Effects of hydrocarbon impurities,vibrational relaxation,and boundary-layer-induced pressure rise on the ignition of H2–O2‒Ar mixtures behind reflected shock waves

The results of an experimental and theoretical study of the ignition of H₂–O₂?Ar mixtures behind reflected shock waves are reported. The experiments are performed with mixtures containing from 0.15 to 8.0% H₂ and from 0.75 to 2.0% O₂ at temperatures of 980–1800 K and a total gas concentration of (1.0 ± 0.1) × 10^?5 mol/cm³. The progress of the process is monitored by recording the time evolution of the pressure behind the reflected shock wave and the intensity of the chemiluminescence of electronically excited OH1 radicals (λ = 308 ± 2.5 nm). A numerical model capable of predicting the effects of additional factors, such as hydrocarbon impurities, the vibrational relaxation of the test mixture, and boundary-layer-induced pressure rise, is developed and used to simulate our own and published experimental data on the ignition of H₂–O₂?Ar mixtures. It is demonstrated that the best agreement between experimental and theoretical results is achieved when all the additional factors are taken into account. A sensitivity analysis shows that the effects of the vibrational relaxation of the test mixture and the presence of hydrocarbon impurities are significant only for lean mixtures, whereas the influence of the boundary-layer-induced pressure rise is important across a wide range of stoichiometries at long ignition delay times. Additionally, an analytical model is developed, which takes into account the finite time of the chain?propagation reactions O + H₂ and OH + H₂. The predictions of the numerical and analytical models are demonstrated to be in close agreement for a wide range of mixture compositions and experimental conditions.     

Kinetics of ignition of saturated hydrocarbons by nonequilibrium plasma: C2H6- to C5H12-containing mixtures

The kinetics of ignition in C_nH_2n + 2:O₂:Ar mixtures for n=2 to 5 has been studied experimentally and numerically after a high-voltage nanosecond discharge. The ignition delay time behind a reflected shock wave was measured with and without the discharge. It was shown that the initiation of the discharge with a specific deposited energy of 10-30 mJ/cm³ leads to an order of magnitude decrease in the ignition delay time. Discharge processes and following chain chemical reactions with energy release were simulated. The generation of atoms, radicals and excited and charged particles was numerically simulated using the measured time-resolved discharge current and electric field in the discharge phase. The calculated densities of the active particles were used as input data to simulate plasma-assisted ignition. The sensitivity of the results to variation in electron cross sections, reaction rates and radical composition was investigated. Good agreement was obtained between the calculated ignition delay times and the experimental data. The analysis of the simulation results showed that the effect of nonequilibrium plasma on the ignition delay is associated with faster development of chain reactions, due to atoms and radicals produced by the electron impact dissociation of molecules in the discharge phase. Finally, we studied the role of various hydrocarbon radicals in the plasma-assisted ignition of the mixtures under consideration.     

A shock tube study of the rate constants of HO2 and CH3 reactions

HO₂ and CH₃ are major intermediate species presented during the oxidation of natural gas at intermediate temperatures and high pressures. Previous theoretical calculations have identified several product channels for HO₂ and CH₃ reactions, with CH₃ + HO₂ → CH₃O + OH and CH₃ + HO₂ → CH₄ + O₂ being the dominant reaction pathways. Both reaction pathways play an important role in the kinetics of CH₄ oxidation as CH₃ + HO₂ → CH₃O + OH is a chain-branching reaction whereas CH₃ + HO₂ → CH₄ + O₂ a chain termination reaction.H₂O₂/CH₄/Ar mixtures were shock-heated to a temperature between 1054 and 1249 K near 3.5 atm to initiate the reaction. OH radicals yielded from H₂O₂ thermal decomposition react with H₂O₂ and CH₄ respectively to produce HO₂ and CH₃ in the reacting system. Using laser absorption spectroscopy, time-histories of H₂O, OH and HO₂ were measured behind reflected shock waves. The rate constant of reaction CH₃ + HO₂ → CH₃O + OH was determined to be 6.8 × 10¹² cm³ mol^?1 s^?1 with an uncertainty factor of 1.4. The rate constant of the competing CH₃ + HO₂ → CH₄ + O₂ reaction was determined to be 4.4 × 10¹² cm³ mol^?1 s^?1, with an uncertainty factor of 2.1. In addition, the rate constants of two other major reactions of the reacting system, H₂O₂ (+M) → 2OH (+M) and OH + CH₄ → CH₃O + OH, were found to have excellent agreement with values recommended in literature.     

Shock tube and kinetic study of C2H6/H2/O2/Ar mixtures at elevated pressures

Using a high-pressure shock tube facility, the ignition delay times of stoichiometric C₂H₆/H₂/O₂ diluted in argon were obtained behind reflected shock wave at elevated pressures (p = 1.2, 4.0 and 16.0 atm) with ethane blending ratios from 0 to 100%. The measured ignition delay times were compared to the previous correlations, and the results show that the ignition delay times of ethane from different studies exhibit an obvious difference. Meanwhile, numerical studies were conducted with three generally accepted kinetic mechanisms and the results show that only NUIG Aramco Mech 1.3 agrees well with the measurements under all test conditions. Sensitivity analysis was made to interpret the poor prediction of the other two mechanisms. Furthermore, the effect of ethane blending ratio on the ignition delay times of the mixtures was analyzed and the results show that ethane blending ratio gives a non-linear effect on the auto-ignition of hydrogen. Finally, chemical interpretations on this non-linear effect were made from the reaction pathway analysis and normalized H radical consumption analysis.     

Effects of CO addition on laminar flame characteristics and chemical reactions of H2 and CH4 in oxy-fuel (O2/CO2) atmosphere

An experimental study is conducted to investigate the effect of CO addition on the laminar flame characteristics of H₂ and CH₄ flames in a constant-volume combustion system. In addition, one-dimensional laminar premixed flame propagation processes at the same conditions are simulated with the update mechanisms. Results show that all mechanisms could well predict the laminar flame speeds of CH₄/CO/O₂/CO₂ mixtures, when Z_CO is large. For mixtures with lower CO, the experimental laminar flame speeds are always smaller than the calculated ones with Han mechanism. For mixtures with larger or smaller Z_CO2, GRI 3.0, San diego and USC 2.0 mechanisms all overvalue or undervalue the laminar flame speeds. When CO ratio in the CH₄/CO blended fuels increases, laminar flame speed firstly increases and then decreases for the CH₄/CO/O₂/CO₂ mixtures. For H₂/CO/O₂/CO₂ mixtures, San diego, Davis and Li mechanisms all undervalue the laminar flame speeds of H₂/CO/CO₂/CO₂ mixtures. Existing models could not well predict the nonlinear trend of the laminar flame speeds, due to complex chemical effects of CO on CH₄/CO or H₂/CO flames. Then, the detailed thermal, kinetic and diffusive effects of CO addition on the laminar flame speeds are discussed. Kinetic sensitivity coefficient is far larger than thermal and diffusive ones and this indicates CO addition influences laminar flame speeds mainly by the kinetic effect. Based on this, radical pool and sensitivity analysis are conducted for CH₄/CO/O₂/CO₂ and H₂/CO/O₂/CO₂ mixtures. For CH₄/CO/O₂/CO₂ mixtures, elementary reaction R38H + O₂ ↔ O + OH and R99 OH + CO ↔ H + CO₂ are the most important branching reactions with positive sensitivity coefficients when CO ratio is relative low. As CO content increases in the CH₄/CO blended fuel, the oxidation of CO plays a more and more important role. When CO ratio is larger than 0.9, the importance of R99 OH + CO ↔ H + CO₂ is far larger than that of R38H + O₂ ↔ O + OH. The oxidation of CO dominates the combustion process of CH₄/CO/O₂/CO₂ mixtures. For H₂/CO/O₂/CO₂ mixtures, the most important elementary reaction with positive and negative sensitivity coefficients are R29 CO + OH ↔ CO₂ + H and R13H + O₂(+M) ↔ HO₂(+M) respectively. The sensitivity coefficient of R29 CO + OH ↔ CO₂ + H is increasing and then decreasing with the addition of CO in the mixture. Chemical kinetic analysis shows that the chemical effect of CO on the laminar flame propagation of CH₄/CO/O₂/CO₂ and H₂/CO/O₂/CO₂ mixtures could be divided into two stages and the critical CO mole fraction is 0.9.     

Shock tube study of ethylamine pyrolysis and oxidation

Ethylamine (CH₃CH₂NH₂) pyrolysis and oxidation were studied using laser absorption behind reflected shock waves. For ethylamine pyrolysis, NH₂ time-histories were measured in 2000 ppm ethylamine/argon mixtures. For ethylamine oxidation, ignition delay times, and NH₂ and OH time-histories were measured in ethylamine/O₂/argon mixtures. Measurements covered the temperature range of 1200–1448 K, with pressures near 0.85, 1.35 and 2 atm, and fuel mixtures with equivalence ratios of 0.75, 1 and 1.25 in 0.2%, 0.8% and 4% O₂/argon. Simulations using the recent Li et al. mechanism gave significantly shorter ignition delay times and higher intermediate radical species concentrations than the experimental results. The reaction rate constants for the two major ethylamine decomposition pathways were modified in the Li et al. mechanism to improve the prediction of the time-histories of NH₂ and OH in ethylamine pyrolysis. In addition, recommendations from recent studies of ethylamine + OH reactions were implemented. With these modifications, the Modified Li et al. mechanism provides significantly improved agreement with the species time-history measurements and the ignition delay time data.     

Numerical analysis on the combined transport effects of H2 and CO2 on the laminar premixed flame characteristics of biogas-hydrogen blends

The combined and respective transport effects of H₂ and CO₂ on the flame structure, laminar flame speed and radical pool of the BG40H60 blends at different equivalence ratios are investigated quantitatively with the numerical simulation in this study. The results show that H₂ transport dominates the decrease and enhancement of HRR and mole fractions of minor species at the fuel-lean and fuel-rich conditions. However, H₂ or CO₂ transport hardly affects concentrations of major species expect for H₂ and CO₂. Besides, the dominated H₂ transport contributes to the decreased/increased laminar flame speed at the fuel-lean/fuel-rich condition, while the OH radical can reflect the laminar flame speed variation caused by the H₂ and CO₂ transport. Based on the rate-of-production (ROP) analysis of OH radical, the most sensitive reactions to H₂ and CO₂ transport are OH + H₂H₂O + H/H + O₂O + OH and OH + CH₂OHCO + H₂O at the fuel-lean and fuel-rich conditions respectively. The major production reactions (H + O₂O + OH, H + HO₂ = 2OH, O + H₂H + OH, 2OH = O + H₂O) of OH radical are suppressed or improved more significantly with the H₂ and CO₂ transport at the fuel-lean or fuel-rich condition, leading to the suppressed or improved OH radical pool and the flame propagation at the fuel-lean or fuel-rich condition. Furthermore, it is demonstrated that CO₂ transport suppresses the reaction of OH + H₂H₂O + H considerably to improve the OH radical pool at the fuel-rich condition and cannot be neglected when investigating the flame propagation of biogas-hydrogen blends.     

Effects of N2O addition on the ignition of H2–O2 mixtures: Experimental and detailed kinetic modeling study

Ignition delay times of H₂/O₂ mixtures highly diluted with Ar and doped with various amounts of N₂O (100, 400, 1600, 3200 ppm) were measured in a shock tube behind reflected shock waves over a wide range of temperatures (940–1675 K). The pressure range investigated during this work (around 1.6, 13 and 32 atm) allows studying the effect of N₂O on hydrogen ignition at pressure conditions that have never been heretofore investigated. Ignition delay times were decreased when N₂O was added to the mixture only for the higher nitrous oxide concentrations, and some changes in the activation energy were also observed at 1.5 and 32 atm. When it occurred, the decrease in the ignition delay time was proportional to the amount of N₂O added and depended on pressure and temperature conditions. A detailed chemical kinetics model was developed using kinetic mechanisms from the literature. This model predicts well the experimental data obtained during this study and from the literature. The chemical analysis using this model showed that the decrease in the ignition delay time was mainly due to the reaction N₂O + M ? N₂ + O + M which provides O atoms to strengthen the channel O + H₂ ? OH + H.     

Effect of hydrogen and syngas addition on the ignition of iso-octane/air mixtures

There is worldwide interest in using renewable fuels within the existing infrastructure. Hydrogen and syngas have shown significant potential as renewable fuels, which can be produced from a variety of biomass sources, and used in various transportation and power generation systems, especially as blends with hydrocarbon fuels. In the present study, a reduced mechanism containing 38 species and 74 reactions is developed to examine the ignition behavior of iso-octane/H₂ and iso-octane/syngas blends at engine relevant conditions. The mechanism is extensively validated using the shock tube and RCM ignition data, as well as three detailed mechanisms, for iso-octane/air, H₂/air and syngas/air mixtures. Simulations are performed to characterize the effects of H₂ and syngas on the ignition of iso-octane/air mixtures using the closed homogenous reactor model in CHEMKIN software. The effect of H₂ (or syngas) is found to be small for blends containing less than 50% H₂ (or syngas) by volume. However, for H₂ mole fractions above 50%, it increases and decreases the ignition delay at low (T < 900 K) and high temperatures (T > 1000 K), respectively. For H₂ fractions above 80%, the ignition is influenced more strongly by H₂ chemistry rather than by i-C₈H₁₈ chemistry, and does not exhibit the NTC behavior. Nevertheless, the addition of a relatively small amount of i-C₈H₁₈ (a low cetane number fuel) can significantly enhance the ignitability of H₂-air mixtures at NTC temperatures, which are relevant for HCCI and PCCI dual fuel engines. The CO addition seems to have a negligible effect on the ignition of i-C₈H₁₈/H₂/air mixtures, indicating that the ignition of i-C₈H₁₈/syngas blends is essentially determined by i-C₈H₁₈ and H₂ oxidation chemistries. The sensitivity and reaction path analysis indicates that i-C₈H₁₈ oxidation is initiated with the production of alkyl radical by H abstraction through reaction: i-C₈H₁₈ + O₂ = C₈H₁₇ + HO₂. Subsequently, the ignition chemistry in the NTC region is characterized by a competition between two paths represented by reactions R2 (C₈H₁₇ + O₂ = C₈H₁₇O₂) and R8 (C₈H₁₇ + O₂ = C₈H₁₆ + HO₂), with the R8 path dominating, and increasing the ignition delay. As the amount of H₂ in the blend becomes significant, it opens up another path for the consumption of OH through reaction R36 (H₂ + OH = H₂O + H), which slows down the ignition process. However, for T > 1100 K, the presence of H₂ decreases ignition delay primarily due to reactions R31 (O₂ + H = OH + O) and R35 (H₂O₂ + M = OH + OH + M).     

Study on the mechanism of the ignition process of ammonia/hydrogen mixture under high-pressure direct-injection engine conditions

As environmental problems and energy crisis become more serious, ammonia is one of the potential alternative fuels. In order to better use ammonia as fuel in power equipment, the ignition process was studied under high-pressure direct-injection engine condition. In the paper, the Homogeneous model in Chemkin package was selected for numerical calculation. In the six cases with different hydrogen mixing ratios, the effect of initial temperature, pressure, equivalence ratio and hydrogen mixing ratio on ignition delay time (IDT) were studied. It conducted that IDT could be effectively reduced when adding 10–50% hydrogen to ammonia. Then, after sensitivity analysis of NH₃/H₂ mixtures, the key equations and free radicals affecting combustion characteristics were found. The rate of production (ROP) of the key radicals were carried out. It was found that the hydrogen provided the initial concentration of H radical before the start fire, which greatly improved the ROP of OH radical of R1(H + O₂=O + OH) compared to the original H needed to break the N–H chemical bond in pure ammonia. And the OH radical was related to the consumption of NH₃ by R31(NH₃+OH=NH₂+H₂O).     

Comparative study on the effect of CO2 and H2O dilution on laminar burning characteristics of CO/H2/air mixtures

A study on the effect of CO₂ and H₂O dilution on the laminar burning characteristics of CO/H₂/air mixtures was conducted at elevated pressures using spherically expanding flames and CHEMKIN package. Experimental conditions for the CO₂ and H₂O diluted CO/H₂/air/mixtures of hydrogen fraction in syngas from 0.2 to 0.8 are the pressures from 0.1 to 0.3 MPa, initial temperature of 373 K, with CO₂ or H₂O dilution ratios from 0 to 0.15. Laminar burning velocities of the CO₂ and H₂O diluted CO/H₂/air/mixtures were measured and calculated using the mechanism of Davis et al. and the mechanism of Li et al. Results show that the discrepancy exists between the measured values and the simulated ones using both Davis and Li mechanisms. The discrepancy shows different trends under CO₂ and H₂O dilution. Chemical kinetics analysis indicates that the elementary reaction corresponding to peak ROP of OH consumption for mixtures with CO/H₂ ratio of 20/80 changes from reaction R3 (OH + H₂ = H + H₂O) to R16 (HO₂+H = OH + OH) when CO₂ and H₂O are added. Sensitivity analysis was conducted to find out the dominant reaction when CO₂ and H₂O are added. Laminar burning velocities and kinetics analysis indicate that CO₂ has a stronger chemical effect than H₂O. The intrinsic flame instability is promoted at atmospheric pressure and is suppressed at elevated pressure for the CO₂ and H₂O diluted mixtures. This phenomenon was interpreted with the parameters of the effective Lewis number, thermal expansion ratio, flame thickness and linear theory.     

An improved H2/O2 mechanism based on recent shock tube/laser absorption measurements

An updated H₂/O₂ reaction mechanism is presented that incorporates recent reaction rate determinations in shock tubes from our laboratory. These experiments used UV and IR laser absorption to monitor species time-histories and have resulted in improved high-temperature rate constants for the following reactions: H+O₂=OH+OH₂O₂(+M)=2OH(+M)OH+H₂O₂=HO₂+H₂OO₂+H₂O=OH+HO₂ The updated mechanism also takes advantage of the results of other recent rate coefficient studies, and incorporates the most current thermochemical data for OH and HO₂. The mechanism is tested (and its performance compared to that of other H₂/O₂ mechanisms) against recently reported OH and H₂O concentration time-histories in various H₂/O₂ systems, such as H₂ oxidation, H₂O₂ decomposition, and shock-heated H₂O/O₂ mixtures. In addition, the mechanism is validated against a wide range of standard H₂/O₂ kinetic targets, including ignition delay times, flow reactor species time-histories, laminar flame speeds, and burner-stabilized flame structures. This validation indicates that the updated mechanism should perform reliably over a range of reactant concentrations, stoichiometries, pressures, and temperatures from 950 to greater than 3000 K.     

Simultaneous production of H2 and C2 hydrocarbons by using a novel configuration solid-electrolyte + fixed bed reactor

A novel combined single chamber solid electrolyte plus fixed bed reactor configuration was developed for the simultaneous production of H₂ and C₂ hydrocarbons from a humidified CH₄ atmosphere. Hence, a Pt/YSZ/Ag solid electrolyte cell was placed on the top of an active oxidative coupling catalyst powder bed Ce–Na₂WO₄/SiO₂. H₂ was produced via steam electrolysis in a Pt cathode of the solid electrolyte cell (H₂O + 2e⁻ → H₂ + O²⁻). Simultaneously, the produced O²⁻ ions were electrochemically pumped to the Ag anode, leading to the C_2s production, via oxidative coupling of CH₄ (4CH₄ + 3O²⁻ → C₂H₄ + C₂H₆ + 3H₂O + 6e⁻). Additionally, non-reacted O²⁻ molecules desorbed to the gas phase (2O²⁻ → O₂+4e⁻) and reacted with CH₄ in the catalyst bed leading to an increase of C_2s yield. The influence of different reaction parameters was investigated together with long-term reaction experiments, confirming the stability of this configuration for its practical application. The obtained results demonstrated that the addition of an active catalyst bed strongly enhances both: the efficiency of the single chamber steam electrolysis and the oxidative coupling process.     

Multi-species measurements in 1-butanol pyrolysis behind reflected shock waves

The kinetics of 1-butanol pyrolysis were investigated by measuring multi-species time histories using shock tube/laser absorption methods. Species time histories of OH, H₂O, C₂H₄, CO, and CH₄ were measured behind reflected shock waves using UV and IR laser absorption during the high-temperature decomposition of 1% 1-butanol/argon mixtures. Initial reflected shock temperatures and pressures for these experiments covered 1250–1650 K and 1.3–1.9 atm. Measured OH and H₂O time histories are in good agreement with previous experimental studies; measured C₂H₄, CO, and CH₄ time histories are the first reported for this fuel in shock tube experiments.Production pathways and sensitivities for the measured species are analyzed using the recent Sarathy et al. (2012) [37] detailed mechanism. Simulations using this mechanism underpredict H₂O, OH, and C₂H₄ mole fractions, overpredict CH₄ mole fractions, and significantly underpredict CO mole fractions at early times. As discussed in past papers and confirmed in this study, the branching ratios of H abstraction rates from 1-butanol, which are not precisely known, can significantly affect H₂O time history simulations. These simulations show that H₂O is produced primarily through H-atom abstraction from 1-butanol by OH, and therefore H₂O time histories are extremely sensitive to 1-butanol decomposition channels that contribute to the OH radical pool. Simulations also show that more C₂H₄ would be produced by faster decomposition of 1-butanol through several channels that also affect H₂O production. Finally, simulations show that CO time histories are strongly sensitive to 1-butanol decomposition into nC₃H₇ and CH₂OH, especially at early times. Evidence is presented that indicates this decomposition pathway is too slow in the simulations by a factor of three to five at conditions of the current study.     

Shock tube study on ignition delay of multi-component syngas mixtures – Effect of equivalence ratio

Ignition delays were measured in a shock tube for syngas mixtures with argon as diluent at equivalence ratios of 0.3, 1.0 and 1.5, pressures of 0.2, 1.0 and 2.0 MPa and temperatures from 870 to 1350 K. Results show that the influences of equivalence ratio on the ignition of syngas mixtures exhibit different tendency at different temperatures and pressures. At low pressure, the ignition delay increases with an increase in equivalence ratio at tested temperature. At high pressures, however, an opposite behavior is presented, that is, increasing equivalence ratio inhibits the ignition at high temperature and vice versa at intermediate temperature. The affecting degree of equivalence ratio on ignition delay is different for each mixture at given condition, especially for the syngas with high CO concentration. Sensitivity analyses demonstrate that reaction H + O₂ = O + OH (R1) dominates the syngas oxidation under all conditions. With the increase of CO mole fraction, reactions CO + OH = CO₂ + H (R27) and CO + HO₂ = CO₂ + OH (R29) become more important in the syngas ignition kinetics. With the increase of pressure, the reactions related to HO₂ and H₂O₂ play the dominate role. The opposite influence of equivalence ratio on ignition delay at high- and intermediate-temperatures is chemically interpreted through kinetic analyses.     

Visible-light sensitive hydrogen evolution photocatalyst ZnRh2O4

We investigated the ability of the oxide ZnRh₂O₄ to serve as a solar H₂-evolution photocatalyst due to the predicted potential of its conduction band bottom, which may allow thermodynamically favorable H₂ evolution in spite of its small band-gap of 1.2 eV. ZnRh₂O₄ produced H₂ in the presence of HCHO, but only scarcely in the presence of CH₃OH, indicating that the potential of the valence band top of ZnRh₂O₄ lies at ∼0.1 V (vs. SHE). Thus, the conduction band bottom potential (∼−1.1 V) lies much more negative than the potential of H⁺/H₂, allowing thermodynamically favorable H₂ evolution. In addition, the irradiated-light-wavelength dependence of the quantum efficiency (QE) for H₂ evolution was consistent with the solar spectrum, and the QE was quite high (∼27%), even at a wavelength of 770 ± 25 nm. Taken together, our findings indicate that ZnRh₂O₄ can utilize solar light effectively, not only the entire range of UV and visible light, but is also sensitive to infrared light.     

Promotion of H2 production from ethanol steam reforming by zeolite basicity

The effect of the basicity of zeolite as a metallic catalyst substrate on ethanol steam reforming reaction was investigated. Catalysts with various basicities were prepared using an ion exchange process with aqueous solutions including Na⁺, K⁺ and Cs⁺ after an impregnation process of Ni on Na-Y zeolite (referred to as Ni/Na-Y, Ni/K-Y and Ni/Cs-Y, respectively). Infrared spectroscopy indicated that the OH bonds of ethanol molecules adsorbed on zeolites were weakened with increasing zeolite basicity. H₂ production at 300 °C increased in the order of Ni/Cs-Y > Ni/K-Y > Ni/Na-Y, and selectivity for a high production ratio of H₂ to C₂H₄ was significantly promoted by exchanging Na⁺ for K⁺ or Cs⁺. H₂ production at 500 °C was also enhanced by the zeolite basicity; however, degradation of catalytic activity was mainly caused by carbon deposition on the three samples at this temperature. Ni/Cs-Y, with higher H₂ production than Ni/Na-Y, also exhibited higher resistance to carbon deposition. Increase of the zeolite basicity was effective for selective acceleration of the dehydrogenation reaction with ethanol, inhibition of coke deposition, and the promotion of H₂ production.     

Numerical analysis on influence of hydrogen peroxide (H2O2) addition on the combustion and emissions characteristics of NH3/CH4-air (O2/N2)/ H2O2 mixture

In this work, extensive chemical kinetic modeling is performed to analyze the combustion and emissions characteristics of premixed NH₃/CH₄–O₂/N₂/H₂O₂ mixtures at different replacement percentages of air with hydrogen peroxide (H₂O₂). This work is comprehensively discusses the ignition delay time, flame speed, heat release rate, and NOx & CO emissions of premixed NH₃/CH₄–O₂/N₂/H₂O₂ mixtures. Important intermediate crucial radicals such as OH, HO₂, HCO, and HNO effect on the above-mentioned parameters is also discussed in detail. Furthermore, correlations were obtained for the laminar flame speed, NO, and CO emissions with important radicals such as OH, HO₂, HCO, and HNO. The replacement of air with H₂O₂ increases flame speed and decreases the ignition delay time of the mixture significantly. Also, increases the CO and NOx concentration in the products. The CO and NOx emissions can be controlled by regulating the H₂O₂ concentration and equivalence ratios. Air replacement with H₂O₂ enhances the reactions rate and concentration of intermediate radicals such as O/H, HO₂, and HCO in the mixture. These intermediate radicals closely govern the combustion chemistry of the NH₃/CH₄– O₂/N₂/H₂O₂ mixture. A linear correlation is observed between the flame speed and peak mole fraction of OH + HO₂ radicals, and 2nd degree polynomial correlation is observed for the peak mole fraction of NO and CO with HNO + OH and HCO + OH radicals, respectively.     

A dynamical model for the generation of H2 in microhydrated Al clusters

A dynamical model is proposed to describe the generation of H₂ in the Al_n + H₂O reactions in order to deal with the complexity of the potential energy surface. For that purpose electronic structure Density Functional Theory and Transition State Theory computations have been carried out on the Al₁₇⁺·(H₂O) system. The results are compared with the findings of previous flow-tube experiments, in which Al₁₇⁺ is found to be highly reactive with just one water molecule; that makes this system ideal for modelling. The energy ordering in terms of the activation energies of the various processes is: cluster distortions ≈ -OH migrations < -H migrations < O-H bond breaking < H₂ release. The time-dependent results are reasonably consistent with the experiments and suggest that the lowest-lying structures of the oxo type (H₂Al₁₇O⁺ structures) play the most relevant role in the production of H₂. The sensitivity towards energy removal from the reacting system and the impact of tunnelling have been analysed as well as the possible role of a second water molecule as a catalyst of the water-splitting step by a Grotthuss-relay mechanism.     

Solar syngas production from CO2 and H2O in a two-step thermochemical cycle via Zn/ZnO redox reactions: Thermodynamic cycle analysis

Solar syngas production from CO₂ and H₂O is considered in a two-step thermochemical cycle via Zn/ZnO redox reactions, encompassing: 1) the ZnO thermolysis to Zn and O₂ using concentrated solar radiation as the source of process heat, and 2) Zn reacting with mixtures of H₂O and CO₂ yielding high-quality syngas (mainly H₂ and CO) and ZnO; the ZnO is recycled to the first, solar step, resulting in net reaction βCO₂ + (1 − β)H₂O → βCO + (1 − β)H₂. Syngas is further processed to liquid hydrocarbon fuels via Fischer-Tropsch or other catalytic processes. Second-law thermodynamic analysis is applied to determine the cycle efficiencies attainable with and without heat recuperation for varying molar fractions of CO₂:H₂O and solar reactor temperatures in the range 1900-2300 K. Considered is the energy penalty of using Ar dilution in the solar step below 2235 K for shifting the equilibrium to favor Zn production.