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.
Water Photo-Oxidation Reaction on Clean and Doped Two-Dimensional Graphitic C2N
Apr 2020
Publication
In the search for new efficient photo-catalysts for hydrogen production through water splitting the main attention has been paid to tuning the band gap width and its position with respect to vacuum level. However actual electro-catalytic activity for the water oxidation reaction on a catalyst surface is no less important than those quantities. In this work we evaluate from first principles the thermodynamics of the reaction on relatively new candidates for water splitting: two-dimensional C2N and that doped with phosphorus. We find that the 4-step reaction usually expected for water splitting will not proceed on these systems resulting in oxygen atoms left strongly adsorbed to the surface. Another option a 3-step reaction is also found to be unfavorable. We also test an effect of higher oxygen coverage on the reaction thermodynamics as suggested elsewhere. We find that indeed the doubled O-coverage makes the 4-step reaction feasible for the doped C2N. However an unacceptably high anode potential is required to make this reaction proceed. We thus conclude that the materials under consideration may not be efficient electro-catalysts for water splitting.
A Review on Recent Advances in Hydrogen Energy, Fuel Cell, Biofuel and Fuel Refining via Ultrasound Process Intensification
Mar 2021
Publication
Hydrogen energy is one of the most suitable green substitutes for harmful fossil fuels and has been investigated widely. This review extensively compiles and compares various methodologies used in the production storage and usage of hydrogen. Sonochemistry is an emerging synthesis process and intensification technique adapted for the synthesis of novel materials. It manifests acoustic cavitation phenomena caused by ultrasound where higher rates of reactions occur locally. The review discusses the effectiveness of sonochemical routes in developing fuel cell catalysts fuel refining biofuel production chemical processes for hydrogen production and the physical chemical and electrochemical hydrogen storage techniques. The operational parameters and environmental conditions used during ultrasonication also influence the production rates which have been elucidated in detail. Hence this review's major focus addresses sonochemical methods that can contribute to the technical challenges involved in hydrogen usage for energy.
Suitable Site Selection for Solar‐Based Green Hydrogen in Southern Thailand Using GIS‐MCDM Approach
May 2022
Publication
Climate change mitigation efforts are in dire need of greener and more versatile fuel al‐ ternatives to fossil fuels. Green hydrogen being both renewable and flexible has the potential to offset fossil fuels as the primary fuel source. Countries around the world are planning to develop their green hydrogen industries and accurate potential assessment is vital. This study employed the consolidation of a geographic information system (GIS) and the analytical hierarchy process (AHP) technique of multicriteria decision making (MCDM) for the potential assessment of green hydrogen in southern Thailand through the selection of suitable sites for solar‐based green hy‐ drogen production. Technical economic and environmental criteria with 10 sub‐criteria were con‐ sidered for the selection of suitable sites. With 0.243 (24.3%) weight the distance from protected areas turned out to be the most important sub‐criterion whereas the criterion of elevation with a 0.017 (1.7%) score was considered the least important. Southern Thailand is a well‐suited area for solar‐based green hydrogen production with a 4302 km2 area of high suitability and a 3350 km2 area of moderate suitability. These suitable areas can be utilized to develop the green hydrogen industry of Thailand and the method developed can be employed for the assessment of green hydrogen potential in other parts of the country. Studies like these are vital for the development of green hydrogen road maps for Thailand to develop its hydrogen policy and promote investments in the sector.
Hydrous Hydrazine Decomposition for Hydrogen Production Using of Ir/CeO2: Effect of Reaction Parameters on the Activity
May 2021
Publication
In the present work an Ir/CeO2 catalyst was prepared by the deposition–precipitation method and tested in the decomposition of hydrazine hydrate to hydrogen which is very important in the development of hydrogen storage materials for fuel cells. The catalyst was characterised using different techniques i.e. X-ray photoelectron spectroscopy (XPS) transmission electron microscopy (TEM) scanning electron microscopy (SEM) equipped with X-ray detector (EDX) and inductively coupled plasma—mass spectroscopy (ICP-MS). The effect of reaction conditions on the activity and selectivity of the material was evaluated in this study modifying parameters such as temperature the mass of the catalyst stirring speed and concentration of base in order to find the optimal conditions of reaction which allow performing the test in a kinetically limited regime.
Novel Biofuel Cell Using Hydrogen Generation of Photosynthesis
Nov 2020
Publication
Energies based on biomaterials attract a lot of interest as next-generation energy because biomaterials are environmentally friendly materials and abundant in nature. Fuel cells are also known as the clean and important next-generation source of energy. In the present study to develop the fuel cell based on biomaterials a novel biofuel cell which consists of collagen electrolyte and the hydrogen fuel generated from photochemical system II (PSII) in photosynthesis has been fabricated and its property has been investigated. It was found that the PSII solution in which PSII was extracted from the thylakoid membrane using a surfactant generates hydrogen by the irradiation of light. The typical hydrogen-generating rate is approximately 7.41 × 1014 molecules/s for the light intensity of 0.5 mW/cm2 for the PSII solution of 5 mL. The biofuel cell using the PSII solution as the fuel exhibited approximately 0.12 mW/cm2 . This result indicates that the fuel cell using the collagen electrolyte and the hydrogen fuel generated from PSII solution becomes the new type of biofuel cell and will lead to the development of the next-generation energy
Electronic Structure and d-Band Center Control Engineering over Ni-Doped CoP3 Nanowall Arrays for Boosting Hydrogen Production
Jun 2021
Publication
To address the challenge of highly efficient water splitting into H2 successful fabrication of novel porous three-dimensional Ni-doped CoP3 nanowall arrays on carbon cloth was realized resulting in an effective self-supported electrode for the electrocatalytic hydrogen-evolution reaction. The synthesized samples exhibit rough curly and porous structures which are beneficial for gaseous transfer and diffusion during the electrocatalytic process. As expected the obtained Ni-doped CoP3 nanowall arrays with a doping concentration of 7% exhibit the promoted electrocatalytic activity. The achieved overpotentials of 176 mV for the hydrogen-evolution reaction afford a current density of 100 mA cm−2 which indicates that electrocatalytic performance can be dramatically enhanced via Ni doping. The Ni-doped CoP3 electrocatalysts with increasing catalytic activity should have significant potential in the field of water splitting into H2. This study also opens an avenue for further enhancement of electrocatalytic performance through tuning of electronic structure and d-band center by doping.
Towards the Rational Design of Stable Electrocatalysts for Green Hydrogen Production
Feb 2022
Publication
Now it is time to set up reliable water electrolysis stacks with active and robust electro‐ catalysts to produce green hydrogen. Compared with catalytic kinetics much less attention has been paid to catalyst stability and the weak understanding of the catalyst deactivation mechanism restricts the design of robust electrocatalysts. Herein we discuss the issues of catalysts’ stability evaluation and characterization and the degradation mechanism. The systematic understanding of the degradation mechanism would help us to formulate principles for the design of stable catalysts. Particularly we found that the dissolution rate for different 3d transition metals differed greatly: Fe dissolves 114 and 84 times faster than Co and Ni. Based on this trend we designed Fe@Ni and FeNi@Ni core‐shell structures to achieve excellent stability in a 1 A cm−2 current density as well as good catalytic activity at the same time
Spin Pinning Effect to Reconstructed Oxyhydroxide Layer on Ferromagnetic Oxides for Enhanced Water Oxidation
Jun 2021
Publication
Producing hydrogen by water electrolysis suffers from the kinetic barriers in the oxygen evolution reaction (OER) that limits the overall efficiency. With spin-dependent kinetics in OER to manipulate the spin ordering of ferromagnetic OER catalysts (e.g. by magnetization) can reduce the kinetic barrier. However most active OER catalysts are not ferromagnetic which makes the spin manipulation challenging. In this work we report a strategy with spin pinning effect to make the spins in paramagnetic oxyhydroxides more aligned for higher intrinsic OER activity. The spin pinning effect is established in oxideFM/oxyhydroxide interface which is realized by a controlled surface reconstruction of ferromagnetic oxides. Under spin pinning simple magnetization further increases the spin alignment and thus the OER activity which validates the spin effect in rate-limiting OER step. The spin polarization in OER highly relies on oxyl radicals (O∙) created by 1st dehydrogenation to reduce the barrier for subsequent O-O coupling.
Storable Energy Production from Wind over Water
Apr 2020
Publication
The current status of a project is described which aims to demonstrate the technical and economic feasibility of converting the vast wind energy available over the globe’s oceans and lakes into storable energy. To this end autonomous high-performance sailing ships are equipped with hydrokinetic turbines whose output is stored either in electric batteries or is fed into electrolysers to produce hydrogen which then is compressed and stored in tanks. In the present paper the previous analytical studies which showed the potential of this “energy ship concept” are summarized and progress on its hardware demonstration is reported involving the conversion of a model sailboat to autonomous operation. The paper concludes with a discussion of the potential of this concept to achieve the IPCC-mandated requirement of reducing the global CO2 emissions by about 45% by 2030 reaching net zero by 2050.
Fabrication of Highly Textured 2D SnSe Layers with Tunable Electronic Properties for Hydrogen Evolution
Jun 2021
Publication
Hydrogen is regarded to be one of the most promising renewable and clean energy sources. Finding a highly efficient and cost-effective catalyst to generate hydrogen via water splitting has become a research hotspot. Two-dimensional materials with exotic structural and electronic properties have been considered as economical alternatives. In this work 2D SnSe films with high quality of crystallinity were grown on a mica substrate via molecular beam epitaxy. The electronic property of the prepared SnSe thin films can be easily and accurately tuned in situ by three orders of magnitude through the controllable compensation of Sn atoms. The prepared film normally exhibited p-type conduction due to the deficiency of Sn in the film during its growth. First-principle calculations explained that Sn vacancies can introduce additional reactive sites for the hydrogen evolution reaction (HER) and enhance the HER performance by accelerating electron migration and promoting continuous hydrogen generation which was mirrored by the reduced Gibbs free energy by a factor of 2.3 as compared with the pure SnSe film. The results pave the way for synthesized 2D SnSe thin films in the applications of hydrogen production.
Site-Dependent Environmental Impacts of Industrial Hydrogen Production by Alkaline Water Electrolysis
Jun 2017
Publication
Industrial hydrogen production via alkaline water electrolysis (AEL) is a mature hydrogen production method. One argument in favor of AEL when supplied with renewable energy is its environmental superiority against conventional fossil-based hydrogen production. However today electricity from the national grid is widely utilized for industrial applications of AEL. Also the ban on asbestos membranes led to a change in performance patterns making a detailed assessment necessary. This study presents a comparative Life Cycle Assessment (LCA) using the GaBi software (version 6.115 thinkstep Leinfelden-Echterdingen Germany) revealing inventory data and environmental impacts for industrial hydrogen production by latest AELs (6 MW Zirfon membranes) in three different countries (Austria Germany and Spain) with corresponding grid mixes. The results confirm the dependence of most environmental effects from the operation phase and specifically the site-dependent electricity mix. Construction of system components and the replacement of cell stacks make a minor contribution. At present considering the three countries AEL can be operated in the most environmentally friendly fashion in Austria. Concerning the construction of AEL plants the materials nickel and polytetrafluoroethylene in particular used for cell manufacturing revealed significant contributions to the environmental burden.
Wittichenite Semiconductor of Cu3BiS3 Films for Efficient Hydrogen Evolution from Solar Driven Photoelectrochemical Water Splitting
Jun 2021
Publication
A highly efficient low-cost and environmentally friendly photocathode with long-term stability is the goal of practical solar hydrogen evolution applications. Here we found that the Cu3BiS3 film-based photocathode meets the abovementioned requirements. The Cu3BiS3-based photocathode presents a remarkable onset potential over 0.9 VRHE with excellent photoelectrochemical current densities (~7 mA/cm2 under 0 VRHE) and appreciable 10-hour long-term stability in neutral water solutions. This high onset potential of the Cu3BiS3-based photocathode directly results in a good unbiased operating photocurrent of ~1.6 mA/cm2 assisted by the BiVO4 photoanode. A tandem device of Cu3BiS3-BiVO4 with an unbiased solar-to-hydrogen conversion efficiency of 2.04% is presented. This tandem device also presents high stability over 20 hours. Ultimately a 5 × 5 cm2 large Cu3BiS3-BiVO4 tandem device module is fabricated for standalone overall solar water splitting with a long-term stability of 60 hours.
A Combined Chemical-Electrochemical Process to Capture CO2 and Produce Hydrogen and Electricity
Sep 2021
Publication
Several carbon sequestration technologies have been proposed to utilize carbon dioxide (CO2 ) to produce energy and chemical compounds. However feasible technologies have not been adopted due to the low efficiency conversion rate and high-energy requirements. Process intensification increases the process productivity and efficiency by combining chemical reactions and separation operations. In this work we present a model of a chemical-electrochemical cyclical process that can capture carbon dioxide as a bicarbonate salt. The proposed process also produces hydrogen and electrical energy. Carbon capture is enhanced by the reaction at the cathode that displaces the equilibrium into bicarbonate production. Literature data show that the cyclic process can produce stable operation for long times by preserving ionic balance using a suitable ionic membrane that regulates ionic flows between the two half-cells. Numerical simulations have validated the proof of concept. The proposed process could serve as a novel CO2 sequestration technology while producing electrical energy and hydrogen.
Study of Activity and Super-Capacitance Exhibited by Bifunctional Raney 2.0 Catalyst for Alkaline Water-Splitting Electrolysis
Dec 2020
Publication
Low-cost high-performance coatings for hydrogen production via electrolytic water-splitting are of great importance for de-carbonising energy. In this study the Raney2.0 coating was analysed using various electrochemical techniques to assess its absolute performance and it was confirmed to have an extremely low overpotential for hydrogen evolution of just 28 mV at 10 mA/cm2. It was also confirmed to be an acceptable catalyst for oxygen evolution making it the highest performing simple bifunctional electrocatalyst known. The coating exhibits an extremely high capacitance of up to 1.7 F/cm2 as well as being able to store 0.61 J/cm2 in the form of temporary hydride deposits. A new technique is presented that performs a best-fit of a transient simulation of an equivalent circuit containing a constant phase element to cyclic voltammetry measurements. From this the roughness factor of the coating was calculated to be approximately 40000 which is the highest figure ever reported for this type of material. The coating is therefore an extremely useful improved bifunctional coating for the continued roll-out of alkaline electrolysis for large-scale renewable energy capture via hydrogen production.
Comparison of Hydrogen Powertrains with the Battery Powered Electric Vehicle and Investigation of Small-Scale Local Hydrogen Production Using Renewable Energy
Jan 2021
Publication
Climate change is one of the major problems that people face in this century with fossil fuel combustion engines being huge contributors. Currently the battery powered electric vehicle is considered the predecessor while hydrogen vehicles only have an insignificant market share. To evaluate if this is justified different hydrogen power train technologies are analyzed and compared to the battery powered electric vehicle. Even though most research focuses on the hydrogen fuel cells it is shown that despite the lower efficiency the often-neglected hydrogen combustion engine could be the right solution for transitioning away from fossil fuels. This is mainly due to the lower costs and possibility of the use of existing manufacturing infrastructure. To achieve a similar level of refueling comfort as with the battery powered electric vehicle the economic and technological aspects of the local small-scale hydrogen production are being investigated. Due to the low efficiency and high prices for the required components this domestically produced hydrogen cannot compete with hydrogen produced from fossil fuels on a larger scale
Estimation of Hydrogen Production using Wind Energy in Algeria
Aug 2015
Publication
In response to problems involved in the current crisis of petrol in Algeria with the decrease in the price of the oil barrel the rate of growth in domestic electricity demand and with an associated acceleration of global warming as a result of significantly increased greenhouse gas (GHG) emissions renewable energy seems today as a clean and strategic substitution for the next decades. However the greatest obstacles which face electric energy comes from renewable energy systems are often referred to the intermittency of these sources as well as storage and transport problems the need for their conversion into a versatile energy carrier in its use storable transportable and environmentally acceptable are required. Among all the candidates answering these criteria hydrogen presents the best answer. In the present work particular attention is paid to the production of hydrogen from wind energy. The new wind map of Algeria shows that the highest potential wind power was found in Adrar Hassi-R'Mel and Tindouf regions. The data obtained from these locations have been analyzed using Weibull probability distribution function. The wind energy produced in these locations is exploited for hydrogen production through water electrolysis. The objective of this paper is to realize a technological platform allowing the evaluation of emergent technologies of hydrogen production from wind energy using four wind energy conversion systems of 600 1250 1500 and 2000 kW rated capacity. The feasibility study shows that using wind energy in the selected sites is a promising solution. It is shown that the turbine " De Wind D7" is sufficient to supply the electricity and hydrogen with a least cost and a height capacity factor. The minimum cost of hydrogen production of 1.214 $/kgH2 is obtained in Adrar.
An Investigation of a (Vinylbenzyl) Trimethylammonium and N-Vinylimidazole-Substituted Poly (Vinylidene Fluoride-Co-Hexafluoropropylene) Copolymer as an Anion-Exchange Membrane in a Lignin-Oxidising Electrolyser
Jun 2021
Publication
Electrolysis is seen as a promising route for the production of hydrogen from water as part of a move to a wider “hydrogen economy”. The electro-oxidation of renewable feedstocks offers an alternative anode couple to the (high-overpotential) electrochemical oxygen evolution reaction for developing low-voltage electrolysers. Meanwhile the exploration of new membrane materials is also important in order to try and reduce the capital costs of electrolysers. In this work we synthesise and characterise a previously unreported anion-exchange membrane consisting of a fluorinated polymer backbone grafted with imidazole and trimethylammonium units as the ion-conducting moieties. We then investigate the use of this membrane in a lignin-oxidising electrolyser. The new membrane performs comparably to a commercially-available anion-exchange membrane (Fumapem) for this purpose over short timescales (delivering current densities of 4.4 mA cm−2 for lignin oxidation at a cell potential of 1.2 V at 70 °C during linear sweep voltammetry) but membrane durability was found to be a significant issue over extended testing durations. This work therefore suggests that membranes of the sort described herein might be usefully employed for lignin electrolysis applications if their robustness can be improved.
Low-Cost and Durable Bipolar Plates for Proton Exchange Membrane Electrolyzers
Mar 2017
Publication
Cost reduction and high efficiency are the mayor challenges for sustainable H2 production via proton exchange membrane (PEM) electrolysis. Titanium-based components such as bipolar plates (BPP) have the largest contribution to the capital cost. This work proposes the use of stainless steel BPPs coated with Nb and Ti by magnetron sputtering physical vapor deposition (PVD) and vacuum plasma spraying (VPS) respectively. The physical properties of the coatings are thoroughly characterized by scanning electron atomic force microscopies (SEM AFM); and X-ray diffraction photoelectron spectroscopies (XRD XPS). The Ti coating (50μm) protects the stainless steel substrate against corrosion while a 50- fold thinner layer of Nb decreases the contact resistance by almost one order of magnitude. The Nb/ Ti-coated stainless steel bipolar BPPs endure the harsh environment of the anode for more than 1000h of operation under nominal conditions showing a potential use in PEM electrolyzers for large-scale H2 production from renewables.
Electrocatalytic Properties for the Hydrogen Evolution of the Electrodeposited Ni–Mo/WC Composites
May 2021
Publication
The catalytical activity for the hydrogen evolution reaction (HER) of the electrodeposited Ni–Mo/WC composites is examined in 1 M KOH solution. The structure surface morphology and surface composition is investigated using the scanning electron microscopy X-ray diffraction and X-ray photoelectron spectroscopy. The electrocatalytic properties for the HER is evaluated based on the cathodic polarization electrochemical impedance cyclic voltammetry and chronopotentiometry methods. The obtained results prove the superior catalytic activity for the HER of Ni–Mo/WC composites to Ni–Mo alloy. The catalytic activity of Ni–Mo/WC electrodes is determined by the presence of WC nanoparticles and Mo content in the metallic matrix. The best electrocatalytic properties are identified for Ni–Mo/WC composite with the highest Mo content and the most oxidized surface among the studied coatings. The impedance results reveal that the observed improvement in the catalytic activity is the consequence of high real surface area and high intrinsic catalytic activity of the composite.
Hydrogen for Australia’s Future
Aug 2018
Publication
The Hydrogen Strategy Group chaired by Australia’s Chief Scientist Dr Alan Finkel has today released a briefing paper on the potential domestic and export opportunities of a hydrogen industry in Australia.
Like natural gas hydrogen can be used to heat buildings and power vehicles. Unlike natural gas or petrol when hydrogen is burned there are no CO2 emissions. The only by-products are water vapour and heat.
Hydrogen is the most abundant element in the universe not freely available as a gas on Earth but bound into many common substances including water and fossil fuels.
Hydrogen was first formally presented as a credible alternative energy source in the early 1970s but never proved competitive at scale as an energy source – until now. We find that the worldwide demand for hydrogen is set to increase substantially over coming decades driven by Japan’s decision to put imported hydrogen at the heart of its economy. Production costs are falling technologies are progressing and the push for non-nuclear low-emissions fuels is building momentum. We conclude that Australia is remarkably well-positioned to benefit from the growth of hydrogen industries and markets.
Like natural gas hydrogen can be used to heat buildings and power vehicles. Unlike natural gas or petrol when hydrogen is burned there are no CO2 emissions. The only by-products are water vapour and heat.
Hydrogen is the most abundant element in the universe not freely available as a gas on Earth but bound into many common substances including water and fossil fuels.
Hydrogen was first formally presented as a credible alternative energy source in the early 1970s but never proved competitive at scale as an energy source – until now. We find that the worldwide demand for hydrogen is set to increase substantially over coming decades driven by Japan’s decision to put imported hydrogen at the heart of its economy. Production costs are falling technologies are progressing and the push for non-nuclear low-emissions fuels is building momentum. We conclude that Australia is remarkably well-positioned to benefit from the growth of hydrogen industries and markets.
Instantaneous Hydrogen Production from Ammonia by Non-thermal Arc Plasma Combining with Catalyst
Jul 2021
Publication
Owing to the storage and transportation problems of hydrogen fuel exploring new methods of the realtime hydrogen production from ammonia becomes attractive. In this paper non-thermal arc plasma (NTAP) combining with NiO/Al2O3 catalyst is developed to produce hydrogen from ammonia with high efficiency and large scale. The effects of ammonia gas flow rate and discharge power on the gas temperature electron density the hydrogen production rate and energy efficiency were investigated. Experimental results show that the optical emission spectrum of NTAP working with pure ammonia medium was dominated by the atom spectrum of Hα Hβ and molecular spectrum of NH component. Under the optimum experimental condition of plasma discharge the highest energy efficiency of hydrogen production reached 783.4 L/kW·h at NH3 gas flow rate of 30 SLM. When the catalyst was added and heated by the NTAP simultaneously the energy efficiency further increased to 1080.0 L/kW·h.
Hydrothermal Synthesis of Iridium-Substituted NaTaO3 Perovskites
Jun 2021
Publication
Iridium-containing NaTaO3 is produced using a one-step hydrothermal crystallisation from Ta2O5 and IrCl3 in an aqueous solution of 10 M NaOH in 40 vol% H2O2 heated at 240 °C. Although a nominal replacement of 50% of Ta by Ir was attempted the amount of Ir included in the perovskite oxide was only up to 15 mol%. The materials are formed as crystalline powders comprising cube-shaped crystallites around 100 nm in edge length as seen by scanning transmission electron microscopy. Energy dispersive X-ray mapping shows an even dispersion of Ir through the crystallites. Profile fitting of powder X-ray diffraction (XRD) shows expanded unit cell volumes (orthorhombic space group Pbnm) compared to the parent NaTaO3 while XANES spectroscopy at the Ir LIII-edge reveals that the highest Ir-content materials contain Ir4+. The inclusion of Ir4+ into the perovskite by replacement of Ta5+ implies the presence of charge-balancing defects and upon heat treatment the iridium is extruded from the perovskite at around 600 °C in air with the presence of metallic iridium seen by in situ powder XRD. The highest Ir-content material was loaded with Pt and examined for photocatalytic evolution of H2 from aqueous methanol. Compared to the parent NaTaO3 the Ir-substituted material shows a more than ten-fold enhancement of hydrogen yield with a significant proportion ascribed to visible light absorption.
A Comprehensive Review of Microbial Electrolysis Cells (MEC) Reactor Designs and Configurations for Sustainable Hydrogen Gas Production
Nov 2015
Publication
Hydrogen gas has tremendous potential as an environmentally acceptable energy carrier for vehicles. A cutting edge technology called a microbial electrolysis cell (MEC) can achieve sustainable and clean hydrogen production from a wide range of renewable biomass and wastewaters. Enhancing the hydrogen production rate and lowering the energy input are the main challenges of MEC technology. MEC reactor design is one of the crucial factors which directly influence on hydrogen and current production rate in MECs. The rector design is also a key factor to upscaling. Traditional MEC designs incorporated membranes but it was recently shown that membrane-free designs can lead to both high hydrogen recoveries and production rates. Since then multiple studies have developed reactors that operate without membranes. This review provides a brief overview of recent advances in research on scalable MEC reactor design and configurations.
On Capital Utilization in the Hydrogen Economy: The Quest to Minimize Idle Capacity in Renewables-rich Energy Systems
Oct 2020
Publication
The hydrogen economy is currently experiencing a surge in attention partly due to the possibility of absorbing variable renewable energy (VRE) production peaks through electrolysis. A fundamental challenge with this approach is low utilization rates of various parts of the integrated electricity-hydrogen system. To assess the importance of capacity utilization this paper introduces a novel stylized numerical energy system model incorporating the major elements of electricity and hydrogen generation transmission and storage including both “green” hydrogen from electrolysis and “blue” hydrogen from natural gas reforming with CO2 capture and storage (CCS). Concurrent optimization of all major system elements revealed that balancing VRE with electrolysis involves substantial additional costs beyond reduced electrolyzer capacity factors. Depending on the location of electrolyzers greater capital expenditures are also required for hydrogen pipelines and storage infrastructure (to handle intermittent hydrogen production) or electricity transmission networks (to transmit VRE peaks to electrolyzers). Blue hydrogen scenarios face similar constraints. High VRE shares impose low utilization rates of CO2 capture transport and storage infrastructure for conventional CCS and of hydrogen transmission and storage infrastructure for a novel process (gas switching reforming) that enables flexible power and hydrogen production. In conclusion all major system elements must be considered to accurately reflect the costs of using hydrogen to integrate higher VRE shares.
Techno-economic Assessment of Hydrogen Production from Seawater
Nov 2022
Publication
Population growth and the expansion of industries have increased energy demand and the use of fossil fuels as an energy source resulting in release of greenhouse gases (GHG) and increased air pollution. Countries are therefore looking for alternatives to fossil fuels for energy generation. Using hydrogen as an energy carrier is one of the most promising alternatives to replace fossil fuels in electricity generation. It is therefore essential to know how hydrogen is produced. Hydrogen can be produced by splitting the water molecules in an electrolyser using the abondand water resources which are covering around ⅔ of the Earth's surface. Electrolysers however require high-quality water with conductivity in the range of 0.1–1 μS/cm. In January 2018 there were 184 offshore oil and gas rigs in the North Sea which may be excellent sites for hydrogen production from seawater. The hydrogen production process reported in this paper is based on a proton exchange membrane (PEM) electrolyser with an input flow rate of 300 L/h. A financially optimal system for producing demineralized water from seawater with conductivity in the range of 0.1–1 μS/cm as the input for electrolyser by WAVE (Water Application Value Engine) design software was studied. The costs of producing hydrogen using the optimised system was calculated to be US$3.51/kg H2. The best option for low-cost power generation using renewable resources such as photovoltaic (PV) devices wind turbines as well as electricity from the grid was assessed considering the location of the case considered. All calculations were based on assumption of existing cable from the grid to the offshore meaning that the cost of cables and distribution infrastructure were not considered. Models were created using HOMER Pro (Hybrid Optimisation of Multiple Energy Resources) software to optimise the microgrids and the distributed energy resources under the assumption of a nominal discount rate inflation rate project lifetime and CO2 tax in Norway. Eight different scenarios were examined using HOMER Pro and the main findings being as follows:<br/>The cost of producing water with quality required by the electrolyser is low compared with the cost of electricity for operation of the electrolyser and therefore has little effect on the total cost of hydrogen production (less than 1%).<br/>The optimal solution was shown to be electricity from the grid which has the lowest levelised cost of energy (LCOE) of the options considered. The hydrogen production cost using electricity from the grid was about US$ 5/kg H2.<br/>Grid based electricity resulted in the lowest hydrogen production cost even when costs for CO2 emissions in Norway that will start to apply in 2025 was considered being approximately US$7.7/kg H2.<br/>From economical point of view wind energy was found to be a more economical than solar.
Cogeneration of Green Hydrogen in a Cascade Hydropower Plant
Apr 2021
Publication
Hydrogen is today an indispensable feedstock in various process industries but the method of its production is mostly not in line with accepted environmental guidelines. With emerging electro-energetic systems with a large share of renewable sources hydrogen is also becoming an important energy carrier which with the possibility of storing surplus energy ensures greater stability of power system operation and energy supply. Therefore the use of electricity from renewable sources is important for the production of green hydrogen using electrolysis. The first part of the article describes the possibilities for hydrogen cogeneration in one of the run-of-river hydropower plants in Slovenia. The implementation costs of the necessary equipment for hydrogen production in the case-study power plant its production costs and the profitability of hydrogen production compared to the sale of electricity are estimated. The criteria according to which the production of hydrogen is more profitable than the sale of electricity at current prices and guaranteed sales is also defined. In the second part of the article a scenario for the use of hydrogen for heating and mobility needs in the nearby local community is presented. For the regular supply of hydrogen in the range of up to 30 kg/h the necessary investment costs for the installation of the appropriate equipment in the hydropower plant are calculated along with an estimation of the payback period of the investment.
Sustainable Hydrogen Production by Plasmonic Thermophotocatalysis
Feb 2021
Publication
A vision of hydrogen based economy and clean sustainable fossil fuels-free world inspires the scientific community to put much effort into the development of visible-light-driven photochemistry and efficient solar energy harvesting. The unique features of plasmonic nanomaterials such as capability of significant electric field amplification an extreme local heating generation of high energy charge carriers and broad tunability of optical properties coupled to catalytically active surfaces provide an exciting opportunity for hydrogen production with solar photochemistry. This review sums up recent progress in the development of plasmonic thermophotocatalysis paying particular attention to sustainable production of hydrogen. We approach the subject from a broad bottom-up perspective beginning with the brief description of plasmon-related phenomena and plasmon-assisted photochemistry through the demonstration of various plasmonic nanostructures their synthesis and hydrogen production efficiency ending with the idea of continuous-flow reactors and their future implementation in hydrogen production by plasmonic thermophotocatalysis. Finally we summarize the review and highlight the remaining challenges that have to be faced before the widespread commercialization of this technology.
Controlled Biosynthesis of ZnCdS Quantum Dots with Visible-Light-Driven Photocatalytic Hydrogen Production Activity
May 2021
Publication
The development of visible-light-responsive photocatalysts with high efficiency stability and eco-friendly nature is beneficial to the large-scale application of solar hydrogen production. In this work the production of biosynthetic ternary ZnCdS photocatalysts (Eg = 2.35–2.72 eV) by sulfate-reducing bacteria (SRB) under mild conditions was carried out for the first time. The huge amount of biogenic S2− and inherent extracellular proteins (EPs) secreted by SRB are important components of rapid extracellular biosynthesis. The ternary ZnCdS QDs at different molar ratios of Zn2+and Cd2+ from 15:1 to 1:1 were monodisperse spheres with good crystallinity and average crystallite size of 6.12 nm independent of the molar ratio of Cd2+ to Zn2+. All the ZnCdS QDs had remarkable photocatalytic activity and stability for hydrogen evolution under visible light without noble metal cocatalysts. Especially ZnCdS QDs at Zn/Cd = 3:1 showed the highest H2 production activity of 3.752 mmol·h−1·g−1. This excellent performance was due to the high absorption of visible light the high specific surface area and the lower recombination rate between photoexcited electrons and holes. The adhered inherent EPs on the ZnCdS QDs slowed down the photocorrosion and improved the stability in photocatalytic hydrogen evolution. This study provides a new direction for solar hydrogen production.
How Green is Blue Hydrogen?
Jul 2021
Publication
Hydrogen is often viewed as an important energy carrier in a future decarbonized world. Currently most hydrogen is produced by steam reforming of methane in natural gas (“gray hydrogen”) with high carbon dioxide emissions. Increasingly many propose using carbon capture and storage to reduce these emissions producing so-called “blue hydrogen” frequently promoted as low emissions. We undertake the first effort in a peer-reviewed paper to examine the lifecycle greenhouse gas emissions of blue hydrogen accounting for emissions of both carbon dioxide and unburned fugitive methane. Far from being low carbon greenhouse gas emissions from the production of blue hydrogen are quite high particularly due to the release of fugitive methane. For our default assumptions (3.5% emission rate of methane from natural gas and a 20-year global warming potential) total carbon dioxide equivalent emissions for blue hydrogen are only 9%-12% less than for gray hydrogen. While carbon dioxide emissions are lower fugitive methane emissions for blue hydrogen are higher than for gray hydrogen because of an increased use of natural gas to power the carbon capture. Perhaps surprisingly the greenhouse gas footprint of blue hydrogen is more than 20% greater than burning natural gas or coal for heat and some 60% greater than burning diesel oil for heat again with our default assumptions. In a sensitivity analysis in which the methane emission rate from natural gas is reduced to a low value of 1.54% greenhouse gas emissions from blue hydrogen are still greater than from simply burning natural gas and are only 18%-25% less than for gray hydrogen. Our analysis assumes that captured carbon dioxide can be stored indefinitely an optimistic and unproven assumption. Even if true though the use of blue hydrogen appears difficult to justify on climate ground
Transient Numerical Modeling and Model Predictive Control of an Industrial-scale Steam Methane Reforming Reactor
Mar 2021
Publication
A steam methane reforming reactor is a key equipment in hydrogen production and numerical analysis and process control can provide a critical insight into its reforming mechanisms and flexible operation in real engineering applications. The present paper firstly studies the transport phenomena in an industrial-scale steam methane reforming reactor by transient numerical simulations. Wall effect and local non thermal equilibrium is considered in the simulations. A temperature profile of the tube outer wall is given by user defined functions integrated into the ANSYS FLUENT software. Dynamic simulations show that the species distribution is closely related to the temperature distribution which makes the temperature of the reactor tube wall an important factor for the hydrogen production of the reformer and the thermal conductivity of the catalyst network is crucial in the heat transfer in the reactor. Besides there exists a delay of the reformer's hydrogen production when the temperature profile of the tube wall changes. Among inlet temperature inlet mass flow rate and inlet steam-to-carbon (S/C) ratio the mass flow rate is the most influencing factor for the hydrogen production. The dynamic matrix control (DMC) scheme is subsequently designed to manipulate the mole fraction of hydrogen of the outlet to the target value by setting the temperature profile trajectory of the reforming tube with time. The proportional-integral control strategy is also studied for comparison. The closed-loop simulation results show that the proposed DMC control strategy can reduce the overshoot and have a small change of the input variable. In addition the disturbances of feed disturbance can also be well rejected to assure the tracking performance indicating the superiority of the DMC controller. All the results give insight to the theoretical analysis and controller design of a steam methane reformer and demonstrate the potential of the CFD modeling in study the transport mechanism and the idea of combining CFD modelling with controller design for the real application.
Synergetic Effect of Multiple Phases on Hydrogen Desorption Kinetics and Cycle Durability in Ball Milled MgH2–PrF3–Al–Ni Composite
Jan 2021
Publication
A new MgH2–PrF3–Al–Ni composite was prepared by ball milling under hydrogen atmosphere. After initial dehydrogenation and rehydrogenation Pr3Al11 MgF2 PrH3 and Mg2NiH4 nanoparticles formed accompanying the main phase MgH2. The hydrogen absorption-desorption properties were measured by using a Sieverts-type apparatus. The results showed that the MgH2–PrF3–Al–Ni composite improved cycle stability and enhanced hydrogen desorption kinetics. The improvement of hydrogen absorption-desorption properties is ascribed to the synergetic effect of the in situ formed Pr3Al11 MgF2 PrH3 and Mg2NiH4 nanoparticles. This work provides an important inspiration for the improvement of hydrogen storage properties in Mg-based materials.
Influence of Cs Promoter on Ethanol Steam-Reforming Selectivity of Pt/m-ZrO2 Catalysts at Low Temperature
Sep 2021
Publication
The decarboxylation pathway in ethanol steam reforming ultimately favors higher selectivity to hydrogen over the decarbonylation mechanism. The addition of an optimized amount of Cs to Pt/m-ZrO2 catalysts increases the basicity and promotes the decarboxylation route converting ethanol to mainly H2 CO2 and CH4 at low temperature with virtually no decarbonylation being detected. This offers the potential to feed the product stream into a conventional methane steam reformer for the production of hydrogen with higher selectivity. DRIFTS and the temperature-programmed reaction of ethanol steam reforming as well as fixed bed catalyst testing revealed that the addition of just 2.9% Cs was able to stave off decarbonylation almost completely by attenuating the metallic function. This occurs with a decrease in ethanol conversion of just 16% relative to the undoped catalyst. In comparison with our previous work with Na this amount is—on an equivalent atomic basis—just 28% of the amount of Na that is required to achieve the same effect. Thus Cs is a much more efficient promoter than Na in facilitating decarboxylation.
Facile Synthesis of Palladium Phosphide Electrocatalysts and their Activity for the Hydrogen Oxidation, Hydrogen Evolutions, Oxygen Reduction and Formic Acid Oxidation Reactions
Nov 2015
Publication
We demonstrate a new approach for producing highly dispersed supported metal phosphide powders with small particle size improved stability and increased electrocatalytic activity towards some useful reactions. The approach involves a one-step conversion of metal supported on high surface area carbon to the metal phosphide utilising a very simple and scalable synthetic process. We use this approach to produce PdP2 and Pd5P2 particles dispersed on carbon with a particle size of 4.5–5.5 nm by converting a commercially available Pd/C powder. The metal phosphide catalysts were tested for the oxygen reduction hydrogen oxidation and evolution and formic acid oxidation reactions. Compared to the unconverted Pd/C material we find that alloying the P at different levels shifts oxide formation on the Pd to higher potentials leading to greater stability during cycling studies (20% more ECSA retained 5k cycles) and in thermal treatment under air. Hydrogen absorption within the PdP2 and Pd5P2 particles is enhanced. The phosphides compare favourably to the most active catalysts reported to date for formic acid oxidation especially PdP2 and there is a significant decrease in poisoning of the surface compared to Pd alone. The mechanistic changes in the reactions studied are rationalised in terms of increased water activation on the surface phosphorus atoms of the catalyst. One of the catalysts PdP2/C is tested in a fuel cell as anode and cathode catalyst and shows good performance.
Hydrogen Production via Steam Reforming: A Critical Analysis of MR and RMM Technologies
Jan 2020
Publication
Hydrogen as the energy carrier of the future’ has been a topic discussed for decades and is today the subject of a new revival especially driven by the investments in renewable electricity and the technological efforts done by high-developed industrial powers such as Northern Europe and Japan. Although hydrogen production from renewable resources is still limited to small scale local solutions and R&D projects; steam reforming (SR) of natural gas at industrial scale is the cheapest and most used technology and generates around 8 kg CO2 per kg H2. This paper is focused on the process optimization and decarbonization of H2 production from fossil fuels to promote more efficient approaches based on membrane separation. In this work two emerging configurations have been compared from the numerical point of view: the membrane reactor (MR) and the reformer and membrane module (RMM) proposed and tested by this research group. The rate of hydrogen production by SR has been calculated according to other literature works a one-dimensional model has been developed for mass heat and momentum balances. For the membrane modules the rate of hydrogen permeation has been estimated according to mass transfer correlation previously reported by this research group and based on previous experimental tests carried on in the first RMM Pilot Plant. The methane conversion carbon dioxide yield temperature and pressure profile are compared for each configuration: SR MR and RMM. By decoupling the reaction and separation section such as in the RMM the overall methane conversion can be increased of about 30% improving the efficiency of the system.
Heat to Hydrogen by RED—Reviewing Membranes and Salts for the RED Heat Engine Concept
Dec 2021
Publication
The Reverse electrodialysis heat engine (REDHE) combines a reverse electrodialysis stack for power generation with a thermal regeneration unit to restore the concentration difference of the salt solutions. Current approaches for converting low-temperature waste heat to electricity with REDHE have not yielded conversion efficiencies and profits that would allow for the industrialization of the technology. This review explores the concept of Heat-to-Hydrogen with REDHEs and maps crucial developments toward industrialization. We discuss current advances in membrane development that are vital for the breakthrough of the RED Heat Engine. In addition the choice of salt is a crucial factor that has not received enough attention in the field. Based on ion properties relevant for both the transport through IEMs and the feasibility for regeneration we pinpoint the most promising salts for use in REDHE which we find to be KNO3 LiNO3 LiBr and LiCl. To further validate these results and compare the system performance with different salts there is a demand for a comprehensive thermodynamic model of the REDHE that considers all its units. Guided by such a model experimental studies can be designed to utilize the most favorable process conditions (e.g. salt solutions).
Membrane-Based Electrolysis for Hydrogen Production: A Review
Oct 2021
Publication
Hydrogen is a zero-carbon footprint energy source with high energy density that could be the basis of future energy systems. Membrane-based water electrolysis is one means by which to produce high-purity and sustainable hydrogen. It is important that the scientific community focus on developing electrolytic hydrogen systems which match available energy sources. In this review various types of water splitting technologies and membrane selection for electrolyzers are discussed. We highlight the basic principles recent studies and achievements in membrane-based electrolysis for hydrogen production. Previously the NafionTM membrane was the gold standard for PEM electrolyzers but today cheaper and more effective membranes are favored. In this paper CuCl–HCl electrolysis and its operating parameters are summarized. Additionally a summary is presented of hydrogen production by water splitting including a discussion of the advantages disadvantages and efficiencies of the relevant technologies. Nonetheless the development of cost-effective and efficient hydrogen production technologies requires a significant amount of study especially in terms of optimizing the operation parameters affecting the hydrogen output. Therefore herein we address the challenges prospects and future trends in this field of research and make critical suggestions regarding the implementation of comprehensive membrane-based electrolytic systems.
Thermodynamic Analysis of the Gasification of Municipal Solid Waste
May 2017
Publication
This work aims to understand the gasification performance of municipal solid waste (MSW) by means of thermodynamic analysis. Thermodynamic analysis is based on the assumption that the gasification reactions take place at the thermodynamic equilibrium condition without regard to the reactor and process characteristics. First model components of MSW including food green wastes paper textiles rubber chlorine-free plastic and polyvinyl chloride were chosen as the feedstock of a steam gasification process with the steam temperature ranging from 973 K to 2273 K and the steam-to-MSW ratio (STMR) ranging from 1 to 5. It was found that the effect of the STMR on the gasification performance was almost the same as that of the steam temperature. All the differences among the seven types of MSW were caused by the variation of their compositions. Next the gasification of actual MSW was analyzed using this thermodynamic equilibrium model. It was possible to count the inorganic components of actual MSW as silicon dioxide or aluminum oxide for the purpose of simplification due to the fact that the inorganic components mainly affected the reactor temperature. A detailed comparison was made of the composition of the gaseous products obtained using steam hydrogen and air gasifying agents to provide basic knowledge regarding the appropriate choice of gasifying agent in MSW treatment upon demand.
Hydrogen Production: State of Technology
May 2020
Publication
Presently hydrogen is for ~50% produced by steam reforming of natural gas – a process leading to significant emissions of greenhouse gas (GHG). About 30% is produced from oil/naphtha reforming and from refinery/chemical industry off-gases. The remaining capacity is covered for 18% from coal gasification 3.9% from water electrolysis and 0.1% from other sources. In the foreseen future hydrogen economy green hydrogen production methods will need to supply hydrogen to be used directly as fuel or to generate synthetic fuels to produce ammonia and other fertilizers (viz. urea) to upgrade heavy oils (like oil sands) and to produce other chemicals. There are several ways to produce H2 each with limitations and potential such as steam reforming electrolysis thermal and thermo-chemical water splitting dark and photonic fermentation; gasification and catalytic decomposition of methanol. The paper reviews the fundamentals and potential of these alternative process routes. Both thermo-chemical water splitting and fermentation are marked as having a long term but high "green" potential.
Hollow Cobalt Sulfide Nanocapsules for Electrocatalytic Selective Transfer Hydrogenation of Cinnamaldehyde with Water
Feb 2021
Publication
Designing nanostructured electrocatalysts for selective transfer hydrogenation of α β-unsaturated aldehydes with water as the hydrogen source is highly desirable. Here a facile self-templating strategy is designed for the synthesis of CoS2 and CoS2-x nanocapsules (NCs) as efficient cathodes for selective transfer hydrogenation of cinnamaldehyde a model α β-unsaturated aldehyde. The hollow porous structures of NCs are rich in active sites and improve mass transfer resulting in high turnover frequency. The specific adsorption of the styryl block on pristine CoS2 NCs is conducive to the selective formation of half-hydrogenated hydrocinnamaldehyde with 91.7% selectivity and the preferential adsorption of the C = O group induced by sulfur vacancies on defective CoS2-x NCs leads to the full-hydrogenated hydrocinnamyl alcohol with 92.1% selectivity. A cross-coupling of carbon and hydrogen radicals may be involved in this electrochemical hydrogenation reaction. Furthermore this selective hydrogenation method is also effective for other α β-unsaturated aldehydes illustrating the universality of the method.
How Do Dissolved Gases Affect the Sonochemical Process of Hydrogen Production: An Overview of Thermodynamic and Mechanistic Effects – On the “Hot Spot Theory”
Dec 2020
Publication
Although most of researchers agree on the elementary reactions behind the sonolytic formation of molecular hydrogen (H2) from water namely the radical attack of H2O and H2O2 and the free radicals recombination several recent papers ignore the intervention of the dissolved gas molecules in the kinetic pathways of free radicals and hence may wrongly assess the effect of dissolved gases on the sonochemical production of hydrogen. One may fairly ask to which extent is it acceptable to ignore the role of the dissolved gas and its eventual decomposition inside the acoustic cavitation bubble? The present opinion paper discusses numerically the ways in which the nature of dissolved gas i.e. N2 O2 Ar and air may influence the kinetics of sonochemical hydrogen formation. The model evaluates the extent of direct physical effects i.e. dynamics of bubble oscillation and collapse events if any against indirect chemical effects i.e. the chemical reactions of free radicals formation and consequently hydrogen emergence it demonstrates the improvement in the sonochemical hydrogen production under argon and sheds light on several misinterpretations reported in earlier works due to wrong assumptions mainly related to initial conditions. The paper also highlights the role of dissolved gases in the nature of created cavitation and hence the eventual bubble population phenomena that may prevent the achievement of the sonochemical activity. This is particularly demonstrated experimentally using a 20 kHz Sinaptec transducer and a Photron SA 5 high speed camera in the case of CO2-saturated water where degassing bubbles are formed instead of transient cavitation.
A Review of Recent Developments in Molecular Dynamics Simulations of the Photoelectrochemical Water Splitting Process
Jun 2021
Publication
In this review we provide a short overview of the Molecular Dynamics (MD) method and how it can be used to model the water splitting process in photoelectrochemical hydrogen production. We cover classical non-reactive and reactive MD techniques as well as multiscale extensions combining classical MD with quantum chemical and continuum methods. Selected examples of MD investigations of various aqueous semiconductor interfaces with a special focus on TiO2 are discussed. Finally we identify gaps in the current state-of-the-art where further developments will be needed for better utilization of MD techniques in the field of water splitting.
Aqueous Phase Reforming of the Residual Waters Derived from Lignin-rich Hydrothermal Liquefaction: Investigation of Representative Organic Compounds and Actual Biorefinery Streams
Sep 2019
Publication
Secondary streams in biorefineries need to be valorized to improve the economic and environmental sustainability of the plants. Representative model compounds of the water fraction from the hydrothermal liquefaction (HTL) of biomass were subjected to aqueous phase reforming (APR) to produce hydrogen. Carboxylic and bicarboxylic acids hydroxyacids alcohols cycloketones and aromatics were identified as model compounds and tested for APR. The tests were performed with a Pt/C catalyst and the influence of the carbon concentration (0.3–1.8 wt. C%) was investigated. Typically the increase of the concentration negatively affected the conversion of the feed toward gaseous products without influencing the selectivity toward hydrogen production. A synthetic ternary mixture (glycolic acid acetic acid lactic acid) was subjected to APR to evaluate any differences in performance compared to the tests with single compounds. Indeed glycolic acid reacted faster in the mixture than in the corresponding single compound test while acetic acid remained almost unconverted. The influence of the reaction time temperature and carbon concentration was also evaluated. Finally residual water resulting from the HTL of a lignin-rich stream originating from an industrial-scale lignocellulosic ethanol process was tested for the first time after a thorough characterization. In this framework the stability of the catalyst was studied and found to be correlated to the presence of aromatics in the aqueous feedstock. For this reason the influence of an extraction procedure for the selective removal of these compounds was explored leading to an improvement in the APR performance.
Progress and Prospects of Hydrogen Production: Opportunities and challenges
Jan 2021
Publication
This study presents an overview of the current status of hydrogen production in relation to the global requirement for energy and resources. Subsequently it symmetrically outlines the advantages and disadvantages of various production routes including fossil fuel/biomass conversion water electrolysis microbial fermentation and photocatalysis (PC) in terms of their technologies economy energy consumption and costs. Considering the characteristics of hydrogen energy and the current infrastructure issues it highlights that onsite production is indispensable and convenient for some special occasions. Finally it briefly summarizes the current industrialization situation and presents future development and research directions such as theoretical research strengthening renewable raw material development process coupling and sustainable energy use.
Comparative Analysis of Energy and Exergy Performance of Hydrogen Production Methods
Nov 2020
Publication
The study of the viability of hydrogen production as a sustainable energy source is a current challenge to satisfy the great world energy demand. There are several techniques to produce hydrogen either mature or under development. The election of the hydrogen production method will have a high impact on practical sustainability of the hydrogen economy. An important profile for the viability of a process is the calculation of energy and exergy efficiencies as well as their overall integration into the circular economy. To carry out theoretical energy and exergy analyses we have estimated proposed hydrogen production using different software (DWSIM and MATLAB) and reference conditions. The analysis consolidates methane reforming or auto-thermal reforming as the viable technologies at the present state of the art with reasonable energy and exergy efficiencies but pending on the impact of environmental constraints as CO2 emission countermeasures. However natural gas or electrolysis show very promising results and should be advanced in their technological and maturity scaling. Electrolysis shows a very good exergy efficiency due to the fact that electricity itself is a high exergy source. Pyrolysis exergy loses are mostly in the form of solid carbon material which has a very high integration potential into the hydrogen economy.
The Optimization of Hybrid Power Systems with Renewable Energy and Hydrogen Generation
Jul 2018
Publication
This paper discusses the optimization of hybrid power systems which consist of solar cells wind turbines fuel cells hydrogen electrolysis chemical hydrogen generation and batteries. Because hybrid power systems have multiple energy sources and utilize different types of storage we first developed a general hybrid power model using the Matlab/SimPowerSystemTM and then tuned model parameters based on the experimental results. This model was subsequently applied to predict the responses of four different hybrid power systems for three typical loads without conducting individual experiments. Furthermore cost and reliability indexes were defined to evaluate system performance and to derive optimal system layouts. Finally the impacts of hydrogen costs on system optimization was discussed. In the future the developed method could be applied to design customized hybrid power systems.
Comparison Between Hydrogen Production by Alkaline Water Electrolysis and Hydrogen Production by PEM Electrolysis
Sep 2021
Publication
Hydrogen is an ideal clean energy source that can be used as an energy storage medium for renewable energy sources. The water electrolysis hydrogen production technology which is one of the mainstream hydrogen production methods can be used to produce high-purity hydrogen and other energy sources can be converted into hydrogen storage by electrolysis. Hydrogen production by alkaline water electrolysis and hydrogen production by PEM electrolysis are all water electrolysis hydrogen production technologies that have been industrially applied. From the application point of view the paper compares the working principle of the two kinds of electrolyzers the process flow of hydrogen production equipment advantages and disadvantages. This article provides a reference for relevant researchers.
Experimental and Theoretical Insights to Demonstrate the Hydrogen Evolution Activity of Layered Platinum Dichalcogenides Electrocatalysts
Mar 2021
Publication
Hydrogen is a highly efficient and clean renewable energy source and water splitting through electrocatalytic hydrogen evolution is a most promising approach for hydrogen generation. Layered transition metal dichalcogenides-based nano-structures have recently attracted significant interest as robust and durable catalysts for hydrogen evolution. We systematically investigated the platinum (Pt) based dichalcogenides (PtS2 PtSe2 and PtTe2) as highly energetic and robust hydrogen evolution electrocatalysts. PtTe2 catalyst unveiled the rapid hydrogen evolution process with the low overpotentials of 75 and 92 mV (vs. RHE) at a current density of 10 mA cm−2 and the small Tafel slopes of 64 and 59 mV/dec in acidic and alkaline medium respectively. The fabricated PtTe2 electrocatalyst explored a better catalytic activity than PtS2 and PtSe2. The density functional theory estimations explored that the observed small Gibbs free energy for H-adsorption of PtTe2 was given the prominent role to achieve the superior electrocatalytic and excellent stability activity towards hydrogen evolution due to a smaller bandgap and the metallic nature. We believe that this work will offer a key path to use Pt based dichalcogenides for hydrogen evolution electrocatalysts.
Insights into the Principles, Design Methodology and Applications of Electrocatalysts Towards Hydrogen Evolution Reaction
Apr 2021
Publication
The electrolysis of water for sustainable hydrogen producing is a crucial segment of various emerging clean-energy technologies. However pursuing an efficient and cheap alternative catalyst to substitute state-of-the-art platinum-group electrocatalysts remains a prerequisite for the commercialization of this technology. Typically precious-metal-free catalysts have always much lower activities towards hydrogen production than that of Pt-group catalysts. To explore high-performance catalysts maximally exposed active sites rapid charge transfer ability and desirable electronic configuration are essentially demanded. Herein the fundamentals of hydrogen evolution reaction will be briefly described and the main focus will be on the interfacial engineering strategies by means of constructing defect structure creating heterojunction phase engineering lattice strain control designing hierarchical architecture and doping heteroatoms to effectively proliferate the catalytic active sites facilitate the electron diffusion and regulate the electronic configuration of numerous transition metals and their nitrides carbides sulfides phosphides as well as oxides achieving a benchmark performance of platinum-free electrocatalysts for the hydrogen evolution reaction. This review unambiguously offers proof that the conventional cheap and earth-abundant transition metal-based substances can be translated into an active water splitting catalyst by the rational and controllable interfacial designing.
Hydrothermal Conversion of Lignin and Black Liquor for Phenolics with the Aids of Alkali and Hydrogen Donor
Jun 2019
Publication
The potentials of phenolic productions from lignin and black liquor (BL) via hydrothermal technology with the aids of alkalis and hydrogen donors were investigated by conducting batch experiments in micro-tube reactors with 300 °C sub-critical water as the solvent. The results showed that all the employed alkalis improved lignin degradation and thus phenolics production and the strong alkalis additionally manifested deoxygenation to produce more phenolics free of methoxyl group(s). Relatively hydrogen donors more visibly facilitated phenolics formation. Combination of strong alkali and hydrogen donors exhibited synergistically positive effects on producing phenolics (their total yield reaching 22 wt%) with high selectivities to phenolics among which the yields of catechol and cresols respectively peaked 16 and 3.5 wt%. BL could be hydrothermally converted into phenolics at high yields (approaching 10 wt% with the yields of catechol and cresols of about 4 and 2 wt% respectively) with the aids of its inherent alkali and hydrogen donors justifying its cascade utilization.
Evaluation of Stability and Catalytic Activity of Ni Catalysts for Hydrogen Production by Biomass Gasification in Supercritical Water
Mar 2019
Publication
Supercritical water gasification is a promising technology for wet biomass utilization. In this paper Ni and other metal catalysts were synthesized by wet impregnation. The stability and catalytic activities of Ni catalysts were evaluated. Firstly catalytic activities of Ni Fe Cu catalysts supported on MgO were tested using wheat straw as raw material in a batch reactor at 723 K and water density of 0.07 cm3/g. Experimental results showed that the order of metal catalyst activity for hydrogen generation was Ni/MgO > Fe/MgO > Cu/MgO. Secondly the influence of different supports on Ni catalysts performance was investigated. The results showed that the order of the Ni catalysts’ activity with different supports was Ni/MgO > Ni/ZnO > Ni/Al2O3 > Ni/ZrO2. Finally the effects of Ni loading and the amount of Ni catalyst addition on hydrogen production and the stability of Ni/MgO catalyst were studied. It was found that serious deactivation of Ni catalyst in the process of supercritical water gasification took place. Even if carbon deposited on the catalyst surface was removed by high temperature calcination and the catalyst was reduced with hydrogen the activity of used catalyst was only partially restored.
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