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.
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