Production & Supply Chain
Development and Functionalization of Visible-Light-Driven Water-Splitting Photocatalysts
Jan 2022
Publication
With global warming and the depletion of fossil resources our fossil fuel-dependent society is expected to shift to one that instead uses hydrogen (H2) as a clean and renewable energy. To realize this the photocatalytic water-splitting reaction which produces H2 from water and solar energy through photocatalysis has attracted much attention. However for practical use the functionality of water-splitting photocatalysts must be further improved to efficiently absorb visible (Vis) light which accounts for the majority of sunlight. Considering the mechanism of water-splitting photocatalysis researchers in the various fields must be employed in this type of study to achieve this. However for researchers in fields other than catalytic chemistry ceramic (semiconductor) materials chemistry and electrochemistry to participate in this field new reviews that summarize previous reports on water-splitting photocatalysis seem to be needed. Therefore in this review we summarize recent studies on the development and functionalization of Vis-light-driven water-splitting photocatalysts. Through this summary we aim to share current technology and future challenges with readers in the various fields and help expedite the practical application of Vis-light-driven water-splitting photocatalysts.
A New Sustainable Hydrogen Clean Energy Paradigm
Feb 2018
Publication
We analyze the feasibility of a novel hydrogen fuel cell electric generator to provide power with zero noise and emissions for myriad ground based applications. The hydrogen fuel cell electric generator utilizes a novel scalable apparatus that safely generates 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 sodium hydroxide (NaOH) byproduct of the hydrogen producing reaction is collected within the apparatus for later reprocessing by electrolysis to recover the Na reactant. The detailed analysis shows that the novel hydrogen fuel cell electric generator will be capable of meeting the clean power requirements for residential and commercial buildings including single family homes and light commercial establishments under a wide range of geographic and climatic conditions.
Probability of Occurrence of ISO 14687-2 Contaminants in Hydrogen: Principles and Examples from Steam Methane Reforming and Electrolysis (Water and Chlor-alkali) Production Processes Model
Apr 2018
Publication
According to European Directive 2014/94/EU hydrogen providers have the responsibility to prove that their hydrogen is of suitable quality for fuel cell vehicles. Contaminants may originate from hydrogen production transportation refuelling station or maintenance operation. This study investigated the probability of presence of the 13 gaseous contaminants (ISO 14687-2) in hydrogen on 3 production processes: steam methane reforming (SMR) process with pressure swing adsorption (PSA) chlor-alkali membrane electrolysis process and water proton exchange membrane electrolysis process with temperature swing adsorption. The rationale behind the probability of contaminant presence according to process knowledge and existing barriers is highlighted. No contaminant was identified as possible or frequent for the three production processes except oxygen (frequent for chlor-alkali membrane process) carbon monoxide (frequent) and nitrogen (possible) for SMR with PSA. Based on it a hydrogen quality assurance plan following ISO 19880-8 can be devised to support hydrogen providers in monitoring the relevant contaminants.
Promotion Effect of Proton-conducting Oxide BaZr0.1Ce0.7Y0.2O3−δ on the Catalytic Activity of Ni Towards Ammonia Synthesis from Hydrogen and Nitrogen
Aug 2018
Publication
In this report for the first time it has been observed that proton-conducting oxide BaZr0.1Ce0.7Y0.2O3−δ (BZCY) has significant promotion effect on the catalytic activity of Ni towards ammonia synthesis from hydrogen and nitrogen. Renewable hydrogen can be used for ammonia synthesis to save CO2 emission. By investigating the operating parameters of the reaction the optimal conditions for this catalyst were identified. It was found that at 620 °C with a total flow rate of 200 mL min−1 and a H2/N2 mol ratio of 3 an activity of approximately 250 μmol g−1 h−1 can be achieved. This is ten times larger than that for the unpromoted Ni catalyst under the same conditions although the stability of both catalysts in the presence of steam was not good. The specific activity of Ni supported on proton-conducting oxide BZCY is approximately 72 times higher than that of Ni supported on non-proton conductor MgO-CeO2. These promotion effects were suspected to be due to the proton conducting nature of the support. Therefore it is proposed that the use of proton conducting support materials with highly active ammonia synthesis catalysts such as Ru and Fe will provide improved activity of at lower temperatures.
Economic Viability and Environmental Efficiency Analysis of Hydrogen Production Processes for the Decarbonization of Energy Systems
Aug 2019
Publication
The widespread penetration of hydrogen in mainstream energy systems requires hydrogen production processes to be economically competent and environmentally efficient. Hydrogen if produced efficiently can play a pivotal role in decarbonizing the global energy systems. Therefore this study develops a framework which evaluates hydrogen production processes and quantifies deficiencies for improvement. The framework integrates slack-based data envelopment analysis (DEA) with fuzzy analytical hierarchy process (FAHP) and fuzzy technique for order of preference by similarity to ideal solution (FTOPSIS). The proposed framework is applied to prioritize the most efficient and sustainable hydrogen production in Pakistan. Eleven hydrogen production alternatives were analyzed under five criteria including capital cost feedstock cost O&M cost hydrogen production and CO2 emission. FAHP obtained the initial weights of criteria while FTOPSIS determined the ultimate weights of criteria for each alternative. Finally slack-based DEA computed the efficiency of alternatives. Among the 11 three alternatives (wind electrolysis PV electrolysis and biomass gasification) were found to be fully efficient and therefore can be considered as sustainable options for hydrogen production in Pakistan. The rest of the eight alternatives achieved poor efficiency scores and thus are not recommended.
Compact Heat Integrated Reactor System of Steam Reformer, Shift Reactor and Combustor for Hydrogen Production from Ethanol
Jun 2020
Publication
A compact heat integrated reactor system (CHIRS) of a steam reformer a water gas shift reactor and a combustor were designed for stationary hydrogen production from ethanol. Different reactor integration concepts were firstly studied using Aspen Plus. The sequential steam reformer and shift reactor (SRSR) was considered as a conventional system. The efficiency of the SRSR could be improved by more than 12% by splitting water addition to the shift reactor (SRSR-WS). Two compact heat integrated reactor systems (CHIRS) were proposed and simulated by using COMSOL Multiphysics software. Although the overall efficiency of the CHIRS was quite a bit lower than the SRSR-WS the compact systems were properly designed for portable use. CHIRS (I) design combining the reactors in a radial direction was large in reactor volume and provided poor temperature control. As a result the ethanol steam reforming and water gas shift reactions were suppressed leading to lower hydrogen selectivity. On the other hand CHIRS (II) design combining the process in a vertical direction provided better temperature control. The reactions performed efficiently resulting in higher hydrogen selectivity. Therefore the high performance CHIRS (II) design is recommended as a suitable stationary system for hydrogen production from ethanol.
Optimal Design and Operation of Integrated Wind-hydrogen-electricity Networks for Decarbonising the Domestic Transport Sector in Great Britain
Nov 2015
Publication
This paper presents the optimal design and operation of integrated wind-hydrogen-electricity networks using the general mixed integer linear programming energy network model STeMES (Samsatli and Samsatli 2015). The network comprises: wind turbines; electrolysers fuel cells compressors and expanders; pressurised vessels and underground storage for hydrogen storage; hydrogen pipelines and electricity overhead/underground transmission lines; and fuelling stations and distribution pipelines.<br/>The spatial distribution and temporal variability of energy demands and wind availability were considered in detail in the model. The suitable sites for wind turbines were identified using GIS by applying a total of 10 technical and environmental constraints (buffer distances from urban areas rivers roads airports woodland and so on) and used to determine the maximum number of new wind turbines that can be installed in each zone.<br/>The objective is the minimisation of the total cost of the network subject to satisfying all of the demands of the domestic transport sector in Great Britain. The model simultaneously determines the optimal number size and location of each technology whether to transmit the energy as electricity or hydrogen the structure of the transmission network the hourly operation of each technology and so on. The cost of distribution was estimated from the number of fuelling stations and length of the distribution pipelines which were determined from the demand density at the 1 km level.<br/>Results indicate that all of Britain's domestic transport demand can be met by on-shore wind through appropriately designed and operated hydrogen-electricity networks. Within the set of technologies considered the optimal solution is: to build a hydrogen pipeline network in the south of England and Wales; to supply the Midlands and Greater London with hydrogen from the pipeline network alone; to use Humbly Grove underground storage for seasonal storage and pressurised vessels at different locations for hourly balancing as well as seasonal storage; for Northern Wales Northern England and Scotland to be self-sufficient generating and storing all of the hydrogen locally. These results may change with the inclusion of more technologies such as electricity storage and electric vehicles.
Development of Water Electrolysis in the European Union
Feb 2014
Publication
In view of the recent interest in the transformation of renewable energy into a new energy vector that did not produce by combustion greenhouse gases emissions the Fuel Cells and Hydrogen Joint Undertaking (FCH JU) commissioned this report to a consultancy to get a better understanding of the industrial perspectives of water electrolysis in Europe. and the role that public support has in that evolution.
Future Cost and Performance of Water Electrolysis: An Expert Elicitation Study
Nov 2017
Publication
The need for energy storage to balance intermittent and inflexible electricity supply with demand is driving interest in conversion of renewable electricity via electrolysis into a storable gas. But high capital cost and uncertainty regarding future cost and performance improvements are barriers to investment in water electrolysis. Expert elicitations can support decision-making when data are sparse and their future development uncertain. Therefore this study presents expert views on future capital cost lifetime and efficiency for three electrolysis technologies: alkaline (AEC) proton exchange membrane (PEMEC) and solid oxide electrolysis cell (SOEC). Experts estimate that increased R&D funding can reduce capital costs by 0–24% while production scale-up alone has an impact of 17–30%. System lifetimes may converge at around 60000–90000 h and efficiency improvements will be negligible. In addition to innovations on the cell-level experts highlight improved production methods to automate manufacturing and produce higher quality components. Research into SOECs with lower electrode polarisation resistance or zero-gap AECs could undermine the projected dominance of PEMEC systems. This study thereby reduces barriers to investment in water electrolysis and shows how expert elicitations can help guide near-term investment policy and research efforts to support the development of electrolysis for low-carbon energy systems.
Effect of Syngas Fuel Compositions on the Occurrence of Instability of Laminar Diffusion Flame
Dec 2020
Publication
The paper presents a numerical investigation of the critical roles played by the chemical compositions of syngas on laminar diffusion flame instabilities. Three different flame phenomena – stable flickering and tip-cutting – are formulated by varying the syngas fuel rate from 0.2 to 1.4 SLPM. Following the satisfactory validation of numerical results with Darabkhani et al. [1] the study explored the consequence of each species (H2 CO CH4 CO2 N2) in the syngas composition. It is found that low H2:CO has a higher level of instability which however does not rise any further when the ratio is less than 1. Interestingly CO encourages the heat generation with less fluctuation while H2 plays another significant role in the increase of flame temperature and its fluctuation. Diluting CH4 into syngas further increases the instability level as well as the fluctuation of heat generation significantly. However an opposite effect is found from the same action with either CO2 or N2. Finally considering the heat generation and flame stability the highest performance is obtained from 25%H2+75%CO (81 W) followed by EQ+20%CO2 and EQ+20%N2 (78 W).
Efficient Hydrogen Production with CO2 Capture Using Gas Switching Reforming
Jul 2019
Publication
Hydrogen is a promising carbon-neutral energy carrier for a future decarbonized energy sector. This work presents process simulation studies of the gas switching reforming (GSR) process for hydrogen production with integrated CO2 capture (GSR-H2 process) at a minimal energy penalty. Like the conventional steam methane reforming (SMR) process GSR combusts the off-gas fuel from the pressure swing adsorption unit to supply heat to the endothermic reforming reactions. However GSR completes this combustion using the chemical looping combustion mechanism to achieve fuel combustion with CO2 separation. For this reason the GSR-H2 plant incurred an energy penalty of only 3.8 %-points relative to the conventional SMR process with 96% CO2 capture. Further studies showed that the efficiency penalty is reduced to 0.3 %-points by including additional thermal mass in the reactor to maintain a higher reforming temperature thereby facilitating a lower steam to carbon ratio. GSR reactors are standalone bubbling fluidized beds that will be relatively easy to scale up and operate under pressurized conditions and the rest of the process layout uses commercially available technologies. The ability to produce clean hydrogen with no energy penalty combined with this inherent scalability makes the GSR-H2 plant a promising candidate for further research.
Study on Hydrogen from Renewable Resources in the EU
Feb 2016
Publication
Hydrogen can be produced from a broad range of renewable energy sources acting as a unique energy hub providing low or zero emission energy to all energy consuming sectors. Technically and efficiently producing hydrogen from renewable sources is a key enabler for these developments.<br/>Traditionally hydrogen has been produced from fossil sources by steam methane reforming of natural gas. At present the technology of choice to produce renewable ‘green’ hydrogen is water electrolysis using renewable electricity. The FCH JU has been supporting research and development of electrolyser technology and application projects aiming to increase the energy efficiency of electrolytic hydrogen production from renewable sources and to reduce costs.<br/>This study complements these activities by focusing on renewable hydrogen generation other than electrolysis. In this report these alternative hydrogen generation technologies are described characterized by their technical capabilities maturity and economic performance and assessed for their future potential.<br/>A methodology has been devised to first identify and structure a set of relevant green hydrogen pathways (eleven pathways depicted in the figure below) analyse them at a level of detail allowing a selection of those technologies which fit into and promise early commercialization in the framework of FCH 2 JU’s funding program.<br/>These originally proposed eleven pathways use solar thermal energy sunlight or biomass as major energy input.
Integration of Chemical Looping Combustion for Cost-effective CO2 Capture from State-of-the-art Natural Gas Combined Cycles
May 2020
Publication
Chemical looping combustion (CLC) is a promising method for power production with integrated CO2 capture with almost no direct energy penalty. When integrated into a natural gas combined cycle (NGCC) plant however CLC imposes a large indirect energy penalty because the maximum achievable reactor temperature is far below the firing temperature of state-of-the-art gas turbines. This study presents a techno-economic assessment of a CLC plant that circumvents this limitation via an added combustor after the CLC reactors. Without the added combustor the energy penalty amounts to 11.4%-points causing a high CO2 avoidance cost of $117.3/ton which is more expensive than a conventional NGCC plant with post-combustion capture ($93.8/ton) with an energy penalty of 8.1%-points. This conventional CLC plant would also require a custom gas turbine. With an added combustor fired by natural gas a standard gas turbine can be deployed and CO2 avoidance costs are reduced to $60.3/ton mainly due to a reduction in the energy penalty to only 1.4%-points. However due to the added natural gas combustion after the CLC reactor CO2 avoidance is only 52.4%. Achieving high CO2 avoidance requires firing with clean hydrogen instead increasing the CO2 avoidance cost to $96.3/ton when a hydrogen cost of $15.5/GJ is assumed. Advanced heat integration could reduce the CO2 avoidance cost to $90.3/ton by lowering the energy penalty to only 0.6%-points. An attractive alternative is therefore to construct the plant for added firing with natural gas and retrofit the added combustor for hydrogen firing when CO2 prices reach very high levels.
Effect of TiO2 on Electrocatalytic Behavior of Ni-Mo Alloy Coating for Hydrogen Energy
Jun 2018
Publication
Ni-Mo-TiO2 composite coating has been developed through electrodeposition method by depositing titanium dioxide (TiO2) nanoparticles parallel to the process of Ni-Mo alloy coating. The experimental results explaining the increased electrocatalytic activity of Ni-Mo alloy coating on incorporation of TiO2 nanoparticles into its alloy matrix is reported here. The effect of addition of TiO2 on composition morphology and phase structure of TiO2 – composite coating is studied with special emphasis on its electrocatalytic activity for hydrogen evolution reaction (HER) in 1.0 M KOH solution. The electrocatalytic activity of alloy coatings were validated using cyclic voltammetry (CV) and chronopotentiometry (CP) techniques. Under optimal condition TiO2 – composite alloy coating represented as (Ni-Mo-TiO2)2.0 A dm 2 is found to exhibit the highest electrocatalytic activity for HER compared to its binary alloy counterpart. The increased electrocatalytic activity of (Ni-Mo-TiO2)2.0 A dm 2 composite coating was attributed to the increased Mo content porosity and roughness of coating affected due to addition of TiO2 nanoparticles supported by SEM EDX XRD and AFM study. The increased electrocatalytic activity of (Ni-Mo-TiO2)2.0 A dm 2 coating was found due to decreased Rct and increased Cdl values demonstrated by EIS study. Better electrocatalytic activity of (Ni-Mo-TiO2)2.0 A dm 2 coating compared to (Ni-Mo)2.0 A dm 2 coating has been explained through mechanism. Experimental study revealed that (Ni-Mo-TiO2)2.0 A dm 2 composite coating follows Volmer-Heyrovsky mechanism compared to Tafel mechanism in case of (Ni-Mo-TiO2)2.0 A dm 2 coating assessed on the basis of Tafel slopes.
Photocatalytic Hydrogen Production by Biomimetic Indium Sulfide Using Mimosa Pudica Leaves as Template
Jan 2019
Publication
Biomimetic sulfur-deficient indium sulfide (In2.77S4) was synthesized by a template-assisted hydrothermal method using leaves of Mimosa pudica as a template for the first time. The effect of this template in modifying the morphology of the semiconductor particles was determined by physicochemical characterization revealing an increase in surface area decrease in microsphere size and pore size and an increase in pore volume density in samples synthesized with the template. X-ray photoelectron spectroscopy (XPS) analysis showed the presence of organic sulfur (Ssingle bondO/Ssingle bondC/Ssingle bondH) and sulfur oxide species (single bondSO2 SO32− SO42−) at the surface of the indium sulfide in samples synthesized with the template. Biomimetic indium sulfide also showed significant amounts of Fe introduced as a contaminant present on the Mimosa pudica leaves. The presence of these sulfur and iron species favors the photocatalytic activity for hydrogen production by their acting as a sacrificial reagent and promoting water oxidation on the surface of the templated particles respectively. The photocatalytic hydrogen production rates over optimally-prepared biomimetic indium sulfide and indium sulfide synthesized without the organic template were 73 and 22 μmol g−1 respectively indicating an improvement by a factor of three in the templated sample.
Low-carbon Hydrogen Via Integration of Steam Methane Reforming with Molten Carbonate Fuel Cells at Low Fuel Utilization
Feb 2021
Publication
Hydrogen production is critical to many modern chemical processes – ammonia synthesis petroleum refining direct reduction of iron and more. Conventional approaches to hydrogen manufacture include steam methane reforming and autothermal reforming which today account for the lion's share of hydrogen generation. Without CO2 capture these processes emit about 8.7 kg of CO2 for each kg of H2 produced. In this study a molten carbonate fuel cell system with CO2 capture is proposed to retrofit the flue gas stream of an existing Steam Methane Reforming plant rated at 100000 Nm3 h−1 of 99.5% pure H2. The thermodynamic analysis shows direct CO2 emissions can be reduced by more than 95% to 0.4 to 0.5 kg CO2 /kg H2 while producing 17% more hydrogen (with an increase in natural gas input of approximately 37%). Because of the additional power and hydrogen generation of the carbonate fuel cell the efficiency debit associated with CO2 capture is quite small reducing the SMR efficiency from 76.6% without capture to 75.6% with capture. In comparison the use of standard amine technology for CO2 capture reduces the efficiency below 70%. This demonstrates the synergistic nature of the carbonate fuel cells which can reform natural gas to H2 while simultaneously capturing CO2 from the SMR flue gas and producing electricity giving rise to a total system with very low emissions yet high efficiency.
High-pressure Hydrogen Production with Inherent Sequestration of a Pure Carbon Dioxide Stream Via Fixed Bed Chemical Looping
Feb 2019
Publication
The proof of concept for the production of pure pressurized hydrogen from hydrocarbons in combination with the sequestration of a pure stream of carbon dioxide with the reformer steam iron cycle is presented. The iron oxide based oxygen carrier (95% Fe2O3 5% Al2O3) is reduced with syngas and oxidized with steam at 1023 K. The carbon dioxide separation is achieved via partial reduction of the oxygen carrier from Fe2O3 to Fe3O4 yielding thermodynamically to a product gas only containing CO2 and H2O. By the subsequent condensation of steam pure CO2 is sequestrated. After each steam oxidation phase an air oxidation was applied to restore the oxygen carrier to hematite level. Product gas pressures of up to 30.1 bar and hydrogen purities exceeding 99% were achieved via steam oxidations. The main impurities in the product gas are carbon monoxide and carbon dioxide which originate from solid carbon depositions or from stored carbonaceous molecules inside the pores of the contact mass. The oxygen carrier samples were characterized using elemental analysis BET surface area measurement XRD powder diffraction SEM and light microscopy. The maximum pressure of 95 bar was demonstrated for hydrogen production in the steam oxidation phase after the full oxygen carrier reduction significantly reducing the energy demand for compressors in mobility applications.
Anchoring of Turbulent Premixed Hydrogen/Air Flames at Externally Heated Walls
Oct 2020
Publication
A joint experimental and numerical investigation of turbulent flame anchoring at externally heated walls is presented. The phenomenon has primarily been studied for laminar flames and micro-combustion while this study focuses on large-scale applications and elevated Reynolds number flows. Therefore a novel burner design is developed and examined for a diverse set of operating conditions. Hydroxyl radical chemiluminescence measurements are employed to validate the numerical method. The numerical investigation evaluates the performance of various hydrogen/air kinetics Reynolds-averaged turbulence models and the eddy dissipation concept (EDC) as a turbulence-chemistry interaction model. Simulation results show minor differences between detailed chemical mechanisms but pronounced deviations for a reduced kinetic. The baseline k-ω turbulence model is assessed to most accurately predict flame front position and shape. Universal applicability of EDC modelling constants is contradicted. Conclusively the flame anchoring concept is considered a promising approach for pilot flames in continuous combustion devices.
Hydrogen and Hydrogen-derived Fuels through Methane Decomposition of Natural Gas – GHG Emissions and Costs
May 2020
Publication
Hydrogen can be produced from the decomposition of methane (also called pyrolysis). Many studies assume that this process emits few greenhouse gas (GHG) because the reaction from methane to hydrogen yields only solid carbon and no CO2. This paper assesses the life-cycle GHG emissions and the levelized costs for hydrogen provision from methane decomposition in three configurations (plasma molten metal and thermal gas). The results of these configurations are then compared to electrolysis and steam methane reforming (SMR) with and without CO2capture and storage (CCS). Under the global natural gas supply chain conditions hydrogen from methane decomposition still causes significant GHG emissions between 43 and 97 g CO2-eq./MJ. The bandwidth is predominately determined by the energy source providing the process heat i.e. the lowest emissions are caused by the plasma system using renewable electricity. This configuration shows lower GHG emissions compared to the “classical” SMR (99 g CO2-eq./MJ) but similar emissions to the SMR with CCS (46 g CO2-eq./MJ). However only electrolysis powered with renewable electricity leads to very low GHG emissions (3 g CO2-eq./MJ). Overall the natural gas supply is a decisive factor in determining GHG emissions. A natural gas supply with below-global average GHG emissions can lead to lower GHG emissions of all methane decomposition configurations compared to SMR. Methane decomposition systems (1.6 to 2.2 €/kg H2) produce hydrogen at costs substantially higher compared to SMR (1.0 to 1.2 €/kg) but lower than electrolyser (2.5 to 3.0 €/kg). SMR with CCS has the lowest CO2abatement costs (24 €/t CO2-eq. other > 141 €/t CO2-eq.). Finally fuels derived from different hydrogen supply options are assessed. Substantially lower GHG emissions compared to the fossil reference (natural gas and diesel/gasoline) are only possible if hydrogen from electrolysis powered by renewable energy is used (>90% less). The other hydrogen pathways cause only slightly lower or even higher GHG emissions.
Effect of Anion Exchange Ionomer Content on Electrode Performance in AEM Water Electrolysis
Aug 2020
Publication
Anion exchange membrane water electrolysis (AEMWE) has acquired substantial consideration as a cost-effective hydrogen production technology. The anion ionomer content in the catalyst layers during hydrogen and oxygen evolution reaction (HER and OER) is of ultimate significance. Herein an in-situ half-cell analysis with reference electrodes was carried out for simultaneous potential measurements and identification of the influence of the anion exchange ionomer (AEI) content on anode and cathode performance. The measured half-cell potentials proved the influence of AEI content on the catalytic activity of HER and OER which was supported by the rotating disk electrode (RDE) measurements. Cathode overpotential of Ni/C was not negligible and more affected by the AEI content than anode with the optimized AEI content of 10 wt% while NiO anode OER overpotential was independent of the AEI content. For the same AEI content PGM catalysts showed higher electroactivity than Ni-based catalysts for HER and OER and the cathode catalyst's intrinsic activity is of high importance in the AEM electrolysis operation. Post-mortem analysis by SEM mapping of both AEI and catalyst distributions on the electrode surface showed the effect of AEI loading on the catalyst morphology which could be related to the electrode performance.
Smart Designs of Mo Based Electrocatalysts for Hydrogen Evolution Reaction
Dec 2021
Publication
As a sustainable and clean energy source hydrogen can be generated by electrolytic water splitting (i.e. a hydrogen evolution reaction HER). Compared with conventional noble metal catalysts (e.g. Pt) Mo based materials have been deemed as a promising alternative with a relatively low cost and comparable catalytic performances. In this review we demonstrate a comprehensive summary of various Mo based materials such as MoO2 MoS2 and Mo2C. Moreover state of the art designs of the catalyst structures are presented to improve the activity and stability for hydrogen evolution including Mo based carbon composites heteroatom doping and heterostructure construction. The structure–performance relationships relating to the number of active sites electron/ion conductivity H/H2O binding and activation energy as well as hydrophilicity are discussed in depth. Finally conclusive remarks and future works are proposed.
Kinetics Study and Modelling of Steam Methane Reforming Process Over a NiO/Al2O3 Catalyst in an Adiabatic Packed Bed Reactor
Dec 2016
Publication
Kinetic rate data for steam methane reforming (SMR) coupled with water gas shift (WGS) over an 18 wt. % NiO/α-Al2O3 catalyst are presented in the temperature range of 300–700 °C at 1 bar. The experiments were performed in a plug flow reactor under the conditions of diffusion limitations and away from the equilibrium conditions. The kinetic model was implemented in a one-dimensional heterogeneous mathematical model of catalytic packed bed reactor developed on gPROMS model builder 4.1.0®. The mathematical model of SMR process was simulated and the model was validated by comparing the results with the experimental values. The simulation results were in excellent agreement with the experimental results. The effect of various operating parameters such as temperature pressure and steam to carbon ratio on fuel and water conversion (%) H2 yield (wt. % of CH4) and H2 purity was modelled and compared with the equilibrium values.
Production of H2-rich Syngas from Excavated Landfill Waste through Steam Co-gasification with Biochar
Jun 2020
Publication
Gasification of excavated landfill waste is one of the promising options to improve the added-value chain during remediation of problematic old landfill sites. Steam gasification is considered as a favorable route to convert landfill waste into H2-rich syngas. Co-gasification of such a poor quality landfill waste with biochar or biomass would be beneficial to enhance the H2 concentration in the syngas as well as to improve the gasification performance. In this work steam co-gasification of landfill waste with biochar or biomass was carried out in a lab-scale reactor. The effect of the fuel blending ratio was investigated by varying the auxiliary fuel content in the range of 15e35 wt%. Moreover co-gasification tests were carried out at temperatures between 800 and 1000°C. The results indicate that adding either biomass or biochar enhances the H2 yield where the latter accounts for the syngas with the highest H2 concentration. At 800°C the addition of 35 wt% biochar can enhance the H2 concentration from 38 to 54 vol% and lowering the tar yield from 0.050 to 0.014 g/g-fuel-daf. No apparent synergetic effect was observed in the case of biomass co-gasification which might cause by the high Si content of landfill waste. In contrast the H2 production increases non-linearly with the biochar share in the fuel which indicates that a significant synergetic effect occurs during co-gasification due to the reforming of tar over biochar. Increasing the temperature of biochar co-gasification from 800 to 1000°C elevates the H2 concentration but decreases the H2/CO ratio and increases the tar yield. Furthermore the addition of biochar also enhances the gasification efficiency as indicated by increased values of the energy yield ratio.
Advanced Hydrogen and CO2 Capture Technology for Sour Syngas
Apr 2011
Publication
A key challenge for future clean power or hydrogen projects via gasification is the need to reduce the overall cost while achieving significant levels of CO2 capture. The current state of the art technology for capturing CO2 from sour syngas uses a physical solvent absorption process (acid gas removal–AGR) such as Selexol™ or Rectisol® to selectively separate H2S and CO2 from the H2. These two processes are expensive and require significant utility consumption during operation which only escalates with increasing levels of CO2 capture. Importantly Air Products has developed an alternative option that can achieve a higher level of CO2 capture than the conventional technologies at significantly lower capital and operating costs. Overall the system is expected to reduce the cost of CO2 capture by over 25%.<br/>Air Products developed this novel technology by leveraging years of experience in the design and operation of H2 pressure swing adsorption (PSA) systems in its numerous steam methane reformers. Commercial PSAs typically operate on clean syngas and thus need an upstream AGR unit to operate in a gasification process. Air Products recognized that a H2 PSA technology adapted to handle sour feedgas (Sour PSA) would enable a new and enhanced improvement to a gasification system. The complete Air Products CO2 Capture technology (CCT) for sour syngas consists of a Sour PSA unit followed by a low-BTU sour oxycombustion unit and finally a CO2 purification / compression system.
Operational Challenges for Low and High Temperature Electrolyzers Exploiting Curtailed Wind Energy for Hydrogen Production
Jan 2021
Publication
Understanding the system performance of different electrolyzers could aid potential investors achieve maximum return on their investment. To realize this system response characteristics to 4 different summarized data sets of curtailed renewable energy is obtained from the Irish network and was investigated using models of both a Low Temperature Electrolyzer (LTE) and a High Temperature Electrolyzer (HTE). The results indicate that statistical parameters intrinsic to the method of data extraction along with the thermal response time of the electrolyzers influence the hydrogen output. A maximum hydrogen production of 5.97 kTonne/year is generated by a 0.5 MW HTE when the electrical current is sent as a yearly average. Additionally the high thermal response time in a HTE causes a maximum change in the overall flowrate of 65.7% between the 4 scenarios when compared to 7.7% in the LTE. This evaluation of electrolyzer performance will aid investors in determining scenario specific application of P2G for maximizing hydrogen production.
Direct Route from Ethanol to Pure Hydrogen through Autothermal Reforming in a Membrane Reactor: Experimental Demonstration, Reactor Modelling and Design
Nov 2020
Publication
This work reports the integration of thin (~3e4 mm thick) Pd-based membranes for H2 separation in a fluidized bed catalytic reactor for ethanol auto-thermal reforming. The performance of a fluidized bed membrane reactor has been investigated from an experimental and numerical point of view. The demonstration of the technology has been carried out over 50 h under reactive conditions using 5 thin Pd-based alumina-supported membranes and a 3 wt%Pt-10 wt%Ni catalyst deposited on a mixed CeO2/SiO2 support. The results have confirmed the feasibility of the concept in particular the capacity to reach a hydrogen recovery factor up to 70% while the operation at different fluidization regimes oxygen-to-ethanol and steam-to-ethanol ratios feed pressures and reactor temperatures have been studied. The most critical part of the system is the sealing of the membranes where most of the gas leakage was detected. A fluidized bed membrane reactor model for ethanol reforming has been developed and validated with the obtained experimental results. The model has been subsequently used to design a small reactor unit for domestic use showing that 0.45 m2 membrane area is needed to produce the amount of H2 required for a 5 kWe PEM fuel-cell based micro-CHP system.
Hydrogen Production as a Clean Energy Carrier through Heterojunction Semiconductors for Environmental Remediation
Apr 2022
Publication
Today as a result of the advancement of technology and increasing environmental problems the need for clean energy has considerably increased. In this regard hydrogen which is a clean and sustainable energy carrier with high energy density is among the well-regarded and effective means to deliver and store energy and can also be used for environmental remediation purposes. Renewable hydrogen energy carriers can successfully substitute fossil fuels and decrease carbon dioxide (CO2 ) emissions and reduce the rate of global warming. Hydrogen generation from sustainable solar energy and water sources is an environmentally friendly resolution for growing global energy demands. Among various solar hydrogen production routes semiconductor-based photocatalysis seems a promising scheme that is mainly performed using two kinds of homogeneous and heterogeneous methods of which the latter is more advantageous. During semiconductor-based heterogeneous photocatalysis a solid material is stimulated by exposure to light and generates an electron–hole pair that subsequently takes part in redox reactions leading to hydrogen production. This review paper tries to thoroughly introduce and discuss various semiconductor-based photocatalysis processes for environmental remediation with a specific focus on heterojunction semiconductors with the hope that it will pave the way for new designs with higher performance to protect the environment.
A Novel Exergy-based Assessment on a Multi-production Plant of Power, Heat and Hydrogen: Integration of Solid Oxide Fuel Cell, Solid Oxide Electrolyzer Cell and Rankine Steam Cycle
Feb 2021
Publication
Multi-production plant is an idea highlighting cost- and energy-saving purposes. However just integrating different sub-systems is not desired and the output and performance based on evaluation criteria must be assessed. In this study an integrated energy conversion system composed of solid oxide fuel cell (SOFC) solid oxide electrolyzer cell (SOEC) and Rankine steam cycle is proposed to develop a multi-production system of power heat and hydrogen to alleviate energy dissipation and to preserve the environment by utilizing and extracting the most possible products from the available energy source. With this regard natural gas and water are used to drive the SOEC and the Rankine steam cycle respectively. The required heat and power demand of the electrolyzer are designed to be provided by the fuel cell and the Rankine cycle. The feasibility of the designed integrated system is evaluated through comprehensive exergy-based analysis. The technical performance of the system is evaluated through exergy assessment and it is obtained that the SOFC and the SOEC can achieve to the high exergy efficiency of 84.8% and 63.7% respectively. The designed system provides 1.79 kg/h of hydrogen at 125 kPa. In addition the effective designed variables on the performance of the designed integrated system are monitored to optimize the system’s performance in terms of technical efficiency cost-effectivity and environmental considerations. This assessment shows that 59.4 kW of the available exergy is destructed in the combustion chamber. Besides the techno-economic analysis and exergoenvironmental assessment demonstrate the selected compressors should be re-designed to improve the cost-effectivity and decline the negative environmental impact of the designed integrated energy conversion system. In addition it is calculated that the SOEC has the highest total cost and also the highest negative impact on the environment compared to other designed units in the proposed integrated energy conversion system.
Integration of Gas Switching Combustion and Membrane Reactors for Exceeding 50% Efficiency in Flexible IGCC Plants with Near-zero CO2 Emissions
Jul 2020
Publication
Thermal power plants face substantial challenges to remain competitive in energy systems with high shares of variable renewables especially inflexible integrated gasification combined cycles (IGCC). This study addresses this challenge through the integration of Gas Switching Combustion (GSC) and Membrane Assisted Water Gas Shift (MAWGS) reactors in an IGCC plant for flexible electricity and/or H2 production with inherent CO2 capture. When electricity prices are high H2 from the MAWGS reactor is used for added firing after the GSC reactors to reach the high turbine inlet temperature of the H-class gas turbine. In periods of low electricity prices the turbine operates at 10% of its rated power to satisfy the internal electricity demand while a large portion of the syngas heating value is extracted as H2 in the MAWGS reactor and sold to the market. This product flexibility allows the inflexible process units such as gasification gas treating air separation unit and CO2 compression transport and storage to operate continuously while the plant supplies variable power output. Two configurations of the GSC-MAWGS plant are presented. The base configuration achieves 47.2% electric efficiency and 56.6% equivalent hydrogen production efficiency with 94.8–95.6% CO2 capture. An advanced scheme using the GSC reduction gases for coal-water slurry preheating and pre-gasification reached an electric efficiency of 50.3% hydrogen efficiency of 62.4% and CO2 capture ratio of 98.1–99.5%. The efficiency is 8.4%-points higher than the pre-combustion CO2 capture benchmark and only 1.9%-points below the unabated IGCC benchmark.
Studies of the Impact of Hydrogen on the Stability of Gaseous Mixtures of THT
Dec 2020
Publication
One of the most important requirements concerning the quality of natural gases guaranteeing their safe use involves providing the proper level of their odorization. This allows for the detection of uncontrolled leakages of gases from gas networks installations and devices. The concentration of an odorant should be adjusted in such a manner that the gas odor in a mixture with air would be noticeable by users (gas receivers). A permanent odor of gas is guaranteed by the stability of the odorant molecule and its resistance to changes in the composition of odorized gases. The article presents the results of experimental research on the impact of a hydrogen additive on the stability of tetrahydrothiophene (THT) mixtures in methane and in natural gas with a hydrogen additive. The objective of the work was to determine the readiness of measurement infrastructures routinely used in monitoring the process of odorizing natural gas for potential changes in its composition. One of the elements of this infrastructure includes the reference mixtures of THT used to verify the correctness of the readings of measurement devices. The performed experimental tests address possible changes in the composition of gases supplied via a distribution network resulting from the introduction of hydrogen. The lack of interaction between hydrogen and THT has been verified indirectly by assessing the stability of its mixtures with methane and natural gas containing hydrogen. The results of the presented tests permitted the identification of potential hazards for the safe use of gas from a distribution network resulting from changes in its composition caused by the addition of hydrogen.
Role of the Sulphur Source in the Solvothermal Synthesis of Ag-CdS Photocatalysts: Effects on the Structure and Photoactivity for Hydrogen Production
Dec 2020
Publication
The aim of this work is to study the influence of the sulphur source (elemental sulphur thiourea and L-cysteine) in the solvothermal synthesis of Ag-CdS over its growth structuration and state of Ag and how these changes influence on its photoactivity. The differences in the generation rate of the S2− from the sulphur sources during the solvothermal synthesis determine the nucleation and growth pathways of CdS affecting to the silver state and its incorporation into the CdS lattice. The hydrogen production on Ag-CdS photocatalysts decreases according the sequence: thiourea > elemental sulphur >> L-cysteine. The changes in the photoactivity of Ag-CdS samples are analysed in terms of the differences in the insertion of Ag+ into the CdS lattice the formation of composites between CdS and Ag2S and the formation of CdS crystalline domains with strong confinement effect derived from the different sulphur source used in the solvothermal synthesis
Biomass Steam Gasification with In-Situ CO2 Capture for Enriched Hydrogen Gas Production: A Reaction Kinetics Modelling Approach
Aug 2010
Publication
Due to energy and environmental issues hydrogen has become a more attractive clean fuel. Furthermore there is high interest in producing hydrogen from biomass with a view to sustainability. The thermochemical process for hydrogen production i.e. gasification is the focus of this work. This paper discusses the mathematical modeling of hydrogen production process via biomass steam gasification with calcium oxide as sorbent in a gasifier. A modelling framework consisting of kinetics models for char gasification methanation Boudouard methane reforming water gas shift and carbonation reactions to represent the gasification and CO2 adsorption in the gasifier is developed and implemented in MATLAB. The scope of the work includes an investigation of the influence of the temperature steam/biomass ratio and sorbent/biomass ratio on the amount of hydrogen produced product gas compositions and carbon conversion. The importance of different reactions involved in the process is also discussed. It is observed that hydrogen production and carbon conversion increase with increasing temperature and steam/biomass ratio. The model predicts a maximum hydrogen mole fraction in the product gas of 0.81 occurring at 950 K steam/biomass ratio of 3.0 and sorbent/biomass ratio of 1.0. In addition at sorbent/biomass ratio of 1.52 purity of H2 can be increased to 0.98 mole fraction with all CO2 present in the system adsorbed.
Instantaneous Hydrogen Production from Ammonia by Non-thermal Arc Plasma Combining with Catalyst
Jul 2021
Publication
Owing to the storage and transportation problems of hydrogen fuel exploring new methods of the realtime hydrogen production from ammonia becomes attractive. In this paper non-thermal arc plasma (NTAP) combining with NiO/Al2O3 catalyst is developed to produce hydrogen from ammonia with high efficiency and large scale. The effects of ammonia gas flow rate and discharge power on the gas temperature electron density the hydrogen production rate and energy efficiency were investigated. Experimental results show that the optical emission spectrum of NTAP working with pure ammonia medium was dominated by the atom spectrum of Hα Hβ and molecular spectrum of NH component. Under the optimum experimental condition of plasma discharge the highest energy efficiency of hydrogen production reached 783.4 L/kW·h at NH3 gas flow rate of 30 SLM. When the catalyst was added and heated by the NTAP simultaneously the energy efficiency further increased to 1080.0 L/kW·h.
H2 Green Hydrogen Discussion Paper: Victorian Hydrogen Investment Program
Nov 2019
Publication
This discussion paper is for stakeholders who would like to shape the development of Victoria’s emerging green hydrogen sector identifying competitive advantages and priority focus areas for industry and the Victorian Government.<br/>The Victorian Government is using this paper to focus on the economic growth and sector development opportunities emerging for a Victorian hydrogen industry powered by renewable energy also known as ‘green’ hydrogen. In addition this paper seeks input from all stakeholders on how where and when the Victorian Government can act to establish a thriving green hydrogen economy.<br/>Although green hydrogen is the only type of hydrogen production within the scope of this discussion paper the development of the VHIP aligns with the policies projects and initiatives which support these other forms of hydrogen production. The VHIP is considering the broad policy landscape and actively coordinating with related hydrogen programs policies and strategies under development including the Council of Australian Governments (COAG) Energy Council’s National Hydrogen Strategy to ensure a complementary approach. In Victoria there are several programs and strategies in development and underway that have linkages with hydrogen and the VHIP.
Improvement in Hydrogen Production with Plasma Reformer System
Jun 2016
Publication
In our previous studies of a plasma reformer system the effects of temperature of the reactants and input voltage have not been considered. In the present investigation the plasma reformer system has been modified to study the influence of the reactants’ temperature and input voltage on hydrogen production experimentally. The plasma reformer system includes a supersonic atomizer a plasma generator and a controlling device. In the experiment the operating parameters include the temperature of the reactants and the input voltage. The temperature of the reactants varies from 25 °C to 50 °C and the input voltage ranges from 12.5 V to 14.5 V. Results show that the increase in temperature of the reactants and input voltage will improve the production of hydrogen. In addition the improvement of heating on the reactants shows significant influence on hydrogen production.
Towards an Understanding of Hydrogen Supply Chains: A Structured Literature Review Regarding Sustainability Evaluation
Oct 2021
Publication
Hydrogen technologies have received increased attention in research and development to foster the shift towards carbon-neutral energy systems. Depending on the specific production techniques transportation concepts and application areas hydrogen supply chains (HSCs) can be anything from part of the energy transition problem to part of the solution: Even more than battery-driven electric mobility hydrogen is a polyvalent technology and can be used in very different contexts with specific positive or negative sustainability impacts. Thus a detailed sustainability evaluation is crucial for decision making in the context of hydrogen technology and its diverse application fields. This article provides a comprehensive structured literature review in the context of HSCs along the triple bottom line dimensions of environmental economic and social sustainability analyzing a total of 288 research papers. As a result we identify research gaps mostly regarding social sustainability and the supply chain stages of hydrogen distribution and usage. We suggest further research to concentrate on these gaps thus strengthening our understanding of comprehensive sustainability evaluations for HSCs especially in social sustainability evaluation. In addition we provide an additional approach for discussion by adding literature review results from neighboring fields highlighting the joint challenges and insights regarding sustainability evaluation.
Platinum Single-atom Catalyst Coupled with Transition Metal/Metal Oxide Heterostructure for Accelerating Alkaline Hydrogen Evolution Reaction
Jun 2021
Publication
Single-atom catalysts provide an effective approach to reduce the amount of precious metals meanwhile maintain their catalytic activity. However the sluggish activity of the catalysts for alkaline water dissociation has hampered advances in highly efficient hydrogen production. Herein we develop a single-atom platinum immobilized NiO/Ni heterostructure (PtSA-NiO/Ni) as an alkaline hydrogen evolution catalyst. It is found that Pt single atom coupled with NiO/Ni heterostructure enables the tunable binding abilities of hydroxyl ions (OH*) and hydrogen (H*) which efficiently tailors the water dissociation energy and promotes the H* conversion for accelerating alkaline hydrogen evolution reaction. A further enhancement is achieved by constructing PtSA-NiO/Ni nanosheets on Ag nanowires to form a hierarchical three-dimensional morphology. Consequently the fabricated PtSA-NiO/Ni catalyst displays high alkaline hydrogen evolution performances with a quite high mass activity of 20.6 A mg−1 for Pt at the overpotential of 100 mV significantly outperforming the reported catalysts.
Origin of the Catalytic Activity at Graphite Electrodes in Vanadium Flow Batteries
Jun 2021
Publication
For many electrochemical devices that use carbon-based materials such as electrolyzers supercapacitors and batteries oxygen functional groups (OFGs) are considered essential to facilitate electron transfer. Researchers implement surface-active OFGs to improve the electrocatalytic properties of graphite felt electrodes in vanadium flow batteries. Herein we show that graphitic defects and not OFGs are responsible for lowering the activation energy barrier and thus enhance the charge transfer properties. This is proven by a thermal deoxygenation procedure in which specific OFGs are removed before electrochemical cycling. The electronic and microstructural changes associated with deoxygenation are studied by quasi in situ X-ray photoelectron and Raman spectroscopy. The removal of oxygen groups at basal and edge planes improves the activity by introducing new active edge sites and carbon vacancies. OFGs hinder the charge transfer at the graphite–electrolyte interface. This is further proven by modifying the sp2 plane of graphite felt electrodes with oxygen-containing pyrene derivatives. The electrochemical evolution of OFGs and graphitic defects are studied during polarization and long-term cycling conditions. The hypothesis of increased activity caused by OFGs was refuted and hydrogenated graphitic edge sites were identified as the true reason for this increase.
Charge Carrier Mapping for Z-scheme Photocatalytic Water-splitting Sheet via Categorization of Microscopic Time-resolved Image Sequences
Jun 2021
Publication
Photocatalytic water splitting system using particulate semiconductor materials is a promising strategy for converting solar energy into hydrogen and oxygen. In particular visible-light-driven ‘Z-scheme’ printable photocatalyst sheets are cost-effective and scalable. However little is known about the fundamental photophysical processes which are key to explaining and promoting the photoactivity. Here we applied the pattern-illumination time-resolved phase microscopy for a photocatalyst sheet composed of Mo-doped BiVO4 and Rh-doped SrTiO3 with indium tin oxide as the electron mediator to investigate photo-generated charge carrier dynamics. Using this method we successfully observed the position- and structure-dependent charge carrier behavior and visualized the active/inactive sites in the sheets under the light irradiation via the time sequence images and the clustering analysis. This combination methodology could provide the material/synthesis optimization methods for the maximum performance of the photocatalyst sheets.
Highly Selective Porous Separator with Thin Skin Layer for Alkaline Water Electrolysis
Feb 2022
Publication
Advanced porous separators with thin selective skin layers to reduce the hydrogen permeation are developed for applications in alkaline water electrolysis. A thin skin layer based on crosslinked polyvinyl alcohol (cPVA) is fabricated on a porous substrate by a facile and scalable ultrasonic spray coating process. As the number of ultrasonic spraying cycles increases the resulting separator demonstrates a decrease in the large-diameter pore fraction an increase in the bubble-point pressure and a reduction in the hydrogen permeability without a significant increase in the areal resistance. As a result the optimized separator with a cPVA skin layer combines a low ionic resistance of 0.267 Ω cm2 a high bubble point pressure of 2.71 bar and a low hydrogen permeability of 1.12 × 10− 11 mol cm− 2 s − 1 bar− 1 . The electrolytic cell assembled with cPVAZ-30 achieves current densities of 861 mA cm− 2 and 1890 mA cm− 2 at 2.0 V and 2.6 V respectively in a 30 wt% KOH electrolyte solution at 80 ◦C.
High-pressure PEM Water Electrolyser Performance Up to 180 Bar Differential Pressure
Feb 2024
Publication
Proton exchange membrane (PEM) electrolysers (PEMEL) are key for converting and storing excess renewable energy. PEMEL water electrolysis offers benefits over alkaline water electrolysers including a large dynamic range high responsiveness and high current densities and pressures. High operating pressures are important because it contributes to reduce the costs and energy-use related to downstream mechanical compression. In this work the performance of a high-pressure PEMEL system has been characterized up to 180 bar. The electrolyser stack has been characterized with respect to electrochemical performance net H2 production rate and water crossover and the operability and performance of the thermal- and gas management systems of the test bench has been assessed. The tests show that the voltage increase upon pressurization from 5 to 30 bar is 30 % smaller than expected but further pressurization reduces performance. The study confirms that highpressure PEMEL has higher energy consumption than state-of-the-art electrolyser systems with mechanical compressors. However there can be a business case for high-pressure PEMEL if the trade-off between stack efficiency and system efficiency is balanced.
Selected Aspects of Hydrogen Production via Catalytic Decomposition of Hydrocarbons
Feb 2021
Publication
Owing to the high hydrogen content hydrocarbons are considered as an alternative source for hydrogen energy purposes. Complete decomposition of hydrocarbons results in the formation of gaseous hydrogen and solid carbonaceous by-product. The process is complicated by the methane formation reaction when the released hydrogen interacts with the formed carbon deposits. The present study is focused on the effects of the reaction mixture composition. Variations in the inlet hydrogen and methane concentrations were found to influence the carbon product’s morphology and the hydrogen production efficiency. The catalyst containing NiO (82 wt%) CuO (13 wt%) and Al2O3 (5 wt%) was prepared via a mechanochemical activating procedure. Kinetics of the catalytic process of hydrocarbons decomposition was studied using a reactor equipped with McBain balances. The effects of the process parameters were explored in a tubular quartz reactor with chromatographic analysis of the outlet gaseous products. In the latter case the catalyst was loaded piecemeal. The texture and morphology of the produced carbon deposits were investigated by nitrogen adsorption and electron microscopy techniques.
Study of Activity and Super-Capacitance Exhibited by Bifunctional Raney 2.0 Catalyst for Alkaline Water-Splitting Electrolysis
Dec 2020
Publication
Low-cost high-performance coatings for hydrogen production via electrolytic water-splitting are of great importance for de-carbonising energy. In this study the Raney2.0 coating was analysed using various electrochemical techniques to assess its absolute performance and it was confirmed to have an extremely low overpotential for hydrogen evolution of just 28 mV at 10 mA/cm2. It was also confirmed to be an acceptable catalyst for oxygen evolution making it the highest performing simple bifunctional electrocatalyst known. The coating exhibits an extremely high capacitance of up to 1.7 F/cm2 as well as being able to store 0.61 J/cm2 in the form of temporary hydride deposits. A new technique is presented that performs a best-fit of a transient simulation of an equivalent circuit containing a constant phase element to cyclic voltammetry measurements. From this the roughness factor of the coating was calculated to be approximately 40000 which is the highest figure ever reported for this type of material. The coating is therefore an extremely useful improved bifunctional coating for the continued roll-out of alkaline electrolysis for large-scale renewable energy capture via hydrogen production.
The Role of Critical Minerals in Clean Energy Transitions
May 2021
Publication
Minerals are essential components in many of today’s rapidly growing clean energy technologies – from wind turbines and electricity networks to electric vehicles. Demand for these minerals will grow quickly as clean energy transitions gather pace. This new World Energy Outlook Special Report provides the most comprehensive analysis to date of the complex links between these minerals and the prospects for a secure rapid transformation of the energy sector.
Alongside a wealth of detail on mineral demand prospects under different technology and policy assumptions it examines whether today’s mineral investments can meet the needs of a swiftly changing energy sector. It considers the task ahead to promote responsible and sustainable development of mineral resources and offers vital insights for policy makers including six key IEA recommendations for a new comprehensive approach to mineral security."
Link to International Energy Agency website
Alongside a wealth of detail on mineral demand prospects under different technology and policy assumptions it examines whether today’s mineral investments can meet the needs of a swiftly changing energy sector. It considers the task ahead to promote responsible and sustainable development of mineral resources and offers vital insights for policy makers including six key IEA recommendations for a new comprehensive approach to mineral security."
Link to International Energy Agency website
Enhanced Hydrogen Generation Efficiency of Methanol using Dielectric Barrier Discharge Plasma Methodology and Conducting Sea Water as an Electrode
Aug 2020
Publication
In this work methanol decomposition method has been discussed for the production of hydrogen gas with the application of plasma. A simple dielectric barrier discharge (DBD) plasma reactor was designed for this purpose with two types of electrode. The DBD plasma reactor was experimented by substituting one of the metal electrodes with feebly conducting sea water which yielded better efficiency in producing hydrogen gas. Experimental parameters such as; discharge voltage and time were varied by maintaining a discharge gap of 1.5 mm and the plasma discharge characteristics were studied. Filamentary type micro-discharges were found to be formed which was observed as numerous streamer clusters in the current waveform. Gas chromatographic study confirmed the production of hydrogen gas with residence time around 3.6 min. Although the concentration (%) of H2 was high (98.1 %) and consistent with copper electrode assembly the rate of formation and concentration was found to be the highest (98.7 %) for water electrode for specific discharge voltage. The energy efficiency was found to be 0.5 mol H2/kWh and 1.2 mol H2/kWh for metal (Cu) and water electrodes respectively. The electrode material significantly affects the plasma condition and hence the rate of hydrogen production. Compositional analysis of the water used as electrode showed a minimal change in the composition even after the completion of the experiment as compared to the untreated water. Methanol degradation study shows the presence of untreated methanol in the residue of the plasma reactor which has been confirmed from the absorption spectra.
Hydrothermal Synthesis of Iridium-Substituted NaTaO3 Perovskites
Jun 2021
Publication
Iridium-containing NaTaO3 is produced using a one-step hydrothermal crystallisation from Ta2O5 and IrCl3 in an aqueous solution of 10 M NaOH in 40 vol% H2O2 heated at 240 °C. Although a nominal replacement of 50% of Ta by Ir was attempted the amount of Ir included in the perovskite oxide was only up to 15 mol%. The materials are formed as crystalline powders comprising cube-shaped crystallites around 100 nm in edge length as seen by scanning transmission electron microscopy. Energy dispersive X-ray mapping shows an even dispersion of Ir through the crystallites. Profile fitting of powder X-ray diffraction (XRD) shows expanded unit cell volumes (orthorhombic space group Pbnm) compared to the parent NaTaO3 while XANES spectroscopy at the Ir LIII-edge reveals that the highest Ir-content materials contain Ir4+. The inclusion of Ir4+ into the perovskite by replacement of Ta5+ implies the presence of charge-balancing defects and upon heat treatment the iridium is extruded from the perovskite at around 600 °C in air with the presence of metallic iridium seen by in situ powder XRD. The highest Ir-content material was loaded with Pt and examined for photocatalytic evolution of H2 from aqueous methanol. Compared to the parent NaTaO3 the Ir-substituted material shows a more than ten-fold enhancement of hydrogen yield with a significant proportion ascribed to visible light absorption.
A Review on Recent Advances in Hydrogen Energy, Fuel Cell, Biofuel and Fuel Refining via Ultrasound Process Intensification
Mar 2021
Publication
Hydrogen energy is one of the most suitable green substitutes for harmful fossil fuels and has been investigated widely. This review extensively compiles and compares various methodologies used in the production storage and usage of hydrogen. Sonochemistry is an emerging synthesis process and intensification technique adapted for the synthesis of novel materials. It manifests acoustic cavitation phenomena caused by ultrasound where higher rates of reactions occur locally. The review discusses the effectiveness of sonochemical routes in developing fuel cell catalysts fuel refining biofuel production chemical processes for hydrogen production and the physical chemical and electrochemical hydrogen storage techniques. The operational parameters and environmental conditions used during ultrasonication also influence the production rates which have been elucidated in detail. Hence this review's major focus addresses sonochemical methods that can contribute to the technical challenges involved in hydrogen usage for energy.
Alkaline Water Electrolysis Powered by Renewable Energy: A Review
Feb 2020
Publication
Alkaline water electrolysis is a key technology for large-scale hydrogen production powered by renewable energy. As conventional electrolyzers are designed for operation at fixed process conditions the implementation of fluctuating and highly intermittent renewable energy is challenging. This contribution shows the recent state of system descriptions for alkaline water electrolysis and renewable energies such as solar and wind power. Each component of a hydrogen energy system needs to be optimized to increase the operation time and system efficiency. Only in this way can hydrogen produced by electrolysis processes be competitive with the conventional path based on fossil energy sources. Conventional alkaline water electrolyzers show a limited part-load range due to an increased gas impurity at low power availability. As explosive mixtures of hydrogen and oxygen must be prevented a safety shutdown is performed when reaching specific gas contamination. Furthermore the cell voltage should be optimized to maintain a high efficiency. While photovoltaic panels can be directly coupled to alkaline water electrolyzers wind turbines require suitable converters with additional losses. By combining alkaline water electrolysis with hydrogen storage tanks and fuel cells power grid stabilization can be performed. As a consequence the conventional spinning reserve can be reduced which additionally lowers the carbon dioxide emissions.
Oxygen Carriers for Chemical-looping Water Splitting to Hydrogen Production: A Critical Review
Oct 2021
Publication
Chemical looping water splitting (CLWS) process using metal oxides or perovskites as oxygen carriers (OCs) is capable of producing pure H2 in an efficient simple and flexible way. The OCs are first reduced by hydrocarbon fuels and then oxidized by steam in a cyclic way. After the condensation of the gaseous mixture of steam and H2 from the oxidation step pure H2 is obtained. In recent years great efforts for CLWS have been made to improve the redox activity and stability of OCs. In this paper the development of the OCs for hydrogen production from CLWS were discussed. Effects of supports and additives on the performances of OCs were compared based on redox reactions in CLWS. Fe-based OCs with CeO2 Al2O3 ZrO2 CuO MoO3 Rh etc. are very attractive for the CLWS process. Issues and challenges for the development of OCs were analyzed.
Water Electrolysis for the Production of Hydrogen to Be Employed in the Ironmaking and Steelmaking Industry
Nov 2021
Publication
The way to decarbonization will be characterized by the huge production of hydrogen through sustainable routes. Thus the basic production way is water electrolysis sustained by renewable energy sources allowing for obtaining “green hydrogen”. The present paper reviews the main available technologies for the water electrolysis finalized to the hydrogen production. We describe the fundamental of water electrolysis and the problems related to purification and/or desalinization of water before electrolysis. As a matter of fact we describe the energy efficiency issues with particular attention to the potential application in the steel industry. The fundamental aspects related to the choice of high-temperature or low-temperature technologies are analyzed.
Seasonal Storage and Alternative Carriers: A Flexible Hydrogen Supply Chain Model
May 2017
Publication
A viable hydrogen infrastructure is one of the main challenges for fuel cells in mobile applications. Several studies have investigated the most cost-efficient hydrogen supply chain structure with a focus on hydrogen transportation. However supply chain models based on hydrogen produced by electrolysis require additional seasonal hydrogen storage capacity to close the gap between fluctuation in renewable generation from surplus electricity and fuelling station demand. To address this issue we developed a model that draws on and extends approaches in the literature with respect to long-term storage. Thus we analyse Liquid Organic Hydrogen Carriers (LOHC) and show their potential impact on future hydrogen mobility. We demonstrate that LOHC-based pathways are highly promising especially for smaller-scale hydrogen demand and if storage in salt caverns remains uncompetitive but emit more greenhouse gases (GHG) than other gaseous or hydrogen ones. Liquid hydrogen as a seasonal storage medium offers no advantage compared to LOHC or cavern storage since lower electricity prices for flexible operation cannot balance the investment costs of liquefaction plants. A well-to-wheel analysis indicates that all investigated pathways have less than 30% GHG-emissions compared to conventional fossil fuel pathways within a European framework.
Catalyst Distribution Optimization Scheme for Effective Green Hydrogen Production from Biogas Reforming
Sep 2021
Publication
Green hydrogen technology has recently gained in popularity due to the current economic and ecological trends that aim to remove the fossil fuels share in the energy mix. Among various alternatives biogas reforming is an attractive choice for hydrogen production. To meet the authorities’ requirements reforming biogas-enriched natural gas and sole biogas is tempting. Highly effective process conditions of biogas reforming are yet to be designed. The current state of the art lacks proper optimization of the process conditions. The optimization should aim to allow for maximization of the process effectiveness and limitation of the phenomena having an adverse influence on the process itself. One of the issues that should be addressed in optimization is the uniformity of temperature inside a reactor. Here we show an optimization design study that aims to unify temperature distribution by novel arrangements of catalysts segments in the model biogas reforming reactor. The acquired numerical results confirm the possibility of the enhancement of reaction effectiveness coming from improving the thermal conditions. The used amount of catalytic material is remarkably reduced as a side effect of the presented optimization. To ensure an unhindered perception of the reaction improvement the authors proposed a ratio of the hydrogen output and the amount of used catalyst as a measure.
Hydrogen Production in the Light of Sustainability: A Comparative Study on the Hydrogen Production Technologies Using the Sustainability Index Assessment Method
Sep 2021
Publication
Hydrogen as an environmentally friendly energy carrier has received special attention to solving uncertainty about the presence of renewable energy and its dependence on time and weather conditions. This material can be prepared from different sources and in various ways. In previous studies fossil fuels have been used in hydrogen production but due to several limitations especially the limitation of the access to this material in the not-too-distant future and the great problem of greenhouse gas emissions during hydrogen production methods. New methods based on renewable and green energy sources as energy drivers of hydrogen production have been considered. In these methods water or biomass materials are used as the raw material for hydrogen production. In this article after a brief review of different hydrogen production methods concerning the required raw material these methods are examined and ranked from different aspects of economic social environmental and energy and exergy analysis sustainability. In the following the current position of hydrogen production is discussed. Finally according to the introduced methods their advantages and disadvantages solar electrolysis as a method of hydrogen production on a small scale and hydrogen production by thermochemical method on a large scale are introduced as the preferred methods.
Reversible Solid-oxide Cell Stack Based Power-to-x-to-power Systems: Comparison of Thermodynamic Performance
Jun 2020
Publication
The increasing penetration of variable renewable energies poses new challenges for grid management. The economic feasibility of grid-balancing plants may be limited by low annual operating hours if they work either only for power generation or only for power storage. This issue might be addressed by a dual-function power plant with power-to-x capability which can produce electricity or store excess renewable electricity into chemicals at different periods. Such a plant can be uniquely enabled by a solid-oxide cell stack which can switch between fuel cell and electrolysis with the same stack. This paper investigates the optimal conceptual design of this type of plant represented by power-to-x-to-power process chains with x being hydrogen syngas methane methanol and ammonia concerning the efficiency (on a lower heating value) and power densities. The results show that an increase in current density leads to an increased oxygen flow rate and a decreased reactant utilization at the stack level for its thermal management and an increased power density and a decreased efficiency at the system level. The power-generation efficiency is ranked as methane (65.9%) methanol (60.2%) ammonia (58.2%) hydrogen (58.3%) syngas (53.3%) at 0.4 A/cm2 due to the benefit of heat-to-chemical-energy conversion by chemical reformulating and the deterioration of electrochemical performance by the dilution of hydrogen. The power-storage efficiency is ranked as syngas (80%) hydrogen (74%) methane (72%) methanol (68%) ammonia (66%) at 0.7 A/cm2 mainly due to the benefit of co-electrolysis and the chemical energy loss occurring in the chemical synthesis reactions. The lost chemical energy improves plant-wise heat integration and compensates for its adverse effect on power-storage efficiency. Combining these efficiency numbers of the two modes results in a rank of round-trip efficiency: methane (47.5%)>syngas (43.3%) ≈ hydrogen (42.6%)>methanol (40.7%)>ammonia (38.6%). The pool of plant designs obtained lays the basis for the optimal deployment of this balancing technology for specific applications.
Dynamic Simulation and Thermoeconomic Analysis of a Hybrid Renewable System Based on PV and Fuel Cell Coupled with Hydrogen Storage
Nov 2021
Publication
The production of “green hydrogen” is currently one of the hottest topics in the field of renewable energy systems research. Hydrogen storage is also becoming more and more attractive as a flexible solution to mitigate the power fluctuations of solar energy systems. The most promising technology for electricity-to-hydrogen conversion and vice versa is the reversible solid-oxide cell (SOC). This device is still very expensive but it exhibits excellent performance under dynamic operating conditions compared to the competing devices. This work presents the dynamic simulation of a prototypal renewable plant combining a 50 kW photovoltaic (PV) field with a 50 kW solid-oxide electrolyzer cell (SOEC) and a compressed hydrogen tank. The electricity is used to meet the energy demand of a dwelling located in the area of Campi Flegrei (Naples). The SOC efficiency is simulated by developing a mathematical model in MATLAB®. The model also calculates the cell operating temperature as a function of the input current. Once the optimal values of the operating parameters of the SOC are calculated the model is integrated in the transient system simulation tool (TRNSYS) for dynamic analysis. Furthermore this work presents a parametric analysis of the hydrogen storage system (HSS). The results of the energy and environmental analyses show that the proposed system can reach a primary energy saving by 70% and an amount of saved CO2 of 28 tons/year. Some possible future market scenarios are considered for the economic analysis. In the most realistic case the optimal configuration shows a simple pay back lower than 10 years and a profit index of 46%.
Analysis of Trends and Emerging Technologies in Water Electrolysis Research Based on a Computational Method: A Comparison with Fuel Cell Research
Feb 2018
Publication
Water electrolysis for hydrogen production has received increasing attention especially for accumulating renewable energy. Here we comprehensively reviewed all water electrolysis research areas through computational analysis using a citation network to objectively detect emerging technologies and provide interdisciplinary data for forecasting trends. The results show that all research areas increase their publication counts per year and the following two areas are particularly increasing in terms of number of publications: “microbial electrolysis” and “catalysts in an alkaline water electrolyzer (AWE) and in a polymer electrolyte membrane water electrolyzer (PEME).”. Other research areas such as AWE and PEME systems solid oxide electrolysis and the whole renewable energy system have recently received several review papers although papers that focus on specific technologies and are cited frequently have not been published within the citation network. This indicates that these areas receive attention but there are no novel technologies that are the center of the citation network. Emerging technologies detected within these research areas are presented in this review. Furthermore a comparison with fuel cell research is conducted because water electrolysis is the reverse reaction to fuel cells and similar technologies are employed in both areas. Technologies that are not transferred between fuel cells and water electrolysis are introduced and future water electrolysis trends are discussed.
The Membrane-assisted Chemical Looping Reforming Concept for Efficient H2 Production with Inherent CO2 Capture: Experimental Demonstration and Model Validation
Feb 2018
Publication
In this work a novel reactor concept referred to as Membrane-Assisted Chemical Looping Reforming (MA-CLR) has been demonstrated at lab scale under different operating conditions for a total working time of about 100 h. This reactor combines the advantages of Chemical Looping such as CO2 capture and good thermal integration with membrane technology for a better process integration and direct product separation in a single unit which in its turn leads to increased efficiencies and important benefits compared to conventional technologies for H2 production. The effect of different operating conditions (i.e. temperature steam-to-carbon ratio or oxygen feed in the reactor) has been evaluated in a continuous chemical looping reactor and methane conversions above 90% have been measured with (ultra-pure) hydrogen recovery from the membranes. For all the cases a maximum recovery factor of around 30% has been measured which could be increased by operating the concept at higher pressures and with more membranes. The optimum conditions have been found at temperatures around 600°C for a steam-to-carbon ratio of 3 and diluted air in the air reactor (5% O2). The complete demonstration has been carried out feeding up to 1 L/min of CH4 (corresponding to 0.6 kW of thermal input) while up to 1.15 L/min of H2 was recovered. Simultaneously a phenomenological model has been developed and validated with the experimental results. In general good agreement is observed with overall deviations below 10% in terms of methane conversion H2 recovery and separation factor. The model allows better understanding of the behavior of the MA-CLR concept and the optimization and design of scaled-up versions of the concept.
Effect of Au Plasmonic Material on Poly M-Toluidine for Photoelectrochemical Hydrogen Generation from Sewage Water
Feb 2022
Publication
This study provides H2 gas as a renewable energy source from sewage water splitting reaction using a PMT/Au photocathode. So this study has a dual benefit for hydrogen generation; at the same time it removes the contaminations of sewage water. The preparation of the PMT is carried out through the polymerization process from an acid medium. Then the Au sputter was carried out using the sputter device under different times (1 and 2 min) for PMT/Au-1 min and PMT/Au-2min respectively. The complete analyses confirm the chemical structure such as XRD FTIR HNMR SEM and Vis-UV optical analyses. The prepared electrode PMT/Au is used for the hydrogen generation reaction using Na2S2O3 or sewage water as an electrolyte. The PMT crystalline size is 15 nm. The incident photon to current efficiency (IPCE) efficiency increases from 2.3 to 3.6% (at 390 nm) and the number of H2 moles increases from 8.4 to 33.1 mmol h−1 cm−2 for using Na2S2O3 and sewage water as electrolyte respectively. Moreover all the thermodynamic parameters such as activation energy (Ea) enthalpy (∆H*) and entropy (∆S*) were calculated; additionally a simple mechanism is mentioned for the water-splitting reaction.
Experimental Characterization and Energy Performance Assessment of a Sorption-Enhanced Steam–Methane Reforming System
Aug 2021
Publication
The production of blue hydrogen through sorption-enhanced processes has emerged as a suitable option to reduce greenhouse gas emissions. Sorption-enhanced steam–methane reforming (SESMR) is a process intensification of highly endothermic steam–methane reforming (SMR) ensured by in situ carbon capture through a solid sorbent making hydrogen production efficient and more environmentally sustainable. In this study a comprehensive energy model of SESMR was developed to carry out a detailed energy characterization of the process with the aim of filling a current knowledge gap in the literature. The model was applied to a bench-scale multicycle SESMR/sorbent regeneration test to provide an energy insight into the process. Besides the experimental advantages of higher hydrogen concentration (90 mol% dry basis 70 mol% wet basis) and performance of CO2 capture the developed energy model demonstrated that SESMR allows for substantially complete energy self-sufficiency through the process. In comparison to SMR with the same process conditions (650 ◦C 1 atm) performed in the same experimental rig SESMR improved the energy efficiency by about 10% further reducing energy needs.
Ranking Locations for Hydrogen Production Using Hybrid Wind-Solar: A Case Study
Apr 2021
Publication
Observing the growing energy demand of modern societies many countries have recognized energy security as a looming problem and renewable energies as a solution to this issue. Renewable hydrogen production is an excellent method for the storage and transfer of energy generated by intermittent renewable sources such as wind and solar so that they can be used at a place and time of our choosing. In this study the suitability of 15 cities in Fars province Iran for renewable hydrogen production was investigated and compared by the use of multiple multi-criteria decision-making methods including ARAS SAW CODAS and TOPSIS. The obtained rankings were aggregated by rank averaging Borda method and Copeland method. Finally the partially ordered set ranking technique was used to reach a general consensus about the ranking. The criteria that affect hydrogen production were found to be solar energy potential wind energy potential population air temperature natural disasters altitude relative humidity land cost skilled labor infrastructure topographic condition and distance from main roads. These criteria were weighted using the best–worst method (BWM) based on the data collected by a questionnaire. Solar energy potential was estimated using the Angstrom model. Wind energy potential was estimated by using the Weibull distribution function for each month independently. The results of the multi-criteria decision-making methods showed Izadkhast to be the most suitable location for renewable hydrogen production in the studied area.
A Hybrid Intelligent Model to Predict the Hydrogen Concentration in the Producer Gas from a Downdraft Gasifier
Apr 2022
Publication
This research work presents an artificial intelligence approach to predicting the hydrogen concentration in the producer gas from biomass gasification. An experimental gasification plant consisting of an air-blown downdraft fixed-bed gasifier fueled with exhausted olive pomace pellets and a producer gas conditioning unit was used to collect the whole dataset. During an extensive experimental campaign the producer gas volumetric composition was measured and recorded with a portable syngas analyzer at a constant time step of 10 seconds. The resulting dataset comprises nearly 75 hours of plant operation in total. A hybrid intelligent model was developed with the aim of performing fault detection in measuring the hydrogen concentration in the producer gas and still provide reliable values in the event of malfunction. The best performing hybrid model comprises six local internal submodels that combine artificial neural networks and support vector machines for regression. The results are remarkably satisfactory with a mean absolute prediction error of only 0.134% by volume. Accordingly the developed model could be used as a virtual sensor to support or even avoid the need for a real sensor that is specific for measuring the hydrogen concentration in the producer gas.
Stronger Together: Multi-annual Variability of Hydrogen Production Supported by Wind Power in Sweden
Mar 2021
Publication
Hydrogen produced from renewable electricity will play an important role in deep decarbonisation of industry. However adding large electrolyser capacities to a low-carbon electricity system also increases the need for additional electricity generation from variable renewable energies. This will require hydrogen production to be variable unless other sources provide sufficient flexibility. Existing sources of flexibility in hydro-thermal systems are hydropower and thermal generation which are both associated with sustainability concerns. In this work we use a dispatch model for the case of Sweden to assess the power system operation with large-scale electrolysers assuming that additional wind power generation matches the electricity demand of hydrogen production on average. We evaluate different scenarios for restricting the flexibility of hydropower and thermal generation and include 29 different weather years to test the impact of variable weather regimes. We show that (a) in all scenarios electrolyser utilisation is above 60% on average (b) the inter-annual variability of hydrogen production is substantial if thermal power is not dispatched for electrolysis and (c) this problem is aggravated if hydropower flexibility is also restricted. Therefore either long-term storage of hydrogen or backup hydrogen sources may be necessary to guarantee continuous hydrogen flows. Large-scale dispatch of electrolysis capacity supported by wind power makes the system more stable if electrolysers ramp down in rare hours of extreme events with low renewable generation. The need for additional backup capacities in a fully renewable electricity system will thus be reduced if wind power and electrolyser operation are combined in the system.
Progress and Prospects of Hydrogen Production: Opportunities and challenges
Jan 2021
Publication
This study presents an overview of the current status of hydrogen production in relation to the global requirement for energy and resources. Subsequently it symmetrically outlines the advantages and disadvantages of various production routes including fossil fuel/biomass conversion water electrolysis microbial fermentation and photocatalysis (PC) in terms of their technologies economy energy consumption and costs. Considering the characteristics of hydrogen energy and the current infrastructure issues it highlights that onsite production is indispensable and convenient for some special occasions. Finally it briefly summarizes the current industrialization situation and presents future development and research directions such as theoretical research strengthening renewable raw material development process coupling and sustainable energy use.
Comparison Between Hydrogen Production by Alkaline Water Electrolysis and Hydrogen Production by PEM Electrolysis
Sep 2021
Publication
Hydrogen is an ideal clean energy source that can be used as an energy storage medium for renewable energy sources. The water electrolysis hydrogen production technology which is one of the mainstream hydrogen production methods can be used to produce high-purity hydrogen and other energy sources can be converted into hydrogen storage by electrolysis. Hydrogen production by alkaline water electrolysis and hydrogen production by PEM electrolysis are all water electrolysis hydrogen production technologies that have been industrially applied. From the application point of view the paper compares the working principle of the two kinds of electrolyzers the process flow of hydrogen production equipment advantages and disadvantages. This article provides a reference for relevant researchers.
Exploring the Competitiveness of Hydrogen-fueled Gas Turbines in Future Energy Systems
Oct 2021
Publication
Hydrogen is currently receiving attention as a possible cross-sectoral energy carrier with the potential to enable emission reductions in several sectors including hard-to-abate sectors. In this work a techno-economic optimization model is used to evaluate the competitiveness of time-shifting of electricity generation using electrolyzers hydrogen storage and gas turbines fueled with hydrogen as part of the transition from the current electricity system to future electricity systems in Years 2030 2040 and 2050. The model incorporates an emissions cap to ensure a gradual decline in carbon dioxide (CO2) levels targeting near-zero CO2 emissions by Year 2050 and this includes 15 European countries. The results show that hydrogen gas turbines have an important role to play in shifting electricity generation and providing capacity when carbon emissions are constrained to very low levels in Year 2050. The level of competitiveness is however considerably lower in energy systems that still allow significant levels of CO2 emissions e.g. in Year 2030. For Years 2040 and 2050 the results indicate investments mainly in gas turbines that are partly fueled with hydrogen with 30e77 vol.-% hydrogen in biogas although some investments in exclusively hydrogen-fueled gas turbines are also envisioned. Both open cycle and combined cycle gas turbines (CCGT) receive investments and the operational patterns show that also CCGTs have a frequent cyclical operation whereby most of the start-stop cycles are less than 20 h in duration.
Analysis of Photon-driven Solar-to-hydrogen Production Methods in the Netherlands
Oct 2021
Publication
Hydrogen is deemed necessary for the realization of a sustainable society especially when renewable energy is used to generate hydrogen. As most of the photon-driven hydrogen production methods are not commercially available yet this study has investigated the techno economic and overall performance of four different solar-to hydrogen methods and photovoltaics-based electrolysis methods in the Netherlands. It was found that the photovoltaics-based electrolysis is the cheapest option with production cost of 9.31 $/kgH2. Production cost based on photo-catalytic water splitting direct bio-photolysis and photoelectrochemical water splitting are found to be 18.32 $/kgH2 18.45 $/kgH2 and 18.98 $/kgH2 respectively. These costs are expected to drop significantly in the future. Direct bio-photolysis (potential cost of 3.10 $/kgH2) and photo-catalytic water splitting (3.12 $/kgH2) may become cheaper than photovoltaics-based electrolysis. Based on preferences of three fictional technology investors i.e. a short-term a green and a visionary investor the overall performance of these methods are determined. Photovoltaics-based electrolysis is the most ideal option with photoelectrochemical water splitting a complementary option. While photovoltaics-based electrolysis has an advantage on the short-term because it is a non-integrated energy system on the long-term this might lead to relatively higher cost and performance limitations. Photochemical water splitting are integrated energy systems and have an advantage on the long-term because they need a relatively low theoretical overpotential and benefit from increasing temperatures. Both methods show performance improvements by the use of quantum dots. Bio-photolysis can be self-sustaining and can use wastewater to produce hydrogen but sudden temperature changes could lead to performance decrease.
A Combined Chemical-Electrochemical Process to Capture CO2 and Produce Hydrogen and Electricity
Sep 2021
Publication
Several carbon sequestration technologies have been proposed to utilize carbon dioxide (CO2 ) to produce energy and chemical compounds. However feasible technologies have not been adopted due to the low efficiency conversion rate and high-energy requirements. Process intensification increases the process productivity and efficiency by combining chemical reactions and separation operations. In this work we present a model of a chemical-electrochemical cyclical process that can capture carbon dioxide as a bicarbonate salt. The proposed process also produces hydrogen and electrical energy. Carbon capture is enhanced by the reaction at the cathode that displaces the equilibrium into bicarbonate production. Literature data show that the cyclic process can produce stable operation for long times by preserving ionic balance using a suitable ionic membrane that regulates ionic flows between the two half-cells. Numerical simulations have validated the proof of concept. The proposed process could serve as a novel CO2 sequestration technology while producing electrical energy and hydrogen.
Onshore, Offshore or In-turbine Electrolysis? Techno-economic Overview of Alternative Integration Designs for Green Hydrogen Production into Offshore Wind Power Hubs
Aug 2021
Publication
Massive investments in offshore wind power generate significant challenges on how this electricity will be integrated into the incumbent energy systems. In this context green hydrogen produced by offshore wind emerges as a promising solution to remove barriers towards a carbon-free economy in Europe and beyond. Motivated by the recent developments in Denmark with the decision to construct the world’s first artificial Offshore Energy Hub this paper investigates how the lowest cost for green hydrogen can be achieved. A model proposing an integrated design of the hydrogen and offshore electric power infrastructure determining the levelised costs of both hydrogen and electricity is proposed. The economic feasibility of hydrogen production from 2 Offshore Wind Power Hubs is evaluated considering the combination of different electrolyser placements technologies and modes of operations. The results show that costs down to 2.4 €/kg can be achieved for green hydrogen production offshore competitive with the hydrogen costs currently produced by natural gas. Moreover a reduction of up to 13% of the cost of wind electricity is registered when an electrolyser is installed offshore shaving the peak loads.
Thermodynamic Analysis of the Gasification of Municipal Solid Waste
May 2017
Publication
This work aims to understand the gasification performance of municipal solid waste (MSW) by means of thermodynamic analysis. Thermodynamic analysis is based on the assumption that the gasification reactions take place at the thermodynamic equilibrium condition without regard to the reactor and process characteristics. First model components of MSW including food green wastes paper textiles rubber chlorine-free plastic and polyvinyl chloride were chosen as the feedstock of a steam gasification process with the steam temperature ranging from 973 K to 2273 K and the steam-to-MSW ratio (STMR) ranging from 1 to 5. It was found that the effect of the STMR on the gasification performance was almost the same as that of the steam temperature. All the differences among the seven types of MSW were caused by the variation of their compositions. Next the gasification of actual MSW was analyzed using this thermodynamic equilibrium model. It was possible to count the inorganic components of actual MSW as silicon dioxide or aluminum oxide for the purpose of simplification due to the fact that the inorganic components mainly affected the reactor temperature. A detailed comparison was made of the composition of the gaseous products obtained using steam hydrogen and air gasifying agents to provide basic knowledge regarding the appropriate choice of gasifying agent in MSW treatment upon demand.
Life Cycle Assessment and Water Footprint of Hydrogen Production Methods: From Conventional to Emerging Technologies
Oct 2020
Publication
A common sustainability issue arising in production systems is the efficient use of resources for providing goods or services. With the increased interest in a hydrogen (H2) economy the life-cycle environmental performance of H2 production has special significance for assisting in identifying opportunities to improve environmental performance and to guide challenging decisions and select between technology paths. Life cycle impact assessment methods are rapidly evolving to analyze multiple environmental impacts of the production of products or processes. This study marks the first step in developing process-based streamlined life cycle analysis (LCA) of several H2 production pathways combining life cycle impacts at the midpoint (17 problem-oriented) and endpoint (3 damage-oriented) levels using the state-of-the-art impact assessment method ReCiPe 2016. Steam reforming of natural gas coal gasification water electrolysis via proton exchange membrane fuel cell (PEM) solid oxide electrolyzer cell (SOEC) biomass gasification and reforming and dark fermentation of lignocellulosic biomass were analyzed. An innovative aspect is developed in this study is an analysis of water consumption associated with H2 production pathways by life-cycle stage to provide a better understanding of the life cycle water-related impacts on human health and natural environment. For water-related scope Water scarcity footprint (WSF) quantified using Available Water Remaining (AWARE) method was applied as a stand-alone indicator. The paper discusses the strengths and weaknesses of each production pathway identify the drivers of environmental impact quantify midpoint environmental impact and its influence on the endpoint environmental performance. The findings of this study could serve as a useful theoretical reference and practical basis to decision-makers of potential environmental impacts of H2 production systems.
Analysis of Standard and Innovative Methods for Allocating Upstream and Refinery GHG Emissions to Oil Products
Sep 2017
Publication
Alternative fuel policies need accurate and transparent methods to find the embedded carbon intensity of individual refinery products. This study investigates different ways of allocating greenhouse gases emissions deriving from refining and upstream crude oil supply. Allocation methods based on mass energy content economic value and innovatively added-value are compared with the marginal refining emissions calculated by CONCAWE’s linear-programming model to the average EU refinery which has been adopted as reference in EU legislation. Beside the most important transportation fuels (gasoline diesel kerosene/jet fuel and heavy fuel oil) the analysis extends to petroleum coke and refinery hydrogen. Moreover novel criteria based on the implications due to hydrogen usage by each fuel pathway have been introduced to test the consistency of the analyzed approaches. It is found that only two economic-based allocation methods are consistent with the introduced criteria. These two methods also give negative refinery emissions for heavy products which is coherent with the marginal emissions calculated through the CONCAWE refinery model. The recommended allocation methods are transparent and use only publicly available statistical data so they may be useful not only for future EU legislation but also in jurisdictions where a representative refinery model is not available.
Transient Reversible Solid Oxide Cell Reactor Operation – Experimentally Validated Modeling and Analysis
Oct 2018
Publication
A reversible solid oxide cell (rSOC) reactor can operate efficiently in both electrolysis mode and in fuel cell mode. The bidirectional operability enables rSOC reactors to play a central role as an efficient energy conversion system for energy storage and sector coupling for a renewable energy driven society. A combined system for electrolysis and fuel cell operation can result in complex system configurations that should be able to switch between the two modes as quickly as possible. This can lead to temperature profiles within the reactor that can potentially lead to the failure of the reactor and eventually the system. Hence the behavior of the reactor during the mode switch should be analyzed and optimal transition strategies should be taken into account during the process system design stage. In this paper a one dimensional transient reversible solid oxide cell model was built and experimentally validated using a commercially available reactor. A simple hydrogen based system model was built employing the validated reactor model to study reactor behavior during the mode switch. The simple design leads to a system efficiency of 49% in fuel cell operation and 87% in electrolysis operation where the electrolysis process is slightly endothermic. Three transient operation strategies were studied. It is shown that the voltage response to transient operation is very fast provided the reactant flows are changed equally fast. A possible solution to ensure a safe mode switch by controlling the reactant inlet temperatures is presented. By keeping the rate of change of reactant inlet temperatures five to ten times slower than the mode switch a safe transition can be ensured.
How to Give a renewed Chance to Natural Gas as Feed for the Production of Hydrogen: Electric MSR Coupled with CO2 Mineralization
Sep 2021
Publication
Recent years have seen a growing interest in water electrolysis as a way to store renewable electric energy into chemical energy through hydrogen production. However today the share of renewable energy is still limited and there is the need to have a continuous use of H2 for industrial chemicals applications. Firstly the paper discusses the use of electrolysis - connected to a conventional grid - for a continuous H2 production in terms of associated CO2 emissions and compares such emissions with conventional methane steam reforming (MSR). Therefore it explores the possibility to use electrical methane steam reforming (eMSR) as a way to reduce the CO2 emissions. As a way to have zero emissions carbon mineralization of CO2 is coupled - instead of in-situ carbon capture and storage technology (CCS) - to eMSR; associated relevant cost of production is evaluated for different scenarios. It appears that to minimize such production cost carbonate minerals must be reused in the making of other industrial products since the amount of carbonates generated by the process is quite significant.
Hydrogen Production Technologies Overview
Jan 2019
Publication
Hydrogen energy became the most significant energy as the current demand gradually starts to increase. Hydrogen energy is an important key solution to tackle the global temperature rise. The key important factor of hydrogen production is the hydrogen economy. Hydrogen production technologies are commercially available while some of these technologies are still under development. This paper reviews the hydrogen production technologies from both fossil and non-fossil fuels such as (steam reforming partial oxidation auto thermal pyrolysis and plasma technology). Additionally water electrolysis technology was reviewed. Water electrolysis can be combined with the renewable energy to get eco-friendly technology. Currently the maximum hydrogen fuel productions were registered from the steam reforming gasification and partial oxidation technologies using fossil fuels. These technologies have different challenges such as the total energy consumption and carbon emissions to the environment are still too high. A novel non-fossil fuel method [ammonia NH3] for hydrogen production using plasma technology was reviewed. Ammonia decomposition using plasma technology without and with a catalyst to produce pure hydrogen was considered as compared case studies. It was showed that the efficiency of ammonia decomposition using the catalyst was higher than ammonia decomposition without the catalyst. The maximum hydrogen energy efficiency obtained from the developed ammonia decomposition system was 28.3% with a hydrogen purity of 99.99%. The development of ammonia decomposition processes is continues for hydrogen production and it will likely become commercial and be used as a pure hydrogen energy source.
Multi-Criteria Comparative Analysis of Clean Hydrogen Production Scenarios
Aug 2020
Publication
Different hydrogen production scenarios need to be compared in regard to multiple and often distinct aspects. It is well known that hydrogen production technologies based on environmentally-friendly renewable energy sources have higher values of the economic indicators than methods based on fossil fuels. Therefore how should this decision criterion (environmental) prevail over the other types of decision criteria (technical and economic) to make a scenario where hydrogen production only uses renewable energy sources the most attractive option for a decision-maker? This article presents the results of a multi-variant comparative analysis of scenarios to annually produce one million tons of pure hydrogen (99.999%) via electrolysis in Poland. The compared variants were found to differ in terms of electricity sources feeding the electrolyzers. The research demonstrated that the scenario where hydrogen production uses energy from photovoltaics only becomes the best option for the environmental criterion weighting value at 61%. Taking the aging effect of photovoltaic installation (PV) panels and electrolyzers after 10 years of operation into account the limit value of the environmental criterion rises to 63%. The carried out analyses may serve as the basis for the creation of systems supporting the development of clean and green hydrogen production technologies.
Optimal Operation of the Hydrogen-based Energy Management System with P2X Demand Response and Ammonia Plant
Jul 2021
Publication
Hydrogen production is the key in utilizing an excess renewable energy. Many studies and projects looked at the energy management systems (EMSs) that allow to couple hydrogen production with renewable generation. In the majority of these studies however hydrogen demand is either produced for powering fuel cells or sold to the external hydrogen market. Hydrogen demand from actual industrial plants is rarely considered. In this paper we propose an EMS based on the industrial cluster of GreenLab Skive (GLS) that can minimize the system’s operational cost or maximize its green hydrogen production. EMS utilizes a conventional and P2X demand response (DR) flexibility from electrolysis plant hydrogen storage tank electric battery and hydrogen-consuming plants to design the optimal schedule with maximized benefits. A potential addition to the existing components at GLS - an ammonia plant is modelled to identify its P2X potential and assess the economic viability of its construction. The results show a potential reduction of 51.5–61.6% for the total operational cost of the system and an increase of the share of green hydrogen by 10.4–37.6% due to EMS operation.
A New Energy System Based on Biomass Gasification for Hydrogen and Power Production
Apr 2020
Publication
In this paper a new gasification system is developed for the three useful outputs of electricity heat and hydrogen and reported for practical energy applications. The study also investigates the composition of syngas leaving biomass gasifier. The composition of syngas is represented by the fractions of hydrogen carbon dioxide carbon monoxide and water. The integrated energy system comprises of an entrained flow gasifier a Cryogenic Air Separation (CAS) unit a double-stage Rankine cycle Water Gas Shift Reactor (WGSR) a combined gas–steam power cycle and a Proton Exchange Membrane (PEM) electrolyzer. The whole integrated system is modeled in the Aspen plus 9.0 excluding the PEM electrolyzer which is modeled in Engineering Equation Solver (EES). A comprehensive parametric investigation is conducted by varying numerous parameters like biomass flow rate steam flow rate air input flow rate combustion reactor temperature and power supplied to the electrolyzer. The system is designed in a way to supply the power produced by the steam Rankine cycle to the PEM electrolyzer for hydrogen production. The overall energy efficiency is obtained to be 53.7% where the exergy efficiency is found to be 45.5%. Furthermore the effect of the biomass flow rate is investigated on the various system operational parameters.
Experimental Study of Hydrogen Production Using Electrolyte Nanofluids with a Simulated Light Source
Dec 2021
Publication
In this research we conducted water electrolysis experiments of a carbon black (CB) based sodium sulfate electrolyte using a Hoffman voltameter. The main objective was to investigate hydrogen production in such systems as well as analyse the electrical properties and thermal properties of nanofluids. A halogen lamp mimicking solar energy was used as a radiation source and a group of comparative tests were also conducted with different irradiation areas. The results showed that by using CB and light it was possible to increase the hydrogen production rate. The optimal CB concentration was 0.1 wt %. At this concentration the hydrogen production rate increased by 30.37% after 20 min of electrolysis. Hence we show that using CB in electrolytes irradiated by solar energy could save the electrical energy necessary for electrolysis processes.
Techno-Economic Assessment of Natural Gas Pyrolysis in Molten Salts
Jan 2022
Publication
Steam methane reforming with CO2 capture (blue hydrogen) and water electrolysis based on renewable electricity (green hydrogen) are commonly assumed to be the main supply options in a future hydrogen economy. However another promising method is emerging in the form of natural gas pyrolysis (turquoise hydrogen) with pure carbon as a valuable by-product. To better understand the potential of turquoise hydrogen this study presents a techno-economic assessment of a molten salt pyrolysis process. Results show that moderate reactor pressures around 12 bar are optimal and that reactor size must be limited by accepting reactor performance well below the thermodynamic equilibrium. Despite this challenge stemming from slow reaction rates the simplicity of the molten salt pyrolysis process delivers high efficiencies and promising economics. In the long-term carbon could be produced for 200–300 €/ton granting access to high-volume markets in the metallurgical and chemical process industries. Such a scenario makes turquoise hydrogen a promising alternative to blue hydrogen in regions with public resistance to CO2 transport and storage. In the medium-term expensive first-of-a-kind plants could produce carbon around 400 €/ton if hydrogen prices are set by conventional blue hydrogen production. Pure carbon at this cost level can access smaller high-value markets such as carbon anodes and graphite ensuring profitable operation even for first movers. In conclusion the economic potential of molten salt pyrolysis is high and further demonstration and scale-up efforts are strongly recommended.
How Flexible Electricity Demand Stabilizes Wind and Solar Market Values: The Case of Hydrogen Electrolyzers
Nov 2021
Publication
Wind and solar energy are often expected to fall victim to their own success: the higher their share in electricity generation the more their revenue in electricity markets (their “market value”) declines. While market values may converge to zero in conventional power systems this study argues that “green” hydrogen production can effectively and permanently halt the decline by adding flexible electricity demand in low-price hours. To support this argument this article further develops the merit order model and uses price duration curves to include flexible hydrogen electrolysis and to derive an analytical formula for the minimum market value of renewables in the long-term market equilibrium. This hydrogen-induced minimum market value is quantified for a wide range of parameters using Monte Carlo simulations and complemented with results from a more detailed numerical electricity market model. It is shown that—due to flexible hydrogen production alone—market values across Europe will likely stabilize above €19 ± 9 MWh− 1 for solar energy and above €27 ± 8 MWh− 1 for wind energy in 2050 (annual mean estimate ± standard deviation). This is in the range of the projected levelized cost of renewables and other types of flexible electricity demand may further increase renewable market values. Market-based renewables may hence be within reach.
Evaluation of Stability and Catalytic Activity of Ni Catalysts for Hydrogen Production by Biomass Gasification in Supercritical Water
Mar 2019
Publication
Supercritical water gasification is a promising technology for wet biomass utilization. In this paper Ni and other metal catalysts were synthesized by wet impregnation. The stability and catalytic activities of Ni catalysts were evaluated. Firstly catalytic activities of Ni Fe Cu catalysts supported on MgO were tested using wheat straw as raw material in a batch reactor at 723 K and water density of 0.07 cm3/g. Experimental results showed that the order of metal catalyst activity for hydrogen generation was Ni/MgO > Fe/MgO > Cu/MgO. Secondly the influence of different supports on Ni catalysts performance was investigated. The results showed that the order of the Ni catalysts’ activity with different supports was Ni/MgO > Ni/ZnO > Ni/Al2O3 > Ni/ZrO2. Finally the effects of Ni loading and the amount of Ni catalyst addition on hydrogen production and the stability of Ni/MgO catalyst were studied. It was found that serious deactivation of Ni catalyst in the process of supercritical water gasification took place. Even if carbon deposited on the catalyst surface was removed by high temperature calcination and the catalyst was reduced with hydrogen the activity of used catalyst was only partially restored.
Current Status and Development Trend of Wind Power Generation-based Hydrogen Production Technology
Jan 2019
Publication
The hydrogen production technology by wind power is an effective mean to improve the utilization of wind energy and alleviate the problem of wind power curtailment. First the basic principles and technical characteristics of the hydrogen production technology by wind power are briefly introduced. Then the history of the hydrogen production technology is reviewed and on this basis the hydrogen production system by wind power is elaborated in detail. In addition the prospect of the application of the hydrogen production technology by wind power is analyzed and discussed. In the end the key technology of the hydrogen production by wind power and the problems to be solved are comprehensively reviewed. The development of hydrogen production technology by wind power is analyzed from many aspects which provides reference for future development of hydrogen production technology by wind power
Hydrogen Production in the Swedish Power Sector: Considering Operational Volatilities and Long-term Uncertainties
Nov 2020
Publication
With more renewables on the Swedish electricity market while decommissioning nuclear power plants electricity supply increasingly fluctuates and electricity prices are more volatile. There is hence a need for securing the electricity supply before energy storage solutions become widespread. Electricity price fluctuations moreover affect operating income of nuclear power plants due to their inherent operational inflexibility. Since the anticipated new applications of hydrogen in fuel cell vehicles and steel production producing hydrogen has become a potential source of income particularly when there is a surplus supply of electricity at low prices. The feasibility of investing in hydrogen production was investigated in a nuclear power plant applying Swedish energy policy as background. The analysis applies a system dynamics approach incorporating the stochastic feature of electricity supply and prices. The study revealed that hydrogen production brings alternative opportunities for large-scale electricity production facilities in Sweden. Factors such as hydrogen price will be influential and require in-depth investigation. This study provides guidelines for power sector policymakers and managers who plan to engage in hydrogen production for industrial applications. Although this study was focused upon nuclear power sources it can be extended to hydrogen production from renewable energy sources such as wind and solar.
Ultra-clean Hydrogen Production by Ammonia Decomposition
Jan 2016
Publication
A rigorous heterogeneous mathematical model is used to simulate a cascade of multi-stage fixed bed membrane reactors (MSFBMR) with inter-stage heating and fresh sweep gas for the decomposition of ammonia to produce high purity hydrogen suitable for the PEM fuel cells. Different reactor configurations are compared. The comparison between a single fixed bed reactor (FBR) and a single fixed bed membrane reactor (FBMR) shows that the FBMR is superior to the FBR and gives 60.48% ammonia conversion higher than the FBR. However 20.91% exit ammonia conversion obtained by the FBMR is considered to be poor. The FBMR is limited by the kinetics at low temperatures. The numerical results show that the MSFBMR of four beds achieve 100.0% ammonia conversion. It was found that the membrane plays the prime role in the displacement of the thermodynamic equilibrium. The results also show that a linear relationship exists between the number of beds and the feed temperature and a correlation has been developed. A critical point for an effective hydrogen permeation zone has been identified. It is observed that the diffusion limitation is confined to a slim region at the entrance of the reactor. It is also observed that the heat load assumes a maximum inflection point and explanations offered. The results show that the multi-stage configuration has a promising potential to be applied successfully on-site for ultra-clean hydrogen production.
Hydrogen Generation by Photocatalytic Reforming of Potential Biofuels: Polyols, Cyclic Alcohols, and Saccharides
Jan 2018
Publication
We have studied hydrogen gas production using photocatalysis from C2-C5 carbon chain polyols cyclic alcohols and mono and di-saccharides using palladium nanoparticles supported on a TiO2 catalyst. For many of the polyols the hydrogen evolution rate is found to be dictated by the number of hydroxyl groups and available a-hydrogens in the structure. However the rule only applies to polyols and cyclic alcohols while the sugar activity is limited by the bulky structure of those molecules. There was also evidence of ring opening in photocatalytic reforming of cyclic alcohols that involved dehydrogenation and decarbonylation of a CC bond.
The Global Status of CCS 2019: Targeting Climate Change
Dec 2019
Publication
CCS is an emissions reduction technology critical to meeting global climate targets. The Global Status of CCS 2019 documents important milestones for CCS over the past 12 months its status across the world and the key opportunities and challenges it faces. We hope this report will be read and used by governments policy-makers academics media commentators and the millions of people who care about our climate.
Earth-Abundant Electrocatalysts for Water Splitting: Current and Future Directions
Mar 2021
Publication
Of all the available resources given to mankind the sunlight is perhaps the most abundant renewable energy resource providing more than enough energy on earth to satisfy all the needs of humanity for several hundred years. Therefore it is transient and sporadic that poses issues with how the energy can be harvested and processed when the sun does not shine. Scientists assume that electro/photoelectrochemical devices used for water splitting into hydrogen and oxygen may have one solution to solve this hindrance. Water electrolysis-generated hydrogen is an optimal energy carrier to store these forms of energy on scalable levels because the energy density is high and no air pollution or toxic gas is released into the environment after combustion. However in order to adopt these devices for readily use they have to be low-cost for manufacturing and operation. It is thus crucial to develop electrocatalysts for water splitting based on low-cost and land-rich elements. In this review I will summarize current advances in the synthesis of low-cost earth-abundant electrocatalysts for overall water splitting with a particular focus on how to be linked with photoelectrocatalytic water splitting devices. The major obstacles that persist in designing these devices. The potential future developments in the production of efficient electrocatalysts for water electrolysis are also described.
Resource Assessment for Hydrogen Production
Jul 2020
Publication
This analysis was conducted in support of the U.S. Department of Energy's H2@Scale initiative and this report examines the resources required to meet demand for an additional 10 million metric tonnes (MMT) of hydrogen in 2040. The technical potential of hydrogen production from fossil nuclear and renewable energy resources is presented. Updated maps describe the geographical distribution of hydrogen production potential from renewable energy resources. The results conclude that the technical resource availability of domestic energy resources is sufficient to meet an additional 10 MMT of hydrogen demand in 2040 without placing significant pressure on existing resources. While this level of hydrogen demand could result in a significant increase in renewable energy consumption in particular the technical potential of each resource is estimated to be sufficient to meet the demand. Future research to enable the large-scale integration of hydrogen in the U.S. energy and other sectors will include analyzing the geographic distribution of resources in relation to hydrogen demand for a variety of applications. Additional techno-economic analysis is also needed to understand the economic potential of hydrogen in other industries beyond transportation; such analysis is currently being undertaken by a multi-lab project initiated by DOE in 2016. Finally information from techno-economic analyses should be used to continually update and inform R&D targets for energy production hydrogen production and hydrogen utilization technologies.
Heat Recovery from a PtSNG Plant Coupled with Wind Energy
Nov 2021
Publication
Power to substitute natural gas (PtSNG) is a promising technology to store intermittent renewable electricity as synthetic fuel. Power surplus on the electric grid is converted to hydrogen via water electrolysis and then to SNG via CO2 methanation. The SNG produced can be directly injected into the natural gas infrastructure for long-term and large-scale energy storage. Because of the fluctuating behaviour of the input energy source the overall annual plant efficiency and SNG production are affected by the plant operation time and the standby strategy chosen. The re-use of internal (waste) heat for satisfying the energy requirements during critical moments can be crucial to achieving high annual efficiencies. In this study the heat recovery from a PtSNG plant coupled with wind energy based on proton exchange membrane electrolysis adiabatic fixed bed methanation and membrane technology for SNG upgrading is investigated. The proposed thermal recovery strategy involves the waste heat available from the methanation unit during the operation hours being accumulated by means of a two-tanks diathermic oil circuit. The stored heat is used to compensate for the heat losses of methanation reactors during the hot-standby state. Two options to maintain the reactors at operating temperature have been assessed. The first requires that the diathermic oil transfers heat to a hydrogen stream which is used to flush the reactors in order to guarantee the hot-standby conditions. The second option entails that the stored heat being recovered for electricity production through an Organic Rankine Cycle. The electricity produced is used to compensate the reactors heat losses by using electrical trace heating during the hot-standby hours as well as to supply energy to ancillary equipment. The aim of the paper is to evaluate the technical feasibility of the proposed heat recovery strategies and how they impact on the annual plant performances. The results showed that the annual efficiencies on an LHV basis were found to be 44.0% and 44.3% for the thermal storage and electrical storage configurations respectively.
Roadmap to Hybrid Offshore System with Hydrogen and Power Co-generation
Sep 2021
Publication
Constrained by the expansion of the power grid the development of offshore wind farms may be hindered and begin to experience severe curtailment or restriction. The combination of hydrogen production through electrolysis and hydrogen-to-power is considered to be a potential option to achieve the goal of low-carbon and energy security. This work investigates the competitiveness of different system configurations to export hydrogen and/or electricity from offshore plants with particular emphasis on unloading the mixture of hydrogen and electricity to end-users on land. Including the levelized energy cost and net present value a comprehensive techno-economic assessment method is proposed to analyze the offshore system for five scenarios. Assuming that the baseline distance is 10 km the results show that exporting hydrogen to land through pipelines shows the best economic performance with the levelized energy cost of 3.40 $/kg. For every 10 km increase in offshore distance the net present value of the project will be reduced by 5.69 MU$ and the project benefit will be positive only when the offshore distance is less than 53.5 km. An important finding is that the hybrid system under ship transportation mode is not greatly affected by the offshore distance. Every 10% increase in the proportion of hydrogen in the range of 70%–100% can increase the net present value by 1.43–1.70 MU$ which will increase by 7.36–7.37 MU$ under pipeline transportation mode. Finally a sensitivity analysis was carried out to analyze the wind speed electricity and hydrogen prices on the economic performance of these systems.
Computational Intelligence Approach for Modeling Hydrogen Production: A Review
Mar 2018
Publication
Hydrogen is a clean energy source with a relatively low pollution footprint. However hydrogen does not exist in nature as a separate element but only in compound forms. Hydrogen is produced through a process that dissociates it from its compounds. Several methods are used for hydrogen production which first of all differ in the energy used in this process. Investigating the viability and exact applicability of a method in a specific context requires accurate knowledge of the parameters involved in the method and the interaction between these parameters. This can be done using top-down models relying on complex mathematically driven equations. However with the raise of computational intelligence (CI) and machine learning techniques researchers in hydrology have increasingly been using these methods for this complex task and report promising results. The contribution of this study is to investigate the state of the art CI methods employed in hydrogen production and to identify the CI method(s) that perform better in the prediction assessment and optimization tasks related to different types of Hydrogen production methods. The resulting analysis provides in-depth insight into the different hydrogen production methods modeling technique and the obtained results from various scenarios integrating them within the framework of a common discussion and evaluation paper. The identified methods were benchmarked by a qualitative analysis of the accuracy of CI in modeling hydrogen production providing extensive overview of its usage to empower renewable energy utilization.
Production Costs for Synthetic Methane in 2030 and 2050 of an Optimized Power-to-Gas Plant with Intermediate Hydrogen Storage
Aug 2019
Publication
The publication gives an overview of the production costs of synthetic methane in a Power-to-Gas process. The production costs depend in particularly on the electricity price and the full load hours of the plant sub-systems electrolysis and methanation. The full-load hours of electrolysis are given by the electricity supply concept. In order to increase the full-load hours of methanation the size of the intermediate hydrogen storage tank and the size of the methanation are optimised on the basis of the availability of hydrogen. The calculation of the production costs for synthetic methane are done with economics for 2030 and 2050 and the expenditures are calculated for one year of operation. The sources of volume of purchased electricity are the short-term market long-term contracts direct-coupled renewable energy sources or seasonal use of surpluses. Gas sales are either traded on the short-term market or guaranteed by long-term contracts. The calculations show that an intermediate storage tank for hydrogen adjustment of the methanation size and operating electrolysis and methanation separately increase the workload of the sub-system methanation. The gas production costs can be significantly reduced. With the future expected development of capital expenditures operational expenditure electricity prices gas costs and efficiencies an economic production of synthetic natural gas for the years 2030 especially for 2050 is feasible. The results show that Power-to-Gas is an option for long-term large-scale seasonal storage of renewable energy. Especially the cases with high operating hours for the sub-system methanation and low electricity prices show gas production costs below the expected market prices for synthetic gas and biogas.
Life Cycle Assessments on Battery Electric Vehicles and Electrolytic Hydrogen: The Need for Calculation Rules and Better Databases on Electricity
May 2021
Publication
LCAs of electric cars and electrolytic hydrogen production are governed by the consumption of electricity. Therefore LCA benchmarking is prone to choices on electricity data. There are four issues: (1) leading Life Cycle Impact (LCI) databases suffer from inconvenient uncertainties and inaccuracies (2) electricity mix in countries is rapidly changing year after year (3) the electricity mix is strongly fluctuating on an hourly and daily basis which requires time-based allocation approaches and (4) how to deal with nuclear power in benchmarking. This analysis shows that: (a) the differences of the GHG emissions of the country production mix in leading databases are rather high (30%) (b) in LCA a distinction must be made between bundled and unbundled registered electricity certificates (RECs) and guarantees of origin (GOs); the residual mix should not be applied in LCA because of its huge inaccuracy (c) time-based allocation rules for renewables are required to cope with periods of overproduction (d) benchmarking of electricity is highly affected by the choice of midpoints and/or endpoint systems and (e) there is an urgent need for a new LCI database based on measured emission data continuously kept up-to-date transparent and open access.
A Comparison of Steam Reforming Concepts in Solid Oxide Fuel Cell Systems
Mar 2020
Publication
Various concepts have been proposed to use hydrocarbon fuels in solid oxide fuel cell (SOFC) systems. A combination of either allothermal or adiabatic pre-reforming and water recirculation (WR) or anode off-gas recirculation (AOGR) is commonly used to convert the fuel into a hydrogen rich mixture before it is electrochemically oxidised in the SOFC. However it is unclear how these reforming concepts affect the electrochemistry and temperature gradients in the SOFC stack. In this study four reforming concepts based on either allothermal or adiabatic pre-reforming and either WR or AOGR are modelled on both stack and system level. The electrochemistry and temperature gradients in the stack are simulated with a one-dimensional SOFC model and the results are used to calculate the corresponding system efficiencies. The highest system efficiencies are obtained with allothermal pre-reforming and WR. Adiabatic pre-reforming and AOGR result in a higher degree of internal reforming which reduces the cell voltage compared to allothermal pre-reforming and WR. Although this lowers the stack efficiency higher degrees of internal reforming reduce the power consumption by the cathode air blower as well leading to higher system efficiencies in some cases. This illustrates that both stack and system operation need to be considered to design an efficient SOFC system and predict potentially deteriorating temperature gradients in the stack.
Is Hydrogen the Future of Nuclear Energy?
Jan 2008
Publication
The traditionally held belief is that the future of nuclear energy is electricity production. However another possible future exists: nuclear energy used primarily for the production of hydrogen. The hydrogen in turn would be used to meet our demands for transport fuels (including liquid fuels) materials such as steel and fertilizer and peak-load electricity production. Hydrogen would become the replacement for fossil fuels in these applications that consume more than half the world’s energy. Such a future would follow from several factors: (a) concerns about climatic change that limit the use of fossil fuels (b) the fundamental technological differences between hydrogen and electricity that may preferentially couple different primary energy sources with either hydrogen or electricity and (c) the potential for other technologies to competitively produce electricity but not hydrogen. Electricity (movement of electrons) is not fundamentally a large-scale centralized technology that requires centralized methods of production distribution or use. In contrast hydrogen (movement of atoms) is intrinsically a large-scale centralized technology. The large-scale centralized characteristics of nuclear energy as a primary energy source hydrogen production systems and hydrogen storage systems naturally couple these technologies. This connection suggests that serious consideration be given to hydrogen as the ultimate product of nuclear energy and that nuclear systems be designed explicitly for hydrogen production.
Toward Design of Synergistically Active Carbon-Based Catalysts for Electrocatalytic Hydrogen Evolution
Apr 2014
Publication
Replacement of precious catalyst with cost-effective alternatives would be significantly beneficial for hydrogen production via electrocatalytic hydrogen evolution reaction (HER). All candidates thus far are exclusively metallic catalysts which suffer inherent corrosion and oxidation susceptibility during acidic proton-exchange membrane electrolysis. Herein based on theoretical predictions we designed and synthesized nitrogen (N) and phosphorus (P) dual-doped graphene as a non-metallic electrocatalyst for sustainable and efficient hydrogen production. The N and Phetero-atoms could coactivate the adjacent C atom in the graphene matrix by affecting its valence orbital energy levels to induce a synergistically enhanced reactivity toward HER. As a result the dual-doped graphene showed higher electrocatalytic HER activity than single-doped ones and comparable performance to some of the traditional metallic catalysts.
Electrified Hydrogen Production from Methane for PEM Fuel Cells Feeding: A Review
May 2022
Publication
The greatest challenge of our times is to identify low cost and environmentally friendly alternative energy sources to fossil fuels. From this point of view the decarbonization of industrial chemical processes is fundamental and the use of hydrogen as an energy vector usable by fuel cells is strategic. It is possible to tackle the decarbonization of industrial chemical processes with the electrification of systems. The purpose of this review is to provide an overview of the latest research on the electrification of endothermic industrial chemical processes aimed at the production of H2 from methane and its use for energy production through proton exchange membrane fuel cells (PEMFC). In particular two main electrification methods are examined microwave heating (MW) and resistive heating (Joule) aimed at transferring heat directly on the surface of the catalyst. For cases the catalyst formulation and reactor configuration were analyzed and compared. The key aspects of the use of H2 through PEM were also analyzed highlighting the most used catalysts and their performance. With the information contained in this review we want to give scientists and researchers the opportunity to compare both in terms of reactor and energy efficiency the different solutions proposed for the electrification of chemical processes available in the recent literature. In particular through this review it is possible to identify the solutions that allow a possible scale-up of the electrified chemical process imagining a distributed production of hydrogen and its consequent use with PEMs. As for PEMs in the review it is possible to find interesting alternative solutions to platinum with the PGM (Platinum Group Metal) free-based catalysts proposing the use of Fe or Co for PEM application.
Potential and Economic Analysis of Solar-to-Hydrogen Production in the Sultanate of Oman
Aug 2021
Publication
Hydrogen production using renewable power is becoming an essential pillar for future sustainable energy sector development worldwide. The Sultanate of Oman is presently integrating renewable power generations with a large share of solar photovoltaic (PV) systems. The possibility of using the solar potential of the Sultanate can increase energy security and contribute to the development of the sustainable energy sector not only for the country but also for the international community. This study presents the hydrogen production potential using solar resources available in the Sultanate. About 15 locations throughout the Sultanate are considered to assess the hydrogen production opportunity using a solar PV system. A rank of merit order of the locations for producing hydrogen is identified. It reveals that Thumrait and Marmul are the most suitable locations whereas Sur is the least qualified. This study also assesses the economic feasibility of hydrogen production which shows that the levelized cost of hydrogen (LCOH) in the most suitable site Thumrait is 6.31 USD/kg. The LCOH in the least convenient location Sur is 7.32 USD/kg. Finally a sensitivity analysis is performed to reveal the most significant influential factor affecting the future’s green hydrogen production cost. The findings indicate that green hydrogen production using solar power in the Sultanate is promising and the LCOH is consistent with other studies worldwide.
Improved Hydrogen-Production-Based Power Management Control of a Wind Turbine Conversion System Coupled with Multistack Proton Exchange Membrane Electrolyzers
Mar 2020
Publication
This paper deals with two main issues regarding the specific energy consumption in an electrolyzer (i.e. the Faraday efficiency and the converter topology). The first aspect is addressed using a multistack configuration of proton exchange membrane (PEM) electrolyzers supplied by a wind turbine conversion system (WTCS). This approach is based on the modeling of the wind turbine and the electrolyzers. The WTCS and the electrolyzers are interfaced through a stacked interleaved DC–DC buck converter (SIBC) due to its benefits for this application in terms of the output current ripple and reliability. This converter is controlled so that it can offer dynamic behavior that is faster than the wind turbine avoiding overvoltage during transients which could damage the PEM electrolyzers. The SIBC is designed to be connected in array configuration (i.e. parallel architecture) so that each converter operates at its maximum efficiency. To assess the performance of the power management strategy experimental tests were carried out. The reported results demonstrate the correct behavior of the system during transient operation.
Calculation and Analysis of Efficiencies and Annual Performances of Power-to-Gas Systems
Mar 2017
Publication
This paper describes a generic and systematic method to calculate the efficiency and the annual performance for Power-to-Gas (PtG) systems. This approach gives the basis to analytically compare different PtG systems using different technologies under different boundary conditions. To have a comparable basis for efficiency calculations a structured break down of the PtG system is done. Until now there has not been a universal approach for efficiency calculations. This has resulted in a wide variety of efficiency calculations used in feasibility studies and for business-case calculations. For this the PtG system is divided in two sub-systems: the electrolysis and the methanation. Each of the two sub-systems consists of several subsystem boundary levels. Staring from the main unit i.e. the electrolysis stack and/or methanation reactor further units that are required to operate complete PtG system are considered with their respective subsystem boundary conditions. The paper provides formulas how the efficiency of each level can be calculated and how efficiency deviations can be integrated which are caused by the extended energy flow calculations to and from energy users and thermal losses. By this a sensitivity analysis of the sub-systems can be gained and comprehensive goal functions for optimizations can be defined. In a second step the annual performance of the system is calculated as the ratio of useable output and energetic input over one year. The input is the integral of the annual need of electrical and thermal energy of a PtG system depending on the different operation states of the plant. The output is the higher heating value of the produced gas and – if applicable – heat flows that are used externally. The annual performance not only evaluates the steady-state operating efficiency under full load but also other states of the system such as cold standby or service intervals. It is shown that for a full system operation assessment and further system concept development the annual performance is of much higher importance than the steady-state system efficiency which is usually referred to. In a final step load profiles are defined and the annual performance is calculated for a specific system configuration. Using this example different operation strategies are compared.
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