Publications
Site-Dependent Environmental Impacts of Industrial Hydrogen Production by Alkaline Water Electrolysis
Jun 2017
Publication
Industrial hydrogen production via alkaline water electrolysis (AEL) is a mature hydrogen production method. One argument in favor of AEL when supplied with renewable energy is its environmental superiority against conventional fossil-based hydrogen production. However today electricity from the national grid is widely utilized for industrial applications of AEL. Also the ban on asbestos membranes led to a change in performance patterns making a detailed assessment necessary. This study presents a comparative Life Cycle Assessment (LCA) using the GaBi software (version 6.115 thinkstep Leinfelden-Echterdingen Germany) revealing inventory data and environmental impacts for industrial hydrogen production by latest AELs (6 MW Zirfon membranes) in three different countries (Austria Germany and Spain) with corresponding grid mixes. The results confirm the dependence of most environmental effects from the operation phase and specifically the site-dependent electricity mix. Construction of system components and the replacement of cell stacks make a minor contribution. At present considering the three countries AEL can be operated in the most environmentally friendly fashion in Austria. Concerning the construction of AEL plants the materials nickel and polytetrafluoroethylene in particular used for cell manufacturing revealed significant contributions to the environmental burden.
Detecting Hydrogen Concentrations During Admixing Hydrogen in Natural Gas Grids
Aug 2021
Publication
The first applications of hydrogen in a natural gas grid will be the admixing of low concentrations in an existing distribution grid. For easy quality and process control it is essential to monitor the hydrogen concentration in real time preferably using cost effective monitoring solutions. In this paper we introduce the use of a platinum based hydrogen sensor that can accurately (at 0.1 vol%) and reversibly monitor the concentration of hydrogen in a carrier gas. This carrier gas that can be nitrogen methane or natural gas has no influence on the accuracy of the hydrogen detection. The hydrogen sensor consists of an interdigitated electrode on a chip coated with a platinum nanocomposite layer that interacts with the gas. This chip can be easily added to a gas sensor for natural gas and biogas that was already developed in previous research. Just by the addition of an extra chip we extended the applicability of the natural gas sensor to hydrogen admixing. The feasibility of the sensor was demonstrated in our own (TNO) laboratory and at a field test location of the HyDeploy program at Keele University in the U.K
Electronic Structure and d-Band Center Control Engineering over Ni-Doped CoP3 Nanowall Arrays for Boosting Hydrogen Production
Jun 2021
Publication
To address the challenge of highly efficient water splitting into H2 successful fabrication of novel porous three-dimensional Ni-doped CoP3 nanowall arrays on carbon cloth was realized resulting in an effective self-supported electrode for the electrocatalytic hydrogen-evolution reaction. The synthesized samples exhibit rough curly and porous structures which are beneficial for gaseous transfer and diffusion during the electrocatalytic process. As expected the obtained Ni-doped CoP3 nanowall arrays with a doping concentration of 7% exhibit the promoted electrocatalytic activity. The achieved overpotentials of 176 mV for the hydrogen-evolution reaction afford a current density of 100 mA cm−2 which indicates that electrocatalytic performance can be dramatically enhanced via Ni doping. The Ni-doped CoP3 electrocatalysts with increasing catalytic activity should have significant potential in the field of water splitting into H2. This study also opens an avenue for further enhancement of electrocatalytic performance through tuning of electronic structure and d-band center by doping.
Assessment of a Fuel Cell Based-hybrid Energy System to Generate and Store Electrical Energy
Jan 2022
Publication
Solid oxide fuel cells (SOFC) have significant applications and performance and their integration into coupled and cascading energy systems can improve the overall performance of the process. Furthermore due to the constant time performance of the fuel cell the problem of fuel starvation may arise by changing the amount of load which can adversely affect the overall performance of the process. In the present study the excess heat of the SOFC is converted into electrical energy in two stages using different heat generators. The coupled energy system in the present article has a new configuration in which the relationship of its components is different from the systems reported in the literature. Furthermore since the use of an energy storage system can improve the overall reliability the energy produced by the coupled energy cycle is stored by a storage technology for peak consumption times. The introduced system can generate approximately 580 W of electrical power with an efficiency of 80%. The highest and lowest share in power generation is related to fuel cell with 82% and thermoelectric generator with 5%. The rest of the system power (i.e. 13%) is produced by thermionic generator. In addition the system requires 0.025 kg per hour of hydrogen fuel. It was also found that to operate the system for 5 h a day requires a storage system with a size of 3.3 m3 . Moreover two key issues to enhance the storage system performance are: adjusting the initial pressure of the system to values close to the peak (optimal) value and using turbines and/or pumps with higher efficiencies. With the aim of supplying 5 kWh of electrical energy five different scenarios based on the design of various effective parameters have been presented.
Interface Instabilities of Growing Hydrides
Jul 2016
Publication
Formation of metal hydrides is a serious complication that occur when hydride forming metals such as zirconium niobium vanadium and magnesium are exposed to long term hydrogen environment. The main concern is that the hydride as being a brittle material has very poor fracture mechanical properties. Formation of hydride is associated with transportation of hydrogen along the gradients of increasing hydrostatic stress which leads to crack tips and other stress concentrators where it forms the hydride. In the present study the thermodynamics of the evolving hydrides is studied. The process is driven by the release of free strain chemical and gradient energies. A phase field model is used to capture the driving forces that the release of the free energy causes. The study gives the conditions that lead to hydride advancement versus retreat and under which conditions the metal-hydride interface becomes unstable and develops a waviness. The spatial frequency spectrum leading to instability is found to depend on the ratio of the elastic strain energy density and parameters related to the interface energy.
Large-scale Stationary Hydrogen Storage via Liquid Organic Hydrogen Carriers
Aug 2021
Publication
Large-scale stationary hydrogen storage is critical if hydrogen is to fulfill its promise as a global energy carrier. While densified storage via compressed gas and liquid hydrogen is currently the dominant approach liquid organic molecules have emerged as a favorable storage medium because of their desirable properties such as low cost and compatibility with existing fuel transport infrastructure. This perspective article analytically investigates hydrogenation systems' technical and economic prospects using liquid organic hydrogen carriers (LOHCs) to store hydrogen at a large scale compared to densified storage technologies and circular hydrogen carriers (mainly ammonia and methanol). Our analysis of major system components indicates that the capital cost for liquid hydrogen storage is more than two times that for the gaseous approach and four times that for the LOHC approach. Ammonia and methanol could be attractive options as hydrogen carriers at a large scale because of their compatibility with existing liquid fuel infrastructure. However their synthesis and decomposition are energy and capital intensive compared to LOHCs. Together with other properties such as safety these factors make LOHCs a possible option for large-scale stationary hydrogen storage. In addition hydrogen transportation via various approaches is briefly discussed. We end our discussions by identifying important directions for future research on LOHCs.
Development of a Pneumatic Actuated Low-pressure Direct Injection Gas Injector for Hydrogen-fueled Internal Combustion Engines
Dec 2022
Publication
Mixture formation is one of the greatest challenges for the development of robust and efficient hydrogen-fueled internal combustion engines. In many reviews and research papers authors pointed out that direct injection (DI) has noteworthy advantages over a port fuel injection (PFI) such as higher power output higher efficiency the possibility of mixture stratification to control NOx-formation and reduce heat losses and above all to mitigate combustion abnormalities such as back-firing and pre-ignitions. When considering pressurized gas tanks for on-vehicle hydrogen storage a low-pressure (LP) injection system is advantageous since the tank capacity can be better exploited accordingly. The low gas density upstream of the injector requires cross-sectional areas far larger than any other injectors for direct injection in today's gasoline or diesel engines. The injector design proposed in this work consists of a flat valve seat to enable the achievement of lifetime requirements in heavy-duty applications. The gas supply pressure is used as the energy source for the actuation of the valve plate by means of a pneumatic actuator. This article describes the design and the performed tests carried out to prove the concept readiness of the new LP-DI-injector.
Advanced Hydrogen Storage of the Mg–Na–Al System: A Review
May 2021
Publication
A solid-state storage system is the most practical option for hydrogen because it is more convenient and safer. Metal hydrides especially MgH2 are the most promising materials that offer high gravimetric capacity and good reversibility. However the practical application of MgH2 is restricted by slow sorption kinetics and high stability of thermodynamic properties. Hydrogen storage performance of MgH2 was enhanced by introducing the Mg–Na–Al system that destabilises MgH2 with NaAlH4. The Mg–Na–Al system has superior performance compared to that of unary MgH2 and NaAlH4. To boost the performance of the Mg–Na–Al system the ball milling method and the addition of a catalyst were introduced. The Mg–Na–Al system resulted in a low onset decomposition temperature superior cyclability and enhanced kinetics performances. The Al12Mg17 and NaMgH3 that formed in situ during the dehydrogenation process modify the reaction pathway of the Mg–Na–Al system and alter the thermodynamic properties. In this paper the overview of the recent progress in hydrogen storage of the Mg–Na–Al system is detailed. The remaining challenges and future development of Mg–Na–Al system are also discussed. This paper is the first review report on hydrogen storage properties of the Mg–Na–Al system.
Optimal Scheduling of a Hydrogen-Based Energy Hub Considering a Stochastic Multi-Attribute Decision-Making Approach
Jan 2023
Publication
Nowadays the integration of multi-energy carriers is one of the most critical matters in smart energy systems with the aim of meeting sustainable energy development indicators. Hydrogen is referred to as one of the main energy carriers in the future energy industry but its integration into the energy system faces different open challenges which have not yet been comprehensively studied. In this paper a novel day-ahead scheduling is presented to reach the optimal operation of a hydrogen-based energy hub based on a stochastic multi-attribute decision-making approach. In this way the energy hub model is first developed by providing a detailed model of Power-to-Hydrogen (P2H) facilities. Then a new multi-objective problem is given by considering the prosumer’s role in the proposed energy hub model as well as the integrated demand response program (IDRP). The proposed model introduces a comprehensive approach from the analysis of the historical data to the final decision-making with the aim of minimizing the system operation cost and carbon emission. Moreover to deal with system uncertainty the scenario-based method is applied to model the renewable energy resources fluctuation. The proposed problem is defined as mixed-integer non-linear programming (MINLP) and to solve this problem a simple augmented e-constrained (SAUGMECON) method is employed. Finally the simulation of the proposed model is performed on a case study and the obtained results show the effectiveness and benefits of the proposed scheme.
Characterising Hydrogen Induced Cracking of Alloy 625+ Using Correlative SEM - EDX and NanoSIMS
Dec 2020
Publication
Hydrogen induced cracking behaviour of O&G nickel alloy 625+ (UNS N07716) was investigated. Deuterium was introduced electrochemically into samples by cathodic polarisation (3.5 wt.% NaCl.D2O) under different mechanical conditions. Subsequently deuterium distributions were mapped using NanoSIMS. Deuterium was used as an isotopic tracer instead of hydrogen to avoid the detection of hydrogen artefacts. Complimentary image analysis using scanning electron microscopy (SEM) and low voltage energy dispersive X-ray (EDX) allowed the identification of microstructural features corresponding to deuterium enrichments. The results provided experimental evidence of enrichments at dislocation slip bands (DSB) twin boundary and grain boundary features that include σ precipitates.
Alternative Fuels for Internal Combustion Engines
Aug 2020
Publication
The recent transport electrification trend is pushing governments to limit the future use of Internal Combustion Engines (ICEs). However the rationale for this strong limitation is frequently not sufficiently addressed or justified. The problem does not seem to lie within the engines nor with the combustion by themselves but seemingly rather with the rise in greenhouse gases (GHG) namely CO2 rejected to the atmosphere. However it is frequent that the distinction between fossil CO2 and renewable CO2 production is not made or even between CO2 emissions and pollutant emissions. The present revision paper discusses and introduces different alternative fuels that can be burned in IC Engines and would eliminate or substantially reduce the emission of fossil CO2 into the atmosphere. These may be non-carbon fuels such as hydrogen or ammonia or biofuels such as alcohols ethers or esters including synthetic fuels. There are also other types of fuels that may be used such as those based on turpentine or even glycerin which could maintain ICEs as a valuable option for transportation.
Magnesium-Based Materials for Hydrogen Storage—A Scope Review
Sep 2020
Publication
Magnesium hydride and selected magnesium-based ternary hydride (Mg2FeH6 Mg2NiH4 and Mg2CoH5) syntheses and modification methods as well as the properties of the obtained materials which are modified mostly by mechanical synthesis or milling are reviewed in this work. The roles of selected additives (oxides halides and intermetallics) nanostructurization polymorphic transformations and cyclic stability are described. Despite the many years of investigations related to these hydrides and the significant number of different additives used there are still many unknown factors that affect their hydrogen storage properties reaction yield and stability. The described compounds seem to be extremely interesting from a theoretical point of view. However their practical application still remains debatable.
Methanol Synthesis Using Captured CO2 as Raw Material: Techno-economic and Environmental Assessment
Aug 2015
Publication
The purpose of this paper is to assess via techno-economic and environmental metrics the production of methanol (MeOH) using H2 and captured CO2 as raw materials. It evaluates the potential of this type of carbon capture and utilisation (CCU) plant on (i) the net reduction of CO2 emissions and (ii) the cost of production in comparison with the conventional synthesis process of MeOH Europe. Process flow modelling is used to estimate the operational performance and the total purchased equipment cost; the flowsheet is implemented in CHEMCAD and the obtained mass and energy flows are utilised as input to calculate the selected key performance indicators (KPIs). CO2 -based metrics are used to assess the environmental impact. The evaluated MeOH plant produces 440 ktMeOH/yr and its configuration is the result of a heat integration process. Its specific capital cost is lower than for conventional plants. However raw materials prices i.e. H2 and captured CO2 do not allow such a project to be financially viable. In order to make the CCU plant financially attractive the price of MeOH should increase in a factor of almost 2 or H2 costs should decrease almost 2.5 times or CO2 should have a value of around 222 €/t under the assumptions of this work. The MeOH CCU-plant studied can utilise about 21.5% of the CO2 emissions of a pulverised coal (PC) power plant that produces 550MWnet of electricity. The net CO2 emissions savings represent 8% of the emissions of the PC plant (mainly due to the avoidance of consuming fossil fuels as in the conventional MeOH synthesis process). The results demonstrate that there is a net but small potential for CO2 emissions reduction; assuming that such CCU plants are constructed in Europe to meet the MeOH demand growth and the quantities that are currently imported the net CO2 emissions reduction could be of 2.71 MtCO2/yr.
Life-Cycle Greenhouse Gas Emissions Of Biomethane And Hydrogen Pathways In The European Union
Oct 2021
Publication
Gaseous fuels with low life-cycle emissions of greenhouse gases (GHG) play a prominent role in the European Union’s (EU) decarbonization plans. Renewable and low-GHG hydrogen are highlighted in the ambitious goals for a cross-sector hydrogen economy laid out in the European Commission’s Hydrogen Strategy. Renewable hydrogen and biomethane are given strong production incentives in the Commission’s proposed revision to the Renewable Energy Directive (REDII). The EU uses life-cycle analysis (LCA) to determine whether renewable gas pathways meet the GHG reduction thresholds for eligibility in the REDII. This study aims to support European policymakers with a better understanding of the uncertainties regarding gaseous fuels’ roles in meeting climate goals. Life-cycle GHG analysis is complex and differences in methodology as well as data inputs and assumptions can spell the difference between a renewable gas pathway qualifying or not for REDII eligibility at the 50% to 80% GHG reduction level. It is thus important for European policymakers to use robust LCA to ensure that policy only supports gas pathways consistent with a vision of deep decarbonization. For this purpose we conduct sensitivity analysis of the life-cycle GHG emissions of a number of low-GHG gas pathways including biomethane produced from four feedstocks: wastewater sludge manure landfill gas (LFG) and silage maize; and hydrogen produced from eight sources: natural gas combined with carbon capture and storage (CCS) coal with CCS biomass gasification renewable electricity 2030 EU grid electricity wastewater sludge biomethane manure biomethane and LFG biomethane. For each pathway we estimate the life-cycle GHG intensity using a default central case identify key parameters that strongly affect the fuel’s GHG intensity and conduct a sensitivity analysis by changing these key parameters according to the range of possible values collected from the literature. Figure ES1 summarizes the full range of possible GHG intensities for each gaseous pathway we analyzed in this study—biomethane is depicted in the top figure and hydrogen is shown in the bottom. The bars represent the GHG intensity of the central case and vertical error bars indicate the maximum and minimum GHG intensity of each pathway according to our sensitivity analysis. The dotted orange horizontal line illustrates the fossil comparator which is 94 grams of carbon dioxide equivalent per megajoule (gCO2e/MJ) for transport fuels in the REDII. The dotted yellow line represents the GHG intensity of a 65% GHG reduction goal for biomethane used in the transportation sector or 70% GHG reduction for hydrogen. Pathways are situated from left to right in increasing order of GHG intensity of the central case. Comparing the central cases of the four biomethane pathways the waste-based biomethane pathways generally have negative GHG intensity. However considering the uncertainty in these GHG intensities manure biomethane might have more limited carbon reduction potential in the 100-year timeframe if methane leakage from its production process is high. In contrast wastewater sludge biomethane and LFG biomethane even after accounting for uncertainties retain relatively low GHG emissions. On the other hand biomethane produced from silage maize can have much higher emissions; in the central case we find that silage maize biogas only reduces GHG emissions by 30% relative to the fossil comparator—the low carbon reduction potential is due to the significant emissions emerging from direct and indirect land use change involved in growing maize. Taking into account the variation in assumptions silage maize biomethane can be worse for the climate than fossil fuels.
Catalytic Hydrogen Production, Storage and Application
Jul 2021
Publication
Hydrogen is a clean fuel for transportation and energy storage. It has several attractive features including a higher energy content by weight use in fuel cells that produces only water as a by-product storage in small and large quantities by various methods and established transportation and infrastructures. A hydrogen economy consists of three steps i.e. hydrogen production storage and applications. All three steps involved in a hydrogen economy can be divided into catalytic and non-catalytic approaches. For catalytic processes the efficiency highly depends on the type and physico-chemical characteristics of the catalysts. Therefore for the improvement of these catalytic processes the development of highly efficient and stable catalysts is highly required.
Analysis of Hydrogen Production Potential from Waste Plastics by Pyrolysis and In Line Oxidative Steam Reforming
Oct 2021
Publication
A study was carried out on the valorization of different waste plastics (HDPE PP PS and PE) their mixtures and biomass/HDPE mixtures by means of pyrolysis and in line oxidative steam reforming. A thermodynamic equilibrium simulation was used for determining steam reforming data whereas previous experimental results were considered for setting the pyrolysis volatile stream composition. The adequacy of this simulation tool was validated using experimental results obtained in the pyrolysis and in line steam reforming of different plastics. The effect the most relevant process conditions i.e. temperature steam/plastic ratio and equivalence ratio have on H2 production and reaction enthalpy was evaluated. Moreover the most suitable conditions for the oxidative steam reforming of plastics of different nature and their mixtures were determined. The results obtained are evidence of the potential interest of this novel valorization route as H2 productions of up to 25 wt% were obtained operating under autothermal conditions.
Optimisation-based System Designs for Deep Offshore Wind Farms including Power to Gas Technologies
Feb 2022
Publication
A large deployment of energy storage solutions will be required by the stochastic and non-controllable nature of most renewable energy sources when planning for higher penetration of renewable electricity into the energy mix. Various solutions have been suggested for dealing with medium- and long-term energy storage. Hydrogen and ammonia are two of the most frequently discussed as they are both carbon-free fuels. In this paper the authors analyse the energy and cost efficiency of hydrogen and ammonia-based pathways for the storage transportation and final use of excess electricity from an offshore wind farm. The problem is solved as a linear programming problem simultaneously optimising the size of each problem unit and the respective time-dependent operational conditions. As a case study we consider an offshore wind farm of 1.5 GW size located in a reference location North of Scotland. The energy efficiency and cost of the whole chain are evaluated and compared with competitive alternatives namely batteries and liquid hydrogen storage. The results show that hydrogen and ammonia storage can be part of the optimal solution. Moreover their use for long-term energy storage can provide a significant cost-effective contribution to an extensive penetration of renewable energy sources in national energy systems.
Calibrating a Ductile Damage Model for Two Pipeline Steels: Method and Challenges
Dec 2020
Publication
This work is part of a project that aims to develop a micromechanics based damage law taking into account hydrogen assisted degradation. A 'vintage' API 5L X56N and a 'modern' API 5L X70M pipeline steel have been selected for this purpose. The paper focuses on an experimental calibration of ductile damage properties of the well known complete Gurson model for the two steels in absence of hydrogen. A basic microstructural characterization is provided showing a banded ferrite-pearlite microstructure for both steels. Charpy impact tests showed splits at the fracture surface for the X70 steel. Double-notched round bar tensile tests are performed aiming to provide the appropriate input for damage model calibration. The double-notched nature of the specimens allows to examine the material state at maximum load in the unfailed notch and the final material state in the failed notch. Different notch radii are used capturing a broad range of positive stress triaxialities. The notches are optically monitored for transverse necking in two perpendicular directions (transverse to rolling and through thickness) to reveal any anisotropy in plastic deformation and/or damage. It is explained how the occurrence of splits at the segregation zone and anisotropy complicate the calibration procedure. Calibration is done for each steel and acceptable results are obtained. However the occurrence of splits did not allow to evaluate the damage model for the highest levels of tested stress triaxiality.
Photovoltaic and Hydrogen Plant Integrated with a Gas Heat Pump for Greenhouse Heating: A Mathematical Study
Feb 2018
Publication
Nowadays the traditional energy sources used for greenhouse heating are fossil fuels such as LPG diesel and natural gas. The global energy demand will continue to grow and alternative technologies need to be developed in order to improve the sustainability of crop production in protected environments. Innovative solutions are represented by renewable energy plants such as photovoltaic wind and geothermal integrated systems however these technologies need to be connected to the power grid in order to store the energy produced. On agricultural land power grids are not widespread and stand-alone renewable energy systems should be investigated especially for greenhouse applications. The aim of this research is to analyze by means of a mathematical model the energy efficiency of a photovoltaic (8.2 kW) hydrogen (2.5 kW) and ground source gas heat pump (2.2 kW) integrated in a stand-alone system used for heating an experimental greenhouse tunnel (48 m2 ) during the winter season. A yearlong energy performance analysis was conducted for three different types of greenhouse cover materials a single layer polyethylene film an air inflated-double layer polyethylene film and a double acrylic or polycarbonate. The results of one year showed that the integrated system had a total energy efficiency of 14.6%. Starting from the electric energy supplied by the photovoltaic array the total efficiency of the hydrogen and ground source gas heat pump system was 112% if the coefficient of the performance of the heat pump is equal to 5. The heating system increased the greenhouse air temperatures by 3–9 ◦C with respect to the external air temperatures depending on the greenhouse cover material used.
HyDeploy Report: Exemption
Oct 2018
Publication
Exemption is requested from the obligation set out in Regulation 8(1) of the Gas Safety (Management) Regulations 1996 (GSMR) to convey only natural gas that is compliant with the Interchangeability requirements of Part I of Schedule 3 of the GSMR within the G3 element of the Keele University gas distribution network (KU-GDN). The KU-GDN is owned and operated by Keele University. The proposed conveyance of non-compliant gas (hereafter called the “HyDeploy Field Trial”) will last for one year of injection and is part of a Network Innovation Competition Project “HyDeploy”. The project aims to demonstrate that natural gas containing hydrogen at a level above that normally permitted by Schedule 3 of the GSMR can be safely and efficiently conveyed and inform decisions on the feasibility and strategy for wider deployment of natural gas containing hydrogen in Great Britain’s (GB’s) gas transmission and gas distribution systems.<br/>Click the supplements tab for the other documents from this report.
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