Production & Supply Chain

A hydrogen purification system based on the technology of the electrochemical hydrogen compression and purification is introduced. This system is developed within the scope of the project MEMPHYS. Therefore the project its targets and the different work stages are presented. The technology of the electrochemical purification and the state of the art of hydrogen purification are described. Early measurements in the project have been carried out and the results are shown and discussed. The ability of the technology to recover hydrogen from a gas mixture can be recognized and an outlook into further optimizations shows the future potential. A big advantage is the simultaneous compression of the purified hydrogen up to 200 bar therefore facilitating the transportation and storage.

Application of Solid Oxide Fuel Cells (SOFC) in gasification-based power plants would represent a turning point in the power generation sector allowing to considerably increase the electric efficiency of coal-fired power stations while reducing CO2 and other pollutant emissions. The aim of this paper is the thermodynamic assessment of a SOFC-based IGFC plant with methanation reactor hydrogen post-firing and CO2 capture by physical absorption. The configuration proposed allows to obtain a very high net efficiency (51.6%) overcoming the main limits of configurations assessed in previous works.

The pyrolysis-catalytic steam reforming of six agricultural biomass waste samples as well as the three main components of biomass was investigated in a two stage fixed bed reactor. Pyrolysis of the biomass took place in the first stage followed by catalytic steam reforming of the evolved pyrolysis gases in the second stage catalytic reactor. The waste biomass samples were rice husk coconut shell sugarcane bagasse palm kernel shell cotton stalk and wheat straw and the biomass components were cellulose hemicellulose (xylan) and lignin. The catalyst used for steam reforming was a 10 wt.% nickel-based alumina catalyst (NiAl2O3). In addition the thermal decomposition characteristics of the biomass wastes and biomass components were also determined using thermogravimetric analysis (TGA). The TGA results showed distinct peaks for the individual biomass components which were also evident in the biomass waste samples reflecting the existence of the main biomass components in the biomass wastes. The results for the two-stage pyrolysis-catalytic steam reforming showed that introduction of steam and catalyst into the pyrolysis-catalytic steam reforming process significantly increased gas yield and syngas production notably hydrogen. For instance hydrogen composition increased from 6.62 to 25.35 mmol g 1 by introducing steam and catalyst into the pyrolysis-catalytic steam reforming of palm kernel shell. Lignin produced the most hydrogen compared to cellulose and hemicellulose at 25.25 mmol g 1. The highest residual char production was observed with lignin which produced about 45 wt.% char more than twice that of cellulose and hemicellulose.

Laser-induced nuclear processes in ultra-dense hydrogen H(0) give ejection of bunches of mesons similar to known baryon annihilation processes. This process was recently described as useful for relativistic interstellar travel (Holmlid and Zeiner-Gundersen 2020) and more precise experimental results exist now. The mesons are identified from their known decay time constants at rest as slow charged kaons slow neutral long-lived kaons and slow charged pions. Other observed time constants are interpreted as relativistically dilated decays for fast mesons of the same three types with kinetic energy up to 100 MeV for the kaons. Mouns are observed with kinetic energy of >100 MeV as decay products from the mesons. These particle energies are much too high to be due to nuclear fusion in hydrogen and the only known process which can give such energies is baryon annihilation. A model of the annihilation process starting with two protons or two neutrons gives good agreement with the observed meson types and their masses and kinetic energies thus now giving the complete energetics of the process. The process works with both D(0) and p(0). The efficiency from mass (of two baryons) to useful energy is 46% (contrary to 0.3% for T + D fusion) and the main non-recoverable energy loss is to neutrinos. Neutrons are not formed or ejected so this is an aneutronic process. The energy which can be extracted from ordinary hydrogen is 11.4 TWh per kg. This annihilation method is well suited for small and medium energy applications in the kW to MW range but scaling-up to GW power stations requires further development. It is unlikely that this energy production method can be used for weapons since there is no ignition or chain reaction.

External magnetic fields affect various electrochemical processes and can be used to enhance the efficiency of the electrochemical water splitting reaction. However the driving forces behind this effect are poorly understood due to the analytical challenges of the available interface-sensitive techniques. Here we present a set-up based on magneto- and electro-optical probing which allows to juxtapose the magnetic properties of the electrode with the electrochemical current densities in situ at various applied potentials and magnetic fields. On the example of an archetypal hydrogen evolution catalyst Pt (in a form of Co/Pt superlattice) we provide evidence that a magnetic field acts on the electrochemical double layer affecting the local concentration gradient of hydroxide ions which simultaneously affects the magneto-optical and magnetocurrent response.

Hydrogen generation by the reaction of pure Al powder in water with the addition of Al(OH)3 γ- Al2O3 α-Al2O3 or TiO2 at mild temperatures was investigated. It was found that the reaction of Al with water is promoted and the reaction induction time decreases greatly by the above hydroxide and oxides. X-ray diffraction analyses revealed that the hydroxide and oxide phases have no any change during the Al-water reaction indicating that they are just as catalysts to assist the reaction of Al with water. A possible mechanism was proposed which shows that hydroxide and oxides could dissociate water molecules and promote the hydration of the passive oxide film on Al particle surfaces.

This paper proposes a parameter adjustable dynamic mass and energy balance simulation model for an industrial alkaline water electrolyzer plant that enables cost and energy efficiency optimization by means of system dimensioning and control. Thus the simulation model is based on mathematical models and white box coding and it uses a practicable number of fixed parameters. Zero-dimensional energy and mass balances of each unit operation of a 3 MW and 16 bar plant process were solved in MATLAB functions connected via a Simulink environment. Verification of the model was accomplished using an analogous industrial plant of the same power and pressure range having the same operational systems design. The electrochemical mass flow and thermal behavior of the simulation and the industrial plant were compared to ascertain the accuracy of the model and to enable modification and detailed representation of real case scenarios so that the model is suitable for use in future plant optimization studies. The thermal model dynamically predicted the real case with 98.7 % accuracy. Shunt currents were the main contributor to relative low Faraday efficiency of 86 % at nominal load and steady-state operation and heat loss to ambient from stack was only 2.6 % of the total power loss.

This study presents a computational fluid dynamic (CFD) study of Dimethyl Ether steam reforming (DME-SR) in a large scale Circulating Fluidized Bed (CFB) reactor. The CFD model is based on Eulerian–Eulerian dispersed flow and solved using commercial software (ANSYS FLUENT). The DME-SR reactions scheme and kinetics in the presence of a bifunctional catalyst of CuO/ZnO/Al₂O₃+ZSM-5 were incorporated in the model using in-house developed user-defined function. The model was validated by comparing the predictions with experimental data from the literature. The results revealed for the first time detailed CFB reactor hydrodynamics gas residence time temperature distribution and product gas composition at a selected operating condition of 300 °C and steam to DME mass ratio of 3 (molar ratio of 7.62). The spatial variation in the gas species concentrations suggests the existence of three distinct reaction zones but limited temperature variations. The DME conversion and hydrogen yield were found to be 87% and 59% respectively resulting in a product gas consisting of 72 mol% hydrogen. In part II of this study the model presented here will be used to optimize the reactor design and study the effect of operating conditions on the reactor performance and products.

The present study describes hydrogen generation from N_aBH₄ in the presence of acid accelerator boric oxide or  B₂O₃ using seawater as a reactant. Reaction times and temperatures are adjusted using various delivery methods: bulk addition funnel and metering pump. It is found that the transition metal catalysts typically used to generate hydrogen gas are poisoned by seawater. B₂O₃ is not poisoned by seawater; in fact reaction times are considerably faster in seawater using  B₂O₃. Reaction times and temperatures are compared for pure water and seawater for each delivery method. It is found that using B2O3 with pure water bulk addition is 97% complete in 3 min; pump metering provides a convenient method to extend the time to 27 min a factor of 9 increase above bulk addition. Using  B₂O₃ with seawater as a reactant bulk addition is 97% complete in 1.35 min; pump metering extends the time to 23 min a factor of 17 increase above bulk. A second acid accelerator sodium bisulfate or NaHSO4 is investigated here for use with NaBH4 in seawater. Because it is non-reactive in seawater i.e. no spontaneous H₂ generation NaHSO₄ can be stored as a solution in seawater; because of its large solubility it is ready to be metered into NaBH₄. With N_aHSO₄ in seawater pump metering increases the time to 97% completion from 3.4 min to 21 min. Metering allows the instantaneous flow rate of H₂ and reaction times and temperatures to be tailored to a particular application. In one application the seawater hydrogen generator characterized here is ideal for supplying H₂ gas directly to Proton Exchange Membrane fuel cells in sea surface or subsea environments where a reliable source of power is needed.

Power- and biomass-to-liquid fuel processes (PBtL) can utilize renewable energy and residual forestry waste to produce liquid synthetic fuels which have the potential to mitigate the climate impacts of the current transportation infrastructure including the long-haul aviation sector. In a previous study we demonstrated that implementing a solid oxide electrolysis cell (SOEC) in the PBtL process can significantly increase the energy efficiency of fuel production by supplying the produced hydrogen to a reverse water gas shift (RWGS) reactor to generate syngas which is then fed downstream to a Fischer–Tropsch (FT) reactor. The tail gas emitted from the FT reactor consists primarily of a mixture of hydrogen carbon monoxide and methane and is often recycled to the entrained flow gasifier located at the beginning of the process. In this analysis we investigate the efficiency gains of the PBtL process as a result of redirecting the tail gas of the FT reactor to the anode of an SOEC to serve as fuel. Supplying fuel to an SOEC can lower the electrical work input required to facilitate steam electrolysis when reacting electrochemically with oxide ions in the anode which in turn can reduce oxygen partial pressures and thus alleviate material degradation. Accordingly we develop a thermodynamic framework to reveal the performance limits of fuel-assisted SOECs (FASOECs) and provide strategies to minimize oxygen partial pressures in the SOEC anode. Additionally we elucidate how much fuel is required to match the heating demands of a cell when steam is supplied to the cathode over a broad range of inlet temperatures and demonstrate the influence of a set of reaction pathways of the supplied fuel on the operating potential of an FASOEC and the corresponding efficiency gain of the PBtL process. Based on preliminary calculations we estimate that implementing an FASOEC in the PBtL process can increase the energy efficiency of fuel production to more than 90% depending on the amount of FT tail gas available to the system.