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

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 metathesis have achieved technical maturity and acceptance, and significant developmental 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 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

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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-/calciumaluminate, 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 UOPs 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 Uhdes STAR process). With the dehydrogenation reaction being favoured by high temperatures and low partial pressures, all commercially available technologies keep the process temperature at or below approximately 650C, because higher tempera-

tures 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 3255%, with selectivities to propylene 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), 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 Uhdes 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 endo-

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PDH process technology parameters

Catalyst Reaction system Main source for heat supply UOP Oleex Pt-Sn on alumina Fluidised bed system consisting of several radial-ow adiabatic reactors in series and an external regenerator (CCR) Preheating of the feed and intermediate products before each reactor Uhde STAR process Lummus CATOFIN Pt-Sn on zinc/calcium aluminate Chromia on alumina Fixed-bed system consisting of Fixed-bed system consisting of an externally red tubular reactor a number of axial-ow adiabatic and an adiabatic reactor in series reactors connected in series External ring of the tubular reactor and selective hydrogen combustion in the adiabatic reactor Discontinuous (7 hours normal operation, 1-hour regeneration) 5 570590 6 40 89 Heating the catalyst during catalyst regeneration

Operating mode Continuous (510 days catalyst cycle time) Pressure, bara 2 Temperature, C 580650 LHSV, [m_ liq. feed/(m_ catalyst * h)] 4 Per-pass conversion propane, % 35 Selectivity propene, mol-% 8991

Discontinuous (620 minutes reaction cycle) 0.30.5 560650 <1 4865 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, hydrogen 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 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 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 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 separation section is very limited, with significantly lower catalyst and chemical consumption costs. Energy efciency Due to the endothermic nature of the dehydro-genation reaction, PDH processes are quite energy intensive and a careful design

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HP steam Combustion air Fuel gas Fuel gas

Reformer
O2/air

Feed preheater

Gas separation

Fractionation

Olefin product

Oxyreactor
Heat recovery Paraffin feed Boiler feed water Process condensate Process steam

Raw gas compression

Figure 1 STAR process block-ow diagram

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 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 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

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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-tohydrocarbon 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 fresh feed, sent to a depropaniser column for the removal of any C4+ prior to sending it back to the reaction sections.

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 Uhdes 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 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 PDH catalyst performance Figure 2 Reactor system of STAR process pressure for hydrocarbons The commercialised STAR for oxydehydrogenation of light parafns to ensure high per-pass

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conversion. Therefore, an effisupplied 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 intermedicosts (Figure 2). ate product from the In principle, oxidative dehyreformer (upstream of the dro-genation is a commercially Figure 3 Efuent 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-actiPetrotex. 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 intermeoxyreactor 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 elimitime 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 distribution 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.

Efuent boiler
Extensive experience in ammonia technology was put to use when designing the heatrecovery 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 dehydro2009 genation plants consists

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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).

Egyptian natural gas

Ethylene import

Gas fractionaton

Propane

PDH (Uhde STAR Process)

Propylene

PP (base spherpol) H2

PP

H2 rich gas

EPP petrochemical complex, Port Said

Offsites and utilities

Supplying polypropylene

Figure 5 Block-ow diagram of the EPP petrochemical complex in Port Said, Egypt

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 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

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 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 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 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

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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 neighbouring UGDC gas fractionation plant. This further increases the Egyptian value chain and gives the project a long-term and secure feedstock 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.

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 1 CMAI, Propylene Markets and Tech Conference, Bangkok, 2007. Max Heinritz-Adrian is global marketing manager for Uhde GmbH gasication 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.

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 conventional 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 onpurpose technologies has increased significantly. The process discussed in this article can further

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