Publications

Hydrogen sulfide corrosion is one of the main reasons of steels destruction in the oil and gas industry. Damages appear as a result of corrosion and hydrogen embrittlement and corrosion cracking occurs when the load is applied. The influence of the steels structure on its stress corrosion cracking under the loads in hydrogen sulfide environment is insufficiently studied. The aim of the study is to determine the influence of the steels structure on its corrosion hydrogenation and corrosion cracking in the NACE hydrogen sulfide solution.<br/>It was established that the corrosion rate and hydrogenation of steel У8 in the NACE solution grows when the structure dispersion increases from perlite to sorbite troostite and martensite. The corrosion rate and hydrogenation of steel 45 are the greatest in pearlite-ferrite while the smallest - in sorbite.<br/>The corrosion of steels У8 and 45 in the NACE solution is localized: the average size of the ulcers is 50 ... 80 μm on the steel У8 and 45 ... 65 μm on steel 45. The depth of ulcers is maximal on the steel У8 with the martensite structure (~ 260 μm) and on the steel 45 with the troostite structure (~ 210 μm).<br/>Static load (σ = 300 MPa) increases the hydrogenation of steels in the hydrogen sulfide environment. The concentration of hydrogen in steel У8 with troostite structure increases by ~ 1.8 times. The concentration of hydrogen in steel 45 with troostite and martensite structures increases by ~ 1.2...1.3 and by ~ 1.4...1.6 times respectively.<br/>The steel У8 with martensite and perlite structures and steel 45 with troostite structure has the lowest resistance to corrosion cracking. Steels destruction depends on both hydrogen permeation and the corrosion localization which leads to the increase of the microelectrochemical heterogeneity of the surfaces.

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.

Experiments in an obstructed semi-confined vertical combustion channel with a height of 6 m (cross-section 0.4 × 0.4 m) inside a safety vessel of the hydrogen test center HYKA at the Karlsruhe Institute of Technology (KIT) are reported. In the work homogeneous hydrogen-air-mixtures as well as mixtures with different well-defined H2-concentration gradients were ignited either at the top or at the bottom end of the channel. The combustion characteristics were recorded using pressure sensors and sensors for the detection of the flame front that were distributed along the complete channel length. In the tests slow subsonic and fast sonic deflagrations as well as detonations were observed and the conditions for the flame acceleration (FA) to speed of sound and deflagration-to-detonation transition (DDT) are compared with the results of similar experiments performed earlier in a larger semi-confined horizontal channel.

Consequence modelling of high potential risks of usage and transportation of cryogenic liquids yet requires substantial improvements. Among the cryogenics liquid hydrogen (LH2) needs especial treatments and a comprehensive understanding of spill and spread of liquid and dispersion of vapor. Even though many of recent works have shed lights on various incidents such as spread dispersion and explosion of the liquid over land less focus was given on spill and spread of LH2 onto water. The growing trend in ship transportation has enhanced risks such as ships’ accidental releases and terrorist attacks which may ultimately lead to the release of the cryogenic liquid onto water. The main goal of the current study is to present a computational fluid dynamic (CFD) approach using OpenFOAM to model release and spread of LH2 over water substrate and discuss previous approaches. It also includes empirical heat transfer equations due to boiling and computation of evaporation rate through an energy balance. The results of the proposed model will be potentially used within another coupled model that predicts gas dispersion]. This work presents a good practice approach to treat pool dynamics and appropriate correlations to identify heat flux from different sources. Furthermore some of the previous numerical approaches to redistribute or in some extend manipulate the LH2 pool dynamic are brought up for discussion and their pros and cons are explained. In the end the proposed model is validated by modelling LH2 spill experiment carried out in 1994 at the Research Centre Juelich in Germany.

Catastrophic rupture of onboard hydrogen storage in a fire is a safety concern. Different passive e.g. fireproofing materials the thermally activated pressure relief device (TPRD) and active e.g. initiation of TPRD by fire sensors safety systems are being developed to reduce hazards from and associated risks of high-pressure hydrogen storage tank rupture in a fire. The probability of such low-frequency highconsequences event is a function of fire resistance rating (FRR) i.e. the time before tank without TPRD ruptures in a fire the probability of TPRD failure etc. This safety issue is “confirmed” by observed recently cases of CNG tanks rupture due to blocked or failed to operate TPRD etc. The increase of FRR by any means decreases the probability of tank rupture in a fire particularly because of fire extinction by first responders on arrival at an accident scene.<br/>This study of socio-economic effects of safety applies a quantitative risk assessment (QRA) methodology to an example of hydrogen vehicles with passive tank protection system on roads in London.<br/>The risk is defined here through the cost of human loss per fuel cell hydrogen vehicle (FCHV) fire accident and fatality rate per FCHV per year. The first step in the methodology is the consequence analysis based on validated deterministic engineering tools to estimate the main identified hazards: overpressure in the blast wave at different distances and the thermal hazards from a fireball in the case of catastrophic tank rupture in a fire. The population can be exposed to slight injury serious injury and fatality after an accident. These effects are determined based on criteria by Health and Safety Executive (UK) and a cost metrics is applied to the number of exposed people in these three harm categories to estimate the cost per an accident. The second step in the methodology is either the frequency or the probability analysis. Probabilities of a vehicle fire and failure of the thermally activated pressure relief device are taken from published sources. A vulnerability probit function is employed to calculate the probability of emergency operations’ failure to prevent tank rupture as a function of a storage tank FRR and time of fire brigade arrival. These later results are integrated to estimate the tank rupture frequency and fatality rate. The risk is presented as a function of fire resistance rating.<br/>The QRA methodology allows to calculate the cost of human loss associated with an FCHV fire accident and demonstrates how the increase of FRR of onboard storage as a safety engineering measure would improve socio-economics of FCHV deployment and public acceptance of the technology.

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.

Stationary pressure vessels for the storage of large volumes of gaseous hydrogen at high pressure (>70 MPa) are typically manufactured from Cr-Mo steels. These steels display hydrogen-enhanced fatigue crack growth but pressure vessels can be manufactured using defect-tolerant design methodologies. However storage volumes are limited by the wall thickness that can be reliably manufactured for quench and tempered Cr-Mo steels typically not more than 25-35 mm. High-hardenability steels can be manufactured with thicker walls which enables larger diameter pressure vessels and larger storage volumes. The goal of this study is to assess the fracture and fatigue response of high hardenability Ni-Cr-Mo pressure vessel steels for use in high-pressure hydrogen service at pressure in excess of 1000 bar. Standardized fatigue crack growth tests were performed in gaseous hydrogen at frequency of 1Hz and for R-ratios in the range of 0.1 to 0.7. Elastic-plastic fracture toughness measurements were also performed. The measured fatigue and fracture behavior is placed into the context of previous studies on fatigue and fracture of Cr-Mo steels for gaseous hydrogen.

Explosion relief panels or doors are often used in industrial buildings to reduce damages caused by gas explosions. Decades of research have contributed to the understanding of the phenomena involved in gas explosions in order to establish an effective method to predict reliably the explosion overpressure. All the methods predict a monotonic increase of the overpressure with the concentration of the gas in the range from the lower explosion limit to the stoichiometric one. Nevertheless in few cases a non-monotonic behaviour of the maximum developed pressure as a function of hydrogen concentration was reported in the literature. The non-monotonic behaviour was also observed during experimental tests performed at the Scalbatraio laboratory at the University of Pisa in a 25 m3 vented combustion test facility with a vent area of 112 m2. This paper presents the results obtained during the tests and investigates the possible explanations of the phenomena.

Studying thermal ignition mechanisms is a key step for evaluating many ignition hazards. In the present work two-dimensional simulations with detailed chemistry are used to study the reaction pathways of the transient flow and ignition of a stoichiometric hydrogen-air mixture by moving hot spheres. For temperatures above the ignition threshold ignition takes place after a short time between the front stagnation point and separation location depending upon the sphere's surface temperature. Closer to the threshold the volume of gas adjacent to the separation region ignites homogeneously after a longer time. These results demonstrate the importance of boundary layer development and flow separation in the ignition process.

Since the rapid development of hydrogen stationary and vehicle fuel cells the last decade it is of importance to improve the prediction of overpressure generated during an accidental explosion which could occur in a confined part of the system. To this end small-scale vented hydrogen–air explosions were performed in a transparent cubic enclosure with a volume of 3375 cm3. The flame propagation was followed with a high speed camera and the overpressure inside the enclosure was recorded using high frequency piezoelectric transmitters. The effects of vent area and ignition location on the amplitude of pressure peaks in the enclosed volume were investigated. Indeed vented deflagration generates several pressures peaks according to the configuration and each peak can be the dominating pressure. The parametric study concerned three ignition locations and five square vent sizes.