Production & Supply Chain
Renewable Hydrogen Production from Butanol: A Review
Dec 2017
Publication
Hydrogen production from butanol is a promising alternative when it is obtained from bio-butanol or bio-oil due to the higher hydrogen content compared to other oxygenates such as methanol ethanol or propanol. Catalysts and operating conditions play a crucial role in hydrogen production. Ni and Rh are metals mainly used for butanol steam reforming oxidative steam reforming and partial oxidation. Additives such as Cu can improve catalytic activity in many folds. Moreover support–metal interaction and catalyst preparation technique also play a decisive role in the stability and hydrogen production capacity of catalyst. Steam reforming technique as an option is more frequently researched due to higher hydrogen production capability in comparison to other thermochemical techniques despite its endothermic nature. The use of the oxidative steam reforming and partial oxidation has the advantages of requiring less energy and longer stability of catalysts. However the hydrogen yield is less. This article brings together and examines the latest research on hydrogen production from butanol via steam reforming oxidative steam reforming and partial oxidation reactions. In addition the review examines a few thermodynamic studies based on sorption-enhanced steam reforming and dry reforming where there is potential for hydrogen extraction.
Hydrocarbon Production by Continuous Hydrodeoxygenation of Liquid Phase Pyrolysis Oil with Biogenous Hydrogen Rich Synthesis Gas
Feb 2019
Publication
This paper presents a beneficial combination of biomass gasification and pyrolysis oil hydrodeoxygenation for advanced biofuel production. Hydrogen for hydrodeoxygenation (HDO) of liquid phase pyrolysis oil (LPP oil) was generated by gasification of softwood. The process merges dual fluidized bed (DFB) steam gasification which produces a hydrogen rich product gas and the HDO of LPP oil. Synthesis gas was used directly without further cleaning and upgrading by making use of the water gas-shift (WGS) reaction. The water needed for the water gas-shift reaction was provided by LPP oil. HDO was successfully performed in a lab scale over 36 h time on stream (TOS). Competing reactions like the Boudouard reaction and Sabatier reaction were not observed. Product quality was close to Diesel fuel specification according to EN 590 with a carbon content of 85.4 w% and a residual water content of 0.28 w%. The water-gas shift reaction was confirmed by CO/CO2-balance high water consumption and 28% less hydrogen consumption during HDO.
Hydrogen Production by Electrochemical Reaction Using Ethylene Glycol with Terephthalic Acid
Jan 2021
Publication
In this study ethylene glycol (EG) and terephthalic acid (TPA) were used to generate hydrogen using copper electrodes in an alkaline aqueous solution and the corresponding reaction mechanism was experimentally investigated. Both EG and TPA produced hydrogen; however TPA consumed OH− inhibiting the production of intermediary compounds of EG and causing EG to actively react with H2O ultimately leading to enhanced hydrogen production. In addition the initiation potential of water decomposition of the EG and TPA alkaline aqueous solution was 1.0 V; when 1.8 V (vs. RHE) was applied the hydrogen production reached 440 mmol L−1 which was substantially greater than the hydrogen production rate of 150 mmol L−1 during water decomposition.
Carbon Capture and Storage (CCS): The Way Forward
Mar 2018
Publication
Mai Bui,
Claire S. Adjiman,
André Bardow,
Edward J. Anthony,
Andy Boston,
Solomon Brown,
Paul Fennell,
Sabine Fuss,
Amparo Galindo,
Leigh A. Hackett,
Jason P. Hallett,
Howard J. Herzog,
George Jackson,
Jasmin Kemper,
Samuel Krevor,
Geoffrey C. Maitland,
Michael Matuszewski,
Ian Metcalfe,
Camille Petit,
Graeme Puxty,
Jeffrey Reimer,
David M. Reiner,
Edward S. Rubin,
Stuart A. Scott,
Nilay Shah,
Berend Smit,
J. P. Martin Trusler,
Paul Webley,
Jennifer Wilcox and
Niall Mac Dowell
Carbon capture and storage (CCS) is broadly recognised as having the potential to play a key role in meeting climate change targets delivering low carbon heat and power decarbonising industry and more recently its ability to facilitate the net removal of CO2 from the atmosphere. However despite this broad consensus and its technical maturity CCS has not yet been deployed on a scale commensurate with the ambitions articulated a decade ago. Thus in this paper we review the current state-of-the-art of CO2 capture transport utilisation and storage from a multi-scale perspective moving from the global to molecular scales. In light of the COP21 commitments to limit warming to less than 2 °C we extend the remit of this study to include the key negative emissions technologies (NETs) of bioenergy with CCS (BECCS) and direct air capture (DAC). Cognisant of the non-technical barriers to deploying CCS we reflect on recent experience from the UK's CCS commercialisation programme and consider the commercial and political barriers to the large-scale deployment of CCS. In all areas we focus on identifying and clearly articulating the key research challenges that could usefully be addressed in the coming decade.
Biomass Gasification as an Industrial Process with Effective Proof-of-concept: A Comprehensive Review on Technologies, Processes and Future Developments
Apr 2022
Publication
The search for alternatives to fossil energy traditional sources led to the development of a set of energy conversion processes which include biomass thermochemical conversion technologies such as torrefaction pyrolysis hydrothermal liquefaction or gasification. These conversion technologies have shown significant evolutions and there are already several examples available of application on an industrial scale. Biomass gasification processes have also presented significant developments mainly when associated with the production of syngas with potential for energy recovery or to produce synthetic fuels but mainly due to its potential to be used as a sustainable hydrogen production technology. In the present work a bibliographic review of the current state-of-the-art of the biomass gasification is carried out focusing in the gasification technologies syngas cleaning processes simulation methodologies on process parameters. Finally future developments and possibilities are also analyzed and discussed with the introduction of a new approach to hydrogen production based on the use of an adapted combustion process with air deficit.
Advanced Steam Reforming of Bio-Oil with Carbon Capture: A Techno-Economic and CO2 Emissions Analysis
Apr 2022
Publication
A techno-economic analysis has been used to evaluate three processes for hydrogen production from advanced steam reforming (SR) of bio-oil as an alternative route to hydrogen with BECCS: conventional steam reforming (C-SR) C-SR with CO2 capture (C-SR-CCS) and sorption-enhanced chemical looping (SE-CLSR). The impacts of feed molar steam to carbon ratio (S/C) temperature pressure the use of hydrodesulphurisation pretreatment and plant production capacity were examined in an economic evaluation and direct CO2 emissions analysis. Bio-oil C-SR-CC or SE-CLSR may be feasible routes to hydrogen production with potential to provide negative emissions. SE-CLSR can improve process thermal efficiency compared to C-SR-CCS. At the feed molar steam to carbon ratio (S/C) of 2 the levelised cost of hydrogen (USD 3.8 to 4.6 per kg) and cost of carbon avoided are less than those of a C-SR process with amine-based CCS. However at higher S/C ratios SE-CLSR does not have a strong economic advantage and there is a need to better understand the viability of operating SE-CLSR of bio-oil at high temperatures (>850 ◦C) with a low S/C ratio (e.g. 2) and whether the SE-CLSR cycle can sustain low carbon deposition levels over a long operating period.
Hydrogen Production from Biomass and Organic Waste Using Dark Fermentation: An Analysis of Literature Data on the Effect of Operating Parameters on Process Performance
Jan 2022
Publication
In the context of hydrogen production from biomass or organic waste with dark fermentation this study analysed 55 studies (339 experiments) in the literature looking for the effect of operating parameters on the process performance of dark fermentation. The effect of substrate concentration pH temperature and residence time on hydrogen yield productivity and content in the biogas was analysed. In addition a linear regression model was developed to also account for the effect of nature and pretreatment of the substrate inhibition of methanogenesis and continuous or batch operating mode. The analysis showed that the hydrogen yield was mainly affected by pH and residence time with the highest yields obtained for low pH and short residence time. High hydrogen productivity was favoured by high feed concentration short residence time and low pH. More modest was the effect on the hydrogen content. The mean values of hydrogen yield productivity and content were respectively 6.49% COD COD−1 135 mg L−1 d −1 51% v/v while 10% of the considered experiments obtained yield productivity and content of or higher than 15.55% COD COD−1 305.16 mg L−1 d −1 64% v/v. Overall this study provides insight into how to select the optimum operating conditions to obtain the desired hydrogen production.
Accelerated Degradation for Solid Oxide Electrolysers: Analysis and Prediction of Performance for Varying Operating Environments
Jan 2022
Publication
Solid oxide electrolysis cells (SOECs) are an efficient technology for the production of green hydrogen that has great potential to contribute to the energy transition and decarbonization of industry. To date however time- and resource-intensive experimental campaigns slow down the development and market penetration of the technology. In order to speed-up the evaluation of SOEC performance and durability accelerated testing protocols are required. This work provides the results of experimental studies on the performance of a SOEC stack operated under accelerated degradation conditions. In order to initiate and accelerate degradation experiments were performed with high steam partial pressures at the gas inlet higher voltages and lower temperatures and high steam conversion rates. Thereby different types and degrees of impact on performance were observed which were analyzed in detail and linked to the underlying processes and degradation mechanisms. In this context significantly higher degradation rates were found compared to operation under moderate operating conditions with the different operating strategies varying in their degradation acceleration potential. The results also suggest that a few hundred hours of operation may be sufficient to predict long-term performance with the proposed operating strategies providing a solid basis for accelerated assessment of SOEC performance evolution and lifetime.
A Developed Plasmatron Design to Enhance Production of Hydrogen in Synthesis Gas Produced by a Fuel Reformer System
Jan 2022
Publication
Feeding IC engines with hydrogen‐rich syngas as an admixture to hydrocarbon fuels can decrease pollutant emissions particularly NOx. It offers a potential technique for low‐environmen‐ tal impact hydrocarbon fuel use in automotive applications. However hydrogen‐rich reformate gas (syngas) production via fuel reforming still needs more research and optimization. In this paper we describe the effect of a plasma torch assembly design on syngas yield and composition during plasma‐assisted reforming of gasoline. Additionally erosion resistance of the cathode‐emitting ma‐ terial under the conditions of gasoline reforming was studied using hafnium metal and lanthanated tungsten alloy. The gasoline reforming was performed with a noncatalytic nonthermal low‐current plasma system in the conditions of partial oxidation in an air and steam mixture. To find the most efficient plasma torch assembly configuration in terms of hydrogen production yield four types of anode design were tested i.e. two types of the swirl ring and two cathode materials while varying the inlet air and fuel flow rates. The experimental results showed that hydrogen was the highest proportion of the produced syngas. The smooth funnel shape anode design in Ring 1 at air/fuel flow rates of 24/4 27/4.5 and 30/5 g/min respectively was more effective than the edged funnel shape. Lanthanated tungsten alloy displayed higher erosion resistance than hafnium metal.
A Direct Synthesis of Platinum/Nickel Co-catalysts on Titanium Dioxide Nanotube Surface from Hydrometallurgical-type Process Streams
Aug 2018
Publication
Solutions that simulate hydrometallurgical base metal process streams with high nickel (Ni) and minor platinum (Pt) concentrations were used to create Pt/Ni nanoparticles on TiO2 nanotube surfaces. For this electrochemical deposition – redox replacement (EDRR) was used that also allowed to control the nanoparticle size density and Pt/Ni content of the deposited nanoparticles. The Pt/Ni nanoparticle decorated titanium dioxide nanotubes (TiO2 nanotubes) become strongly activated for photocatalytic hydrogen (H2) evolution. Moreover EDRR facilitates nanoparticle formation without the need for any additional chemicals and is more effective than electrodeposition alone. Actually a 10000-time enrichment level of Pt took place on the TiO2 surface when compared to Pt content in the solution with the EDRR method. The results show that hydrometallurgical streams offer great potential as an alternative raw material source for industrial catalyst production when coupled with redox replacement electrochemistry.
The Role of Effectiveness Factor on the Modeling of Methanol Steam Reforming Over CuO/ZnO/Al2O3 Catalyst in a Multi-tubular Reactor
Jan 2022
Publication
A pseudo-homogeneous model for the methanol steam reforming process was developed based on reaction kinetics over a CuO/ZnO/Al2O3 catalyst and non-adiabatic heat and mass transfer performances in a co-current packed-bed reactor. A Thiele modulus method and an intraparticle distribution method were applied for predicting the effectiveness factors for main reactions and providing insights into the diffusion-reaction process in a cylindrical catalyst pellet. The results of both methods are validated and show good agreements with the experimental data but the intraparticle distribution method provides better predictions. Results indicate that increases in catalyst size and bulk fluid temperature amplify the impact of intraparticle diffusion limitations showing a decrease in effectiveness factors. To satisfy the requirements of a high temperature polymer electrolyte membrane fuel cell stack the optimized operating conditions which bring the methanol and CO concentrations to less than 1% vol in the reformate stream are determined based on the simulation results.
Magnesium Gasar as a Potential Monolithic Hydrogen Absorbent
Feb 2021
Publication
The study focuses on the aspect of using the structure of gasars i.e. materials with directed open porosity as a potential hydrogen storage. The structure of the tested gasar is composed of a large number of thin open tubular pores running through the entire longitudinal section of the sample. This allows hydrogen to easily penetrate into the entire sample volume. The analysis of pore distribution showed that the longest diffusion path needed for full penetration of the metal structure with hydrogen is about L = 50–70 μm regardless of the external dimensions of the sample. Attempts to hydrogenate the magnesium gasar structure have shown its ability to accumulate hydrogen at a level of 1 wt%. The obtained results were compared with the best result was obtained for the ZK60 alloy after equal channel angular pressing (ECAP) and crushed to a powder form. The result obtained exceeded 4 wt% of hydrogen accumulated in the metal structure at theoretical 6.9 wt% maximum capacity. A model analysis of the theoretic absorption capacity of pure magnesium was also carried out based on the concentration of vacancies in the metal structure. The theoretical results obtained correlate well with experimental data.
Progress in Catalytic Hydrogen Production from Formic Acid over Supported Metal Complexes
Mar 2021
Publication
Formic acid is a liquid organic hydrogen carrier giving hydrogen on demand using catalysts. Metal complexes are known to be used as efficient catalysts for the hydrogen production from formic acid decomposition. Their performance could be better than those of supported catalysts with metal nanoparticles. However difficulties to separate metal complexes from the reaction mixture limit their industrial applications. This problem can be resolved by supporting metal complexes on the surface of different supports which may additionally provide some surface sites for the formic acid activation. The review analyzes the literature on the application of supported metal complexes in the hydrogen production from formic acid. It shows that the catalytic activity of some stable Ru and Ir supported metal complexes may exceed the activity of homogeneous metal complexes used for deposition. Non-noble metal-based complexes containing Fe demonstrated sufficiently high performance in the reaction; however they can be poisoned by water present in formic acid. The proposed review could be useful for development of novel catalysts for the hydrogen production.
Baseload Electricity and Hydrogen Supply Based on Hybrid PV-wind Power Plants
Sep 2019
Publication
The reliable supplies of electricity and hydrogen required for 100% renewable energy systems have been found to be achievable by utilisation of a mix of different resources and storage technologies. In this paper more demanding parameter conditions than hitherto considered are used in measurement of the reliability of variable renewable energy resources. The defined conditions require that supply of baseload electricity (BLEL) and baseload hydrogen (BLH2) occurs solely using cost-optimised configurations of variable photovoltaic solar power onshore wind energy and balancing technologies. The global scenario modelling is based on hourly weather data in a 0.45° × 0.45° spatial resolution. Simulations are conducted for Onsite and Coastal Scenarios from 2020 to 2050 in 10-year time-steps. The results show that for 7% weighted average cost of capital Onsite BLEL can be generated at less than 119 54 41 and 33 €/MWhel in 2020 2030 2040 and 2050 respectively across the best sites with a maximum 20000 TWh annual cumulative generation potential. Up to 20000 TWhH2HHV Onsite BLH2 can be produced at less than 66 48 40 and 35 €/MWhH2HHV in 2020 2030 2040 and 2050 respectively. A partially flexible electricity demand at 8000 FLh could significantly reduce the costs of electricity supply in the studied scenario. Along with battery storage power-to-hydrogen-to-power is found to have a major role in supply of BLEL beyond 2030 as both a daily and seasonal balancing solution. Batteries are not expected to have a significant role in the provision of electricity to water electrolysers.
Sustainable Hydrogen Production: A Role for Fusion
Apr 2007
Publication
This Meeting Report summarises the findings of a two-day workshop in April 2007 at the Culham Science Centre and Worcester College Oxford which explored the potential for large-scale Hydrogen production through methods other than electrolysis.<br/>Operating at the cusp of research and policy-making the UK Energy Research Centre's mission is to be the UK's pre-eminent centre of research and source of authoritative information and leadership on sustainable energy systems. The Centre takes a whole systems approach to energy research incorporating economics engineering and the physical environmental and social sciences while developing and maintaining the means to enable cohesive research in energy. A key supporting function of UKERC is the Meeting Place based in Oxford which aims to bring together members of the UK energy community and overseas experts from different disciplines to learn identify problems develop solutions and further the energy debate.
Hydrolysis-Based Hydrogen Generation Investigation of Aluminium System Adding Low-Melting Metals
Mar 2021
Publication
In this age of human civilization there is a need for more efficient cleaner and renewable energy as opposed to that provided by nonrenewable sources such as coal and oil. In this sense hydrogen energy has been proven to be a better choice. In this paper a portable graphite crucible metal smelting furnace was used to prepare ten multi-element aluminum alloy ingots with different components. The microstructure and phase composition of the ingots and reaction products were analyzed by X-ray diffraction (XRD) scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). The reaction was carried out in a constant temperature water bath furnace at 60°C and the hydrogen production performance of the multi-element aluminum alloys in different proportions was compared by the drainage gas collection method. The experimental results show that the as-cast microstructure of Al–Ga–In–Sn aluminum alloy is composed of a solid solution of Al and part of Ga and a second phase of In3Sn. After the hydrolysis reaction the products were dried at 150°C and then analyzed by XRD. The products were mainly composed of AlOOH and In3Sn. Alloys with different compositions react at the same hydrolysis temperature and the hydrogen production performance is related to the ratio of low-melting-point metal elements. By comparing two different ratios of Ga–In–Sn (GIS) the hydrogen production capacity and production rate when the ratio is 6:3:1 are generally higher than those when the ratio is 7:2:1. The second phase content affects the hydrogen production performance.
Opportunities and Challenges for Thermally Driven Hydrogen Production Using Reverse Electrodialysis System
Jul 2019
Publication
Ongoing and emerging renewable energy technologies mainly produce electric energy and intermittent power. As the energy economy relies on banking energy there is a rising need for chemically stored energy. We propose heat driven reverse electrodialysis (RED) technology with ammonium bicarbonate (AmB) as salt for producing hydrogen. The study provides the authors’ perspective on the commercial feasibility of AmB RED for low grade waste heat (333 K–413 K) to electricity conversion system. This is to our best of knowledge the only existing study to evaluate levelized cost of energy of a RED system for hydrogen production. The economic assessment includes a parametric study and a scenario analysis of AmB RED system for hydrogen production. The impact of various parameters including membrane cost membrane lifetime cost of heating inter-membrane distance and residence time are studied. The results from the economic study suggests RED system with membrane cost less than 2.86 €/m2 membrane life more than 7 years and a production rate of 1.19 mol/m2/h or more are necessary for RED to be economically competitive with the current renewable technologies for hydrogen production. Further salt solubility residence time and inter-membrane distance were found to have impact on levelized cost of hydrogen LCH. In the present state use of ammonium bicarbonate in RED system for hydrogen production is uneconomical. This may be attributed to high membrane cost low (0.72 mol/m2/h) hydrogen production rate and large (1281436 m2) membrane area requirements. There are three scenarios presented the present scenario market scenario and future scenario. From the scenario analysis it is clear that membrane cost and membrane life in present scenario controls the levelized cost of hydrogen. In market scenario and future scenario the hydrogen production rate (which depends on membrane properties inter-membrane distance etc.) the cost of regeneration system and the cost of heating controls the levelized cost of hydrogen. For a thermally driven RED system to be economically feasible the membrane cost not more than 20 €/m2; hydrogen production rate of 3.7 mol/m2/h or higher and cost of heating not more than 0.03 €/kWh for low grade waste heat to hydrogen production.
The Role of the Substrate on the Mechanical and Thermal Stability of Pd Thin Films During Hydrogen (De)sorption
Nov 2020
Publication
In this work we studied the mechanical and thermal stability of ~100 nm Pd thin films magnetron sputter deposited on a bare oxidized Si(100) wafer a sputtered Titanium (Ti) intermediate layer and a spin-coated Polyimide (PI) intermediate layer. The dependence of the film stability on the film morphology and the film-substrate interaction was investigated. It was shown that a columnar morphology with elongated voids at part of the grain boundaries is resistant to embrittlement induced by the hydride formation (α↔β phase transitions). For compact film morphology depending on the rigidity of the intermediate layer and the adherence to the substrate complete transformation (Pd-PI-SiO2/Si) or partly suppression (Pd-Ti-SiO2/Si) of the α to β-phase was observed. In the case of Pd without intermediate layer (Pd-SiO2/Si) buckling delamination occurred. The damage and deformation mechanisms could be understood by the analysis of the stresses and dislocation (defects) behavior near grain boundaries and the film-substrate interface. From diffraction line-broadening combined with microscopy analysis we showed that in Pd thin films stresses relax at critical stress values via different relaxation pathways depending on film-microstructure and film-substrate interaction. On the basis of the in-situ hydriding experiments it was concluded that a Pd film on a flexible PI intermediate layer exhibits free-standing film-like behavior besides being strongly clamped on a stiff SiO2/Si substrate.
Energy Technology Perspectives 2020- Special Report on Carbon Capture Utilisation and Storage
Sep 2020
Publication
Energy Technology Perspectives 2020 is a major new IEA publication focused on the technology needs and opportunities for reaching international climate and sustainable energy goals. This flagship report offers vital analysis and advice on the clean energy technologies the world needs to meet net-zero emissions objectives.
The report’s comprehensive analysis maps out the technologies needed to tackle emissions in all parts of the energy sector including areas where technology progress is still lacking such as long-distance transport and heavy industries. It shows the amount of emissions reductions that are required from electrification hydrogen bioenergy and carbon capture utilisation and storage. It also provides an assessment of emissions from existing infrastructure and what can be done to address them.
Link to Document on IEA website
The report’s comprehensive analysis maps out the technologies needed to tackle emissions in all parts of the energy sector including areas where technology progress is still lacking such as long-distance transport and heavy industries. It shows the amount of emissions reductions that are required from electrification hydrogen bioenergy and carbon capture utilisation and storage. It also provides an assessment of emissions from existing infrastructure and what can be done to address them.
Link to Document on IEA website
Mechanism of Action of Polytetrafluoroethylene Binder on the Performance and Durability of High-temperature Polymer Electrolyte Fuel Cells
Feb 2021
Publication
In this work new insights into impacts of the polytetrafluoroethylene (PTFE) binder on high temperature polymer electrolyte fuel cells (HT-PEFCs) are provided by means of various characterizations and accelerated stress tests. Cathodes with PTFE contents from 0 wt% to 60 wt% were fabricated and compared using electrochemical measurements. The results indicate that the cell with 10 wt% PTFE in the cathode catalyst layer (CCL) shows the best performance due to having the lowest mass transport resistance and cathode protonic resistance. Moreover cyclic voltammograms show that Pt (100) edge and corner sites are significantly covered by PTFE and phosphate anions when the PTFE content is higher than 25 wt%. Open-circuit and low load-cycling conditions are applied to accelerate degradation processes of the HT-PEFCs. The PTFE binder shows a network structure in the pores of the catalyst layer which reduces phosphoric acid leaching during the aging tests. In addition the high binder HT-PEFCs more easily suffer from a mass transport problem leading to more severe performance degradation.
A Study on the Characteristics of Academic Topics Related to Renewable Energy Using the Structural Topic Modelling and the Weak Signal Concept
Mar 2021
Publication
It is important to examine in detail how the distribution of academic research topics related to renewable energy is structured and which topics are likely to receive new attention in the future in order for scientists to contribute to the development of renewable energy. This study uses an advanced probabilistic topic modeling to statistically examine the temporal changes of renewable energy topics by using academic abstracts from 2010–2019 and explores the properties of the topics from the perspective of future signs such as weak signals. As a result in strong signals methods for optimally integrating renewable energy into the power grid are paid great attention. In weak signals interest in large-capacity energy storage systems such as hydrogen supercapacitors and compressed air energy storage showed a high rate of increase. In not-strong-but-well-known signals comprehensive topics have been included such as renewable energy potential barriers and policies. The approach of this study is applicable not only to renewable energy but also to other subjects.
Synthesis and Characterisation of Platinum-cobalt-manganese Ternary Alloy Catalysts Supported on Carbon Nanofibers: An Alternative Catalyst for Hydrogen Evolution Reaction
Mar 2020
Publication
A systematic method for obtaining a novel electrode structure based on PtCoMn ternary alloy catalyst supported on graphitic carbon nanofibers (CNF) for hydrogen evolution reaction (HER) in acidic media is proposed. Ternary alloy nanoparticles (Co0.6Mn0.4 Pt) with a mean crystallite diameter under 10 nm were electrodeposited onto a graphitic support material using a two-step pulsed deposition technique. Initially a surface functionalisation of the carbon nanofibers is performed with the aid of oxygen plasma. Subsequently a short galvanostatic pulse electrodeposition technique is applied. It has been demonstrated that if pulsing current is employed compositionally controlled PtCoMn catalysts can be achieved. Variations of metal concentration ratios in the electrolyte and main deposition parameters such as current density and pulse shape led to electrodes with relevant catalytic activity towards HER. The samples were further characterised using several physico-chemical methods to reveal their morphology structure chemical and electrochemical properties. X-ray diffraction confirms the PtCoMn alloy formation on the graphitic support and energy dispersive X-ray spectroscopy highlights the presence of the three metallic components from the alloy structure. The preliminary tests regarding the electrocatalytic activity of the developed electrodes display promising results compared to commercial Pt/C catalysts. The PtCoMn/CNF electrode exhibits a decrease in hydrogen evolution overpotential of about 250 mV at 40 mA cm−2 in acidic solution (0.5 M H2SO4) when compared to similar platinum based electrodes (Pt/CNF) and a Tafel slope of around 120 mV dec−1 indicating that HER takes place under the Volmer-Heyrovsky mechanismm
Multi-Objective Optimal Design of a Hydrogen Supply Chain Powered with Agro-Industrial Wastes from the Sugarcane Industry: A Mexican Case Study
Jan 2022
Publication
This paper presents an optimization modeling approach to support strategic planning for designing hydrogen supply chain (HSC) networks. The energy source for hydrogen production is proposed to be electricity generated at Mexican sugar factories. This study considers the utilization of existing infrastructure in strategic areas of the country which brings several advantages in terms of possible solutions. This study aims to evaluate the economic and environmental implications of using biomass wastes for energy generation and its integration to the national energy grid where the problem is addressed as a mixed-integer linear program (MILP) adopting maximization of annual profit and minimization of greenhouse gas emissions as optimization criteria. Input data is provided by sugar companies and the national transport and energy information platform and were represented by probability distributions to consider variability in key parameters. Independent solutions show similarities in terms of resource utilization while also significant differences regarding economic and environmental indicators. Multi-objective optimization was performed by a genetic algorithm (GA). The optimal HSC network configuration is selected using a multi-criteria decision technique i.e. TOPSIS. An uncertainty analysis is performed and main economic indicators are estimated by investment assessment. Main results show the trade-off interactions between the HSC elements and optimization criteria. The average internal rate of return (IRR) is estimated to be 21.5% and average payback period is 5.02 years.
Recent Advances in Biomass Pretreatment Technologies for Biohydrogen Production
Jan 2022
Publication
Hydrogen is an economical source of clean energy that has been utilized by industry for decades. In recent years demand for hydrogen has risen significantly. Hydrogen sources include water electrolysis hydrocarbon steam reforming and fossil fuels which emit hazardous greenhouse gases and therefore have a negative impact on global warming. The increasing worldwide population has created much pressure on natural fuels with a growing gap between demand for renewable energy and its insufficient supply. As a result the environment has suffered from alarming increases in pollution levels. Biohydrogen is a sustainable energy form and a preferable substitute for fossil fuel. Anaerobic fermentation photo fermentation microbial and enzymatic photolysis or combinations of such techniques are new approaches for producing biohydrogen. For cost-effective biohydrogen production the substrate should be cheap and renewable. Substrates including algal biomass agriculture residue and wastewaters are readily available. Moreover substrates rich in starch and cellulose such as plant stalks or agricultural waste or food industry waste such as cheese whey are reported to support dark- and photo-fermentation. However their direct utilization as a substrate is not recommended due to their complex nature. Therefore they must be pretreated before use to release fermentable sugars. Various pretreatment technologies have been established and are still being developed. This article focuses on pretreatment techniques for biohydrogen production and discusses their efficiency and suitability including hybrid-treatment technology
Achievements of European Projects on Membrane Reactor for Hydrogen Production
May 2017
Publication
Membrane reactors for hydrogen production can increase both the hydrogen production efficiency at small scale and the electric efficiency in micro-cogeneration systems when coupled with Polymeric Electrolyte Membrane fuel cells. This paper discusses the achievements of three European projects (FERRET FluidCELL BIONICO) which investigate the application of the membrane reactor concept to hydrogen production and micro-cogeneration systems using both natural gas and biofuels (biogas and bio-ethanol) as feedstock. The membranes used to selectively separate hydrogen from the other reaction products (CH4 CO2 H2O etc.) are of asymmetric type with a thin layer of Pd alloy (<5 μm) and supported on a ceramic porous material to increase their mechanical stability. In FERRET the flexibility of the membrane reactor under diverse natural gas quality is validated. The reactor is integrated in a micro-CHP system and achieves a net electric efficiency of about 42% (8% points higher than the reference case). In FluidCELL the use of bio-ethanol as feedstock for micro-cogeneration Polymeric Electrolyte Membrane based system is investigated in off-grid applications and a net electric efficiency around 40% is obtained (6% higher than the reference case). Finally BIONICO investigates the hydrogen production from biogas. While BIONICO has just started FERRET and FluidCELL are in their third year and the two prototypes are close to be tested confirming the potentiality of membrane reactor technology at small scale.
Progress in Biofuel Production from Gasification
May 2017
Publication
Biofuels from biomass gasification are reviewed here and demonstrated to be an attractive option. Recent progress in gasification techniques and key generation pathways for biofuels production process design and integration and socio-environmental impacts of biofuel generation are discussed with the goal of investigating gasification-to-biofuels’ credentials as a sustainable and eco-friendly technology. The synthesis of important biofuels such as bio-methanol bio-ethanol and higher alcohols bio-dimethyl ether Fischer Tropsch fuels bio-methane bio-hydrogen and algae-based fuels is reviewed together with recent technologies catalysts and reactors. Significant thermodynamic studies for each biofuel are also examined. Syngas cleaning is demonstrated to be a critical issue for biofuel production and innovative pathways such as those employed by Choren Industrietechnik Germany and BioMCN the Netherlands are shown to allow efficient methanol generation. The conversion of syngas to FT transportation fuels such as gasoline and diesel over Co or Fe catalysts is reviewed and demonstrated to be a promising option for the future of biofuels. Bio-methane has emerged as a lucrative alternative for conventional transportation fuel with all the advantages of natural gas including a dense distribution trade and supply network. Routes to produce H2 are discussed though critical issues such as storage expensive production routes with low efficiencies remain. Algae-based fuels are in the research and development stage but are shown to have immense potential to become commercially important because of their capability to fix large amounts of CO2 to rapidly grow in many environments and versatile end uses. However suitable process configurations resulting in optimal plant designs are crucial so detailed process integration is a powerful tool to optimize current and develop new processes. LCA and ethical issues are also discussed in brief. It is clear that the use of food crops as opposed to food wastes represents an area fraught with challenges which must be resolved on a case by case basis.
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.
Life Cycle Assessment of Substitute Natural Gas Production from Biomass and Electrolytic Hydrogen
Feb 2021
Publication
The synthesis of a Substitute Natural Gas (SNG) that is compatible with the gas grid composition requirements by using surplus electricity from renewable energy sources looks a favourable solution to store large quantities of electricity and to decarbonise the gas grid network while maintaining the same infrastructure. The most promising layouts for SNG production and the conditions under which SNG synthesis reduces the environmental impacts if compared to its fossil alternative is still largely untapped. In this work six different layouts for the production of SNG and electricity from biomass and fluctuating electricity are compared from the environmental point of view by means of Life Cycle Assessment (LCA) methodology. Global Warming Potential (GWP) Cumulative Energy Demand (CED) and Acidification Potential (AP) are selected as impact indicators for this analysis. The influence of key LCA methodological aspects on the conclusions is also explored. In particular two different functional units are chosen: 1 kg of SNG produced and 1 MJ of output energy (SNG and electricity). Furthermore different approaches dealing with co-production of electricity are also applied. The results show that the layout based on hydrogasification has the lowest impacts on all the considered cases apart from the GWP and the CED with SNG mass as the functional unit and the avoided burden approach. Finally the selection of the multifunctionality approach is found to have a significant influence on technology ranking.
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.
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.
The Role of Hydrogen in the Transition from a Petroleum Economy to a Low-carbon Society
Jun 2021
Publication
A radical decarbonization pathway for the Norwegian society towards 2050 is presented. The paper focuses on the role of hydrogen in the transition when present Norwegian petroleum export is gradually phased out. The study is in line with EU initiatives to secure cooperation opportunities with neighbouring countries to establish an international hydrogen market. Three analytical perspectives are combined. The first uses energy models to investigate the role of hydrogen in an energy and power market perspective without considering hydrogen export. The second uses an economic equilibrium model to examine the potential role of hydrogen export in value creation. The third analysis is a socio-technical case study on the drivers and barriers for hydrogen production in Norway. Main conclusions are that access to renewable power and hydrogen are prerequisites for decarbonization of transport and industrial sectors in Norway and that hydrogen is a key to maintain a high level of economic activity. Structural changes in the economy impacts of new technologies and key enablers and barriers in this transition are discussed.
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.
Pd Catalysts Supported on Bamboo-Like Nitrogen-Doped Carbon Nanotubes for Hydrogen Production
Mar 2021
Publication
Bamboo-like nitrogen-doped carbon nanotubes (N-CNTs) were used to synthesize supported palladium catalysts (0.2–2 wt.%) for hydrogen production via gas phase formic acid decomposition. The beneficial role of nitrogen centers of N-CNTs in the formation of active isolated palladium ions and dispersed palladium nanoparticles was demonstrated. It was shown that although the surface layers of N-CNTs are enriched with graphitic nitrogen palladium first interacts with accessible pyridinic centers of N-CNTs to form stable isolated palladium ions. The activity of Pd/N-CNTs catalysts is determined by the ionic capacity of N-CNTs and dispersion of metallic nanoparticles stabilized on the nitrogen centers. The maximum activity was observed for the 0.2% Pd/N-CNTs catalyst consisting of isolated palladium ions. A ten-fold increase in the concentration of supported palladium increased the contribution of metallic nanoparticles with a mean size of 1.3 nm and decreased the reaction rate by only a factor of 1.4.
From Post-Combustion Carbon Capture to Sorption-Enhanced Hydrogen Production: A State-of-the-Art Review of Carbonate Looping Process Feasibility
Oct 2018
Publication
Carbon capture and storage is expected to play a pivotal role in achieving the emission reduction targets established by the Paris Agreement. However the most mature technologies have been shown to reduce the net efficiency of fossil fuel-fired power plants by at least 7% points increasing the electricity cost. Carbonate looping is a technology that may reduce these efficiency and economic penalties. Its maturity has increased significantly over the past twenty years mostly due to development of novel process configurations and sorbents for improved process performance. This review provides a comprehensive overview of the calcium looping concepts and statistically evaluates their techno-economic feasibility. It has been shown that the most commonly reported figures for the efficiency penalty associated with calcium looping retrofits were between 6 and 8% points. Furthermore the calcium-looping-based coal-fired power plants and sorption-enhanced hydrogen production systems integrated with combined cycles and/or fuel cells have been shown to achieve net efficiencies as high as 40% and 50–60% respectively. Importantly the performance of both retrofit and greenfield scenarios can be further improved by increasing the degree of heat integration as well as using advanced power cycles and enhanced sorbents. The assessment of the economic feasibility of calcium looping concepts has indicated that the cost of carbon dioxide avoided will be between 10 and 30 € per tonne of carbon dioxide and 10–50 € per tonne of carbon dioxide in the retrofit and greenfield scenarios respectively. However limited economic data have been presented in the current literature for the thermodynamic performance of calcium looping concepts.
Gas Switching Reforming for Flexible Power and Hydrogen Production to Balance Variable Renewables
May 2019
Publication
Variable renewable energy (VRE) is expected to play a major role in the decarbonization of the electricity sector. However decarbonization via VRE requires a fleet of flexible dispatchable plants with low CO2 emissions to supply clean power during times with limited wind and sunlight. These plants will need to operate at reduced capacity factors with frequent ramps in electricity output posing techno-economic challenges. This study therefore presents an economic assessment of a new near-zero emission power plant designed for this purpose. The gas switching reforming combined cycle (GSR-CC) plant can produce electricity during times of low VRE output and hydrogen during times of high VRE output. This product flexibility allows the plant to operate continuously even when high VRE output makes electricity production uneconomical. Although the CO2 avoidance cost of the GSR-CC plant (€61/ton) was similar to the benchmark post-combustion CO2 capture plant under baseload operation GSR-CC clearly outperformed the benchmark in a more realistic scenario where continued VRE expansion forces power plants into mid-load operation (45% capacity factor). In this scenario GSR-CC promises a 5 %-point higher annualized investment return than the post-combustion benchmark. GSR-CC therefore appears to be a promising concept for a future scenario with high VRE market share and CO2 prices provided that a large market for clean hydrogen is established.
Hydrogen Production from Instant Noodle Wastewater by Organic Electrocatalyst Coated on PVC Surface
Mar 2020
Publication
The potential of electron-donating capability in methoxy groups of antioxidant containing protein (ACAP) as organic catalyst is restricted by its low isoelectric point. The goal of this study is to construct endure ACAP based metal-free organic catalyst for hydrogen production from electrolysis of noodle wastewater. The ACAP was coated thermomechanically on PVC sheet and its performance was tested during electrolysis of noodle wastewater. The morphological analysis phase analysis and elemental analysis of coated materials have shown a simultaneous pattern with electrolysis performances. The use of graphite flake to cover turmeric ACAP obstructs the electron to attack directly the positive charge of ACAP so that the electrocatalytic endurance increases while maintaining the hydrogen production rate. The combination of phenolic and enzymatic ACAPs is found to have the slowest reaction rate and lowest hydrogen production. The phenolic compound inhibits the enzymatic reaction.
MELCOR Analysis of a SPARC Experiment for Spray-PAR Interaction During a Hydrogen Release
Oct 2020
Publication
A series of experiments were performed in the SPARC (spray-aerosol-recombiner-combustion) test facility to simulate a hydrogen mitigation system with the actuation of a PAR (passive auto-catalytic re-combiner) and spray system. In this study the SPARC-SPRAY-PAR (SSP1) experiment is chosen to benchmark the MELCOR (a lumped-parameter code for severe accident analysis) predictions against test data. For this purpose firstly we prepared the base input model of the SPARC test vessel and tested it by a simple verification problem with well-defined boundary conditions. The implementation of a currently used PAR correlation in MELCOR is shown to be appropriate for the simulation of a PAR actuation experiment. In an SSP1 experiment the PAR is reacting with hydrogen and the spray actuation starts as soon as hydrogen injection is complete. The MELCOR simulation well predicts the pressure behavior and the gas flow affected by operating both a PAR and spray system. However the local hydrogen concentration measurement near the inlet nozzle is much higher than the volume average-value by MELCOR since high jet flow from the nozzle is dispersed in the corresponding cell volume. The experimental reproduction of the phenomena we expect or conversely the identification of phenomena we do not understand will continue to support the verification of analytical models using experimental data and to analyze the impact of spray on PAR operations in severe accident conditions.
Advances in Reforming and Partial Oxidation of Hydrocarbons for Hydrogen Production and Fuel Cell Applications
May 2019
Publication
One of the most attractive routes for the production of hydrogen or syngas for use in fuel cell applications is the reforming and partial oxidation of hydrocarbons. The use of hydrocarbons in high temperature fuel cells is achieved through either external or internal reforming. Reforming and partial oxidation catalysis to convert hydrocarbons to hydrogen rich syngas plays an important role in fuel processing technology. The current research in the area of reforming and partial oxidation of methane methanol and ethanol includes catalysts for reforming and oxidation methods of catalyst synthesis and the effective utilization of fuel for both external and internal reforming processes. In this paper the recent progress in these areas of research is reviewed along with the reforming of liquid hydrocarbons from this an overview of the current best performing catalysts for the reforming and partial oxidizing of hydrocarbons for hydrogen production is summarized.
Continuous Hydrogen Regeneration Through the Oxygen Vacancy Control of Metal Oxides Using Microwave Irradiation
Nov 2018
Publication
The amount of hydrogen gas generated from metal oxide materials based on a thermochemical water-splitting method gradually reduces as the surface of the metal oxide oxidizes during the hydrogen generation process. To regenerate hydrogen the oxygen reduction process of a metal oxide at high temperatures (1000–2500 °C) is generally required. In this study to overcome the problem of an energy efficiency imbalance in which the required energy of the oxygen reduction process for hydrogen regeneration is higher than the generated hydrogen energy we investigated the possibility of the oxygen reduction of a metal oxide with a low energy using microwave irradiation. For this purpose a macroporous nickel-oxide structure was used as a metal oxide catalyst to generate hydrogen gas and the oxidized surface of the macroporous nickel-oxide structure could be reduced by microwave irradiation. Through this oxidation reduction process ∼750 μmol g−1 of hydrogen gas could be continuously regenerated. In this way it is expected that oxygen-enriched metal oxide materials can be efficiently reduced by microwave irradiation with a low power consumption of <∼4% compared to conventional high-temperature heat treatment and thus can be used for efficient hydrogen generation and regeneration processes in the future.
A Comparative Technoeconomic Analysis of Renewable Hydrogen Production Using Solar Energy
May 2016
Publication
A technoeconomic analysis of photoelectrochemical (PEC) and photovoltaic-electrolytic (PV-E) solar-hydrogen production of 10 000 kg H2 day−1 (3.65 kilotons per year) was performed to assess the economics of each technology and to provide a basis for comparison between these technologies as well as within the broader energy landscape. Two PEC systems differentiated primarily by the extent of solar concentration (unconcentrated and 10× concentrated) and two PV-E systems differentiated by the degree of grid connectivity (unconnected and grid supplemented) were analyzed. In each case a base-case system that used established designs and materials was compared to prospective systems that might be envisioned and developed in the future with the goal of achieving substantially lower overall system costs. With identical overall plant efficiencies of 9.8% the unconcentrated PEC and non-grid connected PV-E system base-case capital expenses for the rated capacity of 3.65 kilotons H2 per year were $205 MM ($293 per m2 of solar collection area (mS−2) $14.7 WH2P−1) and $260 MM ($371 mS−2 $18.8 WH2P−1) respectively. The untaxed plant-gate levelized costs for the hydrogen product (LCH) were $11.4 kg−1 and $12.1 kg−1 for the base-case PEC and PV-E systems respectively. The 10× concentrated PEC base-case system capital cost was $160 MM ($428 mS−2 $11.5 WH2P−1) and for an efficiency of 20% the LCH was $9.2 kg−1. Likewise the grid supplemented base-case PV-E system capital cost was $66 MM ($441 mS−2 $11.5 WH2P−1) and with solar-to-hydrogen and grid electrolysis system efficiencies of 9.8% and 61% respectively the LCH was $6.1 kg−1. As a benchmark a proton-exchange membrane (PEM) based grid-connected electrolysis system was analyzed. Assuming a system efficiency of 61% and a grid electricity cost of $0.07 kWh−1 the LCH was $5.5 kg−1. A sensitivity analysis indicated that relative to the base-case increases in the system efficiency could effect the greatest cost reductions for all systems due to the areal dependencies of many of the components. The balance-of-systems (BoS) costs were the largest factor in differentiating the PEC and PV-E systems. No single or combination of technical advancements based on currently demonstrated technology can provide sufficient cost reductions to allow solar hydrogen to directly compete on a levelized cost basis with hydrogen produced from fossil energy. Specifically a cost of CO2 greater than ∼$800 (ton CO2)−1 was estimated to be necessary for base-case PEC hydrogen to reach price parity with hydrogen derived from steam reforming of methane priced at $12 GJ−1 ($1.39 (kg H2)−1). A comparison with low CO2 and CO2-neutral energy sources indicated that base-case PEC hydrogen is not currently cost-competitive with electrolysis using electricity supplied by nuclear power or from fossil-fuels in conjunction with carbon capture and storage. Solar electricity production and storage using either batteries or PEC hydrogen technologies are currently an order of magnitude greater in cost than electricity prices with no clear advantage to either battery or hydrogen storage as of yet. Significant advances in PEC technology performance and system cost reductions are necessary to enable cost-effective PEC-derived solar hydrogen for use in scalable grid-storage applications as well as for use as a chemical feedstock precursor to CO2-neutral high energy-density transportation fuels. Hence such applications are an opportunity for foundational research to contribute to the development of disruptive approaches to solar fuels generation systems that can offer higher performance at much lower cost than is provided by current embodiments of solar fuels generators. Efforts to directly reduce CO2 photoelectrochemically or electrochemically could potentially produce products with higher value than hydrogen but many as yet unmet challenges include catalytic efficiency and selectivity and CO2 mass transport rates and feedstock cost. Major breakthroughs are required to obtain viable economic costs for solar hydrogen production but the barriers to achieve cost-competitiveness with existing large-scale thermochemical processes for CO2 reduction are even greater.
Biomass Potential for Producing Power via Green Hydrogen
Dec 2021
Publication
Hydrogen (H2 ) has become an important energy vector for mitigating the effects of climate change since it can be obtained from renewable sources and can be fed to fuel cells for producing power. Bioethanol can become a green H2 source via Ethanol Steam Reforming (ESR) but several variables influence the power production in the fuel cell. Herein we explored and optimized the main variables that affect this power production. The process includes biomass fermentation bioethanol purification H2 production via ESR syngas cleaning by a CO-removal reactor and power production in a high temperature proton exchange membrane fuel cell (HT-PEMFC). Among the explored variables the steam-to-ethanol molar ratio (S/E) employed in the ESR has the strongest influence on power production process efficiency and energy consumption. This effect is followed by other variables such as the inlet ethanol concentration and the ESR temperature. Although the CO-removal reactor did not show a significant effect on power production it is key to increase the voltage on the fuel cell and consequently the power production. Optimization was carried out by the response surface methodology (RSM) and showed a maximum power of 0.07 kWh kg−1 of bioethanol with an efficiency of 17% when ESR temperature is 700 ◦C. These values can be reached from different bioethanol sources as the S/E and CO-removal temperature are changed accordingly with the inlet ethanol concentration. Because there is a linear correlation between S/E and ethanol concentration it is possible to select a proper S/E and CO-removal temperature to maximize the power generation in the HT-PEMFC via ESR. This study serves as a starting point to diversify the sources for producing H2 and moving towards a H2 -economy.
Recent Progress in the Steam Reforming of Bio-Oil for Hydrogen Production: A Review of Operating Parameters, Catalytic Systems and Technological Innovations
Dec 2021
Publication
The present review focuses on the production of renewable hydrogen through the catalytic steam reforming of bio-oil the liquid product of the fast pyrolysis of biomass. Although in theory the process is capable of producing high yields of hydrogen in practice certain technological issues require radical improvements before its commercialization. Herein we illustrate the fundamental knowledge behind the technology of the steam reforming of bio-oil and critically discuss the major factors influencing the reforming process such as the feedstock composition the reactor design the reaction temperature and pressure the steam to carbon ratio and the hour space velocity. We also emphasize the latest research for the best suited reforming catalysts among the specific groups of noble metal transition metal bimetallic and perovskite type catalysts. The effect of the catalyst preparation method and the technological obstacle of catalytic deactivation due to coke deposition metal sintering metal oxidation and sulfur poisoning are addressed. Finally various novel modified steam reforming techniques which are under development are discussed such as the in-line two-stage pyrolysis and steam reforming the sorption enhanced steam reforming (SESR) and the chemical looping steam reforming (CLSR). Moreover we argue that while the majority of research studies examine hydrogen generation using different model compounds much work must be done to optimally treat the raw or aqueous bio-oil mixtures for efficient practical use. Moreover further research is also required on the reaction mechanisms and kinetics of the process as these have not yet been fully understood.
Kinetic Modeling and Quantum Yields: Hydrogen Production via Pd‐TiO2 Photocatalytic Water Splitting under Near‐UV and Visible Light
Jan 2022
Publication
A palladium (Pd) doped mesoporous titanium dioxide (TiO2) photocatalyst was used to produce hydrogen (H2) via water splitting under both near‐UV and visible light. Experiments were carried out in the Photo‐CREC Water‐II Reactor (PCW‐II) using a 0.25 wt% Pd‐TiO2 photocatalyst initial pH = 4 and 2.0 v/v% ethanol as an organic scavenger. After 6 h of near‐UV irradiation this photocatalyst yielded 113 cm3 STP of hydrogen (H2). Furthermore after 1 h of near‐UV photoreduc‐ tion followed by 5 h of visible light the 0.25 wt% Pd‐TiO2 photocatalyst yielded 5.25 cm3 STP of H2. The same photocatalyst photoreduced for 24 h under near‐UV and subsequently exposed to 5 h of visible light yielded 29 cm3 STP of H2. It was observed that the promoted redox reactions led to the production of hydrogen and by‐products such as methane ethane ethylene acetaldehyde carbon monoxide carbon dioxide and hydrogen peroxide. These redox reactions could be modeled using an “in series‐parallel” reaction network and Langmuir Hinshelwood based kinetics. The proposed rate equations were validated using statistical analysis for the experimental data and calculated kinetic parameters. Furthermore Quantum yields (QYୌ%) based on the H produced were also established at promising levels: (a) 34.8% under near‐UV light and 1.00 g L−1 photocatalyst concen‐ tration; (b) 8.8% under visible light and 0.15 g L−1. photocatalyst concentration following 24 h of near‐UV.
Cyclic Voltammetry of a Cobaloxime Catalyst
Jul 2019
Publication
<br/>Cyclic Voltammetry Measurements performed on a Cobaloxime Catalyst designed for photochemical hydrogen production.
Laser Powder Bed Fusion of WE43 in Hydrogen-argon-gas Atmosphere
Sep 2020
Publication
Growing demand for individual and especially complex parts with emphasis on biomedical or lightweight applications enhances the importance of laser powder bed fusion. Magnesium alloys offer both biocompatibility and low density but feature a very high melting point of oxide layers while the evaporation temperature of pure magnesium is much lower. This impedes adequate part quality and process reproducibility. To weaken this oxide layer and enhance processability a 2 %-hydrogen-argon-gas atmosphere was investigated. A machine system was modified to the use of the novel inert gas to determine the influence of gas atmosphere on hollow cuboids and solid cubes. While processing a 20.3 % decrease in structure width and 20.6 % reduction in standard deviation of the cuboids was determined. There was no significate influence on relative density of solid cubes although eight of the ten highest density specimen were fabricated with the hydrogen addition.
Multi-Tubular Reactor for Hydrogen Production CFD Thermal Design and Experimental Testing
Jan 2019
Publication
This study presents the Computational Fluid Dynamics (CFD) thermal design and experimental tests results for a multi-tubular solar reactor for hydrogen production based on the ferrite thermochemical cycle in a pilot plant in the Plataforma Solar de Almería (PSA). The methodology followed for the solar reactor design is described as well as the experimental tests carried out during the testing campaign and characterization of the reactor. The CFD model developed for the thermal design of the solar reactor has been validated against the experimental measurements with a temperature error ranging from 1% to around 10% depending on the location within the reactor. The thermal balance in the reactor (cavity and tubes) has been also solved by the CFD model showing a 7.9% thermal efficiency of the reactor. CFD results also show the percentage of reacting media inside the tubes which achieve the required temperature for the endothermic reaction process with 90% of the ferrite pellets inside the tubes above the required temperature of 900 °C. The multi-tubular solar reactor designed with aid of CFD modelling and simulations has been built and operated successfully
Techno-economic calculations of small-scale hydrogen supply systems for zero emission transport in Norway
Jun 2019
Publication
In Norway where nearly 100% of the power is hydroelectric it is natural to consider water electrolysis as the main production method of hydrogen for zero-emission transport. In a start-up market with low demand for hydrogen one may find that small-scale WE-based hydrogen production is more cost-efficient than large-scale production because of the potential to reach a high number of operating hours at rated capacity and high overall system utilization rate. Two case studies addressing the levelized costs of hydrogen in local supply systems have been evaluated in the present work: (1) Hydrogen production at a small-scale hydroelectric power plant (with and without on-site refuelling) and (2) Small hydrogen refuelling station for trucks (with and without on-site hydrogen production). The techno-economic calculations of the two case studies show that the levelized hydrogen refuelling cost at the small-scale hydroelectric power plant (with a local station) will be 141 NOK/kg while a fleet of 5 fuel cell trucks will be able to refuel hydrogen at a cost of 58 NOK/kg at a station with on-site production or 71 NOK/kg at a station based on delivered hydrogen. The study shows that there is a relatively good business case for local water electrolysis and supply of hydrogen to captive fleets of trucks in Norway particularly if the size of the fleet is sufficiently large to justify the installation of a relatively large water electrolyzer system (economies of scale). The ideal concept would be a large fleet of heavy-duty vehicles (with a high total hydrogen demand) and a refuelling station with nearly 100% utilization of the installed hydrogen production capacity.
Pathways to Low-cost Clean Hydrogen Production with Gas Switching Reforming
Feb 2020
Publication
Gas switching reforming (GSR) is a promising technology for natural gas reforming with inherent CO2 capture. Like conventional steam methane reforming (SMR) GSR can be integrated with CO2 -gas shift and pressure swing adsorption units for pure hydrogen production. The resulting GSR-H2 process concept was techno-economically assessed in this study. Results showed that GSR-H2 can achieve 96% CO2 capture at a CO2 avoidance cost of 15 $/ton (including CO2 transport and storage). Most components of the GSR-H2 process are proven technologies but long-term oxygen carrier stability presents an important technical uncertainty that can adversely affect competitiveness when the material lifetime drops below one year. Relative to the SMR benchmark GSR-H2 replaces some fuel consumption with electricity consumption making it more suitable to regions with higher natural gas prices and lower electricity prices. Some minor alterations to the process configuration can adjust the balance between fuel and electricity consumption to match local market conditions. The most attractive commercialization pathway for the GSR-H2 technology is initial construction without CO2 capture followed by simple retrofitting for CO2 capture when CO2 taxes rise and CO2 transport and storage infrastructure becomes available. These features make the GSR-H2 technology robust to almost any future energy market scenario.
Evaluation of Sorbents for High Temperature Removal of Tars, Hydrogen Sulphide, Hydrogen Chloride and Ammonia from Biomass-derived Syngas by Using Aspen Plus
Jan 2020
Publication
Biomass gasification is a promising technology to produce secondary fuels or heat and power offering considerable advantages over fossil fuels. An important aspect in the usage of producer gas is the removal of harmful contaminants from the raw syngas. Thus the object of this study is the development of a simulation model for a gasifier including gas clean-up for which a fluidized-bed gasifier for biomass-derived syngas production was considered based on a quasi-equilibrium approach through Gibbs free energy minimisation and including an innovative hot gas cleaning constituted by a combination of catalyst sorbents inside the gasification reactor catalysts in the freeboard and subsequent sorbent reactors by using Aspen Plus software. The gas cleaning chain simulates the raw syngas clean-up for several organic and inorganic contaminants i.e. toluene benzene naphthalene hydrogen sulphide hydrogen chloride and ammonia. The tar and inorganic contaminants final values achieved are under 1 g/Nm3 and 1 ppm respectively.
Hydrogen Production Using Solar Energy - Technical Analysis
Mar 2019
Publication
This paper presents a case study concerning a plant for hydrogen production and storage having a daily capacity of 100kg. The plant is located in Cluj-Napoca Romania. It produces hydrogen by means of water electrolysis while the energy is provided using solar energy. We performed the calculations for four different technical solutions used for the hydrogen production and storage plant and also we considered three scenarios regarding the sub-systems of the hydrogen production and storage plant efficiency. The conclusion of this study is that one can maximize the conversion of solar radiation into chemical energy in the form of hydrogen by hybridizing the solar hydrogen production system namely using both electrical energy as well as thermal energy in the form of steam.
Assessment of Hydrogen Direct Reduction for Fossil-free Steelmaking
Aug 2018
Publication
Climate policy objectives require zero emissions across all sectors including steelmaking. The fundamental process changes needed for reaching this target are yet relatively unexplored. In this paper we propose and assess a potential design for a fossil-free steelmaking process based on direct reduction of iron ore with hydrogen. We show that hydrogen direct reduction steelmaking needs 3.48 MWh of electricity per tonne of liquid steel mainly for the electrolyser hydrogen production. If renewable electricity is used the process will have essentially zero emissions. Total production costs are in the range of 361–640 EUR per tonne of steel and are highly sensitive to the electricity price and the amount of scrap used. Hydrogen direct reduction becomes cost competitive with an integrated steel plant at a carbon price of 34–68 EUR per tonne CO2 and electricity costs of 40 EUR/MWh. A key feature of the process is flexibility in production and electricity demand which allows for grid balancing through storage of hydrogen and hot-briquetted iron or variations in the share of scrap used.
Bioanode and Biocathode Performance in a Microbial Electrolysis Cell
Jan 2017
Publication
The bioanode is important for a microbial electrolysis cell (MEC) and its robustness to maintain its catalytic activity affects the performance of the whole system. Bioanodes enriched at a potential of +0.2 V (vs. standard hydrogen electrode) were able to sustain their oxidation activity when the anode potential was varied from 0.3 up to +1.0 V. Chronoamperometric test revealed that the bioanode produced peak current density of 0.36 A/m2 and 0.37 A/m2 at applied potential 0 and +0.6 V respectively. Meanwhile hydrogen production at the biocathode was proportional to the applied potential in the range from 0.5 to 1.0 V. The highest production rate was 7.4 L H2/(m2 cathode area)/day at 1.0 V cathode potential. A limited current output at the bioanode could halt the biocathode capability to generate hydrogen. Therefore maximum applied potential that can be applied to the biocathode was calculated as 0.84 V without overloading the bioanode
A Numerical Performance Study of a Fixed-bed Reactor for Methanol Synthesis by CO2 Hydrogenation
Mar 2021
Publication
Synthetic fuels are needed to replace their fossil counterparts for clean transport. Presently their production is still inefficient and costly. To enhance the process of methanol production from CO2 and H2 and reduce its cost a particle-resolved numerical simulation tool is presented. A global surface reaction model based on the Langmuir-Hinshelwood-Hougen-Watson kinetics is utilized. The approach is first validated against standard benchmark problems for non-reacting and reacting cases. Next the method is applied to study the performance of methanol production in a 2D fixed-bed reactor under a range of parameters. It is found that methanol yield enhances with pressure catalyst loading reactant ratio and packing density. The yield diminishes with temperature at adiabatic conditions while it shows non-monotonic change for the studied isothermal cases. Overall the staggered and the random catalyst configurations are found to outperform the in-line system.
Modelling and Optimization of a Flexible Hydrogen-fueled Pressurized PEMFC Power Plant for Grid Balancing Purposes
Feb 2021
Publication
In a scenario characterized by an increasing penetration of non-dispatchable renewable energy sources and the need of fast-ramping grid-balancing power plants the EU project GRASSHOPPER aims to setup and demonstrate a highly flexible PEMFC Power Plant hydrogen fueled and scalable to MW-size designed to provide grid support.<br/>In this work different layouts proposed for the innovative MW-scale plant are simulated to optimize design and off-design operation. The simulation model details the main BoP components performances and includes a customized PEMFC model validated through dedicated experiments.<br/>The system may operate at atmospheric or mild pressurized conditions: pressurization to 0.7 barg allows significantly higher net system efficiency despite the increasing BoP consumptions. The additional energy recovery from the cathode exhaust with an expander gives higher net power and net efficiency adding up to 2%pt and reaching values between 47%LHV and 55%LHV for currents between 100% and 20% of the nominal value.
Chitosan Flocculation Associated with Biofilms of C. Saccharolyticus and C. Owensensis Enhances Biomass Retention in a CSTR
Jun 2021
Publication
Cell immobilization and co-culture techniques have gained attention due to its potential to obtain high volumetric hydrogen productivities (QH2). Chitosan retained biomass in the fermentation of co-cultures of Caldicellulosiruptor saccharolyticus and C. owensensis efficiently up to a maximum dilution rate (D) of 0.9 h−1. Without chitosan wash out of the co-culture occurred earlier accompanied with approximately 50% drop in QH2 (D > 0.4 h−1). However butyl rubber did not show as much potential as carrier material; it did neither improve QH2 nor biomass retention in continuous culture. The population dynamics revealed that C. owensensis was the dominant species (95%) in the presence of chitosan whereas C. saccharolyticus was the predominant (99%) during cultivation without chitosan. In contrast the co-culture with rubber as carrier maintained the relative population ratios around 1:1. This study highlighted chitosan as an effective potential carrier for immobilization thereby paving the way for cost – effective hydrogen production.
PEM Fuel Cell Performance with Solar Air Preheating
Feb 2020
Publication
Proton Exchange Membrane Fuel Cells (PEMFC) have proven to be a promising energy conversion technology in various power applications and since it was developed it has been a potential alternative over fossil fuel-based engines and power plants all of which produce harmful by-products. The inlet air coolant and reactants have an important effect on the performance degradation of the PEMFC and certain power outputs. In this work a theoretical model of a PEM fuel cell with solar air heating system for the preheating hydrogen of PEM fuel cell to mitigate the performance degradation when the fuel cell operates in cold environment is proposed and evaluated by using energy analysis. Considering these heating and energy losses of heat generation by hydrogen fuel cells the idea of using transpired solar collectors (TSC) for air preheating to increase the inlet air temperature of the low-temperature fuel cell could be a potential development. The aim of the current article is applying solar air preheating for the hydrogen fuel cells system by applying TSC and analyzing system performance. Results aim to attention fellow scholars as well as industrial engineers in the deployment of solar air heating together with hydrogen fuel cell systems that could be useful for coping with fossil fuel-based power supply systems.
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.
Life-cycle Assessment of Hydrogen Technologies with the Focus on EU Critical Raw Materials and End-of-life Strategies
Aug 2020
Publication
We present the results of a life-cycle assessment (LCA) for the manufacturing and end-of-life (EoL) phases of the following fuel-cell and hydrogen (FCH) technologies: alkaline water electrolyser (AWE) polymer-electrolyte-membrane water electrolyser (PEMWE) high-temperature (HT) and low-temperature (LT) polymer-electrolyte-membrane fuel cells (PEMFCs) together with the balance-of-plant components. New life-cycle inventories (LCIs) i.e. material inputs for the AWE PEMWE and HT PEMFC are developed whereas the existing LCI for the LT PEMFC is adopted from a previous EU-funded project. The LCA models for all four FCH technologies are created by modelling the manufacturing phase followed by defining the EoL strategies and processes used and finally by assessing the effects of the EoL approach using environmental indicators. The effects are analysed with a stepwise approach where the CML2001 assessment method is used to evaluate the environmental impacts. The results show that the environmental impacts of the manufacturing phase can be substantially reduced by using the proposed EoL strategies (i.e. recycled materials being used in the manufacturing phase and replacing some of the virgin materials). To point out the importance of critical materials (in this case the platinum-group metals or PGMs) and their recycling strategies further analyses were made. By comparing the EoL phase with and without the recycling of PGMs an increase in the environmental impacts is observed which is much greater in the case of both fuel-cell systems because they contain a larger quantity of PGMs.
Methane Pyrolysis in a Molten Gallium Bubble Column Reactor for Sustainable Hydrogen Production: Proof of Concept & Techno-economic Assessment
Dec 2020
Publication
Nowadays nearly 50% of the hydrogen produced worldwide comes from Steam Methane Reforming (SMR) at an environmental burden of 10.5 tCO2 eq/tH2 accelerating the consequences of global warming. One way to produce clean hydrogen is via methane pyrolysis using melts of metals and salts. Compared to SMR significant less CO2 is produced due to conversion of methane into hydrogen and carbon making this route more sustainable to generate hydrogen. Hydrogen is produced with high purity and solid carbon is segregated and deposited on the molten bath. Carbon may be sold as valuable co-product making industrial scale promising. In this work methane pyrolysis was performed in a quartz bubble column using molten gallium as heat transfer agent and catalyst. A maximum conversion of 91% was achieved at 1119 °C and ambient pressure with a residence time of the bubbles in the liquid of 0.5 s. Based on in-depth analysis of the carbon it can be characterized as carbon black. Techno-economic and sensitivity analyses of the industrial concept were done for different scenarios. The results showed that if co-product carbon is saleable and a CO2 tax of 50 euro per tonne is imposed to the processes the molten metal technology can be competitive with SMR.
Decarbonization Synergies From Joint Planning of Electricity and Hydrogen Production: A Texas Case Study
Oct 2020
Publication
Hydrogen (H2) shows promise as an energy carrier in contributing to emissions reductions from sectors which have been difficult to decarbonize like industry and transportation. At the same time flexible H2 production via electrolysis can also support cost-effective integration of high shares of variable renewable energy (VRE) in the power system. In this work we develop a least-cost investment planning model to co-optimize investments in electricity and H2 infrastructure to serve electricity and H2 demands under various low-carbon scenarios. Applying the model to a case study of Texas in 2050 we find that H2 is produced in approximately equal amounts from electricity and natural gas under the least-cost expansion plan with a CO2 price of $30–60/tonne. An increasing CO2 price favors electrolysis while increasing H2 demand favors H2 production from Steam Methane Reforming (SMR) of natural gas. H2 production is found to be a cost effective solution to reduce emissions in the electric power system as it provides flexibility otherwise provided by natural gas power plants and enables high shares of VRE with less battery storage. Additionally the availability of flexible electricity demand via electrolysis makes carbon capture and storage (CCS) deployment for SMR cost-effective at lower CO2 prices ($90/tonne CO2) than for power generation ($180/tonne CO2 ). The total emissions attributable to H2 production is found to be dependent on the H2 demand. The marginal emissions from H2 production increase with the H2 demand for CO2 prices less than $90/tonne CO2 due to shift in supply from electrolysis to SMR. For a CO2 price of $60/tonne we estimate the production weighted-average H2 price to be between $1.30–1.66/kg across three H2 demand scenarios. These findings indicate the importance of joint planning of electricity and H2 infrastructure for cost-effective energy system decarbonization.
CCS Deployment at Dispersed Industrial Sites: Element Energy for the Department for Business Energy and Industrial Strategy (BEIS)
Aug 2020
Publication
This report identifies and assesses a range of high-level deployment options for industrial carbon capture usage and storage (CCUS) technology located in non-clustered ‘dispersed’ sites that are isolated from potential carbon dioxide transport infrastructure in the UK.
It provides:
It provides:
- an identification of the challenges and barriers to CCUS deployment specifically at these dispersed sites
- an appraisal of the range of high-level options for CCUS deployment and the risks associated with each challenge
- an assessment of the most promising options based on their cost risk and emission reduction potential
- BEIS commissioned Element Energy to produce the report.
Membrane Based Purification of Hydrogen System (MEMPHYS)
Feb 2019
Publication
A hydrogen purification system based on the technology of the electrochemical hydrogen compression and purification is introduced. This system is developed within the scope of the project MEMPHYS. Therefore the project its targets and the different work stages are presented. The technology of the electrochemical purification and the state of the art of hydrogen purification are described. Early measurements in the project have been carried out and the results are shown and discussed. The ability of the technology to recover hydrogen from a gas mixture can be recognized and an outlook into further optimizations shows the future potential. A big advantage is the simultaneous compression of the purified hydrogen up to 200 bar therefore facilitating the transportation and storage.
Dynamic System Modeling of Thermally-integrated Concentrated PV-electrolysis
Feb 2021
Publication
Understanding the dynamic response of a solar fuel processing system utilizing concentrated solar radiation and made of a thermally-integrated photovoltaic (PV) and water electrolyzer (EC) is important for the design development and implementation of this technology. A detailed dynamic non-linear process model is introduced for the fundamental system components (i.e. PV EC pump etc.) in order to investigate the coupled system behavior and performance synergy notably arising from the thermal integration. The nominal hydrogen production power is ∼2 kW at a hydrogen system efficiency of 16–21% considering a high performance triple junction III-V PV module and a proton exchange membrane EC. The device operating point relative to the maximum power point of the PV was shown to have a differing influence on the system performance when subject to temperature changes. The non-linear coupled behavior was characterised in response to step changes in water flowrate and solar irradiance and hysteresis of the current-voltage operating point was demonstrated. Whilst the system responds thermally to changes in operating conditions in the range of 0.5–2 min which leads to advantageously short start-up times a number of control challenges are identified such as the impact of pump failure electrical PV-EC disconnection and the potentially damaging accentuated temperature rise at lower water flowrates. Finally the simulation of co-generation of heat and hydrogen for various operating conditions demonstrates the significant potential for system efficiency enhancements and the required development of control strategies for demand matching is discussed.
Integrating IT-SOFC and Gasification Combined Cycle with Methanation Reactor and Hydrogen Firing for Near Zero-emission Power Generation from Coal
Apr 2011
Publication
Application of Solid Oxide Fuel Cells (SOFC) in gasification-based power plants would represent a turning point in the power generation sector allowing to considerably increase the electric efficiency of coal-fired power stations while reducing CO2 and other pollutant emissions. The aim of this paper is the thermodynamic assessment of a SOFC-based IGFC plant with methanation reactor hydrogen post-firing and CO2 capture by physical absorption. The configuration proposed allows to obtain a very high net efficiency (51.6%) overcoming the main limits of configurations assessed in previous works.
Design of an Efficient, High Purity Hydrogen Generation Apparatus and Method for a Sustainable, Closed Clean Energy Cycle
Jul 2015
Publication
In this paper we present a detailed design study of a novel apparatus for safely generating hydrogen (H2) on demand according to a novel method using a controlled chemical reaction between water (H2O) and sodium (Na) metal that yields hydrogen gas of sufficient purity for direct use in fuel cells without risk of contaminating sensitive catalysts. The apparatus consists of a first pressure vessel filled with liquid H2O with an overpressure of nitrogen (N2) gas above the H2O reactant and a second pressure vessel that stores solid Na reactant. Hydrogen gas is generated above the solid Na when H2O reactant is introduced using a regulator that senses when the downstream pressure of H2 gas above the solid Na reactant has dropped below a threshold value. The sodium hydroxide (NaOH) byproduct of the hydrogen producing reaction is collected within the apparatus for later reprocessing by electrolysis to recover the Na reactant.
Pyrolysis-catalytic Steam Reforming of Agricultural Biomass Wastes and Biomass Components for Production of Hydrogen/syngas
Oct 2018
Publication
The pyrolysis-catalytic steam reforming of six agricultural biomass waste samples as well as the three main components of biomass was investigated in a two stage fixed bed reactor. Pyrolysis of the biomass took place in the first stage followed by catalytic steam reforming of the evolved pyrolysis gases in the second stage catalytic reactor. The waste biomass samples were rice husk coconut shell sugarcane bagasse palm kernel shell cotton stalk and wheat straw and the biomass components were cellulose hemicellulose (xylan) and lignin. The catalyst used for steam reforming was a 10 wt.% nickel-based alumina catalyst (NiAl2O3). In addition the thermal decomposition characteristics of the biomass wastes and biomass components were also determined using thermogravimetric analysis (TGA). The TGA results showed distinct peaks for the individual biomass components which were also evident in the biomass waste samples reflecting the existence of the main biomass components in the biomass wastes. The results for the two-stage pyrolysis-catalytic steam reforming showed that introduction of steam and catalyst into the pyrolysis-catalytic steam reforming process significantly increased gas yield and syngas production notably hydrogen. For instance hydrogen composition increased from 6.62 to 25.35 mmol g 1 by introducing steam and catalyst into the pyrolysis-catalytic steam reforming of palm kernel shell. Lignin produced the most hydrogen compared to cellulose and hemicellulose at 25.25 mmol g 1. The highest residual char production was observed with lignin which produced about 45 wt.% char more than twice that of cellulose and hemicellulose.
Bibliometric Analysis of Global Trends around Hydrogen Production Based on the Scopus Database in the Period 2011–2021
Dec 2022
Publication
Given the increase in population and energy demand worldwide alternative methods have been adopted for the production of hydrogen as a clean energy source. This energy offers an alternative energy source due to its high energy content and without emissions to the environment. In this bibliometric analysis of energy production using electrolysis and taking into account the different forms of energy production. In this analysis it was possible to evaluate the research trends based on the literature in the Scopus database during the years 2011–2021. The results showed a growing interest in hydrogen production from electrolysis and other mechanisms with China being the country with the highest number of publications and the United States TOP in citations. The trend shows that during the first four years of this study (2011–2014) the average number of publications was 74 articles per year from 2015 to 2021 where the growth is an average of 209 articles the journal that published the most on this topic is Applied Energy followed by Energy contributing with almost 33% in the research area. Lastly the keyword analysis identified six important research points for future discussions which we have termed clusters. The study concludes that new perspectives on clean hydrogen energy generation environmental impacts and social acceptance could contribute to the positive evolution of the hydrogen energy industry.
Energy Production by Laser-induced Annihilation in Ultradense Hydrogen H(0)
Feb 2021
Publication
Laser-induced nuclear processes in ultra-dense hydrogen H(0) give ejection of bunches of mesons similar to known baryon annihilation processes. This process was recently described as useful for relativistic interstellar travel (Holmlid and Zeiner-Gundersen 2020) and more precise experimental results exist now. The mesons are identified from their known decay time constants at rest as slow charged kaons slow neutral long-lived kaons and slow charged pions. Other observed time constants are interpreted as relativistically dilated decays for fast mesons of the same three types with kinetic energy up to 100 MeV for the kaons. Mouns are observed with kinetic energy of >100 MeV as decay products from the mesons. These particle energies are much too high to be due to nuclear fusion in hydrogen and the only known process which can give such energies is baryon annihilation. A model of the annihilation process starting with two protons or two neutrons gives good agreement with the observed meson types and their masses and kinetic energies thus now giving the complete energetics of the process. The process works with both D(0) and p(0). The efficiency from mass (of two baryons) to useful energy is 46% (contrary to 0.3% for T + D fusion) and the main non-recoverable energy loss is to neutrinos. Neutrons are not formed or ejected so this is an aneutronic process. The energy which can be extracted from ordinary hydrogen is 11.4 TWh per kg. This annihilation method is well suited for small and medium energy applications in the kW to MW range but scaling-up to GW power stations requires further development. It is unlikely that this energy production method can be used for weapons since there is no ignition or chain reaction.
Acorn: Developing Full-chain Industrial Carbon Capture and Storage in a Resource- and Infrastructure-rich Hydrocarbon Province
Jun 2019
Publication
Juan Alcalde,
Niklas Heinemann,
Leslie Mabon,
Richard H. Worden,
Heleen de Coninck,
Hazel Robertson,
Marko Maver,
Saeed Ghanbari,
Floris Swennenhuis,
Indira Mann,
Tiana Walker,
Sam Gomersal,
Clare E. Bond,
Michael J. Allen,
Stuart Haszeldine,
Alan James,
Eric J. Mackay,
Peter A. Brownsort,
Daniel R. Faulkner and
Steve Murphy
Research to date has identified cost and lack of support from stakeholders as two key barriers to the development of a carbon dioxide capture and storage (CCS) industry that is capable of effectively mitigating climate change. This paper responds to these challenges through systematic evaluation of the research and development process for the Acorn CCS project a project designed to develop a scalable full-chain CCS project on the north-east coast of the UK. Through assessment of Acorn's publicly-available outputs we identify strategies which may help to enhance the viability of early-stage CCS projects. Initial capital costs can be minimised by infrastructure re-use particularly pipelines and by re-use of data describing the subsurface acquired during oil and gas exploration activity. Also development of the project in separate stages of activity (e.g. different phases of infrastructure re-use and investment into new infrastructure) enables cost reduction for future build-out phases. Additionally engagement of regional-level policy makers may help to build stakeholder support by situating CCS within regional decarbonisation narratives. We argue that these insights may be translated to general objectives for any CCS project sharing similar characteristics such as legacy infrastructure industrial clusters and an involved stakeholder-base that is engaged with the fossil fuel industry.
Magnetic Field Enhancement of Electrochemical Hydrogen Evolution Reaction Probed by Magneto-optics
Nov 2020
Publication
External magnetic fields affect various electrochemical processes and can be used to enhance the efficiency of the electrochemical water splitting reaction. However the driving forces behind this effect are poorly understood due to the analytical challenges of the available interface-sensitive techniques. Here we present a set-up based on magneto- and electro-optical probing which allows to juxtapose the magnetic properties of the electrode with the electrochemical current densities in situ at various applied potentials and magnetic fields. On the example of an archetypal hydrogen evolution catalyst Pt (in a form of Co/Pt superlattice) we provide evidence that a magnetic field acts on the electrochemical double layer affecting the local concentration gradient of hydroxide ions which simultaneously affects the magneto-optical and magnetocurrent response.
Simple Hydrogen Gas Production Method Using Waste Silicon
Jan 2022
Publication
We investigated a simple and safe method for producing hydrogen using Si powder which is discarded in the semiconductor industry. Using the reaction of generating hydrogen from Si powder and an aqueous NaOH solution a simple hydrogen generator that imitated Kipp’s apparatus was produced. Then by combining this apparatus with a polymer electrolyte fuel cell an automatic hydrogen generation system based on the amount of electric power required was proposed. Furthermore it was found that hydrogen can also be generated using non-poisonous and deleterious substances Ca(OH)2 and Na2CO3 instead of the deleterious substance NaOH and adding water to the mixture with Si powder. The by-products Na2SiO3 and CaCO3 can be used as raw materials for glass. The simple hydrogen generator produced in this study can be used as a fuel supply source for small-scale power generation systems as an auxiliary power source.
Catalysis of Oxides in Hydrogen Generation by the Reaction of Al with Water
Sep 2013
Publication
Hydrogen generation by the reaction of pure Al powder in water with the addition of Al(OH)3 γ- Al2O3 α-Al2O3 or TiO2 at mild temperatures was investigated. It was found that the reaction of Al with water is promoted and the reaction induction time decreases greatly by the above hydroxide and oxides. X-ray diffraction analyses revealed that the hydroxide and oxide phases have no any change during the Al-water reaction indicating that they are just as catalysts to assist the reaction of Al with water. A possible mechanism was proposed which shows that hydroxide and oxides could dissociate water molecules and promote the hydration of the passive oxide film on Al particle surfaces.
Analysis of Wind to Hydrogen Production and Carbon Capture Utilisation and Storage Systems for Novel Production of Chemical Energy Carriers
Apr 2022
Publication
As the offshore energy landscape transitions to renewable energy useful decommissioned or abandoned oil and gas infrastructure can be repurposed in the context of the circular economy. Oil and gas platforms for example offer opportunity for hydrogen (H2) production by desalination and electrolysis of sea water using offshore wind power. However as H2 storage and transport may prove challenging this study proposes to react this H2 with the carbon dioxide (CO2) stored in depleted reservoirs. Thus producing a more transportable energy carriers like methane or methanol in the reservoir. This paper presents a novel thermodynamic analysis of the Goldeneye reservoir in the North Sea in Aspen Plus. For Goldeneye which can store 30 Mt of CO2 at full capacity if connected to a 4.45 GW wind farm it has the potential to produce 2.10 Mt of methane annually and abate 4.51 Mt of CO2 from wind energy in the grid.
Dynamic Energy and Mass Balance Model for an Industrial Alkaline Water Electrolyzer Plant Process
Nov 2021
Publication
This paper proposes a parameter adjustable dynamic mass and energy balance simulation model for an industrial alkaline water electrolyzer plant that enables cost and energy efficiency optimization by means of system dimensioning and control. Thus the simulation model is based on mathematical models and white box coding and it uses a practicable number of fixed parameters. Zero-dimensional energy and mass balances of each unit operation of a 3 MW and 16 bar plant process were solved in MATLAB functions connected via a Simulink environment. Verification of the model was accomplished using an analogous industrial plant of the same power and pressure range having the same operational systems design. The electrochemical mass flow and thermal behavior of the simulation and the industrial plant were compared to ascertain the accuracy of the model and to enable modification and detailed representation of real case scenarios so that the model is suitable for use in future plant optimization studies. The thermal model dynamically predicted the real case with 98.7 % accuracy. Shunt currents were the main contributor to relative low Faraday efficiency of 86 % at nominal load and steady-state operation and heat loss to ambient from stack was only 2.6 % of the total power loss.
Hydrogen Energy
Feb 2007
Publication
The problem of anthropogenically driven climate change and its inextricable link to our global society’s present and future energy needs are arguably the greatest challenge facing our planet. Hydrogen is now widely regarded as one key element of a potential energy solution for the twenty-first century capable of assisting in issues of environmental emissions sustainability and energy security. Hydrogen has the potential to provide for energy in transportation distributed heat and power generation and energy storage systems with little or no impact on the environment both locally and globally. However any transition from a carbon-based (fossil fuel) energy system to a hydrogen-based economy involves significant scientific technological and socio-economic barriers. This brief report aims to outline the basis of the growing worldwide interest in hydrogen energy and examines some of the important issues relating to the future development of hydrogen as an energy vector.
Link to document download on Royal Society Website
Link to document download on Royal Society Website
Hydrogen Production by Steam Reforming of DME in a Large Scale CFB Reactor. Part I: Computational Model and Predictions
Oct 2015
Publication
This study presents a computational fluid dynamic (CFD) study of Dimethyl Ether steam reforming (DME-SR) in a large scale Circulating Fluidized Bed (CFB) reactor. The CFD model is based on Eulerian–Eulerian dispersed flow and solved using commercial software (ANSYS FLUENT). The DME-SR reactions scheme and kinetics in the presence of a bifunctional catalyst of CuO/ZnO/Al2O3+ZSM-5 were incorporated in the model using in-house developed user-defined function. The model was validated by comparing the predictions with experimental data from the literature. The results revealed for the first time detailed CFB reactor hydrodynamics gas residence time temperature distribution and product gas composition at a selected operating condition of 300 °C and steam to DME mass ratio of 3 (molar ratio of 7.62). The spatial variation in the gas species concentrations suggests the existence of three distinct reaction zones but limited temperature variations. The DME conversion and hydrogen yield were found to be 87% and 59% respectively resulting in a product gas consisting of 72 mol% hydrogen. In part II of this study the model presented here will be used to optimize the reactor design and study the effect of operating conditions on the reactor performance and products.
Hydrogen‐Rich Gas Production from Two‐Stage Catalytic Pyrolysis of Pine Sawdust with Calcined Dolomite
Jan 2022
Publication
Tao Xu,
Jue Xu and
Yongping Wu
The potential of catalytic pyrolysis of biomass for hydrogen and bio‐oil production has drawn great attention due to the concern of clean energy utilization and decarbonization. In this paper the catalytic pyrolysis of pine sawdust with calcined dolomite was carried out in a novel moving bed reactor with a two‐stage screw feeder. The effects of pyrolysis temperature (700–900 °C) and catalytic temperature (500–800 °C) on pyrolysis performance were investigated in product distribution gas composition and gas properties. The results showed that with the temperature increased pyrolysis gas yield in‐ creased but the yield of solid and liquid products decreased. With the increase in temperature the CO and H2 content increased significantly while the CO2 and CH4 decreased correspondingly. The calcined dolomite can remove the tar by 44% and increased syngas yield by 52.9%. With the increasing catalytic temperature the catalytic effect of calcined dolomite was also enhanced.
Acid Acceleration of Hydrogen Generation Using Seawater as a Reactant
Jul 2016
Publication
The present study describes hydrogen generation from NaBH4 in the presence of acid accelerator boric oxide or B2O3 using seawater as a reactant. Reaction times and temperatures are adjusted using various delivery methods: bulk addition funnel and metering pump. It is found that the transition metal catalysts typically used to generate hydrogen gas are poisoned by seawater. B2O3 is not poisoned by seawater; in fact reaction times are considerably faster in seawater using B2O3. Reaction times and temperatures are compared for pure water and seawater for each delivery method. It is found that using B2O3 with pure water bulk addition is 97% complete in 3 min; pump metering provides a convenient method to extend the time to 27 min a factor of 9 increase above bulk addition. Using B2O3 with seawater as a reactant bulk addition is 97% complete in 1.35 min; pump metering extends the time to 23 min a factor of 17 increase above bulk. A second acid accelerator sodium bisulfate or NaHSO4 is investigated here for use with NaBH4 in seawater. Because it is non-reactive in seawater i.e. no spontaneous H2 generation NaHSO4 can be stored as a solution in seawater; because of its large solubility it is ready to be metered into NaBH4. With NaHSO4 in seawater pump metering increases the time to 97% completion from 3.4 min to 21 min. Metering allows the instantaneous flow rate of H2 and reaction times and temperatures to be tailored to a particular application. In one application the seawater hydrogen generator characterized here is ideal for supplying H2 gas directly to Proton Exchange Membrane fuel cells in sea surface or subsea environments where a reliable source of power is needed.
Thermal Efficiency of On-site, Small-scale Hydrogen Production Technologies using Liquid Hydrocarbon Fuels in Comparison to Electrolysis a Case Study in Norway
Oct 2018
Publication
The main goal of this study was to assess the energy efficiency of a small-scale on-site hydrogen production and dispensing plant for transport applications. The selected location was the city of Narvik in northern Norway where the hydrogen demand is expected to be 100 kg/day. The investigated technologies for on-site hydrogen generation starting from common liquid fossil fuels such as heavy naphtha and diesel were based on steam reforming and partial oxidation. Water electrolysis derived by renewable energy was also included in the comparison. The overall thermal efficiency of the hydrogen station was computed including compression and miscellaneous power consumption.
Enhancing the Efficiency of Power- and Biomass-to-liquid Fuel Processes Using Fuel-assisted Solid Oxide Electrolysis Cells
Apr 2022
Publication
Power- and biomass-to-liquid fuel processes (PBtL) can utilize renewable energy and residual forestry waste to produce liquid synthetic fuels which have the potential to mitigate the climate impacts of the current transportation infrastructure including the long-haul aviation sector. In a previous study we demonstrated that implementing a solid oxide electrolysis cell (SOEC) in the PBtL process can significantly increase the energy efficiency of fuel production by supplying the produced hydrogen to a reverse water gas shift (RWGS) reactor to generate syngas which is then fed downstream to a Fischer–Tropsch (FT) reactor. The tail gas emitted from the FT reactor consists primarily of a mixture of hydrogen carbon monoxide and methane and is often recycled to the entrained flow gasifier located at the beginning of the process. In this analysis we investigate the efficiency gains of the PBtL process as a result of redirecting the tail gas of the FT reactor to the anode of an SOEC to serve as fuel. Supplying fuel to an SOEC can lower the electrical work input required to facilitate steam electrolysis when reacting electrochemically with oxide ions in the anode which in turn can reduce oxygen partial pressures and thus alleviate material degradation. Accordingly we develop a thermodynamic framework to reveal the performance limits of fuel-assisted SOECs (FASOECs) and provide strategies to minimize oxygen partial pressures in the SOEC anode. Additionally we elucidate how much fuel is required to match the heating demands of a cell when steam is supplied to the cathode over a broad range of inlet temperatures and demonstrate the influence of a set of reaction pathways of the supplied fuel on the operating potential of an FASOEC and the corresponding efficiency gain of the PBtL process. Based on preliminary calculations we estimate that implementing an FASOEC in the PBtL process can increase the energy efficiency of fuel production to more than 90% depending on the amount of FT tail gas available to the system.
Methanol Reforming Processes for Fuel Cell Applications
Dec 2021
Publication
Hydrogen production through methanol reforming processes has been stimulated over the years due to increasing interest in fuel cell technology and clean energy production. Among different types of methanol reforming the steam reforming of methanol has attracted great interest as reformate gas stream where high concentration of hydrogen is produced with a negligible amount of carbon monoxide. In this review recent progress of the main reforming processes of methanol towards hydrogen production is summarized. Different catalytic systems are reviewed for the steam reforming of methanol: mainly copper- and group 8–10-based catalysts highlighting the catalytic key properties while the promoting effect of the latter group in copper activity and selectivity is also discussed. The effect of different preparation methods different promoters/stabilizers and the formation mechanism is analyzed. Moreover the integration of methanol steam reforming process and the high temperature–polymer electrolyte membrane fuel cells (HT-PEMFCs) for the development of clean energy production is discussed.
Production of Hydrogen by Chemical Looping Reforming of Methane and Biogas using a Reactive and Durable Cu-based Oxygen Carrier
Apr 2022
Publication
The objective of this work was to assess the suitability of a synthetic Cu-based oxygen carrier in a continuous pilot plant for the production of blue and green hydrogen through the autothermal Chemical Looping Reforming (CLRa). In CLRa methane is converted to a H2 + CO mixture through partial oxidation and reforming reactions in the fuel reactor. The degree of the partial oxidation of methane was defined by controlling the oxygen flow in the air reactor. Steam was used as reforming gas in natural gas to produce blue H2 but the existing CO2 in biogas was the reforming gas to produce green H2. Operating at 950 ◦C in the fuel and air reactors CH4 conversion and H2 yield parameters were 96 % and 2.60 mol of H2 per mole of CH4 respectively. These experimental results were close to the theoretical values that could be achieved in the CLRa process. Furthermore the physico-chemical characterization of the samples extracted from the pilot plant throughout the experimental campaign revealed that the Cu-based oxygen carrier maintained its mechanical integrity and chemical stability under harsh operating conditions. Therefore it can be concluded that Cu-based oxygen carriers can be considered a promising alternative to Ni-based materials for the production of blue and green hydrogen through the CLRa process.
Techno-economic Analysis on Renewable Energy Via Hydrogen, Views from Macro and Micro Scopes
Mar 2019
Publication
This paper addresses from both macro- and micro- areal coverage in introducing hydrogen system in terms of cost and performance where the produced hydrogen from surplus photovoltaic (PV) power is stored. Feed-in tariff in Japan had successful achievement for great expansion of renewable energy systems (RES) causing problematic operation due to excess power by overcapacity of RES. One of the candidate approaches to overcome this surplus energy by RES is Power to gas (P2G) system using electrolysis cells (ECs) fuel cells (FCs) or co-firing in gas turbines both for energy conversion as well as power balancing. Numerous studies had been investigated on P2G however within our knowledge no study had been addressed the system from both coverages with different capacity and scales. We investigate micro level (zero emission building in our university) and macro level (Kyushu one of big regions in Japan). We describe for macro side preliminary result on economic analysis of using surplus power of RES via production and storage of hydrogen while for micro side research design.
Pathways to Hydrogen as an Energy Carrier
Feb 2007
Publication
When hydrogen is used as an alternative energy carrier it is very important to understand the pathway from the primary energy source to the final use of the carrier. This involves for example the understanding of greenhouse gas emissions associated with the production of hydrogen and throughout the lifecycle of a given utilization pathway as well as various energy or exergy1 efficiencies and aspects involved. This paper which is based on a talk given at the Royal Society in London assesses and reviews the various production pathways for hydrogen with emphasis on emissions energy use and energy efficiency. The paper also views some aspects of the breaking of the water molecule and examines some new emerging physical evidence which could pave the way to a new and more feasible pathway.
Link to document download on Royal Society Website
Link to document download on Royal Society Website
Combined Dehydrogenation and Hydrogen-based Power Generation
Jan 2018
Publication
An energy production from the combination of dehydrogenation and combined cycle power generation is proposed. The delivered system is established from three main modules: dehydrogenation combustion and combined cycle. The heat in the system is circulated thoroughly to enhance the energy efficiency due to optimum energy recovery. The Pt/Al2O3 catalyst is applied in the dehydrogenation module due to superior activity to accelerate the dehydrogenation of MCH. The toluene emitted from the MCH is recirculated to the hydrogenation plant while the hydrogen is further utilized as the fuel in the combustion. Although the high-temperature condition is necessary to perform high yield dehydrogenation the proposed system is capable of carrying out self-heating mechanism with no external heat. With the optimum configuration the delivered system can produce 100.0 MW of electricity from 100 t/h of MCH with 50.19% of energy efficiency.
State of the Art of Hydrogen Production via Pyrolysis of Natural Gas
Jul 2020
Publication
Fossil fuels have to be substituted by climate neutral fuels to contribute to CO2 reduction in the future energy system. Pyrolysis of natural gas is a well-known technical process applied for production of e. g. carbon black.
In the future it might contribute to carbon dioxide-free hydrogen production. Production of hydrogen from natural gas pyrolysis has thus gained interest in research and energy technology in the near past. If the carbon by-product of this process can be used for material production or can be sequestrated the produced hydrogen has a low carbon footprint.
This article reviews literature on the state of the art of methane/ natural gas pyrolysis process developments and at-tempts to assess the technology readiness level (TRL).
In the future it might contribute to carbon dioxide-free hydrogen production. Production of hydrogen from natural gas pyrolysis has thus gained interest in research and energy technology in the near past. If the carbon by-product of this process can be used for material production or can be sequestrated the produced hydrogen has a low carbon footprint.
This article reviews literature on the state of the art of methane/ natural gas pyrolysis process developments and at-tempts to assess the technology readiness level (TRL).
Methodology for the Development of Hybrid Renewable Energy Systems (HRES) with Pumped Storage and Hydrogen Production on Lemnos Island
Apr 2022
Publication
The non-interconnected islands of Greece can benefit from the comprehensive use of RES to avoid water droughts and ensure energy autonomy. The present paper analyzes an HRES with two possible operating scenarios. Both of them include a wind park of 27.5 MW capacity an 1175 m3/day desalination plant and a 490000 m3/day water tank in Lemnos Greece. Regarding the wind power 70% is used in the HRES while the rest is channeled directly to the grid. The main difference comes down to how the wind energy is stored either in the form of hydraulic energy or in the form of hydrogen. The lifespan of the system is 25 years such as the produced stochastic series of rainfall temperature and wind of the area. Through the comparison of the operating scenarios the following results arise: (i) the water needs of the island are fully covered and the irrigation needs have a reliability of 66% in both scenarios. (ii) Considering the energy needs the pumping storage seems to be the most reliable solution. (iii) However depending on the amount of wind energy surplus the use of hydrogen could produce more energy than the hydroelectric plant.
Multi-objective Optimal Configurations of a Membrane Reactor for Steam Methane Reforming
Nov 2021
Publication
The combination of traditional reactor and permeable membrane is beneficial to increase the production rate of the target product. How to design a high efficiency and energy saving membrane reactor is one of the key problems to be solved urgently. This paper utilizes finite-time thermodynamics and nonlinear programming to solve the optimal configurations of the membrane reactor of steam methane reforming (MR-SMR) for two optimization objectives that is heat exchange rate minimization and power consumption minimization. The exterior wall temperature and fixed hydrogen production rate are regarded as the control variable and constraint respectively. The results indicate that the hydrogen production rate and heat exchange rate in MR-SMR are increased by 108.58% and 58.42% respectively while the power consumption is reduced by 33.44% compared with those in the traditional reactor under the same condition. Compared with the results in reference reactor (MR-SMR obtained with initial values) the heat exchange rate is reduced by 1.40% by optimizing the exterior wall temperature and the power consumption is reduced by 5.10% by optimizing the exterior wall temperature and molar flow rate of sweep gas. The optimal distributions of exterior wall temperatures in the optimal reactors of minimum heat exchange rate and power consumption have a theoretical guiding significance for the thermal design of the membrane reactors.
Exchange Current Density of Reversible Solid Oxide Cell Electrodes
Mar 2022
Publication
Reversible solid oxide cells (r-SOCs) can be operated in either solid oxide fuel cell or solid oxide electrolysis cell mode. They are expected to become important in the support of renewable energy due to their high efficiency for both power generation and hydrogen generation. The exchange current density is one of the most important parameters in the quantification of electrode performance in solid oxide cells. In this study four different fuel electrodes and two different air electrodes are fabricated using different materials and the microstructures are compared. The temperature fuel humidification and oxygen concentration at the air electrode are varied to obtain the apparent exchange current density for the different electrode materials. In contrast to ruthenium-and-gadolinia-doped ceria (Rh-GDC) as well as nickel-and-gadolinia-doped ceria (Ni-GDC) electrodes significant differences in the apparent exchange current density were observed between electrolysis and fuel cell modes for the nickel-scandia-stabilized zirconia (Ni-ScSZ) cermet. Variation of gas concentration revealed that surface adsorption sites were almost completely vacant for all these electrodes. The apparent exchange current densities obtained in this study are useful as a parameter for simulation of the internal properties of r-SOCs.
Advances and Challenges of MOF Derived Carbon-based Electrocatalysts and Photocatalyst for Water Splitting: A Review
Apr 2022
Publication
Environmental pollution and energy shortage are substantial fears to the modern world's long-term sustainability. Water splitting is an essential technique for eco - friendly and sustainable energy storage as well as a pollution-free method to produce hydrogen. In this regards Metal–organic frameworks have emerged as the most competent multifunctional materials in recent times due to its large surface areas adjustable permeability easy compositional alteration and capability for usage as precursors with a wide range of morphological forms. Further MOF-derived carbon-based nanomaterials also offer significant benefits in terms of tunable morphological features and hierarchical permeability as well as ease of functionalization making them extremely effective as catalysts or catalysts supports for a wide variety of important reactions. Recent developments in carbon-based MOFs as catalysts for overall water splitting are discussed in this review. We explore how MOFs and carbon-based MOFs might well be beneficial as well as which methods should be explored for future development. We divided our review into two sections: photocatalytic and electrocatalytic water splitting and we gathered published literature on carbon-based MOFs materials for their outstanding activity offers helpful methods for catalysts design and analysis as well as difficulties This study highlights the developments in MOF derived materials as photo and electro catalysts by explaining respective approaches for their use in overall water splitting.
New Insights into the Electrochemical Behaviour of Porous Carbon Electrodes for Supercapacitors
Aug 2018
Publication
Activated carbons with different surface chemistry and porous textures were used to study the mechanism of electrochemical hydrogen and oxygen evolution in supercapacitor devices. Cellulose precursor materials were activated with different potassium hydroxide (KOH) ratios and the electrochemical behaviour was studied in 6 M KOH electrolyte. In situ Raman spectra were collected to obtain the structural changes of the activated carbons under severe electrochemical oxidation and reduction conditions and the obtained data were correlated to the cyclic voltammograms obtained at high anodic and cathodic potentials. Carbon-hydrogen bonds were detected for the materials activated at high KOH ratios which form reversibly under cathodic conditions. The influence of the specific surface area narrow microporosity and functional groups in the carbon electrodes on their chemical stability and hydrogen capture mechanism in supercapacitor applications has been revealed.
Large Transition State Stabilization From a Weak Hydrogen Bond
Jul 2020
Publication
A series of molecular rotors was designed to study and measure the rate accelerating effects of an intramolecular hydrogen bond. The rotors form a weak neutral O–H⋯O[double bond length as m-dash]C hydrogen bond in the planar transition state (TS) of the bond rotation process. The rotational barrier of the hydrogen bonding rotors was dramatically lower (9.9 kcal mol−1) than control rotors which could not form hydrogen bonds. The magnitude of the stabilization was significantly larger than predicted based on the independently measured strength of a similar O–H⋯O[double bond length as m-dash]C hydrogen bond (1.5 kcal mol−1). The origins of the large transition state stabilization were studied via experimental substituent effect and computational perturbation analyses. Energy decomposition analysis of the hydrogen bonding interaction revealed a significant reduction in the repulsive component of the hydrogen bonding interaction. The rigid framework of the molecular rotors positions and preorganizes the interacting groups in the transition state. This study demonstrates that with proper design a single hydrogen bond can lead to a TS stabilization that is greater than the intrinsic interaction energy which has applications in catalyst design and in the study of enzyme mechanisms.
An Extended Flamelet-based Presumed Probability Density Function for Predicting Mean Concentrations of Various Species in Premixed Turbulent Flames
Sep 2020
Publication
Direct Numerical Simulation (DNS) data obtained by Dave and Chaudhuri (2020) from a lean complex-chemistry hydrogen-air flame associated with the thin-reaction-zone regime of premixed turbulent burning are analyzed to perform a priori assessment of predictive capabilities of the flamelet approach for evaluating mean species concentrations. For this purpose dependencies of mole fractions and rates of production of various species on a combustion progress variable c obtained from the laminar flame are averaged adopting either the actual Probability Density Function (PDF) P (c) extracted from the DNS data or a common presumed β-function PDF. On the one hand the results quantitatively validate the flamelet approach for the mean mole fractions of all species including radicals but only if the actual PDF P (c) is adopted. The use of the β-function PDF yields substantially worse results for the radicals’ concentrations. These findings put modeling the PDF P (c) on the forefront of the research agenda. On the other hand the mean rate of product creation and turbulent burning velocity are poorly predicted even adopting the actual PDF. These results imply that in order to evaluate the mean species concentrations the flamelet approach could be coupled with another model that predicts the mean rate and turbulent burning velocity better. Accordingly the flamelet approach could be implemented as post-processing of numerical data yielded by that model. Based on the aforementioned findings and implications a new approach to building a presumed PDF is developed. The key features of the approach consist in (i) adopting a re-normalized flamelet PDF for intermediate values of c and (ii) directly using the mean rate of product creation to calibrate the presumed PDF. Capabilities of the newly developed PDF for predicting mean species concentrations are quantitively validated for all species including radicals.
Business Models for Low Carbon Hydrogen Production: A Report for BEIS
Aug 2020
Publication
Low carbon hydrogen could have a significant role to play in meeting the UK’s Net Zero target: the Committee on Climate Change (CCC) estimates that up to 270TWh of low carbon hydrogen could be needed in its ‘Further Ambition’ scenario. However at present there is no large-scale production of low carbon hydrogen in the UK not least as it is more costly than most high carbon alternatives. For hydrogen to be the viable option envisaged by the CCC projects may need to be deployed from the 2020s.<br/>BEIS has commissioned Frontier Economics to develop business models to support low carbon hydrogen production. This report builds on the earlier Carbon Capture Usage and Storage (CCUS) business models consultation2 and develops business models for BEIS to consider further. This report is a milestone in BEIS’ longer term process of developing hydrogen business models. It forms a part of BEIS’ wider research into a range of decarbonisation options across the economy.<br/>Further analysis will be required before a final decision is made.
Hydrogen Production from Natural Gas and Biomethane with Carbon Capture and Storage – A Techno-environmental Analysis
Mar 2020
Publication
This study presents an integrated techno-environmental assessment of hydrogen production from natural gas and biomethane combined with CO2 capture and storage (CCS). We have included steam methane reforming (SMR) and autothermal reforming (ATR) for syngas production. CO2 is captured from the syngas with a novel vacuum pressure swing adsorption (VPSA) process that combines hydrogen purification and CO2 separation in one cycle. As comparison we have included cases with conventional amine-based technology. We have extended standard attributional Life Cycle Assessment (LCA) following ISO standards with a detailed carbon balance of the biogas production process (via digestion) and its by-products. The results show that the life-cycle greenhouse gas (GHG) performance of the VPSA and amine-based CO2 capture technologies is very similar as a result of comparable energy consumption. The configuration with the highest plant-wide CO2 capture rate (almost 100% of produced CO2 captured) is autothermal reforming with a two-stage water-gas shift and VPSA CO2 capture – because the latter has an inherently high CO2 capture rate of 98% or more for the investigated syngas. Depending on the configuration the addition of CCS to natural gas reforming-based hydrogen production reduces its life-cycle Global Warming Potential by 45–85 percent while the other environmental life-cycle impacts slightly increase. This brings natural gas-based hydrogen on par with renewable electricity-based hydrogen regarding impacts on climate change. When biomethane is used instead of natural gas our study shows potential for net negative greenhouse gas emissions i.e. the net removal of CO2 over the life cycle of biowaste-based hydrogen production. In the special case where the biogas digestate is used as agricultural fertiliser and where a substantial amount of the carbon in the digestate remains in the soil the biowaste-based hydrogen reaches net-negative life cycle greenhouse gas emissions even without the application of CCS. Addition of CCS to biomethane-based hydrogen production leads to net-negative emissions in all investigated cases.
Thermal Hydrogen: An Emissions Free Hydrocarbon Economy
Apr 2017
Publication
Envisioned below is an energy system named Thermal Hydrogen developed to enable economy-wide decarbonization. Thermal Hydrogen is an energy system where electric and/or heat energy is used to split water (or CO2) for the utilization of both by-products: hydrogen as energy storage and pure oxygen as carbon abatement. Important advantages of chemical energy carriers are long term energy storage and extended range for electric vehicles. These minimize the need for the most capital intensive assets of a fully decarbonized energy economy: low carbon power plants and batteries. The pure oxygen pre-empts the gas separation process of “Carbon Capture and Sequestration” (CCS) and enables hydrocarbons to use simpler more efficient thermodynamic cycles. Thus the “externality” of water splitting pure oxygen is increasingly competitive hydrocarbons which happen to be emissions free. Methods for engineering economy-wide decarbonization are described below as well as the energy supply carrier and distribution options offered by the system.
Achieving High-rate Hydrogen Recovery from Wastewater Using Customizable Alginate Polymer Gel Matrices Encapsulating Biomass
Jul 2018
Publication
In addition to methane gas higher-value resources such as hydrogen gas are produced during anaerobic wastewater treatment. They are however immediately consumed by other organisms. To recover these high-value resources not only do the desired phenotypes need to be retained in the anaerobic reactor but the undesired ones need to be washed out. In this study a well-established alginate-based polymer gel with and without a coating layer was used to selectively encapsulate hydrogen-producing biomass in beads to achieve high-rate recovery of hydrogen during anaerobic wastewater treatment. The effect of cross-linking agents Ca2+ Sr2+ and Ba2+ as well as a composite coating on the beads consisting of alternating layers of polyethylenimine and silica hydrogel were investigated with respect to their performance specifically their mass transfer characteristics and their differential ability to retain the encapsulated biomass. Although the coating reduced the escape rate of encapsulated biomass from the beads all alginate polymer matrices without coating effectively retained biomass. Fast diffusion of dissolved organic carbon (DOC) through the polymer gel was observed in both Ca-alginate and Sr-alginate without coating. The coating however decreased either the diffusivity or the permeability of the DOC depending on whether the DOC was from synthetic wastewater (more lipids and proteins) or real brewery wastewater (more sugars). Consequently the encapsulation system with coating became diffusion limited when brewery wastewater with high chemical oxygen demand was fed resulting in a lower hydrogen production rate than the uncoated encapsulation systems. In all cases the encapsulated biomass was able to produce hydrogen even at a hydraulic residence time of 45 min. Although there are limitations to this system the used of encapsulated biomass for resource recovery from wastewater shows promise particularly for high-rate systems in which the retention of specific phenotypes is desired.
Debunking the Myths of Hydrogen Production and Water Consumption
Dec 2020
Publication
In our factsheet where we debunk 3 myths around hydrogen production and water consumption: electrolysis uses vast amounts of water; electrolysis uses freshwater resources only and electrolysis is bound to create water stress in water-scarce regions.
Recent Advancements in Chemical Looping Water Splitting for the Production of Hydrogen
Oct 2016
Publication
Chemical looping water splitting or chemical looping hydrogen is a very promising technology for the production of hydrogen. In recent years extensive research has enabled remarkable leaps towards a successful integration of the chemical looping technology into a future hydrogen infrastructure. Progress has been reported with iron based oxygen carriers for stable hydrogen production capacity over consecutive cycles without significant signs of degradation. The high stability improvements were achieved by adding alien metal oxides or by integrating the active component into a mineral structure which offers excellent resistance towards thermal stress. Prototype systems from small μ-systems up to 50 kW have been operated with promising results. The chemical looping water splitting process was broadened in terms of its application area and utilization of feedstocks using a variety of renewable and fossil resources. The three-reactor system was clearly advantageous due to its flexibility heat integration capabilities and possibility to produce separate pure streams of hydrogen CO2 and N2. However two-reactor and single fixed-bed reactor systems were successfully operated as well. This review aims to survey the recently presented literature in detail and systematically summarize the gathered data.
Design and Cost Considerations for Practical Solar-hydrogen Generators
Oct 2014
Publication
Solar-hydrogen generation represents a promising alternative to fossil fuels for the large-scale implementation of a clean-fuel transportation infrastructure. A significant amount of research resources has been allocated to the development of photoelectrochemical components (i.e. photovoltaic and water splitting catalysts) that are able to spontaneously split water in the presence of solar irradiation which has led to major advances in the solar-fuels field. At the same time only limited attention has been given to understanding the key aspects that drive economically viable solar-fuel generators. This study presents a generalized approach to understand the economic factors behind the design of solar-hydrogen generators composed of photovoltaic components integrated with water electrolyzers. It evaluates the underpinning effects of the material selection for the light absorption and water splitting components on the cost of the generated fuel ($ per Kg of H2). The results presented in this work provide insights into important engineering aspects related to the sizing of devices and the use of light concentration components that when optimized can lead to costs below $2.90 per kilogram of hydrogen after compression and distribution. Most significantly the analysis demonstrates that the cost of hydrogen is defined primarily by the light-absorbing component (up to 97% of the cost) while the material selection for the electrolysis components has to a large extent minor effects. The findings presented here can help direct research and development efforts towards the fabrication of deployable solar-hydrogen generators that are cost competitive with commercial energy sources.
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