Spain
A Review of Techno-economic Data for Road Transportation Fuels
May 2019
Publication
Worldwide the road transport sector typically arises as one of the main sources of air pollutants due to its high energy intensity and the use of fossil fuels. Thus governments and social agents work on the development and prospective planning of decarbonisation strategies oriented towards sustainable transport. In this regard the increase in the use of alternative fuels is the recurrent approach to energy planning e.g. through the promotion of electric vehicles biofuels natural gas liquefied petroleum gas etc. However there is a lack of comprehensive information on the techno-economic performance of production pathways for alternative fuels. The acquisition of robust techno-economic data is still a challenge for energy planners modellers analysts and policy-makers when building their prospective models to support decision-making processes. Hence this article aims to fill this gap through a deep literature review including the most representative production routes for a wide range of road transportation fuels. This led to the development of datasets including investment costs operating and maintenance costs and transformation efficiencies for more than 40 production pathways. The techno-economic data presented in this work are expected to be especially useful to those energy actors interested in performing long-term studies on the transition to a sustainable transport system.
Modifications in the Composition of CuO/ZnO/Al2O3 Catalyst for the Synthesis of Methanol by CO2 Hydrogenation
Jun 2021
Publication
Renewable methanol obtained from CO2 and hydrogen provided from renewable energy was proposed to close the CO2 loop. In industry methanol synthesis using the catalyst CuO/ZnO/Al2O3 occurs at a high pressure. We intend to make certain modification on the traditional catalyst to work at lower pressure maintaining high selectivity. Therefore three heterogeneous catalysts were synthesized by coprecipitation to improve the activity and the selectivity to methanol under mild conditions of temperature and pressure. Certain modifications on the traditional catalyst Cu/Zn/Al2O3 were employed such as the modification of the synthesis time and the addition of Pd as a dopant agent. The most efficient catalyst among those tested was a palladium-doped catalyst 5% Pd/Cu/Zn/Al2O3. This had a selectivity of 64% at 210 °C and 5 bar.
Achievements of European Projects on Membrane Reactor for Hydrogen Production
May 2017
Publication
Membrane reactors for hydrogen production can increase both the hydrogen production efficiency at small scale and the electric efficiency in micro-cogeneration systems when coupled with Polymeric Electrolyte Membrane fuel cells. This paper discusses the achievements of three European projects (FERRET FluidCELL BIONICO) which investigate the application of the membrane reactor concept to hydrogen production and micro-cogeneration systems using both natural gas and biofuels (biogas and bio-ethanol) as feedstock. The membranes used to selectively separate hydrogen from the other reaction products (CH4 CO2 H2O etc.) are of asymmetric type with a thin layer of Pd alloy (<5 μm) and supported on a ceramic porous material to increase their mechanical stability. In FERRET the flexibility of the membrane reactor under diverse natural gas quality is validated. The reactor is integrated in a micro-CHP system and achieves a net electric efficiency of about 42% (8% points higher than the reference case). In FluidCELL the use of bio-ethanol as feedstock for micro-cogeneration Polymeric Electrolyte Membrane based system is investigated in off-grid applications and a net electric efficiency around 40% is obtained (6% higher than the reference case). Finally BIONICO investigates the hydrogen production from biogas. While BIONICO has just started FERRET and FluidCELL are in their third year and the two prototypes are close to be tested confirming the potentiality of membrane reactor technology at small scale.
Absence of Spillover of Hydrogen Adsorbed on Small Palladium Clusters Anchored to Graphene Vacancies
May 2021
Publication
Experimental evidence exists for the enhancement of the hydrogen storage capacity of porous carbons when these materials are doped with metal nanoparticles. One of the most studied dopants is palladium. Dissociation of the hydrogen molecules and spillover of the H atoms towards the carbon substrate has been advocated as the reason for the enhancement of the storage capacity. We have investigated this mechanism by performing ab initio density functional molecular dynamics (AIMD) simulations of the deposition of molecular hydrogen on Pd6 clusters anchored on graphene vacancies. The clusters are initially near-saturated with atomic and molecular hydrogen. This condition would facilitate the occurrence of spillover since our energy calculations based on density functional theory indicate that migration of preadsorbed H atoms towards the graphene substrate becomes exothermic on Pd clusters with high hydrogen coverages. However AIMD simulations show that the H atoms prefer to intercalate and absorb within the Pd cluster rather than migrate to the carbon substrate. These results reveal that high activation barriers exist preventing the spillover of hydrogen from the anchored Pd clusters to the carbon substrate.
Perspectives on Cathodes for Protonic Ceramic Fuel Cells
Jun 2021
Publication
Protonic ceramic fuel cells (PCFCs) are promising electrochemical devices for the efficient and clean conversion of hydrogen and low hydrocarbons into electrical energy. Their intermediate operation temperature (500–800 °C) proffers advantages in terms of greater component compatibility unnecessity of expensive noble metals for the electrocatalyst and no dilution of the fuel electrode due to water formation. Nevertheless the lower operating temperature in comparison to classic solid oxide fuel cells places significant demands on the cathode as the reaction kinetics are slower than those related to fuel oxidation in the anode or ion migration in the electrolyte. Cathode design and composition are therefore of crucial importance for the cell performance at low temperature. The different approaches that have been adopted for cathode materials research can be broadly classified into the categories of protonic–electronic conductors oxide-ionic–electronic conductors triple-conducting oxides and composite electrodes composed of oxides from two of the other categories. Here we review the relatively short history of PCFC cathode research discussing trends highlights and recent progress. Current understanding of reaction mechanisms is also discussed.
Hydrogen Permeation Studies of Composite Supported Alumina-carbon Molecular Sieves Membranes: Separation of Diluted Hydrogen from Mixtures with Methane
Jun 2020
Publication
One alternative for the storage and transport of hydrogen is blending a low amount of hydrogen (up to 15 or 20%) into existing natural gas grids. When demanded hydrogen can be then separated close to the end users using membranes. In this work composite alumina carbon molecular sieves membranes (Al-CMSM) supported on tubular porous alumina have been prepared and characterized. Single gas permeation studies showed that the H2/CH4 separation properties at 30 °C are well above the Robeson limit of polymeric membranes. H2 permeation studies of the H2–CH4 mixture gases containing 5–20% of H2 show that the H2 purity depends on the H2 content in the feed and the operating temperature. In the best scenario investigated in this work for samples containing 10% of H2 with an inlet pressure of 7.5 bar and permeated pressure of 0.01 bar at 30 °C the H2 purity obtained was 99.4%.
Analysis of Samples Cleaning Methods Prior to Hydrogen Content Determination in Steel
May 2020
Publication
There are multiple references to sample cleaning methods prior to hydrogen content determination or hydrogen spectroscopy analysis but there is still no unified criteria; different authors use their own “know-how” to perform this task. The aim of this paper is to solve or at least clarify this issue. In this work the most commonly used sample cleaning methods are compared. Then five different methodologies are applied on certified hydrogen content calibration pins and on high strength steel concrete-prestressing strands and the three main situations regarding hydrogen content in the microstructural net (non-charged charged and charged and uncharged) are studied. It was concluded that the HCl solution C-3.5 cleaning method recommended by ASTM G1 introduces large amounts of hydrogen in the samples; but can be useful for eliminating superficial oxides if necessary. The rest of the methods had similar results; but the more complete ones that involve ultrasounds and last longer than 8 min are not appropriated when important diffusion may occur on the samples during their application. Simple methods that involve acetone or trichloroethylene and last around 1 min are preferable for almost all situations as these are faster easier and cheaper. As a final recommendation as trichloroethylene is toxic the simple acetone method is in general the most convenient one for regular hydrogen content analysis.
Investigation of Praseodymium and Samarium Co-doped Ceria as an Anode Catalyst for DIR-SOFC Fueled by Biogas
Aug 2020
Publication
The Pr and Sm co-doped ceria (with up to 20 mol.% of dopants) compounds were examined as catalytic layers on the surface of SOFC anode directly fed by biogas to increase a lifetime and the efficiency of commercially available DIR-SOFC without the usage of an external reformer.
The XRD SEM and EDX methods were used to investigate the structural properties and the composition of fabricated materials. Furthermore the electrical properties of SOFCs with catalytic layers deposited on the Ni-YSZ anode were examined by a current density-time and current density-voltage dependence measurements in hydrogen (24 h) and biogas (90 h). Composition of the outlet gasses was in situ analysed by the FTIR-based unit.
It has been found out that Ce0.9Sm0.1O2-δ and Ce0.8Pr0.05Sm0.15O2-δ catalytic layers show the highest stability over time and thus are the most attractive candidates as catalytic materials in comparison with other investigated lanthanide-doped ceria enhancing direct internal reforming of biogas in SOFCs.
The XRD SEM and EDX methods were used to investigate the structural properties and the composition of fabricated materials. Furthermore the electrical properties of SOFCs with catalytic layers deposited on the Ni-YSZ anode were examined by a current density-time and current density-voltage dependence measurements in hydrogen (24 h) and biogas (90 h). Composition of the outlet gasses was in situ analysed by the FTIR-based unit.
It has been found out that Ce0.9Sm0.1O2-δ and Ce0.8Pr0.05Sm0.15O2-δ catalytic layers show the highest stability over time and thus are the most attractive candidates as catalytic materials in comparison with other investigated lanthanide-doped ceria enhancing direct internal reforming of biogas in SOFCs.
The Role of the Testing Rate on Small Punch Tests for the Estimation of Fracture Toughness in Hydrogen Embrittlement
Dec 2020
Publication
In this paper different techniques to test notched Small Punch (SPT) samples in fracture conditions in aggressive environments are studied based on the comparison of the micromechanisms at different rates. Pre-embrittled samples subsequently tested in air at rates conventionally employed (0.01 and 0.002 mm/s) are compared to embrittled ones tested in environment at the same rates (0.01 and 0.002 mm/s) and at a very slow rate (5E-5 mm/s). A set of samples tested in environment under a set of constant loads that produce very slow rates completes the experimental results. As a conclusion it is recommended to test SPT notched specimens in environment at very slow rates of around E-6 mm/s when characterizing in Hydrogen Embrittlement (HE) scenarios in order to allow the interaction material-environment to govern the process.
Enhancing Energy Recovery in Form of Biogas, from Vegetable and Fruit Wholesale Markets By-Products and Wastes, with Pretreatments
Jun 2021
Publication
Residues and by-products from vegetables and fruit wholesale markets are suitable for recovery in the form of energy through anaerobic digestion allowing waste recovery and introducing them into the circular economy. This suitability is due to their composition structural characteristics and to the biogas generation process which is stable and without inhibition. However it has been observed that the proportion of methane and the level of degradation of the substrate is low. It is decided to study whether the effect of pretreatments on the substrate is beneficial. Freezing ultrafreezing and lyophilization pretreatments are studied. A characterization of the substrates has been performed the route of action of pretreatment determined and the digestion process studied to calculate the generation of biogas methane hydrogen and the proportions among these. Also a complete analysis of the process has been performed by processing the data with mathematical and statistical methods to obtain disintegration constants and levels of degradation. It has been observed that the three pretreatments have positive effects when increasing the solubility of the substrate increasing porosity and improving the accessibility of microorganisms to the substrate. Generation of gases are greatly increased reaching a methane enrichment of 59.751%. Freezing seems to be the best pretreatment as it increases the biodegradation level the speed of the process and the disintegration constant by 306%.
Production of Hydrogen by Chemical Looping Reforming of Methane and Biogas using a Reactive and Durable Cu-based Oxygen Carrier
Apr 2022
Publication
The objective of this work was to assess the suitability of a synthetic Cu-based oxygen carrier in a continuous pilot plant for the production of blue and green hydrogen through the autothermal Chemical Looping Reforming (CLRa). In CLRa methane is converted to a H2 + CO mixture through partial oxidation and reforming reactions in the fuel reactor. The degree of the partial oxidation of methane was defined by controlling the oxygen flow in the air reactor. Steam was used as reforming gas in natural gas to produce blue H2 but the existing CO2 in biogas was the reforming gas to produce green H2. Operating at 950 ◦C in the fuel and air reactors CH4 conversion and H2 yield parameters were 96 % and 2.60 mol of H2 per mole of CH4 respectively. These experimental results were close to the theoretical values that could be achieved in the CLRa process. Furthermore the physico-chemical characterization of the samples extracted from the pilot plant throughout the experimental campaign revealed that the Cu-based oxygen carrier maintained its mechanical integrity and chemical stability under harsh operating conditions. Therefore it can be concluded that Cu-based oxygen carriers can be considered a promising alternative to Ni-based materials for the production of blue and green hydrogen through the CLRa process.
Standalone Renewable Energy and Hydrogen in an Agricultural Context: A Demonstrative Case
Feb 2019
Publication
Standalone renewable energy is widely used to power irrigation systems. However in agricultural facilities electricity from the grid and diesel are also consumed. The design and sizing of renewable generation involves difficulties derived from the different seasonal profiles of production and demand. If the generation is 100% renewable a considerable energy surplus is usually included. This paper is focused on a renewable energy system which has been installed in a vineyard located in the northeast of Spain. With energy from the photovoltaic fields the wastewater treatment plant of the winery a drip irrigation system and other ancillary consumptions are fed. The favourable effect of combining consumptions with different seasonal profiles is shown. The existence of some deferrable loads and the energy management strategy result in an aggregate consumption curve that is well suited to production. Besides the required energy storage is relatively small. The surplus energy is used for the on-site production of hydrogen by the electrolysis of water. The hydrogen refuels a hybrid fuel cell electric vehicle used for the mobility of workers in the vineyard. In summary electricity and hydrogen are produced on-site (to meet the energy needs) from 100% renewable sources and without operating emissions.
Polymer–Ceramic Composite Membranes for Water Removal in Membrane Reactors
Jun 2021
Publication
Methanol can be obtained through CO2 hydrogenation in a membrane reactor with higher yield or lower pressure than in a conventional packed bed reactor. In this study we explore a new kind of membrane with the potential suitability for such membrane reactors. Silicone–ceramic composite membranes are synthetized and characterized for their capability to selectively remove water from a mixture containing hydrogen CO2 and water at temperatures typical for methanol synthesis. We show that this membrane can achieve selective permeation of water under such harsh conditions and thus is an alternative candidate for use in membrane reactors for processes where water is one of the products and the yield is limited by thermodynamic equilibrium.
A Hybrid Intelligent Model to Predict the Hydrogen Concentration in the Producer Gas from a Downdraft Gasifier
Apr 2022
Publication
This research work presents an artificial intelligence approach to predicting the hydrogen concentration in the producer gas from biomass gasification. An experimental gasification plant consisting of an air-blown downdraft fixed-bed gasifier fueled with exhausted olive pomace pellets and a producer gas conditioning unit was used to collect the whole dataset. During an extensive experimental campaign the producer gas volumetric composition was measured and recorded with a portable syngas analyzer at a constant time step of 10 seconds. The resulting dataset comprises nearly 75 hours of plant operation in total. A hybrid intelligent model was developed with the aim of performing fault detection in measuring the hydrogen concentration in the producer gas and still provide reliable values in the event of malfunction. The best performing hybrid model comprises six local internal submodels that combine artificial neural networks and support vector machines for regression. The results are remarkably satisfactory with a mean absolute prediction error of only 0.134% by volume. Accordingly the developed model could be used as a virtual sensor to support or even avoid the need for a real sensor that is specific for measuring the hydrogen concentration in the producer gas.
Optimization of a Solar Hydrogen Storage System: Safety Considerations
Sep 2007
Publication
Hydrogen has been extensively used in many industrial applications for more than 100 years including production storage transport delivery and final use. Nevertheless the goal of the hydrogen energy system implies the use of hydrogen as an energy carrier in a more wide scale and for a public not familiarised with hydrogen technologies and properties.<br/>The road to the hydrogen economy passes by the development of safe practices in the production storage distribution and use of hydrogen. These issues are essential for hydrogen insurability. We have to bear in mind that a catastrophic failure in any hydrogen project could damage the insurance public perception of hydrogen technologies at this early step of development of hydrogen infrastructures.<br/>Safety is a key issue for the development of hydrogen economy and a great international effort is being done by different stakeholders for the development of suitable codes and standards concerning safety for hydrogen technologies [1 2]. Additionally to codes and standards different studies have been done regarding safety aspects of particular hydrogen energy projects during the last years [3 4]. Most of such have been focused on hydrogen production and storage in large facilities transport delivery in hydrogen refuelling stations and utilization mainly on fuel cells for mobile and stationary applications. In comparison safety considerations for hydrogen storage in small or medium scale facilities as usual in hydrogen production plants from renewable energies have received relatively less attention.<br/>After a brief introduction to risk assessment for hydrogen facilities this paper reports an example of risk assessment of a small solar hydrogen storage system applied to the INTA Solar Hydrogen Production and Storage facility as particular case and considers a top level Preliminary Failure Modes and Effects Analysis (FMEA) for the identification of hazard associated to the specific characteristics of the facility.
Compatibility of Materials with Hydrogen Particular Case- Hydrogen Assisted Stress Cracking of Titanium Alloys
Sep 2007
Publication
A review of the effect of hydrogen on materials is addressed in this paper. General aspects of the interaction of hydrogen and materials hydrogen embrittlement low temperature effects material suitability for hydrogen service and materials testing are the main subjects considered in the first part of the paper. As a particular case of the effect of hydrogen in materials the hydride formation of titanium alloys is considered. Alpha titanium alloys are considered corrosion resistant materials in a wide range of environments. However hydrogen absorption and the possible associated problems must be taken into account when considering titanium as a candidate material for high responsibility applications. The sensitivity of three different titanium alloys Ti Gr-2 Ti Gr-5 and Ti Gr-12 to the Hydrogen Assisted Stress Cracking phenomena has been studied by means of the Slow Strain Rate Technique (SSRT). The testing media has been sea water and hydrogen has been produced on the specimen surface during the test by cathodic polarization. Tested specimens have been characterized by metallography and scanning electron microscopy. Results obtained show that the microstructure of the materials particularly the β phase content plays an important role on the sensitivity of the studied alloys to the Hydrogen Assisted Stress Cracking Phenomena.
Techno-Economics Optimization of H2 and CO2 Compression for Renewable Energy Storage and Power-to-Gas Applications
Nov 2021
Publication
The decarbonization of the industrial sector is imperative to achieve a sustainable future. Carbon capture and storage technologies are the leading options but lately the use of CO2 is also being considered as a very attractive alternative that approaches a circular economy. In this regard power to gas is a promising option to take advantage of renewable H2 by converting it together with the captured CO2 into renewable gases in particular renewable methane. As renewable energy production or the mismatch between renewable production and consumption is not constant it is essential to store renewable H2 or CO2 to properly run a methanation installation and produce renewable gas. This work analyses and optimizes the system layout and storage pressure and presents an annual cost (including CAPEX and OPEX) minimization. Results show the proper compression stages need to achieve the storage pressure that minimizes the system cost. This pressure is just below the supercritical pressure for CO2 and at lower pressures for H2 around 67 bar. This last quantity is in agreement with the usual pressures to store and distribute natural gas. Moreover the H2 storage costs are higher than that of CO2 even with lower mass quantities; this is due to the lower H2 density compared with CO2 . Finally it is concluded that the compressor costs are the most relevant costs for CO2 compression but the storage tank costs are the most relevant in the case of H2.
Optimal Energy Management System Using Biogeography Based Optimization for Grid-connected MVDC Microgrid with Photovoltaic, Hydrogen System, Electric Vehicles and Z-source Converters
Oct 2021
Publication
Currently the technology associated with charging stations for electric vehicles (EV) needs to be studied and improved to further encourage its implementation. This paper presents a new energy management system (EMS) based on a Biogeography-Based Optimization (BBO) algorithm for a hybrid EV charging station with a configuration that integrates Z-source converters (ZSC) into medium voltage direct current (MVDC) grids. The EMS uses the evolutionary BBO algorithm to optimize a fitness function defining the equivalent hydrogen consumption/generation. The charging station consists of a photovoltaic (PV) system a local grid connection two fast charging units and two energy storage systems (ESS) a battery energy storage (BES) and a complete hydrogen system with fuel cell (FC) electrolyzer (LZ) and hydrogen tank. Through the use of the BBO algorithm the EMS manages the energy flow among the components to keep the power balance in the system reducing the equivalent hydrogen consumption and optimizing the equivalent hydrogen generation. The EMS and the configuration of the charging station based on ZSCs are the main contributions of the paper. The behaviour of the EMS is demonstrated with three EV connected to the charging station under different conditions of sun irradiance. In addition the proposed EMS is compared with a simpler EMS for the optimal management of ESS in hybrid configurations. The simulation results show that the proposed EMS achieves a notable improvement in the equivalent hydrogen consumption/generation with respect to the simpler EMS. Thanks to the proposed configuration the output voltage of the components can be upgraded to MVDC while reducing the number of power converters compared with other configurations without ZSC.
Hydrogen vs. Battery-Based Propulsion Systems in Unipersonal Vehicles—Developing Solutions to Improve the Sustainability of Urban Mobility
May 2021
Publication
The percentage of the population in urban areas has increased by ten points from 2000 (46%) to 2020 (56%); it is expected to reach up to 70% by 2050. This undoubtedly will encourage society to use alternative transports. On the other hand the widespread fear of pandemics seems to be here to stay and it is causing most people to leave public transport to use private cars and a few have chosen unipersonal electric vehicles. As a consequence the decision of using private cars negatively affects the air quality and consequently urban population health. This paper aims to demonstrate a sustainable solution for urban mobility based on a hydrogen powered unipersonal electric vehicle which as shown provides great advantages over the conventional battery powered unipersonal electric vehicle. To show this the authors have developed both vehicles in comparable versions using the same platform and ensuring that the total weight of the unipersonal electric vehicle was the same in both cases. They have been subjected to experimental tests that support the features of the hydrogen-based configuration versus the battery-based one including higher specific energy more autonomy and shorter recharge time.
The Potential of Gas Switching Partial Oxidation Using Advanced Oxygen Carriers for Efficient H2 Production with Inherent CO2 Capture
May 2021
Publication
The hydrogen economy has received resurging interest in recent years as more countries commit to net-zero CO2 emissions around the mid-century. “Blue” hydrogen from natural gas with CO2 capture and storage (CCS) is one promising sustainable hydrogen supply option. Although conventional CO2 capture imposes a large energy penalty advanced process concepts using the chemical looping principle can produce blue hydrogen at efficiencies even exceeding the conventional steam methane reforming (SMR) process without CCS. One such configuration is gas switching reforming (GSR) which uses a Ni-based oxygen carrier material to catalyze the SMR reaction and efficiently supply the required process heat by combusting an off-gas fuel with integrated CO2 capture. The present study investigates the potential of advanced La-Fe-based oxygen carrier materials to further increase this advantage using a gas switching partial oxidation (GSPOX) process. These materials can overcome the equilibrium limitations facing conventional catalytic SMR and achieve direct hydrogen production using a water-splitting reaction. Results showed that the GSPOX process can achieve mild efficiency improvements relative to GSR in the range of 0.6–4.1%-points with the upper bound only achievable by large power and H2 co-production plants employing a highly efficient power cycle. These performance gains and the avoidance of toxicity challenges posed by Ni-based oxygen carriers create a solid case for the further development of these advanced materials. If successful results from this work indicate that GSPOX blue hydrogen plants can outperform an SMR benchmark with conventional CO2 capture by more than 10%-points both in terms of efficiency and CO2 avoidance.
No more items...