Experimental studies on wind influence on hydrogen release from low pressure pipelines

At the DIMNP (Department of Mechanical, Nuclear and Production Engineering) laboratories of University of Pisa (Italy) a pilot plant called HPBT (Hydrogen Pipe Break Test) was built in cooperation with the Italian Fire Brigade Department. The apparatus consists of a 12 m³ tank connected with a 50 m long pipe. At the far end of the pipeline a couple of flanges have been used to house a disc with a hole of the defined diameter. The plant has been used to carry out experiments of hydrogen release. During the experimental activity, data have been acquired about the gas concentration and the length of release as function of internal pressure and release hole diameter. The information obtained by the experimental activity will be the basis for the development of a new specific normative framework arranged to prevent fire and applied to hydrogen. This study is focused on hydrogen concentration as function of wind velocity and direction. Experimental data have been compared with theoretical and computer models (such as CFD simulations).     

CFD modelling of accidental hydrogen release from pipelines

Although nowadays hydrogen is distributed mainly by trailers, in the future distribution by means of pipelines will be more suitable if larger amounts of hydrogen are produced on industrial scale. Therefore from the safety point of view it is essential to compare hydrogen pipelines to natural gas pipelines, whose use is well established today. Within the paper we compare safety implications in accidental situations. In the analysis we do not consider technological aspects such as compressors or seals.     

Dynamic behaviour of non-isothermal compressible natural gases mixed with hydrogen in pipelines

This paper focuses on non-isothermal transient flow in mixed hydrogen–natural gas pipelines. The effect of hydrogen injection into natural gas pipelines has been investigated in particular the pressure and temperature conditions, Joule–Thomson effect, linepack and energy consumption of the compressor station. The gas flow is described by a set of partial differential equations resulting from the conservation of mass, momentum and energy. Real gas effects are determined by the predictive Soave–Redlich–Kwong group contribution method. The Yamal-Europe gas pipeline on Polish territory has been selected as case study.     

Recommendations on X80 steel for the design of hydrogen gas transmission pipelines

By limiting the pipes thickness necessary to sustain high pressure, high-strength steels could prove economically relevant for transmitting large gas quantities in pipelines on long distance. Up to now, the existing hydrogen pipelines have used lower-strength steels to avoid any hydrogen embrittlement. The CATHY-GDF project, funded by the French National Agency for Research, explored the ability of an industrial X80 grade for the transmission of pressurized hydrogen gas in large diameter pipelines. This project has developed experimental facilities to test the material under hydrogen gas pressure. Indeed, tensile, toughness, crack propagation and disc rupture tests have been performed. From these results, the effect of hydrogen pressure on the size of some critical defects has been analyzed allowing proposing some recommendations on the design of X80 pipe for hydrogen transport. Cost of Hydrogen transport could be several times higher than natural gas one for a given energy amount. Moreover, building hydrogen pipeline using high grade steels could induce a 10 to 40% cost benefit instead of using low grade steels, despite their lower hydrogen susceptibility.     

Thermodynamics of spontaneous dissociation and dissociative adsorption of hydrogen molecules and hydrogen atom adsorption and absorption on steel under pipelining conditions

While hydrogen pipelines have attracted increased attention, safety of the pipelines has been a concern in terms of hydrogen embrittlement (HE) occurring upon hydrogen atom (H) generation and permeation in the steels. In this work, thermodynamic analyses regarding H generation and adsorption on pipeline steels by two potential mechanisms, i.e., spontaneous dissociation and dissociative adsorption, were conducted through theoretical calculations based on Gibbs free energy change of the H generation reactions. Moreover, H adsorption free energy and configurations were determined based on density functional theory (DFT) calculations. Effects of H adsorption site, H coverage and hydrostatic stress on H adsorption and absorption were discussed. Spontaneous dissociation of hydrogen gas molecules to generate hydrogen atoms is thermodynamically impossible. Dissociative adsorption is thermodynamically feasible at wide temperature and pressure ranges. Particularly, an increased hydrogen gas partial pressure and elevated temperature favor the dissociative adsorption of hydrogen. Hydrogen atoms generated by dissociative adsorption mechanism can adsorb stably at On-Top (OT) and 2-fold (2F) Cross-Bridge sites of Fe (100), while hydrogen adsorption at 2F site is more stable due to a higher electron density and a stronger electronic hybridization between Fe and H. The influence of H atom coverage on dissociative adsorption occurs at low coverages only, i.e., 0.25–1.00 ML as determined in this work. External stresses make dissociative adsorption more difficult to occur compared with a fully relaxed steel. Both tetrahedral sites (TS) and octahedral sites (OS) can potentially host absorbed H atoms at subsurface of the steel. Absorbed H atoms will be predominantly trapped at TS due to a low energy path and exothermic feature. Diffusion of H atoms from steel surface to the subsurface is more difficult compared with the dissociative adsorption.     

High-yield hydrogen production from glucose by supercritical water gasification without added catalyst

Continuous supercritical water gasification of glucose is investigated with a recently developed updraft gasification apparatus under various conditions: temperatures of 600–767 °C, residence times of 15–60 s, glucose concentrations of 1.8–15 wt% and without added a catalyst. The experimental gas yields are compared with predicted values at equilibrium that are estimated via Gibbs free energy minimization. Total gas yields and hydrogen gas yield increase with temperature. At 740 °C and 1.8 wt%, hydrogen gas yields become very high (10.5–11.2 mol/mol glucose). The hydrogen gas yields do not vary significantly with different residence times. The hydrogen gas yield decreases to 5.7 mol/mol glucose at 15 wt%, a value very close to the predicted value (6.3 mol/mol glucose). Only acetic acid is detected in the liquid effluents at temperatures above 740 °C, while 42 products are detected at 600 °C. The highest hydrogen gas yield obtained in this study is 11.5 mol/mol glucose at 25 MPa, 767 °C, and 1.8 wt%, for 60 s; this value is very close to the theoretical equilibrium hydrogen yield of 11.9 mol/mol glucose. Under these conditions, the carbon efficiency is very high (91%) and total organic carbon (TOC) in the liquid product is very low (23 ppm), indicating that glucose is almost completely converted to gaseous products. Comparison with other work under similar operating conditions shows that the current reactor is capable of attaining higher hydrogen gas yields at temperatures above 650 °C. Possible explanations for the higher hydrogen gas yields are presented.     

Leakage and diffusion behavior of a buried pipeline of hydrogen-blended natural gas

Buried pipelines are one method of conservation transfer for widely used gases such as natural gas and hydrogen. The safety of these pipelines is of great importance because of the potential leakage risks posed by the flammable gas and the special properties of the hydrogen mixture. Estimating the leakage behavior and quantifying the diffusion range outside the pipeline are important but challenging goals due to the hydrogen mixture and presence of soil. This study provides essential information about the diffusion behavior and concentration distribution of underground hydrogen and natural gas mixture leakages. Therefore, a large-scale experimental system was developed to simulate high-pressure leaks of hydrogen mixture natural gas from small holes in three different directions from a pipeline buried in soil. The diffusion of hydrogen-doped natural gas in soil was experimentally measured under different conditions, such as different hydrogen mixture ratios, release pressures, and leakage directions. The experimental results verified the applicability of the gas leakage mass flow model, with an error of 6.85%. When a larger proportion of a single component was present in the hydrogen-doped natural gas, the leakage pressure showed a greater diffusion range. In addition, the diffusion range of hydrogen-doped natural gas in the leakage direction was larger at 3 o'clock than that at 12 o'clock. The hydrogen blend carried methane and diffused, which shortened the methane saturation time. Moreover, a quantitative relationship between the concentration of hydrogen-doped natural gas and the diffusion distance over which the hydrogen-doped natural gas reached the lower limit of the explosion was obtained by quantitative analysis of the experimental data.     

Hydrogen solubility in molten TiAl alloys

In this work, the hydrogen solubility in a titanium–aluminium (TiAl) binary alloy melt was investigated through a theoretical analysis and the results compared subsequently with values determined experimentally. Determination of the theoretical values of hydrogen solubility is based on a modified version of Sievert’s law, in which hydrogen solubility is related to the activity coefficient of the alloy melt and the hydrogen solubility in pure liquid metals. The activity coefficient is obtained in terms of the free volume theory, in which excess entropy is sufficiently taken into account. The experimental values of the hydrogen solubility in the two alloy melts, Ti45Al and Ti47Al, were determined to validate the calculated values. This was performed using hydrogen charging apparatus. The experimental values obtained were in good agreement with the calculated values.     

Enhancing the production of hydrogen via water–gas shift reaction using Pd-based membrane reactors

In this work, it is described an experimental study regarding the performance of a Pd–Ag membrane reactor recently proposed and suitable for the production of ultra-pure hydrogen. A dense metallic permeator tube was assembled by an innovative annealing and diffusion welding technique from a commercial flat sheet membrane of Pd–Ag. A “finger-like” configuration of the self-supported membrane has been designed and used as a packed-bed membrane reactor (MR) for producing ultra-pure hydrogen via water–gas shift reaction (WGS).     

Hydride destabilization in core–shell nanoparticles

We present a model that describes the effect of elastic constraint on the thermodynamics of hydrogen absorption and desorption in biphasic core–shell nanoparticles, where the core is a hydride forming metal. In particular, the change of the hydride formation enthalpy and of the equilibrium pressure for the metal/hydride transformation are described as a function of nanoparticles radius, shell thickness, and elastic properties of both core and shell. To test the model, the hydrogen sorption isotherms of Mg–MgO core–shell nanoparticles, synthesized by inert gas condensation, were measured by means of optical hydrogenography. The model's predictions are in good agreement with the experimentally determined plateau pressure of hydrogen absorption. The features that a core–shell systems should exhibit in view of practical hydrogen storage applications are discussed with reference to the model and the experimental results.     

Experimental study of hydrogen explosion in repeated pipe congestion – Part 2: Effects of increase in hydrogen concentration in hydrogen-methane-air mixture

Hydrogen is seen as an important energy carrier for the future which offers carbon free emissions. At present it is mainly used in refueling hydrogen fuel cell cars. However, it can also be used together with natural gas in existing gas fired equipment with the benefit of lower carbon emissions. This can be achieved by introducing hydrogen into existing natural gas pipelines. These pipelines are designed, constructed and operated to safely transport natural gas, which is mostly methane. Because hydrogen has significantly different physical and chemical properties than natural gas, any addition of hydrogen my adversely affect the integrity of the pipeline network, increasing the likelihood and consequences of an accidental leak. Since it increases the likelihood and consequences of an accidental leak, it increases the risk of explosion. In order to address various safety issues related to addition of hydrogen in to a natural gas pipeline a EU project NATURALHY was introduced. A major objective of the NATURALHY project was to identify how much hydrogen could be introduced into the natural gas pipeline network. Such that it does not adversely impact the safety of the pipeline network and significantly increase the risk to the public. This paper reports experimental work conducted to measure the explosion overpressure generated by ignition of hydrogen-methane-air mixture in a highly congested region consisting of interconnected pipes. The composition of the methane/hydrogen mixture used was varied from 0% hydrogen (100% methane) to 100% hydrogen (0% methane) to understand its effect on generated explosion overpressure. It was observed that the maximum overpressures generated by methane-hydrogen mixtures with 25% (by volume) or less hydrogen content are not likely to be significantly greater than those generated by methane alone. Therefore, it can be concluded that the addition of less than 25% by volume of hydrogen into pipeline networks would not significantly increase the risk of explosion.     

Development and validation of a laminar flame speed correlation for the CFD simulation of hydrogen-enriched gasoline engines

In this paper, a laminar flame speed correlation was developed and validated for the computational fluid dynamics (CFD) simulation of hydrogen-enriched gasoline engines. This correlation was derived through the tabulated data which was determined by a self-developed calculation program according to the flame temperature-based mixing rule. Wide ranges of hydrogen volume fractions (0–10%), equivalence ratios (0.6–1.5), unburned gas temperatures (300–2500 K), pressures (1–50 bar) and residual gas mass fractions (0–20%) were simultaneously considered in this correlation to cover the burning conditions encountered in SI engines. The estimated values of the new correlation were found to be in satisfying agreement with the experimental data under normal burning conditions. Moreover, the new correlation was implemented in the extended coherent flame model to evaluate its suitability for CFD simulation. Satisfying agreement between the experimental and calculated results was observed under all examined hydrogen addition levels. This indicated that the new correlation was suitable for the CFD simulation of hydrogen-enriched gasoline engines.     

Experimental investigation and theoretical analysis on measurement of hydrogen adsorption in vacuum system

A volumetric apparatus for hydrogen adsorption measurement aimed at vacuum system was constructed. The performance of the apparatus was assessed by using the composite adsorbent that includes molecular sieve 5A and differential proportion of PdO and Ag₂O. In order to avoid the accumulative error, the whole system is evacuated every time for each point of pressure, instead of changing pressure step-by-step and summing up the amount of adsorption at each step. Iterative calculation of processing experimental data is used. Experimental results and theoretical analysis showed that the volumetric apparatus, the procedure and the method of data processing described in this paper can provide an accurate measurement of hydrogen adsorption in vacuum system. The capacities of freshly activated composite adsorbent for hydrogen are found to increase markedly at low pressure after consecutive adsorption–desorption cycles. The phenomenon is known as the so-called “conditioning effect”. Besides the experimental errors, the large discrepancies on the reported adsorptive capacities of hydrogen on various adsorbents may be due to incomplete conditioning of the adsorbent, composition of the adsorbent and the slow rate of approach to equilibrium.     

Comparative study of turbulence models performance for refueling of compressed hydrogen tanks

Compressed hydrogen gas is a popular mode of fuel storage for hydrogen powered vehicles. When hydrogen gas is filled at high pressure, the gas temperature increases. The maximum gas temperature should be within acceptable safety standards. Numerical studies can help optimize the filling process. There is a high level of turbulence in the flow as the high velocity inlet jet is penetrating the nearly stagnant gas in the tank. Selection of a suitable turbulence model is important for accurate simulation of flow and heat transfer during filling of hydrogen tanks. In the present work, a comparative study is performed to identify suitable turbulence model for compressed hydrogen tank filling problem. Numerical results obtained with different turbulence models are compared with available experimental data. Considering accuracy, convergence and the computational expenses, it is observed that the realizable k-ε model is the most suitable turbulence model for hydrogen tank filling problem.     

Feasibility analysis of blending hydrogen into natural gas networks

Hydrogen fuel has the potential to mitigate the negative effects of greenhouse gases and climate change by neutralizing carbon emissions. Transporting large volume of hydrogen through pipelines needs hydrogen-specific infrastructure such as hydrogen pipelines and compressors, which can become an economic barrier. Thus, the idea of blending hydrogen into existing natural gas pipelines arises as a potential alternative for transporting hydrogen economically by using existing natural gas grids. However, there are several potential issues that must be considered when blending hydrogen into natural gas pipelines. Hydrogen has different physical and chemical properties from natural gas, including a smaller size and lighter weight, which require higher operating pressures to deliver the same amount of energy as natural gas. Additionally, hydrogen's small molecular size and lower ignition energy make it more likely to permeate through pipeline materials and seals, leading to degradation, and its wider flammability limits make it a safety hazard when leaks occur. In this study, we investigate these potential issues through simulation and technical surveys. We develop a gas hydraulic model to simulate the physical characteristics of a transmission and a distribution pipeline. This model is used throughout the study to visualize the potential impacts of switching from natural gas to hydrogen, and to investigate potential problems and solutions. Furthermore, we develop a Real-Time Transient Model (RTTM) to address the compatibility of current computational pipeline monitoring (CPM) based leak detection methods with blended hydrogen. Finally, we suggest the optimal hydrogen concentration for this model, and investigate the amount of carbon reduction that could be achieved, while considering the energy needs of the system.     

A theoretical framework for calculating full-scale jet fires induced by high-pressure hydrogen/natural gas transient leakage

Previous experimental results on full-scale jet fires induced by high-pressure hydrogen/natural gas transient leakage can only be suitable for solving practical engineering problems, or testing the limitation of previous models. Thus, this paper presents a theoretical framework for the high-pressure hydrogen/natural gas leakage and the subsequent jet fire. The proposed framework consists of a transient leakage model, a notional nozzle model, a jet flame size model, a radiative fraction correlation and a line source radiation model. The framework is validated by comparing the model predictions and experimental measurements of mass flow rate, total flame height and thermal radiation field of hydrogen, natural gas, hydrogen/natural gas mixture jet fires with a flame height up to 100 m. The comparison shows that the theoretical framework can give considerable predictions to properties of full-scale jet fires induced by high-pressure hydrogen/natural gas transient leakage.     

Some fundamental aspects in electrochemical hydrogen purification/compression

The electrochemical concentration of hydrogen from a poor hydrogen–inert gas mixture has been investigated by means of an electrochemical cell similar in construction to a hydrogen–air fuel cell, hydrogen being transported as hydrated protons, thorough a Nafion membrane, from the inlet (anode) to the outlet (cathode) compartments of the cell. Galvanostatic and tensiostatic mode of operation have been investigated: in the first case and erratic behaviour of the cell has been observed, mainly because of the non-controllable variations of the membrane water content. Under tensiostatic condition the role of the applied voltage, feed flow rate, water vapour content in the feed mixture and temperature has been studied, with two different designs of the gas feed distribution plates. From the analysis of experimental data it is possible to evaluate the current efficiency, the hydrogen recovery, the hydrogen purity, the exergy gain and the coefficient of performance of the cell.     

An MILP model for the reformation of natural gas pipeline networks with hydrogen injection

A mixed integer linear programming (MILP) model is proposed for the reformation of natural gas pipelines. The model is based on the topology of existing pipelines, the load and pressure at each node and the design factors of the region and minimizes the annual substitution depreciation cost of pipelines, the annual construction depreciation cost of compressor stations and the operating cost of existing compressor stations. Considering the nonlinear pressure drop equations, the model is linearized by a piecewise method and solved by the Gurobi optimizer. Two cases of natural gas pipeline networks with hydrogen injection are presented. Several adjustments are applied to the original natural gas pipeline network to ensure that our design scheme can satisfy the safety and economic requirements of gas transportation. Thus, this work is likely to serve as a decision-support tool for the reformation of pipeline networks with hydrogen injection.     

Technical prospects for commercial and residential distribution and utilization of hydrogen

Hydrogen has been suggested as a fuel gas to eventually replace natural gas in commercial and residential heating and cooking applications. After transmission from a production site to a city gate, the delivery of hydrogen would be through the pipelines of conventional (natural gas) distribution systems. It would be combusted in appliances with suitably modified burners. Through a recent technology survey sponsored by NASA (Marshall Space Flight Center, Huntsville, Alabama) and through experimental and analytical efforts at the Institute of Gas Technology, we have assembled preliminary technical assessments for the distribution and utilization of hydrogen in this role.

The flow rates and pressures of a gas distribution system using hydrogen probably will be different from those for natural gas. Increased operating pressures are predicted for hydrogen flow conditions of equivalent (to natural gas) energy delivery. Procedures will have to accommodate various safety aspects, but leakage is not considered an especially severe problem with hydrogen.

Operating conditions for appliance burners will be different for hydrogen in terms of primary air and probably delivery pressures. Flashback and noisy operation must be prevented. Replacement of burners for hydrogen operation is possible.     

Continuous supercritical water gasification of isooctane: A promising reactor design

A new design of supercritical water gasification system was developed to achieve high hydrogen gas yield and good gas–liquid flow stability. The apparatus consisted of a reaction zone, an insulation zone and a cooling zone that were directly connected to the reaction zone. The reactor was set up at an inclination of 75° from vertical position, and feed and water were introduced at the bottom of the reactor. The performances of this new system were investigated with gasification of isooctane at various experimental conditions – reaction temperatures of 601–676 °C, residence times of 6–33 s, isooctane concentrations of 5–33 wt%, and oxidant (hydrogen peroxide) concentrations up to 4507 mmol/L without using catalysts. A significant increase in hydrogen gas yield, almost four times higher than that from the previous up-down gasifier configuration (B. Veriansyah, J. Kim, J.D. Kim, Y.W. Lee, Hydrogen Production by Gasification of Isooctane using Supercritical Water, Int. J. Green Energy. 5 (2008) 322–333) was observed with the present gasifier configuration. High hydrogen gas yield (6.13 mol/mol isooctane) was obtained at high reaction temperature of 637 °C, a low feed concentration of 9.9 wt% and a long residence time of 18 s in the presence of 2701.1 mmol/L hydrogen peroxide. At this condition, the produced gases mainly consisted of hydrogen (59.5 mol%), methane (14.8 mol%) and carbon dioxide (22.0 mol%), and a small amount of carbon monoxide (1.6 mol%) and C₂–C₃ species (2.1 mol%). Reaction mechanisms of supercritical water gasification of isooctane were also presented.