Production & Supply Chain
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%.
Enhanced Hydrogen Generation Efficiency of Methanol using Dielectric Barrier Discharge Plasma Methodology and Conducting Sea Water as an Electrode
Aug 2020
Publication
In this work methanol decomposition method has been discussed for the production of hydrogen gas with the application of plasma. A simple dielectric barrier discharge (DBD) plasma reactor was designed for this purpose with two types of electrode. The DBD plasma reactor was experimented by substituting one of the metal electrodes with feebly conducting sea water which yielded better efficiency in producing hydrogen gas. Experimental parameters such as; discharge voltage and time were varied by maintaining a discharge gap of 1.5 mm and the plasma discharge characteristics were studied. Filamentary type micro-discharges were found to be formed which was observed as numerous streamer clusters in the current waveform. Gas chromatographic study confirmed the production of hydrogen gas with residence time around 3.6 min. Although the concentration (%) of H2 was high (98.1 %) and consistent with copper electrode assembly the rate of formation and concentration was found to be the highest (98.7 %) for water electrode for specific discharge voltage. The energy efficiency was found to be 0.5 mol H2/kWh and 1.2 mol H2/kWh for metal (Cu) and water electrodes respectively. The electrode material significantly affects the plasma condition and hence the rate of hydrogen production. Compositional analysis of the water used as electrode showed a minimal change in the composition even after the completion of the experiment as compared to the untreated water. Methanol degradation study shows the presence of untreated methanol in the residue of the plasma reactor which has been confirmed from the absorption spectra.
Optimization of Geothermal- and Solar-driven Clean Electricity and Hydrogen Production Multi-generation Systems to Address the Energy Nexus
Jan 2022
Publication
Given the limited sources of fossil fuels mankind should find new ways to meet its energy demands. In this regard geothermal and solar energy are acknowledged as reliable safe promising and clean means for this purpose. In this research study a comparative analysis is applied on geothermal and solar-driven multi-generation systems for clean electricity and hydrogen production through energy and exergy assessments. The system consists of an organic Rankine cycle a proton electrolyte membrane electrolyzer and a thermoelectric generator subsystem. The Engineering Equation Solver software has been utilized in order to model the system and obtain the output contours sensitivity analysis and exergy destruction. The results were calculated considering the ambient temperature of Bandar Abbas city as a case study considering the geothermal system due to better performance in comparison to the solar system. According to the sensitivity analysis the turbine efficiency evaporator inlet temperature thermoelectric generator suitability criterion pump efficiency and evaporator inlet mass flow rate are the most influential parameters. Also the exergy analysis showed that the utmost system's exergy destruction is pertinent to the evaporator and the least is related to the pump. In addition the system produces 352816 kWh and 174.913 kg of electrical power and hydrogen during one year.
Scenario-Based Techno-Economic Analysis of Steam Methane Reforming Process for Hydrogen Production
Jun 2021
Publication
Steam methane reforming (SMR) process is regarded as a viable option to satisfy the growing demand for hydrogen mainly because of its capability for the mass production of hydrogen and the maturity of the technology. In this study an economically optimal process configuration of SMR is proposed by investigating six scenarios with different design and operating conditions including CO2 emission permits and CO2 capture and sale. Of the six scenarios the process configuration involving CO2 capture and sale is the most economical with an H2 production cost of $1.80/kg-H2. A wide range of economic analyses is performed to identify the tradeoffs and cost drivers of the SMR process in the economically optimal scenario. Depending on the CO2 selling price and the CO2 capture cost the economic feasibility of the SMR-based H2 production process can be further improved.
Metal‐Supported Biochar Catalysts for Sustainable Biorefinery, Electrocatalysis and Energy Storage Applications: A Review
Feb 2022
Publication
Biochar (BCH) is a carbon‐based bio‐material produced from thermochemical conversion of biomass. Several activation or functionalization methods are usually used to improve physicochemical and functional properties of BCHs. In the context of green and sustainable future development activated and functionalized biochars with abundant surface functional groups and large surface area can act as effective catalysts or catalyst supports for chemical transformation of a range of bioproducts in biorefineries. Above the well‐known BCH applications their use as adsorbents to remove pollutants are the mostly discussed although their potential as catalysts or catalyst supports for advanced (electro)catalytic processes has not been comprehensively explored. In this review the production/activation/functionalization of metal‐supported biochar (M‐BCH) are scrutinized giving special emphasis to the metal‐functionalized biochar‐based (electro)catalysts as promising catalysts for bioenergy and bioproducts production. Their performance in the fields of biorefinery processes and energy storage and conversion as electrode materials for oxygen and hydrogen evolutions oxygen reduction and supercapacitors are also reviewed and discussed.
Hollow CdS-Based Photocatalysts
Oct 2020
Publication
In recent years photocatalytic technology driven by solar energy has been extensively investigated to ease energy crisis and environmental pollution. Nevertheless efficiency and stability of photocatalysts are still unsatisfactory. To address these issues design of advanced photocatalysts is important. Cadmium sulphide (CdS) nanomaterials are one of the promising photocatalysts. Among them hollow-structured CdS featured with enhanced light absorption ability large surface area abundant active sites for redox reactions and reduced diffusion distance of photogenerated carriers reveals a broad application prospect. Herein main synthetic strategies and formation mechanism of hollow CdS photocatalysts are summarized. Besides we comprehensively discuss the current development of hollow-structured CdS nanomaterials in photocatalytic applications including H2 production CO2 reduction and pollutant degradation. Finally brief conclusions and perspectives on the challenges and future directions for hollow CdS photocatalysts are proposed.
Simulation of a Multi-Functional Energy System for Cogeneration of Steam, Power and Hydrogen in a Coke Making Plant
Mar 2013
Publication
In this paper a multifunctional energy system (MES) is proposed for recovering energy from the extra of coke oven gas (COG) which is usually flared or vented out as a waste stream in coke making plants. The proposed system consists of a pressure swing adsorption (PSA) unit for extracting some of the hydrogen from COG a gas turbine for producing heat and power from PSA offgas and a heat recovery steam generator (HRSG) for generating the steam required by the plant's processes. o assess the performance of the system practically simulations are carried out on the basis of the design and operational conditions of Zarand Coke Making Plant in Iran. The results indicate that by utilizing about 4.39 tons of COG per hour 6.5 MW of net electric power can be approximately produced by the gas turbine which can supply the coke making plant's total electrical power demand. Furthermore through recovering heat from gas turbine's exhaust close to 57% of the plant's steam demand can be supplied by the HRSG unit. It is also found that around 350 kilograms per hour of nearly pure hydrogen (99.9% purity) at 200 bar can be produced by the PSA unit. According to the sensitivity analysis results if the hydrogen content of the coke oven gas decreases by about 10% the gross power output of the gas turbine also declines by around 5.2% due to the reduction of LHV of the PSA offgas. Moreover economic evaluation of the system shows that the payback period of the investment which is estimated at 36.1 M$ is about 5.5 years. The net present value (NPV) and internal rate of return on investment (ROI) are calculated to be 17.6% and 43.3 M$ respectively.
Sub-second and Ppm-level Optical Sensing of Hydrogen Using Templated Control of Nano-hydride Geometry and Composition
Apr 2021
Publication
The use of hydrogen as a clean and renewable alternative to fossil fuels requires a suite of flammability mitigating technologies particularly robust sensors for hydrogen leak detection and concentration monitoring. To this end we have developed a class of lightweight optical hydrogen sensors based on a metasurface of Pd nano-patchy particle arrays which fulfills the increasing requirements of a safe hydrogen fuel sensing system with no risk of sparking. The structure of the optical sensor is readily nano-engineered to yield extraordinarily rapid response to hydrogen gas (<3 s at 1 mbar H2) with a high degree of accuracy (<5%). By incorporating 20% Ag Au or Co the sensing performances of the Pd-alloy sensor are significantly enhanced especially for the Pd80Co20 sensor whose optical response time at 1 mbar of H2 is just ~0.85 s while preserving the excellent accuracy (<2.5%) limit of detection (2.5 ppm) and robustness against aging temperature and interfering gases. The superior performance of our sensor places it among the fastest and most sensitive optical hydrogen sensors.
Options for Producing Low-carbon Hydrogen at Scale
Feb 2018
Publication
Low-carbon hydrogen has the potential to play a significant role in tackling climate change and poor air quality. This policy briefing considers how hydrogen could be produced at a useful scale to power vehicles heat homes and supply industrial processes.
Four groups of hydrogen production technologies are examined:
Thermochemical Routes to Hydrogen
These methods typically use heat and fossil fuels. Steam methane reforming is the dominant commercial technology and currently produces hydrogen on a large scale but is not currently low carbon. Carbon capture is therefore essential with this process. Innovative technology developments may also help and research is underway. Alternative thermal methods of creating hydrogen indicate biomass gasification has potential. Other techniques at a low technology readiness level include separation of hydrogen from hydrocarbons using microwaves.
Electrolytic Routes to Hydrogen
Electrolytic hydrogen production also known as electrolysis splits water into hydrogen and oxygen using electricity in an electrolysis cell. Electrolysis produces pure hydrogen which is ideal for low temperature fuel cells for example in electric vehicles. Commercial electrolysers are on the market and have been in use for many years. Further technology developments will enable new generation electrolysers to be commercially competitive when used at scale with fluctuating renewable energy sources.
Biological Routes to Hydrogen
Biological routes usually involve the conversion of biomass to hydrogen and other valuable end products using microbial processes. Methods such as anaerobic digestion are feasible now at a laboratory and small pilot scale. This technology may prove to have additional or greater impact and value as route for the production of high value chemicals within a biorefinery concept.
Solar to Fuels Routes to Hydrogen
A number of experimental techniques have been reported the most developed of which is ‘solar to fuels’ - a suite of technologies that typically split water into hydrogen and oxygen using solar energy. These methods have close parallels with the process of photosynthesis and are often referred to as ‘artificial photosynthesis’ processes. The research is promising though views are divided on its ultimate utility. Competition for space will always limit the scale up of solar to fuels.
The briefing concludes that steam methane reforming and electrolysis are the most likely technologies to be deployed to produce low-carbon hydrogen at volume in the near to mid-term providing that the challenges of high levels of carbon capture (for steam methane reforming) and cost reduction and renewable energy sources (for electrolysis) can be overcome.
Four groups of hydrogen production technologies are examined:
Thermochemical Routes to Hydrogen
These methods typically use heat and fossil fuels. Steam methane reforming is the dominant commercial technology and currently produces hydrogen on a large scale but is not currently low carbon. Carbon capture is therefore essential with this process. Innovative technology developments may also help and research is underway. Alternative thermal methods of creating hydrogen indicate biomass gasification has potential. Other techniques at a low technology readiness level include separation of hydrogen from hydrocarbons using microwaves.
Electrolytic Routes to Hydrogen
Electrolytic hydrogen production also known as electrolysis splits water into hydrogen and oxygen using electricity in an electrolysis cell. Electrolysis produces pure hydrogen which is ideal for low temperature fuel cells for example in electric vehicles. Commercial electrolysers are on the market and have been in use for many years. Further technology developments will enable new generation electrolysers to be commercially competitive when used at scale with fluctuating renewable energy sources.
Biological Routes to Hydrogen
Biological routes usually involve the conversion of biomass to hydrogen and other valuable end products using microbial processes. Methods such as anaerobic digestion are feasible now at a laboratory and small pilot scale. This technology may prove to have additional or greater impact and value as route for the production of high value chemicals within a biorefinery concept.
Solar to Fuels Routes to Hydrogen
A number of experimental techniques have been reported the most developed of which is ‘solar to fuels’ - a suite of technologies that typically split water into hydrogen and oxygen using solar energy. These methods have close parallels with the process of photosynthesis and are often referred to as ‘artificial photosynthesis’ processes. The research is promising though views are divided on its ultimate utility. Competition for space will always limit the scale up of solar to fuels.
The briefing concludes that steam methane reforming and electrolysis are the most likely technologies to be deployed to produce low-carbon hydrogen at volume in the near to mid-term providing that the challenges of high levels of carbon capture (for steam methane reforming) and cost reduction and renewable energy sources (for electrolysis) can be overcome.
Blue Hydrogen
Apr 2021
Publication
The urgency of reaching net-zero emissions requires a rapid acceleration in the deployment of all emissions reducing technologies. Near-zero emissions hydrogen (clean hydrogen) has the potential to make a significant contribution to emissions reduction in the power generation transportation and industrial sectors.
As part of the Circular Carbon Economy: Keystone to Global Sustainability series with the Center on Global Energy Policy at Columbia University SIPA this report explores the potential contribution of blue hydrogen to climate mitigation.
The report looks at:
As part of the Circular Carbon Economy: Keystone to Global Sustainability series with the Center on Global Energy Policy at Columbia University SIPA this report explores the potential contribution of blue hydrogen to climate mitigation.
The report looks at:
- Cost drivers for renewable hydrogen and hydrogen produced with fossil fuels and CCS;
- Resource requirements and cost reduction opportunities for clean hydrogen; and
- Policy recommendations to drive investment in clean hydrogen production.
- Blue hydrogen is well placed to kickstart the rapid increase in the utilisation of clean hydrogen for climate mitigation purposes but requires strong and sustained policy to incentivise investment at the rate necessary to meet global climate goals.
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.
Australian Hydrogen Hubs Study
Nov 2019
Publication
Arup have conducted interviews with targeted industry and government stakeholders to gather data and perspectives to support the development of this study. Arup have also utilised private and publicly available data sources building on recent work undertaken by Geoscience Australia and Deloitte and the comprehensive stakeholder engagement process to inform our research. This study considers the supply chain and infrastructure requirements to support the development of export and domestic hubs. The study aims to provide a succinct “Hydrogen Hubs” report for presentation to the hydrogen working group.
The hydrogen supply chain infrastructure required to produce hydrogen for export and domestic hubs was identified along with feedback from the stakeholder engagement process. These infrastructure requirements can be used to determine the factors for assessing export and domestic hub opportunities. Hydrogen production pathways transportation mechanisms and uses were also further evaluated to identify how hubs can be used to balance supply and demand of hydrogen.
A preliminary list of current or anticipated locations has been developed through desktop research Arup project knowledge and the stakeholder consultation process. Over 30 potential hydrogen export locations have been identified in Australia through desktop research and the stakeholder survey and consultation process. In addition to establishing export hubs the creation of domestic demand hubs will be essential to the development of an Australian hydrogen economy. It is for this reason that a list of criteria has been developed for stakeholders to consider in the siting and design of hydrogen hubs. The key considerations explored are based on demand supply chain infrastructure and investment and policy areas.
Based on these considerations a list of criteria were developed to assess the viability of export and domestic hydrogen hubs. Criteria relevant to assessing the suitability of export and domestic hubs include:
A framework that includes the assessment criteria has been developed to aid decision making rather than recommending specific locations that would be most appropriate for a hub. This is because there are so many dynamic factors that go into selecting a location of a hydrogen hub that it is not appropriate to be overly prescriptive or prevent stakeholders from selecting the best location themselves or from the market making decisions based on its own research and knowledge. The developed framework rather provides information and support to enable these decision-making processes.
The hydrogen supply chain infrastructure required to produce hydrogen for export and domestic hubs was identified along with feedback from the stakeholder engagement process. These infrastructure requirements can be used to determine the factors for assessing export and domestic hub opportunities. Hydrogen production pathways transportation mechanisms and uses were also further evaluated to identify how hubs can be used to balance supply and demand of hydrogen.
A preliminary list of current or anticipated locations has been developed through desktop research Arup project knowledge and the stakeholder consultation process. Over 30 potential hydrogen export locations have been identified in Australia through desktop research and the stakeholder survey and consultation process. In addition to establishing export hubs the creation of domestic demand hubs will be essential to the development of an Australian hydrogen economy. It is for this reason that a list of criteria has been developed for stakeholders to consider in the siting and design of hydrogen hubs. The key considerations explored are based on demand supply chain infrastructure and investment and policy areas.
Based on these considerations a list of criteria were developed to assess the viability of export and domestic hydrogen hubs. Criteria relevant to assessing the suitability of export and domestic hubs include:
- Health and safety provisions;
- Environmental considerations;
- Economic and social considerations;
- Land availability with appropriate zoning and buffer distances & ownership (new terminals storage solar PV industries etc.);•
- Availability of gas pipeline infrastructure;
- Availability of electricity grid connectivity backup energy supply or co-location of renewables;
- Road & rail infrastructure (site access);
- Community and environmental concerns and weather. Social licence consideration;
- Berths (berthing depth ship storage loading facilities existing LNG and/or petroleum infrastructure etc.);
- Port potential (current capacity & occupancy expandability & scalability);
- Availability of or potential for skilled workers (construction & operation);
- Availability of or potential for water (recycled & desalinated);
- Opportunity for co-location with industrial ammonia production and future industrial opportunities;
- Interest (projects priority ports state development areas politics etc.);
- Shipping distance to target market (Japan & South Korea);
- Availability of demand-based infrastructure (i.e. refuelling stations).
A framework that includes the assessment criteria has been developed to aid decision making rather than recommending specific locations that would be most appropriate for a hub. This is because there are so many dynamic factors that go into selecting a location of a hydrogen hub that it is not appropriate to be overly prescriptive or prevent stakeholders from selecting the best location themselves or from the market making decisions based on its own research and knowledge. The developed framework rather provides information and support to enable these decision-making processes.
A Solar Thermal Sorption-enhanced Steam Methane Reforming (SE-SMR) Approach and its Performance Assessment
Feb 2022
Publication
This paper proposes an integration of concentrating solar power (CSP) with a sorption-enhanced steam methane reforming (SE-SMR) process and assesses its overall solar-to-fuel conversion performance. A thermodynamic treatment of the SE-SMR process for H2 production is presented and evaluated in an innovative two reactors system configuration using CSP as a heat input. Four metal carbonate/metal oxide pairs are considered and the equilibrium thermodynamics reveals that CaCO3/CaO pair is the most suitable candidate for this process. Additionally a reactor-scale thermodynamic model is developed to determine the optimum operating conditions for the process. For the carbonation step temperatures between 700 and 900 K and steam-to-methane ratio ≥4 are found to be the most favorable. Furthermore an advanced process model which utilizes operating conditions determined from the reactor-scale model is developed to evaluate the process efficiency. The model predicts that the proposed process can achieve a solar-to-fuel efficiency ~41% for calcination temperature of 1500 K and carbonation temperature of 800 K without considering any solid heat recovery. An additional 2.5% increase in the process efficiency is feasible with the consideration of the solid heat recovery. This study shows the thermodynamic feasibility of integrating the SE-SMR process with CSP technologies.
Ex Situ Thermo-catalytic Upgrading of Biomass Pyrolysis Vapors Using a Traveling Wave Microwave Reactor
Sep 2016
Publication
Microwave heating offers a number of advantages over conventional heating methods such as rapid and volumetric heating precise temperature control energy efficiency and lower temperature gradient. In this article we demonstrate the use of 2450 MHz microwave traveling wave reactor to heat the catalyst bed for thermo-catalytic upgrading of pyrolysis vapors. HZSM-5 catalyst was tested at three different temperatures (290 330 and 370°C) at a catalyst to biomass ratio of 2. Results were compared with conventional heating and induction heating method of catalyst bed. The yields of aromatic compounds and coke deposition were dependent on temperature and method of heating. Microwave heating yielded higher aromatic compounds and lower coke deposition. Microwave heating was also energy efficient compared to conventional reactors. The rate of catalyst deterioration was lower for catalyst heated in microwave system.
Suspension Plasma Sprayed Coatings Using Dilute Hydrothermally Produced Titania Feedstocks for Photocatalytic Applications
May 2015
Publication
Titanium dioxide coatings have potential applications including photocatalysts for solar assisted hydrogen production solar water disinfection and self-cleaning windows. Herein we report the use of suspension plasma spraying (SPS) for the deposition of conformal titanium dioxide coatings. The process utilises a nanoparticle slurry of TiO2 (ca. 6 and 12 nm respectively) in water which is fed into a high temperature plasma jet (ca. 7000–20 000 K). This facilitated the deposition of adherent coatings of nanostructured titanium dioxide with predominantly anatase crystal structure. In this study suspensions of nano-titanium dioxide made via continuous hydrothermal flow synthesis (CHFS) were used directly as a feedstock for the SPS process. Coatings were produced by varying the feedstock crystallite size spray distance and plasma conditions. The coatings produced exhibited ca. 90–100% anatase phase content with the emainder being rutile (demonstrated by XRD). Phase distribution was homogenous throughout the coatings as determined by micro-Raman spectroscopy. The coatings had a granular surface with a high specific surface area and consisted of densely packed agglomerates interspersed with some melted material. All of the coatings were shown to be photoactive by means of a sacrificial hydrogen evolution test under UV radiation and compared favourably with reported values for CVD coatings and compressed discs of P25.
Kinetic Parameters Estimation via Dragonfly Algorithm (DA) and Comparison of Cylindrical and Spherical Reactors Performance for CO2 Hydrogenation to Hydrocarbons
Oct 2020
Publication
Climate change and global warming as well as growing global demand for hydrocarbons in industrial sectors make great incentives to investigate the utilization of CO2 for hydrocarbons production. Therefore finding an in-depth understanding of the CO2 hydrogenation reactors along with simulating reactor responses to different operating conditions are of paramount importance. However the reaction mechanisms for CO2 hydrogenation and their corresponding kinetic parameters have been disputable yet. In this regard considering the previously proposed Langmuir-Hinshelwood-Hougen-Watson (LHHW) mechanism which considered CO2 hydrogenation as a combination of reverse water gas shift (RWGS) and Fischer-Tropsch (FT) reactions and using a one-dimensional pseudo-homogeneous non-isothermal model kinetic parameters of the rate expressions are estimated via fitting experimental and modelling data through a novel swarm intelligence optimization technique called dragonfly algorithm (DA). The predicted reactants conversion using DA algorithm are closer to the experimental data (with about 4% error) comparing to those obtained by the artificial bee colony (ABC) algorithm and are in significant agreement with available literature data. The proposed model is used to assess the effect of reactor configuration on the performance and temperature fluctuations. Results show that axial flow spherical reactor (AFSR) and radial flow spherical reactor (RFSR) exhibiting the same surface area with that of the cylindrical reactor (CR) i.e. AFSR-2 and RFSR-2-i are the most efficient exhibiting hydrocarbons selectivity of 40.330% and 40.286% at CO2 conversion of 53.763% and 53.891%. In addition it is revealed that the location of the jacket has an essential role in controlling the reactor temperature.
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.
Microwave Absorption of Aluminum/Hydrogen Treated Titanium Dioxide Nanoparticles
Dec 2018
Publication
Interactions between incident electromagnetic energy and matter are of critical importance for numerous civil and military applications such as photocatalysis solar cells optics radar detection communications information processing and transport et al. Traditional mechanisms for such interactions in the microwave frequency mainly rely on dipole rotations and magnetic domain resonance. In this study we present the first report of the microwave absorption of Al/H2 treated TiO2 nanoparticles where the Al/H2 treatment not only induces structural and optical property changes but also largely improves the microwave absorption performance of TiO2 nanoparticles. Moreover the frequency of the microwave absorption can be finely controlled with the treatment temperature and the absorption efficiency can reach optimal values with a careful temperature tuning. A large reflection loss of −58.02 dB has been demonstrated with 3.1 mm TiO2 coating when the treating temperature is 700 °C. The high efficiency of microwave absorption is most likely linked to the disordering-induced property changes in the materials. Along with the increased microwave absorption properties are largely increased visible-light and IR absorptions and enhanced electrical conductivity and reduced skin-depth which is likely related to the interfacial defects within the TiO2 nanoparticles caused by the Al/H2 treatment.
Dual Z-scheme Charge Transfer in TiO2–Ag–Cu2O Composite for Enhanced Photocatalytic Hydrogen Generation
Apr 2015
Publication
Photocatalytic hydrogen generation is one of the most promising solutions to convert solar power into green chemical energy. In this work a multi-component TiO2–Ag–Cu2O composite was obtained through simple impregnation-calcination of Cu2O and subsequent photodeposition of Ag onto electrospun TiO2 nanotubes. The resulting TiO2–Ag–Cu2O photocatalyst exhibits excellent photocatalytic H2 evolution activity due to the synergetic effect of Ag and Cu2O on electrospun TiO2nanotubes. A dual Z-scheme charge transfer pathway for photocatalytic reactions over TiO2–Ag–Cu2O composite was proposed and discussed. This work provides a prototype for designing Z-scheme photocatalyst with Ag as an electron mediator.
Raw Biomass Electroreforming Coupled to Green Hydrogen Generation
Mar 2021
Publication
Despite the tremendous progress of coupling organic electrooxidation with hydrogen generation in a hybrid electrolysis electroreforming of raw biomass coupled to green hydrogen generation has not been reported yet due to the rigid polymeric structures of raw biomass. Herein we electrooxidize the most abundant natural amino biopolymer chitin to acetate with over 90% yield in hybrid electrolysis. The overall energy consumption of electrolysis can be reduced by 15% due to the thermodynamically and kinetically more favorable chitin oxidation over water oxidation. In obvious contrast to small organics as the anodic reactant the abundance of chitin endows the new oxidation reaction excellent scalability. A solar-driven electroreforming of chitin and chitin-containing shrimp shell waste is coupled to safe green hydrogen production thanks to the liquid anodic product and suppression of oxygen evolution. Our work thus demonstrates a scalable and safe process for resource upcycling and green hydrogen production for a sustainable energy future.
Parametric Study of Pt/C-Catalysed Hydrothermal Decarboxylation of Butyric Acid as a Potential Route for Biopropane Production
Jun 2021
Publication
Sustainable fuel-range hydrocarbons can be produced via the catalytic decarboxylation of biomass-derived carboxylic acids without the need for hydrogen addition. In this present study 5 wt% platinum on carbon (Pt/C) has been found to be an effective catalyst for hydrothermally decarboxylating butyric acid in order to produce mainly propane and carbon dioxide. However optimisation of the reaction conditions is required to minimise secondary reactions and increase hydrocarbon selectivity towards propane. To do this reactions using the catalyst with varying parameters such as reaction temperatures residence times feedstock loading and bulk catalyst loading were carried out in a batch reactor. The highest yield of propane obtained was 47 wt% (close to the theoretical decarboxylation yield of 50 wt% on butyric acid basis) corresponding to a 96% hydrocarbon selectivity towards propane. The results showed that the optimum parameters to produce the highest yield of propane from the range investigated were 0.5 g butyric acid (0.57 M aqueous solution) 1.0 g Pt/C (50 mg Pt content) at 300 °C for 1 h. The reusability of the catalyst was also investigated which showed little or no loss of catalytic activity after four cycles. This work has shown that Pt/C is a suitable and potentially hydrothermally stable heterogeneous catalyst for making biopropane a major component of bioLPG from aqueous butyric acid solutions which can be sourced from bio-derived feedstocks via acetone-butanol-ethanol (ABE) fermentation.
Life Cycle Assessment of Improved High Pressure Alkaline Electrolysis
Aug 2015
Publication
This paper investigates environmental impacts of high pressure alkaline water electrolysis systems. An advanced system with membranes on polymer basis is compared to a state-of-the-art system with asbestos membranes using a Life Cycle Assessment (LCA) approach. For the advanced system a new improved membrane technology has been investigated within the EU research project “ELYGRID”. Results indicate that most environmental impacts are caused by the electricity supply necessary for operation. During the construction phase cell stacks are the main contributor to environmental impacts. New improved membranes have relatively small contributions to impacts caused by cell construction within the advanced systems. As main outcome the systems comparison illustrates a better ecological performance of the new developed system
Onshore, Offshore or In-turbine Electrolysis? Techno-economic Overview of Alternative Integration Designs for Green Hydrogen Production into Offshore Wind Power Hubs
Aug 2021
Publication
Massive investments in offshore wind power generate significant challenges on how this electricity will be integrated into the incumbent energy systems. In this context green hydrogen produced by offshore wind emerges as a promising solution to remove barriers towards a carbon-free economy in Europe and beyond. Motivated by the recent developments in Denmark with the decision to construct the world’s first artificial Offshore Energy Hub this paper investigates how the lowest cost for green hydrogen can be achieved. A model proposing an integrated design of the hydrogen and offshore electric power infrastructure determining the levelised costs of both hydrogen and electricity is proposed. The economic feasibility of hydrogen production from 2 Offshore Wind Power Hubs is evaluated considering the combination of different electrolyser placements technologies and modes of operations. The results show that costs down to 2.4 €/kg can be achieved for green hydrogen production offshore competitive with the hydrogen costs currently produced by natural gas. Moreover a reduction of up to 13% of the cost of wind electricity is registered when an electrolyser is installed offshore shaving the peak loads.
Fuel Cells and Hydrogen Observatory Hydrogen Molecule Market Report
Sep 2021
Publication
The purpose of the hydrogen molecule market analysis is to track changes in the structure of hydrogen supply and demand in Europe. This report is mainly focused on presenting the current landscape - that will allow for future year-on-year comparisons in order to assess the progress Europe is making with regards to deployment of clean hydrogen production capacities as well as development of demand for clean hydrogen from emerging new hydrogen applications in the mobility sector or in industry. The following report summarizes the hydrogen molecule market landscape and contains data about hydrogen production and consumption in the EEA countries (EU countries together with Switzerland Norway Iceland and Liechtenstein). Hydrogen production capacity is presented by country and by technology whereas the hydrogen consumption data is presented by country and by end-use sector. The analysis undertaken for this report was completed using data available at the end of 2019. Hydrogen market (on both the demand and supply side) is dominated by ammonia and refining industries with three countries (DE NL PL) responsible for almost half hydrogen consumption. Today hydrogen is overwhelmingly produced by reforming of fossil fuels (mostly natural gas). Clean hydrogen production capacities are insignificant with blue hydrogen capacities at below 1% and green hydrogen production capacity below 0.1% of total.
Enabling Low-carbon Hydrogen Supply Chains Through Use of Biomass and Carbon Capture and Storage: A Swiss Case Study
Jul 2020
Publication
This study investigates the optimal design of low-carbon hydrogen supply chains on a national scale. We consider hydrogen production based on several feedstocks and energy sources namely water with electricity natural gas and biomass. When using natural gas we couple hydrogen production with carbon capture and storage. The design of the hydrogen biomass and carbon dioxide (CO2 ) infrastructure is performed by solving an optimization problem that determines the optimal selection size and location of the hydrogen production technologies and the optimal structure of the hydrogen biomass and CO2 O2 networks. First we investigate the rationale behind the optimal design of low-carbon hydrogen supply chains by referring to an idealized system configuration and by performing a parametric analysis of the most relevant design parameters of the supply chains such as biomass availability. This allows drawing general conclusions independent of any specific geographic features about the minimum-cost and minimum-emissions system designs and network structures. Moreover we analyze the Swiss case study to derive specific guidelines concerning the design of hydrogen supply chains deploying carbon capture and storage. We assess the impact of relevant design parameters such as location of CO2 storage facilities techno-economic features of CO2 capture technologies and network losses on the optimal supply chain design and on the competition between the hydrogen and CO2 networks. Findings highlight the fundamental role of biomass (when available) and of carbon capture and storage for decarbonizing hydrogen supply chains while transitioning to a wider deployment of renewable energy sources.
Selected Aspects of Hydrogen Production via Catalytic Decomposition of Hydrocarbons
Feb 2021
Publication
Owing to the high hydrogen content hydrocarbons are considered as an alternative source for hydrogen energy purposes. Complete decomposition of hydrocarbons results in the formation of gaseous hydrogen and solid carbonaceous by-product. The process is complicated by the methane formation reaction when the released hydrogen interacts with the formed carbon deposits. The present study is focused on the effects of the reaction mixture composition. Variations in the inlet hydrogen and methane concentrations were found to influence the carbon product’s morphology and the hydrogen production efficiency. The catalyst containing NiO (82 wt%) CuO (13 wt%) and Al2O3 (5 wt%) was prepared via a mechanochemical activating procedure. Kinetics of the catalytic process of hydrocarbons decomposition was studied using a reactor equipped with McBain balances. The effects of the process parameters were explored in a tubular quartz reactor with chromatographic analysis of the outlet gaseous products. In the latter case the catalyst was loaded piecemeal. The texture and morphology of the produced carbon deposits were investigated by nitrogen adsorption and electron microscopy techniques.
Water Photo-Electrooxidation Using Mats of TiO2 Nanorods, Surface Sensitized by a Metal–Organic Framework of Nickel and 1,2-Benzene Dicarboxylic Acid
Apr 2021
Publication
Photoanodes comprising a transparent glass substrate coated with a thin conductive film of fluorine-doped tin oxide (FTO) and a thin layer of a photoactive phase have been fabricated and tested with regard to the photo-electro-oxidation of water into molecular oxygen. The photoactive layer was made of a mat of TiO2 nanorods (TDNRs) of micrometric thickness. Individual nanorods were successfully photosensitized with nanoparticles of a metal–organic framework (MOF) of nickel and 12-benzene dicarboxylic acid (BDCA). Detailed microstructural information was obtained from SEM and TEM analysis. The chemical composition of the active layer was determined by XRD XPS and FTIR analysis. Optical properties were determined by UV–Vis spectroscopy. The water photooxidation activity was evaluated by linear sweep voltammetry and the robustness was assessed by chrono-amperometry. The OER (oxygen evolution reaction) photo-activity of these photoelectrodes was found to be directly related to the amount of MOF deposited on the TiO2 nanorods and was therefore maximized by adjusting the MOF content. The microscopic reaction mechanism which controls the photoactivity of these photoelectrodes was analyzed by photo-electrochemical impedance spectroscopy. Microscopic rate parameters are reported. These results contribute to the development and characterization of MOF-sensitized OER photoanodes.
The ‘Green’ Ni-UGSO Catalyst for Hydrogen Production under Various Reforming Regimes
Jun 2021
Publication
A new spinelized Ni catalyst (Ni-UGSO) using Ni(NO3)2·6H2O as the Ni precursor was prepared according to a less material intensive protocol. The support of this catalyst is a negative-value mining residue UpGraded Slag Oxide (UGSO) produced from a TiO2 slag production unit. Applied to dry reforming of methane (DRM) at atmospheric pressure T = 810 °C space velocity of 3400 mL/(h·g) and molar CO2/CH4 = 1.2 Ni-UGSO gives a stable over 168 h time-on-stream methane conversion of 92%. In this DRM reaction optimization study: (1) the best performance is obtained with the 10–13 wt% Ni load; (2) the Ni-UGSO catalysts obtained from two different batches of UGSO demonstrated equivalent performances despite their slight differences in composition; (3) the sulfur-poisoning resistance study shows that at up to 5.5 ppm no Ni-UGSO deactivation is observed. In steam reforming of methane (SRM) Ni-UGSO was tested at 900 °C and a molar ratio of H2O/CH4 = 1.7. In this experimental range CH4 conversion rapidly reached 98% and remained stable over 168 h time-on-stream (TOS). The same stability is observed for H2 and CO yields at around 92% and 91% respectively while H2/CO was close to 3. In mixed (dry and steam) methane reforming using a ratio of H2O/CH4 = 0.15 and CO2/CH4 = 0.97 for 74 h and three reaction temperature levels (828 °C 847 °C and 896 °C) CH4 conversion remains stable; 80% at 828 °C (26 h) 85% at 847 °C (24 h) and 95% at 896 °C (24 h). All gaseous streams have been analyzed by gas chromatography. Both fresh and used catalysts are analyzed by scanning electron microscopy-electron dispersive X-ray spectroscopy (SEM-EDXS) X-ray diffraction (XRD) and thermogravimetric analysis (TGA) coupled with mass spectroscopy (MS) and BET Specific surface. In the reducing environment of reforming such catalytic activity is mainly attributed to (a) alloys such as FeNi FeNi3 and Fe3Ni2 (reduction of NiFe2O4 FeNiAlO4) and (b) to the solid solution NiO-MgO. The latter is characterized by a molecular distribution of the catalytically active Ni phase while offering an environment that prevents C deposition due to its alkalinity.
Shining the Light on Clean Hydrogen
Jun 2021
Publication
Clean hydrogen:
- What's driving the excitement?
- Will hydrogen stay on the main stage of the energy transition?
- What is the market for clean hydrogen today?
Overview of Biomass Conversion to Electricity and Hydrogen and Recent Developments in Low-Temperature Electrochemical Approaches
Nov 2020
Publication
Biomass is plant or animal material that stores both chemical and solar energies and that is widely used for heat production and various industrial processes. Biomass contains a large amount of the element hydrogen so it is an excellent source for hydrogen production. Therefore biomass is a sustainable source for electricity or hydrogen production. Although biomass power plants and reforming plants have been commercialized it remains a difficult challenge to develop more effective and economic technologies to further improve the conversion efficiency and reduce the environmental impacts in the conversion process. The use of biomass-based flow fuel cell technology to directly convert biomass to electricity and the use of electrolysis technology to convert biomass into hydrogen at a low temperature are two new research areas that have recently attracted interest. This paper first briefly introduces traditional technologies related to the conversion of biomass to electricity and hydrogen and then reviews the new developments in flow biomass fuel cells (FBFCs) and biomass electrolysis for hydrogen production (BEHP) in detail. Further challenges in these areas are discussed.
Asymmetric Solvation of the Zinc Dimer Cation Revealed by Infrared Multiple Photon Dissociation Spectroscopy of Zn2+(H2O)n (n = 1–20)
Jun 2021
Publication
Investigating metal-ion solvation—in particular the fundamental binding interactions—enhances the understanding of many processes including hydrogen production via catalysis at metal centers and metal corrosion. Infrared spectra of the hydrated zinc dimer (Zn2+(H2O)n; n = 1–20) were measured in the O–H stretching region using infrared multiple photon dissociation (IRMPD) spectroscopy. These spectra were then compared with those calculated by using density functional theory. For all cluster sizes calculated structures adopting asymmetric solvation to one Zn atom in the dimer were found to lie lower in energy than structures adopting symmetric solvation to both Zn atoms. Combining experiment and theory the spectra show that water molecules preferentially bind to one Zn atom adopting water binding motifs similar to the Zn+(H2O)n complexes studied previously. A lower coordination number of 2 was observed for Zn2+(H2O)3 evident from the highly red-shifted band in the hydrogen bonding region. Photodissociation leading to loss of a neutral Zn atom was observed only for n = 3 attributed to a particularly low calculated Zn binding energy for this cluster size.
Past, Present and Near Future: An Overview of Closed, Running and Planned Biomethanation Facilities in Europe
Sep 2021
Publication
The power-to-methane technology is promising for long-term high-capacity energy storage. Currently there are two different industrial-scale methanation methods: the chemical one (based on the Sabatier reaction) and the biological one (using microorganisms for the conversion). The second method can be used not only to methanize the mixture of pure hydrogen and carbon dioxide but also to methanize the hydrogen and carbon dioxide content of low-quality gases such as biogas or deponia gas enriching them to natural gas quality; therefore the applicability of biomethanation is very wide. In this paper we present an overview of the existing and planned industrial-scale biomethanation facilities in Europe as well as review the facilities closed in recent years after successful operation in the light of the scientific and socioeconomic context. To outline key directions for further developments this paper interconnects biomethanation projects with the competitiveness of the energy sector in Europe for the first time in the literature. The results show that future projects should have an integrative view of electrolysis and biomethanation as well as hydrogen storage and utilization with carbon capture and utilization (HSU&CCU) to increase sectoral competitiveness by enhanced decarbonization.
Setting Thresholds to Define Indifferences and Preferences in PROMETHEE for Life Cycle Sustainability Assessment of European Hydrogen Production
Jun 2021
Publication
The Life Cycle Sustainability Assessment (LCSA) is a proven method for sustainability assessment. However the interpretation phase of an LCSA is challenging because many different single results are obtained. Additionally performing a Multi-Criteria Decision Analysis (MCDA) is one way—not only for LCSA—to gain clarity about how to interpret the results. One common form of MCDAs are outranking methods. For these type of methods it becomes of utmost importance to clarify when results become preferable. Thus thresholds are commonly used to prevent decisions based on results that are actually indifferent between the analyzed options. In this paper a new approach is presented to identify and quantify such thresholds for Preference Ranking Organization METHod for Enrichment Evaluation (PROMETHEE) based on uncertainty of Life Cycle Impact Assessment (LCIA) methods. Common thresholds and this new approach are discussed using a case study on finding a preferred location for sustainable industrial hydrogen production comparing three locations in European countries. The single LCSA results indicated different preferences for the environmental economic and social assessment. The application of PROMETHEE helped to find a clear solution. The comparison of the newly-specified thresholds based on LCIA uncertainty with default thresholds provided important insights of how to interpret the LCSA results regarding industrial hydrogen production.
Energy Optimization of a Sulfur-Iodine Thermochemical Nuclear Hydrogen Production Cycle
Dec 2021
Publication
The use of nuclear reactors is a large studied possible solution for thermochemical water splitting cycles. Nevertheless there are several problems that have to be solved. One of them is to increase the efficiency of the cycles. Hence in this paper a thermal energy optimization of a SulfureIodine nuclear hydrogen production cycle was performed by means a heuristic method with the aim of minimizing the energy targets of the heat exchanger network at different minimum temperature differences. With this method four different heat exchanger networks are proposed. A reduction of the energy requirements for cooling ranges between 58.9-59.8% and 52.6-53.3% heating compared to the reference design with no heat exchanger network. With this reduction the thermal efficiency of the cycle increased in about 10% in average compared to the reference efficiency. This improves the use of thermal energy of the cycle.
The Impact of Operating Conditions on the Performance of a CH4 Dry Reforming Membrane Reactor for H2 Production
May 2020
Publication
Biogas is a promising resource for the production of H2 since it liberates energy by recycling waste along with the reduction of CO2. In this paper the biogas dry reforming membrane reactor is proposed to produce H2 for use in fuel cells. Pd/Cu alloy membrane is used to enhance the performance of the biogas dry reforming reactor. This study aims at understanding the effect of operating parameters such as feed ratio of sweep gas pressure in the reactor and reaction temperature on the performance of the biogas dry reforming membrane reactor. The effect of the molar ratio of the supplied CH4:CO2 feed ratio of the sweep gas and the valve located at the outlet of the reaction chamber on the performance of biogas dry reforming are investigated. Besides the thermal efficiency of the proposed reactor is also evaluated. The results show that the concentration of H2 in the closed valve condition is higher than that of the open valve and the optimum feed ratio of the sweep gas to produce H2 is 1 irrespective of the molar ratio of supplied CH4:CO2. Also H2 selectivity and CO selectivity increases and decreases respectively when the reaction temperature increases irrespective of the molar ratio of supplied CH4:CO2. Therefore the thermal efficiency of the closed valve is higher than that of the opened valve. Also the thermal efficiency is the maximum when the feed ratio of the sweep gas is 1 due to high H2 production performance.
A Holistic Consideration of Megawatt Electrolysis as a Key Component of Sector Coupling
May 2022
Publication
In the future hydrogen (H2) will play a significant role in the sustainable supply of energy and raw materials to various sectors. Therefore the electrolysis of water required for industrial‐ scale H2 production represents a key component in the generation of renewable electricity. Within the scope of fundamental research work on cell components for polymer electrolyte membrane (PEM) electrolyzers and application‐oriented living labs an MW electrolysis system was used to further improve industrial‐scale electrolysis technology in terms of its basic structure and systems‐ related integration. The planning of this work as well as the analytical and technical approaches taken along with the essential results of research and development are presented herein. The focus of this study is the test facility for a megawatt PEM electrolysis stack with the presentation of the design processing and assembly of the main components of the facility and stack.
Flare Gas Monetization and Greener Hydrogen Production via Combination with Crypto Currency Mining and Carbon Dioxide Capture
Jan 2022
Publication
In view of the continuous debates on the environmental impact of blockchain technologies in particular crypto currency mining accompanied by severe carbon dioxide emissions a technical solution has been considered assuming direct monetization of associated petroleum gas currently being flared. The proposed approach is based on the technology of low-temperature steam reforming of hydrocarbons which allows flare gas conditioning towards the requirements for fuel for gas piston and gas turbine power plants. The generation of electricity directly at the oil field and its use for on-site crypto currency mining transforms the process of wasteful flaring of valuable hydrocarbons into an economically attractive integrated processing of natural resources. The process is not carbon neutral and is not intended to compete zero-emission technologies but its combination with technologies for carbon dioxide capture and re-injection into the oil reservoir can both enhance the oil recovery and reduce carbon dioxide emissions into the atmosphere. The produced gas can be used for local transport needs while the generated heat and electricity can be utilized for on-site food production and biological carbon dioxide capture in vertical greenhouse farms. The suggested approach allows significant decrease in the carbon dioxide emissions at oil fields and although it may seem paradoxically on-site cryptocurrency mining actually may lead to a decrease in the carbon footprint. The amount of captured CO2 could be transformed into CO2 emission quotas which can be spent for the production of virtually “blue” hydrogen by steam reforming of natural gas in locations where the CO2 capture is technically impossible and/or unprofitable.
H2 Green Hydrogen Discussion Paper: Victorian Hydrogen Investment Program
Nov 2019
Publication
This discussion paper is for stakeholders who would like to shape the development of Victoria’s emerging green hydrogen sector identifying competitive advantages and priority focus areas for industry and the Victorian Government.<br/>The Victorian Government is using this paper to focus on the economic growth and sector development opportunities emerging for a Victorian hydrogen industry powered by renewable energy also known as ‘green’ hydrogen. In addition this paper seeks input from all stakeholders on how where and when the Victorian Government can act to establish a thriving green hydrogen economy.<br/>Although green hydrogen is the only type of hydrogen production within the scope of this discussion paper the development of the VHIP aligns with the policies projects and initiatives which support these other forms of hydrogen production. The VHIP is considering the broad policy landscape and actively coordinating with related hydrogen programs policies and strategies under development including the Council of Australian Governments (COAG) Energy Council’s National Hydrogen Strategy to ensure a complementary approach. In Victoria there are several programs and strategies in development and underway that have linkages with hydrogen and the VHIP.
Photoelectrochemical Hydrogen Production by Screen-Printed Copper Oxide Electrodes
May 2021
Publication
In this work copper oxides-based photocathodes for photoelectrochemical cells (PEC) were produced for the first time by screen printing. A total 7 × 10−3 g/m2 glycerine trioleate was found as optimum deflocculant amount to assure stable and homogeneous inks based on CuO nano-powder. The inks were formulated considering different binder amounts and deposited producing films with homogenous thickness microstructure and roughness. The as-produced films were thermally treated to obtain Cu2O- and Cu2O/CuO-based electrodes. The increased porosity obtained by adding higher amounts of binder in the ink positively affected the electron transfer from the surface of the electrode to the electrolyte thus increasing the corresponding photocurrent values. Moreover the Cu2O/CuO system showed a higher charge carrier and photocurrent density than the Cu2O-based one. The mixed Cu2O/CuO films allowed the most significant hydrogen production especially in slightly acid reaction conditions.
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.
Thermodynamic Analysis of Hydrogen Production via Chemical Looping Steam Methane Reforming Coupled with In Situ CO2 Capture
Dec 2014
Publication
A detailed thermodynamic analysis of the sorption enhanced chemical looping reforming of methane (SE-CL-SMR) using CaO and NiO as CO2 sorbent and oxygen transfer material (OTM) respectively was conducted. Conventional reforming (SMR) and sorption enhanced reforming (SE-SMR) were also investigated for comparison reasons. The results of the thermodynamic analysis show that there are significant advantages of both sorption enhanced processes compared to conventional reforming. The presence of CaO leads to higher methane conversion and hydrogen purity at low temperatures. Addition of the OTM in the SECL-SMR process concept minimizes the thermal requirements and results in superior performance compared to SE-SMR and SMR in a two-reactor concept with use of pure oxygen as oxidant/sweep gas.
Hydrogen Production in Methane Decomposition Reactor Using Solar Thermal Energy
Nov 2021
Publication
This study investigates the decomposition of methane using solar thermal energy as a heat source. Instead of the direct thermal decomposition of the methane at a temperature of 1200 ◦C or higher a catalyst coated with carbon black on a metal foam was used to lower the temperature and activation energy required for the reaction and to increase the yield. To supply solar heat during the reaction a reactor suitable for a solar concentrating system was developed. In this process a direct heating type reactor with quartz was initially applied and a number of problems were identified. An indirect heating type reactor with an insulated cavity and a rotating part was subsequently developed followed by a thermal barrier coating application. Methane decomposition experiments were conducted in a 40 kW solar furnace at the Korea Institute of Energy Research. Conversion rates of 96.7% and 82.6% were achieved when the methane flow rate was 20 L/min and 40 L/min respectively.
Analysing Future Demand, Supply, and Transport of Hydrogen
Jun 2021
Publication
Hydrogen is crucial to Europe’s transformation into a climate-neutral continent by mid-century. This study concludes that the European Union (EU) and UK could see a hydrogen demand of 2300 TWh (2150-2750 TWh) by 2050. This corresponds to 20-25% of EU and UK final energy consumption by 2050. Achieving this future role of hydrogen depends on many factors including market frameworks legislation technology readiness and consumer choice.
The document can be download on their website
The document can be download on their website
A Perspective on Hydrogen Investment, Deployment and Cost Competitiveness
Feb 2021
Publication
Deployment and investments in hydrogen have accelerated rapidly in response to government commitments to deep decarbonisation establishing hydrogen as a key component in the energy transition.
To help guide regulators decision-makers and investors the Hydrogen Council collaborated with McKinsey & Company to release the report ‘Hydrogen Insights 2021: A Perspective on Hydrogen Investment Deployment and Cost Competitiveness’. The report offers a comprehensive perspective on market deployment around the world investment momentum as well as implications on cost competitiveness of hydrogen solutions.
The document can be downloaded from their website
To help guide regulators decision-makers and investors the Hydrogen Council collaborated with McKinsey & Company to release the report ‘Hydrogen Insights 2021: A Perspective on Hydrogen Investment Deployment and Cost Competitiveness’. The report offers a comprehensive perspective on market deployment around the world investment momentum as well as implications on cost competitiveness of hydrogen solutions.
The document can be downloaded from their website
A Process for Hydrogen Production from the Catalytic Decomposition of Formic Acid over Iridium—Palladium Nanoparticles
Jun 2021
Publication
The present study investigates a process for the selective production of hydrogen from the catalytic decomposition of formic acid in the presence of iridium and iridium–palladium nanoparticles under various conditions. It was found that a loading of 1 wt.% of 2% palladium in the presence of 1% iridium over activated charcoal led to a 43% conversion of formic acid to hydrogen at room temperature after 4 h. Increasing the temperature to 60 °C led to further decomposition and an improvement in conversion yield to 63%. Dilution of formic acid from 0.5 to 0.2 M improved the decomposition reaching conversion to 81%. The reported process could potentially be used in commercial applications.
A Mountain to Climb? Tracking Progress in Scaling Up Renewable Gas Production in Europe
Oct 2019
Publication
In the last couple of years there has been increasing recognition by key players in the European gas industry that to mitigate the risk of terminal decline in the context of a decarbonising energy system there will need to be rapid scale up of decarbonised gas. This has led to several projections of the scale of decarbonised gas which could potentially be supplied by 2030 2040 or 2050. This paper joint with the Sustainable Gas Institute at Imperial College London considers the very significant rate of scale up and the significant cost reductions contemplated by such projections. Based on a database of actual announced projects (both committed and in earlier stages of development) for production of decarbonised gas it then considers the extent to which project activity is consistent with meeting the ambitious projections. It identifies a significant gap in current levels of activity largely because there is not yet sufficient economic incentive for investors to develop the required projects. It is intended that this paper will form the basis of continued tracking of the level of activity over the coming years to help inform industry players of further actions which may be required.
Platinum Single-atom Catalyst Coupled with Transition Metal/Metal Oxide Heterostructure for Accelerating Alkaline Hydrogen Evolution Reaction
Jun 2021
Publication
Single-atom catalysts provide an effective approach to reduce the amount of precious metals meanwhile maintain their catalytic activity. However the sluggish activity of the catalysts for alkaline water dissociation has hampered advances in highly efficient hydrogen production. Herein we develop a single-atom platinum immobilized NiO/Ni heterostructure (PtSA-NiO/Ni) as an alkaline hydrogen evolution catalyst. It is found that Pt single atom coupled with NiO/Ni heterostructure enables the tunable binding abilities of hydroxyl ions (OH*) and hydrogen (H*) which efficiently tailors the water dissociation energy and promotes the H* conversion for accelerating alkaline hydrogen evolution reaction. A further enhancement is achieved by constructing PtSA-NiO/Ni nanosheets on Ag nanowires to form a hierarchical three-dimensional morphology. Consequently the fabricated PtSA-NiO/Ni catalyst displays high alkaline hydrogen evolution performances with a quite high mass activity of 20.6 A mg−1 for Pt at the overpotential of 100 mV significantly outperforming the reported catalysts.
Nickel-Based Electrocatalysts for Water Electrolysis
Feb 2022
Publication
Currently hydrogen production is based on the reforming process leading to the emission of pollutants; therefore a substitute production method is imminently required. Water electrolysis is an ideal alternative for large-scale hydrogen production as it does not produce any carbon-based pollutant byproducts. The production of green hydrogen from water electrolysis using intermittent sources (e.g. solar and eolic sources) would facilitate clean energy storage. However the electrocatalysts currently required for water electrolysis are noble metals making this potential option expensive and inaccessible for industrial applications. Therefore there is a need to develop electrocatalysts based on earth-abundant and low-cost metals. Nickel-based electrocatalysts are a fitting alternative because they are economically accessible. Extensive research has focused on developing nickel-based electrocatalysts for hydrogen and oxygen evolution. Theoretical and experimental work have addressed the elucidation of these electrochemical processes and the role of heteroatoms structure and morphology. Even though some works tend to be contradictory they have lit up the path for the development of efficient nickel-based electrocatalysts. For these reasons a review of recent progress is presented herein.
Hydrogen-Rich Gas Production from Two-Stage Catalytic Pyrolysis of Pine Sawdust with Nano-NiO/Al2O3 Catalyst
Feb 2022
Publication
Hydrogen production from biomass pyrolysis is economically and technologically attractive from the perspectives of energy and the environment. The two-stage catalytic pyrolysis of pine sawdust for hydrogen-rich gas production is investigated using nano-NiO/Al2O3 as the catalyst at high temperatures. The influences of residence time (0–30 s) and catalytic temperature (500–800 ◦C) on pyrolysis performance are examined in the distribution of pyrolysis products gas composition and gas properties. The results show that increasing the residence time decreased the solid and liquid products but increased gas products. Longer residence times could promote tar cracking and gas-phase conversion reactions and improve the syngas yield H2/CO ratio and carbon conversion. The nano-NiO/A12O3 exhibits excellent catalytic activity for tar removal with a tar conversion rate of 93% at 800 ◦C. The high catalytic temperature could significantly improve H2 and CO yields by enhancing the decomposition of tar and gas-phase reactions between CO2 and CH4 . The increasing catalytic temperature increases the dry gas yield and carbon conversion but decreases the H2/CO ratio and low heating value.
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.
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