Production & Supply Chain
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.
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.
Characterization of the Inducible and Slow-Releasing Hydrogen Sulfide and Persulfide Donor P*: Insights into Hydrogen Sulfide Signaling
Jun 2021
Publication
Hydrogen sulfide (H2S) is an important mediator of inflammatory processes. However controversial findings also exist and its underlying molecular mechanisms are largely unknown. Recently the byproducts of H2S per-/polysulfides emerged as biological mediators themselves highlighting the complex chemistry of H2S. In this study we characterized the biological effects of P* a slow-releasing H2S and persulfide donor. To differentiate between H2S and polysulfide-derived effects we decomposed P* into polysulfides. P* was further compared to the commonly used fast-releasing H2S donor sodium hydrogen sulfide (NaHS). The effects on oxidative stress and interleukin-6 (IL-6) expression were assessed in ATDC5 cells using superoxide measurement qPCR ELISA and Western blotting. The findings on IL-6 expression were corroborated in primary chondrocytes from osteoarthritis patients. In ATDC5 cells P* not only induced the expression of the antioxidant enzyme heme oxygenase-1 via per-/polysulfides but also induced activation of Akt and p38 MAPK. NaHS and P* significantly impaired menadione-induced superoxide production. P* reduced IL-6 levels in both ATDC5 cells and primary chondrocytes dependent on H2Srelease. Taken together P* provides a valuable research tool for the investigation of H2S and per-/polysulfide signalling. These data demonstrate the importance of not only H2S but also per-/polysulfides as bioactive signaling molecules with potent anti-inflammatory and in particular antioxidant properties.
From Post-Combustion Carbon Capture to Sorption-Enhanced Hydrogen Production: A State-of-the-Art Review of Carbonate Looping Process Feasibility
Oct 2018
Publication
Carbon capture and storage is expected to play a pivotal role in achieving the emission reduction targets established by the Paris Agreement. However the most mature technologies have been shown to reduce the net efficiency of fossil fuel-fired power plants by at least 7% points increasing the electricity cost. Carbonate looping is a technology that may reduce these efficiency and economic penalties. Its maturity has increased significantly over the past twenty years mostly due to development of novel process configurations and sorbents for improved process performance. This review provides a comprehensive overview of the calcium looping concepts and statistically evaluates their techno-economic feasibility. It has been shown that the most commonly reported figures for the efficiency penalty associated with calcium looping retrofits were between 6 and 8% points. Furthermore the calcium-looping-based coal-fired power plants and sorption-enhanced hydrogen production systems integrated with combined cycles and/or fuel cells have been shown to achieve net efficiencies as high as 40% and 50–60% respectively. Importantly the performance of both retrofit and greenfield scenarios can be further improved by increasing the degree of heat integration as well as using advanced power cycles and enhanced sorbents. The assessment of the economic feasibility of calcium looping concepts has indicated that the cost of carbon dioxide avoided will be between 10 and 30 € per tonne of carbon dioxide and 10–50 € per tonne of carbon dioxide in the retrofit and greenfield scenarios respectively. However limited economic data have been presented in the current literature for the thermodynamic performance of calcium looping concepts.
Effect of Copper Cobalt Oxide Composition on Oxygen Evolution Electrocatalysts for Anion Exchange Membrane Water Electrolysis
Nov 2020
Publication
Copper cobalt oxide nanoparticles (CCO NPs) were synthesized as an oxygen evolution electrocatalyst via a simple co-precipitation method with the composition being controlled by altering the precursor ratio to 1:1 1:2 and 1:3 (Cu:Co) to investigate the effects of composition changes. The effect of the ratio of Cu2+/Co3+ and the degree of oxidation during the co-precipitation and annealing steps on the crystal structure morphology and electrocatalytic properties of the produced CCO NPs were studied. The CCO1:2 electrode exhibited an outstanding performance and high stability owing to the suitable electrochemical kinetics which was provided by the presence of sufficient Co3+ as active sites for oxygen evolution and the uniform sizes of the NPs in the half cell. Furthermore single cell tests were performed to confirm the possibility of using the synthesized electrocatalyst in a practical water splitting system. The CCO1:2 electrocatalyst was used as an anode to develop an anion exchange membrane water electrolyzer (AEMWE) cell. The full cell showed stable hydrogen production for 100 h with an energetic efficiency of >71%. In addition it was possible tomass produce the uniform highly active electrocatalyst for such applications through the co-precipitation method.
Storable Energy Production from Wind over Water
Apr 2020
Publication
The current status of a project is described which aims to demonstrate the technical and economic feasibility of converting the vast wind energy available over the globe’s oceans and lakes into storable energy. To this end autonomous high-performance sailing ships are equipped with hydrokinetic turbines whose output is stored either in electric batteries or is fed into electrolysers to produce hydrogen which then is compressed and stored in tanks. In the present paper the previous analytical studies which showed the potential of this “energy ship concept” are summarized and progress on its hardware demonstration is reported involving the conversion of a model sailboat to autonomous operation. The paper concludes with a discussion of the potential of this concept to achieve the IPCC-mandated requirement of reducing the global CO2 emissions by about 45% by 2030 reaching net zero by 2050.
Electrosynthesized Ni-P Nanospheres with High Activity and Selectivity Towards Photoelectrochemical Plastics Reforming
May 2021
Publication
Photoelectrochemical reforming of plastic waste offers an environmentally-benign and sustainable route for hydrogen generation. Nonetheless little attention was paid to develop electrocatalysts that can efficiently and selectively catalyze oxidative transformation of valueless plastic wastes into valued chemicals. Herein we report on facile electrosynthesis of nickel-phosphorus nanospheres (nanoNi-P) and their versatility in catalyzing hydrogen generation water oxidation and reforming of polyethylene terephthalate (PET). Notably composite of nanoNi-P with carbon nanotubes (CNT/nanoNi-P) requires −180 mV overpotential to drive hydrogen generation at -100 mA cm−2. Besides CV-activated nanoNi-P (nanoNi-P(CV)) was shown to be capable of reforming PET into formate with high selectivity (Faradic efficiency= ∼100 %). Efficient and selective generation of hydrogen and formate from PET reforming is realized utilizing an Earth-abundant photoelectrochemical platform based on nanoNi-P(CV)-modified TiO2 nanorods photoanode and CNT/nanoNi-P cathode. This work paves a path for developing artificial leaf for simultaneous environmental mitigation and photosynthesis of renewable fuels and valued chemicals.
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.
Volumetric Analysis Technique for Analyzing the Transport Properties of Hydrogen Gas in Cylindrical-shaped Rubbery Polymers
Mar 2021
Publication
We report volumetric analysis techniques to analyze the transport properties of hydrogen dissolved in cylindrical-shaped polymers. The techniques utilize the volume measurement of the released hydrogen from rubber by gas collection in a graduated cylinder after charging sample with high-pressure hydrogen and subsequent decompression. We further improve the graduated cylinder with some modifications such as reading the electrical capacitance of the water level using electrodes and changing the sample loading position. From the measurement results the uptake (C∞) diffusion coefficient (D) and solubility (S) of hydrogen are quantified with an upgraded diffusion analysis program. These methods are applied to three cylindrical rubbers. Dual adsorption behaviors with increasing pressure are observed for all the samples. C∞ follows Henry’s law up to ~15 MPa whereas Langmuir model applies up to 90 MPa. D shows Knudsen and bulk diffusion behavior below and above pressure respectively. A COMSOL simulation is compared with experimental observations.
Synthesizing the High Surface Area g-C3N4 for Greatly Enhanced Hydrogen Production
Jul 2021
Publication
Adjusting the structure of g-C3N4 to significantly enhance its photocatalytic activity has attracted considerable attention. Herein a novel sponge-like g-C3N4 with a porous structure is prepared from the annealing of protonated melamine under N2/H2 atmosphere (PH-CN). Compared to bulk g-C3N4 via calcination of melamine under ambient atmosphere (B-CN) PH-CN displays thinner nanosheets and a higher surface area (150.1 m2/g) which is a benefit for shortening the diffusion distance of photoinduced carriers providing more active sites and finally favoring the enhancement of the photocatalytic activity. Moreover it can be clearly observed from the UV-vis spectrum that PH-CN displays better performance for harvesting light compared to B-CN. Additionally the PH-CN is prepared with a larger band gap of 2.88 eV with the Fermi level and conduction band potential increased and valence band potential decreased which could promote the water redox reaction. The application experiment results show that the hydrogen evolution rate on PH-CN was nearly 10 times higher than that of B-CN which was roughly 4104 μmol h−1 g−1. The method shown in this work provides an effective approach to adjust the structure of g-C3N4with considerable photocatalytic hydrogen evolution activity.
Hydrous Hydrazine Decomposition for Hydrogen Production Using of Ir/CeO2: Effect of Reaction Parameters on the Activity
May 2021
Publication
In the present work an Ir/CeO2 catalyst was prepared by the deposition–precipitation method and tested in the decomposition of hydrazine hydrate to hydrogen which is very important in the development of hydrogen storage materials for fuel cells. The catalyst was characterised using different techniques i.e. X-ray photoelectron spectroscopy (XPS) transmission electron microscopy (TEM) scanning electron microscopy (SEM) equipped with X-ray detector (EDX) and inductively coupled plasma—mass spectroscopy (ICP-MS). The effect of reaction conditions on the activity and selectivity of the material was evaluated in this study modifying parameters such as temperature the mass of the catalyst stirring speed and concentration of base in order to find the optimal conditions of reaction which allow performing the test in a kinetically limited regime.
In Situ Neutron Radiography Investigations of Hydrogen Related Processes in Zirconium Alloys
Jun 2021
Publication
In situ neutron radiography experiments can provide information about diffusive processes and the kinetics of chemical reactions. The paper discusses requirements for such investigations. As examples of the zirconium alloy Zircaloy-4 the hydrogen diffusion the hydrogen uptake during high-temperature oxidation in steam and the reaction in nitrogen/steam and air/steam atmospheres results of in situ neutron radiography investigations are reviewed and their benefit is discussed.
Hydrogen-Rich Gas Production from Two-Stage Catalytic Pyrolysis of Pine Sawdust with Nano-NiO/Al2O3 Catalyst
Feb 2022
Publication
Hydrogen production from biomass pyrolysis is economically and technologically attractive from the perspectives of energy and the environment. The two-stage catalytic pyrolysis of pine sawdust for hydrogen-rich gas production is investigated using nano-NiO/Al2O3 as the catalyst at high temperatures. The influences of residence time (0–30 s) and catalytic temperature (500–800 ◦C) on pyrolysis performance are examined in the distribution of pyrolysis products gas composition and gas properties. The results show that increasing the residence time decreased the solid and liquid products but increased gas products. Longer residence times could promote tar cracking and gas-phase conversion reactions and improve the syngas yield H2/CO ratio and carbon conversion. The nano-NiO/A12O3 exhibits excellent catalytic activity for tar removal with a tar conversion rate of 93% at 800 ◦C. The high catalytic temperature could significantly improve H2 and CO yields by enhancing the decomposition of tar and gas-phase reactions between CO2 and CH4 . The increasing catalytic temperature increases the dry gas yield and carbon conversion but decreases the H2/CO ratio and low heating value.
Hydrothermal Synthesis of Iridium-Substituted NaTaO3 Perovskites
Jun 2021
Publication
Iridium-containing NaTaO3 is produced using a one-step hydrothermal crystallisation from Ta2O5 and IrCl3 in an aqueous solution of 10 M NaOH in 40 vol% H2O2 heated at 240 °C. Although a nominal replacement of 50% of Ta by Ir was attempted the amount of Ir included in the perovskite oxide was only up to 15 mol%. The materials are formed as crystalline powders comprising cube-shaped crystallites around 100 nm in edge length as seen by scanning transmission electron microscopy. Energy dispersive X-ray mapping shows an even dispersion of Ir through the crystallites. Profile fitting of powder X-ray diffraction (XRD) shows expanded unit cell volumes (orthorhombic space group Pbnm) compared to the parent NaTaO3 while XANES spectroscopy at the Ir LIII-edge reveals that the highest Ir-content materials contain Ir4+. The inclusion of Ir4+ into the perovskite by replacement of Ta5+ implies the presence of charge-balancing defects and upon heat treatment the iridium is extruded from the perovskite at around 600 °C in air with the presence of metallic iridium seen by in situ powder XRD. The highest Ir-content material was loaded with Pt and examined for photocatalytic evolution of H2 from aqueous methanol. Compared to the parent NaTaO3 the Ir-substituted material shows a more than ten-fold enhancement of hydrogen yield with a significant proportion ascribed to visible light absorption.
Analysis of Photon-driven Solar-to-hydrogen Production Methods in the Netherlands
Oct 2021
Publication
Hydrogen is deemed necessary for the realization of a sustainable society especially when renewable energy is used to generate hydrogen. As most of the photon-driven hydrogen production methods are not commercially available yet this study has investigated the techno economic and overall performance of four different solar-to hydrogen methods and photovoltaics-based electrolysis methods in the Netherlands. It was found that the photovoltaics-based electrolysis is the cheapest option with production cost of 9.31 $/kgH2. Production cost based on photo-catalytic water splitting direct bio-photolysis and photoelectrochemical water splitting are found to be 18.32 $/kgH2 18.45 $/kgH2 and 18.98 $/kgH2 respectively. These costs are expected to drop significantly in the future. Direct bio-photolysis (potential cost of 3.10 $/kgH2) and photo-catalytic water splitting (3.12 $/kgH2) may become cheaper than photovoltaics-based electrolysis. Based on preferences of three fictional technology investors i.e. a short-term a green and a visionary investor the overall performance of these methods are determined. Photovoltaics-based electrolysis is the most ideal option with photoelectrochemical water splitting a complementary option. While photovoltaics-based electrolysis has an advantage on the short-term because it is a non-integrated energy system on the long-term this might lead to relatively higher cost and performance limitations. Photochemical water splitting are integrated energy systems and have an advantage on the long-term because they need a relatively low theoretical overpotential and benefit from increasing temperatures. Both methods show performance improvements by the use of quantum dots. Bio-photolysis can be self-sustaining and can use wastewater to produce hydrogen but sudden temperature changes could lead to performance decrease.
Converting Sewage Water into H2 Fuel Gas Using Cu/CuO Nanoporous Photocatalytic Electrodes
Feb 2022
Publication
This work reports on H2 fuel generation from sewage water using Cu/CuO nanoporous (NP) electrodes. This is a novel concept for converting contaminated water into H2 fuel. The preparation of Cu/CuO NP was achieved using a simple thermal combustion process of Cu metallic foil at 550 ◦C for 1 h. The Cu/CuO surface consists of island-like structures with an inter-distance of 100 nm. Each island has a highly porous surface with a pore diameter of about 250 nm. X-ray diffraction (XRD) confirmed the formation of monoclinic Cu/CuO NP material with a crystallite size of 89 nm. The prepared Cu/CuO photoelectrode was applied for H2 generation from sewage water achieving an incident to photon conversion efficiency (IPCE) of 14.6%. Further the effects of light intensity and wavelength on the photoelectrode performance were assessed. The current density (Jph) value increased from 2.17 to 4.7 mA·cm−2 upon raising the light power density from 50 to 100 mW·cm−2 . Moreover the enthalpy (∆H*) and entropy (∆S*) values of Cu/CuO electrode were determined as 9.519 KJ mol−1 and 180.4 JK−1 ·mol−1 respectively. The results obtained in the present study are very promising for solving the problem of energy in far regions by converting sewage water to H2 fuel.
The Potential of Green Ammonia Production to Reduce Renewable Power Curtailment and Encourage the Energy Transition in China
Apr 2022
Publication
The pursuing of inter-regional power transmission to address renewable power curtailment in China has resulted in disappointing gains. This paper evaluates the case of local green ammonia production to address this issue. An improved optimization-based simulation model is applied to simulate lifetime green manufacturing and the impacts of main institutional incentives and oxygen synergy on investment are analysed. Levelized cost of ammonia is estimated at around 820 USD/t which is about twice the present price. The operating rate ammonia price the electrical efficiency of electrolysers and the electricity price are found to be the key factors in green ammonia investment. Carbon pricing and value-added tax exemption exert obvious influences on the energy transition in China. A subsidy of approximately 450 USD/t will be required according to the present price; however this can be reduced by 100 USD/t through oxygen synergy. Compared to inter-regional power transmission green ammonia production shows both economic and environmental advantages. Therefore we propose an appropriate combination of both options to address renewable power curtailment and the integration of oxygen manufacturing into hydrogen production. We consider the findings and policy implications will contribute to addressing renewable power curtailment and boosting the hydrogen economy in China.
Hydrogen Production on Demand by Redox-mediated Electrocatalysis: A Kinetic Study
Aug 2020
Publication
Producing hydrogen from water using a redox mediator on solid electrocatalyst particles in a reactor offers several advantages over classical electrolysis in terms of safety membrane degradation purity and flexibility. Herein vanadium-mediated hydrogen evolution on a commercial and low-cost Mo2C electrocatalyst is studied through the development of a reaction kinetics model. Based on a proposed mechanistic reaction scheme we established a kinetic rate law dependent on the concentration of V2+ the state-of-charge of the vanadium electrolyte from a vanadium redox flow battery and the amount of available catalytic sites on solid Mo2C. Kinetic experiments in transient conditions reveals a first-order dependence on both the concentration of V2+ and the concentration of catalytic active sites and a power law with an exponential factor of 0.57 was measured on the molar ratio V2+/V3+ i.e. on the electrochemical driving force generated on the Mo2C particles. The kinetic rate law was validated by studying the rate of reaction in steady-state conditions using a specially developed rotating ring-disk device (RRD) methodology. The kinetic model was demonstrated to be a useful tool to predict the hydrogen production via the chemical oxidation of V2+ over Mo2C at low pH (> 1 M H2SO4). For a perspective the model was implemented in a semi-batch reactor. The simulations highlight the optimal state-of-charge (SOC) to carry out the reaction in an efficient way for a given demand in hydrogen.
Bibliometric Analysis of Global Trends around Hydrogen Production Based on the Scopus Database in the Period 2011–2021
Dec 2022
Publication
Given the increase in population and energy demand worldwide alternative methods have been adopted for the production of hydrogen as a clean energy source. This energy offers an alternative energy source due to its high energy content and without emissions to the environment. In this bibliometric analysis of energy production using electrolysis and taking into account the different forms of energy production. In this analysis it was possible to evaluate the research trends based on the literature in the Scopus database during the years 2011–2021. The results showed a growing interest in hydrogen production from electrolysis and other mechanisms with China being the country with the highest number of publications and the United States TOP in citations. The trend shows that during the first four years of this study (2011–2014) the average number of publications was 74 articles per year from 2015 to 2021 where the growth is an average of 209 articles the journal that published the most on this topic is Applied Energy followed by Energy contributing with almost 33% in the research area. Lastly the keyword analysis identified six important research points for future discussions which we have termed clusters. The study concludes that new perspectives on clean hydrogen energy generation environmental impacts and social acceptance could contribute to the positive evolution of the hydrogen energy industry.
Thermodynamic Assessment of the Novel Concept of the Energy Storage System Using Compressed Carbon Dioxide, Methanation and Hydrogen Generator
Jul 2021
Publication
The main aim of this paper is to characterize the concept of a novel energy storage system based on compressed CO2 storage installation that uses an infrastructure of depleted coal mines to provide required volume of tanks and additionally hydrogen generators and a methanation installation to generate synthetic natural gas that can be used within the system or taken out of it e.g. to a gas grid. A detailed mathematical model of the proposed solution was built using own codes and Aspen Plus software. Thermodynamic evaluation aiming at determining parameters composition and streams in all the most important nodes of the system for the nominal point and when changing a defined decision variable δ (in the range from 0.1 to 0.9) was made. The evaluation was made based on the storage efficiency volume of the tanks and flows of energy within the system. The storage efficiency in the nominal point reached 45.08% but was changing in the range from 35.06% (for δ = 0.1) to 63.93% (for δ = 0.9). For the nominal value of δ equal to 0.5 volume of the low-pressure tank (LPT) was equal to 132869 m3 while of the high pressure tank (HPT) to 1219 m3 . When changing δ these volumes were changing from 101900 m3 to 190878 m3 (for LPT) and from 935 to 1751 m3 (for HPT) respectively. Detailed results are presented in the paper and indicate high storage potential of the proposed solution in regions with underground mine infrastructure.
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