metathesis have achieved technical maturity and acceptance, and significant

developmental efforts have made them competitive with co-production

technologies in the market
Private-sector companies specialising in specific value chains, such as the
propylene value chain, are growing in the marketplace
The tight propylene market and high oil prices have continuously driven up
prices for propylene and propylene derivatives.
As a result, while in 2003 more than 97% of all propylene was produced from
steam crackers and refineries, and only 3% by on-purpose technologies, 10%
of worldwide propylene production by 2012 will be provided by on-purpose
technologies, mainly PDH and metathesis plants.
Metathesis was first commercially applied to propylene production at the

$800/ton.1 The EPPC PDH/PP project at Port Said, Egypt, is the first project
in the world to apply the Uhde STAR process with oxydehydrogenation.
PDH chemistry
Paraffin dehydrogenation reaction chemistry, although quite simple from a
stochiometric point of view, is very complex due to its strongly endothermic
nature and significant conversion limitations caused by thermodynamic
equilibrium. Side reactions include the cracking of hydrocarbons and hydro-
genolysis, as well as oligomerisation, cyclisation, hydrogenation of olefins,
deep dehydrogenation and eventually the formation of coke and tar laydown
on the catalyst, which requires frequent catalyst regeneration (ie, burning off
of coke and tar laydown on the catalyst with oxygen or air).
Two main catalytic systems have been identified and commercialised for light
paraffin dehydrogenation, the first being supported chromia catalysts (ie,
chromia on alumina support), which are doped with alkali metals to add
alkalinity and suppress unwanted side reactions, and the second supported
platinum or platinum-tin catalysts, with different support materials. These
materials include alumina or zinc-/ calcium-aluminate, and potentially
further modifiers such as alkali metals, again to reduce the acidity of the
support and suppress side reactions. While chromia catalysts were already
used commercially for butane dehydrogenation in the 1940s (UOP), platinum
catalysts have only been used since the 1960s, when they were first applied in
UOP’s proprietary Pacol process. Today, both catalyst systems are used in
commercially available PDH processes (ie, chromia catalyst in Lummus
CATOFIN and platinum-tin catalysts in UOP Oleflex and Uhde’s STAR
process).
With the dehydrogenation reaction
being favoured by high temperatures and low partial pressures, all

www.eptq.com PTQ Q1 2008 83