Liquid pump-enabled hydrogen refueling system for heavy duty fuel cell vehicles: Pump performance and J2601-compliant fills with precooling

We have developed a hydrogen (H₂) refueling solution capable of delivering precooled, compressed gaseous hydrogen for heavy duty vehicle (HDV) refueling applications. The system uses a submerged pump to deliver pressurized liquid H₂ from a cryogenic storage tank to a dispensing control loop that vaporizes the liquid and adjusts the pressure and temperature of the resulting gas to enable refueling at 35 MPa and temperatures as low as ?40 °C. A full-scale mobile refueler was fabricated and tested over a 6-month campaign to validate its performance. We report results from tests involving a total of 9000 kg of liquid H₂ pumped and 1350 filling cycles over a range of conditions. Notably, the system was able to repeatably complete multiple, back-to-back 30 kg filling cycles in under 6 min each, in full compliance with the SAE J2601-2 standard, demonstrating its potential for rapid-throughput HDV refueling applications.     

Screen channel LAD bubble point tests in liquid hydrogen

This paper presents experimental results for the liquid hydrogen bubble point tests for liquid acquisition devices (LADs) operating in low gravity cryogenic propulsion systems. The purpose of the test was to investigate parameters that affect screen channel LAD performance in a low pressure liquid hydrogen (LH₂) propellant tank and to demonstrate several ways to increase the LH₂ bubble point pressure. Three fine mesh screen channel LAD samples were tested in LH₂ over the range of 16.7 K < T < 21.1 K and 31.5 kPa < P < 155 kPa using gaseous helium and hydrogen as pressurant gases. Results show that bubble point pressure is affected by screen mesh type, liquid temperature and pressure, and type of pressurization gas. Higher bubble points are achieved by using a finer mesh screen and pressurizing and subcooling the liquid with gaseous helium. In addition, there is evidence that the screen pore is itself temperature dependent.     

Simulation on a proposed large-scale liquid hydrogen plant using a multi-component refrigerant refrigeration system

A proposed liquid hydrogen plant using a multi-component refrigerant (MR) refrigeration system is explained in this paper. A cycle that is capable of producing 100 tons of liquid hydrogen per day is simulated. The MR system can be used to cool feed normal hydrogen gas from 25 °C to the equilibrium temperature of −193 °C with a high efficiency. In addition, for the transition from the equilibrium temperature of the hydrogen gas from −193 °C to −253 °C, the new proposed four H₂ Joule–Brayton cascade refrigeration system is recommended. The overall power consumption of the proposed plant is 5.35 kWh/kg_LH2, with an ideal minimum of 2.89 kWh/kg_LH2. The current plant in Ingolstadt is used as a reference, which has an energy consumption of 13.58 kWh/kg_LH2 and an efficiency of 21.28%: the efficiency of the proposed system is 54.02% or more, where this depends on the assumed efficiency values for the compressors and expanders. Moreover, the proposed system has some smaller-size heat exchangers, much smaller compressor motors, and smaller crankcase compressors. Thus, it could represent a plant with the lowest construction cost with respect to the amount of liquid hydrogen produced in comparison to today’s plants, e.g., in Ingolstadt and Leuna. Therefore, the proposed system has many improvements that serve as an example for future hydrogen liquefaction plants.     

Liquid pump-enabled hydrogen refueling system for heavy duty fuel cell vehicles: Fuel cell bus refueling demonstration at Stark Area Regional Transit Authority (SARTA)

We have demonstrated a hydrogen (H₂) refueling solution capable of delivering precooled, compressed gaseous hydrogen for heavy duty vehicle (HDV) refueling applications by refueling transit buses over a three-month period under real-world conditions. The system uses a submerged pump to deliver pressurized liquid H₂ from a cryogenic storage tank to a dispensing control loop that vaporizes the liquid and adjusts the pressure and temperature of the resulting gas to enable refueling at 35 MPa and temperatures as low as −40 °C, consistent with the SAE J2601 standard. Using our full-scale mobile refueler, we completed 118 individual bus filling events using 13 different vehicles, involving a total of 3,700 kg of H₂ dispensed. We report filling statistics from the entire campaign, details on individual fills (including fill times, final state of charge, benefits of pre-cooled fills, and back-to-back filling capabilities), and discuss transit agency feedback on technology performance. In our final test, the system successfully completed an endurance test using a single dispenser involving 52 consecutive individual fills over an 11.5-h period, dispensing 1,322 kg of H₂ with an average fill rate of 3.4 kg/min and peak rate of 7.1 kg/min, and reaching an average SOC of 97.6% across all fills.     

Compressed hydrogen production via reaction between liquid ammonia and alkali metal hydride

Ammonia NH₃ is recognized as one of the attractive hydrogen H₂ carriers because it has a high hydrogen content of 18 mass% and it is easily liquefied under about 1 MPa of pressure at a room temperature. NH₃ can react with alkali metal hydrides and generate H₂ even at room temperature, resulting that metal amides are formed as reaction products. The H₂ generation is exothermic reaction, and it is not effectively prevented by H₂ partial pressure in a closed system as thermodynamic properties. In this work, we demonstrated the production of compressed H₂ by the reaction between liquid NH₃ and lithium hydride LiH in a closed pressure vessel, where liquid NH₃ would realize better kinetic properties for the reaction with metal hydride than gaseous NH₃. Actually, more than 12 MPa H₂ was obtained within several hours.     

CFD computations of liquid hydrogen releases

Hydrogen is widely recognized as an attractive energy carrier due to its low-level air pollution and its high mass-related energy density. However, its wide flammability range and high burning velocity present a potentially significant hazard. A significant fraction of hydrogen is stored and transported as a cryogenic liquid (liquid hydrogen, or LH₂) as it requires much less volume compared to gaseous hydrogen. In order to exist as a liquid, H₂ must be cooled to a very low temperature, 20.28 K. LH₂ is a common liquid fuel for rocket applications. It can also be used as the fuel storage in an internal combustion engine or fuel cell for transport applications. Models for handling liquid releases, both two-phase flashing jets and pool spills, have been developed in the CFD-model FLACS. The very low normal boiling point of hydrogen (20 K) leads to particular challenges as this is significantly lower than the boiling points of oxygen (90 K) and nitrogen (77 K). Therefore, a release of LH₂ in the atmosphere may induce partial condensation or even freezing of the oxygen and nitrogen present in the air. A pool model within the CFD software FLACS is used to compute the spreading and vaporization of the liquid hydrogen depositing on the ground where the partial condensation or freezing of the oxygen and nitrogen is also taken into account. In our computations of two-phase jets the dispersed and continuous phases are assumed to be in thermodynamic and kinematic equilibrium. Simulations with the new models are compared against selected experiments performed at the Health and Safety Laboratory (HSL).     

Hydrogen solubility,interfacial tension,and density of the liquid organic hydrogen carrier system diphenylmethane/dicyclohexylmethane

In the present study, physico-chemical properties of the liquid organic hydrogen carrier (LOHC) system diphenylmethane/dicyclohexylmethane in the presence of dissolved hydrogen are presented for temperatures up to 523 K and pressures up to 10 MPa. Solubility of hydrogen, interfacial tension, and liquid density were measured by the isochoric saturation method, the pendant-drop method, and vibrating-tube method, respectively, which are realized in two experimental setups. The solubility of hydrogen increases with increasing temperature and pressure. For the fully hydrogenated dicyclohexylmethane, it is about 50% higher than for the non-hydrogenated diphenylmethane and similar to that of a mixture from a deliberately stopped hydrogenation process containing also partially hydrogenated cyclohexylphenylmethane. While the interfacial tension decreases slightly with increasing hydrogen pressure at constant temperature, the density remains approximately constant. The latter properties obtained for different mixtures with similar degree of hydrogenation show that the influence of the presence of cyclohexylphenylmethane is small.     

Hydrogen tank first filling experiments at the JRC-IET GasTeF facility

Storage of gases under pressure, including hydrogen, is a well-known technology. However the use of hydrogen in vehicles at pressures much higher than those applicable in natural gas cars still requires safety and performance studies with respect to the verification and validation of the existing standards and regulations. The JRC-IET has developed a facility, GasTeF, for carrying out tests on full-scale high pressure vehicle's tanks for hydrogen or natural gas. A typical test performed in GasTeF is the hydrogen cycling, in which tanks are filled and slowly emptied using hydrogen pressurised up to 88 MPa, for at least 1000 times in line with the requirements of the EU regulation on type-approval of hydrogen-powered motor vehicles. The temperature evolution of the gas inside and outside the tank is monitored using a thermocouples array system specifically designed for this purpose. This paper presents the first experimental results on the temperature distribution during hydrogen cycling tests.     

Hydrogen carrier by ammonia borane-ammonia system with low-vapor pressure

Ammonia (NH₃) absorption of ammonia borane (AB) was evaluated as potential hydrogen and/or NH₃ storage system for hydrogen transportation in this work. The thermodynamic properties of the AB-NH₃ system, the physical properties such as density and kinematic viscosity, and the stability of AB stored in liquid NH₃ were evaluated. The enthalpy and entropy values of the AB-NH₃ system were determined to be −19.87 kJ/mol and 67.76 J/mol·K, respectively. The structural identification of AB after NH₃ removal revealed that NH₃ can be removed completely from AB. Both volumetric and gravimetric hydrogen densities of the AB-NH₃ system were higher than those of liquid NH₃ under the vapor pressure of 0.1 MPa. The kinematic viscosity of the AB-NH₃ system is moderate, which is easy to handle. According to the stability evaluation from ¹¹B NMR results, high stability for both AB and NH₃ was confirmed at room temperature. The study also demonstrates that storing AB in liquid NH₃ is efficient for hydrogen transportation although temperature control is important for maintaining AB purity. Overall, the findings provide new insights into the AB-NH₃ system and its potential applications in energy storage.     

Vehicle refueling with liquid hydrogen thermal compression

We have modeled an approach for dispensing pressurized hydrogen to 350 and/or 700 bar vehicle vessels. Instead of relying on compressors, this concept stores liquid hydrogen in cryogenic pressure vessels where pressurization occurs through heat transfer, reducing the station energy footprint from 12 kW h/kgH₂ of energy from the US grid mix to 1.5–2 kW h/kgH₂ of heating. This thermal compression station presents capital cost and reliability advantages by avoiding the expense and maintenance of high-pressure hydrogen compressors, at the detriment of some evaporative losses. The total installed capital cost for a 475 kg/day thermal compression hydrogen refueling station is estimated at about $611,500, an almost 60% cost reduction over today's refueling station cost. The cost for 700 bar dispensing is $5.23/kg H₂ for a conventional station vs. $5.45/kg H₂ for a thermal compression station. If there is a demand for 350 bar H₂ in addition to 700 bar dispensing, the cost of dispensing from a thermal compression station drops to $4.81/kg H₂, which is similar to the cost of a conventional station that dispenses 350 bar H₂ only. Thermal compression also offers capacity flexibility (wide range of pressure, temperature, and station demand) that makes it appealing for early market applications.     

Evaluation of a thermally-driven metal-hydride-based hydrogen compressor

Currently, the hydrogen storage method used aboard fuel cell electric vehicles utilizes pressures up to 70 MPa. Attaining such high pressures requires mechanical gas compression or hydrogen liquefaction followed by heating to form a high-pressure gas, and these processes add to the cost and reduce the energy efficiency of a hydrogen fueling system. In previous work we have evaluated the use of high-pressure electrolysis, in which hydrogen is generated from water and the electrolyzer boosts the hydrogen pressure to values from 13 to 45 MPa. While electrolytic compression is a novel and energy efficient method to produce high-pressure hydrogen, it has several limitations at present and will require more development work. Another concept is to use hydrogen absorbing alloys that form metal hydrides, in combination with a heat engine (hot and cold reservoirs), to drive a cyclic process in which hydrogen gas is absorbed and desorbed to compress hydrogen. Furthermore, by using a thermally-driven compressor, the hot and cold reservoirs can be obtained using renewable energy such as sunlight for heating together with ambient air or water for cooling. In this work we evaluated the thermodynamics and kinetics of a prototype metal hydride hydrogen compressor (MHHC) built for us by a research group in China. The compressor utilized a hydrogen input pressure of approximately 14 MPa, and, operating between an initial temperature of approximately 300 K and a final temperature of 400 K, a pressure of approximately 41 MPa was attained. In a series of experiments with those conditions the average compression ratio for a single-stage compression was approximately three. In the initial compression cycles, up to 300 g of hydrogen was compressed for each 100 K temperature cycle. The enthalpy of the metallic-alloy-hydriding reaction was found to be approximately 20.5 kJ per mole of H₂, determined by measuring the pressure composition isotherm at three temperatures and using a Van't Hoff plot. The thermodynamic efficiency of the compressor, as measured by the value of the compression work performed divided by the heat energy added and removed in one complete cycle, was determined via first and second law analyses. The Carnot efficiency was approximately 25%, the first law efficiency was approximately 3–5%, and the second law efficiency was approximately 12–20%, depending on the idealized compression cycle used to assign a value to the compression work, as well as other assumptions. These efficiencies compare favorably with values reported for other thermally-driven compressors.     

Influence of dissolved hydrogen on the viscosity and interfacial tension of the liquid organic hydrogen carrier system based on diphenylmethane by surface light scattering and molecular dynamics simulations

In hydrogenation and dehydrogenation processes of liquid organic hydrogen carriers (LOHCs), molecular hydrogen (H₂) is present, but its influence on the thermophysical properties of the LOHC compounds is still hardly known. This study provides experimental results from surface light scattering and predictions from molecular dynamics simulations on the influence of dissolved H₂ on the liquid viscosity, interfacial tension, and liquid density of the LOHC system based on diphenylmethane at varying degree of hydrogenation, process-relevant temperatures up to 573 K, and pressures up to 7 MPa. First-time measurements of the viscosity of bicyclic hydrocarbon compounds in the presence of dissolved H₂ at saturation conditions reveal a negligible effect of pressure. The interfacial tension decreases independently of the LOHC composition by about 6% at 7 MPa. The simulations can adequately represent the effect of H₂ on the interfacial tension and evidence a weak enrichment of H₂ at the interface.     

Efficiency analysis of depressurization process and pressure control strategies for liquid hydrogen storage system in microgravity

In order to investigate dynamic characteristics of pressure fluctuation and thermal efficiency of a liquid hydrogen (LH₂) storage system during depressurization process under microgravity condition, a transient CFD model of LH₂ tank is established. Based on the assumption of lumped vapor, a UDF code is developed to solve phase change and heat transfer between liquid phase and vapor one. The thermal efficiency is provided for assessing the performance of different pressure control methods. Results show that raising the injection velocity and decreasing the temperature of the injection liquid can enhance the effect of fluid mixing and shorten the depressurization time. Increasing the pressure lower limit can also improve the efficiency of depressurization process. The model can predict the tendency of pressure changes in the tank, and provide theoretical guide to design LH₂ tank and optimize its parameters for space application.     

In-situ hydrogen wettability characterisation for underground hydrogen storage

Hydrogen storage in subsurface aquifers or depleted gas reservoirs represents a viable long-term energy storage solution. There is currently a scarcity of subsurface petrophysical data for the hydrogen system. In this work, we determine the wettability and Interfacial Tension (IFT) of the hydrogen-brine-quartz system using captive bubble, pendant drop and in-situ 3D micro-Computed Tomography (CT) methods. Effective contact angles ranged between 29° and 39° for pressures 6.89–20.68 MPa and salinities from distilled water to 5000 ppm NaCl brine. In-situ methods, novel to hydrogen investigations, confirmed the water-wet system with the mean of the macroscopic and apparent contact angle distributions being 39.77° and 59.75° respectively. IFT decreased with increasing pressure in distilled water from 72.45 mN/m at 6.89 MPa to 69.43 mN/m at 20.68 MPa. No correlation was found between IFT and salinity for the 1000 ppm and 5000 ppm brines. Novel insights into hydrogen wetting in multiphase environments allow accurate predictions of relative permeability and capillary pressure curves for large scale simulations.     

Boosting the dehydrogenation efficiency of dodecahydro-N-ethylcarbazole by assembling Pt nanoparticles on the single-layer Ti3C2Tx MXene

As the candidates for large-scale hydrogen storage, liquid organic hydrogen carriers (LOHCs) exhibit evident advantages in hydrogen storage density and convenience of storage and transportation. Among them, NECZ (N-ethylcarbazole)/12H-NECZ (dodecahydro-N-ethylcarbazole) is considered as a typical system with the lower hydrogenation/dehydrogenation temperature. However, the low dehydrogenation efficiency restrict its commercial applications. In this work, the single-layer Ti₃C₂T_x MXene was employed as the support to load the Pt nanoparticles for the 12H-NECZ dehydrogenation reaction. The effect of transition metals, loading amounts and morphologies of catalysts were analyzed. It was found that the 3 wt% Pt/S–Ti₃C₂T_x catalyst exhibited the best catalytic performance with 100% conversion, 91.55% selectivity of NECZ and 5.62 wt% hydrogen release amount at 453 K, 101.325 kPa for 7 h. The product distributions and kinetics analysis suggested that the elementary reaction from 4H-NECZ to NECZ was the rate-limiting step. The selectivity of NECZ is sensitive to the dehydrogenation temperature. Combined with the XRD, SEM, HRTEM, XPS, BET and FT-IR results, it could be indicated that the special two-dimension structure of S–Ti₃C₂T_x and electronic effect between Pt and S–Ti₃C₂T_x enhanced the dehydrogenation efficiency of 12H-NECZ. The measurements of cyclic dehydrogenation indicated that the Pt/S–Ti₃C₂T_x catalyst exhibited good stability after 42 h. This work brought a new strategy for the design of efficient catalysts using two-dimensional materials in the applications of the liquid organic storage hydrogen technology.     

Study on the harm effects of releases from liquid hydrogen tank by consequence modeling

The accidental releases of hydrogen from liquid storage and the subsequent consequences are studied from a harm perspective rather than a standpoint of risk. The cold, thermal and overpressure effects from hydrogen cold cloud, fireball, jet fire, flash fire, and vapor cloud explosion are evaluated in terms of two kinds of effect distances based on lethal and harmful criteria. Results show that for instantaneous release, the sequence of effect distances is vapor cloud explosion > flash fire > cold cloud > fireball, and for continuous release, the sequence is vapor cloud explosion > flash fire > jet fire > cold cloud. An overall comparison between instantaneous and continuous release reveals that the catastrophic rupture, rather than leakages, is the dominant event. Besides, the effect distances of liquid hydrogen tank are compared with those of 70 MPa gaseous storage with equivalent mass. Compared with 70 MPa gaseous storage, the liquid hydrogen storage may be safer under leak scenarios but more dangerous under catastrophic rupture scenario.     

Modeling the diffusion of flammable hydrogen cloud under different liquid hydrogen leakage conditions in a hydrogen refueling station

Constructing hydrogen refueling stations will be popular for hydrogen energy use in the future, and investigating the diffusion characteristics of hydrogen in a leakage incident is quite significant. The instantaneous evolution of flammable hydrogen clouds arising from liquid hydrogen leakage in a hydrogen refueling station is predicted using Ansys Fluent, and parametric analyses are conducted to reveal the effects of storage pressure, source height, and leakage direction on the distributions of the flammable regions. In addition, the feasibilities of heating the ceiling or the ground of the station after the leakage of liquid hydrogen to accelerate the hydrogen dilution are examined. The results show that the flammable region is stabilized at 90 s, the corresponding flammable hydrogen cloud volume is about 333 m³, and the extensions of downwind and vertical directions reach 10 m and 9.3 m. Storage pressure has a finite effect on the downwind diffusion distance of the flammable cloud. A lower source height tends to format the high-concentration hydrogen cloud near the ground while a higher source height helps separate the flammable clouds from the ground. The upward leakage direction leads to the maximum downwind diffusion distance of about 10.2 m while the downward leakage direction makes the high hydrogen concentration region confined below the ceiling. Just maintaining the ceiling at the initial temperature of 300 K is effective for accelerating the hydrogen dilution in the upward leakage. The maximum hydrogen concentration and the flammable volume can be reduced at rates of 0.35 vol % and 8% for every 50 K increase in heating temperature. For the downward leakage, keeping the ground at the initial temperature just works for the first 40 s in reducing the maximum hydrogen concentration, while increasing the heating temperature receives a gradually declined effect on reducing the flammable volume.     

Large-scale long-distance land-based hydrogen transportation systems: A comparative techno-economic and greenhouse gas emission assessment

Interest in hydrogen as an energy carrier is growing as countries look to reduce greenhouse gas (GHG) emissions in hard-to-abate sectors. Previous works have focused on hydrogen production, well-to-wheel analysis of fuel cell vehicles, and vehicle refuelling costs and emissions. These studies use high-level estimates for the hydrogen transportation systems that lack sufficient granularity for techno-economic and GHG emissions analysis. In this work, we assess and compare the unit costs and emission footprints (direct and indirect) of 32 systems for hydrogen transportation. Process-based models were used to examine the transportation of pure hydrogen (hydrogen pipeline and truck transport of gaseous and liquified hydrogen), hydrogen-natural gas blends (pipeline), ammonia (pipeline), and liquid organic hydrogen carriers (pipeline and rail). We used sensitivity and uncertainty analyses to determine the parameters impacting the cost and emission estimates. At 1000 km, the pure hydrogen pipelines have a levelized cost of $0.66/kg H₂ and a GHG footprint of 595 gCO₂eq/kg H₂. At 1000 km, ammonia, liquid organic hydrogen carrier, and truck transport scenarios are more than twice as expensive as pure hydrogen pipeline and hythane, and more than 1.5 times as expensive at 3000 km. The GHG emission footprints of pure hydrogen pipeline transport and ammonia transport are comparable, whereas all other transport systems are more than twice as high. These results may be informative for government agencies developing policies around clean hydrogen internationally.     

Hydrogen storage properties of carbon aerogel synthesized by ambient pressure drying using new catalyst triethylamine

In this paper, we report here the hydrogen storage capacity of activated carbon aerogel synthesized by ambient pressure drying using a new catalyst. The carbon aerogel (CA) has been synthesized by the sol-gel method using resorcinol (R) and formaldehyde (F). For drying of RF wet gel instead of expensive and unsafe supercritical process, we have used ambient pressure drying. To avoid shrinkage which may occur due to this mode of drying, instead of usual catalyst (C): Na₂CO₃, organic catalyst triethylamine (TEA), which is known to be a condensing agent has been used. In order to find out the effect of change of R/C ratio on hydrogen sorption, three different R/C namely CA 1000, CA 2000, and CA 3000 were taken. Structural and microstructural details have been studied employing XRD, SEM, TEM, nitrogen adsorption, FTIR, and Raman spectroscopy. TEM and nitrogen adsorption studies have revealed that aerogel with R/C 1000 exhibits a higher degree of micropore density. The hydrogen storage capacities for all R/C ratios have been determined. It has been found that carbon aerogel (CA) with R/C = 1000, exhibits the highest hydrogen adsorption capacity out of the three aerogels. At liquid nitrogen temperature, the hydrogen storage capacity of aerogel with R/C = 1000 for the as-synthesized and activated carbons have been found to be 4.00 wt % and 4.80 wt %. A viable reason for the occurrence of high hydrogen storage capacity at liquid nitrogen temperature for aerogel with R/C = 1000 has been put forward.