Easy Mathematical Model for Pressure Swing Adsorption

Pressure Swing Adsorption

Pressure swing adsorption (PSA) removes impurities under pressure according to their affinities to an adsorbent.

From: Advances in Bioenergy , 2021

22nd European Symposium on Computer Aided Process Engineering

Joakim Beck , ... Eric S Fraga , in Computer Aided Chemical Engineering, 2012

Abstract

Pressure swing adsorption (PSA) is a cyclic adsorption process for gas separation and purification. PSA offers a broad range of design possibilities influencing the device behaviour. In the last decade much attention has been devoted towards simulation and optimisation of various PSA cycles. The PSA beds are modelled with hyperbolic/parabolic partial differential algebraic equations and the separation performance should be assessed at cyclic steady state (CSS). Detailed mathematical models together with the CSS constraint makes design difficult. We propose a surrogate based optimisation procedure based on kriging for the design of PSA systems. The numerical implementation is tested with a genetic algorithm, with a multi-start sequential quadratic programming method and with an efficient global optimisation algorithm. The case study is the design of a dual piston PSA system for the separation of a binary gas mixture of N ₂ and CO₂.

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21st European Symposium on Computer Aided Process Engineering

Harish Khajuria , Efstratios N. Pistikopoulos , in Computer Aided Chemical Engineering, 2011

1 Introduction

Pressure swing adsorption (PSA) is at the forefront of gas separation technology. Modern PSA systems used in the industry can vary from 2 adsorbent beds separating air, to 16 bed system producing pure hydrogen in excess of 100, 000  Nm³/hr. In spite of receiving continuous attention from the system engineering community, rigorous design and control of industrial scale PSA operation remains a challenging task (Nikoliü et.al., 2009; Nilchan and Pantelides, 1998). This is because of the fact that PSA operation is not only highly nonlinear and dynamic but also poses extra challenges due to its unique property of exhibiting only a cyclic steady state (CSS). The absence of a true steady state is attributed to the fact that a PSA system comprises of a network of bed interconnecting valves, whose active status keep changing over time. This study is concerned with exploring the benefits of integration of the controller design problem during the process design stage in order to obtain improved PSA design with superior real time operability.

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Advanced Ultrasupercritical Thermal Power Plant and Associated Auxiliaries

Swapan Basu , Ajay Kumar Debnath , in Power Plant Instrumentation and Control Handbook (Second Edition), 2019

3.1.2.1.2 Air Separation Unit Using Pressure Swing Adsorption

PSA is a noncryogenic air separation process that is commonly used in commercial practice. This process as depicted in Fig. 13.3B, ASU by PSA method, involves the adsorption of the gas by adsorbents such as zeolite and silica in a high-pressure gas column.

In the PSA process, the air is drawn from the ambient atmosphere and compressed into high-pressure gas. The gas will be transferred into a column that is filled with the desired adsorbent materials, depending on the required gas. The system will be pressurized for a predetermined period and depressurized to atmospheric pressure, where the low sorbing gas will slowly leave the column first, followed by the other gases. If the adsorption process occurs under vacuum conditions instead of a pressurized environment, the process will be called vacuum swing adsorption (VSA). Generally, there are two or more adsorbent columns in the PSA process to avoid system downtime during the pressurized and depressurized processes. The PSA is appropriate to be utilized at a relatively lower daily production volume of 20–100 tons of oxygen and an oxygen purity ≥ 90%. Until now, M/s Praxair has pushed the production limit to 218 tons of oxygen per day with the purity up to 95% by integrating the PSA and VSA into one process, namely vacuum pressure swing adsorption (VPSA).

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CO2 adsorption by swing technologies and challenges on industrialization

Niloufar Fouladi , ... Hamid Reza Rahimpour , in Advances in Carbon Capture, 2020

11.4.7 CO₂ PSA processes configurations

PSA processes can be categorized into single-bed processes and multibed processes based on the number of adsorbers. Fig. 11.5 indicates a schematic representation of an ordinary single-bed PSA. Here is a short review of the process description: at the beginning, valves 1, 2, and 3 are opened and valve 4 is closed. The pressure of the bed is increased by the gas feed which involves CO₂, till the pressure P _H is achieved and the column is saturated with CO₂.

Fig. 11.5. Schematic representation of single-bed PSA (RPSA) [30].

Through these adsorption and pressurization processes, CO₂ recovers in the raffinate flow. Valves 1 and 3 are closed, then in order to depressurize the column to the pressure P _L valve 4 is opened. At the time that P _L is obtained and stabilized, valves 2 and 3 and 4 are closed and valve 1 would be opened, i.e., the food stream is stopped or it is lead to other place, for extraction of the residual CO₂ by pumping from the column into a CO₂ storage equipment. This process is termed as blowdown; the column pressure is lightly less than P _L. The next step is the column to be purged with a part of CO₂ lean gas, which was captured by opening valves 2 and 3. The gas should be recycled into the CO₂ lean gas storage or it might be vented to the atmosphere (which is undesirable).

The cycle time of single-bed adsorptions is usually shorter than multibed PSA (Fig. 11.5). Therefore, single-bed PSA is also called rapid PSA (RPSA). RPSA also has larger pressure drops. Multicolumn PSA comprise two or more columns which are interconnected and continuous feed and product flow are achievable [30].

A diversity of configurations PSA cycle has been proposed for CO₂ capture from exhaust gases. At the pressure level around atmospheric, in postcombustion applications, the most popular PSA procedures are based on adsorbent regeneration below atmospheric condition (vacuum pressure swing adsorption, VPSA). Instead of applying vacuum pressure, as an alternate to vacuum pressures, pressurizing of upstream exhaust gas has been investigated, which is believed to be inapplicable with regard to high energy requirement. Different arrangement of process steps are applicable to achieve the desired CO ₂ content and recovery, so the main properties of optimization of the process, becomes energy requirement for applying the gas separating operation, i.e., 90% recovery for CO₂ (RCO₂) and 95% purity for CO₂ (ϑCO₂). Some studies indicate that a single-step operation can provide comparable performance with approximately equal energy consumption, but high vacuum condition is required which are not simply applicable in large scale. Besides, the results of the experiments on the same PSA system combination does not confirm the output of the simulation every time. This is an indication of level of sophistication of these systems and the need for additional validation of the results [28].

For precombustion CO₂ separation processes, normally a one-step PSA is adequate. However, usually, sophisticated PSA arrangement is applied, implementing several columns and various scheduling of cycles. However, complicated PSA configurations is normally applied, containing several columns working in parallel with different scheduling of cycles. Exemplary, although increasing the number of pressure equalization steps, leads to an increase in the performance of the system, it also makes the system more complicated. It could also introduce as an alternative method to use two-stage system which is also called dual PSA concept. However, the main focus of the literature is on single-stage PSA designs [28].

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Current and future oxygen (O2) supply technologies for oxy-fuel combustion

N.M. Prosser , M.M. Shah , in Oxy-Fuel Combustion for Power Generation and Carbon Dioxide (CO2) Capture, 2011

10.3 Vacuum pressure swing adsorption technology

Pressure swing adsorption systems for oxygen production were first used in the 1970s. Since then, the technology has rapidly improved. The early systems operated the entire operational sequence above atmospheric pressure. However, incorporation of a sub-atmospheric regeneration step much more fully utilized the characteristics of the adsorbent. This vacuum pressure swing adsorption method resulted in a significant decrease in energy consumption ( Smolarek et al., 2000). In 1989, the first vacuum pressure swing adsorption installation was started up. Today's VPSA systems use less than 50% of the power of the earlier PSA designs. One-bed systems and two-bed systems are employed. The one-bed systems offer capital savings, but are limited to about one-half of the production of a two-bed system because a single machine provides both feed as well as vacuum functions as opposed to the individual feed and vacuum blowers of the two-bed system.

A simplified two-bed schematic is shown in Fig. 10.4. The feed air blower supplies air to the on-stream adsorbent vessel. Nitrogen, water vapor, carbon dioxide, and atmospheric hydrocarbons are preferentially adsorbed, while most of the oxygen and argon pass through. The product oxygen stream is available at a natural pressure of 0.2–0.35 barg (3–5 psig) from the system. An oxygen compressor is used when higher pressures are needed. The oxygen purity is 90–93% by volume. System capacity and efficiency suffer dramatically above 93% oxygen purity. The off-stream adsorbent vessel is regenerated under vacuum (0.3–0.7 bara, 4–10 psia) using the vacuum pump (blower). The nitrogen, carbon dioxide, and moisture desorb during this time. At the end of the desorption period, a small quantity of product oxygen is used to purge the remaining desorbed contaminants prior to repressurizing the bed for the adsorption step. Today's advanced systems have a cycle time of less than one minute. There is a period of time during each cycle in which no oxygen is produced. The surge tank, which is a low pressure storage vessel downstream of the adsorbent bed, enables a smooth supply of gas oxygen to the customer.

10.4. Two-bed oxygen VPSA system

In addition to the step improvement that the introduction of VPSA enabled, innovations in every area of system and component design and operation have led to continued, large improvements in capital cost and energy efficiency. Development can be divided into four subject areas: adsorbent materials, process design, system design, and component packaging. Adsorbent advances have been the key to substantially reducing the cost of VPSA oxygen. Today's VPSA bed sizes are less than one-tenth that of the early systems. In addition to the reduction in vessel size and adsorbent requirements, improved adsorbent has enabled a reduction in the size of the machinery and all other components, and has led to lower power consumption. Lithium exchanged Type X (LiX) zeolites are the most cost effective for air separation (Chao, 1989). They provide a large increase in nitrogen working capacity. Of the many process design improvements, an example is the incorporation of performance enhancing steps such as pressure equalization and product purge (Baksh et al., 1996). System design improvements over the years have greatly simplified VPSAs. Today's systems use fewer adsorbent beds and valves, and significantly less adsorbent than the earlier commercial units. Component packaging improvements have enabled compact, skid mounted equipment layouts. This reduces overall cost by reducing the engineering and field installation costs through efficient shop assembly. Also, this has led to shorter project schedules and increased equipment recoverability. Figure 10.5 illustrates the marked improvement in total VPSA oxygen cost since its early commercialization, and the improvement with respect to capacity.

10.5. VPSA oxygen cost and capacity improvement (Shah, 2005).

The maximum capacity available from a VPSA plant is dictated by the capacity of commercially available blowers used for feed and vacuum service, and by vessel size constraints. Higher capacities are generally achieved with the installation of multiple VPSA plants; however, due to economies of scale there is a practical limit above which cryogenic supply becomes more economically attractive. Figure 10.6 illustrates the typical range of economic application for VPSA systems. In addition to this, VPSA systems are best suited to applications with modest oxygen pressure requirements due to the large expense of an oxygen compressor to deliver higher pressures. For application in an oxy-coal installation VPSA is not the economical choice primarily because of the large oxygen production rates needed. The lower purity of VPSA also would add cost for the CO₂ purification system.

10.6. Oxygen supply system typical economic ranges.

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CO2 Sorption

Soonchul Kwon , ... Manvendra K. Dubey , in Coal Gasification and Its Applications, 2011

Pressure Swing Adsorption (PSA)

Pressure swing adsorption (PSA) has been applied to separate gas mixtures, such as carbon dioxide capture in ammonia production and in hydrogen purification. ^6,13,18–32

In terms of the high cost-effectiveness, PSA is viewed as an attractive approach due to its simple operation, high performance at ambient temperatures, high regeneration rate, and low energy intensity. ³³

In the PSA process, gas species can be separated from a gas mixture at high pressure and low temperature, by being passed through a reactor containing the sorbent. The pressure is then reduced, releasing CO₂ from the adsorbent surface relatively easily since electrons between adsorbent and adsorbate are not shared.

Figures 10.3 and 10.4a illustrate examples of pressure swing adsorption systems. PSA operation includes: ^13,29 (1) pressurization of the inlet gas (over 3 atm), (2) adsorption with inlet gas at high pressure, (3) depressurization to atmospheric pressure, releasing CO₂ at the bottom of desorption column, and (4) desorption CO₂ gas from the adsorbent with purging gas at ~1 atm. After flue gases are introduced into one chamber column 1 is pressurized, resulting in the CO₂ adsorption. The applied pressure is transferred to column 2. When column 2 is pressurized, column 1 is depressurized to ~1 atm and carbon dioxide is separated from the flue gas. For the desorption steps, the inlet CO₂ gas stream is stopped and N₂ is only introduced to desorb CO₂ after depressurization. The cycle continues as a switching mode from adsorption column to desorption column.

Figure 10.3. Schematic diagram of pressure swing adsorption system. ³⁴

Figure 10.4. Operational steps of pressure and vacuum swing adsorption systems. ^5,13 (a) Pressure swing adsorption system. (b) Vacuum swing adsorption system.

The mechanism of the PSA system is based on either equilibrium thermodynamics selectivity or kinetics selectivity. Thermodynamic equilibrium selectivity depends on the different gas concentrations at equilibrium state of the gas molecular mixture for the separation processes. For PSA using equilibrium selectivity, strongly adsorptive gas components remain in the adsorbent column, whereas weakly adsorbed species are discharged in the high-pressure gas streams.

Kinetic selectivity, on the other hand, is based upon having different diffusion rates of gas molecules in the non-equilibrium system. Faster diffusing gas species go to the sorbent column while the slower diffusing gases flow out. Thus, the diffusion rate determines the selectivity mechanism. For the optimization of the PSA process, operating conditions and system factors are determined by the rate-determining mechanism.

Operating processes have evolved to improve the efficiency of PSA separations. To optimize the bed size and sorbent usage, different adsorptive sorbents such as activated carbon and zeolites, which have strong CO₂ affinity, are utilized within the layered sorbent bed where activated carbon sorbents are placed ahead of a zeolite sorbents. ²⁰ In the first layered column, activated carbon mainly adsorbs CO₂ species and zeolites in the second layered column capture the residual CO₂ components. This approach was introduced in the 1970s; but it was not well suited for industrial facilities due to the many limiting factors, including the low sorption capacity of adsorbents and unstable operating controls.

PSA has three significant drawbacks. First of all, the short cycle times bring high "switch" losses, which are the losses of feed gas in the bed after venting out in the depressurization step. ³⁵ In addition, the short cycle times can cause the rate change of inlet flow, leading to the unstable pressure in the column during the plant operation. Secondly, PSA processes typically add impurities to the gas components at low pressures and these components will adsorb more strongly than carbon dioxide. Thirdly, PSA has a low cost-effectiveness for CO₂ recovery from flue gas steams. CO₂ recovery costs can lower when the CO₂ concentration in a flue gas stream is high. However, separation processes operate at thousands of kPa and cannot separate CO₂ to less than about 10 kPa partial pressure due to the low CO₂ partial pressures. Thus, compression systems are used to reduce high pressure to the normal operating pressure, but this additional energy demand causes extra costs. In spite of these weaknesses, PSA still plays a significant role in the hybrid system due to low cost and simple operation.

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FUELS – HYDROGEN PRODUCTION | Gas Cleaning: Pressure Swing Adsorption

S.D. Sharma , in Encyclopedia of Electrochemical Power Sources, 2009

Plant Capacity and Size

Pressure swing adsorption plants are usually much larger than cryogenic gas separation plants and this is because of poorer load capacity of the adsorbents and long cycle time of the plant. The size of the PSA plants could be further reduced by developing adsorbents with higher load capacity, low mass transfer resistance, and higher thermal conductivity. The development of hollow fiber adsorber is a consequence of addressing some of these issues.

Economic separation with feed gases having less than 50% hydrogen content is the main issue particularly for the future hydrogen economy as syngas generated from the gasification of biomass and coal or reforming of methane could have less than 50% hydrogen. The use of carbon nanotubes could be an answer to this challenge because of their selectivity for hydrogen.

The use of multilayered adsorber in PSA has great potential to achieve high-purity recovery and production with smaller size beds. However, refraction and interlayer interference have to be minimized with the development of better adsorbents and optimization of layering sequence.

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Hybrid processes based on membrane technology

Patricia Luis , in Fundamental Modelling of Membrane Systems, 2018

8.4.2 Example 2: Hybrid Pressure Swing Adsorption—Gas Permeation for Gas Separation

Pressure swing adsorption (PSA) is an alternative to cryogenic gas separation that achieves very high purity. Gas permeation using membranes has also become a common technology for gas separation, mainly when product purity requirements are less severe. Esteves and Mota (2002) presented an optimized gas separation process integrating membranes and PSA aiming at the separation of H₂/CH₄ mixtures, improving product purity and/or recovery compared to the stand-alone systems. Fig. 8.12 presents the schematic diagram of the hybrid cyclic process developed for bulk separation of a binary mixture using a membrane device and a dual-bed PSA unit. The membrane has the objective of performing the bulk separation operating in countercurrent flow mode to maximize the average driving force. Both the permeate and retentate streams are sent to the PSA at different steps for higher purity and recovery. The retentate is sent directly to the PSA but the permeate stream is stored in an intermediate tank before being sent to the adsorbent unit. Basically the following steps are proposed: (1) incomplete pressurization (PR₁) of one of the PSA beds with the permeate stream, which is stored in the intermediate tank; (2) the adsorbent bed is pressurized with regular feed gas to complete the pressurization step (PR₂); (3) the high pressure adsorption step (HPA) is initiated by feeding the PSA with the residue stream from the membrane; (4) cocurrent blowdown (CD) to recover the residual amount of component A; (5) countercurrent blowdown (BD) and purge (PG) to recover component B and regenerate the bed for the next cycle. In this process, each bed as well as the membrane is operating in batch but the whole process is continuous and it operates in cyclic steady state (Esteves and Mota, 2002).

Fig. 8.12. Cycle sequence of hybrid membrane-PSA process.

Reproduced with permission from Esteves, I.A.A.C., Mota, J.P.B., 2002. Simulation of a new hybrid membrane/pressure swing adsorption process for gas separation. Desalination 148, 275–280.

Fig. 8.13 shows the H₂ recovery and purity for the stand-alone PSA and the hybrid process as a function of the feed flow rate (Esteves and Mota, 2002). An increase of the feed flow rate results in longer bed coverage at the end of the HPA step and decreases the purity of CH₄. In addition, the hybrid system allows a higher feed throughput than the stand-alone PSA unit for the same separation performance. Thus the hybrid using membrane gas permeation increases the treatment capacity of the overall process.

Fig. 8.13. Impact of feed flow rate on H₂ product purity (A) and recovery (B) for stand-alone PSA (△, P,   =   35   bar; ▴, P,   =   2.5   bar) and for the hybrid gas permeation-PSA (□, P,  =   35   bar; ▪, P,   =   25   bar).

Reproduced with permission from Esteves, I.A.A.C., Mota, J.P.B., 2002. Simulation of a new hybrid membrane/pressure swing adsorption process for gas separation. Desalination 148, 275–280.

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Hydrogen Production

Mohamed A. Fahim , ... Amal Elkilani , in Fundamentals of Petroleum Refining, 2010

11.4.3.3 Pressure Swing Adsorption (PSA)

The reformed gas from the shift converter which contains 65–70 vol% hydrogen can be purified by adsorption instead of amine treatment and methanation. The process produces a higher purity hydrogen stream (99.9%).

PSA is a cyclic process involving the adsorption of impurities (CO, CO₂, CH₄ and N₂) from a hydrogen-rich gas stream at high pressure on a solid adsorbent such as a molecular sieve. The operation is carried out at room temperature and at the reformed gas pressure of 20–25 bar (294–368   psia). Several adsorption vessels (adsorbers) are employed as shown in Figure 11.4. The feed gas is switched from one adsorption vessel to another. While adsorption takes place in one vessel, the adsorbent in another vessel is being regenerated. A complete pressure swing cycle for each adsorber goes like this:

Figure 11.4. Pressure swing adsorption cycle (Stocker and Whysall, 1998)

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Adsorption takes place in a fresh adsorber producing high purity gas. The impurities are adsorbed onto the internal surfaces of the adsorbent bed. When this adsorber reaches its adsorption capacity and no more impurities can be removed, it is taken off-line, and the feed is switched to another fresh adsorber.

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To recover the hydrogen trapped in the adsorbent void spaces in the adsorber, the adsorber is depressurised from the product side in the same direction as the feed flow direction (cocurrent), and high-purity hydrogen is withdrawn. The hydrogen is used internally in the system to repressurise and purge other adsorbers.

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The bed is then partly regenerated by depressurising in a countercurrent flow of gas from other beds, and the desorbed impurities are rejected to the PSA off-gas.

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The adsorbent is then purged with high-purity hydrogen (taken from another adsorber on cocurrent depressurisation) at constant off-gas pressure to further regenerate the bed.

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The adsorber is then repressurised with hydrogen prior to being returned to the feed step. The hydrogen for repressurisation is provided from the cocurrent depressurisation and with a slipstream from the hydrogen product. When the adsorber has reached the adsorption pressure, the cycle has been completed, and the adsorber is ready for the next adsorption step.

In addition to hydrogen production, PSA technology is used for purifying hydrogen streams from other units in the refinery, in petrochemical units, the steel industry and hydrogen for fuel cells. The advantages of the PSA process are:

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High purity of hydrogen: 99.9%. Conventional units with amine treating and methanation seldom achieve purity higher than 98%.

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Purity in conventional units depends on the quantity of inerts in the feed. The PSA process yields over 99.9% purity regardless of feed quality.

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The conventional process requires severe steam reforming operating conditions in the reformer furnace to get over 97% H₂ purity. The PSA process allows less severe operating conditions and still achieves high purity. However, this results in 3–8% unreacted methane in the purge stream.

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Purity can be increased on request.

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High efficiency of hydrogen recovery: up to 90%.

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PSA technology is more reliable and requires less capital cost.

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Operating costs in the PSA process are lower due to lower energy expenditures. The PSA purge is used as furnace fuel. Considerable steam is produced and can be exported to other units in the refinery.

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History of Proton Exchange Membrane Fuel Cells and Direct Methanol Fuel Cells

Noriko Hikosaka Behling , in Fuel Cells, 2013

7.5.1.1.3.3 PSA Peugeot Citroen

PSA has taken a long-term view of fuel cell technology and is moving rather slowly on FCV development. From early on, it has indicated that the commercialization of fuel cells would take place between 2010 and 2020. It views using fuel cells as range extenders or as auxiliary power units. In 2001, it introduced the Taxi PAC in 2001, with a 5.5 kW H Power fuel cell as a range extender. In 2002, it presented the H₂O Firefighter , which used fuel cells for an auxiliary power unit that charged the batteries. In 2004, PSA developed a four-wheel vehicle, the Quark , with a 1.5 kW fuel cell developed by MES-DEA, a Swiss energy company. ⁴³⁷ The fuel cell also served as a range extender. In October 2006, PSA unveiled the Peugeot 207 ePURE , powered by a 50 kW lithium-ion battery, CEA's 20 kW GENEPAC PEMFC, and an electric motor. ⁴³⁸ The fuel cell was used as a range extender. The Peugeot 207 ePURE had five compressed hydrogen tanks (70 MPa) containing 3 kg of hydrogen. In 2007, the company unveiled the Peugeot Flux, a futuristic design car, at the Frankfurt Motor Show. ⁴³⁹ The car had a hydrogen internal combustion engine. In 2008, PSA developed the H₂Origin Light Utility Urban Vehicle , powered by a 10 kW Intelligent Energy PEMFC, a 180 V Panasonic nickel–metal hydride battery pack, and an electric motor. ⁴⁴⁰ The fuel cell also was used as a range extender. The H2Origin had a top speed of around 60 mph and a driving range of 186 miles. ⁴⁴¹ In 2009, PSA unveiled the Peugeot 307 CC FiSyPAC FCV hybrid , a fully electric vehicle, based on a Peugeot 307 coupe cabriolet. ⁴⁴² The FCV hybrid was powered by a 17 kW GENEPAC fuel cell stack, developed by the French Atomic Energy Commission (CEA), and a 13 kW Li-ion battery pack (with energy densities of 100 Wh/L and 88 Wh/kg). The fuel cell served as a range extender, giving the EV demonstrator a range of 310 miles at 62 mpg.

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PSA clearly has made considerable use of fuel cells as range extenders in electric vehicles. The FiSyPAC demonstrator ranked among the world's top performers, needing less than 1 kg of hydrogen per 62 miles. ⁴⁴³ PSA also successfully quadrupled the fuel cell's lifespan and increased its efficiency by nearly 20 percent since 2006.

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It still has the view that fuel cells have a number of unresolved challenges, including cost, lifespan, the need for lithium-ion batteries, and the need for an infrastructure to market hydrogen to the general public. ⁴⁴³ Nonetheless, PSA believes that it would be able to mass market vehicles with fuel cell range extenders in the 2020–2025 period.

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