Challenges and opportunities for using formate to store, transport, and use hydrogen

Grubel, Katarzyna; Jeong, Hyangsoo; Yoon, Chang Won; Autrey, Tom

doi:10.1016/j.jechem.2019.05.016

Cited by 85 publications

(56 citation statements)

References 120 publications

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“…It is a liquid at room temperature (normal melting point is 8 • C). Compared to MeOH, FA stores less H 2 by weight (4.4%), but the thermodynamic barrier for the release of H 2 (and CO 2 ) is significantly lower [50,75].…”

Section: Formic Acidmentioning

confidence: 99%

Application of Liquid Hydrogen Carriers in Hydrogen Steelmaking

Andersson

2021

Energies

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Steelmaking is responsible for approximately one third of total industrial carbon dioxide (CO2) emissions. Hydrogen (H2) direct reduction (H-DR) may be a feasible route towards the decarbonization of primary steelmaking if H2 is produced via electrolysis using fossil-free electricity. However, electrolysis is an electricity-intensive process. Therefore, it is preferable that H2 is predominantly produced during times of low electricity prices, which is enabled by storage of H2. This work compares the integration of H2 storage in four liquid carriers, methanol (MeOH), formic acid (FA), ammonia (NH3) and perhydro-dibenzyltoluene (H18-DBT), in H-DR processes. In contrast to conventional H2 storage methods, these carriers allow for H2 storage in liquid form at ambient moderate overpressures, reducing the storage capacity cost. The main downside to liquid H2 carriers is that thermochemical processes are necessary for both the storage and release processes, often with significant investment and operational costs. The carriers are compared using thermodynamic and economic data to estimate operational and capital costs in the H-DR context considering process integration options. It is concluded that the use of MeOH is promising compared to both the other considered carriers. For large storage volumes, MeOH-based H2 storage may also be an attractive option for the underground storage of compressed H2. The other considered liquid H2 carriers suffer from large thermodynamic barriers for hydrogenation (FA) or dehydrogenation (NH3, H18-DBT) and higher investment costs. However, for the use of MeOH in an H-DR process to be practically feasible, questions regarding process flexibility and the optimal sourcing of CO2 and heat must be answered.

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Section: Formic Acidmentioning

confidence: 99%

Application of Liquid Hydrogen Carriers in Hydrogen Steelmaking

Andersson

2021

Energies

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“…The free energy change of formate-bicarbonate conversion is nearly zero, hence the equilibrium shifts efficiently even by small change in reaction temperature. [24] Hydrogenation of bicarbonate is thermodynamically favored unlike CO 2 hydrogenation to methanol or formic acid therefore it is a viable process for industry. Furthermore, Pd and Ru are the two most studied metals for the catalysis of formate-bicarbonate conversion reactions.…”

Section: Catalysts Used For Formate-bicarbonate Conversionmentioning

confidence: 99%

“…Hydrogen capacities of selected formate salts at their solubility limits at 20°C. [24] Formate bicarbonate salts. However, it is interesting to note that gravimetric energy density of NH HCO 2 is higher than KHCO in the range of 20-80°C though the volumetric density of KHCO 2 is higher.…”

Section: Effect Of Formate Cation or Alkali Metal On Formate-bicarbonmentioning

confidence: 99%

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Formate‐Bicarbonate Cycle as a Vehicle for Hydrogen and Energy Storage

Bahuguna

Sasson

2020

ChemSusChem

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In recent years, hydrogen has been considered a promising energy carrier for a sustainable energy economy in the future. An easy solution for the safer storage of hydrogen is challenging and efficient methods are still being explored in this direction. Despite having some progress in this area, no cost‐effective and easily applicable solutions that fulfill the requirements of industry are yet to be claimed. Currently, the storage of hydrogen is largely limited to high‐pressure compression and liquefaction or in the form of metal hydrides. Formic acid is a good source of hydrogen that also generates CO2 along with hydrogen on decomposition. Moreover, the hydrogenation of CO2 is thermodynamically unfavorable and requires high energy input. Alkali metal formates are alternative mild and noncorrosive sources of hydrogen. On decomposition, these metal formates release hydrogen and generate bicarbonates. The generated bicarbonates can be catalytically charged back to alkali formates under optimized hydrogen pressure. Hence, the formate‐bicarbonate‐based systems being carbon neutral at ambient condition has certain advantages over formic acid. The formate‐bicarbonate cycle can be considered as a vehicle for hydrogen and energy storage. The whole process is carbon‐neutral, reversible, and sustainable. This Review emphasizes the various catalytic systems employed for reversible formate‐bicarbonate conversion. Moreover, a mechanistic investigation, the effect of temperature, pH, kinetics of reversible formate‐bicarbonate conversion, and new insights in the field are also discussed in detail.

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“…It is because formic acid is a very kinetically stable liquid at room temperature and contains 4.4 wt% hydrogen, that fulfil the announced targets by the United States Department of Energy (DOE). 5 The dehydrogenation (DH) process of formic acid to H2 and CO2 is thermodynamically quite favorable by ΔG = -32.9 kJ mol -1 and it shows 100% atom efficient catalytic storage. Moreover, formic acid can be used as an important intermediate, by-product and product in the chemical industry as well as biomass processes.…”

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confidence: 99%

Robust Mesoporous Zr-MOF with Pd Nanoparticles for Formic-Acid-Based Chemical Hydrogen Storage

Garai

Yavuz

2021

Matter

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Formic acid is a compelling chemical storage platform for hydrogen gas but the lack of an efficient dehydrogenation catalyst is preventing its commercial use. In this issue of Matter, Wang et al. reports a fine-tuned zirconium metal-organic-framework with palladium nanoparticles that effectively dehydrogenates formic acid without degradation.Mesoporosity in solid structures with pores between the diameters of 2~50 nm offers diverse applications including adsorption, catalysis, energy storage and conversion. 1 The scope of materials reach far and beyond, with the likes of activated carbon, silica, zeolites, and most recently metal organic frameworks (MOFs). Each class of mesoporous materials have advantages over the others but it's not common to have many features in one. The competition between stability and functionality is steep, where a resilient structure often needs to be devoid of reactive sites.

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Challenges and opportunities for using formate to store, transport, and use hydrogen

Abstract: Blue carbon on the rise: challenges and opportunities

Cited by 85 publications

References 120 publications

Application of Liquid Hydrogen Carriers in Hydrogen Steelmaking

Application of Liquid Hydrogen Carriers in Hydrogen Steelmaking

Formate‐Bicarbonate Cycle as a Vehicle for Hydrogen and Energy Storage

Robust Mesoporous Zr-MOF with Pd Nanoparticles for Formic-Acid-Based Chemical Hydrogen Storage

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