Production & Supply Chain
Power-to-fuels Via Solid-oxide Electrolyzer: Operating Window and Techno-economics
May 2019
Publication
Power-to-fuel systems via solid-oxide electrolysis are promising for storing excess renewable electricity by efficient electrolysis of steam (or co-electrolysis of steam and CO2) into hydrogen (or syngas) which can be further converted into synthetic fuels with plant-wise thermal integration. Electrolysis stack performance and durability determine the system design performance and long-term operating strategy; thus solid-oxide electrolyzer based power-to-fuels were investigated from the stack to system levels. At the stack level the data from a 6000-h stack testing under laboratory isothermal conditions were used to calibrate a quasi-2D model which enables to predict practical isothermal stack performance with reasonable accuracy. Feasible stack operating windows meeting various design specifications (e.g. specific syngas composition) were further generated to support the selection of operating points. At the system level with the chosen similar stack operating points various power-to-fuel systems including power-to-hydrogen power-to-methane power-to-methanol (dimethyl ether) and power-to-gasoline were compared techno-economically considering system-level heat integration. Several operating strategies of the stack were compared to address the increase in stack temperature due to degradation. The modeling results show that the system efficiency for producing H2 methane methanol/dimethyl ether and gasoline decreases sequentially from 94% (power-to-H2) to 64% (power-to-gasoline) based on a higher heating value. Co-electrolysis which allows better heat integration can improve the efficiency of the systems with less exothermic fuel-synthesis processes (e.g. methanol/dimethyl ether) but offers limited advantages for power-to-methane and power-to-gasoline systems. In a likely future scenario where the growing amount of electricity from renewable sources results in increasing periods of a negative electricity price solid oxide electrolyser based power-to-fuel systems are highly suitable for levelling the price fluctuations in an economic way.
Role of the Sulphur Source in the Solvothermal Synthesis of Ag-CdS Photocatalysts: Effects on the Structure and Photoactivity for Hydrogen Production
Dec 2020
Publication
The aim of this work is to study the influence of the sulphur source (elemental sulphur thiourea and L-cysteine) in the solvothermal synthesis of Ag-CdS over its growth structuration and state of Ag and how these changes influence on its photoactivity. The differences in the generation rate of the S2− from the sulphur sources during the solvothermal synthesis determine the nucleation and growth pathways of CdS affecting to the silver state and its incorporation into the CdS lattice. The hydrogen production on Ag-CdS photocatalysts decreases according the sequence: thiourea > elemental sulphur >> L-cysteine. The changes in the photoactivity of Ag-CdS samples are analysed in terms of the differences in the insertion of Ag+ into the CdS lattice the formation of composites between CdS and Ag2S and the formation of CdS crystalline domains with strong confinement effect derived from the different sulphur source used in the solvothermal synthesis
Energy Optimization of a Sulfur-Iodine Thermochemical Nuclear Hydrogen Production Cycle
Dec 2021
Publication
The use of nuclear reactors is a large studied possible solution for thermochemical water splitting cycles. Nevertheless there are several problems that have to be solved. One of them is to increase the efficiency of the cycles. Hence in this paper a thermal energy optimization of a SulfureIodine nuclear hydrogen production cycle was performed by means a heuristic method with the aim of minimizing the energy targets of the heat exchanger network at different minimum temperature differences. With this method four different heat exchanger networks are proposed. A reduction of the energy requirements for cooling ranges between 58.9-59.8% and 52.6-53.3% heating compared to the reference design with no heat exchanger network. With this reduction the thermal efficiency of the cycle increased in about 10% in average compared to the reference efficiency. This improves the use of thermal energy of the cycle.
Studies of the Impact of Hydrogen on the Stability of Gaseous Mixtures of THT
Dec 2020
Publication
One of the most important requirements concerning the quality of natural gases guaranteeing their safe use involves providing the proper level of their odorization. This allows for the detection of uncontrolled leakages of gases from gas networks installations and devices. The concentration of an odorant should be adjusted in such a manner that the gas odor in a mixture with air would be noticeable by users (gas receivers). A permanent odor of gas is guaranteed by the stability of the odorant molecule and its resistance to changes in the composition of odorized gases. The article presents the results of experimental research on the impact of a hydrogen additive on the stability of tetrahydrothiophene (THT) mixtures in methane and in natural gas with a hydrogen additive. The objective of the work was to determine the readiness of measurement infrastructures routinely used in monitoring the process of odorizing natural gas for potential changes in its composition. One of the elements of this infrastructure includes the reference mixtures of THT used to verify the correctness of the readings of measurement devices. The performed experimental tests address possible changes in the composition of gases supplied via a distribution network resulting from the introduction of hydrogen. The lack of interaction between hydrogen and THT has been verified indirectly by assessing the stability of its mixtures with methane and natural gas containing hydrogen. The results of the presented tests permitted the identification of potential hazards for the safe use of gas from a distribution network resulting from changes in its composition caused by the addition of hydrogen.
Electrified Hydrogen Production from Methane for PEM Fuel Cells Feeding: A Review
May 2022
Publication
The greatest challenge of our times is to identify low cost and environmentally friendly alternative energy sources to fossil fuels. From this point of view the decarbonization of industrial chemical processes is fundamental and the use of hydrogen as an energy vector usable by fuel cells is strategic. It is possible to tackle the decarbonization of industrial chemical processes with the electrification of systems. The purpose of this review is to provide an overview of the latest research on the electrification of endothermic industrial chemical processes aimed at the production of H2 from methane and its use for energy production through proton exchange membrane fuel cells (PEMFC). In particular two main electrification methods are examined microwave heating (MW) and resistive heating (Joule) aimed at transferring heat directly on the surface of the catalyst. For cases the catalyst formulation and reactor configuration were analyzed and compared. The key aspects of the use of H2 through PEM were also analyzed highlighting the most used catalysts and their performance. With the information contained in this review we want to give scientists and researchers the opportunity to compare both in terms of reactor and energy efficiency the different solutions proposed for the electrification of chemical processes available in the recent literature. In particular through this review it is possible to identify the solutions that allow a possible scale-up of the electrified chemical process imagining a distributed production of hydrogen and its consequent use with PEMs. As for PEMs in the review it is possible to find interesting alternative solutions to platinum with the PGM (Platinum Group Metal) free-based catalysts proposing the use of Fe or Co for PEM application.
The Influence of Hydrogen Sulfide Contaminations on Hydrogen Production in Chemical Looping Processes
Aug 2021
Publication
Chemical looping with iron-based oxygen carriers enables the production of hydrogen from various fossil and biogenic primary energy sources. In applications with real producer gases such as biogas or gasified biomass hydrogen sulfide represents one of the most challenging contaminants. The impact of H2S on the reactivity of a Fe2O3/Al2O3 oxygen carrier material in chemical looping hydrogen production was investigated in the present work. First potential sulfur deactivation mechanisms are discussed in detail on the basis of thermodynamic data. Afterwards an experimental study in a fixed-bed reactor system gave experimental evidence on the fate of sulfur in chemical looping hydrogen systems. The chemisorption of hydrogen sulfide (H2S) was identified as the main cause for the accumulative adsorption of H2S in the reduction phase and was confirmed by ex-situ ICP-EOS analysis. In the subsequent steam oxidation step significant quantities of H2S were released resulting in an undesirable contamination of the hydrogen product gas. The reason was found as weakened sulfur bonds through increasing reactor temperatures caused by the exothermic oxidation reactions. In additional air oxidation steps no further contaminants as sulfur dioxide were identified. A profound interpretation was achieved through the fulfillment of the overall sulfur mass balance within a mean deviation of 3.7%. Quantitative investigations showed that the hydrogen consumption decreased by 12% throughout the reduction phase in the event of 100 ppm H2S in the feed gas
Solar Thermochemical Hydrogen Production in the USA
Jul 2021
Publication
Hydrogen produced from renewable energy has the potential to decarbonize parts of the transport sector and many other industries. For a sustainable replacement of fossil energy carriers both the environmental and economic performance of its production are important. Here the solar thermochemical hydrogen pathway is characterized with a techno-economic and life-cycle analysis. Assuming a further increase of conversion efficiency and a reduction of investment costs it is found that hydrogen can be produced in the United States of America at costs of 2.1–3.2 EUR/kg (2.4–3.6 USD/kg) at specific greenhouse gas emissions of 1.4 kg CO2-eq/kg. A geographical potential analysis shows that a maximum of 8.4 × 1011 kg per year can be produced which corresponds to about twelve times the current global and about 80 times the current US hydrogen production. The best locations are found in the Southwest of the US which have a high solar irradiation and short distances to the sea which is beneficial for access to desalinated water. Unlike for petrochemical products the transport of hydrogen could potentially present an obstacle in terms of cost and emissions under unfavorable circumstances. Given a large-scale deployment low-cost transport seems however feasible.
FPGA-Based Implementation of an Optimization Algorithm to Maximize the Productivity of a Microbial Electrolysis Cell
Jun 2021
Publication
In this work the design of the hardware architecture to implement an algorithm for optimizing the Hydrogen Productivity Rate (HPR) in a Microbial Electrolysis Cell (MEC) is presented. The HPR in the MEC is maximized by the golden section search algorithm in conjunction with a super-twisting controller. The development of the digital architecture in the implementation step of the optimization algorithm was developed in the Very High Description Language (VHDL) and synthesized in a Field Programmable Gate Array (FPGA). Numerical simulations demonstrated the feasibility of the proposed optimization strategy embedded in an FPGA Cyclone II. Results showed that only.
Hollow Cobalt Sulfide Nanocapsules for Electrocatalytic Selective Transfer Hydrogenation of Cinnamaldehyde with Water
Feb 2021
Publication
Designing nanostructured electrocatalysts for selective transfer hydrogenation of α β-unsaturated aldehydes with water as the hydrogen source is highly desirable. Here a facile self-templating strategy is designed for the synthesis of CoS2 and CoS2-x nanocapsules (NCs) as efficient cathodes for selective transfer hydrogenation of cinnamaldehyde a model α β-unsaturated aldehyde. The hollow porous structures of NCs are rich in active sites and improve mass transfer resulting in high turnover frequency. The specific adsorption of the styryl block on pristine CoS2 NCs is conducive to the selective formation of half-hydrogenated hydrocinnamaldehyde with 91.7% selectivity and the preferential adsorption of the C = O group induced by sulfur vacancies on defective CoS2-x NCs leads to the full-hydrogenated hydrocinnamyl alcohol with 92.1% selectivity. A cross-coupling of carbon and hydrogen radicals may be involved in this electrochemical hydrogenation reaction. Furthermore this selective hydrogenation method is also effective for other α β-unsaturated aldehydes illustrating the universality of the method.
Recent Advances in Seawater Electrolysis
Jan 2022
Publication
Hydrogen energy as a clean and renewable energy has attracted much attention in recent years. Water electrolysis via the hydrogen evolution reaction at the cathode coupled with the oxygen evolution reaction at the anode is a promising method to produce hydrogen. Given the shortage of freshwater resources on the planet the direct use of seawater as an electrolyte for hydrogen production has become a hot research topic. Direct use of seawater as the electrolyte for water electrolysis can reduce the cost of hydrogen production due to the great abundance and wide availability. In recent years various high-efficiency electrocatalysts have made great progress in seawater splitting and have shown great potential. This review introduces the mechanisms and challenges of seawater splitting and summarizes the recent progress of various electrocatalysts used for hydrogen and oxygen evolution reaction in seawater electrolysis in recent years. Finally the challenges and future opportunities of seawater electrolysis for hydrogen and oxygen production are presented.
Enhanced Hydrogen Generation from Hydrolysis of MgLi Doped with Expanded Graphite
Apr 2021
Publication
Hydrolysis of Mg-based materials is considered as a potential means of safe and convenient real-time control of H2 release enabling efficient loading discharge and utilization of hydrogen in portable electronic devices. At present work the hydrogen generation properties of MgLi-graphite composites were evaluated for the first time. The MgLi-graphite composites with different doping amounts of expanded graphite (abbreviated as EG hereinafter) were synthesized through ball milling and the hydrogen behaviors of the composites were investigated in chloride solutions. Among the above doping systems the 10 wt% EG-doped MgLi exhibited the best hydrogen performance in MgCl2 solutions. In particular the 22 h-milled MgLi-10 wt% EG composites possessed both desirable hydrogen conversion and rapid reaction kinetics delivering a hydrogen yield of 966 mL H2 g−1 within merely 2 min and a maximum hydrogen generation rate of 1147 mL H2 min−1 g−1 as opposed to the sluggish kinetics in the EG-free composites. Moreover the EG-doped MgLi showed superior air-stable ability even under a 75 RH% ambient atmosphere. For example the 22 h-milled MgLi-10 wt% EG composites held a fuel conversion of 89% after air exposure for 72 h rendering it an advantage for Mg-based materials to safely store and transfer in practical applications. The similar favorable hydrogen performance of MgLi-EG composites in (simulate) seawater may shed light on future development of hydrogen generation technologies.
Towards the Hydrogen Economy—A Review of the Parameters That Influence the Efficiency of Alkaline Water Electrolyzers
May 2021
Publication
Environmental issues make the quest for better and cleaner energy sources a priority. Worldwide researchers and companies are continuously working on this matter taking one of two approaches: either finding new energy sources or improving the efficiency of existing ones. Hydrogen is a well-known energy carrier due to its high energy content but a somewhat elusive one for being a gas with low molecular weight. This review examines the current electrolysis processes for obtaining hydrogen with an emphasis on alkaline water electrolysis. This process is far from being new but research shows that there is still plenty of room for improvement. The efficiency of an electrolyzer mainly relates to the overpotential and resistances in the cell. This work shows that the path to better electrolyzer efficiency is through the optimization of the cell components and operating conditions. Following a brief introduction to the thermodynamics and kinetics of water electrolysis the most recent developments on several parameters (e.g. electrocatalysts electrolyte composition separator interelectrode distance) are highlighted.
Thermodynamic Analysis of Hydrogen Production via Chemical Looping Steam Methane Reforming Coupled with In Situ CO2 Capture
Dec 2014
Publication
A detailed thermodynamic analysis of the sorption enhanced chemical looping reforming of methane (SE-CL-SMR) using CaO and NiO as CO2 sorbent and oxygen transfer material (OTM) respectively was conducted. Conventional reforming (SMR) and sorption enhanced reforming (SE-SMR) were also investigated for comparison reasons. The results of the thermodynamic analysis show that there are significant advantages of both sorption enhanced processes compared to conventional reforming. The presence of CaO leads to higher methane conversion and hydrogen purity at low temperatures. Addition of the OTM in the SECL-SMR process concept minimizes the thermal requirements and results in superior performance compared to SE-SMR and SMR in a two-reactor concept with use of pure oxygen as oxidant/sweep gas.
Integration of a Dark Fermentation Effluent in a Microalgal-based Biorefinery for the Production of High-added Value Omega-3 Fatty Acids
Mar 2019
Publication
Dark fermentation is an anaerobic digestion process of biowaste used to produce hydrogen- for generation of energy- that however releases high amounts of polluting volatile fatty acids such as acetic acid in the environment. In order for this biohydrogen production process to become more competitive the volatile fatty acids stream can be utilized through conversion to high added-value metabolites such as omega-3 fatty acids. The docosahexaenoic acid is one of the two most known omega-3 fatty acids and has been found to be necessary for a healthy brain and proper cardiovascular function. The main source is currently fish which obtain the fatty acid from the primary producers microalgae through the food chain. Crypthecodinium cohnii a heterotrophic marine microalga is known for accumulating high amounts of docosahexaenoic acid while offering the advantage of assimilating various carbon sources such as glucose ethanol glycerol and acetic acid. The purpose of this work was to examine the ability of a C. cohnii strain to grow on different volatile fatty acids as well as on a pre-treated dark fermentation effluent and accumulate omega-3. The strain was found to grow well on relatively high concentrations of acetic butyric or propionic acid as main carbon source in a fed-batch pH-auxostat. Most importantly C. cohnii totally depleted the organic acid content of an ultra-filtrated dark fermentation effluent after 60 h of fed-batch cultivation therefore offering a bioprocess not only able to mitigate environmental pollutants but also to provide a solution for a sustainable energy production process. The accumulated docosahexaenoic acid content was as high as 29.8% (w/w) of total fatty acids.
Molybdenum Carbide Microcrystals: Efficient and Stable Catalyst for Photocatalytic H2 Evolution From Water in The Presence Of Dye Sensitizer
Sep 2016
Publication
Rod-like molybdenum carbide (Mo2C) microcrystals were obtained from the pyrolysis of Mo-containing organic-inorganic hybrid composite. We investigated the photocatalytic H2 evolution activity of Mo2C by constructing a Mo2C-dye sensitizer photocatalyst system. A high quantum efficiency of 29.7% was obtained at 480 nm. Moreover Mo2C catalyst can be easily recycled by simple filtration.
Raw Biomass Electroreforming Coupled to Green Hydrogen Generation
Mar 2021
Publication
Despite the tremendous progress of coupling organic electrooxidation with hydrogen generation in a hybrid electrolysis electroreforming of raw biomass coupled to green hydrogen generation has not been reported yet due to the rigid polymeric structures of raw biomass. Herein we electrooxidize the most abundant natural amino biopolymer chitin to acetate with over 90% yield in hybrid electrolysis. The overall energy consumption of electrolysis can be reduced by 15% due to the thermodynamically and kinetically more favorable chitin oxidation over water oxidation. In obvious contrast to small organics as the anodic reactant the abundance of chitin endows the new oxidation reaction excellent scalability. A solar-driven electroreforming of chitin and chitin-containing shrimp shell waste is coupled to safe green hydrogen production thanks to the liquid anodic product and suppression of oxygen evolution. Our work thus demonstrates a scalable and safe process for resource upcycling and green hydrogen production for a sustainable energy future.
Methane Emissions from Natural Gas and LNG Imports: An Increasingly Urgent Issue for the Future of Gas in Europe
Nov 2020
Publication
Pressure is mounting on the natural gas and LNG community to reduce methane emissions and this is most urgent in EU countries following the adoption of much tougher greenhouse gas reduction targets of 2030 and the publication of the European Commission’s Methane Strategy. With rapidly declining indigenous EU production and therefore rising import dependence there are increasing calls for emissions from imported pipeline gas and LNG to be quantified and based on actual measurements as opposed to standard emission factors. The Methane Strategy promises to be a significant milestone in that process. Companies which are supplying (or intending to supply) natural gas to the EU – the largest global import market for pipeline gas and a very significant market for LNG – would be well advised to pay close attention to how the regulation of methane emissions is unfolding and to make an immediate and positive response. Failure to do so could accelerate the demise of natural gas in European energy balances faster than would otherwise have been the case and shorten the time available for transition to decarbonised gases – specifically hydrogen – using existing natural gas infrastructure.<br/>This EU initiative will (and arguably already has) attracted attention from non-EU governments and companies involved in global gas and LNG trade. We have already seen deliveries of `carbon neutral’ LNG cargos to Asia as well as a long-term LNG contract in which the greenhouse gas content of cargos will be measured reported and verified (MRV) according to an agreed methodology. Natural gas and LNG exports if based on these standards or those set out in the EU Methane Strategy may be able to command premium prices from buyers eager to demonstrate their own GHG reduction credentials to governments customers and civil society.
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).
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.
No more items...