Kinetic models of natural gas combustion in an internal combustion engine

In this study, combustion of methane was simulated using four kinetic models of methane in CHEMKIN 4.1.1 for 0-D closed internal combustion (IC) engine reactor. Two detailed (GRIMECH3.0 & UBC MECH2.0) and two reduced (One step & Four steps) models were examined for various IC engine designs. The detailed models (GRIMECH3.0, & UBC MECH2.0) and 4-step models successfully predicted the combustion while global model was unable to predict any combustion reaction. This study illustrated that the detailed model sh...     

Kinetic model for laser-assisted reactions

A bimolecular expression has been developed for the prediction of reactive rate constants and cross sections in non-resonant laser fields. The result is a function of the laser power density, the electronic transition moment, the spectral detuning and the parameters which define the internuclear potential. The final form is based on a phenomenological model and is the result of treating the reaction as a unimolecular process. Available data are discussed in terms of a van der Waals potential and are correlated as a function of the long-range attraction. Agreement with published results is very good. The model is used to make predictions of branching ratios in several systems and a discussion of the molecular properties requisite to successful experiments is presented.     

Improving effect of boron carbide on the combustion and thermal oxidation characteristics of amorphous boron

Boron carbide (B₄C) is one of the main products from the primary combustion of boron (B)-based propellants and has a significant influence on the secondary combustion of B. To systematically evaluate its effects on the secondary combustion of B, mixtures of B₄C and B in different mass ratios were prepared. To study the ignition temperatures and combustion flames of the samples, a xenon lamp ignition experimental system and a flame shape test system were designed, respectively. A thermogravimetry–differential scanning calorimetry–Fourier transform infrared spectroscopy combined thermal analysis system was used to study the thermal oxidation characteristics and analyze the gaseous products of the samples. The results indicate that B₄C reduces the heat absorption at the beginning of the ignition, but subsequently prevents the rapid rise of sample temperature. During the stable combustion stage, the maximum flame length under optical density 10⁻⁴ (OD4) filter was 20.4 mm, and the maximum flame length under 580 nm + OD4 filters (represents the combustion of B element) was 16.7 mm. The samples contained a small amount of HBO₂ and H₃BO₃, which led to slight mass loss during the low temperature section of the thermal oxidation process. During the high temperature section, the oxidation of B and B₄C caused considerable mass gain. The gaseous products of the thermal oxidation process include CO₂, CO, and H₂O. In general, the B content of 60% was the most beneficial to decrease the oxidation temperature, increase the combustion intensity, and improve the heat-releasing ability of the samples.

     

Ignition and combustion characteristics of compound of magnesium and boron

Compound of magnesium and boron (MB) is promising to be the ideal substitute of amorphous boron which is usually used as the raw material of boron-based fuel-rich propellants. In this study, the physical characteristics of MB and amorphous boron were studied by the scanning electron microscope, X-ray diffraction and X-ray photoelectron spectroscopy. The thermal reaction characteristics and the ignition and combustion characteristics were investigated through TG/DSC experiments and laser ignition experiments. The experimental results show that the MB particle is much more regular than amorphous boron, which favors for the preparation of boron-based fuel-rich propellants. Magnesium exists in the form of elementary substance, and boron oxide is produced during the preparation of MB which results in the longer ignition delay time of MB. The content of magnesium and the pressure have effects on the MB combustion performance. Although the combustion of magnesium can provide much heat for the combustion of boron, MB with moderate content of magnesium shows the best combustion performance. On the contrast, the ignition delay time of MB is independent on the content of magnesium and the pressure.     

Kinetic model for reactivity in quaternary water-in-oil microemulsions

A study was carried out on the nitrosation of piperazine (PIP) and N-methylbenzylamine (MeBzAm) by N-methyl-N-nitroso-p-toluenesulfonamide (MNTS) in quaternary microemulsions of tetradecyltrimethylammonium bromide (TTABr)/isooctane/alcohol/water, varying the nature and the concentration of the following alcohols: 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol and 1-decanol keeping the [1-alcohol]/[TTABr] = 4 relationship constant. In addition a study was carried out on the influence of the alcohol concentration, working with molar relationships [1-hexanol]/[TTABr]=3, 4 and 5. On the basis of the molar volumes of the alcohol and surfactant and the concentration of alcohol at the interface it was possible to calculate the change in its volume with as varying compositions of the microemulsion. In order to interpret the experimental results a kinetic model was devised which takes into account the distribution of the reactants between the different pseudophases and the change in the volume of the interface. The rate constants at the interface of the microemulsion are lower than in pure water and are independent of the nature of the alcohol used as a cosurfactant and the molar relationship [alcohol]/[TTABr]. This independence indicates that the main role of the cosurfactant is to increase the volume of the interface with the consequent dilution of the reactants.     

Kinetic study of the pyrolysis and combustion of tomato plant

A kinetic study of the thermal decomposition of tomato plant has been carried out under different conditions by TG and TG–MS. A total of 24 experiments were performed in a nitrogen atmosphere (pyrolysis runs) and also in an oxidative atmosphere with two different oxygen concentrations (10% and 20% oxygen in nitrogen). Dynamic runs and dynamic + isothermal runs have been carried out to obtain many data of decomposition under different operating conditions.A scheme of five independent reactions for pseudocomponents has been proposed for the pyrolysis process, although only three fractions have probed to be significant, comparing the weight fractions of volatiles evolved with the hemicellulose, cellulose and lignin content of the plant. For the combustion runs, four new reactions have been added: two competitive oxidation reactions for the cellulose and lignin, and two combustion reactions of the carbonaceous residue obtained from pyrolysis. The kinetic parametres have been calculated by integration of the differential equations and minimizing the differences between the experimental and calculated values. It is important to emphasize that the same set of parameters has been proposed for the pyrolysis and combustion runs, and which do not depend on either the heating rate in dynamic runs or whether the run is carried out in a dynamic or isothermal mode. The influence of the oxygen pressure has been also discussed.     

Kinetic model for supercritical water gasification of algae

The article reports the first quantitative kinetics model for supercritical water gasification (SCWG) of real biomass (algae) that describes the formation of the individual gaseous products. The phenomenological model is based on a set of reaction pathways that includes two types of compounds being intermediate between the algal biomass and the final gaseous products. To best correlate the experimental gas yields obtained at 450, 500 and 550 °C, the model allowed one type of intermediate to react to gases more quickly than the other type of intermediate. The model parameters indicate that gas yields increase with temperature because higher temperatures favor production of the more easily gasified intermediate and the production of gas at the expense of char. The model can accurately predict the qualitative influence of the biomass loading and water density on the gas yields. Sensitivity analysis and reaction rate analysis indicate that steam reforming of intermediates is an important source of H(2), whereas direct decomposition of the intermediate species is the main source of CO, CO(2) and CH(4).     

煤粉物化特性对燃烧后灰颗粒物的影响

以三种煤粉在沉降炉中做燃烧实验,用Andersen粒子撞击器分离并捕集燃烧后的灰颗粒物,借助于压汞仪、扫描电镜及能谱、ICP-AES等对煤粉及分级颗粒物进行检测,研究煤粉物化特性对灰颗粒物的粒径分布、形貌、组成、痕量元素的富集等特性的影响。结果表明,煤粉孔结构、组分的赋存方式及含量等影响其破碎行为及组分迁移、转化的过程...     

预测混合煤燃烧性能的数学模型

用热重分析法研究了单种煤的DTG和TG曲线特征，建立了预测混合煤燃烧性能的数学模型。结果表明，各单种煤的DTG曲线呈单峰，峰值温度tmax与其燃料比F的对数呈线性相关关系，tmax=68.86 ln（F）+512.2 （℃）。由组成混合煤的单种煤的燃料比F可推断出混合煤的DTG曲线特征，从而预测混合煤的燃烧性能。如果混合煤的煤质指标满足标准煤的煤质指标要求，则当Fmax/Fmin≤3.20时，混合煤的燃烧性能好；当3.205.71时，混合煤的燃烧性能较差。     

Kinetic model of star-branched polycondensation

A kinetic model was developed for the whole process of star-branched polycondensation of AB type monomers with a multifunctional core, RA_f. The evolution of molecular weight distribution and other molecular parameters during reaction were estimated in terms of the derived expressions. The molecular weight distribution first becomes broader with increasing reaction extent of B groups and the functionality of RA_f, but suddenly turns to be markedly narrower than the Schulz-Flory distribution when the polycondensation approaches completion.     

Kinetic model for an esterification process coupled by pervaporation

A basic kinetic model of an esterification process coupled by pervaporation and a new method for measuring the model parameter had been established. Various effects on the shift of chemical equilibrium of esterification were taken into consideration in this kinetic model. The simulation results of this model coincided well with the experimental results.     

Kinetic model for micellar catalysed hydrolysis of esters-biomolecular reactions

The cationic micelles of cetyltrimethylammonium bromide, cetyldibenzylammonium chloride and cetylpyridinium chloride stabilize the tetrahedral intermediate formed in the hydrolysis of carboxylic esters (e.g.p-nitrophenylbenzoate) to a greater extent, preferring a mechnism, than the anionic intermediate formed in the hydrolysis ofm-nitrophenyl-N-N-diphenylphosphorodiamidate, which prefers aE _1cB mechanism. The co-operative index,n ₁, calculated for these reactions is greater than 1 indicating that the substrate induced micellation is responsible for the observed catalysis. Based on the present kinetic model for a bimolecular reaction the fraction of substrate and nucleophile bound to the micelle have been calculated. The above results suggest that reaction occurs between the substrate solubilised into the micelle and the nucleophile residing at the Stern layer rather than at the micelle-water interface. The equilibrium constant, and critical micelle concentration evaluated using the present model are in agreement with the values obtained by using earlier models, suggesting a method of evaluating these parameters from kinetic data only.     

Kinetic analysis of DSC and thermogravimetric data on combustion of lignite

Thermal analysis increasingly being used to obtain kinetic data relating to sample decomposition. This work involves a comparative study of several methods used to analyse DSC and TG/DTG data obtained on the oxidation of Beypazari lignite. A general computer program was developed and the methods are compared with regard to their accuracy and the ease of interpretation of the kinetics of thermal decomposition. For this study, the ratio method was regarded as the preferred method, because it permits the estimation of reaction order, activation energy and Arrhenius constant simultaneously from a single experiment.The experimental part of this research was supported in part by NATO-SFS Project TU-Energy II. The authors express their appreciation to the NATO-SFS program for providing financial support for this project.     

Kinetic model for methanol conversion over Mg-ZSM-5 zeolite

The catalytic conversion of methanol to olefins over ZSM-5 zeolite modified by ion exchange with Mg exhibits an autocatalytic character. On this basis an overall kinetic model of the reaction was proposed which allowed the determination of rate constants and apparent activation energy.

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ZSM-5, Mg, . , .

     

Kinetic model of electrochemical nucleation

The process of electrochemical nucleation is analyzed in terms of stochastic formation of clusters of different size over the electrode surface. It is shown that the ground equation of the atomistic theory of nucleation can be derived without resort to the thermodynamic approach, in particular, the concept of the nucleus energy and its dependence on the nucleus size.     

Kinetic model of liquid B2O3 gasification in a hydrocarbon combustion environment: I. Heterogeneous surface reactions

As part of an ongoing program to model hydrocarbon assisted boron combustion, a kinetic model has been developed to describe gasification of the ubiquitous boron oxide coating that inhibits particulate boron ignition. This model includes homogeneous gas phase oxidation reactions, multi-component gas phase diffusion, heterogeneous surface reactions, and oxide vaporization. The kinetic processes are treated using a generalized kinetics code, with embeded sensitivity analysis, for the combustion of a one-dimensional (particle radius), spherical particle. This article presents the heterogeneous surface reactions used to describe oxide gasification and presents selected model results for a spherical boron oxide droplet which illustrate the dependence of the oxide gasification rates on the ambient temperature and particle diameter.     

A hybrid rheological model for particulate suspension in zeolite crystal growth

A hybrid constitutive model is developed to represent the thixotropic behavior of particulate suspension during zeolite crystallization from solution. This model is valid over the complete solid fraction range typical for such a process. It employs two internal variables, agglomeration and contiguity, to describe the degree to which the gel particles form short- and long-range networks. The contiguity is used to weigh the effects of hydrodynamic to chain-like network deformation on the suspension viscosity. Heterogeneous nucleation and surface reaction-controlled crystal growth are assumed to describe the evolution of microstructure and solid fraction of gel and crystals. Such a model successfully captures the thixotropic behavior of zeolite particulate suspension by comparison of the predictions with a set of experimental data.     

Kinetic model for the thermal rearrangement of cis- and trans-pinane

On the basis of pyrolysis experiments with cis-pinane ( 1a), trans-pinane ( 1b), beta-citronellene ( 2), and isocitronellene ( 3), rate constants and activation parameters for the thermal rearrangement of the title compounds were calculated. Combining these with experimental parameters (residence time) allows for the kinetic modeling of the thermal rearrangement of 1a, 1b, 2, and 3. The chosen model of competitive first-order reactions describes the thermal behavior of the title compounds in a very good manner over a wide temperature range.     

Detection of the first combustion limit in the heterophase branched chain oxidation of boron

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, p. 1704, July, 1989.