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Review

Perspectives and State of the Art of Membrane Separation Technology as a Key Element in the Development of Hydrogen Economy

by
M. Olga Guerrero-Pérez
Departamento de Ingeniería Química, Universidad de Málaga, E29071 Málaga, Spain
Membranes 2024, 14(11), 228; https://doi.org/10.3390/membranes14110228
Submission received: 28 September 2024 / Revised: 12 October 2024 / Accepted: 16 October 2024 / Published: 30 October 2024
(This article belongs to the Special Issue A Commemorative Special Issue in Honor of Dr. Moises Carreon)
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Abstract

:
Due to the objectives established by the European Union and other countries, hydrogen production will be a key technology in the coming decades. There are several starting materials and procedures for its production. All methods have advantages and disadvantages, and the improvements in their performance and decreases in operational costs will be decisive in determining which of them is implemented. For all cases, including for the storage and transport of hydrogen, membranes determine the performance of the process, as well as the operational costs. The present contribution summarizes the most recent membrane technologies for the main methods of hydrogen production, including the challenges to overcome in each case.

1. Introduction

Hydrogen is an energy carrier that can be produced using many different processes and starting materials. A color terminology that denotes these hydrogen production methods has been established [1]. Table 1 briefly describes the main methods with their advantages and disadvantages. According to this terminology, when hydrogen is produced through water electrolysis, the energy for which is produced using renewable sources (mainly solar), the term “green hydrogen” is used. The European Union established the REPowerEU [2] plan in 2022, in which renewable hydrogen is considered as a substitute for fossil-derived fuels, with the objective of decreasing dependence on Russian fossil fuel imports and accelerating the decarbonization of the European economy. Since most renewable energy sources are intermittent and geographically constrained, there are temporal and spatial gaps between energy availability and consumption by end-users [3]. The transformation of renewable energy into hydrogen, which can be transported, seems to be a solution to this problem, although it could concentrate the production of solar energy in determined areas. In any case, this is quite an ambitious objective, since natural gas and coal are the primary sources used in hydrogen production [4] through coal gasification or steam methane reformation (called grey or black hydrogen). These processes are much less expensive than green hydrogen production and do not require large amounts of water, although natural gas and coal are required as starting materials. In this process, CO2 emissions are produced, and the ability to capture and store them makes this an interesting option; in this case, the term blue hydrogen is used (Table 1). Some companies such as Shell and BP are betting on processes based on blue hydrogen technologies through the steam methane reformation of natural gas with carbon capture and storage (CCS) technologies, with the aim of limiting CO2 emissions; for example, Shell recently announced contracts for blue hydrogen projects in Oman [5] and Ohio [6], whereas BP will increase its focus on blue H2 in this decade [7]. Green hydrogen will be an option in the long run, but it is not currently competitive with blue hydrogen. Thus, green hydrogen is a good option that does not require natural gas, but it is expensive in comparison with other technologies such as blue hydrogen; in addition, it requires large amounts of water and land (for solar panels). In this context, several research groups are focusing on the design of catalysts for seawater electrolysis, although this process is still far from commercial implementation [8,9]. In addition, large deposits of natural hydrogen (white hydrogen) are being discovered, which is a market disruptor, since they are a relatively cheap source of hydrogen. According to recent data (April 2024) from the World Economic Forum [10], the production costs for green hydrogen technologies are in the USD 6–12/Kg range, whereas white hydrogen can be delivered for around USD 1/Kg. We are, therefore, in a situation regarding hydrogen technologies similar to what happened more than a century ago with the black gold rush. No one doubts that decarbonization is necessary, both to avoid CO2 emissions and because fossil fuel resources are limited, or that hydrogen will be the most common fuel in a few decades, since its combustion produces only water and is completely clean. However, there are different methods to produce it from different raw materials. There is also the option of extracting it naturally, although it is not known for sure how much hydrogen there is in the subsoil; this is being explored right now. Everything indicates that the technologies that will be used in the next decade will be green, blue, and white, and the production costs will be decisive in seeing which of the three options prevails in the market. In this context, gas separation membranes [11], together with electrocatalysts, will be decisive. In all processes, membranes will be necessary and will determine their efficiency and effectiveness.
In blue hydrogen production, a light hydrocarbon is used as a starting material (i.e., methane, naphtha, natural gas), mainly using a reforming process (SMR), partial oxidation (POM), or a combination of both (ATR technologies). Thus, there are different configurations, and CCS can be carried out pre- or post-combustion. Precombustion CCS technologies refer to CO2 removal from the starting syngas, whereas post-combustion CCS refers to removal from the exhaust gas. There are different processes for separating CO2 [12], such as absorption (e.g., amine scrubbing) or cryogenic processes [13]. However, these processes are energy-intensive and require the use of corrosive and environmentally harmful absorbents. Because of this, membranes [14,15] play a very important role in industrial-scale H2/CO2 separation due to their economic feasibility, easy operation, cost maintenance, term durability, and design flexibility (Table 2).
Regardless of the method used for hydrogen production, purification is required for almost all applications; for example, fuel cells and ammonia synthesis require high-purity hydrogen gas to operate efficiently and reliably, since impurities, even at a low concentration, can affect their processes [15]. Therefore, there are currently several processes and raw materials involved in hydrogen production processes; in all of them, membranes are decisive in improving efficiency and reducing costs. Therefore, it is the objective of this work to concisely analyze the state-of-the-art membrane technologies that are decisive in hydrogen separation and purification processes and the most recent technologies. Please note that this is not an exhaustive review on membrane technologies for H2 purification.

2. Blue Hydrogen: CO2/H2 Separation Membranes

As already introduced, hydrogen is commonly generated through the steam reformation of methane, and this process mainly yields a CO and H2 mixture. Through the water–gas shift reaction, CO in this mixture is transformed into CO2 (Figure 1). CO2 can be removed from the synthesized gas in order to generate a synthesized gas stream that should find several applications in the chemical industry. The Membrane Technology Research company has developed a commercially available membrane system called Polaris that is able to separate CO2 from syngas [17]. For the production of a purified H2 stream, it is necessary to separate the CO2/H2 mixture.
Thus, commercially available CO2/H2 separation processes are necessary for the development of blue hydrogen technology. Membranes play an important role in this separation, since other technologies such as absorption require the use of amine-based solvents, which are corrosive, expensive, and energy-intensive (Table 3). Membrane technology actually presents some limitations (Table 3) in commercial implementation, but there is an important research effort to overcome these limitations, since it is the most promising technology and present several advantages, such as flexibility, low energy requirements, and low production costs.
The requirements that have been established as an industrial target for hydrogen production include membranes with H2 permeance higher than 1000 GPU and CO2/H2 selectivity higher than 60 [18]. The membranes used for CO2/H2 can be inorganic (metal–organic frameworks, metallic, oxides, ceramics) or organic (polymers, celluloses). Several mechanisms are involved in the membrane separation process, with the most important being solution diffusion (defined by the gas permeability) and molecular sieving (defined by the selectivity). The gas permeability of a membrane is defined as the ease with which atoms or molecules can pass through the membrane in the presence of a pressure differential; this can refer to the membrane thickness and area, the pressure difference, or the permeation flow rate, modeled by equations such as Fick’s law. On the other hand, the selectivity refers to the membrane’s permeability to single atoms/molecules [19,20]. The permeability coefficient is defined as the product of the membrane thickness and the gas flux divided by the pressure gradient. The membrane selectivity is defined by the ratio of the permeability of components to the membrane thickness (αA/B = PA/PB, with PA and PB being the permeability factors of components A and B in a binary mixture) [21]. When the membrane pore size and the kinetic diameter of the molecules that penetrate (Table 2) are similar, the gas transport is dominated by the molecular sieving mechanism. The graph of the selectivity versus the permeability is known as the “Robeson Plot”, and it is commonly used for showing membrane performance [22]. These mechanisms mainly include thermodynamic and kinetic contributions; depending on the type of material and the process conditions, each of them can be dominant [23]. The goal when designing a CO2/H2 membrane is to achieve both high selectivity and high permeability, in addition to a long lifetime and high robustness.
Inorganic membranes present several advantages since they present high durability and stability in a wide range of conditions [24,25]. They can be dense membranes (mainly ceramic and metallic membranes) or porous membranes (such as zeolite, MOF, and carbon-based membranes). Zeolites have been widely investigated as promising materials for CO2/H2 separation since they exhibit high selectivity [26] and can be synthetized as hollow fibers [27,28,29] using scalable methods, such as electrospinning [30], which reduce the membrane cost significantly and increase the packing density of the membrane module [31]. In addition, their properties can be modulated through functionalization, for example, with amines, to increase selectivity at low pressures. In a recent study, Karanikolos and coworkers [32] proposed this approach. These studies, based on zeolite materials, are promising. MOF (metal–organic framework) membranes are also gaining attention due to their tunable properties (pore size, chemical surface groups, surface area, etc.), which can be modulated through the use of different metals and organic linkers. A recent study by Keskin et al. reviewed the use of MOF membranes for CO2 capture [33], showing how these membranes can efficiently separate CO2/H2 mixtures, especially more recently developed membranes (glass, ultrathin, and hybrid). In this case, the MOF materials are designed with functional groups able to alter their affinity towards desired/undesired species (such as impurities like H2O or H2S that may be present) and tailor the size and shape of the pores [30]. Computational modelling is helping to guide the experimental design of membranes with the desired properties [34], since hypothetical MOF materials can be computationally generated, exploring several combinations of components. To gain an understanding of the status of MOF materials research, Keskin et al. performed a bibliographic study, shown in Figure 1 [35]. Figure 2a presents all the hypothetical MOF materials that could be prepared, underlining (in red) those that have already been synthetized (about 100,000, whose crystallographic information files have been deposited into the Cambridge Structural Database); those that have been computationally generated are shown in dark blue. Figure 2b illustrates the number of published papers related to these materials, which increases every year due to the high potential of these materials; however, it should be noted that the percentage of studies related to simulation and using machine learning is increasing. Thus, the potential of MOF materials, including their use for the preparation of membranes for CO2/H2 separation, is a hot topic that is still developing, although promising results have already been reported [36,37].
These inorganic materials can be combined with a polymeric material to prepare mixed-matrix membranes (MMMs) that present the advantages of a polymer matrix (mechanical and tensile strength) with organic/inorganic material. Usually, zeolites, MOFs, and carbons are used as fillers for the fabrication of these MMMs. Figure 3 illustrates the separation performance of several MMMs in which polymers were loaded with different amounts of MOF materials. Figure 3a illustrates how the H2/CO2 separation performance increased with respect to both the bare polymer (marked with a circle) and the bare MOF material (marked with a pentagon); Figure 3b shows the hydrogen permeability for several MMMs.

3. Green Hydrogen: Membranes for Electrolyzers

In the case of green hydrogen production, H2 streams are produced through water electrolysis that is carried out in an electrolyzer. As explained in the introduction, one of the main challenges in green hydrogen technology is to reduce its operational costs with respect to blue hydrogen. Although fuel cell technology and water electrolyzers have made significant progress in the past few decades, their commercialization still faces many challenges, such as the short lifespan of fuel cells. Performance degradation is caused by a variety of complex factors, including the degradation of electrode materials, a loss of catalysts, mechanical damage to the membrane electrode assembly, and fluctuations in the operating conditions [40]. In this sense, membranes are a very relevant cost associated with fuel cell and electrolyzer performance, since they are responsible for the lifetime, power density, and efficiency of these devices.
There are different electrolysis technologies that require different types of membranes; however, in all cases, membranes play an essential role, as they are required to facilitate ion transfer and to act as a barrier to separate anode and cathode gases [41,42]. Table 4 summarizes the schematic data regarding the three main technologies: PEMWE (proton-exchange membrane water electrolysis), AEMWE (anion-exchange membrane water electrolysis), and BPMWE (bipolar membrane water electrolysis). PEMWE electrolyzers are commercially available, and this technology is well known. There are several commercial membranes based on different polymeric materials, such as perfluorosulfocic acid (PFSA) or polytetrafluoroethylene (PTFE). Since the synthesis of these polymers includes toxic intermediates, there is a significant research effort to develop low-cost non-fluorinated polymers [43] that present additional advantages, such as biodegradability and high thermal stability [43]. Despite the high number of commercial membrane technologies available for electrolyzers and fuel cells, there is still a need to increase their durability and performance and to lower their cost. In the case of AEMWE technology, there are also commercially available membranes that are stable under high pH based on hydrocarbon polymers, such as polyolefins [44], polyfluorenes [45], polyphenylenes [46], polyarylene piperidinium [47], or imidazolium [48]. The durability of these membranes is frequently limited by phenyl [49] and polystyrene [50] electrochemical degradation. Another important issue for these membranes is the interfacial resistance between the membrane and the electrode, which causes low current density. To overcome these problems, several solutions have been proposed; these include the zero-gap cell design (Figure 4), which comprises porous electrodes on each side of the membrane [51,52,53], facilitating a reduction in cell resistance to the gas bubbles, as well as to the electrolyte.
Bipolar membranes [55,56] are composed of cation- and anion-exchange layers that selectively transport H+ and OH− and are used in BPMWE electrolyzers, integrating alkaline and acid half reactions at different pHs (Table 4). In this manner, both OER (oxygen evolution reaction) and HER (hydrogen evolution reaction) can be carried out at their optimal pH. Alkaline OER can be catalyzed using low-cost and abundant elements, such as Fe or Ni, whereas the acid OER uses in PEMWE electrolyzers requires the use of noble metals. Although there have been advances in the development of noble metal-free electrocatalysts for acid OER, they are not currently available [57]. In addition to avoiding the use of noble metals, another advantage is that BPMWE technologies allow for the use of impure water, since the alkaline pH at the anode limits the Cl− oxidation to corrosive byproducts [58,59]. Thus, this technology could allow for the development of direct seawater electrolysis, which represents a promising solution regarding the main disadvantages associated with green H2 production, namely, that fresh water is required [60].

4. White Hydrogen and Transportation: H2/CH4 Separation

The separation of methane from hydrogen is quite relevant to refinery off-gas processing [61], and it is required in the case of white hydrogen, since natural hydrogen is usually found as a mixture with methane. In addition, an option for hydrogen transportation is the injection of 6–10% hydrogen in natural gas pipelines. This H2/CH4 gas mixture (hydrogen-enriched natural gas) can be utilized directly for power generation, or the hydrogen and methane can be purified in place for the desired end use. Thus, there are several applications in which H2/CH4 separation is required, and membrane technology is one of the most useful and economically viable options for this. The materials required for the preparation of H2/CH4 separation membranes are the same as those discussed for H2/CO2 separation: inorganic materials, such as zeolites, MOF [62] carbons, polymers, and MMMs [63]. According to the kinetic diameter (Table 4), the permeability of CO2 is higher than that of CH4; subsequently, the selectivity for H2/CH4 is higher than for H2/CO2 in most types of membranes (Figure 5) [64,65]. Although a large number of commercial membranes are available for this separation, there are still some challenges to overcome [63], since, for most of the actual applications, they have to be used in harsh conditions (high temperature and pressure and in the presence of impurities such as water vapor), and it is necessary to extend the lifetime of the membranes and their mechanical properties in these environments. In addition, and in order to achieve the performance that the applications require, the microstructure of the membranes should be well controlled, and the thickness has to be reduced in order to build membrane modules.

5. Conclusions and Perspectives

The demand for hydrogen as a fuel is increasing due to the objectives of the European Union and other countries to achieve decarbonization. There are different raw materials and processes used to obtain hydrogen while avoiding the use of fossil fuel resources, and all of them present advantages and disadvantages (Table 5), as has been explored. However, in all cases, including for the storage and transport of hydrogen, membranes are the key to achieving lower-cost processes and improving their efficiency.
In the case of blue hydrogen and white hydrogen technologies, H2/CH4 and H2/CO2 membrane separations are required. Although several commercial membranes are available, there are still some challenges to overcome (Table 5) in order to improve the selectivity, improve the mechanical properties, and decrease the costs. For green hydrogen technology, membranes are a key component of all electrolyzer varieties, as exposed in this study. In addition, the most recent electrolyzer technology, based on bipolar membranes, is crucial for the development of direct seawater electrolysis.

Funding

This study was funded by “H2EXCELLENCE—Fuels Cells and Green Hydrogen Centers of Vocational Excellence towards affordable, secure and sustainable energy for Europe (Project number: 101104447)”.

Institutional Review Board Statement

Not applicable.

Data Availability Statement

No new data were created or analyzed in this study. Data sharing is not applicable to this article.

Acknowledgments

I would like to dedicate this article to Moises A. Carreon, from the Colorado School of Mines. I had the pleasure of working with him a long time ago, during my postdoc at the University of Cincinnati, where we collaborated on the development of novel inorganic materials with catalytic applications [66,67]. He continued his research in this field, focusing on the design of porous crystalline materials with applications in gas separation [68]. It is deeply regrettable for humanity that he could not continue his important research due to his premature loss. He was an amazing person who positively impacted his colleagues and students. His memory will live on.

Conflicts of Interest

The author declare no conflict of interests.

References

  1. Hermesmann, M.; Müller, T.E. Green, Turquoise, Blue, or Grey? Environmentally friendly Hydrogen Production in Transforming Energy Systems. Prog. Energy Combust. Sci. 2022, 90, 100996. [Google Scholar] [CrossRef]
  2. Available online: https://ec.europa.eu/commission/presscorner/detail/en/ip_22_3131 (accessed on 29 October 2024).
  3. Mei, J.; Meng, X.; Tang, X.; Li, H.; Hansanien, H.; Alharbi, M.; Dong, Z.; Shen, J.; Sun, C.; Fan, F.; et al. An accurate parameter estimation method of the voltage model for proton exchange membrane fuel cells. Energies 2024, 17, 2917. [Google Scholar] [CrossRef]
  4. Innovation Insights Brief 2019. New Hydrogen Economy Hope or Hype? World Energy Council. 2019. Available online: https://www.worldenergy.org/assets/downloads/WEInsights-Brief-New-Hydrogen-economy-Hype-or-Hope-ExecSum.pdf (accessed on 3 September 2024).
  5. Available online: https://www.ogj.com/energy-transition/article/55131133/shell-lets-contracts-for-blue-hydrogen-project-in-oman (accessed on 3 September 2024).
  6. Available online: https://hydrogen-central.com/trillium-h2-power-llc-selects-the-shell-blue-hydrogen-process/ (accessed on 3 September 2024).
  7. Available online: https://www.hydrogeninsight.com/production/bp-increases-hydrogen-pipeline-to-2-9-million-tonnes-a-year-with-focus-on-blue-h2-this-decade/2-1-1594716 (accessed on 3 September 2024).
  8. Liu, Y.; Wang, Y.; Fornasiero, P.; Tian, G.; Strasser, P.; Yang, X.-Y. Long-term Durability of Seawater Electrolysis for Hydrogen: From Catalysts to Systems. Angew. Chem. Int. Ed. 2024, e202412087. [Google Scholar]
  9. Kumar, S.S.; Lim, H. An overview of water electrolysis technologies for green hydrogen production. Energy Rep. 2022, 8, 13793–13813. [Google Scholar] [CrossRef]
  10. World Economic Forum Report. White Hydrogen: 5 Critical Questions Answered. Available online: https://www.weforum.org/agenda/2024/08/white-hydrogen-5-critical-questions-answered/ (accessed on 4 September 2024).
  11. Lu, H.T.; Li, W.; Miandoab, E.S.; Kanehashi, S.; Hu, G. The opportunity of membrane technology for hydrogen purification in the power to hydrogen (P2H) roadmap: A review. Front. Chem. Sci. Eng. 2021, 15, 464–482. [Google Scholar] [CrossRef]
  12. D’Alessandro, D.M.; Smit, B.; Long, J.R. Carbon dioxide capture: Prospects for New Materials. Angew. Chem. Int. Ed. 2010, 49, 6058–6082. [Google Scholar] [CrossRef]
  13. Alhumaidan, F.S.; Halabi, M.A.; Rana, M.S.; Vinoba, M. Blue hydrogen: Current status and future technologies. Energy Convers. Manag. 2023, 283, 116840. [Google Scholar] [CrossRef]
  14. Chang, R.W.; Lin, C.J.; Hiou, S.Y.H.; Banares, M.A.; Guerrero-Perez, M.O.; Aranda, R.M.M. Enhanced cyclic CO2/N2 separation performance stability on chemically modified N-doped ordered mesoporous carbon. Catal. Today 2020, 356, 88–94. [Google Scholar] [CrossRef]
  15. Herm, Z.R.; Krishna, R.; Long, J.R. CO2/CH4, CH4/H2 and CO2/CH4/H2 separations at high pressures using Mg2(dobdc). Microporous Mesoporous Mater. 2012, 151, 481–487. [Google Scholar] [CrossRef]
  16. Lin, H.; Freeman, B.D. Gas solubility, diffusivity and permeability in poly (ethylene oxide). J. Membr. Sci. 2004, 239, 105–117. [Google Scholar] [CrossRef]
  17. Li, S.; Pyrzynski, T.; Meyer, H.; Klinghoffer, N.; Tamale, T. Membrane Absorption Process for CO2 Capture. US Patent US20190282953A1, 19 September 2019. [Google Scholar]
  18. Ku, A.Y.; Kulkarni, P.; Shisher, R.; Wei, W. Membrane performance requirements for carbon dioxide capture using hydrogen-selective membranes in integrated gasification combined cycle (IGCC) power plants. J. Membrane Sci. 2011, 367, 233–239. [Google Scholar] [CrossRef]
  19. Li, M.C.; Liu, X.; Lv, K.; Sun, J.; Dai, C.; Liao, B.; Liu, C.; Mei, C.; Wu, Q.; Hubbe, M. Cellulose nanomaterials in oil and gas industry: Current status and future perspectives. Prog. Mater. Sci. 2023, 139, 101187. [Google Scholar] [CrossRef]
  20. Yasuda, H. Units of gas permeability constants. J. Appl. Polym. Sci. 1975, 19, 2529–2536. [Google Scholar] [CrossRef]
  21. Freeman, B.D. Basis of Permeability/Selectivity Tradeoff Relations in Polymeric Gas Separation Membranes. Macromolecules 1999, 32, 375–380. [Google Scholar]
  22. Patel, H.D.; Acharya, N.K. Transport properties of polymer blends and composite membranes for selective permeation of hydrogen. Int. J. Hydrog. Energy 2023, 48, 37796–37810. [Google Scholar] [CrossRef]
  23. Carreon, M.A. Microporous Crystalline Molecular Sieve Membranes for Molecular Gas Separations: What is next? ACS Mater. Lett. 2022, 4, 868–873. [Google Scholar] [CrossRef]
  24. Escolastico, S.; Solis, C.; Kjolseth, C.; Serra, J.M. Outstanding hydrogen permeation through CO2 stable dual-phase ceramic membranes. Energy Environ. Sci. 2014, 7, 3736–3746. [Google Scholar] [CrossRef]
  25. Li, H.; Hass-Santo, K.; Schygulla, U.; Dittmeyer, R. Inorganic microporous membranes for H2 and CO2 separation–Review of experimental and modeling progress. Chem. Eng. Sci. 2015, 127, 401–417. [Google Scholar] [CrossRef]
  26. Wang, L.; Zhag, C.; Gao, X.; Pen, L.; Jiang, J.; Gu, X. Preparation of defect-free DDR zeolite membranes by eliminating template with ozone at low temperature. J. Membr. Sci. 2017, 539, 152–160. [Google Scholar] [CrossRef]
  27. Liu, H.; Gao, X.; Wang, S.; Hong, Z.; Wang, X.; Gu, X. SSZ-13 zeolite membranes on four-channel Al2O3 hollow fibers for CO2 separation. Sep. Purif. Technol. 2021, 267, 118611. [Google Scholar] [CrossRef]
  28. Schneider, M.; Rodriguez-Castellon, E.; Guerrero-Perez, M.O.; Hotza, D.; de Noni, A.; de Fatima Peralta Muniz Moreira, R. Advances in electrospun composite polymer/zeolite and geopolymer nanofibers: A comprehensive review. Sep. Pur. Tech. 2024, 340, 126684. [Google Scholar] [CrossRef]
  29. Guerrero-Perez, M.O. Research progress son the applications of electrospun nanofibers in catalysis. Catalysts 2022, 12, 9. [Google Scholar] [CrossRef]
  30. Calzado-Delgado, M.; Guerrero-Perez, M.O.; Yeung, K.L. A new versatile x-y-z electrospinning equipment for nanofiber synthesis in both far and near field. Sci. Rep. 2022, 12, 4872. [Google Scholar] [CrossRef]
  31. Ahmed, F.E.; Lalia, B.S.; Hashaikeh, R. A review on electrospinning for membrane fabrication: Challenges and applications. Desalination 2015, 356, 15–30. [Google Scholar] [CrossRef]
  32. Kuppireddy, S.; Varghese, A.M.; Araj, H.A.; Hart, P.; Romantani, T.; Bampos, G.; Karanikolos, G.N. A combined experimental and simulations assessment of CO2 capture and CO2/H2 separation performance of aminosilane-grafted MCM-41 and pore-epanded MCM-41. Micro. Meso. Mat. 2024, 377, 113220. [Google Scholar] [CrossRef]
  33. Kemir, H.; Aksu, G.O.; Gulbalkan, H.C.; Keskin, S. MOF Membranes for CO2 Capture: Past, Present and Future. Carbon Capture Sci. Technol. 2022, 2, 100026. [Google Scholar]
  34. Shah, M.; McCarthy, M.C.; Sachdeva, S.; Lee, A.K.; Jeong, H.K. Current Status of Metal-Organic Framework Membranes for Gas Separations: Promises and Challenges. Ind. Eng. Chem. Res. 2012, 51, 2179–2199. [Google Scholar] [CrossRef]
  35. Demir, H.; Daglar, H.; Gulbalkan, H.C.; Aksu, G.O.; Keskin, S. Recent advances in computational modeling of MOFs: From molecular simulations to machine learning. Coord. Chem. Rev. 2023, 484, 215112. [Google Scholar] [CrossRef]
  36. Song, H.; Peng, Y.; Wang, C.; Shu, L.; Zhu, C.; Wang, Y.; He, H.; Yang, W. Structure Regulation of MOF Nanosheet Membrane for Accurate H2/CO2 Separatiion. Angewandte Chemie Int. Ed. 2023, 62, e202218472. [Google Scholar] [CrossRef]
  37. Sanchez-Lainez, J.; Zornoza, B.; Orsi, A.F.; Lozinska, M.M.; Dawson, D.M.; Ashbrook, S.E.; Francis, S.M.; Wright, P.A.; Benoit, V.; Llewellyn, P.L.; et al. Synthesis of ZIF-93/11 Hybrid Nanoparticles via Post-Synthetic Modification of ZIF-93 and Their Use for H2/CO2 Separation. Chem. A Eur. J. 2018, 24, 11211–11219. [Google Scholar] [CrossRef] [PubMed]
  38. Bitter, J.H.; Tashvigh, A.A. Recent Advances in Polybenzimmidazole Membranes for Hydrogen Purification. Ind. Eng. Chem. Res. 2022, 61, 6125–6134. [Google Scholar] [CrossRef]
  39. Al-Rowaili, F.N.; Khaled, M.; Jamal, A.; Zahid, U. Mixed matrix membranes for H2/CO2 gas separation—A critical review. Fuel 2023, 333, 126285. [Google Scholar] [CrossRef]
  40. Meng, X.; Mei, J.; Tang, X.; Jiang, J.; Sun, C.; Song, K. The Degradation Prediction of Proton Excange Membrane Fuel Cell Performance Based on a Transformer Model. Energies 2024, 17, 3050. [Google Scholar] [CrossRef]
  41. Ng, W.K.; Wong, W.Y.; Rosli, N.A.H.; Loh, K.S. Commercial Anion Exchange Membranes (AEMs) for Fuel Cell and Water Electrolyzer Applications: Performance, Durability, and Material Advancement. Separations 2023, 10, 424. [Google Scholar] [CrossRef]
  42. Park, E.J.; Arges, C.G.; Xu, H.; Kim, Y.S. Membrane Strategies for Water Electrolysis. ACS Energy Lett. 2022, 7, 3447–3457. [Google Scholar] [CrossRef]
  43. Wang, Z.; Hao, L.; Yang, F.; Wei, Q. Mesoporous Silica Membranes Silylated by Fluorinated and Non-Fluorinated Alkylsilanes for the separation of methyl Terc-Butyl Ether from Water. Membranes 2020, 10, 70. [Google Scholar] [CrossRef]
  44. Motz, R.; Li, D.G.; Keane, A.; Manriquez, L.D.; Park, E.J.; Maurya, S.; Chung, H.; Fujimoto, C.; Jeon, J.; Pagels, M.K.; et al. Performance and durability of anion exchange membrane water electrolyzers using down-selected polymer electrolytes. J. Mater. Chem. A 2021, 9, 22670–22683. [Google Scholar] [CrossRef]
  45. Wang, Y.; Ban, T.; Guo, M.; Zhu, X. Polu(fluorenyl-indolinedione) based hydroxide conducting membrane for anion exchange membrane water electrolyzers. Int. J. Hyd. En. 2024, 49C, 1123–1133. [Google Scholar] [CrossRef]
  46. Park, E.J.; Maurya, S.; Hibbs, M.R.; Fujimoto, C.H.; Kreuer, K.-D.; Kim, Y.S. Alkaline Stability of Quaternized Diels-Alder Polyphenylenes. Macromolecules 2019, 52, 5419–5428. [Google Scholar] [CrossRef]
  47. Olsson, J.S.; Pham, T.H.; Jannasch, P. Poly(arylene piperidinium) Hydroxide Ion Excange Membranes: Synthesis, Alkaline Stability, and Conductivity. Adv. Funct. Mater. 2018, 28, 1702758. [Google Scholar] [CrossRef]
  48. Fan, J.T.; Willdorf-Cohen, S.; Schibli, E.M.; Paula, Z.; Li, W.; Skalski, T.J.G.; Sergeenko, A.T.; Hohenadel, A.; Frisken, B.J.; Magliocca, E.; et al. Poly(bis-arylimidazoliums) possessing high hydroxide ion exchange capacity and high alkaline stability. Nat. Commun. 2019, 10, 2306. [Google Scholar] [CrossRef]
  49. Li, D.; Matanovic, I.; Lee, A.S.; Park, E.J.; Fujimoto, C.; Chung, H.T.; Kim, Y.S. Phenyl oxidation impacts the durability of alkaline membrane water electrolyzer. ACS Appl. Mater. Inter 2019, 11, 9696–9701. [Google Scholar] [CrossRef] [PubMed]
  50. Xing, X.; Zhu, X.P.; Li, H.N.; Jiang, Y.; Ni, J.R. Electrochemical oxidation of nitrogen-heterocyclic compounds at boron-doped diamond electrode. Chemosphere 2012, 86, 368–375. [Google Scholar] [CrossRef] [PubMed]
  51. Phillips, R.; Dunnill, C.W. Zero gap alkaline electrolysis cell design for renewable energy storage as hydrogen gas. RSC Advances 2016, 6, 100643–100651. [Google Scholar] [CrossRef]
  52. Faqeeh, A.H.; Symes, M.D. Zero-gap bipolar membrane water electrolyzers: Principles, challenges and practical insights. Electrochim. Acta 2024, 493, 144345. [Google Scholar] [CrossRef]
  53. de Groot, M.T.; Vreman, A.W. Ohmic resistance in zero gap alkaline electrolysis with a Zirfon diaphragm. Electroquim. Acta 2021, 369, 137684. [Google Scholar] [CrossRef]
  54. Philips, R.; Edwards, A.; Rome, B.; Jones, D.R.; Dunnil, C.W. Minimising the ohmic resistance of an alkaline electrolysis cell through effective cell design. Int. J. Hyd. Ener. 2017, 42, 23986–23994. [Google Scholar] [CrossRef]
  55. Parnamae, R.; Mareev, S.; Nikonenko, V.; Melnikov, S.; Sheldeshow, N.; Zabolotskii, V.; Hamalers, H.V.M.; Tedesco, M. Bipolar membranes: A review on principles, latest developments and applications. J. Membr. Sci. 2021, 617, 118538. [Google Scholar] [CrossRef]
  56. Giesbrecht, P.K.; Freund, S.M. Recent Advances in Bipolar Membrane Design and Applications. Chem. Mat. 2020, 32, 8060–8090. [Google Scholar] [CrossRef]
  57. Li, J.; Tian, W.; Li, Q.; Zhao, S. Acidic Oxygen Evolution Reaction: Fundamental Understanding and Electrocatalysts Design. ChemSusChem 2024, 17, e202400239. [Google Scholar] [CrossRef]
  58. Marin, D.H.; Perryman, J.T.; Hubert, M.A.; Lindquist, G.A.; Chen, L.; Aleman, A.M.; Kamat, G.A.; Niemann, V.A.; Stevens, M.B.; Regmi, Y.N.; et al. Hydrogen production with seawater-resilient bipolar membrane electorlyzers. Joule 2023, 7, 765–781. [Google Scholar] [CrossRef]
  59. Tang, J.; Su, C.; Shao, Z. Advanced membrane-based electrode engineering toward efficient and durable water electrolysis and cost-effective seawater electrolysis in membrane electrolyzers. Exploration 2023, 4, 20220112. [Google Scholar] [CrossRef] [PubMed]
  60. Adisasmito, S.; Khoiruddin, K.; Sutrisna, P.D.; Wenten, I.G.; Siagian, U.W.R. Bipolar Membrane Seawater Splitting for Hydrogen Production: A Review. ACS Omega 2024, 9, 14704–14727. [Google Scholar] [CrossRef] [PubMed]
  61. Li, J.R.; Kuppler, R.J.; Zhou, H.C. Selective gas adsorption and separation in metal-organic frameworks. Chem. Soc. Rev. 2009, 38, 1477–1504. [Google Scholar] [CrossRef] [PubMed]
  62. Schneider, M.; Rodríguez-Castellón, E.; Guerrero-Pérez, M.O.; Hotza, D.; Junior, A.N.; Moreira, R. Hierarchically porous composites containing mining tailings-based geopolymer and zeolite 13X: Application for carbon dioxide sequestration, Adsorption. Res. Sq. 2024; in press. [Google Scholar] [CrossRef]
  63. Zhou, R.; Pan, Y.; Xing, W.; Xu, N. Advanced microporous membranes for H2/CH4 separation: Challenges and perspectives. Adv. Membr. 2021, 1, 100011. [Google Scholar] [CrossRef]
  64. Tseng, H.H.; Wang, C.-T.; Zhuang, G.L.; Uchytil, P.; Reznickova, J.; Setnickova, K. Enhanced H2/CH4 and H2/CO2 separation by carbon molecular sieve membrane coated on titania modified alumina support: Effects of TiO2 intermediate layer preparation variables on interfacial adhesion. J. Membr. Sci. 2016, 510, 391–404. [Google Scholar] [CrossRef]
  65. Chen, X.; Fan, Y.; Wu, L.; Zhang, L.; Guan, D.; Ma, C.; Li, N. Ultra-selective molecular-sieving gas separation membranas enabled by multi-covalent-crosslinking of microporous polymer blends. Nat. Commun. 2021, 12, 6140. [Google Scholar] [CrossRef]
  66. Carreon, M.A.; Guliants, V.V.; Guerrero-Perez, M.O.; Bañares, M.A. Mesostructured mixed Mo–V–Nb oxides for propane ammoxidation. Catal. Commun. 2009, 10, 416–420. [Google Scholar]
  67. Carreon, M.A.; Guerrero-Pérez, V.V.G.M.O.; Bañares, M.A. Phase transformations in mesostructured VPO/surfactant composites. Microporous Mesoporous Mater. 2004, 71, 57–63. [Google Scholar] [CrossRef]
  68. Carreon, M.A. Porous crystals as membranes. Science 2020, 367, 624–625. [Google Scholar] [CrossRef]
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Figure 1. Scheme of the process for hydrogen and synthesis gas via carbon gasification or natural gas reformation with precombustion CCS.
Figure 1. Scheme of the process for hydrogen and synthesis gas via carbon gasification or natural gas reformation with precombustion CCS.
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Figure 2. (a) The large cube represents the MOF space with an almost infinite number of materials, including synthesized and hypothetical MOFs. (b) The number of published papers having the keywords (i) “MOF”, (ii) “MOF” and “Simulation”, and (iii) “MOF” and “Machine Learning” in their titles and abstracts. Data were retrieved from the Web of Science on 17 October 2022. Reproduced with permission from [35].
Figure 2. (a) The large cube represents the MOF space with an almost infinite number of materials, including synthesized and hypothetical MOFs. (b) The number of published papers having the keywords (i) “MOF”, (ii) “MOF” and “Simulation”, and (iii) “MOF” and “Machine Learning” in their titles and abstracts. Data were retrieved from the Web of Science on 17 October 2022. Reproduced with permission from [35].
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Figure 3. (a) H2/CO2 gas separation performance of a polymer with 20 wt% loaded MOF material [37]). The Robeson upper bounds are denoted with continuous lines, while the estimated upper bound at 180 °C is denoted with a dashed line. (b) Performance comparison of different derivatives and random copolymer membranes for the separation of H2/CO2 [38]. Reproduced with permission from [39].
Figure 3. (a) H2/CO2 gas separation performance of a polymer with 20 wt% loaded MOF material [37]). The Robeson upper bounds are denoted with continuous lines, while the estimated upper bound at 180 °C is denoted with a dashed line. (b) Performance comparison of different derivatives and random copolymer membranes for the separation of H2/CO2 [38]. Reproduced with permission from [39].
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Figure 4. Schematic of the zero-gap cell design versus the traditional cell design. Reproduced with permission from [54].
Figure 4. Schematic of the zero-gap cell design versus the traditional cell design. Reproduced with permission from [54].
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Figure 5. (a) Gas permeability and (b) selectivity as a function of reaction temperature for several membranes enabled by multi-covalent crosslinking of microporous polymer blends, thermally treated at the indicated temperature for 10–20 h under 200 ppm of O2. (c) Gas permeability and (d) selectivity for crosslinked membranes treated at 250 °C, versus treated time. (e) Gas permeability and (f) selectivity as a function of O2 concentration for crosslinked membranes treated at 250 °C for 10 h. Reproduced with permission from [65].
Figure 5. (a) Gas permeability and (b) selectivity as a function of reaction temperature for several membranes enabled by multi-covalent crosslinking of microporous polymer blends, thermally treated at the indicated temperature for 10–20 h under 200 ppm of O2. (c) Gas permeability and (d) selectivity for crosslinked membranes treated at 250 °C, versus treated time. (e) Gas permeability and (f) selectivity as a function of O2 concentration for crosslinked membranes treated at 250 °C for 10 h. Reproduced with permission from [65].
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Table 1. Main H2 production methods with the most important pros and cons associated with them. Note that, for the sake of simplicity and to focus on this study’s contents, other methods, such as those in which the energy for the water electrolysis is provided by nuclear energy, are not included in this table.
Table 1. Main H2 production methods with the most important pros and cons associated with them. Note that, for the sake of simplicity and to focus on this study’s contents, other methods, such as those in which the energy for the water electrolysis is provided by nuclear energy, are not included in this table.
BlackGreyBlueGreenWhite
Gasification of coalMethane steam reformingProduced from fossil fuels (i.e., grey or black), where CO2 is captured and storedProduced via electrolysis of water using electricity from renewable sources (wind or solar)Naturally produced in the Earth’s crust
Cons
  • CO2 emissions.
  • Fossil fuel source required.
  • CO2 emissions.
  • Fossil fuel source required.
  • Fossil fuel source required.
  • High production costs.
  • Large amount of freshwater required.
  • Solar energy requires the use of large surfaces of land or sea.
  • Cheap (it does not require energy conversion/manufacturing processes).
  • It is quite a new technology, and geological surveys are required.
Pros
  • Low production costs.
  • Available raw material.
  • Low production costs.
  • Low production costs in comparison with green hydrogen.
  • Low CO2 emissions.
  • Renewable
  • Zero CO2 emissions.
  • May be renewable.
  • Low environmental impact.
Table 2. Physical properties of hydrogen, methane, and CO2 gas molecules [16].
Table 2. Physical properties of hydrogen, methane, and CO2 gas molecules [16].
Molecular Weight (g/mol)Kinetic Diameter (A)Critical Volume (cm3/mole)Critical Temperature
(K)
H222.8965.133.24
CH4163.8099.2191.05
CO2443.3093.9304.21
Table 3. Main limitations and advantages of the current technology processes for CO2/H2 separation.
Table 3. Main limitations and advantages of the current technology processes for CO2/H2 separation.
AbsorptionAdsorptionDistillationMembranes
AdvantagesCommercially available technology with high CO2 removal rates.High number of adsorbents available with high adsorption capacity.Available for high CO2 concentrations.Low capital and operation costs.
Flexibility.
Simple operation.
LimitationsUse of corrosive absorbents, energy- and cost-intensive processes, low absorption capacity.The advantages that adsorption presents, such as decreased pressure requirements and a sensitivity to impurities, do not seem to be sufficiently profitable to replace current absorption processes with it.High operation costs.They are more expensive than absorption and adsorption and may present low flux, high fouling, and some instability under high T and P working conditions.
Table 4. Reactions involved in PEMWE, AEMWE, and BPMWE technologies.
Table 4. Reactions involved in PEMWE, AEMWE, and BPMWE technologies.
PEMWEAEMWEBPMWE
Reactions occurring at the anode and cathode2H+ + 2e− → H2
H2O → 2H+ + 0.5O2 + 2e−		2H2O + 2e− → 2OH− + H2
2OH− → H2O + 0.5O2 + 2e−		2OH−→ H2O + 0.5O2 + 2e−
2H+ + 2e−→ H2
HER acid
OER acid		HER alkaline
OER alkaline		HER acid
OER alkaline
Membrane selective to:Protons (H+)Anions (OH−)Bipolar membrane (OH− and H+)
Table 5. Summary of the main pros and cons and state of the art of membranes for H2 production with blue and green technologies.
Table 5. Summary of the main pros and cons and state of the art of membranes for H2 production with blue and green technologies.
Blue H2Green H2
Most promising membrane typeMixed-matrix membranes (MMMs).Bipolar membranes.
Main advantages of H2 production technologyLow costs. CO2 emissions are avoided. Captured CO2 can be used as a raw material.Renewable.
Main disadvantages of membrane technologyLow flux, high fouling, instability under high T and P.Poor lifetime, power density, and efficiency.
Main problems to be solvedAbsorption methods are less expensive. It is necessary to decrease the membrane costs to compete with them and avoid the use of dangerous and corrosive sorbents.Green H2 technology consumes a large amount of fresh water. It is necessary to develop electrolysis technology compatible with sea water; in this context, bipolar technologies are promising.
For large-scale production, it will be desirable to use the O2 produced as a by-product.
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Guerrero-Pérez, M.O. Perspectives and State of the Art of Membrane Separation Technology as a Key Element in the Development of Hydrogen Economy. Membranes 2024, 14, 228. https://doi.org/10.3390/membranes14110228

AMA Style

Guerrero-Pérez MO. Perspectives and State of the Art of Membrane Separation Technology as a Key Element in the Development of Hydrogen Economy. Membranes. 2024; 14(11):228. https://doi.org/10.3390/membranes14110228

Chicago/Turabian Style

Guerrero-Pérez, M. Olga. 2024. "Perspectives and State of the Art of Membrane Separation Technology as a Key Element in the Development of Hydrogen Economy" Membranes 14, no. 11: 228. https://doi.org/10.3390/membranes14110228

APA Style

Guerrero-Pérez, M. O. (2024). Perspectives and State of the Art of Membrane Separation Technology as a Key Element in the Development of Hydrogen Economy. Membranes, 14(11), 228. https://doi.org/10.3390/membranes14110228

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