Production & Supply Chain
Energy-efficient Conversion of Microalgae to Hydrogen and Power
Jun 2017
Publication
An integrated system for H2 production from microalgae and its storage is proposed employing enhanced process integration technology (EPI). EPI consists of two core technologies i.e. exergy recovery and process integration. The proposed system includes a supercritical water gasification H2 separation hydrogenation and combined cycle. Microalga Chlorella vulgaris is used as a material for evaluation. The produced syngas is separated to produce highly pure H2. Furthermore to store the produced H2 liquid organic H2 carrier of toluene-and-methylcyclohexane cycle is adopted. The remaining gas is used as fuel for combustion in combined cycle to generate electricity. The effects of fluidization velocity and gasification pressure to energy efficiency are evaluated. From process modelling and calculation it is shown that high total energy efficiency about 60% can be achieved. In addition about 40% of electricity generation efficiency can be realized.
Methodology for the Development of Hybrid Renewable Energy Systems (HRES) with Pumped Storage and Hydrogen Production on Lemnos Island
Apr 2022
Publication
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.
Aqueous Phase Reforming in a Microchannel Reactor: The Effect of Mass Transfer on Hydrogen Selectivity
Aug 2013
Publication
Aqueous phase reforming of sorbitol was carried out in a 1.7 m long 320 mm ID microchannel reactor with a 5 mm Pt-based washcoated catalyst layer combined with nitrogen stripping. The performance of this microchannel reactor is correlated to the mass transfer properties reaction kinetics hydrogen selectivity and product distribution. Mass transfer does not affect the rate of sorbitol consumption which is limited by the kinetics of the reforming reaction. Mass transfer significantly affects the hydrogen selectivity and the product distribution. The rapid consumption of hydrogen in side reactions at the catalyst surface is prevented by a fast mass transfer of hydrogen from the catalyst site to the gas phase in the microchannel reactor. This results in a decrease of the concentration of hydrogen at the catalyst surface which was found to enhance the desired reforming reaction rate at the expense of the undesired hydrogen consuming reactions. Compared to a fixed bed reactor the selectivity to hydrogen in the microchannel reactor was increased by a factor of 2. The yield of side products (mainly C3 and heavier hydrodeoxygenated species) was suppressed while the yield of hydrogen was increased from 1.4 to 4 moles per mole of sorbitol fed.
Recent Advancements in Chemical Looping Water Splitting for the Production of Hydrogen
Oct 2016
Publication
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.
Hydrolysis-Based Hydrogen Generation Investigation of Aluminium System Adding Low-Melting Metals
Mar 2021
Publication
In this age of human civilization there is a need for more efficient cleaner and renewable energy as opposed to that provided by nonrenewable sources such as coal and oil. In this sense hydrogen energy has been proven to be a better choice. In this paper a portable graphite crucible metal smelting furnace was used to prepare ten multi-element aluminum alloy ingots with different components. The microstructure and phase composition of the ingots and reaction products were analyzed by X-ray diffraction (XRD) scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). The reaction was carried out in a constant temperature water bath furnace at 60°C and the hydrogen production performance of the multi-element aluminum alloys in different proportions was compared by the drainage gas collection method. The experimental results show that the as-cast microstructure of Al–Ga–In–Sn aluminum alloy is composed of a solid solution of Al and part of Ga and a second phase of In3Sn. After the hydrolysis reaction the products were dried at 150°C and then analyzed by XRD. The products were mainly composed of AlOOH and In3Sn. Alloys with different compositions react at the same hydrolysis temperature and the hydrogen production performance is related to the ratio of low-melting-point metal elements. By comparing two different ratios of Ga–In–Sn (GIS) the hydrogen production capacity and production rate when the ratio is 6:3:1 are generally higher than those when the ratio is 7:2:1. The second phase content affects the hydrogen production performance.
Hydrocarbon Production by Continuous Hydrodeoxygenation of Liquid Phase Pyrolysis Oil with Biogenous Hydrogen Rich Synthesis Gas
Feb 2019
Publication
This paper presents a beneficial combination of biomass gasification and pyrolysis oil hydrodeoxygenation for advanced biofuel production. Hydrogen for hydrodeoxygenation (HDO) of liquid phase pyrolysis oil (LPP oil) was generated by gasification of softwood. The process merges dual fluidized bed (DFB) steam gasification which produces a hydrogen rich product gas and the HDO of LPP oil. Synthesis gas was used directly without further cleaning and upgrading by making use of the water gas-shift (WGS) reaction. The water needed for the water gas-shift reaction was provided by LPP oil. HDO was successfully performed in a lab scale over 36 h time on stream (TOS). Competing reactions like the Boudouard reaction and Sabatier reaction were not observed. Product quality was close to Diesel fuel specification according to EN 590 with a carbon content of 85.4 w% and a residual water content of 0.28 w%. The water-gas shift reaction was confirmed by CO/CO2-balance high water consumption and 28% less hydrogen consumption during HDO.
Modelling and Optimization of a Flexible Hydrogen-fueled Pressurized PEMFC Power Plant for Grid Balancing Purposes
Feb 2021
Publication
In a scenario characterized by an increasing penetration of non-dispatchable renewable energy sources and the need of fast-ramping grid-balancing power plants the EU project GRASSHOPPER aims to setup and demonstrate a highly flexible PEMFC Power Plant hydrogen fueled and scalable to MW-size designed to provide grid support.<br/>In this work different layouts proposed for the innovative MW-scale plant are simulated to optimize design and off-design operation. The simulation model details the main BoP components performances and includes a customized PEMFC model validated through dedicated experiments.<br/>The system may operate at atmospheric or mild pressurized conditions: pressurization to 0.7 barg allows significantly higher net system efficiency despite the increasing BoP consumptions. The additional energy recovery from the cathode exhaust with an expander gives higher net power and net efficiency adding up to 2%pt and reaching values between 47%LHV and 55%LHV for currents between 100% and 20% of the nominal value.
Enhanced Production of Hydrogen from Methanol Using Spark Discharge Generated in a Small Portable Reactor
Nov 2021
Publication
An efficient production of hydrogen from a mixture of methanol and water is possible in a spark discharge. In this discharge there is a synergistic effect of high-energy electrons and high temperature interactions which enables an efficient course of endothermic processes such as the production of hydrogen from methanol. The water to methanol molar ratio of 1:1 was kept constant during the study. While the discharge power and feed flow rate were varied from 15 to 55 W and from 0.25 to 2 mol/h respectively which corresponded to the residence time of the reactants in the plasma zone from 58 to 7 ms. The cooled gas mixture contained 56 to 60% of H2. Other gaseous products of the process were CO CO2 and a small amount of CH4. The maximum energy yield was 16.2 mol(H2)/kWh which represents 20% of the theoretical energy yield when the substrates are in a liquid phase.
Anchoring of Turbulent Premixed Hydrogen/Air Flames at Externally Heated Walls
Oct 2020
Publication
A joint experimental and numerical investigation of turbulent flame anchoring at externally heated walls is presented. The phenomenon has primarily been studied for laminar flames and micro-combustion while this study focuses on large-scale applications and elevated Reynolds number flows. Therefore a novel burner design is developed and examined for a diverse set of operating conditions. Hydroxyl radical chemiluminescence measurements are employed to validate the numerical method. The numerical investigation evaluates the performance of various hydrogen/air kinetics Reynolds-averaged turbulence models and the eddy dissipation concept (EDC) as a turbulence-chemistry interaction model. Simulation results show minor differences between detailed chemical mechanisms but pronounced deviations for a reduced kinetic. The baseline k-ω turbulence model is assessed to most accurately predict flame front position and shape. Universal applicability of EDC modelling constants is contradicted. Conclusively the flame anchoring concept is considered a promising approach for pilot flames in continuous combustion devices.
Compact Heat Integrated Reactor System of Steam Reformer, Shift Reactor and Combustor for Hydrogen Production from Ethanol
Jun 2020
Publication
A compact heat integrated reactor system (CHIRS) of a steam reformer a water gas shift reactor and a combustor were designed for stationary hydrogen production from ethanol. Different reactor integration concepts were firstly studied using Aspen Plus. The sequential steam reformer and shift reactor (SRSR) was considered as a conventional system. The efficiency of the SRSR could be improved by more than 12% by splitting water addition to the shift reactor (SRSR-WS). Two compact heat integrated reactor systems (CHIRS) were proposed and simulated by using COMSOL Multiphysics software. Although the overall efficiency of the CHIRS was quite a bit lower than the SRSR-WS the compact systems were properly designed for portable use. CHIRS (I) design combining the reactors in a radial direction was large in reactor volume and provided poor temperature control. As a result the ethanol steam reforming and water gas shift reactions were suppressed leading to lower hydrogen selectivity. On the other hand CHIRS (II) design combining the process in a vertical direction provided better temperature control. The reactions performed efficiently resulting in higher hydrogen selectivity. Therefore the high performance CHIRS (II) design is recommended as a suitable stationary system for hydrogen production from ethanol.
Dynamic Energy and Mass Balance Model for an Industrial Alkaline Water Electrolyzer Plant Process
Nov 2021
Publication
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.
Analysis of Wind to Hydrogen Production and Carbon Capture Utilisation and Storage Systems for Novel Production of Chemical Energy Carriers
Apr 2022
Publication
As the offshore energy landscape transitions to renewable energy useful decommissioned or abandoned oil and gas infrastructure can be repurposed in the context of the circular economy. Oil and gas platforms for example offer opportunity for hydrogen (H2) production by desalination and electrolysis of sea water using offshore wind power. However as H2 storage and transport may prove challenging this study proposes to react this H2 with the carbon dioxide (CO2) stored in depleted reservoirs. Thus producing a more transportable energy carriers like methane or methanol in the reservoir. This paper presents a novel thermodynamic analysis of the Goldeneye reservoir in the North Sea in Aspen Plus. For Goldeneye which can store 30 Mt of CO2 at full capacity if connected to a 4.45 GW wind farm it has the potential to produce 2.10 Mt of methane annually and abate 4.51 Mt of CO2 from wind energy in the grid.
Effects of CO2 sequestration on lipid and biomass productivity in microalgal biomass production
Mar 2017
Publication
The study is focused on the technology and manipulation of production strategies for the cultivation of biomass from four strains of microalgae. Species of microalgae studied are: Chlorella vulgaris Dunaliella Scenedesmus quadricauda and Synechococcus spp. The effects of the rate and amount of CO2 removal from the atmosphere and sequestration with dissolved oxygen on lipid production from accumulated biomass were studied. Also the rate of sequestration of both total and dissolved carbon was investigated. Daily measurements of total organic and inorganic carbon sequestrated optical densities proximate analysis and kinetic parameters of the growing and cultivated microalga were monitored and carried out during the two phases of cultivation: dark and light phases. The values of maximum rate of carbon (IV) oxide removed rmax varied from 11.73 mg L -1 min -1 to 18.84 mg L -1 min -1 from Chlorella vulgaris to Synechoccocus spp. Important parameters such as biomass productivity maximum pH values obtained at cultivation lipid content of the produced biomass and the hydraulic detection time for all four strains of microalgae were considered and presented in comparison and with their individual and collective effects. The ratios of the rate of CO2 absorption constant and the constant for the CO2 desorption rate (k1/k2) occurred highest in Dunaliella suggesting that with a high uptake of CO2 the algal strain is more effective in CO2 CO2 sequestration. The best biomass producer in this study was the C. vulgaris (Xmax = 5400 mg L-1 and Px = 35.1 mg L h -1) where biomass productivity is Px and the maximum cellular concentration is Xmax. C. vulgaris has the highest lipids productivity of 27% while Synechoccocus has the least (11.72%). In general biomass productivity may be inversely related; this fact may be explained by greater metabolic involvement of lipid biosynthesis. This pioneer study may be advanced further to developing models for strategic manipulation and optimisation approach in micro algal biomass cultivation.
High-stability, High-capacity Oxygen Carriers: Iron Oxide-perovskite Composite Materials for Hydrogen Production by Chemical Looping
Jun 2015
Publication
Iron oxide has been widely used as an oxygen carrier material (OCM) for hydrogen production by chemical looping due to its favourable thermodynamic properties. In spite of this iron oxide loses much of its activity after redox cycling mainly due to sintering and agglomeration. Perovskites such as La0.7Sr0.3FeO3-d (LSF731) have been suggested as potential candidate OCMs for hydrogen production due to their excellent oxygen transport properties and stability under cycling. However hydrogen production per cycle for a similar carrier weight is lower than with iron oxide. This work proposes the use of composite OCMs made of iron oxide clusters embedded in an LSF731 matrix. The perovskite matrix facilitates oxygen transport to the iron oxide clusters while preventing agglomeration. Two preparation methods mechanical mixing and a modified Pechini method were used to obtain composite materials with different iron oxide weight fractions 11 and 30 wt.%. The reactivity of these OCMs was studied in a thermogravimetric analyser. Hydrogen production and carrier stability were investigated in a microreactor over 25 redox cycles while periodically feeding carbon monoxide and water in order to produce carbon dioxide and hydrogen in separate streams. Hydrogen production was stable over 25 cycles for LSF731 and the composite OCM with 30 wt.% iron oxide produced by the modified Pechini method but iron oxide particles alone underwent a decrease in the hydrogen production with cycling. The hydrogen production during the 25th cycle was eight times higher for the composite material than for iron oxide alone and four times higher than for LSF731. The hydrogen production was therefore also higher than that expected from a simple combination of the iron oxide and LSF731 alone indicating a synergetic effect whereby the LSF731 may have a higher effective oxygen capacity when in the form of the composite material.
Exchange Current Density of Reversible Solid Oxide Cell Electrodes
Mar 2022
Publication
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.
Electrocatalyst Derived from NiCu–MOF Arrays on Graphene Oxide Modified Carbon Cloth for Water Splitting
Apr 2022
Publication
Electrocatalysts are capable of transforming water into hydrogen oxygen and therefore into energy in an environmentally friendly and sustainable manner. However the limitations in the research of high performance catalysts act as an obstructer in the development of using water as green energy. Here we report on a delicate method to prepare novel bimetallic metal organic framework derived electrocatalysts (C–NiCu–BDC–GO–CC) using graphene oxide (GO) modified carbon cloth as a 3D flexible and conductive substrate. The resultant electrocatalyst C–NiCu–BDC– GO–CC exhibited very low electron transfer resistance which benefited from its extremely thin 3D sponge-like morphology. Furthermore it showed excellent oxygen evolution reaction (OER) activity achieving 10 mA/cm2 at a low overpotential of 390 mV in 1 M KOH electrolyte with a remarkable durability of 10 h.
Theoretical Insights into the Hydrogen Evolution Reaction on the Ni3N Electrocatalyst
Jun 2021
Publication
Ni-based catalysts are attractive alternatives to noble metal electrocatalysts for the hydrogen evolution reaction (HER). Herein we present a dispersion-corrected density functional theory (DFT-D3) insight into HER activity on the (111) (110) (001) and (100) surfaces of metallic nickel nitride (Ni3N). A combination of water and hydrogen adsorption was used to model the electrode interactions within the water splitting cell. Surface energies were used to characterise the stabilities of the Ni3N surfaces along with adsorption energies to determine preferable sites for adsorbate interactions. The surface stability order was found to be (111) < (100) < (001) < (110) with calculated surface energies of 2.10 2.27 2.37 and 2.38 Jm−2 respectively. Water adsorption was found to be exothermic at all surfaces and most favourable on the (111) surface with Eads = −0.79 eV followed closely by the (100) (110) and (001) surfaces at −0.66 −0.65 and −0.56 eV respectively. The water splitting reaction was investigated at each surface to determine the rate determining Volmer step and the activation energies (Ea) for alkaline HER which has thus far not been studied in detail for Ni3N. The Ea values for water splitting on the Ni3N surfaces were predicted in the order (001) < (111) < (110) < (100) which were 0.17 0.73 1.11 and 1.60 eV respectively overall showing the (001) surface to be most active for the Volmer step of water dissociation. Active hydrogen adsorption sites are also presented for acidic HER evaluated through the ΔGH descriptor. The (110) surface was shown to have an extremely active Ni–N bridging site with ΔGH = −0.05 eV.
Dynamic modelling of a direct internal reforming solid oxide fuel cell stack based on single cell experiments
May 2018
Publication
Direct internal reforming enables optimal heat integration and reduced complexity in solid oxide fuel cell (SOFC) systems but thermal stresses induced by the increased temperature gradients may inflict damage to the stack. Therefore the development of adequate control strategies requires models that can accurately predict the temperature profiles in the stack. A 1D dynamic modelling platform is developed in this study and used to simulate SOFCs in both single cell and stack configurations. The single cell model is used to validate power law and Hougen-Watson reforming kinetics derived from experiments in previous work. The stack model based on the same type of cells accounts for heat transfer in the inactive area and to the environment and is validated with data reported by the manufacturer. The reforming kinetics are then implemented in the stack model to simulate operation with direct internal reforming. Although there are differences between the temperature profiles predicted by the two kinetic models both are more realistic than assuming chemical equilibrium. The results highlight the need to identify rate limiting steps for the reforming and hydrogen oxidation reactions on anodes of functional SOFC assemblies. The modelling approach can be used to study off-design conditions transient operation and system integration as well as to develop adequate energy management and control strategies.
Recent Progress and Approaches on Transition Metal Chalcogenides for Hydrogen Production
Dec 2021
Publication
Development of efficient and affordable photocatalysts is of great significance for energy production and environmental sustainability. Transition metal chalcogenides (TMCs) with particle sizes in the 1–100 nm have been used for various applications such as photocatalysis photovoltaic and energy storage due to their quantum confinement effect optoelectronic behavior and their stability. In particular TMCs and their heterostructures have great potential as an emerging inexpensive and sustainable alternative to metal-based catalysts for hydrogen evolution. Herein the methods used for the fabrication of TMCs characterization techniques employed and the different methods of solar hydrogen production by using different TMCs as photocatalyst are reviewed. This review provides a summary of TMC photocatalysts for hydrogen production.
Electrochemical and Mechanical Stability of Catalyst Layers in Anion Exchange Membrane Water Electrolysis
Dec 2021
Publication
Anion exchange membrane (AEM) water electrolysis is considered a promising solution to future cost reduction of electrochemically produced hydrogen. We present an AEM water electrolyzer with CuCoOx as the anode catalyst and Aemion as membrane and electrode binder. Full cell experiments in pure water and 0.1 M KOH revealed that the optimum binder content depended on the type of electrolyte employed. Online dissolution measurements suggested that Aemion alone was not sufficient to establish an alkaline environment for thermodynamically stabilizing the synthesized CuCoOx in a neutral electrolyte feed. A feed of base is thus indispensable to ensure the thermodynamic stability of such non-noble catalyst materials. Particle loss and delamination of the catalyst layer during MEA operation could be reduced by employing a heat treatment step after electrode fabrication. This work summarizes possible degradation pathways for low-cost anodes in AEMWE and mitigation strategies for enhanced system durability and performance.
Challenges and Important Considerations When Benchmarking Single-cell Alkaline Electrolyzers
Nov 2021
Publication
This study outlines an approach to identifying the difficulties associated with the bench-marking of alkaline single cells under real electrolyzer conditions. A challenging task in the testing and comparison of different catalysts is obtaining reliable and meaningful benchmarks for these conditions. Negative effects on reproducibility were observed due to the reduction in conditioning time. On the anode side a stable passivation layer of NiO can be formed by annealing of the Ni foams which is even stable during long-term operation. Electrical contact resistance and impedance measurements showed that most of the contact resistance derived from the annealed Ni foam. Additionally analysis of various overvoltages indicated that most of the total overvoltage comes from the anode and cathode activation overpotential. Different morphologies of the substrate material exhibited an influence on the performance of the alkaline single cell based on an increase in the ohmic resistance.
State of the Art of Hydrogen Production via Pyrolysis of Natural Gas
Jul 2020
Publication
Fossil fuels have to be substituted by climate neutral fuels to contribute to CO2 reduction in the future energy system. Pyrolysis of natural gas is a well-known technical process applied for production of e. g. carbon black.
In the future it might contribute to carbon dioxide-free hydrogen production. Production of hydrogen from natural gas pyrolysis has thus gained interest in research and energy technology in the near past. If the carbon by-product of this process can be used for material production or can be sequestrated the produced hydrogen has a low carbon footprint.
This article reviews literature on the state of the art of methane/ natural gas pyrolysis process developments and at-tempts to assess the technology readiness level (TRL).
In the future it might contribute to carbon dioxide-free hydrogen production. Production of hydrogen from natural gas pyrolysis has thus gained interest in research and energy technology in the near past. If the carbon by-product of this process can be used for material production or can be sequestrated the produced hydrogen has a low carbon footprint.
This article reviews literature on the state of the art of methane/ natural gas pyrolysis process developments and at-tempts to assess the technology readiness level (TRL).
Advances and Challenges of MOF Derived Carbon-based Electrocatalysts and Photocatalyst for Water Splitting: A Review
Apr 2022
Publication
Environmental pollution and energy shortage are substantial fears to the modern world's long-term sustainability. Water splitting is an essential technique for eco - friendly and sustainable energy storage as well as a pollution-free method to produce hydrogen. In this regards Metal–organic frameworks have emerged as the most competent multifunctional materials in recent times due to its large surface areas adjustable permeability easy compositional alteration and capability for usage as precursors with a wide range of morphological forms. Further MOF-derived carbon-based nanomaterials also offer significant benefits in terms of tunable morphological features and hierarchical permeability as well as ease of functionalization making them extremely effective as catalysts or catalysts supports for a wide variety of important reactions. Recent developments in carbon-based MOFs as catalysts for overall water splitting are discussed in this review. We explore how MOFs and carbon-based MOFs might well be beneficial as well as which methods should be explored for future development. We divided our review into two sections: photocatalytic and electrocatalytic water splitting and we gathered published literature on carbon-based MOFs materials for their outstanding activity offers helpful methods for catalysts design and analysis as well as difficulties This study highlights the developments in MOF derived materials as photo and electro catalysts by explaining respective approaches for their use in overall water splitting.
Batteries and Hydrogen Technology: Keys for a Clean Energy Future
May 2020
Publication
As governments focus on dealing with the Covid-19 health emergency they are increasingly turning their attention to the impact of shutting down their economies and how to revive them quickly through stimulus measures. Economic recovery packages offer a unique opportunity to create jobs while supporting clean energy transitions around the world.
Energy efficiency and renewable energy like wind and solar PV – the cornerstones of any clean energy transition – are good places to start. Those industries employ millions of people across their value chains and offer environmentally sustainable ways to create jobs and help revitalise the global economy.
But more than just renewables and efficiency will be required to put the world on track to meet climate goals and other sustainability objectives. IEA analysis has repeatedly shown that a broad portfolio of clean energy technologies will be needed to decarbonise all parts of the economy. Batteries and hydrogen-producing electrolysers stand out as two important technologies thanks to their ability to convert electricity into chemical energy and vice versa. This is why they also deserve a place in any economic stimulus packages being discussed today.
Link to Document on IEA Website
Energy efficiency and renewable energy like wind and solar PV – the cornerstones of any clean energy transition – are good places to start. Those industries employ millions of people across their value chains and offer environmentally sustainable ways to create jobs and help revitalise the global economy.
But more than just renewables and efficiency will be required to put the world on track to meet climate goals and other sustainability objectives. IEA analysis has repeatedly shown that a broad portfolio of clean energy technologies will be needed to decarbonise all parts of the economy. Batteries and hydrogen-producing electrolysers stand out as two important technologies thanks to their ability to convert electricity into chemical energy and vice versa. This is why they also deserve a place in any economic stimulus packages being discussed today.
Link to Document on IEA Website
Biomass Potential for Producing Power via Green Hydrogen
Dec 2021
Publication
Hydrogen (H2 ) has become an important energy vector for mitigating the effects of climate change since it can be obtained from renewable sources and can be fed to fuel cells for producing power. Bioethanol can become a green H2 source via Ethanol Steam Reforming (ESR) but several variables influence the power production in the fuel cell. Herein we explored and optimized the main variables that affect this power production. The process includes biomass fermentation bioethanol purification H2 production via ESR syngas cleaning by a CO-removal reactor and power production in a high temperature proton exchange membrane fuel cell (HT-PEMFC). Among the explored variables the steam-to-ethanol molar ratio (S/E) employed in the ESR has the strongest influence on power production process efficiency and energy consumption. This effect is followed by other variables such as the inlet ethanol concentration and the ESR temperature. Although the CO-removal reactor did not show a significant effect on power production it is key to increase the voltage on the fuel cell and consequently the power production. Optimization was carried out by the response surface methodology (RSM) and showed a maximum power of 0.07 kWh kg−1 of bioethanol with an efficiency of 17% when ESR temperature is 700 ◦C. These values can be reached from different bioethanol sources as the S/E and CO-removal temperature are changed accordingly with the inlet ethanol concentration. Because there is a linear correlation between S/E and ethanol concentration it is possible to select a proper S/E and CO-removal temperature to maximize the power generation in the HT-PEMFC via ESR. This study serves as a starting point to diversify the sources for producing H2 and moving towards a H2 -economy.
Numerical Analysis of VPSA Technology Retrofitted to Steam Reforming Hydrogen Plants to Capture CO2 and Produce Blue H2
Feb 2022
Publication
The increasing demand for energy and commodities has led to escalating greenhouse gas emissions the chief of which is represented by carbon dioxide (CO2). Blue hydrogen (H2) a lowcarbon hydrogen produced from natural gas with carbon capture technologies applied has been suggested as a possible alternative to fossil fuels in processes with hard-to-abate emission sources including refining chemical petrochemical and transport sectors. Due to the recent international directives aimed to combat climate change even existing hydrogen plants should be retrofitted with carbon capture units. To optimize the process economics of such retrofit it has been proposed to remove CO2 from the pressure swing adsorption (PSA) tail gas to exploit the relatively high CO2 concentration. This study aimed to design and numerically investigate a vacuum pressure swing adsorption (VPSA) process capable of capturing CO2 from the PSA tail gas of an industrial steam methane reforming (SMR)-based hydrogen plant using NaX zeolite adsorbent. The effect of operating conditions such as purge-to-feed ratio and desorption pressure were evaluated in relation to CO2 purity CO2 recovery bed productivity and specific energy consumption. We found that conventional cycle configurations namely a 2-bed 4-step Skarstrom cycle and a 2-bed 6-step modified Skarstrom cycle with pressure equalization were able to concentrate CO2 to a purity greater than 95% with a CO2 recovery of around 77% and 90% respectively. Therefore the latter configuration could serve as an efficient process to decarbonize existing hydrogen plants and produce blue H2.
Combined Hydrogen Production and Electricity Storage using a Vanadium Manganese Redox Dual-flow Battery
Aug 2021
Publication
A redox dual-flow battery is distinct from a traditional redox flow battery (RFB) in that the former includes a secondary energy platform in which the pre-charged electrolytes can be discharged in external catalytic reactors through decoupled redox-mediated hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). The concept offers several advantages over conventional electrolysis in terms of safety durability modularity and purity. In this work we demonstrate a vanadium-manganese redox-flow battery in which Mn3+/Mn2+ and V3+/V2+ respectively mediate the OER and the HER in Mo2C-based and RuO2-based catalysts. The flow battery demonstrates an average energy efficiency of 68% at a current density of 50 mA ⋅ cm−2 (cell voltage = 1.92 V) and a relative energy density 45% higher than the conventional all-vanadium RFB. Both electrolytes are spontaneously discharged through redox-mediated HER and OER with a faradic efficiency close to 100%.
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.
Potential and Economic Analysis of Solar-to-Hydrogen Production in the Sultanate of Oman
Aug 2021
Publication
Hydrogen production using renewable power is becoming an essential pillar for future sustainable energy sector development worldwide. The Sultanate of Oman is presently integrating renewable power generations with a large share of solar photovoltaic (PV) systems. The possibility of using the solar potential of the Sultanate can increase energy security and contribute to the development of the sustainable energy sector not only for the country but also for the international community. This study presents the hydrogen production potential using solar resources available in the Sultanate. About 15 locations throughout the Sultanate are considered to assess the hydrogen production opportunity using a solar PV system. A rank of merit order of the locations for producing hydrogen is identified. It reveals that Thumrait and Marmul are the most suitable locations whereas Sur is the least qualified. This study also assesses the economic feasibility of hydrogen production which shows that the levelized cost of hydrogen (LCOH) in the most suitable site Thumrait is 6.31 USD/kg. The LCOH in the least convenient location Sur is 7.32 USD/kg. Finally a sensitivity analysis is performed to reveal the most significant influential factor affecting the future’s green hydrogen production cost. The findings indicate that green hydrogen production using solar power in the Sultanate is promising and the LCOH is consistent with other studies worldwide.
Production of Hydrogen and Methane from Lignocellulose Waste by Fermentation. A Review of Chemical Pretreatment for Enhancing the Efficiency of the Digestion Process
May 2020
Publication
In Poland lignocellulose wastes constitute about 43% of municipal waste (∼4 417 Gg). Anaerobic and/or dark fermentation are sustainable methods of lignocellulosic waste-management and contribute greatly to ever increasing demand for energy and products. This paper presents the results of the theoretical potential of methane and hydrogen yields from lignocellulosic wastes. Also state-of-the-art methods in the field of lignocellulose fermentation as well as its development and pretreatment are discussed. The main reason for applying pretreatment is the decomposition (decrystallization) of cellulose and hemicellulose and cleavage of polymers into monomers which may be more easily digested by bacteria in DF and AD fermentation processes. At current price levels the cheapest methods are basic and acidic pretreatments. Acidic pretreatment is very efficient (especially using sulfuric acids) solubilizing up to 80% of lignocellulose but strong acids produce inhibitors and are highly corrosive. Alkaline pretreatment is a competitive and even more efficient (>80%) method to acidic pretreatment especially for some rigid materials that acid cannot solubilize. Oxidative pretreatment is usually expensive but can support the sacharisation process by either alkaline or acidic methods; in the case of NMMO efficiency reaching 82%. Ion-liquid pretreatment is selective (almost 100% sacharisation) but very costly and is too expensive for hydrogen production. The last methods can be profitable if some valuable by-products results. An efficient chemical pretreatment should be preceded by physical comminution e.g. mechanical which is the cheapest one.
A Fundamental Viewpoint on the Hydrogen Spillover Phenomenon of Electrocatalytic Hydrogen Evolution
Jun 2021
Publication
Hydrogen spillover phenomenon of metal-supported electrocatalysts can significantly impact their activity in hydrogen evolution reaction (HER). However design of active electrocatalysts faces grand challenges due to the insufficient understandings on how to overcome this thermodynamically and kinetically adverse process. Here we theoretically profile that the interfacial charge accumulation induces by the large work function difference between metal and support (∆Φ) and sequentially strong interfacial proton adsorption construct a high energy barrier for hydrogen transfer. Theoretical simulations and control experiments rationalize that small ∆Φ induces interfacial charge dilution and relocation thereby weakening interfacial proton adsorption and enabling efficient hydrogen spillover for HER. Experimentally a series of Pt alloys-CoP catalysts with tailorable ∆Φ show a strong ∆Φ-dependent HER activity in which PtIr/CoP with the smallest ∆Φ = 0.02 eV delivers the best HER performance. These findings have conclusively identified ∆Φ as the criterion in guiding the design of hydrogen spillover-based binary HER electrocatalysts
Thermodynamic Analysis of the Gasification of Municipal Solid Waste
May 2017
Publication
This work aims to understand the gasification performance of municipal solid waste (MSW) by means of thermodynamic analysis. Thermodynamic analysis is based on the assumption that the gasification reactions take place at the thermodynamic equilibrium condition without regard to the reactor and process characteristics. First model components of MSW including food green wastes paper textiles rubber chlorine-free plastic and polyvinyl chloride were chosen as the feedstock of a steam gasification process with the steam temperature ranging from 973 K to 2273 K and the steam-to-MSW ratio (STMR) ranging from 1 to 5. It was found that the effect of the STMR on the gasification performance was almost the same as that of the steam temperature. All the differences among the seven types of MSW were caused by the variation of their compositions. Next the gasification of actual MSW was analyzed using this thermodynamic equilibrium model. It was possible to count the inorganic components of actual MSW as silicon dioxide or aluminum oxide for the purpose of simplification due to the fact that the inorganic components mainly affected the reactor temperature. A detailed comparison was made of the composition of the gaseous products obtained using steam hydrogen and air gasifying agents to provide basic knowledge regarding the appropriate choice of gasifying agent in MSW treatment upon demand.
Free Stream Behavior of Hydrogen Released from a Fluidic Oscillating Nozzle
May 2021
Publication
The H2 internal combustion engine (ICE) is a key technology for complete decarbonization of the transport sector. To match or exceed the power density of conventional combustion engines H2 direct injection (DI) is essential. Therefore new injector concepts that meet the requirements of a H2 operation have to be developed. The macroscopic free stream behavior of H2 released from an innovative fluidic oscillating nozzle is investigated and compared with that of a conventional multi-hole nozzle. This work consists of H2 flow measurements and injection tests in a constant volume chamber using the Schlieren method and is accompanied by a LES simulation. The results show that an oscillating H2 free stream has a higher penetration velocity than the individual jets of a multi-hole nozzle. This behavior can be used to inject H2 far into the combustion chamber in the vertical direction while the piston is still near bottom dead center. As soon as the oscillation of the H2 free stream starts the spray angle increases and therefore H2 is also distributed in the horizontal direction. In this phase of the injection process spray angles comparable to those of a multi-hole nozzle are achieved. This behavior has a positive effect on H2 homogenization which is desirable for the combustion process.
Production of H2-rich Syngas from Excavated Landfill Waste through Steam Co-gasification with Biochar
Jun 2020
Publication
Gasification of excavated landfill waste is one of the promising options to improve the added-value chain during remediation of problematic old landfill sites. Steam gasification is considered as a favorable route to convert landfill waste into H2-rich syngas. Co-gasification of such a poor quality landfill waste with biochar or biomass would be beneficial to enhance the H2 concentration in the syngas as well as to improve the gasification performance. In this work steam co-gasification of landfill waste with biochar or biomass was carried out in a lab-scale reactor. The effect of the fuel blending ratio was investigated by varying the auxiliary fuel content in the range of 15e35 wt%. Moreover co-gasification tests were carried out at temperatures between 800 and 1000°C. The results indicate that adding either biomass or biochar enhances the H2 yield where the latter accounts for the syngas with the highest H2 concentration. At 800°C the addition of 35 wt% biochar can enhance the H2 concentration from 38 to 54 vol% and lowering the tar yield from 0.050 to 0.014 g/g-fuel-daf. No apparent synergetic effect was observed in the case of biomass co-gasification which might cause by the high Si content of landfill waste. In contrast the H2 production increases non-linearly with the biochar share in the fuel which indicates that a significant synergetic effect occurs during co-gasification due to the reforming of tar over biochar. Increasing the temperature of biochar co-gasification from 800 to 1000°C elevates the H2 concentration but decreases the H2/CO ratio and increases the tar yield. Furthermore the addition of biochar also enhances the gasification efficiency as indicated by increased values of the energy yield ratio.
A Developed Plasmatron Design to Enhance Production of Hydrogen in Synthesis Gas Produced by a Fuel Reformer System
Jan 2022
Publication
Feeding IC engines with hydrogen‐rich syngas as an admixture to hydrocarbon fuels can decrease pollutant emissions particularly NOx. It offers a potential technique for low‐environmen‐ tal impact hydrocarbon fuel use in automotive applications. However hydrogen‐rich reformate gas (syngas) production via fuel reforming still needs more research and optimization. In this paper we describe the effect of a plasma torch assembly design on syngas yield and composition during plasma‐assisted reforming of gasoline. Additionally erosion resistance of the cathode‐emitting ma‐ terial under the conditions of gasoline reforming was studied using hafnium metal and lanthanated tungsten alloy. The gasoline reforming was performed with a noncatalytic nonthermal low‐current plasma system in the conditions of partial oxidation in an air and steam mixture. To find the most efficient plasma torch assembly configuration in terms of hydrogen production yield four types of anode design were tested i.e. two types of the swirl ring and two cathode materials while varying the inlet air and fuel flow rates. The experimental results showed that hydrogen was the highest proportion of the produced syngas. The smooth funnel shape anode design in Ring 1 at air/fuel flow rates of 24/4 27/4.5 and 30/5 g/min respectively was more effective than the edged funnel shape. Lanthanated tungsten alloy displayed higher erosion resistance than hafnium metal.
Properties of the Hydrogen Oxidation Reaction on Pt/C catalysts at Optimised High Mass Transport Conditions and its Relevance to the Anode Reaction in PEFCs and Cathode Reactions in Electrolysers
Jul 2015
Publication
Using a high mass transport floating electrode technique with an ultra-low catalyst loading (0.84–3.5 μgPt cm−2) of commonly used Pt/C catalyst (HiSPEC 9100 Johnson Matthey) features in the hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER) were resolved and defined which have rarely been previously observed. These features include fine structure in the hydrogen adsorption region between 0.18 < V vs. RHE < 0.36 V vs. RHE consisting of two peaks an asymptotic decrease at potentials greater than 0.36 V vs. RHE and a hysteresis above 0.1 V vs. RHE which corresponded to a decrease in the cathodic scan current by up to 50% of the anodic scan. These features are examined as a function of hydrogen and proton concentration anion type and concentration potential scan limit and temperature. We provide an analytical solution to the Heyrovsky–Volmer equation and use it to analyse our results. Using this model we are able to extract catalytic properties (without mass transport corrections; a possible source of error) by simultaneously fitting the model to HOR curves in a variety of conditions including temperature hydrogen partial pressure and anion/H+ concentration. Using our model we are able to rationalise the pH and hydrogen concentration dependence of the hydrogen reaction. This model may be useful in application to fuel cell and electrolyser simulation studies.
Modulating Electronic Structure of Metal-organic Frameworks by Introducing Atomically Dispersed Ru for Efficient Hydrogen Evolution
Mar 2021
Publication
Developing high-performance electrocatalysts toward hydrogen evolution reaction is important for clean and sustainable hydrogen energy yet still challenging. Herein we report a single-atom strategy to construct excellent metal-organic frameworks (MOFs) hydrogen evolution reaction electrocatalyst (NiRu0.13-BDC) by introducing atomically dispersed Ru. Significantly the obtained NiRu0.13-BDC exhibits outstanding hydrogen evolution activity in all pH especially with a low overpotential of 36 mV at a current density of 10 mA cm−2 in 1 M phosphate buffered saline solution which is comparable to commercial Pt/C. X-ray absorption fine structures and the density functional theory calculations reveal that introducing Ru single-atom can modulate electronic structure of metal center in the MOF leading to the optimization of binding strength for H2O and H* and the enhancement of HER performance. This work establishes single-atom strategy as an efficient approach to modulate electronic structure of MOFs for catalyst design.
Development of an Operation Strategy for Hydrogen Production Using Solar PV Energy Based on Fluid Dynamic Aspects
Apr 2017
Publication
Alkaline water electrolysis powered by renewable energy sources is one of the most promising strategies for environmentally friendly hydrogen production. However wind and solar energy sources are highly dependent on weather conditions. As a result power fluctuations affect the electrolyzer and cause several negative effects. Considering these limiting effects which reduce the water electrolysis efficiency a novel operation strategy is proposed in this study. It is based on pumping the electrolyte according to the current density supplied by a solar PV module in order to achieve the suitable fluid dynamics conditions in an electrolysis cell. To this aim a mathematical model including the influence of electrode-membrane distance temperature and electrolyte flow rate has been developed and used as optimization tool. The obtained results confirm the convenience of the selected strategy especially when the electrolyzer is powered by renewable energies.
Decarbonising the UK’s Gas Network - Realising the Green Power-to-hydrogen Opportunity in the East Network
Aug 2020
Publication
Although the UK has done a great job of decarbonising electricity generation to get to net zero we need to tackle harder-to-decarbonise sectors like heat transport and industry. Decarbonised gas – biogases hydrogen and the deployment of carbon capture usage and storage (CCUS) – can make our manufacturing more sustainable minimise disruption to families and deliver negative emissions.
Developing the capability to produce hydrogen at scale is one of the key challenges in the race to meet the UK’s ambitious net zero targets. Using the East Neuk of Fife - with its abundant on- and offshore renewables resource and well-developed electricity and gas networks – as a test bed we investigated the use of surplus electricity generated by renewables to produce green hydrogen which could then be used to heat homes and businesses carbon-free.
Aims
The study focused on answering a number of important questions around bringing power-to-hydrogen to Fife including:
How much low-cost low-carbon electricity would be available to a power-to-hydrogen operator in Fife and how much hydrogen could be produced today and in 2040? How much hydrogen storage would be required to meet demand under three end-use cases: injection into the natural gas grid; use in a dedicated hydrogen grid for heating; and use as transport fuel for a small fleet of vehicles? What if any network upgrades could be avoided by implementing power-to-hydrogen? Which hydrogen end-use markets would be most attractive for a power-to-hydrogen operator? What are the regulatory legislative or market barriers to be overcome to realise large-scale deployment of power-to-hydrogen?
The study
Our expert researchers used a high-level model of the European electricity system and established wholesale prices generation volumes by generation type and constrained generation in Fife. Considering both the present day and a 2040 picture based on National Grid’s Two Degrees Future Energy Scenarios our team explored a number of configurations of power generation and hydrogen end-use to assess the value associated with producing hydrogen.
Alongside this modelling our team conducted a comprehensive review of power-to-hydrogen legislation and regulation and reports and academic papers to identify the current characteristics and direction of the sector observe where most progress had been made and identify lessons learned.
This report and any attachment is freely available on the ENA Smarter Networks Portal here. IGEM Members can download the report and any attachment directly by clicking on the pdf icon above.
Developing the capability to produce hydrogen at scale is one of the key challenges in the race to meet the UK’s ambitious net zero targets. Using the East Neuk of Fife - with its abundant on- and offshore renewables resource and well-developed electricity and gas networks – as a test bed we investigated the use of surplus electricity generated by renewables to produce green hydrogen which could then be used to heat homes and businesses carbon-free.
Aims
The study focused on answering a number of important questions around bringing power-to-hydrogen to Fife including:
How much low-cost low-carbon electricity would be available to a power-to-hydrogen operator in Fife and how much hydrogen could be produced today and in 2040? How much hydrogen storage would be required to meet demand under three end-use cases: injection into the natural gas grid; use in a dedicated hydrogen grid for heating; and use as transport fuel for a small fleet of vehicles? What if any network upgrades could be avoided by implementing power-to-hydrogen? Which hydrogen end-use markets would be most attractive for a power-to-hydrogen operator? What are the regulatory legislative or market barriers to be overcome to realise large-scale deployment of power-to-hydrogen?
The study
Our expert researchers used a high-level model of the European electricity system and established wholesale prices generation volumes by generation type and constrained generation in Fife. Considering both the present day and a 2040 picture based on National Grid’s Two Degrees Future Energy Scenarios our team explored a number of configurations of power generation and hydrogen end-use to assess the value associated with producing hydrogen.
Alongside this modelling our team conducted a comprehensive review of power-to-hydrogen legislation and regulation and reports and academic papers to identify the current characteristics and direction of the sector observe where most progress had been made and identify lessons learned.
This report and any attachment is freely available on the ENA Smarter Networks Portal here. IGEM Members can download the report and any attachment directly by clicking on the pdf icon above.
Overview of Power Electronic Converter Topologies Enabling Large-Scale Hydrogen Production via Water Electrolysis
Feb 2022
Publication
Renewable power-to-hydrogen (P2H) technology is one of the most promising solutions for fulfilling the increasing global demand for hydrogen and to buffer large-scale fluctuating renewable energies. The high-power high-current ac/dc converter plays a crucial role in P2H facilities transforming medium-voltage (MV) ac power to a large dc current to supply hydrogen electrolyzers. This work introduces the general requirements and overviews several power converter topologies for P2H systems. The performances of different topologies are evaluated and compared from multiple perspectives. Moreover the future trend of eliminating the line frequency transformer (LFT) is discussed. This work can provide guidance for future designing and implementing of power-electronics-based P2H systems.
Electrolyzer Modeling and Real-time Control for Optimized Production of Hydrogen Gas
Oct 2020
Publication
We present a method that operates an electrolyzer to meet the demand of a hydrogen refueling station in a cost-effective manner by solving a model-based optimal control problem. To formulate the underlying problem we first conduct an experimental characterization of a Siemens SILYZER 100 polymer electrolyte membrane electrolyzer with 100 kW of rated power. We run experiments to determine the electrolyzer’s conversion efficiency and thermal dynamics as well as the overload-limiting algorithm used in the electrolyzer. The resulting detailed nonlinear models are used to design a real-time optimal controller which is then implemented on the actual system. Each minute the controller solves a deterministic receding-horizon problem which seeks to minimize the cost of satisfying a given hydrogen demand while using a storage tank to take advantage of time-varying electricity prices and photovoltaic inflow. We illustrate in simulation the significant cost reduction achieved by our method compared to others in the literature and then validate our method by demonstrating it in real-time operation on the actual system.
Editorial—Special Issue “Catalysis for Energy Production”
Jun 2021
Publication
The rapid increase in anthropogenic greenhouse gas concentrations in the last several decades means that the effects of climate change are fast becoming the familiar horsemen of a planetary apocalypse. Catalysis one of the pillars of the chemical and petrochemical industries will play a critical role in the effort to reduce the flow of greenhouse gases into the atmosphere. This Special Issue is timely as it provides a collection of high-quality manuscripts in a diverse range of topics which include the production of green hydrogen via water electrolysis the steam reforming of ethanol propane or glycerol the dry reforming of methane and the autothermal reforming of diesel surrogate fuel. The topic of the transformation of biomass waste to chemicals is also well represented as is the tackling of CO2 emissions via novel utilization technologies. The Editors are grateful to all authors for their valuable contributions and confident that this Special Issue will prove valuable to scholars university professors and students alike.
Hydrogen Gas Quality for Gas Network Injection: State of the Art of Three Hydrogen Production Methods
Jun 2021
Publication
The widescale distribution of hydrogen through gas networks is promoted as a viable and cost-efficient option for optimising its application in heat industry and transport. It is a key step towards achieving decarbonisation targets in the UK. A key consideration before the injection of hydrogen into the UK gas networks is an assessment of the difference in hydrogen contaminants presence from different production methods. This information is essential for gas regulation and for further purification requirements. This study investigates the level of ISO 14687 Grade D contaminants in hydrogen from steam methane reforming proton exchange membrane water electrolysis and alkaline electrolysis. Sampling and analysis of hydrogen were carried out by the National Physical Laboratory following ISO 21087 guidance. The results of analysis indicated the presence of nitrogen in hydrogen from electrolysis and water carbon dioxide and particles in all samples analysed. The contaminants were at levels below or at the threshold limits set by ISO 14687 Grade D. This indicates that the investigated production methods are not a source of contaminants for the eventual utilisation of hydrogen in different applications including fuel cell electric vehicles (FCEV’s). The gas network infrastructure will require a similar analysis to determine the likelihood of contamination to hydrogen gas.
The Potential of Hydrogen Hydrate as a Future Hydrogen Storage Medium
Dec 2020
Publication
Hydrogen is recognized as the “future fuel” and the most promising alternative of fossil fuels due to its remarkable properties including exceptionally high energy content per unit mass (142 MJ/kg) low mass density and massive environmental and economical upsides. A wide spectrum of methods in H2 production especially carbon-free approaches H2purification and H2storage have been investigated to bring this energy source closer to the technological deployment. Hydrogen hydrates are among the most intriguing material paradigms for H2storage due to their appealing properties such as low energy consumption for charge and discharge safety cost-effectiveness and favorable environmental features. Here we comprehensively discuss the progress in understanding of hydrogen clathrate hydrates with an emphasis on charging/discharging rate of H2 (i.e. hydrate formation and dissociation rates) and the storage capacity. A thorough understanding on phase equilibrium of the hydrates and its variation through different materials is provided. The path toward ambient temperature and pressure hydrogen batteries with high storage capacity is elucidated. We suggest that the charging rate of H2 in this storage medium and long cyclic performance are more immediate challenges than storage capacity for technological translation of this storage medium. This review and provided outlook establish a groundwork for further innovation on hydrogen hydrate systems for promising future of hydrogen fuel.
Clean Hydrogen Production by Ultrasound (Sonochemistry): The Effect of Noble Gases
Feb 2022
Publication
Power ultrasonic (> 100 kHz) splits water into free radicals and hydrogen. As a result water sonochemistry is considered as an alternative clean and fossil-fuel-free hydrogen production technique. In this research work the impact of rare gases (Xe Ar and He) on the sonochemical production of hydrogen as well as the population of active bubbles has been investigated computationally for various sonicated frequencies (213-515 kHz) and intensities (1-2 W/cm²). It has been found that both the H2 yielding and the bubble population size for H2 yielding are in the order Xe>Ar>He whatever the imposed sonolytic parameters (i.e. frequency and power). These findings were principally ascribed to the thermal conductivity of the saturating gases which is in the reverse order (He>Ar>Xe). Besides the difference between Ar and Xe is condensed in comparison with the He gas. For wave frequencies larger than 213 kHz however all saturating gases (Xe Ar and He) behave identically with the influence of thermal conductivity of these gases on the optimal radius muted. At 213 kHz however this impact is plainly visible (Ropt (Ar and Xe)>Ropt (He)). As per the results obtained helium's inefficiency as a saturating gas for hydrogen production is verified but xenon's maximal efficacy is reached when water is saturated with it. These results support the fewer experimental data reported in this emerging branch of sonochemistry while the discussed results in the present (i.e. noble gases effect on sono-hydrogen production) are treated for the first time consequently our work is considered as a guideline for increasing the efficacy of hydrogen production in a sonochemical reactor.
Advanced Optimal Planning for Microgrid Technologies Including Hydrogen and Mobility at a Real Microgrid Testbed
Apr 2021
Publication
This paper investigates the optimal planning of microgrids including the hydrogen energy system through mixed-integer linear programming model. A real case study is analyzed by extending the only microgrid lab facility in Austria. The case study considers the hydrogen production via electrolysis seasonal storage and fuelling station for meeting the hydrogen fuel demand of fuel cell vehicles busses and trucks. The optimization is performed relative to two different reference cases which satisfy the mobility demand by diesel fuel and utility electricity based hydrogen fuel production respectively. The key results indicate that the low emission hydrogen mobility framework is achieved by high share of renewable energy sources and seasonal hydrogen storage in the microgrid. The investment optimization scenarios provide at least 66% and at most 99% carbon emission savings at increased costs of 30% and 100% respectively relative to the costs of the diesel reference case (current situation)
Sustainable Hydrogen Production by Plasmonic Thermophotocatalysis
Feb 2021
Publication
A vision of hydrogen based economy and clean sustainable fossil fuels-free world inspires the scientific community to put much effort into the development of visible-light-driven photochemistry and efficient solar energy harvesting. The unique features of plasmonic nanomaterials such as capability of significant electric field amplification an extreme local heating generation of high energy charge carriers and broad tunability of optical properties coupled to catalytically active surfaces provide an exciting opportunity for hydrogen production with solar photochemistry. This review sums up recent progress in the development of plasmonic thermophotocatalysis paying particular attention to sustainable production of hydrogen. We approach the subject from a broad bottom-up perspective beginning with the brief description of plasmon-related phenomena and plasmon-assisted photochemistry through the demonstration of various plasmonic nanostructures their synthesis and hydrogen production efficiency ending with the idea of continuous-flow reactors and their future implementation in hydrogen production by plasmonic thermophotocatalysis. Finally we summarize the review and highlight the remaining challenges that have to be faced before the widespread commercialization of this technology.
Methanol Steam Reforming for Hydrogen Generation Via Conventional and Membrane Reactors: A Review
Sep 2013
Publication
Variable renewable energy (VRE) is expected to play a major role in the decarbonization of the electricity sector. However decarbonization via VRE requires a fleet of flexible dispatchable plants with low CO2 emissions to supply clean power during times with limited wind and sunlight. These plants will need to operate at reduced capacity factors with frequent ramps in electricity output posing techno-economic challenges. This study therefore presents an economic assessment of a new near-zero emission power plant designed for this purpose. The gas switching reforming combined cycle (GSR-CC) plant can produce electricity during times of low VRE output and hydrogen during times of high VRE output. This product flexibility allows the plant to operate continuously even when high VRE output makes electricity production uneconomical. Although the CO2 avoidance cost of the GSR-CC plant (€61/ton) was similar to the benchmark post-combustion CO2 capture plant under baseload operation GSR-CC clearly outperformed the benchmark in a more realistic scenario where continued VRE expansion forces power plants into mid-load operation (45% capacity factor). In this scenario GSR-CC promises a 5 %-point higher annualized investment return than the post-combustion benchmark. GSR-CC therefore appears to be a promising concept for a future scenario with high VRE market share and CO2 prices provided that a large market for clean hydrogen is established.
A Tale of Two Phase Diagrams Interplay of Ordering and Hydrogen Uptake in Pd–Au–H
Apr 2021
Publication
Due to their ability to reversibly absorb/desorb hydrogen without hysteresis Pd–Au nanoalloys have been proposed as materials for hydrogen sensing. For sensing it is important that absorption/desorption isotherms are reproducible and stable over time. A few studies have pointed to the influence of short and long range chemical order on these isotherms but many aspects of the impact of chemical order have remained unexplored. Here we use alloy cluster expansions to describe the thermodynamics of hydrogen in Pd–Au in a wide concentration range. We investigate how different chemical orderings corresponding to annealing at different temperatures as well as different external pressures of hydrogen impact the behavior of the material with focus on its hydrogen absorption/desorption isotherms. In particular we find that a long-range ordered L12 phase is expected to form if the H2 pressure is sufficiently high. Furthermore we construct the phase diagram at temperatures from 250 K to 500 K showing that if full equilibrium is reached in the presence of hydrogen phase separation can often be expected to occur in stark contrast to the phase diagram in para-equilibrium. Our results explain the experimental observation that absorption/desorption isotherms in Pd–Au are often stable over time but also reveal pitfalls for when this may not be the case.
Tantalum (Oxy)Nitride: Narrow Bandgap Photocatalysts for Solar Hydrogen Generation
Jul 2017
Publication
Photocatalytic water splitting which directly converts solar energy into hydrogen is one of the most desirable solar-energy-conversion approaches. The ultimate target of photocatalysis is to explore efficient and stable photocatalysts for solar water splitting. Tantalum (oxy)nitride-based materials are a class of the most promising photocatalysts for solar water splitting because of their narrow bandgaps and sufficient band energy potentials for water splitting. Tantalum (oxy)nitride-based photocatalysts have experienced intensive exploration and encouraging progress has been achieved over the past years. However the solar-to-hydrogen (STH) conversion efficiency is still very far from its theoretical value. The question of how to better design these materials in order to further improve their water-splitting capability is of interest and importance. This review summarizes the development of tantalum (oxy)nitride-based photocatalysts for solar water spitting. Special interest is paid to important strategies for improving photocatalytic water-splitting efficiency. This paper also proposes future trends to explore in the research area of tantalum-based narrow bandgap photocatalysts for solar water splitting.
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