Chemical Kinetic Simulations Research Articles

Frhodo: A program for simulating chemical kinetic measurements and optimizing kinetic mechanisms

Chemical kinetic simulations are frequently used to extract kinetic and mechanistic information from experimental data by fitting simulations to the data. For simple systems of consecutive single channel reactions this is a relatively straightforward task. However, as the complexity of the system increases and particularly for systems involving competitive multi-channel reactions manually optimizing a mechanism to obtain the best fits to a range of experimental data quickly becomes a time-intensive and challenging process, especially when rate coefficients have pressure and temperature dependencies. There is considerable potential for exploiting automated optimization methods to rapidly screen reaction mechanisms and optimize the fit by adjusting rate coefficients within well-defined constraints. A new chemical kinetics simulation program, Frhodo, has been developed for this purpose. The program allows either manual simulation of individual experiments or fully automated optimization against a range of experimental data by adjusting user selected reactions within user defined constraints. Frhodo incorporates machine learning-based optimization routines that work by either minimizing standardized residuals or through Bayesian parameter estimation. Frhodo's optimization capabilities are demonstrated by reexamining two previously studied systems of relevance to combustion. Dissociation of diacetyl followed by recombination of methyl radicals is an example of a sequence of single channel, consecutive reactions. Pyrolysis of 2-methyl furan exemplifies multi-channel, unimolecular reactions that are often encountered and have temperature and pressure dependencies in the rate coefficients of the channels and branching ratios between them. For both systems the optimization routines resulted in solutions similar to the original studies. Comments are made on the strengths and limitations of the approach.

Experimental and modelling study of hydrogen ignition in CO2 bath gas

Direct-fired supercritical CO2 power cycles, operating on natural gas or syngas, have been proposed as future energy technologies with 100 % carbon capture at a price competitive with existing fossil fuel technologies. Likewise, blue or green hydrogen may be used for power generation to counter the intermittency of renewable power technologies. In this work, ignition delay times (IDTs) of hydrogen were measured in a high concentration of CO2 bath gas over 1050 – 1300 K and pressures between 20 and 40 bar. Measured datasets were compared with chemical kinetic simulations using AramcoMech 2.0 and the University of Sheffield supercritical CO2 (UoS sCO2 2.0) chemical kinetic mechanisms. The UoS sCO2 2.0 mechanism was recently developed to model IDTs of methane, hydrogen, and syngas in CO2 bath gas. Sensitivity analyses were used to identify important reactions and to illustrate the trends observed among various datasets. The performance of both mechanisms was evaluated quantitatively by comparing the average absolute error between the predicted and experimental IDTs, which showed UoS sCO2 2.0 as the superior mechanism for modelling hydrogen IDTs in CO2 bath gas. The importance of OH time-histories is identified as the most appropriate next step in further validation of the kinetic mechanism.

Molecular Dynamics Simulation on the Pyrolysis Process of PODE3-5

This paper investigates the pyrolysis of PODEn (n = 3, 4, 5) using ReaxFF molecular dynamics simulation. A large-scale model, which contains 2000 PODEn molecules, is simulated at 3000 K. The higher frequencies of the initial PODEn decomposition reaction at α or β C-O bond show that the α or β C-O bond in PODEn is not easy to break, which is approximately half the number of the other type of C-O bond dissociation. Furthermore, the bond dissociation energies (BDEs) are calculated using the ReaxFF method. The BDE of α or β C-O bond is higher than that of the other C-O bond, ~3–11 kcal/mol, indicating that BDE is one of the factors causing the different proportions of bonds broken. The evolution of pyrolysis products is also investigated. The results reveal that long-chain pyrolysis products from the initial PODEn decomposition are prone to further reaction, while a large amount of CH3O and CH3 remains in the system. This helps explain the difficulty in α and β C-O bond dissociation reactions. The results of the pyrolysis products are consistent with the result in further chemical kinetic simulation. The C2 species in pyrolysis products is relatively low, especially for C2H4 and C2H3, which is around zero. This supports the ability of PODEn to reduce soot emission.

Exergy analysis and investigation on effect of inlet valve closing temperature and hydrogen enrichment in syngas composition in an HCCI engine

This study presents the parametric investigation of syngas fuelled homogeneous charge compression ignition (HCCI) engine. The chemical kinetic simulation of the syngas HCCI engine is performed using the stochastic reactor model (SRM). This study first compares and evaluates the performance of different reaction mechanisms for the HCCI engine. The experimental combustion pressure data is compared with numerically investigated combustion pressure to validate the reaction mechanisms. Results indicate that a numerically simulated combustion pressure using a detailed reaction mechanism consisting of 173 reactions and 32 species (CRECK-2014) is well-matched with the profile of experimental combustion pressure. The validated reaction mechanism is further used to investigate the HCCI engine at different engine speeds for various equivalence ratio (ϕ), syngas composition (hydrogen addition (H2:CO)) and inlet valve closing temperature (Tivc). The sensitivity analysis is performed to find the prominent reactions in the oxidation reaction mechanism. Based on the combustion characteristics, syngas HCCI maps are developed. The effect of engine operating conditions on combustion and emission characteristics is also investigated. Furthermore, the result of engine operating parameters on converting fuel energy into physical exergy, chemical exergy, work exergy, and heat loss exergy is also briefly discussed.

Characteristics of Premixed Flames of Hot and Diluted Mixtures

ABSTRACT Internal recirculation of product gases and mixing with fresh reactants, to form a hot and diluted combustible mixture, has been demonstrated to result in lower pollutant emissions. With sufficient amount of product gas recirculation, the mixture can reach above its auto-ignition temperature with low oxygen mass fractions (<4 wt%), resulting in distributed reactions instead of a flame. Some of the technologies with this feature are Moderate or Intense Low oxygen Dilution (MILD) combustion, FLameless OXidation (FLOX) and Colorless Distributed Combustion (CDC). However, if the amount of product gas recirculation is not enough and the auto ignition condition is not reached, premixed reactants of the hot and diluted mixture can be established. In this study, characteristics of such hot and diluted mixtures is studied which include the ignition delay time and the flame attributes such as laminar flame speed, S L and thermal flame thickness, . A perfectly stirred reactor (PSR) using the hot and diluted mixture as the inlet was further examined to simulate the main combustor and combustion efficiency η, and CO and NOx emissions were obtained. The investigations are performed at different product gas recirculation amounts , equivalence ratios ϕ and operating pressures P, using chemical kinetic simulations. The thermo-chemical state of the recirculated product gases was obtained using a PSR with varying residence times (τ) to simulate different “burntness” levels (smaller τ simulates lower “burntness” level). The hot and diluted mixture temperature is higher, while oxygen and fuel mole fraction are lower for higher ξ, ϕ, P, and τ. Radical species’ mole fraction is higher for higher ξ, ϕ, and lower P, τ. Lower is observed for higher ξ, ϕ, P and smaller τ. Higher S L is observed for higher ξ, ϕ and lower P. Lower is observed for higher ξ, ϕ and P. S L and are found to be higher or lower with variation in τ, depending on ξ, ϕ and P, owing to variation in temperature and radicals’ concentration. Higher η is observed for higher ξ, P, lower ϕ, τ, and higher residence time of gases (τ reac ) inside the main combustor. Lower CO is observed with increase in ξ, P and decrease in τ, while exhaust NOx increases with ϕ and mostly remains unchanged with increase in ξ, while inconsistent trends are observed with change in P and τ.

Soot volume fraction and size measurements over laminar pool flames and pre-vaporised non-premixed flames of biofuels, methyl esters and blends with diesel

Previous studies have demonstrated that methyl ester-based biodiesels produce significantly less soot compared to petroleum diesel in standard diffusion flames. However, the roles of the oxygen content and the degrees of unsaturation (DoU) of the biodiesels on their sooting propensity have not been independently analysed. In the present study, the relationship between soot yield of biodiesels and the DoU of the fuel is systematically analysed in laminar pool flames and pre-vaporised diffusion flames. The spatial distribution of soot volume fraction of the flames fuelled with four biodiesel fuels, two methyl esters and their blends with diesel are quantitatively measured using laser induced incandescence. All six biofuels have different DoU but similar oxygen mass fractions, so that the effect of the DoU on soot formation could be separately considered. The soot yield using biodiesels was measured to be lower than that of diesel fuel by a factor up to 7.5 in pool flames and by a factor of 4.0 in vapour flames. In both flame setups, the soot reduction effect of biodiesels ranks in order of DoU. The more saturated the fuel molecule is, the lower the soot yield. The soot reduction effect of the blending ratio with biodiesel was found to be non-linear, and different in pool and vapour flames. The morphology, size, and number density of soot particles were analysed using scanning electronic microscopy. The results suggest that the shape of primary soot particles is close to spherical and the structure of the point-contact aggregates is similar in all cases. Biofuels not only produce smaller particle sizes, but also fewer particles compared to diesel. Chemical kinetic simulations suggest that blending of biodiesels reduces the soot yield primarily by slowing the soot surface growth process, and secondarily by prohibiting the soot nucleation and inception. Both the nucleation (C3H3 and benzene) and growth species (C2H2) for soot formation take place more quickly and intensely for the combustion of more unsaturated fuels, which results in the correspondingly larger soot yield.

A comparative study on soot and PAH formation of C10 naphthenic ring-containing species in laminar coflow diffusion flames

C10 naphthenic ring-containing species are important components in transportation fuels and have been widely used for surrogate formulation of diesel and jet fuels to represent cycloalkanes or aromatic fractions. In this study, experimental and modeling studies were carried out to compare the formation of typical polycyclic aromatic hydrocarbons (PAHs) and soot in coflow methane/air diffusion flames doped with n-butylcyclohexane, decalin and tetralin. The laser-induced incandescence (LII) and laser-induced fluorescence (LIF) techniques were applied to measure 2D maps of soot volume fractions and relative PAH concentrations, respectively. Yield sooting index (YSI) was obtained experimentally to indicate the fuel sooting tendency. It can be observed that the soot volume fractions, sooting tendencies and pyrene concentrations of C10 naphthenic ring-containing species follow the order of tetralin > decalin > n-butylcyclohexane. The chemical kinetic simulation reveals that decalin decomposes through two main pathways, including the H-atom abstraction route and ring opening route. Especially, the pathway of ring opening reactions coupled with dehydrogenation results in the strongest benzene formation process among the test components. In the reacting system of tetralin flames, ring opening reactions are suppressed, while the dominant decomposition way of tetralin is via H-atom abstraction reactions, which offer a more direct pathway to form naphthalene and indene without benzene formation, leading to the highest naphthalene concentration of tetralin flame and the strongest soot formation process among all the test components. This fundamental investigation aims to provide valuable data on sooting behaviors and PAH formation characteristics of typical C10 naphthenic ring-containing species and get insight into the kinetic pathways from fuels to soot precursors. Useful information has been obtained for soot reduction from the perspective of the fuel design and surrogate formulation in terms of the sooting tendency.

Experimental and Numerical Study on the Effect of Nitric Oxide on Autoignition and Knock in a Direct-Injection Spark-Ignition Engine

&lt;div class="section abstract"&gt;&lt;div class="htmlview paragraph"&gt;Nitric Oxide (NO) can significantly influence the autoignition reactivity and this can affect knock limits in conventional stoichiometric SI engines. Previous studies also revealed that the role of NO changes with fuel type. Fuels with high RON (Research Octane Number) and high Octane Sensitivity (S = RON - MON (Motor Octane Number)) exhibited monotonically retarding knock-limited combustion phasing (KL-CA50) with increasing NO. In contrast, for a high-RON, low-S fuel, the addition of NO initially resulted in a strongly retarded KL-CA50 but beyond the certain amount of NO, KL-CA50 advanced again. The current study focuses on same high-RON, low-S Alkylate fuel to better understand the mechanisms responsible for the reversal in the effect of NO on KL-CA50 beyond a certain amount of NO. Experiments were conducted to measure the responses of KL-CA50 and trace-autoignition CA50, the latter being indicative of CA50 at which end-gas autoignition starts to become measurable from the apparent heat-release rate. Chemical-kinetics simulations were conducted to reveal the role of NO for end-gas autoignition, with a specific focus on sequential autoignition in a thermally stratified end-gas.&lt;/div&gt;&lt;div class="htmlview paragraph"&gt;The simulation results reveal that the magnitude of low-temperature heat release (LTHR) generally increases with NO. However, the relative importance of NO for enhancing LTHR diminishes when the LTHR inherent to a fuel’s chemistry is strong, such as at lower temperatures in a thermal boundary layer. This rendered more uniform LTHR within a hypothetical thermal boundary and led to a more sequential (&lt;i&gt;i.e.&lt;/i&gt; slower) autoignition event. It was also revealed that a change in compression ratio influences the importance of intermediate-temperature heat release (ITHR) due to changes of the temperature-pressure history of the end-gas. Together with the condition where end-gas autoignition occurs more sequentially, the shorter time spent in LTHR and ITHR regime can counter the increase in autoignition reactivity at high NO levels and allow KL-CA50 to advance.&lt;/div&gt;&lt;/div&gt;

Sustainability analysis of methane-to-hydrogen-to-ammonia conversion by integration of high-temperature plasma and non-thermal plasma processes

The Covid era has made us aware of the need for resilient, self-sufficient, and local production. We are likely willing to pay an extra price for that quality. Ammonia (NH3) synthesis accounts for 2 % of global energy production and is an important point of attention for the development of green energy technologies. Therefore, we propose a thermally integrated process for H2 production and NH3 synthesis using plasma technology, and we evaluate its techno-economic performance and CO2 footprint by life cycle assessment (LCA). The key is to integrate energy-wise a high-temperature plasma (HTP) process, with a (low-temperature) non-thermal plasma (NTP) process and to envision their joint economic potential. This particularly means raising the temperature of the NTP process, which is typically below 100 °C, taking advantage of the heat released from the HTP process. For that purpose, we proposed the integrated process and conducted chemical kinetics simulations in the NTP section to determine the thermodynamically feasible operating window of this novel combined plasma process. The results suggest that an NH3 yield of 2.2 mol% can be attained at 302 °C at an energy yield of 1.1 g NH3/kWh. Cost calculations show that the economic performance is far from commercial, mainly because of the too low energy yield of the NTP process. However, when we base our costs on the best literature value and plausible future scenarios for the NTP energy yield, we reach a cost prediction below 452 $/tonne NH3, which is competitive with conventional small-scale Haber-Bosch NH3 synthesis for distributed production. In addition, we demonstrate that biogas can be used as feed, thus allowing the proposed integrated reactor concept to be part of a biogas-to-ammonia circular concept. Moreover, by LCA we demonstrate the environmental benefits of the proposed plant, which could cut by half the carbon emissions when supplied by photovoltaic electricity, and even invert the carbon balance when supplied by wind power due to the avoided emissions of the carbon black credits.

Modeling of gaseous emissions and soot in 3D-CFD in-cylinder simulations of spark-ignition engines: A methodology to correlate numerical results and experimental data

In order to reduce development costs and time-to market, 1D and 3D CFD tools can support engine design providing reliable estimations of the tailpipe emissions. In particular, 3D-CFD in-cylinder simulations can evaluate formation of both soot and gaseous pollutants inside the combustion chamber. The main issue in such kind of simulations is the validation against experimental findings. In fact, the complexity of the emission measurements does not allow a straightforward one-to-one comparison between numerical and experimental results. Therefore the present paper aims at providing, on the one hand, a robust numerical framework for both gaseous and solid emissions, on the other hand a dedicated post-processing for a fair comparison between simulations and experiments. From a numerical standpoint, a simplified approach is dedicated to gaseous emissions, while a more detailed one is reserved to soot modeling. The latter is based on the Sectional Method, whose reaction rates are tabulated following 0D chemical kinetic simulations of a purposely designed surrogate in a constant pressure reactor. Simulations and experiments proposed in the present analysis are referred to a high-performance turbocharged direct-injection spark-ignition engine operated at part-load and low rpms. On equal performance, revving speed and mean mixture quality, different injection timings are investigated. The developed numerical approach and post-processing ensure a good agreement between simulations and experiments.

Assessment on combustion chemistry of coal volatiles for various pyrolysis temperatures

Carrying out in-depth research on the formation characteristics and mechanisms of organic products in coal combustion will help to provide theoretical guidance for the emission reduction of coal-fired pollutants. Since the combustion of coal volatiles plays a vital role in the whole process of coal combustion, this work took coal pyrolysis gases as fuels and focused on the organic pollutants such as alkanes, olefins and aromatics in the combustion of coal pyrolysis gases. To explore the effects of three pyrolysis temperatures of 600 °C, 750 °C and 900 °C on the formation characteristics and mechanisms of hydrocarbon products during coal pyrolysis gases combustion, the online detection was carried out by gas chromatography (GC) and gas chromatography-mass spectrometer (GC-MS) on the counterflow diffusion flame platform, combined with chemical reaction kinetics simulations. The results showed that rising pyrolysis temperature had an inhibitory effect on the formation of light hydrocarbons and aromatic hydrocarbons, such as acetylene (C2H2), propyne (PC3H4), 1,3-butadiene (C4H6-13), vinylacetylene (C4H4), diacetylene (C4H2), benzene (C6H6), toluene (C6H5CH3) and naphthalene (C10H8), during the combustion of pyrolysis gases. Among three mechanisms used in this study, Creck mechanism was more accurate and applicable than KM2 mechanism and AramcoMech 3.0 mechanism. As the pyrolysis temperature rose, the rate of the reactions which dominated the formation of C2H2, propargyl (C3H3), C6H6 and C10H8 decreased continuously, because the decrease of CH3 concentration and the increase of H concentration inhibited the forward progress of these reactions. In addition, with rising pyrolysis temperature, less C3H3 was converted to butadiene (C4H6), C6H6 and Fulvene, and more inclined to its upstream reactants, allene (AC3H4) and PC3H4. The tendency of phenyl (C6H5) to form C6H6 was strengthened. Meanwhile, less C10H8 was generated from C4H4 and C6H5, but the dominant role of this reaction was still enhanced.

(Invited) Kinetics of Dye-Sensitized Water Oxidation Catalysis in Natural Sunlight

The couplings of ultrafast electronic excitation, charge injection and charge transfer processes to the catalytic cycles involved in water oxidation using molecular dye-catalyst photoelectrosynthesis systems are examined using detailed stochastic chemical kinetics simulations. By modeling the full timescale from subpicoseconds to many minutes and assuming illumination by the sun (AM 1.5), we have gained insights to how 4-photon catalytic cycle works when stimulated by relatively rare interactions with light. In this talk the model will be described, and its predictions for how catalyst and dye state populations evolve over time and how the flow of the catalytic cycle works will be discussed.

Shock tube study of natural gas oxidation at propulsion relevant conditions

Global climate change and rising crude oil prices have motivated search of clean, sustainable and economic fuel. Methane, having the highest hydrogen to carbon ratio is ideally the best option towards carbon neutral emissions and reduce greenhouse gas emissions. However, there the economic benefits are minimal when using pure methane because of purification costs. Natural gas primarily consists of methane but with appreciable amounts of C2C4 alkanes which significantly impact oxidation performance, especially when compared to pure methane at high pressures and temperatures, studies of natural gas have been scarce and there is new interest in studying natural gas for its application to propulsion devices. This single pulse shock tube study investigates the effect of natural gas composition on species yields as a function of temperature at various stoichiometric conditions (φ ≈ 0.5, 1.0, 2.0) and high pressure (240 atm) over a nominal reaction time of 2.5 ms. The experimentally measured speciation results for one real natural gas sample from Boise, ID (USA) and a reference natural gas sample are compared to species yield predictions using well established chemical kinetic mechanisms, to check the feasibility of using these mechanisms in the design of propulsion devices. The chemical kinetic simulations are carried out using the constant pressure approach as well as the changing pressure approach which considers the exact measured pressure change in the shock tube. The experiments provide a large speciation data set for optimizing chemical kinetic mechanisms for natural gas applications and to understand the effect of composition on natural gas chemical kinetics. The predictions vary significantly between models tested and effect of composition variation was evident. Aramco Mech 3.0 could predict the experiments almost perfectly, especially at fuel rich conditions.

Detailed chemical kinetics simulation of hydrogen hydrothermal combustion characteristics: Special effects of supercritical H2O/CO2 mixtures

Hydrothermal combustion of hydrogen is a key process in the H2O/CO2 mixed working medium thermal power generation polygeneration technology, a new coal utilization path. The flammability and stability of hydrogen hydrothermal combustion were evaluated using detailed chemical kinetics coupled with the chemical dynamics simulation method in this paper. The findings reveal that in supercritical water, pure hydrogen is difficult to burn; however, CO2 can dramatically reduce the ignition delay time and lower the critical ignition temperature of hydrogen. This is because free radicals produced by CO2 are actively involved in the chain-branching process of hydrogen oxidation, which promotes hydrogen ignition and combustion stability. Compared with gas combustion, hydrogen hydrothermal combustion has lower ignition temperature and can combust at lower parameters. Water is active in the reaction process, which produces the necessary free radicals for ignition, promotes combustion and influences the path of reaction, resulting in a relatively slow reaction rate.

Laminar flame speed correlations of ammonia/hydrogen mixtures at high pressure and temperature for combustion modeling applications

Ammonia/hydrogen mixtures are among the most promising solutions to decarbonize the transportation and energy sector. The implementation of these alternative energy carriers in practical systems requires developing suitable numerical tools, able to estimate their burning velocities as a function of both thermodynamic conditions and mixture quality. In this study, laminar flame speed correlations for ammonia/hydrogen/air mixtures are provided for high pressures (40 bar–130 bar) and elevated temperatures (720 K–1200 K), and equivalence ratios ranging from 0.4 to 1.5. Based on an extensive dataset of chemical kinetics simulations for ammonia/hydrogen blends (0-20-40-60-80-90-100 mol% of hydrogen), dedicated correlations are derived using a regression fitting. Besides these blend-specific correlations, a generalized (i.e., hydrogen-content adaptive) formulation, with hydrogen content used as additional parameter, is proposed and compared to the dedicated correlations.

Accelerating reactive-flow simulations using vectorized chemistry integration

The high cost of chemistry integration is a significant computational bottleneck for realistic reactive-flow simulations using operator splitting. Here we present a methodology to accelerate the solution of the chemical kinetic ordinary differential equations using single-instruction, multiple-data vector processing on CPUs using the OpenCL framework. First, we compared several vectorized integration algorithms using chemical kinetic source terms and analytical Jacobians from the pyJac software against a widely used integration code, CVODEs. Next, we extended the OpenFOAM computational fluid dynamics library to incorporate the vectorized solvers, and we compared the accuracy of a fourth-order linearly implicit integrator–both in vectorized form and a corresponding method native to OpenFOAM—with the community standard chemical kinetics library Cantera. We then applied our methodology to a variety of chemical kinetic models, turbulent intensities, and simulation scales to examine a range of engineering and scientific scale problems, including (pseudo) steady-state as well as time-dependent Reynolds-averaged Navier–Stokes simulations of the Sandia flame D and the Volvo Flygmotor bluff-body stabilized, premixed flame. Subsequently, we compared the performance of the vectorized and native OpenFOAM integrators over the studied models and simulations and found that our vectorized approach performs up to 33–35× faster than the native OpenFOAM solver with high accuracy.

Hydrogen gas transfer between a borehole and claystone: experiment and geochemical model

The Hydrogen Transfer experiment, located at the Mont Terri underground rock laboratory in Switzerland, is an in situ experimental study of the interactions and transport of hydrogen injected into a borehole installed within Opalinus Clay, a claystone formation. A Python-based model was developed to analyse and model the experimental data, for diffusion of dissolved gases and solutes in claystone pore water, for thermodynamic modelling of gas–water–solid phase equilibria in the injection interval and for simulations of chemical equilibria and reaction kinetics in claystone and injection interval. The developed model reproduces the temporal evolution of gas pressure, composition and solute concentrations measured in situ with a minimum set of adjustable parameters. The effective diffusion coefficients for dissolved gases in Opalinus Clay derived by the modelling of experimental data were found to be very close to values measured in other experimental studies. It was discovered that an accurate description of the temporal variations in hydrogen injection and temporal changes in the inflow of formation water is essential for modelling of microbially mediated hydrogen consumption in the injection interval.

Chemical kinetic investigation on NOx emission of SI engine fueled with gasoline-ethanol fuel blends

Understanding the nitrogen oxide (NOx) formation chemical kinetic mechanism and analyzing the effect of relevant influence parameters are the effective strategy for NOx emission control. Based on the essential role of ethanol-gasoline blends among oxygenate alternative fuel, the experiments in a GDI (gasoline direct injection) SI (spark ignition) engine and the chemical kinetic simulation were carried out. According to the validated model, seven NO contributing reactions and three reaction pathways were observed. Besides the thermal NO formation pathway, two other pathways with N2O and NNH through NH-HNO-NO have nonnegligible places in the high engine speed condition. As for the parameters, initial temperature aggravates NO emission, initial pressure and ethanol fraction inhibit NO, which influence it through thermal NO pathway and have slight impact on the other two pathways. While with the increase of equivalence ratio (ER) from 0.5 to 1.0, ER promotes first and then resists NO formation, getting highest emission when ER equals to 0.85. In a lean burn condition, the thermal pathway is highly inhibited and the N2O pathway is sharply accelerated. Through current work, NOx producing mechanism under high-speed condition is investigated comprehensively, which not only completes the total NO formation pathways from atmospheric N2 but also provides reference for the designing and modification of low harmful NOx emitting gasoline-ethanol engines.

Surface Engineering on Commercial Cu Foil for Steering C2H4/CH4 Ratio in CO2 Electroreduction.

Designing catalysts with high selectivity toward C2 products in CO2 electroreduction is crucial to energy storage and sustainable development. Here, we propose a Cu foil kinetic model with abundant nanocavities possessing higher reaction rate constant k to steer the ratio of C2H4 to the competing CH4 during CO2 electroreduction. Chemical kinetic simulation demonstrates that the nanocavities could enrich the adsorbed CO surface concentration (θCOad), while the higher k helps to lower the C-C coupling barrier for CO intermediates, thus favoring the formation of C2H4. The commercial Cu foil treated with cyclic voltammetry is used to match this model, displaying a remarkable C2H4/CH4 ratio of 4.11, which is 18 times larger than that on the pristine Cu foil. This work offers a handy strategy for surface modification and provides new insights into the C-C coupling and the C2H4 selectivity in terms of mass transfer flux and energy barrier.

Numerical Evaluation of the Effect of Fuel Blending with CO2 and H2 on the Very Early Corona-Discharge Behavior in Spark Ignited Engines

Reducing green-house gases emission from light-duty vehicles is compulsory in order to slow down the climate change. The application of High Frequency Ignition systems based on the Corona discharge effect has shown the potential to extend the dilution limit of engine operating conditions promoting lower temperatures and faster combustion events, thus, higher thermal and indicating efficiency. Furthermore, predicting the behavior of Corona ignition devices against new sustainable fuel blends, including renewable hydrogen and biogas, is crucial in order to deal with the short-intermediate term fleet electric transition. The numerical evaluation of Corona-induced discharge radius and radical species under those conditions can be helpful in order to capture local effects that could be reached only with complex and expensive optical investigations. Using an extended version of the Corona one-dimensional code previously published by the present authors, the simulation of pure methane and different methane–hydrogen blends, and biogas–hydrogen blends mixed with air was performed. Each mixture was simulated both for 10% recirculated exhaust gas dilution and for its corresponding dilute upper limit, which was estimated by means of chemical kinetics simulations integrated with a custom misfire detection criterion.