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.     

Effects of hydrogen addition on cellular instabilities of the spherically expanding propane flames

An experimental study on the effects of hydrogen addition on the instabilities of spherically expanding propane–air flames was conducted in a constant volume combustion vessel over a wide range of mixture compositions and initial temperatures and pressures. The measured laminar burning velocities were compared with those calculatedvalues by using one dimensional freely propagating flames and a recently developed detailed kinetic mechanism. Goodagreementwas obtained between the experiment and calculation. The schlieren images show that for lean mixture combustion, hydrogen addition willincrease the hydrodynamic instability due to the decreased flame thickness and increase the diffusional-thermal instability due to the decreased Lewis number. While forrich mixture combustion, the flame front is initially destabilized and later tends to the stabilized with the increase of hydrogen fraction. This is due to the competing effects of the hydrodynamic instability and the diffusional-thermal instability.     

Role of chemical kinetics on the detonation properties of hydrogen /natural gas/air mixtures

The first part of the present work is to validate a detailed kinetic mechanism for the oxidation of hydrogen–methane–air mixtures in detonation waves. A series of experiments on auto-ignition delay times have been performed by shock tube technique coupled with emission spectrometry for H₂/CH₄/O₂ mixtures highly diluted in argon. The CH₄/H₂ ratio was varied from 0 to 4 and the equivalence ratio from 0.4 to 1. The temperature range was from 1250 to 2000 K and the pressure behind reflected shock waves was between 0.15 and 1.6 MPa. A correlation was proposed between temperature (K), concentration of chemical species (mol m^-3)${\mathrm{m}}^{-3})$ and ignition delay times. The experimental auto-ignition delay times were compared to the modelled ones using four different mechanisms from the literature: GRI [Smith PG, Golden DM, Frenklach M, Moriarty NW, Goldenberg M, et al. 〈$〈$http://www.me.berkeley.edu/gri_mech/〉$〉$], Marinov et al. [Aromatic and polycyclic aromatic hydrocarbon formation in a laminar premixed n  -butane flame. Combust Flame 1998; 114:192–213], Hughes et al. [〈$〈$http://www.chem.leeds.ac.uk/Combustion/Combustion.html〉$〉$], Konnov [Detailed reaction mechanism for small hydrocarbons combustion. Release 0.5 〈$〈$http://homepages.vub.ac.be/∼$\sim$akonnov/〉$〉$, 2000]. A large discrepancy was generally found between the different models. Konnov's model, which auto-ignition delay times predictions were the closest to the measured ones, has been selected to calculate ignition delay times in the detonation waves. The second part of the study concerned the experimental determination of the detonation properties, namely detonation velocity and cell size. Effect of the initial composition, hydrogen to methane ratio and the amount of oxygen in the mixture, as well as the initial pressure on the detonation velocity and on the cell size were investigated. The ratio of methane/(methane +$+$ hydrogen) varied between 0 and 0.6 for two different equivalence ratios (0.75 and 1) while the initial pressure was fixed to 10 kPa. A correlation was established between the characteristic cell size and the ignition delay time behind the leading shock of the detonation. It was clearly shown that methane has an important inhibitor effect on the detonation of these combustible mixtures.     

Ignition properties of methane/hydrogen mixtures in a rapid compression machine

We investigate changes in the combustion behavior of methane, the primary component of natural gas, upon hydrogen addition by characterizing the autoignition behavior of methane/hydrogen mixtures in a rapid compression machine (RCM). Ignition delay times were measured under stoichiometric conditions at pressures between 15 and 70 bar, and temperatures between 950 and 1060 K; the hydrogen fraction in the fuel varied between 0 and 1. The ignition delay times in methane/hydrogen mixtures are well correlated with the ignition delay times of the pure fuels by using a simple mixing relation reported in the literature. Simulations of the ignition delay times using various chemical mechanism are also reported. The mechanism given by Petersen et al. shows excellent agreement with the measurements for all mixtures studied. Initial results on fuel–lean mixtures show a modest effect of equivalence ratio on the delay times.     

Power-law type rate equation for propane ATR over Pt–Ni/Al2O3 catalyst

Kinetics of autothermal reforming (ATR) of propane on bimetallic Pt–Ni catalyst supported over δ-Al₂O₃ is investigated at 673 K with the purpose of obtaining an easy-to-implement power-law type rate equation. The rate expression is proposed for conditions extending up to 20% propane conversion and has reaction orders of 1.64, 2.44 and −0.59 in propane, oxygen and steam partial pressures, respectively. Parameters estimated by non-linear regression analysis in the MATLAB™ environment can be reliably used for propane ATR in the steam-to-carbon ratio range of 2.0–3.0 and carbon-to-oxygen ratio range of 3.0–5.4. The apparent activation energy is calculated as 46 ± 4 kJ mol⁻¹ in the 653–693 K interval.     

Calculation of the upper flammability limit of methane/hydrogen/air mixtures at elevated pressures and temperatures

The results of three different numerical methods to calculate flammability limits—namely (1) the calculation of planar flames with the inclusion of a (radiation) heat loss term in the energy conservation equation, and the application of (2) a limiting burning velocity and of (3) a limiting flame temperature—are compared with experimental data on the upper flammability limit (UFL) of methane/hydrogen/air mixtures with hydrogen fuel molar fractions of 20% and 40%, at initial pressures up to 10 bar and initial temperatures up to 200 °C. The application of a limiting burning velocity is found to predict the pressure dependence of the UFL well, while the application of a limiting flame temperature generally is found to slightly underestimate the temperature dependence of the UFL.     

Simulation of hydrogen and hydrogen-assisted propane ignition in pt catalyzed microchannel

This paper deals with self-ignition of catalytic microburners from ambient cold-start conditions. First, reaction kinetics for hydrogen combustion is validated with experimental results from the literature, followed by validation of a simplified pseudo-2D microburner model. The model is then used to study the self-ignition behavior of lean hydrogen/air mixtures in a Platinum-catalyzed microburner. Hydrogen combustion on Pt is a very fast reaction. During cold start ignition, hydrogen conversion reaches 100% within the first few seconds and the reactor dynamics are governed by the “thermal inertia” of the microburner wall structure. The self-ignition property of hydrogen can be used to provide the energy required for propane ignition. Two different modes of hydrogen-assisted propane ignition are considered: co-feed mode, where the microburner inlet consists of premixed hydrogen/propane/air mixtures; and sequential feed mode, where the inlet feed is switched from hydrogen/air to propane/air mixtures after the microburner reaches propane ignition temperature. We show that hydrogen-assisted ignition is equivalent to selectively preheating the inlet section of the microburner. The time to reach steady state is lower at higher equivalence ratio, lower wall thermal conductivity, and higher inlet velocity for both the ignition modes. The ignition times and propane emissions are compared. Although the sequential feed mode requires slightly higher amount of hydrogen, the propane emissions are at least an order of magnitude lower than the other ignition modes.     

A numerical study on the effects of H2 addition in non-premixed turbulent combustion of C3H8–H2–N2 mixture using a steady flamelet approach

This study has been implemented in two sections. At first, the turbulent jet flame of DLR-B is simulated by combining the k–ε turbulence model and a steady flamelet approach. The DLR-B flame under consideration has been experimentally investigated by Meier et al. who obtained velocity and scalar statistics. The fuel jet composition is 33.2% H₂, 22.1% CH₄ and 44.7% N₂ by volume. The jet exit velocity is 63.2 m/s resulting in a Reynolds number of 22,800. Our focus in the first part is to validate the developed numerical code. Comparison with experiments showed good agreement for temperature and species distribution. At the second part, we exchanged methane with propane in the fuel composition whilst maintaining all other operating conditions unchanged. We investigated the effect of hydrogen concentration on C₃H₈–H₂–N₂ mixtures so that propane mole fraction extent is fixed. The hydrogen volume concentration rose from 33.2% up to 73.2%. The achieved consequences revealed that hydrogen addition produces elongated flame with increased levels of radiative heat flux and CO pollutant emission. The latter behavior might be due to quenching of CO oxidation process in the light of excessive cold air downstream of reaction zone.     

Structured reactors as alternative to pellets catalyst for propane oxidative steam reforming

The performance of a Pt/CeO₂ catalyst as packed bed, coated on monolith and as self-structured bed has been evaluated during C₃H₈ oxidative steam reforming. Structured bed, prepared by a new aqueous tape casting method, combining high total porosity (80%) with a self-supported channel structure, offers a better and more efficient control of heat and mass transfer along the catalytic bed, showing, especially at high gas hourly space velocity (30 × 10⁴ h⁻¹), better performance in terms of fuel conversion, hydrogen production and low by-products formation coupled with an economy of the catalyst of about to 43% with respect to the traditional packed bed system.     

Co-production of hydrogen and fibrous carbons by methane decomposition using K2CO3/carbon hybrid as the catalyst

Methane decomposition was conducted by using K₂CO₃/carbon hybrids as the catalysts, and hydrogen-rich gas (with hydrogen content of about 87%) and fibrous carbons can be simultaneously obtained together with high and stable methane conversion (up to about 90% at 850 °C). Effects of K₂CO₃ on methane conversion, hydrogen content and fibrous carbons were investigated by changing the reaction temperature and space velocity. The results indicate that K₂CO₃ can greatly promote methane activation and conversion, taking responsibility for the continuous formation of CO and a trace of CO₂. The oxygen transfer from K₂CO₃ probably provides convenience for the formation and growth of fibrous carbons.     

Methane cracking using Ni supported on porous and non-porous alumina catalysts

Porous and non-porous alumina catalysts were used as nickel supports to catalyze methane cracking. Different operating parameters were studied in a thermal gravimetric analyzer, including methane and hydrogen partial pressures, temperature and flow rate. During CH₄ cracking, carbon builds up on the catalyst surface and therefore the catalyst requires periodic regeneration. Cycling tests were performed, using air during the regeneration phase to burn off the carbon. The results showed that the non-porous catalyst performed better than the porous catalyst in terms of cracking during the first cycle. Full regeneration of the catalysts by oxidizing the deposited carbon was achieved at 550 °C, while oxidation was very slow at 500 °C. After full regeneration, the performance of the porous catalyst became considerably better than the non-porous. The porous catalyst kept its activity for 24 cracking/regeneration cycles, while the non-porous catalyst lost half of its activity by the second cracking cycle and almost all of its activity after six cycles. NiAl₂O₄ formation and Ni sintering caused the non-porous catalyst activity loss. TPO results showed that two carbon types were deposited on the catalysts, namely Cβ and Cγ, where Cβ is more active than Cγ.     

Hydrogen production by sorption enhanced steam reforming of propane: A thermodynamic investigation

Thermodynamic features of hydrogen production by sorption enhanced steam reforming (SESR) of propane have been studied with the method of Gibbs free energy minimization and contrasted with propane steam reforming (SR). The effects of pressure (1-5 atm), temperature (700-1100 K) and water to propane ratio (WPR, 1-18) on equilibrium compositions and carbon formation are investigated. The results suggest that atmospheric pressure and a WPR of 12 are suitable for hydrogen production from both SR and SESR of propane. High WPR is favourable to inhibit carbon formation. The minimum WPR required to eliminate carbon production is 6 in both SR and SESR. The most favourable temperature for propane SR is approximately 950 K at which 1 mol of propane has the capacity to produce 9.1 mol of hydrogen. The optimum temperature for SESR is approximately 825 K, which is over 100 K lower than that for SR. Other key benefits include enhanced hydrogen production of nearly 10 mol (stoichiometric value) of hydrogen per mole of propane at 700 K, increased hydrogen purity (99% compared with 74% in SR) and no CO₂ or CO production with the only impurity being CH₄, all indicating a great potential of SESR of propane for hydrogen production.     

An energy-efficient plasma methane pyrolysis process for high yields of carbon black and hydrogen

A novel thermal plasma process was developed, which enables economically viable commercial-scale hydrogen and carbon black production. Key aspects of this process are detailed in this work. Selectivity and yield of both solid, high-value carbon and gaseous hydrogen are given particular attention. For the first time, technical viability is demonstrated through lab scale reactor data which indicate methane feedstock conversions of >99%, hydrogen selectivity of >95%, solid recovery of >90%, and the ability to produce carbon particles of varying crystallinity having the potential to replace traditional furnace carbon black. The energy intensity of this process was established based on real-time operation data from the first commercial plant utilizing this process. In its current stage, this technology uses around 25 kWh per kg of H2 produced, much less than water electrolysis which requires approximately 60 kWh per kg of H2 produced. This energy intensity is expected to be reduced to 18–20 kWh per kg of hydrogen with improved heat recovery and energy optimization.     

Effect of vent size on vented hydrogen-air explosion

In this paper, the effect of vent size on vented hydrogen-air explosion in the room was studied by numerical simulation. Analysis of the explosion temperature, overpressure, dynamic pressure and wind velocity under different vent sizes indicate that these explosion parameters have different change rules inside and outside the room. Inside the room, the vent size has little effect on the explosion temperature, dynamic pressure and wind velocity, but it has a significant impact on the explosion overpressure. As the scaled vent size $K_v$ ($A_v/V^{2/3}$) increases from 0.1 to 0.3, the difference between the maximum internal peak overpressure is 87.8%. Outside the room, as the vent size increases, the high-temperature range (above 800 K) first decreases and then increases, while the explosion dynamic pressure and hurricane zone caused by explosion wind gradually decrease. The maximum high-temperature range (32.5 m for $K_v$ = 0.1) and hurricane zone (41.1 m for $K_v$ = 0.1) can reach 7.0 times and 8.9 times the length of the room, respectively. The explosion dynamic pressure can reach the same order of magnitude as the explosion overpressure under the same vent size. Therefore, these damage effects outside the room cannot be ignored. During the change of vent sizes, for $K_v$ ≤ 0.3, the explosion parameters change drastically and the disaster effect is significant. For example, external explosion that affect the discharge of internal explosion overpressure occur; explosion that occurs in masonry structures can destroy the structural integrity of the brick walls. Therefore, $K_v$ = 0.3 can be used as a reference for hydrogen-air venting safety design.     

Flammability limits of hydrogen-enriched natural gas

This paper reports both the lower and upper flammability limits of hydrogen-enriched natural gas with hydrogen fractions of 20%, 40%, 60% and 80% respectively as well as these of natural gas and hydrogen, measured by using a constant volume combustion chamber together with a high-speed schlieren photographic system. Based on investigating pressure rise history inside the combustion chamber as well as flame photos, the effect of hydrogen enrichment on the flammability characteristics is discussed. Our experimental results show that the flammability limits of methane-hydrogen mixtures can be used for hydrogen-enriched natural gas as long as their hydrogen fractions are the same. In this paper, the flammability data of methane-hydrogen mixtures available in the literature are reviewed. Correlations for both the lower and upper flammability limits of methane-hydrogen mixtures are summarized.