Dispersion and catalytic ignition of hydrogen leaks within enclosed spaces

An experimental investigation is conducted into the nature of catalytic ignition of leaked hydrogen gas within an enclosure, and the nature of hydrogen dispersion under varied venting conditions. Using a 1/16th linear scale two-car garage as a model, and a platinum foil as a catalytic surface, it is found that for all conditions tested, catalytic ignition is observed after the leaked hydrogen comes in contact with the catalytic surface, which is initially at or near room temperature. After ignition, these surface reactions lead to steady-state surface temperatures in the range of 600–800 K, dependent on inlet conditions in terms of mixture composition and flow rate. In addition, varying the venting opportunities from the garage walls suggests that not only total area, but also the number and position of vents may impact the nature of hydrogen accumulation within an enclosed structure.     

Safety assessment of unignited hydrogen discharge from onboard storage in garages with low levels of natural ventilation

This study is driven by the need to understand requirements to safe blow-down of hydrogen onboard storage tanks through a pressure relief device (PRD) inside a garage-like enclosure with low natural ventilation. Current composite tanks for high pressure hydrogen storage have been shown to rupture in 3.5–6.5 min in fire conditions. As a result a large PRD venting area is currently used to release hydrogen from the tank before its catastrophic failure. However, even if unignited, the release of hydrogen from such PRDs has been shown in our previous studies to result in unacceptable overpressures within the garage capable of causing major damage and possible collapse of the structure. Thus, to prevent collapse of the garage in the case of a malfunction of the PRD and an unignited hydrogen release there is a clear need to increase blow-down time by reducing PRD venting area. Calculations of PRD diameter to safely blow-down storage tanks with inventories of 1, 5 and 13 kg hydrogen are considered here for a range of garage volumes and natural ventilation expressed in air changes per hour (ACH). The phenomenological model is used to examine the pressure dynamics within a garage with low natural ventilation down to the known minimum of 0.03 ACH. Thus, with moderate hydrogen flow rate from the PRD and small vents providing ventilation of the enclosure there will be only outflow from the garage without any air intake from outside. The PRD diameter, which ensures that the pressure in the garage does not exceed a value of 20 kPa (accepted in this study as a safe overpressure for civil structures) was calculated for varying garage volumes and natural ventilation (ACH). The results are presented in the form of simple to use engineering nomograms. The conclusion is drawn that PRDs currently available for hydrogen-powered vehicles should be redesigned along with either a change of requirements for the fire resistance rating or innovative design of the onboard storage system as hydrogen-powered vehicles are intended for garage parking. Further research is needed to develop safety strategies and engineering solutions to tackle the problem of fire resistance of onboard storage tanks and requirements to PRD performance. Regulation, codes and standards in the field should address this issue.     

Experimental study of hydrogen release accidents in a vehicle garage

Storing a hydrogen fuel-cell vehicle in a garage poses a potential safety hazard because of the accidents that could arise from a hydrogen leak. A series of tests examined the risk involved with hydrogen releases and deflagrations in a structure built to simulate a one-car garage. The experiments involved igniting hydrogen gas that was released inside the structure and studying the effects of the deflagrations. The “garage” measured 2.72 m high, 3.64 m wide, and 6.10 m long internally and was constructed from steel using a reinforced design capable of withstanding a detonation. The front face of the garage was covered with a thin, transparent plastic film. Experiments were performed to investigate extended-duration (20-40 min) hydrogen leaks. The effect that the presence of a vehicle in the garage has on the deflagration was also studied. The experiments examined the effectiveness of different ventilation techniques at reducing the hydrogen concentration in the enclosure. Ventilation techniques included natural upper and lower openings and mechanical ventilation systems. A system of evacuated sampling bottles was used to measure hydrogen concentration throughout the garage prior to ignition, and at various times during the release. All experiments were documented with standard and infrared (IR) video. Flame front propagation was monitored with thermocouples. Pressures within the garage were measured by four pressure transducers mounted on the inside walls of the garage. Six free-field pressure transducers were used to measure the pressures outside the garage.     

Helium dispersion following release in a 1/4-scale two-car residential garage

A series of experiments are described in which helium was released at a constant rate into a 1.5 m × 1.5 m × 0.75 m enclosure designed as a 1/4-scale model of a two-car garage. The purpose was to provide reference datasets for testing and validating computational fluid dynamics (CFD) models and to experimentally characterize the effects of a number of variables on the mixing behavior within an enclosure and the exchange of helium with the outside surroundings. Helium was used as a surrogate for hydrogen, and the total volume released was scaled as the amount that would be released by a typical hydrogen-fueled automobile with a full tank. Temporal profiles of helium were measured at seven vertical locations within the enclosure during and following 1-h and 4-h releases. Idealized vents in one wall sized to provide air exchange rates typical of actual garages were used. The effects of vent size, number, and location were investigated using three different vent combinations. The dependence on leak location was considered by releasing helium at three different points within the enclosure.     

Thermal design analysis of a 1 L cryogenic liquid hydrogen tank for an unmanned aerial vehicle

Thermal design analysis of a 1-L cryogenic liquid hydrogen storage tank without vacuum insulation for a small unmanned aerial vehicle was carried out in the present study. To prevent excess boil-off of cryogenic liquid hydrogen, the storage tank consisted of a 1-L inner vessel, an outer vessel, insulation layers and a vapor-cooled shield. For a cryogenic storage tank considered in this study, the appropriate heat inleak was allowed to supply the boil-off gas hydrogen to a proton electrolyte membrane fuel cell as fuel. In an effort to accommodate the hydrogen mass flow rate required by the fuel cell and to minimize the storage tank volume, a thermal analysis for various insulation materials was implemented here and their insulation performances were compared. The present thermal analysis showed that the Aerogel thermal insulations provided outstanding performance at the non-vacuum atmospheric pressure condition. With the Aerogel insulation, the tank volume for storing 1-L liquid hydrogen at 20 K could be designed within a storage tank volume of 7.2 L. In addition, it was noted that the exhaust temperature of boil-off hydrogen gas was mainly affected by the location of a vapor-cooled shield as well as thermal conductivity of insulation materials.     

Hydrogen dispersion phenomenon in nominally closed spaces

The hydrogen dispersion phenomenon in an enclosure depends on the ratio of the gas buoyancy-induced momentum and diffusive motions. Random diffusive motions of individual gas particles become dominative when the release momentum is low, and a uniform hydrogen concentration appears in the enclosure instead of the gas cumulation below the ceiling. The expected hydrogen behavior could be projected by the Froude number, which value ~1 predicts a decline of buoyancy. This paper justifies this hypothesis by demonstrating full-scale experimental results of hydrogen dispersion within a confined space under six different release variations. During the experiments, hydrogen was released into the test room of 60 m³ volume in two methods: through a nozzle and through 21 points evenly distributed on the emission box cover (multi-point release). Each release method was tested with three volume flow rates (3.2 × 10⁻³ m³/s, 1.6 × 10⁻³ m³/s, 3.3 × 10⁻⁴ m³/s). The tests confirm the decrease of hydrogen buoyancy and its stratification tendencies when the Mach, Reynolds, and Froud number values decrease. Because the hydrogen dispersion phenomenon would impact fire and explosive hazards, the presented experimental results could help fire protection systems be in an enclosure designed, allowing their effectiveness optimization.     

Pressure effects of an ignited release from onboard storage in a garage with a single vent

A numerical study has been performed comparing the hazards, in particular overpressures, arising from the sustained unignited and ignited release from an onboard hydrogen storage tank at 700 bar through a 3.34 mm diameter orifice, representing a thermally activated pressure relief device (TPRD) in a small garage with a single vent equivalent in area to small window. It has been demonstrated how the overpressure predicted in the case of an unignited release using both CFD and an analytical model is in the region of 0.55 kPa and thus unlikely to cause structural damage. However, the overpressure predicted for the ignited release is two orders of magnitude greater, reaching over 55 kPA in less than 1 s and thus potentially causing destruction of the structure.It has been shown that whilst the overpressures resulting from the unignited release are unlikely to cause harm, the garage is engulfed by a flammable atmosphere in less than 1 s and the oxygen is depleted to levels dangerous to people within this time. In the case of the ignited release, whilst the resultant overpressures are the primary safety concern, it has been shown how the thermal effects resulting from the release extend almost 9 m from the jet in 1.5 s.     

Evaluation of feeding strategies in upflow anaerobic sludge bed reactor for hydrogenogenesis at psychrophilic temperature

The present work evaluated the biohydrogen production from a 0.4 L upflow anaerobic sludge blanket reactor type (UASB) operating at psychrophilic temperature (21 ± 2 °C) at different feeding strategies varying hydraulic retention times (HRT) and sucrose concentration in the feeding. First strategy (24 h/31c) fed semi-continuously 31 g_sucrose L⁻¹ at 24 h HRT; second strategy (12 h/19c) fed semi-continuously 19 g_sucrose L⁻¹ at 12 h HRT; third strategy (4 h/8c) fed continuously 8.3 g_sucrose L⁻¹ at 4 h HRT.After 70 days of operation, the UASB accumulated 65.44 L H₂. The average HY for the whole operation during the three strategies was 62.6 NmL H₂ g_sucrose⁻¹, and average hydrogen content was 69.04%. In general terms, the best operation strategy was 12 h/19c since it presented good set of results, the best HY (70.6 NmL H₂ g_sucrose⁻¹) and a comparable hydrogen production rate (2.6 L (L d)⁻¹) to that obtained in 4 h/8c strategy (3.17 L (L d)⁻¹). The average gross energy potential rate from the 12 h/19c strategy was 46.21 kJ (L d)⁻¹, whereas energy heating losses were circumvented due to operation at psychrophilic regime. Indeed, psychrophilic or room temperatures should be broadly regarded as an effective alternative towards net energy gains in biohydrogen production.     

Performance of hydrogen storage tank with TPRD in an engulfing fire

The performance of a composite hydrogen storage tank with TPRD in an engulfing fire is studied. The non-adiabatic tank blowdown model, including in fire conditions, using the under-expanded jet theory is described. The model input includes thermal parameters of hydrogen and tank materials, heat flux from a fire to the tank, TPRD diameter and TPRD initiation delay time. The unsteady heat transfer from surroundings through the tank wall and liner to hydrogen accounts for the degradation of the composite overwrap resin and melting of the liner. The model is validated against the blowdown experiment and the destructive fire test with a tank without TPRD. The model accurately reproduces experimentally measured hydrogen pressure and temperature dynamics, blowdown time, and tank's fire-resistance rating, i.e. time to tank rupture in a fire without TPRD. The lower limit for TPRD orifice diameter sufficient to prevent the tank rupture in a fire and, at the same time, to reduce the flame length and mitigate the pressure peaking phenomenon in a garage to exclude its destruction, is assessed for different tanks, e.g. it is 0.75 mm for largest studied 244 L, 70 MPa tank. The phenomenon of Type IV tank liner melting for TPRD with lower diameter is revealed and its influence on hydrogen blowdown is assessed. This phenomenon facilitates the blowdown yet requires further detailed experimental validation.     

Hydrogen dispersion in a closed environment

The highly combustible nature of hydrogen poses a great hazard, creating a number of problems with its safety and handling. As a part of safety studies related to the use of hydrogen in a confined environment, it is extremely important to have a good knowledge of the dispersion mechanism.The present work investigates the concentration field and flammability envelope from a small scale leak. The hydrogen is released into a 0.47 m × 0.33 m x 0.20 m enclosure designed as a 1/15 – scale model of a room in a nuclear facility. The performed tests evaluates the influence of the initial conditions at the leakage source on the dispersion and mixing characteristics in a confined environment. The role of the leak location and the presence of obstacles, are also analyzed. Throughout the test, during the release and the subsequent dispersion phase, temporal profiles of hydrogen concentration are measured using thermal conductivity gauges within the enclosure. In addition, the BOS (Background Oriented Schlieren) technique is used to visualise the cloud evolution inside the enclosure. These instruments allow the observation and quantification of the stratification effects.     

Safety study of a hydrogen leak in a fuel cell vehicle using computational fluid dynamics

This paper analyzes safety aspects inside a Fuel Cell vehicle using Computational Fluid Dynamics (CFD) tools. The research considers an introduction of a leak of hydrogen inside the vehicle, and its dispersion for a set of typical ventilation conditions is analyzed. The leak of hydrogen has been modelled according to the properties of hydrogen and depending on the pressure difference between the hydrogen storage tank (200 bar) and the atmosphere. The parameters considered for the simulations are the flow rate of cabin ventilation air and hydrogen’s leak. The results obtained for the hydrogen molar concentration are investigated in different sections of the vehicle. Significant differences between front and rear areas are observed, with higher hydrogen concentrations near the rear ventilation vents. The volume of the vehicle within ignition risk (4–75% hydrogen concentration) is also investigated. Finally, different risk mitigation measures are also proposed.     

Effects of substrate concentration and hydraulic retention time on hydrogen production from common reed by enriched mixed culture in continuous anaerobic bioreactor

This study aims to investigate the effect of substrate concentration and hydraulic retention time (HRT) on hydrogen production in a continuous anaerobic bioreactor from unhydrolyzed common reed (Phragmites australis) an invasive wetland and perennial grass. The bioreactor has capacity of 1 L and working volume of 600 mL. It was operated at pH 5.5, temperature at 37 °C, hydraulic retention time (HRT) 12 h, and variation of substrate concentration from 40, 50, and 60 g COD/L, respectively. Afterward, the HRT was then varied from 12, 8, to 4 h for checking the optimal biohydrogen production. Each condition was run until reach steady state on hydrogen production rate (HPR) which based on hydrogen percentage and daily volume. The results were obtained the peak of substrate concentration was at the 50 g COD/L with HRT 12 h, average HPR and H₂ concentration were 28.71 mL/L/h and 36.29%, respectively. The hydrogen yield was achieved at 106.23 mL H₂/g CODre. The substrate concentration was controlled at 50 g COD/L for the optimal HRT experiments. It was found that the maximum of average HPR and H₂ concentration were 43.28 mL/L/h and 36.96%, respectively peak at HRT 8 h with the corresponding hydrogen yield of 144.35 mL H₂/g CODre. Finally, this study successful produce hydrogen from unhydrolyzed common reed by enriched mixed culture in continuous anaerobic bioreactor.     

Biological hydrogen production from sweet sorghum syrup by mixed cultures using an anaerobic sequencing batch reactor (ASBR)

Continuous biological hydrogen production from sweet sorghum syrup by mixed cultures was investigated by using anaerobic sequencing batch reactor (ASBR). The ASBR was conducted based on the optimum condition obtained from batch experiment i.e. 25 g/L of total sugar concentration, 1.45 g/L of FeSO₄ and pH of 5.0. Feasibility of continuous hydrogen fermentation in ASBR operation at room temperature (30 ± 3 °C) with different hydraulic retention time (HRT) of 96, 48, 24 and 12 hr and cycle periods consisting of filling (20 min), settling (20 min), and decanting (20 min) phases was analyzed. Results showed that hydrogen content decreased with a reduction in HRT i.e. from 42.93% (96 hr HRT) to 21.06% (12 hr HRT). Decrease in HRT resulted in a decrease of solvents produced which was from 10.77 to 2.67 mg/L for acetone and 78.25 mg/L to zero for butanol at HRT of 96 hr-12 hr, respectively. HRT of 24 hr was the optimum condition for ASBR operation indicated by the maximum hydrogen yield of 0.68 mol H₂/mol hexose. The microbial determination in DGGE analysis indicated that the well-known hydrogen producers Clostridia species were dominant in the reacting step. The presence of Sporolactobacillus sp. which could excrete the bacteriocins causing the adverse effect on hydrogen-producing bacteria might responsible for the low hydrogen content obtained.     

Simultaneous hydrogen and ethanol production from a mixture of glucose and xylose using extreme thermophiles I: Effect of substrate and pH

The simultaneous hydrogen and ethanol production from glucose and xylose was investigated. The effect of carbon sources on hydrogen and ethanol production was examined in batches. When the substrate concentration was increased from 1 g/L to 7 g/L, the hydrogen yield decreased from 0.74 mol/mol to 0.15 mol/mol and from 0.67 mol/mol to 0.07 mol/mol for glucose and xylose. The highest ethanol yield of 1.19 mol/(mol·glucose) was obtained at 5 g/L glucose and 6 g/L xylose concentrations. For the co-fermentation of glucose and xylose, the highest ethanol yield 1.54 mol/(mol·hexose) was obtained at 2.5 g/L glucose to 2.5 g/L xylose (1:1). However, the hydrogen yield was not significantly affected by the glucose to xylose ratio. Continuous co-fermentation of glucose and xylose by extreme thermophiles was successfully demonstrated using an upflow anaerobic reactor. The hydrogen production rate, the ethanol concentration, and the substrate degradation efficiency increased along with pH. The optimal pH for the continuous mode was determined to be in the range of 5.8–6.6.     

Natural and forced ventilation of buoyant gas released in a full-scale garage: Comparison of model predictions and experimental data

An increase in the number of hydrogen-fueled applications in the marketplace will require a better understanding of the potential for fires and explosion associated with the unintended release of hydrogen within a structure. Predicting the temporally evolving hydrogen concentration in a structure, with unknown release rates, leak sizes and leak locations is a challenging task. A simple analytical model was developed to predict the natural and forced mixing and dispersion of a buoyant gas released in a partially enclosed compartment with vents at multiple levels. The model is based on determining the instantaneous compartment over-pressure that drives the flow through the vents and assumes that the helium released under the automobile mixes fully with the surrounding air. Model predictions were compared with data from a series of experiments conducted to measure the volume fraction of a buoyant gas (at 8 different locations) released under an automobile placed in the center of a full-scale garage (6.8 m × 5.4 m × 2.4 m). Helium was used as a surrogate gas, for safety concerns. The rate of helium released under an automobile was scaled to represent 5 kg of hydrogen released over 4 h. CFD simulations were also performed to confirm the observed physical phenomena. Analytical model predictions for helium volume fraction compared favorably with measured experimental data for natural and forced ventilation. Parametric studies are presented to understand the effect of release rates, vent size and location on the predicted volume fraction in the garage. Results demonstrate the applicability of the model to effectively and rapidly reduce the flammable concentration of hydrogen in a compartment through forced ventilation.     

Impact of 5-hydroxy methyl furfural on continuous hydrogen production from galactose and glucose feedstock with periodic recovery

A continuous stirred tank reactor (CSTR) was operated for more than 120 days with fixed hydraulic retention time of 6 h at mesophilic temperature along with a periodic recovery phase towards hydrogen production and stimulated by the existence of 5-hydroxy methyl furfural concentration (5-HMF). Interestingly, CSTR mixed with a small amount of 5-HMF, range of 0.3–0.6 g/L showed at least 50% higher hydrogen production rate than control without 5-HMF. However, when 5-HMF concentration was higher than 0.6 g/L, the performance was significantly inhibited. The bacterial community shifted by 5-HMF from Clostridium-dominated to Lactobacillus-dominated population. Regardless of the remain 5-HMF concentration in CSTR, the microbial community and hydrogen producing performance were restored by stop mixing the 5-HMF from the feedstock. The high-rate hydrogen production of 20.0 ± 1.8 L H₂/L/d was achieved in the presence of 5-HMF using the threshold information and recovery strategy.     

Hydrogen cryo-adsorption by hexagonal prism monoliths of MIL-101

Hexagonal prism shaped monoliths of envelope density 0.40–0.467 g/cm³ and remarkable mechanical stability were obtained from MIL-101 powder. The hydrogen adsorption isotherms within an extended pressure range show that the excess adsorption decreases with the increasing density of the pellets. At 77 K and 150 bar, the total volumetric capacity is 46.5 g/L; the discharge to 159 K and 5 bar leads to 45 g/L (38.8 g/L referring to the outer tank volume) supporting MIL-101 as a promising candidate for applications in the 77–160 K range of interest for cryo-adsorption hydrogen storage method. The isosteric adsorption enthalpy evaluated from the experimental data with the van't Hoff equation, using fugacity, is in agreement with the calorimetric heat of adsorption reported in literature. Monoliths of this shape allow the best possible packing density of any sorbent in a container and the primary data reported here on MIL-101 could serve as material engineering properties required for modeling hydrogen storage tanks.     

Effects of size and autoclavation of fruit and vegetable wastes on biohydrogen production by dark dry anaerobic fermentation under mesophilic condition

Fermentative hydrogen production from fruit and vegetable wastes (FVWs) through Dry Fermentation Technology (DFT) was studied through three independent experiments in order to find out the effect of particle size and autoclaving pretreatment on bio-hydrogen production from FVWs and as follows: (1) autoclaved FVWs with sizes < 5 cm (experiment I); (2) raw FVWs with sizes < 5 cm (experiment II) and (3) autoclaved FVWs with sizes > 5 cm (experiment III). The assay with autoclaved waste yielded a higher percentage of hydrogen in the headspace of the dry fermenter reaching a maximum value of 44% in experiment I. However, the maximum hydrogen production was obtained in experiment III with 14573 NmL at a yield of 23.53 NmL H₂/gVS. Profiling of the microbial communities by denaturing gradient gel electrophoresis (DGGE) indicated that the most prominent species were the genera Clostridium, Bifidobacterium, and Lactobacillus.     

Hydrogen permeation from CGH2 vehicles in garages: CFD dispersion calculations and experimental validation

The time and space evolution of the distribution of hydrogen in confined settings was investigated computationally and experimentally for permeation from typical compressed gaseous hydrogen (CGH2) storage systems for buses or cars. The main goal was to examine whether hydrogen is distributed homogeneously within a garage-like facility or whether stratified conditions are developed, under certain conditions. The nominal hydrogen flow rate considered was 1.087 L/min in a bus facility with a volume of 681 m³. The release was assumed to be directed upwards from a 0.15 m diameter hole located at the middle part of the bus cylinders casing. Ventilation rates up to 0.03 air changes per hour (ACH) were considered. Simulated time periods extended up to 20 days. The CFD simulations performed with the ADREA-HF code showed that fully homogeneous conditions exist for low ventilation rates, while stratified conditions prevail for higher ventilation rates. Regarding flow structure it was found that the vertical concentration profiles can be considered as the superposition of the concentration at the floor (driven by diffusion) plus a concentration difference between floor and ceiling (driven by buoyancy forces). In all cases considered this concentration difference was found to be less than 0.5%. The dispersion experiments were performed in a large scale garage-like enclosure of 40 m³ using helium (GARAGE facility). Comparison between CFD simulations and experiments showed that the predicted concentrations were in good agreement with the experimental data. Finally, simulations were performed using two integral models: the fully homogeneous model and a two-layer model and the results were compared both against CFD and the experimental data.     

Measurements of effective diffusion coefficients of helium and hydrogen through gypsum

An experimental apparatus, which was based on the ¼-scale garage previously used for studying helium release and dispersion in our laboratory, was used to obtain effective diffusion coefficients of helium and hydrogen (released as forming gas for safety reasons) through gypsum panel. Two types of gypsum panel were used in the experiments. Helium or forming gas was released into the enclosure from a Fischer burner¹ located near the enclosure floor for a fixed duration and then terminated. Eight thermal-conductivity sensors mounted at different vertical locations above the enclosure floor were used to monitor the temporal and spatial gas concentrations. An electric fan was used inside the enclosure to mix the released gas to ensure a spatially uniform gas concentration to minimize stratification. The temporal variations of the pressure difference between the enclosure interior and the ambience were also measured. An analytical model was developed to extract the effective diffusion coefficients from the experimental data.