Coupling chemical lumping to data-driven optimization for the kinetic modeling of dimethoxymethane (DMM) combustion

The kinetic mechanisms describing the combustion of longer-chain fuels often have limited applicability due to the high number of species involved in their oxidation and decomposition paths. This work proposes a combined methodology for developing compact but accurate kinetic mechanisms of these fuels and applies it to dimethoxymethane (DMM), or oxymethylene ether 1 (OME1). An automatic chemical lumping procedure, performed by grouping structural isomers into pseudospecies, was proposed and applied to a detailed kinetic model of DMM pyrolysis and oxidation, built from state-of-the-art kinetic sub-models. Such a methodology proved particularly efficient in delivering a compact kinetic mechanism, requiring only 11 species instead of 35 to describe DMM sub-chemistry. The obtained lumped kinetic model was then improved through a data-driven optimization procedure, targeting data artificially generated by the reference detailed mechanism. The optimization was performed on the physically-constrained parameters of the modified-Arrhenius rate constants of the controlling reaction steps, identified via local sensitivity analyses. The dissimilarities between the predictions of the detailed and lumped models were minimized using a Curve Matching objective function for a comprehensive and quantitative characterization. Above all, the optimized mechanism was found to behave comparably to the starting detailed one, throughout most of the operating space and target properties (ignition delay times in shock tubes, laminar flame speeds, and speciations in stirred and flow reactors). The successful application of the proposed methodology to the DMM chemistry paves the way for its extensive use in the kinetic modeling of longer OMEs as well as heavier fuels, for which the computational advantages are expected to be even higher

The role of chemistry in the oscillating combustion of hydrocarbons : an experimental and theoretical study

The stable operation of low-temperature combustion processes is an open challenge, due to the presence of undesired deviations from steady-state conditions: among them, oscillatory behaviors have been raising significant interest. In this work, the establishment of limit cycles during the combustion of hydrocarbons in a wellstirred reactor was analyzed to investigate the role of chemistry in such phenomena. An experimental investigation of methane oxidation in dilute conditions was carried out, thus creating quasi-isothermal conditions and decoupling kinetic effects from thermal ones. The transient evolution of the mole fractions of the major species was obtained for different dilution levels (0.0025 <= X-CH4 <= 0.025), inlet temperatures (1080K <= T <= 1190K) and equivalence ratios (0.75 <= Phi <= 1). Rate of production analysis and sensitivity analysis on a fundamental kinetic model allowed to identify the role of the dominating recombination reactions, first driving ignition, then causing extinction. A bifurcation analysis provided further insight in the major role of these reactions for the reactor stability. One-parameter continuation allowed to identify a temperature range where a single, unstable solution exists, and where oscillations were actually observed. Multiple unstable states were identified below the upper branch, where the stable (cold) solution is preferred. The role of recombination reactions in determining the width of the unstable region could be captured, and bifurcation analysis showed that, by decreasing their strength, the unstable range was progressively reduced, up to the full disappearance of oscillations. This affected also the oxidation of heavier hydrocarbons, like ethylene. Finally, less dilute conditions were analyzed using propane as fuel: the coupling with heat exchange resulted in multiple Hopf Bifurcations, with the consequent formation of intermediate, stable regions within the instability range in agreement with the experimental observations

An experimental and kinetic modeling study of NH3 oxidation in a Jet Stirred Reactor

The increasing interest towards renewable, and more sustainable energy sources imposes a widerange analysis of the underlying chemistry, in order to maximize the efficiency of combustion devices and reduce pollutant emissions. In this context, ammonia chemistry has recently gained major attention: it is present in biogas and bio-oil, in trace amounts. Investigating ammonia chemistry can benefit from several studies carried out in the past decades on its pyrolysis and oxidation behavior. However, scarce literature is available on the conditions of interest previously mentioned, since the presence of ammonia in trace amounts results in superoxidative conditions. The available kinetic models of ammonia have been built up by mostly relying on hightemperature data, obtained in ideal reactors. On the other side, few work has been carried out to investigate its oxidation at lower temperatures. In order to further investigate this topic, and to provide a stronger support for kinetic model validation, in this study the oxidation of ammonia in diluted conditions, at relatively low temperatures (T < 1200 K) and a pressure close to atmospheric, is investigated by using a Jet Stirred Reactor. In addition to ammonia conversion, the formation of Nitrogen Oxides (NOx) is also analyzed. At the same time, a detailed kinetic mechanism for ammonia oxidation is developed by leveraging the most recently available kinetic data on experimental and theoretical reaction rates, and is used to analyze the obtained data, after being validated against the literature data in similar conditions

Study of oscillations during methane oxidation with species probing

Biogas has been considered as a renewable energy source with respect to fossil fuels due to its sustainability, security supply, and environmental friendly potential [1-4]. Methane occupies a large part in biogas. It is of great value to review the methane oxidation for a primary understanding of the features associated with biogas combustion. It was found that dynamic behavior in terms of methane oxidation occurred under specific conditions. The first methane oxidation oscillation experiments were conducted by [5] in a jet-stirred reactor (JSR) and were extended to a higher inlet temperature [6]. The map of dynamic behavior was drawn in terms of various C/O ratios and temperatures ranging from 1025-1275 K at a fixed 90% nitrogen bath gas. Recently, Lubrano Lavadera et al. [7] investigated the main parameters, such as, equivalence ratios (0.5-1.5), residence time (1.5-2 s), various bath gases (N2, CO2, He, H2O), on the oscillatory behavior of methane oxidation. However, to our best knowledge, studies of dynamic phenomenology with species probing have never been reported. Because of the heat release in terms of the exothermic or endothermic reactions, the temperature and species oscillations are strongly coupled during fuel oxidation. In order to put emphasis on species dynamic behavior, very diluted conditions are needed to decouple as much as possible temperature and species oscillations. The purpose of this work is to investigate the effects of various parameters: inlet mole fraction of methane (0.1-0.5%), stoichiometric condition (=1) and reactor temperatures (950-1200 K), on the species oscillations during methane oxidation. A detailed kinetic mechanism (POLIMI) [8] is selected to interpret the experimental data

Modeling Non-Premixed Combustion Using Tabulated Kinetics and Different Fame Structure Assumptions

Nowadays, detailed kinetics is necessary for a proper estimation of both flame structure and pollutant formation in compression ignition engines. However, large mechanisms and the need to include turbulence/chemistry interaction introduce significant computational overheads. For this reason, tabulated kinetics is employed as a possible solution to reduce the CPU time even if table discretization is generally limited by memory occupation. In this work the authors applied tabulated homogeneous reactors (HR) in combination with different turbulent-chemistry interaction approaches to model non-premixed turbulent combustion. The proposed methodologies represent good compromises between accuracy, required memory and computational time. The experimental validation was carried out by considering both constant-volume vessel and Diesel engine experiments. First, the ECN Spray A configuration was simulated at different operating conditions and results from different flame structures are compared with experimental data of ignition delay, flame lift-off, heat release rates, radicals and soot distributions. Afterwards, engine simulations were carried out and computed data are validated by cylinder pressure and heat release rate profiles

Experimental and modelling study of the oxidation of methane doped with ammonia

The oxidation of methane doped with ammonia was experimentally and theoretically studied in order to better understand the interactions between these two molecules in combustion processes fed with biogas. Experiments were carried out in a jet-stirred reactor. Several diagnostics were used to quantify reaction products: gas chromatograph for carbon containing species, a NOx analyzer for NO and NO2, and continuous-wave cavity ring-down spectroscopy for ammonia. Experimental data were satisfactorily compared with data computed using a model developed by Politecnico di Milano

Experimental and Modeling Study of the Oxidation of Benzaldehyde

The gas-phase oxidation of benzaldehyde has been investigated in a jet-stirred reactor. Benzaldehyde is an aromatic aldehyde commonly considered in bio-oils surrogates or in the oxidation of fuels such as toluene. However, its oxidation has never been previously investigated experimentally and no product formation profiles were reported in the few pyrolysis studies. In this study 48 species, mainly CO, CO2 and phenol were detected using gas chromatography, which indicate a rapid formation of phenyl radicals. This was confirmed by a kinetic analysis performed using the current version of the CRECK kinetic model, in which reactions have been updated

A kinetic study of the oscillating combustion of hydrogen and syngas in well-stirred reactors

The establishment of permanent oscillations (“limit cycles”) has been often observed in the oxidation of several hydrocarbons in premixed, non-adiabatic systems like well-stirred reactors [1-3]. In such cases, the interaction between mass flow, heat exchange and chemical kinetics results in a periodic extinction and reignition of the system. Several operating parameters have been found to influence the establishment of periodic limit cycles: beyond the fuel type and the dilution level, the oscillatory behavior is affected by the reactor temperature, pressure and residence time. Thus, the high number of parameters makes theoretical analysis a necessary step to understand the causes of such phenomena. The simplest system to be studied is the combustion of hydrogen in a premixed reactor. Such configuration was first studied by Baulch et al. [2, 4, 5]. The oxidation of CO was also separately analyzed [6, 7]. In this work, a kinetic analysis of the hydrogen and syngas oxidation in isothermal, well stirred reactors is carried out. By adopting detailed kinetic mechanisms, the boundaries of the oscillating regions are defined through a parametric study. The Rate of Production (ROP) Analysis is adopted to understand the critical reaction paths

AurkA nuclear localization is promoted by TPX2 and counteracted by protein degradation

The AurkA kinase is a well-known mitotic regulator, frequently overexpressed in tumors. The microtubule-binding protein TPX2 controls AurkA activity, localization, and stability in mitosis. Non-mitotic roles of AurkA are emerging, and increased nuclear localization in interphase has been correlated with AurkA oncogenic potential. Still, the mechanisms leading to AurkA nuclear accumulation are poorly explored. Here, we investigated these mechanisms under physiological or overexpression conditions. We observed that AurkA nuclear localization is influenced by the cell cycle phase and nuclear export, but not by its kinase activity. Importantly, AURKA overexpression is not sufficient to determine its accumulation in interphase nuclei, which is instead obtained when AURKA and TPX2 are co-overexpressed or, to a higher extent, when proteasome activity is impaired. Expression analyses show that AURKA, TPX2, and the import regulator CSE1L are co-overexpressed in tumors. Finally, using MCF10A mammospheres we show that TPX2 co-overexpression drives protumorigenic processes downstream of nuclear AurkA. We propose that AURKA/TPX2 co-overexpression in cancer represents a key determinant of AurkA nuclear oncogenic functions

Numerical investigation of soot formation from microgravity droplet combustion using heterogeneous chemistry

The use of isolated droplets as idealized systems is an established practice to get an insight on the physics of combustion, and an optimal test field to verify physical submodels. In this context, this work examines the dynamics of soot formation from the combustion of hydrocarbon liquid fuels in such conditions. A detailed, heterogeneous kinetic mechanism, describing aerosol and particle behavior through a discrete sectional approach is incorporated. The developed 1-dimensional model accounts for (i) non-luminous and luminous radiative heat losses, and (ii) incomplete thermal accommodation in the calculation of the thermophoretic flux. The combustion of droplets of n-heptane, i.e., the simplest representative species of real fuels, was investigated as test case; an upstream skeletal reduction of the kinetic mechanism was carried out to limit calculation times. After checking the performance of the reduced mechanism against gas-phase experimental data, the transient evolution of the system was analyzed through a comprehensive study, including fiber-suspended (D0 1 mm) droplets. The different steps of soot evolution were quantified, and localized in the region between the flame front and the soot shell, where particle velocity is directed inwards because of thermophoresis, and residence times are much higher than what usually found in diffusion flames. As a result, growth, coalescence, and aggregation steps are significantly enhanced, and soot accumulates in the inner shell, with an evident modification of the particle size distribution, if compared to what observed in conventional combustion conditions. The model exhibits a satisfactory agreement with experimental data on flame temperature and position around the droplet, while for larger droplets an increasing sensitivity to the radiation model was observed. It is found that the latter has a significant impact on the production of soot, while scarcely affecting the location of the soot shell. On the other side, the inclusion of incomplete thermal accommodation in the thermophoretic law brought about more accurate predictions of both volume fractions and shell location, and highlighted the primary role of thermophoresis in these conditions, as already found in literature through more simplified approaches