Research on the design of hydrogen supply system of 70 MPa hydrogen storage cylinder for vehicles

A hydrogen supply system of 70 MPa hydrogen storage cylinder on vehicles is designed, in which a compressor is proposed to use the new type of ion compressor. The system is simulated statically by Aspen Plus. Meanwhile, during the process of hydrogen charged from the third-stage high-pressure hydrogen storage tank to the hydrogen storage cylinder on vehicles, the dynamic variety of the third-stage high-pressure hydrogen storage tank is simulated dynamically by Aspen HYSYS Through the simulation, obtaining the results that there are difference between theoretical calculation and simulation for the volume of third-stage high-pressure hydrogen storage tank and the average volume flow of hydrogen in a third-stage high-pressure hydrogen storage tank varies with its pressure and volume. By comparing the results of Aspen Plus simulation and Aspen HYSYS simulation, there are some differences. The designed system can be applied to hydrogen stations and any operating conditions involving the supply hydrogen.     

Thermodynamic development and design of a concentrating solar thermochemical water-splitting process for co-production of hydrogen and electricity

A concentrating solar plant is proposed for a thermochemical water-splitting process with excess heat used for electricity generation in an organic Rankine cycle. The quasi-steady state thermodynamic model consisting of 23 components and 45 states uses adjustable design parameters to optimize hydrogen production and system efficiency. The plant design and associated thermodynamic model demonstrate that cerium oxide is suitable for thermochemical water-splitting cycles involving the co-production of hydrogen and electricity. Design point analyses at 900 W/m² DNI indicate that a single tower with solar radiation input of 27.74 MW and an aperture area of 9.424 m² yields 10.96 MW total output comprised of 5.55 MW hydrogen (Gibbs free energy) and 5.41 MW net electricity after subtracting off 22.0% of total power generation for auxiliary loads. Pure hydrogen output amounts to 522 tonne/year at 20.73 GWh/year (HHV) or 17.20 GWh/year (Gibbs free energy) with net electricity generation at 14.52 GWh/year using TMY3 data from Daggett, California, USA. Annual average system efficiency is 38.2% with the constituent hydrogen fraction and electrical fraction being 54.2% and 45.8%, respectively. Sensitivity analyses illustrate that increases in particle loop recuperator effectiveness create an increase in hydrogen production and a decrease in electricity generation. Further, recuperator effectiveness has a measurable effect on hydrogen production, but has limited impact on total system efficiency given that 81.1% of excess heat is recuperated within the system for electricity generation.     

Preparation of Ru–Cs catalyst and its application on hydrogen production by ammonia decomposition

Ammonia can be a hydrogen source for many applications including fuel cells. Using Ru or Cs–Ru as the catalyst, hydrogen is generated from ammonia by decomposition reaction. These catalysts are deposited on carbon powder by either chemical reduction or precipitation method in this study. Different carbon powder pre-treatment solutions and catalyst deposition conditions are evaluated. Nitric acid pre-treatment followed by precipitation at pH of 6 produces the highest catalyst loading from solution with given concentration of catalyst precursor. Hydrogen generation rate is measured at different catalyst compositions, ammonia inlet flow rates, decomposition temperatures, amount of catalyst packing, and ratio of Cs/Ru. The optimal condition for the ammonia decomposition reaction is Cs/Ru weight ratio at 3, ammonia inlet flow at 6 ml min⁻¹, reaction temperature at 400 °C. At this condition, the ammonia conversion rate reaches 90% and hydrogen generation rate reaches 29.8 mmol/min-g_cat.     

Energy,exergy, economic and environmental (4E) analysis of using city gate station (CGS) heater waste for power and hydrogen production: A comparative study

This paper deals with energy, exergy, economic, and environmental (4E) analysis of two new combined systems for simultaneous power and hydrogen production. The combined systems are integrated from a city gate station (CGS) system, a Rankine cycle (RC), an absorption power cycle (APC), and a proton exchange membrane (PEM) electrolyzer. Since the pressure of natural gas (NG) in transmission pipeline is high, this pressure is reduced at CGS to a lower pressure. However, this NG has also ample potential to be recovered for multiple productions, too. In the proposed systems, the outlet energy of NG is used for power and hydrogen production by employing RC/APC and PEM electrolyzer. The power sub-cycles are driven by waste heat of CGS, while PEM electrolyzer is driven by this waste heat along with a portion of CGS-Turbine output power. A comprehensive thermodynamic modeling and parametric study of the proposed combined systems are conducted from the 4E analysis viewpoint. The results of two proposed systems are compared with each other, considering a fixed value of 1 MW for RC- and APC-Turbines power. Under the same external conditions and using steam as working fluid of RC, the thermal efficiency of the combined CGS/PEM-RC and -APC systems are obtained 32.9% and 33.6%, respectively. The overall exergy efficiency of the combined CGS/PEM-RC and -APC systems are also calculated by 47.9% and 48.9%, respectively. Moreover, the total sum unit cost of product (SUCP) and CO₂ emission penalty cost rate are obtained 36.9 $/GJ and 0.033 $/yr for the combined CGS/PEM-RC and 36 $/GJ and 0.211 $/yr for the combined CGS/PEM-APC systems, respectively. The results of exergy analysis also revealed that the vapor generator (in both systems) has the main contribution in the overall exergy destruction.     

Energy and exergy analyses of a solar driven Mg–Cl hybrid thermochemical cycle for co-production of power and hydrogen

Analysis and performance assessment of a solar driven hydrogen production plant running on an Mg–Cl cycle, are conducted through energy and exergy methods. The proposed system consists of (a) a concentrating solar power cycle with thermal energy storage, (b) a steam power plant with reheating and regeneration, and (c) a hybrid thermochemical Mg–Cl hydrogen production cycle. The results show that higher steam to magnesium molar ratios are required for full yield of reactants at the hydrolysis step. This ratio even increases at low temperatures, although lowering the highest temperatures appears to be more favorable for linking such a cycle to lower temperature energy sources. Reducing the maximum cycle temperature decreases the plant energy and exergy efficiencies and may cause some undesirable reactions and effects. The overall system energy and exergy efficiencies are found to be 18.8% and 19.9%, respectively, by considering a solar heat input. These efficiencies are improved to 26.9% and 40.7% when the heat absorbed by the molten salt is considered and used as a main energy input to the system. The highest exergy destruction rate occurs in the solar field which accounts for 79% of total exergy destruction of the integrated system.     

Porous medium based burner for efficient and clean combustion of ammonia–hydrogen–air systems

Due to its high hydrogen density and extensive experience base, ammonia (NH₃) has been gaining special attention as a potential green energy carrier. This study focuses on premixed ammonia–hydrogen–air flames under standard temperature and pressure conditions using an inert silicon-carbide (SiC) porous block as a practical and effective medium for flame stabilization. Combustion experiments conducted using a lab scale burner resulted in stable combustion and high combustion efficiencies at very high ammonia concentration levels over a wide range of equivalence ratios. Noticeable power output densities have also been achieved. Preliminary results of NO_x emission measurements indicate NO_x concentrations as low as 35 ppm under rich conditions. The remarkable capability of this specific burner to operate efficiently and cleanly at high ammonia concentration levels, which can easily be achieved by partial cracking of NH₃, is believed to be a key accomplishment in the development of ammonia fired power generation systems.     

A synthetical evaluation of developing low-carbonized coal-fired power technologies in China

This study is attempted to analyze the integrated effects of low-carbonized developments for Chinese coal-fired power industry in two cases by extending a hybrid energy-economic model. The first case is energy efficiency improvement without CCS introduction. The second case is direct carbon removal with CCS technology, while coal controlling policy scenario is set as a baseline for comparison. Here oxy-fuel combustion has been selected as the only carbon capture technology due to its great potential in commercialization. Then the ecological co-benefits, environmental benefits, macroeconomic impacts and water saving effects of CO₂ abatement from Chinese coal-fired power industry are analyzed. Simulation results show that energy saving and coal controlling policy can create huge ecological, environmental and water saving benefits. However, coal controlling policy also will cause great macroeconomic losses. But due to extra energy consumption, the large-scale commercialization of oxy-fuel CCS technology if without CO₂ reuse will cause certain decrease of GDP growth rate and increase water consumption in China. Only when combined with resource usage of the captured CO₂, oxy-fuel CCS introduction in China can have some practical application value.     

Electrochemical growth of MoSx on Cu foam: A highly active and robust three-dimensional cathode for hydrogen evolution

In this paper, we report a highly active and robust three-dimensional (3D) Cu foam@MoS_x electrode for electrocatalytic hydrogen evolution reaction (HER) prepared by a simple and controllable electrochemical deposition method. Highly conductive Cu foam scaffold with exposed 3D frameworks can not only ensure an intimate interface for facilitate a fast electron transfer but also render the deposited amorphous MoS_x with abundant exposed active sites and large contact area for electrolyte diffusion. As a result, the optimized Cu foam@MoS_x electrode exhibits high activity for electrocatalytic H₂ evolution in 0.5 M H₂SO₄, the required overpotentials to reach current densities of 10 and 100 mA cm^?2 are 200 and 250 mV, respectively. Moreover, the Cu foam@MoS_x electrode shows no obvious deactivation after 2000 potential cycling and also retains its outstanding electrocatalytic activity after 10 h bulk electrolysis for H₂ evolution due to the robust adhesion of MoS_x. This work provides a new strategy to the development of highly active HER electrocatalyst by integrating high-surface-area and conductive substrate and the favorable surface structures of active components.     

A first principles study of hydrogen storage in lithium decorated defective phosphorene

In this study, we studied defect-engineering and lithium decoration of 2D phosphorene for effective hydrogen storage using density functional theory. Contrary to graphene, it is found that the presence of point-defects is not preferable for anchoring of H₂ molecules over defective phosphorene. According to previous research, strategies such as defect engineering, metal decoration, and doping enhance the hydrogen storage capacity of several 2D materials. Our DFT simulations show that point defects in phosphorene do not improve the hydrogen storage capacity compared to pristine phosphorene. However, selective lithium decoration over the defective site significantly improves the hydrogen adsorption capacity yielding a binding energy of as high as ?0.48 eV/H₂ in Li-decorated single vacancy phosphorene. Differential charge densities and projected density of states have been computed to understand the interactions and charge transfer among the constituent atoms. Strong polarization of the H₂ molecule is evidenced by the charge accumulation and depletion. The PDOS shows that the presence of Li leads to enhanced charge transfer. The maximum gravimetric density was investigated by sequentially adding H₂ molecules to the Li-decorated single vacancy defective phosphorene. The Li-decorated single vacancy phosphorene is found to possess a gravimetric density of around 5.3% for hydrogen storage.     

Duct-vented hydrogen–air deflagrations: The effect of duct length and hydrogen concentration

Experiments on duct-vented explosions of hydrogen–air mixtures in a 12.3 l cylindrical vessel were conducted, and the effects of duct length and hydrogen concentration on the maximum overpressure and flame behavior within and outside the vented enclosure were investigated. The results show that the maximum overpressure in the vessel first increased and then was maintained nearly unchanged with the length of a relief duct increasing to 2 m. For a given duct length, the maximum overpressure first increased and then decreased when hydrogen concentration increased from 20% to 55%. The burn-up in the duct caused the gas mixtures to move in reverse from the duct to vessel, which consequently decreased the venting efficiency. A pressure wave caused by burn-up in the duct was observed, which resulted in a pressure peak in the external pressure–time histories after it traveled outside the duct. The maximum external overpressure first increased and then decreased with an increase in duct length. For a given duct length, the maximum external overpressure increased with an increase in hydrogen concentration.     

Zero-dimensional single zone engine modeling of an SI engine fuelled with methane and methane-hydrogen blend using single and double Wiebe Function: A comparative study

Combustion modeling plays a key role in an engine simulation to predict in-cylinder pressure development and engine performance with a high level accuracy. Wiebe function, representing mass fraction burned (MFB) as a function of crank angle position, is widely used to predict the combustion process. The work presents a predictive zero-dimensional (Zero-D) single zone engine modeling of an SI engine fuelled with methane and methane-hydrogen blend. In this work, the single and double forms of Wiebe function were used to estimate the combustion process in the modeling. For this purpose, the single and double-Wiebe functions' parameters were calculated using the least squares method by fitting to the MFB curves calculated from experimental pressure data. These Wiebe functions were, then, introduced to the Zero-D single zone engine model developed for the methane and methane-hydrogen blend fueled SI engine to obtain in-cylinder pressure development and gross indicated mean effective pressure (GIMEP) for the engine performance prediction. The results show that the model with double-Wiebe Function fit better than that with single-Wiebe function. In addition, the fitted double-Wiebe function has a significant improvement in the GIMEP prediction for methane-hydrogen blend fueled SI engine modeling rather than the methane-fueled modeling.     

A solid oxide fuel cell operating on liquid organic hydrogen carrier-based hydrogen – A kinetic model of the hydrogen release unit and system performance

In this paper, a kinetic model for the catalytic dehydrogenation of perhydro dibenzyltoluene (H18-DBT), a well-established Liquid Organic Hydrogen Carrier (LOHC) compound, is presented. Kinetic parameters for hydrogen release at a Pt on alumina catalyst in a temperature range between 260 °C and 310 °C are presented. A Solid Oxide Fuel Cell (SOFC) system model was coupled to the hydrogen release from H18-DBT in order to validate the full sequence of LOHC-bound hydrogen-to-electric power. A system layout is described and investigated according to its transient operating behavior and its efficiency. We demonstrate that the maximum efficiency of LOHC-bound hydrogen-to-electricity is 45% at full load, avoiding any critical conditions for the system components.     

Effects of ammonia substitution on combustion stability limits and NOx emissions of premixed hydrogen–air flames

The combustion stability limits and nitrogen oxide (NO_x) emissions of burner-stabilized premixed flames of ammonia (NH₃)-substituted hydrogen (H₂)–air mixtures at normal temperature and pressure are studied to evaluate the potential of partial NH₃ substitution to improve the safety of H₂ use. The effects of NH₃ substitution, nitrogen (N₂) coflow and mixture injection velocity on the stability limits and NO_x emissions of NH₃–H₂–air flames are experimentally determined. Results show a reduction of stability limits with NH₃ substitution and coflow, supporting the potential of NH₃ as a carbon-free, green additive in H₂–air flames and indicating a different tendency from that for no coflow condition. The NO_x emission index is almost constant even with enhanced NH₃ substitution, though the absolute value of NO_x emissions increases in general. At fuel-rich conditions, the NO_x emission index decreases with increasing mixture injection velocity and the existence of coflow. The thermal deNO_x process in the post-flame region is involved in reducing NO_x emissions for the fuel-rich flames.     

Numerical investigation of a high pressure hydrogen jet of 82 MPa with adaptive mesh refinement: Concentration and velocity distributions

To investigate the safety properties of high-pressure hydrogen discharge or leakage, an under-expanded hydrogen jet flow with a storage pressure of 82 MPa from a small jet orifice with a diameter of 0.2 mm is studied by three-dimensional (3D) numerical calculations. The full 3D compressible Navier-Stokes equations are utilized in a domain with a size of about 3 × 3 × 6 m which is discretized by employing an adaptive mesh refinement (AMR) technology to reduce the number of grid cells. By AMR, the local mesh resolutions can narrowly cover the Taylor microscale $l_T$ and direct numerical simulations (DNS) are performed. Both the instantaneous and mean hydrogen concentration distributions in the present jet are discussed. The instantaneous concentrations of hydrogen $C_{{\text{H}}_2}$ on the axis presents significant turbulent pulsating oscillations. The centerline value of the intensity of concentration fluctuation ${\stackrel{?}{\sigma }}_{{\text{H}}_2}$ asymptotically comes to 0.23, which is in a good agreement with the existing experimental results. It substantiates the conclusion that the asymptotic centerline value of ${\stackrel{?}{\sigma }}_{{\text{H}}_2}$ is independent of jet density ratio. The probability distributions function (PDF) of instantaneous axial $C_{{\text{H}}_2}$ agree approximately with the Gaussian distribution while skewing a little to the higher range. The time averaged hydrogen concentration ${\overline{C}}_{{\text{H}}_2}$ along the radial directions can also be described as a Gaussian distribution. The axial ${\overline{C}}_{{\text{H}}_2}$ of 82 MPa hydrogen jet tends to obey the distribution discipline approximated with ${\overline{C}}_{{\text{H}}_2}=4200/(z/\theta )$ where z is the axial distance from the nozzle and $\theta$ is the effective ejection diameter, which is consistent with the experimental results. In addition, the hydrogen tip penetration $Z_{\text{tip}}$ is found to be in a linear relationship with the square root of jet flow time $\sqrt{t}$. Meanwhile, the jet's velocity half-width $L_{\text{Vh}}$ approximately gains an linear relation with z which can be expressed as $L_{\text{Vh}}=0.09z$.     

Feed compositions and gasification potential of several biomasses including a microalgae: A thermodynamic modeling approach

This study presents the relation of the biomass properties with the gasification performance. The potential of microalgae (N. oculta) for gasification also has been investigated. Other biomasses such as palm frond, mangrove, and rice husk were considered as the benchmarks. The performance of a combined gasification process for different biomass was evaluated by developing a thermodynamic model using Aspen Plus. The performance of gasification process was evaluated based on the composition of the producer gas, the cold gas efficiency, and the gasification system efficiency. The effects of biomass composition on the gasification performance was studied by varying the gasification temperature, the oxygen equivalence ratio, and the steam to carbon ratio. It was found that the H/O ratio in the feed biomass has a considerable effect on the H₂/CO ratio of producer gas on the gasification without gasifying agent. The gasification of algae with oxygen exhibited the highest H₂/CO ratio. The highest cold gas efficiency was found during gasification of algae with oxygen, while the highest cold gas efficiency from gasification with steam was exhibited on gasification of palm frond. The highest gasification system efficiency was obtained for palm frond using the oxygen or steam as the gasifying agent.     

Multiphase Nb–TiCo alloys: The significant impact of surface corrosion on the structural stability and hydrogen permeation behaviour

Multiphase Nb_xTi_(100-x)/2Co_(100-x)/2 (x = 30–60) alloys are a promising material for hydrogen separating membranes. These alloy membranes exhibit a rapid decline in hydrogen permeation flux within ∼12 h when operated at 773 K. To address this issue, a dense oxide (e.g. Nb₂O₅, TiO₂ and CoO) layer was prepared between a Pd coating layer and an Nb–TiCo substrate by surface corrosion for improving their thermal stability, and the corrosion resistance of Nb–TiCo alloys was investigated. An increase in the Nb content (x) lowers the corrosion resistance of these alloys, but makes it easier to form the above oxide layer. Substantial enhancement of hydrogen permeability and thermal stability at 773 K was observed for the alloys (x = 30 and 40) after corrosion, which can be ascribed to an increase in hydrogen diffusivity. This improved permeability and stability are closely related to the formation of the above surface oxide layer that impeded interdiffusion between the Pd film and Nb–TiCo substrates. This study demonstrates that insertion of a diffusion barrier between the Pd and Nb-based substrates by surface corrosion is a viable approach to enhance the high-temperature stability of Pd-coated Nb–TiCo alloys, an aspect not widely explored in Nb-based hydrogen separation and purification membranes.     

Anaerobic digestion of maize and cellulose under thermophilic and mesophilic conditions – A comparative study

The aim of this study was to advance in understanding of digestion process of energy crops. Cellulose and maize silage were fermented in batch mode at mesophilic (38 °C) and thermophilic (55 °C) conditions and corresponding organic loads of 5.5 ± 0.2 kgVS/m³, 11.2 ± 0.3 kgVS/m³ and 16.7 ± 0.4 kgVS/m³.For both substrates more stable and faster digestion took place at 38 °C. Due to complex structure maize degradation was characterized by varying digestion rate and longer total digestion time resulting form breakdown of hard-degradable fractions. The digestion retard at increased OLRs of cellulose and lower degradation level obtained for all cellulose series confirm a higher overloading potential for systems dealing with single-component-substrates but also the enhanced sensitivity of such systems to any inconvenient digestion conditions.Based on observed patterns of volatile fatty acids and oxidation-reduction potential, different fermentation mechanisms can be concluded for cellulose and maize, but also for different temperature modes. Conversion of maize at highly reductive conditions with increased concentrations of butyric acid was accompanied by much higher activity of hydrogenotrophic methanogens than for cellulose digestion.Two factors showed a strong potential to influence test results: an insufficient VS content of inoculum, which caused reduced biogas yields, and a high natural biodiversity of maize silage, resulting in higher biogas yields than calculated based on the maize composition.     

Enhancement of hydrogen production in a modified moving bed downdraft gasifier – A thermodynamic study by including tar

A new approach on thermodynamic simulation of the gasification process is conducted by considering the formation of tar using Aspen Plus. The present model shows higher accuracy as compared to the conventional model in term of the composition of producer gas. The tar from pyrolysis process is successfully reduced with high reaction temperature in the combustion zone. A parametric study is performed by varying the split ratio of gasifying agents (steam/oxygen) through three different zones: (i) combustion zone, (ii) counter-current reduction zone, and/or (iii) co-current reduction zone. Introduction of the gasifying agents through the counter-current reduction zone has positive effects on the gasification performances in term of hydrogen concentration, cold gas efficiency, and gasification system efficiency. The effects of O₂ equivalence ratio and steam to carbon ratio (S/C) on the performance of gasification are also investigated. The gasification with oxygen provided the highest cold gas efficiency. A remarkable hydrogen production is achieved from gasification with both oxygen and steam.     

A comparative study on the performance of mesoporous SBA-15 supported Pd–Zn catalysts in partial oxidation and steam reforming of methanol for hydrogen production

Using mesoporous SBA-15 (Santa Barbara Amorphous No. 15, a mesoporous material) as support, Pd–Zn nanocatalysts with varying Pd and Zn content were tested for hydrogen production from methanol by partial oxidation and steam reforming reactions. The physico-chemical characteristics of the synthesized SBA-15 support were confirmed by XRD, N₂ adsorption, SEM and TEM analyses. The PdZn alloy formation during the reduction of Pd–Zn/SBA-15 was revealed by XRD and DRIFT study of adsorbed CO. Also, the correlation between Pd and Zn loadings and PdZn alloy formation was studied by XRD and TPR analyses. The metallic Pd surface area and total uptakes of CO and H₂ were measured by chemisorption at 35 °C. The metallic Pd surface area values are in linear proportion with the Pd loading. The formation of PdZn alloy during high temperature reduction was confirmed by a shift in absorption frequency of CO on Pd sites to lower frequency due to higher electron density at metal particles resulted from back-donation. The reduced Pd–Zn/SBA-15 catalysts were tested for partial oxidation of methanol at different temperatures and found that catalyst with 4.5 wt% Pd and 6.75 wt% Zn on SBA-15 showed better H₂ selectivity with suppressed CO formation due to the enhanced Pd dispersion as well as larger Pd metallic surface area. The O₂/CH₃OH ratio is found to play a significant role in CH₃OH conversion and H₂ selectivity. The performance of 4.5 wt% Pd–6.75 wt% Zn/SBA-15 catalyst in steam reforming of methanol was also tested. Comparatively, the H₂ selectivity is significantly higher than that in partial oxidation, even though the CH₃OH conversion is less. Finally, the long term stability of the catalyst was tested and the nature of PdZn alloy after the reactions was found to be stable as revealed from the XRD pattern of the spent catalysts.     

Laminar-burning velocities of hydrogen–air and hydrogen–methane–air mixtures: An experimental study

The laminar burning velocities of hydrogen–air and hydrogen–methane–air mixtures are very important in designing and predicting the progress of combustion and performance of combustion systems where hydrogen is used as fuel. In this work, laminar flame velocities of hydrogen–air and different composition of hydrogen–methane–air mixtures (from 100% hydrogen to 100% methane) have been measured at ambient temperatures for variable equivalence ratios (ER=0.8–3.2$\mathrm{ER}=0.8–3.2$). A modified test rig has been developed from the former Cardiff University ‘Cloud Chamber’ for this experimental study. The rig comprises of a 250 mm length cylindrical stainless steel explosion bomb enclosed at one end with a stainless steel plug which houses an internal stirrer to allow mixing. The other end is sealed with a 120 mm diameter round quartz window. Optical access for filming flame propagation is afforded via two diametrically opposed quartz windows in both sides. Flame speeds are determined within the bomb using a high-speed Schlieren photographic technique. This method is an accurate way to determine the flame–speed and the burning velocities were then derived using a CHEMKIN computer model to provide the expansion ratio. The design of the test facility ensures the flame is laminar which results in a spherical flame which is not affected by buoyancy. The experimental study demonstrated that increasing the hydrogen percentage in the hydrogen–methane mixture brought about an increase in the resultant burning velocity and caused a widening of the flammability limits. This experiments also suggest that a hydrogen–methane mixture (i.e. 30% hydrogen+70% methane) could be a competitive alternative fuel for existing combustion plants.