Production & Supply Chain

The catalytic steam reforming of biodiesel was examined over Ni-alumina and Ni–ceria–zirconia catalysts at atmospheric pressure. Effects of temperatures of biodiesel preheating/vaporising (190–365 ◦C) and reforming (600–800 ◦C) molar steam to carbon ratio (S/C = 2–3) and residence time in the reformer represented by the weight hourly space velocity ‘WHSV’ of around 3 were examined for 2 h. Ni supported on calcium aluminate and on ceria–zirconia supports achieved steady state hydrogen product stream within 90% of the equilibrium yields although 4% and 1% of the carbon feed had deposited on the catalysts respectively during the combined conditions of start-up and steady state. Addition of dopants to ceria–zirconia supported catalyst decreased the performance of the catalyst. Increase in S/C ratio had the expected positive effects of higher H2 yield and lower carbon deposition.

Due to its characteristics hydrogen is considered the energy carrier of the future. Its use as a fuel generates reduced pollution as if burned it almost exclusively produces water vapor. Hydrogen can be produced from numerous sources both of fossil and renewable origin and with as many production processes which can use renewable or non-renewable energy sources. To achieve carbon neutrality the sources must necessarily be renewable and the production processes themselves must use renewable energy sources. In this review article the main characteristics of the most used hydrogen production methods are summarized mainly focusing on renewable feedstocks furthermore a series of relevant articles published in the last year are reviewed. The production methods are grouped according to the type of energy they use; and at the end of each section the strengths and limitations of the processes are highlighted. The conclusions compare the main characteristics of the production processes studied and contextualize their possible use.

Hydrogen as a strategy clean fuel is receiving more and more attention recently in China in addition to the policy emphasis on H2. In this work we conceive of a hydrogen production process based on a chemical regenerative coal gasification. Instead of using a lumped coal gasification as is traditional in the H2 production process herein we used a two-step gasification process that included coking and char-steam gasification. The sensible heat of syngas accounted for 15–20% of the total energy of coal and was recovered and converted into chemical energy of syngas through thermochemical reactions. Moreover the air separation unit was eliminated due to the adoption of steam as oxidant. As a result the efficiency of coal to H2 was enhanced from 58.9% in traditional plant to 71.6% in the novel process. Further the energy consumption decreased from 183.8 MJ/kg in the traditional plant to 151.2 MJ/kg in the novel process. The components of syngas H2 and efficiency of gasification are herein investigated through experiments in fixed bed reactors. Thermodynamic performance is presented for both traditional and novel coal to hydrogen plants.

Recent years have seen a growing interest in water electrolysis as a way to store renewable electric energy into chemical energy through hydrogen production. However today the share of renewable energy is still limited and there is the need to have a continuous use of H2 for industrial chemicals applications. Firstly the paper discusses the use of electrolysis - connected to a conventional grid - for a continuous H2 production in terms of associated CO2 emissions and compares such emissions with conventional methane steam reforming (MSR). Therefore it explores the possibility to use electrical methane steam reforming (eMSR) as a way to reduce the CO2 emissions. As a way to have zero emissions carbon mineralization of CO2 is coupled - instead of in-situ carbon capture and storage technology (CCS) - to eMSR; associated relevant cost of production is evaluated for different scenarios. It appears that to minimize such production cost carbonate minerals must be reused in the making of other industrial products since the amount of carbonates generated by the process is quite significant.

Hydrogen will become a dominant energy carrier in the future and the efficiency and lifetime cost of its production through water electrolysis is a major research focus. Alongside efforts to offer optimum solutions through plant design and sizing it is also necessary to develop a flexible virtualised replica of renewable hydrogen plants that not only models compatibility with the “plug-and-play” nature of many facilities but that also identifies key elements for optimisation of system operation. This study presents a model for a renewable hydrogen production plant based on real-time historical and present-day datasets of PV connected to a virtualised grid-connected AC microgrid comprising different technologies of batteries electrolysers and fuel cells. Mathematical models for each technology were developed from chemical and physical metrics of the plant. The virtualised replica is the first step toward the implementation of a digital twin of the system and accurate validation of the system behaviour when updated with real-time data. As a case study a solar hydrogen pilot plant consisting of a 60 kW Solar PV a 40 kW PEM electrolyser a 15 kW LIB battery and a 5 kW PEM fuel cell were simulated and analysed. Two effective operational factors on the plant's performance are defined: (i) electrolyser power settings to determine appropriate hydrogen production over twilight periods and/or overnight and (ii) a user-defined minimum threshold for battery state of charge to prevent charge depletion overnight if the electrolyser load is higher than its capacity. The objective of this modelling is to maximise hydrogen yield while both loss of power supply probability (LPSP) and microgrid excess power are minimised. This analysis determined: (i) a hydrogen yield of 38e39% from solar DC energy to hydrogen energy produced (ii) an LPSP <2.6 104 and (iii) < 2% renewable energy lost to the grid as excess electricity for the case study.

This work reports a detailed chemical looping investigation of strontium ferrite (SrFeO_3−δ) a material with the perovskite structure type able to donate oxygen and stay in a nonstoichiometric form over a broad range of oxygen partial pressures starting at temperatures as low as 250°C (reduction in CO measured in TGA). SrFeO_3−δ is an economically attractive simple but remarkably stable material that can withstand repeated phase transitions during redox cycling. Mechanical mixing and calcination of iron oxide and strontium carbonate was evaluated as an effective way to obtain pure SrFeO_3−δ. In–situ XRD was performed to analyse structure transformations during reduction and reoxidation. Our work reports that much deeper reduction from SrFeO_3−δ to SrO and Fe is reversible and results in oxygen release at a chemical potential suitable for hydrogen production. Thermogravimetric experiments with different gas compositions were applied to characterize the material and evaluate its available oxygen capacity. In both TGA and in-situ XRD experiments the material was reduced below δ=0.5 followed by reoxidation either with CO₂ or air to study phase segregation and reversibility of crystal structure transitions. As revealed by in-situ XRD even deeply reduced material regenerates at 900°C to SrFeO_3−δ with a cubic structure. To investigate the catalytic behaviour of SrFeO_3−δ in methane combustion experiments were performed in a fluidized bed rig. These showed SrFeO_3−δ donates O₂ into the gas phase but also assists with CH4 combustion by supplying lattice oxygen. To test the material for combustion and hydrogen production long cycling experiments in a fluidized bed rig were also performed. SrFeO3−δ showed stability over 30 redox cycles both in experiments with a 2-step oxidation performed in CO₂ followed by air as well as a single step oxidation in CO₂ alone. Finally the influence of CO/CO₂ mixtures on material performance was tested; a fast and deep reduction in elevated pCO₂ makes the material susceptible to carbonation but the process can be reversed by increasing the temperature or lowering pCO₂.

This study investigates the decomposition of methane using solar thermal energy as a heat source. Instead of the direct thermal decomposition of the methane at a temperature of 1200 ◦C or higher a catalyst coated with carbon black on a metal foam was used to lower the temperature and activation energy required for the reaction and to increase the yield. To supply solar heat during the reaction a reactor suitable for a solar concentrating system was developed. In this process a direct heating type reactor with quartz was initially applied and a number of problems were identified. An indirect heating type reactor with an insulated cavity and a rotating part was subsequently developed followed by a thermal barrier coating application. Methane decomposition experiments were conducted in a 40 kW solar furnace at the Korea Institute of Energy Research. Conversion rates of 96.7% and 82.6% were achieved when the methane flow rate was 20 L/min and 40 L/min respectively.

The study of the viability of hydrogen production as a sustainable energy source is a current challenge to satisfy the great world energy demand. There are several techniques to produce hydrogen either mature or under development. The election of the hydrogen production method will have a high impact on practical sustainability of the hydrogen economy. An important profile for the viability of a process is the calculation of energy and exergy efficiencies as well as their overall integration into the circular economy. To carry out theoretical energy and exergy analyses we have estimated proposed hydrogen production using different software (DWSIM and MATLAB) and reference conditions. The analysis consolidates methane reforming or auto-thermal reforming as the viable technologies at the present state of the art with reasonable energy and exergy efficiencies but pending on the impact of environmental constraints as CO2 emission countermeasures. However natural gas or electrolysis show very promising results and should be advanced in their technological and maturity scaling. Electrolysis shows a very good exergy efficiency due to the fact that electricity itself is a high exergy source. Pyrolysis exergy loses are mostly in the form of solid carbon material which has a very high integration potential into the hydrogen economy.

A rigorous heterogeneous mathematical model is used to simulate a cascade of multi-stage fixed bed membrane reactors (MSFBMR) with inter-stage heating and fresh sweep gas for the decomposition of ammonia to produce high purity hydrogen suitable for the PEM fuel cells. Different reactor configurations are compared. The comparison between a single fixed bed reactor (FBR) and a single fixed bed membrane reactor (FBMR) shows that the FBMR is superior to the FBR and gives 60.48% ammonia conversion higher than the FBR. However 20.91% exit ammonia conversion obtained by the FBMR is considered to be poor. The FBMR is limited by the kinetics at low temperatures. The numerical results show that the MSFBMR of four beds achieve 100.0% ammonia conversion. It was found that the membrane plays the prime role in the displacement of the thermodynamic equilibrium. The results also show that a linear relationship exists between the number of beds and the feed temperature and a correlation has been developed. A critical point for an effective hydrogen permeation zone has been identified. It is observed that the diffusion limitation is confined to a slim region at the entrance of the reactor. It is also observed that the heat load assumes a maximum inflection point and explanations offered. The results show that the multi-stage configuration has a promising potential to be applied successfully on-site for ultra-clean hydrogen production.

The analysis here presented investigates the influence of electrical load on the operational performances of a plant for hydrogen production from solar energy and its conversion in electricity via a fuel cell. The plant is an actual one currently under construction in Reggio Calabria (Italy) at the site of the Mediterranean university campus; it is composed of a Renewable Energy Source (RES) section (photovoltaic panels) a hydrogen production section and a fuel cell power section feeding the electrical energy demand of the load. Two different load configurations have been analysed and simulations have been carried out through HomerTM simulation code. Results allow interesting conclusions regarding the plant operation to be drawn. The study could have a remarkable role in supporting further research activities aimed at the assessment of the optimal configuration of this type of pioneering plants designed for feeding electrical loads possibly in a self-sufficient way.