Detailed Kinetics Research Articles

Detailed mechanism and kinetics of reactions of anti- and syn-CH3CHOO with HC(O)OH: infrared spectra of conformers of hydroperoxyethyl formate.

The reaction of CH3CHOO with HC(O)OH has a large rate coefficient so that it might play a significant role in the formation of secondary organic aerosols (SOA) in the atmosphere. We investigated the detailed mechanism and kinetics of the reactions of Criegee intermediate anti- and syn-CH3CHOO with HC(O)OH with a step-scan Fourier-transform infrared spectrometer by recording time-resolved absorption spectra of transient species and end products produced upon irradiation at 308 nm of a flowing mixture of CH3CHI2/O2/HC(O)OH at 298 K and 60 Torr. Thirteen bands of hydroperoxyethyl formate [HC(O)OCH(CH3)OOH, HPEF], the hydrogen-transferred adduct of CH3CHOO and HC(O)OH, were observed. Careful analysis deconvoluted these bands into absorption of three conformers of HPEF: a transient HPEF (P2*/P3*), a more stable open-form HPEF (mainly P2), and a stable intramolecularly hydrogen-bonded HPEF (mainly P1). At a later period, the end-product formic acetic anhydride [CH3C(O)OC(O)H, FAA], a dehydrated product of HPEF, was observed; this end-product is the same as that observed in CH2OO + CH3C(O)OH. Theoretical calculations on the reaction pathway scheme were performed to elucidate these reaction paths. Syn-CH3CHOO + HC(O)OH produced conformers P2*/P3* initially, followed by conversion to conformers P2, whereas anti-CH3CHOO + HC(O)OH produced conformers P2 and P1 directly. We derived a rate coefficient for the reaction CH3CHOO + HC(O)OH to be k = (2.1 ± 0.7) × 10-10 cm3 molecule-1 s-1 at 298 K and 40-80 Torr; the rate coefficient appeared to show insignificant conformation-specificity. We also found that FAA was produced mainly from the dehydration of the open-form HPEF (P2) with a rate coefficient k = (1420 ± 70) s-1; the intramolecularly hydrogen-bonded HPEF (P1) is stable.

Enhancing lithium-ion battery safety: Investigating the flame-retardant efficacy of bis(2,2,2-trifluoroethyl) carbonate during ethyl methyl carbonate combustion

Bis(2,2,2-trifluoroethyl) carbonate (BtFEC) is a candidate fire suppressant for lithium-ion batteries (LIBs). The high flammability of the electrolyte is the reason behind the frequent fire incidents reported with LIBs. These incidents are due to various factors, such as a default in the conception of the battery or operational abuse. The flame-retardant effectiveness of BtFEC was investigated by measuring its effect on the oxidation of ethyl methyl carbonate (EMC), a common LIB electrolyte component. Laminar flame speed (LFS) measurements for EMC-BtFEC in air mixtures were carried out at 403 K, 1 atm, for equivalence ratios (ϕ) between 0.8 and 1.4, and with 0.5 % vol. BtFEC. Additional measurements were made at ϕ = 1.1 with BtFEC addition ranging from 0.1 up to 1.4 % vol. To further understand the combustion chemistry of the EMC-BtFEC system, ignition delay times (time at the maximum peak production of the excited radical OH*) and CO time histories were measured in a shock tube with temperatures ranging from 1217 to 1732 K, at near-atmospheric pressure (1.24–1.42 atm), and for three equivalence ratios (ϕ = 0.5, 1.0, and 2.0). These new results constitute an experimental database that was used to evaluate the performance of a model assembled for both BtFEC and EMC using previous work from our group. The updated, detailed chemical kinetics mechanism presented in this study consists of 237 species and 1630 reactions. Sensitivity, rate-of-production, and reaction pathway analyses permitted the oxidation of the BtFEC-EMC system to be described. A flame sensitivity analysis exhibited the significant effect from the reactions H + CF2O ⇆ HF + CFO and CF3 + H ⇆ CF2 + HF, which consume H radicals that are involved in the branching reaction H + O2⇆ OH + O, ultimately reducing the LFS. This study shows that improvements in the base fluorine chemistry are still necessary to obtain better agreement with the experiments, especially at the speciation level.

The mechanism and kinetics of the atmospheric oxidation of CF3(CF2)2CHCH2 (HFC-1447fz) by hydroxyl radicals: ab initio investigation.

The oxidation of 3,3,4,4,5,5,5-heptafluoro-1-pentene (HFC-1447fz) by hydroxyl radicals plays a crucial role in atmospheric conditions. By employing the CCSD(T)/cc-pVTZ//M06-2X/6-311++G(d,p) level of theory, the detailed reaction mechanism, kinetics and atmospheric implications of the degradation of HFC-1447fz by hydroxyl radicals were investigated. Compared to H-abstraction channels, the OH addition reaction is determined to be more favorable initial pathways in the degradation processes of HFC-1447fz. The overall rate coefficient of the degradation of HFC-1447fz by OH radicals is estimated to be 1.66 × 10-12 cm3 molecule-1 s-1 and the lifetime of HFC-1447fz is found to be 7 days at 298 K, which are in good agreement with the reported experimental results. The global warming potential (GWP) for HFC-1447fz on the 50, 100 and 500-year time horizons is estimated using the calculated rate coefficient. Furthermore, the mechanisms of the subsequent reactions of two OH-addition adducts have also been investigated. By TD-DFT calculations, it was found that eleven species can undergo photodissociation, while ten other species are photolytically stable under sunlight.

Detailed numerical simulation and experiments of a steadily burning micron-sized aluminum droplet in hot steam-dominated flows

Detailed numerical simulations are conducted in comparison with experimental results to study the flame structure and burning rate of a steadily burning aluminum droplet in hot steam-dominated environments. The droplet surface temperature, flame temperature, and flame stabilization position are measured along with the droplet burning rate estimated from the droplet size evolution. A numerical model accounting for detailed transport properties and chemical kinetics is presented and applied to unveil the flame structure, species and temperature distributions, and heat/mass transfer between the droplet and the surrounding gas. The numerical results of the temperature, velocity, and species distribution profiles demonstrate that the aluminum vapor flame is of classical diffusion flame structure, where near the droplet, there is a non-negligible amount of AlOAl apart from the main product Al2O3(l). This supports the deposition and formation of an alumina cap on the surface proposed in the literature. The simulation correctly captured the flame temperature and flame stabilization distance for a range of droplet sizes. Net heat flux analysis shows that conduction heat from the flame front accounts for less than 30% of the heat needed in aluminum evaporation, which warrants further quantification on other heat sources. The experimental and numerical results enrich the knowledge of the heat/mass transfer and chemical reactions near the droplet, which helps deepen the understanding of aluminum droplet burning.

Probing O2-dependence of cyclopentyl reactions via isomer-resolved speciation

Modeling chemical kinetics relevant to low-temperature combustion requires complete description of reactions involving critical species such as hydroperoxyalkyl radicals, Q˙OOH, which undergo competing unimolecular reactions and bimolecular reactions with O2. The balance of flux across the two pathways affects rates of chain-branching and depends on temperature, pressure, and oxygen concentration. Accordingly, the influence of [O2] on product formation from alkyl + O2 reactions and the subsequent fate of Q˙OOH and related products is central to the development of an accurate chemical kinetics mechanism. However, chemical reactions consuming Q˙OOH-mediated species are often simplified to such a degree that mechanism truncation error (uncertainty derived from incomplete reaction networks) becomes significant.For the specific purpose of determining the extent to which expanded sub-mechanisms ameliorate inaccuracies in model predictions resulting from mechanism truncation error, the present work integrates speciation measurements from jet-stirred reactor experiments on cyclopentane oxidation with modeling using an expanded detailed chemical kinetics mechanism. The experiments utilize vacuum ultraviolet-absorption spectroscopy and mass spectrometry for isomer-resolved speciation of intermediates produced from cyclopentane oxidation at 835 Torr from 500 – 1000 K. [O2]-dependent experiments were also conducted from 0.12 – 3.66 · 1018 molecules cm–3 at 825 K to examine the influence on species profiles. The expanded mechanism is produced by merging detailed sub-mechanisms for Q˙OOH-mediated species (cyclopentene and 1,2-epoxycyclopentane) produced using Reaction Mechanism Generator (RMG) with an existing detailed mechanism for cyclopentane.Model predictions using the expanded mechanism yielded improvements in species mole fractions for both temperature- and O2-dependence. Ignition delay time simulations were also conducted and show appreciable sensitivity in the negative-temperature coefficient region due to incorporation of the detailed sub-mechanisms due to influence on O˙H radical populations. Sensitivity analysis revealed reactions that merit theoretical rate calculations for additional improvements and include species such as H2O2 and species related to R˙ + O2 reactions of cyclopentene and 1,2-epoxycyclopentane.

Особенности инициирования подвижным источником энергии реакций в плоском слое, расположенном на подложке

In the conditions of the surface treatment of materials and coating application using mixtures of powders (metals, metals and nonmetals, metals and oxides) capable of chemical interactions, problems similar to those of solid-phase combustion theory arise. Currently available publications, which confirm the fact of the reactions, are limited to the analysis of the obtained structures, mechanical properties and the statement of the presence of certain compounds and phases. We present the reduced models for the synthesis of composites on a planar substrate allowing us to analyze qualitative effects. The first model is one-dimensional with a total reaction. The second model corresponds to the synthesis of a matrix-inclusion-type composite. The process is assumed to be driven by a moving heat source. Both models take into account the properties of the substrate. The transition to dimensionless variables reveals both the parameters characteristic of macrokinetics and the parameters typical for modern material synthesis technologies. The numerical solution shows that in the presence of a mobile heat source the reaction zone is sufficiently wide, and the temperature dynamics in general is dissimilar to that of combustion processes. It is shown that there is a parameter region in which partial transformation is observed. Two characteristics of the synthesis process have been determined - the time of the reaction initiation and the time of half-transformation (for a sample of finite size). Taking into account detailed kinetics, similar studies allow us to predict the qualitative composition of synthesis products when changing the conditions and initial composition of powder mixtures.

Shock-tube study of the oxidation of ammonia by N2O

The oxidation of ammonia by N2O was studied by following the time history of ammonia in a shock tube with a spectroscopic laser diagnostic. Dilute (99.5 % Ar) mixtures were studied around atmospheric pressure for several equivalence ratios: 0.25, 0.85, 1.0, and 2.0. The time at which the ammonia concentration reaches 50 % of its original value (τ50%) was also measured. Results were compared to several detailed kinetics models from the literature. Based on past work from the authors and a literature mechanism, a tentative model was also assembled to better represent the experiments at the conditions investigated herein. The quantitative NH3 diagnostic shed light on the limitations associated with the passivation method to counterbalance ammonia adsorption on the reactor's surface and showed that an ammonia diagnostic is necessary and critical to know the initial conditions for dilute mixtures. Experimental results show a relatively large effect of the equivalence ratio on the mixture's reactivity. The main outcome of this study is that while τ50% can be accurately predicted by all models considered, large variations are observed when comparing with the full NH3 time-history profile. Key features of the experimental profiles were not captured by the models, and large variations were observed between the models. Overall, the most recent models and the tentative models from this study performed the best, but more work remains necessary to fully capture the oxidation of ammonia by N2O. The effect of the third-body collision coefficient on N2O (+M) ⇆ N2 + O (+M) was investigated for several species, but no effect was found under the conditions investigated. However, it is likely that studying N2O (+NH3) ⇆ N2 + O (+NH3) is necessary for real-world applications.

Exploring the oxidation behavior of undiluted and diluted iron particles for energy storage: Mössbauer spectroscopic analysis and kinetic modeling.

Iron is an abundant and non-toxic element that holds great potential as energy carrier for large-scale and long-term energy storage. While from a general viewpoint iron oxidation is well-known, the detailed kinetics of oxidation for micrometer sized particles are missing, but required to enable large-scale utilization for energy production. In this work, iron particles are subjected to temperature-programmed oxidation. By dilution with boron nitride a sintering of the particles is prevented enabling to follow single particle effects. The mass fractions of iron and its oxides are determined for different oxidation times using Mössbauer spectroscopy. On the basis of the extracted phase compositions obtained at different times and temperatures (600-700 °C), it can be concluded that also for particles the oxidation follows a parabolic rate law. The parabolic rate constants are determined in this transition region. Knowledge of the particle size distribution and its consideration in modeling the oxidation kinetics of iron powder has proven to be crucial.

Transition of characteristic explosion limits: From hydrogen to diethyl ether

In this work, the explosion limits of three different fuels: hydrogen (H2), propane (C3H8, C3), and diethyl ether (DEE, C2H5OC2H5, C4), are investigated based on detailed chemical kinetics. The results reveal that the explosion limit of H2O2 exhibits the typical Z-shape, while C3H8O2 exhibits a single-NTC response, and DEE-O2 displays a double-NTC response. Sensitivity analysis indicates that the appearance of the NTC response in both the C3 and DEE fuels is intricately linked to low-temperature reaction paths. Moreover, the extents of the NTC responses are comparable for these two fuels with similar low-temperature reaction paths, but operate under different temperature conditions. Specifically, the double-NTC response observed in DEE is attributed to its primary CH and CO bonds, generating C4 and C2 radicals. The oxygen addition and the subsequent pathways of these radicals dominate in distinct temperature ranges. In contrast, C3H8 only possesses the CH bond, resulting in a single-NTC response, as OH radicals are mainly released by C3 radicals through oxygen addition, isomerization, and decomposition reactions. The results of binary fuel mixtures with H2 addition indicate that the reactivity of H2 controls the low-pressure and high-temperature regime, while the C3 and DEE fuels dominate the high-pressure and low-temperature regime. Additionally, a triangular crossover regime is identified between these two regimes due to the switchover of the reactivity. Sensitivity analysis further reveals the transition of the dominating reactions related to different fuels at various pressure-temperature regimes. Finally, based on the explosion limits of the multi-component mixtures, a detailed explosion regime diagram is proposed for carbon-free fuel (H2), alkane fuel (C3H8), and oxygenated ether fuel (DEE). This new regime diagram provides valuable insights for the investigation and utilization of ether fuels and the mixture of different fuels.

Machine Learning Tabulation Scheme for Fast Chemical Kinetics Computation

<div>This study proposes a machine learning tabulation (MLT) method that employs deep neural networks (DNNs) to predict ignition delay and knock propensity in spark ignition (SI) engines. The commonly used Arrhenius model and Livengood–Wu integral for fast knock prediction are not accurate enough to account for residual gas species and may require adjustments or modifications to account for specific engine characteristics. Detailed kinetics modeling is computationally expensive, so the MLT approach is introduced to solve these issues. The MLT method uses precalculated thermochemical states of the mixture that are clustered based on a combustion progress variable. Hundreds of DNNs are trained with the stochastic Levenberg–Marquardt (SLM) optimization algorithm, reducing training time and memory requirements for large-scale problems. MLT has high interpolation accuracy, eliminates the need for table storage, and reduces memory requirements by three orders of magnitude. The proposed MLT approach can operate across a wider range of conditions and handle a variety of fuels, including those with complex reaction mechanisms. MLT computational time is independent of the reaction mechanism’s size. It demonstrates a remarkable capability to reduce computation time by a factor of approximately 300 when dealing with complex reaction mechanisms comprising 621 species. MLT has the potential to significantly advance our understanding of complex combustion processes and aid in the design of more efficient and environmentally friendly combustion engines. In summary, the MLT approach has acceptable accuracy with less computation cost than detailed kinetics, making it ideal for fast model-based knock detection. This article presents a detailed description of the MLT method, including its workflow, challenges involved in data generation, pre-processing, data classification and regression, and integration into the engine cycle simulation. The results of the study are summarized, which includes validation against kinetics for ignition delay and engine simulation for knock angle prediction. The conclusions are presented along with future work.</div>

Modeling the curing kinetics of two thermoset adhesives under varying temperature conditions

AbstractThis paper presents detailed curing kinetics models for two thermoset adhesives. The cure kinetics were characterized using differential scanning calorimetry in both anisothermal and isothermal modes. The Sestak–Berggren autocatalytic model was applied to describe the anisothermal cure kinetics of the two adhesives with the Malek and undetermined coefficients methods determining their kinetic parameters. The Kamal autocatalytic model was adopted for the isothermal curing processes with the Kenny analytical‐graphical method determining the kinetic parameters. A modified Kamal model was developed by introducing a concept of the maximum degree of cure (DOC) and temperature‐depended kinetic parameters to describe the isothermal cure kinetics of the adhesive with a typical exothermic peak, and an extended Kamal model was further proposed by adding an initial‐phase‐control term to the modified Kamal model to describe the isothermal cure kinetics of the adhesive with two exothermic peaks. The results showed that the presented curing kinetics models with the determined parameters can precisely predict the evolutions of the DOC of the two thermoset adhesives in both anisothermal and isothermal modes.

A Simplified Chemical Reactor Network Approach for Aeroengine Combustion Chamber Modeling and Preliminary Design

In a time when low emission solutions and technologies are of utmost importance regarding the sustainability of the aviation sector, this publication introduces a reduced-order physics-based model for combustion chambers of aeroengines, which is capable of reliably producing accurate pollutant emission and combustion efficiency estimations. The burner is subdivided into three volumes, with each represented by a single perfectly stirred reactor, thereby resulting in a simplified three-element serial chemical reactor network configuration, reducing complexity, and promoting the generality and ease of use of the model, without requiring the proprietary engine information needed by other such models. A tuning method is proposed to circumvent the limitations of its simplified configuration and the lack of detailed geometric data for combustors in literature. In contrast to most similar frameworks, this also provides the model with the ability to simultaneously predict the combustion efficiency and all pollutant emissions of interest (NOx, CO and unburnt hydrocarbons) more effectively by means of implementing a detailed chemical kinetics model. Validation against three correlation methods and actual aeroengine configurations demonstrates accurate performance and emission trend predictions. Integrated within two distinct combustion chamber low-emission preliminary design processes, the proposed model evaluates each new design, thereby displaying the ability to be employed in terms of optimizing a combustor’s overall performance given its sensitivity to geometric changes. Overall, the proposed model proves its worth as a reliable and valuable tool for use towards a greener future in aviation.

Trimetallic Alloy as an Electrocatalyst for Direct Low Temperature Fuel Cells: The Case of MF Oxidation on Pt3Pd3Sn2

Methyl formate (MF) has been considered an attractive hydrogen carrier alternative fuel due to its high energy density, ease of storage and transport, and low boiling point (32o C @ 1 atmosphere) liquid. However, the low number of publications on efficient anodic catalysts is impeding the development of a direct methyl formate fuel cell (DMFFC).In this study, a first-principles density functional theory (DFT) calculation was performed to study the MF electro-oxidation on the surface of the Pt3Pd3Sn2 (111) alloy. This surface was proven to be the most active in the anodic oxidation of other small organic molecules1,2. A detailed thermochemistry and kinetics study of MF oxidation was carried out to determine the active sites, most probable reaction pathway for the oxidation of CH3OCHO to CO2, and analyzed the dehydrogenation steps via direct (HCOOH pathway) and indirect (CO pathway) mechanisms.The potential required for complete oxidation of MF to CO2 is 0.66 V. The study revealed that Sn plays an essential role in the mitigation of CO poisoning through water activation and surface oxide reaction mechanisms in a bifunctional manner. Furthermore, based on our findings, Pt and Pd work synergistically to enhance the utilization of active sites for the initiation of MF oxidation and promote HCOOH oxidation, which accelerates the kinetics of the electrochemical reaction.

Mechanistic Insights into Anion-Induced Electrochromism of Ru(II)-Based Metallo-Supramolecular Polymer.

The metallo-supramolecular polymer (MSP) is considered one of the most promising electrodes for electrochromic devices due to its intrinsically stable redox properties. Nevertheless, despite extensive work focusing on improving the electrochromic and electrochemical properties of MSPs, little experimental evidence exists from in-depth investigations on the anion-induced electrochromism of MSPs. Herein, Ru-based metallo-supramolecular polymer (polyRu) films with excellent electrochromic performance were fabricated through a novel electrochemical deposition method, and the electrochromic mechanism was further understood. The polyRu films possess fast reaction kinetics with a short switching time of 4.0 s (colored) and 2.8 s (bleached) and highly reversible redox properties due to the resulting impacts on the capacitive behaviors (containing surface, near-surface and intercalation pseudo-capacitance) of the perchlorate ions in the electrochromic process. Moreover, the electrochromic degradation of the polyRu films is considered to stem from the numerous nanopores in the film induced by ClO4- transport and the exchange of counter anions from Cl- to ClO4-. In addition, a physical model, revealing the transport of conduction ions and the evolution of the structure and properties of the polyRu film during the electrochromic process, is presented. It is observed that the charge balance of Ru3+ and Ru2+, achieved through the adsorption/desorption of ClO4- on the film, provides electrochromic and electrochemical reversibility to the polyRu film under positive/negative bias. Correspondingly, a transformation from polyRu·(Cl-)2n to polyRu·(ClO4-)x(Cl-)2n-x in the polyRu film is induced by a counter anion exchange from Cl- to ClO4-. Revealing the detailed perchlorate ion transfer kinetics and electrochromic mechanism in this film can offer new insights into the application of metallo-supramolecular polymers in electrochromic devices.

Experimental and modeling study of the combustion of ethyl methyl carbonate, a battery electrolyte

Ethyl methyl carbonate (EMC) is one of the main constituents of the electrolyte in lithium-ion batteries (LIBs). To understand better fire events involving LIBs and try to prevent them, the combustion of EMC was studied experimentally, and the results were analyzed using modern detailed kinetics models. Shock tubes were used to collect ignition delay times (IDTs) and CO time histories, while laminar flame speeds were measured in a closed vessel. All experiments were carried out near atmospheric pressure. The shock tube experiments were performed for three equivalence ratios (0.5, 1.0, and 2.0) with the IDTs measured with “fuel-air” mixtures and the CO spectroscopic laser measurements in mixtures highly diluted in 99.25% He/Ar. Comparisons with results obtained for other linear carbonates typically found in LIBs, such as dimethyl carbonate and diethyl carbonate, are also presented. Numerical predictions from recent detailed chemical kinetics mechanisms (Takahashi et al., 2022, Grégoire et al., 2023) did not capture well the combustion behavior of EMC in some of our conditions. Sensitivity analyses suggest that EMC decomposition reactions and subsequent combustion chemistry of the formed intermediates, i.e. methanol and ethylene, still need improvement.

Self-consistent model and numerical approach for laser-induced non-equilibrium plasma

This paper presents a self-consistent multi-dimensional mathematical model and a numerical approach for simulating the low-temperature plasma induced by the femtosecond laser filament. Addressing limitations in current models, we analyze key aspects of the laser plasma behavior, including plasma generation, detailed chemical kinetics, energy exchange channels, total energy balance, and hydrodynamics. The developed model and LOTASFOAM code are applied to study the temporal and spatial decay of the plasma produced by a femtosecond laser pulse in pure nitrogen at atmospheric pressure. The paper also includes a discussion on the spatial and temporal dynamics of electronically excited states of nitrogen in the decaying laser plasma.

Kinetics of silica-assisted pyro-hydrolysis of CaCl2 waste for the recovery of hydrochloric acid (HCl): Effect of interaction between CaCl2 and SiO2

Pyro-hydrolysis of CaCl2 waste for HCl acid regeneration is a circular process enabling the sustainable development of the critical energy mineral extraction industry. However, the lack of detailed kinetic information has posed challenges in implementing this technology. An acidic additive such as silica (i.e., SiO2) is essential to make this reaction thermodynamically available, yet its reaction kinetics are still unknown. This study aims to reveal the detailed reaction kinetics of the SiO2-assisted pyro-hydrolysis of CaCl2 under two typical industrial settings for the feeding of reactants, physical mixing of powders and spray feeding where CaCl2 solution is expected to initially undertake drying and subsequently deposit onto the solid silica powders for a close contact. The isothermal experiment results revealed that the HCl release rate is strongly temperature-dependent. Comparatively, the CaCl2-deposited silica demonstrated a significantly faster release of HCl than the physically mixed sample, achieving 92% HCl release within 30 min at 800 °C. SEM analysis confirmed a closer inter-particle contact for the CaCl2-deposited sample, which is responsive to the accelerated HCl release. In addition, the experimental results were successfully fitted by a variable activation energy model which discovered a steady increase of the activation energy with the progression of the HCl release for both feedstock modes. This is primarily due to the continuous change on the formation of intermediates. The model also confirmed a lower activation energy for the CaCl2-deposited sample than its physically mixed counterpart at any given conversion extent of CaCl2. In contrast, for the physically mixed sample, the loose inter-particle contact led to the formation of a stable intermediate, Ca(OH)Cl, which can readily reverse to CaCl2, thereby slowing down the overall HCl release rate.

Estimation and testing of single-step oxidation reactions for hydrogen and methane in low-oxygen, elevated pressure conditions

Advanced combustion concepts, such as moderate or intense low-oxygen dilution (MILD) combustion, offer a reduction in NOx emissions and increased thermal efficiency. MILD is characterised by low-oxygen, high-temperature conditions, where finite-rate chemistry effects are significant. Modelling this regime using reduced or single-step chemistry remains a challenge in part due to the finite-rate chemistry. This work proposes a generalised method for assigning Arrhenius coefficients of a single-step reaction using the outputs of a detailed mechanism. Assigning the typical chemical conservation equation to a progress variable, activation energy and pre-exponential factor for an Arrhenius kinetics global reaction are determined for hydrogen and methane across a number of conditions, with the proposed method extended to n-heptane as well. The temperature exponent in the modified Arrhenius equation is determined by minimising the ignition delay error between detailed and single-step simulations. Functional forms of each coefficient are calculated from a multivariate regression, dependent on initial temperature, pressure, and oxidant mole fraction. The predicted mechanisms are compared against the detailed kinetics in closed homogeneous batch reactors, with comparisons for hydrogen extended to both laminar opposed flow diffusion flames, and computational fluid dynamics (CFD) simulations. Ignition delay and equilibrium temperature are both well predicted for all three fuels in the batch reactors. Notably, the negative temperature coefficient behaviour of n-heptane is successfully recreated with the single-step mechanism. Temperature and heat release of hydrogen flames are well captured in both opposed flow laminar flames, and in turbulent CFD simulations. The computational time was also significantly reduced through the single-step mechanisms, resulting in ∼100 times reduction in compute time for CFD simulations. The function form of the Arrhenius coefficients shows promise for extension outside of the ranges and fuels analysed herein, and presents interesting phenomena for exploring how initial reactant temperature and pressure influence the effective activation energy of an oxidation process.

Annular swirling jet reactor for converting hydrocarbons to olefins and aromatics

This paper describes a novel reactor for high temperature thermochemical conversion of ethane to olefins. The central feature is an efficient flow pattern with a large recirculation zone that provides stable and compact 2500 °C flame and a thin conical annular swirling jet that provides fast transfer of mass, momentum, and heat. The jet is directed through a unique converging–diverging nozzle that maintains relatively low wall temperature and consequently reduces the need for external cooling. The hydrocarbons stream is introduced tangentially through volutes in such a way that there is initially heat transfer with minimal mass transfer followed by fast mixing of countercurrent streams. CFD simulations with detailed kinetics were employed to design and optimize this reactor including the order of the volutes to feed ethane, H2 fuel, oxidizer (O2 and N2 mix), and a cooling N2 gas; oxygen enrichment of the air, and also the overall operating conditions of this flexible and robust reactor. This highly intensified reactor was fabricated and tested at a semi-pilot scale with up to 15 kg/hr feed. The optimized reactor has high selectivity to ethylene and acetylene comparable to conventional steam cracker.

Incorporation of Ag on stable Pt/CeO2 for low-temperature active and high-temperature stable CO oxidation catalyst

Advanced engine technologies and environmental restrictions require new-generation automotive catalysts to be low-temperature (LT) active and high-temperature (HT) stable simultaneously. Here, incorporation of Ag over high temperature (800 °C) treated Pt/CeO2 was applied to address the challenge. Strong Pt-O-Ce bonds in Pt/CeO2 helped improve thermal stability dramatically. Detailed reaction kinetics analysis indicated Eley-Rideal (ER) mechanism for Ag/CeO2 catalysts and Mars-van Krevelen (Mvk) mechanism for both Pt/CeO2 and Ag/Pt/CeO2 catalyst. After calcined at 800 °C, CO adsorbed on ionic Pt site could be readily oxidized by neighbouring oxygen species at a temperature as low as 132 °C over Ag/Pt/CeO2, about 60 °C lower than Pt/CeO2 and Ag/CeO2. Raman spectroscopy and XPS results suggested that incorporation of Ag created more oxygen defects over Pt/CeO2 and oxygen species on Ag nanoparticles might be more active than bare Pt/CeO2 which would enhance the low-temperature activity for Ag/Pt/CeO2. It might be an effective and cost-efficient approach to develop new catalysts for vehicle emission oxidation.