Production & Supply Chain

Hydrogen production through methanol reforming processes has been stimulated over the years due to increasing interest in fuel cell technology and clean energy production. Among different types of methanol reforming the steam reforming of methanol has attracted great interest as reformate gas stream where high concentration of hydrogen is produced with a negligible amount of carbon monoxide. In this review recent progress of the main reforming processes of methanol towards hydrogen production is summarized. Different catalytic systems are reviewed for the steam reforming of methanol: mainly copper- and group 8–10-based catalysts highlighting the catalytic key properties while the promoting effect of the latter group in copper activity and selectivity is also discussed. The effect of different preparation methods different promoters/stabilizers and the formation mechanism is analyzed. Moreover the integration of methanol steam reforming process and the high temperature–polymer electrolyte membrane fuel cells (HT-PEMFCs) for the development of clean energy production is discussed.

This paper addresses from both macro- and micro- areal coverage in introducing hydrogen system in terms of cost and performance where the produced hydrogen from surplus photovoltaic (PV) power is stored. Feed-in tariff in Japan had successful achievement for great expansion of renewable energy systems (RES) causing problematic operation due to excess power by overcapacity of RES. One of the candidate approaches to overcome this surplus energy by RES is Power to gas (P2G) system using electrolysis cells (ECs) fuel cells (FCs) or co-firing in gas turbines both for energy conversion as well as power balancing. Numerous studies had been investigated on P2G however within our knowledge no study had been addressed the system from both coverages with different capacity and scales. We investigate micro level (zero emission building in our university) and macro level (Kyushu one of big regions in Japan). We describe for macro side preliminary result on economic analysis of using surplus power of RES via production and storage of hydrogen while for micro side research design.

An energy production from the combination of dehydrogenation and combined cycle power generation is proposed. The delivered system is established from three main modules: dehydrogenation combustion and combined cycle. The heat in the system is circulated thoroughly to enhance the energy efficiency due to optimum energy recovery. The Pt/Al2O3 catalyst is applied in the dehydrogenation module due to superior activity to accelerate the dehydrogenation of MCH. The toluene emitted from the MCH is recirculated to the hydrogenation plant while the hydrogen is further utilized as the fuel in the combustion. Although the high-temperature condition is necessary to perform high yield dehydrogenation the proposed system is capable of carrying out self-heating mechanism with no external heat. With the optimum configuration the delivered system can produce 100.0 MW of electricity from 100 t/h of MCH with 50.19% of energy efficiency.

The non-interconnected islands of Greece can benefit from the comprehensive use of RES to avoid water droughts and ensure energy autonomy. The present paper analyzes an HRES with two possible operating scenarios. Both of them include a wind park of 27.5 MW capacity an 1175 m3/day desalination plant and a 490000 m3/day water tank in Lemnos Greece. Regarding the wind power 70% is used in the HRES while the rest is channeled directly to the grid. The main difference comes down to how the wind energy is stored either in the form of hydraulic energy or in the form of hydrogen. The lifespan of the system is 25 years such as the produced stochastic series of rainfall temperature and wind of the area. Through the comparison of the operating scenarios the following results arise: (i) the water needs of the island are fully covered and the irrigation needs have a reliability of 66% in both scenarios. (ii) Considering the energy needs the pumping storage seems to be the most reliable solution. (iii) However depending on the amount of wind energy surplus the use of hydrogen could produce more energy than the hydroelectric plant.

Reversible solid oxide cells (r-SOCs) can be operated in either solid oxide fuel cell or solid oxide electrolysis cell mode. They are expected to become important in the support of renewable energy due to their high efficiency for both power generation and hydrogen generation. The exchange current density is one of the most important parameters in the quantification of electrode performance in solid oxide cells. In this study four different fuel electrodes and two different air electrodes are fabricated using different materials and the microstructures are compared. The temperature fuel humidification and oxygen concentration at the air electrode are varied to obtain the apparent exchange current density for the different electrode materials. In contrast to ruthenium-and-gadolinia-doped ceria (Rh-GDC) as well as nickel-and-gadolinia-doped ceria (Ni-GDC) electrodes significant differences in the apparent exchange current density were observed between electrolysis and fuel cell modes for the nickel-scandia-stabilized zirconia (Ni-ScSZ) cermet. Variation of gas concentration revealed that surface adsorption sites were almost completely vacant for all these electrodes. The apparent exchange current densities obtained in this study are useful as a parameter for simulation of the internal properties of r-SOCs.

Activated carbons with different surface chemistry and porous textures were used to study the mechanism of electrochemical hydrogen and oxygen evolution in supercapacitor devices. Cellulose precursor materials were activated with different potassium hydroxide (KOH) ratios and the electrochemical behaviour was studied in 6 M KOH electrolyte. In situ Raman spectra were collected to obtain the structural changes of the activated carbons under severe electrochemical oxidation and reduction conditions and the obtained data were correlated to the cyclic voltammograms obtained at high anodic and cathodic potentials. Carbon-hydrogen bonds were detected for the materials activated at high KOH ratios which form reversibly under cathodic conditions. The influence of the specific surface area narrow microporosity and functional groups in the carbon electrodes on their chemical stability and hydrogen capture mechanism in supercapacitor applications has been revealed.

Direct Numerical Simulation (DNS) data obtained by Dave and Chaudhuri (2020) from a lean complex-chemistry hydrogen-air flame associated with the thin-reaction-zone regime of premixed turbulent burning are analyzed to perform a priori assessment of predictive capabilities of the flamelet approach for evaluating mean species concentrations. For this purpose dependencies of mole fractions and rates of production of various species on a combustion progress variable c obtained from the laminar flame are averaged adopting either the actual Probability Density Function (PDF) P (c)  extracted from the DNS data or a common presumed β-function PDF. On the one hand the results quantitatively validate the flamelet approach for the mean mole fractions of all species including radicals but only if the actual PDF P (c) is adopted. The use of the β-function PDF yields substantially worse results for the radicals’ concentrations. These findings put modeling the PDF P (c) on the forefront of the research agenda. On the other hand the mean rate of product creation and turbulent burning velocity are poorly predicted even adopting the actual PDF. These results imply that in order to evaluate the mean species concentrations the flamelet approach could be coupled with another model that predicts the mean rate and turbulent burning velocity better. Accordingly the flamelet approach could be implemented as post-processing of numerical data yielded by that model. Based on the aforementioned findings and implications a new approach to building a presumed PDF is developed. The key features of the approach consist in (i) adopting a re-normalized flamelet PDF for intermediate values of c and (ii) directly using the mean rate of product creation to calibrate the presumed PDF. Capabilities of the newly developed PDF for predicting mean species concentrations are quantitively validated for all species including radicals.

This study presents an integrated techno-environmental assessment of hydrogen production from natural gas and biomethane combined with CO₂ capture and storage (CCS). We have included steam methane reforming (SMR) and autothermal reforming (ATR) for syngas production. CO₂ is captured from the syngas with a novel vacuum pressure swing adsorption (VPSA) process that combines hydrogen purification and CO₂ separation in one cycle. As comparison we have included cases with conventional amine-based technology. We have extended standard attributional Life Cycle Assessment (LCA) following ISO standards with a detailed carbon balance of the biogas production process (via digestion) and its by-products. The results show that the life-cycle greenhouse gas (GHG) performance of the VPSA and amine-based CO₂ capture technologies is very similar as a result of comparable energy consumption. The configuration with the highest plant-wide CO₂ capture rate (almost 100% of produced CO₂ captured) is autothermal reforming with a two-stage water-gas shift and VPSA CO₂ capture – because the latter has an inherently high CO₂ capture rate of 98% or more for the investigated syngas. Depending on the configuration the addition of CCS to natural gas reforming-based hydrogen production reduces its life-cycle Global Warming Potential by 45–85 percent while the other environmental life-cycle impacts slightly increase. This brings natural gas-based hydrogen on par with renewable electricity-based hydrogen regarding impacts on climate change. When biomethane is used instead of natural gas our study shows potential for net negative greenhouse gas emissions i.e. the net removal of CO₂ over the life cycle of biowaste-based hydrogen production. In the special case where the biogas digestate is used as agricultural fertiliser and where a substantial amount of the carbon in the digestate remains in the soil the biowaste-based hydrogen reaches net-negative life cycle greenhouse gas emissions even without the application of CCS. Addition of CCS to biomethane-based hydrogen production leads to net-negative emissions in all investigated cases.

In addition to methane gas higher-value resources such as hydrogen gas are produced during anaerobic wastewater treatment. They are however immediately consumed by other organisms. To recover these high-value resources not only do the desired phenotypes need to be retained in the anaerobic reactor but the undesired ones need to be washed out. In this study a well-established alginate-based polymer gel with and without a coating layer was used to selectively encapsulate hydrogen-producing biomass in beads to achieve high-rate recovery of hydrogen during anaerobic wastewater treatment. The effect of cross-linking agents Ca²+ Sr²⁺ and Ba²⁺ as well as a composite coating on the beads consisting of alternating layers of polyethylenimine and silica hydrogel were investigated with respect to their performance specifically their mass transfer characteristics and their differential ability to retain the encapsulated biomass. Although the coating reduced the escape rate of encapsulated biomass from the beads all alginate polymer matrices without coating effectively retained biomass. Fast diffusion of dissolved organic carbon (DOC) through the polymer gel was observed in both Ca-alginate and Sr-alginate without coating. The coating however decreased either the diffusivity or the permeability of the DOC depending on whether the DOC was from synthetic wastewater (more lipids and proteins) or real brewery wastewater (more sugars). Consequently the encapsulation system with coating became diffusion limited when brewery wastewater with high chemical oxygen demand was fed resulting in a lower hydrogen production rate than the uncoated encapsulation systems. In all cases the encapsulated biomass was able to produce hydrogen even at a hydraulic residence time of 45 min. Although there are limitations to this system the used of encapsulated biomass for resource recovery from wastewater shows promise particularly for high-rate systems in which the retention of specific phenotypes is desired.

Chemical looping water splitting or chemical looping hydrogen is a very promising technology for the production of hydrogen. In recent years extensive research has enabled remarkable leaps towards a successful integration of the chemical looping technology into a future hydrogen infrastructure. Progress has been reported with iron based oxygen carriers for stable hydrogen production capacity over consecutive cycles without significant signs of degradation. The high stability improvements were achieved by adding alien metal oxides or by integrating the active component into a mineral structure which offers excellent resistance towards thermal stress. Prototype systems from small μ-systems up to 50 kW have been operated with promising results. The chemical looping water splitting process was broadened in terms of its application area and utilization of feedstocks using a variety of renewable and fossil resources. The three-reactor system was clearly advantageous due to its flexibility heat integration capabilities and possibility to produce separate pure streams of hydrogen CO₂ and N₂. However two-reactor and single fixed-bed reactor systems were successfully operated as well. This review aims to survey the recently presented literature in detail and systematically summarize the gathered data.