Energy analysis of innovative systems with metallic membranes

12 Energy analysis of innovative systems with metallic membranes Vincenzo Spallina,1 Fausto Gallucci2 1

Department of Chemical Engineering and Analytical Science, University of Manchester, Manchester, United Kingdom; 2Inorganic Membranes and Membrane Reactors, Sustainable Process Engineering, Department of Chemical Engineering and Chemistry, Eindhoven, University of Technology (TU/e), Eindhoven, The Netherlands

Introduction The current fossil fuelebased economy is the major responsible for greenhouse gas effect and climate change. It is widely accepted that the global warming can be avoided by combining various solutions such as carbon capture and sequestration (CCS), fuel switching, and a large use of renewable energy sources [1,2]. Major concerns on environmental consequences of fossil fuel usage have pushed several governments to support greenhouse gas emission reduction policies. EU, for example, set a very high target of reduction of greenhouse gas emissions by 20% within 2020, together with an increase by 20% of energy efficiency and renewable share in the energy production [3]. A hydrogen-based economy has shown potential to be a key part of the solution. H2 represents an important product for the chemical industry [4], and its use as automotive fuel will increase beyond the current 600 billion Nm3/y [5]. Traditionally, hydrogen is produced via steam reforming (SR) of hydrocarbons such as natural gas (NG), naphtha oil, or methanol/ethanol [6]. Two main routes are typically used for H2 production: in the first case, a multitubular fixed bed reactor (fired tubular reformerd FTR) is used to convert fuel into syngas and an external furnace is used to provide the heat of reaction; in the second case an autothermal reforming (ATR) reactor is employed in which an oxidant (air or pure oxygen) is fed to the system [6e9]. The major reactions Current Trends and Future Developments on (Bio-) Membranes. https://doi.org/10.1016/B978-0-12-818332-8.00012-0 © 2020 Elsevier Inc. All rights reserved.

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occurring in the reforming are steam methane reforming (SR, Eq. 12.1), methane partial oxidation (POX, Eq. 12.2), and water gas shift (WGS, Eq. 12.3) as listed below: CH4 þ H2 O43H2 þ CO DH298K ¼ 206:2 kJ=mol 0

(12.1)

1 ¼ 38 kJ=mol CH4 þ O2 42H2 þ CO DH298K 0 2

(12.2)

CO þ H2 O4H2 þ CO2 DH298K ¼ 41:2 kJ=mol 0

(12.3)

Several conversion and separation steps are required in a conventional SR processes such as feedstock pretreatment and sulfur compounds abatement, high temperature reforming, WGS reactor(s), and final H2 separation in a pressure swing adsorption (PSA) unit in order to reach a high H2 purity of 99.999%. Compared to conventional fuel processing technology for light hydrocarbons, membranes-based technology is a promising technology for integration into a reaction and separation process involving pure hydrogen generation from light hydrocarbons [10]: they can work at high temperatures and pressures with high permselectivity but limited permeation flux. Membrane technology has been in strong development over the past 50 years and during this period has established a time and tested manufacturing method spanning from a variety of applications such as microfiltration of bacteria, gas separation, water treatment, and reverse osmosis. Membranes hold many advantages [11,12] such as: • Mild process conditions; • Typically, low energy consumption; • Continuous process; • Ease of scaling up. Among different membrane types [13], metallic palladium alloy is the most promising for high-flux hydrogen separation. Moreover, due to the suitable range of operating conditions, dense palladium membranes allow carrying out both the reaction and pure hydrogen separation in the same device. The hydrogen transport in the palladium membranes occurs through a solution/diffusion mechanism, which follows six different activated steps [14]: • dissociation of molecular hydrogen at the gas/metal interface; • adsorption of the atomic hydrogen on membrane surface; • dissolution of atomic hydrogen into the palladium matrix; • diffusion of atomic hydrogen through the membrane; • recombination of atomic hydrogen to form hydrogen molecules at the gas/metal interface; • desorption of hydrogen molecules.

Chapter 12 Energy analysis of innovative systems with metallic membranes

The most relevant issue associated with Pd membranes is the phase transition also called “hydrogen embrittlement” which occurs when Pd is contacted with H2 at temperature below 300 C and pressure below 20 MPa; the b-hydride nucleates and the pure Pd brittles and therefore it becomes very easy to destroy [15,16]. Other than that, Pd-based membranes’ performances are strongly affected by contaminants poisoning, especially sulfur compounds, Hg vapor, chlorine, as well as some decay in the performance is expected in presence of CO and also H2O which could be reduced by adding other metals [17]. Finally, in presence of coking, the carbon atoms penetrate into the Pd lattice and cause the failure. In order to increase the mechanical stability, Pd membranes are usually deposited on a ceramic and metallic layers (supported membranes) and also different engineering solutions have been proposed to build up the membrane module (tubular, hollow fiber, and planar) [18]. Pd-based membranes have been tested under different conditions in terms of temperature (300,600 C), H2 partial pressure difference (up to 4 bar) reaching different permeability (up to 4.7  104 mol$m2$s1$Pa1) which is affected by the selectivity required and the steam conditions [11,18]. Currently, different membrane modules of 0.65 m2 module have been produced and tested for different applications [19] capable of handling up to 2.7 ton per day (200 Nm3/h) synthesis gas slipstream from a methanol synthesis plant in Tjeldbergodden [19]. In FCHeBIONICO (http://www.bionicoproject.eu/), a biogas membrane reactor with hydrogen production capacity of approximately 100 kg day1 has been built and will be tested on-site. All these advances in Pd membranes have been followed by different design to assess the expected performance of the integrated system for very relevant industrial processes [20]. As it will be discussed later, the membranes represent a part of the required engineering while the complete plant would require different reactors and separation unit, as well as different power devices to run the entire system. The design and engineering of the complete plant is extremely important at this stage since the assessment of the expected technoeconomic and environmental performance is only partly affected by the cost of the membranes. Therefore, in this chapter, the current state of the art on the integrated membrane and membrane reactor is discussed from an energy and technoeconomic point of view. Three major Pd-based membrane and membrane reactor applications: - Pure H2 production is considered for large-scale production and in case of combined heat and power (CHP) generation

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including the use of polymer electrolyte membrane fuel cells (PEMFCs); - Pd-based membranes are discussed for power generation with integrated CCS; - Dehydrogenation process for the production of olefins using Pd-based membranes and membrane reactors. For the selected configurations, several energy analyses have been carried out in the past and the effect of the most important parameters is discussed. Whether available an overview on the costs is presented to provide a comparison of the membrane technologies and their profitability with respect to the state-ofthe-art technologies.

Hydrogen production Hydrogen production is the most studied application for the Pdbased membranes. NG is the most used feedstock for H2 production especially in small and medium application such as CHP generation as well as PEM microcogeneration. The conventional natural gas SR requires typically one fired or ATR unit, two WGS reactors operated at different temperature to achieve high CO conversion (>98%), and, in case of PEMFC, the CO in the fuel to the anode needs to be lower than 10 ppm and therefore a preferential oxidizer unit or a methanator is used to achieve the desired specifications for the fuel cell. Instead, in presence of a high-selective Pd membrane reactor, pure H2 and humidified H2 are produced in a single unit as shown in Fig. 12.1. Two possible configurations are considered: heated membrane reactor and ATR. Roses et al. [22] have carried out a comprehensive technoeconomic assessment to produce H2 for fuel cell vehicle fleet using four configurations: (i) the conventional steam reforming coupled with a WGS reactor and PSA (named SR-PSA), (ii) a thermally heated steam reforming membrane reactor (SR-MR), (iii) an autothermal reforming membrane reactor (ATR-MR), and (iv) a steam reforming and WGS membrane reactor (WGS-MR). As shown in Table 12.1, for a fixed amount of produced H2, the amount of NG decreases using SRMR and ATR-MR. This can be explained by the lower exergy losses associated to a lower operating temperature in the reformer and the simultaneous separation. In terms of electricity demand, the membrane-based processes present higher consumptions due to the low H2 pressure at the permeate side while in case of SRPSA, H2 is separated at high pressure and the compressor is not

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297

Figure 12.1 Comparison of different routes from natural gas to pure H2 using conventional technologies and membrane reactors as presented in Roses et al. [21]. ATR, autothermal reforming; NG, natural gas; PEM, polymer electrolyte membrane. Copyright 2015. Reproduced with permission from Elsevier.

Table 12.1 Performance comparison

NG H2 output NG compressor Air compressor H2 compressor Total efficiency Capital cost O&M cost Capital recovery cost Production cost Cost of H2 production

units

SR-PSA

SR-MR

ATR-MR

WGS-MR

kWHHV kWHHV kW kW kW % $ $/a $/kgH2 $/kgH2 $/kgH2

222.6 177.1 11.7

203 177.1 18

234.6 177.1 19.1

79.6 392,745 19,637 3.46 1.27 4.73

7.3 87.3 373,552 18,845 3.29 1.33 4.62

195.9 177.1 22.8 4.4 7.3 90.4 382,383 19,357 3.38 1.41 4.79

7.3 75.5 372,704 18,717 3.28 1.5 4.78

ATR-MR, autothermal reforming membrane reactor; NG, natural gas; O&M, operation and maintenance; SR-MR, steam reforming membrane reactor; SR-PSA, steam reforming pressure swing adsorption; WGS-MR, steam reforming water gas shift. Data adapted from L. Roses, G. Manzolini, S. Campanari, E. De Wit, M. Walter, Techno-economic assessment of membrane reactor technologies for pure hydrogen production for fuel cell vehicle fleets, Energy Fuel. 27 (2013) 4423e4431. doi:10.1021/ef301960e.

required. The ATR-MR system is also penalized for the air compression. From an economic point of view, the capital cost of the membrane-based process is between 3% and 5% lower than the reference plant due to the reduced number of components, while

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the operating cost increases significantly up to 18% (in case of WGS-MR) due to the power requirements. The comparison in the cost of H2 production does not show a significant change. Only the SR-MR results more convenient than the benchmark technology (2% cheaper) which however poses some real engineering challenges for the design of a heated membrane reactor with respect to simpler adiabatic solutions of ATR-MR and WGS-MR. Di Marcoberardino et al. [21] have therefore investigated different options of a fluidized bed membrane reactor operated in autothermal conditions to use the produced H2 in a PEM for micro-CHP system for a 5 kWel. The work has been carried out aiming at a full optimization of the system from a thermodynamic point to achieve 40% of net electric efficiency and 90% of total system efficiency comparing different configuration and operating conditions. As presented in Fig. 12.2, different parameters have been considered such as membrane area, reforming operating pressure, steam-to-carbon ratio, permeate pressure using vacuum pump as well as with the use of sweep gas flowrate. A good compromise between efficiency and membrane area occurs at 8 bar; S/C 2.5; 600 C for the sweep gas case. Despite the negative effects on the electrical efficiency of the system, the results for the vacuum pump cases showed that some advantages could be obtained mainly from the simpler configuration of the reactor. Other options for decentralized H2 production with membrane reactor have been investigated using biogas as feedstock

Figure 12.2 Sensitivity analysis on the net electrical efficiency of different membrane area and permeate pressure as presented in Di Marcoberardino et al. [21]. Copyright 2015. Reproduced with permission from Elsevier.

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299

[23,24]. Compared to a reference biogas-to-H2 plant in which biogas is converted into CO2-H2-rich stream and pure H2 separated in a PSA, the adoption of membrane reactor results over 20% points more efficient. From an economic point of view, hydrogen production cost shows lower value with respect to the reference cases (4 V/kgH2 vs. 4.2 V/kgH2) for a fixed H2 production rate (100 kg day1) and delivery pressure of (20 bar). Two different biogas compositions have been compared, featuring typical landfill and anaerobic digestion cases. In case of biogas from anaerobic digestion, the efficiency is slightly higher due to the higher CH4 contents (because of less N2 and CO2). Ethanol (EtOH) is considered as an attractive feedstock due to its relatively high hydrogen content, abundant availability, nontoxicity, storage or handling ease, and safety, and it can be produced from biomass. Membrane reactors for EtOH reforming have been extensively studied in Borgognoni et al. [25] using a CH4/EtOH cofeeding unit, Basile et al. [26] in a packed bed membrane reactor (PB-MR), and Gallucci et al. [27] in a fluidized membrane reactor. Spallina et al. [28], have presented the experimental demonstration and modeling of an autothermal fluidized bed reactor using air and EtOH. The demonstration has been carried out in a 5 membranes large lab-scale prototype, which has been operated close to industrial operating conditions up to 550 C and 4 bar. The reactor model has been simulated using a combination of CSTRs in series and in parallel (Fig. 12.3) to simulate the presence of the emulsion and bubble phase inside the reactor, and the resulting gas profile is shown in Fig. 12.4.

Figure 12.3 Reactor model used for the simulation of an EtOH membrane reactor in Spallina et al. [28]. Copyright from Creative Commons Attribution Non Commericial-No Derivatives License (CC BY NC ND). Reproduced with permission from Elsevier.

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Figure 12.4 Simulated gas composition profiles for an EtOH autothermal membrane reactor as presented in Spallina et al. [28]. Copyright from Creative Commons Attribution Non Commerical-No Derivatives License (CC BY NC ND). Reproduced with permission from Elsevier.

De Falco [29] has investigated an ethanol membrane reformer integrated with a PEM fuel cell for automotive vehicles, delivering an optimized design of a 0.2 m3 reactor with four membranes (0.285 m2 of membrane area) operated at 400 C for the production of 64 NL$min1 of H2 to work in a PEMFC of 4 kWel. Foresti and Manzolini [30] have designed the full-scale plant for stationary application in micro-CHP configuration (Fig. 12.5) and compared with conventional reforming. Since EtOH is already diluted with water, additional H2O is not required to moderate the steam-to-carbon ratio. The

Figure 12.5 Process layout for an EtOH-to-H2 plant as proposed in Foresti and Manzolini [30]. PEM, polymer electrolyte membrane. Copyright 2016. Reproduced with permission from Elsevier.

Chapter 12 Energy analysis of innovative systems with metallic membranes

configuration proposed in this work includes an ATR system of 5 kWel in which the retentate gas is burned in an external burner to provide the required heat for the EtOHeH2O preheating and evaporation. In presence of a sweep gas, the net electric efficiency is higher than 40% while the membrane area can be limited below 0.4 m2 at 12 bar; H2O-to-EtOH ratio of 3.6; sweep-to-EtOH ratio of 1.6. For the case with a vacuum pump, the electrical efficiency of the system decreases due to the energy cost for the H2 compression while the membrane area is reduced. Recently, a glycerol reforming membrane reactor has been proposed in fluidized bed reactor configuration since it is a byproduct of biodiesel and at the moment does not have a big market. The thermodynamic study shows that the conversion is mostly given by a methane formation and WGS reactor [31].

Precombustion CO2 capture for production The advantage of integrating membrane reactors with CO2 capture technologies lies on the possibility to shift the equilibrium toward the products to obtain a CO2-rich stream ate retentate which is also available at high pressure and therefore it is easy to be separated and sent to long-term storage. Based on this technology, De Falco et al. [32] proposed a membrane reactor process at 650 C where after CO2 is separated from the retentate, the remaining gases (mostly H2 and unconverted CO and CH4) are used as fuel in a gas turbine to produce additional electricity for the plant. According to Iaquaniello et al. [33], about 30% of cost reduction is expected in comparison with a conventional steam methane reforming plant. Manzolini et al. [34] combined an air separation unit (ASU) in their system to completely oxidize the retentate species and use the pure N2 (from ASU) as sweep gas to obtain a H2/N2 gas for power generation. In their configuration, the membrane reactor was operated at 600 C and 10 bar, fully integrated in an advanced large-scale combined cycle. Depending on the thermodynamic and economic assumptions, the achieved CO2 avoidance cost can be lower than 50 V/tCO2. Two membrane reactors plant configurations have been proposed in Jordal et al. [35] integrated in a natural gas combined cycle (NGCC) with CO2 capture, with expected performance of 48%. A recent work from Spallina et al. [36] has compared two membrane-assisted reforming technologies and the conventional H2 production plant from a technoeconomic point of view.

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The two reactor configurations are shown in Fig. 12.6. The first case (Fig. 12.6, left) represents a Pd-based membrane reactor where the H2 produced is separated at high purity and part of the H2 permeates through other U-shaped membranes and reacts with air in the permeate side in order to supply the heat for the reforming reaction. The second case (Fig. 12.6, right) combines chemical looping reforming and membrane reactor [37,38]: in the fuel reactor, the oxygen carrier reacts with fuel to form H2 and CO2 via WGS/SR and gasesolid reaction with the oxygen carrier so that H2 permeates through the membranes, and CO2 (þH2O and traces of unconverted species) is available at the retentate, while in the air reactor, the oxygen carrier is oxidized with air and heated up so that the overall system does not require external heat supply. The two reactor concepts have been simulated using a Matlab code at steady state conditions. The gas The results show that the maximum H2 efficiency is reached in the MA-CLR (Fig 12.7). As already discussed for other membranebased process, the H2 is separated at low pressures leading to a higher electricity import. The combination of reforming efficiency with the electricity import/export results in an equivalent reforming efficiency in which the hybrid MA-CLR shows an efficiency of 82%, which is similar compared with the efficiency of the current reference technology (81%) and much higher when CO2 capture systems are installed in the process (67%). Furthermore, 91% of the total CO2 emissions are avoided. The cost analysis shows that a similar cost of H2 production is achieved compared to the

permeate retentate O2-depleted air

O2-depleted air

air

retentate permeate MeO

Me

NG+H2O NG+H2O

air

Figure 12.6 Reactor configuration for H2 production with CO2 capture from Ref. [36]. Copyright from Creative Commons Attribution Non Commercial-No Derivatives License (CC BY NC ND). Reproduced with permission from Elsevier.

Chapter 12 Energy analysis of innovative systems with metallic membranes

303

Figure 12.7 Simulated gas composition profiles for the fluidized-bed membrane reactor (FB-MR, left) and membrane-assisted chemical looping reforming (MA-CLR, right) a presented in Spallina et al. [36]. Copyright from Creative Commons Attribution Non Commerical-No Derivatives License (CC BY NC ND). Reproduced with permission from Elsevier.

reference case and well below that SR with precombustion separation using methyl-di-ethanol-amine (MDEA) process so that the CO2 avoidance of membrane-based technologies ranges from 3.6 V/tCO2 to 8 V/tCO2 (compared to >100 V/tCO2 of benchmark technology). The application of Pd-based H2-selective membranes has been studied also in integrated gasification combined cycle (IGCC) plants with CO2 capture [39e41]. Gazzani et al. [41] have performed a membrane process design and full technoeconomic assessment of an IGCC with different modules to produce H2/N2-rich mixture for a gas turbine (Figure 12.8). Two different layouts have been considered: (1) A first design was calculated where all the hydrogen is separated at high pressure to feed the gas turbine. This configuration features large membrane surface area requirements due to the high pressure at the permeate side and very high performances. (2) A second layout (Fig. 12.8) was introduced to optimize the amount of H2 separated at high pressure (as in the previous case) and at low pressure to feed the postfiring of the heat recovery steam generator. In the second case, the efficiency is approximately the same due to some rearrangement in the steam cycle and large H2 recovery with a reduced membrane area is obtained The A sensitivity analysis showed that the cost reduction of the module is the key for further economic improvement to the overall performance of the plant. A cost reduction of the membrane module would decrease the CO2 avoidance cost up to 8 V/tCO2

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Table 12.2 Technoeconomic assessment of the MA-CLR concept and comparison to the other technologies

CO2 capture Inlet fuel Input Pure H2 hH2 H2 yield Net electric output Steam to export mCH4,eq hH2,eq ECO2 ECO2,eq HR Total erected cost Natural gas Electricity cost Steam Cost of hydrogen CO2 avoidance

1

kg s MWLHV kg s1 Nm3/h % molH2/molNG MWe kg s1 kg s1 % kgCO2/Nm3H2 kgCO2/Nm3H2 Gcal/kNm3H2 MV MV/y MV/y MV/y cV/Nm3H2 V/tCO2, eq

SR

SR

N/A

MDEA

2.62 121.94 0.75 30259 74.0% 2.49 0.06 4.02 2.41 81.0% 0.82 0.76 3.24 89.34 31.68 0.02 1.34 21.08 -

2.62 121.94 0.70 28211 69.0% 2.32 1.93 0.25 2.88 67.0% 0.14 0.16 3.79 131.98 31.68 1.06 0.09 27.97 114.95

FB-MR

MA-CLR

2.62 121.94 0.85 34375 83.8% 2.83 7.98 0.76 2.88 76.3% 0.21 20.08 3.24 97.02 31.68 4.81 0.26 21.98 7.98

2.62 121.94 0.92 36965 90.1% 3.04 7.80 0.66 2.88 82.1% 0.07 6.14 3.02 99.48 31.68 4.69 1.02 21.3 L3.61

Partly reprinted from V. Spallina, D. Pandolfo, A. Battistella, MC. Romano, M. Van Sint Annaland, F. Gallucci, Techno-economic assessment of membrane assisted fluidized bed reactors for pure H2 production with CO2 capture, Energy Convers. Manag.120 (2016) 257e273. doi:10.1016/j.enconman.2016.04.073.; Copyright from Creative Commons Attribution Non Commercial-No Derivatives License (CC BY NC ND). Reproduced with permission from Elsevier.

Figure 12.8 Two-stage membrane separation layout as proposed in Gazzani et al. [41]. HRSG, heat recovery steam generator; HTS, high-temperature shift. Copyright 2014. Reproduced with permission from Elsevier.

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305

while both permeability and support thickness would affect the performance up to 8 V/tCO2 (Fig. 12.9). A more ambitious configuration has been studied from Rezvani et al. [42] in which the IGCC system is configured with a water gas shift membrane reactor (WGS-MR) and an oxygen transport membrane (OTM) system instead of a physical absorption unit. This has the function to utilize the remaining combustibles in the gas coming from the retentate side of WGS-MR. With respect to conventional CO2 capture technology, this configuration shows an electric efficiency of 1 percentage point higher (36.4% vs. 35.1%), a similar investment cost (approximately 1600e1650 V/kWel) and overall a CO2 avoidance cost of 65 V/tonCO2.

Chemicals production In the longer term, the increasing demand of olefins production would face a larger grown and implementation of new processes such as on-purpose propylene production technologies which should be able to stabilize the supply/demand balance. In particular, propane dehydrogenation (PDH) appeared the most suitable for satisfy the gap between conventional processes such as steam cracking and fluid catalytic cracking which are widely used for the production of olefins [43].

Figure 12.9 Sensitivity analysis on CO2 avoidance cost for the main parameters taken from Ref. [41]. Copyright 2014. Reproduced with permission from Elsevier.

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The PDH reaction is highly endothermic and therefore thermodynamically promoted at high operating temperatures and low pressures. The current state-of-the-art technologies operate at around 650 C, and since the side reactions are not limited by thermodynamic, a longer contact time results in lower selectivity to propylene which is typically limited to a propane conversion (32%e55%), with a selectivity to propylene below 90%. Membranes and membrane reactors have been proposed for the PDH process in the last years. Choi et al. [44] report a detailed modeling analysis of ceramic hollow fiber membranesdwith catalyst placement on the shell side for PDH, by integrating a twodimensional (2-D) nonisothermal model of a PB-MR including downstream separations processes resulting in þ45% increase of propylene production using the same amount of catalyst. Gbenedio et al. [45] developed a highly compact multifunctional Pd/ alumina hollow fiber membrane reactor. Moparthi et al. [46] addressed the economic feasibility of silica and palladium composite membranes for gaseous dehydrogenation reaction schemes and presented the economic assessment of dehydrogenation reaction schemes using a conceptual designebased simulation methodology for the comparative economic assessment of membrane reactors with conventional reactor processes resulting in an increases of 60%e70% excess profits using membrane reactors when compared with the conventional technology. Ricca et al. [47,48] have performed the full demonstration of PDH process (Fig. 12.10). In this configuration, the propane is fed in a two-stage PDH process with an intermediate membrane

Figure 12.10 Schematic of the propane dehydrogenation (PDH) using membrane reactor process [47]. Copyright 2017. Reproduced with permission from Elsevier.

Chapter 12 Energy analysis of innovative systems with metallic membranes

separator. The membrane reactor configuration leads to a moderate shift in the equilibrium propylene yield increasing the performance. While the reaction selectivity for propylene was similar in both the membrane and conventional reactors, catalyst deactivation rates were generally higher in the membrane reactors. The potential of membrane deactivation likely owing to adsorption of hydrocarbon species on the membrane surface can reduce the industrial applicability of this scheme. The results presented were consistent with the ones obtained also in Collins et al. [49] using both zeolite and Pd-based membrane integrated reactors. Rahimpour et al. [50] have summarized many other reactions considered with Pd-bases membranes for the production of fine chemicals (i.e., unsaturated aldehydes in the synthesis of fragrances and pharmaceuticals) and other dehydrogenation of cyclohexane to benzene, propane, isobutene, n-butane, and methylcyclohexane. Other options in reactive conditions include the selective dehydrogenation of unsaturated alcohols to unsaturated aldehydes, due to the removal of produced hydrogen during dehydrogenation, which results in more progress of the reaction. For those promising applications, no performance comparison has been carried out and therefore not further consideration can be added from an energy analysis point of view.

Conclusions and future trends This chapter has presented the current state of the art on the energy analysis for the metallic membrane and membrane reactor to combine the catalytic reaction separation of high pure H2. The current research on the integration of a Pd-based membrane and membrane reactor has been widely implemented for pure hydrogen production using different feedstocks and the results are consistently confirming the advantages from a technoeconomic point of view. The higher H2 production is often balanced from a higher electricity demand; however, in a lowcost electricity scenario or in case of CHP with PEM fuel cells, the H2 membrane reactor would improve the overall efficiency. In case of decarbonization of power generation, the performance is slightly higher than state-of-the-art technology; however other technologies seem to be more efficient despite the cost reduction in terms of CO2 avoidance is particularly interesting both for coal and NG. Augmentation of product yield/selectivity and thermodynamically shifting the reactions are the main superiorities of the membrane reactors. New process for high-value chemicals are currently

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under study and the results in terms of yield are very interesting. In particular, for on-purpose PDH, the integration of membrane separation, during the reaction or downstream, the process could reduce significantly the cost at the reactor level, lowering the operating temperature, and gas separation process by increasing the pressure and the conversion/selectivity. Despite membranes are already an established technology in the gas separation industry, the possibility to integrate reaction, and separation represents a large opportunity for energy, oil and gas, and chemical companies which are currently massively investigating the opportunity of making a membrane reactor ready to be commercialized.

List of acronyms ASU ATR CCS CLR FB FTR HHV IGCC LHV MDEA MR NG NGCC OTM PB PDH PEM POX PSA SR WGS

Air separation unit Autothermal reforming Carbon capture and storage Chemical looping reforming Fluidized bed Fired tubular reforming Higher heating value Integrated gasification combined cycle Lower heating value Methyl-di-ethanol-amine Membrane reactor Natural gas Natural gas combined cycle Oxygen transport membrane Packed bed Propane dehydrogenation Polymer electrolyte membrane fuel cell Preferential oxidation Pressure swing adsorption Steam reforming Water gas shift

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Chapter 12 Energy analysis of innovative systems with metallic membranes

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