Production & Supply Chain

This paper deals with two main issues regarding the specific energy consumption in an electrolyzer (i.e. the Faraday efficiency and the converter topology). The first aspect is addressed using a multistack configuration of proton exchange membrane (PEM) electrolyzers supplied by a wind turbine conversion system (WTCS). This approach is based on the modeling of the wind turbine and the electrolyzers. The WTCS and the electrolyzers are interfaced through a stacked interleaved DC–DC buck converter (SIBC) due to its benefits for this application in terms of the output current ripple and reliability. This converter is controlled so that it can offer dynamic behavior that is faster than the wind turbine avoiding overvoltage during transients which could damage the PEM electrolyzers. The SIBC is designed to be connected in array configuration (i.e. parallel architecture) so that each converter operates at its maximum efficiency. To assess the performance of the power management strategy experimental tests were carried out. The reported results demonstrate the correct behavior of the system during transient operation.

Membrane separation is a compelling technology for hydrogen separation. Among the different types of membranes used to date the mixed-matrix membranes (MMMs) are one of the most widely used approaches for enhancing separation performances and surpassing the Robeson upper bound limits for polymeric membranes. In this review we focus on the recent progress in MMMs for hydrogen separation. The discussion first starts with a background introduction of the current hydrogen generation technologies followed by a comparison between the membrane technology and other hydrogen purification technologies. Thereafter state-of-the-art MMMs comprising emerging filler materials that include zeolites metal-organic frameworks covalent organic frameworks and graphene-based materials are highlighted. The binary filler strategy which uses two filler materials to create synergistic enhancements in MMMs is also described. A critical evaluation on the performances of the MMMs is then considered in context before we conclude with our perspectives on how MMMs for hydrogen separation can advance moving forward.

Growing human activity has led to a critical rise in global energy consumption; since the current main sources of energy production are still fossil fuels this is an industry linked to the generation of harmful byproducts that contribute to environmental deterioration and climate change. One pivotal element with the potential to take over fossil fuels as a global energy vector is renewable hydrogen; but for this to happen reliable solutions must be developed for its carbon-free production. The objective of this study was to perform a comprehensive review on several hydrogen production technologies mainly focusing on water splitting by green-electrolysis integrated on hydrogen’s value chain. The review further deepened into three leading electrolysis methods depending on the type of electrolyzer used—alkaline proton-exchange membrane and solid oxide—assessing their characteristics advantages and disadvantages. Based on the conclusions of this study further developments in applications like the efficient production of renewable hydrogen will require the consideration of other types of electrolysis (like microbial cells) other sets of materials such as in anion-exchange membrane water electrolysis and even the use of artificial intelligence and neural networks to help design plan and control the operation of these new types of systems.

Green hydrogen production is essential to meeting the conference of the parties’ (COP) decarbonization goals; however this method of producing hydrogen is not as cost-effective as hydrogen production from fossil fuels. This study analyses an off-grid photovoltaic energy system designed to feed a proton-exchange membrane water electrolyzer for hydrogen production to evaluate the optimal electrolyzer size. The system has been analyzed in Baghdad the capital of Iraq using experimental meteorological data. The 12 kWp photovoltaic array is positioned at the optimal annual tilt angle for the selected site. The temperature effect on photovoltaic modules is taken into consideration. Several electrolyzers with capacities in the range of 2–14 kW were investigated to assess the efficiency and effectiveness of the system. The simulation process was conducted using MATLAB and considering the project life span from 2021 to 2035. The results indicate that various potentially cost-competitive alternatives exist for systems with market combinations resembling renewable hydrogen wholesale. It has been found that the annual energy generated by the analyzed photovoltaic system is 18892 kWh at 4313 operating hours and the obtained hydrogen production cost ranges from USD 5.39/kg to USD 3.23/kg. The optimal electrolyzer capacity matches a 12 kWp PV system equal to 8 kW producing 37.5 kg/year/kWp of hydrogen for USD 3.23/kg.

A redox dual-flow battery is distinct from a traditional redox flow battery (RFB) in that the former includes a secondary energy platform in which the pre-charged electrolytes can be discharged in external catalytic reactors through decoupled redox-mediated hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). The concept offers several advantages over conventional electrolysis in terms of safety durability modularity and purity. In this work we demonstrate a vanadium-manganese redox-flow battery in which Mn3+/Mn2+ and V3+/V2+ respectively mediate the OER and the HER in Mo2C-based and RuO2-based catalysts. The flow battery demonstrates an average energy efficiency of 68% at a current density of 50 mA ⋅ cm−2 (cell voltage = 1.92 V) and a relative energy density 45% higher than the conventional all-vanadium RFB. Both electrolytes are spontaneously discharged through redox-mediated HER and OER with a faradic efficiency close to 100%.

Autothermal reforming of bioethanol (ATR of C2H5OH) over promoted Ni/Ce0.8La0.2O1.9 catalysts was studied to develop carbon-neutral technologies for hydrogen production. The regulation of the functional properties of the catalysts was attained by adjusting their nanostructure and reducibility by introducing various types and content of M promoters (M = Pt Pd Rh Re; molar ratio M/Ni = 0.003–0.012). The composition–characteristics–activity correlation was determined using catalyst testing in ATR of C2H5OH thermal analysis N2 adsorption X-ray diffraction transmission electron microscopy and EDX analysis. It was shown that the type and content of the promoter as well as the preparation mode (combined or sequential impregnation methods) determine the redox properties of catalysts and influence the textural and structural characteristics of the samples. The reducibility of catalysts improves in the following sequence of promoters: Re < Rh < Pd < Pt with an increase in their content and when using the co-impregnation method. It was found that in ATR of C2H5OH over bimetallic Ni-M/Ce0.8La0.2O1.9 catalysts at 600 ◦C the hydrogen yield increased in the following row of promoters: Pt < Rh < Pd < Re at 100% conversion of ethanol. The introduction of M leads to the formation of a NiM alloy under reaction conditions and affects the resistance of the catalyst to oxidation sintering and coking. It was found that for enhancing Ni catalyst performance in H2 production through ATR of C2H5OH the most effective promotion is with Re: at 600 ◦C over the optimum 10Ni-0.4Re/Ce0.8La0.2O1.9 catalyst the highest hydrogen yield 65% was observed.

Mg attracts much research interest as anode material for Ni-MH batteries thanks to its lightweight cost-effectiveness and high theoretical capacity (2200 mA h g⁻¹). However its practical application is tremendously challenged by the poor hydrogen sorption kinetics passivation from aggressive aqueous electrolytes and insulating nature of MgH₂. Mg-based alloys exhibit enhanced hydrogen sorption kinetics and electrical conductivity but significant amount of costly transition metal elements are required. In this work we have for the first time utilized non-alloyed but catalyzed Mg as anode for Ni-MH batteries. 5 mol.% TiF3 was added to nanosized Mg for accelerating the hydrogen sorption kinetics. Several strategies for preventing the problematic passivation of Mg have been studied including protective encapsulation of the electrode and utilizing room-temperature/high-temperature ionic liquids and an alkaline polymer membrane as working electrolyte. Promising electrochemical performance has been achieved in this Mg–TiF₃ composite anode based Ni-MH batteries with room for further improvements.

Anion exchange membrane water electrolysis (AEMWE) is considered the next generation of green hydrogen production method because it uses low-cost non-noble metal oxide electrocatalyst electrodes and can store highpurity hydrogen under high pressure. However the commercialization of AEMWE with non-precious metal oxide electrocatalysts is challenging due to low electrocatalytic activity and durability. Overcoming the low kinetics caused by four-electron transfer is vital in addressing the low activity of non-noble metal oxide electrocatalysts for oxygen evolution reaction. This article overviews the synthesis methods and related techniques for various anode electrodes applied to AEMWE systems. We highlight effective strategies that have been developed to improve the performance and durability of the non-precious electrocatalysts and ensure the stable operation of AEMWE followed by a critical perspective to encourage the development of this technology.

This paper assesses the optimal design criteria of a flexible power and biomass to methanol (PBtM) plant conceived to operate both without green hydrogen addition (baseline mode) and with hydrogen addition (enhanced mode) following an intermittent use of the electrolysis system which is turned on when the electricity price allows an economically viable hydrogen production. The assessed plant includes a gasification section syngas cleaning and compression methanol synthesis and purification and heat recovery steam cycle to be flexibly operated. A sorption-enhanced gasification technology allows to produce a tailored syngas for the downstream synthesis in both the baseline and enhanced operating conditions by controlling the in-situ CO2 separation rate. Two designs are assessed for the methanol synthesis unit with two different reactor sizes: (i) a larger reactor designed on the enhanced operation mode (enhanced reactor design – ERD) and (ii) a smaller reactor designed on the baseline operation mode (baseline reactor design – BRD). The ERD design resulted to be preferable from the techno economic perspectives resulting in 20% lower cost of the e-MeOH (30.80 vs. 37.76 €/ GJLHV) with the baseline assumptions (i.e. 80% of electrolyzer capacity factor and 2019 Denmark day-ahead market electricity price). Other important outcomes are: (i) high electrolysis capacity factor is needed to obtain competitive cost of e-MeOH and (ii) advantages of flexibly operated PBtM plants with respect to inflexible PBtM plants are significant in scenarios with high penetration of intermittent renewables leading to low average prices of electricity but also longer periods of high peak prices.

Variable renewable energy (VRE) has seen rapid growth in recent years. However VRE deployment requires a fleet of dispatchable power plants to supply electricity during periods with limited wind and sunlight. These plants will operate at reduced utilization rates that pose serious economic challenges. To address this challenge this paper presents the techno-economic assessment of flexible power and hydrogen production from integrated gasification combined cycles (IGCC) employing the gas switching combustion (GSC) technology for CO₂ capture and membrane assisted water gas shift (MAWGS) reactors for hydrogen production. Three GSC-MAWGS-IGCC plants are evaluated based on different gasification technologies: Shell High Temperature Winkler and GE. These advanced plants are compared to two benchmark IGCC plants one without and one with CO₂ capture. All plants utilize state-of-the-art H-class gas turbines and hot gas clean-up for maximum efficiency. Under baseload operation the GSC plants returned CO₂ avoidance costs in the range of 24.9–36.9 €/ton compared to 44.3 €/ton for the benchmark. However the major advantage of these plants is evident in the more realistic mid-load scenario. Due to the ability to keep operating and sell hydrogen to the market during times of abundant wind and sun the best GSC plants offer a 6–11%-point higher annual rate of return than the benchmark plant with CO₂ capture. This large economic advantage shows that the flexible GSC plants are a promising option for balancing VRE provided a market for the generated clean hydrogen exists.