Catalysis Today 127 (2007) 113–131

www.elsevier.com/locate/cattod

Oxidative dehydrogenation of ethane and propane: How far from

commercial implementation?
F. Cavani *, N. Ballarini, A. Cericola
Dipartimento di Chimica Industriale e dei Materiali, Alma Mater Studiorum Università di Bologna, Viale Risorgimento 4, 40136 Bologna, Italy1

Available online 2 July 2007

Abstract
This review examines the recent literature on the oxidative dehydrogenation (ODH) of ethane and propane, which aims for the synthesis of the
corresponding alkenes. The following aspects are discussed: (a) the main features affecting the catalytic properties of systems based on supported
vanadium oxide and molybdenum oxide; (b) the characteristics of catalysts producing outstanding olefin yields; (c) advantages in selectivity gained
by means of either special reactor configurations or non-conventional conduction of the reaction; (d) the contribution of homogeneous reactions to
the formation of olefins during the oxidation of alkanes.
# 2007 Elsevier B.V. All rights reserved.

Keywords: Oxidative dehydrogenation; Olefins production; Propane; Ethane; Reactor configurations

1. Introduction In fact, the production of chemicals starting from alkanes –

The demand for olefins, especially ethylene and propylene, is
expected to increase significantly in the near future. At the
present time, the main sources of olefins are: steam cracking,
fluid-catalytic-cracking, and catalytic dehydrogenation.
Although these processes are widely used, an intense research
activity is taking place to develop catalysts for the oxidative
dehydrogenation (ODH) of alkanes, due to the following reasons:
1. In steam cracking, ethylene is the preferred product, but the
demand for propylene is growing faster than that for
ethylene, especially in Western Europe [1]. Also, in the case
of FCC, smaller amounts of propylene are produced.
Therefore, the current production of olefins is not in line
with the forecast market demand for olefins.
2. Dehydrogenation’s thermodynamic constraints limit alkane
conversion; furthermore, a major problem is coking, which
causes rapid catalyst deactivation.
Therefore, the need exists for new technologies devoted to
the production of specific olefins, which have none of the
disadvantages characterizing dehydrogenation.
* Corresponding author. Tel.: +39 0512093680; fax: +39 0512093680.
E-mail address: fabrizio.cavani@unibo.it (F. Cavani).
1
INSTM, Research Unit of Bologna. A partner of NoE Idecat, FP6 of the EU.
0920-5861/$ – see front matter # 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.cattod.2007.05.009
by means of oxidative processes – has been one of the most
studied topics in recent decades. As pointed out by Brazdil [2]:
‘‘The direct conversion of ethane and propane to commodity
chemical intermediates has the potential to radically transform
the chemical industry. The effectiveness of the catalyst, that is
the activity for alkane conversion and the selectivity to desired
products, will ultimately determine the economic attractiveness
of an alkane-based chemical process. The successful commer-
cial technologies will be those that link catalyst performance
characteristics with innovative process designs’’. However, in
the case of alkenes produced from alkanes, the lower cost of the
feedstock is not a real incentive, since current commercial
technologies for olefin production already use fuel-grade
feedstocks. In this case, conversely, the improved energy
efficiency (ODH is exothermal, while dehydrogenation and
cracking are endothermal), and process simplicity are effective
incentives. This implies that – while in the production of, say,
acrylonitrile from propane – a yield of 60% is sufficient to
obtain a cost equivalency with the current technology from
propylene (due to the difference in cost between propane and
propylene), in the case of propylene synthesis by propane ODH,
better olefin yields are needed than those obtained with current
technologies. In other words, the potential advantages offered
by ODH are not enough to convince companies to abandon
well-established technologies, carried out in completely
depreciated, highly reliable, and efficient plants, unless a
114 F. Cavani et al. / Catalysis Today 127 (2007) 113–131
better yield than that currently achieved can be obtained.
Furthermore, Lange [3] underlined that more exothermal
reactions imply higher ‘‘energy losses’’ (i.e., the difference
between the combustion heat of feed and that of the product)
and, hence, higher fixed costs, especially if the production of
CO2, the main by-product in alkane ODH, is taken into account.
A large number of reviews dealing with the ODH of light
alkanes have been published since the early 1990s [4–21]. In
the present review, we attempt to offer an answer to the
following questions on the scientific and technological aspects
of ethane and propane ODH:
Which key factors are the chief determinants of the
performance of metal oxide-based catalysts?
Have research efforts led to catalysts that can oxidize
alkanes to olefins with yields comparable to those obtained with
current technologies for alkenes production?
Does the use of either peculiar reactor configurations (e.g.,
membrane-type reactors) or non-conventional methods for the
conduction of reactions (e.g., cyclic feeding of reactants) make
it possible to improve performances as compared to the
traditional configurations?
Indeed, it is quite difficult to obtain a uniform picture
concerning those significant catalyst characteristics that
determine the performance in alkane ODH, due to the
following reasons:
1. The majority of papers focus on some specific aspects that
may affect the reactivity of the catalysts investigated. For
instance, in the case of supported metal oxide catalysts, in
addition to the usual morphological aspects, some of the
important features affecting the performance are: the degree
of agglomeration of Me cations (from isolated units to bulk
Me oxide); acid–base characteristics; the valence state of the
metal cation under reaction conditions; the collective
electronic properties of the solid. Some of these features
may also be significant for bulk metal oxides, with the
additional role played by structural defects, degree of
crystallinity, etc. Experimental evidence is often provided to
indicate that each of the above-mentioned aspects is the
crucial one, and the reader may sometimes have the
impression that the crucial factor may be any one of them,
depending on what the investigator is looking for. Obviously,
a collective interpretation is missing, which would be
capable of bringing all these aspects together and outlining a
general picture.
2. It is also apparent that contradictory information derives
from different experimental conditions, not so much
regarding the procedure used for catalyst preparation and
thermal treatment, as the conditions for catalytic tests. The
latter may vary greatly, and key operative parameters are not
only the reaction temperature, pressure and contact time, but
also the feed ratio between oxygen and alkane. Very often
oxygen-lean conditions are used, in order to obtain better
selectivity to the olefin; this, however, implies that total
oxygen conversion is reached and that, depending on the
temperature, reactions leading to the formation of H2 may
become significant (see Section 8). Therefore, the redox
properties of the gas phase (either reducing or oxidizing)
with regard to the metal cations are greatly affected by these
operative parameters. This not only generates a dynamic
situation with in situ modification of the active surface, but
may also have implications on the reaction mechanism, even
with a change in the rate-determining step of the reaction.
Furthermore, this may affect the gas-phase concentration of
by-products and co-products (e.g., CO2 and H2O), the
presence of which may substantially alter the nature of the
cation oxidation state, degree of agglomeration, and type of
interaction with the support. This implies that reaction
conditions may affect the nature of the catalyst character-
istics. This problem may be overcome in part by studying
catalyst characteristics under working conditions (in situ
reactivity) and, even more so, by coupling this with a
concomitant analysis of the reaction products. Over the past
10 years, the effort made by many groups to develop such
experimental techniques is worth mentioning [22–33]. Thus,
the study of the dynamic changes introduced in the catalyst
as a consequence of reaction conditions was made possible.
Nevertheless, sometimes the thorough characterization of
the catalyst downloaded post-catalytic tests (the ‘‘spent’’
catalyst) and the comparison of ante-reaction features may
be sufficient to understand whether significant changes in
catalyst characteristics occurred during catalytic tests.
For reasons of brevity, this review does not discuss the
literature published on the ODH of alkanes when carried out
with oxidants other than O2. Indeed, the use of less
conventional oxidants, i.e., N2O [34] and CO2, may lead to
significant breakthroughs in this field, due to the possibility of
either generating peculiar O species with specific reactivity to
the hydrocarbon, or carrying out an in situ control on the active
phase properties.
In general, two different approaches for the ODH of light
alkanes with O2 are used:
(a) The combination of exothermal alkane combustion with the
endothermal dehydrogenation, at temperatures higher than
700 8C. The use of O2 enables to overcome thermodynamic
limitations and to avoid catalyst regeneration.
(b) A true ODH occurring with redox-type catalysts already at
temperatures lower than 500 8C. Amongst the catalysts
used, the most investigated ones are those based either on
vanadium oxide or on molybdenum oxide.
2. A classical system for alkane ODH: supported
vanadium oxide
A great number of papers deal with the study of the catalytic
properties of vanadium oxide-based catalysts in propane and
ethane ODH. Below is a brief summary of some significant
points, over which the scientific community seems to find
general agreement; some controversial points are also
mentioned. Although it cannot be stated that this is the
definitive picture of supported vanadium oxide catalysts,
nevertheless these points represent a good starting point for
 F. Cavani et al. / Catalysis Today 127 (2007) 113–131
both scientific debate and a deeper comprehension of this
important class of ODH catalysts.
Some significant points concerning the reactivity of these
systems are:
1. In propane ODH, the catalytic activity of vanadium oxide
catalysts increases with the V2O5 loading, while rates per V-
atom reach a maximum on VOx domains of intermediate
size, providing a balance between the activity of surface VOx
species and their accessibility to reactants. The selectivity to
the corresponding olefins shows a peak for intermediate
values of active phase loading, which corresponds to the
development of the monolayer structure. In fact, the olefin
formation rate (per V atom) is influenced by vanadia surface
density and reaches its peak value at intermediate surface
densities [35–38]. The initial selectivity ratio is affected by
the surface density of active sites, thus suggesting that
isolated structures prevailing at low surface densities are
more selective for propane ODH [36,37,39]. Isolated sites
are beneficial for propylene selectivity, but they do not
completely cover the support surface, on which the
hydrocarbons can be adsorbed and further oxidized to
COx. A high selectivity to propylene can be achieved by fully
covering the support with well-dispersed vanadia species;
however, polymeric V species can be conducive to
consecutive propylene combustion reactions [40]. Small
V2O5 crystallites above single-layer surface vanadia cover-
age do not contribute to propane ODH because of their low
dispersion and small number of active surface sites. It has
also been reported that, in the case of propane ODH, the
apparent activation energy for propylene combustion is
lower than that for alkene formation and the difference
between these two activation energies decreases with
increasing surface density [35–37]. This is due to the fact
that the C–H bond energy in propylene allylic C atom is
weaker than the C–H bond in the sec-C atom of propane, and
the corresponding activation energy is also lower. Thus, for
low reaction temperatures, the consecutive oxidative attack
on propylene has an advantage over the direct activation of
propane. Therefore, the highest selectivity of alkene is
obtained for catalysts containing predominantly isolated
monovanadate species and operating at high temperatures
that however avoid homogeneous reactions (e.g., lower than
550 8C) [28,36]. The same conclusion was reported by other
authors, for reactivity tests performed in a multi-channel
microreactor and with a V2O5-Al2O3 catalyst deposited on
the reactor wall [41]. Above 500–550 8C, additional
contributions to propylene formation may derive from the
contribution of homogeneous reactions and of catalytic
dehydrogenation as well, especially when operation is
carried out under oxygen-lean conditions.
In contrast with the above-mentioned findings, the results
obtained by Lemonidou and co-workers [27] showed that in
titania and zirconia-supported vanadium oxide, the ability of
vanadium to activate the C–H bond in propane weakens when
increasing VOx density. Other authors found no significant
variations in TOF with V2O5 content in zirconia-supported
115
vanadium oxide [25]. It was suggested that these discrepancies
might be due to differences in the molecular structure of
surface vanadia species, the latter being a function of the
operational conditions (i.e., propane/oxygen feed ratio) [27].
2. For both propane and ethane, reactivity data for catalysts
made of supported vanadium oxide are consistent both with
kinetically relevant steps involving the dissociation of C–H
bonds (methylenic C atom in propane) and with a Mars-van
Krevelen redox mechanism involving lattice oxygen in C–H
bond activation. The resulting alkyl species desorb as olefin
and the remaining O–H group recombines with neighboring
O–H groups in order to form water and reduced V centers;
the latter are re-oxidized by irreversible dissociative
chemisorption of O2. Surface oxygen, O–H groups and,
especially, oxygen vacancies are the most abundant reactive
intermediates during ODH on active VOx domains [42–44].
The contribution to COx formation, conversely, mainly
derives from adsorbed O species, at least in ethane ODH
[45].
3. The extent of V reduction during steady-state ODH is much
lower than for stoichiometric reduction of V5+ to V4+ or V3+
[22–25,28,46]. Furthermore, only a fraction of the reduced
centers are active in catalytic turnovers, while the rest are re-
oxidized in time scales much longer than turnover times. The
number of catalytically significant reduced centers depends
only on alkane/O2 ratios. The fraction of V-atoms that exist
as catalytically reduced centers increases with increasing
vanadia surface density and domain size up to surface
densities typical of polyvanadate monolayers, and then
reaches nearly constant values at higher surface densities;
therefore, both isolated and polymeric species are active, but
polymerized surface VO4 species are more extensively
reduced than the isolated species during steady-state alkane
oxidation. The selectivity to propylene formation is affected
by surface reduction: the higher the surface reduction, the
higher the selectivity [47]. The use of N2O to replace O2
causes the development of a more reduced, and more
selective, surface [40,48,49]. The extent of reduction of the
surface V5+ species also depends on the specific oxide
support: V2O5-ZrO2 > V2O5-Al2O3 > V2O5-SiO2; the reac-
tivity, TOF, in ethane ODH follows the same ranking [23,24].
4. ODH turnover rates increase as the energy of the absorption
edge in the UV–visible DR spectrum decreases; the
electronic transitions responsible for the absorption edge
have been found to be mechanistically related to the redox
cycles involving lattice oxygens responsible for ODH
turnovers of alkanes. The stability of activated complexes
in C–H bond dissociation steps depends on the ability of the
active oxide domains to transfer electrons from lattice
oxygen atoms to metal centers [50].
5. The role of the support on the reactivity of vanadium oxide in
alkane ODH has been investigated by many authors
[27,37,46,47,51–75]. In general, in propane ODH catalysts
made of V oxide supported on silica are more selective than
those made with the alumina support, and the latter are more
selective than those supported on titania, mainly because of
the lower extent of parallel propane combustion, especially
116 F. Cavani et al. / Catalysis Today 127 (2007) 113–131
at low vanadia loading [51,52,59,61]. However, in this case,
also, there are several contrasting indications in literature,
and this is likely to be due to the different characteristics of
the supports used and the different nature of the active
species developed. With a silica support, one major problem
is the hydrolysis of the Si–O–V bond in the reaction
environment, with a development of segregated vanadium
oxide. Interactions with supports determine the type of VOx
structures present at a given surface density, but apparently
turnover rates do not depend on the identity of the support
when differences in VOx structure are taken into account.
Therefore, the relative rates of ODH to form propylene and
of secondary propylene oxidation to COx do not depend on
the identity of the support or on VOx surface density or
structure [37]. Conversely, Wachs and co-workers [53–55]
found that in propane ODH, turnover frequency (TOF)
values vary by more than an order of magnitude with the
specific oxide support for both the isolated and polymeric
surface VOx species. Therefore, the support may have a
significant effect on the reaction parameters for the oxidative
dehydrogenation of propane on supported vanadium oxide
catalysts [60], because the support cation is a ligand that
directly influences the reactivity of the bridging V–O-
support bond, and the catalytic active site, by controlling its
basic character with the support electronegativity [53].
Evidence has been reported indicating that the O atom
bridging V to the support may be the one participating in the
catalytic cycle in isolated V species [27,47,54–56,60,76].
For instance, concurrent trends have been reported of the
activity per active site and the number of anchoring bonds
per site as a function of the surface density [76]. An inverse
trend was found between the steady-state catalytic TOF and
the support electronegativity for methanol oxidation over
supported vanadium oxide-based catalysts [57]. The same
was found in alkanes ODH [56]; the more electronegative
supports lead to higher activity, because the higher the
difference between the electronegativity of active metal
cations or support cations with oxygen, the stronger the bond
[58].
6. The reduction and catalytic properties of active VOx domains
can be significantly affected by the formation of binary
dispersed structures. For example, VOx-CrOx and VOx-MoOx
mixed structures lead to a higher propane ODH rate and
selectivity than VOx domains present at similar surface
densities on pure Al2O3 supports [26,77–79]. The formation of
V–O–Cr and V–O–Mo bonds occurs above Mo + V mono-
layer coverages [80]. In titania-supported vanadium oxide, the
increased selectivity is ascribed to the easier desorption of
propylene from the less acidic surface, thus preventing the
consecutive total combustion of propylene. The selectivity to
propylene can be also correlated with the work function values
which decrease in the series: VWTi > VTi > VFe-
Ti > VAlTi > VCaTi [81]. This implies that the lower the
surface energy barrier for transfer of electrons from the
catalyst to the reacting molecules is, the higher the selectivity
is to the partial oxidation product. It is argued that owing to the
decrease in this energy barrier the re-oxidation step in the
catalytic reaction is fast, thus preventing the presence of
intermediate non-selective electrophilic oxygen species on the
surface [81]. The relatively inert secondary surface metal
oxide additives (MoOx and WOx) are able to weakly adsorb
propane in a precursor state that supplies the catalytic active
VOx sites for propane activation to propylene, while the
surface CrOx modifier has greater intrinsic activity for propane
activation than the surface VOx sites [82]. With different metal
oxides, turnover rates reflect C–H bond cleavage activation
energies which, in turn, are influenced by the reducibility of
these metal oxides. The relative propane ODH and propylene
combustion rates depend not only on C–H bond energy
differences but also on the adsorption enthalpies for propylene
and propane, which reflect the Lewis acidity of cations
involved in the bonding of molecules on oxide surfaces. For
instance, the observed difference in activation energies
between propane ODH and propylene combustion increases
as the Lewis acidity of the cations increases
(V5+ < Mo6+ < W6+) [83].
7. Additives (e.g., P, K, Ca, Ni, Cr, Nb, Mg, Au, Zn and Mo),
sometimes added in relevant amount with respect to V,
modify acid–basic and redox properties of supported
vanadium oxide [38,59,84–92]. Modification of these
properties affects catalytic performance in ODH; in samples
where an increase of the concentration of acid sites is
observed (due to the increase in the electronegativity of the
additive ions), the total activity increases [84–88]. The
addition of alkali and alkaline earth dopants decreases the
activity and increases the selectivity to propylene in propane
ODH [59,88]. The order of the increasing selectivities to
propylene in propane ODH follows the order of the
increasing basicity and the increasing M–O bond energy.
On the contrary, selectivity to ethylene in the ODH of ethane
does not depend on the acidic properties or on the M–O bond
strength [84–87]. Also, the basicity of the support may
greatly affect selectivity [62]; it is thought that the use of a
basic metal oxide support results in improved selectivity
because of the possible rapid desorption of the electron-rich
propylene product before further combustion to COx. For
instance, the addition of MgO to Al2O3 [88] or the use of
MgAl2O4 [89] as supports for vanadium oxide positively
affect the selectivity to propylene [38].
3. Vanadium incorporated in hosting structures
A key factor in the design of efficient catalysts for alkane
ODH is the isolation of active sites [7,11,93]. Therefore, the
isomorphous substitution of active metal species, e.g.,
vanadium, into microporous and mesoporous materials is an
attractive strategy for designing new catalysts for this reaction
[9,94–105]. The main drawback of these systems is that they do
not always maintain the structure if high V contents are
incorporated; furthermore, the incorporated V species may
sometimes be easily withdrawn from the structure during the
reaction. In many cases, site isolation has been achieved by
simply depositing the active phase by impregnation over these
high-surface-area supports.
 F. Cavani et al. / Catalysis Today 127 (2007) 113–131
Examples include V-containing high-surface siliceous
materials, such as MCM-41 [49,100,106–111], MCM-48
[112] or SBA-15 [112–115]. In these systems, the catalytic
activity of vanadium is strongly influenced by its local
environment and the co-existence of acid sites in the host
material. An inert matrix seems to be required in order to
achieve high selectivities in the ODH of propane [96,97], while
acid materials are preferred for the ODH of ethane [101–105].
In the case of VCoAPO-18, the presence of both acid sites
(related to the presence of Co2+ cations) and redox sites (related
to the presence of V5+/4+ and Co3+/2+) seems to be an important
factor in achieving high selectivities to ethylene during the
ODH of ethane [116]. An outstanding value of ethylene
productivity, close to10 kg olefin per kg of catalyst per hour, has
been reported for a VOx-MCM-48 catalyst containing 2.8 wt.%
vanadium oxide [117].
One of the best performing catalysts in propane ODH is the
VOx-SBA-15 system [113,115], prepared by an alcoholic
impregnation method, in which the introduction of V species
onto the inner walls of SBA-15 provides a system with a large
concentration of accessible, isolated and structurally well-
defined active sites. Vanadium species anchored to the surface
showed structural properties similar to those on mesoporous
VOx-MCM and conventional V2O5–SiO2 catalysts, but a higher
surface concentration of isolated or low polymeric VOx species
could be achieved with the VOx-SBA-15 system. Moreover, the
authors hypothesized that the large pore diameter of the
material might favor the diffusion of propylene outside of the
pores, thus preventing deep oxidation.
4. Supported molybdenum oxide
There are many analogies between catalysts based on
supported vanadium oxide and those based on supported
molybdenum oxide [56,80,118–132] and chromium oxide
[133–143]. More specifically, in the case of molybdena-based
systems:
1. In general, catalysts are less active than vanadia-based
catalysts, regardless of the support used [56]. Propane ODH
rates per Mo atom increase with increasing Mo surface
density and reach a maximum value for samples with
4.5 Mo/nm2; this behavior reflects an increase in the
reactivity of surface Mo species. Turnover rates are higher
on two-dimensional domains than on isolated monomers,
and increase as the MoOx domain size increases. While the
surface density further increases, TOF decreases as a result
of the loss of accessibility caused by the formation of MoO3
crystallites. The ratio of rate constants for propane ODH and
propane combustion reactions increases with increasing
surface density and then remains constant [118]. The size of
MoOx domains also affects the Mo O strength; stronger
Mo O bonds show lower ODH activity [119].
2. In alumina-supported samples, alumina contributes to the
primary deep oxidation and dehydrogenation routes of
ethane to COx and coke respectively, which proceed
effectively over the acidic centers. The molybdena phase
117
is involved in the ODH of ethane and the secondary
overoxidation of ethylene to COx [120]. Loadings corre-
sponding to higher than the monolayer coverage lead to a
decrease in catalytic activity, due to the growth of Al2MoO4
crystallites. Selectivity to ethylene increases when loading
increases up to 15 wt.% and then remains constant. The best
catalytic performance can be achieved with highly dispersed
two-dimensional molybdenum species, which fully encap-
sulate the alumina surface [121].
3. The activation of the ethane C–H bond proceeds through the
formation of alkoxides, which decompose to ethylene and a
surface OH group or are oxidized to surface-bound
oxygenates (acetaldehyde) [122]. When the support is
alumina, the latter produces the formation of oxygenates and
full oxidation; the lower acid strength of molybdena
(compared to alumina) permits the rapid desorption of the
olefin [123]. Surface pathways were found to play a
significant role, even at temperatures at which homogeneous
reactions also occurred, thus indicating the possible
occurrence of a heterogeneous–homogeneous reaction
scheme at high temperatures. In non-oxidative conditions,
lattice oxygen activated ethane at the same temperature as in
the presence of oxygen, leading mainly to ethylene
production, since lattice oxygen was found to be less
reactive to ethylene. More labile forms of oxygen, resulting
from adsorption of gas-phase oxygen on the surface, are
probably responsible for the extensive ethylene degradation
observed at high conversion levels [124].
4. The presence of alkali (Cs, K, Li) affects the structure of
MoOx domains and influences their electronic and catalytic
properties [125,126]. Propane ODH turnover rates decreases
monotonically while increasing both the dopant/Mo atomic
ratio and the basicity of the alkali oxide (Cs > K > Li).
These basic oxides inhibit the initial reduction of MoOx by
strengthening Mo–O bonds; as a result, rate-determining
C–H bond activation step, which involves the local reduction
of Mo centers, proceed more slowly. The stronger inhibition
of secondary propylene combustion reflects the weaker
Lewis acidity of Mo sites when modified by the basic
dopants; this accounts for the higher selectivity to propylene.
With zirconia-supported MoO3, potassium addition not only
prevents crystalline Zr(MoO4)2 formation, thus suppressing
the interaction of molybdenum oxide and zirconia phases,
but also fosters the formation of three-dimensional
molybdenum oxide and two-dimensional polymolybdates
[128]. Both propylene selectivity and yield are enhanced
thanks to a certain amount of added potassium.
5. A conversion versus selectivity chart
Figs. 1 and 2 compare the performances of several catalysts
for ethane and propane ODH, respectively. For each catalyst,
the best olefin yield value is given, obtained in correspondence
to a set value of conversion and selectivity. Tables 1 and 2 list
the catalyst type, temperature and W/F value at which that yield
was obtained, as well as the corresponding olefin productivity;
numbers given in the first column correspond to the points in the
118 F. Cavani et al. / Catalysis Today 127 (2007) 113–131
Fig. 1. A molar selectivity vs. conversion chart for ODH of ethane. Numbers in
the figure correspond to numbers given in the first column of Table 1. Top:
catalysts containing V as the main active element. Bottom: other catalysts.
Catalytic systems reported in the literature for the period 2000–2006 and giving
alkane conversion higher than 10% have been included. Systems operating in
millisecond-contact-time reactors have not been reported.
figures. Catalysts producing less than 10% conversion have not
been reported.
In recent years, the use of combinatorial/parallel systems,
including genetic algorithm and evolutionary catalyst selection
approaches, has considerably improved the number of catalytic
systems that can be prepared and studied, thus making an
important contribution to the discovery of new catalytic
systems [181,187,189,263–269].
In the case of ethane ODH, most catalysts reported in
literature give ethylene yields lower than 20%. Catalysts giving
outstanding performance are those based on NiO oxide (NiO-
Al2O3, Ni/Nb/O and NiO-MgO) [167,168,174,182,270,271],
and mixed molybdates (Mo/V/Sb/O, Mo/V/Nb/O and Mo/V/
Te/Nb/O) [145,162,164,272,273]. In NiO-based catalysts, Ni
interacts strongly with the support when the latter is alumina,
by forming surface nickel aluminate-like species in the
submonolayer regime, while NiO crystallites form on top of
Fig. 2. A molar selectivity vs. conversion chart for ODH of propane. Numbers
in the figure correspond to numbers given in the first column of Table 2. Top:
catalysts containing V as the main active element. Bottom: other catalysts.
Catalytic systems reported in the literature for the period 2000–2006 and giving
alkane conversion higher than 10% have been included. Systems operating in
millisecond-contact-time reactors have not been reported.
the nickel/alumina interface for multilayer coverages [168]. Ni
promotion with V, Mo, Co, Nb, and Ta significantly modifies
both structural and catalytic properties in ethane ODH.
Promoters are intercalated between nickel and alumina, thus
reducing the strong nickel–alumina interaction and inhibiting
nickel incorporation into the alumina lattice. The interaction
with the support improves the catalytic performance, since
unsupported NiO is unselective to ethylene. The introduction of
niobium was the most beneficial for ethane ODH, thus
increasing the reactivity to ethane by more than 50% while
maintaining the high ethylene selectivity. It is possible that
apart from improving the dispersion of the nickel phase, Nb
facilitates the C–H bond activation by acting as an electron
transfer promoter. In fact, the formation of a mixed oxide
(Ni0.85Nb0.15Ox) led to the development of a catalyst
characterized by excellent activity and selectivity for propane
ODH [167].
 F. Cavani et al. / Catalysis Today 127 (2007) 113–131 119

Table 1
A comparison of the performance of some catalysts for ethane ODH to ethylene
No. T (8C) W/F (g s ml1) Productivity ðg C¼
2 =ðgcat hÞÞ Catalyst References
1 475 1.05 0.07 Zr-V/P/O [144]
2 400 1.80 0.33 Mo/V/Sb/O [145]
3 510 0.04 0.79 V2O5-Al2O3 [54]
4 500 11.25 0.00 Mo/V/O [146]
5 590 0.04 0.37 V/Ce/O [147]
6 580 0.06 0.43 V2O5-Al2O3 mesop [79]
7 700 0.20 0.15 V/Ti/P/O [148]
8 550 0.36 0.06 V2O5-TiO2 [56]
9 550 0.03 0.80 V/P/O-TiO2 [149–152]
10 550 0.75 0.03 V/P/O-Al2O3 [153]
11 600 0.06 0.63 V2O5-Al2O3 mesop [154]
12 700 0.10 1.45 V/Mg/O mesop [155]
13 600 0.10 0.82 V/Mg/O mesop [156]
14 280 – – Mo/V/Nb/O [157]
15 500 – – V2O5-ZrO2 colloid depos. [158]
16 340 0.55 0.28 Mo/V/Te/O [159]
17 580 0.06 0.67 V/Mo/O-Al2O3 mesop [79]
18 580 0.06 0.34 V/Mo/O-Al2O3 [79]
19 500 – – Ni/V/Sb/O [160]
20 500 – – Co/V/Sb/O [160]
21 500 – – Sn/V/Sb/O [160]
22 500 – – Bi/V/Sb/O [160]
23 600 0.60 0.03 VAPO-5 [101]
24 600 0.60 0.02 Mg-VAPO-5 [101,161]
25 400 3.21 0.09 Mo/V/Te/Nb/O [162]
26 400 2.35 0.34 Mo/V/Te/Nb/O [162,163]
27 400 0.92 0.18 Mo/V/Nb/O [164]
28 570 0.15 0.24 V2O5-Al2O3 [35]
29 600 0.30 0.10 Co-VAPO-5 [103]
30 600 0.06 0.53 V2O5-Al2O3 [103]
31 600 0.13 0.14 V-MCM-41 [100]
32 600 0.02 0.76 V-MCM-41 [100]
33 500 0.31 0.06 V2O5-MgO-SiO2 [165]
34 600 0.18 0.19 V-CoAPO-18 [116,166]
35 600 1.02 0.02 VAPO-18 [116]
36 540 0.28 0.13 MoO3/Al2O3 [76]
37 400 0.54 0.41 Ni/Nb/O [167]
38 400 0.55 0.04 NiO-Al2O3 + prom [168]
39 400 0.13 0.06 Ga/Cr/O-Zr/P/O [169]
40 600 0.18 0.11 Co-APO-18 [116]
41 600 – – MoO3(Cl)-SiO2/TiO2 [170]
42 500 1.00 0.18 Co/Cr/Sn/W/O [171]
43 500 1.00 0.14 Cr/Mo/O [171]
44 600 – – MoO3(Cl)-SiO2/TiO2 [172]
45 550 – – Co-Ca hydroxyapatite [173]
46 600 0.12 6.35 NiO-MgO [174]
47 580 0.06 0.33 MoO3-Al2O3 mesop [79]
48 380 0.60 0.09 Nb/P/Mo/O (pom)/Pyr [175]
49 400 – 0.18 Mo/V/Te(Sb)/Nb/O [176]
50 550 0.36 0.16 MoO3-Al2O3 [56]
51 700 0.12 0.30 La/Na/Al/O [177]
52 700 0.12 0.25 La-SAPO-34 [178]
53 700 0.12 0.44 SAPO-34 [179]
54 550 – – Co-hydroxyapatite [180]
55 300 2.88 0.08 Ni/Ta/Nb/O [181]
56 450 1.07 0.15 Ni/O-Al2O3 [182]
57 260 – – Mo/Mn/V/W/O [183]
58 630 – – Li/Dy/Mg/O [184]
59 660 1.20 0.13 Fe/P/O [185]
60 700 0.20 3.86 Sr/La/Nd/O [186]
61 500 0.40 0.37 Co/Cr/Sn/W/O [187]
62 600 2.29 0.03 MoO3-SiO2-TiO2 sol–gel [188]
63 867 0.04 23.90 Sm/Na/P/O [189]
120 F. Cavani et al. / Catalysis Today 127 (2007) 113–131
Table 1 (Continued )
No. T (8C) W/F (g s ml1) Productivity ðg C¼
64 855 0.04 18.00
65 940 0.08 15.65
66 550 – –
67 660 0.60 1.20
68 660 0.59 1.28
69 680 0.59 1.23
70 650 0.20 0.66
Mo/V/Nb mixed oxides have been known since the 1970s to
be efficient catalysts for ethane ODH [164,274–280]; the same
catalysts also produce acetic acid from ethane, and the
formation of the latter compound is boosted, over that of
ethylene, by both the use of specific reaction conditions (e.g.,
high pressure), and the incorporation of promoters. The Mo/V/
Nb/O system is selective to ethylene, but is only moderately
active at temperatures lower than 300 8C [164,281,282]. Mo/V/
Te/Nb/O catalysts, prepared by hydrothermal synthesis [162],
were found to be extremely active and highly selective in the
ODH of ethane, especially those with a Mo–V–Te–Nb atomic
ratio of 1–0.15–0.16–0.17 and heat-treated at 600–650 8C. On
the best catalyst, selectivities higher than 80% at ethane
conversion levels higher than 80% (75% ethylene yield) were
obtained at relatively low reaction temperatures (340–400 8C).
The catalytic performance was mainly related to the presence of
orthorhombic Te2M20O57 (M = Mo, V, Nb) and (V, Nb)-
substituted u-Mo5O14. Also Mo/V/Sb mixed oxides are active
and selective in ethane ODH; Ueda et al. [283,284] reported a
selectivity to the olefin of 64% at an ethane conversion of
16.8% at 380 8C with a Mo6V2Sb1Ox catalyst. More recently
[145], selectivity to ethylene higher than 80% at an ethane
conversion of 65% was reported for samples prepared by heat
treatment in N2 at 600 8C. The good catalytic performance of
this catalyst has been attributed to the presence of
(SbO)2M20O56 (M = Mo, V) crystalline phase, similarly to
that proposed for the Mo/V/Te/Nb/O system.
Other systems giving excellent performance are those based
on RE oxides and oxychlorides, often in combination with alkali
or alkaline earth metal oxides: Sr/La/Nd/O [190], Sr/La/Fe/Cl/O,
Sr/La/Cu/Cl/O, Y/Ba/Cu/O [192–194], Li/Dy/Mg/O [184], Sm/
Na/P/O [189]. With these catalysts, which operate at reaction
temperatures higher than 700 8C, the mechanism is not the
conventional redox one, and includes the relevant contribution of
homogeneous reactions [see Section 7]. These systems yield
ethylene productivities higher than 1 kg kgcat1 h1, which is the
limit value below which the productivity is too low to be
interesting for commercial application. Conversely, with the
other catalytic systems, the ethylene productivity achieved is
lower than 1, with the sole exception of NiO/MgO [174].
Excellent performances have also been observed with Fe/P/
O [185] and mesoporous V/Mg/O [155] catalysts.
In the case of propane ODH, Fig. 2 shows that the best yields
reported are lower than 30%. In general, the main problem
encountered in propane ODH is the presence of the consecutive
reaction of olefin combustion that rapidly decreases the
propylene yield when the conversion of the alkane is increased.
2 =ðgcat hÞÞ Catalyst References
Sm/Sr/O [189]
Sr/La/Nd/O [190]
Co/P/O-TiO2 [191]
La/Sr/Fe/Cl/O [192]
La/Sr/Cu/Cl/O [193]
Y/Ba/Cu/O [194]
Na/Ca/O [195]
Furthermore, oxygen becomes the limiting reactant, due to both
the propane/oxygen feed ratio usually employed and the high
O2 consumption in combustion reaction; consequently, propane
conversions lower than 40% (with total oxygen conversion) are
usually obtained.
The best performance in propane ODH has been obtained
with non-reducible alkali or alkaline earth metal oxides
[231,285,286]. For instance, with a Li/Dy-doped MgO
catalyst, at 650 8C, the propylene yield is close to 24%,
but if the formation of ethylene is also taken into account,
the overall olefin yield is close to 48%. Addition of Li to
MgO increased reaction rate and selectivity to olefins from
40 to 70% [231,238]; lithium is, therefore, an essential
ingredient of the catalyst in order to create the active site.
Doping with Cl slightly improved the olefin selectivity, but
chloride-free catalysts showed superior stability with time-
on-stream.
With these systems, the reaction mechanism includes the
activation of propane (the rate-determining step) on the
catalyst and the generation of propyl radicals that undergo a
radical-chain mechanism in the gas phase [285]; the catalyst
acts as an initiator, but may also affect conversion and
selectivity via quenching and chain termination. Oxygen
influences the radical gas-phase chemistry significantly,
because the type and concentration of chain propagator
radicals are greatly increased. Moreover, oxygen facilitates the
removal of hydrogen from the surface OH species that are
formed during the activation of propane on the catalyst. A
specific role has been attributed to the small fraction of O ions
that can be removed from the surface of Li/MgO catalysts
[286]; in fact, it has been hypothesized that the sites containing
this reactive oxygen are responsible for the activation of
propane.
A similar oxycracking mechanism has also been reported for
a catalyst made of CoNx supported on alumina [287]; the
overall selectivity to olefins (propylene + ethylene, the latter
being the predominant product) obtained at 600 8C was 49%,
with a propane conversion of 77%.
Catalytic systems that are known to exhibit good performance
in propane ODH are Ni(Co)MoO4 [19,262,288,289] and V/Mg
mixed oxides [290–300]; however, usually the selectivity is good
only for moderate propane conversion. Systems also giving good
performance are made of isolated vanadium oxide impregnated
either on MCF silica [214] or on SBA-15 [113–115], and of
molybdenum oxide impregnated over Mg/Al mixed oxide
derived from thermal decomposition of a Mg/Al hydrotalcite
[259].
 F. Cavani et al. / Catalysis Today 127 (2007) 113–131 121

Table 2
A comparison of the performance of some catalysts for propane ODH to propylene
No. T (8C) W/F (g s ml1) Productivity ðg C¼
3 =ðgcat hÞÞ Catalyst Refereces
1 600 0.03 0.38 V-MCM-41 [100]
2 550 1.14 0.03 V-MCM-41 [98]
3 550 0.36 0.05 V-MCM-41 [98]
4 550 0.60 0.05 V2O5-SiO2 [98]
5 550 0.15 0.19 V-ITQ6 [196]
6 455 0.10 0.58 V2O5-ZrO2 [197]
7 450 – – V2O5-Al2O3 [40]
8 500 0.08 5.47 V-MCM-48 [117]
9 500 0.04 9.34 V-MCM-48 [117]
10 500 0.24 1.45 V/Mg/O [198]
11 500 – – Mn/V/Cr/W/O–Al2O3 [199]
12 500 – – V2O5/K-SiO2 [86]
13 280 – – V2O5/Ca-TiO2 [81]
14 400 1.00 0.01 V2O5/K-TiO2 [200,201]
15 480 0.60 0.16 V/Mg/Al/O [202]
16 500 0.50 0.06 V/silic. beta [203]
17 445 1.00 0.03 V/Zr/O-PILC [204]
18 500 – – V/Nb/O [205,206]
19 450 0.06 0.24 V2O5-Ga2O3 [207]
20 500 0.07 0.23 V/Mg/Al/O [208]
21 550 0.60 0.10 V/Nb/O gel [209]
22 500 0.60 0.14 V/Sb/O [210]
23 500 – – V/Nb/O-Sb2O4 [211]
24 425 0.48 0.21 V/Nb/O [212]
25 500 0.15 1.81 V/Sb/O-TiO2 [213]
26 550 1.00 0.18 V-MCF [214]
27 550 1.00 0.08 V-MCM-41 [214]
28 550 1.00 0.11 V-SBA-15 [214]
29 550 1.00 0.05 V2O5-SiO2 [214]
30 512 0.40 0.02 V/Na-V, Al-MCM-22 [215]
31 450 1.00 – V2O5/Ca hydr.apat. [216]
32 475 1.33 0.05 V2O5/K-Al2O3 [87]
33 500 0.36 0.05 V2O5-TiO2 [56]
34 500 0.06 0.60 V2O5-MgO/TiO2 [217]
35 500 0.30 0.06 V2O5-ZrO2 [27]
36 500 – 0.40 V2O5-Al2O3 [59]
37 500 – 1.43 V2O5-TiO2 [59]
38 500 – – V2O5-MgO-TiO2 [88]
39 500 0.17 1.41 V/Al/F/O [218]
40 400 0.48 0.02 V/Nb/O-TiO2 [219]
41 600 2.14 0.12 V-SBA-15 [114]
42 425 0.60 0.20 Ni/V/O [220]
43 450 0.08 6.22 V/Mg/O mesop [221]
44 600 0.75 0.33 V-SBA-15 [115]
45 500 0.60 0.20 V-HMS [222]
46 500 0.60 0.21 V-HMS [108]
47 500 0.60 0.03 V2O5-SmVO4 [223]
48 475 – – V/W/O [224]
49 400 0.60 0.11 Ni/V/O [225]
50 350 0.34 0.01 V2O5/Zn-Al2O3 [226]
51 370 0.24 0.05 V2O5-CeO2 [227]
52 450 0.60 0.03 V/Sm/O [228,229]
53 500 0.24 0.26 V-MCM-41 [110]
54 500 0.30 0.28 V2O5-TiO2-SiO2 [230]
55 550 0.42 0.05 Mo/Li/O-Al2O3 [125]
56 650 0.50 0.33 Mg/Dy/Li/Cl/O [231]
57 650 0.50 0.65 Mg/Dy/Li/Cl/O C3= + C2= [231]
58 300 0.67 0.04 Ce/Ni/O [232]
59 450 3.00 0.01 Ni/Al/O [233]
60 500 0.17 0.16 Ga-USY [234]
61 580 0.07 0.63 Ga-MFI [235]
62 450 – – Ni/Mo/O-V-MCM-41 [236]
63 450 – – Ni/Mo/O-V-MCM-41 + prom N2O [236]
122 F. Cavani et al. / Catalysis Today 127 (2007) 113–131
Table 2 (Continued )
No. T (8C) W/F (g s ml1) Productivity ðg C¼
3 =ðgcat hÞÞ Catalyst Refereces
64 450 0.50 0.05 Ni/Mo/O + Sb/O + prom N2O [237]
65 550 0.21 0.69 Cr-MCF silica [133]
66 550 0.21 0.18 Cr-MCM-41 [133]
67 550 0.21 0.34 Cr-SBA-15 [133]
68 650 0.03 2.32 Li/MgO [238]
69 550 – – MoO3(Cl)-SiO2/TiO2 [239]
70 500 0.80 0.14 Co/Mo/O-MCM-41 [240]
71 300 0.25 0.55 Ni/Ti/O [241]
72 275 0.25 0.47 Ni/Zr/O [242]
73 550 – – Cr2O3-kieshelgur [134]
74 470 0.13 0.12 MoO3-Al2O3 [80]
75 500 0.36 0.06 MoO3-Al2O3 [56]
76 550 0.80 0.33 Mn/P/O [243]
77 500 0.80 0.06 MoO3/K-ZrO2 [128]
78 550 – – Na/W/O-SiO2 [244]
79 600 0.60 0.30 Mn/Mo/O [245]
80 500 – – P/O-C nanofibers [246]
81 400 0.74 0.01 Nb2O5-TiO2 [219]
82 560 1.00 0.09 Co/W/O [247]
83 560 1.00 0.15 Ni/Mo/O [248]
84 460 – – Ga/Mo/O [249,250]
85 535 – – Mg/Mo/(V)/O [251]
86 450 0.80 0.19 Cr2O3-Al2O3 [252]
87 420 0.80 0.20 Cr/Mo/Cs/O-Al2O3 [253]
88 500 0.80 0.38 Cr2O3-Al2O3 [254]
89 450 1.00 0.10 Co/Sr/O-hydr.apatite [255,256]
90 500 1.50 0.12 Ag/Mo/P/O [257]
91 550 0.60 0.06 MoO3-SmVO4 [258]
92 600 – – Mo/Mg/Al/O (from HT) [259]
93 550 5.00 0.02 MoO3/K-SiO2-TiO2 [260]
94 550 0.38 0.08 TS-1 [261]
95 450 0.80 0.19 Cr2O3-Al2O3 [138]
96 450 – – Cr/Mo/O-Al2O3 [139]
97 500 0.42 0.05 MoO3-Al2O3 [131]
98 420 0.38 0.21 Ni/Co/Mo/O [262]

K-doped, SiO2/TiO2-supported MoO3 also exhibits good
performance in propane ODH [127,170,172,188,239,
260,301,302]. The doping with chlorine alters the relative
surface concentration of Si versus Ti, the electronic structure of
surface MoOx domains, the oxygen environment around
supported MoOx species in the Si/Ti network and finally the
redox properties of Mo sites. These modifications led to an
increase of the selectivity to the olefin (also observed in the case
of ethane ODH), also ascribed to the MoOx species sharing
more complex ligands with silica and titania, with the indirect
participation of chlorine. The best propylene yield reported
with this catalyst was close to 26%; however, the productivity
achieved was very low.
Also gas-phase promoters added in the feed stream, such as
N2O, may improve the catalytic performance [303–305].
Table 2 also shows that the productivity achieved is, for the
majority of catalysts, much lower than 1 kg olefin per kg of
catalyst per hour. The low values reported are due to several
factors: (i) the low intrinsic catalyst activity, (ii) the use of very
alkane-diluted feed streams, and (iii) the use of low flow rates.
Exceptions are the VOx-MCM-48 catalyst [117] and mesopor-
ous V/Mg/O [221], both giving propylene productivity
significantly higher than 1 h1.
6. Staged feed of oxygen, membrane-type reactors,
alternate feed of reactants
Several studies have explored approaches that minimize O2
concentrations in contact with the catalyst by separating
hydrocarbon and oxygen, either temporally or spatially, using
cyclic and membrane reactors, respectively. The reason for this
is that the coexistence of alkanes and O2 leads to undesired
combustion reactions, due to the unselective role that weakly
adsorbed O species may play.
Lower O2 concentrations can be maintained throughout the
reactor length by staging O2 introduction; staging also makes it
possible to feed an amount of oxygen that would lead to
explosive mixtures in the co-feed mode. Oxygen transport
membranes or multiple injection points can be used to
implement these methods [306–325]. Tonkovich et al. [306]
reported 53% ethylene selectivity at 95% ethane conversion
when using porous alumina membranes and a MgO/LiO/
Sm2O3 catalyst at 600 8C, whereas the selectivity was only 8%
at similar conversion and temperature in a co-feed reactor. Also
in the case of alumina-supported vanadium oxide catalyst, a
better ethylene yield was obtained with a packed-bed
membrane reactor (porous alumina membrane) with respect
 F. Cavani et al. / Catalysis Today 127 (2007) 113–131
to a conventional packed-bed reactor configuration [282]. It is
worth noting that in the case of propane ODH, conversely, the
use of CMRs and of oxygen distribution, in general, has not
brought remarkable improvements if compared to the conven-
tional reactor configurations. Santamaria and co-workers [324]
reported that in catalytic membrane reactors (CMRs), the
propylene yields in propane ODH can be optimized with
membranes that combine the appropriate V loading in the
active layer with a sufficiently resistant diffusion layer.
Waku et al. [311] found that in ethane ODH catalyzed by
V2O5-Al2O3 co-feed and staged-O2 introduction modes led to
similar ethane dehydrogenation and combustion rates, despite
significant differences in the average O2 concentrations.
However, the rate of ethylene combustion was lower when
oxygen was introduced gradually, due to the lower contribution
of homogeneous ethylene combustion pathways.
Some studies investigate the concept of fluidized bed
membrane reactors (FLBMR) with distributed oxidant supply
for alkanes ODH. Klose and co-workers [316] compared a
conventional fluidized bed reactor and a packed-bed membrane
reactor with a FLBMR, for the ODH of ethane using an
alumina-supported vanadium oxide catalyst. For identical
overall feed rates, the distributed oxidant feeding in the
FLBMR significantly improved the selectivity to ethylene. The
beneficial effect of oxidant dosing over the membrane was most
significant at high temperatures and with long contact times.
The maximum ethylene yield observed in the FLBMR was
37%. In addition to high productivity, for the FLBMR a more
favorable operation range with respect to the oxygen–
hydrocarbon ratio was observed; this indicates a lower
sensitivity to oscillations and disturbances in the reactant
feed, corresponding to higher safety in operation.
Yang et al. [307,326] reported much higher ethylene
selectivity (80%) at 84% conversion by using a mixed oxide
ion conductor (Ba0.5Sr0.5Co0.8Fe0.2Ox) as catalyst and a
membrane, than in a co-feed reactor. These are outstanding
results, comparable to those obtained in thermal cracking. A
dense perovskite hollow fiber membrane was also studied for
ethane ODH [317], and compared with the performance of a
disk-shaped membrane [307,318]. An improved selectivity was
also obtained in the case of propane ODH; at 23–27% propane
conversion a selectivity of 44% to propylene was reported,
versus a 15% selectivity achieved in the fixed-bed reactor [327].
Similarly, a better ethylene yield in ethane ODH as compared to
steam cracking was obtained by Mirodatos and co-workers
[328], with a reactor using dense mixed-ion electron
conducting membranes, made of Ba0.5Sr0.5Co0.8Fe0.2O3; the
application of a surface catalyst at the permeate side (V/MgO
micrograins, Pd nano clusters) further enhanced the perfor-
mance (75% yield). This was attributed to the importance of
surface exchange phenomena for oxygen permeation.
Takehira et al. [310,329] reported a drastic enhancement in
the rate of ethylene formation when using an electrochemical
reactor Au/YSZ/Ag with yttria-stabilized zirconia (YSZ) as
solid electrolyte, and a MoV2O8 catalyst film on the
electrochemical cell, at 500 8C, under oxygen pumping through
the cell, as compared to the conventional fixed-bed reactor. The
123
enhancement effect was attributed to the supply of dissociated
oxygen through the YSZ.
The extrapolation of the concept of controlling O2
concentration is represented by the so-called redox-decoupling
or cyclic technology, which operates through the separation of
the two steps included in the Mars-van Krevelen mechanism,
i.e., (i) oxidation of the hydrocarbon by the catalyst, which must
be able to draw off hydrogen and supply oxygen, for either the
formation of water or its insertion onto the substrate, and which,
therefore, undergoes simultaneous reduction (two electrons per
each O2 ion furnished) and (ii) oxidation of the reduced
catalyst by molecular oxygen. Several papers report the
application of this type of operation for alkanes ODH
[52,199,330–343]; in many cases, an improved selectivity to
the olefin as compared to the co-feed operation and for the same
level of alkane conversion has been achieved whereas, in other
cases, no effective improvement has been reported. For
instance, catalysts made of V2O5-SiO2 showed a remarkably
improved selectivity to propylene with respect to the co-feed
conditions for propane ODH, whereas the same remarkable
effect was not observed with catalysts in which vanadium oxide
was deposited on alumina or titania [52,336] (Fig. 3). Indeed,
the very high selectivity to propylene obtained at low propane
conversion in the redox mode was due to the relevant
contribution of dehydrogenation to olefin formation over the
strongly reduced catalyst.
One condition for obtaining an improved selectivity with the
cyclic operation is the presence of catalysts in which the V sites
are highly dispersed; this was achieved by preparing vanadium
oxide–silica cogels, with a V2O5 content lower than 10% [336].
The improvement in selectivity to propylene was around 30
percentage points (60% selectivity in cyclic mode versus 30%
in co-feed mode) for a propane conversion of 35% (Fig. 3). The
same positive effect on selectivity was obtained with Mg/V/O
catalysts [333–335].
The same concept has been used also with an alkane
dehydrogenation catalyst [332,344–346], to shift the equilibrium
Fig. 3. A comparison of the selectivity to propylene obtained by cyclic feed
(redox mode) (full symbols) and co-feed (open symbols), for supported
vanadium oxide catalysts [52]. V2O5-Al2O3 (^), V2O5-TiO2 (*), V2O5-
SiO2 (&), and V2O5-TiO2/Al2O3 (~).
124 F. Cavani et al. / Catalysis Today 127 (2007) 113–131
of the reaction through a catalyst selective in H2 combustion.
This can be carried out by feeding O2 together with the alkane; a
(post)transition metal or its oxide can be used to selectively
oxidize hydrogen [347–349]. Catalysts selective in H2 combus-
tion in the presence of alkane and alkene are made of Pt/Sn-SiO2
or In2O3-SiO2 as long as the O2 fed is less than half the H2
[350,351], or Bi2O3-SiO2 [352], or W-doped ceria (Ce0.9W0.1Oy)
[345]. Propylene yield enhancements of 1.6 above equilibrium
were achieved by the selective H2 removal using O2 staging, with
dehydrogenation catalysts made of small Pt clusters within Na-
[Fe]ZSM5; more than 90% of the O2 introduced was used to form
H2O from H2, even when hydrocarbons were the predominant
available reactants [353].
This approach has the advantage of the energy released by
exothermic oxidation, which is needed to aid dehydrogenation.
However, by mixing oxygen, hydrogen, and hydrocarbons at
high temperatures, a dangerous mixture can be obtained. The
separation of reactants using dense ion-conducting oxides or
oxygen-selective membranes reduces the risk of explosion;
however, as an alternative approach, the cyclic concept can be
applied. Specifically, a solid oxygen carrier (SOC) is used to
selectively remove H2 from the reactor and improve product
yield [263,345,346]. Then, oxygen is flowed to re-oxidize the
reduced SOC; the latter is typically a metal oxide that can
easily sustain the redox cycle. The reduction of SOC by H2 can
be either endo- or exothermic, depending on the type of oxide;
in the latter case, the reduction provides the energy gain to
support the endothermic dehydrogenation; otherwise, during
the re-oxidation step the heat released is stored in the catalytic
bed and carried over to the next cycle. The authors reported that
the best SOC was Ce0.9W0.1Ox (selectivity to H2 oxidation
higher than 97%), which – when coupled with a dehydrogena-
tion catalyst – made it possible to enhance the conversion
and selectivity to propylene compared to a conventional
dehydrogenation reactor.
7. The contribution of homogeneous reactions to olefins
formation: short-bed reactors and non-redox-type
catalysts
In 1993, Huff and Schmidt first reported the selective ODH
of ethane over a Pt-loaded honeycomb catalyst at millisecond
contact time (short-bed reactors) and high reaction temperature
(850–1000 8C) [354]. This technology appeared promising for
both the compactness of its reactor and the potential energy
efficiency that would allegedly result from its autothermal
(adiabatic) operation. Since then, several teams have been
investigating this possibility [190,355–379]. The optimal
catalyst contains a low Pt loading, deposited on a monolithic
large-pore support [354,380,381], based on either mullite [355]
or Ba/Mn aluminate [357] (best performance 62% ethane
conversion with 72% selectivity, and with H2 addition in the
feed), or g-alumina [371,382] (best ethylene yield 50%). Other
systems reported include Pt/Sn [362,363,366,380] (best
conversion 70%, with 85% selectivity to ethylene, and with
H2 addition in feed), Pt/Rh gauzes [356,377], LaMnO3 [383]
(best ethylene yield 55%), and LaMnO3 supported on ceramic
foam (57% ethylene yield in ethane ODH) [369,373], Pt-
LaMnO3 [374] (best ethylene yield 59%), Er/Sr/O-SiO2/Al2O3
[384] (best ethylene yield 55%), Cr/O-ZrO2 [385], or even Ba/
Mn aluminate [382]. An improved selectivity to ethylene can be
obtained by feeding CO and H2 (sacrificial fuels) that are
preferentially oxidized in place of ethane [362,372,380], or
by adding chlorine, which improves the Pt dispersion [386].
The typical per-pass ethylene molar yield of an ethane steam-
cracker unit is 48%, with a selectivity close to 80% (78% molar
yield upon recycling of the unconverted ethane). Therefore,
yields achieved in short-bed reactors are comparable to those
of commercial cracking units, and better than yields to
olefins (ethylene + propylene) obtained in commercial naphtha
steam-cracker units.
The formation of ethylene requires two steps: a catalytic
exothermal oxidation of a fraction of the feed to CO/H2 and
CO2/H2O followed by an endothermic thermal (uncatalyzed)
cracking of the remaining ethane to ethylene (oxycracking)
[111,370,380,382]; the same occurs in the case of propane, in
which propylene and ethylene form via gas-phase oxidative
pyrolysis [387,388]. The role of the catalyst is limited to
initiating the exothermic oxidation reactions and determining
the heat release, while it does not affects the cracking reaction
significantly [358–361,375]; a partial reforming of the
hydrocarbon downstream of the combustion zone was not
ruled out [361]. The mechanism is therefore quite different
from redox-type ODH, since it includes the important
contribution of non-catalytic homogeneous reactions at high
temperature; at these temperatures ignition is followed by gas-
phase cracking (pyrolysis), thus producing alkenes and
methane.
Indeed, the same reaction can be carried out without
catalytic ignition at 850 8C, with residence time 0.1–0.4 s, and
with an ethylene yield of 68% [389]. The reaction proceeds
thermally through conventional cracking, but the addition of O2
improves the conversion and makes the overall reaction become
thermoneutral with a O2/ethane 0.2 molar feed ratio. Although
similar yields are obtained in non-catalyzed oxidative
pyrolysis, the use of the catalyst makes it possible to operate
in a more energy-efficient manner, with lower contact times and
reactor volumes.
In addition to ethane, the oxycracking of higher hydro-
carbons was also studied [364,365]. While ethane cracks to
ethylene, methane and COx, propane, n-butane, n-pentane and
hexane were found to crack to propylene and ethylene (and
methane and COx) rather than undergo dehydrogenation; in
general, however, yields to olefins were low. An opportunity
for the oxycracking of alkanes has been described by Lange
et al. [361], with the concomitant production of synthesis gas
and unsaturated hydrocarbons for subsequent carbonylation or
hydroformylation. Examples include the production of
synthesis gas and ethylene or ethyne for hydroformylation
to 1-propanol or butanediol, respectively, or the co-production
of propylene or propyne with synthesis gas followed by
production of 1-butanol or methylmetacrylate.
With non-redox-type catalysts the formation of olefins also
occurs by heterogeneously initiated homogeneous reactions
 F. Cavani et al. / Catalysis Today 127 (2007) 113–131
under more conventional conditions, i.e., with residence times
higher than 0.1 s and temperatures in the 600–750 8C range
[285–287,390–394]. Catalysts described are based on Li/Dy/
Cl-MgO [184,285,286,390,393] (best ethylene yield 77% from
ethane, and best olefins yield 50% from propane), Li-Y2O3
[391] (best ethylene yield 51% from n-butane), Co/N-Al2O3
[287], RE oxide-based catalysts [48,189,190] (best ethylene
yield 46% from ethane, and best olefins yield 45% from
propane), and perovskite-type halo-oxides (La/Sr/Fe/X/O)
[192] (best ethylene yield 57.6%). Rare earth oxides offer
the additional advantage of higher thermal stability and less
sintering problems, compared to Pt-based systems. In the case
of Li/Dy-MgO catalysts, it has been demonstrated that chlorine
plays an important role [184], since the active sites reside in
molten LiCl. O2 is dissolved dissociatively in LiCl, forming
hypochlorite OCl which, at high temperatures, decomposes to
radical species. The latter activate the alkane by homolytic
hydrogen abstraction, and the alkane radicals react further with
OH to form an olefin. The main problem of these very active
systems, however, is the catalyst stability, since their excellent
performance is maintained only as long as the halogen is not
removed, in the form of HCl, from the catalytically active
phase.
Therefore, under these conditions the catalyst plays the role
of a radical initiator, generating alkyl fragments that are then
transformed into the olefins in the gas phase. In the case of
propane, in general the performance is worse than that obtained
in catalytic dehydrogenation (the latter gives a selectivity to
propylene of 85% with propane conversion around 65–70%),
with propylene yields that are lower than 25%, but if the
formation of ethylene is also included, the overall selectivity to
olefins becomes considerably higher [48,189,394].
The contribution of non-catalytic homogeneous reactions in
alkanes ODH has been discussed in several papers
[8,13,155,186,285,396–402]. The reaction conditions leading
to a main contribution of radicalic, homogeneous reactions
have been widely discussed by Sinev [398]; in general, the
latter are aided by both the use of reaction temperatures higher
than 500 8C and the presence of large void fractions in the
reactor. The formation of free radicals may occur on the catalyst
surface (this is an energetically feasible process); radicals may
then desorb into the gas phase, where the reaction proceeds
(heterogeneously initiated homogeneous reactions) [396].
Under certain circumstances, these gas-phase reactions may
be more selective than the completely heterogeneous process,
and this may be one reason for the increased selectivity to the
olefins which is sometimes observed when the reaction
temperature is increased [13]. Certain thermochemical para-
meters of surface active sites, particularly the H-atom affinity
E[O–H] and the oxygen binding energy E[O] govern the
kinetics of elementary heterogeneous reactions of free radicals
[398].
In their paper, Lange et al. [361] examined the economics of
oxycracking to assess its potential as an alternative to steam
cracking. The authors concluded that: (i) investment savings
achieved with the oxycracker reactor (smaller and cheaper than
a steam-cracking furnace) were significantly offset by the cost
125
of the O2 plant; (ii) variable costs were substantially similar for
the two cases; (iii) potential savings in investments for the
oxycracker was finally limited to the US$ 13/t that corresponds
to 3% of the total manufacturing cost. This is too small to justify
the cost of developing a new technology and the risk of
commercializing it. The authors also reported that improve-
ments in alkene yields can be realized by (a) tuning the catalyst
porosity to allow for gas-phase reactions, and (b) tuning the
chemical nature of the support to favor the complete oxidation
of the hydrocarbon ‘‘fuel’’ to CO2/H2O instead of CO/H2.
Further yield improvement can also be achieved by reactor
design and heat management, in particular by preheating the
feed and minimizing heat losses. Reactive ‘‘fuel’’ components
(H2, CO, methanol, and acetone) can be added to the feed in
order to spare valuable hydrocarbons for subsequent cracking.
Wolf et al. [395] compared three different concepts for
olefins production from propane, (i) the commercial catalytic
dehydrogenation, (ii) the autothermal oxidative dehydrogena-
tion over a Pt/alumina catalyst and (iii) the ODH with a titania-
supported vanadium oxide catalyst. If exclusive propylene
production is the objective, both oxidative process variants did
not reveal an alternative to the non-oxidative propane
conversion neither for consumption of energy nor raw material.
On the contrary, if olefins are the desired products, the
autothermal oxidative propane conversion might compete with
the commercial non-oxidative process while the isothermal
ODH did not show any advantage.
8. The formation of H2 during ODH
Another aspect concerns the significant formation of
molecular H2 [13,403]. While the formation of H2 may be
expected with non-reducible metal oxides catalysts and high
reaction temperatures, which are more conducive to cracking
phenomena, H2 formation is unexpected under conditions that
are typically considered to lead to the co-formation of H2O.
The formation of H2 under the typical conditions for alkanes
ODH has been mentioned by some authors [403–406]. Sinev
et al. [403] considered non-oxidative dehydrogenation and
coking as the most important hydrogen formation pathways in
propane ODH. Moreover, it was suggested that other reactions
were involved, generally indicated as free-radical oxidations.
Recent papers confirm that considerable amounts of H2 are
produced under conditions of propane ODH, with vanadium
oxide-based catalysts [46,52,336–340].
Under the reaction conditions typically used for propane
ODH, bulk vanadium oxide modifies its characteristics on the
basis of the reaction conditions, and specifically of gas-phase
composition and temperature. Indeed, in most cases ODH is
carried out using O2 as the limiting reactant, since hydrocarbon-
rich conditions may lead to a better selectivity to the olefin. This
implies that the total conversion of oxygen is reached,
especially when temperatures higher than 500 8C are used.
This causes the vanadium oxide stoichiometry to change along
the catalytic fixed-bed, from V2O5 in the aerobic section of the
reactor, to reduced vanadium oxide (V2O4, V2O3) in the
fraction of bed that operates in the absence of molecular oxygen
126 F. Cavani et al. / Catalysis Today 127 (2007) 113–131
[407]. This corresponds to a change in the type of reaction
occurring inside the reactor. In the first part of the catalytic bed,
propane is oxidized to acetic acid, propylene, CO, CO2 and
H2O. In the reducing section, conversely, propane is
dehydrogenated to propylene and to aromatics/coke; however,
one important contribution to H2 generation derives from WGS,
which is efficiently catalyzed by V2O3 [340]. Therefore, these
self-adapting properties of vanadium oxide make it possible to
combine the formation of CO and H2O with the WGS reaction,
and to obtain H2 and CO2 as main products. However, when
catalytic systems more selective to propylene, made of
alumina- or silica-supported vanadium oxide, were used, the
formation of H2 was exclusively due to the catalytic
dehydrogenation [46]. This result was attributed to the fact
that, in these catalysts, vanadium was not reduced below the
oxidation state V4+, even under reaction conditions leading to
the total oxygen conversion. Consequently, these catalysts
produced less H2 than bulk vanadium oxide.
9. Conclusions
Over the past few years, significant steps forward have been
made in the study of new catalyst types and reactor
configurations for the ODH of ethane and propane. Especially
in the case of ethane, the ethylene yield values reported with
some catalysts are comparable to, or even better than, the
corresponding values obtained by steam cracking. The case of
propane ODH is different because the best yields reported are
still far from being interesting for industrial implementation.
Conditions leading to best propylene yields also lead to the co-
production of significant amounts of ethylene; therefore, the
finding of a catalyst capable of combining industrially
acceptable conversion/productivity with specificity to this
olefin is still the major objective. Moreover, for both ethane and
propane ODH, very little information is reported in literature
concerning catalysts lifetime.
It is evident that, in the future, the greatest efforts will be
devoted to the study of catalysts and/or reactor configurations
that are capable of maintaining high selectivity to propylene
under conditions leading to high propane conversion.
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