Advanced propane dehydrogenation
Oxdehydrogenation-based on-purpose propane dehydrogenation can close the
propylene supply-demand gap
Max Heinritz-Adrian and Sascha Wenzel Uhde GmbH
Fekry Youssef Egyptian Propylene & Polypropylene Company
T
he world is currently witnessing a signifi-
cant change in the propylene market as it
moves away from co-production and
towards more on-purpose production and the
supply of propylene. By applying the principle of
oxydehydrogenation, the feasibility of on-purpose
propylene production by propane dehydrogena-
tion (PDH) is further improved. The first plant
based on this principle is now under realisation in
Port Said, Egypt.
Propylene market
Propylene is one of the most important interme-
diate petrochemical products. Over many years,
it has maintained a remarkable growth in
demand that is mainly attributed to the signifi-
cant growth in polypropylene (PP) demand,
which absorbs more than 60% of all the propyl-
ene produced worldwide. PP has grown into one
of the most widely applied plastic products, and
its broadness in application which is continu-
ously expanding and its superior features in
many applications continue to drive demand.
Other important propylene derivatives include
acrylic acid, acrylonitrile, cumene/phenol and
propylene oxide.
Although most propylene has been produced
as a co-product to ethylene in steam crackers
and as a byproduct in refineries, we are currently
witnessing a significant change in the propylene
supply chain with a move away from co-produc-
tion and towards on-purpose production. There
are several reasons for this change:
The growth in demand for propylene has
outpaced the growth in demand for ethylene for
many years and will continue to do so
Due to significantly better feasibility, a large
share of new cracker projects for ethylene
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production is based on ethane feedstock yielding
no propylene co-production
Several on-purpose propylene production tech-
nologies such as propane dehydrogenation
(PDH) and metathesis have achieved technical
maturity and acceptance, and significant devel-
opmental efforts have made themcompetitive
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 tech-
nologies, 10% of worldwide propylene production
by 2012 will be provided by on-purpose technol-
ogies, mainly PDH and metathesis plants.
Metathesis was first commercially applied to
propylene production at the BASF/FINA Port
Arthur Cracker, USA, and several plants have
been built in Asia since then. PDH was commer-
cialised in the 1990s, with six PDH plants having
been started up (one is co-production) in
Thailand, Malaysia, Korea and Belgium, out of
which five apply UOP technology and one
(owned and operated by Borealis in Kallo near
Antwerp, Belgium) employs Lummus technol-
ogy. In the first five years of the 21st century,
two PDH projects started up; namely, the SPC
plant in Al-Jubail, Saudi Arabia, employing
Lummus technology and the Basell/Sonatrach
joint venture in Tarragona, Spain, employing
UOP technology. A total of five PDH projects are
currently under realisation in Egypt, Saudi
Arabia and Thailand. Development for most of
PTQ Q1 2008 1
 these projects had already begun in the 1990s.
However, only after the long-expected tightening
of the propylene market materialised did they
finally begin to move forward.
Although additional propylene production
capacity will come on stream in the next few
years, propylene prices are expected to remain
above $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 endo-
thermic nature and significant conversion
limitations caused by thermodynamic equilibrium.
Side reactions include the cracking of hydrocar-
bons 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 identi-
fied and commercialised for light paraffin
dehydrogenation, the first being supported chro-
mia catalysts (ie, chromia on alumina support),
which are doped with alkali metals to add alka-
linity 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 commer-
cially for butane dehydrogenation in the 1940s
(UOP), platinum catalysts have only been used
since the 1960s, when they were first applied in
UOPs proprietary Pacol process. Today, both
catalyst systems are used in commercially availa-
ble PDH processes (ie, chromia catalyst in
Lummus CATOFIN and platinum-tin catalysts in
UOP Oleflex and Uhdes STAR process).
With the dehydrogenation reaction being
favoured by high temperatures and low partial
pressures, all commercially available technolo-
gies keep the process temperature at or below
approximately 650C, because higher tempera-
2 PTQ Q1 2008
tures would lead to a significant increase in side
reactions and therefore a decrease in the selec-
tivity of the main reaction for propylene
production. Furthermore, the most significant
side reactions are not limited by thermodynamic
equilibrium. As a result, the higher retention
times required to achieve higher per-pass conver-
sions also have a strongly negative impact on
propylene selectivity. At the same time, partial
pressure is kept low by applying absolute pres-
sures slightly above atmospheric pressure or
even under vacuum, or by using a diluent to
reduce the hydrocarbon partial pressure. As a
result of these considerations, all the technical
processes for PDH have limited conversion in
the range of 3255%, with selectivities to propyl-
ene in the range of 8791 mole%.
As the significant amount of coke laydown
leads to a fairly quick deactivation of the catalyst
(ie, in therange of minutes to a few days), differ-
ent reactor systems are applied to account for
the regeneration needs. Continuous systems
applied are moving-bed systems and fluidised
bed systems. Discontinuous (fixed-bed) systems
applied are heated fixed-bed systems (as in
Uhdes STAR process) and adiabatic fixed-bed
systems.
Key factors in PDH design
Product work-up sections for all the PDH tech-
nologies are very similar, as the side products,
and therefore the separation tasks, are also simi-
lar. When comparing different PDH technologies,
several key components need to be evaluated to
find the differences and advantages of one tech-
nology over the other. Table 1 lists certain data
generally available in the industry for commer-
cial PDH technology.
Reaction system Due to the endothermic nature
of the reaction, the fairly high temperature (to
achieve acceptable conversion) and catalyst
regeneration requirements, the reaction systems
for each process are quite complex and therefore
relatively high in investment. An effective design
of the reaction system applied with respect to
certain design criteria is essential. Key parame-
ters are an optimised temperature profile to
achieve high space-time yields (ie, high conver-
sion and selectivity at high space velocity), an
optimised operation/regeneration system that
minimises the effort for the regeneration of the
catalyst and an efficient heat supply to the endo-
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 PDH process technology parameters
UOP Oleflex Uhde STAR process Lummus CATOFIN
Catalyst Pt-Sn on alumina Pt-Sn on zinc/calcium aluminate Chromia on alumina
Reaction system Fluidised bed system consisting of Fixed-bed system consisting of Fixed-bed system consisting of
several radial-flow adiabatic reactors in an externally fired tubular reactor a number of axial-flow adiabatic
series and an external regenerator (CCR) and an adiabatic reactor in series reactors connected in series

Main source for Preheating of the feed and External firing of the tubular reactor Heating the catalyst during
heat supply intermediate products and selective hydrogen combustion catalyst regeneration
before each reactor in the adiabatic reactor

Operating mode Continuous (510 days Discontinuous (7 hours normal Discontinuous (620
catalyst cycle time) operation, 1-hour regeneration) minutes reaction cycle)
Pressure, bara 2 5 0.30.5
Temperature, C 580650 570590 560650
LHSV, [m_ liq. feed/(m_ catalyst * h)] 4 6 <1
Per-pass conversion propane, % 35 40 4865
Selectivity propene, mol-% 8991 89 88

Table 1

thermic dehydrogenation reaction to allow full
utilisation of the catalyst activity.
Raw gas compression For the separation and
production of the propylene product the raw
product consisting of propane, propylene, hydro-
gen and side products the gas needs to be
compressed to higher pressures (in the range of
1535 bar). Since the dehydrogenation reaction
is commercially realised at fairly low pressures,
as previously described, the raw gas compression
requires significant investment and energy costs.
As the STAR process operates in the presence of
steam, the absolute pressure of the reaction
section can be increased while keeping the
partial pressure of hydrocarbons low (and thus
conversion high). As a result, the process has a
relatively higher suction pressure, resulting in
lower cost (Capex and Opex) for raw gas
compression.
Propane consumption The propane consumption
of a PDH plant typically makes up more than
80% of all operating costs and more than 60% of
the cost of production. Propane consumption is
determined by the product selectivity achieved in
the reaction system and the recovery of propyl-
ene product (as well as unconverted propane) in
the separation section. An optimisation of Capex
vs Opex needs to be considered in terms of high
conversion vs high selectivity in the reaction
section, as well as high recovery/high sophistica-
tion vs low recovery/low sophistication in the
separation section. An evaluation and optimisa-
tion of the process design with respect to these
issues has resulted in the product recovery being
optimised to achieve a recovery of more than
99.5% of the propylene produced in the reaction
section, while keeping it simple indesign.
Catalyst and chemicals The factors for the cost of
catalyst and chemicals include the specific cost
of the catalyst, catalyst inventory (as determined
by the space-time yield), catalyst make-up (if
any), catalyst lifetime and chemicals
consumption.
The catalyst for the process has demonstrated
a lifetime of up to seven years in commercial
application. Together with the optimised reac-
tion concept incorporating oxydehydro-genation,
it provides for the highest space-time yields (and
lowest catalyst inventory) in the industry. The
addition of steam to the system already converts
part of the coke and tar laydown mainly to CO2
during the operation and thus allows longer
operation cycles, as well as shorter and simpler
regeneration. Regeneration takes place only in
the presence of steam and air, and no chemicals
addition is required for catalyst reactivation (eg,
chlorinating) or for coke suppression (eg,
sulphiding). Therefore, no caustic wash down-
stream of the reaction section for the removal of
chlorine is required, and no environmental
concerns that may arise from the use of chlorine
in the process have to be considered. Chemical
consumption in the downstream separation
section is very limited, with significantly lower
catalyst and chemical consumption costs.
Energy efficiency Due to the endothermic nature
of the dehydro-genation reaction, PDH processes
are quite energy intensive and a careful design

www.digitalrefining.com/article/1000632 PTQ Q1 2008 3

 HP steam
Combustion
air
Fuel gas
Reformer
Feed
O2/air
preheater
Oxyreactor
Heat
recovery
Paraffin feed
Boiler feed water
Process condensate
Process steam
Figure 1 STAR process block-flow diagram
with respect to energy efficiency is essential for
their viability. In the STAR process, the heat
from the hot reactor product is effectively recov-
ered for the production of HP steam. Preheating
of the boiler feed water and the feed/steam
mixture supplies heat for the downstream sepa-
ration section, which in addition to the reduced
energy consumption for raw gas compression, as
previously described, provides for high energy
efficiency.
Process evolution
The STAR process was originally developed by
Phillips Petroleum (now ConocoPhillips).
Development began in the 1960s with two
primary objectives: the aromatisation of C6+ cuts
and the dehydrogenation of light paraffins for
the production of light olefins. The main devel-
opment took place in the 1980s, for isobutane
dehydrogenation as well as for propane dehydro-
genation. Commercialisation of the technology
took place in the early 1990s, when two commer-
cial process plants for the dehydrogenation of
isobutane to isobutene were built and commis-
sioned, with MTBE being the downstream
product of both plants. The first plant, a 100 000
mtpa plant for Coastal Chem Inc at Cheyenne,
Wyoming, USA, was commissioned in 1992 and
4 PTQ Q1 2008
Fuel gas
Olefin
Gas product
Fractionation
separation
Raw gas
compression
the second plant, a 40 000 mtpa unit for PBA at
Ensenada, Argentina, was commissioned in
1994.
In 1999, Uhde GmbH acquired the process
technology and catalyst, including all associated
patents and rights from Phillips Petroleum.
Directly after acquisition of the technology, a
pilot plant was installed at Uhdes R&D centre in
Ennigerloh, Germany, with the aim of further
enhancing the technology by adding an oxydehy-
drogenation section downstream of the main
reactor. The pilot plant was started up in early
2001 and the developmental work took place
between 2001 and 2003. In 2006, Uhde signed a
contract for the lump-sum turnkey supply of a
PDH/PP plant complex based on the STAR proc-
ess for the oxydehydrogenation of propane and
the Basell Spheripol process for propylene
polymerisation for Egyptian Propylene & PP
Company, to be built at Port Said, Egypt, with a
capacity of 350 000 mtpa. The plant complex is
scheduled to start up in 2010.
Process description
The acronym STAR stands for steam active
reforming, describing one of the main process
features whereby the reaction takes place in the
presence of steam. Propane feed, together with
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propane recycle and steam diluent, is heated up
through heat exchange with the reactor effluent
and a fired preheater, then admitted to the main
reactor, the process reformer, an externally fired
tubular reactor, which will be discussed in more
detail. Most of the propane conversion takes
place in the reformer.
The intermediate product from the reformer is
cooled by steam and condensate injection, thereby
adjusting the inlet temperature and steam-to-
hydrocarbon ratio for the second reactor, the
oxyreactor. In the oxyreactor, oxygen is injected
into the process gas shortly above the catalyst
bed. The oxygen selectively converts the hydrogen
from the intermediate product in the top part of
the catalyst bed (selective hydrogen combustion
SHC), which shifts the thermodynamic equilib-
rium of the dehydrogenation reaction to higher
equilibrium conversion and at the same time
provides the necessary heat for the further dehy-
drogenation reaction taking place in the same
catalyst bed (Figure 1).
Heat from the hot process gas is utilised for the
production of steam in the effluent boiler, feed
preheating and supplying heat for the downstream
separation section. The process gas is further
cooled down and process condensate is separated.
The process gas containing propylene, propane and
hydrogen, as well as methane, ethane, ethylene and
CO2 is compressed in the raw gas compression and
The reactor design in the STAR process is simi-
sent to the gas-treating section, which comprises
lar to Uhdes reaction section design for syngas
an MDEA wash for the removal of CO2 and a cold production with its ammonia technology. The
box (LTRS) for the recovery of
propylene and propane from
light ends. The separated liquid
C3 fraction is sent to fractiona-
tion, which consists of a
de-ethaniser column for the
removal of C2- and a C3- splitter
column for the production of
high-purity propylene (ie, poly-
mer-grade or chemical-grade,
as required). Unconverted
propane from the C3- splitter
bottoms is, together with fresh
feed, sent to a depropaniser
column for the removal of any
C4+ prior to sending it back to
the reaction sections.
PDH catalyst performance Figure 2 Reactor system of STAR process pressure for hydrocarbons
The commercialised STAR for oxydehydrogenation of light paraffins to ensure high per-pass
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catalyst consists of platinum based on a basic
calcium and zinc aluminate, which is highly
stable in the presence of steam and oxygen at
high temperature. The catalyst is robust and
stable in operation, and has demonstrated an
expected lifetime of more than five years in
commercial application. In fact, one of the
commercial plants has used one load of catalyst
for almost seven years without interruption. As
the catalyst tolerates oxygen-containing compo-
nents as well as some levels of olefins and C4+ in
the feed, typically no upstream guard beds need
to be considered in the process.
The catalyst combines a high activity and
selectivity for the dehydrogenation reaction, as
well as for the selective hydrogen combustion in
the oxy-dehydrogenation section. Therefore, the
same catalyst is used in the reformer and the
oxydehydrogenation section. No start-of-run
(SOR) and end-of-run (EOR) need to be
considered.
The operational cycle of the reactor system is
seven hours of normal operation, followed by
one hour of regeneration. Thus, a surplus of only
one-seventh (14.3%) is required to compensate
for the capacity loss due to regeneration
requirements.
Reactor design and oxydehydrogenation
conversion of propane to
propylene is first achieved in a
steam reformer-type reactor.
This reactor design has been
used in over 60 plants built by
Uhde for various applications
(eg, ammonia and hydrogen).
Additional conversion then
takes place in the oxyreactor,
the design of which is based
on the secondary reformer
used in ammonia plants. Uhde
has built more than 40 of
these reactors. The oxyreactor
operates at an absolute exit
pressure of 5.3 bar absolute
with steam as the diluent, thus
maintaining a low partial
PTQ Q1 2008 5
 conversion. Therefore, an effi- supplied by the selective
cient heat recovery from the hot exothermic combustion of
product gas is possible, and the hydrogen, leading to a more
suction pressure for raw gas uniform heat supply
compression is 3.5 bar absolute. compared to an external
This relatively high suction firing.
pressure lowers compression Cooling of the intermedi-
costs (Figure 2). ate product from the
In principle, oxidative dehy- reformer (upstream of the
dro-genation is a commercially Figure 3 Effluent boiler oxyreactor) by the injection
proven concept, installed in of steam and condensate
seven commercial plants in the 1970s and early allows for the adjustment of the oxyreactor
1980s, with a total capacity of more than one entrance temperature and also increases the
million tons per annum (tpa) butadiene produc- steam-to-hydrocarbon rate, thus reducing coke
tion based on the so-called Oxo-D process by laydown on the catalyst. Therefore, the de-acti-
Petrotex. vation of the catalyst in the oxyreactor (back part
With oxydehydrogenation, part of the conver- of the overall reaction system) is similar to the
sion is moved to the oxyreactor. The applied reformer, and so the oxyreactor can be operated
shift of the endothermic equilibrium by selective on the same operational cycle as the reformer.
hydrogen combustion at the top segment of the After steam/ condensate injection, the interme-
oxyreactor catalyst bed allows for more efficient diate product enters the oxyreactor at the bottom
utilisation of catalyst activity throughout the and passes into one centrally arranged tube,
entire reaction section. As a result, the space- which conducts the gas to the top. This elimi-
time yield and, therefore, the overall catalyst nates troublesome external hot piping to the
requirement are reduced significantly. This head of the reactor. Process gas flow discharged
allows for smaller reactors, thereby reducing from the central tube is reversed at the top of
investment cost. Applying the oxydehydrogena- the oxyreactor and directed over a gas distribu-
tion step also increases the propylene yield. In tor for even distribution. Air or oxygen is
addition, a portion of the heat ofreaction for the admitted to the system and uniformly distributed
endothermic dehydrogenation is internally directly over the catalyst surface via a proprietary
oxygen-distribution
system. In other words,
process gas and oxygen
are rapidly mixed and
directly contacted with
the catalyst bed to
achieve high selectivities
for the conversion of
hydrogen with oxygen.

Effluent boiler
Extensive experience in
ammonia technology
was put to use when
designing the heat-
recovery system. Similar
to the fired-tube boiler
used for HP steam
generation in ammonia
plants, the effluent
Figure 4 3D model of the EPP petrochemical complex in Port Said, Egypt, to start up in boiler used for dehydro-
2009 genation plants consists

6 PTQ Q1 2008 www.digitalrefining.com/article/1000632

of a refractory lined
inlet chamber. The
Egyptian
steam drum is mounted natural gas
on top of the process
gas cooler, and is
supported by downcom-
ers and risers. Erection fractionaton
costs are low due to
shop assembly, and
access for maintenance
and inspection is easy.
Operation is based on a
reliable, free convection
flow, where there are no
heated dead ends on the
water side where debris
can settle (Figure 3).
Figure 5 Block-flow diagram of the EPP petrochemical complex in Port Said, Egypt
Supplying
polypropylene
In late 2006, Uhde was awarded the lump-sum
turnkey contract for a greenfield petrochemical
complex by Egyptian Propylene and
Polypropylene Company (EPP). Location of the
complex is Port Said, approximately 170 km
north east of Cairo, close to the mouth of the
Suez Canal. The expected startup is in 2009. EPP
is investing some $680 million in this new petro-
chemical complex, which consists of a PDH plant,
PP plant, and offsites and utilities plant, as
shown in Figures 4 and 5.
The PDH plant is designed to produce 350 000
mtpa of polymer-grade propylene based on the
enhanced STAR process technology with oxydehy-
drogenation. Feedstock to the PDH plant will be
propane from Egyptian natural gas sources. The
propylene produced will be converted to polypro-
pylene in a 350 000 mtpa PP plant applying
Basells Spheripol process. The PP plant will
produce a wide range of high-quality PP plastic
pellets. EPP will supply the PP to both the domestic
and export markets.
When planning the complex, special attention
was given to the coupling of the PDH and PP
plant not just with regard to the utility supply,
but also integration of these process plants. Some
examples of the plant integration are as follows:
Typically, a bleed stream produced in the PP
plant consisting of unconverted propylene with
propane as an impurity had to be reprocessed
inside the PP plant. When combining a PDH
plant with a PP plant, such streams can be easily
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Ethylene
import
Gas
PDH Propylene PP
PP
(Uhde STAR
Propane (base spherpol)
Process)
H2
H2 rich gas
Offsites and
utilities
EPP petrochemical
complex, Port Said
recycled to the PDH plant, as the necessary sepa-
ration equipment is available
Hydrogen required in the polymerisation reac-
tors of the PP plant can be produced from a
hydrogen-rich gas stream drawn off in the PDH
plant using pressure swing adsorption (PSA)
Process oxygen required for the oxydehydro-
genation section in the PDH plant is produced in
an air-separation unit that also produces all the
service nitrogen required for the overall complex
(eg, for pneumatic transport of the pellets in the
PP plant)
Central refrigeration supplies cryogenic service
to the PDH plant and chilled water to the PP
plant
The steam system consisting of HP, MP and
LP headers is designed and optimised for maxi-
mum flexibility, while integrating the steam
requirements of both process plants at different
pressure levels efficiently.
Low-level heat in the PDH plant is utilised to
preheat all the boiler feed water required for the
overall complex
Flaring and water usage is minimised.
Besides the technology selection and the opti-
misation performed in the design, EPP has
managed to build certain key competitive advan-
tages in developing and contracting the complex,
including location, feed supply and low energy
and labour costs, and contracting concept.
Port Said is strategically well located at the
mouth of the Suez Canal connecting the
Mediterranean and the Red Sea. Therefore, the
PTQ Q1 2008 7
 project is perfectly connected and can provide
product to many different regions in the world at
a competitive cost. Propane feed is supplied from
Egyptian natural gas, mainly from the neigh-
bouring UGDC gas fractionation plant. This
further increases the Egyptian value chain and
gives the project a long-term and secure feed-
stock supply. Furthermore, the plant location
provides direct access to fresh water and
energy supply. The cost for energy and labour in
Egypt is at an attractively low level in regional
comparison. The plant was designed and built
under a lump-sum turnkey EPC contract. This
provides for full single-point responsibility with
a true wraparound guarantee.
Summary and outlook
Propylene demand is expected to grow annually,
with a 5.4% increase in the period from 2007 to
2012.1 Steam cracking as the biggest conven-
tional source of propylene will no longer be able
to supply enough propylene to the market as
cracker feedstock moves from naphtha towards
ethane, thus producing no propylene byproduct.
The resulting supply-demand gap can only be
overcome by on-purpose propylene production
technologies like PDH and metathesis. In recent
years, the share of propylene produced by on-
purpose technologies has increased significantly.
The process discussed in this article can further
8 PTQ Q1 2008
enhance the feasibility of on-purpose propylene
production by applying the oxydehydrogenation
principle. Advantages of this technology are a
lower reactor size and lower compression costs.
The PDH plant in EPPs new petrochemical
complex in Egypt, expected to start up in 2009,
will be the first application for the advanced
oxydehydrogenation technology.
References
1CMAI, Propylene Markets and Tech Conference, Bangkok, 2007.
Max Heinritz-Adrian is global marketing manager for Uhde GmbH
gasification technology in Werdohl, Germany.
Email: max.heinritz-adrian@thysenkrupp.com
Sascha Wenzel is senior process engineer for Uhde GmbH in
Werdohl, Germany. Email: sascha.wenzel@thyssenkrupp.com
Fekry Youssef is chief process engineer for Egyptian Propylene
& Polypropylene Companys Port Said petrochemical complex in
Egypt.
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