Advanced propane
dehydrogenation
Oxdehydrogenation-based on-purpose propane dehydrogenation can close the
propylene supply-demand gap. Reactor design and the effect of thermodynamic
equilibrium on conversion, volume and required compression are discussed
Max Heinritz-Adrian and Sascha Wenzel Uhde GmbH
Fekry Youssef Egyptian Propylene & Polypropylene Company
T
he world is currently witnessing
a significant 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 dehydrogenation
(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
intermediate petrochemical products.
Over many years, it has maintained a
remarkable growth in demand that is
mainly attributed to the significant
growth in polypropylene (PP) demand,
which absorbs more than 60% of all the
propylene produced worldwide. PP has
grown into one of the most widely
applied plastic products, and its
broadness in application — which is
continuously 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-production 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 production is based on ethane
feedstock yielding no propylene co-
production
— Several on-purpose propylene
production technologies such as
propane dehydrogenation (PDH) and
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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
BASF/FINA Port Arthur Cracker, USA,
and several plants have been built in
Asia since then. PDH was commercialised
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
technology. 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
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 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
PTQ Q1 2008 83
commercially available technologies
keep the process temperature at or below
approximately 650°C, because higher
temperatures would lead to a significant
increase in side reactions and therefore a
decrease in the selectivity 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 conversions also
have a strongly negative impact on
propylene selectivity. At the same time,
partial pressure is kept low by applying
absolute pressures 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 32–55%, with
selectivities to propylene in the range of
87–91 mole%.
As the significant amount of coke
laydown leads to a fairly quick
deactivation of the catalyst (ie, in
the range of minutes to a few days),
different 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 Uhde’s STAR process) and adiabatic
fixed-bed systems.
Key factors in PDH design
Product work-up sections for all the PDH
technologies are very similar, as the side
products, and therefore the separation
tasks, are also similar. When comparing
different PDH technologies, several key
components need to be evaluated to find
the differences and advantages of one
technology over the other. Table 1 lists
certain data generally available in the
industry for commercial 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
parameters are an optimised temperature
profile to achieve high space-time yields
(ie, high conversion 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 endothermic
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, hydrogen and side products
— the gas needs to be compressed to
higher pressures (in the range of 15–35
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 propylene 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 sophistication vs low recovery/low
sophistication in the separation section.
An evaluation and optimisation 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
in design.
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 reaction
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 downstream 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

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 (5–10 days’ Discontinuous (7 hours’ normal Discontinuous (6–20
catalyst cycle time) operation, 1-hour regeneration) minutes’ reaction cycle)
Pressure, bara 2 5 0.3–0.5
Temperature, °C 580–650 570–590 560–650
LHSV, [m_ liq. feed/(m_ catalyst * h)] 4 6 <1
Per-pass conversion propane, % 35 40 48–65
Selectivity propene, mol-% 89–91 89 88

Table 1

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Figure 1 STAR process — block-flow diagram
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 with respect to energy efficiency
is essential for their viability. In the
STAR process, the heat from the hot
reactor product is effectively recovered
for the production of HP steam.
Preheating of the boiler feed water and
the feed/steam mixture supplies heat for
the downstream separation 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 development took place in the
1980s, for isobutane dehydrogenation as
well as for propane dehydrogenation.
Commercialisation of the technology
took place in the early 1990s, when two
commercial process plants for the
dehydrogenation of isobutane to
isobutene were built and commissioned,
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 the second
86 PTQ Q1 2008 www.eptq.com
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 Uhde’s R&D
centre in Ennigerloh, Germany, with the
aim of further enhancing the technology
by adding an oxydehydrogenation
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 process 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
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
equilibrium of the dehydrogenation
reaction to higher equilibrium
conversion and at the same time
provides the necessary heat for the
further dehydrogenation 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 sent to the gas-
treating section, which comprises an
MDEA wash for the removal of CO2 and
a cold box (LTRS) for the recovery of
propylene and propane from light ends.
The separated liquid C3 fraction is sent to
fractionation, 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,
polymer-grade or chemical-grade, as
required). Unconverted propane from
the C3- splitter bottoms is, together with

Figure 2 Reactor system of STAR process
for oxydehydrogenation of light paraffins
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
The commercialised STAR 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 components
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
The reactor design in the STAR process is
similar to Uhde’s reaction section design
for syngas production with its ammonia
technology. The conversion of propane
to propylene is first achieved in a steam
reformer-type reactor. This reactor
design has been used in over 60 plants
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Figure 3 Effluent boiler
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
pressure for hydrocarbons to ensure
high per-pass conversion. Therefore, an
efficient heat recovery from the hot
product gas is possible, and the suction
pressure for raw gas compression is 3.5
bar absolute. This relatively high suction
pressure lowers compression costs
(Figure 2).
In principle, oxidative dehydro-
genation is a commercially proven
concept, installed in seven commercial
plants in the 1970s and early 1980s,
with a total capacity of more than one
million tons per annum (tpa) butadiene
production based on the so-called Oxo-
D process by Petrotex.
With oxydehydrogenation, part of
the conversion is moved to the
oxyreactor. The applied shift of the
endothermic equilibrium by selective
hydrogen combustion at the top
segment of the oxyreactor catalyst bed
allows for more efficient utilisation of
catalyst activity throughout the entire
reaction section. As a result, the space-
time yield and, therefore, the overall
catalyst requirement are reduced
significantly. This allows for smaller
reactors, thereby reducing investment
cost. Applying the oxydehydrogenation
step also increases the propylene yield.
In addition, a portion of the heat
of reaction for the endothermic
dehydrogenation is internally supplied
by the selective exothermic combustion
of hydrogen, leading to a more uniform
heat supply compared to an external
firing.
Cooling of the intermediate product
from the reformer (upstream of the
oxyreactor) by the injection of steam
and condensate allows for the
adjustment of the oxyreactor entrance
temperature and also increases the
steam-to-hydrocarbon rate, thus
reducing coke laydown on the catalyst.
Therefore, the de-activation of the
catalyst in the oxyreactor (back part of
the overall reaction system) is similar to
the reformer, and so the oxyreactor can
be operated on the same operational
cycle as the reformer. After steam/
condensate injection, the intermediate
product enters the oxyreactor at the
bottom and passes into one centrally
arranged tube, which conducts the gas
to the top. This eliminates troublesome
external hot piping to the head of the
reactor. Process gas flow discharged
from the central tube is reversed at the
top of the oxyreactor and directed over
a gas distributor for even distribution.
Air or oxygen is admitted to the system
and uniformly distributed 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 boiler used for
dehydrogenation plants consists of a
refractory lined inlet chamber. The
steam drum is mounted on top of the
process gas cooler, and is supported by
downcomers and risers. Erection 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).
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 petrochemical
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 oxydehydrogenation.
Feedstock to the PDH plant will be
propane from Egyptian natural gas
sources. The propylene produced will be
converted to polypropylene in a 350 000
mtpa PP plant applying Basell’s 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 recycled to the PDH plant, as
the necessary separation equipment
is available
— Hydrogen required in the
polymerisation reactors 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
oxydehydrogenation section in the PDH
plant is produced in an air-separation
unit that also produces all the service
nitrogen required for the overall Figure 4 3D model of the EPP petrochemical complex in Port Said, Egypt, to start up
complex (eg, for pneumatic transport of in 2009
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 maximum 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 optimisation performed in the
design, EPP has managed to build
certain key competitive advantages in
developing and contracting the
complex, including location, feed Figure 5 Block-flow diagram of the EPP petrochemical complex in Port Said, Egypt
supply and low energy and labour costs,
and contracting “concept”. Summary and outlook Egypt, expected to start up in 2009, will
Port Said is strategically well located Propylene demand is expected to grow be the first application for the advanced
at the mouth of the Suez Canal annually, with a 5.4% increase in the oxydehydrogenation technology.
connecting the Mediterranean and the period from 2007 to 2012.1 Steam
Red Sea. Therefore, the project is cracking as the biggest conventional
perfectly connected and can provide source of propylene will no longer be
product to many different regions in the able to supply enough propylene to the References
1 CMAI, Propylene Markets and Tech
world at a competitive cost. Propane market as cracker feedstock moves from Conference, Bangkok, 2007.
feed is supplied from Egyptian natural naphtha towards ethane, thus producing
gas, mainly from the neighbouring no propylene byproduct. The resulting
UGDC gas fractionation plant. This supply-demand gap can only be
further increases the Egyptian value overcome by on-purpose propylene
chain and gives the project a long-term production technologies like PDH and
and secure feedstock supply. metathesis. In recent years, the share of Max Heinritz-Adrian is global marketing
Furthermore, the plant location provides propylene produced by on-purpose manager for Uhde GmbH gasification
direct access to fresh water and technologies has increased significantly. technology in Werdohl, Germany. Email:
energy supply. The cost for energy and The process discussed in this article max.heinritz-adrian@thysenkrupp.com
labour in Egypt is at an attractively can further enhance the feasibility of Sascha Wenzel is senior process engineer
low level in regional comparison. The on-purpose propylene production by for Uhde GmbH in Werdohl, Germany.
plant was designed and built under a applying the oxydehydrogenation Email: sascha.wenzel@thyssenkrupp.com
lump-sum turnkey EPC contract. This principle. Advantages of this technology Fekry Youssef is chief process engineer
provides for full single-point are a lower reactor size and lower for Egyptian Propylene & Polypropylene
responsibility with a true wraparound compression costs. The PDH plant in Company’s Port Said petrochemical
guarantee. EPP’s new petrochemical complex in complex in Egypt.

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