Catalytic Oxidative dehydrogenation

The new technology of catalytic oxidative dehydrogenation (ODH) may completely change the
way some of the most important organic chemicals are manufactured. The conversion of alkanes like
ethane (a byproduct of petroleum processing and present in natural gas) to olefins (ethylene!
propylene! the butenes! and butadiene) is in great demand in worldwide chemical industry. High
operational costs and environmental issues have made this conversion profitable only on a very large
scale. "ith successful development of ODH! high yields of olefins will be possible through the
conversion of much smaller volumes of alkanes.
#ompared with the conventional steamcracking method of dehydrogenating alkanes to olefins and
current catalytic dehydrogenation processes! ODH could reduce costs! lower greenhouse gas
emissions! and save energy. #apital and operational efficiencies are gained by eliminating the need for
a furnace and for decoking shutdowns! lowering operating temperatures! lessening material demands!
conducting fewer maintenance operations! and using a greater proportion of the alkanes in the olefin
conversion process.
$ow molecular weight alkenes! such as ethene and propene! can be formed via nonoxidative
dehydrogenation of the corresponding alkane. %onoxidative dehydrogenation reactions are
endothermic and lead to the concurrent formation of carbon and of lower molecular weight alkanes!
both of which decrease alkene yields. Oxidative dehydrogenation (ODH) of light alkanes offers a
potentially attractive route to alkenes! since the reaction is exothermic and avoids the thermodynamic
constraints of nonoxidative routes by forming water as a byproduct. &n addition! carbon deposition
during ODH is eliminated! leading to stable catalytic activity. However! the yield of alkenes obtained
by ODH on most catalysts is limited by alkene combustion to #O and #O
'
(#O
x
( relevant example concerns catalytic conversion of nbutane to butenes by oxidative
dehydrogenation (ODH) as an alternative process to direct dehydrogenation. &t is well known that
supported vanadium pentoxide is a promising catalyst for the ODH of nbutane. )gO supported
vanadium was reported as a very selective catalyst in the oxidative dehydrogenation of propane and n
butane! while *(+
'
O
,
supported vanadium catalyst was found to present a good selectivity to olefin
products for ethane ODH but a poor selectivity in the ODH of nbutane. The acidbase character of the
support explained this different behavior. On )gO! a support with basic properties! the interaction
between vanadium species and the supports leads to the formation of vanadate compounds. &n the case
of more acid supports! such as -iO' or (+'O, a weak interaction is expected leading to less dispersed
vanadium species on the surface which! in turns favors the formation of .'O/ crystallites
#atalytic cracking gives many byproducts and is not necessarily optimi0ed with respect to propene
yield. 1ropane dehydrogenation! on the other hand! yields propene as the main product. The problem is
that the dehydrogenation e2uilibrium favors propene only at high temperature or low pressure! adding
to the overall cost of the process. The need for cryogenic separation of the unconverted propane and
produced propene also adds to the process costs. &mprovements of the dehydrogenation process to
make it commercially more attractive focus on increasing the yield by shifting the e2uilibrium through
removal of one of the reaction products. Thus! in situ removal of hydrogen will shift the
dehydrogenation e2uilibrium to the product side. This can be done either physically by means of a
membrane! or chemically by in situ catalytic oxidation using a (post) transition metal or its oxide. The
latter approach has the additional advantage of energy release by exothermic oxidation where it is
needed to aid the dehydrogenation. However! mixing oxygen! hydrogen! and hydrocarbons at high
temperatures creates a highly dangerous mixture. The risk of explosion may be reduced by separating
the reactants in space using oxygenselective membranes.