Production & Supply Chain
Simulation Methodology for an Off-grid Solar–battery–water Electrolyzer Plant: Simultaneous Optimization of Component Capacities and System Control
Oct 2021
Publication
The capacity of each component in an off-grid water electrolyzer hydrogen production plant integrated with solar photovoltaics and a battery energy storage system represents a significant factor affecting the viability and reliability of the system. This paper describes a novel method that optimizes simultaneously the component capacities and finite-state machine based control of the system to minimize the cost of green hydrogen production. The components and control in the system are referenced to a proton exchange membrane water electrolyzer stack with a fixed nominal power of 4.5 kW. The end results are thus scalable by changing the nominal power of the electrolyzer. Simulations are carried out based on data collected from a residential solar photovoltaic installation with 300 s time resolution. Optimization of the system is performed with particle swarm optimization algorithm. A sensitivity analysis performed over the prices of the different components reveals that the price of the water electrolyzer has the greatest impact on the green hydrogen production cost. It is found that the price of the battery has to be below 0.3 e/Wh to become a feasible solution as overnight energy storage.
Asymmetric Solvation of the Zinc Dimer Cation Revealed by Infrared Multiple Photon Dissociation Spectroscopy of Zn2+(H2O)n (n = 1–20)
Jun 2021
Publication
Investigating metal-ion solvation—in particular the fundamental binding interactions—enhances the understanding of many processes including hydrogen production via catalysis at metal centers and metal corrosion. Infrared spectra of the hydrated zinc dimer (Zn2+(H2O)n; n = 1–20) were measured in the O–H stretching region using infrared multiple photon dissociation (IRMPD) spectroscopy. These spectra were then compared with those calculated by using density functional theory. For all cluster sizes calculated structures adopting asymmetric solvation to one Zn atom in the dimer were found to lie lower in energy than structures adopting symmetric solvation to both Zn atoms. Combining experiment and theory the spectra show that water molecules preferentially bind to one Zn atom adopting water binding motifs similar to the Zn+(H2O)n complexes studied previously. A lower coordination number of 2 was observed for Zn2+(H2O)3 evident from the highly red-shifted band in the hydrogen bonding region. Photodissociation leading to loss of a neutral Zn atom was observed only for n = 3 attributed to a particularly low calculated Zn binding energy for this cluster size.
Kinetic Parameters Estimation via Dragonfly Algorithm (DA) and Comparison of Cylindrical and Spherical Reactors Performance for CO2 Hydrogenation to Hydrocarbons
Oct 2020
Publication
Climate change and global warming as well as growing global demand for hydrocarbons in industrial sectors make great incentives to investigate the utilization of CO2 for hydrocarbons production. Therefore finding an in-depth understanding of the CO2 hydrogenation reactors along with simulating reactor responses to different operating conditions are of paramount importance. However the reaction mechanisms for CO2 hydrogenation and their corresponding kinetic parameters have been disputable yet. In this regard considering the previously proposed Langmuir-Hinshelwood-Hougen-Watson (LHHW) mechanism which considered CO2 hydrogenation as a combination of reverse water gas shift (RWGS) and Fischer-Tropsch (FT) reactions and using a one-dimensional pseudo-homogeneous non-isothermal model kinetic parameters of the rate expressions are estimated via fitting experimental and modelling data through a novel swarm intelligence optimization technique called dragonfly algorithm (DA). The predicted reactants conversion using DA algorithm are closer to the experimental data (with about 4% error) comparing to those obtained by the artificial bee colony (ABC) algorithm and are in significant agreement with available literature data. The proposed model is used to assess the effect of reactor configuration on the performance and temperature fluctuations. Results show that axial flow spherical reactor (AFSR) and radial flow spherical reactor (RFSR) exhibiting the same surface area with that of the cylindrical reactor (CR) i.e. AFSR-2 and RFSR-2-i are the most efficient exhibiting hydrocarbons selectivity of 40.330% and 40.286% at CO2 conversion of 53.763% and 53.891%. In addition it is revealed that the location of the jacket has an essential role in controlling the reactor temperature.
SNG Generation via Power to Gas Technology: Plant Design and Annual Performance Assessment
Nov 2020
Publication
Power to gas (PtG) is an emerging technology that allows to overcome the issues due to the increasingly widespread use of intermittent renewable energy sources (IRES). Via water electrolysis power surplus on the electric grid is converted into hydrogen or into synthetic natural gas (SNG) that can be directly injected in the natural gas network for long-term energy storage. The core units of the Power to synthetic natural gas (PtSNG) plant are the electrolyzer and the methanation reactors where the renewable electrolytic hydrogen is converted to synthetic natural gas by adding carbon dioxide. A technical issue of the PtSNG plant is the different dynamics of the electrolysis unit and the methanation unit. The use of a hydrogen storage system can help to decouple these two subsystems and to manage the methanation unit for assuring long operation time and reducing the number of shutdowns. The purpose of this paper is to evaluate the energy storage potential and the technical feasibility of the PtSNG concept to store intermittent renewable sources. Therefore different plant sizes (1 3 and 6 MW) have been defined and investigated by varying the ratio between the renewable electric energy sent to the plant and the total electric energy generated by the renewable energy source (RES) facility based on a 12 MW wind farm. The analysis has been carried out by developing a thermochemical and electrochemical model and a dynamic model. The first allows to predict the plant performance in steady state. The second allows to forecast the annual performance and the operation time of the plant by implementing the control strategy of the storage unit. The annual overall efficiencies are in the range of 42–44% low heating value (LHV basis). The plant load factor i.e. the ratio between the annual chemical energy of the produced SNG and the plant capacity results equal to 60.0% 46.5% and 35.4% for 1 3 and 6 MW PtSNG sizes respectively.
Nickel Sulfides Supported by Carbon Spheres as Efficient Catalysts for Hydrogen Evolution Reaction
Jun 2021
Publication
Ni3S2 and NiS supported on carbon spheres are successfully synthesized by a facile hydrothermal method. And then a series of physical characterizations included XRD (X-ray diffraction) EDS (energy dispersive spectroscopy) FESEM (field emission scanning electron microscopy) and XPS (X-ray photo-electron spectroscopy) were used to analyze the samples. XRD was used to confirm that NiNi3S2 S2 and NiS were successfully fabricated. FESEM indicated that Ni3S2 and NiS disperse well on carbon spheres. Electrochemical tests showed that nickel sulfides supported by carbon spheres exhibited excellent hydrogen evolution performance. The excellent catalytic activity is attributed to the synergistic effect of carbon spheres and transition metal sulfides of which the carbon spheres act to enhance the electrical conductivity and the dispersion of Ni3S2 and NiS thus providing more active sites for the hydrogen evolution reaction.
Carbons Formed in Methane Thermal and Thermocatalytic Decomposition Processes: Properties and Applications
Jun 2021
Publication
The hydrogen economy will play a key role in future energy systems. Several thermal and catalytic methods for hydrogen production have been presented. In this review methane thermocatalytic and thermal decomposition into hydrogen gas and solid carbon are considered. These processes known as the thermal decomposition of methane (TDM) and thermocatalytic decomposition (TCD) of methane respectively appear to have the greatest potential for hydrogen production. In particular the focus is on the different types and properties of carbons formed during the decomposition processes. The applications for carbons are also investigated.
The ‘Green’ Ni-UGSO Catalyst for Hydrogen Production under Various Reforming Regimes
Jun 2021
Publication
A new spinelized Ni catalyst (Ni-UGSO) using Ni(NO3)2·6H2O as the Ni precursor was prepared according to a less material intensive protocol. The support of this catalyst is a negative-value mining residue UpGraded Slag Oxide (UGSO) produced from a TiO2 slag production unit. Applied to dry reforming of methane (DRM) at atmospheric pressure T = 810 °C space velocity of 3400 mL/(h·g) and molar CO2/CH4 = 1.2 Ni-UGSO gives a stable over 168 h time-on-stream methane conversion of 92%. In this DRM reaction optimization study: (1) the best performance is obtained with the 10–13 wt% Ni load; (2) the Ni-UGSO catalysts obtained from two different batches of UGSO demonstrated equivalent performances despite their slight differences in composition; (3) the sulfur-poisoning resistance study shows that at up to 5.5 ppm no Ni-UGSO deactivation is observed. In steam reforming of methane (SRM) Ni-UGSO was tested at 900 °C and a molar ratio of H2O/CH4 = 1.7. In this experimental range CH4 conversion rapidly reached 98% and remained stable over 168 h time-on-stream (TOS). The same stability is observed for H2 and CO yields at around 92% and 91% respectively while H2/CO was close to 3. In mixed (dry and steam) methane reforming using a ratio of H2O/CH4 = 0.15 and CO2/CH4 = 0.97 for 74 h and three reaction temperature levels (828 °C 847 °C and 896 °C) CH4 conversion remains stable; 80% at 828 °C (26 h) 85% at 847 °C (24 h) and 95% at 896 °C (24 h). All gaseous streams have been analyzed by gas chromatography. Both fresh and used catalysts are analyzed by scanning electron microscopy-electron dispersive X-ray spectroscopy (SEM-EDXS) X-ray diffraction (XRD) and thermogravimetric analysis (TGA) coupled with mass spectroscopy (MS) and BET Specific surface. In the reducing environment of reforming such catalytic activity is mainly attributed to (a) alloys such as FeNi FeNi3 and Fe3Ni2 (reduction of NiFe2O4 FeNiAlO4) and (b) to the solid solution NiO-MgO. The latter is characterized by a molecular distribution of the catalytically active Ni phase while offering an environment that prevents C deposition due to its alkalinity.
In Situ Irradiated X-Ray Photoelectron Spectroscopy on Ag-WS2 Heterostructure For Hydrogen Production Enhancement
Oct 2020
Publication
The hot electron transition of noble materials to catalysis accelerated by localized surface plasmon resonances (LSPRs) was detected by in situ irradiated X-ray photoelectron spectroscopy (ISI-XPS) in this article. This paper synthesized an Ag Nanowire (AgNW) @ WS2 core-shell structure with an ultra-thin shell of WS2(3 ∼ 7 nm) and characterized its photocatalytic properties. The AgNW@WS2 core-shell structure exhibited different surface-enhanced Raman spectroscopy (SERS) effects by changing shell thickness indicating that the effect of AgNW could be controlled by WS2 shell. Furthermore the hydrogen production of AgNW@WS2 could reach to 356% of that of pure WS2. The hot electrons arising from the LSPRs effect broke through the Schottky barrier between WS2 and AgNW and transferred to the WS2 shell whose photocatalytic effect was thus enhanced. In addition when the LSPRs effect was intensified by reducing the shell thickness the hot electron transition of noble materials to catalysis was accelerated.
Shining the Light on Clean Hydrogen
Jun 2021
Publication
Clean hydrogen:
- What's driving the excitement?
- Will hydrogen stay on the main stage of the energy transition?
- What is the market for clean hydrogen today?
Enhanced Performance and Durability of Low Catalyst Loading PEM Water Electrolyser Based on a Short-side Chain Perfluorosulfonic Ionomer
Sep 2016
Publication
Water electrolysis supplied by renewable energy is the foremost technology for producing ‘‘green” hydrogen for fuel cell vehicles. In addition the ability to rapidly follow an intermittent load makes electrolysis an ideal solution for grid-balancing caused by differences in supply and demand for energy generation and consumption. Membrane-electrode assemblies (MEAs) designed for polymer electrolyte membrane (PEM) water electrolysis based on a novel short-side chain (SSC) perfluorosulfonic acid (PFSA) membrane Aquivion with various cathode and anode noble metal loadings were investigated in terms of both performance and durability. Utilizing a nanosized Ir0.7Ru0.3O solid solution anode catalyst and a supported Pt/C cathode catalyst in combination with the Aquivion membrane gave excellent electrolysis performances exceeding 3.2 A cm-2 at 1.8 V terminal cell voltage ( 80% efficiency) at 90 ºC in the presence of a total catalyst loading of 1.6 mg cm−2. A very small loss of efficiency corresponding to 30 mV voltage increase was recorded at 3 A cm 2 using a total noble metal catalyst loading of less than 0.5 mg cm−2 (compared to the industry standard of 2 mg cm−2). Steady-state durability tests carried out for 1000 h at 1 A cm -2 showed excellent stability for the MEA with total noble metal catalyst loading of 1.6 mg cm−2 (cell voltage increase 5 lV/h). Moderate degradation rate (cell voltage increase 15 lV/h) was recorded for the low loading 0.5 mg cm-2 MEA. Similar stability characteristics were observed in durability tests at 3 A cm−2. These high performance and stability characteristics were attributed to the enhanced proton conductivity and good stability of the novel membrane the optimized structural properties of the the enhanced proton conductivity and good stability of the novel membrane the optimized structural properties of the the enhanced proton conductivity and good stability of the novel membrane the optimized structural properties of the Ir and Ru oxide solid solution and the enrichment of Ir species on the surface for the anodic catalyst.
Physicochemical Properties of Proton-conducting SmNiO3 Epitaxial Films
Mar 2019
Publication
Proton conducting SmNiO3 (SNO) thin films were grown on (001) LaAlO3 substrates for systematically investigating the proton transport properties. X-ray Diffraction and Atomic Force Microscopy studies reveal that the as-grown SNO thin films have good single crystallinity and smooth surface morphology. The electrical conductivity measurements in air indicate a peak at 473 K in the temperature dependence of the resistance of the SNO films probably due to oxygen loss on heating. A Metal-Insulator-Transition occurs at 373 K for the films after annealing at 873 K in air. In a hydrogen atmosphere (3% H2/97% N2) an anomalous peak in the resistance is found at 685 K on the first heating cycle. Electrochemical Impedance Spectroscopy studies as a function of temperature indicate that the SNO films have a high ionic conductivity (0.030 S/cm at 773 K) in a hydrogen atmosphere. The activation energy for proton conductivity was determined to be 0.23 eV at 473–773 K and 0.37 eV at 773–973 K respectively. These findings demonstrate that SNO thin films have good proton conductivity and are good candidate electrolytes for low temperature proton-conducting Solid Oxide Fuel Cells.
Microwave Absorption of Aluminum/Hydrogen Treated Titanium Dioxide Nanoparticles
Dec 2018
Publication
Interactions between incident electromagnetic energy and matter are of critical importance for numerous civil and military applications such as photocatalysis solar cells optics radar detection communications information processing and transport et al. Traditional mechanisms for such interactions in the microwave frequency mainly rely on dipole rotations and magnetic domain resonance. In this study we present the first report of the microwave absorption of Al/H2 treated TiO2 nanoparticles where the Al/H2 treatment not only induces structural and optical property changes but also largely improves the microwave absorption performance of TiO2 nanoparticles. Moreover the frequency of the microwave absorption can be finely controlled with the treatment temperature and the absorption efficiency can reach optimal values with a careful temperature tuning. A large reflection loss of −58.02 dB has been demonstrated with 3.1 mm TiO2 coating when the treating temperature is 700 °C. The high efficiency of microwave absorption is most likely linked to the disordering-induced property changes in the materials. Along with the increased microwave absorption properties are largely increased visible-light and IR absorptions and enhanced electrical conductivity and reduced skin-depth which is likely related to the interfacial defects within the TiO2 nanoparticles caused by the Al/H2 treatment.
Overview of the Hydrogen Production by Plasma-Driven Solution Electrolysis
Oct 2022
Publication
This paper reviews the progress in applying the plasma-driven solution electrolysis (PDSE) which is also referred to as the contact glow-discharge electrolysis (CGDE) or plasma electrolysis for hydrogen production. The physicochemical processes responsible for the formation of PDSE and effects occurring at the discharge electrode in the cathodic and anodic regimes of the PDSE operation are described. The influence of the PDSE process parameters especially the discharge polarity magnitude of the applied voltage type and concentration of the typical electrolytic solutions (K2CO3 Na2CO3 KOH NaOH H2SO4 ) presence of organic additives (CH3OH C2H5OH CH3COOH) temperature of the electrolytic solution the active length and immersion depth of the discharge electrode into the electrolytic solution on the energy efficiency (%) energy yield (g(H2 )/kWh) and hydrogen production rate (g(H2 )/h) is presented and discussed. This analysis showed that in the cathodic regime of PDSE the hydrogen production rate is 33.3 times higher than that in the anodic regime of PDSE whereas the Faradaic and energy efficiencies are 11 and 12.5 times greater respectively than that in the anodic one. It also revealed the energy yield of hydrogen production in the cathodic regime of PDSE in the methanol–water mixture as the electrolytic solution is 3.9 times greater compared to that of the alkaline electrolysis 4.1 times greater compared to the polymer electrolyte membrane electrolysis 2.8 times greater compared to the solid oxide electrolysis 1.75 times greater than that obtained in the microwave (2.45 GHz) plasma and 5.8% greater compared to natural gas steam reforming.
Hydrogen Production via Steam Reforming: A Critical Analysis of MR and RMM Technologies
Jan 2020
Publication
Hydrogen as the energy carrier of the future’ has been a topic discussed for decades and is today the subject of a new revival especially driven by the investments in renewable electricity and the technological efforts done by high-developed industrial powers such as Northern Europe and Japan. Although hydrogen production from renewable resources is still limited to small scale local solutions and R&D projects; steam reforming (SR) of natural gas at industrial scale is the cheapest and most used technology and generates around 8 kg CO2 per kg H2. This paper is focused on the process optimization and decarbonization of H2 production from fossil fuels to promote more efficient approaches based on membrane separation. In this work two emerging configurations have been compared from the numerical point of view: the membrane reactor (MR) and the reformer and membrane module (RMM) proposed and tested by this research group. The rate of hydrogen production by SR has been calculated according to other literature works a one-dimensional model has been developed for mass heat and momentum balances. For the membrane modules the rate of hydrogen permeation has been estimated according to mass transfer correlation previously reported by this research group and based on previous experimental tests carried on in the first RMM Pilot Plant. The methane conversion carbon dioxide yield temperature and pressure profile are compared for each configuration: SR MR and RMM. By decoupling the reaction and separation section such as in the RMM the overall methane conversion can be increased of about 30% improving the efficiency of the system.
An Overview of Water Electrolysis Technologies for Green Hydrogen Production
Oct 2022
Publication
Decarbonizing the planet is one of the major goals that countries around the world have set for 2050 to mitigate the effects of climate change. To achieve these goals green hydrogen that can be produced from the electrolysis of water is an important key solution to tackle global decarbonization. Consequently in recent years there is an increase in interest towards green hydrogen production through the electrolysis process for large-scale implementation of renewable energy based power plants and other industrial and transportation applications. The main objective of this study was to provide a comprehensive review of various green hydrogen production technologies especially on water electrolysis. In this review various water electrolysis technologies and their techno-commercial prospects including hydrogen production cost along with recent developments in electrode materials and their challenges were summarized. Further some of the most successful results also were described. Moreover this review aims to identify the gaps in water electrolysis research and development towards the techno-commercial perspective. In addition some of the commercial electrolyzer performances and their limitations also were described along with possible solutions for cost-effective hydrogen production Finally we outlined our ideas and possible solutions for driving cost-effective green hydrogen production for commercial applications. This information will provide future research directions and a road map for the development/implementation of commercially viable green hydrogen projects.
Hydrogen Production and Carbon Sequestration by Steam Methane Reforming and Fracking with Carbon Dioxide
Feb 2020
Publication
An opportunity to sequester large amounts of carbon dioxide (CO2) is made possible because hydraulic fracturing is used to produce most of America's natural gas. CO2 could be extracted from natural gas and water using steam methane reforming pressurized to its supercritical phase and used instead of water to fracture additional hydrocarbon-bearing rock. The useful energy carrier that remains is hydrogen with carbon returned to the ground. Research on the use of supercritical CO2 is reviewed with proppant entrainment identified as the major area where technical advances may be needed. The large potential for greenhouse-gas reduction through sequestration of CO2 and avoidance of methane leakage from the natural gas system is quantified.
Performance Study on Methanol Steam Reforming Rib Micro-Reactor with Waste Heat Recovery
Mar 2020
Publication
Automobile exhaust heat recovery is considered to be an effective means to enhance fuel utilization. The catalytic production of hydrogen by methanol steam reforming is an attractive option for onboard mobile applications due to its many advantages. However the reformers of conventional packed bed type suffer from axial temperature gradients and cold spots resulting from severe limitations of mass and heat transfer. These disadvantages limit reformers to a low efficiency of catalyst utilization. A novel rib microreactor was designed for the hydrogen production from methanol steam reforming heated by automobile exhaust and the effect of inlet exhaust and methanol steam on reactor performance was numerically analyzed in detail with computational fluid dynamics. The results showed that the best operating parameters were the counter flow water-to-alcohol (W/A) of 1.3 exhaust inlet velocity of 1.1 m/s and exhaust inlet temperature of 773 K when the inlet velocity and inlet temperature of the reactant were 0.1 m/s and 493 K respectively. At this condition a methanol conversion of 99.4% and thermal efficiency of 28% were achieved together with a hydrogen content of 69.6%.
Analysis of Hydrogen Production Costs in Steam-Methane Reforming Considering Integration with Electrolysis and CO2 Capture
Aug 2022
Publication
Global hydrogen production is dominated by the Steam-Methane Reforming (SMR) route which is associated with significant CO2 emissions and excess process heat. Two paths to lower specific CO2 emissions in SMR hydrogen production are investigated: (1) the integration of CO2 capture and compression for subsequent sequestration or utilization and (2) the integration of electrolysis for increased hydrogen production. In both cases the excess process heat is utilized to drive the emissions reduction options. Four different design regimes for integration of carbon capture and compression with the SMR process are identified. Techno-economic analyses are performed to study the effect of CO2 mitigation on hydrogen production costs compared to grey hydrogen production without emissions mitigation options. Integration with electrolysis is shown to be less attractive compared to the proposed heat and power integration schemes for the SMR process with CO2 capture and compression for subsequent sequestration or utilization which can reduce emissions by 90% with hydrogen production costs increasing only moderately by 13%. This blue hydrogen production is compared in terms of costs and emissions against the emerging alternative production by electrolysis in the context of renewable and fossil electricity generation and electricity mixes while considering life-cycle emissions.
Hydrogen Separation and Purification from Various Gas Mixtures by Means of Electrochemical Membrane Technology in the Temperature Range 100–160 ◦C
Apr 2021
Publication
This paper reports on an experimental evaluation of the hydrogen separation performance in a proton exchange membrane system with Pt-Co/C as the anode electrocatalyst. The recovery of hydrogen from H2/CO2 H2/CH4 and H2/NH3 gas mixtures were determined in the temperature range of 100–160 ◦C. The effects of both the impurity concentration and cell temperature on the separation performance of the cell and membrane were further examined. The electrochemical properties and performance of the cell were determined by means of polarization curves limiting current density open-circuit voltage hydrogen permeability hydrogen selectivity hydrogen purity and cell efficiencies (current voltage and power efficiencies) as performance parameters. High purity hydrogen (>99.9%) was obtained from a low purity feed (20% H2 ) after hydrogen was separated from H2/CH4 mixtures. Hydrogen purities of 98–99.5% and 96–99.5% were achieved for 10% and 50% CO2 in the feed respectively. Moreover the use of proton exchange membranes for electrochemical hydrogen separation was unsuccessful in separating hydrogen-rich streams containing NH3 ; the membrane underwent irreversible damage.
Time-phased Geospatial Siting Analysis for Renewable Hydrogen Production Facilities under a Billion-kilogram-scale Build-out using California as an Example
Jun 2022
Publication
For renewable hydrogen to be a significant part of the future decarbonized energy and transportation sectors a rapid and massive build-out of hydrogen production facilities will be needed. This paper describes a geospatial modeling approach to identifying the optimal locations for renewable hydrogen fuel production throughout the state of California based on least-cost generation and transport. This is accomplished by (1) estimating and projecting California renewable hydrogen demand scenarios through the year 2050 (2) identifying feedstock locations (3) excluding areas not suitable for development and (4) selecting optimal site locations using commercial geospatial modeling software. The findings indicate that there is a need for hundreds of new renewable hydrogen production facilities in the decades preceding the year 2050. In selecting sites for development feedstock availability by technology type is the driving factor."
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