Modeling of Soot Formation in Gas Burner Using Reduced Chemical Kinetics Coupled with CFD Code

A computational study of soot formation in ethylene/air coflow jet diffusion flame at atmospheric pres-sure was conducted using a reduced mechanism and soot formation model. A 20-step mechanism was derived from the full mechanism using sensitivity analysis,reaction path analysis and quasi steady state(QSS) approximation. The model in premixed flame was validated and with computing savings in diffusion flame was applied by incor-porating into a CFD code. Simulations were performed to explore the effect of coflow air on flame structure and soot formation. Thermal radiation was calculated by a discrete-ordinates method,and soot formation was predicted by a simple two-equation soot model. Model results are in good agreement with those from experiment data and detailed mechanism at atmospheric conditions. The soot nucleation,growth,and oxidation by OH are all enhanced by decrease in coflow air velocity. The peak soot volume fraction region appears in the lower annular region be-tween the peak flame temperature and peak acetylene concentration locations,and the high soot oxidation rate due to the OH attack occurs in the middle annular region because of high temperature.

A tool model for predicting atmospheric chemical kinetics with sensitivity analysis

A package(a tool model) for program of predicting atmospheric chemical kinetics with sensitivity analysis is presented. The new direct method of calculating the first order sensitivity coefficients using sparse matrix technology to chemical kinetics is included in the tool model, it is only necessary to triangularize the matrix related to the Jacobian matrix of the model equation. The Gear type procedure is used to integrate a model equation and its coupled auxiliary sensitivity coefficient equations. The FORTRAN subroutines of the model equation, the sensitivity coefficient equations, and their Jacobian analytical expressions are generated automatically from a chemical mechanism. The kinetic representation for the model equation and its sensitivity coefficient equations, and their Jacobian matrix is presented. Various FORTRAN subroutines in packages, such as SLODE, modified MA28, Gear package, with which the program runs in conjunction are recommended. The photo\|oxidation of dimethyl disulfide is used for illustration.

Numerical study of CNG engine combustion using CFD with detailed chemical kinetics

A three dimensional model which considers the effects of turbulence and detailed chemi cal kinetics is built to simulate the combustion process of engine fueled by compressed nature gas （CNG）. The model is accomplished by integrating CFD software KIVA3V and chemical kinetic soft- ware CHEMKINII. Meanwhile, a turbulence combustion model which is suitable for describing the reaction rate under the coupled simulation is developed to balance the effects of turbulence and de tailed chemical kinetics. To reduce the computation time, subsequent development of the simulation code is realized, which enables the simulation code to have the function of parallel computing and run on parallel computing facility based on message passing interface （MPI）. The coupled software is used to simulate the combustion process of spark ignition CNG engine. The results show that sim ulation data have a good consistency with experimental results and parallel computing has good effi ciency and accelerate ratio.

Chemical Kinetics for NO Emissions in System of Methane-Air Turbulent-Jet Diffusion Flame

An explicit expression for local, instantaneous NO production rate model was proposed to simulate NO formation in turbulent methane-air combustion. The average production rates of mixture fraction and scalar dissipation were obtained from asymptotes through approximation of two single-variable probability-density function. The theory predicted significant contributions from the Zeldovich mechanism, but negligible contributions from the nitrous-oxide mechanism in the oxygenconsumption zone. The proposed model was used to simulate NO formation in the pilot methane-air jet diffusion combustion. The simulation results were compared with those obtained by the CFD software FLUENT module. Validation of predictions with the experimental data given by Sandia National Laboratory of the USA indicates that the proposed model yields better results than other models, and the deviation is under 5%. And in some complete reaction zones, the simulation results are even the same as the experimental data. Realizable κ-ε model, Reynold stress model and standard κ-ε model were also investigated to predict the turbulent combustion reaction, which shows that the simulation results of velocities, temperatures, and concentrations of combustion productions by standard κ-ε model are in accordance with the experimental data.

RANS Simulation of Methane Diffusion Flame： Comparison of Two Chemical Kinetics Mechanisms

Turbulent non-premixed combustion of gaseous fuels is of importance for many technical applications, especially for the steel and refractory industry. Accurate turbulent flow and temperature fields are of major importance in order to predict details on the concentration fields. The performances of the GRI-Mech 3.0 and the Jones and Lindstedt mechanisms are compared. Detailed chemistry is included with the GRI-Mech 3.0 and J-L kinetic mechanisms in combination with the laminar flamelet combustion model. The combustion system selected for this comparison is a confined non-premixed methane flame surrounded by co-flowing air The simulation results are compared with experimental data of Lewis and Smoot （2001）.

Utilizing neural networks to supplant chemical kinetics tabulation through mass conservation and weighting of species depletion

Artificial Neural Networks(ANNs)have emerged as a powerful tool in combustion simulations to replace memory-intensive tabulation of integrated chemical kinetics.Complex reaction mechanisms,however,present a challenge for standard ANN approaches as modeling multiple species typically suffers from inaccurate predictions on minor species.This paper presents a novel ANN approach which can be applied on complex reaction mechanisms in tabular data form,and only involves training a single ANN for a complete reaction mechanism.The approach incorporates a network architecture that automatically conserves mass and employs a particular loss weighting based on species depletion.Both modifications are used to improve the overall ANN performance and individual prediction accuracies,especially for minor species mass fractions.To validate its effectiveness,the approach is compared to standard ANNs in terms of performance and ANN complexity.Four distinct reaction mechanisms(H_(2),C_(7)H_(16),C_(12)H_(26),OME_(34))are used as a test cases,and results demonstrate that considerable improvements can be achieved by applying both modifications.

A data-driven reduced-order model for stiff chemical kinetics using dynamics-informed training

A data-based reduced-order model(ROM)is developed to accelerate the time integration of stiff chemically reacting systems by effectively removing the stiffness arising from a wide spectrum of chemical time scales.Specifically,the objective of this work is to develop a ROM that acts as a non-stiff surrogate model for the time evolution of the thermochemical state vector(temperature and species mass fractions)during an otherwise highly stiff and nonlinear ignition process.The model follows an encode-forecast-decode strategy that combines a nonlinear autoencoder(AE)for dimensionality reduction(encode and decode steps)with a neural ordinary differential equation(NODE)for modeling the dynamical system in the AE-provided latent space(forecasting step).By means of detailed timescale analysis by leveraging the dynamical system Jacobians,this work shows how data-based projection operators provided by autoencoders can inherently construct the latent spaces by removing unnecessary fast timescales,even more effectively than physics-based counterparts based on an eigenvalue analysis.A key finding is that the most significant degree of stiffness reduction is achieved through an end-to-end training strategy,where both AE and neural ODE parameters are optimized simultaneously,allowing the discovered latent space to be dynamics-informed.In addition to end-to-end training,this work highlights the vital contribution of AE nonlinearity in the stiffness reduction task.For the prediction of homogeneous ignition phenomena for H2-air and C2H4-air mixtures,the proposed ROM achieves several ordersof-magnitude increase in the integration time step size when compared to(a)a baseline CVODE solver for the full-chemical system,(b)statistical technique–principal component analysis(PCA),and(c)computational singular perturbation(CSP),a vetted physics-based stiffness-reducing modeling framework.

Nanotechnology combining photoacoustic kinetics and chemical kinetics for thrombosis diagnosis and treatment

Thrombotic disease is a major problem that endangers human health. At present, MRI and CT are commonly used clinically to diagnose thrombosis, and thrombolytic drugs are used for treatment), but the diagnosis time is lagging, the utilization of drugs is low, and the resulting systemic toxicity problems such as side effects lead to poor treatment effects. Nanotechnology combining photoacoustic dynamics and chemical dynamics has shown great application value in tumor targeting, diagnosis, detection and treatment. It has also become a new direction in the diagnosis and treatment of thrombotic diseases, and has created new applications in the field of nanomaterials. This review summarizes the new progress of this combination in the diagnosis and treatment of thrombotic diseases according to the differences in the construction of the nanotherapy system, at the same time, we put forward some new problems and prospects for the integration of thrombosis diagnosis and treatment.

Comparison of Invariant Manifolds for Model Reduction in Chemical Kinetics

A modern approach to model reduction in chemical kinetics is often based on the notion of slow invariant manifold.The goal of this paper is to give a comparison of various methods of construction of slow invariant manifolds using a simple Michaelis-Menten catalytic reaction.We explore a recently introduced Method of Invariant Grids(MIG)for iteratively solving the invariance equation.Various initial approximations for the grid are considered such as Quasi Equilibrium Manifold,Spectral Quasi Equilibrium Manifold,Intrinsic Low Dimensional Manifold and Symmetric Entropic Intrinsic Low Dimensional Manifold.Slow invariant manifold was also computed using the Computational Singular Perturbation(CSP)method.A comparison between MIG and CSP is also reported.

EFFECTIVE SOLUTION METHOD OF CHEMICAL REACTION KINETICS WITH DIFFUSE

The time integration method with four-order accuracy, self-starting and implicit for the diffuse chemical reaction kinetics equation or the transient instantaneous temperature filed equation was presented. The examples show that both accuracy and stability are better than Runge-Kutta method with four-order. The coefficients of the equation are stored with sparse matrix pattern, so an algorithm is presented which combines a compact storage scheme with reduced computation cost. The computation of the competitive and consecutive reaction in the rotating packed bed, taken as examples, shows that the method is effective.

Rebuilding the theory of isotope fractionation for evaporation of silicate melts under vacuum condition

Isotope eff ects are pivotal in understanding silicate melt evaporation and planetary accretion processes.Based on the Hertz-Knudsen equation,the current theory often fails to predict observed isotope fractionations of laboratory experiments due to its oversimplified assumptions.Here,we point out that the Hertz-Knudsen-equation-based theory is incomplete for silicate melt evaporation cases and can only be used for situations where the vaporized species is identical to the one in the melt.We propose a new model designed for silicate melt evaporation under vacuum.Our model considers multiple steps including mass transfer,chemical reaction,and nucleation.Our derivations reveal a kinetic isotopic fractionation factor(KIFF orα)αour model=[m(^(1)species)/m(^(2)species)]^(0.5),where m(species)is the mass of the reactant of reaction/nucleation-limiting step or species of diffusion-limiting step and superscript 1 and 2 represent light and heavy isotopes,respectively.This model can eff ectively reproduce most reported KIFFs of laboratory experiments for various elements,i.e.,Mg,Si,K,Rb,Fe,Ca,and Ti.And,the KIFF-mixing model referring that an overall rate of evaporation can be determined by two steps jointly can account for the eff ects of low P_(H2)pressure,composition,and temperature.In addition,we find that chemical reactions,diffusion,and nucleation can control the overall rate of evaporation of silicate melts by using the fitting slope in ln(−ln f)versus ln(t).Notably,our model allows for the theoretical calculations of parameters like activation energy(E_(a)),providing a novel approach to studying compositional and environmental eff ects on evaporation processes,and shedding light on the formation and evolution of the proto-solar and Earth-Moon systems.

Kinetics and fractionation of hydrogen isotopes during gas formation from representative functional groups

A gold tube simulation device was used to study the cleavage of representative compounds into gas.The goal of this study is to investigate hydrogen isotope composition change of gaseous hydrocarbons during maturity.Gas chromatography and isotopic analyses were conducted to determine how the yield of natural gas components and their hydrogen isotopic composition were related to experimental temperature and heating rate.A chemical kinetic model for the generation of each component of the natural gas and for the hydrogen isotopic fractionation was established and calibrated based on the results.Results indicate that the hydrogen isotopic fractionation during the evolution of various gas-forming organic materials can be satisfactorily described by chemical kinetic models.During regular methane generation,the reactions at low-activation-energy region had a greater contribution than the high-activation-energy region.While the reactions with high-activation-energy region had greater contribution of deuterium-rich methane.Compared with carbon isotope fractionation,this results in a greater hydrogen isotopic fractionation,which is more sensitive to changes in maturity.This study lays a foundation for further investigations of genesis and maturity of natural gas provided by hydrogen isotopic fractionation.It also provides fundamental knowledge for investigating the filling history of natural gas reservoir and for identifying.

Theoretical estimation of sonochemical yield in bubble cluster in acoustic field

In order to learn more about the physical phenomena occurring in cloud cavitation,the nonlinear dynamics of a spherical cluster of cavitation bubbles and cavitation bubbles in cluster in an acoustic field excited by a square pressure wave are numerically investigated by considering viscosity,surface tension,and the weak compressibility of the liquid.The theoretical prediction of the yield of oxidants produced inside bubbles during the strong collapse stage of cavitation bubbles is also investigated.The effects of acoustic frequency,acoustic pressure amplitude,and the number of bubbles in cluster on bubble temperature and the quantity of oxidants produced inside bubbles are analyzed.The results show that the change of acoustic frequency,acoustic pressure amplitude,and the number of bubbles in cluster have an effect not only on temperature and the quantity of oxidants inside the bubble,but also on the degradation types of pollutants,which provides a guidance in improving the sonochemical degradation of organic pollutants.

Reaction mechanism and kinetics of pressurized pyrolysis of Chinese oil shale in the presence of water

A study of reaction mechanisms and chemical kinetics of pressurized pyrolysis of Chinese Liushuhe oil shale in the presence of water were conducted using an autoclave for simulating and modeling in-situ underground thermal degradation.It was found that the oil shale was first pyrolyzed to form pyrobitumen,shale oil,shale gas and residue,then the pyrobitumen was further pyrolyzed to form more shale oil,shale gas,and residue.It means that there are two consecutive and parallel reactions.With increasing temperature,the pyrobitumen yield,as intermediate,first reached a maximum,then decreased to approximately zero.The kinetics results show that both these reactions are first order.The activation energy of pyrobitumen formation from oil shale is lower than that of shale oil formation from pyrobitumen.

Pyrolysis and combustion kinetics of lycopodium particles in thermogravimetric analysis

Biomass is a kind of renewable energy which is used increasingly in different types of combustion systems or in the production of fuels like bio-oil. Lycopodium is a cellulosic particle, with good combustion properties, of which microscopic images show that these particles have spherical shapes with identical diameters of 31 μm. The measured density of these particles is 1.0779 g/cm2. Lycopodium particles contain 64.06% carbon, 25.56% oxygen, 8.55% hydrogen and 1.83% nitrogen, and no sulfur. Thermogravimetric analysis in the nitrogen environment indicates that the maximum of particle mass reduction occurs in the temperature range of 250-550 ℃ where the maximum mass reduction in the DTG diagrams also occurs in. In the oxygen environment, an additional peak can also be observed in the temperature range of 500-600 ℃, which points to solid phase combustion and ignition temperature of lycopodium particles. The kinetics of reactions is determined by curve fitting and minimization of error.

Chemical Analysis of NO_x Removal Under Different Reduced Electric Fields

This work presents a chemical kinetic analysis of different species involved in nitrogen-oxygen mixed gas induced by stationary corona discharge at room temperature and atmospheric pressure.This study takes into account twenty different chemical species participating in one hundred and seventy selected chemical reactions.The reaction rate coefficients are taken from the literature,and the density is analyzed by the continuity equation without the diffusion term.A large number of investigations considered the removal of NOx showing the effects of N,O and O3 radicals.The aim of the present simulation is to complete these studies by analysing various plasma species under different reduced electric fields in the range of 100-200 Td（1 Td=10-21 V·m^2）.In particular,we analyze the time evolution of depopulation（10^-9-10^-3s）of NOx.We have found that the depopulation rate of NO and NO2 is substantially affected by the rise of reduced electric field as it grows from 100 Td to 200 Td.This allows us to ascertain the important role played by the reduced electric field.

Chemical Kinetic Aspects of Solid State Reaction Producing Wollastonite from Rice Husk Silica and Limestone

An industrial mineral wollastonite (CaSiO3) was produced under solid state conditions from rice husk silica and limestone. Reaction was carried out at 900'C to 1300'C for 1 h. The product batches were subjected to XRD and chemical analysis techniques specific for wollastonite. Mole fractions of different product batches were calculated on the basis of accumulated data to study the kinetics. Specific rate constants and reaction rate were also found out. Various probable models of mechanism for reaction were considered and testified with the laid down criterion for suggesting the suitable one. The resulting data were treated with Arrhenius equation as well and activation energy was calculated--therefrom. In addition to finding it's value from the slope of Arrhenius curve, an alternate method was also applied for this purpose. Both of the values were observed to be comparable. The activation energy required for performed reaction was found to be almost one third of that reported for synthesizing CaSiO3 by using quartz. This referred to the economical preparation of wollastonite by using rice husk as a source of silica instead of quartz.

Mechanism and Kinetics Analysis of NO/SO_2/N_2/O_2 Dissociation Reactions in Non-Thermal Plasma

The kinetics mechanism of the dissociation reactions in a NO/SO2/N2/O2 system was investigated in consideration of energetic electrons＇ impacts on a non-thermal plasma. A model was derived from the Boltzmann equation and molecule collision theory to predict the dissociation reaction rate coefficients. Upon comparison with available literature, the model was confirmed to be acceptably accurate in general. Several reaction rate coefficients of the NO/SO2/N2/O2 dissociation system were derived according to the Arrhenius formula. The activation energies of each plasma reaction were calculated by quantum chemistry methods. The relation between the dissociation reaction rate coefficient and electron temperature was established to describe the importance of each reaction and to predict relevant processes of gaseous chemical reactions. The sensitivity of the mechanism of NO/SO2/N2/O2 dissociation reaction in a non-thermal plasma was also analysed.

Reaction kinetics of isopropyl palmitate synthesis

In this study, the kinetics of isopropyl palmitate synthesis including the reaction mechanism was studied based on the two-step noncatalytic method. The liquid-phase diffusion effect on the reaction process was eliminated by adjusting the stirring rate. The results showed that the two-step reaction followed a tetrahedral mechanism and conformed to second-order reaction kinetics. Nucleophilic attack on the carbonyl carbon afforded an intermediate, containing a tetrahedral carbon center. The intermediate ultimately decomposed by elimination of the leaving group, affording isopropyl palmitate. The experimental data were analyzed at different temperatures by the integral method. The kinetic equations of the each step were deduced, and the activation energy and frequency factor were obtained. Experiments were performed to verify the feasibility of kinetic equations, and the result showed that the kinetic equations were reliable. This study could be very signi ficant to both industrial application and determining the continuous production of isopropyl palmitate.

OPTIMIZATION OF A REDUCED CHEMICAL KINETIC MODEL FOR HCCI ENGINE SIMULATIONS BY MICRO-GENETIC ALGORITHM

A reduced chemical kinetic model （44 species and 72 reactions） for the homogeneous charge compression ignition （HCCI） combustion of n-heptane was optimized to improve its autoignition predictions under different engine operating conditions. The seven kinetic parameters of the optimized model were determined by using the combination of a micro-genetic algorithm optimization methodology and the SENKIN program of CHEMKIN chemical kinetics software package. The optimization was performed within the range of equivalence ratios 0.2-1.2, initial temperature 310- 375 K and initial pressure 0, 1-0.3 MPa, The engine simulations show that the optimized model agrees better with the detailed chemical kinetic model （544 species and 2 446 reactions） than the original model does.