China, People’s Republic
Numerical Simulation of Hydrogen Release From High-Pressure Storage Vessel
Sep 2009
Publication
In this paper the deflagration region and characteristics of the hydrogen flow which was generated by high-pressure hydrogen discharge from storage vessels were studied. A 3-D analytic model is established based on the species transfer model and the SST k −ω turbulence model. The established model is applied to the research of the flow characteristics of the hydrogen under-expanded jet under different filling pressures of 30 MPa 35 MPa and 40 MPa respectively. The evolution process of hydrogen combustible cloud is analyzed under the filling pressure of 30 MPa. It is revealed that a supersonic jet is formed after the high-pressure hydrogen discharge outlet In the vicinity of the Mach disk the hydrogen jet velocity and temperature reach the maximum values and the variation of filling pressure has little effect on the peak values of the hydrogen jet flow velocity and temperature during the considered pressure range. In the rear of the Mach disk the variation rates of the hydrogen flow velocity and temperature are in inversely proportional to the hydrogen filling pressure. At the preliminary stage the discharged hydrogen is apple-shaped which expands along the radial and then the axial growth rate of the hydrogen cloud increases with the passage of time.
Hybrid Water Electrolysis: A New Sustainable Avenue for Energy-Saving Hydrogen Production
Oct 2021
Publication
Developing renewable energy-driven water splitting for sustainable hydrogen production plays a key role in achieving the carbon neutrality goal. Nevertheless the efficiency of traditional pure water electrolysis is severely hampered by the anodic oxygen evolution reaction (OER) due to its sluggish kinetics. In this context replacing OER with thermodynamically more favorable oxidation reactions to produce hydrogen via hybrid water electrolysis becomes an energy-saving hydrogen production scheme. Here the recent advances in hybrid water electrolysis are critically reviewed. First the fundamentals of electrochemical oxidation of typical organic molecules such as urea hydrazine and biomass are presented. Then the recent achievements in electrocatalysts for hybrid water electrolysis are introduced with an emphasis on outlining catalyst design strategies and the correlation between catalyst structure and performance. Finally future perspectives in this field for a sustainable hydrogen economy are proposed.
Study on Critical Technologies and Development Routes of Coal-based Hydrogen Energy
Jul 2019
Publication
Hydrogen is considered a secondary source of energy commonly referred to as an energy carrier. It has the highest energy content when compared to other common fuels by weight having great potential for further development. Hydrogen can be produced from various domestic resources but based on the fossil resource conditions in China coal-based hydrogen energy is considered to be the most valuable because it is not only an effective way to develop clean energy but also a proactive exploration of the clean usage of traditional coal resources. In this article the sorption-enhanced water–gas shift technology in the coal-to-hydrogen section and the hydrogen-storage and transport technology with liquid aromatics are introduced and basic mechanisms technical advantages latest progress and future R&D focuses of hydrogen-production and storage processes are listed and discussed. As a conclusion after considering the development frame and the business characteristics of CHN Energy Group a conceptual architecture for developing coal-based hydrogen energy and the corresponding supply chain is proposed.
Effect of α′ Martensite Content Induced by Tensile Plastic Prestrain on Hydrogen Transport and Hydrogen Embrittlement of 304L Austenitic Stainless Steel
Aug 2018
Publication
Effects of microstructural changes induced by prestraining on hydrogen transport and hydrogen embrittlement (HE) of austenitic stainless steels were studied by hydrogen precharging and tensile testing. Prestrains higher than 20% at 20 °C significantly enhance the HE of 304L steel as they induce severe α′ martensite transformation accelerating hydrogen transport and hydrogen entry during subsequent hydrogen exposure. In contrast 304L steel prestrained at 50 and 80 °C and 316L steel prestrained at 20 °C exhibit less HE due to less α′ after prestraining. The increase of dislocations after prestraining has a negligible influence on apparent hydrogen diffusivity compared with pre-existing α′. The deformation twins in heavily prestrained 304L steel can modify HE mechanism by assisting intergranular (IG) fracture. Regardless of temperature and prestrain level HE and apparent diffusivity ( Dapp ) increase monotonously with α′ volume fraction ( fα′ ). Dapp can be described as log Dapp=log(Dα′sα′/sγ)+log[fα′/(1−fα′)] for 10%<fα′<90% with Dα′ is diffusivity in α′ sα′ and sγ are solubility in α′ and austenite respectively. The two equations can also be applied to these more typical duplex materials containing both BCC and FCC phases.
Towards the Rational Design of Stable Electrocatalysts for Green Hydrogen Production
Feb 2022
Publication
Now it is time to set up reliable water electrolysis stacks with active and robust electro‐ catalysts to produce green hydrogen. Compared with catalytic kinetics much less attention has been paid to catalyst stability and the weak understanding of the catalyst deactivation mechanism restricts the design of robust electrocatalysts. Herein we discuss the issues of catalysts’ stability evaluation and characterization and the degradation mechanism. The systematic understanding of the degradation mechanism would help us to formulate principles for the design of stable catalysts. Particularly we found that the dissolution rate for different 3d transition metals differed greatly: Fe dissolves 114 and 84 times faster than Co and Ni. Based on this trend we designed Fe@Ni and FeNi@Ni core‐shell structures to achieve excellent stability in a 1 A cm−2 current density as well as good catalytic activity at the same time
Towards Global Cleaner Energy and Hydrogen Production: A Review and Application ORC Integrality with Multigeneration Systems
Apr 2022
Publication
The current evidential effect of carbon emissions has become a societal challenge and the need to transition to cleaner energy sources/technologies has attracted wide research attention. Technologies that utilize low-grade heat like the organic Rankine cycle (ORC) and Kalina cycle have been proposed as viable approaches for fossil reduction/carbon mitigation. The development of renewable energy-based multigeneration systems is another alternative solution to this global challenge. Hence it is important to monitor the development of multigeneration energy systems based on low-grade heat. In this study a review of the ORC’s application in multigeneration systems is presented to highlight the recent development in ORC integrality/application. Beyond this a new ORC-CPVT (concentrated photovoltaic/thermal) integrated multigeneration system is also modeled and analyzed using the thermodynamics approach. Since most CPVT systems integrate hot water production in the thermal stem the proposed multigeneration system is designed to utilize part of the thermal energy to generate electricity and hydrogen. Although the CPVT system can achieve high energetic and exergetic efficiencies while producing thermal energy and electricity these efficiencies are 47.9% and 37.88% respectively for the CPVT-ORC multigeneration configuration. However it is noteworthy that the electricity generation from the CPVT-ORC configuration in this study is increased by 16%. In addition the hot water cooling effect and hydrogen generated from the multigeneration system are 0.4363 L/s 161 kW and 1.515 L/s respectively. The environmental analysis of the system also shows that the carbon emissions reduction potential is enormous.
Intelligent Natural Gas and Hydrogen Pipeline Dispatching Using the Coupled Thermodynamics-Informed Neural Network and Compressor Boolean Neural Network
Feb 2022
Publication
Natural gas pipelines have attracted increasing attention in the energy industry thanks to the current demand for green energy and the advantages of pipeline transportation. A novel deep learning method is proposed in this paper using a coupled network structure incorporating the thermodynamics-informed neural network and the compressor Boolean neural network to incorporate both functions of pipeline transportation safety check and energy supply predictions. The deep learning model is uniformed for the coupled network structure and the prediction efficiency and accuracy are validated by a number of numerical tests simulating various engineering scenarios including hydrogen gas pipelines. The trained model can provide dispatchers with suggestions about the number of phases existing during the transportation as an index showing safety while the effects of operation temperature pressure and compositional purity are investigated to suggest the optimized productions.
Ordered Clustering of Single Atomic Te Vacancies in Atomically Thin PtTe2 Promotes Hydrogen Evolution Catalysis
Apr 2021
Publication
Exposing and stabilizing undercoordinated platinum (Pt) sites and therefore optimizing their adsorption to reactive intermediates offers a desirable strategy to develop highly efficient Pt-based electrocatalysts. However preparation of atomically controllable Pt-based model catalysts to understand the correlation between electronic structure adsorption energy and catalytic properties of atomic Pt sites is still challenging. Herein we report the atomically thin two-dimensional PtTe2 nanosheets with well-dispersed single atomic Te vacancies (Te-SAVs) and atomically well-defined undercoordinated Pt sites as a model electrocatalyst. A controlled thermal treatment drives the migration of the Te-SAVs to form thermodynamically stabilized ordered Te-SAV clusters which decreases both the density of states of undercoordinated Pt sites around the Fermi level and the interacting orbital volume of Pt sites. As a result the binding strength of atomically defined Pt active sites to H intermediates is effectively reduced which renders PtTe2 nanosheets highly active and stable in hydrogen evolution reaction.
Study on Flake Formation Behavior and Its Influence Factors in Cr5 Steel
Apr 2018
Publication
A flake is a crack that is induced by trapped hydrogen within steel. To study its formation mechanism previous studies mostly focused on the formation process and magnitude of hydrogen pressure in hydrogen traps such as cavities and cracks. However according to recent studies the hydrogen leads to the decline of the mechanical properties of steel which is known as hydrogen embrittlement is another reason for flake formation. In addition the phenomenon of stress induced hydrogen uphill diffusion should not be neglected. All of the three behaviors are at work simultaneously. In order to further explore the formation mechanism of flakes in steel the process of flake initiation and growth were studied with the following three coupling factors: trap hydrogen pressure hydrogen embrittlement and stress induced hydrogen re-distribution. The analysis model was established using the finite element method and a crack whose radius is 0.5 mm was set in its center. The cohesive method and Bilinear Traction Separate Law (BTSL) were used to address the coupling effect. The results show that trap hydrogen pressure is the main driving force for flake formation. After the high hydrogen pressure was generated around the trap a stress field formed. In addition the trap is the center of stress concentration. Then hydrogen is concentrated in a distribution around this trap and most of the steel mechanical properties are reduced. The trap size is a key factor for defining the critical hydrogen content for flake formation and propagation. However when the trap size exceeds the specified value the critical hydrogen content does not change any more. As for the crack whose radius is 0.5 mm the critical hydrogen content of Cr5VMo steel is 2.2 ppm which is much closer to the maximum safe hydrogen concentration of 2.0 ppm used in China. The work presented in this article increases our understanding of flake formation and propagation mechanisms in steel.
Velocity Measurements of Hydrogen Jets Using the Optical Flow Method
Sep 2021
Publication
Concentration and velocity measurements are crucial for developing and validating hydrogen jet models which provide scientific bases for hydrogen safety analyses. The concentration fields have been visualized and accurately measured using laser diagnostic methods based on lase Rayleigh and Raman scattering techniques. However the velocity measurements are more challenging. Particle image velocimetry (PIV) has been commonly used for measuring velocities in turbulent flows by seeding tracer particles into the flow and assuming the particles intimately following the flow. However sometimes the particle seeding is difficult or disturbs the flow. Moreover simultaneously concentration and velocity measurements are very difficult when using PIV systems to measure the velocities. Therefore the optical flow velocimetry (OFV) method was used to resolve the velocity fields from the scalar fields or particle images of hydrogen jets. In the present work the velocity field and particle images of hydrogen jets were simulated using FLUENT with the large eddy simulation (LES) model and the particle images were then used to resolve the velocity field by the OFV method. The OFV results were compared with the CFD simulations to verify their accuracy. The results show that the OFC method was an efficient low-cost way to extract the velocity fields from particle images. The OFV method accurately located the large vortices in the flow and the velocity distribution of the high-velocity gradients regions was consistent with the CFD results. The present study lays a foundation for using the OFV method to directly resolve the velocity fields from the concentration fields of hydrogen jets measured by laser diagnostics.
Effect of Deformation Microstructures on Hydrogen Embrittlement Sensitivity and Failure Mechanism of 304 Austenitic Stainless Steel: The Significant Role of Rolling Temperature
Feb 2022
Publication
Metastable austenitic stainless steels (ASSs) have excellent ductility but low strength so that their usage as load-bearing components is significantly limited. Rolling is an effective method of increasing strength whereas the effect of rolling temperature on microstructural evolution the hydrogen embrittlement (HE) sensitivity and fracture mechanisms is still unclear. In present study the effect of cold/warm rolling on detailed microstructural characteristics of 304 ASS was quantitatively investigated and the corresponding HE sensitivity was evaluated via slow strain rate test. The results suggest that cold-rolling led to high strength but poor plasticity and deteriorated HE sensitivity while warm-rolled samples provided combination of high strength and ductility and also superior HE resistance. Compared with 18% α′-martensite in cold -rolled steel warm-rolled specimens consisted of complete austenite less twins and lower dislocation density,moreover the favorable {112} ND and {110} ND textures replaced the harmful {001} ND texture. Based on in-situ EBSD observation during SSRT the HE sensitivity was governed by the combined effect of pre-deformation microstructures and the dynamic microstructural evolution. Advanced method of time-of-flight secondary ion mass spectrometry was used to observe the distribution of hydrogen and the hydrogen content of specimens was determined by the gas chromatograph thermal desorption analysis method. An exceedingly small amount of hydrogen entered the warm-rolled samples while a large amount of hydrogen was trapped at grain boundaries of cold-rolled sample leading to complete intergranular fracture. Therefore warm rolling is an effective pathway for obtaining high combination of strength and ductility together with excellent HE sensitivity.
Comparison of Two-layer Model for High Pressure Hydrogen Jets with Notional Nozzle Model Predictions and Experimental Data
Oct 2015
Publication
A two-layer reduced order model of high pressure hydrogen jets was developed which includes partitioning of the flow between the central core jet region leading to the Mach disk and the supersonic slip region around the core. The flow after the Mach disk is subsonic while the flow around the Mach disk is supersonic with a significant amount of entrained air. This flow structure significantly affects the hydrogen concentration profiles downstream. The predictions of this model are compared to previous experimental data for high pressure hydrogen jets up to 20 MPa and to notional nozzle models and CFD models for pressures up to 35 MPa using ideal gas properties. The results show that this reduced order model gives better predictions of the mole fraction distributions than previous models for highly underexpanded jets. The predicted locations of the 4% lower flammability limit also show that the two-layer model much more accurately predicts the measured locations than the notional nozzle models. The comparisons also show that the CFD model always underpredicts the measured mole fraction concentrations.
Effects of Oxidants on Hydrogen Spontaneous Ignition: Experiments and Modelling
Sep 2017
Publication
Experiments were performed on the influence of oxidants (air pure oxygen O2 and pure nitrous oxide N2O at atmospheric pressure) in the straight expansion tube after the burst disk on the hydrogen spontaneous ignition. The lowest pressure at which the spontaneous ignition is observed has been researched for a 4 mm diameter tube with a length of 10 cm for the two oxidant gases. The ignition phenomenon is observed with a high speed camera and the external overpressures are measured. Numerical simulations have also been conducted with the high resolution CFD approach detailed chemistry formerly developed by Wen and co-workers. Comparison is made between the predictions and the experimental data.
Risk Assessment on Life Safety and Financial Loss for Road Accident of Fuel Cell Vehicles
Sep 2017
Publication
Vehicular use of hydrogen is the first attempt to apply hydrogen energy in consumers’ environment in large scale and has raised safety concerns in both public authorities and private bodies such as fire services and insurance companies. This paper analyzes typical accident progressions of hydrogen fuel cell vehicles in a road collision accident. Major hydrogen consequences including impinging jet fires and catastrophic tank ruptures are evaluated separately in terms of accident duration and hazard distances. Results show that in a 70 MPa fuel cell car accident the hazards associated with hydrogen releases would normally last for no more than 1.5 min due to the empty of the tank. For the safety of general public a perimeter of 100 m is suggested in the accident scene if no hissing sound is heard. However the perimeter can be reduced to 10 m once the hissing sound of hydrogen release is heard. Furthermore risks of fatalities injuries and damages are all quantified in financial terms to assess the impacts of the accident. Results show that costs of fatalities and injuries contribute most to the overall financial loss indicating that the insurance premium of fatalities and injuries should be set higher than that of property loss.
Mn-based Borohydride Synthesized by Ball-milling KBH4 and MnCl2 for Hydrogen Storage
Dec 2013
Publication
In this work a mixed-cation borohydride (K2Mn(BH4)4) with P21/n structure was successfully synthesized by mechanochemical milling of the 2KBH4–MnCl2 sample under argon. The structural and thermal decomposition properties of the borohydride compounds were investigated using XRD Raman spectroscopy FTIR TGA-MS and DSC. Apart from K2Mn(BH4)4 the KMnCl3 and unreacted KBH4 compounds were present in the milled 2KBH4–MnCl2. The two mass loss regions were observed for the milled sample: one was from 100 to 160 °C with a 1.6 ± 0.1 wt% loss (a release of majority hydrogen and trace diborane) which was associated with the decomposition of K2Mn(BH4)4 to form KBH4 boron and finely dispersed manganese; the other was from 165 to 260 °C with a 1.9 ± 0.1 wt% loss (only hydrogen release) which was due to the reaction of KBH4 with KMnCl3 to give KCl boron finely dispersed manganese. Simultaneously the formed KCl could dissolve in KBH4 to yield a K(BH4)xCl1−x solid solution and also react with KMnCl3 to form a new compound K4MnCl6.
Estimation of Filling Time for Compressed Hydrogen Refueling
Mar 2019
Publication
In order to facilitate the application of hydrogen energy and ensure its safety the compressed hydrogen storage tank on board needs to be full of hydrogen gas within 3 minutes. Therefore to meet this requirement the effects of refueling parameters on the filling time need to be investigated urgently. For the purpose of solving this issue a novel analytical solution of filling time is obtained from a lumped parameter model in this paper. According to the equation of state for real gas and dimensionless numbers Nu and Re the function relationships between the filling time and the refueling parameters are presented. These parameters include initial temperature initial pressure inflow temperature final temperature and final pressure. These equations are used to fit the reference data the results of fitting show good agreement. Then the values of fitting parameters are further utilized so as to verify the validity of these formulas. We believe this study can contribute to control the hydrogen filling time and ensure the safety during fast filling process.
Blending Ammonia into Hydrogen to Enhance Safety through Reduced Burning Velocity
Sep 2019
Publication
Laminar burning velocities (SL) of hydrogen/ammonia mixtures in air at atmospheric pressure were studied experimentally and numerically. The blending of hydrogen with ammonia two fuels that have been proposed as promising carriers for renewable energy causes the laminar flame speed of the mixture SL to decrease significantly. However details of this have not previously available. Systematic measurements were therefore performed for a series of hydrogen/ammonia mixtures with wide ranges of mole fractions of blended ammonia (XNH3) and equivalence ratio using a heat flux method based on heat flux of a flat flame transferred to the burner surface. It was found that the mixture of XNH3 = 40% has a value of SL close to that of methane which is the dominant component of natural gas. Using three chemical kinetic mechanisms available in the literature i.e. the well-known GRI-Mech 3.0 mechanism and two mechanisms recently released SL were also modelled for the cases studied. However the discrepancies between the experimental and numerical results can exceed 50% with the GRI-Mech 3.0 mechanism. Discrepancies were also found between the numerical results obtained with different mechanisms. These results can contribute to an increase in both the safety and efficiency of the coutilization of these two types of emerging renewable fuel and to guiding the development of better kinetic models.
Improving Hydrogen Embrittlement Resistance of Hot-Stamped 1500 MPa Steel Parts That Have Undergone a Q&P Treatment by the Design of Retained Austenite and Martensite Matrix
Nov 2020
Publication
Hydrogen embrittlement is one of the largest obstacles against the commercialisation of ultra-high strength quenching and partitioning (Q&P) steels with ultimate tensile strength over 1500 MPa including the hot stamped steel parts that have undergone a Q&P treatment. In this work the influence of partitioning temperature on hydrogen embrittlement of ultra-high strength Q&P steels is studied by pre-charged tensile tests with both dog-bone and notched samples. It is found that hydrogen embrittlement resistance is enhanced by the higher partitioning temperature. Then the hydrogen embrittlement mechanism is analysed in terms of hydrogen retained austenite and martensite matrix. Thermal desorption analysis (TDA) shows that the hydrogen trapping properties are similar in the Q&P steels which cannot explain the enhancement of hydrogen embrittlement resistance. On the contrary it is found that the relatively low retained austenite stability after the higher temperature partitioning ensures more sufficient TRIP effect before hydrogen-induced fracture. Additionally dislocation recovery and solute carbon depletion at the higher partitioning temperature can reduce the flow stress of the martensite matrix improving its intrinsic toughness and reducing its hydrogen sensitivity both of which result in the higher hydrogen embrittlement resistance.
Conceptual Design of Pyrolytic Oil Upgrading Process Enhanced by Membrane-Integrated Hydrogen Production System
May 2019
Publication
Hydrotreatment is an efficient method for pyrolytic oil upgrading; however the trade-off between the operational cost on hydrogen consumption and process profit remains the major challenge for the process designs. In this study an integrated process of steam methane reforming and pyrolytic oil hydrotreating with gas separation system was proposed conceptually. The integrated process utilized steam methane reformer to produce raw syngas without further water–gas-shifting; with the aid of a membrane unit the hydrogen concentration in the syngas was adjusted which substituted the water–gas-shift reactor and improved the performance of hydrotreater on both conversion and hydrogen consumption. A simulation framework for unit operations was developed for process designs through which the dissipated flow in the packed-bed reactor along with membrane gas separation unit were modelled and calculated in the commercial process simulator. The evaluation results showed that the proposed process could achieve 63.7% conversion with 2.0 wt% hydrogen consumption; the evaluations of economics showed that the proposed process could achieve 70% higher net profit compared to the conventional plant indicating the potentials of the integrated pyrolytic oil upgrading process.
To Adopt CCU Technology or Not? An Evolutionary Game between Local Governments and Coal-Fired Power Plants
Apr 2022
Publication
Carbon dioxide capture and utilization (CCU) technology is a significant means by which China can achieve its ambitious carbon neutrality goal. It is necessary to explore the behavioral strategies of relevant companies in adopting CCU technology. In this paper an evolutionary game model is established in order to analyze the interaction process and evolution direction of local governments and coal-fired power plants. We develop a replicator dynamic system and analyze the stability of the system under different conditions. Based on numerical simulation we analyze the impact of key parameters on the strategies of stakeholders. The simulation results show that the unit prices of hydrogen and carbon dioxide derivatives have the most significant impact: when the unit price of hydrogen decreases to 15.9 RMB/kg or the unit price of carbon dioxide derivatives increases to 3.4 RMB/kg the evolutionary stabilization strategy of the system changes and power plants shift to adopt CCU technology. The results of this paper suggest that local governments should provide relevant support policies and incentives for CCU technology deployment as well as focusing on the synergistic development of CCU technology and renewable energy hydrogen production technology
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