Institution of Gas Engineers & Managers

Our contribution demonstrates that hydrogen storage in stationary Liquid Organic Hydrogen Carrier (LOHC) systems becomes much simpler and significantly more efficient if both the LOHC hydrogenation and the LOHC dehydrogenation reaction are carried out in the same reactor using the same catalyst. The finding that the typical dehydrogenation catalyst for hydrogen release from perhydro dibenzyltoluene (H18-DBT) Pt on alumina turns into a highly active and very selective dibenzyltoluene hydrogenation catalyst at temperatures above 220 °C paves the way for our new hydrogen storage concept. Herein hydrogenation of H0-DBT and dehydrogenation of H18-DBT is carried out at the same elevated temperature between 290 and 310 °C with hydrogen pressure being the only variable for shifting the equilibrium between hydrogen loading and release. We demonstrate that the heat of hydrogenation can be provided at a temperature level suitable for effective dehydrogenation catalysis. Combined with a heat storage device of appropriate capacity or a high pressure steam system this heat could be used for dehydrogenation.

Fuel cells are promising technologies for zero-emission energy conversion. They are used in several applications such as power plants cars and even submarines. Hydrogen supply is crucial for such systems and using Proton Exchange Membrane Fuel Cell in dead-end mode is a solution to save hydrogen. Since water and impurities accumulate inside the stack purging is necessary. However the importance of operating parameters is not well known for fuel cells working in closed environments. A Design of Experiment approach studying time between two purges and cell performance was conducted on an air-breathing stack in a closed environment. The most influential parameters on the time between two purges are the relative humidity and the current load. Convection in the closed environment can decrease the stability of the fuel cell. A linear model with interactions between these last three parameters was found to accurately describe the studied responses.

A technoeconomic analysis of photoelectrochemical (PEC) and photovoltaic-electrolytic (PV-E) solar-hydrogen production of 10 000 kg H₂ day⁻¹ (3.65 kilotons per year) was performed to assess the economics of each technology and to provide a basis for comparison between these technologies as well as within the broader energy landscape. Two PEC systems differentiated primarily by the extent of solar concentration (unconcentrated and 10× concentrated) and two PV-E systems differentiated by the degree of grid connectivity (unconnected and grid supplemented) were analyzed. In each case a base-case system that used established designs and materials was compared to prospective systems that might be envisioned and developed in the future with the goal of achieving substantially lower overall system costs. With identical overall plant efficiencies of 9.8% the unconcentrated PEC and non-grid connected PV-E system base-case capital expenses for the rated capacity of 3.65 kilotons H₂ per year were $205 MM ($293 per m² of solar collection area (m_S⁻²) $14.7 W_H2P⁻¹) and $260 MM ($371 mS−2 $18.8 W_H2P⁻¹) respectively. The untaxed plant-gate levelized costs for the hydrogen product (LCH) were $11.4 kg⁻¹ and $12.1 kg⁻¹ for the base-case PEC and PV-E systems respectively. The 10× concentrated PEC base-case system capital cost was $160 MM ($428 m_S−2 $11.5 WH₂P⁻¹) and for an efficiency of 20% the LCH was $9.2 kg−1. Likewise the grid supplemented base-case PV-E system capital cost was $66 MM ($441 _mS⁻² $11.5 W_H2P⁻¹) and with solar-to-hydrogen and grid electrolysis system efficiencies of 9.8% and 61% respectively the LCH was $6.1 kg⁻¹. As a benchmark a proton-exchange membrane (PEM) based grid-connected electrolysis system was analyzed. Assuming a system efficiency of 61% and a grid electricity cost of $0.07 kWh⁻¹ the LCH was $5.5 kg⁻¹. A sensitivity analysis indicated that relative to the base-case increases in the system efficiency could effect the greatest cost reductions for all systems due to the areal dependencies of many of the components. The balance-of-systems (BoS) costs were the largest factor in differentiating the PEC and PV-E systems. No single or combination of technical advancements based on currently demonstrated technology can provide sufficient cost reductions to allow solar hydrogen to directly compete on a levelized cost basis with hydrogen produced from fossil energy. Specifically a cost of CO₂ greater than ∼$800 (ton CO₂)−1 was estimated to be necessary for base-case PEC hydrogen to reach price parity with hydrogen derived from steam reforming of methane priced at $12 GJ⁻¹ ($1.39 (kg H₂)⁻¹). A comparison with low CO₂ and CO₂-neutral energy sources indicated that base-case PEC hydrogen is not currently cost-competitive with electrolysis using electricity supplied by nuclear power or from fossil-fuels in conjunction with carbon capture and storage. Solar electricity production and storage using either batteries or PEC hydrogen technologies are currently an order of magnitude greater in cost than electricity prices with no clear advantage to either battery or hydrogen storage as of yet. Significant advances in PEC technology performance and system cost reductions are necessary to enable cost-effective PEC-derived solar hydrogen for use in scalable grid-storage applications as well as for use as a chemical feedstock precursor to CO₂-neutral high energy-density transportation fuels. Hence such applications are an opportunity for foundational research to contribute to the development of disruptive approaches to solar fuels generation systems that can offer higher performance at much lower cost than is provided by current embodiments of solar fuels generators. Efforts to directly reduce CO₂ photoelectrochemically or electrochemically could potentially produce products with higher value than hydrogen but many as yet unmet challenges include catalytic efficiency and selectivity and CO₂ mass transport rates and feedstock cost. Major breakthroughs are required to obtain viable economic costs for solar hydrogen production but the barriers to achieve cost-competitiveness with existing large-scale thermochemical processes for CO₂ reduction are even greater.

We present the results of a life-cycle assessment (LCA) for the manufacturing and end-of-life (EoL) phases of the following fuel-cell and hydrogen (FCH) technologies: alkaline water electrolyser (AWE) polymer-electrolyte-membrane water electrolyser (PEMWE) high-temperature (HT) and low-temperature (LT) polymer-electrolyte-membrane fuel cells (PEMFCs) together with the balance-of-plant components. New life-cycle inventories (LCIs) i.e. material inputs for the AWE PEMWE and HT PEMFC are developed whereas the existing LCI for the LT PEMFC is adopted from a previous EU-funded project. The LCA models for all four FCH technologies are created by modelling the manufacturing phase followed by defining the EoL strategies and processes used and finally by assessing the effects of the EoL approach using environmental indicators. The effects are analysed with a stepwise approach where the CML2001 assessment method is used to evaluate the environmental impacts. The results show that the environmental impacts of the manufacturing phase can be substantially reduced by using the proposed EoL strategies (i.e. recycled materials being used in the manufacturing phase and replacing some of the virgin materials). To point out the importance of critical materials (in this case the platinum-group metals or PGMs) and their recycling strategies further analyses were made. By comparing the EoL phase with and without the recycling of PGMs an increase in the environmental impacts is observed which is much greater in the case of both fuel-cell systems because they contain a larger quantity of PGMs.

Hydrogen technologies have experienced cycles of excessive expectations followed by disillusion. Nonetheless a growing body of evidence suggests these technologies form an attractive option for the deep decarbonisation of global energy systems and that recent improvements in their cost and performance point towards economic viability as well. This paper is a comprehensive review of the potential role that hydrogen could play in the provision of electricity heat industry transport and energy storage in a low-carbon energy system and an assessment of the status of hydrogen in being able to fulfil that potential. The picture that emerges is one of qualified promise: hydrogen is well established in certain niches such as forklift trucks while mainstream applications are now forthcoming. Hydrogen vehicles are available commercially in several countries and 225 000 fuel cell home heating systems have been sold. This represents a step change from the situation of only five years ago. This review shows that challenges around cost and performance remain and considerable improvements are still required for hydrogen to become truly competitive. But such competitiveness in the medium-term future no longer seems an unrealistic prospect which fully justifies the growing interest and policy support for these technologies around the world.

Low-carbon hydrogen is an essential element in the transition to net-zero emissions by 2050. Hydrogen production from biomass is a promising bio-energy with carbon capture and storage (BECCS) scheme that could produce low-carbon hydrogen and generate the carbon dioxide removal (CDR) envisioned to be required to offset hard-to-abate emissions. Here we design a BECCS supply chain for hydrogen production from biomass with carbon capture and storage and quantify at high spatial resolution the technical potential for hydrogen production and CDR in Europe. We consider sustainable biomass feedstocks that have minimal impacts on food security and biodiversity namely agricultural residues and waste. We find that this BECCS supply chain can produce up to 12.5 Mtons of H2 per year (currently ~10 Mtons of H2 per year are used in Europe) and remove up to 133 Mtons CO2 per year from the atmosphere (or 3% of European total greenhouse gas emissions). We then perform a geospatial analysis to quantify transportation distances between where biomass feedstocks are located and potential hydrogen users and find that 20% of hydrogen potential is located within 25 km from hard-toelectrify industries. We conclude that BECCS supply chains for hydrogen production from biomass represent an overlooked near-term opportunity to generate carbon dioxide removal and low-carbon hydrogen.

The effects of thermomechanical processing on the microstructure and hydrogen embrittlement properties of ultrahigh-strength low-alloy transformation-induced plasticity (TRIP)-aided bainitic ferrite (TBF) steels were investigated to apply to automobile forging parts such as engine and drivetrain parts. The hydrogen embrittlement properties were evaluated by conducting conventional tensile tests after hydrogen charging and constant load four-point bending tests with hydrogen charging. The 0.4 mass%C-TBF steel achieved refinement of the microstructure improved retained austenite characteristics and strengthening owing to thermomechanical processing. This might be attributed to dynamic and static recrystallizations during thermomechanical processing in TBF steels. Moreover the hydrogen embrittlement resistances were improved by the thermomechanical processing in TBF steels. This might be caused by the refinement of the microstructure an increase in the stability of the retained austenite and low hydrogen absorption of the thermomechanically processed TBF steels.

If Hydrogen is expected to be highly valuable some improvements should be conducted mainly regarding the storage safety. To prevent from high pressure hydrogen composite tanks bursting the comprehension of the thermo-mechanics phenomena in the case of fire should be improved. To understand the kinetic of strength loss the heat flux produced by fire of various intensities should be assessed. This is the objective of this real scale experimental campaign which will allow studying in future works the strength loss of composite high-pressure vessels in similar fire conditions to the ones determined in this study. Fire calibration tests were performed on metallic cylinder vessels. These tests with metallic cylinders are critical in the characterization of the thermal load of various fire sources (pool fire propane gas fire hydrogen gas fire) so as to evaluate differences related to different thermal load. Radiant panels were also used as thermal source for reference of pure radiation heat transfer. The retained thermal load might be representative of accidental situations in worst case scenarios and relevant for a standardized testing protocol. The tests performed show that hydrogen gas fires and heptane pool fire allow reaching the target in terms of absorbed energy regarding the results of risk analysis performed previously. Other considerations can be taken into account that will led to retain an hydrogen gas fire for further works. Firstly hydrogen gas fire is the more realistic scenario: Hydrogen is the combustible that we every time find near an hydrogen storage. Secondly as one of the objectives of the project is to make recommendations for standardization issues it's important to note that gas fires are not too complex to calibrate control and reproduce. Finally due to previous considerations Hydrogen gas fire will be retained for thermal load of composite cylinders in future works.

A new type of high strength corrosion-resistant magnesium alloy was prepared by adding 1% rare earth Gd to AM50 and then treated with hot extrusion method. The stress corrosion properties of the new materials in air pure water 0.5 mol/L NaCl and 0.5 mol/L Na2_SO₄ solution were studied by the slow strain rate tensile (SSRT) test in situ open circuit potential test Tafel curve test stereomicroscope SEM and EDS. The results showed the following. The stress corrosion sensitivity of the material in different environments was Na2_SO₄> NaCl > distilled water > air. According to the Tafel curves measured at 0 and 100 MPa the corrosion voltage decreased little and the corrosion current density increased rapidly under 100 Pa. This was because the film of the corrosion product ruptured to form a large cathode and a small anode which resulted in a large instantaneous corrosion current. The mechanism of hydrogen embrittlement and anodic dissolution together affected the stress corrosion behavior of the alloy. In distilled water hydrogen embrittlement played a major role while in NaCl and Na2_SO₄solution hydrogen embrittlement and anodic dissolution were both affected. The direct reason of the stress corrosion crack (SCC) samples’ failure was the cracks expanding rapidly at the bottom of pit which was caused by corrosion.

Hydrogen fuelled vehicles can play a key role in the decarbonisation of transport and reducing emissions. To ensure the durability of fuel cells a specification has been developed (ISO 14687) setting upper limits to the amount fraction of a series of impurities. Demonstrating conformity with this standard requires demonstrating by measurement that the actual levels of the impurities are below the thresholds. Currently the industry is unable to do so for measurement standards and sensitive dedicated analytical methods are lacking. In this work we report on the development of such measurement standards and methods for four reactive components: formaldehyde formic acid hydrogen chloride and hydrogen fluoride. The primary measurement standard is based on permeation and the analytical methods on highly sensitive and selective laser-based spectroscopic techniques. Relative expanded uncertainties at the ISO 14687 threshold level in hydrogen of 4% (formaldehyde) 8% (formic acid) 5% (hydrogen chloride) and 8% (hydrogen fluoride) have been achieved.