Production & Supply Chain
Energy, Exergy, and Environmental Analyses of Renewable Hydrogen Production Through Plasma Gasification of Microalgal Biomass
Feb 2021
Publication
In this study an energy exergy and environmental (3E) analyses of a plasma-assisted hydrogen production process from microalgae is investigated. Four different microalgal biomass fuels namely raw microalgae (RM) and three torrefied microalgal fuels (TM200 TM250 and TM300) are used as the feedstock for steam plasma gasification to generate syngas and hydrogen. The effects of steam-tobiomass (S/B) ratio on the syngas and hydrogen yields and energy and exergy efficiencies of plasma gasification (hEn;PG hEx;PG) and hydrogen production(hEn;H2 hEx;H2 ) are taken into account. Results show that the optimal S/B ratios of RM TM200 TM250 and TM300 are 0.354 0.443 0.593 and 0.760 respectively occurring at the carbon boundary points (CBPs) where the maximum values of hEn;PG hEx;PG hEn;H2 and hEx;H2 are also achieved. At CBPs torrefied microalgae as feedstock lower thehEn;PG hEx;PG hEn;H2 and hEx;H2 because of their improved calorific value after undergoing torrefaction and the increased plasma energy demand compared to the RM. However beyond CBPs the torrefied feedstock displays better performance. A comparative life cycle analysis indicates that TM300 exhibits the highest greenhouse gases (GHG) emissions and the lowest net energy ratio (NER) due to the indirect emissions associated with electricity consumption.
Green Hydrogen: A New Flexibility Source for Security Constrained Scheduling of Power Systems with Renewable Energies
Apr 2021
Publication
Green hydrogen i.e. the hydrogen generated from renewable energy sources (RES) will significantly contribute to a successful energy transition. Besides to facilitate the integration and storage of RES this promising energy carrier is well capable to efficiently link various energy sectors. By introduction of green hydrogen as a new flexibility source to power systems it is necessary to investigate its possible impacts on the generation scheduling and power system security. In this paper a security-constrained multi-period optimal power flow (SC-MPOPF) model is developed aiming to determine the optimal hourly dispatch of generators as well as power to hydrogen (P2H) units in the presence of large-scale renewable energy sources (RES). The proposed model characterizes the P2H demand flexibility in the proposed SC-MPOPF model taking into account the electrolyzer behavior reactive power support of P2H demands and hydrogen storage capability. The developed SC-MPOPF model is applied to IEEE 39-bus system and the obtained numerical results demonstrate the role of P2H flexibility on cost as well as RES's power curtailment reduction.
Insights into the Principles, Design Methodology and Applications of Electrocatalysts Towards Hydrogen Evolution Reaction
Apr 2021
Publication
The electrolysis of water for sustainable hydrogen producing is a crucial segment of various emerging clean-energy technologies. However pursuing an efficient and cheap alternative catalyst to substitute state-of-the-art platinum-group electrocatalysts remains a prerequisite for the commercialization of this technology. Typically precious-metal-free catalysts have always much lower activities towards hydrogen production than that of Pt-group catalysts. To explore high-performance catalysts maximally exposed active sites rapid charge transfer ability and desirable electronic configuration are essentially demanded. Herein the fundamentals of hydrogen evolution reaction will be briefly described and the main focus will be on the interfacial engineering strategies by means of constructing defect structure creating heterojunction phase engineering lattice strain control designing hierarchical architecture and doping heteroatoms to effectively proliferate the catalytic active sites facilitate the electron diffusion and regulate the electronic configuration of numerous transition metals and their nitrides carbides sulfides phosphides as well as oxides achieving a benchmark performance of platinum-free electrocatalysts for the hydrogen evolution reaction. This review unambiguously offers proof that the conventional cheap and earth-abundant transition metal-based substances can be translated into an active water splitting catalyst by the rational and controllable interfacial designing.
Techno-economic Modelling of Water Electrolysers in the Range of Several MW to Provide Grid Services While Generating Hydrogen for Different Applications: A Case Study in Spain Applied to Mobility with FCEVs
Jun 2019
Publication
The use of hydrogen as energy carrier is a promising option to decarbonize both energy and transport sectors. This paper presents an advanced techno-economic model for calculation of optimal dispatch of large-scale multi MW electrolysis plants in order to obtain a more accurate evaluation of the feasibility of business cases related to the supply of this fuel for different end uses combined with grid services' provision. The model is applied to the Spanish case using different scenarios to determine the minimum demand required from the FCEV market so that electrolysis facilities featuring several MW result in profitable business cases. The results show that grid services contribute to the profitability of hydrogen production for mobility given a minimum but considerable demand from FCEV fleets.
Techno-economic Assessment of Electrolytic Hydrogen in China Considering Wind-solar-load Characteristic
Jan 2023
Publication
Hydrogen production by electrolysis is considered an essential means of consuming renewable energy in the future. However the current assessment of the potential of renewable energy electrolysis for hydrogen production is relatively simple and the perspective is not comprehensive. Here we established a Combined Wind and Solar Electrolytic Hydrogen system considering the influence of regional wind-solar-load characteristics and transmission costs to evaluate the hydrogen production potential of 31 provincial-level regions in China in 2050. The results show that in 2050 the levelized cost of hydrogen (LCOH) in China’s provincial regions will still be higher than 10 ¥/kg which is not cost-competitive compared to the current hydrogen production from fossil fuels. It is more cost-effective to deploy wind turbines than photovoltaic in areas with similar wind and solar resources or rich in wind resources. Wind-solar differences impact LCOH equipment capacity configuration and transmission cost composition while load fluctuation significantly impacts LCOH and electricity storage configuration. In addition the sensitivity analysis of 11 technical and economic parameters showed differences in the response performance of LCOH changes to different parameters and the electrolyzer conversion efficiency had the most severe impact. The analysis of subsidy policy shows that for most regions (except Chongqing and Xizang) subsidizing the unit investment cost of wind turbines can minimize LCOH. Nevertheless from the perspective of comprehensive subsidy effect subsidy cost and hydrogen energy development it is more cost-effective to take subsidies for electrolysis equipment with the popularization of hydrogen
Delivering Clean Growth: CCUS Cost Challenge Taskforce Report
Jul 2018
Publication
An independent report by the CCUS Cost Challenge Taskforce setting out the industry’s view on how best to progress carbon capture usage and storage (CCUS) in the UK in order to enable the UK to have the option of deploying CCUS at scale during the 2030s subject to costs coming down sufficiently.
Facile Synthesis of Palladium Phosphide Electrocatalysts and their Activity for the Hydrogen Oxidation, Hydrogen Evolutions, Oxygen Reduction and Formic Acid Oxidation Reactions
Nov 2015
Publication
We demonstrate a new approach for producing highly dispersed supported metal phosphide powders with small particle size improved stability and increased electrocatalytic activity towards some useful reactions. The approach involves a one-step conversion of metal supported on high surface area carbon to the metal phosphide utilising a very simple and scalable synthetic process. We use this approach to produce PdP2 and Pd5P2 particles dispersed on carbon with a particle size of 4.5–5.5 nm by converting a commercially available Pd/C powder. The metal phosphide catalysts were tested for the oxygen reduction hydrogen oxidation and evolution and formic acid oxidation reactions. Compared to the unconverted Pd/C material we find that alloying the P at different levels shifts oxide formation on the Pd to higher potentials leading to greater stability during cycling studies (20% more ECSA retained 5k cycles) and in thermal treatment under air. Hydrogen absorption within the PdP2 and Pd5P2 particles is enhanced. The phosphides compare favourably to the most active catalysts reported to date for formic acid oxidation especially PdP2 and there is a significant decrease in poisoning of the surface compared to Pd alone. The mechanistic changes in the reactions studied are rationalised in terms of increased water activation on the surface phosphorus atoms of the catalyst. One of the catalysts PdP2/C is tested in a fuel cell as anode and cathode catalyst and shows good performance.
High Purity, Self-sustained, Pressurized Hydrogen Production from Ammonia in a Catalytic Membrane Reactor
Dec 2021
Publication
The combination of catalytic decomposition of ammonia and in situ separation of hydrogen holds great promise for the use of ammonia as a clean energy carrier. However finding the optimal catalyst – membrane pair and operation conditions have proved challenging. Here we demonstrate that cobalt-based catalysts for ammonia decomposition can be efficiently 2 used together with a Pd-Au based membrane to produce high purity hydrogen at elevated pressure. Compared to a conventional packed bed reactor the membrane reactor offers several operational advantages that result in energetic and economic benefits. The robustness and durability of the combined system has been demonstrated for more than 1000 h on stream yielding a very pure hydrogen stream (>99.97 % H2) and recovery (>90 %). When considering the required hydrogen compression for storage/utilization and environmental issues the combined system offers the additional advantage of production of hydrogen at moderate pressures along with full ammonia conversion. Altogether our results demonstrate the possibility of deploying high pressure (350 bar) hydrogen generators from ammonia with H2 efficiencies of circa 75% without any external energy input and/or derived CO2 emissions.
Life Cycle Assessment of Natural Gas-based Chemical Looping for Hydrogen Production
Dec 2014
Publication
Hydrogen production from natural gas combined with advanced CO2 capture technologies such as iron-based chemical looping (CL) is considered in the present work. The processes are compared to the conventional base case i.e. hydrogen production via natural gas steam reforming (SR) without CO2 capture. The processes are simulated using commercial software (ChemCAD) and evaluated from a technical point of view considering important key performance indicators such as hydrogen thermal output net electric power carbon capture rate and specific CO2 emissions. The environmental evaluation is performed using Life Cycle Analysis (LCA) with the following system boundaries considered: i) hydrogen production from natural gas coupled to CO2 capture technologies based on CL ii) upstream processes such as: extraction and processing of natural gas ilmenite and catalyst production and iii) downstream processes such as: H2 and CO2 compression transport and storage. The LCA assessment was carried out using the GaBi6 software. Different environmental impact categories following here the CML 2001 impact assessment method were calculated and used to determine the most suitable technology. Sensitivity analyses of the CO2 compression transport and storage stages were performed in order to examine their effect on the environmental impact categories.
Aqueous Phase Reforming of the Residual Waters Derived from Lignin-rich Hydrothermal Liquefaction: Investigation of Representative Organic Compounds and Actual Biorefinery Streams
Sep 2019
Publication
Secondary streams in biorefineries need to be valorized to improve the economic and environmental sustainability of the plants. Representative model compounds of the water fraction from the hydrothermal liquefaction (HTL) of biomass were subjected to aqueous phase reforming (APR) to produce hydrogen. Carboxylic and bicarboxylic acids hydroxyacids alcohols cycloketones and aromatics were identified as model compounds and tested for APR. The tests were performed with a Pt/C catalyst and the influence of the carbon concentration (0.3–1.8 wt. C%) was investigated. Typically the increase of the concentration negatively affected the conversion of the feed toward gaseous products without influencing the selectivity toward hydrogen production. A synthetic ternary mixture (glycolic acid acetic acid lactic acid) was subjected to APR to evaluate any differences in performance compared to the tests with single compounds. Indeed glycolic acid reacted faster in the mixture than in the corresponding single compound test while acetic acid remained almost unconverted. The influence of the reaction time temperature and carbon concentration was also evaluated. Finally residual water resulting from the HTL of a lignin-rich stream originating from an industrial-scale lignocellulosic ethanol process was tested for the first time after a thorough characterization. In this framework the stability of the catalyst was studied and found to be correlated to the presence of aromatics in the aqueous feedstock. For this reason the influence of an extraction procedure for the selective removal of these compounds was explored leading to an improvement in the APR performance.
Modeling of Thermal Performance of a Commercial Alkaline Electrolyzer Supplied with Various Electrical Currents
Nov 2021
Publication
Hydrogen produced by solar and other clean energy sources is an essential alternative to fossil fuels. In this study a commercial alkaline electrolyzer with different cell numbers and electrode areas are simulated for different pressure temperature thermal resistance and electrical current. This alkaline electrolyzer is considered unsteady in simulations and different parameters such as temperature are obtained in terms of time. The obtained results are compared with similar results in the literature and good agreement is observed. Various characteristics of this alkaline electrolyzer as thermoneutral voltage faraday efficiency and cell voltage are calculated and displayed. The outlet heat rate and generated heat rate are obtained as well. The pressure and the temperature in the simulations are between 1 and 100 bar and between 300 and 360 Kelvin respectively. The results show that the equilibrium temperature is reached 2-3 hours after the time when the Alkaline electrolyzer starts to work.
Electrolyzers Enhancing Flexibility in Electric Grids
Nov 2017
Publication
This paper presents a real-time simulation with a hardware-in-the-loop (HIL)-based approach for verifying the performance of electrolyzer systems in providing grid support. Hydrogen refueling stations may use electrolyzer systems to generate hydrogen and are proposed to have the potential of becoming smarter loads that can proactively provide grid services. On the basis of experimental findings electrolyzer systems with balance of plant are observed to have a high level of controllability and hence can add flexibility to the grid from the demand side. A generic front end controller (FEC) is proposed which enables an optimal operation of the load on the basis of market and grid conditions. This controller has been simulated and tested in a real-time environment with electrolyzer hardware for a performance assessment. It can optimize the operation of electrolyzer systems on the basis of the information collected by a communication module. Real-time simulation tests are performed to verify the performance of the FEC-driven electrolyzers to provide grid support that enables flexibility greater economic revenue and grid support for hydrogen producers under dynamic conditions. The FEC proposed in this paper is tested with electrolyzers however it is proposed as a generic control topology that is applicable to any load.
Cotton Stalk Activated Carbon-supported Co–Ce–B Nanoparticles as Efficient Catalysts for Hydrogen Generation Through Hydrolysis of Sodium Borohydride
Nov 2019
Publication
Porous cotton stalk activated carbons (CSAC) were prepared by phosphoric acid activation of cotton stalks in a fluidized bed. The CSAC-supported Co–B and Co–Ce–B catalysts were prepared by the impregnation-chemical reduction method. The samples were characterized by the nitrogen adsorption XRD FTIR and TEM measurements. The effects of the sodium borohydride (NaBH4) and sodium hydroxide (NaOH) concentrations reaction temperature and recyclability on the rate of NaBH4 hydrolysis over the CSAC-supported Co–Ce–B catalysts were systematically investigated. The results showed that the agglomeration of the Co–Ce–B nanoclusters on the CSAC support surface was significantly reduced with the introduction of cerium. The CSAC-supported Co–Ce–B catalyst exhibited superior catalytic activity and the average hydrogen generation rate was 16.42 L min−1 g−1 Co at 25°C which is higher than the most reported cobalt-based catalysts. The catalytic hydrolysis of NaBH4 was zero order with respect to the NaBH4 concentration and the hydrogen generation rate decreased with the increase in the NaOH concentration. The activation energy of the hydrogen generation reaction on the prepared catalyst was estimated to be 48.22 kJ mol−1. A kinetic rate equation was also proposed.
An Investigation of a (Vinylbenzyl) Trimethylammonium and N-Vinylimidazole-Substituted Poly (Vinylidene Fluoride-Co-Hexafluoropropylene) Copolymer as an Anion-Exchange Membrane in a Lignin-Oxidising Electrolyser
Jun 2021
Publication
Electrolysis is seen as a promising route for the production of hydrogen from water as part of a move to a wider “hydrogen economy”. The electro-oxidation of renewable feedstocks offers an alternative anode couple to the (high-overpotential) electrochemical oxygen evolution reaction for developing low-voltage electrolysers. Meanwhile the exploration of new membrane materials is also important in order to try and reduce the capital costs of electrolysers. In this work we synthesise and characterise a previously unreported anion-exchange membrane consisting of a fluorinated polymer backbone grafted with imidazole and trimethylammonium units as the ion-conducting moieties. We then investigate the use of this membrane in a lignin-oxidising electrolyser. The new membrane performs comparably to a commercially-available anion-exchange membrane (Fumapem) for this purpose over short timescales (delivering current densities of 4.4 mA cm−2 for lignin oxidation at a cell potential of 1.2 V at 70 °C during linear sweep voltammetry) but membrane durability was found to be a significant issue over extended testing durations. This work therefore suggests that membranes of the sort described herein might be usefully employed for lignin electrolysis applications if their robustness can be improved.
A Multiobjective Optimization of a Catalyst Distribution in a Methane/Steam Reforming Reactor Using a Genetic Algorithm
May 2020
Publication
The presented research focuses on an optimization design of a catalyst distribution inside a small-scale methane/steam reforming reactor. A genetic algorithm was used for the multiobjective optimization which included the search for an optimum of methane conversion rate and a minimum of the difference between highest and lowest temperatures in the reactor. For the sake of computational time the maximal number of the segment with different catalyst densities was set to be thirty in this study. During the entire optimization process every part of the reactor could be filled either with a catalyst material or non-catalytic metallic foam. In both cases the porosity and pore size was also specified. The impact of the porosity and pore size on the active reaction surface and permeability was incorporated using graph theory and three-dimensional digital material representation. Calculations start with the generation of a random set of possible reactors each with a different catalyst distribution. The algorithm calls reforming simulation over each of the reactors and after obtaining concentration and temperature fields the algorithms calculated fitness function. The properties of the best reactors are combined to generate a new population of solutions. The procedure is repeated and after meeting the coverage criteria the optimal catalyst distribution was proposed. The paper is summarized with the optimal catalyst distribution for the given size and working conditions of the system.
Towards Computer-Aided Graphene Covered TiO2-Cu(CuxOy) Composite Design for the Purpose of Photoinduced Hydrogen Evolution
May 2021
Publication
In search a hydrogen source we synthesized TiO2-Cu-graphene composite photocatalyst for hydrogen evolution. The catalyst is a new and unique material as it consists of copper-decorated TiO2 particles covered tightly in graphene and obtained in a fluidized bed reactor. Both reduction of copper from Cu(CH3COO) at the surface of TiO2 particles and covering of TiO2-Cu in graphene thin layer by Chemical Vapour Deposition (CVD) were performed subsequently in the flow reactor by manipulating the gas composition. Obtained photocatalysts were tested in regard to hydrogen generation from photo-induced water conversion with methanol as sacrificial agent. The hydrogen generation rate for the most active sample reached 2296.27 µmol H2 h−1 gcat−1. Combining experimental and computational approaches enabled to define the optimum combination of the synthesis parameters resulting in the highest photocatalytic activity for water splitting for green hydrogen production. The results indicate that the major factor affecting hydrogen production is temperature of the TiO2-Cu-graphene composite synthesis which in turn is inversely correlated to photoactivity.
Development of Visible-Light-Driven Rh–TiO2-CeO2 Hybrid Photocatalysts for Hydrogen Production
Jul 2021
Publication
Visible-light-driven hydrogen production through photocatalysis has attracted enormous interest owing to its great potential to address energy and environmental issues. However photocatalysis possesses several limitations to overcome for practical applications such as low light absorption efficiency rapid charge recombination and poor stability of photocatalysts. Here the preparation of efficient noble metal–semiconductor hybrid photocatalysts for photocatalytic hydrogen production is presented. The prepared ternary Rh–TiO2–CeO2 hybrid photocatalysts exhibited excellent photocatalytic performance toward the hydrogen production reaction compared with their counterparts ascribed to the synergistic combination of Rh TiO2 and CeO2.
Heat to Hydrogen by RED—Reviewing Membranes and Salts for the RED Heat Engine Concept
Dec 2021
Publication
The Reverse electrodialysis heat engine (REDHE) combines a reverse electrodialysis stack for power generation with a thermal regeneration unit to restore the concentration difference of the salt solutions. Current approaches for converting low-temperature waste heat to electricity with REDHE have not yielded conversion efficiencies and profits that would allow for the industrialization of the technology. This review explores the concept of Heat-to-Hydrogen with REDHEs and maps crucial developments toward industrialization. We discuss current advances in membrane development that are vital for the breakthrough of the RED Heat Engine. In addition the choice of salt is a crucial factor that has not received enough attention in the field. Based on ion properties relevant for both the transport through IEMs and the feasibility for regeneration we pinpoint the most promising salts for use in REDHE which we find to be KNO3 LiNO3 LiBr and LiCl. To further validate these results and compare the system performance with different salts there is a demand for a comprehensive thermodynamic model of the REDHE that considers all its units. Guided by such a model experimental studies can be designed to utilize the most favorable process conditions (e.g. salt solutions).
On the Climate Impacts of Blue Hydrogen Production
Nov 2021
Publication
Natural gas based hydrogen production with carbon capture and storage is referred to as blue hydrogen. If substantial amounts of CO2 from natural gas reforming are captured and permanently stored such hydrogen could be a low-carbon energy carrier. However recent research raises questions about the effective climate impacts of blue hydrogen from a life cycle perspective. Our analysis sheds light on the relevant issues and provides a balanced perspective on the impacts on climate change associated with blue hydrogen. We show that such impacts may indeed vary over large ranges and depend on only a few key parameters: the methane emission rate of the natural gas supply chain the CO2 removal rate at the hydrogen production plant and the global warming metric applied. State-of-the-art reforming with high CO2 capture rates combined with natural gas supply featuring low methane emissions does indeed allow for substantial reduction of greenhouse gas emissions compared to both conventional natural gas reforming and direct combustion of natural gas. Under such conditions blue hydrogen is compatible with low-carbon economies and exhibits climate change impacts at the upper end of the range of those caused by hydrogen production from renewable-based electricity. However neither current blue nor green hydrogen production pathways render fully “net-zero” hydrogen without additional CO2 removal.
SNG Generation via Power to Gas Technology: Plant Design and Annual Performance Assessment
Nov 2020
Publication
Power to gas (PtG) is an emerging technology that allows to overcome the issues due to the increasingly widespread use of intermittent renewable energy sources (IRES). Via water electrolysis power surplus on the electric grid is converted into hydrogen or into synthetic natural gas (SNG) that can be directly injected in the natural gas network for long-term energy storage. The core units of the Power to synthetic natural gas (PtSNG) plant are the electrolyzer and the methanation reactors where the renewable electrolytic hydrogen is converted to synthetic natural gas by adding carbon dioxide. A technical issue of the PtSNG plant is the different dynamics of the electrolysis unit and the methanation unit. The use of a hydrogen storage system can help to decouple these two subsystems and to manage the methanation unit for assuring long operation time and reducing the number of shutdowns. The purpose of this paper is to evaluate the energy storage potential and the technical feasibility of the PtSNG concept to store intermittent renewable sources. Therefore different plant sizes (1 3 and 6 MW) have been defined and investigated by varying the ratio between the renewable electric energy sent to the plant and the total electric energy generated by the renewable energy source (RES) facility based on a 12 MW wind farm. The analysis has been carried out by developing a thermochemical and electrochemical model and a dynamic model. The first allows to predict the plant performance in steady state. The second allows to forecast the annual performance and the operation time of the plant by implementing the control strategy of the storage unit. The annual overall efficiencies are in the range of 42–44% low heating value (LHV basis). The plant load factor i.e. the ratio between the annual chemical energy of the produced SNG and the plant capacity results equal to 60.0% 46.5% and 35.4% for 1 3 and 6 MW PtSNG sizes respectively.
Design and Analysis of a New Renewable-Nuclear Hybrid Energy System for Production of Hydrogen, Fresh Water and Power
Nov 2021
Publication
This paper investigates an integrated system where solar energy system (with 75MWp bifacial PV arrays) and nuclear power plant (with 2×10MWt HTR-10 type pebble bed reactors) are hybridized and integrated with a 72MWe capacity high-temperature solid oxide electrolysis (SOE) unit to produce hydrogen fresh water and electrical power. Bifacial PV plant is integrated to system for supplying electricity with a low LCOE and zero-carbon system. A Rankine cycle is integrated to generate power from the steam that generated from nuclear heat. According to the available irradiance; the steam is diverted between steam turbine and high-temperature electrolyzer for hydrogen and power generation. Multi-effect desalination unit is integrated to exploit the excess heat to generate fresh water. A system performance assessment is carried out by energy and exergy efficiencies thermodynamically. The bifacial PV plant is analyzed in six selected latitudes in order to assess the feasibility and applicability of the system. Numerous time-dependent analyses are carried out to study the effects of varying inputs such as solar radiation intensity. For 20MWt nuclear 75MWp solar capacity; hydrogen productions are found to be between 0.036 and 0.562kg/s. Among the Northern Hemisphere latitudes the peak daily hydrogen production rate is expected to reach 25.9 tons of hydrogen per day for the 75 °N case mostly with the influence of low temperature and high albedo. The pitch distance change is increased the hydrogen production rate by 28% between 3 m and 7 m tracker spacing. The overall system energy efficiency is obtained between 21.8% and 24.2% where the overall system exergy efficiency is found between 18.6% and 21.1% under dynamic conditions for the 45°N latitude case.
Photocatalytic Production of Hydrogen from Binary Mixtures of C-3 Alcohols on Pt/TiO2: Influence of Alcohol Structure
Oct 2018
Publication
The effect of alcohol structure on photocatalytic production of H2 from C-3 alcohols was studied on 0.5% Pt/TiO2. A C-2 alcohol (ethanol) was also included for comparative purposes. For individual reactions from 10% v/v aqueous solutions of alcohols hydrogen production followed the order ethanol ≈ propan-2-ol > propan-1- ol > propane-123-triol > propane-12-diol > propane-13-diol. The process was found to be quite sensitive to the presence of additional alcohols in the reaction medium as evidenced by competitive reactions. Therefore propan-2-ol conversion was retarded in the presence of traces of the other alcohols this effect being particularly significant for vicinal diols. Additional experiments showed that adsorption of alcohols on Pt/TiO2 followed the order propane-123-triol > propane-12-diol > propane-13-diol > propan-1-ol > ethanol > propan-2-ol. Adsorption studies (DRIFT) and monitoring of reaction products showed that the main photocatalyzed process for propan-2-ol and propan-1-ol transformation is dehydrogenation to the corresponding carbonyl compound (especially for propan-2-ol both in the liquid and the gas phase). In the case of liquid-phase transformation of propan-1-ol ethane was also detected which is indicative of the dissociative mechanism to lead to the corresponding C-1 alkane. All in all competitive reactions proved to be very useful for mechanistic studies.
Optimising Onshore Wind with Energy Storage Considering Curtailment
May 2022
Publication
Operating energy storage alongside onshore wind can improve its economics whilst providing a pathway for otherwise curtailed generation. In this work we present a framework to evaluate the economic potential of onshore wind co-located with battery storage (BS) and a hydrogen electrolyser (HE). This model is applied to a case study in Great Britain using historic data and considering local network charges and the cost of using curtailed power capturing an often neglected element of competition. We use a Markov Chain to model wind curtailment and determine the optimised scheduling of the storage as we vary price parameters and storage sizing. Finally by considering storage CAPEX and comparing against the case with no storage we can determine the value added (or lost) by different sized BS and HE for an onshore wind owner as a function of power purchase agreement (PPA) and green hydrogen market price. Results show that value added increases when HE is increased and when BS is decreased. Additionally a 10 MW electrolysers uses 27% more curtailed wind than 10 MW BS.
The Development of an Assessment Framework to Determine the Technical Hydrogen Production Potential from Wind and Solar Energy
Jun 2022
Publication
Electrolytic hydrogen produced from wind and solar energy is considered a long-term option for multi-sectoral decarbonization. The study objective is to develop a framework for assessing country-level hydrogen technical potential from wind and solar energy. We apply locational suitability and zonal statistical analyses methods in a geographic information system-based environment to derive granular insights on non-captive technically exploitable hydrogen potential in high-resource locations. Seven setback factors were considered for locational suitability and integrated with modules developed for evaluating the wind and solar resource penetration from open-source theoretical renewable resource geospatial data and electricity-to-hydrogen conversion analyses. The technique applied in this study would be a relevant contribution to determining national and regional-wide electrolytic hydrogen production potentials in other jurisdictions with requisite adjustments to data and technical constraints. The results from the case study country Canada – a major hydrogen-producing country – show that the technical hydrogen potentials from wind and solar energy are approximately 1897 and 448 million metric tonnes per year respectively at least 6.3 times greater than global hydrogen demand in 2019. When we integrated locational data on enabling infrastructure we discovered that the lack of access to power transmission lines in low-population-density areas of the country significantly reduces the exploitable wind- and solar-based hydrogen potential by over 80% and 6% respectively. The findings of this study show that in the absence of spatial data on infrastructural constraints the exploitable hydrogen potential in a jurisdiction can be overestimated leading to improper guidance for policy and decision-makers.
Proton Exchange Membrane Electrolyzer Emulator for Power Electronics Testing Applications
Mar 2021
Publication
This article aims to develop a proton exchange membrane (PEM) electrolyzer emulator. This emulator is realized through an equivalent electrical scheme. It allows taking into consideration the dynamic operation of PEM electrolyzers which is generally neglected in the literature. PEM electrolyzer dynamics are reproduced by the use of supercapacitors due to the high value of the equivalent double-layer capacitance value. Steady-state and dynamics operations are investigated in this work. The design criteria are addressed. The PEM electrolyzer emulator is validated by using a 400-W commercial PEM electrolyzer. This emulator is conceived to test new DC-DC converters to supply the PEM ELs and their control as well avoiding the risk to damage a real electrolyzer for experiment purposes. The proposed approach is valid both for a single cell and for the whole stack emulation.
Boosting the H2 Production Efficiency via Photocatalytic Organic Reforming: The Role of Additional Hole Scavenging System
Nov 2021
Publication
The simultaneous photocatalytic H2 evolution with environmental remediation over semiconducting metal oxides is a fascinating process for sustainable fuel production. However most of the previously reported photocatalytic reforming showed nonstoichiometric amounts of the evolved H2 when organic substrates were used. To explain the reasons for this phenomenon a careful analysis of the products and intermediates in gas and aqueous phases upon the photocatalytic hydrogen evolution from oxalic acid using Pt/TiO2 was performed. A quadrupole mass spectrometer (QMS) was used for the continuous flow monitoring of the evolved gases while high performance ion chromatography (HPIC) isotopic labeling and electron paramagnetic resonance (EPR) were employed to understand the reactions in the solution. The entire consumption of oxalic acid led to a ~30% lower H2 amount than theoretically expected. Due to the contribution of the photoKolbe reaction mechanism a tiny amount of formic acid was produced then disappeared shortly after the complete consumption of oxalic acid. Nevertheless a much lower concentration of formic acid was generated compared to the nonstoichiometric difference between the formed H2 and the consumed oxalic acid. Isotopic labeling measurements showed that the evolved H2 HD and/or D2 matched those of the solvent; however using D2O decreased the reaction rate. Interestingly the presence of KI as an additional hole scavenger with oxalic acid had a considerable impact on the reaction mechanism and thus the hydrogen yield as indicated by the QMS and the EPR measurements. The added KI promoted H2 evolution to reach the theoretically predictable amount and inhibited the formation of intermediates without affecting the oxalic acid degradation rate. The proposed mechanism by which KI boosts the photocatalytic performance is of great importance in enhancing the overall energy efficiency for hydrogen production via photocatalytic organic reforming.
Techno-Economic Evaluation of Hydrogen Production via Gasification of Vacuum Residue Integrated with Dry Methane Reforming
Dec 2021
Publication
The continuous rise of global carbon emissions demands the utilization of fossil fuels in a sustainable way. Owing to various forms of emissions our environment conditions might be affected necessitating more focus of scientists and researchers to upgrade oil processing to more efficient manner. Gasification is a potential technology that can convert fossil fuels to produce clean and environmentally friendly hydrogen fuel in an economical manner. Therefore this study analyzed and examined it critically. In this study two different routes for the production of high-purity hydrogen from vacuum residue while minimizing the carbon emissions were proposed. The first route (Case I) studied the gasification of heavy vacuum residue (VR) in series with dry methane reforming (DMR). The second route studied the gasification of VR in parallel integration with DMR (Case II). After investigating both processes a brief comparison was made between the two routes of hydrogen production in terms of their CO2 emissions energy efficiency energy consumption and environmental and economic impacts. In this study the two vacuum-residue-to-hydrogen (VRTH) processes were simulated using Aspen Plus for a hydrogen production capacity of 50 t/h with 99.9 wt.% purity. The results showed that Case II offered a process energy efficiency of 57.8% which was slightly higher than that of Case I. The unit cost of the hydrogen product for Case II was USD 15.95 per metric ton of hydrogen which was almost 9% lower than that of Case I. In terms of the environmental analysis both cases had comparably low carbon emissions of around 8.3 kg of CO2/kg of hydrogen produced; with such high purity the hydrogen could be used for production of other products further downstream or for industrial applications.
Energy Efficiency Based Control Strategy of a Three-Level Interleaved DC-DC Buck Converter Supplying a Proton Exchange Membrane Electrolyzer
Aug 2019
Publication
To face the intensive use of natural gas and other fossil fuels to generate hydrogen water electrolysis based on renewable energy sources (RES) seems to be a viable solution. Due to their fast response times and high efficiency proton exchange membrane electrolyzer (PEM EL) is the most suitable technology for long-term energy storage combined with RES. Like fuel cells the development of fit DC-DC converters is mandatory to interface the EL to the DC grid. Given that PEM EL operating voltages are quite low and to meet requirements in terms of output current ripples new emerging interleaved DC-DC converter topologies seem to be the best candidates. In this work a three-level interleaved DC-DC buck converter has been chosen to supply a PEM EL from a DC grid. Therefore the main objective of this paper is to develop a suitable control strategy of this interleaved topology connected to a PEM EL emulator. To design the control strategy investigations have been carried out on energy efficiency hydrogen flow rate and specific energy consumption. The obtained experimental results validate the performance of the converter in protecting the PEM EL during transient operations while guaranteeing correct specific energy consumption.
Techno-Economic Analysis of Low Carbon Hydrogen Production from Offshore Wind Using Battolyser Technology
Aug 2022
Publication
A battolyser is a combined battery electrolyser in one unit. It is based on flow battery technology and can be adapted to produce hydrogen at a lower efficiency than an electrolyser but without the need for rare and expensive materials. This paper presents a method of determining if a battolyser connected to a wind farm makes economic sense based on stochastic modelling. A range of cost data and operational scenarios are used to establish the impact on the NPV and LCOE of adding a battolyser to a wind farm. The results are compared to adding a battery or an electrolyser to a wind farm. Indications are that it makes economic sense to add a battolyser or battery to a wind farm to use any curtailed wind with calculated LCOE at £56/MWh to £58/MWh and positive NPV over a range of cost scenarios. However electrolysers are still too expensive to make economic sense.
R&D Status on Thermochemical IS Process for Hydrogen Production at JAEA
Nov 2012
Publication
Thermochemical hydrogen production process is one of the candidates of industrial fossil fuel free hydrogen production. Japan Atomic Energy Agency (JAEA) has been conducting R&D of the thermochemical water splitting iodine-sulfur (IS) process since the end of 1980s. This paper presents the recent study on the IS process in JAEA. In 2005-2009 test-fabrication of components collection of design database improvement of process components for higher thermal efficiency and proposition of composition measurement method were carried out. On the basis of them the integrity test of process components is carried out in 2010-2014 to examine their integrities in severe process environments. At present a Bunsen reactor which produces acids and incidental equipments has been already manufactured using corrosion resistant materials such as glass lining steel and fluoroplastic lining steel. Flow tests to examine the functionality and integrity of the materials are planned in 2012.
Hydrogen Production Methods Based on Solar and Wind Energy: A Review
Jan 2023
Publication
Several research works have investigated the direct supply of renewable electricity to electrolysis particularly from photovoltaic (PV) and wind generator (WG) systems. Hydrogen (H2 ) production based on solar energy is considered to be the newest solution for sustainable energy. Different technologies based on solar energy which allow hydrogen production are presented to study their benefits and inconveniences. The technology of water decomposition based on renewable energy sources to produce hydrogen can be achieved by different processes (photochemical systems; photocatalysis systems photo-electrolysis systems bio-photolysis systems thermolysis systems thermochemical cycles steam electrolysis hybrid processes and concentrated solar energy systems). A comparison of the different methods for hydrogen production based on PV and WG systems was given in this study. A comparative study of different types of electrolyzers was also presented and discussed. Finally an economic assessment of green hydrogen production is given. The hydrogen production cost depends on several factors such as renewable energy sources electrolysis type weather conditions installation cost and the productivity of hydrogen per day. PV/H2 and wind/H2 systems are both suitable in remote and arid areas. Minimum maintenance is required and a power cycle is not needed to produce electricity. The concentrated CSP/H2 system needs a power cycle. The hydrogen production cost is higher if using wind/H2 rather than PV/H2 . The green energy sources are useful for multiple applications such as hydrogen production cooling systems heating and water desalination.
Review on the Status of the Research on Power‐to‐Gas Experimental Activities
Aug 2022
Publication
In recent years power‐to‐gas technologies have been gaining ground and are increasingly proving their reliability. The possibility of implementing long‐term energy storage and that of being able to capture and utilize carbon dioxide are currently too important to be ignored. However sys‐ tems of this type are not yet experiencing extensive realization in practice. In this study an overview of the experimental research projects and the research and development activities that are currently part of the power‐to‐gas research line is presented. By means of a bibliographical and sitographical analysis it was possible to identify the characteristics of these projects and their distinctive points. In addition the main research targets distinguishing these projects are presented. This provides an insight into the research direction in this regard where a certain technological maturity has been achieved and where there is still work to be done. The projects found and analyzed amount to 87 mostly at laboratory scale. From these what is most noticeable is that research is currently focusing heavily on improving system efficiency and integration between components.
Two-Dimensional Photocatalysts for Energy and Environmental Applications
Jun 2022
Publication
The depletion of fossil fuels and onset of global warming dictate the achievement of efficient technologies for clean and renewable energy sources. The conversion of solar energy into chemical energy plays a vital role both in energy production and environmental protection. A photocatalytic approach for H2 production and CO2 reduction has been identified as a promising alternative for clean energy production and CO2 conversion. In this process the most critical parameter that controls efficiency is the development of a photocatalyst. Two-dimensional nanomaterials have gained considerable attention due to the unique properties that arise from their morphology. In this paper examples on the development of different 2D structures as photocatalysts in H2 production and CO2 reduction are discussed and a perspective on the challenges and required improvements is given.
Economic Dispatch Model of Nuclear High-Temperature Reactor with Hydrogen Cogeneration in Electricity Market
Dec 2021
Publication
Hydrogen produced without carbon emissions could be a useful fuel as nations look to decarbonize their electricity transport and industry sectors. Using the iodine–sulfur (IS) cycle coupled with a nuclear heat source is one method for producing hydrogen without the use of fossil fuels. An economic dispatch model was developed for a nuclear-driven IS system to determine hydrogen sale prices that would make such a system profitable. The system studied is the HTTR GT/H2 a design for power and hydrogen cogeneration at the Japan Atomic Energy Agency’s High Temperature Engineering Test Reactor. This study focuses on the development of the economic model and the role that input data plays in the final calculated values. Using a historical price duration curve shows that the levelized cost of hydrogen (LCOH) or breakeven sale price of hydrogen would need to be 98.1 JPY/m3 or greater. Synthetic time histories were also used and found the LCOH to be 67.5 JPY/m3 . The price duration input was found to have a significant effect on the LCOH. As such great care should be used in these economic dispatch analyses to select reasonable input assumptions.
Far Off-shore Wind Energy-based Hydrogen Production: Technological Assessment and Market Valuation Designs
Jan 2020
Publication
This article provides a techno-economic study on coupled offshore wind farm and green hydrogen production via sea water electrolysis (OWF-H2). Offshore wind energy wind farms (OWF) and water electrolysis (WE) technologies are described. MHyWind (the tool used to perform simulations and optimisations of such plants) is presented as well as the models of the main components in the study. Three case studies focus on offshore wind farms either stand-alone or connected to the grid via export cables coupled with a battery and electrolysis systems either offshore or onshore. Exhaustive searches and optimisations performed allowed for rules of thumb to be derived on the sizing of coupled OWF-H2 plants that minimize costs of hydrogen production (LCoH2 in €/kgH2): Non-connected OWF-H2 coupled to a battery offers the lowest LCoH2 without the costs of H2 transportation when compared to cases where the WE is installed onshore and connected to the OWF. Using a simple power distribution heuristic increasing the number of installed WE allows the system to take advantage of more OWF energy but doesn’t improve plant efficiency whereas a battery always does. Finally within the scope of this study it is observed that power ratios of optimized plant architectures (leading to the lowest LCoH2) are between 0.8-0.9 for PWE/POWF and 0.3-0.35 for PBattery/POWF.
Co-production of Hydrogen and Power from Black Liquor Via Supercritical Water Gasification, Chemical Looping and Power Generation
Mar 2019
Publication
An integrated system to harvest efficiently the energy from the waste of pulp mill industry which is black liquor (BL) is proposed and evaluated. The proposed system consists of the supercritical water gasification (SCWG) of BL syngas chemical looping and power generation. To minimize the exergy loss throughout the system and to optimize the energy efficiency process design and integration is conducted by employing the principles of exergy recovery and process integration methods. Hydrogen is set as the main output while power is produced by utilizing the heat generated throughout the process. Process simulation is conducted using a steady state process simulator Aspen Plus. Energy efficiency is defined into three categories: hydrogen production efficiency power generation efficiency and total energy efficiency. From process simulation both of the integrated systems show very high total energy efficiency of about 73%.
From Biogas to Hydrogen: A Techno-Economic Study on the Production of Turquoise Hydrogen and Solid Carbons
Sep 2022
Publication
Biogas is a renewable feedstock that can be used to produce hydrogen through the decomposition of biomethane. However the economics of the process are not well studied and understood especially in cases where solid carbons are also produced and which have a detrimental effect on the performance of the catalysts. The scale as well as product diversification of a biogas plant to produce hydrogen and other value-added carbons plays a crucial role in determining the feasibility of biogasto-hydrogen projects. Through a techno-economic study using the discounted cash flow method it has been shown that there are no feasible sizes of plants that can produce hydrogen at the target price of USD 3/kg or lower. However for self-funded anaerobic digestor plants retrofitting modular units for hydrogen production would only make financial sense at biogas production capacities of more than 412 m3/h. A sensitivity analysis has also shown that the cost competitiveness is dependent on the type of carbon formed and low-grade carbon black has a negative effect on economic feasibility. Hydrogen produced from biogas would thus not be able to compete with grey hydrogen production but rather with current green hydrogen production costs.
Current Legislative Framework for Green Hydrogen Production by Electrolysis Plants in Germany
Mar 2022
Publication
(1) The German energy system transformation towards an entirely renewable supply is expected to incorporate the extensive use of green hydrogen. This carbon-free fuel allows the decarbonization of end-use sectors such as industrial high-temperature processes or heavy-duty transport that remain challenging to be covered by green electricity only. However it remains unclear whether the current legislative framework supports green hydrogen production or is an obstacle to its rollout. (2) This work analyzes the relevant laws and ordinances regarding their implications on potential hydrogen production plant operators. (3) Due to unbundling-related constraints potential operators from the group of electricity transport system and distribution system operators face lacking permission to operate production plants. Moreover ownership remains forbidden for them. The same applies to natural gas transport system operators. The case is less clear for natural gas distribution system operators where explicit regulation is missing. (4) It is finally analyzed if the production of green hydrogen is currently supported in competition with fossil hydrogen production not only by the legal framework but also by the National Hydrogen Strategy and the Amendment of the Renewable Energies Act. It can be concluded that in recent amendments of German energy legislation regulatory support for green hydrogen in Germany was found. The latest legislation has clarified crucial points concerning the ownership and operation of electrolyzers and the treatment of green hydrogen as a renewable energy carrier.
Projecting the Future Cost of PEM and Alkaline Water Electrolysers; a CAPEX Model Including Electrolyser Plant Size and Technology Department
Oct 2022
Publication
The investment costs of water electrolysis represent one key challenge for the realisation of renewable hydrogen-based energy systems. This work presents a technology cost assessment and outlook towards 2030 for alkaline electrolysers (AEL) and PEM electrolysers (PEMEL) in the MW to GW range taking into consideration the effects of plant size and expected technology developments. Critical selected data was fitted to a modified power law to describe the cost of an electrolyser plant based on the overall capacity and a learning/technology development rate to derive cost estimations for different PEMEL and AEL plant capacities towards 2030. The analysis predicts that the CAPEX gap between AEL and PEMEL technologies will decrease significantly towards 2030 with plant size until 1 e10 MW range. Beyond this only marginal cost reductions can be expected with CAPEX values approaching 320e400 $/kW for large scale (greater than 100 MW) plants by 2030 with subsequent cost reductions possible. Learning rates for electrolysers were estimated at 25 e30% for both AEL and PEMEL which are significantly higher than the learning rates reported in previous literature.
HydroGenerally - Episode 1: The Colours of Hydrogen
Mar 2022
Publication
This first episode was inspired by an Innovate UK KTN perspective commenting on the UK government’s Hydrogen Strategy released by the Department of Business Energy and Industrial Strategy (BEIS) in August 2021. Following the publication of this perspective it was very evident to our Innovate UK KTN experts that the uses and challenges of ‘blue’ and ‘green’ hydrogens were generating a strong debate depending on their application areas.
Over a 20-minute discussion Simon Steffan and Sam try to answer the questions: how is hydrogen currently produced? How will it be produced in the future? And how will it fit in with the energy system?
The podcast can be found on their website
Over a 20-minute discussion Simon Steffan and Sam try to answer the questions: how is hydrogen currently produced? How will it be produced in the future? And how will it fit in with the energy system?
The podcast can be found on their website
Assessment of Fossil-free Steelmaking Based on Direct Reduction Applying High-temperature Electrolysis
Jun 2021
Publication
Preventing humanity from serious impact of climate crisis requires carbon neutrality across all economic sectors including steel industry. Although fossil-free steelmaking routes receiving increasing attention fundamental process aspects especially approaches towards the improvement of efficiency and flexibility are so far not comprehensively studied. In this paper optimized process concepts allowing for a gradual transition towards fossil-free steelmaking based on the coupling of direct reduction process electric arc furnace and electrolysis are presented. Both a high-temperature and low-temperature electrolysis were modeled and possibilities for the integration into existing infrastructure are discussed. Various schemes for heat integration especially when using high-temperature electrolysis are highlighted and quantified. It is demonstrated that the considered direct reduction-based process concepts allow for a high degree of flexibility in terms of feed gas composition when partially using natural gas as a bridge technology. This allows for an implementation in the near future as well as the possibility of supplying power grid services in a renewable energy system. Furthermore it is shown that an emission reduction potential of up to 97.8% can be achieved with a hydrogen-based process route and 99% with a syngas-based process route respectively provided that renewable electricity is used.
Green Hydrogen Production Via Electrochemical Conversion of Components from Alkaline Carbohydrate Degradation
Nov 2021
Publication
Water electrolysis is a promising approach for the sustainable production of hydrogen however the unfavorable thermodynamics and sluggish kinetics of oxygen evolution reaction (OER) are associated with high anodic potentials. To lower the required potentials an effective strategy is proposed to substitute OER with partial oxidation of degradation products of carbohydrate origin from the waste stream of a chemical pulping industry. In this work two different catalytic materials e PdNi and NiO are investigated comparatively to understand their catalytic performance for the oxidation of carbohydrate alkaline degradation products (CHADs). PdNi can catalyze CHADs with low potential requirements (0.11 V vs. Hg/HgO at 150 mA cm2 ) but is limited to current densities opportunities to study earth-abundant electrocatalysts to efficiently oxidize biomass-derived substances.
Optimal Strategies of Deployment of Far Offshore Co-located Wind-wave Energy Farms
Nov 2021
Publication
The most profitable offshore energy resources are usually found away from the coast. Nevertheless the accessibility and grid integration in those areas are more complicated. To avoid this problematic large scale hydrogen production is being promoted for far offshore applications. The main objective of this paper is to analyze the ability of wave energy converters to maximize hydrogen production in hybrid wind and wave far offshore farms. To that end wind and wave resource data are obtained from ERA5 for different locations in the Atlantic ocean and a Maximum Covariance Analysis is proposed for the selection of the most representative locations. Furthermore the suitability of different sized wave energy converters for auxiliary hydrogen production in the far offshore wind farms is also analysed. On that account the hydrodynamic parameters of the oscillating bodies are obtained via simulations with a Boundary Element Method based code and their operation is modelled using the software tool Matlab. The combination of both methodologies enables to perform a realistic assessment of the contribution of the wave energy converters to the hydrogen generation of an hybrid energy farm especially during those periods when the wind turbines would be stopped due to the variability of the wind. The obtained results show a considerable hydrogen generation capacity of the wave energy converters up to 6.28% of the wind based generation which could remarkably improve the efficiency of the far offshore farm and bring important economical profit. Wave energy converters are observed to be most profitable in those farms with low covariance between wind and waves where the disconnection times of the wind turbines are prone to be more prolonged but the wave energy is still usable. In such cases a maximum of 101.12 h of equivalent rated production of the wind turbine has been calculated to be recovered by the wave energy converters.
Cow Dung Gasification Process for Hydrogen Production Using Water Vapor as Gasification Agent
Jun 2022
Publication
In recent years with the development of hydrogen energy economy there is an increasing demand for hydrogen in the market and hydrogen production through biomass will provide an important way to supply clean environmentally friendly and highly efficient hydrogen. In this study cow dung was selected as the biomass source and the efficiency of the biomass to hydrogen reaction was explored by coupling high temperature pyrolysis and water vapor gasification. The experimental conditions of gasification temperature water mass fraction heating rate and feed temperature were systematically studied and optimized to determine the optimal conditions for in situ hydrogen production by gasification of cow dung. The relationship of each factor to the yield of hydrogen production by gasification of cow dung semi-coke was investigated in order to elucidate the mechanism of the hydrogen production. The experiment determined the optimal operating parameters of in situ gasification: gasification temperature 1173 K water mass fraction 80% heating rate 10 K/min and feed temperature 673 K. The semi-coke treatment separated high temperature pyrolysis and water vapor gasification and reduced the influence on gasification of volatile substances such as tar extracted from pyrolysis. The increase of semi-coke preparation temperature increases the content of coke reduces the volatile matter and improves the yield of hydrogen; the small size of semi-coke particles and large specific surface area are beneficial to the gasification reaction.
Acidic or Alkaline? Towards a New Perspective on the Efficiency of Water Electrolysis
Aug 2016
Publication
Water electrolysis is a promising technology for enabling the storage of surplus electricity produced by intermittent renewable power sources in the form of hydrogen. At the core of this technology is the electrolyte and whether this is acidic or alkaline affects the reaction mechanisms gas purities and is of significant importance for the stability and activity of the electrocatalysts. This article presents a simple but precise physical model to describe the voltage-current characteristic heat balance gas crossover and cell efficiency of water electrolyzers. State-of-the-art water electrolysis cells with acidic and alkaline electrolyte are experimentally characterized in order to parameterize the model. A rigorous comparison shows that alkaline water electrolyzers with Ni-based catalysts but thinner separators than those typically used is expected be more efficient than acidic water electrolysis with Ir and Pt based catalysts. This performance difference was attributed mainly to a similar conductivity but approximately 38-fold higher diffusivities of hydrogen and oxygen in the acidic polymer electrolyte membrane (Nafion) than those in the alkaline separator (Zirfon filled with a 30 wt% KOH solution). With reference to the detailed analysis of the cell characteristics perspectives for the improvement of the efficiency of water electrolyzers are discussed.
Electrical Double Layer Mechanism Analysis of PEM Water Electrolysis for Frequency Limitation of Pulsed Currents
Nov 2021
Publication
This paper proposes a method for improving hydrogen generation using pulse current in a proton exchange membrane-type electrolyzer (PEMEL). Traditional methods of electrolysis using direct current are known as the simplest approach to produce hydrogen. However it is highly dependent on environmental variables such as the temperature and catalyst used to enhance the rate of electrolysis. Therefore we propose electrolysis using a pulse current that can apply several dependent variables rather than environmental variables. The proposed method overcomes the difficulties in selecting the frequency of the pulse current by deriving factors affecting hydrogen generation while changing the concentration generated by the cell interface during the pulsed water-electrolysis process. The correlation between the electrolyzer load and the frequency characteristics was analyzed and the limit value of the applicable frequency of the pulse current was derived through electrical modeling. In addition the operating characteristics of PEMEL could be predicted and the PEMEL using the proposed pulse current was verified through experiments.
The Route from Green H2 Production through Bioethanol Reforming to CO2 Catalytic Conversion: A Review
Mar 2022
Publication
Currently a progressively different approach to the generation of power and the production of fuels for the automotive sector as well as for domestic applications is being taken. As a result research on the feasibility of applying renewable energy sources to the present energy scenario has been progressively growing aiming to reduce greenhouse gas emissions. Following more than one approach the integration of renewables mainly involves the utilization of biomass-derived raw material and the combination of power generated via clean sources with conventional power generation systems. The aim of this review article is to provide a satisfactory overview of the most recent progress in the catalysis of hydrogen production through sustainable reforming and CO2 utilization. In particular attention is focused on the route that starting from bioethanol reforming for H2 production leads to the use of the produced CO2 for different purposes and by means of different catalytic processes passing through the water–gas shift stage. The newest approaches reported in the literature are reviewed showing that it is possible to successfully produce “green” and sustainable hydrogen which can represent a power storage technology and its utilization is a strategy for the integration of renewables into the power generation scenario. Moreover this hydrogen may be used for CO2 catalytic conversion to hydrocarbons thus giving CO2 added value.
The Hydrogen Grand Challenge
Apr 2016
Publication
More than 90% of the world’s growing energy demand is satisfied by fossil fuels (BP Statistical Review … 2015)1. One consequence of the unrestrained use of this technology is the continuous increase of the CO2 level of the atmosphere2. There are also the challenges associated with the limitations of the corresponding resources (Hubbert 1956; BP Statistical Review … 2015). Climate change as a consequence of the growing CO2 level (see text footnote 2 ESRL Global Monitoring Division 2015) has been identified as one of the most critical challenges facing mankind and requires immediate action: “The Paris Agreement aims to strengthen the global response to the threat of climate change ( … ) by low greenhouse gas emissions development in a manner that does not threaten food production” (United Nations Framework … 2015). How to reach the corresponding significant reduction of CO2 emission by 2050 is not defined in this document but it implies that mankind must transform its energy technology from a fossil to a renewable basis. Numerous studies and publications have indicated that the sun’s energy and its derivatives (wind water) are by far sufficient to supply world’s energy demand (see e.g. Smalley 2005; Züttel et al. 2010); but the large daily and seasonal power variation of renewable energy is an additional complication for a wide spread replacement of fossil energy by renewable energy.
Electric-field-promoted Photo-electrochemical Production of Hydrogen from Water Splitting
Jul 2021
Publication
Given that conversion efficiencies of incident solar radiation to liquid fuels e.g. H2 are of the order of a few percent or less as quantified by ‘solar to hydrogen’ (STH) economically inexpensive and operationally straightforward ways to boost photo-electrochemcial (PEC) H2 production from solar-driven water splitting are important. In this work externally-applied static electric fields have led to enhanced H2 production in an energy-efficient manner with up to ~30–40% increase in H2 (bearing in mind fieldinput energy) in a prototype open-type solar cell featuring rutile/titania and hematite/iron-oxide (Fe2O3) respectively in contact with an alkaline aqueous medium (corresponding to respective relative increases of STH by ~12 and 16%). We have also performed non-equilibrium ab-initio molecular dynamics in both static electric and electromagnetic (e/m) fields for water in contact with a hematite/iron-oxide (0 0 1) surface observing enhanced break-up of water molecules by up to ~70% in the linear-response régime. We discuss the microscopic origin of such enhanced water-splitting based on experimental and simulation-based insights. In particular we external-field direction at the hematite surfaces and scrutinise properties of the adsorbed water molecules and OH– and H3O+ species e.g. hydrogen bonds between water-protons and the hematite surfaces’ bridging oxygen atoms as well as interactions between oxygen atoms in adsorbed water molecules and underlying iron atoms.
Synthesis and Characterization of Biogenic Iron Oxides of Different Nanomorphologies from Pomegranate Peels for Efficient Solar Hydrogen Production
Feb 2020
Publication
An eco-friendly green synthesis of mesoporous iron oxide (hematite) using pomegranate peels through a low-cost and massive product method was investigated. The mass of pomegranate peels was varied to control the morphology of the produced hematite (Fe2O3). The structures textures and optical properties of the products were investigated by FTIR XRD FE-SEM and UV–Vis spectroscopy. Three different Fe2O3 morphologies were obtained; Fe2O3(I) nanorod like shape Fe2O3(II) nanoparticles and Fe2O3(III) nanoporous structured layer. The bandgap values for Fe2O3 (I) (II) and (III) were 2.71 2.95 and 2.29 eV respectively. The newly hematite samples were used as promising photoelectrodes supported on graphite substrate for the photoelectrochemical (PEC) water splitting toward the efficient production of solar hydrogen. The number of generated hydrogen moles was calculated per active area to be 50 molh−1 cm−2 for electrode III which decreased to 15.3molh−1 cm−2 for electrode II. The effects of temperature (30–70 ◦C) on the PEC behavior of the three electrodes were addressed. Different thermodynamic parameters were calculated for the three electrodes which showed activation energies of 13.4 16.8 and 15.2 kJmol−1 respectively. The electrode stability was addressed as a function of the number of runs and exposure time in addition to electrochemical impedance study. Finally the conversion efficiency of the incident photon to-current(IPCE) was estimated under the monochromatic illumination. The optimum value was ∼11% @ 390nm for Fe2O3(III) electrode
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.
The Challenges of Integrating the Principles of Green Chemistry and Green Engineering to Heterogeneous Photocatalysis to Treat Water and Produce Green H2
Jan 2023
Publication
Nowadays heterogeneous photocatalysis for water treatment and hydrogen production are topics gaining interest for scientists and developers from different areas such as environmental technology and material science. Most of the efforts and resources are devoted to the development of new photocatalyst materials while the modeling and development of reaction systems allowing for upscaling the process to pilot or industrial scale are scarce. In this work we present what is known on the upscaling of heterogeneous photocatalysis to purify water and to produce green H2. The types of reactors successfully used in water treatment plants are presented as study cases. The challenges of upscaling the photocatalysis process to produce green H2 are explored from the perspectives of (a) the adaptation of photoreactors (b) the competitiveness of the process and (c) safety. Throughout the text Green Chemistry and Engineering Principles are described and discussed on how they are currently being applied to the heterogeneous photocatalysis process along with the challenges that are ahead. Lastly the role of automation and high-throughput methods in the upscaling following the Green Principles is discussed.
Energy, Exergy, and Economic Analysis of Cryogenic Distillation and Chemical Scrubbing for Biogas Upgrading and Hydrogen Production
Mar 2022
Publication
Biogas is one of the most important sources of renewable energy and hydrogen production which needs upgrading to be functional. In this study two methods of biogas upgrading from organic parts of municipal waste were investigated. For biogas upgrading this article used a 3E analysis and simulated cryogenic separation and chemical scrubbing. The primary goal was to compare thermoeconomic indices and create hydrogen by reforming biomethane. The exergy analysis revealed that the compressor of the refrigerant and recovery column of MEA contributed the most exergy loss in the cryogenic separation and chemical scrubbing. The total exergy efficiency of cryogenic separation and chemical scrubbing was 85% and 84%. The energy analysis revealed a 2.07% lower energy efficiency for chemical scrubbing. The capital energy and total annual costs of chemical absorption were 56.51 26.33 and 54.44 percent lower than those of cryogenic separation respectively indicating that this technology is more economically feasible. Moreover because the thermodynamic efficiencies of the two methods were comparable the chemical absorption method was adopted for hydrogen production. The biomethane steam reforming was simulated and the results indicated that this method required an energy consumption of 90.48 MJ kgH2 . The hydrogen production intensity equaled 1.98 kmoleH2 kmolebiogas via a 79.92% methane conversion.
Advanced Optimal Planning for Microgrid Technologies Including Hydrogen and Mobility at a Real Microgrid Testbed
Apr 2021
Publication
This paper investigates the optimal planning of microgrids including the hydrogen energy system through mixed-integer linear programming model. A real case study is analyzed by extending the only microgrid lab facility in Austria. The case study considers the hydrogen production via electrolysis seasonal storage and fuelling station for meeting the hydrogen fuel demand of fuel cell vehicles busses and trucks. The optimization is performed relative to two different reference cases which satisfy the mobility demand by diesel fuel and utility electricity based hydrogen fuel production respectively. The key results indicate that the low emission hydrogen mobility framework is achieved by high share of renewable energy sources and seasonal hydrogen storage in the microgrid. The investment optimization scenarios provide at least 66% and at most 99% carbon emission savings at increased costs of 30% and 100% respectively relative to the costs of the diesel reference case (current situation)
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.
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.
Artificial Neural Networks for Predicting Hydrogen Production in Catalytic Dry Reforming: A Systematic Review
May 2021
Publication
Dry reforming of hydrocarbons alcohols and biological compounds is one of the most promising and effective avenues to increase hydrogen (H2 ) production. Catalytic dry reforming is used to facilitate the reforming process. The most popular catalysts for dry reforming are Ni-based catalysts. Due to their inactivation at high temperatures these catalysts need to use metal supports which have received special attention from researchers in recent years. Due to the existence of a wide range of metal supports and the need for accurate detection of higher H2 production in this study a systematic review and meta-analysis using ANNs were conducted to assess the hydrogen production by various catalysts in the dry reforming process. The Scopus Embase and Web of Science databases were investigated to retrieve the related articles from 1 January 2000 until 20 January 2021. Forty-seven articles containing 100 studies were included. To determine optimal models for three target factors (hydrocarbon conversion hydrogen yield and stability test time) artificial neural networks (ANNs) combined with differential evolution (DE) were applied. The best models obtained had an average relative error for the testing data of 0.52% for conversion 3.36% for stability and 0.03% for yield. These small differences between experimental results and predictions indicate a good generalization capability.
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.
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.
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.
Feasibility of Hydrogen Production from Steam Reforming of Biodiesel (FAME) Feedstock on Ni-supported Catalysts
Jan 2015
Publication
The catalytic steam reforming of biodiesel was examined over Ni-alumina and Ni–ceria–zirconia catalysts at atmospheric pressure. Effects of temperatures of biodiesel preheating/vaporising (190–365 ◦C) and reforming (600–800 ◦C) molar steam to carbon ratio (S/C = 2–3) and residence time in the reformer represented by the weight hourly space velocity ‘WHSV’ of around 3 were examined for 2 h. Ni supported on calcium aluminate and on ceria–zirconia supports achieved steady state hydrogen product stream within 90% of the equilibrium yields although 4% and 1% of the carbon feed had deposited on the catalysts respectively during the combined conditions of start-up and steady state. Addition of dopants to ceria–zirconia supported catalyst decreased the performance of the catalyst. Increase in S/C ratio had the expected positive effects of higher H2 yield and lower carbon deposition.
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.
Main Hydrogen Production Processes: An Overview
May 2021
Publication
Due to its characteristics hydrogen is considered the energy carrier of the future. Its use as a fuel generates reduced pollution as if burned it almost exclusively produces water vapor. Hydrogen can be produced from numerous sources both of fossil and renewable origin and with as many production processes which can use renewable or non-renewable energy sources. To achieve carbon neutrality the sources must necessarily be renewable and the production processes themselves must use renewable energy sources. In this review article the main characteristics of the most used hydrogen production methods are summarized mainly focusing on renewable feedstocks furthermore a series of relevant articles published in the last year are reviewed. The production methods are grouped according to the type of energy they use; and at the end of each section the strengths and limitations of the processes are highlighted. The conclusions compare the main characteristics of the production processes studied and contextualize their possible use.
Technical Potential of On-site Wind Powered Hydrogen Producing Refuelling Stations in the Netherlands
Aug 2020
Publication
This study assesses the technical potential of wind turbines to be installed next to existing fuelling stations in order to produce hydrogen. Hydrogen will be used for Fuel Cell Vehicle refuelling and feed-in existing local gas grids. The suitable fuelling stations are selected through a GIS assessment applying buffer zones and taking into account risks associated with wind turbine installation next to built-up areas critical infrastructures and ecological networks. It was found that 4.6% of existing fuelling stations are suitable. Further a hydrogen production potential assessment was made using weather station datasets land cover data and was expressed as potential future Fuel Cell Electric Vehicle demand coverage. It was found that for a 30% FCEV drivetrain scenario these stations can produce 2.3% of this demand. Finally a case study was made for the proximity of those stations in existing gas distribution grids.
Experimental Study and Thermodynamic Analysis of Hydrogen Production through a Two-Step Chemical Regenerative Coal Gasification
Jul 2019
Publication
Hydrogen as a strategy clean fuel is receiving more and more attention recently in China in addition to the policy emphasis on H2. In this work we conceive of a hydrogen production process based on a chemical regenerative coal gasification. Instead of using a lumped coal gasification as is traditional in the H2 production process herein we used a two-step gasification process that included coking and char-steam gasification. The sensible heat of syngas accounted for 15–20% of the total energy of coal and was recovered and converted into chemical energy of syngas through thermochemical reactions. Moreover the air separation unit was eliminated due to the adoption of steam as oxidant. As a result the efficiency of coal to H2 was enhanced from 58.9% in traditional plant to 71.6% in the novel process. Further the energy consumption decreased from 183.8 MJ/kg in the traditional plant to 151.2 MJ/kg in the novel process. The components of syngas H2 and efficiency of gasification are herein investigated through experiments in fixed bed reactors. Thermodynamic performance is presented for both traditional and novel coal to hydrogen plants.
Hydrogen Fuel and Electricity Generation from a New Hybrid Energy System Based on Wind and Solar Energies and Alkaline Fuel Cell
Apr 2021
Publication
Excessive consumption of fossil fuels has led to depletion of reserves and environmental crises. Therefore turning to clean energy sources is essential. However these energy sources are intermittent in nature and have problems meeting long-term energy demand. The option suggested by the researchers is to use hybrid energy systems. The aim of this paper is provide the conceptual configuration of a novel energy cycle based on clean energy resources. The novel energy cycle is composed of a wind turbine solar photovoltaic field (PV) an alkaline fuel cell (AFC) a Stirling engine and an electrolyzer. Solar PV and wind turbine convert solar light energy and wind kinetic energy into electricity respectively. Then the generated electricity is fed to water electrolyzer. The electrolyzer decomposes water into oxygen and hydrogen gases by receiving electrical power. So the fuel cell inlets are provided. Next the AFC converts the chemical energy contained in hydrogen into electricity during electrochemical reactions with by-product (heat). The purpose of the introduced cycle is to generate electricity and hydrogen fuel. The relationships defined for the components of the proposed cycle are novel and is examined for the first time. Results showed that the output of the introduced cycle is 10.5 kW of electricity and its electrical efficiency is 56.9%. In addition the electrolyzer uses 9.9 kW of electricity to produce 221.3 grams per hour of hydrogen fuel. The share of the Stirling engine in the output power of the cycle is 9.85% (1033.7 W) which is obtained from the dissipated heat of the fuel cell. In addition wind turbine is capable of generating an average of 4.1 kW of electricity. However 238.6 kW of cycle exergy is destroyed. Two different scenarios are presented for solar field design.
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.
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.
A Flexible Analytical Model for Operational Investigation of Solar Hydrogen Plants
Nov 2021
Publication
Hydrogen will become a dominant energy carrier in the future and the efficiency and lifetime cost of its production through water electrolysis is a major research focus. Alongside efforts to offer optimum solutions through plant design and sizing it is also necessary to develop a flexible virtualised replica of renewable hydrogen plants that not only models compatibility with the “plug-and-play” nature of many facilities but that also identifies key elements for optimisation of system operation. This study presents a model for a renewable hydrogen production plant based on real-time historical and present-day datasets of PV connected to a virtualised grid-connected AC microgrid comprising different technologies of batteries electrolysers and fuel cells. Mathematical models for each technology were developed from chemical and physical metrics of the plant. The virtualised replica is the first step toward the implementation of a digital twin of the system and accurate validation of the system behaviour when updated with real-time data. As a case study a solar hydrogen pilot plant consisting of a 60 kW Solar PV a 40 kW PEM electrolyser a 15 kW LIB battery and a 5 kW PEM fuel cell were simulated and analysed. Two effective operational factors on the plant's performance are defined: (i) electrolyser power settings to determine appropriate hydrogen production over twilight periods and/or overnight and (ii) a user-defined minimum threshold for battery state of charge to prevent charge depletion overnight if the electrolyser load is higher than its capacity. The objective of this modelling is to maximise hydrogen yield while both loss of power supply probability (LPSP) and microgrid excess power are minimised. This analysis determined: (i) a hydrogen yield of 38e39% from solar DC energy to hydrogen energy produced (ii) an LPSP <2.6 104 and (iii) < 2% renewable energy lost to the grid as excess electricity for the case study.
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.
The Use of Strontium Ferrite in Chemical Looping Systems
May 2020
Publication
This work reports a detailed chemical looping investigation of strontium ferrite (SrFeO3−δ) a material with the perovskite structure type able to donate oxygen and stay in a nonstoichiometric form over a broad range of oxygen partial pressures starting at temperatures as low as 250°C (reduction in CO measured in TGA). SrFeO3−δ is an economically attractive simple but remarkably stable material that can withstand repeated phase transitions during redox cycling. Mechanical mixing and calcination of iron oxide and strontium carbonate was evaluated as an effective way to obtain pure SrFeO3−δ. In–situ XRD was performed to analyse structure transformations during reduction and reoxidation. Our work reports that much deeper reduction from SrFeO3−δ to SrO and Fe is reversible and results in oxygen release at a chemical potential suitable for hydrogen production. Thermogravimetric experiments with different gas compositions were applied to characterize the material and evaluate its available oxygen capacity. In both TGA and in-situ XRD experiments the material was reduced below δ=0.5 followed by reoxidation either with CO2 or air to study phase segregation and reversibility of crystal structure transitions. As revealed by in-situ XRD even deeply reduced material regenerates at 900°C to SrFeO3−δ with a cubic structure. To investigate the catalytic behaviour of SrFeO3−δ in methane combustion experiments were performed in a fluidized bed rig. These showed SrFeO3−δ donates O2 into the gas phase but also assists with CH4 combustion by supplying lattice oxygen. To test the material for combustion and hydrogen production long cycling experiments in a fluidized bed rig were also performed. SrFeO3−δ showed stability over 30 redox cycles both in experiments with a 2-step oxidation performed in CO2 followed by air as well as a single step oxidation in CO2 alone. Finally the influence of CO/CO2 mixtures on material performance was tested; a fast and deep reduction in elevated pCO2 makes the material susceptible to carbonation but the process can be reversed by increasing the temperature or lowering pCO2.
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.
Hydrogen Production in Methane Decomposition Reactor Using Solar Thermal Energy
Nov 2021
Publication
This study investigates the decomposition of methane using solar thermal energy as a heat source. Instead of the direct thermal decomposition of the methane at a temperature of 1200 ◦C or higher a catalyst coated with carbon black on a metal foam was used to lower the temperature and activation energy required for the reaction and to increase the yield. To supply solar heat during the reaction a reactor suitable for a solar concentrating system was developed. In this process a direct heating type reactor with quartz was initially applied and a number of problems were identified. An indirect heating type reactor with an insulated cavity and a rotating part was subsequently developed followed by a thermal barrier coating application. Methane decomposition experiments were conducted in a 40 kW solar furnace at the Korea Institute of Energy Research. Conversion rates of 96.7% and 82.6% were achieved when the methane flow rate was 20 L/min and 40 L/min respectively.
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.
Comparative Analysis of Energy and Exergy Performance of Hydrogen Production Methods
Nov 2020
Publication
The study of the viability of hydrogen production as a sustainable energy source is a current challenge to satisfy the great world energy demand. There are several techniques to produce hydrogen either mature or under development. The election of the hydrogen production method will have a high impact on practical sustainability of the hydrogen economy. An important profile for the viability of a process is the calculation of energy and exergy efficiencies as well as their overall integration into the circular economy. To carry out theoretical energy and exergy analyses we have estimated proposed hydrogen production using different software (DWSIM and MATLAB) and reference conditions. The analysis consolidates methane reforming or auto-thermal reforming as the viable technologies at the present state of the art with reasonable energy and exergy efficiencies but pending on the impact of environmental constraints as CO2 emission countermeasures. However natural gas or electrolysis show very promising results and should be advanced in their technological and maturity scaling. Electrolysis shows a very good exergy efficiency due to the fact that electricity itself is a high exergy source. Pyrolysis exergy loses are mostly in the form of solid carbon material which has a very high integration potential into the hydrogen economy.
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.
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.
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.
Electric Load Influence on Performances of a Composite Plant for Hydrogen Production from RES and its Conversion in Electricity
Nov 2019
Publication
The analysis here presented investigates the influence of electrical load on the operational performances of a plant for hydrogen production from solar energy and its conversion in electricity via a fuel cell. The plant is an actual one currently under construction in Reggio Calabria (Italy) at the site of the Mediterranean university campus; it is composed of a Renewable Energy Source (RES) section (photovoltaic panels) a hydrogen production section and a fuel cell power section feeding the electrical energy demand of the load. Two different load configurations have been analysed and simulations have been carried out through HomerTM simulation code. Results allow interesting conclusions regarding the plant operation to be drawn. The study could have a remarkable role in supporting further research activities aimed at the assessment of the optimal configuration of this type of pioneering plants designed for feeding electrical loads possibly in a self-sufficient way.
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.
Hydrogen Production Technologies: Current State and Future Developments
Mar 2013
Publication
Hydrogen (H2) is currently used mainly in the chemical industry for the production of ammonia and methanol. Nevertheless in the near future hydrogen is expected to become a significant fuel that will largely contribute to the quality of atmospheric air. Hydrogen as a chemical element (H) is the most widespread one on the earth and as molecular dihydrogen (H2) can be obtained from a number of sources both renewable and nonrenewable by various processes. Hydrogen global production has so far been dominated by fossil fuels with the most significant contemporary technologies being the steam reforming of hydrocarbons (e.g. natural gas). Pure hydrogen is also produced by electrolysis of water an energy demanding process. This work reviews the current technologies used for hydrogen (H2) production from both fossil and renewable biomass resources including reforming (steam partial oxidation autothermal plasma and aqueous phase) and pyrolysis. In addition other methods for generating hydrogen (e.g. electrolysis of water) and purification methods such as desulfurization and water-gas shift reactions are discussed.
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.
Transitioning Remote Arctic Settlements to Renewable Energy Systems – A Modelling Study of Longyearbyen, Svalbard
Nov 2019
Publication
As transitioning away from fossil fuels to renewable energy sources comes on the agenda for a range of energy systems energy modelling tools can provide useful insights. If large parts of the energy system turns out to be based on variable renewables an accurate representation of their short-term variability in such models is crucial. In this paper we have developed a stochastic long-term energy model and applied it to an isolated Arctic settlement as a challenging and realistic test case. Our findings suggest that the stochastic modelling approach is critical in particular for studies of remote Arctic energy systems. Furthermore the results from a case study of the Norwegian settlement of Longyearbyen suggest that transitioning to a system based on renewable energy sources is feasible. We recommend that a solution based mainly on renewable power generation but also including energy storage import of hydrogen and adequate back-up capacity is taken into consideration when planning the future of remote Arctic settlements.
Optimal Day-ahead Dispatch of an Alkaline Electrolyser System Concerning Thermal–electric Properties and State-transitional Dynamics
Oct 2021
Publication
Green hydrogen is viewed as a promising energy carrier for sustainable development goals. However it has suffered from high costs hindering its implementation. For a stakeholder who considers both renewable energy and electrolysis units it is important to exploit the flexibility of such portfolios to maximize system operational revenues. To this end an electrolyser model that can characterize its dynamic behavior is required in both electric and thermal aspects. In this paper we develop a comprehensive alkaline electrolyser model that is capable of describing its hydrogen production properties temperature variations and state transitions (among production stand-by and off states). This model is further used to study the optimal dispatch of an electrolyser based on a real-world hybrid wind/electrolyser system. The results show the model can effectively capture the coupling between thermal–electric dynamics and on–off performance of an electrolyser. The flexible operation strategy based on this model is proven to significantly increase daily revenues under different spot price conditions for electricity. Comparing the model with the ones derived from conventional modeling methods reveals this model offers more operating details and highlights several operational features such as the preference for working at partial load conditions although at the expense of more computing resources. It is suggested to use this model in studies related to energy integration operation planning and control scheme development in which the multi-domain dynamic properties of electrolysers in electricity/gas/heat need to be properly characterized. A sensitivity analysis on key parameters of such electrolyser system is also introduced to connect the daily operation with long-term planning.
Renewable Hydrogen Implementations for Combined Energy Storage, Transportation and Stationary Applications
Dec 2019
Publication
The purpose of this paper is to discuss the potential of hydrogen obtained from renewable sources for energy generation and storage systems. The first part of analysis will address such issues as various methods of green hydrogen production storage and transportation. The review of hydrogen generation methods will be followed by the critical analysis and the selection of production method. This selection is justified by the results of the comparative research on alternative green hydrogen generation technologies with focus on their environmental impacts and costs. The comparative analysis includes the biomass-based methods as well as water splitting and photo-catalysis methods while water electrolysis is taken as a benchmark. Hydrogen storage and transportation issues will be further discussed in purpose to form the list of recommended solutions. In the second part of the paper the technology readiness and technical feasibility for joint hydrogen applications will be analysed. This will include the energy storage and production systems based on renewable hydrogen in combination with hydrogen usage in mobility systems as well as the stationary applications in buildings such as combined heat and power (CHP) plants or fuel cell electric generators. Based on the analysis of the selected case studies the author will discuss the role of hydrogen for the carbon emission reduction with the stress on the real value of carbon footprint of hydrogen depending on the gas source storage transportation and applications.
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.
Research Requirements to Move the Bar Forward Using Aqueous Formate Salts as H2 Carriers for Energy Storage Applications
Nov 2020
Publication
In this perspective on hydrogen carriers we focus on the needs for the development of robust active catalysts for the release of H2 from aqueous formate solutions which are non-flammable non-toxic thermally stable and readily available at large scales at reasonable cost. Formate salts can be stockpiled in the solid state or dissolved in water for long term storage and transport using existing infrastructure. Furthermore formate salts are readily regenerated at moderate pressures using the same catalyst as for the H2 release. There have been several studies focused on increasing the activity of catalysts to release H2 at moderate temperatures i.e. < 80 °C below the operating temperature of a proton exchange membrane (PEM) fuel cell. One significant challenge to enable the use of aqueous formate salts as hydrogen carriers is the deactivation of the catalyst under operating conditions. In this work we provide a review of the most efficient heterogeneous catalysts that have been described in the literature their proposed modes of deactivation and the strategies reported to reactivate them. We discuss potential pathways that may lead to deactivation and strategies to mitigate it in a variety of H2 carrier applications. We also provide an example of a potential use case employing formate salts solutions using a fixed bed reactor for seasonal storage of energy for a microgrid application.
Techno-Economic Analysis of Hydrogen and Electricity Production by Biomass Calcium Looping Gasification
Feb 2022
Publication
Combined cycle biomass calcium looping gasification is proposed for a hydrogen and electricity production (CLGCC–H) system. The process simulation Aspen Plus is used to conduct techno-economic analysis of the CLGCC–H system. The appropriate detailed models are set up for the proposed system. Furthermore a dual fluidized bed is optimized for hydrogen production at 700 °C and 12 bar. For comparison calcium looping gasification with the combined cycle for electricity (CLGCC) is selected with the same parameters. The system exergy and energy efficiency of CLGCC–H reached as high as 60.79% and 64.75% while the CLGCC system had 51.22% and 54.19%. The IRR and payback period of the CLGCC–H system based on economic data are calculated as 17.43% and 7.35 years respectively. However the CLGCC system has an IRR of 11.45% and a payback period of 9.99 years respectively. The results show that the calcium looping gasification-based hydrogen and electricity coproduction system has a promising market prospect in the near future.
Flare Gas Monetization and Greener Hydrogen Production via Combination with Crypto Currency Mining and Carbon Dioxide Capture
Jan 2022
Publication
In view of the continuous debates on the environmental impact of blockchain technologies in particular crypto currency mining accompanied by severe carbon dioxide emissions a technical solution has been considered assuming direct monetization of associated petroleum gas currently being flared. The proposed approach is based on the technology of low-temperature steam reforming of hydrocarbons which allows flare gas conditioning towards the requirements for fuel for gas piston and gas turbine power plants. The generation of electricity directly at the oil field and its use for on-site crypto currency mining transforms the process of wasteful flaring of valuable hydrocarbons into an economically attractive integrated processing of natural resources. The process is not carbon neutral and is not intended to compete zero-emission technologies but its combination with technologies for carbon dioxide capture and re-injection into the oil reservoir can both enhance the oil recovery and reduce carbon dioxide emissions into the atmosphere. The produced gas can be used for local transport needs while the generated heat and electricity can be utilized for on-site food production and biological carbon dioxide capture in vertical greenhouse farms. The suggested approach allows significant decrease in the carbon dioxide emissions at oil fields and although it may seem paradoxically on-site cryptocurrency mining actually may lead to a decrease in the carbon footprint. The amount of captured CO2 could be transformed into CO2 emission quotas which can be spent for the production of virtually “blue” hydrogen by steam reforming of natural gas in locations where the CO2 capture is technically impossible and/or unprofitable.
Rational Design and Application of Covalent Organic Frameworks for Solar Fuel Production
Jul 2021
Publication
Harnessing solar energy and converting it into renewable fuels by chemical processes such as water splitting and carbon dioxide (CO2 ) reduction is a highly promising yet challenging strategy to mitigate the effects arising from the global energy crisis and serious environmental concerns. In recent years covalent organic framework (COF)-based materials have gained substantial research interest because of their diversified architecture tunable composition large surface area and high thermal and chemical stability. Their tunable band structure and significant light absorption with higher charge separation efficiency of photoinduced carriers make them suitable candidates for photocatalytic applications in hydrogen (H2) generation CO2 conversion and various organic transformation reactions. In this article we describe the recent progress in the topology design and synthesis method of COF-based nanomaterials by elucidating the structure-property correlations for photocatalytic hydrogen generation and CO2 reduction applications. The effect of using various kinds of 2D and 3D COFs and strategies to control the morphology and enhance the photocatalytic activity is also summarized. Finally the key challenges and perspectives in the field are highlighted for the future development of highly efficient COF-based photocatalysts.
Efficient Renewable-to-Hydrogen Conversion via Decoupled Electrochemical Water Splitting
Aug 2020
Publication
Water electrolysis powered by renewables provides a green approach to hydrogen production to support the ‘‘hydrogen economy.’’ However the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) are tightly coupled in both time and space in traditional water electrolysis which brings inherent operational challenges such as the mixture of H2/O2 and the limited HER rate caused by the sluggish kinetics of OER. Against this background decoupling H2 and O2 production in water electrolysis by using the auxiliary redox mediator was first proposed in 2013 in which O2 and H2 are produced at different times rates and/or locations. The decoupling strategy offers not only a new way to facilitate renewables to H2 but it can also be applied in other chemical or electrochemical processes. This review describes recent efforts to develop high-performance redox mediators optimized strategies in decoupled water electrolysis the design of electrolyzer configuration the challenges faced and the prospective directions.
Comparison of Hydrogen Powertrains with the Battery Powered Electric Vehicle and Investigation of Small-Scale Local Hydrogen Production Using Renewable Energy
Jan 2021
Publication
Climate change is one of the major problems that people face in this century with fossil fuel combustion engines being huge contributors. Currently the battery powered electric vehicle is considered the predecessor while hydrogen vehicles only have an insignificant market share. To evaluate if this is justified different hydrogen power train technologies are analyzed and compared to the battery powered electric vehicle. Even though most research focuses on the hydrogen fuel cells it is shown that despite the lower efficiency the often-neglected hydrogen combustion engine could be the right solution for transitioning away from fossil fuels. This is mainly due to the lower costs and possibility of the use of existing manufacturing infrastructure. To achieve a similar level of refueling comfort as with the battery powered electric vehicle the economic and technological aspects of the local small-scale hydrogen production are being investigated. Due to the low efficiency and high prices for the required components this domestically produced hydrogen cannot compete with hydrogen produced from fossil fuels on a larger scale
Blue Hydrogen
Apr 2021
Publication
The urgency of reaching net-zero emissions requires a rapid acceleration in the deployment of all emissions reducing technologies. Near-zero emissions hydrogen (clean hydrogen) has the potential to make a significant contribution to emissions reduction in the power generation transportation and industrial sectors.
As part of the Circular Carbon Economy: Keystone to Global Sustainability series with the Center on Global Energy Policy at Columbia University SIPA this report explores the potential contribution of blue hydrogen to climate mitigation.
The report looks at:
As part of the Circular Carbon Economy: Keystone to Global Sustainability series with the Center on Global Energy Policy at Columbia University SIPA this report explores the potential contribution of blue hydrogen to climate mitigation.
The report looks at:
- Cost drivers for renewable hydrogen and hydrogen produced with fossil fuels and CCS;
- Resource requirements and cost reduction opportunities for clean hydrogen; and
- Policy recommendations to drive investment in clean hydrogen production.
- Blue hydrogen is well placed to kickstart the rapid increase in the utilisation of clean hydrogen for climate mitigation purposes but requires strong and sustained policy to incentivise investment at the rate necessary to meet global climate goals.
Synergetic Effect of Multiple Phases on Hydrogen Desorption Kinetics and Cycle Durability in Ball Milled MgH2–PrF3–Al–Ni Composite
Jan 2021
Publication
A new MgH2–PrF3–Al–Ni composite was prepared by ball milling under hydrogen atmosphere. After initial dehydrogenation and rehydrogenation Pr3Al11 MgF2 PrH3 and Mg2NiH4 nanoparticles formed accompanying the main phase MgH2. The hydrogen absorption-desorption properties were measured by using a Sieverts-type apparatus. The results showed that the MgH2–PrF3–Al–Ni composite improved cycle stability and enhanced hydrogen desorption kinetics. The improvement of hydrogen absorption-desorption properties is ascribed to the synergetic effect of the in situ formed Pr3Al11 MgF2 PrH3 and Mg2NiH4 nanoparticles. This work provides an important inspiration for the improvement of hydrogen storage properties in Mg-based materials.
Control of Electrons’ Spin Eliminates Hydrogen Peroxide Formation During Water Splitting
Jul 2017
Publication
The production of hydrogen through water splitting in a photoelectrochemical cell suffers from an overpotential that limits the efficiencies. In addition hydrogen-peroxide formation is identified as a competing process affecting the oxidative stability of photoelectrodes. We impose spin-selectivity by coating the anode with chiral organic semiconductors from helically aggregated dyes as sensitizers; Zn-porphyrins and triarylamines. Hydrogen peroxide formation is dramatically suppressed while the overall current through the cell correlating with the water splitting process is enhanced. Evidence for a strong spin-selection in the chiral semiconductors is presented by magnetic conducting (mc-)AFM measurements in which chiral and achiral Zn-porphyrins are compared. These findings contribute to our understanding of the underlying mechanism of spin selectivity in multiple electron-transfer reactions and pave the way toward better chiral dye-sensitized photoelectrochemical cells.
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.
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.
The Role of Hydrogen in the Transition from a Petroleum Economy to a Low-carbon Society
Jun 2021
Publication
A radical decarbonization pathway for the Norwegian society towards 2050 is presented. The paper focuses on the role of hydrogen in the transition when present Norwegian petroleum export is gradually phased out. The study is in line with EU initiatives to secure cooperation opportunities with neighbouring countries to establish an international hydrogen market. Three analytical perspectives are combined. The first uses energy models to investigate the role of hydrogen in an energy and power market perspective without considering hydrogen export. The second uses an economic equilibrium model to examine the potential role of hydrogen export in value creation. The third analysis is a socio-technical case study on the drivers and barriers for hydrogen production in Norway. Main conclusions are that access to renewable power and hydrogen are prerequisites for decarbonization of transport and industrial sectors in Norway and that hydrogen is a key to maintain a high level of economic activity. Structural changes in the economy impacts of new technologies and key enablers and barriers in this transition are discussed.
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.
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