, and it clearly indicates that MIIMoO4 and MIII 2 (-
MoO4)3 are located in the bulk of the catalyst, while the
bismuth molybdate phase is on the surface [32]. The
divalent and trivalent metal components in the bulk support
the migration of active oxygen species to the surface (i.e.,
the bismuth molybdate phase), leading to an enhanced
oxygen mobility [62, 63]. Jung et al. [39] have previously
synthesized the CoxNi9-xFe3Bi1Mo12O51 catalysts
(x = 1–8) to investigate the effect of two divalent metal
components. However, none of the prepared CoxNi9-x-
Fe3Bi1Mo12O51 catalysts showed a superior catalytic
activity compared to the Co9Fe3Bi1Mo12O51 catalyst.
 Table 3 Multicomponent bismuth molybdates with various metal promoters for the production of 1,3-butadiene via the oxidative dehydrogenation reaction
Catalyst MIIa MIIIb Experimental variable Propertyc Reaction Activity (%)d (reaction time) Ref.
temperature
(C)

BiMoZrx oxide Zr Zr content (x = 0–0.5) Oxygen mobility 440 Y & 68 with BiMoZr0.4 (after 2 h) [35]
BiVxMo1-x oxide V V/Mo ratio (x = 0–1.00) Oxygen mobility, oxygen capacity, 420 X = 72.2, Y = 64 with BiV0.6Mo0.4 (after 8 h) [2]
adsorption ability
BiMoLax La La content (x = 0–0.4) Oxygen mobility, adsorption ability 440 X = 74.6, Y = 71.2 with BiMoLa0.2 (after [53]
100 h)
BiMoFex oxide Fe Fe content (x = 0–1.00) Oxygen mobility, coexistence of 420 X = 68.6, S = 91.4, Y = 62.7 with BiMoFe0.65 [56]
Bi3Mo2FeO12 and Fe2(MoO4)3 (after 6 h)
NixFe3Bi1Mo12O42?x Ni Fe Ni content (x = 2–10) Oxygen mobility, surface acidity 420 X & 59, Y = 53.0 with Ni9Fe3Bi1Mo12O51 [38]
(after 6 h)
Co9Fe3Bi1Mo12O51 Co Fe Compared to c-Bi2MoO6 Oxygen mobility, surface acidity 420 X & 56, S & 93 (after 6 h) [59]
Co9Fe3Bi1Mo12O51 Co Fe Reactant (1-butene, 2-butene, and their Selective oxygen species in catalyst 420 1-butene [ mixture [ 2-butene (after 6 h) [60]
mixture)
Co9Fe3Bi1Mo12O51 Co Fe Calcination temperatures (475–675 C) Oxygen mobility, formation of the 420 X & 66.5, S & 90 calcined at 475 C (after 6 h) [55]
b-CoMoO4 phase
MII9 Fe3Bi1Mo12O51 MII Fe MII component (MII = Mg, Mn, Co, Oxygen mobility 420 Co [ Ni [ Mn & Mg [ Zn (after 6 h) [39]
Ni, and Zn)
BiFe0.65NixMo oxide Ni Fe Ni content (x = 0–0.2) Oxygen mobility 420 X = 86.4, Y = 77.1 with BiFe0.65Ni0.05Mo (after [37]
100 h)
Co9Fe3Bi1Mo12O51 Co Fe Steam to n-butene ratio/reaction Reaction conditions 380-460 Maximum at 15/420 C/675 h-1 [32]
temperature/gas hourly space
Oxidative Dehydrogenation of n-Butenes to 1,3-Butadiene over Bismuth Molybdate and Ferrite…

velocity
Bi–Fe–Me–Mo oxide Me Fe Me component (Me = Ni, Co, Zn, Mn, Oxygen mobility 420 Ni [ Co [ Zn [ Mn [ Cu X = 85.7, S = 83.8, [61]
and Cu) Y = 71.8 with BiFe0.65Ni0.05Mo (after 14 h)
a
Divalent metal
b
Trivalent metal
c
Parameters influencing catalyst performance
d
X conversion of n-butene, S selectivity for 1,3-butadiene, Y yield for 1,3-butadiene
29

123
30
Fig. 5 Parameters influencing the catalyst performance of multicomponent bismuth molybdate: oxygen mobility (a in [56], b in [2]), surface
acidity (c in [38]), and phase composition (d in [55])
Although multicomponent bismuth molybdates composed
of five metal components, Co–Mo–Bi–Fe–Sb–K oxide [64,
65], have been studied for the partial oxidation of propy-
lene, they have not been used for the production of BD via
an ODH reaction.
Owing to their excellent catalytic activity, multicom-
ponent bismuth molybdate catalysts are widely used in
various areas, such as the selective oxidation of propane
[57] and propanol [58]. Although bismuth molybdates are
the most widely used catalysts in the production of BD via
ODH, other metal oxide catalysts have been also
investigated.
Iron-based catalysts (ferrites) are considered as one of
the most effective catalysts for the ODH of n-butene. The
major difference between the bismuth molybdate and fer-
rite catalysts lies in the catalytic reaction pathway, which is
influenced by their respective crystalline structures. It is
well known that ferrite catalysts have a spinel structure,
which is a cubic crystal system with the chemical formula
123
E. Hong et al.
of A2?B23?O42-. In this crystalline system, the oxide is
arranged in a cubic lattice, with the cations A and B
occupying some or all of the tetrahedral and octahedral
sites within the lattice. According to the positions of the
divalent and trivalent metal cations, the spinel structure can
be categorized into three groups: (a) a normal type spinel
structure, in which the divalent cations are located in
tetrahedral sites and the trivalent cations are in octahedral
sites, (b) an inverse spinel type structure, in which the
divalent cations are located in octahedral sites, and the
trivalent cations are in both tetrahedral and octahedral sites,
and (c) a random spinel type structure, where the divalent
and trivalent cations are located in both octahedral and
tetrahedral sites.
The reaction pathway of the ferrite catalysts, which
includes a redox cycle, was proposed by Gibson and
Hightower [66, 67] (Fig. 6). According to this mechanism,
hydrogen abstraction occurs via two consecutive steps. The
first step is a homolytic cleavage to produce the C4H8 allyl
Oxidative Dehydrogenation of n-Butenes to 1,3-Butadiene over Bismuth Molybdate and Ferrite…
Fig. 6 Proposed mechanism for
the oxidative dehydrogenation
of butenes over ferrite catalysts
to butadiene [67]
intermediate (p-bonded to the Fe3? ion), and the OH-
group. The second step is a heterolytic cleavage, where a
H? attaches to the lattice O2- species and leaves the
C4H6-–Fe3? complex. This complex is divided into Fe2?,
from the reduction of Fe3? to Fe2?, and BD. In this reac-
tion pathway, the initial abstraction of the a-hydrogen from
n-butene to form the p-allyl intermediate is considered as
the rate-determining step in the ODH of n-butene. This
means that the abstraction of the a-hydrogen from n-butene
is significantly influenced by the acid properties of the
catalyst [68]. For example, Lee et al. [68–70] have reported
that although the catalytic performance of ZnFe2O4 is not
directly correlated to its total acidity and acid strength, its
surface acidity (total acidity/surface area) is closely related
to the catalyst performance.
Many studies have revealed that the selectivity of the
ferrite catalysts depends on their crystallographic structure
(c-Fe2O3 [ a-Fe2O3, [71]), specific surface area [72],
crystal size [73, 74], and metal–oxygen bond strength [75].
In addition, it has been reported [76] that the addition of
foreign cations into the spinel structure of ferrites modifies
the electronic properties of the catalytic system. Thus, such
modifications have been widely attempted to improve the
catalytic activity of ferrite catalysts such as CuFe2O4 [77],
CoFe2O4 [77], MgFe2O4 [30, 66], MgCrFe2O4 [30],
ZnFe2O4 [78, 79], ZnAlFe2O4 [76, 78], and MnFe2O4 [68].
Among these different metal ferrite catalysts, ZnFe2O4 has
received a great deal of interest because it has a high
density of selective oxidation sites but a low density of
combustion sites [26, 80], leading to the high catalytic
activity observed in the ODH of n-butene. Lee et al. [68]
studied the ODH of n-butene to BD over the MeIIFe2O4
31
catalyst with different transition metals (MeII = Zn, Mg,
Mn, Ni, Co, and Cu). The catalytic activities of metal
ferrites increase in the following order, with respect to an
increasing surface acidity: CuFe2O4 \ CoFe2O4 \ NiFe2-
O4 \ MnFe2O4 \ MgFe2O4 \ ZnFe2O4. Nonetheless, the
ferrite catalysts suffer from catalytic deactivation due to the
irreversible reduction of Fe3? to Fe2?. In order to suppress
this unfavorable reduction reaction, experimental measures
such as the addition of phosphorous [81] and the use of
mixed catalysts [82] have been tried. The use of ferrite
catalysts under different reaction conditions is summarized
in Table 4.
For the production of BD, both bismuth molybdates and
ferrite-based catalysts mainly function in the temperature
range of 400–500 C. However, Golunski et al. [27] have
used Pd metal-promoted Fe2O3 catalyst for an ODH reac-
tion that was performed at 150 C. Although the catalyst is
rapidly deactivated at this temperature, it is well worthy
enough to develop better catalysts that can operate at rel-
atively low temperatures. Jung et al. [84] have applied
ZnFe2O4 and Co9Fe3Bi1Mo12O51 catalysts to a dual-bed
reaction system in order to measure the synergetic effect of
these two catalysts. This system can promote the reaction
of n-butene isomers, composed of 1-butene, trans-2-
butene, and cis-2-butene, because reactant activity is
dependent on the type of catalyst used.
Although a large number of research papers have been
published on the ODH reaction of n-butene to BD, further
studies should be carried out to obtain more robust results
in terms of using different catalyst materials, their syner-
getic effect, as well as long-term stability. Potential can-
didates that have been investigated for the ODH reaction of
123
32 E. Hong et al.

Table 4 Ferrite catalysts for the production of 1,3-butadiene via the oxidative dehydrogenation reaction
Catalyst Experimental variable Reaction Activity (%)a (reaction time) Ref.
temperature
(C)

ZrFe2-xAlxO4 Fe, Al content (0.0 \ x \ 1.0), 420 X = 55, Y = 36 with ZrFe1Al1O4 calcined at 750 C [76]
Calcination temperature (550, 750 C) (after 1 h)
MeIIFe2O4 MeII = Zn, Mg, Mn, Ni, Co, and Cu 420 Zn [ Mg [ Mn [ Ni [ Co [ Cu/ X & 71, Y = 67.8 [68]
with ZnFe2O4 (after 6 h)
ZnFe2O4 Addition of phosphorous compound, 500 ZnFe2O4 with 1.5 wt% H3PO4; X = 78, S = 91.7, [81]
oxygen to n-butene ratio (feed) Y = 71.5 (after 450 h)
ZnFe2O4 Addition of cesium-exchanged 420 X & 81, Y = 79.1 with ZnFe2O4-Cs2.5H0.5PW12O40 [82]
heteropolyacid (HPA), pretreatment (after 6 h)
temperature
ZnFe2O4 pH value in the co-precipitation method 420 X & 86, Y = 80.2 at pH 9 (after 6 h) [69]
(3–12)
ZnFe2O4 pH value in the co-precipitation method 420 X & 83, Y = 78.9 at pH 8 (after 6 h) [70]
(6-12) using aqueous buffer solution
MgFe2O4, Chromium substitution, the effect of 300–450 MgFe1.8Cr0.2O4 with steam; X = 60, S = 87 at 450 C [30]
MgFe1.8Cr0.2O4 steam, reaction temperatures (not indicated)
ZnCrxFe2-xO4 Addition of chromium, the effect of pre- 325–400 X = 71, Y = 58 with ZnCr0.25Fe1.75O4 at 400 C/ [83]
MgCrxFe2-xO4 reduction, reaction temperature X = 64, Y = 58 with MgCr1Fe1O4 at 325 C (not
indicated)
a
X conversion of n-butene, S selectivity for 1,3-butadiene, Y yield for 1,3-butadiene

n-butane include phosphorus- [85, 86] and vanadium-based
[87–89] catalysts (with vanadium-magnesium oxide-based
catalyst studied for the ODH reaction of n-butene, [90]). As
the catalytic activities of existing catalysts are relatively
low, developing a new and efficient catalyst for the pro-
duction of BD is a worthy challenge.
5 Conclusions
In this study, we have summarized the experimental vari-
ables and reaction conditions used in the production of BD
via an ODH reaction utilizing bismuth molybdates and
ferrites as catalysts. BD is effectively produced by an ODH
reaction over heterogeneous metal oxide catalysts such as
bismuth molybdate and ferrite. The lattice oxygen and its
properties (mobility and capacity) in metal oxide catalysts
are crucial factors that determine catalyst performance as
an ODH reaction follows the MvK mechanism. In a pure
phase bismuth molybdate, only oxygen properties influence
the catalyst performance. However, the catalyst activity in
a multicomponent bismuth molybdate is associated with
more complex parameters, such as adsorption ability and
the formation of the metal molybdate phase as Bi-Mo-Me
with a single metal promoter and MIIMIIIBiMo with two
metal promoters. In ferrite catalysts, the abstraction of the
a-hydrogen from n-butene to form the allyl intermediate is
a rate-determining step, which is closely related to surface
acidity. In addition, metal ferrite catalysts have also been
studied because the addition of foreign cations into the
crystalline structure of ferrite can modify the catalyst’s
properties. Among the various metal ferrite catalysts,
ZnFe2O4 shows the highest activity because it has a high
density of selective oxidation sites but a low density of
combustion sites. In order to facilitate the preparation of
better catalysts to be used in an ODH reaction, it is nec-
essary to understand their distinct reaction mechanism,
identify the most appropriate catalyst compositions, and
correctly control the reaction conditions.
Acknowledgments This work was supported by the Energy Effi-
ciency and Resources of the Korea Institute of Energy Technology
Evaluation and Planning (KETEP) granted financial resource from the
Ministry of Trade, Industry and Energy, Republic of Korea (No.
2014021194).
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