Chemical Kinetic Model Research Articles

A kinetic study of nonthermal plasma pyrolysis of methane: Insights into hydrogen and carbon material production

Nonthermal plasma-assisted methane pyrolysis has emerged as a promising approach for hydrogen production under mild conditions while simultaneously yielding valuable carbon materials. Herein, we develop a plasma chemical kinetic model to elucidate the underlying reaction mechanisms involved in methane pyrolysis to hydrogen and solid carbon within a gliding arc (GA) reactor. A zero-dimensional (0D) chemical kinetics model was developed to simulate the plasma chemistry during the GA-based methane pyrolysis process, incorporating reactions involving electrons, excited species, ions, and heavy species. The model accurately predicted methane conversion and product selectivity in agreement with the experimental data. A strong correlation between hydrogen production and methane conversion was observed, primarily driven by the reaction CH4 + H → CH3 + H2, contributing 44.2% to hydrogen formation and 37.7% to methane depletion. Electron impact collisions with hydrocarbons play a secondary role, accounting for 31.1% of H2 formation. This work provides a detailed investigation into the mechanism of solid carbon formation in GA-assisted methane pyrolysis. Most of the solid carbon originates from the electron impact dissociation of C2H2 through reactions e + C2H2 → e + C2 + H2/2H and subsequent C2 condensation. C2 radicals are highlighted as the major contributors to solid carbon formation, accounting for 95.0% of the total carbon yield, which might be due to the relatively low C–H dissociation energy in C2H2. This kinetic study offers a comprehensive understanding of the mechanisms behind H2 and solid carbon formation during GA-assisted methane pyrolysis.

Laminar burning characteristics of ammonia and hydrogen blends at elevated initial pressures up to 2.5 MPa

Ammonia is a highly promising alternative fuel, and blending it with hydrogen can mitigate its poor combustion performance. However, the combustion mechanism of ammonia-hydrogen mixtures requires further validation through measurements of laminar burning velocity, particularly under high-pressure conditions relevant to practical combustors. Experimental data at high initial pressures (>1.0 MPa) are notably scarce. In this study, experiments were conducted using an outwardly propagating spherical flame in a high-pressure, high-temperature, constant-volume combustion chamber to determine the laminar burning velocities of ammonia-hydrogen blends at elevated initial pressures. The effects of different equivalence ratios (0.6 ∼ 1.4), volumetric hydrogen ratios (0.1 ∼ 0.6), and initial pressures (0.1 ∼ 2.5 MPa) were evaluated. Chemical kinetics of ammonia and hydrogen combustion was investigated at high pressures. The experimental results were compared with the simulation results under a wide range of conditions using several existing mechanisms to evaluate their applicability. The results show that the laminar burning velocity increases first and then decreases as the equivalence ratio (ϕ) increases and reaches a maximum value around ϕ of 1.1. The laminar burning velocity increases non-linearly with the volumetric hydrogen ratio, with more pronounced acceleration at higher hydrogen ratios. In contrast, the laminar burning velocity decreases non-linearly with the increasing initial pressure, and this reduction becomes progressively slower as the initial pressure rises. The predictive performance of the mechanisms by Okafor et al. and Gotama et al. is relatively satisfactory under certain conditions, but further optimization based on experimental data is necessary. Additionally, reaction pathway analysis of ammonia-hydrogen combustion indicates that introducing hydrogen increases the concentration of active radicals such as OH, O, and H, thereby enhancing ammonia combustion. Sensitivity analysis of the laminar burning velocity identified the critical elementary reactions across varying pressures, providing strong support for optimizing ammonia-hydrogen chemical kinetics models and developing simulation models for practical combustion systems.

Revealing the flame inhibition effect of phytic acid (PA) by PIV measurements and detailed chemical kinetic modeling of counterflow CH4/PA/air flames

As industrialization continues to deepen, polymers have become ubiquitous in daily life. However, their flammable characteristics pose significant safety risks. Therefore, supporting the global goal of sustainable development necessitates the development of high-performance, environmentally friendly flame retardants. Biomass phytic acid (PA) has emerged as a promising option because of its high phosphorus content and excellent biocompatibility. However, its combustion behaviors and chemical kinetic mechanisms remain unclear. In this study, quantum chemical calculation methods were used to construct a detailed PA chemical reaction kinetic model. A series of experiments were conducted to validate the model and evaluate PA's flame suppression effect. Utilizing a counterflow flame burner and particle image velocimetry (PIV), the inhibitory effect of various PA concentrations was examined based on the laminar flame speed of CH4/PA/Air mixture. The results revealed that a merely 0.2 % addition of PA could reduce the laminar flame speed by 38.9 %, demonstrating its significant flame suppression effect. Building on the foundational GRI-Mech 3.0 and integrating PA's pyrolysis and reaction mechanism, this study developed for the first time a detailed chemical model of CH4/PA/Air combustion. This model integrated PA's thermal decomposition module and thermodynamic data via ab-initio quantum chemical calculations, thereby accurately predicting global kinetic indicators such as laminar flame speed. Results suggested that the key reactions, such as PO2+H + M→HOPO + M, HOPO2+H→PO2+H2O, and HOPO + OH→PO2+H2O primarily influenced the laminar flame speed. Moreover, the CFD simulation elucidated the complex interaction between PA and flame structures. A detailed analysis of the spatial distribution of key parameters such as temperature, combustion radicals, and effective inhibition radicals unveiled the PA's flame suppression mechanism in support of the practical application of this eco-friendly flame retardant.

Combined control of PM and NOx emissions from small-scale combustions by electrostatic precipitation

Electrostatic precipitators (ESPs) have demonstrated promise in reducing particulate matter (PM) emissions, but their potential for simultaneously reducing NOx in small-scale combustion systems remains largely unexplored. This study examines the potential of ESP with DC corona discharge of negative polarity to reduce both PM and NOx emissions from small-scale combustion. A chemical kinetic model is first developed to predict NOx removal in the ESP. The model accounts for the non-uniform electric field distribution and inhomogeneity of non-thermal plasma in chemical kinetic while remaining simple enough for practical engineering applications. This allows for the optimisation of ESP parameters during the initial design phase. Using this model, the ESP was developed and applied with different energisation regimes to control emissions from a 15 kW pellet combustion heating unit. The initial concentrations for PM and NOx were 48 mg/m3 and 305 mg/m3, respectively (0 °C, 101.3 kPa; at reference O2 = 10 %vol.). The efficiency of the ESP was both theoretically and experimentally determined for various operational regimes at voltages ranging from 6.8 to 11 kV. At 11 kV, the ESP demonstrated a PM removal efficiency of 99.99 % and a NOx removal efficiency of 38 %, achieving compliance with Ecodesign Directive limits. The model's predictions showed reasonable agreement with experimental data, with a slight miscalculation for both particle precipitation and NOx removal. These findings have significant implications for the design and operation of ESPs in small-scale biomass combustion systems, offering a foundation for optimising these devices for combined NOx and particulate matter control.

Basal State Calibration of a Chemical Reaction Network Model for Autophagy.

The modulation of autophagy plays a dual role in tumor cells, with the potential to both promote and suppress tumor proliferation. In order to gain a deeper understanding of the nature of autophagy, we have developed a chemical reaction kinetic model of autophagy and apoptosis based on the mass action kinetic models that have been previously described in the literature. It is regrettable that the authors did not provide all of the information necessary to reconstruct their model, which made their simulation results irreproducible. In this study, based on an extensive literature review, we have identified concentrations for each species in the stress-free, homeostatic state. These ranges were randomly sampled to generate sets of initial concentrations, from which the simulations were run. In every case, abnormal behavior was observed, with apoptosis and autophagy being activated, even in the absence of stress. Consequently, the model failed to reproduce even the basal conditions. Detailed examination of the model revealed erroneous reactions, which were corrected. The influential kinetic parameters of the corrected model were identified and optimized using the Optima++ code. The model is now capable of simulating homeostatic states, and provides a suitable basis for further model development to describe cell response to various stresses.

Fuel blend combustion for decarbonization

The utilization of fossil fuels is currently transforming to low-carbon or zero-carbon fuels, which is one of the solutions to global warming. Hydrogen and ammonia are regarded as promising zero-carbon fuels in power supply and transportation scenarios but the availability of hydrogen and their distinctly different chemical activity constrain their large-scale direct utilizations. Fuel blends with physical and chemical complementary are considered as the effective approaches in the utilization of hydrogen and ammonia because no significant modification to the existing end-user infrastructures is needed. This paper reports recent progress in the fundamental combustion behaviors of fuel blends, focusing on hydrogen-hydrocarbon blends and ammonia-hydrocarbon blends. Firstly, laminar flame behaviors, auto- and forced-ignition characteristics, and pollutant emissions of binary fuels containing hydrogen are reviewed, all of which are supplemented with a discussion on the governing hydrogen-enriched combustion chemistry. Subsequently, the hydrogen-enriched flame responses to the flow conditions are discussed, including the turbulent burning velocity and statistical structures, the flashback swirl flames, thermoacoustic instabilities, and the jet ignition characteristics; Furthermore, with the increasing concern over ammonia as a zero carbon fuel and its extremely weak reactivity, recent progress on combustion of fuel blends containing ammonia are also reviewed. The fundamental combustion chemistry studies including laminar burning velocity, the ignition delay times data collection, as well as the attempts for chemical kinetic modeling development for fuel blend with ammonia are presented. The literature reported ammonia containing blends of turbulent flame characteristics are presented. Finally, from an engineering point of view, examples using hydrogen blends in practical internal combustion engines and in gas turbines are introduced, including the topic of engine efficiency performance and pollutant emissions and different combustors for gas turbines. It is suggested that fuel blends with hydrogen or ammonia that potentially monitors the overall reactivity will be one realistic solution to de-carbonization, on the basis of current transportation and power generation systems.

Experimental and kinetic study of methanol/ethanol assisted oxidative degradation of ammonia in supercritical water

Ammonia is a refractory intermediate during supercritical water oxidation (SCWO) of nitrogen-containing wastes, and alcohols are usually introduced as auxiliary fuels to accelerate its degradation. The kinetics of methanol/ethanol assisted oxidative degradation of ammonia in supercritical water have been investigated in a flow reactor, covering alcohol-to-ammonia ratios of 0.2–2.0. During SCWO of ammonia-methanol mixtures, ammonia was mostly converted to N2, with N2O as the main by-product. Increasing methanol concentration facilitated effectively the degradation of ammonia. For the cases with ethanol assistance, high concentrations of HCN were detected at the investigated temperature. Increase in ethanol concentration enhanced ammonia conversion, but had a non-monotonic influence on N2 production. A detailed chemical kinetic model was developed by integrating the nitrogen chemistry with methanol/ethanol mechanisms. The model performance was further validated by comparing to the present and literature data. The model reproduced the ammonia conversions at different conditions fairly well, but overpredicted the N2 yield and underpredicted the NO2 and HCN yields slightly. Based on the model, reaction mechanism was inferred and important elementary steps were identified through kinetic analyses. Finally, the influence of process parameters on ammonia degradation rate was numerically explored. This study is expected to facilitate the application of SCWO technology for N-containing wastes treatment.

Experimental and kinetic modeling investigation of NOx control in coal combustion by ammonia reburning

The carbon peaking and carbon neutrality goals present urgent demands for the green low-carbon transformation of the energy system. As a potential alternative energy, ammonia (NH3) used as reburning fuel in the coal-fired boilers will achieve both low-carbon and low-NOx emissions. To investigate ammonia reburning, experimental and chemical kinetic modeling were conducted in a tube flow reactor at 1023–1573 K under both ammonia and coal combustion conditions. Factors are researched including the combustion atmospheres of NH3/N2/O2 (PM-NH3) and coal/N2/O2 (PM-Coal), different inlet CO concentrations, reburning temperatures and reburning fuel ratios. The results indicate that ammonia reburning can effectively reduce NO emissions by about 95 %. The C-N reaction exhibits a positive effect on NO reduction at low temperature and a negative effect at high temperatures. As the CCO increases from 0 % to 4 % at 1573 K, the optimum temperature window size increases from 225 K to 413 K, and NO reduction rises from 31.25 % to 97.5 %. The whole ammonia reburning process includes NO rapid reduction stage (NRS), NO oxidation stage (NOS), and NO slowly re-reduction stage (NRRS) at high temperature. The chemical kinetic modeling indicates that the C-N reaction obviously shortens the residence time of the NRS and increases the ROP in the NOS, which together undercut NO reduction compared to PM-NH3 case. The promotion of the oxidation path of NH3-NH2-HNO-NO results in the NOS appearance and NRS ending. Moreover, this path affected by C-N reaction is primarily responsible for NO reduction cutoff in the PM-coal case.

Modeling of Spray Combustion and Heat Transfer of MMH/N2O4 in a Small Rocket Engine Using Different Mechanisms

Although various hypergolic propellants like MMH/N2O4 (monomethylhydrazine/dinitrogen tetroxide) are widely used in small rocket engines, there remains a lack of in-depth study conducted on their chemical reactions and spray combustion behaviors. To fill this research gap, a simplified chemical kinetic model that is suitable for three-dimensional simulation was proposed in this paper for MMH/N2O4. Then, numerical investigation was conducted using the Volume of Fluid (VOF) model to explore the transient injection and atomization of MMH/N2O4 impinging jets in a small bipropellant thruster. Also, the instantaneous formation and evolution of the fan-shaped liquid film were analyzed. With the spray distribution determined, the proposed kinetic model and two existing mechanisms were applied to simulate spray combustion and heat transfer within the thruster, respectively, under the Euler–Lagrange framework. According to the research results, the liquid film covered nearly the entire chamber wall with a sawtooth pattern, which protected against the high temperatures of the engine wall. Notably, the two existing mechanisms showed significant errors in predicting temperature changes around the wall due to the excessively simplified reaction pathways. In contrast, the proposed model enabled the accurate prediction of the chamber pressure, wall temperature, and thrust with an error of less than 10%. Given the high accuracy achieved by the proposed numerical method, it provides a valuable reference for the development of advanced space engines.

A detailed chemical kinetic model for methanol and ammonia co-oxidation under hydrothermal flames: Reaction mechanism and flame characteristics

A detailed chemical kinetic model for ammonia and methanol co-oxidation under hydrothermal flames was established with pressure and thermodynamic corrections. Simulation model was validated by comparing with experimental temperature rise, and methanol and ammonia removal efficiencies. Species evolutions, reaction paths, and reaction sensitivities for pure ammonia combustion, and ammonia and methanol co-oxidation under hydrothermal flames were analyzed. Ammonia concentration begins to decrease only when methanol is consumed in a certain amount in the ammonia and methanol co-oxidation under hydrothermal flames, indicating the addition of methanol promotes the degradation of ammonia. Moreover, reaction heat is more conductive to ignition and the conversion of ammonia to nitrogen than active free radicals provided from methanol. The ignition delay time presents a minimum as a function of ammonia/methanol concentration ratio, with the minimum values of ignition delay time present at approximately ωNH3/ωCH3OH = 1 for different methanol concentrations. Higher preheating temperatures favor more NOX but less N2O formation, while higher ammonia concentrations favor both NOX and N2O formations. The presence of ammonia increases the laminar flame speed and permits a lower extinction temperature, indicating the mixture of methanol and ammonia can improve the stability of hydrothermal flames.

Atmospheric Degradation Mechanism of Isoamyl Acetate Initiated by OH Radicals and Cl Atoms Revealed by Quantum Chemical Calculations and Kinetic Modeling.

Isoamyl acetate is one of the volatile organic compound class molecules relevant to agricultural and industrial applications. With the growing interest in isoamyl acetate applications in industry, the atmospheric fate of isoamyl acetate must be considered. Reaction mechanisms, potential energy profiles, and rate constants of isoamyl acetate reaction with atmospheric relevant oxidant OH radicals and Cl atoms have been obtained from the quantum chemical calculations and kinetic modeling. The geometry optimizations were conducted using M06-2X/6-311++G(3df,3pd) followed by single point-energy calculations at the DLPNO-CCSD(T) method with an extrapolated complete basis set. The rate constants were calculated by solving the master equation. A hydrogen-abstraction reaction dominates the first step of isoamyl acetate degradation, while the addition-substitution reaction plays a small role in the degradation products. The kinetic study was conducted to evaluate the rate constants within a temperature range of 200-400 K. The total rate constants for the isoamyl acetate degradation reactions initiated by the OH radical and Cl atom were determined to be 6.96 × 10-12 and 1.27 × 10-10 cm3 molecule-1 s-1, respectively, under standard temperature and pressure conditions. The product degradation mechanism, ozone formation potential, and atmospheric impacts were discussed.

Species selection for automatic chemical kinetic mechanism generation

AbstractMany important chemical kinetic systems require detailed chemical kinetic models to resolve. These detailed kinetic models can involve thousands of species and hundreds of thousands of chemical reactions, making them difficult to construct by hand. Modern automatic mechanism generation algorithms can mostly be divided into two classes: rule and rate based. Rule‐based generators choose species based on user defined constraints on species and reaction classes. Rate‐based generators generate a much larger set of potentially important species and reactions and then choose which ones to add based on running simulations of species and reactions deemed important and calculating the flux to potentially important species. In principle, the latter is preferable, as it requires the user to make far fewer assumptions about what is important in the system. However, while the effectiveness of the rate‐based approach has been demonstrated in a wide variety of systems, it has also been demonstrated to have difficulty picking up important low‐flux chemistries. Here we present a discussion of the challenges associated with rate‐based mechanism generation and new algorithms that are able to efficiently mitigate these challenges improving species selection during mechanism generation in a set of case studies.

Theoretical Kinetics of Radical-Radical Reaction NH2ṄH + ṄH2 and Its Implications for Monomethylhydrazine Pyrolysis Mechanism.

Significant discrepancies were observed between the experiments and the simulations for ṄH2 time-histories in monomethylhydrazine pyrolysis with the robust mechanism proposed by Pascal and Catoire. The rate of formation analyses for ṄH2 indicated the significance of the reaction NH2ṄH + ṄH2 = H2NN + NH3, which has not been well-defined. In this study, ab initio calculations were performed for the theoretical description of the NH2ṄH + ṄH2 chemistry. Most stationary points on the potential energy surface were quantified at the CCSD(T)/CBS//M06-2X/aug-cc-pVTZ level, and the multireference methods were employed for barrier-less reaction and some transition states. The temperature- and pressure-dependent rate coefficients were determined using classical and microcanonical variational transition state theories. Four primary reaction channels were identified as competitive: 1) The H atom abstraction reaction yielding N2H2(T) + NH3, dominating at 1350-3000 K across the 0.001-100 atm pressure range. 2) The H atom abstraction reaction forming N2H2(S) + NH3, dominating at 800-1350 K and competing with the processes of chemical activation and collisional stabilization below 800 K. 3) The chemical-activated reaction resulting in H2NN(S) + NH3, dominating below 800 K at 0.001 atm. 4) The collisional-stabilized recombination reaction leading to N3H5, becoming significant as pressure increases and dominating below 600 and 650 K at 1 and 100 atm, respectively. The implications of newly calculated NH2ṄH + ṄH2 kinetics for the monomethylhydrazine pyrolysis mechanism were evaluated, and updates were implemented. Sensitivity analyses indicated the necessity of additional research efforts to comprehend the dynamics of CH3NH2 unimolecular and N2H2 + ṄH2 reaction systems. The rate coefficients presented in this study can be employed to develop the chemical kinetic model of nitryl-containing systems.

Comparative Study of n-C5 Bond Dissociation Energies and H-Atom Abstraction via H for Alkane, Alcohol, Methyl Ether, Nitroso, Nitro, Nitrite, and Nitrate.

Energetic materials have a wide range of applications, for many of which new materials are constantly developed. For understanding how energetic materials are chemically converted, it is essential to systematically understand how relevant functional groups affect the stability and properties of such materials. Here, the impact of nitroso, nitro, nitrite, and nitrate functional groups on a pentyl moiety is studied theoretically, focusing on bond dissociation energies and H atom abstraction via Ḣ. The nitroso group is found to imply the strongest effects, while the nitro group appears to exert a stabilizing effect on the pentyl moiety. Importantly, the nitrogenated functional groups generally stabilize the pentyl moiety, in contrast to alcohol and methyl ether functional groups. Therefore, it is concluded that using analogies to the chemistries of the latter two functional groups for chemical kinetic modeling of nitrogenated functional groups is not adequate. Based on the presented bond dissociation energies and rate coefficients, it is to be expected that unimolecular bond fissions at the nitrogenated functional groups will dominate over a wide temperature range. Building on the provided data, future detailed chemical kinetic modeling efforts for nitroso, nitro, nitrite, and nitrate compounds can be aided or initiated.

The response of daytime nitrate formation to source emissions reduction based on chemical kinetic and thermodynamic model

Particulate nitrate is an important component of particulate matter and poses a significant threat to the ecosystem and human health. The gas-phase formation pathway of nitrate is extremely important, which mainly comprises the NO2 oxidation process triggered by OH radicals and the nitrate partitioning process. The response of nitrate to source emission reduction during different pollution periods remains unclear. Here, we applied the chemical kinetic and thermodynamics model to explore the importance oxidation process and partitioning process during different pollution periods based on high-time resolution observation data. The result indicated that with the aggravation of pollution, the partitioning process gradually ceases to be a limiting step in the formation of nitrates. The results of the influencing factor analysis indicate that NO2 concentration and aerosol pH values play a more significant role in the formation of nitrates. Specifically, during the clean period, nitrate formation is sensitive to both NO2 concentration and pH values, but during the pollution period, it becomes sensitive only to NO2 concentration. By combining source apportionment, we explored the response of nitrate formation to source emission reduction, and the results showed that the control of vehicle exhaust emissions and coal combustion sources is more effective in mitigating nitrate pollution. Additionally, this study also emphasized the importance of early prevention and control of pollution sources. This research provides scientific evidence for the precise management and control of nitrates.

Numerical investigation of vacuum ultra-violet emission in Ar/O2 inductively coupled plasmas

Abstract Controlling fluxes of vacuum ultraviolet (VUV) radiation is important in a number of industrial and biomedical applications of low pressure plasma sources because, depending on the process, VUV radiation may be desired, required to a certain degree, or unwanted. In this work, the emission of VUV radiation from O atoms is investigated in low-pressure Ar/O2 inductively coupled plasmas via numerical simulations. For this purpose, a self-consistent Ar/O2 plasma-chemical reaction scheme has been implemented in a zero dimensional plasma chemical kinetics model and is used to investigate VUV emission from excited O atoms (3s 5S 2 0 and 3s 3S 1 0 ) at 130 and 135 nm. The model is extensively compared with experimental measurements of absolute VUV emission intensities, electron densities and Ar excited state densities. In addition, oxygen VUV emission intensities are investigated as a function of pressure, Ar/O2 mixture, and power deposition and the dominant reaction pathways leading to oxygen VUV emission are identified and described. In general terms, absolute oxygen VUV emission intensities increase with power and oxygen fraction over the ranges investigated and peak emission intensities are found for pressures between 5–50 Pa. The emission is dominated by the 130 nm resonance line from the decay of the O(3s 3S 1 0 ) state to the ground state. Besides, at low pressure (0.3–1 Pa), the flux of oxygen VUV photons to surfaces is much lower than that of positive ions, whereas oxygen VUV fluxes dominate at higher pressure, ≳ 5–50 Pa depending on O2 fraction. Finally, oxygen atom fluxes to surfaces are, in general, larger than those of VUV photons for the parameter space investigated.

Automatization of theoretical kinetic data generation for tabulated TS models building - Part II: 1,2 to 1,5-H-shift reactions in alkyl radicals

Branched alkanes make up a significant fraction of sustainable alternative fuels. The accurate chemical kinetic modeling of the pyrolysis and oxidation of those fuels requires the availability of accurate kinetic data for branched structures. The accurate theoretical calculation of these data for substituted cyclic transition states (TS) is a challenge because of the large number of configurations that can be created, especially in the larger TS cycles. These configurations originate from all the possible combinations of the orientations of the substituents (axial or equatorial) on the cyclic TS and diastereomers in the reactants, which makes the rigorous counting of the multiple parallel pathways complicated. In this paper, the isomerisation reactions of branched alkyl radicals are theoretically investigated using the code presented in the Part I of this paper series. The 1,2 to 1,5-H-shift reactions are studied within the tabulated transition state models approach, where chain substituents are represented by methyl groups, and all combinations of substitutions in the model TSs are included in a table with their computed rate constants. The rate constants computed for hundreds of reactions with our code demonstrate the necessity to consider all the TS configurations in order to get accurate data. The presence of spectator substituents in the cyclic transition state is shown to have a major impact on the rate constants, increasing their values by more than a factor of 10 for some cases. The tabulated TS models (TMTS) method is validated by comparisons with available experimental data in the literature and is one of the only approach able to accurately capture the impact of branching on the rate constants of isomerizations for large alkyl radicals, which are still difficult to calculate with high-level on-the-fly ab initio calculations.

The pronounced NTC behavior of 1,2,4-trimethylbenzene at high-pressure oxidation

This study presents experimental and modeling results of the 1,2,4-trimethylbenzene (T124MBZ) oxidation in a jet-stirred reactor at equivalence ratios of 0.4 and 2.0, temperature range of 450–1000 K, and pressure of 12.0 atm. Compared with the oxidation at atmospheric pressure, a pronounced negative temperature coefficient (NTC) behavior of T124MBZ was observed between 622 K and 773 K under fuel-lean condition. A detailed chemical kinetic model involving 865 species and 5092 reactions was developed. In addition, the model was validated against experimental results of laminar burning velocities and ignition delay times. The present model reasonably reproduces these experimental data. The dominant consumption channels for T124MBZ are H-abstraction reactions on methyl groups by OH radicals. The H-abstraction reactions on the 1- and 2- methyl sites by OH radicals are the most promoting in pre- and mid- NTC phases, and H2O2(+M) = 2OH(+M) is the most promoting in the post-NTC phase, while the reaction on the 4-methyl site is the most inhibiting across pre-, mid-, and post-NTC phases. This difference arises from the fact that the dominant consumption pathway for 2,4-dimethylbenzyl and 2,5-dimethylbenzyl involves H-transfer, while the 4-methyl site cannot undergo an H-transfer reaction due to the absence of adjacent methyl groups. The competition between the two consumption channels of ·QOOH radicals (decomposition and second O2 addition), resulting in the reduction of OH radicals as temperature increases, leads to diminished OH production. This causes the emergence of pronounced NTC behavior at high pressure.

An experimental and modeling study of propane oxidation kinetics in low temperature supercritical water

Propane oxidation in supercritical water was investigated at iso-thermal iso-baric conditions using a batch reactor facility. Mixtures were comprised of 0.014 % propane by volume with an equivalence ratio of 0.8 and a total density of 222 mg/mL or 610 mg/mL. Reaction times ranged from 8 to 30 min for a temperature of 375ºC at 220 or 400 bar, or 400ºC at 220 bar. Major reaction products were CO and CO2 and minor products were propene, acetone, ethene, ethanol, methane, methanol and hydrogen. New detailed chemical kinetic models were developed by combining and refining existing models using genetic optimization. Model predictions exhibited excellent agreement with experimental observations, and indicated that rates of H-abstraction and OH addition reactions involving alkanes and alkenes are affected by the supercritical water environment. Model accuracy was highly sensitive to the rates of CH3O2H = CH3O + OH and CH3 + H2O2 = CH4 + HO2.

Development of Detailed and Reduced Chemical Kinetic Models for Ammonia Gas Turbines

Abstract The power generation sector has been recently moving towards decarbonization and there is an increased interest in replacing conventional fossil fuels with fuels that produce reduced/zero carbon emissions. One such fuel is ammonia (NH3). However, ammonia is hard to ignite, has a low flame speed, and produces a significantly large amount of nitrogen oxide (NOx) emissions. Hence, using 100% ammonia as fuel in gas turbines requires significant modifications and the development of novel combustors. Blending hydrogen with ammonia, however, helps in having better control over the combustion properties. Before utilizing hydrogen-blended ammonia in an actual gas turbine combustor, thorough simulation studies are required to evaluate its performance, possible hazards, and emissions. The literature lacks well-validated chemical kinetic models for the combustion of hydrogen-blended ammonia for undiluted mixtures at gas turbine-relevant conditions (~20 bar). Hence, in this work, we develop a detailed chemical kinetic model for hydrogen blended ammonia combustion and validate it with a wide range of experimental data for both dilute and undiluted mixtures relevant to gas turbine operating conditions. The detailed chemical kinetic mechanism was reduced to a smaller version (32 species mechanism) without significant loss in accuracy using the direct relation graph with error propagation (DRGEP) and full species sensitivity analysis. The resultant mechanism can predict a wide range of experimental results with the least cumulative error and will be a valuable tool in CFD simulations that will enable the development of gas turbines for zero-carbon power generation.