China, People’s Republic
Hydrogen Trapping Behavior in Vanadium Microalloyed TRIP-Assisted Annealed Martensitic Steel
Jun 2019
Publication
Transformation induced plasticity (TRIP)-assisted annealed martensitic (TAM) steel combines higher tensile strength and elogangtion and has been increasingly used but appears to bemore prone to hydrogen embrittlement (HE). In this paper the hydrogen trapping behavior and HE of TRIP-assisted annealed martensitic steels with different vanadium additions had been investigated by means of hydrogen charging and slow strain rate tensile tests (SSRT) microstructral observartion and thermal desorption mass spectroscope (TDS). Hydrogen charging test results indicates that apparent hydrogen diffusive index Da is 1.94 × 10−7/cm2·s−1 for 0.21 wt.% vanadium steel while the value is 8.05 × 10−7/cm2·s−1 for V-free steel. SSRT results show that the hydrogen induced ductility loss ID is 76.2% for 0.21 wt.%V steel compared with 86.5% for V-free steel. The trapping mechanism of the steel containing different V contents is analyzed by means of TDS and Transmission electron microscope (TEM) observations. It is found out that the steel containing 0.21 wt.%V can create much more traps for hydrogen trapping compared with lower V steel which is due to vanadium carbide (VC) precipitates acting as traps capturing hydrogen atoms.The relationship between hydrogen diffusion and hydrogentrapping mechanism is discussed in details.
Numerical Solution for Thermodynamic Model of Charge-discharge Cycle in Compressed Hydrogen Tank
Mar 2019
Publication
The safety and convenience of hydrogen storage are significant for fuel cell vehicles. Based on mass conservation equation and energy conservation equation two thermodynamic models (single zone model and dual zone model) have been established to study the hydrogen gas temperature and tank wall temperature for compressed hydrogen storage tank. With two models analytical solution and Euler solution for single zone (gas zone) charge-discharge cycle have been compared Matlab/Simulink solution and Euler solution for dual zone (gas zone wall zone) charge-discharge cycle have been compared. Three charge-discharge cycle cases (Case 1 constant inflow temperature; Case 2 variable inflow temperature; Case 3 constant inflow temperature variable outflow temperature) and two compressed hydrogen tanks (Type III 25L Type IV 99L) charge-discharge cycle are studied by Euler method. Results show Euler method can well predict hydrogen temperature and tank wall temperature.
A Numerical Simulation on the Leakage Event of a High-Pressure Hydrogen Dispenser
Dec 2021
Publication
For the sake of the increasing demand of hydrogen fuel cell vehicles there are more concerns on the safety of hydrogen refueling stations. As one of the key pieces of equipment the hydrogen dispenser has drawn attention on this aspect since it involves massive manual operations and may be bothered by a high probability of failure. In this paper a numerical study is conducted to simulate the possible leakage events of the hydrogen dispenser based on a prototype in China whose working pressure is 70 MPa. The leakage accident is analyzed with respect to leakage sizes leak directions and the time to stop the leakage. It is found that due to the large mass flow rate under such high pressure the leak direction and the layout of the components inside the dispenser become insignificant and the ignitable clouds will form inside the dispenser in less than 1 s if there is a leakage of 1% size of the main tube. The ignitable clouds will form near the vent holes outside the dispenser which may dissipate quickly if the leakage is stopped. On the other hand the gas inside the dispenser will remain ignitable for a long time which asks for a design with no possible ignition source inside. The results can be useful in optimizing the design of the dispenser regarding the reaction time and sensitivity requirements of the leakage detector the size and amount of vent holes etc.
Recent Progress in the Steam Reforming of Bio-Oil for Hydrogen Production: A Review of Operating Parameters, Catalytic Systems and Technological Innovations
Dec 2021
Publication
The present review focuses on the production of renewable hydrogen through the catalytic steam reforming of bio-oil the liquid product of the fast pyrolysis of biomass. Although in theory the process is capable of producing high yields of hydrogen in practice certain technological issues require radical improvements before its commercialization. Herein we illustrate the fundamental knowledge behind the technology of the steam reforming of bio-oil and critically discuss the major factors influencing the reforming process such as the feedstock composition the reactor design the reaction temperature and pressure the steam to carbon ratio and the hour space velocity. We also emphasize the latest research for the best suited reforming catalysts among the specific groups of noble metal transition metal bimetallic and perovskite type catalysts. The effect of the catalyst preparation method and the technological obstacle of catalytic deactivation due to coke deposition metal sintering metal oxidation and sulfur poisoning are addressed. Finally various novel modified steam reforming techniques which are under development are discussed such as the in-line two-stage pyrolysis and steam reforming the sorption enhanced steam reforming (SESR) and the chemical looping steam reforming (CLSR). Moreover we argue that while the majority of research studies examine hydrogen generation using different model compounds much work must be done to optimally treat the raw or aqueous bio-oil mixtures for efficient practical use. Moreover further research is also required on the reaction mechanisms and kinetics of the process as these have not yet been fully understood.
Experimental Study on Hydrogen/Air Premixed Flame Propagation in Closed Rectangular Channels
Sep 2019
Publication
An experimental study of hydrogen/air premixed flame propagation in a closed rectangular channel with the inhibitions (N2 or CO2) was conducted to investigate the inhibiting effect of N2 and CO2 on the flame properties during its propagation. Both Schlieren system and the pressure sensor were used to capture the evolution of flame shape and pressure changes in the channel. It was found that both N2 and CO2 have considerable inhibiting effect on hydrogen/air premixed flames. Compared with N2 CO2 has more prominent inhibition which has been interpreted from thermal and kinetic standpoints. In all the flames the classic tulip shape was observed. With different inhibitor concentration the flame demonstrated three types of deformation after the classic tulip inversion. A simple theoretical analysis has also been conducted to indicate that the pressure wave generated upon the first flame-wall contact can affect the flame deformation depending on its meeting moment with the flame front. Most importantly the meeting moment is always behind the start of tulip inversion which suggests the non-dominant role of pressure wave on this featured phenomenon.
Numerical Simulation of Homogenous/Inhomogeneous Hydrogen-air Explosion in a Rectangular Channel
Sep 2019
Publication
Hydrogen is one of the promising energy sources in the future because it has the advantages of clean combustion products high efficiency and renewable energy. However hydrogen has the characteristics of low ignition energy wide flammable range (4% -75%) and fast burning flame speed which can cause explosion hazards. Typically the accidental release of hydrogen into confined or semi confined enclosures can often lead to a flammable hydrogen-air mixture with concentration gradients and possible flame acceleration and deflagration-to-detonation transition (DDT). The present study aims to test the capability of our in-house density-based solver ExplosionEngFoam for flame acceleration (FA) and deflagration-to-detonation transition (DDT) in homogenous/inhomogeneous hydrogen-air mixtures. The solver is based on the open source computational fluid dynamics (CFD) platform OpenFOAM and uses the modified Weller et al.’s combustion model taking into account LD and RT instabilities turbulence and non-unity Lewis number etc. Numerical simulations were conducted for both homogeneous and inhomogeneous mixtures in a long enclosed channel with 5.4 m in length and 0.06 m in height. The predictions demonstrate good quantitative agreement with the experimental measurements in flame tip position speed and pressure profiles by Boeck et al. The flow characteristics such as flame fine structure wave evolution etc. were also discussed.
Voltammetric and Galvanostatic Methods for Measuring Hydrogen Crossover in Fuel Cell
Dec 2021
Publication
Hydrogen crossover rate is an important indicator for characterizing the membrane degradation and failure in proton exchange membrane fuel cell. Several electrochemical methods have been applied to quantify it. But most of established methods are too rough to support follow-up applications. In this paper a systematic and consistent theoretical foundation for electrochemical measurements of hydrogen crossover is established for the first time. Different electrochemical processes occurring throughout the courses of applying potentiostatic or galvanostatic excitations on fuel cell are clarified and the linear current–voltage behavior observed in the steady-state voltammogram is reinterpreted. On this basis we propose a modified galvanostatic charging method with high practicality to achieve accurate electrochemical measurement of hydrogen crossover and the validity of this method is fully verified. This research provides an explicit framework for implementation of galvanostatic charging method and offers deeper insights into the principles of electrochemical methods for measuring hydrogen crossover.
An Ammonia-Hydrogen Energy Roadmap for Carbon Neutrality: Opportunity and Challenges in China
Nov 2021
Publication
China has promised to reach the peak carbon dioxide emission (ca. 10 billion tons) by 2030 and carbon neutrality by 2060. To realize these goals it is necessary to develop hydrogen energy and fuel cell techniques. However the high cost and low intrinsic safety of high-pressure hydrogen storage limit their commercialization. NH3 is high in hydrogen content easily liquefied at low pressure and free of carbon and the technology of NH3 synthesis has been commercialized nationwide. It is worth noting that the production of NH3 in China is about 56 million tons per year accounting for 35% of worldwide production. Hence with the well established infrastructure for NH3 synthesis and transportation and the demand for clean energy in China it is feasible to develop a green and economical energy roadmap viz. “Clean low-pressure NH3 synthesis → Safe and economical NH3 storage and transportation → Carbon-free efficient NH3-H2 utilization” for low-carbon or even carbon-free energy production.<br/>Currently the academic and industrial communities in China are striving to make technological breakthroughs in areas such as photocatalytic water splitting electrocatalytic water splitting mild-condition NH3 synthesis low-temperature NH3 catalytic decomposition and indirect or direct NH3 fuel cells with significant progress.<br/>Taking full advantage of the NH3 synthesis industry and readjusting the industrial structure it is viable to achieve energy saving and emission reduction in NH3 synthesis industry (440 million tons CO2 per year) as well as promote a new energy industry and ensure national energy security. Therefore relevant academic and industrial communities should put effort on mastering the key technologies of “Ammonia-Hydrogen” energy conversion and utilization with complete self-dependent intellectual property. It is envisioned that through the establishment of “Renewable Energy-Ammonia-Hydrogen” circular economy a green technology chain for hydrogen energy industry would pose as a promising pathway to achieve the 2030 and 2060 goals.
Formation and Dissociation Behaviour Studies of Hydrogen Hydrate in the Presence of Tetrahydrofuran by using High Pressure DSC
Mar 2019
Publication
Significant challenges still remain in the development of suitable materials for storing hydrogen for practical applications. Clathrate hydrates as a special inclusion compounds could be tailored by changing the storage pressure and temperature to adapt ambient conditions. In this work the hydrates were adopted to encage hydrogen in tetrahydrofuran (THF) aqueous solution with concentration of 3.0 mol%. The formation and dissociation behaviours were investigated by a high pressure micro-differential scanning calorimeter at the operating pressure of 18 MPa 25 MPa and 34 MPa. Experimental results show that the memory water only affects the hydrate formation behaviour instead of the hydrate dissociation behaviour. The dissociation temperature of the THF-H2 hydrate increases with the increase of the operating pressure and its dissociation equilibrium data can be obtained. The dissociation temperatures of the THF-H2 hydrate are 9.26 ℃ 10.94 ℃ and 12.67 ℃ at the operating pressure of 18 MPa 25 MPa and 34 MPa respectively. It is fundamental for performing the kinetics and microscopic experiments.
Investigating the Hydrogen Storage Capacity of Surfactant Modified Graphene
Mar 2019
Publication
As the depletion of traditional fossil fuels and environmental pollution become a serious problem of human society researchers are actively finding renewable green energy sources. Considered as a clean efficient and renewable alternative Hydrogen energy is considered the most promising energy source. However the safe and efficient storage of hydrogen has become the major problem that hinders its application. To solve this gap this paper proposes to utilize surfactant modified graphene for hydrogen storage. With Hummers method and ultrasonic stripping method this study prepared graphene from graphene oxide with NaBH4. Surfactant sodium dodecylbenzene sulfonate (SDBS) was used as a dispersant during the reduction process to produce the dispersion-stabilized graphene suspensions. The characteristics of the graphene suspensions then were examined by XRD SEM TEM FT-IR Raman XPS TG and N2 adsorption-desorption tests. The hydrogen adsorption properties of the samples were investigated with Langmuir and Freundlich fitting. The results show that the adsorption behavior is consistent with the Freundlich adsorption model and the process is a physical adsorption.
Predicting Radiative Characteristics of Hydrogen and Hythane Jet Fires Using Firefoam
Sep 2013
Publication
A possible consequence of pressurized hydrogen release is an under-expanded jet fire. Knowledge of the flame length radiative heat flux and fraction as well as the effects of variations in ground reflectance is important for safety assessment. The present study applies an open source CFD code FireFOAM to study the radiation characteristics of hydrogen and hydrogen/methane jet fires. For combustion the eddy dissipation concept for multi-component fuels recently developed by the authors in the large eddy simulation (LES) framework is used. The radiative heat is computed with the finite volume discrete ordinates model in conjunction with the weighted-sum-of-gray-gases model for the absorption/emission coefficient. The pseudo-diameter approach is used in which the corresponding parameters are calculated using the correlations of Birch et al. [22]. The predicted flame length and radiant fraction are in good agreement with the measurements of Schefer et al. [2] Studer et al. [3] and Ekoto et al. [6]. In order to account for the effects of variation in ground surface reflectance the emissivity of hydrogen flames was modified following Ekoto et al. [6]. Four cases with different ground reflectance are computed. The predictions show that the ground surface reflectance only has minor effect on the surface emissive power of the hydrogen jet fire. The radiant fractions fluctuate from 0.168 to 0.176 close to the suggested value of 0.16 by Ekoto et al.[6] based on the analysis of their measurements.
The Dependence of Fatigue Crack Growth on Hydrogen in Warm-rolled 316 Austenitic Stainless Steel
Sep 2019
Publication
The fatigue crack growth rate of warm-rolled AISI 316 austenitic stainless steel was investigated by controlling rolling strain and temperature in argon and hydrogen gas atmospheres. The fatigue crack growth rates of warm-rolled 316 specimens tested in hydrogen decreased with increasing rolling temperature especially 400 °C. By controlling the deformation temperature and strain the influences of microstructure (including dislocation structure deformation twins and α′ martensite) and its evolution on hydrogen-induced degradation of mechanical properties were separately discussed. Deformation twins deceased and dislocations became more uniform with the increase in rolling temperature inhibiting the formation of dynamic α′ martensite during the crack propagation. In the cold-rolled 316 specimens deformation twins accelerated hydrogen-induced crack growth due to the α′ martensitic transformation at the crack tip. In the warm-rolled specimens the formation of α′ martensite around the crack tip was completely inhibited which greatly reduced the fatigue crack growth rate in hydrogen atmosphere.
Heat Transfer Analysis for Fast Filling of On-board Hydrogen Tank
Mar 2019
Publication
The heat transfer analysis in the filling process of compressed on-board hydrogen storage tank has been the focus of hydrogen storage research. The initial conditions mass flow rate and heat transfer coefficient have certain influence on the hydrogen filling performance. In this paper the effects of mass flow rate and heat transfer coefficient on hydrogen filling performance are mainly studied. A thermodynamic model of the compressed hydrogen storage tank was established by Matlab/Simulink. This 0D model is utilized to predict the hydrogen temperature hydrogen pressure tank wall temperature and SOC (State of Charge) during filling process. Comparing the simulated results with the experimental data the practicability of the model can be verified. The simulated results have certain meaning for improving the hydrogenation parameters in real filling process. And the model has a great significance to the study of hydrogen filling and purification.
Evaluation of Performance Characteristics of a Novel Hydrogen-fuelled Free-piston Engine Generator
Mar 2020
Publication
In this work we present the experimental results obtained from hydrogen fuelled spark-ignited dual piston free-piston engine generator (FPEG) prototype operated in two-stroke and four-stroke mode. The FPEG testing was successfully conducted at 3.7 compression ratio engine speed between 5 Hz and 11 Hz and with different equivalence ratios. The FPEG technical details experimental set-up and operational control are explained in detail. Performance indicators show that both equivalence ratio and engine speed affect the engine operation characteristics. For every set of specified FPEG parameters appropriate range of equivalence ratio is recommended to prevent unwanted disturbance to electric generator operation. Both two-stroke and four-stroke cycle mode were tested and the results showed different combustion characteristics with the two thermodynamic cycles. Four-stroke cycle mode could operate with indicated thermal efficiency gain up to 13.2% compared with the two-stroke cycle.
Development of a Gaseous and Solid-state Hybrid System for Stationary Hydrogen Energy Storage
Jun 2020
Publication
Hydrogen can serve as a carrier to store renewable energy in large scale. However hydrogen storage still remains a challenge in the current stage. It is difficult to meet the technical requirements applying the conventional storage of compressed gaseous hydrogen in high-pressure tanks or the solid-state storage of hydrogen in suitable materials. In the present work a gaseous and solid-state (G-S) hybrid hydrogen storage system with a low working pressure below 5 MPa for a 10 kW hydrogen energy storage experiment platform is developed and validated. A Ti−Mn type hydrogen storage alloy with an effective hydrogen capacity of 1.7 wt% was prepared for the G-S hybrid hydrogen storage system. The G-S hybrid hydrogen storage tank has a high volumetric hydrogen storage density of 40.07 kg H2 m−3 and stores hydrogen under pressure below 5 MPa. It can readily release enough hydrogen at a temperature as low as −15 °C when the FC system is not fully activated and hot water is not available. The energy storage efficiency of this G-S hybrid hydrogen storage system is calculated to be 86.4%−95.9% when it is combined with a FC system. This work provides a method on how to design a G-S hydrogen storage system based on practical demands and demonstrates that the G-S hybrid hydrogen storage is a promising method for stationary hydrogen storage application.
Hydrogen Diffusion Mechanism around a Crack Tip in Type 304L Austenite Stainless Steel Considering the Influence of the Volume Expansion of Strain-Induced Martensite Transformation
Sep 2019
Publication
Strain-induced martensite transformation (SIMT) commonly exists around a crack tip of metastable austenite stainless steels. The influence of the volume expansion of the SIMT on the hydrogen diffusion was investigated by hydrogen diffusion modelling around a crack tip in type 304L austenite stainless steel. The volume expansion changed the tensile stress state into pressure stress state at the crack tip resulting in a large stress gradient along the crack propagation direction. Compared to the analysis without considering the volume expansion effect this volume expansion further accelerated the hydrogen transport from the inner surface to a critical region ahead of the crack tip and further increased the maximum value of the hydrogen concentration at the critical position where the strain-induced martensite fraction approximates to 0.1 indicating that the volume expansion of the SIMT further increased the hydrogen embrittlement susceptibility.
A Host-guest Approach to Fabricate Metallic Cobalt Nanoparticles Embedded in Silk-derived N-doped Carbon Fibers for Efficient Hydrogen Evolution
Feb 2017
Publication
Hydrogen evolution reaction (HER) plays a key role in generating clean and renewable energy. As the most effective HER electrocatalysts Pt group catalysts suffer from severe problems such as high price and scarcity. It is highly desirable to design and synthesize sustainable HER electrocatalysts to replace the Pt group catalysts. Due to their low cost high abundance and high activities cobalt-incorporated N-doped nanocarbon hybrids are promising candidate electrocatalysts for HER. In this report we demonstrated a robust and eco-friendly host-guest approach to fabricate metallic cobalt nanoparticles embedded in N-doped carbon fibers derived from natural silk fibers. Benefiting from the one-dimensional nanostructure the well-dispersed metallic cobalt nanoparticles and the N-doped thin graphitized carbon layer coating the best Co-based electrocatalyst manifests low overpotential (61 mV@10 mA/cm2) HER activity that is comparable with commercial 20% Pt/C and good stability in acid. Our findings provide a novel and unique route to explore high-performance noble-metal-free HER electrocatalysts.
Self-ignition and Flame Propagation of Pressurized Hydrogen Released Through Tubes
Sep 2019
Publication
The spontaneous ignition of hydrogen released from the high pressure tank into the downstream pipes with different lengths varied from 0.3m to 2.2m has been investigated experimentally. In this study the development of shock wave was recorded by pressure sensors and photoelectric sensors were used to confirm the presence of a flame in the pipe. In addition the development of jet flame was recorded by high-speed camera and IR camera. The results show that the minimal release pressure in different tube when self-ignition of hydrogen occurred could decrease first and then increase with the increase of the aspect of pipe. And the minimum release pressure of hydrogen self-ignition was 3.87MPa. When the flame of self-ignition hydrogen spouted out of the tube Mach disk was observed. The method of CFD was adopted. The development of shock wave at the tube exit was reproduced and structures as barrel shock the reflected shock and the Mach disk are presented. Because of these special structures the flame at the nozzle is briefly extinguished and re-ignited. At the same time the complete development process of the jet flame was recorded including the formation and separation of the spherical flame. The flame structure exhibits three typical levels before the hemispherical flame separation.
A Study on the Influential Factors of Stress Corrosion Cracking in C110 Casing Pipe
Jan 2022
Publication
In this paper we analyze the potential factors affecting the hydrogen sulfide type of stress corrosion cracking in C110 casing pipes. In order to further study these cracking factors the methods of material property testing scanning electron microscopy XRD TEM and 3D ultra-depth-of-field were applied in the experiments. Besides that an HTHP autoclave was independently designed by the laboratory to simulate the actual corrosion environment and the potential factors affecting the stress corrosion cracking of C110 casing pipes were determined. The test results showed that the chemical composition metallographic structure hardness and non-metallic inclusions of the two types of C110 casing pipes were all qualified. In fact there remains a risk of stress corrosion cracking when the two kinds of C110 casing pipes serve under long-term field-working conditions. It is considered in this paper that the precipitates on the material surface stress damage and pitting corrosion are all critical factors affecting the stress corrosion cracking of casing pipes.
Inhibition of Confined Hydrogen Explosion by Inert Gases
Sep 2019
Publication
"This paper is aimed at revealing the inhibiting effects of He Ar N2 and CO2 on confined hydrogen explosion. The flame characteristics under thermo diffusive instability and hydrodynamic instability are analyzed using Lewis number and ratio of density ratio to flame thickness. The inhibiting effects of inert gas on confined hydrogen explosion are evaluated using maximum explosion pressure and maximum pressure rise rate. The inhibiting mechanism is obtained by revealing thermal diffusivity maximum mole fraction and net reaction rate of active radicals. The results demonstrated that the strongest destabilization effect of hydrodynamic instability and thermodiffusive instability occurs when the inert gas is Ar and CO2 respectively. Taking maximum explosion pressure and maximum rate of pressure rise as an indicator the effects of confined hydrogen explosion inhibition from strong to weak are CO2 N2 Ar and He. Laminar burning velocity thermal diffusivity maximum mole fraction and net reaction rate of active radicals continues to decrease in the order of He Ar N2 and CO2. The elementary reactions of generating and consuming active radicals at the highest net reaction rate are mainly consisted of R1 (H+O2=OH+O) R2 (H2+O=OH+H) R3 (H2+OH=H2O+H) and R10 (HO2+H=2OH).
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